Colored photosensitive resin composition, color filter, and component for display device or display device

Abstract

To provide a colored photosensitive resin composition excellent in storage stability and curing reactivity and also excellent in solvent resistance of a cured product.SOLUTION: The colored photosensitive resin composition contains: an alkali-soluble resin which is a copolymer containing a constituent unit (A) derived from an unsaturated carboxylic acid or an anhydride thereof, and a constituent unit (B) derived from an epoxy compound represented by formula (b1); a coloring material; a photopolymerizable compound; a photopolymerization initiator; and a solvent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to a colored photosensitive resin composition, a color filter, and a component for a display device or a display device. [Background technology]

[0002] A known colored photosensitive resin composition used in the manufacture of color filters is a resin composition containing an alkali-soluble resin, a colorant (pigment or dye), a photopolymerizable compound, and a photopolymerization initiator.

[0003] Patent Document 1 discloses a copolymer containing methacrylic acid and benzyl methacrylate as constituent monomers as the alkali-soluble resin. Patent Document 2 discloses a copolymer containing methacrylic acid and glycidyl methacrylate as constituent monomers as the alkali-soluble resin. Patent Document 3 discloses a copolymer containing methacrylic acid and 3,4-epoxytricyclo[5.2.1.0 2,6 A copolymer containing decyl acrylate as a constituent monomer is disclosed. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 9-134004 [Patent Document 2] Japanese Patent Publication No. 2011-237728 [Patent Document 3] Japanese Patent Publication No. 2007-333847 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, the colored photosensitive resin composition disclosed in Patent Document 1 has the drawback of poor solvent resistance of the cured product. The colored photosensitive resin composition disclosed in Patent Document 2 has the drawback of poor stability, such as increasing in viscosity over time. Furthermore, the solvent resistance of the cured product was not sufficient. The colored photosensitive resin composition disclosed in Patent Document 3 has excellent storage stability, but it has poor reactivity with carboxylic acids and requires a curing temperature of 230°C or higher.

[0006] Therefore, an object of the present invention is to provide a colored photosensitive resin composition that has excellent storage stability, excellent curing reactivity, and excellent solvent resistance of the cured product. Another object of the present invention is to provide a color filter formed from a colored photosensitive resin composition having the above characteristics, and a display device component or display device equipped with the color filter. [Means for solving the problem]

[0007] As a result of diligent research to achieve the above objective, the present inventors have found that a colored photosensitive resin composition using a copolymer containing specific structural units as an alkali-soluble resin exhibits excellent storage stability, cures at relatively low temperatures, and has excellent solvent resistance in the cured product. The present invention was completed based on these findings.

[0008] In other words, this disclosure includes alkali-soluble resins, colorants, photopolymerizable compounds, photopolymerization initiators, and solvents. The alkali-soluble resin comprises a constituent unit (A) derived from an unsaturated carboxylic acid or its anhydride, and the following formula (b1) [ka] (In the formula, R b1 R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. b2 R represents a divalent hydrocarbon group which may contain heteroatoms. b3 This represents a divalent organic group having two or more epoxy groups. Provided is a colored photosensitive resin composition which is a copolymer containing a structural unit (B) derived from an epoxy compound represented by [[ID=END]]

[0009] The epoxy compound is represented by the following formula (b3)

Chemical formula

Chemical formula

[0010] The copolymer preferably further comprises a constituent unit (C) derived from at least one compound selected from the group consisting of (c1) to (c4) below. (c1) Styrene which may be substituted with alkyl groups (c2)N-substituted maleimide (c3) N-vinyl compound (c4) The following formula (2) [ka] (In the formula, R 11 R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. 12 (where X represents a monovalent hydrocarbon group which may contain heteroatoms.) Unsaturated carboxylic acid derivatives represented by

[0011] Preferably, the copolymer has a content of 2 to 50% by weight of component (A), 10 to 98% by weight of component (B), and 0 to 80% by weight of component (C) relative to the total constituent units of the copolymer.

[0012] The colorant may be a pigment and / or a dye.

[0013] This disclosure also provides a color filter which is a cured product of the aforementioned colored photosensitive resin composition.

[0014] This disclosure further provides a display device component or display device comprising the aforementioned color filter. [Effects of the Invention]

[0015] The present invention provides a colored photosensitive resin composition that exhibits excellent storage stability, excellent curing reactivity, and excellent solvent resistance of the cured product. Furthermore, it provides a color filter which is a cured product of the colored photosensitive resin composition having the above-mentioned properties, and a display device component or display device equipped with the color filter. [Modes for carrying out the invention]

[0016] The colored photosensitive resin composition relating to this disclosure is mainly used as a colored pattern forming material and comprises an alkali-soluble resin, a colorant, a photopolymerizable compound, a photopolymerization initiator, and a solvent.

[0017] <Alkali-soluble resin> In this disclosure, a copolymer is used as the alkali-soluble resin, comprising a constituent unit (A) derived from an unsaturated carboxylic acid or its anhydride, and a constituent unit (B) derived from an epoxy compound represented by formula (b1). The copolymer may further contain a constituent unit (C) derived from at least one compound selected from the group consisting of (c1) to (c4). Furthermore, it may also contain a constituent unit (D) described later, as a constituent unit other than constituent units (A) to (C).

[0018] [Constituent Unit (A)] The constituent unit (A) can be introduced into the copolymer by polymerizing an unsaturated carboxylic acid or its acid anhydride (a) with an epoxy compound (b) represented by formula (b1).

[0019] The unsaturated carboxylic acid or its acid anhydride (a) is not particularly limited, but 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 copolymerizability and developability. The unsaturated carboxylic acid or its acid anhydride (a) can be used alone or in combination of two or more.

[0020] The proportion (content) of constituent unit (A) in the copolymer is not particularly limited, but for example, it is preferably 2 to 50% by weight, more preferably 3 to 40% by weight, even more preferably 5 to 25% by weight, and particularly preferably 10 to 20% by weight relative to the total amount of constituent units constituting the copolymer. When the proportion of constituent unit (A) is within the above range, the cured product tends to have excellent solvent resistance. When the proportion of constituent unit (A) is below the above upper limit, excessive development is suppressed, and therefore the product tends to have excellent solvent resistance. In this disclosure, the proportion of constituent unit in the copolymer is based on the weight of the compound (monomer) used in copolymerization. For example, the proportion of constituent unit (A) in the copolymer means the ratio of the amount of unsaturated carboxylic acid or its acid anhydride (a) used to the total amount (100% by weight) of the compound used in copolymerization.

[0021] [Constituent Unit (B)] The constituent unit (B) can be introduced into the copolymer by polymerizing an epoxy compound (b) represented by the following formula (b1) with an unsaturated carboxylic acid or its acid anhydride (a). [ka]

[0022] In formula (b1), R b1 R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. b2 R represents a divalent hydrocarbon group which may contain heteroatoms. b3 This represents a divalent organic group having two or more epoxy groups.

[0023] R b1 Examples of C1-C7 alkyl groups in include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, hexyl, and heptyl groups. From the viewpoint of copolymerizability and reactivity, R b1 The hydrogen atom, methyl group, or ethyl group is preferred.

[0024] R b2In a divalent hydrocarbon group which may contain a heteroatom, the heteroatom may be bonded to the terminal of the hydrocarbon group or interposed between the carbon atoms constituting the hydrocarbon group. The heteroatom is not particularly limited, but examples include a nitrogen atom, an oxygen atom, and a sulfur atom. b2 It may have substituents.

[0025] R b2 Examples of divalent hydrocarbon groups that may contain heteroatoms include linear or branched alkylene groups such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene (alkylene groups having 1 to 12 carbon atoms are preferred, alkylene groups having 1 to 6 carbon atoms are more preferred, and alkylene groups having 1 to 3 carbon atoms are particularly preferred); and cycloalkylene groups such as 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, and cyclohexylidene (cycloalkylene groups having 3 to 12 carbon atoms are preferred, and cycloalkylene groups having 4 to 10 carbon atoms are more preferred). Examples include cycloalkylene groups having 5 to 8 carbon atoms, which are particularly preferred; oxyalkylene groups such as oxymethylene groups, oxyethylene groups, and oxypropylene groups (oxyalkylene groups having 1 to 12 carbon atoms are preferred, and oxyalkylene groups having 1 to 6 carbon atoms are more preferred); thioalkylene groups such as thiomethylene groups, thioethylene groups, and thiopropylene groups (thioalkylene groups having 1 to 12 carbon atoms are preferred, and thioalkylene groups having 1 to 6 carbon atoms are more preferred); aminoalkylene groups such as aminomethylene groups, aminoethylene groups, and aminopropylene groups (aminoalkylene groups having 1 to 12 carbon atoms are preferred, and aminoalkylene groups having 1 to 6 carbon atoms are more preferred); and divalent groups formed by the bonding of two or more of these. Among these, linear alkylene groups having 1 to 3 carbon atoms are preferred, and ethylene groups are more preferred from the viewpoint of storage stability.

[0026] R b3is a divalent organic group having two or more epoxy groups. That is, a divalent organic group having at least two epoxy groups. The epoxy groups are preferably epoxy groups other than alicyclic epoxy groups. This is because ordinary epoxy groups (epoxy groups other than alicyclic epoxy groups) have superior reactivity compared to alicyclic epoxy groups, leading to the copolymer of this disclosure exhibiting good curability even at relatively low temperatures. Furthermore, in the epoxy compound (b) represented by formula (b1), if the structure around the epoxy groups is crowded, the reactivity of the epoxy groups decreases. Therefore, by using epoxy groups other than alicyclic epoxy groups to improve curability, good solvent resistance and curability can be achieved. An alicyclic epoxy group refers to a group composed of two adjacent carbon atoms and an oxygen atom constituting an alicyclic ring, such as a cyclohexene oxide group. The at least two epoxy groups may be the same or different. 3b It may have substituents.

