JP7250600B2 - Photosensitive resin composition - Google Patents

Description

The present invention relates to a photosensitive resin composition.

A photosensitive resin composition is used in photolithography, and is a material whose solubility in a developing solution changes depending on whether or not it is exposed to light. The photolithography method is frequently used in the manufacture of members for image display devices, the manufacture of circuit boards for electronic equipment, the manufacture of semiconductor elements, and the like. In such a technical field, it is required that a molded article can be obtained with a fine pattern and that the developing speed is high.

One of the applications of the photosensitive resin composition is a material for color filters used in image display devices such as liquid crystal display devices. A color filter is usually produced by applying a photosensitive resin composition containing a coloring material such as a pigment and a photocurable resin to a transparent substrate, followed by an exposure step, a development step, and a heat treatment (post-baking) step. Manufactured by etc. Conventionally, glass plates have been widely used as transparent substrates, but it is conceivable that color filters using transparent substrates made of resin will increase in the future. In recent years, the use of coloring materials with low heat resistance to form color filters has also increased. Thus, when using a resin-made transparent substrate and a coloring material with low heat resistance, a photosensitive resin composition that can be molded at a low heat treatment temperature is required.

JP 2018-155924 A JP 2014-162814 A

The present invention has been made to solve the above problems, and the purpose thereof is to:
An object of the present invention is to provide a photosensitive resin composition which can obtain the effect of heat treatment (post-baking) at a low temperature and which can form a molded article having excellent solvent resistance.

The photosensitive resin composition of the present invention comprises an alkali-soluble resin, a coloring material, a polyfunctional monomer, a photopolymerization initiator, and a solvent, and the alkali-soluble resin is a constituent unit having an acrylate group in its side chain. , a structural unit having an acid group in the side chain, and a structural unit having a ring structure in the main chain.
In one embodiment, the alkali-soluble resin has a double bond equivalent weight of 200 g/eq to 1000 g/eq.
In one embodiment, the content of the structural unit having an acid group in the side chain is 10 parts by weight (parts by weight) to 70 parts by weight (parts by weight) with respect to 100 parts by weight (parts by weight) of the alkali-soluble resin. ).
In one embodiment, the content of the structural unit having a ring structure in the main chain is 5 parts by weight to 50 parts by weight with respect to 100 parts by weight of the alkali-soluble resin.
According to another aspect of the invention, an alkali-soluble resin is provided. This alkali-soluble resin contains a structural unit having an acrylate group in its side chain, a structural unit having an acid group in its side chain, and a structural unit having a ring structure in its main chain.
In one embodiment, the alkali-soluble resin has a double bond equivalent of 200 g/eq to 1000 g/eq.
In one embodiment, the content of the structural unit having an acid group in the side chain is 10 parts by weight to 70 parts by weight with respect to 100 parts by weight of the alkali-soluble resin.
In one embodiment, the content of the structural unit having a ring structure in the main chain is 5 parts by weight to 50 parts by weight with respect to 100 parts by weight of the alkali-soluble resin.
According to another aspect of the present invention, a method for manufacturing a molded body is provided. The method for producing the molded article includes applying the photosensitive resin composition to a resin substrate to form a coating layer, and curing the coating layer and heating at 200° C. or less. .

ADVANTAGE OF THE INVENTION According to this invention, the effect of heat processing (post-baking) is acquired by low temperature, and the photosensitive resin composition which can form the molded object excellent in solvent resistance can be provided.

1 is a schematic cross-sectional view of a molded body formed from a photosensitive resin composition according to one embodiment of the present invention; FIG.

A. Outline of Photosensitive Resin Composition The photosensitive resin composition of the present invention contains an alkali-soluble resin, a coloring material, a polyfunctional monomer, a photopolymerization initiator, and a solvent. The alkali-soluble resin includes a structural unit having an acrylate group in its side chain, a structural unit having an acid group in its side chain, and a structural unit having a ring structure in its main chain.

In the present invention, by containing an alkali-soluble resin containing a structural unit having an acrylate group (side chain acrylate group) in the side chain, the effect of heat treatment (post-baking) can be obtained at a low temperature (for example, 200 ° C. or less). Moreover, it is possible to provide a photosensitive resin composition capable of forming a molded article having excellent solvent resistance. In general, acrylate groups and methacrylate groups do not have much difference in properties, and resins having acrylate groups and resins having methacrylate groups are often used for the same purposes. On the other hand, the present invention is characterized by using an alkali-soluble resin having an acrylate group, as distinguished from an alkali-soluble resin having a methacrylate group. is. In one embodiment, the alkali-soluble resin does not have a methacrylate group in its side chain.

The side chain acrylate group content in the alkali-soluble resin can be expressed in terms of double bond equivalent. The double bond equivalent of the alkali-soluble resin is preferably 200 g/eq to 1000 g/eq, more preferably 300 g/eq to 1000 g/eq, still more preferably 500 g/eq to 900 g/eq, especially It is preferably 550 g/eq to 700 g/eq. Within such a range, the above effects are more pronounced. The double bond equivalent is the weight average molecular weight per double bond (acrylate group) in the alkali-soluble resin, and can be calculated by the following formula.
Double bond equivalent (g/eq) = total monomer amount (g) used in alkali-soluble resin (polymer after addition of compound having acrylate group)/mol of added compound having acrylate group

In addition, in the present invention, the alkali-soluble resin has a ring structure in the main chain, so that when a pigment is used as a coloring material, the coloring material (pigment) has excellent dispersibility, and the coloring material ( A photosensitive resin composition in which the pigment) is difficult to aggregate can be obtained. Moreover, by having a ring structure in the main chain, an alkali-soluble resin having high solubility in alkali can be obtained.

FIG. 1 is a schematic cross-sectional view of a molded body formed from a photosensitive resin composition according to one embodiment of the present invention. According to the photosensitive resin composition of the present invention, the tapered molded body 10 is formed by containing the alkali-soluble resin having the structural unit having the acid group in the side chain and the structural unit having the ring structure in the main chain. obtain. As shown in FIG. 1, a tapered molded body means a molded body whose upper part is narrower than its lower part in a cross-sectional view, and also includes a molded body with substantially no diameter difference in the height direction. is. The taper angle (angle a in FIG. 1) of the molded body is preferably 90° or less, more preferably 85° or less, still more preferably 60° to 80°. A tapered molded article has an advantage of being excellent in adhesion to a substrate. Further, when a tapered color filter, a photospacer, or the like is formed using the photosensitive resin composition, it is possible to prevent disconnection during the formation of electrodes by coating, or prevent unnecessary This is advantageous in that it is possible to prevent air bubbles from forming in the liquid crystal due to the formation of air gaps.

In one embodiment, the photosensitive resin composition of the present invention is a mixture of a coloring material dispersion composition (mill base) containing a coloring material and a dispersing agent and a clear resist containing a polyfunctional monomer and a photopolymerization initiator. provided. The alkali-soluble resin may be contained in the colorant-dispersed composition, may be contained in the clear resist, or may be contained in both the colorant-dispersed composition and the clear resist. In one embodiment, the alkali-soluble resin is contained in the colorant-dispersed composition. The coloring material dispersion composition containing the above alkali-soluble resin is advantageous in that the coloring material (for example, pigment) has very excellent dispersion stability and the coloring material hardly aggregates over time. The colorant-dispersed composition and/or clear resist contain any appropriate solvent.

The photosensitive resin composition of the present invention is mainly used as a negative photosensitive resin composition, and is suitable for, for example, color filters, photospacers, overcoats, black matrices, black column spacers, inks, paints, sealants and the like. can be used. As described above, the photosensitive resin composition of the present invention can obtain the effect of heat treatment (post-baking) at a low temperature, so it is particularly suitable for coating on resin substrates (for example, PET film).

B. Alkali-Soluble Resin As described above, the alkali-soluble resin includes structural units (A) having an acrylate group in the side chain, structural units (I) having an acid group in the side chain, and structural units (II) having a ring structure in the main chain. )including. The alkali-soluble resin is typically a (meth)acrylic resin. The (meth)acrylic resin is not particularly limited as long as it is a resin obtained by polymerizing a monomer composition containing at least 10% by weight (mass%) or more of a (meth)acrylic monomer such as a (meth)acrylic acid ester. First, the monomer composition may contain other monomers copolymerizable with the (meth)acrylic monomer.

The alkali-soluble resin is a monomer composition containing a monomer (i) having an acid group in the side chain, and a monomer (ii) having a ring structure in the main chain and/or a monomer (ii') capable of forming a ring structure. to form a polymer X, and a compound (a) having an acrylate group in the polymer X with a part of the acid groups (acid groups derived from the monomer (i)) of the polymer X as reaction sites can be obtained by adding Further, instead of the monomer (i) having an acid group in the side chain, or in combination with the monomer (i), the monomer composition may contain a monomer (i') capable of introducing an acid group. good too. Furthermore, the monomer composition may further contain other monomers (iii) constituting other structural units (III). In one embodiment, monomer (i), monomer (i') and/or monomer (iii) are (meth)acrylic monomers, preferably acrylic monomers.

