JP7294146B2 - Colored photosensitive resin composition, partition wall, organic electroluminescence device, image display device and lighting - Google Patents

Description

The present invention relates to a colored photosensitive resin composition used to form partition walls, and further includes partition walls made of the colored photosensitive resin composition, organic electroluminescent elements comprising the partition walls, and organic electroluminescent elements. It relates to an image display device and illumination.
The full contents of the specification, claims and abstract of Japanese Patent Application 2018-011096 filed with the Japan Patent Office on January 26, 2018, and the documents cited herein. All or part of the content of this document is hereby incorporated by reference and incorporated as the disclosure content of this specification.

Conventionally, organic electroluminescence elements included in organic electric field displays and organic electric field lighting have been formed by forming partitions (banks) on a substrate and then laminating various functional layers in the region surrounded by the partitions. manufactured. As a method for easily forming such partition walls, a method of forming them by a photolithography method using a photosensitive resin composition is known.

In addition, as a method of laminating various functional layers in the region surrounded by the partition walls, first, an ink containing a material constituting the functional layers is prepared, and then the prepared ink is injected into the region surrounded by the partition walls. It is known how to Among these methods, the inkjet method is often adopted because it is easy to accurately inject a predetermined amount of ink into a predetermined location.

Furthermore, when the functional layer is formed using ink, the partition wall should be made ink-repellent ( liquid repellency) may be required.
In recent years, partition walls are required to have various properties other than ink repellency, and various photosensitive resin compositions have been developed. For example, from the viewpoint of improving contrast and preventing reflection, there is a demand for colored partition walls. Patent Document 1 describes a negative photosensitive resin composition in which a black organic pigment and a specific alkali-soluble resin are used, and the acid value of the solid content of the composition is set within a specific range to achieve fine line patterns and fine contacts. It is described that it is possible to form partition walls having holes together, that the contained black organic pigment has good dispersibility in an alkaline developer used for development, and that storage stability is good.

WO2013/069789

In recent years, the development of colored barrier ribs has been vigorously pursued. It is necessary to inject a large amount of dilute ink into the partition wall, which naturally requires a thick colored partition wall. Since the light-shielding property required for the colored barrier ribs is per total film thickness, the light-shielding property per unit film thickness tends to be low in thick barrier ribs, that is, the content of the coloring agent tends to be low.
Such a thick-film colored partition wall is also required to exhibit sufficient ink repellency in order to prevent inks from mixing between adjacent regions. Furthermore, the functional layer in the area surrounded by the barrier ribs becomes the pixels of the image display device. Since the layer cannot be formed and causes light emission unevenness, it is also required that the edge portion of the partition has good linearity.

As a result of investigation by the present inventors, when the content of the colorant is reduced in the colored photosensitive resin composition described in Patent Document 1, although the linearity is good, it is difficult to obtain sufficient ink repellency. was found.
Accordingly, an object of the present invention is to provide a colored photosensitive resin composition having high ink repellency and good linearity.
Another object of the present invention is to provide partition walls formed using the colored photosensitive resin composition, an organic electroluminescence device comprising the partition walls, an image display device and illumination comprising the organic electroluminescence device.

As a result of intensive studies by the present inventors, the above problem was solved by using a specific alkali-soluble resin in combination with a colored photosensitive resin composition containing a liquid-repellent agent, even when the content of the coloring agent is small. I found that it can be done, and came to complete the present invention.
That is, the gist of the present invention is as follows.

[1] A colored photosensitive resin composition containing (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, (D) a liquid-repellent agent, and (E) a coloring agent. hand,
The content of the (E) colorant is 20% by mass or less in the total solid content of the colored photosensitive resin composition,
The colored photosensitive resin composition, wherein the (C) alkali-soluble resin contains (c1) an acrylic copolymer resin having an ethylenically unsaturated group in a side chain, and (c2) an epoxy (meth)acrylate resin. thing.

[2] The colored photosensitive resin composition according to [1], wherein the (c1) acrylic copolymer resin having an ethylenically unsaturated group in the side chain has a partial structure represented by the following general formula (I): .

(In formula (I), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. * represents a bond.)

[3] The (c2) epoxy (meth)acrylate resin has a partial structure represented by the following general formula (ii): an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (i): [1] or [2], including at least one selected from the group consisting of epoxy (meth)acrylate resins and epoxy (meth)acrylate resins having a partial structure represented by the following general formula (iii): A colored photosensitive resin composition.

(In formula (i), R ^a represents a hydrogen atom or a methyl group, and R ^b represents a divalent hydrocarbon group which may have a substituent. The benzene ring in formula (i) is further It may be substituted with any substituent. * represents a bond.)

(In formula (ii), each R ^c independently represents a hydrogen atom or a methyl group. R ^d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * represents a bond. .)

(In formula (iii), R ^e represents a hydrogen atom or a methyl group, γ is a single bond, —CO—, an optionally substituted alkylene group, or an optionally substituted 2 represents a valent cyclic hydrocarbon group.The benzene ring in formula (iii) may be further substituted with an optional substituent.* represents a bond.)

[4] The colored photosensitive resin composition according to any one of [1] to [3], wherein the liquid repellent agent (D) has a cross-linking group.
[5] The colored photosensitive resin composition according to any one of [1] to [4], further comprising a chain transfer agent.

[6] Partition walls composed of the colored photosensitive resin composition according to any one of [1] to [5].
[7] An organic electroluminescence device comprising the partition according to [6].
[8] An image display device comprising the organic electroluminescence device of [7].
[9] Lighting including the organic electroluminescent device according to [7].

The present invention can provide a colored photosensitive resin composition having high ink repellency and good linearity.

The present invention will be described in detail below. It should be noted that the following description is an example of the embodiment of the present invention, and the present invention is not specified as long as it does not exceed the gist thereof.
In the present invention, "(meth)acrylic" means "acrylic and/or methacrylic", and "total solid content" refers to all components other than the solvent in the colored photosensitive resin composition. shall mean Furthermore, in the present invention, a numerical range represented by "-" means a range including the numerical values before and after "-" as lower and upper limits.
Further, in the present invention, the term "(co)polymer" means including both a single polymer (homopolymer) and a copolymer (copolymer), and "(acid) anhydride", "(anhydrous)...acid" is meant to include both acids and their anhydrides.
In the present invention, a partition wall material means a bank material, a wall material, and a wall material, and similarly, a partition wall means a bank, a wall, and a wall.
In the present invention, the weight average molecular weight refers to the polystyrene equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).

[1] Colored photosensitive resin composition The colored photosensitive resin composition of the present invention comprises (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, (D) a liquid repellent agent, and (E) a colored photosensitive resin composition containing a colorant, wherein the content of the (E) colorant is 20% by mass or less in the total solid content, and the (C) alkali-soluble resin is It is characterized by containing (c1) an acrylic copolymer resin having an ethylenically unsaturated group in a side chain and (c2) an epoxy (meth)acrylate resin. Further, if necessary, it may contain other components such as a solvent and a chain transfer agent.

In the present invention, the partition is, for example, for partitioning the functional layers (organic layer, light-emitting portion) in the active drive type organic electroluminescent device, and for configuring the functional layer in the partitioned region (pixel region). It is used to form pixels and the like including functional layers and partition walls by ejecting and drying the ink, which is the material of .

[1-1] Components and Composition of Colored Photosensitive Resin Composition Components constituting the colored photosensitive resin composition of the present invention and their composition will be described.
The colored photosensitive resin composition of the present invention contains (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, (D) a liquid repellent agent, and (E) a colorant. , and usually also a solvent.

[1-1-1] Component (A): Ethylenically Unsaturated Compound The colored photosensitive resin composition of the present invention contains (A) an ethylenically unsaturated compound. (A) It is considered that the inclusion of the ethylenically unsaturated compound results in high sensitivity.
The ethylenically unsaturated compound used here means a compound having one or more ethylenically unsaturated bonds in the molecule, and polymerizability, crosslinkability, and accompanying developing solutions for exposed and non-exposed areas It is preferable that the compound has two or more ethylenically unsaturated bonds in the molecule, and the unsaturated bond is derived from a (meth)acryloyloxy group. , that is, a (meth)acrylate compound is more preferable.

In the present invention, it is particularly desirable to use polyfunctional ethylenic monomers having two or more ethylenically unsaturated bonds in one molecule. The number of ethylenically unsaturated groups possessed by the polyfunctional ethylenic monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, and preferably 15. Below, more preferably 10 or less, still more preferably 8 or less, particularly preferably 7 or less. When the content is at least the above lower limit, the polymerizability tends to be improved and the sensitivity tends to be high, and when the content is at most the above upper limit, the developability tends to be better. The number of ethylenically unsaturated groups possessed by the polyfunctional ethylenic monomer is, for example, 2 to 15, preferably 2 to 10, more preferably 3 to 8, and even more preferably 5 to 7. .
Specific examples of ethylenically unsaturated compounds include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds. and esters obtained by an esterification reaction between a polyhydric hydroxy compound such as and an unsaturated carboxylic acid and a polybasic carboxylic acid.

Esters of the aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate, and methacrylic acid esters obtained by replacing the acrylates of these exemplary compounds with methacrylates Similarly, itaconate instead of itaconate, crotonate instead of clonate, maleate instead of maleate, and the like.

Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. etc.
Esters obtained by the esterification reaction of polyhydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids are not necessarily single substances, but are representative. Condensates of acrylic acid, phthalic acid and ethylene glycol; condensates of acrylic acid, maleic acid and diethylene glycol; condensates of methacrylic acid, terephthalic acid and pentaerythritol; acrylic acid, adipic acid, Examples include condensates of butanediol and glycerin.

Other examples of polyfunctional ethylenic monomers used in the present invention include a polyisocyanate compound and a hydroxyl group-containing (meth)acrylic acid ester or a polyisocyanate compound, a polyol and a hydroxyl group-containing (meth)acrylic acid ester. urethane (meth)acrylates such as those obtained; epoxy acrylates such as addition reaction products of polyepoxy compounds and hydroxyl group-containing (meth)acrylic acid esters or (meth)acrylic acid; acrylamides such as ethylenebisacrylamide; Allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate are useful.
Examples of the urethane (meth)acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U -10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B, UV -7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and the like.

Among these, it is preferable to use ester (meth)acrylates or urethane (meth)acrylates as the ethylenically unsaturated compound (A) from the viewpoint of an appropriate taper angle and sensitivity, and dipentaerythritol hexa(meth)acrylate. , dipentaerythritol penta(meth)acrylate, 2-tris(meth)acryloyloxymethylethyl phthalate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate. It is more preferable to use a basic acid anhydride adduct, a dibasic acid anhydride adduct of pentaerythritol tri(meth)acrylate, or the like.
These may be used individually by 1 type, and may use 2 or more types together.

In the present invention, the molecular weight of (A) the ethylenically unsaturated compound is not particularly limited, but from the viewpoint of sensitivity, ink repellency and taper angle, it is preferably 100 or more, more preferably 150 or more, and still more preferably 200 or more. More preferably 300 or more, particularly preferably 400 or more, most preferably 500 or more, preferably 1000 or less, more preferably 700 or less. (A) The molecular weight of the ethylenically unsaturated compound is, for example, 100 to 1000, preferably 150 to 700, more preferably 200 to 700, still more preferably 300 to 700, even more preferably 400 to 700, and 500 ~700 is particularly preferred.
The number of carbon atoms in (A) the ethylenically unsaturated compound is not particularly limited, but from the viewpoint of sensitivity, ink repellency, and taper angle, it is preferably 7 or more, more preferably 10 or more, still more preferably 15 or more, and still more preferably 15 or more. It is preferably 20 or more, particularly preferably 25 or more, preferably 50 or less, more preferably 40 or less, even more preferably 35 or less, particularly preferably 30 or less. (A) The number of carbon atoms in the ethylenically unsaturated compound is, for example, 7 to 50, preferably 10 to 40, more preferably 15 to 35, even more preferably 20 to 30, and even more preferably 25 to 30.
From the viewpoint of sensitivity, ink repellency, and taper angle, ester (meth)acrylates, epoxy (meth)acrylates, and urethane (meth)acrylates are preferred. Among them, pentaerythritol tetra (meth)acrylate and pentaerythritol tri(meth)acrylate dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate and other trifunctional or higher ester (meth)acrylates, 2,2,2-tris(meth)acryloyloxymethylethyl phthal Addition products of acid anhydrides to trifunctional or higher ester (meth)acrylates such as dibasic acid anhydride addition products of acids and dipentaerythritol penta(meth)acrylate improve sensitivity, ink repellency, and taper angle. is more preferable.

The content of (A) the ethylenically unsaturated compound in the colored photosensitive resin composition of the present invention is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass of the total solid content. % by mass or more, more preferably 15% by mass or more, usually 80% by mass or less, preferably 60% by mass or less, more preferably 40% by mass or less, and even more preferably 20% by mass or less. When it is at least the lower limit, the sensitivity and taper angle during exposure tend to be good, and when it is at most the upper limit, the developability tends to be good. The content of (A) the ethylenically unsaturated compound in the total solid content of the colored photosensitive resin composition is, for example, 1 to 80% by mass, preferably 5 to 60% by mass, and 10 to 40% by mass. More preferably, 15 to 20% by mass is even more preferable.

In addition, although the content ratio of (A) ethylenically unsaturated compound to 100 parts by mass of (C) alkali-soluble resin is not particularly limited, it is usually 1 part by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, More preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, usually 150 parts by mass or less, preferably 100 parts by mass or less, more preferably 70 parts by mass or less, even more preferably 50 parts by mass or less, particularly preferably It is preferably 30 parts by mass or less. When it is at least the above lower limit, sensitivity during exposure tends to be good and the taper angle tends to be good, and when it is at most the above upper limit, developability tends to be good. (C) The content ratio of the ethylenically unsaturated compound (A) to 100 parts by mass of the alkali-soluble resin is, for example, 1 to 150 parts by mass, preferably 5 to 100 parts by mass, more preferably 10 to 70 parts by mass. , more preferably 15 to 50 parts by mass, and even more preferably 20 to 30 parts by mass.

[1-1-2] Component (B); Photopolymerization Initiator The colored photosensitive resin composition of the present invention contains (B) a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it is a compound that polymerizes the ethylenically unsaturated bond of the (A) ethylenically unsaturated compound by actinic rays, and a known photopolymerization initiator can be used. can be done.

In the colored photosensitive resin composition of the present invention, a photopolymerization initiator commonly used in this field can be used as (B) the photopolymerization initiator. Examples of such photopolymerization initiators include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; JP-A-2000-56118. Hexaarylbiimidazole derivatives described in JP-A-10-39503; halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, and N-aryl-α-amino acids such as N-phenylglycine described in JP-A-10-39503. , N-aryl-α-amino acid salts, radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; Examples thereof include oxime ester compounds described in publications and the like.

Specifically, for example, titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluoro phenyl), dicyclopentadienyltitanium bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyltitanium bis(2,4,6-trifluorophenyl), dicyclopentadienyltitanium bis(2,4,6-trifluorophenyl) (2,6-difluorophenyl), dicyclopentadienyl titanium di(2,4-difluorophenyl), di(methylcyclopentadienyl) titanium bis(2,3,4,5,6-pentafluorophenyl) , di(methylcyclopentadienyl) titanium bis(2,6-difluorophenyl), dicyclopentadienyl titanium [2,6-di-fluoro-3-(pyro-1-yl)-phenyl] and the like. be done.

Further, biimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer and 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole. dimer, 2-(2′-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2′-methoxyphenyl)-4,5-diphenylimidazole dimer, (4′-methoxyphenyl )-4,5-diphenylimidazole dimer and the like.

Further, halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'- benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2′-(6″-benzofuryl)vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.

Further, halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis( trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl) -s-triazine and the like.

Further, α-aminoalkylphenone derivatives include 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4- morpholinophenyl)-butanone-1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate -, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4 -diethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone and the like.

As a photopolymerization initiator, oxime ester compounds are particularly effective in terms of sensitivity and plate-making properties. Such an oxime ester compound having excellent sensitivity is useful. Oxime ester compounds have a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals, so they are highly sensitive even in small amounts and are stable against thermal reactions. and it is possible to obtain a highly sensitive colored photosensitive resin composition in a small amount.

Examples of oxime ester compounds include compounds represented by the following general formula (IV).

In formula (IV) above, R ^21a represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aromatic ring group.
R ^21b represents any substituent containing an aromatic ring.
R ^22a represents an optionally substituted alkanoyl group or an optionally substituted aryloyl group.
n represents an integer of 0 or 1;

Although the number of carbon atoms in the alkyl group in R ^21a is not particularly limited, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, from the viewpoint of solvent solubility and sensitivity. is. Specific examples of alkyl groups include methyl, ethyl, propyl, cyclopentylethyl, and propyl groups.
Examples of substituents that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl. group, N-acetyl-N-acetoxyamino group, etc., and from the viewpoint of ease of synthesis, it is preferably unsubstituted.

The aromatic ring group for R ^21a includes aromatic hydrocarbon ring groups and aromatic heterocyclic groups. Although the number of carbon atoms in the aromatic ring group is not particularly limited, it is preferably 5 or more from the viewpoint of solubility in the colored photosensitive resin composition. From the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and even more preferably 12 or less.

Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, a furyl group, and the like. Among these, from the viewpoint of developability, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
Examples of the substituent that the aromatic ring group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and groups in which these substituents are linked. From the viewpoint of compatibility, an alkyl group, an alkoxy group, or a group in which these are linked is preferable, and a linked alkoxy group is more preferable.
Among these, from the viewpoint of sensitivity, R ^21a is preferably an optionally substituted alkyl group or an optionally substituted aromatic ring group.

R ^21b is preferably an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group or an optionally substituted diphenylsulfide group. Among these, an optionally substituted carbazolyl group is preferable from the viewpoint of sensitivity.

The number of carbon atoms in the alkanoyl group in R ^22a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably It is 10 or less, more preferably 5 or less. Specific examples of alkanoyl groups include an acetyl group, an ethyloyl group, a propanoyl group and a butanoyl group.
Examples of substituents that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, and an amide group. is preferred.

The number of carbon atoms in the aryloyl group in R ^22a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less. Specific examples of the aryloyl group include a benzoyl group and a naphthoyl group.
Examples of substituents that the aryloyl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, an alkyl group, etc. From the viewpoint of ease of synthesis, unsubstituted groups are preferred. .
Among these, from the viewpoint of sensitivity, R ^22a is preferably an optionally substituted alkanoyl group, more preferably an unsubstituted alkanoyl group, and even more preferably an acetyl group.

A photoinitiator may be used individually by 1 type, or may be used in combination of 2 or more types.
For the purpose of increasing sensitivity, the photopolymerization initiator can be blended with a sensitizing dye and a polymerization accelerator depending on the wavelength of the image exposure light source, if necessary. Examples of sensitizing dyes include the xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, JP-A-3-239703 and JP-A-5-289335. 3-Ketocoumarin compounds described in JP-A-3-239703, JP-A-5-289335, and pyrromethenes described in JP-A-6-19240. Dyes, other, Japanese Patent Laid-Open No. 47-2528, Japanese Patent Laid-Open No. 54-155292, Japanese Patent Publication No. 45-37377, Japanese Patent Laid-Open No. 48-84183, Japanese Patent JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-69 , JP-A-57-168088, JP-A-5-107761, JP-A-5-210240, JP-A-4-288818 having a dialkylaminobenzene skeleton described in A dye etc. can be mentioned.

Preferred among these sensitizing dyes are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone , benzophenone compounds such as 3,4-diaminobenzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5 ] benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-oxazole, 2-(p-dimethylaminophenyl ) benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)- 1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine and p-dialkylaminophenyl group-containing compounds such as (p-diethylaminophenyl)pyrimidine. Among these, the most preferred is 4,4'-dialkylaminobenzophenone.
The sensitizing dyes may also be used singly or in combination of two or more.

Examples of the polymerization accelerator include aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, and aliphatic amines such as n-butylamine and N-methyldiethanolamine. A polymerization accelerator may be used individually by 1 type, or may be used in combination of 2 or more type.

Although the content of (B) the photopolymerization initiator in the colored photosensitive resin composition of the present invention is not particularly limited, the total solid content of the colored photosensitive resin composition is usually 0.01% by mass or more, preferably 0 .1% by mass or more, more preferably 1% by mass or more, more preferably 2% by mass or more, particularly preferably 3% by mass or more, usually 25% by mass or less, preferably 20% by mass or less, more preferably 15% by mass % or less, more preferably 10 mass % or less, even more preferably 7 mass % or less, and particularly preferably 5 mass % or less. When it is at least the above lower limit, a coating film is formed without causing film reduction during development, and there is a tendency for sufficient ink repellency to occur. tends to be easier. The content of the photopolymerization initiator (B) in the total solid content of the colored photosensitive resin composition is, for example, 0.01 to 25% by mass, preferably 0.01 to 20% by mass, and 0.1 ~15% by mass is more preferred, 1 to 10% by mass is more preferred, 2 to 7% by mass is even more preferred, and 3 to 5% by mass is particularly preferred.

Further, the blending ratio of (B) the photopolymerization initiator to (A) the ethylenically unsaturated compound in the colored photosensitive resin composition is 1 part by mass with respect to 100 parts by mass of the (A) ethylenically unsaturated compound. 5 parts by mass or more is preferable, 10 parts by mass or more is more preferable, 15 parts by mass or more is even more preferable, 20 parts by mass or more is particularly preferable, and 200 parts by mass or less is preferable, and 100 parts by mass or less is preferable. is more preferable, 50 parts by mass or less is more preferable, and 30 parts by mass or less is particularly preferable. When the lower limit value or more is used, appropriate sensitivity tends to be obtained, and when the upper limit value or less is used, a desired pattern shape tends to be easily formed. (A) The blending ratio of the photopolymerization initiator (B) to 100 parts by mass of the ethylenically unsaturated compound is, for example, 1 to 200 parts by mass, preferably 5 to 100 parts by mass, more preferably 10 to 100 parts by mass. It is preferably 15 to 50 parts by mass, and even more preferably 20 to 30 parts by mass.

Moreover, it is preferable to use a chain transfer agent in combination with the photopolymerization initiator. Examples of chain transfer agents include mercapto group-containing compounds, carbon tetrachloride, and the like, and it is more preferable to use compounds having a mercapto group because they tend to have a high chain transfer effect. This is probably because bond cleavage is likely to occur due to the small SH bond energy, and hydrogen abstraction reaction and chain transfer reaction are likely to occur. Effective in improving sensitivity and surface curability.

Mercapto group-containing compounds include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H)-quinazoline, β- Mercapto group-containing compounds having an aromatic ring such as mercaptonaphthalene and 1,4-dimethylmercaptobenzene; hexanedithiol, decanedithiol, butanediol bis(3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol Bis(3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tristhioglycolate, trishydroxyethyl tristhiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), butanediol bis (3-mercaptobutyrate), ethylene glycol bis (3-mercaptobutyrate), trimethylolpropane tris (3- mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine Aliphatic mercapto group-containing compounds such as -2,4,6(1H,3H,5H)-trione, particularly compounds having a plurality of mercapto groups.

Among these, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred among the mercapto group-containing compounds having an aromatic ring, and among the aliphatic mercapto group-containing compounds, trimethylolpropane tris (3- mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate) rate), pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H) - Trione is preferred.

In terms of sensitivity, aliphatic mercapto group-containing compounds are preferred, and specifically, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and pentaerythritol. tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5- Tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is preferred, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate) is more preferred.
These various things can be used individually by 1 type, or in mixture of 2 or more types.

Among these, from the viewpoint of increasing the taper angle, one or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole, and a photopolymerization initiator are combined. , is suitable for use as a photoinitiator system. For example, 2-mercaptobenzothiazole may be used, 2-mercaptobenzimidazole may be used, or 2-mercaptobenzothiazole and 2-mercaptobenzimidazole may be used in combination.
From the viewpoint of sensitivity, it is preferable to use one or more selected from the group consisting of pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate). Furthermore, from the viewpoint of sensitivity, one or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole, and pentaerythritol tetrakis (3-mercaptopropionate), It is preferable to use one or more selected from the group consisting of pentaerythritol tetrakis(3-mercaptobutyrate) in combination with a photopolymerization initiator.