[0027] R b3 Because the divalent organic group in has two or more epoxy groups, the amount of epoxy groups per molecule of acrylic monomer increases, and therefore the crosslinking density of the cured copolymer containing the monomer as a constituent unit increases. For this reason, the formed cured film takes on a dense structure, which is thought to improve solvent resistance. Note that the number of epoxy groups in epoxy compound (b) represented by formula (b1), i.e., R b3 The number of epoxy groups in the divalent organic group is preferably 2 to 10, more preferably 2 to 6, and even more preferably 2 to 4. Being within this range tends to result in good solvent resistance and curability.

[0028] R b3 Examples of organic groups in this context include hydrocarbon groups, heterocyclic groups, and groups in which two or more of these are linked by a single bond or a linking group.

[0029] Examples of the hydrocarbon groups include linear or branched alkylene groups such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene (e.g., alkylene groups having 1 to 12 carbon atoms); monocyclic or polycyclic cycloalkylene groups such as 1,2-cyclopentylene and 1,2-cyclohexylene (e.g., cycloalkylene groups having 3 to 12 carbon atoms); and arylene groups such as phenylene. Examples of the heterocyclic groups include 5 to 10-membered heterocycloalkylene groups and heteroarylene groups containing at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur atoms (e.g., heterocycles containing oxygen atoms such as furan rings; heterocycles containing nitrogen atoms such as pyrrole rings and pyridine rings; and groups obtained by removing two hydrogen atoms from the structural formula of heterocycles containing sulfur atoms such as thiophene rings). Examples of the linking groups include heteroatoms such as nitrogen atoms, oxygen atoms, and sulfur atoms (e.g., ether bonds (-O-), thioether bonds (-S-), etc.), carbonyl groups (-CO-), ester bonds (-COO-), amide bonds (-CONH-), and carbonate bonds (-OCOO-).

[0030] That is, R b3 This indicates a divalent group in which at least two hydrogen atoms in these organic groups are substituted with epoxy groups.

[0031] R b3 Preferably, the group has two or more epoxy groups, and the two or more hydrocarbon groups are linked via a linking group containing an oxygen atom (particularly an ether bond). In this case, the two or more hydrocarbon groups other than the epoxy group are preferably linear or branched alkylene groups (particularly alkylene groups with 1 to 4 carbon atoms in the main chain), monocyclic or polycyclic cycloalkylene groups (particularly cycloalkylene groups with 5 to 8 carbon atoms) which may have substituents such as alkyl groups, and more preferably ethylene groups, cyclohexene groups, and norbornene groups which may have substituents. The two or more hydrocarbon groups may be the same or different. Note that the number of carbon atoms in the main chain of the alkylene group is R b2This refers to the number of carbon atoms in the shortest carbon chain of the alkylene group, from the carbon atom bonded to the O- to the carbon atom bonded to the OH.

[0032] Examples of the epoxy compound (b) include the compound represented by the following formula (b2).

[0033] [ka]

[0034] In formula (b2), R b1 R in equation (b1) b1 This is similar to what was described above, and represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. b2 R in equation (b1) b2 This is similar to what was described earlier, and represents a divalent hydrocarbon group which may contain heteroatoms. b4 represents a divalent hydrocarbon group that is identical or different, has an epoxy group, and may also contain a heteroatom. nb1 represents an integer of 2 or more.

[0035] R b4 In this context, a divalent hydrocarbon group having an epoxy group and possibly containing heteroatoms means a divalent hydrocarbon group in which one or more hydrogen atoms are substituted for an epoxy group and which may contain heteroatoms. The epoxy group is preferably an epoxy group other than an alicyclic epoxy group. 4b It may have substituents.

[0036] R b4Examples of divalent hydrocarbon groups that may contain heteroatoms include linear or branched alkylene groups such as methylene, methylmethylene, dimethylmethylene, and ethylene (alkylene groups with 1 to 8 carbon atoms are preferred, and alkylene groups with 2 to 4 carbon atoms are more preferred); monocyclic or polycyclic cycloalkylene groups such as 1,2-cyclopentylene (cycloalkylene groups with 3 to 12 carbon atoms are preferred, cycloalkylene groups with 4 to 10 carbon atoms are more preferred, and cycloalkylene groups with 5 to 8 carbon atoms are particularly preferred); oxyalkylene groups such as oxymethylene, oxyethylene, and oxypropylene; thioalkylene groups such as thiomethylene, thioethylene, and thiopropylene; aminoalkylene groups such as aminomethylene, aminoethylene, and aminopropylene; and divalent groups formed by the bonding of two or more of these. b4 This represents a group in which at least one hydrogen atom of a divalent hydrocarbon group, which may contain these heteroatoms, is substituted with an epoxy group.

[0037] R b4 In this context, the divalent hydrocarbon groups, excluding epoxy groups and which may contain heteroatoms, are preferably linear or branched alkylene groups (particularly alkylene groups with 1 to 4 carbon atoms in the main chain), monocyclic or polycyclic cycloalkylene groups (particularly cycloalkylene groups with 5 to 8 carbon atoms) which may have substituents such as alkyl groups, and more preferably ethylene groups, cyclohexene groups, and norbornene groups which may have substituents. Note that the R in two or more parentheses with nb1 is b4 They may be the same or they may be different.

[0038] From the viewpoint of storage stability, the epoxy compound (b1) is preferably a compound represented by the following formula (b3) or a compound represented by the following formula (b4). The epoxy compound (b1) can be used alone or in combination of two or more types.

[0039] [ka]

[0040] In equation (b3), R b1 R in equation (b1) b1 This is similar to what was described above, and represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. b2 R in equation (b1) b2 This is similar to what was described earlier, and represents a divalent hydrocarbon group which may contain heteroatoms. b5 R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, either identical or different. b6 represents a divalent hydrocarbon group, which may be the same or different and may contain single bonds or heteroatoms. nb2 and nb3 are each integers greater than or equal to 0, and the sum of nb2 and nb3 is 2 or greater. The oxirane ring may have an alkyl group having 1 to 6 carbon atoms.

[0041] The two groups within the brackets in the formula do not necessarily have to be in the order shown in formula (b3). That is, the compound represented by formula (b3) has nb2 and nb3 of the two groups (constituent units) within the brackets in the formula, and the arrangement of these groups may be in the order shown in formula (b3), reversed, alternating, or a certain number consecutively. To explain in more detail, the two groups within the brackets are -C(R b5 )2-C(R b5 )(R b6 A group represented by -C2H3O)- (hereinafter referred to as the "L group") and -C(R b5 )(R b6 -C2H3O)-C(R b5 The group represented by )2- (hereinafter referred to as the "R group") is -L as shown in formula (b3) above. nb2 -R nb3 - is also acceptable, -R nb3 -L nb2 - may also be the case. Also, if nb2 and nb3 are each 2 or more, -LRRL ··· They can be arranged alternately like this, or a certain number can be arranged consecutively.

[0042] [ka]

[0043] In formula (b4), R b1 R in equation (b1) b1 This is similar to what was described above, and represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. b2 R in equation (b1) b2 This is similar to what was described earlier, and represents a divalent hydrocarbon group which may contain heteroatoms. b7 R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, either identical or different. b8 represents a divalent hydrocarbon group bonded to ring Z, which may be the same or different and may contain single bonds or heteroatoms. m represents an integer from 1 to 3. Ring Z represents an alicyclic hydrocarbon ring having 3 to 20 carbon atoms. nb4 represents an integer of 2 or more. The oxirane ring may have an alkyl group having 1 to 6 carbon atoms. Ring Z is R b7 and R b8 The other group may be an alkyl group having 1 to 6 carbon atoms.

[0044] R b5 and R b7 The alkyl group having 1 to 6 carbon atoms in the compound is not particularly limited, but examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, and hexyl groups.

[0045] R b6 and R b8The divalent hydrocarbon group in which heteroatoms may be present is, for example, a linear or branched alkylene group such as methylene, methylmethylene, dimethylmethylene, ethylene, propylene, trimethylene, butylene, pentylene, and hexylene (alkylene groups having 1 to 18 carbon atoms are preferred, alkylene groups having 2 to 12 carbon atoms are more preferred, and alkylene groups having 3 to 8 carbon atoms are particularly preferred); or a cycloalkylene group such as 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, and cyclohexylidene (cycloalkylene groups having 3 to 12 carbon atoms are preferred, and cycloalkylene groups having 4 to 10 carbon atoms are particularly preferred). Examples include: a C5-C8 cycloalkylene group is more preferred; an oxyalkylene group such as an oxymethylene group, oxyethylene group, or oxypropylene group (an oxyalkylene group having 1 to 12 carbon atoms is preferred, and an oxyalkylene group having 1 to 6 carbon atoms is more preferred); a thioalkylene group such as an thiomethylene group, thioethylene group, or thiopropylene group (an thioalkylene group having 1 to 12 carbon atoms is preferred, and an thioalkylene group having 1 to 6 carbon atoms is more preferred); an aminoalkylene group such as an aminomethylene group, aminoethylene group, or aminopropylene group (an aminoalkylene group having 1 to 12 carbon atoms is preferred, and an aminoalkylene group having 1 to 6 carbon atoms is more preferred); and a divalent group formed by the bonding of two or more of these.

[0046] R b6 From the viewpoint of storage stability, linear or branched alkylene groups having 1 to 18 carbon atoms are preferred, and more preferably linear or branched alkylene groups having 3 to 8 carbon atoms. b8 From the viewpoint of storage stability, a single bond is preferable.

