CN114729073A - (meth) acrylate, curable resin composition, and cured product - Google Patents
(meth) acrylate, curable resin composition, and cured product Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/734—Ethers
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- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
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- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/106—Esters of polycondensation macromers
- C08F222/1063—Esters of polycondensation macromers of alcohol terminated polyethers
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/40—Ortho- or ortho- and peri-condensed systems containing four condensed rings
- C07C2603/42—Ortho- or ortho- and peri-condensed systems containing four condensed rings containing only six-membered rings
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Abstract
The purpose of the present invention is to provide a novel (meth) acrylate which is a material for forming a cured product that can maintain high insulation properties for a long period of time under high temperature and high humidity, a curable resin composition containing the same, and a cured product obtained by curing the curable resin composition. The novel (meth) acrylic acid esters are prepared by using the following general formula (1) or(2) And (4) showing. In the formula (1), R1～R4Each independently is H or methyl, R5～R7Independently represents a halogen group, an alkyl group, an alkoxy group or an aryl group, AO represents an ethyleneoxy group or a propyleneoxy group, m and n independently represent an integer of 0 to 5, p represents an integer of 0 to 2, and r and s independently represent an integer of 0 to 15; in the formula (2), R1～R4Each independently is H or methyl, R5～R7Independently represents a halogen group, an alkyl group, an alkoxy group or an aryl group, AO represents an ethyleneoxy group or a propyleneoxy group, m and n independently represent an integer of 0 to 5, p represents an integer of 0 to 2, and r and s independently represent an integer of 0 to 15;
Description
Technical Field
The present invention relates to a novel (meth) acrylate, a curable resin composition containing the (meth) acrylate, and a cured product obtained by curing the curable resin composition.
Background
With the recent miniaturization of electronic components, the distance between the wirings of a circuit board has become narrow, and the insulation of an insulating film used between the wirings has become more and more important for the miniaturization of electronic components. In particular, electronic components such as circuit boards are used in severe environments such as high temperature and high humidity, and insulating films for electronic components are required to maintain high insulation even in such severe environments.
Conventionally, photosensitive polyimide has been used as an insulating film for such applications, but since a step of applying heat at 300 to 400 ℃ is included in a film formation step, there is a possibility that the performance of an electronic component may be deteriorated by heat.
Further, acrylic and epoxy photosensitive materials other than polyimide have the following problems: when used under severe environments such as high temperature and high humidity, insulation deterioration is likely to occur.
Patent document 1 discloses a thermally conductive sheet body that can realize a semiconductor device having high insulation reliability, the thermally conductive sheet body including a thermosetting resin and an inorganic filler dispersed in the thermosetting resinThe volume resistivity of the cured product of the thermally conductive sheet at 175 ℃ measured after applying a voltage of 1000V for 1 minute according to JIS K6911 was 1.0X 108Omega · m or more.
Patent document 2 discloses a photosensitive resin composition having excellent light-shielding properties and insulation properties and having a high resistance, which contains (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator having a specific structure, and (d) a high-resistance carbon black as a color material.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2015-146387
Patent document 2: international publication No. 2019/065789
Disclosure of Invention
Problems to be solved by the invention
However, the cured films obtained from the thermal conductive sheet disclosed in patent document 1 and the photosensitive resin composition disclosed in patent document 2 cannot maintain high insulation properties for a long time under high temperature and high humidity.
The purpose of the present invention is to provide a novel (meth) acrylate which is a material for forming a cured product that can maintain high insulation properties for a long period of time under high temperature and high humidity conditions, a curable resin composition containing the (meth) acrylate, and a cured product obtained by curing the curable resin composition.
Means for solving the problems
The present inventors have made extensive studies to solve the above problems, and as a result, have found that the above objects can be achieved by a novel (meth) acrylate, a curable resin composition, and a cured product shown below, and have completed the present invention.
The present invention relates to a (meth) acrylic acid ester represented by the following general formula (1) or (2).
In the formula (1), the reaction mixture is,R1～R4each independently is H or methyl, R5～R7Independently represents a halogen group, an alkyl group, an alkoxy group or an aryl group, AO represents an ethyleneoxy group or an propyleneoxy group, m and n independently represent an integer of 0 to 5, p represents an integer of 0 to 2, and r and s independently represent an integer of 0 to 15.
In the formula (2), R1～R4Each independently is H or methyl, R5～R7Independently represents a halogen group, an alkyl group, an alkoxy group or an aryl group, AO represents an ethyleneoxy group or an propyleneoxy group, m and n independently represent an integer of 0 to 5, p represents an integer of 0 to 2, and r and s independently represent an integer of 0 to 15.
The curable resin composition of the present invention contains at least one of the (meth) acrylates, a base polymer, a polymerization initiator, and a solvent.
The content of the (meth) acrylate in the curable resin composition is preferably 20 to 100 parts by mass with respect to 100 parts by mass of the base polymer.
