(METH)acrylate polymer, photosensitive resin composition, cured product, and use therefor

Abstract

The purpose of the present invention is to provide: a (meth)acrylate polymer that is capable of suppressing pattern line thickening during exposure, of forming a fine pattern, and of yielding a cured product with excellent solvent resistance, weather resistance, and heat resistance; and a photosensitive resin composition. The present invention relates to a (meth)acrylate polymer including a constituent unit (A) derived from a tertiary carbon-containing (meth)acrylate monomer having a structure in which an oxygen atom adjacent to a (meth)acryloyl group is bonded with a tertiary carbon atom, a constituent unit (B) derived from a monomer having a hydroxyl group, and a constituent unit (C) derived from a (meth)acrylate monomer having ultraviolet absorption ability and / or radical scavenging ability.

Description

(Meth)acrylate polymer, photosensitive resin composition, cured product, and uses thereof

[0001] The present invention relates to a (meth)acrylate polymer, a photosensitive resin composition, a cured product, and uses thereof. More specifically, the present invention relates to a (meth)acrylate polymer, a photosensitive resin composition, a cured product, and uses thereof that can suppress line thickening of a pattern during exposure, enable the formation of a fine pattern, and provide a cured product that is excellent in solvent resistance, weather resistance, and heat resistance.

[0002]

[0003] Various studies have been conducted on the application of (meth)acrylate polymers and photosensitive resin compositions containing the same to various applications, such as optical components such as color filters used in liquid crystal displays and solid-state imaging devices, inks, printing plates, printed wiring boards, semiconductor devices, photoresists, organic insulating films, and organic protective films, as well as electrical and electronic devices, and resins and resin compositions having excellent properties required for each application have been developed.

[0003] In recent years, optical components, electrical and electronic devices, etc. have become smaller, thinner, and more energy-efficient, and this has led to demands for higher performance from the various components used in them. To meet such demands, research has been conducted on (meth)acrylate polymers that can be used as materials for various components, etc., and photosensitive resin compositions containing the same, and various photosensitive resin compositions have been developed to date (for example, Patent Documents 1 to 4).

[0004] Japanese Patent Laid-Open No. 9-3394 Japanese Patent Laid-Open No. 10-231326 Japanese Patent Laid-Open No. 2015-124254 Japanese Patent Laid-Open No. 2017-160460

[0005] However, when a photosensitive resin composition containing a conventional (meth)acrylate polymer is exposed to light to form a pattern, the resulting pattern has problems such as thick lines, difficulty in forming a fine pattern, and poor developability. Furthermore, when a conventional (meth)acrylate polymer is used together with a coloring material, which is a raw material for a color filter, etc., there is a problem that the coloring material elutes from the raw material into a cleaning solvent during the production of the color filter, and therefore further improvement in the solvent resistance of the (meth)acrylate polymer is desired. Furthermore, heat resistance and weather resistance have also become required for various members and parts using the photosensitive resin composition.

[0006] The present invention has been made in view of the above-mentioned current situation, and aims to provide a (meth)acrylate polymer and a photosensitive resin composition that can suppress line thickening of a pattern during exposure, enable the formation of a fine pattern, and give a cured product that is excellent in solvent resistance, weather resistance, and heat resistance.

[0007] The present inventors have conducted extensive research into (meth)acrylate polymers useful for applications such as color filters, and have found that a (meth)acrylate polymer containing a specific tertiary carbon atom-containing (meth)acrylate monomer, a structural unit derived from a monomer having a hydroxyl group, and a structural unit derived from a (meth)acrylate monomer having ultraviolet absorption ability and / or radical scavenging ability can suppress pattern line thickening during exposure, enable the formation of fine patterns, and give cured products that are also excellent in solvent resistance, weather resistance, and heat resistance, thereby completing the present invention.

[0008] That is, the present invention provides the following aspects: <1> A (meth)acrylate polymer characterized by having a structural unit (A) derived from a tertiary carbon-containing (meth)acrylate monomer having a structure in which the oxygen atom adjacent to a (meth)acryloyl group is bonded to a tertiary carbon atom, a structural unit (B) derived from a monomer having a hydroxyl group, and a structural unit (C) derived from a (meth)acrylate monomer having ultraviolet absorbing ability and / or radical scavenging ability. <2> The (meth)acrylate polymer according to <1> above, characterized in that the tertiary carbon-containing (meth)acrylate monomer is a monomer represented by the following general formula (1):

[0009]

[0010] (In the formula, R １ represents a hydrogen atom or a methyl group. ２ and R ３ are the same or different and represent an organic group. ４ , R ５ and R ６ are the same or different and represent a hydrogen atom or an organic group; R ４ , R ５ and R ６At least one of R is a hydrogen atom. ２ , R ３ , R ４ , R ５ and R ６ may be bonded to each other to form a ring.) <3> The (meth)acrylate polymer according to <1> or <2> above, wherein the (meth)acrylate monomer having UV absorption ability and / or radical scavenging ability includes at least one monomer selected from the group consisting of hindered phenol compounds having a (meth)acryloyl group and hindered amine compounds having a (meth)acryloyl group. <4> The (meth)acrylate polymer according to <3> above, wherein the at least one monomer selected from the group consisting of hindered phenol compounds having a (meth)acryloyl group and hindered amine compounds having a (meth)acryloyl group has a maximum absorption peak in the wavelength region of 250 to 400 nm. <5> The (meth)acrylate polymer according to <3> or <4> above, wherein the at least one monomer selected from the group consisting of hindered phenol compounds having a (meth)acryloyl group and hindered amine compounds having a (meth)acryloyl group has a benzotriazole group which may have a substituent. <6> The (meth)acrylate polymer according to any one of the above items <3> to <5>, wherein the at least one monomer selected from the group consisting of hindered phenol compounds having a (meth)acryloyl group and hindered amine compounds having a (meth)acryloyl group is a hindered phenol compound represented by the following general formula (4):

[0011]

[0012] (In the formula, R ７ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. ８represents a group having a (meth)acryloyl group. X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cyano group, or a nitro group. <7> The (meth)acrylate polymer according to any one of <1> to <6> above, further comprising a structural unit (D) derived from a monomer having a homopolymer glass transition temperature of 0°C or lower. <8> A photosensitive resin composition comprising the (meth)acrylate polymer according to any one of <1> to <7> above, a polyfunctional monomer, and a photopolymerization initiator. <9> The photosensitive resin composition according to <8> above, further comprising a colorant. <10> The photosensitive resin composition according to <8> or <9> above, which is a resist for a color filter. <11> The photosensitive resin composition according to <8> above, which is a resist for an insulating film. <12> A cured product obtained by curing the photosensitive resin composition according to any one of <8> to <11> above. <13> A member for a display device, comprising the cured product according to the above item <12>. <14> A member for a semiconductor device, comprising the cured product according to the above item <12>.

[0013] The (meth)acrylate polymer of the present invention can suppress line thickening of a pattern during exposure, can form a fine pattern, and can give a cured product that is excellent in solvent resistance, heat resistance, and weather resistance.

[0014] The present invention will be described in detail below. A combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention. In this specification, "(meth)acrylate" means "acrylate" and "methacrylate." Furthermore, "(meth)acrylic acid" means "acrylic acid" and "methacrylic acid."

[0015] 1. (Meth)acrylate Polymer The (meth)acrylate polymer of the present invention is characterized by having a structural unit (A) derived from a tertiary carbon-containing (meth)acrylate monomer having a structure in which an oxygen atom adjacent to a (meth)acryloyl group is bonded to a tertiary carbon atom, a structural unit (B) derived from a monomer having a hydroxyl group, and a structural unit (C) derived from a (meth)acrylate monomer having ultraviolet absorption ability and / or radical scavenging ability. Because the (meth)acrylate polymer of the present invention has the above structure, it is possible to suppress line thickening of patterns during exposure, form fine patterns, and give cured products that have excellent solvent resistance, heat resistance, and weather resistance.

[0016] The (meth)acrylate polymer of the present invention can suppress line thickening of a pattern during exposure, is capable of forming a fine pattern, and can give a cured product having excellent solvent resistance, heat resistance, and weather resistance. Conventionally, when a coating film of a composition containing a polymer is formed and exposed through a photomask, weak light reaches not only the light-irradiated area (e.g., non-photomask area) but also the vicinity of the light-irradiated area due to light refraction, etc., and a polymer with good curability will cure even in such weakly irradiated areas, resulting in line thickening of the formed pattern, making it difficult to form a fine pattern. In the present invention, the presence of the structural unit (C) suppresses curing in the weakly irradiated areas near the light-irradiated area during exposure, suppressing line thickening of the formed pattern and enabling the formation of a good fine pattern.

[0017] Furthermore, if the glass transition temperature of the polymer is low, the developability is improved, and areas that are weakly irradiated with ultraviolet light are easily washed away during development, allowing for the formation of fine patterns, but the solvent resistance of the cured product is poor. In the present invention, by including the above-mentioned structural unit (C), it is possible to achieve both good pattern formation and solvent resistance. Furthermore, it is also possible to improve the weather resistance and heat resistance of the cured product.

[0018] Furthermore, by including the structural unit (A), upon heating, the portion subsequent to the tertiary carbon in the side chain is eliminated to generate a carboxyl group, which then crosslinks with the hydroxyl group of the structural unit (B), resulting in excellent curability. Furthermore, even when the resin is cured, the thickening of the pattern line due to shrinkage is suppressed, and solvent resistance is also improved.

