JP5367065B2 - Olefin compound, epoxy resin, curable resin composition and cured product thereof, LED device - Google Patents

Abstract

Disclosed is a novel alicyclic epoxy resin which enables the production of a cured material having excellent resistance to thermal deterioration and excellent optical properties. The epoxy resin is produced by using an olefin compound represented by formula (1) as a raw material and epoxidizing the olefin compound. [In the formula, there are multiple R's, and the multiple R's independently represent a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms; and P represents a linear alkyl chain linker having 6 to 20 carbon atoms in total and having a branched structure.]

Description

  The present invention relates to a novel olefin compound and an epoxy resin derived from the olefin compound, which are suitable for use in electrical and electronic materials. 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. Furthermore, it is related with the LED device sealed with the cured resin composition.

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

  In addition, in the field of optoelectronics, particularly in recent years, advanced information technology has developed a technology that makes use of optical signals instead of conventional signal transmission in order to smoothly transmit and process vast amounts of information. . In particular, in the field of optical components such as optical waveguides, blue LEDs, and optical semiconductors, development of resin materials having excellent transparency is desired. In response to these demands, alicyclic epoxy compounds have attracted attention.

  An alicyclic epoxy compound is superior in terms of electrical insulation and transparency as compared with a glycidyl ether type epoxy compound, and is used in various ways as a transparent sealing material. However, alicyclic epoxy compounds with improved heat resistance and light resistance have been demanded particularly in fields requiring advanced heat / light properties such as LED applications (see Patent Documents 1 to 3).

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

  An object of this invention is to provide the novel alicyclic epoxy resin which gives the hardened | cured material which is excellent in a heat-resistant deterioration characteristic and an optical characteristic.

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

(In the formula, a plurality of R's are present independently and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and P is a chain alkyl having a branched structure having 6 to 20 carbon atoms in total. An olefin compound represented by a chain linker),
(2)
The olefin compound according to item (1), wherein the linker P has a structure having a main chain of 3 or more carbon atoms and an alkyl branched chain in at least one position;
(3)
The olefin compound according to (1) or (2) above, wherein the linker P has two or more alkyl groups that are branched from the main chain,
(4)
The olefin compound according to any one of (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 (1) to (4) above;
(6)
The epoxy resin according to the above item (5), epoxidized with hydrogen peroxide or peracid,
(7)
A curable resin composition comprising the epoxy resin according to the above item (5) or (6) and a curing agent and / or a curing catalyst;
(8)
Hardened | cured material formed by hardening | curing curable resin composition of previous clause (7),
(9)
An LED device sealed with and / or die-bonded with the curable resin composition according to (7) above,
About.

  The olefin compound of the present invention is a raw material of an epoxy resin (epoxy resin of the present invention) that provides a cured product excellent in heat resistance, light resistance, or moisture resistance such as heat resistance and heat resistance, as well as adhesiveness. Become. The curable resin composition of the present invention containing the epoxy resin of the present invention is useful for a wide range of applications such as electric / electronic materials, molding materials, casting materials, laminated materials, paints, adhesives, resists and the like. Moreover, since the epoxy resin of this invention does not have an aromatic ring, it is very useful for an optical material.

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

(In the formula, a plurality of R's are present independently and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and P is a chain alkyl having a branched structure having 6 to 20 carbon atoms in total. It is a chain linker.)

  In the above formula (1), the chain alkyl chain linker represented by P has as its main chain an alkyl chain in which two alcoholic hydroxyl groups of a diol used as a raw material are bonded as described below, and the alkyl chain It is a structure which has the alkyl chain branched from. The branched alkyl chain may be branched from any carbon atom constituting the main chain, and includes, for example, a case where the branched alkyl chain is branched from a carbon to which an alcoholic hydroxyl group is bonded. Specific examples of such chain alkyl chain linkers are shown below.

(In the above formula, the linker P is bonded to the oxygen atom of the formula (1) with *.)
In the olefin compound of the present invention, the linker P has a structure having an alkyl branched chain with respect to the main chain alkylene group and is not particularly limited as long as the total carbon number is 6 to 20, but the main chain carbon number is not limited. Is 3 or more, preferably 3 to 10, preferably having at least one alkyl branched chain, and particularly preferably having two or more alkyl branched chains. The number of carbon atoms in the alkyl branched chain is preferably 2 to 17 from the viewpoint of heat resistant coloration.
From the viewpoint of imparting heat resistance, heat resistance coloring property, moisture resistance and high illuminance retention, those having an alkyl branched chain from two or more carbon atoms having different main chain alkylene groups are particularly preferred. In this case, those having 2 or more carbon atoms in the branched chain are preferred.

  The olefin compound represented by the formula (1) includes a cyclohexene carboxylic acid derivative and a diol having a structure in which an alkyl chain to which an alcoholic hydroxyl group is bonded has an alkyl chain branched from the alkyl chain. Obtained by reaction. As the cyclohexene carboxylic acid derivative, the following formula (2)

(In the formula, each R is independently present and represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X represents a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms or a halogen atom.)
The compound represented by these is mentioned.
Specific examples of the compound of the formula (2) include cyclohexene carboxylic acid, methyl cyclohexene carboxylate, ethyl cyclohexenecarboxylate, propyl cyclohexenecarboxylate, butyl cyclohexenecarboxylate, hexylcyclohexenecarboxylate, and (cyclohexenylmethyl) cyclohexenecarboxylate. Octylcyclohexenecarboxylate, cyclohexenecarboxylic acid chloride, cyclohexenecarboxylic acid bromide, methylcyclohexenecarboxylic acid, methylcyclohexenecarboxylate, ethyl methylcyclohexenecarboxylate, methylcyclohexenecarboxylate, (methylcyclohexenylmethyl) methylcyclohexenecarboxylate, Examples include methylcyclohexene carboxylic acid chloride, The present invention is not limited to these. These may be used alone or in combination of two or more.
The diol in the present invention is a diol having a chain alkyl chain having a branched structure and having a total carbon number of 6 to 20.
Specific examples of the compound include those described below.

