Photosensitive resin composition, cured product, color filter, member for display device, and display device

Abstract

The present application provides a photosensitive resin composition which is excellent in storage stability, and which is excellent in curing reactivity and in solvent resistance of a cured product. A photosensitive resin composition comprising: an alkali-soluble resin which is a copolymer containing a constitutional unit (A) derived from an unsaturated carboxylic acid or an acid anhydride thereof and a constitutional unit (B) derived from a compound represented by the following formula (1) (in the formula, R 1 and R 2 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 optionally having an alkyl group having 1 to 3 carbon atoms as a substituent, etc. n represents an integer of 0 to 7), wherein the alkali-soluble resin is a copolymer having an exothermic peak top temperature of 180 to 220°C when temperature is increased at a rate of 5°C / minute using a differential scanning calorimeter.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to a photosensitive resin composition, a cured product, a color filter, a member for a display device, and a display device. This application claims priority to Japanese Patent Application Nos. 2020-039964 and 2020-039965 filed in Japan on March 9, 2020, the contents of which are hereby incorporated by reference. BACKGROUND

[0002] As a photosensitive resin composition used when manufacturing an insulating film, a color filter, a color filter protective film, a microlens, there are known a resin composition containing an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator, a resin composition further containing a colorant (pigment, dye).

[0003] In Patent Literature 1 and Patent Literature 4, as the alkali-soluble resin, a copolymer containing methacrylic acid and glycidyl methacrylate as constituent monomers is disclosed. In Patent Literature 2 and Patent Literature 5, as the alkali-soluble resin, a copolymer containing methacrylic acid and 3,4-epoxytricyclo[5.2.1.04 2,6 ]decyl acrylate as constituent monomers is disclosed. In Patent Literature 3, as the alkali-soluble resin, a copolymer containing methacrylic acid and benzyl methacrylate as constituent monomers is disclosed.

[0004] PRIOR ART DOCUMENTS

[0005] PATENT LITERATURE

[0006] Patent Literature 1: Japanese Patent Application Publication No. H11-133600

[0007] Patent Literature 2: Japanese Patent Application Publication No. 2006-171160

[0008] Patent Literature 3: Japanese Patent Application Publication No. H9-134004

[0009] Patent Literature 4: Japanese Patent Application Publication No. 2011-237728

[0010] Patent Literature 5: Japanese Patent Application Publication No. 2007-333847 SUMMARY

[0011] PROBLEMS TO BE SOLVED BY THE INVENTION

[0012] However, the photosensitive resin compositions disclosed in Patent Literature 1 and Patent Literature 4 have a drawback of low stability such as thickening over time. Further, the solvent resistance of the cured product is also insufficient. The photosensitive resin compositions disclosed in Patent Literature 2 and Patent Literature 5 are excellent in storage stability, but have poor reactivity with carboxylic acids, and require a curing temperature of 230°C or higher. The photosensitive resin composition disclosed in Patent Literature 3 has a drawback of low solvent resistance of the cured product.

[0013] Therefore, an object of the present disclosure is to provide a photosensitive resin composition which is excellent in storage stability, and which is excellent in curing reactivity and solvent resistance of the cured product.

[0014] Further, another object of the present disclosure is to provide a cured product of the photosensitive resin composition having the above-described properties, a color filter as the cured product, and a display device member or display device provided with the color filter.

[0015] Technical Solution

[0016] The present inventors have conducted intensive studies in order to achieve the above-described objects, and as a result, have found that according to a photosensitive resin composition using, as an alkali-soluble resin, a copolymer containing a specific constitutional unit, and having an exothermic peak top temperature of 180 to 220°C, the storage stability is excellent, curing proceeds even at a low temperature, and the solvent resistance of the cured product is excellent. The present disclosure is based on these insights.

[0017] That is, the present disclosure provides a photosensitive resin composition containing:

[0018] an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent,

[0019] The alkali-soluble resin is a copolymer containing a constitutional unit (A) derived from an unsaturated carboxylic acid or an acid anhydride thereof, and a constitutional unit (B) derived from a compound represented by the following formula (1),

[0020] [Chemical Formula 1]

[0021]

[0022] (In the formula, R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. X represents a single bond or a divalent hydrocarbon group optionally containing a hetero atom. Y represents a methylene group or an ethylene group optionally having an alkyl group having 1 to 3 carbon atoms as a substituent, an oxygen atom, or a sulfur atom optionally bonded to an oxygen atom. n represents an integer of 0 to 7),

[0023] wherein the alkali-soluble resin is a copolymer having an exothermic peak top temperature of 180 to 220°C when temperature is increased at a rate of 5°C / min using a differential scanning calorimeter.

[0024] Also, the copolymer can further include a constituent unit (C) derived from at least one compound selected from the group consisting of (c1) to (c4) below.

[0025] (c1) styrene optionally substituted with an alkyl group;

[0026] (c2) N-substituted maleimide;

[0027] (c3) N-vinyl compound; and

[0028] (c4) an unsaturated carboxylic acid derivative represented by the following formula (2),

[0029] [Chemical Formula 2]

[0030]

[0031] (In the formula, R 11 represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. R 12 represents a hydrocarbon group optionally containing a hetero atom. Z represents a hetero atom).

[0032] Also, the proportion of the constituent unit (A) can be 2 to 60% by weight, the proportion of the constituent unit (B) can be 40 to 98% by weight, and the proportion of the constituent unit (C) can be 0 to 85% by weight, with respect to the total constituent units of the copolymer.

[0033] Also, the photosensitive resin composition of the present disclosure can further include a color material.

[0034] Also, the color material can be a pigment and / or a dye.

[0035] Further, the present disclosure provides a cured product of the photosensitive resin composition.

[0036] Further, the present disclosure provides a color filter which is a cured product of the photosensitive resin composition.

[0037] Furthermore, the present disclosure provides a member for a display device or a display device including the color filter.

[0038] Effects of the Invention

[0039] According to the present invention, a photosensitive resin composition with excellent storage stability, excellent curing reactivity, and excellent solvent resistance of the cured product is provided. Furthermore, a cured product of the photosensitive resin composition having the above-mentioned properties, a color filter as the cured product, and a component or display device having the color filter are provided. Detailed Implementation

[0040] 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. The photosensitive resin composition comprises an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. Furthermore, the photosensitive resin composition disclosed herein may also include a colorant.

[0041] Alkali-soluble resins

[0042] In this disclosure, as an alkali-soluble resin, a copolymer is used that comprises a constituent unit (A) derived from an unsaturated carboxylic acid or its anhydride and a constituent unit (B) derived from a compound represented by formula (1). The copolymer exhibits an exothermic peak temperature of 180–220 °C when heated at a rate of 5 °C / min using a differential scanning calorimeter. The copolymer may also further comprise a constituent unit (C) derived from at least one compound selected from the group consisting of (c1) to (c4). Furthermore, a constituent unit (D), described later, may also be included as a constituent unit other than constituent units (A) to (C).

[0043] [Constructing Unit (A)]

[0044] The constituent unit (A) can be introduced into the copolymer by copolymerizing an unsaturated carboxylic acid or its anhydride (a).

[0045] There are no particular limitations on the unsaturated carboxylic acid or its anhydride (a). 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. Among these, acrylic acid and methacrylic acid are particularly preferred from the viewpoint of copolymerization and developability. The unsaturated carboxylic acid or its anhydride (a) can be used alone or in combination of two or more.

[0046] The proportion (content) of the constitutional unit (A) with respect to the total constitutional units of the copolymer is not particularly limited, and for example, it is preferably 2 to 60% by weight, more preferably 3 to 40% by weight, and further preferably 5 to 20% by weight. The proportion of the constitutional unit (A) is within the above range, whereby there is a tendency that the solvent resistance and the developability of the cured product are excellent. Note that in the present disclosure, the proportion of the constitutional unit in the copolymer is based on the weight of the compound (monomer) used in the copolymerization. For example, the proportion of the constitutional unit (A) in the copolymer is the proportion of the amount of use of the unsaturated carboxylic acid or the acid anhydride thereof (a) with respect to the total amount (100% by weight) of the compounds used for the copolymerization.

[0047] [Constitutional unit (B)]

[0048] The constitutional unit (B) can be introduced into the copolymer by subjecting a compound represented by the following formula (1) to copolymerization.

[0049] [Chemical formula 3]

[0050]

[0051] In formula (1), R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. X represents a single bond or a divalent hydrocarbon group optionally containing a hetero atom. Y represents a methylene group or an ethylene group optionally having an alkyl group having 1 to 3 carbon atoms as a substituent, an oxygen atom, or a sulfur atom optionally bonded to an oxygen atom. n represents an integer of 0 to 7.

[0052] As the alkyl group having 1 to 7 carbon atoms in R 1 and R 2 , for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a pentyl group, a hexyl group, a heptyl group, and the like can be mentioned. In the case where n is 2 or more, the n R 2 may be the same or different. From the viewpoint of copolymerizability and reactivity, R 1 and R 2 are preferably a hydrogen atom, a methyl group, or an ethyl group.

[0053] In the divalent hydrocarbon group of X optionally containing a hetero atom, the hetero atom can be bonded to the terminal of the hydrocarbon group or can be interposed between the carbon atoms constituting the hydrocarbon group. The hetero atom is not particularly limited, and for example, a nitrogen atom, an oxygen atom, a sulfur atom can be mentioned.

