Copolymer and photosensitive resin composition

Abstract

To provide a copolymer that contributes to the improvement of developability and gives a cured resin film with excellent solvent resistance.SOLUTION: The copolymer comprises a structural unit (a) having an acid group, a structural unit (b) having a group represented by the following formula (1-1) (wherein R1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R2 and R3 are each, independently, a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a linking site with a residue obtained by removing the groups of formula (1-1) from the structural unit (b)), and a structural unit (c) having a conjugated diene site in a side chain.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a copolymer, a photosensitive resin composition, a photosensitive colored composition, a cured resin film, and an image display element. [Background technology]

[0002] In recent years, from the viewpoint of resource and energy saving, photosensitive resin compositions that can be cured by active energy rays such as ultraviolet rays and electron beams have been widely used in the fields of various coatings, printing, paints, adhesives, etc. In the field of electronic materials such as printed wiring boards, photosensitive resin compositions that can be cured by active energy rays are also used for solder resists and resists for color filters, etc. The properties required for curable photosensitive resin compositions are becoming more and more diverse and sophisticated, and among them, short-time curing properties that take productivity into consideration and low-temperature curing properties that suppress thermal damage to members to which they are applied are required.

[0003] A color filter generally comprises a transparent substrate such as a glass substrate, red (R), green (G) and blue (B) pixels formed on the transparent substrate, a black matrix formed at the boundary between the pixels, and a protective film formed on the pixels and the black matrix. A color filter having such a configuration is usually manufactured by sequentially forming a black matrix, pixels and a protective film on a transparent substrate. Various methods have been proposed for forming pixels and black matrices (hereinafter, the pixels and black matrices are referred to as "colored patterns"). Among them, the pigment / dye dispersion method, which uses a photosensitive resin composition as a resist and produces a colored pattern by a photolithography process that repeats coating, exposure, development and baking, is currently mainstream because it provides a colored pattern with excellent durability and few defects such as pinholes.

[0004] In general, photosensitive resin compositions used in photolithography contain an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a colorant, and a solvent. Although the pigment / dye dispersion method has the above advantages, it often has a problem that the photosensitive resin composition is required to have high heat resistance because baking is repeated to form a black matrix, and R, G, and B patterns, and the types of colorants that can be used are limited to colorants that can withstand high baking temperatures.

[0005] In recent years, photosensitive resin compositions have been proposed that have low-temperature curing properties that are also suitable for use with components with low heat resistance, such as organic electroluminescence (EL) devices. For example, Patent Document 1 discloses a colored composition having a specific partial structure and a hydroxyl group as a photosensitive resin composition that can give a cured product with excellent solvent resistance even under low-temperature curing conditions and can be suitably used for applications such as color filters. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent Publication No. 2021-102759 Summary of the Invention [Problem to be solved by the invention]

[0007] However, in recent years, there is a demand for even lower temperature curing properties, and as a result, there is a concern that the film will not be cured sufficiently, resulting in a trade-off in terms of reduced solvent resistance. Therefore, even when cured at low temperature conditions, the cured product is required to have high solvent resistance. In addition, the photosensitive resin composition is also required to have excellent developability.

[0008] The present disclosure provides a copolymer that contributes to improved developability and provides a cured resin film having excellent solvent resistance, and a photosensitive resin composition and a photosensitive coloring composition using the copolymer. The present disclosure further provides a cured resin film having excellent solvent resistance, and an image display element having the same. [Means for solving the problem]

[0009] The present disclosure includes the following aspects. [1] A structural unit (a) having an acid group; A structural unit (b) having a group represented by the following formula (1-1) or the following formula (1-2), A structural unit (c) having a conjugated diene moiety in a side chain; having Optionally, A structural unit (pb) having a group represented by the following formula (1): A copolymer having the formula: [ka] (In formula (1-1), R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a linking site with the residue obtained by removing the group of formula (1-1) from the structural unit (b). [ka] (In formula (1-2), R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R 4 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a linking site with the residue obtained by removing the group of formula (1-2) from the structural unit (b). [ka] (In formula (1), R 1 and R 4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a linking site with a residue obtained by removing the group of formula (1) from the structural unit (pb). [2] the structural unit (c) having a conjugated diene moiety in a side chain is a structural unit derived from a conjugated diene-containing monomer (mc), The copolymer according to [1], wherein the conjugated diene moiety is a furan ring. [3] The copolymer according to [2], wherein the conjugated diene-containing monomer (mc) is a furan ring-containing (meth)acrylate. [4] R in the structural unit (b) 1 and R 4 are each independently a hydrocarbon group having 1 to 3 carbon atoms; R 2 and R 3 and each independently represent a hydrogen atom or a methyl group. [5] The copolymer according to any one of [1] to [4], further comprising a structural unit (d) derived from an alkyl (meth)acrylate in which the alkyl group has 1 to 12 carbon atoms. [6] The copolymer according to any one of [1] to [5], having an acid value of 10 to 300 KOHmg / g. [7] The weight average molecular weight is 1,000 to 50,000, The copolymer according to any one of [1] to [6], having an ethylenically unsaturated group equivalent of 300 to 10,000 g / mol. [8] The content of the structural unit (a) is 5 to 50 mol % based on all structural units of the copolymer, the total content of the structural units (b) and (pb) is 5 to 50 mol % based on the total structural units of the copolymer; The copolymer according to any one of [1] to [7], wherein the content of the structural unit (c) is 5 to 50 mol % in all structural units of the copolymer. [9] Further having a structural unit (d) derived from an alkyl (meth)acrylate in which the alkyl group has 1 to 12 carbon atoms, The copolymer according to any one of [1] to [8], wherein the content of the structural unit (d) is 1 to 50 mol % based on all structural units of the copolymer.

[10] The copolymer according to any one of [1] to [9], wherein a content ratio (molar ratio) of the structural unit (b) to the structural unit (c) is 10:90 to 90:10.

[11] A copolymer (A) according to any one of [1] to [9], A reactive diluent (B); A photopolymerization initiator (C); A solvent (D); Optionally, a resin precursor (PA), A photosensitive resin composition comprising: The resin precursor (PA) A structural unit (a) having an acid group; A structural unit (pb) having a group represented by the following formula (1), A structural unit (c) having a conjugated diene moiety in a side chain; A photosensitive resin composition which is a copolymer containing the following: [ka] (In formula (1), R 1 and R 4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a linking site with a residue obtained by removing the group of formula (1) from the structural unit (pb).

[12] the content of the structural unit (b) is 0.1 to 45 mol % based on all structural units of the copolymer (A) and the resin precursor (PA); the content of the structural unit (pb) is 0 to 49 mol % in all structural units of the copolymer (A) and the resin precursor (PA), The photosensitive resin composition according to

[11] , wherein the total content of the structural unit (b) and the structural unit (pb) is 5 to 50 mol % of all structural units of the copolymer (A) and the resin precursor (PA).

[13] With respect to 100 parts by mass in total of the copolymer (A), the resin precursor (PA), and the reactive diluent (B), The copolymer (A) and the resin precursor (PA) are contained in a total of 10 parts by mass to 90 parts by mass, The reactive diluent (B) is contained in an amount of 10 parts by mass to 90 parts by mass, The photopolymerization initiator (C) is contained in an amount of 0.1 to 30 parts by mass, The photosensitive resin composition according to

[11] or

[12] , comprising 30 parts by mass to 1,000 parts by mass of the solvent (D).

[14] A photosensitive coloring composition comprising the photosensitive resin composition according to any one of

[11] to

[13] and a coloring agent (E).

[15] With respect to 100 parts by mass in total of the copolymer (A), the resin precursor (PA), and the reactive diluent (B), The copolymer (A) and the resin precursor (PA) are contained in a total of 10 parts by mass to 90 parts by mass, The reactive diluent (B) is contained in an amount of 10 parts by mass to 90 parts by mass, The photopolymerization initiator (C) is contained in an amount of 0.1 to 30 parts by mass, The solvent (D) is contained in an amount of 30 parts by mass to 1,000 parts by mass, The colorant (E) is contained in an amount of 3 parts by mass to 80 parts by mass. The photosensitive coloring composition according to

[14] .

[16] A cured resin film comprising a cured product of the photosensitive resin composition according to any one of

[11] to

[13] .

[17] A resin cured film comprising a cured product of the photosensitive coloring composition according to

[14] or

[15] .

[18] A color filter having a color pattern made of a cured product of the photosensitive coloring composition according to

[14] or

[15] .

[19]

[18] An image display element comprising the color filter according to

[18] .

[20] The method includes a step of converting a resin precursor (PA) into a copolymer (A) in the presence of a basic catalyst and a solvent (PD), The resin precursor (PA) A structural unit (a) having an acid group; A structural unit (pb) having a group represented by the following formula (1), A structural unit (c) having a conjugated diene moiety in a side chain; having The copolymer (A) is A structural unit (a) having an acid group; A structural unit (b) having a group represented by the following formula (1-1) or the following formula (1-2), A structural unit (c) having a conjugated diene moiety in a side chain; A method for producing a copolymer (A) having the above formula: [ka] (In formula (1), R 1 and R 4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a linking site with a residue obtained by removing the group of formula (1) from the structural unit (pb). [ka] (In formula (1-1), R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a linking site with the residue obtained by removing the group of formula (1-1) from the structural unit (b). [ka] (In formula (1-2), R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R 4is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a linking site with the residue obtained by removing the group of formula (1-2) from the structural unit (b). Effect of the Invention

[0010] According to the present disclosure, it is possible to provide a copolymer that contributes to improving developability and gives a resin cured film having excellent solvent resistance, and a photosensitive resin composition and a photosensitive coloring composition using the copolymer. It is also possible to provide a resin cured film having excellent solvent resistance obtained by curing the photosensitive resin composition and the photosensitive coloring composition, a color filter, and an image display element including the same. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, embodiments of the present invention will be described in detail, however, the present invention is not limited to the embodiments described below.

[0012] In this specification, when "to" is used to describe a numerical range, the numerical values ​​at both ends are the upper and lower limits, respectively, and are included in the numerical range.

[0013] In this specification, "(meth)acrylic acid" means methacrylic acid or acrylic acid, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acryloyloxy" means acryloyloxy or methacryloyloxy.

[0014] In this specification, the term "ethylenically unsaturated bond" means a double bond formed between carbon atoms other than carbon atoms forming an aromatic ring, and the term "ethylenically unsaturated group" means a group having an ethylenically unsaturated bond.

[0015] In this specification, the term "structural unit" refers to a unit derived from a polymerizable compound used as a monomer or a unit obtained by further modifying a unit derived from a polymerizable compound used as a monomer.

[0016] [Copolymer (A)] The copolymer (A) of one embodiment contains a structural unit (a) having an acid group, a structural unit (b) having a group represented by the following formula (1-1) or the following formula (1-2), a structural unit (c) having a conjugated diene moiety in a side chain, and optionally a structural unit (pb) having a group represented by the following formula (1). The copolymer (A) has a structural unit (b) having an ethylenically unsaturated group and a structural unit (c) having a conjugated diene moiety in a side chain, and the two are crosslinked by a Diels-Alder reaction. Therefore, when the copolymer (A) is used in a photosensitive resin composition, the low-temperature curing property is improved. In addition, when the copolymer (A) is used together with a reactive diluent (B) described later, the ethylenically unsaturated group of the structural unit (b) reacts with the reactive diluent (B), and good adhesion of the cured film to the substrate is obtained. [ka] (In formula (1-1), R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a linking site with the residue obtained by removing the group of formula (1-1) from the structural unit (b). [ka] (In formula (1-2), R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R 4 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a linking site with the residue obtained by removing the group of formula (1-2) from the structural unit (b). [ka] (In formula (1), R 1 and R 4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R 2 and R 3are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a linking site with a residue obtained by removing the group of formula (1) from the structural unit (pb).

[0017] Copolymer (A) may further contain, as necessary, a structural unit (d) derived from an alkyl (meth)acrylate in which the alkyl group has 1 to 12 carbon atoms. Copolymer (A) may further contain, as necessary, a structural unit (e) other than the structural units (a) to (d) and the structural unit (pb).

[0018] (Structural unit (a) having an acid group) The structural unit (a) having an acid group (also simply referred to as "structural unit (a)") is not particularly limited as long as it is a structural unit having an acid group and does not have an ethylenically unsaturated group. When the copolymer (A) has the structural unit (a) having an acid group, good alkaline developability can be obtained when the copolymer (A) is used in a photosensitive resin composition. Examples of the acid group include a carboxy group, a sulfo group, and a phospho group. Among these acid groups, the carboxy group is preferred as the acid group of the structural unit (a) in terms of ease of availability.

[0019] The structural unit (a) having an acid group is preferably a structural unit derived from a monomer (ma) having an acid group and an ethylenically unsaturated bond (hereinafter, also simply referred to as monomer (ma)). Specific examples of the monomer (ma) include unsaturated carboxylic acids or anhydrides thereof such as (meth)acrylic acid, α-bromo(meth)acrylic acid, β-furyl(meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, α-cyanocinnamic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, and citraconic anhydride; unsaturated sulfonic acids such as 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, and p-styrenesulfonic acid; and unsaturated phosphonic acids such as vinylphosphonic acid. The monomer (ma) is preferably an unsaturated carboxylic acid or an anhydride thereof, more preferably (meth)acrylic acid or a (meth)acrylate having a carboxylic acid group, and even more preferably (meth)acrylic acid.

[0020] The monomer (ma) having an acid group and an ethylenically unsaturated bond may be used alone or in combination of two or more kinds.