  A general esterification method can be applied to the reaction of the cyclohexenecarboxylic acid derivative and the diol. Specifically, general esterification reactions can be applied, such as Fischer esterification using acid catalysts, acid halides under basic conditions, alcohol reactions, and condensation reactions using various condensing agents (ADVANCED ORGANIC CHEMISTRY). Part B: Reaction and Synthesis p135, 145-147, 151, etc.). Specific examples include esterification reactions between alcohols and carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980), and transesterification reactions of carboxylic acid esters (Japan). It can also be produced by using Japanese Patent Laid-Open No. 2006-052187.

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

The olefin compound of the present invention represented by the formula (1) can be oxidized to form the epoxy resin of the present invention. Examples of the oxidation method include, but are not limited to, a method of oxidizing with a peracid such as peracetic acid, a method of oxidizing with a hydrogen peroxide solution, and a method of oxidizing with air (oxygen).
Specific examples of the epoxidation method using peracid include the method described in Japanese Patent Application Laid-Open No. 2006-52187.
Various methods can be applied to the method of epoxidation with hydrogen peroxide solution. Specifically, Japanese Patent Application Laid-Open No. 59-108793, Japanese Patent Application Laid-Open No. 62-234550, Japanese Patent Application Laid-Open No. No. 5-291919, Japanese Patent Application Laid-Open No. 11-349579, Japanese Patent Publication No. 1-33341, Japanese Patent Publication No. 2001-17864, Japanese Patent Publication No. 3-57102, etc. Various methods can be applied.

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

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

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

  As the quaternary ammonium salt used in the reaction, a quaternary ammonium salt having a total carbon number of 10 or more, preferably 25 to 100, more preferably 25 to 55 can be preferably used. In particular, the alkyl chain is all aliphatic chains. Some are preferred.

Specifically, tridecanylmethylammonium salt, dilauryldimethylammonium salt, trioctylmethylammonium salt, trialkylmethyl (a mixed type of a compound in which the alkyl group is an octyl group and a compound in which the decanyl group is a compound) ammonium salt, trihexa Examples include decylmethylammonium salt, trimethylstearylammonium salt, tetrapentylammonium salt, cetyltrimethylammonium salt, benzyltributylammonium salt, dicetyldimethylammonium salt, tricetylmethylammonium salt, and di-cured tallow alkyldimethylammonium salt. It is not limited to.
There are no particular limitations on the anionic species of these salts, and specific examples include halide ions, nitrate ions, sulfate ions, hydrogen sulfate ions, acetate ions, carbonate ions, and the like, but are not limited thereto.

When the number of carbon atoms exceeds 100, the hydrophobicity becomes too strong, and the solubility of the quaternary ammonium salt in the organic layer may deteriorate. When the number of carbon atoms is less than 10, the hydrophilicity is increased, and the compatibility of the quaternary ammonium salt with the organic layer is similarly deteriorated.
The amount of quaternary ammonium salt used is preferably 0.01 to 10 times the valence of the tungstic acid used. More preferably, it is 0.05-6.0 times equivalent, More preferably, it is 0.05-4.5 times equivalent.

For example, since tungstic acid is divalent with H ₂ WO ₄ , the quaternary ammonium salt is preferably in the range of 0.02 to 20 mol per 1 mol of tungstic acid. Moreover, since it is trivalent in the case of tungstophosphoric acid, it is similarly 0.03 to 30 mol, and in the case of silicotungstic acid, it is tetravalent, so 0.04 to 40 mol is preferable.
When the amount of quaternary ammonium salt used is lower than 0.01 times the valence of tungstic acids, the epoxidation reaction is difficult to proceed (in some cases, the reaction proceeds faster), and by-products The problem that it is easy to do occurs. When the amount is more than 10 times equivalent, not only is the post-treatment difficult, but there is a function of suppressing the reaction, which is not preferable.

In the reaction, a buffer solution is preferably used. Any buffer can be used, but it is preferable to use an aqueous phosphate solution in this reaction. The pH is preferably adjusted between pH 4 and 10, more preferably pH 5-9. When the pH is less than 4, the hydrolysis reaction and polymerization reaction of the epoxy group easily proceed. Moreover, when pH10 is exceeded, reaction will become extremely slow and the problem that reaction time is too long will arise.
In particular, in the present invention, when the tungstic acid as a catalyst is dissolved, the pH is preferably adjusted to be between 5 and 9.

For example, in the case of a phosphoric acid-phosphate aqueous solution, which is a preferable buffer, 0.1 to 10 mol% equivalent of phosphoric acid (or a phosphate such as sodium dihydrogen phosphate) is used. And a method of adjusting pH with a basic compound (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, etc.). Here, it is preferable that the pH is added so that the above-mentioned pH is obtained when hydrogen peroxide is added. It is also possible to adjust using sodium dihydrogen phosphate or disodium hydrogen phosphate. The preferred phosphate concentration is 0.1 to 60% by weight, preferably 1 to 45% by weight.
In this reaction, a buffer solution is not used, and a phosphate such as disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate or sodium tripolyphosphate (or a hydrate thereof) is directly added without adjusting the pH. It doesn't matter. In the sense of simplifying the process, there is no troublesome pH adjustment, and direct addition is particularly preferred. The amount of phosphate used in this case is usually 0.1 to 5 mol% equivalent, preferably 0.2 to 4 mol% equivalent, more preferably 0.3 to 3 mol% equivalent to hydrogen peroxide. is there. In this case, if the amount exceeds 5 mol% equivalent to hydrogen peroxide, pH adjustment is required. If the amount is less than 0.1 mol% equivalent, the resulting epoxy resin hydrolyzate tends to proceed or the reaction is slow. The harmful effect of becoming.

