KR20110135917A - Diolefin compound, epoxy resin and composition thereof - Google Patents

Abstract

[식 중, 복수 존재하는 R은 각각 독립적으로 존재하고, 수소원자 또는 탄소수 1∼6개의 알킬기를 나타낸다. 또한, P는 탄소수 1∼6개의 알킬렌기 또는 직접 결합을 나타낸다] An object of the present invention is to provide a novel alicyclic epoxy resin that gives a cured product excellent in heat resistance, optical properties, and toughness.
The epoxy resin which concerns on this invention uses a diolefin compound represented by following formula (1) as a raw material, and is obtained by epoxidizing this.
Formula (1)

[In formula, two or more R exists independently and represents a hydrogen atom or a C1-C6 alkyl group. P represents an alkylene group having 1 to 6 carbon atoms or a direct bond]

Description

Diolefin compound, epoxy resin, and its composition {DIOLEFIN COMPOUND, EPOXY RESIN AND COMPOSITION THEREOF}

The present invention relates to novel diolefin compounds and epoxy resins suitable for use in electrical and electronic materials.

Epoxy resins are cured with various curing agents, and are generally cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, and electrical properties, and are used in a wide range of fields such as adhesives, paints, laminates, molding materials, mold materials, and resists. It is becoming. In recent years, especially in the field of semiconductor-related materials, electronic devices such as mobile phones equipped with cameras, ultra-thin liquid crystals, plasma TVs, and light-weight notebook computers, such as light, thin, short and small, have been pouring in. As a result, epoxy resins have been used. Very high properties have also been demanded for representative package materials. In particular, the tip package is complicated in structure, and it is increasing that sealing is difficult unless it is liquid sealing. For example, what has a cavity down type structure like EnhancedBGA needs partial sealing, and it cannot cope with transfer molding. For this reason, development of a high performance liquid epoxy resin is calculated | required.

In addition, RTM has been recently used as a composite material, a vehicle body of a vehicle, or a structural member of a ship because of its simplicity in manufacturing method. In such a composition, since it is easy to impregnate carbon fiber etc., the low viscosity epoxy resin is calculated | required.

In addition, in the field of optoelectronics, in particular, in recent years, in order to smoothly transmit and process a large amount of information, a technology of utilizing an optical signal instead of a signal transmission by a conventional electrical wiring has been developed. Among them, in the field of optical components such as optical waveguides, blue LEDs and optical semiconductors, development of resin materials excellent in transparency is required. Attention to these demands is given to alicyclic epoxy compounds.

The alicyclic epoxy compound is superior in terms of electrical insulation and transparency in comparison with the glycidyl ether type epoxy compound, and is often used in transparent sealing materials and the like. However, especially in the field where high thermal and optical characteristics, such as LED use, are required, the alicyclic epoxy compound which further improved heat resistance and light resistance is calculated | required (refer patent document 1-3).

Japanese Patent Publication No. 2006-52187 Japanese Patent Publication No. 2007-510772 Japanese Patent Publication No. 2007-16073

An object of this invention is to provide the novel alicyclic epoxy resin which gives the hardened | cured material excellent in heat resistance, an optical characteristic, and toughness.

MEANS TO SOLVE THE PROBLEM The present inventors came to complete this invention, as a result of earnestly examining in view of the above fact. That is, the present invention,

(1) a diolefin compound characterized by the following formula (1),

[In formula, two or more R exists independently and represents a hydrogen atom or a C1-C6 alkyl group. P represents an alkylene group having 1 to 6 carbon atoms or a direct bond]

(2) an epoxy resin obtained by oxidizing the diolefin compound according to item (1);

(3) In the above (2),

Epoxy resin, characterized in that the epoxidation using hydrogen peroxide or peracid,

(4) an epoxy resin composition comprising the epoxy resin as described in the above item (2) or (3), a curing agent and / or a curing catalyst,

(5) It is related with the hardened | cured material formed by hardening | curing the epoxy resin composition as described in said (4).

The epoxy resin of this invention gives hardened | cured material excellent in a mechanical characteristic (especially toughness). The curable resin composition of this invention containing the epoxy resin of this invention is useful for a wide range of uses, such as an electrical and electronic material, a molding material, a casting material, a laminated material, coating material, an adhesive agent, and a resist. Moreover, since the epoxy resin of this invention does not have an aromatic ring, curable resin composition containing it is very useful for an optical material.

This invention relates to the diolefin compound characterized by the following formula (1), and the epoxy resin obtained by epoxidizing this by oxidation.

[In formula, two or more R exists independently and represents a hydrogen atom or a C1-C6 alkyl group. P represents an alkylene group having 1 to 6 carbon atoms or a direct bond]

The diolefin compound represented by said formula (1) is obtained by reaction of cyclohexene carboxylic acid derivative and cyclic acetal containing diol. As a cyclohexene carboxylic acid derivative, it is a compound represented by following formula (2),

[In formula, two or more R exists independently and represents a hydrogen atom or a C1-C6 alkyl group. X represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom]

Specifically, cyclohexene carboxylic acid, cyclohexene carboxylic acid methyl, cyclohexene carboxylic acid ethyl, cyclohexene carboxylic acid propyl, cyclohexene carboxylic acid butyl, cyclohexene carboxylic acid hexyl, (cyclohexenylmethyl) Cyclohexene carboxylate, cyclohexene carboxylic acid octyl, cyclohexene carboxylic acid chloride, cyclohexene carboxylic acid bromide, methylcyclohexene carboxylic acid, methylcyclohexene carboxylic acid methyl, methylcyclohexene carboxylic acid ethyl, Methylcyclohexene carboxylic acid propyl, (methylcyclohexenylmethyl) methylcyclohexene carboxylate, methylcyclohexene carboxylic acid chloride, etc. are mentioned, It is not limited to these. These may be used independently and may be used together 2 or more types.

In addition, the said cyclic acetal containing diol is obtained by reaction of a trimethylol alkane derivative and hydroxyl group containing carboaldehydes, for example. Examples of the trimethylolalkane derivative include trimethylolpropane, trimethylolmethane, trimethylolethane, trimethylolbutane, and the like, but the trimethylolalkane derivative is not limited to these compounds as long as the three hydrogen atoms of the alkane are substituted with methylol groups. These may be used independently and may be used together 2 or more types. The hydroxyl group-containing carboaldehydes are not particularly limited as long as they are compounds having a hydroxyl group and a formyl group in the molecular structure. However, it is preferable that groups other than a hydroxyl group and a formyl group are aliphatic alkyl chains. Specific examples of the compound include hydroxyethyl aldehyde, hydroxypropyl aldehyde, hydroxy pivalaldehyde, and the like, but are not limited thereto. These may be used independently and may be used together 2 or more types. Such a compound can be easily produced by, for example, an aldol reaction of aldehydes. For example, if it is hydroxy pivalaldehyde, it is obtained by the aldol reaction of isobutyl aldehyde and formaldehyde (Japanese Patent Laid-Open No. 2007-70339).

As a reaction method of the trimethylol alkane derivative and the hydroxyl group-containing carboaldehydes, a general cyclic acetalization reaction may be applied, for example, a method in which the reaction is carried out by azeotropic dehydration using a solvent such as toluene or xylene as a reaction medium ( U.S. Patent No. 2945008), a method of dissolving polyhydric alcohol in concentrated hydrochloric acid and then slowly adding aldehydes (Japanese Patent Application Laid-Open No. 48-96590), a method of using water as a reaction medium (US Patent No. 3092640), a method of using an organic solvent as a reaction medium (JP-A-7-215979), a method of using a solid acid catalyst (JP-A-2007-230992), and the like are known.

As the reaction between the cyclohexenecarboxylic acid derivative and the cyclic acetal-containing diol, a general esterification method can be adapted. Specifically, general esterification reactions can be adapted, and Fischer esterification using an acid catalyst, acid halides under basic conditions, alcohol reactions, and condensation reactions using various condensing agents can be cited (ADVANCED ORGANIC CHMISTRY). Part B: Reaction and Synthsis p. 135, 145-147, 151, etc.). Specific examples include esterification reactions of alcohols with carboxylic acids (Tetrahedron Vol. 36 p. 2409 (1980), Tetrahedron Letter p.4475 (1980), and transesterification reactions of carboxylic acid esters (Japanese Patent Laid-Open No. 2006-). 052187) may be used.

As a preferable structure of the diolefin compound of the said Formula (1) synthesize | combined in this way, in said Formula (1), it is preferable that R is any one of a hydrogen atom, a methyl group, an ethyl group, and a butyl group, and especially substituent R couple | bonds with an olefin. In order to improve the reactivity, R bonded to the olefin is preferably one of a hydrogen atom and a methyl group, particularly preferably a hydrogen atom.

Since the substituent R directly connected to the cyclic acetal imparts a modification to the structure, a methyl group, an ethyl group, a propyl group, or the like is preferable. Moreover, since it is easy to obtain a raw material on the market, it is preferable to become an ethyl group. However, about this structure, since it can synthesize | combine easily by reaction of a corresponding aldehyde and formaldehyde (or its synthetic equivalent), it can synthesize | combine as needed (US Patent No. 3097245).

Bonding group P is a C1-C6 alkylene group, and a C1-C4 alkylene group is preferable. The alkylene group may be any of linear, branched or cyclic. This structure is one of factors which are effective in the characteristic of final hardened | cured material, More preferably, it is C2-C4. Although this bonding group P may be directly connected, since it may cause instability of a structure, it is preferable that it is the said C1-C6 alkylene group. If the alkylene chain is too large (more than 6 carbon atoms), there is a fear that sufficient heat resistance may not be maintained in the cured product.

