Photosensitive resin composition, cured resin film, and image display element

Abstract

A photosensitive resin composition which contains a copolymer (A-1), a copolymer (A-2), a photopolymerization initiator (C), and a solvent (D), wherein: the copolymer (A-1) contains a constituent unit (a) having a hydroxy group and a blocked isocyanate group, a constituent unit (b) having a nitrogen atom, and a constituent unit (c) having an acid group; and the unsaturated group equivalent of the copolymer (A-2) is 30-3,000 g / mol.

Description

Photosensitive resin composition, resin cured film, and image display element

[0001] This disclosure relates to a photosensitive resin composition, a resin cured film, and an image display element.

[0002] In recent years, with the widespread adoption of liquid crystal displays (LCDs), there has been extensive research being conducted on color filters used as components of LCDs, as well as on the overcoat layers and interlayer insulating films provided on these color filters.

[0003] Japanese Patent Publication No. 2019-53266

[0004] This disclosure provides a photosensitive resin composition that yields a resin-cured film with good developability, solvent resistance, and excellent adhesion. Furthermore, this disclosure provides a resin-cured film with excellent solvent resistance and adhesion, and an image display element comprising the same.

[0005] The disclosure includes the following embodiments: [Embodiment 1] A photosensitive resin composition comprising a copolymer (A-1), a copolymer (A-2), a photopolymerization initiator (C), and a solvent (D), wherein the copolymer (A-1) comprises a constituent unit (a) having a hydroxyl group and a blocked isocyanate group, a constituent unit (b) having a nitrogen atom, and a constituent unit (c) having an acid group, and the unsaturated group equivalent of the copolymer (A-2) is 30 to 3000 g / mol. [Embodiment 2] A photosensitive resin composition comprising a copolymer (A-1), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D), wherein the copolymer (A-1) comprises a constituent unit (a) having a hydroxyl group and a blocked isocyanate group, a constituent unit (b) having a nitrogen atom, and a constituent unit (c) having an acid group. [Aspect 3] A photosensitive resin composition comprising a copolymer (A-1), a copolymer (A-2), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D), wherein the copolymer (A-1) comprises a constituent unit (a) having a hydroxyl group and a blocked isocyanate group, a constituent unit (b) having a nitrogen atom, and a constituent unit (c) having an acid group, and the unsaturated group equivalent of the copolymer (A-2) is 30 to 3000 g / mol. [Aspect 4] The photosensitive resin composition according to any one of aspects 1 to 3, wherein the constituent unit (b) is a constituent unit derived from an amide group-containing ethylenically unsaturated compound. [Aspect 5] The photosensitive resin composition according to any one of aspects 1 to 4, wherein the constituent unit (b) is a constituent unit derived from an ethylenically unsaturated compound containing an amide group and a hydroxyl group. [Aspect 6] The photosensitive resin composition according to any one of aspects 1 to 5, wherein the constituent unit (a) is a constituent unit having at least one selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2). (In formula (1), R １ and R ２ Each of the following independently represents an alkyl group having 1 to 10 carbon atoms, n1 and n2 independently represent integers from 0 to 2, and * represents a linking site. (In formula (2), R３ and R ４ (Each of the above states independently represents an alkyl group having 1 to 10 carbon atoms, n3 and n4 each independently represent an integer from 0 to 2, and * represents a linking site.) [Aspect 7] The photosensitive resin composition according to any one of aspects 1 to 5, wherein the blocking agent constituting the blocked isocyanate group of the constituent unit (a) is at least one selected from the group consisting of pyrazole compounds, oxime compounds, and phenol compounds. [Aspect 8] The photosensitive resin composition according to any one of aspects 1 to 7, wherein the copolymer (A-1) further contains constituent units other than the constituent units (a) to (c). [Aspect 9] The photosensitive resin composition according to any one of aspects 1 to 8, wherein the copolymer (A-1) has a blocked isocyanate group equivalent of 200 to 3000 g / mol and a hydroxyl group equivalent of 100 to 5000 g / mol. [Aspect 10] The photosensitive resin composition according to any one of aspects 1 to 9, wherein the copolymer (A-1) has an acid value of 5 to 400 KOH mg / g and a weight-average molecular weight of 3,000 to 50,000. [Aspect 11] The photosensitive resin composition according to any one of aspects 1 to 10, wherein, of the total constituent units of the copolymer (A-1), the content of constituent unit (a) is 1 to 50 mol%, the content of constituent unit (b) is 1 to 50 mol%, and the content of constituent unit (c) is 1 to 70 mol%. [Aspect 12] A photosensitive colored composition containing the photosensitive resin composition according to any one of aspects 1 to 11 and a coloring agent (E). [Aspect 13] A resin-cured film which is a cured product of the photosensitive resin composition according to any one of aspects 1 to 11. [Aspect 14] A color filter having a colored pattern which is a cured product of the photosensitive colored composition according to aspect 12. [Aspect 15] An image display element comprising the color filter described in aspect 14 above.

[0006] According to this disclosure, it is possible to provide a photosensitive resin composition that yields a resin-cured film with good developability, as well as excellent solvent resistance and adhesion. Furthermore, it is possible to provide a resin-cured film with excellent solvent resistance and adhesion, and an image display element comprising the same.

[0007] The embodiments of the present invention will be described in detail below. However, the present invention is not limited to the embodiments shown below.

[0008] In this specification, when "~" is used for a numerical range, the numbers at both ends are the upper and lower limits, respectively, and are included in the numerical range. If multiple upper or lower limits are listed, a numerical range can be created from all combinations of upper and lower limits. Similarly, if multiple numerical ranges are listed, separate numerical ranges can be created by individually selecting and combining upper and lower limits from those ranges.

[0009] In this specification, "(meth)acrylic acid" means methacrylic acid or acrylic acid, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acryloyl" means acryloyl or methacryloyl. In this specification, "(poly)alkylene glycol" means alkylene glycol or polyalkylene glycol.

[0010] In this specification, "ethylenically unsaturated bond" means a double bond formed between carbon atoms excluding the carbon atoms forming the aromatic ring, "ethylenically unsaturated group" means a group having an ethylenically unsaturated bond, and "ethylenically unsaturated compound" means a compound having an ethylenically unsaturated bond.

[0011] In this specification, "constituent unit" means a unit derived from the polymerizable compound used as a monomer, or a unit obtained by further modifying a unit derived from the polymerizable compound used as a monomer after polymerization.

[0012] In this specification, the acid value of a copolymer is the acid value of a curable polymer measured according to JIS K6901:2008 5.3.2. That is, the acid value represents the number of mg of potassium hydroxide required to neutralize the acidic components contained in 1 g of copolymer.

[0013] In this specification, the total nitrogen equivalent of a copolymer is the mass of the copolymer per mole of nitrogen in the copolymer. The total nitrogen equivalent can be obtained by dividing the mass of the copolymer by the number of nitrogen atoms in the copolymer (g / mol). In this specification, the total nitrogen equivalent of a copolymer is a theoretical value calculated from the charged amount of raw materials used in producing the copolymer.

[0014] In this specification, the nitrogen equivalent (b) of a copolymer is the mass of the copolymer per mole of nitrogen contained in the structural unit (b) having a nitrogen atom in the copolymer. The nitrogen equivalent (b) can be obtained by dividing the mass of the copolymer by the number of nitrogen atoms contained in the structural unit (b) having a nitrogen atom in the copolymer (g / mol). In this specification, the nitrogen equivalent (b) of a copolymer is a theoretical value calculated from the charged amount of raw materials used in producing the copolymer.

[0015] In this specification, the blocked isocyanato group equivalent of a copolymer is the mass of the copolymer per mole of blocked isocyanato groups in the copolymer. The blocked isocyanato group equivalent can be obtained by dividing the mass of the copolymer by the number of blocked isocyanato groups in the copolymer (g / mol). In this specification, the blocked isocyanato group equivalent of a copolymer is a theoretical value calculated from the charged amount of raw materials used in producing the copolymer.

[0016] In this specification, the hydroxyl group equivalent of a copolymer is the mass of the copolymer per mole of hydroxy groups in the copolymer. The hydroxyl group equivalent can be obtained by dividing the mass of the copolymer by the number of hydroxy groups in the copolymer (g / mol). In this specification, the hydroxyl group equivalent of a copolymer is a theoretical value calculated from the charged amount of raw materials used in producing the copolymer.

[0017] In this specification, the unsaturated group equivalent of a copolymer is the mass of the copolymer per mole of ethylenically unsaturated groups in the copolymer. The unsaturated group equivalent can be determined by dividing the mass of the copolymer by the number of ethylenically unsaturated groups in the copolymer (g / mol). In this specification, the unsaturated group equivalent of a copolymer is a theoretical value calculated from the amount of raw materials used in the production of the copolymer.

[0018] In this specification, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are defined as values ​​obtained by measuring using gel permeation chromatography (GPC) under the following conditions and using a standard polystyrene calibration curve. Column: Two Showdex® LF-804 columns (Resonac Co., Ltd.) connected in series. Column temperature: 40°C. Sample: 0.2% by mass tetrahydrofuran solution of the substance to be measured. Developing solvent: Tetrahydrofuran. Detector: Differential refractometer (Showdex® RI-71S) (Resonac Co., Ltd.). Flow rate: 1 mL / min.

[0019] <Photosensitive Resin Composition> The photosensitive resin composition of one embodiment contains copolymer (A-1), copolymer (A-2), photopolymerization initiator (C), and solvent (D), wherein the unsaturated group equivalent of copolymer (A-2) is 30 to 3000 g / mol. The photosensitive resin composition of one embodiment contains copolymer (A-1), reactive diluent (B), photopolymerization initiator (C), and solvent (D). The photosensitive resin composition of one embodiment contains copolymer (A-1), copolymer (A-2), reactive diluent (B), photopolymerization initiator (C), and solvent (D), wherein the unsaturated group equivalent of copolymer (A-2) is 30 to 3000 g / mol. The photosensitive resin composition polymerizes and hardens upon irradiation with light to form a cured resin film. The photosensitive resin composition of one embodiment exhibits good low-temperature curing properties and can form a resin-cured film with sufficient hardness and solvent resistance. Furthermore, since the photosensitive resin composition has excellent alkali developability, fine patterns can be formed by developing it with an alkaline aqueous solution. Therefore, the photosensitive resin composition is suitably used, for example, as a resist.

[0020] [Copolymer (A-1)] The copolymer (A-1) has a hydroxy group, a structural unit (a) having a blocked isocyanato group (hereinafter, also simply referred to as "structural unit (a)"), a structural unit (b) having a nitrogen atom (hereinafter, also simply referred to as "structural unit (b)"), and a structural unit (c) having an acid group (hereinafter, also simply referred to as "structural unit (c)"). The copolymer (A-1) may contain at least one selected from the group consisting of a structural unit (d) having a hydroxy group (hereinafter, also simply referred to as "structural unit (d)") and other structural units (e) other than the structural units (a) to (d) (hereinafter, also simply referred to as "structural unit (e)") as needed.

[0021] The weight average molecular weight of the copolymer (A-1) is preferably 3,000 or more, more preferably 4,000 or more, still more preferably 5,000 or more, and even more preferably 6,000 or more. The weight average molecular weight of the copolymer (A-1) is preferably 50,000 or less, more preferably 30,000 or less, still more preferably 20,000 or less, and even more preferably 15,000 or less. When the weight average molecular weight of the copolymer (A-1) is 3,000 or more, the curability of the photosensitive resin composition or the photosensitive coloring composition is good, and the solvent resistance of the cured product tends to be better. When the weight average molecular weight of the copolymer (A-1) is 5,000 or less, the storage stability of the photosensitive resin composition or the photosensitive coloring composition tends to be good.