[0054] As the divalent hydrocarbon group optionally containing the hetero atom, for example, there can be mentioned: alkylene groups (preferably alkylene groups having 1 to 12 carbon atoms, more preferably alkylene groups having 1 to 6 carbon atoms, particularly preferably alkylene groups having 1 to 3 carbon atoms) such as methylene, ethylene, propylene, trimethylene, and the like; thioalkylene groups (preferably thioalkylene groups having 1 to 12 carbon atoms, more preferably thioalkylene groups having 1 to 6 carbon atoms) such as thiomethylene, thioethylene, thio-propylene, and the like; aminoalkylene groups (preferably aminoalkylene groups having 1 to 12 carbon atoms, more preferably aminoalkylene groups having 1 to 6 carbon atoms) such as aminomethylene, aminoethylene, aminopropylene, and the like; and the like. Among them, from the viewpoint of storage stability, alkylene groups having 1 to 3 carbon atoms are preferred, and methylene is more preferred.

[0055] The methylene or ethylene group of Y optionally having an alkyl group having 1 to 3 carbon atoms as a substituent is not particularly limited, and methylene or ethylene is preferred, and methylene is more preferred.

[0056] The sulfur atom of Y optionally bonded to an oxygen atom, for example, there can be mentioned a sulfur atom, a sulfonyl group, and the like.

[0057] As the compound represented by the formula (1), for example, there can be mentioned a compound represented by the following formula (la).

[0058] [Chemical Formula 4]

[0059]

[0060] R in the formula (la) 1 , R 2 , X, Y, and n are the same as the meanings described in the formula (1).

[0061] As a specific example of the compound represented by the formula (1), there can be mentioned the following compounds.

[0062] [Chemical Formula 5]

[0063]

[0064] The proportion (content) of the constitutional unit (B) with respect to the total constitutional units of the copolymer is not particularly limited, and is preferably 40 to 98% by weight, more preferably 60 to 95% by weight, and further preferably 75 to 90% by weight. The proportion of the constitutional unit (B) is within the above range, whereby there is a tendency that the cured product is excellent in solvent resistance and developability.

[0065] [Constitutional Unit (C)]

[0066] The constitutional unit (C) is a constitutional unit derived from at least one compound selected from the group consisting of (c1) to (c4) below: styrene optionally substituted with an alkyl group (c1), an N-substituted maleimide (c2), an N-vinyl compound (c3), and the unsaturated carboxylic acid derivative represented by the formula (2) (c4). The constitutional unit (C) has a function of imparting hardness to a cured product (cured film), a function of making a copolymerization reaction smooth, a function of improving solubility in a solvent, a function of improving adhesion to a substrate, and the like.

[0067] The constitutional unit (C) can be introduced into a copolymer by applying copolymerization to at least one compound selected from the group consisting of (c1) to (c4) above.

[0068] (styrene (c1))

[0069] The alkyl group in the styrene optionally substituted with an alkyl group (c1) is not particularly limited, and, for example, a carbon number 1 to 7 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, and the like can be exemplified. Among these, a carbon number 1 to 4 alkyl group such as a methyl group or an ethyl group is preferred, and a methyl group is more preferred. The alkyl group can be bonded to any of the vinyl group and the benzene ring of the styrene.

[0070] As representative examples of the styrene optionally substituted with an alkyl group (c1), styrene, α-methylstyrene, vinyltoluene (o-vinyltoluene, m-vinyltoluene, p-vinyltoluene), and the like can be exemplified. The styrene optionally substituted with an alkyl group (c1) can be used alone or in combination of two or more.

[0071] (N-substituted maleimide (c2))

[0072] As the N-substituted maleimide (c2), for example, a compound represented by the following formula (3) can be exemplified.

[0073] [Chemical Formula 6]

[0074]

[0075] In the formula (3), R 21 represents an organic group.

[0076] As the organic group, for example, a hydrocarbon group, a heterocyclic group can be exemplified. As the hydrocarbon group, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, and the like (for example, C 1-6alkyl groups, etc.); cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, norbornyl, and the like cycloalkyl groups; phenyl, and the like aryl groups; benzyl, and the like aralkyl groups; groups having two or more of these bonded together; and the like. As the heterocyclic group, for example, five- to ten-membered heterocyclic alkyl groups and heteroaryl groups containing at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom can be exemplified.

[0077] As the N-substituted maleimide (c2), for example, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, and the like N-alkylmaleimides; N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cyclooctylmaleimide, N-adamantylmaleimide, N-norbornylmaleimide, and the like N-cycloalkylmaleimides; N-phenylmaleimide, and the like N-arylmaleimides; N-benzylmaleimide, and the like N-aralkylmaleimides can be exemplified. The N-substituted maleimide (c2) can be used alone or in combination of two or more.

[0078] As the N-vinyl compound (c3), for example, N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-methylacetamide, N-vinylpyrrolidone, N-vinylcarbazole, N-vinylpiperidone, N-vinylcaprolactam, and the like can be exemplified. The N-vinyl compound (c3) can be used alone or in combination of two or more.

[0079] The unsaturated carboxylic acid derivative (c4) can be represented by the following formula (2).

[0080] [Chemical Formula 7]

[0081]

[0082] In formula (2), R 11 represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. R 12 represents a hydrocarbon group optionally containing a heteroatom. Z represents a heteroatom.

[0083] As the alkyl group having 1 to 7 carbon atoms in R 11 , for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a hexyl group, and the like can be exemplified. 11 A hydrogen atom or a methyl group is particularly preferable as R

[0084] As the alkyl group having 1 to 7 carbon atoms in R 12As the hydrocarbon group optionally containing a hetero atom in the above-mentioned groups, for example, an alkyl group, a heteroalkyl group, an alkenyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, and a group in which two or more of the above-mentioned groups are linked can be exemplified. As the hetero atom, for example, a nitrogen atom, an oxygen atom, and a sulfur atom can be exemplified.

[0085] As the alkyl group, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, an isodecyl group, a lauryl group, a stearyl group, and the like can be exemplified.

[0086] As the heteroalkyl group, for example, a group represented by -R 13 -O)m-R 14 group (in the formula, R 13 represents an alkylene group having 1 to 12 carbon atoms. R 14 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms. m represents an integer of 1 or more), a group represented by -R 15 -NR 16 R 17 group (in the formula, R 15 represents an alkylene group having 1 to 12 carbon atoms. R 16 and R 17 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).

[0087] As the alkenyl group, for example, an allyl group, a 3-butenyl group, a 5-hexenyl group, and the like can be exemplified.

[0088] As the cycloalkyl group, for example, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, an adamantyl group, a norbornyl group, and the like can be exemplified.

[0089] As the heterocycloalkyl group, for example, a group containing a cyclic ether structure (for example, a group containing a cyclic ether having three or more rings), such as an oxetane ring, an oxolane ring, an oxane ring, an oxepane ring, and the like can be exemplified.

[0090] As the aryl group, for example, a phenyl group, a naphthyl group, and the like can be exemplified.

[0091] The unsaturated carboxylic acid derivative (C4) shown in formula (2) is not particularly limited. Examples include: methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isodecanyl methacrylate, lauryl methacrylate, stearyl methacrylate, and other alkyl-containing (meth)acrylates; N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, N,N-diisopropylaminoethyl methacrylate, and other alkylamino (meth)acrylates; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and other alkylamino (meth)acrylates. Hydroxyl-containing methacrylates such as 2-hydroxybutyl acrylate and 4-hydroxybutyl methacrylate; methoxydiethylene glycol methacrylate, ethoxydiethylene glycol methacrylate, isooctoxydiethylene glycol methacrylate, phenoxytriethylene glycol methacrylate, methoxytriethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, and polyalkylene glycol methacrylates; alkylene-containing methacrylates such as allyl methacrylate; cyclohexyl methacrylate, 1-adamantane methacrylate, isobornyl methacrylate, tricyclo[5,2,1,0] 2,6Decane-8-ol (meth)acrylate and other (meth)acrylates with monocyclic or polycyclic cycloalkyl groups; glycidyl acrylate, 2-methylglycidyl acrylate, 2-ethylglycidyl acrylate, 2-glycidyloxyethyl acrylate, 3-glycidyloxypropyl acrylate, glycidyloxyphenyl acrylate and other (meth)acrylates with epoxy groups (epoxyethylene acrylate); oxetane acrylate, 3-methyl-3-oxetane acrylate, 3-(meth)acrylate Ethyl-3-oxetane ester, (meth)acrylate (3-methyl-3-oxetane) methyl ester, (meth)acrylate (3-ethyl-3-oxetane) methyl ester, (meth)acrylate 2-(3-methyl-3-oxetane) ethyl ester, (meth)acrylate 2-(3-ethyl-3-oxetane) ethyl ester, (meth)acrylate 2-[(3-methyl-3-oxetane)methoxy] ethyl ester, (meth)acrylate 2-[(3-ethyl-3-oxetane)methoxy] ethyl ester, (meth)acrylate 3-[(3-methyl-3-oxetane)methoxy] ethyl ester [3,4-[(3-ethyl-3-oxetyl-3-oxetyl)methoxy]propyl acrylate, etc. (meth)acrylates containing oxetyl groups, such as 3-[(3-ethyl-3-oxetyl)methoxy]propyl acrylate; (meth)acrylates containing oxetyl groups, such as tetrahydrofurfuryl acrylate; 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methyl acrylate, 2-(3,4-epoxycyclohexyl)ethyl acrylate, 2-(3,4-epoxycyclohexyl)ethyl acrylate, 3-(3,4-epoxycyclohexyl)propyl acrylate, etc. (Meth)acrylates containing alicyclic epoxy groups, etc., and (meth)acrylates having heterocyclic alkyl groups (e.g., groups containing cyclic ethers with three or more membered rings); (meth)acrylates having aryl groups, such as phenyl (meth)acrylate and benzyl (meth)acrylate; (meth)acrylates containing alkoxysilyl groups, such as 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane, 3-(meth)acryloyloxypropyltriethoxysilane, and 8-(meth)acryloyloxyoctyltrimethoxysilane. The unsaturated carboxylic acid derivative (c4) shown in formula (2) can be used alone or in combination of two or more.

