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

Abstract

The invention provides a polymer, a photosensitive resin composition containing the polymer, and a cured product thereof, wherein the polymer can form a cured product with excellent solvent resistance even under low-temperature curing conditions and has excellent storage stability. The present invention relates to a polymer characterized by having a structure represented by formula (1) (in the formula, X represents a hydrogen atom or a methyl group. And L represents a linear or branched divalent organic group. And Y represents an organic group which is decomposed by the action of an acid or heat and generates a vinyl ether group in a polymer side chain. ) A structural unit (A) represented by formula (1). # imgabs0 #

Description

Technical Field

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

[0002] Various studies have been conducted on the use of photosensitive resin compositions in various applications such as various optical components such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, organic insulating films, organic protective films, etc. used in liquid crystal display devices or solid-state imaging elements, or motor / electronic equipment, and resins or resin compositions with excellent properties required for each application have been developed.

[0003] In recent years, the miniaturization, thinning, and energy saving of optical components, motors, electronic devices, etc. have been progressing, and with this, higher quality performance is required for various components used. In order to meet such requirements, research has been conducted on resins and photosensitive resin compositions as materials for various components.

[0004] Resins and photosensitive resin compositions that meet various requirements have been developed so far (Patent Documents 1 to 7).

[0005] For example, Patent Document 1 describes a photocurable composition containing a compound having a specific group and a photopolymerization initiator as a composition having sufficient photocurability, capable of obtaining a high-resolution pattern by photolithography, and having excellent thermal decomposition properties during firing, wherein the specific group has a (meth)acryloyl group and an acetal group or a hemiacetal group.

[0006] In addition, for example, Patent Document 2 describes a photosensitive resin composition having high sensitivity and capable of obtaining a cured film having high transparency and excellent ITO sputtering resistance, the composition comprising a polymer having a weight average molecular weight greater than 1000, a photoacid generator, and a solvent, the polymer comprising: a monomer unit having a residue that generates a carboxyl group or a phenolic hydroxyl group by the action of an acid; and a monomer unit having a group having 3 to 16 carbon atoms and having an ethylenically unsaturated bond at the terminal.

[0007] In addition, for example, Patent Document 3 describes a resin composition comprising an alkali-soluble resin having a structure derived from a vinyl ether compound and a basic compound as a resin composition having excellent storage stability, and Patent Document 4 describes a negative resist composition comprising at least a constituent component having a vinyl ether structure protected by acetal in the molecule.

[0008] In addition, Patent Documents 5 to 7 describe polyfunctional (meth)acrylates having an acetal structure.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent Application Publication No. 2003-195497

[0012] Patent Document 2: Japanese Patent Application Publication No. 2011-209682

[0013] Patent Document 3: Japanese Patent Application Publication No. 2018-53031

[0014] Patent Document 4: Japanese Patent Application Publication No. 2002-148805

[0015] Patent Document 5: Japanese Patent Application Publication No. 2003-201267

[0016] Patent Document 6: Japanese Patent Application Publication No. 2007-45924

[0017] Patent Document 7: Japanese Patent Application Publication No. 2013-10726 Summary of the invention

[0018] Problems to be solved by the invention

[0019] As described above, various studies have been conducted on resins and photosensitive resin compositions. However, when a photosensitive resin composition containing an existing resin is used together with a colorant as a raw material for a color filter, for example, the colorant is eluted from the raw material into a cleaning solvent during the manufacture of the color filter. Therefore, the solvent resistance of the resin is required to be further improved.

[0020] In addition, in recent years, especially in the use of color filters, due to the high quality and expansion of the use of color liquid crystal display devices, etc., there is a strong demand for higher performance such as high brightness and high contrast of display panels. However, in the manufacture of color filters, if the firing treatment process (post-curing process) after exposure and development is carried out at a high temperature higher than 200°C, the obtained cured product will have discoloration such as yellowing, and there is a problem that the desired color cannot be fully colored. In addition, if the firing treatment process is carried out at a high temperature, unnecessary reactions will occur and by-products will be produced, and there is also a problem of reducing the characteristics of the substrate and the cured film. In order to suppress this unnecessary reaction and efficiently obtain a color filter with desired characteristics, it is hoped that the curing reaction can be fully carried out even under the heating conditions of a relatively low temperature below 200°C. In addition, if the curable resin composition can be cured at a relatively low temperature, the manufacturing efficiency of the color filter can also be improved.

[0021] On the other hand, a resin that readily undergoes a curing reaction even under relatively low-temperature heating conditions generally has a problem of low storage stability due to its high reactivity.

[0022] The present invention is made in view of the above-mentioned current situation, and its purpose is to provide a polymer that can provide a cured product with excellent solvent resistance even under low-temperature curing conditions and excellent storage stability, a photosensitive resin composition containing the polymer, and a cured product thereof. In addition, the present invention also aims to provide a monomer compound that can be used for the production of the polymer, and a method for producing the polymer and the monomer compound.

[0023] Means for solving problems

[0024] The present inventors have conducted various studies on polymers that can be used in photosensitive resin compositions, and as a result, have found that by preparing a polymer having a specific structure, a cross-linking reaction can be performed well even under low-temperature curing conditions of 160° C. or less, a cured product having excellent solvent resistance can be provided, and a resin having excellent storage stability can be provided, thereby completing the present invention.

[0025] That is, the present invention provides the following aspects of the invention.

[0026] [1] A polymer characterized by having a structural unit (A) represented by the following formula (1).

[0027] [Chemistry 1]

[0028]

[0029] (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 the action of an acid or heat to generate a vinyl ether group in the polymer side chain.)

[0030] [2] The polymer according to [1] above, wherein the structural unit (A) is represented by the following formula (1-1).

[0031] [Chemistry 2]

[0032]

[0033] (wherein X represents a hydrogen atom or a methyl group. 1 represents a linear or branched divalent organic group. 2 It represents an organic group having 1 to 20 carbon atoms.

[0034] [3] The polymer according to [1] or [2], further comprising a structural unit (B) containing an acid group.

[0035] [4] The polymer according to any one of [1] to [3], further comprising a structural unit (C) having a ring structure in the main chain.

[0036] [5] A polymer solution comprising the polymer according to any one of [1] to [4] above and a polar solvent.

[0037] [6] A polymer solution comprising the polymer described in any one of [1] to [4] above or the polymer solution described in [5] above, and a basic dispersant and / or a basic compound.

[0038] [7] A colorant dispersion comprising the polymer solution according to [6] above and a colorant.

[0039] [8] A photosensitive resin composition, characterized in that it contains: the polymer described in any one of [1] to [4] above, the polymer solution described in [5] above, the polymer solution described in [6] above, or the colorant dispersion described in [7] above; a polymerizable compound; and a photopolymerization initiator and / or a photoacid generator.

[0040] [9] The photosensitive resin composition according to [8] above, which is used for forming a color filter.

[0041]

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

[0042]

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

[0043] [Chemistry 3]

[0044]

[0045] (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 the action of an acid or heat to generate a vinyl ether group in the polymer side chain.)

[0046]

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

[0047] [Chemistry 4]

[0048]

[0049] (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 the action of an acid or heat to generate a vinyl ether group in the polymer side chain.)

[0050]

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

[0051] [Chemistry 5]

[0052]

[0053] (Where R 7 represents a hydrogen atom or a methyl group. 8 represents a linear or branched divalent organic group. 9 It represents an organic group having 1 to 20 carbon atoms (excluding groups containing (meth)acryloyl groups).

[0054]

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

[0055] [Chemistry 6]

[0056]

[0057] (Where R 7 represents a hydrogen atom or a methyl group. 8 represents a linear or branched divalent organic group. 10 represents a hydrogen atom or an organic group having 1 to 20 carbon atoms (excluding groups containing a (meth)acryloyl group).

[0058] Effects of the Invention

[0059] The polymer and photosensitive resin composition of the present invention have excellent storage stability, can be fully cured even under low-temperature curing conditions, and can provide a cured product with excellent solvent resistance. The polymer and photosensitive resin composition of the present invention can be widely used in various applications such as optical components, motor / electronic components, and display devices. DETAILED DESCRIPTION

[0060] The present invention is described in detail below.

[0061] In addition, the embodiment in which two or more of the preferred embodiments of the present invention described below are combined is also a preferred embodiment of the present invention.

[0062] In addition, in this specification, "(meth)acrylate" means "acrylate and / or methacrylate", and "(meth)acrylic acid" means "acrylic acid and / or methacrylic acid".

[0063] 1. Polymer

[0064] The polymer of the present invention is characterized by having a structural unit (A) represented by the following formula (1).

[0065] [Chemistry 7]

[0066]

[0067] (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 the action of an acid or heat to generate a vinyl ether group in the polymer side chain.)

[0068] The polymer of the present invention can provide a cured product having excellent solvent resistance even under low-temperature curing conditions by having the structural unit (A), and has excellent storage stability. The reason for this is believed to be that, since the polymer has a group that is decomposed by the action of an acid or heat to generate a vinyl ether group, a vinyl ether group is generated during curing, and cationic polymerization based on the vinyl ether group is performed, thereby enabling the cross-linking reaction of the polymer to proceed sufficiently. In addition, it is believed that the vinyl ether group as a curing reactive group is protected during the storage of the polymer, so that the self-cross-linking reaction of the polymer is suppressed, and the storage stability is excellent.

[0069] The polymer of the present invention is described in detail below.

[0070] (1) Structural unit (A)

[0071] The polymer of the present invention has a structural unit (A) represented by the above formula (1). In addition, in this specification, "structural unit" means a repeating (structural) unit in the structure of a polymer.

[0072] In the above formula (1), X represents a hydrogen atom or a methyl group. X is preferably a hydrogen atom because the polymer has high hydrophilicity and excellent developability.

[0073] In the above formula (1), L represents a linear or branched divalent organic group. Examples of the divalent organic group represented by L include a linear or branched divalent hydrocarbon group which may have a substituent.

[0074] Examples of the linear or branched divalent hydrocarbon group include divalent aliphatic hydrocarbon groups. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group.

[0075] Examples of the divalent saturated aliphatic hydrocarbon group include alkylene groups such as methylene, ethylene, propylene, isopropylene, butylene, isobutylene, tert-butylene, pentylene, neopentylene, hexylene, heptylene, octylene, 2-ethylhexylene, nonylene, decylene, undecylene and dodecylene.

[0076] The saturated aliphatic hydrocarbon group has preferably 1 to 10 carbon atoms, more preferably 2 to 4 carbon atoms.

[0077] Examples of the divalent unsaturated aliphatic hydrocarbon group include alkenylene groups such as vinylene, propenylene, isopropenylene, butenylene, butadienylene, pentenylene, hexenylene and heptenylene, and alkynylene groups such as ethynylene, propynylene, 1-butynylene and 2-butynylene.

[0078] The unsaturated aliphatic hydrocarbon group has preferably 1 to 10 carbon atoms, more preferably 2 to 4 carbon atoms.

[0079] Among them, the divalent aliphatic hydrocarbon group is preferably a divalent saturated aliphatic hydrocarbon group from the viewpoint of being able to impart flexibility to the side chain.

[0080] In the above-mentioned 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.

[0081] Furthermore, the above-mentioned hydrocarbon group may have a substituent such as an alkoxy group.

[0082] As the above-mentioned straight-chain or branched divalent organic group, for example, preferably there can be mentioned the above-mentioned straight-chain or branched divalent hydrocarbon group; or a group containing the above-mentioned straight-chain or branched divalent hydrocarbon group and a bond such as -O-, -COO-, -CO-, -NH-, -S-, -SO-, -SO2-.

[0083] In the group containing the above-mentioned straight-chain or branched divalent hydrocarbon group and a bond such as -O-, -COO-, -CO-, -NH-, -S-, -SO-, or -SO2-, the above-mentioned divalent hydrocarbon group or bond may contain only one kind or two or more kinds.

[0084] From the viewpoint of good copolymerizability, the 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-.

[0085] The divalent organic group represented by L is preferably -COO-R 1 -(R 1 represents a linear or branched divalent organic group).

[0086] As the above R 1 The linear or branched divalent organic group represented by may preferably include the above-mentioned linear or branched divalent hydrocarbon group, or a group comprising the above-mentioned linear or branched divalent hydrocarbon group and a bond such as -O-, -COO-, -CO-, -NH-, -S-, -SO-, or -SO2-, among which -R 3 -(OR 4 )n-(where R 3 and R 4 are the same or different and represent a divalent saturated aliphatic hydrocarbon group. n represents an integer greater than 0).

[0087] The above R 3 and R 4 The divalent saturated aliphatic hydrocarbon group represented is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 2 carbon atoms.

[0088] The above n is preferably an integer of 0 to 10, more preferably 1.

[0089] The divalent organic group represented by L has preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 5 carbon atoms.

[0090] In the above formula (1), Y represents an organic group that decomposes by the action of acid or heat to generate a vinyl ether group (-O-CH=CH2) in the polymer side chain. Examples of such an organic group include a vinyl ether group protected by acetal.

[0091] Examples of the group in which the vinyl ether group is acetal-protected include groups containing a -O-CH(CH 3 )-O- bonding group, and preferably -O-CH(CH 3 )-OR2 If the above polymer has such a group, then under the action of acid or heat, -OR 2 The vinyl ether group (-O-CH=CH2) is generated in the side chain of the above polymer. 2 It represents an organic group having 1 to 20 carbon atoms.

[0092] As the above R 2 As the organic group represented, preferably, there can be mentioned a monovalent hydrocarbon group which may have a substituent.

[0093] Examples of the monovalent hydrocarbon group include a hydrocarbon group having a chain structure or a hydrocarbon group including a cyclic structure.

[0094] Examples of the hydrocarbon group having the chain structure include aliphatic hydrocarbon groups.

[0095] Examples of the aliphatic hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, pentyl, isopentyl, neopentyl, hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, heptyl, 2-methylhexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3-ethylpentyl, 2,2,3-trimethylbutyl, octyl, methylheptyl, dimethylhexyl, 2-ethylhexyl, 3-ethylhexyl, trimethylpentyl, 3-ethyl-2-methylpentyl, 2-ethyl-3-methylpentyl, 2,2,3,3-tetramethyl Alkyl groups such as butyl, nonyl, methyloctyl, 3,7-dimethyloctyl, dimethylheptyl, 3-ethylheptyl, 4-ethylheptyl, trimethylhexyl, 3,3-diethylpentyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl; alkenyl groups such as vinyl, n-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 1-pentenyl, 2-pentenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 3-methyl-1-butenyl, 1-hexenyl, 2-hexenyl, 1-heptenyl, 2-heptenyl, 1-octenyl or 2-octenyl; and the like.

[0096] Examples of the hydrocarbon group containing a cyclic structure include a hydrocarbon group having a cyclic structure or a hydrocarbon group having a cyclic structure and a chain structure.

[0097] Examples of the hydrocarbon group having a cyclic structure include an alicyclic hydrocarbon group and an aromatic hydrocarbon group.

[0098] Examples of the alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl.

[0099] Examples of the aromatic hydrocarbon group include aryl groups such as a phenyl group and a naphthyl group.

[0100] Examples of the hydrocarbon group having a cyclic structure and a chain structure include a hydrocarbon group composed of a combination of the above-mentioned hydrocarbon group having a cyclic structure and a hydrocarbon group having a chain structure, such as benzyl, phenethyl, biphenylyl, tolyl, and xylyl.

[0101] The monovalent hydrocarbon group has preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 3 carbon atoms.

[0102] In addition, in the above-mentioned monovalent 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.

[0103] The monovalent hydrocarbon group may have a substituent such as an alkoxy group, an amide group, an amino group, etc. When 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.

[0104] Among them, from the perspective of good low temperature curing properties, the above R 2 The organic group represented is preferably -R 5 (excluding groups containing carbonyl groups) or -CO-R 6 , more preferably -CO-R 6 .

[0105] It should be noted that R 5 and R 6 The same or different, represent an organic group, preferably a hydrocarbon group, or a group comprising a hydrocarbon group and at least one bond selected from the group consisting of -O- and -COO-, more preferably an aliphatic hydrocarbon group, or a group comprising an aliphatic hydrocarbon group and at least one bond selected from the group consisting of -O- and -COO-, and further preferably an alkyl group.

[0106] The above R 6 The carbon number of the organic group represented is preferably 1 to 19, more preferably 1 to 10, further preferably 1 to 5, and most preferably 3. By controlling the carbon number within the above range, both storage stability and low-temperature curing properties can be achieved.

[0107] The structural unit (A) is preferably a structural unit represented by the following formula (1-1) from the viewpoint of good low-temperature curability.

[0108] [Chemistry 8]

[0109]

[0110] (wherein X represents a hydrogen atom or a methyl group.1 represents a linear or branched divalent organic group. 2 It represents an organic group having 1 to 20 carbon atoms.