[0047] Examples of alicyclic hydrocarbon rings having 3 to 20 carbon atoms in ring Z include cycloalkane rings with 3 to 20 members (preferably 3 to 15 members, particularly preferably 5 to 12 members) such as cyclopropane rings, cyclobutane rings, cyclopentane rings, cyclohexane rings, and cyclooctane rings; monocyclic alicyclic hydrocarbon rings with 3 to 20 members (preferably 3 to 15 members, particularly preferably 5 to 10 members) such as cycloalkene rings, cyclopropene rings, cyclobutene rings, cyclopentene rings, and cyclohexene rings; adamantane rings; norbornane rings, norbornene rings, bornane rings, isobornane rings, tricyclo[5.2.1.0 2,6 ] Decane ring, tetracyclo[4.4.0.1 2,5 .1 7,10 ] Rings containing norbornane rings such as dodecane rings; perhydroindene rings, decalin rings (perhydronaphthalene rings), perhydrofluorene rings (tricyclo[7.4.0.0 3,8 [Tridecane ring), perhydroanthracene ring, or other polycyclic aromatic condensed rings are hydrogenated (preferably fully hydrogenated rings); tricyclo[4.2.2.1 2,5 Examples include 2-6 ring bridged hydrocarbon rings, such as bicyclic, tricyclic, and tetracyclic bridged hydrocarbon rings (e.g., bridged hydrocarbon rings with 6-20 carbon atoms), such as undecane rings. Among these, 5-12 member cycloalkane rings or norbornane rings are preferred from the viewpoint of storage stability.

[0048] nb2 and nb3 are integers greater than or equal to 0. The sum of nb2 and nb3 is not particularly limited as long as it is 2 or greater, but is preferably between 2 and 20, more preferably between 2 and 12, even more preferably between 2 and 8, particularly preferably between 2 and 4, and most preferably 3.

[0049] nb4 is not particularly limited as long as it is an integer of 2 or greater, but for example it is preferably 2 to 20, more preferably 2 to 12, even more preferably 2 to 8, particularly preferably 2 to 4, and most preferably 3. m is not particularly limited as long as it is an integer of 1 to 3, but for example it is preferably 1.

[0050] In the compounds represented by formula (b3) and formula (b4), the C1-C6 alkyl group that the oxirane ring may have is not particularly limited, but examples include C1-C6 alkyl groups. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, pentyl group, hexyl group, and the like.

[0051] Examples of C1-C6 alkyl groups that ring Z may have include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, pentyl, and hexyl groups.

[0052] In the compounds represented by formula (b3) and formula (b4), it is preferable that a hydrocarbon chain with a certain number of carbon atoms exists between the main chain of the polyethylene oxide group and the epoxy group. That is, in the compound represented by formula (b3), R b6 The alkylene group has good storage stability because it is a linear or branched alkylene group having 1 to 18 carbon atoms (more preferably 3 to 8 carbon atoms). Furthermore, in the compound represented by formula (b4), the ring Z has good storage stability because it is a 5 to 12-membered cycloalkane ring or norbornane ring. This is thought to be because when the hydrocarbon chain between the polyethylene oxide group main chain and the epoxy group is of the above type, the structure around the epoxy group becomes crowded, reducing its reactivity and thus improving storage stability. On the other hand, the compound has the characteristic of curing even at relatively low temperatures during the curing stage.

[0053] Specific examples of compounds represented by formula (b3) include the compounds represented by formula (b3-1) and formula (b3-2) below. [ka] [ka]

[0054] Specific examples of compounds represented by formula (b4) include the compounds represented by formula (b4-1), formula (b4-2), and formula (b4-3). [ka] [ka] [ka]

[0055] The proportion (content) of constituent unit (B) in the copolymer is not particularly limited, but it is preferably 10 to 98% by weight of the total constituent units, more preferably 50 to 95% by weight, even more preferably 70 to 92% by weight, and particularly preferably 80 to 90% by weight. When the proportion of constituent unit (B) is above the lower limit, the amount of epoxy groups contained in the copolymer is suitable for curing, so it cures even at relatively low temperatures, and the crosslinked structure of the cured product becomes denser, resulting in a tendency for excellent solvent resistance. When the proportion of constituent unit (B) is below the upper limit, the amount of hydroxyl groups contained in the copolymer is appropriate, so it tends to have excellent solvent resistance, especially to highly polar solvents. In addition, the copolymer becomes hydrophilic, so it tends to have excellent developability (fast development speed and less residue).

[0056] [Constituent Unit (C)] The constituent unit (C) is derived from at least one compound selected from the group consisting of styrene (c1), which may be substituted with an alkyl group, N-substituted maleimide (c2), N-vinyl compound (c3), and an unsaturated carboxylic acid derivative (c4) represented by formula (2). The constituent unit (C) has functions such as imparting hardness to the cured product (cured film), facilitating copolymerization reactions, increasing solubility in solvents, and improving adhesion to the substrate.

[0057] The constituent unit (C) can be introduced into the copolymer by polymerizing at least one compound selected from the group consisting of (c1) to (c4) together with an unsaturated carboxylic acid or its anhydride (a) and an epoxy compound represented by formula (b1).

[0058] (Styrene(c1)) The alkyl group in styrene(c1), which may be substituted with an alkyl group, is not particularly limited, but examples include C1-C7 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, and hexyl groups. Among these, C1-C4 alkyl groups such as methyl or ethyl groups are preferred, and methyl groups are more preferred. The alkyl group may be bonded to either the vinyl group or the benzene ring of styrene.

[0059] Typical examples of styrene(c1) which may be substituted with alkyl groups include styrene, α-methylstyrene, and vinyltoluene (o-vinyltoluene, m-vinyltoluene, p-vinyltoluene). Among these, styrene is preferred. Styrene(c1) which may be substituted with alkyl groups can be used alone or in combination of two or more types.

[0060] (N-substituted maleimide (c2)) Examples of N-substituted maleimides (c2) include compounds represented by the following formula (3). [ka]

[0061] In formula (3), R 21 This indicates a monovalent organic group.

[0062] Examples of the monovalent organic group include hydrocarbon groups and heterocyclic groups. Examples of hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and hexyl groups (e.g., alkyl groups with 1 to 6 carbon atoms); cycloalkyl groups such as cyclopentyl, cyclohexyl, cyclooctyl, adamantyl, and norbornyl groups; aryl groups such as phenyl groups; aralkyl groups such as benzyl groups; and groups formed by the bonding of two or more of these groups. Examples of heterocyclic groups include 5 to 10-membered heterocycloalkyl groups and heteroaryl groups containing at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur atoms.

[0063] The N-substituted maleimide (c2) is not particularly limited, but examples include N-alkyl maleimides such as N-methyl maleimide, N-ethyl maleimide, and N-propyl maleimide; N-cycloalkyl maleimides such as N-cyclopentyl maleimide, N-cyclohexyl maleimide, N-cyclooctyl maleimide, N-adamantyl maleimide, and N-norbornyl maleimide; N-aryl maleimides such as N-phenyl maleimide; and N-aralkyl maleimides such as N-benzyl maleimide. Among these, N-cyclohexyl maleimide is preferred. The N-substituted maleimide (c2) can be used alone or in combination of two or more.

[0064] (N-vinyl compound (c3)) The N-vinyl compound (c3) is not particularly limited, but examples include N-vinylformamide, N-vinylacetamide, N-vinylisopropylamide, N-vinyl-N-methylacetamide, N-vinylpyrrolidone, N-vinylcarbazole, N-vinylpiperidone, and N-vinylcaprolactam. The N-vinyl compound (c3) can be used alone or in combination of two or more.

[0065] (Unsaturated carboxylic acid derivative (C4)) The unsaturated carboxylic acid derivative (c4) can be represented by the following formula (2). [Chemical]

[0066] In formula (2), R 11 represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. R 12 represents a monovalent hydrocarbon group which may contain a hetero atom. X represents a hetero atom.

[0067] Examples of the alkyl group having 1 to 7 carbon atoms in R 11 include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, hexyl group and the like. As R 11 , a hydrogen atom or a methyl group is particularly preferable.

[0068] Examples of the monovalent hydrocarbon group which may contain a hetero atom in R 12 include, for example, alkyl group, heteroalkyl group, alkenyl group, cycloalkyl group, heterocycloalkyl group, aryl group, and a group formed by linking two or more of these. Note that the carbon atom in R 12 is bonded to X.

[0069] Examples of the alkyl group include alkyl groups having 1 to 23 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, hexyl group, octyl group, decyl group, dodecyl group, isodecyl group, lauryl group, stearyl group and the like.

[0070] Examples of the heteroalkyl group include, for example, -(R 13 -O)p-R 14 group (wherein 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. p represents an integer of 1 or more.), -R 15 -NR 16 R 17 group (wherein R 15 represents an alkylene group having 1 to 12 carbon atoms. R 16 and R 17These each represent either the same or different hydrogen atoms or alkyl groups having 1 to 4 carbon atoms.

[0071] Examples of the aforementioned alkenyl group include alkenyl groups having 2 to 23 carbon atoms, such as allyl groups, 3-butenyl groups, and 5-hexenyl groups.

[0072] Examples of the cycloalkyl groups include cyclopentyl groups, cyclohexyl groups, cyclooctyl groups, adamantyl groups, norbornyl groups, and other cycloalkyl groups having 3 to 12 carbon atoms.

[0073] Examples of the heterocycloalkyl group include groups containing cyclic ether structures such as oxetane rings, oxolane rings, oxane rings, and oxepan rings (for example, cyclic ether-containing groups with three or more members).

[0074] Examples of the aryl group include aryl groups having 6 to 12 carbon atoms, such as phenyl groups and naphthyl groups.

