JP2010254628A - Diolefin compound, epoxy compound, curable resin composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alicyclic epoxy compound having excellent adhesion and heat-resistant transparency or its composition. <P>SOLUTION: The epoxy compound is prepared by oxidizing an unsaturated double bond of a diolefin compound represented by formula (1) (wherein R<SB>1</SB>-R<SB>5</SB>are each hydrogen atom or 1C-6C alkyl). Since the epoxy compound has a structure in which alicyclic epoxy groups are bonded by a linker containing one ether bond and ester bond, a cured product having excellent mechanical characteristics, adhesion and transparency is obtained. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a novel diolefin compound and epoxy compound 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, white LEDs (Light Emitting Diodes), and optical semiconductors, development of resins having excellent transparency is desired. In response to these demands, alicyclic epoxy compounds have attracted attention.

  An alicyclic epoxy compound is superior in terms of electrical insulation and transparency as compared with a glycidyl ether type epoxy compound, and is used in various ways as a transparent sealing material. However, since the alicyclic epoxy compound having a generally known structure is hard and inferior in toughness, improvement in adhesion and mechanical properties has been demanded. In order to improve this toughness, studies are underway to introduce saturated aliphatic chains such as lactone compounds and adipic acid and saturated aliphatic rings such as cyclohexanedimethanol into alicyclic epoxy compounds (Patent Document 1, Patent Document 2). However, it is still unsatisfactory, and epoxy resin compositions containing these compounds often have poor adhesion to silver-plated lead frames when used, for example, as an optical semiconductor encapsulant. The problem was.

  On the other hand, alicyclic epoxy compounds having a polyether in the structure have also been studied. Since these have a polyether structure, they are excellent in toughness, but they are inferior in heat-resistant transparency and have a problem of heat-resistant coloring of cured products when used in applications requiring transparency.

Japanese Patent No. 2906275 JP 2006-52187 A

  An object of this invention is to provide the alicyclic epoxy compound which is excellent in adhesiveness and heat-resistant transparency, and the curable resin composition which uses this epoxy compound as an essential component.

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 provides (1) the following formula (1)

(In Formula (1), R < ₁ > -R < ₅ > represents a hydrogen atom or a C1-C6 alkyl group, respectively) The diolefin compound (2) characterized by the above-mentioned in Formula (1) , R ₁ is a hydrogen atom, one of R ₂ and R ₃ is a methyl group, the other is a hydrogen atom, one of R ₄ and R ₅ is a methyl group, and the other is a hydrogen atom, (3) Epoxy compound obtained by oxidizing the diolefin compound according to (1) or (2) above (4) Epoxidized using either hydrogen peroxide or peracid Epoxy compound as described in (3) (5) Curable resin composition containing the epoxy compound as described in (3) or (4) above and a curing agent and / or a curing catalyst (6) As described in (5) above Hardness obtained by curing a curable resin composition Concerning a chemical.

Since the epoxy compound of the present invention has a structure in which alicyclic epoxy groups are bonded by a linker having one ether bond and an ester bond, it gives a cured product excellent in mechanical properties, adhesion, and transparency. Therefore, the curable fat composition of the present invention containing the epoxy compound of the present invention has a wide range of uses such as electric / electronic materials, molding materials, casting materials, laminated materials, paints, adhesives, resists, etc., particularly low colorability. Therefore, it is extremely useful for optical materials.
The diolefin compound of the present invention is useful because it easily becomes a raw material for the epoxy compound of the present invention.

  The diolefin compound of the present invention is obtained by reacting a cyclohexene carboxylic acid derivative with a diglycol compound. The cyclohexene carboxylic acid derivative includes the following formula (a)

（式中、Ｒ_１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 ₁ 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, cyclohexene carboxylic acid, cyclohexene carboxylate methyl, cyclohexene carboxylate ethyl, cyclohexene carboxylate propyl, cyclohexene carboxylate butyl, cyclohexene carboxylate hexyl, (cyclohexenylmethyl) cyclohexene carboxylate, 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.

