CN116348522A - Alkali-soluble resin containing polymerizable unsaturated group, photosensitive resin composition containing the resin as essential component, and cured product thereof - Google Patents

Alkali-soluble resin containing polymerizable unsaturated group, photosensitive resin composition containing the resin as essential component, and cured product thereof Download PDF

Info

Publication number
CN116348522A
CN116348522A CN202180072635.0A CN202180072635A CN116348522A CN 116348522 A CN116348522 A CN 116348522A CN 202180072635 A CN202180072635 A CN 202180072635A CN 116348522 A CN116348522 A CN 116348522A
Authority
CN
China
Prior art keywords
formula
alkali
acid
general formula
resin composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202180072635.0A
Other languages
Chinese (zh)
Inventor
滑川崇平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Chemical and Materials Co Ltd
Original Assignee
Nippon Steel and Sumikin Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Steel and Sumikin Chemical Co Ltd filed Critical Nippon Steel and Sumikin Chemical Co Ltd
Publication of CN116348522A publication Critical patent/CN116348522A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders

Abstract

The present invention provides a photosensitive resin composition which has high heat resistance, does not generate heat sagging and can keep a rectangular cross section shape, and a cured product thereof. The alkali-soluble resin containing a polymerizable unsaturated group of the present invention is represented by the following general formula (1), and has a carboxyl group and a polymerizable unsaturated group in one molecule. (in the formula (1), X 1 Represents tetravalent aromatic ring-containing groups, Y 1 Represents a divalent aromatic ring-containing group. X is X 1 And Y 1 Part of the hydrogen atoms of (2) may be replaced by a straight-chain or branched hydrocarbon group having 1 to 20 carbon atoms. V (V) 1 Is a substituent represented by the following general formula (2). The average value of the values of l is 0.2 to 4.0.Q (Q) 1 Is a hydrogen atom or a straight-chain or branched hydrocarbon group having 1 to 20 carbon atoms.) (in the formula (2), R 1 Represents a hydrogen atom or a methyl group. L represents a substituent represented by the following general formula (3). * Represents a site bonded to an oxygen atom (O) in formula (1). ) (in the formula (3), M represents a divalent or trivalent residue derived from a dicarboxylic acid, a tricarboxylic acid or an acid monoanhydride of these, and p is 1 or 2.* Represents a site bonded to an oxygen atom (O) in formula (2). )