[0075] Examples of heteroatoms in X include nitrogen atoms, oxygen atoms, and sulfur atoms.

[0076] The unsaturated carboxylic acid derivative (c4) represented by formula (2) is not particularly limited, but examples include alkyl-containing (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate; alkylamino-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, and N,N-diisopropylaminoethyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. , hydroxyl group-containing (meth)acrylates such as 4-hydroxybutyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, isooctyloxydiethylene glycol (meth)acrylate, phenoxytriethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, and other polyalkylene glycol (meth)acrylates having heteroalkyl groups; alkenyl group-containing (meth)acrylates such as allyl (meth)acrylate; cyclohexyl (meth)acrylate, 1-adamantyl (meth)acrylate, isobolonyl (meth)acrylate, tricyclo[5,2,1,0 2,6(meth)acrylates having monocyclic or polycyclic cycloalkyl groups such as decane-8-ol (meth)acrylate; (meth)acrylates having epoxy groups (oxyranyl groups) such as glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3-glycidyloxypropyl (meth)acrylate, glycidyloxyphenyl (meth)acrylate, oxetanyl (meth)acrylate, 3 -Methyl-3-oxetanyl(meth)acrylate, 3-ethyl-3-oxetanyl(meth)acrylate, (3-methyl-3-oxetanyl)methyl(meth)acrylate, (3-ethyl-3-oxetanyl)methyl(meth)acrylate, 2-(3-methyl-3-oxetanyl)ethyl(meth)acrylate, 2-(3-ethyl-3-oxetanyl)ethyl(meth)acrylate, 2-[(3-methyl-3-oxetanyl)methyloxy]ethyl(meth)acrylate, 2-[(3-ethyl-3-oxetanyl )methyloxy]ethyl (meth)acrylate, 3-[(3-methyl-3-oxetanyl)methyloxy]propyl (meth)acrylate, 3-[(3-ethyl-3-oxetanyl)methyloxy]propyl (meth)acrylate, and other (meth)acrylates having an oxetanyl group, such as tetrahydrofurfuryl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-( (Meth)acrylates having heterocycloalkyl groups (e.g., cyclic ether-containing groups of 3 or more members), such as (meth)acrylates containing alicyclic epoxy groups, such as 3,4-epoxycyclohexyl)ethyl (meth)acrylate, 2-(3,4-epoxycyclohexylmethyloxy)ethyl (meth)acrylate, and 3-(3,4-epoxycyclohexylmethyloxy)propyl (meth)acrylate; (meth)acrylates having aryl groups, such as phenyl (meth)acrylate and benzyl (meth)acrylate;Examples of alkoxysilyl group-containing (meth)acrylates include 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldiethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, and 8-(meth)acryloxyoctyltrimethoxysilane. The unsaturated carboxylic acid derivative (c4) represented by formula (2) can be used alone or in combination of two or more. Among these, methyl (meth)acrylate is preferred.

[0077] The proportion (content) of constituent unit (C) in the copolymer is not particularly limited, but is preferably 0 to 80% by weight relative to the total constituent units, more preferably 1 to 60% by weight, even more preferably 5 to 40% by weight, particularly preferably 10 to 30% by weight, and most preferably 15 to 25% by weight. When the proportion of constituent unit (C) is 1% by weight or more (particularly 5% by weight or more), functions such as imparting hardness to the cured product (cured film), facilitating the copolymerization reaction, increasing solubility in the solvent, and improving adhesion to the substrate are effectively expressed. When the proportion of constituent unit (C) is below the above upper limit, the proportions of constituent units (A) and (B) become relatively larger, so the functions of constituent units (A) and (B) are effectively expressed.

[0078] [Component Unit (D)] The copolymers of this disclosure may contain constituent units (D) other than the constituent units (A) to (C) described above. Examples of constituent units (D) include constituent units derived from (meth)acrylamide and (meth)acrylonitrile.

[0079] If the copolymer of the present disclosure includes structural unit (A) and structural unit (B) but does not include structural unit (C), the total amount of structural unit (A) and structural unit (B) is preferably 90% by weight or more, more preferably 95% by weight or more, even more preferably 99% by weight or more, and may be substantially 100% by weight. Also, if the copolymer of the present disclosure includes structural unit (A), structural unit (B), and structural unit (C), the total amount of structural units (A) to (C) is preferably 90% by weight or more, more preferably 95% by weight or more, even more preferably 99% by weight or more, and may be substantially 100% by weight.

[0080] The weight-average molecular weight (Mw) of the copolymer is not particularly limited, but is preferably 6,000 to 60,000, more preferably 7,000 to 30,000, even more preferably 8,000 to 20,000, and particularly preferably 8,500 to 15,000. The molecular weight distribution (ratio of weight-average molecular weight to number-average molecular weight: Mw / Mn) of the copolymer is not particularly limited, but is preferably 6.0 or less (e.g., 1.5 to 6.0), more preferably 2.0 to 5.0, and even more preferably 3.0 to 4.0. The weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be measured, for example, by GPC using polystyrene as a standard substance, and are preferably measured by the method used in the examples.

[0081] The copolymer of this disclosure functions as a binder resin for the colored photosensitive resin composition relating to this disclosure.

[0082] <Method for producing copolymers> The copolymers in this disclosure can be produced by copolymerizing an unsaturated carboxylic acid or its anhydride (a), an epoxy compound represented by formula (b1) (b), and optionally at least one compound selected 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 such as unsaturated carboxylic acids or their anhydrides (a) may be collectively referred to as "monomers".

[0083] In the method for producing the copolymer of the present disclosure, copolymerization may be carried out in the presence of a polymerization initiator. Conventional or known radical polymerization initiators can be used as the polymerization initiator, and examples include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), diethyl-2,2'-azobis(2-methylpropionate), and dibutyl-2,2'-azobis(2-methylpropionate); organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, and 1,1-bis(t-butylperoxy)cyclohexane; and hydrogen peroxide. When using a peroxide as a radical polymerization initiator, it may be combined with a reducing agent to form a redox-type initiator. Among these, azo compounds are preferred, and 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and dimethyl-2,2'-azobis(2-methylpropionate) are more preferred.

[0084] The amount of polymerization initiator used is not particularly limited as long as it does not hinder a smooth copolymerization reaction, but for example, 1 to 20 parts by weight and more preferably 5 to 15 parts by weight per 100 parts by weight of the total amount of monomers.

[0085] The copolymerization reaction described herein can be carried out by conventional methods used in the production 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 may be supplied to the reaction system together, or some or all of them may be added dropwise to the reaction system. For example, polymerization can be carried out by adding a solution in which the polymerization initiator is dissolved in the polymerization solvent dropwise to a monomer or a mixture of monomer and polymerization solvent that has been kept at a constant temperature, or by adding a solution in which the monomer and polymerization initiator have been dissolved in the polymerization solvent beforehand, dropwise to a polymerization solvent that has been kept at a constant temperature (dropwise polymerization method).

[0086] The copolymers of this disclosure are preferably obtained by copolymerization in a polymerization solvent. The polymerization solvent can be appropriately selected according to the monomer composition, etc., and for example, ethers (diethyl ether; ethylene glycol mono or dialkyl ether, diethylene glycol mono or dialkyl ether, propylene glycol mono or dialkyl ether, propylene glycol mono or diaryl ether, dipropylene glycol mono or dialkyl ether, tripropylene glycol mono or dialkyl ether, 1,3-propanediol mono or dialkyl ether, 1,3-butanediol mono or dialkyl ether, 1,4-butanediol mono or dialkyl ether, glycol ethers such as glycerin mono, di or trialkyl ether, etc.; cyclic ethers such as tetrahydrofuran and dioxane), esters (methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, C 5-6 Cycloalkanediol mono or diacetate, C 5-6 Carboxylic acid esters such as cycloalkane dimethanol mono or diacetate; ethylene glycol monoalkyl ether acetate, ethylene glycol mono or diacetate, diethylene glycol monoalkyl ether acetate, diethylene glycol mono or diacetate, propylene glycol monoalkyl ether acetate, propylene glycol mono or diacetate, dipropylene glycol monoalkyl ether acetate, dipropylene glycol mono or diacetate, 1,3-propanediol monoalkyl ether acetate, 1,3-propanediol mono or diacetate, 1,3-butanediol monoalkyl ether acetate, 1,3-butanediol mono or diacetate, 1,4-butanediol monoalkyl ether acetate, 1,4-butanediol mono or diacetate, glycerin mono, di or triacetate, glycerin mono or di C 1-4(Alkyl ether di or monoacetate, tripropylene glycol monoalkyl ether acetate, tripropylene glycol mono or diacetate, and other glycol acetates or glycol 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 Cycloalkanediol, C 5-6 Examples include cycloalkane dimethanol, hydrocarbons (such as aromatic hydrocarbons like benzene, toluene, and xylene; aliphatic hydrocarbons like hexane; alicyclic hydrocarbons like cyclohexane, etc.); and mixed solvents thereof.

[0087] The reaction temperature in the polymerization reaction can be appropriately selected depending on the type and composition of the monomers and is not particularly limited, but for example, 30 to 150°C is preferred.

[0088] The reaction solution containing the copolymer obtained by the above method can be purified by precipitation or reprecipitation as necessary. The solvent used for precipitation or reprecipitation may be an organic solvent, 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 (aliphatic halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene), nitro compounds (nitromethane, nitroethane, 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, isopropyl alcohol, butanol, etc.), carboxylic acids (acetic acid, etc.), and mixed solvents containing these solvents.

[0089] <Colorants> In this disclosure, the colorant can be any material that has coloring properties, and the color and material can be appropriately selected depending on the application, such as a color filter. Specifically, any pigment, dye, or natural pigment can be used as the colorant, but pigments and / or dyes are preferred for color filter applications because high color purity, brightness, and contrast are required.

