TWI889771B - Photosensitive resin composition, cured product, color filter, display device member, and display device - Google Patents

Abstract

The present provides a photosensitive resin composition having excellent storage stability, excellent curing reactivity, and excellent solvent resistance of the cured product. The photosensitive resin composition contains an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the alkali-soluble resin is a copolymer containing a structural unit (A) derived from an unsaturated carboxylic acid or an anhydride thereof and a structural unit (B) derived from a compound represented by the following formula (1), and has a heat generation peak top temperature of 180 to 220 ℃ that appears when the temperature is raised at a rate of 5 ℃/min using a differential scanning calorimeter.

(In the formula, R¹ and R² each represent a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. X represents a single bond or a divalent hydrocarbon group, etc. Y represents a methylene group or an ethylene group which may have an alkyl group having 1 to 3 carbon atoms as a substituent. n represents an integer of 0 to 7)

Description

Photosensitive resin composition, cured product, color filter, display device component, and display device

This disclosure relates to a photosensitive resin composition, a cured product, a color filter, a display device component, and a display device. This application claims priority to and incorporates the contents of Japanese Patent Application Nos. 2020-039964 and 2020-039965, filed in Japan on March 9, 2020.

Photosensitive resin compositions used in the manufacture of insulating films, color filters, color filter protective films, and microlenses include those containing an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator, and those further containing a colorant (pigment or dye).

Patent Documents 1 and 4 disclose copolymers containing methacrylic acid and glycidyl methacrylate as constituent monomers. Patent Documents 2 and 5 disclose copolymers containing methacrylic acid and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate as constituent monomers. Patent Document 3 discloses a copolymer containing methacrylic acid and benzyl methacrylate as constituent monomers.

[Prior Art Literature]

[Patent Literature]

Patent document 1: Japanese Patent Application Laid-Open No. 11-133600.

Patent Document 2: Japanese Patent Application Publication No. 2006-171160.

Patent Document 3: Japanese Patent Application Laid-Open No. 9-134004.

Patent Document 4: Japanese Patent Application Publication No. 2011-237728.

Patent Document 5: Japanese Patent Application Publication No. 2007-333847.

However, the photosensitive resin compositions disclosed in Patents 1 and 4 suffer from low stability, such as increased viscosity over time. Furthermore, the cured product exhibits insufficient solvent resistance. While the photosensitive resin compositions disclosed in Patents 2 and 5 exhibit excellent storage stability, they exhibit poor reactivity with carboxylic acids and require a curing temperature above 230°C. The photosensitive resin composition disclosed in Patent 3 also exhibits low solvent resistance in the cured product.

Therefore, the object of the present invention is to provide a photosensitive resin composition having excellent storage stability, excellent curing reactivity, and excellent solvent resistance of the cured product.

Another object of the present invention is to provide a cured product of the photosensitive resin composition having the above-mentioned properties, a color filter of the cured product, and a display device component or display device having the color filter.

As a result of diligent research to achieve the above-mentioned objectives, the inventors have discovered a photosensitive resin composition that utilizes a copolymer containing specific structural units and having a peak exothermic temperature of 180 to 220°C as an alkali-soluble resin. This composition exhibits excellent storage stability, can be cured at relatively low temperatures, and exhibits excellent solvent resistance in the cured product. The present invention was completed based on these discoveries.

That is, the present disclosure provides a photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein:

The alkali-soluble resin is a copolymer containing a constituent unit (A) derived from an unsaturated carboxylic acid or its anhydride and a constituent unit (B) derived from a compound represented by the following formula (1), and exhibiting a heating peak temperature of 180 to 220°C when heated at a rate of 5°C/min using a differential scanning calorimeter.

(In the formula, ^R1 and ^R2 are the same or different and represent a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, X represents a single bond or a divalent alkyl group which may contain a heteroatom, Y represents a methylene or ethylene group which may have an alkyl group having 1 to 3 carbon atoms as a substituent, an oxygen atom, or a sulfur atom which may be bonded to an oxygen atom, and n represents an integer from 0 to 7.)

The aforementioned copolymer may further contain a constituent unit (C) derived from at least one compound selected from the group consisting of (c1) to (c4) below.

(c1) Styrene which may be substituted with an alkyl group;

(c2) N-substituted cis-butylenediamide;

(c3) N-vinyl compounds;

(c4) An unsaturated carboxylic acid derivative represented by the following formula (2).

(In the formula, R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, R ¹² represents a alkyl group which may contain a heteroatom, and Z represents a heteroatom)

Relative to the total constituent units of the copolymer, the proportion of the constituent unit (A) may be 2 to 60% by weight, the proportion of the constituent unit (B) may be 40 to 98% by weight, and the proportion of the constituent unit (C) may be 0 to 85% by weight.

The photosensitive resin composition disclosed herein may further contain a colorant.

The aforementioned coloring material may be a pigment and/or dye.

Furthermore, the present disclosure provides a cured product of the aforementioned photosensitive resin composition.

Furthermore, the present disclosure provides a color filter that is a cured product of the aforementioned photosensitive resin composition.

This disclosure provides a display device component or a display device that includes the aforementioned color filter.

The present invention provides a photosensitive resin composition with excellent storage stability, excellent curing reactivity, and excellent solvent resistance of the cured product. Furthermore, a cured product of the photosensitive resin composition having the aforementioned properties, a color filter formed from the cured product, and a display device component or display device incorporating the color filter can be provided.

The photosensitive resin composition disclosed herein is primarily used as a forming material for insulating films, color filter protective films, microlenses, colored patterns, and transparent films. It contains an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. Furthermore, the photosensitive resin composition disclosed herein may further contain a colorant.

<Alkaline soluble resin>

In the present disclosure, the alkali-soluble resin used is a copolymer containing a constituent unit (A) derived from an unsaturated carboxylic acid or its anhydride and a constituent unit (B) derived from the compound represented by the aforementioned formula (1), and exhibiting a peak exothermic temperature of 180 to 220°C when heated at a rate of 5°C/min using a differential scanning calorimeter. The aforementioned copolymer may further contain a constituent unit (C) derived from at least one compound selected from the group consisting of (c1) to (c4). Furthermore, the copolymer may further contain the constituent unit (D) described below as a constituent unit other than the constituent units (A) to (C).

[Constituent unit (A)]

The constituent unit (A) can be introduced into the copolymer by copolymerizing an unsaturated carboxylic acid or its anhydride (a).

The unsaturated carboxylic acid or its anhydride (a) is not particularly limited. Examples include: α,β-unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; α,β-unsaturated dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid; anhydrides of α,β-unsaturated monocarboxylic acids such as methacrylic anhydride; and anhydrides of α,β-unsaturated dicarboxylic acids such as maleic anhydride and itaconic anhydride. Of these, acrylic acid and methacrylic acid are particularly preferred from the perspective of copolymerizability and developing properties. The unsaturated carboxylic acid or its anhydride (a) may be used alone or in combination of two or more.

The ratio (content) of the constituent units (A) relative to the total constituent units of the aforementioned copolymer is not particularly limited, but is preferably 2 to 60% by weight, more preferably 3 to 40% by weight, and even more preferably 5 to 20% by weight. By maintaining the ratio of the constituent units (A) within the above range, the cured product tends to have superior solvent resistance or developability. Furthermore, in this disclosure, the ratio of the constituent units in the copolymer refers to the weight of the compounds (monomers) used in the copolymerization. For example, the ratio of the constituent units (A) in the copolymer relative to the total weight of the compounds used in the copolymerization (100% by weight) refers to the ratio of the unsaturated carboxylic acid or its anhydride (a) used.

[Constituent unit (B)]

The constituent unit (B) can be introduced into the copolymer by copolymerizing the compound represented by the following formula (1).

In formula (1), ^R1 and ^R2 are the same or different and represent a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. X represents a single bond or a divalent alkyl group which may contain a heteroatom. Y represents a methylene or ethylene group which may have an alkyl group having 1 to 3 carbon atoms as a substituent, an oxygen atom, or a sulfur atom which may be bonded to an oxygen atom. n represents an integer from 0 to 7.

Examples of the C1-7 alkyl group in ^R1 and ^R2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, and heptyl. When n is 2 or greater, the n ^R2 groups may be the same or different. From the perspective of copolymerizability and reactivity, ^R1 and ^R2 are preferably hydrogen atoms, methyl groups, or ethyl groups.

In a divalent hydrocarbon group X that may contain a heteroatom, the heteroatom may be bonded to the terminal end of the hydrocarbon group or interposed between the carbon atoms that constitute the hydrocarbon group. The heteroatom is not particularly limited, and examples thereof include nitrogen, oxygen, and sulfur atoms.

Examples of the aforementioned divalent alkyl groups that may contain heteroatoms include: alkylene groups such as methylene, ethylene, propylene, and trimethylene (preferably alkylene groups having 1 to 12 carbon atoms, more preferably alkylene groups having 1 to 6 carbon atoms, and even more preferably alkylene groups having 1 to 3 carbon atoms); alkylene sulfides such as thiomethylene, ethylene, and propylene (preferably alkylene sulfides having 1 to 12 carbon atoms, more preferably alkylene sulfides having 1 to 6 carbon atoms); and aminoalkylene groups such as aminomethylene, aminoethylene, and aminopropylene (preferably aminoalkylene groups having 1 to 12 carbon atoms, more preferably aminoalkylene groups having 1 to 6 carbon atoms). Among these, from the perspective of stability, alkylene groups having 1 to 3 carbon atoms are preferred, and methylene is more preferred.

The methylene or ethylidene group of Y which may have an alkyl group having 1 to 3 carbon atoms as a substituent is not particularly limited, but is preferably a methylene or ethylidene group, and more preferably a methylene group.

Examples of the sulfur atom in Y that can bond to an oxygen atom include a sulfur atom, a sulfonyl group, etc.

The compound represented by the aforementioned formula (1) can be exemplified by the compound represented by the following formula (1a).

In formula (1a), R ¹ , R ² , X, Y, and n are the same as those described for formula (1).

Specific examples of the compound represented by formula (1) include the following compounds.

