TWI422592B - Olefin compounds, epoxy resins, hardened resin compositions and hardened products thereof, LED devices - Google Patents

Description

Olefin compound, epoxy resin, curable resin composition and cured product thereof, LED device

This invention relates to a novel olefinic compound suitable for use in electrical and electronic materials and an epoxy resin derived therefrom. Further, the present invention also relates to a curable resin composition containing the epoxy resin and a cured product obtained by curing the curable resin composition. And an LED device sealed with the curable resin composition.

The epoxy resin is cured by various curing agents and is generally used as a cured product excellent in mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., and is widely used in adhesives, coatings, laminates, molding materials, and the like. Casting materials, photoresist and other fields. In recent years, especially in the field of semiconductor-related materials, camera-equipped mobile phones, ultra-thin LCD or plasma TVs, and lightweight notebook computers have been light, thin, short, and small. Therefore, the requirements for the characteristics of the outer casing material represented by epoxy resin are also very high. In particular, the construction of the tip outer casing is complicated, and the things that are difficult to seal under the non-liquid seal increase. For example, an enhanced spherical array (EnhancedBGA) or the like is a high heat dissipation type structure, and it is necessary to perform partial sealing so that transfer molding cannot be performed. Therefore, the development of high-performance liquid epoxy resin is expected.

Further, in recent years, RTM (Resin Transfer Molding) has been used as a structural material of a composite material, a vehicle body, or a ship. The epoxy resin having a low viscosity is preferred because of the ease of impregnation of carbon fibers or the like in the composition.

In addition, in the field of optoelectronics, in particular, with the recent high level of informationization, in order to smoothly transmit and process huge amounts of information, the technology for utilizing optical signals has been developed in place of the conventional signal transmission by wires. Among them, in the field of optical components such as an optical waveguide, a blue LED, and an optical semiconductor, development of a resin material excellent in transparency is desired. For these requirements, alicyclic epoxy compounds have attracted attention.

The alicyclic epoxy compound is superior to the epoxy propylene ether type epoxy compound in terms of electrical insulating properties and transparency, and is used in a variety of transparent sealing materials. However, an alicyclic epoxy compound which is expected to have higher heat resistance and light resistance is desired in the field of high heat and light characteristics such as LED use (see Patent Documents 1 to 3).

Patent Document 1: Japanese Laid-Open Patent Publication No. 2006-52187.

Patent Document 2: Japanese Laid-Open Patent Publication No. 2007-510772.

Patent Document 3: Japanese Laid-Open Patent Publication No. 2007-16073.

An object of the present invention is to provide a novel alicyclic epoxy resin which can provide a cured product excellent in heat deterioration resistance characteristics and optical characteristics.

The inventors of the present invention have completed the present invention in view of the above-described status quo.

That is, the present invention relates to:

(1) An olefin compound represented by the following formula (1),

(In the formula, R in the plural exists independently, and represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and P is a chain alkyl chain linking group having a branched structure of 6 to 20 carbon atoms in total. ).

(2) The olefin compound according to the above (1), wherein the linking group P has a structure having a main chain of 3 or more carbon atoms and an alkyl group at least at one position.

(3) The olefin compound according to the above (1) or (2), wherein the linking group P has two or more alkyl groups which are branched in a main chain.

(4) The olefin compound according to any one of the above (1) to (3), which is represented by the following formula (D-1) or (D-2):

(5) An epoxy resin obtained by oxidizing the olefin compound according to any one of the above (1) to (4).

(6) The epoxy resin according to (5) above, which is epoxidized using hydrogen peroxide or a peracid.

(7) A curable resin composition comprising the epoxy resin and the curing agent and/or the curing catalyst described in the above (5) or (6).

(8) A cured product obtained by curing the curable resin composition described in the above (7).

(9) An LED device sealed and/or die bonded by the curable resin composition described in the above (7).

The olefin compound of the present invention is a raw material of an epoxy resin (epoxy resin of the present invention) which can provide a cured product which is excellent in heat deterioration resistance such as adhesion, heat resistance, and heat-resistant coloring property, and also excellent in light resistance and moisture resistance. . The curable resin composition of the present invention containing the epoxy resin of the present invention is suitable for use in a wide range of applications such as electric and electronic materials, molding materials, casting materials, laminated materials, paints, adhesives, and photoresists. Further, since the epoxy resin of the present invention does not have an aromatic ring, it is extremely suitable for an optical material.

The olefin compound of the present invention is represented by the following formula (1).

(wherein R in the plural exists independently, and represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Further, P is a chain alkyl chain linking group having a branched structure of 6 to 20 carbon atoms in total group).

In the above formula (1), the chain alkyl chain linking group represented by P is as follows, in which an alkyl chain having two alcoholic hydroxyl groups bonded to a diol as a raw material is used as a main chain. The structure of an alkyl chain branched by the alkyl chain. The branched alkyl chain may be branched by any carbon atom constituting the main chain, and for example, may also be branched by a carbon having an alcoholic hydroxyl group bonded thereto. Specific examples of such a chain alkyl chain linking group are shown below.

(In the above formula, the linking group P of * is bonded to the oxygen atom of the formula (1).)

In the olefin compound of the present invention, the linking group P has a structure in which an alkyl group is bonded to an alkyl group in the main chain, and the total carbon number is from 6 to 20, and is not particularly limited. The chain has a carbon number of 3 or more (preferably 3 to 10) and at least one alkyl branch, and particularly preferably has 2 or more alkyl branches. From the viewpoint of heat-resistant coloring property, the number of carbon atoms of the alkyl branch is preferably from 2 to 17.

From the viewpoint of imparting heat resistance, heat-resistant coloring property, moisture resistance, and high illuminance retention ratio, it is particularly preferred that two or more carbon atoms different from the main chain alkyl group have an alkyl group. In this case, it is preferred that the number of carbon atoms in the branch is two or more.

The olefin compound represented by the above formula (1) is a structure in which a cyclohexanecarboxylic acid derivative and an alkyl chain having an alcoholic hydroxyl group bonded to the main chain and having an alkyl chain branched from the alkyl chain are used. The reaction of the diol is obtained. The cyclohexanecarboxylic acid derivative may, for example, be a compound represented by the following formula (2).

(wherein R is independently present and represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Further, X represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms or a halogen atom.)

Specific examples of the compound of the formula (2) include cyclohexanecarboxylic acid, methyl cyclohexanecarboxylate, cyclohexanecarboxyethyl ester, propylcyclohexanecarboxylate, and butylcyclohexanecarboxylate. Hexyl cyclohexanecarboxylate, cyclohexanecarboxylic acid (cyclohexenylmethyl) ester, octyl cyclohexanecarboxylate, cyclohexanecarboxylic acid chloride, cyclohexanecarboxylic acid bromide, methylcyclohexane Alkanoic acid, methyl methylcyclohexanecarboxylate, ethyl methylcyclohexanecarboxylate, propyl methylcyclohexanecarboxylate, methylcyclohexanecarboxylic acid (cyclohexenylmethyl) ester And methylcyclohexanecarboxylic acid chloride or the like, but is not limited thereto. These may be used alone or in combination of two or more.

Further, the diol in the present invention is a diol having a chain-chain alkyl chain having a branched structure and having a total carbon number of 6 to 20.

Specific examples of the compound include the compounds described below.

For the reaction of a cyclohexanecarboxylic acid derivative with a diol, a general esterification method can be used. Specifically, a general esterification reaction can be used, and examples thereof include Fischer esterification using an acid catalyst, acid halide under an alkaline condition, reaction of an alcohol, condensation reaction using various condensing agents, and the like. (ADVANCED ORGANIC CHEMISTRY PartB: Reaction and Synthsis p135, 145-147, 151, etc.). Further, as a specific example, an esterification reaction of an alcohol with a carboxylic acid (Tetrahedron vol. 36 p. 2409 (1980), Tetrahedron Letter p. 4475 (1980)), and a transesterification reaction of a carboxylic acid ester (Japanese special) may also be used. Open 2006-052187) to manufacture.

A preferred structure of the olefin compound of the above formula (1) thus synthesized is preferably any one of a hydrogen atom, a methyl group, an ethyl group and a butyl group in the above formula (1), particularly when substituted When the group R is bonded to an olefin, in order to enhance the reactivity, it is bonded to R of the olefin, preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

The olefin compound of the present invention represented by the above formula (1) can be produced by oxidation of the epoxy resin of the present invention. Examples of the method of oxidation include a method of oxidizing by a peracid such as peracetic acid, a method of oxidizing by hydrogen peroxide water, a method of oxidizing by air (oxygen), and the like, but are not limited thereto.

The method of epoxidation by peracid is specifically, for example, the method described in JP-A-2006-52187.

For the epoxidation method using hydrogen peroxide water, various methods can be used. Specifically, JP-A-59-108793, JP-A-62-234550, JP-A No. 5-213919, and Japanese Laid-Open Patent Publication No. H11-349579, No. Hei.

Hereinafter, a particularly preferred method for producing the epoxy resin of the present invention is exemplified.

First, the olefin compound, the polyacid, and the quaternary ammonium salt of the present invention are reacted in an emulsified state of an organic substance and hydrogen peroxide water.

The polyacid used in the present invention is not particularly limited as long as it has a polyacid structure, and is preferably a polyacid containing tungsten or molybdenum, more preferably a polyacid containing tungsten, particularly preferably a tungstate. class.

Specific examples of the polyacid and the polyacid salt include a tungsten-based acid selected from the group consisting of tungstic acid, 12-phosphoric acid, 12-boron-tungstic acid, 18-phosphoric acid, and 12-telluric acid. A molybdenum-based acid of molybdic acid and phosphomolybdic acid, and the like.

Examples of the comparative cation of the salt include a quaternary ammonium ion, an alkaline earth metal ion, an alkali metal ion, and the like. Among them, particularly preferred comparative cations include sodium ions, potassium ions, calcium ions, and ammonium ions.

