JP2013166941A - Curable resin composition, cured product thereof, and resin material for electronic parts - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition enabling non-organic solvent-based vanish adjustment, and being capable of attaining excellent heat resistance, a low dielectric constant and a low dielectric loss tangent.SOLUTION: A curable resin composition includes as the essential components (A) an epoxy resin, (B) an acid group-containing radically polymerizable monomer, (C) a radical polymerization initiator, and (D) a radically polymerizable monomer other than the (B) component. (A) The epoxy resin to be used is a polyglycidyl ether of a polyfunctional phenol of a molecular structure with a plurality of phenols with alicyclic hydrocarbon groups serving as a coupling group. The mass ratio of (B) the acid group-containing radically polymerizable monomer and (D) the radically polymerizable monomer other than the (B) component is in a range of 20/80 to 80/20.

Description

  The present invention is capable of adjusting a varnish in a non-organic solvent system, and can obtain a cured product that exhibits excellent heat resistance and low dielectric constant and low dielectric loss tangent. , Interlayer insulation material for build-up substrates, adhesive film for build-up, semiconductor sealing material, die attach agent, flip-chip mounting underfill material, grab top material, TCP liquid sealing material, conductive adhesive, liquid crystal sealing material The present invention relates to a curable resin composition suitable as an insulating material for various electronic component materials such as a cover lay for flexible substrates and resist ink, and a cured product thereof.

  An epoxy resin composition containing an epoxy resin and its curing agent as essential components is excellent in various physical properties such as high heat resistance, moisture resistance, and dimensional stability. Electronic parts such as conductive paste, conductive adhesives such as conductive paste and other adhesives, liquid sealing materials such as underfill, liquid crystal sealing materials, flexible substrate coverlays, build-up adhesive films, paints, photoresist materials, Widely used in color materials, fiber reinforced composite materials, etc.

  Among these applications, in the field of resin materials for various electronic components that require high fluidity, such as printed wiring boards, resist inks, conductive pastes, and underfill agents, in response to environmental impacts such as recent VOC problems. Non-solvent resin compositions are actively developed. For example, for printed wiring board materials, liquid epoxy resins typified by low molecular weight bisphenol type epoxy resins, and epoxy resin curing agents typified by acid anhydrides The non-solvent varnish which mix | blended is widely used. However, a cured product obtained by curing such low molecular weight bisphenol type epoxy resin with a curing agent for epoxy resin does not have a sufficient level of moisture resistance and heat resistance itself, and when using lead-free solder or mounting a high-frequency type semiconductor device There was a problem of insufficient resistance to heat history at the time.

  Moreover, a dicyclopentadiene type epoxy resin is known as an epoxy resin excellent in moisture resistance of a cured product (Patent Document 1 below). However, although this dicyclopentadiene type epoxy resin is excellent in moisture resistance of a cured product, it is solid at room temperature, so that it is an organic solvent for application to electronic materials such as printed wiring board insulating materials and build-up adhesive films. In addition to the inevitable use, the above-mentioned VOC problem remains, and when applied to the above-described electronic components compatible with lead-free solder, the resistance to thermal history has not reached a sufficient level. Furthermore, in the technical field of electronic component materials such as printed wiring board materials and build-up adhesive films, in recent years, signal speeds and frequencies have increased in various electronic devices, and as a result, a low dielectric constant is maintained. However, there is a demand for an insulating material that realizes a low dielectric loss tangent. The dicyclopentadiene type epoxy resin has a relatively low dielectric constant and dielectric loss tangent of the cured product itself, and has good dielectric properties, but has recently been required. The level was not reached.

  Furthermore, as a varnish for non-solvent printed wiring boards, a technology for mixing and varnishing a vinyl ester resin obtained by reacting a novolak type epoxy resin or a bisphenol type epoxy resin with methacrylic acid with an unsaturated monomer is also known. (Patent Document 2 below). However, when a vinyl ester resin obtained by reacting a novolak epoxy resin with methacrylic acid is used, its varnish viscosity is remarkably high, impairing the impregnation of the glass cloth, and the printed wiring board productivity is low. It was. On the other hand, when a vinyl ester resin obtained by reacting a liquid bisphenol-type epoxy resin with methacrylic acid is used, the varnish viscosity is low, but the heat resistance is not sufficient.

Japanese Patent No. 3735896 Japanese Patent No. 3415610

  Therefore, the problem to be solved by the present invention can be adjusted to a varnish without using an organic solvent, and after the curing reaction, the cured product has excellent heat resistance, low dielectric constant and low It is an object of the present invention to provide a curable resin composition that gives a dielectric loss tangent, and a cured product that combines high heat resistance, low dielectric constant, and low dielectric loss tangent.

The present inventors have found that in order to solve the above problem, a result of intensive studies, the epoxy resin (A), the acid group-containing radically polymerizable monomer (B), LA radical polymerization initiator (C), and the (B ) A curable resin composition comprising the other radical polymerizable monomer (D) as an essential component, wherein the epoxy resin (A) includes a plurality of phenols having an alicyclic hydrocarbon group as a linking group. Polyglycidyl ether of a polyfunctional phenol having a molecular structure to which a group is bonded, and the radical radical polymerizable monomer (B) and the other radical polymerizable monomer (B) component (D) ) And the former / the latter = 20/80 to 80/20, and curing them by a so-called in-situ polymerization reaction in which these are cured continuously or simultaneously, that is, the monomer ( B) The above-mentioned polyfunctional acid group Together are reacted with epoxy groups in the epoxy resin (A), the by polymerizing a radical polymerizable group resulting from the monomer (B), the pre-cure, the total weight to 10 mass solventless or composition % Viscosity resin composition having a viscosity measured using an E-type viscometer under a temperature condition of 25 ° C. when containing an organic solvent of 5% or less, in the range of 5 to 500 mPa · s , After curing, it was found that excellent heat resistance and dielectric properties were exhibited, and the present invention was completed.

