Resin composition, modified resin composition, and method for manufacturing a modified resin composition

Abstract

A resin composition comprising a copolymer (A), a basic catalyst (B), and a solvent (C), wherein the copolymer (A) is a copolymer having a structural unit (a) having an acid group and a structural unit (pb) having a group represented by the following formula (1) (wherein R1 and R4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R2 and R3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * indicates a connection portion with a residue excluding the group of formula (1) from the structural unit (pb)), and the basic catalyst (B) is a basic catalyst having a pKa (acidity constant) of 4 to 12 at 25°C.

Description

Technology Field

[0001] The content of the present disclosure relates to a resin composition, a modified resin composition, a photosensitive resin composition, a photosensitive coloring composition, a resin cured film, an image display element, a method for manufacturing a resin composition, and a method for manufacturing a modified resin composition. Background Technology

[0002] Recently, from the perspective of resource and energy conservation, photosensitive resin compositions curable by active energy rays, such as ultraviolet rays and electron beams, are widely used in fields such as various coatings, printing, paints, and adhesives. In the field of electronic materials, such as printed circuit boards, photosensitive resin compositions curable by active energy rays are also used as solder resists and resists for color filters. While the required characteristics for curable photosensitive resin compositions are becoming increasingly diverse and sophisticated, among them, short-time curing properties considering productivity and low-temperature curing properties that suppress thermal damage to the applied components are required.

[0003] A color filter generally consists of 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 this configuration is typically manufactured by sequentially forming the black matrix, pixels, and the protective film on the transparent substrate. Various methods have been proposed for forming the pixels and the black matrix (hereinafter, the pixels and the black matrix are referred to as "coloring patterns"). Among these, the pigment / dye dispersion method, which produces the coloring pattern using a photolithography process that involves repeating coating, exposure, development, and baking with a photosensitive resin composition as a resist, has become the current mainstream method because it provides a coloring pattern with excellent durability and few defects such as pinholes.

[0004] Generally, photosensitive resin compositions used in photolithography processes contain an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a colorant, and a solvent. While pigment / dye dispersion methods offer the aforementioned advantages, problems often arise due to limitations. Specifically, since baking is repeated to form patterns of a black matrix, R, G, and B, high heat resistance is required for the photosensitive resin composition, and the types of colorants that can be used are restricted to those capable of withstanding high baking temperatures.

[0005] Recently, photosensitive resin compositions having low-temperature curing properties suitable for materials with low heat resistance, such as organic EL, have been proposed. For example, Patent Document 1 discloses a coloring composition having a specific partial structure and hydroxyl groups as a photosensitive resin composition that can provide a cured product with excellent solvent resistance even under low-temperature curing conditions and can be used suitablely for applications such as color filters. Prior art literature

[0006] Japanese Patent Publication No. 2021-102759 The problem to be solved

[0007] However, recently, even greater low-temperature curing properties are required. Consequently, there is a concern that film curing may not be sufficient, leading to a decrease in solvent resistance due to a trade-off. Therefore, it is required that the produced cured product possesses high solvent resistance even when cured under low-temperature conditions. In addition to this, it is also required that the photosensitive resin composition possesses excellent developability.

[0008] The present disclosure provides a resin composition capable of efficiently introducing ethylenically unsaturated groups into a resin. Furthermore, it provides a modified resin composition that imparts a resin cured film having excellent solvent resistance by contributing to improved developability, and a photosensitive resin composition and a photosensitive coloring composition using the same. The present disclosure also provides a resin cured film having excellent solvent resistance and an image display element having the same. means of solving the problem

[0009] The present disclosure includes the following aspects.

[0010] [1]

[0011] copolymer (A) and,

[0012] Basic catalyst (B) and,

[0013] A resin composition containing a solvent (C),

[0014] The above copolymer (A) is,

[0015] A structural unit (a) having a saturation, and

[0016] A copolymer containing a structural unit (pb) having a group represented by the following formula (1),

[0017] The above basic catalyst (B) is a resin composition that is a basic catalyst having a pKa (acidity constant) of 4 to 12 at 25°C.

[0018]

[0019] (In Equation (1), R 1 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 2 and R 3 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a connection site between the structural unit (pb) and a residue excluding the group of Formula (1).

[0020] [2]

[0021] Modified copolymer (A2) and,

[0022] Basic catalyst (B) and,

[0023] A modified resin composition containing a solvent (C),

[0024] The above modified copolymer (A2) is,

[0025] A structural unit (a) having a saturation, and

[0026] A structural unit (pb) having a group represented by the following formula (1), and

[0027] It contains a structural unit (b) having a group represented by the following formula (1-1) or the following formula (1-2), and

[0028] The above basic catalyst (B) is a modified resin composition having a basic catalyst with a pKa (acidity constant) of 4 to 12 at 25°C.

[0029]

[0030] (In Equation (1), R 1 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 2 and R 3 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a connection site between the structural unit (pb) and a residue excluding the group of Formula (1).

[0031]

[0032] (In Equation (1-1), R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 2 and R 3 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * indicates a connection site with a residue excluding the group of Formula (1-1) from the structural unit (b).

[0033]

[0034] (In Equation (1-2), R 2 and R 3Each is 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 * indicates a connection site between the structural unit (b) and a residue excluding the group of Formula (1-2).

[0035] [3]

[0036] The modified resin composition described in [2], wherein the basic catalyst (B) is at least one selected from the group consisting of pyridine and pyridine derivatives and imidazole compounds.

[0037] [4]

[0038] A modified resin composition described in [2] or [3] in which 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.

[0039] [5]

[0040] A modified resin composition described in any one of [2] to [4], wherein the ethylenically unsaturated group equivalent of the modified copolymer (A2) is 300 to 10000 g / mol.

[0041] [6]

[0042] A modified resin composition described in any one of [2] to [5], and

[0043] Reactive diluent (D) and,

[0044] A photosensitive resin composition containing a photopolymerization initiator (E).

[0045] [7]

[0046] A modified resin composition described in any one of [2] to [5], and

[0047] Reactive diluent (D) and,

[0048] A photopolymerization initiator (E) and,

[0049] A photosensitive coloring composition containing a coloring agent (F).

[0050] [8]

[0051] [6] A resin cured film consisting of a cured product of the photosensitive resin composition described in [6].

[0052] [9]

[0053] [7] A resin cured film consisting of a cured product of the photosensitive coloring composition described in [7].

[0054]

[10]

[0055] A color filter having a color pattern made of a cured photosensitive color composition described in [7].

[0056]

[11]

[0057] Image display element having a color filter as described in

[10] .

[0058]

[12]

[0059] A process (I) for preparing a resin composition containing a copolymer (A), a basic catalyst (B), and a solvent (C), and

[0060] The above copolymer (A) is,

[0061] A structural unit (a) having a saturation, and

[0062] A copolymer containing a structural unit (pb) having a group represented by the following formula (1),

[0063] A method for preparing a resin composition in which the above basic catalyst (B) is a basic catalyst having a pKa (acidity constant) of 4 to 12 at 25°C.

[0064]

[0065] (In Equation (1), R 1 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 2 and R 3 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a connection site between the structural unit (pb) and a residue excluding the group of Formula (1).

[0066]

[13]

[0067]

[12] A resin composition obtained by the manufacturing method described in

[12] has a heating process (II) in which it is maintained for 30 to 300 minutes under conditions of 50 to 100°C, and

[0068] In the above heating process (II), the copolymer (A) is converted into a modified copolymer (A2), and

[0069] The above modified copolymer (A2) is,

[0070] A structural unit (a) having a saturation, and

[0071] A structural unit (pb) having a group represented by the following formula (1), and

[0072] A method for preparing a modified resin composition containing a structural unit (b) having a group represented by the following formula (1-1) or the following formula (1-2).

[0073]

[0074] (In Equation (1), R 1 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 2 and R 3 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a connection site between the structural unit (pb) and a residue excluding the group of Formula (1).

[0075]

[0076] (In Equation (1-1), R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 2 and R 3 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * indicates a connection site with a residue excluding the group of Formula (1-1) from the structural unit (b).

[0077]

[0078] (In Equation (1-2), R2 and R 3 Each is 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 * indicates a connection site between the structural unit (b) and a residue excluding the group of Formula (1-2). Effects of the invention

[0079] According to the present disclosure, a resin composition capable of efficiently introducing ethylenically unsaturated groups into a resin can be provided. Additionally, a modified resin composition that imparts a resin cured film having excellent solvent resistance by contributing to improved developability, and a photosensitive resin composition and a photosensitive coloring composition using the same can be provided. Furthermore, a resin cured film with excellent solvent resistance formed by curing the photosensitive resin composition and the photosensitive coloring composition, a color filter, and an image display element equipped with the same can be provided. Specific details for implementing the invention

[0080] Embodiments of the present invention will be described in detail below. However, the present invention is not limited to the embodiments shown below.

[0081] In this specification, when "~" is used for a numerical range, the values ​​at both ends are the upper and lower limits, respectively, and are included in the numerical range. If multiple upper or lower limits are specified, a numerical range can be created from all combinations of the upper and lower limits. Similarly, if multiple numerical ranges are specified, separate numerical ranges can be created by individually selecting and combining the upper and lower limits from these numerical ranges.

[0082] 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.

[0083] In this specification, "ethylenically unsaturated bond" means a double bond formed between carbon atoms excluding carbon atoms forming an aromatic ring, and "ethylenically unsaturated group" means a group having an ethylenically unsaturated bond.

[0084] In this specification, "structural unit" means 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.

[0085] <Resin Composition>

[0086] A resin composition of one embodiment contains a copolymer (A), a basic catalyst (B), and a solvent (C).

[0087] [Copolymer(A)]

[0088] 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). As the copolymer (A) has the structural unit (pb) having a group represented by the following formula (1), conversion to the structural unit (b) proceeds through the action of the basic catalyst (B) described below, thereby introducing an ethylenically unsaturated group into the copolymer (A). By using this in a photosensitive resin composition, a resin cured film with improved developability and good solvent resistance can be obtained.

[0089]

[0090] (In Equation (1), R 1 and R 4Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 2 and R 3 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a connection site between the structural unit (pb) and a residue excluding the group of Formula (1).

[0091] The copolymer (A) may additionally contain, if necessary, a structural unit (c) having a hydroxyl group, a structural unit (d) having a block isocyanate group, or a combination thereof. The copolymer (A) may additionally contain, if necessary, other structural units (e) other than structural units (a) to (d) and (pb).

[0092] (Structural unit having a genus(a))

[0093] A structural unit (a) having an acid group (also referred to simply as "structural unit (a)") is not particularly limited as long as it does not have an ethylenically unsaturated group and has an acid group. When a modified copolymer (A2) obtained by converting copolymer (A) is used in a photosensitive resin composition, good alkali developability can be obtained because the copolymer (A) has a structural unit (a) having an acid group. Examples of acid groups include carboxyl groups, sulfonate groups, and phospho groups. Among these acid groups, a carboxyl group is preferred as the acid group of the structural unit (a) due to ease of availability.

[0094] The structural unit (a) having an acid group is preferably a structural unit derived from a monomer (ma) having an ethylenically unsaturated bond with an acid group (hereinafter also referred to simply as monomer (ma)). Specific examples of monomer (ma) include unsaturated carboxylic acids or their anhydrides such as (meth)acrylic acid, α-bromo(meth)acrylic acid, β-pril(meth)acrylic acid, crotonic acid, cinnamic acid, α-cyanosinnamic acid, maleic acid, maleic anhydride, monomethyl maleic acid, monoethyl maleic acid, monoisopropyl maleic acid, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride; unsaturated sulfonic acids such as 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, p-styrenesulfonic acid; and unsaturated phosphonic acids such as vinylphosphonic acid. The monomer (ma) is preferably an unsaturated carboxylic acid or its anhydride, more preferably (meth)acrylic acid or a (meth)acrylate having a carboxylic acid group, and even more preferably (meth)acrylic acid.

[0095] Monomers (ma) having acid groups and ethylenically unsaturated bonds may be used alone or in combination of two or more types.

[0096] The content of structural unit (a) is preferably 5 to 50 mol% of the total structural units of copolymer (A), more preferably 8 to 40 mol%, and even more preferably 10 to 30 mol%. If the content of structural unit (a) is 5 mol% or more, good developability of the photosensitive resin composition using the modified copolymer (A2) converted from copolymer (A) is obtained. If the content of structural unit (a) is 50 mol% or less, the content of structural unit (pb) can be sufficiently secured, so the effect attributable to structural unit (b) can be sufficiently secured.

[0097] (Structural unit (pb) having a group represented by Equation (1))

[0098] A structural unit (pb) having a group represented by formula (1) (also referred to simply as “structural unit (pb)”) is a structural unit that does not have an acid group and an ethylenically unsaturated group, and has a group represented by the following formula (1).

[0099]

[0100] (In Equation (1), R 1 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 2 and R 3 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a connection site between the structural unit (pb) and a residue excluding the group of Formula (1).

[0101] The group represented by Equation (1) does not have to be of only one type. R of each structural unit 1 They may be different, and the R of each structural unit 2 They may also be different, and the R of each structural unit 3 They may also be different, and the R of each structural unit 4 It is okay if they are all different.

[0102] In Equation (1), R 1 and R 4 Each is 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, since a conversion reaction from a structural unit (pb) to a structural unit (b) having a group represented by Formula (1-1) or Formula (1-2) described later is likely to occur, it is more preferable that it be a hydrocarbon group having 1 to 3 carbon atoms. R 1 and R 4 It is preferably an alkyl group having 1 to 5 carbon atoms, preferably a methyl or ethyl group, and particularly preferably an ethyl group. R 1 and R 4 It may be the same or different. Since the monomer (m-pb) described later can be easily manufactured, R 1and R 4 It is desirable that it be the same.