[0021] The content of the structural unit (a) is preferably 5 mol% or more, more preferably 8 mol% or more, and even more preferably 10 mol% or more, based on the total structural units of the copolymer (A). The content of the structural unit (a) is preferably 50 mol% or less, more preferably 40 mol% or less, and even more preferably 30 mol% or less, based on the total structural units of the copolymer (A). Any combination of these lower limit values ​​and upper limit values ​​may be used. The content of the structural unit (a) is preferably 5 to 50 mol%, more preferably 8 to 40 mol%, and even more preferably 10 to 30 mol% based on the total structural units of the copolymer (A). When the content of the structural unit (a) is 5 mol% or more, the photosensitive resin composition using the copolymer (A) has good developability. When the content of the structural unit (a) is 50 mol% or less, the contents of the structural unit (b) and the structural unit (c) can be sufficiently ensured, and therefore the effects due to the structural unit (b) and the structural unit (c) can be sufficiently ensured.

[0022] (Structural unit (b) having a group represented by formula (1-1) or formula (1-2)) The structural unit (b) having a group represented by formula (1-1) or formula (1-2) (also simply referred to as "structural unit (b)") is a structural unit having a group represented by the following formula (1-1) or formula (1-2). When the copolymer (A) has the structural unit (b), the dienophile portion of the structural unit (b) and the conjugated diene portion of the structural unit (c) described below can be crosslinked by the Diels-Alder reaction. Therefore, when the copolymer (A) is used in a photosensitive resin composition, the low-temperature curing property is improved. The ethylenically unsaturated group of the structural unit (b) can also react with the reactive diluent (B) contained in the photosensitive resin composition. This allows the cured film to have good adhesion to the substrate. [ka] (In formula (1-1), R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R 2 and R 3are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a linking site with the residue obtained by removing the group of formula (1-1) from the structural unit (b). [ka] (In formula (1-2), R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R 4 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a linking site with the residue obtained by removing the group of formula (1-2) from the structural unit (b).

[0023] The group represented by formula (1-1) may not be of one type. 1 may be different, and R 2 may also be different, and R 3 The same applies to the group represented by formula (1-2).

[0024] In formula (1-1) and formula (1-2), R 1 and R 4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 5 carbon atoms. In particular, a hydrocarbon group having 1 to 3 carbon atoms is more preferred since the conversion reaction from the structural unit (pb) to the structural unit (b) having a group represented by formula (1-1) or formula (1-2) is easily caused. R 1 and R 4 R is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably an ethyl group. 1 and R 4 may be the same or different. Since the monomer (m-pb) described later can be easily produced, R 1 and R 4 are preferably the same.

[0025] In formula (1-1) and formula (1-2), R 2 and R3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. In particular, since the conversion reaction from the structural unit (pb) to the structural unit (b) having a group represented by formula (1-1) or formula (1-2) is likely to occur, a hydrogen atom or a methyl group is more preferable, and a hydrogen atom is particularly preferable. R 2 and R 3 may be the same or different. Since the monomer (m-pb) described later can be easily produced, R 2 and R 3 are preferably the same.

[0026] The structural unit (b) can be obtained by carrying out a dealcoholization reaction and a decarboxylation reaction of a structural unit (pb) having a group represented by the following formula (1) (also simply referred to as "structural unit (pb)") in a solvent (PD) using a basic catalyst. [ka] (In formula (1), R 1 and R 4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a linking site with a residue obtained by removing the group of formula (1) from the structural unit (pb).

[0027] The structural unit (pb) is a structural unit derived from a monomer (m-pb) (also simply referred to as "monomer (m-pb)") having a group represented by the above formula (1). The monomer (m-pb) may be used alone or in combination of two or more kinds.

[0028] The monomer (m-pb) is a monomer having an ethylenically unsaturated bond and a group represented by the above formula (1).

[0029] In formula (1), R 1 , R 2 , R3 and R 4 is similar to that described above.

[0030] Examples of the monomer (m-pb) include a compound obtained by a urethane reaction between an isocyanato group in an isocyanate compound having an ethylenically unsaturated group such as a vinyl group or a (meth)acryloyloxy group in the molecule and a hydroxy group in a hydroxy group-containing compound represented by the following formula (2). [ka] (In formula (2), R 1 , R 2 , R 3 and R 4 is R in formula (1). 1 , R 2 , R 3 and R 4 is the same as

[0031] As a method for subjecting the above-mentioned isocyanate compound having an ethylenically unsaturated group and the hydroxyl group-containing compound represented by formula (2) to a urethane reaction, a conventionally known method can be used.

[0032] The urethanization reaction can be carried out regardless of the presence or absence of a solvent. When the urethanization reaction is carried out using a solvent, the solvent to be used may be any solvent that is inactive to the isocyanato group, and any known solvent may be used.

[0033] The urethane reaction is generally preferably carried out at a temperature of -10°C or higher and 90°C or lower, more preferably at a temperature of 5°C or higher and 70°C or lower, and even more preferably at a temperature of 10°C or higher and 40°C or lower.

[0034] When carrying out the above urethanization reaction, a urethanization catalyst such as dibutyltin dilaurate and a polymerization inhibitor such as phenothiazine, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol (BHT) may be used as necessary.

[0035] An example of an isocyanate compound having an ethylenically unsaturated group that can be used as a raw material for the monomer (m-pb) is an isocyanate compound represented by the following formula (3). [ka] (In formula (3), R 5 represents a hydrogen atom or a methyl group, R 6 -CO-, -COOR 7 - (where R 7 is an alkylene group having 1 to 6 carbon atoms.) or -COO-R 8 O-CONH-R 9 - (where R 8 is an alkylene group having 2 to 6 carbon atoms, R 9 represents an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms, which may have a substituent.

[0036] In the isocyanate compound represented by formula (3), R 6 Due to the ease of preparation of isocyanate compounds, -COOR 7 - is preferred, R 7 It is more preferable that the alkylene group has 1 to 4 carbon atoms.

[0037] Specific examples of the isocyanate compound represented by the above formula (3) include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, and methacryloyl isocyanate.

[0038] The isocyanate compound used as a raw material for the monomer (m-pb) may be a reaction product obtained by reacting an equimolar amount of a hydroxyalkyl (meth)acrylate with a diisocyanate compound (hydroxyalkyl (meth)acrylate:diisocyanate compound=1 mol:1 mol).

[0039] The alkyl group of the hydroxyalkyl (meth)acrylate is preferably an ethyl group or an n-propyl group, and more preferably an ethyl group, for ease of reaction.

[0040] Examples of the diisocyanate compound include hexamethylene diisocyanate, 2,4-(or 2,6-)tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 3,5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate (IPDI), m-(or p-)xylene diisocyanate, 1,3-(or 1,4-)bis(isocyanatomethyl)cyclohexane, and lysine diisocyanate.

[0041] Examples of the other isocyanate compounds used as raw materials for the monomer (m-pb) include 1,1-bis(methacryloyloxymethyl)methyl isocyanate, 1,1-bis(methacryloyloxymethyl)ethyl isocyanate, 1,1-bis(acryloyloxymethyl)methyl isocyanate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate.

[0042] As the isocyanate compound used as a raw material for the monomer (m-pb), from the viewpoint of low-temperature curing properties, an isocyanato group-containing (meth)acrylate is preferable, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 1,1-bis(methacryloyloxymethyl)ethyl isocyanate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate and methacryloyl isocyanate are more preferable, and 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate and 1,1-bis(methacryloyloxymethyl)ethyl isocyanate are even more preferable.

[0043] Examples of the hydroxyl group-containing compound represented by formula (2) used as a raw material for the monomer (m-pb) include malic acid ester, 2-methylmalic acid ester, 3-methylmalic acid ester, 2,3-dimethylmalic acid ester, etc. Among them, malic acid ester is preferred from the viewpoints of ease of conversion reaction to the structural unit (b) having a group represented by formula (1-1) or formula (1-2) and ease of availability.

[0044] The number of carbon atoms (-COOR) of the two ester moieties contained in the hydroxyl group-containing compound represented by formula (2) is 1 and COOR 4 R in 1 and R 4 The number of carbon atoms in each of these groups is 1 to 20, preferably 1 to 5, and more preferably 1 to 3.

[0045] From the viewpoint of availability, it is particularly preferable that the hydroxy group-containing compound represented by formula (2) is diethyl malate.

[0046] Specifically, the monomer (m-pb) is preferably one or more selected from 2-[(diethyl malate)carbonylamino]ethyl acrylate, [(diethyl malate)carbonylamino]methyl acrylate, 2-[(diethyl malate)carbonylamino]propyl acrylate, and 2-[(diethyl malate)carbonylamino]butyl acrylate, and from the viewpoint of ease of production, 2-[(diethyl malate)carbonylamino]ethyl acrylate is particularly preferred.

[0047] The total content of the structural units (b) and (pb) is preferably from 5 to 50 mol %, more preferably from 8 to 40 mol %, and even more preferably from 10 to 30 mol %, of all the structural units in the copolymer (A).

[0048] The content of the structural unit (b) in all structural units of the copolymer (A) is preferably from 0.1 to 45 mol %, more preferably from 0.5 to 35 mol %, and even more preferably from 1 to 25 mol %.

[0049] (Structural unit (c) having a conjugated diene moiety in the side chain) The structural unit (c) having a conjugated diene moiety in the side chain (also simply referred to as "structural unit (c)") is not limited as long as it does not have an acid group, a group represented by the above formula (1-1), a group represented by the above formula (1-2), or a group represented by the above formula (1), and has a conjugated diene moiety. The structural unit (c) may be of only one type, or of two or more types. By containing the structural unit (c) in the copolymer (A), the dienophile moiety of the structural unit (b) and the conjugated diene moiety of the structural unit (c) can be crosslinked by a Diels-Alder reaction.

[0050] Examples of the conjugated diene moiety of the structural unit (c) having a conjugated diene moiety in the side chain include acyclic aliphatic hydrocarbon skeletons such as 1,3-butadiene skeleton; aromatic hydrocarbon skeletons such as anthracene ring; cyclic dienes such as cyclopentadiene, dicyclopentadiene, and cyclohexa-2,4-dienone ring; and heterocyclic skeletons such as imidazole ring, furan ring, triazine ring, thiophene ring, pyrrole ring, thiophene-1-oxide ring, thiophene-1,1-dioxide ring, 1,2-dihydropyridine ring, 2H-thiopyran-1,1-dioxide ring, and pyran-2-one ring. Among these conjugated diene moieties, from the viewpoint of excellent reactivity in the Diels-Alder reaction, cyclic dienes and heterocyclic skeletons are preferred, and furan ring is more preferred.

[0051] The structural unit (c) is preferably a structural unit derived from a conjugated diene-containing monomer (mc) (hereinafter, also simply referred to as "monomer (mc)"). The monomer (mc) is a monomer that does not have an acid group, a group represented by the above formula (1-1), a group represented by the above formula (1-2), or a group represented by the above formula (1), and has a conjugated diene moiety and an ethylenically unsaturated bond. From the viewpoint of ease of synthesis of the copolymer (A), the monomer (mc) is preferably a monomer having a vinyl group or a (meth)acryloyloxy group as an ethylenically unsaturated group, and more preferably a monomer having a (meth)acryloyloxy group.

[0052] Examples of the conjugated diene-containing monomer (mc) include a compound obtained by urethane-forming an isocyanate compound having an ethylenically unsaturated group and an isocyanato group, and a compound having a conjugated diene moiety and active hydrogen. A conventionally known method can be used as a method for urethane-forming the above-mentioned isocyanate compound and a compound having a conjugated diene moiety and active hydrogen.

[0053] Examples of the isocyanate compound used as a raw material for the monomer (mc) include the isocyanate compounds exemplified as raw materials for the above-mentioned monomer (m-pb), and the same applies to preferred compounds.

[0054] Examples of compounds having a conjugated diene moiety and active hydrogen that are used as raw materials for the monomer (mc) include 2,4-hexadiene-1-ol, 2-(hydroxymethyl)anthracene, 2-hydroxymethyl-1-methylimidazole, 1-(2-hydroxyethyl)imidazole, 4(5)-(hydroxymethyl)imidazole, 1-(3-aminopropyl)imidazole, furfuryl alcohol, 2,5-furan diol, furfurylamine, 5-methylfurfurylamine, etc. Among these compounds, compounds containing one functional group having active hydrogen are preferred from the viewpoint of excellent reactivity in the Diels-Alder reaction, and 2,4-hexadiene-1-ol, 1-(2-hydroxyethyl)imidazole, furfuryl alcohol, and furfurylamine are more preferred, with furfuryl alcohol being even more preferred.

[0055] As the conjugated diene-containing monomer (mc), it is preferable to use a furan ring-containing (meth)acrylate such as 2-[(2-furanylmethoxy)carbonylamino]ethyl (meth)acrylate, furfuryl (meth)acrylate, etc. Among these furan ring-containing (meth)acrylates, the monomer (mc) is preferably 2-[(2-furanylmethoxy)carbonylamino]ethyl methacrylate, since it is easily available.

[0056] The conjugated diene-containing monomer (mc) may be used alone or in combination of two or more kinds.

[0057] The content of the structural unit (c) in the copolymer (A) can be appropriately determined depending on the application of the copolymer (A). The content of the structural unit (c) is preferably 5 mol% or more, more preferably 8 mol% or more, and even more preferably 10 mol% or more. The content of the structural unit (c) is preferably 50 mol% or less, more preferably 40 mol% or less, and even more preferably 30 mol% or less. Any combination of these lower limit values ​​and upper limit values ​​may be used. The content of the structural unit (c) is preferably 5 to 50 mol%, more preferably 8 to 40 mol%, and even more preferably 10 to 30 mol%. When the content of the structural unit (c) is 5 mol% or more, the amount of crosslinking with the structural unit (b) can be sufficiently secured, and a photosensitive resin composition using the copolymer (A) can have better low-temperature curing properties. In addition, a cured product with better solvent resistance can be obtained. When the content of the structural unit (c) is 50 mol % or less, the contents of the structural units (a) and (b) can be sufficiently ensured.