Moreover, in this invention, as a diglycol compound, following formula (b)

(In the formula, R _{2 to} R ₅ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
Specifically, diethylene glycol, dipropylene glycol, dibutylene glycol and the like can be mentioned.

  The diglycol compound used in the present invention contains a molecule having a structure represented by the formula (b) as a main component, but may contain a structural isomer such as a primary alcohol. include.

A general esterification method can be applied as the reaction between the cyclohexenecarboxylic acid derivative and the diglycol compound. Specifically, esterification reaction of a cyclohexene carboxylic acid derivative and a diglycol compound (a method described in documents such as Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980) can be applied), or A transesterification reaction of cyclohexenecarboxylic acid ester (a method described in JP-A-2006-52187 or the like can be applied) can be applied. Any method may be used in the present invention, and specific examples include the following methods.
The cyclohexenecarboxylic acid derivative and the diglycol compound are esterified by dehydration under acidic conditions. For example, acidic catalysts (mineral acids such as sulfuric acid and phosphoric acid; organic acids such as toluenesulfonic acid, methanesulfonic acid, and ion exchange resin; heteropolyacids such as tungstic acid and molybdic acid, activated clay in solvents such as toluene and xylene In addition, inorganic acids, stannic chloride, zinc chloride, ferric chloride, and the like, and other organic and inorganic acid salts exhibiting acidity are added, and esterification is performed. You may react, performing azeotropic dehydration as needed.

The diolefin compound of the present invention thus synthesized has a structure represented by the formula (1). In general, the resulting diolefin body generally exhibits a liquid state (25 ° C.) due to its structure. In the diolefin compound of the present invention, in the formula (1), all R ₁ are hydrogen atoms, one of R ₂ and R ₃ is a methyl group, the other is a hydrogen atom, and one of R ₄ and R ₅ is methyl. Compounds in which the other is a hydrogen atom are preferred.

The diolefin compound of the present invention represented by the formula (1) can be oxidized to form the epoxy compound 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. Examples of peracids that can be used include formic acid, acetic acid, propionic acid, maleic acid, benzoic acid, m-chlorobenzoic acid, organic acids such as phthalic acid, and acid anhydrides thereof. Among these, it is preferable to use formic acid, acetic acid, and phthalic anhydride from the viewpoint of the efficiency of reacting with hydrogen peroxide to produce an organic peracid, the reaction temperature, the ease of operation, and the economy. Formic acid or acetic acid is more preferably used from the viewpoint of simplicity of reaction operation.

  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.

  An example of the epoxidation method using hydrogen peroxide, which is a preferable method for obtaining the epoxy compound of the present invention, is described below.

  As a specific method, the raw material diolefin compound of the present invention is reacted with a heteropolyacid and a quaternary ammonium salt in an organic substance and hydrogen peroxide water emulsion state.

  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.

Specific examples of the heteropolyacid include tungsten acids such as tungstic acid, 12-tungstophosphoric acid, 12-tungstoboric acid, 18-tungstophosphoric acid, and 12-tungstosilicic acid, and molybdenum-based acids such as molybdic acid and phosphomolybdic acid. Of the salt.
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, etc. Although such metal 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, any quaternary ammonium salt having a total carbon number of 10 or more can be used, and in particular, those whose alkyl chains are all aliphatic chains are preferred.
Specifically, tridecanylmethylammonium salt, dilauryldimethylammonium salt, trioctylmethylammonium salt, trialkylmethyl (mixed type of octyl group and decanyl group) ammonium salt, trihexadecylmethylammonium salt, trimethylstearylammonium salt , Tetrapentylammonium salt, cetyltrimethylammonium salt, benzyltributylammonium salt, dicetyldimethylammonium salt, tricetylmethylammonium salt, di-cured tallow alkyldimethylammonium salt, and the like.