[0111] In the above formula (1-1), R 1 and R 2 Respectively with the above R 1 and R 2 same.

[0112] The polymer having the structural unit (A) can be obtained, for example, by polymerizing a monomer component including a monomer capable of introducing the structural unit (A).

[0113] The monomer that can introduce the structural unit (A) is not particularly limited as long as it is a monomer that can give a polymer having the structural unit (A) by polymerization, and examples thereof include monomers represented by the following formula (2).

[0114] CH2=CXL-Y(2)

[0115] (In the formula, X, L and Y are the same as X, L and Y in formula (1) respectively.)

[0116] Among them, as the monomer represented by the above formula (2), preferably, from the viewpoint of excellent synthesis stability, a monomer compound represented by the following formula (a) can be mentioned.

[0117] [Chemistry 9]

[0118]

[0119] (Where R 7 represents a hydrogen atom or a methyl group. 8 represents a linear or branched divalent organic group. 9 It represents an organic group having 1 to 20 carbon atoms.

[0120] In the above formula (a), R 8 The linear or branched divalent organic group represented by is preferably the same as R in the above formula (1-1). 1 The linear or branched divalent organic groups represented are the same groups.

[0121] In addition, as R 9 The organic group having 1 to 20 carbon atoms represented by is preferably the same as R in the above formula (1-1). 2 The same groups are represented by the organic groups having 1 to 20 carbon atoms. 9 The organic group represented by 6 In this formula, R 6It is preferably a hydrocarbon group, and more preferably a chain saturated hydrocarbon group. 6 The number of carbon atoms of the organic group represented is preferably 1 to 19, more preferably 1 to 10, further preferably 1 to 5, and most preferably 3.

[0122] Specific examples of the monomer compound represented by the above formula (a) include 2-(2-(1-acetoxyethoxy)ethoxy)ethyl (meth)acrylate, 2-(2-(1-isopropoxyethoxy)ethoxy)ethyl (meth)acrylate, 2-(2-(1-ethoxyethoxy)ethoxy)ethyl (meth)acrylate, 2-(2-(1-propionyloxyethoxy)ethoxy)ethyl (meth)acrylate, 2-(2-(1-butoxyethoxy)ethoxy)ethyl (meth)acrylate, and 2-(2-(1-formyloxyethoxy)ethoxy)ethyl (meth)acrylate. From the viewpoint of synthesis, 2-(2-(1-propionyloxyethoxy)ethoxy)ethyl (meth)acrylate and 2-(2-(1-butoxyethoxy)ethoxy)ethyl (meth)acrylate are preferred, and 2-(2-(1-butoxyethoxy)ethoxy)ethyl (meth)acrylate is most preferred.

[0123] The above-mentioned monomer compounds may be used alone or in combination of two or more.

[0124] It should be noted that among the monomer compounds represented by the above formula (a), R 7 represents a hydrogen atom or a methyl group, R 8 represents a linear or branched divalent organic group, R 9 The compound having an organic group having 1 to 20 carbon atoms (excluding a group containing a (meth)acryloyl group) is a novel compound. Such a novel monomer compound is also one of the present invention.

[0125] The polymer may contain only one type of the structural unit (A) or two or more types of the structural unit (A).

[0126] From the viewpoint of good low-temperature curability, the content of the structural unit (A) is preferably 1 to 100% by mass, more preferably 5 to 50% by mass, and even more preferably 10 to 40% by mass based on 100% by mass of all structural units of the polymer.

[0127] (2) Structural unit (B)

[0128] The polymer of the present invention preferably further has a structural unit (B) containing an acid group. By having the structural unit (B), a vinyl ether group is easily generated from the structural unit (A) during curing, and cationic polymerization based on the vinyl ether group is further performed. The vinyl ether group reacts with the acid group, and the self-crosslinking reaction of the polymer is easily performed, so that a more solid cured product can be formed. In addition, the polymer becomes alkali-soluble, and the developability becomes good.

[0129] As the acid group, for example, functional groups that react with alkaline water to neutralize such as carboxyl, phenolic hydroxyl, carboxylic acid anhydride, phosphoric acid, and sulfonic acid groups can be mentioned, and only one of these functional groups may be present, or two or more thereof may be present. Among them, from the perspective of better developability, carboxyl and carboxylic acid anhydride groups are preferred, and carboxyl groups are more preferred.

[0130] The polymer having the structural unit (B) containing an acid group can be obtained by the following methods: 1) a method of polymerizing a monomer component containing a monomer containing an acid group; or 2) a method of polymerizing a monomer component containing a monomer containing a hydroxyl group to obtain a precursor polymer (base polymer), and then reacting a polyacid or a polyacid anhydride with the hydroxyl group of the precursor polymer (base polymer) to introduce an acid group. These methods may be combined.

[0131] In the method 1) above, a structural unit derived from an acid group-containing monomer can be obtained as the structural unit (B).

[0132] Examples of the acid group-containing monomer include compounds having the acid group and a polymerizable double bond (carbon-carbon double bond) in the molecule. Examples of the polymerizable double bond include (meth)acryloyl, vinyl, allyl, methallyl, etc. Among them, (meth)acryloyl is preferred.

[0133] Specific examples of the above-mentioned monomers containing acid groups include, for example, unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid, and vinyl benzoic acid; unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid; long-chain unsaturated monocarboxylic acids with extended chains between unsaturated groups and carboxyl groups such as (meth) acrylate β-carboxyethyl, succinic acid mono(2-acryloyloxyethyl), and succinic acid mono(2-methacryloyloxyethyl); unsaturated anhydrides such as maleic anhydride and itaconic anhydride; unsaturated compounds containing phosphoric acid groups such as Light Ester P-1M (produced by Kyoeisha Chemical); and the like. Among these, carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, long-chain unsaturated monocarboxylic acids, and unsaturated anhydrides) are preferred from the perspectives of versatility and availability. From the perspectives of reactivity and alkali solubility, the above-mentioned monomers containing acid groups are more preferably unsaturated monocarboxylic acids, and more preferably (meth) acrylic acid.

[0134] In the method 2), a precursor polymer (prepolymer) having hydroxyl groups is prepared in advance, and then the hydroxyl groups are reacted with a polybasic acid or a polybasic acid anhydride to introduce acid groups (carboxyl groups), thereby producing a polymer having a structural unit (B) containing an acid group.

[0135] When a polymer having a structural unit containing an acid group is produced by such a method, the acid group is present at a position relatively far from the polymer main chain, and a crosslinking reaction is easily performed during curing of the polymer, thereby further improving curability.

[0136] In the method 2) above, a structural unit containing a carboxyl group produced by reacting a polybasic acid or a polybasic acid anhydride with a structural unit derived from a hydroxyl group-containing monomer can be obtained as the structural unit (B).

[0137] Examples of the hydroxyl group-containing monomer include the same monomer compounds as those described below as the hydroxyl group-containing monomer that provides the structural unit (D).

[0138] Examples of the polybasic acid or polybasic acid anhydride include the same compounds as those described below as the acid group-containing compounds.

[0139] The specific reaction method will be described in the later-described method for producing the polymer.

[0140] In the method 2), an epoxy group may be used instead of the hydroxyl group. That is, the following method may be used: a polymer having an epoxy group is prepared in advance, and then the acid group of a monomer containing an acid group is subjected to an addition reaction with the epoxy group to open the epoxy group, and a polybasic acid or polybasic acid anhydride is reacted with the hydroxyl group generated at this time to generate a carboxyl group.

[0141] Examples of the epoxy group-containing monomer used when preparing the above-mentioned epoxy group-containing polymer include glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, vinyl benzyl glycidyl ether, allyl glycidyl ether, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and vinyl epoxycyclohexane. Among them, glycidyl (meth)acrylate and (3,4-epoxycyclohexyl)methyl (meth)acrylate are preferred, and glycidyl (meth)acrylate is more preferred.

[0142] The polymer may contain only one type of the structural unit (B) or two or more types of the structural unit (B).

[0143] The content ratio of the above-mentioned structural unit (B) relative to 100 mass% of all the structural units of the above-mentioned polymer is preferably 0 to 80 mass%. From the perspective of good developability, the content ratio of the above-mentioned structural unit (B) relative to 100 mass% of all the structural units of the above-mentioned polymer is more preferably 3 to 80 mass%, further preferably 5 to 45 mass%, and further more preferably 10 to 30 mass%.

[0144] (3) Structural unit (C)

[0145] The above-mentioned polymer is preferably a polymer having a ring structure in the main chain. By having a ring structure in the main chain, the heat resistance of the above-mentioned polymer can be improved. As the above-mentioned ring structure, an imide ring, a tetrahydrofuran ring, a lactone ring etc. can be enumerated. Like this, the above-mentioned polymer preferably further has a structural unit (C) having a ring structure in the main chain.

[0146] Examples of the monomer that can introduce the structural unit (C) include monomers having a ring structure containing a double bond in the molecule, monomers that form a polymer having a ring structure in the main chain by cyclopolymerization, and monomers that form a ring structure after polymerization. Among them, from the perspectives of good heat resistance, solvent resistance, hardness, colorant dispersibility, etc., at least one monomer selected from the group consisting of N-substituted maleimide monomers, dialkyl-2,2'-(oxydimethylene) diacrylate monomers, and α-(unsaturated alkoxyalkyl) acrylate monomers is preferred, and from the perspective of further excellent solvent resistance, N-substituted maleimide monomers are more preferred.

[0147] The structural unit (C) can be said to be a structural unit derived from such a monomer that can introduce the structural unit (C).

[0148] As the above-mentioned N-substituted maleimide monomer, for example, N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, N-tert-butylmaleimide, N-dodecylmaleimide, N-benzylmaleimide, N-naphthylmaleimide, etc. can be mentioned, and one or more of them can be used. Among them, from the aspects of transparency, heat coloration resistance, and water spot suppression, N-phenylmaleimide, N-benzylmaleimide, and N-cyclohexylmaleimide are preferred, and N-benzylmaleimide is particularly preferred.

[0149] Examples of the N-benzylmaleimide include benzylmaleimide; alkyl-substituted benzylmaleimide such as p-methylbenzylmaleimide and p-butylbenzylmaleimide; phenolic hydroxyl-substituted benzylmaleimide such as p-hydroxybenzylmaleimide; halogen-substituted benzylmaleimide such as o-chlorobenzylmaleimide, o-dichlorobenzylmaleimide and p-dichlorobenzylmaleimide; and the like.

[0150] Examples of the dialkyl-2,2'-(oxydimethylene) diacrylate monomers include dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, diethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(n-butyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, and di(n-butyl)-2,2'-[oxybis(methylene)]bis-2-acrylate. bis(methylene)]bis-2-acrylate, di(isobutyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(tert-butyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(tert-amyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(stearyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(lauryl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, etc. Among these, dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate is more preferred from the perspectives of transparency, dispersibility, ease of industrial availability, etc.

[0151] Examples of the α-(unsaturated alkoxyalkyl) acrylate monomers include α-(allyloxymethyl) acrylate monomers. Specific examples of the α-(allyloxymethyl) acrylate monomers include α-allyloxymethyl acrylic acid; α-allyloxymethyl methacrylate methyl, α-allyloxymethyl methacrylate ethyl, α-allyloxymethyl methacrylate n-propyl, α-allyloxymethyl methacrylate isopropyl, α-allyloxymethyl methacrylate n-butyl, α-allyloxymethyl methacrylate sec-butyl, α-allyloxymethyl methacrylate tert-butyl, α-allyloxymethyl methacrylate n-pentyl, α-allyloxymethyl methacrylate sec-pentyl, α-allyloxymethyl methacrylate tert-amyl methacrylate, n-hexyl α-allyloxy methacrylate, sec-hexyl α-allyloxy methacrylate, n-heptyl α-allyloxy methacrylate, n-octyl α-allyloxy methacrylate, sec-octyl α-allyloxy methacrylate, tert-octyl α-allyloxy methacrylate, 2-ethylhexyl α-allyloxy methacrylate, octyl α-allyloxy methacrylate, nonyl α-allyloxy methacrylate, decyl α-allyloxy methacrylate, undecyl α-allyloxy methacrylate, decyl α-allyloxy methacrylate, α-allyloxymethyl) acrylate, 1,2-dioctyl meth ... Alkyl acrylate monomers; (α-allyloxymethyl) acrylate alkoxyalkyl ester monomers such as methoxyethyl α-allyloxy methacrylate, methoxyethoxyethyl α-allyloxy methacrylate, methoxyethoxyethoxyethyl α-allyloxy methacrylate, 3-methoxybutyl α-allyloxy methacrylate, ethoxyethyl α-allyloxy methacrylate, ethoxyethoxyethyl α-allyloxy methacrylate, phenoxyethyl α-allyloxy methacrylate, and phenoxyethoxyethyl α-allyloxy methacrylate;α-allyloxy methacrylate hydroxyethyl, α-allyloxy methacrylate hydroxypropyl, α-allyloxy methacrylate hydroxybutyl, α-allyloxy methacrylate fluoroethyl, α-allyloxy methacrylate difluoroethyl, α-allyloxy methacrylate chloroethyl, α-allyloxy methacrylate dichloroethyl, α-allyloxy methacrylate bromoethyl, α-allyloxy methacrylate dibromoethyl, α-allyloxy methacrylate vinyl, α-allyloxy methacrylate allyl, α-allyloxy methacrylate methyl allyl, α-allyloxy methacrylate crotonyl, α-allyloxy methacrylate propargyl, α-allyloxy methacrylate cyclopentyl, α-allyloxy methacrylate cyclohexyl, α-allyloxy methacrylate 4-methylcyclohexyl, α-allyloxy 4-tert-butylcyclohexyl methacrylate, tricyclodecyl α-allyloxymethacrylate, isobornyl α-allyloxymethacrylate, adamantyl α-allyloxymethacrylate, dicyclopentadienyl α-allyloxymethacrylate, phenyl α-allyloxymethacrylate, methyl phenyl α-allyloxymethacrylate, dimethylphenyl α-allyloxymethacrylate, trimethylphenyl α-allyloxymethacrylate, 4-tert-butylphenyl α-allyloxymethacrylate, benzyl α-allyloxymethacrylate, diphenylmethyl α-allyloxymethacrylate, diphenylethyl α-allyloxymethacrylate, triphenylmethyl α-allyloxymethacrylate, cinnamyl α-allyloxymethacrylate, naphthyl α-allyloxymethacrylate, anthracene α-allyloxymethacrylate, etc. Among them, the (α-allyloxymethyl) alkyl acrylate monomer is preferred. As the above-mentioned (α-allyloxymethyl) alkyl acrylate monomer, α-allyloxymethyl methacrylate (also called methyl-(α-allyloxymethyl) acrylate) is particularly preferred from the perspectives of transparency, dispersibility, and ease of industrial availability. ;

[0152] The α-(unsaturated alkoxyalkyl)acrylate monomer can be produced by a production method disclosed in, for example, International Publication No. 2010 / 114077.

[0153] As a monomer that can introduce the structural unit (C), alkyl 2-(hydroxyalkyl)acrylates can also be mentioned. Alkyl 2-(hydroxyalkyl)acrylates can react with (meth)acrylic acid to form a lactone ring structure in the main chain.

[0154] Examples of the alkyl 2-(hydroxyalkyl)acrylate include alkyl 2-(1-hydroxyalkyl)acrylate and alkyl 2-(2-hydroxyalkyl)acrylate. Specifically, examples include methyl 2-(1-hydroxymethyl)acrylate, ethyl 2-(1-hydroxymethyl)acrylate, isopropyl 2-(1-hydroxymethyl)acrylate, n-butyl 2-(1-hydroxymethyl)acrylate, tert-butyl 2-(1-hydroxymethyl)acrylate, and 2-ethylhexyl 2-(1-hydroxymethyl)acrylate. Among them, methyl 2-(1-hydroxymethyl)acrylate and ethyl 2-(1-hydroxymethyl)acrylate are preferred.

[0155] The polymer may contain only one type of the structural unit (C) or two or more types of the structural unit (C).

[0156] The content of the structural unit (C) is preferably 0 to 50% by mass, more preferably 1 to 50% by mass, further preferably 1.5 to 20% by mass, and still more preferably 2 to 15% by mass, based on 100% by mass of all structural units of the polymer.

[0157] (4) Structural unit (D)

[0158] The above polymer may have another structural unit (D) in addition to the above structural units (A), (B), and (C).

[0159] Examples of the other structural unit (D) include structural units derived from the following monomers.