[0058] The content ratio of the structural unit (b) is preferably 10 mol% or more, more preferably 15 mol% or more, and even more preferably 20 mol% or more, based on the total of the structural unit (b) and the structural unit (c). The content ratio of the structural unit (b) is preferably 90 mol% or less, more preferably 50 mol% or less, and even more preferably 40 mol% or less, based on the total of the structural unit (b) and the structural unit (c). Any combination of these lower limit values ​​and upper limit values ​​may be used. The content ratio (molar ratio) of the structural unit (b) and the structural unit (c) is preferably 10:90 to 90:10, more preferably 15:85 to 50:50, and even more preferably 20:80 to 40:60. When it is within the above range, the crosslinking amount of the structural unit (b) and the structural unit (c) can be sufficiently secured, and good developability when used as a photosensitive resin composition and good solvent resistance of the cured film can be obtained.

[0059] (Structural unit (d) derived from alkyl(meth)acrylate having an alkyl group with 1 to 12 carbon atoms) The structural unit (d) derived from an alkyl(meth)acrylate having an alkyl group with 1 to 12 carbon atoms (also simply referred to as "structural unit (d)") is not limited as long as it does not have an acid group, an ethylenically unsaturated group, a group represented by the above formula (1), or a hydroxy group, and is a structural unit derived from an alkyl(meth)acrylate having an alkyl group with 1 to 12 carbon atoms. When the copolymer (A) has the structural unit (d), it is easy to control the solubility and adhesion of the cured film.

[0060] The structural unit (d) is preferably a structural unit derived from a (meth)acrylate monomer (md) (hereinafter, simply referred to as monomer (md)) having an alkyl group with 1 to 12 carbon atoms in the alkyl group. Specific examples of the monomer (md) include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl (meth)acrylate. Among these, from the viewpoints of availability and reactivity in synthesizing the resin precursor (PA), 2-ethylhexyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and methyl (meth)acrylate are preferred.

[0061] The monomer (md) may be used alone or in combination of two or more kinds.

[0062] The content of the structural unit (d) is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, based on the total structural units of the copolymer (A). The content of the structural unit (d) is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less, based on the total structural units of the copolymer (A). Any combination of these lower limit values ​​and upper limit values ​​may be used. The content of the structural unit (d) is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, and even more preferably 5 to 40 mol% based on the total structural units of the copolymer (A). When the content of the structural unit (d) is 1 mol% or more, it is easy to control the solubility and adhesion of the cured film. When the content of the structural unit (d) is 50 mol% or less, the content of the structural units (a) to (c) can be sufficiently ensured, so that sufficient developability and low-temperature curability of the photosensitive resin composition and sufficient solvent resistance of the cured film can be obtained.

[0063] (Structural units (a) to (d) and structural units (e) other than the structural unit (pb)) The copolymer (A) may contain a structural unit (e) (also simply referred to as "structural unit (e)") other than the structural units (a) to (d) and the structural unit (pb) as necessary. By including the structural unit (e) in the copolymer (A), it is possible to impart additional required functions.

[0064] The other structural unit (e) is a structural unit derived from a monomer (me) having another ethylenically unsaturated group copolymerizable with the monomers (ma), (m-pb), (mc), and (md) (also simply referred to as monomer (me)). Specific examples include hydroxyl group-containing monomers, aromatic vinyl compounds, cyclic olefins having a norbornene structure, dienes, (meth)acrylic acid esters, (meth)acrylic acid amides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides, glycidyl (meth)acrylates, (meth)acrylic acid anilides, (meth)acrylonitrile, and acrolein.

[0065] The hydroxyl group-containing monomer is a monomer having a hydroxyl group and an ethylenically unsaturated group. Specific examples of the hydroxyl group-containing monomer include (meth)acrylic acid ester derivatives having a hydroxyl group, specifically, hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; 2-hydroxy-3-phenoxypropyl (meth)acrylate, etc. Among them, hydroxyalkyl (meth)acrylates are preferred from the viewpoints of reactivity during synthesis of the resin precursor (PA), low-temperature curing property of the photosensitive resin composition containing the copolymer (A), and ease of availability. As the hydroxyalkyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate are preferred, and from the viewpoint of reducing the glass transition temperature of the copolymer (A), 4-hydroxybutyl (meth)acrylate is more preferred.

[0066] Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, methoxystyrene, p-nitrostyrene, p-cyanostyrene, and p-acetylaminostyrene.

[0067] Cyclic olefins having a norbornene structure include norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, and tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodec-3-ene, 8-ethyltetracyclo[4.4.0.1 2,5 .1 7,10 ]dodec-3-ene, dicyclopentadiene, tricyclo[5.2.1.0 2,6 ]dec-8-ene, tricyclo[4.4.0.1 2,5 ]undec-3-ene, tricyclo[6.2.1.0 1,8]undec-9-ene, tetracyclo[4.4.0.1 2,5 .1 7,10 .0 1,6 ]dodec-3-ene, 8-ethylidenetetracyclo[4.4.0.1 2,5 .1 7,12 ]dodec-3-ene, pentacyclo[6.5.1.1 3,6 .0 2,7 .0 9,13 ]pentadec-4-ene and the like.

[0068] The dienes include butadiene, isoprene, chloroprene, and the like.

[0069] Examples of (meth)acrylic acid esters include benzyl (meth)acrylate, rosin (meth)acrylate, norbornyl (meth)acrylate, 5-ethylnorbornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl acrylate, tetrahydrofurfuryl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, and 5-ethylnorbornyl (meth)acrylate. p)acrylate, triphenylmethyl (meth)acrylate, phenyl (meth)acrylate, cumyl (meth)acrylate, 4-phenoxyphenyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol mono(meth)acrylate, biphenyloxyethyl (meth)acrylate, naphthalene (meth)acrylate, anthracene (meth)acrylate, ethoxylated phenyl (meth)acrylate, and the like.

[0070] Examples of the (meth)acrylic acid amide include (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diisopropylamide, and (meth)acrylic acid anthracenylamide.

[0071] Examples of the vinyl compound include vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, and vinyltoluene.

[0072] Examples of the unsaturated dicarboxylic acid diester include diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate.

[0073] Examples of monomaleimides include N-phenylmaleimide, N-cyclohexylmaleimide, and N-laurylmaleimide.

[0074] Among these, from the viewpoints of availability and reactivity in synthesizing the resin precursor (PA), aromatic vinyl compounds and aromatic group-containing (meth)acrylates are preferred, and styrene and benzyl (meth)acrylate are more preferred.

[0075] The monomer (me) may be used alone or in combination of two or more kinds.

[0076] When the copolymer (A) contains the structural unit (e), its content is preferably 5 to 50 mol %, more preferably 8 to 40 mol %, and even more preferably 10 to 30 mol % of all structural units of the copolymer (A). By setting the content of the structural unit (e) within the above range, it is possible to impart additional functions by the structural unit (e) while sufficiently securing the functions of the structural units (a) to (d), or to adjust the functions obtained from the structural units (a) to (d) to an appropriate range.

[0077] [Ethylenically unsaturated group equivalent of copolymer (A)] The ethylenically unsaturated group equivalent of the copolymer (A) is preferably 300 g / mol or more, more preferably 1000 g / mol or more, and even more preferably 2000 g / mol or more. The ethylenically unsaturated group equivalent of the copolymer (A) is preferably 10000 g / mol or less, more preferably 8000 g / mol or less, and even more preferably 6500 g / mol or less. Any combination of these lower limit values ​​and upper limit values ​​may be used. The ethylenically unsaturated group equivalent of the copolymer (A) is preferably 300 to 10000 g / mol, more preferably 1000 to 8000 g / mol, and even more preferably 2000 to 6500 g / mol. When it is 300 g / mol or more, the storage stability as a photosensitive resin composition is good. When it is 10000 g / mol or less, the solvent resistance of the cured product is good even when cured at a low temperature.

[0078] The "ethylenically unsaturated group equivalent" is the mass of a polymer per 1 mole of ethylenically unsaturated groups in the polymer. The ethylenically unsaturated group equivalent (g / mol) of the copolymer (A) is determined by dividing the mass of the copolymer (A) by the number of moles of the ethylenically unsaturated groups contained in the copolymer (A).

[0079] In the present specification, R in formula (1-1) and formula (1-2) in copolymer (A) 2 and R 3When all are hydrogen atoms, the ethylenically unsaturated group equivalent is a value calculated from the conversion rate of the structural unit (pb) to the structural unit (b) calculated from the area ratio of the NMR spectrum obtained under the following conditions using an NMR device (e.g., Bruker ULTRA SHIELD PLUS 400 (400 MHz), Bruker) and the charged amounts of the monomers (ma), (m-pb), and (mc) to (me) used in producing the resin precursor (PA). The measurement sample may contain the resin precursor (PA). In this case, the value obtained for the mixture of the copolymer (A) and the resin precursor (PA) is determined as the ethylenically unsaturated group equivalent of the copolymer (A). When the measurement sample contains the resin precursor (PA), the conversion rate of the structural unit (pb) to the structural unit (b) is also a value for the mixture of the copolymer (A) and the resin precursor (PA).

[0080] (NMR conditions) Measurement method: 1 H-NMR Lock solvent: CDCl3 Internal standard: TSP-d4 (sodium trimethylsilylpropionate) = 0 ppm Temperature: room temperature Sample preparation: Powder sample (20 mg) / CDCl3 (1 mL) + TSP-d4 (5 mg)

[0081] (Sample preparation method) 20 mg of the dried copolymer (A) is precisely weighed out, dissolved in 1 mL of CDCl3 in a 20 mL sample bottle, shaken for 5 minutes in an ultrasonic cleaner, and then sealed in a 5 mmφ NMR sample tube. NMR measurement is performed immediately after sampling.

[0082] The conversion rate from structural unit (pb) to structural unit (b) is detected at 2.5 to 3.0 ppm - CR 2 -CHR 3 The spectrum of "-CH2-" of -C(=O)- (i.e. -CH-CH2-C(=O)-) and -C(=O)-CR detected at 6.5 to 7.0 ppm 3 =CR 2 -C(=O)- and -C(=O)-CR2 =CR 3 It is calculated based on the spectral area ratio of -C(=O)- (i.e., -C(=O)-CH=CH-C(=O)-) using the following formula. Conversion rate from structural unit (pb) to structural unit (b) = (-C(=O)-CH=CH-C(=O)-) / {(-CH-CH2-C(=O)-)+(-C(=O)-CH=CH-C(=O)-)}×100(%)

[0083] R of formula (1-1) and formula (1-2) in copolymer (A) 2 and R 3 When the structural unit (pb) contains a structural unit (b) having a group represented by formula (1-1) or formula (1-2), at least one or both of which is a hydrocarbon group having 1 to 20 carbon atoms, the conversion rate of the structural unit (pb) to the structural unit (b) is a value calculated from the area ratio of the NMR spectrum obtained by the same method as above.

[0084] For example, R 2 are all hydrogen atoms, and R 3 When all of the structural units are methyl groups, the conversion rate from structural unit (pb) to structural unit (b) is -CR 2 -CHR 3 The spectrum of -CH(CH3)- in -C(=O)- (i.e. -CH-CH(CH3)-C(=O)-) and -C(=O)-CR 3 =CR 2 -C(=O)- and -C(=O)-CR 2 =CR 3 It is calculated based on the area ratio of the "CH3" spectrum of -C(=O)- (i.e., -C(=O)-C(CH3)=CH-C(=O)- and -C(=O)-CH=C(CH3)-C(=O)-) using the following formula. Conversion rate from structural unit (pb) to structural unit (b) = {(-C(=O)-C(CH3)=CH-C(=O)-) + (-C(=O)-CH=C(CH3)-C(=O)-)} / {(-CH-CH(CH3)-C(=O)-) + (-C(=O)-C(CH3)=CH-C(=O)-) + (-C(=O)-CH=C(CH3)-C(=O)-)} x 100 (%)

[0085] For example, R 2 and R 3 When all of the structural units are methyl groups, the conversion rate from structural unit (pb) to structural unit (b) is -CR 2 -CHR 3 The spectrum of -CH(CH3)- in -C(=O)- (i.e. -C(CH3)-CH(CH3)-C(=O)-) and -C(=O)-CR 3 =CR 2 -C(=O)- and -C(=O)-CR 2 =CR 3 It is calculated using the following formula based on the area ratio of the spectrum of "CH3" of -C(=O)- (i.e. -C(=O)-C(CH3)=C(CH3)-C(=O)-). Conversion rate from structural unit (pb) to structural unit (b) = {(-C(=O)-C(CH3)=C(CH3)-C(=O)-) / 2} / [(-C(CH3)-CH(CH3)-C(=O)-)+{(-C(=O)-C(CH3)=C(CH3)-C(=O)-) / 2}] x 100(%)

[0086] R 2 and R 3 Even when is other than the above examples, the conversion rate of the structural unit (pb) to the structural unit (b) can be calculated similarly based on the area ratio of the NMR spectrum.