Description

Alkali-soluble resin containing polymerizable unsaturated group, photosensitive resin composition containing the resin as essential component, and cured product thereof
Technical Field
The present invention relates to an alkali-soluble resin containing a polymerizable unsaturated group, a photosensitive resin composition containing the resin as an essential component, and a cured product thereof.
Background
With recent increases in performance and high definition of electronic devices, display parts, and the like, miniaturization and high density of electronic parts used therein have been demanded. Further, the processability of the insulating material used for these materials is also demanded to be fine and the cross-sectional shape of the processed pattern to be optimized. As an effective means for micromachining an insulating material, a method of patterning by exposure and development is known, in which a photosensitive resin composition is used, but many characteristics such as high sensitivity, adhesion to a substrate, reliability, heat resistance, chemical resistance and the like are required.
An insulating material composed of a conventional photosensitive resin composition uses a photo-curing reaction caused by a reaction between a photoreactive alkali-soluble resin and a photopolymerization initiator, and mainly uses i-rays (365 nm) of one of the line spectrums of a mercury lamp as an exposure wavelength for performing photo-curing. However, the i-ray is absorbed by the photosensitive resin itself or the colorant, and the photocuring degree is lowered. Further, if the film is thick, the absorption amount increases. Therefore, the exposed portions generate a difference in crosslinking density in the film thickness direction. Thus, even if the surface of the coating film is sufficiently photo-cured, it is difficult to cause a difference in crosslinking density between the exposed portion and the unexposed portion due to the difficulty in photo-curing at the bottom surface of the coating film. Thus, it is difficult to obtain an insulating material composed of a photosensitive resin composition which has desired pattern dimensional stability, development margin, pattern adhesion, edge shape and cross-sectional shape of a pattern and can be developed with high resolution.
Generally, as a photosensitive resin composition for such use, a photosensitive resin composition containing a polyfunctional photocurable monomer having a polymerizable unsaturated bond, an alkali-soluble binder resin, a photopolymerization initiator, or the like is used, and a photosensitive resin composition or the like disclosed as a technique for use as a material for a color filter can be employed. For example, patent documents 1 and 2 disclose, as a binder resin, a copolymer of (meth) acrylic acid or (meth) acrylic acid ester having a carboxyl group with maleic anhydride and other polymerizable monomers.
Further, patent document 3 discloses the following: an alkali-soluble unsaturated compound having a polymerizable unsaturated group and a carboxyl group in one molecule is effective for forming a negative pattern such as a color filter.
On the other hand, patent documents 4, 5, 6 and 7 disclose liquid resins using a reaction product of an epoxy (meth) acrylate having a bisphenol fluorene structure and an acid anhydride.
Further, patent documents 8, 9 and 10 disclose an alkali developable unsaturated resin composition formed by copolymerization of dihydroxypropyl acrylate and acid dianhydride or an alkali developable unsaturated resin composition formed by copolymerization of acid monoanhydride and acid dianhydride with dihydroxypropyl acrylate. In this case, the acid dianhydride and the dihydroxypropyl acrylate are copolymerized to obtain an oligomer.
Patent document 11 discloses polyfunctional of an alkali-soluble resin composition in which the molecular weight of a carboxyl group-containing copolymer is increased.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 61-213213
Patent document 2: japanese patent laid-open No. 1-152449
Patent document 3: japanese patent laid-open No. 4-340965
Patent document 4: japanese patent laid-open No. 4-345673
Patent document 5: japanese patent laid-open No. 4-345608
Patent document 6: japanese patent laid-open No. 4-355450
Patent document 7: japanese patent laid-open No. 4-363311
Patent document 8: japanese patent laid-open No. 5-339356
Patent document 9: japanese patent laid-open No. 7-3122
Patent document 10: international publication No. 94/00801
Patent document 11: japanese patent laid-open No. 9-325494
Disclosure of Invention
Problems to be solved by the invention
However, since the copolymers disclosed in patent document 1 and patent document 2 are random copolymers, the distribution of the alkali dissolution rate occurs in the light irradiated portion and the light non-irradiated portion, and the margin at the time of the developing operation becomes narrow, and it is therefore difficult to obtain a pattern shape or a fine pattern of sharp angles.
Further, since the alkali-soluble unsaturated compound described in patent document 3 is insoluble by light irradiation, it is predicted that the combination of the binder resin and the polyfunctional polymerizable monomer is more sensitive than the combination. Here, examples of the compound described in patent document 3 include a compound obtained by arbitrarily adding an acrylic acid and an acid anhydride of a polymerizable unsaturated bond group to a hydroxyl group of a phenol oligomer. In the compound of patent document 3, since a wide distribution occurs in the molecular weight of each molecule and the amount of carboxyl groups, the distribution of the alkali dissolution rate of the alkali-soluble resin becomes wide, and thus it is difficult to form a fine negative pattern.
Examples of the resins described in patent document 4, patent document 5, patent document 6, and patent document 7 include reaction products of epoxy (meth) acrylate and acid monoanhydride. Since the molecular weight of the reaction product is small, it is difficult to increase the alkali solubility of the exposed portion and the unexposed portion, and thus a fine pattern cannot be formed.
Further, since the number of polymerizable unsaturated bonds in the copolymers described in patent document 8, patent document 9, patent document 10 and patent document 11 is small, the crosslinking density cannot be sufficiently obtained, and there is room for improvement in the copolymer structure such as increasing the ratio of polymerizable unsaturated bonds in one molecule.
In addition, it is also desired that the photosensitive resin composition has a cross-sectional shape of a pattern in various resists for color filters, resists for insulating films for semiconductor devices, and the like, and is less deformed after a heat curing step after exposure and development, that is, has high heat resistance. In particular, when a fine line pattern of 10 μm or less or a via hole pattern (via pattern) of 50 μm or less in diameter is formed, it is required to keep the pattern shape rectangular with little change in pattern size due to thermal sagging.
Alternatively, a photosensitive resin composition for producing a cured film for an insulating film or the like is required to be capable of forming a pattern having a nearly rectangular shape while achieving both high adhesion to a substrate and suppression of residues.
The purpose of the present invention is to provide a photosensitive resin composition which has high heat resistance and can maintain a rectangular cross-sectional shape without sagging due to heat, or can form a pattern shape that is nearly rectangular while achieving both high adhesion to a substrate and suppression of residues, and a cured product thereof. Another object of the present invention is to provide a technique effective especially when the properties required for the heat resistance of the cured product are strict.
Solution to the problem
The present inventors have made intensive studies to solve the above problems, and as a result, have found that a photosensitive resin composition using an alkali-soluble resin containing a polymerizable unsaturated group, which is obtainable by the following reaction, is suitable for forming a cured film or the like requiring photo patterning, which is excellent in heat resistance: a resin (a resin similar to a phenol aralkyl resin) in the form of a divalent aromatic compound having two hydroxyl groups bonded to an aromatic ring group (a compound having two phenolic hydroxyl groups directly bonded to an aromatic ring such as bisphenol or naphthalene diphenol, etc.) is reacted with a carboxyl group-containing (meth) acrylate, and the resulting polyol compound having a polymerizable unsaturated group is reacted with a dicarboxylic acid, tricarboxylic acid or acid monoanhydride thereof.
The alkali-soluble resin of the present invention is an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule, which is represented by the following general formula (1).
[ chemical formula 1]
Figure BDA0004195622870000041
In the formula (1), X 1 Represents tetravalent aromatic ring-containing groups, Y 1 Represents a divalent aromatic ring-containing group. X is X 1 And Y 1 Part of the hydrogen atoms of (2) may be substituted with a straight-chain or branched hydrocarbon group having 1 to 20 carbon atoms. V (V) 1 Is a substituent represented by the following general formula (2). The average value of the values of 1 is 0.2 to 4.0.Q (Q) 1 Is a hydrogen atom or a straight-chain or branched hydrocarbon group having 1 to 20 carbon atoms.
[ chemical formula 2]
Figure BDA0004195622870000042
In the formula (2), R 1 Represents a hydrogen atom or a methyl group. L represents a substituent represented by the following general formula (3). * Represents a site bonded to an oxygen atom (O) in formula (1).
[ chemical formula 3]
Figure BDA0004195622870000051
In the formula (3), M represents a divalent or trivalent residue derived from a dicarboxylic acid, a tricarboxylic acid or an acid monoanhydride of these, and p is 1 or 2.* Represents a site bonded to an oxygen atom (O) in formula (2).
The photosensitive resin composition of the present invention contains the following components as essential components: (i) the above alkali-soluble resin; (ii) A photopolymerizable monomer having at least one polymerizable unsaturated group; and (iii) a photopolymerization initiator.
The cured product of the present invention is obtained by curing the photosensitive resin composition.
Effects of the invention
According to the present invention, by containing the alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule represented by the general formula (1), it is possible to provide a photosensitive resin composition which has high heat resistance and can maintain a rectangular cross-sectional shape without causing sagging due to heat, and a cured product thereof. Alternatively, the substrate can be formed in a pattern shape substantially rectangular while achieving both high adhesion to the substrate and suppression of residues. Further, a technique effective in the case where the characteristics required for the heat resistance of the cured product are strict can be provided.
Detailed Description
The following describes embodiments of the present invention, but the present invention is not limited to the following embodiments. In the present invention, when the content of each component is 0 in the first decimal place, description below the decimal point may be omitted.
The photosensitive resin composition according to one embodiment of the present invention contains, as essential components: (i) an alkali-soluble resin represented by the general formula (1); (ii) A photopolymerizable monomer having at least one polymerizable unsaturated group; and (iii) a photopolymerization initiator. The following describes the respective components.
[ alkali-soluble resin ]
The alkali-soluble resin represented by the general formula (1) is described below.
An alkali-soluble resin represented by the following general formula (1) has a carboxyl group and a polymerizable unsaturated group in one molecule. The alkali-soluble resin can be obtained by the following reaction: a resin (a resin similar to a phenol aralkyl resin) in the form of a divalent aromatic compound having two hydroxyl groups bonded to an aromatic ring (a compound having two phenolic hydroxyl groups directly bonded to an aromatic ring such as bisphenol or naphthalene diphenol) is reacted with a cyclic ether compound such as epichlorohydrin, the resulting epoxy compound having two or more glycidyl ether groups is reacted with a carboxylic acid compound having an unsaturated group such as (meth) acrylic acid, and the resulting polyol compound having a polymerizable unsaturated group is reacted with a dicarboxylic acid, tricarboxylic acid or acid-monoanhydride thereof.
[ chemical formula 4]
Figure BDA0004195622870000061
In the formula (1), X 1 Represents tetravalent aromatic ring-containing groups, Y 1 Represents a divalent aromatic ring-containing group. X is X 1 And Y 1 Part of the hydrogen atoms of (2) may be replaced by a straight-chain or branched hydrocarbon group having 1 to 20 carbon atoms. In addition, V 1 Is a substituent represented by the following general formula (2). In addition, l represents a number of 0 to 20, and the average value of the values of l is preferably 0.2 to 4.0.Q (Q) 1 Is a hydrogen atom or a straight-chain or branched hydrocarbon group having 1 to 20 carbon atoms.
[ chemical formula 5]
Figure BDA0004195622870000062
In the formula (2), R 1 Represents a hydrogen atom or a methyl group. L represents a substituent represented by the following general formula (3). * Represents a site bonded to an oxygen atom (O) in formula (1).
[ chemical formula 6]
Figure BDA0004195622870000063
In the formula (3), M represents a divalent or trivalent residue derived from a dicarboxylic acid, a tricarboxylic acid or an acid monoanhydride of these, and p is 1 or 2.* Represents a site bonded to an oxygen atom (O) in formula (2).
For example, the alkali-soluble resin represented by the general formula (1) may be an alkali-soluble resin derived from a bisphenol aralkyl resin represented by the following general formula (4). X in formula (4) 2 、Y 2 、V 2 And Q 2 Respectively correspond to X in the formula (1) 1 、Y 1 、V 1 And Q 1 。
[ chemical formula 7]
Figure BDA0004195622870000071
