TW201437245A - Epoxy acrylate resin and manufacturing method thereof, acid anhydride adduct of epoxy acrylate, curable resin composition, alkali developable photosensitive resin composition and cured product thereof - Google Patents

Abstract

An epoxy acrylate, an acid adduct and composition thereof are provided, wherein the epoxy acrylate gives a cured product having excellent reliability of heat resistance against soldering, coating hardness, adhesion property and chemical resistance, etc., and is suitable for use in circuit board materials, etc. A curable resin composition and an alkali developable photosensitive resin composition of the invention includes an epoxy acrylate resin, an acid anhydride adduct of epoxy acrylate, a resin thereof and an initiator. The epoxy acrylate resin is obtained by reacting (meth)acrylic acid with a epoxy resin derived from a compound formed by substituting benzene ring aralkyl of bisphenol F or novolac-type phenolic resin. The acid anhydride adduct of epoxy acrylate is obtained by esterifying at least a portion of an OH group of the epoxy acrylate resin by polyvalent carboxylic acid anhydride.

Description

Epoxy acrylate resin, method for producing the same, epoxy acrylate anhydride adduct, curable resin composition, alkali-developable photosensitive resin composition, and cured product thereof

The present invention relates to an epoxy acrylate resin, an epoxy acrylate anhydride adduct, a curable resin composition using the same, and an alkali-developable type, which are excellent in developability and excellent in adhesion and solder heat resistance. The photosensitive resin composition and the cured product thereof can be applied to: a protective film (overcoat) of a printed wiring board, a permanent protective film such as an undercoat layer, an insulating layer, a solder resist ink, and an insulating layer of a build-up substrate. A material or the like, or a solder resist ink which can be used for producing a printed wiring board, particularly a flexible printed wiring board, which can be developed with a dilute alkali solution.

From the viewpoint of the use of the solder resist ink for the insulating protective film of the exposed conductor circuit of the printed wiring board and the use of the portion where the solder is not required to adhere to the solder of the circuit, the coating film forming method is usually applied by screen printing. The cloth and the hardened film are required to have solder heat resistance, moisture resistance, adhesion, chemical resistance, plating resistance, and electrolytic corrosion resistance. The types of solder resists are thermosetting type and ultraviolet curing type. The former mainly uses epoxy resin, and the latter mostly An epoxy acrylate resin is used. However, in recent years, the miniaturization of the conductor circuit pattern in various printed wiring boards, the improvement in positional accuracy, and the further miniaturization of the mounted components have led to the formation of an insulating film using a solder resist to a screen printing method. Image formation is becoming mainstream. Further, the development of the resist by the photo method has previously used an organic solvent, but from the viewpoint of air pollution or safety, it is desirable to use a dilute aqueous alkali solution. Due to this background, the solder resist produces an unsatisfactory problem using the epoxy or epoxy acrylate resin corresponding to the previous screen printing.

For the photo method and the development of a dilute alkali aqueous solution, for example, a phenol novolak type is known. An epoxy acrylate resin, a bisphenol A epoxy acrylate resin, or a half esterified product obtained by the reaction of these epoxy acrylate resin and acid dianhydride (Patent Document 1 and Patent Document 2). However, when such a known epoxy acrylate resin or an anhydride modified product thereof is used as a resin composition for a solder resist, the developability of a dilute alkali aqueous solution is satisfied, but the curing temperature is required to be at least 180 ° C or more in order to stabilize physical properties. Not only is the cost of the heating device expensive, but also, for example, when the glass epoxy substrate is used for the core substrate, there is a fear that the curing temperature is too high to cause discoloration or warpage of the substrate. Further, the cured film obtained from these known epoxy acrylate resins or their anhydride-modified materials has solder heat resistance, moisture resistance, adhesion, chemical resistance, plating resistance, and electrolytic corrosion resistance. Full question.

In recent years, with the increase in density of printed wiring boards, it is required to mount an insulating layer for a wafer such as a build-up substrate or a chip scale package (CSP) for a multi-chip module (MCM). When the known epoxy acrylate resin or its anhydride modified product is used as a resin composition for a solder resist, the above-mentioned known epoxy acrylate resin or heat-resistant cycle property may have a problem that sufficient reliability cannot be exhibited.

As described above, from the viewpoint of heat resistance of the substrate material, manufacturing equipment, and the like, low-temperature curing cannot be achieved, development of the diluted alkali water by the photo method cannot be achieved, and the solder resist of the printed wiring board cannot be sufficiently satisfied. Solder heat resistance, moisture resistance, adhesion, chemical resistance, plating resistance, electrolytic corrosion resistance, and reliability required for an insulating layer cured film such as a high-density mounting substrate such as MCM. Further, an aromatically modified phenol novolac type epoxy resin is known, but an alkali-developable resin composition or a cured product thereof has not been studied (Patent Document 3).

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 61-243869

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2003-026762

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2010-235819

Accordingly, it is an object of the present invention to provide a novel epoxy acrylate resin and an anhydride adduct thereof which can achieve light or heat hardening, and provide a low temperature hardening which can achieve a temperature below 160 ° C and a utilization of a light alkali by photo method A curable resin for developing water and a curable resin composition which is a main resin component. In addition, it is an object of the present invention to provide a curable resin composition which is excellent in reliability such as developability, solder heat resistance, coating film hardness, adhesion, and chemical resistance required for a solder resist or an insulating film of a printed wiring board. And its hardened material.