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

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

At this time, buffer solution (or water and phosphate) and tungstic acid were added to adjust pH, then quaternary ammonium salt, organic solvent and olefin compound were added and hydrogen peroxide was added dropwise to the mixture after stirring in two layers. The technique of doing is used.
Alternatively, while stirring water, an organic solvent and an olefin compound, tungstic acid and phosphoric acid (or phosphates) are added, pH is adjusted, quaternary ammonium salt is added, and the mixture is stirred in two layers. Alternatively, a method of dropping hydrogen peroxide may be used.

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

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

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

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

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

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

After quenching hydrogen peroxide (or before quenching), the reaction product is extracted from the 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 above organic solvent is added and the operation is performed. Perform extraction.
The organic solvent used in this case is 0.5 to 10 times, preferably 0.5 to 5 times by weight with respect to the raw material olefin compound. This operation is repeated several times as necessary, and then the organic layer is separated. If necessary, the organic layer is washed with water and purified.
The obtained organic layer may be an ion exchange resin, a metal oxide (especially silica gel or alumina is preferred), activated carbon (especially chemical activated carbon is particularly preferred), or a complex metal salt (especially a basic complex metal salt). Are preferably removed), a mineral with a viscosity (especially a layered viscosity mineral such as montmorillonite is preferred) and the like, and after washing with water and filtration, the solvent is distilled off to obtain the desired epoxy resin.
In some cases, it may be further purified by distillation. As the distillation method, distillation may be performed by a technique such as thin film or rotary molecular distillation.

  The epoxy resin thus obtained has the formula (3)

(In the formula, a plurality of R and P have the same meaning as in formula (1).)
The main component is a molecule represented by formula (4)

(In the formula, any combination of (A) to (D) may be used. R and P have the same meaning as in formula (1).)
The compounds of various structures as shown in FIG. Depending on the reaction conditions, polymerized high molecular weight polymer of epoxy groups and other side reaction products are formed.

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

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

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

  Other epoxy resins that can be used in combination with the epoxy resin of the present invention include novolac type epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins, phenol aralkyl type epoxy resins and the like. Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, -Hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4-bis Polycondensates with (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene, etc. and their modified products, halogenated bisphenols such as tetrabromobisphenol A, glycidyl ethers derived from alcohols, fats Cyclic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, silsesquioxane epoxy resin (chain, cyclic, ladder, or a mixed structure of at least two of these glycidyl groups and siloxane structures) // Epoxy resin having epoxycyclohexane structure), etc. However, it is not limited to these.

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

  Furthermore, as a compound having a cyclohexene structure other than the above, an acetal compound obtained by an acetal reaction between a cyclohexene aldehyde derivative and an alcohol is exemplified. As a reaction method, it can be produced by applying a general acetalization reaction. For example, a method of carrying out a reaction while azeotropically dehydrating using a solvent such as toluene or xylene as a reaction medium (US Pat. No. 2,945,008), concentrated hydrochloric acid A method in which polyhydric alcohol is dissolved in the reaction mixture and the reaction is carried out while gradually adding aldehydes (Japanese Patent Laid-Open No. 48-96590), a method using water as a reaction medium (US Pat. No. 3,092,640), reaction A method using an organic solvent as a medium (Japanese Patent Laid-Open No. 7-215979), a method using a solid acid catalyst (Japanese Patent Laid-Open No. 2007-230992), and the like are disclosed. A cyclic acetal structure is preferable from the viewpoint of structural stability.

Specific examples of these epoxy resins include ERL-4221, UVR-6105, ERL-4299 (all trade names, all manufactured by Dow Chemical), Celoxide 2021P, Eporide GT401, EHPE3150, EHPE3150CE (all trade names, all Daicel). Chemical Industry) and dicyclopentadiene diepoxide, and the like, but are not limited to these (Reference: Review Epoxy Resin Basic Edition I p76-85).
These may be used alone or in combination of two or more.

Hereinafter, each curable resin composition will be referred to.
Thermal curing with a curing agent (curable resin composition A)
Examples of the curing agent contained in the curable resin composition A of the present invention include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds. Specific examples of the curing agent that can be used include nitrogen-containing compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and a polyamide resin synthesized from ethylenediamine. Amide compound); bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [1 , 1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols ( Enol, 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, Polyphenols such as polycondensates with 1,4′-bis (methoxymethyl) benzene and their modified products, halogenated bisphenols such as tetrabromobisphenol A, condensates of terpenes and phenols; Imidazole, trifluoroborane - amine complex, a compound of guanidine derivatives, such as condensation products of terpenes and phenols, but are not limited thereto. These may be used alone or in combination of two or more.
In the present invention, compounds having an acid anhydride structure and / or a carboxylic acid structure represented by the above-mentioned acid anhydride compounds and carboxylic acid compounds are particularly preferable.

  Examples of the compound having an acid anhydride structure include methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2 , 1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride Products, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride and the like are preferable, and methylhexahydrophthalic anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, 2,4-cyclohexanetricarboxylic acid-1,2-anhydride is particularly preferred. From the viewpoint of improving hardness, insulation, heat resistance or imparting high transparency, it is preferable to use a compound having an acid anhydride structure as a curing agent.