That is, the present invention, the epoxy resin (A), the acid group-containing radically polymerizable monomer (B), LA radical polymerization initiator (C), and (B) the other radical polymerizable monomer component ( A curable resin composition having D) as an essential component, wherein the epoxy resin (A) is a polyfunctional phenol having a molecular structure in which a plurality of phenols are bonded with an alicyclic hydrocarbon group as a linking group. polyglycidyl ethers der is, the mass ratio of the acid group-containing radically polymerizable monomer and (B) wherein (B) and other radical polymerizable monomer component (D) is the former / the latter = 20 / It is in the range of 80-80 / 20, and is measured using an E-type viscometer under a temperature condition of 25 ° C. when no solvent or an organic solvent of 10% by mass or less is included with respect to the total mass of the composition be characterized in that that the viscosity is in the range of 5~500mPa · s It relates to a curable resin composition.

  The present invention further relates to a cured product obtained by reacting the curable resin composition in situ.

  The present invention further relates to a resin material for electronic parts comprising the curable resin composition.

  According to the present invention, it is possible to adjust to a varnish without using an organic solvent, and after the curing reaction, the cured product has excellent heat resistance and curability that provides a low dielectric constant and a low dielectric loss tangent. A resin composition and a cured product having both high heat resistance, low dielectric constant, and low dielectric loss tangent can be provided.

Hereinafter, the present invention will be described in detail.
The curable resin composition of the present invention, as a thermosetting resin component, an epoxy resin (A), the acid group-containing radically polymerizable monomer (B), LA radical polymerization initiator (C), and the (B ) A curable resin composition comprising the other radical polymerizable monomer (D) as an essential component, wherein the epoxy resin (A) includes a plurality of phenols having an alicyclic hydrocarbon group as a linking group. Polyglycidyl ethers of polyfunctional phenols having a molecular structure to which a kind is bonded are used. Then, by reacting these continuously or simultaneously, that is, the reaction between the epoxy group and the acid group and the polymerization reaction of the radical polymerizable group are performed simultaneously or continuously without distinguishing them as reaction steps. It is characterized by that. By adopting a curing system that cures by in-situ polymerization reaction in this way, heat resistance and dielectric properties in cured products can be obtained, whether they are non-organic solvent systems or liquid compositions, and even low-viscosity compositions. The characteristics can be dramatically improved.

  The epoxy resin (A) used in the present invention is a polyglycidyl ether of polyfunctional phenol having a molecular structure in which a plurality of phenols are bonded with an alicyclic hydrocarbon group as a linking group.

  Here, the phenols constituting the epoxy resin (A) are, for example, phenol, cresol, xylenol, ethylphenol, isopropylphenol, butylphenol, octylphenol, nonylphenol, vinylphenol, isopropenylphenol, allylphenol, phenylphenol, benzylphenol. , Chlorophenol, bromophenol (each including o, m, and p-isomers), bisphenol A, naphthol, dihydroxynaphthalene, and the like. Among these, phenol and cresol are particularly preferable from the viewpoint of excellent fluidity and curability.

  In addition, the alicyclic hydrocarbon group constituting the epoxy resin (A) is a connecting group of the phenol skeleton part that forms the glycidyl ether structure portion of the epoxy resin, and has a cyclohexane ring or a cyclohexene ring. Is preferable from the viewpoint of excellent water resistance improvement effect of the cured product. Among these, since this effect is particularly remarkable, specifically, unsaturated groups such as dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnorborna-2-ene, α-pinene, β-pinene, and limonene. A divalent alicyclic hydrocarbon group derived from an unsaturated bond in the molecular skeleton of the alicyclic compound is preferable. These alicyclic hydrocarbon groups may be present alone or in combination of two or more. Furthermore, among these, it is preferable that it is a bivalent complex alicyclic hydrocarbon group resulting from the unsaturated bond in the molecular skeleton of dicyclopentadiene from the point which is excellent in the heat resistance and moisture resistance of hardened | cured material.

  The epoxy resin (A) used in the present invention is a polyglycidyl ether of polyphenol having a structure in which a plurality of phenols are bonded via the above linking group, and depends on the number of aromatic hydrocarbon nuclei repeated by the linking group. Although various molecular weights can be obtained, as described above, the epoxy resin (A) contains 10 to 35% by weight of the binuclear compound in the resin, in addition to the low dielectric loss tangent, and further has heat resistance and low resistance. A cured product having a linear expansion coefficient can be obtained.

  Here, the content ratio of the binuclear compound is a resin component composed of two phenolic compounds per molecule in the epoxy resin (A).

  The epoxy resin (A) satisfies the above structural and molecular weight distribution conditions and has an epoxy equivalent of 253 to 350 g / eq. Is preferable from the point of becoming an epoxy resin excellent in curability and heat resistance, and those having an ICI melt viscosity at 150 ° C. in the range of 0.1 to 40 dPa · s are preferable.

  In order to obtain said epoxy resin (A), what is necessary is just to carry out the polyaddition reaction of the phenols and unsaturated alicyclic compound which were mentioned above, and to make the obtained intermediate and epihalohydrin react.

  Here, the production condition of the intermediate polyaddition reaction product is not particularly limited, but the content of the binuclear compound of the epoxy resin (A) is set in the range of 10 to 35% by weight. In order to achieve this, it is preferable to adjust the molar ratio of the phenol and unsaturated alicyclic compound during the reaction, for example, phenols / unsaturated alicyclic compound = 2.5 / 1 to 5/1 (molar ratio). ) Within the range of (), a preferred intermediate for obtaining the desired epoxy resin can be obtained.