The present invention is an epoxy acrylate resin represented by the following general formula (1): [Chemical Formula 1]

(herein, R ₁ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, R ₂ represents an aralkyl group represented by the following formula (a), R ₆ represents hydrogen or a methyl group, and n represents a number of 1 to 20; , p represents the number from 0.1 to 2.5)

(here, R ₃ to R ₅ represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms).

Further, the present invention is the epoxy acrylate resin, wherein the general formula (a) is an aralkyl group derived from styrene.

Furthermore, the present invention provides a method for producing an epoxy acrylate resin, which comprises reacting (meth)acrylic acid with an epoxy resin represented by the following formula (2);

(H Here, G represents a glycidyl group, and R ₁ , R ₂ , n and p are synonymous with the general formula (1)).

Further, the present invention is an epoxy acrylate anhydride adduct represented by the following formula (3), which is obtained by reacting a polybasic acid compound with the epoxy acrylate resin;

(here, R ₁ , R ₂ , R ₆ , n, p are synonymous with the formula (1), X represents hydrogen or a polybasic acid group represented by -OC-A(COOH) _m , and A is a residue of a polybasic acid More than 10 mol% of X is the polybasic acid group; m represents 1, 2 or 3).

Further, the present invention is a curable resin composition comprising the above epoxy acrylate resin, epoxy acrylate anhydride adduct, and a polymerization initiator.

Furthermore, the present invention is an alkali-developable photosensitive resin composition comprising the above-described epoxy acrylate anhydride adduct and a photopolymerization initiator, and the alkali-developable photosensitive resin composition, among which Contains epoxy resin.

Further, the present invention is a cured product obtained by curing the curable resin composition or the alkali-developable photosensitive resin composition.

According to the present invention, a novel epoxy acrylate resin capable of hardening by light or heat and an acid anhydride adduct thereof can be formed, and a resin composition containing an epoxy acrylate resin or an acid anhydride adduct can achieve low temperature hardening at 160 ° C or lower. And the development of dilute alkali water by photofabrication, and It is excellent in reliability required for insulating layers such as solder heat resistance, coating film hardness, adhesion, and chemical resistance, and is therefore suitable not only as a solder resist for printed wiring boards, but also as a build-up substrate or CSP. The material of the interlayer insulating film for the wafer mounting substrate.

1 is a gel permeation Chromatography (GPC) chart of an epoxy acrylate resin.

Figure 2 is a GPC chart of an acid anhydride adduct.

Hereinafter, the present invention will be described in detail.

The epoxy acrylate resin of the present invention is a compound represented by the above formula (1), and may be a single compound of n = 1, or may be an oligomer containing n different components. The average number of repetitions n (number average) is 1 to 20, preferably 1 to 5.

In the formula (1), R ₁ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. R ₁ is preferably hydrogen or an alkyl group having 1 to 6 carbon atoms or a phenyl group, more preferably hydrogen. R ₆ is hydrogen or methyl.

R ₂ represents the aralkyl group represented by the formula (a). R ₃ to R ₅ represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ₃ is preferably hydrogen or an alkyl group having 1 to 6 carbon atoms or a phenyl group, more preferably hydrogen. R ₄ to R _{5 are} preferably hydrogen or an alkyl group having 1 to 6 carbon atoms, more preferably hydrogen or methyl. R ₄ to R ₅ may be the same or different, and when one is a hydrocarbon group, the other is preferably hydrogen. The average value of p represents a number from 0.1 to 2.5, preferably from 0.2 to 2.0, more preferably from 0.3 to 1.5. Here, the average refers to an average of the number of R ₂ present per one benzene ring to which the aralkyl group R _{2 of} the formula (a) is bonded.

The method for synthesizing the epoxy acrylate resin of the formula (1) is not limited. First, it is preferred to synthesize a novolac type phenol resin or a dihydroxyphenylmethane from a phenol and a formaldehyde (referred to as these The phenol resin is aralkylated by an aralkylating agent. Then, it is preferred to react an aralkylated phenol resin with epichlorohydrin to form an epoxy resin of the formula (2) in which an OH group is a glycidyl ether group, and to make it with (meth)acrylic acid. The method of class reaction. However, the phenols may be aralkylated, and may also be formed into an epoxy resin for aralkylation. Further, when an epoxy resin is produced by reacting with epichlorohydrin, an epoxy group is opened to form a small amount of a structural component obtained by polymerization, but the component may be mixed.

The aralkylation is advantageously carried out using an aromatic olefin such as a styrene or an aralkyl halide or an aralkyl alcohol such as benzyl chloride or benzyl alcohol as an aralkylating agent in the presence of an acid catalyst. When styrene is used, R ₂ becomes an α-methylbenzyl group, and when benzyl chloride is used, R ₂ becomes a benzyl group.

The reaction of making phenolic resin or aralkylated phenolic resin into epoxy resin is public It is known that these well-known reactions can be employed. Advantageously, a method of carrying out the reaction in the presence of a base catalyst using an excess of epichlorohydrin. For example, a method of producing a novolac type epoxy resin from a novolac type phenol resin can be employed. Further, an epoxy resin of the formula (2) can be obtained by reacting an aralkylated phenol resin with epichlorohydrin. Further, the epoxy resin represented by the formula (2) is disclosed in Japanese Patent Laid-Open No. 2010-235819 or World Patent No. WO2012/043213.