[0160] A monomer containing a hydroxyl group such as hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2,3-hydroxypropyl (meth)acrylate;

[0161] Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, n-pentyl (meth)acrylate, sec-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, tricyclodecyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, (meth)acrylate monomers such as 4-(1-methoxy)ethoxycyclohexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, 1,4-dioxaspiro[4,5]dec-2-yl methacrylic acid, (meth)acryloylmorpholine, 4-(meth)acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane, and 4-(meth)acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane;

[0162] Aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, and methoxystyrene;

[0163] Epoxy-containing monomers such as glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, vinyl benzyl glycidyl ether, allyl glycidyl ether, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and vinyl epoxycyclohexane;

[0164] (Meth)acrylamides such as N,N-dimethyl (meth)acrylamide and N-hydroxymethyl (meth)acrylamide;

[0165] Macromonomers having a (meth)acryloyl group at one end of the polymer molecular chain, such as polystyrene, poly(methyl)acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, and polycaprolactam;

[0166] Conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene;

[0167] Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate;

[0168] 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;

[0169] N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, N-vinylmorpholine, and N-vinylacetamide;

[0170] Vinyltoluene, styrene and other styrene derivatives;

[0171] Unsaturated isocyanates such as isocyanatoethyl (meth)acrylate and allyl isocyanate; and the like.

[0172] Among them, the structural unit (D) is preferably a structural unit derived from at least one monomer selected from the group consisting of a hydroxyl group-containing monomer, a (meth)acrylate monomer, and a styrene derivative.

[0173] The polymer may contain only one type of the structural unit (D) or two or more types of the structural unit (D).

[0174] The content of the structural unit (D) is preferably 0 to 99% by mass, more preferably 1 to 99% by mass, further preferably 2 to 80% by mass, and further preferably 10 to 70% by mass, based on 100% by mass of all structural units of the polymer.

[0175] When the polymer contains two or more of the structural units (D), the content ratio of each structural unit (D) can be appropriately set according to the use and purpose of the polymer of the present invention.

[0176] The acid value of the polymer is preferably 10 to 200 mgKOH / g, more preferably 20 to 150 mgKOH / g, and even more preferably 50 to 130 mgKOH / g from the viewpoint of good developability.

[0177] The acid value is a value measured by a neutralization titration method using a potassium hydroxide (KOH) solution, and is an acid value per 1 g of the resin solid content.

[0178] The weight average molecular weight of the polymer is preferably 1000 to 100000. From the viewpoint of good low temperature curability, the weight average molecular weight of the polymer is more preferably 3000 to 50000, and even more preferably 5000 to 20000.

[0179] The weight average molecular weight is a value measured by gel permeation chromatography (GPC) according to the method described in Examples.

[0180] The vinyl ether equivalent of the polymer is preferably 200 to 50,000 g / mol. From the perspective of improving curability and storage stability, the vinyl ether equivalent is more preferably 300 to 10,000 g / mol, and further preferably 400 to 2,000 g / mol. The vinyl ether group herein refers to a vinyl ether group generated when all acetal bonds in the polymer are deprotected, and refers to a vinyl ether group potentially present in the polymer.

[0181] The vinyl ether equivalent refers to the mass of the solid content of the polymer solution per 1 mol of vinyl ether groups of the polymer. The mass of the solid content of the polymer solution refers to the mass of the monomer components constituting the polymer. The vinyl ether equivalent can be obtained by dividing the mass (g) of the polymer solid content of the polymer solution by the vinyl ether groups (mol) of the polymer. In addition, titration and various analyses such as elemental analysis, NMR, IR, or differential scanning calorimetry can also be used for measurement.

[0182] The polymer may have a polymerizable double bond in the side chain. By having a polymerizable double bond in the side chain, the curability of the polymer can be improved. As the polymerizable double bond, the above-mentioned polymerizable double bond can be cited. Among them, from the aspect of reactivity, (meth)acryloyl is preferred.

[0183] When the polymer has a polymerizable double bond in a side chain, the double bond equivalent of the polymer is preferably 400 to 50,000 g / mol, more preferably 500 to 10,000 g / mol, and even more preferably 600 to 2,000 g / mol from the viewpoint of improving curability.

[0184] The double bond here refers to a double bond having free radical polymerizability, that is, a polymerizable double bond represented by a (meth)acryloyl group. For example, a double bond generated by adding tetrahydrophthalic anhydride to a hydroxyl group is not included in the calculation as a double bond equivalent because it is not reactive.

[0185] The above-mentioned double bond equivalent is the mass of the solid component of the polymer solution relative to each 1 mol of double bonds of the above-mentioned polymer. The mass of the solid component of the above-mentioned polymer solution refers to the mass of the monomer components constituting the above-mentioned polymer. The above-mentioned double bond equivalent can be obtained by dividing the mass (g) of the polymer solid component of the polymer solution by the double bond amount (mol) of the polymer. In addition, various analyses such as titration and elemental analysis, NMR, IR, or differential scanning calorimetry can also be used for measurement.

[0186] 2. Method for producing polymer

[0187] The method for producing the polymer of the present invention is not particularly limited as long as the above-mentioned polymer can be obtained, and an example thereof includes a method of polymerizing a monomer component containing a monomer that can introduce the above-mentioned structural unit (A) and, if necessary, the structural units (B), (C), and (D) by a known method. The amount of each monomer can be appropriately adjusted so that the content of each structural unit in the polymer reaches the desired range.

[0188] There is no particular limitation on the method for polymerizing the above-mentioned monomer components, and commonly used methods such as bulk polymerization, solution polymerization, and emulsion polymerization can be used. Among them, solution polymerization is preferred from the perspective of industrial advantage and easy adjustment of structures such as molecular weight. In addition, the polymerization mechanism of the above-mentioned monomer components can use a polymerization method based on a mechanism such as free radical polymerization, anionic polymerization, cationic polymerization, and coordination polymerization. From the perspective of industrial advantage, a polymerization method based on a free radical polymerization mechanism is preferred.

[0189] The molecular weight of the polymer obtained by polymerizing the above-mentioned monomer components can be controlled by adjusting the amount and type of the polymerization initiator, the polymerization temperature, the type and amount of the chain transfer agent, and the like.

[0190] As the above-mentioned polymerization initiator, known peroxides or azo compounds usually used as polymerization initiators can be enumerated. As the above-mentioned chain transfer agent, compounds with sulfhydryl groups such as alkyl mercaptan, mercaptocarboxylic acids, mercaptocarboxylic acid esters usually used as chain transfer agents can be enumerated. They can be used only one, or two or more can be used in combination. In addition, their addition amount can be appropriately set according to known methods.

[0191] Examples of the solvent used in the polymerization include aromatic hydrocarbon solvents such as toluene, xylene, and benzene; aliphatic hydrocarbon solvents such as hexane, pentane, heptane, and cyclohexane; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; halogenated hydrocarbon solvents such as chlorobenzene, dichloromethane, chloroform, and 1,2-dichloroethane; nitrile solvents such as acetonitrile, propionitrile, and valeronitrile; ester solvents such as methyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate; dimethylformamide (DMF), dimethylacetamide, N-methylpropane, and N-methylpyrrolidone. Amide solvents such as 1,2-dimethoxyethane (DME), 1,4-dioxane, tetrahydrofuran (THF), tetrahydropyran (THP), anisole, diethylene glycol dimethyl ether (diglyme), diethylene glycol ethyl ether (carbitol), cyclopentyl methyl ether (CPME), propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and other ether solvents; fluorine solvents such as perfluorohexane, perfluorocyclohexane, pentafluorobenzene, octafluorotoluene; DMSO, nitromethane, etc.

[0192] These solvents may be used alone or in combination of two or more.

[0193] The amount of the solvent used is not particularly limited and can be appropriately set by a known method.

[0194] Regarding the polymerization conditions, the polymerization temperature may be appropriately set according to the type and amount of the monomers used, the type and amount of the polymerization initiator, etc., and is preferably 40 to 130° C., more preferably 50 to 120° C. The polymerization time may also be appropriately set, and is preferably 1 to 15 hours, more preferably 2 to 11 hours.

[0195] As a method for producing the above-mentioned polymer, it is preferred that the step of polymerizing monomer components including a monomer (a) containing a group that generates a vinyl ether group by the action of an acid or heat and a monomer (b) containing an acid group is included. Such a method for producing a polymer having a structural unit (A) represented by the above formula (1) and a structural unit (B) containing an acid group (polymer production method 1) including the step (P-1) of polymerizing monomer units including a monomer containing a group that generates a vinyl ether group by the action of an acid or heat and a monomer containing an acid group is also one of the present invention.

[0196] Process (P-1)

[0197] Examples of the monomer having a group that generates a vinyl ether group by the action of an acid or heat include monomers that can introduce the structural unit (A), and preferably include monomer compounds represented by the formula (a).

[0198] Examples of the acid group-containing monomer include the same monomers as those mentioned above for the acid group-containing monomer.

[0199] The polymerization in the step (P-1) can be carried out by the same method as the above-mentioned polymerization method. In the above-mentioned polymerization, additives such as the above-mentioned polymerization initiator and chain transfer agent, and solvents can be used as appropriate.

[0200] The polymerization of the above-mentioned step (P-1) is preferably carried out in the presence of a basic compound. By polymerizing the above-mentioned monomer components in the presence of a basic compound, the generation of the vinyl ether group of the above-mentioned monomer (a) can be suppressed by the acid group possessed by the monomer unit containing the acid group, so that the target polymerization reaction is carried out well. In addition, since the acidity of the reaction system is neutralized and the generation of the vinyl ether group is suppressed, gelation can be suppressed and a polymer with excellent storage stability can be obtained. In addition, in order to improve the storage stability of the obtained polymer, a basic compound can be added after the polymerization.

[0201] Examples of the alkaline compound include: ammonia; primary amines such as methylamine; secondary amines such as dimethylamine; tertiary amines such as triethylamine and diethylmethylamine; aliphatic amines such as dimethylethanolamine, n-butylamine and diethylamine; cyclic aliphatic amines such as cyclohexylamine; heterocyclic amines such as piperidine, morpholine, N-ethylpiperidine, N-ethylmorpholine and pyridine; aromatic amines such as benzylamine, N-methylaniline and N,N-dimethylaniline; tetraalkylammonium halides such as tetramethylammonium chloride and tetraethylammonium chloride; tetraalkylammonium organic acid salts such as tetramethylammonium acetate; tetraalkylammonium inorganic acid salts such as tetramethylammonium hydrogen sulfate and tetraethylammonium hydrogen sulfate; (hydroxy)alkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and monohydroxyethyltrimethylammonium hydroxide; hydroxides of alkali metals such as sodium and potassium; hydroxides of transition metals such as barium, strontium, calcium and lanthanum; free salts of complex salts such as [Pt(NH3)6](OH)4, etc. Among them, secondary amines, tertiary amines, and heterocyclic amines are preferred, and tertiary amines are more preferred, from the viewpoint of suppressing deprotection.

[0202] In addition, the boiling point of the alkaline compound is preferably 20 to 220° C., more preferably 30 to 150° C., and even more preferably 50 to 100° C. If the boiling point of the alkaline compound is equal to or lower than the firing temperature after the coating film is formed, the alkaline compound volatilizes during firing, thereby converting the neutralized side chain carboxylate into a carboxylic acid. The carboxylic acid can promote cationic polymerization of the vinyl ether and crosslinking by acetalization with the side chain carboxylic acid.

[0203] In the above step (P-1), the amount of the basic compound used is not particularly limited as long as it is an amount that can inhibit 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 monomer.

[0204] In addition, the following method for producing a polymer having a structural unit (A) represented by the above formula (1) and a structural unit (B) containing an acid group is also one of the present invention, and the production method comprises a step (Q-1) of polymerizing a monomer component containing a monomer containing a group that generates a vinyl ether group by the action of an acid or heat, and a monomer containing a hydroxyl group, and a step (Q-2) of reacting a compound containing an acid group with the polymer obtained in the above step (Q-1) (polymer production method 2).

[0205] Process (Q-1)

[0206] In the above-mentioned method 2 for producing a polymer, first, monomer components including a monomer (a) having a group that generates a vinyl ether group by the action of an acid or heat and a monomer having a hydroxyl group are polymerized.

[0207] Examples of the monomer containing a group that generates a vinyl ether group by the action of an acid or heat and the monomer containing a hydroxyl group in the step (Q-1) include the same monomers as those described above.

[0208] The polymerization reaction in the step (Q-1) can be carried out by the same method as the above-mentioned polymerization method. In the above-mentioned polymerization, additives such as the above-mentioned polymerization initiator and chain transfer agent, and solvents can be used.

[0209] Process (Q-2)

[0210] In the above-mentioned method 2 for producing a polymer, next, a compound containing an acid group is reacted with the polymer obtained in the above-mentioned step (Q-1).

[0211] By reacting the polymer with the acid group-containing compound, the hydroxyl group of the polymer reacts with the acid group of the acid group-containing compound, thereby adding the acid group-containing compound.

[0212] As the compound containing an acid group, polyacids or polyacid anhydrides are preferred, for example, carboxylic acids such as succinic acid, maleic acid, phthalic acid, tetrahydrophthalic acid, and trimellitic acid; carboxylic acid anhydrides such as succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, itaconic anhydride, and trimellitic anhydride; etc. Among them, carboxylic anhydrides are preferred, and succinic anhydride is more preferred from the perspective of higher addition reactivity.

[0213] The amount of the acid group-containing compound used may be appropriately set depending on the application and purpose of the polymer to be obtained, the desired acid value, and the like.

[0214] The reaction of the polymer and the compound containing an acid group in the above-mentioned step (Q-2) is preferably carried out in the presence of a basic compound. An acid group is generated at the polymer terminal by the addition reaction of the compound containing an acid group, but it is immediately neutralized by the basic compound. Therefore, in the group of the obtained polymer that generates a vinyl ether group by the action of an acid or heat, the vinyl ether group is easily protected, and the reaction between the polymers is suppressed, so the synthesis and storage stability of the polymer become better.

[0215] Examples of the basic compound include the same compounds as those mentioned above.

[0216] In the above step (Q-2), the amount of the above basic compound used is not particularly limited as long as it can inhibit 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 structural unit used in the above step (Q-1).

[0217] When producing a polymer having a polymerizable double bond in a side chain, for example, after the step (Q-1), a polymerizable double bond can be introduced into the side chain of the polymer by addition-reacting (meth)acrylic acid with an epoxy group.

[0218] In addition, a polymerizable double bond can be introduced into the side chain of the polymer by addition-reacting an unsaturated isocyanate with a hydroxyl group instead of the above-mentioned (meth)acrylic acid.

[0219] In addition, a polymerizable double bond can be introduced into the side chain of the polymer by allowing an epoxy-containing compound to react with an acid group. For example, after preparing a polymer having an acid group (base polymer), the above-mentioned epoxy-containing monomer is reacted with the acid group to introduce a polymerizable double bond through an addition reaction based on the cleavage of the epoxy group.

[0220] The addition reaction of the (meth)acrylic acid, the unsaturated isocyanate, and the epoxy group-containing compound is not particularly limited and can be carried out by a known method. In addition, a commonly used catalyst, solvent, etc. can be used in the addition reaction.

[0221] In the manufacturing method of the above-mentioned polymer, as described above, it is preferred to use a basic compound, and the above-mentioned basic compound may also remain (exist) after the manufacture of the polymer, and a polymer solution comprising the above-mentioned polymer and the above-mentioned basic compound is also one of the preferred modes in the present invention. Such a polymer solution has good storage stability. The above-mentioned polymer solution may also further include a polar solvent described later.

[0222] In the manufacturing method of the above-mentioned polymer, in addition to the above-mentioned reaction step, other steps may also be included. As the above-mentioned other steps, for example, an aging step, a neutralization step, a dilution step, a drying step, a concentration step, a refining step, etc. may be cited. These steps may be carried out by known methods.

[0223] 3. Method for producing monomeric compound

[0224] As a monomer that can introduce the structural unit (A), a method for producing the monomer compound represented by the formula (a) is described. Examples of the method for producing the monomer compound include a method of reacting a carboxylic acid compound or an alcohol compound with a vinyl ether group-containing (meth)acrylate compound.

[0225] Examples of the vinyl ether group-containing (meth)acrylate compound include compounds represented by the following formula (3).

[0226] CH2=C(R 11 )-COO-R 12-O-CH=CH2(3)

[0227] (Where R 11 represents a hydrogen atom or a methyl group. 12 represents a linear or branched divalent organic group.

[0228] As R in the above formula (3) 12 The organic group represented by can be exemplified by the same organic group as R in the above formula (a). 8 The organic groups represented are the same groups.

[0229] Specific preferred examples of the vinyl ether group-containing (meth)acrylate compound include 2-(2-vinyloxyethoxy)ethyl acrylate and 2-(2-vinyloxyethoxy)ethyl methacrylate.