These anionic species are not particularly limited, 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 catalyst in the organic layer becomes poor. When the number of carbon atoms is 25 or less, the hydrophilicity becomes strong. The solubility is deteriorated, which is not preferable.

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 an aqueous phosphate solution is used 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 6 or more, there is a problem that 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. In addition, a method of adjusting pH with a basic compound (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, etc.) is exemplified, but the method is not limited thereto. 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. The hydrogen peroxide used in this reaction preferably has a hydrogen peroxide concentration of 10 to 40% by weight because of easy handling. When this concentration exceeds 40% by weight, it is not preferable because handling becomes difficult and the decomposition reaction of the produced epoxy compound also easily proceeds.

  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 0.8 to the compound 1 having a carbon-carbon double bond as a reaction substrate. 5 to 2.5. When the weight ratio exceeds 10, the progress of the reaction is extremely slow, which is not preferable. Specific examples of usable organic solvents 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 can. 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; Tolyl compounds 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 each component after addition may be used.

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 15-60 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 lot 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. As a method for quenching hydrogen peroxide, a reducing agent can be used, and quenching may be performed with a basic compound. In the present invention, it is particularly preferable to carry out both of them. 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 an organic solvent (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 a solution of water or an 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 hydrogen peroxide quench (or before quenching), the organic and aqueous layers are separated. If necessary, wash the organic layer with water (if the organic solvent is small, specifically, the organic layer and the aqueous layer do not separate, or if no organic solvent is used, add the above-mentioned organic solvent and wash with water. The organic solvent used in this case is 0.5 to 10 times, preferably 0.5 to 5 times by weight with respect to the compound of formula (1)), or extraction of the reaction product from the aqueous layer. I do.

  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 preferred), clay minerals (especially lamellar viscosity minerals such as montmorillonite are preferred), impurities are removed, water washing, filtration and the like are performed, and then the solvent is distilled off to obtain the desired epoxy compound. .

  The epoxy compound thus obtained has the formula (2)

（式中、Ｒ_１〜Ｒ_５は水素原子、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（３）

(Wherein R _{1 to} R _{5 each} represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), the molecule represented by the formula (3)

（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。Ｒ１〜Ｒ５は式（１）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. R1 to R5 represent the same meaning as in formula (1).)
The compounds of various structures as shown in FIG. In addition, polymerized high molecular weight polymer of epoxies and other side reaction products are generated depending on reaction conditions.

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

Hereinafter, it describes about the curable resin composition of this invention containing the epoxy compound 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 compound of the present invention can be used alone or in combination with other epoxy resins. When used in combination, the proportion of the epoxy compound 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 compound of this invention as a modifier of 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 compound 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 Or solids such as silsesquioxane-based epoxy resins (epoxy resins having a glycidyl group and / or an epoxycyclohexane structure in a siloxane structure having a chain structure, a cyclic structure, a ladder structure, or a mixture of at least two of them) Liquid epoxy resins are listed, but are not limited to these There.

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 ethylenediamine and amine compounds (amines, 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 modified products thereof, 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 group of the epoxy resin. 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 of the present invention, a curing catalyst 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 phosphonium salts such as quaternary ammonium salts, triphenylbenzylphosphonium salts, triphenylethylphosphonium salts, tetrabutylphosphonium salts (the counter ions of quaternary salts are halogen, organic acid ions, water There is no special designation such as oxide ion , In particular an organic acid ion, a hydroxide ion.) Include metal compounds such as tin octylate. When using a hardening accelerator, 0.1-5.0 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 content of the phosphorus-containing compound is preferably 0.6 times or less with respect to the total amount of the epoxy resin components in the curable resin composition A of the present invention. If it exceeds 0.6 times, 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 compound 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 uniformly used as necessary using an extruder, a kneader, a roll, etc. Mix well until it becomes, potting the curable resin composition A, melting (without melting in the case of a liquid), molding using a casting or transfer molding machine, and further at 80-200 ° C. 2-10 The cured product of the present invention can be obtained by heating for a period of time.