[0087] The modification rate of the copolymer (A) refers to the conversion rate of the structural unit (pb) to the structural unit (b) calculated by the above-mentioned measurement method. In other words, the modification rate of the copolymer (A) means the modification rate calculated by the following formula (X). Modification rate [%] = structural unit (b) / (structural unit (pb) + (b)) [molar ratio] × 100 (X) The number of moles of the structural unit (b) in formula (X) means the total number of moles of the structural unit having formula (1-1) and the structural unit having formula (1-2).

[0088] The modification rate of the copolymer (A) is preferably 20% or more, more preferably 30% or more, further preferably 40% or more, and particularly preferably 50% or more. The modification rate of the copolymer (A) may be 60% or more. The modification rate of the copolymer (A) may be 100%, but from the viewpoint of reducing the influence on developability, solvent resistance, etc. due to the basic catalyst used in the conversion reaction remaining in the photosensitive resin composition, it may be 99% or less, or 95% or less.

[0089] In the present specification, the copolymer (A) is R 2 and R 3 When the copolymer (A) contains a structural unit (b) having a group represented by formula (1-1) or formula (1-2), in which at least one or both of the above is a hydrocarbon group having 1 to 20 carbon atoms, the ethylenically unsaturated group equivalent is a value calculated from the amount of halogen bonded to the copolymer (A). The amount of halogen bonded to the copolymer (A) is evaluated as follows in accordance with JIS K 0070:1992.

[0090] That is, the dried copolymer (A) is dissolved in chloroform, an appropriate amount of Wiess's solution is added, and the mixture is stirred. The mixture is then sealed and left in a dark place at 23°C for 1 hour. A potassium iodide solution and water are added to the solution, and the resulting solution is titrated with a sodium thiosulfate solution. When the solution turns slightly yellow, a few drops of starch solution are added, and titration is continued until the blue color disappears. The ethylenically unsaturated bonds in the copolymer (A) react with halogen molecules in a 1:1 ratio. Therefore, the ethylenically unsaturated group equivalent of the copolymer (A) is obtained by dividing the mass (g) of the copolymer (A) used in the measurement by the amount of substance (mol) of halogen molecules bonded to the copolymer (A) obtained by this measurement. The measurement sample may contain a resin precursor (PA). In this case, the value obtained for the mixture of the copolymer (A) and the resin precursor (PA) is determined as the ethylenically unsaturated group equivalent of the copolymer (A).

[0091] [Acid value of copolymer (A)] The acid value of the copolymer (A) is preferably 10 KOHmg / g or more, more preferably 15 KOHmg / g or more, and even more preferably 20 KOHmg / g or more. The acid value of the copolymer (A) is preferably 300 KOHmg / g or less, more preferably 200 KOHmg / g or less, and even more preferably 150 KOHmg / g or less. Any combination of these lower limit values ​​and upper limit values ​​may be used. The acid value of the copolymer (A) is preferably 10 to 300 KOHmg / g, more preferably 15 to 200 KOHmg / g, and even more preferably 20 to 150 KOHmg / g. When it is 10 KOHmg / g or more, the developability is good. When it is 300 KOHmg / g or less, the storage stability is good.

[0092] "Acid value" refers to the acid value of a curable polymer measured according to JIS K6901:2008 5.3. In other words, the acid value means the number of milligrams of potassium hydroxide required to neutralize the acidic components contained in 1 g of copolymer. The measurement sample may contain a resin precursor (PA). In this case, the value obtained for the mixture of copolymer (A) and resin precursor (PA) is determined as the acid value of copolymer (A).

[0093] [Weight average molecular weight of copolymer (A)] The weight average molecular weight of the copolymer (A) is preferably 1000 or more, more preferably 3000 or more, and even more preferably 5000 or more. The weight average molecular weight of the copolymer (A) is preferably 50000 or less, more preferably 40000 or less, and even more preferably 30000 or less. Any combination of these lower limit values ​​and upper limit values ​​may be used. The weight average molecular weight of the copolymer (A) is preferably 1000 to 50000, more preferably 3000 to 40000, and even more preferably 5000 to 30000. When the weight average molecular weight is 1000 or more, when the copolymer (A) is used as a raw material for a photosensitive resin composition, defects such as chipping are unlikely to occur in the cured resin film after development. When the weight average molecular weight is 50000 or less, the photosensitive resin composition containing the copolymer (A) has a sufficiently short development time and is excellent in practical use.

[0094] In this specification, the weight average molecular weight refers to a weight average molecular weight calculated as standard polystyrene using gel permeation chromatography (GPC) under the following conditions. Column: Showdex (trademark) Two LF-804 columns (manufactured by Resonac Co., Ltd.) were used connected in series. Column temperature: 40℃ Sample: 0.2% by mass solution of the object to be measured in tetrahydrofuran Developing solvent: Tetrahydrofuran Detector: Differential refractometer (Shodex (trademark) RI-71S) (manufactured by Resonac Co., Ltd.) Flow rate: 1mL / min The measurement sample may contain the resin precursor (PA). In this case, the value obtained for the mixture of the copolymer (A) and the resin precursor (PA) is determined as the weight average molecular weight of the copolymer (A).

[0095] [Method for producing copolymer (A)] (Method of producing resin precursor (PA)) The resin precursor (PA) is a copolymer that does not have the structural unit (b) and contains a structural unit (a) having an acid group, a structural unit (pb) having a group represented by the following formula (1), and a structural unit (c) having a conjugated diene moiety in a side chain, and may optionally contain a structural unit selected from the structural units (d) and (e). [ka] (In formula (1), R 1 and R 4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a linking site with a residue obtained by removing the group of formula (1) from the structural unit (pb). Resin precursor (PA) can be produced by copolymerizing monomers (ma), (m-pb), and (mc) corresponding to structural units (a), (pb), and (c) contained in resin precursor (PA). The ratio of structural units (a), (pb), and (c) contained in resin precursor (PA) is equal to the ratio of each monomer (ma), (m-pb), and (mc) in the total of all monomers used as raw materials for resin precursor (PA) (hereinafter sometimes referred to as "raw material monomers").

[0096] Therefore, the proportions of the monomers (ma), (m-pb) and (mc) in the raw material monomers used as raw materials for the resin precursor (PA) are preferably 5 to 50 mol% for (ma), 5 to 50 mol% for (m-pb) and 5 to 50 mol% for (mc), more preferably 8 to 40 mol% for (ma), 8 to 40 mol% for (m-pb) and 8 to 40 mol% for (mc), and even more preferably 10 to 30 mol% for (ma), 10 to 30 mol% for (m-pb) and 10 to 30 mol% for (mc).

[0097] When producing a resin precursor (PA) containing the structural unit (d), a monomer (md) may be used as the raw material monomer of the resin precursor (PA) in addition to the monomers (ma), (m-pb), and (mc). In this case, the ratio of the monomer (md) in the raw material monomers used as the raw material of the resin precursor (PA) is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, and further preferably 5 to 40 mol%.

[0098] When producing a resin precursor (PA) containing the structural unit (e), a monomer (me) may be used as the raw material monomer of the resin precursor (PA) in addition to the monomers (ma), (m-pb), and (mc). In this case, the ratio of the monomer (me) in the raw material monomers used as the raw material of the resin precursor (PA) is preferably 5 to 50 mol%, more preferably 8 to 40 mol%, and further preferably 10 to 30 mol%.

[0099] The copolymerization reaction of the raw material monomers (monomers (ma), (m-pb), and (mc), and monomers (md) and (me) used as necessary) used in producing the resin precursor (PA) can be carried out in the presence or absence of a polymerization solvent according to a radical polymerization method known in the art. Specifically, for example, a method can be used in which the raw material monomers, a polymerization initiator, and a polymerization solvent are mixed to prepare a raw material monomer solution, and the solution is polymerized in a nitrogen gas atmosphere at a temperature of 50 to 100° C. for 1 to 20 hours.

[0100] As the polymerization solvent used in producing the resin precursor (PA), those usable as the solvent (PD) described below can be used alone or in combination of two or more kinds.

[0101] The temperature at which the raw material monomers are copolymerized is preferably a temperature at which the urethane bond in the structural unit (b) does not dissociate.

[0102] Specifically, the temperature at which the raw material monomers are copolymerized can be set to 50 to 100°C, preferably 60 to 90°C, and more preferably 65 to 85°C.

[0103] Examples of the polymerization initiator used when copolymerizing raw material monomers include 2,2'-azobis(2,4-dimethylvaleronitrile), azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, and t-butylperoxy-2-ethylhexanoate. The polymerization initiator may be used alone or in combination of two or more. The amount of the polymerization initiator used may be 0.5 to 20 parts by mass, and preferably 1.0 to 16 parts by mass, per 100 parts by mass of raw material monomer (total amount of monomers charged).

[0104] When producing the resin precursor (PA), additives such as a polymerization inhibitor, a chain transfer agent, a photosensitizer, a filler, and a plasticizer may be used as necessary within a range that does not impair the effects of the present invention.

[0105] (Conversion reaction from resin precursor (PA) to copolymer (A)) The copolymer (A) can be produced by converting the structural unit (pb) contained in the resin precursor (PA) to the structural unit (b) in the presence of a basic catalyst and a solvent (PD). For example, a resin precursor composition containing the resin precursor (PA), a basic catalyst, and a solvent (PD) is maintained at a temperature of 0 to 150°C for 0.1 to 10 hours. This allows a dealcoholization reaction and a decarboxylation reaction of the resin precursor (PA) to be carried out, converting the structural unit (pb) contained in the resin precursor (PA) to the structural unit (b), and generating a reaction liquid containing the copolymer (A) and the solvent (PD). The resin precursor (PA) may remain in this reaction liquid.

[0106] [Basic catalyst] The basic catalyst is a compound represented by the formula (1) in which the structural unit (pb) contained in the resin precursor (PA) has R 2 and the carbon atom to which R is bonded. 3The basic catalyst is not particularly limited as long as it can form a double bond between the carbon atom to which the carbon atom is bonded. The basic catalyst may be used alone or in combination of two or more kinds.

[0107] As the basic catalyst, it is preferable to use one having a pKa (acidity constant; also called acid dissociation constant) of 4 to 15 at 25°C. The basic catalyst having a pKa of 4 or more at 25°C includes one having a pKa of 4 or more in an aqueous solution, and one that is too acidic to be measured in an aqueous solution and has a pKa of 4 or more in an aqueous solution calculated from the measurement result in an organic solvent. The pKa of the basic catalyst at 25°C may be 15 or less, 13 or less, or 11 or less. The pKa of the basic catalyst at 25°C may be 4 or more, 5 or more, 6 or more, or 7 or more. The combination of these lower limit values ​​and upper limit values ​​may be any combination. When the pKa of the basic catalyst at 25°C is 15 or less, it is possible to suppress the decrease in activity due to the formation of a salt with the acid group of the structural unit (a).

[0108] An example of the basic catalyst is a compound represented by the following formula (4). R 10 N=CR 11 -NR 12 R 13 (4) (In formula (4), R 10 , R 12 and R 13 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R 11 is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or -N(R 14 ) 2 (wherein R 14 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and two R 14 may be the same or different from each other.) and R 10 , R 11 , R 12 , R 13 and two R 14Any two or more of the groups may be bonded to form a cyclic structure.)

[0109] The basic catalyst also includes, for example, a compound represented by formula (5). R 15 N=CR 16 -NR 17 R 18 (5) (In formula (5), R 15 , R 16 , R 17 and R 18 is a hydrocarbon group, R 15 and R 18 and form a ring structure, R 15 and R 18 The sum of the carbon atoms of R is 3 to 20. 16 and R 17 and form a ring structure, R 16 and R 17 The sum of the carbon atoms is 3 to 20.

[0110] In the compound represented by formula (5), R forming a cyclic structure 15 and R 18 The sum of the numbers of carbon atoms is 3 to 20, and preferably 3 to 10 from the viewpoint of availability.

[0111] In the compound represented by formula (5), R forming a cyclic structure 16 and R 17 The sum of the numbers of carbon atoms is 3 to 20, and preferably 3 to 10 from the viewpoint of availability.

[0112] Specific examples of the compound represented by formula (4) or formula (5) include 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) (pKa 12.5), 1,5-diazabicyclo[4.3.0]-5-nonene (pKa 12.7), and 1,1,3,3-tetramethylguanidine (pKa 13.6). In particular, it is preferable to use 1,8-diazabicyclo[5.4.0]-7-undecene from the viewpoints of the strength of catalytic activity, compatibility with solvents, ease of availability, etc.

[0113] Examples of basic catalysts include alkylamines and cyclic diamines.

[0114] Examples of alkylamines include diisopropylamine (pKa 11.05), trimethylamine, and triethylamine (pKa 10.7).

[0115] Examples of cyclic diamines include 1,4-diazabicyclo[2.2.2]octane (DABCO) (pKa 8.8).

[0116] From the viewpoint of efficiently proceeding with the conversion reaction of the resin precursor (PA), the basic catalyst is preferably at least one selected from the group consisting of pyridine, pyridine derivatives, and imidazole compounds. Without being bound by any theory, pyridine, pyridine derivatives, and imidazole compounds have a relatively low pKa, and therefore maintain activity without forming a salt with the acid group of the structural unit (a), and have high nucleophilicity due to resonance stabilization. Therefore, by using at least one selected from the group consisting of pyridine, pyridine derivatives, and imidazole compounds, the structural unit (pb) contained in the resin precursor (PA) can be efficiently converted to introduce an ethylenically unsaturated group. Therefore, the resin precursor (PA) can be efficiently converted into the copolymer (A) described later. The photosensitive resin composition using the copolymer (A) can provide a cured film that is excellent in low-temperature curability and developability and excellent in solvent resistance.