[0103] In Equation (1), R 2 and R 3 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. In particular, since a conversion reaction from a structural unit (pb) to a structural unit (b) having a group represented by Formula (1-1) or Formula (1-2) described later is likely to occur, it is more preferable that it be a hydrogen atom or a methyl group, and particularly preferable that it be a hydrogen atom. R 2 and R 3 It may be the same or different. Since the monomer (m-pb) described later can be easily manufactured, R 2 and R 3 It is desirable to have something like this.

[0104] The structural unit (pb) is a structural unit derived from a monomer (m-pb) having a group represented by the above formula (1) (also referred to simply as “monomer (m-pb)”). The monomer (m-pb) may be used alone or in combination of two or more types.

[0105] Monomer (m-pb) is a monomer having an ethylenically unsaturated bond and a group represented by the above formula (1).

[0106] Examples of monomers (m-pb) include isocyanato groups in isocyanate compounds having ethylenically unsaturated groups such as vinyl groups and (meth)acryloyloxy groups in the molecule, and compounds in which hydroxyl groups in hydroxyl group-containing compounds represented by the following formula (4) are urethane-reacted.

[0107]

[0108] (In Equation (4), R 1 , R 2 , R 3 and R 4 is R in Equation (1) 1 , R2 , R 3 and R 4 It is the same as.)

[0109] A conventionally known method can be used to urethane-react the above-mentioned isocyanate compound having an ethylene unsaturated group and the hydroxyl group-containing compound represented by formula (4).

[0110] The above urethane reaction can be carried out regardless of the presence or absence of a solvent. When carrying out the above urethane reaction using a solvent, the solvent used should be inert to isocyanate groups, and known solvents may be used.

[0111] The above urethane reaction is generally preferably carried out at a temperature of -10°C or higher and 90°C or lower, more preferably at a temperature of 5°C or higher and 70°C or lower, and even more preferably at a temperature of 10°C or higher and 40°C or lower.

[0112] When carrying out the above urethane reaction, a urethane catalyst such as dibutyltin dilauric acid, and a polymerization inhibitor such as phenothiazine, hydroquinone monomethyl ether, or 2,6-di-tert-butyl-4-methylphenol (BHT) may be used as needed.

[0113] Examples of isocyanate compounds having an ethylenically unsaturated group used as a raw material for monomer (m-pb) include isocyanate compounds represented by the following formula (5).

[0114]

[0115] (In Equation (5), R 9 represents a hydrogen atom or a methyl group, and R 10 -CO-, -COOR 11 -(Here, R 11 is an alkylene group having 1 to 6 carbon atoms) or -COO-R 12 O-CONH-R 13 -(Here, R 12is an alkylene group having 2 to 6 carbon atoms, and R 13 ...is an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms that may have substituents.)

[0116] In the isocyanate compound represented by Equation (5), R 10 From the ease of preparation of silver isocyanate compounds, -COOR 11 It is desirable that..., R 11 It is more preferable that this be an alkylene group having 1 to 4 carbon atoms.

[0117] Examples of isocyanate compounds represented by the above formula (5) include, specifically, 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, methacryloyl isocyanate, etc.

[0118] As the isocyanate compound used as a raw material for the monomer (m-pb), the reaction product obtained by reacting a hydroxyalkyl (meth)acrylate and a diisocyanate compound at an equimolar ratio (hydroxyalkyl (meth)acrylate: diisocyanate compound = 1 mol: 1 mol) may be used.

[0119] The alkyl group of the above hydroxyalkyl (meth)acrylate is preferably an ethyl group or an n-propyl group for ease of reaction, and more preferably an ethyl group.

[0120] Examples of the above diisocyanate compounds 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, lysine diisocyanate, etc.

[0121] Other isocyanate compounds mentioned above used as raw materials for monomer (m-pb) include 1,1-bis(methacryloyloxymethyl)methylisocyanate, 1,1-bis(methacryloyloxymethyl)ethylisocyanate, 1,1-bis(acryloyloxymethyl)methylisocyanate, and 1,1-bis(acryloyloxymethyl)ethylisocyanate.

[0122] As for the isocyanate compound used as a raw material for the monomer (m-pb), from the perspective of low-temperature curability, an isocyanate compound having a (meth)acryloyl group or a (meth)acryloyloxy group is preferred, and an isocyanato group-containing (meth)acrylate is more preferred, and 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. 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, and 1,1-bis(methacryloyloxymethyl)ethyl isocyanate are more preferred.

[0123] Examples of hydroxyl group-containing compounds represented by formula (4) used as raw materials for monomer (m-pb) include malic acid esters, 2-methylmalic acid esters, 3-methylmalic acid esters, 2,3-dimethylmalic acid esters, etc. Among these, malic acid esters are preferred from the perspective of ease of conversion reaction to structural unit (b) having a group represented by formula (1-1) or formula (1-2) and ease of obtaining.

[0124] The number of carbon atoms in two ester sites (-COOR) included in the hydroxyl group-containing compound represented by formula (4) 1 and COOR 4 R in 1 and R 4 The number of carbon atoms) is 1 to 20 each, but it is preferable that it is 1 to 5 each, and more preferable that it is 1 to 3.

[0125] The hydroxyl group-containing compound represented by formula (4) is particularly preferred to be diethyl malate from the perspective of ease of availability.

[0126] Specifically, as the monomer (m-pb), it is preferable to be 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 perspective of ease of manufacturing, it is particularly preferable to be 2-[(diethyl malate)carbonylamino]ethyl acrylate.

[0127] The content of the structural unit (pb) is preferably 3 to 40 mol% of the total structural units of the copolymer (A), more preferably 5 to 35 mol%, and even more preferably 10 to 30 mol%. If 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 the modified copolymer (A2) into which ethylenically unsaturated groups have been introduced in a photosensitive resin composition, good low-temperature curing properties and developability are obtained. If the content of the structural unit (pb) is 40 mol% or less, the content of the structural unit (a) can be sufficiently secured, and by using the modified copolymer (A2) in a photosensitive resin composition, sufficient developability is obtained.

[0128] (Structural unit having a hydroxyl group (c))

[0129] The copolymer (A) may, if necessary, contain a structural unit (c) having a hydroxyl group (also referred to simply as "structural unit (c)"). The structural unit (c) is not limited to having an acid group, an ethylenically unsaturated group, or a block isocyanate group, and is a structural unit having a hydroxyl group. By having the copolymer (A) having a structural unit (c) having a hydroxyl group, crosslinking with the structural unit (d) having a block isocyanate group described later proceeds upon heating. As a result, when the modified copolymer (A2) obtained by converting the copolymer (A) is used in a photosensitive resin composition, good solvent resistance of the cured product is obtained even under thermal curing under low temperature conditions.

[0130] The structural unit (c) having a hydroxyl group is preferably a structural unit derived from a monomer (mc) having a hydroxyl group and an ethylenically unsaturated group (hereinafter also referred to simply as monomer (mc). Specific examples of monomer (mc) include (meth)acrylic acid ester derivatives having a hydroxyl group, specifically hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; and 2-hydroxy-3-phenoxypropyl (meth)acrylate. Among them, hydroxyalkyl (meth)acrylate is preferred from the perspective of reactivity when synthesizing copolymer (A), low-temperature curing properties of the photosensitive resin composition containing the modified copolymer (A2), and ease of availability. As for hydroxyalkyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate are preferred, and 4-hydroxybutyl (meth)acrylate is more preferred from the perspective of lowering the glass transition temperature of copolymer (A).

[0131] Monomers (mc) having hydroxyl groups and ethylenically unsaturated groups may be used alone or in combination of two or more types.

[0132] The content of structural unit (c) is preferably 3 to 40 mol% of the total structural units of copolymer (A), more preferably 5 to 30 mol%, and even more preferably 8 to 25 mol%. If the content of structural unit (c) is 3 mol% or more, sufficient crosslinking of the hydroxyl group of structural unit (c) and the block isocyanate group of structural unit (d) can be secured. As a result, the low-temperature curing properties of the photosensitive resin composition using the modified copolymer (A2) converted from copolymer (A) are improved. If the content of structural unit (c) is 40 mol% or less, sufficient content of structural unit (a) and structural unit (pb) can be secured, so a sufficient amount of ethylenically unsaturated groups can be introduced into the copolymer (A). Accordingly, sufficient developability of the cured product of the photosensitive resin composition using the modified copolymer (A2) after conversion is obtained. In addition, since the content of the structural unit (d) can be sufficiently secured, the amount of bridging with the structural unit (c) is sufficiently secured.

[0133] (Structural unit having block isocyanate (d))

[0134] The copolymer (A) may, if necessary, contain a structural unit (d) having a block isocyanate group (also referred to simply as "structural unit (d)"). The structural unit (d) is a structural unit that does not have an acid group and an ethylenically unsaturated group and does not correspond to the structural unit (pb), and is not particularly limited as long as it is a structural unit having a block isocyanate group. By having the structural unit (d) having a block isocyanate group in the copolymer (A), crosslinking with the structural unit (c) having a hydroxyl group proceeds upon heating. The crosslinking is formed, for example, by the reaction between the isocyanate group and the hydroxyl group generated by the decomposition of the blocking agent. If the blocking agent is a compound having an alkyl carboxylate structure, crosslinking can be formed by the ester exchange between the alkyl carboxylate structure and the hydroxyl group described later, even without the dissociation of the blocking agent. By this, when the modified copolymer (A2) is used in the photosensitive resin composition, good solvent resistance of the cured product is obtained even during thermal curing under low temperature conditions.

[0135] The structural unit (d) having a blocked isocyanate group has a structure in which the isocyanate group is blocked by a blocking agent. The reaction between the isocyanate group and the blocking agent can be carried out regardless of the presence or absence of a solvent. If a solvent is used, it is necessary to use a solvent that is inert to the isocyanate group. In the blocking reaction, organometallic salts such as tin, zinc, and lead, or tertiary amines may be used as catalysts. The blocking reaction can generally be carried out at -20 to 150°C, but it is preferable to carry out it at 0 to 100°C.

[0136] Blocking agents that block isocyanato groups include, for example, lactam compounds such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; alcohol compounds such as methanol, ethanol, propanol, butanol, ethylene glycol, methylcellosolve, butylcellosolve, methylcarbitol, benzyl alcohol, phenylcellosolve, furfuryl alcohol, and cyclohexanol; Phenol compounds such as phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, butylphenol (such as o-isopropylphenol, p-tert-butylphenol), p-tert-octylphenol, nonylphenol, dinonylphenol, styreneated phenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, thymol, 1-naphthol, p-nitrophenol, p-chlorophenol, etc.; active methylene compounds such as dimethyl malonicate, diethyl malonicate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, etc.; mercaptan compounds such as butyl mercaptan, thiophenol, tert-dodecyl mercaptan, etc.; amine compounds such as diphenylamine, phenylnaphthylamine, aniline, carbazole, etc. Examples include acid amide compounds such as acetanilide, acetanisidide, acetamide, and benzamide; imide compounds such as imide succinate and imide maleate; imidazole compounds such as imidazole, 2-methylimidazole, and 2-ethylimidazole; pyrazole compounds such as pyrazole and 3,5-dimethylpyrazole; urea compounds such as urea, thiourea, and ethyleneurea; carbamic acid compounds such as phenyl N-phenylcarbamate and 2-oxazolidone; imine compounds such as ethyleneimine and polyethyleneimine; oxime compounds such as formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketooxime, methyl isobutyl ketooxime, and cyclohexanone oxime; and bisulfites such as sodium bisulfite and potassium bisulfite.

[0137] Blocks may be used alone or in combination of two or more types.

[0138] In one embodiment, as a blocking agent, from the perspective of improving low-temperature curability and solvent resistance as a photosensitive resin composition, a blocking agent having a dissociation rate of 5 to 99 mass% when heat-treated at 100°C for 30 minutes is preferred, one or more selected from the group consisting of 3,5-dimethylpyrazole, methyl ethyl keto oxime, 4-methyl hydroxybenzoate, 2-methyl hydroxybenzoate, and 3,5-xylenol is more preferred, and 3,5-dimethylpyrazole is even more preferred.

[0139] In the present specification, the dissociation rate of the blocked isocyanato group is defined as the value obtained by measuring the mass loss ratio of the blocked isocyanato group-containing compound by HPLC analysis after preparing an n-octanol solution in which the concentration of the blocked isocyanato group-containing compound is 20 mass%, adding 1 mass% of dibutyltin laurate and 3 mass% of phenothiazine (polymerization inhibitor) to the solution, and heating at 100°C for 30 minutes. As the blocked isocyanato group-containing compound, a compound in which the isocyanato group of 2-isocyanatoethylacrylate is blocked by the blocking agent to be measured is used. If a blocking agent is used in which the dissociation rate is within the above range, sufficient stability of the copolymer (A) during synthesis can be ensured, the baking temperature during the production of the cured film can be set sufficiently low, and sufficient solvent resistance of the cured film can also be ensured.

[0140] In one embodiment, as a blocking agent, a blocking agent having an alkyl carboxylate structure is preferred from the perspective of improving low-temperature curability and solvent resistance as a photosensitive resin composition. In this case, the structural unit (d) having a block isocyanato group has an alkyl carboxylate structure. An alkyl carboxylate structure refers to a structure having an alkyloxycarbonyl group, and a structure having an alkyloxycarbonyl group having 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 hydroxyl group of the structural unit (c) to form a cross-linked structure. Therefore, a photosensitive resin composition using a modified copolymer (A2) converted from a copolymer (A) having a structural unit having an alkyl carboxylate structure can provide a cured film with excellent solvent resistance even when cured at a low temperature of 50°C to 150°C.

[0141] It is more preferable that the structural unit having the alkyl carboxylate structure be a structural unit having a group represented by the following formula (2) or a group represented by the following formula (3).

