JP5511047B2 - Diolefin compound, epoxy resin, and curable resin composition - Google Patents

Description

  The present invention relates to a novel epoxy resin, a diolefin compound as a raw material thereof, and a curable resin composition suitable for electrical and electronic material applications using the epoxy resin.

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 has been used as a composite material, a car body or a ship structural material because of its simplicity of manufacturing method. For such a composition, a low-viscosity epoxy resin is desired because it can be easily impregnated into carbon fiber or the like.

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

JP 2006-52187 A

  Cycloaliphatic epoxy resins are used in various types of transparent sealing materials because of their superior electrical insulation and transparency compared to glycidyl ether type epoxy resins. The problem of inferior toughness remains, and studies are underway to improve this defect (Patent Document 1).

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 provides (1) the following formula (1)

(In the formula, a plurality of R's are present independently and each represents a hydrogen atom or a methyl group.)
A diolefin compound represented by:
(2) The diolefin compound according to item (1), wherein all Rs in formula (1) are hydrogen atoms,
(3) An epoxy resin obtained by oxidizing the diolefin compound according to (1) or (2) above,
(4) The epoxy resin according to item (3), wherein hydrogen peroxide or peracid is used during oxidation,
(5) A curable resin composition comprising the epoxy resin according to (3) or (4) above and a curing agent or a curing catalyst as essential components,
(6) A cured product obtained by curing the curable resin composition according to (5) above,
(7) Following formula (6)

(In the formula, R represents a hydrogen atom or a methyl group.)
And a compound represented by the following formula (7)

The manufacturing method of the diolefin compound represented by Formula (1) as described in the preceding clause (1) characterized by making the compound represented by these react.
(8) A method for producing an epoxy resin, characterized in that the diolefin compound obtained by the production method described in (7) above is oxidized using hydrogen peroxide or a peracid.
About.

  The present invention relates to a liquid epoxy resin that gives a cured product excellent in toughness, and a diolefin compound as a raw material thereof. The curable fat composition of the present invention containing the epoxy resin of the present invention is required to have a wide range of applications such as electric / electronic materials, molding materials, casting materials, laminated materials, paints, adhesives, resists, etc. It is extremely useful for optical material applications.

The diolefin compound of the present invention can be produced by a reaction between a cyclohexenecarboxylic acid derivative represented by the above formula (6) and a dimethanol derivative of tricyclodecane represented by the above formula (7). Specific methods include esterification reactions of cyclohexene carboxylic acid derivatives with tricyclodecane dimethanol (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980), etc.). Or a transesterification reaction of cyclohexenecarboxylic acid ester (a method described in JP-A-2006-52187 can be applied).
Examples of the cyclohexene carboxylic acid derivative include cyclohexene carboxylic acid and methylcyclohexene carboxylic acid (the substitution position of the methyl group is not particularly specified).

  As a general technique, there is a technique of esterifying a cyclohexenecarboxylic acid derivative and a dimethanol derivative of tricyclodecane by a dehydration reaction under acidic conditions. For example, acidic catalyst (mineral acids such as sulfuric acid and phosphoric acid; organic acids such as toluenesulfonic acid and methanesulfonic acid; heteropolyacids such as tungstic acid and molybdic acid; And other organic acid or inorganic acid salts such as clay, inorganic acid, stannic chloride, zinc chloride, and ferric chloride are added), and esterification is performed by azeotropic dehydration.

  The diolefin compound synthesized in this way has the structure of the above formula (1). The substituent R is selected from either a hydrogen atom or a methyl group, but in the present invention, it is preferred that all are hydrogen atoms from the viewpoint of curability. In general, the resulting diolefin compound generally exhibits a liquid state due to its structure.

It can be set as the epoxy resin of this invention by oxidizing (epoxidizing) the diolefin compound of this invention shown by the said Formula (1). 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 oxidation method using peracid include the method described in JP-A-2006-52187.
When oxidation is carried out using hydrogen peroxide, JP-A-59-108793, JP-A-62-234550, JP-A-5-213919, JP-A-11-349579, JP-B-1 Various methods such as those disclosed in Japanese Patent No. 33471, Japanese Patent Application Laid-Open No. 2001-17864, Japanese Patent Publication No. 3-57102, and the like can be applied.
The method for producing the epoxy resin of the present invention is not particularly limited, and any method may be used, but a method using hydrogen peroxide is more preferable because a low-viscosity epoxy resin can be obtained. An example of an oxidation method using hydrogen peroxide will be described below.