[0117] Specific examples of pyridine and pyridine derivatives include pyridine (pKa 5.2); C1-4 alkylpyridines such as methylpyridine (picoline) (pKa 6.75) and ethylpyridine; di-C1-4 alkylpyridines such as dimethylpyridine (lutidine) (pKa 6.47-6.6); tri-C1-4 alkylpyridines such as trimethylpyridine (collidine) (pKa 7.48); and 4-aminopyridine derivatives having an amino group at the 4-position such as 4-aminopyridine (pKa 9.17), 4-dimethylaminopyridine (pKa 9.7), 4-diethylaminopyridine, 4-pyrrolidinopyridine, 4-piperidinopyridine, and 2-methyl-4-dimethylaminopyridine. Among them, from the viewpoint of conversion efficiency of the structural unit (pb) contained in the copolymer (A), 4-aminopyridine derivatives are preferred, 4-aminopyridine derivatives having a tertiary amino group at the 4-position are more preferred, 4-dialkylaminopyridine is further preferred, and 4-dimethylaminopyridine is particularly preferred. Note that "C1-4 alkyl" means that the number of carbon atoms in the alkyl group is 1 to 4.

[0118] Examples of the imidazole compound include 2-methylimidazole (pKa 7.75) and 1,2-dimethylimidazole (pKa 7.8).

[0119] The content of the basic catalyst is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the resin precursor (PA). When the content of the basic catalyst is 0.01 parts by mass or more, the reaction rate for converting the structural unit (pb) contained in the resin precursor (PA) to the structural unit (b) tends to be sufficiently fast, which is preferable. When the content of the basic catalyst is 10 parts by mass or less, the effect of the basic catalyst can be suppressed when curing the photosensitive resin composition containing the copolymer (A) produced using the resin precursor composition.

[0120] [Solvent (PD)] Examples of the solvent (PD) include (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, and 3-methoxy-1-butanol; hydroxy group-containing carboxylic acid esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, and methyl 2-hydroxy-3-methylbutyrate; and hydroxy group-containing solvents such as diethylene glycol; as well as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene ... (Poly)alkylene glycol monoalkyl ether acetates such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones; methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, Examples of the solvent include esters such as dipropionate, ethyl acetate, n-butyl acetate, i-propyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; and non-hydroxyl group-containing solvents such as carboxylic acid amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. The solvent (PD) may be used alone or in combination of two or more.

[0121] Among these solvents (PD), it is preferable to use ethers from the viewpoints of availability, cost, and stability during resist preparation, and specifically, it is more preferable to use one or more selected from propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, and 3-methoxy-1-butanol.

[0122] The content of the solvent (PD) is preferably 30 to 1,000 parts by mass, more preferably 50 to 800 parts by mass, based on 100 parts by mass of the total of the components other than the solvent (PD) contained in the resin precursor composition. When the content of the solvent (PD) is 30 parts by mass or more, a stable polymerization reaction can be performed, which is preferable. When the content of the solvent (PD) is 1,000 parts by mass or less, the viscosity of the resin precursor composition can be appropriately adjusted, which is preferable.

[0123] The conversion reaction for converting the structural unit (pb) to the structural unit (b) is preferably carried out under temperature conditions at which the urethane bond in the structural unit (b) does not dissociate.

[0124] Specifically, the temperature of the conversion reaction for converting the structural unit (pb) to the structural unit (b) can be set to 0 to 150°C, preferably 50 to 120°C, and more preferably 60 to 100°C.

[0125] The retention time for retaining the resin precursor composition under the above temperature conditions for the above conversion reaction can be 0.1 to 10 hours, preferably 0.3 to 5 hours, and more preferably 0.5 to 3 hours. The retention time can be appropriately determined depending on the content of the structural unit (pb) contained in the resin precursor (PA) in the resin precursor composition, the content of the basic catalyst, the temperature conditions, and the like.

[0126] The atmosphere in the reaction vessel in which the above conversion reaction is carried out can be, for example, an atmosphere containing air, dry air, nitrogen gas, helium gas, etc., and is preferably a dry air or nitrogen gas atmosphere.

[0127] The pressure inside the reaction vessel in which the conversion reaction is carried out is not particularly limited, but is preferably normal pressure.

[0128] (Reaction Pathway) In the conversion reaction from the resin precursor (PA) to the copolymer (A), it is presumed that the structural unit (pb) contained in the resin precursor (PA) is converted to the structural unit (b) via the reaction pathway shown below. [ka]

[0129] That is, in the structural unit (pb) having a group represented by formula (1) contained in the resin precursor (PA), H of -NH- in the urethane bond and H of the ester moiety (-COOR 1 or -COOR 4 ) A dealcoholization reaction occurs.

[0130] This results in the formation of a heterocyclic group represented by formula (1-3) and / or formula (1-4). The heterocyclic group represented by formula (1-3) is a heterocyclic group represented by formula (1) R 4 Dealcoholization of the ester moiety containing (-R 4 The heterocyclic group represented by formula (1-4) is formed by the reaction of R 1 Dealcoholization of the ester moiety containing (-R 1 OH). [ka] (In formula (1-3), R 1 , R 2 and R 3 is R in formula (1). 1 , R 2 and R 3where * represents the linking site with the residue obtained by removing the group of formula (1-3) from the structural unit (pb). [ka] (In formula (1-4), R 2 , R 3 and R 4 is R in formula (1). 2 , R 3 and R 4 where * represents the linking site with the residue obtained by removing the group of formula (1-4) from the structural unit (pb).

[0131] Next, decarboxylation (-CO2) occurs at the heterocyclic moiety in the group having the heterocyclic ring represented by the above formula (1-3), thereby converting the group having the heterocyclic ring represented by the formula (1-3) into the group represented by the following formula (1-1). [ka] (In formula (1-1), R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a linking site with the residue obtained by removing the group of formula (1-1) from the structural unit (b).

[0132] On the other hand, in the group having a heterocycle represented by the above formula (1-4), decarboxylation (-CO2) occurs at the heterocycle portion, whereby the group having a heterocycle represented by the formula (1-4) is converted to the group represented by the following formula (1-2). [ka] (In formula (1-2), R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R 4 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a linking site with the residue obtained by removing the group of formula (1-2) from the structural unit (b).

[0133] As a result of performing transition state calculations in the formation pathway of each product using wB97XD as the functional and 6-31+g(d) as the basis function in the density functional theory, it is presumed that the conversion reaction of converting the above-mentioned structural unit (pb) to the structural unit (b) has a lower activation barrier in the reaction pathway of formula (1), formula (1-4), and formula (1-2) than the reaction pathway of formula (1), formula (1-3), and formula (1-1), and is the main conversion route. Therefore, it is presumed that the structural unit having the group represented by formula (1-2) and the structural unit having the group represented by formula (1-1) are mixed in the copolymer (A), and that the structural unit having the group represented by formula (1-2) is more present than the structural unit having the group represented by formula (1-1).

[0134] <Photosensitive resin composition and photosensitive coloring composition> The photosensitive resin composition of one embodiment contains a copolymer (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D). The photosensitive resin composition may contain a resin precursor (PA). The photosensitive coloring composition of one embodiment further contains a colorant (E).

[0135] The content of the structural unit (b) is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, and even more preferably 1 mol% or more, based on the total structural units of the copolymer (A) and the resin precursor (PA). The content of the structural unit (b) is preferably 45 mol% or less, more preferably 35 mol% or less, and even more preferably 25 mol% or less, based on the total structural units of the copolymer (A) and the resin precursor (PA). Any combination of these lower limit values ​​and upper limit values ​​may be used. The content of the structural unit (b) is preferably 0.1 to 45 mol%, more preferably 0.5 to 35 mol%, and even more preferably 1 to 25 mol% based on the total structural units of the copolymer (A) and the resin precursor (PA). When the content of the structural unit (b) is 0.1 mol% or more, the amount of crosslinking with the structural unit (c) can be sufficiently secured, and good low-temperature curing properties of the photosensitive resin composition using the copolymer (A) can be obtained. In addition, crosslinking by photocuring with the reactive diluent (B) also proceeds, so good developability can be obtained. When the content of the structural unit (b) is 45 mol % or less, the content of the structural unit (a) can be sufficiently ensured, and sufficient developability can be obtained.

[0136] The content of the structural unit (pb) is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, based on the total structural units of the copolymer (A) and the resin precursor (PA). The content of the structural unit (pb) is preferably 49 mol% or less, more preferably 40 mol% or less, and even more preferably 30 mol% or less, based on the total structural units of the copolymer (A) and the resin precursor (PA). Any combination of these lower and upper limits may be used. The content of the structural unit (pb) is preferably 0 to 49 mol%, more preferably 5 to 40 mol%, and even more preferably 10 to 30 mol% based on the total structural units of the copolymer (A) and the resin precursor (PA).

[0137] The total content of the structural unit (b) and the structural unit (pb) is preferably 5 mol% or more, more preferably 8 mol% or more, and even more preferably 10 mol% or more, based on the total structural units of the copolymer (A) and the resin precursor (PA). The content of the structural unit (pb) is preferably 50 mol% or less, more preferably 40 mol% or less, and even more preferably 30 mol% or less, based on the total structural units of the copolymer (A) and the resin precursor (PA). The combination of these lower and upper limits may be any combination.

[0138] The total content of the copolymer (A) and the resin precursor (PA) optionally contained in the photosensitive resin composition or the photosensitive coloring composition is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 60 parts by mass or more, based on 100 parts by mass of the total of the copolymer (A), the resin precursor (PA), and the reactive diluent (B). The total content of the copolymer (A) and the resin precursor (PA) optionally contained in the photosensitive resin composition or the photosensitive coloring composition is preferably 90 parts by mass or less, more preferably 85 parts by mass or less, and even more preferably 80 parts by mass or less, based on 100 parts by mass of the total of the copolymer (A), the resin precursor (PA), and the reactive diluent (B). The combination of these lower limit values ​​and upper limit values ​​may be any combination. The total content of the copolymer (A) and the resin precursor (PA) optionally contained in the photosensitive resin composition or the photosensitive coloring composition is preferably 10 to 90 parts by mass, more preferably 30 to 85 parts by mass, and even more preferably 60 to 80 parts by mass, relative to 100 parts by mass of the total of the copolymer (A), the resin precursor (PA), and the reactive diluent (B). When the total content of the copolymer (A) and the resin precursor (PA) is 10 parts by mass or more, a photosensitive resin composition or a photosensitive coloring composition having better low-temperature curing properties and capable of forming a cured product with good solvent resistance can be obtained. When the total content of the copolymer (A) and the resin precursor (PA) is 90 parts by mass or less, the content of the reactive diluent (B) can be sufficiently secured, so that the strength of the cured product and the adhesion to the substrate are good.

[0139] The content of the resin precursor (PA) may be 0 to 20 parts by mass, 0 to 10 parts by mass, or 0 to 5 parts by mass, based on 100 parts by mass of the copolymer (A). From the viewpoint of improving the solvent resistance of the cured resin film, the resin precursor (PA) may not be contained.

[0140] [Reactive diluent (B)] The reactive diluent (B) is a monomer having at least one ethylenically unsaturated bond as a polymerizable functional group in the molecule. The reactive diluent (B) may be a monofunctional monomer or a polyfunctional monomer having a plurality of polymerizable functional groups. By containing the reactive diluent (B), the viscosity of the photosensitive resin composition or the photosensitive coloring composition can be set to an appropriate range according to the application. In addition, since the photosensitive resin composition or the photosensitive coloring composition contains the reactive diluent (B), it has good photocurability and can form a cured product having good strength and adhesion to the substrate. The reactive diluent (B) may be used alone or in combination of two or more kinds.

[0141] Examples of monofunctional monomers used as the reactive diluent (B) include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxymethyl (meth)acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 5 ... Examples of the monofunctional monomer include (meth)acrylates such as 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerin mono(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, glycidyl(meth)acrylate, 2,2,2-trifluoroethyl(meth)acrylate, 2,2,3,3-tetrafluoropropyl(meth)acrylate, and half(meth)acrylates of phthalic acid derivatives; aromatic vinyl compounds such as styrene, α-methylstyrene, α-chloromethylstyrene, and vinyltoluene; and carboxylic acid esters such as vinyl acetate and vinyl propionate. The monofunctional monomer may be used alone or in combination of two or more kinds.

[0142] Examples of polyfunctional monomers used as the reactive diluent (B) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylol glycol di(meth)acrylate, tetra ... dipentaerythritol tri(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryl Examples of the methacrylate include (meth)acrylates such as propyloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (for example, a reaction product of tolylene diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, or the like with 2-hydroxyethyl (meth)acrylate), and tris(hydroxyethyl)isocyanurate tri(meth)acrylate; aromatic vinyl compounds such as divinylbenzene, diallyl phthalate, and diallyl benzene phosphonate; dicarboxylic acid esters such as divinyl adipate; triallyl cyanurate, methylene bis(meth)acrylamide, and condensates of polyhydric alcohols and N-methylol (meth)acrylamide. The polyfunctional monomers may be used alone or in combination of two or more kinds.

[0143] Among these monomers, it is preferable to use a polyfunctional (meth)acrylate as the reactive diluent (B) because a photosensitive resin composition or a photosensitive coloring composition having good photocurability can be obtained. It is more preferable to use a polyfunctional (meth)acrylate having three or more functional groups, and it is even more preferable to use trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, or dipentaerythritol hexa(meth)acrylate.