[0022] The molecular weight distribution (Mw / Mn) of copolymer (A-1) is preferably 1.1 or higher, more preferably 1.3 or higher, even more preferably 1.5 or higher, and even more preferably 1.7 or higher. The molecular weight distribution (Mw / Mn) of copolymer (A-1) is preferably 5 or lower, more preferably 4 or lower, even more preferably 2.5 or lower, and even more preferably 2.3 or lower. When the molecular weight distribution (Mw / Mn) of copolymer (A-1) is 1.1 or higher, it tends to be easier to control the reaction conditions during synthesis. When the molecular weight distribution (Mw / Mn) of copolymer (A-1) is 5 or lower, the storage stability of the photosensitive resin composition or photosensitive colored composition and the solvent resistance of its cured product tend to be better.

[0023] The total nitrogen equivalent of copolymer (A-1) is preferably 50 g / mol or more, more preferably 100 g / mol or more, even more preferably 200 g / mol or more, and even more preferably 300 g / mol or more. The total nitrogen equivalent of copolymer (A-1) is preferably 5000 g / mol or less, more preferably 3000 g / mol or less, even more preferably 2000 g / mol or less, and even more preferably 1000 g / mol or less. When the total nitrogen equivalent of copolymer (A-1) is 50 g / mol or more, the solvent resistance of the photosensitive resin composition or photosensitive colored composition tends to be good. When the total nitrogen equivalent of copolymer (A-1) is 5000 g / mol or less, the fine wire adhesion of the cured product of the photosensitive resin composition or photosensitive colored composition tends to be better.

[0024] The nitrogen equivalent (b) of copolymer (A-1) is preferably 100 g / mol or more, more preferably 300 g / mol or more, even more preferably 500 g / mol or more, and even more preferably 1000 g / mol or more. The nitrogen equivalent (b) of copolymer (A-1) is preferably 6000 g / mol or less, more preferably 5000 g / mol or less, even more preferably 4000 g / mol or less, and even more preferably 3000 g / mol or less. When the nitrogen equivalent (b) of copolymer (A-1) is 100 g / mol or more, the solvent resistance of the photosensitive resin composition or photosensitive colored composition tends to be good. When the nitrogen equivalent (b) of copolymer (A-1) is 6000 g / mol or less, the fine wire adhesion of the cured product of the photosensitive resin composition or photosensitive colored composition tends to be better.

[0025] The block isocyanate group equivalent of copolymer (A-1) is preferably 200 g / mol or more, more preferably 300 g / mol or more, and even more preferably 400 g / mol or more. The block isocyanate group equivalent of copolymer (A-1) is preferably 3000 g / mol or less, more preferably 2000 g / mol or less, even more preferably 1500 g / mol or less, and even more preferably 1000 g / mol or less. When the block isocyanate group equivalent of copolymer (A-1) is 200 g / mol or more, the storage stability of the photosensitive resin composition or photosensitive colored composition tends to be good. When the block isocyanate group equivalent of copolymer (A-1) is 3000 g / mol or less, the solvent resistance of the cured product of the photosensitive resin composition or photosensitive colored composition tends to be better.

[0026] The hydroxyl group equivalent of copolymer (A-1) is preferably 100 g / mol or more, more preferably 200 g / mol or more, even more preferably 300 g / mol or more, and even more preferably 400 g / mol or more. The hydroxyl group equivalent of copolymer (A-1) is preferably 5000 g / mol or less, more preferably 4000 g / mol or less, even more preferably 3000 g / mol or less, and even more preferably 2000 g / mol or less. When the hydroxyl group equivalent of copolymer (A-1) is 100 g / mol or more, the storage stability of the photosensitive resin composition or photosensitive colored composition tends to be good. When the hydroxyl group equivalent of copolymer (A-1) is 5000 g / mol or less, the solvent resistance of the cured product of the photosensitive resin composition or photosensitive colored composition tends to be better.

[0027] The acid value of copolymer (A-1) is preferably 5 KOH mg / g or more, more preferably 10 KOH mg / g or more, even more preferably 15 KOH mg / g or more, and even more preferably 20 KOH mg / g or more. The acid value of copolymer (A-1) is preferably 400 KOH mg / g or less, more preferably 300 KOH mg / g or less, even more preferably 200 KOH mg / g or less, and even more preferably 100 KOH mg / g or less. When the acid value of copolymer (A-1) is 5 KOH mg / g or more, the storage stability of the photosensitive resin composition or photosensitive colored composition tends to be good. When the acid value of copolymer (A-1) is 400 KOH mg / g or less, the solvent resistance of the cured product of the photosensitive resin composition or photosensitive colored composition tends to be better.

[0028] (Constituent unit (a) having a blocked isocyanate group) Constituent unit (a) is not particularly limited as long as it has a structure in which the isocyanate group is blocked by the addition of a blocking agent. Constituent unit (a) may be one type or two or more types. In one embodiment, constituent unit (a) is a constituent unit derived from a blocked isocyanate group-containing monomer (m-a) (hereinafter also simply referred to as "monomer (m-a)"). The copolymer (A-1) having constituent unit (a) allows crosslinking with reactive functional groups contained in the photosensitive resin composition or photosensitive colored composition to proceed when heated, forming a cured product with a high crosslink density. As a result, the obtained cured product has good solvent resistance even under low-temperature curing conditions. Crosslinking is formed, for example, by the reaction of isocyanate groups generated by the dissociation of the blocking agent upon heating with reactive functional groups. Examples of reactive functional groups include hydroxyl groups, acidic groups, and optionally amino groups contained in copolymer (A-1). Since copolymer (A-1) has a hydroxyl group, if the blocking agent is a compound having an alkyloxycarbonyl group, crosslinking can be formed by transesterification even without dissociation of the blocking agent.

[0029] In one embodiment, the monomer (m-a) has an ethylenically unsaturated group and a blocked isocyanate group. Examples of the ethylenically unsaturated group include a vinyl group and a (meth)acryloyloxy group.

[0030] Monomer (m-a) can be produced, for example, by blocking the isocyanate group of an isocyanate compound having an ethylenically unsaturated bond with a blocking agent. The blocking reaction can be carried out with or without the presence of a solvent. Organometallic salts containing metals such as tin, zinc, and lead, or tertiary amines may be used as catalysts in the blocking reaction.

[0031] Examples of isocyanate compounds having an ethylenically unsaturated bond include the compound represented by the following formula (3).

[0032] (In formula (3), R ５represents a hydrogen atom or a methyl group; R ６ is -CO-, -COOR ７ - (where R ７ is an alkylene group having 1 to 6 carbon atoms.) or -COO-R ８ O-CONH-R ９ - (where R ８ is an alkylene group having 2 to 6 carbon atoms, and R ９ is an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms which may have a substituent.) is shown.)

[0033] In the isocyanate compound represented by the formula (3), R ６ is preferably -COOR ７ - from the viewpoint of the reactivity of the isocyanato group after deblocking, and it is more preferable that R ７ is an alkylene group having 1 to 4 carbon atoms.

[0034] As the isocyanate compound having an ethylenically unsaturated bond, a reaction product obtained by reacting a hydroxyalkyl (meth) acrylate such as hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate with a diisocyanate compound in equimolar amounts (hydroxyalkyl (meth) acrylate:diisocyanate compound = 1 mol:1 mol) may be used.

[0035] Examples of the diisocyanate compound include hexamethylene diisocyanate, 2,4- (or 2,6-) tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 3,5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate (IPDI), m- (or p-) xylene diisocyanate, 1,3- (or 1,4-) bis (isocyanatomethyl) cyclohexane, lysine diisocyanate, and the like.

[0036] From the viewpoint of the low-temperature curability of the photosensitive resin composition or the photosensitive coloring composition, the structural unit (a) is preferably a structural unit derived from a blocked isocyanato group-containing (meth) acrylate obtained by blocking an isocyanato group-containing (meth) acrylate.

[0037] Examples of isocyanato group-containing (meth)acrylates include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, 1,1-bis(acryloyloxymethyl)methyl isocyanate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate, 1,1-bis(methacryloyloxymethyl)methyl isocyanate, and 1,1-bis(methacryloyloxymethyl)ethyl isocyanate. Among these, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, and 1,1-bis(methacryloyloxymethyl)ethyl isocyanate are preferred.

[0038] Examples of blocking agents include lactam compounds such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; alcohol compounds such as methanol, ethanol, propanol, 1-methoxy-2-propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, and cyclohexanol; phenols such as phenol, 2,6-dimethylphenol, cresol, 3,5-xylenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol, and other butylphenols, p-tert-octylphenol, nonylphenol, dinonylphenol, styrene-phenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, thymol, 1-naphthol, p-nitrophenol, and p-chlorophenol; dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetate. Active methylene compounds such as methyl mercaptan; mercaptan compounds such as butyl mercaptan, thiophenol, tert-dodecyl mercaptan; amine compounds such as diisopropylamine, diphenylamine, phenylnaphthylamine, aniline, carbazole; acid amide compounds such as acetanilide, acetanisidide, acetic acid amide, benzamide; imide compounds such as succinimide, maleimide; imidazole compounds such as imidazole, 2-methylimidazole, 2-ethylimidazole; pyrazole, Examples include pyrazole compounds such as 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 ketoxime, methyl isobutyl ketoxime, and cyclohexanone oxime; and bisulfites such as sodium bisulfite and potassium bisulfite. The blocking agents may be used alone or in combination of two or more types.

[0039] In one embodiment, the blocking agent is preferably at least one selected from the group consisting of pyrazole compounds, oxime compounds, and phenol compounds, and more preferably at least one selected from 3,5-dimethylpyrazole, methyl 4-hydroxybenzoate, and methyl ethyl ketoxime, from the viewpoint of the low-temperature curability of the photosensitive resin composition or photosensitive colored composition.

[0040] In constituent unit (a), the dissociation rate of the blocked isocyanate group when heated at 100°C for 30 minutes is preferably 5 to 99%, more preferably 10 to 90%, and most preferably 15 to 80%. The dissociation rate may be, if necessary, for example, 8 to 70%, 15 to 60%, or 30 to 50%. When the above dissociation rate is 99% or less, it tends to suppress the regeneration of the isocyanate group in constituent unit (a) and the occurrence of unintended crosslinking reactions during the synthesis of copolymer (A-1) and during the storage of the photosensitive resin composition or photosensitive colored composition. When the above dissociation rate is 5% or more, good curability can be obtained even if the heating temperature for curing the photosensitive resin composition or photosensitive colored composition is sufficiently low, and a cured product with better solvent resistance tends to be obtained.

[0041] Examples of blocking agents whose dissociation rate is suitable from the viewpoint of the stability of the copolymer (A-1) and the low-temperature curability of the photosensitive resin composition or photosensitive colored composition include γ-butyrolactam, 1-methoxy-2-propanol, 2,6-dimethylphenol, diisopropylamine, methyl ethyl ketoxime, and 3,5-dimethylpyrazole, with 3,5-dimethylpyrazole and methyl ethyl ketoxime being preferred.

[0042] The above dissociation rate can be considered to be the same as the dissociation rate of the blocked isocyanate group when the blocked isocyanate group-containing monomer (m-a) is heated at 100°C for 30 minutes, and is calculated by the following method. Specifically, an n-octanol solution with a monomer (m-a) concentration of 20% by mass is prepared. To the obtained n-octanol solution, 1% by mass of dibutylsus laurate is added as a catalyst and 3% by mass of phenothiazine is added as a polymerization inhibitor, and the solution is heated at 100°C for 30 minutes. The n-octanol solution after heating is analyzed by high-performance liquid chromatography (HPLC) to determine the mass of monomer (m-a) in the n-octanol solution. Using the result, the mass reduction rate of monomer (m-a) is calculated and determined as the dissociation rate when heated at 100°C for 30 minutes.