The olefin compound of this invention shown by said formula (1) can be used as the epoxy resin of this invention by oxidizing. Examples of the oxidation method include a method of oxidizing with peracid such as peracetic acid, a method of oxidizing with hydrogen peroxide, a method of oxidizing with air (oxygen), and the like.

Specifically as a epoxidation method by peracid, the method of Unexamined-Japanese-Patent No. 2006-52187, etc. are mentioned. Examples of the peracid that can be used include organic acids such as formic acid, acetic acid, propionic acid, maleic acid, benzoic acid, m-chlorobenzoic acid and phthalic acid, and acid anhydrides thereof. Among them, formic acid, acetic acid and phthalic anhydride are preferably used in view of efficiency, reaction temperature, simplicity of operation and economical efficiency in generating organic peracid by reacting with hydrogen peroxide, and especially formic acid or acetic acid in view of simplicity of reaction operation. It is more preferable to use.

In the epoxidation method using hydrogen peroxide solution, various methods can be applied. Specifically, Japanese Patent Application Laid-Open No. 59-108793, Japanese Patent Application Laid-Open No. 62-234550, Japanese Patent Application Laid-Open No. 5-213919, The methods as listed in Japanese Patent Laid-Open No. 11-349579, Japanese Patent Laid-Open No. Hei 1-33471, Japanese Patent Laid-Open No. 2001-17864, Japanese Patent Laid-Open No. 3-57102 and the like can be adapted.

Hereinafter, the method especially preferable for obtaining the epoxy resin of this invention is illustrated.

First, the diolefin compound, polyacids, and quaternary ammonium salts of the present invention are reacted with two layers of an organic substance and hydrogen peroxide solution.

The polyacids used in the present invention are not particularly limited as long as they are compounds having a polyacid structure. Polyacids containing tungsten or molybdenum are preferable, polyacids containing tungsten are more preferable, and tungstate salts are particularly preferable. .

Specific polyacids and polyacids included in the polyacids include tungstic acid, molybdic acid and phosphmolybdenum selected from tungstic acid, 12- tungstophosphoric acid, 12- tungstoboric acid, 18- tungstophosphoric acid and 12- tungstosilic acid. Molybdenum acids selected from acids and the like, salts thereof and the like.

Examples of counter cations of these salts include ammonium ions, alkaline earth metal ions, and alkali metal ions.

Specific examples thereof include, but are not limited to, alkaline earth metal ions such as calcium ions and magnesium ions, and alkali metal ions such as sodium, potassium and cesium. Particularly preferred counter cations are sodium ions, potassium ions, calcium ions and ammonium ions.

The amount of polyacid to be used is 1.0 to 20 mmol, preferably 2.0 to 20 mmol, more preferably 2.5 to 1 mol of the diolefin compound of the present invention in terms of metal elements (moles of tungsten atoms if tungsten acid, molybdenum atoms if molybdate). 10 mmol.

As the quaternary ammonium salt, a quaternary ammonium salt having 10 or more, preferably 25 to 100, total carbon atoms can be preferably used, and in particular, all of the alkyl chains are aliphatic chains.

Specifically, tridecanylmethylammonium salt, dilauryldimethylammonium salt, trioctylmethylammonium salt, trialkylmethyl (a mixed type of a compound having an alkyl group octyl group and a decanyl group) ammonium salt, trihexadecylmethylammonium salt, trimethylstearylammonium salt, Tetrapentylammonium salt, cetyltrimethylammonium salt, benzyltributylammonium salt, dicetyldimethylammonium salt, tricetylmethylammonium salt, dicured tallow alkyldimethylammonium salt, and the like, but are not limited thereto. It is especially preferable that it is 25-100 carbon atoms.

The anion type of these salts is not particularly limited, and specific examples include halide ions, nitrate ions, sulfate ions, hydrogen sulfate ions, acetate ions, carbonate ions, and the like.

When the carbon number exceeds 100, the hydrophobicity may become so strong that the solubility of the quaternary ammonium salt into the organic layer may be deteriorated. If the carbon number is less than 10, the hydrophilicity is strong, and likewise, the compatibility of the quaternary ammonium salt with the organic layer is deteriorated, which is not preferable.

The amount of quaternary ammonium salt used is preferably 0.01 to 0.8 equivalents or 1.1 to 10 times the equivalents of the hydrolyzate of the tungstic acids used. More preferably, it is 0.05-0.7 times equivalent or 1.2-6.0 times equivalent, More preferably, it is 0.05-0.5 times equivalent, or 1.3-4.5 times equivalent.

For example, if tungstic acid is H ₂ WO ₄ and divalent, the carboxylate salt of quaternary ammonium is preferably 0.02 to 1.6 mol or 2.2 to 20 mol per mole of tungstic acid. Moreover, since it is trivalent if it is tungstophosphoric acid, it is 0.03-2.4 mol or 3.3-30 mol, and 0.04-3.2 mol or 4.4-40 mol is preferable because it is tetravalent if it is silic tungstic acid.

Although all can be used as a buffer, it is preferable to use an aqueous solution of phosphate in this reaction. As pH, what adjusted between pH 4-10 is preferable, More preferably, it is pH 5-9. When pH is less than 4, the hydrolysis reaction and polymerization reaction of an epoxy group will advance easily. Moreover, when exceeding pH 10, a reaction becomes extremely slow and the problem that reaction time is too long arises.

Especially in this invention, when melt | dissolving tungstic acid which is a catalyst, it is preferable to adjust so that it may become between pH 5-9.

In the case of using a phosphate-phosphate aqueous solution, which is a preferred buffer, for example, 0.1-10 molar equivalents of phosphoric acid (or phosphate such as sodium dihydrogen phosphate) are used with respect to hydrogen peroxide. Sodium, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate and the like). Here, it is preferable to add pH so that pH may be mentioned above when hydrogen peroxide is added. Moreover, it is also possible to adjust using sodium dihydrogen phosphate, disodium hydrogen phosphate, etc. Preferred concentrations of the phosphate salt are 0.1 to 60% by weight, preferably 5 to 45% by weight.

In this reaction, a phosphate such as disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, sodium tripolyphosphate or the like (or its hydrate) may be added directly without using a buffer solution. In the sense of simplification of the process, it is particularly preferable to add directly since there is no trouble of pH adjustment. The usage-amount of phosphate in this case is 0.1-5 mol% equivalent normally with respect to hydrogen peroxide, Preferably it is 0.2-4 mol% equivalent, More preferably, it is 0.3-3 mol% equivalent. At this time, if it exceeds 5 mol% equivalent with respect to hydrogen peroxide, pH adjustment is necessary, and when it is less than 0.1 mol% equivalent, the disadvantages, such as hydrolyzate of the produced | generated epoxy resin, tend to advance or a reaction slows down will arise.

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 its ease of handling. When the concentration exceeds 40% by weight, it is not preferable because not only the handling becomes difficult but also the decomposition reaction of the resulting epoxy resin tends to proceed.

This reaction uses an organic solvent. As the quantity of the organic solvent to be used, it is 0.3-10 in weight ratio with respect to the diolefin compound 1 which is a reaction substrate, Preferably it is 0.3-5, More preferably, it is 0.5-2.5. When it exceeds 10 by weight, it is not preferable because the progress of the reaction is extremely slow. Specific examples of the organic solvent that can be used include alkanes such as hexane, cyclohexane and heptane, aromatic hydrocarbon compounds such as toluene and xylene, alcohols such as methanol, ethanol, isopropanol, butanol, hexanol and cyclohexanol. In some cases, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and anone, ethers such as diethyl ether, tetrahydrofuran and dioxane, esters such as ethyl acetate, butyl acetate and methyl formate Nitrile compounds, such as a compound and acetonitrile, can also be used.

As a specific reaction operation method, when reacting, for example in a batch reaction kiln, a diolefin compound, hydrogen peroxide (aqueous solution), heteropolyacids (catalyst), a buffer, a quaternary ammonium salt, and an organic solvent are added and stirred in two layers. . There is no specific designation of the stirring speed. Since heat is often generated at the time of addition of hydrogen peroxide, the method of gradually adding hydrogen peroxide after adding each component may be sufficient.

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

In addition, although reaction time is based also on reaction temperature, catalyst amount, etc., from a viewpoint of industrial production, reaction for a long time is unpreferable since it consumes enormous energy. As a preferable range, it is 1 to 48 hours, Preferably it is 3 to 36 hours, More preferably, it is 4 to 24 hours.

After completion of the reaction, an excess of hydrogen peroxide is quenched. It is preferable to perform a quenching process using a basic compound. Moreover, it is also preferable to use a reducing agent and a basic compound together. As a preferable processing method, after neutralizing and adjusting to pH 6-10 with a basic compound, the method of quenching the residual hydrogen peroxide using a reducing agent is mentioned. When pH is less than 6, the exotherm at the time of reducing excess hydrogen peroxide may become large and a decomposition product may arise.

Examples of the reducing agent include sodium sulfite, sodium thiosulfate, hydrazine, oxalic acid and vitamin C. The amount of the reducing agent used is usually 0.01 to 20 times mole, more preferably 0.05 to 10 times mole, and still more preferably 0.05 to 3 times mole, relative to the mole number of the excess hydrogen peroxide.

Examples of the basic compound include metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide and calcium hydroxide, metal carbonates such as sodium carbonate and potassium carbonate, phosphates such as sodium phosphate and sodium hydrogen phosphate, and basic solids such as ion exchange resin and alumina. .

The amount used may be water or an organic solvent (for example, aromatic hydrocarbons such as toluene, xylene, ketones such as methyl isobutyl ketone, methyl ethyl ketone, hydrocarbons such as cyclohexane, heptane, octane, methanol, ethanol, isopropyl alcohol, etc.). Dissolving in various solvents such as alcohols), the amount thereof is usually 0.01 to 20 times mole, more preferably 0.05 to 10 times mole, and still more preferably 0.05 to 3 times mole with respect to the mole number of excess hydrogen peroxide. These may be added as a solution of water or the above-mentioned organic solvent, or may be added in a single body.

When using a solid base which does not dissolve in water or an organic solvent, it is preferable to use an amount of 1 to 1000 times by weight relative to the amount of hydrogen peroxide remaining in the system. More preferably, it is 10 to 500 times, More preferably, it is 10 to 300 times. When using a solid base which does not dissolve in water or an organic solvent, you may process after separation of the water layer and organic layer mentioned later.

After quenching (or before quenching) of hydrogen peroxide, if the organic layer and the aqueous layer are not separated or the organic solvent is not used at this time, the above-mentioned organic solvent is added to perform the operation, and the reaction product is extracted from the aqueous layer. The organic solvent used at this time is 0.5 to 10 times by weight with respect to the raw material diolefin compound, Preferably it is 0.5 to 5 times. After repeating this operation several times as needed, an organic layer is isolate | separated and the said organic layer is washed with water and refine | purified as needed.

The obtained organic layer is preferably an ion exchange resin or metal oxide (particularly preferably silica gel or alumina), activated carbon (particularly chemically activated activated carbon), composite metal salt (particularly basic composite metal salt). The impurities are removed by a viscosity mineral (particularly, a layered viscosity mineral such as montmorillonite is preferred), and the like is further washed with water and filtered, and then the solvent is distilled off to obtain the target epoxy compound. In some cases, further purification may be performed by column chromatography or distillation.

The epoxy resin of this invention obtained in this way is Formula (3).

[In formula, two or more R exists independently and represents a hydrogen atom or a C1-C6 alkyl group. P represents an alkylene group having 1 to 6 carbon atoms or a direct bond]

Although the structure represented by is the main structure, Equation (4)

[In formula, the combination of (A)-(D) may be any combination. In addition, R and P have the same meaning as in formula (3)]

Compounds of various structures represented by are mixed. In addition, a high molecular weight or other side reaction product obtained by polymerizing epoxy groups is generated depending on the reaction conditions.

The obtained epoxy resin can be used as various resin raw materials, such as an epoxy acrylate and its derivative (s), an oxazolidone type compound, or a cyclic carbonate compound, for example.

Hereinafter, it describes about curable resin composition of this invention containing the epoxy resin of this invention.

Curable resin composition of this invention contains the epoxy resin of this invention as an essential component. In the curable resin composition of this invention, two types of methods, thermosetting (curable resin composition A) by a hardening | curing agent, and cationic curing (curable resin composition B) which make an acid a hardening catalyst, can be adapted.

In curable resin composition A and curable resin composition B, the epoxy resin of this invention can be used individually or in combination with another epoxy resin. When using together, 30 weight% or more is preferable and, as for the ratio to the total epoxy resin of the epoxy resin of this invention, 40 weight% or more is especially preferable. However, when using the epoxy resin of this invention as a modifier of curable resin composition, it adds in 1 to 30weight% of a ratio.

As another epoxy resin which can be used together with the epoxy resin of this invention, a novolak-type epoxy resin, a bisphenol-A epoxy resin, a biphenyl type epoxy resin, a triphenylmethane type epoxy resin, a phenol aralkyl type epoxy resin, etc. are mentioned. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpendiphenol, 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, dihydroxynaphthalene etc.), formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxy Benzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis ( Polycondensates such as methoxymethyl) -1,1'-biphenyl, 1,4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene, and modified substances thereof and tetrabromobisphenol A Such as halogenated bisphenols and alcohols Glycidyl ether derivatives, alicyclic epoxy resins, glycidylamine epoxy resins, glycidyl ester epoxy resins, silsesquioxane epoxy resins derived from (chain, cyclic, ladder, or two of them) Although the solid or liquid epoxy resin, such as glycidyl group and / or epoxycyclohexane structure, is mentioned for the siloxane structure of the above-mentioned mixed structure, It is not limited to these.

When using curable resin composition of this invention especially for optical use, it is preferable to use together the epoxy resin of this invention, an alicyclic epoxy resin, and the epoxy resin of a silsesquioxane structure. Especially in the case of an alicyclic epoxy resin, the compound which has an epoxy cyclohexane structure in a frame | skeleton is preferable, and the epoxy resin obtained by the oxidation reaction of the compound which has a cyclohexene structure is especially preferable.

As these epoxy resins, the esterification reaction of cyclohexene carboxylic acid and alcohols, or the esterification reaction of cyclohexene methanol and carboxylic acids (Tetrahedron Vol. 36, p. 2409 (1980), Tetrahedron Letter p. 4475 (1980), etc.) ), Or Tischenko Reaction of cyclohexenealdehyde (methods disclosed in JP-A 2003-170059, JP-A-2004-262871, etc.), and also transesterification of cyclohexene carboxylic acid esters (Japan And the method of oxidizing the compound which can be produced by the method described in Japanese Patent Application Laid-Open No. 2006-052187 and the like.

The alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but may be ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, or 1,6- Diols such as hexanediol and cyclohexanedimethanol, triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol, and tetraols such as pentaerythritol Can be mentioned. Examples of the carboxylic acids include, but are not limited to, oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, cyclohexanedicarboxylic acid, and the like.

Moreover, the acetal compound by the acetal reaction of a cyclohexene aldehyde derivative and an alcohol body is mentioned. As a reaction method, it can be manufactured by applying a common acetalization reaction, for example, the method of performing reaction while carrying out azeotropic dehydration using solvents, such as toluene and xylene, to a reaction medium (US Patent No. 2945008), and concentrated hydrochloric acid After dissolving the alcohol, the reaction is carried out while gradually adding aldehydes (Japanese Patent Application Laid-open No. 48-96590), a method of using water in the reaction medium (US Pat. No. 3092640), and an organic solvent in the reaction medium. (Japanese Patent Laid-Open No. 7-215979), a method of using a solid acid catalyst (Japanese Patent Laid-Open No. 2007-230992), and the like are disclosed. Preference is given to cyclic acetal structures because of the stability of the structure.

Specific examples of these epoxy resins include ERL-4221, UVR-6105, ERL-4299 (all trade names, all manufactured by Dow Chemical Company), CELLOXIDE 2021P, EPOLIDE GT401, EHPE3150, EHPE3150CE (all trade names, all manufactured by Daicel Chemical Industries Limited), and dish Although clopentadiene diepoxide etc. can be mentioned, It is not limited to these (Reference: General epoxy resin basic piece I, p.76-85).

These may be used independently and may be used together 2 or more types.

Moreover, solid or liquid epoxy, such as a silsesquioxane type epoxy resin (epoxy resin which has glycidyl group and / or epoxy cyclohexane structure in siloxane structure of linear, cyclic, ladder shape, or mixed structure of 2 or more of these) Adding a resin is also effective.

Reference is made about each curable resin composition below.

Thermosetting with Curing Agent (Curable Resin Composition A)

As a hardening | curing agent which curable resin composition A of this invention contains, an amine compound, an acid anhydride type compound, an amide type compound, a phenol type compound, a carboxylic acid type compound, etc. are mentioned, for example. As a specific example of the hardening | curing agent which can be used, the polyamide resin synthesize | combined from diamino diphenylmethane, diethylene triamine, triethylene tetramine, diamino diphenyl sulfone, isophorone diamine, dicyandiamide, the dimer of linolenic acid, and ethylenediamine , Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butane Tetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclo Hexane-1,3,4-tricarboxylic acid-3,4-anhydride, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpendiphenol, 4,4'-biphenol, 2,2'-ratio Phenol, 3,3 ', 5,5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroqui , Resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol , Dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopenta Diene, furfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4'-bis Polycondensates with (chloromethyl) benzene, 1,4'-bis (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, imidazole, trifluoroborane-amine complex, guanidine Although derivatives, condensates of terpenes and phenols, etc. are mentioned, It is not limited to these. These may be used independently and may use 2 or more types.

Especially in this invention, the compound which has the acid anhydride structure and / or carboxylic acid structure represented by the above-mentioned acid anhydride and carboxylic acid resin is preferable.

Examples of the compound having an acid anhydride structure include methyl tetrahydrophthalic anhydride, methylnadic anhydride, nadacid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, and bicyclo [2,2,1]. Heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3, 4-anhydrides are preferred, and methylhexahydrophthalic anhydride and cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride are particularly preferred. It is preferable to use the compound which has an acid anhydride structure as a hardening | curing agent from a viewpoint of improving hardness, insulation, heat resistance, or providing high transparency.

Especially as a compound which has a carboxylic acid structure (henceforth a polycarboxylic acid), 2-4 functional polycarboxylic acid is preferable, More preferably, it is obtained by addition-reacting 2-4 functional polyhydric alcohol and an acid anhydride. Polycarboxylic acids are preferred. It is preferable to use polycarboxylic acid as a hardening | curing agent from a viewpoint that there are few volatilizations of a hardening | curing agent, a hardening defect hardly arises, and a tough composition is easy to be obtained.

Although it will not specifically limit, if it is a compound which has an alcoholic hydroxyl group as a 2-4 functional polyhydric alcohol, Ethylene glycol, propylene glycol, 1, 3- propanediol, 1, 2- butanediol, 1, 4- butanediol, 1, 5- pentane Diol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentylglycol, tricyclodecanedimethanol, norbor Diols such as nendiol, triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol, tetraols such as pentaerythritol and ditrimethylolpropane, and the like. Can be mentioned.

Particularly preferred polyhydric alcohols having 2 to 4 functionalities include cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentylglycol, tricyclodecanedimethanol and nord It is branched chain and cyclic alcohol, such as bornendiol.

As an acid anhydride in the production of the polycarboxylic acid, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2, 2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxyl Acid-3,4-anhydride and the like are preferred.

Although it does not specifically designate on the conditions of addition reaction, One of the specific reaction conditions is a method of reacting an acid anhydride and a polyhydric alcohol, heating at 40-150 degreeC under conditions of a noncatalyst and a solvent, and taking out as it is after completion | finish of reaction. However, it is not limited to this reaction condition.

The acid anhydride and the polycarboxylic acid may be used alone or in combination of two or more. In that case, the ratio of an acid anhydride and a polycarboxylic acid is 90 / 10-20 / 80 by the weight ratio, Especially preferably, it is 80 / 20-30 / 70.

In the curable resin composition A of this invention, 0.5-1.5 equivalent is preferable as a functional group equivalent with respect to 1 equivalent of epoxy groups of an epoxy resin. Preferably it is 0.7-1.1 equivalent, Especially preferably, it is 0.8-1.0 equivalent. When less than 0.5 equivalent or more than 1.5 equivalent with respect to 1 equivalent of epoxy groups, hardening becomes incomplete and there exists a possibility that favorable hardened | cured material property may not be obtained.

In curable resin composition A of this invention, you may use a hardening accelerator together with a hardening | curing agent. Specific examples of curing accelerators that can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1 -Benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-sia Noethyl-2-undecylimidazole, 2,4-diamino-6 (2'-methylimidazole (1 ')) ethyl-s-triazine, 2,4-diamino-6- (2 '-Undecylimidazole (1')) ethyl-s-triazine, 2,4-diamino-6- (2'-ethyl, 4-methylimidazole (1 ')) ethyl-s-tri Azine, 2,4-diamino-6- (2'-methylimidazole (1 ')) ethyl-s-triazine isocyanuric acid adduct, 2 of 2-methylimidazole isocyanuric acid : 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole , Various imidazoles of 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole And salts of polyhydric carboxylic acids such as imidazoles with phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalene dicarboxylic acid, maleic acid and oxalic acid, and amides such as dicyandiamide, 1 Diaza compounds, such as 8-diaza-bicyclo (5.4.0) undecene-7, salts, such as tetraphenylborate and phenol novolak, salts with the said polyhydric carboxylic acid or phosphinic acid, tetra Ammonium salts such as butylammonium bromide, cetyltrimethylammonium bromide, trioctylmethylammonium bromide, triphenylphosphine, tri (toluyl) phosphine, tetraphenylphosphonium bromide and tetraphenylphosphonium tetraphenylborate Phenolic compounds, such as a phonium compound and 2,4,6-trisaminomethylphenol, an amine adduct, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristic acid) ), Zinc compounds such as zinc zinc phosphate (such as zinc octyl phosphate and zinc stearyl phosphate), tin compounds such as tin octylate, and various metal compounds, and microcapsule type curing accelerators having these curing accelerators as microcapsules. Can be mentioned. Which of these hardening accelerators is used is suitably selected by the characteristic calculated | required by the obtained transparent resin composition called transparency, hardening rate, working conditions, etc., for example. It is preferable to use a zinc compound from a viewpoint that transparency is high and it is hard to color. A hardening accelerator is normally used in 0.001-15 weight part with respect to 100 weight part of epoxy resins.

Curable resin composition A of this invention can also be made to contain a phosphorus containing compound as a flame retardance provision component. The phosphorus-containing compound may be of a reactive type or of an additive type. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphate esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), and 4,4'-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10- Phosphanes such as oxides; Although phosphorus containing epoxy compounds, red phosphorus, etc. which are obtained by making an epoxy resin react with the active hydrogen of the said phosphanes are mentioned, Phosphate esters, a phosphane, or a phosphorus containing epoxy compound are preferable, and 1, 3- phenylene bis (dixyl Particular preference is given to rillenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4'-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds. As for content of a phosphorus containing compound, phosphorus containing compound / all the epoxy resin = 0.1-0.6 (weight ratio) are preferable. If it is less than 0.1, flame retardancy is insufficient, and if it exceeds 0.6, there is a possibility that it will adversely affect the hygroscopicity and dielectric properties of the cured product.

Moreover, binder resin can also be mix | blended with curable resin composition A of this invention as needed. As the binder resin, butyral resin, acetal resin, acrylic resin, epoxy-nylon resin, NBR-phenol resin, epoxy-NBR resin, polyamide resin, polyimide resin, silicone resin and the like, It is not limited to these. It is preferable that the compounding quantity of binder resin is a range which does not impair flame retardance and heat resistance of hardened | cured material, and is 0.05-50 weight part normally with respect to 100 weight part of resin components, Preferably 0.05-20 weight part is used as needed.

An inorganic filler can be added to curable resin composition A of this invention as needed. As the inorganic filler, powders such as crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, forsterite, steatite, spinel, titania, talc or beads which spheronized them Although these etc. are mentioned, It is not limited to these. These may be used independently and may use 2 or more types. The content of these inorganic fillers occupies 0 to 95 weight% in curable resin composition A of this invention. In addition, to the curable resin composition A of the present invention, release agents such as silane coupling agents, stearic acid, palmitic acid, zinc stearate and calcium stearate, various compounding agents such as pigments, and various thermosetting resins can be added.

When the curable resin composition A of the present invention is used in an optical material, especially an optical semiconductor encapsulant, by using a nanoorder-level filler as the particle diameter of the inorganic filler used, mechanical strength and the like can be compensated without compromising transparency. Do. As a reference as a nanoorder level, it is preferable to use the filler whose average particle diameter is 500 nm or less, especially the average particle diameter is 200 nm or less from a transparency viewpoint.

When using curable resin composition A of this invention for an optical material, especially an optical semiconductor sealing agent, fluorescent substance can be added as needed. The phosphor has a function of forming white light by, for example, absorbing a part of blue light generated from a blue LED element and generating wavelength-converted yellow light. The fluorescent substance is previously dispersed in the curable resin composition, and then 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, aluminate of rare earth elements, thiogallate, orthosilicate, etc. are illustrated. More specifically, examples thereof include phosphors such as YAG phosphor, TAG phosphor, orthosilicate phosphor, thiogallate phosphor, and sulfide phosphor, and include 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. As the particle size of the related phosphor, a particle size known in the art is used, but the average particle size is preferably 1 to 250 µm, particularly 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.

When the curable resin composition A of the present invention is used in an optical material, especially an optical semiconductor encapsulant, a thixotropic imparting agent including fine silica powder (also called aerosil or aerosol) is added for the purpose of preventing sedimentation upon curing of various phosphors. can do. As such a fine silica powder, for example, Aerosil 50, Aerosil 90, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT600, Aerosil R972, Aerosil R974, Aerosil R202, Aerosil R812, Aerosil R812S, Aerosil R805, RY200, RX200 (manufactured by NIPPON AEROSIL CO. LTD.), And the like.

In the curable resin composition A of the present invention, an optical material, especially an optical semiconductor sealant, may contain an amine compound as a light stabilizer or a phosphorus compound or a phenolic compound as an antioxidant for coloring prevention purposes.

Examples of the amine compound include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate and tetrakis (2, 2,6,6-tetramethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6 Mixed ester of, 6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane Cargo, decanesibisbis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-undecaneoxy-2,2,6,6-tetramethylpiperidine-4- I) carbonate, 2,2,6,6, -tetramethyl-4-piperidyl methacrylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1 , 2,2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1- [2- [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propy Onyloxy] -2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl-methacrylate, bis (1,2,2,6 , 6-pentamethyl-4-piperidinyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate, decane dibis (2,2,6, 6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethylhydroperoxide and octane, N, N ', N ", N"'-tetrakis- ( 4,6-bis- (butyl- (N-methyl-2,2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecan -1,10-diamine, dibutylamine, 1,3,5-triazineN, N'-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylene Polycondensates of diamines with N- (2,2,6,6-tetramethyl-4-piperidyl) butyl amine, 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]], with dimethyl succinate Polymer of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol, 2,2,4,4-tetramethyl-20- (β-lauryloxycarbonyl) ethyl-7 Oxa-3,20-diazadispiro [5.11.2] henicoic acid-21-one, β-alanine, N- (2,2,6,6-tetramethyl-4-piperidinyl ) -Dodecyl ester / tetradecyl ester, N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, 2 , 2,4,4-tetramethyl-7-oxa-3,20-diazaspiro [5,1,11,2] henicoic acid-21-one, 2,2,4,4-tetramethyl-21 Oxa-3,20-diazacyclo- [5,1,11,2] -henicoic acid-20-propanoic acid dodecyl ester / tetradecyl ester, propanediic acid, [(4-methoxyphenyl) -methylene ] -Bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester, higher fatty acid ester of 2,2,6,6-tetramethyl-4-piperidinol, 1,3- Hindered amines, such as benzene dicarboxyamide and N, N'-bis (2,2,6,6- tetramethyl-4- piperidinyl), benzo, such as an octabenzone Phenone compounds, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2-hydroxy-5-methylphenyl) benzotriazole , 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimide-methyl) -5-methylphenyl] benzotriazole, 2- (3-tert-butyl-2-hydroxy -5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-pentylphenyl) benzotriazole, methyl3- (3- (2H-benzotriazole-2 -Yl) -5-tert-butyl-4-hydroxyphenyl) propionate reaction product of polyethylene glycol, 2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol and the like Benzoate compounds such as benzotriazole compound, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and 2- (4,6-diphenyl-1 Although triazine type compounds, such as a 3, 5- triazin-2-yl) -5- [(hexyl) oxy] phenol, etc. are mentioned, Especially, it is a hindered amine type compound.

The commercial item shown next can be used as an amine compound which is the said light stabilizer.

It does not specifically limit as a commercially available amine compound, For example, CIBA SPECIALTY CHEMICALS CORP. TINUVIN765, TINUVIN770DF, TINUVIN144, TINUVIN123, TINUVIN622LD, TINUVIN152, CHIMASSORB944, ADEKA CORPORATION as products LA-52, LA-57, LA-62, LA-63P, LA-77Y, LA-81, LA-82, LA- 87 and the like.

It does not specifically limit as said phosphorus compound, For example, 1,1,3-tris (2-methyl-4- ditridecyl phosphite-5-tert- butylphenyl) butane, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritoldiphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritoldiphosphite, phenylbisphenol A pentaerythritoldiphosphite, dicyclohexylpenta Erythritol diphosphite, tris (diethylphenyl) phosphite, tris (di-isopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) force Fight, Tris (2,6-di-tert-butylphenyl) phosphite, Tris (2,6-di-tert-butylphenyl) phosphite, 2,2'-methylenebis (4,6-di-tert- Butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite , 2,2'-methylene Bis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2'-ethylidenebis (4-methyl-6-tert-butylphenyl) (2- tert-butyl-4-methylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butyl Phenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di -tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2 , 6-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2, 4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di- tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-pe Neilphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, tributyl phosphate, trimethylphosphate, tricresylphosphate, triphenylphosphate And trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenyl monosoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate and the like.

A commercial item can also be used for the said phosphorus compound. It is not specifically limited as a commercial phosphorus compound, For example, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB as ADEKA CORPORATION products 2112, ADK STAB 260, ADK STAB 522A, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 135A, ADK STAB 3010, ADK STAB TPP.

It does not specifically limit as a phenol compound, For example, 2, 6- di-tert- butyl- 4-methyl phenol, n-octadecyl-3- (3, 5- di-tert- butyl- 4-hydroxyphenyl ) Propionate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 2,4-di-tert-butyl-6-methylphenol, 1,6-hexanediol-bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris (3,5-di-tert-butyl-4-hydroxy Benzyl) -isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, pentaerythryl-tetrakis- [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis- [2- [3- (3-tert-butyl-4-hydroxy-5- Methylphenyl) -propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, triethylene glycol-bis [3- (3-t-butyl- 5-methyl-4-hydroxyphenyl) propionate], 2,2'-butylidenebis (4,6-di-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis ( 4-ethyl-6-tert-butylphenol), 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenolacrylate, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenylacrylate, 4,4'-thiobis (3-methyl-6-tert-butyl Phenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 2-tert-butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,4 -Di-tert-pentylphenol, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), Bis- [3,3-bis- (4'-hydroxy-3'-tert-butylphenyl) -butanoic acid] -glycol ester, 2,4-di-tert-butylphenol, 2,4-di-tert -Pentylphenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenylacrylate, bis- [3,3-bis -(4'-hydroxy-3'-tert-butylphenyl) -butanoic acid] -glycol ester, etc. are mentioned. have.

A commercial item can also be used for the said phenol type compound. It does not specifically limit as a phenol type compound commercially available, For example, CIBA SPECIALTY CHEMICALS CORP. IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1135, IRGANOX245, IRGANOX259, IRGANOX295, IRGANOX3114, IRGANOX1098, IRGANOX1520L, ADEKA CORPORATION products as ADK STAB AO-20, ADK STAB AOAO AOAO AO-30 ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-90, ADK STAB AO-330, SUMITOMO CHEMICAL CO., LTD. The products include Sumilizer GA-80, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), and Sumilizer GP.

In addition, a commercially available additive can be used as a coloring inhibitor of resin. For example, CIBA SPECIALTY CHEMICALS CORP. As a product, TINUVIN328, TINUVIN234, TINUVIN326, TINUVIN120, TINUVIN477, TINUVIN479, CHIMASSORB2020FDL, CHIMASSORB119FL, etc. are mentioned.

It is preferable to contain at least 1 type or more among the said phosphorus compound, an amine compound, and a phenol type compound, Although it does not specifically limit as the compounding quantity, It is the range of 0.005-5.0 weight% with respect to the said curable resin composition.

Curable resin composition A of this invention is obtained by mixing each component uniformly. Curable resin composition A of this invention can be easily made into the hardened | cured material by the method similar to the method known conventionally. 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 sufficiently mixed until required to be uniform using an extruder, a kneader, a roll, or the like as necessary. The cured product of the present invention can be obtained by obtaining a curable resin composition, molding the curable resin composition after melting and molding using a mold or a transfer molding machine, and further heating at 80 to 200 ° C. for 2 to 10 hours.

In addition, 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, and the like as a curable resin composition varnish. It can be made into hardened | cured material of curable resin composition A of this invention by impregnating the base material of glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc., and hot-press molding the prepreg obtained by heat-drying. have. The solvent at this time is 10 to 70 weight% normally in the mixture of curable resin composition of this invention and the said solvent, The quantity which preferably occupies 15 to 70 weight% is used. Moreover, the epoxy resin hardened | cured material containing carbon fiber can also be obtained by RTM system as a liquid composition.

Moreover, curable resin composition A of this invention can be used also as a modifier of a film type composition. Specifically, it can be used when improving the flexibility characteristics and the like in the B stage. Such a film type resin composition is obtained as a sheet-like adhesive agent by apply | coating curable resin composition A of this invention on a peeling film as said curable resin composition varnish, removing a solvent under heating, and performing B stage formation. This sheet-like adhesive agent can be used as an interlayer insulation layer in a multilayer board | substrate.

Next, the case where curable resin composition A of this invention is used as a sealing material or die-bonding material of an optical semiconductor is demonstrated in detail.

When using curable resin composition A of this invention as a sealing material or die-bonding material of optical semiconductors, such as a high brightness white LED, an epoxy resin by fully mixing additives, such as the epoxy resin, hardening | curing agent, coupling material, antioxidant, and a light stabilizer of this invention, A composition is prepared and used for a sealing material or both a die bond material and a sealing material. As a mixing method, it mixes by room temperature or warming using a kneader, three rolls, a universal mixer, a planetary mixer, a homo mixer, a homo disper, a bead mill, etc.

Optical semiconductor devices such as high-brightness white LEDs generally include semiconductor chips such as GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, InN, AlN, InGaN, etc., stacked on substrates such as sapphire, spinel, SiC, Si, and ZnO. It is made by adhering to a lead frame, a heat sink, or a package using an adhesive agent (die bond material). There is also a type in which wires such as gold wires are connected to allow a current to flow. The semiconductor chip is sealed with a sealing material such as an epoxy resin in order to protect it from heat and moisture and to serve as a lens function. Curable resin composition A of this invention can be used as this sealing material and die-bonding material. It is preferable to use curable resin composition A of this invention for both a die bond material and a sealing material on account of process conditions.

As a method of adhering a semiconductor chip to a substrate using the curable resin composition A of the present invention, the curable resin composition A of the present invention is applied by a dispenser, potting, or screen printing, followed by mounting a semiconductor chip to perform heat curing. The semiconductor chip can be bonded. The heating may be performed by hot air circulation, infrared, or high frequency. As for heating conditions, 1 minute-about 24 hours are preferable at 80-230 degreeC. For the purpose of reducing the internal stress generated at the time of heat curing, for example, after pre-curing at 80 to 120 ° C for 30 minutes to 5 hours, it can be post-cured at 120 to 180 ° C for 30 minutes to 10 hours.

As a method of molding a sealing material, as described above, an injection method of molding by heating and curing the sealing material after injecting the sealing material into the mold into which the substrate on which the semiconductor chip is fixed is formed, and pre-injecting the sealing material onto the mold, and fixing it thereon. The compression molding method etc. which mold-release a semiconductor chip, perform heat-hardening, and mold-release from a metal mold | die are used. Examples of the injection method include a dispenser, transfer molding, injection molding, and the like. The heating may be performed by hot air circulation, infrared, or high frequency.

As for heating conditions, 1 minute-about 24 hours are preferable at 80-230 degreeC. For the purpose of reducing the internal stress generated at the time of heat curing, for example, after pre-curing at 80 to 120 ° C for 30 minutes to 5 hours, it can be post-cured at 120 to 180 ° C for 30 minutes to 10 hours.

In addition, the curable resin composition A of the present invention can be used for general purposes in which thermosetting resins such as epoxy resins are used, and specifically, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.) and insulation In addition to a material (including a printed circuit board, an electric wire coating, etc.) and a sealing material, additives to other resins such as acrylic acid ester resins, such as sealing materials, cyanate resin compositions for substrates, and curing agents for resists, etc. may be mentioned.

Examples of the adhesive include adhesives for civil engineering, construction, automobiles, general office, medical, as well as electronic materials. Among these, as adhesives for electronic materials, mounting such as interlayer adhesives of multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcement underfills, anisotropic conductive films (ACF), and anisotropic conductive pastes (ACP), etc. And adhesives for use.

Examples of the sealing agent include potting, dipping, transfer mold sealing, condenser, transistor, diode, light emitting diode, IC and LSI, potting sealing such as IC, LSI type COB, COF and TAB, underfill such as flip chip, QFP, And sealing (including reinforcing underfill) when mounting IC packages such as BGA and CSP.

The hardened | cured material of this invention obtained by hardening | curing curable resin composition A of this invention can be used for various uses including an optical component material. The optical material refers to a material generally used for the purpose of passing light such as visible light, infrared rays, ultraviolet rays, X-rays, and lasers in the material. More specifically, the following are mentioned besides LED sealing materials, such as a lamp type and a SMD type. Liquid crystal display peripheral materials, such as liquid crystal films, such as a board | substrate material, a light guide plate, a prism sheet, a polarizing plate, a retardation plate, a viewing angle correction film, an adhesive agent, and a polarizer protective film in the liquid crystal display field. In addition, the sealing material, anti-reflective film, optical correction film, housing material, protective film of front glass, front glass substitute material, adhesive, which are expected to be the next generation flat panel display, of LED used in LED display device Mold material, sealing material of LED, protective film of front glass, front glass substitute material, adhesive, substrate material in plasma address liquid crystal (PALC) display, light guide plate, prism sheet, deflection plate, retardation plate, viewing angle correction film, adhesive , Polarizer protective film, protective film of front glass in organic EL (electro luminescence) display, front glass substitute material, adhesive, and various film substrates in field emission display (FED), protection of front glass Film, windshield alternative material, adhesive. In the field of optical recording, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical card, pickup lens , Protective films, sealants, adhesives and the like.

In the field of optical instruments, it is a lens material of a still camera, a finder prism, a target prism, a finder cover, and a light receiving sensor part. It is also a shooting lens and finder for video cameras. Moreover, it is a projection lens of a projection TV, a protective film, a sealing material, an adhesive agent, etc. Lens materials, sealing materials, adhesives, films and the like of optical sensing devices. In the field of optical components, fiber materials, lenses, waveguides, sealing materials, adhesives, and the like around optical switches in optical communication systems are used. Optical fiber materials, ferrules, sealants, adhesives and the like around optical connectors. Optical passive components and optical circuit components include lenses, waveguides, LED sealants, CCD sealants, adhesives, and the like. Substrate materials around the optoelectronic integrated circuit (OEIC), fiber materials, sealing materials for devices, adhesives and the like. In the optical fiber field, it is an optical fiber for communication infrastructure and a digital device in a home, such as industrial sensors, displays, and markers, such as decorative display lighting and light guides. In semiconductor integrated circuit peripheral materials, it is a resist material for microlithography for LSI and ultra-LSI materials. In the field of automobile / transporter, automobile lamp reflector, bearing retainer, gear part, corrosion-resistant coat, switch part, head lamp, engine parts, electric parts, various interior / exterior products, drive engine, brake oil tank, automotive antirust steel plate, Interior panels, interior materials, wire harnesses for protection and binding, fuel hoses, automotive lamps and glass replacements. Moreover, it is the multilayer glass for railroad cars. Moreover, it is a toughness-imparting agent of the structural material of an aircraft, an engine peripheral member, a wire harness for protection and binding, and a corrosion-resistant coat. In the field of construction, it is a material for interior and processing, electrical cover, sheet, glass interlayer, glass substitute, and solar cell peripheral material. In agriculture, it is a house coating film. Next-generation opto-electronic functional organic materials include organic EL element peripheral materials, organic photorefractive elements, optical amplification elements that are photo-light conversion devices, photo-computation elements, substrate materials around organic solar cells, fiber materials, sealing materials for elements, adhesives, etc. to be.

Curable Resin Composition B (Cation Curing with Acid Curing Catalyst)

Curable resin composition B of this invention hardened | cured using an acidic curing catalyst contains a photoinitiator or a thermal polymerization initiator as an acidic curing catalyst. Moreover, you may contain various well-known compounds, materials, etc., such as a diluent, a polymerizable monomer, a polymerizable oligomer, a polymerization start adjuvant, and a photosensitizer. Moreover, you may contain various well-known additives, such as an inorganic filler, a coloring pigment, a ultraviolet absorber, antioxidant, and a stabilizer as needed.

As an acidic curing catalyst, a cationic polymerization initiator is preferable and a photocationic polymerization initiator is especially preferable. As a cationic polymerization initiator, what has onium salts, such as an iodonium salt, a sulfonium salt, and a diazonium salt, is mentioned, These can be used individually or in 2 or more types.

Examples of active energy ray cationic polymerization initiators include metal fluoroboron complexes and boron trifluoride complexes (US Pat. No. 3379653), bis (perfluoroalkylsulfonyl) methane metal salts (US Pat. No. 3,566,616), aryldiazonium compounds. (US Patent No. 3708296), Aromatic Onium Salt of Group VIa Element (US Patent No. 4058400), Aromatic Onium Salt of Group Va Element (US Patent No. 4003055), Dicarbonyl Chelate of Group IIIa-Va Elements (US 4068091), thiopyryllium salt (US Pat. No. 4,393,655), VIb group elements in the MF ₆ -anion form (US Pat. No. 441478; M is selected from phosphorus, antimony and arsenic), arylsulfonium complexes ( U.S. Pat. No. 4,191951), aromatic iodonium complex salts and aromatic sulfonium complex salts (US Pat. No. 4256828), and bis [4- (diphenylsulfonio) phenyl] sulphide-bis-hexafluorometal salts (Journal of Polymer Science, Polymer Chemistry, Vol. 2, p. 1789 (1984)). In addition, it is also possible to use mixed ligand metal salts and silanol-aluminum complexes of iron compounds.

Moreover, as a specific example, "ADEKA OPTOMER SP150", "ADEKA OPTOMER SP170" (all are ASAHI DENKA CO., LTD. Product), "UVE-1014" (GENERAL ELECTRIC COMPANY product), "CD-1012" (SARTOMER COMPANY, INC. Products), "RP-2074" (product of RHODIA INC.), Etc. are mentioned.

The usage-amount of the said cationic polymerization initiator becomes like this. Preferably it is 0.01-50 mass parts with respect to 100 mass parts of epoxy resin components, More preferably, it is 0.1-10 mass parts.

In addition, it is possible to simultaneously use one kind or two or more kinds of these photocationic polymerization initiators, known polymerization initiation aids and photosensitizers. As an example of a polymerization start adjuvant, for example, benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinolpropane-1-one, N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2 -Ethyl anthraquinone, 2-tert-butyl anthraquinone, 1-chloroanthraquinone, 2-amyl anthraquinone, 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxide Santone, 2,4-diisopropyl thioxanthone, acetophenone dimethyl ketal, benzophenone, 4-methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler Photo radical polymerization initiators, such as a ketone, are mentioned. The usage-amount of superposition | polymerization start adjuvant, such as radical photopolymerization initiator, is 0.01-30 weight part with respect to 100 weight part of components which can radical-polymerize, Preferably it is 0.1-10 weight part.

Specific examples of the photosensitizer include anthracene, 2-isopropyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, acridine orange , Acridine yellow, phosphine R, benzoflavin, cetoflavin T, perylene, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethanolamine, triethylamine, etc. Can be mentioned. The usage-amount of a photosensitizer is 0.01-30 weight part with respect to 100 weight part of all epoxy resin components, Preferably it is 0.1-10 weight part.

Moreover, various compounding agents, such as an inorganic filler, a silane coupling material, a mold release agent, and a pigment, and various thermosetting resins can be added to curable resin composition B of this invention as needed. Specific examples are as described above.

Curable resin composition B of this invention is obtained by mixing each component uniformly. Moreover, after melt | dissolving in homogeneous solvents, such as polyethyleneglycol monoethyl ether, cyclohexanone, (gamma) -butyrolactone, and making it uniform, it is also possible to remove and use a solvent by drying. The solvent at this time is 10 to 70 weight% normally in the mixture of curable resin composition B of this invention and the said solvent, The quantity which preferably occupies 15 to 70 weight% is used. Although curable resin composition B of this invention can be hardened by ultraviolet irradiation, it is determined according to each hardening conditions, since it depends on the compounding of curable resin composition about the amount of ultraviolet irradiation. What is necessary is just the irradiation amount which harden | cures curable resin composition, and what is necessary is just to satisfy | fill the hardening conditions favorable adhesive strength of hardened | cured material. Since light needs to permeate | transmit to the detail at the time of this hardening, high transparency is calculated | required in the epoxy resin and curable resin composition B of this invention. Moreover, in these epoxy resin photocuring, it is difficult to harden | cure completely completely only by light irradiation, and in the application which heat resistance is calculated | required, it is necessary to complete reaction hardening completely by heating after light irradiation.

When heating is performed after light irradiation, heating can be performed in the hardening temperature area | region of normal curable resin composition B. For example, the range of 30 minutes-7 days is suitable at normal temperature-150 degreeC. Although it changes by mix | blending of curable resin composition B, it is effective in the hardening promotion after light irradiation especially in a high temperature range, and is effective in a short heat processing. In addition, the lower the temperature, the longer the heat treatment is required. There is also an effect that the aging treatment is performed by curing after such heating.

Moreover, since the shape of the hardened | cured material obtained by hardening | curing these curable resin composition B can also be variously taken 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 method of molding varies depending on the part to be adapted and the member, but molding methods such as casting method, casting method, screen printing method, spin coating method, spraying method, transfer method and dispenser method can be used. It is not limited. As the molding die, an abrasive glass, a hard stainless abrasive plate, a polycarbonate plate, a polyethylene terephthalate plate, a polymethyl methacrylate plate, or the like can be applied. Moreover, in order to improve mold release property with a shaping | molding die, a polyethylene terephthalate film, a polycarbonate film, a polyvinyl chloride film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a polyimide film, etc. can be applied.

For example, when using for a cationic curable resist, the photocationic type curable resin composition B of this invention which melt | dissolved in organic solvents, such as polyethyleneglycol monoethyl ether, cyclohexanone, (gamma) -butyrolactone, is copper foil laminated board or ceramic substrate first Alternatively, a coating film is formed on a substrate such as a glass substrate by a screen printing or spin coating method with a film thickness of 5 to 160 µm. Then, after preliminarily drying the coating film at 60 to 110 ° C, ultraviolet rays (for example, low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, xenon lamp, laser light, etc.) are irradiated through a negative film having a desired pattern. The post-exposure baking process is performed at 70-120 degreeC. Thereafter, the unexposed portion is dissolved (developed) with a solvent such as polyethylene glycol monoethyl ether, and then, if necessary, sufficient by ultraviolet irradiation and / or heating (for example, 0.5 to 3 hours at 100 to 200 ° C). Curing is performed to obtain a cured product. In this way, it is also possible to obtain a printed wiring board.

The hardened | cured material formed by hardening | curing curable resin composition B of this invention can be used for various uses including an optical component material. The optical material refers to a general material used for the purpose of passing light such as visible light, infrared ray, ultraviolet ray, X-ray, laser, etc. in the material. More specifically, the following are mentioned other than sealing materials for LEDs, such as a lamp type or SMD type. It is peripheral material of liquid crystal display devices, such as liquid crystal films, such as a board | substrate material, a light guide plate, a prism sheet, a polarizing plate, a retardation plate, a viewing angle correction film, an adhesive agent, and a polarizer protective film in the liquid crystal display field. In addition, the sealing material, anti-reflection film, optical correction film, housing material, front glass protective film, front glass replacement material, adhesive, and the LED display device of LED which are expected as next-generation flat panel display Mold material, sealing material of LED, protective film of front glass, front glass substitute material, adhesive, substrate material in plasma address liquid crystal (PALC) display, light guide plate, prism sheet, deflection plate, retardation plate, viewing angle correction film, Adhesive, polarizer protective film, protective film of front glass in organic EL (electro luminescence) display, front glass substitute material, adhesive, and various film substrates in field emission display (FED), protection of front glass Film, windshield alternative material, adhesive. In the field of optical recording, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), disc substrate material for optical card, pickup lens , Protective films, sealants, adhesives and the like.

In the field of optics, it is a lens material of a still camera, a finder prism, a target prism, a finder cover, and a light receiving sensor part. Moreover, it is a shooting lens and a finder of a video camera. Moreover, it is a projection lens of a projection TV, a protective film, a sealing material, an adhesive agent, etc. Light sensing device lens materials, sealing materials, adhesives, films and the like. In the field of optical components, fiber materials, lenses, waveguides, sealing materials, adhesives, and the like around optical switches in optical communication systems are used. Optical fiber materials, ferrules, sealants, adhesives and the like around optical connectors. Optical passive components and optical circuit components include lenses, waveguides, LED sealants, CCD sealants, adhesives, and the like. Substrate materials around the optoelectronic integrated circuit (OEIC), fiber materials, sealing materials for devices, adhesives and the like. In the optical fiber field, it is an optical fiber for communication infrastructure and a digital device in a home, such as industrial sensors, displays, and markers, such as decorative display lighting and light guides. In semiconductor integrated circuit peripheral materials, it is a resist material for microlithography for LSI and ultra-LSI materials. In the field of automobile / transporter, automobile lamp reflector, bearing retainer, gear part, corrosion-resistant coat, switch part, head lamp, engine parts, electric parts, various interior / exterior products, drive engine, brake oil tank, automotive antirust steel plate, Interior panels, interior materials, wire harnesses for protection and binding, fuel hoses, automotive lamps and glass replacements. Moreover, it is the multilayer glass for railroad cars. Moreover, it is a toughness-imparting agent of the structural material of an aircraft, an engine peripheral member, a wire harness for protection and binding, and a corrosion-resistant coat. In the field of construction, it is a material for interior and processing, electrical cover, sheet, glass interlayer, glass substitute, and solar cell peripheral material. In agriculture, it is a house coating film. Next-generation opto-electronic functional organic materials include organic EL element peripheral materials, organic photorefractive elements, optical amplification elements that are photo-light conversion devices, photo-computation elements, substrate materials around organic solar cells, fiber materials, sealing materials for elements, adhesives, etc. to be.

Examples of the sealing agent include potting such as capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, dipping, transfer mold sealing, potting seals such as IC, LSI type COB, COF, TAB, underfills such as flip chip, and BGA. And sealing at the time of mounting IC packages such as CSP (including reinforcing underfill).

Other applications of the optical material include general uses in which the curable resin composition B is used. For example, adhesives, paints, coatings, molding materials (including sheets, films, FRP, etc.), insulating materials (printed substrates, Electrical wire coating, etc.), an additive to other resins, etc., in addition to the sealing agent. Examples of the adhesive include adhesives for electronic materials, in addition to civil engineering, construction, automobile, general office, and medical adhesives. Among these, as adhesives for electronic materials, mounting such as interlayer adhesives of multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcement underfills, anisotropic conductive films (ACF), and anisotropic conductive pastes (ACP), etc. And adhesives for use.

Example

Next, although an Example demonstrates this invention further more concretely, a part is a weight part below unless there is particular notice. The present invention is not limited to these examples.

In addition, in the Example, the epoxy equivalent was based on JISK-7236, and the viscosity was measured using the E-type viscosity meter in 25 degreeC. In addition, the analysis conditions in gas chromatography (henceforth "GC") use HP5-MS (0.25mm ID * 15m, film thickness 0.25micrometer) as a separation column, The column oven temperature is set to 100 degreeC of initial stage temperatures. It set to, and heated up at the speed | rate of 15 degreeC per minute, and hold | maintained at 300 degreeC for 60 minutes. In addition, helium was used as a carrier gas. In addition, it is as follows in the measurement of gel permeation chromatography ("GPC" hereafter). The column is a Shodex SYSTEM-21 column (KF-803L, KF-802.5 (× 2), KF-802), the connecting eluent is tetrahydrofuran, the flow rate is 1 ml / min. Column temperature was 40 degreeC, and detection was performed by UV (254 nm), and the analytical curve used the standard polystyrene made from Shodex.

Example 1

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

(Manufactured according to Japanese Patent Application Laid-Open No. 2007-126447, GPC area% is> 99% (detector RI)) 109 parts, 126 parts of 3-cyclohexene carboxylic acid, 2 parts of paratoluenesulfonic acid are added, and 10 is heated under reflux. The reaction was carried out while removing water. After the completion of the reaction, the mixture was washed twice with 50 parts of 10% by weight aqueous sodium hydrogen carbonate solution, and the obtained organic layer was washed twice with 50 parts of water, and then the organic solvent was concentrated with a rotary evaporator to obtain the diolefin compound (D-1) of the present invention. This 209 part was obtained. The form was liquid, the purity by gas chromatography was 96%, and the result of analysis by gel permeation chromatography confirmed that the purity was> 98%. The viscosity was 2070 mPa * s (25 degreeC E-type viscosity meter).

Example 2

15 parts of water, 0.95 parts of 12- tungstophosphoric acid, 0.78 of disodium hydrogen phosphate, 2.7 parts of dicured tallow alkyldimethylammonium acetate (LION AKZO CO., LTD. Product, 50% hexane solution, ARQUAD 2HT acetate) was added to form a tungstic acid catalyst, and then 120 parts of toluene and 109 parts of the diolefin compound D-1 obtained in Example 1 were added and stirred again to form an emulsion state. It was in sum. The solution was heated to 50 ° C, 55 parts of 35% by weight of hydrogen peroxide solution was added with vigorous stirring, and stirred at 50 ° C for 13 hours. As the progress of the reaction was confirmed by GC, the conversion rate of the substrate after the reaction was> 99%, and the raw material peak disappeared.

Subsequently, after neutralizing with an aqueous 1% sodium hydroxide solution, 25 parts of 20% aqueous sodium thiosulfate aqueous solution was added, followed by stirring for 30 minutes, and allowed to stand. Take out the organic layer separated into two layers, add 10 parts of silica gel (Wakogel C-300), 20 parts of activated carbon (CAP SUPER, NORIT, CAP SUPER), 20 parts of bentonite (HOJUN CO., LTD., Bengel-SH) After stirring at room temperature for 1 hour, it filtered. After wash | cleaning the obtained filtrate three times with 100 parts of water, 99 parts of epoxy resins (EP-1) of this invention which have following formula (6) as a main component were obtained by distilling an organic solvent off.

From the measurement result of GPC, it confirmed that 98% of compounds of the skeleton of formula (6) were contained. In the GC measurement, the purity was 93%.

Moreover, the viscosity was 13500 mPa * s (30 degreeC E-type viscosity meter), and epoxy equivalent was 248g / eq.

Example 3

Column chromatography was performed using 105 parts of silica gel (Wakogel C-300, manufactured by WAKO PURE CHEMICAL INDUSTRIES, LTD.) With respect to 15 parts of the obtained epoxy resin (EP-1), using a developing solvent of ethyl acetate: hexane = 1: 4. Purification was carried out.

The obtained epoxy resin (EP-2) was 13 parts, and the purity of the obtained epoxy resin confirmed that 98% or more of compounds of the skeleton of said formula (6) were contained from the measurement result of GPC. In addition, the purity was about 99% in the GC measurement.

Moreover, the viscosity was 11000 mPa * s (30 degreeC E-type viscosity meter), and epoxy equivalent was 236g / eq.

Examples 4, 5, 6

Methyl hexahydrophthalic anhydride (NEW JAPAN CHEMICAL CO., LTD., RIKACID MH700G, hereinafter referred to as H1) as a curing agent for the epoxy resins (EP-1, EP-2) of the present invention obtained in Examples 1 and 2 , Bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride (manufactured by NEW JAPAN CHEMICAL CO., LTD., Referred to as RIKACID HNA-100, hereinafter H2), hexadecyltrimethyl as a curing accelerator. Ammonium hydroxide (25% methanol solution from TOKYO CHEMICAL INDUSTRY CO., LTD., Referred to as C1) was used, and the mixture was blended at the compounding ratio (parts by weight) shown in Table 1 below, followed by defoaming for 20 minutes. A curable composition was obtained.

The heat resistance characteristic test was done in the way shown below using the obtained curable resin composition. The results are shown in Table 1. In addition, curing conditions are 150 degreeC * 1 hour after the precure of 120 degreeC * 3 hours.

(Heat resistance test)

After performing curable resin composition obtained in Examples 4-6 for 20 minutes by vacuum defoaming, it carefully casted to the metal mold | die for test pieces of width 7mm, length 5cm, and thickness of about 800 micrometers, and then covered with the polyimide film from the top. The casting was cured under the above conditions to obtain a test piece for dynamic viscoelasticity. Table 1 shows the results of the dynamic viscoelasticity test under the conditions shown below using these test pieces.

Measuring conditions

Dynamic Viscoelasticity Meter: TA-instruments, DMA-2980

Measurement temperature range: -30 ° C to 280 ° C

Temperature rise rate: 2 ℃ / min

Test piece size: The thing cut out to 5 mm x 50 mm was used (thickness about 800 micrometers).

Analysis condition

Tg: The peak point of Tan-δ in the dynamic viscoelasticity (DMA) measurement was Tg.

25 degreeC elastic modulus: The elasticity modulus at 25 degreeC was measured.

Example 7, 8, Comparative Example 1

Epoxy resins (EP-1, EP-2) of the present invention obtained in Examples 2 and 3, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate (manufactured by Dow Chemical Company, ERL-4221 Epoxy equivalent 140g / eq. Hereinafter referred to as EP-3), using H1 as a curing agent and C1 as a curing accelerator, blended at the compounding ratio (parts by weight) shown in Table 2 below, and defoaming for 20 minutes. Inventive and comparative curable compositions were obtained.

The thermal durability transmittance | permeability test and the LED test were done in the way shown below using the obtained curable resin composition. The results are shown in Table 2. In addition, hardening conditions are 140 degreeC * 2 hours after the precure of 120 degreeC * 2 hours.

(Heat durability transmittance test)

After performing the obtained curable resin composition for 20 minutes by vacuum defoaming, it casted carefully on the glass substrate which created the dam with the heat resistant tape so that it might become 30 mm x 20 mm x height 1mm. The casting water was hardened under predetermined curing conditions to obtain a test piece for transmittance having a thickness of 1 mm.

Using these test pieces, the transmittance | permeability (measurement wavelength: 375 nm) in 96 degreeC standing back and forth in 150 degreeC oven was measured with the spectrophotometer, and the change rate was computed.

(LED test)

The resulting curable resin composition was subjected to vacuum degassing for 20 minutes, and then filled in a syringe, and a surface mounted LED package having an outer diameter of 5 mm x 5 mm with a chip having a center emission wave of 465 nm using a precision ejection device (4.4 mm inner diameter and 1.25 mm outer wall height). To mold. Then, the test LED was obtained by hardening on predetermined hardening conditions.

(1) LED lighting test

The lighting test performed the lighting test at 30 mA which is a specified electric current. Detailed conditions are shown below. As a measurement item, illuminance before and after lighting for 100 hours was measured using the integrating sphere, and the illuminance retention of the test LED was calculated.

Lighting detailed condition

Luminous Wavelength: 465nm

Driving method: Constant current method, 30mA (30mA specified light emitting device)

Driving environment: 85 ℃, 85%

Evaluation: When the fall of illuminance is less than 5%, (circle) and 5% or more and less than 10%, (triangle | delta) and 10% or more are called x.

(2) LED thermocycling test

In the thermal cycling test, a cycle of -40 ° C. × 15 minutes to 120 ° C. × 15 minutes was repeated for 2 minutes by the time required for raising and lowering the temperature by a cold shock test, and cracking and peeling to the test LED at 100 and 500 times were performed. The presence or absence of the occurrence was visually observed. Evaluation is set to (circle) when a crack and peeling generate | occur | produce, and there is no crack and peeling.

Example 9, Comparative Example 2

Epoxy resin (EP-1) of the present invention obtained in Examples 2 and 3, epoxy resin (EP-3) as a comparative example, bis (3,4-epoxycyclohexylmethyl) adipate (manufactured by Dow Chemical Company, ERL- 4229 epoxy equivalent 196 g / eq. Hereinafter referred to as EP-4) using a phosphorus quaternary salt (manufactured by NIPPON CHEMICAL INDUSTRIAL CO., LTD., PX-4MP, hereinafter C2) as a curing agent and a curing accelerator. After mix | blending in the compounding ratio (weight part) shown in following Table 3, defoaming was performed for 20 minutes, and this invention and the comparative curable resin composition were obtained.

The LED lighting test was done by the method shown below using the obtained curable resin composition. The results are shown in Table 3. In addition, curing conditions are 130 degreeC * 5 hours after the precure of 110 degreeC * 3 hours.

(LED lighting test A)

The resulting curable resin composition was subjected to vacuum defoaming for 20 minutes, and then filled in a syringe, and a surface mounted LED package having an outer diameter of 5 mm x 5 mm with a chip having a center emission wave of 465 nm using a precision ejection device (4.4 mm inner diameter and 1.25 mm outer wall height). To mold. Then, the test LED was obtained by hardening on predetermined hardening conditions.

The lighting test performed the lighting test at 60 mA which is twice the specified current. Detailed conditions are shown below. As a measurement item, the illumination intensity before and after lighting for 200 hours was measured using the integrating sphere, and the illumination retention ratio of the test LED was computed.

Lighting detailed condition

Luminous Wavelength: 465nm

LED device:

Driving method: Constant current method, 60mA (30mA specified light emitting device)

Driving environment: 85 ℃, 85%

(LED lighting test B)

In addition, under the same environment as the LED lighting test described above (i.e., 85 ° C. and 85% of the conditions), the test LED is stored without lighting, and the illuminance before and after 200 hours of maintenance is measured using an integrating sphere to determine the test LED. The roughness retention was calculated.

Synthesis Example 1

12 parts of dicyclopentadiene dimethanol, methyl hexahydrophthalic anhydride (product of NEW JAPAN CHEMICAL CO., LTD., RIKACID MH, hereinafter acid anhydride H-) while purging nitrogen with a stirrer, a reflux condenser, and a flask equipped with a stirring device. 73 parts, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride (manufactured by MITSUBISHI GAS CHEMICAL COMPANY, INC., H-TMAn, hereinafter referred to as H-4) is added, A curing agent composition (HA-), which is a mixture of a polycarboxylic acid and an acid anhydride, was subjected to heating and stirring at 40 ° C for 1 hour, followed by heating and stirring at 60 ° C for 1 hour (GPC confirms that dicyclopentadienedimethanol is 0.5% or less). 100 parts of 1) were obtained. The functional group equivalent of the obtained compound was 171 g / eq. (The carboxylic acid and the acid anhydride are considered to be monofunctional groups, respectively.).

Synthesis Example 2

10 parts of 2,4-diethylpentanediol (product of KYOWA HAKKO CHEMICAL CO., LTD., KYOWADIOL PD-9) while purging nitrogen with a stirrer, reflux condenser, and a flask equipped with a stirrer, acid anhydride (H- 3) 73 parts was added and the hardening | curing agent composition which is a mixture of a polycarboxylic acid and an acid anhydride by carrying out 1 hour at 40 degreeC, and heat-stirring at 60 degreeC for 1 hour (GPC confirms the loss | disappearance of dicyclopentadiene methanol). 60 parts of (HA-2) were obtained. The functional group equivalent of the obtained compound was 170 g / eq.

Example 10, 11

As the epoxy resin (EP-1) of the present invention obtained in Example 2, the curing agent composition (HA-1) (HA-2) obtained in Synthesis Examples 1 and 2, respectively, and the phosphate ester zinc complex (KING INDUSTRIES, Using INC. Product, XC-9206, hereinafter referred to as AD-1) and hindered amine compound (ADEKA CORPORATION, LA-52, hereinafter AD-2), The curable composition of this invention was obtained.

(Heat durability transmittance test)

After performing the obtained curable resin composition for 20 minutes by vacuum defoaming, it casted carefully on the glass substrate which created the dam with the heat resistant tape so that it might become 30 mm x 20 mm x height 1mm. The casting was cured at 150 ° C for 3 hours after the preliminary curing at 110 ° C for 2 hours to obtain a test piece for transmittance having a thickness of 1 mm. Using the obtained test piece, the transmittance (measurement wavelength: 400 nm) before and after 96 hours standing in a 150 degreeC oven was measured with the spectrophotometer, and the change rate was computed.

From the above result, it turns out that the epoxy resin of this invention can provide the curable resin composition of this invention excellent in the optical characteristic and toughness (from a heat-resistant cyclic test).

Although this invention was demonstrated in detail with reference to the specific embodiment, it is clear for those skilled in the art for various changes and correction to be possible, without leaving | separating the mind and range of this invention.

In addition, this application is based on the JP Patent application (patent application 2009-067197) of an application on March 19, 2009, The whole is taken in into consideration. Also, all references cited herein are taken as a whole.

Claims (5)

The diolefin compound represented by following formula (1).

[In formula, two or more R exists independently and represents a hydrogen atom or a C1-C6 alkyl group. P represents an alkylene group having 1 to 6 carbon atoms or a direct bond] It is obtained by oxidizing the diolefin compound of Claim 1, The epoxy resin characterized by the above-mentioned. The method of claim 2,
Epoxy resin characterized by epoxidation using hydrogen peroxide or peracid. An epoxy resin composition comprising the epoxy resin according to claim 2 or 3, a curing agent and / or a curing catalyst. Hardened | cured material formed by hardening | curing the epoxy resin composition of Claim 4.