Polymer and method for producing same, photosensitive resin composition, cured product, and monomer compound and method for producing same

Abstract

The present invention provides: a polymer that has excellent storage stability and can yield a cured product having excellent solvent resistance even under low-temperature curing conditions; a photosensitive resin composition that contains the polymer; and a cured product of the photosensitive resin composition. The present invention is a polymer characterized by having a structural unit (A) represented by formula (1) (in the formula, X represents a hydrogen atom or a methyl group. L represents a linear or branched divalent organic group. Y represents an organic group that is decomposed by acid or heat and generates a vinyl ether group in a polymer side chain.).

Description

Polymer and its manufacturing method, photosensitive resin composition, cured product, and monomer compound and its manufacturing method

[0001] The present invention relates to a polymer and a method for producing the same, a photosensitive resin composition, a cured product, and a monomer compound and a method for producing the same. More specifically, the present invention relates to a polymer and a method for producing the same, a photosensitive resin composition, a cured product, and a monomer compound and a method for producing the same, which can give a cured product having excellent solvent resistance even under low-temperature curing conditions and also has excellent storage stability.

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

[0003] Resins and photosensitive resin compositions that meet various requirements have been developed to date (Patent Documents 1 to 7). For example, Patent Document 1 describes a photocurable composition that contains a compound having a specific group that has a (meth)acryloyl group and an acetal group or a hemiacetal group, and a photopolymerization initiator, as a composition that has sufficient photocurability, allows formation of a high-resolution pattern by photolithography, and exhibits excellent thermal decomposition properties during baking.

[0004] Furthermore, for example, Patent Document 2 describes a photosensitive resin composition that can give a cured film having high sensitivity, high transparency, and excellent ITO sputtering resistance, and that contains a polymer having a weight-average molecular weight of more than 1,000, a monomer unit having a residue that generates a carboxyl group or a phenolic hydroxyl group in the presence of an 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.

[0005] For example, Patent Document 3 describes a resin composition having excellent storage stability, which contains an alkali-soluble resin having a structure derived from a vinyl ether compound and a basic compound, and Patent Document 4 describes a negative resist composition containing at least a component having a vinyl ether structure protected by acetal in the molecule. Furthermore, Patent Documents 5 to 7 describe polyfunctional (meth)acrylic acid esters having an acetal structure.

[0006] JP 2003-195497 A JP 2011-209682 A JP 2018-53031 A JP 2002-148805 A JP 2003-201267 A JP 2007-45924 A JP 2013-10726 A

[0007] As described above, various resins and photosensitive resin compositions have been investigated to date, but when a photosensitive resin composition containing a conventional resin is used together with a colorant as a raw material for, for example, a color filter, there is a problem that the colorant elutes from the raw material into a cleaning solvent during the production of the color filter. Therefore, there has been a demand for further improvement in the solvent resistance of resins.

[0008] Furthermore, in recent years, particularly in color filter applications, the improvement in quality and expansion of applications of color liquid crystal display devices and the like have led to a strong demand for higher performance, such as higher brightness and contrast, of display panels. However, in the production of color filters, if the baking process (post-curing process) after exposure and development is performed at a high temperature above 200°C, discoloration such as yellowing occurs in the resulting cured product, preventing sufficient high coloration of the desired color. Furthermore, if the baking process is performed at a high temperature, unwanted reactions occur, producing by-products and degrading the properties of the substrate and the cured film. In order to suppress such unwanted reactions and efficiently obtain color filters with desired properties, it is desirable for the curing reaction to proceed sufficiently even under relatively low heating conditions of 200°C or less. Furthermore, if the curable resin composition can be cured at a relatively low temperature, the production efficiency of color filters can also be improved.

[0009] On the other hand, resins that readily undergo a curing reaction even under heating conditions at relatively low temperatures generally have high reactivity, and therefore have the problem of low storage stability.

[0010] The present invention has been made in view of the above-mentioned current situation, and aims to provide a polymer that can give a cured product having excellent solvent resistance even under low-temperature curing conditions and also excellent storage stability, a photosensitive resin composition containing the polymer, and a cured product thereof. It is also an object of the present invention to provide a monomer compound that can be used in producing the polymer, and methods for producing the polymer and the monomer compound.

[0011] The present inventors have conducted extensive research into polymers that can be used in photosensitive resin compositions, and have found that by using a polymer having a specific structure, the crosslinking reaction proceeds well even under low-temperature curing conditions of 160°C or less, a cured product having excellent solvent resistance can be obtained, and a resin having excellent storage stability can also be obtained, which has led to the completion of the present invention.

[0012] That is, the present invention provides the following aspects: [1] A polymer characterized by having a structural unit (A) represented by the following formula (1):

[0013] (In the formula, X represents a hydrogen atom or a methyl group. L represents a linear or branched divalent organic group. Y represents an organic group that decomposes with an acid or heat to produce a vinyl ether group in a polymer side chain.) [2] The polymer according to the above [1], wherein the structural unit (A) is represented by the following formula (1-1):

[0014]

[0015] (wherein X represents a hydrogen atom or a methyl group. R １ represents a linear or branched divalent organic group. ２represents an organic group having 1 to 20 carbon atoms.) [3] The polymer according to [1] or [2] above, further comprising an acid group-containing structural unit (B). [4] The polymer according to any one of [1] to [3] above, further comprising a structural unit (C) having a ring structure in the main chain. [5] A polymer solution comprising the polymer according to any one of [1] to [4] above and a polar solvent. [6] A polymer solution comprising the polymer according to any one of [1] to [4] above or the polymer solution according to [5] above, a basic dispersant and / or a basic compound. [7] A colorant dispersion comprising the polymer solution according to [6] above and a colorant. [8] A photosensitive resin composition comprising the polymer according to any one of [1] to [4] above, the polymer solution according to [5] above, the polymer solution according to [6] above, or the colorant dispersion according to [7] above, a polymerizable compound, and a photopolymerization initiator and / or a photoacid generator. [9] The photosensitive resin composition according to the above item [8], which is used for forming a color filter.

[10] A cured product obtained by curing the photosensitive resin composition according to the above item [8] or [9].

[11] A method for producing a polymer having a structural unit (A) represented by the following formula (1) and an acid group-containing structural unit (B), the method comprising: a step (P-1) of polymerizing a monomer component containing a group that generates a vinyl ether group by the action of acid or heat, and the acid group-containing monomer:

[0016]

[0017] (In the formula, X represents a hydrogen atom or a methyl group. L represents a linear or branched divalent organic group. Y represents an organic group that decomposes by acid or heat to produce a vinyl ether group on a side chain of the polymer.)

[12] A method for producing a polymer having a structural unit (A) represented by the following formula (1) and an acid group-containing structural unit (B), the method comprising: a step (Q-1) of polymerizing monomer components including a monomer containing a group that produces a vinyl ether group by acid or heat, and a hydroxyl group-containing monomer; and a step (Q-2) of reacting the polymer obtained in the step (Q-1) with an acid group-containing compound.

[0018]

[0019] (In the formula, X represents a hydrogen atom or a methyl group. L represents a linear or branched divalent organic group. Y represents an organic group that decomposes with an acid or heat to produce a vinyl ether group in a polymer side chain.)

[13] A monomer compound represented by the following formula (a):

[0020]

[0021] (In the formula, R ７ represents a hydrogen atom or a methyl group. ８ represents a linear or branched divalent organic group. ９ represents an organic group having 1 to 20 carbon atoms (excluding groups containing a (meth)acryloyl group).

[14] A method for producing a monomer compound represented by the following formula (a-1), the method comprising a step of reacting a vinyl ether group-containing (meth)acrylate compound with a carboxylic acid compound, and wherein the amount of the carboxylic acid compound used in the reaction step is 1 equivalent or more relative to 1 equivalent of the vinyl ether group of the vinyl ether group-containing (meth)acrylate compound.

[0022]

[0023] (In the formula, R ７ represents a hydrogen atom or a methyl group. ８ represents a linear or branched divalent organic group. １０ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms (excluding groups containing a (meth)acryloyl group).

[0024] The polymer and photosensitive resin composition of the present invention have excellent storage stability, can be sufficiently cured even under low-temperature curing conditions, and can give a cured product with excellent solvent resistance. The polymer and photosensitive resin composition of the present invention can be widely used in various applications such as optical components, electric / electronic components, and display devices.

[0025] The present invention will be described in detail below. 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. Furthermore, in this specification, "(meth)acrylate" means "acrylate and / or methacrylate," and "(meth)acrylic acid" means "acrylic acid and / or methacrylic acid."

[0026] 1. Polymer The polymer of the present invention is characterized by having a structural unit (A) represented by the following formula (1):

[0027]

[0028] (In the formula, X represents a hydrogen atom or a methyl group, L represents a linear or branched divalent organic group, and Y represents an organic group that decomposes with acid or heat to produce a vinyl ether group in the polymer side chain.)

[0029] The polymer of the present invention, which has the structural unit (A), can provide a cured product with excellent solvent resistance even under low-temperature curing conditions, and has excellent storage stability. This is thought to be because the polymer has a group that decomposes with acid or heat to generate a vinyl ether group, and therefore, during curing, the vinyl ether group is generated, and cationic polymerization by the vinyl ether group proceeds, allowing the crosslinking reaction of the polymer to proceed sufficiently. Furthermore, during storage of the polymer, the vinyl ether group, which is a curing reactive group, is protected, so that the self-crosslinking reaction of the polymer is suppressed, resulting in excellent storage stability. The polymer of the present invention will be described in detail below.

[0030] (1) Structural Unit (A) The polymer of the present invention has a structural unit (A) represented by the above formula (1). In this specification, the term "structural unit" refers to a repeating (structural) unit in the structure of the polymer.

[0031] In the above formula (1), X represents a hydrogen atom or a methyl group. X is preferably a hydrogen atom, as this provides a polymer with high hydrophilicity and excellent developability. In the above formula (1), L represents a linear or branched divalent organic group. Examples of the divalent organic group represented by L include linear or branched divalent hydrocarbon groups which may have a substituent.

[0032] The linear or branched divalent hydrocarbon group may be a divalent aliphatic hydrocarbon group, which may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group.

[0033] Examples of the divalent saturated aliphatic hydrocarbon group include alkylene groups such as methylene, ethylene, propylene, isopropylene, butylene, isobutylene, t-butylene, pentylene, neopentylene, hexamethylene, heptylene, octylene, 2-ethylhexylene, nonylene, decylene, undecylene, and dodecylene. The saturated aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, and more preferably 2 to 4 carbon atoms.

[0034] Examples of the divalent unsaturated aliphatic hydrocarbon group include alkenylene groups such as vinylene, propenylene, isopropenylene, butenylene, butadienylene, pentenylene, hexenylene, and heptenylene, and alkynylene groups such as ethynylene, propynylene, 1-butynylene, and 2-butynylene. The unsaturated aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, and more preferably 2 to 4 carbon atoms.

[0035] Among these, the divalent aliphatic hydrocarbon group is preferably a divalent saturated aliphatic hydrocarbon group, since this group can impart flexibility to the side chain.

[0036] At least one atom constituting the divalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom, and the hydrocarbon group may have a substituent such as an alkoxy group.

[0037] The linear or branched divalent organic group may be, for example, the linear or branched divalent hydrocarbon group, or a combination of the linear or branched divalent hydrocarbon group and -O-, -COO-, -CO-, -NH-, -S-, -SO-, or -SO ２Preferred examples of the linear or branched divalent hydrocarbon group include a group containing a bond such as -O-, -COO-, -CO-, -NH-, -S-, -SO-, -SO ２ The group containing a bond such as - may contain only one kind of the above divalent hydrocarbon group or bond, or may contain two or more kinds of the above divalent hydrocarbon group or bond. In terms of good copolymerizability, the above bond is preferably at least one kind of bond selected from the group consisting of -O-, -COO-, and -CO-, and more preferably at least one kind of bond selected from the group consisting of -O- and -COO-.

[0038] Among these, the divalent organic group represented by L is —COO—R １ - (R １ represents a linear or branched divalent organic group. １ The linear or branched divalent organic group represented by the formula (I) is preferably the linear or branched divalent hydrocarbon group, or a combination of the linear or branched divalent hydrocarbon group and —O—, —COO—, —CO—, —NH—, —S—, —SO—, —SO ２ Among these, groups containing bonds such as -R ３ -(O-R ４ ) ｎ - (wherein, R ３ and R ４ are the same or different and represent a divalent saturated aliphatic hydrocarbon group. n represents an integer of 0 or more. ３ and R ４ The divalent saturated aliphatic hydrocarbon group represented by the formula (I) is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 or 2 carbon atoms. The above n is preferably an integer of 0 to 10, and more preferably 1.

[0039] The divalent organic group represented by L preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 5 carbon atoms.

[0040] In the above formula (1), Y is a group that decomposes with acid or heat to form a vinyl ether group (—O—CH═CH) on the polymer side chain.２ ) is represented by an organic group that forms a vinyl ether group. Examples of such organic groups include a group in which a vinyl ether group is acetal-protected. Examples of the above-mentioned group in which a vinyl ether group is acetal-protected include —O—CH(CH ３ )—O—, and preferably, —O—CH(CH ３ )-O-R ２ When the polymer has such a group, the group can be converted by acid or heat into a group represented by —O—R ２ is eliminated, and a vinyl ether group (—O—CH═CH) is attached to the side chain of the polymer. ２ ) is generated. Preferably, R ２ represents an organic group having 1 to 20 carbon atoms.

[0041] The above R ２ The organic group represented by the formula (I) is preferably a monovalent hydrocarbon group which may have a substituent.

[0042] The monovalent hydrocarbon group may be a hydrocarbon group having a chain structure or a hydrocarbon group containing a cyclic structure.

[0043] Examples of the hydrocarbon group having a chain structure include aliphatic hydrocarbon groups. Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a sec-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a hexyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 2,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a heptyl group, a 2-methylhexyl group, a 3-methylhexyl group, a 2,2-dimethylpentyl group, a 2,3-dimethylpentyl group, a 2,4-dimethylpentyl group, a 3-ethylpentyl group, a 2,2,3-trimethylbutyl group, an octyl group, a methylheptyl group, a dimethylhexyl group, a 2-ethylhexyl group, a 3-ethylhexyl group, a trimethylpentyl group, a 3-ethyl-2-methylpentyl group, a 2-ethyl-3-methylpentyl group, a 2,2,3,3-tetramethylbutyl ... methylbutyl group, nonyl group, methyloctyl group, 3,7-dimethyloctyl group, dimethylheptyl group, 3-ethylheptyl group, 4-ethylheptyl group, trimethylhexyl group, 3,3-diethylpentyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, etc. Examples thereof include alkyl groups; and alkenyl groups such as vinyl groups, n-propenyl groups, isopropenyl groups, 1-butenyl groups, 2-butenyl groups, 1-pentenyl groups, 2-pentenyl groups, 2-methyl-1-butenyl groups, 2-methyl-2-butenyl groups, 3-methyl-1-butenyl groups, 1-hexenyl groups, 2-hexenyl groups, 1-heptenyl groups, 2-heptenyl groups, 1-octenyl groups, and 2-octenyl groups.

