Polymers and methods for producing the same, photosensitive resin compositions, cured products, and monomer compounds and methods for producing the 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

[Technical Field]

[0001] The present invention relates to polymers and methods for producing the same, photosensitive resin compositions, cured products, and monomer compounds and methods for producing the same. More specifically, the present invention relates to polymers and methods for producing the same, photosensitive resin compositions, cured products, and monomer compounds and methods for producing the same, which can yield cured products with excellent solvent resistance even under low-temperature curing conditions and also have excellent storage stability. [Background technology]

[0002] Regarding photosensitive resin compositions, various applications in optical components and electrical / electronic equipment, such as color filters used in liquid crystal display devices and solid-state image sensors, inks, printing plates, printed circuit boards, semiconductor elements, photoresists, organic insulating films, and organic protective films, are being investigated, and resins and resin compositions with excellent properties required for each application are being developed. In recent years, there has been a growing trend towards miniaturization, thinning, and energy efficiency in optical components, electrical and electronic equipment, and consequently, higher performance is required for the various components used. To meet these demands, research is being conducted on resins and photosensitive resin compositions that serve as materials for various components.

[0003] To date, various resins and photosensitive resin compositions have been developed to meet diverse requirements (Patent Documents 1-7). For example, Patent Document 1 describes a photocurable composition containing a compound having a specific group having a (meth)acryloyl group and an acetal group or a hemiacetal group, and a photopolymerization initiator, which has sufficient photocurability, allows for obtaining high-resolution patterns by photolithography, and exhibits excellent thermal decomposition properties during firing.

[0004] Further, for example, Patent Document 2 discloses, as a photosensitive resin composition from which a cured film having high sensitivity, high transparency and excellent ITO sputtering resistance can be obtained, comprising: a polymer having a monomer unit having a residue that generates a carboxy group or a phenolic hydroxyl group by an acid, a monomer unit having a group with 3 to 16 carbon atoms having an ethylenically unsaturated bond at a terminal, and having a weight average molecular weight of more than 1000; a photoacid generator; and a solvent. A photosensitive resin composition containing the above is described.

[0005] Further, for example, Patent Document 3 describes, as a resin composition excellent in storage stability, a resin composition containing 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 constituent component having a vinyl ether structure protected by an acetal in the molecule thereof. Further, Patent Documents 5 to 7 each describe a polyfunctional (meth)acrylic acid ester having an acetal structure. [Prior Art Documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Unexamined Patent Publication No. 2003-195497 [Patent Document 2] Japanese Unexamined Patent Publication No. 2011-209682 [Patent Document 3] Japanese Unexamined Patent Publication No. 2018-53031 [Patent Document 4] Japanese Unexamined Patent Publication No. 2002-148805 [Patent Document 5] Japanese Unexamined Patent Publication No. 2003-201267 [Patent Document 6] Japanese Unexamined Patent Publication No. 2007-45924 [Patent Document 7] Japanese Unexamined Patent Publication No. 2013-10726 [Summary of the Invention] [Problems to be Solved by the Invention]

[0007] As mentioned above, various studies have been conducted on resins and photosensitive resin compositions. However, when conventional photosensitive resin compositions containing resins are used together with colorants as raw materials for products such as color filters, there has been a problem in that the colorants leach from the raw materials into the washing solvent during the manufacturing of the color filters. Therefore, further improvement in the solvent resistance of resins has been required.

[0008] Furthermore, in recent years, particularly in color filter applications, the increasing quality and expanding applications of color liquid crystal display devices have led to a strong demand for higher performance, such as higher brightness and contrast in display panels. However, in the manufacturing of color filters, if the firing process (post-curing process) after exposure and development is performed at temperatures exceeding 200°C, discoloration such as yellowing occurs in the resulting cured product, making it difficult to achieve sufficient high coloring in the desired color. In addition, performing the firing process at high temperatures also leads to unwanted reactions and the generation of by-products, which degrade the properties of the substrate and cured film. To suppress such unwanted reactions and efficiently obtain color filters with the desired properties, it is desirable that the curing reaction proceeds sufficiently even under relatively low heating conditions of 200°C or below. Moreover, if the curable resin composition can be cured at relatively low temperatures, the manufacturing efficiency of color filters can also be improved.

[0009] On the other hand, resins that readily undergo curing reactions even under relatively low heating conditions generally have high reactivity, which can lead to problems such as poor storage stability.

[0010] This invention has been made in view of the above-mentioned circumstances, and aims to provide a polymer that can give a cured product with excellent solvent resistance even under low-temperature curing conditions and also has excellent storage stability, a photosensitive resin composition containing the polymer, and a cured product thereof. It also aims to provide a monomer compound that can be used in the production of the polymer, and a method for producing the polymer and monomer compound. [Means for solving the problem]

[0011] The inventors of the present invention conducted various studies on polymers that can be used in photosensitive resin compositions and discovered that by using a polymer with a specific structure, the crosslinking reaction can proceed well even under low-temperature curing conditions of 160°C or below, yielding a cured product with excellent solvent resistance and excellent storage stability, thus completing the present invention.

[0012] In other words, the present invention provides the invention in the following aspects. [1] A polymer characterized by having a structural unit (A) represented by the following formula (1).

[0013] [ka] (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 upon acid or heat to produce vinyl ether groups in the polymer side chains.) [2] The polymer according to [1] above, characterized in that the above structural unit (A) is represented by the following formula (1-1).

[0014] [ka]

[0015] (In the formula, X represents a hydrogen atom or a methyl group. R 1 R represents a linear or branched divalent organic group. 2 (This represents an organic group with 1 to 20 carbon atoms.) [3] The polymer according to [1] or [2] above, further characterized by having an acid group-containing structural unit (B). [4] The polymer according to any of [1] to [3] above, further characterized by having a structural unit (C) having a ring structure in the main chain. [5] A polymer solution characterized by comprising the polymer described in any of [1] to [4] above, and a polar solvent. [6] A polymer solution characterized by comprising a polymer described in any of [1] to [4] above or a polymer solution described in [5] above, and a basic dispersant and / or a basic compound. [7] A colorant dispersion characterized by comprising the polymer solution described in [6] above and a colorant. [8] A photosensitive resin composition comprising a polymer according to any of [1] to [4] above, a polymer solution according to [5] above, a polymer solution according to [6] above, or a 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 [8] above, characterized in that it is for forming a color filter.

[10] A cured product characterized by being obtained by curing the photosensitive resin composition described in [8] or [9] above.

[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 monomer that generates a vinyl ether group by acid or heat, and the acid group-containing monomer.

[0016] [ka]

[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 upon acid or heat to produce vinyl ether groups in the polymer side chains.)

[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 a monomer component including a monomer containing a group that generates a vinyl ether group by acid or heat, and a hydroxyl group-containing monomer; and a step (Q-2) of reacting an acid group-containing compound with the polymer obtained in step (Q-1).

[0018] [ka]

[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 upon acid or heat to produce vinyl ether groups in the polymer side chains.)

[13] A monomer compound characterized by being represented by the following formula (a).

[0020] [ka]

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

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

[0022] [ka]

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

[0024] The polymer and photosensitive resin composition of the present invention exhibit excellent storage stability, cures sufficiently even under low-temperature curing conditions, and yields cured products with excellent solvent resistance. The polymer and photosensitive resin composition of the present invention can be widely applied to various uses such as optical components, electrical and electronic components, and display devices. [Modes for carrying out the invention]

[0025] The present invention will be described in detail below. Furthermore, combinations of two or more of the individual preferred embodiments of the present invention described below are also preferred embodiments 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] [ka]

[0028] (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 upon acid or heat to produce vinyl ether groups in the polymer side chains.)

[0029] The polymer of the present invention, having the above structural unit (A), can yield a cured product with excellent solvent resistance even under low-temperature curing conditions, and exhibits excellent storage stability. This is thought to be because it has a group that decomposes upon contact with acid or heat to generate vinyl ether groups. During curing, vinyl ether groups are generated, allowing cationic polymerization by the vinyl ether groups to proceed and enabling sufficient crosslinking of the polymer. Furthermore, during storage of the polymer, the vinyl ether groups, which are the curing reactive groups, are protected, thus suppressing the self-crosslinking reaction of the polymer and 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, "structural unit" means a repeating (structural) unit in the structure of the polymer.

[0031] In formula (1) above, X represents a hydrogen atom or a methyl group. It is preferable that X is a hydrogen atom because the polymer has high hydrophilicity and excellent developability. In formula (1) above, L represents a linear or branched divalent organic group. Examples of divalent organic groups represented by L include linear or branched divalent hydrocarbon groups, which may have substituents.

[0032] Examples of the linear or branched divalent hydrocarbon groups mentioned above include divalent aliphatic hydrocarbon groups. These aliphatic hydrocarbon groups may be saturated or unsaturated.

[0033] Examples of the above-mentioned divalent saturated aliphatic hydrocarbon groups 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 number of carbon atoms in the saturated aliphatic hydrocarbon group is preferably 1 to 10, and more preferably 2 to 4.

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

[0035] Among these, the above divalent aliphatic hydrocarbon group is preferably a divalent saturated aliphatic hydrocarbon group from the viewpoint that flexibility can be imparted to the side chain.

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

[0037] Preferable examples of the linear or branched divalent organic group include the above linear or branched divalent hydrocarbon group, or a group containing the above linear or branched divalent hydrocarbon group and a bond such as -O-, -COO-, -CO-, -NH-, -S-, -SO-, or -SO2-. The group containing the linear or branched divalent hydrocarbon group and a bond such as -O-, -COO-, -CO-, -NH-, -S-, -SO-, or -SO2- may contain only one type of the above divalent hydrocarbon group or bond, or may contain two or more types thereof. From the viewpoint of good copolymerizability, the above bond is preferably at least one bond selected from the group consisting of -O-, -COO- and -CO-, and more preferably at least one bond selected from the group consisting of -O- and -COO-.

[0038] Among these, the divalent organic group represented by L above is -COO-R 1 -(R 1 represents a linear or branched divalent organic group.), and is preferably a group represented by this formula. The above R 1The linear or branched divalent organic group represented by is preferably a linear or branched divalent hydrocarbon group, or a group containing a linear or branched divalent hydrocarbon group and a bond such as -O-, -COO-, -CO-, -NH-, -S-, -SO-, -SO2-, etc., but among them, -R 3 -(OR 4 ) n -(In the formula, R 3 and R 4 represents a divalent saturated aliphatic hydrocarbon group, either identical or different. n represents an integer of 0 or greater. Groups represented by ) are more preferably listed. The above R 3 and R 4 The divalent saturated aliphatic hydrocarbon group represented by is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 2 carbon atoms. The above value of n is preferably an integer between 0 and 10, and more preferably 1.

[0039] The number of carbon atoms in the divalent organic group represented by L above is preferably 1 to 20, more preferably 1 to 10, and even more preferably 5.

[0040] In formula (1) above, Y represents an organic group that decomposes upon contact with acid or heat, generating a vinyl ether group (-O-CH=CH2) in the polymer side chain. Examples of such organic groups include groups in which a vinyl ether group has been protected with an acetal. Examples of groups in which the vinyl ether group is protected with an acetal include groups containing an -O-CH(CH3)-O- bond, preferably -O-CH(CH3)-OR 2 Examples of groups represented by are shown. When the above polymer has such a group, it can be converted by acid or heat to -OR 2 The group is eliminated, and a vinyl ether group (-O-CH=CH2) is formed in the side chain of the polymer. Here, preferably, 2 This represents an organic group with 1 to 20 carbon atoms.

[0041] The above R 2The organic group represented is preferably a monovalent hydrocarbon group which may have substituents.

[0042] Examples of the monovalent hydrocarbon groups mentioned above include hydrocarbon groups with a chain structure or hydrocarbon groups containing a cyclic structure.

[0043] Examples of hydrocarbon groups in the chain-like structure described above include aliphatic hydrocarbon groups. Examples of the above aliphatic hydrocarbon groups include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, sec-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3-ethylpentyl group, 2,2,3-trimethylbutyl group, octyl group, methylheptyl group, dimethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, trimethylpentyl group, 3-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2,2,3,3-teto 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. Alkyl groups include 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, or 2-octenyl groups, and other alkenyl groups.

[0044] Examples of hydrocarbon groups containing the above-mentioned cyclic structure include hydrocarbon groups with a cyclic structure, or hydrocarbon groups having both a cyclic structure and a chain structure.

[0045] Examples of the cyclic hydrocarbon groups described above include alicyclic hydrocarbon groups and aromatic hydrocarbon groups. Examples of the alicyclic hydrocarbon groups mentioned above include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclododecyl groups. Examples of the above-mentioned aromatic hydrocarbon groups include aryl groups such as phenyl groups and naphthyl groups.

[0046] The hydrocarbon groups having the above-mentioned cyclic and chain structures include hydrocarbon groups consisting of a combination of the aforementioned cyclic hydrocarbon group and a chain hydrocarbon group, such as the benzyl group, phenethyl group, biphenyl group, tolyl group, and xylyl group.