The ratio (content) of the constituent units (B) relative to the total constituent units of the aforementioned copolymer is not particularly limited, but is preferably 40 to 98 weight percent, more preferably 60 to 95 weight percent, and even more preferably 75 to 90 weight percent. By maintaining the ratio of the constituent units (B) within the above range, the cured product tends to have superior solvent resistance or developability.

[Constituent unit (C)]

The constituent unit (C) is a constituent unit derived from at least one compound selected from the group consisting of alkyl-substituted styrenes (c1), N-substituted cis-butylenediimides (c2), N-vinyl compounds (c3), and unsaturated carboxylic acid derivatives (c4) represented by the aforementioned formula (2). The constituent unit (C) has the function of imparting hardness to the cured product (cured film), stabilizing the copolymerization reaction, improving solubility in solvents, and improving adhesion to the substrate.

The constituent unit (C) can be introduced into the copolymer by copolymerizing at least one compound selected from the group consisting of (c1) to (c4).

(Styrene (c1))

The alkyl group in the alkyl-substituted styrene (c1) is not particularly limited. Examples include alkyl groups having 1 to 7 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and hexyl. Preferred among these groups are alkyl groups having 1 to 4 carbon atoms, such as methyl or ethyl, and more preferably, methyl. The aforementioned alkyl group may be bonded to either the vinyl group or the benzene ring of the styrene.

Representative examples of alkyl-substituted styrenes (c1) include styrene, α-methylstyrene, and vinyltoluene (o-vinyltoluene, m-vinyltoluene, and p-vinyltoluene). Alkyl-substituted styrenes (c1) may be used alone or in combination of two or more.

(N-substituted cis-butylenediimide (c2))

Examples of N-substituted butylenediimide (c2) include the compound represented by the following formula (3).

In formula (3), R ²¹ represents an organic group.

Examples of the aforementioned organic groups include alkyl groups and heterocyclic groups. Examples of alkyl groups include alkyl groups (e.g., C _1-6 alkyl groups) such as methyl, ethyl, propyl, isopropyl, butyl, and hexyl; cycloalkyl groups such as cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, and norbornyl; aryl groups such as phenyl; aralkyl groups such as benzyl; and groups formed by bonding two or more of these groups. Examples of heterocyclic groups include 5- to 10-membered heterocycloalkyl and heteroaryl groups containing at least one hetero atom selected from the group consisting of nitrogen, oxygen, and sulfur atoms.

The N-substituted cis-butenediamide (c2) is not particularly limited, and examples thereof include N-alkyl cis-butenediamides such as N-methyl cis-butenediamide, N-ethyl cis-butenediamide, and N-propyl cis-butenediamide; N-cyclopentyl cis-butenediamide, N-cyclohexyl cis-butenediamide, and N-cyclohexyl cis-butenediamide. N-cycloalkyl cis-butenediamides such as cyclooctyl cis-butenediamide, N-adamantyl cis-butenediamide, and N-norbornyl cis-butenediamide; N-aryl cis-butenediamides such as N-phenyl cis-butenediamide; and N-aralkyl cis-butenediamides such as N-benzyl cis-butenediamide. N-substituted cis-butenediamides (c2) can be used alone or in combination of two or more.

(N-vinyl compound (c3))

The N-vinyl compound (c3) is not particularly limited. Examples thereof include N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-methylacetamide, N-vinylpyrrolidone, N-vinylcarbazole, N-vinylpiperidone, and N-vinylcaprolactam. The N-vinyl compound (c3) may be used alone or in combination of two or more.

(Unsaturated carboxylic acid derivatives (c4))

The unsaturated carboxylic acid derivative (c4) can be represented by the following formula (2).

In formula (2), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. R ¹² represents a alkyl group which may contain a heteroatom. Z represents a heteroatom.

Examples of the alkyl group having 1 to 7 carbon atoms in R ¹¹ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and hexyl. R ¹¹ is particularly preferably a hydrogen atom or a methyl group.

Examples of the alkyl group that may contain a heteroatom in R ¹² include alkyl groups, heteroalkyl groups, alkenyl groups, cycloalkyl groups, heterocycloalkyl groups, aryl groups, and groups formed by linking two or more of these groups. Examples of the heteroatom include nitrogen, oxygen, and sulfur atoms.

Examples of the aforementioned alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, octyl, decyl, dodecyl, isodecyl, lauryl, stearyl, and other alkyl groups with 1 to 23 carbon atoms.

Examples of the heteroalkyl group include -( ^R13 -O) ^mR14 (wherein ^R13 represents an alkylene group having 1 to 12 carbon atoms, ^R14 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and m represents an integer greater than 1), and ^-R15 - ^NR16R17 (wherein ^R15 represents an alkylene group having 1 to 12 carbon atoms, and ^R16 and ^{R17 each} represent the same or different hydrogen atoms or an alkyl group having 1 to 4 carbon atoms).

Examples of the alkenyl group include allyl, 3-butenyl, 5-hexenyl, and other alkenyl groups having 2 to 23 carbon atoms.

Examples of the aforementioned cycloalkyl group include cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, norbornyl and other cycloalkyl groups having 3 to 12 carbon atoms.

Examples of the aforementioned heterocycloalkyl group include cyclohexane ring, tetrahydrofuran ring, tetrahydropyran ring, cyclohexane ring, and other groups containing a cyclic ether structure (e.g., a group containing a cyclic ether with three or more members).

Examples of the aforementioned aryl group include phenyl, naphthyl, and other aryl groups having 6 to 12 carbon atoms.

The unsaturated carboxylic acid derivative (c4) represented by formula (2) is not particularly limited, and examples thereof include (meth)acrylates having an alkyl group, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate; N,N-dimethylaminoethyl (meth)acrylate, N,N- (Meth)acrylates containing alkylamino groups, such as diethylaminoethyl and N,N-diisopropylaminoethyl (meth)acrylate; (Meth)acrylates containing hydroxyl groups, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; (Meth)acrylates containing hydroxyl groups, such as methoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, and isooctyloxydiethylene glycol (meth)acrylate. (Meth)acrylates having heteroalkyl groups, such as polyalkylene glycol (meth)acrylates, such as phenoxytriethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate; (Meth)acrylates having alkenyl groups, such as allyl (meth)acrylate; cyclohexyl (meth)acrylate, 1-adamantyl (meth)acrylate, isoborneol (meth)acrylate, tricyclo[5,2,1,02,6]decane-8- (Meth)acrylates having a monocyclic or polycyclic cycloalkyl group, such as alcohol (meth)acrylate; (meth)acrylates having an epoxy (or epoxyethylene) group, such as glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3-glycidyloxypropyl (meth)acrylate, and glycidyloxyphenyl (meth)acrylate; (meth)acrylates having an epoxy (or epoxyethylene) group, such as glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3-glycidyloxypropyl (meth)acrylate, and glycidyloxyphenyl (meth)acrylate; (meth)acrylates having an epoxy (or epoxyethylene) group; butyl (meth)acrylate, 3-methyl-3-oxycyclobutyl (meth)acrylate, 3-ethyl-3-oxycyclobutyl (meth)acrylate, (3-methyl-3-oxycyclobutyl)methyl (meth)acrylate, (3-ethyl-3-oxycyclobutyl)methyl (meth)acrylate, 2-(3-methyl-3-oxycyclobutyl)ethyl (meth)acrylate, 2-(3-ethyl-3-oxycyclobutyl)ethyl (meth)acrylate, 2-[(3-methyl- (Meth)acrylates having an oxycyclobutyl group, such as 2-[(3-ethyl-3-oxycyclobutyl)methyloxy]ethyl (meth)acrylate, 3-[(3-methyl-3-oxycyclobutyl)methyloxy]propyl (meth)acrylate, and 3-[(3-ethyl-3-oxycyclobutyl)methyloxy]propyl (meth)acrylate; (Meth)acrylates having a tetrahydrofuranyl group, such as tetrahydrofurfuryl (meth)acrylate; (Meth)acrylates having a tetrahydrofuranyl group, such as tetrahydrofurfuryl (meth)acrylate; (meth)acrylates containing an alicyclic cyclooxy group such as 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 2-(3,4-epoxycyclohexylmethyloxy)ethyl (meth)acrylate, and 3-(3,4-epoxycyclohexylmethyloxy)propyl (meth)acrylate; (meth)acrylates containing a heterocyclic alkyl group (for example, a group containing a cyclic ether having three or more ring members); Acrylates; (meth)acrylates containing aromatic groups such as phenyl (meth)acrylate and benzyl (meth)acrylate; (meth)acrylates containing alkoxysilyl groups such as 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, and 8-(meth)acryloxyoctyltrimethoxysilane. The unsaturated carboxylic acid derivative (c4) represented by formula (2) can be used alone or in combination of two or more.

The ratio (content) of the constituent unit (C) relative to the total constituent units of the aforementioned copolymer is not particularly limited, but is preferably 0 to 85% by weight, more preferably 1 to 60% by weight, and even more preferably 2 to 40% by weight. By keeping the ratio of the constituent unit (C) within this range, the cured product tends to have excellent solvent resistance.

[Constituent unit (D)]

The aforementioned copolymer disclosed herein may contain a constituent unit (D) other than the aforementioned constituent units (A) to (C). Constituent unit (D) may be, for example, a constituent unit derived from (meth)acrylamide or (meth)acrylonitrile.

When the copolymer described herein contains the constituent units (A) and (B) and does not contain the constituent unit (C), the total amount of the constituent units (A) and (B) relative to the total constituent units is preferably 90% by weight or more, more preferably 95% by weight or more, and even more preferably 99% by weight or more, and may be substantially 100% by weight. Furthermore, when the copolymer described herein contains the constituent units (A), (B), and (C), the total amount of the constituent units (A) to (C) relative to the total constituent units is preferably 90% by weight or more, more preferably 95% by weight or more, and even more preferably 99% by weight or more, and may be substantially 100% by weight.

The weight-average molecular weight (Mw) of the copolymer is not particularly limited, but is preferably 1,000 to 1,000,000, more preferably 3,000 to 300,000, and even more preferably 5,000 to 100,000. The molecular weight distribution of the copolymer (the ratio of the weight-average molecular weight to the number-average molecular weight: Mw/Mn) is not particularly limited, but is preferably 5.0 or less, more preferably 1.0 to 4.5, and even more preferably 1.0 to 4.0. In this disclosure, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be measured, for example, by GPC using polystyrene as a standard, but are preferably measured by the method used in the Examples.