The curable resin composition preferably further contains a polyfunctional monomer and/or an epoxy resin.
The cured product of the present invention is a cured product obtained by curing the curable resin composition.
The water absorption of the cured product is preferably 1% or less.
Effects of the invention
The cured product obtained by curing the curable resin composition of the present invention uses the (meth) acrylate represented by the general formula (1) and/or (2), and therefore has very low water absorption and can maintain high insulation properties for a long period of time under high temperature and high humidity.
Detailed Description
< the (meth) acrylate represented by the general formula (1) or (2) >)
The novel (meth) acrylate of the present invention is represented by the following general formula (1) or (2) (hereinafter, also referred to collectively as (meth) acrylate X). In the present invention, the term (meth) acrylate means acrylate, methacrylate or a mixture thereof. Other compounds described in the same manner also have similar meanings.
In the formula (1), R1～R4Each independently is H or methyl, R5～R7Independently represents a halogen group, an alkyl group, an alkoxy group or an aryl group, AO represents an ethyleneoxy group or an propyleneoxy group, m and n independently represent an integer of 0 to 5, p represents an integer of 0 to 2, and r and s independently represent an integer of 0 to 15.
In the formula (2), R1～R4Each independently is H or methyl, R5～R7Independently represents a halogen group, an alkyl group, an alkoxy group or an aryl group, AO represents an ethyleneoxy group or an propyleneoxy group, m and n independently represent an integer of 0 to 5, p represents an integer of 0 to 2, and r and s independently represent an integer of 0 to 15.
In the above formula, the halogen group is not particularly limited, and examples thereof include fluorine, chlorine, bromine, iodine and the like.
In the above formula, the alkyl group is not particularly limited, and may be a linear, branched, cyclic alkyl group or an alkyl group obtained by combining these. The number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 to 10, preferably 1 to 5, and more preferably 1 to 3.
In the above formula, the alkoxy group is not particularly limited, and may be a linear, branched or cyclic alkoxy group or a combination thereof. The number of carbon atoms of the alkoxy group is not particularly limited, but is usually 1 to 10, preferably 1 to 5, and more preferably 1 to 3.
In the above formula, the aryl group is not particularly limited, and may be an aromatic hydrocarbon group or an aromatic heterocyclic group. In addition, the aryl group may have a substituent.
In the above formula, AO is an ethyleneoxy group or a propyleneoxy group, and when m and n are integers of 2 or more, AO may be only an ethyleneoxy group, may be only a propyleneoxy group, and may be an ethyleneoxy group and a propyleneoxy group.
In the above formula, m and n are each independently an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 0 or 1, and still more preferably 0.
In the above formula, p is an integer of 0 to 2, preferably 0 or 1, more preferably 0.
In the above formula, r and s are each independently an integer of 0 to 15, preferably an integer of 0 to 10, more preferably an integer of 0 to 5, and still more preferably 0.
Examples of the (meth) acrylate represented by the above general formula (1) include (meth) acrylates represented by the following formula (3).
For example, a (meth) acrylic ester represented by the above general formula (1) can be synthesized by reacting a compound represented by the following general formula (4) with (meth) acrylic anhydride in the presence of a base catalyst.
In the formula (4), R5～R7AO, m, n, p, r and s are the same as described above.
Examples of the base catalyst include sodium amide (sodium amide), triethylamine, tributylamine, trioctylamine, pyridine, dimethylaminopyridine, N-dimethylaniline, 1, 5-diazabicyclo [4,3,0] nonene-5 (DBN), 1, 8-diazabicyclo [5,4,0] undecene-7 (DBU), sodium hydroxide, potassium hydroxide, sodium hydride, sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate, silver oxide, sodium methoxide, and potassium tert-butoxide.
Examples of the (meth) acrylate represented by the above general formula (2) include (meth) acrylates represented by the following formula (5).
For example, a (meth) acrylic ester represented by the above general formula (2) can be synthesized by reacting a compound represented by the following general formula (6) with (meth) acrylic anhydride in the presence of a basic catalyst.
In the formula (6), R5～R7AO, m, n, p, r and s are the same as described above.
Examples of the base catalyst include the above-mentioned base catalysts.
< curable resin composition >
The curable resin composition of the present invention contains at least one of the (meth) acrylate X, a base polymer, a polymerization initiator, and a solvent.
The content of the (meth) acrylate X in the curable resin composition is not particularly limited, but is preferably 20 to 100 parts by mass, more preferably 20 to 80 parts by mass, and even more preferably 20 to 40 parts by mass, based on 100 parts by mass of the base polymer, from the viewpoint of reducing the water absorption rate of the resulting cured product and from the viewpoint of film-forming properties.
