Polymer, polymer composition, resin composition, cured product, method for preserving polymer, and method for preserving polymer composition

Abstract

To provide a polymer which affords a cured product having excellent storage stability and suppressed oxidative deterioration.SOLUTION: A polymer comprises: a constitutional unit (A) represented by the general formula (1) in the figure; and a constitutional unit (B) derived from a monomer selected from the group consisting of a hindered phenol compound having a polymerizable group, a hindered amine compound having a polymerizable group, a cyano(meth)acrylate compound, a melamine compound having a polymerizable group, and a thiol compound having a polymerizable group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polymer, a polymer composition, a resin composition, a cured product, a method for storing a polymer, and a method for storing a polymer composition, more particularly to a polymer, a polymer composition, a resin composition, a cured product, a method for storing a polymer, and a method for storing a polymer composition that can give a cured product in which oxidative degradation is suppressed and that has excellent storage stability. [Background technology]

[0002] Various applications of resin compositions have been studied for various uses, such as color filters used in liquid crystal display devices and solid-state imaging devices, inks, printing plates, printed wiring boards, semiconductor devices, photoresists, organic insulating films, organic protective films, and other optical components and electrical and electronic devices, and resins and resin compositions having excellent properties required for each use have been developed. In recent years, optical components and electrical and electronic devices have become smaller, thinner, and more energy-efficient, and this has led to demands for higher performance from the various components used in these devices. To meet these demands, research is being conducted on resins and resin compositions that are used as materials for these components.

[0003] Resins and resin compositions have been developed to meet various requirements. For example, a photosensitive resin composition that can give a cured film with high sensitivity, transparency, and excellent ITO sputtering resistance includes a photosensitive resin composition containing a polymer including a monomer unit having a residue that generates a carboxyl group or a phenolic hydroxyl group when exposed to acid and a monomer unit having a group having 3 to 16 carbon atoms and an ethylenically unsaturated bond at its terminal, a photoacid generator, and a solvent (Patent Document 1), and a photosensitive resin composition that can give a cured product with excellent solvent resistance even under low-temperature curing conditions includes a photosensitive resin composition containing a polymer having a group that generates a vinyl ether group when exposed to acid or heat (Patent Document 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2011-209682 [Patent Document 2] International Publication No. 2023 / 248976 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the polymers described in Patent Documents 1 and 2 have an acetal structure, which has the problem that such polymers tend to yellow due to oxidative degradation.Furthermore, such polymers generally have high reactivity, which also has the problem of low storage stability.

[0006] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a polymer, a polymer composition, and a resin composition that can give a cured product that has excellent storage stability and is inhibited from oxidative degradation. [Means for solving the problem]

[0007] The present inventors have conducted extensive research on polymers and have found that, even when a polymer has an acetal structure, the polymer can be further inhibited from oxidative degradation, inhibited from yellowing due to heat, and have excellent storage stability by further containing a structural unit derived from a specific compound. Furthermore, the present inventors have also found that, for example, combining a polymer having an acetal structure with a specific compound can also result in a polymer composition that can give a cured product with excellent storage stability and inhibited oxidative degradation, and have thus completed the present invention.

[0008] That is, the present invention includes the following aspects. <1> The composition comprises a structural unit (A) represented by the following general formula (1) and a structural unit (B) derived from at least one monomer selected from the group consisting of a hindered phenol compound having a polymerizable group, a hindered amine compound having a polymerizable group, a cyano(meth)acrylate compound, a melamine compound having a polymerizable group, and a thiol compound having a polymerizable group: A polymer characterized by:

[0009] [ka]

[0010] (In the formula, X represents a hydrogen atom or a methyl group. L represents a divalent organic group. A 1 is an oxygen atom, a sulfur atom, or -NR 3 - represents R 3 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 2 -OR 4 , -SR 5 or -NR 6 R 7 Represents R 4 , R 5 , R 6 and R 7 are the same or different and represent a hydrogen atom or an organic group having 1 to 20 carbon atoms. 1 and R 2 represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. <2> The structural unit (A) has a structure in which a vinyl ether group is generated at the end of the side chain by the action of an acid or heat. <1> The polymer according to claim 1. <3> Above A 2 is -O-(CO)-R 8 (R 8 represents a hydrocarbon group having 1 to 19 carbon atoms. <1> or <2> The polymer according to claim 1. <4> The above-mentioned compound further characterized in that it has a structural unit (C) having an acid group. <1> ~ <4> The polymer according to any one of the preceding claims. <5> A polymer composition comprising a polymer having a structural unit (A) represented by the following general formula (1) and at least one compound selected from the group consisting of hindered phenol compounds, hindered amine compounds, cyano(meth)acrylate compounds, melamine compounds, and thiol compounds:

[0011] [ka]

[0012] (In the formula, X represents a hydrogen atom or a methyl group. L represents a divalent organic group. A 1 is an oxygen atom, a sulfur atom, or -NR 3 - represents R 3 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 2 -OR 4 , -SR 5 or -NR 6 R 7 Represents R 4 , R 5 , R 6 and R 7 are the same or different and represent a hydrogen atom or an organic group having 1 to 20 carbon atoms. 1 and R 2 represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. <6> The structural unit (A) has a structure in which a vinyl ether group is generated at the end of the side chain by the action of an acid or heat. <5> The polymer composition according to claim 1. <7> The above A in the general formula (1) 2 is -O-(CO)-R 8 (In the formula, R 8 represents a hydrocarbon group having 1 to 19 carbon atoms. <5> or <6> The polymer composition according to claim 1. <8> The polymer is characterized by having a structural unit (C) having an acid group. <5> ~ <7> The polymer composition according to any one of the preceding claims. <9> the above <1> ~ <4> or the polymer described in any one of <5> ~ <8> 10. A resin composition comprising the polymer composition according to any one of claims 1 to 9 and a polymerizable compound. <10> The above-mentioned composition further comprising a photopolymerization initiator. <9> The resin composition according to claim 1. <11> The above-mentioned composition characterized in that it is used for a color filter. <9> or <10> The resin composition according to claim 1. <12> the above <9> ~ <11> A cured product of the resin composition according to any one of the preceding items. <13> A method for storing a polymer having a structural unit (A) represented by the following general formula (1) in a container, wherein the oxygen concentration in the gas phase in the container is 10% by volume or less, and / or the ratio of the free space volume of the gas phase in the container to the volume of the container is 15% or less.

[0013] [ka]

[0014] (In the formula, X represents a hydrogen atom or a methyl group. L represents a divalent organic group. A 1 is an oxygen atom, a sulfur atom, or -NR 3 - represents R 3 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 2 -OR 4 , -SR 5 or -NR 6 R 7 Represents R 4 , R 5 , R 6 and R 7 are the same or different and represent a hydrogen atom or an organic group having 1 to 20 carbon atoms. 1 and R 2 represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. <14> A method for storing a polymer composition in a container, the polymer composition comprising a polymer having a structural unit (A) represented by the following general formula (1) and at least one compound selected from the group consisting of hindered phenol compounds, hindered amine compounds, cyano(meth)acrylate compounds, melamine compounds, and thiol compounds, wherein the oxygen concentration in the gas phase in the container is 10% by volume or less, and / or the ratio of the free space volume of the gas phase in the container to the volume of the container is 15% or less.

[0015] [ka]

[0016] (In the formula, X represents a hydrogen atom or a methyl group. L represents a divalent organic group. A 1 is an oxygen atom, a sulfur atom, or -NR 3 - represents R 3 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. 2 -OR 4 , -SR 5 or -NR 6 R 7 Represents R 4 , R 5 , R 6 and R 7 are the same or different and represent a hydrogen atom or an organic group having 1 to 20 carbon atoms. 1 and R 2 represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. [Effects of the Invention]

[0017] The polymer and polymer composition of the present invention can give a cured product that has excellent storage stability and is inhibited from oxidative degradation. DETAILED DESCRIPTION OF THE INVENTION

[0018] The present invention will be described in detail below. Note that a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

[0019] 1. Polymer The polymer of the present invention is characterized by having a structural unit (A) represented by the above general formula (1) and a structural unit (B) derived from at least one monomer selected from the group consisting of a hindered phenol compound having a polymerizable group, a hindered amine compound having a polymerizable group, a cyano(meth)acrylate compound, and a melamine compound having a polymerizable group. In this specification, such a polymer of the present invention is also referred to as a "polymer (X)."

[0020] The reason why the polymer (X) of the present invention can provide a cured product with excellent storage stability and suppressed oxidative degradation is believed to be as follows. Specifically, the structural unit (A) has an acetal structure. By having such a structure, the polymer (X) forms a vinyl ether group at its terminal during curing, enabling it to provide a good cured product. However, when the polymer (X) has an acetal structure, hydrogen atoms adjacent to heteroatoms, such as oxygen atoms, are easily abstracted, which makes it easy to generate radicals. These radicals react with oxygen in the air, resulting in oxidative degradation of the polymer. The polymer (X) of the present invention further contains the structural unit (B), which can suppress the generation of such radicals and capture them, thereby presumably effectively suppressing oxidative degradation of the polymer. The structural units contained in the polymer (X) of the present invention are described below.

[0021] <Constituent unit (A)> The polymer (X) of the present invention has a structural unit (A) represented by the above general formula (1). In the above general formula (1), X represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom in view of good hydrophilicity.

[0022] In the general formula (1), L represents a divalent organic group. Examples of the divalent organic group include an optionally substituted divalent hydrocarbon group, and a group containing an optionally substituted divalent hydrocarbon group and at least one bonding group selected from the group consisting of -O-, -COO-, -CO-, -NH-, -S-, -SO-, and -SO2-.

[0023] Examples of the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

[0024] Examples of the divalent aliphatic hydrocarbon group include alkylene groups such as methylene, ethylene, propylene, isopropylene, butylene, isobutylene, t-butylene, and pentylene, and alkynylene groups such as vinylene, propenylene, isopropenylene, butenylene, butadienylene, and pentenylene.

[0025] Examples of the divalent alicyclic hydrocarbon group include cycloalkylene groups such as cyclopropylene, cyclobutylene, and cyclopentylene.

[0026] Examples of the divalent aromatic hydrocarbon group include arylene groups such as a phenylene group and a naphthylene group.

[0027] Among these, the hydrocarbon group is preferably an aliphatic hydrocarbon group, and more preferably an alkylene group, in that it can suppress thermal discoloration.

[0028] The hydrocarbon group may contain a heteroatom, and examples of the heteroatom include an oxygen atom, a sulfur atom, and a nitrogen atom.

[0029] The hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 2 carbon atoms.

[0030] Examples of the substituent that the hydrocarbon group may have include a thiol group, a thioether group, a hydroxyl group, and a carboxyl group.

[0031] The above-mentioned linking group is preferably at least one type of linking group selected from the group consisting of -O-, -COO-, and -CO-, and more preferably at least one type of linking group selected from the group consisting of -O- and -COO-, in terms of good copolymerizability.

[0032] Among these, the divalent organic group is preferably -CO-(O-CH2-CH2) because of its good hydrophilicity. n- (n represents an integer of 1 to 5) is preferred.

[0033] In the above general formula (1), A 1 is an oxygen atom, a sulfur atom, or -NR 3 - represents R 3 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R 3 The hydrocarbon group represented by the formula (I) is preferably a monovalent aliphatic hydrocarbon group or a hydrocarbon group which may have a substituent, and the substituent is more preferably an aromatic group, and further preferably a phenyl group.

[0034] R 3 The hydrocarbon group represented by the formula (I) preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 5 carbon atoms.

[0035] In the above general formula (1), A 2 -OR 4 , -SR 5 or -NR 6 R 7 Represents R 4 , R 5 , R 6 and R 7 are the same or different and represent a hydrogen atom or an organic group having 1 to 20 carbon atoms. R 4 , R 5 , R 6 and R 7 Examples of the organic group represented by the formula include groups obtained by adding one hydrogen atom to the above-mentioned divalent organic groups to make them monovalent.

[0036] Among them, R 4 is -CO-R a1 (R a1 represents a hydrocarbon group which may have a substituent. R a1 The hydrocarbon group represented by the formula (I) is preferably an aliphatic hydrocarbon group, and more preferably an alkyl group. R a1The hydrocarbon group represented by the formula (I) preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 3 to 12 carbon atoms. The substituent is preferably a thiol group or a group having a thioether bond, and by having such a substituent, radical scavenging ability can be imparted.

[0037] Among them, R 5 is preferably a hydrocarbon group which may have a substituent, and more preferably an alkyl group which may have a substituent. The substituent is more preferably a hydroxyl group or a carboxyl group, and even more preferably a carboxyl group. R 5 The organic group represented by the formula (I) preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 3 to 12 carbon atoms.

[0038] Among them, R 6 and R 7 are the same or different and are preferably hydrocarbon groups which may have a substituent, and more preferably alkyl groups which may have a substituent. The above substituent is more preferably an aromatic group, and even more preferably a phenyl group. R 6 and R 7 The organic group represented by the formula (I) preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 2 carbon atoms.