In the formula (4), X 2 Is a tetravalent substituent represented by the following general formula (5) derived from bisphenol compound, Y 2 Is a divalent substituent represented by the following general formula (6). In the following general formula (5) and general formula (6), a part of hydrogen atoms may be substituted with a straight-chain or branched hydrocarbon group having 1 to 20 carbon atoms. V (V) 2 Is a substituent represented by the general formula (2). m represents a number of 0 to 20, and the average value of the values of m is preferably 0.2 to 4.0.Q (Q) 2 Is a hydrogen atom or a straight or branched hydrocarbon group of 1 to 20.
In the above general formula (4), X is 2 And two Y 2 In the case of the bonded structure, as represented by the following general formula (5), the two bonding sites may be on only one of the benzene rings, or may be Y with one bonding site on each of the two benzene rings 2 Bonding form. In one embodiment of the present invention, the description is made on the form in which two bonding sites are bonded to one benzene ring.
[ chemical formula 8]
Figure BDA0004195622870000072
In the formula (5), the oxygen atoms (O) and Y in the formula (4) 2 Or Q 2 Bonding sites. The upper and lower bonding sites (bonding sites at the 4-position and 4' -position) in formula (5) are preferably sites bonded to the oxygen atom (O) in formula (4), and the left and right bonding sites (other bonding sites) are preferably sites bonded to Y in formula (4) 2 Or Q 2 The bonding site is not limited thereto.
[ chemical formula 9]
Figure BDA0004195622870000081
In the formula (6), X in the formula (4) 2 Bonding sites.
[ chemical formula 10]
Figure BDA0004195622870000082
In the formula (2), R 1 Represents a hydrogen atom or a methyl group. L represents a substituent represented by the following general formula (3). * Represents a site bonded to an oxygen atom (O) in formula (4).
[ chemical formula 11]
Figure BDA0004195622870000083
In the formula (3), M represents a divalent or trivalent residue derived from a dicarboxylic acid, a tricarboxylic acid or an acid monoanhydride of these, and p is 1 or 2.* Represents a site bonded to an oxygen atom (O) in formula (2).
Since the alkali-soluble resin represented by the general formula (1) according to one embodiment of the present invention has both a polymerizable unsaturated group and a carboxyl group, the photosensitive resin composition containing the alkali-soluble resin has excellent photocurability, good developability, and patterning characteristics. It is considered that the above technique is effective when the photosensitive resin composition is formed into a cured product, particularly when heat resistance is required.
[ method for producing photosensitive resin composition ]
(Process for producing alkali-soluble resin)
First, a method for producing the alkali-soluble resin represented by the general formula (1) will be described in detail, taking the alkali-soluble resin represented by the general formula (4) as an example.
The alkali-soluble resin represented by the general formula (4) is X 2 Is a tetravalent substituent represented by the general formula (5) derived from bisphenol compound, Y 2 Is a divalent substituent represented by the general formula (6), Q 2 Is hydrogen atom, V 2 An alkali-soluble resin (hereinafter referred to as bisphenol aralkyl alkali-soluble resin) having a polymerizable double bond and a carboxyl group in one molecule, which is a substituent represented by the general formula (2).
The alkali-soluble resin represented by the general formula (4) can be obtained by the following reaction: a bisphenol aralkyl resin in the form of an aromatic ring group-containing bonded bisphenol compound is reacted with a cyclic ether compound such as epichlorohydrin, then the resulting epoxy compound is reacted with a carboxylic acid compound containing an unsaturated group such as (meth) acrylic acid, and then the resulting polyhydric alcohol compound having a polymerizable unsaturated group is reacted with a dicarboxylic acid, tricarboxylic acid or acid monoanhydride thereof.
Specifically, the alkali-soluble resin represented by the general formula (4) can be obtained by the following reaction: an epoxy compound having a biphenyl skeleton represented by the following general formula (8) and having two or more glycidyl ether groups, wherein the epoxy compound is obtained by substituting a glycidyl group for a hydrogen atom of a phenolic hydroxyl group of a bisphenol aralkyl resin represented by the following general formula (7), is reacted with (meth) acrylic acid, and a polycarboxylic acid or an anhydride thereof is added to the obtained polyhydric alcohol compound having a polymerizable unsaturated group. The method for producing the epoxy compound having a biphenyl skeleton may be, for example, the method described in International publication No. 2011/74517. In the preparation of the resin represented by the following general formula (8), the resin is usually obtained as a mixture of molecules having different values n.
[ chemical formula 12]
Figure BDA0004195622870000091
In the formula (7), n represents a number of 0 to 20, and the average value of the values of n is preferably 0.2 to 4.0.
[ chemical formula 13]
Figure BDA0004195622870000101
In the formula (8), o represents a number of 0 to 20, and the average value of the values of o is preferably 0.2 to 4.0.W represents a glycidyl group.
As a polymerization method of the bisphenol aralkyl resin, general phenol resins and a preparation method of the phenol aralkyl resin can be referred to.
Specifically, the epoxy compound represented by the general formula (8) can be obtained by reacting bisphenol aralkyl resin represented by the general formula (7) with epichlorohydrin. The method for producing the polyhydric hydroxyl resin as a raw material of the epoxy resin is explained.
As a first stage, the polyhydric hydroxyl resin can be obtained by condensing the bisphenol with the crosslinking agent in the absence of a catalyst or in the presence of an acidic catalyst.
Examples of the above biphenols include 4,4' -dihydroxybiphenyl and the like.
Further, examples of the above-mentioned crosslinking agent include: 4,4' -bis (hydroxymethyl) biphenyl, 4' -bis (chloromethyl) biphenyl, 4' -bis (bromomethyl) biphenyl, 4' -bis (methoxymethyl) biphenyl, 4' -bis (ethoxymethyl) biphenyl, and the like. Among the above-mentioned crosslinking agents, 4' -bis (chloromethyl) biphenyl, 4' -bis (hydroxymethyl) biphenyl, 4' -bis (methoxymethyl) biphenyl are preferable.
The acidic catalyst may be appropriately selected from known inorganic acids and organic acids. Examples of the above-mentioned acidic catalyst include: inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as formic acid, oxalic acid and p-toluenesulfonic acid, lewis acids such as aluminum chloride, solid acids such as activated clay and zeolite, and the like.
As the second stage, an epoxy compound having a biphenyl skeleton represented by the general formula (8) having two or more glycidyl ether groups can be obtained by substituting a glycidyl group for a hydrogen atom of a phenolic hydroxyl group of the bisphenol aralkyl resin represented by the general formula (7). The preparation method can be carried out in the same manner as in the usual epoxidation reaction of a hydroxyl group. For example, there are the following methods: after dissolving bisphenol aralkyl resin in excessive epichlorohydrine, the bisphenol aralkyl resin is reacted for 1 to 10 hours at 20 to 150 ℃ in the presence of alkali metal hydroxide such as sodium hydroxide.
The reaction of such an epoxy compound with (meth) acrylic acid can be carried out by a known method. For example, 1 mole of (meth) acrylic acid is used relative to 1 mole of epoxy group. In order to react all of the epoxy groups with (meth) acrylic acid, it is preferable to add (meth) acrylic acid in a small excess amount compared to the mole of epoxy groups and carboxyl groups and the like. It is also possible to use a resin obtained by reacting (meth) acrylic acid partially or completely with (meth) acrylic acid ester containing carboxyl groups. The carboxyl group-containing (meth) acrylate is a compound having one carboxyl group and one or more (meth) acrylate groups in the molecule. Examples of the carboxyl group-containing (meth) acrylate include: 2-propenoxyethylphthalic acid, 2-propenoxyethylhexahydrophthalic acid, 2-propenoxyethylsuccinic acid, 2-propenoxyhexanoic acid, 2-methacryloxyhexanoic acid, and the like.
The reaction product obtained by the above reaction is an epoxy (meth) acrylate represented by the following general formula (9).
[ chemical formula 14]
Figure BDA0004195622870000111
In the formula (9), q represents a number of 0 to 20, and the average value of the values of q is preferably 0.2 to 4.0.W (W) 1 Is a substituent represented by the following general formula (10), and W is 1 Is a substituent having a polymerizable unsaturated group in the molecule.
[ chemical formula 15]
Figure BDA0004195622870000112
In the formula (10), R 2 Represents a hydrogen atom or a methyl group. * Represents a site bonded to an oxygen atom (O) in formula (9).
The solvent, catalyst and other reaction conditions used at this time are not particularly limited. For example, it is preferable that the solvent has no hydroxyl group and has a boiling point higher than the reaction temperature. Examples of such solvents include: cellosolve-based solvents including ethyl cellosolve acetate and butyl cellosolve acetate; high boiling point ether-based or ester-based solvents including Diglyme (Diglyme), ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and the like; ketone solvents including cyclohexanone and diisobutyl ketone. Examples of the catalyst include: ammonium salts including tetraethylammonium bromide, triethylbenzyl ammonium chloride, and the like; known catalysts such as phosphines including triphenylphosphine and tris (2, 6-dimethoxyphenyl) phosphine.
The alkali-soluble resin represented by the general formula (4) can be obtained by reacting the hydroxyl group of the compound represented by the general formula (9) with a dicarboxylic acid, a tricarboxylic acid or an acid monoanhydride of these.
Examples of the above dicarboxylic acid or tricarboxylic acid or acid monoanhydrides of these include: saturated chain hydrocarbon dicarboxylic or tricarboxylic acids, saturated cyclic hydrocarbon dicarboxylic or tricarboxylic acids, unsaturated dicarboxylic or tricarboxylic acids, aromatic hydrocarbon dicarboxylic or tricarboxylic acids, or acid monoanhydrides of these, and the like. The hydrocarbon residues (structures other than carboxyl groups) of these acid anhydrides may be substituted with substituents such as alkyl groups, cycloalkyl groups, and aromatic groups.
Examples of acid anhydrides of saturated chain hydrocarbon dicarboxylic or tricarboxylic acids include: succinic acid, acetylsuccinic acid, adipic acid, azelaic acid, citramalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutarate (oxoglutarate), pimelic acid, sebacic acid, suberic acid, diglycolic acid, and other acid anhydrides.
Further, examples of the acid monoanhydrides of the saturated cyclic hydrocarbon dicarboxylic acid or tricarboxylic acid include: acid monoanhydrides such as hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornanedicarboxylic acid, hexahydrotrimellitic acid, and the like.
Further, examples of the acid monoanhydrides of the unsaturated di-or tri-carboxylic acids include: maleic acid, itaconic acid, tetrahydrophthalic acid, methyl endomethylene tetrahydrophthalic acid, chlormycolic acid, and the like.
Further, examples of the acid monoanhydrides of the aromatic hydrocarbon dicarboxylic acid or tricarboxylic acid include: acid monoanhydrides such as phthalic acid and trimellitic acid.
Among the acid anhydrides of the above dicarboxylic acid or tricarboxylic acid, succinic acid, hexahydrophthalic acid, hexahydrotrimellitic acid, maleic acid, itaconic acid, tetrahydrophthalic acid, phthalic acid, and acid anhydrides of trimellitic acid are preferable, and succinic acid, hexahydrotrimellitic acid, maleic acid, itaconic acid, tetrahydrophthalic acid, phthalic acid, and acid anhydrides of trimellitic acid are more preferable. The acid monoanhydride of the dicarboxylic acid or tricarboxylic acid may be used alone or in combination of two or more.
The reaction temperature at which the hydroxyl group of the compound represented by the general formula (10) is reacted with a dicarboxylic acid or a tricarboxylic acid or an acid monoanhydride of these to synthesize the alkali-soluble resin represented by the general formula (4) is preferably 20 to 120 ℃, more preferably 40 to 90 ℃. The molar ratio of the acid anhydride in synthesizing the compound represented by the general formula (4) can be arbitrarily changed for the purpose of adjusting the acid value of the alkali-soluble resin represented by the general formula (4).
Thus, an alkali-soluble resin represented by the general formula (4) can be obtained.
The alkali-soluble resin represented by the general formula (1) is not limited to the alkali-soluble resin obtained by the above-described method. For example, a known naphthalene diphenol aralkyl resin or biphenyl diphenol aralkyl resin may be used instead of the bisphenol aralkyl resin represented by the general formula (7). Alternatively, a known bisphenol aralkyl resin obtained by using an aromatic compound other than a biphenyl compound (a crosslinking agent used in the case of synthesizing a naphthalene diphenol aralkyl resin described later, or the like) as a crosslinking agent may be used instead of the bisphenol aralkyl resin represented by the general formula (7).
In the case of using a naphthalenediol aralkyl resin, various naphthalenediols such as 1, 5-naphthalenediol, 1, 6-naphthalenediol, 1, 7-naphthalenediol, 1, 8-naphthalenediol, 2, 6-naphthalenediol, and 2, 7-naphthalenediol can be used as the material instead of the above-mentioned diphenols.
As the crosslinking agent in the case of synthesizing the naphthalene diphenol aralkyl resin, it is possible to use: halogenated alkyl compounds such as 1, 4-bis (chloromethyl) benzene, 1, 4-bis (chloroethyl) benzene, 4' -bis (chloromethyl) biphenyl, 4' -bis (bromomethyl) biphenyl, and 4,4' -bis (chloromethyl biphenyl) ether; alcohols such as terephthalyl alcohol, p-bis (hydroxyethyl) benzene, 4 '-bis (hydroxymethyl) biphenyl, 2, 6-bis (hydroxymethyl) naphthalene, and 2,2' -bis (hydroxymethyl) diphenyl ether; dialkyl ethers of the alcohols such as 4,4 '-bis (methoxymethyl) biphenyl, 4' -bis (ethoxymethyl) biphenyl, and terephthalyl dimethyl ether; divinyl compounds such as divinylbenzene and divinylbenzene.