The base polymer is not particularly limited, and examples thereof include: a poly (meth) acrylic resin, a polyurethane resin, a polyethylene resin, a polystyrene resin, a polyethylene resin, a polypropylene resin, a polyimide resin, a polyamide resin, a polyacetal resin, a polycarbonate resin, a polyester resin, an epoxy resin, a phenol resin, a urea resin, a melamine resin, a polyphenylene ether resin, a polyphenylene sulfide resin, a polyether sulfone resin, a polyether ether ketone resin, and the like, and these may be used alone or in combination of two or more. Among them, a poly (meth) acrylic resin is preferably used.
The monomer for forming the poly (meth) acrylic resin is not particularly limited, and examples thereof include alkyl (meth) acrylates, alkoxy group-containing (meth) acrylates, alicyclic group-containing (meth) acrylates, aryl group-containing (meth) acrylates, hydroxyl group-containing (meth) acrylates, epoxy group-containing (meth) acrylates, and carboxyl group-containing (meth) acrylates. These may be used alone or in combination of two or more.
Examples of the alkyl (meth) acrylate include: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, sec-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, isostearyl (meth) acrylate, heneicosyl (meth) acrylate, behenyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate, and the like. These may be used alone or in combination of two or more.
Examples of the (meth) acrylate containing an alkoxy group include 2-methoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, and ethylcarbitol (meth) acrylate. These may be used alone or in combination of two or more.
Examples of the (meth) acrylate containing an alicyclic group include cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and adamantyl (meth) acrylate. These may be used alone or in combination of two or more.
Examples of the aryl group-containing (meth) acrylate include aryl group-containing (meth) acrylates having 6 to 15 carbon atoms such as phenyl (meth) acrylate, benzyl (meth) acrylate, and phenoxyethyl (meth) acrylate. These may be used alone or in combination of two or more.
Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, and 12-hydroxylauryl (meth) acrylate. These may be used alone or in combination of two or more.
Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate and epoxycyclohexyl (meth) acrylate. These may be used alone or in combination of two or more.
Examples of the (meth) acrylate having a carboxyl group include acrylic acid, methacrylic acid, carboxyethyl (meth) acrylate, carboxybutyl (meth) acrylate, and carboxypentyl (meth) acrylate. These may be used alone or in combination of two or more.
In addition, 2- (meth) acryloyloxyethylsuccinic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, vinyl acetate, vinyl propionate, styrene, α -methylstyrene, N-vinylcaprolactam, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, N-butylmaleimide, laurylmaleimide, a polysiloxane (silicone) -containing monomer, and the like can also be used as a comonomer. These may be used alone or in combination of two or more.
From the viewpoint of reducing the water absorption of the cured product, the alicyclic group-containing (meth) acrylate is preferably used in an amount of 20 mass% or more, more preferably 30 mass% or more, based on the total monomers forming the poly (meth) acrylic resin. From the same viewpoint, the aromatic group-containing (meth) acrylate is preferably used in an amount of 10 mass% or more, more preferably 20 mass% or more, based on the total monomers forming the poly (meth) acrylic resin. From the same viewpoint, the carboxyl group-containing monomer is preferably used in an amount of 5 mass% or more, more preferably 10 mass% or more, based on the total monomers forming the poly (meth) acrylic resin.
The weight average molecular weight of the poly (meth) acrylic resin is not particularly limited, but is preferably 5000 to 100000, and more preferably 10000 to 30000, from the viewpoint of easy formation of a fine pattern (hereinafter, also referred to as good image resolution) when the poly (meth) acrylic resin is contained in a curable resin composition. The above range is also preferable for the weight average molecular weight of other types of base polymers. The weight average molecular weight of the base polymer containing the poly (meth) acrylic resin is a value in terms of polystyrene measured using Gel Permeation Chromatography (GPC), and is a value measured in accordance with JIS 7252-4. The weight average molecular weight described in the examples described later is also a value obtained according to the description of this item.
The acid value of the poly (meth) acrylic resin is not particularly limited, but is preferably 10 to 200(mgKOH/g), more preferably 30 to 100(mgKOH/g), from the viewpoint of resolution.
As the polymerization initiator, a photopolymerization initiator is preferably used. The photopolymerization initiator is not particularly limited, and examples thereof include: benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, and alkyl ethers thereof; acetophenones such as acetophenone, 2-dimethoxy-2-phenylacetophenone, 1-dichloroacetophenone and the like; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; thioxanthones such as 2, 4-dimethylthioxanthone, 2, 4-diisopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone; 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinyl-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1; acylphosphine oxides, xanthones, and the like. These photopolymerization initiators may be used alone, or two or more of them may be used in combination.
The content of the photopolymerization initiator is not particularly limited, and is preferably 1 part by weight or more, more preferably 5 parts by weight or more, and preferably 15 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total polymerizable raw materials in the curable resin composition.