[0092] The proportion (content) of the constituent unit (C) relative to all the constituent units of the 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. When the proportion of the constituent unit (C) is within the above range, there is a tendency for the cured product to have excellent solvent resistance.

[0093] [Constructing Unit (D)]

[0094] The copolymers described in this disclosure may also include constituent units (D) other than those described in constituent units (A) to (C). Examples of constituent units (D) include those derived from (meth)acrylamide and (meth)acrylonitrile.

[0095] In the case where the copolymer described in this disclosure comprises constituent unit (A) and constituent unit (B) but does not contain constituent unit (C), the total amount of constituent unit (A) and constituent unit (B) relative to all constituent units is preferably 90% by weight or more, more preferably 95% by weight or more, even more preferably 99% by weight or more, and substantially may also be 100% by weight. Furthermore, in the case where the copolymer described in this disclosure comprises constituent unit (A), constituent unit (B), and constituent unit (C), the total amount of constituent units (A) to (C) relative to all constituent units is preferably 90% by weight or more, more preferably 95% by weight or more, even more preferably 99% by weight or more, and substantially may also be 100% by weight.

[0096] 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 weight-average molecular weight to 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. It should be noted that in this disclosure, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using polystyrene as a standard substance via GPC, and are preferably values ​​determined by the method used in the examples.

[0097] The polymer described in this disclosure exhibits an exothermic peak temperature of 180–220°C when heated using a differential scanning calorimeter at a rate of 5°C / min. It should be noted that, in this disclosure, the exothermic peak temperature is preferably determined, for example, by the method used in the embodiments described later.

[0098] The copolymers described in this disclosure function as binder resins in the photosensitive resin compositions of this disclosure.

[0099] <Methods for manufacturing copolymers>

[0100] The copolymers described in this disclosure can be produced by copolymerizing an unsaturated carboxylic acid or its anhydride (a), a compound (b) having a polycyclic aliphatic group having an epoxy group on the ring and a group having an unsaturated bond, at least one compound selected as needed from the group consisting of (c1) to (c4), and a compound corresponding to the constituent unit (D). Hereinafter, compounds that can be introduced into copolymers of unsaturated carboxylic acids or their anhydrides (a), etc., are generally referred to as "monomers".

[0101] In the copolymer manufacturing method disclosed herein, copolymerization can also be applied in the presence of a polymerization initiator. As the polymerization initiator, conventional and even known free radical polymerization initiators can be used, for example, azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylpentanonitrile), 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile), 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, lauroyl peroxide, tert-butyl peroxypentanoate, and 1,1-bis(tert-butylperoxy)cyclohexane; and hydrogen peroxide. When a peroxide is used as a free radical polymerization initiator, a redox initiator can also be prepared by combining it with a reducing agent. Azo compounds are preferred, and 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylpentanonitrile), and dimethyl-2,2'-azobis(2-methylpropionate) are more preferred.

[0102] The amount of polymerization initiator used can be appropriately selected within a range that does not hinder smooth copolymerization, and there is no particular limitation. For example, it is preferably 1 to 20 parts by weight relative to the total amount of monomer (100 parts by weight), and more preferably 3 to 15 parts by weight.

[0103] In this disclosure, copolymerization can be carried out using conventional methods employed in the manufacture of acrylic polymers and styrene polymers, such as solution polymerization, bulk polymerization, suspension polymerization, bulk-suspension polymerization, and emulsion polymerization. The monomer and polymerization initiator can be supplied to the reaction system in a single step, or they can be added dropwise to the reaction system in part or all. For example, polymerization can be carried out by adding a solution of the polymerization initiator dissolved in the polymerization solvent dropwise to a monomer or a mixture of monomer and polymerization solvent maintained at a constant temperature; or by adding a solution of the monomer and polymerization initiator pre-dissolved in the polymerization solvent dropwise to a polymerization solvent maintained at a constant temperature (dropwise polymerization), etc.

[0104] The copolymers described in this disclosure are preferably copolymerized in a polymerization solvent. The polymerization solvent can be appropriately selected based on the monomer composition, etc., and examples include: ethers (diethyl ether; ethylene glycol mono- or dialkyl ethers, diethylene glycol mono- or dialkyl ethers, propylene glycol mono- or dialkyl ethers, propylene glycol mono- or diaryl ethers, dipropylene glycol mono- or dialkyl ethers, tripropylene glycol mono- or dialkyl ethers, 1,3-propanediol mono- or dialkyl ethers, 1,3-butanediol mono- or dialkyl ethers, 1,4-butanediol mono- or dialkyl ethers, glycerol mono-, di- or trialkyl ethers, etc., and other diol ethers; cyclic ethers such as tetrahydrofuran and dioxane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, C... 5-6 Cycloalkyl diol mono or diacetate, C 5-6 Carboxylic acid esters such as cycloalkanediol mono- or diacetate; ethylene glycol monoalkyl ether acetates, ethylene glycol mono- or diacetate, diethylene glycol monoalkyl ether acetates, diethylene glycol mono- or diacetate, propylene glycol monoalkyl ether acetates, propylene glycol mono- or diacetate, dipropylene glycol monoalkyl ether acetates, dipropylene glycol mono- or diacetate, 1,3-propanediol monoalkyl ether acetates, 1,3-propanediol mono- or diacetate, 1,3-butanediol monoalkyl ether acetates, 1,3-butanediol mono- or diacetate, 1,4-butanediol monoalkyl ether acetates, 1,4-butanediol mono- or diacetate, glycerol mono-, di- or triacetate, glycerol mono- or di-C 1-4 Alkyl ether diacetates or monoacetic acids, tripropylene glycol monoalkyl ether acetates, tripropylene glycol monoacetates or diacetates, etc. (diol acetates or diol ether acetates, etc.), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 3,5,5-trimethyl-2-cyclohexen-1-one, etc.), amides (N,N-dimethylacetamide, N,N-dimethylformamide, etc.), sulfoxides (dimethyl sulfoxide, etc.), alcohols (methanol, ethanol, propanol, C... 5-6 Cycloalkyldiol, C 5-6 Hydrocarbons (such as cycloalkanesimil, etc.), aromatic hydrocarbons (such as benzene, toluene, xylene, etc., aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane, etc.), and their mixed solvents, etc.

[0105] The polymerization temperature can be appropriately selected according to the type and composition of the monomer, without any particular limitation. For example, it is preferred to be 30 to 150°C.

[0106] The reaction solution containing the copolymer obtained by the above method can be purified as needed by precipitation or reprecipitation. The solvent used for precipitation or reprecipitation can be any organic solvent and water, or a mixture 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, nitrobenzene, etc.); nitriles (acetonitrile, benzonitrile, etc.); ethers (chain ethers such as diethyl ether, diisopropyl 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, ethylene carbonate, propylene carbonate, etc.); alcohols (methanol, ethanol, propanol, isopropanol, butanol, etc.); carboxylic acids (acetic acid, etc.); and mixed solvents containing these solvents.

[0107] <Color material>

[0108] In this disclosure, any colorant (coloring agent) can be used as a coloring material, and the color and material can be appropriately selected according to the application such as a color filter. Specifically, any type of pigment, dye, or natural pigment can be used as a colorant, but for applications requiring high color purity, brightness, and contrast, pigments and / or dyes are preferred.

[0109] The aforementioned pigments can be any type of organic or inorganic pigment. For example, organic pigments include compounds classified as pigments in the Color Index (CI; published by The Society of Dyers and Colourists). Specifically, pigments with attached Color Index (CI) names can be listed below.

[0110] CI Yellow Pigment 1, CI Yellow Pigment 3, CI Yellow Pigment 12, CI Yellow Pigment 13, CI Yellow Pigment 14, CI Yellow Pigment 16, CI Yellow Pigment 17, CI Yellow Pigment 20, CI Yellow Pigment 24, CI Yellow Pigment 31, CI Yellow Pigment 55, CI Yellow Pigment 83, CI Yellow Pigment 86, CI Yellow Pigment 93, CI Yellow Pigment 94, CI Yellow Pigment 109, CI Yellow Pigment 110, CI Yellow Pigment 117, CI Yellow Pigment 125, CI Yellow Pigment 137, CI Yellow Pigment 138, CI Yellow Pigment 139, CI Yellow Pigment 147, CI Yellow Pigment 148, CI Yellow Pigment 150, CI Yellow Pigment 153, CI Yellow Pigment 154, CI Yellow Pigment 155, CI Yellow Pigment 166, CI Yellow Pigment 168, CI Yellow Pigment 180, CI Yellow Pigment 194, CI Yellow Pigment 211, CI Yellow Pigment 214, and other yellow pigments.

[0111] CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 24, CI Pigment Orange 31, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 42, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51, CI Pigment Orange 55, CI Pigment Orange 59, CI Pigment Orange 61, CI Pigment Orange 64, CI Pigment Orange 65, CI Pigment Orange 68, CI Pigment Orange 70, CI Pigment Orange 71, CI Pigment Orange 72, CI Pigment Orange 73, CI Pigment Orange 74, etc., are orange pigments.

[0112] CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 5, CI Pigment Red 9, CI Pigment Red 17, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 41, CI Pigment Red 97, CI Pigment Red 105, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 149, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red Red pigments including Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 192, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 209, CI Pigment Red 214, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 221, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 262, CI Pigment Red 264, CI Pigment Red 265, CI Pigment Red 272, etc.

[0113] CI pigment purple 1, CI pigment purple 19, CI pigment purple 23, CI pigment purple 29, CI pigment purple 32, CI pigment purple 36, CI pigment purple 38 and other purple pigments.

[0114] CI Pigment Blue 15, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 60, CI Pigment Blue 80, and other blue pigments.

[0115] CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, and other green pigments.

[0116] CI Pigment Brown 23, CI Pigment Brown 25, and other brown pigments.

[0117] CI Pigment Black 1, CI Pigment Black 7, and other black pigments.

