JP7443713B2 - Photosensitive resin composition, cured product, and image display device - Google Patents

Description

The present invention relates to a photosensitive resin composition used to form partition walls, and further relates to a cured product obtained by curing the photosensitive resin composition and an image display device equipped with the cured product.

Conventionally, organic electroluminescent devices included in organic field displays and organic field lighting have been manufactured by forming barrier ribs (banks) on a substrate and then laminating various functional layers within the area surrounded by the barrier ribs. Manufactured. As a method of 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 for laminating various functional layers within an area surrounded by partition walls, first, an ink containing the material constituting the functional layer is prepared, and then the prepared ink is injected into an area surrounded by partition walls. There are known ways to do this. 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 forming a functional layer using ink, ink repellency ( Liquid repellency) may be required.
Furthermore, in recent years, various properties other than ink repellency have been required for partition walls, and various photosensitive resin compositions have been developed.
Patent Document 1 describes that by using a specific alkali-soluble resin and a chain transfer agent in combination, the amount of outgas generated can be reduced and the taper angle can be increased. Further, Patent Document 2 describes that by using a specific fluorine-containing polymerizable resin, excellent antifouling properties and scratch resistance can be imparted to the surface of a cured coating film.

International Publication No. 2018/043746 Japanese Patent Application Publication No. 2012-092308

In recent years, barrier ribs have been actively developed. For example, in order to form a functional layer of a predetermined thickness using ink containing components with low solvent solubility, diluted ink is applied to the area surrounded by the barrier ribs. It is necessary to inject a large amount of ink, and thick partition walls are naturally required. Even such thick-film partition walls are required to exhibit sufficient ink repellency in order to prevent inks from mixing with each other between adjacent regions. On the other hand, the functional layer in the area surrounded by the partition wall (pixel area) becomes the pixel of the image display device, but even if the ink repellency is increased, the pixel area will not be contaminated and can be coated using the inkjet method. It is also required that the ink be uniformly wetted and spread within the pixel area when applied.

The present inventors investigated and found that Patent Documents 1 and 2 do not contain any description of thick film partition walls, and the liquid repellent agents and photosensitive resin compositions described in these documents do not contain any description of thick film partition walls. The ink repellency was not sufficient, and the wetting and spreading properties of pixel areas during inkjet coating were insufficient.
SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a photosensitive resin composition that has high ink repellency and can form partition walls that have good wettability and spreadability over pixel areas during inkjet coating.

As a result of intensive studies, the present inventors have found that the above problems can be solved by using a specific liquid repellent, and have completed the present invention.
That is, the gist of the present invention is as follows.

[1] A photosensitive resin composition containing (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, and (D) a liquid repellent,
The liquid repellent (D) has a repeating unit (i) represented by the following general formula (D-1-1) and a partial structure (ii) represented by the following general formula (D-1-2). A photosensitive resin composition comprising a resin (D-1).

(In the formula, L represents a polycyclic aliphatic hydrocarbon skeleton that may have a substituent.
However, L has one or more fluorine-containing organic groups having 1 to 30 carbon atoms as the substituent.
* represents a bond. )

(In the formula, R ¹¹ represents a hydrogen atom or a methyl group.
g represents an integer from 0 to 6.
* represents a bond. )

[2] The photosensitivity according to [1], wherein the repeating unit (i) in the resin (D-1) is a repeating unit (i-2) represented by the following general formula (D-1-4). Resin composition.

(In the formula, R ¹ to R ⁴ each independently represent a hydrogen atom or an arbitrary substituent.
However, at least one of R ¹ to R ⁴ is a fluorine-containing organic group having 1 to 30 carbon atoms.
n represents an integer from 0 to 2.
* represents a bond. )

[3] The photosensitive resin composition according to [1] or [2], wherein the resin (D-1) further has a repeating unit (iii) represented by the following general formula (D-1-5). .

(In the formula, R ⁵ represents the partial structure (ii).
* represents a bond. )

[4] The photosensitive resin composition according to any one of [1] to [3], wherein the content of the liquid repellent (D) is 0.3% by mass or more based on the total solid content.
[5] The photosensitive resin composition according to any one of [1] to [4], wherein the content of the liquid repellent (D) is 5% by mass or less based on the total solid content.
[6] The photosensitive resin composition according to any one of [1] to [5], further comprising (E) a colorant.

[7] The photosensitive resin composition according to any one of [1] to [6], which is used for forming partition walls.
[8] A cured product obtained by curing the photosensitive resin composition according to any one of [1] to [7].
[9] An image display device comprising the cured product according to [8].

ADVANTAGE OF THE INVENTION According to the present invention, it is possible to provide a photosensitive resin composition capable of forming a partition wall that has high ink repellency and has good wetting and spreading properties in pixel areas during inkjet coating.

The present invention will be explained in detail below. Note that the following description is an example of the embodiment of the present invention, and the present invention is not limited to these unless it exceeds 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 photosensitive resin composition. shall mean. Furthermore, in the present invention, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as lower and upper limits.
In addition, in the present invention, the term "(co)polymer" includes both a single polymer (homopolymer) and a copolymer (copolymer), and also includes "(acid)anhydride", "(Anhydrous)...acid" means to include both acids and their anhydrides.
In the present invention, a partition wall material refers to a bank material, a wall material, and a wall material, and similarly, a partition wall refers to a bank, a wall, and a wall.
In the present invention, the weight average molecular weight refers to the weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography).

[1] Photosensitive resin composition The photosensitive resin composition of the present invention contains (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, and (D) a liquid repellent. do. Furthermore, it may further contain other components as required, such as a coloring agent, a chain transfer agent, a solvent, and the like.

In the present invention, a partition wall is, for example, a partition wall for partitioning a functional layer (organic layer, light emitting part) in an active drive type organic electroluminescent device, and a partition wall for configuring a functional layer in the partitioned area (pixel area). It is used to form pixels, etc., including functional layers and partition walls, by discharging and drying ink, which is the material of the material.

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

[1-1-1] Component (A); Ethylenically unsaturated compound The photosensitive resin composition of the present invention contains (A) an ethylenically unsaturated compound. (A) Containing the ethylenically unsaturated compound is considered to increase sensitivity.
The ethylenically unsaturated compound used here refers to a compound having one or more ethylenically unsaturated bonds in its molecule, but it has polymerizability, crosslinkability, and associated developer solution 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, in order to expand the difference in solubility in In other words, it is more preferably a (meth)acrylate compound.

In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated bonds in one molecule. The number of ethylenically unsaturated groups that the polyfunctional ethylenic monomer has is not particularly limited, but is preferably 2 or more, more preferably 3 or more, even more preferably 5 or more, and preferably 15. The number is more preferably 10 or less, further preferably 8 or less, particularly preferably 7 or less. When the amount is equal to or more than the lower limit, polymerizability tends to be improved and sensitivity becomes higher, and when the amount is less than the upper limit, the developability tends to be better.
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, aromatic polyhydroxy compounds Examples include esters obtained by an esterification reaction between polyhydric hydroxy compounds such as esters, etc., and unsaturated carboxylic acids and polybasic carboxylic acids.

Examples of the ester of the aliphatic polyhydroxy compound and unsaturated carboxylic acid 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, glycerol acrylate, and methacrylic acid esters in which the acrylate of these exemplary compounds is replaced with methacrylate. , itaconate ester instead of itaconate, crotonate ester instead of cronate, maleate ester instead of maleate, and the like.

Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic esters and methacrylic 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 polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids are not necessarily single products, but are typical examples. Specific examples include 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.

In addition, examples of the polyfunctional ethylenic monomer used in the present invention include a polyisocyanate compound and a hydroxyl group-containing (meth)acrylic ester, or a polyisocyanate compound, a polyol, and a hydroxyl group-containing (meth)acrylic ester. Urethane (meth)acrylates such as those obtained; Epoxy acrylates such as addition reaction products of polyvalent epoxy compounds and hydroxyl group-containing (meth)acrylic acid esters or (meth)acrylic acid; Acrylamides such as ethylene bisacrylamide; Allyl esters such as diallyl phthalate; 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 Gosei Kagaku Kogyo Co., Ltd.).

Among these, from the viewpoint of appropriate taper angle and sensitivity, it is preferable to use esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids or urethane (meth)acrylates as the ethylenically unsaturated compound (A), Dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dibasic acid anhydride adduct of dipentaerythritol penta(meth)acrylate , a dibasic acid anhydride adduct of pentaerythritol tri(meth)acrylate, etc. are more preferably used.
These may be used alone or in combination of two or more.

In the present invention, the molecular weight of the ethylenically unsaturated compound (A) is not particularly limited, but from the viewpoints of sensitivity, ink repellency, and taper angle, it is preferably 100 or more, more preferably 150 or more, even more preferably 200 or more, Even more preferably 300 or more, particularly preferably 400 or more, most preferably 500 or more, preferably 1000 or less, more preferably 700 or less.
The number of carbon atoms in the ethylenically unsaturated compound (A) 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, even more preferably 15 or more, and even more It is preferably 20 or more, particularly preferably 25 or more, preferably 50 or less, more preferably 40 or less, still more preferably 35 or less, particularly preferably 30 or less.

The content of the ethylenically unsaturated compound (A) in the 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 in the total solid content. % or more, more preferably 15% by mass or more, particularly preferably 20% by mass or more, and usually 80% by mass or less, preferably 60% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass. It is as follows. When the amount 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.

Further, the content ratio of (A) ethylenically unsaturated compound to 100 parts by mass of (C) alkali-soluble resin is not particularly limited, but 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 20 parts by mass or more, particularly preferably 30 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, still more preferably 60 parts by mass or less, particularly preferably It is preferably 50 parts by mass or less. When the value is equal to or more than the lower limit, the sensitivity during exposure tends to be good and the taper angle tends to be good, and when the value is equal to or less than the upper limit, the developability tends to be good.

[1-1-2] Component (B); Photopolymerization initiator The 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 ethylenically unsaturated compound (A) with actinic rays, and any known photopolymerization initiator may be used. I can do it.

In the photosensitive resin composition of the present invention, as the photopolymerization initiator (B), a photopolymerization initiator commonly used in this field can be used. Examples of such photopolymerization initiators include metallocene compounds containing titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; hexane compounds described in JP-A 2000-56118; Aryl biimidazole derivatives; halomethylated oxadiazole derivatives described in JP-A-10-39503, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl- Radical activators such as α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; oximes described in JP-A No. 2000-80068, JP-A No. 2006-36750, etc. Examples include ester compounds.

Specifically, for example, metallocene compounds include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluorophenyl ), dicyclopentadienyl titanium bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis(2,4,6-trifluorophenyl), dicyclopentadienyl titanium di( 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-(pyrro-1-yl)-phenyl], etc. .

In addition, as biimidazole derivatives, 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 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, as halomethylated oxadiazole derivatives, 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, Examples include 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.

Further, as halomethyl-s-triazine derivatives, 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, as α-aminoalkylphenone derivatives, 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 -t, 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, and when using alkali-soluble resins containing phenolic hydroxyl groups, they are disadvantageous in terms of sensitivity. Oxime ester compounds with excellent sensitivity are useful. Oxime ester compounds have a structure that absorbs ultraviolet light, 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. Therefore, it is possible to obtain a highly sensitive photosensitive resin composition in a small amount.

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

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

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

Examples of the aromatic ring group for R ^21a include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive resin composition. Further, 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 phenyl group, naphthyl group, pyridyl group, furyl group, etc. Among these, from the viewpoint of developability, phenyl group or naphthyl group is preferable, and phenyl group is more preferable.
Examples of substituents that the aromatic ring group may have include hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, alkyl groups, alkoxy groups, and groups in which these substituents are linked. From the viewpoint of properties, an alkyl group, an alkoxy group, or a group formed by connecting these groups is preferable, and a connected alkoxy group is more preferable.
Among these, from the viewpoint of sensitivity, R ^21a is preferably an alkyl group that may have a substituent or an aromatic ring group that may have a substituent.

Preferably, R ^21b includes an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, or an optionally substituted diphenyl sulfide group. Among these, an optionally substituted carbazolyl group is preferred from the viewpoint of sensitivity.

Further, 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 the alkanoyl group include an acetyl group, an ethyl group, a propanoyl group, a butanoyl group, and the like.
Examples of substituents that the alkanoyl group may have include aromatic ring groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, etc. From the viewpoint of ease of synthesis, it should be unsubstituted. is preferred.

Further, 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, it is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably It is 10 or less. Specific examples of the aryloyl group include benzoyl group and 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, and from the viewpoint of ease of synthesis, it is preferably unsubstituted. .
Among these, from the viewpoint of sensitivity, R ^22a is preferably an alkanoyl group that may have a substituent, more preferably an unsubstituted alkanoyl group, and even more preferably an acetyl group.

The photopolymerization initiators may be used alone or in combination of two or more.
The photopolymerization initiator may contain a sensitizing dye and a polymerization accelerator depending on the wavelength of the image exposure light source, if necessary, for the purpose of increasing the sensitivity. Examples of sensitizing dyes include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, and coumarin having a heterocycle as described in JP-A-3-239703 and JP-A-5-289335. Dyes, 3-ketocoumarin compounds described in JP-A-3-239703 and JP-A-5-289335, pyrromethene dyes as described in JP-A-6-19240, and others, JP-A-47-2528, JP-A-47-2528, JP-A-54-155292, JP-A-45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005 Publication, JP-A-59-56403, JP-A-2-69, JP-A-57-168088, JP-A-5-107761, JP-A-5-210240, JP-A-4-288818 Examples include dyes having a dialkylaminobenzene skeleton described in publications.

Among these sensitizing dyes, preferred 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, and 3,3'-diaminobenzophenone. , 3,4-diaminobenzophenone and other benzophenone compounds; 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 , (p-diethylaminophenyl)pyrimidine and other p-dialkylaminophenyl group-containing compounds. The most preferred among these is 4,4'-dialkylaminobenzophenone.
The sensitizing dyes may also be used alone 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. One type of polymerization accelerator may be used alone, or two or more types may be used in combination.

The content ratio of the photopolymerization initiator (B) in the 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 in the total solid content of the photosensitive resin composition. At least 1% by mass, more preferably at least 1% by mass, even more preferably at least 2% by mass, particularly preferably at least 3% by mass, and usually at most 25% by mass, preferably at most 20% by mass, more preferably at most 15% by mass. , more preferably 10% by mass or less, even more preferably 7% by mass or less, particularly preferably 5% by mass or less. By setting the above lower limit value or more, a coating film is formed without film loss during development, and sufficient ink repellency tends to occur, and by setting the above upper limit value or less, a desired pattern shape can be formed. It tends to be easier.

In addition, the blending ratio of (B) photopolymerization initiator to (A) ethylenically unsaturated compound in the photosensitive resin composition is 1 part by mass or more per 100 parts by mass of (A) ethylenically unsaturated compound. is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, and preferably 200 parts by mass or less, and 100 parts by mass or less. It is more preferably 50 parts by mass or less, even more preferably 30 parts by mass or less. Setting the sensitivity at or above the lower limit value tends to provide appropriate sensitivity, and setting it at or below the upper limit value tends to make it easier to form a desired pattern shape.

Further, it is preferable to use a chain transfer agent in combination with the photopolymerization initiator. Examples of the chain transfer agent include compounds containing a mercapto group, carbon tetrachloride, and the like, and it is more preferable to use a compound having a mercapto group because it tends to have a high chain transfer effect. This is thought to be because bond cleavage is likely to occur due to the small S--H bond energy, and hydrogen abstraction reactions and chain transfer reactions are likely to occur. Effective for improving sensitivity and surface hardening.

Examples of 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 with aromatic rings 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, trishydroxyethyltristhiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), butanediol bis(3-mercaptobutyrate), ethylene glycol bis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine Examples include 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 mercapto group-containing compounds having an aromatic ring, and trimethylolpropane tris (3-mercapto group-containing compounds) are preferred among aliphatic mercapto group-containing compounds. mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), 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) - Trion is preferred.

In addition, from the viewpoint of sensitivity, aliphatic mercapto group-containing compounds are preferred, and specifically, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), 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, and pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate) is more preferred.
Various types of these can be used singly or in combination of two 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 photopolymerization initiator system. For example, 2-mercaptobenzothiazole may be used, 2-mercaptobenzoimidazole may be used, or 2-mercaptobenzothiazole and 2-mercaptobenzimidazole may be used in combination.
Further, 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).

The content of the chain transfer agent in the 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, based on the total solid content of the photosensitive resin composition. 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, even more preferably 2% by mass or less. It is. Setting the value above the lower limit value tends to increase the sensitivity, and setting the value below the upper limit value tends to make it easier to form a desired pattern.

Further, the content ratio of the chain transfer agent to the (B) photoinitiator in the photosensitive resin composition is preferably 5 parts by mass or more, and 10 parts by mass based on 100 parts by mass of the (B) photoinitiator. The above is more preferable, more preferably 15 parts by weight or more, particularly preferably 20 parts by weight or more, and preferably 500 parts by weight or less, more preferably 300 parts by weight or less, even more preferably 100 parts by weight or less, and 50 parts by weight or less. is particularly preferred. Setting the value above the lower limit value tends to result in high sensitivity, and setting the value below the upper limit value tends to make it easier to form a desired pattern.