Although the content of the chain transfer agent in the colored photosensitive resin composition of the present invention is not particularly limited, it is usually 0.01% by mass or more, preferably 0.1% by mass, based on the total solid content of the colored photosensitive resin composition. Above, more preferably 0.5% by mass or more, still more preferably 0.8% by mass or more, usually 5% by mass or less, preferably 4% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass % or less. The sensitivity tends to increase when the concentration is equal to or higher than the lower limit, and the desired pattern tends to be easily formed when the concentration is equal to or lower than the upper limit. The content of the chain transfer agent in the total solid content of the colored photosensitive resin composition is, for example, 0.01 to 5% by mass, preferably 0.1 to 4% by mass, and 0.5 to 3% by mass. is more preferred, and 0.8 to 2% by mass is even more preferred.

Further, the content ratio of the chain transfer agent to the photopolymerization initiator (B) in the colored photosensitive resin composition is preferably 5 parts by weight or more, and 10 parts by weight with respect to 100 parts by weight of the photopolymerization initiator (B). More preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, preferably 500 parts by mass or less, more preferably 300 parts by mass or less, further preferably 100 parts by mass or less, 50 parts by mass The following are particularly preferred. The lower limit value or more tends to increase the sensitivity, and the upper limit value or less tends to facilitate formation of a desired pattern. (B) The content ratio of the chain transfer agent to 100 parts by mass of the photopolymerization initiator is, for example, 5 to 500 parts by mass, preferably 10 to 300 parts by mass, more preferably 15 to 100 parts by mass, and 20 to 50 parts by mass. Parts by mass are more preferred.

[1-1-3] Component (C): Alkali-Soluble Resin The colored photosensitive resin composition of the present invention contains (C) an alkali-soluble resin. In the present invention, the alkali-soluble resin is not particularly limited as long as it can be developed with a developer, but the developer is preferably an alkaline developer, so it is preferable to use a resin containing a carboxyl group or a hydroxyl group. A carboxyl group-containing resin is preferable from the viewpoint of being excellent in
In addition, an alkali-soluble resin having an ethylenically unsaturated group is used for the reason that it is possible to obtain partition walls with an appropriate taper angle, suppress the outflow of the liquid repellent agent due to development or thermal melting of the partition walls, and maintain the ink repellency. preferable.

The (C) alkali-soluble resin of the colored photosensitive resin composition of the present invention is (c1) an acrylic copolymer resin having an ethylenically unsaturated group in a side chain (hereinafter sometimes referred to as "(c1) acrylic copolymer resin"). There is.). (c1) The acrylic copolymer resin having an ethylenically unsaturated group in the side chain has a flexible skeleton, so that the radicals generated during exposure have a high degree of freedom within the film, and the loss of radicals due to oxygen on the film surface. It is thought that the activity can be suppressed, the curability of the film surface increases, and the liquid repellent agent can be easily captured in the vicinity of the surface. Furthermore, it is believed that the side chain ethylenically unsaturated groups can sufficiently capture the liquid repellent agent oriented on the film surface. The liquid-repellent agent sufficiently trapped on the film surface increases ink repellency, suppresses adhesion of ink to partition walls and mixing of ink injected between adjacent regions, and the organic electroluminescent element is uniform in each pixel. It is thought that it will come to emit light at
On the other hand, (C) alkali-soluble resin of the colored photosensitive resin composition of the present invention further includes (c2) epoxy (meth)acrylate resin. (c2) Epoxy (meth)acrylate resin has a rigid skeleton, so that the adhesion to the substrate does not become too high, the residue at the edge of the partition is suppressed, and the skirting is also suppressed at the edge of the partition. is considered to be linear. It is thought that if the linearity of the edge portions of the partition walls can be improved in this way, the functional layer can be uniformly formed in the regions surrounded by the partition walls, and uneven light emission can be suppressed. Furthermore, since resistance unevenness can be suppressed, it is thought that current concentration, which causes a deterioration in life, is less likely to occur.
Therefore, in the colored photosensitive resin composition of the present invention, as the (C) alkali-soluble resin, both (c1) an acrylic copolymer resin having an ethylenically unsaturated group in the side chain and (c2) an epoxy (meth)acrylate resin By including, it is considered that both ink repellency and linearity can be compatible.

The (c1) acrylic copolymer resin having an ethylenically unsaturated group in the side chain is described in detail below.

[(c1) acrylic copolymer resin having an ethylenically unsaturated group in the side chain]
(c1) Acrylic copolymer resin has an ethylenically unsaturated group in a side chain. By having an ethylenically unsaturated group, it is considered that photocuring by exposure occurs to form a stronger film, and the liquid-repellent agent is less likely to flow out during development.

(Partial structure represented by general formula (I))
(c1) The partial structure containing a side chain having an ethylenically unsaturated group, which the acrylic copolymer resin has, is not particularly limited. It preferably has a partial structure represented by (I).

In formula (I), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. * represents a bond.

Among the partial structures represented by the formula (I), the partial structures represented by the following general formula (I') are preferable from the viewpoint of sensitivity and alkali developability.

In formula (I'), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. R ^X represents a hydrogen atom or a polybasic acid residue.

A polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylenetetrahydrophthalic acid. One or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid can be mentioned.
Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred from the viewpoint of patterning properties, and more preferred. is tetrahydrophthalic acid, biphenyltetracarboxylic acid.

(c1) The content of the partial structure represented by the general formula (I) contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but is preferably 10 mol% or more, and 20 mol. % or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, particularly preferably 50 mol% or more, most preferably 65 mol% or more, and preferably 95 mol% or less, 90 mol % or less, more preferably 85 mol % or less, even more preferably 80 mol % or less, particularly preferably 75 mol % or less, most preferably 70 mol % or less. When the content is at least the lower limit, the ink repellency tends to be improved. (c1) The content of the partial structure represented by the general formula (I) contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is, for example, 10 to 95 mol%, and 20 ~85 mol% is preferred, 30 to 80 mol% is more preferred, 40 to 75 mol% is even more preferred, and 50 to 70 mol% is even more preferred.

(c1) The content of the partial structure represented by the general formula (I') contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but is preferably 10 mol% or more, 20 mol% or more is more preferable, 30 mol% or more is still more preferable, 40 mol% or more is still more preferable, 50 mol% or more is particularly preferable, 65 mol% or more is most preferable, and 95 mol% or less is preferable, It is more preferably 90 mol % or less, still more preferably 85 mol % or less, still more preferably 80 mol % or less, particularly preferably 75 mol % or less, most preferably 70 mol % or less. When the content is at least the above lower limit, alkali development tends to be facilitated, and when the content is at most the above upper limit, development adhesion tends to be ensured. (c1) The content of the partial structure represented by the general formula (I′) contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is, for example, 10 to 95 mol%, 20 to 80 mol % is preferred, 30 to 75 mol % is more preferred, 40 to 70 mol % is even more preferred, and 50 to 65 mol % is even more preferred.

(Partial structure represented by general formula (II))
(c1) When the acrylic copolymer resin having an ethylenically unsaturated group in the side chain contains the partial structure represented by the general formula (I), the other partial structure is not particularly limited, but From a viewpoint, it is also preferable to have a partial structure represented by the following general formula (II), for example.

In the above formula (II), ^R3 represents a hydrogen atom or a methyl group, ^R4 represents an optionally substituted alkyl group, an optionally substituted aryl group (aromatic ring group) , or represents an optionally substituted alkenyl group.

( ^R4 )
In formula (II), R ⁴ represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkenyl group.
Alkyl groups for R ⁴ include linear, branched and cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, particularly preferably 8 or more, and preferably 20 or less, It is more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. When the content is equal to or higher than the lower limit, the film strength tends to increase and the development adhesion tends to be improved.

Specific examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentanyl, and dodecanyl groups. Among these, from the viewpoint of developability, a dicyclopentanyl group or a dodecanyl group is preferred, and a dicyclopentanyl group is more preferred.
Examples of substituents that the alkyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxyl group. , an acryloyl group, a methacryloyl group, etc., and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

The aryl group (aromatic ring group) for R ⁴ includes a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The carbon number is preferably 6 or more, preferably 24 or less, more preferably 22 or less, even more preferably 20 or less, and particularly preferably 18 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.
The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene groups such as ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
Further, the aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. , imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furfuran ring, thienofuran ring, benzoisoxazole ring, benzoiso thiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring groups such as Among these, from the viewpoint of developability, a benzene ring group or a naphthalene ring group is preferred, and a benzene ring group is more preferred.
Examples of substituents that the aryl group may have include methyl, ethyl, propyl, methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligo An ethylene glycol group, a phenyl group, a carboxyl group and the like can be mentioned, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

Alkenyl groups for R ⁴ include linear, branched and cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, and even more preferably 16 or less. , 14 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

Specific examples of alkenyl groups include a vinyl group, an allyl group, a 2-propen-2-yl group, a 2-buten-1-yl group, a 3-buten-1-yl group, a 2-penten-1-yl group, 3-penten-2-yl group, hexenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group and the like. Among these, a vinyl group or an allyl group is preferred, and a vinyl group is more preferred, from the viewpoint of developability.

Examples of substituents that the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. etc., and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

Thus, R ⁴ represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkenyl group. From the viewpoint of developability and film strength, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable.

(c1) The content of the partial structure represented by the general formula (II) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but is preferably 1 mol% or more, and 5 mol% or more. is more preferably 10 mol% or more, particularly preferably 20 mol% or more, preferably 70 mol% or less, more preferably 60 mol% or less, further preferably 50 mol% or less, and 40 mol% or less Especially preferred. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

(Partial structure represented by general formula (III))
(c1) When the acrylic copolymer resin contains a partial structure represented by the general formula (I), another partial structure to be included is represented by the following general formula (III) from the viewpoint of heat resistance and film strength. Preferably, substructures are included.

In the above formula (III), R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or a substituted represents an optionally substituted alkynyl group, a hydroxyl group, a carboxyl group, a halogen atom, an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkylsulfide group. t represents an integer of 0 to 5;

( ^R6 )
In the above formula (III), R ⁶ is an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxyl group, or a carboxyl group. , a halogen atom, an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkylsulfide group.
Alkyl groups for R ⁶ include linear, branched and cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, preferably 20 or less, more preferably 18 or less, It is more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

Specific examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentanyl, and dodecanyl groups. Among these, from the viewpoint of developability and film strength, a dicyclopentanyl group or a dodecanyl group is preferred, and a dicyclopentanyl group is more preferred.
Examples of substituents that the alkyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxyl group. , an acryloyl group, a methacryloyl group, etc., and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

Alkenyl groups for R ⁶ include linear, branched and cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, and even more preferably 16 or less. , 14 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

Specific examples of alkenyl groups include a vinyl group, an allyl group, a 2-propen-2-yl group, a 2-buten-1-yl group, a 3-buten-1-yl group, a 2-penten-1-yl group, 3-penten-2-yl group, hexenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group and the like. Among these, a vinyl group or an allyl group is preferred, and a vinyl group is more preferred, from the viewpoint of developability.

Examples of substituents that the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. etc., and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

Alkynyl groups for R ⁶ include linear, branched and cyclic alkynyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, and even more preferably 16 or less. , 14 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

Specific examples of alkynyl groups include 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1, 4-pentadien-3-yl group, 1,3-pentadien-5-yl group, 1-hexyn-6-yl group, and the like.

Examples of substituents that the alkynyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. etc., and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

The halogen atom for R ⁶ includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among these, a fluorine atom is preferable from the viewpoint of ink repellency.

Alkoxy groups for R ⁶ include linear, branched and cyclic alkoxy groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and even more preferably 14 or less. , 12 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

Specific examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, and isobutoxy groups.

Examples of substituents that the alkoxy group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. , an acryloyl group, a methacryloyl group, etc., and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

The alkylsulfide group for R ⁶ includes linear, branched and cyclic alkylsulfide groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and even more preferably 14 or less. , 12 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

Specific examples of alkylsulfide groups include methylsulfide, ethylsulfide, propylsulfide, and butylsulfide groups. Among these, a methylsulfide group or an ethylsulfide group is preferable from the viewpoint of developability.

Substituents that the alkyl group in the alkylsulfide group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group, acryloyl group, methacryloyl group, etc., and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferred.

Thus, R ⁶ is an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxyl group, a carboxyl group, a halogen represents an atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or an optionally substituted alkyl sulfide group. preferable.

In formula (III), t represents an integer of 0 to 5, and t is preferably 0 from the viewpoint of ease of production.

(c1) The content of the partial structure represented by the general formula (III) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but is preferably 1 mol% or more, and 2 mol% or more. is more preferably 5 mol% or more, particularly preferably 8 mol% or more, preferably 50 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, and 20 mol% or less Especially preferred. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced. (c1) The content of the partial structure represented by the general formula (III) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is, for example, 1 to 50 mol%, and 2 to 40 mol. %, more preferably 5 to 30 mol %, even more preferably 8 to 20 mol %.

(Partial structure represented by general formula (IV))
(c1) When the acrylic copolymer resin having an ethylenically unsaturated group in the side chain has a partial structure represented by the general formula (I), the other partial structure may be the following general formula from the viewpoint of developability: It is also preferred to have a partial structure represented by (IV).

In formula (IV) above, ^R7 represents a hydrogen atom or a methyl group.

(c1) The content of the partial structure represented by the general formula (IV) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but is preferably 5 mol% or more, It is more preferably 10 mol % or more, more preferably 20 mol % or more, more preferably 80 mol % or less, more preferably 70 mol % or less, and even more preferably 60 mol % or less. When the content is equal to or higher than the lower limit, the developability tends to be improved, and when the content is equal to or lower than the upper limit, the development adhesion tends to be improved. (c1) The content of the partial structure represented by the general formula (IV) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is, for example, 5 to 80 mol%, 10 to 70 mol % is preferred, and 20 to 60 mol % is more preferred.

On the other hand, the acid value of the (c1) acrylic copolymer resin is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, still more preferably 40 mgKOH/g or more, and even more preferably 50 mgKOH/g or more. , 60 mgKOH/g or more is particularly preferable, 150 mgKOH/g or less is preferable, 140 mgKOH/g or less is more preferable, 130 mgKOH/g or less is still more preferable, and 120 mgKOH/g or less is even more preferable. When the content is equal to or higher than the lower limit, the developability tends to be improved, and when the content is equal to or lower than the upper limit, the development adhesion tends to be improved. The acid value of the acrylic copolymer resin (c1) is, for example, 10 to 150 mgKOH/g, preferably 30 to 140 mgKOH/g, more preferably 50 to 130 mgKOH/g, and even more preferably 60 to 120 mgKOH/g.

(c1) The weight average molecular weight (Mw) of the acrylic copolymer resin is not particularly limited, but is usually 1000 or more, preferably 2000 or more, more preferably 4000 or more, still more preferably 6000 or more, still more preferably 7000 or more, and particularly preferably is 8,000 or more, and is usually 30,000 or less, preferably 20,000 or less, more preferably 15,000 or less, and still more preferably 10,000 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the amount of residue tends to be reduced. (c1) The weight average molecular weight (Mw) of the acrylic copolymer resin is, for example, 1000 to 30000, preferably 2000 to 20000, more preferably 4000 to 15000, more preferably 6000 to 15000, more preferably 7000 to 10000. More preferably, 8,000 to 10,000 is particularly preferred.

The content of (c1) acrylic copolymer resin contained in (C) alkali-soluble resin is not particularly limited, but is preferably 10% by mass or more, more preferably 30% by mass or more, further preferably 50% by mass or more, and 70% by mass. % or more is particularly preferable, 95 mass % or less is preferable, 90 mass % or less is more preferable, and 85 mass % or less is even more preferable. When the content is at least the lower limit, the ink repellency tends to be improved. The content of (c1) acrylic copolymer resin contained in (C) alkali-soluble resin is, for example, 10 to 95% by mass, preferably 30 to 90% by mass, more preferably 50 to 85% by mass, and 70% by mass. ~85% by mass is more preferred.

The content of (c1) acrylic copolymer resin is preferably 10% by mass or more, and 30% by mass or more, based on the total mass of (c1) acrylic copolymer resin and (c2) epoxy (meth)acrylate resin. is more preferably 50% by mass or more, particularly preferably 70% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less. When the content is at least the lower limit, the ink repellency tends to be improved. The content of (c1) acrylic copolymer resin relative to the total mass of (c1) acrylic copolymer resin and (c2) epoxy (meth)acrylate resin is, for example, 10 to 95% by mass, and 30 to 90% by mass. is preferred, 50 to 85 mass % is more preferred, and 70 to 85 mass % is even more preferred.

Specific examples of the (c1) acrylic copolymer resin are described in detail below. The (c1) acrylic copolymer resin includes, for example, (c1-a) a carboxyl group copolymer having an ethylenically unsaturated group in a side chain.

(c1-a) carboxyl group-containing copolymer having ethylenically unsaturated groups in side chains (c1-a-1) copolymerization of unsaturated carboxylic acid and compound containing two or more ethylenically unsaturated groups Coalescing As a carboxyl group-containing copolymer having an ethylenically unsaturated group in the side chain, for example, allyl (meth) acrylate, 3-allyloxy-2-hydroxypropyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) Compounds containing two or more ethylenically unsaturated groups such as acrylates, methallyl (meth)acrylate, N,N-diallyl (meth)acrylamide, or vinyl (meth)acrylate, 1-chlorovinyl (meth)acrylate, 2-Phenyl vinyl (meth) acrylate, 1-propenyl (meth) acrylate, vinyl crotonate, a compound containing two or more ethylenically unsaturated groups such as vinyl (meth) acrylamide, and (meth) acrylic acid The ratio of the unsaturated carboxylic acid, or further unsaturated carboxylic acid ester, etc. to the total of the former compound containing two or more ethylenically unsaturated groups is 10 to 90 mol%, preferably 30 to 80 mol%. Examples thereof include copolymers obtained by copolymerizing to a certain degree.

The acid value of this copolymer is preferably 30 to 250 mgKOH/g from the viewpoint of developability, and the weight average molecular weight (Mw) is preferably 1000 to 30000 from the viewpoint of development solubility.

(c1-a-2) Epoxy Group-Containing Unsaturated Compound-Modified Carboxyl Group-Containing Copolymer Further, as a carboxyl group-containing copolymer having an ethylenically unsaturated group in a side chain, for example, a carboxyl group-containing copolymer, A modified carboxyl group-containing copolymer modified by reacting an epoxy group-containing unsaturated compound to add the epoxy group of the epoxy group-containing unsaturated compound to a part of the carboxyl groups of the carboxyl group-containing copolymer can be mentioned.
As the carboxyl group-containing copolymer, from the viewpoint of patterning properties, a carboxyl group-containing copolymer (meth)acrylate-(meth)acrylic acid copolymer, and styrene-(meth)acrylate-(meth)acrylic Acid copolymers and the like are preferred.
In addition, the epoxy group-containing unsaturated compounds include allyl glycidyl ether, glycidyl (meth)acrylate, α-ethylglycidyl (meth)acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, monoalkyl mono itaconate, Aliphatic epoxy group-containing unsaturated compounds such as glycidyl esters, monoalkyl monoglycidyl fumarate, monoalkyl monoglycidyl maleate, and 3,4-epoxycyclohexylmethyl (meth)acrylate, 2,3-epoxycyclopentylmethyl Alicyclic epoxy group-containing unsaturated compounds such as (meth)acrylate and 7,8-epoxy[tricyclo[5.2.1.0]dec-2-yl]oxyethyl (meth)acrylate can be mentioned.
These epoxy group-containing unsaturated compounds can be obtained by reacting 5 to 90 mol %, preferably about 30 to 70 mol %, of the carboxyl groups of the carboxyl group-containing copolymer. In addition, reaction can be implemented by a well-known method.

The acid value of this epoxy group-containing unsaturated compound-modified carboxyl group-containing copolymer is preferably 30 to 250 mgKOH/g from the viewpoint of developability, and the weight average molecular weight ( Mw) is preferably between 1,000 and 300,000.

(c1-a-3) Unsaturated carboxylic acid-modified epoxy group- and carboxyl group-containing (co)polymer Further, as a carboxyl group-containing copolymer having an ethylenically unsaturated group in the side chain, for example, (meth)acrylic acid Unsaturated carboxylic acid such as the above-mentioned aliphatic epoxy group-containing unsaturated compound or alicyclic epoxy group-containing unsaturated compound, or further unsaturated carboxylic acid ester, styrene, etc., the former carboxyl group-containing unsaturated compound The copolymer obtained by copolymerizing so that the proportion of the total is 10 to 90 mol%, preferably about 30 to 80 mol%, is reacted with an unsaturated carboxylic acid such as (meth)acrylic acid. Examples thereof include modified epoxy group- and carboxyl group-containing copolymers modified by adding carboxyl groups of unsaturated carboxylic acids to the epoxy groups of the copolymer.

The acid value of this unsaturated carboxylic acid-modified epoxy group- and carboxyl group-containing copolymer is preferably 30 to 250 mgKOH/g from the viewpoint of developability, and from the viewpoint of developability and film strength, the weight average molecular weight (Mw) is preferably from 1,000 to 300,000.

(c1-a-4) acid-modified epoxy group-containing copolymer Further, as a carboxyl group-containing (co)polymer having an ethylenically unsaturated group in a side chain, an epoxy group-containing (meth)acrylate and an ethylenically unsaturated compound With respect to the copolymer, an ethylenically unsaturated monocarboxylic acid is added to at least a portion of the epoxy groups of the copolymer, and a polybasic acid (anhydride) is added to at least a portion of the hydroxyl groups generated by the addition. and an acid-modified epoxy group-containing (co)polymer obtained by adding.
Specifically, a copolymer of 5 to 99 mol% of an epoxy group-containing (meth)acrylate such as glycidyl (meth)acrylate and usually 1 to 95 mol% of an ethylenically unsaturated compound such as (meth)acrylic acid ester. To usually 10 to 100 mol% of the epoxy groups contained in the copolymer, an ethylenically unsaturated monocarboxylic acid is added, and usually 10 to 100 mol% of the hydroxyl groups generated when further added, a polybasic acid Acid-modified epoxy group-containing (co)polymers obtained by adding (anhydrides) can be mentioned.

Here, the copolymerization ratio of the epoxy group-containing (meth)acrylate in the copolymer is not particularly limited, but is usually 5 mol% or more, preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more. mol % or more, more preferably 40 mol % or more, particularly preferably 50 mol % or more, and usually 90 mol % or less, preferably 85 mol % or less, more preferably 80 mol % or less. When the content is at least the lower limit, the ink repellency tends to be improved. The copolymerization ratio of the epoxy group-containing (meth)acrylate in the copolymer is, for example, 5 to 90 mol%, preferably 10 to 90 mol%, more preferably 20 to 85 mol%, and 30 to 85 mol%. % is more preferred, 40 to 80 mol % is even more preferred, and 50 to 80 mol % is particularly preferred.
On the other hand, the copolymerization ratio of the ethylenically unsaturated compound in the copolymer is not particularly limited, but is usually 1 mol% or more, preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol%. Above, particularly preferably 30 mol% or more, usually 90 mol% or less, preferably 80 mol% or less, more preferably 70 mol% or less, still more preferably 60 mol% or less, particularly preferably 50 mol% or less . When the content is at least the lower limit, the film strength tends to improve, and when the content is at most the upper limit, ink repellency and developability tend to improve. The copolymerization ratio of the ethylenically unsaturated compound in the copolymer is, for example, 1 to 90 mol%, preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and 20 to 60 mol%. More preferably, 30 to 50 mol % is even more preferable.