[0144] The content of the reactive diluent (B) in the photosensitive resin composition or the photosensitive coloring composition is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and even more preferably 30 parts by mass or more, relative to the total 100 parts by mass of the copolymer (A), the resin precursor (PA), and the reactive diluent (B). The content of the reactive diluent (B) in the photosensitive resin composition or the photosensitive coloring composition is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 60 parts by mass or less, relative to the total 100 parts by mass of the copolymer (A), the resin precursor (PA), and the reactive diluent (B). The combination of these lower limit values ​​and upper limit values ​​may be any combination. The content of the reactive diluent (B) in the photosensitive resin composition or the photosensitive coloring composition is preferably 10 to 90 parts by mass, more preferably 15 to 70 parts by mass, and even more preferably 30 to 60 parts by mass, relative to the total 100 parts by mass of the copolymer (A), the resin precursor (PA), and the reactive diluent (B). When the content of the reactive diluent (B) is 10 parts by mass or more, the effect of containing the reactive diluent (B) becomes significant. When the content of the reactive diluent (B) is 90 parts by mass or less, the content of the copolymer (A) can be sufficiently secured, so that a photosensitive resin composition or a photosensitive coloring composition having better low-temperature curing property can be obtained.

[0145] [Photopolymerization initiator (C)] The photopolymerization initiator (C) is not particularly limited, but examples thereof include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,-1-(O-acetyloxime); benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin butyl ether; acetophenone compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4'-(1-t-butyldioxy-1-methylethyl)acetophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; 2-benzyl-2-dimethylamino-1-(4-morpholinyl)-1-methylethyl-2-phenylacetophenone; (1-phenyl)butanone-1; anthraquinone compounds such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; xanthone; thioxanthone compounds such as thioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; ketal compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone compounds such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, and 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone; and acylphosphine oxide-based photopolymerization initiators. The photopolymerization initiator (C) may be used alone or in combination of two or more.

[0146] The content of the photopolymerization initiator (C) in the photosensitive resin composition or the photosensitive coloring composition is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 10 parts by mass or more, based on 100 parts by mass of the total of the copolymer (A), the resin precursor (PA), and the reactive diluent (B). The content of the photopolymerization initiator (C) in the photosensitive resin composition or the photosensitive coloring composition is preferably 30 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, based on 100 parts by mass of the total of the copolymer (A), the resin precursor (PA), and the reactive diluent (B). The combination of these lower limit values ​​and upper limit values ​​may be any combination. The content of the photopolymerization initiator (C) in the photosensitive resin composition or the photosensitive coloring composition is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the total of the copolymer (A), the resin precursor (PA), and the reactive diluent (B). When the content of the photopolymerization initiator (C) is 0.1 parts by mass or more, a photosensitive resin composition or a photosensitive coloring composition having good photocurability can be obtained. When the content of the photopolymerization initiator (C) is 30 parts by mass or less, it is possible to prevent the physical properties of the cured product of the photosensitive resin composition or the photosensitive coloring composition from being adversely affected by the amount of the photopolymerization initiator (C) being too large.

[0147] Solvent As the solvent (D), the same solvent (PD) used in the production of the copolymer (A) can be used. The solvent (D) in the photosensitive resin composition or the photosensitive coloring composition and the solvent (PD) used in the production of the copolymer (A) may be the same or different.

[0148] The content of the solvent (D) in the photosensitive resin composition or the photosensitive coloring composition is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, based on 100 parts by mass of the total of the copolymer (A), the resin precursor (PA) and the reactive diluent (B). The content of the solvent (D) in the photosensitive resin composition or the photosensitive coloring composition is preferably 1,000 parts by mass or less, more preferably 800 parts by mass or less, based on 100 parts by mass of the total of the copolymer (A), the resin precursor (PA) and the reactive diluent (B). The combination of these lower limit values ​​and upper limit values ​​may be any combination. The content of the solvent (D) in the photosensitive resin composition or the photosensitive coloring composition is preferably 30 to 1,000 parts by mass, more preferably 50 to 800 parts by mass, based on 100 parts by mass of the total of the copolymer (A), the resin precursor (PA) and the reactive diluent (B). When the content of the solvent (D) is 30 parts by mass or more, the viscosity of the photosensitive resin composition or the photosensitive coloring composition can be set in an appropriate range. When the content of the solvent (D) is 1,000 parts by mass or less, the solvent (D) can be easily removed when removing the solvent (D) from the coating film formed by applying the photosensitive resin composition or the photosensitive coloring composition to a substrate.

[0149] Colorant (E) The photosensitive coloring composition may further contain a colorant (E). The photosensitive coloring composition containing the colorant (E) can be used as a material for a color filter.

[0150] The colorant (E) is not particularly limited as long as it is soluble or dispersible in the solvent (D), and examples thereof include dyes and pigments.

[0151] As the dye, from the viewpoints of solubility in the solvent (D) and the alkaline developer, interaction with other components in the photosensitive coloring composition, heat resistance, etc., it is preferable to use an acid dye having an acid group such as a carboxy group or a sulfo group, a salt of an acid dye with a nitrogen compound, or a sulfonamide adduct of an acid dye.

[0152] Examples of such dyes are: acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; solvent blue 38, 44, 70; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114 , 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; Food Yellow 3 and derivatives thereof. Among these, azo-based, xanthene-based, anthraquinone-based, or phthalocyanine-based acid dyes are preferred. The dyes can be used alone or in combination of two or more kinds.

[0153] Examples of pigments include yellow pigments such as CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, and 214; orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73; and CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 1 Examples of the pigments include red pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 60, etc.; violet pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38, etc.; green pigments such as CI Pigment Green 7, 36, 58, 59, etc.; brown pigments such as CI Pigment Brown 23, 25, etc.; black pigments such as CI Pigment Black 1, 7, carbon black, titanium black, iron oxide, etc. The pigments can be used alone or in combination of two or more kinds.

[0154] The colorant (E) can be appropriately determined depending on, for example, the color of the intended colored pattern (black matrix and pixels). The colorant (E) may be used alone or in combination of two or more. When two or more types of colorants (E) are used, a dye and a pigment may be used in combination.

[0155] When a pigment is used as the colorant (E), a known dispersant may be blended in the photosensitive coloring composition from the viewpoint of improving the dispersibility of the pigment. As the dispersant, it is preferable to use a polymer dispersant having excellent dispersion stability over time. Examples of the polymer dispersant include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic modified ester-based dispersants. As the polymer dispersant, those commercially available under the trade names EFKA (manufactured by EFKA CHEMICALS BV), Disperbyk (manufactured by BYK-Chemie), Disparlon (manufactured by Kusumoto Chemicals Co., Ltd.), and SOLSPERSE (manufactured by Lubrizol) may be used. The content of the dispersant may be appropriately set according to the type and amount of the pigment used as the colorant (E).

[0156] The content of the colorant (E) in the photosensitive coloring composition is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, relative to the total of 100 parts by mass of the copolymer (A), the resin precursor (PA), and the reactive diluent (B). The content of the colorant (E) in the photosensitive coloring composition is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 60 parts by mass or less, relative to the total of 100 parts by mass of the copolymer (A), the resin precursor (PA), and the reactive diluent (B). The combination of these lower limit values ​​and upper limit values ​​may be any combination. The content of the colorant (E) in the photosensitive coloring composition is preferably 3 to 80 parts by mass, more preferably 5 to 70 parts by mass, and even more preferably 10 to 60 parts by mass, relative to the total of 100 parts by mass of the copolymer (A), the resin precursor (PA), and the reactive diluent (B). When the content of the colorant (E) is 3 parts by mass or more, the effect of containing the colorant (E) becomes significant, and a photosensitive coloring composition suitable as a material for a color pattern of a color filter can be obtained. When the content of the colorant (E) is 80 parts by mass or less, the colorant (E) does not interfere with the curing property of the photosensitive coloring composition, and a photosensitive coloring composition having good low-temperature curing property can be obtained.

[0157] [Other ingredients] In addition to the copolymer (A), the solvent (D), the reactive diluent (B), the photopolymerization initiator (C), and the colorant (E) that is included as needed, the resin composition of one embodiment may contain known additives such as coupling agents, leveling agents, and thermal polymerization inhibitors as needed. The amount of the additives to be added is not particularly limited as long as it is within a range that does not inhibit the effects of the present invention.

[0158] <Method for producing photosensitive resin composition and photosensitive coloring composition> The photosensitive resin composition of one embodiment can be produced by a method of mixing the copolymer (A), the reactive diluent (B), the photopolymerization initiator (C), the solvent (D), and the resin precursor (PA) that is used optionally, using a known mixing device. The photosensitive coloring composition of one embodiment can be produced by a method of mixing the copolymer (A), the reactive diluent (B), the photopolymerization initiator (C), the solvent (D), the colorant (E), and the resin precursor (PA) that is used optionally, using a known mixing device.

[0159] When producing a photosensitive resin composition or a photosensitive coloring composition, a reaction liquid containing a copolymer (A) obtained by converting the structural unit (pb) to the structural unit (b) in the resin precursor composition, a solvent (PD), and an optional resin precursor (PA) may be used as it is as a raw material. In this case, the solvent (PD) contained in the reaction liquid can be used as a part or all of the solvent (D) contained in the photosensitive resin composition or the photosensitive coloring composition.

[0160] When producing a photosensitive resin composition or a photosensitive coloring composition, the copolymer (A) isolated by a known method from a reaction solution containing the above-mentioned copolymer (A) and a solvent (PD) may be used as a raw material.

[0161] The photosensitive resin composition or the photosensitive coloring composition contains a copolymer (A) having a structural unit (b) having a group represented by formula (1-1) or formula (1-2), a reactive diluent (B), and a photopolymerization initiator (C), and therefore, by irradiation with light, the reactive diluent (B) polymerizes together with the ethylenically unsaturated group contained in the structural unit (b) of the copolymer (A), thereby exhibiting good photocurability.

[0162] For these reasons, when a cured product is formed using a photosensitive resin composition or a photosensitive coloring composition, it can be cured at a lower temperature than when a conventional resin composition is used. Therefore, when a baking process is performed after a coating film formed on a substrate is exposed to light, the photosensitive resin composition or the photosensitive coloring composition can form a cured product having excellent solvent resistance, since the crosslinking reaction proceeds sufficiently even if the baking process temperature is lowered.

[0163] Therefore, when a cured product is formed using a photosensitive resin composition or a photosensitive coloring composition, less energy is required for heating to cure. In addition, by using a photosensitive resin composition or a photosensitive coloring composition, a cured product can be formed on a substrate having low heat resistance such as a resin substrate without causing any damage to the substrate. Furthermore, even when a photosensitive coloring composition having low heat resistance is used as the coloring agent (E), a cured product in which the inherent properties of the coloring agent (E) are exerted can be formed.

[0164] The photosensitive coloring composition can obtain a cured product having excellent solvent resistance even if the baking temperature is low, so that the colorant (E) is not easily eluted. Therefore, it is also possible to increase the content of the colorant (E) in the photosensitive coloring composition. A photosensitive coloring composition having a high content of the colorant (E) can be used, for example, as a material for the coloring pattern of a color filter to form a color filter having excellent color reproducibility.

[0165] The copolymer (A) contained in the photosensitive resin composition or the photosensitive coloring composition has a structural unit (a) having an acid group, so that the photosensitive resin composition or the photosensitive coloring composition has good alkaline developability. Since such a photosensitive resin composition or photosensitive coloring composition has excellent alkaline developability, for example, it is applied to a substrate to form a coating film, and exposed through a photomask corresponding to a predetermined pattern shape, and the unexposed part is developed with an alkaline aqueous solution, and then baked at a sufficiently low temperature to form a cured product having a predetermined pattern shape and excellent solvent resistance.

[0166] The photosensitive resin composition and the photosensitive coloring composition can be suitably used as a material for a color filter.

[0167] For these reasons, the photosensitive resin composition and the photosensitive coloring composition are extremely useful as materials for forming components of image display elements, such as pixels of color filters, black matrices, protective films for color filters, photospacers, protrusions for liquid crystal alignment, microlenses, and insulating films for touch panels.

[0168] <Cured resin film> The cured resin film in one embodiment is made of a cured product of a photosensitive resin composition or a photosensitive coloring composition.

[0169] The resin cured film can be produced, for example, by applying a photosensitive resin composition or a photosensitive coloring composition onto a substrate, volatilizing and removing the solvent (D) to form a coating film, exposing the coating film to light to cure it, and then carrying out a baking treatment.

[0170] When forming a resin cured film having a predetermined pattern shape, for example, the following method can be used. That is, a photosensitive resin composition or a photosensitive coloring composition is applied onto a substrate, and the solvent (D) is removed by volatilization to form a coating film. Next, the coating film is exposed to light through a photomask having a predetermined pattern shape to photocure the exposed portion. Next, the unexposed portion of the coating film is developed with an alkaline aqueous solution. Thereafter, the developed coating film is baked to form a resin cured film having a predetermined pattern shape.

[0171] In producing the cured resin film, known methods can be used for the coating method of the photosensitive resin composition or the photosensitive coloring composition, the exposure method of the coating film, and the development method.

[0172] The conditions of the baking treatment carried out when producing a resin cured film can be appropriately determined according to the composition of the photosensitive resin composition or the photosensitive coloring composition, the film thickness of the coating film, the material of the substrate, and the like. The baking treatment can be carried out at a temperature of, for example, 70°C to 250°C. When the baking treatment temperature is 70°C or higher, the crosslinking reaction by the Diels-Alder reaction between the dienophile moiety of the structural unit (b) and the conjugated diene moiety of the structural unit (c) is promoted. As a result, a good degree of curing is obtained, and a cured product having excellent solvent resistance is obtained. The baking treatment temperature is preferably 75°C or higher, more preferably 80°C or higher. When the baking treatment temperature is 250°C or lower, it is a condition that can be endured by a material with low heat resistance, and discoloration of the photosensitive resin composition or the photosensitive coloring composition can be suppressed, which is preferable. The photosensitive resin composition and the photosensitive coloring composition have good low-temperature curing properties. Therefore, the temperature of the baking treatment can be set to 160°C or less depending on the heat resistance of the base material on which the resin cured film is formed. For example, when a resin substrate is used as the base material, the temperature may be set to 150°C or less, 120°C or less, or 100°C or less.