[0039] In the above general formula (1), R 1 and R 2 Examples of the organic group represented by the formula include groups obtained by adding one hydrogen atom to the above-mentioned divalent organic groups to make them monovalent. Among them, R 1 and R 2 The organic group represented by the formula (I) is preferably a hydrocarbon group which may have a substituent, and more preferably an aliphatic hydrocarbon group which may have a substituent. The above substituent is more preferably an aromatic group, and even more preferably a phenyl group. R 1 and R 2 The organic group represented by the formula (I) preferably has 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and even more preferably 1 to 2 carbon atoms.

[0040] The structural unit (A) preferably has a structure in which a vinyl ether group (-O-CH=CH2) is generated at the side chain terminal by acid or heat. With such a structure, when the polymer is cured and heated, a vinyl ether group is generated at the side chain terminal, facilitating the crosslinking reaction, and allowing for the production of a cured product with excellent heat resistance and solvent resistance.

[0041] Examples of the structure in which a vinyl ether group is generated at the side chain terminal by the action of an acid or heat include a group in which a vinyl ether group is protected with an acetal. Examples of the vinyl ether group that has been acetal-protected include a group containing a bonding group of -O-CH(CH3)-O-. 1 is preferably an oxygen atom, and R 1 and R 2 is preferably a hydrogen atom. 2 -OR b1 (R b1 represents an organic group having 1 to 20 carbon atoms. When the polymer has such a group, the above-mentioned -OR b1 is eliminated, and a vinyl ether group (-O-CH=CH2) is generated in the side chain of the polymer.

[0042] A in the above general formula (1) 2 -O-(CO)-R has good low-temperature curing properties. 8 (In the formula, R 8 represents a hydrocarbon group having 1 to 19 carbon atoms. 8 The hydrocarbon group represented by the formula (I) is more preferably an alkyl group.

[0043] The polymer (X) having the structural unit (A) can be obtained by polymerizing a monomer into which the structural unit (A) can be introduced. Examples of the monomer into which the structural unit (A) can be introduced include the monomer (a) represented by the following general formula (2):

[0044] [ka] (In the formula, X, L, A 1 , A 2 , R 1 and R 2 are the same as general formula (1).

[0045] The polymer (X) may have only one type of the structural unit (A), or may have two or more types.

[0046] The content of the structural unit (A) in the polymer (X) is preferably 1 to 90 mass%, more preferably 5 to 50 mass%, and even more preferably 15 to 30 mass%, relative to 100 mass% of all structural units of the polymer, in terms of good low-temperature curing properties.

[0047] <Constituent Unit (B)> The polymer (X) of the present invention has a structural unit (B) derived from at least one monomer selected from the group consisting of hindered phenol compounds having a polymerizable group, hindered amine compounds having a polymerizable group, cyano(meth)acrylate compounds, melamine compounds having a polymerizable group, and thiol compounds having a polymerizable group.

[0048] Preferred examples of the polymerizable group include polymerizable double bonds such as (meth)acryloyl, vinyl, allyl, and methallyl groups, with (meth)acryloyl being particularly preferred.

[0049] The hindered phenol compound has at least one hindered phenol group, which has a bulky substituent bonded to at least one carbon atom adjacent to the carbon atom to which the hydroxyl group of the phenol is bonded.

[0050] Examples of the hindered phenol compound having a polymerizable group include compounds represented by the following general formula (3).

[0051] [ka] (In the formula, R 31 and R 32 are the same or different and represent a hydrogen atom or an organic group. 31 and R 32 At least one of R is an organic group having four or more atoms other than hydrogen atoms. 33 , R 34 and R 35 are the same or different and represent a hydrogen atom or a substituent. 34 ~X 35 At least one of the groups has a polymerizable group.)

[0052] R 31 and R 32 Examples of the organic group represented by R include the same groups as those described above. 31 and R 32 At least one of the above is an organic group having 4 or more atoms other than hydrogen atoms. In the organic group, the number of atoms other than hydrogen atoms is preferably 4 to 12, and more preferably 4 to 8.

[0053] The organic group having four or more atoms other than hydrogen atoms is preferably a hydrocarbon group having four or more carbon atoms, a benzophenone group which may have a substituent, a benzotriazole group which may have a substituent, or a triazine group which may have a substituent. Examples of the substituent include a halogen atom, a hydrocarbon group, an alkoxy group, a cyano group, and a nitro group. Among these, the organic group having four or more atoms other than hydrogen atoms is preferably a benzotriazole group which may have a substituent, in that it can further improve the heat resistance and weather resistance of the polymer.

[0054] R 33 , R 34 , R 35 Examples of the substituent represented by R include the above-mentioned organic groups, as well as halogen atoms, alkoxy groups, cyano groups, and nitro groups. 33 , R 34 , R 35 The organic group represented by the formula (I) preferably has 1 to 15 carbon atoms, more preferably 2 to 15 carbon atoms, and even more preferably 3 to 12 carbon atoms.

[0055] R 33 , X 34 , and X 35 The substituent represented by -R is preferably a group having a polymerizable group at the terminal, more preferably a group having a (meth)acryloyl group, c1 -O-CO-CR c2 =CH2(R c1 represents an alkylene group having 1 to 12 carbon atoms, and R c2 represents a hydroxyl group or a methyl group.

[0056] In the above general formula (3), R 33 , R 34 and R 35 At least one of the groups is preferably a group having a polymerizable group at its terminal, and the rest are preferably hydrogen atoms.

[0057] An example of the hindered phenol compound having a polymerizable group is RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.).

[0058] Examples of the hindered amine compound having a polymerizable group include compounds represented by the following general formula (4).

[0059] [ka]

[0060] (In formula (4), R 41 , R 42 , R 44 and R 45 are the same or different and represent an organic group having 1 to 20 carbon atoms. 43 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms. 46 represents a substituent, at least one of which is a substituent having a (meth)acryloyl group. n represents an integer of 1 to 20. m represents an integer of 1 to (n+1).

[0061] In the above general formula (4), R 41 , R 42 , R 44 and R 45 Examples of the organic group represented by R include the same groups as those mentioned above. Among them, a monovalent hydrocarbon group is preferred, a monovalent aliphatic hydrocarbon group is more preferred, and an alkyl group is even more preferred. 41 , R 42 , R 44 and R 45 The organic group represented by the formula (I) preferably has 1 to 20 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 carbon atom.

[0062] In the above general formula (4), R 43 Examples of the organic group represented by the formula (I) include the same groups as the organic groups described above, but are preferably aliphatic hydrocarbon groups and alkoxy groups, and more preferably alkyl groups and alkoxy groups. R 43The organic group represented by the formula (I) preferably has 1 to 20 carbon atoms, and more preferably 1 to 15 carbon atoms.

[0063] In the above general formula (4), n preferably represents an integer of 1 to 6, and more preferably an integer of 1 to 3.

[0064] In the above general formula (4), R 46 The substituent represented by the formula (3) is R 33 ~R 35 The same groups as the substituents represented by R 46 When there are multiple R, they may be the same or different. 46 At least one of the groups is a group having a (meth)acryloyl group, and -R d1 -O-CO-CR d2 =CH2(R d1 represents a direct bond or an alkylene group having 1 to 12 carbon atoms, and R d2 represents a hydroxyl group or a methyl group.

[0065] m represents an integer of 1 to (n+1), preferably an integer of 1 to 7, and more preferably an integer of 1 to 4.

[0066] Examples of the hindered amine compound having a polymerizable group include Adekastab LA-82 (manufactured by ADEKA Corporation) and Adekastab LA-87 (manufactured by ADEKA Corporation).

[0067] Examples of the cyano(meth)acrylate compound include Uvinal (registered trademark) 3035, Uvinal 3039, and Uvinal 3030FF manufactured by BASF.

[0068] The thiol compound having the polymerizable group may be a product obtained by adding a compound having both a thiol and a functional group reactive with a vinyl ether group to a vinyl ether group-containing monomer. The functional group reactive with a vinyl ether is preferably a carboxyl group.

[0069] In particular, in terms of being able to suppress heat-resistant discoloration, the above-mentioned structural unit (B) is preferably a structural unit derived from a monomer of a hindered phenol or hindered amine compound, and more preferably a structural unit derived from a monomer of a hindered phenol compound.

[0070] The polymer having the structural unit (B) can be obtained by polymerizing a monomer component containing at least one monomer (b) selected from the group consisting of the hindered amine compound having a polymerizable group, the cyano(meth)acrylate compound, the melamine compound having a polymerizable group, and the thiol compound having a polymerizable group.

[0071] The polymer (X) may have only one type of the structural unit (B), or may have two or more types.

[0072] The content of the structural unit (B) in the polymer (X) is preferably 0.1 to 50 mass%, more preferably 1 to 20 mass%, and even more preferably 1 to 5 mass%, relative to 100 mass% of all structural units of the polymer, in terms of good heat discoloration resistance.

[0073] <Constituent Unit (C)> The polymer (X) preferably further contains a structural unit (C) having an acid group. The structural unit (C) makes the polymer alkali-soluble and improves developability. The structural unit (C) also facilitates the generation of vinyl ether groups from the structural unit (A) during curing, and the resulting vinyl ether groups react with acid groups to facilitate the self-crosslinking reaction of the polymer, resulting in the formation of a stronger cured product.

[0074] Examples of the acid group include functional groups that undergo a neutralization reaction with alkaline water, such as a carboxyl group, a phenolic hydroxyl group, a carboxylic anhydride group, a phosphoric acid group, and a sulfonic acid group, and the composition may have only one of these groups or two or more of these groups. Among these, a carboxyl group or a carboxylic anhydride group is preferred, and a carboxyl group is more preferred, in terms of improving developability.

[0075] The polymer having the structural unit (C) having an acid group can be prepared, for example, by a method (1) of polymerizing a monomer component containing an acid group-containing monomer; a method (2) of polymerizing a monomer containing a hydroxyl group-containing monomer to obtain a hydroxyl group-containing polymer, and then reacting a polybasic acid or a polybasic acid anhydride with the hydroxyl groups of the polymer to introduce an acid group (carboxyl group); a method (3) of polymerizing a monomer component containing an epoxy group-containing monomer to obtain an epoxy group-containing polymer, and then subjecting the epoxy groups of the polymer to an addition reaction with the acid groups of the acid group-containing monomer to ring-open the epoxy groups, and then reacting the hydroxyl groups generated in this process with a polybasic acid or a polybasic acid anhydride to introduce an acid group (carboxyl group); or a combination of these methods.

[0076] In the above method (1), the structural unit (C) is a structural unit derived from an acid group-containing monomer. Examples of the acid group-containing monomer include compounds having the above-mentioned acid group and polymerizable double bond in the molecule. Specific examples of the acid group-containing monomer include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, cinnamic acid, and vinylbenzoic acid; unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid; long-chain unsaturated monocarboxylic acids in which the unsaturated group and the carboxyl group are chain-extended, such as β-carboxyethyl (meth)acrylate, mono(2-acryloyloxyethyl) succinate, and mono(2-methacryloyloxyethyl) succinate; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; and phosphoric acid group-containing unsaturated compounds such as Light Ester P-1M (manufactured by Kyoeisha Chemical Co., Ltd.). Among these, carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, long-chain unsaturated monocarboxylic acids, and unsaturated acid anhydrides) are preferred from the viewpoints of versatility and availability. In terms of reactivity, alkali solubility, etc., the acid group-containing monomer is more preferably an unsaturated monocarboxylic acid, and even more preferably (meth)acrylic acid.

[0077] In the above method (2), the structural unit (C) is a structural unit containing an acid group (carboxyl group) introduced by reacting a structural unit derived from a hydroxyl group-containing monomer with a polybasic acid or a polybasic acid anhydride.

[0078] Examples of the hydroxyl group-containing monomer include compounds having a hydroxyl group and the above-mentioned polymerizable double bond, and specific examples include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2,3-hydroxypropyl (meth)acrylate.

[0079] Examples of the polybasic acid or polybasic acid anhydride include polybasic acids such as succinic acid, maleic acid, phthalic acid, and tetrahydrophthalic acid; dibasic acid anhydrides such as succinic anhydride (also known as succinic anhydride), maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, and itaconic anhydride; and polybasic acid anhydrides such as trimellitic anhydride. Among these, polybasic acid anhydrides are preferred, with succinic anhydride and tetrahydrophthalic anhydride being more preferred, and succinic anhydride being most preferred.

[0080] In the above method (3), the structural unit (C) is a structural unit containing a carboxyl group produced by reacting a structural unit derived from an epoxy group-containing monomer with an acid group-containing monomer, and then reacting the resulting structural unit with a polybasic acid or a polybasic acid anhydride.