Specific examples thereof include tetramethylammonium ion, benzyltriethylammonium ion, decanyl methylammonium ion, dilauryldimethylammonium ion, trioctylmethylammonium ion, and trialkylmethyl group ( Mixed type of octyl and sulfhydryl) ammonium ion, trisylmethylammonium ion, trimethyl stearyl ammonium ion, tetraamylammonium ion, cetyltrimethylammonium ion, benzyltributylammonium ion, Alkaline ammonium ion such as capryl methylammonium ion, dicetyldimethylammonium ion, alkaline earth metal ion such as calcium ion or magnesium ion, alkali metal ion such as sodium, potassium or cesium, but not Limited to these.

The amount of the polyacid to be used is 0.5 to 20 mmol, preferably 0.5 to 20 mmol, in terms of metal element (tungsten acid is a tungsten atom and molybdic acid is a molybdenum atom), based on 1 mol of the olefin compound of the present invention. 1.0 to 20 millimolar, more preferably 2.5 to 15 millimolar.

For the quaternary ammonium salt used in the reaction, it is preferred to use a quaternary ammonium salt having a total carbon number of 10 or more (preferably 25 to 100, more preferably 25 to 55), particularly in which the alkyl chain is aliphatic. The chain is better.

Specific examples thereof include a mixture of a trimethyl ester methylammonium salt, a dilauryldimethylammonium salt, a trioctylmethylammonium salt, and a trialkylmethyl group (a compound in which an alkyl group is an octyl group and a mercapto group). Ammonium salt, trisylmethylammonium salt, trimethylstearyl ammonium salt, tetraamyl ammonium salt, cetyl trimethyl ammonium salt, benzyl tributyl ammonium salt, dicetyl dimethyl ammonium salt And cetylmethylammonium salt, dihardened tallow alkyldimethylammonium salt, etc., but are not limited thereto.

Further, the anion source of the salt is not particularly limited, and specific examples thereof include a halide ion, a nitrate ion, a sulfate ion, a hydrogen sulfate ion, an acetate ion, and a carbonate ion, but are not limited thereto.

If the carbon number is more than 100, the hydrophobicity is too strong, and the solubility of the organic layer of the quaternary ammonium salt may be deteriorated. When the carbon number is less than 10, the hydrophilicity becomes strong, and the compatibility with the organic layer of the quaternary ammonium salt is deteriorated, which is not preferable.

The amount of the quaternary ammonium salt used is preferably 0.01 to 10 equivalents per several times the valence of the tungstate used. More preferably, it is 0.05 to 6.0 equivalents, still more preferably 0.05 to 4.5 equivalents.

For example, in the case of tungstic acid, it is divalent in H ₂ WO ₄ , and the quaternary ammonium salt is preferably in the range of 0.02 to 20 mol with respect to 1 mol of tungstic acid. Further, in the case of phosphotungstic acid, it is trivalent, and the same is preferably 0.03 to 30 mol, and if it is tungstic acid, it is tetravalent, and preferably 0.04 to 40 mol.

When the amount of the quaternary ammonium salt used is less than 0.01 times the number of times the valence of the tungstic acid, the epoxidation reaction is difficult to proceed (the reaction proceeds rapidly as the case may be), and the problem of easily forming by-products is generated. . When it is more than 10 times equivalent, not only the post-treatment becomes troublesome, but also the action of suppressing the reaction is required, which is not preferable.

In the case of the reaction, it is preferred to use a buffer. Any one of the buffers may be used, but it is preferred to use an aqueous phosphate solution in the present reaction. The pH is preferably adjusted to be between pH 4 and 10, more preferably pH 5 to 9. When the pH is less than 4, the epoxy group is easily subjected to a hydrolysis reaction and a polymerization reaction. Further, when the pH exceeds 10, the reaction becomes extremely slow, and the reaction time is too long.

In particular, in the present invention, when the tungstic acid of the catalyst is dissolved, it is preferably adjusted to a pH of from 5 to 9.

When the buffer solution is used, when it is a phosphate-phosphate aqueous solution of a preferred buffer, 0.1 to 10 mol% of phosphoric acid (or a phosphate such as sodium dihydrogen phosphate) is used with respect to the hydrogen peroxide water. A method of pH adjustment using a basic compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate or the like. Here, the pH is preferably added so as to be the above-described pH when hydrogen peroxide is added. Further, it can also be adjusted using sodium dihydrogen phosphate or disodium hydrogen phosphate. The concentration of the preferred phosphate is from 0.1 to 60% by weight, preferably from 1 to 45% by weight.

Further, in the present reaction, a phosphate such as sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium phosphate or sodium tripolyphosphate (or a hydrate thereof) may be directly added thereto without using a buffer. Since the steps are simplified, that is, no complicated pH adjustment is required, it is particularly preferable to add directly. The amount of the phosphate used in this case is usually 0.1 to 5 mol% equivalent, preferably 0.2 to 4 mol% equivalent, more preferably 0.3 to 3 mol% equivalent, based on the hydrogen peroxide. At this time, if the hydrogen peroxide is more than 5 mol% equivalent, the pH adjustment must be performed, and when it is less than 0.1 mol% equivalent, the generated epoxy resin is likely to become a hydrolyzate or the reaction is slow. And other drawbacks.

This reaction is epoxidized using hydrogen peroxide. The hydrogen peroxide used in the reaction is preferably an aqueous solution having a concentration of hydrogen peroxide of 10 to 40% by weight because of its ease of handling. When the concentration exceeds 40% by weight, the handling becomes difficult, and the resulting epoxy resin is also easily subjected to a decomposition reaction, which is not preferable.

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 based on the olefin compound 1 of the reaction substrate. When the ratio exceeds 10 by weight, the progress of the reaction becomes extremely slow, which is not preferable. Specific examples of the organic solvent which can be used include an alkane such as hexane, cyclohexane or heptane, an aromatic hydrocarbon compound such as toluene or xylene, methanol, ethanol, isopropanol, butanol, hexanol or cyclohexane. Alcohols such as alcohols. Further, as the case may be, a ketone such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone or cyclohexanone, an ether such as diethyl ether, tetrahydrofuran or dioxane, ethyl acetate, butyl acetate or formic acid may be used. An ester compound such as an ester or a nitrile compound such as acetonitrile. Particularly preferred solvents are alkane such as hexane, cyclohexane or heptane, and aromatic hydrocarbon compounds such as toluene and xylene.

At this time, after adding buffer (or water and phosphate) and tungstic acid for pH adjustment, a quaternary ammonium salt, an organic solvent, and an olefin compound are added, and after stirring in two layers, the method of dripping hydrogen peroxide is used. .

Alternatively, the method may be as follows: adding tungstic acid, phosphoric acid (or phosphate) under stirring water, an organic solvent, and an olefin compound to adjust the pH, adding a quaternary ammonium salt, and stirring the mixture in two layers. A method of dropping hydrogen peroxide is used.

Specific reaction operation method, for example, when the reaction is carried out in a batch reactor, an olefin compound, hydrogen peroxide (aqueous solution), a polyacid (catalyst), a buffer solution, a quaternary ammonium salt and an organic solvent are added, The layers were stirred. The stirring speed is not specifically specified. When hydrogen peroxide is added, heat is often generated, so that it is also possible to slowly add hydrogen peroxide after adding each component.

The reaction temperature is not particularly limited, and is preferably 0 to 90 ° C, more preferably 0 to 75 ° C, particularly preferably 15 ° C to 60 ° C. When the reaction temperature is too high, the hydrolysis reaction is easily carried out, and if the reaction temperature is low, the reaction rate is extremely slow.

Further, although the reaction time varies depending on the reaction temperature, the amount of the catalyst, and the like, it is considered from the viewpoint of industrial production, and it takes a long time to consume a lot of energy, which is not preferable. The preferred range is from 1 to 48 hours, more preferably from 3 to 36 hours, still more preferably from 4 to 24 hours.

After the reaction is completed, a quenching treatment of excess hydrogen peroxide is performed. Quenching treatment is preferably carried out using a basic compound. Further, it is also preferable to use a reducing agent together with a basic compound. A preferred treatment method is a method in which the pH of the neutral compound is adjusted to pH 6 to 10, and then the residual hydrogen peroxide is quenched by using a reducing agent. When the pH is less than 6, the heat generated when the excess hydrogen peroxide is reduced is large, and there is a possibility that a decomposition product is formed.

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 moles, more preferably 0.05 to 10 moles, still more preferably 0.05 to 3 moles, per mole of excess hydrogen peroxide.

These are preferably added as an aqueous solution, and the concentration thereof is preferably from 0.5 to 30% by weight.

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 ion exchange resins. , alkaline solids such as alumina.

The amount of use thereof is such that it can be dissolved in water or an organic solvent (for example, an aromatic hydrocarbon such as toluene or xylene, a ketone such as methyl isobutyl ketone or methyl ethyl ketone, a hydrocarbon such as cyclohexane, heptane or octane, or methanol. A solvent such as an alcohol such as ethanol or isopropyl alcohol may be used, and the amount thereof is usually 0.01 to 20 moles, more preferably 0.05 to 10 times, relative to the molar amount of excess hydrogen peroxide. More preferably, it is 0.05 to 3 times Mo. These may be added as a solution of water or the above organic solvent, or may be added singly.

When a solid base which is insoluble in water or an organic solvent is used, it is preferably used in an amount of from 1 to 1000 times by weight based on the amount of hydrogen peroxide remaining in the system. More preferably, it is 10 to 500 times, and more preferably 10 to 300 times. When a solid base which is not dissolved in water or an organic solvent is used, it may be treated after being separated into an aqueous layer and an organic layer as described later.

After quenching of hydrogen peroxide (or before quenching), the reaction product is extracted with an aqueous layer. When quenching, when the organic layer and the aqueous layer are not separated, or when the reaction is carried out without using an organic solvent, the organic solvent may be added and the organic solvent used for the extraction of the reaction product in the aqueous layer may be carried out. The weight ratio is 0.5 to 10 times, preferably 0.5 to 5 times, based on the olefin compound. After repeating the operation as many times as necessary, the organic layer is separated, and the organic layer is washed with water as needed for purification.