B-1. Structural unit (I) having an acid group in the side chain
If the alkali-soluble resin has the structural unit (I) having an acid group in its side chain, it is possible to obtain a photosensitive resin composition having excellent alkali developability. Examples of the monomer constituting the structural unit (I) having an acid group in the side chain (monomer (i) having an acid group) include acrylic acid, methacrylic acid, 2-(meth)acryloyloxyethyl succinic acid, itacon Acids, monomers having a carboxyl group such as ω-carboxy-polycaprolactone monoacrylate; monomers having a carboxylic acid anhydride group such as maleic anhydride and itaconic anhydride. Among them, acrylic acid is preferred. These monomers may be used alone or in combination of two or more.

A monomer (i') into which an acid group can be introduced may be used as a monomer constituting the structural unit (I) having an acid group in its side chain. Monomer (i') is a monomer capable of imparting an acid group after polymerization. Examples of the monomer (i′) include monomers having a hydroxyl group such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate; monomers having an epoxy group such as glycidyl acrylate and glycidyl methacrylate; Examples thereof include monomers having an isocyanate group such as isocyanatoethyl methacrylate. These monomers may be used alone or in combination of two or more. Preferably, an acrylic monomer is used as the monomer (i'). The post-treatment for imparting an acid group varies depending on the type of the monomer (i') used. , an acid anhydride such as maleic anhydride may be added. When the monomer (i') having an epoxy group is used, for example, a compound having an amino group and an acid group such as N-methylaminobenzoic acid or N-methylaminophenol is added, or (meth) An acid anhydride (eg, succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride) may be added to the hydroxyl group formed after addition of an acid such as acrylic acid. Further, when the monomer (i') having an isocyanate group is used, a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid may be added.

The content of the structural unit (I) having an acid group in the side chain is preferably 10 parts by weight to 70 parts by weight, more preferably 15 parts by weight to 65 parts by weight, with respect to 100 parts by weight of the alkali-soluble resin. and more preferably 15 to 60 parts by weight.

In the monomer composition forming the alkali-soluble resin, the content of the monomer (i) having an acid group is preferably 10 parts by weight to 70 parts by weight with respect to 100 parts by weight of all the monomers in the monomer composition. , more preferably 15 to 65 parts by weight, more preferably 15 to 60 parts by weight. Further, the content of the monomer (i') capable of introducing an acid group in the monomer composition forming the alkali-soluble resin is preferably from 10 parts by weight to 100 parts by weight of all the monomers in the monomer composition. 70 parts by weight, more preferably 15 to 65 parts by weight, even more preferably 15 to 60 parts by weight.

B-2. Structural unit (A) having an acrylate group in the side chain
The structural unit (A) having an acrylate group in its side chain can be obtained by adding a compound having an acrylate group using a part of the acid group of the structural unit (I) having an acid group in its side chain as a reaction point. can be done.

When the acid group of the structural unit (I) having an acid group in its side chain is a carboxyl group, examples of the compound having an acrylate group include a compound having an epoxy group and an acrylate group, a compound having an isocyanate group and an acrylate group, and the like. can be used. Examples of compounds having an epoxy group and an acrylate group include glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl acrylate. Among them, glycidyl acrylate and/or 4-hydroxybutyl acrylate glycidyl ether can be preferably used. Compounds having an isocyanate group and a double bond include 2-isocyanatoethyl acrylate and the like. When the acid group of the structural unit (I) having an acid group in its side chain is a carboxylic anhydride group, a compound having a hydroxyl group and an acrylate group can be used as the compound having an acrylate group. Examples of compounds having a hydroxyl group and a double bond include 2-hydroxyethyl acrylate.

The amount of the compound having an acrylate group added is preferably 15 parts by weight or more, more preferably 100 parts by weight of the polymer X (that is, the polymer before addition of the compound having an acrylate group). It is 20 parts by weight or more, more preferably 25 parts by weight or more. Within such a range, it is possible to obtain the effect of heat treatment (post-baking) at a low temperature and to obtain a photosensitive resin composition capable of forming a molded article having excellent solvent resistance. Also, a photosensitive resin composition having excellent exposure sensitivity can be obtained. By using such a photosensitive resin composition, it is possible to form a dense cured coating film, which is excellent in adhesion to substrates, and to form a molded article having high strength. Further, when the addition amount of the compound having an acrylate group is within the above range, sufficient hydroxyl groups are generated by the addition of the compound having an acrylate group, and a photosensitive resin composition having excellent solubility in an alkaline developer can be obtained. . The upper limit of the added amount of the compound having an acrylate group is preferably 150 parts by weight or less, more preferably 100 parts by weight or less, and still more preferably 80 parts by weight or less with respect to 100 parts by weight of the polymer X. be.

B-3. Structural unit (II) having a ring structure in the main chain
Examples of the structural unit (II) having a ring structure in the main chain include structural units having a maleimide structure, an N-substituted maleimide structure, a lactone ring structure, a glutaric anhydride structure, a maleic anhydride structure, and the like. Of these, a maleimide structure or an N-substituted maleimide structure is preferred. By using an alkali-soluble resin having a structural unit having a maleimide structure or an N-substituted maleimide structure in its main chain, a resin having high alkali solubility can be obtained. Specifically, the structural unit (II) having a ring structure in the main chain is preferably at least one selected from structural units represented by general formulas (1) to (3). ) is more preferred. By using an alkali-soluble resin (preferably a (meth)acrylic resin) having a structural unit represented by the general formula (1), it is possible to obtain a photosensitive resin composition capable of forming a molded article having high strength. .

式（４）～（７）中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６はそれぞれ独立して、水素原子または炭素数が１～３０の直鎖状もしくは分岐状のアルキル基であり、好ましくは水素原子または炭素数が１～１０の直鎖状もしくは分岐状のアルキル基であり、より好ましくは水素原子または炭素数が１～５の直鎖状もしくは分岐状のアルキル基であり、さらに好ましくはメチル基である。 The structural unit (II) having a ring structure in its main chain may be at least one selected from structural units represented by general formulas (4) to (7). Among them, structural units represented by general formula (4) or (7) are preferred.

In formulas (4) to (7), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a linear or branched chain having 1 to 30 carbon atoms. an alkyl group, preferably a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms group, more preferably a methyl group.

The structural unit (II) having a ring structure in its main chain can be composed of the monomer (ii) having a ring structure in its main chain. Monomer (ii) having a ring structure in the main chain includes, for example, maleimide, benzylmaleimide, phenylmaleimide, naphthylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide. , No-chlorophenylmaleimide, Nm-chlorophenylmaleimide, Np-chlorophenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, No- Aromatic-substituted maleimides such as methoxyphenylmaleimide, Nm-methoxyphenylmaleimide and Np-methoxyphenylmaleimide; alkyl-substituted maleimides such as cyclohexylmaleimide, methylmaleimide, ethylmaleimide, propylmaleimide and isopropylmaleimide; be done. Of these, maleimide, benzylmaleimide, phenylmaleimide and cyclohexylmaleimide are preferred, benzylmaleimide, phenylmaleimide and cyclohexylmaleimide are more preferred, and benzylmaleimide is even more preferred. The above monomers may be used alone or in combination of two or more.

式（８）および（９）中、Ｒ^１、Ｒ^２およびＲ^３は上記で説明したとおりである。 A monomer (ii') capable of forming a ring structure by an intramolecular cyclization process may be used as a monomer constituting the structural unit (II) having a ring structure in the main chain. The monomer (ii') forms structural units represented by general formulas (4) to (7). Monomer (ii') includes, for example, 1,6-dienes represented by general formula (8) or (9).

In formulas (8) and (9), R ¹ , R ² and R ³ are as explained above.

The content of the structural unit (II) having a ring structure in the main chain is preferably 5 parts by weight to 50 parts by weight, more preferably 8 parts by weight to 30 parts by weight, with respect to 100 parts by weight of the alkali-soluble resin. and more preferably 10 to 25 parts by weight.

In the monomer composition forming the alkali-soluble resin, the content of the monomer (ii) having a ring structure in the main chain is preferably 5 parts by weight to 50 parts by weight with respect to 100 parts by weight of all the monomers in the monomer composition. parts, more preferably 8 to 30 parts by weight, still more preferably 10 to 25 parts by weight. Further, the content of the monomer (ii') capable of forming a ring structure in the monomer composition forming the alkali-soluble resin is preferably from 5 parts by weight to 100 parts by weight of the total monomers in the monomer composition. 50 parts by weight, more preferably 8 to 30 parts by weight, still more preferably 10 to 25 parts by weight.