[0118] In addition, examples of the aforementioned inorganic pigments include: titanium dioxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, chrome yellow, zinc yellow, iron oxide red (red iron oxide (III)), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, brown earth, titanium black, synthetic iron black, carbon black, etc.

[0119] In this disclosure, the pigment can also be purified and used by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, or a combination thereof. Furthermore, the pigment can also be used by modifying the surface of its particles with resin.

[0120] In addition, the dyes mentioned above can be appropriately selected from various oil-soluble dyes, direct dyes, acid dyes, metal complex dyes, etc. For example, dyes with color index (CI) names can be listed below.

[0121] CI Solvent Yellow 4, CI Solvent Yellow 14, CI Solvent Yellow 15, CI Solvent Yellow 24, CI Solvent Yellow 82, CI Solvent Yellow 88, CI Solvent Yellow 94, CI Solvent Yellow 98, CI Solvent Yellow 162, CI Solvent Yellow 179, CI Acid Yellow 17, CI Acid Yellow 29, CI Acid Yellow 40, CI Acid Yellow 76, and other yellow dyes.

[0122] Orange dyes including CI Solvent Orange 2, CI Solvent Orange 7, CI Solvent Orange 11, CI Solvent Orange 15, CI Solvent Orange 26, CI Solvent Orange 56, CI Acid Orange 51, and CI Acid Orange 63.

[0123] CI Solvent Red 45, CI Solvent Red 49, CI Acid Red 91, CI Acid Red 92, CI Acid Red 97, CI Acid Red 114, CI Acid Red 138, CI Acid Red 151 and other red dyes.

[0124] CI Solvent Blue 35, CI Solvent Blue 37, CI Solvent Blue 59, CI Solvent Blue 67, CI Acid Blue 80, CI Acid Blue 83, CI Acid Blue 90 and other blue dyes.

[0125] CI Acid Green 9, CI Acid Green 16, CI Acid Green 25, CI Acid Green 27 and other green dyes.

[0126] In this disclosure, the colorant can be used alone or in combination of two or more.

[0127] The content of the colorant relative to the solid components of the photosensitive resin composition is not particularly limited, but is preferably 3 to 50% by weight, more preferably 5 to 30% by weight. Here, "solid components" refers to components other than the solvent mentioned above.

[0128] In this disclosure, when using pigments as colorants, they can be used in conjunction with pigment dispersants and pigment dispersing aids as desired. Examples of such pigment dispersants include cationic, anionic, nonionic, and amphoteric dispersants (surfactants); and polymer dispersants such as acrylic copolymers, polyesters, polyurethanes, polyethyleneimine, and polyallylamine.

[0129] The aforementioned pigment dispersants can be commercially available pigment dispersants, such as: Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, and BYK-LPN21116 (all manufactured by BYK Chemie (BYK) Co., Ltd.) as acrylic copolymers; Ajisper PB821, Ajisper PB822, and Ajisper PB880 (manufactured by Ajinomoto Fine-Techno Co., Ltd.) as polyesters; Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, and Disperbyk-182 (all manufactured by BYK Chemie (BYK) Co., Ltd.) and Solsperse 76500 (manufactured by Lubrizol (Co., Ltd.) as polyurethanes; and Solsperse 76500 (manufactured by Lubrizol (Co., Ltd.) as polyethyleneimine. 24000 (made by Lubrizol Corporation), etc.

[0130] These pigment dispersants can be used alone or in combination of two or more. The content of the pigment dispersant relative to 100 parts by weight of the pigment is usually 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. If the content of the pigment dispersant is within the above range, there is a tendency to obtain a pigment dispersion in a uniformly dispersed state, which is therefore preferred.

[0131] Examples of pigment dispersing aids include, for instance, pigment derivatives, specifically, copper phthalocyanine, pyrrolopyrrole dione, and sulfonic acid derivatives of quinophthalone. The content of the pigment dispersing aid can be appropriately determined without hindering the purpose of the invention disclosed herein.

[0132] <Photopolymerizable compounds>

[0133] In this disclosure, the term "photopolymerizable compound" is not particularly limited, but examples include: polyfunctional vinyl compounds, polyfunctional thiols, and polyfunctional epoxy compounds.

[0134] As a multifunctional vinyl compound, there are no particular limitations as long as the compound has two or more vinyl groups. Examples 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 two-terminated hydroxylated polymers such as polybutadiene, polyisoprene, and polycaprolactone; and di(meth)acrylates of glycerol, 1,2,4'-butanetriol, and trihydroxy... Poly(meth)acrylates of polyols with three or more ternary groups, such as methylalkanes, tetrahydroxymethylalkanes, pentaerythritol, and dipentaerythritol; poly(meth)acrylates of polyalkylene glycol adducts of polyols with three or more ternary groups; poly(meth)acrylates of cyclic polyols such as 1,4-cyclohexanediol and 1,4-dihydroxybenzene; and oligomeric (meth)acrylates such as polyester (meth)acrylates, epoxy (meth)acrylates, urethane (meth)acrylates, and silicone (meth)acrylates. Among these, polyfunctional (meth)acrylates having two or more (meth)acryloyl groups are preferred. Polyfunctional vinyl compounds can be used alone or in combination of two or more.

[0135] As a polyfunctional thiol compound, there are no particular limitations as long as the compound has two or more thiol groups. Examples include: hexanedithiol, decanedithiol, 1,4-butanediol dithiopropionate, 1,4-butanediol dithioglycolate, ethylene glycol dithioglycolate, ethylene glycol dithiopropionate, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropionate, trimethylolpropane tri(3-mercaptobutyrate), pentaerythritol tetrathioglycolate, pentaerythritol tetrathiopropionate, tri(2-hydroxyethyl) isocyanurate of trimercaptopropionate, 1,4-dimethyl... Mercaptobenzene, 2,4,6-trimercaptotriazine, 2-(N,N-dibutylamino)-4,6-dimercaptotriazine, tetraethylene glycol bis(3-mercaptopropionate), trimethylolpropane tri(3-mercaptopropionate), tris(3-mercaptopropynoxyethyl)isocyanurate, pentaerythritol tetra(3-mercaptopropionate), dipentaerythritol tetra(3-mercaptopropionate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, pentaerythritol tetra(3-mercaptobutyryl), etc. Polyfunctional thiols can be used alone or in combination of two or more.

[0136] As a multifunctional epoxy compound, there are no particular limitations as long as it has two or more epoxy groups. For example, glycidyl ether type epoxy compounds [glycidyl ethers generated by the reaction of polyhydroxy compounds (bisphenols, polyphenols, alicyclic polyols, aliphatic polyols, etc.) with epichlorohydrin (e.g., ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, etc. (poly)C] 2-4 Alkylene glycol diglycidyl ethers; diglycidyl ethers of polyphenols such as resorcinol and hydroquinone; diglycidyl ethers of alicyclic polyols such as cyclohexanediol, cyclohexanediol, and hydrogenated bisphenols; bisphenols (4,4'-dihydroxybiphenyl, bisphenol A, and other bis(hydroxyphenyl)alkanes, etc.) or their C... 2-3 Epoxy alkane adducts such as diglycidyl ethers, linear phenolic epoxy resins (phenol linear phenolic or cresol linear phenolic epoxy resins, etc.); glycidyl ester type epoxy compounds; alicyclic epoxy compounds (or cyclic aliphatic epoxy resins); heterocyclic epoxy resins (triglycidyl isocyanurate (TGIC); hydantoin type epoxy resins, etc.); glycidyl amine type epoxy compounds [reaction products of amines and epichlorohydrin, for example, N-glycidyl aromatic amines {tetraglycidyl...] Examples of polyfunctional epoxy compounds include glyceryl diaminodiphenylmethane (TGDDM), triglycidyl aminophenol (such as triglycidyl p-aminophenol (TGPAP) and triglycidyl m-aminophenol (TGMAP)), diglycidyl aniline (DGA), diglycidyl toluidine (DGT), tetraglycidyl xylenediamine (such as tetraglycidyl m-xylenediamine (TGMXA)), and N-glycidyl alicyclic amines (such as tetraglycidyl diaminocyclohexane). These polyfunctional epoxy compounds can be used alone or in combination of two or more.

[0137] The photopolymerizable compound can be used alone or in combination of two or more. The content of the photopolymerizable compound relative to 100 parts by weight of the alkali-soluble resin is typically 10 to 300 parts by weight, preferably 30 to 200 parts by weight, and more preferably 40 to 150 parts by weight. Furthermore, when the photosensitive resin composition includes a colorant, the content of the photopolymerizable compound relative to 100 parts by weight of the colorant is typically 10 to 1000 parts by weight, preferably 50 to 600 parts by weight, and more preferably 100 to 500 parts by weight. When the content of the photopolymerizable compound is within the above range, sufficient curing occurs, resulting in good adhesion.

[0138] Photopolymerization initiators

[0139] In this disclosure, there is no particular limitation on the photopolymerization initiator, but examples include: photoradical polymerization initiators and photocationic polymerization initiators.

[0140] Photoradical polymerization initiators are compounds that generate free radicals through light irradiation, initiating a curing reaction (free radical polymerization) of photopolymerizable compounds contained in a photosensitive resin composition. Photoradical polymerization initiators can be used alone or in combination of two or more.

[0141] Examples of photoradical polymerization initiators include: thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, oxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, anthracene compounds, etc.

[0142] Examples of the thioxanthone compounds include, for example, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, etc.

[0143] Examples of acetophenone compounds include, for example: diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, benzoil dimethyl ketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, 2-(2-methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)- Butanone, 2-(2-ethylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-propylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-butylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2,3-dimethylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2,4-dimethylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-chlorobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2 2-(2-bromobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-chlorobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(4-chlorobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-bromobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(4-bromobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone Oligomers of dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-methyl-4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-methyl-4-bromobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(2-bromo-4-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, and 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propane-1-one, etc.