[0043] The dissociation temperature at which the dissociation rate of the block isocyanate group of constituent unit (a) reaches 80% or more in 30 minutes is preferably 80°C or higher, more preferably 90°C or higher, and even more preferably 100°C or higher. When the above dissociation temperature is 80°C or higher, it tends to suppress the regeneration of the isocyanate group of constituent unit (a) and the occurrence of unintended crosslinking reactions during the synthesis of copolymer (A-1) and during the storage of the photosensitive resin composition or photosensitive colored composition. The above dissociation temperature may be 160°C or lower. When the above dissociation temperature is 160°C or lower, good curability can be obtained even if the heating temperature for curing the photosensitive resin composition or photosensitive colored composition is sufficiently low, and a cured product with better solvent resistance tends to be obtained.

[0044] The above dissociation temperature is calculated by the following method. Specifically, an n-octanol solution with a monomer (m-a) concentration of 20% by mass is prepared. To the obtained n-octanol solution, 1% by mass of dibutylsulata laurate is added as a catalyst and 3% by mass of phenothiazine is added as a polymerization inhibitor, and the solution is heated for 30 minutes under several different temperature conditions. The n-octanol solutions heated under different temperature conditions are analyzed by high-performance liquid chromatography (HPLC) to determine the mass of monomer (m-a) in the n-octanol solution. Using these results, the temperature at which the mass reduction rate of monomer (m-a) is 80% or more is extracted. The lowest temperature among these is determined as the dissociation temperature at which the dissociation rate of the blocked isocyanate group is 80% or more in 30 minutes.

[0045] The constituent unit (a) is preferably at least one selected from a constituent unit derived from a compound in which acryloyloxyethyl isocyanate is blocked with 3,5-dimethylpyrazole, represented by the following formula (4) (dissociation temperature at which the dissociation rate of the blocked isocyanate group is 80% or more in 30 minutes: 120°C, dissociation rate when heated at 100°C for 30 minutes: 35%), and a constituent unit derived from a compound in which methacryloyloxyethyl isocyanate is blocked with methyl ethyl ketoxime, represented by the following formula (5) (dissociation temperature at which the dissociation rate of the blocked isocyanate group is 80% or more in 30 minutes: 130°C, dissociation rate when heated at 100°C for 30 minutes: 18%).

[0046]

[0047] In one embodiment, from the viewpoint of low-temperature curability of the photosensitive resin composition or photosensitive colored composition, compounds having an alkyloxycarbonyl group are preferred as the blocking agent, and activated methylene compounds having an alkyloxycarbonyl group are more preferred. When a compound having an alkyloxycarbonyl group is used as the blocking agent, the photosensitive resin composition or photosensitive colored composition can provide a cured film with excellent solvent resistance even when cured at a low temperature of 50°C to 150°C.

[0048] In this embodiment, the constituent unit (a) preferably has at least one selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2).

[0049] (In formula (1), R １ and R ２ Each of the following independently represents an alkyl group having 1 to 10 carbon atoms, n1 and n2 independently represent integers from 0 to 2, and * represents a linking site.

[0050] (In formula (2), R ３ and R ４ Each of the following independently represents an alkyl group having 1 to 10 carbon atoms, n3 and n4 independently represent integers from 0 to 2, and * represents a linking site.

[0051] In the above formula (1), R １ and R ２ Each of them is preferably an alkyl group having 2 to 6 carbon atoms, and more preferably an alkyl group having 2 to 3 carbon atoms, R １ and R ２ It is most preferable that both are ethyl groups. １ and R ２ When n1 is an ethyl group, ethanol is produced by a transesterification reaction when the photosensitive resin composition or photosensitive colored composition is heat-cured. The produced ethanol is readily evaporated and removed by heating during heat curing, which is preferable. It is preferable that both n1 and n2 in the above formula (1) are 0.

[0052] In the above formula (2), R ４ R is preferably an alkyl group having 2 to 6 carbon atoms, more preferably an alkyl group having 2 to 3 carbon atoms, and even more preferably an ethyl group. ４ When n is an ethyl group, ethanol is produced by a transesterification reaction when the photosensitive resin composition or photosensitive colored composition is heat-cured. The produced ethanol is readily evaporated and removed by heating during heat curing, which is preferable. It is preferable that both n3 and n4 in formula (2) above are 0.

[0053] In this embodiment, the rate of denaturation of the blocked isocyanate group when a constituent unit (a) having a blocked isocyanate group is heated at 100°C for 30 minutes is calculated in the same manner as the rate of denaturation of the blocked isocyanate group when a monomer (m-a) containing a blocked isocyanate group is heated at 100°C for 30 minutes. Specifically, the rate of mass reduction of the monomer (m-a) is calculated by adding a catalyst and a polymerization inhibitor to an n-octanol solution with a monomer (m-a) concentration of 20% by mass and heating at 100°C for 30 minutes, and this is determined as the denaturation rate when heated at 100°C for 30 minutes. The rate of denaturation of the blocked isocyanate group is preferably 5 to 99%, more preferably 10 to 90%, and most preferably 15 to 80%.

[0054] The content of constituent unit (a) is preferably 1 mol% or more, more preferably 3 mol% or more, even more preferably 5 mol% or more, and even more preferably 10 mol% or more, preferably 50 mol% or less, more preferably 40 mol% or less, even more preferably 30 mol% or less, and even more preferably 20 mol% or less, out of the total constituent units of copolymer (A-1). When the content of constituent unit (a) is 1 mol% or more, the low-temperature curability of the photosensitive resin composition or photosensitive colored composition tends to be good, and the solvent resistance of the cured product tends to be better. When the content of constituent unit (a) is 50 mol% or less, the content of constituent unit (b) and constituent unit (c) can be sufficiently secured, and the developability of the photosensitive resin composition or photosensitive colored composition tends to be better.

[0055] (Constituent unit (b) having a nitrogen atom) Constituent unit (b) is not particularly limited as long as it does not have an isocyanate group or a blocked isocyanate group and has a nitrogen atom. Constituent unit (b) may be one type or two or more types. Although not bound by any theory, constituent unit (b) can improve the developability of the photosensitive resin composition or photosensitive colored composition in order to improve adhesion to the substrate.

[0056] The constituent unit (b) may be a constituent unit derived from a nitrogen atom-containing ethylenically unsaturated compound (m-b) (hereinafter sometimes referred to as "compound (m-b)") that does not have an isocyanate group or a blocked isocyanate group. Compound (m-b) is not particularly limited as long as it does not have an isocyanate group or a blocked isocyanate group and has a nitrogen atom and an ethylenically unsaturated group. Specific examples include amide group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, imide group-containing ethylenically unsaturated compounds, and cyano group-containing ethylenically unsaturated compounds.

[0057] Examples of amide group-containing ethylenically unsaturated compounds include N-alkyl(meth)acrylamides such as (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, and N-isopropyl(meth)acrylamide; N,N-dialkyl(meth)acrylamides such as N,N-dimethyl(meth)acrylamide and N,N-diethyl(meth)acrylamide; N,N-alkylenebis(meth)acrylamides such as N,N-methylenebisacrylamide; and N-hydroxyalkyl(meth)acrylamides such as N-(hydroxymethyl)(meth)acrylamide and N-(2-hydroxyethyl)(meth)acrylamide. Examples include lylamide, diacetone (meth)acrylamide, N-vinylacetamide, N-hydroxyalkylaminoalkyl (meth)acrylamide, N-(2-aminoethyl)acrylamide hydrochloride, N-(3-aminopropyl)methacrylamide hydrochloride, N-(t-butoxycarbonyl-aminopropyl)methacrylamide, N,N-dialkylaminoalkyl (meth)acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, (meth)acryloylmorpholine, p-acetamidostyrene, (meth)acrylamide anilide, and 2-acrylamide-2-methylpropanesulfonic acid. Amino group-containing ethylenically unsaturated compounds are compounds that do not have an amide group but have an amino group. Examples of amino group-containing ethylenically unsaturated compounds include aminoalkyl (meth)acrylate, N-alkylaminoalkyl (meth)acrylate, and N,N-dialkylaminoalkyl (meth)acrylate such as 3-(N,N-dimethylamino)propyl (meth)acrylate. Examples of imide group-containing ethylenically unsaturated compounds include maleimide compounds such as maleimide, N-alkylmaleimide, and N-arylmaleimides such as phenylmaleimide, as well as N-alkylitaconimide and N-arylitaconimide. Examples of cyano group-containing ethylenically unsaturated compounds include (meth)acrylonitrile, p-cyanostyrene, and α-cyanocinnamic acid. Other examples of compound (m-b) include vinylpyridine and p-nitrostyrene.Among these, compound (m-b) is preferably at least one selected from the group consisting of amide group-containing ethylenically unsaturated compounds and imide group-containing ethylenically unsaturated compounds, from the viewpoint of developability and adhesion, more preferably at least one selected from the group consisting of N,N-dialkyl(meth)acrylamide, (meth)acryloylmorpholine, N-hydroxyalkyl(meth)acrylamide, cyclic amides such as N-vinylpyrrolidone, and maleimide compounds, and even more preferably at least one selected from the group consisting of N,N-dialkyl(meth)acrylamide, N-hydroxyalkyl(meth)acrylamide, cyclic amides such as N-vinylpyrrolidone, and maleimide compounds. In particular, from the viewpoint of simultaneously improving adhesion and solvent resistance, compound (m-b) is preferably a compound having a functional group reactive with an isocyanate group, more preferably an ethylenically unsaturated compound containing an amide group and a hydroxyl group, and even more preferably an N-hydroxyalkyl(meth)acrylamide.

[0058] The content of constituent unit (b) is preferably 1 mol% or more, more preferably 3 mol% or more, even more preferably 5 mol% or more, and even more preferably 10 mol% or more, preferably 50 mol% or less, more preferably 40 mol% or less, and even more preferably 30 mol% or less, of the total constituent units of copolymer (A-1). When the content of constituent unit (b) is 1 mol% or more, the developability and the solvent resistance and fine wire adhesion of the resin cured film tend to be better. When the content of constituent unit (b) is 50 mol% or less, the content of constituent unit (a) can be sufficiently secured, and the amount of crosslinking by thermal curing is sufficiently secured, so the solvent resistance tends to be better. When the content of constituent unit (b) is 50 mol% or less, the storage stability of the photosensitive resin composition or photosensitive colored composition tends to be good.

[0059] (Constituent unit (c) having an acidic group) The constituent unit (c) having an acidic group is not particularly limited as long as it does not have a nitrogen atom and has an acidic group. Examples of acidic groups include carboxyl groups, sulfo groups, and phospho groups (-P(=O)(OH)). ２Examples include the following. Among these acid groups, the carboxyl group is preferred due to its availability. The constituent unit (c) may be one type or two or more types. The copolymer (A-1) having constituent unit (c) provides the photosensitive resin composition or photosensitive colored composition with good developability.

[0060] The constituent unit (c) is a constituent unit derived from an acid group-containing monomer (m-c) (hereinafter also simply referred to as "monomer (m-c)"). In one embodiment, the acid group-containing monomer (m-c) does not have a nitrogen atom and has an ethylenically unsaturated group and an acid group. Examples of monomers (m-c) include unsaturated carboxylic acids or their anhydrides, unsaturated sulfonic acids, unsaturated phosphonic acids, and the like.

[0061] Examples of monomers (m-c) include unsaturated carboxylic acids or their anhydrides such as (meth)acrylic acid, α-bromo(meth)acrylic acid, β-furyl(meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and 2-(meth)acryloyloxyethyl succinic acid; unsaturated sulfonic acids such as p-styrene sulfonic acid; and unsaturated phosphonic acids such as vinylphosphonic acid. These monomers (m-c) may be used individually or in combination of two or more.

[0062] The content of constituent unit (c) is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, of the total constituent units of copolymer (A-1). From the viewpoint of adhesion of the cured product, it is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less. From the viewpoint of solvent resistance of the cured product, it is preferably 60 mol% or less, more preferably 50 mol% or less, and even more preferably 30 mol% or less. When the content of constituent unit (c) is 1 mol% or more, the developability tends to be better. When the content of constituent unit (c) is 70 mol% or less, the content of constituent unit (b) can be sufficiently secured, and the solvent resistance and fine line adhesion of the cured resin film tend to be better. When the content of constituent unit (c) is 70 mol% or less, the storage stability of the photosensitive resin composition or photosensitive colored composition tends to be good.