A specific method of oxidation using hydrogen peroxide is to oxidize using quaternary ammonium salts using tungstic acids as catalysts.
Examples of tungstic acids include tungsten acids such as tungstic acid, tungstophosphoric acid, silicotungstic acid, and salts thereof. Specific examples of counter cations of these salts include tetramethylammonium ion, benzyltriethylammonium ion, tridecanylmethylammonium ion, dilauryldimethylammonium ion, trioctylmethylammonium ion, trialkylmethyl (octyl group and decanyl group). Quaternary ammonium such as ammonium ion, trihexadecylmethylammonium ion, trimethylstearylammonium ion, tetrapentylammonium ion, cetyltrimethylammonium ion, benzyltributylammonium ion, tricaprylmethylammonium ion, dicetyldimethylammonium ion Ions, calcium ions, magnesium ions and other alkaline earth metal ions Potassium ions, potassium ions, alkali metal ions such as cesium ions include, but are not limited thereto.

In the present invention, a salt with a quaternary ammonium ion is preferable, and an organic tungstic acid having excellent compatibility with a diolefin compound is particularly preferable.
Organized tungstic acids can be produced by reacting a tungsten-based acid or a salt thereof with a quaternary ammonium salt. Specific examples of the quaternary ammonium salt include 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 group) ) Ammonium salt, trihexadecylmethylammonium salt, trimethylstearylammonium salt, tetrapentylammonium salt, cetyltrimethylammonium salt, benzyltributylammonium salt, dicetyldimethylammonium salt, tricetylmethylammonium salt, di-cured tallow alkyldimethylammonium salt However, it is not limited to these. Among these quaternary ammonium salts, quaternary ammonium salts having a total carbon number of 10 or more, preferably 25 to 100 are preferable, and all alkyl chains are particularly preferably aliphatic chains. If the carbon number of the quaternary ammonium salt exceeds 100, the hydrophobicity may become too strong and the solubility in the organic layer may deteriorate, and if the carbon number is 10 or less, the hydrophilicity becomes too strong. Similarly, the compatibility with the organic layer may deteriorate, which is not preferable.
The anionic species in the quaternary ammonium salt is not particularly limited, and examples thereof include halide ions, nitrate ions, sulfate ions, hydrogen sulfate ions, acetate ions, and carbonate ions.

The reaction between the tungstic acid and the quaternary ammonium salt is preferably carried out in a two-layer system of water or a water-organic layer. In particular, it is known that the structure of tungstic acid changes depending on its pH, and it is preferable to adjust the pH of the aqueous layer between 2 and 6. For adjusting the pH of the aqueous layer, various commonly used buffer solutions such as phosphoric acid and tartaric acid can be used. However, in this production method, the pH adjustment is particularly easy and the compatibility of the phosphorus atom with the metal salt is particularly important. It is preferable to use a phosphate buffer because of its goodness.
Specifically, a quaternary ammonium salt is added while stirring an aqueous solution in which tungstic acids are dissolved. When the progress of the reaction is slow, the reaction proceeds easily when heated to about 40 to 90 ° C. The organized tungsten-based catalyst produced by the reaction is deposited in the aqueous layer. The target tungsten-based catalyst can be obtained by filtering the deposited salt or extracting and separating it with an organic solvent. The shape of the obtained catalyst varies depending on the combination of the tungstic acid used in the reaction and the quaternary ammonium salt, such as crystalline or resinous.
At this time, for simplification of the process, the obtained catalyst may not be isolated and the olefin compound represented by the above formula (1) may be added as it is to carry out the oxidation reaction.
The structure of the tungsten-based catalyst obtained by the above method is not clear, but the structure is such that the counter ion of tungstic acid involves protons, quaternary ammonium cations, and metal ions of the buffer used for pH adjustment. Presumed.

  The amount of hydrogen peroxide used when oxidizing the diolefin compound represented by the formula (1) using hydrogen peroxide is preferably 30% by mass or less in the reaction system. When the concentration of hydrogen peroxide exceeds 30% by mass, the decomposition reaction of the produced epoxy resin also tends to proceed, which is not preferable.