The curable resin composition may contain a photopolymerization initiator. Examples of the photopolymerization initiation aid include: trifunctional thiol compounds such as 1,3, 5-tris (3-mercaptopropionyloxyethyl) -isocyanurate and 1,3, 5-tris (3-mercaptobutyloxyethyl) -isocyanurate (manufactured by showa electric corporation, Karenz MT (registered trademark) NR1) and trimethylolpropane tris (3-mercaptopropionate); tetrafunctional thiol compounds such as pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by showa electric corporation, Karenz MT (registered trademark) PEI); and polyfunctional mercaptans such as hexafunctional mercaptan compounds such as dipentaerythritol hexa (3-propionate). These photopolymerization initiation aids may be used alone or in combination of two or more.
The curable resin composition may contain a thermal polymerization initiator. Examples of the thermal polymerization initiator include: organic peroxides such as cumene hydroperoxide, dicumyl peroxide (diisopropylbenone peroxide), di-tert-butyl peroxide, lauryl peroxide, benzoyl peroxide, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxy-2-ethylhexanoate, and tert-amyl peroxy-2-ethylhexanoate; azo compounds such as 2,2 '-azobis (isobutyronitrile), 1' -azobis (cyclohexanecarbonitrile), 2 '-azobis (2, 4-dimethylvaleronitrile), and dimethyl 2, 2' -azobis (2-methylpropionate). These thermal polymerization initiators may be used alone, or two or more thereof may be used in combination.
Examples of the solvent include: ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate; alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; chloroform, dimethylsulfoxide, and the like. These solvents may be used alone, or two or more of them may be used in combination. The content of the solvent is not particularly limited, and may be appropriately adjusted according to the optimum viscosity and the like when the composition is used.
The curable resin composition may further contain a polyfunctional monomer other than the (meth) acrylate X. The polyfunctional monomer is not particularly limited, and examples thereof include: polyfunctional aromatic vinyl monomers such as divinylbenzene, diallyl phthalate and diallyl phenylphosphonate; polyfunctional (meth) acrylates such as (di) ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tri (meth) acrylate of tris (hydroxyethyl) isocyanurate, and the like. Among these, preferred are (di) pentaerythritol tetra (meth) acrylate, (di) pentaerythritol penta (meth) acrylate, (di) pentaerythritol hexa (meth) acrylate, and tri (meth) acrylate of tris (hydroxyethyl) isocyanurate, which have a large number of functional groups. These polyfunctional monomers may be used alone or in combination of two or more.
The content of the polyfunctional monomer in the curable resin composition is not particularly limited, but is preferably 20 to 100 parts by mass, more preferably 20 to 50 parts by mass, and even more preferably 20 to 40 parts by mass, based on 100 parts by mass of the base polymer, from the viewpoints of reducing the water absorption rate of the resulting cured product and film-forming properties.
The curable resin composition may further contain an epoxy resin. The epoxy resin is different from the epoxy resin used as the base polymer, and is an epoxy resin having a smaller molecular weight than the epoxy resin. Therefore, the curable resin composition may contain an epoxy resin as a base polymer, and may further contain an epoxy resin. Representative examples of the epoxy resin include low molecular weight resins, oligomers, and monomers having an epoxy skeleton, and the weight average molecular weight is about 1000 or less. The epoxy resin is not particularly limited, and examples thereof include bisphenol a type epoxy compounds, bisphenol F type epoxy compounds, glycidyl ether type epoxy compounds, glycidyl ester type epoxy compounds, biphenyl type epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, bisphenol a novolac type epoxy compounds, aliphatic polyglycidyl ether compounds, cyclic aliphatic epoxy compounds, polymers of monomers having an epoxy group, copolymers of monomers having an epoxy group and other monomers, and epoxy compounds having a siloxane bonding site. These epoxy resins may be used alone or in combination of two or more.
The content of the epoxy resin in the curable resin composition is not particularly limited, and is preferably 10 to 100 parts by mass, more preferably 10 to 50 parts by mass, and even more preferably 10 to 30 parts by mass, based on 100 parts by mass of the base polymer, from the viewpoint of reducing the water absorption of the resulting cured product and from the viewpoint of film-forming property.
The curable resin composition may further contain a radical polymerizable oligomer such as an unsaturated polyester, an epoxy acrylate, an urethane acrylate, or a polyester acrylate.
The curable resin composition may contain well-known additives such as an adhesion-imparting agent, a coating property-improving agent, a dye, a pigment, an antifoaming agent, a coupling agent, a leveling agent (leveling agent), a sensitizer, a release agent, a lubricant, a plasticizer, an antioxidant, an ultraviolet absorber, a flame retardant, a thickener, and a dispersant, as long as the effects of the present invention are not impaired.
The solid content concentration of the curable resin composition is not particularly limited, but is preferably 10 to 60% by mass, more preferably 20 to 50% by mass, from the viewpoint of film forming property of the resulting cured product.