The aforementioned polymers disclosed herein exhibit a peak exothermic temperature of 180 to 220°C when heated at a rate of 5°C/min using a differential scanning calorimeter. Furthermore, in the present disclosure, the peak exothermic temperature is preferably measured using the method used in the examples described below.

The aforementioned copolymer in this disclosure functions as a binder resin in the photosensitive resin composition of this disclosure.

<Method for producing copolymer>

The copolymers disclosed herein can be produced by copolymerizing an unsaturated carboxylic acid or its anhydride (a), a compound containing a polycyclic aliphatic group having an epoxy group on its ring and a group having an unsaturated bond (b), at least one compound selected from the group consisting of (c1) to (c4) as needed, and a compound corresponding to the aforementioned constituent unit (D). Hereinafter, compounds such as the unsaturated carboxylic acid or its anhydride (a) that can be introduced into the copolymer are collectively referred to as "monomers."

In the method for producing the copolymer disclosed herein, copolymerization can be carried out in the presence of a polymerization initiator. The aforementioned polymerization initiator can be a conventional or well-known free radical polymerization initiator, for example: azo compounds such as 2,2' -azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), diethyl-2,2'-azobis(2-methylpropionate), and dibutyl-2,2'-azobis(2-methylpropionate); organic peroxides such as benzoyl peroxide, lauryl peroxide, t-butyl peroxypivalate, and 1,1-bis(t-butylperoxy)cyclohexane; and hydrogen peroxide. When a peroxide is used as a free radical polymerization initiator, a reducing agent may be combined to form a redox initiator. Azo compounds are preferred, with 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and dimethyl-2,2'-azobis(2-methylpropionate) being more preferred.

The amount of the polymerization initiator used can be appropriately selected within a range that does not impair stable copolymerization and is not particularly limited. For example, relative to the total amount of monomers (100 parts by weight), it is preferably 1 to 20 parts by weight, and more preferably 3 to 15 parts by weight.

In this disclosure, copolymerization can be carried out by conventional methods used to produce acrylic polymers or styrene polymers, such as solution polymerization, bulk polymerization, suspension polymerization, bulk/suspension polymerization, and emulsion polymerization. The monomers and polymerization initiator can be supplied to the reaction system separately, or a portion or all of them can be added dropwise to the reaction system. For example, a polymerization method can be employed in which a solution containing a polymerization initiator dissolved in a polymerization solvent is dripped into a mixture of monomers or monomers and a polymerization solvent maintained at a constant temperature; or a polymerization method in which a solution containing monomers and a polymerization initiator pre-dissolved in a polymerization solvent is dripped into a polymerization solvent maintained at a constant temperature (drop polymerization method).

The aforementioned copolymers in the present disclosure are preferably copolymerized in a polymerization solvent. The polymerization solvent can be appropriately selected according to the monomer composition, and examples thereof include: ethers (chain ethers such as diethyl ether; glycol ethers such as ethylene glycol mono- or dialkyl ether, diethylene glycol mono- or dialkyl ether, propylene glycol mono- or dialkyl ether, propylene glycol mono- or diaryl ether, dipropylene glycol mono- or dialkyl ether, tripropylene glycol mono- or dialkyl ether, 1,3-propylene glycol mono- or dialkyl ether, 1,3-butanediol mono- or dialkyl ether, 1,4-butanediol mono- or dialkyl ether, glycerol mono- or di- or trialkyl ether; cyclic ethers such as tetrahydrofuran and dioxane), esters (methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, C _5-6 cycloalkanediol mono- or diacetate, C Carboxylic acid esters such as _5-6 -cycloalkane dimethanol mono- or diacetate; ethylene glycol monoalkyl ether acetate, ethylene glycol mono- or diacetate, diethylene glycol monoalkyl ether acetate, diethylene glycol mono- or diacetate, propylene glycol monoalkyl ether acetate, propylene glycol mono- or diacetate, dipropylene glycol monoalkyl ether acetate, dipropylene glycol mono- or diacetate, 1,3-propylene glycol monoalkyl ether acetate, 1,3-propylene glycol mono- or diacetate, 1,3-butanediol monoalkyl ether acetate, 1,3-butanediol mono- or diacetate, 1,4-butanediol monoalkyl ether acetate, 1,4-butanediol mono- or diacetate, glycerol mono- or di- or triacetate, glycerol mono- or di-C _1-4 alkyl ether di- or monoacetates, tripropylene glycol monoalkyl ether acetate, tripropylene glycol mono- or diacetate, etc., glycol acetates or glycol ether acetates, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 3,5,5-trimethyl-2-cyclohexene-1-one, etc.), amides (N,N-dimethylacetamide, N,N-dimethylformamide, etc.), sulfoxides (dimethyl sulfoxide, etc.), alcohols (methanol, ethanol, propanol, _C5-6 cycloalkanediols, _C5-6 cycloalkane dimethanol, etc.), hydrocarbons (aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane, etc.), and mixed solvents thereof.

The polymerization temperature can be appropriately selected according to the type or composition of the monomers and is not particularly limited. For example, it is preferably 30 to 150°C.

The reaction solution containing the copolymer obtained by the above method can be purified by precipitation or reprecipitation as needed. The solvent used for precipitation or reprecipitation can be any one of an organic solvent and water, or a mixed solvent thereof. Examples of organic solvents include hydrocarbons (aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene), halogenated hydrocarbons (halogenated aliphatic hydrocarbons such as dichloromethane, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene), nitro compounds (nitromethane, nitroethane, etc.), nitriles (acetonitrile, benzonitrile, etc.), ethers (diethyl ether, dimethylbenzene, etc.), and nitrocarbons. Chain ethers such as isopropyl ether and dimethoxyethane; cyclic ethers such as tetrahydrofuran and dioxane), ketones (acetone, methyl ethyl ketone, diisobutyl ketone, etc.), esters (ethyl acetate, butyl acetate, etc.), carbonates (dimethyl carbonate, diethyl carbonate, ethyl carbonate, propyl carbonate, etc.), alcohols (methanol, ethanol, propanol, isopropyl alcohol, butanol, etc.), carboxylic acids (acetic acid, etc.), and mixed solvents containing these solvents.

<Color material>

In this disclosure, any colorant (colorant) is sufficient as long as it has coloring properties. The color or material can be appropriately selected based on the intended use of the color filter. Specifically, any of pigments, dyes, and natural pigments can be used as colorants. Color filters require high color purity, brightness, and contrast, so pigments and/or dyes are preferred.

The aforementioned pigments may be either organic or inorganic. Organic pigments include compounds classified as pigments in the Color Index (C.I.; published by The Society of Dyers and Colourists). Specifically, the following C.I. names may be cited.

C.I. Paint Yellow 1, C.I. Paint Yellow 3, C.I. Paint Yellow 12, C.I. Paint Yellow 13, C.I. Paint Yellow 14, C.I. Paint Yellow 16, C.I. Paint Yellow 17, C.I. Paint Yellow 20, C.I. Paint Yellow 24, C.I. Paint Yellow 31, C.I. Paint Yellow 55, C.I. Paint Yellow 83, C.I. Paint Yellow 86, C.I. Paint Yellow 93, C.I. Paint Yellow 94, C.I. Paint Yellow 109, C.I. Paint Yellow 110, C.I. Paint Yellow 117, Yellow pigments include C.I. Yellow 125, C.I. Yellow 137, C.I. Yellow 138, C.I. Yellow 139, C.I. Yellow 147, C.I. Yellow 148, C.I. Yellow 150, C.I. Yellow 153, C.I. Yellow 154, C.I. Yellow 155, C.I. Yellow 166, C.I. Yellow 168, C.I. Yellow 180, C.I. Yellow 194, C.I. Yellow 211, and C.I. Yellow 214.

C.I. Paint Orange 5, C.I. Paint Orange 13, C.I. Paint Orange 14, C.I. Paint Orange 24, C.I. Paint Orange 31, C.I. Paint Orange 34, C.I. Paint Orange 36, C.I. Paint Orange 38, C.I. Paint Orange 40, C.I. Paint Orange 42, C.I. Paint Orange 43, C.I. Paint Orange 46, C.I. Paint Orange 4 9. C.I. Paint Orange 51, C.I. Paint Orange 55, C.I. Paint Orange 59, C.I. Paint Orange 61, C.I. Paint Orange 64, C.I. Paint Orange 65, C.I. Paint Orange 68, C.I. Paint Orange 70, C.I. Paint Orange 71, C.I. Paint Orange 72, C.I. Paint Orange 73, C.I. Paint Orange 74 and other orange paints.

C.I. Pigment Red 1, C.I. Pigment Red 2, C.I. Pigment Red 5, C.I. Pigment Red 9, C.I. Pigment Red 17, C.I. Pigment Red 31, C.I. Pigment Red 32, C.I. Pigment Red 41, C.I. Pigment Red 97, C.I. Pigment Red 105, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 144, C.I. Pigment Red 149, C.I. Pigment Red 166, C.I. Pigment Red 168, C.I. Pigment Red 170, C.I. Pigment Red 171, C.I. Pigment Red 175, C.I. Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 178, C.I. Pigment Red 179, C.I. .Red pigments such as C.I. Red 180, C.I. Red 185, C.I. Red 187, C.I. Red 192, C.I. Red 202, C.I. Red 206, C.I. Red 207, C.I. Red 209, C.I. Red 214, C.I. Red 215, C.I. Red 216, C.I. Red 220, C.I. Red 221, C.I. Red 224, C.I. Red 242, C.I. Red 243, C.I. Red 254, C.I. Red 255, C.I. Red 262, C.I. Red 264, C.I. Red 265, and C.I. Red 272.

Purple pigments such as C.I. Paint Purple 1, C.I. Paint Purple 19, C.I. Paint Purple 23, C.I. Paint Purple 29, C.I. Paint Purple 32, C.I. Paint Purple 36, and C.I. Paint Purple 38.