[0047] The number of carbon atoms in the above monovalent hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 3.

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

[0049] In particular, the above R has good low-temperature curing properties. 2 The organic group represented by -R 5 (However, excluding groups containing a carbonyl group.) or -CO-R 6 It is preferable that it be -CO-R 6 It is preferable that it be so. Note that R in the formula 5 and R 6 The same or different groups represent organic groups, preferably hydrocarbon groups, or groups comprising a hydrocarbon group and at least one bond selected from the group consisting of -O- and -COO-, more preferably aliphatic hydrocarbon groups, or groups comprising an aliphatic hydrocarbon group and at least one bond selected from the group consisting of -O- and -COO-, and even more preferably alkyl groups. The above R 6 The number of carbon atoms in the organic group represented 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 above structural unit (A) is preferably a structural unit represented by the following formula (1-1) because it exhibits good low-temperature curing properties.

[0051] [ka]

[0052] (In the formula, X represents a hydrogen atom or a methyl group. R 1 R represents a linear or branched divalent organic group. 2 (This represents an organic group with 1 to 20 carbon atoms.)

[0053] In the above equation (1-1), R 1 and R 2 These are the R mentioned above, respectively. 1 and R 2 It is the same thing.

[0054] A polymer having the above-mentioned structural unit (A) can be obtained, for example, by polymerizing a monomer component that includes a monomer into which the above-mentioned structural unit (A) can be introduced. The monomers into which the above structural unit (A) can be introduced are not particularly limited as long as a polymer having the above structural unit (A) can be obtained by polymerization, but examples include monomers represented by the following formula (2). CH2=CXL-Y (2) (In the formula, X, L, and Y are the same as X, L, and Y in formula (1), respectively.)

[0055] Among these, the monomer compound represented by formula (a) below is preferred as the monomer represented by formula (2) above, due to its excellent synthetic stability.

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

[0057] In the above equation (a), R 8 The linear or branched divalent organic group represented by is R in formula (1-1) above. 1 Preferred examples include groups similar to the linear or branched divalent organic group represented by . Also, R 9 As an organic group having 1 to 20 carbon atoms represented by the above formula (1-1), R 2 Groups similar to the organic group with 1 to 20 carbon atoms represented by the above R are preferred. 9 As for organic groups represented by -CO-R 6 This is preferable. R in the formula 6 The above R is preferably a hydrocarbon group, and more preferably a chain-like saturated hydrocarbon group. 6 The number of carbon atoms in the organic group represented is preferably 1 to 19, more preferably 1 to 10, even more preferably 1 to 5, and most preferably 3.

[0058] Specific examples of monomer compounds represented by the above formula (a) include, for example, 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-butyroxyethoxy)ethoxy)ethyl (meth)acrylate, and 2-(2-(1-formiloxyethoxy)ethoxy)ethyl (meth)acrylate. From a synthetic standpoint, 2-(2-(1-propionyloxyethoxy)ethoxy)ethyl (meth)acrylate and 2-(2-(1-butyroxyethoxy)ethoxy)ethyl (meth)acrylate are preferred, with 2-(2-(1-butyroxyethoxy)ethoxy)ethyl (meth)acrylate being the most preferred. The above monomeric compounds may be used individually or in combination of two or more.

[0059] Furthermore, among the monomer compounds represented by the above formula (a), R 7 R represents a hydrogen atom or a methyl group. 8 R represents a linear or branched divalent organic group. 9 The compound in question is a novel compound representing an organic group having 1 to 20 carbon atoms (excluding groups containing (meth)acryloyl groups). Such novel monomeric compounds are also part of the present invention.

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

[0061] The content of the above 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, based on 100% by mass of the total structural units of the polymer, in terms of good low-temperature curability.

[0062] (2) Structural unit (B) The polymer of the present invention preferably further has an acid group-containing structural unit (B). Having the above structural unit (B) facilitates the generation of vinyl ether groups from the above structural unit (A) during curing, leading to further cationic polymerization by the vinyl ether groups. Furthermore, the reaction between the vinyl ether groups and the acid groups facilitates the self-crosslinking reaction of the polymer, resulting in the formation of a stronger cured product. Additionally, the polymer becomes alkali-soluble, improving its developability. Examples of the above-mentioned acidic groups include carboxyl groups, phenolic hydroxyl groups, carboxylic acid anhydride groups, phosphoric acid groups, sulfonic acid groups, and other functional groups that react with alkaline water in a neutralization reaction. The material may have only one of these groups or two or more. Among these, carboxyl groups and carboxylic acid anhydride groups are preferred, with carboxyl groups being more preferred, as they result in even better developability.

[0063] Polymers having the above-mentioned 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 introducing an acid group by reacting the hydroxyl group of the precursor polymer (base polymer) with a polybasic acid or polybasic acid anhydride. These methods may be combined.

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

[0065] Specific examples of the above acid group-containing monomers include, for example, 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 chain between the unsaturated group and the carboxyl group is extended, such as β-carboxyethyl (meth)acrylate, mono(2-acryloyloxyethyl) succinate, and mono(2-methacryloyloxyethyl) succinate; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; and phosphoric acid-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 viewpoint of versatility and availability. In terms of reactivity, alkali solubility, and other factors, the above acid group-containing monomer is more preferably an unsaturated monocarboxylic acid, and even more preferably (meth)acrylic acid.

[0066] In the method described in 2) above, a precursor polymer having a hydroxyl group is prepared in advance, and then a polybasic acid or polybasic acid anhydride is reacted with the hydroxyl group to introduce an acid group (carboxyl group), thereby obtaining a polymer having an acid group-containing structural unit (B). When polymers containing acidic group structural units are produced using this method, the acidic groups are located relatively far from the main chain of the polymer. This facilitates the crosslinking reaction during the curing of the polymer, thereby improving its curability. In the method described in 2) above, 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 monomers mentioned above include monomer compounds similar to the hydroxyl group-containing monomers described later as monomers that give structural unit (D). Examples of the polybasic acid or polybasic anhydride mentioned above include compounds similar to those described later as acid group-containing compounds. The specific reaction method will be explained later in the section on polymer manufacturing methods.

[0068] In the method described in 2) above, epoxy groups can also be used instead of hydroxyl groups. That is, a polymer having epoxy groups can be prepared in advance, and then the epoxy groups can be ring-opened by adding the acid group of an acid group-containing monomer to the epoxy groups. A carboxyl group can then be produced by reacting the resulting hydroxyl group with a polybasic acid or polybasic anhydride.

[0069] Examples of epoxy group-containing monomers used when preparing the polymer having the epoxy group mentioned above include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, vinylbenzylglycidyl ether, allylglycidyl ether, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and vinylcyclohexene oxide. Among these, glycidyl (meth)acrylate and (3,4-epoxycyclohexyl)methyl (meth)acrylate are preferred, and glycidyl (meth)acrylate is more preferred.

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

[0071] The content of the above structural unit (B) is preferably 0 to 80% by mass relative to 100% by mass of the total structural units of the polymer, and 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 the total structural units of the polymer, in terms of good developability.

[0072] (3) Structural unit (C) The above polymer is preferably a polymer having a ring structure in its main chain. Having a ring structure in the main chain can improve the heat resistance of the polymer. Examples of the above ring structure include an imide ring, a tetrahydrofuran ring, a lactone ring, etc. Thus, the above polymer is further preferably having a structural unit (C) having a ring structure in its main chain.

[0073] Examples of monomers into which the above structural unit (C) can be introduced include monomers having a double bond-containing ring structure within the molecule, monomers that undergo cyclization polymerization to form polymers having a ring structure in the main chain, and monomers that form a ring structure after polymerization. Among these, 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 from the viewpoint of good heat resistance, solvent resistance, hardness, and colorant dispersibility, and N-substituted maleimide monomers are more preferred in that they have even better solvent resistance. The above structural unit (C) can be said to be a monomer-derived structural unit into which such a structural unit (C) can be introduced.

[0074] Examples of the above N-substituted maleimide monomers include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, Nt-butylmaleimide, N-dodecylmaleimide, N-benzylmaleimide, and N-naphthylmaleimide, and one or more of these can be used. Among these, N-phenylmaleimide, N-benzylmaleimide, and N-cyclohexylmaleimide are preferred from the viewpoint of transparency, heat resistance to coloring, and suppression of water unevenness, and N-benzylmaleimide is particularly preferred.

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

[0076] Examples of the above dialkyl-2,2'-(oxydimethylene) diacrylate monomers 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) Examples include dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 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 viewpoint of transparency, dispersibility, and ease of industrial availability.

[0077] Examples of the above-mentioned α-(unsaturated alkoxyalkyl)acrylate monomers include α-(allyloxymethyl)acrylate monomers. Specific examples of the above α-(allyloxymethyl)acrylate monomers include, for example, α-allyloxymethylacrylic acid; α-allyloxymethylacrylate 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-allyl Alkyl-(α-allyloxymethyl)acrylate monomers such as t-octyl oxymethylacrylate, 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 melicyl α-allyloxymethylacrylate;Alkoxyalkyl-(α-allyloxymethyl)acrylate monomers such as α-allyloxymethylacrylate methoxyethyl, α-allyloxymethylacrylate methoxyethoxyethyl, α-allyloxymethylacrylate methoxyethoxyethoxyethyl, α-allyloxymethylacrylate 3-methoxybutyl, α-allyloxymethylacrylate ethoxyethyl, α-allyloxymethylacrylate ethoxyethoxyethyl, α-allyloxymethylacrylate phenoxyethyl, α-allyloxymethylacrylate 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 metharyl, α-Allyloxymethylacrylate clotyl, α-Allyloxymethylacrylate propagyl, α-Allyloxymethylacrylate cyclopentyl, α-Allyloxymethylacrylate cyclohexyl, α-Allyloxymethylacrylate 4-methylcyclohexyl, α-Allyloxymethylacrylate Examples include 4-t-butylcyclohexyl lylate, 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. Of the alkyl-(α-allyloxymethyl)acrylate monomers mentioned above, methyl α-allyloxymethylacrylate (also referred to as methyl-(α-allyloxymethyl)acrylate) is particularly preferred from the viewpoint of transparency, dispersibility, and ease of industrial availability.

[0078] The above-mentioned α-(unsaturated alkoxyalkyl)acrylate monomers can be produced, for example, by the manufacturing method disclosed in International Publication No. 2010 / 114077.

[0079] Another monomer that can introduce the above structural unit (C) is alkyl 2-(hydroxyalkyl)acrylate. Alkyl 2-(hydroxyalkyl)acrylate can react with (meth)acrylic acid to form a lactone ring structure in the main chain.

[0080] Examples of the above-mentioned alkyl 2-(hydroxyalkyl)acrylates include alkyl 2-(1-hydroxyalkyl)acrylates and alkyl 2-(2-hydroxyalkyl)acrylates. Specifically, 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, and ethylhexyl 2-(1-hydroxymethyl)acrylate. Among these, methyl 2-(1-hydroxymethyl)acrylate and ethyl 2-(1-hydroxymethyl)acrylate are preferred.

[0081] The above polymer may have only one of the above structural units (C), or it may have two or more of them.

[0082] The content of the above 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, based on 100% by mass of the total structural units of the above polymer.

[0083] (4) Structural unit (D) The polymer described above may have structural units (D) other than the structural units (A), (B), and (C) described above. Other structural units (D) mentioned above include, for example, the monomer-derived structural units listed below. Hydroxyl group-containing monomers such as hydroxyalkyl (meth)acrylates including 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 methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, s-butyl methacrylate, n-amyl methacrylate, s-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, tridecyl methacrylate, octyl methacrylate, isooctyl methacrylate, lauryl methacrylate, stearyl methacrylate, benzyl methacrylate, phenyl methacrylate, isobornyl methacrylate, adamantyl methacrylate, tricyclodecanyl methacrylate, cyclohexyl methacrylate, dicyclopene methacrylate (meth)acrylic acid ester monomers such as tanyl, 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]deca-2-ylmethacrylic 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 (meth)acrylate glycidyl, (meth)acrylate β-methylglycidyl, (meth)acrylate β-ethylglycidyl, vinylbenzylglycidyl ether, allylglycidyl ether, (meth)acrylate (3,4-epoxycyclohexyl)methyl, 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-vinylmorpholin, and N-vinylacetamide; Vinyltoluene, styrene, and other styrene derivatives; Unsaturated isocyanates such as (meth)acrylate isocyanatoethyl and allyl isocyanate; etc.

[0084] In particular, the above 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 described above may have only one type of structural unit (D), or it may have two or more types.

[0086] The content of the above 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, based on 100% by mass of the total structural units of the above polymer. If the polymer contains two or more of the above structural units (D), the proportion of each structural unit (D) can be appropriately set according to the application and purpose of the polymer of the present invention.