In the oxidation reaction, phosphoric acid is used for the purpose of adjusting the pH at the stage where hydrogen peroxide used for the reaction is mixed, preferably between 2 and 6, more preferably between 3 and 5. Add aqueous phosphate solution. The concentration of the phosphoric acid-phosphate aqueous solution that can be used is usually 0.1 to 20% by mass, preferably 0.1 to 10% by mass. When the pH at this stage is less than 2, the hydrolysis reaction or polymerization reaction of the epoxy group is likely to proceed, and when the pH exceeds 6, the reaction rate becomes extremely slow and a long reaction time is required. The problem of becoming.
The method for adjusting the pH by adding a phosphoric acid-phosphate aqueous solution is not limited at all, but for simplicity, 0.1 to 10 molar equivalents of phosphoric acid (or dihydrogen phosphate with respect to hydrogen peroxide used in the reaction). A method of finely adjusting the pH with a basic compound (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, etc.) after adding a phosphate such as sodium may be used.

  An organic solvent may be used during the oxidation reaction. 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; alcohols such as methanol, ethanol, isopropanol, butanol, hexanol and cyclohexanol. Can be mentioned. 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; nitriles such as acetonitrile Compounds and the like can also be used. The amount of the organic solvent that can be used is usually 10 or less, preferably 5 or less, more preferably 2.25 or less with respect to the diolefin compound 1 represented by the formula (1) by mass ratio. A mass ratio exceeding 10 is not preferable because the progress of the reaction becomes extremely slow.

As a specific reaction operation method, the diolefin compound represented by the formula (1), hydrogen peroxide, a tungsten-based catalyst, a pH adjusting solution, and a solvent as necessary are added to the reaction vessel and stirred as described above. The temperature is raised to a predetermined reaction temperature, and a reaction is performed for a predetermined time described later. Although there is no particular designation for the stirring speed, it is preferable to stir at a stirring speed higher than the degree at which the contents of the reaction vessel separated into two layers of an oil layer and an aqueous layer are emulsified in a stationary state.
Since hydrogen peroxide often generates heat when added, a method of gradually adding it after adding each component may be used. Alternatively, a method of adding hydrogen peroxide, a tungsten-based catalyst, a pH adjusting solution, and a solvent as necessary, and then gradually adding the diolefin compound represented by the formula (1) may be used.
In addition, a tungsten catalyst prepared in advance can be added, or it can be used in the reaction as it is after it is prepared in the reaction system.

  Although reaction temperature is not specifically limited, Usually, it is 0-90 degreeC, Preferably it is 0-75 degreeC, More preferably, it is 15-75 degreeC. In addition, when the acidity of the reaction solution is high, the reaction is likely to proceed, while the hydrolysis reaction is also likely to proceed. Therefore, it is effective to suppress the reaction temperature to some extent. Specifically, the reaction temperature when the pH of the reaction solution is approximately 4.0 or less is preferably 60 ° C. or less.

  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 great deal of energy. The reaction time is usually 1 to 100 hours, preferably 3 to 72 hours, more preferably 5 to 48 hours.

  After completion of the reaction, quenching of excess hydrogen peroxide is performed. As a method for quenching hydrogen peroxide, a reducing compound can be used, and a basic compound may be used. In the present invention, it is particularly preferable to carry out both of them.

  Examples of the reducing agent include sodium sulfite, sodium thiosulfate, hydrazine, and oxalic acid. The amount of the reducing agent used is 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 of excess hydrogen peroxide. .

Basic compounds include metal hydroxides such as caustic soda, caustic potash, magnesium hydroxide and calcium hydroxide, metal carbonates such as sodium carbonate and potassium carbonate, phosphates such as sodium phosphate and sodium hydrogen phosphate, and Kyowa. Examples thereof include basic solids such as composite metal salts such as Kyoward 500 manufactured by Chemical Industry, ion exchange resins, and alumina.
The amount of the basic compound used is water or an organic solvent (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 and isopropyl. In the case of a substance that dissolves in various solvents such as alcohols such as alcohol, it is usually 0.01 to 20 times mol, more preferably 0.05 to 10 times mol, more preferably moles of excess hydrogen peroxide. Preferably it is 0.05-3 times mole. These may be added as a solution of water or an organic solvent (described above) 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. When a solid base that does not dissolve in water or an organic solvent is used, a quench treatment may be performed after separation of the aqueous layer and the organic layer described later.