Blue pigments such as C.I. Blue 15, C.I. Blue 15:3, C.I. Blue 15:4, C.I. Blue 15:6, C.I. Blue 60, and C.I. Blue 80.

Green pigments such as C.I. Green 7, C.I. Green 36, and C.I. Green 58.

Brown pigments such as C.I. Pigment Brown 23 and C.I. Pigment Brown 25.

Black pigments such as C.I. Pigment Black 1 and C.I. Pigment Black 7.

In addition, the above-mentioned inorganic pigments include, for example, titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc yellow, ferric oxide (red iron (III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, umber, titanium black, synthetic iron black, carbon black, etc.

In this disclosure, the pigment can be purified and used by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, or a combination thereof. Furthermore, the pigment can be used after its particle surface is modified with a resin.

Furthermore, the dyes mentioned above can be appropriately selected from various oil-soluble dyes, direct dyes, acid dyes, metal complex dyes, etc., for example, the following Color Index (C.I.) names can be cited.

Yellow dyes such as C.I. Solvent Yellow 4, C.I. Solvent Yellow 14, C.I. Solvent Yellow 15, C.I. Solvent Yellow 24, C.I. Solvent Yellow 82, C.I. Solvent Yellow 88, C.I. Solvent Yellow 94, C.I. Solvent Yellow 98, C.I. Solvent Yellow 162, C.I. Solvent Yellow 179, C.I. Acid Yellow 17, C.I. Acid Yellow 29, C.I. Acid Yellow 40, and C.I. Acid Yellow 76.

Orange dyes such as C.I. Solvent Orange 2, C.I. Solvent Orange 7, C.I. Solvent Orange 11, C.I. Solvent Orange 15, C.I. Solvent Orange 26, C.I. Solvent Orange 56, C.I. Sour Orange 51, and C.I. Sour Orange 63.

Red dyes such as C.I. Solvent Red 45, C.I. Solvent Red 49, C.I. Acid Red 91, C.I. Acid Red 92, C.I. Acid Red 97, C.I. Acid Red 114, C.I. Acid Red 138, and C.I. Acid Red 151.

Blue dyes such as C.I. Solvent Blue 35, C.I. Solvent Blue 37, C.I. Solvent Blue 59, C.I. Solvent Blue 67, C.I. Acid Blue 80, C.I. Acid Blue 83, and C.I. Acid Blue 90.

Green dyes such as C.I. Acid Green 9, C.I. Acid Green 16, C.I. Acid Green 25, and C.I. Acid Green 27.

The color materials disclosed herein may be used alone or in combination of two or more.

The colorant content relative to the solid content of the photosensitive resin composition is not particularly limited, but is preferably 3 to 50% by weight, more preferably 5 to 30% by weight. "Solid content" herein refers to ingredients other than the aforementioned solvent, for example.

In this disclosure, when pigments are used as colorants, they may be used together with pigment dispersants and pigment dispersing aids as needed. Examples of such pigment dispersants include cationic, anionic, nonionic, and amphoteric dispersants (surfactants); and polymer dispersants such as acrylic copolymers, polyesters, polyurethanes, polyethyleneimines, and polyallylamines.

Commercially available pigment dispersants can be used, such as acrylic copolymers Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, and BYK-LPN21116 (all manufactured by BYK), polyesters Ajisper PB821, Ajisper PB822, and Ajisper PB880 (manufactured by Ajinomoto Fine-Techno Co., Ltd.), polyurethanes Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, and Disperbyk-182 (all manufactured by BYK), SOLSPERSE 76500 (manufactured by Lubrizol Corporation), and polyethyleneimine SOLSPERSE 24000 (manufactured by Lubrizol Corporation).

These pigment dispersants can be used alone or as a mixture of two or more. The pigment dispersant content is typically less than 100 parts by weight, preferably 1 to 70 parts by weight, more preferably 10 to 70 parts by weight, and even more preferably 30 to 60 parts by weight, relative to 100 parts by weight of pigment. A pigment dispersant content within this range is preferred because it tends to produce a uniformly dispersed pigment dispersion.

Examples of the pigment dispersing aid include pigment derivatives, specifically copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinoline yellow. The content of the pigment dispersing aid can be appropriately determined within a range that does not hinder the purpose of the present invention.

<Photopolymerizable compound>

In this disclosure, the photopolymerizable compound is not particularly limited, and examples thereof include polyfunctional vinyl compounds, polyfunctional thiol compounds, and polyfunctional epoxy compounds.

The polyfunctional vinyl compound is not particularly limited as long as it is a compound having two or more vinyl groups. Examples thereof include: di(meth)acrylates of alkylene glycols such as ethylene glycol and propylene glycol; di(meth)acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; di(meth)acrylates of double-terminal hydroxylated polymers such as double-terminal hydroxylated polybutadiene, double-terminal hydroxylated polyisoprene, and double-terminal hydroxylated polycaprolactone; glycerol, 1,2,4-butanetriol, trihydroxymethyl alkane, Poly(meth)acrylates of trivalent or higher polyols such as tetrahydroxymethane, pentaerythritol, and dipentaerythritol; poly(meth)acrylates of polyalkylene glycol adducts of trivalent or higher polyols; poly(meth)acrylates of cyclic polyols such as 1,4-cyclohexanediol and 1,4-benzenediol; and oligo(meth)acrylates such as polyester (meth)acrylates, epoxy (meth)acrylates, urethane (meth)acrylates, and silicone (meth)acrylates. Preferred among these are polyfunctional (meth)acrylates having two or more (meth)acryloyl groups. Polyfunctional vinyl compounds may be used alone or in combination of two or more.

The polyfunctional thiol compound is not particularly limited as long as it is a compound having two or more thiol groups, and examples thereof include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthiol acetate, ethylene glycol bisthiol acetate, ethylene glycol bisthiol propionate, trihydroxymethylpropane trithiol acetate, trihydroxymethylpropane trithiol propionate, trihydroxymethylpropane tris(3-butylenebutyrate), pentaerythritol tetrathiol acetate, pentaerythritol tetrathiol propionate, tris(2-hydroxyethyl) isocyanurate of tris(2-hydroxyethyl)tri ... , 2-(N,N-dibutylamino)-4,6-diol-s-triazine , Tetraethylene glycol bis-3-butylpropionate, trihydroxymethylpropane tri-3-butylpropionate, tris(3-butylpropynyloxyethyl)isocyanurate, pentaerythritol tetra-3-butylpropionate, dipentaerythritol tetra-3-butylpropionate, 1,4-bis(3-butylbutyloxy)butane, 1,3,5-tris(3-butylbutyloxyethyl)- ... -2,4,6(1H,3H,5H)-trione, pentaerythritol tetra(3-hydroxybutyrate), etc. The polyfunctional thiol compound can be used alone or in combination of two or more.

The polyfunctional epoxy compound is not particularly limited as long as it is a compound having two or more epoxy groups. Examples thereof include epoxy propoxy ether-type epoxy compounds [polyhydroxy compounds (diphenols, polyvalent phenols, alicyclic polyols, aliphatic polyols, etc.)] and epichlorohydrin to form epoxy propoxy ethers (e.g., ethylene glycol diepoxypropyl ether, diethylene glycol diepoxypropyl ether, polyethylene glycol diepoxypropyl ether, etc. (poly) C _2-4- Alkanediol diglycidyl ether; diglycidyl ether of polyvalent phenols such as resorcinol and hydroquinone; diglycidyl ether of alicyclic polyols such as cyclohexanediol, cyclohexanedimethanol, and hydrogenated bisphenols; bisphenols (bis(hydroxyphenyl)alkanes such as 4,4'-dihydroxybiphenyl and bisphenol A) or their C _2-3 epoxy adducts of diglycidyl ether, etc.), novolac type epoxy resins (phenol novolac type or cresol novolac type epoxy resins, etc.), epoxypropyl ester type epoxy compounds, aliphatic epoxy compounds (or epoxy aliphatic epoxy resins), hybrid epoxy resins (triglycidyl isocyanurate (TGIC), hydantoin type epoxy resins, etc.), epoxypropylamine type epoxy compounds [amines and epichlorohydrin Examples of the reaction product include N-epoxypropyl aromatic amines {tetraepoxypropyldiaminodiphenylmethane (TGDDM), triepoxypropylaminophenol (TGPAP, TGMAP, etc.), diepoxypropylaniline (DGA), diepoxypropyltoluidine (DGT), tetraepoxypropylxylenediamine (TGMXA, etc.), and N-epoxypropyl alicyclic amines (tetraepoxypropylbisaminocyclohexane, etc.). The polyfunctional epoxy compound can be used alone or in combination of two or more.

Photopolymerizable compounds can be used alone or as a mixture of two or more. The content of the photopolymerizable compound is typically 10 to 300 parts by weight, preferably 30 to 200 parts by weight, and more preferably 40 to 150 parts by weight, per 100 parts by weight of the alkali-soluble resin. Furthermore, when the photosensitive resin composition contains a colorant, the content of the photopolymerizable compound is typically 10 to 1000 parts by weight, preferably 50 to 600 parts by weight, and more preferably 100 to 500 parts by weight, per 100 parts by weight of the colorant. A content of the photopolymerizable compound within this range ensures sufficient curing and good adhesion.

<Photopolymerization initiator>

In this disclosure, the photopolymerization initiator is not particularly limited, and examples thereof include photoradical polymerization initiators and photocationic polymerization initiators.

Photoradical polymerization initiators are compounds that generate free radicals upon exposure to light, initiating the curing reaction (free radical polymerization) of the photopolymerizable compound contained in the photosensitive resin composition. Photoradical polymerization initiators can be used alone or as a mixture of two or more.

Examples of photo-radical polymerization initiators include thiophenone compounds, acetophenone compounds, diimidazole compounds, tris(III) compounds, and compounds, oxime compounds, onium salt compounds, benzoin compounds, diphenyl ketone compounds, α-diketone compounds, polynuclear quinone compounds, diazo compounds, imidosulfonate compounds, anthracene compounds, etc.

Examples of the aforementioned thiothione compounds include thiothione, 2-chlorothiothione, 2-methylthiothione, 2-isopropylthiothione, 4-isopropylthiothione, 2,4-dimethylthiothione, 2,4-diethylthiothione, 2,4-diisopropylthiothione, 2,4-dichlorothiothione, and 1-chloro-4-propoxythiothione.