[0142]

[0143] (In Equation (2), R 5 and R 6 Each represents an alkyl group having 1 to 10 carbon atoms independently, n1 and n2 each represent an integer from 0 to 2 independently, and * represents a connection site with a residue excluding the block isocyanato group from the structural unit (d).

[0144]

[0145] (Equation (3), R 7 and R 8 Each represents an alkyl group having 1 to 10 carbon atoms independently, n3 and n4 each represent an integer from 0 to 2 independently, and * represents a connection site with a residue excluding the block isocyanato group from the structural unit (d).

[0146] The group represented by Equation (2) does not have to be of only one type. R of each structural unit 5 They may be different, and the R of each structural unit 6 Each may be different, each structural unit's n1 may be different, and each structural unit's n2 may also be different. The same applies to the group represented by Equation (3).

[0147] R in the above equation (2) 5 and R 6 Each is independently an alkyl group having 1 to 10 carbon atoms. R 5 and R 6 It is preferable that each is independently an alkyl group having 2 to 6 carbon atoms, and more preferable that it is an alkyl group having 2 to 3 carbon atoms, and R 5 and R 6 It is most desirable that both of these are ethyl groups.

[0148] R 5 and R 6 In the case where this is an ethyl group, when heat-curing the photosensitive resin composition containing the modified copolymer (A2), R 5 and R 6 Ethanol is produced by ester exchange with the hydroxyl group of this structural unit (c). It is desirable that the ethanol produced during the thermal curing of the photosensitive resin composition is easily evaporated and removed by heating to thermally cure the photosensitive resin composition.

[0149] n1 and n2 in the above equation (2) each independently represent integers from 0 to 2. It is preferable that n1 and n2 each independently be 0 or 1, and it is more preferable that both are 0.

[0150] R in the above equation (3) 7 and R 8 Each is independently an alkyl group having 1 to 10 carbon atoms. R 7It is preferable that the alkyl group has 2 to 6 carbon atoms, more preferable that it has 2 to 3 carbon atoms, and even more preferable that it is an ethyl group.

[0151] R 7 In the case where this is an ethyl group, when heat-curing the photosensitive resin composition containing the modified copolymer (A2), R 7 Ethanol is produced by ester exchange with the hydroxyl group of this structural unit (c). It is desirable that the ethanol produced during the thermal curing of the photosensitive resin composition is easily evaporated and removed by heating to thermally cure the photosensitive resin composition.

[0152] R 8 It is preferable that the alkyl group has 1 to 6 carbon atoms, more preferable that it has 1 to 3 carbon atoms, and even more preferable that it is a methyl group.

[0153] n3 and n4 in the above equation (3) each represent an integer from 0 to 2 independently. It is preferable that n3 and n4 each be 0 or 1 independently, and more preferable that both be 0.

[0154] From the perspective of ease of proceeding ester exchange with the hydroxyl group of the structural unit (c) and low-temperature curability as a photosensitive resin composition, it is preferable that the structural unit (d) has a group represented by formula (2).

[0155] The structural unit (d) having a block isocyanate group is preferably a structural unit derived from a monomer (md) having an ethylenically unsaturated bond with a block isocyanate group (also referred to simply as monomer (md)). The monomer (md) may be used alone or in combination of two or more types. Specific examples of groups having an ethylenically unsaturated bond include vinyl groups, (meth)acryloyloxy groups, etc.

[0156] Examples of monomers (md) include isocyanate compounds having ethylenically unsaturated groups and reaction products of blocking agents. As for isocyanate compounds having ethylenically unsaturated groups, the same as the isocyanate compound used as a raw material for the above monomer (m-pb) can be used.

[0157] The structural unit having the group represented by formula (2) or (3) is preferably a structural unit derived from a monomer having an ethylenically unsaturated bond with the group represented by formula (2) or (3). Specific examples of the group having an ethylenically unsaturated bond include vinyl groups, (meth)acryloyloxy groups, etc.

[0158] Examples of monomers having ethylenically unsaturated bonds with groups represented by formula (2) or (3) include isocyanate compounds having ethylenically unsaturated groups, malonic acid diesters, or acetoacetic acid esters.

[0159] As an isocyanate compound having an ethylenically unsaturated group, the same as the isocyanate compound used as a raw material for the monomer (m-pb) described above can be used.

[0160] Examples of malonic acid diesters include dimethyl malonic acid, diethyl malonic acid, di(n-propyl malonic acid), and di(i-propyl malonic acid. From the perspective of ease of availability, cost, and quality, diethyl malonic acid and dimethyl malonic acid are preferred.

[0161] Examples of acetoacetic acid esters include methyl acetoacetate and ethyl acetoacetate.

[0162] Specific examples of monomers having ethylenically unsaturated bonds with the group represented by formula (2) include Carens (trademark) MOI-DEM (Resonac Co., Ltd.) and Carens (trademark) AOI-DEM (Resonac Co., Ltd.).

[0163] The reaction between an isocyanate compound having an ethylenically unsaturated group and a malonic acid diester or an acetoacetic acid ester can be carried out regardless of the presence or absence of a solvent. When carrying out the above reaction using a solvent, a solvent that is inert to the isocyanate group is used. In the above reaction, organometallic salts such as tin, zinc, and lead, or tertiary amines may be used as catalysts.

[0164] The above reaction can generally be carried out at a temperature of -20 to 150°C, and it is preferable to carry out it at a temperature of 25 to 130°C. If the temperature of the above reaction is -20°C or higher, a sufficient reaction rate is obtained. On the other hand, if the temperature of the above reaction is 150°C or lower, gelation caused by the polymerization of raw materials having C=C (double bond) can be prevented.

[0165] The content of structural unit (d) is preferably 5 to 45 mol% of the total structural units of copolymer (A), more preferably 10 to 40 mol%, and even more preferably 15 to 35 mol%. If the content of structural unit (d) is 5 mol% or more, sufficient crosslinking of the block isocyanate group of structural unit (d) and the hydroxyl group of the structural unit (c) described above can be secured. As a result, the low-temperature curing properties of the photosensitive resin composition using the modified copolymer (A2) converted from copolymer (A) are improved. If the content of structural unit (d) is 45 mol% or less, sufficient content of structural unit (a) and structural unit (pb) can be secured, and sufficient content of structural unit (a) and structural unit (b) of the modified copolymer (A2) can be secured, so sufficient developability of the cured product is obtained. In addition, the content of the structural unit (c) can be sufficiently secured, and the amount of bridging with the structural unit (d) can be sufficiently secured.

[0166] (Structural units (a)–(d) and structural units (e) other than structural unit (pb))

[0167] The copolymer (A) may, if necessary, contain a structural unit (e) other than structural units (a) to (d) and structural unit (pb) (also referred to simply as “structural unit (e)”). Structural unit (e) is a structural unit other than structural units (a) to (d) and structural unit (pb) that does not have an acid group, an ethylenically unsaturated group, a hydroxyl group, or a block isocyanate group. By having structural unit (e) in the copolymer (A), additional necessary functions can be imparted.

[0168] Other structural units (e) are structural units derived from monomers (ma), (m-pb), (mc), and (md) that have other ethylenically unsaturated groups and are copolymerizable with monomers (me) (also referred to simply as monomer (me)). 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, monomaleimide, glycidyl (meth)acrylate, (meth)acrylic acid anilide, (meth)acrylonitrile, acrolein, etc.

[0169] Examples of aromatic vinyl compounds include styrene, α-methylstyrene, o-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, methoxystyrene, p-nitrostyrene, p-cyanostyrene, p-acetylaminostyrene, etc.

[0170] As cyclic olefins having a norbornene structure, norbornene (bicyclo[2.2.1]hepto-2-ene), 5-methylbicyclo[2.2.1]hepto-2-ene, tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodeca-3-ene, 8-ethyltetracyclo[4.4.0.1 2,5 .1 7,10 ]dodeca-3-ene, dicyclopentadiene, tricyclo[5.2.1.0 2,6 ]Deca-8-en, Tricyclo[4.4.0.1 2,5 ]Undeca-3-en, tricyclo[6.2.1.0 1,8]Undeca-9-en, tetracyclo[4.4.0.1 2,5 .1 7,10 .0 1,6 ]dodeca-3-ene, 8-ethylidene tetracyclo[4.4.0.1 2,5 .1 7,12 ]Dodeca-3-en, pentacyclo[6.5.1.1 3,6 .0 2,7 .0 9,13 Examples include ]pentadeca-4-en.

[0171] Examples of dienes include butadiene, isoprene, and chloroprene.

[0172] As (meth)acrylic acid esters, 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, dicyclofentanyl (meth)acrylate, Dicyclopentenyloxyethyl acrylate, isobornyl (meth)acrylate, adamantyl (meth)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, Examples include naphthalene (meth)acrylate, anthracene (meth)acrylate, ethoxylated phenyl (meth)acrylate, etc.

[0173] Examples of (meth)acrylic acid amides include (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diisopropylamide, (meth)acrylic acid anthracenilamide, etc.

[0174] Examples of vinyl compounds include vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, vinyltoluene, etc.

[0175] Examples of unsaturated dicarboxylic acid diesters include diethyl citraconic acid, diethyl maleate, diethyl fumarate, and diethyl itaconate.

[0176] Examples of monomaleimides include N-phenylmaleimide, N-cyclohexylmaleimide, and N-laurylmaleimide.

[0177] Among these, from the perspective of ease of availability and reactivity when synthesizing copolymer (A), aromatic vinyl compounds, aromatic group-containing (meth)acrylates, and alkyl (meth)acrylates having 1 to 12 carbon atoms of an alkyl group are preferred, styrene, benzyl (meth)acrylate, dicyclofentanyl (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.

[0178] Monomers (me) may be used alone or in combination of two or more types.

[0179] When the copolymer (A) contains a structural unit (e), the content is preferably 1 to 50 mol% of the total structural units of the copolymer (A), more preferably 3 to 45 mol%, and even more preferably 5 to 40 mol%. By setting the content of the structural unit (e) to the above range, the functions of structural units (a), (pb), (c), and (d) can be sufficiently secured, additional functions provided by the structural unit (e) can be imparted, or the functions obtained from structural units (a), (pb), (c), and (d) can be adjusted to an appropriate range.

[0180] [Basic catalyst (B)]

[0181] The basic catalyst (B) is a basic catalyst having a pKa (acidity constant; also called the acid dissociation constant) of 4 to 12 at 25°C. 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, and may be 5 or more, 6 or more, or 7 or more. Any combination of these lower and upper limits is acceptable. If the pKa at 25°C is 4 or more, a high conversion rate from structural unit (pb) to structural unit (b) can be obtained. If the pKa of the basic catalyst (B) at 25°C is 12 or less, the conversion rate from structural unit (pb) to structural unit (b) is controlled within an appropriate range, and further reaction and consumption of structural unit (b) can be suppressed. In addition, good developability is obtained because the storage stability as a photosensitive resin composition is good. The basic catalyst (B) having a pKa of 4 or higher at 25°C includes one having a pKa of 4 or higher in an aqueous solution, and one having an acidity that is too strong to be measured in an aqueous solution, and a pKa of 4 or higher in an aqueous solution calculated from the measurement result in an organic solvent.

[0182] Specific examples of basic catalysts (B) include pyridine and pyridine derivatives, imidazole compounds, alkylamines, cyclic diamines, etc. Also, “C1-4 alkyl” means that the number of carbon atoms in the alkyl group is 1 to 4.

[0183] Specific examples of pyridine and pyridine derivatives include pyridine (pKa 5.2); C1-4 alkylpyridines such as methylpyridine (picoline) (pKa 6.75) and ethylpyridine; diC1-4 alkylpyridines such as dimethylpyridine (rutidine) (pKa 6.47-6.6); triC1-4 alkylpyridines such as trimethylpyridine (colidine) (pKa 7.48); and 4-aminopyridine derivatives having an amino group at the 4th 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 perspective of the conversion efficiency of the structural unit (pb) included in the copolymer (A), a 4-aminopyridine derivative is preferred, a 4-aminopyridine derivative having a tertiary amino group at the 4th position is more preferred, a 4-diC1-4 alkylaminopyridine is even more preferred, and a 4-dimethylaminopyridine is particularly preferred.

[0184] Examples of imidazole compounds include 2-methylimidazole (pKa 7.75) and 1,2-dimethylimidazole (pKa 7.8).

[0185] Examples of alkylamines include diisopropylamine (pKa 11.05), trimethylamine, and triethylamine (pKa 10.7).

[0186] Examples of cyclic diamines include 1,4-diazabicyclo[2.2.2]octane (DABCO) (pKa 8.8).

[0187] Among these, since it has high nucleation due to resonance stabilization, it is preferable to use at least one selected from the group consisting of pyridine, pyridine derivatives, and imidazole compounds, more preferable to use at least one selected from the group consisting of pyridine derivatives and imidazole compounds, and even more preferable to use a 4-aminopyridine derivative. By doing so, the structural unit (pb) included in the copolymer (A) can be efficiently converted to introduce an ethylenically unsaturated group. Therefore, the copolymer (A) can be efficiently converted into the modified copolymer (A2) described later. The photosensitive resin composition using the modified copolymer (A2) can impart a cured film with excellent low-temperature curability and developability, and excellent solvent resistance.

[0188] 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.

[0189] Basic catalyst (B) may be used alone or in combination of two or more types.

[0190] The content of the basic catalyst (B) is preferably 0.01 to 10 parts by mass per 100 parts by mass of the copolymer (A), more preferably 0.1 to 8 parts by mass, and even more preferably 0.5 to 6 parts by mass. If the content of the basic catalyst (B) is 0.01 parts by mass or more, it is preferable that the reaction rate of converting the structural unit (pb) included in the copolymer (A) into the structural unit (b) is sufficiently fast. If 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 a modified copolymer (A2) that has been converted from the copolymer (A).