[0063] (Constituent unit (d) having a hydroxyl group) Constituent unit (d) is not particularly limited as long as it does not have a nitrogen atom or an acid group and has a hydroxyl group. Constituent unit (d) may be one type or two or more types. Although not bound by any theory, constituent unit (d) can improve the developability of the photosensitive resin composition or photosensitive colored composition in order to improve adhesion to the substrate.

[0064] From the viewpoint of reactivity with constituent unit (a), constituent unit (d) preferably has a group represented by the following formula (6): -(R １０ -O) ｎ５ -H (6) (In formula (6), R １０ (where n5 is a divalent hydrocarbon group, and n5 represents an integer between 2 and 20.)

[0065] In formula (6), R １０ The number of carbon atoms is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3. In formula (6), R １０ The carbon atoms are preferably saturated hydrocarbon groups having 2 to 6 carbon atoms, more preferably saturated hydrocarbon groups having 2 to 4 carbon atoms, and even more preferably saturated hydrocarbon groups having 2 or 3 carbon atoms. A single constituent unit (d) contains multiple -(R １０-O)- may be one type or multiple types. -(R １０ If there are multiple types of -O), then all n5 are of type -(R １０ This refers to the total number of -O)-. n5 is preferably an integer between 2 and 10, more preferably an integer between 2 and 6.

[0066] The constituent unit (d) is a constituent unit derived from a monomer (m-d) (hereinafter also simply referred to as "monomer (m-d)") that does not have a nitrogen atom or an acid group, but has a hydroxyl group. In one embodiment, monomer (m-d) does not have a nitrogen atom or an acid group, but has an ethylenically unsaturated group and a hydroxyl group. Examples of ethylenically unsaturated groups include vinyl groups and (meth)acryloyloxy groups.

[0067] Examples of monomers (m-d) include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; 2-hydroxy-3-phenoxypropyl (meth)acrylate; and polyalkylene glycol mono(meth)acrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polybutylene glycol mono(meth)acrylate, polyethylene glycol polybutylene glycol mono(meth)acrylate, and propylene glycol polybutylene glycol mono(meth)acrylate. These monomers (m-d) may be used individually or in combination of two or more.

[0068] As for the monomer (m-d), among the above monomers, at least one selected from 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate is preferred, and at least one selected from polyethylene glycol mono(meth)acrylate and polypropylene glycol mono(meth)acrylate is more preferred, from the viewpoint of solvent resistance and fine wire adhesion of the resin cured film.

[0069] The content of constituent unit (d) is preferably 1 mol% or more, more preferably 3 mol% or more, even more preferably 5 mol% or more, preferably 60 mol% or less, more preferably 50 mol% or less, even more preferably 30 mol% or less, and even more preferably 20 mol% or less, out of the total constituent units of copolymer (A-1). When the content of constituent unit (d) is 1 mol% or more, the developability and the solvent resistance and fine wire adhesion of the resin cured film tend to be better. When the content of constituent unit (d) is 60 mol% or less, the content of constituent unit (a) can be sufficiently secured, and the amount of crosslinking by thermal curing is sufficiently secured, so the solvent resistance tends to be better. When the content of constituent unit (d) is 60 mol% or less, the storage stability of the photosensitive resin composition or photosensitive colored composition tends to be good.

[0070] (Other constituent units (e)) Constituent unit (e) is not particularly limited as long as it is a constituent unit that does not fall under constituent units (a) to (d). Constituent unit (e) may be only one type or two or more types.

[0071] The constituent unit (e) is a constituent unit derived from other monomers (m-e) (hereinafter also simply referred to as "monomer (m-e)") that do not have a nitrogen atom, an acid group, or a hydroxyl group and are copolymerizable with monomers (m-a) to (m-d). Specific examples of monomers (m-e) include aromatic vinyl compounds, cyclic olefins having a norbornene structure, conjugated dienes, (meth)acrylic acid esters, vinyl compounds, unsaturated dicarboxylic acid diesters, epoxy group-containing ethylenically unsaturated compounds, and acrolein. Among these, aromatic vinyl compounds, cyclic olefins having a norbornene structure, and (meth)acrylic acid esters having a ring structure are preferred from the viewpoint of heat resistance. From the viewpoint of adhesion to fine wires, aromatic vinyl compounds and (meth)acrylic acid esters having a ring structure, such as alicyclic hydrocarbon group-containing (meth)acrylates and aromatic group-containing (meth)acrylates, are preferred.

[0072] Examples of aromatic vinyl compounds include styrene, α-methylstyrene, o-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, and methoxystyrene.

[0073] Examples of cyclic olefins having a norbornene structure include norbornene(bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, and tetracyclo[4.4.0.1]hept-2-ene. ２，５ 1. ７，１０ ] 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-ene, tricyclo[6.2.1.0 １，８ ]Undeka-9-ene, tetracyclo[4.4.0.1 ２，５ 1. ７，１０ . 0 １，６ ] Dodeca-3-ene, 8-ethylidenetetracyclo[4.4.0.1 ２，５ 1. ７，１２ ] Dodeca-3-ene, pentacyclo[6.5.1.1 ３，６ . 0 ２，７. 0 ９，１３ Examples include pentadeca-4-ene.

[0074] Examples of conjugated dienes include butadiene, isoprene, and chloroprene.

[0075] Examples of (meth)acrylic acid esters include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and dodecyl (meth)acrylate; cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, rosin (meth)acrylate, norbornyl (meth)acrylate. Alicyclic hydrocarbon group-containing (meth)acrylates such as 5-ethylnorbornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate; benzyl (meth)acrylate, triphenylmethyl (meth)acrylate, phenyl (meth)acrylate, cumyl (meth)acrylate, 4-phenoxyphenyl (meth)acrylate, phenoxyphenyl (meth)acrylate, phenyl Examples of (meth)acrylic acid esters having a polyalkylene oxide structure include aromatic group-containing (meth)acrylates such as oxyethyl (meth)acrylate, biphenyloxyethyl (meth)acrylate, naphthalene (meth)acrylate, anthracene (meth)acrylate, and ethoxyphenyl (meth)acrylate; tetrahydrofurfuryl (meth)acrylate; fluorinated alkyl (meth)acrylates such as 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, and perfluoro-n-propyl (meth)acrylate; and alkoxy polyalkylene glycol (meth)acrylates such as methoxypolyethylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, and methoxypolypropylene glycol (meth)acrylate; and aryloxy polyalkylene glycol (meth)acrylates such as phenoxypolyethylene glycol (meth)acrylate and nonylphenoxypolyethylene glycol mono(meth)acrylate.In (meth)acrylic acid esters having a polyalkylene oxide structure, the number of moles of alkylene oxide added is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0076] Examples of vinyl compounds include vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, and vinyl acetate.

[0077] Examples of unsaturated dicarboxylic acid diesters include diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate.

[0078] Examples of epoxy group-containing ethylenically unsaturated compounds include epoxy group-containing (meth)acrylic acid ester derivatives such as oxyranyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxyranyl ethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3-glycidyloxypropyl (meth)acrylate, glycidyloxyphenyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and 3,4-epoxycyclohexyl ( Examples include epoxy group-containing (meth)acrylates such as meth)acrylate, 3,4-epoxycyclohexylmethyl(meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl(meth)acrylate, 2-(3,4-epoxycyclohexylmethyloxy)ethyl(meth)acrylate, 3-(3,4-epoxycyclohexylmethyloxy)propyl(meth)acrylate, and other epoxy group-containing alicyclic carbocyclic compounds containing epoxy groups such as 3,4-epoxycyclohexane rings; vinyl ether compounds containing epoxy groups; and allyl ether compounds containing epoxy groups.

[0079] The content of constituent unit (e) is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, preferably 90 mol% or less, more preferably 80 mol% or less, and even more preferably 60 mol% or less, of the total constituent units of copolymer (A-1). When the content of constituent unit (e) is 1 mol% or more, the desired function tends to be imparted. When the content of constituent unit (e) is 90 mol% or less, the content of constituent units (a) to (d) can be sufficiently secured, and the amount of crosslinking by thermosetting is sufficiently secured, so solvent resistance tends to be better. In addition, the developability of the photosensitive resin composition or photosensitive colored composition tends to be better.

[0080] [Copolymer (A-2)] Copolymer (A-2) is a copolymer that does not fall under copolymer (A-1), and its unsaturated group equivalent is 30 to 3000 g / mol. Copolymer (A-2) is not particularly limited, but resins such as (meth)acrylic resin, (meth)acryloyl group-containing epoxy resin, and vinyl ester resin, which are commonly used in negative-type resists, are preferred, and resins containing ethylenically unsaturated groups such as vinyl groups and (meth)acryloyl groups, and substituents that contribute to alkali solubility such as carboxyl groups, phosphoric acid groups, and sulfo groups are preferred. By using such resins, it is possible to provide a photosensitive resin composition and a photosensitive colored composition that have better fine-line adhesion and developability.

[0081] Among these resins, (meth)acrylic resins having (meth)acryloyl groups and carboxyl groups are particularly preferred from the viewpoint of easily providing resins with a wide range of properties. This resin can be synthesized, for example, by polymerizing a (meth)acryloyl group-containing monomer and, if necessary, other polymerizable monomers using a known radical polymerization method to obtain a base polymer, and then introducing (meth)acryloyl groups and carboxyl groups into this base polymer.

[0082] As a method for introducing (meth)acryloyl groups, for example, a method is to polymerize a base polymer using a polymerizable monomer having reactive groups such as a hydroxyl group, amino group, carboxyl group, epoxy group, or isocyanate group, add a polymerization inhibitor and a catalyst, then add a (meth)acryloyl group-containing compound having a functional group that can react with these reactive groups, and react under conditions of 50 to 150°C. As a method for adding carboxyl groups, for example, a method of reacting a base polymer having a hydroxyl group with a polybasic acid or its anhydride, a method of reacting a base polymer having a carboxyl group with a compound containing an epoxy group and a (meth)acryloyl group, and then reacting with a polybasic acid or its anhydride, and a method of reacting a base polymer having an epoxy group with a compound containing a carboxyl group and a (meth)acryloyl group, and then reacting with a polybasic acid or its anhydride. Alternatively, carboxyl groups may be left in the base polymer. Examples of polybasic acids or their anhydrides include succinic anhydride.

[0083] The weight-average molecular weight of copolymer (A-2) is preferably 3,000 or more, more preferably 4,000 or more, even more preferably 5,000 or more, and even more preferably 6,000 or more. The weight-average molecular weight of copolymer (A-2) is preferably 50,000 or less, more preferably 30,000 or less, even more preferably 20,000 or less, and even more preferably 15,000 or less. When the weight-average molecular weight of copolymer (A-2) is 3,000 or more, the curability of the photosensitive resin composition or photosensitive colored composition tends to be good, and the solvent resistance of the cured product tends to be better. When the weight-average molecular weight of copolymer (A-2) is 50,000 or less, the storage stability of the photosensitive resin composition or photosensitive colored composition tends to be good.

[0084] The acid value of copolymer (A-2) is preferably 5 KOH mg / g or more, more preferably 10 KOH mg / g or more, even more preferably 25 KOH mg / g or more, and even more preferably 30 KOH mg / g or more. The acid value of copolymer (A-2) is preferably 300 KOH mg / g or less, more preferably 200 KOH mg / g or less, even more preferably 150 KOH mg / g or less, and even more preferably 100 KOH mg / g or less. When the acid value of copolymer (A-2) is 5 KOH mg / g or more, the solvent resistance of the cured product of the photosensitive resin composition or photosensitive colored composition tends to be better. When the acid value of copolymer (A-2) is 300 KOH mg / g or less, the storage stability of the photosensitive resin composition or photosensitive colored composition tends to be good.