Examples of the acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzyldimethyl ketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-oxolinylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-oxolinylphenyl)butane-1-one, 2-(2-methylbenzyl)-2-dimethylamino-1-(4-oxolinylphenyl)-butanone, and 2-(3-methylbenzyl)-2-dimethylamino-1-(4-oxolinylphenyl)-butanone. , 2-(4-methylbenzyl)-2-dimethylamino-1-(4-fluoroquinoline phenyl)-butanone, 2-(2-ethylbenzyl)-2-dimethylamino-1-(4-fluoroquinoline phenyl)-butanone, 2-(2-propylbenzyl)-2-dimethylamino-1-(4-fluoroquinoline phenyl)-butanone, 2-(2-butylbenzyl)-2-dimethylamino-1-(4-fluoroquinoline phenyl)-butanone, 2-(2,3-dimethylbenzyl)-2-dimethylamino-1-(4-fluoroquinoline phenyl)-butanone, 2-(2,4-dimethylbenzyl)-2-dimethylamino-1-(4-fluoroquinoline phenyl)-butanone, 2-(2-chlorobenzyl)-2- dimethylamino-1-(4-fluoroquinolinephenyl)-butanone, 2-(2-bromobenzyl)-2-dimethylamino-1-(4-fluoroquinolinephenyl)-butanone, 2-(3-chlorobenzyl)-2-dimethylamino-1-(4-fluoroquinolinephenyl)-butanone, 2-(4-chlorobenzyl)-2-dimethylamino-1-(4-fluoroquinolinephenyl)-butanone, 2-(3-bromobenzyl)-2-dimethylamino-1-(4-fluoroquinolinephenyl)-butanone, 2-(4-bromobenzyl)-2-dimethylamino-1-(4-fluoroquinolinephenyl)-butanone, 2-(2-methoxybenzyl)-2-dimethylamino-1-(4-fluoroquinolinephenyl)-butanone, 2- (3-methoxybenzyl)-2-dimethylamino-1-(4-fluorinylphenyl)-butanone, 2-(4-methoxybenzyl)-2-dimethylamino-1-(4-fluorinylphenyl)-butanone, 2-(2-methyl-4-methoxybenzyl)-2-dimethylamino-1-(4-fluorinylphenyl)-butanone, 2-(2-methyl-4-bromobenzyl)-2-dimethylamino-1-(4-fluorinylphenyl)-butanone, 2-(2-bromo-4-methoxybenzyl)-2-dimethylamino-1-(4-fluorinylphenyl)-butanone, oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, etc.

Examples of the aforementioned diimidazole compounds include: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)diimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)diimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)diimidazole, and imidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboalkoxy groups.

The above three Examples of the compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-trichloromethane. , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-tri 、2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-tri , 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-〔2-(5-methylfuran-2-yl)vinyl〕-1,3,5-tri , 2,4-bis(trichloromethyl)-6-〔2-(furan-2-yl)vinyl〕-1,3,5-tri , 2,4-bis(trichloromethyl)-6-〔2-(4-diethylamino-2-methylphenyl)vinyl〕-1,3,5-tri , 2,4-bis(trichloromethyl)-6-〔2-(3,4-dimethoxyphenyl)vinyl〕-1,3,5-tri wait.

Examples of the aforementioned oxime compounds include O-ethoxycarbonyl-α-oxyimino-1-phenylpropane-1-one, etc.

Examples of the aforementioned benzoin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the aforementioned diphenyl ketone compounds include diphenyl ketone, methyl o-benzoylbenzoate, 4-phenyldiphenyl ketone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(tert-butylcarbonylperoxy)diphenyl ketone, and 2,4,6-trimethyldiphenyl ketone.

Examples of the anthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene.

The aforementioned photocatalytic polymerization initiator is a compound that generates acid upon exposure to light, initiating the curing reaction (cationic polymerization) of the photopolymerizable compound contained in the photosensitive resin composition. It consists of a cationic portion that absorbs light and an anionic portion that is an acid-generating source. Photocatalytic polymerization initiators can be used alone or in combination of two or more.

Examples of photocatalytic polymerization initiators include diazonium salt compounds, iodonium salt compounds, strontium salt compounds, phosphonium salt compounds, selenium salt compounds, Salt compounds, ammonium salt compounds, bromine salt compounds, etc.

Examples of the anionic portion of the photocatalytic polymerization initiator include: [(Y) _sB (Phf) _4-s ] ^- (wherein, Y represents a phenyl group or a biphenyl group, Phf represents a phenyl group in which at least one hydrogen atom is substituted by at least one selected from a perfluoroalkyl group, a perfluoroalkoxy group, and a halogen atom, and s is an integer from 0 ^to 3), _BF4- , [(Rf) _{kPF6 -k} ] ^- (Rf: an alkyl group in which at least 80% of the hydrogen atoms are substituted by fluorine atoms, k: an integer from ⁰ to 5 ⁾ , _AsF6- , _SbF6- , _SbF5OH- , ^etc.

Examples of the photocatalytic polymerization initiator include (4-hydroxyphenyl)methylbenzylcoppertris(pentafluorophenyl)borate, 4-(4-biphenylthio)phenyl-4-biphenylphenylcoppertris(pentafluorophenyl)borate, 4-(phenylthio)phenyldiphenylcoppertris(pentafluorophenyl)borate, [4-(4-biphenylthio)phenyl]-4-biphenylphenylcoppertris(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]coppertris(pentafluoroethyl)trifluorophosphate, diphenyl[4- (Phenylthio)phenyl]copper tetrakis(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]copper hexafluorophosphate, 4-(4-biphenylthio)phenyl-4-biphenylphenylcopper tris(pentafluoroethyl) trifluorophosphate, bis[4-(diphenyldihydrothio)phenyl]sulfide phenyl tris(pentafluorophenyl)borate, [4-(2-thiatonylthio)phenyl]phenyl-2-thiatonylcopper tris(pentafluorophenyl)borate, 4-(phenylthio)phenyldiphenylcopper hexafluoroantimonate, etc.

The following photopolymerization initiators can be used: CYRACURE UVI-6970, CYRACURE UVI-6974, CYRACURE UVI-6990, CYRACURE UVI-950 (all manufactured by Union Carbide, USA), Irgacure 250, Irgacure 261, Irgacure 264 (all manufactured by BASF), CG-24-61 (manufactured by Ciba-Geigy), OPTOMER SP-150, OPTOMER SP-151, OPTOMER SP-170, OPTOMER SP-171 (all manufactured by ADEKA Co., Ltd.), DAICAT II" (made by Daicel Co., Ltd.), "UVAC1590", "UVAC1591" (all made by Daicel-Cytec Co., Ltd.), "CI-2064", "CI-2639", "CI-2624", "CI-2481", "CI-2734", "CI-2855", "CI-2823", "CI-2758", "CIT-1682" (all made by Japan Soda Co., Ltd. Co., Ltd.), "PI-2074" (tetrakis(pentafluorophenyl)borate toluene methyl isopropyl iodide, manufactured by Rhodia), "FFC509" (manufactured by 3M), "BBI-102", "BBI-101", "BBI-103", "MPI-103", "TPS-103", "MDS-103", "DTS-103", "NAT-103", "NDS-103" (all manufactured by Midori Kagaku Co., Ltd.), "CD-1010", "CD-1011", "CD-1012" (all manufactured by Sartomer, USA), "CPI-100P", "CPI-101A" (all manufactured by San-Apro Co., Ltd.), etc.

The photopolymerization initiator content (the total amount when two or more types are present) is preferably, for example, 0.1 to 100 parts by weight, more preferably 0.5 to 50 parts by weight, and even more preferably 3 to 20 parts by weight, per 100 parts by weight of the total photopolymerizable compound contained in the photosensitive resin composition. When the photopolymerization initiator content is below this range, curability tends to be reduced. On the other hand, when the photopolymerization initiator content is above this range, the cured product tends to be easily colored.

<Solvent>

Examples of the solvent include ethers (chain ethers such as diethyl ether; glycol ethers such as ethylene glycol mono- or dialkyl ether, diethylene glycol mono- or dialkyl ether, propylene glycol mono- or dialkyl ether, propylene glycol mono- or diaryl ether, dipropylene glycol mono- or dialkyl ether, tripropylene glycol mono- or dialkyl ether, 1,3-propylene glycol mono- or dialkyl ether, 1,3-butanediol mono- or dialkyl ether, 1,4-butanediol mono- or dialkyl ether, glycerol mono- or di- or trialkyl ether; cyclic ethers such as tetrahydrofuran and dioxane), esters (methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, C _5-6 cycloalkanediol mono- or diacetate, C Carboxylic acid esters such as _5-6 -cycloalkane dimethanol mono- or diacetate; ethylene glycol monoalkyl ether acetate, ethylene glycol mono- or diacetate, diethylene glycol monoalkyl ether acetate, diethylene glycol mono- or diacetate, propylene glycol monoalkyl ether acetate, propylene glycol mono- or diacetate, dipropylene glycol monoalkyl ether acetate, dipropylene glycol mono- or diacetate, 1,3-propylene glycol monoalkyl ether acetate, 1,3-propylene glycol mono- or diacetate, 1,3-butanediol monoalkyl ether acetate, 1,3-butanediol mono- or diacetate, 1,4-butanediol monoalkyl ether acetate, 1,4-butanediol mono- or diacetate, glycerol mono- or di- or triacetate, glycerol mono- or di-C _These solvents may be used alone or in combination of two or more.

In addition to the above-mentioned ingredients, the photosensitive resin composition disclosed herein may contain, for example: resins such as novolac resins, phenol resins, imide resins, and carboxyl-containing resins; hardeners, hardening accelerators, and additives (fillers, defoaming agents, flame retardants, antioxidants, UV absorbers, colorants, stress reducers, mobility enhancers, waxes, resins, crosslinking agents, halogen scavengers, leveling agents, and wettability modifiers).