[0090] The aforementioned pigments may be either organic or inorganic pigments. Examples of organic pigments include compounds classified as pigments in the Color Index (CI; published by The Society of Dyers and Colourists). Specifically, examples include those with the following Color Index (CI) names.

[0091] CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 83, CI Pigment Yellow 86, CI Pigment Yellow 93, CI Pigment Yellow 94, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow Yellow pigments such as 117, CI Pigment Yellow 125, CI Pigment Yellow 137, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 147, CI Pigment Yellow 148, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 180, CI Pigment Yellow 194, CI Pigment Yellow 211, CI Pigment Yellow 214, etc.

[0092] Orange pigments such as 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.

[0093] 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 Red pigments such as Pigment 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, and CI Pigment Red 272.

[0094] Violet pigments such as CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, and CI Pigment Violet 38.

[0095] Blue pigments such as CI Pigment Blue 15, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, CI Pigment Blue 60, and CI Pigment Blue 80.

[0096] Green pigments such as CI Pigment Green 7, CI Pigment Green 36, and CI Pigment Green 58.

[0097] Brown pigments such as CI Pigment Brown 23 and CI Pigment Brown 25.

[0098] Black pigments such as CI Pigment Black 1 and CI Pigment Black 7.

[0099] Examples of the inorganic pigments include titanium dioxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, lead yellow, zinc yellow, red iron(III) oxide, cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.

[0100] In this disclosure, pigments may be purified by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, or a combination thereof before use. Furthermore, the pigments may be used after their particle surface has been modified with a resin.

[0101] Furthermore, the aforementioned dyes can be appropriately selected from various oil-soluble dyes, direct dyes, acid dyes, metal complex dyes, etc., and examples include those with the following color index (CI) names.

[0102] Yellow dyes such as 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, etc.

[0103] Orange dyes such as 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.

[0104] Red dyes such as 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, and CI Acid Red 151.

[0105] Blue dyes such as CI Solvent Blue 35, CI Solvent Blue 37, CI Solvent Blue 59, CI Solvent Blue 67, CI Acid Blue 80, CI Acid Blue 83, and CI Acid Blue 90.

[0106] Green dyes such as CI Acid Green 9, CI Acid Green 16, CI Acid Green 25, and CI Acid Green 27.

[0107] In this disclosure, the colorants can be used alone or in combination of two or more types.

[0108] The colorant content is typically 1 to 30% by weight, preferably 3 to 15% by weight, of the solid content of the colored photosensitive resin composition. Here, "solid content" refers to components other than the solvent, which will be described later.

[0109] When pigments are used as colorants in this disclosure, they may be used together with pigment dispersants and pigment dispersing aids as desired. Examples of pigment dispersants include cationic, anionic, nonionic, and amphoteric dispersants (surfactants); and polymer dispersants such as acrylic copolymers, polyesters, polyurethanes, polyethyleneimines, and polyallylamines.

[0110] The aforementioned pigment dispersant can be a commercially available product. Examples include acrylic copolymers such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, and BYK-LPN21116 (all manufactured by BYK Corporation); polyesters such as Azisper PB821, Azisper PB822, and Azisper PB880 (manufactured by Ajinomoto Fine Techno Co., Ltd.); polyurethanes such as Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, and Disperbyk-182 (all manufactured by BYK Corporation); Solsperse 76500 (manufactured by Lubrizol Corporation); and polyethyleneimine such as Solsperse 24000 (manufactured by Lubrizol Corporation).

[0111] These pigment dispersants can be used individually or in combination of two or more. The content of the pigment dispersant is not particularly limited, but is, for example, 100 parts by weight or less, 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, per 100 parts by weight of pigment. A pigment dispersant content within the above range is preferable because it tends to yield a pigment dispersion with a uniform dispersion state.

[0112] Examples of the aforementioned pigment dispersion aids include pigment derivatives, specifically copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone. The content of the pigment dispersion aid can be appropriately determined within a range that does not impede the objective of the invention according to this disclosure.

[0113] <Photopolymerizable compound> The photopolymerizable compounds disclosed herein are not particularly limited, but examples include polyfunctional vinyl compounds, polyfunctional thiol compounds, and polyfunctional epoxy compounds.

[0114] The polyfunctional vinyl compound is not particularly limited as long as it is a compound having two or more vinyl groups, but 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 hydroxylated polymers such as hydroxypolybutadiene at both ends, hydroxypolyisoprene at both ends, and hydroxypolycaprylactone at both ends; glycerin, 1,2,4-butanetriol, and trimethylol. Examples include poly(meth)acrylates of trivalent or higher polyhydric alcohols such as alkanes, tetramethylolalkanes, pentaerythritol, and dipentaerythritol; poly(meth)acrylates of polyalkylene glycol adducts of trivalent or higher polyhydric alcohols; poly(meth)acrylates of cyclic polyols such as 1,4-cyclohexanediol and 1,4-benzenediol; and oligo(meth)acrylates such as polyester(meth)acrylate, epoxy(meth)acrylate, urethane(meth)acrylate, and silicone resin(meth)acrylate. 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.

[0115] The polyfunctional thiol compounds are not particularly limited as long as they are compounds having two or more thiol groups, but examples include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, and 1,4-dimethylmercaptobenzene. Examples include 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, tetraethylene glycol bis-3-mercaptopropionate, trimethylolpropane tris-3-mercaptopropionate, tris(3-mercaptopropynyloxyethyl) isocyanurate, pentaerythritol tetrakiss-3-mercaptopropionate, dipentaerythritol tetrakiss-3-mercaptopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and pentaerythritol tetrakiss(3-mercaptobutyrate). Polyfunctional thiol compounds can be used individually or in combination of two or more.

[0116] The polyfunctional epoxy compound is not particularly limited as long as it is a compound having two or more epoxy groups, but for example, glycidyl ether type epoxy compounds [glycidyl ethers produced by the reaction of polyhydroxy compounds (bisphenols, polyhydric phenols, alicyclic polyhydric alcohols, aliphatic polyhydric alcohols, etc.) with epichlorohydrin (e.g., (poly)C such as ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, etc.] 2-4Alkylene glycol diglycidyl ethers; diglycidyl ethers of polyhydric phenols such as resorcinol and hydroquinone; diglycidyl ethers of alicyclic polyhydric alcohols such as cyclohexanediol, cyclohexanedimethanol, and hydrogenated bisphenols; bisphenols (such as 4,4'-dihydroxybiphenyl and bis(hydroxyphenyl)alkanes like bisphenol A) or their C 2-3 Examples include diglycidyl ethers of alkylene oxide adducts, novolac-type epoxy resins (phenol novolac-type or cresol novolac-type 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.), and glycidylamine-type epoxy compounds [reaction products of amines and epichlorohydrin, for example, N-glycidyl aromatic amines {tetraglycidyldiaminodiphenylmethane (TGDDM), triglycidylaminophenol (TGPAP, TGMAP, etc.), diglycidylaniline (DGA), diglycidyltoluidine (DGT), tetraglycidylxylylenediamine (TGMXA, etc.), etc.}, and N-glycidyl alicyclic amines (tetraglycidylbisaminocyclohexane, etc.)]. Polyfunctional epoxy compounds can be used alone or in combination of two or more.

[0117] The photopolymerizable compound can be used alone or in a mixture of two or more. The content of the photopolymerizable compound is not particularly limited, but is preferably, for example, 1 to 100 parts by weight, more preferably 5 to 60 parts by weight, and even more preferably 10 to 40 parts by weight, per 100 parts by weight of the alkali-soluble resin. Similarly, the content of the photopolymerizable compound is not particularly limited, but is preferably, for example, 10 to 800 parts by weight, more preferably 50 to 500 parts by weight, and even more preferably 200 to 300 parts by weight, per 100 parts by weight of the colorant. When the content of the photopolymerizable compound is within the above range, sufficient curing occurs and good adhesion is obtained.

[0118] <Photopolymerization initiator> In this disclosure, the photopolymerization initiator is not particularly limited, but examples include photoradical polymerization initiators and photocationic polymerization initiators.

[0119] A photoradical polymerization initiator is a compound that generates radicals upon irradiation with light, thereby initiating the curing reaction (radical polymerization) of photopolymerizable compounds contained in a colored photosensitive resin composition. Photoradical polymerization initiators can be used alone or in combination of two or more types.

[0120] 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, imidosulfonate compounds, and anthracene compounds.

[0121] Examples of the thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0122] Examples of the acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, and 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-bromobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-chlorobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-bromobenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(4-bromobenzyl)-2-dimethylamino-1-(4-morpholinophenyl) Examples include butanone, 2-(2-methoxybenzyl)-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-(3-methoxybenzyl)-2-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, and oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one.

[0123] Examples of the biimidazole compounds include 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 in which the phenyl group at the 4,4',5,5'-position is substituted with a carboalkoxy group.

[0124] Examples of the aforementioned triazine compounds include 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-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6- Examples include [2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

[0125] Examples of the oxime compound include O-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one.

[0126] Examples of the benzoin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

[0127] Examples of the benzophenone compounds mentioned above include benzophenone, o-methyl benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone.

[0128] Examples of the anthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene.

[0129] The aforementioned photocationic polymerization initiator is a compound that generates acid upon irradiation with light, thereby initiating the curing reaction (cationic polymerization) of the photopolymerizable compound contained in the colored photosensitive resin composition. It consists of a cation portion that absorbs light and an anion portion that serves as the source of acid generation. The photocationic polymerization initiator can be used alone or in combination of two or more types.

[0130] Examples of photocationic polymerization initiators include diazonium salt compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, selenium salt compounds, oxonium salt compounds, ammonium salt compounds, bromine salt compounds, and the like.

