WO2011145733A1 - Diolefin compound, epoxy resin, curable resin composition, and cured article - Google Patents

Abstract

Disclosed is a novel alicyclic epoxy resin which provides a cured article having excellent heat resistance, optical properties, and toughness. The epoxy resin comprises a diolefin compound represented by formula (1) as a starting material and is obtained by the epoxidation of the compound. In formula (1), a plurality of R₁'s and R₂'s each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Description

Diolefin compound, epoxy resin, curable resin composition and cured product thereof

The present invention relates to a novel diolefin compound and an epoxy resin suitable for electrical and electronic material applications.

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 with excellent transparency is desired. In response to these requirements, alicyclic epoxy resins have attracted attention.

Alicyclic epoxy compounds are superior in terms of electrical insulation and transparency as compared with glycidyl ether type epoxy compounds, and are used in various kinds of transparent sealing materials. However, alicyclic epoxy compounds with improved heat resistance and light resistance have been demanded particularly in fields where advanced heat / light properties such as LED applications are required (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 the present invention is to provide a novel alicyclic epoxy resin that gives a cured product having excellent heat resistance, optical properties, and toughness.

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

(In the formula, a plurality of R ₁ and R ₂ each independently exist, and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
A diolefin compound represented by:
(2)
An epoxy resin obtained by oxidizing the diolefin compound according to item (1),
(3)
The epoxy resin according to item (2), which is epoxidized using hydrogen peroxide or peracid,
(4)
A curable resin composition comprising the epoxy resin according to any one of (2) and (3) above, a curing agent and / or a curing accelerator,
(5)
Hardened | cured material formed by hardening | curing curable resin composition of previous clause (4),
About.

The epoxy resin of the present invention gives a cured product having excellent mechanical properties (particularly toughness). The curable fat composition containing the epoxy resin of the present invention is useful for a wide range of applications such as electric / electronic materials, molding materials, casting materials, laminated materials, paints, adhesives, resists and the like. Moreover, since the epoxy resin of this invention does not have an aromatic ring, the curable resin composition containing it is very useful for an optical material.

The present invention is the following formula (1)

(In the formula, a plurality of R ₁ and R ₂ each independently exist, and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
And an epoxy resin obtained by epoxidizing the compound by oxidation.

The diolefin compound represented by the formula (1) is obtained by a reaction between a cyclohexene methanol derivative and a decahydronaphthalenedicarboxylic acid derivative. The cyclohexene methanol derivative is not particularly limited as long as it is a cyclohexene having a hydroxymethyl group, and preferably 3-cyclohexene methanol, 3-methyl-3-cyclohexene methanol, 4-methyl-3-cyclohexene methanol, 2-methyl-3- Examples thereof include cyclohexene methanol, and 3-cyclohexene methanol is particularly preferable, but is not limited thereto. These may be used alone or in combination of two or more.

Examples of decahydronaphthalenedicarboxylic acid derivatives include hydrogenation of naphthalenedicarboxylic acid or its ester by nuclear hydrogenation, and hydroformylation of tetrahydronaphthalene excluding the resulting compound and tetralin, followed by oxidation with carboxylic acid. Or by further esterification with alcohol. In order to further increase the reactivity, decahydronaphthalenedicarboxylic acid excluding tetralin dicarboxylic acid may be acid halided.
Specifically, decahydronaphthalenedicarboxylic acid, dimethyl decahydronaphthalenedicarboxylate, diethyl decahydronaphthalenedicarboxylate, dipropyl decahydronaphthalenedicarboxylate, dibutyl decahydronaphthalenedicarboxylate, dicyclohexyl decahydronaphthalenedicarboxylate, methyl decahydronaphthalenedicarboxyl Dimethyl acid, cyclohexyldecahydronaphthalenedicarboxylate, and the like.

A general esterification method can be applied as a reaction between the cyclohexene methanol derivative and the decahydronaphthalenedicarboxylic acid derivative. Specific examples include Fischer® esterification using an acid catalyst, acid halide under basic conditions, alcohol reaction, condensation reaction using various condensing agents (ADVANCED®ORGANIC®CHEMISTRY Part B: Reaction and Syntehsis®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 of carboxylic acid esters (Japan) (Japanese Patent Laid-Open No. 2006-052187) may be used.

As a preferable structure of the diolefin compound of the formula (1) synthesized as described above, it is preferable that R ₁ in the formula (1) is any one of a hydrogen atom, a methyl group, an ethyl group, and a butyl group. In particular, when the substituent R ₁ is bonded to an olefin, in order to improve the reactivity, R ₁ bonded to the olefin is preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom.
The substituent R ₂ directly connected to the decahydronaphthalene structure is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group or the like. Moreover, the thing which becomes a hydrogen atom from the ease of acquisition of the raw material from a market is preferable.
Further, the diolefin compound of the formula (1) is preferably 2,6-substituted, 1,4-substituted, 2,3-substituted, 1,8-substituted, and particularly preferably 2,6-substituted.