  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, cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone as necessary, and curable. A resin composition varnish was used, and the prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and dried by heating was subjected to hot press molding. It can be set as the hardened | cured material of curable resin composition. 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 carbon fiber by the RTM system as it is can also be obtained.

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. When obtaining such a film-type resin composition, the curable resin composition of the present invention is applied to the release film by applying the varnish, removing the solvent under heating, and performing a B-stage adhesion. Get the agent. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

  Furthermore, general applications in which a thermosetting resin such as an epoxy resin is used are mentioned, for example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (printed boards, In addition to the encapsulating material, the encapsulating material, a cyanate resin composition for the substrate, and an additive to other resins such as an acrylate-based resin as the curing agent for the resist may be used.

  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.

In the curable resin composition B of the present invention, one or more polymerization initiation assistants and, if necessary, a photosensitizer can be used in combination with the cationic polymerization initiator.
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 radical photopolymerization initiator, is 0.01-30 weight part with respect to 100 weight part of resin components, 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 epoxy resin components, Preferably it is 0.1-10 weight part.

  Furthermore, various compounding agents such as an inorganic filler, a silane coupling material, a release agent, and a pigment, 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 heating and / or ultraviolet irradiation (for example, Reference: Review Epoxy Resin Vol. 1 Basic Edition I p82-84). Since the amount varies depending on the composition of the curable resin composition B, the curing conditions are determined in accordance with each composition. Basically, the cured product should be capable of expressing the strength required for the purpose of use. It ’s fine. Usually, these epoxy resin-based compositions are difficult to be completely cured only by light irradiation. Therefore, in applications requiring heat resistance, it is necessary to complete the reaction by heating after light irradiation. Moreover, since it is necessary to permeate | transmit the irradiation light in the case of photocuring to detail, the highly transparent compound and composition are desired in the epoxy resin and curable resin composition B of this invention. 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 normal 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 hardened | cured material obtained by making these curable resin composition B harden | cure can take various according to a use, it is not specifically limited, For example, it can also be set as shapes, such as a film form, a sheet form, and a bulk form. 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 in a cation curable resist, first, the photocation curable resin composition B of the present invention dissolved in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone, γ-butyrolactone, The composition of the present invention was applied to a substrate having a 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, and the coating film was preliminarily dried at 60 to 110 ° C. Thereafter, ultraviolet rays (for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a laser beam, etc.) are irradiated through a negative film having a desired pattern, followed by post-exposure baking at 70 to 120 ° C. Thereafter, the unexposed portion 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 (eg, 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. In addition, although the above-mentioned method is a case of a negative resist, the curable resin composition B of this invention can also be used as a positive resist.

  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 deflection 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 field of optical equipment, they are still camera lens materials, finder prisms, target prisms, finder covers, and light receiving sensor parts. 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, and automotive defenses 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. In addition, 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 is used. For example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), In addition to insulating materials (including printed circuit boards and wire coatings), sealants, additives to other resins and the like can be mentioned. 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 analytical conditions in gas chromatography (hereinafter referred to as GC) were HP5-MS (0.25 mm ID x 15 m, film thickness 0.25 μm) for the separation column, and the column oven temperature was set to an initial temperature of 100 ° C. The temperature was raised at a rate of 15 ° C. per minute and held at 300 ° C. for 25 minutes. Helium was used as a carrier gas. Furthermore, in the measurement of gel permeation chromatography (hereinafter referred to as GPC), it 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, reflux condenser, stirrer, and Dean-Stark tube, while purging with nitrogen, 100 parts of toluene, 39.1 parts of 3-cyclohexene-1-carboxylic acid, 20.1 parts of dipropylene glycol, p -1 part of toluenesulfonic acid was added, and the reaction was performed for 15 hours while dehydrating using a Dean-Stark tube under reflux conditions. After completion of the reaction, 3 parts of sodium tripolyphosphate was added and stirred at 100 ° C. for 1 hour. After cooling to room temperature, washing was performed 3 times with 100 parts of water, 100 parts of silica gel and 1 part of activated carbon were added to the obtained organic layer, and the mixture was stirred at room temperature for 2 hours, followed by filtration. By removing the solvent from the obtained filtrate, the following formula (4)