B-4. Other structural units (III)
The alkali-soluble resin may further have another structural unit (III). Other structural units include a structural unit (III-1) having two or more oxyalkylene groups in a side chain; a structural unit (III-2) having a biphenyl group in a side chain; '), monomer (ii), structural unit (III-3) derived from other monomer (iii-3) polymerizable with any of monomer (ii'), and the like.

(Structural unit (III-1) having two or more oxyalkylene groups in side chains)
The alkali-soluble resin has a structural unit (III-1) having two or more oxyalkylene groups in the side chain, thereby forming a photosensitive resin composition having a high crosslink density and a high breaking strength. Obtainable. Moreover, a photosensitive resin composition having particularly excellent colorant dispersibility can be obtained.

式（１０）中、Ｒ^７、Ｒ^８およびＲ^９はそれぞれ独立して、水素原子またはメチル基であり、好ましくは水素原子である。Ｒ^１０は、炭素数が１～２０の直鎖状もしくは分岐状のアルキル基、炭素数が２～２０の直鎖状もしくは分岐状のアルケニル基または炭素数が６～２０の芳香族炭化水素基であり、好ましくは水素原子、炭素数が１～２０の直鎖状のアルキル基、炭素数が２～２０の直鎖状のアルケニル基または炭素数が６～２０の芳香族炭化水素基であり、より好ましくは炭素数が１～１０の直鎖状のアルキル基または炭素数が６～１２の芳香族炭化水素基であり、さらに好ましくは炭素数が１～５の直鎖状のアルキル基、フェニル基またはビフェニル基であり、特に好ましくはメチル基、フェニル基またはビフェニル基である。なお、アルキル基、アルケニル基および芳香族炭化水素基は、置換基を有していてもよい。ＡＯは、オキシアルキレン基を表す。ＡＯで表されるオキシアルキレン基の炭素数は２～２０であり、好ましくは２～１０であり、より好ましくは２～５であり、さらに好ましくは２である。構成単位（ＩＩＩ－１）は１種または２種以上のオキシアルキレン基を含み得る。ｘは０～２の整数を表す。ｙは０または１を表す。ｎ１は、オキシアルキレン基の平均付加モル数を表し、２以上であり、好ましくは２～１００であり、より好ましくは２～５０であり、さらに好ましくは２～１５である。ｎ１がこのような範囲であれば、基材との密着性に優れる成形体（例えば、カラーフィルター）を形成し得る感光性樹脂組成物の材料となり得る感光性樹脂を得ることができる。 Examples of structural units (III-1) having two or more oxyalkylene groups in side chains include structural units represented by general formula (10).

In formula (10), ^R7 , ^R8 and ^R9 are each independently a hydrogen atom or a methyl group, preferably a hydrogen atom. R ¹⁰ is a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms. is preferably a hydrogen atom, a linear alkyl group having 1 to 20 carbon atoms, a linear alkenyl group having 2 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms. , more preferably a linear alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, more preferably a linear alkyl group having 1 to 5 carbon atoms, It is a phenyl group or a biphenyl group, and particularly preferably a methyl group, a phenyl group or a biphenyl group. In addition, the alkyl group, the alkenyl group and the aromatic hydrocarbon group may have a substituent. AO represents an oxyalkylene group. The oxyalkylene group represented by AO has 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, and still more preferably 2 carbon atoms. Structural unit (III-1) may contain one or more oxyalkylene groups. x represents an integer of 0 to 2; y represents 0 or 1; n1 represents the average number of added moles of the oxyalkylene group, and is 2 or more, preferably 2-100, more preferably 2-50, still more preferably 2-15. If n1 is within such a range, it is possible to obtain a photosensitive resin that can be used as a material for a photosensitive resin composition capable of forming a molded article (for example, a color filter) having excellent adhesion to a substrate.

The structural unit (III-1) having two or more oxyalkylene groups in its side chain is composed of the monomer (iii-1) having two or more oxyalkylene groups in its side chain. Examples of the monomer (iii-1) include ethoxylated o-phenylphenol (meth)acrylate (2 mol of EO), phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate (4 mol of EO), methoxypolyethylene glycol (meth)acrylate (4 mol of EO), ) acrylate (9 mol of EO), methoxypolyethylene glycol (meth)acrylate (13 mol of EO), methoxytriethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, butoxydiethylene glycol (meth) acrylate, 2-ethylhexyl diethylene glycol (meth) acrylate , methoxy dipropylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate (EO4-17 mol), nonylphenoxy polypropylene glycol (meth) acrylate (PO5 mol), EO-modified cresol ( meth)acrylate (2 mol of EO) and the like. These monomers may be used alone or in combination of two or more. In the present specification, notations such as "EO 2 mol" and "PO 5 mol" represent the average number of added moles of oxyalkylene groups.

(Structural unit (III-2) having a biphenyl group in the side chain)
When the alkali-soluble resin has a structural unit (A) having a biphenyl group in its side chain, it is possible to obtain a photosensitive resin composition having excellent dispersion stability of the coloring material. Moreover, by using an alkali-soluble resin having a structural unit (A) having a biphenyl group in its side chain, a photosensitive resin composition having excellent development speed can be obtained.

Preferably, the structural unit (III-2) having a biphenyl group in its side chain is a structural unit derived from a (meth)acrylic monomer.

式（１２）中、ｎ２は１～１０であり、好ましくは１または２である。 Examples of the structural unit (III-2) having a biphenyl group in the side chain include biphenyl (meth)acrylate, o-biphenyloxyethyl (meth)acrylate (ethoxylated o-phenylphenol (meth)acrylate), o-biphenyl Oxyethoxyethyl (meth) acrylate, m-biphenyloxyethyl acrylate, p-biphenyloxyethyl (meth) acrylate, o-biphenyloxy-2-hydroxypropyl (meth) acrylate, p-biphenyloxy-2-hydroxypropyl (meth) ) acrylate, m-biphenyloxy-2-hydroxypropyl (meth)acrylate, N-(meth)acryloyloxyethyl-o-biphenyl=carbamate, N-(meth)acryloyloxyethyl-p-biphenyl=carbamate, N-( Structural units derived from monomers (iii-2) having a biphenyl group in the side chain such as meth)acryloyloxyethyl-m-biphenyl=carbamate, o-phenylphenol glycidyl ether acrylate, and o-biphenyloxypropyl (meth)acrylate. be done. Among them, structural units derived from acrylic monomers are preferred. By using an acrylic monomer having no methyl group in the double bond portion, it is possible to obtain a photosensitive resin that can be used as a material for a photosensitive resin composition having a high development rate. In one embodiment, the structural unit (III-2) having a biphenyl group in its side chain is a structural unit derived from the monomer (iii-2) represented by general formula (11) or (12). More preferably, the structural unit (III-2) having a biphenyl group in its side chain is a structural unit derived from the monomer (iii-2) represented by general formula (12). In addition, you may use the said monomer individually or in combination of 2 or more types.

In formula (12), n2 is 1-10, preferably 1 or 2.

(Structural unit (III-3) derived from other monomer (iii-3))
Structural units (III-3) derived from the other monomer (iii-3) are, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n- Butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, phenyl (meth)acrylate acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, butoxyethylene glycol (meth)acrylate, 2-ethylhexylethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate, phenoxyethyl (meth)acrylate, vinyl Phenoxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tricyclodecyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclodecyloxyethyl (meth)acrylate, nonylphenoxyethylene glycol ( (Meth)acrylates, nonylphenoxypropylene glycol, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate and other (meth)acrylates, (meth)acryloylmorpholine (morpholino (meth)acrylate), (meth)acrylamide , N-methyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-butyl (meth)acrylamide, N-isobutyl (meth)acrylamide, Nt-butyl (meth)acrylamide, Nt-octyl (meth) ) acrylamide, diacetone (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-cyclohexyl (meth)acrylamide, N-phenyl (meth)acrylamide, N-benzyl (meth) (Meth)acrylic acid amides such as acrylamide, N-triphenylmethyl (meth)acrylamide, N,N-dimethyl(meth)acrylamide, aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene, butadiene, isoprene ethylene or substituted ethylene compounds such as butadiene or substituted butadiene compounds such as ethylene, propylene, vinyl chloride and acrylonitrile; and structural units derived from monomers (iii-3) such as vinyl esters such as vinyl acetate. These monomers may be used alone or in combination of two or more.

The content of the structural unit (III) is preferably 85 parts by weight or less, more preferably 70 parts by weight or less, and still more preferably 5 parts by weight to 55 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. is.