[0191] [Solvent(C)]

[0192] As a solvent (C), for example, (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, 3-methoxy-1-butanol; hydroxyl 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, methyl 2-hydroxy-3-methylbutyrate; and hydroxyl group-containing solvents such as diethylene glycol; and (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc.; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; Esters of 3-methyl methoxypropionate, 3-methyl ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, 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, ethyl 2-oxobutyrate, etc.; aromatic hydrocarbons such as toluene and xylene; Examples include hydroxyl group-free solvents such as carboxylic acid amides, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. Solvent (C) may be used alone or in combination of two or more types.

[0193] Among these solvents (C), it is preferable to use ethers such as (poly)alkylene glycol monoalkyl ether, (poly)alkylene glycol monoalkyl ether acetate, and other ethers from the perspective of ease of availability, cost, and stability during resist production, 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.

[0194] The content of the solvent (C) is preferably 30 to 1,000 parts by mass per 100 parts by mass of the total of components other than the solvent (C), and more preferably 50 to 800 parts by mass. It is preferable that the content of the solvent (C) be 30 parts by mass or more, as this allows for a stable reaction when converting the structural unit (pb) included in the copolymer (A). It is preferable that the content of the solvent (C) be 1,000 parts by mass or less, as this allows for appropriate adjustment of the viscosity of the resin composition.

[0195] [Method for manufacturing copolymer (A)]

[0196] A copolymer (A) can be prepared by copolymerizing monomers (ma) and (m-pb) corresponding to each of the structural units (a) and (pb) included in the copolymer (A). The ratio of structural units (a) and (pb) included in the copolymer (A) is equivalent to the ratio of each monomer (ma) and (m-pb) in the total sum of all monomers used as raw materials for the copolymer (A) (hereinafter referred to as "raw material monomers").

[0197] Accordingly, the ratio of each monomer (ma) and (m-pb) among the raw monomers used as raw materials for copolymer (A) is preferably 5 to 50 mol% for (ma) and 3 to 40 mol% for (m-pb), more preferably 8 to 40 mol% for (ma) and 5 to 35 mol% for (m-pb), and even more preferably 10 to 30 mol% for (ma) and 10 to 30 mol% for (m-pb).

[0198] When manufacturing a copolymer (A) that includes a structural unit (c), it is preferable to use monomer (mc) in addition to monomer (ma) and (m-pb) as raw material monomers for copolymer (A). In that case, the proportion of monomer (mc) among the raw material monomers used as raw materials for copolymer (A) is preferably 3 to 40 mol%, more preferably 5 to 30 mol%, and even more preferably 8 to 25 mol%.

[0199] When manufacturing a copolymer (A) that includes a structural unit (d), it is preferable to use monomer (md) in addition to monomer (ma) and (m-pb) as raw material monomers for copolymer (A). In that case, the proportion of monomer (md) among 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%.

[0200] When manufacturing a copolymer (A) that includes a structural unit (e), it is preferable to use monomer (me) in addition to monomer (ma) and (m-pb) as raw material monomers for copolymer (A). In that case, the proportion of monomer (me) among the raw material monomers used as raw materials for copolymer (A) is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, and even more preferably 5 to 40 mol%.

[0201] The copolymerization reaction of raw monomers (monomer (ma), and (m-pb), and monomers (mc), (md), and (me)) used when manufacturing copolymer (A) can be carried out in the presence or absence of a polymerization solvent according to radical polymerization methods already known in the art. Specifically, for example, a method can be used in which raw monomers, a polymerization initiator, and a polymerization solvent are mixed to form a raw monomer solution, and the polymerization reaction is carried out for 1 to 20 hours at a temperature of 50 to 100°C under a nitrogen gas atmosphere.

[0202] As a polymerization solvent used when manufacturing copolymer (A), solvents that can be used as solvents (C) may be used alone or in combination of two or more types.

[0203] When the raw monomer includes monomers (mc) and (md), it is preferable that the temperature at which the raw monomer is copolymerized be lower than the temperature at which the dissociation rate of the block isocyanate group of monomer (md), which has an ethylenically unsaturated bond with the block isocyanate group, reaches 80% or more within 30 minutes. This is because it inhibits gelation caused by the dissociation of the block isocyanate group of monomer (md) to form isocyanate groups within the raw monomer solution during the copolymerization reaction, and the reaction with the hydroxyl group of the hydroxyl group-containing monomer (mc). It is more preferable that the temperature at which the raw monomer is copolymerized be lower than the temperature at which the dissociation rate of the block isocyanate group of monomer (md) reaches 80% or more within 30 minutes.

[0204] Specifically, the temperature at which the raw monomer is copolymerized can be 50 to 100°C, preferably 60 to 90°C, and more preferably 65 to 85°C.

[0205] Examples of polymerization initiators used when copolymerizing raw monomers include 2,2'-azobis(2,4-dimethylvaleronitrile), azobisisobutylonitrile, azobisisovaleronitrile, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, etc. The polymerization initiator may be used alone or in combination of two or more types. The amount of polymerization initiator used may be 0.5 to 20 parts by mass per 100 parts by mass of raw monomer (total amount of monomer input), and preferably 1.0 to 16 parts by mass.

[0206] When manufacturing the copolymer (A), additives such as polymerization inhibitors, chain transfer agents, photosensitizers, fillers, and plasticizers may be used as needed, to the extent that the effects of the present invention are not impaired.

[0207] [Method for manufacturing a resin composition]

[0208] A resin composition is obtained by mixing a copolymer (A), a basic catalyst (B), and a solvent (C). When the copolymer (A) is synthesized by the manufacturing method described above, it may also be prepared by adding a basic catalyst (B) to the reaction solution. In this case, the solvent used in the synthesis of the copolymer (A) may be used as is as solvent (C), or a new solvent may be added.

[0209] Modified Resin Composition

[0210] A modified resin composition of one embodiment contains a modified copolymer (A2), a basic catalyst (B), and a solvent (C). The modified resin composition may also contain a copolymer (A).

[0211] The basic catalyst (B) and the solvent (C) can be the same as those used in the resin composition, and the preferred form and amount are also the same. In addition, the amount of the basic catalyst (B) is based on 100 parts by mass of the total copolymer (A) and the modified copolymer (A2).

[0212] [Modified copolymer (A2)]

[0213] A 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 the following formula (1-2). The modified copolymer (A2) can be obtained by converting a portion of the structural unit (pb) of the copolymer (A) into the structural unit (b) through the dealolation and decarboxylation reactions of the structural unit (pb) by the action of a basic catalyst (B). Since the modified copolymer (A2) has a structural unit (b) having an ethylenically unsaturated group, good photocuring properties are obtained and low-temperature curing properties are improved when the modified copolymer (A2) is used in a photosensitive resin composition. In addition, when the modified copolymer (A2) is used together with the reactive diluent (D) described later, the ethylenically unsaturated group of the structural unit (b) reacts with the reactive diluent (D), and good adhesion to the substrate of the cured film is obtained.

[0214]

[0215] (In Equation (1), R 1 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 2 and R 3 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a connection site between the structural unit (pb) and a residue excluding the group of Formula (1).

[0216]

[0217] (In Equation (1-1), R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 2 and R 3 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * indicates a connection site with a residue excluding the group of Formula (1-1) from the structural unit (b).

[0218]

[0219] (In Equation (1-2), R 2 and R 3 Each is 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 * indicates a connection site between the structural unit (b) and a residue excluding the group of Formula (1-2).

[0220] The modified copolymer (A2) may further contain, if necessary, a structural unit (c) having a hydroxyl group and a structural unit (d) having a block isocyanate group. The modified copolymer (A2) may further contain, if necessary, other structural units (e) other than structural units (a) to (d) and structural unit (pb).

[0221] Structural units (a), (pb), (c), (d), and (e) may be the same as copolymer (A). Preferred embodiments are the same, except for the content of structural unit (pb).

[0222] The content of structural units (pb) is preferably 1 to 35 mol% of the total structural units of the modified copolymer (A2) and copolymer (A), more preferably 2 to 30 mol%, and even more preferably 3 to 25 mol%.

[0223] (Structural unit (b) having a group represented by Equation (1-1) or Equation (1-2))

[0224] A structural unit (b) having a group represented by Equation (1-1) or Equation (1-2) (also referred to simply as “structural unit (b)”) is a structural unit that does not have a group and has a group represented by Equation (1-1) or Equation (1-2) below.

[0225]

[0226] (In Equation (1-1), R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 2 and R 3Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * indicates a connection site with a residue excluding the group of Formula (1-1) from the structural unit (b).

[0227]

[0228] (In Equation (1-2), R 2 and R 3 Each is 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 * indicates a connection site between the structural unit (b) and a residue excluding the group of Formula (1-2).

[0229] The group represented by Equation (1-1) does not have to be of only one type. R of each structural unit 1 They may be different, and the R of each structural unit 2 They may also be different, and the R of each structural unit 3 Each may also be different. The same applies to the energy represented by Equation (1-2).

[0230] Among Equations (1-1) and (1-2), R 1 , R 2 , R 3 and R 4 It is the same as described above for Equation (1).

[0231] The content of structural unit (b) is preferably 2 to 39 mol% of the total structural units of the modified copolymer (A2) and copolymer (A), more preferably 3 to 33 mol%, and even more preferably 7 to 27 mol%.

[0232] (Reaction Pathway)

[0233] In the conversion reaction from copolymer (A) to modified copolymer (A2), the structural unit (pb) contained in copolymer (A) is presumed to be converted into the structural unit (b) by the reaction pathway shown below.

[0234]

[0235] That is, in the structural unit (pb) having a group represented by formula (1) included in the copolymer (A), the H of -NH- in the urethane bond and the ester portion (-COOR 1 or -COOR 4 A take-alcohol reaction occurs due to ).

[0236] By this, a unit having a complex ring represented by Equation (1-3) and / or Equation (1-4) is formed. The unit having a complex ring represented by Equation (1-3) is R in the unit represented by Equation (1). 4 Dealolation reaction of the ester portion including (-R 4 It is formed by OH). The unit having a complex ring represented by Equation (1-4) is R in the unit represented by Equation (1). 1 Dealolation reaction of the ester portion including (-R 1 It is formed by OH.

[0237]

[0238] (In Equation (1-3), R 1 , R 2 and R 3 R in Equation (1) 1 , R 2 and R 3 ...is the same as, and * indicates the connection between the structural unit (pb) and the residue excluding the group of Equation (1-3).

[0239]

[0240] (In Equation (1-4), R 2 , R 3 and R 4 is R in Equation (1) 2 , R 3 and R 4 ...is the same as, and * indicates the connection between the structural unit (pb) and the residue excluding the group of Equation (1-4).

[0241] Next, in the complex ring represented by the above equation (1-3), decarbonation (-CO2) occurs in the complex ring portion. As a result, the complex ring represented by the equation (1-3) is converted into the complex ring represented by the following equation (1-1).

[0242]

[0243] (In Equation (1-1), R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 2 and R 3 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * indicates a connection site with a residue excluding the group of Formula (1-1) from the structural unit (b).

[0244] Meanwhile, in the complex ring represented by the above equation (1-4), decarbonation (-CO2) occurs in the complex ring portion. As a result, the complex ring represented by the equation (1-4) is converted into the complex ring represented by the following equation (1-2).

[0245]

[0246] (In Equation (1-2), R 2 and R 3 Each is 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 * indicates a connection site between the structural unit (b) and a residue excluding the group of Formula (1-2).

[0247] In the density functional method, when wB97XD was used as the functional and 6-31+g(d) as the basis function, the transition state calculations in the production pathways of each product were performed. As a result, it is presumed that the transformation reaction that converts the above-described structural unit (pb) into structural unit (b) has a lower activation barrier in the reaction pathways of Equation (1), Equation (1-4), and Equation (1-2) compared to the reaction pathways of Equation (1), Equation (1-3), and Equation (1-1), and serves as the main transformation route. Therefore, it is presumed that in the modified copolymer (A2), structural units having the group represented by Equation (1-2) and structural units having the group represented by Equation (1-1) are mixed, and that structural units having the group represented by Equation (1-2) exist in greater numbers than structural units having the group represented by Equation (1-1).

[0248] [Ethylene unsaturated group equivalent of modified copolymer (A2)]

[0249] 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 10,000 g / mol or less, more preferably 7,000 g / mol or less, and even more preferably 4,000 g / mol or less. Any combination of these lower and upper limits is acceptable. If it is 300 g / mol or more, the storage stability as a photosensitive resin composition is good. If it is 10,000 g / mol or less, the solvent resistance of the cured product is good even when cured at a low temperature.

[0250] "Ethylene unsaturated group equivalent" is the mass of the polymer per mole of ethylene unsaturated group of the polymer. The ethylene unsaturated group equivalent (g / mol) of the modified copolymer (A2) is obtained by dividing the mass of the modified copolymer (A2) by the number of moles of ethylene unsaturated groups contained in the modified copolymer (A2).

[0251] In this specification, R of formulas (1-1) and (1-2) in the modified copolymer (A2) 2 and R 3 In the case where all atoms are hydrogen atoms, the ethylenically unsaturated group equivalent is a value calculated from the conversion rate from structural unit (pb) to structural unit (b), calculated from the area ratio of the NMR spectrum acquired under the following conditions using an NMR device (e.g., Bruker ULTRA SHIELD PLUS 400 (400 MHz), Bluecasa), and the input amounts of monomer (ma), (m-pb), and (mc) to (me) used when preparing copolymer (A). Additionally, the measurement sample may contain copolymer (A). In this case, the value obtained for a mixture of modified copolymer (A2) and copolymer (A) is determined as the ethylenically unsaturated group equivalent of the modified copolymer (A2). When the measurement sample contains copolymer (A), the conversion rate from structural unit (pb) to structural unit (b) is also a value for a mixture of modified copolymer (A2) and copolymer (A).