[0230] Examples of the carboxylic acid compound include aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, enanthic acid, heptanoic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, and stearic acid; monocarboxylic acid compounds such as formic acid, benzoic acid, β-carboxyethyl (meth)acrylate, mono(2-acryloyloxyethyl) succinate, and mono(2-methacryloyloxyethyl) succinate; and dicarboxylic acid compounds such as oxalic acid, malonic acid, succinic acid, tartaric acid, malic acid, maleic acid, gluconic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, and 5-norbornene dicarboxylic acid.

[0231] Among them, monocarboxylic acids are preferred, aliphatic carboxylic acids and formic acid are more preferred, and acetic acid, propionic acid, butyric acid and formic acid are further preferred from the perspective of easy copolymerization of the product. In addition, propionic acid and butyric acid are further preferred from the perspective of improved curability and storage stability after polymerization, and butyric acid is most preferred.

[0232] As the alcohol compound, for example, preferred examples include methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, isobutanol, isopentanol, propylene glycol monomethyl ether, propylene glycol monobutyl ether and other monoalcohols having 1 to 10 carbon atoms; (poly)ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, tetraethylene glycol, (poly)propylene glycol and other polyols having 1 to 10 carbon atoms. Among them, monoalcohols are preferred, and ethanol, isopropanol, and propylene glycol monomethyl ether are more preferred, because the product is easily copolymerized.

[0233] The above-mentioned carboxylic acid compounds and alcohol compounds may be used alone or in combination of two or more thereof. Among them, carboxylic acid compounds are preferred from the viewpoint of better storage stability.

[0234] In addition, from the perspective of easily achieving both storage stability and low-temperature curing properties, the above-mentioned carboxylic acid compound and alcohol compound are preferably compounds with 1 to 19 carbon atoms, more preferably compounds with 1 to 10 carbon atoms, further preferably compounds with 1 to 5 carbon atoms, and most preferably compounds with 4 carbon atoms.

[0235] In the above reaction, the carboxylic acid compound or alcohol compound is preferably mixed in an amount of 1 or more, more preferably 1 to 20 equivalents, further preferably 1.1 to 10 equivalents, and further more preferably 1.2 to 2 equivalents, relative to 1 equivalent of the above vinyl ether group-containing (meth)acrylate compound. By using 1 or more equivalent, the reaction substrate itself acts as a self-catalyst, and the reaction can be promoted.

[0236] The above reaction is not particularly limited and can be carried out by a known method such as mixing the components and heating them. In addition, the above reaction does not necessarily require the use of a solvent, but a solvent may be used.

[0237] The solvent used in the above reaction includes, for example, 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, dichloromethane, 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 one or two 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.

[0238] In the above reaction, known additives such as a catalyst and a polymerization inhibitor may be added.

[0239] Examples of the catalyst include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, trichloroacetic acid, dichloroacetic acid, pyruvic acid, and glycolic acid; aliphatic polycarboxylic acids such as oxalic acid, maleic acid, oxaloacetic acid, malonic acid, fumaric acid, tartaric acid, and citric acid; aromatic carboxylic acids such as benzoic acid and terephthalic acid; aromatic sulfonic acids or salts thereof such as benzenesulfonic acid, p-toluenesulfonic acid, pyridinium p-toluenesulfonate, and quinolinium p-toluenesulfonate; sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, nickel sulfate, and copper sulfate. , zirconium sulfate and other sulfates; sodium bisulfate, potassium bisulfate and other bisulfates; sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, polyphosphoric acid and other inorganic acids; phosphovanadomolybdic acid, phosphotungstomolybdic acid, silicotungstomolybdic acid and other heteropoly acids; acidic zeolites and other acid catalysts described in paragraph

[0043] of Japanese Patent Publication No. 2003-201267; and unsaturated compounds containing phosphoric acid groups such as 2-methacryloyloxyethyl acid phosphate and 2-acryloyloxyethyl acid phosphate, and commercially available products such as Light Ester P-1M and Light Ester P-2M (made by Kyoeisha Chemical). The above catalysts can be used alone or in combination of two or more.

[0240] The amount of the catalyst used is preferably 0.001 to 10 parts by mass, more preferably 0.005 to 1 part by mass, and even more preferably 0.008 to 0.05 parts by mass, based on 100 parts by mass of the vinyl ether group-containing (meth)acrylate compound.

[0241] Among them, in the above reaction, it is preferred to use p-toluenesulfonic acid as a catalyst from the viewpoint of rapid reaction.

[0242] Examples of the polymerization inhibitor include quinone-based polymerization inhibitors such as hydroquinone, methoxyhydroquinone, benzoquinone, and p-tert-butylcatechol; alkylphenol-based polymerization inhibitors such as 2,2'-methylenebis(4-methyl-tert-butylphenol), 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, and 2,4,6-tri-tert-butylphenol; amine-based polymerization inhibitors such as alkylated diphenylamine, N,N'-diphenyl-p-phenylenediamine, and phenothiazine; N-oxyls such as 4-hydroxy-2,2,6,6-tetramethylpiperidin-N-oxyl; copper dithiocarbamate-based polymerization inhibitors such as dimethyl copper dithiocarbamate, diethyl copper dithiocarbamate, and dibutyl copper dithiocarbamate, etc. These may be used alone or in combination of two or more.

[0243] The amount of the polymerization inhibitor used is preferably 0.001 to 10 parts by mass, more preferably 0.005 to 1 part by mass, and even more preferably 0.01 to 0.5 parts by mass, based on 100 parts by mass of the vinyl ether group-containing (meth)acrylate compound.

[0244] 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 further preferably 20 to 60°C.

[0245] The reaction time is, for example, preferably 0.1 to 20 hours, more preferably 1 to 15 hours, further preferably 2 to 12 hours.

[0246] The method for producing the above-mentioned monomer compound may further include other steps such as a purification step in addition to the above-mentioned reaction step. The above-mentioned other steps may be performed by a known method.

[0247] As the purification step, an acid-base extraction method is preferred. The target product can be purified efficiently by separating the unreacted carboxylic acid compound and alcohol into the water layer using an alkaline aqueous solution and concentrating the oil layer.

[0248] After the synthesis of the above-mentioned monomer compound, a basic compound may be added to the monomer compound in order to improve the storage stability of the monomer compound. Examples of the basic compound include the same compounds as those mentioned above.

[0249] The above-mentioned monomer compound can be produced by the above-mentioned production method. Among the above-mentioned monomer compounds, the monomer compound represented by the following formula (a-1) is preferably produced by the following method: the method includes a step of reacting a (meth)acrylate compound containing a vinyl ether group with a carboxylic acid compound, and in the above-mentioned reaction step, the amount of the above-mentioned carboxylic acid compound is 1 equivalent or more relative to 1 equivalent of the vinyl ether group of the above-mentioned (meth)acrylate compound containing a vinyl ether group. Such a method for producing the above-mentioned formula (a-1) is a new production method and is one of the present invention.

[0250] [Chemistry 10]

[0251]

[0252] (Where R 7 represents a hydrogen atom or a methyl group. 8 represents a linear or branched divalent organic group. 10 It represents a hydrogen atom or an organic group having 1 to 20 carbon atoms (excluding groups containing a (meth)acryloyl group).

[0253] As R 10 The organic group having 1 to 20 carbon atoms represented by may include, in addition to the group containing a (meth)acryloyl group, the group having the same carbon atoms as R 6 The organic groups represented are the same groups.

[0254] 4. Polymer solution

[0255] The polymer is preferably prepared into a polymer solution together with a polar solvent. By adding a polar solvent to the polymer to prepare a polymer solution, the storage stability of the polymer can be improved. The reason for improving the storage stability of the polymer by adding a polar solvent is not clear, but it is believed that the deprotection of the acetal group is suppressed by the interaction with the acetal structure, so that the storage stability can be improved while maintaining solvent resistance.

[0256] Such a polymer solution containing the above-mentioned polymer and a polar solvent is also one of the present invention.

[0257] Examples of the polar solvent include protic polar solvents and aprotic polar solvents.

[0258] Examples of the protic polar solvent include water, alcoholic solvents, amine solvents, and phenolic solvents. Among them, the protic polar solvent is preferably an alcoholic solvent.

[0259] As the alcohol solvent, preferably saturated alcohols can be mentioned, and monofunctional alcohols (monoalcohols), polyols, glycol monoethers, etc. can be mentioned. Specific examples of the alcohol solvent include primary alcohols such as methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monophenyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol mono-n-butyl ether, tripropylene glycol, tripropylene glycol mono-n-butyl ether, etc.;

[0260] 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;

[0261] Tertiary alcohols such as tert-butyl alcohol, tert-pentanol, tert-hexanol, etc.

[0262] Among them, the alcohol solvent is preferably a secondary alcohol or a tertiary alcohol from the viewpoint of suppressing the deprotection of the acetal group and being able to reduce the viscosity of the polymer solution.

[0263] The alcohol solvent preferably has 1 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and even more preferably 3 to 6 carbon atoms, since the boiling point is relatively low and the solvent can be easily removed by heating.

[0264] As the alcohol solvent, propylene glycol monomethyl ether is particularly preferred.

[0265] Examples of the amine solvent include diethyleneamine, dimethylamine, and oleylamine.

[0266] Examples of the phenolic solvent include phenol, cresol, o-cresol, m-cresol, p-cresol, and xylenol.

[0267] Preferred examples of the aprotic solvent include ether solvents, ether acetate solvents, and amide solvents. Among them, the aprotic solvent is more preferably an amide solvent.

[0268] Examples of the ether solvent include tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl ether.

[0269] Examples of the ether acetate solvent include one or two 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.

[0270] Examples of the amide solvent include N,N-diethylformamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetramethylurea, etc. In terms of compatibility with the copolymer, N,N-dimethylformamide is preferred.

[0271] The polar solvent is preferably at least one solvent selected from the group consisting of alcohol solvents, ether solvents and amide solvents, and more preferably at least one solvent selected from the group consisting of alcohol solvents and amide solvents.

[0272] The boiling point of the polar solvent is preferably 70 to 180°C, more preferably 100 to 170°C, and even more preferably 110 to 160°C, from the viewpoint of being easily removed by heating and having a certain boiling point to easily form a flat film.

[0273] The polymer solution may contain one or more polar solvents.

[0274] Relative to 100% by mass of polymer solids, the content of the above-mentioned polar solvent in the above-mentioned polymer solution is preferably 10% by mass or more, more preferably 30% by mass or more, and further preferably 40% by mass or more. In addition, from the aspect that the concentration adjustment in the resin composition becomes easy, relative to 100% by mass of polymer solids, the content of the above-mentioned polar solvent is preferably 1000% by mass or less, more preferably 300% by mass or less, and further preferably 200% by mass or less.

[0275] The polymer solution may be prepared by mixing a polymer purified from a polymerization solution containing the polymer obtained during polymerization with the polar solvent, or by adding the polar solvent to a polymerization solution containing the polymer. In the case where the polar solvent is added to a polymerization solution containing the polymer, the polymer solution may contain a polymerization solvent.

[0276] The polymer solution may contain other components in addition to the polymer and the polar solvent.

[0277] 5. Polymer solution

[0278] The polymer or polymer solution can be made into a polymer solution together with an alkaline dispersant and / or an alkaline compound. The storage stability of the polymer solution is excellent. A polymer solution comprising such a polymer or polymer solution and an alkaline dispersant and / or an alkaline compound is also one of the present invention. In addition, neutralization of the polymer or alkaline dispersant with an alkaline compound is also one of the preferred embodiments of the present invention.

[0279] Examples of the basic compound include the above-mentioned basic compounds. The basic compound may be a basic compound in which the basic compound used for the production of the polymer as described above remains.

[0280] As the alkaline dispersant, preferably, there can be mentioned a polymer dispersant having a basic functional group. The polymer dispersant having a basic functional group may be neutralized with the alkaline compound as described above, and for example, a neutralized amine salt is also included.

[0281] Examples of the alkaline dispersant include Disperbyk (registered trademark)-108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164, etc. (all manufactured by BYK Chemical (Japan) Co., Ltd.), SOLSPERSE (registered trademark)-3000, 9000, 13 000, 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. (manufactured by Lubrizol Corporation of Japan), AJISPER (registered trademark) PA111, PB711, PB821, PB822, PB824, etc. (manufactured by AJINOMOTO Fine Techno Co., Ltd.), Disparlon (registered trademark) 1831, 1850, 1860, DA-703-50, DA-7301, DA-325, DA234, etc. (all manufactured by Kusumoto Chemicals Co., Ltd.).

[0282] From the viewpoint of good dispersion stability, 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.

[0283] In addition, in this specification, "total solid content" means the total amount of components forming a solidified material (components excluding the solvent and the curing catalyst which volatilize when forming the solidified material).

[0284] From the viewpoint of good storage stability, the content of the basic compound in the polymer solution is preferably 1 to 50 mass %, more preferably 3 to 45 mass %, and even more preferably 5 to 35 mass %, based on 100 mass % of the total solid content of the polymer solution.

[0285] The content of the polymer in the polymer solution is preferably 5 to 80 mass %, more preferably 10 to 75 mass %, and even more preferably 15 to 70 mass %, based on 100 mass % of the total solid content of the polymer solution.

[0286] In addition, from the viewpoint of further excellent storage stability, the epoxy equivalent of the polymer in the polymer solution is preferably 1000 g / mol or more, more preferably 5000 g / mol or more, and further preferably has no epoxy group.

[0287] The epoxy equivalent can be determined by dividing the mass (g) of the polymer solid content by the number of moles (mol) of epoxy groups contained in the polymer.

[0288] 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, based on 100 parts by mass of the total solid content of the polymer solution.

[0289] The method for preparing the polymer solution is not particularly limited, and an example thereof includes mixing the components contained in the polymer solution by a known mixing means.

[0290] 6. Pigment dispersion

[0291] The polymer solution may further contain a colorant. A colorant dispersion containing the polymer solution and the colorant is also one of the present invention. The colorant dispersion has excellent storage stability.

[0292] The coloring material is not particularly limited, and examples thereof include known pigments and dyes.

[0293] From the perspective of being able to fully meet the recent demands for high color purity and high brightness, the content of the above-mentioned colorant in the above-mentioned colorant dispersion is preferably 1 to 80 mass %, more preferably 5 to 70 mass %, and even more preferably 10 to 60 mass %, based on 100 mass % of the total solid content of the colorant dispersion.

[0294] As the content of the polymer and the alkaline dispersant in the colorant dispersion, preferably, the same range as the content of the polymer and the alkaline dispersant in the polymer solution, respectively.

[0295] The colorant dispersion may further contain a solvent, and examples of the solvent include a polymerization solvent for the polymer, the polar solvent, and the like.

[0296] From the viewpoint of good storage stability, the amount of the solvent in the 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.

[0297] The method for preparing the colorant dispersion is not particularly limited, and the colorant dispersion can be prepared by mixing and dispersing the components contained in the colorant dispersion by a known mixing and dispersing means.

[0298] 7. Photosensitive resin composition

[0299] 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 a photoacid generator is also one of the present invention. The photosensitive resin composition of the present invention has excellent storage stability due to the inclusion of the above-mentioned polymer, and can provide a cured product with excellent solvent resistance even under low-temperature curing conditions.

[0300] The content of the polymer is preferably 5 to 80% by mass, more preferably 10 to 75% by mass, and even more preferably 15 to 70% by mass, relative to 100% by mass of the total solid content of the photosensitive resin composition.

[0301] When the photosensitive resin composition includes the polymer solution, the content of the polar solvent is preferably 10 to 1000 parts by mass, more preferably 30 to 300 parts by mass, and even more preferably 40 to 200 parts by mass based on 100 parts by mass of the total solid content of the photosensitive resin composition.

[0302] When the photosensitive resin composition contains the colorant dispersion, the content of the 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 photosensitive resin composition.

[0303] When the photosensitive resin composition contains the colorant dispersion, the content of the 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 photosensitive resin composition.

[0304] (Polymerizable compound)

[0305] The above-mentioned polymerizable compound is a low molecular weight compound having a polymerizable unsaturated bond (also referred to as a polymerizable unsaturated group) which can be polymerized by irradiation with free radicals, electromagnetic waves (e.g., infrared rays, ultraviolet rays, X-rays, etc.), active energy rays such as electron beams, etc., and examples thereof include monofunctional compounds having one polymerizable unsaturated group in the molecule and polyfunctional compounds having two or more polymerizable unsaturated groups.

[0306] Examples of the monofunctional compound include: N-substituted maleimide monomers; (meth)acrylates; (meth)acrylamides; unsaturated monocarboxylic acids; unsaturated polycarboxylic acids; unsaturated monocarboxylic acids with extended chains between unsaturated groups and carboxyl groups; unsaturated acid anhydrides; aromatic vinyls; conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds; unsaturated isocyanates; etc. In addition, monomers having active methylene groups or active methine groups may also be used.