[0081] The epoxy group-containing monomer includes a compound having an epoxy group and a polymerizable double bond in the molecule, and preferably an epoxy group-containing (meth)acrylate. Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, vinylbenzyl glycidyl ether, allyl glycidyl ether, (3,4-epoxycyclohexyl)methyl (meth)acrylate, vinylcyclohexene oxide, etc. Among these, glycidyl (meth)acrylate and (3,4-epoxycyclohexyl)methyl (meth)acrylate are preferred, and glycidyl (meth)acrylate is more preferred.

[0082] Examples of the acid group-containing monomer, polybasic acid or polybasic acid anhydride in the above method (3) include the same as those mentioned above.

[0083] Of these, it is preferable that the structural unit (C) contains a structural unit derived from the above method (2), since the acid group formed is separated from the main chain, thereby improving developability. The polymer may have only one type of the structural unit (C), or may have two or more types.

[0084] The content of the structural unit (C) in the polymer is preferably 1 to 50% by mass, more preferably 3 to 30% by mass, and even more preferably 5 to 15% by mass, relative to 100% by mass of all structural units of the polymer, in terms of good developability.

[0085] <Constituent Unit (D)> The polymer (X) preferably further comprises a structural unit (D) having a ring structure in the main chain. By comprising the structural unit (D), the heat resistance of the polymer can be further improved. Examples of the ring structure include an imide ring, a tetrahydrofuran ring, and a lactone ring.

[0086] Examples of monomers into which the structural unit (D) can be introduced include monomers having a double bond-containing ring structure in the molecule, monomers that undergo cyclopolymerization to form a polymer having a ring structure in the main chain, and monomers that form a ring structure after polymerization. Among these, from the viewpoints of good heat resistance, solvent resistance, hardness, colorant dispersibility, etc., the structural unit (D) is preferably a structural unit derived from at least one monomer selected from the group consisting of N-substituted maleimide monomers, dialkyl-2,2'-(oxydimethylene)diacrylate monomers, and α-(unsaturated alkoxyalkyl)acrylate monomers, and more preferably a structural unit derived from an N-substituted maleimide monomer in terms of even better solvent resistance.

[0087] Examples of the N-substituted maleimide monomer include the N-substituted maleimide monomers described in JP-A-2023-75463. Among them, from the viewpoint of heat resistance, N-phenylmaleimide, N-benzylmaleimide, and N-cyclohexylmaleimide are preferred, and N-benzylmaleimide is more preferred.

[0088] Examples of the dialkyl-2,2'-(oxydimethylene) diacrylate monomer include compounds described in JP-A-2023-75463. Among them, dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate is preferred from the viewpoints of transparency, dispersibility, and ease of industrial availability.

[0089] Examples of the α-(unsaturated alkoxyalkyl) acrylate monomer include the α-(allyloxymethyl) acrylate monomer described in JP-A-2023-75463. Among them, methyl α-allyloxymethylacrylate (also referred to as methyl-(α-allyloxymethyl)acrylate) is preferred from the viewpoints of transparency, dispersibility, and ease of industrial availability.

[0090] The polymer (X) may have only one type of the structural unit (D), or may have two or more types.

[0091] The content of the structural unit (D) in the polymer (X) is preferably 0.1 to 50 mass%, more preferably 0.5 to 30 mass%, and even more preferably 1 to 5 mass%, relative to 100 mass% of all structural units of the polymer, in terms of good heat discoloration resistance.

[0092] <Constituent Unit (E)> The polymer (X) preferably further contains a structural unit (E) derived from a hydroxyl group-containing monomer. Examples of the hydroxyl group-containing monomer include the same hydroxyl group-containing monomers as those mentioned above.

[0093] The content of the structural unit (E) in the polymer (X) is preferably 1 to 60% by mass, more preferably 3 to 50% by mass, and even more preferably 5 to 20% by mass, relative to 100% by mass of all structural units of the polymer, in order to achieve good developability.

[0094] <Constituent Unit (F)> The polymer (X) may have a structural unit (F) other than the structural units (A) to (E) described above. Examples of the structural unit (F) include structural units derived from the epoxy group-containing monomers described above, as well as structural units derived from the following monomers: Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, s-butyl (meth)acrylate, n-amyl (meth)acrylate, s-amyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentaerythritol (meth)acrylate (Meth)acrylic acid ester monomers such as tungsten, 4-(1-methoxy)ethoxycyclohexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, 1,4-dioxaspiro[4,5]dec-2-yl methacrylic acid, (meth)acryloylmorpholine, 4-(meth)acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, and 4-(meth)acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane; Aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, and methoxystyrene; (Meth)acrylamides such as N,N-dimethyl(meth)acrylamide and N-methylol(meth)acrylamide; Macromonomers having a (meth)acryloyl group at one end of the polymer molecular chain, such as polystyrene, polymethyl (meth)acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, and polycaprolactam; Conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, and 4-hydroxybutyl vinyl ether; N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine, and N-vinylacetamide; Unsaturated isocyanates such as isocyanatoethyl (meth)acrylate and allyl isocyanate; and the like.

[0095] The polymer (X) may have only one type of the structural unit (F), or may have two or more types.

[0096] The content of the structural unit (F) in the polymer (X) is preferably 10 to 80 mass%, more preferably 20 to 60 mass%, and even more preferably 30 to 40 mass%, relative to 100 mass% of all structural units of the polymer, in terms of good heat discoloration resistance.

[0097] The acid value of the polymer (X) is preferably from 10 to 150 mgKOH / g, more preferably from 30 to 100 mgKOH / g, and even more preferably from 50 to 80 mgKOH / g, in terms of good developability. The acid value is a value obtained by measurement by neutralization titration using a potassium hydroxide (KOH) solution, and is an acid value per 1 g of resin solid content.

[0098] The weight average molecular weight of the polymer (X) is preferably 1,000 to 1,000,000, more preferably 2,000 to 20,000, and even more preferably 5,000 to 15,000, in terms of good low-temperature curing properties. The weight average molecular weight is a value obtained by measurement using gel permeation chromatography (GPC) in the manner described in the Examples.

[0099] The vinyl ether equivalent of the polymer (X) is preferably 200 to 20,000 g / mol, more preferably 300 to 5,000 g / mol, and even more preferably 500 to 2,000 g / mol, in view of good low-temperature curing properties. The vinyl ether group here refers to a vinyl ether group that is generated when all acetal bonds in a polymer are deprotected, and refers to a vinyl ether group that is potentially present in the polymer.

[0100] The vinyl ether equivalent is the mass of the solid content of the polymer solution per 1 mol of vinyl ether groups of the polymer. The mass of the solid content of the polymer solution is the mass of the monomer components constituting the polymer (X). The vinyl ether equivalent can be determined by dividing the mass (g) of the polymer solid content of the polymer solution by the vinyl ether groups (mol) of the polymer.

[0101] The polymer (X) may have a polymerizable double bond in a side chain. By having a polymerizable double bond in a side chain, the curability of the polymer can be improved. Examples of the polymerizable double bond include the polymerizable double bonds described above. Among them, a (meth)acryloyl group is preferred in terms of reactivity.

[0102] When the polymer (X) has a polymerizable double bond in a side chain, the polymerizable double bond equivalent of the polymer (X) is preferably 200 to 20,000 g / mol, more preferably 300 to 5,000 g / mol, and even more preferably 500 to 2,000 g / mol, in terms of good reactivity. The polymerizable double bond here refers to a double bond that is radically polymerizable, i.e., a polymerizable double bond typified by a (meth)acryloyl group, and a double bond such as that formed by adding tetrahydrophthalic anhydride to a hydroxyl group is not included in the calculation of the polymerizable double bond equivalent because it has no reactivity.

[0103] The polymerizable double bond equivalent is the mass of the solid content of the polymer solution per 1 mol of polymerizable double bonds in the polymer. The mass of the solid content of the polymer solution is the mass of the monomer components that constitute the polymer. The polymerizable double bond equivalent can be determined by dividing the mass (g) of the polymer solid content of the polymer solution by the amount (mol) of double bonds in the polymer.

[0104] <Method of producing polymer> The method for producing the polymer (X) of the present invention is not particularly limited as long as it can produce the above-mentioned polymer, and examples thereof include a method in which a monomer component containing the above-mentioned structural unit (A) and structural unit (B) and, if necessary, a monomer capable of introducing structural units (C), (D), and (E) is polymerized by a known method. The amount of each monomer can be appropriately adjusted so that the content of each structural unit in the polymer falls within the desired range.

[0105] The method for polymerizing the monomer components is not particularly limited, and commonly used techniques such as bulk polymerization, solution polymerization, and emulsion polymerization can be used. Among these, solution polymerization is preferred because it is industrially advantageous and allows for easy structural adjustment such as molecular weight. Furthermore, the polymerization mechanism of the monomer components can be based on a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, and coordination polymerization, but a polymerization method based on a radical polymerization mechanism is preferred because of its industrial advantages. The molecular weight of the polymer obtained by polymerizing the above-mentioned monomer components can be controlled by adjusting the amount and type of polymerization initiator, the polymerization temperature, the type and amount of chain transfer agent, and the like.

[0106] Examples of the polymerization initiator include known peroxides and azo compounds that are commonly used as polymerization initiators. Examples of the chain transfer agent include compounds having a mercapto group, such as alkyl mercaptans, mercaptocarboxylic acids, and mercaptocarboxylic acid esters, that are commonly used as chain transfer agents. These may be used alone or in combination of two or more. The amounts of these agents added can be appropriately determined using known methods.

[0107] Examples of the solvent used in the polymerization include aromatic hydrocarbon solvents such as toluene, xylene, and benzene; aliphatic hydrocarbon solvents such as hexane, pentane, heptane, and cyclohexane; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; halogenated hydrocarbon solvents such as chlorobenzene, dichloromethane, chloroform, and 1,2-dichloroethane; nitrile solvents such as acetonitrile, propionitrile, and valeronitrile; ester solvents such as methyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate; amide solvents such as dimethylformamide (DMF), dimethylacetamide, and N-methylpyrrolidone; Examples of suitable solvents include ether solvents such as ethyl ether, diisopropyl ether, 1,2-dimethoxyethane (DME), 1,4-dioxane, tetrahydrofuran (THF), tetrahydropyran (THP), anisole, diethylene glycol dimethyl ether (diglyme), diethylene glycol ethyl ether (carbitol), cyclopentyl methyl ether (CPME), propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether; fluorine-based solvents such as perfluorohexane, perfluorocyclohexane, pentafluorobenzene, and octafluorotoluene; and DMSO and nitromethane. These may be used alone or in combination of two or more. The amount of the solvent used is not particularly limited and can be appropriately determined by a known method. Propylene glycol monomethyl ether acetate is most preferred because it is highly volatile and easily forms a coating film.

[0108] The polymerization is preferably carried out in the presence of a basic compound, which inhibits the formation of vinyl ether groups in the monomer (a) that can introduce the structural unit (A), thereby allowing the desired polymerization reaction to proceed smoothly.

[0109] Examples of the basic compound include ammonia; primary amines such as methylamine; secondary amines such as dimethylamine; tertiary amines such as triethylamine and diethylmethylamine; aliphatic amines such as dimethylethanolamine, n-butylamine, and diethylamine; cycloaliphatic amines such as cyclohexylamine; heterocyclic amines such as piperidine, morpholine, N-ethylpiperidine, N-ethylmorpholine, and pyridine; aromatic amines such as benzylamine, N-methylaniline, and N,N-dimethylaniline; tetraalkylammonium halides such as tetramethylammonium chloride and tetraethylammonium chloride; organic acid salts of tetraalkylammonium such as tetramethylammonium acetate; inorganic acid salts of tetraalkylammonium such as tetramethylammonium hydrogen sulfate and tetraethylammonium hydrogen sulfate; (hydroxy)alkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and monohydroxyethyltrimethylammonium hydroxide; hydroxides of alkali metals such as sodium and potassium; hydroxides of transition metals such as barium, strontium, calcium, and lanthanum; and free salts of complex salts such as [Pt(NH3)6](OH)4. Among these, secondary amines, tertiary amines and heterocyclic amines are preferred, and tertiary amines are more preferred, from the viewpoint of suppressing deprotection.

[0110] The amount of the basic compound used is not particularly limited and can be appropriately determined by a known method.

[0111] Regarding the polymerization conditions, the polymerization temperature may be appropriately set depending on the type and amount of the monomer used, the type and amount of the polymerization initiator, etc., and is, for example, preferably 40 to 130° C., more preferably 50 to 100° C. Similarly, the polymerization time can also be appropriately set and is, for example, preferably 1 to 15 hours, more preferably 2 to 11 hours.

[0112] In particular, the method for producing the polymer (X) preferably includes a step (1) of polymerizing a monomer component containing at least the monomer (a) and the monomer (b), in terms of efficient production. The polymerization step (1) is as described above. The monomer components used in the polymerization step may contain other monomers in addition to the monomers (a) and (b). Examples of such other monomers include monomers that can introduce the structural units (C), (D), and (E). The content of these monomers may be adjusted appropriately so that the content of each structural unit in the polymer falls within the desired range.