を主成分とする化合物を５１．３部得た。
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９４％、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。粘度は５６ｍＰａ・ｓ（２５℃ Ｅ型粘度計）であった。

As a main component, 51.3 parts of a compound were obtained.
The obtained diolefin compound was liquid, and it was confirmed that the purity by gas chromatography was 94% and the result by analysis by gel permeation chromatography was 98%. The viscosity was 56 mPa · s (25 ° C. E-type viscometer).

Example 2
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen, and 42 parts of the diolefin compound represented by the formula (4) obtained in Example 1, 5 parts of water, 38 parts of toluene, 12 parts -0.35 part of tungstophosphoric acid, 0.38 of disodium hydrogen phosphate, 0.7 part of trioctylmethylammonium acetate (50% by weight xylene solution manufactured by Lion Akzo) was added to obtain a liquid in an emulsion state. This solution was heated to 50 ° C., and 26 parts by weight of 35% by weight hydrogen peroxide solution was added with vigorous stirring, followed by stirring at 50 ° C. for 10 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, 28 parts by weight 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 (5).

を主成分とする本発明のエポキシ化合物を４０部得た。
ＧＰＣの測定結果より、本発明のエポキシ化合物は、式（５）の骨格の化合物（ＥＰ−１）を８５％含有していることを確認した。
また、その粘度は５９２ｍＰａ・ｓ（２５℃ Ｅ型粘度計）であり、エポキシ当量は２０６ｇ／ｅｑ．であった。

40 parts of the epoxy compound of the present invention containing as a main component was obtained.
From the GPC measurement results, it was confirmed that the epoxy compound of the present invention contained 85% of the skeleton compound (EP-1) of the formula (5).
Moreover, the viscosity is 592 mPa * s (25 degreeC E-type viscosity meter), and an epoxy equivalent is 206 g / eq. Met.

  Next, 20 parts of the obtained epoxy compound (EP-1), 40 parts of silica gel (Wakogel C-300) and 100 parts of toluene were added and stirred sufficiently, and then the solvent was distilled off with a rotary evaporator. The obtained epoxy-supported silica gel was charged onto a silica gel column previously laminated with 200 parts, and the compound of formula (5) was obtained by silica gel column chromatography using a volume ratio of hexane: ethyl acetate = 3: 1 as a developing solvent. And the obtained fraction was solvent recovered with a rotary evaporator to obtain a colorless mixture containing the compound of the formula (5). The epoxy equivalent of the obtained mixture was 193 g / eq. The viscosity was 563 mPa · s (25 ° C. E-type viscometer). The purity of the compound of formula (5) by GPC was about 95%. Furthermore, in the GC measurement, the purity was about 99%.

Example 3
Epoxy compound (EP-1) of the present invention obtained in Example 2 and methylhexahydrophthalic anhydride (trade name Rikacid MH700G, manufactured by Shin Nippon Rika Co., Ltd., hereinafter referred to as H1) as a curing agent, curing acceleration Hexadecyltrimethylammonium hydroxide (manufactured by Tokyo Chemical Industry Co., Ltd., 25 wt% methanol solution, hereinafter referred to as C1) was used as an agent, and the mixture was blended at the blending ratio (parts by mass) shown in Table 1 below and stirred and mixed. Thereafter, vacuum defoaming was performed for 20 minutes to obtain a curable resin composition of the present invention.