After the hydrogen peroxide quench (or before the quench), the organic and aqueous layers are separated. If necessary, the organic layer is washed with water (when the organic solvent is small and the organic layer and the aqueous layer are not separated, or when the organic solvent is not used, the above organic solvent is added and washed with water. The organic solvent is 0.5 to 10 times, preferably 0.5 to 5 times in mass ratio with respect to the obtained raw material polyvalent alkene compound.) Alternatively, the reaction product is extracted from the aqueous layer.
The obtained organic layer is treated with an ion exchange resin, a metal oxide, activated carbon or the like as necessary. Preferably particular metal oxides in the present invention, MgO and specific examples thereof, CaO, SrO, BaO, BeO , ZnO, CeO 2, Ce 2 O 3, Al 2 O 3, TiO, Ti 2 O 3, TiO 2 , TiO ₃ , Ti ₃ O ₅ , SiO ₂ , ZrO ₂ , FeO, Fe ₂ O ₃ , Fe ₃ O ₄ , ZrO ₂ , NiO, CoO, Co ₃ O ₄ , CuO, Cu ₂ O, AgO, Ag ₂ O _{, TiO 2 -Al 2 O 3,} TiO 2 -SiO 2, TiO 2 -ZrO 2, TiO 2 -MgO, TiO 2 -Al 2 O 3, TiO 2 -WO 3, TiO 2 -MoO 3, ZnO-SiO 2 _{, Al 2 O 3 -SiO 2,} Al 2 O 3 -ZrO 2, SiO 2 -MgO, SiO 2 -WO 3, SiO 2 -ZrO 2, chabazite, erionite, offretite, mordenite, ferrierite, Kurainotairora , Anal thyme, cancrinite, dysmondin, gmelinite, lomontite, leucite, scolesite, sodalite, tomsonite, philipsite, hermotome, merlinite, amicite, gallonite, porinite, yuugawaralite, levinite, mazzite, faujasite, natrolite , Mesolite, tomsonite, gonnaldite, edingtnite, duckardite, epistilbite, pikitite, heurlandite, clinoptilolite, stillbite, stellite, valerite, value stellite, kauresite, wairakite, porousite, ashclofin, molecular sieves, montmorillonite, Haloisart, Atapal Jade, Sepiolite, Allophane, Sex clay, activated clay, and the like diatomaceous earth. These metal oxides may be either natural or synthetic, and may be used alone or in combination. In the present invention, a mesoporous body and its active body (for example, active SiO ₂ etc.) are preferable. The treatment with the metal oxide is effective in reducing the amount of the catalyst remaining in the organic solvent. The target epoxy resin can be obtained by distilling off the solvent from the obtained organic layer. In some cases, it may be further purified by distillation. As a distillation method, it can be distilled by a technique such as a thin film or rotary molecular distillation.

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

(In the formula, a plurality of R's are present independently and each represents a hydrogen atom or a methyl group.)
The main component is a compound having a structure represented by formula (3)

(In formulas (A) to (D), R represents a hydrogen atom or a methyl group. * At both ends of formula (3) are each independently any one of (A) to (D).)
The compound of various structures as shown in FIG.

  The epoxy resin of the present invention obtained by the above-described method can be used as various resin raw materials. For example, epoxy acrylate and its derivatives, oxazolidone compounds, cyclic carbonate compounds and the like can be mentioned.

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. The curable resin composition of the present invention is large in a thermosetting resin composition (curable resin composition A) containing a curing agent and a cationic curable resin composition (curable resin composition B) containing an acidic curing catalyst. Separated.

  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 using the epoxy resin of this invention as a modifier of curable resin composition, you may add in the ratio of 1-30 mass%.

  Other epoxy resins that can be used in combination with the epoxy resin of the present invention include novolac 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-hydroxyacetaldehyde Non, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Glycidyl ethers derived from polycondensates with 4-bis (chloromethyl) benzene 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 or epoxycyclohexane structure Epoxy resins) include solid or liquid epoxy resins such as, but not limited thereto.