[1-1-3] Component (C); Alkali-soluble resin The 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 as the developer is preferably an alkaline developer, it is preferable to use a resin containing a carboxyl group or a hydroxyl group. Carboxyl group-containing resins are preferred from the viewpoint of excellent properties.
In addition, partition walls with an appropriate taper angle can be obtained, and ink repellency can be maintained by suppressing the outflow of the liquid repellent agent due to development or thermal melting of the partition walls, and repellency in pixel areas can be suppressed during inkjet coating. More preferred is an alkali-soluble resin having an ethylenically unsaturated group.

In the photosensitive resin composition of the present invention, (C) an alkali-soluble resin is selected from the viewpoint of ink repellency, (c1) an acrylic copolymer resin having an ethylenically unsaturated group in the side chain (hereinafter referred to as "(c1) an acrylic copolymer resin"). (sometimes referred to as "polymer resin"). On the other hand, from the viewpoint of pattern linearity, it is preferable to include (c2) epoxy (meth)acrylate resin.

Furthermore, from the viewpoint of achieving both ink repellency and linearity, it is preferable that the alkali-soluble resin (C) contains both (c1) an acrylic copolymer resin and (c2) an epoxy (meth)acrylate resin.
Below, (c1) the acrylic copolymer resin having an ethylenically unsaturated group in the side chain will be described in detail.

[(c1) Acrylic copolymer resin having ethylenically unsaturated group in side chain]
(c1) The acrylic copolymer resin has an ethylenically unsaturated group in the side chain. It is thought that by having an ethylenically unsaturated group, photocuring occurs upon exposure to light, resulting in a stronger film, and the liquid repellent is less likely to flow out during development.

(Partial structure represented by general formula (I))
(c1) The partial structure of the acrylic copolymer resin containing a side chain having an ethylenically unsaturated group is not particularly limited. It is preferable to have 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.

Further, among the partial structures represented by the formula (I), from the viewpoint of sensitivity and alkali developability, the partial structure represented by the following general formula (I') is preferable.

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.

The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Examples of 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. Examples include one or more selected from acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
Among these, from the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and more preferred. are tetrahydrophthalic acid and biphenyltetracarboxylic acid.

(c1) The content ratio 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, even more preferably 40 mol% or more, particularly preferably 50 mol% or more, most preferably 65 mol% or more, and preferably 95 mol% or less, and 80 mol% or more. % or less, more preferably 85 mol% or less, even more preferably 80 mol% or less, particularly preferably 75 mol% or less, and most preferably 70 mol% or less. When the content is equal to or more than the lower limit, the ink repellency tends to improve, and when the content is equal to or less than the upper limit, the amount of residue tends to be reduced.

(c1) The content ratio 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, More preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, particularly preferably 50 mol% or more, most preferably 65 mol% or more, and preferably 95 mol% or less, It is more preferably 90 mol% or less, even more preferably 85 mol% or less, even more preferably 80 mol% or less, particularly preferably 75 mol% or less, and most preferably 70 mol% or less. When the content is equal to or more than the lower limit, alkali development tends to be easier, and when it is equal to or less than the upper limit, development adhesion tends to be ensured.

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

In the above formula (II), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkyl group that may have a substituent, an aromatic ring group that may have a substituent, or a substituent Represents an alkenyl group that may have.

( ^R4 )
In the formula (II), ^R represents an alkyl group that may have a substituent, an aromatic ring group that may have a substituent, or an alkenyl group that may have a substituent. .
Examples of the alkyl group for R ⁴ include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, even more 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 amount is equal to or more than the lower limit, the film strength tends to increase and development adhesion improves, and when it is equal to or less than the upper limit, the amount of residue tends to be reduced.

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

Examples of the aromatic ring group for R ⁴ include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The number of carbon atoms is preferably 6 or more, more preferably 24 or less, more preferably 22 or less, even more preferably 20 or less, and particularly preferably 18 or less. Setting the amount above the lower limit value tends to improve the development adhesion, and setting it below the upper limit value tends to reduce the amount of residue.
The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, such as a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, and a pyrene ring. Examples include 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 single ring or a condensed ring, such as a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, and a pyrazole ring. , imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrole ring, furofuran ring, thienofuran ring, benzisoxazole 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 Examples include groups such as. Among these, from the viewpoint of developability, a benzene ring group or a naphthalene ring group is preferable, and a benzene ring group is more preferable.
In addition, the substituents that the aromatic ring group may have include methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, and epoxy group. , oligoethylene glycol group, phenyl group, carboxyl group, etc., and from the viewpoint of developability, hydroxyl group and oligoethylene glycol group are preferable.

Examples of the alkenyl group for R ⁴ include linear, branched or cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less. , 14 or less is particularly preferable. Setting the amount above the lower limit value tends to improve the development adhesion, and setting it below the upper limit value tends to reduce the amount of residue.

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

In addition, as substituents that the alkenyl group may have, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group From the viewpoint of developability, hydroxy groups and oligoethylene glycol groups are preferred.

In this way, R ⁴ represents an alkyl group that may have a substituent, an aromatic ring group that may have a substituent, or an alkenyl group that may have a substituent. Among these, from the viewpoint of developability and film strength, alkyl groups or alkenyl groups are preferred, and alkyl groups are more preferred.

(c1) The content ratio 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 preferable, 10 mol% or more is still more preferable, 20 mol% or more is particularly preferable, 70 mol% or less is preferable, 60 mol% or less is more preferable, 50 mol% or less is further preferable, and 40 mol% or less is Particularly preferred. Setting the amount above the lower limit value tends to improve the development adhesion, and setting it below the upper limit value tends to reduce the amount of residue.

(Substructure represented by general formula (III))
(c1) When the acrylic copolymer resin contains a partial structure represented by the above general formula (I), the other partial structure included is represented by the following general formula (III) from the viewpoint of heat resistance and film strength. Preferably, a partial structure is included.

In the above formula (III), R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an alkenyl group that may have a substituent. represents an optionally substituted alkynyl group, hydroxyl group, carboxyl group, halogen atom, optionally substituted alkoxy group, thiol group, or optionally substituted alkyl sulfide group. t represents an integer from 0 to 5.

( ^R6 )
In the formula (III), R ⁶ is an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, a hydroxyl group, or a carboxyl group. , represents a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkyl sulfide group which may have a substituent.
Examples of the alkyl group for R ⁶ include linear, branched, or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, even more preferably 5 or more, and 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. Setting the amount above the lower limit value tends to improve the development adhesion, and setting it below the upper limit value tends to reduce the amount of residue.

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

Examples of the alkenyl group for R ⁶ include linear, branched, or cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less. , 14 or less is particularly preferable. Setting the amount above the lower limit value tends to improve the development adhesion, and setting it below the upper limit value tends to reduce the amount of residue.

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

In addition, as substituents that the alkenyl group may have, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group From the viewpoint of developability, hydroxy groups and oligoethylene glycol groups are preferred.

Examples of the alkynyl group for R ⁶ include linear, branched or cyclic alkynyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less. , 14 or less is particularly preferable. Setting the amount above the lower limit value tends to improve the development adhesion, and setting it below the upper limit value tends to reduce the amount of residue.

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

In addition, as substituents that the alkynyl group may have, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group From the viewpoint of developability, hydroxy groups and oligoethylene glycol groups are preferred.

Examples of the halogen atom in R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom is preferred from the viewpoint of ink repellency.

Examples of the alkoxy group for R ⁶ include linear, branched, or cyclic alkoxy groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less. , 12 or less is particularly preferable. Setting the amount above the lower limit value tends to improve the development adhesion, and setting it below the upper limit value tends to reduce the amount of residue.

Specific examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, and the like.

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

Examples of the alkyl sulfide group for R ⁶ include linear, branched or cyclic alkyl sulfide groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less. , 12 or less is particularly preferable. Setting the amount above the lower limit value tends to improve the development adhesion, and setting it below the upper limit value tends to reduce the amount of residue.

Specific examples of the alkyl sulfide group include a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, a butyl sulfide group, and the like. Among these, a methyl sulfide group or an ethyl sulfide group is preferred from the viewpoint of developability.

In addition, substituents that the alkyl group in the alkyl sulfide 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 preferable.

In this way, R ⁶ is an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, a hydroxyl group, a carboxyl group, or a halogen group. represents an atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or an alkyl sulfide group which may have a substituent, and among these, from the viewpoint of developability, a hydroxyl group or a carboxyl group is preferable, and a carboxyl group is more preferable. preferable.

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

(c1) The content ratio 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 preferable, 5 mol% or more is even more preferable, 8 mol% or more is particularly preferable, 50 mol% or less is preferable, 40 mol% or less is more preferable, 30 mol% or less is further preferable, and 20 mol% or less is Particularly preferred. Setting the amount above the lower limit value tends to improve the development adhesion, and setting it below the upper limit value tends to reduce the amount of residue.

(Substructure 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 above general formula (I), from the viewpoint of developability, the following general formula is included as the other partial structure: It is also preferable to have a partial structure represented by (IV).

In the above formula (IV), R ⁷ represents a hydrogen atom or a methyl group.

(c1) The content ratio 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, even more preferably 20 mol% or more, further preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less. When the amount is equal to or more than the lower limit, the developability tends to improve, and when it is equal to or less than the upper limit, the developer adhesion tends to improve.

On the other hand, the acid value of the acrylic copolymer resin (c1) is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, even more preferably 40 mgKOH/g or more, even more preferably 50 mgKOH/g or more. , is particularly preferably at least 60 mgKOH/g, preferably at most 150 mgKOH/g, more preferably at most 140 mgKOH/g, even more preferably at most 130 mgKOH/g, even more preferably at most 120 mgKOH/g. When the amount is equal to or more than the lower limit, the developability tends to improve, and when it is equal to or less than the upper limit, the developer adhesion tends to improve.

(c1) The weight average molecular weight (Mw) of the acrylic copolymer resin is not particularly limited, but is usually 1,000 or more, preferably 2,000 or more, more preferably 4,000 or more, still more preferably 6,000 or more, even more preferably 7,000 or more, 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, even more preferably 10,000 or less. When the amount is equal to or more than the lower limit, the development adhesion tends to improve, and when the amount is less than the upper limit, the amount of residue tends to be reduced.

The content ratio 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, even more preferably 50% by mass or more, and 70% by mass. % or more, preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less. When the content is equal to or more than the lower limit, the ink repellency tends to improve, and when the content is equal to or less than the upper limit, the amount of residue tends to be reduced.

Further, the content ratio of (c1) acrylic copolymer resin is preferably 10% by mass or more, and 30% by mass or more with respect to the total mass of (c1) acrylic copolymer resin and (c2) epoxy (meth)acrylate resin. is more preferably 50% by mass or more, further 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 equal to or more than the lower limit, ink repellency tends to improve, and when the content is equal to or less than the upper limit, the amount of residue tends to be reduced.

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

[(c2) Epoxy (meth)acrylate resin]
(c2) Epoxy (meth)acrylate resin is produced by adding an ethylenically unsaturated monocarboxylic acid or ester compound to an epoxy resin, optionally reacting with an isocyanate group-containing compound, and then reacting with a polybasic acid or its anhydride. It is a resin made by For example, by ring-opening addition of a carboxyl group of an unsaturated monocarboxylic acid to an epoxy group of an epoxy resin, an ethylenically unsaturated bond is added to the epoxy compound via an ester bond (-COO-), and Examples include those in which one carboxy group of a polybasic acid anhydride is added to the hydroxyl group generated at that time. Also included are those added by simultaneously adding a polyhydric alcohol when adding a polybasic acid anhydride.

Also included in the above (c2) epoxy (meth)acrylate resin is a resin obtained by reacting a compound having a functional group that can further react with the carboxyl group of the resin obtained in the above reaction.
In this way, epoxy (meth)acrylate resin has virtually no epoxy groups due to its chemical structure, and is not limited to "(meth)acrylate", but it is made from an epoxy compound (epoxy resin) as a raw material. And since "(meth)acrylate" is a typical example, it is named this way according to common usage.

Here, the epoxy resin includes a raw material compound before forming a resin by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins. Further, 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 phenolic hydroxyl group of divalent or higher valence, 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 novolac epoxy resin, biphenyl novolac epoxy resin, trisphenol epoxy resin, polymerization of phenol and dicyclopentadiene. Epoxy resin, dihydroxylfluorene type epoxy resin, dihydroxylalkyleneoxylfluorene type epoxy resin, diglycidyl etherified product of 9,9-bis(4'-hydroxyphenyl)fluorene, 1,1-bis(4'-hydroxy Examples include diglycidyl etherified products of (phenyl)adamantane, 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 novolac epoxy resin, cresol novolac epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, and 9,9-bis(4'-hydroxyphenyl)fluorene are used. Diglycidyl etherified products are preferred, and bisphenol A epoxy resins are more preferred.
Specific examples of epoxy resins include bisphenol A epoxy resins (for example, "jER (registered trademark, hereinafter the same) 828", "jER1001", "jER1002", "jER1004", etc. manufactured by Mitsubishi Chemical Corporation), Epoxy resins obtained by the reaction of the alcoholic hydroxyl groups of bisphenol A-type epoxy resins with epichlorohydrin (for example, "NER-1302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent: 323, softening point 76 ° C.)), bisphenol F-type resins (for example, , Mitsubishi Chemical Corporation's "jER807", "EP-4001", "EP-4002", "EP-4004", etc.), epoxy resins obtained by the reaction of the alcoholic hydroxyl group of bisphenol F-type epoxy resin and epichlorohydrin (e.g. , Nippon Kayaku Co., Ltd.'s "NER-7406" (epoxy equivalent: 350, softening point: 66°C)), bisphenol S-type epoxy resin, biphenyl glycidyl ether (e.g., Mitsubishi Chemical's "YX-4000"), phenol novolak type epoxy resin (for example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152", "EP-154" manufactured by Mitsubishi Chemical Company, "DEN-438" manufactured by Dow Chemical Company), (o, m, p-) Cresol novolak type epoxy resin (for example, "EOCN (registered trademark, hereinafter the same)-102S", "EOCN-1020", "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Co., Ltd.), trisphenolmethane type epoxy resin (for example, "EPPN (registered trademark, hereinafter the same applies)" manufactured by Nippon Kayaku Co., Ltd.), "EPPN-502"'',``EPPN-503''), alicyclic epoxy resins (Daicel's ``Celoxide (registered trademark, hereinafter the same applies) 2021P'', ``Celoxide EHPE''), phenolic resins produced by the reaction of dicyclopentadiene and phenol, and glycidyl Epoxy resins represented by the following general formulas (C1) to (C4), etc. are preferably used. It can be used for. Specifically, the epoxy resin represented by the following general formula (C1) was "XD-1000" manufactured by Nippon Kayaku Co., Ltd., and the epoxy resin represented by the following general formula (C2) was "XD-1000" manufactured by Nippon Kayaku Co., Ltd. Examples of the epoxy resin represented by the following general formula (C4) include "ESF-300" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.

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. Note that a plurality of R ^111s present 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. Note that the plurality of R ^121s present in one molecule may be the same or different.

In the above general formula (C3), X represents a linking group represented by the following general formula (C3-1) or (C3-2). However, the molecular structure contains one or more adamantane structures. 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 each independently represent an adamantyl group that may have a substituent, a hydrogen atom, or a substituent. represents an alkyl group having 1 to 12 carbon atoms which may have , or a phenyl group which may have a substituent. * represents a bond.

In the general formula (C4), 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 of the 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, and pentaerythritol tri(meth)acrylate succinic anhydride adduct. 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 these, (meth)acrylic acid is preferred 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, -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 anhydrides thereof. Among these, from the viewpoint of outgas, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferable, and succinic anhydride or tetrahydrophthalic anhydride is more preferable.

By using a polyhydric alcohol, the molecular weight of the (c2) epoxy (meth)acrylate resin can be increased and branching can be introduced into the molecule, which tends to balance the molecular weight and viscosity. Furthermore, the rate of introduction of acid groups into the molecule can be increased, and sensitivity, adhesion, etc. tend to be more balanced.
Examples of the polyhydric alcohol include one or more polyhydric alcohols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. It is preferable that there be.

Examples of the epoxy (meth)acrylate resin include those described in Korean Patent Publication No. 10-2013-0022955 in addition to those mentioned 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, even more preferably 50 mgKOH/g or more, even more preferably 70 mgKOH/g or more, It is particularly preferably at least 80 mgKOH/g, preferably at most 200 mgKOH/g, more preferably at most 180 mgKOH/g, even more preferably at most 150 mgKOH/g, even more preferably at most 120 mgKOH/g, and particularly preferably at most 110 mgKOH/g. When the amount is equal to or more than the lower limit, the developability tends to be improved, and when it is less than the upper limit, the film strength tends to be improved.

(c2) The weight average molecular weight (Mw) of the epoxy (meth)acrylate resin is not particularly limited, but is usually 1000 or more, preferably 2000 or more, more preferably 3000 or more, even more preferably 4000 or more, even more preferably 5000 or more, Particularly preferably 6,000 or more, most preferably 7,000 or more, and usually 30,000 or less, preferably 20,000 or less, more preferably 15,000 or less, still more preferably 10,000 or less. When the content is equal to or more than the lower limit, the film strength tends to improve, and when the content is equal to or less than the upper limit, the amount of residue tends to be reduced.

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

The content ratio of (c2) epoxy (meth)acrylate resin is preferably 5% by mass or more, and 10% by mass or more based on 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, even more 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 more than the lower limit, the amount of residue tends to be reduced, and when the content is equal to or less than the upper limit, the ink repellency tends to be improved.