If the production method of the above intermediate is described in detail, a polyaddition catalyst is added to the phenols which are melted or made into a solution, and after the unsaturated alicyclic compound is appropriately added thereto, the mixture is heated and stirred to advance the polyaddition reaction. Thereafter, unreacted phenols are recovered by distillation to obtain a polyaddition reaction product. Here, the reaction temperature is not particularly limited, but is preferably 40 to 150 ° C. The polyaddition catalyst may be an inorganic acid such as hydrochloric acid or sulfuric acid, an organic acid such as paratoluenesulfonic acid, AlCl ₃ , BF ₃ or the like. And Lewis acid.

  Here, the unsaturated alicyclic compound used for introducing these alicyclic hydrocarbon groups into the resin structure is an aliphatic cyclic hydrocarbon having two or more unsaturated double bonds in one molecule. Examples of the compound include dicyclopentadiene, tetrahydroindene, 4-vinylcyclohexene, 5-vinylnorborna-2-ene, α-pinene, β-pinene, and limonene. Among these, dicyclopentadiene is preferred from the viewpoint of property balance, particularly heat resistance and hygroscopicity. In addition, since dicyclopentadiene is contained in petroleum fractions, industrial dicyclopentadiene may contain other aliphatic or aromatic dienes as impurities, but heat resistance, curability, In consideration of moldability and the like, it is desirable to use a product having a purity of 90% by weight or more of dicyclopentadiene.

  Next, by reacting the polyaddition reaction product thus obtained with epihalohydrin, the desired epoxy resin (A) can be obtained, but this reaction can be carried out by a conventional method.

  For example, first, 2 to 15 equivalents relative to the hydroxyl group of the intermediate, preferably 3 to 10 equivalents of epihalohydrin are added and dissolved from the viewpoint of excellent melt viscosity reduction effect, and then in the polyaddition reaction product. A 0.8 to 1.2 equivalent amount of 10-50% NaOH aqueous solution with respect to the hydroxyl group is appropriately reduced at a temperature of 50-80 ° C for 3-5 hours. Stirring is continued for about 0.5 to 2 hours at that temperature after appropriate reduction, and the lower layer saline solution is discarded after standing. Then, excess epihalohydrin is recovered by distillation to obtain the resin. To this, an organic solvent such as toluene or MIBK is added, and a target resin can be obtained through a water washing-dehydration-filtration-desolvation step. For the purpose of reducing the amount of impurity chlorine, a solvent such as dioxane or DMSO may be used in the reaction.

  As the epihalohydrin used here, epichlorohydrin is the most common, but epiiodohydrin, epibromohydrin, β-methylepichlorohydrin, and the like can also be used.

Next, the acid group-containing radical polymerizable monomer (B) used in the present invention reacts with the epoxy resin (A) and at the same time causes polymerization of acryloyl groups by radical polymerization. In this invention, the heat resistance of hardened | cured material can be improved greatly by hardening by such an in-situ reaction. Such an acid group-containing radically polymerizable monomer (B) specifically includes acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and anhydrides thereof; or
Structural formula 1

（式中、Ｒ^１は炭素原子数２〜１０の脂肪族炭化水素基又は芳香族炭化水素基、Ｘはエステル結合又はカーボネート結合、Ｒ^２は炭素原子数２〜１０の脂肪族炭化水素基又は芳香族炭化水素基を表し、ｎは１〜５の整数を示す。）で表される化合物が挙げられる。

(Wherein R ¹ is an aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 10 carbon atoms, X is an ester bond or carbonate bond, R ² is an aliphatic hydrocarbon group having 2 to 10 carbon atoms, or Represents an aromatic hydrocarbon group, and n represents an integer of 1 to 5.).

  Here, in the structural formula 1, X having an ester bond is a compound obtained by reacting a hydroxyalkyl (meth) acrylate with an aliphatic dicarboxylic acid having 2 to 10 carbon atoms; ) A compound obtained by reacting an acrylate with an aromatic dicarboxylic acid; a reaction between a hydroxyalkyl (meth) acrylate, an aliphatic diol having 2 to 10 carbon atoms, and an aliphatic dicarboxylic acid having 2 to 10 carbon atoms And a compound obtained by reacting a hydroxyalkyl (meth) acrylate, an aliphatic diol having 2 to 10 carbon atoms, and an aromatic dicarboxylic acid.

  Here, examples of the hydroxyalkyl (meth) acrylate include β-hydroxyethyl methacrylate and β-hydroxyethyl acrylate. Examples of the aliphatic dicarboxylic acid having 2 to 10 carbon atoms include succinic anhydride, adipic acid, maleic anhydride, tetrahydrophthalic acid, and cyclohexanedicarboxylic acid. Examples of the aromatic dicarboxylic acid include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid and the like.

  Furthermore, as the aliphatic diol having 2 to 10 carbon atoms, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propane Diol, 3-methyl-1,5-pentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanediethanol, 1,3-cyclohexanedie Nord, 1,4-cyclohexane diethanol, and the like. Of these, butanediol, pentanediol, hexanediol, cyclohexanediol, and cyclohexanedimethanol having 4 to 8 carbon atoms are preferred from the viewpoint of excellent compatibility with the epoxy resin (A).

  In the structural formula 1, as having X as a carbonate bond, for example, after obtaining a polycarbonate diol by transesterification of an aliphatic diol having 2 to 10 carbon atoms and a dialkyl carbonate, (meth) acrylic acid or The compound obtained by making it react with the derivative is mentioned.

Here, as the aliphatic diol having 2 to 10 carbon atoms, for example, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- Hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1, 3-propanediol, 3-methyl-1,5-pentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexane Dimethanol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanediethanol, 1,3-cyclohexane Sanji ethanol, those having 3 to 10 carbon atoms such as 1,4-cyclohexane diethanol, and the like. Of these, butanediol, pentanediol, hexanediol, cyclohexanediol, and cyclohexanedimethanol having 4 to 8 carbon atoms are preferred from the viewpoint of excellent compatibility with the epoxy resin (A).
On the other hand, examples of the dialkyl carbonate include dimethyl carbonate from the viewpoint of reactivity.