When using especially the curable resin composition of this invention for an optical use, combined use with an alicyclic epoxy resin or an epoxy resin of a silsesquioxane structure is preferable. In particular, 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 preferable.
These epoxy resins include esterification reaction of cyclohexene carboxylic acid and alcohols or esterification reaction of cyclohexene methanol and carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980), etc.) Described), or Tyschenko reaction of cyclohexene aldehyde (method described in JP-A-2003-170059, JP-A-2004-262871, etc.), and further transesterification of cyclohexene carboxylic acid ester (JP-A-2006-052187). And the like, which are obtained by oxidizing a compound that can be produced by the method described in Japanese Patent Publication No.
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, the acetal compound by the acetal reaction of a cyclohexene aldehyde derivative and an alcohol form is mentioned. 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 mixture 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), A method using an organic solvent (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.
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, polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride Acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, Bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid- 3, 4 Anhydride, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1,1 '-Biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol Alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, 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 ' -Condensation products with bis (chloromethyl) benzene or 1,4'-bis (methoxymethyl) benzene and their modified products, halogenated bisphenols such as tetrabromobisphenol A, imidazole, trifluoroborane-amine complexes , Guanidine derivatives, condensates of terpenes and phenols, and the like, but are not limited thereto. These may be used alone or in combination of two or more.

  As for the usage-amount of the hardening | curing agent in the curable resin composition A of this invention, 0.7-1.2 equivalent is preferable with respect to 1 equivalent of epoxy groups of an epoxy resin. 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 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 ( And tertiary amines such as 5,4,0) undecene-7, phosphines such as triphenylphosphine, and metal compounds such as tin octylate. When using a hardening accelerator, 5.0 mass parts or less is used as needed with respect to 100 mass parts of epoxy resins.

  The curable resin composition A of the present invention can also 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 ( 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 said phosphanes Contains phosphorus obtained by reacting with An epoxy resin, 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, the curable resin composition A of this invention can contain binder resin 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 usually 50 parts by mass or less with respect to 100 parts by mass of the resin component in the curable resin composition A of the present invention. , Preferably 20 mass parts or less are used as needed.

  The curable resin composition A of the present invention can contain an inorganic filler 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. Furthermore, the curable resin composition A of the present invention includes a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, various compounding agents such as pigments, and various thermosetting resins. Can be added.

  The curable resin composition A of the present invention obtained by uniformly mixing the respective components 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 The cured product of the present invention is obtained by molding the curable resin composition A obtained by thorough mixing using a cast or transfer molding machine after melting and further heating at 80 to 200 ° C. for 2 to 10 hours. Can be obtained.

  Further, the curable resin composition A of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, and the like. The resin composition varnish is used to impregnate a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber and paper, and heat-dried to obtain a curable prepreg by hot press molding. It can be set as the hardened | cured material of a resin composition. In this case, the solvent occupies 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. Moreover, the epoxy resin hardened | cured material which contains a carbon fiber by a RTM system with a liquid composition can also be obtained.

  Further, when the curable resin composition A of the present invention is used in the form of a film or a sheet, it has a characteristic that it is excellent in flexibility and the like in the B stage. Such a film or sheet-shaped resin composition is obtained by applying the varnish of the curable resin composition A of the present invention on a release film, removing the solvent under heating, and performing B-stage. . This film or sheet-shaped resin composition can be used as an adhesive (interlayer insulating layer) in a multilayer substrate or the like.

  Furthermore, as a use of the curable resin composition A of the present invention, a general use in which a thermosetting resin such as an epoxy resin is used, for example, an adhesive, a paint, a coating agent, a molding material (sheet, film, FRP, etc.) ), Insulating materials (including printed circuit boards, wire coatings, etc.), sealing materials, cyanate resin compositions for substrates, and curing agents in acrylic ester resist resin compositions, and other resin systems Examples include additives in the composition.

  Specific examples of the adhesive include civil engineering, architectural, automotive, general office, medical, and electronic materials. 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).

  Sealing agents include potting used for capacitors, transistors, diodes, light emitting diodes, ICs and LSIs, dipping or transfer molding sealants, potting seals used for COBs, COFs and TABs of ICs and LSIs, etc. Examples thereof include an underfill used for a stopper, a flip chip, a QFP sealant, and a sealant (including a reinforcing underfill) used when mounting IC packages such as BGA and CSP.

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. The amount of the cationic polymerization initiator used is preferably 0.01 to 50 parts by mass and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin component.