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

Here, examples of the organic solvent used in the reaction include one or more organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate. In addition, the above-mentioned catalysts include tertiary amines such as triethylamine, benzyldimethylamine, and tribenzylamine, tertiary amines such as tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, and trimethylbenzylammonium chloride. Examples include one or more of quaternary amminium salts, phosphorus compounds such as triphenylphosphine, and stibines such as triphenylstibine. Furthermore, examples of the thermal polymerization inhibitor include one or more of hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, and the like.

Furthermore, 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 per chemical equivalent of the epoxy group of the epoxy resin. The amount can be set to . Further, the temperature during the addition reaction can be generally 60 to 150°C, preferably 80 to 120°C. Furthermore, the amount of polybasic acid (anhydride) to be used is usually 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1 chemical equivalents, per 1 chemical equivalent of the hydroxyl group produced in the addition reaction. The amount can be set to 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 those having a partial structure represented by the following general formula (ii) The resin preferably contains 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), and 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), R ^c each 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, and γ is a single bond, -CO-, an alkylene group that may have a substituent, or a divalent group that may have a substituent. represents a cyclic hydrocarbon group. The benzene ring in formula (iii) may be further substituted with any substituent. * represents a bond.

Among these, first, we will explain in detail about the epoxy (meth)acrylate resin (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (c2-1)") having a partial structure represented by the following general formula (i). 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.

( ^Rb )
In the formula (i), R ^b represents a divalent hydrocarbon group which may have a substituent.
Examples of divalent hydrocarbon groups include divalent aliphatic groups, divalent aromatic ring groups, and groups in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are connected. Can be mentioned.

Examples of divalent aliphatic groups include linear, branched, and cyclic groups. Among these, linear ones are preferable from the viewpoint of development solubility, while annular 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. When the value is equal to or more than the lower limit, the film strength tends to improve, and when the value is equal to or less than the upper limit, the sensitivity tends to improve.

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

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

Further, examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic 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 amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a fused ring. Examples of the divalent aromatic hydrocarbon ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Examples include groups such as a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

Further, the aromatic heterocycle in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the divalent aromatic heterocyclic group 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, pyrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Examples include groups such as a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a shinoline ring, a quinoxaline ring, a phenanthridine ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. Among these, from the viewpoint of production cost, a benzene ring or a naphthalene ring having two free valences is preferred, and a benzene ring having two free valences is more preferred.

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

Furthermore, as a group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups, one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic ring group may be used. Examples include groups in which one or more ring groups are connected.
The number of divalent aliphatic groups is not particularly limited, but 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 amount is equal to or more than the lower limit, the developability tends to be improved, and when it is less than the upper limit, the film strength tends to be improved.
The number of divalent aromatic ring groups is not particularly limited, but 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 amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.

Specific examples of groups that connect one or more divalent aliphatic groups and one or more divalent aromatic ring groups include groups represented by the following formulas (i-A) to (i-F), etc. can be mentioned. Among these, a group represented by the following formula (i-A) is preferred from the viewpoint of skeletal rigidity and membrane hydrophobization.

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

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 meanings as in formula (i) above. R ^Y 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.

The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Examples of 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. Examples include one or more selected from acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
Among these, from the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and more preferred. are tetrahydrophthalic acid and 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 type or two or more types.

Further, 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, It is more preferably 3 or more, more preferably 10 or less, and even more preferably 8 or less. When the amount is equal to or more than the lower limit, the developability tends to be improved, and when it is less than the upper limit, the film strength tends to be improved.

Furthermore, 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, and 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 amount is equal to or more than the lower limit, the developability tends to be improved, and when it is less than the upper limit, the film strength tends to be improved.

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

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

In formula (ii), R ^c each 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 the formula (ii), R ^d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

The number of rings an aliphatic cyclic group has is not particularly limited, but 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 amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
The number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and especially 15 or less. preferable. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.

Specific examples of the aliphatic ring in the aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. Among these, adamantane rings are preferred from the viewpoint of film strength and developability.

On the other hand, the number of rings that the aromatic ring group has 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, 4 or less. is more preferable. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.

Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. 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, even more preferably 15 or less. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.

Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, Examples include a fluorene ring. Among these, fluorene rings are preferred from the viewpoint of patterning properties.

Furthermore, in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, the divalent hydrocarbon group is not particularly limited, but includes, for example, a divalent aliphatic group, a divalent aromatic ring group, and one or more divalent hydrocarbon groups. Examples include a group in which a divalent aliphatic group and one or more divalent aromatic ring groups are connected.

Examples of divalent aliphatic groups include linear, branched, and cyclic groups. 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 amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.

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

The number of rings that the divalent cyclic aliphatic group has is not particularly limited, but 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 amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.

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

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

Further, examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic 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 amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a fused ring. Examples of the divalent aromatic hydrocarbon ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Examples include groups such as a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

Further, the aromatic heterocycle in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the divalent aromatic heterocyclic group 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, pyrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Examples include groups such as a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a shinoline ring, a quinoxaline ring, a phenanthridine ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. Among these, from the viewpoint of production cost, a benzene ring or a naphthalene ring having two free valences is preferred, and a benzene ring having two free valences is more preferred.

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

Furthermore, as a group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups, one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic ring group may be used. Examples include groups in which one or more ring groups are connected.
The number of divalent aliphatic groups is not particularly limited, but 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 amount is equal to or more than the lower limit, the developability tends to be improved, and when it is less than the upper limit, the film strength tends to be improved.
The number of divalent aromatic ring groups is not particularly limited, but 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 amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.

Specific examples of groups that connect one or more divalent aliphatic groups and one or more divalent aromatic ring groups include groups represented by the above formulas (i-A) to (i-F), etc. can be mentioned. Among these, from the viewpoint of achieving both film strength and sensitivity, the group represented by the above formula (iC) is preferable.

The bonding mode of the cyclic hydrocarbon group as a side chain 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 replaced with the side chain. Examples include an embodiment in which a cyclic hydrocarbon group, which is a side chain, includes one carbon atom of an aliphatic group.

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

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.

( ^Rα )
In the formula (ii-1), R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

The number of rings an aliphatic cyclic group has is not particularly limited, but 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 amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
The number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and especially 15 or less. preferable. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.

Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. Among these, adamantane rings are preferred from the viewpoint of achieving both film strength and developability.

On the other hand, the number of rings that the aromatic ring group has 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 amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. Further, 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 amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.

Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, fluorene rings are preferred from the viewpoint of achieving both 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, Examples include 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; carboxyl group. Among these, unsubstituted compounds are preferred from the viewpoint of ease of synthesis.

n represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. When the amount is equal to or more than the lower limit, the developability tends to be improved, and when the amount is less 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, and more preferably an adamantyl group.

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

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

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

In formula (ii-2), R ^c has the same meaning 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 the formula (ii-2), R ^β represents a divalent cyclic hydrocarbon group which may have a substituent.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.

The number of rings that the aliphatic cyclic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
Further, the number of carbon atoms in the aliphatic cyclic group is usually 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 amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. Among these, adamantane rings are preferred from the viewpoint of achieving both film strength and developability.

On the other hand, the number of rings that the aromatic ring group has 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 amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. 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, and preferably 40 or less, more preferably 30 or less, and still more preferably 20 or more. It is preferably 15 or less, particularly preferably 15 or less. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.

Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, fluorene rings are preferred from the viewpoints 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, Examples include 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; carboxyl group. Among these, unsubstituted is preferred from the viewpoint of ease of synthesis.

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

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

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

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

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

The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Examples of 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. Examples include one or more selected from acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
Among these, from the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and more preferred. are tetrahydrophthalic acid and biphenyltetracarboxylic acid.

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

Further, the number of partial structures represented by the formula (ii) contained in one molecule of epoxy (meth)acrylate resin (c2-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, Further, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. Setting the amount above the lower limit value tends to improve sensitivity, and setting it below the upper limit value tends to improve developability.

Furthermore, the number of partial structures represented by the formula (ii-1) contained in one molecule of 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. Setting the amount above the lower limit value tends to improve sensitivity, and setting it below the upper limit value tends to improve developability.

Furthermore, the number of partial structures represented by the formula (ii-2) contained in one molecule of 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. Setting the amount above the lower limit value tends to improve sensitivity, and setting it below the upper limit value tends to improve developability.

Further, the number of partial structures represented by the above formula (ii-3) contained in one molecule of 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. Setting the amount above the lower limit value tends to improve sensitivity, and setting it below the upper limit value tends to improve developability.

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

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

(γ)
In the formula (iii), γ represents a single bond, -CO-, an alkylene group which may have a substituent, or a divalent cyclic hydrocarbon group which may have a substituent.

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

Specific examples of the alkylene group include methylene group, ethylene group, propylene group, butylene group, hexylene group, and heptylene group. From the viewpoint of achieving both film strength and developability, ethylene group or propylene group is preferable, and propylene group group is more preferred.

Examples of substituents that 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; carboxyl group. Among these, unsubstituted compounds are preferred from the viewpoint of ease of synthesis.

Examples of the divalent cyclic hydrocarbon group include a divalent aliphatic cyclic group and a divalent aromatic cyclic group.

The number of rings that the aliphatic cyclic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
Further, the number of carbon atoms in the aliphatic cyclic group is usually 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 amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. Among these, adamantane rings are preferred from the viewpoint of achieving both film strength and developability.

On the other hand, the number of rings that the aromatic ring group has 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 amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. 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, and preferably 40 or less, more preferably 30 or less, and still more preferably 20 or more. It is preferably 15 or less, particularly preferably 15 or less. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, fluorene rings are preferred from the viewpoint of achieving both 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, Examples include alkyl groups having 1 to 5 carbon atoms such as iso-amyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; carboxyl group. Among these, unsubstituted is preferred from the viewpoint of ease of synthesis.

Among these, from the viewpoint of developability, γ is preferably an alkylene group which may have a substituent, and more preferably a dimethylmethylene group.

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

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

In formula (iii-1), R ^e and γ have the same meanings 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.

The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Examples of 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. Examples include one or more selected from acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
Among these, from the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and more preferred. are tetrahydrophthalic acid and biphenyltetracarboxylic acid.

Further, 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. , more preferably 10 or more, preferably 18 or less, and even more preferably 15 or less. Setting the amount above the lower limit value tends to improve sensitivity, and setting it below the upper limit value tends to improve developability.

Further, the number of repeating unit structures represented by the above formula (iii-1) contained in one molecule of epoxy (meth)acrylate resin (c2-3) is not particularly limited, but is preferably 1 or more, and 3 or more is preferred. It is more preferably 5 or more, further preferably 18 or less, and even more preferably 15 or less. Setting the amount above the lower limit value tends to improve sensitivity, and setting it below the upper limit value tends to improve developability.

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

In the present invention, the alkali-soluble resin (C) is (c1) an acrylic copolymer resin having an ethylenically unsaturated group in the side chain, and (c2) the resin other than the epoxy (meth)acrylate resin is International Publication No. 2016/194619. Examples include alkali-soluble resins described in International Publication No. 2017/154439.

The content of the alkali-soluble resin (C) in the photosensitive resin composition of the present invention is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more in the total solid content. , more preferably 30% by mass or more, even 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, and more. Preferably it is 70% by mass or less. When the value is equal to or more than the lower limit, the shape of the partition wall tends to be improved, and when the value is equal to or less than the upper limit, the sensitivity tends to improve.

The total content of (A) ethylenically unsaturated compound and (C) alkali-soluble resin in the total solid content is preferably 10% by mass or more, more preferably 30% by mass or more, and further preferably 60% by mass or more. It is preferably 80% by mass or more, particularly preferably 100% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less. When the value is equal to or more than the lower limit, the sensitivity tends to improve, and when the value is equal to or less than the upper limit, the shape of the partition wall tends to improve.

[1-1-4] Component (D); Liquid repellent The photosensitive resin composition of the present invention contains (D) a liquid repellent. (D) By containing the liquid repellent, it is possible to impart ink repellency to the surface of the obtained partition wall, so it is thought that the obtained partition wall can prevent color mixing in each light emitting part (pixel) of the organic layer.

In addition, (D) the liquid repellent in the photosensitive resin composition of the present invention is a repeating unit (i) represented by the following general formula (D-1-1) (hereinafter referred to as "repeat unit (i)") ), and a resin (D-1) having a partial structure (ii) (hereinafter sometimes referred to as "partial structure (ii)") represented by the following general formula (D-1-2). (hereinafter sometimes referred to as "resin (D-1)"). Since resin (D-1) contains a polycyclic aliphatic hydrocarbon skeleton having a fluorine-containing organic group in its main chain, the fluorine-containing organic group is difficult to thermally decompose, and it is difficult to thermally decompose the fluorine-containing organic group during heat curing when forming a pattern. It is thought that fume containing fluorine atoms is less likely to be generated, the pixel portion is less likely to be contaminated by the fluorine atom-containing component, and wetting and spreading properties during inkjet coating are improved. In addition, by having the partial structure (ii) containing an ethylenically unsaturated bond in the resin (D-1) molecule, the resin (D-1) is fixed on the surface when the coating film is exposed. It is thought that the resin (D-1) becomes difficult to flow out into the developer during the development process, and as a result, the ink repellency of the obtained partition walls can be increased.

<Repeat unit (i)>

(In the formula, L represents a polycyclic aliphatic hydrocarbon skeleton that may have a substituent.
However, L has one or more fluorine-containing organic groups having 1 to 30 carbon atoms as the substituent.
* represents a bond. )

The number of carbon atoms in the polycyclic aliphatic hydrocarbon constituting L is not particularly limited, but is usually 6 or more, preferably 7 or more, and usually 20 or less, preferably 12 or less, and Preferably it is 10 or less. When the amount is at least the lower limit, wetting and spreading properties during inkjet coating tend to improve, and when the amount is at most the upper limit, the ink repellency tends to improve.
Further, the number of rings constituting the polycyclic aliphatic hydrocarbon is not particularly limited, but is preferably 4 or less, preferably 3 or less, and usually 2 or more. When the amount is below the upper limit, wetting and spreading properties during inkjet coating tend to improve.
Specific examples of the polycyclic aliphatic hydrocarbon skeleton include a norbornane skeleton, a dicyclopentane skeleton, and an adamantane skeleton, among which a norbornane skeleton is preferred from the viewpoint of ease of synthesis.

The polycyclic aliphatic hydrocarbon skeleton may have a substituent, and the substituent includes one or more fluorine-containing organic compounds having 1 to 30 carbon atoms.
The structure of the fluorine-containing organic group is not limited, but examples thereof include a group represented by the following general formula (D-1-1-a).

(In the formula, R ¹² represents an alkyl group having 1 to 27 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, and the carbon-carbon bond of the alkyl group may be interrupted by an oxygen atom.
X represents a single bond, -O-, -CO-O-, -O-CO-, or -CO-NH-.
k represents an integer from 0 to 2.
* represents a bond. )

( ^R12 )
In the formula (D-1-1-a), R ¹² represents an alkyl group having 1 to 27 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, and the carbon-carbon bond of the alkyl group is an oxygen atom. It may be interrupted.
The number of carbon atoms in this alkyl group is usually 1 or more, preferably 2 or more, more preferably 4 or more, preferably 25 or less, more preferably 20 or less, even more preferably 10 or less, and particularly preferably 6 or less. By setting the amount above the lower limit value, the ink repellency tends to improve, and by setting it below the upper limit value, the health safety of the material tends to improve.

This alkyl group may be linear or branched.
Further, this alkyl group is preferably a perfluoroalkyl group. This tends to improve ink repellency. Among these, from the viewpoint of ink repellency, perfluoroalkyl groups having 1 to 6 carbon atoms are preferred.

Specific examples of alkyl groups having 1 to 27 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom include -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CHF ₂ , -(CF ₂ ) ₂ CF ₃ , -( _CF2 ) _3CF3 , -( _{CF2 ) 4CF3 ,} -( _CF2 ) _{5CF3 ,} -( _CF2 ) _{6CF3 ,} -( _CF2 ) _{7CF3 .}

Further, specific examples of carbon-carbon bonds of an alkyl group having 1 to 27 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom are interrupted by an oxygen atom include -CF (CF ₃ ). O(CF ₂ ) ₅ CF ₃ , -CF ₂ O(CF ₂ CF ₂ O) _p CF ₃ (p is an integer from 1 to 8), -CF(CF ₃ )O (CF ₂ CF(CF ₃ )O) Examples thereof include _q C ₆ F ₁₃ (q is an integer of 1 to 4), -CF(CF ₃ )O(CF ₂ CF(CF ₃ )O) _r C ₃ F ₇ (r is an integer of 1 to 5).

(X)
In the formula (D-1-1-a), X represents a single bond, -O-, -CO-O-, -O-CO-, or -CO-NH-. Among these, single bonds are preferred from the viewpoint of wetting and spreading properties during inkjet coating.

Among the groups represented by the formula (D-1-1-a), from the viewpoint of wetting and spreading properties during inkjet coating, -CO-O-(CH ₂ ) ₂ -C ₄ F ₉ , -CO-O --(CH ₂ ) ₂ --C ₆ F ₁₃ , --C ₄ F ₉ and --C ₆ F ₁₃ are preferred.

As mentioned above, L represents a polycyclic aliphatic hydrocarbon skeleton that may have a substituent, and the substituent other than the fluorine-containing organic group having 1 to 30 carbon atoms is not particularly limited, but for example, the following general formula Examples include a group represented by (D-1-1-b).