[0044] The hydrocarbon group containing a cyclic structure includes a hydrocarbon group having a cyclic structure, and a hydrocarbon group having a cyclic structure and a chain structure.

[0045] Examples of the hydrocarbon group having a cyclic structure include alicyclic hydrocarbon groups and aromatic hydrocarbon groups. Examples of the alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclododecyl. Examples of the aromatic hydrocarbon group include aryl groups such as phenyl and naphthyl.

[0046] The hydrocarbon group having a cyclic structure and a chain structure includes a hydrocarbon group formed by combining the above-mentioned hydrocarbon group having a cyclic structure and a hydrocarbon group having a chain structure, and examples thereof include a benzyl group, a phenethyl group, a biphenyl group, a tolyl group, and a xylyl group.

[0047] The monovalent hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 3 carbon atoms.

[0048] The monovalent hydrocarbon group may have at least one atom substituted with an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom. The monovalent hydrocarbon group may also have a substituent such as an alkoxy group, an amide group, or an amino group. When the substituent contains a carbon atom, the number of carbon atoms in the substituent is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6.

[0049] Among these, the above-mentioned R ２ The organic group represented by -R ５ (However, groups containing a carbonyl group are excluded.) or -CO-R ６ is preferably —CO—R ６ It is more preferable that R ５ and R ６are the same or different and represent an organic group, preferably a hydrocarbon group or a group containing a hydrocarbon group and at least one bond selected from the group consisting of -O- and -COO-, more preferably an aliphatic hydrocarbon group or a group containing an aliphatic hydrocarbon group and at least one bond selected from the group consisting of -O- and -COO-, and even more preferably an alkyl group. ６ The number of carbon atoms in the organic group represented by the formula (I) is preferably 1 to 19, more preferably 1 to 10, even more preferably 1 to 5, and most preferably 3. By controlling the number of carbon atoms within the above range, it is possible to achieve both storage stability and low-temperature curing properties.

[0050] The structural unit (A) is preferably a structural unit represented by the following formula (1-1) in that it has good low-temperature curing properties.

[0051]

[0052] (wherein X represents a hydrogen atom or a methyl group. R １ represents a linear or branched divalent organic group. ２ represents an organic group having 1 to 20 carbon atoms.

[0053] R in the above formula (1-1) １ and R ２ are the above-mentioned R １ and R ２ It is the same as:

[0054] The polymer having the structural unit (A) can be obtained, for example, by polymerizing a monomer component containing a monomer capable of introducing the structural unit (A). The monomer capable of introducing the structural unit (A) is not particularly limited as long as it can be polymerized to obtain a polymer having the structural unit (A), and examples thereof include a monomer represented by the following formula (2): CH ２ =CXL-Y (2) (wherein X, L, and Y are the same as X, L, and Y in formula (1), respectively.)

[0055] Among these, as the monomer represented by the above formula (2), a monomer compound represented by the following formula (a) is preferred in terms of excellent synthesis stability.

[0056] (In the formula, R ７ represents a hydrogen atom or a methyl group. ８ represents a linear or branched divalent organic group. ９ represents an organic group having 1 to 20 carbon atoms.

[0057] In the above formula (a), R ８ The linear or branched divalent organic group represented by the formula (1-1) includes R １ Preferred examples of the divalent organic group include the same groups as the linear or branched divalent organic group represented by R ９ As the organic group having 1 to 20 carbon atoms represented by the formula (1-1), R ２ Preferred examples of the organic group having 1 to 20 carbon atoms are the same as those represented by the above R ９ The organic group represented by the formula: ６ In the formula, R ６ is preferably a hydrocarbon group, more preferably a chain saturated hydrocarbon group. ６ The organic group represented by the formula (I) preferably has 1 to 19 carbon atoms, more preferably 1 to 10 carbon atoms, even more preferably 1 to 5 carbon atoms, and most preferably 3 carbon atoms.

[0058] Specific examples of the monomer compound represented by the formula (a) include 2-(2-(1-acetoxyethoxy)ethoxy)ethyl (meth)acrylate, 2-(2-(1-isopropoxyethoxy)ethoxy)ethyl (meth)acrylate, 2-(2-(1-ethoxyethoxy)ethoxy)ethyl (meth)acrylate, 2-(2-(1-propionyloxyethoxy)ethoxy)ethyl (meth)acrylate, 2-(2-(1-butyloxyethoxy)ethoxy)ethyl (meth)acrylate, and 2-(2-(1-formyloxyethoxy)ethoxy)ethyl (meth)acrylate. From the viewpoint of synthesis, 2-(2-(1-propionyloxyethoxy)ethoxy)ethyl (meth)acrylate and 2-(2-(1-butyloxyethoxy)ethoxy)ethyl (meth)acrylate are preferred, and 2-(2-(1-butyloxyethoxy)ethoxy)ethyl (meth)acrylate is most preferred. The above monomer compounds may be used alone or in combination of two or more.

[0059] Among the monomer compounds represented by the formula (a), R ７ represents a hydrogen atom or a methyl group, R ８ represents a linear or branched divalent organic group, R ９ represents an organic group having 1 to 20 carbon atoms (excluding groups containing a (meth)acryloyl group), is a novel compound. Such novel monomer compounds also constitute the present invention.

[0060] The polymer may have only one type of the structural unit (A), or may have two or more types.

[0061] The content of the structural unit (A) is preferably 1 to 100% by mass, more preferably 5 to 50% by mass, and even more preferably 10 to 40% by mass, relative to 100% by mass of all structural units of the polymer, in terms of good low-temperature curing properties.

[0062] (2) Structural Unit (B) The polymer of the present invention preferably further contains an acid group-containing structural unit (B). By containing the structural unit (B), vinyl ether groups are more likely to be generated from the structural unit (A) during curing, which promotes cationic polymerization by the vinyl ether groups. Furthermore, the vinyl ether groups react with acid groups, facilitating the self-crosslinking reaction of the polymer, thereby forming a stronger cured product. Furthermore, the polymer becomes alkali-soluble, improving developability. Examples of the acid groups include functional groups that undergo a neutralization reaction with alkaline water, such as carboxyl groups, phenolic hydroxyl groups, carboxylic anhydride groups, phosphoric acid groups, and sulfonic acid groups. Only one of these groups may be present, or two or more groups may be present. Among these, carboxyl groups and carboxylic anhydride groups are preferred, and carboxyl groups are more preferred, in terms of further improving developability.

[0063] The polymer having the acid group-containing structural unit (B) can be obtained by 1) polymerizing a monomer component containing an acid group-containing monomer, or 2) polymerizing a monomer component containing a hydroxyl group-containing monomer to obtain a precursor polymer (base polymer), and then reacting a polybasic acid or a polybasic acid anhydride with the hydroxyl groups of the precursor polymer (base polymer) to introduce acid groups. These methods may be combined.

[0064] In the method 1), a structural unit derived from an acid group-containing monomer is obtained as the structural unit (B). Examples of the acid group-containing monomer include compounds having the above-mentioned acid group and a polymerizable double bond (carbon-carbon double bond) in the molecule. Examples of the polymerizable double bond include a (meth)acryloyl group, a vinyl group, an allyl group, and a methallyl group. Of these, a (meth)acryloyl group is preferred.

[0065] 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 phosphate 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 standpoints of versatility, availability, and the like. 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.

[0066] In the above method 2), a precursor polymer (prepolymer) having hydroxyl groups is prepared in advance, and then a polybasic acid or polybasic acid anhydride is reacted with the hydroxyl groups to introduce acid groups (carboxyl groups), thereby producing a polymer having an acid group-containing structural unit (B). When a polymer having an acid group-containing structural unit is produced in this manner, the acid group is located relatively far from the main chain of the polymer, which makes it easier for the crosslinking reaction to proceed during curing of the polymer, thereby further improving curability. In the above method 2), a structural unit containing a carboxyl group is obtained as the structural unit (B) by reacting a structural unit derived from a hydroxyl group-containing monomer with a polybasic acid or polybasic acid anhydride.

[0067] Examples of the hydroxyl group-containing monomer include the same monomer compounds as the hydroxyl group-containing monomers described below as monomers that provide the structural unit (D). Examples of the polybasic acid or polybasic acid anhydride include the same compounds as the acid group-containing compounds described below. Specific reaction methods will be described in the polymer production method described below.

[0068] In the above method 2), epoxy groups can also be used instead of the hydroxyl groups. That is, a polymer having epoxy groups can be prepared in advance, and then the epoxy groups can be subjected to an addition reaction with acid groups of an acid group-containing monomer to ring-open the epoxy groups, and the hydroxyl groups thus generated can be reacted with a polybasic acid or a polybasic acid anhydride to produce carboxyl groups.

[0069] Examples of the epoxy group-containing monomer used in preparing the polymer having an epoxy group 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.

[0070] The polymer may have only one type of the structural unit (B), or may have two or more types.

[0071] The content of the structural unit (B) is preferably 0 to 80% by mass, relative to 100% by mass of all structural units of the polymer. In terms of good developability, the content is more preferably 3 to 80% by mass, even more preferably 5 to 45% by mass, and even more preferably 10 to 30% by mass, relative to 100% by mass of all structural units of the polymer.

[0072] (3) Structural Unit (C) The polymer is preferably a polymer having a ring structure in the main chain. By having a ring structure in the main chain, the heat resistance of the polymer can be improved. Examples of the ring structure include an imide ring, a tetrahydrofuran ring, and a lactone ring. Thus, the polymer preferably further has a structural unit (C) having a ring structure in the main chain.

[0073] Examples of monomers that can introduce the structural unit (C) 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., 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 is preferred, and N-substituted maleimide monomers are more preferred in terms of even better solvent resistance. It can be said that the structural unit (C) is a structural unit derived from such a monomer that can introduce the structural unit (C).

[0074] Examples of the N-substituted maleimide monomer include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-t-butylmaleimide, N-dodecylmaleimide, N-benzylmaleimide, and N-naphthylmaleimide, and one or more of these can be used. Among these, from the viewpoints of transparency, heat coloration resistance, and suppression of water-based unevenness, N-phenylmaleimide, N-benzylmaleimide, and N-cyclohexylmaleimide are preferred, and N-benzylmaleimide is particularly suitable.

[0075] Examples of the N-benzylmaleimide include benzylmaleimide; alkyl-substituted benzylmaleimides such as p-methylbenzylmaleimide and p-butylbenzylmaleimide; phenolic hydroxyl group-substituted benzylmaleimides such as p-hydroxybenzylmaleimide; and halogen-substituted benzylmaleimides such as o-chlorobenzylmaleimide, o-dichlorobenzylmaleimide and p-dichlorobenzylmaleimide.

[0076] Examples of the dialkyl-2,2'-(oxydimethylene)diacrylate monomer include dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-butyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, and di(isobutyl)-2,2'-[oxybis(methylene)]bis-2-propenoate. Examples of suitable hydroxybis(methylene)-2,2'-diol include di(t-butyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(t-amyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(stearyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(lauryl)-2,2'-[oxybis(methylene)]bis-2-propenoate, and di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate. Among these, dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate is more preferred from the viewpoints of transparency, dispersibility, ease of industrial availability, and the like.

[0077] Examples of the α-(unsaturated alkoxyalkyl)acrylate monomer include α-(allyloxymethyl)acrylate monomers. Specific examples of the α-(allyloxymethyl)acrylate monomer include α-allyloxymethylacrylic acid; methyl α-allyloxymethylacrylate, ethyl α-allyloxymethylacrylate, n-propyl α-allyloxymethylacrylate, i-propyl α-allyloxymethylacrylate, n-butyl α-allyloxymethylacrylate, s-butyl α-allyloxymethylacrylate, t-butyl α-allyloxymethylacrylate, n-amyl α-allyloxymethylacrylate, s-amyl α-allyloxymethylacrylate, t-amyl α-allyloxymethylacrylate, n-hexyl α-allyloxymethylacrylate, s-hexyl α-allyloxymethylacrylate, n-heptyl α-allyloxymethylacrylate, n-octyl α-allyloxymethylacrylate, s-octyl α-allyloxymethylacrylate, and α-allyloxymethylacrylate. alkyl-(α-allyloxymethyl)acrylate monomers such as t-octyl α-allyloxymethylacrylate, 2-ethylhexyl α-allyloxymethylacrylate, capryl α-allyloxymethylacrylate, nonyl α-allyloxymethylacrylate, decyl α-allyloxymethylacrylate, undecyl α-allyloxymethylacrylate, lauryl α-allyloxymethylacrylate, tridecyl α-allyloxymethylacrylate, myristyl α-allyloxymethylacrylate, pentadecyl α-allyloxymethylacrylate, cetyl α-allyloxymethylacrylate, heptadecyl α-allyloxymethylacrylate, stearyl α-allyloxymethylacrylate, nonadecyl α-allyloxymethylacrylate, eicosyl α-allyloxymethylacrylate, ceryl α-allyloxymethylacrylate, and melissyl α-allyloxymethylacrylate;Alkoxyalkyl-(α-allyloxymethyl)acrylate monomers such as methoxyethyl α-allyloxymethylacrylate, methoxyethoxyethyl α-allyloxymethylacrylate, methoxyethoxyethoxyethyl α-allyloxymethylacrylate, 3-methoxybutyl α-allyloxymethylacrylate, ethoxyethyl α-allyloxymethylacrylate, ethoxyethoxyethyl α-allyloxymethylacrylate, phenoxyethyl α-allyloxymethylacrylate, and phenoxyethoxyethyl α-allyloxymethylacrylate;Hydroxyethyl α-allyloxymethylacrylate, hydroxypropyl α-allyloxymethylacrylate, hydroxybutyl α-allyloxymethylacrylate, fluoroethyl α-allyloxymethylacrylate, difluoroethyl α-allyloxymethylacrylate, chloroethyl α-allyloxymethylacrylate, dichloroethyl α-allyloxymethylacrylate, bromoethyl α-allyloxymethylacrylate, dibromoethyl α-allyloxymethylacrylate, vinyl α-allyloxymethylacrylate, allyl α-allyloxymethylacrylate, methallyl α-allyloxymethylacrylate, crotyl α-allyloxymethylacrylate, propargyl α-allyloxymethylacrylate, cyclopentyl α-allyloxymethylacrylate, cyclohexyl α-allyloxymethylacrylate, 4-methylcyclohexyl α-allyloxymethylacrylate, α-allyloxymethyl acrylate Examples of the acrylate monomer include 4-t-butylcyclohexyl acrylate, tricyclodecanyl α-allyloxymethylacrylate, isobornyl α-allyloxymethylacrylate, adamantyl α-allyloxymethylacrylate, dicyclopentadienyl α-allyloxymethylacrylate, phenyl α-allyloxymethylacrylate, methylphenyl α-allyloxymethylacrylate, dimethylphenyl α-allyloxymethylacrylate, trimethylphenyl α-allyloxymethylacrylate, 4-t-butylphenyl α-allyloxymethylacrylate, benzyl α-allyloxymethylacrylate, diphenylmethyl α-allyloxymethylacrylate, diphenylethyl α-allyloxymethylacrylate, triphenylmethyl α-allyloxymethylacrylate, cinnamyl α-allyloxymethylacrylate, naphthyl α-allyloxymethylacrylate, and anthranyl α-allyloxymethylacrylate. Among these, alkyl(α-allyloxymethyl)acrylate monomers are preferred. As the alkyl-(α-allyloxymethyl)acrylate monomer, methyl α-allyloxymethylacrylate (also referred to as methyl-(α-allyloxymethyl)acrylate) is particularly preferred from the viewpoints of transparency, dispersibility, ease of industrial availability, etc.;

[0078] The α-(unsaturated alkoxyalkyl)acrylate monomer can be produced, for example, by the production method disclosed in WO 2010 / 114077.