The obtained organic layer, if necessary, is an ion exchange resin or a metal oxide (especially, cerium oxide gel or alumina, etc.), activated carbon (wherein, in particular, a living activated carbon is preferred), a composite metal salt (wherein In particular, it is preferable to use an alkaline composite metal salt, a viscosity mineral (in particular, a layered viscosity mineral such as microcrystalline kaolinite) to remove impurities, and then to wash and filter the solvent, and then to remove the solvent. The purpose of the epoxy resin.

Further, it may be further purified by distillation depending on the case. The distillation method can be carried out by a method such as thin film or rotary molecular distillation.

The epoxy resin thus obtained is of the formula (3)

(In the formula, R and P in the plural are expressed in the same meaning as in the formula (1).)

The molecule represented by the main component is mixed with the formula (4) (wherein, a combination of (A) to (D) may be any combination. Further, R and P have the same meanings as in the formula (1). ) Compounds of various configurations as indicated. Further, depending on the reaction conditions, a polymer or other side reaction product in which epoxy groups are polymerized with each other is formed.

The obtained epoxy resin, for example, can be used as epoxy acrylate and its derivatives, Various resin materials such as an oxazolidone compound or a cyclic carbonate compound are used.

Hereinafter, the curable resin composition of the present invention containing the epoxy resin of the present invention will be described.

The curable resin composition of the present invention contains the epoxy resin of the present invention as an essential component. In the curable resin composition of the present invention, two methods of thermosetting (curable resin composition A) by a curing agent and cation curing (curable resin composition B) using an acid as a curing catalyst can be used.

In the curable resin composition A and the curable resin composition B, the epoxy resin of the present invention or another epoxy resin may be used alone. When used in combination, the epoxy resin of the present invention preferably accounts for 30% by weight or more and 40% by weight or more based on the total epoxy resin. However, when the epoxy resin of the present invention is used as a modifier for a curable resin composition, it is added in a proportion of 1 to 30% by weight.

Other epoxy resins which can be used together with the epoxy resin of the present invention include novolak type epoxy resin, bisphenol A type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol aralkyl Type epoxy resin, etc. Specific examples thereof include bisphenol A, bisphenol S, thiodiphenol, bismuth bisphenol, stilbene, 4,4'-biphenol, 2,2'-biphenol, and 3,3'. ,5,5'-tetramethyl-[1,1'-biphenyl]-4,4'-diol, hydroquinone, resorcinol, 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, dicyclopentadiene, furfural, 4,4'-bis(chloromethyl)- 1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 1,4'-bis(chloromethyl)benzene, 1,4'-bis ( a condensed polymer such as methoxymethyl)benzene or the like, a denatured product thereof, a halogenated bisphenol such as tetrabromobisphenol A, an epoxypropyl etherate derived from an alcohol, an alicyclic epoxy resin, Epoxypropylamine epoxy resin, epoxy propyl ester epoxy resin, sesquiterpene oxide epoxy resin (chain, ring, ladder, or a solid or liquid epoxy resin having a mixed structure of at least two or more kinds of a nonoxyl structure having an epoxy group and/or an epoxy group having an epoxycyclocyclohexane structure, etc., but is not limited thereto. .

In particular, when the curable resin composition of the present invention is used for optical use, it is preferred to use an epoxy resin of the present invention in combination with an alicyclic epoxy resin or a sesquioxane. In particular, in the case of an alicyclic epoxy resin, a compound having an epoxycyclohexane structure in the skeleton is preferred, and an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexane structure is particularly preferred.

The compound having a cyclohexane structure may, for example, be an esterification reaction of a cyclohexanecarboxylic acid with an alcohol or an esterification reaction of a cyclohexane methanol with a carboxylic acid (Tetrahedron vol. 36 p. 2409 (1980), Tetrahedron Letter p. 4475 (1980), etc., or a Tischenko reaction of cyclohexane aldehyde (Japanese Unexamined Patent Publication No. 2003-170059, No. 2004-262871, etc.) The method described in the above, and a compound produced by a transesterification reaction of a cyclohexanecarboxylic acid ester (method described in JP-A-2006-052187).

The alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, and examples thereof include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, and 1,4-butanediol. , glycols such as 5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxyl Triols such as methyl-1,4-butanediol, tetraols such as pentaerythritol, and the like. Further, examples of the carboxylic acid include oxalic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, adipic acid, and cyclohexanedicarboxylic acid, but are not limited thereto.

Further, examples of the compound having a cyclohexane structure other than the above may be an acetal compound obtained by reacting a cyclohexane-based formaldehyde derivative with an acetal of an alcohol.

The reaction method can be produced by a general acetalization reaction. For example, a method of performing a reaction under azeotropic dehydration using a solvent such as toluene or xylene in a reaction medium is disclosed (U.S. Patent No. 2945008); After the polyol is dissolved in concentrated hydrochloric acid, the reaction is carried out under the gradual addition of an aldehyde (JP-A-48-96590); the method of using water in the reaction medium (U.S. Patent No. 3092640), in the reaction A method of using an organic solvent for a medium (Japanese Patent Laid-Open No. Hei 7-215979), a method using a solid acid catalyst (JP-A-2007-230992), and the like. The cyclic acetal structure is preferred in view of the stability of the structure.

Specific examples of such epoxy resins include ERL-4221, UVR-6105, and ERL-4299 (all of which are trade names, all manufactured by Dow Chemical), CELLOXIDE 2021 P, EPOLEAD GT401, EHPE 3150, and EHPE 3150CE (all of which are trade names). , all are made by Daicel Chemical Industry Co., Ltd.) and dicyclopentadiene diepoxide, but are not limited to these (Reference: General Epoxy Resin, Basic Code I p76-85).

These may be used alone or in combination of two or more.

Hereinafter, each curable resin composition will be described.

Thermal hardening by hardener (curable resin composition A)

The curing agent contained in the curable resin composition A of the present invention may, for example, be an amine compound, an acid anhydride compound, a guanamine compound, a phenol compound or a carboxylic acid compound. Specific examples of the hardener which can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylguanidine, isophoronediamine, dicyandiamide, and linolenic oil. Nitrogen-containing compounds (amines, guanamine compounds) such as polyamine resins synthesized from acid dimers and ethylene diamines; bisphenol A, bisphenol F, bisphenol S, bisphenol, stilbene, 4 , 4'-biphenol, 2,2'-biphenol, 3,3',5,5'-tetramethyl-[1,1'-biphenyl]-4,4'-diol, hydroquinone, Resorcinol, naphthalenediol, tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenols (phenol, alkyl-substituted phenol, naphthalene Phenol, alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) with formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, bicyclo Pentadiene, furfural, 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 1 , 4'-bis(chloromethyl)benzene, 1,4'-bis(methoxymethyl)benzene and the like, and the denatured products thereof, a polyphenol such as a halogenated bisphenol such as bromobisphenol A or a condensate of hydrazine or a phenol; a compound of imidazole, a trifluoroborane-amine complex, an anthracene derivative, a condensate of hydrazine and a phenol, and the like, But it is not limited to these. These may be used alone or in combination of two or more.

In the present invention, in particular, a compound having an acid anhydride structure and/or a carboxylic acid structure represented by the above-described acid anhydride-based compound or carboxylic acid-based compound is preferred.

a compound having an acid anhydride structure, particularly methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, butane tetracarboxylic anhydride, double ring [2,2,1]heptane-2,3-dicarboxylic anhydride, methylbicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, cyclohexane-1,3,4- A tricarboxylic acid-3,4-anhydride or the like is preferred, and among them, methyl hexahydrophthalic anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, 1,2 are particularly preferred. , 4-cyclohexanetricarboxylic acid-1,2-anhydride. It is considered from the viewpoint of improvement in hardness, insulation, heat resistance or imparting high transparency. The hardener is preferably a compound having an anhydride structure.

a compound having a carboxylic acid structure (hereinafter referred to as a polycarboxylic acid), particularly preferably a 2-4-functional polycarboxylic acid, more preferably a 2-4 functional polyol, or a polycarboxylate obtained by an addition reaction with an acid anhydride. acid. It is preferable to use a polycarboxylic acid as a curing agent from the viewpoint that the curing agent has less volatilization, is less likely to cause hardening failure, and is easy to obtain a composition having strong toughness.

The 2 to 4 functional polyol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, and examples thereof include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, and 1,4-. Butylene glycol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3 - diols such as propylene glycol, neopentyl glycol, tricyclodecane dimethanol, dicyclopentadiene dimethanol, norene diol, glycerol, trimethylolethane, trimethylolpropane, trihydroxyl Triols such as methylbutane and 2-hydroxymethyl-1,4-butanediol, tetraols such as neopentyl alcohol and ditrimethylolpropane, and the like.

Particularly preferred 2 to 4 functional polyols are cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, and three A branched or cyclic alcohol such as cyclodecane dimethanol, dicyclopentadiene dimethanol or norbornene diol.

An acid anhydride for producing a polycarboxylic acid, preferably methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butane IV Carboxylic anhydride, bicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, methylbicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, cyclohexane-1,3 , 4-tricarboxylic acid-3,4-anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride, and the like.

The conditions of the addition reaction are not particularly limited. For one of the specific reaction conditions, the following method can be used: the anhydride and the polyol are reacted while heating at 40 to 150 ° C under the conditions of no catalyst or solvent. Remove directly after the reaction is completed. However, it is not limited to the reaction conditions.

The acid anhydride and the polycarboxylic acid may be used alone or in combination of two or more. In this case, the ratio of the acid anhydride to the polycarboxylic acid is preferably from 90/10 to 20/80 by weight, and preferably from 80/20 to 30/70.

The amount of the curing agent used in the curable resin composition A of the present invention is preferably from 0.7 to 1.2 equivalents per equivalent of the epoxy group of the total epoxy resin. When the amount is less than 0.7 equivalents or more than 1.2 equivalents per equivalent of the epoxy group, the hardening is incomplete and good cured physical properties cannot be obtained.