[0085] The unsaturated group equivalent of copolymer (A-2) is 30 g / mol or more, preferably 100 g / mol or more, more preferably 200 g / mol or more, and even more preferably 300 g / mol or more. The unsaturated group equivalent of copolymer (A-2) is 3000 g / mol or less, preferably 2000 g / mol or less, more preferably 1500 g / mol or less, and even more preferably 1000 g / mol or less. When the unsaturated group equivalent of copolymer (A-2) is 30 g / mol or more, the storage stability of the photosensitive resin composition or photosensitive colored composition tends to be good. When the unsaturated group equivalent of copolymer (A-2) is 3000 g / mol or less, the compatibility with copolymer (A-1) and reactive diluent (B) is good, and sufficient photocurability tends to be obtained.

[0086] In a preferred embodiment, copolymer (A-2) is a copolymer in which an ethylenically unsaturated compound having a functional group reactive with epoxy groups is added to at least a portion of the epoxy groups of a copolymer precursor containing epoxy groups, and a polybasic acid or its anhydride is added to the hydroxyl group formed by ring-opening of the epoxy group. The copolymer precursor may contain other structural units other than those containing epoxy groups. A preferred example of other structural units is a structural unit (e) that does not have epoxy groups.

[0087] The constituent units containing epoxy groups are derived from epoxy group-containing monomers. Specific examples of epoxy group-containing monomers include compounds similar to the epoxy group-containing ethylenically unsaturated compounds mentioned above.

[0088] Examples of ethylenically unsaturated compounds having a functional group that reacts with an epoxy group include (meth)acrylic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl succinic acid, α-bromo(meth)acrylic acid, β-furyl(meth)acrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, itaconic acid, and citraconic acid, among other unsaturated carboxylic acids. (Meth)acrylic acid is preferred.

[0089] Examples of polybasic acids include adipic acid, itaconic acid, succinic acid, oxalic acid, malonic acid, phthalic acid, fumaric acid, maleic acid, glutaric acid, tartaric acid, glutamic acid, and sebacic acid. Examples of polybasic anhydrides include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, maleic anhydride, itaconic anhydride, ethyl maleic anhydride, methylitaconic anhydride, chlormaleic anhydride, citraconic anhydride, 2-norvonene-5,6-dicarboxylic acid anhydride, 4-[2-(methacryloyloxy)ethoxycarbonyl]phthalic anhydride, succinic anhydride, and cyclohexanetricarboxylic acid anhydride.

[0090] In another preferred embodiment, copolymer (A-2) is a copolymer obtained by adding an ethylenically unsaturated compound having a functional group reactive with the acid group to some of the acid groups of a copolymer precursor containing an acid group-containing structural unit. Specific examples and preferred examples of the acid group-containing structural unit are the same as those for structural unit (c) above. The copolymer precursor may contain structural units other than the acid group-containing structural unit. A preferred example of the other structural unit is structural unit (e) above.

[0091] Examples of ethylenically unsaturated compounds having a functional group that reacts with an acid group include epoxy group-containing ethylenically unsaturated compounds.

[0092] [Reactive Diluent (B)] The reactive diluent (B) may be any low molecular weight compound having at least one ethylenically unsaturated group, and is not particularly limited. In this disclosure, a low molecular weight compound is a compound with a molecular weight of less than 1,000. Examples of ethylenically unsaturated groups include vinyl groups, allyl groups, (meth)acryloyloxy groups, etc. From the viewpoint of improving reactivity, a reactive diluent having multiple ethylenically unsaturated groups (also called a polyfunctional reactive diluent) is preferred. Specific examples of the reactive diluent (B) include aromatic vinyl compounds; aromatic allyl compounds such as diallyl phthalate and diallylbenzenephosphonate; vinyl carboxylates such as vinyl acetate and vinyl adipate; monofunctional (meth)acrylates; polyfunctional (meth)acrylates; triallyl cyanurate, etc.

[0093] Specific examples of aromatic vinyl compounds include styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, and divinylbenzene.

[0094] Specific examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, β-hydroxyethyl (meth)acrylate, and hydroxypropyl (meth)acrylate.

[0095] Specific examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tri(meth)acrylic acid esters of tris(hydroxyethyl) isocyanurate.

[0096] Among these, as the reactive diluent (B), polyfunctional (meth)acrylates are preferred from the viewpoint of improving reactivity, and at least one selected from dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate is more preferred.

[0097] The reactive diluent (B) may be used alone or in combination of two or more types.

[0098] [Photopolymerization Initiator (C)] The photopolymerization initiator (C) is not particularly limited as long as it is a compound that generates radicals upon light irradiation. Examples of photopolymerization initiators (C) include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; alkylphenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4-(1-t-butyldioxy-1-methylethyl)acetophenone, 1-hydroxycyclohexylphenyl ketone, and 2-hydroxy-2-methyl-1-phenylpropan-1-one; anthraquinone compounds such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; ketal compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal; and benzophenone Examples include benzophenone compounds such as 4-(1-t-butyldioxy-1-methylethyl)benzophenone and 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone; oxime esters such as 1,2-octanedione, 1-[4-(phenylthio)phenyl]-,2-(o-benzoyl oxime), ethanone, and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,-1-(O-acetyl oxime); 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1; acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; and xanthones. The photopolymerization initiator (C) may be used alone or in combination of two or more types.

[0099] [Solvent (D)] Solvent (D) is not particularly limited, but when copolymer (A-1) is a (meth)acrylic copolymer, glycol ether is preferred from the viewpoint of its solubility. Specific examples include (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, 3-methoxy-1-butanol, 1,3-propanediol monoalkyl ether, 1,3-butanediol monoalkyl ether, 1,4-butanediol monoalkyl ether, etc. Examples include: ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, propylene glycol monophenyl ether, and other propylene glycol monoaryl ethers; ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether; and (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Among these, at least one selected from propylene glycol monomethyl ether, 3-methoxy-1-butanol, and propylene glycol monomethyl ether acetate is preferred from the viewpoint of availability and reactivity. Solvent (D) may be used alone or in combination of two or more.

[0100] Other specific examples of solvent (D) include monoalcohols other than (poly)alkylene glycol monoalkyl ethers. Specific examples of monoalcohols include primary alcohols such as propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, and dodecyl alcohol; secondary alcohols such as benzyl alcohol; and tertiary alcohols such as tert-butyl alcohol and diacetone alcohol.

[0101] Solvent (D) Other specific examples include other ethers such as tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyethyl acetate, ethyl hydroxyethyl acetate, methyl 2-hydroxy-3-methylbutyrate, and methyl-3-methoxybutyl ethyl acetate. Examples include esters such as acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-butyl acetate, n-propyl acetate, i-propyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; and carboxylic acid amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0102] <Photosensitive Coloring Composition> The photosensitive coloring composition comprises the above-mentioned photosensitive resin composition and a coloring agent (E).

[0103] [Colorant (E)] As the colorant (E), at least one selected from the group consisting of known dyes and pigments can be used. When used in a color filter, it is preferable to use a dye as the colorant (E) from the viewpoint of color reproduction. When a dye is used as the colorant (E), a coloring pattern with higher brightness can be obtained compared to when a pigment is used, and a photosensitive colored composition exhibiting good alkaline developability can be obtained.

[0104] As dyes, it is preferable to use acidic dyes having acidic groups such as carboxyl groups, salts of acidic dyes with nitrogen compounds, or sulfonamide adducts of acidic dyes, from the viewpoint of solubility in solvent (D) and alkaline developer, interaction with other components in the photosensitive coloring composition, and heat resistance. 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 (VALIFAST BLUE 2620); acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114 ,129,133,134,138,143,145,150,151,158,176,183,198,211,215,216,217,249,252,257,260,266,274;acid violet Examples include 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; solvent yellow 82 and their derivatives. Among these, azo, xanthene, anthraquinone, or phthalocyanine acid dyes are preferred. Depending on the desired pixel color, the dyes may be used individually or in combination of two or more.

[0105] Examples of pigments include yellow pigments such as C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; orange pigments such as C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; C.I. Examples include red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, and 265; blue pigments such as C.I. Pigment Blue 15, 15:3, 15:4, 15:6, and 60; violet pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, and 38; green pigments such as C.I. Pigment Green 7, 36, and 58; brown pigments such as C.I. Pigment Brown 23 and 25; and black pigments such as C.I. Pigment Black 1, 7, carbon black, titanium black, and iron oxide. Pigments may be used individually or in combination of two or more, depending on the desired color of the pixel.

[0106] When a pigment is used as the coloring agent (E), a known dispersant may be added to the photosensitive coloring composition from the viewpoint of improving the dispersibility of the pigment. As the dispersant, it is preferable to use a polymer dispersant that has excellent dispersion stability over time. Examples of polymer dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic-modified ester-based dispersants. Such polymer dispersants may be those that are commercially available under trade names such as EFKA (EFKA Chemicals BV), DISPERBYK (BIC Chemie), Disparon (Kusumoto Chemicals Co., Ltd.), and SOLSPERSE (Lubrizol). The content of the dispersant should be appropriately set according to the type and amount of pigment used as the coloring agent (E).

[0107] The content of the colorant (E) in the photosensitive colored composition is preferably 0.1 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, based on 100 parts by mass of the total of copolymer (A-1), copolymer (A-2), and reactive diluent (B). The content of the colorant (E) in the photosensitive colored composition is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 60 parts by mass or less, based on 100 parts by mass of the total of copolymer (A-1), copolymer (A-2), and reactive diluent (B). When the content of the colorant (E) is 0.1 parts by mass or more, the effect of including the colorant (E) becomes significant, and a photosensitive colored composition suitable as a material for the coloring pattern of a color filter tends to be obtained. When the content of the colorant (E) is 80 parts by mass or less, the colorant (E) does not interfere with the curability of the photosensitive colored composition, and a photosensitive colored composition with good low-temperature curability tends to be obtained.

[0108] The content of solvent (D) in the photosensitive coloring composition is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, even more preferably 100 parts by mass or more, preferably 1000 parts by mass or less, more preferably 700 parts by mass or less, and even more preferably 500 parts by mass or less, based on 100 parts by mass of the total of the components excluding solvent (D).

[0109] [Other Additives] The photosensitive resin composition or photosensitive colored composition may optionally contain one or more known additives such as leveling agents, thermal polymerization inhibitors, and sensitizers. The amount of additives is not particularly limited, as long as it does not hinder the effects of the present invention.

[0110] <Content of each component of the photosensitive resin composition> The content of copolymer (A-1) is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, relative to the total of copolymer (A-1), copolymer (A-2), and reactive diluent (B).

[0111] The content of copolymer (A-1) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 25 parts by mass or more, preferably 70 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less, based on 100 parts by mass of the total components excluding solvent (D).

[0112] When the photosensitive resin composition contains copolymer (A-2), the content of copolymer (A-2) is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, based on the total of copolymer (A-1), copolymer (A-2), and reactive diluent (B).

[0113] When the photosensitive resin composition contains copolymer (A-2), the mass ratio of copolymer (A-1) to copolymer (A-2) is preferably 10:90 to 90:10, more preferably 20:80 to 80:20, and even more preferably 30:70 to 70:30.

[0114] When the photosensitive resin composition contains a reactive diluent (B), the content of the reactive diluent (B) is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, based on the total of copolymer (A-1), copolymer (A-2), and reactive diluent (B).

[0115] The content of the photopolymerization initiator (C) is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 1 part by mass or more, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less, based on 100 parts by mass of the total of copolymer (A-1), copolymer (A-2), and reactive diluent (B).

[0116] The content of solvent (D) is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, even more preferably 100 parts by mass or more, preferably 1000 parts by mass or less, more preferably 700 parts by mass or less, and even more preferably 500 parts by mass or less, based on 100 parts by mass of the total components excluding solvent (D).