[0144] Examples of the biimidazole compounds include, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, and imidazole compounds obtained by substituting the phenyl group at the 4,4',5,5'-position with an alkoxycarbonyl group.

[0145] Examples of triazine compounds include, for instance: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperyl-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-piperyl-1,3,5-triazine. -[2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

[0146] Examples of such oxime compounds include O-ethoxycarbonyl-α-oxime-phenylpropane-1-one.

[0147] Examples of benzoin compounds include, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.

[0148] Examples of benzophenone compounds include, for example, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, 3,3',4,4≡-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc.

[0149] Examples of the anthracene compounds include, for example, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene.

[0150] The photocationic polymerization initiator is a compound that generates acid upon light irradiation, initiating a curing reaction (cationic polymerization) of the photopolymerizable compound contained in the photosensitive resin composition. It comprises a light-absorbing cationic portion and an anionic portion that serves as the acid generation source. The photocationic polymerization initiator can be used alone or in combination of two or more.

[0151] Examples of photocationic polymerization initiators include: diazonium salts, iodonium salts, sulfonium salts, phosphonium salts, selenium salts, oxonium salts, ammonium salts, and bromide salts.

[0152] Anionic components that serve as initiators for photocationic polymerization include, for example: [(Y)] s B(Phf) 4-s ] - (In the formula, Y represents phenyl or biphenyl. Phf represents a phenyl group in which at least one hydrogen atom is substituted by at least one selected from perfluoroalkyl, perfluoroalkoxy, and halogen atoms. s is an integer from 0 to 3), BF4 - 、[(Rf) k PF 6-k ] - (Rf: alkyl group in which more than 80% of hydrogen atoms are replaced by fluorine atoms, k: an integer from 0 to 5), AsF6 - SbF6 - SbF5OH - wait.

[0153] Examples of photocationic polymerization initiators include: (4-hydroxyphenyl)methylbenzylsulfonium tetra(pentafluorophenyl)borate, 4-(4-biphenylthio)phenyl-4-biphenylphenylsulfonium tetra(pentafluorophenyl)borate, 4-(phenylthio)phenyl diphenylsulfonium phenyl tri(pentafluorophenyl)borate, [4-(4-biphenylthio)phenyl]-4-biphenylphenylsulfonium phenyl tri(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium tri(pentafluoroethyl)trifluorophosphate, and diphenyl[4-(phenylthio)phenyl]sulfonium tri(pentafluoroethyl)trifluorophosphate. Phenyl[4-(phenylthio)phenyl]sulfonium tetra(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, 4-(4-biphenylthio)phenyl-4-biphenylphenylsulfonium tri(pentafluoroethyl)trifluorophosphate, sulfide bis[4-(diphenylsulfonium)phenyl]phenyl tri(pentafluorophenyl)borate, [4-(2-thioxanthoneylthio)phenyl]phenyl-2-thioxanthoneylsulfonium tri(pentafluorophenyl)borate, 4-(phenylthio)phenyl diphenylsulfonium hexafluoroantimonate, etc.

[0154] As photocationic polymerization initiators, the following can be used: "CyracureUVI-6970", "CyracureUVI-6974", "CyracureUVI-6990", "CyracureUVI-950" (all manufactured by Union Carbide, USA); "Irgacure250", "Irgacure261", "Irgacure264" (all manufactured by BASF); "CG-24-61" (manufactured by Ciba Geigy); "OptomerSP-150", "OptomerSP-151", "OptomerSP-170", "OptomerSP-171" (all manufactured by ADEKA Co., Ltd.); "DAICAT" II” (manufactured by DAICEL Corporation); “UVAC1590”, “UVAC1591” (manufactured by DAICEL-Cytec Corporation); “CI-2064”, “CI-2639”, “CI-2624”, “CI-2481”, “CI-2734”, “CI-2855”, “CI-2823”, “CI-2758”, “CIT-1682” (manufactured by Nippon Soda Corporation); “PI-2074” (manufactured by Rhodia Corporation, tetra(pentafluorophenyl)borate toluene cumyl iodine ononium salt); “FFC5” 09 (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 Chemical Co., Ltd.); "CD-1010", "CD-1011", "CD-1012" (all manufactured by Sartamer, Inc., USA); "CPI-100P", "CPI-101A" (all manufactured by San-Apro Co., Ltd.), and other commercially available products.

[0155] The content of the photopolymerization initiator (the total amount when two or more are contained) is, for example, 0.1 to 100 parts by weight, preferably 0.5 to 50 parts by weight, and more preferably 3 to 20 parts by weight, relative to 100 parts by weight of the total amount of the photopolymerizable compound contained in the photosensitive resin composition. If the content of the photopolymerization initiator is lower than the above range, there is a tendency for reduced curability. On the other hand, if the content of the photopolymerization initiator exceeds the above range, there is a tendency for the cured product to become easily colored.

[0156] Solvent

[0157] As solvents, examples include: ethers (diethyl ether; mono- or dialkyl ethers of ethylene glycol, diethylene glycol, propylene glycol, propylene glycol, diaryl ethers, tripropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, glycerol mono- or dialkyl ethers, etc., such as diol ethers; 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 Cycloalkyl diol mono or diacetate, C 5-6 Carboxylic acid esters such as cycloalkanediol mono- or diacetate; ethylene glycol monoalkyl ether acetates, ethylene glycol mono- or diacetate, diethylene glycol monoalkyl ether acetates, diethylene glycol mono- or diacetate, propylene glycol monoalkyl ether acetates, propylene glycol mono- or diacetate, dipropylene glycol monoalkyl ether acetates, dipropylene glycol mono- or diacetate, 1,3-propanediol monoalkyl ether acetates, 1,3-propanediol mono- or diacetate, 1,3-butanediol monoalkyl ether acetates, 1,3-butanediol mono- or diacetate, 1,4-butanediol monoalkyl ether acetates, 1,4-butanediol mono- or diacetate, glycerol mono-, di- or triacetate, glycerol mono- or di-C 1-4 Alkyl ether diacetates or monoacetates, tripropylene glycol monoalkyl ether acetates, tripropylene glycol monoacetates or diacetates, etc. (diol acetates or diol ether acetates, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 3,5,5-trimethyl-2-cyclohexen-1-one, etc.). These solvents can be used alone or in mixtures of two or more.

[0158] In addition to the components described above, the photosensitive resin composition disclosed herein may also include, for example, resins such as phenolic varnish resin, phenolic resin, imide resin, and carboxyl-containing resin; curing agent; curing accelerator; and additives (fillers, defoamers, flame retardants, antioxidants, ultraviolet absorbers, colorants, stress-reducing agents, flexibility enhancers, waxes, resins, crosslinking agents, halogen traps, leveling agents, wetting improvers, etc.).

[0159] The concentration of the alkali-soluble resin in the photosensitive resin composition disclosed herein is not particularly limited, but is, for example, 2 to 60% by weight, preferably 5 to 30% by weight.

[0160] As a method for preparing the photosensitive resin composition disclosed herein, for example, methods such as dissolving an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and other additives as needed in a solvent may be included.

[0161] When the photosensitive resin composition disclosed herein contains a colorant, the preparation method may include, for example, the following methods: dispersing the colorant such as pigment in a solvent by coexisting with a pigment dispersant as needed, and preparing a colorant dispersion; or dissolving an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and other additives as needed in a solvent, mixing them with the colorant dispersion, and further adding solvent as needed.

[0162] The photosensitive resin compositions disclosed herein are typically sealed in containers for distribution and storage. The photosensitive resin compositions disclosed herein exhibit excellent stability during distribution and storage.

[0163] <Cured product>

[0164] Curing the photosensitive resin composition of this disclosure yields a cured product with excellent physical properties. For example, by applying the above-mentioned photosensitive resin composition to various substrates or plates using a conventional coating unit such as a spin coater, dip coater, roller coater, or slot coater to form a coating film, and then curing the coating film, a cured product can be obtained. Curing is performed, for example, by subjecting the photosensitive resin composition to light irradiation and / or heat treatment.

[0165] The light irradiation may use, for example, mercury lamps, xenon lamps, carbon arc lamps, metal halide lamps, sunlight, electron beam sources, laser sources, LED light sources, etc., preferably with a cumulative irradiation dose of, for example, 500–5000 mJ / cm². 2 Irradiation within the range.

[0166] Preferably, the heat treatment is performed at a temperature of 60–300°C (preferably 100–250°C) for 1–120 minutes (preferably 1–60 minutes).

[0167] Examples of substrates or base materials include silicon wafers, metals, plastics, glass, and ceramics. The thickness of the cured coating is preferably 0.05 to 20 μm, and more preferably 0.1 to 10 μm.

[0168] The cured product (cured coating) disclosed herein has excellent solvent resistance and high insulation properties, and is therefore useful as a protective film (color filter protective film, etc.), an insulating film, or a microlens forming material.

[0169] <Color Filter>

[0170] The color filter disclosed herein is a cured product of the photosensitive resin composition disclosed herein. The color filter disclosed herein may also have a colored pattern formed from the photosensitive resin composition. The color filter can be manufactured, for example, by a process of forming a colored pattern on a substrate using the photosensitive resin composition; and a process of post-bake the colored pattern.

[0171] As a method for forming a color filter pattern using the photosensitive resin composition disclosed herein, for example, the following methods can be listed: applying the photosensitive resin composition disclosed herein onto a substrate or other resin layer using a conventional coating unit such as a spin coater, removing volatile components such as solvents to form a color layer, and exposing and developing the color layer through a photomask, etc.

[0172] Examples of substrates include flat-surfaced substrates such as glass substrates, silicone substrates, polycarbonate substrates, polyester substrates, aromatic polyamide substrates, polyamide-imide substrates, polyimide substrates, Al substrates, and GaAs substrates. These substrates can undergo pretreatment processes such as reagent treatment using reagents like silane coupling agents, plasma treatment, ion plating, sputtering, vapor phase reaction treatment, and vacuum evaporation.