In the case of using a known bisphenol aralkyl resin obtained by using an aromatic compound other than a biphenyl compound as a crosslinking agent, an alkali-soluble resin can be obtained by synthesizing the bisphenol aralkyl resin represented by the general formula (7) in the same manner as in the case of using the bisphenol aralkyl resin except that the crosslinking agent (excluding the biphenyl compound) is used. In the case of using a naphthalene diphenol aralkyl resin or a biphenyl diphenol aralkyl resin, the alkali-soluble resin of the present invention can be obtained by the same method.
(Process for producing photosensitive resin composition)
Next, a method for producing the photosensitive resin composition according to an embodiment of the present invention will be described. The photosensitive resin composition of the present invention contains (ii) a photopolymerizable monomer having at least one polymerizable unsaturated group and (iii) a photopolymerization initiator, in addition to the alkali-soluble resin represented by the general formula (1) described above. The following describes the respective components.
The photosensitive resin composition contains an alkali-soluble resin represented by the general formula (1) as (i) an alkali-soluble resin. The content of the component (i) in the solid component (the solid component includes a monomer that becomes a solid component after curing) other than the solvent in the photosensitive resin composition is preferably 30 mass% or more and 80 mass% or less.
Examples of the photopolymerizable monomer having at least one polymerizable unsaturated group as the component (ii) include: monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, and the like. In the case where a crosslinked structure between molecules of the alkali-soluble resin is required to be formed, a photopolymerizable monomer having two or more polymerizable unsaturated groups is preferably used, and a photopolymerizable monomer having three or more polymerizable unsaturated groups is more preferably used. These compounds may be used alone or in combination of two or more.
The blending ratio [ (i)/(ii) ] of the component (ii) to the alkali-soluble resin [ (i) component ] (i) ] is preferably 20/80 to 90/10, more preferably 40/60 to 80/20. Here, if the blending ratio of the alkali-soluble resin is sufficiently large, the cured product after the photo-curing reaction becomes sufficiently hard. Further, since the acid value of the coating film becomes sufficiently high, the coating film is sufficiently soluble in an alkali developer, and the edges of the pattern are less likely to shake in the unexposed portions and are easily made clear. In contrast, if the proportion of the alkali-soluble resin is not excessively large, the proportion of the photoreactive functional group in the resin can be sufficiently increased, and a crosslinked structure can be sufficiently formed by the photocuring reaction. Further, since the acid value in the resin component is not excessively high, the solubility in the alkali developer is easily suppressed to a predetermined range, and a pattern having only the target thickness line width is easily formed in the exposure portion, so that defects in the pattern are less likely to occur.
Examples of the photopolymerization initiator as the component (iii) include: acetophenones such as acetophenone, 2-diethoxy acetophenone, p-dimethyl acetophenone, p-dimethylamino propiophenone, dichloro acetophenone, trichloroacetophenone, and p-tert-butyl acetophenone; alkylbenzene ketones such as 1-hydroxycyclohexyl phenyl ketone; benzophenone such as benzophenone, 2-chlorobenzophenone, p' -bis (dimethylaminobenzophenone); benzoin ethers such as benzil (benzoin), benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.; biimidazole compounds such as 2- (O-chlorophenyl) -4, 5-phenylbiimidazole, 2- (O-chlorophenyl) -4, 5-di (m-methoxyphenyl)) biimidazole, 2- (O-fluorophenyl) -4, 5-diphenylbiimidazole, 2- (O-methoxyphenyl) -4, 5-diphenylbiimidazole, and 2,4, 5-triarylbiimidazole; halomethyl diazole compounds such as 2-trichloromethyl-5-styryl-1, 3, 4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3, 4-oxadiazole, and 2-trichloromethyl-5- (p-methoxystyryl) -1,3, 4-oxadiazole; halomethyl-s-triazine compounds such as 2,4, 6-tris (trichloromethyl) -1,3, 5-triazine, 2-methyl-4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2-phenyl-4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-chlorophenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (3, 4, 5-trimethoxystyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-methylthiostyryl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine; o-acyl oxime compounds such as 1, 2-octanedione, 1- [4- (phenylsulfanyl) phenyl ] -,2- (O-benzoyl oxime), 1- (4-phenylsulfanyl) butane-1, 2-dione-2-oxime-O-benzoate, 1- (4-methylsulfanyl) butane-1, 2-dione-2-oxime-O-acetate, and 1- (4-methylsulfanyl) butane-1-ketoxime-O-acetate; sulfur compounds such as benzyl dimethyl ketal, thioxanthone, 2-chlorothioxanthone, 2, 4-diethylthioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone; anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1, 2-benzanthraquinone, and 2, 3-diphenylanthraquinone; organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, cumene peroxide and the like; thiol compounds such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole; tertiary amines such as triethanolamine and triethylamine. These photopolymerization initiators may be used alone or in combination of two or more.
The content of the photopolymerization initiator as the component (iii) is preferably 0.1 to 10 parts by mass, more preferably 2 to 5 parts by mass, relative to 100 parts by mass of the total amount of the (i) alkali-soluble resin and the (ii) photopolymerizable monomer. Here, if the amount of the photopolymerization initiator added is 0.1 part by mass or more, the sensitivity is sufficiently high, and if the amount of the photopolymerization initiator added is 10 parts by mass or less, a flare in which a tapered shape (a shape in the film thickness direction of the developed pattern cross section) is unclear and a drag-and-drop state is not likely to occur. In addition, the possibility of generation of decomposed gas when exposed to high temperature in the subsequent step is low.
The photosensitive resin composition according to one embodiment of the present invention may contain (iv) an epoxy compound.
(iv) The epoxy compound (c) may be used without particular limitation as a commercially available known compound such as an epoxy resin. Examples of the epoxy resin include: bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy resin, biphenyl type epoxy resin, bisphenol fluorene type epoxy compound, phenol novolac (phenol novolac) type epoxy compound, cresol novolac (cresol novolac) type epoxy compound, glycidyl ether of polyhydric alcohol, glycidyl ester of polybasic carboxylic acid, polymer containing glycidyl (meth) acrylate as a unit, alicyclic epoxy compound represented by 3, 4-epoxycyclohexane carboxylic acid [ (3, 4-epoxycyclohexyl) methyl ], 1, 2-epoxy-4- (2-epoxyethyl) cyclohexane adduct of 2, 2-bis (hydroxymethyl) -1-butanol (for example, "EHPE3150", manufactured by Kagaku Kogyo Co., ltd.), phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, epoxypolybutadiene (for example, "NISSO-PB JP-100", caesada silicone type), epoxy compound having a skeleton. Preferably, these components are compounds having an epoxy equivalent of 100 to 300g/eq and a number average molecular weight of 100 to 5000. (iv) The component (A) may be used alone or in combination of two or more. In the case where it is required to increase the crosslinking density of the alkali-soluble resin, a compound having at least two or more epoxy groups is preferable.
The content of the epoxy compound (iv) is preferably 10 parts by mass or more and 40 parts by mass or less relative to 100 parts by mass of the total of the component (i) and the component (ii). Here, one of the purposes of adding the epoxy compound is to reduce the amount of carboxyl groups remaining when forming a cured film after patterning so as to improve the reliability of the cured film, and by setting the addition amount of the epoxy compound to 10 parts by mass or more, the moisture resistance reliability when used as an insulating film can be further improved. Further, by setting the amount of the epoxy compound to 40 parts by mass or less, the amount of the photosensitive group in the resin component in the photosensitive resin composition can be sufficiently increased, so that the sensitivity for patterning is sufficient.
The photosensitive resin composition according to one embodiment of the present invention may further contain a dispersoid as the (v) component.
As the dispersoids of the component (v), known dispersoids which can be used in photosensitive resin compositions can be used without particular limitation as long as they can be dispersed with an average particle diameter of 1 to 1000nm (average particle diameter measured by a laser diffraction/scattering particle diameter analyzer or a dynamic light scattering particle diameter analyzer). Examples of dispersoids include: organic pigments such as azo pigments, condensed azo pigments, azomethine pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, reduced (threne) pigments, perylene pigments, pyrene pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, thioindigo pigments, and the like; inorganic pigments such as titanium oxide pigments and composite oxide pigments; pigments such as carbon black pigments (colorants that are substantially insoluble in the medium); an organic filler such as acrylic polymer particles and urethane polymer particles; inorganic fillers such as silica, talc, mica, glass fibers, carbon fibers, calcium silicate, magnesium carbonate, calcium sulfate, and barium sulfate; nanoparticles of metals or metal oxides, and the like.
These (v) dispersoids may be used singly or in combination of plural kinds depending on the function of the target photosensitive resin composition. Examples of the light-shielding resist used in the preparation of the black matrix of the color filter include: carbon black, titanium black, black organic pigments. Examples of the colored resist used in the preparation of the pixels of the color filter include: red, orange, yellow, green, blue, violet organic pigments. Examples of the solder resist used in the preparation of the insulating film of the printed wiring board include: organic pigments, inorganic fillers. Examples of decorative resists used in the design of the front surface glass of a touch screen include: carbon black, titanium black, black organic pigments, white pigments. Examples of the transparent resist having high hardness, high refractive index, and high durability include: transparent fillers such as silica and titania. These (v) dispersoids can be used by appropriately selecting them.
Further, examples of the case where the (v) dispersoids are light-shielding materials include: black organic pigments, mixed color organic pigments, and black inorganic pigments. In this case, (v) the dispersoid (light shielding material) varies depending on the application, but a dispersoid excellent in insulation properties, heat resistance, light resistance and solvent resistance is preferable. Here, examples of the black organic pigment as the light shielding material include: perylene black, aniline black, cyanine black, lactam black. Examples of the color-mixed organic pigment as the light-shielding material include: two or more pigments selected from red, blue, green, violet, yellow, cyanine, magenta, and the like are mixed to simulate a darkened pigment. Examples of the black inorganic pigment as the light shielding material include: carbon black, chromium oxide, iron oxide, titanium black. These (v) dispersoids may be used singly or in combination.
Examples of the organic pigment that can be used as the component (v) include pigments numbered as follows in the name of Color Index (Color Index), but are not limited thereto.
Pigment red 2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272, 279, etc
Pigment orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc
Pigment yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214, etc
Pigment green 7, 36, 58, etc
Pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 80, etc
Pigment violet 19, 23, 37, etc
Further, as another dispersion, a known rubber component may be added to improve impact resistance, adhesion to a plating metal during processing, and the like. In order to secure developability, the rubber component is preferably a crosslinked elastic polymer having a carboxyl group. Examples of the rubber component include: crosslinked acrylic rubber having carboxyl groups, crosslinked NBR having carboxyl groups, crosslinked MBS having carboxyl groups. When the rubber component is used, it is preferable to add 3 to 10 parts by mass of rubber having an average primary particle diameter of 0.1 μm or less to 100 parts by mass of the resin component.
(v) Preferably, the dispersion is prepared by dispersing the dispersion in a solvent together with a dispersing agent, and then blended as a photosensitive resin composition. As the solvent used in this case, only one or two or more solvents which are exemplified as the solvent for dissolving the photosensitive resin composition of the present invention may be used alone or in combination.