(In the formula, R ¹³ represents an alkyl group, an alkenyl group, or an alkynyl group.
Z represents a single bond, -O-, -CO-O-, -O-CO-, or -CO-NH-.
* represents a bond. )

( ^R13 )
The alkyl group in R ¹³ may be linear, branched, or cyclic.
The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 15 or less, more preferably 8 or less. When the amount is equal to or more than the lower limit, the ink repellency tends to improve, and when it is equal to or less than the upper limit, the wetting and spreading properties during inkjet coating tend to improve.

Specific examples of alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group. group, octyl group, nonyl group, decyl group, adamantyl group, cyclopentyl group, cyclohexyl group, and cyclooctyl group.

The alkenyl group in R ¹³ may be linear, branched, or cyclic.
The number of carbon atoms in the alkenyl group is not particularly limited, but is usually 2 or more, preferably 3 or more, preferably 10 or less, and more preferably 8 or less. When the amount is equal to or more than the lower limit, the ink repellency tends to improve, and when it is equal to or less than the upper limit, the wetting and spreading properties during inkjet coating tend to improve.
Specific examples of alkenyl groups include vinyl, allyl, butenyl, and pentenyl groups.

The alkynyl group in R ¹³ may be linear, branched, or cyclic.
The number of carbon atoms in the alkynyl group is not particularly limited, but is usually 2 or more, preferably 3 or more, preferably 10 or less, and more preferably 8 or less. When the amount is equal to or more than the lower limit, the ink repellency tends to improve, and when it is equal to or less than the upper limit, the wetting and spreading properties during inkjet coating tend to improve.
A specific example of the alkynyl group is an ethynyl group.

(Z)
In the formula (D-1-1-b), Z represents a single bond, -O-, -CO-O-, -O-CO-, or -CO-NH-. Among these, single bonds are preferred from the viewpoint of wetting and spreading properties during inkjet coating.

As described above, the polycyclic aliphatic hydrocarbon skeleton may have a substituent other than the fluorine-containing organic group having 1 to 30 carbon atoms, but from the viewpoint of ease of synthesis, it is preferably unsubstituted.

Among the repeating units (i) in the resin (D-1), from the viewpoint of ink repellency, repeating units (i-1) represented by the following general formula (D-1-3) (hereinafter referred to as "repeating units") (i-1)") is preferable.

(Each hydrogen atom in the formula may be independently substituted with a substituent.
However, one or more of the hydrogen atoms in the formula is substituted with a fluorine-containing organic group having 1 to 30 carbon atoms.
n represents an integer from 0 to 2.
* represents a bond. )

As the fluorine-containing organic group having 1 to 30 carbon atoms and other substituents in formula (D-1-3), those listed in formula (D-1-1) can be preferably employed.

In formula (D-1-3), n represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0 from the viewpoint of developability.

Furthermore, among the repeating units (i) in the resin (D-1), from the viewpoint of ink repellency and ease of synthesis, repeating units (i-2 ) (hereinafter sometimes referred to as "repeat unit (i-2)") is preferable.

(In the formula, R ¹ to R ⁴ each independently represent a hydrogen atom or an arbitrary substituent.
However, at least one of R ¹ to R ⁴ is a fluorine-containing organic group having 1 to 30 carbon atoms.
n represents an integer from 0 to 2.
* represents a bond. )

As the fluorine-containing organic group having 1 to 30 carbon atoms in R ¹ to R ⁴ , those listed in formula (D-1-1) can be preferably employed.
Similarly, as arbitrary substituents for R ¹ to R ⁴ , those listed as substituents for the polycyclic aliphatic hydrocarbon skeleton in formula (D-1-1) can be preferably employed.

Among these, from the viewpoint of ink repellency, each of R ¹ to R ⁴ is preferably independently a hydrogen atom or a fluorine-containing organic group having 1 to 30 carbon atoms. In this case, the number of fluorine-containing organic groups in R ¹ to R ⁴ is not particularly limited, but is preferably 3 or less, more preferably 2 or less, and even more preferably 1. When the amount is below the upper limit, the wetting and spreading properties during inkjet tend to improve.

Further, n represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0 from the viewpoint of developability.

Specific examples of the repeating unit (i) include the following. The resin (D-1) may contain one type of these or two or more types thereof.

Among these, from the viewpoint of ink repellency, it is preferable to have a repeating unit represented by formula (D-1-22) or a repeating unit represented by formula (D-1-24).

<Partial structure (ii)>
The resin (D-1) has a partial structure represented by the following general formula (D-1-2).

(In the formula, R ¹¹ represents a hydrogen atom or a methyl group.
g represents an integer from 0 to 6.
* represents a bond. )

In formula (D-1-2), R ¹¹ represents a hydrogen atom or a methyl group, and from the viewpoint of ink repellency, a hydrogen atom is preferable.
Further, in formula (D-1-2), g represents an integer of 0 to 6, but from the viewpoint of ease of synthesis, an integer of 2 to 4 is preferable.

The partial structure (ii) may be contained in the repeating units (i), (i-1), (i-2) or in another repeating unit, but the From the viewpoint of wetting and spreading properties during inkjet application in the process, a repeating unit (iii) represented by the following general formula (D-1-5) (hereinafter sometimes referred to as "repeat unit (iii)"), Alternatively, it is preferably contained in the repeating unit (iv) represented by the following general formula (D-1-6) (hereinafter sometimes referred to as "repeat unit (iv)").

<Repeat unit (iii)>

(In the formula, R ⁵ represents the partial structure (ii).
* represents a bond. )

Specific examples of the repeating unit (iii) include the following. The resin (D-1) may contain one type of these or two or more types thereof.

<Repeat unit (iv)>

(In the formula, R ⁶ represents a hydrogen atom or a methyl group.
R ⁷ represents the partial structure (ii) or a group represented by the following general formula (D-1-7).

(In the formula, R ⁸ represents a hydrogen atom or a methyl group.
* represents a bond. )

Specific examples of the repeating unit (iv) include the following. The resin (D-1) may contain one type of these or two or more types thereof.

Among these repeating units, from the viewpoint of wetting and spreading properties during inkjet coating, it is preferable to contain the repeating unit (iii), and the repeating unit represented by the formula (D-1-31) or the formula ( It is more preferable to contain a repeating unit represented by D-1-32).

Further, the resin (D-1) may further contain other repeating units. Other repeating units include the repeating unit (v) represented by the following general formula (D-1-8) (hereinafter sometimes referred to as "repeat unit (v)") and the following general formula (D -1-9) and a repeating unit represented by the following general formula (D-1-10). Further, the repeating unit (iii) includes a repeating unit represented by the following general formula (D-1-11) obtained using the method described in International Publication No. 2017/154439.
The resin (D-1) may contain one type of these or two or more types thereof.

(In formula (D-1-11), R ⁵ and R ⁷ have the same meanings as the above formula (D-1-5) and the above formula (D-1-6).)

The combination of repeating units contained in the resin (D-1) is not particularly limited, but from the viewpoint of ink repellency and wetting and spreading properties during inkjet coating, combinations of repeating units represented by the above formula (D-1-21) and A combination of repeating units represented by the formula (D-1-31), a repeating unit represented by the formula (D-1-21) and a repeating unit represented by the formula (D-1-32), A combination, a combination of a repeating unit represented by the formula (D-1-22) and a repeating unit represented by the formula (D-1-31), a repeat represented by the formula (D-1-22) A combination of a unit and a repeating unit represented by the above formula (D-1-32), a repeating unit represented by the above formula (D-1-23) and a repeating unit represented by the above formula (D-1-31) A combination of units, a combination of a repeating unit represented by the above formula (D-1-23) and a repeating unit represented by the above formula (D-1-32), a combination of a repeating unit represented by the above formula (D-1-24), A combination of a repeating unit represented by the above formula (D-1-31) and a repeating unit represented by the above formula (D-1-24) and a repeating unit represented by the above formula (D-1-32). Combinations of repeating units are preferred.

The content ratio of the repeating unit (i) in the resin (D-1) is not particularly limited, but it is usually 20 mol% or more, preferably 30 mol% or more, more preferably 40 mol% or more, based on the total repeating units. Moreover, it is usually 80 mol% or less, preferably 70 mol% or less, and more preferably 60 mol% or less. When the amount is equal to or more than the lower limit, the ink repellency tends to be improved, and when it is equal to or less than the upper limit, the wetting and spreading properties during inkjet coating tend to be improved.

When the resin (D-1) contains the repeating unit (i-1), its content is not particularly limited, but it is usually 20 mol% or more, preferably 30 mol% or more, and 40 mol% of the total repeating units. % or more, and usually 80 mol% or less, preferably 70 mol% or less, and more preferably 60 mol% or less. When the amount is equal to or more than the lower limit, the ink repellency tends to be improved, and when it is equal to or less than the upper limit, the wetting and spreading properties during inkjet coating tend to be improved.

When the resin (D-1) contains the repeating unit (i-2), its content is not particularly limited, but it is usually 20 mol% or more, preferably 30 mol% or more, and 40 mol% of the total repeating units. % or more, and usually 80 mol% or less, preferably 70 mol% or less, and more preferably 60 mol% or less. When the amount is equal to or more than the lower limit, the ink repellency tends to be improved, and when it is equal to or less than the upper limit, the wetting and spreading properties during inkjet coating tend to be improved.

Further, when the resin (D-1) contains the repeating unit (iii), its content is not particularly limited, but it is usually 20 mol% or more, preferably 30 mol% or more, and usually It is 80 mol% or less, preferably 70 mol% or less, and more preferably 60 mol% or less. When the amount is equal to or more than the lower limit, the wetting and spreading properties during inkjet coating tend to be good, and when the amount is less than the upper limit, the ink repellency tends to be good.

Further, when the resin (D-1) contains the repeating unit (iv), its content is not particularly limited, but it is usually 20 mol% or more, preferably 30 mol% or more, and usually It is 80 mol% or less, preferably 70 mol% or less, and more preferably 60 mol% or less. When the amount is equal to or more than the lower limit, the wetting and spreading properties during inkjet coating tend to be good, and when the amount is less than the upper limit, the ink repellency tends to be good.

The content of fluorine atoms in the resin (D-1) is not particularly limited, but is usually 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and usually 50% by mass or less. Yes, and preferably 40% by mass or less. When the amount is equal to or more than the lower limit, it tends to exhibit high ink repellency, and when it is equal to or less than the upper limit, the wetting and spreading properties during inkjet coating tend to improve.

Further, the double bond equivalent of the resin (D-1) is not particularly limited, but is usually 400 g/mol or more, preferably 700 g/mol or more, more preferably 1000 g/mol or more, and usually 2000 g/mol or less. , 1700 g/mol or less is preferable, and 1400 g/mol or less is more preferable. When the amount is at least the lower limit, wetting and spreading properties during inkjet coating tend to improve, and when it is at most the upper limit, high ink repellency tends to be exhibited.

The weight average molecular weight of the resin (D-1) is not particularly limited, but is usually at least 1,000, preferably at least 2,000, more preferably at least 3,000, even more preferably at least 3,500. Moreover, it is usually 10,000 or less, preferably 7,000 or less, and more preferably 5,000 or less. When the amount is equal to or more than the lower limit, it tends to exhibit high ink repellency, and when it is equal to or less than the upper limit, the wetting and spreading properties during inkjet coating tend to improve.

The method for producing resin (D-1) is not particularly limited, and conventionally known methods can be employed. For example, it is possible to adopt the method described in International Publication No. 2016/194619, and it can be produced by the following steps ((a) to (b) steps). Note that the resin obtained in step (a) can also be used as resin (D-1), or as described in International Publication No. 2017/154439, the resin obtained in step (b) can be used as resin (D-1). Furthermore, the resin obtained by carrying out step (c) can also be used as resin (D-1).

(a) Step: Step of preparing a precursor polymer containing the repeating unit (i-1) or (i-2) and the repeating unit (v) (b) Step: For the precursor polymer, the partial structure Step (c) of reacting alcohol containing (ii) to open the succinic acid skeleton in the repeating unit (v) to generate a carboxyl group or its ester in the precursor polymer to obtain a ring-opened precursor polymer. Step: Optionally, reacting the ring-opened precursor polymer with an epoxy compound.

The content of the liquid repellent (D) in the photosensitive resin composition of the present invention is not particularly limited, but is usually 0.01% by mass or more, preferably 0.05% by mass or more, and 0.1% by mass in the total solid content. The above is more preferable, 0.2% by weight or more is even more preferable, 0.3% by weight or more is particularly preferable, and usually 5% by weight or less, preferably 3% by weight or less, more preferably 2% by weight or less, 1% by weight or less. % or less is more preferable. When the value is equal to or more than the lower limit, it tends to exhibit high ink repellency, and when it is equal to or less than the upper limit, it tends to suppress the liquid repellent from flowing out into the pixel area.

The content of the resin (D-1) in the photosensitive resin composition of the present invention is not particularly limited, but is usually 0.01% by mass or more, preferably 0.05% by mass or more, and 0.1% by mass in the total solid content. % or more, more preferably 0.2% by mass or more, particularly preferably 0.3% by mass or more, and usually 5% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less, 1 It is more preferably less than % by mass. When the value is equal to or more than the lower limit, it tends to exhibit high ink repellency, and when it is equal to or less than the upper limit, it tends to suppress the liquid repellent from flowing out into the pixel area.

Further, the content ratio of the resin (D-1) in the liquid repellent (D) is not particularly limited, but is usually 10% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more. , more preferably 90% by mass or more, and usually 100% by mass or less. By setting the amount to be equal to or higher than the lower limit value, the wetting and spreading properties during inkjet coating tend to improve.

The liquid repellent (D) in the photosensitive resin composition of the present invention may contain a liquid repellent other than the resin (D-1).
Examples of other liquid repellents include perfluoroalkyl sulfonic acids, perfluoroalkyl carboxylic acids, perfluoroalkyl alkylene oxide adducts, perfluoroalkyl trialkylammonium salts, oligomers containing perfluoroalkyl groups and hydrophilic groups, and perfluoroalkyl Examples include fluorine-containing organic compounds such as oligomers containing a group and a lipophilic group, urethanes containing a perfluoroalkyl group and a hydrophilic group, and perfluoroalkyl phosphate esters.
Further, these compounds preferably have an epoxy group or an ethylenically unsaturated group as a crosslinking group.
Commercial products of fluorine-containing organic compounds having these crosslinking groups include "Megafac (registered trademark, hereinafter the same) F116", "Megafac F120", "Megafac F142D", and "Megafac F144D" manufactured by DIC Corporation. , "Megafuck F150", "Megafuck F160", "Megafuck F171", "Megafuck F172", "Megafuck F173", "Megafuck F177", "Megafuck F178A", "Megafuck F178K", " Megafuck 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", " ``Megafac RS402'', ``Megafac RS501'', ``Megafac RS502'', ``Megafac RS-72-K'', ``DEFENSA (registered trademark, hereinafter the same) MCF300'', ``DEFENSA MCF310'', ``DEFENSA MCF312'', "DEFENSA MCF323", "Florado FC430", "Florado FC431", "FC-4430", "FC4432" made by 3M Japan, "Asahi Guard (registered trademark) AG710" made by AGC, "Surflon" made by AGC Seimi Chemical (Registered trademark, same hereinafter) S-382'', ``Surflon SC-101'', ``Surflon SC-102'', ``Surflon SC-103'', ``Surflon SC-104'', ``Surflon SC-105'', ``Surflon Fluorine-containing organic compounds commercially available under trade names such as "SC-106" and "Optool (registered trademark) DAC-HP" manufactured by Daikin Industries, Ltd. can be used.

On the other hand, in the photosensitive resin composition of the present invention, a surfactant may be used together with (D) a liquid repellent. The surfactant can be used for the purpose of improving the coating properties of the photosensitive resin composition as a coating solution and the developability of the coating film, and among them, fluorine-based or silicone-based surfactants are preferred.
In particular, silicone-based surfactants are preferable because they have the effect of removing the residue of the photosensitive resin composition from unexposed areas during development and also have the function of expressing wetting and spreading properties, and polyether-modified silicone More preferred are surfactants.

As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group at at least one of the terminal, main chain, and side chain is suitable. 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 perfluorododecyl sulfonate, 1,1,2,2,8,8,9, Examples include 9,10,10-decafluorododecane and 1,1,2,2,3,3-hexafluorodecane. These commercially available products include, for example, "BM-1000" and "BM-1100" manufactured by BM Chemie, "Megafac F142D", "Megafac F172", "Megafac F173", and "Megafac F183" manufactured by DIC Corporation. ", "Megafac F470," "Megafac F475," "Megafac F554," "Megafac F559," "FC430" manufactured by 3M Japan, and "DFX-18" manufactured by Neos.

In addition, examples of silicone surfactants include "DC3PA", "SH7PA", "DC11PA", "SH21PA", "SH28PA", "SH29PA", "8032Additive", "SH8400", manufactured by Dow Corning Toray Industries, Inc. Commercially available products such as "BYK323" and "BYK330" manufactured by BYK Chemie Co., Ltd. can be mentioned.
The surfactant may include things other than fluorine-based surfactants and silicone-based surfactants, and other surfactants include nonionic, anionic, cationic, and amphoteric surfactants. It will 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, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitol fatty acid esters, polyoxy Examples include ethylene sorbitol fatty acid esters. Examples of these commercially available products include polyoxyethylene surfactants such as "Emulgen (registered trademark, the same hereinafter) 104P" and "Emulgen A60" manufactured by Kao Corporation.