[0252] (NMR conditions)

[0253] Measurement method: 1 H-NMR

[0254] Rock solvent: CDCl3

[0255] Internal standard: TSP-d4 (sodium trimethylsilylpropionate) = 0 ppm

[0256] Temperature: Room temperature

[0257] Sample preparation: Powder sample (20 mg) / CDCl3 (1 mL) + TSP-d4 (5 mg)

[0258] (Sample preparation method)

[0259] 20 mg of dried modified copolymer (A2) or a mixture of modified copolymer (A2) and copolymer (A) is weighed, CDCl3 (1 mL) is added and dissolved in a 20 mL sample bottle, shaken for 5 minutes with an ultrasonic cleaner, then sealed in a 5 mmφ NMR sample tube, and NMR measurement is performed immediately after sampling.

[0260] The conversion rate from structural unit (pb) to structural unit (b) is -CR detected as 2.5–3.0 ppm. 2 -CHR 3 The spectrum of "-CH2-" in -C(=O)- (i.e., -CH-CH2-C(=O)-) and -C(=O)-CR detected at 6.5–7.0 ppm 3 =CR 2 -C(=O)- and -C(=O)-CR 2 It is calculated by the following formula based on the area ratio of the spectrum of =CR3-C(=O)-(i.e., -C(=O)-CH=CH-C(=O)-).

[0261] Conversion rate from structural unit (pb) to structural unit (b) = {(-C(=O)-CH=CH-C(=O)-) / [(-CH-CH2-C(=O)-)+(-C(=O)-CH=CH-C(=O)-)]}×100(%)

[0262] In this specification, the modified copolymer (A2) is R 2 and R 3 When a structural unit (b) having a group represented by Formula (1-1) or Formula (1-2) in which at least one or both are hydrocarbon groups having 1 to 20 carbon atoms is included, the ethylenically unsaturated group equivalent is a value calculated from the amount of halogen bound to the modified copolymer (A2). The amount of halogen bound to the modified copolymer (A2) is evaluated as follows in accordance with JIS K 0070:1992.

[0263] That is, the dried modified copolymer (A2) is dissolved in chloroform, and an appropriate amount of Wijs solution is added and stirred. Afterward, it is sealed and left in a dark place at 23°C for 1 hour. Potassium iodide solution and water are added to this solution and stirred, and the resulting solution is titrated with a sodium thiosulfate solution. When the solution turns pale yellow, a few drops of starch solution are added, and titration is performed 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 the amount of substance (mol) of halogen molecules bonded to the modified copolymer (A2) obtained by this measurement, and is obtained by dividing the mass (g) of the modified copolymer (A2) used for measurement. Also, the measurement sample may contain copolymer (A). In this case, the value obtained for the mixture of the modified copolymer (A2) and the copolymer (A) is determined as the ethylenically unsaturated group equivalent of the modified copolymer (A2).

[0264] [Sanga]

[0265] The acid value of copolymer (A) and the acid value of modified copolymer (A2) or a mixture of copolymer (A) and modified copolymer (A2) is preferably 10 KOH mg / g or higher, more preferably 15 KOH mg / g or higher, and even more preferably 20 KOH mg / g or higher. The acid value of copolymer (A) and the acid value of modified copolymer (A2) or a mixture of copolymer (A) and modified copolymer (A2) is preferably 300 KOH mg / g or lower, more preferably 200 KOH mg / g or lower, and even more preferably 150 KOH mg / g or lower. Any combination of these lower and upper limits is acceptable. If it is 10 KOH mg / g or higher, the developability is good. If it is 300 KOH mg / g or lower, the storage stability is good.

[0266] "Acid value" refers to the acid value of a curable polymer measured according to JIS K6901:2008 5.3. That is, the acid value refers to the number of milligrams of potassium hydroxide required to neutralize the acidic component contained in 1 g of copolymer.

[0267] [Weight Average Molecular Weight]

[0268] The weight average molecular weight of copolymer (A) and the weight average molecular weight of the modified copolymer (A2) or the mixture of copolymer (A) and the modified copolymer (A2) is preferably 1,000 or more, more preferably 3,000 or more, and even more preferably 5,000 or more. The weight average molecular weight of copolymer (A) and the weight average molecular weight of the modified copolymer (A2) or the mixture of copolymer (A) and the 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 is acceptable. If it is 1,000 or more, when the modified copolymer (A2) is used as a raw material for a photosensitive resin composition, it is difficult for problems such as cracks to occur in the resin cured film after development. If it is 50,000 or less, the photosensitive resin composition containing the modified copolymer (A2) has a sufficiently short development time and excellent practicality.

[0269] In this specification, the weight average molecular weight refers to the weight average molecular weight equivalent to standard polystyrene measured using gel permeation chromatography (GPC) under the following conditions.

[0270] Column: Showdex (trademark). Use two LF-804s (Kabushiki Kaisha Resonac) connected in series.

[0271] Column temperature: 40℃

[0272] Sample: 0.2 mass% tetrahydrofuran solution of the object to be measured

[0273] Developing solvent: tetrahydrofuran

[0274] Detector: Differential Refractometer (Showdex (trademark) RI-71S) (Resonac Co., Ltd.)

[0275] Flow rate: 1 mL / min

[0276] [Block Isocyanatian Equation]

[0277] The block isocyanate group equivalent of copolymer (A) and the block isocyanate group equivalent of the modified copolymer (A2) or the mixture of copolymer (A) and the modified copolymer (A2) are preferably 100 to 2000 g / mol, more preferably 200 to 1500 g / mol, and even more preferably 300 to 1300 g / mol. If it is 100 g / mol or more, the photosensitive resin composition containing the modified copolymer (A2) has better developability. If it is 2000 g / mol or less, the photosensitive resin composition containing the modified copolymer (A2) can form a resin cured film having better hardness.

[0278] "Block isocyanate equivalent" refers to the mass of the polymer per 1 mole of block isocyanate groups of the polymer. The block isocyanate equivalent (g / mol) of a copolymer is obtained by dividing the mass of the copolymer by the number of moles of block isocyanate groups contained in the copolymer. In this specification, the theoretical value calculated from the amount of monomer input used when manufacturing the copolymer is used as the "block isocyanate equivalent."

[0279] [Hydroxyl group equivalent]

[0280] The hydroxyl group equivalent of copolymer (A) and the hydroxyl group equivalent of the modified copolymer (A2) or the mixture of copolymer (A) and the modified copolymer (A2) are preferably 200 to 5000 g / mol, more preferably 400 to 4000 g / mol, and even more preferably 800 to 3000 g / mol. If it is 200 g / mol or more, the photosensitive resin composition containing the modified copolymer (A2) has better developability. If it is 5000 g / mol or less, the photosensitive resin composition containing the modified copolymer (A2) can form a resin cured film having better hardness.

[0281] "Hydroxyl group equivalent" refers to the mass of the polymer per mole of hydroxyl groups. The hydroxyl group equivalent (g / mol) of a copolymer is obtained by dividing the mass of the copolymer by the number of moles of hydroxyl groups contained in the copolymer. In this specification, the theoretical value calculated from the amount of monomer input used when manufacturing the copolymer is used as the "hydroxyl group equivalent."

[0282] [Method for manufacturing a modified resin composition]

[0283] A modified resin composition can be obtained by converting the structural unit (pb) of the copolymer (A) in the resin composition into a structural unit (b) and modifying the copolymer (A) into a modified copolymer (A2). For example, a resin composition containing a copolymer (A), a basic catalyst (B), and a solvent (C) is maintained at a temperature of, for example, 0 to 150°C for 0.1 to 10 hours. By doing so, a dealolysis reaction and a decarboxylation reaction of the copolymer (A) are carried out, converting the structural unit (pb) contained in the copolymer (A) into a structural unit (b), and a modified resin composition containing the modified copolymer (A2), the basic catalyst (B), and the solvent (C) can be produced. In the modified resin composition, the copolymer (A) may remain. The content of copolymer (A) in the modified resin composition may be 0 to 20 mass parts, 0 to 10 mass parts, or 0 to 5 mass parts per 100 mass parts of the modified copolymer (A2). In one embodiment, the modified resin composition does not contain 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 and upper limits may be used. The conversion reaction time may be 30 minutes or more, or 60 minutes or more. The conversion reaction time may be 300 minutes or less, or 180 minutes or less. Any combination of these lower and upper limits may be used.

[0284] <Photosensitive resin composition, and photosensitive coloring composition>

[0285] A 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 also contain a copolymer (A). A photosensitive coloring composition of one embodiment further contains a coloring agent (F).

[0286] The total content of the modified copolymer (A2) and optionally included 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, based on 100 parts by mass of the total of the modified copolymer (A2), copolymer (A), and reactive diluent (D). The total content of the modified copolymer (A2) and optionally included 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, based on 100 parts by mass of the total of the modified copolymer (A2), copolymer (A), and reactive diluent (D). Any combination of these lower and upper limits is acceptable. If the total content of the modified copolymer (A2) and copolymer (A) is 10 parts by mass or more, a photosensitive resin composition or a photosensitive coloring composition can be obtained that can form a cured product having better low-temperature curing properties and good solvent resistance. If the total content of the modified copolymer (A2) and copolymer (A) is 90 parts by mass or less, the content of the reactive diluent (D) can be sufficiently secured, so the strength of the cured product and adhesion to the substrate are good.

[0287] The content of copolymer (A) in the photosensitive resin composition or photosensitive coloring composition may be 0 to 20 mass parts, 0 to 10 mass parts, or 0 to 5 mass parts per 100 mass parts of modified copolymer (A2). From the perspective of improving the solvent resistance of the resin cured film, copolymer (A) may not be included.

[0288] 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, based on 100 parts by mass of the total of the modified copolymer (A2), copolymer (A), and 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 based on 100 parts by mass of the total of the modified copolymer (A2), copolymer (A), and reactive diluent (D). If the content of the basic catalyst (B) is 5 parts by mass or less, the influence of the basic catalyst (B) can be suppressed when curing the photosensitive resin composition.

[0289] [Solvent(C)]

[0290] As for the solvent (C), the same as the solvent (C) used in the resin composition may be used. The solvent (C) in the photosensitive resin composition or the photosensitive coloring composition and the solvent (C) used in the manufacture of the modified copolymer (A2) may be the same or different.

[0291] The content of solvent (C) in the photosensitive resin composition or photosensitive coloring composition is preferably 30 parts by mass or more, and more preferably 50 parts by mass or more, based on 100 parts by mass of the total of the modified copolymer (A2), copolymer (A), and reactive diluent (D). The content of solvent (C) in the photosensitive resin composition or photosensitive coloring composition is preferably 1,000 parts by mass or less, and more preferably 800 parts by mass or less, based on 100 parts by mass of the total of the modified copolymer (A2), copolymer (A), and reactive diluent (D). Any combination of these lower and upper limits is acceptable. If the content of solvent (C) is 30 parts by mass or more, the viscosity of the photosensitive resin composition or photosensitive coloring composition can be set to an appropriate range. If the content of the solvent (C) is 1,000 parts by mass or less, the solvent (C) can be easily excluded when the solvent (C) in the coating film formed by applying the photosensitive resin composition or the photosensitive coloring composition onto a substrate is excluded.

[0292] [Reactive Diluent (D)]

[0293] The reactive diluent (D) is a monomer having at least one ethylenically unsaturated bond as a polymerizable functional group within the molecule. The reactive diluent (D) may be a monofunctional monomer or a polyfunctional monomer having multiple polymerizable functional groups. By including the reactive diluent (D), the viscosity of the photosensitive resin composition or photosensitive coloring composition can be set to an appropriate range according to the application. In addition, since the photosensitive resin composition or photosensitive coloring composition contains the reactive diluent (D), it can form a cured product having good photocurability and good strength and adhesion to the substrate. The reactive diluent (D) may be used alone or in combination of two or more types.

[0294] As monofunctional monomers used as reactive diluents (D), (meth)acrylamide compounds such as (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxymethyl (meth)acrylamide; Methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 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, half (meth)acrylates of phthalic acid derivatives Examples include (meth)acrylates such as styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, aromatic vinyl compounds such as vinyl acetate, vinyl propionate, etc. Monofunctional monomers may be used alone or in combination of two or more types.

[0295] As polyfunctional monomers used as reactive diluents (D), 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, trimethylolpropane tri(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalate diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (e.g., reaction products of tolylene diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, etc., and 2-bedroxyethyl(meth)acrylate), Examples include (meth)acrylates such as tri(meth)acrylate of tris(hydroxyethyl)isocyanurate; aromatic vinyl compounds such as divinylbenzene, diallylphthalate, and diallylbenzenephosphonate; dicarboxylic acid esters such as divinyl adipice; and condensates of trialylcyanurate, methylenebis(meth)acrylamide, polyhydric alcohols, and N-methylol(meth)acrylamide. Polyfunctional monomers may be used alone or in combination of two or more.

[0296] Among these monomers, since a photosensitive resin composition or a photosensitive coloring composition with good photocuring properties can be obtained, it is preferable to use a polyfunctional (meth)acrylate as a reactive diluent (D), it is more preferable to use a polyfunctional (meth)acrylate with three or more functions, 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.

[0297] 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, based on 100 parts by mass of the total of the modified copolymer (A2), copolymer (A), and 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, based on 100 parts by mass of the total of the modified copolymer (A2), copolymer (A), and reactive diluent (D). Any combination of these lower and upper limits is acceptable. If the content of the reactive diluent (D) is 10 parts by mass or more, the effect of containing the reactive diluent (D) becomes significant. If the content of the reactive diluent (D) is 90 parts by mass or less, the content of the modified copolymer (A2) can be sufficiently secured, so a photosensitive resin composition or a photosensitive coloring composition with even better low-temperature curing properties can be obtained.