[0173] The thickness of the dried coloring layer is, for example, 0.6 to 8 μm, preferably 1 to 5 μm.

[0174] Examples of light sources used for radiation exposure include: xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, and low-pressure mercury lamps; and laser sources such as argon ion lasers, YAG lasers, XeCl excimer lasers, and nitrogen lasers. The wavelength of the radiation is preferably in the range of 190–450 nm. The exposure dose of the radiation is typically preferred to be 10–10000 J / m². 2 .

[0175] As an alkaline developing solution, aqueous solutions 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., are preferred.

[0176] The post-baking conditions are typically at 120–280°C for approximately 10–60 minutes. The resulting pixel film thickness is typically 0.5–5 μm, preferably 1–3 μm.

[0177] According to the photosensitive resin composition disclosed herein, colored patterns with excellent curing reactivity and sufficient solvent resistance can be obtained.

[0178] <Components for display devices or display devices>

[0179] The display device component or display device disclosed herein includes the color filter. For example, a color liquid crystal display element can be cited as a component for the display device. Furthermore, a color liquid crystal display device can be cited as a display device. The structure of the color liquid crystal display element and the color liquid crystal display is not particularly limited, and suitable structures can be adopted.

[0180] It should be noted that the various solutions disclosed in this specification can be combined with any other features disclosed in this specification. Furthermore, the various configurations and combinations thereof in each embodiment are merely examples, and appropriate additions, omissions, and other modifications to the configuration can be made without departing from the spirit of the invention. This disclosure is not limited by the embodiments, but only by the claims.

[0181] Example

[0182] The present disclosure will be further described in detail below based on embodiments.

[0183] The weight-average molecular weight (converted to polystyrene) and dispersity (weight-average molecular weight Mw / number-average molecular weight Mn) of the copolymer were determined under the following conditions.

[0184] Device: Detector: RID-20A (Shimadzu Corporation).

[0185] Pump: LC-20AD (Shimadzu Corporation).

[0186] System controller: CBM-20Alite (Shimadzu Corporation).

[0187] Degassing device: DGU-20A3 (Shimadzu Corporation).

[0188] Autosampler: SIL-20A HT (Shimadzu Corporation).

[0189] Chromatographic column: Shodex KF-806L (Showa Denko).

[0190] Eluent: THF (tetrahydrofuran) 0.8 ml / min.

[0191] Temperature: Oven: 40℃, RI: 40℃.

[0192] Detector: RI.

[0193] The exothermic peak temperature was determined by the following method: 5g of the copolymer-containing solution obtained in Manufacturing Examples 1-8 was added dropwise to 50g of heptane while stirring. The resulting precipitate was separated by filtration and dried under reduced pressure to obtain the copolymer as a white powder. Approximately 10mg of this white powder was used as a sample, and the exothermic peak temperature was determined using a differential scanning calorimeter (Mettler Toledo, DSC1) under a nitrogen atmosphere, with the temperature increased from 40°C to 300°C at a rate of 5°C / min.

[0194] [Reference Example 1 / Preparation of Monomer B1]

[0195] A mixed solution was prepared by adding 33.7 g of 5-norbornene-2-methanol, 41.3 g of triethylamine, and 6.5 mg of p-methoxyphenol to 57.2 g of THF (tetrahydrofuran). 42.4 g of methacryloyl chloride was added dropwise over 40 minutes while maintaining the internal temperature below 20 °C, followed by stirring at 20 °C for 4 hours. After confirming the disappearance of 5-norbornene-2-methanol as the starting material by gas chromatography, 100 g of acetate ether and 84.0 g of water were added. After separation, the mixture was washed with 94.8 g of 10% sodium hydroxide aqueous solution and then three times with 68.0 g of water. The resulting organic phase was concentrated at 40 °C and 15 Torr to obtain 48.3 g of crude 5-norbornene-2-methyl acrylate. The purity of the crude product was 93%, and the yield was 86%.

[0196] A mixed solution of 47.5 g of crude 5-norbornene-2-methyl acrylate and 9.4 mg of p-methoxyphenol was added to 141 g of ethyl acetate. While maintaining the internal temperature below 20°C for 1 hour, 72.3 g of mCPBA (3-chloroperoxybenzoic acid containing 30% water) was added, followed by stirring at 20°C for 3 hours. After confirming the disappearance of the starting material by gas chromatography, 278 g of 15% sodium thiosulfate aqueous solution and 141 g of ethyl acetate were added, and the mixture was stirred for 15 minutes. After separation, the mixture was washed with 217 g of 8% sodium bicarbonate aqueous 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-oxatricyclomethacrylic acid [3.2.1.0]. 2,4 Octane-6-ylmethyl ester (hereinafter, sometimes referred to as "monomer B1"). 3-oxatricyclomethacrylic acid [3.2.1.0] 2,4 Octane-6-ylmethyl ester has a purity of 99% and a yield of 71%.

[0197] [Manufacturing Example 1]

[0198] A suitable amount of nitrogen was blown into a 1L flask equipped with a reflux condenser, a dropping funnel, and a stirrer to create a nitrogen atmosphere. 150 parts by weight of propylene glycol monomethyl ether acetate were added to the flask, and the mixture was heated to 80°C while stirring. Then, 7 parts by weight of 2,2'-azobisisobutyronitrile (AIBN) were added while rinsing with 30 parts by weight of propylene glycol monomethyl ether acetate. Next, a mixture of 11 parts by weight of acrylic acid (AA) and 89 parts by weight of monomer B1 with 20 parts by weight of propylene glycol monomethyl ether acetate was added dropwise to the flask over approximately 4 hours using a dropping pump. After the monomer addition was complete, the mixture was maintained at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer-containing solution with a solid content of 34.6% by weight. The weight-average molecular weight (Mw) of the generated copolymer was 19,000, and the dispersion was 3.47.

[0199] [Manufacturing Example 2]

[0200] Using 11 parts by weight of acrylic acid (AA), 79 parts by weight of monomer B1, and 10 parts by weight of styrene (ST) as monomers, a copolymer-containing solution with a solid content of 33.8% by weight was obtained by performing the same operation as in Manufacturing Example 1. The resulting copolymer had a weight-average molecular weight (Mw) of 17,000 and a dispersion of 3.33.

[0201] [Manufacturing Example 3]

[0202] Using 11 parts by weight of acrylic acid (AA), 79 parts by weight of monomer B1, and 10 parts by weight of methyl methacrylate (MMA) as monomers, a copolymer-containing solution with a solid content of 34.2% by weight was obtained by performing the same operation as in Manufacturing Example 1. The resulting copolymer had a weight-average molecular weight (Mw) of 18,500 and a dispersion of 3.41.

[0203] [Manufacturing Example 4]

[0204] Using 11 parts by weight of acrylic acid (AA), 79 parts by weight of monomer B1, and 10 parts by weight of cyclohexylmaleimide (CHMI) as monomers, a copolymer-containing solution with a solid content of 34.4% by weight was obtained by performing the same operation as in Manufacturing Example 1. The resulting copolymer had a weight-average molecular weight (Mw) of 18,000 and a dispersion of 3.40.

[0205] [Manufacturing Example 5]

[0206] Using 11 parts by weight of acrylic acid (AA), 79 parts by weight of monomer B1, and 10 parts by weight of N-vinylpyrrolidone (VP) as monomers, a copolymer-containing solution with a solid content of 34.4% by weight was obtained by performing the same operation as in Manufacturing Example 1. The resulting copolymer had a weight-average molecular weight (Mw) of 17,500 and a dispersion of 3.38.

[0207] [Manufacturing Example 6]

[0208] A suitable amount of nitrogen was blown into a 1L flask equipped with a reflux condenser, dropping funnel, and stirrer to create a nitrogen atmosphere. 150 parts by weight of propylene glycol monomethyl ether acetate were added, and the mixture was heated to 65°C while stirring. Then, while rinsing with 30 parts by weight of propylene glycol monomethyl ether acetate, 14 parts by weight of 2,2'-azobis(2,4-dimethylpentanonitrile) were added. Next, using a dropping pump, a solution consisting 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 in 20 parts by weight of propylene glycol monomethyl ether acetate was added dropwise to the flask over approximately 4 hours. After the monomer addition was complete, the mixture was maintained at the same temperature for approximately 4 hours, and then cooled to room temperature to obtain a copolymer-containing solution with a solid content of 33.8% by weight. The weight-average molecular weight (Mw) of the resulting copolymer was 16,000, and the dispersion was 3.32.

[0209] [Manufacturing Example 7]

[0210] Using 11 parts by weight of acrylic acid (AA), 79 parts by weight of methyl 3,4-epoxycyclohexyl methacrylate (cyclomer M100), and 10 parts by weight of methyl methacrylate (MMA) as monomers, the same procedure as in Manufacturing Example 6 was performed to obtain a copolymer-containing solution with a solid content of 33.4% by weight. The resulting copolymer had a weight-average molecular weight (Mw) of 16,000 and a dispersion of 3.30.

[0211] [Manufacturing Example 8]

[0212] 11 parts by weight of acrylic acid (AA) and 89 parts by weight of 3,4-epoxy tricyclic acrylic acid [5.2.1.0] were used. 2,6 ] Decane-9-yl ester and 3,4-epoxytricyclic acrylate [5.2.1.0] 2,6 Using a mixture of decane-8-yl esters (monomer B2) as the monomer, the same procedures as in Manufacturing Example 1 were performed to obtain a copolymer-containing solution with a solid content of 34.1% by weight. The resulting copolymer had a weight-average molecular weight (Mw) of 18,000 and a dispersion of 3.43.

[0213] Table 1 shows the copolymer composition, weight-average molecular weight, dispersion, and exothermic peak temperature of the copolymers in Examples 1 to 8.