[0117] <Method for producing copolymer (A-1)> The copolymerization reaction for synthesizing copolymer (A-1) can be carried out in or out of the presence of a polymerization solvent according to radical polymerization methods known in the art. For example, the monomer can be dissolved in a solvent, a polymerization initiator can be added to the solution, and the polymerization reaction can be carried out at 40 to 100°C for 1 to 20 hours.

[0118] Polymerization initiators that can be used in this copolymerization reaction include, for example, azo-based thermal polymerization initiators such as azobisisobutyronitrile, azobisisovaleronitrile, and 2,2'-azobis(2,4-dimethylvaleronitrile); and peroxide-based thermal polymerization initiators such as benzoyl peroxide and t-butylperoxy-2-ethylhexanoate. Polymerization initiators may be used individually or in combination of two or more.

[0119] The amount of polymerization initiator used is generally 0.5 to 30 parts by mass, preferably 1 to 25 parts by mass, and more preferably 5 to 20 parts by mass, when the total amount of monomer charged is 100 parts by mass.

[0120] The solvent used in the copolymerization reaction can be the same as the solvent (D) described above. Other examples include glycerin monoalkyl ether, glycerin dialkyl ether, methanol, ethanol, C5-6 cycloalkanediol, C5-6 cycloalkanedimethanol, and ethyl lactate. Note that "C5-6 cycloalkane" means that the cycloalkyl group has 5-6 carbon atoms. The solvent may be used alone or in combination of two or more.

[0121] <Method for producing photosensitive resin composition and photosensitive colored composition> The photosensitive resin composition and the photosensitive colored composition can be produced by mixing each component using a known mixing apparatus.

[0122] When producing a photosensitive resin composition or a photosensitive colored composition, the reaction solution used to produce the copolymer (A-1) can be used as a raw material. In this case, the solvent (D) contained in the reaction solution can be used as part or all of the solvent (D) contained in the photosensitive resin composition or the photosensitive colored composition. When producing a photosensitive resin composition or a photosensitive colored composition, copolymer (A-1) isolated from the reaction solution containing copolymer (A-1) by a known method may also be used as a raw material. In this case, regardless of the type and amount of solvent used when producing copolymer (A-1), the type and content of solvent (D) can be appropriately selected according to the type of copolymer (A-1), the intended use of the photosensitive resin composition or the photosensitive colored composition, etc.

[0123] The photosensitive resin composition and the photosensitive colored composition contain a copolymer (A-1) that includes a hydroxyl group and a structural unit (a) having a blocked isocyanate group, and therefore have good low-temperature curability. As a result, when forming a cured product using the photosensitive resin composition or the photosensitive colored composition, curing can be performed at a lower temperature compared to when using conventional resin compositions. Therefore, when a coating film formed on a substrate is exposed and then subjected to a baking treatment, for example, the photosensitive resin composition or the photosensitive colored composition allows the crosslinking reaction to proceed sufficiently even at a low baking treatment temperature, resulting in the formation of a cured product with excellent solvent resistance and hardness.

[0124] Therefore, when forming a cured product using a photosensitive resin composition or a photosensitive coloring composition, less energy is required for heating to cure. In addition, by using a photosensitive resin composition or a photosensitive coloring composition, a cured product can be formed on a substrate with low heat resistance, such as a resin substrate, without damaging the substrate. Furthermore, even when a coloring agent (E) with low heat resistance is used, a cured product can be formed that exhibits the inherent properties of the coloring agent (E).

[0125] The photosensitive colored composition yields a cured product with excellent solvent resistance and hardness even at low baking temperatures, as the colorant (E) is less likely to leach from the cured product. Therefore, it is possible to increase the content of the colorant (E) in the photosensitive colored composition. A photosensitive colored composition with a high content of colorant (E) can be used, for example, as a material for the coloring pattern of a color filter to form a color filter with excellent color reproduction.

[0126] Since copolymer (A-1) contains a constituent unit (c) having an acid group, the photosensitive resin composition or photosensitive colored composition has good alkali developability. Therefore, by developing with an alkaline aqueous solution, a cured product having a predetermined pattern shape can be formed.

[0127] Based on these findings, the photosensitive resin composition and the photosensitive colored composition are extremely useful as materials for forming components of image display elements, such as pixels in color filters, black matrices, color filter protective films, photospacers, liquid crystal alignment protrusions, microlenses, and insulating films for touch panels.

[0128] <Resin-cured film> The resin-cured film of one embodiment is a cured product of a photosensitive resin composition or a photosensitive colored composition.

[0129] A cured resin film can be manufactured, for example, by applying a photosensitive resin composition or a photosensitive colored composition onto a substrate, volatilizing and removing the solvent (D) to form a coating film, exposing the coating film to light-curing, and then performing a baking treatment. The cured resin film can be manufactured using a baking treatment method at a low temperature and has excellent solvent resistance.

[0130] When forming a resin-cured film having a predetermined pattern shape, for example, the following method can be used. That is, a photosensitive resin composition or a photosensitive colored composition is applied to a substrate, and the solvent (D) 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 to photocur the exposed portion. Then, the unexposed portion of the coating film is developed with an alkaline aqueous solution. After that, the developed coating film is subjected to a baking treatment to form a resin-cured film having a predetermined pattern shape.

[0131] When manufacturing a cured resin film, known methods can be used for applying the photosensitive resin composition or photosensitive colored composition, for exposing the applied film to light, and for developing the film.

[0132] The baking conditions performed when manufacturing a cured resin film can be appropriately determined according to the composition of the photosensitive resin composition or photosensitive colored composition, the film thickness of the coating, the material of the substrate, etc. The baking treatment can be carried out at a temperature of, for example, 70°C to 250°C. When the baking temperature is 70°C or higher, the blocked isocyanate groups contained in the copolymer (A-1) tend to dissociate sufficiently. As a result, isocyanate groups are generated and crosslink with reactive functional groups. If the constituent unit (a) has an alkyloxycarbonyl group, crosslinking by transesterification occurs. As a result, a good degree of curing is obtained, and a cured product with excellent solvent resistance and hardness is obtained. When the constituent unit (a) has an alkyloxycarbonyl group, both deblocking and transesterification reactions can occur, but by adjusting the baking temperature, one of the reactions can be preferentially carried out. The baking temperature is preferably 75°C or higher, and more preferably 80°C or higher. A baking temperature of 250°C or lower is preferable because it is a condition that materials with low heat resistance can withstand, and it can suppress discoloration of the photosensitive resin composition or photosensitive colored composition. The photosensitive resin composition and photosensitive colored composition have good low-temperature curing properties. For this reason, the baking temperature can be set to 160°C or lower, depending on the heat resistance of the substrate on which the resin cured film is formed. For example, when a resin substrate is used as the base material, it may be 150°C or lower, 120°C or lower, or 100°C or lower.

[0133] The baking process performed when manufacturing the resin-cured film can be carried out for, for example, 10 minutes to 4 hours, preferably 20 minutes to 2 hours, and can be appropriately determined depending on the composition of the photosensitive resin composition or photosensitive coloring composition, the baking temperature, the film thickness of the coated film, etc.

[0134] The resin-cured film can be preferably used as a component of, for example, a transparent film, a protective film, an insulating film, an overcoat, a photospacer, a black matrix, a black column spacer, and a color filter.

[0135] <Color Filter> A color filter of one embodiment is provided with a colored pattern which is a cured product of a photosensitive colored composition. Preferably, the color filter has a colored pattern which is a cured product of a photosensitive colored composition, with the copolymer (A-1) being 10% by mass or more and less than 100% by mass of copolymer (A-1), the reactive diluent (B) being more than 0% by mass and 90% by mass or less, the copolymer (A-2) being more than 0% by mass and 90% by mass or less, and the photopolymerization initiator (C) being 0.1 to 20 parts by mass, the colorant (E) being 0.1 to 80 parts by mass, and the solvent (D) being 30 to 1,000 parts by mass of the solvent (D) per 100 parts by mass of the total of copolymer (A-1), copolymer (A-2), and reactive diluent (B).

[0136] A 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.

[0137] In a color filter, at least a portion of the pixels and black matrix are colored patterns which are cured products of the above-mentioned photosensitive colored composition. In a color filter, components other than the materials of the pixels and black matrix can be those of known origin.

[0138] The substrate used in the color filter is not particularly limited, and glass substrates, silicon substrates, polycarbonate substrates, polyester substrates, polyamide substrates, polyamide-imide substrates, polyimide substrates, aluminum substrates, printed circuit boards, array substrates, etc., can be used as appropriate depending on the application.

[0139] <Method for Manufacturing Color Filters> Next, an example method for manufacturing color filters will be described. First, a colored pattern is formed on the substrate. Specifically, a colored pattern that will become the black matrix formed at the boundary of each pixel, and a colored pattern that will become each RGB pixel are sequentially formed on the substrate by the method shown below.

[0140] The colored pattern can be formed by photolithography. Specifically, a photosensitive colored composition is applied to 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 areas are photocured. Next, the unexposed areas of the coating film are 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.

[0141] The method for applying the photosensitive colored composition is not particularly limited, but known methods such as screen printing, roll coating, curtain coating, spray coating, and spin coating can be used.

[0142] Furthermore, after applying the photosensitive coloring composition to the substrate, the substrate may be heated using a heating means such as a circulating oven, infrared heater, or hot plate, if necessary, to volatilize and remove the solvent (D) contained in the coating film. The conditions for heating the substrate to remove the solvent (D) are not particularly limited and can be set appropriately according to the substrate material, the composition of the photosensitive coloring composition, the thickness of the coating film, etc. For example, the substrate can be heated at a temperature of 50°C to 120°C for 30 seconds to 30 minutes.

[0143] Next, the coated film formed in this manner is irradiated with an active energy ray, such as ultraviolet light or excimer laser light, through a negative-type photomask to partially expose it and photo-cure the exposed portion. The amount of active energy irradiated onto the coated film can be appropriately selected according to the composition of the photosensitive coloring composition, for example, 30 to 2000 mJ / cm². ２ This can be done. The light source used for exposure is not particularly limited, but low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, metal halide lamps, etc., can be used.

[0144] The alkaline aqueous solution used for developing the coating film is not particularly limited, but can be used: aqueous solutions of inorganic alkali compounds such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, and potassium hydroxide; aqueous solutions of amine compounds such as ethylamine, diethylamine, and dimethylethanolamine; aqueous solutions of quaternary ammonium salts such as tetramethylammonium sulfate, hydrochloride, or p-toluenesulfonate; aqueous solutions of aniline compounds and their salts 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, hydrochloride, or p-toluenesulfonate; and aqueous solutions of p-phenylenediamine compounds and their salts. Additives such as defoamers and surfactants may be added to the alkaline aqueous solution as needed.

[0145] After developing the coating film using the above-mentioned alkaline aqueous solution, it is preferable to wash the coating film with water and dry it.

[0146] The baking conditions performed when manufacturing color filters can be appropriately determined according to the composition of the photosensitive coloring composition, the film thickness of the coating, the substrate material, etc. The baking temperature can be, for example, 70°C to 210°C. When the baking temperature is 70°C or higher, good curing properties are obtained, and a cured product with excellent solvent resistance and hardness tends to be obtained. The baking temperature is preferably 75°C or higher, and more preferably 80°C or higher. When the baking temperature is 210°C or lower, it is preferable because it is possible to use materials with low heat resistance, such as substrates with low heat resistance, as the material for the color filter.

[0147] When forming a colored pattern on a color filter using a conventional photosensitive resin composition, the hardness of the colored pattern is insufficient if the baking temperature is 200°C or lower. In contrast, the photosensitive colored composition of one embodiment has good low-temperature curing properties, so the baking temperature can be lowered compared to when using a conventional photosensitive resin composition while ensuring the hardness of the colored pattern. Specifically, the baking temperature can be 160°C or lower, depending on the heat resistance of the substrate on which the resin cured film is formed. For example, when a resin substrate is used as the base material to form a colored pattern, the temperature may be 150°C or lower, 120°C or lower, or 100°C or lower.