The diolefin resin 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. Examples of peracids that can be used include organic acids such as formic acid, acetic acid, propionic acid, maleic acid, benzoic acid, m-chlorobenzoic acid, and phthalic acid, and acid anhydrides thereof. Among these, it is preferable to use formic acid, acetic acid, and phthalic anhydride from the viewpoint of the efficiency of reacting with hydrogen peroxide to produce an organic peracid, the reaction temperature, the ease of operation, and the economy. Formic acid or acetic acid is more preferably used from the viewpoint of simplicity of reaction operation.
Various methods can be applied to the epoxidation method using 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 diolefin compound, polyacid and quaternary ammonium salt of the present invention are reacted in two layers of an organic solvent and hydrogen peroxide solution.

The polyacid used in the present invention is not particularly limited as long as it is a compound having a polyacid structure, but polyacids containing tungsten or molybdenum are preferred, polyacids containing tungsten are more preferred, and tungstates are particularly preferred.
Specific polyacids and polyacid salts included in the polyacids include tungsten acids selected from tungstic acid, 12-tungstophosphoric acid, 12-tungstoboric acid, 18-tungstophosphoric acid, 12-tungstosilicic acid, and the like. Examples thereof include molybdenum-based acids selected from molybdic acid and phosphomolybdic acid, and salts thereof.
Examples of the counter cation of these salts include ammonium ions, alkaline earth metal ions, and alkali metal ions.
Specific examples include alkaline earth metal ions such as calcium ions and magnesium ions, alkali metal ions such as sodium, potassium and cesium, but are not limited thereto. Particularly preferred counter cations are sodium ion, potassium ion, calcium ion and ammonium ion.

The amount of the polyacid used is 1.0 to 20 mmol in terms of metal element (tungstenic acid is tungsten atom, molybdic acid is molybdenum atom) to 1 mol of olefin (functional group equivalent) in the diolefin compound of the present invention. , Preferably 2.0 to 20 mmol, more preferably 2.5 to 10 mmol.

As the quaternary ammonium salt, a quaternary ammonium salt having a total carbon number of 10 or more, preferably 25 to 100, more preferably 25 to 55 can be preferably used, and in particular, the alkyl chain is preferably an aliphatic chain. .
Specifically, tridecanylmethylammonium salt, dilauryldimethylammonium salt, trioctylmethylammonium salt, trialkylmethyl (a mixed type of a compound in which the alkyl group is an octyl group and a compound in which the decanyl group is a compound) ammonium salt, trihexa Examples include decylmethylammonium salt, trimethylstearylammonium salt, tetrapentylammonium salt, cetyltrimethylammonium salt, benzyltributylammonium salt, dicetyldimethylammonium salt, tricetylmethylammonium salt, and di-cured tallow alkyldimethylammonium salt. It is not limited to.
The anion species of these salts use carboxylate ions. As the carboxylate ion, acetate ion, carbonate ion and formate ion are preferable. In particular, acetate ion is preferred.
If the quaternary ammonium salt has more than 100 carbon atoms, the hydrophobicity may become too strong and the solubility in the organic layer may deteriorate. On the other hand, when the carbon number of the quaternary ammonium salt is less than 10, the hydrophilicity becomes strong, and the compatibility with the organic layer may be similarly deteriorated.
In general, halogen remains in the quaternary ammonium salt. In the present invention, in particular, it is 1% by weight or less, more preferably 1000 ppm or less, and still more preferably 700 ppm or less. When the total halogen content exceeds 1% by weight, a large amount of halogen remains in the product, which is not preferable.
The amount of tungstic acid and quaternary ammonium carboxylate used is preferably 0.01 to 0.8 times equivalent, or 1.1 to 10 times equivalent to the valence of the tungstic acid used. More preferably 0.05 to 0.7 times equivalent, or 1.2 to 6.0 times equivalent, still more preferably 0.05 to 0.5 times equivalent, or 1.3 to 4.5 times equivalent. is there.
For example, since tungstic acid is divalent with H ₂ WO ₄ , the quaternary ammonium carboxylate is 0.02 to 1.6 mol, or 2.2 to 20 mol per mol of tungstic acid. A range is preferred. In addition, since tungstophosphoric acid is trivalent, it is similarly 0.03 to 2.4 mol, or 3.3 to 30 mol, and in the case of silicotungstic acid, it is tetravalent, so 0.04 to 3.2. Mole or 4.4 to 40 mol is preferred.
When the amount of the quaternary ammonium carboxylate is lower than 1.1 times equivalent of the valence of tungstic acids, the epoxidation reaction is difficult to proceed (in some cases, the reaction proceeds faster), and a by-product is produced. The problem is that things are easy to make. When the amount is more than 10 times the equivalent, not only is the treatment of the excess quaternary ammonium carboxylate difficult, but it also serves to suppress the reaction, which is not preferable.