[0113] The monomer (a) may be a commercially available product or may be synthesized. Examples of a method for producing the monomer (a) include a method of reacting a vinyl ether group-containing (meth)acrylate compound with a carboxylic acid compound, an alcohol compound, a thiol compound, an amine compound, or the like.

[0114] Preferred examples of the vinyl ether group-containing (meth)acrylate compound include 2-(2-vinyloxyethoxy)ethyl acrylate and 2-(2-vinyloxyethoxy)ethyl methacrylate.

[0115] Examples of the carboxylic acid compound include aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, lauric acid, valeric acid, caproic acid, enanthic acid, heptyl acid, octanoic acid, lauric acid, myristic acid, palmitic acid, and stearic acid; monocarboxylic acid compounds such as formic acid, benzoic acid, β-carboxyethyl (meth)acrylate, mono(2-acryloyloxyethyl) succinate, and mono(2-methacryloyloxyethyl) succinate; and dicarboxylic acid compounds such as oxalic acid, malonic acid, succinic acid, tartaric acid, malic acid, maleic acid, gluconic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, and 5-norbornene dicarboxylic acid. Among these, monocarboxylic acids are preferred in that the product is easily copolymerizable, aliphatic carboxylic acids and formic acid are more preferred, and acetic acid, propionic acid, butyric acid and formic acid are even more preferred, and propionic acid, butyric acid and lauric acid are even more preferred in that they improve the curability and storage stability after polymerization, with butyric acid being the most preferred.

[0116] Preferred examples of the alcohol compound include monoalcohols having 1 to 10 carbon atoms, such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, isobutyl alcohol, isoamyl alcohol, propylene glycol monomethyl ether, and propylene glycol monobutyl ether; and polyhydric alcohols having 1 to 10 carbon atoms, such as (poly)ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, tetraethylene glycol, and (poly)propylene glycol. Of these, monoalcohols are preferred because the resulting product is easily copolymerizable, and ethanol, isopropanol, and propylene glycol monomethyl ether are more preferred.

[0117] Examples of the thiol compound include dodecanethiol.

[0118] The amine compound may, for example, be diethylamine.

[0119] The reaction is not particularly limited and can be carried out by a known method such as mixing the components and heating them. The amount of the compound used may be adjusted as appropriate, but it is preferable to mix 1 equivalent or more of the compound, more preferably 1 to 20 equivalents, even more preferably 1.1 to 10 equivalents, and even more preferably 1.2 to 2 equivalents, per equivalent of the vinyl ether group-containing (meth)acrylate compound.

[0120] In the above reaction, it is not necessary to use a solvent, but a solvent may be used. Examples of the solvent include the same solvents as those mentioned above for polymerization.

[0121] In the above reaction, commonly used additives such as catalysts and polymerization inhibitors may also be used. The additives may be known. The amount of each additive used may also be appropriately selected from known techniques.

[0122] The reaction temperature in the above reaction is, for example, preferably 0 to 100°C, more preferably 10 to 80°C, and even more preferably 20 to 60°C. The reaction time is, for example, preferably 0.1 to 20 hours, more preferably 1 to 15 hours, and even more preferably 2 to 12 hours.

[0123] When the polymer (X) has the structural unit (C), the method for producing the polymer preferably further comprises a step (2) of reacting the polymer obtained in the step (1) with an acid group-containing compound.

[0124] In this case, for example, the method for producing the polymer preferably includes a step (1) of polymerizing the monomer (a), the monomer (b), and a monomer component containing an epoxy group-containing monomer or a hydroxyl group-containing monomer, and a step (2) of reacting the polymer obtained in the step (1) with an acid group-containing compound.

[0125] The acid group-containing compound is preferably a polybasic acid or a polybasic acid anhydride, and examples thereof include carboxylic acids such as succinic acid, maleic acid, phthalic acid, tetrahydrophthalic acid, and trimellitic acid; carboxylic acid anhydrides such as succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, itaconic anhydride, and trimellitic anhydride; etc. Among these, carboxylic acid anhydrides are preferred in terms of higher addition reactivity, and succinic anhydride is more preferred. The amount of the acid group-containing compound used may be appropriately determined depending on the use, purpose, desired acid value, etc. of the resulting polymer.

[0126] The reaction in step (2) is preferably carried out in the presence of a basic compound, such as the same basic compounds that may be used in step (1).

[0127] The basic compound is preferably used in an amount of 0.1 to 3 equivalents, more preferably 0.5 to 1.5 equivalents, and most preferably 0.8 to 1.1 equivalents, per equivalent of the polybasic acid or polybasic acid anhydride.

[0128] Furthermore, when producing a polymer having a polymerizable double bond in the side chain, for example, after the above step (1), a polymerizable double bond can be introduced into the side chain of the polymer by addition reacting an epoxy group or a hydroxyl group with a compound having an acid group and a polymerizable double bond, such as (meth)acrylic acid. Alternatively, a polymerizable double bond can be introduced into the side chain of the polymer by addition reacting an unsaturated isocyanate with an acid group or a hydroxyl group instead of (meth)acrylic acid. Addition of an unsaturated isocyanate is most preferred because the product has a urethane bond or an amide bond, improving hydrophilicity.

[0129] The addition reaction of the (meth)acrylic acid, unsaturated isocyanates, etc., described above is not particularly limited and can be carried out by a known method. In addition, during the addition reaction, a catalyst, a solvent, etc. that are usually used may be used.

[0130] The method for producing the polymer may include other steps in addition to the reaction step described above. Examples of the other steps include an aging step, a neutralization step, a dilution step, a drying step, a concentration step, and a purification step. These steps can be carried out by known methods.

[0131] 2. Polymer composition The present invention also relates to a polymer composition comprising a polymer having a structural unit (A) represented by the above general formula (1) and at least one compound selected from the group consisting of hindered phenol compounds, hindered amine compounds, cyano(meth)acrylate compounds, melamine compounds, and thiol compounds.

[0132] The polymer composition of the present invention has excellent storage stability and can provide a cured product in which yellowing due to oxidative degradation is suppressed. The reason why the polymer composition of the present invention can provide a cured product in which yellowing due to oxidative degradation is suppressed is presumably because, like the above-mentioned polymer of the present invention, the polymer composition contains a compound having a specific radical scavenging ability, which can suppress the generation of radicals generated by oxidation of the polymer or capture the radicals, thereby suppressing degradation of the polymer due to radicals.

[0133] The polymer in the polymer composition of the present invention (hereinafter also referred to as "polymer (Y)") may be the same as the polymer (X) described above, but the polymer (Y) may not have the structural unit (B) described above. In this case, the content of the structural unit (A) in the polymer (Y) is preferably 1 to 90 mass%, more preferably 5 to 50 mass%, and even more preferably 15 to 30 mass%, relative to 100 mass% of all structural units. The content of the structural unit (C) in the polymer (Y) is preferably 1 to 50 mass %, more preferably 3 to 30 mass %, and even more preferably 5 to 15 mass %, relative to 100 mass % of all structural units. The content of the structural unit (D) in the polymer (Y) is preferably 0.1 to 50 mass %, more preferably 0.5 to 30 mass %, and even more preferably 1 to 5 mass %, relative to 100 mass % of all structural units. The content of the structural unit (E) in the polymer (Y) is preferably 1 to 60 mass %, more preferably 3 to 50 mass %, and even more preferably 5 to 20 mass %, relative to 100 mass % of all structural units. The content of the structural unit (F) in the polymer (Y) is preferably 10 to 80 mass %, more preferably 20 to 60 mass %, and even more preferably 30 to 40 mass %, relative to 100 mass % of all structural units.

[0134] Examples of the hindered phenol compound in the polymer composition include the above-mentioned hindered phenol compounds having a polymerizable group, as well as Topanol, Irganox 1010, TINUVIN P, TINUVIN PS, TINUVIN 320, TINUVIN 326, TINUVIN 327, TINUVIN 109, TINUVIN 384-2, TINUVIN 234, TINUVIN 328, TINUVIN 329, TINUVIN 360, TINUVIN 213, TINUVIN 571, TINUVIN 1130, TINUVIN 900, TINUVIN 1577FF, TINUVIN 400, TINUVIN 405, TINUVIN 460, and TINUVIN 571 manufactured by BASF. 479, IRGANOX1076, IRGANOX1135, IRGANOX1035, IRGANOX1098, IRGANOX1141, IRGANOX1330, IRGANOX1520L, IRGANOX245, IRGANOX259, IRGANOX3790, IRGANOX3114, IRGANOX5057, IRGANOX565, IRGANOX1222, Adeka Corporation's ADK STAB LA-24, ADK STAB LA-29, ADK STAB LA -31RG, ADK STAB LA-31G, ADK STAB LA-32, ADK STAB LA-34, ADK STAB LA-36, ADK STAB LA-36RG, ADK STAB LA-46, ADK STAB LA-F70, ADK STAB 1413, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-20, Sumika Chemtex Corporation's Sumisorb 100, Sumisorb 250, Sumisorb 300, Sumisorb 320, Sumisorb 340, Sumisorb 350, Sumisorb 300, Sumisorb 110, Sumisorb 120, Sumisorb 130, Sumisorb 400, Sumisorb 200, Sumilizer BBM-S, Sumilizer MB, Sumilizer GM, Sumilizer GS, Viosorb 520, Viosorb 550, Viosorb 580, Viosorb manufactured by Kyodo Pharmaceutical Co., Ltd.582, Viosorb 591, Viosorb 583, Viosorb 100, Viosorb 110, Viosorb 120, Viosorb 130, benzophenone compounds such as Seesorb 701, Seesorb 702, Seesorb 703, Seesorb 705 manufactured by Shipro Chemical Co., Ltd., benzotriazole compounds such as Seesorb 701, and Dithlyzer O, Dithlyzer M, Dithlyzer E, Dithlyzer S manufactured by Sankyo Kasei Co., Ltd. Of these, topanol is preferred as the hindered phenol compound.

[0135] Examples of the hindered amine compound include the above-mentioned hindered amine compounds having a polymerizable group, as well as Adeka STAB LA-52, Adeka STAB LA-57, Adeka STAB LA-63P, Adeka STAB LA-68, Adeka STAB LA-72, Adeka STAB LA-77Y, Adeka STAB LA-77G, Adeka STAB LA-81, Adeka STAB LA-402AF, Adeka STAB LA-40MP, and Adeka STAB LA-40Si, all manufactured by Adeka Corporation; and BASF's TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 744, TINUVIN 765, TINUVIN 770, TINUVIN 622LD, CHIMASSORB 944 FD / LD, and CHIMASSORB 2020 FDL.

[0136] Examples of the cyano(meth)acrylate compound include the same compounds as those mentioned above.

[0137] Examples of the melamine compound include N,N',N''-Tri(m-tolyl)-1,3,5-triazine-2,4,6-triamine.

[0138] Examples of the thiol compound include the thiol compound having the above-mentioned polymerizable group, as well as polyfunctional thiol compounds and monofunctional thiol compounds. Examples of polyfunctional thiols include pentaerythritol tetrakis(3-mercaptobutyrate), Jisnet F (TTCA), Jisnet DB, Santhiol N-1, and Santhiol NW manufactured by Sankyo Kasei Co., Ltd., and examples of monofunctional thiols include dodecanethiol, β-mercaptopropionic acid, and thioglycerol.

[0139] Among these, the at least one compound selected from the group consisting of hindered phenol compounds, hindered amine compounds, cyano(meth)acrylate compounds, melamine compounds, and thiol compounds is preferably at least one compound selected from the group consisting of hindered phenol compounds and thiol compounds, and more preferably a thiol compound, in that yellowing can be further suppressed.

[0140] The content of the at least one compound selected from the group consisting of hindered phenol compounds, hindered amine compounds, cyano(meth)acrylate compounds, melamine compounds, and thiol compounds in the polymer composition may be appropriately selected depending on the purpose and use of the polymer composition. In terms of good heat discoloration resistance, the content is preferably 0.001 to 30 mass%, more preferably 0.1 to 10 mass%, and even more preferably 0.2 to 2 mass%, relative to 100 mass% of the total solid content of polymer (Y).

[0141] The polymer composition may contain other components such as a solvent in addition to the above-mentioned polymer and compound. Examples of other components include antioxidants, such as sulfur-based antioxidants and phosphorus-based antioxidants. These components are also effective in suppressing oxidation of the polymer (Y).

[0142] Examples of the sulfur-based antioxidant include Adeka Stab AO-412S and Adeka Stab AO-503 manufactured by Adeka Corporation, and Sumilizer TPL, Sumilizer TPS, and Sumilizer TP-D manufactured by Sumika Chemtex Corporation.

[0143] Examples of the phosphorus-based antioxidant include tertiary phosphines such as tricyclophosphine and triphenylphosphine, as well as Adeka STAB PEP-8, Adeka STAB PEP-36, Adeka STAB PEP-10, Adeka STAB 2112, Adeka STAB 2112RG, Adeka STAB 1178, Adeka STAB 1500, Adeka STAB C, Adeka STAB 135A, Adeka STAB 3010, and Adeka STAB TPP, all manufactured by Adeka Corporation, and IRGAFOS168, IRGAFOS38, IRGAFOS P-EPQ, IRGAFOS126, IRGAFOS12, and IRGAFOS PUR68, all manufactured by BASF.