[0079] Another example of a monomer capable of introducing the structural unit (C) is a 2-(hydroxyalkyl)acrylic acid alkyl ester, which can react with (meth)acrylic acid to form a lactone ring structure in the main chain.

[0080] Examples of the 2-(hydroxyalkyl)acrylic acid alkyl ester include 2-(1-hydroxyalkyl)acrylic acid alkyl ester, 2-(2-hydroxyalkyl)acrylic acid alkyl ester, etc. Specific examples include methyl 2-(1-hydroxymethyl)acrylate, ethyl 2-(1-hydroxymethyl)acrylate, isopropyl 2-(1-hydroxymethyl)acrylate, n-butyl 2-(1-hydroxymethyl)acrylate, t-butyl 2-(1-hydroxymethyl)acrylate, 2-ethylhexyl 2-(1-hydroxymethyl)acrylate, etc. Of these, methyl 2-(1-hydroxymethyl)acrylate and ethyl 2-(1-hydroxymethyl)acrylate are preferred.

[0081] The polymer may have only one type of the structural unit (C), or may have two or more types.

[0082] The content of the structural unit (C) is preferably 0 to 50% by mass, more preferably 1 to 50% by mass, even more preferably 1.5 to 20% by mass, and even more preferably 2 to 15% by mass, relative to 100% by mass of all structural units in the polymer.

[0083] (4) Structural Unit (D) The polymer may have a structural unit (D) other than the structural units (A), (B), and (C) described above. Examples of the other structural unit (D) include structural units derived from the following monomers: hydroxyl group-containing monomers such as 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; 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, dicyclopentyl (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; epoxy group-containing monomers such as glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, vinylbenzyl glycidyl ether, allyl glycidyl ether, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and vinylcyclohexene oxide; (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; styrene derivatives such as vinyltoluene and styrene; unsaturated isocyanates such as isocyanatoethyl (meth)acrylate and allyl isocyanate; and the like.

[0084] In particular, the structural unit (D) is preferably a structural unit derived from at least one monomer selected from the group consisting of hydroxyl group-containing monomers, (meth)acrylic acid ester monomers, and styrene derivatives.

[0085] The polymer may have only one type of the structural unit (D), or may have two or more types.

[0086] The content of the structural unit (D) is preferably 0 to 99% by mass, more preferably 1 to 99% by mass, even more preferably 2 to 80% by mass, and even more preferably 10 to 70% by mass, relative to 100% by mass of all structural units in the polymer. When the polymer contains two or more types of the structural unit (D), the content of each structural unit (D) can be appropriately set depending on the use and purpose of the polymer of the present invention.

[0087] The acid value of the polymer is preferably 10 to 200 mgKOH / g. In terms of good developability, the acid value of the polymer is more preferably 20 to 150 mgKOH / g, and even more preferably 50 to 130 mgKOH / g. The acid value is a value obtained by measurement by neutralization titration using a potassium hydroxide (KOH) solution, and is the acid value per 1 g of resin solid content.

[0088] The weight-average molecular weight of the polymer is preferably 1,000 to 100,000. In terms of good low-temperature curing properties, the weight-average molecular weight of the polymer is more preferably 3,000 to 50,000, and even more preferably 5,000 to 20,000. The weight-average molecular weight is a value obtained by measurement using gel permeation chromatography (GPC) in accordance with the method described in the examples.

[0089] The vinyl ether equivalent of the polymer is preferably 200 to 50,000 g / mol. From the viewpoint of improving curability and storage stability, the vinyl ether equivalent is more preferably 300 to 10,000 g / mol, and even more preferably 400 to 2,000 g / mol. The vinyl ether group here refers to a vinyl ether group generated when all acetal bonds in the polymer are deprotected, and refers to a vinyl ether group potentially present in the polymer.

[0090] The vinyl ether equivalent is the mass of the solid content of the polymer solution per 1 mol of vinyl ether groups in the polymer. The mass of the solid content of the polymer solution is the mass of the monomer components constituting the polymer. 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. It can also be measured using various analyses such as titration, elemental analysis, NMR, and IR, or differential scanning calorimetry.

[0091] The polymer 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.

[0092] When the polymer has a polymerizable double bond in a side chain, the double bond equivalent of the polymer is preferably 400 to 50,000 g / mol. From the viewpoint of improving curability, the double bond equivalent is more preferably 500 to 10,000 g / mol, and even more preferably 600 to 2,000 g / mol. The double bond here refers to a radically polymerizable double bond. That is, a polymerizable double bond represented by a (meth)acryloyl group, for example, a double bond generated by adding tetrahydrophthalic anhydride to a hydroxyl group, is not included in the calculation of the double bond equivalent because it has no reactivity.

[0093] The double bond equivalent is the mass of the solid content of the polymer solution per 1 mol of double bonds in the polymer. The mass of the solid content of the polymer solution is the mass of the monomer components constituting the polymer. The double bond equivalent can be determined by dividing the mass (g) of the polymer solid content of the polymer solution by the double bond amount (mol) of the polymer. It can also be measured using various analyses such as titration, elemental analysis, NMR, and IR, or differential scanning calorimetry.

[0094] 2. Method for Producing Polymer The method for producing the polymer 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 structural unit (A) and, if necessary, a monomer capable of introducing the structural units (B), (C), and (D) 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 a desired range.

[0095] 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 polymerization methods such as radical polymerization, anionic polymerization, cationic polymerization, and coordination polymerization, but polymerization methods based on radical polymerization mechanisms are preferred because of their industrial advantages. Furthermore, the molecular weight of the polymer obtained by polymerizing the 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.

[0096] 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.

[0097] 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-based 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; DMSO, nitromethane, and the like. 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 using known methods.

[0098] Regarding the polymerization conditions, the polymerization temperature may be appropriately set depending on the type and amount of the monomers used, the type and amount of the polymerization initiator, etc., and is, for example, preferably 40 to 130° C., more preferably 50 to 120° 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.

[0099] Among the methods for producing the above polymers, it is preferable to include a step of polymerizing a monomer component including a monomer (a) containing a group that generates a vinyl ether group when exposed to acid or heat, and an acid group-containing monomer (b). Such a method for producing a polymer having a structural unit (A) represented by formula (1) and an acid group-containing structural unit (B), which method includes a step (P-1) of polymerizing a monomer unit containing a group that generates a vinyl ether group when exposed to acid or heat, and an acid group-containing monomer (polymer production method 1), also constitutes one aspect of the present invention.

[0100] Step (P-1) The monomer having a group that generates a vinyl ether group when exposed to an acid or heat can be a monomer capable of introducing the structural unit (A) described above, and preferably a monomer compound represented by formula (a) described above. Examples of the acid group-containing monomer can be the same as those described above.

[0101] The polymerization in the step (P-1) can be carried out by the same method as the polymerization method described above. In the polymerization, the above-mentioned polymerization initiator, additives such as a chain transfer agent, and solvent may be used as appropriate.

[0102] The polymerization in step (P-1) is preferably carried out in the presence of a basic compound. By polymerizing the monomer components in the presence of a basic compound, the acid groups of the acid group-containing monomer units are prevented from generating vinyl ether groups in the monomer (a), allowing the desired polymerization reaction to proceed smoothly. Furthermore, the acidity of the reaction system is neutralized, suppressing the generation of vinyl ether groups, thereby preventing gelation and allowing the production of a polymer with excellent storage stability to be obtained. Furthermore, a basic compound may be added after polymerization to improve the storage stability of the resulting polymer.

[0103] 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; cyclic aliphatic 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; [Pt(NH ３ ) 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.

[0104] The boiling point of the basic compound is preferably 20 to 220°C, more preferably 30 to 150°C, and even more preferably 50 to 100°C. If the boiling point of the basic compound is equal to or lower than the baking temperature after the coating film is formed, the basic compound volatilizes during baking, and the neutralized side-chain carboxylate salt becomes a carboxylic acid. This carboxylic acid can promote cationic polymerization of the vinyl ether and crosslinking by acetalization with the side-chain carboxylic acid.

[0105] In the step (P-1), the amount of the basic compound used is not particularly limited as long as it can suppress the formation of vinyl ether groups. For example, the amount is preferably 0.5 to 10 equivalents, more preferably 0.8 to 2 equivalents, and even more preferably 0.9 to 1.2 equivalents, relative to 1 equivalent of the acid group-containing monomer.

[0106] The present invention also provides a method for producing a polymer having the structural unit (A) represented by the above formula (1) and the acid group-containing structural unit (B), the method comprising: a step (Q-1) of polymerizing monomer components including a monomer containing a group that generates a vinyl ether group in response to acid or heat, and a hydroxyl group-containing monomer; and a step (Q-2) of reacting the polymer obtained in the step (Q-1) with an acid group-containing compound (polymer production method 2).

[0107] Step (Q-1) In the above-mentioned polymer production method 2, first, a monomer component including a monomer (a) containing a group that generates a vinyl ether group when exposed to acid or heat, and a hydroxyl group-containing monomer is polymerized.

[0108] In the step (Q-1), the monomer containing a group that forms a vinyl ether group when exposed to acid or heat, and the hydroxyl group-containing monomer may be the same as those described above. The polymerization reaction in the step (Q-1) may be carried out in the same manner as the polymerization method described above. In addition, in the polymerization, additives such as the polymerization initiator and chain transfer agent, and solvents may be used.

[0109] Step (Q-2) In the polymer production method 2, the polymer obtained in step (Q-1) is then reacted with an acid group-containing compound. By reacting the polymer with the acid group-containing compound, the hydroxyl groups of the polymer react with the acid groups of the acid group-containing compound, and the acid group-containing compound is added.

[0110] The acid group-containing compound is preferably a polybasic acid or a polybasic acid anhydride, for example, carboxylic acids such as succinic acid, maleic acid, phthalic acid, tetrahydrophthalic acid, trimellitic acid, etc.; carboxylic acid anhydrides such as succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, itaconic anhydride, trimellitic anhydride, etc.; etc. Among them, 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 according to the use, purpose, desired acid value, etc. of the resulting polymer.

[0111] The reaction of the polymer with the acid group-containing compound in step (Q-2) is preferably carried out in the presence of a basic compound. The addition reaction of the acid group-containing compound generates acid groups at the terminals of the polymer, which are immediately neutralized by the basic compound. This facilitates protection of the vinyl ether groups in the resulting polymer by the groups that generate vinyl ether groups when exposed to acid or heat, thereby suppressing reactions between polymers, improving the synthesis and storage stability of the polymer.

[0112] Examples of the basic compound include the same compounds as those mentioned above.

[0113] In the step (Q-2), the amount of the basic compound used is not particularly limited as long as it is capable of suppressing the formation of vinyl ether groups. For example, the amount is preferably 0.5 to 10 equivalents, more preferably 0.8 to 2 equivalents, and even more preferably 0.9 to 1.2 equivalents, relative to 1 equivalent of the structural unit containing an acid group used in the step (Q-1).

[0114] In addition, when producing a polymer having a polymerizable double bond in a side chain, for example, after the above step (Q-1), a polymerizable double bond can be introduced into the side chain of the polymer by addition reaction of (meth)acrylic acid with an epoxy group. Alternatively, a polymerizable double bond can be introduced into the side chain of the polymer by addition reaction of an unsaturated isocyanate with a hydroxyl group instead of the above (meth)acrylic acid.

[0115] Alternatively, a polymerizable double bond can be introduced into the side chain of a polymer by subjecting an epoxy group-containing compound to an addition reaction with an acid group. For example, after preparing a polymer (base polymer) having an acid group, the acid group is reacted with the epoxy group-containing monomer, and the polymerizable double bond can be introduced by an addition reaction resulting from cleavage of the epoxy group.

[0116] The addition reaction of the (meth)acrylic acid, unsaturated isocyanates, and epoxy group-containing compound described above can be carried out by any known method without any particular limitation. In addition, commonly used catalysts, solvents, etc. may be used in the addition reaction.

[0117] In the method for producing the polymer, as described above, it is preferable to use a basic compound, but the basic compound may remain (exist) after the production of the polymer, and a polymer solution containing the polymer and the basic compound is also one of the preferred embodiments of the present invention. Such a polymer solution has good storage stability. The polymer solution may also further contain a polar solvent described below.

[0118] 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.

[0119] 3. Method for Producing Monomer Compound A method for producing the monomer compound represented by the above formula (a) as a monomer into which the structural unit (A) can be introduced will be described. Examples of the method for producing the monomer compound include a method of reacting a vinyl ether group-containing (meth)acrylate compound with a carboxylic acid compound or an alcohol compound.

[0120] Examples of the vinyl ether group-containing (meth)acrylate compound include compounds represented by the following formula (3): CH ２ = C(R １１ )-COO-R １２ —O—CH═CH ２ (3) (wherein, R １１represents a hydrogen atom or a methyl group. １２ represents a linear or branched divalent organic group. １２ The organic group represented by the formula (a) is R ８ The organic group may be the same as the organic group represented by the following formula:

[0121] Specific preferred examples of the vinyl ether group-containing (meth)acrylate compound include 2-(2-vinyloxyethoxy)ethyl acrylate and 2-(2-vinyloxyethoxy)ethyl methacrylate.

[0122] Examples of the carboxylic acid compound include aliphatic carboxylic acids such as acetic acid, propionic acid, butyric 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 terms of ease of copolymerization of the resulting product, and aliphatic carboxylic acids and formic acid are more preferred, with acetic acid, propionic acid, butyric acid, and formic acid being even more preferred. Furthermore, from the viewpoint of improving the curability and storage stability after polymerization, propionic acid and butyric acid are more preferred, and butyric acid is most preferred.

[0123] 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 in that the product is easily copolymerizable, and ethanol, isopropanol, and propylene glycol monomethyl ether are more preferred.

[0124] The carboxylic acid compounds and alcohol compounds may be used alone or in combination of two or more. Among them, carboxylic acid compounds are preferred in terms of better storage stability.

[0125] Furthermore, the carboxylic acid compound and alcohol compound are preferably compounds having 1 to 19 carbon atoms, more preferably compounds having 1 to 10 carbon atoms, even more preferably compounds having 1 to 5 carbon atoms, and most preferably compounds having 4 carbon atoms, in that they can easily achieve both storage stability and low-temperature curing properties.

[0126] In the above reaction, it is preferable to mix 1 equivalent or more of a carboxylic acid compound or an alcohol compound with 1 equivalent of the vinyl ether group-containing (meth)acrylate compound, more preferably 1 to 20 equivalents, even more preferably 1.1 to 10 equivalents, and even more preferably 1.2 to 2 equivalents. By using 1 equivalent or more, the reaction substrate itself acts as an autocatalyst, accelerating the reaction.