Examples of the anionic surfactants include alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate ester salts, and higher alcohol sulfates. Ester salts, aliphatic 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 these, special polymer surfactants are preferred, and special polycarboxylic acid type polymer surfactants are more preferred. Commercially available products can be used as such anionic surfactants. For example, alkyl sulfate salts such as "Emar (registered trademark) 10" manufactured by Kao Corporation, and alkylnaphthalene sulfonates such as "Perex" manufactured by Kao Corporation. (Registered Trademark) NB-L", special polymer surfactants include Kao Corporation's "Homogenol (Registered Trademark, hereinafter the same applies) L-18" and "Homogenol L-100."

Further, examples of the cationic surfactants include quaternary ammonium salts, imidazoline derivatives, alkylamine salts, etc., and examples of the amphoteric surfactants include betaine type compounds, imidazolium salts, imidazolines, and amino acids. Examples include. Among these, quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are more preferred. Commercially available products include, for example, alkylamine salts such as "Acetamin (registered trademark) 24" manufactured by Kao Corporation, and quaternary ammonium salts such as "Cortamine (registered trademark) 24P" and "Cortamine (registered trademark) 24P" manufactured by Kao Corporation. 86W".

Further, surfactants may be used in combination of two or more types, for example, silicone surfactant/fluorine surfactant, silicone surfactant/special polymer surfactant, fluorine surfactant. /Special polymeric surfactant combinations, etc. Among these, a combination of silicone surfactant/fluorosurfactant is preferred. Examples of the silicone surfactant/fluorosurfactant combination include "DFX-18" manufactured by NEOS, "BYK-300" or "BYK-330" manufactured by BYK Chemie, and "S-" manufactured by AGC Seimi Chemical. 393", "KP340" manufactured by Shin-Etsu Silicone / "F-478" or "F-475" manufactured by DIC, "SH7PA" manufactured by Dow Corning Toray / "DS-401" manufactured by Daikin, "L" manufactured by NUC -77''/FC4430 manufactured by 3M Japan.

[1-1-5] Component (E); Colorant The photosensitive resin composition of the present invention may further contain (E) a colorant. By containing the coloring agent (E), it is possible to obtain an appropriate light absorbing property, particularly when used for forming a light blocking member such as a colored partition wall, an appropriate light blocking property.

The type of colorant (E) used in the present invention is not particularly limited, and pigments or dyes may be used. Among these, from the viewpoint of durability, it is preferable to use pigments.

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

Among the organic pigments, it is preferable to use organic colored pigments from the viewpoint of ultraviolet absorbability.
One type of organic coloring pigment may be used alone, or two or more types may be used in combination. In particular, when used for light-shielding applications, it is more preferable to use a combination of organic coloring pigments of different colors, and it is even more preferable to use a combination of organic coloring pigments that exhibit a color close to black.

The chemical structure of these organic pigments is not particularly limited, but examples include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, perylene-based, and the like. Specific examples of pigments that can be used are shown below using pigment numbers. Terms such as "C.I. Pigment Red 2" listed below mean color index (C.I.).

As a red pigment, C. 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, and 254. In addition, in terms of dispersibility and light blocking properties, C. I. Pigment Red 177, 254, and 272 are preferably used. When curing the photosensitive resin composition with ultraviolet rays, it is preferable to use red pigments with low ultraviolet absorbance. From this point of view, C. I. It is more preferable to use Pigment Red 254 and 272.

As the orange pigment, C. 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. Among these, C. I. It is preferable to use Pigment Orange 13, 43, 64, and 72. When curing the photosensitive resin composition with ultraviolet rays, it is preferable to use orange pigments with low ultraviolet absorbance; from this point of view, C. I. It is more preferable to use Pigment Orange 64 and 72.

As a blue pigment, C. 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. Among these, from the viewpoint of light-shielding properties, 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 addition, in terms of dispersibility and light blocking properties, C. I. Pigment Blue 15:6, 16, and 60 are preferably used. When curing the photosensitive resin composition with ultraviolet rays, it is preferable to use blue pigments with low ultraviolet absorbance; from this point of view, C. I. It is more preferable to use Pigment Blue 60.

As a purple pigment, C. 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, and 50. Among these, from the viewpoint of light-shielding properties, C.I. I. Pigment Violet 19, 23, more preferably C.I. I. Pigment Violet 23 may be mentioned.
In addition, in terms of dispersibility and light blocking properties, C. I. It is preferable to use Pigment Violet 23 and 29, and when curing the photosensitive resin composition with ultraviolet rays, it is preferable to use a purple pigment with a low ultraviolet absorbance.From this point of view, C. I. It is more preferable to use Pigment Violet 29.

Examples of organic coloring pigments that can be used in addition to red pigments, orange pigments, blue pigments, and purple pigments include green pigments and yellow pigments.
As a green pigment, C. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Among these, C. I. Pigment Green 7 and 36 can be mentioned.
As a yellow pigment, C. 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, and 208 can be mentioned. Among these, C. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, and 180.

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

Among these, from the viewpoint of light-shielding properties and ink repellency, it is preferable to contain at least one or more of the following pigments.
Red pigment: C. I. Pigment Red 177, 254, 272
Orange pigment: C. I. Pigment orange 43, 64, 72
Blue pigment: C. I. Pigment Blue 15:6,60
Purple pigment: C. I. pigment violet 23, 29

In addition, when using two or more types of organic coloring pigments in combination, the combination of organic coloring pigments is not particularly limited, but from the viewpoint of light shielding, at least one type selected from the group consisting of red pigments and orange pigments, and blue pigments. and at least one selected from the group consisting of purple pigments.
The combination of colors is not particularly limited, but from the viewpoint of light-shielding properties, examples include 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. .

In addition, from the viewpoint of light-shielding properties, it is preferable to use organic black pigments, and in particular, from the viewpoint of suppressing absorption of ultraviolet rays and improving ink repellency, compounds represented by the following general formula (1) (hereinafter referred to as , also referred to as "compound (1)"), geometric isomers of compound (1), salts of compound (1), and salts of geometric isomers of compound (1). It is preferable to use an organic black pigment (hereinafter sometimes referred to as "organic black pigment represented by general 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 each independently represent a hydrogen atom, a halogen atom, R ²¹ , COOH, COOR ²¹ , COO ^- , CONH ₂ , CONHR ²¹ , CONR ²¹ R ²² , CN, OH, OR ²¹ , COCR ²¹ , OOCNH ₂ , OOCNHR ²¹ , OOCNR ²¹ R ²² , NO ₂ , NH ₂ , NHR ²¹ , NR ²¹ R ²² , NHCOR ²² , NR ²¹ COR ²² , N = _CH2 , N= ^CHR21 , N= ^CR21R22 , SH, ^SR21 , ^SOR21 _, ^{SO2R21 , SO3R21} , _{SO3H , SO3-} ^, _{SO2NH2 , SO2NHR} ²¹ or SO ₂ NR ²¹ R ²² ; and from R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , and R ¹⁹ and R ²⁰ At least one combination selected from the group consisting of: can be directly bonded to each other or can be bonded to each other by an oxygen atom, sulfur atom, NH or NR ²¹ bridge; R ²¹ and R ²² are each independently carbon 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 structures (however, substituents in the structural formulas are omitted), and the trans-trans isomer is probably the most stable.

When compound (1) is anionic, its charge can be transferred to any known suitable cation, such as a metal, organic, inorganic or metal-organic cation, in particular an alkali metal, alkaline earth metal, transition metal, primary ammonium , secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium, or a salt compensated with an organometallic complex. Moreover, when the geometric isomer of compound (1) is anionic, a similar salt is preferable.

Regarding the substituents in general formula (1) and their definitions, the following are preferable because the shielding rate tends to be high. 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 a hydrogen atom, a fluorine atom or a chlorine atom, more preferably a hydrogen atom.
R ¹³ and R ¹⁸ each independently preferably represent a 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, and more preferably R ¹¹ 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 the same.

Examples of the alkyl group having 1 to 12 carbon atoms include 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 group, nonyl group, decyl group, undecyl group or dodecyl group.

Examples of the cycloalkyl group having 3 to 12 carbon atoms include a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, a trimethylcyclohexyl group, a tuzyl group, a norbornyl group, a bornyl group, and a norcalyl group. , calyl group, menthyl group, norpinyl group, pinyl group, adamantan-1-yl group or adamantan-2-yl group.

Examples of alkenyl groups having 2 to 12 carbon atoms include vinyl group, allyl group, 2-propen-2-yl group, 2-buten-1-yl group, 3-buten-1-yl group, and 1,3-butadiene group. -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.

Examples of the cycloalkenyl group having 3 to 12 carbon atoms include 2-cyclobuten-1-yl group, 2-cyclopenten-1-yl group, 2-cyclohexen-1-yl group, 3-cyclohexen-1-yl group, 2-cyclohexen-1-yl group, , 4-cyclohexadien-1-yl group, 1-p-menthen-8-yl group, 4(10)-thujen-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadien-1 -yl group, 7,7-dimethyl-2,4-norcaladien-3-yl group, or camphenyl group.

Examples of the alkynyl group having 2 to 12 carbon atoms include 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentyn-5-yl group, and 2-methyl-3-butyn-2-yl group. 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-octyn-8-yl group, 1-nonyn-9-yl group, It is a 1-decyn-10-yl group or a 1-dodecyn-12-yl group.

The 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 a geometric isomer of the compound (2). It is an organic black pigment containing at least one member selected from the group consisting of:

A specific example of such an organic black pigment is the trade name Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF).
This organic black pigment is preferably used after being dispersed using a dispersant, solvent, and method described below. Furthermore, the presence of the sulfonic acid derivative of compound (1), especially the sulfonic acid derivative of compound (2), during dispersion may improve dispersibility and storage stability. It is preferable to include.

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

Furthermore, examples of colorants other than these organic pigments include inorganic black pigments. In addition to the organic pigment, an inorganic black pigment may also be used.

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. Examples of carbon black include the following carbon blacks.

Made by Mitsubishi Chemical: 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
Manufactured by Degussa: Printex (registered trademark, same hereinafter) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex8 5, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBla ck4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Col or Black S170
Manufactured by Cabot: Monarch (registered trademark, same hereinafter) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1 400, Monarch4630, REGAL (registered trademark, same hereinafter) 99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark, the same applies hereinafter) XC72R, ELFTEX (registered trademark) Trademark)-8
Made by Birler: RAVEN (registered trademark, same hereinafter) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RA VEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U , RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

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

The carbon black to be subjected to the resin coating treatment preferably has a total content of Na and Ca of 100 ppm or less. Carbon black usually contains Na, Ca, K, Mg, Al, Fe, etc. mixed in from raw material oil, combustion oil (or gas), reaction stop water, granulation water, and reactor materials during manufacturing. Contains ash with a composition of Among these, Na and Ca are generally contained in amounts of several hundred ppm or more each, but by reducing their content, it is possible to suppress penetration into transparent electrodes (ITO) and other electrodes, and to This tends to prevent short circuits.

A method for reducing the content of ash containing Na and Ca is to carefully select materials with as low a content as possible as raw material oil, fuel oil (or gas), and reaction termination water when producing carbon black. This can be achieved by minimizing the amount of alkaline substances added to adjust the structure. Another method includes a method in which carbon black produced from a furnace is washed with water, hydrochloric acid, etc. to dissolve and remove Na and Ca.

Specifically, after carbon black is mixed and dispersed in water, hydrochloric acid, or hydrogen peroxide, and a poorly soluble solvent is added to the water, the carbon black migrates to the solvent side and completely separates from the water. At the same time, most of the Na and Ca present in the carbon black are dissolved and removed by 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 only the carbon black manufacturing process with carefully selected raw materials or the water or acid dissolution method alone, but it is possible to reduce the total amount of Na and Ca to 100 ppm or less, but by using both methods together The total amount of Na and Ca can be easily reduced to 100 ppm or less.

Further, 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 minute 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. By setting it within the above range, a coating film with good light-shielding properties tends to be obtained. The average particle diameter refers to the number average particle diameter, and particle image analysis involves taking several fields of view of photographs taken at tens of thousands of magnifications using an electron microscope, and measuring approximately 2000 to 3000 particles in these photographs using an image processing device. means the equivalent circle diameter determined by

There are no particular limitations on the method for preparing resin-coated carbon black, but for example, after suitably adjusting the blending amounts of carbon black and resin, 1. After mixing and stirring a resin solution in which a resin and a solvent such as cyclohexanone, toluene, or xylene are mixed and dissolved by heating, and a suspension in which carbon black and water are mixed to separate the carbon black and water, 2. A method of removing water and heating and kneading the resulting composition into a sheet, pulverizing it, and then drying it; 2. A method of mixing and stirring a resin solution and a suspension prepared in the same manner as described above to granulate carbon black and resin, and then separating and heating the resulting granules to remove the remaining solvent and water; 3. A carboxylic acid such as maleic acid or fumaric acid is dissolved in the above-mentioned solvent, carbon black is added, mixed and dried, the solvent is removed to obtain carboxylic acid-impregnated carbon black, and a resin is added to this. method of dry blending; 4. A suspension is prepared by stirring the reactive group-containing monomer component constituting the resin to be coated with water at high speed, and after polymerization, the reactive group-containing resin is obtained from the polymer suspension by cooling. A method may be adopted in which carbon black is added and kneaded, the carbon black and a reactive group are reacted (grafted with carbon black), and the mixture is cooled and pulverized.

The type of resin to be coated is not particularly limited, but synthetic resins are common, and resins that have a benzene ring in their structure have a stronger action as an amphoteric surfactant. Preferred from the viewpoint of dispersibility and dispersion stability.
Specific synthetic resins include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyptal resin, epoxy resin, and alkylbenzene resin, as well as polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and modified polyphenylene. Thermoplastic resins such as oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyamino bismaleimide, 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 sufficient coverage can be obtained by setting the amount to be equal to or more than the lower limit value. On the other hand, by setting the amount to be less than or equal to 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 manner can be used as a coloring agent for colored partition walls according to a conventional method. When such carbon black is used, a colored partition wall with a high light shielding rate and a low surface reflectance tends to be formed at low cost. It is also assumed that by coating the carbon black surface with a resin, there is a function to confine ash containing Na and Ca into the carbon black.

These organic pigments and inorganic pigments are preferably dispersed and used so that the average particle diameter is usually 1 μm or less, preferably 0.5 μm or less, and more preferably 0.25 μm or less. Here, the standard for the average particle diameter is the number of pigment particles.
Further, the average particle diameter of the pigment is a value determined from the pigment particle diameter measured by dynamic light scattering (DLS). Particle size measurement is performed using a sufficiently diluted photosensitive resin composition (usually diluted to give a pigment concentration of about 0.005 to 0.2% by mass. However, if the concentration is recommended by the measuring device) , according to its concentration) and measured at 25°C.

Furthermore, in addition to the above-mentioned organic pigments and inorganic black pigments, dyes may be used. Examples of dyes that can be used as colorants include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like.
Examples of azo dyes include C.I. I. Acid Yellow 11, C. I. Acid Orange 7, C. I. Acid Red 37, C. I. Acid Red 180, C. I. Acid Blue 29, C. I. Direct Red 28, C. I. Direct Red 83, C. I. Direct Yellow 12, C. I. Direct Orange 26, C. I. Direct Green 28, C. I. Direct Green 59, C. I. Reactive Yellow 2, C. I. Reactive Red 17, C. I. Reactive Red 120, C. I. Reactive Black 5, C. I. Disperse Orange 5, C. I. Dispersed Red 58, C. I. Disperse Blue 165, C. I. Basic Blue 41, C. I. Basic Red 18, C. I. Mordant Red 7, C. I. Mordant Yellow 5, C. I. Examples include Mordant Black 7.

Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C. I. Acid Blue 40, C. I. Acid Green 25, C. I. Reactive Blue 19, C. I. Reactive Blue 49, C. I. Dispersed Red 60, C. I. Disperse Blue 56, C. I. Examples include Disperse Blue 60.
In addition, examples of phthalocyanine dyes include C.I. I. Pad Blue 5 etc. are quinoneimine dyes such as C.I. I. Basic Blue 3, C. I. Basic Blue 9 etc. are used as quinoline dyes such as C.I. I. Solvent Yellow 33, C. I. Acid Yellow 3, C. I. Disperse Yellow 64 and the like are used as nitro dyes such as C.I. I. Acid Yellow 1, C. I. Acid Orange 3, C. I. Examples include Disperse Yellow 42.

When the photosensitive resin composition of the present invention contains a colorant (E), the content of the colorant (E) in the total solid content is not particularly limited, but is usually 1% by mass or more, and 3% by mass or more. is preferable, and 4% by mass or more is more preferable. Further, it is usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 12% by mass or less, and particularly preferably 10% by mass or less. Setting the value above the lower limit tends to ensure light-shielding properties, and setting the value below the upper limit allows the content of alkali-soluble resins and ethylenically unsaturated compounds to be relatively increased, which improves the curability of the coating film and the ink repellency. There is a tendency for sexual performance to improve.

[1-1-6] Component (F); Dispersant When the photosensitive resin composition of the present invention contains (E) a colorant, the colorant (E) is finely dispersed and the dispersion state is stabilized. It is preferable to include (F) a dispersant in order to
(F) As the dispersant, a polymer dispersant having a functional group is preferable, and from the viewpoint of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a base thereof; a primary, secondary or tertiary Polymer 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. In particular, 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 preferred from the viewpoint that it can be dispersed with a small amount of dispersant.