[0173] The baking treatment carried out when producing a cured resin film can be carried out for, for example, 10 minutes to 4 hours, preferably 20 minutes to 2 hours, and can be appropriately determined depending on the composition of the photosensitive resin composition or the photosensitive coloring composition, the baking temperature, the film thickness of the coating film, etc.

[0174] The cured resin film is made of a cured product of a photosensitive resin composition or a photosensitive coloring composition, and therefore can be produced by a baking process at a low temperature and has excellent solvent resistance.

[0175] <Color filter> The color filter of one embodiment has a color pattern made of a cured product of a photosensitive coloring composition. The color filter preferably has a color pattern made of a cured product of a photosensitive coloring composition containing 10 to 90 parts by mass of copolymer (A), 10 to 90 parts by mass of reactive diluent (B), 0.1 to 30 parts by mass of photopolymerization initiator (C), 30 to 1,000 parts by mass of solvent (D), and 3 to 80 parts by mass of colorant (E) relative to a total of 100 parts by mass of copolymer (A), optional resin precursor (PA), and reactive diluent (B).

[0176] The color filter may include, for example, a substrate, RGB pixels formed thereon, a black matrix formed at the boundaries of each pixel, and a protective film formed on the pixels and the black matrix.

[0177] In the color filter, the pixels and the black matrix are color patterns formed of the cured product of the above-mentioned photosensitive coloring composition. In the color filter, the components other than the materials of the pixels and the black matrix may be any known materials.

[0178] The substrate used for the color filter is not particularly limited, and a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate, a printed wiring substrate, an array substrate, etc. can be used as appropriate depending on the application.

[0179] <Color filter manufacturing method> Next, an exemplary method for manufacturing a color filter will be described. First, a colored pattern is formed on a substrate. Specifically, a colored pattern that will become a black matrix formed at the boundaries of each pixel, and a colored pattern that will become each of the RGB pixels are sequentially formed on the substrate by the method described below.

[0180] The colored pattern can be formed by photolithography. Specifically, a photosensitive colored composition is applied onto a substrate to form a coating film. The coating film is then exposed to light through a photomask having a predetermined pattern shape to photocure the exposed portion. The unexposed portion of the coating film is then developed with an alkaline aqueous solution. The developed coating film is then subjected to a baking treatment to form a colored pattern having a predetermined pattern shape.

[0181] The method for applying the photosensitive coloring composition is not particularly limited, but any known method such as screen printing, roll coating, curtain coating, spray coating, or spin coating can be used.

[0182] After the photosensitive coloring composition is applied onto the substrate, the substrate may be heated using a heating means such as a circulation oven, an infrared heater, or a hot plate, if necessary, to volatilize and remove the solvent (D) contained in the coating film. The conditions for heating the substrate to remove the solvent (D) are not particularly limited, and may be appropriately set according to the material of the substrate, the composition of the photosensitive coloring composition, the thickness of the coating film, etc. The substrate may be heated, for example, at a temperature of 50°C to 120°C for 30 seconds to 30 minutes.

[0183] Next, the coating film thus formed is irradiated with active energy rays such as ultraviolet rays and excimer laser light through a negative photomask, partially exposed, and photocured in the exposed areas. The amount of active energy radiation irradiated to the coating film may be appropriately selected depending on the composition of the photosensitive coloring composition, and may be, for example, 30 to 2000 mJ / cm. 2 The light source used for exposure is not particularly limited, but may be a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like.

[0184] The alkaline aqueous solution used for developing the coating film is not particularly limited, but may be an aqueous solution of an inorganic alkaline compound such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, or potassium hydroxide; an aqueous solution of an amine compound such as ethylamine, diethylamine, or dimethylethanolamine; an aqueous solution of a quaternary ammonium salt such as sulfate, hydrochloride, or p-toluenesulfonate of tetramethylammonium; an aqueous solution of an aniline compound or a salt thereof such as 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and sulfate, hydrochloride, or p-toluenesulfonate thereof; an aqueous solution of a p-phenylenediamine compound or a salt thereof. In addition, additives such as a defoamer and a surfactant may be added to the alkaline aqueous solution as necessary.

[0185] After the coating film is developed using the above-mentioned aqueous alkaline solution, it is preferable to wash the coating film with water and dry it.

[0186] The conditions of the baking treatment carried out when producing a color filter can be appropriately determined depending on the composition of the photosensitive coloring composition, the thickness of the coating film, the material of the substrate, etc. The baking temperature can be, for example, 70°C to 210°C. When the baking temperature is 70°C or higher, good curability is obtained, and a cured product having excellent solvent resistance is obtained. The baking temperature is preferably 75°C or higher, more preferably 80°C or higher. When the baking temperature is 210°C or lower, it is preferable because a material with low heat resistance, such as a substrate with low heat resistance, can be used as the material of the color filter.

[0187] When a color filter color pattern is formed using a conventional photosensitive coloring composition, if the baking temperature is set to 200° C. or less, the color pattern will lack solvent resistance. In contrast, the photosensitive coloring composition of one embodiment has good low-temperature curing properties, so the baking temperature can be lowered compared to when a conventional photosensitive coloring composition is used while ensuring the solvent resistance of the color pattern. Specifically, the baking temperature can be set to 160° C. or less depending on the heat resistance of the substrate on which the resin cured film is formed. For example, when a color pattern is formed using a resin substrate as the substrate, it may be set to 150° C. or less, 120° C. or less, or 100° C. or less.

[0188] The baking treatment carried out when producing a color filter can be carried out for, for example, 10 minutes to 4 hours, preferably 20 minutes to 2 hours, and can be appropriately determined depending on the composition of the photosensitive coloring composition, the temperature of the baking treatment, the thickness of the coating film, etc.

[0189] The photosensitive coloring composition has good photocurability and low-temperature curability. Therefore, when forming a colored pattern using the photosensitive coloring composition of one embodiment, when the baking temperature is the same as when forming a colored pattern using a conventional photosensitive coloring composition, the baking time can be shortened, and a color filter can be efficiently formed.

[0190] Using the above-mentioned method for manufacturing a colored pattern, a colored pattern that will become each of the RGB pixels and a colored pattern that will become a black matrix formed at the boundaries of each pixel are formed, and then a protective film is formed on the colored pattern (each of the RGB pixels and the black matrix).

[0191] The method for producing the protective film is not particularly limited, and the protective film may be formed using the photosensitive resin composition of one embodiment, or may be formed using known materials and known methods.

[0192] Through the above steps, a color filter is obtained.

[0193] The color filter has a color pattern made of the cured product of the above-mentioned photosensitive coloring composition. Therefore, the color pattern in the color filter can be formed by a method of performing a baking treatment at a low temperature. Therefore, the energy required for the baking treatment can be reduced.

[0194] In addition, it is possible to use a colorant (E) having low heat resistance as the colorant contained in the photosensitive coloring composition used as a material for the color filter. This allows for a wide range of options for the colorant (E). Therefore, for example, it is possible to form a color filter that contains a colorant (E) having low heat resistance and has a color pattern that exhibits the inherent properties of the colorant (E) having low heat resistance.

[0195] Furthermore, the colored pattern in the color filter can be formed on a substrate having low heat resistance such as a resin substrate without interfering with the substrate. Therefore, the number of substrates that can be used can be increased. Specifically, for example, since the color filter can be formed on a substrate having low heat resistance such as a resin substrate, the display can be made flexible. In addition, the colored pattern in the color filter has excellent solvent resistance, so there is little color change.

[0196] Here, the photosensitive coloring composition containing the photopolymerization initiator (C) is used to produce a colored pattern by photocuring the photosensitive coloring composition. However, for example, instead of the photopolymerization initiator (C) contained in the photosensitive coloring composition, a photosensitive coloring composition containing a curing accelerator and a known epoxy resin is used, and a colored pattern made of a cured product of the photosensitive coloring composition containing the copolymer (A) may be formed by applying the composition to a substrate by an inkjet method and then heating the composition.

[0197] <Image display element> The image display element of one embodiment includes a color filter. In the image display element, a known configuration other than the color filter can be adopted. Specific examples of the image display element include a liquid crystal display element, an organic EL display element, a solid-state imaging element such as a CCD element and a CMOS element, and the like.

[0198] The components of the image display element other than the color filter can be manufactured by known methods. For example, when manufacturing a liquid crystal display element as the image display element, it can be manufactured by the following method. First, a color filter is formed on a substrate by the above-mentioned method. Then, electrodes, spacers, etc. are formed in sequence on the substrate having the color filter. Next, electrodes, etc. are formed on another substrate, and the substrate having the color filter is placed opposite to the other substrate and bonded to the other substrate. Then, a predetermined amount of liquid crystal is injected between the opposing substrates and sealed.

[0199] The image display device has a color filter having excellent solvent resistance, and therefore the color change is small. EXAMPLES

[0200] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0201] A synthesis example of the copolymer (A) is shown below.

[0202] [Example 1 (Synthesis Example 1)] (Synthesis of resin precursor (PA)) Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 92.7 g of propylene glycol monomethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed as a solvent (PD), and the mixture was stirred while replacing with nitrogen gas and heated to 78°C.

[0203] Next, 5.8 g (20 mol%) of methacrylic acid as a monomer (ma), 22.3 g (20 mol%) of 2-[(diethyl malate)carbonylamino]ethyl acrylate as a monomer (m-pb), 17.1 g (20 mol%) of 2-[(2-furanylmethoxy)carbonylamino]ethyl methacrylate as a monomer (mc), 24.8 g (40 mol%) of 2-ethylhexyl acrylate as a monomer (md), 21.0 g (30 parts by mass relative to a total of 100 parts by mass of the monomer components) of propylene glycol monomethyl ether as a solvent (PD), and 11.2 g (16 parts by mass relative to a total of 100 parts by mass of the monomer components) of 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) as a polymerization initiator were mixed to prepare a raw material monomer solution.

[0204] The entire amount of the raw material monomer solution was dropped into the solvent (PD) in a flask under normal pressure and nitrogen gas atmosphere using a dropping funnel over a period of one hour. After the dropping was completed, the solution in the flask was stirred and polymerized at 78°C for three hours to obtain a liquid containing the resin precursor (PA) and the solvent (PD).

[0205] (Preparation of Resin Precursor Composition) To a liquid containing the resin precursor (PA) and the solvent (PD) in a flask at normal pressure and under a nitrogen gas atmosphere, 0.2 g (0.2 parts by mass relative to 100 parts by mass of the total of the monomer components of the resin precursor (PA) and the polymerization initiator) of hydroquinone monomethyl ether (MEHQ) as a polymerization inhibitor and 0.7 g (0.8 parts by mass relative to 100 parts by mass of the total of the monomer components of the resin precursor (PA) and the polymerization initiator) of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) (manufactured by San-Apro Co., Ltd.) as a basic catalyst were added, thereby obtaining a resin precursor composition.

[0206] (Synthesis of copolymer (A)) In a flask under normal pressure and in a nitrogen gas atmosphere, the resin precursor composition was stirred and held at 78°C for 30 minutes to convert the structural unit (pb) having a group represented by formula (1) contained in the resin precursor (PA) into a structural unit (b) having a group represented by formula (1-1) or formula (1-2). This resulted in a reaction liquid containing the copolymer (A), the resin precursor (PA), and the solvent (PD). The weight average molecular weight, ethylenically unsaturated group equivalent, and acid value of the mixture of the copolymer (A) and the resin precursor (PA) were measured by the above-mentioned methods and are listed in Table 1.

[0207] To the reaction liquid containing the copolymer (A), resin precursor (PA), and solvent (PD) thus obtained, propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as solvent (D) so that the components other than the solvent were 35 mass %. Thus, a liquid containing the copolymer (A) of Example 1 was obtained.

[0208] [Examples 2 to 7 (Synthesis Examples 2 to 7) and Comparative Example 1 (Comparative Synthesis Example 1)] Liquids containing copolymer (A) of Examples 2 to 9 and liquid containing copolymer (cA) of Comparative Example 1 were obtained in the same manner as in Example 1, except that the monomers and blending amounts shown in Table 1 were used. The weight average molecular weight, ethylenically unsaturated group equivalent, and acid value of the mixtures of copolymer (A) and resin precursor (PA) of Examples 2 to 9 and the mixture of copolymer (cA) and resin precursor (cPA) of Comparative Example 1 were measured by the above-mentioned methods and are shown in Table 1.

[0209] [Comparative Example 2 (Comparative Synthesis Example 2)] Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 78.3 g of propylene glycol monomethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed as a solvent (PD), and the mixture was stirred while replacing with nitrogen gas and heated to 78°C.

[0210] Next, 8.7 g (30 mol%) of methacrylic acid as monomer (ma), 25.6 g (30 mol%) of 2-[(2-furanylmethoxy)carbonylamino]ethyl acrylate as monomer (mc), 24.8 g (40 mol%) of 2-ethylhexyl acrylate as monomer (md), and 9.5 g (16 parts by mass per 100 parts by mass of the total of the monomer components) of 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator were mixed to prepare a raw monomer solution.