[0127] The reaction can be carried out by any known method, such as by mixing the components and heating them, without any particular limitation. Although it is not necessary to use a solvent in the reaction, a solvent may be used. Examples of the solvent used in the reaction include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and heptane; ethers such as diethyl ether and diisopropyl ether; ketones such as acetone and methyl ethyl ketone; polar solvents such as dimethylformamide and dimethyl sulfoxide; halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethane, and chlorobenzene; esters such as ethyl acetate; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; and ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, and propylene glycol monomethyl ether acetate.

[0128] In the above reaction, known additives such as catalysts and polymerization inhibitors may be added. Examples of the catalyst include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butanoic acid, trichloroacetic acid, dichloroacetic acid, pyruvic acid, and glycolic acid; aliphatic polycarboxylic acids such as oxalic acid, maleic acid, oxaloacetic acid, malonic acid, fumaric acid, tartaric acid, and citric acid; aromatic carboxylic acids such as benzoic acid and terephthalic acid; aromatic sulfonic acids or salts thereof such as benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid pyridinium salt, and p-toluenesulfonic acid quinolinium salt; sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, nickel sulfate, copper sulfate, and zirconium sulfate. Examples of suitable catalysts include sulfates; hydrogen sulfates such as sodium hydrogen sulfate and potassium hydrogen sulfate; mineral acids such as sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, and polyphosphoric acid; heteropolyacids such as vanadium phosphate, tungstomolybdic phosphonate, and tungstomolybdic silicoate; and acid catalysts described in paragraph

[0043] of JP-A No. 2003-201267, such as acid zeolites. Other examples include phosphate group-containing unsaturated compounds such as 2-methacryloyloxyethyl acid phosphate and 2-acryloyloxyethyl acid phosphate, and commercially available products such as Light Ester P-1M and Light Ester P-2M (manufactured by Kyoeisha Chemical Co., Ltd.). The above-mentioned catalysts may be used alone or in combination of two or more.

[0129] The amount of the catalyst used is preferably 0.001 to 10 parts by mass, more preferably 0.005 to 1 part by mass, and even more preferably 0.008 to 0.05 parts by mass, relative to 100 parts by mass of the vinyl ether group-containing (meth)acrylate compound. Among these, it is preferable to use p-toluenesulfonic acid as the catalyst in the above reaction because the reaction is rapid.

[0130] Examples of the polymerization inhibitor include quinone-based polymerization inhibitors such as hydroquinone, methoxyhydroquinone, benzoquinone, and p-tert-butylcatechol; alkylphenol-based polymerization inhibitors such as 2,2'-methylene-bis(4-methyl-tert-butylphenol), 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, and 2,4,6-tri-tert-butylphenol; amine-based polymerization inhibitors such as alkylated diphenylamine, N,N'-diphenyl-p-phenylenediamine, and phenothiazine; N-oxyls such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl; and copper dithiocarbamate-based polymerization inhibitors such as copper dimethyldithiocarbamate, copper diethyldithiocarbamate, and copper dibutyldithiocarbamate. These may be used alone or in combination of two or more.

[0131] The amount of the polymerization inhibitor used is preferably 0.001 to 10 parts by mass, more preferably 0.005 to 1 part by mass, and even more preferably 0.01 to 0.5 parts by mass, relative to 100 parts by mass of the vinyl ether group-containing (meth)acrylate compound.

[0132] The reaction conditions are not particularly limited, but for example, the reaction temperature is 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.

[0133] The method for producing the monomer compound may further include other steps such as a purification step in addition to the reaction step described above. The other steps may be carried out by known methods. The purification step is preferably an acid-base extraction method. The target product can be efficiently purified by separating unreacted carboxylic acid compounds and alcohols into an aqueous layer using a basic aqueous solution and concentrating the oil layer.

[0134] After the synthesis of the monomer compound, a basic compound may be added to the monomer compound in order to improve the storage stability of the monomer compound. Examples of the basic compound include the same basic compounds as those described above.

[0135] The above-mentioned monomer compounds can be produced by the production methods described above, but among the above-mentioned monomer compounds, the monomer compound represented by the following formula (a-1) is preferably produced by a method including a step of reacting a vinyl ether group-containing (meth)acrylate compound with a carboxylic acid compound, in which the amount of the carboxylic acid compound used in the reaction step is 1 equivalent or more per equivalent of the vinyl ether group of the vinyl ether group-containing (meth)acrylate compound. Such a method for producing the above formula (a-1) is a novel production method and is one aspect of the present invention.

[0136]

[0137] (In the formula, R ７ represents a hydrogen atom or a methyl group. ８ represents a linear or branched divalent organic group. １０ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms (excluding groups containing a (meth)acryloyl group). １０ The organic group having 1 to 20 carbon atoms represented by the formula (I) can be any of the above-mentioned R except for groups containing a (meth)acryloyl group. ６ The organic group represented by the formula (I) can be the same as the organic group represented by the formula (I).

[0138] 4. Polymer Solution The above-described polymer is preferably prepared as a polymer solution together with a polar solvent. By adding a polar solvent to the above-described polymer to prepare a polymer solution, the storage stability of the polymer is improved. Although the reason why the addition of a polar solvent improves the storage stability of the polymer is unclear, it is believed that the deprotection of the acetal group is suppressed due to interaction with the acetal structure, thereby improving storage stability while maintaining solvent resistance. Such a polymer solution containing the above-described polymer and a polar solvent also constitutes one aspect of the present invention.

[0139] The polar solvent includes a protic polar solvent and an aprotic polar solvent. Examples of the protic polar solvent include water, an alcohol solvent, an amine solvent, and a phenol solvent. Among these, the protic polar solvent is preferably an alcohol solvent.

[0140] The alcohol solvent is preferably a saturated alcohol, and examples thereof include monofunctional alcohols (monoalcohols), polyhydric alcohols, glycol monoethers, etc. Specific examples of the alcohol solvent include primary alcohols such as methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monophenyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol mono-n-butyl ether, tripropylene glycol, and tripropylene glycol mono-n-butyl ether; Examples of the alcohol solvent include secondary alcohols such as isopropanol, 2-butanol, 2-pentanol, 3-pentanol, 2-hexanol, cyclohexanol, 2-heptanol, 3-heptanol, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol monophenyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, and tripropylene glycol monomethyl ether; and tertiary alcohols such as tert-butanol, tert-pentanol, and tert-hexanol. Among these, the alcohol solvent is preferably a secondary alcohol or a tertiary alcohol, in terms of suppressing deprotection of the acetal group and reducing the viscosity of the polymer solution.

[0141] The number of carbon atoms in the alcohol solvent is preferably 1 to 10, more preferably 2 to 8, and even more preferably 3 to 6, in that the boiling point is relatively low and the solvent can be easily removed by heating.

[0142] As the alcohol solvent, propylene glycol monomethyl ether is particularly preferred.

[0143] Examples of the amine solvent include diethyleneamine, dimethylamine, and oleylamine.

[0144] Examples of the phenolic solvent include phenol, cresol, o-cresol, m-cresol, p-cresol, and xylenol.

[0145] Preferred examples of the aprotic solvent include ether solvents, ether acetate solvents, and amide solvents, and among these, the aprotic solvent is more preferably an amide solvent.

[0146] Examples of the ether solvent include tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether.

[0147] Examples of the ether acetate solvent include one or two types of ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, and propylene glycol monomethyl ether acetate.

[0148] Examples of the amide solvent include N,N-diethylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetramethylurea, etc. N,N-dimethylformamide is preferred from the viewpoint of compatibility with the copolymer.

[0149] The polar solvent is preferably at least one solvent selected from the group consisting of alcohol-based solvents, ether-based solvents, and amide-based solvents, and more preferably at least one solvent selected from the group consisting of alcohol-based solvents and amide-based solvents.

[0150] The boiling point of the polar solvent is preferably 70 to 180°C, more preferably 100 to 170°C, and even more preferably 110 to 160°C, in that it is easy to remove by heating, has a certain boiling point, and is easy to form a flat film.

[0151] The polymer solution may contain one or more polar solvents. The content of the polar solvent in the polymer solution is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, relative to 100% by mass of the polymer solids. In order to facilitate concentration adjustment in the resin composition, the content of the polar solvent is preferably 1000% by mass or less, more preferably 300% by mass or less, and even more preferably 200% by mass or less, relative to 100% by mass of the polymer solids.

[0152] The polymer solution may be prepared by mixing the polymer purified from the polymerization solution containing the polymer obtained during polymerization with the polar solvent, or by adding the polar solvent to the polymerization solution containing the polymer. When the polymer solution is prepared by adding the polar solvent to the polymerization solution containing the polymer, the polymer solution may contain the polymerization solvent. The polymer solution may contain components other than the polymer and polar solvent.

[0153] 5. Polymer Solution The above-described polymer or polymer solution can be prepared as a polymer solution together with a basic dispersant and / or a basic compound. The above-described polymer solution has excellent storage stability. A polymer solution containing the above-described polymer or polymer solution and a basic dispersant and / or a basic compound also constitutes one aspect of the present invention. In addition, one preferred embodiment of the present invention is one in which the polymer or basic dispersant is neutralized with a basic compound.

[0154] Examples of the basic compound include the basic compounds described above. As described above, the basic compound may be a residue of a compound used in the production of the polymer.

[0155] Preferred examples of the basic dispersant include polymer dispersants having a basic functional group. The polymer dispersant having a basic functional group may be neutralized with the basic compound as described above, and includes, for example, a neutralized amine salt. Examples of the basic dispersant include Disperbyk (registered trademark)-108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, and 2001. , 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164, etc. (all manufactured by BYK Japan), SOLSPERSE (registered trademark) -3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000 , 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc. (above, Nippon Lube Examples of suitable acrylic resins include acrylic resins manufactured by Ajinomoto Fine-Techno Co., Ltd. (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Ajisper (registered trademark) PA111, PB711, PB821, PB822, and PB824 (all manufactured by Ajinomoto Fine-Techno Co., Ltd.), and Disparlon (registered trademark) 1831, 1850, 1860, DA-703-50, DA-7301, DA-325, and DA234 (all manufactured by Kusumoto Chemicals Co., Ltd.).

[0156] The content of the basic dispersant in the polymer solution is preferably 1 to 50 mass%, more preferably 3 to 45 mass%, and even more preferably 5 to 35 mass%, based on 100 mass% of the total solid content of the polymer solution, in order to achieve good dispersion stability. In this specification, the term "total solid content" refers to the total amount of components that form a cured product (components excluding solvents and the like that volatilize during the formation of a cured product and curing catalysts).

[0157] The content of the basic compound in the polymer solution is preferably 1 to 50 mass%, more preferably 3 to 45 mass%, and even more preferably 5 to 35 mass%, relative to 100 mass% of the total solid content of the polymer solution, in terms of good storage stability.

[0158] The content of the polymer in the polymer solution is preferably 5 to 80 mass%, more preferably 10 to 75 mass%, and even more preferably 15 to 70 mass%, relative to 100 mass% of the total solid content of the polymer solution.

[0159] In addition, the polymer in the polymer solution preferably has an epoxy equivalent of 1000 g / mol or more, more preferably 5000 g / mol or more, and further preferably has no epoxy groups, in order to obtain even more excellent storage stability. The epoxy equivalent can be determined by dividing the mass (g) of the polymer solid content by the number of moles (mol) of epoxy groups contained in the polymer.

[0160] The content of the polar solvent in the polymer solution is preferably 10 to 1,000 parts by mass, more preferably 20 to 800 parts by mass, and even more preferably 30 to 600 parts by mass, relative to 100 parts by mass of the total solid content of the polymer solution.

[0161] The method for preparing the polymer solution is not particularly limited, and examples thereof include a method in which the components contained in the polymer solution are mixed by a known mixing means.

[0162] 6. Colorant Dispersion The above-described polymer solution may further contain a colorant. A colorant dispersion containing the above-described polymer solution and a colorant also constitutes one aspect of the present invention. The above-described colorant dispersion has excellent storage stability.

[0163] The colorant is not particularly limited, and examples thereof include known pigments, dyes, etc. The content of the colorant in the colorant dispersion liquid is preferably 1 to 80% by mass, more preferably 5 to 70% by mass, and even more preferably 10 to 60% by mass, relative to 100% by mass of the total solid content of the colorant dispersion liquid, in order to fully meet recent demands for higher color purity and higher brightness.

[0164] The content of the polymer and the basic dispersant in the colorant dispersion liquid is preferably within the same range as the content of the polymer and the basic dispersant in the polymer solution.

[0165] The colorant dispersion liquid may further contain a solvent, and examples of the solvent include the polymerization solvent for the polymer described above and the polar solvent described above.

[0166] The amount of the solvent in the colorant dispersion liquid is preferably 10 to 1000 parts by mass, more preferably 30 to 300 parts by mass, and even more preferably 40 to 200 parts by mass, relative to 100 parts by mass of the total solid content of the colorant dispersion liquid, in terms of good storage stability.

[0167] The method for preparing the colorant dispersion liquid is not particularly limited, and the colorant dispersion liquid can be prepared by mixing and dispersing the components contained in the colorant dispersion liquid by known mixing and dispersing means.

[0168] 7. Photosensitive Resin Composition The present invention also includes a photosensitive resin composition containing the above-described polymer, polymer solution, polymer solution, or colorant dispersion, a polymerizable compound, and a photopolymerization initiator and / or a photoacid generator. Because the photosensitive resin composition of the present invention contains the above-described polymer, it has excellent storage stability and can provide a cured product that has excellent solvent resistance even under low-temperature curing conditions.

[0169] The content of the polymer is preferably 5 to 80% by mass, more preferably 10 to 75% by mass, and even more preferably 15 to 70% by mass, relative to 100% by mass of the total solid content of the photosensitive resin composition.

[0170] When the photosensitive resin composition contains the polymer solution, the content of the polar solvent is preferably 10 to 1000 parts by mass, more preferably 30 to 300 parts by mass, and even more preferably 40 to 200 parts by mass, relative to 100 parts by mass of the total solid content of the photosensitive resin composition.

[0171] When the photosensitive resin composition contains the colorant dispersion, the content of the basic dispersant is preferably 1 to 50 mass%, more preferably 3 to 45 mass%, and even more preferably 5 to 35 mass%, relative to 100 mass% of the total solid content of the photosensitive resin composition.

[0172] When the photosensitive resin composition contains the colorant dispersion, the content of the colorant is preferably 1 to 80 mass%, more preferably 5 to 70 mass%, and even more preferably 10 to 60 mass%, relative to 100 mass% of the total solid content of the photosensitive resin composition.

[0173] (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, and examples thereof include monofunctional compounds having one polymerizable unsaturated group in the molecule and polyfunctional compounds having two or more polymerizable unsaturated groups.

[0174] 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. Furthermore, monomers having an active methylene group or an active methine group can also be used.