Epoxy group-containing (meth)acrylates include aliphatic epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate and α-ethylglycidyl (meth)acrylate; 3,4-epoxycyclohexylmethyl (meth)acrylate; Alicyclic epoxy group-containing (meth)acrylates such as 3-epoxycyclopentylmethyl (meth)acrylate and 7,8-epoxy[tricyclo[5.2.1.0]dec-2-yl]oxyethyl (meth)acrylate mentioned.

Here, as the ethylenically unsaturated compound such as (meth)acrylic acid ester, for example, one or more mono(meth)acrylates having a partial structure represented by the following general formula (V) may be used. is preferred.

In formula (V), R ^1d to R ^4d each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ^5d and R ^6d each independently represent a hydrogen atom or a C 1 to 10 represents an alkyl group of Also, R ^5d and R ^6d may be linked to form a ring. The ring formed by combining R ^5d and R ^6d is preferably an aliphatic ring, may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.

The number of carbon atoms in the alkyl groups in R ^1d to R ^4d is usually 1 or more and usually 10 or less, preferably 8 or less, more preferably 5 or less. When the amount is not more than the above upper limit, there is a tendency that appropriate development solubility can be obtained.
Among these, from the viewpoint of solubility, R ^1d to R ^4d are preferably hydrogen atoms.

The number of carbon atoms in the alkyl group in R ^5d and R ^6d is usually 1 or more, and is usually 10 or less, preferably 8 or less, more preferably 5 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the film strength tends to be improved.
Among these, from the viewpoint of developing solubility, it is preferable that R ^5d and R ^6d are hydrogen atoms or that R ^5d and R ^6d are linked to form an aliphatic ring having 5 to 6 carbon atoms.

Among the formula (V), mono(meth)acrylates having a structure represented by the following formula (Va), (Vb), or (Vc) are preferred. By introducing these partial structures, it tends to be possible to increase the heat resistance and strength of the mono(meth)acrylate. One of these mono(meth)acrylates may be used, or two or more of them may be used in any combination and ratio.

As the mono(meth)acrylate having a partial structure represented by the formula (V), various known ones can be used. preferable.

In formula (VI), ^R7d represents a hydrogen atom or a methyl group, and ^R8d represents the partial structure of formula (V).

On the other hand, the ethylenically unsaturated compounds include ethylenically unsaturated compounds other than mono(meth)acrylates having a partial structure represented by the formula (V), such as styrene α-, o-, m-, styrenes such as p-alkyl, nitro, cyano, amide and ester derivatives; dienes such as butadiene, 2,3-dimethylbutadiene, isoprene and chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) ) n-propyl acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, Neopentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate , (meth)cyclohexyl acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, (meth)acrylic propargyl acid, phenyl (meth)acrylate, naphthyl (meth)acrylate, anthracenyl (meth)acrylate, anthraninonyl (meth)acrylate, piperonyl (meth)acrylate, salicyl (meth)acrylate, (meth)acrylate furyl acrylate, furfuryl (meth)acrylate, tetrahydrofuryl (meth)acrylate, pyranyl (meth)acrylate, benzyl (meth)acrylate, phenethyl (meth)acrylate, cresyl (meth)acrylate, (meth)acrylate 1,1,1-trifluoroethyl acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, perfluoro-iso-propyl (meth)acrylate, (meth)acrylate triphenylmethyl acrylate, cumyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. (Meth)acrylic acid esters; (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-dipropyl (meth)acrylic acid amides such as amide, (meth)acrylic acid N,N-di-iso-propylamide, (meth)acrylic acid anthracenylamide; (meth)acrylic acid anilide, (meth)acryloylnitrile, Vinyl compounds such as acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, and vinyl acetate; saturated dicarboxylic acid diesters; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide; radically polymerizable such as N-(meth)acryloylphthalimide Compounds are also included.

Among these, from the viewpoint of film strength, it is preferable to use at least one selected from the group consisting of styrene, benzyl (meth)acrylate, and monomaleimide as the ethylenically unsaturated compound. In this case, from the viewpoint of film strength and developability, the copolymerization ratio of at least one selected from the group consisting of styrene, benzyl (meth)acrylate and monomaleimide is usually 1 mol% or more, preferably 3 mol% or more. Also, it is usually 70 mol % or less, preferably 50 mol % or less, more preferably 30 mol % or less, and still more preferably 10 mol % or less.

As the ethylenically unsaturated monocarboxylic acid to be added to the epoxy group contained in the copolymer of the epoxy group-containing (meth)acrylate and the ethylenically unsaturated compound, a known one can be used. Therefore, (meth)acrylic acid is preferred. The amount of the ethylenically unsaturated monocarboxylic acid added to the epoxy groups contained in the copolymer is usually 10 mol% or more, preferably 30 mol% or more, more preferably 50 mol% or more of the epoxy groups contained in the copolymer. It is mol % or more, more preferably 70 mol % or more, and usually 100 mol % or less. By setting the addition ratio of the ethylenically unsaturated monocarboxylic acid to the above lower limit or more, there is a tendency that the curability can be enhanced. In addition, a well-known method can be employ|adopted as a method of adding an ethylenically unsaturated monocarboxylic acid to the said copolymer. The amount of the ethylenically unsaturated monocarboxylic acid added to the epoxy groups contained in the copolymer is, for example, 10 to 100 mol%, preferably 30 to 100 mol%, of the epoxy groups contained in the copolymer. , more preferably 50 to 100 mol %, more preferably 70 to 100 mol %.

The polybasic acid (anhydride) to be added to the hydroxyl group produced when the ethylenically unsaturated monocarboxylic acid is added to the copolymer is not particularly limited, and one known one may be used alone. , two or more of which may be used in any combination and ratio. By adding such a component, alkali solubility can be imparted to the copolymer.

The amount of polybasic acid (anhydride) to be added is usually 1 mol% or more, preferably 5 mol% or more, or more of the hydroxyl groups generated when the ethylenically unsaturated monocarboxylic acid is added to the copolymer. It is preferably 10 mol % or more, more preferably 30 mol % or more, even more preferably 50 mol % or more, and particularly preferably 60 mol % or more. Also, it is usually 100 mol % or less, preferably 90 mol % or less, more preferably 80 mol % or less, and still more preferably 70 mol % or less. When the content is equal to or higher than the lower limit, the developability tends to be improved, and when the content is equal to or lower than the upper limit, the film strength tends to be improved. As a method for adding a polybasic acid (anhydride) to a hydroxyl group generated when an ethylenically unsaturated monocarboxylic acid is added to the copolymer, a known method can be arbitrarily adopted. The amount of addition of the polybasic acid (anhydride) to the hydroxyl groups generated when the ethylenically unsaturated monocarboxylic acid is added to the copolymer is, for example, 1 to 100 mol%, and 5 to 90 mol. %, more preferably 10 to 80 mol %, still more preferably 30 to 80 mol %, even more preferably 50 to 70, particularly preferably 60 to 70.

Modified products of the above epoxy group-containing copolymers with ethylenically unsaturated monocarboxylic acids and polybasic acids (anhydrides) include glycidyl ( Photosensitivity can be further improved by adding a glycidyl ether compound having a meth)acrylate or an ethylenically unsaturated group. Developability can also be improved by adding a glycidyl ether compound having no ethylenically unsaturated groups to some of the carboxy groups formed after addition of the polybasic acid (anhydride). Furthermore, both of these may be added after polybasic acid (anhydride) addition.

Examples of the above acid-modified epoxy group-containing copolymer include resins described in JP-A-8-297366 and JP-A-2001-89533. In addition, the weight average molecular weight (Mw) of the modified product is not particularly limited, but is usually 3000 or more, preferably 5000 or more, and usually 100000 or less, preferably 50000 or less, more preferably 30000 or less, further preferably 20000 or less. , particularly preferably 15,000 or less. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced. The weight average molecular weight (Mw) of the modified product is, for example, 3,000 to 100,000, preferably 3,000 to 50,000, more preferably 5,000 to 30,000, still more preferably 5,000 to 20,000, and even more preferably 5,000 to 15,000.
Further, the molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] is preferably 2.0 to 5.0 from the viewpoint of curability.

The acid value of the acid-modified epoxy group-containing copolymer is not particularly limited, but is preferably 30 mgKOH/g or more, more preferably 40 mgKOH/g or more, still more preferably 50 mgKOH/g or more, and preferably 150 mgKOH/g or less. , 130 mgKOH/g or less is more preferable, 120 mgKOH/g or less is more preferable, 110 mgKOH/g or less is even more preferable, and 100 mgKOH/g or less is particularly preferable. When the content is equal to or higher than the lower limit, the developability tends to be improved, and when the content is equal to or lower than the upper limit, the film strength tends to be improved. The acid value of the acid-modified epoxy group-containing copolymer is, for example, 30 to 150 mgKOH/g, preferably 40 to 130 mgKOH/g, more preferably 40 to 120 mgKOH/g, further preferably 50 to 110 mgKOH/g, 50 to 100 mg KOH/g is even more preferred.

Next, the (c2) epoxy (meth)acrylate resin will be described in detail.

[(c2) epoxy (meth)acrylate resin]
(c2) Epoxy (meth)acrylate resin is obtained by adding an ethylenically unsaturated monocarboxylic acid or an ester compound to an epoxy resin, optionally reacting with an isocyanate group-containing compound, and then further reacting with a polybasic acid or its anhydride. It is a resin that has been For example, ring-opening addition of a carboxyl group of an unsaturated monocarboxylic acid to an epoxy group of an epoxy resin results in addition of an ethylenically unsaturated bond to the epoxy compound via an ester bond (--COO--), One carboxyl group of the polybasic acid anhydride is added to the hydroxyl group generated at that time. Moreover, when adding a polybasic acid anhydride, the thing added by adding a polyhydric alcohol simultaneously is mentioned.

The epoxy (meth)acrylate resin (c2) also includes a resin obtained by reacting the carboxyl group of the resin obtained by the above reaction with a compound having a reactive functional group.
Thus, the epoxy (meth)acrylate resin has substantially no epoxy group due to its chemical structure, and is not limited to "(meth)acrylate", but an epoxy compound (epoxy resin) is a raw material. and "(meth)acrylate" is a typical example, so it is named in this way according to common practice.

Here, the epoxy resin includes a raw material compound before forming a resin by thermosetting, and the epoxy resin can be appropriately selected and used from known epoxy resins. As the epoxy resin, a compound obtained by reacting a phenolic compound and epihalohydrin can be used. The phenolic compound is preferably a compound having a divalent or higher phenolic hydroxyl group, and may be a monomer or a polymer.
Specifically, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolak epoxy resin, biphenyl novolak epoxy resin, trisphenol epoxy resin, polymerization of phenol and dicyclopentane. Epoxy resin, dihydroxylfluorene-type epoxy resin, dihydroxylalkyleneoxylfluorene-type epoxy resin, 9,9-bis(4′-hydroxyphenyl)diglycidyl ether of fluorene, 1,1-bis(4′-hydroxy phenyl)adamantane, and the like, and those having an aromatic ring in the main chain can be preferably used.

Among them, from the viewpoint of high cured film strength, bisphenol A epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, 9,9-bis(4′-hydroxyphenyl)fluorene. A diglycidyl etherate is preferred, and a bisphenol A epoxy resin is more preferred.
Specific examples of epoxy resins include, for example, bisphenol A type epoxy resins (e.g., Mitsubishi Chemical Corporation's "jER (registered trademark, hereinafter the same) 828", "jER1001", "jER1002", "jER1004", etc.), Epoxy resin obtained by reaction of alcoholic hydroxyl group of bisphenol A type epoxy resin and epichlorohydrin (for example, "NER-1302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent: 323, softening point: 76°C)), bisphenol F type resin (for example, , Mitsubishi Chemical Corporation "jER807", "EP-4001", "EP-4002", "EP-4004", etc.), epoxy resin obtained by reaction of alcoholic hydroxyl group of bisphenol F type epoxy resin and epichlorohydrin (e.g. , Nippon Kayaku Co., Ltd. "NER-7406" (epoxy equivalent 350, softening point 66 ° C.)), bisphenol S type epoxy resin, biphenyl glycidyl ether (e.g., Mitsubishi Chemical Co., Ltd. "YX-4000"), phenol novolac type epoxy resin (for example, "EPPN-201" manufactured by Nippon Kayaku, "EP-152" and "EP-154" manufactured by Mitsubishi Chemical, "DEN-438" manufactured by Dow Chemical), (o, m, p-) cresol novolak-type epoxy resin (for example, Nippon Kayaku Co., Ltd. "EOCN (registered trademark, hereinafter the same)-102S", "EOCN-1020", "EOCN-104S"), triglycidyl isocyanurate (For example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Industries, Ltd.), trisphenolmethane type epoxy resin (for example, "EPPN (registered trademark) -501" and "EPPN-502" manufactured by Nippon Kayaku Co., Ltd.) ”, “EPPN-503”), alicyclic epoxy resin (“Celoxide (registered trademark, hereinafter the same) 2021P” and “Celoxide EHPE” manufactured by Daicel), phenolic resin obtained by the reaction of dicyclopentadiene and phenol, glycidyl Epoxy resins (for example, "EXA-7200" manufactured by DIC Corporation, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), epoxy resins represented by the following general formulas (C1) to (C4), etc. are suitable. can be used for Specifically, "XD-1000" manufactured by Nippon Kayaku Co., Ltd. as the epoxy resin represented by the following general formula (C1), and "XD-1000" manufactured by Nippon Kayaku Co., Ltd. as the epoxy resin represented by the following general formula (C2) NC-3000", and "ESF-300" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. as an epoxy resin represented by the following general formula (C4).

In the above general formula (C1), a is an average value and represents a number from 0 to 10. Each R ¹¹¹ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. Plural R ¹¹¹ in one molecule may be the same or different.

In the above general formula (C2), b is an average value and represents a number from 0 to 10. Each R ¹²¹ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. Plural R ¹²¹ in one molecule may be the same or different.

In general formula (C3) above, X represents a linking group represented by general formula (C3-1) or (C3-2) below. However, it contains one or more adamantane structures in its molecular structure. c represents 2 or 3;

In the above general formulas (C3-1) and (C3-2), R ¹³¹ to R ¹³⁴ and R ¹³⁵ to R ¹³⁷ are each independently an optionally substituted adamantyl group, a hydrogen atom, a substituent or an optionally substituted phenyl group. * represents a bond.

In general formula (C4) above, p and q each independently represent an integer of 0 to 4, and R ¹⁴¹ and R ¹⁴² each independently represent an alkyl group having 1 to 4 carbon atoms or a halogen atom. R ¹⁴³ and R ¹⁴⁴ each independently represent an alkylene group having 1 to 4 carbon atoms. x and y each independently represent an integer of 0 or more.

Among these, it is preferable to use an epoxy resin represented by any one of general formulas (C1) to (C4).

Examples of ethylenically unsaturated monocarboxylic acids include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, pentaerythritol tri(meth)acrylate succinic anhydride adduct, penta Erythritol tri(meth)acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta(meth)acrylate succinic anhydride adduct, dipentaerythritol penta(meth)acrylate phthalic anhydride adduct, dipentaerythritol penta(meth)acrylate tetrahydro Examples include phthalic anhydride adducts and reaction products of (meth)acrylic acid and ε-caprolactone. Among them, (meth)acrylic acid is preferable from the viewpoint of sensitivity.

Examples of polybasic acids (anhydrides) include succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4 - ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid , benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and their anhydrides. Among them, from the viewpoint of outgassing, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferable, and succinic anhydride or tetrahydrophthalic anhydride is more preferable.

The use of a polyhydric alcohol tends to increase the molecular weight of the (c2) epoxy (meth)acrylate resin, introduce branches into the molecule, and balance the molecular weight and viscosity. In addition, the rate of introduction of acid groups into the molecule can be increased, and there is a tendency to easily balance sensitivity, adhesion, and the like.
The polyhydric alcohol is, for example, one or more polyhydric alcohols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. Preferably.

Examples of the epoxy (meth)acrylate resin include those described in Korean Patent Publication No. 10-2013-0022955 in addition to those described above.

(c2) The acid value of the epoxy (meth)acrylate resin is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, still more preferably 50 mgKOH/g or more, and even more preferably 70 mgKOH/g or more. 80 mgKOH/g or more is particularly preferable, 200 mgKOH/g or less is preferable, 180 mgKOH/g or less is more preferable, 150 mgKOH/g or less is more preferable, 120 mgKOH/g or less is even more preferable, and 110 mgKOH/g or less is particularly preferable. When the content is equal to or higher than the lower limit, the developability tends to be improved, and when the content is equal to or lower than the upper limit, the film strength tends to be improved. (c2) The acid value of the epoxy (meth)acrylate resin is, for example, 10 to 200 mgKOH/g, preferably 30 to 180 mgKOH/g, more preferably 50 to 150 mgKOH/g, further preferably 70 to 120 mgKOH/g. , 80-110 mg KOH/g is even more preferred.

(c2) The weight average molecular weight (Mw) of the epoxy (meth)acrylate resin is not particularly limited, but is usually 1,000 or more, preferably 2,000 or more, more preferably 3,000 or more, still more preferably 4,000 or more, and even more preferably 5,000 or more. It is particularly preferably 6,000 or more, most preferably 7,000 or more, and is usually 30,000 or less, preferably 20,000 or less, more preferably 15,000 or less, and still more preferably 10,000 or less. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced. (c2) The weight average molecular weight (Mw) of the epoxy (meth)acrylate resin is, for example, 1,000 to 30,000, preferably 2,000 to 20,000, more preferably 3,000 to 20,000, even more preferably 4,000 to 15,000, and 5,000 to 15,000. is more preferred, 6000 to 10000 is particularly preferred, and 7000 to 10000 is most preferred.

(C) The content of the (c2) epoxy (meth)acrylate resin contained in the alkali-soluble resin is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more. 18% by mass or more is particularly preferable, 90% by mass or less is preferable, 70% by mass or less is more preferable, 50% by mass or less is even more preferable, and 30% by mass or less is particularly preferable. When the content is equal to or higher than the lower limit, the amount of residue tends to be reduced, and when the content is equal to or lower than the upper limit, the ink repellency tends to be improved. The content of (c2) epoxy (meth)acrylate resin contained in (C) alkali-soluble resin is, for example, 5 to 90% by mass, preferably 10 to 70% by mass, more preferably 15 to 50% by mass. , 18-30 are more preferred.

In addition, the content of (c2) epoxy (meth)acrylate resin is preferably 5% by mass or more and 10% by mass with respect to the total mass of (c1) acrylic copolymer resin and (c2) epoxy (meth)acrylate resin. % or more, more preferably 15% by mass or more, particularly preferably 20% by mass or more, and preferably 90% by mass or less, more preferably 70% by mass or less, further preferably 50% by mass or less, and 30% by mass or less. is particularly preferred, and 25% by mass or less is even more particularly preferred. When the content is equal to or higher than the lower limit, the amount of residue tends to be reduced, and when the content is equal to or lower than the upper limit, the ink repellency tends to be improved. The content ratio of (c2) epoxy (meth)acrylate resin to the total mass of (c1) acrylic copolymer resin and (c2) epoxy (meth)acrylate resin is, for example, 5 to 90% by mass, and 5 to 70% by mass. % by mass is preferable, 10 to 50% by mass is more preferable, 15 to 30% by mass is even more preferable, and 20 to 25% by mass is even more preferable.

(c2) Epoxy (meth)acrylate resin can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, and in the presence of a catalyst and a thermal polymerization inhibitor, the acid or ester compound having the ethylenically unsaturated bond is added for an addition reaction, and further polybasic acid or its A method of continuing the reaction by adding an anhydride can be used.

Here, the organic solvent used for the reaction includes one or more organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate. Examples of the catalyst include tertiary amines such as triethylamine, benzyldimethylamine and tribenzylamine; One or more of quaternary ammonium salts, phosphorus compounds such as triphenylphosphine, stibines such as triphenylstibine, and the like can be used. Furthermore, the thermal polymerization inhibitor includes one or more of hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, and the like.

The acid or ester compound having an ethylenically unsaturated bond is usually 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents, relative to 1 chemical equivalent of the epoxy group of the epoxy resin. It can be an amount that becomes The temperature during the addition reaction is usually 60 to 150°C, preferably 80 to 120°C. Furthermore, the amount of polybasic acid (anhydride) used is usually 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1 chemical equivalents, relative to 1 chemical equivalent of the hydroxyl groups generated in the addition reaction. It can be an amount that provides a chemical equivalent.

(c2) Among epoxy (meth)acrylate resins, from the viewpoint of film strength and linearity, epoxy (meth)acrylate resins having a partial structure represented by the following general formula (i), and epoxy (meth)acrylate resins represented by the following general formula (ii) and at least one selected from the group consisting of an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (iii).

In formula (i), R ^a represents a hydrogen atom or a methyl group, and R ^b represents a divalent hydrocarbon group which may have a substituent. The benzene ring in formula (i) may be further substituted with any substituent. * represents a bond.

In formula (ii), each R ^c independently represents a hydrogen atom or a methyl group. R ^d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * represents a bond.

In formula (iii), R ^e represents a hydrogen atom or a methyl group, γ is a single bond, —CO—, an optionally substituted alkylene group, or an optionally substituted divalent represents a cyclic hydrocarbon group. The benzene ring in formula (iii) may be further substituted with any substituent. * represents a bond.

Among these, first, the epoxy (meth)acrylate resin having a partial structure represented by the following general formula (i) (hereinafter sometimes referred to as “epoxy (meth)acrylate resin (c2-1)”) is detailed. describe.

In formula (i), R ^a represents a hydrogen atom or a methyl group, and R ^b represents a divalent hydrocarbon group which may have a substituent. The benzene ring in formula (i) may be further substituted with any substituent. * represents a bond.

(R ^b )
In formula (i) above, R ^b represents a divalent hydrocarbon group which may have a substituent.
The divalent hydrocarbon group includes a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked. mentioned.

The divalent aliphatic group includes linear, branched and cyclic ones. Among these, linear ones are preferable from the viewpoint of developing solubility, while cyclic ones are preferable from the viewpoint of reducing permeation of the developer into the exposed area. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The film strength tends to be improved by making it equal to or higher than the lower limit, and the sensitivity tends to be improved by making it equal to or lower than the upper limit.

Specific examples of divalent linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-hexylene and n-heptylene groups. Among these, a methylene group is preferable from the viewpoint of sensitivity and production cost.
Specific examples of the divalent branched aliphatic group include the divalent straight-chain aliphatic group described above and a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and n-butyl as a side chain. groups, iso-butyl groups, sec-butyl groups, tert-butyl groups, and the like.
Although the number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, it is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved. Specific examples of the divalent cyclic aliphatic group include groups obtained by removing two hydrogen atoms from a ring such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring and adamantane ring. be done. Among these, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable from the viewpoint of film strength and developability.

Substituents which the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; and carboxyl group. Among these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

Moreover, a bivalent aromatic-hydrocarbon ring group and a bivalent aromatic heterocyclic group are mentioned as a bivalent aromatic ring group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. The divalent aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Groups such as triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring can be mentioned.

Moreover, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of divalent aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences. ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Groups such as pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring and azulene ring. Among these, a benzene ring or a naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable from the viewpoint of production cost.

Examples of substituents that the divalent aromatic ring group may have include hydroxyl group, methyl group, methoxy group, ethyl group, ethoxy group, propyl group, propoxy group and the like. Among these, unsubstituted is preferred from the viewpoint of curability.

Further, as the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic Groups in which one or more cyclic groups are linked can be mentioned.
Although the number of divalent aliphatic groups is not particularly limited, it is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is equal to or higher than the lower limit, the developability tends to be improved, and when the content is equal to or lower than the upper limit, the film strength tends to be improved.
Although the number of divalent aromatic ring groups is not particularly limited, it is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.

Specific examples of groups in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the following formulas (iA) to (iF), etc. is mentioned. Among these, a group represented by the following formula (iA) is preferable from the viewpoint of rigidity of the skeleton and hydrophobicity of the membrane.