B-5. Polymerization of Alkali-Soluble Resin As described above, the alkali-soluble resin polymerizes the monomer composition containing the monomer to form the polymer X, and furthermore, the acid group possessed by the polymer X (the acid derived from the monomer (i) group) can be obtained by adding the compound (a) having an acrylate group to the polymer X using a part of the group) as a reaction point. Examples of the polymerization method include a solution polymerization method.

The monomer composition may contain any suitable solvent. Examples of solvents include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and propylene glycol monomethyl ether; ketones such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl. esters such as acetate; alcohols such as methanol and ethanol; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; chloroform; These solvents may be used alone or in combination of two or more. The polymerization concentration when polymerizing the monomer composition is preferably 5% to 90% by weight, more preferably 5% to 50% by weight, and still more preferably 10% to 50% by weight. .

The monomer composition may contain any suitable polymerization initiator. Examples of polymerization initiators include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, t-amylperoxy-2. -organic peroxides such as ethylhexanoate and t-butylperoxy-2-ethylhexanoate; 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexanecarbonitrile), azo compounds such as 2,2'-azobis(2,4-dimethylvaleronitrile) and dimethyl 2,2'-azobis(2-methylpropionate); The content of the polymerization initiator is preferably 0.1 to 15 parts by weight, more preferably 0.2 to 10 parts by weight, based on 100 parts by weight of all the monomers in the monomer composition.

The monomer composition may contain any suitable chain transfer agent. Examples of chain transfer agents include monofunctional thiol compounds such as n-dodecylmercaptan and β-mercaptopropionic acid; bifunctional thiol compounds such as mercapto-modified polysiloxane at both ends; side chain polyfunctional mercapto whose side chains are mercapto-modified. modified polysiloxane and the like. The content of the chain transfer agent is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of all the monomers in the monomer composition.

After polymerizing the monomer composition, the compound (a) having an acrylate group is added to the obtained polymer X. Any appropriate method can be adopted as a method for adding the compound (a) having an acrylate group. For example, in the presence of a polymerization inhibitor and a catalyst, a compound having an acrylate group is reacted with a portion of the acid group of the structural unit (I) having an acid group in the side chain to add the acrylate to the side chain. A structural unit (A) having a group can be formed.

Examples of polymerization inhibitors include alkylphenol compounds such as 6-tert-butyl-2,4-xylenol. Examples of catalysts include tertiary amines such as dimethylbenzylamine and triethylamine.

The polymerization temperature for polymerizing the alkali-soluble resin by a solution polymerization method is preferably 40°C to 150°C, more preferably 60°C to 130°C.

The alkali-soluble resin may be a random copolymer or a block copolymer.

The weight average molecular weight of the alkali-soluble resin is preferably 3,000 to 200,000, more preferably measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) solvent. 4,000 to 100,000, more preferably 5,000 to 50,000. Within such a range, it is possible to obtain a photosensitive resin composition that ensures heat resistance and has a viscosity suitable for coating film formation.

The acid value of the alkali-soluble resin is preferably 20 mgKOH/g to 300 mgKOH/g, more preferably 25 mgKOH/g to 200 mgKOH/g, still more preferably 30 mgKOH/g to 150 mgKOH/g. Within such a range, it is possible to obtain a photosensitive resin composition that is excellent in alkali developability, produces little development residue, and is capable of forming a molded article that is excellent in adhesion.

The content of the alkali-soluble resin in the photosensitive resin composition of the present invention is preferably 1% by weight to 50% by weight, more preferably 5% by weight to 40% by weight, based on the total solid content of the composition. is.

C. Colorant In one embodiment, a pigment is used as the colorant. Any appropriate pigment can be used as the pigment. The pigment may be an organic pigment or an inorganic pigment. Examples of organic pigments include azo-based pigments, phthalocyanine-based pigments, polycyclic pigments (quinacridone-based, perylene-based, perinone-based, isoindolinone-based, isoindoline-based, dioxazine-based, thioindigo-based, anthraquinone-based, quinophthalone-based, metal complex-based, diketopyrrolopyrrole-based, etc.), dye lake-based pigments, and the like. Examples of inorganic pigments include white and extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.), chromatic pigments (yellow, cadmium-based, chromium vermilion, nickel-titanium, Chrome titanium, yellow iron oxide, red iron oxide, zinc chromate, red lead, ultramarine blue, Prussian blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.), black pigments (carbon black, bone black, graphite, iron black, titanium black) etc.), luster pigments (pearl pigments, aluminum pigments, bronze pigments, etc.), fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.), and the like. The pigment may be subjected to surface treatments such as rosin treatment, surfactant treatment, resin-based dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, and wax coating, depending on the purpose and application.

The number average primary particle size of the pigment can be any appropriate particle size depending on the type of pigment. The number average primary particle size of the pigment is preferably 100 nm or less, more preferably 50 nm or less. The lower limit of the number average primary particle size of the pigment is, for example, 10 nm. In the present invention, by including the alkali-soluble resin, the dispersibility of the pigment is improved, making it possible to use a pigment with a small particle size.

The number average secondary particle size (initial particle size) of the pigment immediately after preparing the photosensitive resin composition is preferably 200 nm or less, more preferably 150 nm or less, still more preferably 120 nm or less, and particularly preferably is 100 nm or less. The particle size can be measured using a dynamic light scattering particle size distribution analyzer.

A photosensitive resin composition was prepared, and after 7 days in an environment at 40°C, the rate of change of the number average secondary particle size of the pigment with respect to the initial particle size (particle size after 7 days/initial particle size) was , preferably 150% or less, more preferably 130% or less, still more preferably 110% or less, particularly preferably 105% or less, and most preferably less than 100%. The lower limit of the rate of change is, for example, 90%. In the present invention, the stability of pigment dispersion is excellent, and aggregation of pigment over time can be effectively suppressed.

The content of the pigment is preferably 5 parts by weight to 500 parts by weight, more preferably 8 parts by weight to 200 parts by weight, with respect to 100 parts by weight of the alkali-soluble resin in the photosensitive resin composition.

In another embodiment, a dye is used as the colorant. Examples of dyes include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

The content of the dye is preferably 20 to 500 parts by weight, more preferably 30 to 200 parts by weight, per 100 parts by weight of the alkali-soluble resin in the photosensitive resin composition.

The pigment and the dye may be used in combination. In this case, the total content of the pigment and the dye (the content of the coloring material) is preferably 20 parts per 100 parts by weight of the alkali-soluble resin in the photosensitive resin composition. It is from 40 parts by weight to 500 parts by weight, more preferably from 40 parts by weight to 200 parts by weight.

D. Polyfunctional Monomer The photosensitive resin composition of the present invention may contain a polyfunctional monomer. Examples of polyfunctional monomers include polyfunctional aromatic vinyl-based monomers such as divinylbenzene, diallyl phthalate, and diallylbenzene phosphonate; (di)ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane (Meth)acrylates, trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol Tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol di(meth)acrylate, tripentaerythritol tri(meth)acrylate , tripentaerythritol tetra(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, tris(hydroxyethyl) ) polyfunctional (meth)acrylates such as isocyanurate tri(meth)acrylate; and polyfunctional monomers obtained by modifying these monomers with caprolactone or alkylene oxide. Among these, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, Tri(meth)acrylate of tris(hydroxyethyl)isocyanurate and the like are preferred. By using these polyfunctional monomers, it is possible to obtain a molded article with a high cross-linking density due to the large number of functional groups. In the present invention, a binder polymer having an oxyalkylene group is used as described above, while the polyfunctional monomer may or may not have an oxyalkylene group. Preferably, polyfunctional monomers having no oxyalkylene groups are used.

The content of the polyfunctional monomer is preferably 5 parts by weight to 200 parts by weight, more preferably 10 parts by weight to 150 parts by weight, with respect to 100 parts by weight of the alkali-soluble resin in the photosensitive resin composition. , more preferably 30 to 120 parts by weight, and particularly preferably 35 to 100 parts by weight.

E. Photopolymerization Initiator Any appropriate photopolymerization initiator can be used as the photopolymerization initiator. A radical photopolymerization initiator is typically used. Examples of photopolymerization initiators include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether and benzoin ethyl ether; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 2-benzyl-2-dimethyl α-aminoketones such as amino-1-(4-morpholinophenyl)-butanone-1; 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}- α-hydroxyketones such as 2-methyl-propan-1-one; 1,2-octanedione, 1-[4-(phenylthio)-,2-,(O-benzoyloxime)], ethanone, 1-[ 9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime), oxime esters such as IRGACUREOXE03 and IRGACUREOXE04 (manufactured by BASF); acylphosphine oxides and xanthones. These photopolymerization initiators may be used alone or in combination of two or more.

The content of the photopolymerization initiator is preferably 5 parts by weight to 50 parts by weight, more preferably 10 parts by weight to 40 parts by weight, with respect to 100 parts by weight of the alkali-soluble resin in the photosensitive resin composition. be.