The concentration of the alkali-soluble resin in the photosensitive resin composition disclosed herein is not particularly limited, and may be, for example, 2 to 60% by weight, preferably 5 to 30% by weight.

The preparation method of the photosensitive resin composition disclosed herein can be exemplified by dissolving an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and other required additives in a solvent.

When the photosensitive resin composition disclosed herein contains a colorant, the preparation method may include, for example, dispersing the pigment or other colorant in a solvent, if necessary, along with a pigment dispersant, to prepare a colorant dispersion. An alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and other additives, if necessary, are then dissolved in the solvent, mixed with the colorant dispersion, and further solvent is added as needed.

The photosensitive resin composition disclosed herein is typically sealed in a container for distribution and storage. The photosensitive resin composition disclosed herein exhibits excellent storage stability during distribution and storage.

<Hardened Material>

By curing the photosensitive resin composition disclosed herein, a cured product with excellent physical properties can be obtained. For example, the photosensitive resin composition can be applied to various substrates or bases using conventional coating methods such as rotary coaters, dip coaters, roll coaters, or slit coaters to form a coating film, which is then cured to obtain a cured product. Curing is performed, for example, by irradiating the photosensitive resin composition with light and/or applying heat.

The light irradiation may be carried out using, for example, a mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, sunlight, an electron beam source, a laser light source, or an LED light source. Preferably, the light irradiation is carried out at a cumulative dose of, for example, 500 to 5000 mJ/ ^cm2 .

The aforementioned heat treatment is preferably performed at a temperature of 60 to 300°C (preferably 100 to 250°C) for, for example, 1 to 120 minutes (preferably 1 to 60 minutes).

Examples of substrates include silicon wafers, metals, plastics, glass, and ceramics. The thickness of the coating after curing is preferably 0.05 to 20 μm, more preferably 0.1 to 10 μm.

The cured product (the cured coating) disclosed herein has excellent solvent resistance and high insulation properties, and can therefore be used as a protective film (such as a color filter protective film), an insulating film, or a material for forming microlenses.

<Color filter>

The color filter disclosed herein is a cured product of the photosensitive resin composition disclosed herein. The color filter disclosed herein may include a colored pattern formed from the photosensitive resin composition. The color filter can be manufactured, for example, by forming the colored pattern on a substrate using the photosensitive resin composition and then post-baking the colored pattern.

Methods for forming color filter patterns using the photosensitive resin composition disclosed herein include, for example, applying the photosensitive resin composition disclosed herein to a substrate or other resin layer using a conventional coating method such as a rotary coater, removing volatile components such as solvents to form a coloring layer, and then exposing the coloring layer through a photomask for development.

Examples of substrates include glass substrates, polysilicon substrates, polycarbonate substrates, polyester substrates, aromatic polyamide substrates, polyamide imide substrates, polyimide substrates, Al substrates, GaAs substrates, and other flat substrates. These substrates can undergo pre-treatments such as chemical treatment using silane coupling agents, plasma treatment, ion plating, sputtering, gas phase reaction, and vacuum evaporation.

The thickness of the coloring layer after drying is, for example, 0.6 to 8 μm, preferably 1 to 5 μm.

Radiation sources used during exposure include, for example, xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, or laser sources such as argon lasers, YAG lasers, XeCl excimer lasers, and nitrogen lasers. The wavelength of the radiation is preferably in the range of 190 to 450 nm. The radiation exposure dose is generally preferably 10 to 10,000 J/ ^m² .

The alkaline developer used for development is preferably an aqueous solution of sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene, etc.

Post-baking conditions are typically 120 to 280°C for 10 to 60 minutes. The resulting pixel thickness is typically 0.5 to 5 μm, preferably 1 to 3 μm.

The photosensitive resin composition disclosed herein can produce colored patterns with excellent curing reactivity and sufficient solvent resistance.

<Display device component or display device>

The display device component or display device disclosed herein includes the aforementioned color filter. An example of the display device component is a color liquid crystal display element. Furthermore, an example of the display device is a color liquid crystal display device. The structure of the color liquid crystal display element or color liquid crystal display is not particularly limited and may be any appropriate structure.

Furthermore, the various aspects disclosed in this specification may be combined with any other features disclosed in this specification. Furthermore, the various components and combinations in each embodiment are merely examples, and additions, omissions, and other modifications may be made as appropriate without departing from the spirit of the present invention. This disclosure is not limited to the embodiments and is subject to the scope of the patent application.

(Example)

The present disclosure is further described below with reference to the following examples.

The weight average molecular weight (polystyrene equivalent) and dispersity (weight average molecular weight Mw/number average molecular weight Mn) of the copolymer were measured using the following conditions.

Device: Detector: RID-20A (Shimadzu Corporation).

Pump: LC-20AD (Shimadzu Corporation).

System controller: CBM-20Alite (Shimadzu Corporation).

Degasser: DGU-20A3 (Shimadzu).

Auto-injector: SIL-20A HT (Shimadzu).

Pipe string: Shodex KF-806L (Showa Denko).

Eluent: THF (tetrahydrofuran) 0.8 ml/min.

Temperature: Oven: 40°C, RI: 40°C.

Detector: RI.

The exothermic peak temperature was measured using the following method. Specifically, 5 g of the copolymer-containing solution obtained in Preparation Examples 1 to 8 was added dropwise to 50 g of heptane while stirring. The resulting precipitate was filtered and dried under reduced pressure to obtain the copolymer as a white powder. Approximately 10 mg of the white powder was used as a sample and heated from 40°C to 300°C at a rate of 5°C/minute in a nitrogen atmosphere using a differential scanning calorimeter (DSC1 manufactured by METTLER TOLEDO). The exothermic peak temperature was measured.

[Reference Example 1/Production of Monomer B1]

To a mixed solution of 33.7 g of 5-norbornene-2-methanol, 41.3 g of triethylamine, and 6.5 mg of hydroquinone monomethyl ether in 57.2 g of THF (tetrahydrofuran), 42.4 g of methacrylic acid chloride was added dropwise over 40 minutes while maintaining the internal temperature below 20°C. The mixture was then stirred at 20°C for 4 hours. After gas chromatography confirmed the disappearance of the raw material 5-norbornene-2-methanol, 100 g of ethereal acetate and 84.0 g of water were added. After separation, the mixture was washed with 94.8 g of a 10% aqueous sodium hydroxide solution and then three times with 68.0 g of water. The resulting organic phase was concentrated at 40°C and 15 Torr to yield 48.3 g of crude 5-norbornene-2-methacrylate. The purity of the crude product was 93%, and the yield was 86%.

To a mixed solution of 47.5 g of the crude 5-norbornene-2-methacrylate product and 9.4 mg of hydroquinone monomethyl ether in 141 g of ethyl acetate was added 72.3 g of mCPBA (3-chloroperoxybenzoic acid, 30% aqueous solution) over one hour while maintaining the internal temperature below 20°C. The mixture was then stirred at 20°C for three hours. After confirming the disappearance of the starting materials by gas chromatography, 278 g of a 15% aqueous sodium thiosulfate solution and 141 g of ethereal acetate were added and stirred for 15 minutes. After separation, the mixture was washed with 217 g of an 8% aqueous sodium bicarbonate solution and twice with 141 g of water. The organic phase was concentrated and purified by silica gel column chromatography to obtain 29.4 g of 3-oxatricyclo[3.2.1.0 ^2,4 ]octan-6-yl methyl methacrylate (hereinafter referred to as "Monomer B1"). The purity of 3-oxatricyclo[3.2.1.0 ^2,4 ]octan-6-yl methyl methacrylate was 99%, and the yield was 71%.

[Manufacturing Example 1]

A nitrogen atmosphere was created by properly circulating nitrogen through a 1L flask equipped with a reflux cooler, dropping funnel, and stirrer. 150 parts by weight of propylene glycol monomethyl ether acetate was added to the flask and heated to 80°C while stirring. Subsequently, 7 parts by weight of 2,2'-azobisisobutyronitrile (AIBN) was added while washing with 30 parts by weight of propylene glycol monomethyl ether acetate. Subsequently, a mixed solution of 11 parts by weight of acrylic acid (AA) as a monomer, 89 parts by weight of monomer B1, and 20 parts by weight of propylene glycol monomethyl ether acetate was dripped into the flask using a drip pump over approximately 4 hours. After the monomer addition was completed, the mixture was maintained at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer solution with a solids content of 34.6% by weight. The resulting copolymer had a weight-average molecular weight (Mw) of 19,000 and a dispersity of 3.47.

[Manufacturing example 2]

The same procedures as in Preparation Example 1 were followed, except that 11 parts by weight of acrylic acid (AA), 79 parts by weight of monomer B1, and 10 parts by weight of styrene (ST) were used as monomers. A solution containing a copolymer with a solids content of 33.8% by weight was obtained. The resulting copolymer had a weight-average molecular weight (Mw) of 17,000 and a dispersity of 3.33.

[Manufacturing Example 3]

The same procedures as in Preparation Example 1 were followed, except that 11 parts by weight of acrylic acid (AA), 79 parts by weight of monomer B1, and 10 parts by weight of methyl methacrylate (MMA) were used as monomers. A solution containing a copolymer with a solids content of 34.2% by weight was obtained. The resulting copolymer had a weight-average molecular weight (Mw) of 18,500 and a dispersity of 3.41.

[Manufacturing Example 4]

The same procedures as in Preparation Example 1 were followed, except that 11 parts by weight of acrylic acid (AA), 79 parts by weight of monomer B1, and 10 parts by weight of cyclohexyl cis-butylene diimide (CHMI) were used as monomers. A copolymer solution with a solids content of 34.4% by weight was obtained. The resulting copolymer had a weight-average molecular weight (Mw) of 18,000 and a dispersity of 3.40.

[Manufacturing Example 5]

The same procedures as in Preparation Example 1 were followed, except that 11 parts by weight of acrylic acid (AA), 79 parts by weight of monomer B1, and 10 parts by weight of N-vinylpyrrolidone (VP) were used as monomers. A solution containing a copolymer having a solids content of 34.4% by weight was obtained. The resulting copolymer had a weight-average molecular weight (Mw) of 17,500 and a dispersity of 3.38.