  Among these, particularly selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and their anhydrides from the viewpoint of the effect of reducing the viscosity and the heat resistance of the cured product. Of these, acrylic acid and methacrylic acid are preferable, and methacrylic acid is particularly preferable.

  The blending ratio of the epoxy resin (A) and the acid group-containing radical polymerizable monomer (B) detailed above is 100 parts by mass in total of the epoxy resin (A) and the acid group-containing radical polymerizable monomer (B). With respect to the flowability of the composition, the epoxy resin (A) is 40 to 90 parts by mass and the acid group-containing radical polymerizable monomer (B) is 10 to 60 parts by mass. It is preferable from the point that the balance of heat resistance of the cured product is good.

  The radical polymerization initiator (C) used in the present invention is not particularly limited as long as it is used as a thermal radical polymerization initiator. For example, methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1, 1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-hexylperoxy) 3,3,5 -Trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) ) Cyclododecane, n-butyl 4,4-bis (t-butyl pero) B) Valerate, 2,2-bis (t-butylperoxy) butane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, t-butyl hydroperoxide, P-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, α, α '-Bis (t-butylperoxy) diisopropylbenzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, Isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide Id, lauroyl peroxide, cinnamic acid peroxide, m-toluoyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-3-methoxybutylperoxy Dicarbonate, di-2-ethylhexylperoxydicarbonate, di-sec-butylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxy Dicarbonate, α, α′-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl- 1-methyl Ruethyl peroxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 2,5-dimethyl -2,5-bis (2-ethylhexanoylperoxy) hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1-cyclohexyl-1-methylethylperoxy-2- Ethyl hexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, t -Butylperoxylaurate, t-butylperoxy-3,5,5-trimethylhexanoate , T-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-hexyl Peroxybenzoate, t-butylperoxy-m-toluoylbenzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate, t-butylperoxyallyl monocarbonate, 3,3 ′, 4 Examples include 4′-tetra (t-butylperoxycarbonyl) benzophenone. The radical polymerization initiator (C) is used in an amount of 0.001% by mass to 5% by mass with respect to the total mass of the radical polymerizable component and the total mass of the radical polymerization initiator (C). Preferably it is done.

  In the curable resin composition of the present invention, a reaction catalyst for reacting the epoxy resin (A) with the acid group-containing radical polymerizable monomer (B) can be used in combination as appropriate. Examples of the reaction catalyst include tertiary amines such as triethylamine, N, N-benzyldimethylamine, N, N-dimethylphenylamine, N, N-dimethylaniline or diazabicyclooctane; trimethylbenzylammonium chloride, triethylbenzyl Quaternary ammonium salts such as ammonium chloride and methyltriethylammonium chloride; phosphines such as triphenylphosphine and tributylphosphine; imidazoles such as 2-methylimidazole, 1,2-dimethylimidazole and 2-ethyl-4-methylimidazole; Examples include triphenyl stibine and anion exchange resin. From the point which is excellent in the reactivity that the usage-amount of this catalyst is the range used as 0.01-0.5 mass% in the curable resin composition which is a varnish, especially 0.05-0.5 mass%. preferable.

  In the present invention, a curing reaction with a normal curing agent for epoxy resin is caused at a ratio of less than 80%, preferably less than 50%, particularly preferably less than 30% of the epoxy group of the epoxy resin (A). Also good.

Examples of the epoxy resin curing agent that can be used here include amine compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, and guanidine derivatives; dicyandiamide Amide compounds such as polyamide resin synthesized from dimer of linolenic acid and ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride Acid anhydride compounds such as methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride; phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin Polyhydric phenol compounds such as phenol resin, dicyclopentadiene phenol addition resin, triphenylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin; Examples thereof include benzaldehyde resins, naphthol benzaldehyde resins, phenol naphthaldehyde resins, naphthol naphthaldehyde resins, aminotriazine-modified phenol resins (polyhydric phenol compounds in which phenol nuclei are linked by melamine, benzoguanamine, or the like). When using these epoxy resin curing agents, the active hydrogen in the curing agent is less than 0.8 equivalent, preferably 0.5, based on the epoxy group of the bisphenol type epoxy resin (A). The range is less than equivalent, particularly preferably less than 0.3 equivalent.

The curable resin composition of the present invention is described above in terms of being able to impart functionalities such as appropriate flexibility and strength to the cured product according to the application, and further reducing the viscosity of the varnish. B) other radically polymerizable monomer of component (D) you together. Examples of the other radically polymerizable monomer (D) that can be used here include styrene, methylstyrene, halogenated styrene, divinylbenzene, and (meth) acrylic acid esters represented below. Can be mentioned.

  Examples of the monofunctional (meth) acrylate that can be used in the present invention include methyl, ethyl, propyl, butyl, 3-methoxybutyl, amyl, isoamyl, 2-ethylhexyl, octyl, isooctyl, nonyl, isononyl, decyl, isodecyl, dodecyl, Tridecyl, hexadecyl, octadecyl, stearyl, isostearyl, cyclohexyl, benzyl, methoxyethyl, butoxyethyl, phenoxyethyl, nonylphenoxyethyl, glycidyl, dimethylaminoethyl, diethylaminoethyl, isobornyl, dicyclopentanyl, dicyclopentenyl, dicyclo (Meth) acrylate etc. which have substituents, such as pentenyloxyethyl, are mentioned.