[0131] For example, the anionic portion of the photocationic polymerization initiator is [(Y) s B(Phf) 4-s ] -(In the formula, Y represents a phenyl group or a biphenylyl group. Phf represents a phenyl group in which at least one hydrogen atom is substituted with at least one selected from perfluoroalkyl groups, perfluoroalkoxy groups, and halogen atoms. s is an integer from 0 to 3), BF4 - [(Rf) k PF 6-k ] - (Rf: an 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 - Examples include:

[0132] Examples of photocationic polymerization initiators include (4-hydroxyphenyl)methylbenzylsulfonium tetrakis(pentafluorophenyl)borate, 4-(4-biphenylylthio)phenyl-4-biphenylylphenylsulfonium tetrakis(pentafluorophenyl)borate, 4-(phenylthio)phenyldiphenylsulfonium phenyltris(pentafluorophenyl)borate, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium phenyltris(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium tris(pentafluoroethyl)trifluorophosphate, diphenyl[4-(phenylthio)phenyl]sulfonium tetrakis(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, and 4-(4-biphenylylthio)phenyl-4-biphenylylphenylsulfonium Examples include tris(pentafluoroethyl)trifluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide, phenyltris(pentafluorophenyl)borate, [4-(2-thiooxantonylthio)phenyl]phenyl-2-thiooxantonylsulfonium, phenyltris(pentafluorophenyl)borate, and 4-(phenylthio)phenyldiphenylsulfonium hexafluoroantimonate.

[0133] Examples of photocationic polymerization initiators include: "Cyracure UVI-6970", "Cyracure UVI-6974", "Cyracure UVI-6990", "Cyracure UVI-950" (all manufactured by Union Carbide, USA), "Irgacure 250", "Irgacure 261", "Irgacure 264" (all manufactured by BASF), "CG-24-61" (manufactured by Ciba-Geigy), "Optomer SP-150", "Optomer SP-151", "Optomer SP-170", "Optomer SP-171" (all manufactured by ADEKA Corporation), and "DAICAT "II" (manufactured by Daicel Corporation), "UVAC1590", "UVAC1591" (both manufactured by Daicel Cytec Corporation), "CI-2064", "CI-2639", "CI-2624", "CI-2481", "CI-2734", "CI-2855", "CI-2823", "CI-2758", "CIT-1682" (all manufactured by Nippon Soda Co., Ltd.), "PI-2074" (manufactured by Rhodia Corporation, tetrakis(pentafluorophenyl) borate) Commercially available products such as toluicumyliodonium salt, "FFC509" (manufactured by 3M), "BBI-102", "BBI-101", "BBI-103", "MPI-103", "TPS-103", "MDS-103", "DTS-103", "NAT-103", "NDS-103" (all manufactured by Midori Chemical Co., Ltd.), "CD-1010", "CD-1011", "CD-1012" (all manufactured by Sartomer, USA), "CPI-100P", "CPI-101A" (both manufactured by Sunapro Co., Ltd.) can be used.

[0134] The amount of photopolymerization initiator (total amount if two or more types are included) is, for example, 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, and more preferably 1 to 3 parts by weight, per 100 parts by weight of the total amount of photopolymerizable compound contained in the colored photosensitive resin composition. If the amount of photopolymerization initiator falls below the above range, the curability tends to decrease. On the other hand, if the amount of photopolymerization initiator exceeds the above range, the cured product tends to become more easily colored.

[0135] <Solvent> Examples of solvents include ethers (diethyl ether; ethylene glycol mono or dialkyl ether, diethylene glycol mono or dialkyl ether, propylene glycol mono or dialkyl ether, propylene glycol mono or diaryl ether, dipropylene glycol mono or dialkyl ether, tripropylene glycol mono or dialkyl ether, 1,3-propanediol mono or dialkyl ether, 1,3-butanediol mono or dialkyl ether, 1,4-butanediol mono or dialkyl ether, glycerin mono, di or trialkyl ether, and other glycol 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 Cycloalkanediol mono or diacetate, C 5-6 Carboxylic acid esters such as cycloalkane dimethanol mono or diacetate; ethylene glycol monoalkyl ether acetate, ethylene glycol mono or diacetate, diethylene glycol monoalkyl ether acetate, diethylene glycol mono or diacetate, propylene glycol monoalkyl ether acetate, propylene glycol mono or diacetate, dipropylene glycol monoalkyl ether acetate, dipropylene glycol mono or diacetate, 1,3-propanediol monoalkyl ether acetate, 1,3-propanediol mono or diacetate, 1,3-butanediol monoalkyl ether acetate, 1,3-butanediol mono or diacetate, 1,4-butanediol monoalkyl ether acetate, 1,4-butanediol mono or diacetate, glycerin mono, di or triacetate, glycerin mono or di C 1-4Examples include alkyl ether di or monoacetate, glycol acetates such as tripropylene glycol monoalkyl ether acetate, tripropylene glycol mono or diacetate, and glycol ether acetates, as well as ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 3,5,5-trimethyl-2-cyclohexen-1-one, etc.). These solvents may be used individually or in mixtures of two or more.

[0136] In addition to the components described above, the colored photosensitive resin composition of this disclosure may also contain, for example, resins such as novolac resin, phenolic resin, imide resin, and carboxyl group-containing resin, curing agents, curing accelerators, and additives (fillers, defoamers, flame retardants, antioxidants, ultraviolet absorbers, colorants, stress reducers, flexibility imparters, waxes, resins, crosslinking agents, halogen trapping agents, leveling agents, wetting improvers, etc.).

[0137] The content of alkali-soluble resin in the colored photosensitive resin composition of this disclosure is not particularly limited, but is preferably 5 to 80% by weight, more preferably 5 to 70% by weight, more preferably 10 to 60% by weight, even more preferably 15 to 50% by weight, and particularly preferably 20 to 40% by weight.

[0138] The alkali-soluble resin content in the colored photosensitive resin composition of this disclosure is not particularly limited, but is preferably, for example, 30 to 95% by weight, more preferably 40 to 90% by weight, more preferably 50 to 85% by weight, even more preferably 50 to 80% by weight, and particularly preferably 60 to 75% by weight, relative to the solids content of the colored photosensitive resin composition. Here, "solids content" refers to components other than solvents that the colored photosensitive resin composition may contain, for example.

[0139] The content of the photopolymerizable compound in the colored photosensitive resin composition of this disclosure is not particularly limited, but is preferably 1 to 60% by weight, more preferably 2 to 40% by weight, even more preferably 3 to 30% by weight, more preferably 5 to 20% by weight, and particularly preferably 5 to 15% by weight.

[0140] The content of the photopolymerizable compound in the colored photosensitive resin composition of this disclosure is not particularly limited, but is preferably, for example, 3 to 60% by weight, more preferably 5 to 50% by weight, more preferably 10 to 40% by weight, even more preferably 15 to 30% by weight, and particularly preferably 15 to 25% by weight, relative to the solid content of the colored photosensitive resin composition.

[0141] A method for preparing the colored photosensitive resin composition of this disclosure includes, for example, preparing a colorant dispersion by dispersing a colorant such as a pigment in a solvent, optionally with a pigment dispersant; separately, dissolving an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and optionally other additives in the solvent; mixing this with the aforementioned colorant dispersion; and optionally adding more solvent. The colored photosensitive resin composition of this disclosure is usually sealed in a container for distribution and storage. The colored photosensitive resin composition of this disclosure has excellent storage stability during distribution and storage.

[0142] <Color Filter> The color filter according to this disclosure comprises a colored pattern formed from the colored photosensitive resin composition. That is, the color filter according to this disclosure is a cured product of the colored photosensitive resin composition. The color filter can be manufactured, for example, by a step of forming a colored pattern on a substrate using the colored photosensitive resin composition, and a step of post-baking the colored pattern.

[0143] A method for forming a pattern on a color filter using the colored photosensitive resin composition of the present disclosure includes, for example, a method in which the colored photosensitive resin composition of the present disclosure is applied to a substrate or another resin layer by conventional coating means such as a spin coater, volatile components such as solvents are removed to form a colored layer, and the colored layer is exposed to light through a photomask for development.

[0144] Examples of substrates include flat-surface substrates such as glass substrates, silicon substrates, polycarbonate substrates, polyester substrates, aromatic polyamide substrates, polyamide-imide substrates, polyimide substrates, Al substrates, and GaAs substrates. These substrates may be pre-treated with chemical treatments such as silane coupling agents, plasma treatment, ion plating, sputtering, gas-phase reaction treatment, or vacuum deposition.

[0145] The thickness of the colored layer after drying is, for example, 0.6 to 8 μm, preferably 1 to 5 μm.

[0146] Examples of radiation light sources used during exposure include lamp light sources such as 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, as well as laser light 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 to 450 nm. The radiation exposure dose is generally 10 to 10,000 J / m². 2 It is preferable.

[0147] As the alkaline developer used for developing, aqueous solutions of sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, and 1,5-diazabicyclo-[4.3.0]-5-nonene are preferred.

[0148] The post-bake conditions are typically 120-280°C for 10-60 minutes. The film thickness of the pixels formed in this way is typically 0.5-5 μm, preferably 1-3 μm.

[0149] According to the colored photosensitive resin composition of this disclosure, a colored pattern can be obtained that exhibits excellent curing reactivity and sufficient solvent resistance.

[0150] <Components for display devices or display devices> The display device component or display device of this disclosure includes the color filter described above. An example of the display device component is a color liquid crystal display element. An example of the display device is a color liquid crystal display device. The structure of the color liquid crystal display element or color liquid crystal display is not particularly limited and can take any appropriate structure.

