Resin composition, modified resin composition, and method for producing modified resin composition

Abstract

Provided is a resin composition containing a copolymer (A), a basic catalyst (B), and a solvent (C), wherein the copolymer (A) contains a structural unit (a) having an acid group and a structural unit (pb) having a group represented by formula (1) (In formula (1), R1 and R4 each independently are a hydrogen atom or a C1-20 hydrocarbon group, R2 and R3 each independently are a hydrogen atom or a C1-20 hydrocarbon group, and * represents a linking site with a residue obtained by removing the group of formula (1) from the structural unit (pb).), and the basic catalyst (B) has a pKa (acidity constant) at 25°C of 4-12.

Description

Resin composition, modified resin composition, and method for producing modified resin composition

[0001] The present disclosure relates to a resin composition, a modified resin composition, a photosensitive resin composition, a photosensitive colored composition, a cured resin film, an image display element, a method for producing a resin composition, and a method for producing a modified resin composition.

[0002] In recent years, from the viewpoint of resource and energy conservation, photosensitive resin compositions that can be cured by active energy rays such as ultraviolet rays and electron beams have been widely used in fields such as various coatings, printing, paints, and adhesives. 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 as solder resists and color filter resists. The properties required for curable photosensitive resin compositions are becoming increasingly diverse and sophisticated, and among these, short-time curing properties that take productivity into consideration and low-temperature curing properties that suppress thermal damage to applied components are particularly 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 boundaries of 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 the black matrix, pixels, and protective film on the transparent substrate. Various methods have been proposed for forming pixels and black matrices (hereinafter, the pixels and black matrix are referred to as "colored patterns"). Among these, the pigment / dye dispersion method, which uses a photosensitive resin composition as a resist and produces a colored pattern by a photolithography process that involves repeated 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, a photosensitive resin composition used in a photolithography process contains an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a colorant, and a solvent. While the pigment / dye dispersion method has the above advantages, it often has a problem in 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 and are compatible 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 that can be suitably used for applications such as color filters.

[0006] Japanese Patent Application Laid-Open No. 2021-102759

[0007] However, in recent years, there has been a demand for even lower temperature curing properties, which may result in insufficient film curing and a trade-off in reduced solvent resistance. Therefore, even when cured at low temperatures, the resulting 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 resin composition that can efficiently introduce ethylenically unsaturated groups into the resin. It also provides a modified resin composition that contributes to improved developability and provides a cured resin film with excellent solvent resistance, as well as a photosensitive resin composition and a photosensitive coloring composition that use the same. The present disclosure also provides a cured resin film with excellent solvent resistance, and an image display device that includes the same.

[0009] The present disclosure includes the following aspects: [1] A resin composition containing a copolymer (A), a basic catalyst (B), and a solvent (C), wherein the copolymer (A) is a copolymer containing a structural unit (a) having an acid group, and a structural unit (pb) having a group represented by the following formula (1), and the basic catalyst (B) is a basic catalyst having a pKa (acidity constant) at 25°C of 4 to 12: (In formula (1), R １ and R ４ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and 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) from the structural unit (pb). [2] A modified resin composition comprising: a modified copolymer (A2); a basic catalyst (B); and a solvent (C), wherein the modified copolymer (A2) 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 (b) having a group represented by the following formula (1-1) or (1-2), and the basic catalyst (B) is a basic catalyst having a pKa (acidity constant) at 25°C of 4 to 12. (In formula (1), R １ and R ４ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and 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) from the structural unit (pb). (In formula (1-1), R １ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and 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). (In formula (1-2), R ２ and R ３are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and 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 structural unit (b). [3] The modified resin composition according to [2], wherein the basic catalyst (B) is at least one selected from the group consisting of pyridine, pyridine derivatives, and imidazole compounds. [4] The modified resin composition according to [2] or [3], wherein the basic catalyst (B) is at least one selected from pyridine, 4-dimethylaminopyridine, 1,2-dimethylimidazole, triethylamine, and 1,4-diazabicyclo[2.2.2]octane. [5] The modified resin composition according to any one of [2] to [4], wherein the ethylenically unsaturated group equivalent of the modified copolymer (A2) is 300 to 10,000 g / mol. [6] A photosensitive resin composition comprising the modified resin composition according to any one of [2] to [5], a reactive diluent (D), and a photopolymerization initiator (E). [7] A photosensitive coloring composition comprising the modified resin composition according to any one of [2] to [5], a reactive diluent (D), a photopolymerization initiator (E), and a colorant (F). [8] A cured resin film comprising a cured product of the photosensitive resin composition according to [6]. [9] A cured resin film comprising a cured product of the photosensitive coloring composition according to [7].

[10] A color filter having a color pattern comprising a cured product of the photosensitive coloring composition according to [7].

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

[10] .

[12] A method for producing a resin composition, comprising: a step (I) of preparing a resin composition containing a copolymer (A), a basic catalyst (B), and a solvent (C), wherein the copolymer (A) is a copolymer containing a structural unit (a) having an acid group, and a structural unit (pb) having a group represented by the following formula (1), and the basic catalyst (B) is a basic catalyst having a pKa (acidity constant) at 25°C of 4 to 12: (In formula (1), R １ and R ４ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and 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) from the structural unit (pb).)

[13] A method for producing a modified resin composition, comprising a heating step (II) of holding the resin composition obtained by the production method according to

[12] at 50 to 100°C for 30 to 300 minutes, wherein in the heating step (II), the copolymer (A) is converted into a modified copolymer (A2), and the modified copolymer (A2) contains: a structural unit (a) having an acid group; a structural unit (pb) having a group represented by the following formula (1): (In formula (1), R １ and R ４ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and 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) from the structural unit (pb). (In formula (1-1), R １ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and 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). (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, and R ４ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents the linking site with the residue obtained by removing the group of formula (1-2) from the structural unit (b).

[0010] According to the present disclosure, it is possible to provide a resin composition that can efficiently introduce ethylenically unsaturated groups into a resin. Furthermore, it is possible to provide a modified resin composition that contributes to improving developability and gives a cured resin film having excellent solvent resistance, as well as a photosensitive resin composition and a photosensitive coloring composition using the modified resin composition. It is also possible to provide a cured resin 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.

[0011] Hereinafter, embodiments of the present invention will be described in detail, but 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. When multiple upper or lower limits are listed, numerical ranges can be created using all combinations of the upper and lower limits. Similarly, when multiple numerical ranges are listed, separate numerical ranges can be created by individually selecting and combining the upper and lower limits from those numerical ranges.

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

[0014] In this specification, the term "ethylenically unsaturated bond" refers to a double bond formed between carbon atoms excluding carbon atoms forming an aromatic ring, and the term "ethylenically unsaturated group" refers to 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] <Resin Composition> A resin composition of one embodiment contains a copolymer (A), a basic catalyst (B), and a solvent (C).

[0017] [Copolymer (A)] The copolymer (A) does not contain the structural unit (b) described below, but contains a structural unit (a) having an acid group and a structural unit (pb) having a group represented by the following formula (1). When the copolymer (A) has the structural unit (pb) having a group represented by the following formula (1), conversion to the structural unit (b) proceeds under the action of the basic catalyst (B) described below, and an ethylenically unsaturated group is introduced into the copolymer (A). By using this in a photosensitive resin composition, it is possible to obtain a cured resin film with improved developability and good solvent resistance. (In formula (1), R １ and R ４ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and 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) from the structural unit (pb).

[0018] The copolymer (A) may further contain, as necessary, a structural unit (c) having a hydroxy group, a structural unit (d) having a blocked isocyanato group, or a combination thereof. The copolymer (A) may further contain, as necessary, a structural unit (e) other than the structural units (a) to (d) and (pb).

[0019] (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 a modified copolymer (A2) obtained by converting 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, a carboxy group is preferred as the acid group of the structural unit (a) in terms of ease of availability.

[0020] The structural unit (a) having an acid group is preferably a structural unit derived from a monomer (m-a) having an acid group and an ethylenically unsaturated bond (hereinafter also simply referred to as monomer (m-a)). Specific examples of the monomer (m-a) include unsaturated carboxylic acids or anhydrides thereof such as (meth)acrylic acid, α-bromo(meth)acrylic acid, β-furyl(meth)acrylic acid, crotonic 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.

[0021] The monomer (ma) having an acid group and an ethylenically unsaturated bond may be used alone or in combination of two or more kinds.

[0022] 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%, of all structural units in the copolymer (A). When the content of the structural unit (a) is 5 mol% or more, good developability can be obtained for a photosensitive resin composition using a modified copolymer (A2) obtained by converting the copolymer (A). When the content of the structural unit (a) is 50 mol% or less, the content of the structural unit (pb) can be sufficiently ensured, and therefore the effects attributable to the structural unit (b) can be sufficiently ensured.

[0023] (Structural Unit (pb) Having a Group Represented by Formula (1)) The structural unit (pb) having a group represented by formula (1) (also simply referred to as "structural unit (pb)") is a structural unit having a group represented by the following formula (1) and having no acid group or ethylenically unsaturated group. (In formula (1), R １ and R ４are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and 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) from the structural unit (pb).

[0024] The group represented by formula (1) may not be of one type. １ may be different from each other, and R ２ may also be different, and R ３ may also be different, and R ４ may also be different.

[0025] In formula (1), 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 because it facilitates the conversion reaction of the structural unit (pb) to the structural unit (b) having a group represented by formula (1-1) or formula (1-2) described below. １ and R ４ 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.

[0026] In formula (1), R ２ and R ３ 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, a conversion reaction from the structural unit (pb) to the structural unit (b) having a group represented by formula (1-1) or formula (1-2) described later is more preferred, and a hydrogen atom is particularly preferred. R ２ and R３ 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.

[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 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 formula (1).

[0029] 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 (4): (In formula (4), 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

[0030] As a method for carrying out the urethane reaction between the isocyanate compound having an ethylenically unsaturated group and the hydroxy group-containing compound represented by formula (4), a conventionally known method can be used.

[0031] 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 inactive to the isocyanato group, and known solvents can be used.

[0032] The urethane-forming reaction is generally preferably carried out at a temperature of from −10° C. to 90° C., more preferably from 5° C. to 70° C., and even more preferably from 10° C. to 40° C.

[0033] When carrying out the urethanization reaction, a urethanization catalyst such as dibutyltin dilaurate, a polymerization inhibitor such as phenothiazine, hydroquinone monomethyl ether, or 2,6-di-tert-butyl-4-methylphenol (BHT), or the like may be used, if necessary.

[0034] Examples of the isocyanate compound having an ethylenically unsaturated group used as a raw material for the monomer (m-pb) include the isocyanate compound represented by the following formula (5): (In formula (5), R ９ represents a hydrogen atom or a methyl group, and R １０ is -CO-, -COOR １１ - (where R １１ is an alkylene group having 1 to 6 carbon atoms, or —COO—R １２ O-CONH-R １３ - (where R １２ is an alkylene group having 2 to 6 carbon atoms, and R １３ 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.

[0035] In the isocyanate compound represented by formula (5), R １０ is preferably -COOR because of the ease of preparation of the isocyanate compound. １１ - is preferred, and R １１ More preferably, is an alkylene group having 1 to 4 carbon atoms.

[0036] Specific examples of the isocyanate compound represented by the above formula (5) 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.

[0037] As the isocyanate compound used as a raw material for the monomer (m-pb), 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) may be used.

[0038] The alkyl group of the hydroxyalkyl (meth)acrylate is preferably an ethyl group or an n-propyl group, more preferably an ethyl group, for ease of reaction.

[0039] 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.

[0040] 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.

[0041] As the isocyanate compound used as a raw material for the monomer (m-pb), from the viewpoint of low-temperature curing properties, an isocyanate compound having a (meth)acryloyl group or a (meth)acryloyloxy group is preferred, an isocyanate group-containing (meth)acrylate is more preferred, 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 preferred, and 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate and 1,1-bis(methacryloyloxymethyl)ethyl isocyanate are even more preferred.

[0042] Examples of the hydroxy group-containing compound represented by formula (4) 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 these, malic acid ester is preferred from the viewpoints of ease of conversion reaction into the structural unit (b) having a group represented by formula (1-1) or formula (1-2) and ease of availability.