[0214] [Example 1-1]

[0215] In a container, 8.09 g of a copolymer solution prepared by preparing the copolymer as an alkali-soluble resin in Manufacturing Example 1 above, 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.

[0216] [Examples 1-2]

[0217] Using 8.09 g of the copolymer obtained in Manufacturing Example 2 above as an alkali-soluble resin, a copolymer-containing solution was prepared. Otherwise, the same operation as in Examples 1-1 was performed to prepare photosensitive resin compositions 1-2.

[0218] [Examples 1-3]

[0219] Using 8.09 g of the copolymer obtained in Manufacturing Example 3 as an alkali-soluble resin, a copolymer-containing solution was prepared. Otherwise, the same operation as in Examples 1-1 was performed to prepare photosensitive resin compositions 1-3.

[0220] [Examples 1-4]

[0221] Using 8.09 g of the copolymer obtained in Manufacturing Example 4 above as an alkali-soluble resin, a copolymer-containing solution was prepared. Otherwise, the same operation as in Examples 1-1 was performed to prepare photosensitive resin compositions 1-4.

[0222] [Examples 1-5]

[0223] Using 8.09 g of the copolymer obtained in Manufacturing Example 5 as an alkali-soluble resin, a copolymer-containing solution was prepared. Otherwise, the same operation as in Examples 1-1 was performed to prepare photosensitive resin compositions 1-5.

[0224] [Comparative Example 1-1]

[0225] Using 8.09 g of the copolymer obtained in Manufacturing Example 6 as an alkali-soluble resin, a copolymer-containing solution was prepared. Otherwise, the same operation as in Examples 1-1 was performed to prepare photosensitive resin compositions 1-6.

[0226] [Comparative Examples 1-2]

[0227] Using 8.09 g of the copolymer obtained in Manufacturing Example 7 as an alkali-soluble resin, a copolymer-containing solution was prepared. Otherwise, the same operation as in Examples 1-1 was performed to prepare photosensitive resin compositions 1-7.

[0228] [Comparative Examples 1-3]

[0229] Using 8.09 g of the copolymer obtained in Manufacturing Example 8 as an alkali-soluble resin, a copolymer-containing solution was prepared. Otherwise, the same operation as in Examples 1-1 was performed to prepare photosensitive resin compositions 1-8.

[0230] The compositions of the photosensitive resin compositions of the above-described examples and comparative examples are recorded in Table 2.

[0231] [Example 2-1]

[0232] Weigh out 7.7g of pigment CI Pigment Red 254 (as colorant), 3.1g of dispersant DISPERBYK-2000, and 36.0g of solvent MMPGAC into a container. Add 45g of 1.0mm diameter zirconia beads and cover the container. Shake the container for 3 hours using a paint shaker. After 3 hours, separate the pigment dispersion from the zirconia beads, add 45g of 0.5mm zirconia beads, and shake again for 3 hours. Then, separate the pigment dispersion from the zirconia beads, add 45g of 0.3mm zirconia beads, and shake again for 3 hours. Finally, separate the zirconia beads to obtain the pigment dispersion.

[0233] For the obtained pigment dispersion of 4.68g, 8.09g of a copolymer solution prepared by preparing the copolymer as an alkali-soluble resin in Manufacturing Example 1 above, 2.25g of DPHA as a photopolymerizable compound, 0.20g of 1-hydroxycyclohexylphenyl ketone as a photopolymerization initiator, and 15.2g of MMPGAC as a solvent were weighed into a container and stirred for 30 minutes, thereby preparing photosensitive resin composition 2-1.

[0234] [Example 2-2]

[0235] Using 8.09 g of the copolymer obtained in Manufacturing Example 2 above as an alkali-soluble resin, a copolymer-containing solution was prepared. Otherwise, the same operation as in Example 2-1 was performed to prepare photosensitive resin composition 2-2.

[0236] [Examples 2-3]

[0237] Using 8.09 g of the copolymer obtained in Manufacturing Example 3 above as an alkali-soluble resin, a copolymer-containing solution was prepared. Otherwise, the same operation as in Example 2-1 was performed to prepare photosensitive resin composition 2-3.

[0238] [Examples 2-4]

[0239] Using 8.09 g of the copolymer obtained in Manufacturing Example 4 above as an alkali-soluble resin, a copolymer-containing solution was prepared. Otherwise, the same operation as in Example 2-1 was performed to prepare photosensitive resin composition 2-4.

[0240] [Examples 2-5]

[0241] Using 8.09 g of the copolymer obtained in Manufacturing Example 5 as an alkali-soluble resin, a copolymer-containing solution was prepared. Otherwise, the same operation as in Example 2-1 was performed to prepare photosensitive resin composition 2-5.

[0242] [Comparative Example 2-1]

[0243] Using 8.09 g of the copolymer obtained in Manufacturing Example 6 as an alkali-soluble resin, a copolymer-containing solution was prepared. Otherwise, the same operation as in Example 2-1 was performed to prepare photosensitive resin composition 2-6.

[0244] [Comparative Example 2-2]

[0245] Using 8.09 g of the copolymer obtained in Manufacturing Example 7 as an alkali-soluble resin, a copolymer-containing solution was prepared. Otherwise, the same operation as in Example 2-1 was performed to prepare photosensitive resin composition 2-7.

[0246] [Comparative Examples 2-3]

[0247] Using 8.09 g of the copolymer obtained in Manufacturing Example 8 as an alkali-soluble resin, a copolymer-containing solution was prepared, and otherwise the same operation as in Example 2-1 was performed to prepare photosensitive resin composition 2-8.

[0248] The compositions of the photosensitive resin compositions of the above-described examples and comparative examples are recorded in Table 4.

[0249] <Evaluation Experiment>

[0250] 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.

[0251] (1) Storage stability test-1

[0252] 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 immediately after polymerization and the viscosity after one week of storage at 40°C were measured. The viscosity increase rate was calculated according to the following formula. It should be noted that the viscosity (unit: mPa·s) was measured using a viscometer (trade name "LVDV2T", manufactured by Brookfield Company) at a rotation speed of 60 and a temperature of 23°C.

[0253] P: Viscosity immediately after polymerization; Q: Viscosity after storage at 40°C for one week.

[0254] Viscosity increase rate = {(Q / P)×100}-100.

[0255] (2) Solvent resistance test-1

[0256] The photosensitive resin compositions obtained in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-3 were coated onto a glass plate using a spin coater and then cured at 200°C for 30 minutes to produce test pieces. The thickness of the cured coating was 3 μm.

[0257] For the test pieces, γ-butyrolactone (γ-BL) and N-methylpyrrolidone (NMP) were added dropwise, and the pieces were left to stand for 10 minutes. Then, the pieces were washed with water. If the area where the solvent was added showed no change, it was marked with ◎; if a slight trace of solvent remained but disappeared when wiped, it was marked with ○; if a trace of solvent remained and did not disappear when wiped, it was marked with Δ; and if the entire surface changed color, it was marked with ×.

[0258] (3) Solvent resistance test - 2

[0259] In the preparation of the test piece, the curing temperature was set to 230°C. In addition, the solvent resistance test of the cured product was carried out in the same manner as in the solvent resistance test-1.

[0260] The photosensitive resin compositions of Examples 1-1 to 1-5 do not easily thicken even at 40°C and exhibit good storage stability. Furthermore, they show good solvent resistance even at a curing temperature of 200°C, similar to that at 230°C. On the other hand, it is known that the photosensitive resin compositions of Comparative Examples 1-1 to 1-2 gel at 40°C, and as can be understood from this, their storage stability is poor. Furthermore, it is known that the photosensitive resin composition of Comparative Example 3 exhibits good storage stability through the use of monomer B2 (EDCPA), but if the curing temperature is lowered from 230°C to 200°C, it does not cure sufficiently, thus reducing its solvent resistance.

[0261] 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.

[0262] (1) Storage stability test-2

[0263] 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 immediately after polymerization and the viscosity after one week of storage at 40°C were measured. The viscosity increase rate was calculated according to the following formula. It should be noted that the viscosity (unit: mPa·s) was measured using a viscometer (trade name "LVDV2T", manufactured by Brookfield Company) at a rotation speed of 60 and a temperature of 23°C.

[0264] P: Viscosity immediately after polymerization; Q: Viscosity after storage at 40°C for one week.

[0265] Viscosity increase rate = {(Q / P)×100}-100.

[0266] (2) Solvent resistance test - 3

[0267] The photosensitive resin compositions obtained in Examples 2-1 to 2-5 and Comparative Examples 2-1 to 2-3 were coated onto a glass plate using a spin coater and then cured at 200°C for 30 minutes to produce test films. The thickness of the cured coating was 2 μm.

[0268] For the test pieces, γ-butyrolactone (γ-BL) and N-methylpyrrolidone (NMP) were added dropwise, and the pieces were left to stand for 10 minutes. Then, the pieces were washed with water. If the area where the solvent was added showed no change, it was marked with ◎; if a slight trace of solvent remained but disappeared when wiped, it was marked with ○; if a trace of solvent remained and did not disappear when wiped, it was marked with Δ; and if the entire surface changed color, it was marked with ×.

[0269] (3) Solvent resistance test - 4

[0270] In the preparation of the test pieces, the curing temperature was set to 230°C. In addition, the solvent resistance test of the cured product was carried out in the same manner as the solvent resistance test-3.

[0271] The photosensitive resin compositions of Examples 2-1 to 2-5 do not easily thicken even at 40°C and exhibit good storage stability. Furthermore, they show good solvent resistance even at a curing temperature of 200°C, similar to that at 230°C. On the other hand, the photosensitive resin compositions of Comparative Examples 2-1 to 2-2 thicken at 40°C, and as can be understood from this, their storage stability is poor. Moreover, the photosensitive resin composition of Comparative Example 2-3 exhibits good storage stability through the use of monomer B2 (EDCPA), but if the curing temperature is lowered from 230°C to 200°C, it does not cure sufficiently, thus reducing its solvent resistance.