[0019] The structural units constituting the (meth)acrylate polymer of the present invention will be described below. In the present invention, the term "structural unit" refers to a repeating unit constituting the polymer, which is derived from a monomer or the like used in synthesizing the polymer.

[0020] Structural Unit (A) The (meth)acrylate polymer of the present invention has a structural unit (A) derived from a tertiary carbon-containing (meth)acrylate monomer having a structure in which the oxygen atom adjacent to the (meth)acryloyl group is bonded to a tertiary carbon atom. The structural unit (A) is a structural unit derived from a tertiary carbon-containing (meth)acrylate monomer having a structure in which the oxygen atom adjacent to the (meth)acryloyl group is bonded to a tertiary carbon atom, and refers to a structural unit in which the polymerizable carbon-carbon double bond (C═C) in the tertiary carbon-containing (meth)acrylate monomer becomes a single bond (C-C).

[0021] The structure in which the oxygen atom adjacent to the (meth)acryloyl group is bonded to a tertiary carbon atom is a (meth)acryloyl group (CH ２ ═CHR—CO—, where R represents a hydrogen atom or a methyl group) is bonded to a tertiary carbon atom via one oxygen atom.

[0022] In such a structure, heating cleaves the O-C bond between the oxygen atom adjacent to the (meth)acryloyl group and the tertiary carbon atom adjacent thereto, resulting in decomposition into (meth)acrylic acid and a stable compound formed on the tertiary carbon atom side. For example, when the tertiary carbon-containing (meth)acrylate monomer is CH ２ =CHR-CO-O ＊ -R ａ (R represents a hydrogen atom or a methyl group. R ａ represents a monovalent organic group, O ＊ is a tertiary carbon atom.２ =CHR-COOH and R ａ is decomposed into

[0023] In the structural unit (A), when the polymer is heated, -R ａ The carboxyl group is eliminated, forming a carboxyl group at the end of the side chain. The reaction between the formed carboxyl group and the hydroxyl group of the structural unit (B) described below causes cure shrinkage, suppressing line thickening of the pattern. In addition, the curability of the polymer and the solvent resistance of the cured product are improved.

[0024] As the tertiary carbon-containing (meth)acrylate monomer having a structure in which an oxygen atom adjacent to the (meth)acryloyl group is bonded to a tertiary carbon atom, a monomer represented by the following general formula (1) is preferably mentioned.

[0025]

[0026] (In the formula, R １ represents a hydrogen atom or a methyl group. ２ and R ３ are the same or different and represent an organic group. ４ , R ５ and R ６ are the same or different and represent a hydrogen atom or an organic group; R ４ , R ５ and R ６ At least one of R is a hydrogen atom. ２ , R ３ , R ４ , R ５ and R ６ may be bonded to each other to form a ring.

[0027] In the above general formula (1), R ２ and R ３ Examples of the organic group represented by the formula (I) include a monovalent hydrocarbon group, a monovalent hydrocarbon group and a divalent hydrocarbon group, -O-, -CO-, -COO-, -NH-, -S-, -SO-, and -SO ２ and at least one divalent group selected from the group consisting of -.

[0028] The hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms.

[0029] The hydrocarbon group may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group, a nitro group, and a cyano group. In addition, some of the carbon atoms constituting the hydrocarbon group may be substituted with an oxygen atom, a nitrogen atom, or a sulfur atom.

[0030] Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Examples of the divalent hydrocarbon group include a monovalent hydrocarbon group obtained by removing one hydrogen atom from the monovalent hydrocarbon group to make it divalent.

[0031] Examples of the monovalent aliphatic hydrocarbon group include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a sec-butyl group, a pentyl group, an isopentyl group, a neopentyl group, and a hexyl group; and alkenyl groups such as a vinyl group, an n-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, and a 1-pentenyl group.

[0032] Examples of the monovalent alicyclic hydrocarbon group include monocyclic cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group; polycyclic cycloalkyl groups such as a norbornyl group and an adamantyl group; monocyclic cycloalkenyl groups such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group; and polycyclic cycloalkenyl groups such as a norbornenyl group.

[0033] Examples of the monovalent aromatic hydrocarbon group include aryl groups such as phenyl, naphthyl, and anthryl, and aralkyl groups such as benzyl, phenethyl, and phenylpropyl. Further examples include groups formed of a condensed ring of an aromatic ring and an alicyclic ring.

[0034] Of these, as the hydrocarbon group, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group which may have a substituent is preferred, from the viewpoint of improving solubility and dispersibility, an alkyl group or cycloalkyl group which may have a substituent is more preferred, and an alkyl group is even more preferred.

[0035] R ２ and R３ The number of carbon atoms in the organic group represented by the formula (I) is preferably 1 to 20, more preferably 1 to 5, and even more preferably 1 to 3.

[0036] R ２ and R ３ The organic group represented by the formula (I) is preferably an aliphatic hydrocarbon group, more preferably an alkyl group.

[0037] R ４ , R ５ and R ６ The organic group represented by the formula (I) is the same as the above-mentioned R ２ and R ３ Among them, an aliphatic hydrocarbon group or an alicyclic hydrocarbon group is preferable, an aliphatic hydrocarbon group is more preferable, and an alkyl group is even more preferable. ４ , R ５ and R ６ The organic group represented by the formula (I) preferably has 1 to 20 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms.

[0038] R ２ , R ３ , R ４ , R ５ and R ６ may be bonded to each other to form a ring. The ring may be a monocyclic ring or a polycyclic ring. In terms of improving dispersibility, the ring is preferably a 3- to 10-membered ring, more preferably a 4- to 9-membered ring, and even more preferably a 5- to 8-membered ring.

[0039] R ４ , R ５ and R ６ At least one of R in the general formula (1) is a hydrogen atom. ４ When is a hydrogen atom, when the polymer of the present invention is heated, the compound represented by the following general formula (1a) is eliminated, and a carboxy group is generated at the side chain terminal of the structural unit (A).

[0040] (In the formula, R ２ , R ３ , R ５ and R ６ is the same as above.)

[0041] The compound to be eliminated is —CR in the general formula (1). ２ R ３ (CR ４ R ５ R ６ The number of carbon atoms in the portion represented by (a) is preferably 4 to 12, more preferably 4 to 10, and even more preferably 4 to 7, in view of ease of elimination upon heating. Such elimination causes cure shrinkage, which can effectively suppress line thickening of the formed pattern, allowing for the formation of a fine pattern.

[0042] Preferred examples of the tertiary carbon-containing (meth)acrylate monomer include t-butyl (meth)acrylate, t-amyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, and 2-propenoic acid, 1,1-dimethylpropyl ester.

[0043] The (meth)acrylate polymer may have only one type of the structural unit (A), or may have two or more types.

[0044] In terms of excellent curability, the content of the structural unit (A) in the (meth)acrylate polymer is preferably 1 to 60% by mass, more preferably 10 to 55% by mass, even more preferably 15 to 50% by mass, and even more preferably 20 to 50% by mass, relative to 100% by mass of all structural units.

[0045] Structural Unit (B) is a structural unit derived from a monomer having a hydroxyl group, and refers to a structural unit in which a polymerizable carbon-carbon double bond (C═C) in the monomer having a hydroxyl group becomes a single bond (C-C). The monomer having a hydroxyl group is a monomer having one or more hydroxyl groups in one molecule, and is preferably a (meth)acrylate monomer having a hydroxyl group, and more preferably a hydroxyalkyl (meth)acrylate.

[0046] The number of carbon atoms constituting the hydroxyalkyl group of the hydroxyalkyl (meth)acrylate is not particularly limited, but from the viewpoint of improving curability and developability, it is preferably 1 to 10, more preferably 2 to 9, and even more preferably 3 to 8.

[0047] Specific examples of the hydroxyalkyl (meth)acrylate include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, etc. Of these, 2-hydroxyethyl (meth)acrylate is preferred.

[0048] The (meth)acrylate polymer may have only one type of the structural unit (B), or may have two or more types.

[0049] The content of the structural unit (B) in the (meth)acrylate polymer is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and even more preferably 15 to 40% by mass, relative to 100% by mass of all structural units, in terms of excellent developability and curability.

[0050] Structural Unit (C) The structural unit (C) is a structural unit derived from a (meth)acrylate monomer having ultraviolet absorbing ability and / or radical scavenging ability, and refers to a structural unit in which a polymerizable carbon-carbon double bond (C═C) in the (meth)acrylate monomer having ultraviolet absorbing ability and / or radical scavenging ability has been converted into a single bond (C—C).

[0051] The (meth)acrylate monomer having ultraviolet absorbing ability and / or radical scavenging ability is preferably a compound having a (meth)acrylate group and a group having ultraviolet absorbing ability and / or radical scavenging ability.

[0052] Examples of the group having ultraviolet absorbing ability and / or radical scavenging ability include a hindered phenol group, a hindered amine group, a cyanoacrylate group, and a melamine group.

[0053] The (meth)acrylate monomer having ultraviolet absorbing ability and / or radical scavenging ability is not particularly limited as long as it is a compound having a (meth)acryloyl group and a group having ultraviolet absorbing ability and / or radical scavenging ability, but it preferably contains at least one monomer selected from the group consisting of a hindered phenol compound having a (meth)acryloyl group and a hindered amine compound having a (meth)acryloyl group, in order to further suppress line thickening of the pattern during exposure and to form a finer pattern. A hindered phenol compound having a (meth)acryloyl group is more preferred in order to further improve the heat resistance and weather resistance of the polymer.