The epoxy acrylate resin of the present invention is represented by the general formula (1). The epoxy acrylate resin of the formula (1) can be produced by reacting an epoxy resin of the formula (2) with (meth)acrylic acid (referred to as acrylic acid, methacrylic acid or both). Here, among (meth)acrylic acid, acrylic acid is preferable. In addition, acrylic acid and methacrylic acid can be used in combination. The reaction is usually carried out in the range of from 50 ° C to 150 ° C in the range of from 1 hour to 20 hours. The ratio of use of the epoxy resin to (meth)acrylic acid can be such that the molar ratio of the epoxy group to the carboxyl group is equal to or higher than the molar ratio, or in the vicinity thereof (preferably 0.8 to 1.2). use.

The epoxy acrylate anhydride adduct of the present invention is represented by the above formula (3). In the formula (3), X represents hydrogen or a polybasic acid group represented by -OC-A(COOH) _m . A is a residue of a polybasic acid, and m represents 1, 2 or 3. The epoxy acrylate anhydride adduct of the formula (3) can be obtained by reacting an epoxy acrylate resin of the formula (1), a polybasic acid represented by A(COOH) _m+1 or a derivative thereof, preferably an acid anhydride thereof. And got it. Hereinafter, a polybasic acid or a derivative thereof is referred to as an acid anhydride.

In the general formula (1), the general formula (2), and the general formula (3), the common symbols have the same meaning unless otherwise specified.

The reaction of the epoxy acrylate resin of the formula (1) with an acid anhydride typically refers to utilization. An acid anhydride is a reaction in which an OH group in the formula (1) is esterified. In the general formula (3), X does not need to be all the same, and may have hydrogen or a polybasic acid group in one molecule, and not all of them are hydrogen. Preferably, 10 mol% or more, more preferably 20 mol% to 100 mol% of X is the polybasic acid group, and when 90 mol% or more of X, and advantageously 100 mol% is a polybasic acid group, A more preferable curable resin is formed. Since the polybasic acid group is reactive with the base, it is possible to impart alkali solubility to the anhydride adduct or a partial polymerization reaction product (uncured product). By changing the existence ratio of the polybasic acid groups in X, the alkali solubility can be adjusted, and the alkali developability can be optimized.

Anhydride adducts can be used to make epoxy acrylate resins, acid anhydrides or acid anhydrides Manufactured by reaction. Further, the acid anhydride may be trimellitic anhydride or the like, and the trimellitic anhydride is an acid monoanhydride.

A preferred acid anhydride is represented by the following formula (4).

[O(CO) ₂ ] _p A(COOH) _q (4)

(wherein A represents a residue of an aromatic or aliphatic polybasic acid, and may have a substituent. p is 1 or 2, q is 0 or 1, and 2p+q is 2 to 4.)

Examples of the acid dianhydride include diphenyl ether tetracarboxylic anhydride, diphenylsulfonium tetracarboxylic anhydride, biphenyl tetracarboxylic anhydride, naphthalene tetracarboxylic anhydride, perylenetetracarboxylic anhydride, phenanthrene anhydride, and hexafluoroisopropylidene ( Phthalic anhydride), ethylene glycol bis(dehydrated trimellitate), methylcyclohexene tetracarboxylic anhydride, tetramethyldioxane tetracarboxylic anhydride, and the like. Preferably, it is biphenyltetracarboxylic anhydride, diphenyl ether tetracarboxylic anhydride, pyromellitic anhydride, and benzophenone tetracarboxylic anhydride.

The acid monoanhydrides are, for example, maleic anhydride, succinic anhydride, itaconic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydroortho Phthalic anhydride, methyl nadic anhydride, dodecynyl succinic anhydride, chlorinic anhydride, trimellitic anhydride. Preferably, tetrahydrophthalic anhydride is used.

In the general formula (3), in order to obtain a single acid anhydride adduct of X, it is typically obtained by subjecting one type of acid anhydride to a theoretical amount of the epoxy acrylate resin represented by the formula (1). In order to obtain an acid anhydride addition product different in X, it can be obtained by reacting two or more kinds of acid anhydrides or by reacting a polybasic acid having a theoretical amount or less with H of an epoxy acrylate resin. For example, the polybasic acid may also be used in combination with an acid monoanhydride and an acid dianhydride, and it is advantageous to preferably have 10 mol% or more of X, more preferably 20 mol% to 100 mol%, particularly preferably 40 mol% to 80 mol%. The % is a polybasic acid group, and the ratio of the polybasic acid group formed by the acid monoanhydride to the acid dianhydride (acid monoanhydride/acid dianhydride) can be set to about 10/90 to 90/10. Further, when an acid dianhydride is used, a plurality of hydroxyl groups in the formula (1) are reacted with an acid dianhydride to form an oligomer, but the oligomer is also an acid anhydride adduct of the present invention.