[0307] Examples of the polyfunctional compound include the following compounds.

[0308] Bifunctional (meth)acrylate compounds such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol 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;

[0309] Trimethylolpropane tri(meth)acrylate, di(trimethylolpropane) tetra(meth)acrylate, glycerol 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 di(trimethylolpropane) tetra(meth)acrylate, ethylene oxide added pentaerythritol tetra(meth)acrylate, ethylene oxide added dipentaerythritol hexa(meth)acrylate, propylene oxide added trimethylolpropane tri(meth)acrylate, propylene oxide added di(trimethylolpropane) 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 di(trimethylolpropane) tetra(meth)acrylate, ε-caprolactone added pentaerythritol tetra(meth)acrylate, ε-caprolactone added dipentaerythritol hexa(meth)acrylate, dipentaerythritol pentaacrylate succinic acid modified product, pentaerythritol triacrylate succinic acid modified product, dipentaerythritol pentaacrylate phthalic acid modified product, pentaerythritol triacrylate phthalic acid modified product, the following formula:

[0310] [Chemistry 11]

[0311]

[0312] A polyfunctional (meth)acrylate compound having three or more functionalities, such as a denatured product of dipentaerythritol hexaacrylate;

[0313] Ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide divinyl ether, trimethylolpropane trivinyl ether, bis(trimethylolpropane) tetravinyl ether, glycerol trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide addition trimethylolpropane trivinyl ether, ethylene oxide addition bis(trimethylolpropane) tetravinyl ether, ethylene oxide addition pentaerythritol tetravinyl ether, ethylene oxide addition dipentaerythritol hexavinyl ether and other multifunctional vinyl ethers;

[0314] (meth)acrylates containing a vinyl ether group, such as 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, 5-vinyloxypentyl (meth)acrylate, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxymethylcyclohexylmethyl (meth)acrylate, p-vinyloxymethylphenylmethyl (meth)acrylate, 2-(vinyloxyethoxy)ethyl (meth)acrylate, and 2-(vinyloxyethoxyethoxyethoxy)ethyl (meth)acrylate;

[0315] Ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butanediol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, bisphenol F alkylene oxide diallyl ether, trimethylolpropane triallyl ether, bis(trimethylolpropane) tetraallyl ether, glycerol triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide addition trimethylolpropane triallyl ether, ethylene oxide addition bis(trimethylolpropane) tetraallyl ether, ethylene oxide addition pentaerythritol tetraallyl ether, ethylene oxide addition dipentaerythritol hexaallyl ether and other multifunctional allyl ethers;

[0316] Allyl (meth)acrylates containing an allyl group, such as allyl (meth)acrylate; polyfunctional isocyanurates containing a (meth)acryloyl group, such as tris(acryloyloxyethyl)isocyanurate, tris(methacryloyloxyethyl)isocyanurate, alkylene oxide addition tris(acryloyloxyethyl)isocyanurate, and alkylene oxide addition tris(methacryloyloxyethyl)isocyanurate; polyfunctional isocyanurates containing an allyl group, such as triallyl isocyanurate; polyfunctional urethane (meth)acrylates obtained by reacting polyfunctional isocyanates, such as toluene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate, with hydroxyl-containing (meth)acrylates, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; polyfunctional aromatic vinyls, such as divinylbenzene; and the like. These polymerizable compounds may be used alone or in combination of two or more.

[0317] Among the above-mentioned polymerizable compounds, it is preferred to use a multifunctional polymerizable compound from the aspect of further improving the curability of the above-mentioned photosensitive resin composition. The number of functions of the above-mentioned multifunctional polymerizable compound is preferably 3 or more, and more preferably 4 or more. In addition, the above-mentioned number of functions is preferably 10 or less, and more preferably 8 or less.

[0318] The molecular weight of the polymerizable compound is not particularly limited, but is preferably 2000 or less, for example, from the viewpoint of handling.

[0319] As the above-mentioned multifunctional polymerizable compound, from the aspects of reactivity, economy, availability, etc., preferably, a compound having a (meth)acryloyl group such as a multifunctional (meth)acrylate compound, a multifunctional urethane (meth)acrylate compound, an isocyanurate compound containing a (meth)acryloyl group, etc. can be cited, and more preferably, a multifunctional (meth)acrylate compound can be cited. By including a compound having a (meth)acryloyl group, the photosensitivity and curability of the above-mentioned photosensitive resin composition are more excellent, and a cured product with further high hardness and high transparency can be obtained. As the above-mentioned multifunctional polymerizable compound, it is further preferred to use a trifunctional or higher multifunctional (meth)acrylate compound.

[0320] 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.

[0321] (Photopolymerization Initiator)

[0322] Specific examples of the photopolymerization initiator include aminoketone compounds such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1-one ("IRGACURE 907", manufactured by BASF), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone ("IRGACURE 369", manufactured by BASF), and 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)butane-1-one ("IRGACURE 379", manufactured by BASF); 2,2-dimethoxy-1,2-diphenylethane-1-one ("IRGACURE 651", manufactured by BASF), methyl benzoylformate ("DAROCURE 651", manufactured by BASF); MBF", manufactured by BASF), benzyl ketal compounds; 1-hydroxycyclohexyl phenyl ketone ("IRGACURE 184", manufactured by BASF), 2-hydroxy-2-methyl-1-phenylpropane-1-one ("DAROCUR 1173", manufactured by BASF), 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one ("IRGACURE 2959", manufactured by BASF), 2 -hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropane-1-one ("IRGACURE 127", manufactured by BASF), [1-hydroxycyclohexyl phenyl ketone + benzophenone] ("IRGACURE 500", manufactured by BASF); and other alkylphenone compounds exemplified in paragraphs

[0084] to

[0086] of Japanese Patent Application Laid-Open No. 2013-227485 Compounds; 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyl oxime) ("OXE01", manufactured by BASF), ethyl ketone, 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)], ethyl ketone ("OXE03", manufactured by BASF) Oxime ester compounds such as oxime (manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime) ("OXE04", manufactured by BASF); benzophenone compounds; benzoin compounds; thioxanthone compounds; halomethylated triazine compounds; halomethylated oxadiazole compounds; biimidazole compounds; titanocene compounds; benzoate compounds; acridine compounds; phosphine oxide compounds; etc. Among them, aminoketone compounds and oxime ester compounds are preferred. The above-mentioned photopolymerization initiators can be used alone or in combination of two or more.

[0323] The content of the photopolymerization initiator is preferably 0.3 to 20% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 8% by mass, based on 100% by mass of the total solid content of the photosensitive resin composition.

[0324] (Photoacid generator)

[0325] The photosensitive resin composition may further include a photoacid generator. By including the photoacid generator, cationic polymerization can be performed, and a cured product having more excellent solvent resistance can be provided.

[0326] The photoacid generator used in the present invention is a compound that generates acid and free radicals by light irradiation. As the above-mentioned photoacid generator, for example, a compound that generates acid by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beams, X-rays, etc., specifically, well-known compounds such as onium salt compounds, sulfone compounds, sulfonate compounds, quinonediazide compounds, sulfonimide compounds, and diazomethane compounds can be cited. Among them, the above-mentioned 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 further preferably a triarylsulfonium salt.

[0327] Specific examples of the photoacid generator include compounds described in paragraphs

[0112] to

[0117] of JP-A-2021-39186.

[0328] The content of the photoacid generator is not particularly limited as long as it is within a range that can exert the effects of the present invention, and may be appropriately set. 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.

[0329] In addition, the above-mentioned photosensitive resin composition may contain other ingredients other than the above-mentioned ingredients as needed. As the above-mentioned other ingredients, for example, there can be mentioned: solvent; colorant (pigment, dye); dispersant; heat resistance improving agent; leveling agent; developing aid; inorganic particles such as silica particles; coupling agents such as silane, aluminum, and titanium; thermosetting resins such as fillers, phenol resins, and polyvinyl phenol; curing aids such as multifunctional thiol compounds; plasticizers; inhibitors; ultraviolet absorbers; antioxidants; matting agents; defoamers; antistatic agents; slip agents; surface modifiers; thixotropic agents; thixotropic aids; quinone diazide compounds; polyphenol compounds; cationic polymerizable compounds; thermal acid generators; and the like. They can be used alone or in combination of two or more. These other ingredients can be appropriately selected from known substances, and their dosage can also be appropriately set.

[0330] For example, when the photosensitive resin composition is used for a color filter, the photosensitive resin composition preferably contains a coloring material.

[0331] Furthermore, the photosensitive resin composition preferably contains a polyfunctional thiol compound from the viewpoint that crosslinking with a vinyl ether group and promotion of cationic polymerization can be expected.

[0332] Examples of the polyfunctional thiol compound 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-sulfanylbutyryloxy)ethyl)-1,3,5-triazinane-2,4,6-trione, and trimethylolpropane tris(3-mercaptobutyrate).

[0333] <Preparation of Photosensitive Resin Composition>

[0334] There is no particular limitation on the method for preparing the photosensitive resin composition of the present invention, and a known method can be used. For example, a method in which the above-mentioned components are mixed and dispersed using various mixers and dispersers can be cited. The mixing and dispersing step is not particularly limited, and can be carried out using a known method. In addition, other steps that are usually performed may also be further included. When the above-mentioned photosensitive resin composition contains a colorant, it is preferably prepared by a known colorant dispersion treatment step.

[0335] 8. Cured product

[0336] There is no particular limitation on the method for obtaining a cured product using the photosensitive resin composition of the present invention, and a known method may be used. For example, the photosensitive resin composition is applied to a substrate or molded on a substrate, and cured by heating or irradiation with active energy rays such as ultraviolet rays, or a combination thereof to obtain a cured product.

[0337] As a method for producing the above-mentioned cured product, for example, a method including the following steps is preferably mentioned: step (1), applying the above-mentioned photosensitive resin composition on a substrate to form a coating film; step (2), irradiating the formed coating film with light; step (3), developing and removing the unirradiated portion; and step (4), heating the coating film irradiated with light.

[0338] The substrate is not particularly limited and may be appropriately selected depending on the purpose and application. Examples thereof include substrates made of various materials such as a glass plate and a plastic plate.

[0339] In the step (1), the method for applying the photosensitive resin composition to form a coating film is not particularly limited, and the coating can be performed by a known method such as spin coating, slit coating, roll coating, and cast coating.

[0340] In the above-mentioned manufacturing method, it is preferred that the above-mentioned photosensitive resin composition is applied to a substrate and then the applied material is dried to form a coating film. The above-mentioned drying can be carried out by a known method, for example, using a hot plate, an IR oven, a convection oven, etc. The drying conditions can be appropriately selected according to the boiling point of the solvent component contained, the type of curing component, the film thickness, the performance of the dryer, etc., and it is usually preferably carried out at a temperature of 50 to 160° C. for 10 seconds to 300 seconds.

[0341] In the above step (2), there is no particular limitation on the method for irradiating the formed coating film with light, and it can be carried out by a known method. As the light source of the active light used in the light irradiation, for example, there can be mentioned 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 arc lamps, fluorescent lamps, and laser sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, and semiconductor lasers.

[0342] When the coating film is irradiated with light, the light irradiation may be performed through a photomask. As the photomask, a mask having a light shielding portion formed thereon in accordance with a target pattern may be used.

[0343] In the above step (3), after the above light irradiation step, a developing treatment is performed using a developer to remove the unirradiated portion. The irradiated portion is cured by light irradiation, and the cured product is insoluble or poorly soluble in the developer. On the other hand, the unirradiated portion is dissolved in the developer and is therefore removed by the developing treatment to obtain a patterned cured film. The developing treatment can usually be performed at a developing temperature of 10 to 50° C. by immersion developing, spray developing, brush developing, ultrasonic developing, or the like.

[0344] The developer used in the above step (3) is not particularly limited as long as it dissolves the above photosensitive resin composition. An organic solvent or an alkaline aqueous solution is generally used, and a mixture thereof may also be used. It should be noted that when an alkaline aqueous solution is used as the developer, it is preferably washed with water after development. As the organic solvent or alkaline aqueous solution, for example, the same organic solvent or alkaline aqueous solution as that described in Japanese Patent Publication No. 2015-157909 may be cited.

[0345] In the above step (4), the coating film after the development treatment is preferably heated at 150°C or less. In the heating step (post-curing step) after the light irradiation in the above step (4), the heating temperature is preferably 130°C or less, more preferably 120°C or less. The photosensitive resin composition of the present invention can perform a good curing reaction even at a relatively low temperature, and can provide a cured product with excellent solvent resistance. As the lower limit of the heating temperature, from the perspective of maintaining curability, it is preferably 70°C or more, more preferably 80°C or more.

[0346] The heating time in the heating step is not particularly limited, and is preferably 5 to 60 minutes, for example. The heating method is also not particularly limited, and can be performed using a known heating device such as a hot plate, a convection oven, or a high-frequency heater.

[0347] When the cured product obtained by the above production method is a cured film, the film thickness is preferably 0.1 to 50 μm, more preferably 0.5 to 40 μm, and even more preferably 1 to 30 μm in order to fully exhibit the characteristics as a protective film.

[0348] The cured product obtained by the above production method has excellent solvent resistance. A cured product obtained by curing the above photosensitive resin composition is also one of the present invention.

[0349] 9. Purpose

[0350] The polymer and photosensitive resin composition of the present invention have excellent storage stability and can provide a cured product with excellent solvent resistance even under low temperature curing conditions, so it can be appropriately used in applications requiring storage stability and high solvent resistance. The polymer and photosensitive resin composition of the present invention can be appropriately used as an optical material, preferably as an anti-corrosion agent. The curable resin composition of the present invention can be appropriately used as a negative type or a positive type.

[0351] The polymer and photosensitive resin composition of the present invention can be suitably used in various optical components such as color filters, black matrices, photo spacers, black column spacers, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, insulating films, films, organic protective films, etc., or components of motors / electronic devices, etc., such as liquid crystal / organic EL / quantum dot / micro LED liquid crystal display devices or solid-state imaging elements, touch panel display devices, etc. Among them, it is preferably used for color filter formation.

[0352] Example

[0353] The present invention is described in more detail below with reference to Examples, but the present invention is not limited to these Examples. It should be noted that, unless otherwise stated, "parts" means "parts by mass" and "%" means "% by mass".

[0354] Various evaluation methods used in the present examples are as follows.

[0355] < 1 H-NMR measurement>

[0356] The obtained monomer compound was subjected to the following conditions: 1 H-NMR determination.

[0357] Apparatus: Nuclear magnetic resonance apparatus manufactured by Agilent Technologies (600 MHz)

[0358] Determination solvent: deuterated chloroform

[0359] Sample preparation: Several mg to several tens of mg of the obtained monomer compound are dissolved in a measurement solvent.

[0360] <Acid value>

[0361] 3 g of the polymer solution was accurately weighed and dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and titrated using a 0.1 N aqueous KOH solution as a titrant. The titration was performed using an automatic titrator (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value (mgKOH / g) per 1 g of the solid content was determined from the acid value of the polymer solution and the solid content of the polymer solution.

[0362] It should be noted that the solid content of the polymer solution is determined by the following method. That is, about 1 g of the polymer solution is weighed in an aluminum cup, about 3 g of acetone is added to dissolve it, and then it is naturally dried at room temperature. After that, a hot air dryer (trade name: PHH-101, manufactured by Espec) is used to dry it at 140°C under vacuum for 1.5 hours, and then it is naturally cooled in a dryer and the mass is measured. The solid content (mass %) of the polymer solution is calculated from the mass reduction.

[0363] <Vinyl ether equivalent>

[0364] The molar mass (mol) of the vinyl ether group potentially contained in the polymer can be obtained by dividing the mass (g) of the polymer solid content by the molar number (mol) of the vinyl ether group potentially contained in the polymer.

[0365] <Epoxy Equivalent Weight>

[0366] The molecular weight can be determined by dividing the mass (g) of the polymer solid content by the number of moles (mol) of epoxy groups contained in the polymer.

[0367] <Double bond equivalent>

[0368] The molecular weight can be determined by dividing the mass (g) of the polymer solid content by the amount (mol) of double bonds in the polymer.

[0369] <Weight Average Molecular Weight>

[0370] The weight average molecular weight of the polymer was measured by GPC (gel permeation chromatography) using HLC-8220GPC (manufactured by Tosoh Corporation) and column: TSKgel SuperHZM-M (manufactured by Tosoh Corporation) using polystyrene as a standard substance and tetrahydrofuran as an eluent.

[0371] <Storage stability (viscosity change rate)>

[0372] (polymer)

[0373] The viscosity of the polymer was measured at 25°C using a viscometer (VISCOMETER TV-100, manufactured by Toki Sangyo Co., Ltd.). The viscosity change rate is the rate of change of the viscosity before and after storage when the polymer solution is stored at 40°C for 1 week, and represents the ratio (%) of the viscosity after storage when the viscosity before storage is set as 100%. The smaller the value of the viscosity change rate, the better the storage stability of the polymer is evaluated.