[0054] The above-mentioned hindered phenol compound having a (meth)acryloyl group is preferably a compound represented by the following general formula (2).

[0055]

[0056] (In formula (2), X １１ and X １２ are the same or different and represent a hydrogen atom or an organic group. １１ and X １２ At least one of X is an organic group having 4 or more atoms other than hydrogen atoms. １３ , X １４ and X １５ are the same or different and represent a hydrogen atom or a substituent. １３ ~X １５ At least one of the groups is a substituent having a (meth)acryloyl group.

[0057] X １１ and X １２ Examples of the organic group represented by the formula (1) include R ２ and R ３ The organic group represented by X １１ and X １２ At least one of the above is an organic group having 4 or more atoms other than hydrogen atoms. In the organic group, the number of atoms other than hydrogen atoms is preferably 4 to 12, and more preferably 4 to 8.

[0058] As the organic group having four or more atoms other than hydrogen atoms, a hydrocarbon group, an optionally substituted benzophenone group, an optionally substituted benzotriazole group, or an optionally substituted triazine group is preferred. Examples of the substituent include a halogen atom, a hydrocarbon group, an alkoxy group, a cyano group, and a nitro group. Among these, an optionally substituted benzotriazole group is preferred as the organic group having four or more atoms other than hydrogen atoms, since the presence of a bulky group can further improve the heat resistance and weather resistance of the polymer. Furthermore, the benzotriazole skeleton has low solvent solubility, which also contributes to improved chemical resistance.

[0059] X １３ , X １４ and X １５ Examples of the substituent represented by X include the above-mentioned organic groups, as well as halogen atoms, alkoxy groups, cyano groups, and nitro groups. １３ , X １４ , X １５ The organic group represented by the formula (I) preferably has 1 to 15 carbon atoms, more preferably 2 to 15 carbon atoms, and even more preferably 3 to 12 carbon atoms.

[0060] X １３ , X １４ and X １５ The substituent represented by -R is preferably a substituent having a polymerizable functional group at the terminal, more preferably a substituent having a (meth)acryloyl group, ａ１ -O-CO-CR ａ２ =CH ２ (R ａ１ represents a direct bond or an alkylene group having 1 to 12 carbon atoms, R ａ２ represents a hydrogen atom or a methyl group. ) is more preferred. Alternatively, it may be another polymerizable functional group such as an allyl group.

[0061] In the above general formula (2), X １３ , X １４ and X １５ At least one of the groups is a substituent having a polymerizable functional group (preferably a (meth)acryloyl group) at its terminal, and the rest are preferably hydrogen atoms.

[0062] The above-mentioned hindered amine compound having a (meth)acryloyl group is preferably a compound represented by the following general formula (3).

[0063]

[0064] (In formula (3), X ２１ , X ２２ , X ２４ and X ２５ are the same or different and represent an organic group having 1 to 20 carbon atoms. ２３ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. ２６ represents a substituent, at least one of which is a substituent having a (meth)acryloyl group; n represents an integer of 1 to 20; and m represents an integer of 1 to (n+1).

[0065] In the above general formula (3), X ２１ , X ２２ , X ２４ and X ２５ Examples of the organic group represented by X include the same groups as the organic groups described above. Among them, a monovalent hydrocarbon group is preferred, a monovalent aliphatic hydrocarbon group is more preferred, and an alkyl group is even more preferred. ２１ , X ２２ , X ２４ and X ２５ The organic group represented by the formula (I) preferably has 1 to 20 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 carbon atom.

[0066] In the general formula (3), X ２３ Examples of the organic group represented by X include the same groups as the organic groups described above, but are preferably aliphatic hydrocarbon groups and alkoxy groups, and more preferably alkyl groups and alkoxy groups. ２３ The organic group represented by the formula (I) preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms.

[0067] In the above general formula (3), n preferably represents an integer of 1 to 6, and more preferably an integer of 1 to 3.

[0068] In the general formula (3), X ２６The substituent represented by the formula (2) is X １３ ~X １５ The substituents are the same as those represented by the following formula: ２６ When there are a plurality of X, they may be the same or different. ２６ At least one of the groups is a substituent having a (meth)acryloyl group. The substituent having a (meth)acryloyl group is, for example, the above-mentioned X １３ , X １４ and X １５ Examples of the substituent include the same groups as those having a (meth)acryloyl group represented by the following formula:

[0069] m represents an integer of 1 to (n+1), preferably an integer of 1 to 7, and more preferably an integer of 1 to 4.

[0070] The above-mentioned hindered phenol compound having a (meth)acryloyl group and / or hindered amine compound having a (meth)acryloyl group preferably contains a benzotriazole group which may have a substituent. By containing a bulky group such as a benzotriazole group, weather resistance and heat resistance are improved. Among them, a hindered phenol compound represented by the following general formula (4) is more preferred.

[0071]

[0072] (In the formula, R ７ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. ８ represents a group having a (meth)acryloyl group; and X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cyano group, or a nitro group.

[0073] R ７ From the viewpoint of solubility, the hydrocarbon group having 1 to 12 carbon atoms represented by the formula (I) is preferably an aliphatic hydrocarbon group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms.

[0074] R ８ The group having a (meth)acryloyl group represented by the formula (I) is preferably —R ｂ１ -O-CO-CR ｂ２ =CH ２(R ｂ１ represents an alkylene group. ｂ２ represents a hydrogen atom or a methyl group. ｂ１ The alkylene group represented by the formula (I) preferably has 1 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 2 to 8 carbon atoms.

[0075] From the viewpoint of developability, the hydrocarbon group having 1 to 8 carbon atoms represented by X in the above general formula (4) is preferably an aliphatic hydrocarbon group having 1 to 7 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.

[0076] The alkoxy group having 1 to 8 carbon atoms represented by X in the general formula (4) preferably has 1 to 7 carbon atoms, more preferably 1 to 6 carbon atoms, from the viewpoint of developability.

[0077] X in the above general formula (4) is preferably a hydrogen atom or a halogen atom, more preferably a hydrogen atom.

[0078] The above-mentioned hindered phenol compound having a (meth)acryloyl group and hindered amine compound having a (meth)acryloyl group preferably have a maximum absorption peak in the wavelength region of 250 to 400 nm. Having a maximum absorption peak in this range better suppresses line thickening of the pattern during exposure, enabling the formation of a finer pattern. The above-mentioned hindered phenol compound and hindered amine compound more preferably have a maximum absorption peak in the wavelength region of 270 to 400 nm, even more preferably in the wavelength region of 280 to 400 nm. The light absorption characteristics of the above-mentioned compounds can be confirmed by dissolving the compound in a solvent such as N-methylpyrrolidone and measuring the light absorption spectrum in the wavelength region of 250 to 600 nm using a spectrophotometer (e.g., UV3600 (manufactured by Shimadzu Corporation) using a 1 cm quartz cell).

[0079] As the compound having a (meth)acryloyl group and a group having ultraviolet absorbing ability and / or radical scavenging ability, commercially available products may be used, and examples thereof include RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.), Adekastab LA-82 (manufactured by ADEKA Corporation), Adekastab LA-87 (manufactured by ADEKA Corporation), and Sumilizer (registered trademark) GS (manufactured by Sumitomo Chemical Co., Ltd.).

[0080] The (meth)acrylate polymer may have only one type of the structural unit (C), or may have two or more types.

[0081] The content of the structural unit (C) in the (meth)acrylate polymer is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, and even more preferably 3 to 20% by mass, relative to 100% by mass of all structural units, in terms of improving weather resistance and heat resistance.

[0082] Structural Unit (D) The (meth)acrylate polymer preferably further comprises a structural unit (D) derived from a monomer having a homopolymer glass transition temperature of 0°C or lower. By comprising the structural unit (D), the glass transition temperature of the polymer is lowered, thereby improving developability and more effectively suppressing line thickening of the pattern. The glass transition temperature of the homopolymer of the monomer that gives rise to the structural unit (D) is preferably -85°C to 0°C, and more preferably -75°C to -15°C, in terms of favorable developability and patterning.

[0083] The glass transition temperature of the homopolymer is a value obtained by measuring a homopolymer obtained by polymerizing a monomer according to a method in accordance with JIS K7121, and can also be determined by referring to, for example, "POLYMER HANDBOOK THIRD EDITION" (written by J. BRANDRUP and E. H. IMMERGUT, published by John Wiley & Sons, Inc., 1989).

[0084] Examples of the monomers that produce homopolymers with a glass transition temperature of 0° C. or lower include ethyl acrylate (−22° C.), n-butyl acrylate (−56° C.), 2-ethylhexyl acrylate (−70° C.), dodecyl acrylate (−3° C.), etc. Of these, 2-ethylhexyl acrylate and n-butyl acrylate are preferred.

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

[0086] From the viewpoint of achieving both solvent resistance and developability, the content of the structural unit (D) in the (meth)acrylate polymer is preferably 1 to 70% by mass, more preferably 1 to 60% by mass, even more preferably 8 to 55% by mass, still more preferably 10 to 50% by mass, and particularly preferably 10 to 40% by mass, relative to 100% by mass of all structural units.

[0087] Structural Unit (E) The (meth)acrylate polymer may further have a structural unit (E) other than the structural units (A) to (D) described above. Examples of monomers that provide the structural unit (E) to the polymer include monomers that provide a ring structure in the main chain, acid group-containing monomers, (meth)acrylic acid ester monomers, epoxy group-containing monomers, and other copolymerizable monomers. Among these, acid group-containing monomers are preferred from the viewpoint of alkali solubility, and monomers that provide a ring structure in the main chain are preferred from the viewpoint of heat resistance. The (meth)acrylate polymer may have only one type of the structural unit (E), or may have two or more types.

