JP5196663B2 - Diolefin compound, epoxy resin, curable resin composition and cured product thereof - Google Patents

Description

  The present invention relates to a novel diolefin compound and an epoxy resin suitable for use in electrical and electronic materials.

Epoxy resins are generally cured with various curing agents, resulting in cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., adhesives, paints, laminates, moldings It is used in a wide range of fields such as materials, casting materials and resists. In recent years, especially in the field of semiconductor-related materials, electronic devices such as mobile phones with cameras, ultra-thin liquid crystals, plasma TVs, and light-weight notebook computers have become key to light, thin, short, and small. Very high characteristics have been demanded for packaging materials represented by resins. In particular, the structure of the tip package is complicated, and there are an increasing number of things that are difficult to seal without liquid sealing. For example, a cavity down type structure such as Enhanced BGA needs to be partially sealed and cannot be handled by transfer molding. For these reasons, the development of highly functional liquid epoxy resins has been demanded.
In recent years, RTM has been used as a composite material, a car body or a ship structural material because of its simplicity of manufacturing method. In such a composition, a low-viscosity epoxy resin is desired because it is easily impregnated into carbon fiber or the like.

  In addition, in the field of optoelectronics, especially in recent years, advanced information technology, in order to smoothly transmit and process a huge amount of information, technology that utilizes optical signals will be developed instead of conventional signal transmission using electrical wiring. In particular, in the field of optical components such as optical waveguides, blue LEDs, and optical semiconductors, development of resins having excellent transparency is desired. In response to these demands, alicyclic epoxy compounds have attracted attention.

  Compared with glycidyl ether type epoxy compounds, alicyclic epoxy compounds are superior in terms of electrical insulation and transparency, and are used in a variety of transparent sealing materials. On the other hand, the problem that hardened | cured material is hard and inferior toughness remains on the other side of such an excellent point, and examination is advanced in order to improve this fault (patent documents 1, 2).

JP 2006-52187 A. Japanese Patent Laid-Open No. 2007-510772

  An object of this invention is to provide the novel alicyclic epoxy resin which gives the hardened | cured material which is excellent in toughness.

（式中、複数存在するＲはそれぞれ独立して存在し、水素原子、もしくは炭素数１〜６のアルキル基を表す。）
で表されることを特徴とするジオレフィン化合物、
（２）
前項（１）に記載のジオレフィン化合物を酸化することにより得られるエポキシ樹脂、
（３）
過酸化水素、過酸のいずれかを用いてエポキシ化することを特徴とする前項（２）に記載のエポキシ樹脂、
（４）
前項（２）、（３）のいずれか一項に記載のエポキシ化合物と硬化剤および／または硬化触媒を含有する硬化性樹脂組成物、
（５）
前項（４）に記載の硬化性樹脂組成物を硬化してなる硬化物、
に関する。 As a result of intensive studies in view of the actual situation as described above, the present inventors have completed the present invention.
That is, the present invention
(1)
Following formula (1)

(In the formula, a plurality of R's are present independently and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
A diolefin compound characterized by:
(2)
An epoxy resin obtained by oxidizing the diolefin compound according to item (1),
(3)
The epoxy resin as described in (2) above, which is epoxidized using either hydrogen peroxide or peracid,
(4)
A curable resin composition comprising the epoxy compound according to any one of (2) and (3) above, a curing agent and / or a curing catalyst,
(5)
Hardened | cured material formed by hardening | curing curable resin composition of previous clause (4),
About.

  The olefin compound of the present invention is a raw material for an epoxy resin (epoxy resin of the present invention) that gives a cured product having excellent mechanical properties (particularly toughness). The curable fat composition of the present invention containing the epoxy resin of the present invention has a wide range of uses such as electric / electronic materials, molding materials, casting materials, laminated materials, paints, adhesives, resists, and also has an aromatic ring. First, it is very useful for optical materials.

  The olefin compound of the present invention has the following formula (1):

（式中、複数存在するＲはそれぞれ独立して存在し、水素原子、もしくは炭素数１〜６のアルキル基を表す。）
で表される。

(In the formula, a plurality of R's are present independently and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
It is represented by

  The diolefin compound represented by the formula (1) can be obtained by reacting a cyclohexenecarboxylic acid derivative with norbornanediols. As the cyclohexene carboxylic acid derivative, the following formula (2)

（式中、Ｒは水素原子、もしくは炭素数１〜６のアルキル基を表す。またＸはヒドロキシル基、炭素数１〜１０のアルコキシ基、ハロゲン原子を表す。）
で表される化合物で、具体的にはシクロヘキセンカルボン酸、シクロヘキセンカルボン酸メチル、シクロヘキセンカルボン酸エチル、シクロヘキセンカルボン酸プロピル、シクロヘキセンカルボン酸ブチル、シクロヘキセンカルボン酸ヘキシル、（シクロヘキセニルメチル）シクロヘキセンカルボキシレート、シクロヘキセンカルボン酸オクチル、シクロヘキセンカルボン酸クロライド、シクロヘキセンカルボン酸ブロマイド、メチルシクロヘキセンカルボン酸、メチルシクロヘキセンカルボン酸メチル、メチルシクロヘキセンカルボン酸エチル、メチルシクロヘキセンカルボン酸プロピル、（メチルシクロヘキセニルメチル）メチルシクロヘキセンカルボキシレート、メチルシクロヘキセンカルボン酸クロライド、などが挙げられるが、これらに限定されるものではない。これらは単独で用いてもよく、２種以上併用してもよい。

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom.)
In particular, cyclohexenecarboxylic acid, methyl cyclohexenecarboxylate, ethyl cyclohexenecarboxylate, propylcyclohexenecarboxylate, butylcyclohexenecarboxylate, hexylcyclohexenecarboxylate, (cyclohexenylmethyl) cyclohexenecarboxylate, cyclohexene Octyl carboxylate, cyclohexene carboxylic acid chloride, cyclohexene carboxylic acid bromide, methyl cyclohexene carboxylic acid, methyl methyl cyclohexene carboxylate, ethyl methyl cyclohexene carboxylate, propyl methyl cyclohexene carboxylate, (methyl cyclohexenyl methyl) methyl cyclohexene carboxylate, methyl cyclohexene Carboxylic acid chloride, etc. The present invention is not limited to, et al. These may be used alone or in combination of two or more.

Further, in the present invention, the norbornane diol, For example, the alcohol derivative after formylated Roh Ruborunajien (or alkyl-substituted norbornadiene), the resulting formyl group reduction. Or after formylation double bond norbornene carboxaldehyde (or alkyl-substituted norbornene carboxaldehyde), compounds obtained by the process of the alcohol compound can be mentioned up the resulting formyl group reduction.
It can also be synthesized by converting a norbornene dicarboxylic acid or norbornane dicarboxylic acid (or an alkyl-substituted product or alkyl ester thereof) into an alcohol form by reduction of the carboxylic acid.