As the quaternary ammonium salt having a carboxylate ion as an anion, a commercially available product may be used. For example, the raw material quaternary ammonium salt is treated with a metal hydroxide or an ion exchange resin to be converted into a quaternary ammonium hydroxide. Further, it may be produced by a method of reacting with various carboxylic acids. Examples of the raw material quaternary ammonium salt include quaternary ammonium halides and various metal salts. If there is a suitable quaternary ammonium hydroxide, it may be 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 solution, a buffer solution is used in an amount of 0.1 to 10 mol% of phosphoric acid (or phosphorous such as sodium dihydrogen phosphate) with respect to hydrogen peroxide. Acid salt) and adjusting the pH with a basic compound (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, etc.). Here, it is preferable that the pH is added so that the above-mentioned pH is obtained when hydrogen peroxide is added. Moreover, 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 5 to 45% by weight.
In this reaction, a buffer such as disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate or sodium tripolyphosphate (or its hydrate) is used without adjusting the pH. It may be added directly. In the sense of simplifying the process, there is no troublesome pH adjustment, and direct addition is particularly preferred. In this case, the amount of phosphate used 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. It is. At this time, 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 bad 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, preferably 0.3 to 5, more preferably 0.5 to 2.5 by weight with respect to the diolefin compound 1 as a reaction substrate. is there. When the weight ratio exceeds 10, the progress of the reaction is extremely slow, which is not preferable. Specific examples of organic solvents that can be used include alkanes such as hexane, cyclohexane, and heptane, aromatic hydrocarbon compounds such as toluene and xylene, and alcohols such as methanol, ethanol, isopropanol, butanol, hexanol, and cyclohexanol. It is done. In some cases, ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and anone, ethers such as diethyl ether, tetrahydrofuran and dioxane, ester compounds such as ethyl acetate, butyl acetate and methyl formate, and nitriles such as acetonitrile Compounds and the like can also be used.

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

The reaction temperature is not particularly limited, but is preferably 0 to 90 ° C, more preferably 0 to 75 ° C, particularly preferably 15 ° C to 60 ° C. When the reaction temperature is too high, the hydrolysis reaction 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 reaction time is not preferable because it consumes a great deal of energy. A preferred range is 1 to 48 hours, preferably 3 to 36 hours, and more preferably 4 to 24 hours.

After the reaction is complete, quench the excess hydrogen peroxide. The quenching treatment is preferably performed using a basic compound. It is also preferable to use a reducing agent and a basic compound in combination. As a preferred treatment method, there is a method of quenching the remaining hydrogen peroxide using a reducing agent after neutralization adjustment to pH 6 to 10 with a basic compound. When the pH is less than 6, the heat generated when reducing 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. The reducing agent is used in an excess amount of hydrogen peroxide of usually 0.01 to 20 times mol, more preferably 0.05 to 10 times mol, and still more preferably 0.05 to 3 times mol with respect to the number of moles. is there.

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

After the hydrogen peroxide quench (or before quenching), if the organic layer and the aqueous layer are not separated, or if no organic solvent is used, the above-mentioned organic solvent is added and the operation is performed. The reaction product is extracted from the layer. The organic solvent used at this time is 0.5 to 10 times, preferably 0.5 to 5 times in weight ratio to the raw material diolefin compound. This operation is repeated several times as necessary, and 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 or a metal oxide (especially silica gel or alumina is preferred), activated carbon (especially a chemical activated carbon is particularly preferred), or a composite metal salt (especially a basic composite metal salt). Are preferably removed), a mineral with a viscosity (especially, a layered viscosity mineral such as montmorillonite is preferred), and after washing with water and filtration, the solvent is distilled off to obtain the desired epoxy compound. In some cases, it may be further purified by column chromatography or distillation.

The epoxy resin of the present invention thus obtained has the formula (2)

(In the formula, a plurality of R ₁ and R ₂ each independently exist, and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
The main structure is the structure represented by the formula, but a hydrolyzate, an unreacted product, a polymerized polymer obtained by polymerizing epoxy groups, and other by-products are produced depending on the reaction conditions.

The obtained epoxy resin of the present invention can be used as a raw material for various resins 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 types of heat curing with a curing agent (curable resin composition A) and cationic curing (curable resin composition B) using an acid as a curing accelerator (curing catalyst). The method can be adapted.

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 mass or more, particularly preferably 40% by mass or more. However, when the epoxy resin of the present invention is used as a modifier of the curable resin composition, it may be added in a proportion of 1 to 30% by mass.

Other epoxy resins that can be used in combination with the epoxy resin of the present invention include novolak type epoxy resins, bisphenol 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-hydroxyacetofu Non, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Glycidyl ethers derived from polycondensates with 4-bis (chloromethyl) benzene or 1,4-bis (methoxymethyl) benzene and their modified products, halogenated bisphenols such as tetrabromobisphenol A, and alcohols , Cycloaliphatic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, silsesquioxane epoxy resin (chain structure, cyclic structure, ladder structure, or a mixed structure of at least two of these) Has glycidyl group and / or epoxycyclohexane structure Epoxy resin) solid or liquid epoxy resins and the like that, but not limited thereto.