As the compound having a carboxylic acid structure (hereinafter referred to as polycarboxylic acid), a bi- to tetra-functional polycarboxylic acid is particularly preferable, and a 2- to 4-functional polyhydric alcohol is preferably added to an acid anhydride. The polycarboxylic acid obtained by this is preferable. It is preferable to use polycarboxylic acid as the curing agent from the viewpoint that the curing agent is less volatile, poor curing is difficult to occur, and a tough composition is easily obtained.
The 2- to 4-functional polyhydric alcohol is not particularly limited as long as it is a compound having an alcoholic hydroxyl group, but ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol. 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecanedi Diols such as methanol, dicyclopentadiene dimethanol, norbornenediol, triols such as glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, 2-hydroxymethyl-1,4-butanediol, pentaerythritol, dito Tetraols and the like, such as trimethylolpropane.
Particularly preferred bifunctional to tetrafunctional polyhydric alcohols are cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol, tricyclodecane dimethanol, Branched and cyclic alcohols such as cyclopentadienedimethanol and norbornenediol.

  Examples of acid anhydrides for producing polycarboxylic acids include methyltetrahydrophthalic anhydride, methylnadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [ 2,2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3, 4-anhydride, 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride and the like are preferable.

  Although there is no particular designation as a condition for the addition reaction, one specific reaction condition is to react an acid anhydride and a polyhydric alcohol while heating at 40 to 150 ° C. under a catalyst-free and solvent-free condition. In this method, the reaction is taken out after completion of the reaction. However, it is not limited to this reaction condition.

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

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

  In the curable resin composition A of the present invention, a curing accelerator may be used in combination with the curing agent. Specific examples of the curing accelerator that can be used include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole. 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,4-diamino-6 (2′-methyl Imidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-undecylimidazole (1 ′)) ethyl-s-triazine, 2,4-diamino-6 (2′-ethyl, 4-methylimidazole (1 ')) ethyl-s-triazine, 2,4-diamino-6 (2'- Methylimidazole (1 ′)) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethyl Various imidazoles such as imidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and imidazoles and phthalic acid, isophthalic acid, terephthalic acid Acids, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, salts with polyvalent carboxylic acids such as succinic acid, amides such as dicyandiamide, 1,8-diaza-bicyclo (5.4.0) undecene Tertiary amines such as 7 and triphenylphosphine Quaternary ammonium salts such as tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, hexadecyltrimethylammonium salt, cetyltrimethylammonium salt, triphenylbenzylphosphonium salt, triphenylethylphosphine Quaternary phosphonium salts such as phonium salt and tetrabutylphosphonium salt (counter ion of quaternary salt is not particularly specified, such as halogen, organic acid ion, hydroxide ion, etc., but especially organic acid ion, hydroxide ion is Preferably), a metal compound such as tin octylate, and a microcapsule type curing accelerator in which these curing accelerators are formed into microcapsules. Which of these curing accelerators is used is appropriately selected depending on characteristics required for the obtained transparent resin composition, such as transparency, curing speed, and working conditions. A hardening accelerator is normally used in 0.01-5.0 weight part with respect to 100 weight part of all the epoxy resins.

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

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

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

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

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

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

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

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

  An inorganic filler can be added to the curable resin composition A of the present invention as necessary. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These may be used alone or in combination of two or more. The content of these inorganic fillers is 0 to 95% by weight in the curable resin composition A of the present invention. Further, the curable resin composition A of the present invention includes a silane coupling agent, stearic acid, palmitic acid, calcium stearate, zinc carboxylate (zinc 2-ethylhexanoate, zinc stearate, zinc behenate, zinc myristate). And zinc compounds such as zinc phosphate phosphate (octyl zinc phosphate, zinc stearyl phosphate, etc.), various compounding agents such as surfactants, dyes, pigments, UV absorbers, and various thermosetting resins can be added. it can.

When using the curable resin composition A of this invention for an optical semiconductor sealing agent, a fluorescent substance can be added as needed. For example, the phosphor has a function of forming white light by absorbing part of blue light emitted from a blue LED element and emitting wavelength-converted yellow light. After the phosphor is dispersed in advance in the curable resin composition, the optical semiconductor is sealed. There is no restriction | limiting in particular as fluorescent substance, A conventionally well-known fluorescent substance can be used, For example, rare earth element aluminate, thio gallate, orthosilicate, etc. are illustrated. More specifically, phosphors such as a YAG phosphor, a TAG phosphor, an orthosilicate phosphor, a thiogallate phosphor, and a sulfide phosphor can be mentioned, and YAlO ₃ : Ce, Y ₃ Al ₅ O1 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 are exemplified. As the particle size of the phosphor, those having a particle size known in this field are used, and the average particle size is preferably 1 to 250 μm, particularly preferably 2 to 50 μm. When using these fluorescent substance, the addition amount is 1-80 weight part with respect to 100 weight part with respect to a resin component, Preferably, 5-60 weight part is preferable.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  As sealing agents, potting, dipping, transfer mold sealing in applications such as capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, potting sealings, flipping in applications such as ICs, LSIs COB, COF, TAB, etc. Examples include underfill in applications such as chips, and sealing (reinforcing underfill) when mounting IC packages such as BGA and CSP.

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

  The curable resin composition A and the curable resin composition B of the present invention are excellent in heat deterioration characteristics such as heat resistance and heat resistance, moisture resistance, light resistance, and the like, and are particularly suitable for LED device sealants and / or Alternatively, it is preferably used as a die bonding agent. Moreover, the curable resin composition A and the curable resin composition B of the present invention can be applied to a reflector of an LED device due to the above-described excellent characteristics.

EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified. The present invention is not limited to these examples.
In the examples, the epoxy equivalent was measured using an E-type viscometer at JIS K-7236 and the viscosity at 25 ° C. The analysis conditions in gas chromatography (hereinafter referred to as “GC”) were as follows: HP5-MS (0.25 mm ID x 15 m, film thickness 0.25 μm) was used for the separation column, and the column oven temperature was set to the initial temperature 100. The temperature was set at a temperature of 15 ° C. per minute and held at 300 ° C. for 90 minutes. Helium was used as a carrier gas. Furthermore, the measurement in gel permeation chromatography (hereinafter referred to as “GPC”) is as follows. The column is a Shodex SYSTEM-21 column (KF-803L, KF-802.5 (× 2), KF-802), the linking eluent is tetrahydrofuran, and the flow rate is 1 ml / min. The column temperature was 40 ° C., detection was performed at UV (254 nm), and a standard polystyrene manufactured by Shodex was used for the calibration curve.

Example 1
To a flask equipped with a stirrer, a reflux condenser, a stirrer, and a Dean-Stark tube, 150 parts of toluene, 2-butyl-2-ethyl-1,3-propanediol (Kyowa Hakko Chemical Co., Ltd. 80 parts of ethyl propanediol), 126 parts of 3-cyclohexenecarboxylic acid and 2 parts of paratoluenesulfonic acid were added, and the reaction was carried out under heating and refluxing for 10 hours while removing water. After completion of the reaction, the olefinic compound of the present invention is washed twice with 50 parts of a 10% by weight aqueous sodium hydrogen carbonate solution and the organic layer obtained is washed twice with 50 parts of water and then concentrated with a rotary evaporator. 182 parts of (D-1) was obtained. The shape was liquid and the purity 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
A flask equipped with a stirrer, reflux condenser, and stirrer is purged with nitrogen, 15 parts of water, 0.95 parts of 12-tungstophosphoric acid, 0.78 parts of disodium hydrogen phosphate, di-cured tallow alkyldimethylammonium acetate After adding 2.7 parts (50% hexane solution made by Lion Akzo, Acquard 2HT acetate) to produce a tungstic acid catalyst, 120 parts of toluene, 94 parts of the olefin compound D-1 obtained in Example 1 were added. In addition, the mixture was further stirred to obtain a liquid in an emulsion state. The temperature of this solution was raised to 50 ° C., and while stirring vigorously, 55 parts of 35% aqueous hydrogen peroxide was added and stirred as it was at 50 ° C. for 13 hours. When the progress of the reaction was confirmed by GC, the substrate conversion after the completion of the reaction was> 99%, and the raw material peak disappeared (<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, stirred for 30 minutes, and allowed to stand. The organic layer separated into two layers was taken out, and 10 parts of silica gel (Wako Pure Chemical Industries Wakogel C-300), 20 parts of activated carbon (CAPRPER made by NORIT) and 20 parts of bentonite (Bengel SH, made by Hojun) were added at room temperature. And stirred for 1 hour and then filtered. The obtained filtrate was washed with 100 parts of water three times, and the organic solvent was distilled off from the obtained organic layer to obtain the following formula (5).

As a main component, 89 parts of an epoxy resin (EP-1) was obtained.
From the measurement results of GPC, it was confirmed that 98% of the skeleton compound of the formula (5) was contained. Furthermore, in the GC measurement, the purity was 91%. The epoxy equivalent was 215 g / eq. Met.

Example 3
By column chromatography using 105 parts of silica gel (Wakogel C-300, manufactured by Wako Pure Chemical Industries, Ltd.) with 15 parts of the obtained epoxy resin (EP-1), using a developing solvent of ethyl acetate: hexane = 1: 4. Purification was performed.
The obtained epoxy resin (EP-2) is 10 parts, and the purity of the obtained epoxy resin is confirmed to contain 98% or more of the skeleton compound of the formula (5) from the GPC measurement result. did. Furthermore, in the GC measurement, the purity was about 99%. The epoxy equivalent was 207 g / eq. Met.

Example 4
To a flask equipped with a stirrer, a reflux condenser, a stirrer, and a Dean Stark tube, while purging with nitrogen, 150 parts of toluene, 2,4-diethyl-1,5-pentanediol (Kyowa Hakko Chemical Co., Ltd. Kyowa All PD9) ) 80 parts, 126 parts of 3-cyclohexenecarboxylic acid and 2 parts of paratoluenesulfonic acid were added, and the reaction was carried out under heating and refluxing for 10 hours while removing water. After completion of the reaction, the olefinic compound of the present invention is washed twice with 50 parts of a 10% by weight aqueous sodium hydrogen carbonate solution and the organic layer obtained is washed twice with 50 parts of water and then concentrated with a rotary evaporator. 187 parts of (D-2) was obtained. The shape was liquid and the purity 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
A flask equipped with a stirrer, reflux condenser, and stirrer is purged with nitrogen, 15 parts of water, 0.95 parts of 12-tungstophosphoric acid, 0.78 parts of disodium hydrogen phosphate, di-cured tallow alkyldimethylammonium acetate After adding 2.7 parts (50% hexane solution made by Lion Akzo, Acquard 2HT acetate) to produce a tungstic acid catalyst, 120 parts of toluene and 94 parts of the olefin compound D-2 obtained in Example 4 were added. In addition, the mixture was further stirred to obtain a liquid in an emulsion state. The temperature of this solution was raised to 50 ° C., and while stirring vigorously, 55 parts of 35% aqueous hydrogen peroxide was added and stirred as it was at 50 ° C. for 13 hours. When the progress of the reaction was confirmed by GC, the substrate conversion after the completion of the reaction was> 99%, and the raw material peak disappeared (<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, stirred for 30 minutes, and allowed to stand. The organic layer separated into two layers was taken out, and 10 parts of silica gel (Wako Pure Chemical Industries Wakogel C-300), 20 parts of activated carbon (CAPRPER made by NORIT) and 20 parts of bentonite (Bengel SH, made by Hojun) were added at room temperature. And stirred for 1 hour and then filtered. The obtained filtrate was washed with 100 parts of water three times, and the organic solvent was distilled off from the obtained organic layer to obtain the following formula (6).