  The norbornene dicarboxylic acid can be synthesized by Diels-Alder reaction of maleic acid (or maleic anhydride) with cyclopentadiene (or alkylcyclopentadiene) produced by retrodiels alder of dicyclopentadiene (or alkyldicyclopentadiene). .

  A general esterification method can be applied as a reaction between the cyclohexenecarboxylic acid derivative and norbornenediols. Specifically, general esterification reactions can be applied, such as Fischer esterification using acid catalysts, acid halides under basic conditions, alcohol reactions, and condensation reactions using various condensing agents (ADVANCED ORGANIC CHMISTRY). Part B: Reaction and Synthsis p135, 145-147, 151 etc.). Specific examples include esterification reactions between alcohols and carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980), and transesterification reactions of carboxylic acid esters (special It can also be produced by using Kai 2006-052187).

  As a preferable structure of the diolefin compound of the formula (1) synthesized as described above, in the formula (1), R is preferably any one of a hydrogen atom, a methyl group, an ethyl group, and a butyl group. In particular, when the substituent R is bonded to an olefin, in order to improve the reactivity, R bonded to the olefin is preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

The diolefin compound of the present invention represented by the formula (1) can be oxidized to form the epoxy resin of the present invention. Examples of the oxidation method include, but are not limited to, a method of oxidizing with a peracid such as peracetic acid, a method of oxidizing with a hydrogen peroxide solution, and a method of oxidizing with air (oxygen).
Specific examples of the epoxidation method using peracid include the method described in JP-A-2006-52187.
Various methods can be applied to the method of epoxidation with hydrogen peroxide solution. Specifically, JP-A-59-108793, JP-A-62-234550, JP-A-5-213919, Techniques such as those disclosed in JP-A-11-349579, JP-B-1-33471, JP-A-2001-17864, JP-B-3-57102 and the like can be applied.

Hereinafter, a particularly preferable method for obtaining the epoxy resin of the present invention will be exemplified.
First, the diolefin compound, heteropolyacids and quaternary ammonium salt of the present invention are reacted in an emulsion of an organic substance and hydrogen peroxide water.

The heteropolyacid used in the present invention is not particularly limited as long as it is a compound having a heteropolyacid structure, but a heteropolyacid containing tungsten or molybdenum is preferred, a heteropolyacid containing tungsten is more preferred, and tungstates are particularly preferred. Examples of typical heteropolyacids include tungsten acids such as tungstic acid, 12-tungstophosphoric acid, 12-tungstoboric acid, 18-tungstophosphoric acid, 12-tungstosilicic acid, and molybdenum-based acids such as molybdic acid and phosphomolybdic acid. Examples include salts.
Examples of the counter cation of these salts include quaternary ammonium ions, alkaline earth metal ions, and alkali metal ions.
Specifically, tetramethylammonium ion, benzyltriethylammonium ion, tridecanylmethylammonium ion, dilauryldimethylammonium ion, trioctylmethylammonium ion, trialkylmethyl (mixed type of octyl group and decanyl group) ammonium ion, Quaternary ammonium ions such as hexadecylmethylammonium ion, trimethylstearylammonium ion, tetrapentylammonium ion, cetyltrimethylammonium ion, benzyltributylammonium ion, tricaprylmethylammonium ion, dicetyldimethylammonium ion, calcium ion magnesium ion, etc. Alkaline earth metal ions, sodium, potassium, cesium and other alkalis Although such genera ions include, but are not limited to. Among these, sodium ions, potassium ions, calcium ions, and ammonium ions are particularly preferable counter cations.

  The amount of the heteropolyacid used is 0.5 to 20 mmol, preferably 1.0 in terms of metal element (tungstenic acid is tungsten atom, molybdic acid is molybdenum atom) with respect to 1 mol of the diolefin compound of the present invention. -20 mmol, more preferably 2.5-15 mmol.

As the quaternary ammonium salt, a quaternary ammonium salt having a total carbon number of 10 or more, preferably 25 to 100, more preferably 25 to 55 can be preferably used, and in particular, the alkyl chain is preferably an aliphatic chain. .
Specifically, tridecanylmethylammonium salt, dilauryldimethylammonium salt, trioctylmethylammonium salt, trialkylmethyl (a mixed type of a compound in which the alkyl group is an octyl group and a compound in which the decanyl group is a compound) ammonium salt, trihexa Examples include decylmethylammonium salt, trimethylstearylammonium salt, tetrapentylammonium salt, cetyltrimethylammonium salt, benzyltributylammonium salt, dicetyldimethylammonium salt, tricetylmethylammonium salt, and di-cured tallow alkyldimethylammonium salt. It is not limited to.
There are no particular limitations on the anionic species of these salts, and specific examples include halide ions, nitrate ions, sulfate ions, hydrogen sulfate ions, acetate ions, carbonate ions, and the like, but are not limited thereto.
When the number of carbon atoms exceeds 100, the hydrophobicity becomes too strong, and the solubility of the quaternary ammonium salt in the organic layer may deteriorate. When the number of carbon atoms is 10 or less, the hydrophilicity is increased, and the compatibility of the quaternary ammonium salt with the organic layer is similarly deteriorated.
The amount of quaternary ammonium salt used is preferably 0.01 to 10 times the valence of the tungstic acid used. More preferably, it is 0.05-6.0 times equivalent, More preferably, it is 0.05-4.5 times equivalent.
For example, since tungstic acid is divalent with H ₂ WO ₄ , the quaternary ammonium salt is preferably in the range of 0.02 to 20 mol per 1 mol of tungstic acid. Moreover, since it is trivalent in the case of tungstophosphoric acid, it is similarly 0.03 to 30 mol, and in the case of silicotungstic acid, it is tetravalent, so 0.04 to 40 mol is preferable.
When the amount of the quaternary ammonium carboxylate is lower than 0.01 times the valence of tungstic acids, the epoxidation reaction is difficult to proceed (in some cases, the reaction proceeds faster), and a by-product is produced. The problem is that things are easy to make. When the amount is more than 10 times equivalent, not only is the post-treatment difficult, but there is a function of suppressing the reaction, which is not preferable.