[0374] (Photosensitive resin composition)

[0375] The viscosity of the photosensitive resin composition was measured at 25°C using a viscometer (VISCOMETER TV-100, manufactured by Toki Sangyo Co., Ltd.). The viscosity change rate is the change rate of the viscosity before and after the photosensitive resin composition is stored at 40°C for 1 month, and represents the ratio (%) of the viscosity after storage when the viscosity before storage is set to 100%. The smaller the value of the viscosity change rate, the better the storage stability of the photosensitive resin composition is evaluated.

[0376] <Solvent resistance>

[0377] The photosensitive resin composition was spin-coated on a 5 cm square glass substrate, dried at 90°C for 2 minutes, exposed at 100 mJ using a high-pressure mercury lamp, and heat treated (post-cured) at 90°C for 30 minutes to obtain a cured film with a film thickness of 2 μm. After that, the cured film was immersed in 20 g of propylene glycol monomethyl ether at 30°C for 5 minutes and then taken out. The absorbance of the immersion liquid after the cured film was taken out was measured using a spectrophotometer UV3100 (manufactured by Shimadzu Corporation). The larger the absorbance value, the more the colorant was dissolved in the immersion liquid, and the lower the solvent resistance of the photosensitive resin composition was evaluated.

[0378] <Developability>

[0379] The photosensitive resin composition was applied on a 10 cm square glass substrate by spin coating, and after heat treatment (90° C., 3 minutes), the photosensitive resin composition was irradiated at 60 mJ / cm through a photomask having an opening of 30 μm line and space at a distance of 50 μm from the coating film using a UV Aligner (manufactured by Dainippon Scientific Co., Ltd., trade name “MA-1100”) equipped with a 2.0 kW ultrahigh pressure mercury lamp. 2 The film was exposed at an exposure amount of 100 nm (365 nm illumination conversion), a 0.05% potassium hydroxide aqueous solution was spread using a rotary developer to dissolve and remove the unexposed portion, and the remaining exposed portion was washed with pure water for 10 seconds for development, thereby evaluating the developability.

[0380] Specifically, the coating film after development through a photomask as described above was observed using a surface roughness meter (manufactured by Ryoka Systems Co., Ltd., trade name "VertScan 2.0"), and the time required to spray a 0.05% potassium hydroxide aqueous solution to wash away the unexposed portion was defined as the development time.

[0381] (Production Example 1)

[0382] Synthesis of Monomer Compound (A-1)

[0383] In a reaction tank equipped with a thermometer, a stirrer, a gas inlet pipe, a cooling pipe and a drip tank inlet, 100.0 parts of 2-(2-vinyloxyethoxy)ethyl methacrylate and 60.0 parts of acetic acid were added, and the temperature was raised to 60°C, and the reaction was carried out for 12 hours. After the reaction is completed, the reaction tank is cooled, diluted with ethyl acetate, and the contents are transferred to a separatory funnel. Wash twice with an aqueous sodium carbonate solution and twice with water, and extract the oil layer. After using magnesium sulfate to absorb the water in the oil layer, the magnesium sulfate is removed by filtration, and the ethyl acetate in the oil layer is removed by using an evaporator, thereby obtaining a monomer compound (A-1). Utilize 1 The obtained monomer compound was confirmed by H-NMR. As a result, it was confirmed that the peak derived from vinyl ether at around 6.5 ppm disappeared, and the generation of the monomer compound (A-1) was confirmed from the integrated value.

[0384] (Production Example 2)

[0385] Synthesis of Monomer Compound (A-2)

[0386] The same operation as in Production Example 1 was carried out except that 60.0 parts of acetic acid in Production Example 1 was changed to 90.0 parts of isopropyl alcohol, thereby obtaining a monomer compound (A-2).

[0387] (Production Example 3)

[0388] Synthesis of Monomer Compound (A-3)

[0389] The same operation as in Production Example 1 was carried out except that 60.0 parts of acetic acid in Production Example 1 was changed to 46.0 parts of ethanol, thereby obtaining a monomer compound (A-3).

[0390] (Production Example 4)

[0391] Monomer compound (A-4)

[0392] In a reaction tank equipped with a thermometer, a stirrer, a gas inlet pipe, a cooling pipe, and a dripping tank inlet, 30.0 parts of acetic acid and 0.01 parts of p-toluenesulfonic acid were added and stirred, and heated to 30°C to prepare a uniform mixed liquid. Next, 100.0 parts of 2-(2-vinyloxyethoxy)ethyl methacrylate was added dropwise while paying attention to heat release. After the addition was completed, the reaction was carried out at 30°C for 3 hours to obtain a monomer compound (A-4). 1 The obtained monomer compound was confirmed by H-NMR. As a result, it was confirmed that the peak derived from vinyl ether at around 6.5 ppm disappeared, and the generation of the monomer compound (A-4) was confirmed from the integrated value.

[0393] (Production Example 5)

[0394] Synthesis of Monomer Compound (A-5)

[0395] The same operation as in Production Example 4 was carried out except that 30.0 parts of acetic acid in Production Example 4 was changed to 30.0 parts of isopropyl alcohol to obtain a monomer compound (A-5).

[0396] (Production Example 6)

[0397] Synthesis of Monomer Compound (A-6)

[0398] The same operation as in Production Example 4 was carried out except that 30.0 parts of acetic acid in Production Example 4 was changed to 23.0 parts of ethanol, thereby obtaining a monomer compound (A-6).

[0399] (Production Example 7)

[0400] Synthesis of Monomer Compound (A-7)

[0401] The same operation as in Production Example 4 was carried out 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 to obtain a monomer compound (A-7).

[0402] (Production Example 8)

[0403] Synthesis of Monomer Compound (A-8)

[0404] The same operation as in Production Example 7 was carried out except that 32.2 parts of acetic acid in Production Example 7 was changed to 39.8 parts of propionic acid to obtain a monomer compound (A-8).

[0405] (Production Example 9)

[0406] Synthesis of Monomer Compound (A-9)

[0407] The same operation as in Production Example 7 was carried out except that 32.2 parts of acetic acid in Production Example 7 was changed to 47.3 parts of butyric acid, thereby obtaining a monomer compound (A-9).

[0408] (Production Example 10)

[0409] In a reaction tank equipped with a thermometer, a stirrer, a gas inlet pipe, a cooling pipe, and a dripping tank inlet, 107.6 parts of lauric acid and 0.01 parts of p-toluenesulfonic acid were added and stirred, and heated to 50°C to prepare a uniform mixed liquid. Next, 100.0 parts of 2-(2-vinyloxyethoxy)ethyl acrylate was added dropwise while paying attention to heat release. After the addition was completed, the reaction was carried out at 50°C for 3 hours to obtain a monomer compound (A-10). 1 The obtained monomer compound was confirmed by H-NMR. As a result, it was confirmed that the peak derived from vinyl ether at around 6.5 ppm disappeared, and the generation of the monomer compound (A-10) was confirmed from the integrated value.

[0410] [Table 1]

[0411]

[0412] In addition, description in Table 1 shows the following components.

[0413] VEEM: 2-(2-vinyloxyethoxy)ethyl methacrylate

[0414] VEEA: 2-(2-vinyloxyethoxy)ethyl acrylate

[0415] AcOH: acetic acid

[0416] PA: Propionic acid

[0417] BA: butyric acid

[0418] LA: Lauric Acid

[0419] IPA: Isopropyl alcohol

[0420] EtOH: ethanol

[0421] PTSA: p-Toluenesulfonic acid

[0422] AEEM: 2-(2-(1-acetoxyethoxy)ethoxy)ethyl methacrylate

[0423] IEEM: 2-(2-(1-isopropoxyethoxy)ethoxy)ethyl methacrylate

[0424] EEEM: 2-(2-(1-ethoxyethoxy)ethoxy)ethyl methacrylate

[0425] AEEA: 2-(2-(1-acetoxyethoxy)ethoxy)ethyl acrylate

[0426] PEEA: 2-(2-(1-propionyloxyethoxy)ethoxy)ethyl acrylate

[0427] BEEA: 2-(2-(1-butoxyethoxy)ethoxy)ethyl acrylate

[0428] LEEA: 2-(2-(1-lauryloxyethoxy)ethoxy)ethyl acrylate

[0429] According to Preparation Examples 1 to 3, by using 1 equivalent or more of the carboxylic acid compound or alcohol compound relative to 1 equivalent of the (meth)acrylate compound containing a vinyl ether group, the reaction substrate itself acts as a self-catalyst to promote the reaction as described above, thereby enabling the synthesis of the acetal-protected monomer compound under catalyst-free conditions. In addition, according to Preparation Examples 4 to 10, the synthesis can be performed even when an acid catalyst is used.

[0430] (Example 1)

[0431] Synthesis of polymer (B-1)

[0432] 146.7 parts of propylene glycol monomethyl ether acetate were placed in a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a dripping tank inlet, and after nitrogen substitution, the temperature was raised to 60°C. On the other hand, 25.0 parts of propylene glycol monomethyl ether acetate, 23.1 parts of acetic acid, and 0.01 parts of p-toluenesulfonic acid were placed in a beaker as a dripping tank (A), and stirred and mixed to prepare a uniform mixed liquid. Next, 76.9 parts of 2-(2-vinyloxyethoxy)ethyl methacrylate was added dropwise to the mixed liquid while paying attention to heat generation. After the completion of the dropwise addition, the mixture was stirred at 30°C for 3 hours, and then 0.39 parts of triethylamine and 2.9 parts of bis(2-ethylhexyl) peroxydicarbonate ("Peroyl (registered trademark) OPP" manufactured by NOF Corporation) were added as a dropwise addition tank (A). As a dropwise addition tank (B), a mixed solution prepared by stirring and mixing 1.0 parts of n-dodecyl mercaptan and 59.0 parts of propylene glycol monomethyl ether acetate in a beaker was prepared. After the temperature of the reaction tank reached 60°C, the polymerization was carried out by dropping from the dropwise addition tank for 3 hours while maintaining the temperature. After the completion of the dropwise addition, the mixture was kept at 60°C for 6 hours. Afterwards, the mixture was cooled to room temperature to obtain a polymer (B-1). Various physical properties of the obtained polymer are shown in Table 2.

[0433] (Example 2)

[0434] Synthesis of polymer (B-2)

[0435] 133.0 parts of propylene glycol monomethyl ether acetate were placed in a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a drop tank inlet, and after nitrogen substitution, the temperature was raised to 50°C. On the other hand, as the drop tank (A), a mixed solution of 42.9 parts of propylene glycol monomethyl ether acetate, 100.0 parts of methacrylate-2-(2-(1-isopropoxyethoxy)ethoxy)ethyl ester, and 2.0 parts of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was stirred and mixed in a beaker was prepared, and as the drop tank (B), a mixed solution of 2.0 parts of n-dodecyl mercaptan and 58.0 parts of propylene glycol monomethyl ether acetate was stirred and mixed in a beaker was prepared. After the temperature of the reaction tank reached 50°C, the temperature was maintained while dropping from the drop tank over 3 hours to perform polymerization. After the addition was completed, the mixture was kept at 50°C for 7 hours and then cooled to room temperature to obtain a polymer (B-2). Table 2 shows various physical properties of the obtained polymer.

[0436] (Example 3)

[0437] Synthesis of polymer (B-3)

[0438] 109.3 parts of propylene glycol monomethyl ether acetate were placed in a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a drop tank inlet, and after nitrogen substitution, the temperature was raised to 60°C. On the other hand, as a drop tank, a mixed solution of 100.0 parts of propylene glycol monomethyl ether acetate, 100.0 parts of methacrylate-2-(2-(1-ethoxyethoxy)ethoxy)ethyl ester, and 3.5 parts of n-dodecyl mercaptan was stirred and mixed in a beaker, and as an initiator tank, a mixed solution of 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 28.0 parts of propylene glycol monomethyl ether acetate was stirred and mixed in a beaker was prepared. After the temperature of the reaction tank reached 60°C, the temperature was maintained while dropping from the drop tank over 3 hours to perform polymerization. A total of 30 parts in the initiator tank were added to the reaction tank 6 times at 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours after the start of polymerization. 5 parts were added each time. After the dropwise addition was completed, the reaction tank was heated to 70°C and aged for 10 hours. After cooling to room temperature, a polymer (B-3) was obtained. The various physical properties of the obtained polymer are shown in Table 2.

[0439] (Example 4)

[0440] Synthesis of polymer (B-4)

[0441] In a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a drop tank inlet, 115.3 parts of propylene glycol monomethyl ether acetate was added, and after nitrogen substitution, the temperature was raised to 60°C. On the other hand, as a drop tank (A), a mixed solution prepared by stirring and mixing 2.0 parts of N-benzylmaleimide, 38.0 parts of cyclohexyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 30.0 parts of propylene glycol monomethyl ether acetate, and 2.0 parts of n-dodecyl mercaptan in a beaker was prepared, and as a drop tank (B), 60.0 parts of propylene glycol monomethyl ether acetate, 6.9 parts of acetic acid, and 0.002 parts of p-toluenesulfonic acid were added to a beaker and stirred and mixed to prepare a uniform mixed solution. Next, 23.1 parts of 2-(2-vinyloxyethoxy)ethyl methacrylate was added dropwise to the above mixed solution while paying attention to heat generation. After completion of the dropwise addition, the mixture was stirred at 30°C for 3 hours, 0.12 parts of triethylamine was added, and the mixture after stirring and mixing was used as a dropping tank (B). As an initiator tank, a mixed solution was prepared by stirring and mixing 2.9 parts of bis(2-ethylhexyl) peroxydicarbonate ("Peroyl (registered trademark) OPP" manufactured by NOF Corporation) and 27.1 parts of propylene glycol monomethyl ether acetate in a beaker. After the temperature of the reaction tank reached 60°C, the mixture was dripped from the dripping tanks (A) and (B) for 3 hours while maintaining the temperature to carry out polymerization. A total of 30 parts in the initiator tank were divided into 6 times, 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours after the start of polymerization, and 5 parts were added to the reaction tank each time. After the dripping was completed, 60°C was maintained for aging for 6 hours. Thereafter, after cooling to room temperature, 11.5 parts of succinic anhydride, 11.7 parts of triethylamine, and 29.6 parts of propylene glycol monomethyl ether acetate were added to the reaction tank, and the reaction was carried out at 50°C for 1 hour. After the reaction, the mixture was cooled to room temperature to obtain a polymer (B-4). Various physical properties of the obtained polymer are shown in Table 2.

[0442] (Example 5)

[0443] Synthesis of polymer (B-5)

[0444] 146.0 parts of propylene glycol monomethyl ether acetate were placed in a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a drop tank inlet, and after nitrogen substitution, the temperature was raised to 60°C. On the other hand, as a drop tank (A), a mixed solution prepared by stirring and mixing 20.0 parts of cyclohexyl methacrylate, 40.0 parts of 2-hydroxyethyl methacrylate, 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 40.0 parts of propylene glycol monomethyl ether acetate in a beaker was prepared, and as a drop tank (B), 46.5 parts of propylene glycol monomethyl ether acetate, 9.2 parts of isopropyl alcohol, and 0.003 parts of p-toluenesulfonic acid were placed in a beaker and stirred and mixed to prepare a uniform mixed solution. Next, 30.8 parts of 2-(2-vinyloxyethoxy)ethyl methacrylate was dropped into the above mixed solution while paying attention to heat generation. After completion of the dropwise addition, 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 a dropwise addition tank (B).

[0445] After the temperature of the reaction tank reaches 60°C, the polymerization is carried out by dripping from the dripping tank (A) and (B) for 3 hours while maintaining the temperature. After the dripping is completed, the temperature is raised to 70°C and the aging is carried out for 10 hours. After that, after cooling to room temperature, 15.4 parts of succinic anhydride, 15.6 parts of triethylamine, and 42.1 parts of propylene glycol monomethyl ether acetate are added to the reaction tank and reacted at 50°C for 1 hour. After the reaction, the reaction is cooled to room temperature to obtain a polymer (B-5). The various physical properties of the obtained polymer are shown in Table 2.