[0043] The number of carbon atoms in the two ester moieties contained in the hydroxy group-containing compound represented by formula (4) (-COOR １ and COOR ４ R in １ and R ４ The number of carbon atoms in each of the groups (C1, C2, C3, C4, C5) is 1 to 20, preferably 1 to 5, and more preferably 1 to 3.

[0044] The hydroxy group-containing compound represented by formula (4) is particularly preferably diethyl malate from the viewpoint of availability.

[0045] 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.

[0046] The content of the structural unit (pb) is preferably 3 to 40 mol%, more preferably 5 to 35 mol%, and even more preferably 10 to 30 mol%, of the total structural units of the copolymer (A). When the content of the structural unit (pb) is 3 mol% or more, a sufficient amount of ethylenically unsaturated groups can be introduced into the copolymer (A) by a conversion reaction. By using a modified copolymer (A2) into which an ethylenically unsaturated group has been introduced, good low-temperature curing properties and developability can be obtained. When the content of the structural unit (pb) is 40 mol% or less, the content of the structural unit (a) can be sufficiently ensured, and by using the modified copolymer (A2) in a photosensitive resin composition, sufficient developability can be obtained.

[0047] (Structural unit (c) having a hydroxy group) The copolymer (A) may contain a structural unit (c) having a hydroxy group (also simply referred to as "structural unit (c)"), if necessary. The structural unit (c) is not limited as long as it is a structural unit having a hydroxy group and does not have an acid group, an ethylenically unsaturated group, or a blocked isocyanato group. When the copolymer (A) has the structural unit (c) having a hydroxy group, crosslinking with the structural unit (d) having a blocked isocyanato group, which will be described later, progresses upon heating. As a result, when a modified copolymer (A2) obtained by converting the copolymer (A) is used in a photosensitive resin composition, good solvent resistance can be obtained for the cured product even when heat-cured at low temperatures.

[0048] The structural unit (c) having a hydroxy group is preferably a structural unit derived from a monomer (m-c) having a hydroxy group and an ethylenically unsaturated group (hereinafter also simply referred to as monomer (m-c)). Specific examples of the monomer (m-c) include (meth)acrylic acid ester derivatives having a hydroxy 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; and 2-hydroxy-3-phenoxypropyl (meth)acrylate. Among these, hydroxyalkyl (meth)acrylates are preferred from the viewpoints of reactivity during synthesis of the copolymer (A), low-temperature curing properties of the photosensitive resin composition containing the modified copolymer (A2), 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 lowering the glass transition temperature of the copolymer (A), 4-hydroxybutyl (meth)acrylate is more preferred.

[0049] The monomer (mc) having a hydroxy group and an ethylenically unsaturated group may be used alone or in combination of two or more kinds.

[0050] The content of the structural unit (c) is preferably 3 to 40 mol%, more preferably 5 to 30 mol%, and even more preferably 8 to 25 mol%, of the total structural units of the copolymer (A). When the content of the structural unit (c) is 3 mol% or more, a sufficient amount of crosslinking between the hydroxy group of the structural unit (c) and the blocked isocyanato group of the structural unit (d) can be ensured. As a result, the low-temperature curing properties of the photosensitive resin composition using the modified copolymer (A2) obtained by converting the copolymer (A) are improved. When the content of the structural unit (c) is 40 mol% or less, the contents of the structural unit (a) and the structural unit (pb) can be ensured sufficiently, thereby allowing a sufficient amount of ethylenically unsaturated groups to be introduced into the copolymer (A). Therefore, sufficient developability can be obtained for the cured product of the photosensitive resin composition using the modified copolymer (A2) after conversion. In addition, a sufficient content of the structural unit (d) can be ensured, thereby ensuring a sufficient amount of crosslinking with the structural unit (c).

[0051] (Structural Unit (d) Having a Blocked Isocyanato Group) The copolymer (A) may contain a structural unit (d) having a blocked isocyanato group (also simply referred to as "structural unit (d)"), if necessary. The structural unit (d) is not particularly limited as long as it is a structural unit that does not have an acid group or an ethylenically unsaturated group, does not fall under the structural unit (pb), and has a blocked isocyanato group. When the copolymer (A) has the structural unit (d) having a blocked isocyanato group, crosslinking with the structural unit (c) having a hydroxy group proceeds upon heating. The crosslink is formed, for example, by a reaction between an isocyanato group generated by dissociation of the blocking agent and a hydroxy group. When the blocking agent is a compound having a carboxylic acid alkyl ester structure, crosslinking can be formed by transesterification between the carboxylic acid alkyl ester structure and a hydroxy group, as described below, even without dissociation of the blocking agent. As a result, when the modified copolymer (A2) is used in a photosensitive resin composition, good solvent resistance can be obtained for the cured product even when heat cured at low temperatures.

[0052] The structural unit (d) having a blocked isocyanato group has a structure in which an isocyanato group is blocked with a blocking agent. The reaction between the isocyanato group and the blocking agent can be carried out regardless of the presence or absence of a solvent. When a solvent is used, it must be inactive to the isocyanato group. In the blocking reaction, an organic metal salt such as tin, zinc, or lead, or a tertiary amine may be used as a catalyst. The blocking reaction can generally be carried out at a temperature of -20 to 150°C, but is preferably carried out at a temperature of 0 to 100°C.

[0053] Examples of blocking agents for blocking isocyanato groups include lactam compounds such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; alcohol compounds such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, and cyclohexanol; phenol compounds such as phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, o-isopropylphenol, and butylphenols such as p-tert-butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, thymol, 1-naphthol, p-nitrophenol, and p-chlorophenol; mercaptan compounds such as butyl mercaptan, thiophenol, tert-dodecyl mercaptan; amine compounds such as diphenylamine, phenylnaphthylamine, aniline, carbazole; acid amide compounds such as acetanilide, acetanisidide, acetic acid amide, benzamide; imide compounds such as succinimide and maleimide; imidazole compounds such as imidazole, 2-methylimidazole, 2-ethylimidazole; pyrazole compounds such as pyrazole and 3,5-dimethylpyrazole; urea compounds such as urea, thiourea, ethyleneurea; carbamic acid compounds such as N-phenylphenylcarbamate and 2-oxazolidone; imine compounds such as ethyleneimine and polyethyleneimine; oxime compounds such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime;

[0054] The blocking agents may be used alone or in combination of two or more.

[0055] In one embodiment, from the viewpoint of improving the low-temperature curability and solvent resistance of the photosensitive resin composition, the blocking agent is preferably a blocking agent that results in a dissociation rate of blocked isocyanato groups of 5 to 99 mass% when heat-treated at 100°C for 30 minutes, more preferably one or more selected from the group consisting of 3,5-dimethylpyrazole, methyl ethyl ketoxime, methyl 4-hydroxybenzoate, methyl 2-hydroxybenzoate, and 3,5-xylenol, and even more preferably 3,5-dimethylpyrazole.

[0056] In this specification, the dissociation rate of the blocked isocyanato group refers to a value obtained by preparing an n-octanol solution of a blocked isocyanato group-containing compound at a concentration of 20% by mass, adding 1% by mass of dibutyltin laurate and 3% by mass of phenothiazine (a polymerization inhibitor) to the solution, and then heating the solution at 100°C for 30 minutes, after which the mass loss rate of the blocked isocyanato group-containing compound is measured by HPLC analysis. The blocked isocyanato group-containing compound is a compound in which the isocyanato group of 2-isocyanatoethyl acrylate is blocked with the blocking agent to be measured. Using a blocking agent whose dissociation rate falls within the above range can ensure sufficient stability of the copolymer (A) during synthesis, can set the baking temperature during cured film production to a sufficiently low temperature, and can also ensure sufficient solvent resistance of the cured film.

[0057] In one embodiment, a blocking agent having a carboxylic acid alkyl ester structure is also preferred as the blocking agent from the viewpoint of improving the low-temperature curing property and solvent resistance of the photosensitive resin composition. In this case, the structural unit (d) having a blocked isocyanato group has a carboxylic acid alkyl ester structure. The carboxylic acid alkyl ester structure refers to a structure having an alkyloxycarbonyl group, and a structure having an alkyloxycarbonyl group with 1 to 10 carbon atoms in the alkyl group is preferred. By heating the photosensitive resin composition containing the modified copolymer (A2), the alkyloxycarbonyl group undergoes ester exchange with the hydroxy group of the structural unit (c) to form a crosslinked structure. Therefore, a photosensitive resin composition using the modified copolymer (A2) obtained by converting the copolymer (A) containing a structural unit having a carboxylic acid alkyl ester structure can provide a cured film with excellent solvent resistance even when cured at a low temperature of 50°C to 150°C.

[0058] The structural unit having a carboxylic acid alkyl ester structure is more preferably a structural unit having a group represented by the following formula (2) or a group represented by the following formula (3). (In formula (2), R ５ and R ６ each independently represents an alkyl group having 1 to 10 carbon atoms, n1 and n2 each independently represent an integer of 0 to 2, and * represents a linking site with the residue remaining after removing the blocked isocyanato group from the structural unit (d). (In formula (3), R ７ and R ８ each independently represents an alkyl group having 1 to 10 carbon atoms, n3 and n4 each independently represents an integer of 0 to 2, and * represents a linking site with the residue remaining after removing the blocked isocyanato group from the structural unit (d).

[0059] The group represented by formula (2) may not be of one type. ５ may be different from each other, and R ６ The same applies to the group represented by formula (3).

[0060] R in the above formula (2) ５ and R ６ are each independently an alkyl group having 1 to 10 carbon atoms. ５ and R ６ are each independently preferably an alkyl group having 2 to 6 carbon atoms, more preferably an alkyl group having 2 to 3 carbon atoms, and R ５ and R ６ Most preferably, both are ethyl groups.

[0061] R ５ and R ６ is an ethyl group, when the photosensitive resin composition containing the modified copolymer (A2) is thermally cured, R ５ and R ６ The hydroxyl group of the structural unit (c) undergoes transesterification to produce ethanol. The ethanol produced during thermal curing of the photosensitive resin composition is preferred because it can be easily evaporated and removed by heating for thermal curing the photosensitive resin composition.

[0062] In the above formula (2), n1 and n2 each independently represent an integer of 0 to 2. It is preferable that n1 and n2 each independently represent 0 or 1, and it is more preferable that both are 0.

[0063] R in the above formula (3) ７ and R ８ are each independently an alkyl group having 1 to 10 carbon atoms. ７ is preferably an alkyl group having 2 to 6 carbon atoms, more preferably an alkyl group having 2 to 3 carbon atoms, and even more preferably an ethyl group.

[0064] R ７ is an ethyl group, when the photosensitive resin composition containing the modified copolymer (A2) is thermally cured, R ７ The hydroxyl group of the structural unit (c) undergoes transesterification to produce ethanol. The ethanol produced during thermal curing of the photosensitive resin composition is preferred because it can be easily evaporated and removed by heating for thermal curing the photosensitive resin composition.

[0065] R ８is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group.

[0066] In the above formula (3), n3 and n4 each independently represent an integer of 0 to 2. n3 and n4 each independently are preferably 0 or 1, and more preferably both are 0.

[0067] From the viewpoint of ease of transesterification with the hydroxy group of the structural unit (c) and low-temperature curing properties of the photosensitive resin composition, the structural unit (d) preferably has a group represented by formula (2).

[0068] The structural unit (d) having a blocked isocyanato group is preferably a structural unit derived from a monomer (m-d) (also simply referred to as monomer (m-d)) having a blocked isocyanato group and an ethylenically unsaturated bond. The monomer (m-d) may be used alone or in combination of two or more. Specific examples of the group having an ethylenically unsaturated bond include a vinyl group and a (meth)acryloyloxy group.

[0069] Examples of the monomer (m-d) include a reaction product of an isocyanate compound having an ethylenically unsaturated group with a blocking agent. The isocyanate compound having an ethylenically unsaturated group may be the same as the isocyanate compound used as a raw material for the above-mentioned monomer (m-pb).

[0070] The structural unit having a group represented by formula (2) or (3) is preferably a structural unit derived from a monomer having a group represented by formula (2) or (3) and an ethylenically unsaturated bond. Specific examples of the group having an ethylenically unsaturated bond include a vinyl group and a (meth)acryloyloxy group.