It is preferable to use a buffer in the reaction. Any buffer can be used, but it is preferable to use an aqueous phosphate solution in this reaction. The pH is preferably adjusted between pH 4 and 10, more preferably pH 5-9. When the pH is 4 or less, the hydrolysis reaction and polymerization reaction of the epoxy group easily proceed. On the other hand, when the pH is 10 or more, the reaction becomes extremely slow and the reaction time is too long.
In particular, in the present invention, when the tungstic acid as a catalyst is dissolved, the pH is preferably adjusted to be between 5 and 9.
For example, in the case of a phosphoric acid-phosphate aqueous solution, which is a preferable buffer, 0.1 to 10 mol% equivalent of phosphoric acid (or a phosphate such as sodium dihydrogen phosphate) is used. And a method of adjusting pH with a basic compound (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, etc.). Here, it is preferable that the pH is added so that the above-mentioned pH is obtained when hydrogen peroxide is added. It is also possible to adjust using sodium dihydrogen phosphate, disodium hydrogen phosphate, or the like. The preferred phosphate concentration is 0.1 to 60% by weight, preferably 1 to 45% by weight.
In this reaction, a buffer solution is not used, but disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, sodium tripolyphosphate, etc. (or hydrates thereof) are directly added without adjusting pH. It doesn't matter. In the sense of simplifying the process, there is no troublesome pH adjustment, and direct addition is particularly preferable. The amount of phosphate used in this case is usually 0.1 to 5 mol% equivalent, preferably 0.2 to 4 mol% equivalent, more preferably 0.3 to 3 mol% equivalent to hydrogen peroxide. is there. At this time, if the amount exceeds 5 mol% equivalent to hydrogen peroxide, pH adjustment is required, and if it is less than 0.1 mol% equivalent, the resulting hydrolyzate of the epoxy compound is likely to proceed or the reaction is slow. The harmful effect of becoming.

  This reaction is epoxidized using hydrogen peroxide. As the hydrogen peroxide used in this reaction, an aqueous solution having a hydrogen peroxide concentration of 10 to 40% by weight is preferable because of easy handling. When the concentration exceeds 40% by weight, handling becomes difficult and the decomposition reaction of the produced epoxy resin also tends to proceed.

  This reaction uses an organic solvent. The amount of the organic solvent to be used is 0.3 to 10, preferably 0.3 to 5, more preferably 0.5 to 2.5 by weight with respect to the diolefin compound 1 as the reaction substrate. is there. When the weight ratio exceeds 10, the progress of the reaction is extremely slow, which is not preferable. Specific examples of organic solvents that can be used include alkanes such as hexane, cyclohexane and heptane, aromatic hydrocarbon compounds such as toluene and xylene, and alcohols such as methanol, ethanol, isopropanol, butanol, hexanol and cyclohexanol. It is done. In some cases, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and anone; ethers such as diethyl ether, tetrahydrofuran, and dioxane; ester compounds such as ethyl acetate, butyl acetate, and methyl formate; A tolyl compound can also be used. Particularly preferred solvents are alkanes such as hexane, cyclohexane and heptane, and aromatic hydrocarbon compounds such as toluene and xylene.

As a specific reaction operation method, for example, when the reaction is performed in a batch-type reaction kettle, a diolefin compound, hydrogen peroxide (aqueous solution), heteropolyacid (catalyst), buffer solution, quaternary ammonium salt and organic solvent are added. In addition, stir in two layers. There is no specific designation for the stirring speed. Since heat is often generated when hydrogen peroxide is added, a method of gradually adding hydrogen peroxide after each component may be added.
At this time, buffer solution (or water and phosphate) and tungstic acid were added to adjust pH, and then quaternary ammonium salt, organic solvent and diolefin compound were added, and the mixture was stirred in two layers. A technique of dropping hydrogen is used.
Alternatively, while stirring water, an organic solvent, and a diolefin compound, tungstic acids and phosphoric acid (or phosphates) are added, pH is adjusted, and then a quaternary ammonium salt is added and stirred in two layers. However, a method of dropping hydrogen peroxide may be used.

  Although reaction temperature is not specifically limited, 0-90 degreeC is preferable, More preferably, it is 0-75 degreeC, Especially 15 to 60 degreeC is preferable. When the reaction temperature is too high, the hydrolysis reaction tends to proceed, and when the reaction temperature is low, the reaction rate becomes extremely slow.

  Although the reaction time depends on the reaction temperature, the amount of catalyst, etc., from the viewpoint of industrial production, a long-time reaction is not preferable because it consumes a large amount of energy. A preferable range is 1 to 48 hours, preferably 3 to 36 hours, and more preferably 4 to 24 hours.

  After completion of the reaction, quenching of excess hydrogen peroxide is performed. The quenching treatment is preferably performed using a basic compound. It is also preferable to use a reducing agent and a basic compound in combination. As a preferable treatment method, there is a method of quenching the remaining hydrogen peroxide using a reducing agent after adjusting neutralization to pH 6 to 10 with a basic compound. When the pH is 6 or less, heat generated when reducing excess hydrogen peroxide is large, and decomposition products may be generated.

Examples of the reducing agent include sodium sulfite, sodium thiosulfate, hydrazine, oxalic acid, vitamin C and the like. As the amount of the reducing agent used, excess hydrogen peroxide is usually 0.01 to 20 times mol, more preferably 0.05 to 10 times mol, still more preferably 0.05 to 3 times mol, based on the number of moles. is there.
These are preferably added as an aqueous solution, and the concentration is preferably 0.5 to 30% by weight.

Basic compounds include metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide, metal carbonates such as sodium carbonate and potassium carbonate, phosphorus such as sodium phosphate and sodium hydrogen phosphate. Examples thereof include basic solids such as acid salts, ion exchange resins, and alumina.
The amount used is water or organic solvents (for example, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl isobutyl ketone and methyl ethyl ketone, hydrocarbons such as cyclohexane, heptane and octane, methanol, ethanol, isopropyl alcohol, etc. The amount used is usually 0.01 to 20 times mol, more preferably 0.05 to 10 times the number of moles of excess hydrogen peroxide. Mol, more preferably 0.05 to 3 times mol. These may be added as water or a solution of the above-mentioned organic solvent, or may be added alone.
When a solid base that does not dissolve in water or an organic solvent is used, it is preferable to use an amount of 1 to 1000 times by weight with respect to the amount of hydrogen peroxide remaining in the system. More preferably, it is 10-500 times, More preferably, it is 10-300 times. In the case of using a solid base that does not dissolve in water or an organic solvent, the treatment may be carried out after separation of an aqueous layer and an organic layer described later.