[0148] The baking process performed when manufacturing color filters can be carried out for, for example, 10 minutes to 4 hours, preferably 20 minutes to 2 hours, and can be appropriately determined depending on the composition of the photosensitive coloring composition, the temperature of the baking process, the thickness of the coated film, etc.

[0149] The photosensitive colored composition has good photocurability and low-temperature curability. Therefore, when forming a colored pattern using the photosensitive colored composition of one embodiment, if the baking temperature is the same as when forming a colored pattern using a conventional photosensitive resin composition, the baking time can be shortened, and a color filter can be formed efficiently.

[0150] Using the method for manufacturing the colored patterns described above, a colored pattern is formed to represent each RGB pixel, and a colored pattern is formed to represent the black matrix at the boundary of each pixel. After that, a protective film is formed on the colored patterns (each RGB pixel and the black matrix).

[0151] The method for manufacturing the protective film is not particularly limited, and it may be formed using the photosensitive colored composition of one embodiment, or it may be formed using known materials and known methods.

[0152] A color filter can be obtained through the above process.

[0153] The color filter has a colored pattern which is a cured product of the photosensitive colored composition described above. Therefore, the colored pattern in the color filter can be formed by a baking process at a low temperature. Consequently, the energy required for the baking process can be reduced.

[0154] In addition, it is possible to use a colorant (E) with low heat resistance as the colorant (E) contained in the photosensitive coloring composition used as a material for the color filter. This increases the number of options for usable colorants (E). Therefore, for example, it is possible to form a color filter that contains a colorant (E) with low heat resistance and has a coloring pattern that exhibits the inherent properties of the colorant (E) with low heat resistance.

[0155] Furthermore, the colored patterns in color filters can be formed on substrates with low heat resistance, such as resin substrates, without damaging the substrate itself. This increases the range of usable substrates. Specifically, for example, since color filters can be formed on substrates with low heat resistance, such as resin substrates, flexible displays become possible. In addition, the colored patterns in color filters have excellent solvent resistance and hardness, resulting in minimal color change.

[0156] Here, we have described an example in which a colored pattern is produced using a photosensitive colored composition containing a photopolymerization initiator (C) and a method of photocuring the photosensitive colored composition. However, for example, instead of the photopolymerization initiator (C), a photosensitive colored composition containing a curing accelerator and a known epoxy resin may be used, and a colored pattern, which is a cured product of the photosensitive colored composition containing copolymer (A-1), may be formed by applying it to a substrate by an inkjet method and then heating it.

[0157] <Image Display Element> An image display element in one embodiment includes a color filter. Other components of the image display element can be those known to be used. Specific examples of image display elements include solid-state image sensors such as liquid crystal display elements, organic EL display elements, CCD elements, and CMOS elements.

[0158] The components of an image display element other than the color filter 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 shown 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 another substrate and bonded together with the substrate having the color filter, facing each other. Then, a predetermined amount of liquid crystal is injected between the opposing substrates and sealed.

[0159] The image display element is equipped with a color filter that has excellent solvent resistance and hardness, resulting in minimal color distortion.

[0160] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

[0161] <Method for measuring acid value> The number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of copolymer was measured according to JIS K6901:2008 5.3.2. Measuring instrument: 776 Dosimat (Metrohm) Mixed indicator: Mixed indicator of bromothymol blue and phenol red

[0162] Examples of the synthesis of copolymer (A-1) and copolymer (cA-1) are shown below.

[0163] [Synthesis Example 1] In a flask equipped with a stirring device, dropping funnel, condenser, thermometer, and gas inlet tube, 124.4 g of propylene glycol monomethyl ether was added as solvent (D), and the mixture was stirred while purging with nitrogen, and the temperature was raised to 78°C.

[0164] Next, a raw material monomer solution was prepared by mixing 41.9 g (16 mol%) of AOI-DEM as monomer (m-a), 8.6 g (10 mol%) of dimethylacrylamide as monomer (m-b), 8.2 g (11 mol%) of methacrylic acid as monomer (m-c), 18.1 g (16 mol%) of 2-hydroxyethyl methacrylate as monomer (m-d), 71.9 g (47 mol%) of benzyl methacrylate as monomer (m-e), 18.0 g of V-65 (Fujifilm Wako Pure Chemical Industries, Ltd.) as a polymerization initiator (12.1 parts by mass per 100 parts by mass of the total monomer components), and 80.8 g of propylene glycol monomethyl ether acetate and 41.6 g of propylene glycol monomethyl ether as solvent (D).

[0165] The entire amount of the prepared raw material monomer solution was added dropwise over 1 hour using a dropping funnel to solvent (D) in a flask under atmospheric pressure and nitrogen gas atmosphere. After the addition was complete, the solution in the flask was stirred and polymerized at 78°C for 3 hours to obtain a reaction solution containing copolymer (A-1) and solvent (D). To the reaction solution thus obtained, propylene glycol monomethyl ether acetate was added as solvent (D) so that the non-solvent components accounted for 35% by mass, to obtain a liquid containing copolymer (A-1) of Synthesis Example 1.

[0166] [Synthesis Examples 2-29, Comparative Synthesis Examples 1-3] Liquids containing copolymers (A-1) from Synthesis Examples 2-29 and liquids containing copolymers (cA-1) from Comparative Synthesis Examples 1-3 were obtained in the same manner as in Synthesis Example 1, except that the monomers, solvent (D), and polymerization initiator and their respective amounts were used as listed in Table 1. The amount of polymerization initiator added was adjusted according to the desired weight-average molecular weight.

[0167] Table 1 shows the weight-average molecular weight, molecular weight distribution, total nitrogen equivalent, nitrogen equivalent (b), blocked isocyanate group equivalent, hydroxyl group equivalent, and acid value of copolymers (A-1) from synthesis examples 1 to 29 and copolymers (cA-1) from comparative synthesis examples 1 to 3.

[0168]

[0169] An example of the synthesis of copolymer (A-2) is shown below.

[0170] [Synthesis Example 30] 260.1 g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube as solvent (D), and the mixture was stirred while purging with nitrogen, and the temperature was raised to 118°C.

[0171] Next, a raw material monomer solution was prepared by mixing 228.3 g (80 mol%) of glycidyl methacrylate, 44.2 g (10 mol%) of dicyclopentanyl methacrylate, 35.4 g (10 mol%) of benzyl methacrylate, 16.8 g of TBO (t-butyl peroxy-2-ethylhexanoate, polymerization initiator) (5.5 parts by mass per 100 parts by mass of the total monomer components), and 141.7 g of propylene glycol monomethyl ether acetate as solvent (D).

[0172] The entire volume of the prepared raw material monomer solution was added dropwise over 1 hour using a dropping funnel to solvent (D) in a flask under atmospheric pressure and nitrogen gas atmosphere. After the addition was complete, the solution in the flask was stirred and polymerized at 120°C for 2 hours to obtain a liquid containing the copolymer precursor and solvent (D).

[0173] In a flask at atmospheric pressure under a 6 mol% oxygen gas atmosphere, a liquid containing a copolymer precursor and solvent (D) was added. This liquid was then mixed with 1.3 g of hydroquinone monomethyl ether (MEHQ) as a polymerization inhibitor (0.3 parts by mass per 100 parts by mass of the monomer components of the copolymer precursor and acrylic acid), 1.3 g of triparatylphosphine (Hokko Sangyo Co., Ltd.) as a catalyst (0.3 parts by mass per 100 parts by mass of the monomer components of the copolymer precursor and acrylic acid), and 112.3 g of acrylic acid (80 moles per 100 moles of the monomer components of the copolymer precursor). The mixture was then stirred and held at 120°C for 720 minutes. Next, 64.3 g of succinic anhydride (32 moles per 100 moles of the monomer components of the copolymer precursor) was added. The mixture was then stirred and held at 115°C for 120 minutes to obtain a reaction solution containing copolymer (A-2) and solvent (D).

[0174] To the reaction solution containing the copolymer (A-2) obtained in this way and solvent (D), propylene glycol monomethyl ether acetate (Tokyo Chemical Industries, Ltd.) was added as solvent (D) so that the components other than the solvent amounted to 45% by mass, to obtain a liquid containing the copolymer (A-2) of Synthesis Example 30.

[0175] [Synthesis Example 31] A liquid containing copolymer (A-2) of Synthesis Example 31 was obtained in the same manner as in Synthesis Example 30, except that the raw materials and their proportions listed in Table 2 were used.

[0176] [Synthesis Example 32] In a flask equipped with a stirring device, dropping funnel, condenser, thermometer, and gas inlet tube, 229.1 g of propylene glycol monomethyl ether acetate was added as solvent (D), and the mixture was stirred while purging with nitrogen, and the temperature was raised to 118°C.

[0177] Next, a raw material monomer solution was prepared by mixing 52.6 g (10 mol%) of dicyclopentanyl methacrylate, 176.7 g (42 mol%) of benzyl methacrylate, 98.7 g (48 mol%) of methacrylic acid, 19.7 g of TBO (t-butyl peroxy-2-ethylhexanoate, polymerization initiator) (6.0 parts by mass per 100 parts by mass of the total monomer components), and 105.0 g of propylene glycol monomethyl ether acetate as solvent (D).

[0178] The entire volume of the prepared raw material monomer solution was added dropwise over 1 hour using a dropping funnel to solvent (D) in a flask under atmospheric pressure and nitrogen gas atmosphere. After the addition was complete, the solution in the flask was stirred and polymerized at 120°C for 2 hours to obtain a liquid containing the copolymer precursor and solvent (D).

[0179] To a liquid containing a copolymer precursor and solvent (D) in a flask at atmospheric pressure under a 6 mol% oxygen gas atmosphere, 1.1 g of hydroquinone monomethyl ether (MEHQ) as a polymerization inhibitor (0.3 parts by mass per 100 parts by mass of the total monomer components of the copolymer precursor and glycidyl methacrylate), 1.1 g of triparatylphosphine (Hokko Sangyo Co., Ltd.) as a catalyst (0.3 parts by mass per 100 parts by mass of the total monomer components of the copolymer precursor and glycidyl methacrylate), and 52.3 g of glycidyl methacrylate (15 moles per 100 moles of the total monomer components of the copolymer precursor) were added, and the mixture was held at 120°C for 300 minutes while stirring.

[0180] To the reaction solution containing the copolymer (A-2) obtained in this way and solvent (D), propylene glycol monomethyl ether acetate (Tokyo Chemical Industries, Ltd.) was added as solvent (D) so that the components other than the solvent amounted to 40% by mass, to obtain a liquid containing the copolymer (A-2) of Synthesis Example 32.

[0181] [Synthesis Example 33] A liquid containing copolymer (A-2) of Synthesis Example 33 was obtained in the same manner as in Synthesis Example 32, except that the raw materials and their proportions listed in Table 2 were used.

[0182] Table 2 shows the weight-average molecular weight, acid value, and unsaturated group equivalent of copolymers (A-2) from synthesis examples 30 to 33.