  Examples of the polyfunctional (meth) acrylate include 1,3-butylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol. Di (meth) such as neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, tricyclodecane dimethanol, ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol Di (meth) acrylate of diol obtained by adding 2 mol or more of ethylene oxide or propylene oxide to 1 mol of 1,6-hexanediol, acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate , Di (meth) acrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol, Diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A Di (meth) acrylate, 3 mol or more of ethylene oxide or propylene oxide added to 1 mol of trimethylolpropane, diol or tri (meth) acrylate of triol, 4 mol or more of ethylene oxide or propylene per 1 mol of bisphenol A Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra of diol obtained by adding oxide Meth) acrylate, dipentaerythritol poly (meth) acrylate, ethylene oxide-modified phosphoric acid (meth) acrylate, ethylene oxide-modified alkylated phosphoric acid (meth) acrylate.

  In addition to the above (meth) acrylates, functional oligomers containing ethylenic double bonds such as urethane (meth) acryl oligomers and epoxy (meth) acryl oligomers may be added as necessary. These can be used alone or in combination of two or more at any ratio.

The compounding ratio of the acid group-containing radical polymerizable monomer (B) to the other radical polymerizable monomer (D) of the component (B) is the former / the latter = 20/80 to 80/20. It is a range. In addition, other radical polymerizable monomer (B) component with respect to the total of the epoxy resin (A), the acid group-containing radical polymerizable monomer (B), and the radical polymerizable monomer (D) ( The amount of D) can be adjusted as appropriate depending on the intended use, viscosity, and flow characteristics. For example, when adjusting to a room temperature liquid varnish, the epoxy resin (A), acid group-containing radical polymerizable monomer The proportion is preferably 5 to 40 parts by mass with respect to 100 parts by mass of the total mass of the monomer (B) and the radical polymerizable monomer (D).

  The curable resin composition of the present invention described in detail above can further use a flame retardant from the viewpoint of imparting flame retardancy to the cured product. Examples of the flame retardant used here include halogen-based flame retardants such as polybrominated diphenyl ether, polybrominated biphenyl, tetrabromobisphenol A, and tetrabromobisphenol A type epoxy resin, and phosphorus-based flame retardants, nitrogen-based flame retardants, and silicones. Non-halogen flame retardants such as flame retardants, inorganic flame retardants, and organic metal salt flame retardants. Of these, non-halogen flame retardants are preferred because of the recent high demand for non-halogens.

  Various compounding agents, such as a silane coupling agent, a mold release agent, an ion trap agent, a pigment, can be added to the curable resin composition of this invention as needed.

  The curable resin composition of the present invention can be easily obtained as a liquid composition by uniformly stirring the above-described components.

  As described above, the curable resin composition of the present invention is a liquid composition at room temperature without using an organic solvent, or a composition exhibiting high fluidity at the time of melting. A small amount may be used in combination. Examples of the organic solvent that can be used here include acetone, methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, N, N-dimethylformamide, methanol, ethanol, and the like. The amount of the organic solvent used is preferably 10% by mass or less in the composition.

The curable resin composition of this invention can be manufactured by mixing each above-mentioned component uniformly. Here, when adjusting the curable resin composition of the present invention to a liquid composition at room temperature (25 ° C.), it has excellent fluidity before curing, and exhibits extremely high heat resistance after curing. Is expressed. Specifically, the varnish obtained by uniformly mixing the above-mentioned components has a viscosity measured at 25 ° C. using an E-type viscometer (“TV-20 type” cone plate type manufactured by Toki Sangyo Co., Ltd.). It is the range of 5-500 mPa * s, and it is more preferable that it is 5-350 mPa * s.

  As described above, the cured product of the curable resin composition of the present invention is obtained by in-situ polymerization reaction of a composition obtained by uniformly mixing the above-described components in a use state corresponding to various uses. is there. Here, as described above, the in-situ reaction is performed simultaneously or continuously without distinguishing the reaction between the epoxy group and the acid group and the polymerization reaction of the radical polymerizable group as reaction steps. Is.

  Specifically, the curing temperature at the time of performing the in-situ reaction is preferably in the temperature range of 50 to 250 ° C., and in particular, after curing at 50 to 100 ° C. to obtain a tack-free cured product. Furthermore, it is preferable to perform the treatment under a temperature condition of 120 to 200 ° C.

  The curable resin composition described in detail above is a laminate for printed wiring boards, an interlayer insulating material for build-up boards, an adhesive film for build-ups, a die attach agent, an underfill material for flip chip mounting, a grab top material, and for TCP. Liquid sealing materials, conductive adhesives, liquid crystal sealing materials, flexible circuit board cover lays, resin materials for electronic circuit boards such as resist inks, semiconductor sealing materials, optical materials such as optical waveguides and optical films, resin casting Coating materials such as materials, adhesives and insulating paints; Various optical semiconductor devices such as LEDs, phototransistors, photodiodes, photocouplers, CCDs, EPROMs, photosensors; Various uses such as CFRP and other fiber reinforced resin molded products Can be applied to. Among these, from the viewpoints of particularly high heat resistance, low dielectric constant, and low dielectric loss tangent, electronic component materials such as electronic circuit board resin materials and semiconductor sealing materials are preferable. In particular, in the present invention, it is a liquid composition at room temperature and has excellent heat resistance and reflow resistance after curing, and a material having a low dielectric constant and a low dielectric loss tangent. It is particularly useful in various applications such as an adhesive film for up, a liquid sealing material, and an underfill material for flip chip mounting.