After the hydrogen peroxide quench (or before quenching), if the organic layer and the aqueous layer are not separated, or if no organic solvent is used, the above-mentioned organic solvent is added and the operation is performed. The reaction product is extracted from the layer. The organic solvent used at this time is 0.5 to 10 times, preferably 0.5 to 5 times in weight ratio to the raw material diolefin compound. This operation is repeated several times as necessary, and the separated organic layer is purified by washing with water as necessary.
The obtained organic layer may be an ion exchange resin, a metal oxide (especially, silica gel, alumina, etc. are preferred), activated carbon (especially, preferably a chemical activated carbon), a composite metal salt (especially a basic composite metal salt). Are preferably removed), a mineral with a viscosity (in particular, a layered viscosity mineral such as montmorillonite is preferred), and after washing with water and filtration, the solvent is distilled off to obtain the desired epoxy resin.
In some cases, it may be further purified by distillation. As the distillation method, distillation may be performed by a technique such as thin film or rotary molecular distillation.

  The epoxy resin thus obtained has the formula (3)

（式中、複数存在するＲはそれぞれ独立して存在し、水素原子、もしくは炭素数１〜６のアルキル基を表す。）
で表される分子を主成分とするが、式（４）

(In the formula, a plurality of R's are present independently and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
The main component is a molecule represented by formula (4)

（式中、Ａ〜Ｄの組み合わせはどのような組み合わせでも構わない。Ｒは式（３）におけるのと同じ意味を表す。）
に示すような各種の構造の化合物が混在する。またエポキシ基同士の重合した高分子量体や、その他副反応物が反応条件によっては生成する。

(In the formula, any combination of A to D may be used. R represents the same meaning as in formula (3).)
The compounds of various structures as shown in FIG. Further, polymerized high molecular weight polymer of epoxy groups and other side reaction products are generated depending on the reaction conditions.

  The obtained epoxy resin can be used as various resin raw materials such as epoxy acrylate and derivatives thereof, oxazolidone compounds, and cyclic carbonate compounds.

Hereinafter, it describes about the curable resin composition of this invention containing the epoxy resin of this invention.
The curable resin composition of the present invention contains the epoxy resin of the present invention as an essential component. In the curable resin composition of the present invention, two methods of heat curing with a curing agent (curable resin composition A) and cationic curing with an acid as a curing catalyst (curable resin composition B) can be applied.

  In the curable resin composition A and the curable resin composition B, the epoxy resin of the present invention can be used alone or in combination with other epoxy resins. When used in combination, the proportion of the epoxy resin of the present invention in the total epoxy resin is preferably 30% by weight or more, particularly preferably 40% by weight or more. However, when using the epoxy resin of this invention as a modifier of a curable resin composition, it adds in the ratio of 1 to 30 weight%.

  Examples of other epoxy resins that can be used in combination with the epoxy resin of the present invention include novolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, and phenol aralkyl type epoxy resins. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetaldehyde Non, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Glycidyl ethers derived from polycondensates with 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, and alcohols , Cycloaliphatic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, silsesquioxane epoxy resin (chain structure, cyclic structure, ladder structure, or a mixed structure of at least two of them) Has glycidyl group and / or epoxycyclohexane structure Solid or liquid epoxy resin having an epoxy resin) and the like although not limited thereto.

When using especially the curable resin composition of this invention for an optical use, combined use with an alicyclic epoxy resin or an epoxy resin of a silsesquioxane structure is preferable. Particularly in the case of an alicyclic epoxy resin, a compound having an epoxycyclohexane structure in the skeleton is preferable, and an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure is particularly preferable.
These epoxy resins include esterification reaction of cyclohexene carboxylic acid and alcohols or esterification reaction of cyclohexene methanol and carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980), etc.) Described), or Tyschenko reaction of cyclohexene aldehyde (method described in JP-A-2003-170059, JP-A-2004-262871, etc.), and further transesterification of cyclohexene carboxylic acid ester (JP-A-2006-052187). And the like, which are obtained by oxidizing a compound that can be produced by the method described in Japanese Patent Publication No.
The alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentane. Diols, diols such as 1,6-hexanediol and cyclohexanedimethanol, triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol, pentaerythritol, etc. And tetraols. Examples of carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid.

Furthermore, the acetal compound by the acetal reaction of a cyclohexene aldehyde derivative and an alcohol form is mentioned. As a reaction method, it can be produced by applying a general acetalization reaction. For example, a method of carrying out a reaction while azeotropically dehydrating using a solvent such as toluene or xylene as a reaction medium (US Pat. No. 2,945,008), concentrated hydrochloric acid A method in which polyhydric alcohol is dissolved in the mixture and then the reaction is carried out while gradually adding aldehydes (Japanese Patent Laid-Open No. 48-96590), a method using water as a reaction medium (US Pat. No. 3,092,640), A method using an organic solvent (Japanese Patent Laid-Open No. 7-215979), a method using a solid acid catalyst (Japanese Patent Laid-Open No. 2007-230992), and the like are disclosed. A cyclic acetal structure is preferable from the viewpoint of structural stability.
Specific examples of these epoxy resins include ERL-4221, UVR-6105, ERL-4299 (all trade names, all manufactured by Dow Chemical), Celoxide 2021P, Eporide GT401, EHPE3150, EHPE3150CE (all trade names, all Daicel). Chemical Industry) and dicyclopentadiene diepoxide, and the like, but are not limited to these (Reference: Review Epoxy Resin Basic Edition I p76-85).
These may be used alone or in combination of two or more.

Hereinafter, each curable resin composition will be referred to.
Thermal curing with a curing agent (curable resin composition A)
Examples of the curing agent contained in the curable resin composition A of the present invention include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and nitrogen-containing compounds such as polyamide resins synthesized from linolenic acid and ethylenediamine (amine, Amide compounds); phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methyl hexahydro Phthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, Cyclohe Acid anhydrides such as sun-1,3,4-tricarboxylic acid-3,4-anhydride; carboxylic acid resins obtained by addition reaction of various alcohols, carbinol-modified silicones and the above-mentioned acid anhydrides; bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [1,1′-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol) , Naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphth ) And formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1 Polycondensation with '-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4'-bis (chloromethyl) benzene, 1,4'-bis (methoxymethyl) benzene, etc. And their modified products, polyphenols such as halogenated bisphenols such as tetrabromobisphenol A, condensates of terpenes and phenols; imidazole, trifluoroborane-amine complexes, guanidine derivative compounds, etc. Limited to is not. These may be used alone or in combination of two or more.
In the present invention, compounds having an acid anhydride structure and / or a carboxylic acid structure represented by the aforementioned acid anhydrides and carboxylic acid resins are particularly preferable.

  In the curable resin composition A of the present invention, the amount of the curing agent used is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy groups of all epoxy resins. When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.