[0446] (Example 6)

[0447] Synthesis of polymer (B-6)

[0448] In a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a dropping tank inlet, 160.8 parts of propylene glycol monomethyl ether acetate was added, stirred and mixed, and then replaced with nitrogen, and then heated to 50° C. On the other hand, as a dropping tank (A), a mixed solution of 15.0 parts of 2-(2-(1-acetoxyethoxy)ethoxy)ethyl methacrylate, 70.0 parts of methyl methacrylate, 15.0 parts of methacrylic acid, 2.0 parts of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 15.0 parts of propylene glycol monomethyl ether acetate was stirred and mixed in a beaker was prepared, and as a dropping tank (B), a mixed solution of 2.0 parts of n-dodecyl mercaptan and 58.0 parts of propylene glycol monomethyl ether acetate was added and stirred and mixed in a beaker was prepared. After the temperature of the reaction tank reached 50°C, the polymerization was carried out by dropping from the dropping tanks (A) and (B) for 3 hours while maintaining the temperature. After the dropping was completed, the temperature was maintained at 50°C for 7 hours of aging. After cooling to room temperature, a polymer (B-6) was obtained. The various physical properties of the obtained polymer are shown in Table 2.

[0449] (Example 7)

[0450] Synthesis of polymer (B-7)

[0451] In a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a dropping tank inlet, 190.8 parts of propylene glycol monomethyl ether acetate and 14.3 parts of triethylamine were added, and after nitrogen substitution, the temperature was raised to 60°C. On the other hand, as a dropping tank, a mixed solution of 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 was stirred and mixed in a beaker was prepared, and as an initiator tank, 2.0 parts of bis(2-ethylhexyl) peroxydicarbonate ("Peroyl (registered trademark) OPP" manufactured by NOF Corporation) was prepared. 9 parts of propylene glycol monomethyl ether acetate and 27.1 parts of propylene glycol monomethyl ether acetate are stirred and mixed in a beaker to form a mixed solution. After the temperature of the reaction tank reaches 60°C, while maintaining the temperature, dripping is started from the dripping tank for 3 hours to carry out polymerization. The total of 30 parts in the initiator tank is divided into 6 times at 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours from the start of polymerization, and 5 parts are added to the reaction tank each time. After the addition is completed, 60°C is maintained for 6 hours of maturation. After cooling to room temperature, a polymer (B-7) is obtained. The various physical properties of the obtained polymer are shown in Table 2.

[0452] (Example 8)

[0453] Synthesis of polymer (B-8)

[0454] In a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a drop tank inlet, 172.6 parts of propylene glycol monomethyl ether acetate and 23.9 parts of triethylamine were added, and after nitrogen substitution, the temperature was raised to 50°C. On the other hand, as a drop tank (A), a mixed solution prepared by stirring and mixing 5.0 parts of N-cyclohexylmaleimide, 20.0 parts of methacrylic acid, 20.0 parts of propylene glycol monomethyl ether acetate, and 3.0 parts of n-dodecyl mercaptan in a beaker was prepared, and as a drop tank (B), 15.0 parts of propylene glycol monomethyl ether acetate, 17.3 parts of acetic acid, and 0.006 parts of p-toluenesulfonic acid were added to a beaker and stirred and mixed to prepare a uniform mixed solution. Next, 57.7 parts of 2-(2-vinyloxyethoxy)ethyl methacrylate was added dropwise to the mixed solution while paying attention to heat generation. After the dropwise addition was completed, it was stirred at 30°C for 3 hours to prepare a drop tank (B). As an initiator tank, prepare a mixed solution of 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 by stirring and mixing. After the temperature of the reaction tank reaches 50°C, while maintaining the temperature, dripping is started from the dripping tank (A) and (B) for 3 hours to carry out polymerization. The total of 30 parts in the initiator tank is divided into 6 times at 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours from the start of polymerization, and 5 parts are added to the reaction tank each time. After the dripping is completed, 50°C is maintained for 7 hours of maturation. After cooling to room temperature, a polymer (B-8) is obtained. Various physical properties of the obtained polymer are shown in Table 2.

[0455] (Example 9)

[0456] Synthesis of polymer (B-9)

[0457] In a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a dropping tank inlet, 145.8 parts of propylene glycol monomethyl ether acetate was charged, and after nitrogen substitution, the temperature was raised to 60° C. On the other hand, as a dropping tank (A), a mixed solution prepared by stirring and mixing 10.0 parts of N-benzylmaleimide, 30.0 parts of cyclohexyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 2.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 30.0 parts of propylene glycol monomethyl ether acetate in a beaker was prepared, and as a dropping tank (B), 57.5 parts of propylene glycol monomethyl ether acetate, 6.9 parts of acetic acid, and 0.002 parts of p-toluenesulfonic acid were charged in a beaker and stirred and mixed to prepare a uniform mixed solution. Next, 23.1 parts of 2-(2-vinyloxyethoxy)ethyl methacrylate was added dropwise to the mixed solution while paying attention to the heat release. After the addition was completed, 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 as a dropping tank (B). After the temperature of the reaction tank reached 60°C, the polymerization was carried out by dropping from the dropping tanks (A) and (B) for 3 hours while maintaining the 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, 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 tank and reacted at 50°C for 1 hour. After the reaction, the mixture was cooled to room temperature to obtain a polymer (B-9). Various physical properties of the obtained polymer are shown in Table 2.

[0458] (Example 10)

[0459] Synthesis of polymer (B-10)

[0460] 228.3 parts of propylene glycol monomethyl ether acetate were placed in a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a dropping tank inlet, and after nitrogen substitution, the temperature was raised to 60° C. On the other hand, as a dropping tank (A), a mixed solution of 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 bis(2-ethylhexyl) peroxydicarbonate ("Peroyl (registered trademark) OPP" manufactured by NOF Corporation), and 30.0 parts of propylene glycol monomethyl ether acetate was stirred and mixed in a beaker was prepared, and as a dropping tank (B), a mixed solution of 2.5 parts of n-dodecyl mercaptan and 57.5 parts of propylene glycol monomethyl ether acetate was placed in a beaker and stirred and mixed was prepared. After the temperature of the reaction tank reaches 60°C, while maintaining the temperature, dripping is started from the dripping tanks (A) and (B) for 3 hours to carry out polymerization. After the dripping is completed, 60°C is maintained for 6 hours of aging. After cooling to room temperature, 26.2 parts of 2-methacryloyloxyethyl isocyanate, 16.8 parts of triethylamine, and 0.2 parts of ANTAGE W400 are added, and the oxygen / nitrogen mixed gas with an oxygen concentration adjusted to 7% is bubbled at 20 ml / min, and the reaction is carried out at 90°C for 2 hours. After cooling to room temperature, 16.6 parts of succinic anhydride are added, and the reaction is carried out at 50°C for 1 hour. After the reaction is completed, it is cooled to room temperature to obtain a polymer (B-10). The various physical properties of the obtained polymer are shown in Table 2.

[0461] (Example 11)

[0462] Synthesis of polymer (B-11)

[0463] 263.7 parts of propylene glycol monomethyl ether acetate were placed in a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a dripping tank inlet, and after nitrogen substitution, the temperature was raised to 60°C. On the other hand, as a dripping tank, a mixed solution of 15.0 parts of N-benzylmaleimide, 15.0 parts of cyclohexyl methacrylate, 25.0 parts of glycidyl methacrylate, 20.0 parts of 2-hydroxyethyl methacrylate, 25.0 parts of 2-(2-(1-isopropoxyethoxy)ethoxy)ethyl methacrylate, 3.0 parts of n-dodecyl mercaptan, and 25.0 parts of propylene glycol monomethyl ether acetate was stirred and mixed in a beaker was prepared. As an initiator tank, a mixed solution of 2.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 28.0 parts of propylene glycol monomethyl ether acetate was stirred and mixed in a beaker was prepared. After the temperature of the reaction tank reaches 60°C, the polymerization is carried out by dripping from the dripping tank for 3 hours while maintaining the temperature. The total of 30 parts in the initiator tank is divided into 6 times at 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours after the start of the polymerization, and 5 parts are added to the reaction tank each time. After the dripping is completed, the reaction tank is heated to 70°C and matured for 10 hours. After cooling to room temperature, 5.1 parts of acrylic acid, 12.2 parts of triethylamine, and 0.2 parts of ANTAGE W400 are added, and the oxygen concentration is adjusted to 7% by bubbling an oxygen / nitrogen mixed gas at 20 ml / min, and the reaction is carried out at 110°C for 7 hours. After cooling to room temperature, 12.0 parts of succinic anhydride are added and reacted at 50°C for 1 hour. After the reaction is completed, it is cooled to room temperature to obtain a polymer (B-11). The various physical properties of the obtained polymer are shown in Table 2.

[0464] (Example 12)

[0465] Synthesis of polymer (B-12)

[0466] 215.7 parts of propylene glycol monomethyl ether acetate were placed in a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a drop tank inlet, and after nitrogen substitution, the temperature was raised to 60°C. On the other hand, as a drop tank (A), a mixed solution prepared by stirring and mixing 5.0 parts of N-phenylmaleimide, 5.0 parts of cyclohexyl methacrylate, 35.0 parts of glycidyl methacrylate, 35.0 parts of 2-hydroxyethyl methacrylate, and 5.0 parts of propylene glycol monomethyl ether acetate in a beaker was prepared, and as a drop tank (B), 68.0 parts of propylene glycol monomethyl ether acetate, 3.7 parts of ethanol, and 0.002 parts of p-toluenesulfonic acid were placed in a beaker and stirred and mixed to prepare a uniform mixed solution. Next, 16.3 parts of 2-(2-vinyloxyethoxy)ethyl methacrylate was dropped into the mixed solution while paying attention to heat generation. After the addition was completed, 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 form a drop tank (B). As an initiator tank, a mixed solution was prepared by stirring and mixing 2.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 28.0 parts of propylene glycol monomethyl ether acetate in a beaker. After the temperature of the reaction tank reached 60°C, the polymerization was carried out by dropping from the drop tanks (A) and (B) for 3 hours while maintaining the temperature. A total of 30 parts in the initiator tank were divided into 6 times, 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours after the start of the polymerization, and 5 parts were added to the reaction tank each time. After the addition was completed, the reaction tank was heated to 70°C and aged for 10 hours. After cooling to room temperature, 14.0 parts of methacrylic acid, 26.9 parts of triethylamine, and 0.2 parts of ANTAGEW400 were added, and the mixture was reacted at 110°C for 7 hours while bubbling an oxygen / nitrogen mixed gas with an oxygen concentration adjusted to 7% 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 completed, the mixture was cooled to room temperature to obtain a polymer (B-12). The various physical properties of the obtained polymer are shown in Table 2.

[0467] (Example 13)

[0468] Synthesis of polymer (B-13)

[0469] 145.3 parts of propylene glycol monomethyl ether acetate were placed in a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a drop tank inlet, and after nitrogen substitution, the temperature was raised to 60°C. On the other hand, as a drop tank (A), a mixed solution prepared by stirring and mixing 2.0 parts of N-benzylmaleimide, 38.0 parts of cyclohexyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 30.0 parts of propylene glycol monomethyl ether acetate, and 2.0 parts of n-dodecyl mercaptan in a beaker was prepared, and as a drop tank (B), 30.0 parts of propylene glycol monomethyl ether acetate, 7.3 parts of acetic acid, and 0.002 parts of p-toluenesulfonic acid were placed in a beaker and stirred and mixed to prepare a uniform mixed solution. Next, 22.7 parts of 2-(2-vinyloxyethoxy)ethyl acrylate was dropped into the above mixed solution while paying attention to heat generation. After the addition is completed, the mixture is stirred at 30°C for 3 hours, and 0.12 parts of triethylamine is added. The mixed solution obtained by stirring and mixing is used as the dropping tank (B). As the initiator tank, a mixed solution is prepared by stirring and mixing 2.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 28.0 parts of propylene glycol monomethyl ether acetate in a beaker. After the temperature of the reaction tank reaches 60°C, while maintaining the temperature, it takes 3 hours to start dropping from the dropping tanks (A) and (B) to perform polymerization. A total of 30 parts in the initiator tank are divided into 6 times at 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours after the start of polymerization, and 5 parts are added to the reaction tank each time. After the addition is completed, the temperature is raised to 70°C and the aging is performed for 6 hours. After cooling to room temperature, 11.5 parts of succinic anhydride, 11.7 parts of triethylamine, and 29.6 parts of propylene glycol monomethyl ether acetate were added to the reaction tank and reacted at 50°C for 1 hour. After the reaction, the mixture was cooled to room temperature to obtain a polymer (B-13). The various physical properties of the obtained polymer are shown in Table 2.

[0470] (Example 14)

[0471] Synthesis of polymer (B-14)

[0472] 145.3 parts of propylene glycol monomethyl ether acetate were placed in a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a drop tank inlet, and after nitrogen substitution, the temperature was raised to 60°C. On the other hand, as a drop tank (A), a mixed solution prepared by stirring and mixing 2.0 parts of N-benzylmaleimide, 38.0 parts of cyclohexyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 30.0 parts of propylene glycol monomethyl ether acetate, and 2.0 parts of n-dodecyl mercaptan in a beaker was prepared, and as a drop tank (B), 30.0 parts of propylene glycol monomethyl ether acetate, 8.5 parts of propionic acid, and 0.002 parts of p-toluenesulfonic acid were placed in a beaker and stirred and mixed to prepare a uniform mixed solution. Next, 21.5 parts of 2-(2-vinyloxyethoxy)ethyl acrylate was dropped into the above mixed solution while paying attention to heat generation. After the addition is completed, the mixture is stirred at 30°C for 3 hours, and 0.12 parts of triethylamine is added. The mixed solution obtained by stirring and mixing is used as the dropping tank (B). As the initiator tank, a mixed solution is prepared by stirring and mixing 2.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 28.0 parts of propylene glycol monomethyl ether acetate in a beaker. After the temperature of the reaction tank reaches 60°C, while maintaining the temperature, it takes 3 hours to start dropping from the dropping tanks (A) and (B) to perform polymerization. A total of 30 parts in the initiator tank are divided into 6 times at 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours after the start of polymerization, and 5 parts are added to the reaction tank each time. After the addition is completed, the temperature is raised to 70°C and the aging is performed for 6 hours. After cooling to room temperature, 11.5 parts of succinic anhydride, 11.7 parts of triethylamine, and 29.6 parts of propylene glycol monomethyl ether acetate were added to the reaction tank and reacted at 50°C for 1 hour. After the reaction, the mixture was cooled to room temperature to obtain a polymer (B-14). The various physical properties of the obtained polymer are shown in Table 2.

[0473] (Example 15)

[0474] Synthesis of polymer (B-15)

[0475] In a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a drop tank inlet, 146.8 parts of propylene glycol monomethyl ether acetate was added, and after nitrogen substitution, the temperature was heated to 60°C. On the other hand, as a drop tank (A), a mixed solution prepared by stirring and mixing 2.0 parts of N-benzylmaleimide, 35.5 parts of cyclohexyl methacrylate, 1.0 part of methyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 30.0 parts of propylene glycol monomethyl ether acetate, and 2.0 parts of n-dodecyl mercaptan in a beaker was prepared, and as a drop tank (B), 28.5 parts of propylene glycol monomethyl ether acetate, 10.1 parts of butyric acid, and 0.002 parts of p-toluenesulfonic acid were added to a beaker and stirred and mixed to prepare a uniform mixed solution. Next, 21.4 parts of 2-(2-vinyloxyethoxy)ethyl acrylate was added dropwise to the above mixed solution while paying attention to heat generation. After the addition is completed, the mixture is stirred at 30°C for 3 hours, and 0.12 parts of triethylamine is added. The mixed solution obtained by stirring and mixing is used as the dropping tank (B). As the initiator tank, a mixed solution is prepared by stirring and mixing 2.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 28.0 parts of propylene glycol monomethyl ether acetate in a beaker. After the temperature of the reaction tank reaches 60°C, while maintaining the temperature, it takes 3 hours to start dropping from the dropping tanks (A) and (B) to perform polymerization. A total of 30 parts in the initiator tank are divided into 6 times at 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours after the start of polymerization, and 5 parts are added to the reaction tank each time. After the addition is completed, the temperature is raised to 70°C and the aging is performed for 6 hours. After cooling to room temperature, 11.5 parts of succinic anhydride, 11.7 parts of triethylamine, and 29.6 parts of propylene glycol monomethyl ether acetate were added to the reaction tank and reacted at 50°C for 1 hour. After the reaction, the mixture was cooled to room temperature to obtain a polymer (B-15). The various physical properties of the obtained polymer are shown in Table 2.