[0144] <Monomer Composition> Furthermore, a monomer composition containing a monomer component including the monomer (a) capable of introducing the structural unit (A) and at least one compound selected from the group consisting of the hindered phenol compounds, hindered amine compounds, cyano(meth)acrylate compounds, melamine compounds, and thiol compounds is also one preferred embodiment of the present invention.

[0145] The monomer component may contain, in addition to the monomer (a), the monomer (b) and the monomers (c) to (f) into which the structural units (C) to (F) can be introduced. The content of these can be adjusted appropriately so that the content of each of the structural units described above falls within the desired range.

[0146] Examples of the hindered phenol compound, hindered amine compound, cyano(meth)acrylate compound, melamine compound, and thiol compound used in the above-mentioned monomer composition include the same compounds as those contained in the above-mentioned polymer composition.

[0147] In the above monomer composition, the content of at least one compound selected from the group consisting of hindered phenol compounds, hindered amine compounds, cyano(meth)acrylate compounds, melamine compounds, and thiol compounds is preferably 0.001 to 30 mass%, more preferably 0.1 to 10 mass%, and even more preferably 0.2 to 2 mass%, relative to 100 mass% of the total solid content of the monomers.

[0148] The monomer composition may contain other components such as a solvent in addition to the polymer and compound described above. Examples of other components include antioxidants, such as the sulfur-based antioxidants and phosphorus-based antioxidants described above. These components are also effective in suppressing oxidation of the monomer.

[0149] 3.Resin composition The present invention also relates to a resin composition comprising the polymer (X) or the polymer composition described above and a polymerizable compound. The resin composition of the present invention also comprises the polymer (X) or the polymer composition described above, and therefore can provide a cured product with excellent storage stability and suppressed yellowing due to oxidative degradation. Furthermore, the polymerizable compound can impart radical curability.

[0150] The content of the polymer (X) in the resin composition is preferably 1 to 90 mass %, more preferably 5 to 50 mass %, and even more preferably 10 to 30 mass %, relative to 100 mass % of the total solid content of the resin composition.

[0151] The content of the polymer composition in the resin composition is preferably 1 to 90 mass%, more preferably 5 to 50 mass%, and even more preferably 10 to 30 mass%, relative to 100 mass% of the total solid content of the resin composition.

[0152] (polymerizable compound) The polymerizable compound is a low molecular weight compound having a polymerizable unsaturated bond (also referred to as a polymerizable unsaturated group) that can be polymerized by irradiation with active energy rays such as free radicals, electromagnetic waves (e.g., infrared rays, ultraviolet rays, X-rays, etc.), and electron beams. Examples of the polymerizable compound include monofunctional compounds having one polymerizable unsaturated group in the molecule and polyfunctional compounds having two or more polymerizable unsaturated groups.

[0153] Examples of the monofunctional compound include N-substituted maleimide monomers, (meth)acrylic acid esters, (meth)acrylamides, unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, unsaturated monocarboxylic acids in which the unsaturated group and the carboxyl group are chain-extended, unsaturated acid anhydrides, aromatic vinyls, conjugated dienes, vinyl esters, vinyl ethers, N-vinyl compounds, unsaturated isocyanates, etc. Monomers having an active methylene group or an active methine group can also be used.

[0154] Examples of the polyfunctional compound include the following compounds. bifunctional (meth)acrylate compounds such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, bisphenol A alkylene oxide di(meth)acrylate, and bisphenol F alkylene oxide di(meth)acrylate;

[0155] Trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, ethylene oxide-added trimethylolpropane tri(meth)acrylate, ethylene oxide-added ditrimethylolpropane tetra(meth)acrylate, ethylene oxide-added pentaerythritol tetra(meth)acrylate, ethylene oxide-added dipentaerythritol hexa(meth)acrylate, propylene oxide-added trimethylolpropane tri(meth)acrylate, propylene oxide-added ditrimethylolpropane tetra(meth)acrylate, propylene oxide-added pentaerythritol tetra(meth)acrylate, propylene oxide-added dipentaerythritol hexa(meth)acrylate, ε-caprolactone-added trimethylolpropane tri(meth)acrylate, ε-caprolactone-added ditrimethylolpropane tetra(meth)acrylate, ε-caprolactone-added pentaerythritol tetra(meth)acrylate, ε-caprolactone-added dipentaerythritol hexa(meth)acrylate, dipentaerythritol pentaacrylate succinic acid-modified product, pentaerythritol triacrylate succinic acid-modified product, dipentaerythritol pentaacrylate phthalic acid-modified product, pentaerythritol triacrylate phthalic acid-modified product,

[0156] [ka]

[0157] a tri- or higher functional (meth)acrylate compound such as a modified product of dipentaerythritol hexaacrylate represented by the formula:

[0158] polyfunctional vinyl ethers such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, and ethylene oxide-added dipentaerythritol hexavinyl ether;

[0159] vinyl ether group-containing (meth)acrylic acid esters such as 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 5-vinyloxypentyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, and 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate;

[0160] Ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerin triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylolpropane triallyl ether, ethylene polyfunctional allyl ethers such as ethylene oxide-added ditrimethylolpropane tetraallyl ether, ethylene oxide-added pentaerythritol tetraallyl ether, and ethylene oxide-added dipentaerythritol hexaallyl ether;

[0161] Allyl group-containing (meth)acrylic acid esters such as allyl (meth)acrylate; polyfunctional (meth)acryloyl group-containing isocyanurates such as tri(acryloyloxyethyl)isocyanurate, tri(methacryloyloxyethyl)isocyanurate, alkylene oxide-added tri(acryloyloxyethyl)isocyanurate, and alkylene oxide-added tri(methacryloyloxyethyl)isocyanurate; polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; polyfunctional urethane (meth)acrylates obtained by reacting polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate with hydroxyl group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; polyfunctional aromatic vinyls such as divinylbenzene; etc. These polymerizable compounds may be used alone or in combination of two or more.

[0162] Among the polymerizable compounds, it is preferable to use a polyfunctional polymerizable compound from the viewpoint of further enhancing the curability of the resin composition. The number of functionalities of the polyfunctional polymerizable compound is preferably 3 or more, more preferably 4 or more. The number of functionalities is preferably 10 or less, more preferably 8 or less. The molecular weight of the polymerizable compound is not particularly limited, but is preferably 2000 or less from the viewpoint of handling.

[0163] Among the polyfunctional polymerizable compounds, from the viewpoints of reactivity, economy, availability, etc., preferred are compounds having a (meth)acryloyl group, such as polyfunctional (meth)acrylate compounds, polyfunctional urethane (meth)acrylate compounds, and (meth)acryloyl group-containing isocyanurate compounds, and more preferred are polyfunctional (meth)acrylate compounds. By including a compound having a (meth)acryloyl group, the resin composition has better photosensitivity and curability, and a cured product with even higher hardness and transparency can be obtained. It is even more preferred to use a trifunctional or higher polyfunctional (meth)acrylate compound as the polyfunctional polymerizable compound.

[0164] The content of the polymerizable compound is preferably 1 to 90 mass %, more preferably 5 to 60 mass %, and even more preferably 10 to 40 mass %, relative to 100 mass % of the total solid content of the resin composition.

[0165] (Photopolymerization initiator) The resin composition preferably further contains a photopolymerization initiator. By containing the photopolymerization initiator, the resin composition can be used as a photosensitive resin composition, and the curing reaction of the resin composition can proceed more easily, thereby producing a stronger cured product.

[0166] Specific examples of the photopolymerization initiator include aminoketone compounds such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("IRGACURE907", manufactured by BASF), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 ("IRGACURE369", manufactured by BASF), and 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one ("IRGACURE379", manufactured by BASF); 2,2-dimethoxy-1,2-diphenylethan-1-one ("IRGACURE651", manufactured by BASF), phenylglyoxylic acid methyl ester ("DAROCURE"); benzyl ketal compounds such as 1-hydroxycyclohexylphenyl ketone ("IRGACURE184", BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one ("DAROCUR1173", BASF), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one ("IRGACURE2959", BASF), 2-hydroxy Hydroketone compounds such as 1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one ("IRGACURE 127", manufactured by BASF) and [1-hydroxy-cyclohexyl-phenyl-ketone + benzophenone] ("IRGACURE 500", manufactured by BASF); as well as other alkylphenone compounds exemplified in paragraphs

[0084] to

[0086] of JP 2013-227485 A;1,2-Octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime) ("OXE01", manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) ("OXE02", manufactured by BASF), 1,2-Octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone ("OXE03", manufactured by BASF), 1-[9-ethyl Examples of suitable photopolymerization initiators include oxime ester compounds such as [-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) ("OXE04", manufactured by BASF); benzophenone compounds; benzoin compounds; thioxanthone compounds; halomethylated triazine compounds; halomethylated oxadiazole compounds; biimidazole compounds; titanocene compounds; benzoic acid ester compounds; acridine compounds; and phosphine oxide compounds. Among these, aminoketone compounds and oxime ester compounds are preferred. The photopolymerization initiators may be used alone or in combination of two or more.

[0167] The content of the photopolymerization initiator is preferably 0.01 to 50% by mass, more preferably 0.1 to 20% by mass, and even more preferably 1 to 10% by mass, relative to 100% by mass of the total solid content of the resin composition.

[0168] The resin composition may further contain components other than those described above. The other components may be appropriately selected depending on the purpose and application of the resin composition. Examples of the other components include solvents; colorants (pigments, dyes); dispersants; heat resistance improvers; leveling agents; inorganic fine particles such as silica, titanium, and zirconia fine particles; organic fine particles such as acrylic, polystyrene, and polyolefin fine particles; silane-based, aluminum-based, and titanium-based coupling agents; fillers; resins; plasticizers; polymerization initiators; heat curing agents; polymerization inhibitors; ultraviolet absorbers; antioxidants such as hindered phenol-based antioxidants; antioxidants such as thioether-based antioxidants; antioxidants such as phosphorus-based antioxidants; matting agents; antifoaming agents; antistatic agents; slip agents; surface modifiers; thixotropic agents; and acid generators. These may be used alone or in combination of two or more. These components may be appropriately selected from known components, and the amounts used may be appropriately determined.

[0169] The coloring material is not particularly limited as long as it is soluble or dispersible in a solvent, and examples thereof include dyes, pigments, etc. As the dye, it is preferable to use an acid dye having an acidic group such as a carboxylic acid or sulfonic acid group, a salt of an acid dye with a nitrogen compound, a sulfonamide of an acid dye, etc., from the viewpoints of solubility in a solvent or an alkaline developer, interaction with other components in the photosensitive polymer composition, heat resistance, etc.

[0170] Examples of such dyes include acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 11 4,129,133,134,138,143,145,150,151,158,176,183,198,211,215,216,217,249,252,257,260,266,274;acid violet 6B, 7, 9, 17, 19;acid Yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; Food Yellow 3 and derivatives thereof. Among these, azo-based, xanthene-based, anthraquinone-based, or phthalocyanine-based acid dyes are preferred. These can be used alone or in combination of two or more types depending on the desired pixel color.

[0171] Examples of pigments include yellow pigments such as CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, and 214; orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73; and CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, Examples of suitable pigments include red pigments such as CI Pigment Blue 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, and 265; blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, and 60; violet pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, and 38; green pigments such as CI Pigment Green 7, 36, and 58; brown pigments such as CI Pigment Brown 23 and 25; and black pigments such as CI Pigment Black 1, 7, carbon black, titanium black, and iron oxide. These pigments can be used alone or in combination depending on the desired color of the color filter. Depending on the desired color of the color filter, the content of the colorant is 5 to 80 parts by weight, preferably 5 to 70 parts by weight, and more preferably 10 to 60 parts by weight per 100 parts by weight of the resin composition.

[0172] When a pigment is used as the colorant, a known dispersant may be blended into the photosensitive polymer composition to improve the dispersibility of the pigment. It is preferable to use a polymeric dispersant that exhibits excellent dispersion stability over time. Examples of polymeric dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic modified ester-based dispersants. Commercially available polymeric dispersants such as EFKA (manufactured by EFKA Chemicals BV), Disperbyk (manufactured by BYK), Disparlon (manufactured by Kusumoto Chemicals Co., Ltd.), and SOLSPERSE (manufactured by Zeneca) may be used. The blending amount of the dispersant may be appropriately determined depending on the type of pigment used.