The curable tree of the present invention can be obtained by blending a photopolymerization initiator or a radical polymerization initiator in the epoxy acrylate resin and the epoxy acrylate anhydride adduct of the present invention. A lipid composition or an alkali-developable photosensitive resin composition. In addition, it is also advantageous to formulate multifunctional acrylates. 30% by weight or more, preferably 50% by weight or more, and more preferably 70% by weight or more of the resin component (resin and resin component after curing) in the resin composition of the present invention may be the epoxy acrylate of the present invention. Or anhydride adduct. In addition, the resin composition of the present invention is used in the sense of including both a curable resin composition and an alkali-developable photosensitive resin composition, unless otherwise specified. Further, the resin composition in which the epoxy acrylate anhydride adduct is blended is an alkali-developable photosensitive resin composition, and the resin composition in which the epoxy acrylate resin is blended is a curable resin composition, and both of them are blended. The resin composition is a curable resin composition or an alkali-developable photosensitive resin composition. In addition, the resin composition in which the epoxy acrylate anhydride adduct is prepared and the alkali-developable photosensitive resin composition also exhibit curability, and thus may be a curable resin composition. Further, in the general formula (1) and the general formula (3), only a part or all of the OH group in the general formula (1) may be referred to as a difference in OX, and therefore, the resin may be Anhydride adducts are collectively referred to and are also referred to as resins of the present invention.

As the photopolymerization initiator, various known photopolymerization initiators can be used. Preferred photopolymerization Examples of the initiator include benzoin, benzoin, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1,1-dichlorobenzene. Ethyl ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinol propane, N,N-dimethylaminoacetophenone, 2- Methyl hydrazine, 2-ethyl hydrazine, 2-tert-butyl hydrazine, 1-chloroindole, 2-pentyl hydrazine, 2-isopropyl thioxanthone, 2,4-dimethyl thiophene Tons of ketone, acetophenone dimethyl ketal, benzophenone, 4-methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminodiphenyl Ketone and so on. These can be used individually or in mixture of 2 or more types.

The photopolymerization initiator is used in an amount of from 0 part by weight to 100 parts by weight, preferably from 0.5 part by weight to 40 parts by weight, based on 100 parts by weight of the epoxy acrylate anhydride adduct of the formula (3). It is preferably from 1 part by weight to 10 parts by weight. Further, the photopolymerization initiator is used in an amount of usually from 0 part by weight to 50 parts by weight, preferably from 1 part by weight to 20 parts by weight, based on 100 parts by weight of the resin composition. When a thermal polymerization initiator is used, a photopolymerization initiator may not be used. However, since the photosensitive resin composition of the present invention is excellent in exposure and developability, a photopolymerization initiator is used as a photocurable resin composition. More favorable.

Further, one or two or more kinds of these photopolymerization initiators and known photo-sensitizers can be used at the same time. Examples of the photosensitizer include michione, N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, triethanolamine, triethylamine, and the like. The photosensitizer is used in an amount of from 0 part by weight to 20 parts by weight, preferably from 0.02 part by weight to 10 parts by weight, more preferably from 0.05 part by weight to 2 parts by weight based on 100 parts by weight of the compound of the formula (1). Share. In addition, the amount of the photosensitizer used is usually from 0 part by weight to 10 parts by weight, preferably from 0.01 part by weight to 5 parts by weight, per 100 parts by weight of the alkali-developable photosensitive resin composition.

For thermal polymerization, it is preferred to formulate a radical polymerization initiator, which is only photohardened. When you are not, you can also not deploy. Preferred radical polymerization initiators are exemplified by well-known benzoyl peroxide, p-chlorobenzidine peroxide, diisopropyl peroxycarbonate, di-2-ethylhexyl peroxycarbonate, peroxidation. Peroxide such as t-butyl pivalate, and 1,1'-azobiscyclohexane-1-carbonitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), 2 , 2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis-(methyl isobutyrate), α,α-azobis An azo compound such as (isobutyronitrile) or 4,4'-azobis-(4-cyanovaleric acid). The amount of the thermal polymerization initiator used is from 0 part by weight to 100 parts by weight, preferably from 0.02 part by weight to 60 parts by weight, more preferably 100 parts by weight to the compound of the formula (1). It is 0.05 parts by weight to 2 parts by weight. In addition, the amount of the thermal polymerization initiator used is from 0 part by weight to 50 parts by weight, preferably from 0.01 part by weight to 30 parts by weight, per 100 parts by weight of the curable resin composition of the present invention.

The cured product of the present invention can be obtained by hardening the resin composition of the present invention. In order to improve characteristics such as adhesion, hardness, alkali resistance, and flatness of the cured product, a resin composition containing the acid anhydride adduct of the above formula (3) may be blended as needed: epoxy resin ( Phenolic novolac epoxy resin, cresol novolac epoxy resin, trisphenol methane epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, etc., or these epoxy resins and (methyl) An epoxy (meth) acrylate obtained by reacting acrylic acid, or a reaction product obtained by reacting the epoxy (meth) acrylate with the acid anhydride, or the like, or a polymerizable unsaturated resin. Monofunctional and polyfunctional (meth) acrylates. The resin composition containing the epoxy acrylate resin of the general formula (1) can be formulated in the same manner as needed.

Examples of the polyfunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate. 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol diacrylate, neopentyl glycol adipate diacrylate, hydroxypivalate Acid neopentyl glycol acrylate, dicyclopentanyl diacrylate, caprolactone modified dicyclopentenyl diacrylate, ethylene oxide (Ethylene Oxide, EO) modified phosphodiacrylate, allylate ring Hexyl diacrylate, isocyanuric acid diacrylate, trimethylolpropane triacrylate, propionic acid modified dipentaerythritol tri(meth)acrylate, dipentaerythritol hexaacrylate, pentaerythritol tri(meth)acrylate, Propylene Oxide (PO) modified trimethylolpropane triacrylate, tris(propylene decyloxyethyl)isocyanurate, propionic acid modified dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate , caprolactone modified dipentaerythritol hexaacrylate, 1,3-bis(3-propenyloxypropyl)-1,1,3,3-tetra Dioxasiloxane, 1,3-bis(3-propenyloxypropyl)-1,1,3,3-tetramethyldioxane, and the like.