[0071] Examples of the monomer having a group represented by formula (2) or (3) and an ethylenically unsaturated bond include a reaction product of an isocyanate compound having an ethylenically unsaturated group with a malonic acid diester or an acetoacetic acid ester.

[0072] As the isocyanate compound having an ethylenically unsaturated group, the same isocyanate compounds as those used as raw materials for the above-mentioned monomer (m-pb) can be used.

[0073] Examples of malonic acid diesters include dimethyl malonate, diethyl malonate, di(n-propyl) malonate, and di(i-propyl) malonate. From the viewpoints of availability, cost, and quality, diethyl malonate and dimethyl malonate are preferred.

[0074] Examples of acetoacetic acid esters include methyl acetoacetate and ethyl acetoacetate.

[0075] Specific examples of the monomer having a group represented by formula (2) and an ethylenically unsaturated bond include Karenz (trademark) MOI-DEM (Resonac Co., Ltd.) and Karenz (trademark) AOI-DEM (Resonac Co., Ltd.).

[0076] The reaction of an isocyanate compound having an ethylenically unsaturated group with a malonic acid diester or an acetoacetic acid ester can be carried out regardless of the presence or absence of a solvent. When the reaction is carried out using a solvent, a solvent inactive to the isocyanato group is used. In the reaction, a catalyst such as an organic metal salt of tin, zinc, lead, or the like, or a tertiary amine may be used.

[0077] The reaction can generally be carried out at a temperature of -20 to 150°C, preferably 25 to 130°C. When the reaction temperature is -20°C or higher, a sufficient reaction rate can be obtained. On the other hand, when the reaction temperature is 150°C or lower, gelation due to polymerization of raw materials having a C=C (double bond) can be prevented.

[0078] The content of the structural unit (d) is preferably 5 to 45 mol%, more preferably 10 to 40 mol%, and even more preferably 15 to 35 mol%, of the total structural units of the copolymer (A). When the content of the structural unit (d) is 5 mol% or more, the amount of crosslinking between the blocked isocyanato group of the structural unit (d) and the hydroxy group of the structural unit (c) can be sufficiently ensured. As a result, the low-temperature curing properties of the photosensitive resin composition using the modified copolymer (A2) obtained by converting the copolymer (A) are improved. When the content of the structural unit (d) is 45 mol% or less, the content of the structural unit (a) and the structural unit (pb) can be sufficiently ensured, and the content of the structural unit (a) and the structural unit (b) of the modified copolymer (A2) can be sufficiently ensured, thereby obtaining sufficient developability of the cured product. In addition, the content of the structural unit (c) can be sufficiently ensured, and the amount of crosslinking with the structural unit (d) can be sufficiently ensured.

[0079] (Structural Unit (e) Other Than Structural Units (a) to (d) and 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. The structural unit (e) is a structural unit other than the structural units (a) to (d) and the structural unit (pb) that does not have an acid group, an ethylenically unsaturated group, a hydroxy group, or a blocked isocyanate group. When the copolymer (A) contains the structural unit (e), it can be imparted with additional required functions.

[0080] The other structural unit (e) is a structural unit derived from a monomer (me) (also simply referred to as monomer (me)) having another ethylenically unsaturated group that is copolymerizable with the monomers (m-a), (m-pb), (m-c), and (m-d). Specific examples include 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)acrylate, (meth)acrylic acid anilide, (meth)acrylonitrile, and acrolein.

[0081] Examples of aromatic vinyl compounds include styrene, α-methylstyrene, o-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, methoxystyrene, p-nitrostyrene, p-cyanostyrene, and p-acetylaminostyrene.

[0082] Examples of 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]hept-2-ene. 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.

[0083] Examples of dienes include butadiene, isoprene, and chloroprene.

[0084] Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, benzyl (meth)acrylate, isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, rosin (meth)acrylate, norbornyl (meth)acrylate, 5-ethylnorbornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl acrylate, isobornyl (meth)acrylate, and adamantyl (meth)acrylate. 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, 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.

[0085] 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.

[0086] Examples of the vinyl compound include vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, and vinyltoluene.

[0087] Examples of the unsaturated dicarboxylic acid diester include diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate.

[0088] Examples of monomaleimides include N-phenylmaleimide, N-cyclohexylmaleimide, and N-laurylmaleimide.

[0089] Among these, from the viewpoints of availability and reactivity during synthesis of the copolymer (A), aromatic vinyl compounds, aromatic group-containing (meth)acrylates, and alkyl (meth)acrylates in which the alkyl group has 1 to 12 carbon atoms are preferred, styrene, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and methyl (meth)acrylate are more preferred, and 2-ethylhexyl (meth)acrylate and methyl (meth)acrylate are even more preferred.

[0090] The monomers (me) may be used alone or in combination of two or more.

[0091] When copolymer (A) contains structural unit (e), its content is preferably 1 to 50 mol %, more preferably 3 to 45 mol %, and even more preferably 5 to 40 mol %, of all structural units in copolymer (A). By setting the content of structural unit (e) within the above range, it is possible to impart additional functions by structural unit (e) while sufficiently ensuring the functions of structural units (a), (pb), (c), and (d), or to adjust the functions obtained from structural units (a), (pb), (c), and (d) within appropriate ranges.

[0092] [Basic Catalyst (B)] The basic catalyst (B) has a pKa (acidity constant; also referred to as acid dissociation constant) at 25°C of 4 to 12. The pKa of the basic catalyst (B) at 25°C is 12 or less, and may be 11 or less, or 10 or less. The pKa of the basic catalyst (B) at 25°C is 4 or more, 5 or more, 6 or more, or 7 or more. Any combination of these lower and upper limits may be used. When the pKa at 25°C is 4 or more, a high conversion rate from the structural unit (pb) to the structural unit (b) can be obtained. When the pKa at 25°C is 12 or less, the conversion rate from the structural unit (pb) to the structural unit (b) can be controlled within an appropriate range, and further reaction and consumption of the structural unit (b) can be suppressed. In addition, the photosensitive resin composition has good storage stability, resulting in good developability. The basic catalyst (B) having a pKa of 4 or more at 25°C includes those having a pKa of 4 or more in aqueous solution, and those which are too acidic to be measured in aqueous solution but whose pKa in aqueous solution is converted from the results of measurement in an organic solvent to 4 or more.

[0093] Specific examples of the basic catalyst (B) include pyridine and pyridine derivatives, imidazole compounds, alkylamines, cyclic diamines, etc. Note that "C1-4 alkyl" means that the alkyl group has 1 to 4 carbon atoms.

[0094] 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 to 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 these, from the viewpoint of the conversion efficiency of the structural unit (pb) contained in the copolymer (A), a 4-aminopyridine derivative is preferred, a 4-aminopyridine derivative having a tertiary amino group at the 4-position is more preferred, a 4-diC1-4 alkylaminopyridine is further preferred, and 4-dimethylaminopyridine is particularly preferred.

[0095] Examples of the imidazole compound include 2-methylimidazole (pKa 7.75) and 1,2-dimethylimidazole (pKa 7.8).

[0096] Examples of alkylamines include diisopropylamine (pKa 11.05), trimethylamine, and triethylamine (pKa 10.7).

[0097] Examples of cyclic diamines include 1,4-diazabicyclo[2.2.2]octane (DABCO) (pKa 8.8).

[0098] Among these, at least one selected from the group consisting of pyridine, pyridine derivatives, and imidazole compounds is preferably used because of its high nucleophilicity resulting from resonance stabilization. It is more preferable to use at least one selected from the group consisting of pyridine derivatives and imidazole compounds, and it is even more preferable to use a 4-aminopyridine derivative. This allows the structural unit (pb) contained in the copolymer (A) to be efficiently converted to introduce an ethylenically unsaturated group. Therefore, the copolymer (A) can be efficiently converted into the modified copolymer (A2) described below. A photosensitive resin composition using the modified copolymer (A2) can provide a cured film that has excellent low-temperature curing properties and developability, and excellent solvent resistance.

[0099] In one embodiment, the basic catalyst (B) is preferably at least one selected from pyridine, 4-dimethylaminopyridine, 1,2-dimethylimidazole, triethylamine, and 1,4-diazabicyclo[2.2.2]octane, more preferably at least one selected from 4-dimethylaminopyridine, 1,2-dimethylimidazole, triethylamine, and 1,4-diazabicyclo[2.2.2]octane, and even more preferably at least one selected from 4-dimethylaminopyridine, triethylamine, and 1,4-diazabicyclo[2.2.2]octane.

[0100] The basic catalyst (B) may be used alone or in combination of two or more kinds.

[0101] The content of the basic catalyst (B) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and even more preferably 0.5 to 6 parts by mass, relative to 100 parts by mass of the copolymer (A). When the content of the basic catalyst (B) is 0.01 part by mass or more, the reaction rate for converting the structural unit (pb) contained in the copolymer (A) to the structural unit (b) tends to be sufficiently fast, which is preferable. When the content of the basic catalyst (B) is 10 parts by mass or less, the influence of the basic catalyst (B) can be suppressed when curing a photosensitive resin composition containing the modified copolymer (A2) obtained by converting the copolymer (A).

[0102] [Solvent (C)] Examples of the solvent (C) 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; and ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol (Poly)alkylene glycol monoalkyl ether acetates such as monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl ether, Examples of hydroxy group-free solvents include esters such as ethyl propionate, 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 carboxylic acid amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.The solvent (C) may be used alone or in combination of two or more kinds.

[0103] Among these solvents (C), from the viewpoints of availability, cost, and stability during resist preparation, it is preferable to use ethers such as (poly)alkylene glycol monoalkyl ethers, (poly)alkylene glycol monoalkyl ether acetates, and other ethers, 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.

[0104] The content of solvent (C) is preferably 30 to 1,000 parts by mass, more preferably 50 to 800 parts by mass, per 100 parts by mass of the total of the components other than solvent (C). A content of solvent (C) of 30 parts by mass or more is preferred because a stable reaction can be carried out when converting the structural unit (pb) contained in copolymer (A). A content of solvent (C) of 1,000 parts by mass or less is preferred because the viscosity of the resin composition can be appropriately adjusted.

[0105] [Method for Producing Copolymer (A)] Copolymer (A) can be produced by copolymerizing monomers (m-a) and (m-pb), which correspond to the structural units (a) and (pb) contained in copolymer (A), respectively. The proportions of the structural units (a) and (pb) contained in copolymer (A) are the same as the proportions of the respective monomers (m-a) and (m-pb) in the total of all the monomers used as raw materials for copolymer (A) (hereinafter, sometimes referred to as "raw material monomers").

[0106] Therefore, the proportions of the monomers (m-a) and (m-pb) in the raw material monomers used as raw materials for copolymer (A) are preferably 5 to 50 mol% for (m-a) and 3 to 40 mol% for (m-pb), more preferably 8 to 40 mol% for (m-a) and 5 to 35 mol% for (m-pb), and even more preferably 10 to 30 mol% for (m-a) and 10 to 30 mol% for (m-pb).

[0107] When producing a copolymer (A) containing the structural unit (c), the raw material monomers for the copolymer (A) may be the monomer (m-c) in addition to the monomers (m-a) and (m-pb). In this case, the proportion of the monomer (m-c) in the raw material monomers used as the raw material for the copolymer (A) is preferably 3 to 40 mol%, more preferably 5 to 30 mol%, and even more preferably 8 to 25 mol%.

[0108] When copolymer (A) containing structural unit (d) is produced, monomer (m-d) may be used as raw material monomers for copolymer (A) in addition to monomers (m-a) and (m-pb). In this case, the proportion of monomer (m-d) in the raw material monomers used as raw materials for copolymer (A) is preferably 5 to 45 mol%, more preferably 10 to 40 mol%, and even more preferably 15 to 35 mol%.

[0109] When producing a copolymer (A) containing the structural unit (e), the raw material monomers for the copolymer (A) may be the monomer (me) in addition to the monomers (m-a) and (m-pb). In this case, the proportion of the monomer (me) in the raw material monomers used as raw materials for the copolymer (A) is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, and even more preferably 5 to 40 mol%.