[0298] [Photopolymerization initiator(E)]

[0299] The photopolymerization initiator (E) is not particularly limited, but, for example, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl-]-, -1-(O-acetyloxime); benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether; acetophenone compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4'-(1-t-butyldioxy-1-methylethyl)acetophenone; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1; Examples include anthraquinone compounds such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; xanthones; thioxantone compounds such as thioxantone, 2,4-dimethylthioxantone, 2,4-diisopropylthioxantone, and 2-chlorothioxantone; ketal compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone compounds such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, and 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone; and acylphosphine oxide-based photopolymerization initiators. The photopolymerization initiator (E) may be used alone or in combination of two or more types.

[0300] 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, based on 100 parts by mass of the total of the modified copolymer (A2), copolymer (A), and 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, based on 100 parts by mass of the total of the modified copolymer (A2), copolymer (A), and reactive diluent (D). Any combination of these lower and upper limits is acceptable. If the content of the photopolymerization initiator (E) is 0.1 parts by mass or more, a photosensitive resin composition or a photosensitive coloring composition with good photocuring properties can be obtained. If the content of the photopolymerization initiator (E) is 30 parts by mass or less, it is possible to prevent adverse effects on the physical properties of the cured product of the photosensitive resin composition or photosensitive coloring composition due to an excessive amount of the photopolymerization initiator (E).

[0301] [Colorant(F)]

[0302] The photosensitive coloring composition may further contain a coloring agent (F). The photosensitive coloring composition containing the coloring agent (F) can be used as a material for a color filter.

[0303] The coloring agent (F) is not particularly limited as long as it is dissolved or dispersed in the solvent (C), and examples include dyes, pigments, etc.

[0304] As for the dye, it is preferable to use an acid dye having acid groups such as carboxyl groups and sulfonate groups, a salt of an acid dye with a nitrogen compound, or a sulfonamide adduct of an acid dye, from the perspective of solubility in a solvent (C) and an alkaline developer, interaction with other components in the photosensitive coloring composition, and heat resistance.

[0305] 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; 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; Examples include 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, xanthen, anthraquinone, or phthalocyanine acid dyes are preferred. The dyes may be used alone or in combination of two or more types.

[0306] Examples of pigments include yellow pigments such as CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 60; violet pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38; green pigments such as CI Pigment Green 7, 36, 58, 59; brown pigments such as CI Pigment Brown 23, 25; Examples of black pigments include CI pigment black 1, 7, carbon black, titanium black, iron oxide, etc. Pigments can be used individually or in combination of two or more types.

[0307] The coloring agent (F) can be appropriately determined, for example, according to the color of the intended coloring pattern (black matrix and pixel). The coloring agent (F) may be used alone or in combination of two or more types. When using two or more types of coloring agents (F), a combination of dyes and pigments may be used.

[0308] When using a pigment as the coloring agent (F), a known dispersant may be incorporated into the photosensitive coloring composition from the perspective of improving the dispersibility of the pigment. As the dispersant, it is preferable to use a polymeric dispersant that has excellent dispersion stability over time. Examples of polymeric 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. As polymeric dispersants, commercially available products under trade names such as EFKA (EFKA CHEMICALS BV), Disperbyk (Big Chem), Disparon (Kusumoto Kasei Co., Ltd.), and SOLSPERSE (Lubrizol) may be used. The content of the dispersant may be appropriately set according to the type and amount of the pigment used as the coloring agent (F).

[0309] The content of the coloring agent (F) in the photosensitive coloring composition is preferably 3 parts by mass or more with respect to 100 parts by mass of the total of the modified copolymer (A2), copolymer (A), and reactive diluent (D), more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more. The content of the coloring agent (F) in the photosensitive coloring composition is preferably 80 parts by mass or less with respect to 100 parts by mass of the total of the modified copolymer (A2), copolymer (A), and reactive diluent (D), more preferably 70 parts by mass or less, and even more preferably 60 parts by mass or less. Any combination of these lower and upper limits is acceptable. If the content of the coloring agent (F) is 3 parts by mass or more, the effect of containing the coloring agent (F) becomes significant, and a photosensitive coloring composition suitable as a material for the coloring pattern of a color filter is obtained. If the content of the coloring agent (F) is 80 parts by mass or less, the coloring agent (F) does not impede the curability of the photosensitive coloring composition, and a photosensitive coloring composition with good low-temperature curability can be obtained.

[0310] [Other ingredients]

[0311] In addition to the modified copolymer (A2), solvent (C), reactive diluent (D), photopolymerization initiator (E), and coloring agent (F) contained as needed, known additives such as coupling agents, leveling agents, and thermal polymerization inhibitors may be added as needed to the photosensitive resin composition or photosensitive coloring composition of one embodiment. The amount of additives added should be within a range that does not impede the effects of the present invention and is not particularly limited.

[0312] <Method for manufacturing a photosensitive resin composition and a photosensitive coloring composition>

[0313] A photosensitive resin composition of one embodiment can be prepared by a method of mixing a modified copolymer (A2), a basic catalyst (B), a solvent (C), a reactive diluent (D), a photopolymerization initiator (E), and an optionally used copolymer (A) using a known mixing device. A photosensitive coloring composition of one embodiment can be prepared by a method of mixing a modified copolymer (A2), a basic catalyst (B), a solvent (C), a reactive diluent (D), a photopolymerization initiator (E), a coloring agent (F), and an optionally used copolymer (A) using a known mixing device.

[0314] When preparing a photosensitive resin composition or a photosensitive coloring composition, a reaction solution (i.e., a modified resin composition) comprising a modified copolymer (A2) obtained by converting the structural unit (pb) of a copolymer (A) into a structural unit (b) in the resin composition as a raw material, a basic catalyst (B), a solvent (C), and a copolymer (A) of any component may be used as is. In this case, the solvent (C) included in the reaction solution may be used as part or all of the solvent (C) included in the photosensitive resin composition or the photosensitive coloring composition.

[0315] Since the photosensitive resin composition or photosensitive coloring composition contains a modified copolymer (A2) having a structural unit (b) having a group represented by formula (1-1) or formula (1-2), a reactive diluent (D), and a photopolymerization initiator (E), when irradiated with light, the reactive diluent (D) polymerizes together with the ethylenically unsaturated group included in the structural unit (b) of the modified copolymer (A2), thereby exhibiting good photocuring properties.

[0316] In addition, if the photosensitive resin composition or photosensitive coloring composition comprises a modified copolymer (A2) containing a structural unit (c) having a hydroxyl group and a structural unit (d) having a block isocyanate group, it also has good low-temperature curing properties.

[0317] In this regard, when a cured product is formed using a photosensitive resin composition or a photosensitive coloring composition, it can be cured at a lower temperature compared to when a conventional resin composition is used. Therefore, when a baking treatment is performed after, for example, a coating film formed on a substrate is exposed to light, the photosensitive resin composition or the photosensitive coloring composition can form a cured product with excellent solvent resistance because the crosslinking reaction proceeds sufficiently even if the baking treatment temperature is low.

[0318] Therefore, when forming a cured product using a photosensitive resin composition or a photosensitive coloring composition, the energy required for heating to cure is minimal. Furthermore, 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 damage to the substrate. Additionally, regarding the photosensitive coloring composition, even if a coloring agent (F) with low heat resistance is used, a cured product can be formed in which the inherent characteristics of the coloring agent (F) are exhibited.

[0319] Since the photosensitive coloring composition yields a cured product with excellent solvent resistance even when the baking temperature is low, the coloring agent (F) is difficult to leach out. Therefore, it is possible to increase the content of the coloring agent (F) in the photosensitive coloring composition. A photosensitive coloring composition with a high content of the coloring agent (F) can be used, for example, as a material for the coloring pattern of a color filter to form a color filter with excellent color reproducibility.

[0320] Since the modified copolymer (A2) included in the photosensitive resin composition or photosensitive coloring composition has a structural unit (a) having an acid group, the photosensitive resin composition or photosensitive coloring composition has good alkali developability. Since the photosensitive resin composition or photosensitive coloring composition has excellent alkali developability, for example, by applying it onto a substrate to form a coating film, exposing it through a photomask corresponding to a predetermined pattern shape, developing the unexposed portion with an alkaline aqueous solution, and then baking it at a sufficiently low temperature, a cured product with excellent solvent resistance having a predetermined pattern shape can be formed.

[0321] The photosensitive resin composition and the photosensitive coloring composition can be suitably used as materials for color filters.

[0322] In this regard, photosensitive resin compositions and photosensitive coloring compositions are very useful as materials for forming components of image display elements, such as pixels of color filters, black matrices, color filter protective films, photospacers, liquid crystal alignment protrusions, microlenses, and insulating films for touch panels.

[0323] <Resin hardening film>

[0324] A resin cured film of one embodiment is composed of a cured product of a photosensitive resin composition or a photosensitive coloring composition.

[0325] A resin cured film can be manufactured, for example, by a method of applying a photosensitive resin composition or a photosensitive coloring composition onto a substrate, volatilizing and removing a solvent (C) to form a coating film, exposing the coating film to light to photocuring, and then performing a baking treatment.

[0326] When forming a resin cured film having a predetermined pattern shape, for example, the method described below may be used. That is, a photosensitive resin composition or a photosensitive coloring composition is applied onto a substrate, and a solvent (C) is evaporated and removed to form a coating film. Next, the coating film is exposed to light through a photomask having a predetermined pattern shape, and the exposed portion is photocured. Subsequently, the unexposed portion of the coating film is developed with an alkaline aqueous solution. After that, a resin cured film having a predetermined pattern shape is formed by performing a baking treatment on the developed coating film.

[0327] In manufacturing a resin cured film, known methods may be used for the method of applying a photosensitive resin composition or a photosensitive coloring composition, the method of exposing the coated film, and the method of developing.

[0328] The conditions for the baking treatment performed when manufacturing a resin cured film can be appropriately determined according to the composition of the photosensitive resin composition or photosensitive coloring composition, the film thickness of the coating film, the material of the substrate, etc. The baking treatment can be performed, for example, at a temperature of 70°C to 250°C. If the temperature of the baking treatment is 70°C or higher, the block isocyanato group of the structural unit (d) having a block isocyanato group included in the modified copolymer (A2) in the photosensitive resin composition or photosensitive coloring composition is sufficiently dissociated. As a result, an isocyanato group is generated and cross-links with the hydroxyl group of the structural unit (c) having a hydroxyl group. If the structural unit (d) has a carboxylic acid alkyl ester structure, cross-linking occurs through ester exchange between the carboxylic acid alkyl ester structure and the hydroxyl group. As a result, a good degree of curing is obtained, and a cured product having excellent solvent resistance is obtained. When the structural unit (d) has an alkyl carboxylate structure, both the deblocking reaction and the transesterification reaction may occur, but by adjusting the baking temperature, one of the reactions can be carried out preferentially. The temperature of the baking treatment is preferably 75°C or higher, and more preferably 80°C or higher. If the temperature of the baking treatment is 250°C or lower, it is a condition that can withstand materials with low heat resistance, and it is desirable because it can suppress discoloration of the photosensitive resin composition or photosensitive coloring composition. The photosensitive resin composition and the photosensitive coloring composition have good low-temperature curing properties. For this reason, the temperature of the baking treatment can be set to 160°C or lower depending on the heat resistance of the substrate forming the resin cured film, and 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.

[0329] The baking treatment performed when manufacturing a resin cured film can be performed for, for example, 10 minutes to 4 hours, preferably 20 minutes to 2 hours, and can be appropriately determined according to the composition of the photosensitive resin composition or photosensitive coloring composition, the temperature of the baking treatment, the thickness of the coating film, etc.

[0330] The resin cured film consists of a cured product of a photosensitive resin composition or a photosensitive coloring composition. For this reason, the resin cured film can be manufactured using a baking process at a low temperature, and furthermore, it has excellent solvent resistance.

[0331] Color Filter

[0332] A color filter of one embodiment has a color pattern formed from a cured product of a photosensitive coloring composition. The color filter preferably has a color pattern formed from a cured product of a photosensitive coloring composition containing 10 to 90 parts by mass of the modified copolymer (A2) and copolymer (A), 0.05 to 9 parts by mass of a basic catalyst (B), 10 to 90 parts by mass of a 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 coloring agent (F), based on a total of 100 parts by mass of the modified copolymer (A2), a copolymer of any component (A), and a reactive diluent (D).

[0333] The color filter may include, for example, a substrate, RGB pixels formed thereon, a black matrix formed at the boundary of each pixel, and a protective film formed on the pixels and the black matrix.

[0334] In the color filter, the pixels and the black matrix are a colored pattern formed from a cured product of the above-described photosensitive coloring composition. In the color filter, components other than the materials of the pixels and the black matrix may be known.

[0335] The substrate used for color filters is not particularly limited, and glass substrates, silicon substrates, polycarbonate substrates, polyester substrates, polyamide substrates, polyamideimide substrates, polyimide substrates, aluminum substrates, printed circuit boards, array substrates, etc., can be appropriately used depending on the application.

[0336] Method for manufacturing color filters

[0337] Next, an exemplary method for manufacturing a color filter is described. First, a coloring pattern is formed on a substrate. Specifically, a coloring pattern that becomes a black matrix formed at the boundary of each pixel on the substrate, and a coloring pattern that becomes each RGB pixel, are sequentially formed by the method shown below.

[0338] A colored pattern can be formed by photolithography. Specifically, a photosensitive colored composition is applied onto a substrate to form a coating film. Then, the coating film is exposed to light through a photomask having a predetermined pattern shape, and the exposed portion is photocured. Subsequently, the unexposed portion of the coating film is developed with an alkaline aqueous solution. After that, a baking treatment is performed on the developed coating film to form a colored pattern having a predetermined pattern shape.