[0151] Each embodiment disclosed herein can be combined with any other features disclosed herein. Furthermore, each configuration and combination thereof in each embodiment is merely an example, and additions, omissions, and other modifications are permitted as appropriate, without departing from the spirit of the invention. This disclosure is not limited by the embodiments, but is limited only by the scope of the claims. [Examples]

[0152] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. The weight-average molecular weight (polystyrene equivalent) and molecular weight dispersion (weight-average molecular weight Mw / number-average molecular weight Mn) of the copolymer were measured using the following apparatus. Equipment: Detector: RID-20A (Shimadzu Corporation) Pump: LC-20AD (Shimadzu Corporation) System controller: CBM-20Alite (Shimadzu Corporation) Degasser: DGU-20A3 (Shimadzu Corporation) Auto Injector: SIL-20A HT (Shimadzu Corporation) Column: Shodex KF-806L (Showa Denko) Eluent: THF (tetrahydrofuran) 0.8 ml / min Temperature: Oven: 40℃, RI: 40℃ Detector: RI

[0153] [Synthesis Example 1 / Preparation of Monomer B1] (first step) A solution containing 213 g of 1,2-epoxy-9-decene and 60 g of 2-hydroxyethyl methacrylate was charged and maintained at 38°C. 18 g of ethyl acetate solution containing 1.9 g of boron trifluoride diethyl ether complex was added dropwise over 2 hours, and the mixture was stirred for 3 hours. Then, 250 g of ethyl acetate and 220 g of water were added and stirred, after which the organic layer was recovered. The organic layer weighed 526 g. Gas chromatography concentrations of 2-hydroxyethyl methacrylate and ethyl acetate in the organic layer were 0.9% by weight and 48.3% by weight, respectively. The remaining 50.8% by weight was considered to be the 1,2-epoxy-9-decene adduct of 2-hydroxyethyl methacrylate (crude product) and used in the next step. 1 The average number of 1,2-epoxy-9-decene added to the adduct, as determined by 1H-NMR, was 3.0.

[0154] (Second process) To the solution obtained by dissolving 140 mg of methoquinone in 200 g of the 1,2-epoxy-9-decene adduct of 2-hydroxyethyl methacrylate (crude product) obtained in the first step, 143 g of ethyl acetate solution of 28 wt% peracetic acid was added over 2 hours while maintaining the internal temperature below 50°C. The mixture was then stirred at 55°C for 7 hours. After confirming the disappearance of the starting material (1,2-epoxy-9-decene adduct of 2-hydroxyethyl methacrylate) by NMR, the mixture was cooled to room temperature, washed once with 340 g of water, and the aqueous layer was separated. Then, 120 g of 10 wt% aqueous sodium hydroxide solution was added to the organic layer for washing, and the aqueous layer was separated. The organic layer was then washed twice with water, and the aqueous layer was separated again. Finally, 70 g of the target monomer B1 was obtained by removing low-boiling components such as solvents using an evaporator at 40°C, 10 mmHg, and for 2 hours. The yield was 80%. The yield was calculated by comparing the actual yield of monomer B1 obtained with the theoretical yield calculated from the amount of raw material (2-hydroxyethyl methacrylate) used.

[0155] [Synthesis Example 2 / Creation of Monomer B2] (first step) A solution of 200 g of 1,2-epoxy-4-vinylcyclohexane and 70 g of 2-hydroxyethyl methacrylate was charged and maintained at 38°C. 18 g of ethyl acetate solution containing 1.9 g of boron trifluoride diethyl ether complex was added dropwise over 2 hours, and the mixture was stirred for 3 hours. Then, 252 g of ethyl acetate and 224 g of water were added and stirred, after which the organic layer was recovered. The organic layer weighed 524 g. Gas chromatography concentrations of 2-hydroxyethyl methacrylate and ethyl acetate in the organic layer were 1.2% by weight and 47.8% by weight, respectively. The remaining 51% by weight was used in the next step as a 1,2-epoxy-4-vinylcyclohexane adduct of 2-hydroxyethyl methacrylate (crude product). 1 The average number of 1,2-epoxy-4-vinylcyclohexane additions to the adduct, as determined by 1H-NMR, was 3.0.

[0156] (Second process) To the solution obtained by dissolving 140 mg of methoquinone in 200 g of the crude product of the 1,2-epoxy-4-vinylcyclohexane adduct of 2-hydroxyethyl methacrylate obtained in the first step, 182 g of ethyl acetate solution of 28 wt% peracetic acid was added over 2 hours while maintaining the internal temperature below 50°C. The mixture was then stirred at 55°C for 7 hours. After confirming the disappearance of the starting material (1,2-epoxy-4-vinylcyclohexane adduct of 2-hydroxyethyl methacrylate) by NMR, the mixture was cooled to room temperature, washed once with 400 g of water, and the aqueous layer was separated. The organic layer was then washed with 132 g of 10 wt% aqueous sodium hydroxide solution, the aqueous layer was separated, and the organic layer was washed twice with water to separate the aqueous layer. Finally, low-boiling point components such as solvents were removed using an evaporator at 40°C, 10 mmHg, and for 2 hours to obtain 94.0 g of the target monomer B2. The yield was 84%. The yield was calculated by comparing the actual yield of monomer B2 obtained with the theoretical yield calculated from the amount of raw material (2-hydroxyethyl methacrylate) used.

[0157] [Manufacturing Example 1] A nitrogen atmosphere was created by flowing an appropriate amount of nitrogen into a 1 L flask equipped with a reflux condenser, a dropping funnel, and a stirrer. 150 parts by weight of propylene glycol monomethyl ether acetate was placed in the flask and heated to 80°C while stirring. Then, a solution of 10 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 40 parts by weight of propylene glycol monomethyl ether acetate, and a solution of 15 parts by weight of acrylic acid (AA) as monomer and 85 parts by weight of monomer B1 dissolved in 10 parts by weight of propylene glycol monomethyl ether acetate were added dropwise to the flask using a dropping pump over approximately 4 hours. After the addition was complete, the solution was maintained at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer solution with a solid content of 35.7% by weight. The weight-average molecular weight Mw of the resulting copolymer was 10,500, and the molecular weight dispersion was 3.25.

[0158] [Manufacturing Example 2] The same procedure as in Production Example 1 was followed, except that 15 parts by weight of acrylic acid (AA) and 85 parts by weight of monomer B2 were used as monomers, to obtain a copolymer solution with a solid content of 35.1% by weight. The weight-average molecular weight Mw of the resulting copolymer was 10,300, and the molecular weight dispersion was 3.56.

[0159] [Manufacturing Example 3] The same procedure as in Production Example 1 was followed, except that 15 parts by weight of acrylic acid (AA), 65 parts by weight of monomer B2, and 20 parts by weight of styrene (ST) were used as monomers, to obtain a copolymer solution with a solid content of 34.1% by weight. The weight-average molecular weight Mw of the resulting copolymer was 8,800, and the molecular weight dispersion was 3.18.

[0160] [Manufacturing Example 4] The same procedure as in Production Example 1 was followed, except that 15 parts by weight of acrylic acid (AA), 65 parts by weight of monomer B2, and 20 parts by weight of methyl methacrylate (MMA) were used as monomers, to obtain a copolymer solution with a solid content of 34.8% by weight. The weight-average molecular weight Mw of the resulting copolymer was 9,700, and the molecular weight dispersion was 3.10.

[0161] [Manufacturing Example 5] The same procedure as in Production Example 1 was followed, except that 15 parts by weight of acrylic acid (AA), 65 parts by weight of monomer B2, and 20 parts by weight of N-cyclohexylmaleimide were used as monomers, to obtain a copolymer solution with a solid content of 35.2% by weight. The weight-average molecular weight Mw of the resulting copolymer was 9,400, and the molecular weight dispersion was 3.20.

[0162] [Manufacturing Example 6] A 1 L flask equipped with a reflux condenser, dropping funnel, and stirrer was supplied with an appropriate amount of nitrogen to create a nitrogen atmosphere. 150 parts by weight of propylene glycol monomethyl ether acetate was added, and the flask was heated to 65°C while stirring. Then, a solution of 10 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) dissolved in 40 parts by weight of propylene glycol monomethyl ether acetate, and a solution of 15 parts by weight of acrylic acid (AA), 65 parts by weight of glycidyl methacrylate (GMA), and 10 parts by weight of methyl methacrylate (MMA) dissolved in 10 parts by weight of propylene glycol monomethyl ether acetate were added dropwise to the flask using a dropping pump over approximately 4 hours. After the addition was complete, the flask was maintained at the same temperature for approximately 4 hours, and then cooled to room temperature to obtain a copolymer solution with a solid content of 34.5% by weight. The weight-average molecular weight Mw of the resulting copolymer was 8,000, and the molecular weight dispersion was 1.90.

[0163] [Manufacturing Example 7] The same procedure as in Production Example 6 was followed, except that 15 parts by weight of acrylic acid (AA), 65 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate (cyclomer M100), and 10 parts by weight of methyl methacrylate (MMA) were used as monomers, to obtain a copolymer solution with a solid content of 33.8% by weight. The weight-average molecular weight Mw of the resulting copolymer was 8,200, and the molecular weight dispersion was 1.91.

[0164] [Manufacturing Example 8] 15 parts by weight of acrylic acid (AA) as monomer, 65 parts by weight of 3,4-epoxytricyclo[5.2.1.0 2,6] Decane-9-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6 The same procedure as in Production Example 6 was followed, except that a mixture of decane-8-yl acrylate (monomer B3) and 10 parts by weight of methyl methacrylate (MMA) were used to obtain a copolymer solution with a solid content of 35.1% by weight. The weight-average molecular weight Mw of the resulting copolymer was 9,300, and the molecular weight dispersion was 2.04.