Examples of polymeric dispersants include urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants consisting of monomers and macromonomers having amino groups, and polyoxyethylene alkyl ethers. Examples include a polyoxyethylene diester dispersant, a polyether phosphate dispersant, a polyester phosphate dispersant, a sorbitan aliphatic ester dispersant, an aliphatic modified polyester dispersant, and the like.

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

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 polymer dispersant and/or an acrylic polymer dispersant having a functional group; It is particularly preferred to include.
Further, 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 preferable.

Urethane-based and acrylic-based polymer dispersants include, for example, DISPERBYK-160 to 167, 182 series (all urethane-based), DISPERBYK-2000, 2001, BYK-LPN21116 (all acrylic-based), etc. (all of the above are manufactured by BYK Chemie) ).
To specifically illustrate a preferable chemical structure as a urethane-based polymer dispersant, 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, Examples include dispersion resins having a weight average molecular weight of 1,000 to 200,000, which are obtained by reacting active hydrogen with a compound having a tertiary amino group in the molecule. By treating these with a quaternizing agent such as benzyl chloride, all or part of the tertiary amino groups can be converted into 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, tolydine diisocyanate, etc. Aromatic diisocyanates, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanates such as dimer acid diisocyanate, isophorone diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), ω, ω Alicyclic diisocyanates such as '-diisocyanate dimethylcyclohexane, xylylene diisocyanate, aliphatic diisocyanates with aromatic rings such as α, α, α', α'-tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1, 6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris(isocyanate phenylmethane), tris(isocyanate phenyl) thiophosphate triisocyanates, trimers thereof, water adducts, polyol adducts thereof, and the like. Preferred polyisocyanates are trimers of organic diisocyanates, and most preferred are trimers of tolylene diisocyanate and isophorone diisocyanate.
These may be used alone or in combination of two or more.

As a method for producing isocyanate trimers, the polyisocyanates are treated with a suitable trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylic acid salts, etc. to form isocyanate groups. After the trimerization is stopped by adding a catalyst poison, unreacted polyisocyanate is removed by solvent extraction and thin film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

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

Polyether ester 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, such as poly(polyester diols). Oxytetramethylene) adipate and the like. The most preferred polyether glycols are polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or 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, aliphatic glycols such as 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, xylene Aromatic glycols such as lene glycol and bishydroxyethoxybenzene, N-alkyl dialkanolamines such as N-methyldiethanolamine, etc.), such as polyethylene adipate, polybutylene adipate, and polyhexamethylene adipate. , polyethylene/propylene adipate, etc., or polylactone diols or polylactone monools obtained using the above diols or monohydric alcohols having 1 to 25 carbon atoms as an initiator, such as polycaprolactone glycol, polymethylvalerolactone, and these. A mixture of two or more types may be mentioned. The most preferred polyester glycol is polycaprolactone glycol or polycaprolactone using an alcohol having 1 to 25 carbon atoms as an initiator.

Examples of polycarbonate glycol include poly(1,6-hexylene) carbonate, poly(3-methyl-1,5-pentylene) carbonate, etc.; examples of polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, etc. can be mentioned.
These may be used alone or in combination of two or more.

The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and 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, nitrogen atom, or sulfur atom, includes hydrogen atoms in functional groups such as hydroxyl groups, amino groups, and thiol groups, and among them, amino groups, especially primary The hydrogen atom of the amino group 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 such 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, and N,N-dimethyl-1,3-propanediamine. , 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 has a nitrogen-containing heterocyclic structure, examples of the nitrogen-containing heterocycle include a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring, a benzimidazole ring, and a benzo ring. 5-membered nitrogen-containing hetero rings such as triazole ring, benzoxazole ring, benzothiazole ring, and benzothiadiazole ring; 6-membered nitrogen-containing hetero rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring, etc. Examples include rings. Among these nitrogen-containing heterocycles, an imidazole ring or a triazole ring is preferred.

Specific examples of these compounds having an imidazole ring and an amino group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, and 1-(2-aminoethyl)imidazole. Further, 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, and 3-amino-1,2,4-triazole. preferable.
These may be used alone or in combination of two or more.

The preferred blending ratio of raw materials when producing a urethane polymer dispersant is 100 parts by mass of a polyisocyanate compound and 10 parts of a compound with a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule. -200 parts by weight, preferably 20-190 parts by weight, more preferably 30-180 parts by weight, and 0.2-25 parts by weight, preferably 0.3 parts by weight 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 during production usually 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. Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tertiary-butanol, and other alcohols; chlorides such as methylene chloride and chloroform; ethers such as tetrahydrofuran and diethyl ether; dimethylformamide and N-methyl Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used. These may be used alone or in combination of two or more.

In the above production, a urethanization reaction catalyst is usually used. Examples of this catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stannath octoate, iron-based catalysts such as iron acetylacetonate and ferric chloride, triethylamine, triethylenediamine, etc. Examples include grade amine type. These may be used alone or in combination of two or more.

The amount of the compound having active hydrogen and a tertiary amino group in the same molecule is preferably controlled within the range of 1 to 100 mgKOH/g based on the amine value after reaction. More preferably, it is in the range of 5 to 95 mgKOH/g. The amine value is a value obtained by neutralizing and titrating a basic amino group with an acid and expressed in mg of KOH in correspondence with the acid value. When the amount is equal to or more than the lower limit, the dispersion ability tends to be improved, and when the amount is less than the upper limit, the developability tends to be improved.

In addition, when isocyanate groups remain in the polymeric dispersant in the above reaction, it is preferable to crush the isocyanate groups with an alcohol or an amino compound because 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, and more preferably 3,000 to 50,000. When the amount is equal to or more than the lower limit, the dispersibility and dispersion stability tend to improve, and when the amount is less than the upper limit, the solubility tends to improve and the dispersibility improves.

The acrylic polymer dispersant includes an unsaturated group-containing monomer having a functional group (the functional group referred to herein is the functional group described above as a functional group contained in the polymer dispersant); It is preferable to use a random copolymer, a graft copolymer, or a block copolymer with an unsaturated group-containing monomer having no functional group. These copolymers can be produced by known methods.

Examples of unsaturated group-containing monomers having functional groups include (meth)acrylic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethyl phthalic acid, and 2-(meth)acrylic acid. unsaturated monomers having a carboxyl group such as loyloxyethyl hexahydrophthalic acid and acrylic acid dimer; tertiary amino groups such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate and quaternized products thereof; A specific example is an unsaturated monomer having a quaternary ammonium base. These may be used alone or in combination of two or more.

Examples of unsaturated group-containing monomers that do not have functional groups 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, poly2-hydroxyethyl (meth)acrylate macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, poly Examples include macromonomers such as caprolactone macromonomer. These may be used alone or in combination of two or more.

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 not having a functional group. In addition to partial structures derived from unsaturated group-containing monomers containing the above-mentioned functional groups, the block may also contain partial structures derived from unsaturated group-containing monomers that do not contain the above-mentioned functional groups. may be contained in the A block in either random copolymerization or block copolymerization. Further, the content of the partial structure not containing a 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 types of monomers. These may be contained in the B block in either random copolymerization or block copolymerization.
The AB or BAB block copolymer is prepared, for example, by the living polymerization method shown below.
Living polymerization methods include anionic living polymerization methods, cationic living polymerization methods, and radical living polymerization methods. Among these, in the anionic living polymerization method, the polymerization active species is an anion, and is represented by the following scheme, for example.

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 each an integer of 1 or more.

In the radical living polymerization method, the polymerization active species is a radical, and is shown, for example, in 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 , j and k are each an integer of 1 or more, and R ^a is a hydrogen atom or 1 It is a valent organic group, and R ^b is a hydrogen atom or a monovalent organic group different from R ^a .

When synthesizing this acrylic polymer dispersant, the methods described in Japanese Patent Application Laid-Open No. 9-62002 and P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), B. C. Anderson, G. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Miji, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Collection of Polymer Papers, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Organic Synthetic Chemistry, 43, 300 (1985), D. Y. Sogoh, W. R. Known methods such as those 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 may be an AB block copolymer or a BAB block copolymer. /B block ratio is preferably 1/99 to 80/20, especially 5/95 to 60/40 (mass ratio), and by keeping it within this range, a balance between dispersibility and storage stability can be ensured. Tend.
Further, the amount of quaternary ammonium base in 1 g of AB block copolymer or BAB block copolymer that can be used in the present invention is usually preferably 0.1 to 10 mmol; By keeping it within this range, there is a tendency to ensure good dispersibility.

Note that such block copolymers may normally contain amino groups generated during the manufacturing process, but the amine value is about 1 to 100 mgKOH/g, and from the viewpoint of dispersibility, Preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, even 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 the dispersant such as these block copolymers is expressed by the mass of KOH equivalent to the amount of base per gram 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 the dispersant sample into a 100 mL beaker and dissolve it in 50 mL of acetic acid. This solution is neutralized and titrated with a 0.1 mol/L HClO ₄ acetic acid solution using an automatic titrator equipped with a pH electrode. The inflection point of the titration pH curve is taken as the titration end point, and the amine value is determined by the following formula.

Amine value [mgKOH/g] = (561 × V) / (W × S) [However, W: Dispersant sample weighed amount [g], V: Titration amount at the titration end point [mL], S: Dispersant Represents the solid content concentration [mass%] of the sample. ]
In addition, the acid value of this block copolymer depends on the presence or absence and type of acidic groups that are the source of the acid value, but in general, the lower the better, it is usually 10 mgKOH/g or less, and its weight average molecular weight (Mw ) is preferably in the range of 1000 to 100,000. By keeping it within the above range, there is a tendency that good dispersibility can be ensured.

When the polymer dispersant has a quaternary ammonium base as a functional group, the specific structure of the polymer dispersant is not particularly limited. It is preferable to have the unit (i).

In the above formula (i), R ³¹ to R ³³ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or a substituent-containing aryl group. represents an optionally aralkyl group;
Two or more of R ³¹ to R ³³ may be bonded to each other 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.

The number of carbon atoms in the alkyl group which may have a substituent in R ³¹ to R ³³ of the above formula (i) is not particularly limited, but it is preferably 1 or more and 10 or less, and 6 It is more preferable that it is below. Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc. Among these, methyl, ethyl, propyl, butyl , a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be either linear or branched. It may also contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

The number of carbon atoms in the aryl group which may have a substituent in R ³¹ to R ³³ of the above formula (i) is not particularly limited, but is usually 6 or more, and preferably 16 or less, and 12 It is more preferable that it is below. Specific examples of the aryl group include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group, anthracenyl group, etc. Among these, phenyl group, methylphenyl group, ethylphenyl 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 the above formula (i) is not particularly limited, but is usually 7 or more, and preferably 16 or less, and 12 It is more preferable that it is below. Specific examples of aralkyl groups include phenylmethyl group (benzyl group), phenylethyl group (phenethyl group), phenylpropyl group, phenylbutyl group, phenylisopropyl group, etc. Among these, phenylmethyl group, phenylethyl group A phenylpropyl group, or a phenylbutyl group is preferable, and a phenylmethyl group or a phenylethyl group is more preferable.

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, and it is more preferable that R ³¹ and R ³³ are a methyl group, and R ³² is a phenylmethyl group. .

In addition, 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 "repeat unit (ii)") ) is preferable.

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

As the alkyl group which may have a substituent in R ³⁵ and R ³⁶ of the above formula (ii), those exemplified as R ³¹ to R ³³ of the above formula (i) can be preferably employed.
As the aryl group which may have a substituent in R ³⁵ and R ³⁶ of the above formula (ii), those exemplified as R ³¹ to R ³³ of the above formula (i) can be preferably employed.
As the aralkyl group which may have a substituent in R ³⁵ and R ³⁶ of the above formula (ii), those exemplified as R ³¹ to R ³³ of the above formula (i) can be preferably employed.

Among these, it is preferable that R ³⁵ and R ³⁶ are each independently an alkyl group which may have a substituent, and 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 of the above formula (i) and R ³⁵ and R ³⁶ of the above formula (ii) may have include a halogen atom, an alkoxy group, Examples include benzoyl group and hydroxyl group.

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., and are preferred. is a -COO-R ⁴⁴ - group.
In the above formula (i), examples of the counter anion Y ^- include 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) are Based on the total content of repeating units, it is preferably 60 mol% or less, more preferably 50 mol% or less, even more preferably 40 mol% or less, particularly preferably 35 mol% or less, Moreover, 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.

Further, the content ratio of the repeating unit represented by the formula (i) to all 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, further preferably 50 mol% or less, more preferably 30 mol% or less, and 20 mol% or less. is more preferable, and particularly preferably 15 mol% or less.

Further, the content ratio of the repeating unit represented by the formula (ii) to all 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 preferable, more preferably 30 mol% or less, and particularly preferably 25 mol% or less.

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

In the above formula (iii), R ⁴⁰ is an ethylene group or a propylene group; R ⁴¹ is an alkyl group that may have a substituent; R ⁴² is a hydrogen atom or a methyl group; n is 1 to It is an integer of 20.

The number of carbon atoms in the optionally substituted alkyl group in R ⁴¹ of the above formula (iii) is not particularly limited, but is 1 or more, preferably 2 or more, and 10 or less. It is preferably 6 or less, and more preferably 6 or less. Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc. Among these, methyl, ethyl, propyl, butyl , a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be either linear or branched. It may also contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

Further, n in the above formula (iii) is 1 or more, preferably 2 or more, and preferably 10 or less, from the viewpoint of compatibility and dispersibility with binder components such as solvents, and is preferably 10 or less, and 5 or less. It is more preferable that

Further, the content ratio of the repeating unit represented by the formula (iii) to all 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, further preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. When it is within the above range, it tends to be possible to achieve both compatibility with binder components such as solvents and dispersion stability.

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

In the above formula (iv), R is ^an alkyl group that may have a substituent, an aryl group that may have a substituent, or an aralkyl group that may have a substituent; ³⁹ is a hydrogen atom or a methyl group.

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

The number of carbon atoms in the optionally substituted aryl group in R ³⁸ of the above formula (iv) is not particularly limited, but is usually 6 or more, preferably 16 or less, and 12 or less. More preferably, it is 8 or less. Specific examples of the aryl group include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group, anthracenyl group, etc. Among these, phenyl group, methylphenyl group, ethylphenyl 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 ³⁸ of the above formula (iv) is not particularly limited, but is usually 7 or more, preferably 16 or less, and 12 or less. More preferably, it is 10 or less. Specific examples of aralkyl groups include phenylmethyl group (benzyl group), phenylethyl group (phenethyl group), phenylpropyl group, phenylbutyl group, phenylisopropyl group, etc. Among these, phenylmethyl group, phenylethyl group A phenylpropyl group, or a phenylbutyl group is preferable, and a phenylmethyl group or a phenylethyl group is more preferable.

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

Further, from the viewpoint of dispersibility, the content ratio of the repeating unit represented by the formula (iv) to all repeating units of the polymer dispersant is preferably 30 mol% or more, and 40 mol% or more. The content is more preferably 50 mol% or more, further preferably 80 mol% or less, and 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 styrenic monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acrylic acid chloride; (meth)acrylamide, N- Examples include repeating units derived from monomers such as (meth)acrylamide monomers such as methylol acrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and N-methacryloylmorpholine.

From the viewpoint of further improving dispersibility, the polymer dispersant includes an A block having repeating units (i) and repeating units (ii), and a B block having no repeating units (i) and repeating units (ii). It is preferable that it is a block copolymer having the following. The block copolymer is preferably an AB block copolymer or a BAB block copolymer. Surprisingly, by introducing not only a quaternary ammonium base but also a tertiary amino group into the A block, the dispersing ability of the dispersant tends to be significantly improved. Further, it is preferable that the B block has a repeating unit (iii), and more preferably a repeating unit (iv).

In the A block, the repeating unit (i) and the repeating unit (ii) may be contained in either random copolymerization or block copolymerization. In addition, two or more types of repeating units (i) and repeating units (ii) may be contained in one A block, and in that case, each repeating unit can be randomly copolymerized, It may be contained in any form of block copolymerization.

Further, repeating units other than repeating unit (i) and repeating unit (ii) may be contained in the A block, and examples of such repeating units include the above-mentioned (meth)acrylic acid ester monomer. Examples include repeating units derived from polymers. 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 the block.

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

When the photosensitive resin composition of the present invention contains (F) a dispersant, its content is not particularly limited, but it is preferably 0.1% by mass or more, and 0.1% by mass or more in the total solid content of the photosensitive resin composition. The content is more preferably .5% by mass or more, and even more preferably 0.8% by mass or more. Moreover, it is preferably 8% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, and particularly preferably 1% by mass or less. When the amount is equal to or more than the lower limit, the generation of residue due to aggregates tends to be suppressed, and when it is equal to or less than the upper limit, sensitivity and developability tend to improve.

[1-1-7] Ultraviolet absorber The photosensitive resin composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber is added for the purpose of controlling the photocuring distribution by causing the ultraviolet absorber to absorb a specific wavelength of the light source used for exposure. By adding an ultraviolet absorber, effects such as increasing the taper angle can be obtained. As the ultraviolet absorber, from the viewpoint of inhibiting light absorption of the photopolymerization initiator (B), for example, a compound having an absorption maximum in the wavelength range of 250 nm to 400 nm can be used.
The ultraviolet absorber preferably contains one or both of a benzotriazole compound and a triazine compound. Containing one or both of a benzotriazole compound and a triazine compound reduces the light absorption rate at the bottom of the initiator film, weakening the curing at the bottom of the coating, making the partition walls vertical, and increasing the taper angle. It is thought that the effect of increasing is obtained.