[0339] The method of 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 may be used.

[0340] In addition, after applying a photosensitive coloring composition onto a substrate, if necessary, the solvent (C) contained in the coating film may be evaporated and removed by heating the substrate using a heating means such as a circulating oven, an infrared heater, or a hot plate. The conditions for heating the substrate to remove the solvent (C) are not particularly limited and may be set appropriately according to the material of the substrate, the composition of the photosensitive coloring composition, the thickness of the coating film, etc. For example, the heating of the substrate may be performed at a temperature of 50°C to 120°C for 30 seconds to 30 minutes.

[0341] Next, an active energy line, such as ultraviolet light or excimer laser light, is irradiated onto the coating film formed in this way through a negative-type photomask, partially exposed, and the exposed area is photocured. The amount of active energy dose irradiated onto the coating film may be appropriately selected according to the composition of the photosensitive coloring composition, and for example, it can be 30 to 2000 mJ / cm². The light source used for exposure is not particularly limited, but a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, etc., can be used.

[0342] The alkaline aqueous solution used for developing the coating film is not particularly limited, but may be an aqueous solution of an inorganic alkali compound such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide; an aqueous solution of an amine compound such as ethylamine, diethylamine, dimethyl ethanolamine; an aqueous solution of a quaternary ammonium salt such as tetramethylammonium sulfate, hydrochloride, or p-toluenesulfonate; an aqueous solution of an aniline compound and its salt 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-methanesulfonamideethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and their sulfates, hydrochlorides, or p-toluenesulfonates; or an aqueous solution of a p-phenylenediamine compound and its salt. In addition, additives such as antifoaming agents and surfactants may be added to the alkaline aqueous solution as needed.

[0343] After developing the coating film using the above alkaline aqueous solution, it is preferable to wash and dry the coating film.

[0344] The conditions for the baking treatment performed when manufacturing a color filter can be appropriately determined according to the composition of the photosensitive coloring composition, the thickness of the coating film, the material of the substrate, etc. The temperature of the baking treatment can be, for example, 70°C to 210°C. If the baking temperature is 70°C or higher, good curability is obtained, and a cured product having excellent solvent resistance is obtained. The temperature of the baking treatment is preferably 75°C or higher, and more preferably 80°C or higher. If the temperature of the baking treatment is 210°C or lower, it is desirable because materials with low heat resistance, such as substrates with low heat resistance, can be used as the material for the color filter.

[0345] When forming a color pattern of a color filter using a conventional photosensitive coloring composition, if the baking treatment temperature is set to 200°C or lower, the solvent resistance of the coloring pattern becomes insufficient. In this regard, since the photosensitive coloring composition of one embodiment has good low-temperature curing properties, the baking treatment temperature can be lowered compared to the case where a conventional photosensitive coloring composition is used while ensuring the solvent resistance of the coloring pattern. Specifically, the baking treatment temperature can be set to 160°C or lower depending on the heat resistance of the substrate forming the resin cured film. For example, when forming a coloring pattern using a resin substrate as the substrate, the temperature may be set to 150°C or lower, 120°C or lower, or 100°C or lower.

[0346] The baking treatment performed when manufacturing a color filter can be performed for, for example, 10 minutes to 4 hours, preferably 20 minutes to 2 hours, and can be appropriately determined according to the composition of the photosensitive coloring composition, the temperature of the baking treatment, the thickness of the coating film, etc.

[0347] The photosensitive coloring composition has good photocurability and low-temperature curability. For this reason, when forming a coloring pattern using the photosensitive coloring composition of one embodiment, if the baking temperature is made equal to that of forming a coloring pattern using a conventional photosensitive coloring composition, the baking time can be shortened, and a color filter can be formed efficiently.

[0348] Using the above-described method for manufacturing a coloring pattern, a coloring pattern that becomes each RGB pixel and a coloring pattern that becomes a black matrix formed at the boundary of each pixel are formed, and then a protective film is formed on the coloring pattern (each RGB pixel and the black matrix).

[0349] The method of manufacturing the protective film is not particularly limited, and it may be formed using a photosensitive resin composition of one embodiment, or it may be formed using known materials and known methods.

[0350] A color filter is obtained through the above process.

[0351] The color filter has a color pattern formed from a cured product of the above-described photosensitive coloring composition. For this reason, 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.

[0352] In addition, as a colorant (F) included in the photosensitive coloring composition used as a material for a color filter, it is possible to use one with low heat resistance. Because of this, the range of available colorants (F) can be increased. Therefore, for example, it is possible to form a color filter that includes a colorant (F) with low heat resistance and has a coloring pattern in which the inherent characteristics of the colorant (F) with low heat resistance are exhibited.

[0353] Furthermore, the coloring pattern in the color filter can be formed on a substrate with low heat resistance, such as a resin substrate, without causing damage to the substrate. Therefore, the range of usable substrate options can be expanded. Specifically, for example, since the color filter can be formed on a substrate with low heat resistance, such as a resin substrate, the display can be made flexible. In addition, the coloring pattern in the color filter has excellent solvent resistance, resulting in minimal color change.

[0354] Here, an example has been described of a case in which a colored pattern is manufactured by using a photosensitive colored composition containing a photopolymerization initiator (E) and a method of photocuring the photosensitive colored composition. However, for example, instead of the photopolymerization initiator (E) included in the photosensitive colored composition, a photosensitive colored composition containing a curing accelerator and a known epoxy resin may be used, and a colored pattern consisting of a cured product of a photosensitive colored composition containing a modified copolymer (A2) may be formed by using an inkjet method and then heating.

[0355] Image display element

[0356] An image display element of one embodiment is provided with a color filter. In the image display element, known components other than the color filter may be adopted. Specific examples of the image display element include, for instance, solid-state imaging elements such as liquid crystal display elements, organic EL display elements, CCD elements, and CMOS elements.

[0357] Components other than the color filter in an image display element can be manufactured by known methods. For example, when manufacturing a liquid crystal display element as an image display element, it can be manufactured using the method described below. First, a color filter is formed on a substrate using the method described above. Then, electrodes, spacers, etc., are sequentially formed on the substrate having the color filter. Next, electrodes, etc., are formed on a separate substrate and placed opposite the substrate having the color filter to be joined together. After that, a predetermined amount of liquid crystal is injected between the opposing substrates and sealed.

[0358] Since the image display element is equipped with a color filter having excellent solvent resistance, there is minimal color change.

[0359] Examples

[0360] The present invention will be explained more specifically below through examples and comparative examples, but the present invention is not limited to the following examples.

[0361] Synthesis examples of modified copolymer (A2) are shown below.

[0362] [Example 1 (Synthetic Example 1)]

[0363] (Synthesis of copolymer(A))

[0364] 282.6 g of propylene glycol monomethyl ether (Tokyo Kasei High School Co., Ltd.) was added as a solvent (C) to a flask equipped with a stirring device, a dropping lot, a condenser, a thermometer, and a gas inlet tube, stirred while purging with nitrogen gas, and heated to 78°C.

[0365] Next, 17.2 g (20 mol%) of methacrylic acid as monomer (ma), 49.7 g (15 mol%) of 2-[(diethyl malate)carbonylamino]ethyl acrylate as monomer (m-pb), 19.5 g (15 mol%) of 2-hydroxyethyl methacrylate as monomer (mc), 90.3 g (30 mol%) of the reaction product of 2-isocyanatoethyl acrylate and diethyl malonicate as monomer (md), 36.8 g (20 mol%) of 2-ethylhexyl acrylate as monomer (me), 64.0 g (30 parts by mass per 100 parts by mass of the total monomer components) of propylene glycol monomethyl ether as solvent (C), and 34.2 g (on 100 parts by mass of the total monomer components A raw monomer solution was prepared by mixing 16 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) (Fujifilm Wako Junyaku Co., Ltd.).

[0366] The entire amount of the prepared raw monomer solution was added dropwise over 1 hour using a dropping lot to a solvent (C) in a flask under atmospheric pressure in a nitrogen gas atmosphere. After the dropping was finished, the solution in the flask was polymerized at 78°C for 3 hours while stirring to obtain a liquid containing copolymer (A) and solvent (C).

[0367] (Preparation of resin composition)

[0368] A resin composition was obtained by adding 0.4 g of hydroquinone monomethyl ether (MEHQ) as a polymerization inhibitor (0.2 parts by mass per 100 parts by mass of the monomer components of copolymer (A)) and 10.7 g of 4-dimethylaminopyridine (Kanto Chemical Co., Ltd.) as a basic catalyst (B) to a liquid containing a copolymer (A) and a solvent (C) in a flask at atmospheric pressure in a nitrogen gas atmosphere.

[0369] (Synthesis of modified copolymer (A2))

[0370] In a flask under atmospheric pressure with a nitrogen gas atmosphere, the resin composition was maintained at 78°C for 90 minutes while stirring, and the structural unit (pb) having a group represented by Formula (1) included in the copolymer (A) was converted into a structural unit (b) having a group represented by Formula (1-1) or Formula (1-2). By this, a reaction solution containing the copolymer (A), the modified copolymer (A2), and the solvent (C) was obtained. The conversion rate from the structural unit (pb) to the structural unit (b) was determined by the method described above and is listed in Table 1. The weight average molecular weight, ethylenically unsaturated group equivalent, and acid value of the mixture of the copolymer (A) and the modified copolymer (A2) were measured by the method described above and are listed in Table 1. The block isocyanate group equivalent and the hydroxyl group equivalent of the mixture of the copolymer (A) and the modified copolymer (A2) were calculated and are listed in Table 1.

[0371] In a reaction solution containing the copolymer (A) obtained in this way, the modified copolymer (A2), and the solvent (C), propylene glycol monomethyl ether acetate (Tokyo Kasei High School Co., Ltd.) was added as the solvent (C) so that the component other than the solvent was 35 mass%, thereby obtaining a liquid (modified resin composition) containing the modified copolymer (A2) of Example 1.

[0372] [Examples 2–6 (Synthetic Examples 2–6), Comparative Examples 1–2 (Comparative Synthetic Examples 1–2)]

[0373] Liquids (modified resin compositions) containing the modified copolymer (A2) of Examples 2 to 6 and liquids (modified resin compositions) containing the modified copolymer (cA2) of Comparative Examples 1 to 2 were obtained in the same manner as Example 1, except that the monomers and blending amounts listed in Table 1 were used and the time for the conversion reaction from the structural unit (pb) to the structural unit (b) was as listed in Table 1. The conversion rate to the structural unit (b) of Examples 2 to 6 and the conversion rate to the structural unit (b) of Comparative Examples 1 to 2 were determined by the above-described method and listed in Table 1. The weight average molecular weight, ethylenically unsaturated group equivalent, and acid value of the mixture of the copolymer (A) of Examples 2 to 6 and the modified copolymer (A2) and the mixture of the copolymer (cA) of Comparative Examples 1 to 2 were measured by the above-described method and listed in Table 1. The block isocyanate group equivalents and hydroxyl group equivalents of the mixture of copolymer (A) and modified copolymer (A2) of Examples 2 to 6 and the mixture of copolymer (cA) and modified copolymer (cA2) of Comparative Examples 1 to 2 were calculated and listed in Table 1.

[0374] [Comparative Example 3 (Comparative Synthesis Example 3)]

[0375] (Synthesis of copolymer (cA))

[0376] 142.7 g of propylene glycol monomethyl ether acetate (Tokyo Kasei High School Co., Ltd.) was added as a solvent (C) to a flask equipped with a stirring device, a dropping lot, a condenser, a thermometer, and a gas inlet tube, stirred while purging with nitrogen gas, and heated to 78°C.

[0377] Next, 66.2 g (20 mol%) of 2-[(diethyl)carbonylamino]ethyl acrylate as monomer (m-pb), 39.0 g (30 mol%) of 2-hydroxyethyl methacrylate as monomer (mc), 25.1 g (10 mol%) of 2-[(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate as monomer (md), 73.6 g (40 mol%) of 2-ethylhexyl acrylate as monomer (me), and 32.7 g (16 parts by mass per 100 parts by mass of the total monomer components) of 2,2'-azobis(2,4-dimethylvaleronitrile) (Fujifilm Wako Junyaku Co., Ltd.) as polymerization initiator were mixed to prepare a raw monomer solution.

[0378] The entire amount of the prepared raw monomer solution was added dropwise over 1 hour using a dropping lot to a solvent (C) in a flask under atmospheric pressure in a nitrogen gas atmosphere. After the dropping was finished, the solution in the flask was polymerized at 78°C for 3 hours while stirring to obtain a liquid containing copolymer (cA) and solvent (C).

[0379] (Preparation of resin composition)

[0380] 0.4 g of hydroquinone monomethyl ether (MEHQ) as a polymerization inhibitor (0.2 parts by mass per 100 parts by mass of the monomer components of copolymer (cA)) and 10.2 g of 4-dimethylaminopyridine (Kanto Chemical Co., Ltd.) as a basic catalyst (5 parts by mass per 100 parts by mass of the monomer components of copolymer (cA)) were added to a liquid containing copolymer (cA) and solvent (C) in a flask under atmospheric pressure in a nitrogen gas atmosphere, and a resin composition was obtained.

[0381] (Synthesis of modified copolymer (cA2))

[0382] 10 g of succinic anhydride (SA) (Shin Nippon Ricah Co., Ltd.) (10 moles per 100 moles of the total monomer used in the synthesis of copolymer (cA)) and 0.9 g of lithium naphthenate (Toei Kako Co., Ltd.) as a catalyst (0.4 parts by mass per 100 parts by mass of the total monomer and succinic anhydride used in the synthesis of copolymer (cA)) were added to the resin composition and an addition reaction was carried out by maintaining at 78°C for 90 minutes, thereby converting the structural unit (pb) having a group represented by Formula (1) contained in the copolymer (cA) into a structural unit (b) having a group represented by Formula (1-1) or Formula (1-2). By this, a reaction solution containing copolymer (cA), modified copolymer (cA2), and solvent (C) was obtained. The conversion rate from structural unit (pb) to structural unit (b) was determined by the method described above and is listed 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 method described above and are listed in Table 1. The block isocyanate group equivalent and hydroxyl group equivalent of the mixture of copolymer (cA) and modified copolymer (cA2) were calculated and are listed in Table 1.