[0165] Table 1 shows the copolymer composition, weight-average molecular weight, and degree of dispersion of the copolymers in production examples 1 to 8.

[0166] [Example 1] 7.7g of CI Pigment Red 254 pigment, 3.1g of DISPERBYK-2000 as a dispersant, and 36.0g of MMPGAC as a solvent were weighed into containers. 45g of 1.0mm diameter zirconia beads were then added, and the containers were sealed. The mixture was shaken in a paint shaker for 3 hours. After 3 hours, the pigment dispersion and zirconia beads were separated, 45g of 0.5mm zirconia beads were added, and the mixture was shaken again in a paint shaker for another 3 hours. The pigment dispersion and zirconia beads were then separated again, 45g of 0.3mm zirconia beads were added, and the mixture was shaken again in a paint shaker for another 3 hours. Finally, the zirconia beads were separated to obtain the pigment dispersion. To 4.68 g of the obtained pigment dispersion, 8.09 g of the copolymer obtained in Production Example 1 as an alkali-soluble resin (as a copolymer-containing solution), 2.25 g of DPHA as a photopolymerizable compound, 0.20 g of 1-hydroxycyclohexylphenyl ketone as a photopolymerization initiator, and 18.8 g of MMPGAC as a solvent were weighed into a container and stirred for 30 minutes to prepare the colored photosensitive resin composition 1.

[0167] [Example 2] A colored photosensitive resin composition 2 was prepared by performing the same procedure as in Example 1, except that 8.09 g of the copolymer obtained in Production Example 2 was used as the copolymer-containing solution as the alkali-soluble resin.

[0168] [Example 3] A colored photosensitive resin composition 3 was prepared by performing the same procedure as in Example 1, except that 8.09 g of the copolymer obtained in Production Example 3 was used as the copolymer-containing solution as the alkali-soluble resin.

[0169] [Example 4] A colored photosensitive resin composition 4 was prepared by performing the same procedure as in Example 1, except that 8.09 g of the copolymer obtained in Production Example 4 was used as the copolymer-containing solution as the alkali-soluble resin.

[0170] [Example 5] A colored photosensitive resin composition 5 was prepared by performing the same procedure as in Example 1, except that 8.09 g of the copolymer obtained in Production Example 5 was used as the copolymer-containing solution as the alkali-soluble resin.

[0171] [Comparative Example 1] A colored photosensitive resin composition 6 was prepared by performing the same procedure as in Example 1, except that 8.09 g of the copolymer obtained in Production Example 6 was used as the copolymer-containing solution as the alkali-soluble resin.

[0172] [Comparative Example 2] A colored photosensitive resin composition 7 was prepared by performing the same procedure as in Example 1, except that 8.09 g of the copolymer obtained in Production Example 7 was used as the copolymer-containing solution as the alkali-soluble resin.

[0173] [Comparative Example 3] A colored photosensitive resin composition 8 was prepared by performing the same procedure as in Example 1, except that 8.09 g of the copolymer obtained in Production Example 8 was used as the copolymer-containing solution as the alkali-soluble resin.

[0174] Table 2 shows the compositions of the colored photosensitive resin compositions for the examples and comparative examples.

[0175] <Evaluation Test> The following evaluation tests were performed using each of the colored photosensitive resin compositions obtained in the examples and comparative examples. The results are shown in Table 3.

[0176] (1) Storage stability test The colored photosensitive resin compositions obtained in the examples and comparative examples were stored in an oven at 40°C for one week. The viscosity immediately after polymerization and the viscosity after storage at 23°C for one week were measured. The viscosity increase rate was calculated using the following formula. Viscosity (unit: mPa·s) was measured using a viscometer (product name "LVDV2T", Brookfield Corporation) under conditions of a rotation speed of 60 and a temperature of 23°C. P: Viscosity immediately after polymerization, Q: Viscosity after storage at 40°C for one week. Viscosity increase rate={(Q / P)×100}-100

[0177] (2) Solvent resistance test - 1 Test specimens were prepared by applying the colored photosensitive resin compositions obtained in the examples and comparative examples to a glass plate using a spin coater, and then heating and curing them at 150°C for 30 minutes. The thickness of the cured coating was 4 μm.

[0178] One drop each of γ-butyrolactone (γ-BL) and N-methylpyrrolidone (NMP) was added to the test specimen, and it was left for 10 minutes. After washing with water, if there was no change at all in the area where the solvent was applied, it was marked as ◎; if a slight solvent trace remained but could be wiped away, it was marked as ○; if a solvent trace remained and could not be wiped away, it was marked as △; and if the entire surface was discolored, it was marked as ×.

[0179] (3) Solvent resistance test - 2 In preparing the test specimens, the solvent resistance test of the cured product was performed in the same manner as in Solvent Resistance Test-1, except that the curing temperature was set to 230°C.

[0180] The colored photosensitive resin compositions of Examples 1 to 5 showed good storage stability, with minimal thickening even at 23°C. Furthermore, they exhibited good solvent resistance even at a curing temperature of 150°C, similar to the case at 230°C. On the other hand, the colored photosensitive resin compositions of Comparative Examples 1 and 2 showed poor storage stability, as evidenced by their thickening at 23°C. In addition, while the colored photosensitive resin composition of Comparative Example 3 showed good storage stability by using monomer B3 (E-DCPA), it was found that its solvent resistance decreased when the curing temperature was lowered from 230°C to 150°C, resulting in insufficient curing.

[0181] [Table 1]

[0182] [Table 2]

[0183] [Table 3]

[0184] The components used in the manufacturing examples, examples, and comparative examples are described below. Monomer B1: See Synthesis Example 1. Monomer B2: See Synthesis Example 2. GMA: Glycidyl methacrylate (manufactured by NOF Corporation) Cyclomer M100: 3,4-Epoxycyclohexylmethyl methacrylate (manufactured by Daicel Corporation) Monomer B3: 3,4-Epoxytricyclo[5.2.1.0 2,6 ] Decane-9-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6 A mixture of decane-8-yl acrylate (product name "E-DCPA", manufactured by Daicel Corporation) ST: Styrene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) MMA: Methyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) CHMI:N-Cyclohexylmaleimide (manufactured by Nippon Shokubai Co., Ltd.) MMPGAC: Propylene glycol monomethyl ether acetate (manufactured by Daicel Corporation) PR 254: CI Pigment Red 254 (manufactured by Tokyo Chemical Industry Co., Ltd.) DISPERBYK-2000: Amine value 4 mg KOH / g, non-volatile content 40% (manufactured by Bic Chemie Japan) DHPA: Dipentaerythritol hexaacrylate (product name "KAYARAD DPHA"; manufactured by Nippon Kayaku Co., Ltd.) 1-Hydroxycyclohexylphenyl ketone (manufactured by Fujifilm Wako Pure Chemical Corporation)

Claims

1. It contains alkali-soluble resin, colorant, photopolymerizable compound, photopolymerization initiator, and solvent. The alkali-soluble resin comprises a constituent unit (A) derived from an unsaturated carboxylic acid or its anhydride, and the following formula (b1) 【Chemistry 1】 (In the formula, R ｂ１ R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. ｂ２ R represents a divalent hydrocarbon group which may contain a heteroatom. ｂ３ This represents a divalent organic group having two or more epoxy groups. A copolymer comprising a constituent unit (B) derived from an epoxy compound represented by, The epoxy compound is of the following formula (b3) 【Chemistry 2】 (In the formula, R b1 represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. R b2 represents a divalent hydrocarbon group which may contain a heteroatom. R b5 represents the same or different hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R b6 represents the same or different divalent hydrocarbon group which may contain a single bond or a heteroatom. nb2 and nb3 are each integers of 0 or more, and the sum of nb2 and nb3 is 2 or more. The oxirane ring may have an alkyl group having 1 to 6 carbon atoms. The two groups in brackets do not necessarily have to be in the order shown in formula (b3).) Compounds represented by the following formula (b4) 【Transformation 3】 (In the formula, R b1 represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. R b2 represents a divalent hydrocarbon group which may contain a heteroatom. R b7 represents the same or different hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R b8 is a group bonded to ring Z, which may contain a single bond or a divalent hydrocarbon group which may contain a heteroatom. m represents an integer from 1 to 3. Ring Z represents an alicyclic hydrocarbon ring having 3 to 20 carbon atoms. nb4 represents an integer of 2 or more. The oxirane ring may have an alkyl group having 1 to 6 carbon atoms. Ring Z may have an alkyl group having 1 to 6 carbon atoms as a group other than R b7 and R b8.) A colored photosensitive resin composition comprising at least one selected from the group consisting of compounds represented by [formula].

2. The colored photosensitive resin composition according to claim 1, wherein the copolymer further comprises a constituent unit (C) derived from at least one compound selected from the group consisting of (c1) to (c4) below. (c1) Styrene which may be substituted with an alkyl group (c2) N-substituted maleimide (c3) N-vinyl compound (c4) The following formula (2) 【Chemistry 4】 (In the formula, R １１ R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms. １２ (where X represents a monovalent hydrocarbon group that may contain heteroatoms.) Unsaturated carboxylic acid derivatives represented by

3. The colored photosensitive resin composition according to claim 2, wherein the content of component (A) is 2 to 50% by weight, the content of component (B) is 10 to 98% by weight, and the content of component (C) is 0 to 80% by weight, relative to the total constituent units of the copolymer.

4. The colored photosensitive resin composition according to any one of claims 1 to 3, wherein the coloring material is a pigment and / or a dye.

5. A color filter which is a cured product of a colored photosensitive resin composition according to any one of claims 1 to 4.

6. A display device component or display device comprising the color filter described in claim 5.

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