[0110] The copolymerization reaction of the raw material monomers (monomers (m-a) and (m-pb), and monomers (m-c), (m-d), and (me) used as needed) used in producing the copolymer (A) 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.

[0111] As the polymerization solvent used in producing the copolymer (A), those usable as the solvent (C) can be used alone or in combination of two or more kinds.

[0112] When the raw material monomers include monomers (m-c) and (m-d), the temperature at which the raw material monomers are copolymerized is preferably below the temperature at which the dissociation rate of the blocked isocyanato group of monomer (m-d) having a blocked isocyanato group and an ethylenically unsaturated bond reaches 80% or more in 30 minutes. This is to prevent the blocked isocyanato group of monomer (m-d) from dissociating to generate an isocyanato group in the raw material monomer solution during the copolymerization reaction, which then reacts with the hydroxy group of the hydroxy group-containing monomer (m-c) to cause gelation. The temperature at which the raw material monomers are copolymerized is more preferably 20 to 50°C lower than the temperature at which the dissociation rate of the blocked isocyanato group of monomer (m-d) reaches 80% or more in 30 minutes.

[0113] 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.

[0114] Examples of polymerization initiators used in copolymerizing raw material monomers include 2,2'-azobis(2,4-dimethylvaleronitrile), azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, and t-butylperoxy-2-ethylhexanoate. These polymerization initiators may be used alone or in combination of two or more. The amount of 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 monomers (total amount of monomers charged).

[0115] When producing the copolymer (A), additives such as a polymerization inhibitor, a chain transfer agent, a photosensitizer, a filler, and a plasticizer may be used as needed within a range that does not impair the effects of the present invention.

[0116] [Method for producing resin composition] The resin composition is obtained by mixing the copolymer (A), the basic catalyst (B), and the solvent (C). When the copolymer (A) is synthesized by the above-mentioned production method, the resin composition can also be produced by adding the basic catalyst (B) to the reaction solution. In this case, the solvent used in the synthesis of the copolymer (A) may be used as the solvent (C) as it is, or a new solvent may be added.

[0117] <Modified Resin Composition> The modified resin composition of one embodiment contains the modified copolymer (A2), the basic catalyst (B), and the solvent (C). The modified resin composition may also contain the copolymer (A).

[0118] The basic catalyst (B) and the solvent (C) may be the same as those used in the resin composition, and the preferred forms and amounts are also the same. The amount of the basic catalyst (B) is based on 100 parts by mass of the total of the copolymer (A) and the modified copolymer (A2).

[0119] [Modified Copolymer (A2)] The modified copolymer (A2) of one embodiment 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 (b) having a group represented by the following formula (1-1) or (1-2). The modified copolymer (A2) can be obtained by converting a portion of the structural unit (pb) of the copolymer (A) to the structural unit (b) through a dealcoholization reaction and a decarboxylation reaction of the structural unit (pb) under the action of a basic catalyst (B). The modified copolymer (A2) having the structural unit (b) having an ethylenically unsaturated group provides good photocurability and improved low-temperature curability when used in a photosensitive resin composition. In addition, when the modified copolymer (A2) is used together with a reactive diluent (D) described below, the ethylenically unsaturated group of the structural unit (b) reacts with the reactive diluent (D), resulting in good adhesion of the cured film to the substrate. (In formula (1), R １ and R ４ are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and 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) from the structural unit (pb). (In formula (1-1), R １ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and 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). (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, and R ４ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents the linking site with the residue obtained by removing the group of formula (1-2) from the structural unit (b).

[0120] The modified copolymer (A2) may further contain, as necessary, a structural unit (c) having a hydroxy group and a structural unit (d) having a blocked isocyanato group. The modified copolymer (A2) may further contain, as necessary, a structural unit (e) other than the structural units (a) to (d) and the structural unit (pb).

[0121] The structural units (a), (pb), (c), (d), and (e) can be the same as those in the copolymer (A). Except for the content of the structural unit (pb), preferred embodiments are also the same.

[0122] The content of the structural unit (pb) is preferably 1 to 35 mol %, more preferably 2 to 30 mol %, and even more preferably 3 to 25 mol %, of all structural units in the modified copolymer (A2) and the copolymer (A).

[0123] (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)") does not have an acid group and is a structural unit having a group represented by the following formula (1-1) or formula (1-2): (In formula (1-1), R １is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and 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). (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, and R ４ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents the linking site with the residue obtained by removing the group of formula (1-2) from the structural unit (b).

[0124] The group represented by formula (1-1) does not have to be of one type. １ may be different from each other, and R ２ may also be different, and R ３ The same applies to the group represented by formula (1-2).

[0125] In formula (1-1) and formula (1-2), R １ , R ２ , R ３ and R ４ is the same as described above for equation (1).

[0126] The content of the structural unit (b) is preferably 2 to 39 mol %, more preferably 3 to 33 mol %, and even more preferably 7 to 27 mol %, of all structural units in the modified copolymer (A2) and the copolymer (A).

[0127] (Reaction Pathway) In the conversion reaction from copolymer (A) to modified copolymer (A2), the structural unit (pb) contained in copolymer (A) is presumed to be converted to structural unit (b) via the reaction path shown below.

[0128] That is, in the structural unit (pb) having a group represented by formula (1) contained in the copolymer (A), H of —NH— in the urethane bond and H of the ester moiety (—COOR １ or -COOR ４ ) A dealcoholization reaction occurs.

[0129] This results in the formation of a group having a heterocycle represented by formula (1-3) and / or formula (1-4). The group having a heterocycle represented by formula (1-3) is formed by the reaction of R ４ Dealcoholization reaction of the ester moiety containing (-R ４ The heterocyclic group represented by formula (1-4) is formed by the reaction of R １ Dealcoholization reaction of the ester moiety containing (-R １ OH). (In formula (1-3), R １ , R ２ and R ３ is R in formula (1). １ , R ２ and R ３ and * represents the linking site with the residue obtained by removing the group of formula (1-3) from the structural unit (pb). (In formula (1-4), R ２ , R ３ and R ４ is R in formula (1). ２ , R ３ and R ４ and * represents the linking site with the residue obtained by removing the group of formula (1-4) from the structural unit (pb).

[0130] Next, in the group having a heterocycle represented by the above formula (1-3), decarboxylation (—CO ２ As a result, the group having a heterocycle represented by formula (1-3) is converted into a group represented by the following formula (1-1). (In formula (1-1), R １ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and 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).

[0131] On the other hand, in the group having a heterocycle represented by the above formula (1-4), decarboxylation (—CO ２As a result, the heterocyclic ring-containing group represented by formula (1-4) is converted into a group represented by the following formula (1-2). (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, and R ４ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents the linking site with the residue obtained by removing the group of formula (1-2) from the structural unit (b).

[0132] As a result of performing transition state calculations on the production pathways of each product using density functional theory with wB97XD as the functional and 6-31+g(d) as the basis function, it is presumed that the conversion reaction for converting the above-mentioned structural unit (pb) to the structural unit (b) has a lower activation barrier in the reaction pathways of formula (1), formula (1-4), and formula (1-2) than in the reaction pathways of formula (1), formula (1-3), and formula (1-1), and is the main conversion route. Therefore, it is presumed that the modified copolymer (A2) contains a mixture of structural units having a group represented by formula (1-2) and structural units having a group represented by formula (1-1), and that the structural units having a group represented by formula (1-2) are present in greater amounts than the structural units having a group represented by formula (1-1).

[0133] [Ethylenically unsaturated group equivalent of modified copolymer (A2)] The ethylenically unsaturated group equivalent of the modified copolymer (A2) is preferably 300 g / mol or more, more preferably 500 g / mol or more, and even more preferably 1000 g / mol or more. The ethylenically unsaturated group equivalent of the modified copolymer (A2) is preferably 10000 g / mol or less, more preferably 7000 g / mol or less, and even more preferably 4000 g / mol or less. Any combination of these lower and upper limits may be used. When the equivalent is 300 g / mol or more, the storage stability of the photosensitive resin composition is good. When the equivalent is 10000 g / mol or less, the solvent resistance of the cured product is good even when cured at low temperatures.

[0134] The "ethylenically unsaturated group equivalent" is the mass of a polymer per 1 mol of ethylenically unsaturated groups in the polymer. The ethylenically unsaturated group equivalent (g / mol) of the modified copolymer (A2) is determined by dividing the mass of the modified copolymer (A2) by the number of moles of ethylenically unsaturated groups contained in the modified copolymer (A2).

[0135] In this specification, R in formula (1-1) and formula (1-2) in the modified copolymer (A2) ２ and R ３ are all hydrogen atoms, the ethylenically unsaturated group equivalent is a value calculated from the conversion rate of structural unit (pb) to structural unit (b), calculated from the area ratio of an NMR spectrum obtained under the following conditions using an NMR apparatus (e.g., Bruker ULTRA SHIELD PLUS 400 (400 MHz), Bruker), and the amounts of monomers (m-a), (m-pb), and (m-c) to (m-e) used in producing copolymer (A). The measurement sample may contain copolymer (A). In this case, the value obtained for the mixture of modified copolymer (A2) and copolymer (A) is determined to be the ethylenically unsaturated group equivalent of modified copolymer (A2). When the measurement sample contains copolymer (A), the conversion rate of structural unit (pb) to structural unit (b) is also a value for the mixture of modified copolymer (A2) and copolymer (A).

[0136] (NMR conditions) Measurement method: １ H-NMR lock solvent: CDCl ３ Internal standard: TSP-d ４ (Sodium trimethylsilylpropionate) = 0 ppm Temperature: Room temperature Sample preparation: Powder sample (20 mg) / CDCl ３ (1mL)+TSP-d ４ (5 mg)

[0137] (Sample Preparation Method) 20 mg of the dried modified copolymer (A2) or the mixture of the modified copolymer (A2) and the copolymer (A) was weighed out accurately and placed in a 20 mL sample bottle with CDCl ３ (1 mL) is added and dissolved, and the mixture is shaken in an ultrasonic cleaner for 5 minutes, then sealed in a 5 mmφ NMR sample tube, and NMR measurement is performed immediately after sampling.

[0138] The conversion rate from structural unit (pb) to structural unit (b) is detected at 2.5 to 3.0 ppm - CR ２ -CHR ３ -C(=O)- (i.e., -CH-CH ２ -C(=O)-) "-CH ２ -" spectrum and -C(=O)-CR detected at 6.5 to 7.0 ppm. ３ =CR ２ —C(═O)— and —C(═O)—CR ２ =CR ３ Based on the spectral area ratio of -C(=O)- (i.e., -C(=O)-CH=CH-C(=O)-), the conversion rate from structural unit (pb) to structural unit (b) is calculated using the following formula: Conversion rate from structural unit (pb) to structural unit (b) = {(-C(=O)-CH=CH-C(=O)-) / [(-CH-CH ２ -C(=O)-)+(-C(=O)-CH=CH-C(=O)-)]}×100(%)

[0139] In this specification, the modified copolymer (A2) is R ２ and R ３ When the modified copolymer (A2) contains a structural unit (b) having a group represented by formula (1-1) or formula (1-2), at least one of which 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 modified copolymer (A2). The amount of halogen bonded to the modified copolymer (A2) is evaluated as follows in accordance with JIS K 0070:1992.

[0140] Specifically, the dried modified copolymer (A2) is dissolved in chloroform, an appropriate amount of Wiess's solution is added, and the mixture is stirred. The container is then sealed and left in a dark place at 23°C for 1 hour. Potassium iodide solution and water are added to the solution, and the mixture is stirred. The resulting solution is titrated with sodium thiosulfate solution. When the solution turns pale yellow, a few drops of starch solution are added, and the titration is continued until the blue color disappears. The ethylenically unsaturated bonds in the modified copolymer (A2) react with halogen molecules in a 1:1 ratio. Therefore, the ethylenically unsaturated group equivalent of the modified copolymer (A2) is determined by dividing the mass (g) of the modified copolymer (A2) used in the measurement by the molar amount (mol) of halogen molecules bonded to the modified copolymer (A2) determined by this measurement. The measurement sample may also contain copolymer (A). In this case, the value obtained for the mixture of the modified copolymer (A2) and copolymer (A) is determined as the ethylenically unsaturated group equivalent of the modified copolymer (A2).