[0087] The acid value of the above polymer is preferably 10 to 200 mg KOH / g. The acid value of the above polymer is more preferably 20 to 150 mg KOH / g, and even more preferably 50 to 130 mg KOH / g, in terms of good developability. The above acid value is obtained by a neutralization titration method using potassium hydroxide (KOH) solution and represents the acid value per gram of resin solids.

[0088] The weight-average molecular weight of the above polymer is preferably 1,000 to 100,000. More preferably, the weight-average molecular weight of the above polymer is 3,000 to 50,000, and even more preferably 5,000 to 20,000, in terms of good low-temperature curability. The above weight-average molecular weight is obtained by measuring it using gel permeation chromatography (GPC) as described in the examples.

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

[0090] The vinyl ether equivalent mentioned above is the mass of solids in the polymer solution per mole of vinyl ether groups of the polymer. The mass of solids in the polymer solution refers to the mass of monomer components constituting the polymer. The vinyl ether equivalent can be determined by dividing the mass (g) of polymer solids in the polymer solution by the number of vinyl ether groups (mol) of the polymer. It can also be measured using various analytical methods such as titration, elemental analysis, NMR, IR, and differential scanning calorimetering.

[0091] The above polymer may have polymerizable double bonds in its side chains. Having polymerizable double bonds in the side chains can improve the curability of the polymer. Examples of polymerizable double bonds include those described above. Among these, (meth)acryloyl groups are preferred in terms of reactivity.

[0092] When the polymer has polymerizable double bonds in its side chains, the double bond equivalent of the polymer is preferably 400 to 50,000 g / mol. More preferably, the double bond equivalent is 500 to 10,000 g / mol, and even more preferably 600 to 2,000 g / mol, in terms of improving curability. The double bond referred to here is a double bond that exhibits radical polymerization. That is, a polymerizable double bond, such as the (meth)acryloyl group. For example, a double bond formed by adding tetrahydrophthalic anhydride to a hydroxyl group is not reactive and is therefore not included in the calculation of double bond equivalents.

[0093] The above double bond equivalent is the mass of solids in the polymer solution per mole of double bonds in the polymer. The mass of solids in the polymer solution is the mass of monomeric components constituting the polymer. The above double bond equivalent can be determined by dividing the mass (g) of polymer solids in the polymer solution by the amount (mol) of double bonds in the polymer. It can also be measured using various analytical methods such as titration, elemental analysis, NMR, IR, and differential scanning calorimetering.

[0094] 2. Method for producing polymers The method for producing the polymer of the present invention is not particularly limited as long as the polymer described above is obtained. For example, a method of polymerizing a monomer component containing the above-mentioned structural unit (A) and monomers into which structural units (B), (C), and (D) can be introduced as needed, by a known method. The amount of each monomer can be appropriately adjusted so that the content of each structural unit in the polymer is within a desired range.

[0095] The method for polymerizing the above monomer components is not particularly limited, and commonly used methods 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 adjustment of the molecular weight and other structural parameters. Furthermore, while polymerization methods based on mechanisms such as radical polymerization, anionic polymerization, cationic polymerization, and coordination polymerization can be used for the polymerization mechanism of the above monomer components, polymerization methods based on the radical polymerization mechanism are preferred because they are industrially advantageous. Furthermore, the molecular weight of the polymer obtained by polymerizing the above monomer components can be controlled by adjusting the amount and type of polymerization initiator, the polymerization temperature, and the type and amount of chain transfer agent.

[0096] Examples of polymerization initiators include known peroxides and azo compounds commonly used as polymerization initiators. Examples of chain transfer agents include compounds having a mercapto group, such as alkyl mercaptans, mercaptocarboxylic acids, and mercaptocarboxylic acid esters, commonly used as chain transfer agents. These may be used individually or in combination of two or more. The amounts added can be appropriately determined by known methods.

[0097] The solvents used in the above polymerization include, for example, 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; and die Examples of ether-based solvents include ethyl ether, diisopropyl ether, 1,2-dimethoxyethane (DME), 1,4-dioxane, tetrahydrofuran (THF), tetrahydropyran (THP), anisole, diethylene glycol dimethyl ether (diglym), diethylene glycol ethyl ether (carbitol), cyclopentyl methyl ether (CPME), propylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether; fluorine-based solvents such as perfluorohexane, perfluorocyclohexane, pentafluorobenzene, and octafluorotoluene; and DMSO and nitromethane. You may use only one of these, or you may use two or more. The amount of solvent used is not particularly limited and can be appropriately determined by known methods.

[0098] Regarding the polymerization conditions described above, the polymerization temperature can be set appropriately depending on the type and amount of monomer used, the type and amount of polymerization initiator, etc., but for example, 40 to 130°C is preferred, and 50 to 120°C is more preferred. Similarly, the polymerization time can be set appropriately, for example, 1 to 15 hours is preferred, and 2 to 11 hours is more preferred.

[0099] As a method for producing the above polymer, it is preferable to include a step of polymerizing monomer components including a monomer (a) containing a group that generates a vinyl ether group by acid or heat, and an acid group-containing monomer (b). A method for producing a polymer having a structural unit (A) and an acid group-containing structural unit (B) represented by the above formula (1), wherein the production method includes a step (P-1) of polymerizing monomer units including a monomer containing a group that generates a vinyl ether group by acid or heat, and an acid group-containing monomer (polymer production method 1), is also one of the present inventions.

[0100] Process (P-1) Examples of monomers having a group that generates a vinyl ether group upon contact with the above-mentioned acid or heat include monomers into which the above-mentioned structural unit (A) can be introduced, and preferably, monomer compounds represented by the above formula (a) are included. Examples of the above-mentioned acid group-containing monomers include those similar to those described above.

[0101] The polymerization in step (P-1) described above can be carried out in the same manner as the polymerization method described above. In the polymerization described above, additives such as polymerization initiators and chain transfer agents, as well as solvents, may be used as appropriate.

[0102] The polymerization in step (P-1) described above is preferably carried out in the presence of a basic compound. By polymerizing the monomer components in the presence of a basic compound, the formation of vinyl ether groups in monomer (a) by the acid groups of the acid group-containing monomer units is suppressed, and the desired polymerization reaction can proceed smoothly. Furthermore, since the acidity of the reaction system is neutralized and the formation of vinyl ether groups is suppressed, gelation can be suppressed, and a polymer with excellent storage stability can be obtained. In addition, to improve the storage stability of the obtained polymer, a basic compound may be added after polymerization.

[0103] Examples of the basic compounds mentioned above 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; tetraalkylammonium organic salts such as tetramethylammonium acetate; tetraalkylammonium inorganic salts such as tetramethylammonium bisulfate and tetraethylammonium bisulfate; (hydroxy)alkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and monohydroxyethyltrimethylammonium hydroxide; hydroxides of alkali metals such as sodium and potassium; hydroxides of transition metals such as barium, strontium, calcium, and lanthanum; and free salts of complex salts such as [Pt(NH3)6](OH)4. In particular, from the standpoint of suppressing deprotection, it is preferable that the amine be a secondary amine, a tertiary amine, or a heterocyclic amine, and more preferably a tertiary amine.

[0104] Furthermore, the basic compound preferably has a boiling point of 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 firing temperature after coating film formation, the basic compound will volatilize during firing, causing the neutralized side-chain carboxylate salt to become a carboxylic acid. This carboxylic acid makes it possible to promote the cationic polymerization of vinyl ether and crosslinking by acetalization with the side-chain carboxylic acid.

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

[0106] Furthermore, a method for producing a polymer having a structural unit (A) and an acid group-containing structural unit (B) represented by the above formula (1), comprising the steps of polymerizing a monomer component including a monomer containing a group that generates a vinyl ether group by acid or heat, and a hydroxyl group-containing monomer (Q-1), and reacting the polymer obtained in step (Q-1) with an acid group-containing compound (Q-2), is also one of the present inventions.

[0107] Process (Q-1) In the polymer production method 2 described above, first, monomer components including monomer (a) containing a group that generates a vinyl ether group by acid or heat, and monomer components containing a hydroxyl group are polymerized.

[0108] In the above step (Q-1), the monomer containing a group that generates a vinyl ether group by acid or heat, and the monomer containing a hydroxyl group, are the same as those described above. The polymerization reaction in step (Q-1) described above can be carried out in the same manner as the polymerization method described above. In addition, additives such as polymerization initiators and chain transfer agents, as well as solvents, may be used in the polymerization.

[0109] Process (Q-2) In the polymer production method 2 described above, the polymer obtained in step (Q-1) is then reacted with an acid group-containing compound. By reacting the above polymer with an 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 above acid group-containing compounds are preferably polybasic acids or polybasic acid anhydrides, such as carboxylic acids like succinic acid, maleic acid, phthalic acid, tetrahydrophthalic acid, and trimellitic acid; and carboxylic acid anhydrides like succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, itaconic acid anhydride, and trimellitic acid anhydride. Among these, carboxylic acid anhydrides are preferred due to their higher addition reactivity, and succinic anhydride is even more preferred. The amount of the above acid group-containing compound used should be appropriately determined according to the intended use, purpose, and desired acid value of the resulting polymer.

[0111] The reaction between the polymer and the acid group-containing compound in step (Q-2) above is preferably carried out in the presence of a basic compound. Although an acid group is formed at the terminal end of the polymer by the addition reaction of the acid group-containing compound described above, it is immediately neutralized by the basic compound. As a result, the vinyl ether group is more easily protected at the group that generates a vinyl ether group by acid or heat in the resulting polymer, and the reaction between polymers is suppressed, thus improving the synthesis and storage stability of the polymer.

[0112] Examples of the basic compounds mentioned above include those similar to the basic compounds described above.

[0113] In the above step (Q-2), 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, it 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 constituent unit used in the above step (Q-1).

[0114] Furthermore, when producing a polymer having polymerizable double bonds in its side chains, for example, after step (Q-1) above, polymerizable double bonds can be introduced into the side chains of the polymer by adding (meth)acrylic acid to the epoxy group. Furthermore, polymerizable double bonds can also be introduced into the side chains of polymers by adding unsaturated isocyanates to the hydroxyl groups instead of (meth)acrylic acid.

[0115] Furthermore, polymerizable double bonds can also be introduced into the side chains of polymers by adding an epoxy group-containing compound to an acid group. For example, after preparing a polymer (base polymer) having an acid group, the aforementioned epoxy group-containing monomer can be reacted with the acid group to introduce a polymerizable double bond through an addition reaction caused by the cleavage of the epoxy group.

[0116] The addition reactions of (meth)acrylic acid, unsaturated isocyanates, and epoxy group-containing compounds described above are not particularly limited and can be carried out by known methods. In addition, commonly used catalysts and solvents may be used in the above addition reactions.

[0117] In the polymer manufacturing method described above, it is preferable to use a basic compound as stated above. However, the basic compound may remain (be present) after the polymer is manufactured, and a polymer solution containing the polymer and the basic compound is also one of the preferred forms in the present invention. Such a polymer solution has good storage stability. The polymer solution may also further contain a polar solvent, as described later.

[0118] The above polymer production method may include other steps in addition to the reaction step described above. Examples of these other steps include a maturation step, a neutralization step, a dilution step, a drying step, a concentration step, a purification step, and so on. These steps can be carried out by known methods.

[0119] 3. Method for producing monomer compounds A method for producing a monomer compound represented by the above formula (a) will be described, as a monomer into which the above structural unit (A) can be introduced. One example of a method for producing the above monomer compound is to react 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 compounds mentioned above include the compound represented by the following formula (3). CH2=C(R 11 )-COO-R 12 -O-CH=CH2(3) (In the formula, R 11 R represents a hydrogen atom or a methyl group. 12 (This represents a linear or branched divalent organic group.) R in equation (3) above 12 The organic group represented by is R in formula (a) above. 8 Examples of organic groups similar to those represented by the symbol are shown.

[0121] Specific examples of the vinyl ether group-containing (meth)acrylate compounds mentioned above include, for example, 2-(2-vinyloxyethoxy)ethyl acrylate and 2-(2-vinyloxyethoxy)ethyl methacrylate.

[0122] Examples of the carboxylic acid compounds mentioned above include aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, heptylic 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-norbornenedicarboxylic acid. Among these, monocarboxylic acids are preferred because the products are easily copolymerized, aliphatic carboxylic acids and formic acid are more preferred, and acetic acid, propionic acid, butyric acid, and formic acid are even more preferred. Furthermore, from the viewpoint of improving curability and storage stability after polymerization, propionic acid and butyric acid are even more preferred, and butyric acid is the most preferred.

[0123] Examples of the above alcohol compounds 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. Among these, monoalcohols are preferred because the products are easily copolymerized, and ethanol, isopropanol, and propylene glycol monomethyl ether are more preferred.

[0124] The above-mentioned carboxylic acid compounds and alcohol compounds may be used individually or in combination of two or more. Among these, carboxylic acid compounds are preferred because they offer better storage stability.