In the curable resin composition A of the present invention, a curing accelerator may be used in combination with the curing agent. Specific examples of the hardening accelerator to be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and 2-phenyl-4-methylimidazole. 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'-methylimidazolium (1')) ethyl-symmetric three 2,4-Diamino-6(2'-undecylimidazolium (1'))ethyl-symmetric three 2,4-Diamino-6(2'-ethyl, 4-methylimidazolium (1')) ethyl-symmetric three 2,4-Diamino-6(2'-methylimidazolium(1'))ethyl-symmetric three ‧ Trimeric isocyanate adduct, 2:3 adduct of 2-methylimidazolium trimeric isocyanate, 2-phenylimidazole trimer isocyanate adduct, 2-phenyl-3,5 -dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole Various imidazoles, and such imidazoles and polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyroic acid, naphthalene dicarboxylic acid, maleic acid, oxalic acid, and the like a guanamine such as a salt or a dicyandiamide; a tertiary amine such as 1,8-difluorene (5.4.0) eleven-7-ene; a phosphine such as triphenylphosphine; or a tetrabutylammonium salt; a tetra-ammonium salt such as triisophenylmethylammonium salt, trimethylsulfonium ammonium salt, hexadecyltrimethylammonium salt, cetyltrimethylammonium salt, triphenylbenzylphosphonium salt, or the like a quaternary phosphonium salt such as a phenylethyl sulfonium salt or a tetramethyl phosphonium salt (the relative ions of the quaternary salt are halogen, organic acid ions, hydroxide ions, etc., although specifically specified, but particularly organic acid ions, hydrogen Oxide ions are preferred), metal compounds such as tin octylate, etc. Hardening accelerator and the like of the microencapsulated microcapsule type curing accelerator. Which of these curing accelerators is used, for example, is appropriately selected depending on the properties required for the transparent resin composition obtained by the transparency, the curing speed, and the working conditions. The hardening accelerator is usually used in an amount of from 0.01 to 50 parts by weight based on 100 parts by weight of the total epoxy resin.

The curable resin composition A of the present invention may contain a phosphorus-containing compound as a flame retardancy-imparting component. The phosphorus-containing compound may be either a reactive type or an additive type. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, toluene phosphate, trixyl phosphate, toluene diphenyl phosphate, toluene-2,6-dixyl phosphate, and 1,3. - Phosphate esters such as phenylene bis(dimethyl cresyl phosphate), 1,4-phenylene bis(dimethyl methacrylate), 4,4'-biphenyl (dimethyl methacrylate); 9,10- a phosphine such as a dihydro-9-oxo-10-phosphaphenanthrene-10-oxide; a phosphorus-containing epoxy compound obtained by reacting an epoxy resin with an active hydrogen of the above phosphine, and a red phosphorus And preferably, a phosphate ester, a phosphine or a phosphorus-containing epoxy compound, particularly preferably 1,3-phenylene bis(dimethyl methacrylate), 1,4-phenylene bis (phosphoric acid di bisphosphate) Toluene ester), 4,4'-biphenyl (dixyl phosphate) or phosphorus-containing epoxy compound. The content of the phosphorus-containing compound is preferably a phosphorus-containing compound/total epoxy resin = 0.1 to 0.6 (weight ratio). When the thickness is less than 0.1, the flame retardancy is insufficient, and if it exceeds 0.6, the hygroscopicity and dielectric properties of the cured product are adversely affected.

Further, in the curable resin composition A of the present invention, an antioxidant may be added as needed. Examples of the antioxidant that can be used include a phenol-based, sulfur-based, and phosphoric acid-based antioxidant. The antioxidant may be used singly or in combination of two or more. The amount of the antioxidant to be used is usually from 0.008 to 1 part by weight, preferably from 0.01 to 0.5 part by weight, per 100 parts by weight of the resin component in the curable resin composition A of the present invention.

Examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphoric acid-based antioxidant. Specific examples of the phenolic antioxidant include, for example, 2,6-di-tertiary butyl-p-cresol, butylated hydroxyanisamine, 2,6-di-tri-butyl-p-ethylphenol, Stearyl-β-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-tertiarybutyl-4-hydroxybenzene Propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tertiary butylanilino)-1,3,5-triazine, Monophenols such as 2,4-bis[(octylthio)methyl]-o-cresol; 2,2'-methylenebis(4-methyl-6-tertiary butylphenol), 2, 2'-methylenebis(4-ethyl-6-tertiary butylphenol), 4,4'-thiobis(3-methyl-6-tertiary butylphenol), 4,4'- Butylene bis(3-methyl-6-tertiary butyl phenol), triethylene glycol-bis[3-(3-tri-butyl-5-methyl-4-hydroxyphenyl)propionate] 1,6-hexanediol-bis[3-(3,5-di-tri-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylene double (3,5 -di-tertiary butyl-4-hydroxy-phenylpropanamide), 2,2-thio-divinyl bis[3-(3,5 Di-tertiary butyl-4-hydroxyphenyl)propionate], 3,5-di-tertiary butyl-4-hydroxybenzyl phosphate-diethyl ester, 3,9-bis[1,1 -Dimethyl-2-{β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoxy}ethyl]2,4,8,10-tetra Bisphenols such as snail [5.5] undecane, bis(3,5-di-tri-butyl-4-hydroxybenzyl sulfonate); 1,1,3-tris(2-methyl-4) -hydroxy-5-tertiary butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) Benzene, tetra-[methylene-3-(3',5'-di-tertiarybutyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis-(4'-hydroxy-3'-tertiary butylphenyl)butyrate]diol, tris-(3,5-di-tri-butyl-4-hydroxybenzyl)-isocyanate, 1, 3,5-tris(3',5'-di-tertiary butyl-4'-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, tocopherol Such as polymeric phenols.

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

Specific examples of the phosphate-based antioxidant include, for example, triphenyl phosphate, diphenylisodecyl phosphate, phenyl diisononyl phosphate, tris(nonylphenyl) phosphate, diisodecyl neopentyl tetraphosphate. Alcohol ester, tris(2,4-di-tert-butylphenyl) phosphate, cyclopentaerythritol bis(octadecyl) phosphate, cyclopentaerythritol diphosphate (2,4-di-tris) Butyl phenyl) ester, cyclopentatetramethyl bis(2,4-di-tert-butyl-4-methylphenyl) phosphate, hydrogen bis[2-tributyl-6-- Phosphates such as 4-{2-(octadecyloxycarbonyl)ethyl}phenyl] ester; 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-tertiary butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide, 10-decyloxy- An oxophosphorus oxide such as 9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide.

These oxidizing agents may be used alone or in combination of two or more. In the present invention, a phosphorus-based antioxidant is particularly preferred.

Further, in the curable resin composition A of the present invention, a light stabilizer may be added as needed.

The light stabilizer is preferably a hindered amine light stabilizer, particularly HALS. HALS is not particularly limited, and representatives may include dibutylamine ‧1,3,5-triazine‧N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl-1, a polycondensate of 6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, dimethyl-1-(2-hydroxyethyl) succinate 4-hydroxy-piperidine polycondensate, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{ (2,2,6,6-tetramethyl-4-piperidinyl) fluorenylene}hexamethylene {(2,2,6,6-tetramethyl-4-piperidinyl)pyrene Amino}], bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxybenzene Methyl]butylmalonate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-five Methyl-4-piperidinyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, 2-(3, 5-di-tertiary butyl-4-hydroxybenzyl)-2-n-butylmalonic acid bis(,2,2,6,6-pentamethyl-4-piperidinyl), etc. HALS can only One type may be used or two or more types may be used in combination.

Further, in the curable resin composition A of the present invention, a binder resin may be blended as needed. Examples of the binder resin include a butyraldehyde resin, an acetal resin, an acrylic resin, an epoxy-resistant resin, an NBR-phenol resin, an epoxy-NBR resin, a polyamide resin, and a polyruthenium resin. An amine resin, a polysiloxane resin, or the like, but is not limited thereto. 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 by weight, per 100 parts by weight of the resin component. Share.

In the curable resin composition A of the present invention, an inorganic filler may be added as needed. Examples of the inorganic filler include crystalline cerium oxide, molten cerium oxide, aluminum oxide, zircon, calcium silicate, calcium carbonate, cerium carbide, cerium nitride, boron nitride, zirconium oxide, magnesium silicate, and a block. Powders such as talc, spinel, titanium oxide, talc, or the like, or the like, are not limited thereto. These may be used alone or in combination of two or more. The content of the inorganic filler is used in an amount of from 0 to 95% by weight in the curable resin composition A of the present invention. Further, in the curable resin composition A of the present invention, a decane coupling agent, stearic acid, palmitic acid, calcium stearate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, or the like) may be added. Zinc compound such as zinc octadecanoate or zinc myristate or zinc phosphate (zinc octyl phosphate, zinc stearyl phosphate, etc.), surfactants, dyes, pigments, ultraviolet absorbers, and the like, various heats Curable resin.

When the curable resin composition A of the present invention is used for an optical semiconductor encapsulant, a phosphor may be added as needed. The phosphor, for example, absorbs a part of the blue light emitted by the blue LED element, converts the wavelength, and emits yellow light, thereby having the effect of forming white light. After the phosphor is previously dispersed in the curable resin composition, the photo-semiconductor is sealed. The phosphor is not particularly limited, and a conventional phosphor can be used, and examples thereof include an aluminate of a rare earth element, a thiogallate, a decanoate, and the like. More specifically, YAG (yttrium aluminum garnet) phosphor, TAG (yttrium aluminum garnet) phosphor, orthosilicate phosphor, thiogallate phosphor, sulfide fluorescent The phosphor such as a body may, for example, be YAlO ₃ :Ce, Y ₃ Al ₅ Ol ₂ :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. The particle diameter of the phosphor may be a known particle diameter in the art, but the average particle diameter is preferably from 1 to 250 μm, particularly preferably from 2 to 50 μm. When such a phosphor is used, the amount thereof is from 1 to 80 parts by weight, preferably from 5 to 60 parts by weight, per 100 parts by weight of the resin component.