The proportion of the dispersoid to be used for forming the dispersoid dispersion may be 1 to 95% by mass based on the total solid content of the photosensitive resin composition of the present invention. The solid component refers to a component other than a solvent in the composition. The solid component also includes a component (ii) which becomes a solid component after photocuring. The reason why the amount of the dispersoid to be added is in a wide range of 1 to 95 mass% is that there are various cases ranging from the case of using an organic dispersoid having a small specific gravity such as acrylic resin particles or rubber particles to the case of using a large specific gravity dispersoid such as metal particles or metal oxide particles. In the case of adding a dispersoid for coloring purposes, it is preferably 5 to 80% by mass. By setting the content to more than 5% by mass in the solid component, the dispersion can be easily given a function to be given, for example, a desired coloring can be achieved, and a desired light-shielding property can be given. When the content of the photosensitive resin is 80 mass% or less in the solid content, the content of the photosensitive resin which is originally used as a binder can be sufficiently increased, and the developability and film forming ability can be ensured. Therefore, when the component (v) in the solid component is a colorant (including a light shielding material), the content thereof is preferably 10 to 70% by mass, more preferably 20 to 60% by mass.
In order to stably disperse the dispersoid, the dispersoid dispersion may contain a known dispersing agent such as a polymer dispersing agent. As the dispersant, a known compound used for pigment dispersion (such as a commercially available compound having a name of a dispersant, a dispersing wetting agent, a dispersing accelerator, etc.) or the like can be used.
Examples of dispersants include: cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, pigment derivative type dispersants (dispersion aids). In particular, the dispersant is preferably a cationic polymer dispersant having a cationic functional group such as an imidazole group, a pyrrole group, a pyridine group, a primary amine group, a secondary amine group, or a tertiary amine group as an adsorption point to a dispersant such as a pigment, having an amine value in the range of 1 to 100mgKOH/g, and a number average molecular weight in the range of 1 to 10 thousands. The amount of the dispersant to be added is preferably 1 to 35% by mass, more preferably 2 to 25% by mass, based on the dispersoid. Although a high-viscosity material such as a resin generally has a function of stabilizing dispersion, a material having no dispersion-promoting ability is not regarded as a dispersant. But is not limited to use for the purpose of stabilizing dispersion.
When the component (i) is co-dispersed in the dispersion liquid, the component (ii) and the component (iii) are mixed together with the component (i) and the component (iv) optionally added, and the solvent is added as needed, so that a photosensitive resin composition containing a dispersoid can be produced.
The photosensitive resin composition according to one embodiment of the present invention may contain a solvent.
Examples of the solvent include: alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; terpenes such as alpha-or beta-terpineol; ketones such as acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and the like. These may be dissolved singly or in combination and mixed to prepare a homogeneous solution-like composition.
The photosensitive resin composition of the present invention may contain additives such as a curing agent, a curing accelerator, a thermal polymerization inhibitor, an antioxidant, a chain transfer agent, a plasticizer, a leveling agent, a defoaming agent, a coupling agent, a surfactant, and an ultraviolet absorber, as necessary. In order to control the properties of the cured product, resins such as vinyl resin, polyester resin, polyamide resin, polyimide resin or a precursor thereof, polybenzoxazole resin or a precursor thereof, polyurethane resin, polyether resin, and melamine resin may be added.
As the curing agent, for example, a known compound known as a curing agent generally applicable to epoxy compounds can be used. Examples of the curing agent include: amine-based compounds, polycarboxylic acid-based compounds, amino resins, dicyandiamide, lewis acid complexes, phenol resins, and the like.
As the curing accelerator, for example, known compounds known as curing accelerators, curing catalysts, latent curing agents, and the like which are generally applied to epoxy compounds can be used. Examples of the curing accelerator include: tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, lewis acids, organometallic compounds, imidazoles, diazabicyclo compounds, and the like. Examples of thermal polymerization inhibitors and antioxidants include: hydroquinone, hydroquinone monomethyl ether, pyrogallol, t-butylcatechol, phenothiazine, hindered phenol antioxidants, and phosphorus heat stabilizers. Examples of the chain transfer agent include: thiol compounds, halogen compounds, quinone compounds, α -methylstyrene dimers, and the like. Examples of plasticizers include: dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, and the like. Examples of defoamers and leveling agents include: silicone-based, fluorine-based, acrylic-based compounds, and the like. Examples of the coupling agent include: vinyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3- (glycidoxy) propyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, 3-aminopropyl triethoxysilane, 3- (phenylamino) propyl trimethoxysilane, 3-ureido propyl triethoxysilane, and the like. Examples of the surfactant include: fluorine-based surfactants, silicone-based surfactants, and the like. Examples of the ultraviolet absorber include: benzotriazole compounds, benzophenone compounds, triazine compounds, and the like.
The photosensitive resin composition of the present invention preferably contains, in a solid component other than a solvent (including a monomer that becomes a solid component after curing in the solid component), 70 mass% or more in total of (i) the alkali-soluble resin represented by the general formula (1), (ii) the photopolymerizable monomer, (iii) the photopolymerization initiator, and (iv) the epoxy compound as an optional component, and (v) the dispersoid, more preferably 80 mass% or more, and still more preferably 90 mass% or more. The amount of the solvent varies depending on the target viscosity, but is preferably 10 to 80% by mass relative to the total amount.
Thus, the photosensitive resin composition of the present invention can be obtained.
The photosensitive resin composition containing the alkali-soluble resin represented by the general formula (1) prepared as described above, typified by a solder resist, a plating resist, and an etching resist used for producing a circuit board, can provide a cured film excellent in heat resistance and having excellent dimensional accuracy and pattern cross-sectional shape, which is a cured film formed by a photolithography method such as a color filter or a light shielding film of a liquid crystal display device, an organic EL display device, a LED display device, an image sensor, or the like.
Specific examples of each step of the film formation method using the coating and drying of the photosensitive resin composition are described.
The coating film (cured product) of the present invention can be obtained, for example, by applying a solution of the photosensitive resin composition onto a substrate or the like, and drying the same, and curing the same by irradiation with light (including ultraviolet rays, radiation rays, and the like). A photomask or the like is used to provide a portion irradiated with light and a portion not irradiated with light, and only the portion irradiated with light is cured, and the other portion is dissolved with an alkali solution, thereby obtaining a coating film of a desired pattern.
Specific examples of the steps of the film formation method by coating and drying the photosensitive resin composition are as follows. When the photosensitive resin composition is coated on a substrate, any method selected from known solution dipping methods, spraying methods, methods using a roll coater, a knife coater (land coater), a slit coater, a spin coater, and the like can be used. After being coated to a desired thickness by these methods, the solvent is removed (prebaked), thereby forming a coating film. The pre-baking may be performed by heating with an oven, a hot plate, or the like, vacuum drying, or a combination of these. The heating temperature and heating time of the pre-baking may be appropriately selected depending on the solvent used, for example, at 80 to 120℃for 1 to 10 minutes.
The radiation used for exposure may be, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, or the like, but the wavelength range of the radiation is preferably 250 to 450nm. Further, examples of the developer suitable for the alkali development include: sodium carbonate, potassium hydroxide, diethanolamine, tetramethylammonium hydroxide, and the like. These developer solutions can be appropriately selected according to the characteristics of the resin layer, and it is also effective to add a surfactant as needed. The development temperature is preferably 20 to 35 ℃, and a commercially available developing machine, ultrasonic cleaner, or the like can be used to precisely form a fine image. After alkali development, washing with water is usually performed. As the development treatment method, a spray development method, a dip development method, a puddle (immersion) development method, or the like can be used.
After the development is performed in this way, the heat treatment (post baking) is carried out at 180 to 250℃for 20 to 100 minutes. The post baking is performed for the purpose of improving adhesion between the patterned coating film and the substrate, and the like. It can be performed by heating with an oven, a hot plate, or the like, similarly to the prebaking. The patterned coating film of the present invention is formed through the above steps using photolithography. Then, polymerization or curing (both are sometimes collectively referred to as curing) is completed by means of heat, resulting in a cured film pattern. The curing temperature in this case is preferably 160 to 250 ℃.
The photosensitive resin composition of the present invention has a larger number of polymerizable unsaturated groups than conventional photosensitive resin compositions, and thus has improved photocurability, and thus can have an improved crosslink density after curing without increasing the number of photopolymerization initiators. That is, when ultraviolet rays or electron beams are irradiated to a thick film, the cured portion is cured to the bottom, and therefore, the solubility difference between the exposed portion and the unexposed portion with respect to the alkali developer is eliminated, so that the pattern dimensional stability, the development margin, and the pattern adhesion are improved, and a pattern can be formed with high resolution. In the case of a thin film, the residual film amount in the exposed portion can be greatly improved by increasing the sensitivity, and peeling during development can be suppressed.
The photosensitive composition of the present invention is extremely useful for, for example, a solder resist, a plating resist, an etching resist, or an insulating film for multilayer formation of a wiring board for producing a circuit board, various insulating films of a semiconductor device, a gate insulating film of a semiconductor, a photosensitive adhesive (particularly, an adhesive having heat-bonding properties required after patterning by photolithography).
Examples
Embodiments of the present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited to these examples and comparative examples. In the present invention, when the content of each component is 0 in the first decimal place, description below the decimal point may be omitted.
First, a description will be given of a synthesis example of an alkali-soluble resin containing a polymerizable unsaturated group represented by the general formula (1) as the component (i). The resins in these synthesis examples were evaluated as follows, unless otherwise specified.
[ concentration of solid content ]
The resin solutions, photosensitive resin compositions, and the like (1 g) obtained in synthesis examples 1 and 2 and comparative synthesis example were impregnated into a glass filter [ mass: w (W) 0 (g) In performing inWeighing (W) 1 (g) The mass [ W ] of the material after heating at 160℃for 2 hours was used 2 (g) The value is calculated from the following equation.
Solid content concentration (mass%) =100× (W 2 -W 0 )/(W 1 -W 0 )
[ acid value ]
The acid value was measured as follows. The resin solution was dissolved in tetrahydrofuran, and titrated with a 1/10N-KOH aqueous solution using a potential difference titration apparatus "COM-1600" (manufactured by Pingzhou Kogyo Co., ltd.) to obtain the acid value as the amount of KOH required for each 1g of solid content.
[ molecular weight ]
Molecular weight was measured by Gel Permeation Chromatography (GPC) ("HLC-8320 GPC", manufactured by Tosoh corporation, column chromatography: TSKgelSuperH2000 (two) +TSKgelSuperH3000 (one) +TSKgelSuperH4000 (one) +TSKgelSuperH5000 (one) (manufactured by Tosoh corporation), solvent: tetrahydrofuran, temperature: 40 ℃ C., speed: 0.6 ml/min), and the weight average molecular weight (Mw) was determined as a value converted to standard polystyrene (manufactured by Tosoh corporation, PS-oligomer kit).
The abbreviations described in synthesis examples 1 to 3 and comparative synthesis examples are as follows.
BPAEA: the reaction product of 4,4 '-biphenol and 4,4' -dichloromethyl biphenyl (biphenyl aralkyl resin) with epichlorohydrin, and the obtained epoxy compound (199 g/eq of epoxy equivalent, W in the general formula (8) is glycidyl) was further reacted with acrylic acid to obtain a compound (equivalent reaction product of epoxy group and carboxyl group)
BNAEA: the reaction product of 1, 6-dihydroxynaphthalene and terephthaloyl dimethyl ether (naphthalene diphenol aralkyl resin) is reacted with epichlorohydrin, and the obtained epoxy compound (epoxy equivalent 166) is further reacted with acrylic acid to obtain a compound (equivalent reaction product of epoxy group and carboxyl group).
BPDA:3,3', 4' -biphenyltetracarboxylic dianhydride
THPA:1,2,3, 6-tetrahydrophthalic anhydride
SA: succinic anhydride
Tea b: tetraethylammonium bromide
PGMEA: propylene glycol monomethyl ether acetate
The following synthesis examples 1 and 2 are synthesis examples of alkali-soluble resins having a carboxyl group and a polymerizable unsaturated group in one molecule, which are represented by the general formula (1). Further, comparative synthesis example is an epoxy acrylate acid adduct of bisphenol a type epoxy compound, which is an alkali-soluble resin containing a polymerizable unsaturated group having a different skeleton from the alkali-soluble resin represented by the general formula (1). Further, the following synthesis example 3 is a synthesis example of an alkali-soluble resin having a carboxyl group and a polymerizable unsaturated group in one molecule, which is represented by the general formula (1).