[0125] Furthermore, the above-mentioned carboxylic acid compounds and alcohol compounds 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, as these are good choices for achieving both storage stability and low-temperature curability.

[0126] In the above reaction, it is preferable to mix 1 equivalent or more of a carboxylic acid compound or 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 autocatalyzably, and the reaction is promoted.

[0127] The above reaction is not particularly limited and can be carried out by known methods such as mixing each component and heating it. Furthermore, while it is not necessary to use a solvent in the above reaction, one may use one. Examples of solvents used in the above reaction include one or two of the following: 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 catalysts mentioned above 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 their salts such as benzenesulfonic acid, p-toluenesulfonic acid, pyridinium salt of p-toluenesulfonic acid, and quinolinium salt of p-toluenesulfonic acid; and sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, nickel sulfate, copper sulfate, zirconium sulfate, etc. Sulfates; bisulfates such as sodium bisulfate and potassium bisulfate; mineral acids such as sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, and polyphosphate; heteropoly acids such as phosphovanadidomolybdic acid, phosphotungstomolybdic acid, and crystallinetungstomolybdic acid; acid zeolites, etc., as described in paragraph

[0043] of Japanese Patent Publication No. 2003-201267; and other phosphate-containing unsaturated compounds such as 2-methachloroyloxyethyl acid phosphate and 2-acryloyloxyethyl acid phosphate. Commercially available examples include Light Ester P-1M and Light Ester P-2M (manufactured by Kyoeisha Chemical). The above catalysts may be used individually or in combination of two or more.

[0129] The amount of the above 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, per 100 parts by mass of the vinyl ether group-containing (meth)acrylate compound. In particular, due to its rapid reaction rate, p-toluenesulfonic acid is preferred as a catalyst in the above reaction.

[0130] Examples of the polymerization inhibitors mentioned above 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-oxyl compounds 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 individually or in combination of two or more types.

[0131] The amount of 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, per 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 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 above monomer compound may further include other steps, such as a purification step, in addition to the reaction step described above. These other steps may be carried out by known methods. Acid-base extraction is preferred as the purification process. Unreacted carboxylic acid compounds and alcohols are separated into the aqueous layer using a basic aqueous solution, and the target product can be efficiently purified by concentrating the oil layer.

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

[0135] The monomer compounds can be produced by the manufacturing method described above. However, among the monomer compounds, the monomer compound represented by the following formula (a-1) is preferably produced by a method that includes a step of reacting a vinyl ether group-containing (meth)acrylate compound with a carboxylic acid compound, wherein the amount of the carboxylic acid compound used in the reaction step is 1 equivalent or more per 1 equivalent of vinyl ether groups in the vinyl ether group-containing (meth)acrylate compound. Such a method for producing the above formula (a-1) is a novel manufacturing method and is one of the present inventions.

[0136] [ka]

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

[0138] 4. Polymer solution The polymer described above is preferably prepared as a polymer solution with a polar solvent. Adding a polar solvent to the polymer to prepare a polymer solution improves the storage stability of the polymer. The reason why the addition of a polar solvent improves the storage stability of the polymer is not entirely clear, but it is thought 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 polymer solutions containing the polymers and polar solvents described above are also part of the present invention.

[0139] Examples of the above-mentioned polar solvents include protic polar solvents and aprotic polar solvents. Examples of the above-mentioned protic polar solvents include water, alcohol-based solvents, amine-based solvents, and phenol-based solvents. Among these, the above-mentioned protic polar solvent is preferably an alcohol-based solvent.

[0140] As the alcohol-based solvent mentioned above, saturated alcohols are preferred, and examples include monofunctional alcohols (monoalcohols), polyhydric alcohols, glycol monoethers, etc. Specific examples of the alcohol-based 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; 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, or tripropylene glycol monomethyl ether; Examples include tertiary alcohols such as tert-butanol, tert-pentanol, and tert-hexanol. In particular, the above-mentioned alcohol-based solvent is preferably a secondary or tertiary alcohol, as it suppresses the deprotection of the acetal group and can reduce the viscosity of the polymer solution.

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

[0142] Propylene glycol monomethyl ether is particularly preferred as the alcohol-based solvent.

[0143] Examples of the amine-based solvents mentioned above include diethyleneamine, dimethylamine, and oleylamine.

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

[0145] Preferred aprotic solvents include ether-based solvents, ether acetate-based solvents, and amide-based solvents. Among these, amide-based solvents are more preferable.

[0146] Examples of the ether-based solvents mentioned above include tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether.

[0147] Examples of the above-mentioned ether acetate solvents 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 above-mentioned amide solvents include N,N-diethylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and tetramethylurea. N,N-dimethylformamide is preferred from the viewpoint of compatibility with copolymers.

[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 above 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 easily removed by heating, has a boiling point of a certain degree, and is suitable for forming a flat film.

[0151] The polymer solution described above may contain one or more polar solvents. The content of the polar solvent in the above 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, based on 100% by mass of the polymer solids. Furthermore, 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, based on 100% by mass of the polymer solids.

[0152] The above 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 described above may contain other components besides the polymer and polar solvent mentioned above.

[0153] 5. Polymerization solution The polymer or polymer solution described above can be used to form a polymer solution together with a basic dispersant and / or a basic compound. The polymer solution described above has excellent storage stability. A polymer solution containing the polymer or polymer solution described above, along with a basic dispersant and / or a basic compound, is also one of the present inventions. Furthermore, it is also a preferred embodiment of the present invention that the polymer or basic dispersant is neutralized with a basic compound.

[0154] Examples of the basic compounds mentioned above include those listed above. As described above, the basic compounds may be those that remain after being used in the production of polymers.

[0155] Preferred basic dispersants include polymeric dispersants having basic functional groups. The polymeric dispersants having basic functional groups may be neutralized with the basic compound as described above, and may also include, for example, neutralized amine salts. Examples of the above basic dispersants 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 Big Chemie Japan Co., Ltd.), 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, Japan Lube) Examples include Rizol Co., Ltd., Azisper® PA111, PB711, PB821, PB822, PB824, etc. (all manufactured by Ajinomoto Fine Techno Co., Ltd.), and Disparon® 1831, 1850, 1860, DA-703-50, DA-7301, DA-325, DA234, etc. (all manufactured by Kusumoto Chemical Co., Ltd.).

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

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

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

[0159] Furthermore, the polymer in the polymer solution described above preferably has an epoxy equivalent of 1000 g / mol or more, more preferably 5000 g / mol or more, and even more preferably does not contain epoxy groups, in terms of having even better storage stability. The above epoxy equivalent can be determined by dividing the mass (g) of the polymer solids by the number of moles (mol) of epoxy groups contained in the polymer.

[0160] Furthermore, the content of the polar solvent in the polymer solution is preferably 10 to 1000 parts by mass, more preferably 20 to 800 parts by mass, and even more preferably 30 to 600 parts by mass, per 100 parts by mass of the total solid content of the polymer solution.

[0161] The method for preparing the polymer solution described above is not particularly limited, and one method is to mix each component contained in the polymer solution using known mixing means.

[0162] 6. Colorant dispersion liquid The polymer solution described above may further contain a colorant. A colorant dispersion containing the polymer solution described above and a colorant is also part of the present invention. The above colorant dispersion has excellent storage stability.

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

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

[0165] The above-mentioned colorant dispersion may further contain a solvent, and examples of such solvents include the polymerization solvent for the polymer mentioned above and the polar solvent mentioned above.

[0166] The amount of the solvent in the above-mentioned colorant dispersion 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, based on 100 parts by mass of the total solid content of the colorant dispersion, in terms of good storage stability.

[0167] The method for preparing the above-mentioned colorant dispersion is not particularly limited, and it can be prepared by mixing and dispersing each component contained in the above-mentioned colorant dispersion using known mixing and dispersion methods.

[0168] 7. Photosensitive resin composition A photosensitive resin composition comprising the above-mentioned polymer, polymer solution, polymer solution, or colorant dispersion, a polymerizable compound, and a photopolymerization initiator and / or photoacid generator is also part of the present invention. Because the photosensitive resin composition of the present invention contains the above-mentioned polymer, it has excellent storage stability and can provide a cured product with excellent solvent resistance even under low-temperature curing conditions.

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

[0170] When the above photosensitive resin composition contains the above polymer solution, the content of the above 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, based on 100 parts by mass of the total solid content of the above photosensitive resin composition.

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

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

[0173] (polymerizable compound) The polymerizable compounds described above are low-molecular-weight compounds having polymerizable unsaturated bonds (also called polymerizable unsaturated groups) that can be polymerized by irradiation with free radicals, electromagnetic waves (e.g., infrared rays, ultraviolet rays, X-rays, etc.), electron beams, or other active energy rays. Examples 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 compounds mentioned above include N-substituted maleimide monomers; (meth)acrylic acid esters; (meth)acrylamides; unsaturated monocarboxylic acids; unsaturated polycarboxylic acids; unsaturated monocarboxylic acids in which the chain between the unsaturated group and the carboxyl group is extended; unsaturated acid anhydrides; aromatic vinyls; conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; unsaturated isocyanates; and so on. Monomers having active methylene groups or active methine groups can also be used.

[0175] Examples of the polyfunctional compounds mentioned above include the following compounds. Difunctional (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 Dimethylolpropane tetra(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 succinate modified, pentaerythritol triacrylate succinate modified, dipentaerythritol pentaacrylate phthalate modified, pentaerythritol triacrylate phthalate modified, the following formula:

[0177] [ka]

[0178] Polyfunctional (meth)acrylate compounds with three or more functions, such as modified dipentaerythritol hexaacrylate represented by [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 hexanyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, and ethylene oxide-added dipentaerythritol hexanyl ether;

[0180] Vinyl ether group-containing (meth)acrylic acid esters such as (meth)acrylate 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 2-(vinyloxyethoxyethoxyethoxy)ethyl;

[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 (meth)acrylate; polyfunctional (meth)acryloyl group-containing isocyanurates such as tri(acryloyloxyethyl)isocyanurate, tri(methacryloyloxyethyl)isocyanurate, alkylene oxide-added tri(acryloyloxyethyl)isocyanurate, alkylene oxide-added tri(methacryloyloxyethyl)isocyanurate; polyfunctional allyl group-containing isocyanurates such as triallyl isocyanurate; polyfunctional urethane (meth)acrylates obtained by the reaction of polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, 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 individually or in combination of two or more.

[0183] Among the polymerizable compounds mentioned above, it is preferable to use a polyfunctional polymerizable compound from the viewpoint of further improving the curability of the photosensitive resin composition. The number of functionalities in the polyfunctional polymerizable compound is preferably 3 or more, and more preferably 4 or more. Furthermore, the number of functionalities is preferably 10 or less, and more preferably 8 or less. The molecular weight of the polymerizable compound is not particularly limited, but from the viewpoint of handling, it is preferably 2000 or less.

[0184] Among the polyfunctional polymerizable compounds mentioned above, from the viewpoint of reactivity, economy, and availability, 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 preferably polyfunctional (meth)acrylate compounds. By including a compound having a (meth)acryloyl group, the above photosensitive resin composition becomes superior in photosensitivity and curability, and a cured product with even higher hardness and transparency can be obtained. It is even more preferable to use a polyfunctional (meth)acrylate compound with three or more functions 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, based on 100% by mass of the total solid content of the photosensitive resin composition.

[0186] (Photopolymerization initiator) Specific examples of the above photopolymerization initiators include, for example, aminoketone compounds such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("IRGACURE 907", BASF), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 ("IRGACURE 369", BASF), and 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one ("IRGACURE 379", BASF); 2,2-dimethoxy-1,2-diphenylethane-1-one ("IRGACURE 651", BASF), and phenylglyoxylic acid methyl ester ("DAROCURE 651"). Benzyl ketal compounds such as "MBF" (manufactured by BASF); 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 Hydroketone compounds such as -1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]-phenyl}-2-methylpropan-1-one ("IRGACURE 127", manufactured by BASF), [1-hydroxy-cyclohexyl-phenyl-ketone + benzophenone] ("IRGACURE 500", manufactured by BASF); and other alkylphenone compounds exemplified in paragraphs

[0084] to

[0086] of Japanese Patent Application Publication No. 2013-227485;1,2-Octanedione, 1-[4-(phenylthio)phenyl]-,2-(O-benzoyl oxime) ("OXE01", manufactured by BASF), Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime) ("OXE02", manufactured by BASF), 1,2-Octanedione, 1-[4-(phenylthio)-,2-,(O-benzoyl oxime)], Ethanone ("OXE03", manufactured by BASF), 1-[9-ethyl Examples include oxime ester compounds such as -6-(2-methylbenzoyl)-9H-carbazole-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, etc.; phosphine oxide compounds; etc. Among these, aminoketone compounds and oxime ester compounds are preferred. The above photopolymerization initiators may be used individually or in combination of two or more.

[0187] The content of the above-mentioned 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, based on 100% by mass of the total solid content of the above-mentioned photosensitive resin composition.