  When the curable resin composition of the present invention is used for a laminated board for a printed wiring board, specifically, a varnish obtained by blending the above-described components is made of paper, glass cloth, glass nonwoven fabric, aramid paper, aramid By impregnating various fiber base materials such as cloth, glass mat, and glass roving cloth, and heating at a heating temperature corresponding to the solvent type used, preferably 50 to 170 ° C., a laminate as a cured product can be obtained. it can. In the present invention, it is possible to adjust a varnish excellent in fluidity, so that a fiber base necessary for laminate production is laminated in advance without impregnating and curing the prepreg, and impregnated with the varnish. It can be produced by curing by an in situ polymerization reaction. Under the present circumstances, it is preferable to prepare so that the resin part in a laminated board may be 20-60 mass%.

  When the curable resin composition of the present invention is used as a die attach agent or a conductive paste, for example, a method of dispersing fine conductive particles in the curable resin composition to obtain a composition for an anisotropic conductive film. And a paste resin composition for circuit connection and an anisotropic conductive adhesive which are liquid at room temperature.

  Further, in order to produce a buildup substrate using the curable resin composition of the present invention as an interlayer insulating material for a buildup substrate, for example, a circuit is formed by using a curable resin composition appropriately blended with rubber, filler, etc. The coated wiring board is applied using a spray coating method, a curtain coating method, or the like, and then cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. Such operations are sequentially repeated as desired, and a build-up substrate can be obtained by alternately building up and forming a resin insulating layer and a conductor layer having a predetermined circuit pattern.

  The method for producing an adhesive film for buildup from the curable resin composition of the present invention is, for example, a multilayer printed wiring board in which the curable resin composition of the present invention is applied on a support film to form a resin composition layer. And an adhesive film for use.

  When the curable resin composition of the present invention is used for an adhesive film for build-up, the adhesive film is applied to the circuit board at the same time as the circuit board is laminated under the temperature condition of lamination in the vacuum laminating method (usually 70 ° C to 140 ° C). It is important to exhibit fluidity (resin flow) that allows resin filling in existing via holes or through holes, and it is preferable to blend the above-described components so as to exhibit such characteristics.

  Here, the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. It is usually preferable to allow resin filling in this range. When laminating both surfaces of the circuit board, it is desirable to fill about 1/2 of the through hole.

  Specifically, the method for producing the adhesive film described above is, after preparing the varnish-like curable resin composition of the present invention, coating the varnish-like composition on the surface of the support film, further heating, Or it can manufacture by drying an organic solvent by hot air spraying etc. and forming the layer ((alpha)) of a curable resin composition.

  The thickness of the formed layer (α) is usually not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.

  In addition, the said layer ((alpha)) may be protected with the protective film mentioned later. By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches.

  The above-mentioned support film and protective film are made of polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, and further. Examples thereof include metal foil such as pattern paper, copper foil, and aluminum foil. In addition, the support film and the protective film may be subjected to a release treatment in addition to the mud treatment and the corona treatment.

  Although the thickness of a support film is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is used in 25-50 micrometers. Moreover, it is preferable that the thickness of a protective film shall be 1-40 micrometers.

  The above support film is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film is peeled after the adhesive film is heat-cured, adhesion of dust and the like in the curing process can be prevented. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance.

  Next, the method for producing a multilayer printed wiring board using the adhesive film obtained as described above is, for example, when the layer (α) is protected with a protective film, Lamination is performed on one or both sides of the circuit board by, for example, vacuum laminating so that α) is in direct contact with the circuit board. The laminating method may be a batch method or a continuous method using a roll. Further, the adhesive film and the circuit board may be heated (preheated) as necessary before lamination.

The laminating conditions are preferably a pressure bonding temperature (laminating temperature) of 70 to 140 ° C., a pressure bonding pressure of preferably 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m 2), Lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less.

  When the curable resin composition of the present invention is used for a semiconductor sealing material, it can be prepared by blending a filler with the curable resin composition. As the filler, silica is usually used, and the filling ratio is preferably in the range of 30 to 95% by mass per 100 parts by mass of the curable resin composition. Among them, flame retardancy and moisture resistance are preferred. In order to improve solder crack resistance and decrease the linear expansion coefficient, it is particularly preferably 70 parts by mass or more, and in order to significantly increase these effects, 80 parts by mass or more can further enhance the effect. it can.

  In order to produce an optical semiconductor device from the curable resin composition of the present invention, for example, the above curable resin composition is applied to an optical semiconductor to which an electrode such as a lead wire is attached, for example, with the curable resin composition of the present invention. Examples include a method of sealing and curing by a molding method such as transfer molding and casting, and a method of previously mounting an optical semiconductor on a circuit board, sealing it with the curable resin composition of the present invention, and curing. . Specifically, it can be obtained by pouring into a mold set with an optical semiconductor element, followed by heat curing under the above temperature conditions.

  As described above, the optical semiconductor device specifically includes an optical semiconductor device in which a light receiving element or a light emitting element such as an LED, a phototransistor, a photodiode, a photocoupler, a CCD, an EPROM, or a photosensor is sealed. Among them, an LED device, particularly a high-intensity LED device is particularly preferable, and a blue to white LED device having a main emission peak at a wavelength of 350 to 550 nm and a quaternary LED device are particularly preferable.

  Next, when the curable resin composition of the present invention is used in a fiber reinforced resin molded product, each component constituting the curable resin composition of the present invention is uniformly mixed to prepare a varnish, and then this is reinforced fiber It can be produced by impregnating a reinforced substrate made of the above, followed by in situ polymerization reaction.

  Specifically, the curing temperature at the time of performing the in-situ reaction is preferably in the temperature range of 50 to 250 ° C., and in particular, after curing at 50 to 100 ° C. to obtain a tack-free cured product. Furthermore, it is preferable to perform the treatment under a temperature condition of 120 to 200 ° C.

  In the present invention, the varnish viscosity is significantly lower than that of the conventional CFRP varnish, so that the heating temperature when impregnating the varnish into the fiber reinforcement is kept low, or in the normal temperature range of 5 to 40 ° C. Impregnation is possible. On the other hand, the molded product obtained by impregnating the fiber reinforcement and in-situ curing in spite of such a low viscosity varnish is not inferior to the conventional CFRP molded product in strength, but rather has a drastic heat resistance. improves.