As described above, the benzene ring in formula (i) may be further substituted with optional substituents. Examples of the substituent include hydroxyl group, methyl group, methoxy group, ethyl group, ethoxy group, propyl group, propoxy group and the like. The number of substituents is also not particularly limited, and may be one or two or more.
Among these, from the viewpoint of curability, unsubstituted is preferred.

Further, the partial structure represented by the formula (i) is preferably a partial structure represented by the following formula (i-1) from the viewpoint of development solubility.

In formula (i-1), R ^a and R ^b have the same definitions as in formula (i) above. ^RY represents a hydrogen atom or a polybasic acid residue. * represents a bond. The benzene ring in formula (i-1) may be further substituted with any substituent.

A polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylenetetrahydrophthalic acid. One or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid can be mentioned.
Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred from the viewpoint of patterning properties, and more preferred. is tetrahydrophthalic acid, biphenyltetracarboxylic acid.

The repeating unit structure represented by the formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (c2-1) may be one or two or more.

The number of partial structures represented by the formula (i) contained in one molecule of the epoxy (meth)acrylate resin (c2-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, 3 or more is more preferable, 10 or less is preferable, and 8 or less is more preferable. When the content is equal to or higher than the lower limit, the developability tends to be improved, and when the content is equal to or lower than the upper limit, the film strength tends to be improved.

The number of partial structures represented by the formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (c2-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more. It is preferably 3 or more, more preferably 10 or less, and even more preferably 8 or less. When the content is equal to or higher than the lower limit, the developability tends to be improved, and when the content is equal to or lower than the upper limit, the film strength tends to be improved.

Specific examples of the epoxy (meth)acrylate resin (c2-1) are given below.

Next, the epoxy (meth)acrylate resin having a partial structure represented by the following general formula (ii) (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (c2-2)") will be described in detail. .

In formula (ii), each R ^c independently represents a hydrogen atom or a methyl group. R ^d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * represents a bond.

( ^Rd )
In formula (ii) above, R ^d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
The cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.

Although the number of rings possessed by the aliphatic ring group is not particularly limited, it is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.
The number of carbon atoms in the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly 15 or less. preferable. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.

Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring and the like. Among these, an adamantane ring is preferable from the viewpoint of film strength and developability.

On the other hand, the number of rings possessed by the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less, and 4 or less. is more preferred. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.

Aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, particularly preferably 12 or more, and preferably 40 or less, and 30 or less. It is more preferably 20 or less, and particularly preferably 15 or less. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.

Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, A fluorene ring and the like can be mentioned. Among these, a fluorene ring is preferable from the viewpoint of patterning properties.

In addition, the divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited. and a group in which a divalent aliphatic group and one or more divalent aromatic ring groups are linked.

The divalent aliphatic group includes linear, branched and cyclic ones. Among these, linear ones are preferred from the viewpoint of improving developability, while cyclic ones are preferred from the viewpoint of film strength. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.

Specific examples of divalent linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-hexylene and n-heptylene groups. Among these, a methylene group is preferable from the viewpoint of sensitivity.
Specific examples of the divalent branched aliphatic group include the divalent straight-chain aliphatic group described above and a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and n-butyl as a side chain. groups, iso-butyl groups, sec-butyl groups, tert-butyl groups, and the like.

Although the number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, it is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.

Specific examples of the divalent cyclic aliphatic group include groups obtained by removing two hydrogen atoms from a ring such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring and adamantane ring. be done. Among these, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable from the viewpoint of film strength.

Substituents which the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; and carboxyl group. Among these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

Moreover, a bivalent aromatic-hydrocarbon ring group and a bivalent aromatic heterocyclic group are mentioned as a bivalent aromatic ring group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. The divalent aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Groups such as triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring can be mentioned.

Moreover, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of divalent aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences. ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Groups such as pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring and azulene ring. Among these, a benzene ring or a naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable from the viewpoint of production cost.

Examples of substituents that the divalent aromatic ring group may have include hydroxyl group, methyl group, methoxy group, ethyl group, ethoxy group, propyl group, propoxy group and the like. Among these, unsubstituted is preferred from the viewpoint of curability.

Further, as the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic Groups in which one or more cyclic groups are linked can be mentioned.
Although the number of divalent aliphatic groups is not particularly limited, it is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is equal to or higher than the lower limit, the developability tends to be improved, and when the content is equal to or lower than the upper limit, the film strength tends to be improved.
Although the number of divalent aromatic ring groups is not particularly limited, it is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.

Specific examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include the groups represented by the above formulas (iA) to (iF), etc. is mentioned. Among these, the group represented by the above formula (iC) is preferable from the viewpoint of achieving both film strength and sensitivity.

The bonding mode of the side chain cyclic hydrocarbon group to these divalent hydrocarbon groups is not particularly limited, but for example, one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with the side chain. and a mode in which a cyclic hydrocarbon group, which is a side chain, is formed including one of the carbon atoms of the aliphatic group.

Moreover, the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-1) from the viewpoint of sensitivity.

In formula (ii-1), R ^c has the same meaning as in formula (ii) above. R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent. n is an integer of 1 or more. The benzene ring in formula (ii-1) may be further substituted with any substituent. * represents a bond.

(R ^α )
In formula (ii-1) above, R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent.
The cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.

Although the number of rings possessed by the aliphatic ring group is not particularly limited, it is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, and more preferably 3 or less. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.
The number of carbon atoms in the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly 15 or less. preferable. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.

Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring and adamantane ring. Among these, an adamantane ring is preferable from the viewpoint of compatibility between film strength and developability.

On the other hand, the number of rings possessed by the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.
Aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.

Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring and the like. Among these, a fluorene ring is preferable from the viewpoint of compatibility between film strength and developability.

Examples of substituents that the cyclic hydrocarbon group may have include hydroxyl group, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, Alkyl groups having 1 to 5 carbon atoms such as amyl group and iso-amyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; nitro group; cyano group; Among these, unsubstituted is preferred from the viewpoint of ease of synthesis.

Although n represents an integer of 1 or more, 2 or more is preferable, and 3 or less is preferable. When the content is equal to or higher than the lower limit, the developability tends to be improved, and when the content is equal to or lower than the upper limit, the film strength tends to be improved.

Among these, from the viewpoint of achieving both film strength and developability, R ^α is preferably a monovalent aliphatic cyclic group, more preferably an adamantyl group.

As described above, the benzene ring in formula (ii-1) may be further substituted with optional substituents. Examples of the substituent include hydroxyl group, methyl group, methoxy group, ethyl group, ethoxy group, propyl group, propoxy group and the like. The number of substituents is also not particularly limited, and may be one or two or more. Among these, from the viewpoint of curability, unsubstituted is preferred.

Specific examples of the partial structure represented by formula (ii-1) are given below.

Further, the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-2) from the viewpoint of development adhesion.

In formula (ii-2), R ^c has the same definition as in formula (ii) above. R ^β represents a divalent cyclic hydrocarbon group which may have a substituent. The benzene ring in formula (ii-2) may be further substituted with any substituent. * represents a bond.

( ^Rβ )
In formula (ii-2) above, R ^β represents a divalent cyclic hydrocarbon group which may have a substituent.
The cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.

Although the number of rings possessed by the aliphatic ring group is not particularly limited, it is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.
The number of carbon atoms in the aliphatic ring group is generally 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.
Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring and the like. Among these, an adamantane ring is preferable from the viewpoint of compatibility between film strength and developability.

On the other hand, the number of rings possessed by the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.
Aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. In addition, the number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, preferably 40 or less, more preferably 30 or less, and further preferably 20 or less. It is preferred, and 15 or less is particularly preferred. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.

Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring and the like. Among these, a fluorene ring is preferable from the viewpoint of film strength and developability.

Examples of substituents that the cyclic hydrocarbon group may have include hydroxyl group, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, Alkyl groups having 1 to 5 carbon atoms such as amyl group and iso-amyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; nitro group; cyano group; Among these, non-substituted groups are preferred from the viewpoint of ease of synthesis.

Among these, R ^β is preferably a divalent aliphatic cyclic group, more preferably a divalent adamantane cyclic group, from the viewpoint of achieving both film strength and developability.
On the other hand, from the viewpoint of achieving both film strength and developability, ^Rβ is preferably a divalent aromatic ring group, more preferably a divalent fluorene ring group.

As described above, the benzene ring in formula (ii-2) may be further substituted with optional substituents. Examples of the substituent include hydroxyl group, methyl group, methoxy group, ethyl group, ethoxy group, propyl group, propoxy group and the like. The number of substituents is also not particularly limited, and may be one or two or more. Among these, from the viewpoint of curability, unsubstituted is preferred.

Specific examples of the partial structure represented by formula (ii-2) are given below.

On the other hand, the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-3) from the viewpoint of developability.

In formula (ii-3), R ^c and R ^d have the same definitions as in formula (ii) above. R ^Z represents a hydrogen atom or a polybasic acid residue.

A polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylenetetrahydrophthalic acid. One or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid can be mentioned.
Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred from the viewpoint of patterning properties, and more preferred. is tetrahydrophthalic acid, biphenyltetracarboxylic acid.

The partial structure represented by the formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin (c2-2) may be one type or two or more types.

The number of partial structures represented by the formula (ii) contained in one molecule of the epoxy (meth)acrylate resin (c2-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, Moreover, 20 or less are preferable, 15 or less are more preferable, and 10 or less are more preferable. The sensitivity tends to be improved by making it equal to or higher than the lower limit, and the developability tends to improve by making it equal to or lower than the upper limit. The number of partial structures represented by the formula (ii) contained in one molecule of the epoxy (meth)acrylate resin (c2-2) is, for example, 1 to 20, preferably 3 to 15, and 3 to 10 is more preferred.

The number of partial structures represented by the formula (ii-1) contained in one molecule of the epoxy (meth)acrylate resin (c2-2) is not particularly limited, but is preferably 1 or more, and more preferably 3 or more. It is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The sensitivity tends to be improved by making it equal to or higher than the lower limit, and the developability tends to improve by making it equal to or lower than the upper limit. The number of partial structures represented by the formula (ii-1) contained in one molecule of the epoxy (meth)acrylate resin (c2-2) is, for example, 1 to 20, preferably 3 to 15, 3 to 10 are more preferred.

In addition, the number of partial structures represented by the formula (ii-2) contained in one molecule of the epoxy (meth)acrylate resin (c2-2) is not particularly limited, but is preferably 1 or more, and more preferably 3 or more. It is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The sensitivity tends to be improved by making it equal to or higher than the lower limit, and the developability tends to improve by making it equal to or lower than the upper limit. The number of partial structures represented by the formula (ii-2) contained in one molecule of the epoxy (meth)acrylate resin (c2-2) is, for example, 1 to 20, preferably 3 to 15, 3 to 10 are more preferred.

The number of partial structures represented by the formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin (c2-2) is not particularly limited, but is preferably 1 or more, and more preferably 3 or more. It is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The sensitivity tends to be improved by making it equal to or higher than the lower limit, and the developability tends to improve by making it equal to or lower than the upper limit. The number of partial structures represented by the formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin (c2-2) is, for example, 1 to 20, preferably 3 to 15, 3 to 10 are more preferred.

Next, the epoxy (meth)acrylate resin having a partial structure represented by the following general formula (iii) (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (c2-3)") will be described in detail. .

In formula (iii), R ^e represents a hydrogen atom or a methyl group, γ is a single bond, —CO—, an optionally substituted alkylene group, or an optionally substituted divalent represents a cyclic hydrocarbon group. The benzene ring in formula (iii) may be further substituted with any substituent. * represents a bond.

(γ)
In the above formula (iii), γ represents a single bond, —CO—, an optionally substituted alkylene group, or an optionally substituted divalent cyclic hydrocarbon group.

The alkylene group may be linear or branched, but from the viewpoint of development solubility, it is preferably linear, and from the viewpoint of development adhesion, it is preferably branched. Although the number of carbon atoms is not particularly limited, it is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.

Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and a heptylene group. groups are more preferred.

Examples of substituents which the alkylene group may have include alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; Among these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

The divalent cyclic hydrocarbon group includes a divalent aliphatic ring group or a divalent aromatic ring group.

Although the number of rings possessed by the aliphatic ring group is not particularly limited, it is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.
The number of carbon atoms in the aliphatic ring group is generally 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.
Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring and the like. Among these, an adamantane ring is preferable from the viewpoint of compatibility between film strength and developability.

On the other hand, the number of rings possessed by the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.
Aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. In addition, the number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, preferably 40 or less, more preferably 30 or less, and further preferably 20 or less. It is preferred, and 15 or less is particularly preferred. When the content is equal to or higher than the lower limit, the film strength tends to be improved, and when the content is equal to or lower than the upper limit, developability tends to be improved.
Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring and the like. Among these, a fluorene ring is preferable from the viewpoint of compatibility between film strength and developability.

Examples of substituents that the cyclic hydrocarbon group may have include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, amyl group, Alkyl groups having 1 to 5 carbon atoms such as iso-amyl groups; alkoxy groups having 1 to 5 carbon atoms such as methoxy groups and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; Among these, non-substituted groups are preferred from the viewpoint of ease of synthesis.

Among these, from the viewpoint of developability, γ is preferably an optionally substituted alkylene group, more preferably a dimethylmethylene group.

As described above, the benzene ring in formula (iii) may be further substituted with optional substituents. Examples of the substituent include hydroxyl group, methyl group, methoxy group, ethyl group, ethoxy group, propyl group, propoxy group and the like. The number of substituents is also not particularly limited, and may be one or two or more. Among these, from the viewpoint of curability, unsubstituted is preferred.

On the other hand, the partial structure represented by the formula (iii) is preferably a partial structure represented by the following formula (iii-1) from the viewpoint of development solubility.

In formula (iii-1), R ^e and γ have the same definitions as in formula (iii) above. R ^W represents a hydrogen atom or a polybasic acid residue. * represents a bond. The benzene ring in formula (iii-1) may be further substituted with any substituent.

A polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylenetetrahydrophthalic acid. One or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid can be mentioned.
Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred from the viewpoint of patterning properties, and more preferred. is tetrahydrophthalic acid, biphenyltetracarboxylic acid.

The number of repeating unit structures represented by the formula (iii) contained in one molecule of the epoxy (meth)acrylate resin (c2-3) is not particularly limited, but is preferably 1 or more, more preferably 5 or more. , 10 or more is more preferable, 18 or less is preferable, and 15 or less is more preferable. The sensitivity tends to be improved by making it equal to or higher than the lower limit, and the developability tends to improve by making it equal to or lower than the upper limit. The number of repeating unit structures represented by the formula (iii) contained in one molecule of the epoxy (meth)acrylate resin (c2-3) is, for example, 1 to 18, preferably 5 to 18, and 10 ~15 is more preferred.

The number of repeating unit structures represented by the formula (iii-1) contained in one molecule of the epoxy (meth)acrylate resin (c2-3) is not particularly limited, but is preferably 1 or more, and 3 or more. It is more preferably 5 or more, more preferably 18 or less, and even more preferably 15 or less. The sensitivity tends to be improved by making it equal to or higher than the lower limit, and the developability tends to improve by making it equal to or lower than the upper limit. The number of repeating unit structures represented by the formula (iii-1) contained in one molecule of the epoxy (meth)acrylate resin (c2-3) is, for example, 1 to 18, preferably 3 to 18. , 5 to 15 are more preferred.

Specific examples of the epoxy (meth)acrylate resin (c2-3) are given below.

As described above, the (C) alkali-soluble resin in the present invention contains (c1) an acrylic copolymer resin having an ethylenically unsaturated group in the side chain and (c2) an epoxy (meth)acrylate resin. , and may contain other alkali-soluble resins.

The average acid value of the alkali-soluble resin of component (C) is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, preferably 30 mgKOH/g or more, and preferably 200 mgKOH/g or less. 150 mgKOH/g or less is more preferable, 100 mgKOH/g or less is more preferable, 70 mgKOH/g or less is even more preferable, and 50 mgKOH/g or less is particularly preferable. When the content is equal to or higher than the lower limit, the developability tends to be improved, and when the content is equal to or lower than the upper limit, the development adhesion tends to be improved. The average acid value of the component (C) alkali-soluble resin can be measured by neutralization titration. The average acid value of the component (C) alkali-soluble resin is, for example, 10 to 200 mgKOH/g, preferably 10 to 150 mgKOH/g, more preferably 20 to 100 mgKOH/g, further preferably 20 to 70 mgKOH/g. , 30 to 50 mg KOH/g is even more preferred.

Although the content of (C) the alkali-soluble resin in the colored photosensitive resin composition of the present invention is not particularly limited, the total solid content is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass. more preferably 30% by mass or more, still more preferably 40% by mass or more, particularly preferably 50% by mass or more, most preferably 60% by mass or more, and usually 90% by mass or less, preferably 80% by mass or less, More preferably, it is 70% by mass or less. When the lower limit value or more is used, the shape of the partition wall tends to be improved, and when the upper limit value or less is used, the sensitivity tends to be improved. The content of (C) the alkali-soluble resin in the total solid content of the colored photosensitive resin composition is, for example, 5 to 90% by mass, preferably 10 to 90% by mass, more preferably 20 to 80% by mass. , more preferably 30 to 80% by mass, even more preferably 40 to 80% by mass, particularly preferably 50 to 70% by mass, and most preferably 60 to 70% by mass.

In addition, the total content of (A) the ethylenically unsaturated compound and (C) the alkali-soluble resin in the total solid content is preferably 10% by mass or more, more preferably 30% by mass or more, and further 60% by mass or more. 80% by mass or more is particularly preferable, 100% by mass or less is preferable, 95% by mass or less is more preferable, and 90% by mass or less is even more preferable. When the concentration is equal to or higher than the lower limit, the sensitivity tends to be improved, and when the concentration is equal to or lower than the upper limit, the partition wall tends to have a good shape. The total content of (A) the ethylenically unsaturated compound and (C) the alkali-soluble resin in the total solid content of the colored photosensitive resin composition is, for example, 10 to 100% by mass, and 30 to 95% by mass. is preferred, 60 to 95 mass % is more preferred, and 80 to 90 mass % is even more preferred.

[1-1-4] Component (D): Liquid Repellent The colored photosensitive resin composition of the present invention contains (D) a liquid repellent. (D) Inclusion of the liquid-repellent agent makes it possible to impart ink repellency to the surfaces of the obtained partition walls, and thus it is thought that the obtained partition walls can prevent color mixture in each light-emitting portion (pixel) of the organic layer.

Examples of liquid repellent agents include silicone-containing compounds and fluorine compounds, and preferably liquid repellent agents having a cross-linking group (hereinafter sometimes referred to as "cross-linking group-containing liquid repellent agent"). The cross-linking group includes an epoxy group or an ethylenically unsaturated group, preferably an ethylenically unsaturated group from the viewpoint of suppressing the outflow of the liquid-repellent component to the developer.
When a cross-linking group-containing liquid-repellent agent is used, the cross-linking reaction on the surface of the formed coating film can be accelerated when exposed to light, making it difficult for the liquid-repellent agent to flow out during development. can exhibit high ink repellency.

When a fluorine-based compound is used as the liquid-repellent agent, the fluorine-based compound tends to be oriented on the surface of the partition walls and to work to prevent ink bleeding and color mixing. More specifically, groups containing fluorine atoms tend to repel ink and prevent ink bleeding and color mixing due to ink crossing the partition walls and entering adjacent regions.

Specific examples of the fluorine compound as the liquid repellent include perfluoroalkylsulfonic acid, perfluoroalkylcarboxylic acid, perfluoroalkylalkylene oxide adduct, perfluoroalkyltrialkylammonium salt, perfluoroalkyl group and hydrophilic group. oligomer containing perfluoroalkyl group and lipophilic group oligomer containing perfluoroalkyl group and hydrophilic group and lipophilic group urethane containing perfluoroalkyl and hydrophilic group perfluoroalkyl ester perfluoroalkyl phosphate Mention may be made of fluorine-containing organic compounds such as esters.
These compounds preferably have an epoxy group or an ethylenically unsaturated group as a substituent as a cross-linking group.
Commercially available fluorine-containing compounds having these cross-linking groups include DIC's "Megafac (registered trademark, hereinafter the same) F116", "Megafac F120", "Megafac F142D", "Megafac F144D", "Megafuck F150", "Megafuck F160", "Megafuck F171", "Megafuck F172", "Megafuck F173", "Megafuck F177", "Megafuck F178A", "Megafuck F178K", "Megafuck F178K" Fuck F179", "Megafuck F183", "Megafuck F184", "Megafuck F191", "Megafuck F812", "Megafuck F815", "Megafuck F824", "Megafuck F833", "Megafuck RS101" , “Megafuck RS102”, “Megafuck RS105”, “Megafuck RS201”, “Megafuck RS202”, “Megafuck RS301”, “Megafuck RS303”, “Megafuck RS304”, “Megafuck RS401”, “Mega Fac RS402", "Megafac RS501", "Megafac RS502", "Megafac RS-72-K", "DEFENSA (registered trademark, hereinafter the same) MCF300", "DEFENSA MCF310", "DEFENSA MCF312", " DEFENSA MCF323", 3M Japan's "Florado FC430", "Florado FC431", "FC-4430", "FC4432", AGC's "Asahi Guard (registered trademark) AG710", AGC Seimi Chemical Co.'s "Surflon ( Registered trademarks, hereinafter the same.) S-382”, “Surfron SC-101”, “Surfron SC-102”, “Surfron SC-103”, “Surfron SC-104”, “Surfron SC-105”, “Surfron SC -106” and “OPTOOL (registered trademark) DAC-HP” manufactured by Daikin Industries, Ltd., and the like.

Thus, when a fluorine-based compound is used as the liquid repellent agent, the content of fluorine atoms in the liquid repellent agent is not particularly limited, but the fluorine atom content is preferably 1% by mass or more, and more preferably 5% by mass or more. It is preferably 50% by mass or less, more preferably 25% by mass or less. When it is equal to or higher than the lower limit, there is a tendency to exhibit a high contact angle, and when it is equal to or lower than the upper limit, it tends to be possible to suppress the outflow of the liquid-repellent agent to the pixel portion. The content of fluorine atoms in the liquid-repellent agent is, for example, 1 to 50% by mass, preferably 5 to 25% by mass.

The molecular weight of the liquid-repellent agent is not particularly limited, and it may be a low-molecular-weight compound or a high-molecular-weight compound. A high-molecular-weight liquid-repellent agent is preferable because it suppresses the fluidity of the liquid-repellent agent due to post-baking, and can suppress the outflow of the liquid-repellent agent from the bank. 500 or more is more preferable, 100000 or less is preferable, and 10000 or less is more preferable. The number average molecular weight of the liquid repellent agent is, for example, 100 to 100,000, preferably 500 to 10,000.

The content of (D) the liquid repellent agent in the colored photosensitive resin composition of the present invention is not particularly limited, but is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0 in the total solid content. 5% by mass or more, and usually 5% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less. When the concentration is equal to or higher than the lower limit, high ink repellency tends to be exhibited. The content of the (D) liquid repellent agent in the total solid content of the colored photosensitive resin composition is, for example, 0.01 to 5% by mass, preferably 0.1 to 3% by mass, and 0.5 to 2%. % by mass is more preferred.

On the other hand, in the colored photosensitive resin composition of the present invention, a surfactant may be used together with (D) the liquid repellent agent, or a surfactant may be used instead of the (D) liquid repellent agent. Surfactants can be used for the purpose of improving the applicability of the colored photosensitive resin composition as a coating liquid and the developability of the coating film. Among them, fluorine-based or silicone-based surfactants are preferred.
In particular, during development, there is an action to remove the residue of the colored photosensitive resin composition from the unexposed area, also, since it has a function to express the wettability, silicone-based surfactant is preferable, polyether-modified silicone system surfactants are more preferred.