[Manufacturing Example 6]

A nitrogen atmosphere was created by flowing nitrogen through a 1L flask equipped with a reflux cooler, dropping funnel, and stirrer. 150 parts by weight of propylene glycol monomethyl ether acetate was added and heated to 65°C while stirring. 14 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) was then added while washing with 30 parts by weight of propylene glycol monomethyl ether acetate. A solution of 11 parts by weight of acrylic acid (AA), 79 parts by weight of glycidyl methacrylate (GMA), and 10 parts by weight of methyl methacrylate (MMA) dissolved as monomers in 20 parts by weight of propylene glycol monomethyl ether acetate was then added dropwise to the flask using a drip pump over approximately 4 hours. After the monomer addition was completed, the mixture was maintained at the same temperature for approximately 4 hours and then cooled to room temperature to obtain a copolymer solution with a solids content of 33.8% by weight. The resulting copolymer had a weight-average molecular weight (Mw) of 16,000 and a dispersity of 3.32.

[Manufacturing Example 7]

The same procedures as in Preparation Example 6 were followed, except that 11 parts by weight of acrylic acid (AA), 79 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate (Cyclomer M100), and 10 parts by weight of methyl methacrylate (MMA) were used as monomers. A solution containing a copolymer with a solid content of 33.4% by weight was obtained. The resulting copolymer had a weight-average molecular weight (Mw) of 16,000 and a dispersity of 3.30.

[Manufacturing Example 8]

The same procedures as in Preparation Example 1 were followed, except that 11 parts by weight of acrylic acid (AA) and 89 parts by weight of a mixture of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-9-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate (Monomer B2) were used as monomers. A solution containing a copolymer having a solid content of 34.1% by weight was obtained. The resulting copolymer had a weight-average molecular weight (Mw) of 18,000 and a dispersity of 3.43.

The copolymer compositions, weight-average molecular weights, dispersities, and exothermic peak temperatures of Preparation Examples 1 to 8 are shown in Table 1.

[Example 1-1]

Into a container, 8.09 g of a copolymer solution prepared from the copolymer obtained in Preparation Example 1 above, as an alkali-soluble resin, 2.25 g of DPHA as a photopolymerizable compound, 0.20 g of 1-hydroxycyclohexylphenyl ketone as a photopolymerization initiator, and 6.83 g of MMPGAC as a solvent were weighed and stirred for 30 minutes to prepare a photosensitive resin composition 1-1.

[Example 1-2]

Photosensitive resin composition 1-2 was prepared by following the same procedures as in Example 1-1, except that 8.09 g of the copolymer solution prepared from the copolymer obtained in Preparation Example 2 was used as the alkali-soluble resin.

[Example 1-3]

Photosensitive resin composition 1-3 was prepared by following the same procedures as in Example 1-1, except that 8.09 g of the copolymer solution prepared from the copolymer obtained in Preparation Example 3 was used as the alkali-soluble resin.

[Example 1-4]

Photosensitive resin composition 1-4 was prepared by following the same procedures as in Example 1-1, except that 8.09 g of the copolymer solution prepared from the copolymer obtained in Preparation Example 4 was used as the alkali-soluble resin.

[Example 1-5]

Photosensitive resin composition 1-5 was prepared by following the same procedures as in Example 1-1, except that 8.09 g of the copolymer solution prepared from the copolymer obtained in Preparation Example 5 was used as the alkali-soluble resin.

[Comparative Example 1-1]

Photosensitive resin composition 1-6 was prepared by following the same procedures as in Example 1-1, except that 8.09 g of the copolymer solution prepared from the copolymer obtained in Preparation Example 6 was used as the alkali-soluble resin.

[Comparative Example 1-2]

Photosensitive resin composition 1-7 was prepared by following the same procedures as in Example 1-1, except that 8.09 g of the copolymer solution prepared from the copolymer obtained in Preparation Example 7 was used as the alkali-soluble resin.

[Comparative Example 1-3]

Photosensitive resin composition 1-8 was prepared by following the same procedures as in Example 1-1, except that 8.09 g of the copolymer solution prepared from the copolymer obtained in Preparation Example 8 was used as the alkali-soluble resin.

Table 2 shows the composition of the photosensitive resin compositions of the above Examples and Comparative Examples.

[Example 2-1]

In a container, weigh 7.7 g of C.I. Pigment Red 254 (pigment), 3.1 g of DISPERBYK-2000 (dispersant), and 36.0 g of MMPGAC (solvent). Add 45 g of 1.0 mm diameter zirconium dioxide beads and cap. Shake the mixture with a paint shaker for 3 hours. After 3 hours, separate the pigment dispersion and zirconium dioxide beads. Add 45 g of 0.5 mm diameter zirconium dioxide beads and shake the mixture with a paint shaker for another 3 hours. The pigment dispersion and zirconium dioxide beads were then separated. 45 g of 0.3 mm zirconium dioxide beads were added and the mixture was further shaken for 3 hours using a paint mixer. The zirconium dioxide beads were then separated to obtain the pigment dispersion.

To 4.68 g of the resulting pigment dispersion, 8.09 g of a copolymer solution prepared from the copolymer obtained in Preparation Example 1 above (alkaline-soluble resin), 2.25 g of DPHA (photopolymerizable compound), 0.20 g of 1-hydroxycyclohexylphenyl ketone (photopolymerization initiator), and 15.2 g of MMPGAC (solvent) were measured and stirred for 30 minutes to prepare photosensitive resin composition 2-1.

[Example 2-2]

Photosensitive resin composition 2-2 was prepared by following the same procedures as in Example 2-1, except that 8.09 g of the copolymer solution prepared from the copolymer obtained in Preparation Example 2 was used as the alkali-soluble resin.

[Example 2-3]

Photosensitive resin composition 2-3 was prepared by following the same procedures as in Example 2-1, except that 8.09 g of the copolymer solution prepared from the copolymer obtained in Preparation Example 3 was used as the alkali-soluble resin.

[Example 2-4]

Photosensitive resin composition 2-4 was prepared by following the same procedures as in Example 2-1, except that 8.09 g of the copolymer solution prepared from the copolymer obtained in Preparation Example 4 was used as the alkali-soluble resin.

[Example 2-5]

Photosensitive resin composition 2-5 was prepared by following the same procedures as in Example 2-1, except that 8.09 g of the copolymer solution prepared from the copolymer obtained in Preparation Example 5 was used as the alkali-soluble resin.

[Comparative Example 2-1]

Photosensitive resin composition 2-6 was prepared by following the same procedures as in Example 2-1, except that 8.09 g of the copolymer solution prepared from the copolymer obtained in Preparation Example 6 was used as the alkali-soluble resin.

[Comparative Example 2-2]

Photosensitive resin composition 2-7 was prepared by following the same procedures as in Example 2-1, except that 8.09 g of the copolymer solution prepared from the copolymer obtained in Preparation Example 7 was used as the alkali-soluble resin.

[Comparative Example 2-3]

Photosensitive resin composition 2-8 was prepared by following the same procedures as in Example 2-1, except that 8.09 g of the copolymer solution prepared from the copolymer obtained in Preparation Example 8 was used as the alkali-soluble resin.

Table 4 shows the composition of the photosensitive resin compositions of the above Examples and Comparative Examples.

<Evaluation Test>

The following evaluation tests were conducted using the photosensitive resin compositions obtained in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-3. The results are shown in Table 3.

(1) Storage stability test-1

The photosensitive resin compositions obtained in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-3 were stored in an oven at 40°C for one week. The viscosity after polymerization and after storage at 40°C for one week were measured. The viscosity increase rate was calculated using the following formula. Viscosity (unit: mPa·s) was measured using a viscometer (trade name "LVDV2T", manufactured by Brookfield) at 60 rpm and 23°C.

P: viscosity after polymerization, Q: viscosity after storage at 40°C for one week.

Viscosity increase rate = {(Q/P) × 100} - 100.

(2)Solvent resistance test-1

The photosensitive resin compositions obtained in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-3 were applied to a glass plate using a rotary applicator and then cured at 200°C for 30 minutes to produce test pieces. The thickness of the cured coating was 3 μm.

A test piece was dripped with one drop each of γ-butyrolactone (γ-BL) and N-methylpyrrolidone (NMP) and allowed to stand for 10 minutes. After rinsing with water, the area where the solvent was dripped showed no change (◎), a slight trace of solvent remained but disappeared after wiping (○), a trace of solvent remained that could not be wiped off (△), and a complete discoloration was marked as ×.

(3)Solvent resistance test-2

The cured product was tested for solvent resistance in the same manner as in Solvent Resistance Test-1, except that the curing temperature was set at 230°C.

The photosensitive resin compositions of Examples 1-1 to 1-5 showed little viscosity increase even at 40°C, demonstrating excellent storage stability. Furthermore, even at a curing temperature of 200°C, they exhibited the same good solvent resistance as at 230°C. On the other hand, the photosensitive resin compositions of Comparative Examples 1-1 and 1-2 gelled at 40°C, indicating poor storage stability. Furthermore, the photosensitive resin composition of Comparative Example 3 exhibited excellent storage stability due to the use of monomer B2 (EDCPA), but did not fully cure when the curing temperature was lowered from 230°C to 200°C, indicating a decrease in solvent resistance.

Next, the following evaluation tests were conducted using the photosensitive resin compositions obtained in Examples 2-1 to 2-5 and Comparative Examples 2-1 to 2-3. The results are shown in Table 5.

(1) Storage stability test-2

The photosensitive resin compositions obtained in Examples 2-1 to 2-5 and Comparative Examples 2-1 to 2-3 were stored in an oven at 40°C for one week. The viscosity after polymerization and after storage at 40°C for one week were measured. The viscosity increase rate was calculated using the following formula. Viscosity (unit: mPa·s) was measured using a viscometer (trade name "LVDV2T", manufactured by Brookfield) at 60 rpm and 23°C.

P: viscosity after polymerization, Q: viscosity after storage at 40°C for one week.

Viscosity increase rate = {(Q/P) × 100} - 100.

(2)Solvent resistance test-3

The photosensitive resin compositions obtained in Examples 2-1 to 2-5 and Comparative Examples 2-1 to 2-3 were applied to a glass plate using a rotary applicator and then cured at 200°C for 30 minutes to produce test pieces. The thickness of the cured coating was 2 μm.