Synthesis example 1
(Synthesis of alkali-soluble resin (i) -1) represented by the general formula (1)
A1000 ml four-necked flask equipped with a reflux condenser was charged with a 50% PGMEA solution (419.6 g) of BPAEA, THPA (88.3 g), TEAB (1.63 g) and PGMEA (29.2 g), and stirred at 120 to 125℃for 6 hours to obtain an alkali-soluble resin (i) -1. The solid content concentration of the obtained resin was 56.2wt%, the acid value (in terms of solid content) was 113.6mgKOH/g, and the molecular weight (Mw) measured by GPC analysis was 3410.
Synthesis example 2
(Synthesis of alkali-soluble resin (i) -2) represented by the general formula (1)
A1000 ml four-necked flask equipped with a reflux condenser was charged with a 50% PGMEA solution (419.6 g) of BPAEA, SA (58.1 g), TEAB (1.63 g) and PGMEA (5.2 g), and stirred at 120 to 125℃for 6 hours to obtain an alkali-soluble resin (i) -2. The solid content concentration of the obtained resin was 56.1wt%, the acid value (in terms of solid content) was 125.7mgKOH/g, and the molecular weight (Mw) measured by GPC analysis was 3220.
Comparative Synthesis example
(Synthesis of alkali-soluble resin (i) -3)
A1000 ml four-necked flask equipped with a reflux condenser was charged with a 50% PGMEA solution (442.0 g) of a reactant of bisphenol A type epoxy compound (480 g/eq) and acrylic acid, BPDA (20.6 g), THPA (24.3 g), TEAB (0.84 g) and PGMEA (12.0 g), and stirred at 120 to 125℃for 6 hours to obtain an alkali-soluble resin solution (i) -3. The solid content concentration of the obtained resin was 56.1wt%, the acid value (in terms of solid content) was 62.7mgKOH/g, and the molecular weight (Mw) measured by GPC analysis was 9000.
Synthesis example 3
(Synthesis of alkali-soluble resin (i) -4) represented by the general formula (1)
A1000 ml four-necked flask equipped with a reflux condenser was charged with a 50% PGMEA solution (368.5 g) of BNAEA, THPA (88.3 g), TEAB (1.63 g) and PGMEA (54.7 g), and stirred at 120 to 125℃for 6 hours to obtain an alkali-soluble resin (i) -4. The solid content concentration of the obtained resin was 57.0wt%, the acid value (in terms of solid content) was 126.6mgKOH/g, and the molecular weight (Mw) measured by GPC analysis was 2990. The compound obtained is a compound of the general formula (1), wherein X in the general formula (1) 1 Is a tetravalent naphthalene ring, Y 1 Is xylylene, Q 1 Are all hydrogen atoms. In addition, V 1 The structures are as follows: in the general formula (2), R 1 And L is a hydrogen atom, L is a general formula (3), and M is cyclohexene-1, 2-diyl (residue of 1,2,3, 6-tetrahydrophthalic acid) or p=1 in the general formula (3).
[ experiment 1]
In experiment 1, heat resistance of a cured film of an alkali-soluble resin represented by the general formula (1) and a photosensitive resin composition containing the same was evaluated.
[ evaluation ]
[ evaluation of Heat resistance ]
The substrates with the cured films of the alkali-soluble resins (i) -1 to (i) -3 used for the heat resistance evaluation 1 and the heat resistance evaluation 2 were produced in the following manner.
(production of substrate with cured film for Heat resistance evaluation 1 and Heat resistance evaluation 2)
5g of each of the alkali-soluble resins ((i) -1 to (i) -3) obtained in Synthesis examples 1 and 2 and comparative Synthesis example was diluted with 5g of acetone, and then spread on a 125mm×125mm glass substrate "#1737" (manufactured by Corning Co., ltd.) in a thin manner, and dried at 110℃for 60 minutes, to obtain a substrate with a cured film for use in heat resistance evaluation 1 and heat resistance evaluation 2.
(evaluation method)
The heat resistance of the cured film was evaluated by measuring the change in weight under the atmosphere using a thermogravimetric-differential thermal analysis apparatus (TG-DTA). The cured film on the glass substrate was scraped off and measured. The measurement conditions are shown in Table 1.
TABLE 1
Figure BDA0004195622870000261
The results of heat resistance evaluation 1 and heat resistance evaluation 2 of the cured film are shown in tables 2 and 3.
TABLE 2
Figure BDA0004195622870000262
TABLE 3
Figure BDA0004195622870000263
As shown in tables 2 and 3, it is found that the cured product of the alkali-soluble resin containing the polymerizable unsaturated group represented by the general formula (1) has high heat resistance.
Next, photosensitive resin compositions of example 1 and example 2 were prepared in accordance with the amounts (in mass%) shown in Table 4. The blending components used in table 4 were as follows.
(alkali-soluble resin containing polymerizable unsaturated group)
(i) -1: the alkali-soluble resin having a polymerizable unsaturated group obtained in Synthesis example 1
(i) -2: the alkali-soluble resin having a polymerizable unsaturated group obtained in Synthesis example 2
(photopolymerizable monomer)
(ii) The method comprises the following steps Dipentaerythritol hexaacrylate
(photopolymerization initiator)
(iii) The method comprises the following steps 1-hydroxycyclohexyl phenyl ketone (trade name: omnirad184, manufactured by IGM Resins B.V. Co., ltd.)
(solvent)
PGMEA
TABLE 4
Composition of the components Example 1 Example 2
(i)-i 30.1
(i)-2 30.1
(ii) 7.5 7.5
(iii) 0.8 0.8
Solvent(s) 61.6 61.6
A substrate with a cured film containing the photosensitive resin composition of alkali-soluble resin ((i) -1 or (i) -2) for heat resistance evaluation 3 was produced in the following manner.
(production of substrate with cured film for Heat resistance evaluation 3)
The photosensitive resin compositions shown in Table 4 containing the alkali-soluble resins ((i) -1 or (i) -2) were coated on a glass substrate by using a spin coater so that the film thickness after post baking became 1.0 to 1.5. Mu.m, and pre-baked at 90℃for 1 minute, to prepare coated plates. Then, 500W/cm was used 2 The high-pressure mercury lamp of (2) was irradiated with ultraviolet light having a wavelength of 365nm over the entire surface thereof to effect a photo-curing reaction. Then, a heat curing treatment was performed at 230℃for 30 minutes using a hot air dryer, whereby a cured film for heat resistance evaluation 3 was obtained.
(evaluation method)
The heat resistance of the cured film obtained for heat resistance evaluation 3 was evaluated by the same method as the above-described heat resistance evaluation. The cured film on the glass substrate was scraped for measurement. The measurement conditions are shown in Table 5.
TABLE 5
Figure BDA0004195622870000271
The results of the above heat resistance evaluation 3 are shown in Table 6.
TABLE 6
Figure BDA0004195622870000272
As shown in table 6, it is found that the photosensitive resin composition containing the alkali-soluble resin represented by the general formula (1) has high heat resistance.
[ experiment 2]
In experiment 2, various properties required for use of the photosensitive resin composition containing the alkali-soluble resin represented by the general formula (1) in an insulating film or the like were evaluated.
Photosensitive resin compositions of examples 3 to 5 and comparative example 2 were prepared in accordance with the amounts (in mass%) shown in table 7. The ingredients used in table 7 were as follows.
(alkali-soluble resin containing polymerizable unsaturated group)
(i) -1: the alkali-soluble resin obtained in Synthesis example 1
(i) -2: the alkali-soluble resin obtained in Synthesis example 2
(i) -3: comparison of alkali-soluble resin obtained in Synthesis example 1
(i) -4: the alkali-soluble resin obtained in Synthesis example 3
(photopolymerizable monomer)
(ii) The method comprises the following steps Dipentaerythritol hexaacrylate
(photopolymerization initiator)
(iii) -1: omnirad 184 (IGM RESINS B.V. Co., ltd.)
(iii) -2: p, p '-bis (dimethylamino) benzophenone (Michler's ketone)
(epoxy resin)
(iv) The method comprises the following steps Cresol novolak type epoxy resin (YDCN-700-7, epoxy equivalent 200g/eg, softening point 70 ℃ C., nissan iron chemical Co., ltd.)
(solvent)
PGMEA
TABLE 7
Composition of the components Example 3 Example 4 Example 5 Comparative example 2
(i)-1 51.9
(i)-2 52.0
(i)-3 52.0
(i)-4 51.1
(ii) 12.5 12.5 12.5 12.5
(iii)-1 1.3 1.3 1.3 1.3
(iii)-2 0.2 0.2 0.2 0.2
(iv) 6.2 6.2 6.2 6.2
Solvent(s) 27.9 27.8 28.7 27.8
[ evaluation of photosensitive resin compositions of examples 3 to 5 and comparative example 2 ]
The photosensitive resin composition shown in Table 7 was applied to a 125mm X125 mm glass substrate by using a spin coater so that the film thickness after post baking became 10. Mu.m, and pre-baked at 90℃for 3 minutes to prepare a coated plate. Then, 500W/cm was used via a photomask for patterning 2 Ultraviolet rays with a wavelength of 365nm are irradiated by a high-pressure mercury lamp, and a photo-curing reaction is performed on the exposed portion. Then, the exposed coated plate was subjected to spray development with a 1.0wt% aqueous sodium carbonate solution at 23℃for 20 seconds after the time of pattern appearance, and then subjected to spray water washing to remove the unexposed portion of the coating film. Then, a heat curing treatment was performed at 230℃for 30 minutes using a hot air dryer to obtain examples 1 to 1 The cured films of example 3 and comparative example 2.
The cured film was evaluated as follows. The results are shown in Table 8.
(sensitivity)
The photosensitive resin composition shown in Table 7 was applied to a 125mm X125 mm glass substrate by using a spin coater so that the film thickness after post baking became 10. Mu.m, and pre-baked at 90℃for 3 minutes to prepare a coated plate. Then, a photomask having a transmittance of 500W/cm was used, in which the transmittance was continuously changed from 0% to 100% 2 Ultraviolet rays with a wavelength of 365nm are irradiated by a high-pressure mercury lamp, and a photo-curing reaction is performed on the exposed portion. Then, the exposed coated plate was subjected to spray development with a 1.0wt% aqueous sodium carbonate solution at 23℃for a further 10 seconds from the time when the pattern was formed, and then subjected to spray water washing to remove the unexposed portion of the coating film. Then, a heat curing treatment was performed at 230℃for 30 minutes using a hot air dryer, and the minimum exposure (mJ/cm) of the cured film residue was calculated 2 )。
(method for measuring adhesion and residue)
The adhesion of the thin line pattern of the cured film was confirmed by an electron microscope "VHX5000" (manufactured by KEYENCE) and evaluated according to the following criteria.
The adhesion was evaluated as follows.
O: a pattern having an L/S (line width/space width) of 30 μm/30 μm or more is formed
X: no pattern having an L/S (line width/space width) of less than 30 μm/30 μm is formed
The evaluation criteria for the residue were as follows.
O: in a pattern having an L/S (line width/space width) of 30 μm/30 μm or more, there is no residue between the patterns
X: in the patterns with L/S (line width/space width) of 30 μm/30 μm or more, residues between patterns are remarkable
(method for measuring linearity)
The linearity of the thin line pattern of the cured film was confirmed by an electron microscope "VHX5000" (manufactured by KEYENCE) and evaluated according to the following criteria.
O: no peeling or chipping of the fine line pattern from the glass substrate and jaggy at the pattern end were found
X: it was found that the thin line pattern was peeled off or defective from the glass substrate and the end of the pattern was jagged
(Cone shape)
The taper shape was observed by using a scanning electron microscope "VE-7800" (manufactured by KEYENCE Co., ltd.) using a negative photomask provided with a line-space pattern of 1 to 100 μm, and the pattern was exposed and developed, and evaluated according to the following criteria.
And (3) the following materials: the cross-sectional shape being approximately vertical
O: the cross section is trapezoid, and the inner angle between the pattern side surface and the pattern end formed by the glass substrate is 90-60 DEG
Delta: smooth and round cross-sectional shape
X: the cross section is trapezoid, and the inner angle of the pattern end formed by the pattern side surface and the glass substrate is more than 90 DEG
TABLE 8
Example 3 Example 4 Example 5 Comparative example 2
Sensitivity of sensitivity 6 10 13 13
Adhesion of ○ ○ ○ ○
Residues from the treatment of plant diseases ○ ○ ○ ○
Linearity of straight line ○ ○ ○ ○
Conical shape ◎ ◎ ○ △
As shown in table 8, it was found that the photosensitive resin compositions containing the alkali-soluble resin prepared in examples 3 to 5 can form cured film patterns excellent in taper shape while achieving both high adhesion and residue suppression.
As described above, the photosensitive resin composition containing an alkali-soluble resin of the present invention is applicable to a case where a cured film having excellent dimensional accuracy and pattern cross-sectional shape is required to be formed, such as a solder resist, plating resist, etching resist, etc. used for producing a circuit board, the cured film being a cured film formed by photolithography, such as a color filter or a light shielding film of a liquid crystal display device, an organic EL display device, a LED display device, an image sensor, etc.
The present application claims priority based on japanese patent application publication No. 2020-182575 filed on 10 months and 30 days in 2020. The content described in the specification and claims of this application is incorporated into the specification and claims of this application in its entirety.
Industrial applicability
The photosensitive resin composition containing the alkali-soluble resin of the present invention is useful as a resist for an insulating film for producing a solder resist, a plating resist, an etching resist, a semiconductor device, etc. of a circuit board, and a cured product thereof is useful as a protective film for a component part of a liquid crystal display device, an organic EL display device, a LED display device, an image sensor, etc., a color filter, a light shielding film, etc., and various cured films formed by photolithography.