Compounds having a fluoroalkyl or fluoroalkylene group on at least one of the terminal, main chain and side chain are suitable as the fluorosurfactant. Specifically, 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, octaethylene glycol di( 1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol di(1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di(1,1,2,2- tetrafluorobutyl) ether, hexapropylene glycol di(1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2,8,8,9, 9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane and the like can be mentioned. These commercial products include, for example, BM Chemie "BM-1000", "BM-1100", DIC "Megafac F142D", "Megafac F172", "Megafac F173", "Megafac F183" , ``Megafac F470'', ``Megafac F475'', ``FC430'' manufactured by 3M Japan, and ``DFX-18'' manufactured by Neos.

Examples of silicone surfactants include "DC3PA", "SH7PA", "DC11PA", "SH21PA", "SH28PA", "SH29PA", "8032Additive" and "SH8400" manufactured by Dow Corning Toray Co., Ltd. Commercial products such as "BYK323" and "BYK330" manufactured by BYK-Chemie can be mentioned.
Surfactants other than fluorine-based surfactants and silicone-based surfactants may be included, and other surfactants include nonionic, anionic, cationic, and amphoteric surfactants. be done.

Examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, Glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythrityl fatty acid esters, polyoxyethylene pentaerythritic fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbit fatty acid esters, polyoxy Ethylene sorbite fatty acid esters and the like can be mentioned. Examples of these commercially available products include polyoxyethylene-based surfactants such as "Emulgen (registered trademark, hereinafter the same.) 104P" and "Emulgen A60" manufactured by Kao Corporation.

Examples of the anionic surfactant include alkylsulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, polyoxyethylene alkylethersulfonates, alkylsulfates, alkylsulfates, and higher alcohol sulfuric acid. Ester salts, fatty alcohol sulfate ester salts, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, special Examples include polymeric surfactants. Among them, a special polymeric surfactant is preferable, and a special polycarboxylic acid type polymeric surfactant is more preferable. As such anionic surfactants, commercially available products can be used. For example, for alkyl sulfate ester salts, "Emal (registered trademark) 10" manufactured by Kao Corporation, and for alkylnaphthalene sulfonates, "Pelex" manufactured by Kao Corporation (Registered Trademark) NB-L”, and special polymer surfactants such as “Homogenol (registered trademark, hereinafter the same) L-18” and “Homogenol L-100” manufactured by Kao Corporation.

Furthermore, examples of cationic surfactants include quaternary ammonium salts, imidazoline derivatives, and alkylamine salts, and examples of amphoteric surfactants include betaine compounds, imidazolium salts, imidazolines, and amino acids. etc. Among these, quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are more preferred. Commercially available alkylamine salts include "Acetamine (registered trademark) 24" manufactured by Kao Corporation, and quaternary ammonium salts "Cortamine (registered trademark) 24P" and "Cortamine (registered trademark) 24P" manufactured by Kao Corporation. 86W” and the like.

In addition, two or more surfactants may be used in combination. For example, silicone surfactant/fluorosurfactant, silicone surfactant/special polymer surfactant, fluorine surfactant / A combination of special polymeric surfactants. Among them, a combination of silicone surfactant/fluorosurfactant is preferable. In this combination of silicone surfactant / fluorine surfactant, for example, "DFX-18" manufactured by Neos, "BYK-300" or "BYK-330" manufactured by BYK Chemie / "S- 393”, “KP340” manufactured by Shin-Etsu Silicone Co., Ltd. / “F-478” or “F-475” manufactured by DIC, “SH7PA” manufactured by Dow Corning Toray / “DS-401” manufactured by Daikin, “L -77"/"FC4430" manufactured by 3M Japan.

[1-1-5] (E) Colorant The colored photosensitive resin composition of the present invention contains (E) a colorant. By including (E) a coloring agent, it is possible to obtain moderate light absorption properties, particularly when used for forming light-shielding members such as colored barrier ribs, moderate light-shielding properties.

The type of (E) colorant used in the present invention is not particularly limited, and a pigment or a dye may be used. Among these, pigments are preferably used from the viewpoint of durability.

The pigments contained in the (E) colorant may be of one type alone or two or more types. In particular, from the viewpoint of uniform light blocking in the visible region, two or more types are preferable.
(E) The type of pigment that can be used as the colorant is not particularly limited, but examples thereof include organic pigments and inorganic pigments. Among these, it is preferable to use an organic pigment from the viewpoint of controlling the transmission wavelength of the colored photosensitive resin composition for efficient curing.
Organic pigments include organic coloring pigments and organic black pigments. Here, the organic coloring pigment means an organic pigment exhibiting a color other than black, and includes red pigment, orange pigment, blue pigment, purple pigment, green pigment, yellow pigment, and the like.

Among organic pigments, it is preferable to use an organic coloring pigment from the viewpoint of light shielding properties and ultraviolet absorption properties.
The organic coloring pigments may be used singly or in combination of two or more. In particular, when it is used for light-shielding applications, it is more preferable to use a combination of organic coloring pigments having different colors, and it is even more preferable to use a combination of organic coloring pigments exhibiting a color close to black.

Although the chemical structure of these organic pigments is not particularly limited, azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based pigments can be used. Specific examples of pigments that can be used are shown below by pigment numbers. In the following, terms such as "C.I. Pigment Red 2" refer to the Color Index (C.I.).

As a red pigment, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. Among these, C.I. I. Pigment Red 48: 1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment Red 177, 209, 224, 254 may be mentioned. In terms of dispersibility and light-shielding properties, C.I. I. Pigment Red 177, 254, and 272 are preferably used, and when the colored photosensitive resin composition is cured with ultraviolet rays, it is preferable to use a red pigment having a low ultraviolet absorption rate. . I. Pigment Red 254, 272 is more preferably used.

As an orange pigment, C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 can be mentioned. Among these, C.I. I. Pigment Orange 13, 43, 64, 72 is preferably used, and when the colored photosensitive resin composition is cured with ultraviolet rays, it is preferable to use an orange pigment having a low ultraviolet absorption rate. is C.I. I. More preferably, Pigment Orange 64, 72 is used.

As a blue pigment, C.I. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 can be mentioned. Among these, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 60, more preferably C.I. I. Pigment Blue 15:6 may be mentioned.
In terms of dispersibility and light-shielding properties, C.I. I. Pigment Blue 15:6, 16, 60 is preferably used, and when the colored photosensitive resin composition is cured with ultraviolet rays, it is preferable to use a blue pigment having a low ultraviolet absorption rate. is C.I. I. Pigment Blue 60 is more preferably used.

As a purple pigment, C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 can be mentioned. Among these, C.I. I. Pigment Violet 19, 23, more preferably C.I. I. Pigment Violet 23 may be mentioned.
In terms of dispersibility and light-shielding properties, C.I. I. Pigment Violet 23, 29 is preferably used, and when the colored photosensitive resin composition is cured with ultraviolet rays, it is preferable to use a purple pigment having a low ultraviolet absorption rate. I. Pigment Violet 29 is more preferably used.

Examples of organic coloring pigments that can be used in addition to red pigments, orange pigments, blue pigments, and violet pigments include green pigments and yellow pigments.
As a green pigment, C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 can be mentioned. Among these, C.I. I. Pigment Green 7, 36 can be mentioned.
As a yellow pigment, C.I. I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95,97,100,101,104,105,108,109,110,111,116,117,119,120,126,127,127:1,128,129,133,134,136,138,139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208 can be mentioned. Among these, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, 180 can be mentioned.

Among these, it is preferable to use at least one selected from the group consisting of red pigments, orange pigments, blue pigments, and violet pigments from the viewpoint of light-shielding properties and shape control.

Among these, at least one of the following pigments is preferably contained from the viewpoint of light shielding properties and shape control.
Red pigment: C.I. I. Pigment Red 177, 254, 272
Orange pigment: C.I. I. Pigment Orange 43, 64, 72
Blue pigment: C.I. I. pigment blue 15:6,60
Purple pigment: C.I. I. Pigment Violet 23, 29

In addition, when two or more organic coloring pigments are used in combination, the combination of the organic coloring pigments is not particularly limited, but from the viewpoint of light-shielding properties, at least one selected from the group consisting of red pigments and orange pigments and a blue pigment. and at least one selected from the group consisting of violet pigments.
Although the combination of colors is not particularly limited, from the viewpoint of light blocking properties, for example, a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, a combination of a blue pigment, an orange pigment and a violet pigment, and the like. .

Furthermore, a black pigment may be used in addition to these organic coloring pigments. A black pigment may also be used in addition to the organic coloring pigment.
Examples of black pigments include inorganic black pigments and organic black pigments. From the viewpoint of light shielding properties, carbon black and/or organic black pigments are preferably contained.

Among black pigments, it is preferable to use an organic black pigment from the viewpoint of suppressing the absorption of ultraviolet rays and making it easier to control the shape and step. selected from the group consisting of a compound (hereinafter also referred to as "compound (1)"), a geometric isomer of compound (1), a salt of compound (1), and a salt of a geometric isomer of compound (1) It is preferable to use an organic black pigment containing at least one (hereinafter sometimes referred to as "an organic black pigment represented by formula (1)").

In formula (1), R ¹¹ and R ¹⁶ each independently represent a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are each independently hydrogen atom, halogen atom, R ²¹ , COOH, COOR ²¹ , COO ⁻ , CONH ₂ , CONHR ²¹ , ^{CONR21R22 ,} CN, ^OH , ^{OR21 , COCR21} , _OOCNH2 , ^OOCNHR21 , ^OOCNR21R22 , _NO2 , _NH2 , ^NHR21 , ^NR21R22 , ^{NHCOR22 , NR21COR22} , N = _CH2 , N= ^{CHR21 ,} N= ^CR21R22 , SH, ^SR21 , ^SOR21 , _SO2R21 ^{, SO3R21} , _{SO3H , SO3-} ^, _{SO2NH2 , SO2NHR} ^{21 or} _SO2NR21R22 ; and from ^R12 and ^{R13 , R13} and ^R14 , ^R14 and ^R15 , ^R17 and ^R18 , ^R18 and ^R19 , and ^R19 and ^R20 at least one combination selected from the group may be directly bonded to each other or bonded to each other through an oxygen atom, sulfur atom, NH or NR ²¹ bridge; R ²¹ and R ²² are each independently carbon It is an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms or an alkynyl group having 2 to 12 carbon atoms.

Compound (1) and geometric isomers of compound (1) have the following core structure (where the substituents in the structural formula are omitted), the trans-trans isomer being probably the most stable.

When compound (1) is anionic, its charge can be transferred to any known suitable cation such as metallic, organic, inorganic or metal-organic cations, particularly alkali metals, alkaline earth metals, transition metals, primary ammonium , secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium or a salt compensated by an organometallic complex. Also, when the geometric isomer of compound (1) is anionic, it is preferably a similar salt.

Among the substituents of the general formula (1) and their definitions, the following are preferred because they tend to increase the shielding rate. This is because the following substituents have no absorption and are considered not to affect the hue of the pigment.
R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁹ and R ²⁰ are each independently preferably hydrogen, fluorine or chlorine, more preferably hydrogen.
R ¹³ and R ¹⁸ are each independently preferably hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , bromine atom, chlorine atom, CH ₃ , C ₂ H ₅ , N(CH ₃ ) ₂ , N(CH ₃ ) (C ₂ H ₅ ), N(C ₂ H ₅ ) ₂ , α-naphthyl, β-naphthyl, SO ₃ H or SO ₃ ^- , more preferably a hydrogen atom or SO ₃ H, particularly preferably is a hydrogen atom.

R ¹¹ and R ¹⁶ are each independently preferably a hydrogen atom, CH ₃ or CF ₃ , more preferably a hydrogen atom.
Preferably, at least one combination selected from the group consisting of R ¹¹ and R ¹⁶ , R ¹² and R ¹⁷ , R ¹³ and R ¹⁸ , R ¹⁴ and R ¹⁹ , and R ¹⁵ and R ²⁰ is the same, more preferably is the same as R ¹⁶ , R ¹² is the same as R ¹⁷ , R ¹³ is the same as R ¹⁸ , R ¹⁴ is the same as R ¹⁹ , and R ^{15 is} the same as R ²⁰ are identical.

Alkyl groups having 1 to 12 carbon atoms are, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2-methylbutyl group, n- pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group, 2 - ethylhexyl, nonyl, decyl, undecyl or dodecyl.

Cycloalkyl groups having 3 to 12 carbon atoms are, for example, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, trimethylcyclohexyl, thuzyl, norbornyl, bornyl, and norcalyl groups. , karyl group, menthyl group, norpinyl group, pinyl group, adamantan-1-yl group or adamantan-2-yl group.

Alkenyl groups having 2 to 12 carbon atoms are, for example, vinyl group, allyl group, 2-propen-2-yl group, 2-buten-1-yl group, 3-buten-1-yl group, 1,3-butadiene -2-yl group, 2-penten-1-yl group, 3-penten-2-yl group, 2-menthyl-1-buten-3-yl group, 2-methyl-3-buten-2-yl group, 3-methyl-2-buten-1-yl group, 1,4-pentadien-3-yl group, hexenyl group, octenyl group, nonenyl group, decenyl group or dodecenyl group.

Cycloalkenyl groups having 3 to 12 carbon atoms are, for example, 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2 , 4-cyclohexadien-1-yl group, 1-p-menthen-8-yl group, 4(10)-thugen-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadiene-1 -yl group, 7,7-dimethyl-2,4-norcaladien-3-yl group or camphenyl group.

Alkynyl groups having 2 to 12 carbon atoms are, for example, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl group, 1,4-pentadiyn-3-yl group, 1,3-pentadiyn-5-yl group, 1-hexyn-6-yl group, cis-3-methyl-2-penten-4-yn-1-yl group, trans-3-methyl-2-penten-4-yn-1-yl group, 1,3-hexadiyn-5-yl group, 1-octin-8-yl group, 1-nonin-9-yl group, 1-decyn-10-yl group or 1-dodecyn-12-yl group.

A halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The organic black pigment represented by the general formula (1) is preferably a compound represented by the following general formula (2) (hereinafter also referred to as "compound (2)"), and the geometric isomer of compound (2) organic black pigment containing at least one selected from the group consisting of

A specific example of such an organic black pigment is Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF).
This organic black pigment is preferably used by dispersing it with a dispersant, solvent, and method, which will be described later. In addition, when a sulfonic acid derivative of compound (1), particularly a sulfonic acid derivative of compound (2) is present during dispersion, dispersibility and storage stability may be improved. is preferably included.

Examples of organic black pigments other than the organic black pigment represented by the general formula (1) include aniline black and perylene black.

On the other hand, examples of inorganic black pigments include carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black, and titanium black. Among these, carbon black can be preferably used from the viewpoint of light shielding properties and image characteristics. Examples of carbon black include the following carbon blacks.

Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, #5, #10, #20, #25, #30, #32, #33, #40 , #44, #45, #47, #50, #52, #55, #650, #750, #850, #900, #950, #960, #970, #980, #990, #1000, # 2200, #2300, #2350, #2400, #2600, #2650, #3030, #3050, #3150, #3250, #3400, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B , OIL11B, OIL30B, OIL31B
Degussa: Printex (registered trademark, hereinafter the same) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, PrintexA, Printex x L, Printex G, Printex P, Printex U, Printex V, Printex G, Special Black 550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color B black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170
Cabot Corporation: Monarch (registered trademark, the same applies hereinafter) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark, the same applies hereinafter) 99, RE GAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark, hereinafter the same) XC72R, ELFTEX (registered trademark)-8
Birler: RAVEN (registered trademark, hereinafter the same) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN8 90H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U , RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

Carbon black coated with resin may be used. The use of resin-coated carbon black has the effect of improving the adhesion to the glass substrate and the volume resistivity. As the resin-coated carbon black, for example, carbon black described in Japanese Patent Application Laid-Open No. 09-71733 can be preferably used. Resin-coated carbon black is preferably used in terms of volume resistance and dielectric constant.

The total content of Na and Ca is preferably 100 ppm or less as the carbon black to be coated with the resin. Carbon black usually contains Na, Ca, K, Mg, Al, Fe, etc. mixed from raw material oil, combustion oil (or gas), reaction stop water and granulation water at the time of production, and furnace materials of reactors. Contains ash with a composition of Of these, Na and Ca are generally contained in amounts of several hundred ppm or more, respectively. tend to prevent short circuits.

As a method for reducing the content of ash containing these Na and Ca, carefully select those with as little content as possible as raw material oil, fuel oil (or gas) and reaction stop water when producing carbon black. and by minimizing the amount of the alkaline substance added to adjust the structure. Another method is to wash the carbon black produced from the furnace with water or hydrochloric acid to dissolve and remove Na and Ca.

Specifically, carbon black is mixed and dispersed in water, hydrochloric acid, or hydrogen peroxide solution, and then a solvent that is sparingly soluble in water is added. Carbon black migrates to the solvent side and is completely separated from water. Most of Na and Ca present in the carbon black together with the carbon black are dissolved and removed in water and acid. In order to reduce the total amount of Na and Ca to 100 ppm or less, it may be possible to use the carbon black manufacturing process alone with carefully selected raw materials, or the water or acid dissolution method alone. The total amount of Na and Ca can be easily made 100 ppm or less.

Also, the resin-coated carbon black is preferably so-called acidic carbon black having a pH of 6 or less. Since the dispersion diameter (agglomerate diameter) in water becomes small, it is possible to coat even fine units, which is preferable. Furthermore, it is preferable that the average particle diameter is 40 nm or less and the dibutyl phthalate (DBP) absorption amount is 140 mL/100 g or less. Within the above range, there is a tendency to obtain a coating film having good light-shielding properties. The average particle diameter means the number average particle diameter. Particle image analysis is performed by taking photographs taken at tens of thousands of times by electron microscope observation in several fields and measuring about 2000 to 3000 particles in these photographs with an image processing device. means the equivalent circle diameter determined by

The method of preparing the resin-coated carbon black is not particularly limited. A resin solution obtained by mixing a resin with a solvent such as cyclohexanone, toluene, or xylene and dissolving it by heating, and a suspension obtained by mixing carbon black and water are mixed and stirred to separate carbon black and water, 2. A method of forming a composition obtained by removing water and heating and kneading into a sheet, pulverizing, and then drying; A method in which the resin solution and suspension prepared in the same manner as described above are mixed and stirred to granulate the carbon black and resin, and then the resulting granules are separated and heated to remove the remaining solvent and water; 3. A carboxylic acid such as maleic acid or fumaric acid is dissolved in the solvent exemplified above, carbon black is added, mixed and dried, the solvent is removed to obtain a carboxylic acid-impregnated carbon black, and a resin is added thereto. 4. dry blending with a hand; A reactive group-containing monomer component constituting the resin to be coated and water are stirred at high speed to prepare a suspension, which is cooled after polymerization to obtain a reactive group-containing resin from the polymer suspension. A method of adding carbon black, kneading, reacting the carbon black with a reactive group (grafting the carbon black), cooling, and pulverizing can be adopted.

The type of resin to be coated is not particularly limited, but synthetic resins are common, and resins having a benzene ring in the structure have a stronger amphoteric surfactant-like action. It is preferable in terms of dispersibility and dispersion stability.
Specific synthetic resins include thermosetting resins such as phenolic resins, melamine resins, xylene resins, diallyl phthalate resins, glyptal resins, epoxy resins, and alkylbenzene resins, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and modified polyphenylene. Thermoplastic resins such as oxide, polysulfone, polyparaphenyleneterephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyethersulfopolyphenylenesulfone, polyarylate, and polyetheretherketone can be used. The amount of coating resin is preferably 1 to 30% by mass based on the total amount of carbon black and resin. There is a tendency that the coverage can be made sufficient by making it equal to or higher than the above lower limit. On the other hand, when the content is equal to or less than the above upper limit, there is a tendency that adhesion between resins can be prevented and dispersibility can be improved.

Carbon black coated with a resin in this way can be used as a coloring agent for colored partition walls according to a conventional method. When such carbon black is used, there is a tendency that colored partition walls having a high light shielding rate and a low surface reflectance can be formed at low cost. It is also presumed that the coating of the carbon black surface with a resin has a function of confining ash containing Na and Ca in the carbon black.

These pigments are preferably dispersed so that the average particle size is generally 1 μm or less, preferably 0.5 μm or less, more preferably 0.25 μm or less. Here, the standard for the average particle size is the number of pigment particles.
Also, the average particle size of the pigment is a value determined from the pigment particle size measured by dynamic light scattering (DLS). Particle size measurement is performed using a sufficiently diluted colored photosensitive resin composition (usually diluted to prepare a pigment concentration of about 0.005 to 0.2% by mass. However, if the concentration recommended by the measuring instrument is If so, follow the concentration.) and measure at 25°C.

In addition to the organic coloring pigments and black pigments described above, dyes may also be used. Dyes that can be used as colorants include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
Examples of azo dyes include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Mordan Tread 7, C.I. I. Mordant Yellow 5, C.I. I. mordant black 7 and the like.

Examples of anthraquinone dyes include C.I. I. bat blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 and the like can be mentioned.
In addition, as a phthalocyanine dye, for example, C.I. I. Pad Blue 5 and the like are quinone imine dyes, for example, C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes, for example, C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro-based dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Examples include Disperse Yellow 42 and the like.

The content of the (E) colorant in the colored photosensitive resin composition of the present invention is 20% by mass or less in the total solid content. When the content of the coloring agent is small in this way, the coloring agent does not interfere with the orientation of the liquid repellent agent to the surface, and a large amount of the liquid repellent agent is oriented on the surface of the coating film when the coating is dried. Most of the liquid-repellent agent that is not sufficiently bonded flows out during development, and even if the film is cured by heating, the liquid-repellent agent is not replenished from the inside of the film to the surface, and the ink repellency of the obtained partition wall tends to be low. It is believed that there is. Therefore, when the content of the colorant is small, as described above, by using a specific alkali-soluble resin, the liquid repellent agent oriented on the coating surface can be firmly captured by chemical bonds, and the ink repellency can be improved. It is considered possible.

Moreover, when the content of the coloring agent is high, surface roughness may occur. This is because the amount of UV rays that reach the coating film surface and the inside of the coating film differ due to the presence of a large amount of colorant, which causes a difference in photocurability, resulting in a difference in shrinkage between the surface and the inside during post-baking. It is considered that surface roughness occurs on the surface of the coating film. When the surface roughness is strong, it becomes difficult to form a uniform layer when laminating electrodes and other organic layers on the partition walls, so it is preferable that the surface roughness is suppressed. It is thought that the low content of the colorant in the product reduces the difference in photocurability between the coating film surface and the inside of the coating film, thereby suppressing surface roughness.

The content of (E) the colorant in the colored photosensitive resin composition of the present invention is not particularly limited as long as it is 20% by mass or less in the total solid content, preferably 18% by mass or less, more preferably 15% by mass or less. , more preferably 12% by mass or less, particularly preferably 10% by mass or less, more preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more, and particularly preferably 5% by mass or more. By setting it to the above upper limit or less, the alkali-soluble resin and the ethylenically unsaturated compound can be relatively increased, so that the curability and ink repellency of the coating film tend to improve. It tends to be able to secure light-shielding properties. The content of the (E) colorant in the total solid content of the colored photosensitive resin composition is, for example, 2 to 20% by mass, preferably 2 to 18% by mass, more preferably 3 to 15% by mass, 4 to 12% by mass is more preferable, and 5 to 10% by mass is even more preferable.

[1-1-6] (F) Dispersant The colored photosensitive resin composition of the present invention contains (F) a dispersant in order to finely disperse (E) the colorant and stabilize its dispersion state. preferably included.
(F) As the dispersant, a polymer dispersant having a functional group is preferable, and further, from the viewpoint of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a base thereof; primary, secondary or tertiary Polymeric dispersants having functional groups such as amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine are preferred. Above all, polymeric dispersants having basic functional groups such as primary, secondary or tertiary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine disperse pigments. It is particularly preferable from the viewpoint that it can be dispersed with a small amount of dispersant.