[0088] Examples of the acid group-containing monomer include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, cinnamic acid, and vinylbenzoic acid; unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid; long-chain unsaturated monocarboxylic acids in which the unsaturated group and the carboxyl group are chain-extended, such as β-carboxyethyl (meth)acrylate, mono(2-acryloyloxyethyl) succinate, and mono(2-methacryloyloxyethyl) succinate; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; and phosphate group-containing unsaturated compounds such as Light Ester P-1M (manufactured by Kyoeisha Chemical Co., Ltd.). Among these, from the viewpoints of versatility, availability, and the like, carboxylic acid-based monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, and unsaturated acid anhydrides) are preferred, and from the viewpoints of reactivity, heat resistance, and the like, unsaturated monocarboxylic acids are more preferred, and (meth)acrylic acid is even more preferred.

[0089] Examples of the monomer that imparts a ring structure to the main chain include monomers that impart a ring structure to the main chain, such as N-substituted maleimide monomers described in WO 2023 / 162889, dialkyl-2,2'-(oxydimethylene)diacrylate monomers, and α-(unsaturated alkoxyalkyl)acrylate monomers. Among these, N-substituted maleimide monomers are preferred in terms of good dispersibility of colorants, etc., with N-cyclohexylmaleimide, N-phenylmaleimide, and N-benzylmaleimide being more preferred.

[0090] Examples of the (meth)acrylic acid ester monomer include (meth)acrylic acid ester monomers other than the monomers that give the aforementioned structural units (A), (C), or (D), such as methyl (meth)acrylate, ethyl methacrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl methacrylate, n-amyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and N,N-dimethylaminoethyl (meth)acrylate.

[0091] Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, vinylbenzyl glycidyl ether, allyl glycidyl ether, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and vinylcyclohexene oxide.

[0092] Examples of the other copolymerizable monomers include the following compounds: (meth)acrylamides such as N,N-dimethyl(meth)acrylamide and N-methylol(meth)acrylamide; macromonomers having a (meth)acryloyl group at one end of the polymer molecular chain such as polystyrene, polymethyl(meth)acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, and polycaprolactam; conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; styrene aromatic vinyls such as vinyl ether, vinyl toluene, α-methylstyrene, and methoxystyrene; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, methoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, and 2-hydroxyethyl vinyl ether; N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, and N-vinylimidazole; unsaturated isocyanates such as isocyanatoethyl (meth)acrylate and allyl isocyanate; and the like.

[0093] The content of the structural unit (E) in the (meth)acrylate polymer is preferably 0 to 60% by mass, more preferably 0.5 to 50% by mass, and even more preferably 1 to 40% by mass.

[0094] When the (meth)acrylate polymer has the structural unit (e1) derived from the acid group-containing monomer, the content of the structural unit (e1) in the polymer is preferably 1 to 50% by mass, more preferably 5 to 30% by mass, and even more preferably 10 to 20% by mass, relative to 100% by mass of all structural units, from the viewpoint of developability.

[0095] When the (meth)acrylate polymer has a structural unit (e2) derived from a monomer that imparts a ring structure to the main chain, the content of the structural unit (e2) in the polymer is preferably 1 to 30% by mass, more preferably 2 to 30% by mass, even more preferably 5 to 25% by mass, and even more preferably 5 to 20% by mass, relative to 100% by mass of all structural units, in terms of improving heat resistance.

[0096] The acid value of the (meth)acrylate polymer is preferably 20 to 200 mgKOH / g, more preferably 30 to 180 mgKOH / g, and even more preferably 50 to 150 mgKOH / g, in terms of good developability. The acid value can be determined by neutralization titration using a KOH solution, specifically, by the method described in the Examples below.

[0097] The hydroxyl group equivalent of the (meth)acrylate polymer is preferably 150 to 10,000 g / equivalent, more preferably 200 to 750 g / equivalent, and even more preferably 250 to 700 g / equivalent, in view of good developability and solvent resistance. The hydroxyl group equivalent is the hydroxyl group equivalent of the hydroxyl group derived from the structural unit (B), and can be determined by dividing the mass (g) of the polymer solid content by the amount of hydroxyl groups (mol) of the polymer.

[0098] In view of excellent developability and solvent resistance, the weight average molecular weight of the (meth)acrylate polymer is preferably 2000 to 50000, more preferably 4000 to 50000, and even more preferably 5000 to 30000. The weight average molecular weight can be determined by gel permeation chromatography (GPC), specifically, by the method described in the examples below.

[0099] The glass transition temperature (Tg) of the (meth)acrylate polymer is preferably −20° C. or higher, more preferably −10 to 150° C., even more preferably −5 to 130° C., still more preferably 5 to 130° C., and particularly preferably 10 to 130° C., in order to enable good formation of a fine pattern and improve solvent resistance and heat resistance. The glass transition temperature can be determined by the method described in the examples below.

[0100] The (meth)acrylate polymer may have a polymerizable double bond in the side chain, but preferably does not. The polymerizable double bond refers to a double bond having radical polymerizability. When the (meth)acrylate polymer has a polymerizable double bond in the side chain, the curability is improved and the solvent resistance is enhanced. However, the improved curability makes it easier for the curing reaction to proceed even in the vicinity of the light irradiation area during exposure, which may result in insufficient suppression of line thickening of the formed pattern or reduced weather resistance. The polymerizable double bond equivalent of the polymer is preferably 300 g / equivalent or more, more preferably 1000 g / equivalent or more, and even more preferably 1500 g / equivalent or more. The upper limit is, for example, 5000 g / equivalent, which means that the polymer has substantially no polymerizable double bonds. That is, the polymerizable double bond equivalent of the polymer is preferably 300 to 5000 g / equivalent, more preferably 1000 to 5000 g / equivalent, and even more preferably 1500 to 5000 g / equivalent.

[0101] The polymerizable double bond equivalent is the mass of the solid content of the polymer solution per 1 mol of polymerizable double bonds in the (meth)acrylate polymer. The mass of the solid content of the polymer solution is the mass of the monomer components constituting the (meth)acrylate polymer. In this specification, the polymerizable double bond equivalent can be determined by dividing the mass (g) of the solid content of the polymer solution by the amount (mol) of polymerizable double bonds in the polymer. Alternatively, it may be calculated by measuring the number of ethylenic double bonds contained per 1 g of the polymer in accordance with the iodine value test method described in JIS K 0070:1992.

[0102] <Method for Producing (Meth)acrylate Polymer> The method for producing the (meth)acrylate polymer of the present invention is not particularly limited, as long as it is a method that can give a polymer having at least the above-mentioned structural units (A) to (C). Examples include a method of polymerizing a monomer component that includes a monomer that gives the above-mentioned structural units (A) to (C) and a monomer that gives any other structural unit (D) or (E), and a method of polymerizing a monomer component to give a base polymer, and then subjecting another compound to an addition reaction with a group in the base polymer to give a resin having predetermined structural units.

[0103] The method for polymerizing the monomer components is not particularly limited, and commonly used techniques such as bulk polymerization, solution polymerization, and emulsion polymerization can be used. Among these, solution polymerization is preferred because it is industrially advantageous and allows for easy structural adjustment such as molecular weight. Furthermore, polymerization mechanisms based on radical polymerization, anionic polymerization, cationic polymerization, and coordination polymerization can be used for the polymerization mechanism of the monomer components, but polymerization methods based on radical polymerization mechanisms are preferred because of their industrial advantages. The molecular weight of the polymer obtained by polymerizing the monomer components can be controlled by adjusting the amount and type of polymerization initiator, the polymerization temperature, the type and amount of chain transfer agent, and the like.

[0104] The polymerization initiator, chain transfer agent, and solvent used in the polymerization are not particularly limited and may be appropriately selected from known materials. Examples include polymerization initiators such as peroxides and azo compounds, such as t-butylperoxy-2-ethylhexanoate, as described in JP 2015-157909 A, and chain transfer agents such as alkyl mercaptans, mercaptocarboxylic acids (e.g., β-mercaptopropionic acid), and mercaptocarboxylic acid esters. Specific examples of solvents include propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether. The amounts of these used can be appropriately determined. Furthermore, commonly used additives, such as catalysts and polymerization inhibitors, may also be used in the polymerization.

[0105] Regarding the polymerization conditions, the polymerization temperature may be appropriately set depending on the type and amount of the monomer used, the type and amount of the polymerization initiator, etc., and is, for example, preferably 50 to 150° C., more preferably 70 to 120° C. Similarly, the polymerization time can also be appropriately set and is, for example, preferably 1 to 5 hours, more preferably 2 to 4 hours.

[0106] When the (meth)acrylate polymer has a polymerizable double bond in the side chain, it can be produced by a known method, such as a method in which a monomer component that gives the predetermined structural units (A) to (C) and a monomer component containing an acid group-containing monomer are polymerized to obtain a base polymer having an acid group, and then a monomer having an epoxy group and a polymerizable double bond (for example, the above-mentioned epoxy group-containing monomer) is reacted with the obtained base polymer to introduce the polymerizable double bond into the side chain of the base polymer.

[0107] The method for producing the (meth)acrylate polymer may include other steps in addition to the polymerization reaction step. Examples of such steps include an aging step, a neutralization step, a deactivation step of a polymerization initiator or a chain transfer agent, a dilution step, a drying step, a concentration step, and a purification step. These steps can be carried out by known methods.