[0141] [Acid value] The acid value of the copolymer (A) and the acid value of the modified copolymer (A2) or the mixture of the copolymer (A) and the modified copolymer (A2) are preferably 10 KOH mg / g or more, more preferably 15 KOH mg / g or more, and even more preferably 20 KOH mg / g or more. The acid value of the copolymer (A) and the acid value of the modified copolymer (A2) or the mixture of the copolymer (A) and the modified copolymer (A2) are preferably 300 KOH mg / g or less, more preferably 200 KOH mg / g or less, and even more preferably 150 KOH mg / g or less. The combination of these lower and upper limits may be any combination. When the acid value is 10 KOH mg / g or more, the developability is good. When the acid value is 300 KOH mg / g or less, the storage stability is good.

[0142] The "acid value" refers to the acid value of the curable polymer measured in accordance with JIS K6901:2008 5.3. That is, the acid value refers to the number of milligrams of potassium hydroxide required to neutralize the acidic components contained in 1 g of the copolymer.

[0143] [Weight Average Molecular Weight] The weight average molecular weight of copolymer (A) and the weight average molecular weight of modified copolymer (A2) or a mixture of copolymer (A) and modified copolymer (A2) is preferably 1000 or more, more preferably 3000 or more, and even more preferably 5000 or more. The weight average molecular weight of copolymer (A) and the weight average molecular weight of modified copolymer (A2) or a mixture of copolymer (A) and modified copolymer (A2) is preferably 50,000 or less, more preferably 40,000 or less, and even more preferably 30,000 or less. Any combination of these lower and upper limits may be used. When the weight average molecular weight is 1000 or more, when the modified copolymer (A2) 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 50,000 or less, the photosensitive resin composition containing the modified copolymer (A2) has a sufficiently short development time and is excellent in practicality.

[0144] In this specification, the weight-average molecular weight refers to the weight-average molecular weight measured using gel permeation chromatography (GPC) in terms of standard polystyrene under the following conditions: Column: Showdex (trademark) Two LF-804 columns (Resonac Corporation) connected in series were used. Column temperature: 40°C. Sample: 0.2% by mass solution of the object to be measured in tetrahydrofuran. Developing solvent: tetrahydrofuran. Detector: differential refractometer (Shodex (trademark) RI-71S) (Resonac Corporation). Flow rate: 1 mL / min.

[0145] [Blocked Isocyanate Group Equivalent] The blocked isocyanate group equivalent of the copolymer (A) and the blocked isocyanate group equivalent of the modified copolymer (A2) or a mixture of the copolymer (A) and the modified copolymer (A2) is preferably 100 to 2000 g / mol, more preferably 200 to 1500 g / mol, and even more preferably 300 to 1300 g / mol. When the blocked isocyanate group equivalent is 100 g / mol or more, the photosensitive resin composition containing the modified copolymer (A2) has better developability. When the blocked isocyanate group equivalent is 2000 g / mol or less, the photosensitive resin composition containing the modified copolymer (A2) can form a cured resin film with superior hardness.

[0146] The "block isocyanato group equivalent" is the mass of a polymer per 1 mol of blocked isocyanato groups in the polymer. The block isocyanato group equivalent (g / mol) of a copolymer is determined by dividing the mass of the copolymer by the number of moles of blocked isocyanato groups contained in the copolymer. In this specification, the "block isocyanato group equivalent" is a theoretical value calculated from the amounts of monomers charged when producing the copolymer.

[0147] [Hydroxy group equivalent] The hydroxy group equivalent of the copolymer (A) and the hydroxy group equivalent of the modified copolymer (A2) or the mixture of the copolymer (A) and the modified copolymer (A2) is preferably 200 to 5000 g / mol, more preferably 400 to 4000 g / mol, and even more preferably 800 to 3000 g / mol. When the hydroxy group equivalent is 200 g / mol or more, the photosensitive resin composition containing the modified copolymer (A2) has better developability. When the hydroxy group equivalent is 5000 g / mol or less, the photosensitive resin composition containing the modified copolymer (A2) can form a cured resin film with superior hardness.

[0148] "Hydroxy group equivalent" refers to the mass of a polymer per 1 mol of hydroxy groups in the polymer. The hydroxy group equivalent (g / mol) of a copolymer is determined by dividing the mass of the copolymer by the number of moles of hydroxy groups contained in the copolymer. In this specification, the "hydroxy group equivalent" is a theoretical value calculated from the amounts of monomers charged when producing the copolymer.

[0149] [Method for Producing Modified Resin Composition] The modified resin composition can be obtained by converting the structural unit (pb) contained in the copolymer (A) in the resin composition into the structural unit (b), thereby modifying the copolymer (A) to a modified copolymer (A2). For example, a resin composition containing the copolymer (A), a basic catalyst (B), and a solvent (C) 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 copolymer (A) to occur, converting the structural unit (pb) contained in the copolymer (A) into the structural unit (b), thereby producing a modified resin composition containing the modified copolymer (A2), the basic catalyst (B), and the solvent (C). The copolymer (A) may remain in the modified resin composition. The content of the copolymer (A) in the modified resin composition may be 0 to 20 parts by mass, 0 to 10 parts by mass, or 0 to 5 parts by mass per 100 parts by mass of the modified copolymer (A2). In one embodiment, the modified resin composition does not contain the copolymer (A). The temperature condition may be 40°C or higher, 50°C or higher, 60°C or higher, or 70°C or higher. The temperature condition may be 130°C or lower, 110°C or lower, 100°C or lower, or 90°C or lower. Any combination of these lower limit values ​​and upper limit values ​​may be used. The conversion reaction time may be 30 minutes or longer, or 60 minutes or longer. The conversion reaction time may be 300 minutes or shorter, or 180 minutes or shorter. Any combination of these lower limit values ​​and upper limit values ​​may be used.

[0150] <Photosensitive resin composition and photosensitive coloring composition> The photosensitive resin composition of one embodiment contains a modified copolymer (A2), a basic catalyst (B), a solvent (C), a reactive diluent (D), and a photopolymerization initiator (E). The photosensitive resin composition may contain a copolymer (A). The photosensitive coloring composition of one embodiment further contains a colorant (F).

[0151] The total content of the modified copolymer (A2) and the optionally contained copolymer (A) in the photosensitive resin composition or 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, relative to a total of 100 parts by mass of the modified copolymer (A2), the copolymer (A), and the reactive diluent (D). The total content of the modified copolymer (A2) and the optionally contained copolymer (A) in the photosensitive resin composition or 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, relative to a total of 100 parts by mass of the modified copolymer (A2), the copolymer (A), and the reactive diluent (D). The combination of these lower and upper limits may be any combination. When the total content of the modified copolymer (A2) and the copolymer (A) is 10 parts by mass or more, a photosensitive resin composition or 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 modified copolymer (A2) and the copolymer (A) is 90 parts by mass or less, the content of the reactive diluent (D) can be sufficiently ensured, and the strength and adhesion to the substrate of the cured product are good.

[0152] The content of copolymer (A) in the photosensitive resin composition or photosensitive coloring composition may be 0 to 20 parts by mass, 0 to 10 parts by mass, or 0 to 5 parts by mass, relative to 100 parts by mass of the modified copolymer (A2). From the viewpoint of improving the solvent resistance of the cured resin film, copolymer (A) may not be contained.

[0153] The content of the basic catalyst (B) in the photosensitive resin composition or photosensitive coloring composition may be 0.001 parts by mass or more, 0.01 parts by mass or more, or 0.1 parts by mass or more, relative to 100 parts by mass of the total of the modified copolymer (A2), the copolymer (A), and the reactive diluent (D). The content of the basic catalyst (B) in the photosensitive resin composition or photosensitive coloring composition is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less, relative to 100 parts by mass of the total of the modified copolymer (A2), the copolymer (A), and the reactive diluent (D). When the content of the basic catalyst (B) is 5 parts by mass or less, the effect of the basic catalyst (B) when curing the photosensitive resin composition can be suppressed.

[0154] [Solvent (C)] The solvent (C) may be the same as the solvent (C) used in the resin composition. The solvent (C) in the photosensitive resin composition or the photosensitive coloring composition and the solvent (C) used in producing the modified copolymer (A2) may be the same or different.

[0155] The content of the solvent (C) in the photosensitive resin composition or photosensitive coloring composition is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, relative to a total of 100 parts by mass of the modified copolymer (A2), the copolymer (A), and the reactive diluent (D). The content of the solvent (C) in the photosensitive resin composition or photosensitive coloring composition is preferably 1,000 parts by mass or less, more preferably 800 parts by mass or less, relative to a total of 100 parts by mass of the modified copolymer (A2), the copolymer (A), and the reactive diluent (D). Any combination of these lower and upper limits may be used. When the content of the solvent (C) is 30 parts by mass or more, the viscosity of the photosensitive resin composition or photosensitive coloring composition can be set within an appropriate range. When the content of the solvent (C) is 1,000 parts by mass or less, the solvent (C) can be easily removed when removing the solvent (C) from the coating film formed by applying the photosensitive resin composition or photosensitive coloring composition to a substrate.

[0156] [Reactive Diluent (D)] The reactive diluent (D) is a monomer having at least one ethylenically unsaturated bond as a polymerizable functional group in the molecule. The reactive diluent (D) may be a monofunctional monomer or a polyfunctional monomer having multiple polymerizable functional groups. By containing the reactive diluent (D), the viscosity of the photosensitive resin composition or photosensitive coloring composition can be adjusted to an appropriate range depending on the application. In addition, since the photosensitive resin composition or photosensitive coloring composition contains the reactive diluent (D), it has good photocurability and can form a cured product with good strength and adhesion to the substrate. The reactive diluent (D) may be used alone or in combination of two or more.

[0157] Examples of the monofunctional monomer used as the reactive diluent (D) include (meth)acrylamide compounds such as (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, and 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, and 2-phenoxy (meth)acrylate. Examples of the monofunctional monomer include (meth)acrylates such as 2-hydroxypropyl (meth)acrylate, 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 monomers may be used alone or in combination of two or more.

[0158] Examples of polyfunctional monomers used as the reactive diluent (D) 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, ... dipentaerythritol 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 acrylate include (meth)acrylates such as trimethyloxypropyl (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, reaction products 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 diallylbenzene 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.

[0159] Among these monomers, it is preferable to use a polyfunctional (meth)acrylate as the reactive diluent (D) because a photosensitive resin composition or a photosensitive coloring composition having good photocurability can be obtained, and 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.

[0160] The content of the reactive diluent (D) in the photosensitive resin composition or 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 modified copolymer (A2), the copolymer (A), and the reactive diluent (D). The content of the reactive diluent (D) in the photosensitive resin composition or 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 modified copolymer (A2), the copolymer (A), and the reactive diluent (D). Any combination of these lower and upper limits may be used. When the content of the reactive diluent (D) is 10 parts by mass or more, the effect of containing the reactive diluent (D) becomes significant. When the content of the reactive diluent (D) is 90 parts by mass or less, the content of the modified copolymer (A2) can be sufficiently ensured, so that a photosensitive resin composition or photosensitive coloring composition with even better low-temperature curing properties can be obtained.

[0161] [Photopolymerization initiator (E)] The photopolymerization initiator (E) is not particularly limited, and 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-morpholino) Examples of the photopolymerization initiator (E) include 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 4-(1-t-butyldioxy-1-methylethyl)benzophenone and 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone; and acylphosphine oxide photopolymerization initiators. The photopolymerization initiator (E) may be used alone or in combination of two or more.

[0162] The content of the photopolymerization initiator (E) in the photosensitive resin composition or 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 1.0 parts by mass or more, relative to the total 100 parts by mass of the modified copolymer (A2), the copolymer (A), and the reactive diluent (D). The content of the photopolymerization initiator (E) in the photosensitive resin composition or 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, relative to the total 100 parts by mass of the modified copolymer (A2), the copolymer (A), and the reactive diluent (D). The combination of these lower and upper limits may be any combination. When the content of the photopolymerization initiator (E) is 0.1 parts by mass or more, a photosensitive resin composition or photosensitive coloring composition with good photocurability can be obtained. When the content of the photopolymerization initiator (E) 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 due to an excessive amount of the photopolymerization initiator (E).