Further, in addition to the photopolymerization initiator, a photopolymerization initiation aid may be used in combination. Photopolymerization initiation aids can also be used in combination. Specific examples of photopolymerization initiation aids include 1,3,5-tris(3-mercaptopropionyloxyethyl)-isocyanurate and 1,3,5-tris(3-mercaptobutyloxyethyl)-isocyanurate (Showa Denko Co., Ltd., Karenz MT (registered trademark) NR1), trimethylolpropane tris (trifunctional thiol compounds such as 3-mercaptopropionate; pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercapto butyrate) (manufactured by Showa Denko Co., Ltd., Karenz MT (registered trademark) PE1) and other tetrafunctional thiol compounds; dipentaerythritol hexakis (3-propionate) and other hexafunctional thiol compounds.

F. Solvent The photosensitive resin composition of the present invention may contain any suitable solvent. Examples of solvents include ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy esters such as butyl acetate; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene and ethylbenzene; mentioned. The amount of solvent can be set to any appropriate amount depending on the desired viscosity of the photosensitive resin composition. For example, the solvent is preferably contained in a proportion of 50% to 90% by weight, more preferably 60% to 90% by weight, in the photosensitive resin composition.

G. Additives The photosensitive resin composition of the present invention may further contain any other suitable additives as required. Other additives include, for example, aluminum hydroxide, talc, clay, fillers such as barium sulfate, antifoaming agents, coupling agents, leveling agents, sensitizers, release agents, lubricants, plasticizers, antioxidants. agent, UV absorber, flame retardant, polymerization inhibitor, thickener, organic fine particles, inorganic fine particles (zinc oxide, silicon oxide, zirconia, titanium), porous fine particles such as silica, hollow fine particles such as silica etc. Moreover, other resins than the alkali-soluble resin containing a structural unit having an acrylate group in the side chain may be included. When other resins are included, the content of the alkali-soluble resin is preferably 30 parts by weight or more, more preferably 50 parts by weight or more, and still more preferably 65 parts by weight, with respect to 100 parts by weight of the total resin. It is at least 65 parts by weight and less than 100 parts by weight.

(dispersant)
In one embodiment, the photosensitive resin composition may contain a dispersant.

Any appropriate dispersant can be used as the dispersant as long as the effects of the present invention can be obtained. In one embodiment, an anionic dispersant, a nonionic dispersant, a cationic dispersant, a polymer (resin type) dispersant, or the like is used as the dispersant. Among them, a polymer (resin type) dispersant is preferred.

Specific examples of polymer (resin type) dispersants include polyacrylic polymers, polyether polymers, polyester polymers, polyurethane polymers, polyphosphate polymers, polyethyleneimine polymers, polyallylamine polymers, Polymers composed of amino group-containing monomers and macromonomers, polyoxyethylene alkyl ether-based polymers, polyoxyethylene diester-based polymers, polyether phosphate-based polymers, polyester phosphate-based polymers, sorbitan aliphatic ester-based polymers, Aliphatic-modified polyester-based polymers and the like are included. Polycarboxylic acid esters such as polyurethanes and polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, as polymeric (resin type) dispersants, Polysiloxane, long-chain polyaminoamide phosphate, hydrogen group-containing polycarboxylic acid ester, amide formed by reaction of poly(lower alkyleneimine) with polyester having free carboxyl group and its salt, (meth)acrylic acid -Styrene copolymer, (meth)acrylic acid-(meth)acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, polyester, modified polyacrylate, ethylene oxide/polypropylene oxide adduct etc. may be used. A block copolymer is preferably used as the copolymer.

Among the above dispersants, acrylic polymers, block copolymers, and urethane polymers are preferably used.

A commercially available product may be used as the dispersant. Specific examples of commercially available products include trade names “Disperbyk-103”, “Disperbyk-108”, “Disperbyk-109”, “Disperbyk-112”, “Disperbyk-116”, and “Disperbyk-130” manufactured by BYK Japan. ", "Disperbyk-161", "Disperbyk-162", "Disperbyk-163", "Disperbyk-164", "Disperbyk-166", "Disperbyk-167", "Disperbyk-168", "Disperbyk-170", "Disperbyk-171", "Disperbyk-182", "Disperbyk-183", "Disperbyk-185", "Disperbyk-184", "Disperbyk-2000", "Disperbyk-2001", "Disperbyk-2050", "Disperbyk" -2070", "Disperbyk-2096", "Disperbyk-2150", BYK-9077"; trade names "Ajisper PB822" and "Ajisper PN411" manufactured by Ajinomoto Co., Ltd.; trade names "Disperlon DA-375" manufactured by Kusumoto Kasei Co., Ltd. , “Disparon ED-251”; trade name “Nuspers 657NA” manufactured by Elementis; trade names manufactured by TEGO “TEG Disper650”, “TEG Disper652”, “TEG Disper662C”, “TEG Disper670”, “TEG Disper710” , “TEG Disper740W”, “TEG Disper752W” and the like.

As for the structure, resins having a graft structure in which the main chain is an anchor chain having an interaction site with the coloring material and the graft chain is a compatible chain having interaction with the dispersion medium, or a resin with an anchor chain and A resin in which the compatible chain has a block structure is particularly preferably used.

The content of the dispersant is preferably 100 parts by weight or less, more preferably 5 parts by weight to 100 parts by weight, and more preferably 5 parts by weight to 70 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. more preferably 5 to 50 parts by weight, particularly preferably 7 to 40 parts by weight.

The content of the dispersant is preferably 80 parts by weight or less, more preferably 1 part by weight to 80 parts by weight, and more preferably 1 part by weight to 50 parts by weight with respect to 100 parts by weight of the coloring material. and more preferably 1 to 30 parts by weight.

H. Molded Article Production Method The molded article production method of the present invention comprises applying the photosensitive resin composition to a resin substrate to form a coating layer, curing the coating layer, and heating the coating layer. The heating temperature during the heating is 200° C. or lower.

In one embodiment, the molded body can be formed by photolithography. Specifically, a photomask is placed on the coating layer and exposed to light to cure the coating layer, then developed, and the resulting preformed body is heated (post-baked) to obtain a molded body. can be formed. According to photolithography, a compact (for example, a color filter) can be formed with a fine pattern. By using the photosensitive resin composition of the present invention, it is possible to obtain a molded article that is excellent in adhesion to a substrate even if it is formed in a fine pattern.

As the base material, a base material composed of any appropriate resin can be used. Examples of resins constituting the base material include polyethylene, polyvinyl chloride, polyethylene terephthalate, polyvinylidene chloride, polypropylene, polyvinyl alcohol, polyester, polycarbonate, polystyrene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene-vinyl alcohol copolymer. Polymers, ethylene-methacrylic acid copolymers, polyamide resins, cellulose, silicone resins and the like can be mentioned. In one embodiment, the glass transition temperature of the resin forming the substrate is 100° C. or lower.

In one embodiment, a coloring material dispersion composition (hereinafter also referred to as a millbase) containing the alkali-soluble resin and the coloring material, and a clear resist containing the alkali-soluble resin and the polyfunctional monomer are mixed. , the above photosensitive resin composition is prepared. The millbase may further comprise a dispersing agent. Also, the clear resist may further contain a photopolymerization initiator. Also, the millbase and/or clear resist may contain any suitable solvent.

In the mill base, the content of the coloring material is preferably 15 parts by weight to 500 parts by weight, more preferably 20 parts by weight to 400 parts by weight, with respect to 100 parts by weight of the alkali-soluble resin in the mill base. It is preferably 20 to 350 parts by weight.

In the mill base, the content of the dispersant is preferably 2 parts by weight to 80 parts by weight, more preferably 5 parts by weight to 60 parts by weight, with respect to 100 parts by weight of the alkali-soluble resin in the mill base. It is preferably 10 to 50 parts by weight.

In the clear resist, the content of the polyfunctional monomer is preferably 50 parts by weight to 400 parts by weight, more preferably 100 parts by weight to 350 parts by weight, with respect to 100 parts by weight of the alkali-soluble resin in the clear resist. and more preferably 150 to 300 parts by weight.

In the clear resist, the content of the photopolymerization initiator is preferably 5 parts by weight to 200 parts by weight, more preferably 10 parts by weight to 150 parts by weight, with respect to 100 parts by weight of the alkali-soluble resin in the clear resist. and more preferably 10 to 120 parts by weight.

Examples of the method of applying the photosensitive resin composition include methods using a spin coater, bar coater, gravure coater, roll coater, knife coater, applicator, and the like. The drying temperature is preferably 40°C to 200°C, more preferably 70°C to 120°C. The drying time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes.

The photomask is arranged at any appropriate position according to the desired size of the molded body (for example, color filter). The photomask is placed on top of the coating film, and the distance between the coating film and the photomask is preferably 0 μm to 500 μm, more preferably 10 μm to 400 μm, still more preferably 20 μm to 300 μm, particularly preferably 30 μm. ~200 μm.