Claims (9)

1. An alkali-soluble resin represented by the following general formula (1) and having a carboxyl group and a polymerizable unsaturated group in one molecule,
[ chemical formula 1]
Figure FDA0004195622860000011
In the formula (1), X 1 Represents tetravalent aromatic ring-containing groups, Y 1 Represents a divalent aromatic ring-containing group, X 1 And Y 1 Part of hydrogen atoms of (C) may be substituted with a straight-chain or branched hydrocarbon group having 1 to 20 carbon atoms, V 1 The average value of 1 is 0.2 to 4.0 and Q is a substituent represented by the following general formula (2) 1 Is a hydrogen atom or a straight-chain or branched hydrocarbon group having 1 to 20 carbon atoms;
[ chemical formula 2]
Figure FDA0004195622860000012
In the formula (2), R 1 Representing hydrogen atomsA substituent represented by the following general formula (3), wherein L represents a site bonded to an oxygen atom O in the formula (1);
[ chemical formula 3]
Figure FDA0004195622860000013
In formula (3), M represents a divalent or trivalent residue derived from a dicarboxylic acid, a tricarboxylic acid, or an acid monoanhydride of these, p is 1 or 2, and x represents a site bonded to an oxygen atom O in formula (2).
2. The alkali-soluble resin according to claim 1, wherein X 1 Is a tetravalent substituent represented by the following general formula (5), Y 1 In the following general formula (5) and general formula (6), a part of hydrogen atoms may be substituted with a straight-chain or branched hydrocarbon group having 1 to 20 carbon atoms,
[ chemical formula 4]
Figure FDA0004195622860000021
In formula (5), the oxygen atom O, Y in formula (1) 1 Or Q 1 Bonding sites;
[ chemical formula 5]
Figure FDA0004195622860000022
In the formula (6), X in the formula (1) 1 Bonding sites.
3. The alkali-soluble resin according to claim 1, wherein X 1 Is a tetravalent substituent derived from naphthalene diphenol.
4. A photosensitive resin composition comprising, as essential components:
(i) The alkali-soluble resin according to any one of claims 1 to 3;
(ii) A photopolymerizable monomer having at least one polymerizable unsaturated group; and
(iii) A photopolymerization initiator.
5. The photosensitive resin composition according to claim 4, wherein the content of the component (iii) is 0.1 to 10 parts by mass based on 100 parts by mass of the total of the component (i) and the component (ii).
6. The photosensitive resin composition according to claim 4 or claim 5, which contains (iv) an epoxy compound.
7. The photosensitive resin composition according to claim 6, wherein the content of the component (iv) is 10 to 40 parts by mass based on 100 parts by mass of the total of the component (i) and the component (ii).
8. The photosensitive resin composition according to any one of claims 4 to 7, which contains (v) a dispersoid.
9. A cured product obtained by curing the photosensitive resin composition according to any one of claims 4 to 8.
CN202180072635.0A 2020-10-30 2021-10-29 Alkali-soluble resin containing polymerizable unsaturated group, photosensitive resin composition containing the resin as essential component, and cured product thereof Pending CN116348522A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2020-182575 2020-10-30
JP2020182575 2020-10-30
PCT/JP2021/040078 WO2022092281A1 (en) 2020-10-30 2021-10-29 Polymerizable unsaturated group-containing alkali-soluble resin, photosensitive resin composition containing same as essential component, and cured product thereof