< cured product >
The curable resin composition is cured to obtain a cured product of the present invention. Examples of the method for producing the cured product include the following methods: the curable resin composition is cured by injecting the curable resin composition into a molding die (resin die), or by applying the curable resin composition to a substrate (substrate) or various layers to form a desired shape, and then irradiating the substrate or various layers with light (e.g., ultraviolet light) and/or heating the substrate or various layers. The conditions for curing are appropriately adjusted according to the curable resin composition to be used.
The cured product of the present invention has a very low water absorption rate and is characterized by being capable of maintaining high insulation properties for a long time under high temperature and high humidity. The water absorption of the cured product is preferably 1% or less, more preferably 0.9% or less, and still more preferably 0.8% or less.
The use of the cured product of the present invention is not particularly limited, and the cured product can be suitably used as a member requiring insulation properties (for example, an insulating film resist, an insulating sheet, an insulating layer, and the like). Examples of the use include: semiconductor elements/integrated circuits (ICs and the like), discrete semiconductors (diodes, transistors, thermistors and the like), LEDs (LED lamps, chip LEDs, light receiving elements, lenses for optical semiconductors), sensors (temperature sensors, optical sensors, magnetic sensors), passive components (high-frequency devices, resistors, capacitors and the like), mechanical components (connectors, switches, relays and the like), automobile components (circuit systems, control systems, sensors, lamp seals (lamp seals) and the like), adhesives/adhesives (optical components, optical disks, pickup lenses (and the like)), surface protective films, optical films and the like.
Examples
The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
[ production of base Polymer ]
Production example 1-1
20.0g of methacrylic acid, 34.1g of dicyclopentyl methacrylate and 21.0g of benzyl acrylate were placed in a glass flask equipped with a heating, cooling and stirring device, a reflux condenser and a nitrogen inlet. After the gas phase portion in the system was replaced with nitrogen, 4.8g of 2, 2' -azobis (isobutyronitrile) was added, and the mixture was heated to 80 ℃ to react at the same temperature for 8 hours. Thereafter, 20.3g of 3, 4-epoxycyclohexylmethyl methacrylate, 0.2g of triphenylphosphine and 0.1g of methoxyhydroquinone were added. After the gas phase portion in the system was replaced with air, it was heated to 100 ℃ and reacted at the same temperature for 20 hours to obtain a base polymer (A-1). The acid value of the obtained base polymer was 73.3 in terms of solid content. The weight average molecular weight (Mw) of the obtained base polymer by GPC was 14000.
Production examples 1 and 2
2.6g of methacrylic acid, 13.1g of dicyclopentyl methacrylate, 8.3g of 3, 4-epoxycyclohexylmethyl methacrylate, and 72.3g of cyclohexanone were put into a glass flask equipped with a heating, cooling, and stirring device, a reflux condenser, and a nitrogen inlet tube. After the gas phase portion in the system was replaced with nitrogen, 3.6g of 2, 2' -azobis (2, 4-dimethylvaleronitrile) was added, and the mixture was heated to 65 ℃ and reacted at the same temperature for 13 hours to obtain a base polymer (A-2). The acid value of the obtained base polymer was 52.6 in terms of solid content. In addition, the weight average molecular weight (Mw) of the obtained base polymer based on GPC was 5400.
Production examples 1 to 3
2.6g of methacrylic acid, 12.9g of dicyclopentyl acrylate, 8.6g of 3, 4-epoxycyclohexylmethyl methacrylate, and 72.3g of cyclohexanone were put into a glass flask equipped with a heating, cooling, and stirring device, a reflux condenser, and a nitrogen inlet tube. After the gas phase portion in the system was replaced with nitrogen, 3.6g of 2, 2' -azobis (2, 4-dimethylvaleronitrile) was added, and the mixture was heated to 65 ℃ and reacted at the same temperature for 13 hours to obtain a base polymer (A-3). The acid value of the resulting base polymer was 68.8 in terms of solid content. The weight average molecular weight (Mw) of the obtained base polymer by GPC was 7300.
Production examples 1 to 4
2.3g of methacrylic acid, 13.3g of dicyclopentyl acrylate, 8.5g of glycidyl methacrylate, and 72.3g of cyclohexanone were placed in a glass flask equipped with a heating, cooling, and stirring device, a reflux condenser, and a nitrogen inlet tube. After the gas phase portion in the system was replaced with nitrogen, 3.6g of 2, 2' -azobis (2, 4-dimethylvaleronitrile) was added, and the mixture was heated to 65 ℃ and reacted at the same temperature for 13 hours to obtain a base polymer (A-4). The acid value of the obtained base polymer was 42.7 in terms of solid content. The weight average molecular weight (Mw) of the obtained base polymer by GPC was 7200.
Production examples 1 to 5
3.0g of methacrylic acid, 14.1g of dicyclopentyl acrylate, 6.9g of glycidyl methacrylate, and 72.3g of cyclohexanone were placed in a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen inlet tube. After the gas phase portion in the system was replaced with nitrogen, 3.6g of 2, 2' -azobis (2, 4-dimethylvaleronitrile) was added, and the mixture was heated to 65 ℃ and reacted at the same temperature for 13 hours to obtain a base polymer (A-5). The acid value of the obtained base polymer was 57.8 in terms of solid content. The weight average molecular weight (Mw) of the obtained base polymer by GPC was 7100.