[0163] [Colorant (F)] The photosensitive coloring composition may further contain a colorant (F). The photosensitive coloring composition containing the colorant (F) can be used as a material for a color filter.

[0164] The colorant (F) is not particularly limited as long as it is soluble or dispersible in the solvent (C), and examples thereof include dyes and pigments.

[0165] As the dye, from the viewpoint of solubility in the solvent (C) 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, a sulfonamide adduct of an acid dye, etc.

[0166] Examples of such dyes include 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; and 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.

[0167] Examples of pigments include yellow pigments such as C.I. 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 C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73; Examples of suitable pigments include red pigments such as C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, and 265; blue pigments such as C.I. Pigment Blue 15, 15:3, 15:4, 15:6, and 60; violet pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, and 38; green pigments such as C.I. Pigment Green 7, 36, 58, and 59; brown pigments such as C.I. Pigment Brown 23 and 25; and black pigments such as C.I. Pigment Black 1 and 7, carbon black, titanium black, and iron oxide. The pigments may be used alone or in combination of two or more kinds.

[0168] The colorant (F) can be appropriately determined depending on, for example, the color of the intended colored pattern (black matrix and pixels). The colorant (F) may be used alone or in combination of two or more. When two or more types of colorants (F) are used, a dye and a pigment may be used in combination.

[0169] When a pigment is used as the colorant (F), a known dispersant may be blended into the photosensitive coloring composition to improve the dispersibility of the pigment. It is preferable to use a polymer dispersant that has excellent dispersion stability over time. Examples of polymer dispersants 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. Commercially available polymer dispersants under trade names such as EFKA (EFKA CHEMICALS B.V.), Disperbyk (BYK), Disparlon (Kusumoto Chemicals Co., Ltd.), and SOLSPERSE (Lubrizol Corporation) may also be used. The content of the dispersant may be appropriately determined depending on the type and amount of the pigment used as the colorant (F).

[0170] The content of the colorant (F) 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 100 parts by mass of the modified copolymer (A2), the copolymer (A), and the reactive diluent (D). The content of the colorant (F) 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 100 parts by mass of the modified copolymer (A2), the copolymer (A), and the reactive diluent (D). Any combination of these lower and upper limits may be used. When the content of the colorant (F) is 3 parts by mass or more, the effect of containing the colorant (F) is significant, and a photosensitive coloring composition suitable as a material for the colored pattern of a color filter can be obtained. When the content of the colorant (F) is 80 parts by mass or less, the colorant (F) does not interfere with the curing property of the photosensitive coloring composition, and a photosensitive coloring composition with good low-temperature curing properties can be obtained.

[0171] [Other Components] In addition to the modified copolymer (A2), the solvent (C), the reactive diluent (D), the photopolymerization initiator (E), and the colorant (F) contained as needed, the photosensitive resin composition or the photosensitive coloring 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 does not inhibit the effects of the present invention.

[0172] <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 modified copolymer (A2), the basic catalyst (B), the solvent (C), the reactive diluent (D), the photopolymerization initiator (E), and the copolymer (A) used optionally using a known mixing device. The photosensitive coloring composition of one embodiment can be produced by a method of mixing the modified copolymer (A2), the basic catalyst (B), the solvent (C), the reactive diluent (D), the photopolymerization initiator (E), the colorant (F), and the copolymer (A) used optionally using a known mixing device.

[0173] When producing a photosensitive resin composition or a photosensitive coloring composition, a reaction liquid (i.e., a modified resin composition) containing a modified copolymer (A2) obtained by converting the structural unit (pb) of the copolymer (A) to the structural unit (b) in the resin composition, a basic catalyst (B), a solvent (C), and an optional component copolymer (A) can be used as is as a raw material. In this case, the solvent (C) contained in the reaction liquid can be used as part or all of the solvent (C) contained in the photosensitive resin composition or the photosensitive coloring composition.

[0174] The photosensitive resin composition or the photosensitive coloring composition contains the modified copolymer (A2) having the structural unit (b) having a group represented by formula (1-1) or formula (1-2), the reactive diluent (D), and the photopolymerization initiator (E), and therefore, by light irradiation, the reactive diluent (D) polymerizes together with the ethylenically unsaturated group contained in the structural unit (b) of the modified copolymer (A2), thereby exhibiting good photocurability.

[0175] Furthermore, when the photosensitive resin composition or the photosensitive coloring composition contains a modified copolymer (A2) containing a structural unit (c) having a hydroxy group and a structural unit (d) having a blocked isocyanato group, the photosensitive resin composition or the photosensitive coloring composition has even better low-temperature curing properties.

[0176] 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 treatment is performed after exposing a coating film formed on a substrate, for example, the photosensitive resin composition or the photosensitive coloring composition can form a cured product having excellent solvent resistance because the crosslinking reaction proceeds sufficiently even if the baking temperature is low.

[0177] 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 with low heat resistance, such as a resin substrate, without causing any damage to the substrate. Furthermore, with regard to the photosensitive coloring composition, even when a colorant (F) with low heat resistance is used, a cured product can be formed that exhibits the inherent properties of the colorant (F).

[0178] The photosensitive coloring composition can obtain a cured product having excellent solvent resistance even when the baking temperature is low, so the colorant (F) is less likely to be eluted. Therefore, it is also possible to increase the content of the colorant (F) in the photosensitive coloring composition. A photosensitive coloring composition having a high content of the colorant (F) can be used, for example, as a material for the color pattern of a color filter to form a color filter with excellent color reproducibility.

[0179] The modified copolymer (A2) contained in the photosensitive resin composition or photosensitive coloring composition has a structural unit (a) having an acid group, so the photosensitive resin composition or photosensitive coloring composition has good alkaline developability. Since such a photosensitive resin composition or photosensitive coloring composition has excellent alkaline developability, for example, by applying it to a substrate to form a coating film, exposing it through a photomask corresponding to a predetermined pattern shape, developing the unexposed part with an alkaline aqueous solution, and then baking it at a sufficiently low temperature, a cured product having a predetermined pattern shape and excellent solvent resistance can be formed.

[0180] The photosensitive resin composition and the photosensitive coloring composition can be suitably used as materials for color filters.

[0181] 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.

[0182] <Cured Resin Film> The cured resin film of one embodiment comprises a cured product of a photosensitive resin composition or a photosensitive coloring composition.

[0183] The cured resin film can be produced, for example, by a method in which a photosensitive resin composition or a photosensitive coloring composition is applied to a substrate, the solvent (C) is removed by volatilization to form a coating film, the coating film is exposed to light to photocure it, and then a baking treatment is performed.

[0184] When forming a cured resin 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 to a substrate, and the solvent (C) 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 portions. Next, the unexposed portions of the coating film are developed with an alkaline aqueous solution. Thereafter, the developed coating film is subjected to a baking treatment to form a cured resin film having a predetermined pattern shape.

[0185] When producing a cured resin film, known methods can be used for applying the photosensitive resin composition or the photosensitive coloring composition, exposing the applied film, and developing the same.

[0186] The conditions for the baking treatment performed when producing a cured resin film can be appropriately determined depending on the composition of the photosensitive resin composition or photosensitive coloring composition, the film thickness of the coating film, the material of the substrate, and the like. The baking treatment can be performed, for example, at a temperature of 70°C to 250°C. When the baking temperature is 70°C or higher, the blocked isocyanato group of the structural unit (d) having a blocked isocyanato group contained in the modified copolymer (A2) in the photosensitive resin composition or photosensitive coloring composition is sufficiently dissociated. This generates an isocyanato group, which then undergoes a crosslinking reaction with the hydroxy group of the structural unit (c) having a hydroxy group. When the structural unit (d) has a carboxylic acid alkyl ester structure, crosslinking occurs through transesterification between the carboxylic acid alkyl ester structure and the hydroxy group. As a result, a good degree of curing is achieved, and a cured product with excellent solvent resistance is obtained. When the structural unit (d) has a carboxylic acid alkyl ester structure, both a deblocking reaction and a transesterification reaction can occur, but by adjusting the baking temperature, one of the reactions can be preferentially promoted. The baking temperature is preferably 75°C or higher, more preferably 80°C or higher. A baking temperature of 250°C or lower is a condition that can be tolerated by materials with low heat resistance, and is preferable because discoloration of the photosensitive resin composition or photosensitive coloring composition can be suppressed. The photosensitive resin composition and the photosensitive coloring composition have good low-temperature curing properties. Therefore, the baking temperature can be set to 160°C or lower depending on the heat resistance of the substrate on which the resin cured film is formed. For example, when a resin substrate is used as the substrate, it may be set to 150°C or lower, 120°C or lower, or 100°C or lower.

[0187] 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 temperature of the baking treatment, the film thickness of the coating film, etc.

[0188] 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 treatment at a low temperature and has excellent solvent resistance.

[0189] <Color Filter> A 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 the modified copolymer (A2) and the copolymer (A), 0.05 to 9 parts by mass of a basic catalyst (B), 10 to 90 parts by mass of the reactive diluent (D), 0.1 to 30 parts by mass of a photopolymerization initiator (E), 30 to 1,000 parts by mass of a solvent (C), and 3 to 80 parts by mass of a colorant (F), relative to a total of 100 parts by mass of the modified copolymer (A2), the optional copolymer (A), and the reactive diluent (D).

[0190] 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.

[0191] In the color filter, the pixels and black matrix are colored patterns formed from the cured product of the photosensitive coloring composition. In the color filter, known materials can be used for the components other than the materials of the pixels and black matrix.

[0192] 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 board, an array substrate, or the like can be used as appropriate depending on the application.

[0193] <Method for Manufacturing Color Filter> 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.

[0194] The colored pattern can be formed by photolithography. Specifically, a photosensitive colored composition is applied to a substrate to form a coating film. The coating film is then exposed to light through a photomask having a predetermined pattern shape, causing the exposed portions to photocure. The unexposed portions of the coating film are then developed with an alkaline aqueous solution. The developed coating film is then subjected to a baking treatment, thereby forming a colored pattern having a predetermined pattern shape.

[0195] The method for applying the photosensitive coloring composition is not particularly limited, but known methods such as screen printing, roll coating, curtain coating, spray coating, and spin coating can be used.

[0196] After applying the photosensitive coloring composition to the substrate, the solvent (C) contained in the coating film may be evaporated and removed by heating the substrate using a heating means such as a circulation oven, an infrared heater, or a hot plate, as needed. The conditions for heating the substrate to remove the solvent (C) are not particularly limited and may be appropriately set depending on 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.

[0197] Next, the coating film thus formed is partially exposed to active energy rays such as ultraviolet rays or excimer laser light through a negative photomask, and the exposed portions are photocured. The amount of active energy rays irradiated onto 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.

[0198] The alkaline aqueous solution used for developing the coating film is not particularly limited, but examples thereof include aqueous solutions of inorganic alkaline compounds such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, and potassium hydroxide; aqueous solutions of amine compounds such as ethylamine, diethylamine, and dimethylethanolamine; aqueous solutions of quaternary ammonium salts such as tetramethylammonium sulfate, hydrochloride, or p-toluenesulfonate; aqueous solutions of aniline compounds and salts 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, and 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and their sulfates, hydrochlorides, or p-toluenesulfonates; and aqueous solutions of p-phenylenediamine compounds and salts thereof. Additives such as antifoaming agents and surfactants may be added to the alkaline aqueous solution as needed.

[0199] 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.

[0200] The conditions for the baking treatment carried out when producing a color filter can be appropriately determined depending on the composition of the photosensitive coloring composition, the film 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, and 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 for the color filter.

[0201] When a colored pattern of a color filter is formed using a conventional photosensitive coloring composition, if the baking temperature is 200 ° C. or less, the solvent resistance of the colored pattern is insufficient. 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 using a conventional photosensitive coloring composition while ensuring the solvent resistance of the colored pattern. Specifically, the baking temperature can be 160 ° C. or less depending on the heat resistance of the substrate on which the resin cured film is formed. For example, when a colored pattern is formed using a resin substrate as the substrate, it may be 150 ° C. or less, 120 ° C. or less, or 100 ° C. or less.