Examples of benzotriazole compounds include 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 3-[3-tert-butyl- Octyl 5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate, 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl) )-4-hydroxyphenyl]ethylhexyl propionate, 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, 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl) )-4-hydroxyphenyl]propionic acid and C7-9 straight chain and branched alkyl alcohols.

Commercially available benzotriazole compounds include, for example, Sumisorb (registered trademark, hereinafter the same) 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 (manufactured by Sumitomo Chemical), JF77, JF78, JF79, JF80, JF83 ( (manufactured by Johoku Chemical Industry), TINUVIN (registered trademark, same hereinafter) PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN 326, TINUVIN900, "TINUVIN 928", TINUVIN928, TINUVIN1130 (B ASF), EVERSORB70, EVERSORB71, EVERSORB72 , EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81 (manufactured by Eiguang Chemical Industry Co., Ltd., Taiwan), Tomisorb (registered trademark, the same applies hereinafter) 10 0, TomiSorb 600 (manufactured by API Corporation), SEESORB (registered trademark) ) 701, SEESORB702, SEESORB703, SEESORB704, SEESORB706, SEESORB707, SEESORB709 (manufactured by Cipro Kasei), and RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.).

Examples of 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 glycidyl ether reaction product, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-( Examples include 2,4-dibutoxyphenyl)-1,3-5-triazine. Among these, hydroxyphenyltriazine compounds are preferred from the viewpoint of taper angle.
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 Eikoh Chemical Industries, Taiwan), Tomisorb 800 (manufactured by API Corporation), SEESORB100, SEESORB101, SEESORB101S, SEESORB102, S EESORB103, SEESORB105, Benzophenone compounds such as SEESORB106, SEESORB107, and SEESORB151 (manufactured by Cipro 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; α-naphthol, β-naphthol, α-naphthol methyl ether, α-naphthol ethyl ether, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene , 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 and its derivatives such as anthracene and 9,10-dihydroxyanthracene; azo dyes, benzophenone dyes, aminoketone dyes, quinoline dyes, anthraquinone dyes, diphenylcyanoacrylate dyes, triazine dyes, p -dyes such as aminobenzoic acid dyes; and the like. Among these, from the viewpoint of the taper angle, it is preferable to use cinnamic acid derivatives and naphthalene derivatives, and it is particularly preferable to use cinnamic acid derivatives. These light absorbers can be used alone or in combination of two or more.

Among these, from the viewpoint of the taper angle, either or both of benzotriazole compounds and hydroxyphenyltriazine compounds are preferred, and benzotriazole compounds are particularly preferred.

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 photosensitive resin composition of the present invention contains an ultraviolet absorber, its content is not particularly limited, but is usually 0.01% by mass or more, preferably 0.01% by mass or more in the total solid content of the photosensitive resin composition. 05% by mass or more, more preferably 0.1% by mass or more, even 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 or less, The content is more preferably 5% by mass or less, and even more preferably 3% by mass or less. When the taper angle is set at or above the lower limit value, the taper angle tends to increase, and when the taper angle is set at or below the upper limit value, the sensitivity tends to be high.

Furthermore, when the photosensitive resin composition of the present invention contains an ultraviolet absorber, the blending ratio to (B) the photopolymerization initiator is as follows: (B) the blending amount of the ultraviolet absorber to 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, even 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 parts by mass. parts, more preferably 200 parts by mass or less, still more preferably 100 parts by mass or less. Setting the value above the lower limit value tends to increase the taper angle, and setting the value below the upper limit value tends to increase the sensitivity.

[1-1-8] Polymerization inhibitor The photosensitive resin composition of the present invention may contain a polymerization inhibitor. Since the inclusion of a polymerization inhibitor inhibits radical polymerization, it tends to be possible to increase the taper angle of the obtained partition walls.
Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). Among these, from the viewpoint of polymerization inhibition ability, hydroquinone, methylhydroquinone or methoxyphenol are preferred, and methylhydroquinone is more preferred.

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

When the photosensitive resin composition contains a polymerization inhibitor, its content is not particularly limited, but it is usually 0.0005% by mass or more, preferably 0.001% by mass in the total solid content of the photosensitive resin composition. As mentioned above, it is more preferably 0.01% by mass or more, and usually 0.1% by mass or less, preferably 0.08% by mass or less, and more preferably 0.05% by mass or less. There is a tendency that the taper angle can be increased by setting it to the above lower limit value or more, and high sensitivity can be maintained by setting it to the above upper limit value or less.

[1-1-9] Thermal polymerization initiator Furthermore, the photosensitive resin composition of the present invention may contain a thermal polymerization initiator. Containing a thermal polymerization initiator tends to increase the degree of crosslinking of the membrane. Specific examples of such thermal polymerization initiators include azo compounds, organic peroxides, hydrogen peroxide, and the like. These may be used alone or in combination of two or more.

In addition, when a thermal polymerization initiator is used in combination with a photopolymerization initiator in the hope of improving sensitivity or increasing the crosslinking density of the film, the total content ratio of these initiators will exceed the photopolymerization rate in the total solid content of the photosensitive resin composition. It is preferable to set the content ratio of the initiator so that the content ratio of the photopolymerization initiator and the thermal polymerization initiator is the same, and from the viewpoint of sensitivity, the content ratio of the photopolymerization initiator and the thermal polymerization initiator is set so that It is preferred that the amount of the agent be 5 to 300 parts by mass.

[1-1-10] Amino Compound The photosensitive resin composition of the present invention may contain an amino compound to promote thermosetting. In this case, the content of the amino compound in the photosensitive resin composition is usually 40% by mass or less, preferably 30% by mass or less in the total solid content of the photosensitive resin composition. Further, it is usually 0.5% by mass or more, preferably 1% by mass or more. There is a tendency that storage stability can be maintained by setting it below the above-mentioned upper limit, and there is a tendency that sufficient thermosetting property can be ensured by setting it above the above-mentioned lower limit. When the photosensitive resin composition contains an amino compound, the content of the amino compound in the total solid content of the photosensitive resin composition is, for example, 0.5 to 40% by mass, preferably 1 to 30% by mass. .

Examples of the amino compound include amino compounds having at least two functional groups such as a methylol group or an alkoxymethyl group obtained by condensing and modifying a methylol group with an alcohol having 1 to 8 carbon atoms. Specifically, for example, melamine resin obtained by polycondensing melamine and formaldehyde; benzoguanamine resin obtained by polycondensing benzoguanamine and formaldehyde; glycoluril resin obtained by polycondensing glycoluril and formaldehyde; Polycondensed urea resins; resins in which two or more of melamine, benzoguanamine, glycoluril, or urea are copolycondensed with formaldehyde; and modified resins in which the methylol groups of the above-mentioned resins are modified by alcohol condensation. These may be used alone or in combination of two or more. Among the amino compounds, melamine resins and modified resins thereof are preferred, modified resins in which the modification ratio of methylol groups is 70% or more are more preferred, and modified resins in which the modification ratio of methylol groups is 80% or more are particularly preferred.

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

[1-1-11] Silane coupling agent It is also preferable to add a silane coupling agent to the photosensitive resin composition of the present invention in order to improve the adhesion with the substrate. Various types of silane coupling agents can be used, such as epoxy, methacrylic, amino, and imidazole, but epoxy and imidazole silane coupling agents are particularly preferred from the viewpoint of improving adhesion. From the viewpoint of adhesion, its content is usually 20% by mass or less, preferably 15% by mass or less, based on the total solid content of the photosensitive resin composition.

[1-1-12] Inorganic filler In addition, the photosensitive resin composition of the present invention further improves the strength as a cured product and coats it by moderate interaction with an alkali-soluble resin (formation of a matrix structure). An inorganic filler may be contained for the purpose of improving the film's excellent flatness and taper angle. 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 diameter of these inorganic fillers is usually 0.005 to 2 μm, preferably 0.01 to 1 μm. The average particle diameter referred to in this embodiment is a value measured using a laser diffraction scattering particle size distribution measuring device manufactured by Beckman Coulter. Among these inorganic fillers, silica sol and silica sol modified products tend to have excellent dispersion stability and taper angle improvement effects, and are therefore preferably blended. When the photosensitive resin composition of the present invention contains these inorganic fillers, the content is usually 5% by mass or more, preferably 10% by mass or more in the total solid content from the viewpoint of sensitivity, It is usually 80% by mass or less, preferably 70% by mass or less.

[1-1-13] Phosphoric acid-based ethylenic monomer The photosensitive resin composition of the present invention may contain a phosphoric acid-based ethylenic monomer for the purpose of imparting adhesion to the 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 above general formulas (g1), (g2) and (g3), R ⁵¹ represents a hydrogen atom or a methyl group, l and l' are integers of 1 to 10, and m is 1, 2 or 3.

These phosphoric acid-based ethylenic monomers may be used alone or in combination of two or more. When these phosphoric acid-based ethylenic monomers are used, their content is usually preferably 0.02% by mass or more, more preferably 0.05% by mass or more, and 0.02% by mass or more, more preferably 0.05% by mass or more, in the total solid content of the photosensitive resin composition. It is more preferably 1% by mass or more, particularly preferably 0.2% by mass or more. Further, it is preferably 4% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1% by mass or less. When the amount is equal to or more than the lower limit, the effect of improving the adhesion with the substrate tends to be sufficient, and when it is less than the upper limit, the deterioration of the adhesion with the substrate tends to be easily suppressed.

[1-1-14] Solvent The photosensitive resin composition of the present invention usually contains a solvent, and the above-mentioned components are used in a state in which they are dissolved or dispersed in the solvent. 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 Glycol dialkyl ethers such as ether, 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, Ethylene glycol Glycol diacetates such as diacetate, 1,3-butylene glycol diacetate, and 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; acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl Ketones such as butyl ketone, methylhexylketone, methylnonylketone, methoxymethylpentanone; methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, 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, bicyclohexyl; aromatic hydrocarbons such as benzene, toluene, xylene, 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, Chain-like substances such as methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and 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; acetonitrile, Nitriles such as benzonitrile: tetrahydrofuran such as tetrahydrofuran, dimethyltetrahydrofuran, dimethoxytetrahydrofuran, etc.

Commercially available solvents applicable 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).

The above-mentioned solvent is capable of dissolving or dispersing each component in the photosensitive resin composition, and is selected depending on the method of using the photosensitive resin composition of the present invention. It is preferable to select one having a boiling point in the range 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 alone or in combination of two or more. In addition, these solvents have a total solid content in the photosensitive resin composition of usually 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, usually 90% by mass or less, preferably is preferably used in an amount of 50% by mass or less, more preferably 40% by mass or less, even more preferably 35% by mass or less. By setting it to the lower limit value or more, there is a tendency to suppress the occurrence of coating unevenness, and by setting it to the above upper limit value or less, there is a tendency that the occurrence of foreign matter, repellency, etc. can be suppressed.

[1-2] Method for preparing photosensitive resin composition The photosensitive resin composition of the present invention is prepared by mixing the above-mentioned components using a stirrer.
For example, when the colorant (E) contains a solvent-free component such as a pigment, it is preferable to perform a dispersion treatment in advance using a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, etc. Since the colorant (E) is made into fine particles by the dispersion treatment, the coating properties of the photosensitive resin composition are improved.

Dispersion treatment can usually be carried out in a system in which (E) a colorant, a solvent, and (F) a dispersant are used in combination, or in a system in which a part or all of (C) an alkali-soluble resin is optionally used in combination. (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 polymer dispersant as the dispersant (F) because it suppresses thickening of the obtained ink and photosensitive resin composition over time (excellent dispersion stability).
In this way, in the process of producing a 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 photosensitive resin composition can be preferably employed. Further, as the content ratio of each colorant in the colorant (E) in the pigment dispersion, the content ratios described as the content ratios in the photosensitive resin composition can be preferably adopted.

When dispersing the colorant (E) using 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 processing apparatus, etc., and is therefore adjusted as appropriate. A guideline for dispersion is to control the gloss of the ink so that the 20 degree specular gloss (JIS Z8741) of the photosensitive resin composition is in the range of 50 to 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 above dispersion treatment and the other components contained in the photosensitive resin composition are mixed to form a uniform solution. In the manufacturing process of a photosensitive resin composition, fine dust may be mixed into the liquid, so it is desirable to filter the obtained photosensitive resin composition using a filter or the like.

[2] Partition walls and method for forming the same The photosensitive resin composition of the present invention can be suitably used to form partition walls, particularly partition walls for partitioning organic layers of an organic electroluminescent device. A cured product obtained by curing the photosensitive resin composition of the present invention can be used as a partition wall.

The method of forming partition walls using the photosensitive resin composition described above is not particularly limited, and conventionally known methods can be employed. The method for forming the partition wall includes, for example, a coating step of coating a photosensitive resin composition on a substrate to form a photosensitive resin composition layer, and an exposure step of exposing the photosensitive resin composition layer. There are several methods. Specific examples of methods for forming such partition walls include an inkjet method and a photolithography method.

In the inkjet method, a photosensitive resin composition whose viscosity has been adjusted by dilution with a solvent is used as an ink, and ink droplets are ejected onto a substrate along a predetermined pattern of partition walls. is applied onto a substrate to form an uncured barrier rib pattern. Then, the uncured barrier rib pattern is exposed to light to form cured barrier ribs on the substrate. The uncured barrier rib pattern is exposed in the same manner as the exposure step in the photolithography method described later, except that a mask is not used.

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

In the coating process of applying a photosensitive resin composition onto a substrate in the photolithography method, a contact transfer type coating device such as a roll coater, reverse coater, or bar coater or a spinner (rotary type) is used to coat the substrate on which partition walls are to be formed. The photosensitive resin composition is applied using a non-contact type coating device such as a coating device) or a curtain flow coater, and if necessary, the solvent is removed by drying to form a photosensitive resin composition layer.

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

Next, in the developing step, the exposed photosensitive resin composition layer according to the pattern of the partition walls is developed with a developer to form partition walls. The developing method is not particularly limited, and a dipping method, a spray method, etc. can be used. Specific examples of developing solutions 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. Can be mentioned. Moreover, an antifoaming agent and a surfactant can also be added to the developer.

Thereafter, the developed partition walls are post-baked and cured by heating. Post-baking is preferably performed at 150-250°C for 15-60 minutes.

The substrate used for forming the barrier ribs is not particularly limited, and is appropriately selected depending on the type of organic electroluminescent device to be manufactured using the substrate on which the barrier ribs are formed. Suitable materials for the substrate include glass and various resin materials. Specific examples of the resin material include polyesters such as polyethylene terephthalate; polyolefins such as polyethylene and polypropylene; polycarbonate; poly(meth)methacrylic resin; polysulfone; and polyimide. Among these substrate materials, glass and polyimide are preferred because they have excellent heat resistance. Further, depending on the type of organic electroluminescent device to be manufactured, a transparent electrode layer of ITO, ZnO, or the like may be provided in advance on the surface of the substrate on which the partition wall is formed.

Although the shape of the partition walls is not particularly limited, 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 thickness of the partition wall is preferably 5 μm or more, more preferably 7 μm or more, even more preferably 8 μm or more, particularly preferably 10 μm or more, and usually 20 μm or less. The thickness of the partition wall is, for example, 5 to 20 μm, preferably 7 to 20 μm, more preferably 8 to 20 μm, and even more preferably 10 to 20 μm.

[3] Organic electroluminescent device The organic electroluminescent device of the present invention includes the partition wall of the present invention.
Various organic electroluminescent devices are manufactured using a substrate provided with a barrier rib pattern manufactured by the method described above. The method for forming an organic electroluminescent device is not particularly limited, but preferably, after forming a barrier rib pattern on a substrate by the method described above, ink is injected into an area surrounded by the barrier ribs on the substrate to form pixels, etc. An organic electroluminescent device is manufactured by forming an organic layer.
Types of organic electroluminescent 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 stacked in the opening surrounded by the partition walls. Ru. On the other hand, in the top emission type, for example, partition walls 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 the opening surrounded by the partition walls. Created by

When the partition wall has a skirted shape, the ink for forming the organic layer is repelled by the skirt portion of the partition wall, so that the area surrounded by the partition wall may not be sufficiently covered with the ink for forming the organic layer. On the other hand, by creating a good shape with no hemline, the area surrounded by the partition wall can be sufficiently covered with the ink for forming the organic layer. Thereby, for example, the problem of halation in organic EL display elements can be solved.

As the solvent used when forming the ink for forming the organic layer, water, organic solvents, and mixed solvents thereof can be used. The organic solvent is not particularly limited as long as it can be removed from the film formed after the ink is injected. 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, etc. can be mentioned. Further, surfactants, antioxidants, viscosity modifiers, ultraviolet absorbers, etc. can be added to the ink.

As a method for injecting ink into the area 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 to form the organic layer is appropriately selected depending on the type of organic electroluminescent device to be manufactured. When injecting ink by an inkjet method, the viscosity of the ink is not particularly limited as long as the ink can be well ejected from an 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.

Note that examples of the light-emitting layer include organic electroluminescent layers as described in JP-A No. 2009-146691 and Japanese Patent No. 5734681. Alternatively, quantum dots such as those described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may be used.