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 usage-amount of polymerization initiation adjuvants, such as a polymerization initiator, is 0.01-30 mass parts with respect to 100 mass parts of resin components, Preferably it is 0.1-10 mass parts.

  Specific examples of the photosensitizer include anthracene, 2-isopropylthioxatone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acridine orange, acridine yellow, and phosphine R. Benzoflavine, 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 mass parts with respect to 100 mass parts of epoxy resin components, Preferably it is 0.1-10 mass parts.

  Furthermore, in the curable resin composition B of the present invention, various compounding agents such as known compounds such as various thermosetting resins, inorganic fillers, silane coupling agents, mold release agents, pigments, and the like 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 usage-amount at the time of using an organic solvent is 10-70 mass% normally in the mixture of curable resin composition B of this invention and this solvent, Preferably it is 15-70 mass%. 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 Basic Edition I p82-84). Since the amount varies depending on the composition of the curable resin composition B, the curing conditions are determined in accordance with each composition. Basically, the cured product should be capable of expressing the strength required for the purpose of use. It ’s fine. Usually, these epoxy resin-based compositions are difficult to be completely cured only by light irradiation. Therefore, in applications requiring heat resistance, it is necessary to complete the reaction by heating after light irradiation. Moreover, since it is necessary to permeate | transmit the irradiation light in the case of photocuring to detail, the highly transparent compound and composition are desired in the epoxy resin and curable resin composition B of this invention.

  The heating after the light irradiation may be performed in the 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. The conditions for thermosetting vary depending on the composition of the curable resin composition B. Usually, the higher the temperature, the more effective the curing is after light irradiation, and the lower the temperature, the longer the heat treatment is required. . Such post-curing by heating is also effective for removing moisture and deposited organic substances contained in the cured product.

  The cured product obtained by curing the curable resin composition B can have, for example, a film shape, a sheet shape, a bulk shape, and the like, but is not limited thereto, and may be an optimum shape for a specific application. It ’s fine. Examples of the method for forming these various shapes of cured products include, but are not limited to, a casting method, a casting method, a screen printing method, a spin coating method, a spray method, a transfer method, and a dispenser method. Instead, an appropriate method may be employed to obtain a desired 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.

  When the curable resin composition B of the present invention is used as, for example, a cationic curable resist, 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. The film is applied on a substrate such as a tension laminate, 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, 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 ultrahigh pressure mercury lamp, a xenon lamp, a laser beam, etc.) through a negative film having a desired pattern drawn, and then 70 A post-exposure bake treatment is performed 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 (for example, 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 in 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 sheets, interior panels, interior materials, protective / bundling wireness, fuel hoses, automotive lamps and glass substitutes, etc., multilayer glass for railway vehicles, toughness imparting agents for aircraft structural materials, engine peripheral members Protective / bundling wireness and corrosion resistant coating. 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 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 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 is used. For example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), Insulating materials (including printed circuit boards and wire coatings), sealants, additives to other resins, and the like. 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).

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

Example 1
To a flask equipped with a stirrer, reflux condenser, stirrer, and Dean-Stark tube, while purging with nitrogen, 100 parts of toluene, 126 parts of 3-cyclohexene-1-carboxylic acid, 98 parts of tricyclodecane dimethanol, p-toluene 3 parts of sulfonic acid was added, and the reaction was carried out for 15 hours while dehydrating under a reflux condition using a Dean-Stark tube. After completion of the reaction, 5 parts of sodium tripolyphosphate was added and stirred at 100 ° C. for 1 hour. After cooling to room temperature, 300 parts of methyl isobutyl ketone was added, washed with 300 parts of water three times, 100 parts of silica gel and 1 part of activated carbon were added to the resulting organic layer, and the mixture was stirred at room temperature for 2 hours, followed by filtration. It was. By removing the solvent from the obtained filtrate, the following formula (4)

The diolefin compound 190 part of this invention represented by these was obtained.
As a result of GC analysis of the obtained compound, the main peaks had retention times of 13.9 minutes, 14.1 minutes, 14.2 minutes and 14.4 minutes (having several isomers). Therefore, some peaks overlap, and small peaks are omitted). Furthermore, in the measurement by GC-MS (EI), a parent peak appeared at 412 and it was confirmed that this coincided with the formula (4). The viscosity at 25 ° C. was 950 mPa · s.