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 performing a reaction while azeotropically dehydrating using a solvent such as toluene or xylene as a reaction medium (US Pat. No. 2,945,008), A method in which polyhydric alcohol is dissolved in hydrochloric acid and then the reaction is carried out while gradually adding aldehydes (Japanese Patent Laid-Open No. 48-96590), a method using water as a reaction medium (US Pat. No. 3,092,640) Further, a method using an organic solvent as a reaction 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, Epolide GT401, EHPE3150, EHPE3150CE (all trade names, all Daicel) (Chemical Industry) and dicyclopentadiene diepoxide, and the like, but are not limited thereto (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.
Curable resin composition A (thermal curing with curing agent)
Examples of the curing agent contained in the curable resin composition A of the present invention include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and nitrogen-containing compounds such as polyamide resins synthesized from ethylenediamine and amine compounds (amines, Amide compound); phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methyl hexahydro Phthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, Cyclohe Acid anhydrides such as sun-1,2,4-tricarboxylic acid-1,2-anhydride, etc .; carboxylic acid resins obtained by addition reaction of various alcohols, carbinol-modified silicones and the aforementioned acid anhydrides; bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol) , Naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphth ) And formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1 Polycondensation with '-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4'-bis (chloromethyl) benzene or 1,4'-bis (methoxymethyl) benzene And modified products thereof, polyphenols such as halogenated bisphenols such as tetrabromobisphenol A, condensates of terpenes and phenols; imidazole, trifluoroborane-amine complexes, guanidine derivative compounds, etc. Also limited to Not. These may be used alone or in combination of two or more.
In the present invention, compounds having an acid anhydride structure and / or a carboxylic acid structure represented by the above-mentioned acid anhydride compounds and carboxylic acid compounds are particularly preferable.

The amount of the curing agent used in the curable resin composition A of the present invention is preferably 0.6 to 1.2 equivalents, and preferably 0.7 to 1.2 equivalents with respect to 1 equivalent of the epoxy group of the epoxy resin. When less than 0.6 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 (curing catalyst) may be used in combination with the curing agent. Specific examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol and 1,8-diaza-bicyclo ( 5,4,0) tertiary amines such as undecene-7, phosphines such as triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, hexadecyltrimethyl Quaternary ammonium salts such as ammonium hydroxide, quaternary phosphonium salts such as triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, tetrabutylphosphonium salt (the counter ion of the quaternary salt is halogen) Organic acid ions, hydroxide ions, such as, in particular specification is not, in particular organic acid ion, a hydroxide ion.) Include metal compounds such as tin octylate. The curing accelerator is used in an amount of 0.01 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin, if necessary.

The curable resin composition A of the present invention can also contain a phosphorus-containing compound as a flame retardant 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 ( Phosphate esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate) and 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide and 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; active hydrogen of epoxy resin and phosphanes Contains phosphorus obtained by reacting with Epoxy resins, red phosphorus, and the like can be mentioned. Phosphate esters, phosphanes, or phosphorus-containing epoxy resins are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy resins are particularly preferred. As for content of a phosphorus containing compound, 0.6 times or less is preferable with respect to the total amount of the epoxy resin component in the curable resin composition A of this invention. If it exceeds 0.6 times, there is a concern that it may adversely affect the hygroscopicity and dielectric properties of the cured product.

Furthermore, you may add antioxidant to the curable resin composition A of this invention as needed. Antioxidants that can be used include phenol-based, sulfur-based, and phosphorus-based antioxidants. Antioxidants can be used alone or in combination of two or more. The amount of the antioxidant used is usually 0.008 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the resin component A in the curable resin composition of the present invention. .

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-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-thiobis (3- Til-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) ) Propionate], 1,6-hexanediol-bis [3- (3,5-di-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- Bisphenols such as (tilphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, bis (3,5-di-t-butyl-4-hydroxybenzylsulfonate ethyl) 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'-tert-butylphenyl) butyric acid] glycol ester, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -iso Anureate, 1,3,5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol And the like.

Specific examples of the sulfur antioxidant include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyll-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 neopentanetetraylbis (octadecyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2,4 -Phosphites such as -di-t-butyl-4-methylphenyl) phosphite, bis [2-tert-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite ; 9,10-dihydride -9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene- Examples thereof include oxaphosphaphenanthrene oxides such as 10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the like.

These antioxidants can be used alone, but two or more kinds 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 typical 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, a binder resin can be added to the curable resin composition A of the present invention as necessary. 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 within a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 100 parts by weight with respect to 100 parts by weight of the resin component in the curable resin composition A of the present invention. 50 parts by weight, preferably 0.05 to 20 parts by weight are used as required.

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. As the content of these inorganic fillers, an amount occupying 95% by mass or less in A in the curable resin composition of the present invention is used. 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 O ₁₂ : Ce, Y ₄ Al ₂ O ₉ : Ce, Y ₂ O ₂ S: Eu, Sr ₅ (PO ₄ ) ₃ Cl: Eu, (SrEu) O.Al ₂ O _{3 and the} like are exemplified. As the particle size of the phosphor, those having a particle size known in this field are used, and the average particle size is preferably 1 to 250 μm, particularly preferably 2 to 50 μm. When these phosphors are used, the addition amount is 1 to 80 parts by weight, preferably 5 to 60 parts by weight, based on 100 parts by weight of the resin component.