Examples of polymeric dispersants include urethane-based dispersants, acrylic dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants composed of a monomer having an amino group and a macromonomer, and polyoxyethylene alkyl ethers. Examples include system dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

Specific examples of such dispersants include trade names of EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by BYK-Chemie), Disparlon (registered trademark, manufactured by Kusumoto Kasei), and SOLSPERSE. (registered trademark, manufactured by Lubrizol Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and Ajisper (registered trademark, manufactured by Ajinomoto Co., Inc.).
One of these polymer dispersants may be used alone, or two or more thereof may be used in combination.

The weight average molecular weight (Mw) of the polymeric dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less.
Among these, from the viewpoint of pigment dispersibility, (F) the dispersant preferably contains a urethane-based polymer dispersant and/or an acrylic polymer dispersant having a functional group. It is particularly preferred to include
From the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and a polyester bond and/or a polyether bond is preferred.

As urethane-based and acrylic-based polymer dispersants, for example, DISPERBYK-160 to 167, 182 series (all urethane-based), DISPERBYK-2000, 2001, BYK-LPN21116, etc. (all acrylic-based) (all manufactured by BYK-Chemie) ).
A specific example of a preferred chemical structure as a urethane polymer dispersant is, for example, a polyisocyanate compound and a compound having a number average molecular weight of 300 to 10,000 and having one or two hydroxyl groups in the molecule. Dispersion resins having a weight-average molecular weight of 1,000 to 200,000, obtained by reacting a compound having an active hydrogen and a tertiary amino group in the molecule, and the like. By treating these with a quaternizing agent such as benzyl chloride, all or part of the tertiary amino groups can be converted to quaternary ammonium bases.

Examples of the above polyisocyanate compounds include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanate such as dimer acid diisocyanate, isophorone diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), ω,ω Alicyclic diisocyanates such as '-diisocyanate dimethylcyclohexane, xylylene diisocyanate, aliphatic diisocyanates having aromatic rings such as α,α,α',α'-tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1, 6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris(isocyanatophenylmethane), tris(isocyanatophenyl)thiophosphate and triisocyanates such as triisocyanates, trimers thereof, water adducts, and polyol adducts thereof. Preferred polyisocyanates are trimers of organic diisocyanates, most preferred are trimers of tolylene diisocyanate and trimers of isophorone diisocyanate.
These may be used individually by 1 type, and may use 2 or more types together.

As a method for producing a trimer of isocyanate, the above-mentioned polyisocyanates are treated with a suitable trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc. to convert the isocyanate group part After the trimerization is terminated by addition of a catalyst poison, unreacted polyisocyanate is removed by solvent extraction and thin film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

Compounds having a number average molecular weight of 300 to 10,000 and having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, etc., and one terminal hydroxyl group of these compounds has a carbon number. Examples include those alkoxylated with 1 to 25 alkyl groups and mixtures of two or more of these.
Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more thereof. Examples of polyether diols include those obtained by homopolymerizing or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and these. and mixtures of two or more of

Polyetherester diols include those obtained by reacting ether group-containing diols or mixtures with other glycols with dicarboxylic acids or their anhydrides, or by reacting polyester glycols with alkylene oxides, e.g. oxytetramethylene) adipate and the like. The most preferred polyether glycols are polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, and compounds in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol , 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1 ,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2 ,5-hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, 1,9-nonanediol and other aliphatic glycols; bishydroxymethylcyclohexane and other aliphatic glycols; aromatic glycols such as lenglycol and bishydroxyethoxybenzene; N-alkyldialkanolamines such as N-methyldiethanolamine; , polyethylene/propylene adipate, etc., or polylactone diols or polylactone monools obtained by using the above diols or monohydric alcohols having 1 to 25 carbon atoms as initiators, such as polycaprolactone glycol, polymethylvalerolactone and these Mixtures of two or more are included. The most preferred polyester glycol is polycaprolactone glycol or polycaprolactone initiated by an alcohol having 1 to 25 carbon atoms.

Examples of polycarbonate glycols include poly(1,6-hexylene) carbonate and poly(3-methyl-1,5-pentylene) carbonate, and examples of polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. is mentioned.
These may be used individually by 1 type, and may use 2 or more types together.

The compound having one or two hydroxyl groups in the same molecule generally has a number average molecular weight of 300 to 10,000, preferably 500 to 6,000, more preferably 1,000 to 4,000.

A compound having an active hydrogen and a tertiary amino group in the same molecule used in the present invention will be explained.
Active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom, includes hydrogen atoms in functional groups such as a hydroxyl group, an amino group, and a thiol group. A hydrogen atom of the amino group of is preferred.

The tertiary amino group is not particularly limited, but includes, for example, an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically an imidazole ring or a triazole ring.
Examples of compounds having active hydrogen and a tertiary amino group in the same molecule include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dipropylethylenediamine, N,N -dibutylethylenediamine, N,N-dimethyl-1,4-butanediamine, N,N-diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, N,N-dibutyl-1 , 4-butanediamine and the like.

Further, when the tertiary amino group is a nitrogen-containing heterocyclic structure, the nitrogen-containing heterocyclic ring includes a pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzo 5-membered nitrogen-containing hetero ring such as triazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring; 6-membered nitrogen-containing hetero ring such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring ring. Preferred among these nitrogen-containing heterocycles are imidazole rings and triazole rings.

Specific examples of compounds having an imidazole ring and an amino group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, 1-(2-aminoethyl)imidazole and the like. Specific examples of compounds having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5-(2-amino-5-chlorophenyl)-3-phenyl-1H-1 , 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 ,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among them, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, 3-amino-1,2,4-triazole preferable.
These may be used individually by 1 type, and may use 2 or more types together.

A preferred blending ratio of raw materials for producing a urethane-based polymer dispersant is 10 parts by mass of a compound having a number average molecular weight of 300 to 10,000 and having one or two hydroxyl groups in the same molecule per 100 parts by mass of a polyisocyanate compound. to 200 parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and 0.2 to 25 parts by mass, preferably 0.3, of a compound having active hydrogen and a tertiary amino group in the same molecule ~24 parts by mass.

The urethane polymer dispersant is produced according to a known method for producing polyurethane resins. Solvents used in the production generally include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone, esters such as ethyl acetate, butyl acetate, and cellosolve acetate, benzene, toluene, xylene, and hexane. Some alcohols such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethylsulfoxide are used. These may be used individually by 1 type, and may use 2 or more types together.

A urethanization reaction catalyst is usually used for the above production. Examples of this catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate and stannus octoate; iron-based catalysts such as iron acetylacetonate and ferric chloride; class amines, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled within the range of 1 to 100 mgKOH/g in terms of amine value after the reaction. More preferably, it is in the range of 5-95 mgKOH/g. The amine value is a value expressed in mg of KOH corresponding to the acid value obtained by neutralizing and titrating the basic amino group with an acid. When the content is at least the lower limit, the dispersibility tends to be improved, and when the content is at most the upper limit, the developability tends to be improved.

When the isocyanate group remains in the polymer dispersant after the reaction described above, it is preferable to crush the isocyanate group with an alcohol or an amino compound, since the stability of the product over time increases.
The weight-average molecular weight (Mw) of the urethane polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. The dispersibility and dispersion stability tend to be improved by setting the amount to the above lower limit or more, and the dispersibility tends to be improved by improving the solubility and dispersibility by setting the amount to the above upper limit or less.

As the acrylic polymer dispersant, an unsaturated group-containing monomer having a functional group (the functional group here is the functional group described above as the functional group contained in the polymer dispersant), It is preferable to use random copolymers, graft copolymers and block copolymers with unsaturated group-containing monomers having no functional groups. These copolymers can be produced by known methods.

Examples of unsaturated group-containing monomers having functional groups include (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acrylic acid, royloxyethyl hexahydrophthalic acid, unsaturated monomers having a carboxyl group such as acrylic acid dimer, tertiary amino groups such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate and quaternary products thereof, Specific examples include unsaturated monomers having a quaternary ammonium base. These may be used individually by 1 type, and may use 2 or more types together.

Examples of unsaturated group-containing monomers having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( meth)acrylate, t-butyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate Acrylate, isobornyl (meth)acrylate, tricyclodecane (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide, N - N-substituted maleimides such as benzylmaleimide, acrylonitrile, vinyl acetate and polymethyl (meth)acrylate macromonomers, polystyrene macromonomers, poly 2-hydroxyethyl (meth)acrylate macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, poly Examples include macromonomers such as caprolactone macromonomers. These may be used individually by 1 type, and may use 2 or more types together.

The acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer consisting of an A block having a functional group and a B block having no functional group. In addition to the partial structure derived from the unsaturated group-containing monomer containing the functional group, the block may contain a partial structure derived from the unsaturated group-containing monomer that does not contain the functional group. may be contained in the A block in any form of random copolymerization or block copolymerization. The content of the partial structure containing no functional group in the A block is usually 80% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less.

The B block consists of a partial structure derived from an unsaturated group-containing monomer that does not contain the above functional group, but one B block contains partial structures derived from two or more monomers. These may be contained in the B block in any form of random copolymerization or block copolymerization.
The AB or BAB block copolymer is prepared, for example, by the following living polymerization method.
The living polymerization method includes an anion living polymerization method, a cationic living polymerization method, and a radical living polymerization method. Of these, in the anionic living polymerization method, the polymerization active species is an anion, and is represented by, for example, the following scheme.

In the above scheme, Ar ¹ is a monovalent organic group, Ar ² is a monovalent organic group different from Ar ¹ , M is a metal atom, and s and t are integers of 1 or more.

In the radical living polymerization method, the polymerization active species is a radical, and is shown, for example, in the scheme below.

In the above scheme, Ar ¹ is a monovalent organic group, Ar ² is a monovalent organic group different from Ar ¹ , j and k are each an integer of 1 or more, and ^Ra is a hydrogen atom or 1 is a valent organic group, and R ^b is a hydrogen atom or a monovalent organic group different from R ^a .

In synthesizing this acrylic polymer dispersant, Japanese Patent Laid-Open No. 9-62002 and P.S. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), B.P. C. Anderson, G.; D. Andrews et al, Macromolecules, 14, 1601 (1981), K.K. Hatada, K.; Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Kouichi Ugimoto, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Kobunshi Ronbunshu, 46, 189 (1989), M. Kuroki, T.; Aida, J.; Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D. Y. Sogoh, W.; R. A known method such as described in Hertler et al., Macromolecules, 20, 1473 (1987) can be employed.

The acrylic polymer dispersant that can be used in the present invention may be an AB block copolymer or a BAB block copolymer, and the A block constituting the copolymer The /B block ratio is preferably 1/99 to 80/20, particularly 5/95 to 60/40 (mass ratio), and by setting it within this range, it is possible to ensure a balance between dispersibility and storage stability. Tend.
In addition, the amount of the quaternary ammonium base in 1 g of the AB block copolymer and BAB block copolymer that can be used in the present invention is usually preferably 0.1 to 10 mmol. Within the range, there is a tendency to ensure good dispersibility.

Such a block copolymer may usually contain an amino group generated during the production process, and the amine value thereof is about 1 to 100 mgKOH/g, and from the viewpoint of dispersibility, It is preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, still more preferably 50 mgKOH/g or more, and preferably 90 mgKOH/g or less, more preferably 80 mgKOH/g or less, still more preferably 75 mgKOH/g or less.
Here, the amine value of dispersants such as these block copolymers is expressed by the mass of KOH equivalent to the amount of base per 1 g of solid content excluding the solvent in the dispersant sample, and is measured by the following method.
Accurately weigh 0.5 to 1.5 g of a dispersant sample in a 100 mL beaker and dissolve it in 50 mL of acetic acid. Using an automatic titrator equipped with a pH electrode, this solution is neutralized and titrated with a 0.1 mol/L HClO ₄ acetic acid solution. The inflection point of the titration pH curve is defined as the end point of the titration, and the amine value is obtained by the following formula.

Amine value [mgKOH / g] = (561 × V) / (W × S) [W: dispersant sample weighed amount [g], V: titration amount at the end point of titration [mL], S: dispersant It represents the solid content concentration [mass %] of the sample. ]
In addition, the acid value of this block copolymer depends on the presence and type of the acidic group that is the source of the acid value, but it is generally preferable that it is low, usually 10 mgKOH / g or less, and its weight average molecular weight (Mw ) is preferably in the range of 1000 to 100,000. Within the above range, there is a tendency to ensure good dispersibility.

When having a quaternary ammonium base as a functional group, the specific structure of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, a repeating unit represented by the following formula (i) (hereinafter referred to as "repeating (sometimes referred to as unit (i)”).

In the above formula (i), each of R ³¹ to R ³³ is independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or a represents an aralkyl group which may be
two or more of R ³¹ to R ³³ may bond together to form a cyclic structure;
R ³⁴ is a hydrogen atom or a methyl group;
X is a divalent linking group;
Y ⁻ is a counter anion.

Although the number of carbon atoms in the optionally substituted alkyl group in R ³¹ to R ³³ in the above formula (i) is not particularly limited, it is preferably 1 or more and 10 or less. The following are more preferable. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like. is preferably a group, a pentyl group, or a hexyl group, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Also, it may be linear or branched. Moreover, a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group may be included.

Although the number of carbon atoms in the optionally substituted aryl group in R ³¹ to R ³³ in the above formula (i) is not particularly limited, it is usually 6 or more and preferably 16 or less. The following are more preferable. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group and an anthracenyl group. , dimethylphenyl group, or diethylphenyl group, and more preferably phenyl group, methylphenyl group, or ethylphenyl group.

The number of carbon atoms in the optionally substituted aralkyl group in R ³¹ to R ³³ of formula (i) is not particularly limited, but is usually 7 or more and preferably 16 or less, and 12 The following are more preferable. Specific examples of the aralkyl group include phenylmethyl group (benzyl group), phenylethyl group (phenethyl group), phenylpropyl group, phenylbutyl group, phenylisopropyl group and the like. is preferably a group, a phenylpropyl group, or a phenylbutyl group, and more preferably a phenylmethyl group or a phenylethyl group.

Among these, from the viewpoint of dispersibility, it is preferable that R ³¹ to R ³³ are each independently an alkyl group or an aralkyl group. Specifically, R ³¹ and R ³³ are each independently a methyl group, or an ethyl group, and R ³² is preferably a phenylmethyl group or a phenylethyl group, more preferably R ³¹ and R ³³ are methyl groups, and R ³² is a phenylmethyl group. .

Further, when the polymer dispersant has a tertiary amine as a functional group, from the viewpoint of dispersibility, a repeating unit represented by the following formula (ii) (hereinafter sometimes referred to as "repeating unit (ii)" .).

In the above formula (ii), R ³⁵ and R ³⁶ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or a substituted is an aralkyl group which may be
R ³⁵ and R ³⁶ may be linked together to form a cyclic structure;
R ³⁷ is a hydrogen atom or a methyl group;
Z is a divalent linking group.

As the optionally substituted alkyl group for R ³⁵ and R ³⁶ in the above formula (ii), those exemplified for R ³¹ to R ³³ in the above formula (i) can be preferably employed.
As the optionally substituted aryl group for R ³⁵ and R ³⁶ in the above formula (ii), those exemplified for R ³¹ to R ³³ in the above formula (i) can be preferably employed.
As the optionally substituted aralkyl group for R ³⁵ and R ³⁶ in the above formula (ii), those exemplified for R ³¹ to R ³³ in the above formula (i) can be preferably employed.

Among these, R ³⁵ and R ³⁶ are preferably each independently an optionally substituted alkyl group, more preferably a methyl group or an ethyl group.

Examples of substituents that the alkyl group, aralkyl group or aryl group in R ³¹ to R ³³ in the above formula (i) and R ³⁵ and R ³⁶ in the above formula (ii) may have include a halogen atom, an alkoxy group, A benzoyl group, a hydroxyl group, and the like can be mentioned.

In the above formulas (i) and (ii), the divalent linking groups X and Z include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a —CONH—R ⁴³ — group, —COOR ⁴⁴ — group [wherein R ⁴³ and R ⁴⁴ are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms], etc., preferably is a --COO--R ⁴⁴ -- group.
In the above formula (i), the counter anion Y ⁻ includes Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , PF ₆ ⁻ and the like.

The content ratio of the repeating unit represented by the formula (i) is not particularly limited, but from the viewpoint of dispersibility, the content ratio of the repeating unit represented by the formula (i) and the content ratio of the repeating unit represented by the formula (ii) It is preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, and particularly preferably 35 mol% or less, relative to the total content of repeating units, Also, it is preferably 5 mol % or more, more preferably 10 mol % or more, still more preferably 20 mol % or more, and particularly preferably 30 mol % or more.

In addition, the content ratio of the repeating unit represented by the formula (i) in the total repeating units of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 1 mol% or more, and 5 mol. % or more, more preferably 10 mol% or more, preferably 50 mol% or less, more preferably 30 mol% or less, and 20 mol% or less. is more preferable, and 15 mol % or less is particularly preferable.

In addition, the content ratio of the repeating unit represented by the formula (ii) in the total repeating units of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 5 mol% or more, and 10 mol. % or more, more preferably 15 mol% or more, particularly preferably 20 mol% or more, and preferably 60 mol% or less, and 40 mol% or less. is more preferably 30 mol % or less, and particularly preferably 25 mol % or less.

In addition, from the viewpoint of enhancing compatibility with binder components such as solvents and improving dispersion stability, the polymer dispersant is a repeating unit represented by the following formula (iii) (hereinafter referred to as “repeating unit (iii) ).

In the above formula (iii), R ⁴⁰ is an ethylene group or a propylene group; R ⁴¹ is an optionally substituted alkyl group; R ⁴² is a hydrogen atom or a methyl group; 20 integers.

The number of carbon atoms in the optionally substituted alkyl group in R ⁴¹ of formula (iii) is not particularly limited, but is 1 or more, preferably 2 or more, and 10 or less. is preferred, and 6 or less is more preferred. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like. is preferably a group, a pentyl group, or a hexyl group, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Also, it may be linear or branched. Moreover, a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group may be included.

Further, n in the above formula (iii) is 1 or more, preferably 2 or more, and preferably 10 or less, and 5 or less, from the viewpoint of compatibility and dispersibility with respect to a binder component such as a solvent. is more preferable.

In addition, the content ratio of the repeating unit represented by the formula (iii) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol % or more, and preferably 2 mol % or more. It is more preferably 4 mol % or more, more preferably 30 mol % or less, more preferably 20 mol % or less, and even more preferably 10 mol % or less. Within the above range, it tends to be possible to achieve both compatibility with a binder component such as a solvent and dispersion stability.

In addition, from the viewpoint of enhancing the compatibility of the dispersant with a binder component such as a solvent and improving the dispersion stability, the polymer dispersant is a repeating unit represented by the following formula (iv) (hereinafter referred to as “repeating unit (iv )”.).

In formula (iv) above, R ³⁸ is an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group; ³⁹ is a hydrogen atom or a methyl group.

The number of carbon atoms in the optionally substituted alkyl group in R ³⁸ of formula (iv) is not particularly limited, but is 1 or more, preferably 2 or more, and 4 or more. More preferably, it is 10 or less, and more preferably 8 or less. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like. is preferably a group, a pentyl group, or a hexyl group, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Also, it may be linear or branched. Moreover, a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group may be included.

The number of carbon atoms in the optionally substituted aryl group in R ³⁸ of formula (iv) is not particularly limited, but is usually 6 or more, preferably 16 or less, and 12 or less. is more preferable, and 8 or less is even more preferable. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group and an anthracenyl group. , dimethylphenyl group, or diethylphenyl group, and more preferably phenyl group, methylphenyl group, or ethylphenyl group.

Although the number of carbon atoms in the optionally substituted aralkyl group in R ³⁸ of the formula (iv) is not particularly limited, it is usually 7 or more, preferably 16 or less, and 12 or less. is more preferable, and 10 or less is even more preferable. Specific examples of the aralkyl group include phenylmethyl group (benzyl group), phenylethyl group (phenethyl group), phenylpropyl group, phenylbutyl group, phenylisopropyl group and the like. is preferably a group, a phenylpropyl group, or a phenylbutyl group, and more preferably a phenylmethyl group or a phenylethyl group.

Among these, from the viewpoint of solvent compatibility and dispersion stability, R ³⁸ is preferably an alkyl group or an aralkyl group, more preferably a methyl group, an ethyl group or a phenylmethyl group.
Examples of substituents that the alkyl group in R ³⁸ may have include a halogen atom and an alkoxy group. Further, examples of the substituent that the aryl group or aralkyl group may have include a chain alkyl group, a halogen atom, an alkoxy group, and the like. The chain alkyl group represented by R ³⁸ includes both straight chain and branched chain alkyl groups.

In addition, the content of the repeating unit represented by the formula (iv) in the total repeating units of the polymer dispersant is preferably 30 mol% or more, more preferably 40 mol% or more, from the viewpoint of dispersibility. more preferably 50 mol % or more, more preferably 80 mol % or less, more preferably 70 mol % or less.

The polymer dispersant may have repeating units other than repeating unit (i), repeating unit (ii), repeating unit (iii) and repeating unit (iv). Examples of such repeating units include styrene-based monomers such as styrene and α-methylstyrene; (meth)acrylate-based monomers such as (meth)acrylic acid chloride; (meth)acrylamide, N- Repeating units derived from monomers such as (meth)acrylamide-based monomers such as methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate; N-methacryloylmorpholine.

From the viewpoint of further increasing the dispersibility, the polymer dispersant includes an A block having the repeating unit (i) and the repeating unit (ii) and a B block having no repeating unit (i) and the repeating unit (ii) and is preferably a block copolymer. The block copolymer is preferably an AB block copolymer or a BAB block copolymer. Introducing not only a quaternary ammonium base but also a tertiary amino group into the A block unexpectedly tends to significantly improve the dispersing ability of the dispersant. Also, the B block preferably has the repeating unit (iii), and more preferably has the repeating unit (iv).

In the A block, the repeating unit (i) and the repeating unit (ii) may be contained in any form of random copolymerization or block copolymerization. Two or more kinds of repeating units (i) and repeating units (ii) may be contained in one A block. It may be contained in any mode of block copolymerization.

In addition, repeating units other than repeating units (i) and repeating units (ii) may be contained in the A block. Repeating units derived from mers and the like are included. The content of repeating units other than repeating units (i) and repeating units (ii) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. Most preferably it is not contained in a block.

Repeating units other than repeating units (iii) and (iv) may be contained in the B block. Examples of such repeating units include styrene-based monomers such as styrene and α-methylstyrene; (Meth)acrylate-based monomers such as meth)acrylic acid chloride; (meth)acrylamide-based monomers such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate Examples thereof include repeating units derived from monomers such as ether; N-methacryloylmorpholine. The content of repeating units other than repeating units (iii) and repeating units (iv) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and such repeating units are B Most preferably it is not contained in a block.

When the colored photosensitive resin composition of the present invention contains (F) a dispersant, the content is not particularly limited, but the total solid content of the colored photosensitive resin composition is preferably 0.1% by mass or more. , More preferably 0.5% by mass or more, more preferably 1% by mass or more, particularly preferably 1.5% by mass or more, and preferably 8% by mass or less, more preferably 5% by mass or less, 3% by mass or less is more preferable, and 2% by mass or less is particularly preferable. When the concentration is at least the lower limit, the generation of residue due to aggregates tends to be suppressed, and when the concentration is at most the upper limit, sensitivity and developability tend to be improved. When the colored photosensitive resin composition contains (F) a dispersant, the content of (F) the dispersant in the total solid content of the colored photosensitive resin composition is, for example, 0.1 to 8% by mass. , preferably 0.1 to 5% by mass, more preferably 1 to 3% by mass, even more preferably 1.5 to 2% by mass.