[0211] The entire amount of the raw material monomer solution prepared was dropped into the solvent (PD) in a flask at normal pressure in a nitrogen gas atmosphere using a dropping funnel over 1 hour. After the dropping was completed, the solution in the flask was stirred and polymerized at 78°C for 3 hours to obtain a solution containing the copolymer (cA) and the solvent (PD). The weight average molecular weight and acid value of the copolymer (cA) were measured by the above-mentioned method and are listed in Table 1.

[0212] To the reaction liquid containing the copolymer (cA) and solvent (PD) thus obtained, propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as solvent (D) so that the components other than the solvent were 35 mass %. Thus, a liquid containing the copolymer (cA) of Comparative Example 2 was obtained.

[0213] [Table 1]

[0214] The compounds used in Table 1 were as follows: MAA: Methacrylic acid (Kuraray Co., Ltd.) AOI-MDE: Karenz (trademark) AOI-MDE, 2-[(diethyl malate)carbonylamino]ethyl acrylate (manufactured by Resonac Co., Ltd.) MOI-FF: 2-[(2-furanylmethoxy)carbonylamino]ethyl methacrylate (manufactured by Resonac Co., Ltd.) AOI-FF: 2-[(2-furanylmethoxy)carbonylamino]ethyl acrylate (manufactured by Resonac Co., Ltd.) FMA: Furfuryl methacrylate (Tokyo Chemical Industry Co., Ltd.) 2EHA: 2-Ethylhexyl acrylate (manufactured by Toagosei Co., Ltd.) TCDMA: Tricyclodecanyl methacrylate (manufactured by Resonac Co., Ltd.) MMA: Methyl methacrylate (manufactured by Mitsubishi Chemical Corporation) DBU: 1,8-diazabicyclo[5.4.0]-7-undecene (manufactured by San-Apro Co., Ltd.)

[0215] [Examples 8 to 14, Comparative Examples 3 to 4] Mixtures of copolymers (A) and resin precursors (PA) of Synthesis Examples 1 to 7 shown in Table 2 or mixtures of copolymers (cA) and resin precursors (cPA) of Comparative Synthesis Example 1 or copolymers (cA) of Comparative Synthesis Example 2, dipentaerythritol pentaacrylate (manufactured by Toa Gosei Co., Ltd.) as reactive diluent (B), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl-]-,-1-(O-acetyloxime) (manufactured by Ciba Japan Co., Ltd.) as photopolymerization initiator (C), mixtures of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether (338 parts by mass and 257 parts by mass, respectively) as solvent (D), and Valifath Blue 2620 (phthalocyanine dye, manufactured by Orient Chemical Industry Co., Ltd.) as colorant (E) were mixed in the ratios shown in Table 2, and photosensitive coloring compositions of Examples 8 to 14 and Comparative Examples 3 to 4 were prepared.

[0216] The amount of the solvent is not included in the mixture of the copolymer (A) and the resin precursor (PA), the mixture of the copolymer (cA) and the resin precursor (cPA), or the amount of the copolymer (cA) shown in Table 2. The amount of the solvent (D) shown in Table 2 is the sum of the amount of the solvent contained in the liquid containing the copolymer (A) or (cA) obtained in Synthesis Examples 1 to 7 and Comparative Synthesis Examples 1 to 2, and the amount of the solvent added when preparing the photosensitive coloring composition.

[0217] [Table 2]

[0218] [Evaluation of Solvent Resistance] The solvent resistance was evaluated based on the remaining film rate.

[0219] (Remaining film rate) The photosensitive coloring compositions of Examples 8 to 14 and Comparative Examples 3 to 4 were each applied by spin coating onto a square glass substrate (alkali-free glass substrate) measuring 5 cm in length and 5 cm in width in plan view, so that the thickness after exposure was 2.5 μm, to form a coating film. The coating film was then heated at 100° C. for 3 minutes to volatilize and remove the solvent (D) in the coating film.

[0220] Next, the coating film was exposed to ultraviolet light with a wavelength of 365 nm and an energy dose of 100 mJ / cm 2 The coating was exposed to light at 100°C for 20 minutes to cure the exposed portion. The thickness of the cured film was measured with a step gauge. The thickness at this time was designated as X.

[0221] The cured film was then immersed in 20 g of propylene glycol monomethyl ether acetate (PGMEA) at 23° C. for 15 minutes. The immersed coating film was vacuum dried at 40° C. for 30 minutes, and the thickness of the coating film was measured with a step gauge. The thickness at this time was designated as Y.

[0222] The ratio of the thickness Y of the cured film after immersion in PGMEA to the thickness X of the cured film before immersion in PGMEA was calculated as the film remaining ratio using the following formula, and the solvent resistance of the cured film was evaluated. In other words, the closer the film remaining ratio is to 100%, the better the solvent resistance of the cured film. A film remaining ratio of 80% or more was set as the pass mark for evaluation. The film remaining ratios of the cured films are shown in Table 2. Remaining film rate=(Y / X)×100 (%)

[0223] As shown in Table 2, the cured films of the resin compositions of Examples 8 to 14 had a residual film rate (%) of 85% or more after immersion in PGMEA, and had good solvent resistance even when the baking temperature was as low as 100°C.

[0224] [Evaluation of developability] The developability was evaluated based on the solubility and adhesion of the cured film.

[0225] (Solubility) The photosensitive coloring compositions prepared in Examples 8 to 14 and Comparative Examples 3 to 4 were each applied onto a 5 cm square glass substrate (alkali-free glass substrate) by spin coating so that the thickness after exposure was 1.5 μm (application step). The glass substrate onto which the photosensitive coloring composition was applied was heated at 100° C. for 3 minutes to volatilize the solvent and dry the coating film (pre-baking step).

[0226] Next, an ultra-high pressure mercury lamp was used to irradiate 100 mJ / cm 2 The surface of the dried coating film was irradiated with light through a photomask (exposure step). The exposure step was performed by placing a photomask at a position 100 μm away from the coating film. The photomask used had a line and space pattern with a width of 3 to 100 μm. Next, Semiclean DL-A10 developer (manufactured by Yokohama Yushi Kogyo Co., Ltd.) (diluted 300 times) was sprayed onto the surface of the coating film for 60 seconds under conditions of a temperature of 23° C. and a pressure of 0.1 MPa to remove the unexposed area (development step). The dissolved form of the coating film when the developer was sprayed was observed, and the solubility was evaluated according to the following criteria. The results are shown in Table 2. 1: No residue in unexposed areas, no powder in developer, and good pattern shape 2: No residue in unexposed areas, but powder is seen in the developer, and the pattern shape is relatively good. 3: Residue remains in the unexposed areas, and there are some areas where the pattern shape is missing. 4: The film peels off in the exposed area, leaving no pattern behind

[0227] (Adhesion) The glass substrate having the coating film after the development step was left in a dryer at 100°C for 30 minutes to thermally cure the coating film (post-bake step), thereby obtaining a colored pattern. The colored pattern thus obtained was observed using a microscope, and the adhesion was evaluated based on the minimum line width that could be developed (minimum development dimension (μm)). The results are shown in Table 2. Comparative Examples 3 and 4 were not evaluated because the pattern shape was chipped or not remaining. [Industrial Applicability]

[0228] According to the present disclosure, a photosensitive resin composition is provided that contributes to improving developability and gives a resin cured film having excellent solvent resistance. Also, according to the present disclosure, an image display element is provided that has a color filter having a color pattern made of a resin cured film having excellent solvent resistance. The photosensitive resin composition and the photosensitive coloring composition can be preferably used as materials for transparent films, protective films, insulating films, overcoats, photospacers, black matrices, black column spacers, resists for color filters, and the like.

Claims

1. A structural unit (a) having an acid group; A structural unit (b) having a group represented by the following formula (1-1) or the following formula (1-2), A structural unit (c) having a conjugated diene moiety in a side chain; having Optionally, A structural unit (pb) having a group represented by the following formula (1): A copolymer having the formula: 【Chemistry 1】 (In formula (1-1), R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a linking site with a residue obtained by removing the group of formula (1-1) from the structural unit (b). 【Chemistry 2】 (In formula (1-2), R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 4 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a linking site with a residue obtained by removing the group of formula (1-2) from the structural unit (b). 【Chemistry 3】 (In formula (1), R 1 and R 4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a linking site with a residue obtained by removing the group of formula (1) from the structural unit (pb).

2. the structural unit (c) having a conjugated diene moiety in a side chain is a structural unit derived from a conjugated diene-containing monomer (m-c), The copolymer according to claim 1 , wherein the conjugated diene moiety is a furan ring.

3. The copolymer according to claim 2, wherein the conjugated diene-containing monomer (mc) is a furan ring-containing (meth)acrylate.

4. R contained in the structural unit (b) 1 and R 4 are each independently a hydrocarbon group having 1 to 3 carbon atoms; R 2 and R 3 The copolymer according to any one of claims 1 to 3, wherein each of independently represents a hydrogen atom or a methyl group.

5. The copolymer according to any one of claims 1 to 3, further comprising a structural unit (d) derived from an alkyl (meth)acrylate in which the alkyl group has 1 to 12 carbon atoms.

6. The copolymer according to any one of claims 1 to 3, having an acid value of 10 to 300 KOHmg / g.

7. The weight average molecular weight is 1,000 to 50,000; The copolymer according to any one of claims 1 to 3, having an ethylenically unsaturated group equivalent of 300 to 10,000 g / mol.

8. The content of the structural unit (a) is 5 to 50 mol % based on all structural units of the copolymer, the total content of the structural units (b) and (pb) is 5 to 50 mol % based on all structural units of the copolymer; The copolymer according to any one of claims 1 to 3, wherein the content of the structural unit (c) is 5 to 50 mol % of all structural units in the copolymer.

9. Further having a structural unit (d) derived from an alkyl (meth)acrylate in which the alkyl group has 1 to 12 carbon atoms, The copolymer according to any one of claims 1 to 3, wherein the content of the structural unit (d) is 1 to 50 mol % based on all structural units of the copolymer.

10. The copolymer according to any one of claims 1 to 3, wherein the content ratio (molar ratio) of the structural unit (b) to the structural unit (c) is 10:90 to 90:

10.

11. The copolymer (A) according to any one of claims 1 to 3, A reactive diluent (B); A photopolymerization initiator (C); A solvent (D), Optionally, a resin precursor (PA), A photosensitive resin composition comprising: The resin precursor (PA) A structural unit (a) having an acid group; A structural unit (pb) having a group represented by the following formula (1), A structural unit (c) having a conjugated diene moiety in a side chain; A photosensitive resin composition which is a copolymer containing the following: 【Chemistry 4】 (In formula (1), R 1 and R 4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a linking site with a residue obtained by removing the group of formula (1) from the structural unit (pb).

12. the content of the structural unit (b) is 0.1 to 45 mol % based on all structural units of the copolymer (A) and the resin precursor (PA), the content of the structural unit (pb) is 0 to 49 mol % in all structural units of the copolymer (A) and the resin precursor (PA), The photosensitive resin composition according to claim 11, wherein the total content of the structural unit (b) and the structural unit (pb) is 5 to 50 mol% of all structural units of the copolymer (A) and the resin precursor (PA).

13. With respect to 100 parts by mass in total of the copolymer (A), the resin precursor (PA), and the reactive diluent (B), The copolymer (A) and the resin precursor (PA) are contained in a total of 10 parts by mass to 90 parts by mass, The reactive diluent (B) is contained in an amount of 10 parts by mass to 90 parts by mass, The photopolymerization initiator (C) is contained in an amount of 0.1 to 30 parts by mass, The photosensitive resin composition according to claim 11, comprising 30 parts by mass to 1,000 parts by mass of the solvent (D).

14. A photosensitive coloring composition comprising the photosensitive resin composition according to claim 11 and a colorant (E).

15. With respect to 100 parts by mass in total of the copolymer (A), the resin precursor (PA), and the reactive diluent (B), The copolymer (A) and the resin precursor (PA) are contained in a total of 10 parts by mass to 90 parts by mass, The reactive diluent (B) is contained in an amount of 10 parts by mass to 90 parts by mass, The photopolymerization initiator (C) is contained in an amount of 0.1 to 30 parts by mass, The solvent (D) is contained in an amount of 30 parts by mass to 1,000 parts by mass, The colorant (E) is contained in an amount of 3 parts by mass to 80 parts by mass. The photosensitive coloring composition according to claim 14.

16. A cured resin film comprising a cured product of the photosensitive resin composition according to claim 11.

17. A cured resin film comprising a cured product of the photosensitive coloring composition according to claim 14.

18. A color filter having a colored pattern comprising a cured product of the photosensitive coloring composition according to claim 14.

19. An image display device comprising the color filter according to claim 18.

20. The method includes a step of converting a resin precursor (PA) into a copolymer (A) in the presence of a basic catalyst and a solvent (PD), The resin precursor (PA) A structural unit (a) having an acid group; A structural unit (pb) having a group represented by the following formula (1), A structural unit (c) having a conjugated diene moiety in a side chain; having The copolymer (A) is A structural unit (a) having an acid group; A structural unit (b) having a group represented by the following formula (1-1) or the following formula (1-2), A structural unit (c) having a conjugated diene moiety in a side chain; A method for producing a copolymer (A) having the following formula: 【Chemistry 5】 (In formula (1), R 1 and R 4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a linking site with a residue obtained by removing the group of formula (1) from the structural unit (pb). 【Chemistry 6】 (In formula (1-1), R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a linking site with a residue obtained by removing the group of formula (1-1) from the structural unit (b). 【Chemistry 7】 (In formula (1-2), R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms; R 4 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a linking site with a residue obtained by removing the group of formula (1-2) from the structural unit (b).

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