The curable resin composition A of the present invention can be obtained by uniformly mixing the components. The curable resin composition A of the present invention can be easily formed into a cured product by the same method as the conventional method. For example, the epoxy resin and the hardener of the present invention, and optionally a hardening accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent are used as needed, such as an extruder, a kneader, a roll, etc. The curable resin composition is obtained by mixing until it is uniform, and the curable resin composition is molded by potting, melting (non-melting in a liquid state) or a transfer molding machine, and then 80 to 80 The cured product of the present invention is obtained by heating at 200 ° C for 2 to 10 hours.

Further, the curable resin composition A of the present invention can be dissolved in toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethyl acetamide, N, if necessary. a solvent such as methylpyrrolidone as a curable resin composition varnish, and a prepreg obtained by heating and drying a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber or paper, and preparing the prepreg The impregnation body is subjected to hot press forming to obtain a cured product of the curable resin composition A of the present invention. The solvent at this time is usually used in an amount of 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. Further, in the case of a liquid composition, an epoxy resin-containing cured product containing carbon fibers can be directly produced, for example, by RTM.

Further, the curable resin composition A of the present invention can also be used as a modifier of a film-type composition. Specifically, it can be used in the case of improving the flexibility characteristics and the like in the B stage. In the resin composition of the film type, the curable resin composition A of the present invention can be applied to the release film as the curable resin composition varnish, and the solvent can be removed by heating, and then B-staged. A flaky adhesive is obtained. The sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

Curable resin composition B (hardened by cationic cation of acid hardening catalyst)

The curable resin composition B of the present invention which is cured by an acidic curing catalyst contains a photopolymerization initiator or a thermal polymerization initiator as an acid curing catalyst. Further, various well-known compounds, materials, and the like may be contained, such as a diluent, a polymerizable monomer, a polymerizable oligomer, a polymerization initiation aid, and a photosensitizer. Further, various well-known additives such as an inorganic filler, a coloring pigment, an ultraviolet absorber, an antioxidant, and a stabilizer may be contained as needed.

The acid curing catalyst is preferably a cationic polymerization initiator, and a photocationic polymerization initiator is particularly preferred. Examples of the cationic polymerization initiator include those having an iodonium salt, an onium salt, and a diazonium salt. These may be used alone or in combination of two or more.

Examples of active energy ray cationic polymerization initiators are metal fluoroboron salt and boron trifluoride complex (U.S. Patent No. 3,375, 653), bis(perfluoroalkylsulfonyl)methane metal salt (US Patent No. No. 3586616), an aryl diazonium salt compound (U.S. Patent No. 3,708,296), an aromatic sulfonium salt of a Via group element (U.S. Patent No. 4,058,400), an aromatic sulfonium salt of a Group Va element (U.S. Patent No. 4,609,905), Dicarbonyl chelates of Group IIIa to Va elements (U.S. Patent No. 4,406,091), thiopyrylium salt (U.S. Patent No. 4,139,655), and MF ₆ ^- anionic form of Group VIb (US Patent No. No. 4,161,478; M is selected from the group consisting of phosphorus, bismuth and arsenic.), aryl sulfonium salt (U.S. Patent No. 4,231,951), aromatic iodonium salt and aromatic sulfonium salt (U.S. Patent No. 4,256,828), and [4-(Diphenyldihydrothio)phenyl]sulfide-bis-hexafluorometal salt (Journal of Polymer Science, Polymer Chemistry, Vol. 2, item 1789 (1984)). Further, a mixed ligand metal salt of an iron compound and a decyl-aluminum complex may also be used.

Further, specific examples include "ADEKA OPTOMER SP150", "ADEKA OPTOMER SP170" (all manufactured by Asahi Kasei Kogyo Co., Ltd.), "UVE-1014" (manufactured by General Electric Company), and "CD-1012" (manufactured by Sartomer Co., Ltd.) ), "RP-2074" (made by Rhodia Corporation).

The amount of the cationic polymerization initiator to be used is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the total epoxy resin component.

In addition, these photocationic polymerization initiators, one of the known polymerization initiators and the photosensitizer, may be used alone or in combination of two or more. Examples of the polymerization initiator are benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1, 1-di Chloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2- Morpholinol propan-1-one, N,N-dimethylaminoacetophenone, 2-methylindole, 2-ethylhydrazine, 2-tributylphosphonium, 1-chloroindole Bismuth, 2-pentyl hydrazine, 2-isopropyl thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthene Ketone, acetophenone dimethyl ketal, benzophenone, 4-methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminodiphenyl A photoradical polymerization initiator such as ketone or michonone. The amount of the polymerization initiator to be used, such as a photoradical polymerization initiator, is 0.01 to 30 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the photoradical polymerizable component.

Specific examples of the photosensitizer include hydrazine, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropyl Thiophenone, acridine orange, acridine yellow, phosphine R, benzoflavine, thioflavin (setoflavine), hydrazine, ethyl N,N-dimethylaminobenzoate, N,N- Isoamyl dimethylaminobenzoate, triethanolamine, triethylamine, and the like. The amount of the photosensitizer used is 0.01 to 30 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total epoxy resin.

In addition, as the curable resin composition B of the present invention, various compounding agents such as an inorganic filler, a decane coupling material, a release agent, and a pigment, and various thermosetting resins may be added as needed. Specific examples are as described above.

The curable resin composition B of the present invention can be obtained by uniformly mixing the components. Further, it may be dissolved in an organic solvent such as polyethylene glycol monoethyl ether or cyclohexanone or γ-butyrolactone to make it uniform, and then used by drying to remove the solvent. The solvent at this time is usually used in an amount of 10 to 70% by weight (preferably 15 to 70% by weight) in the mixture of the curable resin composition B of the present invention and the solvent. The curable resin composition B of the present invention can be cured by irradiation with ultraviolet rays. However, since the amount of ultraviolet irradiation varies depending on the composition of the curable resin composition, it is determined depending on the respective curing conditions. Specifically, the curing amount of the cured curable resin composition may be cured, and the adhesion strength of the cured product may be good. At the time of the hardening, light must pass through the fine portion, and therefore the epoxy resin and the curable resin composition B of the present invention are expected to have high transparency. Further, these epoxy resin-based photohardening is difficult to completely cure only by light irradiation, and in applications requiring heat resistance, it is necessary to heat the reaction after light irradiation to completely complete the reaction hardening.

When heating is performed after light irradiation, it can be carried out in the hardening temperature range of the usual curable resin composition B. For example, it is preferably in the range of 30 minutes to 7 days from room temperature to 150 °C. Although it changes depending on the blending of the curable resin composition B, particularly in the higher temperature range, the hardening promotion after light irradiation is more effective, and the heat treatment is effective only for a short period of time. Moreover, the lower the temperature, the longer the heat treatment is required. With such heat and post-hardening, it also has the effect of ripening treatment.

In addition, the shape of the cured product obtained by curing the curable resin composition B may be various shapes depending on the application, and is not particularly limited. For example, it may be formed into a film shape, a sheet shape, a block shape or the like. The method of forming varies depending on the location and the member to be used. For example, a molding method such as a casting method, a casting method, a screen printing method, a spin coating method, a spray method, a transfer method, or a dispenser method can be used, but Not limited to these. As the forming mold, a ground glass, a hard stainless steel grinding plate, a polycarbonate plate, a polyethylene terephthalate plate, a polymethyl methacrylate plate or the like can be used. Moreover, in order to improve the release property from the molding die, a polyethylene terephthalate film, a polycarbonate film, a polyvinyl chloride film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, and a polyfluorene can be used. Imine film and the like.

For example, when used in a cationically curable photoresist, the photocationic curable resin composition of the present invention dissolved in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone or γ-butyrolactone is used as a net. A method such as a plate printing or a spin coating method is applied to a substrate such as a copper area laminate, a ceramic substrate or a glass substrate with a film thickness of 5 to 160 μm to form a film. Thereafter, the film is pre-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 ultra-high pressure mercury lamp, a xenon lamp, a laser beam, etc.) through a negative film on which a desired pattern is drawn, and then The post-exposure baking treatment was carried out at 70 to 120 °C. Thereafter, the unexposed portion is removed (developed) by a solvent such as polyethylene glycol monoethyl ether, and then sufficiently cured by irradiation with ultraviolet rays or heating (for example, at 100 to 200 ° C for 0.5 to 3 hours). And get hardened. Thus, a printed wiring board can be obtained.

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 such as optical component materials. The material for optics is generally used as a material used for the purpose of passing light such as visible light, infrared rays, ultraviolet rays, X-rays, and laser light through the material. More specifically, a sealing material for LEDs such as a lamp type or an SMD type, and the following may be mentioned. A material for a liquid crystal display device such as a substrate material such as a substrate material, a light guide plate, a ruthenium sheet, a polarizing plate, a phase difference plate, a viewing angle correction film, an adhesive, or a polarizing element protective film in the liquid crystal display field. In addition, as a next-generation flat panel display, it is expected to be a color PDP (plasma display) sealing material, an antireflection film, an optical correction film, an outer casing material, a front glass protective film, a front glass replacement material, an adhesive, or an LED display. The molding material of the LED used in the device, the sealing material of the LED, the protective film of the front glass, the front glass substitute material, the adhesive, or the substrate material in the plasma address liquid crystal display (PLAC), the light guide plate , enamel sheet, polarizing plate, phase difference plate, viewing angle correction film, adhesive, polarizing element protective film, or protective film for front glass in organic EL (organic electroluminescence) display, front glass replacement material, adhesive, or Various film substrates in a field emission display (FED), a protective film for front glass, a front glass replacement material, and an adhesive. In the field of optical recording, it is a VD (Video CD), CD/CD-ROM, CD-R/RW, DVD-R/DVD-RW, MO/MD, PD (phase change optical disc), optical disc substrate for optical memory card. Materials, pickup lenses, protective films, sealing materials, adhesives, and the like.