[0383] In a reaction solution containing the copolymer (cA) obtained in this way, the modified copolymer (cA2), and the solvent (C), propylene glycol monomethyl ether acetate (Tokyo Kasei High School Co., Ltd.) was added as the solvent (C) so that the component other than the solvent was 35 mass%, thereby obtaining a liquid (modified resin composition) containing the modified copolymer (cA2) of Comparative Example 3.

[0384] [Comparative Example 4 (Comparative Synthesis Example 4)]

[0385] 241.2 g of propylene glycol monomethyl ether (Tokyo Kasei High School Co., Ltd.) was added as a solvent (C) to a flask equipped with a stirring device, a dropping lot, a condenser, a thermometer, and a gas inlet tube, stirred while purging with nitrogen gas, and heated to 78°C.

[0386] Next, 15.5 g (18 mol%) of methacrylic acid as monomer (ma), 18.2 g (14 mol%) of 2-hydroxyethyl methacrylate as monomer (mc), 60.2 g (20 mol%) of the reaction product of 2-isocyanatoethyl acrylate and diethyl malonicate as monomer (md), 88.3 g (48 mol%) of 2-ethylhexyl acrylate as monomer (me), 54.7 g (30 parts by mass per 100 parts by mass of the total monomer components) of propylene glycol monomethyl ether as solvent (C), and 29.2 g (16 parts by mass per 100 parts by mass of the total monomer components) of 2,2'-azobis(2,4-dimethylvaleronitrile) as polymerization initiator (Fujifilm Wako A raw material monomer solution was prepared by mixing Junyaku Kabushiki Kaisha.

[0387] The entire amount of the prepared raw monomer solution was added dropwise over 1 hour using a dropping lot to a solvent (C) in a flask under atmospheric pressure in a nitrogen gas atmosphere. After the dropping was finished, the polymerization reaction was carried out at 78°C for 3 hours while stirring the solution in the flask 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 method described above and are listed in Table 1. The block isocyanate group equivalent and hydroxyl group equivalent of copolymer (cA) were calculated and are listed in Table 1.

[0388] To the reaction solution containing the copolymer (cA) and solvent (C) obtained in this way, propylene glycol monomethyl ether acetate (Tokyo Kasei High School Co., Ltd.) was added as the solvent (C) so that the component other than the solvent was 35 mass%, and a liquid (resin composition) containing the copolymer (cA) of Comparative Example 4 was obtained.

[0389] [Table 1-1]

[0390]

[0391] [Table 1-2]

[0392]

[0393] The following compounds were used as the compounds listed in Tables 1 and 2, respectively.

[0394] MAA: Methacrylic acid (Curare Co., Ltd.)

[0395] AOI-MDE:Kalenz (trademark) AOI-MDE, 2-[(diethyl)carbonylamino]ethyl acrylate (Resonac Co., Ltd.)

[0396] AOI-DEM:Karenz (trademark) AOI-DEM, reaction product of 2-isocyanatoethyl acrylate and diethyl malonicate (malonicate-2-[[[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester, Resonac Co., Ltd.)

[0397] MOI-BP: Carens (trademark) MOI-BP, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (Resonac Co., Ltd.)

[0398] HEMA:2-Hydroxyethyl methacrylate (Nihon Shokubai Co., Ltd.)

[0399] 2EHA:2-ethylhexyl acrylate (Doagosei Co., Ltd.)

[0400] SA: Anhydrous succinic acid (Shin Nippon Rika Kabushiki Kaisha)

[0401] DBU:1,8-Diazabicyclo[5.4.0]-7-Undensen(San'Acro Kabushiki Kaisha)

[0402] DMAP: 4-Dimethylaminopyridine (Kanto Kagaku Kabushiki Kaisha)

[0403] Piridin (Kanto Kagaku Kabushiki Kaisha)

[0404] 1,2-Dimethylimidazole (Tokyo Kasei High School Co., Ltd.)

[0405] Triethylamine (Kanto Kagaku Kabushiki Kaisha)

[0406] DABCO: 1,4-diazabicyclo[2.2.2]octane (Kanto Kagaku Kabushiki Kaisha)

[0407] [Evaluation of Preservation Stability]

[0408] 10 mL of the modified resin composition obtained in Example 1 was weighed into a 20 mL sample bottle, sealed, and stored at 5°C for 3 months. The weight-average molecular weight of the sample after storage was measured, and the rate of increase in weight-average molecular weight was calculated according to the following formula. The rate of increase in weight-average molecular weight was similarly calculated 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 rates of increase in weight-average molecular weight are shown in Table 1. If the rate of increase is within 20%, the storage stability is good.

[0409] 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

[0410] [Examples 7–12, Comparative Examples 5–8]

[0411] Using the modified resin compositions of Examples 1 to 6 and Comparative Examples 1 to 3, and the resin composition of Comparative Example 4, a mixture of the copolymer (A) of Synthesis Examples 1 to 6 and the modified copolymer (A2) shown in Table 2, or a mixture of the copolymer (cA) of Comparative Synthesis Examples 1 to 3 and the modified copolymer (cA2), or the copolymer (cA) of Comparative Synthesis Example 4, a basic catalyst, dipentaerythritol pentaacrylate (Doagosei Co., Ltd.) as a reactive diluent (D), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl-]-, -1-(O-acetyloxime) (Chiba Japan Co., Ltd.) as a photopolymerization initiator (E), and a mixture of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether as a solvent (C) (338 parts by mass each, and 257 parts by mass), and Valifast Blue 2620 (phthalocyanine dye, Orient Kagaku Kogyo Co., Ltd.) as a coloring agent (F) were mixed in the ratios shown in Table 2, and photosensitive coloring compositions of Examples 7 to 12 and Comparative Examples 5 to 8 were prepared.

[0412] 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 copolymer (cA) shown in Table 2. The amount of solvent (C) shown in Table 2 is the sum of the amount of solvent included in the modified resin composition or resin composition obtained in Synthesis Examples 1 to 6 and Comparative Synthesis Examples 1 to 4, and the amount of solvent added when preparing the photosensitive coloring composition.

[0413] [Table 2-1]

[0414]

[0415] [Table 2-2]

[0416]

[0417] [Evaluation of Content]

[0418] Content-effectiveness was evaluated by the residual film rate.

[0419] (Residual film rate)

[0420] The photosensitive coloring compositions of Examples 7 to 12 and Comparative Examples 5 to 8 were each applied by spin coating on a flat, square glass substrate (alkali-free glass substrate) measuring 5 cm in length and 5 cm in width, such that the thickness after exposure was 2.5 μm, thereby forming a coating film. Subsequently, the solvent (C) in the coating film was evaporated and removed by heating at 100°C for 3 minutes.

[0421] Next, the coating film was exposed by irradiating it with ultraviolet light of a wavelength of 365 nm at an energy dose of 100 mJ / cm², and the exposed area was photocured. Afterwards, the coating film was cured by performing a baking treatment at 100°C for 20 minutes to form a cured film. The thickness of the fabricated cured film was measured using a step meter. The thickness at this time was denoted as X.

[0422] Afterward, the prepared cured film was immersed in 20g of propylene glycol monomethyl ether acetate (PGMEA) at 23°C for 15 minutes. After immersion, the coating film was vacuum dried at 40°C for 30 minutes, and the thickness of the coating film was measured using a step gauge. The thickness at this time was denoted as Y.

[0423] Using the following formula, 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 residual film rate, and the solvent resistance of the cured film was evaluated. That is, the closer the residual film rate is to 100%, the better the solvent resistance of the cured film. For evaluation, a residual film rate of 80% or higher was set as the passing line. The residual film rates of the cured film are shown in Table 2.

[0424] Residual film rate = (Y / X) × 100 (%)

[0425] 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 the solvent resistance was good even at a low temperature of 100°C for the baking treatment.

[0426] [Evaluation of Phenomenality]

[0427] Phenotyping was evaluated based on the solubility and adhesion of the hardened film.

[0428] (Solubility)

[0429] The photosensitive coloring compositions prepared in Examples 7 to 12 and Comparative Examples 5 to 8 were each coated onto a 5 cm × 5 cm glass substrate (alkali-free glass substrate) by a spin coating method 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 dry the coating film (pre-bake process).

[0430] Next, light of 100 mJ / cm² was irradiated onto the surface of the dried coating film through a photomask using an ultra-high pressure mercury lamp (exposure process). The exposure process was performed by installing the photomask at a position 100 µm away from the coating film. As the photomask, one having a line and space pattern with a width of 3 to 100 µm was used. Next, Semiclean DL-A10 developer (Yokohama Yushi Kogyo Co., Ltd.) (300-fold dilution) was sprayed onto the surface of the coating film for 60 seconds under conditions of a temperature of 23°C and a pressure of 0.1 MPa to exclude unexposed areas (development process). The dissolution pattern of the coating film when the developer was sprayed was observed, and solubility was evaluated according to the following criteria. The results are shown in Table 2.

[0431] 1: There is no residue in the unexposed area, no powder is visible in the developer, and the pattern shape is good.

[0432] 2: There is no residue in the unexposed area, but powder is visible in the developer, and the pattern shape is relatively good.

[0433] 3: Residue remains in the unexposed area, and there are locations without pattern shapes.

[0434] 4: In the exposure area, the film peels off, and no pattern remains.

[0435] (Adhesion)

[0436] A glass substrate having a coating film after the development process was placed in a dryer at 100°C for 30 minutes to heat-cur the coating film (post-baking process), thereby obtaining a colored pattern. The colored pattern obtained in this way was observed using a microscope, and the adhesion was evaluated based on the minimum line width that could be developed (minimum development dimension (㎛)). The results are shown in Table 2.

[0437] (Industrial Applicability)

[0438] According to the present disclosure, a photosensitive resin composition is provided that imparts a resin cured film having excellent solvent resistance, contributing to an improvement in developability. Furthermore, according to the present disclosure, an image display element is provided that comprises a color filter having a coloring pattern formed from a resin cured film having excellent solvent resistance. The photosensitive resin composition and the photosensitive coloring composition can preferably be used as materials such as a transparent film, a protective film, an insulating film, an overcoat, a photospacer, a black matrix, a black column spacer, and a resist for a color filter.

Claims

Claim 1 A resin composition comprising a copolymer (A), a basic catalyst (B), and a solvent (C), wherein the copolymer (A) is a copolymer having 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) of 4 to 12 at 25°C. (In Equation (1), R 1 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 2 and R 3 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a connection site between the structural unit (pb) and a residue excluding the group of Formula (1). Claim 2 A modified resin composition comprising a modified copolymer (A2), a basic catalyst (B), and a solvent (C), wherein the modified copolymer (A2) comprises 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 the following formula (1-2), and the basic catalyst (B) is a basic catalyst having a pKa (acidity constant) of 4 to 12 at 25°C. (In Equation (1), R 1 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 2 and R 3 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a connection site between the structural unit (pb) and a residue excluding the group of Formula (1). (In Equation (1-1), R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 2 and R 3 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * indicates a connection site with a residue excluding the group of Formula (1-1) from the structural unit (b). (In Equation (1-2), R 2 and R 3 Each is 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 * indicates a connection site between the structural unit (b) and a residue excluding the group of formula (1-2). Claim 3 A modified resin composition according to claim 2, wherein the basic catalyst (B) is at least one selected from the group consisting of pyridine, pyridine derivatives, and imidazole compounds. Claim 4 A 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. Claim 5 A modified resin composition according to claim 2, wherein the ethylenically unsaturated group equivalent of the modified copolymer (A2) is 300 to 10000 g / mol. Claim 6 A photosensitive resin composition comprising a modified resin composition described in any one of claims 2 to 5, a reactive diluent (D), and a photopolymerization initiator (E). Claim 7 A photosensitive coloring composition comprising a modified resin composition described in any one of claims 2 to 5, a reactive diluent (D), a photopolymerization initiator (E), and a coloring agent (F). Claim 8 A resin cured film comprising a cured product of the photosensitive resin composition described in claim 6. Claim 9 A resin cured film comprising a cured product of the photosensitive coloring composition described in claim 7. Claim 10 A color filter having a coloring pattern composed of a cured product of the photosensitive coloring composition described in claim 7. Claim 11 An image display element having a color filter as described in claim 10. Claim 12 A method for preparing a resin composition comprising a copolymer (A), a basic catalyst (B), and a solvent (C), wherein the copolymer (A) is a copolymer having 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) of 4 to 12 at 25°C. (In Equation (1), R 1 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 2 and R 3 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a connection site between the structural unit (pb) and a residue excluding the group of Formula (1). Claim 13 A method for manufacturing a modified resin composition having a heating process (II) in which the resin composition obtained by the manufacturing method described in claim 12 is maintained for 30 to 300 minutes under conditions of 50 to 100°C, and in the heating process (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), and a structural unit (b) having a group represented by the following formula (1-1) or the following formula (1-2). (In Equation (1), R 1 and R 4 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 2 and R 3 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a connection site between the structural unit (pb) and a residue excluding the group of Formula (1). (In Equation (1-1), R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 2 and R 3 Each is independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * indicates a connection site with a residue excluding the group of Formula (1-1) from the structural unit (b). (In Equation (1-2), R 2 and R 3 Each is 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 * indicates a connection site between the structural unit (b) and a residue excluding the group of formula (1-2).

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