[0108] 2. Photosensitive Resin Composition The (meth)acrylate polymer of the present invention can be combined with other components to form a curable resin composition. Among these, a photosensitive resin composition containing the (meth)acrylate polymer, a polyfunctional monomer, and a photopolymerization initiator is preferred. Such a photosensitive resin composition containing the (meth)acrylate polymer, a polyfunctional monomer, and a photopolymerization initiator also constitutes the present invention. Since the photosensitive resin composition contains the (meth)acrylate polymer, it is possible to suppress line thickening of the pattern during exposure, form a fine pattern, and provide a cured product with excellent solvent resistance, heat resistance, and weather resistance.

[0109] The content of the (meth)acrylate polymer in the photosensitive resin composition is preferably 5% by mass or more, and preferably 70% by mass or less, relative to 100% by mass of the total solid content of the photosensitive resin composition. By being in such a range, the effects of the present invention can be more significantly achieved. The content is more preferably 10 to 65% by mass, even more preferably 10 to 50% by mass, particularly preferably 10 to 40% by mass, even more preferably 10 to 35% by mass, and most preferably 15 to 35% by mass, relative to 100% by mass of the total solid content of the photosensitive resin composition. The term "total solid content" refers to the total amount of components that form the cured product (excluding solvents and the like that volatilize during the formation of the cured product).

[0110] (Polyfunctional Monomer) Examples of the polyfunctional monomer include bifunctional (meth)acrylate compounds such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and polyethylene glycol di(meth)acrylate; trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and ethylene Examples of the polyfunctional compounds among the polymerizable compounds described in JP-A No. 2023-49678 include trifunctional or higher polyfunctional (meth)acrylate compounds such as oxide-added trimethylolpropane tri(meth)acrylate; polyfunctional vinyl ethers such as ethylene glycol divinyl ether, diethylene glycol divinyl ether, and polyethylene glycol divinyl ether; vinyl ether group-containing (meth)acrylic acid esters such as 2-vinyloxyethyl (meth)acrylate; and polyfunctional allyl ethers such as ethylene glycol diallyl ether.

[0111] In order to further suppress cure shrinkage, the polyfunctional monomer preferably has a functionality of 3 or more, more preferably 4 or more, and even more preferably 5 or more. In order to further suppress cure shrinkage, the functionality is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less. Only one type of polyfunctional monomer may be used, or two or more types may be used.

[0112] The content of the polyfunctional monomer is not particularly limited as long as the effects of the present invention are exhibited, and may be set appropriately. However, from the viewpoint of achieving better developability, curability, and adhesion, it is preferably 2% by mass or more and suitably 85% by mass or less, relative to 100% by mass of the total solids content of the photosensitive resin composition. The lower limit is more preferably 5% by mass or more, even more preferably 10% by mass or more, and particularly preferably 15% by mass or more. The upper limit is more preferably 75% by mass or less, even more preferably 60% by mass or less, particularly preferably 50% by mass or less, and most preferably 40% by mass or less. That is, the content of the polyfunctional monomer is more preferably 5 to 75% by mass, even more preferably 10 to 60% by mass, particularly preferably 15 to 50% by mass, and most preferably 15 to 40% by mass, relative to 100% by mass of the total solids content of the photosensitive resin composition.

[0113] (Photopolymerization initiator) The photopolymerization initiator is preferably a radically polymerizable photopolymerization initiator. Examples of the photopolymerization initiator include aminoketone compounds such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one ("IRGACURE907", manufactured by BASF Corporation); benzyl ketal compounds such as 2,2-dimethoxy-1,2-diphenylethan-1-one ("IRGACURE651", manufactured by BASF Corporation); hydroketone compounds such as 1-hydroxy-cyclohexyl-phenyl-ketone ("IRGACURE184", manufactured by BASF Corporation); 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime) ("OXE01", manufactured by BASF Corporation); Examples of the photopolymerization initiator include oxime ester compounds such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime) ("OXE02", manufactured by BASF), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime) ("OXE02", manufactured by BASF), alkylphenone compounds, benzophenone compounds, benzoin compounds, thioxanthone compounds, halomethylated triazine compounds, halomethylated oxadiazole compounds, biimidazole compounds, titanocene compounds, benzoic acid ester compounds, acridine compounds, and phosphine oxide compounds, as described in JP-A 2023-49678. The photopolymerization initiators may be used alone or in combination of two or more.

[0114] The content of the photopolymerization initiator is not particularly limited as long as the effects of the present invention are exhibited, and may be set appropriately. However, in order to obtain a cured film with excellent adhesion, the content is preferably 0.5% by mass or more relative to 100% by mass of the total solid content of the photosensitive resin composition. It is more preferably 1% by mass or more, and even more preferably 1.5% by mass or more. Furthermore, in consideration of the balance between the effects of decomposition products of the photopolymerization initiator and economic efficiency, the content is preferably 30% by mass or less. It is more preferably 20% by mass or less, and even more preferably 10% by mass or less. That is, the content of the photopolymerization initiator is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, and even more preferably 1.5 to 10% by mass relative to 100% by mass of the total solid content of the photosensitive resin composition.

[0115] (Other Components) The photosensitive resin composition of the present invention may further contain other components as needed. Examples of such other components include solvents; colorants; thermal radical polymerization initiators; photoacid generators; photobase generators; thermal acid generators; dispersants; heat resistance improvers; leveling agents; development aids; inorganic fine particles such as metal oxide particles; silane-based, aluminum-based, and titanium-based coupling agents; fillers, thermosetting resins such as phenolic resins and polyvinylphenols; curing aids such as polyfunctional thiol compounds; plasticizers; polymerization inhibitors; UV absorbers; antioxidants; matting agents; antifoaming agents; antistatic agents; slip agents; surface modifiers; thixotropic agents; thixotropic aids; quinone diazide compounds; polyhydric phenol compounds; and cationically polymerizable compounds. These may be used alone or in combination of two or more. These other components may be selected from known compounds as appropriate, and the amounts used may be appropriately determined.

[0116] When the photosensitive resin composition is used as a resist for a color filter, for example, it preferably contains a color material. The color material is not particularly limited, and color materials (colorants) such as known pigments and dyes used for color filters can be used.

[0117] The content of the coloring material is preferably 2 to 80% by mass, more preferably 5 to 70% by mass, and even more preferably 10 to 60% by mass, relative to 100% by mass of the total solid content of the photosensitive resin composition.

[0118] Furthermore, when the photosensitive resin composition is used as, for example, a resist for an insulating film, it preferably contains a cationically polymerizable compound. Examples of the cationically polymerizable compound include known epoxy resins, oxetane compounds, oxazolion compounds, etc., and epoxy resins are preferred because of their good reactivity in the step of heating the light-irradiated coating film described below.

[0119] The epoxy resin is not particularly limited, and any known epoxy resin having two or more epoxy groups in one molecule can be used. Specific examples thereof include bisphenol-type epoxy resins; biphenyl-type epoxy resins; fluorene-type epoxy resins; alicyclic epoxy resins; polyfunctional glycidylamine resins such as tetraglycidylaminodiphenylmethane; polyfunctional glycidyl ether resins such as tetraphenylglycidyl ether ethane; phenol novolac-type epoxy resins and cresol novolac-type epoxy resins; reaction products of epichlorohydrin with a polyphenol compound obtained by a condensation reaction of a phenolic compound such as phenol, o-cresol, m-cresol, or naphthol with an aromatic aldehyde having a phenolic hydroxyl group; reaction products of epichlorohydrin with a polyphenol compound obtained by an addition reaction of a phenolic compound with a diolefin compound such as divinylbenzene or dicyclopentadiene; products obtained by epoxidizing a ring-opening polymer of 4-vinylcyclohexene-1-oxide with a peracid; and epoxy resins having a heterocycle such as triglycidyl isocyanurate. Furthermore, chain-extended epoxy resins obtained by combining two or more molecules of these epoxy resins through a reaction with a chain extender such as a polybasic acid, a polyphenol compound, a polyfunctional amino compound, or a polyvalent thiol can also be used.

[0120] The epoxy equivalent of the epoxy resin is preferably 90 to 1000 g / equivalent, more preferably 120 to 500 g / equivalent, and even more preferably 150 to 300 g / equivalent, in view of good reactivity. The epoxy equivalent can be determined by dividing the resin solid content by the number of moles of epoxy groups contained in the resin. The epoxy equivalent can also be determined by a method in accordance with JIS K7236:2001.

[0121] The content of the cationically polymerizable compound is preferably 1 to 70% by mass, more preferably 3 to 60% by mass, and even more preferably 5 to 50% by mass, relative to 100% by mass of the total solid content of the photosensitive resin composition.

[0122] When the photosensitive resin composition is used as a resist for an insulating film, it may contain inorganic fine particles. By not using inorganic fine particles, finer patterns can be formed, and by using inorganic fine particles, resistance to thermal cycles is improved.

[0123] Examples of inorganic fine particles include silica fine particles, glass filler, spherical alumina, crushed alumina, oxides such as magnesium oxide, beryllium oxide, titanium oxide, zirconia, and zinc oxide, nitrides such as boron nitride, silicon nitride, and aluminum nitride, carbides such as silicon carbide, hydroxides such as aluminum hydroxide and magnesium hydroxide, metals and alloys such as copper, silver, iron, aluminum, nickel, and titanium, carbon-based fillers such as diamond and carbon, calcium carbonate, barium sulfate, talc, and mica, which may be surface-treated with a coupling agent, etc. Among these, silica fine particles are preferred because they provide excellent physical properties of the cured product, such as thermal cycle resistance.