The UV irradiation intensity (converted to illuminance at 365 nm) during the exposure is preferably 10 mJ/cm ² to 200 mJ/cm ² , more preferably 20 mJ/cm ² to 150 mJ/cm ² , still more preferably 30 mJ/cm ² . ˜100 mJ/cm ² .

At the time of the development, it is preferable to use an alkaline aqueous solution. This is because high-sensitivity development can be carried out with little burden on the environment. As the alkali component, for example, potassium hydroxide, sodium hydroxide, sodium carbonate and the like are used. The alkali concentration of the alkaline aqueous solution is preferably 0.01 wt% to 5 wt%, more preferably 0.02 wt% to 3 wt%, still more preferably 0.03 wt% to 1 wt%. . If it is such a range, the said photosensitive resin composition can be melt|dissolved appropriately and a molded object can be formed with good developability. A surfactant may be further added to the alkaline aqueous solution.

The heating temperature during post-baking is preferably 90°C to 200°C, more preferably 100°C to 180°C, still more preferably 100°C to 150°C. The heating time is preferably 10 to 90 minutes, more preferably 20 to 60 minutes. A tapered molded body can be obtained by using the photosensitive resin composition and subjecting it to a post-baking step.

In one embodiment, a color filter can be obtained by the manufacturing method described above.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited by these examples. The method for measuring each characteristic value in Production Examples and Examples is as follows.

(1) Weight average molecular weight: Mw
Measurement was performed by GPC (HLC-8220GPC, manufactured by Tosoh Corporation) using THF as an eluent, using TSKgel SuperHZM-N (manufactured by Tosoh Corporation) as a column, and calculated in terms of standard polystyrene.
(2) Solid Content About 0.3 g of the copolymer solution prepared in Production Example was weighed into an aluminum cup, and about 1 g of acetone was added to dissolve the solution, followed by natural drying at room temperature. Then, using a hot air dryer (trade name: PHH-101, manufactured by ESPEC Co., Ltd.), it was dried at 140° C. for 3 hours, allowed to cool in a desiccator, and weighed. The weight of the solid content (resin) in the polymer solution was calculated from the amount of weight loss.
(3) Acid value 1.5 g of the copolymer solution prepared in Production Example was precisely weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and titrated with a 0.1N KOH aqueous solution. Titration was performed using an automatic titrator (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value per 1 g of polymer was obtained from the solid content concentration (mgKOH/g).
(4) Double bond equivalent Calculated by the following formula.
Double bond equivalent (g/eq) = total monomer amount (g) used in alkali-soluble resin (polymer after addition of compound having acrylate group)/mol of added compound having acrylate group

[Production Example 1]
A separable flask equipped with a cooling tube was prepared as a reactor. On the other hand, in the monomer dropping tank, 15 g of (α-allyloxymethyl) methyl acrylate (AOMA), 31 g of methacrylic acid (MAA), 54 g of benzyl methacrylate (BzMA), t-butylperoxy-2- 2 g of ethyl hexanoate (trade name “Perbutyl (registered trademark) O”, manufactured by NOF Corporation, hereinafter also referred to as PBO) was added and mixed with stirring. In addition, 2.0 g of dodecyl mercaptan (nDM) and 30 g of propylene glycol methyl ether acetate (PGMEA) as a chain transfer agent solution were put into a chain transfer agent dropping tank and stirred and mixed.
A reaction vessel was charged with 100 g of PGMEA and 55.7 g of propylene glycol monomethyl ether (PGME), purged with nitrogen, and heated with an oil bath while stirring to raise the temperature of the reaction vessel to 90°C. After the temperature of the reactor was stabilized at 90° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90°C. Thirty minutes after the dropping was completed, 0.5 g of PBO was added. After an additional 30 minutes, the reactor was heated to 115°C. After maintaining the temperature at 115° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and oxygen/nitrogen=7/93 (v/v) mixed gas bubbling was started. Next, 30 g of glycidyl acrylate (GA), 0.3 g of 6-tert-butyl-2,4-xylenol (trade name “Topanol”, manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization inhibitor, and dimethylbenzyl as a catalyst were added to the reactor. 0.5 g of amine (DMBA) was charged and reacted at 110° C. for 1 hour and at 115° C. for 7 hours. Thereafter, the mixture was cooled to room temperature to obtain a copolymer solution (A-1) containing 40.1% by weight of an alkali-soluble resin. The weight average molecular weight (Mw) of the alkali-soluble resin was 13000, the acid value was 78 mgKOH/g, and the double bond equivalent was 560 g/eq. Production conditions, solid content concentration, weight average molecular weight (Mw), acid value and double bond equivalent of the copolymer solution are shown in Table 1 together with Production Examples 2-10.

[Production Example 2]
A separable flask equipped with a cooling tube was prepared as a reactor. On the other hand, 15 g of AOMA, 31 g of MAA, 54 g of BzMA, and 2 g of PBO were put into the monomer dropping tank as a monomer composition, and mixed with stirring. In addition, 2.0 g of nDM and 30 g of PGMEA were added as a chain transfer agent solution into a chain transfer agent dropping tank, and stirred and mixed.
A reactor was charged with 100 g of PGMEA and 55.7 g of PGME, and after purging with nitrogen, the temperature of the reactor was raised to 90° C. by heating with an oil bath while stirring. After the temperature of the reactor was stabilized at 90° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90°C. Thirty minutes after the dropping was completed, 0.5 g of PBO was added. After an additional 30 minutes, the reactor was heated to 115°C. After maintaining the temperature at 115° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and oxygen/nitrogen=7/93 (v/v) mixed gas bubbling was started. Then, 47 g of 4-hydroxybutyl acrylate glycidyl ether (4HBAGE), 0.3 g of topanol, and 0.5 g of DMBA were charged into the reactor and reacted at 110° C. for 1 hour and at 115° C. for 7 hours. Thereafter, the mixture was cooled to room temperature to obtain a copolymer solution (A-2) containing 41.7% by weight of an alkali-soluble resin. The weight average molecular weight (Mw) of the alkali-soluble resin was 13300, the acid value was 64 mgKOH/g, and the double bond equivalent was 630 g/eq. Table 1 shows the production conditions, solid content concentration, weight average molecular weight (Mw), acid value and double bond equivalent of the copolymer solution.

[Production Example 3]
A separable flask equipped with a cooling tube was prepared as a reactor. On the other hand, 15 g of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate (MD), 31 g of MAA, 54 g of BzMA, and 2 g of PBO were charged into the monomer dropping tank as a monomer composition and mixed with stirring. In addition, 2.0 g of nDM and 30 g of PGMEA were added as a chain transfer agent solution into a chain transfer agent dropping tank, and stirred and mixed.
A reactor was charged with 100 g of PGMEA and 55.7 g of PGME, and after purging with nitrogen, the temperature of the reactor was raised to 90° C. by heating with an oil bath while stirring. After the temperature of the reactor was stabilized at 90° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90°C. Thirty minutes after the dropping was completed, 0.5 g of PBO was added. After an additional 30 minutes, the reactor was heated to 115°C. After maintaining the temperature at 115° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and oxygen/nitrogen=7/93 (v/v) mixed gas bubbling was started. Then, 30 g of GA, 0.3 g of topanol, and 0.5 g of DMBA were charged into the reactor and reacted at 110° C. for 1 hour and at 115° C. for 7 hours. Thereafter, the mixture was cooled to room temperature to obtain a copolymer solution (A-3) containing 39.8% by weight of an alkali-soluble resin. The weight average molecular weight (Mw) of the alkali-soluble resin was 12800, the acid value was 79 mgKOH/g, and the double bond equivalent was 560 g/eq. Table 1 shows the production conditions, solid content concentration, weight average molecular weight (Mw), acid value and double bond equivalent of the copolymer solution.

[Production Example 4]
A separable flask equipped with a cooling tube was prepared as a reactor. On the other hand, 15 g of benzylmaleimide (BzMI), 31 g of MAA, 54 g of BzMA, 2 g of PBO, 14 g of PGMEA, and 5.7 g of PGME were added as a monomer composition into the monomer dropping tank and mixed with stirring. In addition, 2.0 g of nDM and 30 g of PGMEA were added as a chain transfer agent solution into a chain transfer agent dropping tank, and stirred and mixed.
A reactor was charged with 86 g of PGMEA and 50 g of PGME, purged with nitrogen, and heated in an oil bath while stirring to raise the temperature of the reactor to 90°C. After the temperature of the reactor was stabilized at 90° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90°C. Thirty minutes after the dropping was completed, 0.5 g of PBO was added. After an additional 30 minutes, the reactor was heated to 115°C. After maintaining the temperature at 115° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and oxygen/nitrogen=7/93 (v/v) mixed gas bubbling was started. Then, 30 g of GA, 0.3 g of topanol, and 0.5 g of DMBA were charged into the reactor and reacted at 110° C. for 1 hour and at 115° C. for 7 hours. Thereafter, the mixture was cooled to room temperature to obtain a copolymer solution (A-4) containing 40.2% by weight of an alkali-soluble resin. The weight average molecular weight (Mw) of the alkali-soluble resin was 12700, the acid value was 77 mgKOH/g, and the double bond equivalent was 560 g/eq. Table 1 shows the production conditions, solid content concentration, weight average molecular weight (Mw), acid value and double bond equivalent of the copolymer solution.