In the field of optical equipment, it is a lens material for a still camera, a finder prism, a target prism, a finder cover, and a light receiving sensor unit. Moreover, it is also a photographic lens and a viewfinder of a video camera. Moreover, it is also a projection lens, a protective film, a sealing material, an adhesive, etc. of a projection television. A material for a lens of an optical sensing machine, a sealing material, an adhesive, a film, or the like. In the field of optical components, it is a fiber material, a lens, a waveguide, a sealing material for components, an adhesive, and the like around the optical switch of the optical communication system. Optical fiber material, ferrule, sealing material, adhesive, etc. around the optical connector. Yuguang passive parts, lenses of optical circuit parts, waveguide paths, LED sealing materials, CCD sealing materials, adhesives, etc. A substrate material, a fiber material, a sealing material for an element, an adhesive, and the like around the optoelectronic integrated circuit (OEIC). In the field of optical fiber, it is used for decorative display illumination, light guide, etc., for industrial use sensors, displays, signs, etc., or for communication infrastructure and digital fiber connection for use in homes. The material surrounding the semiconductor integrated circuit is a photoresist material for micro-etching of LSI and super LSI materials. In the field of automobiles and transport aircraft, it is a lamp reflector for automobile, bearing retainer, gear part, corrosion resistant coating, switch part, headlight, engine parts, electrical equipment parts, various internal and external components, drive engine, brake oil drum , automotive rust-proof steel, inner side panels, interior materials, protection, bundled wire vehicles, fuel hoses, car lights, glass substitutes. Also, the double glazing for the train. In addition, the toughness imparting agent for the structural material of the aircraft, the engine peripheral member, the protection, the wire car for binding, and the corrosion resistant coating. In the field of construction, it is a material for interior decoration, processing, lampshade, seat, glass interlayer film, glass substitute, and solar cell peripheral materials. For agricultural use, it is a film for greenhouse coating. As a next generation light, motor organic material, organic EL element peripheral material, organic photorefractive element, optical amplifying element of optical-optical conversion element, optical computing element, substrate material around organic solar cell, fiber material, component Sealing material, adhesive, etc.

Examples of the sealant include encapsulation, encapsulation, transfer molding, sealing, IC, LSI COB, COF, TAB, etc. in capacitors, transistors, diodes, light-emitting diodes, ICs, and LSIs. In the case of underfill, such as underfill, BGA, CSP, etc., the package of IC package type (underfill for reinforcement).

The other use of the material for the optical material is a general use used for the curable resin composition A or the curable resin composition B, and examples thereof include an adhesive, a coating material, a coating agent, and a molding material (including a sheet, a film, an FRP, etc.). Insulation materials (including printed boards, wire coatings, etc.), sealants, and additives to other resins. When the curable resin composition A or B of the present invention is used as an additive to other resins, it may be used as a curing agent for a cyanate resin composition for a sealing material or a substrate, or as a photoresist. The curing agent is used in the case of an acrylate resin or the like. Examples of the adhesive agent include civil engineering, construction, automotive, general-purpose, medical adhesives, and adhesives for electronic materials. Examples of the adhesive for the electronic material in the above-mentioned materials include an interlayer adhesive for a multilayer substrate such as a thick substrate, a semiconductor adhesive such as a die bond or an underfill, an underfill for BGA reinforcement, and an anisotropic conductive. An adhesive such as a film (ACF) or an anisotropic conductive paste (ACP).

The curable resin composition A and the curable composition B of the present invention are excellent in heat-resistant deterioration properties such as heat resistance and heat-resistant coloring property, moisture resistance, light resistance, and the like, and therefore are particularly used as a sealant and/or crystal of an LED device. It is preferred to use a particulate binder. Moreover, since the curable resin composition A and the curable composition B of the present invention have the above-described excellent characteristics, they can be used for a reflector of an LED device.

Example

Next, the present invention will be more specifically described by way of examples, and the parts represent parts by weight unless otherwise specified. Further, the invention is not limited to the embodiments. Further, in the examples, the epoxy equivalent was measured in accordance with JIS K-7236, and the viscosity was measured at 25 ° C using an E-type viscometer. Further, in the analysis conditions in gas chromatography (hereinafter referred to as "GC"), HP5-MS (0.25 mm ID × 15 m, film thickness: 0.25 μm) was used for the separation column, and the column oven temperature was set to the initial stage. The temperature was raised to 100 ° C at a rate of 15 ° C per minute to 300 ° C and maintained for 90 minutes. Further, helium gas is used as a carrier gas. In addition, the measurement of gel permeation chromatography (hereinafter referred to as "GPC") is as follows. The column is Shodex SYSTEM-21 (KF-803L, KF-802.5 (×2), KF-802), the extracting solution is tetrahydrofuran, the flow rate is 1ml/min, the column temperature is 40 °C, and the detection system is The measurement was carried out using UV (254 nm), and the calibration line was made of standard polystyrene manufactured by Shodex.

Example 1

In a flask equipped with a stirrer, a reflux cooling tube, a stirring device, and a Dean-Stark tube, 150 parts of toluene and 2-butyl-2-ethyl- were added under a nitrogen purge. 80 parts of 1,3-propanediol (butyl ethyl propylene glycol manufactured by Kyowa Fermentation Co., Ltd.), 126 parts of 3-cyclohexanecarboxylic acid, and 2 parts of p-toluenesulfonic acid, and reacted while removing water under reflux 10 hours. After completion of the reaction, the mixture was washed twice with 50 parts of a 10% by weight aqueous sodium hydrogencarbonate solution, and the obtained organic layer was washed twice with water (50 portions), and then the organic solvent was concentrated on a rotary evaporator. The olefin compound (D-1) of the invention was 182 parts. The shape was liquid, and the purity obtained by gas chromatography was 96%. Further, as a result of analysis by gel permeation chromatography, it was confirmed that the purity was >98%.

Example 2

In a flask equipped with a stirrer, a reflux cooling tube and a stirring device, 15 parts of water, 0.95 parts of 12-phosphoric acid, 0.78 parts of disodium hydrogen phosphate, and 2 hardened tallow alkyl dimethyl ammonium were added under a nitrogen purge. 2.7 parts of acetate (manufactured by Lion Akzo, 50% hexane solution, Arquad 2HT acetate) to form a tungstic acid-based catalyst, 120 parts of toluene, and 94 parts of the olefin compound D-1 obtained in Example 1 were added again. Stir and become a liquid in a latex state. The solution was warmed to 50 ° C, and under vigorous stirring, 55 parts of 35% hydrogen peroxide water was added, and the mixture was directly stirred at 50 ° C for 13 hours. As a result of confirming the progress of the reaction by GC, the conversion ratio of the substrate after the completion of the reaction was >99%, and the peak of the raw material disappeared (<1% or less).

Next, after neutralizing with a 1% by weight aqueous sodium hydroxide solution, 25 parts of a 20% by weight aqueous sodium thiosulfate solution was added, and the mixture was stirred for 30 minutes, and allowed to stand. After separating into two layers, the organic layer was taken out, and 10 parts of cerium oxide gel (Wako-gel C-300 manufactured by Wako Pure Chemical Industries, Ltd.), activated carbon (CAP SUPER made by NORIT), and expanded soil (manufactured by Hojun) were added thereto. Ben-gel SH) 20 parts, stirred at room temperature for 1 hour, and then filtered. The obtained filtrate was washed with water three times with 100 parts of water, and the obtained organic layer was distilled off by an organic solvent to obtain 89 parts of an epoxy resin (EP-1) having the following formula (5) as a main component.

From the measurement results of GPC, 98% of the compound containing the skeleton of the formula (5) was confirmed. Further, the purity in the GC measurement was 91%. Further, the epoxy equivalent was 215 g/eq.

Example 3

To 15 parts of the obtained epoxy resin (EP-1), 105 parts of a cerium oxide gel (Wako-gel C-300 and Wako Pure Chemical Industries, Ltd.) was used, and a developing solvent of ethyl acetate:hexane = 1:4 was used. Purified by column chromatography.

The obtained epoxy resin (EP-2) was 10 parts, and the purity of the obtained epoxy resin was determined by GPC measurement, and 98% or more of the compound containing the skeleton of the above formula (5) was confirmed. Further, the purity in the GC measurement was about 99%. Further, the epoxy equivalent was 207 g/eq.

Example 4

In a flask equipped with a stirrer, a reflux cooling tube, a stirring device, and a Dean-Stark tube, 150 parts of toluene and 2,4-diethyl-1,5-pentanediol were added under a nitrogen purge. 80 parts of Waoru PD9, 126 parts of 3-cyclohexanecarboxylic acid, and 2 parts of p-toluenesulfonic acid were reacted under reflux with heating, and the reaction was carried out for 10 hours while removing water. After completion of the reaction, the mixture was washed twice with 50 parts of a 10% by weight aqueous sodium hydrogencarbonate solution, and the obtained organic layer was washed twice with water (50 portions), and then the organic solvent was concentrated on a rotary evaporator. The olefin compound (D-2) of the invention was 187 parts. The shape was liquid, and the purity obtained by gas chromatography was 96%. Further, as a result of analysis by gel permeation chromatography, it was confirmed that the purity was >98%.

Example 5

In a flask equipped with a stirrer, a reflux cooling tube and a stirring device, 15 parts of water, 0.95 parts of 12-phosphoric acid, 0.78 parts of disodium hydrogen phosphate, and 2 hardened tallow alkyl dimethyl ammonium were added under a nitrogen purge. 2.7 parts of acetate (manufactured by Lion Akzo, 50% hexane solution, Arquad 2HT acetate) to form a tungstic acid-based catalyst, 120 parts of toluene, and 94 parts of the olefin compound D-2 obtained in Example 4 were added again. Stir and become a liquid in a latex state. The solution was warmed to 50 ° C, and under vigorous stirring, 55 parts of 35% hydrogen peroxide water was added, and the mixture was directly stirred at 50 ° C for 13 hours. As a result of confirming the progress of the reaction by GC, the conversion ratio of the substrate after the completion of the reaction was >99%, and the peak of the raw material disappeared (<1% or less).