[0202] 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 film thickness of the coating film, etc.

[0203] The photosensitive coloring composition has good photocurability and low-temperature curability. Therefore, when a colored pattern is formed using the photosensitive coloring composition of one embodiment, if the baking temperature is the same as when a colored pattern is formed using a conventional photosensitive coloring composition, the baking time can be shortened, and a color filter can be efficiently formed.

[0204] Using the above-described 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).

[0205] 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.

[0206] Through the above steps, a color filter is obtained.

[0207] The color filter has a color pattern made of the cured product of the photosensitive coloring composition described above. 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.

[0208] In addition, a colorant (F) having low heat resistance can be used as the colorant (F) contained in the photosensitive coloring composition used as a material for the color filter. This allows for a wider range of options for the colorant (F). Therefore, for example, it is possible to form a color filter containing a colorant (F) having low heat resistance and having a color pattern that exhibits the inherent properties of the colorant (F) having low heat resistance.

[0209] Furthermore, the colored pattern in the color filter can be formed on a substrate with low heat resistance, such as a resin substrate, without damaging the substrate. This increases the options for usable substrates. Specifically, for example, since a color filter can be formed on a substrate with low heat resistance, such as a resin substrate, the display can be made more flexible. In addition, the colored pattern in the color filter has excellent solvent resistance, so there is little color change.

[0210] Here, the case where a photosensitive coloring composition containing a photopolymerization initiator (E) is used and a colored pattern is produced using a method of photocuring the photosensitive coloring composition has been described as an example, but for example, instead of the photopolymerization initiator (E) contained in the photosensitive coloring composition, a photosensitive coloring composition containing a curing accelerator and a known epoxy resin is used, and after applying it on a substrate by an inkjet method, a colored pattern made of a cured product of the photosensitive coloring composition containing the modified copolymer (A2) may also be formed using a method of heating.

[0211] <Image Display Element> An image display element according to an embodiment includes a color filter. In the image display element, known components other than the color filter may be used. Specific examples of the image display element include a liquid crystal display element, an organic EL display element, and a solid-state imaging element such as a CCD element or a CMOS element.

[0212] Components other than the color filter in the image display element can be manufactured by known methods. For example, when manufacturing a liquid crystal display element as the image display element, it can be manufactured using the method shown below. First, a color filter is formed on a substrate using the method described above. Then, electrodes, spacers, etc. are formed sequentially 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 and bonded to it. Then, a predetermined amount of liquid crystal is injected between the opposing substrates and sealed.

[0213] The image display device has a color filter with excellent solvent resistance, and therefore, there is little color change.

[0214] The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0215] A synthesis example of the modified copolymer (A2) is shown below.

[0216] Example 1 (Synthesis Example 1) (Synthesis of Copolymer (A)) Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 282.6 g of propylene glycol monomethyl ether (Tokyo Chemical Industry Co., Ltd.) as solvent (C) was placed, and the mixture was stirred while purging with nitrogen gas and heated to 78°C.

[0217] Next, 17.2 g (20 mol%) of methacrylic acid as monomer (m-a), 49.7 g (15 mol%) of 2-[(diethylmalate)carbonylamino]ethyl acrylate as monomer (m-pb), 19.5 g (15 mol%) of 2-hydroxyethyl methacrylate as monomer (m-c), 90.3 g (30 mol%) of the reaction product of 2-isocyanatoethyl acrylate and diethyl malonate as monomer (m-d), and the monomer ( A raw material monomer solution was prepared by mixing 36.8 g (20 mol%) of 2-ethylhexyl acrylate as (me), 64.0 g (30 parts by mass relative to 100 parts by mass of the total of the monomer components) of propylene glycol monomethyl ether as solvent (C), and 34.2 g (16 parts by mass relative to 100 parts by mass of the total of the monomer components) of 2,2′-azobis(2,4-dimethylvaleronitrile) (FUJIFILM Wako Pure Chemical Industries, Ltd.) as a polymerization initiator.

[0218] The entire amount of the raw material monomer solution thus prepared was added dropwise to the solvent (C) in a flask under a nitrogen gas atmosphere at normal pressure using a dropping funnel over 1 hour. After the dropwise addition was completed, the solution in the flask was stirred and subjected to a polymerization reaction at 78°C for 3 hours to obtain a liquid containing the copolymer (A) and the solvent (C).

[0219] (Preparation of Resin Composition) To a liquid containing the copolymer (A) and the solvent (C) in a flask under a nitrogen gas atmosphere and at normal pressure, 0.4 g (0.2 parts by mass relative to 100 parts by mass of the total of the monomer components of the copolymer (A)) of hydroquinone monomethyl ether (MEHQ) as a polymerization inhibitor and 10.7 g (5 parts by mass relative to 100 parts by mass of the total of the monomer components of the copolymer (A)) of 4-dimethylaminopyridine (Kanto Chemical Co., Ltd.) as a basic catalyst (B) were added to obtain a resin composition.

[0220] (Synthesis of Modified Copolymer (A2)) In a flask under normal pressure and a nitrogen gas atmosphere, the resin composition was stirred and maintained at 78°C for 90 minutes to convert the structural unit (pb) having a group represented by formula (1) contained in copolymer (A) to a structural unit (b) having a group represented by formula (1-1) or formula (1-2). This resulted in a reaction liquid containing copolymer (A), modified copolymer (A2), and solvent (C). The conversion rate of structural unit (pb) to structural unit (b) was determined by the method described above and is shown in Table 1. The weight average molecular weight, ethylenically unsaturated group equivalent, and acid value of the mixture of copolymer (A) and modified copolymer (A2) were measured by the methods described above and are shown in Table 1. The blocked isocyanate group equivalent and hydroxyl group equivalent of the mixture of copolymer (A) and modified copolymer (A2) were calculated and are shown in Table 1.

[0221] To the reaction liquid containing the copolymer (A), modified copolymer (A2), and solvent (C) thus obtained, propylene glycol monomethyl ether acetate (Tokyo Chemical Industry Co., Ltd.) was added as solvent (C) so that the components other than the solvent were 35 mass %. This gave a liquid (modified resin composition) containing modified copolymer (A2) of Example 1.

[0222] Examples 2 to 6 (Synthesis Examples 2 and 6), Comparative Examples 1 and 2 (Comparative Synthesis Examples 1 and 2)] Liquids (modified resin compositions) containing modified copolymers (A2) of Examples 2 to 6 and liquids (modified resin compositions) containing modified copolymers (cA2) of Comparative Examples 1 and 2 were obtained in the same manner as in Example 1, except that the monomers and blending amounts shown in Table 1 were used and the time for the conversion reaction from the structural unit (pb) to the structural unit (b) was set as shown in Table 1. The conversion rates to the structural unit (b) of Examples 2 to 6 and Comparative Examples 1 and 2 were determined by the methods described above and are shown in Table 1. The weight average molecular weights, ethylenically unsaturated group equivalents, and acid values ​​of the mixtures of copolymers (A) and modified copolymers (A2) of Examples 2 to 6 and the mixtures of copolymers (cA) and modified copolymers (cA2) of Comparative Examples 1 and 2 were measured by the methods described above and are shown in Table 1. The blocked isocyanate group equivalent and the hydroxy group equivalent of the mixtures of the copolymer (A) and the modified copolymer (A2) in Examples 2 to 6 and the mixtures of the copolymer (cA) and the modified copolymer (cA2) in Comparative Examples 1 and 2 were calculated and are shown in Table 1.

[0223] Comparative Example 3 (Comparative Synthesis Example 3) (Synthesis of Copolymer (cA)) Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 142.7 g of propylene glycol monomethyl ether acetate (Tokyo Chemical Industry Co., Ltd.) was placed as solvent (C), and the mixture was stirred while purging with nitrogen gas, and the temperature was raised to 78°C.

[0224] Next, 66.2 g (20 mol%) of 2-[(diethyl malate)carbonylamino]ethyl acrylate as monomer (m-pb), 39.0 g (30 mol%) of 2-hydroxyethyl methacrylate as monomer (m-c), 25.1 g (10 mol%) of 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate as monomer (m-d), 73.6 g (40 mol%) of 2-ethylhexyl acrylate as monomer (m-e), and 32.7 g (16 parts by mass relative to 100 parts by mass of the total of the monomer components) of 2,2′-azobis(2,4-dimethylvaleronitrile) (Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator were mixed to prepare a raw material monomer solution.

[0225] The entire amount of the raw material monomer solution thus prepared was added dropwise to the solvent (C) in a flask under a nitrogen gas atmosphere at normal pressure using a dropping funnel over 1 hour. After the dropwise addition was completed, the solution in the flask was stirred and subjected to a polymerization reaction at 78°C for 3 hours to obtain a liquid containing the copolymer (cA) and the solvent (C).

[0226] (Preparation of Resin Composition) To a liquid containing copolymer (cA) and solvent (C) in a flask under a nitrogen gas atmosphere at normal pressure, 0.4 g (0.2 parts by mass relative to 100 parts by mass of the total of the monomer components of copolymer (cA)) of hydroquinone monomethyl ether (MEHQ) as a polymerization inhibitor and 10.2 g (5 parts by mass relative to 100 parts by mass of the total of the monomer components of copolymer (cA)) of 4-dimethylaminopyridine (Kanto Chemical Co., Ltd.) as a basic catalyst were added, thereby obtaining a resin composition.

[0227] (Synthesis of Modified Copolymer (cA2)) To the resin composition, 10 g (10 moles per 100 moles of the total of the monomers used in the synthesis of copolymer (cA)) of succinic anhydride (SA) (New Japan Chemical Co., Ltd.) and 0.9 g (0.4 parts by mass per 100 parts by mass of the total of the monomers and succinic anhydride used in the synthesis of copolymer (cA)) of lithium naphthenate (Toei Kako Co., Ltd.) as a catalyst were added, and the mixture was maintained at 78 ° C. for 90 minutes to carry out an addition reaction, and the structural unit (pb) having a group represented by formula (1) contained in copolymer (cA) was converted to a structural unit (b) having a group represented by formula (1-1) or formula (1-2). As a result, a reaction solution containing copolymer (cA), modified copolymer (cA2), and solvent (C) was obtained. The conversion rate of structural unit (pb) to structural unit (b) was determined by the method described above and is shown in Table 1. The weight average molecular weight, ethylenically unsaturated group equivalent, and acid value of the mixture of copolymer (cA) and modified copolymer (cA2) were measured by the above-mentioned methods and are shown in Table 1. The blocked isocyanato group equivalent and hydroxy group equivalent of the mixture of copolymer (cA) and modified copolymer (cA2) were calculated and are shown in Table 1.

[0228] To the reaction liquid containing the copolymer (cA), modified copolymer (cA2), and solvent (C) thus obtained, propylene glycol monomethyl ether acetate (Tokyo Chemical Industry Co., Ltd.) was added as solvent (C) so that the components other than the solvent were 35 mass %, thereby obtaining a liquid (modified resin composition) containing modified copolymer (cA2) of Comparative Example 3.

[0229] Comparative Example 4 (Comparative Synthesis Example 4) Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 241.2 g of propylene glycol monomethyl ether (Tokyo Chemical Industry Co., Ltd.) as solvent (C) was placed, and the mixture was stirred while purging with nitrogen gas and heated to 78°C.

[0230] Next, 15.5 g (18 mol%) of methacrylic acid as monomer (m-a), 18.2 g (14 mol%) of 2-hydroxyethyl methacrylate as monomer (m-c), 60.2 g (20 mol%) of a reaction product of 2-isocyanatoethyl acrylate and diethyl malonate as monomer (m-d), 88.3 g (48 mol%) of 2-ethylhexyl acrylate as monomer (m-e), 54.7 g (30 parts by mass relative to a total of 100 parts by mass of the monomer components) of propylene glycol monomethyl ether as solvent (C), and 29.2 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) (FUJIFILM Wako Pure Chemical Industries, Ltd.) as a polymerization initiator were mixed to prepare a raw material monomer solution.