Further, an inorganic filler (for example, talc, cerium oxide, aluminum oxide, barium sulfate, magnesium oxide, or the like), a thixotropic agent (for example, Aerosil (trade name), etc.), or a thermoplastic elastomer or a rubber component may be added ( An acrylonitrile rubber, a nitrile butadiene rubber, or the like, or a melamine resin (for example, hexamethoxymelamine or hexabutoxy melamine) or a leveling agent (for example, an anthrone, a fluorine-based polymer, an acrylic copolymer, etc.) Or a decane coupling agent (for example, an epoxy group-containing trimethoxy decane, a decyl group-containing trimethoxy decane, etc.), or a coloring pigment (for example, phthalocyanine green, phthalocyanine blue, etc.), or an antifoaming agent, or ultraviolet absorbing agent. Agent, or antioxidant, or polymerization inhibitor, or leveling agent, and the like.

The polyfunctional (meth) acrylate used in the resin composition of the present invention can be used as the polyfunctional (meth) acrylate. Preferably, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, hydroxy(meth)acrylate, 1, 4-butanediol di(meth)acrylate, 1,6-hexanediol (meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate , neopentyl glycol adipate di(meth) acrylate, hydroxypivalic acid neopentyl glycol (meth) acrylate, dicyclopentanyl (meth) acrylate, caprolactone modified bis ( Dicyclopentenyl methacrylate, EO modified di(meth) acrylate, allylated cyclohexyl di(meth) acrylate, isocyanuric acid di(meth) acrylate, trishydroxyl Propane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid modified dipentaerythritol tri(meth)acrylate, pentaerythritol (meth)acrylate, PO modified trimethylolpropane Tris(meth)acrylate, EO modified trimethylolpropane tri(meth)acrylate, tris(propyleneoxyethyl)isocyanurate, propionic acid modified dipentaerythritol penta(methyl) Acrylate, two Pentaerythritol hexa(meth) acrylate, caprolactone modified dipentaerythritol hexa(meth) acrylate, 1,3-bis(3-acryloxypropyl)-1,1,3,3-tetra Dioxazane, 1,3-bis(3-propenyloxypropyl)-1,1,3,3-tetramethyl Dioxane and the like. These polyfunctional (meth) acrylates make the photohardening or thermal hardening more sufficient to improve the chemical resistance, acid resistance, heat resistance, mechanical properties, dielectric constant, dielectric loss of the cured product. The angle tangent may be used alone or in combination of two or more.

Formulating a polyfunctional (meth) acrylate with respect to 100 parts by weight of the resin of the present invention The amount to be used is usually from 5 parts by weight to 100 parts by weight, and in order to further increase the dielectric constant and the dielectric loss tangent, it is preferably selected in the range of 10 parts by weight to 50 parts by weight. When the amount is less than 5 parts by weight, the photocurability is insufficient, and the effect of improving the chemical resistance, acid resistance, heat resistance, mechanical properties, dielectric properties, etc. of the cured product cannot be sufficiently exhibited, or When the amount is more than 100 parts by weight, the surface hardening is too good, so that cracks occur in the surface layer or it is difficult to harden to the inside. Further, the amount used is usually from 2.5 parts by weight to 50 parts by weight, preferably from 5 parts by weight to 25 parts by weight, per 100 parts by weight of the resin composition.

The curable resin composition for producing the cured product of the present invention is required as described above The resin of the present invention (an epoxy acrylate resin or an epoxy acrylate anhydride adduct represented by the formula (1) or (3)), and an additive such as a photopolymerization initiator, but a preferred composition It is a composition as described below. In the case of a photosensitive resin composition containing an epoxy acrylate anhydride addition product, the photopolymerization initiator is 1 part by weight to 20 parts by weight, preferably 1 part by weight to 5 parts by weight based on 100 parts by weight of the resin of the present invention. The light sensitizer is 0.01 parts by weight to 5 parts by weight, preferably 0.5 parts by weight to 2 parts by weight, and the radical polymerization initiator is 0.01 parts by weight to 30 parts by weight, preferably 0.05 parts by weight to 2 parts by weight. The trifunctional or higher polyfunctional (meth) acrylate is 5 parts by weight to 50 parts by weight, preferably 10 parts by weight to 50 parts by weight, and the epoxy resin is 5 parts by weight to 30 parts by weight, preferably 10 parts by weight. 20 parts by weight, the solvent is the amount of the desired viscosity, The other solid content is from 0 part by weight to 50 parts by weight, preferably from 0 part by weight to 20 parts by weight. In the case of a thermosetting resin composition containing an epoxy acrylate resin or an epoxy acrylate anhydride adduct, the radical polymerization initiator is 0.01 to 30 parts by weight based on 100 parts by weight of the resin of the present invention. Preferably, it is 0.05 parts by weight to 2 parts by weight, and the trifunctional or higher polyfunctional (meth) acrylate is 5 parts by weight to 50 parts by weight, preferably 10 parts by weight to 50 parts by weight, and the epoxy resin is 5 parts by weight. 30 parts by weight, preferably 10 parts by weight to 20 parts by weight, the solvent is an amount to obtain a desired viscosity, and the other solid content is 0 parts by weight to 50 parts by weight, preferably 0 parts by weight to 20 parts by weight.