Production examples 1 to 6
9.8g of methacrylic acid, 20.3g of dicyclopentanyl methacrylate and 55.8g of cyclopentanone were placed in a glass flask equipped with a heating, cooling and stirring device, a reflux condenser and a nitrogen gas inlet tube. After the gas phase portion in the system was replaced with nitrogen, 2.7g of 2, 2' -azobis (isobutyronitrile) was added, and the mixture was heated to 80 ℃ to react at the same temperature for 8 hours. Thereafter, the mixture was heated to 100 ℃ and reacted at the same temperature for 2 hours. Thereafter, 11.3g of glycidyl methacrylate, 0.02g of methoxyhydroquinone, 0.001g of 4-benzoyloxy-2, 2,6, 6-tetramethylpiperidine 1-oxyl (BTOX) and 0.1g of dimethylbenzylamine were added. After the gas phase portion in the system was replaced with air, it was heated to 100 ℃ and reacted at the same temperature for 20 hours to obtain a base polymer (A-6). The acid value of the resulting base polymer was 47.5 in terms of solid content. The weight average molecular weight (Mw) of the obtained base polymer by GPC was 7900.
[ (production of meth) acrylic ester ]
Production example 2-1
10.0g of ADAMANTATE E201 (manufactured by Osaka organic chemical Co., Ltd.), 6.2g of methacrylic anhydride, 0.3g of dimethylaminopyridine, and 24.3g of toluene were placed in a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen gas inlet tube. After the gas phase portion in the system was replaced with air, it was heated to 90 ℃ and reacted at the same temperature for 12 hours. Thereafter, 100.0g of methanol was added, and the precipitated solid was filtered and dried to obtain a methacrylic acid ester (C-1) represented by the following formula (3).
Production example 2-2
Into a glass flask equipped with a heating, cooling and stirring device, a reflux condenser and a nitrogen inlet tube were placed ADAMANTATE E201 (10.0 g, Osaka organic chemical Co., Ltd.), 3.5g of acrylic acid, 0.3g of dimethylaminopyridine and 24.3g of toluene. After the gas phase portion in the system was replaced with air, it was heated to 90 ℃ and reacted at the same temperature for 12 hours. Thereafter, 100.0g of methanol was added, and the precipitated solid was filtered and dried to obtain an acrylic ester (C-3) represented by the following formula (7).
[ preparation of curable resin composition ]
Example 1
A curable resin composition (solid content: about 40 mass%) was prepared by mixing 21.4 mass% of the base polymer (A-1), 6.4 mass% of dipentaerythritol hexaacrylate (B-1) as a polyfunctional monomer, 6.4 mass% of the methacrylate (C-1), 4.3 mass% of dicyclopentadiene dimethanol diglycidyl ether (D-1) as an epoxy resin, 1.2 mass% of a photopolymerization initiator (manufactured by IGM Resins B.V., Omnirad 379EG), 0.3 mass% of 3-glycidyl ether oxypropylmethyldiethoxysilane (manufactured by KBM-403, Inc.) as an adhesion imparting agent, and 60 mass% of Propylene Glycol Monomethyl Ether Acetate (PGMEA) as a solvent under light shielding.
Example 2 and comparative examples 1 to 4
A curable resin composition (solid content concentration: about 40 mass%) was prepared in the same manner as in example 1, except that the raw materials shown in table 1 were used in the amounts shown in table 1.
Example 3, comparative examples 5 and 6
A curable resin composition (solid content concentration: about 35 mass%) was prepared in the same manner as in example 1, except that the raw materials shown in table 2 were used in the amounts shown in table 2.
Examples 4 to 6 and comparative example 7
A curable resin composition (solid content concentration: about 35 mass%) was prepared in the same manner as in example 1, except that the raw materials shown in table 3 were used in the amounts shown in table 3.
The raw materials described in tables 1 to 4 are as follows.
Base polymer (A-1): the base Polymer produced in production example 1-1
Base polymer (A-2): base Polymer produced in production examples 1 to 2
Base polymer (A-3): base Polymer produced in production examples 1 to 3
Base polymer (A-4): base Polymer produced in production examples 1 to 4
Base polymer (A-5): base Polymer produced in production examples 1 to 5
Base polymer (A-6): base Polymer produced in production examples 1 to 6
Polyfunctional monomer (B-1): dipentaerythritol hexaacrylate
Methacrylate (C-1): the methacrylic acid ester produced in production example 2-1
Acrylate (C-2): dimethylol tricyclodecane diacrylate
Acrylate (C-3): acrylic ester produced in production example 2-2
Acrylate (C-4): an acrylic ester represented by the following formula (8)
Epoxy resin (D-1): dicyclopentadiene dimethanol diglycidyl ether
Epoxy resin (D-2): VG3101L made by TECHMORE corporation
Photopolymerization initiator (E-1): omnirad 379EG manufactured by IGM Resins B.V. Co
Photopolymerization initiator (E-2): irgacure OXE01 manufactured by Basff Japan
Adhesion-imparting agent (F-1): 3-glycidyloxypropylmethyldiethoxysilane (KBM-403, product of shin-Etsu chemical Co., Ltd.)