The curable resin composition A of the present invention can be obtained by uniformly mixing the above components. 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, until 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 uniform using an extruder, a kneader, a roll, or the like as necessary Mix well to obtain a curable resin composition. After potting and melting the curable resin composition (without melting in the case of liquid), it is molded using a casting or transfer molding machine, and further 80-200 The cured product of the present invention can be obtained by heating at a temperature of 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, N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone as necessary. The prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber and paper, and drying by heating is formed into a curable resin composition varnish by hot press molding. It can be set as the hardened | cured material of curable resin composition A of invention. In this case, the solvent is used in an amount usually accounting for 10 to 70% by mass, preferably 15 to 70% by mass in the mixture of the curable resin composition of the present invention and the solvent A. 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.

In addition, when the curable resin composition A of the present invention is used in the form of a film or a sheet, it has characteristics such as excellent flexibility characteristics in the B stage. Such a film or sheet-shaped resin composition is applied to the release film using the curable resin composition A of the present invention as the curable resin composition varnish, and after removing the solvent under heating, it is made into a B-stage. Is obtained. This film or sheet-shaped resin composition can be used as an adhesive (interlayer insulating layer) in a multilayer substrate or the like.

Curable resin composition B (cationic curing with acidic curing accelerator (curing catalyst))
The curable resin composition B of the present invention that is cured using an acidic curing accelerator contains a photopolymerization initiator or a thermal polymerization initiator as an acidic curing accelerator. 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 accelerator, 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 the active energy ray cationic polymerization initiator include metal fluoroboron complex and boron trifluoride complex (US Pat. No. 3,379,653), bis (perfluoroalkylsulfonyl) methane metal salt (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. 4,0690,055) , dicarbonyl chelate (U.S. Pat. No. 4,068,091) of IIIa ~ Va group elements, thiopyrylium salts (U.S. Pat. No. 4139655), MF ₆ ^- VIb group element in the form of anions (U.S. Patent No. 4,161,478 No. M is selected from phosphorus, antimony and arsenic.) Arylsulfonium complex salts (US Pat. No. 4,231,951), aromatic iodonium complex salts and aromatic sulfonium complex salts (US Pat. No. 4,256,828), and bis [4- (diphenylsulfonio) phenyl] sulfide-bis-hexafluoro Metal salt (Journal of Polymer Science, Polymer Chemistry, Vol. 2, paragraph 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) And "RP-2074" (manufactured by Rhodia).
The amount of the cationic polymerization initiator used is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin component.

In the curable resin composition B of the present invention, one or more polymerization initiation assistants and, if necessary, a photosensitizer can be used in combination with the cationic polymerization initiator.
Specific examples of the polymerization initiation aid include 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-chloro Anthraquinone, 2-amylanthraquinone, 2-isopropylthioxatone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acetophenone dimethyl Ketal, benzophenone, 4-methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis-diethylamino benzophenone, and a polymerization initiator such as Michler's ketone. The amount of the polymerization initiation assistant such as a polymerization initiator used is 0.01 to 30 parts by mass, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin component capable of photoradical polymerization.

Specific examples of the photosensitizer include anthracene, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acridine orange, acridine yellow, phosphine R Benzoflavine, cetoflavin T, perylene, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethanolamine, triethylamine and the like. The amount of the photosensitizer used is 0.01 to 30 parts by mass, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin component.

Furthermore, the curable resin composition B of the present invention includes various compounding agents such as an inorganic filler, a silane coupling material, a release agent, and a pigment, and various compounding agents for various thermosetting resins as necessary. Can be added. 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 use the curable resin composition B of the present invention after uniformly dissolving it in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone or γ-butyrolactone, and then removing the solvent by drying. The solvent at this time is usually 10 to 70% by mass, preferably 15 to 70% by mass in the mixture of the curable resin composition B of the present invention and the solvent.
The curable resin composition B of the present invention can be cured by heating and / or ultraviolet irradiation (for example, Reference: Review Epoxy Resin Vol. 1, Fundamental Edition I p82-84). Since the amount varies depending on the composition of the curable resin composition B, the curing conditions are determined according to each composition. Basically, it is sufficient that the cured product has curing conditions that can express the strength required for the purpose of use. Usually, since these curable resin compositions are difficult to be completely cured only by light irradiation, it is necessary to completely complete the reaction by heating after light irradiation in applications requiring heat resistance. Moreover, since it is necessary to permeate | transmit the irradiation light in the case of photocuring to detail, the highly transparent compound and composition are desired in the epoxy resin and curable resin composition B of this invention.