[Production Example 5]
A separable flask equipped with a cooling tube was prepared as a reactor. On the other hand, 15 g of AOMA, 32 g of MAA, 53 g of BzMA, and 2 g of PBO were put into the monomer dropping tank as a monomer composition, and mixed with stirring. In addition, 2.0 g of nDM and 30 g of PGMEA were added as a chain transfer agent solution into a chain transfer agent dropping tank, and stirred and mixed.
A reactor was charged with 100 g of PGMEA and 55.7 g of PGME, and after purging with nitrogen, the temperature of the reactor was raised to 90° C. by heating with an oil bath while stirring. After the temperature of the reactor was stabilized at 90° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90°C. Thirty minutes after the dropping was completed, 0.5 g of PBO was added. After an additional 30 minutes, the reactor was heated to 115°C. After maintaining the temperature at 115° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and oxygen/nitrogen=7/93 (v/v) mixed gas bubbling was started. Then, 15 g of GA, 0.3 g of topanol, and 0.5 g of DMBA were charged into the reactor and reacted at 110° C. for 1 hour and at 115° C. for 7 hours. Thereafter, the mixture was cooled to room temperature to obtain a copolymer solution (A-5) containing 37.5% by weight of an alkali-soluble resin. The weight average molecular weight (Mw) of the alkali-soluble resin was 10400, the acid value was 130 mgKOH/g, and the double bond equivalent was 985 g/eq. Table 1 shows the production conditions, solid content concentration, weight average molecular weight (Mw), acid value and double bond equivalent of the copolymer solution.

[Production Example 6]
A separable flask equipped with a cooling tube was prepared as a reactor. On the other hand, 15 g of AOMA, 48 g of MAA, 37 g of BzMA, and 2 g of PBO were put into the monomer dropping tank as a monomer composition and mixed with stirring. In addition, 2.0 g of nDM and 30 g of PGMEA were added as a chain transfer agent solution into a chain transfer agent dropping tank, and stirred and mixed.
A reactor was charged with 100 g of PGMEA and 55.7 g of PGME, and after purging with nitrogen, the temperature of the reactor was raised to 90° C. by heating with an oil bath while stirring. After the temperature of the reactor was stabilized at 90° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90°C. Thirty minutes after the dropping was completed, 0.5 g of PBO was added. After an additional 30 minutes, the reactor was heated to 115°C. After maintaining the temperature at 115° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and oxygen/nitrogen=7/93 (v/v) mixed gas bubbling was started. Then, 60 g of GA, 0.3 g of topanol, 0.5 g of DMBA, 31 g of PGMEA, and 13 g of PGME were charged into the reactor and reacted at 110° C. for 1 hour and at 115° C. for 7 hours. Thereafter, the mixture was cooled to room temperature to obtain a copolymer solution (A-6) containing 40.3% by weight of an alkali-soluble resin. The weight average molecular weight (Mw) of the alkali-soluble resin was 17000, the acid value was 40 mgKOH/g, and the double bond equivalent was 340 g/eq. Table 1 shows the production conditions, solid content concentration, weight average molecular weight (Mw), acid value and double bond equivalent of the copolymer solution.

[Production Example 7]
A separable flask equipped with a cooling tube was prepared as a reactor. On the other hand, 31 g of MAA, 69 g of BzMA, and 2 g of PBO were put into the monomer dropping tank as a monomer composition, and stirred and mixed. In addition, 2.0 g of nDM and 30 g of PGMEA were added as a chain transfer agent solution into a chain transfer agent dropping tank, and stirred and mixed.
A reactor was charged with 100 g of PGMEA and 55.7 g of PGME, and after purging with nitrogen, the temperature of the reactor was raised to 90° C. by heating with an oil bath while stirring. After the temperature of the reactor was stabilized at 90° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90°C. Thirty minutes after the dropping was completed, 0.5 g of PBO was added. After an additional 30 minutes, the reactor was heated to 115°C. After maintaining the temperature at 115° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and oxygen/nitrogen=7/93 (v/v) mixed gas bubbling was started. Then, 33 g of glycidyl methacrylate (GMA), 0.3 g of topanol, and 0.5 g of DMBA were charged into the reactor and reacted at 110° C. for 1 hour and at 115° C. for 7 hours. Thereafter, the mixture was cooled to room temperature to obtain a copolymer solution (A-7) containing 40.0% by weight of an alkali-soluble resin. The weight average molecular weight (Mw) of the alkali-soluble resin was 12500, the acid value was 75 mgKOH/g, and the double bond equivalent was 575 g/eq. Table 1 shows the production conditions, solid content concentration, weight average molecular weight (Mw), acid value and double bond equivalent of the copolymer solution.

[Production Example 8]
A separable flask equipped with a cooling tube was prepared as a reactor. On the other hand, 11 g of MAA, 89 g of BzMA, and 2 g of PBO were put into the monomer dropping tank as a monomer composition and mixed with stirring. Further, 1.3 g of nDM and 30 g of PGMEA were added as a chain transfer agent solution into a chain transfer agent dropping tank, and mixed with stirring.
A reactor was charged with 100 g of PGMEA and 55.7 g of PGME, and after purging with nitrogen, the temperature of the reactor was raised to 90° C. by heating with an oil bath while stirring. After the temperature of the reactor was stabilized at 90° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90°C. Thirty minutes after the dropping was completed, 0.5 g of PBO was added. After an additional 30 minutes, the reactor was heated to 115°C. After maintaining the temperature at 115° C. for 1.5 hours, it was cooled to room temperature to obtain a copolymer solution (A-8) containing 35.1% by weight of an alkali-soluble resin. The weight average molecular weight (Mw) of the alkali-soluble resin was 12000, and the acid value was 76 mgKOH/g. Table 1 shows the production conditions, solid content concentration, weight average molecular weight (Mw) and acid value of the copolymer solution.

[Production Example 9]
A separable flask equipped with a cooling tube was prepared as a reactor. On the other hand, 31 g of MAA, 69 g of BzMA, and 2 g of PBO were put into the monomer dropping tank as a monomer composition, and stirred and mixed. In addition, 2.0 g of nDM and 30 g of PGMEA were added as a chain transfer agent solution into a chain transfer agent dropping tank, and stirred and mixed.
A reactor was charged with 100 g of PGMEA and 55.7 g of PGME, and after purging with nitrogen, the temperature of the reactor was raised to 90° C. by heating with an oil bath while stirring. After the temperature of the reactor was stabilized at 90° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90°C. Thirty minutes after the dropping was completed, 0.5 g of PBO was added. After an additional 30 minutes, the reactor was heated to 115°C. After maintaining the temperature at 115° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and oxygen/nitrogen=7/93 (v/v) mixed gas bubbling was started. Then, 47 g of 4HBAGE, 0.3 g of topanol, and 0.5 g of DMBA were charged into the reactor and reacted at 110° C. for 1 hour and at 115° C. for 7 hours. Thereafter, the mixture was cooled to room temperature to obtain a copolymer solution (A-9) containing 41.5% by weight of an alkali-soluble resin. The weight average molecular weight (Mw) of the alkali-soluble resin was 13500, the acid value was 64 mgKOH/g, and the double bond equivalent was 630 g/eq. Table 1 shows the production conditions, solid content concentration, weight average molecular weight (Mw), acid value and double bond equivalent of the copolymer solution.