[0231] The entire amount of the prepared raw material monomer solution was added dropwise over 1 hour using a dropping funnel to solvent (C) in a flask under nitrogen gas atmosphere and normal pressure. After completion of the addition, the solution in the flask was stirred while undergoing a polymerization reaction at 78°C for 3 hours to obtain a reaction solution containing copolymer (cA) and solvent (C). The weight average molecular weight, ethylenically unsaturated group equivalent, and acid value of copolymer (cA) were measured by the above-mentioned methods and are listed in Table 1. The blocked isocyanate group equivalent and hydroxy group equivalent of copolymer (cA) were calculated and are listed in Table 1.

[0232] To the reaction liquid containing the copolymer (cA) and solvent (C) thus obtained, propylene glycol monomethyl ether acetate (Tokyo Chemical Industry Co., Ltd.) was added as solvent (C) so that the components other than the solvent were 35 mass %, thereby obtaining a liquid (resin composition) containing copolymer (cA) of Comparative Example 4.

[0233]

[0234] The following compounds were used as compounds described in Tables 1 and 2: MAA: methacrylic acid (Kuraray Co., Ltd.) AOI-MDE: Karenz™ AOI-MDE, 2-[(diethyl malate)carbonylamino]ethyl acrylate (Resonac Co., Ltd.) AOI-DEM: Karenz™ AOI-DEM, reaction product of 2-isocyanatoethyl acrylate and diethyl malonate (malonic acid-2-[[[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester, Resonac Co., Ltd.) MOI-BP: Karenz™ MOI-BP, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (Resonac Co., Ltd.) HEMA: 2-hydroxyethyl methacrylate (Nippon Shokubai Co., Ltd.) 2EHA: 2-ethylhexyl acrylate (Toagosei Co., Ltd.) SA: succinic anhydride (New Japan Chemical Co., Ltd.) DBU: 1,8-diazabicyclo[5.4.0]-7-undecene (Sanapro Co., Ltd.) DMAP: 4-dimethylaminopyridine (Kanto Chemical Co., Ltd.) Pyridine (Kanto Chemical Co., Ltd.) 1,2-dimethylimidazole (Tokyo Chemical Industry Co., Ltd.) Triethylamine (Kanto Chemical Co., Ltd.) DABCO: 1,4-diazabicyclo[2.2.2]octane (Kanto Chemical Co., Ltd.)

[0235] [Evaluation of storage stability] 10 mL of the modified resin composition obtained in Example 1 was measured and placed in a 20 mL sample bottle, which was then sealed and stored at 5°C for 3 months. The weight average molecular weight of the sample after storage was measured, and the increase rate of the weight average molecular weight was calculated according to the following formula. The increase rate of the weight average molecular weight was calculated in the same manner for the modified resin compositions obtained in Examples 2 to 6 and Comparative Examples 1 to 3, and the resin composition obtained in Comparative Example 4. The increase rate of the weight average molecular weight is shown in Table 1. If the increase rate is within 20%, the storage stability is good. Increase rate of weight average molecular weight (%) = [(weight average molecular weight after storage - weight average molecular weight before storage) / weight average molecular weight before storage] × 100

[0236] [Examples 7 to 12, Comparative Examples 5 to 8] Using the modified resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3, and the resin composition of Comparative Example 4, mixtures of copolymers (A) and modified copolymers (A2) of Synthesis Examples 1 to 6, or mixtures of copolymers (cA) and modified copolymers (cA2) of Comparative Synthesis Examples 1 to 3, or copolymer (cA) of Comparative Synthesis Example 4 shown in Table 2, a basic catalyst, dipentaerythritol pentaacrylate (Toa Gosei Co., Ltd.) as the reactive diluent (D), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl-]-,-1-(O-acetyloxime) (Ciba Japan KK) as the photopolymerization initiator (E), a mixture of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether (338 parts by mass and 257 parts by mass, respectively) as the solvent (C), and Valifast Blue as the colorant (F). 2620 (phthalocyanine dye, Orient Chemical Industry Co., Ltd.) were mixed in the proportions shown in Table 2 to prepare the photosensitive coloring compositions of Examples 7 to 12 and Comparative Examples 5 to 8.

[0237] The amount of solvent is not included in the mixture of copolymer (A) and modified copolymer (A2), or the mixture of copolymer (cA) and modified copolymer (cA2), or the blending amount of copolymer (cA) shown in Table 2. The blending amount of solvent (C) shown in Table 2 is the sum of the amount of solvent contained in the modified resin compositions or resin compositions obtained in Synthesis Examples 1 to 6 and Comparative Synthesis Examples 1 to 4, and the amount of solvent added during the preparation of the photosensitive coloring composition.

[0238]

[0239] [Evaluation of Solvent Resistance] Solvent resistance was evaluated based on the film remaining rate.

[0240] (Film Remaining Rate) The photosensitive coloring compositions of Examples 7 to 12 and Comparative Examples 5 to 8 were each applied by spin coating onto a square glass substrate (alkali-free glass substrate) having a length of 5 cm and a width of 5 cm in plan view, so that the thickness after exposure was 2.5 μm, to form a coating film. Then, the solvent (C) in the coating film was evaporated and removed by heating at 100 ° C. for 3 minutes.

[0241] Next, the coating film was irradiated with ultraviolet light having a wavelength of 365 nm at an energy dose of 100 mJ / cm ２ The coating film was then cured by baking at 100°C for 20 minutes to form a cured film. The thickness of the cured film was measured with a step gauge. The thickness at this time was designated X.

[0242] The resulting cured film was then immersed in 20 g of propylene glycol monomethyl ether acetate (PGMEA) at 23° C. for 15 minutes. After immersion, the coated film was vacuum dried at 40° C. for 30 minutes, and the thickness of the coated film was measured with a step gauge. The thickness at this time was designated Y.

[0243] 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 rate using the following formula, and the solvent resistance of the cured film was evaluated. In other words, the closer the film remaining rate is to 100%, the better the solvent resistance of the cured film. A film remaining rate of 80% or more was set as the pass mark for evaluation. The film remaining rates of the cured film are shown in Table 2. Film remaining rate = (Y / X) x 100 (%)

[0244] As shown in Table 2, the cured films of the resin compositions of Examples 7 to 12 had a residual film rate (%) of 85% or more after immersion in PGMEA, and exhibited good solvent resistance even when the baking temperature was as low as 100°C.

[0245] [Evaluation of Developability] The developability was evaluated based on the solubility and adhesion of the cured film.

[0246] (Solubility) By spin coating method, the photosensitive coloring composition prepared in Examples 7 to 12 and Comparative Examples 5 to 8 was coated on a 5 cm square glass substrate (alkali-free glass substrate) so that the thickness after exposure was 1.5 μm (coating process). The glass substrate coated with the photosensitive coloring composition was heated at 100 ° C. for 3 minutes to volatilize the solvent, and the coating film was dried (pre-baking process).

[0247] Next, an ultra-high pressure mercury lamp was used to irradiate 100 mJ / cm ２The surface of the dried coating film was irradiated with light through a photomask (exposure step). The exposure step was performed by placing the photomask 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 (Yokohama Yushi Kogyo Co., Ltd.) (300-fold diluted) was sprayed onto the surface of the coating film for 60 seconds at a temperature of 23°C and a pressure of 0.1 MPa to remove the unexposed areas (development step). The dissolution state of the coating film when sprayed with the developer was observed, and the solubility was evaluated according to the following criteria. The results are shown in Table 2. 1: No residue was found in the unexposed areas, no powder was observed in the developer, and the pattern shape was good. 2: No residue was found in the unexposed areas, but powder was observed in the developer, and the pattern shape was relatively good. 3: Residue remained in the unexposed areas, and there were areas where the pattern shape was missing. 4: The film peeled off in the exposed areas, and no pattern remained.

[0248] (Adhesion) The glass substrate having the coating film after the development step was left standing 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 adhesion was evaluated based on the minimum line width that could be developed (minimum development dimension (µm)). The results are shown in Table 2.

[0249] According to the present disclosure, a photosensitive resin composition is provided that contributes to improved developability and provides a cured resin film having excellent solvent resistance. Also, according to the present disclosure, an image display element is provided that includes a color filter having a colored pattern formed from a cured resin 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. Copolymer (A), Basic catalyst (B), Solvent (C) and A resin composition containing, The copolymer (A) A structural unit (a) having an acid group, A structural unit (pb) having a group represented by the following formula (1), It is a copolymer containing, The basic catalyst (B) is a resin composition which is a basic catalyst having a pKa (acidity constant) of 4 to 12 at 25°C. 【Chemistry 1】 (In formula (1), R １ and R ４ Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ２ and R ３ Each of these is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents the linkage site with the residue obtained by removing the group of formula (1) from the structural unit (pb).

2. Modified copolymer (A2), Basic catalyst (B), Solvent (C) and A modified resin composition containing, The modified copolymer (A2) A structural unit (a) having an acid group, A structural unit (pb) having a group represented by the following formula (1), A structural unit (b) having a group represented by the following formula (1-1) or the following formula (1-2), It contains, The basic catalyst (B) is a modified resin composition in which the basic catalyst has a pKa (acidity constant) of 4 to 12 at 25°C. 【Chemistry 2】 (In formula (1), R １ and R ４ Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ２ and R ３ Each of these is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents the linkage site with the residue obtained by removing the group of formula (1) from the structural unit (pb). 【Transformation 3】 (In formula (1-1), R １ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and 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).) 【Chemistry 4】 (In formula (1-2), R ２ and R ３ Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ４ (This refers to a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents the linkage site with the residue obtained by removing the group of formula (1-2) from structural unit (b).)

3. The modified resin composition according to claim 2, wherein the basic catalyst (B) is at least one selected from the group consisting of pyridine and pyridine derivatives, and imidazole compounds.

4. The modified resin composition according to claim 2, wherein the basic catalyst (B) is at least one selected from pyridine, 4-dimethylaminopyridine, 1,2-dimethylimidazole, triethylamine, and 1,4-diazabicyclo[2.2.2]octane.

5. The modified resin composition according to claim 2, wherein the ethylenically unsaturated group equivalent of the modified copolymer (A2) is 300 to 10,000 g / mol.

6. A modified resin composition according to any one of claims 2 to 5, Reactive diluent (D), Photopolymerization initiator (E), A photosensitive resin composition containing [a specific substance].

7. A modified resin composition according to any one of claims 2 to 5, Reactive diluent (D), Photopolymerization initiator (E), Coloring agent (F), A photosensitive coloring composition containing [a specific substance].

8. A resin-cured film comprising a cured product of the photosensitive resin composition according to claim 6.

9. A resin-cured film comprising a cured product of the photosensitive coloring composition described in claim 7.

10. A color filter having a colored pattern made of a cured product of the photosensitive colored composition described in claim 7.

11. An image display element comprising the color filter described in claim 10.

12. The process includes a step (I) of preparing a resin composition containing a copolymer (A), a basic catalyst (B), and a solvent (C). The copolymer (A) A structural unit (a) having an acid group, A structural unit (pb) having a group represented by the following formula (1), It is a copolymer containing, The basic catalyst (B) is a basic catalyst having a pKa (acidity constant) of 4 to 12 at 25°C. 【Transformation 5】 (In formula (1), R １ and R ４ Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ２ and R ３ Each of these is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents the linkage site with the residue obtained by removing the group of formula (1) from the structural unit (pb).

13. The method comprises a heating step (II) in which the resin composition obtained by the manufacturing method described in claim 12 is held at a temperature of 50 to 100°C for 30 to 300 minutes. In the heating step (II), the copolymer (A) is converted to a modified copolymer (A2), The modified copolymer (A2) A structural unit (a) having an acid group, A structural unit (pb) having a group represented by the following formula (1), A structural unit (b) having a group represented by the following formula (1-1) or the following formula (1-2), A method for producing a modified resin composition containing the specified material. 【Transformation 6】 (In formula (1), R １ and R ４ Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ２ and R ３ Each of these is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents the linkage site with the residue obtained by removing the group of formula (1) from the structural unit (pb). 【Transformation 7】 (In formula (1-1), R １ R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ２ and R ３ Each of these is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents the linkage site with the residue obtained by removing the group of formula (1-1) from structural unit (b). 【Transformation 8】 (In formula (1-2), R ２ and R ３ Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ４ (This refers to a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents the linkage site with the residue obtained by removing the group of formula (1-2) from structural unit (b).)

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