When heating after light irradiation, it can be carried out in the normal curing temperature range of the curable resin composition B. For example, the temperature is preferably from room temperature to 150 ° C. for 30 minutes to 7 days. Although it changes depending on the composition 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 also exhibited.

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

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

The cured product obtained by curing the curable resin composition A and the curable resin composition B of the present invention can be used for various applications including optical component materials. The optical material refers to general materials used for applications in which light such as visible light, infrared light, ultraviolet light, X-rays, and lasers passes through the material. More specifically, in addition to LED sealing materials such as lamp types and SMD types, in display-related fields, liquid crystal display substrate materials, light guide plates, prism sheets, deflection plates, retardation plates, viewing angle correction films Liquid crystal films including adhesives and polarizer protective films are expected to be used as next-generation flat panel displays for color PDP (plasma display) sealing materials, antireflection films, optical correction films, housing materials, front surfaces Glass protective film, front glass substitute material and adhesive, etc. are LED mold materials used in LED display devices, LED sealing material, front glass protective film, front glass substitute material and adhesive, etc. are plasma Substrate materials, light guide plates, prism sheets, deflector plates, etc. in address liquid crystal (PALC) displays Difference plates, viewing angle correction films, adhesives, polarizer protective films, etc., front glass protective films in organic EL (electroluminescence) displays, front glass substitute materials, adhesives, etc., are various in field emission displays (FED). Examples thereof include a film substrate, a front glass protective film, a front glass substitute material, and 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) and disc substrate materials for optical cards, A pickup lens, a protective film, a sealing material, an adhesive, and the like can be given.

In the optical equipment field, steel camera lens materials, finder prisms, target prisms, finder covers and light-receiving sensor parts, etc., video camera photographic lenses, finder, etc., projection TV projection lenses, protective films, sealing materials, etc. , And adhesives include materials for lenses of optical sensing devices, sealing materials, adhesives, and films. In the field of optical components, fiber materials, lenses, waveguides, element sealing materials and adhesives around optical switches in optical communication systems, optical fiber materials, ferrules, sealing materials and adhesives around optical connectors, etc. In optical passive components and optical circuit components, lenses, waveguides, LED sealing materials, CCD sealing materials and adhesives are used as substrate materials, fiber materials, and device sealing materials around optoelectronic integrated circuits (OEIC). And an adhesive. In the field of optical fibers, lighting for decorative displays, light guides, etc., sensors for industrial use and displays / signs, etc., optical fibers for communication infrastructure and for connecting digital devices in the home, etc. can be mentioned. Examples of peripheral materials for semiconductor integrated circuits include resist materials for microlithography for LSI and VLSI materials. 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 plates, interior panels, interior materials, protective / bundling wire harnesses, fuel hoses, automotive lamps and glass replacements, multilayer glass for railway vehicles, etc., toughening agents for aircraft structural materials, engine peripheral members Protective / bundling wire harnesses and corrosion resistant coatings. In the construction field, interior and processing materials, electrical covers, sheets, glass interlayers, glass substitutes, solar cell peripheral materials, and the like can be mentioned. In agriculture, a film for house covering is exemplified. Next generation optical / electronic functional organic materials include peripheral materials for organic EL elements, organic photorefractive elements, optical amplification elements that are light-to-light conversion devices, optical computing elements, substrate materials around organic solar cells, fiber materials, elements And a sealing material and an adhesive.

As sealing agents, potting used for capacitors, transistors, diodes, light emitting diodes, ICs and LSIs, dipping and transfer mold sealing, potting sealing used for ICs and LSIs such as COB, COF and TAB, flip An underfill used for a chip or the like, and sealing (reinforcing underfill) when mounting IC packages such as BGA and CSP can be given.

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 using the curable resin composition A or curable resin composition B of the present invention as an additive to other resins, for example, when used as a curing agent to a sealant or a cyanate resin composition for a substrate, The case where it uses for acrylic ester-type resin etc. as a hardening agent for resists is mentioned. Examples of the adhesive include civil engineering, architectural use, automobile use, general office use, medical use, and electronic material use. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, semiconductor adhesives such as die bonding agents and underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

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 viscosities at 25 ° C. and 30 ° C. The analysis conditions in gas chromatography (hereinafter referred to as “GC”) were as follows: HP5-MS (0.25 mm IDx 15 m, thickness 0.25 μm) was used for the separation column, and the column oven temperature was set to the initial temperature of 100. The temperature was set at 0 ° C., and the temperature was raised at a rate 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 coupled eluent is tetrahydrofuran, and the flow rate is 1 ml / min. The column temperature was 40 ° C., the detection was performed by RI, and a standard polystyrene made by Shodex was used for the calibration curve.