[0173] The resin composition preferably contains a protic polar solvent such as water or alcohol, since this further suppresses yellowing of the cured product. Of the protic polar solvents, water is more preferred. The content of the protic polar solvent is preferably 0.001 to 30% by mass, more preferably 0.1 to 10% by mass, and even more preferably 0.2 to 2% by mass, relative to 100% by mass of the total solids content of the resin composition. Similarly, the polymer or polymer composition preferably contains a protic polar solvent, and the content of the protic polar solvent in this form is preferably 0.001 to 30% by mass, more preferably 0.1 to 10% by mass, and even more preferably 0.2 to 2% by mass, relative to 100% by mass of the total polymer solid content.

[0174] <Preparation of Resin Composition> The method for preparing the resin composition is not particularly limited and may be a known method, for example, a method in which the above-mentioned components are mixed and dispersed using various mixers or dispersers. The mixing and dispersion step is not particularly limited and may be performed by a known method. In addition, other commonly performed steps may be further included. When the resin composition contains a colorant, it is preferable to prepare it through a known colorant dispersion treatment step.

[0175] 4.Cured product The method for obtaining a cured product using the resin composition of the present invention is not particularly limited, and any known method may be used. For example, the resin composition may be applied to a substrate or molded, and then cured by heating, irradiating with active energy rays such as ultraviolet rays, or a combination of these to obtain a cured product.

[0176] A preferred example of a method for producing the cured product includes a step (1) of applying the resin composition to a substrate to form a coating film, a step (2) of irradiating the formed coating film with light, a step (3) of developing and removing the unirradiated portion, and a step (4) of heating the irradiated coating film.

[0177] The substrate is not particularly limited and may be appropriately selected depending on the purpose and application. Examples include substrates made of various materials such as glass plates and plastic plates.

[0178] In the step (1), the method for applying the resin composition to form a coating film is not particularly limited, and can be any known method such as spin coating, slit coating, roll coating, or cast coating. In the above-mentioned production method, it is preferable to coat the resin composition on a substrate and then dry the coated film to form a coating film. The drying can be carried out by a known method, for example, using a hot plate, an IR oven, a convection oven, etc. The drying conditions are appropriately selected depending on the boiling point of the solvent components contained, the type of curing component, the film thickness, the performance of the dryer, etc., but it is usually preferable to dry at a temperature of 50 to 160°C for 10 to 300 seconds.

[0179] In the above step (2), the method for irradiating the formed coating film with light is not particularly limited and can be performed by any known method. Examples of light sources for actinic rays used for light irradiation 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, low-pressure mercury lamps, carbon arcs, and fluorescent lamps, and laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers.

[0180] When the coating film is irradiated with light, the irradiation may be carried out through a photomask, which may be a mask having a light-shielding portion formed according to a desired pattern.

[0181] In the above step (3), after the light irradiation step, a development process is carried out using a developer to remove the unirradiated portions. The irradiated portions are cured by light irradiation, and the cured product becomes insoluble or poorly soluble in the developer. On the other hand, the unirradiated portions dissolve in the developer and are removed by the development process, resulting in a patterned cured film. The development process can usually be carried out at a development temperature of 10 to 50°C by a method such as immersion development, spray development, brush development, or ultrasonic development.

[0182] The developer used in the step (3) is not particularly limited as long as it dissolves the resin composition, but an organic solvent or an alkaline aqueous solution is usually used, and a mixture thereof may also be used. When an alkaline aqueous solution is used as the developer, it is preferable to wash with water after development. Examples of organic solvents and alkaline aqueous solutions include those described in JP 2015-157909 A.

[0183] In the above step (4), the developed coating film is preferably heated at 150°C or lower. In the heating step (post-curing step) after light irradiation in the above step (4), the heating temperature is preferably 130°C or lower, more preferably 120°C or lower. The resin composition of the present invention allows the curing reaction to proceed smoothly even at relatively low temperatures, and can give a cured product with excellent solvent resistance. The lower limit of the heating temperature is preferably 70°C or higher, more preferably 80°C or higher, in terms of maintaining curability.

[0184] The heating time in the heating step is not particularly limited and is preferably 5 to 60 minutes, for example. The heating method is also not particularly limited and can be performed using known heating equipment such as a hot plate, a convection oven, or a high-frequency heater.

[0185] When the cured product obtained by the above production method is a cured film, the film thickness is preferably 0.1 to 50 μm, more preferably 0.5 to 40 μm, and even more preferably 1 to 30 μm, in order to fully exhibit the properties as a protective film.

[0186] The cured product obtained by the above-mentioned production method has excellent solvent resistance. The cured product obtained by curing the above-mentioned resin composition also constitutes one aspect of the present invention.

[0187] 5.Applications The polymer (X), polymer composition, and resin composition of the present invention have excellent storage stability and can provide cured products that are inhibited from yellowing due to oxidative degradation, and are therefore suitable for use in applications requiring storage stability and resistance to oxidative degradation. The polymer (X), polymer composition, and resin composition of the present invention are suitable for use as optical materials, preferably as resists. The resin composition of the present invention can be suitable for use in both negative-tone and positive-tone applications.

[0188] The polymer (X), polymer composition, and resin composition of the present invention can be suitably used for applications such as color filters, black matrices, photospacers, black column spacers, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, insulating films, films, organic protective films, etc. used in liquid crystal, organic EL, quantum dot, and micro LED liquid crystal displays, solid-state imaging devices, touch panel display devices, etc. Among these, they are preferably used for color filters.

[0189] 6. How to store polymers The present invention also relates to a method for storing a polymer having a structural unit (A) represented by the general formula (1) (hereinafter also referred to as polymer (Z)) in a container, characterized in that the oxygen concentration in the gas phase of the container is 10% by volume or less and / or the ratio of the void volume of the gas phase of the container to the volume of the container is 15% or less. The polymer storage method of the present invention can improve the storage stability of polymer (Z) having an acetal structure such as structural unit (A). The reason why the storage method can improve the storage stability of such polymers is thought to be that by keeping the oxygen concentration in the gas phase of the container below a certain level or keeping the void volume of the gas phase below a certain level, contact between the polymer and oxygen can be reduced, thereby suppressing oxidative degradation of the polymer.

[0190] The storage method is a method for storing the above-mentioned polymer in a container, and the space inside the container is composed of a portion occupied by the polymer (a solid phase portion, or a liquid phase portion in the case of a polymer solution) and a gas phase portion. In the storage method, the oxygen concentration in at least the gas phase portion is 10% by volume or less, preferably 5% by volume or less, and more preferably 3% by volume or less.

[0191] The oxygen concentration in the gas phase is measured by an oxygen concentration meter, specifically by the method described in the examples below.

[0192] It is also preferable that the volume of the gas phase of the container is small, since reducing contact between the polymer and air can suppress oxidative degradation. In the above preservation method, the ratio of the volume of the gas phase space in the container to the volume of the container is at least 15% or less, and preferably 10% or less. In the above preservation method, it is preferable that the oxygen concentration in the gas phase in the container is 10% by volume or less, and the ratio of the space volume of the gas phase in the container to the volume of the container is 15% or less.

[0193] In addition, in the container, the void volume is preferably 15% by volume or less, more preferably 10% by volume or less, and even more preferably 5% by volume or less, relative to 100% by volume of the polymer solution.

[0194] Examples of methods for adjusting the oxygen concentration in the gas phase to the above-mentioned range include a method of supplying an inert gas such as nitrogen gas to the gas phase in the container, and a method of bubbling an inert gas through the liquid phase containing the polymer.

[0195] The container is not particularly limited as long as it is made of a material such as plastic that does not adversely affect the polymer. The size of the container is also not particularly limited as long as it can seal the polymer.

[0196] The preservation method may be such that the oxygen concentration in the gas phase in a container containing the polymer is adjusted to a predetermined range, and then the container is sealed and allowed to stand to preserve the polymer.

[0197] The environment in which the container is left standing is not particularly limited as long as it does not adversely affect the polymer, but the temperature is preferably -50°C to 50°C, more preferably -30°C to 30°C, and the humidity is preferably 1 to 99%, more preferably 5 to 70%.

[0198] The structural unit (A) represented by the general formula (1) contained in the polymer (Z) includes the same structural unit (A) as that of the polymer (X). The polymer (Z) may further include a structural unit other than the structural unit (A). Examples of the other structural unit include the structural units (B) to (F) of the polymer (X).

[0199] The polymer (Z) may be any polymer having at least the structural unit (A), but preferably has the structural unit (A) and the structural unit (B) in the polymer (X), and more preferably is the same polymer as the polymer (X). Accordingly, a method for storing the polymer (X) in a container, characterized in that the oxygen concentration in the gas phase in the container is 10% by volume or less and / or the ratio of the free space volume of the gas phase in the container to the volume of the container is 15% or less, is also a preferred embodiment of the present invention.

[0200] 7. Method for storing polymer composition The present invention also provides a method for storing a polymer composition in a container, the method comprising storing the polymer (Z) and at least one compound selected from the group consisting of hindered phenol compounds, hindered amine compounds, cyano(meth)acrylate compounds, melamine compounds, and thiol compounds, wherein the oxygen concentration in the gas phase in the container is 10% by volume or less and / or the ratio of the free space volume of the gas phase in the container to the volume of the container is 15% or less.

[0201] The polymer composition can be well preserved by the same method as the above-mentioned method for preserving the polymer.

[0202] Examples of the hindered phenol compound, hindered amine compound, cyano(meth)acrylate compound, melamine compound, and thiol compound include the same compounds as those described above. The contents of these compounds are also as described above.

[0203] Therefore, a preferred embodiment of the present invention also includes a method for storing a polymer composition in a container, the method comprising storing the polymer (X) and at least one compound selected from the group consisting of hindered phenol compounds, hindered amine compounds, cyano(meth)acrylate compounds, melamine compounds, and thiol compounds, wherein the oxygen concentration in the gas phase in the container is 10% by volume or less and / or the ratio of the free space volume of the gas phase in the container to the volume of the container is 15% or less.

[0204] Furthermore, a photosensitive resin composition containing the above-mentioned polymer (Z) or a polymer composition containing the polymer (Z), a photopolymerization initiator, and a polyfunctional polymerizable compound can also be well stored in the same manner as the above-mentioned storage method for the polymer (Z) or the polymer composition. A preferred embodiment of the present invention also includes a method for storing a photosensitive resin composition containing the above-mentioned polymer (Z), a photopolymerization initiator, and a polyfunctional polymerizable compound in a container, wherein the oxygen concentration in the gas phase in the container is 10% by volume or less and / or the ratio of the free space volume of the gas phase in the container to the volume of the container is 15% or less. [Example]

[0205] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass." The various evaluation methods used in the present examples are as follows.

[0206] <Weight average molecular weight> The weight average molecular weight of the polymer was measured by GPC (gel permeation chromatography) using polystyrene as a standard substance and tetrahydrofuran as an eluent, with an HLC-8220GPC (manufactured by Tosoh Corporation) and a column: TSKgel SuperHZM-M (manufactured by Tosoh Corporation).

[0207] <Acid value> 3 g of the polymer solution was precisely weighed and dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and titrated using a 0.1 N KOH aqueous solution as a titrant. The titration was carried out using an automatic titrator (product name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value per 1 g of solid content (mg KOH / g) was calculated from the acid value of the polymer solution and the solid content of the polymer solution. The solid content of the polymer solution was determined by the following method. Approximately 1 g of the polymer solution was weighed into an aluminum cup, dissolved in approximately 3 g of acetone, and then naturally dried at room temperature. The solution was then dried under vacuum at 140°C for 1.5 hours using a hot air dryer (product name: PHH-101, manufactured by Espec Corporation), cooled in a desiccator, and then weighed. The solid content (mass%) of the polymer solution was calculated from the mass loss.

[0208] <Vinyl ether equivalent> It was determined by dividing the mass (g) of the polymer solid content by the number of moles (mol) of vinyl ether groups potentially contained in the polymer.

[0209] <Viscosity change rate> The viscosity of the polymer / resin composition / compound shown in Table 2 or Table 3 was measured at 25°C using a viscometer (VISCOMETER TV-100, manufactured by Toki Sangyo Co., Ltd.). The viscosity change rate is the rate of change in viscosity before and after storage when the composition is stored at 40°C for one week, and is expressed as the percentage (%) of the viscosity after storage, with the viscosity before storage being 100%. The smaller the viscosity change rate value, the better the storage stability of the polymer was evaluated to be.

[0210] <Appearance> The polymers / resin compositions / compounds shown in Table 2 or Table 3 were stored at 40° C. for 1 week, and then the appearance was visually observed. The degree of coloration of the appearance was evaluated according to the following criteria. (Evaluation criteria) ◎: A colorless, transparent liquid. ◯: It was a pale yellow liquid. △: Yellow liquid. ×: It was a brown liquid.

[0211] <Heat resistance coloring property b *> The polymer / resin composition / compound shown in Table 2 or Table 3 was spin-coated onto a 5 cm square glass substrate, dried at 100°C for 3 minutes, and then heat-treated at 120°C for 1 hour to obtain a thin film with a thickness of 20 μm. After cooling to room temperature, the b of the thin film after heat treatment was measured using a spectrophotometer ("CM-3700A", manufactured by Konica Minolta). * The values ​​were measured.