[0124] The silica fine particles are not particularly limited, and examples thereof include the SFP series and UFP series (UFP-30, UFP-40, SFP-20M, SFP-30M, SFP-130MC, SFP-120MC, SFP-120MC, SFP-30MHE, UFP-30HH) manufactured by Denka Co., Ltd., and the FB series (FB-5D, FB-8S, FB-15D, FB-20D, FB-40R) manufactured by Nissan Chemical Co., Ltd.; ST-NXS, ST-CXS, ST-S, ST-OS, ST-NS, ST-30, ST-O, ST-N, ST-C, ST-AK, ST-50-T, ST-O-40, ST-CM, ST-30L, ST-OL, ST-AK-L , ST-YL, ST-OYL, ST-AK-YL, ST-ZL, MP-1040, MP-2040, MP-4540M, ST-UP, ST-OUP, ST-PS-S, ST-PS-SO, ST-PS-M, ST-PS-MO) , Organosilica sol series (methanol silica sol, MA-ST-M, MA-ST-L, IPA-ST, IPA-ST-L, IPAST-ZL, IPA-ST-UP, EG-ST, NPC-ST-30, PGM-ST, DMAC-ST, MEK-ST-40, MEK-ST-L, MEK-ST-ZL, MEK-ST-UP, MIBK-ST-L, CHO-ST-M, EAC-ST, PMA-ST, TOL-ST, MEK-AC-2140Z, M MEK-AC-4130Y, MEK-AC5140Z, PMG-AC2140Y, PGM-AC-4130Y, MIBK-AC-2140Z, MIBK-SD-L, MEK-EC-2130Y, EP-M2130Y); SO-C type (SO-C1, SO-C2, SO-C4, SO-C5, SO-C6) and SO-E type (SO-E1, SO-E2, SO-E3, SO-E4, SO-E5, SO-E6) manufactured by Admatechs Co., Ltd.

[0125] The average particle size of the inorganic fine particles is preferably 1 to 1500 nm, more preferably 3 to 800 nm, and even more preferably 5 to 100 nm, in order to provide good mechanical and optical properties to the cured product. The average particle size can be measured by magnifying and observing the inorganic fine particles with a transmission electron microscope (TEM), a field emission transmission electron microscope (FE-TEM), a field emission scanning electron microscope (FE-SEM), or the like, randomly selecting 100 particles, measuring their lengths in the major axis direction, and calculating the arithmetic median.

[0126] The content of the inorganic fine particles is preferably 2 to 80% by mass, more preferably 5 to 70% by mass, and even more preferably 10 to 60% by mass, relative to 100% by mass of the total solid content of the photosensitive resin composition.

[0127] <Preparation of Photosensitive Resin Composition> The method for preparing the photosensitive resin composition is not particularly limited and may be a known method, for example, a method in which the above-mentioned components are mixed and dispersed using various mixers or dispersers. The mixing and dispersion step is not particularly limited and may be performed by a known method. In addition, other steps that are usually performed may be further included. When the photosensitive resin composition contains a colorant, it is preferable to prepare it through a known colorant dispersion treatment step.

[0128] 3. Cured Product The method for obtaining a cured product using the photosensitive resin composition of the present invention is not particularly limited, and any known method may be used. For example, the photosensitive resin composition may be applied to a substrate or molded, and then cured by heating, irradiating with active energy rays such as ultraviolet rays, or a combination of these to obtain a cured product. Such a cured product obtained by curing the photosensitive resin composition also constitutes one aspect of the present invention.

[0129] A preferred example of a method for producing the cured product includes a step (a) of applying a photosensitive resin composition onto a substrate to form a coating film, a step (b) of irradiating the formed coating film with light, and a step (c) of heating the irradiated coating film.

[0130] The substrate is not particularly limited and may be appropriately selected depending on the purpose and application. Examples include substrates made of various materials such as glass plates and plastic plates.

[0131] In the step (a), the method for applying the photosensitive resin composition to form a coating film is not particularly limited, and can be any known method such as spin coating, slit coating, roll coating, casting coating, or dip coating.

[0132] After applying the photosensitive resin composition to a substrate, it is preferable to dry the applied product to form a coating film. The drying can be carried out by a known method, for example, using a hot plate, an IR oven, a convection oven, etc. The drying conditions are appropriately selected depending on the boiling point of the solvent components contained, the type of curable component, the film thickness, the performance of the dryer, etc., but it is usually preferable to perform the drying at a temperature of 50 to 160°C for 10 to 300 seconds.

[0133] In the above step (b), the method for irradiating the formed coating film with light is not particularly limited, and can be carried out by any known method. Examples of the light source of the actinic ray used for light irradiation include lamp light sources such as a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, and a fluorescent lamp, and laser light sources such as an argon ion laser, a YAG laser, an excimer laser, a nitrogen laser, a helium cadmium laser, and a semiconductor laser.

[0134] When the coating film is irradiated with light, the light irradiation may be carried out through a photomask. As the photomask, a mask having a light-shielding portion formed according to the desired pattern may be used. The photosensitive resin composition of the present invention can suppress line thickening of the formed pattern and can form a fine pattern well.

[0135] The method may include a step of performing light irradiation through a photomask, followed by development treatment in a developer to remove unirradiated portions. The light irradiation hardens the irradiated portions, making the cured product insoluble or poorly soluble in the developer. On the other hand, the unirradiated portions dissolve in the developer and are removed by development treatment, thereby obtaining a patterned cured film. The development treatment can usually be performed at a development temperature of 10 to 50°C by a method such as immersion development, spray development, brush development, or ultrasonic development.

[0136] The developer is not particularly limited as long as it dissolves the photosensitive resin composition, but typically an organic solvent or an alkaline aqueous solution is used, or a mixture thereof may be used. When an alkaline aqueous solution is used as the developer, it is preferable to wash with water after development. Examples of organic solvents and alkaline aqueous solutions include those described in JP 2015-157909 A.

[0137] In the above step (c), the coating film is preferably heated at 60 to 300°C, more preferably 70 to 250°C, and even more preferably 80 to 230°C.

[0138] The heating time is not particularly limited, and is preferably 5 to 60 minutes, for example. The heating method is also not particularly limited, and can be performed using known heating equipment such as a hot plate, a convection oven, or a high-frequency heater.

[0139] When the cured product obtained by the above-described production method is a cured film, the film thickness may be appropriately set depending on the application of the cured film. In order to fully meet the demand for low profile components, display devices, and the like using the cured film, the film thickness is preferably 0.1 to 100 μm, more preferably 0.5 to 10 μm, and even more preferably 0.5 to 8 μm.

[0140] The (meth)acrylate polymer and photosensitive resin composition of the present invention can suppress line thickening of a pattern during exposure, enable the formation of a fine pattern, and provide a cured product with excellent solvent resistance. They also have excellent heat resistance and weather resistance. Therefore, they can be suitably used in applications requiring good pattern formation, solvent resistance, heat resistance, or weather resistance.

[0141] Specifically, the (meth)acrylate polymer and photosensitive resin composition of the present invention can be suitably used for various optical components and components of electrical and electronic devices, such as color filters, black matrices, photospacers, black column spacers, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, and insulating films used in liquid crystal, organic EL, quantum dot, and micro LED liquid crystal displays, solid-state imaging devices, and touch panel display devices. Among these, the (meth)acrylate polymer and photosensitive resin composition are preferably used for resists, and more preferably for color filters or insulating films. The photosensitive resin composition is preferably a color filter resist or an insulating film resist.

[0142] 5. Display Device Members The present invention also provides a display device member having a cured product obtained by curing the photosensitive resin composition of the present invention. Examples of the display device include a liquid crystal display device, a solid-state imaging device, and a touch panel display device.

[0143] When the cured product (cured film) is used as a member for a display device, the member may be a film-like single-layer or multi-layer member constituted from the cured film, or may be a member in which another layer is further combined with the single-layer or multi-layer member, or may be a member containing the cured film in its configuration.

[0144] 6. Semiconductor Device Member A semiconductor device member having a cured product obtained by curing the photosensitive resin composition of the present invention also constitutes one aspect of the present invention. Examples of the semiconductor device member include insulating films for semiconductor devices. Examples of the insulating films for semiconductor devices include interlayer insulating films for rewiring.

[0145] When the cured product (insulating film) is used as a semiconductor device member, it can be applied to a method for manufacturing a semiconductor device that uses a semiconductor element as a substrate and includes the above-mentioned method for manufacturing a cured film as part of the process. That is, the cured film formed by the above-mentioned manufacturing method can be formed as a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip-chip device, or a protective film for a semiconductor device having a bump structure, and can be manufactured by combining it with a known method for manufacturing a semiconductor device.