Example 2
To a flask equipped with a stirrer, a reflux condenser, and a stirrer, 12 parts of water, 0.38 part of 12-tungstophosphoric acid, 0.56 part of phosphoric acid and sodium carbonate were added while purging with nitrogen, and the pH was adjusted to 4.7. Adjusted. Further, after adding 0.6 parts of trioctylmethylammonium chloride (manufactured by Tokyo Chemical Industry) to produce a tungstic acid catalyst, 50 parts of toluene, 41 parts of the compound represented by the formula (4) obtained in Example 1 Was added and stirred again to obtain an emulsion solution. This solution was heated to 50 ° C., 24.8 parts of 30% hydrogen peroxide was added with vigorous stirring, and the reaction was carried out by stirring for 15 hours while maintaining the temperature at 50 ° C. When the progress of the reaction was confirmed by GC, the substrate conversion after the completion of the reaction was 99% or more, and the peak due to the raw material disappeared.
Subsequently, 20 parts of a 1% sodium hydroxide aqueous solution and 10 parts of a 20% sodium thiosulfate aqueous solution were added to the reaction solution, and the mixture was stirred for 1 hour. Only the organic layer was taken out from the reaction solution separated into two layers after standing, and 30 parts of toluene was added to the remaining aqueous layer to extract the organic matter in the aqueous layer, and then left to stand again and separated to take out only the organic layer. It was. This extraction / separation operation from the organic layer was further repeated twice. After mixing the obtained organic layers, 20 parts of silica gel was added and stirred at room temperature for 1 hour. The silica gel taken out by filtration is washed with 50 parts of toluene, and then the organic solvent is distilled off from the washing solution using a rotary evaporator.

40 parts of epoxy resin (EP-1) of this invention represented by these were obtained.
As a result of analyzing the epoxy resin (EP-1) by GC, the main peaks were 16.3 minutes, 16.5 minutes, 16.7 minutes, 16.8 minutes, 17.0 minutes, 17.2 minutes, 17 It had retention times of .4 minutes, 17.7 minutes, and 17.9 minutes (there were several isomers, so some of the peaks overlapped, and small peaks were omitted). Furthermore, in the measurement by GC-MS (EI), a parent peak appeared at 444, and it was confirmed that this coincided with the formula (5). The viscosity at 25 ° C. is 45 Pa · s, and the epoxy equivalent is 233 g / eq. Met. Further, when GPC was measured, it was confirmed that the weight average molecular weight was 288.

Example 3
Using 15 parts of silica gel (trade name: Wako Gel C-300, manufactured by Wako Pure Chemical Industries) to 15 parts of the epoxy resin (EP-1) obtained in Example 2, a developing solvent of ethyl acetate: hexane = 1: 4 Was purified by column chromatography to obtain 12 parts of an epoxy resin (EP-2). The epoxy resin (EP-2) was confirmed to contain 98% or more of the skeleton compound of the formula (5) from the GPC measurement results. Furthermore, in the GC measurement, the purity was about 99%. The epoxy equivalent was 205 g / eq. Met.

Examples 4-6
About the epoxy resin (EP-1 and EP-2) of the present invention obtained in Examples 2 and 3, methylhexahydrophthalic anhydride (trade name: Ricacid MH700G, manufactured by Shin Nippon Rika Co., Ltd.) as a curing agent, H1), cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride (trade name H-TMAn, manufactured by Mitsubishi Gas Chemical Co., Inc., hereinafter referred to as H2), and hexadecyltrimethylammonium as a curing accelerator. Using hydroxide (Tokyo Kasei Kogyo Co., Ltd., 25% methanol solution, hereinafter referred to as C1), it was blended at the blending ratio (parts by mass) shown in Table 1 below, and defoamed for 20 minutes. A curable composition was obtained.

(Heat resistance test)
The curable resin compositions obtained in Examples 4 to 6 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. The lid was covered with a polyimide film. The dynamic viscoelasticity test was performed under the conditions shown below using a test piece for dynamic viscoelasticity obtained by curing the cast by heat treatment at 120 ° C for 2 hours and 160 ° C for 2 hours. Carried out. The results are shown in Table 1.
Measurement conditions Dynamic viscoelasticity measuring device: manufactured by TA-instruments, DMA-2980
Measurement temperature range: -30 ° C to 280 ° C
Temperature rising rate: 2 ° C./min Test piece size: 5 mm × 50 mm cut out (thickness is about 800 μm).
Analysis condition Tg: The peak point of Tan δ in DMA measurement was defined as Tg.