Comparative Example 1
A diolefin compound for comparison was obtained in the same manner as in Example 1 except that dipropylene glycol was changed to propylene glycol. The obtained diolefin compound was liquid, and it was confirmed that the purity by gas chromatography was 94% and the result by analysis by gel permeation chromatography was 95%. The viscosity was 85 mPa · s (25 ° C. E-type viscometer).

Comparative Example 2
A diolefin compound for comparison was obtained in the same manner as in Example 1 except that dipropylene glycol was changed to tripropylene glycol. The obtained diolefin compound was liquid, and its purity by gas chromatography was 93%. As a result of analysis by gel permeation chromatography, it was confirmed to be 95%. The viscosity was 42 mPa · s (25 ° C. E-type viscometer).

Comparative Example 3
A diolefin compound for comparison was obtained in the same manner as in Example 1 except that dipropylene glycol was changed to 1,6-hexanediol in Example 1. The obtained diolefin compound was liquid, and its purity by gas chromatography was 92%. As a result of analysis by gel permeation chromatography, it was confirmed that the purity was 94%. The viscosity was 25 mPa · s (25 ° C. E-type viscometer).

Comparative Example 4
A diolefin compound for comparison was obtained in the same manner as in Example 1 except that dipropylene glycol was changed to cyclohexanedimethanol in Example 1. It was confirmed that the obtained diolefin compound was liquid and had a purity of 94% by gas chromatography and a purity of 95% as a result of analysis by gel permeation chromatography. The viscosity was 130 mPa · s (25 ° C. E-type viscometer).

Comparative Example 5
The diolefin compound obtained in Comparative Example 1 was reacted and purified in the same manner as in Example 2 to obtain a comparative epoxy compound EP-2. Epoxy equivalent is 164 g / eq. And the viscosity was 780 mPa · s (25 ° C. E-type viscometer). The purity by GPC was about 98%. Furthermore, in the GC measurement, the purity was about 99%.

Comparative Example 6
The diolefin compound obtained in Comparative Example 2 was reacted and purified in the same manner as in Example 2 to obtain a comparative epoxy compound EP-3. Epoxy equivalent was 222 g / eq. And the viscosity was 324 mPa · s (25 ° C. E-type viscometer). The purity by GPC was about 98%. Furthermore, in the GC measurement, the purity was about 99%.

Comparative Example 7
The diolefin compound obtained in Comparative Example 3 was reacted and purified in the same manner as in Example 2 to obtain a comparative epoxy compound EP-4. Epoxy equivalent is 185 g / eq. The viscosity was 230 mPa · s (25 ° C. E-type viscometer). The purity by GPC was about 98%. Furthermore, in the GC measurement, the purity was about 99%.

Comparative Example 8
The diolefin compound obtained in Comparative Example 4 was reacted and purified in the same manner as in Example 2 to obtain a comparative epoxy compound EP-5. Epoxy equivalent was 198 g / eq. The viscosity was 3.5 Pa · s (25 ° C. E-type viscometer). The purity by GPC was about 98%. Furthermore, in the GC measurement, the purity was about 99%.

Comparative Example 9
About the epoxy compound (EP-2) obtained in Comparative Example 5, methylhexahydrophthalic anhydride (trade name Ricacid MH700G, manufactured by Shin Nippon Rika Co., Ltd., hereinafter referred to as H1) as a curing agent, and a curing accelerator Hexadecyltrimethylammonium hydroxide (manufactured by Tokyo Chemical Industry Co., Ltd., 25% methanol solution, hereinafter referred to as C1) was blended at the blending ratio (parts by mass) shown in Table 1 below and stirred and mixed. Vacuum defoaming was performed for a minute to obtain a comparative curable resin composition.

Comparative Example 10
A comparative curable resin composition was obtained in the same manner as in Comparative Example 9 except that EP-2 was changed to EP-3 in Comparative Example 9.

Comparative Example 11
In Comparative Example 9, a curable resin composition was obtained in the same manner as Comparative Example 9 except that EP-2 was changed to EP-4.