[0146] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

[0147] In the present examples, various physical properties were measured by the following methods. <Weight average molecular weight> The weight average molecular weight (Mw) was determined by gel permeation chromatography (GPC) using polystyrene as a standard substance. The measurement conditions were as follows: Apparatus: Gel permeation chromatography apparatus HLC-8320GPC (manufactured by Tosoh Corporation) Column: TSKgel Super HZM-M (manufactured by Tosoh Corporation) Detector: RI detector for liquid chromatogram Measurement temperature: 40°C Solvent: THF (tetrahydrofuran) Sample concentration: 0.05 g / 10 cc Sample flow rate: 0.6 ml / min

[0148] <Acid Value> 3 g of the polymer solution was weighed out and dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and titrated using a 0.1 N KOH aqueous solution as the titrant. The titration was performed using an automatic titrator (product name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value per 1 g of solids (mg KOH / g) was determined from the acid value of the polymer solution and the solids content of the polymer solution. The solids content of the polymer solution was determined as follows. That is, approximately 1 g of the polymer solution was weighed into an aluminum cup, and approximately 3 g of acetone was added and dissolved, followed by air drying at room temperature. The solution was then dried under vacuum at 160°C for 1.5 hours using a vacuum dryer (product name: VOS-301SD, manufactured by EYELA), and then allowed to cool in a desiccator, and its mass was measured. The solids content (% by mass) of the polymer solution was calculated from the mass loss.

[0149] <Polymerizable double bond equivalent> The polymerizable double bond equivalent was determined by dividing the mass (g) of the polymer solid content by the amount (mol) of polymerizable double bonds in the polymer.

[0150] <Glass Transition Temperature (Tg)> In this example, the glass transition temperature (Tg) of each polymer was calculated. The calculation method was in accordance with the following FOX formula: 1 / (Tg + 273) = Σ[wi / (Tgi + 273)] (where wi is the mass fraction of monomer i, and Tgi is the glass transition temperature (°C) of a homopolymer of monomer i.) For the Tg of the homopolymer of the monomer used in the FOX formula, a value (if multiple glass transition temperatures are listed, the lowest value) described in, for example, "POLYMER HANDBOOK THIRD EDITION" (by J. BRANDRUP and E.H. IMMERGUT, 1989, published by John Wiley & Sons, Inc., pp. VI / 209-VI / 277) was used. For monomers not listed in the "POLYMER HANDBOOK THIRD EDITION," values ​​calculated by computer using commercially available glass transition temperature calculation software (for example, "MATERIALS STUDIO" manufactured by Accelrys Software Inc., version: 4.0.0.0, module: Synthia, conditions: calculation with a weight average molecular weight of 100,000) were used. Specifically, the polymer Tg was calculated using the following formula: 1 / (Tg+273)=w1 / (Tg1+273)+w2 / (Tg2+273)+...Tg: polymer Tg (w1, w2,...: weight fraction of monomers 1, 2,... in the polymer; Tg1, Tg2,...: homopolymer Tg of monomers 1, 2,... constituting the polymer).

[0151] <Heat Resistance> A polymer solution was prepared to a solid content of 20%, spin-coated onto a 5 cm square glass substrate, dried at 100°C for 3 minutes, and then heat-treated at 230°C for 6 hours (coating film thickness: 4 μm). After cooling to room temperature, the yellow index (YI) value of the heat-treated coating film was measured using a spectrophotometer ("CM-3700A", manufactured by Konica Minolta, Inc.).

[0152] <Weather Resistance> A polymer composition was prepared by adding 25 parts of a polyfunctional monomer (dipentaerythritol hexaacrylate) and 5 parts of a photopolymerization initiator (Irgacure 907, manufactured by BASF Japan) to 70 parts (solid content) of the polymer solution. The composition was uniformly coated onto a 5 cm square glass substrate (soda-lime glass AS-2K, manufactured by Toshin Riko Co., Ltd.) using a spin coater (1H-D7, manufactured by Mikasa Co., Ltd.). The coated plate was dried at 100°C for 3 minutes to obtain a laminate. After removing the polymer composition adhering to the edge of the glass substrate, the obtained laminate was exposed to 100 mJ using a high-pressure mercury lamp. The laminate was subjected to a heat treatment at 230°C for 30 minutes using a Perfect Oven incubator (manufactured by Espec Corporation) and then cooled to room temperature to obtain a laminate with a coating film thickness of 2 μm. The obtained laminate was used as a measurement sample and a weather resistance test was performed using the following equipment, conditions, and evaluation method. Equipment: Xenon Weather Meter X25 (manufactured by Suga Test Instruments Co., Ltd.) Conditions: Temperature inside the chamber: 50°C, humidity inside the chamber: 17%, irradiance: 0.45 kW / m ２ , 200 hours Evaluation method: The film thickness reduction rate (%) before and after the test was measured using a laser microscope VK-X3000 manufactured by KEYENCE Corp. The smaller the value, the better the weather resistance was evaluated to be.

[0153] <Development Rate> The photosensitive resin composition was applied to a 10 cm square glass substrate using a spin coater and dried in an oven at 90° C. for 3 minutes. After drying, a photomask having a line and space of 1 to 100 μm was placed 100 μm away from the coating film, and the composition was developed at 100 mJ / cm using a UV aligner (trade name "TME-150RNS", manufactured by TOPCON Corporation) equipped with a 2.0 kW ultra-high pressure mercury lamp. ２ The coating film (film thickness: 2 μm) was then irradiated with ultraviolet light at an intensity of 100 μm (equivalent to 365 nm illuminance). After ultraviolet irradiation, a 0.05% by mass aqueous solution of potassium hydroxide was sprayed onto the coating film (film thickness: 2 μm) using a spin developer to dissolve and remove the unexposed areas, and the remaining exposed areas were developed by rinsing with pure water for 10 seconds to form a line and space pattern. The time required to dissolve and remove the unexposed areas was measured and evaluated as the development time (seconds).

[0154] <Pattern diameter> The diameter of the pattern formed on the glass substrate obtained in the development rate test using a mask with a diameter of 20 μm was measured using a surface roughness meter (manufactured by Ryoka Systems Co., Ltd., product name: VertScan 2.0). It was determined that the closer the obtained pattern diameter was to 20 μm, the better the pattern diameter was.

[0155] <Minimum Adhesion Pattern> A line and space pattern was formed in the same manner as in the development rate test, except that the time for spraying the potassium hydroxide aqueous solution was changed to twice the development time obtained in the development rate test. The size of the smallest pattern that could be formed was observed with an optical microscope and taken as the minimum adhesion pattern. The minimum adhesion pattern was judged to be better the closer it was to 1.

[0156] <Solvent Resistance> A photosensitive resin composition was spin-coated onto a 5 cm square glass substrate, dried at 100°C for 3 minutes, exposed to 200 mJ using a high-pressure mercury lamp, and heat-treated at 150°C for 40 minutes to obtain a cured film with a film thickness of 2 μm. The cured film was then immersed in 20 g of 1-methyl-2-pyrrolidone (NMP) at 40°C for 10 minutes and then removed. The absorbance of the immersion liquid (NMP) after removing the cured film was measured using a UV3600 spectrophotometer (manufactured by Shimadzu Corporation). A higher absorbance value indicates that more colorant was eluted into the immersion liquid, and the photosensitive resin composition was evaluated as having lower solvent resistance.

[0157] <Thermal Cycle Test (TC)> The substrates used in the evaluation of the pattern diameter above were subjected to a heat treatment at 200°C for 1 hour, and then subjected to a thermal cycle test using a thermal shock device (TSA-71S, manufactured by Espec Corporation), with one cycle consisting of 30 minutes at -40°C and 30 minutes at 85°C. The appearance was visually observed every 50 cycles and evaluated according to the following criteria: ◎: No cracks were observed even after 150 cycles. ○: Cracks were observed after 150 cycles. △: Cracks were observed after 100 cycles. ×: Cracks were observed after 50 cycles.

[0158] Example 1 Preparation of Polymer Solution (A-1) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet pipe, a cooling pipe, and a dropping vessel inlet was charged with 32 parts of propylene glycol monomethyl ether acetate (PGMEA) and 54 parts of propylene glycol monomethyl ether (PGME), and the atmosphere was replaced with nitrogen, followed by heating to 90°C. On the other hand, a dropping tank (A) was prepared by stirring and mixing 10 parts of N-benzylmaleimide (BzMI), 12 parts of acrylic acid (AA), 35 parts of tert-butyl methacrylate (TBMA), 18 parts of methyl methacrylate (MMA), 20 parts of 2-hydroxyethyl methacrylate (HEMA), 5 parts of RUVA-93 (RUVA), 10 parts of propylene glycol monomethyl ether acetate (PGMEA), and 3 parts of t-butylperoxy-2-ethylhexanoate ("Perbutyl (registered trademark) O" manufactured by NOF Corporation) in a beaker, and a dropping tank (B) was prepared by stirring and mixing 1.5 parts of β-mercaptopropionic acid and 20 parts of propylene glycol monomethyl ether acetate (PGMEA). After the temperature of the reaction tank reached 90°C, dropwise addition from the dropping tank was initiated over 3 hours while maintaining the same temperature, and polymerization was carried out. After the dropwise addition, the temperature inside the reaction vessel was maintained at 90°C for 30 minutes, and then 1 part of Perbutyl O was added. After maintaining the temperature at 90°C for another 30 minutes, the temperature was raised to 115°C and aging was carried out for 90 minutes. Thereafter, the mixture was cooled to room temperature to obtain a polymer solution (A-1). The physical properties of the obtained polymer are shown in Table 1.

[0159] (Examples 2 to 9, 11 to 17, Comparative Examples 1 to 3) Preparation of polymer solutions (A-2) to (A-9), (A-11) to (A-20) Polymer solutions (A-2) to (A-9), (A-11) to (A-20) were obtained in the same manner as in Example 1, except that the monomer components charged into the dropping tank (A) were blended as shown in Tables 1 and 2. Various physical properties are shown in Tables 1 and 2.