[0183]

[0184] The compounds used in Tables 1 and 2 were as follows: AOI-DEM: Reaction product of Karenz™ AOI (2-isocyanatoethyl acrylate, Resonaq Inc.) and diethyl malonate (malonate-2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester) MOI-DEM: Reaction product of Karenz™ MOI (2-isocyanatoethyl methacrylate, Resonaq Inc.) and diethyl malonate (malonate-2-[[[[2-[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester) AOI-DMM: Reaction product of Karenz™ AOI (2-isocyanatoethyl acrylate, Resonaq Inc.) and dimethyl malonate, (malonate-2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-dimethyl ester) AOI-BP: Reaction product of Karenz™ AOI (2-isocyanatoethyl acrylate, Resonaq Inc.) and 3,5-dimethylpyrazole (2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl acrylate) AOI-AM: Reaction product of Karenz™ AOI (2-isocyanatoethyl acrylate, Resonaq Inc.) and 4-hydroxybenzoate methyl (4-[[[[[(1-oxo-2-propen-1-yl)oxy]ethyl]amino]carbonyl]oxy]-methyl benzoate) DMAA: Dimethylacrylamide, Tokyo Chemical Industry Co., Ltd. ACMO: Acryloylmorpholine, Tokyo Chemical Industry Co., Ltd. HEAA: 2-Hydroxyethylacrylamide, Tokyo Chemical Industry Co., Ltd. DAAM: Diacetoneacrylamide, Tokyo Chemical Industry Co., Ltd. NIPAM: N-Isopropylacrylamide, Tokyo Chemical Industry Co., Ltd. DEAA: N,N-Diethylacrylamide, Tokyo Chemical Industry Co., Ltd. NVP: N-Vinylpyrrolidone, Tokyo Chemical Industry Co., Ltd. PhMI: Phenylmaleimide, Tokyo Chemical Industry Co., Ltd. MAA: Methacrylic acid, Tokyo Chemical Industry Co., Ltd. AA: Acrylic acid, Tokyo Chemical Industry Co., Ltd. HOMS(N): 2-Methacryloyloxyethyl succinic acid, Product name Light Ester HO-MS(N), Kyoeisha Chemical Co., Ltd. HEMA: 2-Hydroxyethyl methacrylate, Tokyo Chemical Industry Co., Ltd. 4HBA: 4-Hydroxybutyl acrylate, Tokyo Chemical Industry Co., Ltd. PE-200: Polyethylene glycol monomethacrylate, Product name Bremmer PE-200, EO unit: approx. 4.5, NOF Corporation BZMA: Benzyl methacrylate, Tokyo Chemical Industry Co., Ltd. 2EHA: 2-Ethylhexyl acrylate, Tokyo Chemical Industry Co., Ltd. MMA: Methyl methacrylate, Tokyo Chemical Industry Co., Ltd. TCDMA: Dicyclopentanyl methacrylate, Tokyo Chemical Industries, Ltd. PME-200: Methoxypolyethylene glycol methacrylate, product name Bremmer PME-200, EO unit: approx. 4, NOF Corporation GMA: Glycidyl methacrylate PGMEA: Propylene glycol monomethyl ether acetate, Tokyo Chemical Industries, Ltd. PGME: Propylene glycol monomethyl ether, Tokyo Chemical Industries, Ltd. MB: 3-Methoxy-1-butanol, Tokyo Chemical Industries, Ltd. V-65: 2,2'-Azobis(2,4-dimethylvaleronitrile) (Fujifilm Wako Pure Chemical Corporation) SA: Succinic anhydride (Tokyo Chemical Industries, Ltd.)

[0185] <Preparation of Photosensitive Colored Compositions> [Examples 1-34, Comparative Examples 1-3] Copolymer (A-1) of Synthesis Examples 1-29 or copolymer (cA-1) of Comparative Synthesis Examples 1-3, copolymer (A-2) of Synthesis Examples 30-33, dipentaerythritol pentaacrylate (Toagosei Co., Ltd.) as a reactive diluent (B), ethanoone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl-]-,-1-(O-acetyloxime) (Ciba Japan Co., Ltd.) as a photopolymerization initiator (C), a mixture of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether or 3-methoxy-1-butanol (338 parts by mass and 257 parts by mass, respectively) as a solvent (D), and Valifast Blue as a colorant (E) 2620 (phthalocyanine dye, Orient Chemical Industry Co., Ltd.) was mixed with the amounts shown in Table 3 to prepare the photosensitive colored compositions of Examples 1 to 34 and Comparative Examples 1 to 3. The amounts of copolymer (A-1) or (cA-1) and copolymer (A-2) in Table 3 do not include the amount of solvent. The amount of solvent (D) in Table 3 is the total amount of solvent contained in the liquid containing copolymer (A-1) or copolymer (cA-1) obtained in the synthesis example or comparative synthesis example, the solvent contained in the liquid containing copolymer (A-2), and the solvent added when preparing the photosensitive colored composition.

[0186]

[0187] <Evaluation of Photosensitive Colored Compositions> The photosensitive colored compositions of Examples 1 to 34 and Comparative Examples 1 to 3 were evaluated by the following methods.

[0188] [Evaluation of Solvent Resistance] Solvent resistance was evaluated by the residual film percentage.

[0189] (Residual film rate) The photosensitive colored compositions of Examples 1 to 34 and Comparative Examples 1 to 3 were each applied by spin coating on an alkali-free glass substrate that was 5 cm long and 5 cm wide in plan view, so that the thickness after exposure was 2.5 μm, to form a coated film. Then, the solvent (D) in the coated film was evaporated and removed by heating at 100°C for 3 minutes.

[0190] Next, the coated film is exposed to ultraviolet light with a wavelength of 365 nm at an energy dose of 100 mJ / cm². ２ The exposed area was photocured by irradiation. Then, the coating film was cured by baking at 85°C for 30 minutes. The thickness of the prepared cured film was measured using a step gauge. This thickness was denoted as X.

[0191] Subsequently, the prepared cured film was immersed in 20 g of propylene glycol monomethyl ether acetate (PGMEA) at 23°C for 15 minutes. After immersion, the cured film was vacuum-dried at 40°C for 30 minutes, and its thickness was measured using a step gauge. This thickness was denoted as Y.

[0192] The solvent resistance of the cured film was evaluated by calculating the residual film percentage as the ratio of the thickness of the cured film after PGMEA immersion to the thickness of the cured film before PGMEA immersion (X) using the following formula. That is, the closer the residual film percentage is to 100%, the better the solvent resistance of the cured film. A residual film percentage of 80% or higher was considered acceptable. The residual film percentages of the cured films are shown in Table 3. Residual film percentage = (Y / X) × 100 (%)

[0193] As shown in Table 3, the cured films of the photosensitive colored compositions of Examples 1 to 34 had a residual film percentage (%) of 80% or more after immersion in PGMEA, and exhibited good solvent resistance even at a low baking temperature of 85°C.

[0194] [Evaluation of Developability] Developability was evaluated based on the adhesion of the cured film to fine lines.

[0195] The photosensitive colored compositions prepared in Examples 1 to 34 and Comparative Examples 1 to 3 were each applied to 5 cm square alkali-free glass substrates by spin coating so that the thickness after exposure was 1.5 μm (coating step). The glass substrates coated with the photosensitive colored compositions were heated at 100°C for 3 minutes to evaporate the solvent and dry the coated film (pre-bake step).

[0196] Next, using an ultra-high pressure mercury lamp, 100 mJ / cm² ２ The surface of the dried coating film was irradiated with light through a photomask (exposure step). The exposure step was performed with the photomask positioned 100 μm away from the coating film. The photomask used had a line and space pattern with a width of 3 to 100 μm. Next, the unexposed areas were removed by spraying semi-clean DL-A10 developer (Yokohama Oil & Fat Industry Co., Ltd.) (300-fold dilution) 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 (development step).

[0197] The glass substrate with the coated film after the development process was left to stand in a 100°C dryer for 30 minutes to heat-cur the coating film (post-bake process) and obtain a colored pattern. The colored pattern obtained in this way was observed using a microscope, and the adhesion of fine lines was evaluated by the minimum line width that could be developed, i.e., the minimum development dimension (μm). The results are shown in Table 3. In Comparative Examples 1 to 3, the film peeled off in the exposed areas, and no pattern remained.

[0198] [Storage Stability] The storage stability of the photosensitive colored compositions of Examples 1-34 and Comparative Examples 1-3 was evaluated according to the following method. 10 g each of the photosensitive colored compositions of Examples 1-34 and Comparative Examples 1-3 were weighed into 20 mL glass containers, and their viscosity was measured to determine the viscosity before storage. Viscosity was measured using an E-type viscometer (RE-80, rotor 1°34'×R24, Toki Sangyo Co., Ltd.) at 25°C and 20 rpm. Subsequently, each sample was stored in a constant temperature incubator maintained at 12°C for 3 months. After that, the viscosity was measured again in the same manner as above to determine the viscosity after storage. Using the viscosity before and after storage, the viscosity increase rate was calculated using the following formula and evaluated according to the criteria shown below. The results are shown in Table 3. Thickness increase rate (%) = (([Viscosity after storage] - [Viscosity before storage]) / [Viscosity before storage]) × 100 (Evaluation criteria for thickness increase rate) Excellent: Thickness increase rate less than 10% Good: Thickness increase rate 10-20% Poor: Thickness increase rate more than 20%

Claims

1. A photosensitive resin composition comprising a copolymer (A-1), a copolymer (A-2), a photopolymerization initiator (C), and a solvent (D), wherein the copolymer (A-1) contains a constituent unit (a) having a hydroxyl group, a constituent unit (b) having a nitrogen atom, and a constituent unit (c) having an acid group, and the unsaturated group equivalent of the copolymer (A-2) is 30 to 3000 g / mol.

2. A photosensitive resin composition comprising a copolymer (A-1), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D), wherein the copolymer (A-1) contains a constituent unit (a) having a hydroxyl group and a blocked isocyanate group, a constituent unit (b) having a nitrogen atom, and a constituent unit (c) having an acid group.

3. A photosensitive resin composition comprising a copolymer (A-1), a copolymer (A-2), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D), wherein the copolymer (A-1) contains a constituent unit (a) having a hydroxyl group, a constituent unit (b) having a nitrogen atom, and a constituent unit (c) having an acid group, and the unsaturated group equivalent of the copolymer (A-2) is 30 to 3000 g / mol.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the constituent unit (b) is a constituent unit derived from an amide group-containing ethylenically unsaturated compound.

5. The photosensitive resin composition according to any one of claims 1 to 3, wherein the constituent unit (b) is a constituent unit derived from an ethylenically unsaturated compound containing an amide group and a hydroxyl group.

6. The photosensitive resin composition according to any one of claims 1 to 3, wherein the constituent unit (a) is a constituent unit having at least one selected from the group consisting of a group represented by the following formula (1) and a group represented by the following formula (2). (In formula (1), R １ and R ２ Each of the following independently represents an alkyl group having 1 to 10 carbon atoms, n1 and n2 independently represent integers from 0 to 2, and * represents a linking site. (In formula (2), R ３ and R ４ Each of the following independently represents an alkyl group having 1 to 10 carbon atoms, n3 and n4 independently represent integers from 0 to 2, and * represents a linking site.

7. The photosensitive resin composition according to any one of claims 1 to 3, wherein the blocking agent constituting the blocked isocyanate group of the constituent unit (a) is at least one selected from the group consisting of pyrazole compounds, oxime compounds, and phenol compounds.

8. The photosensitive resin composition according to any one of claims 1 to 3, wherein the copolymer (A-1) further contains constituent units other than the constituent units (a) to (c).

9. The photosensitive resin composition according to any one of claims 1 to 3, wherein the copolymer (A-1) has a block isocyanate group equivalent of 200 to 3000 g / mol and a hydroxyl group equivalent of 100 to 5000 g / mol.

10. The photosensitive resin composition according to any one of claims 1 to 3, wherein the copolymer (A-1) has an acid value of 5 to 400 KOH mg / g and a weight-average molecular weight of 3,000 to 50,000.

11. The photosensitive resin composition according to any one of claims 1 to 3, wherein, of the total constituent units of the copolymer (A-1), the content of constituent unit (a) is 1 to 50 mol%, the content of constituent unit (b) is 1 to 50 mol%, and the content of constituent unit (c) is 1 to 70 mol%.

12. A photosensitive coloring composition comprising the photosensitive resin composition according to any one of claims 1 to 3 and a coloring agent (E).

13. A resin-cured film which is a cured product of the photosensitive resin composition according to any one of claims 1 to 3.

14. A color filter having a colored pattern which is a cured product of the photosensitive colored composition described in claim 12.

15. An image display element comprising the color filter described in claim 14.

Images