Comparative Example 12
In Comparative Example 9, a curable resin composition was obtained in the same manner as Comparative Example 9 except that EP-2 was changed to EP-5.

(Heat resistance test)
The curable resin compositions obtained in Example 3 and Comparative Examples 9 to 12 were 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 a polyimide film was covered on the mold. Did. A dynamic viscoelasticity test was carried out under the conditions shown below using a test piece obtained by curing the cast by heating in an oven at 150 ° C. for 1 hour after preliminary curing at 120 ° C. for 3 hours. . The results are shown in Table 1.
Measurement conditions Dynamic viscoelasticity measuring device: manufactured by 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.

(Thermo-mechanical property test)
The curable resin composition obtained in Example 3 and Comparative Examples 9 to 12 was cast into a φ5 mm tube made of Teflon (registered trademark), and the cast was subjected to the same conditions as the sample used for the heat resistance property test. Using the test piece obtained by curing, a heat resistance test was performed under the following conditions. The results are shown in Table 1.
Measurement conditions Dynamic viscoelasticity measuring instrument: TM-7000, manufactured by Vacuum Riko Co., Ltd.
Measurement temperature range: 40 ° C to 250 ° C
Temperature rate: 2 ° C./min Test piece size: A material cut into φ2 mm × 15 mm was used.

(Thermal durability transmission test)
On a glass substrate on which a dam was formed with heat-resistant tape so that the curable resin composition obtained in Example 3 and Comparative Examples 9 to 12 was subjected to vacuum defoaming for 20 minutes and then 30 mm × 20 mm × height 1 mm The sample was gently injected and cured under the same conditions as the sample used for the heat resistance property test to obtain a test piece for transmittance having a thickness of 1 mm.
Using these test pieces, transmittance (measurement wavelength: 465 nm) before and after being allowed to stand for 96 hours in an oven at 150 ° C. was measured with a spectrophotometer, and the transmittance retention was calculated. The results are shown in Table 1.

(Silver adhesion test)
0.02 g of the curable resin composition obtained in Example 3 and Comparative Examples 9 to 12 was applied to one end of a 25 mm × 50 mm × 2 mm thick SPCC (cold rolled steel plate) subjected to silver plating. The same SPCC as above was bonded to the coated surface, the bonded portion was sandwiched between clips, and cured under the same conditions as the sample used in the heat resistance characteristic test. Next, the adhesion strength of the tensile shear of the bonded substrates was measured using a tensile tester (A & D TENSILON RTA-500). The results are shown in Table 1.

  From the results of the heat durability transmittance test and the silver adhesion test, it can be seen that the epoxy compound of the present invention and the curable resin composition containing the epoxy compound give a cured product balanced in heat-resistant transparency and adhesion.

  Since the epoxy compound of the present invention gives a cured product excellent in toughness, the curable fat composition of the present invention containing the epoxy compound of the present invention is an electric / electronic material, a molding material, a casting material, a laminate material, a paint, It is extremely useful for a wide range of applications such as adhesives and resists, especially for optical materials requiring low colorability.

Claims (6)

Following formula (1)

(In Formula (1), R < ₁ > -R < ₅ > respectively represents a hydrogen atom or a C1-C6 alkyl group.) The diolefin compound characterized by the above-mentioned. In the formula (1), R ₁ is a hydrogen atom, one of R ₂ and R ₃ is a methyl group, the rest is a hydrogen atom, one of R ₄ and R ₅ is a methyl group, and the rest is a hydrogen atom Item 2. The diolefin compound according to Item 1. The epoxy compound obtained by oxidizing the diolefin compound of Claim 1 or 2. The epoxy compound according to claim 3, wherein the epoxy compound is epoxidized using either hydrogen peroxide or peracid. A curable resin composition comprising the epoxy compound according to claim 3 and a curing agent and / or a curing catalyst. A cured product obtained by curing the curable resin composition according to claim 5.