  In the curable resin composition A of the present invention, a curing accelerator may be used in combination with the curing agent. Specific examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza- Tertiary amines such as bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, etc. Quaternary ammonium salts, triphenylbenzylphosphonium salts, triphenylethylphosphonium salts, quaternary phosphonium salts such as tetrabutylphosphonium salts, and the like can be given. (The counter ion of the quaternary salt is not particularly specified, such as halogen, organic acid ion, hydroxide ion, etc., but organic acid ion and hydroxide ion are particularly preferable), metal compounds such as tin octylate, etc. It is done. When using a hardening accelerator, 0.01-5.0 weight part is used as needed with respect to 100 weight part of epoxy resins.

  The curable resin composition A of the present invention may contain a phosphorus-containing compound as a flame retardant imparting component. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric acid esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; epoxy resin and active hydrogen of the phosphanes A phosphorus-containing product obtained by reacting with Poxy compounds, red phosphorus and the like can be mentioned, and phosphoric esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. The phosphorus-containing compound content is preferably phosphorus-containing compound / total epoxy resin = 0.1 to 0.6 (weight ratio). If it is 0.1 or less, the flame retardancy is insufficient, and if it is 0.6 or more, there is a concern that it may adversely affect the hygroscopicity and dielectric properties of the cured product.

  Furthermore, you may add antioxidant to the curable resin composition A of this invention as needed. Antioxidants that can be used include phenol-based, sulfur-based, and phosphorus-based antioxidants. Antioxidants can be used alone or in combination of two or more. The usage-amount of antioxidant is 0.008-1 weight part normally with respect to 100 weight part with respect to the resin component in the curable resin composition of this invention, Preferably it is 0.01-0.5 weight part. It is.

  Examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant. Specific examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio)- Monophenols such as 6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,4-bis [(octylthio) methyl] -o-cresol; 2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-thiobis (3- Til-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) ) Propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t) -Butyl-4-hydroxy-hydrocinnamamide), 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,5-di-t -Butyl-4-hydroxybenzylphosphonate-diethyl ester, 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5- Bisphenols such as (tilphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, bis (3,5-di-t-butyl-4-hydroxybenzylsulfonate) ethyl 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t- Butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis- (4 '-Hydroxy-3'-tert-butylphenyl) butyric acid] glycol ester, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -iso Anureate, 1,3,5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol And the like.

  Specific examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and the like. .

  Specific examples of phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t- Butylphenyl) phosphite, cyclic neopentanetetrayl bis (octadecyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2,4 -Di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite, etc. 9,10-dihydro 9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -Oxaphosphaphenanthrene oxides such as 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are exemplified.

  These antioxidants can be used alone, but two or more of them may be used in combination. In the present invention, a phosphorus-based antioxidant is particularly preferable.

Furthermore, you may add a light stabilizer to the curable resin composition A of this invention as needed.
As the light stabilizer, hindered amine-based light stabilizers, particularly HALS and the like are suitable. HALS is not particularly limited, but representative examples include dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4- Polycondensate of piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, dimethyl-1- (2-hydroxyethyl) -4-hydroxy succinate -2,2,6,6-tetramethylpiperidine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], bis (1,2,2, 6,6-pentamethyl-4-pi Peridyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (3,5-di -T-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), etc. Only one HALS is used. Two or more types may be used in combination.

  Furthermore, binder resin can also be mix | blended with the curable resin composition A of this invention as needed. Examples of the binder resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. However, it is not limited to these. The blending amount of the binder resin is preferably in a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 0.05 to 20 parts per 100 parts by weight of the resin component. Part by weight is used as needed.

  An inorganic filler can be added to the curable resin composition A of the present invention as necessary. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These may be used alone or in combination of two or more. The content of these inorganic fillers is 0 to 95% by weight in the curable resin composition of the present invention. Furthermore, the curable resin composition of the present invention includes various agents such as silane coupling agents, mold release agents such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, surfactants, dyes, pigments, and ultraviolet absorbers. A compounding agent and various thermosetting resins can be added.

When using the curable resin composition of this invention for an optical semiconductor sealing agent, a fluorescent substance can be added as needed. For example, the phosphor has a function of forming white light by absorbing part of blue light emitted from a blue LED element and emitting wavelength-converted yellow light. After the phosphor is dispersed in advance in the curable resin composition, the optical semiconductor is sealed. There is no restriction | limiting in particular as fluorescent substance, A conventionally well-known fluorescent substance can be used, For example, rare earth element aluminate, thio gallate, orthosilicate, etc. are illustrated. More specifically, phosphors such as a YAG phosphor, a TAG phosphor, an orthosilicate phosphor, a thiogallate phosphor, and a sulfide phosphor can be mentioned, and YAlO ₃ : Ce, Y ₃ Al ₅ O ₁₂ : Ce, Y ₄ Al ₂ O ₉ : Ce, Y ₂ O ₂ S: Eu, Sr ₅ (PO ₄ ) ₃ Cl: Eu, (SrEu) O.Al ₂ O _{3 and the} like are exemplified. As the particle size of the phosphor, those having a particle size known in this field are used, and the average particle size is preferably 1 to 250 μm, particularly preferably 2 to 50 μm. When using these fluorescent substance, the addition amount is 1-80 weight part with respect to 100 weight part with respect to the resin component, Preferably, 5-60 weight part is preferable.

  The curable resin composition A of the present invention is obtained by uniformly mixing each component. The curable resin composition A of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, the epoxy resin of the present invention, a curing agent and, if necessary, a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent are sufficient until uniform using an extruder, kneader, roll, etc. as necessary. To obtain a curable resin composition, potting the curable resin composition, melting (without melting in the case of a liquid), molding using a casting or transfer molding machine, and further 80 to 200 ° C. The cured product of the present invention can be obtained by heating for 2 to 10 hours.

  Further, the curable resin composition A of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone as necessary, and the curable resin composition varnish. The curable resin composition of the present invention is obtained by hot press-molding a prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper and drying by heating. It can be set as the hardened | cured material of the thing A. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition of the present invention and the solvent. Moreover, if it is a liquid composition, the epoxy resin hardened | cured material which contains a carbon fiber by the RTM system as it is can also be obtained as it is.

  Moreover, the curable resin composition A of this invention can be used also as a modifier of a film type composition. Specifically, it can be used to improve the flexibility of the B-stage. In such a film-type resin composition, the curable resin composition A of the present invention is applied onto a release film as the curable resin composition varnish, the solvent is removed under heating, and then B-stage is performed. Thus, it is obtained as a sheet-like adhesive. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

  Furthermore, the curable resin composition A of the present invention can be used for general applications in which thermosetting resins such as epoxy resins are used. Specifically, adhesives, paints, coating agents, molding materials ( Sheet, film, FRP, etc.), insulating materials (including printed circuit boards, wire coatings, etc.), sealing materials, sealing materials, cyanate resin compositions for substrates, and acrylic esters as resist curing agents And additives to other resins and the like.

  Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

  As sealing agents, potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chip For example, underfill for QFP, BGA, CSP, etc., and sealing (including reinforcing underfill) can be used.

Curable resin composition B (cationic curing with acidic curing catalyst)
The curable resin composition B of the present invention that is cured using an acidic curing catalyst contains a photopolymerization initiator or a thermal polymerization initiator as an acidic curing catalyst. Furthermore, you may contain various well-known compounds, materials, such as a diluent, a polymerizable monomer, a polymerizable oligomer, a polymerization start adjuvant, a photosensitizer. Moreover, you may contain various well-known additives, such as an inorganic filler, a color pigment, a ultraviolet absorber, antioxidant, a stabilizer, as needed.

As the acidic curing catalyst, a cationic polymerization initiator is preferable, and a photocationic polymerization initiator is particularly preferable. Examples of the cationic polymerization initiator include those having an onium salt such as an iodonium salt, a sulfonium salt, and a diazonium salt, and these can be used alone or in combination of two or more.
Examples of active energy ray cationic polymerization initiators include metal fluoroboron complex salts and boron trifluoride complex compounds (US Pat. No. 3,379,653), bis (perfluoroalkylsulfonyl) methane metal salts (US Pat. No. 3,586,616), aryldiazonium Compound (US Pat. No. 3,708,296), aromatic onium salt of group VIa element (US Pat. No. 4,058,400), aromatic onium salt of group Va element (US Pat. No. 4069055), dicarbonyl chelate of group IIIa to Va element (US Pat. No. 4068091), thiopyrylium salts (US Pat. No. 4,139,655), group VIb elements in the form of MF ₆ -anions (US Pat. No. 4,161,478; M is selected from phosphorus, antimony and arsenic). Arylsulfonium complex salt (US Pat. No. 4,231,951) , Aromatic iodonium and aromatic sulfonium complexes (US Pat. No. 4,256,828), and bis [4- (diphenylsulfonio) phenyl] sulfide-bis-hexafluorometal salts (Journal of Polymer Science, Polymer Chemistry, Volume 2) 1789 (1984)). In addition, mixed ligand metal salts of iron compounds and silanol-aluminum complexes can also be used.
As specific examples, “Adekaoptomer SP150”, “Adekaoptomer SP170” (all manufactured by Asahi Denka Kogyo Co., Ltd.), “UVE-1014” (manufactured by General Electronics Co., Ltd.), “CD-1012” (Sartomer Company) Product), “RP-2074” (manufactured by Rhodia), and the like.
The amount of the cationic polymerization initiator used is preferably 0.01 to 50 parts by weight and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin component.

  Furthermore, it is possible to simultaneously use one or two or more of these photocationic polymerization initiators, known polymerization initiation assistants and photosensitizers. Examples of polymerization initiators include, for example, benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinolpropan-1-one, N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1- Chloroanthraquinone, 2-amylanthraquinone, 2-isopropylthioxatone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acetophenone di Chiruketaru, benzophenone, 4-methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis-diethylamino benzophenone, and a photo-radical polymerization initiator such as Michler's ketone. The usage-amount of polymerization initiation adjuvants, such as photoradical polymerization initiator, is 0.01-30 weight part with respect to 100 weight part of components which can carry out photoradical, Preferably it is 0.1-10 weight part.

  Specific examples of the photosensitizer include anthracene, 2-isopropylthioxatone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acridine orange, acridine yellow, phosphine R, benzo Examples include flavin, cetoflavin T, perylene, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethanolamine, triethylamine and the like. The usage-amount of a photosensitizer is 0.01-30 weight part with respect to 100 weight part of all the epoxy resin components, Preferably it is 0.1-10 weight part.

  Furthermore, various compounding agents such as inorganic fillers, silane coupling materials, mold release agents, pigments, and various thermosetting resins can be added to the curable resin composition B of the present invention as necessary. . Specific examples are as described above.

  The curable resin composition B of the present invention can be obtained by uniformly mixing each component. It is also possible to dissolve in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone, or γ-butyrolactone and make it uniform, and then use it after removing the solvent by drying. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition B of the present invention and the solvent. The curable resin composition B of the present invention can be cured by irradiating with ultraviolet rays, but the amount of ultraviolet irradiation varies depending on the curable resin composition, and therefore is determined by the respective curing conditions. What is necessary is just the irradiation amount which a photocurable curable resin composition hardens | cures, and should just satisfy | fill the curing conditions with favorable adhesive strength of hardened | cured material. Since it is necessary for light to be transmitted through the details during the curing, the epoxy resin and the curable resin composition B of the present invention are highly transparent. Also. In these epoxy resin-based photocuring, it is difficult to completely cure only by light irradiation, and in applications where heat resistance is required, it is necessary to complete reaction curing by heating after light irradiation.

  The heating after the light irradiation may be performed in the normal curing temperature range of the curable resin composition B. For example, the range of 30 minutes to 7 days at room temperature to 150 ° C. is suitable. Although it changes depending on the blending of the curable resin composition B, the higher the temperature range, the more effective the curing is after light irradiation, and the short heat treatment is effective. Further, the lower the temperature, the longer the heat treatment. By performing such heat after-curing, an effect of aging treatment is obtained.

  Moreover, since the shape of the cured product obtained by curing these curable resin compositions B can be variously selected depending on the application, it is not particularly limited. For example, it may be a film shape, a sheet shape, a bulk shape, or the like. . The molding method varies depending on the applicable part and member. For example, a casting method, a casting method, a screen printing method, a spin coating method, a spray method, a transfer method, a dispenser method, or the like can be applied. Although it is mentioned, it is not limited to these. As the mold, polishing glass, hard stainless steel polishing plate, polycarbonate plate, polyethylene terephthalate plate, polymethyl methacrylate plate, or the like can be applied. In addition, a polyethylene terephthalate film, a polycarbonate film, a polyvinyl chloride film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a polyimide film, or the like can be applied in order to improve releasability from the mold.