Here, the proportion of the resin of the present invention in the solid content is preferably 50% by weight or more. Further, when an epoxy acrylate, a polyfunctional acrylate or the like is blended in the resin composition, when it is a compound represented by the formula (1), it is calculated as a compound represented by the formula (1).

In order to obtain a cured film which can be developed by a dilute aqueous alkali solution and patterned by light, an alkali-developable photosensitive resin composition having a polybasic acid group as X in the general formula (3) is used. In the general formula (3), the proportion of the polybasic acid group in X is from 10% to 100%, preferably from 50% to 100%. When the ratio of the residue of the polybasic acid is less than 10%, the unexposed portion is hardly dissolved in the aqueous alkali solution.

In the resin composition of the present invention, a preferred component is a component exhibiting a curing ratio of 80% to 95% when the curing time is 1 hour in the entire range of 120 ° C to 160 ° C. In this case, a photo or thermal polymerization initiator may be contained as an essential component.

The cured product of the present invention can be obtained by a known method. For example, a resin composition is applied on a printed substrate by a screen printing method, a spray method, a roll coating method, an electrostatic coating method, a spin coating method, or a curtain coating method at a film thickness of 5 μm to 100 μm. The film is processed at room temperature ~140 ° C The heating time is from 1 minute to 120 minutes, and drying is preferably carried out at 60 to 120 ° C for 5 minutes to 60 minutes, followed by ultraviolet irradiation or heating to obtain a cured product. The heat curing condition is usually from 100 ° C to 270 ° C, preferably from 160 ° C to 250 ° C, and the heating time is from 30 minutes to 2 hours.

When the resin composition is an alkali-developable photosensitive resin composition, the method is used After coating and drying, the photomask and the coating film are directly contacted, and then exposed to ultraviolet light for exposure and hardening, followed by 0.1% by weight to 2% by weight of aqueous sodium carbonate solution, 0.1% by weight to 2% by weight of diethanolamine, and 0.1% by weight. An alkali aqueous solution such as a 2% by weight aqueous solution of tetramethylammonium hydroxide is used to dissolve and remove the unirradiated portion of the coating film. Next, it is subjected to thermal hardening at a temperature of from 100 ° C to 270 ° C, preferably from 160 ° C to 250 ° C, for 30 minutes to 2 hours to obtain a cured product.

[Examples]

Hereinafter, the present invention will be more specifically described by way of examples.

(1) Gel permeation chromatography (GPC) determination

An instrument equipped with TSKgel G4000HXL, TSKgel G3000HXL, and TSKgel G2000HXL (trade name) manufactured by Tosoh Corporation was used in series, and the column temperature was set to 40 °C. Further, the elution solution was tetrahydrofuran and set to a flow rate of 1 ml/min, and the detector was an RI (differential refractometer) detector. 0.1 g of the sample was dissolved in 10 ml of tetrahydrofuran (THF). The weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined by using a calibration curve of standard polystyrene.

(2) Softening point

The measurement was carried out by a ring and ball method using an automatic softening point device (manufactured by Mingfeng Co., Ltd., ASP-M4SP (trade name)) according to Japanese Industrial Standard (JIS)-K-2207.

(3) Viscosity

E-type rotational viscometer (trade name) manufactured by BROOKFIELD Determination.

(4) Determination of epoxy equivalent

Using a potentiometric titration apparatus, methyl ethyl ketone was used as a solvent, and a tetraethylammonium bromide acetic acid solution was added thereto, and the measurement was carried out using a 0.1 mol/L perchloric acid-acetic acid solution.

(5) Determination of acid value

The measurement was carried out using a potentiometric titration apparatus using dioxane as a solvent and using a 0.1 N-KOH methanol solution.

(Synthesis of polyvalent hydroxy resin)

Synthesis Example 1

A phenol novolak (manufactured by Showa Denko, BRG-555 (trade name), a hydroxyl equivalent of 105 g/eq., and a softening point of 67 ° C and 150 ° C) as a polyvalent hydroxy compound component was placed in a 1 L four-necked flask. The melt viscosity was 0.08 Pa.s), 105 g, 0.055 g (300 ppm) of p-toluenesulfonic acid as an acid catalyst, and the temperature was raised to 120 °C. Next, 73 g of styrene (0.7 mol) was added dropwise thereto at 120 ° C for 3 hours to cause a reaction. Next, after reacting at 120 ° C for 1 hour, 170 g of styrene-modified multivalent hydroxy resin (StPN (styrene-modified phenol novolak resin)) was obtained. The hydroxyl equivalent is 178 g/eq., the softening point is 78 ° C, and the melt viscosity at 150 ° C is 0.13 Pa. s.