[Production Example 10]
A separable flask equipped with a cooling tube was prepared as a reactor. On the other hand, 15 g of methylmaleimide (MMI), 31 g of MAA, 54 g of BzMA, and 2 g of PBO were charged as a monomer composition into a monomer dropping tank and mixed with stirring. In addition, 2.0 g of nDM and 30 g of PGMEA were added as a chain transfer agent solution into a chain transfer agent dropping tank, and stirred and mixed.
A reactor was charged with 100 g of PGMEA and 55.7 g of PGME, and after purging with nitrogen, the temperature of the reactor was raised to 90° C. by heating with an oil bath while stirring. After the temperature of the reactor was stabilized at 90° C., the monomer composition and the chain transfer agent solution were added dropwise. The monomer composition and the chain transfer agent solution were added dropwise over 180 minutes while maintaining the temperature at 90°C. Thirty minutes after the dropping was completed, 0.5 g of PBO was added. After an additional 30 minutes, the reactor was heated to 115°C. After maintaining the temperature at 115° C. for 1.5 hours, a gas introduction tube was attached to the separable flask, and oxygen/nitrogen=7/93 (v/v) mixed gas bubbling was started. Then, 33 g of GMA, 0.3 g of topanol, and 0.5 g of DMBA were charged into the reactor and reacted at 110° C. for 1 hour and at 115° C. for 7 hours. Thereafter, the mixture was cooled to room temperature to obtain a copolymer solution (A-10) containing 40.2% by weight of an alkali-soluble resin. The weight average molecular weight (Mw) of the alkali-soluble resin was 12700, the acid value was 74 mgKOH/g, and the double bond equivalent was 575 g/eq. Table 1 shows the production conditions, solid content concentration, weight average molecular weight (Mw), acid value and double bond equivalent of the copolymer solution.

[Example 1]
8.73 g of the above copolymer solution (A-1) as an alkali-soluble resin (that is, 3.5 g of resin), DISPERBYK-2001 as a dispersant (manufactured by BYK-Chemie Japan, hereinafter referred to as byk2001) 2.83 g (non-volatile 1.3 g), pigment C.I. I. Pigment Violet 23 (manufactured by Clariant, hereinafter referred to as PV23) 1.6 g, and the dye C.I. I. 6.4 g of Solvent Blue 35 (manufactured by MP Biomedicals, hereinafter referred to as SB35) was weighed into a 225 ml mayonnaise bottle and diluted with PGMEA so that the non-volatile content concentration was 20% by weight. 64 g of zirconia beads with a diameter of 1.0 mm were added to this, and the lid was closed. This was shaken with a paint shaker for 3 hours to obtain a pigment dispersion composition (millbase).
To this pigment dispersion composition were added 12.8 g of DPHA as a polyfunctional monomer, 37.2 g of the above copolymer solution (A-1) as a binder resin (that is, 14.9 g of resin), and ethanone, 1-[, as a photopolymerization initiator. 9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) (trade name “IRGACURE (registered trademark) OXE02” manufactured by BASF Japan, hereinafter OXE02 ) was added and diluted with PGMEA so that the concentration of non-volatile matter was 20% by weight. After removing the zirconia beads, the mixture was filtered through a filter with a pore size of 1.0 μm to prepare a photosensitive resin composition B1.

[Examples 2 to 6, Comparative Examples 1 to 4]
Photosensitive resin compositions B2 to B10 were obtained in the same manner as in Example 1, except that the resins shown in Table 2 were used as the alkali-soluble resin (copolymer solution) contained in the pigment dispersion composition and the clear resist. .

<Evaluation>
The photosensitive resin compositions B1 to B9 were applied onto a 10 cm square glass substrate using a spin coater and dried in an oven at 90° C. for 3 minutes. After drying, a UV aligner (trade name “TME-150RNS”, manufactured by TOPCON Co., Ltd.) equipped with a 2.0 kW ultra-high pressure mercury lamp with a photomask having a dot pattern of 2 to 20 μmφ placed at a distance of 100 μm from the coating film. was irradiated with ultraviolet rays at an intensity of 60 mJ/cm ² (converted to illuminance at 365 nm). After the ultraviolet irradiation, a 0.05% potassium hydroxide aqueous solution was sprayed on the coating film using a spin developing machine to dissolve and remove the unexposed areas, and the remaining exposed areas were developed by washing with pure water for 10 seconds. to form a dot pattern. By this operation, the following evaluations (a) to (c) were performed on the photosensitive resin compositions B1 to B9. Table 2 shows the results.
Furthermore, the dot pattern was heated at 100° C. to obtain a molded body, and the cross-sectional shape of the molded body was observed. Table 2 shows the results.
Also, a dot pattern was formed by the above method, the dot pattern was heated at 150° C. to obtain a molded body, and the cross-sectional shape of the molded body was observed. Table 2 shows the results.
(a) Break time (BT)
BT was defined as the shortest time in which a pattern could be formed during development, and the development speed was evaluated by the BT.
(b) Adhesion Adhesion was evaluated from the minimum mask diameter that can adhere to the substrate with a developing time of BT + 10 seconds. Table 2 lists the minimum mask system.
(c) Cross-Sectional Shape The dot pattern and the shape of the compact were observed using an FE-SEM (trade name “JSM-7600FA”, manufactured by JEOL Ltd.).

(d) Solvent resistance (MNP resistance evaluation by heating at 100 ° C.)
The photosensitive resin compositions B1 to B9 were applied onto a 5 cm square glass substrate using a spin coater and dried in an oven at 100° C. for 5 minutes. After drying, ultraviolet rays were irradiated with an intensity of 60 mJ/cm ² (365 nm illumination conversion) from a high-pressure mercury lamp. After that, heat treatment was performed at 100° C. for 40 minutes to obtain a coating film having a thickness of 5 μm.
Thereafter, the coating film is immersed in 20 g of N-methyl-2-pyrrolidone (NMP) at 40° C. for 10 minutes, and the hue of NMP eluted from the coating film is measured with a spectrophotometer UV3100 (manufactured by Shimadzu Corporation) at 595 nm. was determined.
By measuring the absorbance of the NMP immersion solution after the test in this manner, the amount of pigment component exuding from the coating film was evaluated. Table 2 shows the results. Incidentally, the smaller the absorbance, the less the pigment component oozes out, that is, the molded article (coating film) formed from the photosensitive resin composition has excellent solvent resistance.

(e) Solvent resistance (MNP resistance evaluation by heating at 150 ° C.)
A coating film was obtained in the same manner as in (d) above, except that the heat treatment after the ultraviolet irradiation was performed at 150°C. The coating film was subjected to the same evaluation as in (d) above. Table 2 shows the results.

(f) Pigment Particle Size The particle size (median size) of the pigment contained in the photosensitive resin composition was measured using a dynamic light scattering type particle size distribution analyzer (LB-500, manufactured by Horiba, Ltd.).
The pigment particle size immediately after dispersion (immediately after preparing the photosensitive resin composition) and the pigment particle size after storing the photosensitive resin composition at 40° C. for 7 days were compared. Table 2 shows the results.
The rate of change in Table 2 was calculated by the following formula.
Rate of change = Measured value after storage at 40°C for 7 days/Measured value immediately after dispersion

As is clear from Table 2, when the photosensitive resin composition of the present invention is used, a tapered molded body can be obtained by heat treatment (post-baking) after UV irradiation. Moreover, the photosensitive resin composition of the present invention can obtain the effect of heat treatment (post-baking) at a low temperature and can form a molded article having excellent solvent resistance.

Claims (11)

containing an alkali-soluble resin, a coloring material, a polyfunctional monomer, a photopolymerization initiator, and a solvent;
The alkali-soluble resin comprises a structural unit having an acrylate group in the side chain, a structural unit having an acid group in the side chain, and a structural unit having a ring structure in the main chain,
The structural unit having a ring structure in the main chain is at least one selected from structural units represented by general formulas (4) to (7),

A photosensitive resin composition. 2. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin has a double bond equivalent weight of 200 g/eq to 1000 g/eq. 3. The photosensitive resin composition according to claim 1, wherein the content of the structural unit having an acid group in the side chain is 10 parts by weight to 70 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. The photosensitive resin according to any one of claims 1 to 3, wherein the content of the structural unit having a ring structure in the main chain is 5 parts by weight to 50 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. Composition. Containing a structural unit having an acrylate group in the side chain, a structural unit having an acid group in the side chain, and a structural unit having a ring structure in the main chain,
The structural unit having a ring structure in the main chain is at least one selected from structural units represented by general formulas (4) to (7),

Alkali-soluble resin. 6. The alkali-soluble resin according to claim 5, having a double bond equivalent of 200 g/eq to 1000 g/eq. 7. The alkali-soluble resin according to claim 5, wherein the content of the structural unit having an acid group in the side chain is 10 parts by weight to 70 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. The alkali-soluble resin according to any one of claims 5 to 7, wherein the content of the structural unit having a ring structure in the main chain is 5 parts by weight to 50 parts by weight with respect to 100 parts by weight of the alkali-soluble resin. . Forming a coating layer by applying the photosensitive resin composition according to any one of claims 1 to 4 to a resin substrate, and
Curing the coating layer and heating at 200 ° C. or less,
A method for producing a molded article. 5. The photosensitive resin composition according to any one of claims 1 to 4, wherein the alkali-soluble resin has a structural unit having two or more oxyalkylene groups in its side chain. 11. The photosensitive resin composition according to any one of claims 1 to 4, wherein the alkali-soluble resin has a structural unit (A) having a biphenyl group in its side chain.

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