[0175] 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;

[0176] 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,

[0177]

[0178] a tri- or higher functional (meth)acrylate compound such as a modified product of dipentaerythritol hexaacrylate represented by the formula:

[0179] 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;

[0180] 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;

[0181] polyfunctional allyl ethers such as 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 oxide-added ditrimethylolpropane tetraallyl ether, ethylene oxide-added pentaerythritol tetraallyl ether, and ethylene oxide-added dipentaerythritol hexaallyl ether;

[0182] 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.

[0183] Among the polymerizable compounds, it is preferable to use a polyfunctional polymerizable compound from the viewpoint of further enhancing the curability of the photosensitive 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, for example, 2000 or less from the viewpoint of handling.

[0184] As the polyfunctional polymerizable compound, 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 photosensitive resin composition has better photosensitivity and curability, and a cured product with even higher hardness and transparency can be obtained. It is more preferred to use a trifunctional or higher polyfunctional (meth)acrylate compound as the polyfunctional polymerizable compound.

[0185] The content of the polymerizable compound is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and even more preferably 15 to 40% by mass, relative to 100% by mass of the total solid content of the photosensitive resin composition.

[0186] (Photopolymerization Initiator) 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-one ("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), and phenylglyoxylic acid methyl ester ("DAROCURE benzyl ketal compounds such as 1-hydroxy-cyclohexyl-phenyl-ketone ("IRGACURE184", manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one ("DAROCUR1173", manufactured by BASF), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one ("IRGACURE2959", manufactured by BASF), 2-hydroxy -1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propan-1-one ("IRGACURE 127", manufactured by BASF Corporation), [1-hydroxy-cyclohexyl-phenyl-ketone + benzophenone] ("IRGACURE 500", manufactured by BASF Corporation), and other hydroketone compounds; as well as other alkylphenone compounds exemplified in paragraphs

[0084] to

[0086] of JP-A No. 2013-227485;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 the photopolymerization initiator 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. Of these, aminoketone compounds and oxime ester compounds are preferred. The photopolymerization initiators may be used alone or in combination of two or more.

[0187] The content of the photopolymerization initiator is preferably 0.3 to 20% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 8% by mass, relative to 100% by mass of the total solid content of the photosensitive resin composition.

[0188] (Photoacid Generator) The photosensitive resin composition may also contain a photoacid generator. By containing a photoacid generator, cationic polymerization can proceed, and a cured product having better solvent resistance can be obtained.

[0189] The photoacid generator used in the present invention is a compound that generates an acid and a radical simultaneously upon irradiation with light. Examples of the photoacid generator include compounds that generate an acid upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. Specific examples include known compounds such as onium salt compounds, sulfone compounds, sulfonate ester compounds, quinone diazide compounds, sulfonimide compounds, and diazomethane compounds. Among these, the photoacid generator is preferably at least one selected from the group consisting of onium salt compounds, sulfonimide compounds, and diazomethane compounds, more preferably an onium salt compound, and even more preferably a triarylsulfonium salt. Specific examples of the photoacid generator include the compounds described in paragraphs

[0112] to

[0117] of JP 2021-39186 A.

[0190] The content of the photoacid generator is not particularly limited as long as it is within a range in which the effects of the present invention are exhibited, and may be set as appropriate. For example, the content is preferably 0.3 to 20 mass %, more preferably 0.5 to 10 mass %, and even more preferably 1 to 8 mass %, relative to 100 mass % of the total solid content of the photosensitive resin composition of the present invention.

[0191] The photosensitive resin composition may also contain other components in addition to the above-mentioned components, as necessary. Examples of the other components include solvents; colorants (pigments, dyes); dispersants; heat resistance improvers; leveling agents; development aids; inorganic fine particles such as silica fine particles; silane-based, aluminum-based, and titanium-based coupling agents; fillers; thermosetting resins such as phenolic resins and polyvinylphenols; curing aids such as polyfunctional thiol compounds; plasticizers; polymerization inhibitors; ultraviolet absorbers; antioxidants; matting agents; defoaming agents; antistatic agents; slip agents; surface modifiers; thixotropic agents; thixotropic aids; quinone diazide compounds; polyhydric phenol compounds; cationic polymerizable compounds; and thermal acid generators. These may be used alone or in combination of two or more. These other components can be appropriately selected from known compounds and used, and the amount used can also be appropriately determined. For example, when the photosensitive resin composition is used for a color filter, the photosensitive resin composition preferably contains a colorant.

[0192] The photosensitive resin composition preferably contains a polyfunctional thiol compound, which is expected to promote crosslinking with vinyl ether groups and cationic polymerization. Examples of the polyfunctional thiol compound include tris(3-mercaptopropionyloxy)ethyl isocyanurate, trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(2-(3-sulfanylbutanoyloxy)ethyl)-1,3,5-triazinane-2,4,6-trione, and trimethylolpropane tris(3-mercaptobutyrate).

[0193] <Preparation of Photosensitive Resin Composition> The method for preparing the photosensitive resin composition of the present invention 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 steps that are usually performed may be further included. When the photosensitive resin composition contains a colorant, it is preferable to prepare it through a known colorant dispersion treatment step.

[0194] 8. Cured Product The method for obtaining a cured product using the photosensitive resin composition of the present invention is not particularly limited, and any known method may be used. For example, a method may be used in which the photosensitive resin composition is applied to or molded onto a substrate, and then cured by heating, irradiating with active energy rays such as ultraviolet rays, or a combination of these to obtain a cured product.

[0195] A preferred example of a method for producing the cured product includes the steps of: (1) applying the photosensitive resin composition onto a substrate to form a coating film; (2) irradiating the formed coating film with light; (3) developing and removing the unirradiated portion; and (4) heating the irradiated coating film.

[0196] 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.

[0197] In the step (1), the method for applying the photosensitive resin composition to form a coating film is not particularly limited, and can be performed by known methods such as spin coating, slit coating, roll coating, and cast coating. In the production method, it is preferable to apply the photosensitive resin composition to a substrate and then dry the applied product to form a coating film. The drying can be performed by known methods, for example, using a hot plate, an IR oven, a convection oven, or the like. The drying conditions are appropriately selected depending on the boiling point of the solvent components contained, the type of curable component, the film thickness, the performance of the dryer, etc., but it is usually preferable to perform the drying at a temperature of 50 to 160°C for 10 to 300 seconds.

[0198] In the above step (2), the method for irradiating the formed coating film with light is not particularly limited, and can be any known method. Examples of the light source of the actinic ray used for light irradiation include lamp light sources such as a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, and a fluorescent lamp, and laser light sources such as an argon ion laser, a YAG laser, an excimer laser, a nitrogen laser, a helium cadmium laser, and a semiconductor laser.

[0199] 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.

[0200] In the above step (3), after the light irradiation step described above, 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, thereby obtaining 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.

[0201] The developer used in the step (3) is not particularly limited as long as it dissolves the photosensitive resin composition, but typically an organic solvent or an alkaline aqueous solution is used, or 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 similar to those described in JP 2015-157909 A.

[0202] In the 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 step (4), the heating temperature is preferably 130°C or lower, more preferably 120°C or lower. The photosensitive 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.

[0203] 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.

[0204] When the cured product obtained by the above-described 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.

[0205] The cured product obtained by the above-mentioned production method has excellent solvent resistance. The cured product obtained by curing the above-mentioned photosensitive resin composition also constitutes one aspect of the present invention.

[0206] 9. Applications The polymer and photosensitive resin composition of the present invention have excellent storage stability and can provide a cured product with excellent solvent resistance even under low-temperature curing conditions, and therefore can be suitably used in applications requiring storage stability and high solvent resistance. The polymer and photosensitive resin composition of the present invention are suitably used for optical materials, preferably for resists. The curable resin composition of the present invention can be suitably used for both negative-tone and positive-tone applications.

[0207] The polymer and photosensitive 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 forming color filters.

[0208] 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."

[0209] The various evaluation methods used in the present examples are as follows.

[0210] < １ H-NMR measurement> The obtained monomer compound was measured under the following conditions: １ H-NMR measurement was carried out. Apparatus: Nuclear magnetic resonance spectrometer (600 MHz) manufactured by Agilent Technologies Measurement solvent: deuterated chloroform Sample preparation: Several mg to several tens of mg of the obtained monomer compound were dissolved in the measurement solvent.

[0211] <Acid Value> 3 g of polymer solution was weighed out and dissolved in a mixed solvent of 90 g of acetone and 10 g of water. The solution was titrated using a 0.1 N aqueous solution of KOH as a titrant. The titration was performed using an automatic titrator (product name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.). The acid value per 1 g of solids (mg KOH / g) was determined from the acid value of the polymer solution and the solids content of the polymer solution. The solids content of the polymer solution was determined as follows. Approximately 1 g of the polymer solution was weighed into an aluminum cup, dissolved by adding approximately 3 g of acetone, and then allowed to air dry 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), allowed to cool in a desiccator, and its mass was measured. The solids content (% by mass) of the polymer solution was calculated from the mass loss.

[0212] <Vinyl Ether Equivalent> The vinyl ether equivalent 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.

[0213] <Epoxy Equivalent> The epoxy equivalent was determined by dividing the mass (g) of the polymer solid content by the number of moles (mol) of epoxy groups contained in the polymer.

[0214] <Double Bond Equivalent> The double bond equivalent was determined by dividing the mass (g) of the polymer solid content by the amount of double bonds (mol) of the polymer.

[0215] <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 Super HZM-M (manufactured by Tosoh Corporation).

[0216] <Storage Stability (Viscosity Change Rate)> (Polymer) The viscosity of the polymer 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 a polymer solution is stored at 40°C for one week, and represents the percentage (%) of the viscosity after storage, where the viscosity before storage is taken as 100%. The smaller the viscosity change rate value, the better the storage stability of the polymer was evaluated. (Photosensitive Resin Composition) The viscosity of the photosensitive resin composition 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 a photosensitive resin composition is stored at 40°C for one month, and represents the percentage (%) of the viscosity after storage, where the viscosity before storage is taken as 100%. The smaller the viscosity change rate value, the better the storage stability of the photosensitive resin composition was evaluated.

[0217] <Solvent Resistance> A photosensitive 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 removing 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 photosensitive resin composition was evaluated as having lower solvent resistance.

[0218] <Developability> The photosensitive resin composition was applied to a 10 cm square glass substrate by spin coating, and then subjected to heat treatment (90°C, 3 minutes). After that, the photosensitive resin composition was applied to a 10 cm square glass substrate by spin coating, and the applied film was heated at 90°C for 3 minutes. The applied film was then irradiated with 60 mJ / cm 2 of light 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 having 30 μm line-and-space openings at a distance of 50 μm from the applied film. ２ The coating film was exposed to 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, and the remaining exposed areas were developed by washing with pure water for 10 seconds, thereby evaluating the developability. Specifically, the coating film developed through the photomask as described above was observed with a surface roughness meter (manufactured by Ryoka Systems Co., Ltd., trade name "VertScan 2.0"), and the spraying time of the 0.05% aqueous potassium hydroxide solution required for the unexposed areas to flow was defined as the development time.

[0219] (Production Example 1) Synthesis of Monomer Compound (A-1) 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 of 2-(2-vinyloxyethoxy)ethyl methacrylate and 60.0 parts of acetic acid, heated to 60°C, and reacted for 12 hours. After completion of the reaction, the reaction vessel was cooled, diluted with ethyl acetate, and transferred to a separatory funnel. The contents were washed twice with an aqueous sodium carbonate solution and twice with water, and the oil layer was extracted. After adsorption of 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, thereby obtaining Monomer Compound (A-1). The obtained monomer compound was１ When confirmed by H-NMR, the disappearance of the peak derived from vinyl ether near 6.5 ppm was confirmed, and the production of monomer compound (A-1) was confirmed from the integrated value.

[0220] (Production Example 2) Synthesis of Monomer Compound (A-2) Monomer compound (A-2) was obtained by the same procedure as in Production Example 1, except that 60.0 parts of acetic acid in Production Example 1 was changed to 90.0 parts of isopropanol.

[0221] (Production Example 3) Synthesis of Monomer Compound (A-3) Monomer compound (A-3) was obtained in the same manner as in Production Example 1, except that 60.0 parts of acetic acid in Production Example 1 was changed to 46.0 parts of ethanol.

[0222] (Production Example 4) Monomer Compound (A-4) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping vessel inlet was charged with 30.0 parts of acetic acid and 0.01 parts of p-toluenesulfonic acid, and the mixture was stirred and heated to 30°C to obtain a homogeneous mixture. Subsequently, 100.0 parts of 2-(2-vinyloxyethoxy)ethyl methacrylate was added dropwise, while taking care to avoid heat generation. After the dropwise addition was completed, the mixture was reacted at 30°C for 3 hours to obtain a monomer compound (A-4). The obtained 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 production of monomer compound (A-4) was confirmed from the integrated value.

[0223] (Production Example 5) Synthesis of Monomer Compound (A-5) Monomer compound (A-5) was obtained by the same procedure as in Production Example 4, except that 30.0 parts of acetic acid in Production Example 4 was changed to 30.0 parts of isopropanol.

[0224] (Production Example 6) Synthesis of Monomer Compound (A-6) Monomer compound (A-6) was obtained by the same procedure as in Production Example 4, except that 30.0 parts of acetic acid in Production Example 4 was changed to 23.0 parts of ethanol.

[0225] (Production Example 7) Synthesis of Monomer Compound (A-7) Monomer compound (A-7) was obtained by performing the same operation as in Production Example 4, except that the 30.0 parts of acetic acid in Production Example 4 was changed to 32.2 parts, and the 2-(2-vinyloxyethoxy)ethyl methacrylate was changed to 2-(2-vinyloxyethoxy)ethyl acrylate.

[0226] (Production Example 8) Synthesis of Monomer Compound (A-8) Monomer compound (A-8) was obtained by the same procedure as in Production Example 7, except that 32.2 parts of acetic acid in Production Example 7 was changed to 39.8 parts of propionic acid.

[0227] (Production Example 9) Synthesis of Monomer Compound (A-9) Monomer compound (A-9) was obtained by the same procedure as in Production Example 7, except that 32.2 parts of acetic acid in Production Example 7 was changed to 47.3 parts of butyric acid.

[0228] (Production Example 10) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping tank inlet was charged with 107.6 parts of lauric acid and 0.01 parts of p-toluenesulfonic acid, and the mixture was stirred and heated to 50°C to obtain a homogeneous mixture. Subsequently, 100.0 parts of 2-(2-vinyloxyethoxy)ethyl acrylate was added dropwise, while taking care to avoid heat generation. After the dropwise addition was completed, the mixture was reacted at 50°C for 3 hours to obtain a monomer compound (A-10). The obtained 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 production of monomer compound (A-10) was confirmed from the integrated value.