[0212] <Solvent resistance> The resin composition was spin-coated onto a 5 cm square glass substrate, dried at 90°C for 2 minutes, exposed to 100 mJ using a high-pressure mercury lamp, and heat-treated (post-cured) at 90°C for 30 minutes to obtain a cured film with a thickness of 2 μm. The cured film was then immersed in 20 g of propylene glycol monomethyl ether at 30°C for 5 minutes and then removed. The absorbance of the immersion liquid after removal of the cured film was measured using a UV3100 spectrophotometer (manufactured by Shimadzu Corporation). A higher absorbance value indicates that more colorant was eluted into the immersion liquid, and the resin composition was evaluated as having poor solvent resistance.

[0213] <Developability> The resin composition was applied to a 10 cm square glass substrate by spin coating, and after heat treatment (90°C, 3 minutes), it was irradiated with 60 mJ / cm using a UV aligner (manufactured by Dai Nippon Kaken Co., Ltd., product name "MA-1100") equipped with a 2.0 kW ultra-high pressure mercury lamp through a photomask with 30 μm line and space openings at a distance of 50 μm from the coating film. 2 The resist was exposed to light at an exposure dose of 1000 kJ / cm² (equivalent to 365 nm illuminance), and a 0.05% aqueous potassium hydroxide solution was sprayed using a spin developer to dissolve and remove the unexposed areas. The remaining exposed areas were then developed by washing with pure water for 10 seconds, and the developability was evaluated. Specifically, the coating film developed through the photomask as described above was observed with a surface roughness meter (manufactured by Ryoka Systems Co., Ltd., product name "VertScan2.0"), and the time it took for the unexposed areas to flow after spraying the 0.05% potassium hydroxide aqueous solution was defined as the development time.

[0214] <Line Thickening> The resin composition was applied to a 10 cm square glass substrate by spin coating, and after heat treatment (90°C, 3 minutes), it was irradiated with 60 mJ / cm using a UV aligner (manufactured by Dai Nippon Kaken Co., Ltd., product name "MA-1100") equipped with a 2.0 kW ultra-high pressure mercury lamp through a photomask with 30 μm line and space openings at a distance of 50 μm from the coating film. 2 The resist was exposed to light at an exposure dose of 1000 kJ / cm² (equivalent to 365 nm illuminance), and a 0.05% aqueous potassium hydroxide solution was sprayed using a spin developer to dissolve and remove the unexposed areas. The remaining exposed areas were then developed by washing with pure water for 10 seconds, and the developability was evaluated. Specifically, the coating film developed through the photomask as described above was observed with a surface roughness meter (manufactured by Ryoka Systems Co., Ltd., product name "VertScan2.0") to evaluate line thickening from 30 μm. A smaller value indicates less pattern line thickening and is evaluated as being excellent in miniaturization.

[0215] <Synthesis of monomer compound (BEEA)> A reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping tank inlet was charged with 100.0 parts (0.54 mol) of 2-(2-vinyloxyethoxy)ethyl acrylate and 47.3 parts (0.54 mol) of butyric acid, heated to 60°C, and reacted for 12 hours. After the reaction was completed, the reaction vessel was cooled, diluted with ethyl acetate, and transferred to a separatory funnel. The contents were washed twice with aqueous sodium carbonate solution and twice with water, and the oil layer was extracted. After adsorbing the water in the oil layer using magnesium sulfate, the magnesium sulfate was removed by filtration, and the ethyl acetate in the oil layer was removed using an evaporator, yielding a monomer compound (BEEA). The resulting monomer compound was 1 When confirmed by H-NMR, the disappearance of the peak derived from vinyl ether near 6.5 ppm was confirmed, and the integral value confirmed the production of a monomer compound (BEEA). BEEA: 2-(2-(1-butyloxyethoxy)ethoxy)ethyl acrylate

[0216] <Synthesis of monomer compound (LEEA)> A monomer compound (LEEA) was obtained by carrying out the same operation as in the synthesis of BEEA above, except that 47.3 parts (0.54 mol) of butyric acid was changed to 107.5 parts (0.54 mol) of lauric acid. The description indicates the following: LEEA: 2-(2-(1-lauroxyethoxy)ethoxy)ethyl acrylate

[0217] Example 1 Synthesis of polymer (A-1) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet pipe, a condenser, and a dropping vessel inlet was charged with 233.3 parts of propylene glycol monomethyl ether acetate, and after replacing the atmosphere with nitrogen, the vessel was heated to 60°C. On the other hand, a dropping tank (A) was prepared by stirring and mixing 31.5 parts of BEEA, 2.1 parts of RUVA-93 (manufactured by Otsuka Chemical Co., Ltd., compound name: 2-[2-Hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole), 44.65 parts of cyclohexyl methacrylate (CHMA), 18.75 parts of 2-hydroxyethyl methacrylate (HEMA), 1.0 part of methyl methacrylate (MMA), 2.0 parts of N-benzylmaleimide (BzMI), and 3.5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., V-65) in a beaker, and 2.0 parts of n-dodecyl mercaptan was added to prepare dropping tank (B). After the temperature of the reaction vessel reached 60°C, the temperature was maintained while dropwise addition from the dropping vessels (A) and (B) was initiated over 3 hours to carry out polymerization. After completion of the dropwise addition, the temperature was raised to 70°C and aging was carried out for 10 hours. After cooling to room temperature, 11.5 parts of succinic anhydride (SAH), 11.7 parts of triethylamine (TEA), and 28.0 parts of propylene glycol monomethyl ether acetate were charged into the reaction vessel and the reaction was carried out at 50°C for 1 hour. After the reaction, the vessel was cooled to room temperature to obtain Polymer (A-1) with a solids concentration of 30%. The physical properties of the obtained polymer are shown in Table 1.

[0218] Example 2 Synthesis of polymer (A-2) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet pipe, a condenser, and a dropping vessel inlet was charged with 233.3 parts of propylene glycol monomethyl ether acetate, and after replacing the atmosphere with nitrogen, the vessel was heated to 60°C. On the other hand, a dropping tank (A) was prepared by stirring and mixing 31.5 parts of BEEA, 2.1 parts of LA-82 (ADEKA STAB LA-82, manufactured by ADEKA Corporation, compound name: 1,2,2,6,6-Pentamethyl-4-piperidyl methacrylate), 44.65 parts of cyclohexyl methacrylate, 18.75 parts of 2-hydroxyethyl methacrylate, 1.0 part of methyl methacrylate, 2.0 parts of N-benzylmaleimide, and 3.5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in a beaker, and 2.0 parts of n-dodecyl mercaptan was added to prepare dropping tank (B). After the temperature of the reaction vessel reached 60°C, the temperature was maintained while dropwise addition from the dropping vessels (A) and (B) was initiated over 3 hours to carry out polymerization. After completion of the dropwise addition, the temperature was raised to 70°C and aging was carried out for 10 hours. After cooling to room temperature, 11.5 parts of succinic anhydride, 11.7 parts of triethylamine, and 28.0 parts of propylene glycol monomethyl ether acetate were charged to the reaction vessel and the reaction was carried out at 50°C for 1 hour. After the reaction, the vessel was cooled to room temperature to obtain Polymer (A-2) with a solids concentration of 30%. The physical properties of the obtained polymer are shown in Table 1.

[0219] Example 3 Synthesis of polymer (A-3) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping vessel inlet was charged with 233.3 parts of propylene glycol monomethyl ether acetate, purged with nitrogen, and then heated to 60 ° C. Separately, a dropping vessel (A) was prepared by stirring and mixing 62.0 parts of BEEA, 2.1 parts of RUVA-93, 14.15 parts of cyclohexyl methacrylate, 18.75 parts of 2-hydroxyethyl methacrylate, 1.0 part of methyl methacrylate, 2.0 parts of N-benzylmaleimide, and 3.5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 2.0 parts of n-dodecyl mercaptan was added to dropwise dropping vessel (B). After the temperature of the reaction vessel reached 60°C, the temperature was maintained while dropwise addition from the dropping vessels (A) and (B) was initiated over 3 hours to carry out polymerization. After completion of the dropwise addition, the temperature was raised to 70°C and aging was carried out for 10 hours. After cooling to room temperature, 11.5 parts of succinic anhydride, 11.7 parts of triethylamine, and 28.0 parts of propylene glycol monomethyl ether acetate were charged into the reaction vessel and the reaction was carried out at 50°C for 1 hour. After the reaction, the vessel was cooled to room temperature to obtain Polymer (A-3) with a solids concentration of 30%. The physical properties of the obtained polymer are shown in Table 1.

[0220] Example 4 Synthesis of polymer (A-4) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a condenser, and a dropping vessel inlet was charged with 233.3 parts of propylene glycol monomethyl ether acetate, purged with nitrogen, and then heated to 60 ° C. Separately, a dropping vessel (A) was prepared by stirring and mixing 15.5 parts of BEEA, 2.1 parts of RUVA-93, 60.65 parts of cyclohexyl methacrylate, 18.75 parts of 2-hydroxyethyl methacrylate, 1.0 part of methyl methacrylate, 2.0 parts of N-benzylmaleimide, and 3.5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 2.0 parts of n-dodecyl mercaptan was added to form dropping vessel (B). After the temperature of the reaction vessel reached 60°C, the temperature was maintained while dropwise addition from the dropping vessels (A) and (B) was initiated over 3 hours to carry out polymerization. After completion of the dropwise addition, the temperature was raised to 70°C and aging was carried out for 10 hours. After cooling to room temperature, 11.5 parts of succinic anhydride, 11.7 parts of triethylamine, and 28.0 parts of propylene glycol monomethyl ether acetate were charged into the reaction vessel and the reaction was carried out at 50°C for 1 hour. After the reaction, the vessel was cooled to room temperature to obtain polymer (A-4) with a solids concentration of 30%. The physical properties of the obtained polymer are shown in Table 1.

[0221] Example 5 Synthesis of polymer (A-5) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping vessel inlet was charged with 233.3 parts of propylene glycol monomethyl ether acetate, and after nitrogen substitution, the vessel was heated to 60 ° C. Separately, a dropping vessel (A) was prepared by stirring and mixing 44.4 parts of LEEA, 2.1 parts of RUVA-93, 31.75 parts of cyclohexyl methacrylate, 18.75 parts of 2-hydroxyethyl methacrylate, 1.0 parts of methyl methacrylate, 2.0 parts of N-benzylmaleimide, and 3.5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 2.0 parts of n-dodecyl mercaptan was added to form a dropping vessel (B). After the temperature of the reaction vessel reached 60°C, the temperature was maintained while dropwise addition from the dropping vessels (A) and (B) was initiated over 3 hours to carry out polymerization. After completion of the dropwise addition, the temperature was raised to 70°C and aging was carried out for 10 hours. After cooling to room temperature, 11.5 parts of succinic anhydride, 11.7 parts of triethylamine, and 28.0 parts of propylene glycol monomethyl ether acetate were charged into the reaction vessel and the reaction was carried out at 50°C for 1 hour. After the reaction, the vessel was cooled to room temperature to obtain polymer (A-5) with a solids concentration of 30%. The physical properties of the obtained polymer are shown in Table 1.

[0222] Example 6 Synthesis of polymer (A-6) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a condenser, and a dropping vessel inlet was charged with 233.3 parts of propylene glycol monomethyl ether acetate, purged with nitrogen, and then heated to 60 ° C. Separately, a dropping vessel (A) was prepared by stirring and mixing 33.6 parts of BEEA, 2.1 parts of RUVA-93, 1 part of cyclohexyl methacrylate, 30 parts of 2-hydroxyethyl methacrylate, 3.3 parts of methyl methacrylate, 30.0 parts of N-benzylmaleimide, and 3.5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.1 parts of n-dodecyl mercaptan was added to form dropping vessel (B). After the temperature of the reaction vessel reached 60°C, the temperature was maintained while dropwise addition from the dropping vessels (A) and (B) was initiated over 3 hours to carry out polymerization. After completion of the dropwise addition, the temperature was raised to 70°C and aging was carried out for 10 hours. After cooling to room temperature, 20.8 parts of succinic anhydride, 21 parts of triethylamine, and 45.3 parts of propylene glycol monomethyl ether acetate were charged into the reaction vessel and the reaction was carried out at 50°C for 1 hour. After the reaction, the vessel was cooled to room temperature to obtain polymer (A-6) with a solids concentration of 30%. The physical properties of the obtained polymer are shown in Table 1.