A test piece was dripped with one drop each of γ-butyrolactone (γ-BL) and N-methylpyrrolidone (NMP) and allowed to stand for 10 minutes. After rinsing with water, the area where the solvent was dripped showed no change (◎), a slight trace of solvent remained but disappeared after wiping (○), a trace of solvent remained that could not be wiped off (△), and a complete discoloration was marked as ×.

(3)Solvent resistance test-4

The cured product was tested for solvent resistance in the same manner as in Solvent Resistance Test-3, except that the curing temperature was set at 230°C.

The photosensitive resin compositions of Examples 2-1 to 2-5 showed little viscosity increase even at 40°C, demonstrating excellent storage stability. Furthermore, even at a curing temperature of 200°C, they exhibited the same good solvent resistance as at 230°C. On the other hand, the photosensitive resin compositions of Comparative Examples 2-1 and 2-2 showed increased viscosity at 40°C, indicating poor storage stability. Furthermore, the photosensitive resin composition of Comparative Example 2-3 exhibited excellent storage stability due to the use of monomer B2 (EDCPA), but did not fully cure when the curing temperature was lowered from 230°C to 200°C, indicating a decrease in solvent resistance.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

The following describes the components used in the preparation examples, working examples, and comparative examples.

Monomer B1: 3-oxatricyclo[3.2.1.0 ^2,4 ]octan-6-yl methyl methacrylate (see Reference Example 1).

GMA: Glycidyl methacrylate (manufactured by NOF Corporation).

Cyclomer M100: 3,4-Epoxycyclohexylmethyl methacrylate (manufactured by Daicel Co., Ltd.).

Monomer B2: A mixture of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-9-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-yl acrylate (trade name "E-DCPA", manufactured by Daicel Co., Ltd.).

ST: Styrene (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.).

MMA: Methyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.).

CHMI: Cyclohexyl cis-butenedimide (manufactured by Nippon Catalyst Co., Ltd.).

VP: N-vinylpyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.).

MMPGAC: Propylene glycol monomethyl ether acetate (manufactured by Daicel Co., Ltd.).

PR 254: C.I. Pigment Red 254 (manufactured by Tokyo Chemical Industry Co., Ltd.).

DISPERBYK-2000: Amine value 4 mgKOH/g, non-volatile matter 40% (manufactured by BYK Japan).

DHPA: Dipentatritol hexaacrylate (trade name "KAYARAD DPHA"; manufactured by Nippon Kayaku Co., Ltd.).

1-Hydroxycyclohexylphenyl ketone (manufactured by FUJIFILM Wako Junyaku Co., Ltd.).

In summary, the following notes the structure and variations of this invention.

[1] A photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein:

The alkali-soluble resin is a copolymer containing a constituent unit (A) derived from an unsaturated carboxylic acid or its anhydride and a constituent unit (B) derived from a compound represented by the aforementioned formula (1), and exhibiting a heating peak temperature of 180 to 220°C when heated at a rate of 5°C/min using a differential scanning calorimeter.

(In the formula, ^R1 and ^R2 are the same or different and represent a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, X represents a single bond or a divalent hydrocarbon group which may contain a heteroatom, Y represents a methylene or ethylene group which may have an alkyl group having 1 to 3 carbon atoms as a substituent, an oxygen atom, or a sulfur atom which may be bonded to an oxygen atom, and n represents an integer from 0 to 7).

[2] The photosensitive resin composition as described in [1], wherein the compound represented by the aforementioned formula (1) is the compound represented by the aforementioned formula (1a)

(wherein, R ¹ , R ² , X, Y, and n are the same as those described in formula (1)).

[3] The photosensitive resin composition as described in [1] or [2], wherein the copolymer further contains a constituent unit (C) derived from at least one compound selected from the group consisting of (c1) to (c4) below,

(c1) Styrene which may be substituted with an alkyl group;

(c2) N-substituted cis-butylenediamide;

(c3) N-vinyl compounds;

(c4) the unsaturated carboxylic acid derivative represented by the aforementioned formula (2);

(In the formula, R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. R ¹² represents a alkyl group which may contain a heteroatom. Z represents a heteroatom.)

[4] The photosensitive resin composition as described in any one of [1] to [3], wherein the copolymer further contains a constituent unit (D), and the constituent unit (D) is a constituent unit derived from (meth)acrylamide or (meth)acrylonitrile.

[5] The photosensitive resin composition as described in any one of [1] to [4], wherein the proportion of the constituent unit (A) relative to the total constituent units of the copolymer is 2 to 60% by weight, 3 to 40% by weight, or 5 to 20% by weight.

[6] The photosensitive resin composition as described in any one of [1] to [5], wherein the proportion of the constituent unit (B) relative to the total constituent units of the copolymer is 40 to 98 wt%, 60 to 95 wt%, or 75 to 90 wt%.

[7] The photosensitive resin composition as described in any one of [3], [5], and [6], wherein the ratio of the constituent unit (C) relative to the total constituent units of the copolymer is 0 to 85% by weight, 1 to 60% by weight, or 2 to 40% by weight.

[8] The photosensitive resin composition as described in any one of [3], [5] to [7], wherein the proportion of the constituent unit (A) is 2 to 60% by weight, the content of the constituent unit (B) is 40 to 98% by weight, and the content of the constituent unit (C) is 0 to 85% by weight, relative to the total constituent units of the copolymer.

[9] The photosensitive resin composition according to any one of [1] to [8], wherein the copolymer contains the constituent units (A) and (B) and does not contain the constituent unit (C), and the total amount of the constituent units (A) and (B) relative to the total constituent units is 90% by weight or more, 95% by weight or more, 99% by weight or more, or substantially 100% by weight; and the copolymer contains the constituent units (A), (B) and (C), and the total amount of the constituent units (A) to (C) relative to the total constituent units is 90% by weight or more, 95% by weight or more, 99% by weight or more, or 100% by weight.

[10] The photosensitive resin composition according to any one of [1] to [9], wherein the weight average molecular weight (Mw) of the copolymer is 1,000 to 1,000,000, 3,000 to 300,000, or 5,000 to 100,000.

[11] The photosensitive resin composition according to any one of [1] to [10], wherein the molecular weight distribution (ratio of weight average molecular weight to number average molecular weight: Mw/Mn) of the copolymer is 5.0 or less, 1.0 to 4.5, or 1.0 to 4.0.

[12] The photosensitive resin composition as described in any one of [1] to [11], wherein the polymer exhibits a peak exothermic temperature of 180 to 220°C when heated at a rate of 5°C/min using a differential scanning calorimeter.

[13] The photosensitive resin composition as described in any one of [1] to [12] further contains a colorant.

[14] The photosensitive resin composition as described in [13], wherein the colorant is a pigment and/or dye.

[15] The photosensitive resin composition as described in [13] or [14], wherein the colorant content is 3 to 50% by weight or 5 to 30% by weight relative to the solid content of the photosensitive resin composition.

[16] The photosensitive resin composition according to any one of [1] to [15], wherein the photopolymerizable compound contains at least one selected from the group consisting of a polyfunctional vinyl compound, a polyfunctional thiol compound, and a polyfunctional epoxy compound.

[17] The photosensitive resin composition according to any one of [1] to [16], wherein the content of the photopolymerizable compound is 10 to 300 parts by weight, 30 to 200 parts by weight, or 40 to 150 parts by weight relative to 100 parts by weight of the alkali-soluble resin, and when the photosensitive resin composition contains a colorant, the content of the photopolymerizable compound is 10 to 1000 parts by weight, 50 to 600 parts by weight, or 100 to 500 parts by weight relative to 100 parts by weight of the colorant.

[18] A cured product of the photosensitive resin composition described in any one of [1] to [17].

[19] A color filter, which is a hardened product of the photosensitive resin composition described in any one of [1] to [17].

[20] A component for a display device or a display device, comprising the color filter described in [19].

(Industrial Availability)

The present invention provides a photosensitive resin composition with excellent storage stability, excellent curing reactivity, and excellent solvent resistance of the cured product. Furthermore, a cured product of the photosensitive resin composition having the aforementioned properties, a color filter formed from the cured product, and a display device component or display device incorporating the color filter can be provided.

Claims (8)

A photosensitive resin composition comprises an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the alkali-soluble resin is a copolymer comprising a constituent unit (A) derived from an unsaturated carboxylic acid or its anhydride and a constituent unit (B) derived from a compound represented by the following formula (1), and exhibiting a peak exothermic temperature of 180 to 220°C when heated at a rate of 5°C/min using a differential scanning calorimeter. The content of the constituent unit (A) is 3 to 40% by weight, and the content of the constituent unit (B) is 60 to 95% by weight, relative to the total constituent units of the copolymer. (In the formula, ^R1 and ^R2 are the same or different and represent a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, X represents a single bond or a divalent hydrocarbon group which may contain a heteroatom, Y represents a methylene or ethylene group which may have an alkyl group having 1 to 3 carbon atoms as a substituent, an oxygen atom, or a sulfur atom which may be bonded to an oxygen atom, and n represents an integer from 0 to 7). The photosensitive resin composition of claim 1, wherein the copolymer further comprises a constituent unit (C) derived from at least one compound selected from the group consisting of (c1) to (c4) below: (c1) styrene which may be substituted with an alkyl group; (c2) an N-substituted cis-butylenediimide; (c3) an N-vinyl compound; and (c4) an unsaturated carboxylic acid derivative represented by the following formula (2). (In the formula, R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, R ¹² represents a alkyl group which may contain a heteroatom, and Z represents a heteroatom). The photosensitive resin composition as described in claim 2, wherein the ratio of the aforementioned constituent unit (C) relative to the total constituent units of the aforementioned copolymer is 1 to 85% by weight. The photosensitive resin composition as described in claim 1 or 2 further contains a colorant. The photosensitive resin composition as described in claim 4, wherein the colorant is a pigment and/or dye. A cured product of the photosensitive resin composition described in claim 1 or 2. A color filter, which is a cured product of the photosensitive resin composition described in claim 1 or 2. A display device component or a display device comprising the color filter described in claim 7.