[0229]

[0230] The descriptions in Table 1 represent the following. VEEM: 2-(2-vinyloxyethoxy)ethyl methacrylate VEEA: 2-(2-vinyloxyethoxy)ethyl acrylate AcOH: acetic acid PA: propionic acid BA: butyric acid LA: lauric acid IPA: isopropyl alcohol EtOH: ethanol PTSA: p-toluenesulfonic acid AEEM: 2-(2-(1-acetoxyethoxy)ethoxy)ethyl methacrylate IEEM: 2-(2-(1-isopropoxyethoxy)ethoxy)ethyl methacrylate EEEM: 2-(2-(1-ethoxyethoxy)ethoxy)ethyl methacrylate AEEA: 2-(2-(1-acetoxyethoxy)ethoxy)ethyl acrylate PEEA: 2-(2-(1-propionyloxyethoxy)ethoxy)ethyl acrylate BEEA: 2-(2-(1-butyloxyethoxy)ethoxy)ethyl acrylate LEEA: 2-(2-(1-lauroxyethoxy)ethoxy)ethyl acrylate

[0231] As shown in Production Examples 1 to 3, by using one equivalent or more of a carboxylic acid compound or an alcohol compound per equivalent of a vinyl ether group-containing (meth)acrylate compound, the reaction substrate itself acts autocatalytically to promote the reaction, as described above, and an acetal-protected monomer compound could be synthesized without a catalyst. Furthermore, as shown in Production Examples 4 to 10, similar synthesis was also possible using an acid catalyst.

[0232] Example 1 Synthesis of Polymer (B-1) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping vessel inlet was charged with 146.7 parts of propylene glycol monomethyl ether acetate, and after purging with nitrogen, the vessel was heated to 60°C. Separately, a beaker was charged with 25.0 parts of propylene glycol monomethyl ether acetate, 23.1 parts of acetic acid, and 0.01 parts of p-toluenesulfonic acid as the dropping vessel (A), and the mixture was stirred and mixed to obtain a homogeneous mixture. Subsequently, 76.9 parts of 2-(2-vinyloxyethoxy)ethyl methacrylate was added dropwise to the mixture, taking care to avoid heat generation. After the dropwise addition was completed, the mixture was stirred at 30°C for 3 hours, and then 0.39 parts of triethylamine and 2.9 parts of di-2-ethylhexyl peroxydicarbonate ("PERLOYL (registered trademark) OPP" manufactured by NOF Corporation) were charged and used as a dropping tank (A). As a dropping tank (B), a beaker containing 1.0 part of n-dodecyl mercaptan and 59.0 parts of propylene glycol monomethyl ether acetate was prepared. After the temperature of the reaction tank reached 60°C, dropwise addition from the dropping tank was initiated over 3 hours while maintaining the same temperature, and polymerization was carried out. After the dropwise addition was completed, the temperature was maintained at 60°C and the mixture was aged for 6 hours. Thereafter, the mixture was cooled to room temperature, and a polymer (B-1) was obtained. The physical properties of the obtained polymer are shown in Table 2.

[0233] Example 2 Synthesis of Polymer (B-2) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube, and a dropping vessel inlet was charged with 133.0 parts of propylene glycol monomethyl ether acetate, and after purging with nitrogen, the vessel was heated to 50° C. Separately, a dropping vessel (A) was prepared by stirring and mixing 42.9 parts of propylene glycol monomethyl ether acetate, 100.0 parts of 2-(2-(1-isopropoxyethoxy)ethoxy)ethyl methacrylate, and 2.0 parts of 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), in a beaker. A dropping vessel (B) was prepared by stirring and mixing 2.0 parts of n-dodecyl mercaptan and 58.0 parts of propylene glycol monomethyl ether acetate in a beaker. After the temperature of the reaction vessel reached 50°C, dropwise addition from the dropping vessel was started over 3 hours while maintaining the same temperature, and polymerization was carried out. After completion of the dropwise addition, the temperature was maintained at 50°C and aging was carried out for 7 hours. Thereafter, the mixture was cooled to room temperature, and polymer (B-2) was obtained. The physical properties of the obtained polymer are shown in Table 2.

[0234] Example 3 Synthesis of Polymer (B-3) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube, and a dropping vessel inlet was charged with 109.3 parts of propylene glycol monomethyl ether acetate, and after purging with nitrogen, the vessel was heated to 60° C. Separately, a dropping vessel was prepared by stirring and mixing 100.0 parts of propylene glycol monomethyl ether acetate, 100.0 parts of 2-(2-(1-ethoxyethoxy)ethoxy)ethyl methacrylate, and 3.5 parts of n-dodecyl mercaptan in a beaker. A dropping vessel was prepared by stirring and mixing 2.0 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) (V-65 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 28.0 parts of propylene glycol monomethyl ether acetate in a beaker. After the temperature of the reaction vessel reached 60°C, dropwise addition from the dropping vessel was initiated over 3 hours while maintaining the same temperature, and polymerization was carried out. A total of 30 parts from the initiator vessel was added to the reaction vessel in 5 parts increments, 6 times at 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours after the start of polymerization. After completion of the dropwise addition, the reaction vessel was heated to 70°C and aged for 10 hours. Thereafter, it was cooled to room temperature, and polymer (B-3) was obtained. The physical properties of the obtained polymer are shown in Table 2.

[0235] Example 4 Synthesis of Polymer (B-4) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube, and a dropping vessel inlet was charged with 115.3 parts of propylene glycol monomethyl ether acetate, and after purging with nitrogen, the vessel was heated to 60° C. Separately, a dropping vessel (A) was prepared by stirring and mixing 2.0 parts of N-benzylmaleimide, 38.0 parts of cyclohexyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 30.0 parts of propylene glycol monomethyl ether acetate, and 2.0 parts of n-dodecyl mercaptan in a beaker. A dropping vessel (B) was prepared by stirring and mixing 60.0 parts of propylene glycol monomethyl ether acetate, 6.9 parts of acetic acid, and 0.002 parts of p-toluenesulfonic acid in a beaker. Next, 23.1 parts of 2-(2-vinyloxyethoxy)ethyl methacrylate was added dropwise to the above mixture, taking care to avoid heat generation. After the dropwise addition was completed, the mixture was stirred at 30°C for 3 hours, and 0.12 parts of triethylamine was added and stirred to prepare the dropping tank (B). As the initiator tank, a beaker was prepared in which 2.9 parts of di-2-ethylhexyl peroxydicarbonate ("Perloyl (registered trademark) OPP" manufactured by NOF Corporation) and 27.1 parts of propylene glycol monomethyl ether acetate were stirred and mixed. After the temperature of the reaction tank reached 60°C, dropping was initiated from dropping tanks (A) and (B) over 3 hours while maintaining the same temperature, and polymerization was carried out. A total of 30 parts of the initiator tank was added at 0, 30 minutes, 1 hour, and 1. The mixture was added to the reaction vessel in six portions, 5 parts at a time, over 5 hours, 2 hours, and 2.5 hours. After the completion of the dropwise addition, the temperature was maintained at 60°C and the mixture was aged for 6 hours. After cooling to room temperature, 11.5 parts of succinic anhydride, 11.7 parts of triethylamine, and 29.6 parts of propylene glycol monomethyl ether acetate were added to the reaction vessel and reacted at 50°C for 1 hour. After the reaction, the mixture was cooled to room temperature to obtain Polymer (B-4). The physical properties of the obtained polymer are shown in Table 2.

[0236] Example 5 Synthesis of Polymer (B-5) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube, and a dropping vessel inlet was charged with 146.0 parts of propylene glycol monomethyl ether acetate, and after purging with nitrogen, the vessel was heated to 60° C. Separately, as the dropping vessel (A), a beaker was prepared by stirring and mixing 20.0 parts of cyclohexyl methacrylate, 40.0 parts of 2-hydroxyethyl methacrylate, 2.0 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) (V-65 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 40.0 parts of propylene glycol monomethyl ether acetate. As the dropping vessel (B), a beaker was charged with 46.5 parts of propylene glycol monomethyl ether acetate, 9.2 parts of isopropanol, and 0.003 parts of p-toluenesulfonic acid, and the mixture was stirred and mixed to obtain a uniform mixture. Next, 30.8 parts of 2-(2-vinyloxyethoxy)ethyl methacrylate was added dropwise to the above mixture, while taking care to avoid heat generation. After completion of the addition, the mixture was stirred at 30°C for 3 hours, and then 0.16 parts of triethylamine and 3.5 parts of n-dodecyl mercaptan were added to form a dropping tank (B). After the temperature of the reaction tank reached 60°C, dropwise addition was initiated from the dropping tanks (A) and (B) over 3 hours while maintaining the same temperature, and polymerization was carried out. After completion of the addition, the temperature was raised to 70°C and aging was carried out for 10 hours. After cooling to room temperature, 15.4 parts of succinic anhydride, 15.6 parts of triethylamine, and 42.1 parts of propylene glycol monomethyl ether acetate were charged to the reaction tank, and the reaction was carried out at 50°C for 1 hour. After the reaction, the mixture was cooled to room temperature, and polymer (B-5) was obtained. The physical properties of the obtained polymer are shown in Table 2.

[0237] Example 6 Synthesis of Polymer (B-6) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet pipe, a condenser, and a dropping vessel inlet was charged with 160.8 parts of propylene glycol monomethyl ether acetate, stirred and mixed, then purged with nitrogen, and heated to 50°C. On the other hand, a dropping tank (A) was prepared by stirring and mixing 15.0 parts of 2-(2-(1-acetoxyethoxy)ethoxy)ethyl methacrylate, 70.0 parts of methyl methacrylate, 15.0 parts of methacrylic acid, 2.0 parts of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 15.0 parts of propylene glycol monomethyl ether acetate in a beaker. A dropping tank (B) was prepared by charging 2.0 parts of n-dodecyl mercaptan and 58.0 parts of propylene glycol monomethyl ether acetate in a beaker and stirring and mixing. After the temperature of the reaction tank reached 50°C, dropwise addition was initiated from the dropping tanks (A) and (B) over 3 hours while maintaining the same temperature, and polymerization was carried out. After completion of the dropwise addition, the temperature was maintained at 50°C and the mixture was aged for 7 hours. The mixture was then cooled to room temperature to obtain polymer (B-6). The physical properties of the resulting polymer are shown in Table 2.

[0238] Example 7 Synthesis of Polymer (B-7) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube, and a dropping vessel inlet was charged with 190.8 parts of propylene glycol monomethyl ether acetate and 14.3 parts of triethylamine, and after replacing the atmosphere with nitrogen, the vessel was heated to 60°C. On the other hand, a dropping vessel was prepared by stirring and mixing 10.0 parts of N-phenylmaleimide, 50.0 parts of cyclohexyl methacrylate, 10.0 parts of 2-hydroxyethyl methacrylate, 10.0 parts of acrylic acid, 20.0 parts of 2-(2-(1-ethoxyethoxy)ethoxy)ethyl methacrylate, 20.0 parts of propylene glycol monomethyl ether acetate, and 4.0 parts of n-dodecyl mercaptan in a beaker. As an initiator vessel, a beaker was charged with di-2-ethylhexyl peroxydicarbonate ("PERROIL (registered trademark)" manufactured by NOF Corporation). A mixture of 2.9 parts of "OPP" and 27.1 parts of propylene glycol monomethyl ether acetate was prepared by stirring. After the temperature of the reaction vessel reached 60°C, dropwise addition from the dropping vessel was initiated over 3 hours while maintaining the same temperature, and polymerization was carried out. A total of 30 parts from the initiator vessel was added to the reaction vessel in 5 parts increments in 6 times, at 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours after the start of polymerization. After completion of dropwise addition, the temperature was maintained at 60°C, and the mixture was aged for 6 hours. Thereafter, the mixture was cooled to room temperature, and polymer (B-7) was obtained. The physical properties of the obtained polymer are shown in Table 2.

[0239] Example 8 Synthesis of Polymer (B-8) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube, and a dropping vessel inlet was charged with 172.6 parts of propylene glycol monomethyl ether acetate and 23.9 parts of triethylamine, and the atmosphere was replaced with nitrogen, followed by heating to 50° C. Separately, a dropping vessel (A) was prepared by stirring and mixing 5.0 parts of N-cyclohexylmaleimide, 20.0 parts of methacrylic acid, 20.0 parts of propylene glycol monomethyl ether acetate, and 3.0 parts of n-dodecyl mercaptan in a beaker. A dropping vessel (B) was prepared by stirring and mixing 15.0 parts of propylene glycol monomethyl ether acetate, 17.3 parts of acetic acid, and 0.006 parts of p-toluenesulfonic acid in a beaker. Next, 57.7 parts of 2-(2-vinyloxyethoxy)ethyl methacrylate was added dropwise to the mixture, taking care to avoid heat generation. After the dropwise addition was completed, the mixture was stirred at 30°C for 3 hours to create the dropping tank (B). As an initiator tank, 2.0 parts of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 28.0 parts of propylene glycol monomethyl ether acetate were prepared by stirring. After the temperature of the reaction tank reached 50°C, dropwise addition from the dropping tanks (A) and (B) was initiated over 3 hours while maintaining the same temperature, and polymerization was carried out. A total of 30 parts of the initiator tank was added to the reaction tank in 5 parts increments, 6 times at 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours after the start of polymerization. After the dropwise addition was completed, the temperature was maintained at 50°C and the mixture was aged for 7 hours. The polymer was then cooled to room temperature to obtain Polymer (B-8). The physical properties of the obtained polymer are shown in Table 2.

[0240] Example 9 Synthesis of Polymer (B-9) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet pipe, a condenser, and a dropping vessel inlet was charged with 145.8 parts of propylene glycol monomethyl ether acetate, and the atmosphere was replaced with nitrogen, followed by heating to 60°C. On the other hand, as the dropping tank (A), 10.0 parts of N-benzylmaleimide, 30.0 parts of cyclohexyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 2.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (Fujifilm Wako Pure Chemical Industries, Ltd. V-65), and 30.0 parts of propylene glycol monomethyl ether acetate were stirred and mixed in a beaker, and as the dropping tank (B), 57.5 parts of propylene glycol monomethyl ether acetate, 6.9 parts of acetic acid, and 0.002 parts of p-toluenesulfonic acid were charged in a beaker, stirred and mixed to obtain a homogeneous mixture. Subsequently, 23.1 parts of 2-(2-vinyloxyethoxy)ethyl methacrylate were added dropwise to the mixture, taking care to avoid heat generation. After completion of the dropwise addition, the mixture was stirred at 30°C for 3 hours, and then 0.10 parts of diethylmethylamine and 2.5 parts of n-dodecyl mercaptan were added to form a dropping tank (B). After the temperature of the reaction tank reached 60°C, dropwise addition was initiated from the dropping tanks (A) and (B) over 3 hours while maintaining the same temperature, and polymerization was carried out. 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, 7.7 parts of succinic anhydride, 6.7 parts of diethylmethylamine, and 21.8 parts of propylene glycol monomethyl ether acetate were charged into the reaction tank, and the reaction was carried out at 50°C for 1 hour. After the reaction, the mixture was cooled to room temperature, and polymer (B-9) was obtained. The physical properties of the obtained polymer are shown in Table 2.