Adhesion-imparting agent (F-2): a reaction product of isocyanatopropyltriethoxysilane (KBM 9007, manufactured by shin-Etsu chemical Co., Ltd.) and ureidopropyltrimethoxysilane (T1915, manufactured by Tokyo chemical Co., Ltd.) (manufactured in accordance with example 1 described in International publication No. WO 2014/104195.)
Polymerization inhibitor: methoxy hydroquinone
Surfactants: silicone oil (FZ 2122 manufactured by Dongli Tanking Co., Ltd.)
PGMEA: propylene glycol monomethyl ether acetate
[ evaluation of resolution ]
Examples 1 and 2 and comparative examples 1 to 4
Each of the prepared curable resin compositions was uniformly applied to a glass substrate by a spin coater, and then dried on a hot plate at 90 ℃ for 2 minutes. The obtained coating film was irradiated with 300mJ/cm of light through a mask having a light-shielding portion with a hole pattern2Light (irradiation) of the extra-high pressure mercury lampDegree is 30mW in terms of i-line). The distance between the mask and the substrate (exposure gap) was 50 μm. Thereafter, development was performed using a 2.38% aqueous TMAH solution. After the washing, the resultant was baked at 230 ℃ for 30 minutes to prepare a resist pattern having a film thickness of 8 μm. The resolution (resolution) was evaluated based on the size of the through hole for analysis (resolution) according to the following criteria. The results are shown in table 1.
A: the size of the through hole for image analysis is below 30 μm
B: the size of the through holes is more than 30 μm and less than 50 μm
C: the size of the through hole for image analysis is more than 50 μm in diameter
[ evaluation of insulation ]
Examples 1 and 2 and comparative examples 1 to 4
A glass substrate having a predetermined copper wiring pattern was prepared. Each of the prepared curable resin compositions was uniformly applied to a glass substrate with copper wiring by a spin coater, and then dried on a hot plate at 90 ℃ for 2 minutes. The resulting coating film was irradiated with 300mJ/cm light while shielding the electrodes at both ends of the copper wiring2The light intensity of the extra-high pressure mercury lamp (illuminance: 30mW in terms of i-line). Thereafter, development was performed using a 2.38% TMAH aqueous solution. After washing with water, the resultant was baked at 230 ℃ for 30 minutes to form a cured film having a thickness of 8 μm. This substrate was used as an evaluation substrate. The obtained substrate was placed in a HAST evaluation apparatus (manufactured by ESPEC corporation), and a test was performed under conditions of a temperature of 130 ℃, a humidity of 85%, and an applied voltage of 12V. Insulation was decreased and the resistance value was measured to become lower than 106The insulation was evaluated for the time period of Ω based on the following criteria. The results are shown in table 1.
A: resistance value lower than 106The time of omega is more than 100 hours
B: resistance value lower than 106The time of omega is 80 hours or more and less than 100 hours
C: resistance value lower than 106The time of omega is 50 hours or more and less than 80 hours
D: resistance value lower than 106Omega time is less than 50 hours
[ measurement of Water absorption ]
Examples 1 and 2 and comparative examples 1 to 4
Each of the curable resin compositions prepared in examples 1 and 2 and comparative examples 1 to 4 was uniformly applied to a glass substrate by a spin coater, and then dried on a hot plate at 90 ℃ for 2 minutes. The whole surface of the obtained coating film was irradiated with 300mJ/cm2The light intensity of the extra-high pressure mercury lamp (illuminance: 30mW in terms of i-line). Thereafter, development was performed using a 2.38% TMAH aqueous solution. After washing with water, the resultant was baked at 230 ℃ for 30 minutes to form a cured film having a thickness of 8 μm. The substrate thus obtained was immersed in water at 23 ℃ for 24 hours, and then the moisture content in the cured film was measured using Tg-DTA to determine the water absorption (%). The results are shown in table 1.