[0476] (Example 16)

[0477] Synthesis of polymer (B-16)

[0478] In a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a drop tank inlet, 159.8 parts of propylene glycol monomethyl ether acetate was placed, and after nitrogen substitution, the temperature was raised to 60°C. On the other hand, as a drop tank (A), a mixed solution prepared by stirring and mixing 2.0 parts of N-benzylmaleimide, 22.5 parts of cyclohexyl methacrylate, 1.0 part of methyl methacrylate, 30.0 parts of 2-hydroxyethyl methacrylate, 30.0 parts of propylene glycol monomethyl ether acetate, and 2.0 parts of n-dodecyl mercaptan in a beaker was prepared, and as a drop tank (B), 15.5 parts of propylene glycol monomethyl ether acetate, 23.1 parts of lauric acid, and 0.002 parts of p-toluenesulfonic acid were placed in a beaker, and the temperature was raised to 50°C and stirred and mixed to prepare a uniform mixed solution. Next, 21.4 parts of 2-(2-vinyloxyethoxy)ethyl acrylate was dropped into the above mixed solution while paying attention to heat generation. After the addition is completed, stir at 50°C for 3 hours, add 0.12 parts of triethylamine, and use the mixed solution obtained by stirring and mixing as the dropping tank (B). As the initiator tank, prepare a mixed solution obtained by stirring and mixing 2.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 28.0 parts of propylene glycol monomethyl ether acetate in a beaker. After the temperature of the reaction tank reaches 60°C, while maintaining the temperature, dripping from the dropping tanks (A) and (B) for 3 hours to carry out polymerization. A total of 30 parts in the initiator tank are divided into 6 times at 0 minutes, 30 minutes, 1 hour, 1.5 hours, 2 hours, and 2.5 hours after the start of polymerization, and 5 parts are added to the reaction tank each time. After the addition is completed, the temperature is raised to 70°C and the aging is carried out for 6 hours. After cooling to room temperature, 11.5 parts of succinic anhydride, 11.7 parts of triethylamine, and 29.6 parts of propylene glycol monomethyl ether acetate were added to the reaction vessel and reacted at 50°C for 1 hour. After the reaction, the mixture was cooled to room temperature to obtain a polymer (B-16). The various physical properties of the obtained polymer are shown in Table 2.

[0479] (Comparative Example 1)

[0480] Synthesis of polymer (B-17)

[0481] 143.3 parts of propylene glycol monomethyl ether acetate were added to a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe and a drop tank inlet, and after nitrogen substitution, the temperature was heated to 70°C. On the other hand, as a drop tank (A), a mixed solution of 28.0 parts of 3-carboxymethyl methyl methacrylate, 12.8 parts of azobisisobutyronitrile, and 72.0 parts of propylene glycol monomethyl ether acetate was stirred and mixed in a beaker was prepared, and as a drop tank (B), a mixed solution of 72.0 parts of 4-(1-methoxy)ethoxycyclohexyl methacrylate and 18.0 parts of propylene glycol monomethyl ether acetate was stirred and mixed in a beaker was prepared. After the temperature of the reaction tank reached 70°C, while maintaining the temperature, dripping was started from the drip tanks (A) and (B) for 3 hours to perform polymerization. After the dripping was completed, 70°C was also maintained for 7 hours of aging. After cooling to room temperature, polymer (B-17) was obtained. Table 2 shows various physical properties of the obtained polymer.

[0482] (Comparative Example 2)

[0483] Synthesis of polymer (B-18)

[0484] In a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a drop tank inlet, 143.3 parts of propylene glycol monomethyl ether acetate and 10.8 parts of triethylamine were added, and after nitrogen substitution, the temperature was raised to 70°C. On the other hand, as a drop tank (A), a mixed solution of 28.0 parts of 3-carboxymethyl methyl methacrylate, 12.8 parts of azobisisobutyronitrile, and 72.0 parts of propylene glycol monomethyl ether acetate was stirred and mixed in a beaker was prepared, and as a drop tank (B), a mixed solution of 72.0 parts of 4-(1-methoxy)ethoxycyclohexyl methacrylate and 18.0 parts of propylene glycol monomethyl ether acetate was stirred and mixed in a beaker was prepared. After the temperature of the reaction tank reached 70°C, while maintaining the temperature, dripping was started from the drip tanks (A) and (B) for 3 hours to perform polymerization. After the dripping was completed, 70°C was also maintained for aging for 7 hours. After cooling to room temperature, a polymer (B-18) was obtained. Table 2 shows various physical properties of the obtained polymer.

[0485] (Comparative Example 3)

[0486] Synthesis of polymer (B-19)

[0487] 105.3 parts of propylene glycol monomethyl ether acetate were placed in a reaction tank equipped with a thermometer, a stirrer, a gas introduction pipe, a cooling pipe, and a drop tank inlet, and after nitrogen substitution, the temperature was raised to 70°C. On the other hand, as a drop tank (A), a mixed solution of 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 tert-butyl peroxypivalate ("Luperox (registered trademark) 11" manufactured by Arkema Yoshitomi Co., Ltd.) was prepared in a beaker, and a mixed solution of 2.0 parts of n-dodecyl mercaptan and 78 parts of propylene glycol monomethyl ether acetate was prepared in a drop tank (B). After the temperature of the reaction tank reached 70°C, the polymerization was carried out by dropping from the drop tank over 3 hours while maintaining the temperature. After the completion of the dropwise addition, the temperature was maintained at 70°C for 30 minutes, and then the temperature was raised to 80°C and aged for 180 minutes to obtain a polymer (B-19).

[0488]

[0489] In addition, description in Table 2 shows the following components.

[0490] BzMI: N-Benzylmaleimide

[0491] PMI: N-phenylmaleimide

[0492] CHMI: N-cyclohexylmaleimide

[0493] CHMA: Cyclohexyl methacrylate

[0494] MMA: Methyl Methacrylate

[0495] HEMA: 2-Hydroxyethyl Methacrylate

[0496] MECMA: 4-(1-methoxy)ethoxycyclohexyl methacrylate

[0497] AA: Acrylic acid

[0498] MAA: Methacrylic acid

[0499] AMAA: 3-carboxymethyl methacrylate

[0500] GMA: Glycidyl Methacrylate

[0501] MOI: 2-methacryloyloxyethyl isocyanate

[0502] SAH: Succinic Anhydride

[0503] OPP: Bis(2-ethylhexyl) peroxydicarbonate ("Peroyl (registered trademark) OPP" manufactured by NOF Corporation)

[0504] V70: 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (V-70 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0505] V65: 2,2'-azobis(2,4-dimethylvaleronitrile) (V-65 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0506] AIBN: Azobisisobutyronitrile

[0507] L11: tert-butyl peroxypivalate ("Luperox 11" manufactured by Arkema Yoshitomi Co., Ltd.)

[0508] TEA: triethylamine

[0509] DEMA: Diethylmethylamine

[0510] (Preparation of Photosensitive Resin Composition)

[0511] 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 (registered trademark) OXE02 (manufactured by BASF Japan) were added, and a diluent solvent (propylene glycol monomethyl ether acetate) was further added so that the solid content concentration (non-volatile component) was 20% by mass, and the mixture was stirred to obtain a photosensitive resin composition (C-1).

[0512] (Preparation of Pigment Dispersion 1)

[0513] 12.9 parts of propylene glycol monomethyl ether acetate, 0.4 parts of Disparlon DA-7301 as a basic dispersant, 2.25 parts of CI Pigment Green 58 as a colorant, and 1.5 parts of CI Pigment Yellow 138 were mixed and dispersed in a paint shaker for 3 hours to obtain a pigment dispersion 1 (solid content 22% by mass).

[0514] 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 by the above-mentioned methods.

[0515]

[0516] Tables 2 and 3 show that the polymers of Examples 4 to 16 have faster developing speeds and better solvent resistance than the polymers of Comparative Examples 1 to 3. It is believed that the polymers of Examples 4 to 16 have PEG chains in their acetal monomer units and have high hydrophilicity, which improves the developing speed.

[0517] On the other hand, it is believed that Comparative Examples 1 and 2 have alicyclic structures in the acetal monomer units of the polymer skeleton and the monomer units containing acid groups, so hydrophobicity and steric hindrance are large, so the developing speed slows down, the cross-linking reaction is also difficult to proceed, and the solvent resistance has a tendency to deteriorate. In addition, Comparative Example 3 has high reactivity of acid groups and epoxy groups, so the storage stability of the polymer and the photosensitive resin composition is poor, so the unreacted acid groups are reduced during development, and the developing speed also slows down. And it is believed that compared with the reaction of cationic polymerization of vinyl ether, the cross-linking density of the cross-linking reaction of acid epoxy is low when curing, so the solvent resistance also has a tendency to deteriorate.

[0518] It can be confirmed that the storage stability of Examples 1 to 16 is good compared with Comparative Examples 1 to 3. It is believed that the reason why the storage stability of Examples 11 and 12 is lower than that of other examples is that they are resins having epoxy groups in the side chains and containing a neutralizing amount of triethylamine (basic compound). On the other hand, the reason why the storage stability of the comparative examples is poor is that when the monomers that generate vinyl ethers on the alicyclic skeleton are copolymerized, they are easily detached even during storage, resulting in cross-linking of the vinyl ether groups. On the other hand, in the embodiment with straight or branched chains, the vinyl ether will not be easily detached during storage, the stability is good, and the vinyl ether is detached all at once during low-temperature firing. The detached vinyl ether has high reactivity, so the solvent resistance is also good, which can break the paradoxical relationship between storage stability and solvent resistance.

[0519] Furthermore, since Comparative Example 1 does not contain a basic compound for neutralizing the monomer unit containing an acid group, the removal of the protective group of the vinyl ether is promoted during the storage of the polymer solution, and the vinyl ether group is regenerated to cause crosslinking, so that the storage stability is deteriorated compared with Comparative Example 2. It is believed that Example 6 also has a poorer storage stability than the other examples for the same reason.

[0520] It should be noted that, compared with Comparative Examples 1 to 3, Examples 1 to 3 obtained good results in terms of solvent resistance and storage stability, but it was confirmed that the development speed was slow. This is believed to be due to the fact that the polymer does not have a monomer unit containing an acid group. In addition, it can be confirmed that, compared with Examples 2, 3, 5, 7, 11, and 12, Examples 1, 4, 8, 9, 10, 13, 14, 15, and 16 have a small viscosity change rate and tend to have good storage stability. In this regard, since AEEM, AEEA, PEEA, BEEA, and LEEA have better stability than polymers IEEM and EEEM, carboxylic acids are more preferred than alcohols as protective monomers for vinyl ether groups.

[0521] It is confirmed that compared with Example 4, the developing speed of Example 13 is faster. It is believed that this is due to the effect caused by the glass transition temperature (Tg) of the resin produced by changing from VEEM to VEEA. In addition, Example 15 is compared with Example 14, and similarly Example 14 is compared with Example 13, and the solvent resistance is the same, but it can be confirmed that the viscosity change rate is small and the storage stability is better. It is believed that this is because, when the molecular chain of the carboxylic acid compound forming the acetal monomer unit is longer, it is effective to suppress the detachment of the carboxylic acid compound, and the storage stability is improved. On the other hand, Example 16 is compared with Example 15, and the storage stability is the same, but it can be confirmed that the solvent resistance is deteriorated. It is believed that this is due to, when the molecular chain of the carboxylic acid compound is longer, it is effective to suppress the detachment of the carboxylic acid compound, but when the molecular chain is long, the crosslinking density during thermal curing is reduced, so the solvent resistance is reduced. Therefore, the most preferred carboxylic acid is butyric acid with 4 carbon atoms.

[0522] (Confirmation of the influence of dilution solvent)

[0523] In order to investigate the effect of the dilution solvent on the storage stability of the polymer, the following operation was performed. The storage stability was evaluated using a polymer solution obtained by adding 26 parts of a dilution solvent to 74 parts of the original polymer (B-15) (20 parts of solid content, 54 parts of volatile components). The storage stability evaluation was performed using the increase rate of the weight average molecular weight before and after storage at 40°C for 1 week. The weight average molecular weight of the polymer was measured using the method described above. When the weight average molecular weight of the polymer before storage is set to 100%, the value (%) of the weight average molecular weight after storage is shown in Table 4. The smaller the value of the increase rate of the weight average molecular weight, the better the storage stability of the polymer is evaluated. The dilution solvents used were propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dimethylformamide, diethylene glycol methyl ethyl ether, and 1-butanol. The evaluation results are shown in Table 4.

[0524] [Table 4]

[0525]

[0526] As shown in Table 4, the rate of change of the weight average molecular weight of polymer is small in Embodiments 17, 18, 19 and 20 compared with Embodiment 21. It is thus believed that if alcohol solvents, ether solvents and amide solvents are added to polymers, storage stability is improved. In addition, the rate of change of weight average molecular weight increases in the order of Embodiments 17, 18, 19 and 20. It is thus believed that the storage stability improvement effect increases in the order of ether solvents, alcohol solvents and amide solvents. In addition, it is known that when Embodiment 18 is compared with Embodiment 19, the rate of change of weight average molecular weight is small. It is thus believed that, among alcohol solvents, secondary alcohol solvents are more suitable for improving storage stability than primary alcohol solvents.

[0527] (Confirmation of the influence of dispersant)

[0528] In order to investigate the effect of the addition of dispersants on the storage stability of polymers, the following operation was performed. The storage stability of a polymer solution prepared by adding 10 parts by mass of an amine dispersant Disperbyk-164 (amine value 18 mgKOH / g, solid content 60%, manufactured by BYK-Chemie) relative to 90 parts by mass of polymer (B-5) or polymer (B-11) was evaluated. The storage stability evaluation was performed using the change in acid value before and after storage at 40°C for 1 week. The acid value was determined using the method described above. The smaller the value of the change in acid value, the better the storage stability of the polymer was evaluated. The evaluation results are shown in Table 5. In addition, as a reference, the change in acid value was also evaluated in the same manner for the case of only polymer (B-5) and polymer (B-11).

[0529] [Table 5]

[0530]

[0531] According to Table 5, the acid value change of the resin solutions of Examples 22 to 25 is smaller than that of the resin solutions of Comparative Examples 4 to 5, and the storage stability is excellent. When comparing Examples 22 and 23 containing polymer (B-5) with Examples 24 and 25 containing polymer (B-11), the acid value change of the resin solutions of the examples containing polymer (B-5) is smaller regardless of the presence or absence of an amine-based dispersant. Considering these results, it can be seen that the storage stability is good when the amount of epoxy groups in the resin is small.

[0532] In addition, when comparing Example 22 with Example 23, it can be seen that the acid value change of the resin solution of Example 22 containing an amine dispersant is small and the storage stability is excellent. It is believed that this is due to the suppression of the deprotection of acetal by adding an amine dispersant. On the other hand, when comparing Example 24 with Example 25, it can be seen that the acid value change of the resin solution of Example 24 containing an amine dispersant is large. This tendency is also observed in the comparison between Comparative Example 4 and Comparative Example 5. Based on these results, it is believed that the amine dispersant reduces the storage stability of the resin containing an epoxy group. It is believed that this is due to the promotion of the reaction between the acid group and the epoxy group by the addition of the amine dispersant.

[0533] As described above, it is understood that the polymers of Examples are excellent in storage stability, and when the composition contains an amine-based dispersant, the storage stability is further excellent when the amount of epoxy groups is small.

[0534] Furthermore, when Example 23, Example 25, and Comparative Example 5 are compared, the acid value changes increase in this order, and it is understood that even when no amine-based dispersant is included, the storage stability is more excellent when the amount of epoxy groups is small.

Claims

1. A polymer, characterized in that It has a structural unit (A) represented by the following formula (1), [Chemistry 1] In the formula, X represents a hydrogen atom or a methyl group; L represents a linear or branched divalent organic group; and Y represents an organic group that decomposes by the action of an acid or heat to generate a vinyl ether group in a polymer side chain.

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 represents a linear or branched divalent organic group; R 2 It represents an organic group having 1 to 20 carbon atoms.

3. The polymer according to claim 1 or 2, characterized in that It further has a structural unit (B) containing an acid group.

4. The polymer according to any one of claims 1 to 3, characterized in that It further has a structural unit (C) having a ring structure in the main chain.

5. A polymer solution, characterized in that The method comprises the polymer according to any one of claims 1 to 4 and a polar solvent.

6. A solution for a polymer, characterized in that The method comprises the polymer according to any one of claims 1 to 4 or the polymer solution according to claim 5 , and a basic dispersant and / or a basic compound.

7. A colorant dispersion, characterized in that: The method comprises the polymer solution according to claim 6 and a colorant.

8. A photosensitive resin composition, characterized in that The invention comprises: the polymer according to any one of claims 1 to 4, the polymer solution according to claim 5, the polymer solution according to claim 6 or the colorant dispersion according to claim 7; a polymerizable compound; and a photopolymerization initiator and / or a photoacid generator.

9. The photosensitive resin composition according to claim 8, wherein It is used to form color filters.

10. A solidified product, characterized in that: The photosensitive resin composition according to claim 8 or 9 is cured.

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

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

13. A monomer compound, characterized in that It is represented by the following formula (a), [Chemistry 5] In the formula, R 7 Represents a hydrogen atom or a methyl group; R 8 represents a linear or branched divalent organic group; R 9 It represents an organic group having 1 to 20 carbon atoms, excluding groups containing a (meth)acryloyl group.

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

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