[1-1-7] Ultraviolet Absorber The colored photosensitive resin composition of the present invention may contain an ultraviolet absorber. The UV absorber is added for the purpose of controlling the photocuring distribution by absorbing a specific wavelength of the light source used for exposure. Addition of an ultraviolet absorber provides effects such as improving the taper angle and shape after development and eliminating residues remaining in non-exposed areas after development. As the ultraviolet absorber, from the viewpoint of inhibiting the light absorption of the (B) photopolymerization initiator, for example, a compound having an absorption maximum between wavelengths of 250 nm and 400 nm can be used.
A benzotriazole-based compound and/or a triazine-based compound are desirable as the ultraviolet absorber. By including the benzotriazole-based compound and/or the triazine-based compound, the light absorptance at the bottom of the film of the initiator is reduced, and the bottom size is reduced, thereby increasing the taper angle.

Among the benzotriazole-based compounds, a benzotriazole compound represented by the following general formula (Z1) is preferable from the point of tapered shape.

In the above formula (Z1), R ^1e and R ^2e are each independently a hydrogen atom, an optionally substituted alkyl group, a group represented by the following general formula (Z2), or a group represented by the following general formula (Z3 ) represents a group represented by R ^3e represents a hydrogen atom or a halogen atom.

In formula (Z2) above, R ^4e represents an optionally substituted alkylene group, and R ^5e represents an optionally substituted alkyl group.

In formula (Z3) above, R ^6e represents an optionally substituted alkylene group, and R ^7e represents a hydrogen atom or a methyl group.

(R ^1e and R ^2e )
In formula (Z1), R ^1e and R ^2e are each independently a hydrogen atom, an optionally substituted alkyl group, a group represented by general formula (Z2), or a group represented by general formula (Z3) represents the group represented.
Alkyl groups include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 2 or more, further preferably 4 or more, preferably 10 or less, more preferably 6 or less, It is more preferably 4 or less.

Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl groups. Among these, a tert-butyl group is preferred.
Examples of substituents that the alkyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxyl group. , an acryloyl group, a methacryloyl group, and the like.

( ^R3e )
In formula (Z1), R ^3e represents a hydrogen atom or a halogen atom.
Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
Among these, from the viewpoint of ease of synthesis, R ^3e is preferably a hydrogen atom.

( ^R4e )
In formula (Z2) above, R ^4e represents an optionally substituted alkylene group.
Alkylene groups include linear, branched and cyclic alkylene groups. The number of carbon atoms is usually 1 or more, preferably 2 or more, preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.

Specific examples of the alkylene group include methylene group, ethylene group, propylene group, propylene group, and butylene group. Among these, an ethylene group is preferred.
Examples of substituents that the alkylene group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. , an acryloyl group, a methacryloyl group, and the like.

Among these, R ^4e is preferably an ethylene group.

( ^R5e )
In the formula (Z2), represents an optionally substituted alkyl group.
Alkyl groups include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 4 or more, more preferably 5 or more, still more preferably 7 or more, preferably 15 or less, more preferably 10 or less, It is more preferably 9 or less.

Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and nonyl groups.
Examples of substituents that the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. , an acryloyl group, a methacryloyl group, and the like.
Among these, R ^5e is preferably a heptyl group, an octyl group, or a nonyl group from the viewpoint of a tapered shape.

( ^R6e )
Alkylene groups include linear, branched and cyclic alkylene groups. The number of carbon atoms is usually 1 or more, preferably 2 or more, preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.

Specific examples of the alkylene group include methylene group, ethylene group, propylene group, propylene group, and butylene group. Among these, an ethylene group is preferred.
Examples of substituents that the alkylene group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. , an acryloyl group, a methacryloyl group, and the like.

Among these, from the viewpoint of the tapered shape, R ^1e is a tert-butyl group, R ^2e is a group represented by the general formula (Z2) (provided that R ^4e is a methylene group, and R ^5e is an alkyl group having 7 to 9 carbon atoms ), a compound in which R ^3e is a hydrogen atom, or R ^1e is a hydrogen atom, R ^2e is a group represented by the general formula (Z3) (provided that R ^6e is a methylene group and R ^7e is a methyl group), R ^3e is A compound having a hydrogen atom is preferable, and R ^1e is a tert-butyl group and R ^2e is a group represented by the general formula (Z2) (provided that R ^4e is a methylene group and R ^5e is an alkyl group having 7 to 9 carbon atoms). , R ^3e are hydrogen atoms.

Other benzotriazole compounds include 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, octyl-3[3-tert -butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro -2H-benzotriazol-2-yl)phenyl]propionate mixture, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t Butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'- t-octylphenyl)benzotriazole, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl) -6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol.

Examples of commercially available benzotriazole compounds include Sumisorb (registered trademark, hereinafter the same) 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 (manufactured by Sumitomo Chemical), JF77, JF78, JF79, JF80, JF83 ( Johoku Chemical Industry), TINUVIN (registered trademark, hereinafter the same) PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN 326, TINUVIN900, "TINUVIN 928", TINUVIN928, TINUVIN1130 (manufactured by BASF), EVERSORB70, EVERSORB71, EV ERSORB72 , EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81 (manufactured by Taiwan Eiko Chemical Industry), Tomisorb (registered trademark, hereinafter the same) 100, Tomisorb 600 (API Corporation ), SEESORB (registered trademark) 701, SEESORB702, SEESORB703, SEESORB704, SEESORB706, SEESORB707, SEESORB709 (manufactured by Shipro Kasei Co., Ltd.), RUVA-93 (Otsuka Chemical Co., Ltd.) and the like.

Triazine compounds include 2-[4,6-di(2,4-xylyl)-1,3,5-triazin-2-yl]-5-octyloxyphenol, 2-[4,6-bis( 2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2-(2,4-dihydroxyphenyl)-4 ,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)glycidate reaction product, 2,4-bis[2-hydroxy-4-butoxyphenyl]- 6-(2,4-dibutoxyphenyl)-1,3,5-triazine and the like. Among these, hydroxyphenyltriazine compounds are preferred from the viewpoint of taper angle and exposure sensitivity.
Examples of commercially available triazine compounds include TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, and TINUVIN479 (manufactured by BASF).

Other ultraviolet absorbers include benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, dinaphthalene compounds, phenanthroline compounds, dyes and the like.
More specifically, for example, Sumisorb 130 (manufactured by Sumitomo Chemical), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Taiwan Eiko Chemical Industry Co., Ltd.), Tomisorb 800 (manufactured by API Corporation), SEESORB100, SEESORB101, SEESORB101S, SEESORB102, SEESORB10 3, SEESORB 105, Benzophenone compounds such as SEESORB106, SEESORB107, SEESORB151 (manufactured by Sipro Kasei); benzoate compounds such as Sumisorb 400 (manufactured by Sumitomo Chemical) and phenyl salicylate; 2-ethylhexyl cinnamate, 2-ethylhexyl paramethoxycinnamate, isopropyl methoxycinnamate, methoxy Cinnamic acid derivatives such as isoamyl cinnamate; , 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, etc. naphthalene derivatives; anthracene, anthracene such as 9,10-dihydroxyanthracene and derivatives thereof; azo dyes, benzophenone dyes, aminoketone dyes, quinoline dyes, anthraquinone dyes, diphenylcyanoacrylate dyes, triazine dyes, p - Dyes such as aminobenzoic acid dyes; Among these, from the viewpoint of exposure sensitivity, cinnamic acid derivatives and naphthalene derivatives are preferred, and cinnamic acid derivatives are particularly preferred.

Among these, benzotriazole compounds and/or hydroxyphenyltriazine compounds are preferred, and benzotriazole compounds are particularly preferred, from the viewpoint of tapered shape.

As the ultraviolet absorber, one type of compound may be used alone, or two or more types of compounds may be used in combination.

When the colored photosensitive resin composition of the present invention contains an ultraviolet absorber, the content is not particularly limited, but the total solid content of the colored photosensitive resin composition is usually 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, and usually 15% by mass or less, preferably 10% by mass Below, more preferably 5% by mass or less, still more preferably 3% by mass or less. The taper angle tends to increase when the lower limit value or more is used, and the sensitivity tends to be high when the upper limit value or less is used. When the colored photosensitive resin composition contains an ultraviolet absorber, the content of the ultraviolet absorber in the total solid content of the colored photosensitive resin composition is, for example, 0.01 to 15% by mass, and 0.05. ~10% by mass is preferred, 0.1 to 5% by mass is more preferred, 0.5 to 3% by mass is even more preferred, and 1 to 3% by mass is even more preferred.

Further, when the colored photosensitive resin composition of the present invention contains an ultraviolet absorber, the blending ratio for (B) the photopolymerization initiator is, (B) the amount of the ultraviolet absorber per 100 parts by mass of the photopolymerization initiator. , usually 1 part by mass or more, preferably 10 parts by mass or more, more preferably 30 parts by mass or more, still more preferably 50 parts by mass or more, particularly preferably 80 parts by mass or more, usually 500 parts by mass or less, preferably 300 It is not more than 200 parts by mass, more preferably not more than 100 parts by mass. The taper angle tends to increase when the lower limit value or more is used, and the sensitivity tends to be high when the upper limit value or less is used. (B) The blending amount of the ultraviolet absorber with respect to 100 parts by mass of the photopolymerization initiator is, for example, 1 to 500 parts by mass, preferably 10 to 300 parts by mass, more preferably 30 to 200 parts by mass, and 50 to 100 parts by mass. Parts by weight are more preferred, and 80 to 100 parts by weight are even more preferred.

[1-1-8] Polymerization Inhibitor The colored photosensitive resin composition of the present invention preferably contains a polymerization inhibitor. The inclusion of a polymerization inhibitor inhibits radical polymerization and tends to increase the taper angle of the obtained partition walls.
Polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, 2,6-di-tert-butyl-4-cresol (BHT) and the like. Among these, hydroquinone, methylhydroquinone and methoxyphenol are preferred, and methylhydroquinone is more preferred, from the viewpoint of the ability to inhibit polymerization.

It is preferable to contain one or more polymerization inhibitors. Usually, when producing the (C) alkali-soluble resin, the resin may contain a polymerization inhibitor, which may be used as the polymerization inhibitor of the present invention, or the polymerization inhibitor contained in the resin In addition to the agent, the same or different polymerization inhibitor may be added during the production of the colored photosensitive resin composition.

When the colored photosensitive resin composition contains a polymerization inhibitor, the content is not particularly limited, but the total solid content of the colored photosensitive resin composition is usually 0.0005% by mass or more, preferably 0.001. It is at least 0.01% by mass, more preferably at least 0.01% by mass, and is usually at most 0.1% by mass, preferably at most 0.08% by mass, more preferably at most 0.05% by mass. The taper angle tends to be able to be increased by making it equal to or greater than the lower limit, and the taper angle tends to be able to be kept high by making it equal to or less than the upper limit. When the colored photosensitive resin composition contains a polymerization inhibitor, the content of the polymerization inhibitor in the total solid content of the colored photosensitive resin composition is, for example, 0.0005 to 0.1% by mass, and 0 0.001 to 0.08 mass % is preferred, and 0.01 to 0.05 mass % is more preferred.

[1-1-9] Thermal polymerization initiator Further, the colored photosensitive resin composition of the present invention may contain a thermal polymerization initiator. Inclusion of a thermal polymerization initiator tends to increase the degree of cross-linking of the film. Specific examples of such thermal polymerization initiators include azo compounds, organic peroxides and hydrogen peroxide. These may be used individually by 1 type, and may use 2 or more types together.

In addition, when a thermal polymerization initiator is used in combination with the expectation of improving the sensitivity of the photopolymerization initiator and increasing the crosslink density of the film, the total content of these is the light in the total solid content of the colored photosensitive resin composition. It is preferable that the content ratio of the polymerization initiator is the same, and the combined ratio of the photopolymerization initiator and the thermal polymerization initiator is, from the viewpoint of sensitivity, thermal polymerization with respect to 100 parts by mass of the photopolymerization initiator. It is preferable to use 5 to 300 parts by mass of the initiator.

[1-1-10] Amino Compound The colored photosensitive resin composition of the present invention may contain an amino compound in order to accelerate thermosetting. In this case, the content of the amino compound in the colored photosensitive resin composition is usually 40% by mass or less, preferably 30% by mass or less, based on the total solid content of the colored photosensitive resin composition. Moreover, it is usually 0.5% by mass or more, preferably 1% by mass or more. When the content is equal to or less than the upper limit, storage stability tends to be maintained, and when the content is equal to or greater than the lower limit, sufficient thermosetting property tends to be ensured. When the colored photosensitive resin composition contains an amino compound, the content of the amino compound in the total solid content of the colored photosensitive resin composition is, for example, 0.5 to 40% by mass, and 1 to 30% by mass. is preferred.

The amino compound includes, for example, an amino compound having at least two alkoxymethyl groups obtained by condensation-denaturing a methylol group or a methylol group with an alcohol having 1 to 8 carbon atoms as a functional group. Specifically, for example, melamine resin obtained by polycondensation of melamine and formaldehyde; benzoguanamine resin obtained by polycondensation of benzoguanamine and formaldehyde; glycoluril resin obtained by polycondensation of glycoluril and formaldehyde; Examples include polycondensed urea resins; resins obtained by co-polycondensing two or more of melamine, benzoguanamine, glycoluril, or urea with formaldehyde; and modified resins obtained by modifying the methylol groups of the above resins by alcohol condensation. These may be used individually by 1 type, and may use 2 or more types together. Among these amino compounds, melamine resins and modified resins thereof are preferred, modified resins having a modified ratio of methylol groups of 70% or more are more preferred, and modified resins having a modified ratio of methylol groups of 80% or more are particularly preferred.

Specific examples of the above amino compounds include melamine resins and modified resins thereof, such as "Cymel" (registered trademark) 300, 301, 303, 350, 736, 738, 370, 771, 325, 327 manufactured by Cytec Co., Ltd. 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, and "Nikalac" (registered trademark) MW-390, MW-100LM manufactured by Sanwa Chemical Co., Ltd. , MX-750LM, MW-30M, MX-45, MX-302 and the like. Examples of the benzoguanamine resin and its modified resin include Cymel (registered trademark) 1123, 1125 and 1128 manufactured by Cytech. Examples of the glycoluril resin and modified resin thereof include "Cymel" (registered trademark) 1170, 1171, 1174, and 1172 manufactured by Cytec Co., Ltd., and "Nikalac" (registered trademark) MX manufactured by Sanwa Chemical Co., Ltd. -270 and the like. Examples of the urea resin and its modified resin include "UFR" (registered trademark) 65, 300 manufactured by Cytec Co., Ltd., and "Nikalac" (registered trademark) MX-290 manufactured by Sanwa Chemical Co., Ltd. be done.

[1-1-11] Coatability improver, development improver The colored photosensitive resin composition of the present invention contains a coatability improver and a development improver to improve the coatability and development solubility. may Known cationic, anionic, nonionic, fluorine-based and silicone-based surfactants can be used as coatability improvers or development improvers. Further, as a development modifier, a known one such as an organic carboxylic acid or its anhydride can be used. From the viewpoint of sensitivity, the content thereof is usually 20% by mass or less, preferably 10% by mass or less, relative to the total solid content of the photosensitive resin composition.

[1-1-12] Silane Coupling Agent It is also preferable to add a silane coupling agent to the colored photosensitive resin composition of the invention in order to improve the adhesion to the substrate. Various types of silane coupling agents such as epoxy, methacrylic, amino, and imidazole can be used. From the viewpoint of improving adhesion, epoxy and imidazole silane coupling agents are particularly preferred. From the viewpoint of adhesion, the content thereof is usually 20% by mass or less, preferably 15% by mass or less, relative to the total solid content of the colored photosensitive resin composition.

[1-1-13] Inorganic filler In addition, the colored photosensitive resin composition of the present invention further has an improved strength as a cured product, and an appropriate interaction with an alkali-soluble resin (formation of a matrix structure). An inorganic filler may be contained for the purpose of improving the flatness and taper angle of the coating film. Examples of such inorganic fillers include talc, silica, alumina, barium sulfate, magnesium oxide, titanium oxide, and those surface-treated with various silane coupling agents.

The average particle size of these inorganic fillers is usually 0.005 to 2 μm, preferably 0.01 to 1 μm. Here, the average particle size referred to in the present embodiment is a value measured by a laser diffraction scattering particle size distribution analyzer manufactured by Beckman Coulter. Among these inorganic fillers, silica sol and silica sol-modified products tend to be excellent in the effect of improving the taper angle as well as the dispersion stability, and thus are preferably blended. When the colored photosensitive resin composition of the present invention contains these inorganic fillers, the content thereof is usually 5% by mass or more, preferably 10% by mass or more, based on the total solid content from the viewpoint of sensitivity. , usually 80% by mass or less, preferably 70% by mass or less.

[1-1-14] Adhesion Improving Agent The colored photosensitive resin composition of the present invention may contain a phosphoric acid-based ethylenic monomer for the purpose of imparting adhesion to a substrate. As the phosphoric acid-based ethylenic monomer, (meth)acryloyloxy group-containing phosphates are preferred, and those represented by the following general formulas (g1), (g2) and (g3) are preferred.

In the general formulas (g1), (g2) and (g3), R ⁵¹ represents a hydrogen atom or a methyl group, l and l' are integers of 1-10, and m is 1, 2 or 3.

These phosphoric acid-based ethylenic monomers may be used singly or in combination of two or more. The content ratio when using these phosphoric acid-based ethylenic monomers is usually preferably 0.02% by mass or more, more preferably 0.05% by mass or more, in the total solid content of the colored photosensitive resin composition, and 0 0.1% by mass or more is more preferable, and 0.2% by mass or more is particularly preferable. Moreover, it is preferably 4% by mass or less, more preferably 3% by mass or less, still more preferably 2% by mass or less, and particularly preferably 1% by mass or less. When the lower limit value or more is used, the effect of improving the adhesion to the substrate tends to be sufficient, and when the upper limit value or less is used, deterioration of the adhesion to the substrate tends to be easily suppressed. When the colored photosensitive resin composition contains a phosphoric acid-based ethylenic monomer, the content of the phosphoric acid-based ethylenic monomer in the total solid content of the colored photosensitive resin composition is, for example, 0.02. 4% by mass, preferably 0.05 to 3% by mass, more preferably 0.1 to 2% by mass, and even more preferably 0.2 to 1% by mass.

[1-1-15] Solvent The colored photosensitive resin composition of the present invention usually contains a solvent, and each component described above is dissolved or dispersed in the solvent before use. The solvent is not particularly limited, but includes, for example, the organic solvents described below.

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, tri Glycol monoalkyl ethers such as ethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl Ethers, glycol dialkyl ethers such as diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, di Glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, 3-methoxy-1-butyl acetate; ethylene glycol Glycol diacetates such as diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate; Alkyl acetates such as cyclohexanol acetate; Amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether , diamyl ether, ethyl isobutyl ether, dihexyl ether; Ketones such as butyl ketone, methylhexyl ketone, methyl nonyl ketone, methoxymethylpentanone; methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, tri monohydric or polyhydric alcohols such as ethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol; aliphatics such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane Hydrocarbons; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene and bicyclohexyl; Aromatic hydrocarbons such as benzene, toluene, xylene and cumene; Amyl formate, ethyl formate, ethyl acetate , butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, Chains such as methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone or cyclic esters; alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and amyl chloride; ether ketones such as methoxymethylpentanone; Nitriles such as benzonitrile: tetrahydrofurans such as tetrahydrofuran, dimethyltetrahydrofuran, dimethoxytetrahydrofuran, and the like.

Commercially available solvents corresponding to the above include Mineral Spirit, Valsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and no. 2. Solvesso #150, Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names), and the like.

The solvent is capable of dissolving or dispersing each component in the colored photosensitive resin composition, and is selected according to the method of using the colored photosensitive resin composition of the present invention. , and a boiling point of 60 to 280° C. under atmospheric pressure (1013.25 hPa). More preferably, it has a boiling point of 70 to 260° C., such as propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate.

These solvents can be used singly or in combination of two or more. In addition, these solvents have a content of the total solid content in the colored photosensitive resin composition of usually 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and usually 90% by mass or less. It is preferably used in an amount of 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less. When the content is equal to or higher than the lower limit, the occurrence of coating unevenness tends to be suppressed, and when the content is equal to or lower than the upper limit, the occurrence of foreign matter, repelling, etc. tends to be suppressed. For example, the content of the total solid content in the colored photosensitive resin composition is 10 to 90% by mass, preferably 10 to 50% by mass, more preferably 15 to 40% by mass, and still more preferably 20 to 35% by mass. As such, a solvent may be used.

[1-2] Method for Preparing Colored Photosensitive Resin Composition The colored photosensitive resin composition of the present invention is prepared by mixing the above components with a stirrer.
For example, when the colorant (E) contains a component that does not require a solvent such as a pigment, it is preferably dispersed in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. Since the (E) colorant is finely divided by the dispersion treatment, the application properties of the colored photosensitive resin composition are improved.

Dispersion treatment is usually carried out in a system in which (E) a colorant, a solvent, and (F) a dispersant are used in combination, or optionally in combination with (C) a part or all of an alkali-soluble resin. Preferred (hereinafter, the mixture subjected to the dispersion treatment and the composition obtained by the treatment may be referred to as "ink" or "pigment dispersion"). In particular, it is preferable to use a polymeric dispersant as (F) the dispersant, since the resulting ink and colored photosensitive resin composition are prevented from thickening over time (excellent in dispersion stability).
Thus, in the process of producing the colored photosensitive resin composition, it is preferable to produce a pigment dispersion containing at least (E) a colorant, a solvent, and (F) a dispersant.
As the (E) colorant, organic solvent, and (F) dispersant that can be used in the pigment dispersion, those described as those that can be used in the colored photosensitive resin composition can be preferably employed. . Also, as the content ratio of each colorant in the (E) colorant in the pigment dispersion, the content ratio described as the content ratio in the colored photosensitive resin composition can be preferably employed.

When dispersing (E) the colorant with a sand grinder, glass beads or zirconia beads having a particle size of about 0.1 to 8 mm are preferably used. As for the dispersion treatment conditions, the temperature is usually from 0°C to 100°C, preferably from room temperature to 80°C. The appropriate dispersion time varies depending on the composition of the liquid, the size of the dispersion treatment apparatus, etc., and is therefore adjusted as appropriate. The index of dispersion is to control the glossiness of the ink so that the 20° specular glossiness (JIS Z8741) of the colored photosensitive resin composition is in the range of 50-300.

Further, the dispersed particle size of the pigment dispersed in the ink is usually 0.03 to 0.3 μm, and is measured by a dynamic light scattering method or the like.
Next, the ink obtained by the dispersion treatment and the other components contained in the colored photosensitive resin composition are mixed to form a uniform solution. In the manufacturing process of the colored photosensitive resin composition, since fine dust may be mixed in the liquid, it is desirable to filter the obtained colored photosensitive resin composition with a filter or the like.

[2] Partition walls and method for forming the same The colored photosensitive resin composition of the present invention can be suitably used for forming partition walls, particularly partition walls for partitioning the organic layers of an organic electroluminescence device. The partition wall of the present invention is composed of the colored photosensitive resin composition of the present invention.
The method for forming partition walls using the colored photosensitive resin composition described above is not particularly limited, and conventionally known methods can be employed. As a method for forming the partition walls, for example, a coating step of applying a colored photosensitive resin composition onto a substrate to form a photosensitive resin composition layer, and an exposure step of exposing the photosensitive resin composition layer are performed. A method comprising: Specific examples of the method for forming such partition walls include an inkjet method and a photolithography method.

In the inkjet method, a colored photosensitive resin composition whose viscosity has been adjusted by dilution with a solvent or the like is used as ink, and ink droplets are ejected onto a substrate along a predetermined pattern of partition walls by an inkjet method to obtain a colored photosensitive resin. The composition is applied onto a substrate to form a pattern of uncured barrier ribs. The pattern of uncured barrier ribs is then exposed to form cured barrier ribs on the substrate. The exposure of the uncured barrier rib pattern is performed in the same manner as the exposure step in the photolithography method described later, except that no mask is used.