Publications (1)

Publication Number Publication Date
CN116348522A true CN116348522A (en) 2023-06-27

Family

ID=81384025

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202180072635.0A Pending CN116348522A (en) 2020-10-30 2021-10-29 Alkali-soluble resin containing polymerizable unsaturated group, photosensitive resin composition containing the resin as essential component, and cured product thereof

Country Status (5)

Country Link
JP (1) JPWO2022092281A1 (en)
KR (1) KR20230098173A (en)
CN (1) CN116348522A (en)
TW (1) TW202229370A (en)
WO (1) WO2022092281A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI812336B (en) * 2022-07-08 2023-08-11 新應材股份有限公司 Resin composition and cured film

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63205650A (en) * 1987-02-20 1988-08-25 Unitika Ltd Alkaline development type photosensitive resin composition
JPH01203424A (en) * 1988-02-09 1989-08-16 Toagosei Chem Ind Co Ltd Curable composition
JPH0371137A (en) * 1989-08-11 1991-03-26 Tamura Kaken Kk Photosensitive resin composition
JP6562249B2 (en) * 2015-06-05 2019-08-21 Dic株式会社 (Meth) acrylate resin and resist member

Also Published As

Publication number Publication date
TW202229370A (en) 2022-08-01
KR20230098173A (en) 2023-07-03
WO2022092281A1 (en) 2022-05-05
JPWO2022092281A1 (en) 2022-05-05

Similar Documents

Publication Publication Date Title
JP5133658B2 (en) Photosensitive resin composition for black matrix, cured product and color filter using the same
JPH061938A (en) Alkali-developable photo-sensitive ink for color filter and color filter produced by using the ink
JP3813244B2 (en) Alkali developable unsaturated resin composition and highly sensitive negative pattern forming material using the same
JP2015214684A (en) Alkali-soluble resin, photosensitive resin composition comprising the same, cured product using the same, and touch panel and color filter including said cured product as constituent
JP5449666B2 (en) Alkali-soluble resin and method for producing the same, and photosensitive resin composition, cured product, and color filter using alkali-soluble resin
KR20080049681A (en) Alkali soluble resin, process for producing the same, photosensitive resin composition containing the same, cured product, and color filter
WO2021235299A1 (en) Polymerizable-unsaturated-group-containing alkali-soluble resin, method for producing same, photosensive resin composition, and cured product thereof
JP7260524B2 (en) Method for producing polymerizable unsaturated group-containing alkali-soluble resin, polymerizable unsaturated group-containing alkali-soluble resin, photosensitive resin composition containing same as essential component, and cured film thereof
CN116348522A (en) Alkali-soluble resin containing polymerizable unsaturated group, photosensitive resin composition containing the resin as essential component, and cured product thereof
JP7376978B2 (en) Photosensitive resin composition, method for producing cured product, and method for producing display device
JP7049150B2 (en) A photosensitive resin composition containing a polymerizable unsaturated group-containing alkali-soluble resin as an essential component, and a cured film thereof.
JP7368162B2 (en) Polymerizable unsaturated group-containing alkali-soluble resin, method for producing the same, photosensitive resin composition, and cured film thereof.
JP7250591B2 (en) A method for producing a polymerizable unsaturated group-containing alkali-soluble resin, a polymerizable unsaturated group-containing alkali-soluble resin, a photosensitive resin composition containing the same, a cured product obtained by curing the same, and a touch panel containing the cured product as a constituent component and color filters
CN111886274B (en) Alkali-soluble resin containing unsaturated group, photosensitive resin composition containing the same as essential component, and cured product thereof
JP6289006B2 (en) White photosensitive resin composition, cured product using the same, and touch panel including the cured product as a constituent component
JP7089914B2 (en) A photosensitive resin composition containing an unsaturated group-containing alkali-soluble resin as an essential component and a cured product thereof.
KR20210122191A (en) Polymerizable unsaturated group-containing alkali-soluble resin, photosensitive resin composition containing the same, and cured product of that
JP7478553B2 (en) Hydrogenated compound and its manufacturing method, polymerizable unsaturated group-containing alkali-soluble resin, photosensitive resin composition containing same, cured product obtained by curing the same, and touch panel and color filter containing the cured product as a constituent component
KR20220131162A (en) Photosensitive resin, photosensitive resin composition containing the same, cured product, and color filter
CN111748077A (en) Alkali-soluble resin, hydrogenated compound, method for producing same, resin composition, cured film of resin composition, touch panel, and optical filter
CN111752101A (en) Photosensitive resin composition, cured film, substrate with cured film, and method for producing substrate with cured film
CN111752102A (en) Photosensitive resin composition, cured film, substrate with cured film, and method for producing substrate with cured film
CN112538157A (en) Epoxy acrylate resin, alkali-soluble resin and method for producing the same, curable and photosensitive resin composition and cured product thereof
KR20240064539A (en) Photosensitive resin composition for black resist, light-shielding film cured thereof, color filter and touch panel having that film, and display device having them
CN113867099A (en) Photosensitive resin composition for black resist, method for producing same, light-shielding film, color filter, touch panel, and display device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination