JP5559207B2 - Diolefin compound, epoxy resin, curable resin composition and cured product thereof, and optical semiconductor device - Google Patents

Description

  The present invention relates to a novel diolefin compound suitable for use in electrical and electronic materials and an epoxy resin obtained by oxidizing the compound. The present invention also relates to a curable resin composition comprising the epoxy resin and a cured product thereof. Furthermore, this invention relates to the optical semiconductor device obtained by hardening and sealing with the said curable resin composition.

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

  Also, in the field of optoelectronics, especially with the recent advancement of advanced information technology, in order to smoothly transmit and process a huge amount of information, a technology utilizing optical signals has been developed in place of conventional signal transmission using electrical wiring. Yes. In particular, in the field of optical components such as optical waveguides, blue LEDs, and optical semiconductors, development of resins having excellent transparency is desired. In response to these requirements, alicyclic epoxy resins have attracted attention.

  An alicyclic epoxy resin is superior in terms of electrical insulation and transparency as compared with a glycidyl ether type epoxy resin, and is used in various ways as a transparent sealing material. However, more advanced heat resistance and light resistance characteristics are demanded particularly for use as a member for LED (Patent Documents 1, 2, 3, and 4).

Japanese Unexamined Patent Publication No. 2006-52187 Japan Special Table 2007-510772 Japanese Unexamined Patent Publication No. 2007-16073 European Patent Application No. 0051311

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

As a result of intensive studies in view of the actual situation as described above, the present inventors have completed the present invention.
That is, the present invention
(1) The following formula (1)

(Wherein a plurality of R's each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) and the following (2)

(Wherein a plurality of R's independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and the abundance ratio thereof is trans. Body: cis body = 100: 0 to 25:75 diolefin compound,
(2) The diolefin compound according to the above item (1) obtained by transesterification,
(3) The diolefin compound according to (1) or (2) above, wherein the ratio of the trans isomer to the cis isomer is 100: 0 to 30:70,
(4) An epoxy resin obtained by oxidizing the diolefin compound according to any one of (1) to (3) above,
(5) The epoxy resin according to the above item (4), which is epoxidized using any one of hydrogen peroxide and peracid,
(6) A curable resin composition containing the epoxy resin according to the above item (4) or (5) and a curing agent and / or a curing accelerator,
(7) Hardened | cured material formed by hardening | curing curable resin composition of preceding clause (6),
(8) An optical semiconductor device obtained by curing and sealing the curable resin composition described in (6) above,
About.

According to the curable resin composition containing an epoxy resin obtained by oxidizing the diolefin compound of the present invention, it has excellent heat resistance, optical characteristics (particularly transparency and light resistance characteristics), toughness and low moisture absorption. An excellent cured product can be obtained.
Moreover, the curable fat composition containing the epoxy resin of the present invention is useful for a wide range of applications such as electric / electronic materials, molding materials, casting materials, laminated materials, paints, adhesives, and resists. In particular, since the epoxy resin of the present invention has an alicyclic structure having no aromatic ring, the curable resin composition containing the epoxy resin is extremely useful as an optical material, particularly as a sealing material or bonding material for an optical semiconductor device. .

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

(Wherein a plurality of R's independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) and a diolefin compound (trans form) represented by the following formula (2):

(Wherein a plurality of R's independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and the abundance ratio thereof is trans. Body: cis body = 100: 0 to 25:75.
With such a configuration, the curable resin composition containing an epoxy resin obtained by oxidizing the diolefin compound of the present invention is excellent in heat resistance and light resistance and can form a cured product with low hygroscopicity. The ratio of the trans isomer: cis isomer of the diolefin compound is preferably 100: 0 to 30:70, more preferably 100: 0 to 40:60, and particularly preferably 100: 0 to 45:55. Moreover, since the epoxy resin obtained by oxidizing the diolefin compound of the present invention has an alicyclic structure, it has good optical characteristics. Moreover, since an epoxy equivalent is larger than the epoxy resin of the alicyclic structure generally marketed, the molecular weight between the crosslinking points of hardened | cured material becomes large, and also has toughness.

  The diolefin compounds represented by the above formulas (1) and (2) are usually obtained by the reaction of a cyclohexanedicarboxylic acid derivative and a cyclohexenemethanol derivative, but generally used cyclohexenecarboxylic acid derivatives are cis and trans It is a mixture of the body, and the ratio is approximately a composition ratio of trans isomer: cis isomer = 2: 8. Therefore, when the esterification reaction is carried out as it is, a mixture of trans isomer of formula (1): cis cis isomer of formula (2) = 2: 8 can be formed. Therefore, in order to obtain a diolefin compound or an epoxy resin in a ratio of trans isomer: cis isomer = 100: 0 to 25:75 of the present invention, there are the following two methods. One is dehydration esterification with a cyclohexene methanol derivative using a cyclohexanedicarboxylic acid derivative having 25% or more of the trans isomer obtained by the method described in Japanese Patent Application Laid-Open No. 2008-63311 or Japanese Patent Application Laid-Open No. 2003-128620. There is a method of reacting. In this reaction, the trans isomer may be isomerized to the cis isomer depending on the reaction conditions. The other is a method of isomerizing to the trans isomer after dehydrating esterification.

  In addition to dehydration esterification, there is a method of performing an ester exchange reaction between an alkylesterified cyclohexanedicarboxylic acid derivative and a cyclohexenemethanol derivative. In the transesterification method, there are two possible ways to achieve the trans isomer: cis isomer composition ratio of the present invention. One is a method using a cyclohexanedicarboxylic acid derivative dialkyl ester having a trans isomer of 25% or more obtained by the method described in Japanese Patent Application Laid-Open No. 2009-126854. In this case, the isomerization reaction hardly proceeds during the reaction. . The other is a method of reacting an alkyl esterified cyclohexanedicarboxylic acid derivative having a trans isomer ratio of less than 25% with a cyclohexanemethanol derivative and then isomerizing to make the trans isomer 25% or more.

  In each of the above methods, the method of isomerization after esterification is not an appropriate method because a reaction at a high temperature is required and an olefin may cause a side reaction such as polymerization. The method is preferably a reaction of a cyclohexanedicarboxylic acid derivative containing 25% or more of a trans isomer or an alkyl ester thereof and a cyclohexenemethanol derivative. Since the cis isomer increases as a result, transesterification with little isomerization is most preferable.

In the dehydration esterification reaction, cyclohexanedicarboxylic acid derivatives and cyclohexenemethanol derivatives are usually dissolved or dispersed in non-water-soluble solvents such as toluene, xylene and cyclohexane, and water is discharged out of the system by azeotropic dehydration in the presence of an acid catalyst. While doing the reaction. The reaction is basically carried out under reflux conditions. However, since isomerization and coloration are less at lower temperatures, it is preferable to carry out the reaction by reducing the reflux temperature under reduced pressure in the system.
The catalyst used in the dehydration esterification reaction may be any acid catalyst such as hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, ferric chloride, aluminum chloride, p-toluenesulfonic acid, methanesulfonic acid, tungstic acid. Phosphotungstic acid, etc., but these may be used alone or in combination of two or more. The amount used is usually 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, more preferably 0.3 to 2 parts per 100 parts by weight of the total amount of cyclohexanedicarboxylic acid derivative and cyclohexenemethanol derivative. The range is parts by weight.
A cyclohexene methanol derivative is 1-10 times mole normally with respect to 1 equivalent of carbonyl groups of a cyclohexane dicarboxylic acid derivative, Preferably it is the range of 1-6 times mole. Although the reaction is sufficiently completed even with a theoretical amount of 1 mol, it is unsuitable for use in optical applications because of strong coloring. On the other hand, if the cyclohexene methanol derivative is used in excess, the coloration is reduced, but it is necessary to recover the unreacted cyclohexene methanol derivative after the completion of the reaction.

In the transesterification reaction, the cyclohexenemethanol derivative is usually charged in an amount of 1 to 10 times mol, preferably 1 to 6 times mol, more preferably 1 to 4 times mol based on 1 equivalent of the ester group of the alkylesterified cyclohexanedicarboxylic acid derivative, catalyst. Is usually 1 to 1000 mg, preferably 1 to 500 mg, more preferably 10 to 300 mg, and usually 100 to 200 ° C., preferably 120 to 190 ° C., more preferably 130 to 180 ° C. Let Although the reaction time depends on the reaction temperature, the amount of catalyst, etc., from the viewpoint of industrial production, a long reaction time is not preferable because it consumes a large amount of energy. A preferable range is 2 to 50 hours, preferably 4 to 40 hours, and more preferably 6 to 30 hours. At this time, alcohol as a by-product is discharged from the system as needed. It is also possible to accelerate the reaction by reducing the pressure in the system to facilitate removal of alcohol.
Examples of the catalyst used in the transesterification reaction include tin compounds such as stannous chloride, stannous octoate, dibutyltin laurate, dibutyltin oxide, and dioctyltin oxide, tetrabutoxy titanate, tetraethoxy titanate, and tetrapropoxy titanate. Titanium compounds, sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, calcium hydroxide, lithium hydroxide and other alkali metals, alkaline earth metal compounds, sodium methoxide, sodium ethoxide, potassium tertiary Examples include alkali metal alkoxides such as butoxide, but are not limited thereto, and two or more kinds may be used in combination.

  In both dehydration esterification and transesterification reactions, after completion of the reaction, if necessary, a solvent such as toluene, xylene, cyclohexane, methyl isobutyl ketone is added and washed several times with an alkaline aqueous solution to remove the catalyst and to some extent decolorize. Yes. Thereafter, washing with water is repeated until the wastewater becomes neutral, and finally the diolefin compound of the present invention can be obtained by distilling off the solvent and, if necessary, excess cyclohexenemethanol derivative under heating and reduced pressure. Further, as described in JP-A-2003-488966, the catalyst can be removed by adding a solid adsorbent such as silica gel or activated clay after completion of the reaction.

The cyclohexanedicarboxylic acid derivative used in the present invention is 1,4-cyclohexanedicarboxylic acid or an alkyl-substituted product thereof, and has a trans isomer: cis isomer ratio in the range of 100: 0 to 25:75.
Examples of cyclohexene methanol derivatives that can be used include 3-cyclohexene-1-methanol, 3-methyl-3-cyclohexene-1-methanol, 4-methyl-3-cyclohexene-1-methanol, and 2-methyl-3-cyclohexene-1- Methanol, 5-methyl-3-cyclohexene-1-methanol, 6-methyl-3-cyclohexene-1-methanol, 2,5-dimethyl-3-cyclohexene-1-methanol, 2-ethyl-3-cyclohexene-1- Methanol, 5-ethyl-3-cyclohexene-1-methanol, 2-propyl-3-cyclohexene-1-methanol, 2-butyl-3-cyclohexene-1-methanol, 2-pentyl-3-cyclohexene-1-methanol, 2-hexyl-3-cyclohexene-1-meta , 2-cyclohexyl-3-cyclohexene-1-methanol, 5-propyl-3-cyclohexene-1-methanol, 5-butyl-3-cyclohexene-1-methanol, 5-cyclohexyl-3-cyclohexenemethanol, etc. However, it is not limited to these, and may be used alone or in combination of two or more.

  The diolefin compound of the present invention can be used as a thermosetting polyester cross-linking material in addition to the above-described epoxy resin raw material.

Hereinafter, the epoxy resin of the present invention will be described.
The epoxy resin of the present invention can be obtained by oxidizing the diolefin compound of the present invention. Examples of the oxidation method include, but are not limited to, a method of oxidizing with a peracid such as peracetic acid, a method of oxidizing with a hydrogen peroxide solution, and a method of oxidizing with air (oxygen).
Specific examples of the epoxidation method using peracid include the method described in Japanese Patent Application Laid-Open No. 2006-52187. Examples of peracids that can be used include formic acid, acetic acid, propionic acid, maleic acid, benzoic acid, m-chlorobenzoic acid, organic acids such as phthalic acid, and acid anhydrides thereof. Among these, it is preferable to use formic acid, acetic acid, and phthalic anhydride from the viewpoint of the efficiency of reacting with hydrogen peroxide to produce an organic peracid, the reaction temperature, the ease of operation, and the economy. Formic acid or acetic acid is more preferably used from the viewpoint of simplicity of reaction operation.
Various methods can be applied to the method of epoxidation with hydrogen peroxide solution. Specifically, Japanese Patent Application Laid-Open No. 59-108793, Japanese Patent Application Laid-Open No. 62-234550, Japanese Patent Application Laid-Open No. No. 5-291919, Japanese Patent Laid-Open No. 11-349579, Japanese Patent Publication No. 1-33341, Japanese Patent Publication No. 2001-17864, Japanese Patent Publication No. 3-57102, etc. Can be adapted.

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

The polyacid used in the present invention is not particularly limited as long as it is a compound having a polyacid structure, but polyacids containing tungsten or molybdenum are preferred, polyacids containing tungsten are more preferred, and tungstates are particularly preferred.
Specific polyacids include tungsten acids selected from tungstic acid, 12-tungstophosphoric acid, 12-tungstoboric acid, 18-tungstophosphoric acid and 12-tungstosilicic acid, their salts, molybdic acid or phosphomolybdic acid, etc. And molybdenum-based acids selected from the above and their salts.
Examples of the counter cation of these salts include quaternary ammonium ions, alkaline earth metal ions, and alkali metal ions.

  Specifically, tetramethylammonium ion, benzyltriethylammonium ion, tridecanylmethylammonium ion, dilauryldimethylammonium ion, trioctylmethylammonium ion, trialkylmethyl (mixed type of octyl group and decanyl group) ammonium ion, Quaternary ammonium ions such as hexadecylmethylammonium ion, trimethylstearylammonium ion, tetrapentylammonium ion, cetyltrimethylammonium ion, benzyltributylammonium ion, tricaprylmethylammonium ion, dicetyldimethylammonium ion, calcium ion magnesium ion, etc. Alkaline earth metal ions, sodium, potassium, cesium and other alkalis Although such genera ions include, but are not limited to.

  The amount of the polyacid used is 1.0 to 20 mmol, preferably 2.0 to 1.0 mol in terms of metal element (moles of tungsten atoms for tungstic acid and molybdenum atoms for molybdic acid) with respect to 1 mol of the diolefin compound of the present invention. 20 mmol, more preferably 2.5 to 10 mmol.

As the quaternary ammonium salt, a quaternary ammonium salt having a total carbon number of 10 or more, preferably 25 to 100, can be preferably used, and in particular, the alkyl chain is preferably an aliphatic chain.
Specifically, tridecanylmethylammonium salt, dilauryldimethylammonium salt, trioctylmethylammonium salt, trialkylmethyl (a mixed type of a compound in which the alkyl group is an octyl group and a compound in which the decanyl group is a compound) ammonium salt, trihexa Examples include decylmethylammonium salt, trimethylstearylammonium salt, tetrapentylammonium salt, cetyltrimethylammonium salt, benzyltributylammonium salt, dicetyldimethylammonium salt, tricetylmethylammonium salt, and di-cured tallow alkyldimethylammonium salt. It is not limited to. Particularly preferred are those having 25 to 100 carbon atoms.
There are no particular limitations on the anionic species of these salts, and specific examples include halide ions, nitrate ions, sulfate ions, hydrogen sulfate ions, acetate ions, carbonate ions, and the like, but are not limited thereto.
When the number of carbon atoms exceeds 100, the hydrophobicity becomes too strong, and the solubility of the quaternary ammonium salt in the organic layer may deteriorate. When the number of carbon atoms is less than 10, the hydrophilicity is increased, and the compatibility of the quaternary ammonium salt with the organic layer is similarly deteriorated.

Any buffer can be used, but it is preferable to use an aqueous phosphate solution in this reaction. The pH is preferably adjusted between pH 2 and 6, more preferably pH 3-5. When the pH is less than 2, the epoxy group hydrolysis reaction and polymerization reaction easily proceed. On the other hand, when the pH exceeds 6, the reaction becomes extremely slow and the reaction time is too long.
For example, in the case of a phosphoric acid-phosphate aqueous solution which is a preferable buffer, 0.1 to 10 molar equivalent of phosphoric acid (or a phosphate such as sodium dihydrogen phosphate) is used with respect to hydrogen peroxide. And a method of adjusting pH with a basic compound (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, etc.). Here, it is preferable that the pH is added so that the above-mentioned pH is obtained when hydrogen peroxide is added. It is also possible to adjust using sodium dihydrogen phosphate, disodium hydrogen phosphate, or the like. The preferred phosphate concentration is 0.1 to 60% by weight, preferably 5 to 45% by weight.

This reaction is epoxidized using hydrogen peroxide. As the hydrogen peroxide used in this reaction, an aqueous solution having a hydrogen peroxide concentration of 10 to 40% by weight is preferable because of easy handling. When the concentration exceeds 40% by weight, handling becomes difficult and the decomposition reaction of the produced epoxy resin also tends to proceed.
The amount of polyacid used in the oxidation reaction is usually from 0.1 to 2.0 mol%, preferably from 0.1 to 1.5 mol%, more preferably from 0.1 to 2.0 mol%, based on 1 mol of the diolefin compound. 1 to 1.0 mol%.
The amount of buffer used is usually 0.5 to 150 parts by weight, preferably 0.5 to 100 parts by weight, based on 100 parts by weight of the starting diolefin compound, but the reaction depends on the amount of buffer used. There is no significant change.

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

  As a specific reaction operation method, for example, when the reaction is performed in a batch-type reaction kettle, a diolefin compound, hydrogen peroxide (aqueous solution), polyacids (catalyst), a buffer solution, a quaternary ammonium salt, and an organic solvent are added. In addition, stir in two layers. There is no specific designation for the stirring speed. Since heat is often generated when hydrogen peroxide is added, a method of gradually adding hydrogen peroxide after each component may be added.

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

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

  After completion of the reaction, quenching of excess hydrogen peroxide is performed. The quenching treatment is preferably performed using a basic compound. It is also preferable to use a reducing agent and a basic compound in combination. As a preferred treatment method, there is a method of quenching the remaining hydrogen peroxide using a reducing agent after neutralization adjustment to pH 6-8 with a basic compound. If the pH is less than 6, the heat generated during the reduction of excess hydrogen peroxide is large, which may cause decomposition products.

  Examples of the reducing agent include sodium sulfite, sodium thiosulfate, hydrazine, oxalic acid, vitamin C and the like. As the amount of the reducing agent used, excess hydrogen peroxide is usually 0.01 to 20 times mol, more preferably 0.05 to 10 times mol, still more preferably 0.05 to 3 times mol, based on the number of moles. is there.

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

After the hydrogen peroxide quench (or before quenching), if the organic layer and the aqueous layer are not separated, or if no organic solvent is used, the above-mentioned organic solvent is added and the operation is performed. The reaction product is extracted from the layer. The organic solvent used at this time is 0.5 to 10 times, preferably 0.5 to 5 times in weight ratio to the raw material diolefin compound. This operation is repeated several times as necessary, and the separated organic layer is purified by washing with water as necessary.
The obtained organic layer is subjected to ion exchange resin, metal oxide, activated carbon, composite metal salt, clay mineral, etc., if necessary, to remove impurities, further washed with water, filtered, etc., and then the solvent is distilled off. Thus, the desired epoxy resin can be obtained. In some cases, it may be further purified by distillation. As a distillation method, it can be distilled by a technique such as a thin film or rotary molecular distillation.

  The epoxy resin thus obtained has the formula (3)

(Wherein a plurality of R's independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) and the following (4):

(Wherein a plurality of R's independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and the abundance ratio thereof is trans isomer: cis isomer = 100: 0 to 25:75, preferably 100: 0 to 30:70, more preferably 100: 0 to 40:60, and particularly preferably 100: 0 to 45:55.

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

Hereinafter, it describes about the curable resin composition of this invention containing the epoxy resin of this invention.
The curable resin composition of the present invention contains the epoxy resin of the present invention as an essential component. In the curable resin composition of the present invention, two types of heat curing (curable resin composition A) using a curing agent and / or a curing accelerator and cationic curing (curable resin composition B) using an acid as a curing catalyst are used. This method can be applied.

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

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

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

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

Hereinafter, each curable resin composition will be referred to.
Thermal curing with a curing agent and / or a curing accelerator (curable resin composition A)
Examples of the curing agent contained in the curable resin composition A of the present invention include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride Acid, pyromellitic anhydride, hydrogenated pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, Butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, ethylene glycol bistrimellitate, glycerol Listrimellitate, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, dodecenyl succinic anhydride, polyadipic acid Anhydride, polyazeline acid anhydride, polysebacic acid anhydride, hydrogenated pyromellitic anhydride, dimer acid (oleic acid dimer, linolenic acid dimer, etc.), polycarboxylic acid (phthalic acid, trimellitic acid, Pyromellitic acid, maleic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, methylnadic acid, nadic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, butanetetracarboxylic acid, bicyclo [2,2,1] heptane-2 , 3-dicarboxylic acid, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid, cyclohexane Sun-1,3,4-tricarboxylic acid, a reaction product of the above acid anhydride and a polyhydric alcohol (preferably methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, Methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid Preferred examples of the anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, and polyhydric alcohol include 2- to 4-functional polyhydric alcohols such as cyclohexanedimethanol and 2,4-diethylpentanediol. 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecanedi Branched chain and cyclic aliphatic alcohols such as methanol, norbornenediol, dicyclopentadiene dimethanol), bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2, 2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benza Dehydr, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4 ′ Polycondensates with bis (methoxymethyl) -1,1′-biphenyl, 1,4′-bis (chloromethyl) benzene, 1,4′-bis (methoxymethyl) benzene, etc., and modified products thereof, tetra Examples thereof include, but are not limited to, halogenated bisphenols such as bromobisphenol A, imidazole, trifluoroborane-amine complexes, guanidine derivatives, and condensates of terpenes and phenols. These may be used alone or in combination of two or more.

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

In the curable resin composition A of the present invention, a curing accelerator may be used. Specific examples of the curing accelerator that can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole. 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2′-methyl Imidazole (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-triazine, 2,4-diamino-6 (2'- Methylimidazole (1 ′)) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethyl Various imidazoles such as imidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and imidazoles and phthalic acid, isophthalic acid, terephthalic acid Acids, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, salts with polyvalent carboxylic acids such as succinic acid, amides such as dicyandiamide, 1,8-diaza-bicyclo (5.4.0) undecene Diaza compounds such as 7 and their tetrafes Salts such as ruborate and phenol novolac, salts with the above polycarboxylic acids, or phosphinic acids, ammonium salts such as tetrabutyl ammonium bromide, cetyltrimethyl ammonium bromide, trioctylmethyl ammonium bromide, triphenylphosphine, tri (tolyl) phosphine Phosphines and phosphonium compounds such as tetraphenylphosphonium bromide and tetraphenylphosphonium tetraphenylborate, phenols such as 2,4,6-trisaminomethylphenol, metal compounds such as amine adducts and tin octylate, and curing thereof Examples thereof include a microcapsule-type curing accelerator having a microcapsule as an accelerator. Which of these curing accelerators is used is appropriately selected depending on characteristics required for the obtained transparent resin composition, such as transparency, curing speed, and working conditions. A hardening accelerator is normally used in 0.001-15 weight part with respect to 100 weight part of epoxy resins.
In the present invention, it is desirable to use a curing agent alone or a combination of a curing agent and a curing accelerator.

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

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

  An inorganic filler can be added to the curable resin composition A of the present invention as necessary. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These may be used alone or in combination of two or more. The content of these inorganic fillers is 0 to 95% by weight in the curable resin composition A of the present invention. Furthermore, the curable resin composition A of the present invention includes a silane coupling agent, a release agent such as 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 for an optical material, particularly an optical semiconductor encapsulant, the particle size of the inorganic filler used is transparent by using a nano-order level filler. It is possible to supplement the mechanical strength without impairing the properties. As a standard for the nano-order level, it is preferable from the viewpoint of transparency to use a filler having an average particle size of 500 nm or less, particularly an average particle size of 200 nm or less.

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

  When the curable resin composition A of the present invention is used for an optical material, particularly an optical semiconductor encapsulant, for the purpose of preventing sedimentation during curing of various phosphors, silica fine powder (also called Aerosil or Aerosol) is used. An agent for imparting thixotropic properties can be added. Examples of such silica fine powder include Aerosil 50, Aerosil 90, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT600, Aerosil R972, Aerosil R974, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil R202, Aerosil Aerosil R805, RY200, RX200 (made by Nippon Aerosil Co., Ltd.), etc. are mentioned.

The curable resin composition A of the present invention is an optical material, in particular, an optical semiconductor encapsulant contains an amine compound as a light stabilizer or a phosphorus compound or phenol compound as an antioxidant for the purpose of preventing coloring. can do.
Examples of the amine compound include tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-6- Totramethyl-4-piperidyl) = 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3 , 9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane mixed ester, decanedioic acid bis (2,2,6 , 6-Tetramethyl-4-piperidyl) sebacate, bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) 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) propionyloxy] -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] buty Malonate, decanedioic acid bis (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide 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-diazadecane-1,10-diamine, dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexa Polycondensate of methylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, 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]], dimethyl succinate and Polymer of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 2,2,4,4-tetramethyl-20- (β-lauryloxycarbonyl) ethyl-7-oxa-3 , 20-diazadispiro [5 · 1 · 11 · 2] heneicosan-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-diazadispiro [5,1,11,2] heneicosan-21-one, 2,2,4,4-tetramethyl-21-oxa-3,20-diazadicyclo- [5,1,11,2]- Heneicosane-20-propanoic acid dodecyl ester / tetradecyl ester, propanedioic acid, [(4-methoxyphenyl) -methylene] -bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester, 2 , 2,6,6-tetramethyl-4-piperidinol higher fatty acid ester, 1,3-benzenedicarboxamide, N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl), etc. Hindered amine series, benzophenone series compounds such as octabenzone, 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-tetrahydrophthalimido-methyl) -5-methylphenyl] Benzotriazole, 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-di-tert-pentylphenyl) benzotriazole, methyl Reaction product of 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl) propionate and polyethylene glycol, 2- (2H-benzotriazol-2-yl) -6 -Benzotriazole compounds such as dodecyl-4-methylphenol, 2,4-di benzoate series such as tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[( Hexyl) oxy] triazine compounds such as phenol and the like can be mentioned, and hindered amine compounds are particularly preferable.

The following commercially available products can be used as the amine compound that is the light stabilizer.
The commercially available amine compound is not particularly limited, and for example, TINUVIN 765, TINUVIN 770DF, TINUVIN 144, TINUVIN 123, TINUVIN 622LD, TINUVIN 152, CHIMASSORB 944, and ADEKA, LA-52, LA-57, LA-, manufactured by Ciba Specialty Chemicals. 62, LA-63P, LA-77Y, LA-81, LA-82, LA-87 and the like.

  The phosphorus compound is not particularly limited, and for example, 1,1,3-tris (2-methyl-4-ditridecyl phosphite-5-tert-butylphenyl) butane, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, Dicyclohexylpentaerythritol diphosphite, tris (diethylphenyl) phosphite, tris (di-isopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) Hosuf Ite, tris (2,6-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butyl) Phenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-ethylidenebis (4-methyl-6-tert-butyl) Phenyl) (2-tert-butyl-4-methylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl)- , 4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -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'- Biphenylene diphosphonite, 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-phenylphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl Examples include phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, etc. It is.

  A commercial item can also be used for the said phosphorus compound. It does not specifically limit as a phosphorus compound marketed, For example, as an Adeka product, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB HP-10, ADK STAB 2112, ADK STAB 260 Adeka tab 522A, Adekas tab 1178, Adekas tab 1500, Adekas tab C, Adekas tab 135A, Adekas tab 3010, and Adekas tab TPP.

  The phenol compound is not particularly limited, and examples thereof include 2,6-di-tert-butyl-4-methylphenol and 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-hydroxybenzyl) -isocyanurate, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, pentaerythrine Lithyl-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-butyl) Phenol), 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenol acrylate, 2- [1- (2-hydroxy-3,5-di-) tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 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-pentylphenyl acrylate, bis- [3,3-bis- (4′-hydroxy-3′-tert-butylphenyl) -butanoic acid] -glycol ester and the like.

  A commercial item can also be used for the said phenolic compound. There are no particular limitations on the commercially available phenolic compounds. For example, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, IRGANOX 245, IRGANOX 259, IRGANOX 295, IRGANOX 3114 IRGANOX 1098, Adekas 1520L AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-90, ADK STAB AO-330, SUMITOMO CHEMICAL INDUSTRIES, SUMITIZER GA-80, SUMILIZER MDP-S, Sumili er BBM-S, Sumilizer GM, Sumilizer GS (F), Sumilizer GP, and the like.

  In addition, commercially available additives can be used as an anti-coloring agent for the resin. For example, TINUVIN 328, TINUVIN 234, TINUVIN 326, TINUVIN 120, TINUVIN 477, TINUVIN 479, CHIMASSORB 2020FDL, CHIMASSORB 119FL and the like are manufactured by Ciba Specialty Chemicals.

  It is preferable to contain at least one of the above phosphorus compounds, amine compounds, and phenol compounds, and the amount of the compound is not particularly limited, but is 0.005 to 5 with respect to the curable resin composition. The range is 0.0% by weight.

When using the curable resin composition A of this invention for an optical material, especially an optical semiconductor sealing agent, you may add a zinc salt (zinc complex) as needed for the purpose of a stability improvement. In particular, when an epoxy resin having a silsesquioxane structure is used in combination, it is very effective in preventing penetration of corrosive gas. The zinc salt is a salt and / or complex having zinc ion as a central element, and preferably has a structure having a phosphate ester or phosphoric acid as a counter ion and / or a ligand.
In particular, zinc salts (zinc complexes) of phosphoric acid and phosphoric acid esters having 1 to 30 carbon atoms (monoester, diester, triester, or mixtures thereof) are preferred. Specific examples of alkyl of the phosphate ester having 1 to 30 carbon atoms include methyl, isopropyl, butyl, 2-ethylhexyl, octyl, isodecyl, isostearyl, decanyl, cetyl and the like.
In the present invention, a phosphoric ester having 3 to 15 carbon atoms is particularly preferred, and the ester may be mixed or single, but the main component is preferably a phosphoric monoester. In particular, the molar ratio of monoester, diester and triester in the phosphoric acid ester contained (substitute with the purity of gas chromatography. However, since it is necessary to carry out trimethylsilylation, there is a difference in sensitivity.) In the above, it is preferable that the amount of the monoester is 50 area% or more at the stage of trimethylation treatment.
Such a phosphoric ester compound can be obtained by esterifying alcohol with phosphorus pentoxide, phosphorus oxychloride, phosphorus trichloride, or the like as a phosphorylating agent. These phosphoric acids can be obtained, for example, by reacting with zinc carbonate, zinc hydroxide, etc. (European Patent Application Publication No. 699708).
As the details of the zinc salt (zinc complex) of such a phosphate ester, the ratio of phosphorus atom to zinc atom (P / Zn) is preferably 1.2 to 2.3, more preferably 1.3 to 2.0. Especially preferably, it is 1.4-1.9. That is, in a particularly preferred form, phosphate ester (or phosphoric acid) is 1.9 mol or less per 1 mol of zinc ions, and not a simple ionic structure, but some molecules are involved by ionic bonds (or coordinate bonds). Those having a different structure are preferred.

Here, the ratio of the epoxy resin component to the zinc salt (zinc complex) is 0.01 to 8% by weight, more preferably 0.05 to 5% by weight of the zinc salt (zinc complex) by weight with respect to the epoxy resin component. 0.1 to 4% by weight.
When the amount exceeds 8% by weight, the pot life of the curable resin composition becomes a problem. When the amount is less than 0.01% by weight, the effect is not remarkable.

  The curable resin composition A of the present invention is obtained by uniformly mixing each component. The curable resin composition A of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, the epoxy resin of the present invention, a curing agent, a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent that are added as necessary are uniformly used using an extruder, a kneader, or a roll. Mix thoroughly until it is obtained to obtain a curable resin composition, melt the curable resin composition after molding using a casting or transfer molding machine, and further heat at 80 to 200 ° C. for 2 to 10 hours. Thus, the cured product of the present invention can be obtained.

  Further, the curable resin composition A of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone to obtain a curable resin composition varnish, and glass fiber. The cured product of the present invention can be obtained by hot press-molding a prepreg obtained by impregnating a base material such as carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper and drying by heating. The solvent used in this case is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition A of the present invention and the solvent. Moreover, the resin cured material containing carbon fiber can also be obtained with the RTM (Resin Transfer Molding) system with a liquid composition.

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

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

As the acidic curing catalyst, a cationic polymerization initiator is preferable, and a photocationic polymerization initiator is particularly preferable. Examples of the cationic polymerization initiator include those having an onium salt such as an iodonium salt, a sulfonium salt, and a diazonium salt, and these can be used alone or in combination of two or more.
Examples of active energy ray cationic polymerization initiators include metal fluoroboron complex salts and boron trifluoride complex compounds (US Pat. No. 3,379,653), bis (perfluoroalkylsulfonyl) methane metal salts (US Pat. No. 3,586,616), aryldiazonium Compounds (US Pat. No. 3,708,296), aromatic onium salts of group VIa elements (US Pat. No. 4,058,400), aromatic onium salts of group Va elements (US Pat. No. 4069055), dicarbonyl chelates of group IIIa to Va elements (U.S. Pat. No. 4,068,091), thiopyrylium salts (U.S. Pat. No. 4,139,655), MF ₆ ^- VIb group element in the form of anions,, (U.S. Pat. No. 4,161,478 M is selected from phosphorus, antimony and arsenic.) Arylsulfonium complex salts (US Pat. No. 42319) 1), aromatic iodonium complex salts and aromatic sulfonium complex salts (US Pat. No. 4,256,828), and bis [4- (diphenylsulfonio) phenyl] sulfide-bis-hexafluorometal salts (Journal of Polymer Science, Polymer Chemistry, Volume 2, Section 1789 (1984)). In addition, mixed ligand metal salts of iron compounds and silanol-aluminum complexes can also be used.
As specific examples, “Adekaoptomer SP150”, “Adekaoptomer SP170” (all manufactured by Asahi Denka Kogyo Co., Ltd.), “UVE-1014” (manufactured by General Electronics Co., Ltd.), “CD-1012” (Sartomer Company) Product), “RP-2074” (manufactured by Rhodia), and the like.
The amount of the cationic polymerization initiator used is preferably 0.01 to 50 parts by mass and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin component.

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

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

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

The curable resin composition B of the present invention can be obtained by uniformly mixing each component. It is also possible to dissolve in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone, or γ-butyrolactone and make it uniform, and then use it after removing the solvent by drying. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition B of the present invention and the solvent.
Although the curable resin composition B of the present invention can be cured by irradiating with ultraviolet rays, the ultraviolet irradiation amount varies depending on the curable resin composition, and therefore the curing conditions are determined according to each composition. Basically, it is sufficient that the cured product has curing conditions that can express the strength required for the purpose of use. Usually, these epoxy resin-based compositions are difficult to be completely cured only by light irradiation. Therefore, in applications requiring heat resistance, it is necessary to complete the reaction by heating after light irradiation. Moreover, since it is necessary to permeate | transmit the irradiation light in the case of photocuring to detail, the highly transparent compound and composition are desired in the epoxy resin and curable resin composition B of this invention.

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

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

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

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

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

  Furthermore, the uses of the curable resin composition A and the curable resin composition B of the present invention are not limited to the above, and can be applied to general uses in which thermosetting resins such as epoxy resins are used. . Specifically, in addition to adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (including printed circuit boards, wire coatings, etc.), sealing materials, cyanate resins for substrates Examples of the composition and resist curing agent include additives to other resins such as an acrylic ester resin.

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

  As sealing agents, potting, dipping and transfer mold sealing used for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, potting sealings used for COB, COF, TAB, etc. of ICs and LSIs, flip Examples include underfill used for chips and the like, sealing (reinforcing underfill) when mounting IC packages such as QFP, BGA, and CSP.

EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified. The present invention is not limited to these examples. In the examples, each physical property value was measured as follows.
1) Epoxy equivalent: Measured according to JIS K-7236.
2) Viscosity: Measured using an E-type viscometer at 25 ° C.
3) Gas chromatography (hereinafter referred to as “GC”):
Analysis conditions Separation column: HP5-MS (0.25 mm ID × 15 m, film thickness 0.25 μm)
Column oven temperature: set to an initial temperature of 100 ° C., heated at a rate of 15 ° C. per minute, and held at 300 ° C. for 60 minutes.
Carrier gas: helium 4) Gel permeation chromatography (hereinafter referred to as “GPC”):
Column; Shodex SYSTEM-21 column (KF-803L, KF-802.5 (x2), KF-802)
Linked eluent: tetrahydrofuran, flow rate 1 ml / min.
Column temperature: 40 ° C
Detection; RI

Example 1
Trans isomer: cis isomer = 98: 2 synthesized according to the description of Japanese Patent Application Laid-Open No. 2009-126854, while purging a flask equipped with a stirrer, reflux condenser, stirrer, and Dean-Stark tube with nitrogen purge 200 parts of dimethyl 1,4-cyclohexanedicarboxylate, 336 parts of 3-cyclohexene-1-methanol, and 0.1 part of tetrabutyl orthotitanate were added, 1 hour at 140 ° C., 1 hour at 150 ° C., 1 at 160 ° C. The reaction was carried out for 10 hours at 170 ° C. while removing the produced methanol. After completion of the reaction, 580 parts of toluene was added and washed with 120 parts of a 10% by weight aqueous sodium hydroxide solution three times. Further, the obtained organic layer was washed with 70 parts of water / times until the aqueous layer became neutral, and then rotary. 345 parts of diolefin compounds (D-1) of the present invention were obtained by concentrating an organic solvent with an evaporator. The shape was liquid immediately after concentration, but gradually crystallized at room temperature into white crystals. The isomer ratio by GC was trans isomer: cis isomer = 98: 2, and as a result of analysis by GPC, it was confirmed that the purity was 95%.

Example 2
A flask equipped with a stirrer, reflux condenser, and stirrer is purged with nitrogen, 15 parts of water, 0.95 parts of 12-tungstophosphoric acid, 0.78 parts of disodium hydrogen phosphate, di-cured tallow alkyldimethylammonium acetate After adding 2.7 parts (50% hexane solution made by Lion Akzo, Acquard 2HT acetate) to produce a tungstic acid catalyst, 180 parts of toluene and the diolefin compound (D-1) obtained in Example 1 were added. 118 parts were added, and the mixture was further stirred to obtain an emulsion liquid. The solution was heated to 50 ° C., and 70 parts of 35% by weight hydrogen peroxide was added with vigorous stirring, and the mixture was stirred at 50 ° C. for 13 hours. When the progress of the reaction was confirmed by GC, the raw material peak disappeared.
Then, after neutralizing with a 1% aqueous sodium hydroxide solution, 25 parts of a 20% by weight aqueous sodium thiosulfate solution was added, stirred for 30 minutes, and allowed to stand. The organic layer separated into two layers was taken out, 10 parts of silica gel (Wakogel C-300), 20 parts of activated carbon (CAP SUPER made by NORIT) and 20 parts of bentonite (Bengel SH made by Hojun) were added and stirred at room temperature for 1 hour. And filtered. The obtained filtrate was washed three times with 100 parts of water, and 122 parts of the epoxy resin (E-1) of the present invention was obtained by distilling off the organic solvent from the obtained organic layer. The shape was liquid immediately after concentration, but gradually crystallized at room temperature into white crystals.
The melting point is 57 ° C., and the epoxy equivalent is 206 g / eq. Met. The isomer ratio by GC was trans isomer: cis isomer = 98: 2, and as a result of analysis by GPC, it was confirmed that the purity was 95%.

Example 3
A flask equipped with a stirrer, a reflux condenser, a stirrer, and a Dean-Stark tube was purged with nitrogen, and 172 parts of 1,4-cyclohexanedicarboxylic acid having a trans isomer: cis isomer = 98: 2 and 3-cyclohexene- 224 parts of 1-methanol, 600 parts of toluene and 4 parts of p-toluenesulfonic acid were added, and the reaction was carried out for 6 hours while removing water produced at the reflux temperature. After completion of the reaction, it was washed with 120 parts of a 10% by weight aqueous sodium hydroxide solution three times. Further, the obtained organic layer was washed with 70 parts / time of water until the aqueous layer became neutral, and then the organic solvent was concentrated with a rotary evaporator. As a result, 343 parts of the diolefin compound (D-2) of the present invention was obtained. The shape was liquid. The isomer ratio determined by GC was trans isomer: cis isomer = 50: 50, and analysis by GPC confirmed that the purity was 93%.

Example 4
When the same operation was performed except having changed the diolefin compound D-1 into D-2 in Example 2, 120 parts of epoxy resins (E-2) of this invention were obtained. The shape was liquid immediately after concentration, but crystallized after a few days at room temperature to form white crystals.
The epoxy equivalent was 209 g / eq. Met. The isomer ratio by GC was trans isomer: cis isomer = 50: 50, and as a result of analysis by GPC, it was confirmed that the purity was 92%.

Example 5
173 parts of trans isomer: cis isomer = 80: 20 and 27 parts of trans isomer: cis isomer = 98: 2, 450 parts of 3-cyclohexene-1-methanol, 0.1 part of tetrabutyl orthotitanate were added, and 140 The reaction was carried out at 1 ° C. for 1 hour, 150 ° C. for 1 hour, 160 ° C. for 1 hour and 170 ° C. for 10 hours while removing the produced methanol. After completion of the reaction, 1 part of silica gel (PSQ-60B manufactured by Fuji Silysia Chemical Co., Ltd.) was added. Excess 3-cyclohexene-1-methanol was distilled off with a rotary evaporator, and the silica gel was removed by filtration. As a result, a diolefin compound (D- 340 parts of 3) were obtained. The shape of the obtained compound was liquid. The isomer ratio by GC was trans: cis = 30: 70, and analysis by GPC confirmed that the purity was 97%.

Example 6
When the same operation was performed except having changed the diolefin compound (D-1) into (D-3) in Example 2, 123 parts of epoxy resins (E-3) were obtained. The shape became liquid.
The epoxy equivalent was 203 g / eq. Met. The isomer ratio by GC was trans: cis = 30: 70, and analysis by GPC confirmed that the purity was 94%.

Comparative Example 1
In Example 1, dimethyl 1,4-cyclohexanedicarboxylate having trans isomer: cis isomer = 98: 2 was changed to trans isomer: cis isomer = 17: 83 (manufactured by Iwatani Gas Co., Ltd.), and reaction at 170 ° C. Was changed to 24 hours to obtain 340 parts of a diolefin compound (CD-1). The shape of the obtained compound was liquid. The isomer ratio by GC was trans isomer: cis isomer = 19: 81, and as a result of analysis by GPC, it was confirmed that the purity was 96%.

Comparative Example 2
The same operation was performed except that the diolefin compound (D-1) was changed to (CD-1) in Example 2, and 120 parts of an epoxy resin (CE-1) was obtained. The shape became liquid.
The epoxy equivalent was 216 g / eq. Met. The isomer ratio by GC was trans isomer: cis isomer = 21: 79, and as a result of analysis by GPC, it was confirmed that the purity was 91%.

Synthesis example 1
A flask equipped with a stirrer, a reflux condenser, and a stirrer is purged with nitrogen, 20 parts of tricyclodecane dimethanol, methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid MH or less, acid anhydride 100 parts of product (H-1) was added, reacted at 40 ° C. for 3 hours, and then heated and stirred at 70 ° C. for 1 hour (disappearance of tricyclodecane dimethanol (1 area% or less) was confirmed by GPC). .) 120 parts of a curing agent composition (T-1) containing a polyvalent carboxylic acid (B-1) and an acid anhydride (H-1) were obtained. The obtained curing agent composition is a colorless liquid resin, and the purity by GPC is 55 area% for polyvalent carboxylic acid (B-1; the following formula (5)) and 45 area% for methylhexahydrophthalic anhydride. Met. The functional group equivalent was 201 g / eq. Met.
Formula (5)

Examples 7, 8, 9 and Comparative Examples 3, 4
Epoxy resins (E-1), (E-2), (E-3), (CE-1) and 3,4-epoxycyclohexyl obtained in Examples 2, 4, 6 and Comparative Example 2 as epoxy resins Methyl-3,4-epoxycyclohexylcarboxylate (manufactured by Dow Chemical, UVR-6105 or less epoxy resin (E-4)), as a curing agent, the curing agent composition (T-1) obtained in Synthesis Example 1, Acid anhydride (H-1) and cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (H-TMAn manufactured by Mitsubishi Gas Chemical Co., Ltd., acid anhydride (H-2)), as a curing accelerator Using a quaternary phosphonium salt (manufactured by Nippon Kagaku Kogyo Co., Ltd., Hishicolin PX4MP, hereinafter referred to as catalyst (I-1)), blended at a blending ratio (part by weight) shown in Table 1 below, defoamed for 20 minutes, and the present invention or comparison A curable resin composition was obtained.

The obtained curable resin composition was vacuum degassed for 20 minutes, filled into a syringe, and cast into a surface-mounted LED equipped with a light-emitting element having an emission wavelength of 465 nm using a precision discharge device. Then, LED for a test was obtained by making it harden | cure on the conditions of 120 degreeC * 1 hour +150 degree | times * 3 hours.
As a measurement item, the illuminance before and after lighting for 200 hours was measured using an integrating sphere, and the illuminance retention rate of the test LED was calculated.
Detailed lighting conditions Light emission wavelength: 465nm
Drive system: constant current system, 60 mA (light emitting element regulation current is 30 mA)
Driving environment: temperature 85 ° C, relative humidity 85%

Example 10 and Comparative Example 5
Epoxy resin (E-3) obtained in Example 6 as an epoxy resin, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate (UVR-6105 epoxy resin (E-4) manufactured by Dow Chemical) , Using the acid anhydride (H-1) as a curing agent and 2-ethyl-4-methylimidazole (hereinafter referred to as catalyst (I-2)) as a curing accelerator, and the blending ratio (parts by weight) shown in Table 2 below ) And cast into a mold and cured under the conditions of 120 ° C. · 2 hours + 150 ° C. · 6 hours to prepare a disk specimen having a diameter of 5 cm × thickness of 4 mm. The moisture absorption rate (weight increase rate) of this test piece was measured.
The moisture absorption rate was measured under the following two conditions.
(1) Leave for 24 hours in an environment of 85 ° C and 85% relative humidity (2) Leave for 24 hours in an environment of 121 ° C and 100% relative humidity

  From the above results, it is clear that the curable resin composition containing the epoxy resin of the present invention obtained from the diolefin having the adjusted cis / trans ratio gives a cured product having excellent heat resistance and light resistance. . Moreover, it turns out that the curable resin composition containing the epoxy resin of this invention gives the hardened | cured material excellent in the moisture absorption characteristic compared with the other epoxy resin currently distribute | circulated.

Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
In addition, this application is based on the Japanese patent application (Japanese Patent Application No. 2009-293478) for which it applied on December 24, 2009, The whole is used by reference. Also, all references cited herein are incorporated as a whole.

Claims (7)

Following formula (1)

(Wherein a plurality of R's independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) and a diolefin compound (trans form) represented by the following formula (2):

(Wherein a plurality of R's independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and the abundance ratio thereof is trans. Body: cis body = 98: 2 to 25:75 A thermosetting resin composition containing an epoxy resin obtained by oxidizing a diolefin compound and a curing agent. The diolefin compound according to claim 1 thermosetting resin composition according is obtained by transesterification. The thermosetting resin composition according to claim 1 or 2, wherein the diolefin compound has a ratio of trans form to cis form of 98: 2 to 30:70 . The thermosetting resin composition according to any one of claims 1 to 3, wherein the epoxy resin is epoxidized using either hydrogen peroxide or peracid. Furthermore, the thermosetting resin composition as described in any one of Claims 1-4 containing a hardening accelerator . Hardened | cured material formed by hardening | curing the thermosetting resin composition as described in any one of Claims 1-5 . Curing and sealed with the optical semiconductor device obtained a thermosetting resin composition according to any one of claims 1 to 5.