In the photolithography method, a colored photosensitive resin composition is applied to the entire area of the substrate where the partition walls are to be formed to form a colored photosensitive resin composition layer. After the formed colored photosensitive resin composition layer is exposed according to a predetermined pattern of barrier ribs, the exposed colored photosensitive resin composition layer is developed to form barrier ribs on the substrate.

In the coating step of applying a colored photosensitive resin composition onto a substrate in the photolithography method, a contact transfer coating device such as a roll coater, a reverse coater, a bar coater, or a spinner (rotating A photosensitive resin composition is applied using a non-contact coating device such as a coating device) or a curtain flow coater, and if necessary, the solvent is removed by drying to form a colored photosensitive resin composition layer. .

Next, in the exposure step, a negative mask is used to irradiate the colored photosensitive resin composition with active energy rays such as ultraviolet rays and excimer laser light, and the colored photosensitive resin composition layer is formed according to the partition wall pattern. Partial exposure. For exposure, a light source that emits ultraviolet rays, such as a high-pressure mercury lamp, an extra-high pressure mercury lamp, a xenon lamp, or a carbon arc lamp, can be used. Although the amount of exposure varies depending on the composition of the colored photosensitive resin composition, it is preferably about 10 to 400 mJ/cm ² , for example.

Next, in the developing step, the barrier ribs are formed by developing the exposed colored photosensitive resin composition layer according to the pattern of the barrier ribs with a developer. The development method is not particularly limited, and an immersion method, a spray method, or the like can be used. Specific examples of the developer include organic ones such as dimethylbenzylamine, monoethanolamine, diethanolamine and triethanolamine, and aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia and quaternary ammonium salts. mentioned. Moreover, an antifoaming agent or a surfactant can be added to the developer.

After that, the barrier ribs after development are post-baked and cured by heating. Post-baking is preferably carried out at 150-250° C. for 15-60 minutes.

The substrate used for forming the partition is not particularly limited, and is appropriately selected according to the type of the organic electroluminescence device manufactured using the substrate on which the partition is formed. Suitable substrate materials include glass and various resin materials. Specific examples of the resin material include polyester such as polyethylene terephthalate; polyolefin such as polyethylene and polypropylene; polycarbonate; poly(meth)methacrylic resin; polysulfone; and polyimide. Among these substrate materials, glass and polyimide are preferable because of their excellent heat resistance. Depending on the type of organic electroluminescence element to be manufactured, a transparent electrode layer such as ITO or ZnO may be provided in advance on the surface of the substrate on which the barrier ribs are formed.

The shape and the like of the partition walls are not particularly limited, but when forming a functional layer with a predetermined thickness using an ink containing a component with low solvent solubility, it is preferable to form a thick film. In this case, the partition wall thickness is preferably 5 μm or more, more preferably 7 μm or more, still more preferably 8 μm or more, particularly preferably 10 μm or more, and usually 20 μm or less. The film thickness of the partition walls is, for example, 5 to 20 μm, preferably 7 to 20 μm, more preferably 8 to 20 μm, even more preferably 10 to 20 μm.

[3] Organic Electroluminescent Device The organic electroluminescent device of the present invention comprises the partition wall of the present invention.
Various organic electroluminescence devices are manufactured using the substrate provided with the barrier rib pattern manufactured by the method described above. The method for forming the organic electroluminescence element is not particularly limited, but preferably, after forming a partition pattern on the substrate by the above method, ink is injected into the region surrounded by the partition on the substrate to form pixels and the like. An organic electroluminescence device is manufactured by forming an organic layer.
Types of organic electroluminescence devices include bottom emission type and top emission type.
In the bottom emission type, for example, partition walls are formed on a glass substrate laminated with transparent electrodes, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are laminated in an opening surrounded by the partition walls. be. On the other hand, in the top emission type, for example, barrier ribs are formed on a glass substrate laminated with a metal electrode layer, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are stacked in an opening surrounded by the barrier ribs. created by

In the case where the partition wall has a trailing shape, the ink for forming the organic layer is repelled by the skirt portion of the partition wall, so that the region surrounded by the partition wall may not be sufficiently covered with the ink for forming the organic layer. On the other hand, by forming a good shape without tailing, the inside of the region surrounded by the partition can be sufficiently covered with the ink for forming the organic layer. As a result, for example, the problem of halation in the organic EL display element can be resolved.

Water, an organic solvent, and a mixed solvent thereof can be used as the solvent used when forming the ink for forming the organic layer. The organic solvent is not particularly limited as long as it can be removed from the film formed after injecting the ink. Specific examples of organic solvents include toluene, xylene, anisole, mesitylene, tetralin, cyclohexylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropyl alcohol, ethyl acetate, butyl acetate, 3-phenoxytoluene, and the like. is mentioned. In addition, surfactants, antioxidants, viscosity modifiers, ultraviolet absorbers, and the like can be added to the ink.

As a method for injecting ink into the region surrounded by the partition wall, an inkjet method is preferable because a small amount of ink can be easily injected into a predetermined location. The ink used for forming the organic layer is appropriately selected according to the type of organic electroluminescence element to be manufactured. When the ink is injected by an inkjet method, the viscosity of the ink is not particularly limited as long as the ink can be discharged well from the inkjet head, but is preferably 4 to 20 mPa·s, more preferably 5 to 10 mPa·s. The viscosity of the ink can be adjusted by adjusting the solid content in the ink, changing the solvent, adding a viscosity modifier, and the like.

Examples of the light-emitting layer include organic electroluminescent layers as described in Japanese Patent Application Laid-Open No. 2009-146691 and Japanese Patent No. 5734681. Quantum dots as described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may also be used.

[4] Image Display Device The image display device of the present invention includes the organic electroluminescence device of the present invention. As long as the organic electroluminescence device of the present invention is included, the type and structure of the image display device are not particularly limited, and for example, it can be assembled according to a conventional method using an active drive type organic electroluminescence device. For example, the image display device of the present invention is formed by the method described in "Organic EL Display" (Ohmsha, August 20, 2004, Shizuo Tokito, Chihaya Adachi, Hideyuki Murata). can do. For example, an image may be displayed by combining an organic electroluminescent element that emits white light and a color filter, or an image may be displayed by combining organic electroluminescent elements emitting different colors such as RGB.

[5] Lighting The lighting of the present invention includes the organic electroluminescence device of the present invention. There are no particular restrictions on the type and structure, and the organic electroluminescence device of the present invention can be assembled according to a conventional method. The organic electroluminescence element may be of a simple matrix drive system or an active matrix drive system.
In order for the illumination of the present invention to emit white light, an organic electroluminescent element that emits white light may be used. Alternatively, organic electroluminescence elements emitting different colors may be combined to form a white color by mixing the colors, or a color mixing ratio may be adjusted to provide a toning function.

Hereinafter, the colored photosensitive resin composition of the present invention will be described with reference to specific examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

<Alkali-soluble resin-I>
A copolymer resin containing dicyclopentanyl methacrylate/styrene/glycidyl methacrylate (molar ratio: 0.3/0.1/0.6) as constituent monomers is added with acrylic acid in an equivalent amount to glycidyl methacrylate, Further, an alkali-soluble acrylic copolymer resin obtained by addition reaction of 0.39 mol of tetrahydrophthalic anhydride with respect to 1 mol of the above copolymer resin. The polystyrene equivalent weight average molecular weight (Mw) measured by GPC was 9000, and the solid content acid value was 80 mgKOH/g. (c1) corresponds to an acrylic copolymer resin having an ethylenically unsaturated group in a side chain.

<Alkali-soluble resin-II>
"ZCR-1642H" manufactured by Nippon Kayaku Co., Ltd. (Mw6500, acid value 98 mgKOH/g). (c2) corresponds to epoxy (meth)acrylate resins.

<Alkali-soluble resin-III>

50 g of the epoxy compound (epoxy equivalent weight: 264) having the above structure, 13.65 g of acrylic acid, 60.5 g of methoxybutyl acetate, 0.936 g of triphenylphosphine, and 0.032 g of para-methoxyphenol were attached with a thermometer, a stirrer, and a cooling tube. The mixture was placed in a flask and reacted with stirring at 90° C. until the acid value became 5 mgKOH/g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.

25 parts by mass of the epoxy acrylate solution, 0.74 parts by mass of trimethylolpropane (TMP), 3.95 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), and 2.7 parts by mass of tetrahydrophthalic anhydride (THPA) was placed in a flask equipped with a thermometer, a stirrer and a cooling tube, and the temperature was slowly raised to 105° C. while stirring to react to obtain an alkali-soluble resin-III. The polystyrene equivalent weight average molecular weight (Mw) measured by GPC was 4100, and the solid content acid value was 112 mgKOH/g. (c2) corresponds to epoxy (meth)acrylate resins.

<Alkali-soluble resin-IV>
A copolymer resin containing dicyclopentanyl methacrylate/styrene/glycidyl methacrylate (molar ratio: 2/5/93) as constituent monomers is subjected to an addition reaction of acrylic acid and glycidyl methacrylate in an equivalent amount, and further tetrahydrophthalic anhydride is added to the above. It was added at a molar ratio of 0.1 to 1 mol of the copolymer resin to obtain an alkali-soluble resin-IV. The polystyrene equivalent weight average molecular weight (Mw) measured by GPC was 7700, and the solid content acid value was 28.5 mgKOH/g. (c1) corresponds to an acrylic copolymer resin having an ethylenically unsaturated group in a side chain.

<Alkali-soluble resin-V>
An alkali-soluble acrylic copolymer resin containing cyclohexyl methacrylate/methacrylic acid (molar ratio: 85/15) as constituent monomers. The polystyrene equivalent weight average molecular weight (Mw) measured by GPC was 12300, and the solid content acid value was 94 mgKOH/g.

<Alkali-soluble resin-VI>
An alkali-soluble acrylic copolymer resin containing methyl methacrylate/methacrylic acid (molar ratio: 82/18) as constituent monomers. The polystyrene equivalent weight average molecular weight (Mw) measured by GPC was 11400, and the solid content acid value was 97 mgKOH/g.

<Organic black pigment>
BASF Corporation, "Irgaphor (registered trademark) Black S 0100 CF" (having a chemical structure represented by the following formula (1-1))

<Dispersant-I>
"BYK-LPN21116" manufactured by BYK Chemie (A block having a quaternary ammonium base and a tertiary amino group in the side chain, and a B block having no quaternary ammonium base and tertiary amino group, acrylic AB Block copolymer. Amine value: 70 mgKOH/g. Acid value: 1 mgKOH/g or less.)
The A block of Dispersant-I contains repeating units of the following formulas (1a) and (2a), and the B block contains repeating units of the following formula (3a). The content ratios of the repeating units of the following formulas (1a), (2a), and (3a) in the total repeating units of Dispersant-I are 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively. be.

<Pigment derivative>
"Solsperse 12000" manufactured by Lubrizol

<Solvent-I>
PGMEA: propylene glycol monomethyl ether acetate <solvent-II>
MB: 3-methoxy-1-butanol <photopolymerizable monomer>
DPHA: Dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.

<Photoinitiator>
A compound having the following chemical structure was used.

<Liquid Repellent Agent>
Megafac RS-72-K manufactured by DIC (fluorinated oligomer having an ethylenic double bond)

<Additive-I>
Showa Denko Karenz MT PE1 (pentaerythritol tetrakis (3-mercaptobutyrate)

<Additive-II>
Nippon Kayaku Co., Ltd. KAYAMER PM-21 (methacryloyl group-containing phosphate)

<Preparation of Pigment Dispersions I to III>
The pigment, dispersant, dispersing aid, alkali-soluble resin, and solvent shown in Table 1 were mixed in the mass ratio shown in Table 1. This mixed liquid was subjected to dispersion treatment for 3 hours in the range of 25 to 45° C. using a paint shaker. Zirconia beads with a diameter of 0.5 mm were used as the beads, and 2.5 times the mass of the mixed solution was added. After completion of dispersion, the beads and the dispersion liquid were separated by a filter to prepare pigment dispersion liquids I to III.
The blending ratio of the dispersant and the alkali-soluble resin in Table 1 is the solid content conversion value, and the blending ratio of the solvent includes the amount of the solvent derived from the dispersant and the alkali-soluble resin.

[Examples 1 to 9 and Comparative Examples 1 to 3]
Using the pigment dispersion prepared above, each component was mixed so that the blending ratios shown in Tables 2 and 3 were obtained, and the colored photosensitive resins of Examples 1 to 9 and Comparative Examples 1 to 3 were dissolved by stirring. A composition was prepared. Using the obtained colored photosensitive resin composition, performance evaluation was performed by the method described later.
The mixing ratios of the alkali-soluble resin and the liquid repellent in Tables 2 and 3 are solid content conversion values, and the mixing ratio of the solvent includes the amount of the solvent derived from the alkali-soluble resin and the liquid repellent. On the other hand, the mixing ratio of the pigment dispersion liquid is not the solid content conversion value but the total amount including the solvent.

The method of performance evaluation is explained below.

<Preparation of substrate for measurement>
Using a spinner, each of the colored photosensitive resin compositions was applied onto a glass substrate so as to have a thickness of 10.0 μm after heat curing. Then, it was heated and dried on a hot plate at 100° C. for 90 seconds to obtain a coated substrate. It is spray-developed at 24 ° C. using an aqueous solution in which 0.04% by mass of KOH and 0.07% by mass of Emulgen A-60 (surfactant manufactured by Kao Corporation) are dissolved without exposure processing, The break time was obtained by reading the time until the coating film was completely removed by development.
Next, a coated substrate was obtained by the same procedure and exposed to ultraviolet rays at an exposure amount of 50 mJ/cm ² without using an exposure mask. At this time, the intensity at a wavelength of 365 nm was 45 mW/cm ² . This substrate was subjected to spray development at 24° C. using the developer for a development time 1.2 times the break time, and then washed with pure water for 10 seconds. This substrate was cured by heating in an oven at 230° C. for 30 minutes to obtain a substrate for measurement.

<Measurement of optical density (OD)>
The optical density (OD) of the measurement substrate was measured with a transmission densitometer ("D200-II" manufactured by Gretag Macbeth). Furthermore, the film thickness at the measurement point is measured by a non-contact surface/layer cross-sectional shape measurement system VertScan (R) 2.0 manufactured by Ryoka System Co., Ltd., and from the optical density (OD) and film thickness, per unit film thickness (1 μm) The optical density (unit OD, OD/μm) was calculated. The results are shown in Tables 2 and 3.

<Measurement of PGMEA contact angle>
Using a Drop Master 500 contact angle measurement device manufactured by Kyowa Interface Science Co., Ltd., 0.7 μL of PGMEA (propylene glycol monomethyl ether acetate) was dropped on the measurement substrate under conditions of 23 ° C. and 50% humidity 1 second after Contact angles were measured and the results are shown in Tables 2 and 3. A larger contact angle indicates higher ink repellency.

<Creating a partition>
Using a spinner, each of the colored photosensitive resin compositions was applied onto a glass substrate so as to have a thickness of 10.0 μm after heat curing. After that, it was dried by heating on a hot plate at 100° C. for 90 seconds. The obtained coating film was exposed to ultraviolet rays using a photomask. The exposure dose was 50 mJ/cm ² and the exposure gap was 16 μm. At that time, the intensity at a wavelength of 365 nm was 45 mW/cm ² . As a photomask, a mask having grid-like openings (a mask having a plurality of covering portions of 80 μm×280 μm at intervals of 40 μm) was used. Next, under the same conditions as <Preparation of substrate for measurement>, the substrate was developed with a development time 1.2 times the break time, and then washed with pure water for 10 seconds. This substrate was cured by heating in an oven at 230° C. for 30 minutes to obtain a substrate with grid-like partition walls.

<Evaluation of linearity of edge portion of partition pattern>
The surface of the barrier ribs of the substrate with grid-like barrier ribs was observed with a SEM at a magnification of 6000 to evaluate the linearity of the edge portions of the barrier ribs. If the edge of the partition is straight and there is no residue, it is evaluated as "A". The results are shown in Tables 2 and 3.

<Evaluation of board surface condition>
The surface condition of the measurement substrate was visually observed to evaluate the presence or absence of surface roughness. If the surface was sufficiently glossy, it was rated as "A", and if it was not glossy, it was rated as "B". The results are shown in Tables 2 and 3.
When the surface is glossy, it is in a state close to specular reflection, i.e., a uniform surface with low roughness. is.

From Table 2, the colored photosensitive resin compositions of Examples 1 and 2 have a colorant content of 20% by mass or less in the total solid content, and (c1) acrylic having an ethylenically unsaturated group in the side chain It contains a resin and (c2) an epoxy (meth)acrylate resin, has good light-shielding properties, has a high PGMEA contact angle, exhibits good ink repellency, and has linearity at the edge of the partition wall. It turns out that it is good. Moreover, it can be seen that the surface condition of the substrate is also good, with gloss and no surface roughness.

On the other hand, in the colored photosensitive resin composition of Comparative Example 2, the content of the colorant exceeds 20% by mass in the total solid content, that is, the colorant is excessively contained. In spite of not containing an acrylic resin having a group, the PGMEA contact angle is high, good ink repellency is exhibited, and the linearity of the edge portion of the partition wall is good. From this, it can be seen that the problem of ink repellency and linearity does not exist when the coloring agent is excessively contained. The surface of the substrate was not glossy and had surface roughness.

On the other hand, in the colored photosensitive resin composition of Comparative Example 1, although the content of the coloring agent in Comparative Example 2 was changed to 20% by mass or less, the linearity of the edge portion of the partition walls was good. , the contact angle of PGMEA is low and the ink repellency is poor. From the comparison of Comparative Example 2 and Comparative Example 1, when the content of the coloring agent is 20% by mass or less in the total solid content, the contact angle of PGMEA becomes low, resulting in poor ink repellency. I understand. This is probably because the lower content of the colorant increased the orientation of the liquid-repellent agent toward the surface, and most of the liquid-repellent agent, which was not sufficiently bonded to the film surface, flowed out during development.

Comparative Example 1 does not contain (c1) an acrylic resin having an ethylenically unsaturated group in the side chain and contains (c2) an epoxy (meth)acrylate resin. 3 containing (c1) an acrylic resin having an ethylenically unsaturated group in the side chain and not containing (c2) an epoxy (meth)acrylate resin, the PGMEA contact angle is high and the ink repellency is high. It can be seen that the linearity of the edge portion of the partition wall is poor, although the linearity is good.
This is because (c1) containing an acrylic copolymer resin having an ethylenically unsaturated group in the side chain has a high degree of freedom within the film for radicals generated during exposure due to its flexible skeleton, and the film surface Radical deactivation by oxygen can be suppressed, the film surface has high curability, and the side chain has an ethylenically unsaturated group. It is thought that the PGMEA contact angle is high and the ink repellency is good as a result of the fact that the PGMEA contact angle is high and the ink repellency is good. However, since it does not contain the epoxy (meth)acrylate resin (c2), which tends to prevent the adhesion to the substrate from becoming too high due to having a rigid skeleton, the adhesion to the substrate becomes too high, and the partition walls are formed. It is considered that the straightness of the edge portion was not sufficient.

On the other hand, in the colored photosensitive resin compositions of Examples 1 and 2, the content of the colorant is 20% by mass or less in the total solid content, but (c1) the ethylenically unsaturated group in the side chain By containing an acrylic resin having a flexible skeleton, the degree of freedom in the film of radicals generated during exposure is high, and the deactivation of radicals by oxygen on the film surface can be suppressed, and the curability of the film surface is high. Furthermore, by having an ethylenically unsaturated group in the side chain, the liquid repellent agent oriented on the film surface can be sufficiently captured, and it remains on the film surface without flowing out during development, and the PGMEA contact angle is high. It is considered that the ink repellency is improved. In addition, by containing (c2) epoxy (meth)acrylate resin, the rigid skeleton such as the aromatic ring weakens the bonding force with hydroxyl groups and silanol groups on the substrate, making the unexposed areas easier to develop. It is considered that the straightness of the edge portion of the partition is good. In addition, since the content of the coloring agent is 20% by mass or less in the total solid content, the difference in curability between the surface and the inside of the film is reduced, so the difference in shrinkage between the surface and the inside of the film during heat curing is also reduced. It is considered that the surface condition of the substrate is improved by the heat treatment, and the surface roughness is suppressed.

Examples 3 to 6 used (c1) a pigment dispersion containing an acrylic resin having an ethylenically unsaturated group in the side chain as a dispersing resin. In addition, the linearity of the edge portion of the partition wall was good, and the substrate surface condition was also good, and surface roughness was suppressed. From the comparison between Examples 3 and 4, the higher the ratio of (c1) the acrylic copolymer resin, the higher the contact angle of PGMEA. In addition, from the comparison of Examples 3, 5 and 6, the content of the coloring agent is not particularly limited as long as it is 20% by mass or less in the total solid content, and the PGMEA contact angle is high and the ink repellency is good. It can be seen that the surface condition is good and surface roughness is suppressed.

In Example 7, the type of colorant was changed in Example 3. From the comparison between Example 3 and Example 7, the PGMEA contact angle was high and the ink repellency was good regardless of the type of colorant. , the linearity of the edge portions of the partition walls is good, the substrate surface condition is good, and surface roughness is suppressed.

In Example 8, the type of (c2) epoxy (meth)acrylate resin was changed in Example 3, but from a comparison of Examples 3 and 8, the type of (c2) epoxy (meth)acrylate resin Therefore, it can be seen that the linearity of the edge portion of the partition wall is good.
In Example 9, in Example 3, (c1) alkali-soluble resin-I, which is an acrylic resin having an ethylenically unsaturated group in the side chain, was partially changed to alkali-soluble resin-IV. A comparison of Examples 3 and 9 shows that the PGMEA contact angle is high and the ink repellency is good regardless of the type of acrylic resin (c1) having an ethylenically unsaturated group in the side chain.

Claims (10)

A colored photosensitive resin composition containing (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, (D) a liquid repellent agent, and (E) a coloring agent,
The content of the (E) colorant is 20% by mass or less in the total solid content of the colored photosensitive resin composition,
The (C) alkali-soluble resin contains (c1) an acrylic copolymer resin having an ethylenically unsaturated group in a side chain, and (c2) an epoxy (meth)acrylate resin,
A colored photosensitive resin composition, wherein the content of the (c2) epoxy (meth)acrylate resin relative to the total amount of the (C) alkali-soluble resin is 10% by mass or more and 70% by mass or less. 2. The colored photosensitive resin composition according to claim 1, wherein the (c1) acrylic copolymer resin having an ethylenically unsaturated group in a side chain has a partial structure represented by the following general formula (I).

(In formula (I), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. * represents a bond.) The (c2) epoxy (meth)acrylate resin is an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (i), an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (ii) ) The colored photosensitive resin composition according to claim 1 or 2, comprising at least one selected from the group consisting of acrylate resins and epoxy (meth)acrylate resins having a partial structure represented by the following general formula (iii): thing.

(In formula (i), R ^a represents a hydrogen atom or a methyl group, and R ^b represents a divalent hydrocarbon group which may have a substituent. The benzene ring in formula (i) is further It may be substituted with any substituent. * represents a bond.)

(In formula (ii), each R ^c independently represents a hydrogen atom or a methyl group. R ^d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * represents a bond. .)

(In formula (iii), R ^e represents a hydrogen atom or a methyl group, γ is a single bond, —CO—, an optionally substituted alkylene group, or an optionally substituted 2 represents a valent cyclic hydrocarbon group.The benzene ring in formula (iii) may be further substituted with an optional substituent.* represents a bond.) 4. The colored photosensitive resin composition according to any one of claims 1 to 3, wherein the (D) liquid repellent agent has a cross-linking group. The colored photosensitive resin composition according to any one of claims 1 to 4, further comprising a chain transfer agent. The colored photosensitive resin composition according to any one of claims 1 to 5, wherein the (E) colorant is an organic pigment. A partition made of the colored photosensitive resin composition according to any one of claims 1 to 6. An organic electroluminescence device comprising the partition according to claim 7 . An image display device comprising the organic electroluminescence device according to claim 8 . A lighting comprising the organic electroluminescent device according to claim 8 .