Next, after neutralizing with a 1% by weight aqueous sodium hydroxide solution, 25 parts of a 20% by weight aqueous sodium thiosulfate solution was added, and the mixture was stirred for 30 minutes, and allowed to stand. After separating into two layers, the organic layer was taken out, and 10 parts of cerium oxide gel (Wako-gel C-300 manufactured by Wako Pure Chemical Industries, Ltd.), activated carbon (CAP SUPER made by NORIT), and expanded soil (manufactured by Hojun) were added thereto. Ben-gel SH) 20 parts, stirred at room temperature for 1 hour, and then filtered. The obtained filtrate was washed with water three times with 100 parts of water, and the obtained organic layer was distilled off by an organic solvent to obtain 90 parts of an epoxy resin (EP-3) having the following formula (6) as a main component.

From the measurement results of GPC, 98% of the compound containing the skeleton of the formula (6) was confirmed. Further, the purity in the GC measurement was 91%. Further, the epoxy equivalent was 216 g/eq.

Example 6

To 15 parts of the obtained epoxy resin (EP-3), 105 parts of a cerium oxide gel (Wako-gel C-300 and Wako Pure Chemical Industries, Ltd.) was used, and a developing solvent of ethyl acetate:hexane = 1:4 was used. Purified by column chromatography.

The obtained epoxy resin (EP-4) was 11 parts, and the purity of the obtained epoxy resin was determined by GPC measurement, and it was confirmed that the compound containing the skeleton of the above formula (6) was 98% or more. Further, the purity in the GC measurement was about 99%. Further, the epoxy equivalent was 209 g/eq.

Synthesis Example 1

In Example 1, 80 parts of 2-butyl-2-ethyl-1,3-propanediol (butyl ethyl propylene glycol manufactured by Kyowa Fermentation Co., Ltd.) was changed to neopentyl glycol (Mitsubishi Gas Chemicals Co., Ltd.) The same operation was carried out except for the production of 52 parts of the olefin compound (D-3). The shape was liquid, and the purity by gas chromatography was 97%. Further, as a result of analysis by gel permeation chromatography, it was confirmed that the purity was >98%.

Synthesis Example 2

In the second embodiment, 94 parts of the olefin compound (D-1) was changed to 80 parts of the olefin compound (D-3), and the same operation was carried out, and as a result, the following formula (7) was mainly produced. 56 parts of epoxy resin (EP-5).

From the measurement results of GPC, 98% of the compound containing the skeleton of the formula (7) was confirmed. Further, the purity in the GC measurement was 95%. Further, the epoxy equivalent was 182 g/eq.

Synthesis Example 3

To 15 parts of the obtained epoxy resin (EP-5), 105 parts of a cerium oxide gel (Wako-gel C-300 and Wako Pure Chemical Industries, Ltd.) was used, and a developing solvent of ethyl acetate:hexane = 1:4 was used. Purified by column chromatography.

The obtained epoxy resin (EP-6) was 13 parts, and the purity of the obtained epoxy resin was determined by GPC measurement, and it was confirmed that the compound containing the skeleton of the above formula (7) was 98% or more. Further, the purity in the GC measurement was about 99%. Further, the epoxy equivalent was 180 g/eq.

Synthesis Example 4

In Example 1, 80 parts of 2-butyl-2-ethyl-1,3-propanediol (butyl ethyl propylene glycol manufactured by Kyowa Fermentation Co., Ltd.) was changed to 1,6-hexanediol (Tokyo). The same operation was carried out except that 59 parts of Chemical Industry Co., Ltd. were produced, and 157 parts of an olefin compound (D-4) was obtained. The shape was liquid, and the purity obtained by gas chromatography was 95%. Further, as a result of analysis by gel permeation chromatography, it was confirmed that the purity was >98%.

Synthesis Example 5

In the second embodiment, 94 parts of the olefin compound (D-1) was changed to 83 parts of the olefin compound (D-4), and the same operation was carried out, and as a result, the following formula (8) was mainly produced. 77 parts of epoxy resin (EP-7).

From the measurement results of GPC, 98% of the compound containing the skeleton of the formula (8) was confirmed. Further, the purity in the GC measurement was 90%. Further, the epoxy equivalent was 199 g/eq.

Synthesis Example 6

To 15 parts of the obtained epoxy resin (EP-7), 105 parts of a cerium oxide gel (Wako-gel C-300 and Wako Pure Chemical Industries, Ltd.) was used, and a developing solvent of ethyl acetate:hexane = 1:4 was used. Purified by column chromatography.

The obtained epoxy resin (EP-8) was 9 parts, and the purity of the obtained epoxy resin was determined by GPC measurement, and it was confirmed that the compound containing the skeleton of the above formula (8) was 98% or more. Further, the purity in the GC measurement was about 99%. Further, the epoxy equivalent was 185 g/eq.

Examples 7, 8, and 9, Comparative Examples 1, 2

Epoxy resin (EP-2, EP-3, EP-4) of the present invention obtained in Examples 3, 5, and 6, epoxy resin (EP- manufactured as Synthesis Example 3, Synthesis Example 6 of Comparative Example) 6. EP-8), using a mixture of methyl hexahydrophthalic anhydride and hexahydrophthalic anhydride as a hardener (Nippon Chemical and Chemical Co., Ltd., RIKACID MH700G, hereinafter referred to as H1), double ring [2] , 2,1]heptane-2,3-dicarboxylic anhydride (manufactured by Nippon Chemical and Chemical Co., Ltd., RIKACID HNA-100, hereinafter referred to as H2), and hexadecyltrimethylammonium hydroxide as a hardening accelerator (Tokyo) A 25% methanol solution manufactured by Chemical Industries Co., Ltd., hereinafter referred to as C1), was blended in a blending ratio (parts by weight) shown in the following Table 1 to carry out defoaming for 20 minutes to obtain a curable resin composition of the present invention.

Using the obtained curable resin composition, a heat resistance test, a heat durability transmittance test, and an LED test were carried out in the following manner. The results are shown in Table 1. Further, the heat-resistance test and the hardening conditions in the LED test were 140 ° C × 2 hours after preliminary hardening at 120 ° C × 2 hours.

(heat resistance test)

The curable resin composition obtained in the examples and the comparative examples was subjected to vacuum defoaming for 20 minutes, and then gently cast into a metal mold for a test piece having a width of 7 mm, a length of 5 cm, and a thickness of 800 μm, and then The amine film was made into a lid. The cast material was cured under the above conditions to obtain a test piece for dynamic viscoelasticity. Using these test pieces, a dynamic viscoelasticity test was carried out under the conditions shown below.

Measuring condition

Dynamic viscoelasticity tester: TA-instruments, DMA-2980

Measuring temperature range: -30 ° C ~ 280 ° C

Heating rate: 2 ° C / min

Test piece size: used to cut into 5 mm × 50 mm (thickness about 800 μm).

Parsing condition

Tg: The peak point of Tan-δ in the DMA measurement is regarded as Tg.

(thermal durability transmittance test)

The obtained curable resin composition was subjected to vacuum defoaming for 20 minutes, and then gently cast to a glass substrate which was formed into a dam so as to have a heat-resistant tape of 30 mm × 20 mm × height 1 mm. The cast material was pre-hardened at 120 ° C for 3 hours, and then cured at 150 ° C for 1 hour to obtain a test piece for transmittance of 1 mm in thickness.

Using these test pieces, the transmittance (measuring wavelength: 375 nm or 400 nm) placed in an oven at 150 ° C for 96 hours was measured by a spectrophotometer, and the rate of change was calculated.

(LED lighting test)

The curable resin composition obtained in the examples and the comparative examples was subjected to vacuum defoaming for 20 minutes, and then filled into a syringe, and cast into a 5 mm square surface of an outer diameter of a light-emitting element having an emission wavelength of 465 nm using a precision discharge device. Type LED housing (inner diameter 4.4mm, outer wall height 1.25mm). Thereafter, it was hardened under the above-described hardening conditions to obtain an LED for lighting test. The lighting test is performed by a lighting test with a predetermined current of 30 mA. The detailed conditions are shown below. For the measurement item, the illuminance of the LED for the test was calculated using an integrating sphere to measure the illuminance of the LED for 200 hours before and after the lighting.

Lighting details

Light emission wavelength: 465nm

Drive mode: constant current mode, 30mA (light-emitting component specified current is 30mA)

Drive environment: 85 ° C, 85%

Evaluation: When the illuminance is less than 5%, it is ○, when it is less than 10%, it is △, and when it is 10% or more, it is ×.

When Comparative Examples 7 to 9 and Comparative Examples 1 and 2, the curable resin composition of the present invention is compared with a curable resin composition using an epoxy resin having a similar chain-like linking group, and it is understood that not only heat resistance but also It is excellent in heat-resistant deterioration characteristics such as heat-resistant coloring property and excellent in light resistance. The same tendency can be seen when compared to compounds having similar Tg. From the above results, it is understood that the epoxy resin of the present invention can provide a curable resin composition excellent in heat deterioration resistance characteristics and optical characteristics.

Synthesis Example 7

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 12 parts of dicyclopentadiene dimethanol and methyl hexahydrophthalic anhydride (Nippon Chemical and Chemical Co., Ltd.) were added under a nitrogen purge. RIKACID MH, hereinafter referred to as anhydride H3), 73 parts, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride (H-TMAn, manufactured by Mitsubishi Gas Chemical Co., Ltd., hereinafter referred to as H4), 15 parts at 40 ° C After heating for 2 hours and then heating at 60 ° C for 1 hour (confirmation of dicyclopentadiene dimethanol to 0.5% or less by GPC), a hardener composition (HA) of a mixture of a polycarboxylic acid and an acid anhydride was obtained. -1) 100 parts. The functional group equivalent of the obtained compound was 171 g/eq. (The carboxylic acid and the acid anhydride were each regarded as a monofunctional group).