[0188] (Photoacid generator) The above photosensitive resin composition may also contain a photoacid generator. By including a photoacid generator, cationic polymerization can proceed, resulting in a cured product with superior solvent resistance.

[0189] The photoacid generator used in the present invention is a compound that generates a radical simultaneously with an acid when irradiated with light. Examples of the above photoacid generator are compounds that generate acid upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beams, and X-rays. Specifically, known compounds such as onium salt compounds, sulfone compounds, sulfonic acid ester compounds, quinone diazide compounds, sulfonimide compounds, and diazomethane compounds can be found. In particular, the above 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 above-mentioned photoacid generator include, for example, the compounds described in paragraphs

[0112] to

[0117] of Japanese Patent Publication No. 2021-39186.

[0190] The content of the above-mentioned photoacid generator is not particularly limited as long as the effects of the present invention are exhibited, and can be set as appropriate. For example, it 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, based on 100% by mass of the total solid content of the photosensitive resin composition of the present invention.

[0191] The above photosensitive resin composition may also contain other components besides those described above, as needed. Examples of these other components include solvents; colorants (pigments, dyes); dispersants; heat resistance improvers; leveling agents; developing aids; inorganic fine particles such as silica fine particles; coupling agents such as silane, aluminum, and titanium; fillers, thermosetting resins such as phenolic resins and polyvinylphenols; curing aids such as polyfunctional thiol compounds; plasticizers; polymerization inhibitors; ultraviolet absorbers; antioxidants; matting agents; defoamers; antistatic agents; slip agents; surface modifiers; thixotropes; thixotrope aids; quinone diazide compounds; polyvalent phenolic compounds; cationic polymerizable compounds; and thermoacid generators. These may be used individually or in combination of two or more. These other components can be appropriately selected from known components, and their amounts can also be appropriately set. For example, when the above-mentioned photosensitive resin composition is used for color filter applications, it is preferable that the photosensitive resin composition contains a colorant.

[0192] Furthermore, the above photosensitive resin composition preferably contains a polyfunctional thiol compound, as this can be expected to facilitate crosslinking with vinyl ether groups and promote cationic polymerization. Examples of the above-mentioned polyfunctional thiol compounds include tris(3-mercaptopropionyloxy)ethyl isocyanurate, trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, and 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-triazinan-2,4,6-trione, trimethylolpropane tris(3-mercaptobutyrate), and the like.

[0193] <Preparation of photosensitive resin composition> The method for preparing the photosensitive resin composition of the present invention is not particularly limited and any known method may be used. For example, one method may be to mix and disperse each of the above-mentioned components using various mixers and dispersers. The mixing and dispersion steps are not particularly limited and may be carried out by known methods. In addition, other commonly performed steps may be included. If the above 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 above-mentioned photosensitive resin composition is applied to a substrate or molded, and then cured by heating, irradiation with active energy rays such as ultraviolet light, or a combination thereof to obtain a cured product.

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

[0196] The above-mentioned substrate is not particularly limited and can be appropriately selected according to the purpose and application. Examples include substrates made of various materials such as glass plates and plastic plates.

[0197] In step (1) described above, the method for applying the photosensitive resin composition to form a coating film is not particularly limited and can be carried out by known methods such as spin coating, slit coating, roll coating, and casting coating. In the above manufacturing method, it is preferable to apply the photosensitive resin composition onto a substrate and then dry the coated material to form a coating film. The drying can be carried out by known methods, such as using a hot plate, IR oven, or convection oven. The drying conditions are appropriately selected according to the boiling point of the solvent components, the type of curing component, the film thickness, the performance of the dryer, etc., but it is generally preferable to dry at a temperature of 50 to 160°C for 10 to 300 seconds.

[0198] In step (2) above, the method of irradiating the formed coating with light is not particularly limited and can be carried out by known methods. Examples of light sources for the active light used for light irradiation include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps, as well as laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, and semiconductor lasers.

[0199] When irradiating the above coating with light, the light irradiation may be performed via a photomask. As the photomask, it is preferable to use a mask with light-shielding sections formed according to the desired pattern.

[0200] In step (3) above, after the light irradiation step described above, the material is developed with a developer to remove the unirradiated areas. Due to the light irradiation, the irradiated areas harden, and the hardened material becomes insoluble or sparingly soluble in the developer. On the other hand, the unirradiated areas dissolve in the developer and are removed by the development process, resulting in a patterned hardened film. The development process can usually be carried out at a development temperature of 10 to 50°C using methods such as immersion development, spray development, brush development, or ultrasonic development.

[0201] The developer used in step (3) above is not particularly limited as long as it dissolves the photosensitive resin composition, but usually an organic solvent or an alkaline aqueous solution is used, and a mixture thereof may also be used. When an alkaline aqueous solution is used as the developer, it is preferable to wash with water after development. Examples of organic solvents and alkaline aqueous solutions include those similar to those described in Japanese Patent Application Publication No. 2015-157909.

[0202] In step (4) above, it is preferable to heat the developed coating film at 150°C or lower. In the heating step after light irradiation (post-curing step) in step (4) above, the heating temperature is preferably 130°C or lower, and more preferably 120°C or lower. The photosensitive resin composition of the present invention can provide a cured product with excellent solvent resistance, as the curing reaction proceeds well even at relatively low temperatures. As a lower limit for the heating temperature, it is preferably 70°C or higher, and more preferably 80°C or higher, in order to maintain curability.

[0203] The heating time in the above heating process is not particularly limited, but is preferably 5 to 60 minutes. The heating method is also not particularly limited and can be carried out using known heating equipment such as a hot plate, convection oven, or high-frequency heater.

[0204] When the cured product obtained by the above manufacturing method is a cured film, its 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 its protective film properties.

[0205] The cured product obtained by the above manufacturing method exhibits excellent solvent resistance. A cured product obtained by curing such a photosensitive resin composition is also one of the present inventions.

[0206] 9.Applications The polymer and photosensitive resin composition of the present invention exhibit excellent storage stability and can yield cured products with excellent solvent resistance even under low-temperature curing conditions, making them suitable for applications requiring storage stability and high solvent resistance. The polymer and photosensitive resin composition of the present invention are suitably used for optical materials, and are preferably used for resists. The curable resin composition of the present invention can be suitably used for both negative and positive type resists.

[0207] The polymers and photosensitive resin compositions of the present invention can be suitably used in various applications such as color filters, black matrices, photospacers, black column spacers, inks, printing plates, printed circuit boards, semiconductor elements, photoresists, insulating films, films, and organic protective films used in liquid crystal, organic EL, quantum dot, and micro-LED liquid crystal display devices, solid-state image sensors, and touch panel display devices, as well as components of electrical and electronic equipment. In particular, they are preferably used for forming color filters. [Examples]

[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 "percent mass".

[0209] The various evaluation methods used in this embodiment are as follows.

[0210] < 1 H-NMR Measurement> For the obtained monomer compound, under the following conditions 1 H-NMR measurement was performed. 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 was dissolved in the measurement solvent.

[0211] <Acid Value> 3 g of the polymer solution was accurately weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and titrated using a 0.1N aqueous KOH solution as the titrant. Titration was performed using an automatic titrator (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value per 1 g of solid content (mgKOH / g) was determined from the acid value of the polymer solution and the solid content of the polymer solution. The solid content of the polymer solution was determined by the following method. Specifically, approximately 1 g of the polymer solution was weighed into an aluminum cup, approximately 3 g of acetone was added to dissolve the solution, followed by natural drying at room temperature. Then, after drying at 140°C for 1.5 hours under vacuum using a hot air dryer (trade name: PHH-101, manufactured by Espec Corp.), the mixture was allowed to cool in a desiccator, and the mass was measured. The solid content (mass%) of the polymer solution was calculated from the mass loss.

[0212] <Vinyl Ether Equivalent> It is determined by dividing the mass (g) of the polymer solid content by the number of moles (mol) of potentially contained vinyl ether groups in the polymer.

[0213] <Epoxy Equivalent> It is 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> It is determined by dividing the mass (g) of the polymer solid content by the amount (mol) of double bonds in the polymer.

[0215] <Weight Average Molecular Weight> The weight-average molecular weight of polymers was measured by GPC (gel permeation chromatography) using polystyrene as the standard substance and tetrahydrofuran as the eluent, with an HLC-8220GPC (Tosoh Corporation) and a TSKgel SuperHZM-M column (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 percentage change in viscosity before and after storage when the polymer solution is stored at 40°C for one week, and represents the percentage of the viscosity after storage relative to the viscosity before storage (100%). A smaller viscosity change rate indicates better storage stability of the polymer. (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 represents the percentage change in viscosity before and after storage when the photosensitive resin composition is stored at 40°C for one month, and is expressed as the percentage of the viscosity after storage, with the viscosity before storage set to 100%. A smaller viscosity change rate value indicates better storage stability of the photosensitive resin composition.

[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 then 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 removed. The absorbance of the immersion solution after removal was measured using a UV3100 spectrophotometer (Shimadzu Corporation). A higher absorbance value indicated that more colorant had leached into the immersion solution, and the solvent resistance of the photosensitive resin composition was evaluated as low.

[0218] <Developability> A photosensitive resin composition is applied to a 10 cm square glass substrate by spin coating, followed by heat treatment (90°C, 3 minutes). Then, a UV aligner (manufactured by Dainippon Kaken Co., Ltd., product name "MA-1100") equipped with a 2.0 kW ultra-high pressure mercury lamp is used to expose the film to 60 mJ / cm² via a photomask with a 30 μm line-and-space opening 50 μm from the coated film. 2 The developability was evaluated by exposing the samples to an exposure level equivalent to 365nm illuminance, spraying a 0.05% potassium hydroxide aqueous solution using a spin developer to dissolve and remove the unexposed areas, and then developing the remaining exposed areas by washing them with pure water for 10 seconds. Specifically, the coated film developed via a photomask as described above was observed using a surface roughness meter (Ryoka Systems Co., Ltd., product name "VertScan2.0"), and the development time was defined as the spraying time of the 0.05% potassium hydroxide aqueous solution required for the unexposed areas to run off.

[0219] (Manufacturing Example 1) Synthesis of monomeric compound (A-1) In a reaction vessel equipped with a thermometer, stirrer, gas inlet, condenser, and dropper inlet, 100.0 parts of 2-(2-vinyloxyethoxy)ethyl methacrylate and 60.0 parts of acetic acid were charged, and the mixture was heated to 60°C and reacted for 12 hours. After the reaction was complete, the reaction vessel was cooled, diluted with ethyl acetate, and the contents were transferred to a separatory funnel. The oil layer was washed twice with aqueous sodium carbonate solution and twice with water, and the oil layer was extracted. After adsorbing the water in the oil layer with magnesium sulfate, the magnesium sulfate was removed by filtration, and the ethyl acetate in the oil layer was removed using an evaporator to obtain monomer compound (A-1). 1 ¹H-NMR analysis confirmed the disappearance of the vinyl ether-derived peak around 6.5 ppm, and the integral value confirmed the formation of monomer compound (A-1).

[0220] (Manufacturing example 2) Synthesis of monomeric compound (A-2) Monomeric compound (A-2) was obtained by performing the same procedure as in Production Example 1, except that 60.0 parts of acetic acid in Production Example 1 was replaced with 90.0 parts of isopropanol.

[0221] (Production Example 3) Synthesis of Monomer Compound (A-3) A monomer compound (A-3) was obtained by carrying out the same procedure 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) Into a reaction vessel equipped with a thermometer, a stirrer, a gas introduction tube, a cooling tube and a dropping tank introduction port, 30.0 parts of acetic acid and 0.01 parts of p-toluenesulfonic acid were charged, stirred, and heated to 30°C to obtain a uniform mixed solution. Subsequently, 100.0 parts of 2-(2-vinyloxyethoxy)ethyl methacrylate was added dropwise while paying attention to heat generation. After completion of the dropwise addition, a reaction was carried out at 30°C for 3 hours to obtain a monomer compound (A-4). The obtained monomer compound was 1 When confirmed by 1H-NMR, the disappearance of the peak derived from vinyl ether near 6.5 ppm was confirmed, and the formation of monomer compound (A-4) was confirmed from the integrated value.

[0223] (Production Example 5) Synthesis of Monomer Compound (A-5) A monomer compound (A-5) was obtained by carrying out 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) A monomer compound (A-6) was obtained by carrying out 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) A monomer compound (A-7) was obtained by carrying out the same procedure as in Production Example 4, except that 30.0 parts of acetic acid in Production Example 4 was changed to 32.2 parts, and 2-(2-vinyloxyethoxy)ethyl methacrylate was changed to 2-(2-vinyloxyethoxy)ethyl acrylate.

[0226] (Production Example 8) Synthesis of monomeric compound (A-8) The monomer compound (A-8) was obtained by performing the same procedure as in Production Example 7, except that 32.2 parts of acetic acid in Production Example 7 were replaced with 39.8 parts of propionic acid.