90 parts of an epoxy resin (EP-3) containing as a main component was obtained.
From the measurement results of GPC, it was confirmed that 98% of the compound having the skeleton of formula (6) was contained. Furthermore, in the GC measurement, the purity was 91%. The epoxy equivalent was 216 g / eq. Met.

Example 6
By column chromatography using 105 parts of silica gel (Wakogel C-300, manufactured by Wako Pure Chemical Industries, Ltd.) and developing solvent of ethyl acetate: hexane = 1: 4 with respect to 15 parts of the obtained epoxy resin (EP-3). Purification was performed.
The obtained epoxy resin (EP-4) was 11 parts, and the purity of the obtained epoxy resin was confirmed to contain 98% or more of the skeleton compound of the formula (6) from the GPC measurement result. did. Furthermore, in the GC measurement, the purity was about 99%. The epoxy equivalent was 209 g / eq. Met.

Synthesis example 1
In Example 1, 80 parts of 2-butyl-2-ethyl-1,3-propanediol (produced by Kyowa Hakko Chemical Co., Ltd.) was changed to 52 parts of neopentyl glycol (produced by Mitsubishi Gas Chemical Co., Inc.). Except for the above, the same operation was carried out to obtain 153 parts of an 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 Example 2, it carried out similarly except having changed 94 parts of olefin compounds (D-1) into 80 parts of olefin compounds (D-3). As a result, the following formula (7)

As a main component, 56 parts of an epoxy resin (EP-5) was obtained.
From the measurement results of GPC, it was confirmed that 98% of the compound having the skeleton of formula (7) was contained. Furthermore, in the GC measurement, the purity was 95%. The epoxy equivalent was 182 g / eq. Met.

Synthesis example 3
By column chromatography using 105 parts of silica gel (Wakogel C-300 manufactured by Wako Pure Chemical Industries, Ltd.) with 15 parts of the resulting epoxy resin (EP-5) and using a developing solvent of ethyl acetate: hexane = 1: 4. Purification was performed.
The obtained epoxy resin (EP-6) was 13 parts, and the purity of the obtained epoxy resin was confirmed by GPC measurement results to contain 98% or more of the skeleton compound of the formula (7). did. Furthermore, in the GC measurement, the purity was about 99%. The epoxy equivalent was 180 g / eq. Met.

Synthesis example 4
In Example 1, 80 parts of 2-butyl-2-ethyl-1,3-propanediol (produced by Kyowa Hakko Chemical Co., Ltd.) and 1,6-hexanediol (produced by Tokyo Chemical Industry Co., Ltd.) The same operation was performed except that the amount was changed to 59 parts. As a result, 157 parts of an olefin compound (D-4) was obtained. The shape was liquid and the purity 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 Example 2, it carried out similarly except having changed 94 parts of olefin compounds (D-1) into 83 parts of olefin compounds (D-4). As a result, the following formula (8)

77 parts of an epoxy (EP-7) containing as a main component was obtained.
From the measurement results of GPC, it was confirmed that 98% of the compound having the skeleton of formula (8) was contained. Furthermore, in the GC measurement, the purity was 90%. The epoxy equivalent was 199 g / eq. Met.

Synthesis Example 6
By column chromatography using 105 parts of silica gel (Wakogel C-300, manufactured by Wako Pure Chemical Industries, Ltd.) with 15 parts of the resulting epoxy resin (EP-7), using a developing solvent of ethyl acetate: hexane = 1: 4. Purification was performed.
The obtained epoxy resin (EP-8) was 9 parts, and the purity of the obtained epoxy resin was confirmed to contain 98% or more of the skeleton compound of the formula (8) from the GPC measurement results. did. Furthermore, in the GC measurement, the purity was about 99%. The epoxy equivalent was 185 g / eq. Met.

Examples 7, 8, 9 and Comparative Examples 1 and 2
The epoxy resin (EP-2, EP-3, EP-4) of the present invention obtained in Examples 3, 5, and 6 and, as a comparative example, the epoxy resin (EP-6) produced in Synthesis Example 3 and Synthesis Example 6 EP-8), as a curing agent, a mixture of methylhexahydrophthalic anhydride and hexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid MH700G, hereinafter referred to as H1), bicyclo [2,2 , 1] Heptane-2,3-dicarboxylic acid anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid HNA-100, hereinafter referred to as H2), hexadecyltrimethylammonium hydroxide (Tokyo Chemical Industry Co., Ltd.) as a curing accelerator 25% methanol solution, hereinafter referred to as C1), and blended at the blending ratio (parts by weight) shown in Table 1 below, defoamed for 20 minutes to obtain the curable resin composition of the present invention. .

  Using the obtained curable resin composition, a heat resistance property test, a heat durability transmittance test, and an LED test were performed in the manner described below. The results are shown in Table 1. The curing conditions in the heat resistance characteristic test and the LED test are 140 ° C. × 2 hours after 120 ° C. × 2 hours of preliminary curing.

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

(Thermal durability transmission test)
The obtained curable resin composition was vacuum-defoamed for 20 minutes, and then gently cast on a glass substrate on which a dam was created with a heat-resistant tape so as to be 30 mm × 20 mm × height 1 mm. The cast was cured at 120 ° C. for 1 hour after pre-curing at 120 ° C. for 3 hours to obtain a test piece for transmittance having a thickness of 1 mm.
Using these test pieces, the transmittance (measurement wavelength: 375 nm or 400 nm) before and after being left for 96 hours in a 150 ° C. oven was measured with a spectrophotometer, and the rate of change was calculated.