  For example, when used for a cation curable resist, first, the photo cation curable resin composition B of the present invention dissolved in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone, or γ-butyrolactone is used as a copper-clad laminate, The composition of the present invention is applied to a film thickness of 5 to 160 μm on a substrate such as a ceramic substrate or a glass substrate by a method such as screen printing or spin coating to form a coating film. The coating film is preliminarily dried at 60 to 110 ° C., and then irradiated with ultraviolet rays (for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a laser beam, etc.) through a negative film having a desired pattern. Then, post-exposure baking is performed at 70 to 120 ° C. Thereafter, the unexposed part is dissolved and removed (developed) with a solvent such as polyethylene glycol monoethyl ether, and if necessary, sufficient by irradiation with ultraviolet rays and / or heating (for example, at 100 to 200 ° C. for 0.5 to 3 hours). Curing is performed to obtain a cured product. In this way, it is also possible to obtain a printed wiring board.

  The cured product obtained by curing the curable resin composition A and the curable resin composition B of the present invention can be used for various applications including optical component materials. The optical material refers to general materials used for applications that allow light such as visible light, infrared light, ultraviolet light, X-rays, and lasers to pass through the material. More specifically, in addition to LED sealing materials such as lamp type and SMD type, the following may be mentioned. It is a peripheral material for liquid crystal display devices such as a substrate material, a light guide plate, a prism sheet, a polarizing plate, a retardation plate, a viewing angle correction film, an adhesive, and a film for a liquid crystal such as a polarizer protective film in the liquid crystal display field. In addition, color PDP (plasma display) sealing materials, antireflection films, optical correction films, housing materials, front glass protective films, front glass replacement materials, adhesives, and LED displays that are expected as next-generation flat panel displays LED molding materials, LED sealing materials, front glass protective films, front glass substitute materials, adhesives, and substrate materials for plasma addressed liquid crystal (PALC) displays, light guide plates, prism sheets, deflection plates , Phase difference plate, viewing angle correction film, adhesive, polarizer protective film, front glass protective film in organic EL (electroluminescence) display, front glass substitute material, adhesive, and various in field emission display (FED) Film substrate Front glass protective films, front glass substitute material, an adhesive. In the optical recording field, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical cards, Pickup lenses, protective films, sealing materials, adhesives and the like.

  In the optical equipment field, they are still camera lens materials, finder prisms, target prisms, finder covers, and light receiving sensor sections. It is also a photographic lens and viewfinder for video cameras. Projection lenses for projection televisions, protective films, sealing materials, adhesives, and the like. These include lens materials, sealing materials, adhesives, and films for optical sensing devices. In the field of optical components, they are fiber materials, lenses, waveguides, element sealing materials, adhesives and the like around optical switches in optical communication systems. Optical fiber materials, ferrules, sealing materials, adhesives, etc. around the optical connector. For optical passive components and optical circuit components, there are lenses, waveguides, LED sealing materials, CCD sealing materials, adhesives, and the like. These are substrate materials, fiber materials, device sealing materials, adhesives, etc. around an optoelectronic integrated circuit (OEIC). In the field of optical fiber, it is an optical fiber for lighting, light guides for decorative displays, sensors for industrial use, displays / signs, etc., and for communication infrastructure and home digital equipment connection. As the semiconductor integrated circuit peripheral material, it is a resist material for microlithography for LSI and VLSI material. In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, anti-corrosion coatings, switch parts, headlamps, engine internal parts, electrical parts, various interior and exterior parts, drive engines, brake oil tanks, automobile protection Rusted steel plates, interior panels, interior materials, protective / bundling wireness, fuel hoses, automobile lamps, glass replacements. In addition, it is a multilayer glass for railway vehicles. Further, they are toughness imparting agents for aircraft structural materials, engine peripheral members, protective / bundling wireness, and corrosion-resistant coatings. In the construction field, it is interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials. For agriculture, it is a house covering film. Next-generation optical / electronic functional organic materials include organic EL element peripheral materials, organic photorefractive elements, optical amplification elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, fiber materials, elements Sealing material, adhesive and the like.

  As sealing agents, potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light-emitting diodes, ICs, LSIs, potting sealings for ICs, LSIs such as COB, COF, TAB, flip chip For example, underfill for sealing, and sealing (reinforcing underfill) when mounting IC packages such as BGA and CSP.

  Other uses of the optical material include general uses in which the curable resin composition A or the curable resin composition B is used. For example, adhesives, paints, coating agents, molding materials (sheets, films) , FRP, etc.), insulating materials (including printed circuit boards, wire coatings, etc.), sealants, additives to other resins, and the like. Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

  EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified. The present invention is not limited to these examples. In the examples, the epoxy equivalent was measured using an E-type viscometer at JIS K-7236 and the viscosity at 25 ° C. The analysis conditions in gas chromatography (hereinafter referred to as “GC”) were as follows: HP5-MS (0.25 mm ID x 15 m, film thickness 0.25 μm) was used for the separation column, and the column oven temperature was set to the initial temperature 100. The temperature was set at 0 ° C., the temperature was raised at a rate of 15 ° C. per minute, and held at 300 ° C. for 60 minutes. Helium was used as a carrier gas. Furthermore, the measurement in gel permeation chromatography (hereinafter referred to as “GPC”) is as follows. The column is a Shodex SYSTEM-21 column (KF-803L, KF-802.5 (× 2), KF-802), the linking eluent is tetrahydrofuran, and the flow rate is 1 ml / min. The column temperature was 40 ° C., detection was performed at UV (254 nm), and a standard polystyrene manufactured by Shodex was used for the calibration curve.

Example 1
To a flask equipped with a stirrer, a reflux condenser, a stirrer, and a Dean-Stark tube, while purging with nitrogen, 150 parts of toluene, the following formula (5)

（セラニーズ製）７３部、３−シクロヘキセンカルボン酸１２６部、パラトルエンスルホン酸２部を加え、加熱還流下で１０時間、水を除きながら反応を行った。反応終了後、１０重量％炭酸水素ナトリウム水溶液５０部で２回水洗、さらに得られた有機層を水５０部で２回水洗した後、ロータリーエバポレータで有機溶剤を濃縮することで本発明のジオレフィン化合物（Ｄ-１）が１８０部得られた。得られたジオレフィン化合物は液状であり、ガスクロマトグラフィーによる純度は９５％、ゲルパーミエーションクロマトグラフィーによる分析の結果、＞９８％の純度である事を確認した。

(Celanese) 73 parts, 126 parts of 3-cyclohexenecarboxylic acid and 2 parts of paratoluenesulfonic acid were added, and the reaction was carried out under heating and refluxing for 10 hours while removing water. After completion of the reaction, the diolefin of the present invention is washed twice with 50 parts of a 10% by weight aqueous sodium hydrogen carbonate solution, the organic layer obtained is washed twice with 50 parts of water, and then the organic solvent is concentrated with a rotary evaporator. 180 parts of compound (D-1) was obtained. The obtained diolefin compound was liquid, and it was confirmed that the purity by gas chromatography was 95%, and the result of analysis by gel permeation chromatography was> 98%.