[0227] (Manufacturing example 9) Synthesis of monomeric compound (A-9) The monomer compound (A-9) was obtained by performing the same procedure as in Production Example 7, except that 32.2 parts of acetic acid in Production Example 7 was replaced with 47.3 parts of butyric acid.

[0228] (Manufacturing example 10) In a reaction vessel equipped with a thermometer, stirrer, gas inlet, condenser, and dropper inlet, 107.6 parts of lauric acid and 0.01 parts of p-toluenesulfonic acid were charged and stirred, and heated to 50°C to obtain a homogeneous mixture. Subsequently, 100.0 parts of 2-(2-vinyloxyethoxy)ethyl acrylate were added dropwise, taking care to avoid exothermic reactions. After the addition was complete, the reaction was carried out at 50°C for 3 hours to obtain monomer compound (A-10). 1 ¹H-NMR analysis confirmed the disappearance of the vinyl ether-derived peak around 6.5 ppm, and the integral value confirmed the formation of monomer compound (A-10).

[0229] [Table 1]

[0230] The terms in Table 1 represent the following: VEEM: 2-(2-vinyloxyethoxy)ethyl methacrylate VEEA: 2-(2-vinyloxyethoxy)ethyl acrylate Acetic acid (ATOH) PA: Propionic acid BA: Butyrate 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-butyroxyethoxy)ethoxy)ethyl acrylate LEEA: 2-(2-(1-lauroxyethoxy)ethoxy)ethyl acrylate

[0231] From Production Examples 1-3, by using one equivalent or more of a carboxylic acid compound or alcohol compound per one equivalent of a vinyl ether group-containing (meth)acrylate compound, the reaction was accelerated by the reaction substrate itself acting autocatalyzably, as described above, allowing for the synthesis of acetal-protected monomer compounds without a catalyst. Furthermore, from Production Examples 4-10, similar synthesis was possible using an acid catalyst.

[0232] (Example 1) Synthesis of polymer (B-1) In a reaction vessel equipped with a thermometer, stirrer, gas inlet, condenser, and dropper inlet, 146.7 parts of propylene glycol monomethyl ether acetate were charged, the mixture was purged with nitrogen, and then heated to 60°C. Meanwhile, in a dropper (A) beaker, 25.0 parts of propylene glycol monomethyl ether acetate, 23.1 parts of acetic acid, and 0.01 parts of p-toluenesulfonic acid were charged and stirred to obtain a homogeneous mixture. Subsequently, 76.9 parts of 2-(2-vinyloxyethoxy)ethyl methacrylate were added dropwise to the mixture, taking care to avoid exothermic reactions. After the dropwise addition was complete, the mixture was stirred at 30°C for 3 hours. Then, 0.39 parts of triethylamine and 2.9 parts of di-2-ethylhexyl peroxydicarbonate ("Perloyl® OPP" manufactured by NOF Corporation) were added to the dropping tank (A). For the dropping tank (B), 1.0 part of n-dodecyl mercaptan and 59.0 parts of propylene glycol monomethyl ether acetate were mixed in a beaker and stirred. After the reaction vessel reached 60°C, the temperature was maintained, and the mixture was started dropwise from the dropping tank over 3 hours to carry out polymerization. After the dropwise addition was complete, the temperature was maintained at 60°C and the mixture was aged for 6 hours. After that, it was cooled to room temperature to obtain polymer (B-1). The various physical properties of the obtained polymer are shown in Table 2.

[0233] (Example 2) Synthesis of polymer (B-2) In a reaction vessel equipped with a thermometer, stirrer, gas inlet, condenser, and dropping tank inlet, 133.0 parts of propylene glycol monomethyl ether acetate were charged, the mixture was purged with nitrogen, and then heated to 50°C. On the other hand, for dropping tank (A), a beaker 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) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., V-70). For dropping tank (B), a beaker was prepared by stirring and mixing 2.0 parts of n-dodecyl mercaptan and 58.0 parts of propylene glycol monomethyl ether acetate. After the reaction vessel reached 50°C, polymerization was carried out by starting the addition of the solution from the dropping vessel over a period of 3 hours while maintaining the same temperature. After the addition was complete, the temperature was maintained at 50°C and the mixture was aged for 7 hours. After that, it was cooled to room temperature to obtain polymer (B-2). The various physical properties of the obtained polymer are shown in Table 2.

[0234] (Example 3) Synthesis of polymer (B-3) In a reaction vessel equipped with a thermometer, stirrer, gas inlet, condenser, and dropper inlet, 109.3 parts of propylene glycol monomethyl ether acetate were charged, the mixture was purged with nitrogen, and then heated to 60°C. Meanwhile, a dropper 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. An initiator 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 reaction vessel reached 60°C, polymerization was carried out by dropper addition from the dropper over 3 hours while maintaining the same temperature. The 30 portions of the initiator tank were added to the reaction vessel in six separate additions of 5 portions each, at 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours after the start of polymerization. After the addition was complete, the reaction vessel was heated to 70°C and aged for 10 hours. After that, it was cooled to room temperature to obtain polymer (B-3). The various physical properties of the obtained polymer are shown in Table 2.

[0235] (Example 4) Synthesis of the process (B-4) In a reaction vessel equipped with a thermometer, stirrer, gas inlet, condenser, and dropping tank inlet, 115.3 parts of propylene glycol monomethyl ether acetate were charged, the mixture was purged with nitrogen, and then heated to 60°C. Meanwhile, as dropping tank (A), a beaker 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. As dropping tank (B), a beaker was prepared by charging 60.0 parts of propylene glycol monomethyl ether acetate, 6.9 parts of acetic acid, and 0.002 parts of p-toluenesulfonic acid, stirring and mixing to obtain a homogeneous mixture. Subsequently, 23.1 parts of 2-(2-vinyloxyethoxy)ethyl methacrylate were added dropwise to the above mixture, taking care to avoid exothermic reactions. After the dropwise addition was complete, the mixture was stirred at 30°C for 3 hours, and 0.12 parts of triethylamine were added and stirred to form the dropping tank (B). For the initiator tank, 2.9 parts of di-2-ethylhexyl peroxydicarbonate ("Perloyl® OPP" manufactured by NOF Corporation) and 27.1 parts of propylene glycol monomethyl ether acetate were mixed in a beaker and stirred. After the reaction vessel temperature reached 60°C, the temperature was maintained, and the addition was started dropwise from dropping tanks (A) and (B) over 3 hours to carry out polymerization. A total of 30 parts of the initiator tank were added at 0 minutes, 30 minutes, 1 hour, and 1 hour of polymerization. The mixture was added to the reaction vessel in six separate additions of 5 parts each, at intervals of 5 hours, 2 hours, and 2.5 hours. After the addition was complete, the mixture was aged for 6 hours at a temperature of 60°C. After cooling to room temperature, 11.5 parts succinic anhydride, 11.7 parts triethylamine, and 29.6 parts propylene glycol monomethyl ether acetate were added to the reaction vessel, and the reaction was carried out at 50°C for 1 hour. After the reaction, the mixture was cooled to room temperature to obtain polymer (B-4). The various properties of the obtained polymer are shown in Table 2.

[0236] (Example 5) Synthesis of polymer (B-5) In a reaction vessel equipped with a thermometer, stirrer, gas inlet, condenser, and dropping tank inlet, 146.0 parts of propylene glycol monomethyl ether acetate were charged, the mixture was purged with nitrogen, and then heated to 60°C. Meanwhile, as dropping tank (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) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., V-65), and 40.0 parts of propylene glycol monomethyl ether acetate. As dropping tank (B), a beaker was prepared by stirring and mixing 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 homogeneous mixture. Next, 30.8 parts of 2-(2-vinyloxyethoxy)ethyl methacrylate were added dropwise to the above mixture, taking care to avoid exothermic reactions. After the addition was complete, the mixture was stirred at 30°C for 3 hours, and 0.16 parts of triethylamine and 3.5 parts of n-dodecyl mercaptan were added to prepare dropwise bath (B). After the reaction vessel reached 60°C, polymerization was carried out by dropwise addition from dropwise addition vessels (A) and (B) over a period of 3 hours while maintaining the same temperature. After the addition was completed, the temperature was raised to 70°C and the mixture was aged for 10 hours. After cooling to room temperature, 15.4 parts succinic anhydride, 15.6 parts triethylamine, and 42.1 parts propylene glycol monomethyl ether acetate were added to the reaction vessel and the reaction was carried out at 50°C for 1 hour. After the reaction, the mixture was cooled to room temperature to obtain polymer (B-5). The various properties of the obtained polymer are shown in Table 2.

[0237] (Example 6) Synthesis of polymer (B-6) In a reaction vessel equipped with a thermometer, stirrer, gas inlet, condenser, and dropping tank inlet, 160.8 parts of propylene glycol monomethyl ether acetate were charged, stirred and mixed, then purged with nitrogen, and heated to 50°C. On the other hand, for dropping tank (A), a beaker 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) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., V-70), and 15.0 parts of propylene glycol monomethyl ether acetate. For dropping tank (B), a beaker was prepared by stirring and mixing 2.0 parts of n-dodecyl mercaptan and 58.0 parts of propylene glycol monomethyl ether acetate. After the reaction vessel reached 50°C, polymerization was carried out by starting the addition of the solution from dropper tanks (A) and (B) over a period of 3 hours while maintaining the same temperature. After the addition was complete, the temperature was maintained at 50°C and the mixture was aged for 7 hours. After that, it was cooled to room temperature to obtain polymer (B-6). The various physical properties of the obtained polymer are shown in Table 2.

[0238] (Example 7) Synthesis of polymer (B-7) In a reaction vessel equipped with a thermometer, stirrer, gas inlet, condenser, and dropper inlet, 190.8 parts of propylene glycol monomethyl ether acetate and 14.3 parts of triethylamine were charged, the mixture was purged with nitrogen, and then heated to 60°C. On the other hand, as a dropper inlet, a beaker was prepared containing 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, which were stirred and mixed. As an initiator inlet, a beaker was prepared containing di-2-ethylhexyl peroxydicarbonate (manufactured by NOF Corporation, "Perloyl®") A mixture of 2.9 parts of OPP and 27.1 parts of propylene glycol monomethyl ether acetate was prepared by stirring. After the reaction vessel reached a temperature of 60°C, polymerization was carried out by starting the addition of the solution from the dropping tank over a period of 3 hours while maintaining the same temperature. The total of 30 parts from the initiator tank was added to the reaction vessel in 5 parts at 6 intervals: 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours after the start of polymerization. After the addition was completed, the temperature was maintained at 60°C and the mixture was aged for 6 hours. After that, it was cooled to room temperature to obtain polymer (B-7). The various physical properties of the obtained polymer are shown in Table 2.

[0239] (Example 8) Synthesis of polymer (B-8) In a reaction vessel equipped with a thermometer, stirrer, gas inlet, condenser, and dropping tank inlet, 172.6 parts of propylene glycol monomethyl ether acetate and 23.9 parts of triethylamine were charged, the mixture was purged with nitrogen, and then heated to 50°C. Meanwhile, as dropping tank (A), a beaker 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. As dropping tank (B), a beaker 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. The mixture was stirred and mixed to obtain a homogeneous solution. Subsequently, 57.7 parts of 2-(2-vinyloxyethoxy)ethyl methacrylate was added dropwise to the mixture, taking care to avoid exothermic reactions. After the dropwise addition was complete, the mixture was stirred at 30°C for 3 hours to prepare dropwise addition tank (B). For the 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 mixed and stirred together. After the reaction tank temperature reached 50°C, the mixture was maintained at the same temperature and the addition was started dropwise from dropwise addition tanks (A) and (B) over 3 hours to carry out polymerization. The total of 30 parts of the initiator tank were added to the reaction tank in 5 parts at 6 intervals: 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 complete, the temperature was maintained at 50°C and the mixture was aged for 7 hours. After that, it was cooled to room temperature to obtain polymer (B-8). The various physical properties of the obtained polymer are shown in Table 2.

[0240] (Example 9) Synthesis of polymer (B-9) In a reaction vessel equipped with a thermometer, stirrer, gas inlet, condenser, and dropping tank inlet, 145.8 parts of propylene glycol monomethyl ether acetate were charged, the mixture was purged with nitrogen, and then heated to 60°C. Meanwhile, as dropping tank (A), a beaker was prepared containing 10.0 parts N-benzylmaleimide, 30.0 parts cyclohexyl methacrylate, 30.0 parts 2-hydroxyethyl methacrylate, 2.0 parts 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., V-65), and 30.0 parts propylene glycol monomethyl ether acetate, which were stirred and mixed. As dropping tank (B), a beaker was prepared containing 57.5 parts propylene glycol monomethyl ether acetate, 6.9 parts acetic acid, and 0.002 parts p-toluenesulfonic acid, which were stirred and mixed to obtain a homogeneous mixture. Next, 23.1 parts of 2-(2-vinyloxyethoxy)ethyl methacrylate were added dropwise to the mixture, taking care to avoid exothermic reactions. After the addition was complete, the mixture was stirred at 30°C for 3 hours, and 0.10 parts of diethylmethylamine and 2.5 parts of n-dodecyl mercaptan were added to create dropping tank (B). After the reaction vessel reached 60°C, the temperature was maintained, and the addition of polymers from dropping tanks (A) and (B) was started over 3 hours to carry out the polymerization. After the addition was complete, the temperature was raised to 70°C and the mixture was aged 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 added to the reaction vessel, and the reaction was carried out at 50°C for 1 hour. After the reaction, the mixture was cooled to room temperature to obtain polymer (B-9). The various properties of the obtained polymer are shown in Table 2.