(LED lighting test)
The curable resin compositions obtained in Examples and Comparative Examples were vacuum degassed for 20 minutes, filled in a syringe, and used a precision discharge device to mount a light emitting element having an emission wavelength of 465 nm, an outer diameter of 5 mm square surface It was cast into a mounting type LED package (inner diameter 4.4 mm, outer wall height 1.25 mm). Then, the LED for lighting test is obtained by making it harden | cure on the above-mentioned hardening conditions. In the lighting test, a lighting test was performed at a specified current of 30 mA. Detailed conditions are shown below. As a measurement item, the illuminance before and after lighting for 200 hours was measured using an integrating sphere, and the illuminance retention rate of the test LED was calculated.
Detailed lighting conditions Light emission wavelength: 465nm
Drive system: constant current system, 30 mA (light emitting element specified current is 30 mA)
Driving environment: 85 ° C, 85%
Evaluation: When the decrease in illuminance is less than 5%, ◯ when 5% or more and less than 10%, Δ when 10% or more.

  When Examples 7 to 9 and Comparative Examples 1 and 2 are compared, the curable resin composition of the present invention is more resistant to heat and heat than the curable resin composition using an epoxy resin having a similar chain linker. It can be seen that not only the heat deterioration characteristics such as colorability are excellent, but also the light resistance is excellent. It can be seen that the same tendency is observed even when the compounds having similar Tg are compared. From the above results, it can be seen that the epoxy resin of the present invention can provide a curable resin composition having excellent heat degradation characteristics and optical characteristics.

Synthesis example 7
To a flask equipped with a stirrer, reflux condenser, and stirrer, while purging with nitrogen, 12 parts of dicyclopentadiene dimethanol, methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid MH or less, acid anhydride) 73 parts of 1,2,4-cyclohexanetricarboxylic acid-1,2-anhydride (hereinafter referred to as H-TMAn, hereinafter referred to as H4) manufactured by Mitsubishi Gas Chemical Co., Ltd., and then at 40 ° C. for 2 hours, Curing agent composition which is a mixture of polycarboxylic acid and acid anhydride by heating and stirring at 60 ° C. for 1 hour (GPC confirmed that dicyclopentadiene dimethanol was 0.5% or less). 100 parts of (HA-1) was obtained. The functional group equivalent of the obtained compound was 171 g / eq. (Carboxylic acid and acid anhydride are considered as one functional group each).

Synthesis example 8
To a flask equipped with a stirrer, a reflux condenser and a stirrer, 10 parts of 2,4-diethylpentanediol (Kyowa Hakko Chemical Kyowadiol PD-9) and 50 parts of acid anhydride (H3) were added while purging with nitrogen. In addition, by heating and stirring at 40 ° C. for 2 hours and then at 60 ° C. for 1 hour (GPC confirmed that 2,4-diethylpentanediol was 0.5% or less), polycarboxylic acid and acid 60 parts of a curing agent composition (HA-2) which was a mixture with an anhydride was obtained. The functional group equivalent of the obtained compound was 201 g / eq. Met.

Example 10
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 75.2 parts of the olefin compound D-2 obtained in Example 4 while purging nitrogen, 75 parts of toluene, 10 parts of water, and 12-tungstorin. 0.4 part of acid, 0.60 part of sodium tungstate, 0.60 part of disodium hydrogenphosphate, 0.54 part of trioctylmethylammonium acetate (50% xylene solution from Lion Akzo, TOMAA-50), and this solution The temperature was raised to 48 ° C., and 44 parts of 35% hydrogen peroxide was added while stirring, and the mixture was stirred at 48 ° C. for 16 hours. When the progress of the reaction was confirmed by GC, the substrate conversion after completion of the reaction was> 99%, and the raw material peak was <1%.
Next, the pH was adjusted to 9 with a 30 wt% aqueous sodium hydroxide solution, 20 parts of a 20 wt% aqueous sodium thiosulfate solution was added, and the mixture was stirred for 30 minutes and allowed to stand. The organic layer separated into two layers was taken out, 8 parts of montmorillonite (Kunimine Industries Kunipia F) and 9 parts of activated carbon (CP-1 manufactured by Ajinomoto Fine-Techno) were added, and the mixture was stirred at room temperature for 3 hours and filtered. The obtained filtrate was washed with 100 parts of water three times, and the organic solvent was distilled off from the obtained organic layer, whereby the epoxy resin (EP) of the present invention having the structure of the formula (6) as a main component (EP) 76.4 parts of -9) were obtained. Epoxy equivalent is 210 g / eq. Met.

Synthesis Example 9
In Example 10, 75.2 parts of the olefin compound (D-2) was synthesized by dehydration esterification of 1,4-cyclohexanedimethanol and 3-cyclohexenecarboxylic acid.

The synthesis was carried out in the same manner except that the olefin compound was changed to 72 parts of the structure shown in FIG. 7 to obtain 73 parts of a comparative epoxy resin (EP-10). Epoxy equivalent is 207 g / eq. Met.

Synthesis Example 10
In Example 10, the synthesis was performed in the same manner except that 75.2 parts of the olefin compound (D-2) was changed to 66.9 parts of the olefin compound (D-4), and the skeleton of the formula (8) was the main component. As a result, 67.0 parts of a comparative epoxy resin (EP-11) was obtained. Epoxy equivalent was 196 g / eq. Met.

Synthesis Example 11
In Example 10, 75.2 parts of the olefin compound (D-2) was synthesized by dehydration esterification of adipic acid and 4-cyclohexenemethanol.

Synthesis was carried out in the same manner except that 66.9 parts of the olefin compound having the structure shown in FIG. Epoxy equivalent was 194 g / eq. Met.