[0223] Example 7 Synthesis of polymer (A-7) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a condenser, and a dropping vessel inlet was charged with 233.3 parts of propylene glycol monomethyl ether acetate, purged with nitrogen, and then heated to 60° C. Separately, a dropping vessel (A) was prepared by stirring and mixing 30.9 parts of BEEA, 2.1 parts of RUVA-93, 20 parts of cyclohexyl methacrylate, 7 parts of 2-hydroxyethyl methacrylate, 40 parts of methyl methacrylate, and 3.5 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) (V-65, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 6 parts of n-dodecyl mercaptan was added to form dropping vessel (B). After the temperature of the reaction vessel reached 60°C, the temperature was maintained while dropwise addition from the dropping vessels (A) and (B) was initiated over 3 hours to carry out polymerization. After completion of the dropwise addition, the temperature was raised to 70°C and aging was carried out for 10 hours. After cooling to room temperature, 5.4 parts of succinic anhydride, 5.4 parts of triethylamine, and 23 parts of propylene glycol monomethyl ether acetate were charged into the reaction vessel and the reaction was carried out at 50°C for 1 hour. After the reaction, the vessel was cooled to room temperature to obtain polymer (A-7) with a solids concentration of 30%. The physical properties of the obtained polymer are shown in Table 1.

[0224] (Synthesis Example 1) Synthesis of polymer (B-1) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a condenser, and a dropping vessel inlet was charged with 233.3 parts of propylene glycol monomethyl ether acetate, purged with nitrogen, and then heated to 60 ° C. Separately, a dropping vessel (A) was prepared by stirring and mixing 31.5 parts of BEEA, 46.75 parts of cyclohexyl methacrylate, 18.75 parts of 2-hydroxyethyl methacrylate, 1.0 part of methyl methacrylate, 2.0 parts of N-benzylmaleimide, and 3.5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 2.0 parts of n-dodecyl mercaptan was added to form dropping vessel (B). After the temperature of the reaction vessel reached 60°C, the temperature was maintained while dropwise addition from the dropping vessels (A) and (B) was initiated over 3 hours to carry out polymerization. After completion of dropwise addition, the temperature was raised to 70°C and aging was carried out for 10 hours. After cooling to room temperature, 11.5 parts of succinic anhydride, 11.7 parts of triethylamine, and 28.0 parts of propylene glycol monomethyl ether acetate were charged to the reaction vessel and the reaction was carried out at 50°C for 1 hour. After the reaction, the vessel was cooled to room temperature to obtain polymer (B-1) with a solids concentration of 30%. The physical properties of the obtained polymer are shown in Table 1.

[0225] (Synthesis Example 2) Production of polymer (B-2) A reaction vessel equipped with a thermometer, stirrer, gas inlet, cooling tube, and dropping vessel inlet was charged with 153.9 parts of propylene glycol monomethyl ether acetate and 65.9 parts of propylene glycol monomethyl ether, and after nitrogen substitution, heated to 90 ° C. Separately, a dropping vessel (A) was prepared by stirring and mixing 70.0 parts of methyl methacrylate, 30.0 parts of methacrylic acid, 2.0 parts of t-butyl peroxy-2-ethylhexanoate (PBO), and 10.0 parts of propylene glycol monomethyl ether acetate in a beaker, and a dropping vessel (B) was prepared by stirring and mixing 2.0 parts of n-dodecyl mercaptan and 3.5 parts of propylene glycol monomethyl ether acetate. After the temperature of the reaction vessel reached 90 ° C, the dropping vessel was started over 3 hours while maintaining the same temperature, and polymerization was carried out. After the dropwise addition, the mixture was maintained at 90°C for 30 minutes, then heated to 115°C and aged for 90 minutes. After cooling to room temperature, 16.9 parts of glycidyl methacrylate (GMA), 0.3 parts of triethylamine, and 0.2 parts of Antage W-400 were added, and the mixture was reacted at 115°C for 7 hours while bubbling with oxygen / nitrogen mixed gas adjusted to an oxygen concentration of 7% at 20 ml / min, to obtain polymer (B-2). The physical properties of the obtained polymer are shown in Table 1.

[0226] Example 8 (Preparation of Resin Composition) 0.5 parts of RUVA-93 was added to 99.5 parts of polymer (A-1) in terms of solid content, and a dilution solvent (propylene glycol monomethyl ether acetate) was further added so that the solid content concentration (non-volatile content) became 30% by mass, followed by stirring to obtain resin composition (C-1).

[0227] (Examples 9 to 42, Comparative Examples 1 to 6) Resin compositions (C-2) to (C-35) and resin compositions (D-1) to (D-6) were obtained in the same manner as in Example 8, except that the formulations shown in Tables 2, 3, and 4 were used. The obtained resin compositions were evaluated by the methods described above. The pigment dispersions shown in Table 4 were prepared by the following method. The results are shown in Tables 2 to 4. (Preparation of pigment dispersion) 12.9 parts of propylene glycol monomethyl ether acetate, 0.4 parts of Disparlon DA-7301 as a basic dispersant, 2.25 parts of CI Pigment Green 58 and 1.5 parts of CI Pigment Yellow 138 as colorants were mixed and dispersed for 3 hours using a paint shaker to obtain a pigment dispersion (solid content 22% by mass).

[0228] The descriptions in the table indicate the following: BzMI: N-benzylmaleimide CHMA: Cyclohexyl methacrylate MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate BEEA: 2-(2-(1-butyloxyethoxy)ethoxy)ethyl acrylate LEEA: 2-(2-(1-lauroxyethoxy)ethoxy)ethyl acrylate MAA: methacrylic acid RUVA-93:2-[2-Hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole LA-82:1,2,2,6,6-Pentamethyl-4-piperidyl methacrylate Irganox 1010: Pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (BASF Japan Ltd.) Topanol: 6-tert-Butyl-2,4-xylenol KarenzMT-PE1: Pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Resonac Co., Ltd.) GMA: Glycidyl methacrylate SAH: succinic anhydride V65: 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) TEA: Triethylamine DPHA: Dipentaerythritol hexaacrylate Irg907: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (BASF Japan Ltd., IRGACURE907)

[0229] [Table 1]

[0230] [Table 2]

[0231] [Table 3]

[0232] [Table 4]

[0233] Table 2 confirms that the resin compositions (C-1) to (C-23) of the examples show improved results in terms of viscosity change rate, appearance observation, and heat discoloration resistance compared to the resin compositions (D-1) to (D-3) of the comparative examples. This demonstrates that the addition of compounds with radical scavenging ability, such as RUVA-93 / LA-82, their introduction into copolymerization components, and the addition of thiol compounds can suppress the degradation of polymers with acetal bonds.

[0234] The amount of the compound added or copolymerized can be selected as desired, and a comparison of (C-2) and (C-3) and a comparison of (C-4) and (C-16) reveals that resin degradation can be further suppressed by increasing the amount.

[0235] The mechanism of degradation inhibition is thought to be trapping radicals generated when hydrogen atoms present in acetal bonds are abstracted by oxygen or light, or inhibiting the generation of radicals themselves. Therefore, (D-1) to (D-3) suggest that the presence of double-bond-containing compounds reactive with radicals or the presence of photopolymerization initiators that generate radicals accelerates the degradation of resin compositions. Comparing these results with (C-20) to (C-23) reveals that adding compounds with radical scavenging ability or incorporating them into copolymerization components can improve the storage stability of resin compositions containing such compounds. Comparing (C-8) to (C-14) reveals that thiol compounds are the additives with the highest radical scavenging ability.

[0236] Table 3 shows that the mechanism of degradation inhibition applies not only to resins but also to compounds with acetal bonds.

[0237] Table 4 shows that the resins of the examples have a faster development rate than general alkali-soluble resins of polymer (B-2), and have extremely high solvent resistance, especially under low-temperature baking conditions of 100°C or less. Another feature of the resin compositions of the examples is that they exhibit little line thickening, which is thought to be because the added or copolymerized compound with radical scavenging ability can suppress curing caused by weak diffracted light generated at the edges of the photomask during UV irradiation. It is also clear that the addition of a thiol compound improves solvent resistance, which is thought to be because the radicals generated during exposure react with the thiol compound, extending the life of the radicals.

[0238] (Examples 43 to 44, Comparative Example 7) 18 g of the polymer (B-1) was placed in a storage container (Maruem screw tube No. 5, volume 20 L), and nitrogen gas was introduced at 50 ml / min for 4 minutes. The oxygen concentration in the storage container was measured by aspirating the air in the space using an oxygen concentration meter manufactured by Shin Cosmos Electric. The storage container was then sealed and left to stand for 4 days in an environment of 50°C and 50% humidity. The appearance of the screw tube was then visually observed and evaluated. The evaluation criteria were the same as those for the appearance evaluation method described above. The results are shown in Table 5.

[0239] [Table 5]

[0240] Table 5 shows that when the spatial oxygen concentration is 1% by volume (Example 43), the storage stability is better than when the spatial oxygen concentration is 21% by volume (Comparative Example 7). Replacing the spatial portion with a gas containing an inert gas to lower the oxygen concentration is an effective measure for extending the period during which the transparency of the resin solution can be maintained. It was also found that by filling the polymer solution so that the void volume is as small as possible relative to the volume of the storage container, contact with oxygen can be reduced, thereby suppressing the coloring of the resin (Example 44).

Claims

1. The composition comprises a structural unit (A) represented by the following general formula (1), and a structural unit (B) derived from at least one monomer selected from the group consisting of a hindered phenol compound having a polymerizable group, a hindered amine compound having a polymerizable group, a cyano(meth)acrylate compound, a melamine compound having a polymerizable group, and a thiol compound having a polymerizable group: A polymer characterized by: 【Chemical 1】 (In the formula, X represents a hydrogen atom or a methyl group. L represents a divalent organic group. A １ represents an oxygen atom, a sulfur atom, or —NR ３ - represents. ３ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ２ is -OR ４ , -SR ５ or -NR ６ R ７ Represents R ４ , R ５ , R ６ and R ７ are the same or different and represent a hydrogen atom or an organic group having 1 to 20 carbon atoms. １ and R ２ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.

2. 2. The polymer according to claim 1, wherein the structural unit (A) has a structure in which a vinyl ether group is generated at a side chain terminal by the action of an acid or heat.

3. The above A ２ is -O-(CO)-R ８ (R ８ represents a hydrocarbon group having 1 to 19 carbon atoms.

4. 2. The polymer according to claim 1, further comprising a structural unit (C) having an acid group.

5. The composition contains a polymer having a structural unit (A) represented by the following general formula (1) and at least one compound selected from the group consisting of a hindered phenol compound, a hindered amine compound, a cyano(meth)acrylate compound, a melamine compound, and a thiol compound. A polymer composition comprising: 【Chemistry 2】 (In the formula, X represents a hydrogen atom or a methyl group. L represents a divalent organic group. A １ represents an oxygen atom, a sulfur atom, or —NR ３ - represents. ３ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ２ is -OR ４ , -SR ５ or -NR ６ R ７ Represents R ４ , R ５ , R ６ and R ７ are the same or different and represent a hydrogen atom or an organic group having 1 to 20 carbon atoms. １ and R ２ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.

6. 6. The polymer composition according to claim 5, wherein the structural unit (A) has a structure in which a vinyl ether group is generated at a side chain terminal by the action of an acid or heat.

7. The A in the general formula (1) ２ is -O-(CO)-R ８ (In the formula, R ８ represents a hydrocarbon group having 1 to 19 carbon atoms.

8. 6. The polymer composition according to claim 5, wherein the polymer comprises a structural unit (C) having an acid group.

9. A resin composition comprising the polymer according to claim 1 or the polymer composition according to claim 5, and a polymerizable compound.

10. The resin composition according to claim 9, further comprising a photopolymerization initiator.

11. 10. The resin composition according to claim 9, which is for use in a color filter.

12. A cured product of the resin composition according to claim 9.

13. A method for storing a polymer having a structural unit (A) represented by the following general formula (1) in a container, comprising: The oxygen concentration in the gas phase in the container is 10% by volume or less, and / or the ratio of the space volume of the gas phase in the container to the volume of the container is 15% or less. A method for preserving a polymer, comprising: 【Chemistry 3】 (In the formula, X represents a hydrogen atom or a methyl group. L represents a divalent organic group. A １ represents an oxygen atom, a sulfur atom, or —NR ３ - represents. ３ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ２ is -OR ４ , -SR ５ or -NR ６ R ７ Represents R ４ , R ５ , R ６ and R ７ are the same or different and represent a hydrogen atom or an organic group having 1 to 20 carbon atoms. １ and R ２ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.

14. A method for storing a polymer composition in a container, the method comprising: storing a polymer having a structural unit (A) represented by the following general formula (1); and at least one compound selected from the group consisting of a hindered phenol compound, a hindered amine compound, a cyano(meth)acrylate compound, a melamine compound, and a thiol compound, the method comprising: The oxygen concentration in the gas phase in the container is 10% by volume or less, and / or the ratio of the space volume of the gas phase in the container to the volume of the container is 15% or less. A method for preserving a polymer composition, comprising: 【Chemistry 4】 (In the formula, X represents a hydrogen atom or a methyl group. L represents a divalent organic group. A １ represents an oxygen atom, a sulfur atom, or —NR ３ - represents. ３ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ２ is -OR ４ , -SR ５ or -NR ６ R ７ Represents R ４ , R ５ , R ６ and R ７ are the same or different and represent a hydrogen atom or an organic group having 1 to 20 carbon atoms. １ and R ２ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms.

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