[0241] Example 10 Synthesis of Polymer (B-10) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet pipe, a condenser, and a dropping vessel inlet was charged with 228.3 parts of propylene glycol monomethyl ether acetate, and the atmosphere was replaced with nitrogen, followed by heating to 60°C. On the other hand, a dropping tank (A) was prepared by stirring and mixing 15.0 parts of cyclohexyl methacrylate, 55.0 parts of 2-hydroxyethyl methacrylate, 30.0 parts of 2-(2-(1-acetoxyethoxy)ethoxy)ethyl methacrylate, 2.9 parts of di-2-ethylhexyl peroxydicarbonate (NOF Corporation's "PERLOYL (registered trademark) OPP"), and 30.0 parts of propylene glycol monomethyl ether acetate in a beaker. A dropping tank (B) was prepared by stirring and mixing 2.5 parts of n-dodecyl mercaptan and 57.5 parts of propylene glycol monomethyl ether acetate in a beaker. After the temperature of the reaction tank reached 60°C, dropwise addition was initiated from the dropping tanks (A) and (B) over 3 hours while maintaining the same temperature, and polymerization was carried out. After completion of the dropping, the temperature was maintained at 60°C and the mixture was aged for 6 hours. The mixture was then cooled to room temperature, and 26.2 parts of 2-methacryloyloxyethyl isocyanate, 16.8 parts of triethylamine, and 0.2 parts of Antaji W400 were added. An oxygen / nitrogen mix gas adjusted to an oxygen concentration of 7% was bubbled through at 20 ml / min, and the mixture was reacted at 90°C for 2 hours. After cooling to room temperature, 16.6 parts of succinic anhydride was added, and the mixture was reacted at 50°C for 1 hour. After completion of the reaction, the mixture was cooled to room temperature, and polymer (B-10) was obtained. The physical properties of the obtained polymer are shown in Table 2.

[0242] Example 11 Synthesis of Polymer (B-11) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping vessel inlet was charged with 263.7 parts of propylene glycol monomethyl ether acetate, and after purging with nitrogen, the vessel was heated to 60° C. On the other hand, a dropping vessel was prepared by stirring and mixing 15.0 parts of N-benzylmaleimide, 15.0 parts of cyclohexyl methacrylate, 25.0 parts of glycidyl methacrylate, 20.0 parts of 2-hydroxyethyl methacrylate, 25.0 parts of 2-(2-(1-isopropoxyethoxy)ethoxy)ethyl methacrylate, 3.0 parts of n-dodecyl mercaptan, and 25.0 parts of propylene glycol monomethyl ether acetate in a beaker. As an initiator tank, 2.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 28.0 parts of propylene glycol monomethyl ether acetate were stirred and mixed in a beaker. After the temperature of the reaction tank reached 60°C, dropwise addition from the dropping tank was initiated over 3 hours while maintaining the same temperature, and polymerization was carried out. A total of 30 parts of the initiator tank was added to the reaction tank in 5-part increments in six installments, at 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours after the start of polymerization. After completion of the dropwise addition, the reaction tank was heated to 70°C and aged for 10 hours. After that, it was cooled to room temperature, and 5.1 parts of acrylic acid, 12.2 parts of triethylamine, and 0.2 parts of Antaji W400 were added, and the mixture was reacted at 110°C for 7 hours while bubbling oxygen / nitrogen MIX gas adjusted to an oxygen concentration of 7% at 20 ml / min. After that, it was cooled to room temperature, and 12.0 parts of succinic anhydride was added, and the mixture was reacted at 50°C for 1 hour. After completion of the reaction, it was cooled to room temperature to obtain polymer (B-11). Various physical properties of the obtained polymer are shown in Table 2.

[0243] Example 12 Synthesis of Polymer (B-12) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping vessel inlet was charged with 215.7 parts of propylene glycol monomethyl ether acetate, and after purging with nitrogen, the vessel was heated to 60° C. Separately, a dropping vessel (A) was prepared by stirring and mixing 5.0 parts of N-phenylmaleimide, 5.0 parts of cyclohexyl methacrylate, 35.0 parts of glycidyl methacrylate, 35.0 parts of 2-hydroxyethyl methacrylate, and 5.0 parts of propylene glycol monomethyl ether acetate in a beaker. A dropping vessel (B) was prepared by stirring and mixing 68.0 parts of propylene glycol monomethyl ether acetate, 3.7 parts of ethanol, and 0.002 parts of p-toluenesulfonic acid in a beaker. Next, 16.3 parts of 2-(2-vinyloxyethoxy)ethyl methacrylate was added dropwise to the mixture, taking care to avoid heat generation. After the addition was completed, the mixture was stirred at 30°C for 3 hours, and then 0.08 parts of triethylamine and 2.0 parts of n-dodecyl mercaptan were added to form a dropping tank (B). As an initiator tank, a beaker containing 2.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 28.0 parts of propylene glycol monomethyl ether acetate was prepared by stirring and mixing. After the temperature of the reaction tank reached 60°C, dropwise addition from dropping tanks (A) and (B) was initiated over 3 hours while maintaining the same temperature, and polymerization was carried out. A total of 30 parts of the initiator tank was added to the reaction tank in 5 parts increments, 6 times at 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours after the start of polymerization. After completion of the dropwise addition, the reaction vessel was heated to 70 ° C. and aged for 10 hours. Thereafter, it was cooled to room temperature, and 14.0 parts of methacrylic acid, 26.9 parts of triethylamine, and 0.2 parts of Antaji W400 were added, and the mixture was reacted at 110 ° C. for 7 hours while bubbling oxygen / nitrogen MIX gas adjusted to an oxygen concentration of 7% at 20 ml / min. Thereafter, it was cooled to room temperature, and 26.6 parts of succinic anhydride was added, and the mixture was reacted at 50 ° C. for 1 hour. After completion of the reaction, it was cooled to room temperature to obtain polymer (B-12). Various physical properties of the obtained polymer are shown in Table 2.

[0244] Example 13 Synthesis of Polymer (B-13) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube, and a dropping vessel inlet was charged with 145.3 parts of propylene glycol monomethyl ether acetate, and after purging with nitrogen, the vessel was heated to 60° C. Separately, a dropping vessel (A) was prepared by stirring and mixing 2.0 parts of N-benzylmaleimide, 38.0 parts of cyclohexyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 30.0 parts of propylene glycol monomethyl ether acetate, and 2.0 parts of n-dodecyl mercaptan in a beaker. A dropping vessel (B) was prepared by stirring and mixing 30.0 parts of propylene glycol monomethyl ether acetate, 7.3 parts of acetic acid, and 0.002 parts of p-toluenesulfonic acid in a beaker. Next, 22.7 parts of 2-(2-vinyloxyethoxy)ethyl acrylate was added dropwise to the above mixture, taking care to avoid heat generation. After the dropwise addition was completed, the mixture was stirred at 30°C for 3 hours, and 0.12 parts of triethylamine was added. The mixture was stirred and mixed to form the dropping tank (B). As the initiator tank, 2.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 28.0 parts of propylene glycol monomethyl ether acetate were prepared in a beaker and stirred and mixed. After the temperature of the reaction tank reached 60°C, dropwise addition from the dropping tanks (A) and (B) was initiated over 3 hours while maintaining the same temperature, and polymerization was carried out. A total of 30 parts of the initiator tank was added to the reaction tank in 5 parts increments, 6 times at 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours after the start of polymerization. After the dropwise addition was completed, the temperature was raised to 70°C and aging was carried out for 6 hours. After that, after cooling to room temperature, 11.5 parts of succinic anhydride, 11.7 parts of triethylamine, and 29.6 parts of propylene glycol monomethyl ether acetate were charged into the reaction vessel and reacted at 50°C for 1 hour. After the reaction, the mixture was cooled to room temperature to obtain polymer (B-13). Various physical properties of the obtained polymer are shown in Table 2.

[0245] Example 14 Synthesis of Polymer (B-14) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube, and a dropping vessel inlet was charged with 145.3 parts of propylene glycol monomethyl ether acetate, and after purging with nitrogen, the vessel was heated to 60° C. Separately, a dropping vessel (A) was prepared by stirring and mixing 2.0 parts of N-benzylmaleimide, 38.0 parts of cyclohexyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 30.0 parts of propylene glycol monomethyl ether acetate, and 2.0 parts of n-dodecyl mercaptan in a beaker. A dropping vessel (B) was prepared by stirring and mixing 30.0 parts of propylene glycol monomethyl ether acetate, 8.5 parts of propionic acid, and 0.002 parts of p-toluenesulfonic acid in a beaker. Next, 21.5 parts of 2-(2-vinyloxyethoxy)ethyl acrylate was added dropwise to the above mixture, taking care to avoid heat generation. After the dropwise addition was completed, the mixture was stirred at 30°C for 3 hours, and 0.12 parts of triethylamine was added. The mixture was stirred and mixed to form the dropping tank (B). As the initiator tank, 2.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 28.0 parts of propylene glycol monomethyl ether acetate were prepared in a beaker and stirred and mixed. After the temperature of the reaction tank reached 60°C, dropwise addition from the dropping tanks (A) and (B) was initiated over 3 hours while maintaining the same temperature, and polymerization was carried out. A total of 30 parts of the initiator tank was added to the reaction tank in 5 parts increments, 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours after the start of polymerization. After the dropwise addition was completed, the temperature was raised to 70°C and aging was carried out for 6 hours. After that, after cooling to room temperature, 11.5 parts of succinic anhydride, 11.7 parts of triethylamine, and 29.6 parts of propylene glycol monomethyl ether acetate were charged into the reaction vessel and reacted at 50°C for 1 hour. After the reaction, the mixture was cooled to room temperature to obtain polymer (B-14). Various physical properties of the obtained polymer are shown in Table 2.

[0246] Example 15 Synthesis of Polymer (B-15) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube, and a dropping vessel inlet was charged with 146.8 parts of propylene glycol monomethyl ether acetate, and after purging with nitrogen, the vessel was heated to 60° C. Separately, a dropping vessel (A) was prepared by stirring and mixing 2.0 parts of N-benzylmaleimide, 35.5 parts of cyclohexyl methacrylate, 1.0 part of methyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 30.0 parts of propylene glycol monomethyl ether acetate, and 2.0 parts of n-dodecyl mercaptan in a beaker. A dropping vessel (B) was prepared by stirring and mixing 28.5 parts of propylene glycol monomethyl ether acetate, 10.1 parts of butyric acid, and 0.002 parts of p-toluenesulfonic acid in a beaker. Next, 21.4 parts of 2-(2-vinyloxyethoxy)ethyl acrylate was added dropwise to the above mixture, taking care to avoid heat generation. After the dropwise addition was completed, the mixture was stirred at 30°C for 3 hours, and 0.12 parts of triethylamine was added. The mixture was stirred and mixed to form the dropping tank (B). As the initiator tank, 2.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 28.0 parts of propylene glycol monomethyl ether acetate were prepared in a beaker and stirred and mixed. After the temperature of the reaction tank reached 60°C, dropwise addition from the dropping tanks (A) and (B) was initiated over 3 hours while maintaining the same temperature, and polymerization was carried out. A total of 30 parts of the initiator tank was added to the reaction tank in 5 parts increments, 6 times at 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours after the start of polymerization. After the dropwise addition was completed, the temperature was raised to 70°C and aging was carried out for 6 hours. After that, after cooling to room temperature, 11.5 parts of succinic anhydride, 11.7 parts of triethylamine, and 29.6 parts of propylene glycol monomethyl ether acetate were charged into the reaction vessel and reacted at 50°C for 1 hour. After the reaction, the mixture was cooled to room temperature to obtain polymer (B-15). Various physical properties of the obtained polymer are shown in Table 2.

[0247] Example 16 Synthesis of Polymer (B-16) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube, and a dropping vessel inlet was charged with 159.8 parts of propylene glycol monomethyl ether acetate, and after purging with nitrogen, the vessel was heated to 60° C. Separately, a dropping vessel (A) was prepared by stirring and mixing 2.0 parts of N-benzylmaleimide, 22.5 parts of cyclohexyl methacrylate, 1.0 part of methyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 30.0 parts of propylene glycol monomethyl ether acetate, and 2.0 parts of n-dodecyl mercaptan in a beaker. A dropping vessel (B) was prepared by stirring and mixing 15.5 parts of propylene glycol monomethyl ether acetate, 23.1 parts of lauric acid, and 0.002 parts of p-toluenesulfonic acid in a beaker. The mixture was heated to 50° C. and stirred to obtain a uniform mixture. Next, 21.4 parts of 2-(2-vinyloxyethoxy)ethyl acrylate was added dropwise to the above mixture, taking care to avoid heat generation. After the dropwise addition was completed, the mixture was stirred at 50°C for 3 hours, and 0.12 parts of triethylamine was added. The mixture was stirred and mixed to form the dropping tank (B). As the initiator tank, 2.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 28.0 parts of propylene glycol monomethyl ether acetate were prepared in a beaker and stirred and mixed. After the temperature of the reaction tank reached 60°C, dropwise addition from the dropping tanks (A) and (B) was initiated over 3 hours while maintaining the same temperature, and polymerization was carried out. A total of 30 parts of the initiator tank was added to the reaction tank in 5 parts increments, 6 times at 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours after the start of polymerization. After the dropwise addition was completed, the temperature was raised to 70°C and aging was carried out for 6 hours. After that, after cooling to room temperature, 11.5 parts of succinic anhydride, 11.7 parts of triethylamine, and 29.6 parts of propylene glycol monomethyl ether acetate were charged into the reaction vessel and reacted at 50°C for 1 hour. After the reaction, the mixture was cooled to room temperature to obtain polymer (B-16). Various physical properties of the obtained polymer are shown in Table 2.

[0248] Comparative Example 1 Synthesis of Polymer (B-17) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping vessel inlet was charged with 143.3 parts of propylene glycol monomethyl ether acetate, purged with nitrogen, and then heated to 70°C. Separately, a dropping vessel (A) was prepared by stirring and mixing 28.0 parts of 3-carboxyadamantyl methacrylate, 12.8 parts of azobisisobutyronitrile, and 72.0 parts of propylene glycol monomethyl ether acetate in a beaker. A dropping vessel (B) was prepared by stirring and mixing 72.0 parts of 4-(1-methoxy)ethoxycyclohexyl methacrylate and 18.0 parts of propylene glycol monomethyl ether acetate in a beaker. After the temperature of the reaction vessel reached 70°C, dropwise addition was initiated from the dropping vessels (A) and (B) over 3 hours while maintaining the same temperature, and polymerization was carried out. After completion of the dropping, the mixture was maintained at 70°C and aged for 7 hours. Thereafter, the mixture was cooled to room temperature to obtain polymer (B-17). The physical properties of the obtained polymer are shown in Table 2.

[0249] Comparative Example 2 Synthesis of Polymer (B-18) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping vessel inlet was charged with 143.3 parts of propylene glycol monomethyl ether acetate and 10.8 parts of triethylamine, and the atmosphere was replaced with nitrogen. The mixture was then heated to 70°C. Separately, a dropping vessel (A) was prepared by stirring and mixing 28.0 parts of 3-carboxyadamantyl methacrylate, 12.8 parts of azobisisobutyronitrile, and 72.0 parts of propylene glycol monomethyl ether acetate in a beaker. A dropping vessel (B) was prepared by stirring and mixing 72.0 parts of 4-(1-methoxy)ethoxycyclohexyl methacrylate and 18.0 parts of propylene glycol monomethyl ether acetate in a beaker. After the temperature of the reaction vessel reached 70°C, dropwise addition was initiated from the dropping vessels (A) and (B) over a period of 3 hours while maintaining the same temperature, and polymerization was carried out. After the dropwise addition, the temperature was maintained at 70°C and the mixture was aged for 7 hours. Then, the mixture was cooled to room temperature to obtain polymer (B-18). The physical properties of the obtained polymer are shown in Table 2.