Example 11, Comparative Examples 3, 4, 5
About the epoxy resin (EP-9) of the present invention obtained in Example 10 and, as comparative examples, the epoxy resins (EP-10, EP-11, EP-12) obtained in Synthesis Examples 9, 10, and 11 were cured. An acid anhydride (H1) as an agent, a quaternary phosphonium salt (PX-4MP manufactured by Nippon Kagaku Kogyo Co., Ltd., hereinafter referred to as C2) as a curing accelerator, and blended at a blending ratio (parts by weight) shown in Table 2 below, Defoaming was performed for 20 minutes to obtain a curable resin composition of the present invention.

  Using the obtained curable resin composition, an LED test was performed in the following manner. The results are shown in Table 2. The curing conditions are 140 ° C. × 3 hours after 110 ° C. × 2 hours of preliminary curing.

(LED lighting test A)
The resulting curable resin composition was vacuum degassed for 20 minutes, then filled into a syringe, and using a precision discharge device, an outer diameter 5 mm square surface mount LED package (inner diameter 4) mounted with a chip having a central emission wave of 465 nm. 4 mm, outer wall height 1.25 mm). Thereafter, a test LED was obtained by curing under predetermined curing conditions.
In the lighting test, a lighting test was performed at a specified current of 30 mA. Detailed conditions are shown below. As measurement items, the illuminance before and after lighting for 400 hours, 600 hours, and 800 hours was measured using an integrating sphere, and the illuminance retention rate of the test LED was calculated.
Detailed lighting conditions Light emission wavelength: 465nm
Drive system: constant current system, 30 mA (light emitting element specified current is 30 mA)
Driving environment: 85 ° C, 85%
(LED lighting test B)
Moreover, in the same environment as the above-mentioned LED lighting test (that is, conditions of 85 ° C. and 85%), the test LED is stored without lighting and before and after holding for 400 hours, 600 hours, and 800 hours. The illuminance was measured using an integrating sphere, and the illuminance retention rate of the test LED was calculated.

  The epoxy resin (EP-9) of the present invention obtained in Example 10 and the curing agent compositions (HA-1) (HA-2) and additives obtained in Synthesis Examples 7 and 8 as curing agent compositions, respectively. As a phosphate ester zinc complex (XC-9206 manufactured by King Industries, hereinafter referred to as AD-1) and a hindered amine compound (LA-77 manufactured by ADEKA, hereinafter referred to as AD-2), the blending ratio (weight) shown in Table 3 below is used. Part) to obtain a curable composition of the present invention.

(Thermal durability transmission test)
The obtained curable resin composition was vacuum-defoamed for 20 minutes, and then gently cast on a glass substrate on which a dam was created with a heat-resistant tape so as to be 30 mm × 20 mm × height 1 mm. The cast was cured at 110 ° C. for 3 hours and then cured at 150 ° C. for 3 hours to obtain a transmittance test piece having a thickness of 1 mm. Using the obtained test piece, the transmittance (measurement wavelength: 400 nm) before and after being left in a 150 ° C. oven for 96 hours was measured with a spectrophotometer, and the rate of change was calculated.

Example 14, Comparative Example 6
Epoxy resin (EP-9) of the present invention obtained in Example 10 and 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate (Nippon Kayaku SEJ-01R epoxy equivalent) as a comparative example 130 g / eq., Hereinafter referred to as an epoxy resin (EP-13)), an acid anhydride (H3) is used as a curing agent, and an imidazole compound (2E4MZ manufactured by Shikoku Chemicals, hereinafter referred to as C3) is used as a curing accelerator. The curable resin composition of the present invention was obtained by blending at a blending ratio (parts by weight) shown in Table 4 below.
The obtained curable resin composition was cast into a mold (a disk having a diameter of 50 mm and a thickness of 3 mm), and the cast was cured at 160 ° C. for 5 hours after pre-curing at 120 ° C. for 2 hours. Test specimens were obtained. Using the obtained test piece, a moisture absorption / water absorption test was performed under the following conditions, and the weight increase rate was confirmed. The results are shown in Table 4 below.
(Moisture resistance test 1)
In a thermostatic chamber, at a temperature of 85 ° C and a humidity of 85% for 24 hours (Moisture resistance test 2)
24 hours in a pressure vessel at a temperature of 121 ° C and humidity of 100% (Water resistance test 1)
Boiled 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 and water resistance but also high optical characteristics. In particular, in the results of Example 11 and Comparative Examples 3 to 5, the curable resin composition using the epoxy resin of the present invention not only has good moisture resistance as compared with the one using a simple chain structure ( In the LED lighting test B), the illuminance retention rate of the LED has not only a chain structure but also a high illuminance retention rate as compared with a compound having a cyclic structure, and it can be seen that the LED has high characteristics.

Although the invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
In addition, this application is based on the Japanese patent application (Japanese Patent Application No. 2009-091585) for which it applied on April 3, 2009, The whole is used by reference. Also, all references cited herein are incorporated as a whole.

Claims (9)

Following formula (1)

(In the formula, a plurality of R's are present independently and each represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and P is a chain alkyl having a branched structure having 6 to 20 carbon atoms in total. An olefin compound represented by a chain linker).   The olefin compound according to claim 1, wherein the linker P has a structure having a main chain of 3 or more carbon atoms and having an alkyl branched chain in at least one position.   The olefin compound according to claim 1 or 2, wherein the linker P has two or more alkyl groups present branched from the main chain. The olefin compound according to any one of claims 1 to 3, which is represented by the following formula (D-1) or (D-2).

  The epoxy resin obtained by oxidizing the olefin compound as described in any one of Claims 1-4.   6. The epoxy resin according to claim 5, which is epoxidized using hydrogen peroxide or peracid.   A curable resin composition comprising the epoxy resin according to claim 5 and a curing agent and / or a curing catalyst.   A cured product obtained by curing the curable resin composition according to claim 7.   An LED device encapsulated with the curable resin composition according to claim 7 and / or die-bonded.