[4] Image display device The image display device of the present invention includes the cured product of the present invention.
For example, an image display device including an organic electroluminescent element can be mentioned. There are no particular restrictions on the type or structure of the image display device as long as it includes an organic electroluminescent device, and for example, it can be assembled using an active drive type organic electroluminescent device according to a conventional method. For example, the image display device of the present invention can be formed by the method described in "Organic EL Display" (Ohmsha, published August 20, 2004, written by Shizushi Tokito, Chihaya Adachi, and Hideyuki Murata). can do. For example, an image may be displayed by combining an organic electroluminescent device that emits white light and a color filter, or an image may be displayed by combining organic electroluminescent devices that emit light of different colors, such as RGB.

Hereinafter, the 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 unless the gist thereof is exceeded.
The constituent components of the photosensitive resin compositions used in the following Examples and Comparative Examples are as follows.

<Alkali-soluble resin-I>
A copolymer resin containing dicyclopentanyl methacrylate/styrene/glycidyl methacrylate (molar ratio: 0.30/0.10/0.60) as a constituent monomer is subjected to an addition reaction of acrylic acid in an equal amount to glycidyl methacrylate, An alkali-soluble acrylic copolymer resin, which is further subjected to an addition reaction with tetrahydrophthalic anhydride in an amount of 0.39 mol per mol of the constituent monomers of the copolymer resin. The weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 9000, and the solid content acid value was 80 mgKOH/g. (c1) This corresponds to an acrylic copolymer resin having an ethylenically unsaturated group in the side chain.

<Alkali-soluble resin-II>
A copolymer resin containing dicyclopentanyl methacrylate/styrene/glycidyl methacrylate (molar ratio: 0.02/0.05/0.93) as a constituent monomer is subjected to an addition reaction of an equal amount of acrylic acid with glycidyl methacrylate, and then anhydrous An alkali-soluble acrylic copolymer resin to which tetrahydrophthalic acid is added at a molar ratio of 0.10 per mole of the total number of moles of the constituent monomers of the above copolymer resin. The weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 7700, and the solid content acid value was 28.5 mgKOH/g. (c1) This corresponds to an acrylic copolymer resin having an ethylenically unsaturated group in the side chain.

<Alkali-soluble resin-III>
"ZCR-1642H" manufactured by Nippon Kayaku Co., Ltd. (weight average molecular weight Mw = 6500, acid value = 98 mgKOH/g)

<Dispersant-I>
"BYK-LPN21116" manufactured by BYK Chemie (acrylic A-B block copolymer consisting of an A block with a quaternary ammonium base and a tertiary amino group, and a B block without a quaternary ammonium base and a tertiary amino group) Coalescence.Amine value is 70mgKOH/g.Acid value is 1mgKOH/g or less.)

<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.

<Photopolymerization initiator-I>
A compound having the following chemical structure was used.

<Photopolymerization initiator-II>
A compound having the following chemical structure was used.

<Liquid repellent-I>
(Synthesis of precursor polymer 1)
Maleic anhydride (manufactured by Nippon Shokubai Co., Ltd., 24.3 g, 247.8 mmol), bicyclo[2.2.1]hept-5-ene-2- 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl carboxylate (120.0 g, 247.8 mmol) and dimethyl 2,2'-azobis ( 2-Methylpropionate) (V-601, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., 7.61 g, 30.6 mmol) was weighed and dissolved in methyl ethyl ketone (MEK, 28.5 g). After removing oxygen by bubbling nitrogen through the solution for 10 minutes, the temperature was raised to 60° C. with stirring and maintained for 2 hours. Subsequently, the temperature was raised to 80°C and maintained for 3 hours, and then V-601 (3.81 g, 15.3 mmol) was added and the reaction was continued for a further 3 hours. This reaction mixture was diluted with MEK and then added dropwise to a large amount of methanol to precipitate a polymer. After filtration using a Nutsche filter, the solid was further washed with methanol and dried under vacuum. The weight average molecular weight (Mw) of the obtained precursor polymer 1 was 5400, and the degree of dispersion (Mw/Mn) was 1.72.

(Synthesis of liquid repellent-I)
Into an appropriately sized reaction vessel equipped with a stirrer and condenser, Precursor Polymer 1 (10.0 g) was weighed and dissolved in MEK (10 g). Furthermore, 4-hydroxybutyl acrylate (4HBA, manufactured by Mitsubishi Chemical Corporation, 2.48 g, 17.2 mmol) and triethylamine (2.0 g) were added, and the mixture was heated at 70° C. for 6 hours. Formic acid was added to the reaction solution for acid treatment, and then the solution was added dropwise to a large amount of pure water to precipitate the polymer. PGMEA was added to the filtered solid and concentrated to obtain a PGMEA solution of liquid repellent-I. The weight average molecular weight (Mw) of liquid repellent-I was 4900, the dispersity (Mw/Mn) was 1.81, and the double bond equivalent was 1600 g/mol. Further, the fluorine atom content in liquid repellent-I was 34% by mass.
This liquid repellent-I has a repeating unit represented by the above formula (D-1-22) as the repeating unit (i), and a repeating unit represented by the above formula (D-1-32) as the repeating unit (iii). It has repeating units.

<Liquid repellent-II>
A PGMEA solution of liquid repellent-II was obtained by synthesizing in the same manner as liquid repellent-I except that the amount of triethylamine added was 3.0 g. The weight average molecular weight (Mw) of liquid repellent-II was 4500, the degree of dispersion (Mw/Mn) was 2.05, and the double bond equivalent was 1300 g/mol. Further, the fluorine atom content in the liquid repellent-II was 34% by mass.
This liquid repellent-II has a repeating unit represented by the above formula (D-1-22) as the repeating unit (i), and a repeating unit represented by the above formula (D-1-32) as the repeating unit (iii). It has repeating units.

<Liquid repellent-III>
Same method as liquid repellent-I except that 2-hydroxyethyl methacrylate (HEMA, manufactured by Nippon Shokubai Co., Ltd., 1.45 g, 11.2 mmol) was used instead of 4HBA, and the amount of triethylamine added was 1.0 g. A PGMEA solution of liquid repellent-III was obtained. The weight average molecular weight (Mw) of the liquid repellent-III was 4900, the degree of dispersion (Mw/Mn) was 1.81, and the double bond equivalent was 1600 g/mol. Further, the fluorine atom content in the liquid repellent-III was 36% by mass.
This liquid repellent-III has a repeating unit represented by the above formula (D-1-22) as the repeating unit (i), and a repeating unit represented by the above formula (D-1-31) as the repeating unit (iii). It has repeating units.

<Liquid repellent-IV>
(Synthesis of precursor polymer 2)
In an appropriately sized reaction vessel equipped with a stirrer and condenser, maleic anhydride (4.76 g, 48.5 mmol), 5-tridecafluorohexyl-2-norbornene (20.0 g, 48.5 mmol) and V -601 (1.5 g, 6.0 mmol) was weighed and dissolved in MEK (4.7 g). After bubbling nitrogen through this solution for 10 minutes to remove oxygen, the temperature was raised to 60°C while stirring and maintained for 2 hours. Subsequently, the temperature was raised to 80°C and maintained for 3 hours, and then V-601 (0.74 g, 3.0 mmol) was added and the reaction was continued for a further 3 hours. This reaction mixture was diluted with MEK and then added dropwise to a large amount of methanol to precipitate a polymer. After filtration using a Nutsche filter, the solid was further washed with methanol and dried under vacuum. The weight average molecular weight (Mw) of the obtained precursor polymer 2 was 3,700, and the degree of dispersion (Mw/Mn) was 1.64.

(Synthesis of liquid repellent-IV)
Precursor Polymer 2 (10.0 g) was weighed into an appropriately sized reaction vessel equipped with a stirrer and condenser and dissolved in MEK (10 g). Furthermore, 4HBA (2.83 g, 17.2 mmol) and triethylamine (2.0 g) were added, and the mixture was heated at 70° C. for 6 hours. Formic acid was added to the reaction solution for acid treatment, and then the solution was added dropwise to a large amount of pure water to precipitate the polymer. PGMEA was added to the filtered solid and concentrated to obtain a PGMEA solution of liquid repellent-IV. The weight average molecular weight (Mw) of the liquid repellent-IV was 3900, the degree of dispersion (Mw/Mn) was 1.60, and the double bond equivalent was 1400 g/mol. Further, the fluorine atom content in the liquid repellent-IV was 39% by mass.
This liquid repellent-IV has a repeating unit represented by the above formula (D-1-24) as the repeating unit (i), and a repeating unit represented by the above formula (D-1-32) as the repeating unit (iii). It has repeating units.

<Liquid repellent-V>
Megafac RS-78 (fluorine-based, liquid repellent with polycyclic aliphatic hydrocarbon skeleton and ethylenic double bond) manufactured by DIC Corporation
<Liquid repellent-VI>
Megafac RS-72-k (fluorine-based, liquid repellent with ethylenic double bond) manufactured by DIC Corporation

<Additive-I>
Karenz MT PE1 (pentaerythritol tetrakis (3-mercaptobutyrate) manufactured by Showa Denko)
<Additive-II>
KAYAMER PM-21 (methacryloyl group-containing phosphate) manufactured by Nippon Kayaku Co., Ltd.

<Preparation of pigment dispersion>
The pigment, dispersant, alkali-soluble resin, and solvent listed in Table 1 were mixed at the mass ratio listed in Table 1. This mixed solution was subjected to a dispersion treatment using a paint shaker at a temperature of 25 to 45° C. for 3 hours. Zirconia beads with a diameter of 0.5 mm were used as beads, and 2.5 times the mass of the dispersion was added. After the dispersion was completed, the beads and the dispersion were separated using a filter to prepare a pigment dispersion.
Note that the blending ratio of the solvent in Table 1 also includes the amount of the solvent derived from the dispersant and the alkali-soluble resin.

[Examples 1 to 5 and Comparative Examples 1 to 3]
Using the pigment dispersion prepared above, each component was added so that the solid content of each component in the total solid content was as shown in Table 2, and the total solid content was 31% by mass. , and diluted by adding each solvent so that solvent-I/solvent-II = 80/20 (mass ratio) in all solvents, stirred and dissolved, and prepared Examples 1 to 5 and Comparative Examples 1 to A photosensitive resin composition of No. 3 was prepared. The obtained photosensitive resin composition was filtered through a filter with a pore size of 5 μm, and then evaluated by the method described below.
The blending ratios of the pigment dispersion, alkali-soluble resin, and liquid repellent in Table 2 are calculated in terms of solid content. Moreover, the fluorine atom content rate in the total solid content indicates the content rate (mass %) of fluorine atoms in the liquid repellent (D) in the total solid content of the photosensitive resin composition.

The method of performance evaluation will be explained below.

<Measurement of PGMEA contact angle>
A photosensitive resin composition was coated onto a glass substrate using a spinner so that it had a thickness of 10.0 μm after being heated and cured. This coated substrate was vacuum dried for 1 minute, and then heated and dried on a hot plate at 100° C. for 120 seconds to obtain a coated substrate. Next, using a high-pressure mercury lamp, the entire surface was exposed at 50 mJ/cm ² while cutting off wavelengths of 330 nm or less. At this time, the light intensity at a wavelength of 365 nm was 45 mW/cm ² . Next, this substrate was spray developed at 24°C for 60 seconds using an aqueous solution containing 0.04% by mass of KOH and 0.07% by mass of Emulgen A-60 (surfactant manufactured by Kao Corporation) as a developer. After that, it was washed with pure water for 10 seconds. Finally, this substrate was heated and cured in an oven at 230° C. for 30 minutes to obtain a substrate for contact angle measurement.

Using Drop Master 500 (contact angle measuring device) manufactured by Kyowa Interface Science Co., Ltd., the contact angle was measured 1 second after dropping 0.7 μL of PGMEA onto the surface of the substrate for contact angle measurement under conditions of 23° C. and 50% humidity. did. The results are shown in Table 2. A larger contact angle indicates higher ink repellency.

<Evaluation of inkjet (IJ) wetting and spreading properties>
A photosensitive resin composition was coated onto a glass substrate using a spinner so that it had a thickness of 10.0 μm after being heated and cured. This coated substrate was vacuum dried for 1 minute, and then heated and dried on a hot plate at 100° C. for 120 seconds to obtain a coated substrate. Next, using a high-pressure mercury lamp, wavelengths of 330 nm or less were cut off and exposure was performed at 50 mJ/cm ² . Exposure was performed using a photomask, and the exposure gap was 5 μm. The photomask used had a plurality of rounded rectangular covering portions each having a length of 300 μm, a width of 100 μm, and a radius of curvature of each corner of 30 μm, arranged at intervals of 100 μm in the vertical direction and 10 μm in the horizontal direction. Next, development was performed under the same conditions as in the preparation of the substrate for contact angle measurement, and then heat curing was carried out at 230° C. for 30 minutes in an oven to obtain a barrier rib substrate for IJ. Note that, of the IJ partition substrate, a portion corresponding to the covering portion of the photomask is a pixel portion, and a portion corresponding to the opening portion is a partition.

Inkjet coating was performed on the IJ partition substrate using an IJ apparatus DMP-2831 manufactured by Fuji Film Corporation. As the cartridge head, DMC-11610 QS-256/10AAA (having a nozzle that discharges approximately 10 pL per drop) was used. As the ink, reactive diluent YED216D manufactured by Mitsubishi Chemical Corporation was used alone, 30 drops were discharged per pixel section, and the same operation was performed for 10 pixel sections. The state of the pixel portion from which the ink was ejected was observed with an optical microscope, and the IJ wettability was evaluated according to the following evaluation criteria. The results are shown in Table 2.

[IJ wettability evaluation criteria]
◎: Ink wets and spreads in all pixel areas.
○: Ink repellency (areas where the ink did not spread) was observed in some pixel areas.
×: Ink repellency (areas where the ink did not get wet and spread) was seen in all pixel areas (there was no pixel area where the ink got wet and spread).

Table 2 shows that the photosensitive resin compositions of Examples 1 to 5 have better IJ wetting and spreading properties than the photosensitive resin compositions of Comparative Examples 1 to 3. Examples 1 and 5 and Comparative Examples 1 and 2 each used the same liquid repellent but had different content ratios, but from their comparison, it was found that the IJ wettability was improved by changing the content ratio of the liquid repellent. It turns out that it is not something that can be improved by doing so.

The photosensitive resin compositions of each example contain resin (D-1) as a liquid repellent, and since the fluorine-containing organic group is bonded to the polycyclic aliphatic hydrocarbon skeleton in the main chain, This is thought to be because the fluorine-containing organic groups are less likely to be thermally decomposed, and fumes containing fluorine atoms are less likely to be generated during heat curing during pattern formation, making it difficult for fluorine-containing components to contaminate the pixel area. .

Further, from a comparison of Examples 1 to 4, it can be seen that Examples 2 and 4 have particularly good IJ wetting and spreading properties. The liquid repellent-II contained in the photosensitive resin composition of Example 2 has a low double bond equivalent and a large number of crosslinking groups, making it difficult for the liquid repellent to seep into the pixel area during development and baking. Conceivable. In addition, since the liquid repellent agent-IV contained in the photosensitive resin composition of Example 4 has a structure in which the fluorine-containing organic group is difficult to decompose, it is suppressed from breaking and decomposing during heat curing and contaminating the pixel area. It is thought that this is due to the fact that

Claims (8)

A photosensitive resin composition containing (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, (C) an alkali-soluble resin, and (D) a liquid repellent,
The liquid repellent (D) has a repeating unit (i) represented by the following general formula (D-1-1) and a partial structure (ii) represented by the following general formula (D-1-2). Contains resin (D-1),
A photosensitive resin composition, wherein the repeating unit (i) is a repeating unit (i-2) represented by the following general formula (D-1-4).

(In the formula, L represents a polycyclic aliphatic hydrocarbon skeleton that may have a substituent.
However, L has one or more fluorine-containing organic groups having 1 to 30 carbon atoms as the substituent.
* represents a bond. )

(In the formula, R ¹¹ represents a hydrogen atom or a methyl group.
g represents an integer from 0 to 6.
* represents a bond. )

(In the formula, R ¹ to R ⁴ each independently represent a hydrogen atom or an arbitrary substituent.
However, at least one of R ¹ to R ⁴ is a group represented by the following general formula (D-1-1-a).
n is 0.
* represents a bond. )

(In the formula, R ¹² represents an alkyl group having 1 to 27 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, and the carbon-carbon bond of the alkyl group may be interrupted by one oxygen atom. .
X represents a single bond, -O-, -CO-O-, -O-CO-, or -CO-NH-.
k represents an integer from 0 to 2.
* represents a bond. ) The photosensitive resin composition according to claim 1, wherein the resin (D-1) further has a repeating unit (iii) represented by the following general formula (D-1-5).

(In the formula, R ⁵ represents the partial structure (ii).
* represents a bond. ) The photosensitive resin composition according to claim 1 or 2, wherein the content of the liquid repellent (D) is 0.3% by mass or more in the total solid content. The photosensitive resin composition according to any one of claims 1 to 3, wherein the content of the liquid repellent (D) is 5% by mass or less based on the total solid content. The photosensitive resin composition according to any one of claims 1 to 4, further comprising (E) a colorant. The photosensitive resin composition according to any one of claims 1 to 5, which is used for forming partition walls. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 6. An image display device comprising the cured product according to claim 7.