[0272]

[0273]

[0274]

[0275]

[0276]

[0277] The components used in the manufacturing examples, embodiments, and comparative examples will be described below.

[0278] Monomer B1: 3-oxatricyclomethacrylic acid [3.2.1.0] 2,4 Octane-6-methyl ester (refer to Reference Example 1)

[0279] GMA: Glycidyl methacrylate (Nippon Oil Co., Ltd.)

[0280] Cyclomer M100: 3,4-epoxycyclohexyl methyl methacrylate (manufactured by DAICEL).

[0281] Monomer B2: 3,4-Epoxy Tricyclic Acrylic Acid [5.2.1.0] 2,6 ] Decane-9-yl ester and 3,4-epoxytricyclic acrylate [5.2.1.0] 2,6 A mixture of decane-8-yl esters (trade name "E-DCPA", manufactured by DAICEL Co., Ltd.).

[0282] ST: Styrene (manufactured by FUJIFILM and Koichi Pharmaceutical Co., Ltd.).

[0283] MMA: Methyl methacrylate (manufactured by FUJIFILM and Koichi Pharmaceutical Co., Ltd.).

[0284] CHMI: Cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.)

[0285] VP: N-vinylpyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0286] MMPGAC: Propylene glycol monomethyl ether acetate (manufactured by DAICL).

[0287] PR 254: CI Pigment Red 254 (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0288] DISPERBYK-2000: Amine value 4mgKOH / g, non-volatile components 40% (manufactured by BYK Chemie Japan).

[0289] DHPA: dipentaerythritol hexaacrylate (trade name "KAYARAD DPHA"; manufactured by Nippon Kayaku Co., Ltd.).

[0290] 1-Hydroxycyclohexylphenyl ketone (manufactured by FUJIFILM and Koko Pure Chemical Co., Ltd.)

[0291] In summary, the following notes describe the structure and variations of this invention. [1]

[0293] A photosensitive resin composition comprising:

[0294] Alkali-soluble resins, photopolymerizable compounds, photopolymerization initiators, and solvents.

[0295] 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 formula (1). (In formula (1), R...) 1 and R 2 Each may be the same or different, representing a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. X represents a single bond or a divalent hydrocarbon group optionally containing a heteroatom. Y represents a methylene or ethylene group optionally having an alkyl group having 1 to 3 carbon atoms as a substituent, an oxygen atom, or a sulfur atom optionally bonded to an oxygen atom. n represents an integer from 0 to 7), wherein the alkali-soluble resin is a copolymer with an exothermic peak temperature of 180 to 220°C when heated at a rate of 5°C / min using a differential scanning calorimeter. [2]

[0297] According to the photosensitive resin composition described in [1], wherein,

[0298] The compound represented by formula (1) is the compound of formula (1a) (where R... 1 R 2 X, Y and n represent compounds as described in equation (1). [3]

[0300] According to the photosensitive resin composition described in [1] or [2], wherein,

[0301] The copolymer further comprises a building unit (C) derived from at least one compound selected from the group consisting of (c1) to (c4) below.

[0302] (c1) Styrene optionally substituted with alkyl groups;

[0303] (c2)N-substituted maleimide;

[0304] (c3) N-vinyl compounds; and

[0305] (c4) The unsaturated carboxylic acid derivative shown in formula (2) (where R is a given formula) 11 R represents an alkyl group having 1 to 7 hydrogen atoms or carbon atoms. 12 This indicates a hydrocarbon group that optionally contains a heteroatom. (Z indicates a heteroatom). [4]

[0307] The photosensitive resin composition according to any one of [1] to [3], wherein,

[0308] The copolymer also contains constituent units (D) derived from (meth)acrylamide or (meth)acrylonitrile. [5]

[0310] The photosensitive resin composition according to any one of [1] to [4], wherein,

[0311] The proportion of constituent unit (A) relative to all constituent units of the copolymer is 2 to 60% by weight, 3 to 40% by weight, or 5 to 20% by weight. [6]

[0313] The photosensitive resin composition according to any one of [1] to [5], wherein,

[0314] The proportion of constituent unit (B) relative to all constituent units of the copolymer is 40-98% by weight, 60-95% by weight, or 75-90% by weight. [7]

[0316] The photosensitive resin composition according to any one of [3], [5] and [6], wherein,

[0317] The proportion of the constituent unit (C) relative to all the constituent units of the copolymer is 0-85% by weight, 1-60% by weight, or 2-40% by weight. [8]

[0319] The photosensitive resin composition according to any one of [3], [5] to [7], wherein,

[0320] The proportion of constituent unit (A) to all constituent units of the copolymer is 2 to 60% by weight, the content of constituent unit (B) is 40 to 98% by weight, and the content of constituent unit (C) is 0 to 85% by weight. [9]

[0322] The photosensitive resin composition according to any one of [1] to [8], wherein,

[0323] When the copolymer comprises constituent unit (A) and constituent unit (B) but does not contain constituent unit (C), the total amount of constituent unit (A) and constituent unit (B) is 90% by weight or more, 95% by weight or more, 99% by weight or more, or substantially 100% by weight relative to all constituent units. When the copolymer comprises constituent unit (A), constituent unit (B) and constituent unit (C), the total amount of constituent units (A) to (C) is 90% by weight or more, 95% by weight or more, 99% by weight or more, or 100% by weight relative to all constituent units.

[10]

[0325] The photosensitive resin composition according to any one of [1] to [9], wherein,

[0326] The weight-average molecular weight (Mw) of the copolymer is 1,000–1,000,000, 3,000–300,000, or 5,000–100,000.

[11]

[0328] The photosensitive resin composition according to any one of [1] to

[10] , wherein,

[0329] The molecular weight distribution (weight-average molecular weight to number-average molecular weight: Mw / Mn) of the copolymer is below 5.0, 1.0 to 4.5, or 1.0 to 4.0.

[12]

[0331] The photosensitive resin composition according to any one of [1] to

[11] , wherein,

[0332] The exothermic peak temperature of the polymer when heated at a rate of 5°C / min using a differential scanning calorimeter is 180–220°C.

[13]

[0334] The photosensitive resin composition according to any one of [1] to

[12] , wherein,

[0335] It also includes coloring materials.

[14]

[0337] According to the photosensitive resin composition described in

[13] , wherein,

[0338] The colorant is a pigment and / or dye.

[15]

[0340] According to the photosensitive resin composition described in

[13] or

[14] , wherein,

[0341] The content of the colorant relative to the solid components of the photosensitive resin composition is 3-50% by weight or 5-30% by weight.

[16]

[0343] The photosensitive resin composition according to any one of [1] to

[15] , wherein,

[0344] The photopolymerizable compound comprises at least one selected from the group consisting of polyfunctional vinyl compounds, polyfunctional thiols, and polyfunctional epoxy compounds.

[17]

[0346] The photosensitive resin composition according to any one of [1] to

[16] , wherein,

[0347] 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. 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]

[0349] A cured product of any one of the photosensitive resin compositions described in [1] to

[17] .

[19]

[0351] A color filter is a cured product of the photosensitive resin composition described in any one of [1] to

[17] .

[20]

[0353] A component for a display device or a display device comprising the color filter described in

[19] .

[0354] Industrial availability

[0355] According to the present invention, a photosensitive resin composition with excellent storage stability, excellent curing reactivity, and excellent solvent resistance of the cured product is provided. Furthermore, a cured product of the photosensitive resin composition having the above-mentioned properties, a color filter as the cured product, and a component or display device having the color filter are provided.

Claims

1. A photosensitive resin composition comprising: an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, the alkali-soluble resin is a copolymer comprising a constitutional unit (A) derived from an unsaturated carboxylic acid or an acid anhydride thereof and a constitutional unit (B) introduced by applying copolymerization to a compound represented by the following formula (1), [Chemical Formula 1] In the formula, R 1 and R 2 Each may be the same or different, representing a hydrogen atom or an alkyl group having 1 to 7 carbon atoms; X represents a single bond or a divalent hydrocarbon group optionally containing a heteroatom; Y represents a methylene or ethylene group optionally having an alkyl group having 1 to 3 carbon atoms as a substituent, an oxygen atom, or a sulfur atom optionally bonded to an oxygen atom; n represents an integer from 0 to 7. wherein the alkali-soluble resin is a copolymer having an exothermic peak top temperature of 180 to 220°C when temperature is increased at a rate of 5°C / minute using a differential scanning calorimeter.

2. The photosensitive resin composition according to claim 1, wherein, the copolymer further comprises a constitutional unit (C) derived from at least one compound selected from the group consisting of the following (c1) to (c4), (c1) styrene optionally substituted with an alkyl group; (c2) N-substituted maleimide; (c3) N-vinyl compound; and (c4) an unsaturated carboxylic acid derivative represented by the following formula (2), [Chemical Formula 2] wherein R 11 represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, R 12 represents a hydrocarbon group optionally containing a heteroatom, and Z represents a heteroatom.

3. The photosensitive resin composition according to claim 2, wherein, the proportion of the constitutional unit (A) is 2 to 60% by weight, the proportion of the constitutional unit (B) is 40 to 98% by weight, and the proportion of the constitutional unit (C) is 0 to 85% by weight, with respect to the total constitutional units of the copolymer.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein, a color material is further included.

5. The photosensitive resin composition according to claim 4, wherein, the color material is a pigment and / or a dye.

6. A cured product which is a cured product of the photosensitive resin composition according to any one of claims 1 to 5.

7. A color filter which is a cured product of the photosensitive resin composition according to any one of claims 1 to 5.

8. A member for a display device or a display device comprising the color filter according to claim 7.

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