  Here, the reinforcing fiber may be any of a twisted yarn, an untwisted yarn, or a non-twisted yarn, but the untwisted yarn or the untwisted yarn has both the moldability and mechanical strength of the fiber-reinforced plastic member, preferable. Furthermore, the form of a reinforced fiber can use what the fiber direction arranged in one direction, and a textile fabric. The woven fabric can be freely selected from plain weaving, satin weaving, and the like according to the site and use. Specifically, since it is excellent in mechanical strength and durability, carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber and the like can be mentioned, and two or more of these can be used in combination. Among these, carbon fiber is preferable from the viewpoint that the strength of the molded product is particularly good. As the carbon fiber, various types such as polyacrylonitrile-based, pitch-based, and rayon-based can be used. Among these, a polyacrylonitrile-based one that can easily obtain a high-strength carbon fiber is preferable. Here, the use amount of the reinforcing fiber when the varnish is impregnated into a reinforcing base material made of reinforcing fiber to form a fiber-reinforced composite material is such that the volume content of the reinforcing fiber in the fiber-reinforced composite material is 40 to 85%. The amount is preferably in the range.

  The fiber-reinforced resin molded product of the present invention is a molded product having a cured product of a resin composition for fiber-reinforced composite material and reinforcing fibers, specifically, the amount of reinforcing fibers in the fiber-reinforced resin molded product is: It is in the range of 40 to 70% by mass, and particularly preferably in the range of 50 to 70% by mass from the viewpoint of strength.

  As a method for producing such a fiber reinforced resin molded article, a fiber aggregate is laid on a mold, and a hand layup method or a spray-up method in which the varnish is laminated in multiple layers, either a male type or a female type, Vacuum bag method in which a base made of reinforcing fibers is stacked and impregnated while impregnating varnish, covered with a flexible mold that allows pressure to act on the molded product, and hermetically sealed is vacuum (reduced pressure) molding, reinforcing fibers in advance SMC press method in which a varnish containing varnish is formed into a sheet is compression-molded with a mold, RTM method in which the varnish is injected into a mating die laid with fibers, and a prepreg is produced by impregnating the varnish into a reinforcing fiber, There are methods such as baking this in a large autoclave. Among these, the RTM method is particularly preferred because of its excellent varnish fluidity. Preferred.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, “parts” and “%” are based on weight unless otherwise specified. In addition, each physical property evaluation was measured on condition of the following.
1) Varnish viscosity: Measured at 25 ° C. using an E-type viscometer (“TV-20 type” cone plate type manufactured by Toki Sangyo Co., Ltd.).
2) Glass transition point (dynamic viscoelasticity measurement (DMA method)): The cured product was cut into a width of 5 mm and a length of 50 mm with a diamond cutter, and measured using “DMS6100” manufactured by SII Nanotechnology, Inc. Room temperature to 260 ° C., temperature rising rate: 3 ° C./min, frequency: 1 Hz (sine wave), strain amplitude: 10 μm, dynamic viscoelasticity due to double-end bending of the cured product was measured. The temperature at the maximum value of tan δ was defined as Tg.
3) Thermomechanical analysis (TMA): When measured with a temperature rise rate of 3 ° C./min using a thermomechanical analyzer “TMA / SS6100” manufactured by Seiko Denshi Kogyo Co., Ltd. and changed to 40-60 ° C. The linear expansion coefficient (α1: linear expansion coefficient in the glass region) and the linear expansion coefficient (α2: linear expansion coefficient in the high temperature (rubber) region) when changed to 220 to 240 ° C. were measured.
4) Dielectric constant, dielectric loss tangent: In accordance with JIS-C-6481, the test piece was dried with an impedance material analyzer “HP4291B” manufactured by Agilent Technologies, and then placed in a room at 23 ° C. and 50% humidity. The dielectric constant and dielectric loss tangent at 100 MHz and 1 GHz of the cured product after storage for 24 hours were measured (test piece size 75 × 25 × 2 mm).
5) Differential scanning calorimetry (DSC): The peak of the melting peak in the DSC curve measured under the following conditions was defined as the melting peak temperature.
Equipment: DSC1 manufactured by METTLER TOLEDO
Sample amount; about 5mg
Temperature condition: 10 ° C./min.

  Hereinafter, the present invention will be described in detail by way of examples. The measurement methods for various properties are as follows.

Examples 1-2
1. Epoxy resin composition blending According to the blending shown in Table 1 below, an epoxy resin and a carboxylic acid, a polymerizable compound, a radical polymerization initiator, a curing accelerator, and the like were blended using a stirrer to obtain an epoxy resin composition. . Varnish viscosity was evaluated using this epoxy resin composition.
2. Preparation of cured resin plate of epoxy resin An epoxy resin composition was poured into a mold gap in which a spacer (silicone tube) having a thickness of 2 mm was sandwiched between glass plates, and cured in an oven at 100 ° C. for 1 hour. After confirming that it was in a tack-free state, after-curing was further performed at 170 ° C. for 1 hour to obtain a cured resin plate having a thickness of 2 mm. Using this as a test piece, various evaluation tests were performed. The results are shown in Table 1.

Comparative Example 1
According to the composition shown in Table 1 below, each component was mixed, then press molded at 150 ° C. for 20 minutes, and then cured (aftercured) at 175 ° C. for another 5 hours. A plate-like cured product was obtained. Using this as a test piece, various evaluation tests were performed. The results are shown in Table 1.