Example 1
A flask equipped with a stirrer, a reflux condenser, a stirrer, and a Dean-Stark tube was purged with nitrogen, while 178 parts of dimethyl 2,6-decahydronaphthalenedicarboxylate (H-NDCM, manufactured by Mitsubishi Gas Chemical), cyclohexene-4 -314 parts of methanol and 0.07 part of tetrabutoxytitanium were added and the reaction was carried out while removing methanol produced by the reaction at 120 ° C for 1 hour, 150 ° C for 1 hour, 170 ° C for 1 hour, 180 ° C for 15 hours, Cooled to ° C.
After completion of cooling, 350 parts of toluene was added and homogenized, and then the reaction solution was washed three times with 80 parts of a 10 wt% aqueous sodium hydroxide solution, and further washed with water until the wastewater became neutral at 100 parts / time of water. Then, 285 parts of the diolefin compound of the present invention represented by the following formula (3) was obtained by distilling off toluene and unreacted cyclohexene-4-methanol under reduced pressure by heating with a rotary evaporator.

 

Example 2
In a flask equipped with a stirrer, a reflux condenser, and a stirrer, 212 parts of the diolefin compound of the present invention obtained in Example 1, 212 parts of toluene, 15 parts of water, 1.8 parts of 12-tungstophosphoric acid, phosphorus Add 1.6 parts disodium oxyhydrogen and 5.4 parts trioctylmethylammonium acetate (Lion Akzo 50% xylene solution, TOMAA-50). 113 parts of hydrogen water was added and the mixture was stirred at 50 ± 3 ° C. for 9 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, the pH was adjusted to 9 with a 30% aqueous sodium hydroxide solution, 25 parts of a 20% 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, 50 parts of activated carbon (CP made by Ajinomoto Fine Techno) was added thereto, and the mixture was stirred at room temperature for 4 hours and filtered. The obtained filtrate was washed with 100 parts of water three times and then the organic solvent was distilled off to obtain the following formula (4).

 

215 parts of the epoxy resin (EP-1) of the present invention containing as a main component was obtained.
From the measurement result of GPC, it was confirmed that 98% of the compound having the skeleton of the formula (4) was contained. Furthermore, in the GC measurement, the purity was 92%. The epoxy equivalent was 251 g / eq, and the viscosity was 79000 mPa · s (30 ° C.).

Example 3
To 20 parts of the obtained epoxy resin (EP-1) of the present invention, 300 parts of silica gel (Wakogel C-300 manufactured by Wako Pure Chemical Industries, Ltd.) was used, and ethyl acetate: hexane = 1: 5 → 1: 4 → 1: Purification was performed by column chromatography using 2 developing solvents (changing polarity in order).
The obtained epoxy resin (EP-2) of the present invention was 16 parts, and the purity of the obtained epoxy resin contained 98% or more of the skeleton compound of the formula (4) based on the GPC measurement result. It was confirmed. Furthermore, in the GC measurement, the purity was about 98%. Epoxy equivalent was 229 g / eq. Met.

Examples 4, 5, and 6
About the epoxy resin (EP-1) of the present invention obtained in Examples 1 and 2, as a curing agent, methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid MH700G, hereinafter referred to as H1) Bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid HNA-100, hereinafter referred to as H2), hexadecyltrimethylammonium hydroxide as a curing accelerator (The Tokyo Chemical Industry Co., Ltd. 25% methanol solution, referred to as C1) is blended at the blending ratio (parts by weight) shown in Table 1 below, and then defoamed for 20 minutes to cure the present invention. Sex composition was obtained.

Using the obtained curable resin composition, a heat resistance test was performed in the following manner. The results are shown in Table 1. The curing conditions are 150 ° C. × 1 hour after preliminary curing at 120 ° C. × 3 hours.

(Heat resistance test)
The curable resin compositions obtained in Examples 4 to 6 were vacuum defoamed 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, and then a polyimide film from above. Covered with. The cast was cured under the above conditions to obtain a dynamic viscoelastic test piece. Table 1 shows the results of performing a dynamic viscoelasticity test using these test pieces under the conditions shown below.
Measurement conditions Dynamic viscoelasticity measuring device: manufactured by TA-instruments, DMA-2980
Measurement temperature range: -30 ° C to 280 ° C
Temperature rate: 2 ° C./min Test piece size: 5 mm × 50 mm cut out (thickness is about 800 μm).
Analysis condition Tg: Tan-δ peak point in dynamic viscoelasticity (DMA) measurement was defined as Tg.
Elastic modulus at 25 ° C .: The elastic modulus at 25 ° C. was measured.

 

(Dent test)
Example 7, Comparative Example 1
5.0 parts of the epoxy resin (EP-2) of the present invention obtained in Examples 2 and 3, and 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate (epoxy equivalent 140 g / eq.) As a comparative example. Viscosity: 205 mPa · s (25 ° C.) hereafter referred to as EP-3) 2.8 parts, blended with 3.4 parts of curing agent (H1) and 0.03 part of curing accelerator (C1), respectively, for 20 minutes Defoaming was performed to obtain a curable resin composition (F-1) of the present invention and a comparative curable resin composition (F-2).