[0241] (Example 10) Synthesis of polymer (B-10) In a reaction vessel equipped with a thermometer, stirrer, gas inlet, condenser, and dropping tank inlet, 228.3 parts of propylene glycol monomethyl ether acetate were charged, and after purging with nitrogen, the mixture was heated to 60°C. On the other hand, for dropping tank (A), a beaker 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® OPP"), and 30.0 parts of propylene glycol monomethyl ether acetate. For dropping tank (B), a beaker was prepared by stirring and mixing 2.5 parts of n-dodecyl mercaptan and 57.5 parts of propylene glycol monomethyl ether acetate. After the reaction vessel reached 60°C, polymerization was carried out by dropwise addition from dropwise addition vessels (A) and (B) over a period of 3 hours while maintaining the same temperature. After the addition was completed, the temperature was maintained at 60°C and the mixture was aged for 6 hours. Then, it was cooled to room temperature, and 26.2 parts of 2-methacryloyloxyethyl isocyanate, 16.8 parts of triethylamine, and 0.2 parts of Antige W400 were added. The mixture was reacted at 90°C for 2 hours while bubbling with an oxygen / nitrogen mixed gas adjusted to an oxygen concentration of 7% at a rate of 20 ml / min. After cooling to room temperature, 16.6 parts of succinic anhydride were added, and the mixture was reacted at 50°C for 1 hour. After the reaction was complete, it was cooled to room temperature to obtain polymer (B-10). The various properties of the obtained polymer are shown in Table 2.

[0242] (Example 11) Synthesis of polymer (B-11) In a reaction vessel equipped with a thermometer, stirrer, gas inlet, condenser, and dropper inlet, 263.7 parts of propylene glycol monomethyl ether acetate were charged, the mixture was purged with nitrogen, and then heated to 60°C. On the other hand, as a dropper inlet, a mixture of 15.0 parts N-benzylmaleimide, 15.0 parts cyclohexyl methacrylate, 25.0 parts glycidyl methacrylate, 20.0 parts 2-hydroxyethyl methacrylate, 25.0 parts 2-(2-(1-isopropoxyethoxy)ethoxy)ethyl methacrylate, 3.0 parts n-dodecyl mercaptan, and 25.0 parts propylene glycol monomethyl ether acetate was prepared by stirring and mixing in a beaker. As an initiator tank, a beaker 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. After the reaction vessel temperature reached 60°C, polymerization was carried out by starting the addition of the solution from the dropping tank over 3 hours while maintaining the same temperature. The total of 30 parts of the initiator tank were added to the reaction vessel in 6 portions of 5 parts each at 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours after the start of polymerization. After the addition was completed, the reaction vessel temperature was raised 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 Antige W400 were added. The reaction was carried out at 110°C for 7 hours while bubbling an oxygen / nitrogen mixed gas adjusted to an oxygen concentration of 7% at 20 ml / min. After cooling to room temperature, 12.0 parts of succinic anhydride were added, and the mixture was reacted at 50°C for 1 hour. After the reaction was complete, the mixture was cooled to room temperature to obtain polymer (B-11). The various properties of the obtained polymer are shown in Table 2.

[0243] (Example 12) Synthesis of polymer (B-12) In a reaction vessel equipped with a thermometer, stirrer, gas inlet, condenser, and dropping tank inlet, 215.7 parts of propylene glycol monomethyl ether acetate were charged, the mixture was purged with nitrogen, and then heated to 60°C. Meanwhile, as dropping tank (A), a beaker 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. As dropping tank (B), a beaker 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. The mixture was stirred and mixed to obtain a homogeneous solution. Subsequently, 16.3 parts of 2-(2-vinyloxyethoxy)ethyl methacrylate were added dropwise to the mixture, taking care to avoid exothermic reactions. After the dropwise addition was complete, the mixture was stirred at 30°C for 3 hours, and 0.08 parts of triethylamine and 2.0 parts of n-dodecyl mercaptan were added to create dropwise addition tank (B). 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 mixed in a beaker and stirred together. After the reaction tank reached 60°C, the temperature was maintained, and the mixture was started dropwise from dropwise addition tanks (A) and (B) over 3 hours to carry out polymerization. The total of 30 parts of the initiator tank were added to the reaction tank in 5 parts at 6 times: 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 complete, the reaction tank was heated to 70°C and aged for 10 hours. The mixture was then cooled to room temperature, and 14.0 parts of methacrylic acid, 26.9 parts of triethylamine, and 0.2 parts of Antige W400 were added. The mixture was reacted at 110°C for 7 hours while bubbling with an oxygen / nitrogen mixed gas adjusted to a 7% oxygen concentration at 20 ml / min. After cooling to room temperature, 26.6 parts of succinic anhydride were added, and the mixture was reacted at 50°C for 1 hour. After the reaction was complete, the mixture was cooled to room temperature to obtain polymer (B-12). The various properties of the obtained polymer are shown in Table 2.

[0244] (Example 13) Synthesis of polymer (B-13) In a reaction vessel equipped with a thermometer, stirrer, gas inlet, condenser, and dropping tank inlet, 145.3 parts of propylene glycol monomethyl ether acetate were charged, the mixture was purged with nitrogen, and then heated to 60°C. Meanwhile, as dropping tank (A), a beaker 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. As dropping tank (B), a beaker 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. The mixture was stirred and mixed to obtain a homogeneous solution. Subsequently, 22.7 parts of 2-(2-vinyloxyethoxy)ethyl acrylate were added dropwise to the above mixture, taking care to avoid exothermic reactions. After the dropwise addition was complete, the mixture was stirred at 30°C for 3 hours, and 0.12 parts of triethylamine were added and stirred to form the dropwise addition 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 mixed in a beaker and stirred together. After the reaction vessel temperature reached 60°C, the mixture was maintained at the same temperature and the addition was started dropwise from dropwise addition tanks (A) and (B) over 3 hours to carry out polymerization. The total of 30 parts of the initiator tank were added to the reaction vessel in 5 parts at 6 times: 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 complete, the temperature was raised to 70°C and the mixture was aged for 6 hours. After cooling to room temperature, 11.5 parts succinic anhydride, 11.7 parts triethylamine, and 29.6 parts propylene glycol monomethyl ether acetate were added to the reaction vessel, and the reaction was carried out at 50°C for 1 hour. After the reaction, the mixture was cooled to room temperature to obtain polymer (B-13). The various physical properties of the obtained polymer are shown in Table 2.

[0245] (Example 14) Synthesis of polymer (B-14) In a reaction vessel equipped with a thermometer, stirrer, gas inlet, condenser, and dropping tank inlet, 145.3 parts of propylene glycol monomethyl ether acetate were charged, the mixture was purged with nitrogen, and then heated to 60°C. Meanwhile, for dropping tank (A), a beaker 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. For dropping tank (B), a beaker was prepared by charging 30.0 parts of propylene glycol monomethyl ether acetate, 8.5 parts of propionic acid, and 0.002 parts of p-toluenesulfonic acid, stirring and mixing to obtain a homogeneous mixture. Next, 21.5 parts of 2-(2-vinyloxyethoxy)ethyl acrylate were added dropwise to the above mixture, taking care to avoid exothermic reactions. After the dropwise addition was complete, the mixture was stirred at 30°C for 3 hours, and 0.12 parts of triethylamine were added and stirred 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 mixed in a beaker and stirred together. After the reaction tank temperature reached 60°C, the temperature was maintained, and the addition of the mixture from dropping tanks (A) and (B) was started over 3 hours to carry out polymerization. The total of 30 parts of the initiator tank were added to the reaction tank in 5 parts at 6 intervals: 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 complete, the temperature was raised to 70°C and the mixture was aged for 6 hours. After cooling to room temperature, 11.5 parts succinic anhydride, 11.7 parts triethylamine, and 29.6 parts propylene glycol monomethyl ether acetate were added to the reaction vessel and the reaction was carried out at 50°C for 1 hour. After the reaction, the mixture was cooled to room temperature to obtain polymer (B-14). The various physical properties of the obtained polymer are shown in Table 2.

[0246] (Example 15) Synthesis of polymer (B-15) In a reaction vessel equipped with a thermometer, stirrer, gas inlet, condenser, and dropping tank inlet, 146.8 parts of propylene glycol monomethyl ether acetate were charged, the mixture was purged with nitrogen, and then heated to 60°C. Meanwhile, for dropping tank (A), a beaker 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. For dropping tank (B), a beaker 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. The mixture was stirred and mixed to obtain a homogeneous mixture. Next, 21.4 parts of 2-(2-vinyloxyethoxy)ethyl acrylate were added dropwise to the above mixture, taking care to avoid exothermic reactions. After the dropwise addition was complete, the mixture was stirred at 30°C for 3 hours, and 0.12 parts of triethylamine were added and stirred 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 mixed in a beaker and stirred together. After the reaction vessel temperature reached 60°C, the temperature was maintained, and the addition of the mixture from dropping tanks (A) and (B) was started over 3 hours to carry out polymerization. The total of 30 parts of the initiator tank were added to the reaction vessel in 5 parts at 6 intervals: 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 complete, the temperature was raised to 70°C and the mixture was aged for 6 hours. After cooling to room temperature, 11.5 parts succinic anhydride, 11.7 parts triethylamine, and 29.6 parts propylene glycol monomethyl ether acetate were added to the reaction vessel and the reaction was carried out at 50°C for 1 hour. After the reaction, the mixture was cooled to room temperature to obtain polymer (B-15). The various physical properties of the obtained polymer are shown in Table 2.

[0247] (Example 16) Synthesis of polymer (B-16) In a reaction vessel equipped with a thermometer, stirrer, gas inlet, condenser, and dropping tank inlet, 159.8 parts of propylene glycol monomethyl ether acetate were charged, the mixture was purged with nitrogen, and then heated to 60°C. Meanwhile, for dropping tank (A), a beaker 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. For dropping tank (B), a beaker was prepared by charging 15.5 parts of propylene glycol monomethyl ether acetate, 23.1 parts of lauric acid, and 0.002 parts of p-toluenesulfonic acid, heating to 50°C, stirring and mixing to obtain a homogeneous mixture. Next, 21.4 parts of 2-(2-vinyloxyethoxy)ethyl acrylate were added dropwise to the above mixture, taking care to avoid exothermic reactions. After the dropwise addition was complete, the mixture was stirred at 50°C for 3 hours, and 0.12 parts of triethylamine were added and stirred 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 mixed in a beaker and stirred together. After the temperature of the reaction vessel reached 60°C, the temperature was maintained, and the addition of the mixture from dropping tanks (A) and (B) was started over 3 hours to carry out polymerization. The total of 30 parts of the initiator tank were added to the reaction vessel in 5 parts at 6 intervals: 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 complete, the temperature was raised to 70°C and aged for 6 hours. After cooling to room temperature, 11.5 parts succinic anhydride, 11.7 parts triethylamine, and 29.6 parts propylene glycol monomethyl ether acetate were charged into the reaction vessel and the reaction was carried out at 50°C for 1 hour. After the reaction, the mixture was cooled to room temperature to obtain polymer (B-16). The various physical properties of the obtained polymer are shown in Table 2.

[0248] (Comparative Example 1) Synthesis of polymer (B-17) In a reaction vessel equipped with a thermometer, stirrer, gas inlet, condenser, and dropper inlet, 143.3 parts of propylene glycol monomethyl ether acetate were charged, the mixture was purged with nitrogen, and then heated to 70°C. Meanwhile, a dropper (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 dropper (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 reaction vessel reached 70°C, the mixture was maintained at the same temperature and polymerization was carried out by dropping from dropper (A) and (B) over a period of 3 hours. After the dropper addition was completed, the temperature was maintained at 70°C and the mixture was aged for 7 hours. The mixture was then cooled to room temperature to obtain polymer (B-17). The various properties of the obtained polymer are shown in Table 2.

[0249] (Comparative Example 2) Synthesis of polymer (B-18) In a reaction vessel equipped with a thermometer, stirrer, gas inlet, condenser, and dropper inlet, 143.3 parts of propylene glycol monomethyl ether acetate and 10.8 parts of triethylamine were charged, and after purging with nitrogen, the mixture was heated to 70°C. Meanwhile, a dropper (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 dropper (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 reaction vessel reached 70°C, the mixture was maintained at the same temperature and polymerization was carried out by dropping from dropper (A) and (B) over a period of 3 hours. After the dropper addition was completed, the temperature was maintained at 70°C and the mixture was aged for 7 hours. The mixture was then cooled to room temperature to obtain polymer (B-18). The various properties of the obtained polymer are shown in Table 2.