Synthesis Example 2

(synthesis of epoxy resin)

To a four-neck separable flask, 150 g of StPN obtained in Synthesis Example 1, 468 g of epichlorohydrin, and 70 g of diethylene glycol dimethyl ether were added and stirred to dissolve. After uniformly dissolving, it was kept at 65 ° C under a reduced pressure of 130 mmHg, and 70.3 g of a 48% aqueous sodium hydroxide solution was added dropwise over 4 hours. In the dropwise addition, the refluxed water and epichlorohydrin were separated by a separation tank. Separation, returning epichlorohydrin to the reaction vessel, and discharging the water out of the system for reaction. After completion of the reaction, the salt formed by filtration was removed, and then water-washing was carried out, and epichlorohydrin was distilled off to obtain 185 g of an epoxy resin (StPNE (styrene-modified phenol novolak type epoxy resin)). The resulting resin has an epoxy equivalent of 246. g/eq., softening point is 56 ° C, melt viscosity at 150 ° C is 0.10 Pa. s.

Example 1

(Synthesis of epoxy acrylate resin)

160 g of the epoxy resin obtained in Synthesis Example 2 was dissolved in 40 g of carbitol acetate, and then 46.9 g of acrylic acid, 3.2 g of triphenylphosphine, and 0.1 g of hydroquinone were added, and air was blown at 110 ° C. An epoxy acrylate resin was obtained while reacting for 8 hours. The epoxy equivalent of the epoxy acrylate resin after the reaction was 10875 g/eq., and the viscosity of the solution was 52.5 Pa. s (25 ° C). Further, titration with a 0.1 N-KOH/MeOH (methanol) solution gave an acid value of 3.2 (mg-KOH/g). The GPC chart is shown in Figure 1.

Example 2

(Synthesis of epoxy acrylate anhydride adduct)

74.2 g of tetrahydrophthalic anhydride and 146.6 g of carbitol acetate were added to the epoxy acrylate resin obtained in Example 1, and reacted at 110 ° C for 1.5 hours to obtain an epoxy acrylate anhydride addition. (Acid anhydride adduct A). The epoxy equivalent of the epoxy acrylate anhydride adduct after the reaction is 19022 g/eq., and the viscosity of the resin solution is 3.5 Pa. s (25 ° C). Further, titration with a 0.1 N-KOH/MeOH solution gave an acid value of 55.2 (mg-KOH/g). The GPC chart is shown in Figure 2.

Reference example 1

(Synthesis of epoxy acrylate resin)

160 g of a phenol novolac type epoxy resin (YDPN-638 (trade name) epoxy equivalent of 177 g/eq.) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. was dissolved in 40 g of carbitol acetate, followed by addition of 65.1 g of acrylic acid. 3.2 g of triphenylphosphine and 0.1 g of hydroquinone were reacted for 8 hours while blowing air at 110 ° C to obtain an epoxy acrylate resin. The epoxy equivalent of the epoxy acrylate resin after the reaction is 12000 g/eq., and the viscosity of the solution is 58.0 Pa. s (25 ° C). Further, titration with a 0.1 N-KOH/MeOH solution gave an acid value of 2.5 (mg-KOH/g).

Reference example 2

(Synthesis of epoxy acrylate anhydride adduct)

74.2 g of tetrahydrophthalic anhydride and 146.6 g of carbitol acetate were added to the epoxy acrylate resin obtained in Reference Example 1, and reacted at 110 ° C for 1.5 hours to obtain an epoxy acrylate anhydride addition. (Acid anhydride adduct B). The epoxy equivalent of the epoxy acrylate anhydride adduct after the reaction is 20990 g/eq., and the viscosity of the resin solution is 4.0 Pa. s (25 ° C). Further, titration with a 0.1 N-KOH/MeOH solution gave an acid value of 55.0 (mg-KOH/g).

Example 3

The carbitol acetate in the epoxy acrylate resin solution obtained in Example 1 was removed by distillation under reduced pressure to obtain an epoxy acrylate resin, and then 20 g of the epoxy acrylate resin was added to the fluororesin. In the mold, 0.2 g of dicumyl peroxide was added, and the mixture was heated in an oven at 100 ° C for 30 minutes and at 170 ° C for 1 hour to be hardened.

Comparative example 1

The carbitol acetate in the epoxy acrylate resin solution obtained in Reference Example 1 was removed by distillation under reduced pressure to obtain an epoxy acrylate resin, and then 20 g of the epoxy acrylate resin was added. In a mold made of a fluororesin, 0.2 g of dicumyl peroxide was added, and the mixture was heated in an oven at 100 ° C for 30 minutes and at 170 ° C for 1 hour to be cured.

The physical properties of the cured product obtained in Example 3 and Comparative Example 1 are shown in Table 1.

Example 4 to Example 5 and Comparative Example 2 to Comparative Example 3

Using the epoxy acrylate anhydride adduct A obtained in Example 2, using a bisphenol A type ring Oxygen resin (epoxy resin A; YD-128 (trade name) epoxy equivalent of 188g/eq. manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), biphenyl type epoxy resin (epoxy resin B; manufactured by Mitsubishi Chemical Corporation) YX-4000H (trade name) epoxy equivalent is 195 g/eq.) as an epoxy resin component. Dipentaerythritol hexaacrylate (DPHA (trade name): manufactured by Daicel-Cytec Co., Ltd.) was used as an acrylate component, and Irgacure 907 (trade name, manufactured by BASF) was used as a photopolymerization initiator. A spherical molten cerium oxide FB-60 (trade name, manufactured by Denki Chemical Industries, Ltd.) was used as the cerium oxide component. Further, in Comparative Example 2 to Comparative Example 3, the acid anhydride adduct B obtained in Reference Example 2 was used.