In addition, each component used for the epoxy resin composition of an Example and a comparative example is as follows.
“HP-7200”: Polyglycidyl ether of co-condensation resin of dicyclopentadiene and phenol (“Epiclon HP-7200” manufactured by DIC Corporation, ICI viscosity at 150 ° C .: 0.8 dPa · s)
“Perhexa HC”: 1,1-di (t-hexylperoxy) cyclohexane, trade name “Perhexa HC” manufactured by NOF Corporation “2E4MZ”: 2-ethyl-4-methylimidazole “TD-2131” : Phenol novolac resin (“Phenolite TD-2131” manufactured by DIC, softening point 80 ° C., hydroxyl group equivalent 103 g / eq.)

Comparative Example 2
242 g of methacrylic acid is charged into a four-necked flask, 0.4 g of hydroquinone is added, and then heated to 100 ° C., and 600 g of o-cresol novolac type epoxy resin (DIC made Epiklon N-695, epoxy equivalent: 214) is added. Slowly add and dissolve, then add 1.68 g of triphenylphosphine and react at 120-125 ° C. for 3 hours. After completion of the reaction, 292 g of styrene was added and dissolved uniformly with slow cooling to obtain a resin solution.
150 g of the resin solution thus obtained was added to 1.5 g of 1-cyanoethyl-2-ethyl-4-methylimidazole (“2E4MZ-CN” manufactured by Shikoku Chemicals Co., Ltd.), 1,1-di (t- 1.5 g of hexylperoxy) cyclohexane (“Perhexa HC” manufactured by NOF Corporation) was added and stirred and mixed at room temperature to obtain a varnish with a solid content of 82% by mass, and the viscosity of this varnish was measured.

Next, the obtained varnish was poured into a mold gap in which a spacer (silicone tube) having a thickness of 3 mm was sandwiched between glass plates, heated at 100 ° C. for 1 hour, and then heated at 200 ° C. for 1 hour to obtain a cured product. The dynamic viscoelasticity was measured by the above method and Tg was determined.
The varnish viscosity and Tg values are shown in Table 2.

Comparative Example 3
78.8 g of bisphenol A type epoxy resin (“Epiclon 850S” manufactured by DIC Corporation, epoxy equivalent of 188 g / eq.), Methyltetrahydrophthalic anhydride (“Epiclon B-570” manufactured by DIC Corporation, equivalent of 166 g / eq) .) 71.3 g and dimethylbenzylamine 1.5 g were uniformly stirred and mixed using a stirrer to obtain a varnish having a solid concentration of 52% by mass, and the viscosity of the varnish was measured.
Next, the obtained varnish was poured into a mold gap in which a spacer (silicone tube) having a thickness of 3 mm was sandwiched between glass plates, held at 110 ° C. for 1 hour to be cured, and the cured product was taken out of the mold. The temperature was raised to 165 ° C., and after reaching 165 ° C., curing was carried out by holding at that temperature for 2 hours. Using the obtained cured product as a test piece, dynamic viscoelasticity was measured to obtain Tg.
The varnish viscosity and Tg values are shown in Table 2.

Comparative Example 4
105 g of dimethacrylate of bisphenol A type epoxy resin (“Epiclon 850S” epoxy equivalent of 188 g / eq. Manufactured by DIC Corporation), 45 g of styrene monomer, 1,1-di (t-hexylperoxy) cyclohexane (manufactured by NOF Corporation “ Perhexa HC ") 1.5 g was uniformly mixed using a stirrer to obtain a varnish having a solid concentration of 69% by mass, and the viscosity of the varnish was measured.
Next, the obtained varnish was poured into a gap of a mold in which a spacer (silicone tube) having a thickness of 3 mm was sandwiched between glass plates, held at 100 ° C. for 1 hour to be cured, and the cured product was taken out of the mold. The temperature was raised to 170 ° C., and after reaching 170 ° C., curing was carried out by holding at that temperature for 1 hour. Using the obtained cured product as a test piece, dynamic viscoelasticity was measured to obtain Tg.
The varnish viscosity and Tg values are shown in Table 2.

Claims (7)

Epoxy resin (A), the acid group-containing radically polymerizable monomer (B), LA radical polymerization initiator (C), and said (B) other radical polymerizable monomer component (D) as essential components a curable resin composition in the epoxy resin (a) is, Ri polyglycidyl ethers der polyfunctional phenols having an alicyclic hydrocarbon group a molecular structure in which a plurality of phenols are bonded as binding Semmoto The mass ratio between the acid group-containing radical polymerizable monomer (B) and the other radical polymerizable monomer (D) of the component (B) is the former / the latter = 20/80 to 80/20. Viscosity measured using an E-type viscometer under a temperature condition of 25 ° C. in the case of containing no solvent or an organic solvent of 10% by mass or less based on the total mass of the composition. · s curable resin composition which is a range of . 2. The acid group-containing radically polymerizable monomer (B) is selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and anhydrides thereof. Curable resin composition. The blending ratio of the components (A) to (C) is equivalent ratio of the epoxy group in the epoxy resin (A) and the acid group in the acid group-containing radical polymerizable monomer (B) [ Epoxy group / acid group] is a ratio of 1/1 to 1 / 0.1, and the ratio of the radical polymerization initiator (C) is 0.1 to 3 parts by mass per 100 parts by mass of the composition. The curable resin composition according to claim 1 or 2. The total mass of the acid group-containing radical polymerizable monomer (B) and the other radical polymerizable monomer (D) of the component (B) is the combined mass of the components (A) to (D). hardening resin composition according to Ru any one of claims 1 to 3 range der of 5 to 50 mass%. The curable resin composition as described in any one of Claims 1-4 which contains the hardening | curing agent for other epoxy resins of said (B) component in addition to said each component. Hardened | cured material obtained by carrying out in situ polymerization reaction of the curable resin composition as described in any one of Claims 1-5 . The insulating material for electronic components which consists of a curable resin composition as described in any one of Claims 1-5 .