[0250] (Comparative Example 3) Synthesis of polymer (B-19) In a reaction vessel equipped with a thermometer, stirrer, gas inlet, condenser, and dropper inlet, 105.3 parts of propylene glycol monomethyl ether acetate were charged, the mixture was purged with nitrogen, and then heated to 70°C. Meanwhile, for dropper inlet (A), a beaker was prepared containing 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® 11, manufactured by Arkema Yoshitomi Co., Ltd.), which were stirred and mixed. For dropper inlet (B), 2.0 parts of n-dodecyl mercaptan and 78 parts of propylene glycol monomethyl ether acetate were stirred and mixed. After the temperature of the reaction vessel reached 70°C, polymerization was carried out by starting the addition of the mixture from the dropper inlet over a period of 3 hours while maintaining the same temperature. After the dropwise addition was complete, the temperature was maintained at 70°C for 30 minutes, then raised to 80°C and aged for 180 minutes to obtain polymer (B-19). The various physical properties of the obtained polymer are shown in Table 2.

[0251] [Table 2]

[0252] The terms 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 (manufactured by NOF Corporation as "Perloyl® OPP") V70: 2,2'-Azobis(4-Methoxy-2,4-dimethylvaleronitrile) (V-70, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) V65: 2,2'-Azobis(2,4-dimethylvaleronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., V-65) AIBN: Azobisisobutyronitrile L11: t-butyl peroxypivalate (Luperox 11, manufactured by Arkema Yoshitomi Co., Ltd.) TEA: Triethylamine DEMA: Diethylmethylamine

[0253] (Preparation of photosensitive resin composition) In terms of solid content, 35 parts of polymer (B-1), 30 parts of pigment dispersion 1, 30 parts of dipentaerythritol hexaacrylate (DPHA), and 5 parts of IRGACURE® OXE02 (manufactured by BASF Japan) were added. Further dilution solvent (propylene glycol monomethyl ether acetate) was added to bring the solid content concentration (non-volatile content) to 20% by mass, and the mixture was stirred to obtain photosensitive resin composition (C-1).

[0254] (Preparation of Pigment Dispersion 1) Pigment dispersion 1 (solids content 22% by mass) was obtained by mixing 12.9 parts of propylene glycol monomethyl ether acetate, 0.4 parts of Disparon DA-7301 as a basic dispersant, 2.25 parts of CI Pigment Green 58 as a colorant, and 1.5 parts of CI Pigment Yellow 138 as colorants, and dispersing the mixture in a paint shaker for 3 hours.

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

[0256] [Table 3]

[0257] Tables 2 and 3 show that the polymers of Examples 4-16 developed faster and showed improved solvent resistance compared to the polymers of Comparative Examples 1-3. The acetal monomer units of the polymers in Examples 4-16 have PEG chains and are highly hydrophilic, which is thought to have contributed to the improved development speed. On the other hand, in Comparative Examples 1 and 2, the acetal monomer units and acid group-containing monomer units of the polymer backbone have an alicyclic structure, resulting in high hydrophobicity and steric hindrance. This leads to a slower development rate, less progress in the crosslinking reaction, and a tendency towards poor solvent resistance. In addition, in Comparative Example 3, the high reactivity between the acid group and epoxy group results in poor storage stability of the polymer and photosensitive resin composition. Consequently, there are fewer unreacted acid groups at the time of development, leading to a slower development rate. Furthermore, the crosslinking reaction of acid epoxy results in a lower crosslink density during curing compared to reactions such as the cationic polymerization of vinyl ether, which is thought to have contributed to the tendency towards poor solvent resistance.

[0258] Compared to Comparative Examples 1-3, the storage stability of Examples 1-16 was confirmed to be good. The lower storage stability of Examples 11 and 12 compared to the other examples is thought to be because they have epoxy groups in their side chains and are resins containing triethylamine (a basic compound) in a neutralized amount. On the other hand, the poor storage stability of the comparative examples is because when monomers that produce vinyl ether are copolymerized with an alicyclic skeleton, detachment easily progresses during storage, causing the vinyl ether groups to crosslink. On the other hand, the forms of the examples with linear or branched chains have good stability during storage as vinyl ether does not easily detach, and detachment occurs all at once during low-temperature firing. The detached vinyl ether has high reactivity, resulting in good solvent resistance, thus overcoming the trade-off between storage stability and solvent resistance. Furthermore, in Comparative Example 1, since there was no basic compound to neutralize the acid group-containing monomer units, the protective group of the vinyl ether was removed during storage of the polymer solution, the vinyl ether group was regenerated, and crosslinking progressed. Therefore, it is thought that the storage stability was worse compared to Comparative Example 2. For similar reasons, it is thought that the storage stability of Example 6 was worse than that of the other examples.

[0259] In addition, while Examples 1-3 showed better solvent resistance and storage stability compared to Comparative Examples 1-3, the development speed was found to be slower. This is thought to be because the polymer does not contain acid group-containing monomer units. Furthermore, Examples 1, 4, 8, 9, 10, 13, 14, 15, and 16 showed smaller viscosity changes and a tendency toward better storage stability compared to Examples 2, 3, 5, 7, 11, and 12. This is because the stability of AEEM, AEEA, PEEA, BEEA, and LEEA is better than that of IEM and EEEM in the polymer, so carboxylic acids are preferred over alcohols as the vinyl ether group protecting monomers.

[0260] In Example 13, the development speed was found to be faster compared to Example 4. This is thought to be due to the effect of lowering the glass transition temperature (Tg) of the resin by changing from VEEM to VEEA. Similarly, in Example 15, compared to Example 14, and in Example 14, compared to Example 13, the solvent resistance was equivalent, but the viscosity change rate was smaller, and the storage stability was found to be better. This is thought to be because a longer molecular chain of the carboxylic acid compound that forms the acetal monomer unit is effective in suppressing the detachment of the carboxylic acid compound, thus improving storage stability. On the other hand, in Example 16, compared to Example 15, the storage stability was equivalent, but the solvent resistance was found to be worse. This is thought to be because a longer molecular chain of the carboxylic acid compound is effective in suppressing the detachment of the carboxylic acid compound, but a longer molecular chain reduces the crosslinking density when thermally cured, thus decreasing solvent resistance. Therefore, butyric acid with 4 carbon atoms in the carboxylic acid is the most preferred.

[0261] (Confirmation of the effect of the diluent) To investigate the effect of diluent solvents on the storage stability of polymers, the following procedure was performed. Storage stability was evaluated using a polymer solution prepared by adding 26 parts of diluent solvent to 74 parts of polymer (B-15) in its original state (20 parts solids, 54 parts volatile matter). Storage stability was evaluated by measuring the increase in weight-average molecular weight before and after storage at 40°C for one week. The weight-average molecular weight of the polymer was measured using the method described above. Table 4 shows the weight-average molecular weight (%) after storage, with the weight-average molecular weight of the polymer before storage set to 100%. A smaller increase in weight-average molecular weight indicated better storage stability of the polymer. Five types of diluent 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] [Table 4]

[0263] Table 4 shows that in Examples 17, 18, 19, and 20, the rate of change in the weight-average molecular weight of the polymer was smaller compared to Example 21. From this, it can be considered that adding alcohol solvents, ether-based solvents, or amide-based solvents to the polymer improves its storage stability. Furthermore, the rate of change in weight-average molecular weight increased in the order of Examples 17, 18, 19, and 20. From this, it can be considered that ether-based solvents, alcohol-based solvents, and amide-based solvents are effective in improving storage stability in that order. In addition, it was found that in Example 18, the rate of change in weight-average molecular weight was smaller compared to Example 19. From this, it can be considered that among alcohol solvents, secondary alcohol solvents are more suitable than primary alcohol solvents for improving storage stability.

[0264] (Confirmation of the effect of the dispersant) To investigate the effect of dispersant addition on the storage stability of polymers, the following procedure was performed. Storage stability was evaluated using polymer solutions prepared by adding 10 parts by mass of the amine-based dispersant Disperbyk-164 (amine value 18 mg KOH / g, solids content 60%, manufactured by BYK-Chemie) to 90 parts by mass of polymer (B-5) or polymer (B-11). Storage stability was evaluated by measuring 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. A smaller change in acid value indicated better storage stability of the polymer. The evaluation results are shown in Table 5. For reference, the change in acid value was also evaluated similarly for polymers (B-5) and (B-11) alone.

[0265] [Table 5]

[0266] Table 5 shows that the resin solutions of Examples 22-25 exhibited smaller changes in acid value and superior storage stability compared to the resin solutions of Comparative Examples 4-5. Comparing Examples 22 and 23, which contained polymer (B-5), with Examples 24 and 25, which contained polymer (B-11), the resin solutions of the examples containing polymer (B-5) showed smaller changes in acid value, regardless of the presence or absence of an amine-based dispersant. Considering these results, it was found that a lower amount of epoxy groups in the resin leads to better storage stability.

[0267] Furthermore, comparing Example 22 and Example 23, it was found that the resin solution of Example 22, which contained an amine-based dispersant, showed a smaller change in acid value and superior 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 and Example 25, it was found that the resin solution of Example 24, which contained an amine-based dispersant, showed a larger change in acid value. This trend was also observed when comparing Comparative Example 4 and Comparative Example 5. From these results, it was concluded that amine-based dispersants reduce the storage stability of resins containing epoxy groups. This was thought to be due to the acceleration of the reaction between acid groups and epoxy groups by the addition of amine-based dispersants. From the above, it was found that the polymers of the examples exhibited excellent storage stability, and when the composition includes an amine-based dispersant, a lower amount of epoxy groups resulted in even better storage stability. Furthermore, comparing Example 23, Example 25, and Comparative Example 5, the change in acid value increases in this order, indicating that even without an amine-based dispersant, a lower epoxy group content results in better storage stability.

Claims

1. A polymer characterized by having a structural unit (A) represented by the following formula (1), an acid group-containing structural unit (B), and a structural unit (D) derived from a hydroxyl group-containing monomer other than the structural unit (A) and the acid group-containing structural unit (B). 【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 upon acid or heat to form vinyl ether groups in the polymer side chains.)

2. The polymer according to claim 1, characterized in that 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 (This represents an organic group with 1 to 20 carbon atoms.)

3. Furthermore, the polymer according to claim 1 is characterized by having a structural unit (C) having a ring structure in the main chain.

4. The polymer according to claim 3, characterized in that the structural unit (C) having a ring structure in the main chain is a structural unit derived from at least one monomer selected from the group consisting of N-substituted maleimide monomers, dialkyl-2,2'-(oxydimethylene)diacrylate monomers, and α-(unsaturated alkoxyalkyl)acrylate monomers.

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

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

7. A colorant dispersion characterized by comprising the polymer solution described in claim 6 and a colorant.

8. A photosensitive resin composition comprising a polymer according to any one of claims 1 to 4, a polymerizable compound, and a photopolymerization initiator and / or a photoacid generator.

9. The photosensitive resin composition according to claim 8, characterized in that it is for forming a color filter.

10. A cured product characterized by being obtained by curing the photosensitive resin composition described in claim 8.

11. A method for producing a polymer having a structural unit (A) represented by the following formula (1), an acid group-containing structural unit (B), and a structural unit (D) derived from a hydroxyl group-containing monomer other than the structural unit (A) and the acid group-containing structural unit (B), The manufacturing method includes a step (P-1) of polymerizing a monomer component containing a group that generates a vinyl ether group by acid or heat, and an acid group-containing monomer. A method for producing polymers, characterized by the following: 【Transformation 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 upon acid or heat to form vinyl ether groups in the polymer side chains.)

12. The method for producing a polymer according to claim 11, wherein the step (P-1) is a step of polymerizing the monomer component in the presence of a basic compound, and the amount of the basic compound used is 0.5 to 10 equivalents per equivalent of the acid group-containing monomer.

13. A method for producing a polymer having a structural unit (A) represented by the following formula (1), an acid group-containing structural unit (B), and a structural unit (D) derived from a hydroxyl group-containing monomer other than the structural unit (A) and the acid group-containing structural unit (B), The manufacturing method comprises a step (Q-1) of polymerizing a monomer component containing a monomer that generates a vinyl ether group by acid or heat, and a monomer containing a hydroxyl group, The process includes a step (Q-2) in which an acid group-containing compound is reacted with the polymer obtained in step (Q-1). A method for producing polymers, characterized by the following: 【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 upon acid or heat to form vinyl ether groups in the polymer side chains.)

14. The method for producing a polymer according to claim 13, characterized in that the above step (Q-2) is carried out in the presence of a basic compound, and the amount of the basic compound used is 0.5 to 10 equivalents per equivalent of a constituent unit containing an acid group.

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