[0250] (Comparative Example 3) Synthesis of Polymer (B-19) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet, a cooling tube, and a dropping vessel inlet was charged with 105.3 parts of propylene glycol monomethyl ether acetate, and after nitrogen substitution, the temperature was raised to 70 ° C. On the other hand, as the dropping vessel (A), a beaker was prepared by stirring and mixing 76.4 parts of cyclohexyl methacrylate, 14.7 parts of glycidyl methacrylate, 8.9 parts of methacrylic acid, 50.0 parts of propylene glycol monomethyl ether acetate, and 2.7 parts of t-butyl peroxypivalate ("Luperox (registered trademark) 11" manufactured by Arkema Yoshitomi Co., Ltd.), and a dropping vessel (B) was prepared by stirring and mixing 2.0 parts of n-dodecyl mercaptan and 78 parts of propylene glycol monomethyl ether acetate. After the temperature of the reaction vessel reached 70°C, dropwise addition from the dropping vessel was started over 3 hours while maintaining the same temperature, and polymerization was carried out. After the dropwise addition was completed, the temperature was maintained at 70°C for 30 minutes, and then the temperature was raised to 80°C and aged for 180 minutes to obtain polymer (B-19). The physical properties of the obtained polymer are shown in Table 2.

[0251]

[0252] The descriptions in Table 2 represent the following. BzMI: N-benzylmaleimide, PMI: N-phenylmaleimide, CHMI: N-cyclohexylmaleimide, CHMA: cyclohexyl methacrylate, MMA: methyl methacrylate, HEMA: 2-hydroxyethyl methacrylate, MECMA: 4-(1-methoxy)ethoxycyclohexyl methacrylate, AA: acrylic acid, MAA: methacrylic acid, AMAA: 3-carboxyadamantyl methacrylate, GMA: glycidyl methacrylate, MOI: 2-methacryloyloxyethyl isocyanate, SAH: succinic anhydride, OPP: di-2-ethylhexyl peroxydicarbonate (NOF Corporation, "Perloyl (registered trademark) OPP"), V70: 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (Fujifilm Wako Pure Chemical Industries, Ltd., V-70). V65: 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) AIBN: Azobisisobutyronitrile L11: t-butyl peroxypivalate ("Luperox 11" manufactured by Arkema Yoshitomi Co., Ltd.) TEA: Triethylamine DEMA: Diethylmethylamine

[0253] (Preparation of Photosensitive Resin Composition) 35 parts of polymer (B-1), 30 parts of pigment dispersion 1, 30 parts of dipentaerythritol hexaacrylate (DPHA), and 5 parts of IRGACURE (registered trademark) OXE02 (manufactured by BASF Japan Ltd.) were added 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 20% by mass, followed by stirring to obtain a photosensitive resin composition (C-1).

[0254] (Preparation of Pigment Dispersion 1) 12.9 parts of propylene glycol monomethyl ether acetate, 0.4 parts of Disparlon DA-7301 as a basic dispersant, 2.25 parts of C.I. Pigment Green 58 and 1.5 parts of C.I. Pigment Yellow 138 as colorants were mixed and dispersed for 3 hours using a paint shaker to obtain Pigment Dispersion 1 (solid content 22% by mass).

[0255] Photosensitive resin compositions (C-2) to (C-19) were obtained in the same manner as in Example 1, except for the formulations shown in Table 3. The developability, solvent resistance, and storage stability of the obtained photosensitive resin compositions were evaluated by the methods described above. The results are shown in Table 3.

[0256]

[0257] Tables 2 and 3 confirm that the polymers of Examples 4 to 16 exhibited faster development rates and improved solvent resistance compared to the polymers of Comparative Examples 1 to 3. The improved development rates are believed to be due to the acetal monomer units of the polymers of Examples 4 to 16 containing PEG chains and being highly hydrophilic. On the other hand, the acetal monomer units and acid group-containing monomer units of the polymer backbone in Comparative Examples 1 and 2 have alicyclic structures, resulting in high hydrophobicity and steric hindrance, which slowed the development rate and hindered the crosslinking reaction, leading to a tendency toward poor solvent resistance. Furthermore, the high reactivity of acid groups with epoxy groups in Comparative Example 3 resulted in poor storage stability of the polymer and photosensitive resin composition, resulting in fewer unreacted acid groups at the time of development, leading to a slow development rate. Furthermore, the crosslinking reaction of acid-epoxy polymers results in lower crosslink density upon curing compared to reactions such as cationic polymerization of vinyl ethers, which is believed to have also led to a tendency toward poor solvent resistance.

[0258] It was confirmed that Examples 1 to 16 had better storage stability than Comparative Examples 1 to 3. The lower storage stability of Examples 11 and 12 compared to the other Examples is thought to be due to the resins having epoxy groups in the side chains and containing a neutralizing amount of triethylamine (a basic compound). On the other hand, the poor storage stability of the Comparative Examples is due to the fact that when a monomer that generates a vinyl ether is copolymerized with an alicyclic skeleton, elimination easily proceeds even during storage, resulting in crosslinking of the vinyl ether group. On the other hand, the linear or branched chain structures of the Examples exhibit good stability during storage, with the vinyl ether not easily eliminating. The vinyl ether elimination occurs all at once during low-temperature baking, and the resulting vinyl ether is highly reactive, resulting in good solvent resistance. This overcomes the trade-off between storage stability and solvent resistance. Furthermore, Comparative Example 1 does not contain a basic compound that neutralizes the acid group-containing monomer units. Therefore, elimination of the protecting group from the vinyl ether proceeded during storage of the polymer solution, regenerating the vinyl ether group and promoting crosslinking. This is thought to have resulted in poorer storage stability compared to Comparative Example 2. It is believed that the storage stability of Example 6 was also worse than that of the other Examples for the same reason.

[0259] It was confirmed that Examples 1 to 3 exhibited better solvent resistance and storage stability than Comparative Examples 1 to 3, but had slower development rates. This is thought to be due to the absence of acid group-containing monomer units in the polymers. Furthermore, it was confirmed that Examples 1, 4, 8, 9, 10, 13, 14, 15, and 16 exhibited smaller viscosity change rates and tended to have better storage stability than Examples 2, 3, 5, 7, 11, and 12. This is because the stability of the polymers AEEM, AEEA, PEEA, BEEA, and LEEA is better than that of IEEM and EEEM, and therefore carboxylic acids are preferred over alcohols as the protecting monomer for the vinyl ether group.

[0260] It was confirmed that Example 13 had a faster development rate than Example 4. This is thought to be due to the effect of changing from VEEM to VEEA, which lowered the glass transition temperature (Tg) of the resin. Similarly, Example 15 was compared with Example 14, and it was confirmed that Example 14 had the same solvent resistance but a smaller viscosity change rate and better storage stability than Example 13. This is thought to be because a longer molecular chain of the carboxylic acid compound forming the acetal monomer unit is more effective in suppressing detachment of the carboxylic acid compound, improving storage stability. On the other hand, it was confirmed that Example 16 had the same storage stability but worsened solvent resistance compared to Example 15. This is thought to be because a longer molecular chain of the carboxylic acid compound is more effective in suppressing detachment of the carboxylic acid compound, but a longer molecular chain reduces the crosslink density upon thermal curing, thereby reducing solvent resistance. Therefore, butyric acid, which has a carboxylic acid with four carbon atoms, is most preferred.

[0261] (Confirmation of the Effect of Dilution Solvent) The following procedure was performed to investigate the effect of the dilution solvent on the storage stability of the polymer. A polymer solution was prepared by adding 26 parts of dilution solvent to 74 parts of polymer (B-15) as is (20 parts solids, 54 parts volatiles), and the storage stability was evaluated using this solution. The storage stability was evaluated based on the increase in weight-average molecular weight before and after storage at 40°C for 1 week. The weight-average molecular weight of the polymer was measured by the method described above. Table 4 shows the weight-average molecular weight (%) after storage, where the weight-average molecular weight of the polymer before storage was taken as 100%. The smaller the increase in weight-average molecular weight, the better the storage stability of the polymer was evaluated to be. Five types of dilution solvents were used: propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dimethylformamide, diethylene glycol ethyl methyl ether, and 1-butanol. The evaluation results are shown in Table 4.

[0262]

[0263] From Table 4, it was found that Examples 17, 18, 19, and 20 had a smaller rate of change in the weight-average molecular weight of the polymer compared to Example 21. From this, it is thought that adding an alcohol solvent, an ether solvent, or an amide solvent to the polymer improves storage stability. Furthermore, the rate of change in weight-average molecular weight increases in the order of Examples 17, 18, 19, and 20. From this, it is thought that the effect of improving storage stability is greater in the order of ether solvents, alcohol solvents, and amide solvents. Furthermore, it was found that Example 18 had a smaller rate of change in weight-average molecular weight compared to Example 19. From this, it is thought that among alcohol solvents, secondary alcohol solvents are more suitable than primary alcohol solvents for improving storage stability.

[0264] (Confirmation of the Effect of Dispersant) The following procedure was carried out to investigate the effect of adding a dispersant on the storage stability of the polymer. Storage stability was evaluated using a polymer solution in which 10 parts by mass of an amine-based dispersant, Disperbyk-164 (amine value 18 mg KOH / g, solids content 60%, manufactured by BYK-Chemie), was added to 90 parts by mass of polymer (B-5) or polymer (B-11). The storage stability was evaluated based on the change in acid value before and after storage at 40°C for one week. The acid value was measured using the method described above. The smaller the change in acid value, the better the storage stability of the polymer was evaluated to be. The evaluation results are shown in Table 5. For reference, the change in acid value was also evaluated in the same manner for polymer (B-5) and polymer (B-11) alone.

[0265]

[0266] As can be seen from Table 5, the resin solutions of Examples 22 to 25 had smaller acid value changes and better storage stability than the resin solutions of Comparative Examples 4 and 5. Comparing Examples 22 and 23 containing polymer (B-5) with Examples 24 and 25 containing polymer (B-11), the resin solutions of the Examples containing polymer (B-5) had smaller acid value changes, regardless of the presence or absence of an amine-based dispersant. Considering these results, it was found that the lower the amount of epoxy groups in the resin, the better the storage stability.

[0267] Furthermore, comparing Example 22 with Example 23, it was found that the resin solution of Example 22 containing an amine-based dispersant had a smaller acid value change and better storage stability. This was thought to be due to the suppression of acetal deprotection by the addition of the amine-based dispersant. On the other hand, comparing Example 24 with Example 25, it was found that the resin solution of Example 24 containing an amine-based dispersant had a larger acid value change. This tendency was also observed in the comparison between Comparative Example 4 and Comparative Example 5. From these results, it was thought that the amine-based dispersant reduces the storage stability of resins containing epoxy groups. This is thought to be due to the addition of the amine-based dispersant promoting the reaction between acid groups and epoxy groups. From the above, it was found that the polymers of the examples had excellent storage stability, and that when a composition containing an amine-based dispersant was formed, a lower epoxy group content resulted in better storage stability. Furthermore, comparing Example 23, Example 25, and Comparative Example 5, the acid value change increased in this order, indicating that even when an amine-based dispersant was not included, a lower epoxy group content resulted in better storage stability.

Claims

1. A polymer having a structural unit (A) represented by the following formula (1): 【Chemistry 1】 (In the formula, X represents a hydrogen atom or a methyl group. L represents a linear or branched divalent organic group. Y represents an organic group that decomposes by acid or heat to produce a vinyl ether group in the polymer side chain.)

2. The polymer according to claim 1, wherein the structural unit (A) is represented by the following formula (1-1): 【Chemistry 2】 (In the formula, X represents a hydrogen atom or a methyl group. R １ R represents a linear or branched divalent organic group. ２ represents an organic group having 1 to 20 carbon atoms.

3. The polymer according to claim 1, further comprising an acid group-containing structural unit (B).

4. The polymer according to claim 1, further comprising a structural unit (C) having a ring structure in the main chain.

5. A polymer solution comprising the polymer according to any one of claims 1 to 4 and a polar solvent.

6. A polymer solution comprising the polymer according to any one of claims 1 to 4 and a basic dispersant and / or a basic compound.

7. A colorant dispersion comprising the polymer solution according to claim 6 and a colorant.

8. 5. A photosensitive resin composition comprising the polymer according to claim 1, a polymerizable compound, and a photopolymerization initiator and / or a photoacid generator.

9. 9. The photosensitive resin composition according to claim 8, which is used for forming a color filter.

10. A cured product obtained by curing the photosensitive resin composition according to claim 8.

11. A method for producing a polymer having a structural unit (A) represented by the following formula (1) and an acid group-containing structural unit (B), The production method includes a step (P-1) of polymerizing a monomer component including a monomer containing a group that generates a vinyl ether group by the action of an acid or heat, and an acid group-containing monomer. A method for producing a polymer comprising the steps of: 【Chemistry 3】 (In the formula, X represents a hydrogen atom or a methyl group. L represents a linear or branched divalent organic group. Y represents an organic group that decomposes by acid or heat to produce a vinyl ether group in the polymer side chain.)

12. A method for producing a polymer having a structural unit (A) represented by the following formula (1) and an acid group-containing structural unit (B), The production method includes a step (Q-1) of polymerizing a monomer component including a monomer containing a group that generates a vinyl ether group by the action of an acid or heat, and a hydroxyl group-containing monomer; The method includes a step (Q-2) of reacting the polymer obtained in the step (Q-1) with an acid group-containing compound. A method for producing a polymer comprising the steps of: 【Chemistry 4】 (In the formula, X represents a hydrogen atom or a methyl group. L represents a linear or branched divalent organic group. Y represents an organic group that decomposes by acid or heat to produce a vinyl ether group in the polymer side chain.)

13. A monomer compound represented by the following formula (a): 【Chemistry 5】 (In the formula, R ７ represents a hydrogen atom or a methyl group. ８ R represents a linear or branched divalent organic group. ９ represents an organic group having 1 to 20 carbon atoms (excluding groups containing a (meth)acryloyl group).

14. A method for producing a monomer compound represented by the following formula (a-1), The production method includes a step of reacting a vinyl ether group-containing (meth)acrylate compound with a carboxylic acid compound, In the reaction step, the amount of the carboxylic acid compound used is 1 equivalent or more relative to 1 equivalent of the vinyl ether group of the vinyl ether group-containing (meth)acrylate compound. A method for producing a monomer compound, comprising the steps of: 【Chemistry 6】 (In the formula, R ７ represents a hydrogen atom or a methyl group. ８ R represents a linear or branched divalent organic group. １０ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms (excluding groups containing a (meth)acryloyl group).

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