The components were blended in the proportions (parts by weight) shown in Table 2, and kneaded by a roll mill to prepare photosensitive resin compositions of Examples 4 to 5 and Comparative Examples 2 to 3. The properties of the obtained photosensitive resin compositions of Examples 4 to 5 and Comparative Examples 2 to 3 were evaluated in the following manner.

The drying property of the coating film and the developability to the aqueous alkali solution were such that the photosensitive resin composition was applied to a copper foil laminate in a thickness of 20 μm to 30 μm, and dried at 70 ° C for 30 minutes using a hot air dryer. The film was evaluated. In addition, regarding the adhesion to the substrate, the solder heat resistance, the hardness, the chemical resistance, and the solvent resistance, a high-pressure mercury lamp is used, and the ultraviolet light having a wavelength of 365 nm and an illuminance of 25 mW/cm ² after exposure for 20 seconds is used. The weight % sodium carbonate aqueous solution was developed at 25 ° C for 60 seconds, then heated at 150 ° C for 30 minutes, and the completely cured coating film as a solder resist was evaluated. The results are shown in Table 2.

In addition, the evaluation criteria of each physical property are as follows.

(1) Dryness of the coating film

The drying property of the coating film was evaluated in accordance with JIS K-5400. The evaluation was carried out in the following three stages: ◎: no stickiness was found at all; ○: slight stickiness was found; and ×: significant stickiness was found.

(2) developability

The remaining resin was evaluated by visual observation using a 1% by weight aqueous sodium carbonate solution and developing at 25 ° C for 60 seconds, and then magnifying to 40 times. The evaluation was carried out in three stages: ◎: no resist remained on the copper surface; ○: a very small amount of resist remained on the copper surface; and ×: the resist was clearly left on the copper surface.

(3) Coating hardness

After exposure and development, the hardness of the coating film heated at 145 ° C for 50 minutes was evaluated in accordance with the test method of JIS K-5400.

(4) Adhesion

After exposure and development, cross-cut was performed so as to produce at least 100 grids on the coating film heated at 145 ° C for 50 minutes, and then a peeling test was performed using a tape, and the state of peeling of the grid was visually evaluated. The evaluation was performed in the following three stages: ◎: no peeling was observed at all the measurement points; ○: peeling was found at one to 20 measurement points among 100 measurement points; ×: at 100 measurement points Peeling was observed at 21 or more measurement points.

(5) Solder heat resistance

After exposure and development, the coating film heated at 145 ° C for 50 minutes was immersed in a solder bath of 260 ° C for 20 seconds in accordance with JIS D-0202, and the state of the coating film after immersion was evaluated. The evaluation was carried out in three stages: ◎: the appearance of the coating film was not abnormal; ○: the appearance of the coating film was extremely small; ×: the appearance of the coating film was swollen, melted, and peeled off.

(6) Chemical resistance

After exposure and development, the coating film heated at 145 ° C for 50 minutes was immersed in the following drug at 25 ° C for 1 hour, and the appearance and adhesion after immersion were evaluated.

Acid resistance: 10% by weight aqueous hydrochloric acid solution

Alkali resistance: 10% by weight aqueous caustic soda solution

Solvent resistance: trichloroethane, isopropanol

The evaluation was carried out in three stages: in the test of acid resistance, alkali resistance, and solvent resistance, no abnormality was set to ○; a small amount of swelling was set to Δ; and there was dissolution or swelling. Set to ×.

Claims (10)

An epoxy acrylate resin represented by the following general formula (1): (wherein R ₁ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms; R ₂ represents an aralkyl group represented by the following formula (a); R ₆ represents hydrogen or a methyl group; and n represents a number of 1 to 20; p represents the number from 0.1 to 2.5) (wherein R ₃ to R ₅ represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms). The epoxy acrylate resin according to claim 1, wherein the formula (a) is an aralkyl group derived from styrene. A method for producing an epoxy acrylate resin according to claim 1 or 2, wherein (meth)acrylic acid is reacted with an epoxy resin represented by the following formula (2); [Chemical 3] (wherein G represents a glycidyl group, R ₁ represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, R ₂ represents an aralkyl group represented by the following formula (a), and n represents a number of 1 to 20; wherein p represents Number of 0.1~2.5) (wherein R ₃ to R ₅ represent a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms). An epoxy acrylate anhydride adduct represented by the following formula (3), characterized in that a polybasic acid compound is reacted with an epoxy acrylate resin as described in claim 1 or 2 But (wherein R ₁ , R ₂ , R ₆ , n, p are synonymous with the formula (1), X represents hydrogen or a polybasic acid group represented by -OC-A(COOH) _m , and A is a residue of a polybasic acid, More than 10 mol% of X is the polybasic acid group; m represents 1, 2 or 3). A curable resin composition containing the epoxy acrylate resin and the polymerization initiator as described in claim 1 or 2. A curable resin composition containing the epoxy acrylate anhydride adduct and the polymerization initiator as described in claim 4 of the patent application. An alkali-developable photosensitive resin composition containing the epoxy acrylate anhydride adduct described in item 4 of the patent application and a photopolymerization initiator. The alkali-developable photosensitive resin composition according to claim 7, which further contains an epoxy resin. A cured product obtained by hardening a curable resin composition as described in claim 5 or 6. A cured product obtained by curing the alkali-developable photosensitive resin composition according to Item 7 or Item 8 of the patent application.