Example 2
A flask equipped with a stirrer, a reflux condenser and a stirrer was charged with 15 parts of water, 0.95 parts of 12-tungstophosphoric acid, 0.78 parts of disodium hydrogen phosphate, and di-tallow alkyldimethylammonium acetate 2 while purging with nitrogen. 7 parts (50% by weight hexane solution from Lion Akzo, Acquard 2HT acetate) were added to form a tungstic acid catalyst, and then 120 parts of toluene and 93 parts of the diolefin compound D-1 obtained in Example 2 were used. Was added and stirred again to obtain a liquid in an emulsion state. The temperature of this solution was raised to 50 ° C., and while stirring vigorously, 55 parts of 35% aqueous hydrogen peroxide was added and stirred as it was at 50 ° C. for 13 hours. When the progress of the reaction was confirmed by GC, the substrate conversion after the completion of the reaction was> 99%, and the raw material peak disappeared.
Next, after neutralizing with a 1% by weight aqueous sodium hydroxide solution, 25 parts of a 20% by weight aqueous sodium thiosulfate solution was added, stirred for 30 minutes, and allowed to stand. The organic layer separated into two layers was taken out, 10 parts of silica gel (Wakogel C-300), 20 parts of activated carbon (CAP SUPER made by NORIT) and 20 parts of bentonite (Bengel SH made by Hojun) were added and stirred at room temperature for 1 hour. And filtered. The obtained filtrate was washed with 100 parts of water three times, and the organic solvent was distilled off from the obtained organic layer to obtain the following formula (6).

を主成分とする化合物（ＥＰ−１）を９９部得た。
ＧＰＣの測定結果より、式（６）の骨格の化合物を９８％含有していることを確認した。さらに、ＧＣ測定においては純度９０％であった。またエポキシ当量は２１５ｇ／ｅｑ．であった。

99 parts of a compound (EP-1) containing as a main component was obtained.
From the measurement results of GPC, it was confirmed that 98% of the compound having the skeleton of formula (6) was contained. Furthermore, in the GC measurement, the purity was 90%. The epoxy equivalent was 215 g / eq. Met.

Example 3
By column chromatography using 105 parts of silica gel (Wakogel C-300, manufactured by Wako Pure Chemical Industries, Ltd.) with 15 parts of the obtained epoxy resin (EP-1), using a developing solvent of ethyl acetate: hexane = 1: 4. Purification was performed.
The obtained epoxy resin (EP-2) was 12 parts, and the purity of the obtained epoxy resin was confirmed to contain 98% or more of the skeleton compound of the formula (6) from the GPC measurement results. did. Furthermore, in the GC measurement, the purity was about 99%. The epoxy equivalent was 205 g / eq. Met.

Examples 4, 5, and 6
About the epoxy resins (EP-1 and EP-2) of the present invention obtained in Examples 2 and 3, as a curing agent, methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid MH700G, below) , H1), bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid HNA-100, hereinafter referred to as H2) as a curing accelerator, hexadecyl Using trimethylammonium hydroxide (Tokyo Chemical Industry Co., Ltd. 25% methanol solution, referred to as C1), blended at the blending ratio (parts by weight) shown in Table 1 below, defoamed for 20 minutes, A curable resin composition was obtained.

(Heat resistance test)
The curable resin compositions obtained in the examples and comparative examples were vacuum defoamed for 20 minutes, and then gently poured into a test piece mold having a width of 7 mm, a length of 5 cm, and a thickness of about 800 μm, and then a polyimide film from above. Covered with. The cast was cured under the above conditions to obtain a dynamic viscoelastic test piece. Using these test pieces, a dynamic viscoelasticity test was performed under the conditions shown below.
Measurement conditions: Dynamic viscoelasticity measuring instrument: TA-instruments, DMA-2980
Measurement temperature range: -30 ° C to 280 ° C
Temperature rate: 2 ° C./min Test piece size: 5 mm × 50 mm cut out (thickness is about 800 μm).
Analysis condition Tg: The peak point of Tan-δ in DMA measurement was defined as Tg.

Example 7, Comparative Example 1
The epoxy resin (EP-2) of the present invention obtained in Examples 2 and 3 and (3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate (ERL-manufactured by Dow Chemical Company) as a comparative example. 4221 Epoxy equivalent 140 g / eq. Hereinafter referred to as EP-3), H1 is used as a curing agent, C1 is used as a curing accelerator, and blended at a blending ratio (parts by weight) shown in Table 2 below, and defoamed for 20 minutes. The curable resin composition of the present invention was obtained.

  Using the obtained curable resin composition, a thermal durability transmittance test and an LED test were conducted in the manner described below. The curing conditions are 140 ° C. × 2 hours after preliminary curing at 120 ° C. × 2 hours.

(LED test)
Surface mount type in which the curable resin composition obtained in Example 7 and Comparative Example 1 was vacuum degassed for 20 minutes, filled in a syringe, and mounted with a light emitting element having an emission wavelength of 465 nm using a precision discharge device. It cast into LED ((PHI) 5mm). Thereafter, a test LED was obtained by curing under predetermined curing conditions.
(1) LED reflow test For the test under the following reflow conditions using a high-temperature observation apparatus (SMT Scope SK-5000 manufactured by Sanyo Seiko Co., Ltd.) after moisture absorption of the obtained test LED at 30 ° C 70% x 72Hr The presence or absence of cracks in the LED was visually observed.
The test is performed with n = 3, and the evaluation is made with (OK number) / (test number).
The temperature was raised from 25 ° C. to 150 ° C. at 2 ° C./second, then held at 150 ° C. for 2 minutes, further heated to 260 ° C. at 2 ° C./second, and maintained at 10 ° C., then 1.3 ° C. It cools to room temperature at / second.
(2) LED heat cycle test The heat cycle test is a thermal shock test in which a cycle of −40 ° C. × 15 minutes to 120 ° C. × 15 minutes is repeated 300 times with the time required for temperature increase and decrease as 2 minutes, to the test LED. The presence or absence of cracks was visually observed.

  From the above results, it can be seen that the epoxy resin of the present invention can provide the curable resin composition of the present invention having excellent toughness.

Claims (5)

Following formula (1)

(In the formula, a plurality of R's are present independently and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
The diolefin compound characterized by these. An epoxy resin obtained by oxidizing the diolefin compound according to claim 1. The epoxy resin according to claim 2, wherein the epoxy resin is epoxidized using either hydrogen peroxide or peracid. A curable resin composition comprising the epoxy compound according to claim 2 and a curing agent and / or a curing catalyst. A cured product obtained by curing the curable resin composition according to claim 4.