Using the obtained curable resin compositions (F-1) and (F-2), an LED sealing dent test was conducted. Using a precision discharge device, the syringe was filled and cast into a surface mount LED package (inner diameter 4.4 mm, outer wall height 1.25 mm) having an outer diameter of 5 mm and mounted with a chip having a center emission wave of 465 nm. Then, after 120 degreeC x 2 hours pre-curing, it was made to harden | cure at 150 degreeC x 3 hours, and the LED for a test was obtained. The surface of the obtained LED was visually observed to confirm the presence or absence of a dent. As a result, the LED encapsulated with the curable resin composition (F-1) using the epoxy resin of the present invention had almost no dent, whereas the comparative curable resin composition (F-2). The LED wire encapsulated in (1) had exposed LED wires, and dents were observed intensely.

Example 8, Comparative Examples 2, 3
Epoxy resin (EP-2) of the present invention obtained in Examples 2 and 3, epoxy resin (EP-3), bis (3,4-epoxycyclohexylmethyl) adipate (epoxy equivalent 195 g / eq. Viscosity) as comparative examples For 730 mPa · s (25 ° C.) (hereinafter referred to as EP-4), 3.4 parts of a curing agent (H1) and a quaternary phosphonium salt (PX4MP, hereinafter referred to as C2 manufactured by Nippon Chemical Industry Co., Ltd.) are used as a curing accelerator. And it mix | blended with the compounding ratio (weight part) shown in following Table 2, and deaerated for 20 minutes. 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. The transmittance of each cured product at 400 nm was compared. Further, the obtained test piece was heat-treated at 150 ° C. for 96 hours, and the degree of coloring was evaluated based on the thermal history (transmittance at 400 nm was measured and compared).

 

Synthesis example 1
In Example 2, 212 parts of the diolefin compound of the present invention obtained in Example 1 was synthesized by dehydration esterification of 1,4-cyclohexanedimethanol and 3-cyclohexenecarboxylic acid.

Synthesis was carried out in the same manner except that the diolefin compound having the structure shown in FIG. 1 was changed to 180 parts, and 183 parts of a comparative epoxy resin (EP-5) was obtained. Epoxy equivalent is 207 g / eq. The viscosity was 3700 mPa · s (25 ° C.). Further, by purifying by column chromatography in the same manner as in Example 3, an epoxy resin (EP-6) having an epoxy equivalent of 198 g / eq and a viscosity of 3010 mPa · s (25 ° C.) was obtained.

Example 9, Comparative Example 4
For the epoxy resin (EP-2) of the present invention obtained in Example 3 and, as a comparative example, the epoxy resin (EP-6) obtained in Synthesis Example 1, the acid anhydride (H1), curing as a curing agent A curing accelerator (C1) is used as an accelerator, blended at a blending ratio (parts by weight) shown in Table 3 below, defoamed for 20 minutes, and the curable resin composition of the present invention, a comparative curable resin. A composition was obtained.

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

(LED lighting test)
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.
The lighting test was performed at 60 mA, which is twice the specified current. Detailed conditions are shown below. As a measurement item, the illuminance before and after lighting for each time was measured using an integrating sphere, and the illuminance retention rate of the test LED was calculated.
Detailed lighting conditions Light emission wavelength: 465nm
Drive system: constant current system, 60 mA (light emitting element regulation current is 30 mA)
Driving environment: 85 ° C, 85%

 

Example 10 and Comparative Examples 5 and 6
EP2 as an epoxy resin for examples, EP3 and EP6 as comparative examples, and methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid MH, hereinafter referred to as H3) as a curing agent. 2-ethyl-4-imidazole (2E4MZ, manufactured by Shikoku Kasei Co., Ltd.) at a blending ratio (parts by weight) shown in Table 4 to prepare a composition, poured into a mold, and 120 ° C for 2 hours and 160 ° C for 6 hours. And cured.

The results of measuring the physical properties of the cured product thus obtained are shown in Table 4.
The physical property values were measured by the following methods.
・ IZOD impact test: Conforms to JIS K-6911.
-Water absorption: Rate of weight increase (%) after boiling a disk-shaped test piece having a diameter of 5 cm and a thickness of 4 mm in water at 100 ° C for 24 hours
Moisture absorption rate: weight increase rate (%) after absorbing a disk-shaped test piece having a diameter of 5 cm and a thickness of 4 mm under each condition

 

From the above results, it can be seen that the epoxy resin of the present invention is an epoxy resin excellent in impact resistance and water resistance.

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.
The present application is based on a Japanese patent application (Japanese Patent Application No. 2010-117176) filed on May 21, 2010, which is incorporated by reference in its entirety. Also, all references cited herein are incorporated as a whole.

Claims (5)

1. Following formula (1)
   

   

   
   (In the formula, a plurality of R ₁ and R ₂ each independently exist, and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
   The diolefin compound characterized by these.
2. An epoxy resin obtained by oxidizing the diolefin compound according to claim 1.
3. The epoxy resin according to claim 2, which is epoxidized using hydrogen peroxide or peracid.
4. A curable resin composition containing the epoxy resin according to any one of claims 2 and 3, a curing agent and / or a curing accelerator.
5. Hardened | cured material formed by hardening | curing curable resin composition of Claim 4.