Synthesis Example 8

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 10 parts of 2,4-diethylpentanediol (co-fermentation fermented medicine to obtain Vaou PD-18) was added under a nitrogen purge. 50 parts of the acid anhydride (H3) was heated at 40 ° C for 2 hours, followed by heating and stirring at 60 ° C for 1 hour (the GPC confirmed that 2,4-diethylpentanediol was 0.5% or less), thereby producing a poly 60 parts of hardener composition (HA-2) of a mixture of a carboxylic acid and an acid anhydride. The functional group equivalent of the obtained compound was 201 g/eq.

Example 10

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 75.2 parts of the olefin compound D-2 obtained in Example 4, 75 parts of toluene, 10 parts of water, and 12-phosphoric acid were added under a nitrogen purge. 0.4 parts, 0.60 parts of sodium tungstate, 0.60 parts of disodium hydrogen phosphate, 0.54 parts of trioctylmethylammonium acetate (manufactured by Lion Akzo, 50% xylene solution, TOMAA-50), the solution was heated to 48 ° C, Under stirring, 44 parts of 35% hydrogen peroxide water was added, and the mixture was directly stirred at 48 ° C for 16 hours. The results of the reaction were confirmed by GC, and the conversion ratio of the substrate after the completion of the reaction was >99%, and the peak of the raw material was <1%.

Subsequently, the mixture was adjusted to pH 9 with a 30% by weight aqueous sodium hydroxide solution, and then 20 parts by weight of a 20% by weight aqueous sodium thiosulfate solution was added thereto, and the mixture was stirred for 30 minutes, and allowed to stand. After separating into two layers, the organic layer was taken out, and 8 parts of montmorillonite (Kunipia F manufactured by Kunimine Industries) and 9 parts of activated carbon (CP-1 manufactured by Ajinomoto Fine-Techno) were added thereto, and the mixture was stirred at room temperature for 3 hours. Filter. The obtained filtrate was washed with water for 100 times in 100 parts of water, and the obtained organic layer was distilled off by an organic solvent to obtain an epoxy resin (EP-9) of the present invention having the structure of the above formula (6) as a main component. ) 76.4 parts. The epoxy equivalent was 210 g/eq.

Synthesis Example 9

In Example 10, 75.2 parts of the olefin compound (D-2) was changed to 1,4-cyclohexanedimethanol and 3-cyclohexenecarboxylic acid to be esterified and synthesized as shown in the following scheme (9). In the same manner as in the above, the synthesis of the olefin compound was carried out in the same manner, and 73 parts of a comparative epoxy resin (EP-10) was obtained. The epoxy equivalent was 207 g/eq.

Synthesis Example 10

In the same manner as in Example 10, 75.2 parts of the olefin compound (D-2) was changed to 66.9 parts of the olefin compound (D-4), and the synthesis was carried out in the same manner to obtain the skeleton of the above formula (8) as a main component. The epoxy resin (EP-11) used for comparison was 67.0 parts. The epoxy equivalent was 196 g/eq.

Synthesis Example 11

In Example 10, 75.2 parts of the olefin compound (D-2) was changed to an olefin compound 66.9 having the structure shown in the following (10) synthesized by dehydration and esterification of adipic acid and 4-cyclohexenemethanol. In the same manner as in the above, the synthesis was carried out in the same manner, and 67.2 parts of a comparative epoxy resin (EP-12) was obtained. The epoxy equivalent was 194 g/eq.

Example 11, Comparative Example 3, 4, 5

The epoxy resin (EP-9) obtained in Example 10, and the epoxy resin (EP-10, EP-11, EP-12) obtained as Comparative Examples 9, 10 and 11 of Comparative Example were used as a hardener. An acid anhydride (H1) and a quaternary phosphonium salt (PX-4MP, manufactured by Nippon Chemical Industry Co., Ltd., hereinafter referred to as C2) as a curing accelerator were blended in a mixing ratio (parts by weight) shown in Table 2 below for defoaming for 20 minutes. The curable resin composition of the present invention is obtained.

Using the obtained curable resin composition, the LED test was carried out in the manner shown below. The results are shown in Table 2. Further, the curing conditions were 140 ° C × 3 hours after preliminary hardening at 110 ° C × 2 hours.

(LED lighting test A)

The obtained curable resin composition was subjected to vacuum defoaming for 20 minutes, and then filled into a syringe, and cast into a 5 mm square outer surface mount type LED case (inner diameter) of a wafer loaded with a center light wave of 465 nm using a precision discharge device. 4.4mm, outer wall height 1.25mm). Thereafter, the test was performed by hardening under a predetermined hardening condition to obtain a test LED.

The lighting test is performed by a lighting test with a predetermined current of 30 mA. The detailed conditions are shown below. In the measurement item, the illuminance before and after lighting at each time point of the lighting for 400 hours, 600 hours, and 800 hours was measured using an integrating sphere, and the retention of the illuminance of the test LED was calculated.

Lighting details

Light emission wavelength: 465nm

Drive mode: constant current mode, 30mA (light-emitting component specified current is 30mA)

Drive environment: 85 ° C, 85%

(LED lighting test B)

Moreover, in the same environment as the above-described LED lighting test (that is, conditions of 85 ° C and 85%), the test LEDs were not stored and stored, and the measurement was carried out for 400 hours, 600 hours, and 800 hours using an integrating sphere. The illuminance before and after each time point was used to calculate the retention of the illuminance of the test LED.

Using the epoxy resin (EP-9) of the present invention obtained in Example 10, and the synthetic examples 7 and 8 of the hardener composition, respectively, the hardener composition (HA-1) (HA-2) and the phosphoric acid of the additive were prepared. The ester zinc complex (JC-9206, hereinafter referred to as AD-1) and the hindered amine compound (LA-77 manufactured by Adeka, hereinafter referred to as AD-2) are compounded as shown in Table 3 below. The curable composition of the present invention is obtained in combination with (parts by weight).

(thermal durability transmittance test)

The obtained curable resin composition was subjected to vacuum defoaming for 20 minutes, and then gently cast to a glass substrate which was formed into a dam so as to have a heat-resistant tape of 30 mm × 20 mm × height 1 mm. The cast material was pre-hardened at 110 ° C for 2 hours, and then cured at 150 ° C for 3 hours to obtain a test piece for transmittance of 1 mm in thickness. Using the obtained test piece, the transmittance (measuring wavelength: 400 nm) placed in an oven at 150 ° C for 96 hours was measured by a spectrophotometer, and the rate of change was calculated.

Example 14 and Comparative Example 6

The epoxy resin (EP-9) obtained in Example 10, and 3,4-epoxycyclohexylmethyl-3',4',-epoxycyclohexyl carbonate as a comparative example (SEJ-made by Nippon Kayaku Co., Ltd.) 01R, an epoxy equivalent of 130 g/eq., hereinafter referred to as an epoxy resin (EP-13), an acid anhydride (H3) as a curing agent, and an imidazole compound as a curing accelerator (2E4MZ manufactured by Shikoku Chemical Co., Ltd., hereinafter referred to as The curable resin composition of the present invention was obtained by blending the compounding ratio (parts by weight) shown in the following Table 4 with C3).

The obtained curable resin composition was cast into a metal mold (a disc having a diameter of 50 mm and a thickness of 3 mm), and the cast material was pre-hardened at 120 ° C for 2 hours, and then hardened at 160 ° C for 5 hours to obtain a cured product. Test piece for testing. Using the obtained test piece, moisture absorption and water absorption tests were carried out under the following conditions, and the weight increase rate was confirmed. The results are shown in Table 4 below.

(Humidity resistance test 1) In a constant temperature bath, the environment is at a temperature of 85 ° C and a humidity of 85% for 24 hours.

(Humidity resistance test 2) In a pressure vessel, the temperature is 121 ° C, the humidity is 100%, and the environment is 24 hours.

(Water resistance test 1), boiling in water at about 100 ° C for 24 hours

From the above results, it was confirmed that the epoxy resin composition using the epoxy resin of the present invention has not only high moisture resistance and water resistance but also high optical characteristics. In particular, in the results of Example 11 and Comparative Examples 3 to 5, it is understood that the epoxy resin composition using the epoxy resin of the present invention has better moisture resistance characteristics than those using a simple chain structure (LED). In the lighting test B), as a result of the illuminance retention of the LED, not only the chain structure but also a high illuminance retention ratio compared with a compound having a ring structure is obtained, and the height is characteristic as an LED.

The present invention has been described with reference to the specific embodiments thereof, and various modifications and changes can be made without departing from the spirit and scope of the invention.

In addition, the present invention is based on Japanese Patent Application No. 2009-091585, filed on Jan. Moreover, all reference frames cited herein are used in their entirety in the present invention.

Claims (10)

An olefin compound represented by the following formula (1), (wherein, the plural R exists independently, and represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and P is a chain alkyl chain linking group having a branched structure of 6 to 20 carbon atoms. ). The olefin compound according to claim 1, wherein the linking group P has a structure having a main chain of 3 or more carbon atoms and an alkyl branch at at least one position. The olefin compound according to claim 1, wherein the linking group P has two or more alkyl groups which are branched in a main chain. The olefin compound according to claim 2, wherein the linking group P has two or more alkyl groups which are branched in a main chain. The olefin compound according to any one of claims 1 to 4, which is represented by the following formula (D-1) or (D-2): An epoxy resin obtained by oxidizing an olefin compound according to any one of claims 1 to 5. The epoxy resin of claim 6 is epoxidized using hydrogen peroxide or peracid. A curable resin composition containing the epoxy resin and hardener and/or hardening catalyst of claim 6 or 7. A cured product obtained by hardening a curable resin composition of claim 8 of the patent application. An LED device sealed and/or die bonded by a curable resin composition of the eighth application of the patent application.