[0160] Example 10 Preparation of Polymer Solution (A-10) A reaction vessel equipped with a thermometer, a stirrer, a gas inlet pipe, a cooling pipe, and a dropping vessel inlet was charged with 50 parts of propylene glycol monomethyl ether acetate (PGMEA) and 70 parts of propylene glycol monomethyl ether (PGME), and the atmosphere was replaced with nitrogen, followed by heating to 90°C. On the other hand, a dropping tank (A) was prepared by stirring and mixing 10 parts of N-benzylmaleimide (BzMI), 25 parts of acrylic acid (AA), 35 parts of tert-butyl methacrylate (TBMA), 5 parts of methyl methacrylate (MMA), 20 parts of 2-hydroxyethyl methacrylate (HEMA), 5 parts of RUVA-93 (RUVA), 60 parts of propylene glycol monomethyl ether acetate (PGMEA), and 3 parts of t-butylperoxy-2-ethylhexanoate ("Perbutyl (registered trademark) O" manufactured by NOF Corporation) in a beaker, and a dropping tank (B) was prepared by stirring and mixing 7 parts of β-mercaptopropionic acid and 10 parts of propylene glycol monomethyl ether acetate (PGMEA). After the temperature of the reaction tank reached 90°C, dropwise addition from the dropping tank was initiated over 3 hours while maintaining the same temperature, and polymerization was carried out. After the dropwise addition was completed, the reaction vessel was maintained at 90°C for 30 minutes, and then 1 part of Perbutyl O was added. After maintaining the temperature at 90°C for another 30 minutes, the temperature was raised to 115°C and aging was carried out for 90 minutes. After that, the mixture was cooled to room temperature, and bubbling of an oxygen / nitrogen = 7 / 93 (v / v) mixed gas was started. 20 parts of glycidyl methacrylate, 0.5 parts of triethylamine (TEA) as a catalyst, and 0.2 parts of Antage W-400 (manufactured by Kawaguchi Chemical Industry Co., Ltd.) as a polymerization inhibitor were charged and reacted at 115°C for 11 hours. After that, the mixture was cooled to room temperature to obtain a polymer solution (A-10). Various physical properties are shown in Table 1.

[0161] Comparative Example 4 Preparation of Polymer Solution (A-21) A polymer solution (A-21) was obtained in the same manner as in Example 10, except that the monomer components charged into the dropping tank (A) were blended as shown in Table 2. Various physical properties are shown in Table 2.

[0162] (Examples 18 to 34, Comparative Examples 5 to 9) Using the obtained polymer solutions (A-1) to (A-21), photosensitive resin compositions 1 to 22 were prepared by the following method, and the development rate, pattern diameter, and minimum adhesion pattern were evaluated by the evaluation methods described above. The results are shown in Table 3.

[0163] (Preparation of Colorant Composition) 12.9 parts of propylene glycol monomethyl ether acetate, 0.4 parts of Disparlon DA-7301 as a dispersant, 2.25 parts of C.I. Pigment Green 58 and 1.5 parts of C.I. Pigment Yellow 138 as colorants were mixed and dispersed for 3 hours using a paint shaker to obtain a colorant composition (solid content 22% by mass).

[0164] (Preparation of Photosensitive Resin Compositions) As shown in Table 3, 38 parts by solid content of various polymer solutions, 30 parts of dipentaerythritol hexaacrylate as a polyfunctional monomer, 2 parts of Irgacure OXE-02 (manufactured by BASF Japan) as a photopolymerization initiator, 30 parts of the colorant composition obtained above, RUVA-93 (ultraviolet absorber, manufactured by Otsuka Chemical Co., Ltd.), and further a dilution solvent (propylene glycol monomethyl ether acetate) were added and stirred so that the solid content concentration of the photosensitive resin composition was 20%, thereby obtaining photosensitive resin compositions 1 to 22.

[0165] (Examples 35 to 51, Comparative Examples 10 to 14) Furthermore, using the obtained polymer solutions (A-1) to (A-21), photosensitive resin compositions 23 to 44 were prepared according to the formulations shown in Table 4, and the solvent resistance was evaluated by the evaluation method described above. The results are shown in Table 4.

[0166]

[0167]

[0168] The descriptions in Tables 1 and 2 are as follows: RUVA: RUVA-93 (2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate, manufactured by Otsuka Chemical Co., Ltd.) HALS: Adekastab LA-82 (1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, manufactured by ADEKA Corporation) TBMA: tert-butyl methacrylate TBA: tert-butyl acrylate DMPE: 2-propenoic acid, 1,1-dimethylpropyl ester ECPM: 1-ethylcyclopentyl methacrylate 2EHA: 2-ethylhexyl acrylate BA: butyl acrylate MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate AA: methacrylic acid BzMI: N-benzylmaleimide CHMA: cyclohexyl methacrylate GMA: glycidyl methacrylate

[0169]

[0170]

[0171] From Tables 1 to 4, it was possible to confirm the superiority of the (meth)acrylate polymers, photosensitive resin compositions, and cured products of the examples in terms of developability, solvent resistance, heat resistance, and weather resistance.

[0172] (Examples 52 to 58, Comparative Examples 15 to 16) Furthermore, using the obtained polymer solutions (A-1), (A-9), (A-20), and (A-21), photosensitive resin compositions 45 to 53 were prepared according to the formulations (solid content) shown in Table 5, and the pattern diameter and thermal cycle resistance were evaluated using the evaluation methods described above. The results are shown in Table 5. The descriptions in Table 5 are as follows. Irg907: Irgacure 907, manufactured by BASF Japan Ltd. JER828: Bisphenol A type epoxy resin (epoxy equivalent 186 g / equivalent, manufactured by Mitsubishi Chemical Corporation) YDPN-638: Phenol novolac type epoxy resin (epoxy equivalent 180 g / equivalent, manufactured by Nippon Steel Chemical & Material Co., Ltd.) SFP-30MHE: Silica manufactured by Denka Co., Ltd. (average particle size 600 nm (d50)) PGM-AC-4130Y: Propylene glycol monomethyl ether dispersed silica sol (average particle size 50 nm (d50)) manufactured by Nissan Chemical Industries, Ltd.

[0173]

[0174] Table 5 confirms the superiority of the photosensitive resin compositions of the examples and their cured products in terms of pattern diameter and thermal cycle resistance, and also confirms the effectiveness of having a structure with ultraviolet absorption and / or radical scavenging ability and not having double bonds. Furthermore, the absence of silica fine particles resulted in finer patterns, and their use improved thermal cycle resistance.

Claims

1. A (meth)acrylate polymer characterized by having a structural unit (A) derived from a tertiary carbon-containing (meth)acrylate monomer having a structure in which an oxygen atom adjacent to the (meth)acryloyl group is bonded to a tertiary carbon atom, a structural unit (B) derived from a monomer having a hydroxyl group, and a structural unit (C) derived from a (meth)acrylate monomer having an ultraviolet absorption ability and / or a radical scavenging ability.

2. The tertiary carbon-containing (meth)acrylate monomer is a monomer represented by the following general formula (1), and the (meth)acrylate polymer according to claim 1 is characterized in that. (In the formula, R １ represents a hydrogen atom or a methyl group. R ２ and R ３ are the same or different and represent an organic group. R ４ , R ５ and R ６ are the same or different and represent a hydrogen atom or an organic group, and at least one of R ４ , R ５ and R ６ is a hydrogen atom. R ２ , R ３ , R ４ , R ５ and R ６ may each be combined to form a ring.) 3. The (meth)acrylate polymer according to claim 1 or 2, wherein the (meth)acrylate monomer having an ultraviolet absorption ability and / or a radical scavenging ability contains at least one monomer selected from the group consisting of a hindered phenol compound having a (meth)acryloyl group and a hindered amine compound having a (meth)acryloyl group.

4. The (meth)acrylate polymer according to claim 3, wherein at least one monomer selected from the group consisting of the hindered phenol compound having a (meth)acryloyl group and the hindered amine compound having a (meth)acryloyl group has a maximum absorption peak in the wavelength region of 250 to 400 nm.

5. The (meth)acrylate polymer according to claim 3 or 4, wherein at least one monomer selected from the group consisting of the hindered phenol compound having a (meth)acryloyl group and the hindered amine compound having a (meth)acryloyl group has a benzotriazole group which may have a substituent.

6. The (meth)acrylate polymer according to any one of claims 3 to 5, wherein at least one monomer selected from the group consisting of a hindered phenol compound having the (meth)acryloyl group and a hindered amine compound having the (meth)acryloyl group is a hindered phenol compound represented by the following general formula (4). (In the formula, R ７ represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. R ８ represents a group having a (meth)acryloyl group. X represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a cyano group or a nitro group.) 7. The (meth)acrylate polymer according to any one of claims 1 to 6, further having a structural unit (D) derived from a monomer having a glass transition temperature of the homopolymer of 0 °C or lower.

8. A photosensitive resin composition comprising the (meth)acrylate polymer according to any one of claims 1 to 7, a polyfunctional monomer, and a photopolymerization initiator.

9. The photosensitive resin composition according to claim 8, further comprising a colorant.

10. The photosensitive resin composition according to claim 8 or 9, which is a resist for a color filter.

11. The photosensitive resin composition according to claim 8, which is a resist for an insulating film.

12. A cured product obtained by curing the photosensitive resin composition according to any one of claims 8 to 11.

13. A member for a display device, characterized by having the cured product according to claim 12.

14. A member for a semiconductor device, comprising the cured product according to claim 12.

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