[ measurement of ion migration ]
Example 3, comparative examples 5 and 6
A first substrate having a copper wiring pattern according to IPC-B24 (copper wiring width: 1500 μm, pitch between wirings: 350 μm, wiring thickness: 35 μm) defined in ISO 9455-17 was prepared. After each of the curable resin compositions was uniformly applied to the substrate, which protected the electrodes provided at both ends of the copper wiring, using a spin coater, drying was performed on a hot plate at 100 ℃ for 2 minutes. The resulting coating film was irradiated with 1000mJ/cm2The light intensity of the extra-high pressure mercury lamp (illuminance: 20mW in terms of i-line). Thereafter, firing was performed at 120 ℃ for 45 minutes to form a cured film having a thickness of 35 μm as each evaluation substrate. The obtained evaluation substrate was set in a migration tester (manufactured by Nanzi Kasei K.K., SIR13-SLIM), and a test was performed under conditions of a temperature of 85 ℃, a humidity of 85%, and an applied voltage of 100V, to evaluate the change with time of the resistance value. The results are shown in table 2.
Examples 4 to 6 and comparative example 7
Each evaluation substrate was fabricated in the same manner as described above except that a second substrate having a copper wiring pattern (copper wiring width: 100 μm, pitch between wirings: 100 μm, wiring thickness: 0.1 μm) was used and the thickness of the cured film was adjusted to 6 μm. Tests were carried out in the same manner as described above except that the applied voltage was set to 12V, and the change with time in the resistance value was evaluated. The results are shown in table 3.
[ measurement of relative dielectric constant ]
Each monomer composition (solid content concentration: 45 mass%) was prepared by mixing 100 parts by mass of each monomer of the methacrylic acid ester (C-1), the acrylic acid ester (C-2) or the acrylic acid ester (C-4), 3 parts by mass of a photopolymerization initiator (Irgacure OXE04, manufactured by basf japan) and a solvent (cyclohexanone/propylene glycol monomethyl ether acetate 75/25) under light shielding. Each of the prepared monomer compositions was uniformly applied to an ITO substrate (10 cm. times.10 cm, manufactured by EHC) by means of a spin coater, and then dried on a hot plate at 90 ℃ for 90 seconds to form a coating film. The obtained coating film was irradiated with 90mJ/cm2The light intensity of the extra-high pressure mercury lamp (illuminance: 30mW in terms of i-line) was then baked at 230 ℃ for 30 minutes to obtain a cured film. Then, the ITO substrate on which the cured film was formed was cut into a size of 2.5cm × 5cm, a metal mask having openings was attached to the cured film with a polyimide tape, and gold was deposited on the cured film of the openings 6 times using a gold deposition machine to form gold electrodes (3mm × 3mm, film thickness, etc.)
) A sample for measuring the relative dielectric constant was prepared.
The capacitance of the prepared sample was measured by an impedance analyzer (E4990A, manufactured by delocalized tecchologies) under the following measurement conditions, and the relative dielectric constant was calculated. The results are shown in table 4.
< measurement Condition >
Resonance measurement jig: 16047E
Start: 1kHz
End: 1000kHz
·500mV
< method for calculating relative dielectric constant > ]
The impedance analyzer is used to obtain the value of "C (capacitance)". The relative dielectric constant was calculated according to the following equation.
εr＝Cd/ε0S
εr: relative dielectric constant
ε0: dielectric constant of vacuum
C: capacitance [ pF ]
S: electrode area m2]
d: film thickness [ m ]
[ Table 1]
[ Table 2]
[ Table 3]
[ Table 4]
Industrial applicability
The cured product obtained from the curable resin composition of the present invention can be suitably used as a member requiring insulation properties (for example, an insulating film resist, an insulating sheet, an insulating layer, and the like).
Claims (7)
1. A (meth) acrylate represented by the following general formula (1) or (2),
in the formula (1), R1～R4Each independently is H or methyl, R5～R7Are respectively independentIndependently represents a halogen group, an alkyl group, an alkoxy group or an aryl group, AO represents an ethyleneoxy group or an propyleneoxy group, m and n are each independently an integer of 0 to 5, p is an integer of 0 to 2, r and s are each independently an integer of 0 to 15,
in the formula (2), R1～R4Each independently of the other is H or methyl, R5～R7Independently represents a halogen group, an alkyl group, an alkoxy group or an aryl group, AO represents an ethyleneoxy group or an propyleneoxy group, m and n independently represent an integer of 0 to 5, p represents an integer of 0 to 2, and r and s independently represent an integer of 0 to 15.
2. A curable resin composition comprising at least one of the (meth) acrylate of claim 1, a base polymer, a polymerization initiator, and a solvent.
3. The curable resin composition according to claim 2,
the content of the (meth) acrylate is 20 to 100 parts by mass with respect to 100 parts by mass of the base polymer.
4. The curable resin composition according to claim 2 or 3,
the curable resin composition contains a polyfunctional monomer.
5. The curable resin composition according to any one of claims 2 to 4,
the curable resin composition contains an epoxy resin.
6. A cured product obtained by curing the curable resin composition according to any one of claims 2 to 5.
7. The cured product according to claim 6, wherein,
the water absorption of the cured product is 1% or less.
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| PCT/JP2020/044066 WO2021107031A1 (en) | 2019-11-27 | 2020-11-26 | (meth)acrylate, curable resin composition, and cured product |
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