(Thermo-mechanical property test)
The curable resin compositions obtained in Examples 4 to 6 were subjected to vacuum defoaming for 20 minutes, and then cast with a Teflon (registered trademark) φ2 mm tube, and the cast was used for a heat resistance property test. A thermomechanical property test (TMA test) was performed under the following conditions using a test piece obtained by curing under the same conditions as the sample. The results are shown in Table 1.
Measurement conditions Thermomechanical measuring instrument: TM-7000, manufactured by Vacuum Riko Co., Ltd.
Measurement temperature range: 40 ° C to 250 ° C
Temperature rising rate: 2 ° C./min Test piece size: A material cut into φ2 mm × 15 mm was used.

(Thermal durability transmission test)
The curable resin compositions obtained in Examples 4 to 6 were subjected to vacuum defoaming for 20 minutes, and then gently poured onto a glass substrate on which a dam was made with heat-resistant tape so as to be 30 mm × 20 mm × height 1 mm. Then, after pre-curing at 120 ° C. for 3 hours, it was cured at 150 ° C. for 1 hour to obtain a transmittance test piece having a thickness of 1 mm.
Using these test pieces, the transmittance (measurement wavelength: 400 nm) before and after being allowed to stand for 96 hours in an oven at 150 ° C. was measured with a spectrophotometer, and the transmittance retention was calculated. The results are shown in Table 1.

Example 7, Comparative Example 1
Epoxy resin (EP-2) of the present invention obtained in Example 3 and 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexylcarboxylate (trade name ERL-4221, Dow Chemical Company) as a comparative example Manufactured, epoxy equivalent 140 g / eq., Hereinafter referred to as EP-3), using H1 and H2 as curing agents, blended at a blending ratio (part by mass) shown in Table 2 below, and defoamed for 20 minutes, The curable composition of this invention and the comparative example was obtained.

(LED test)
Surface subjected to vacuum defoaming for 20 minutes on the curable resin composition obtained in Example 7 and Comparative Example 1, and then filled into a syringe and mounted with a light emitting element having an emission wavelength of 465 nm using a precision discharge device It was cast into a mounting type LED. A reflow test and a heat cycle test were performed using test LEDs obtained by subjecting the casting to heat treatment at 120 ° C. for 2 hours and 140 ° C. for 2 hours. The results are shown in Table 2.

(1) LED reflow test After the test LED was moisture-absorbed for 24 hours under a wet heat condition of 30 ° C. and 70% RH, the following was used using a high-temperature observation device (SMT Scope SK-5000, manufactured by Sanyo Seiko Co., Ltd.). The presence or absence of cracks under reflow conditions was visually observed. Each test LED was tested at n = 3 and evaluated by the number at which cracks did not occur.
Reflow conditions: The temperature was raised from 25 ° C. to 150 ° C. at 2 ° C./second and held at 150 ° C. for 2 minutes, then heated to 260 ° C. at 2 ° C./second and held at 260 ° C. for 10 seconds. Cool to room temperature at 3 ° C / second.

(2) LED heat cycle test A heat cycle test is performed on the test LED under the following conditions using a heat cycle tester (TSA-41LA, manufactured by Espec Corporation), and the presence or absence of cracks is visually observed. did.
Heat cycle test conditions: −40 ° C. × 15 minutes / + 120 ° C. × 15 minutes 500 cycles (both the time required for temperature increase and decrease is 2 minutes).

  From the results of the reflow test and the heat cycle test, it can be seen that the epoxy resin of the present invention and the composition give a cured product having excellent toughness.

Example 8, Comparative Example 2
The epoxy resin (EP-1) of the present invention obtained in Example 2, and an epoxy resin represented by the following formula (6) described in Patent Document 1 as a comparative example (epoxy equivalent: 207 g / eq., Viscosity at 25 ° C. 4200 mPa · s, hereinafter referred to as EP-4), using H1 as a curing agent, C1 as a curing catalyst, and blending at a blending ratio (part by mass) shown in Table 3 below, the curable compositions of the present invention and comparative examples I got a thing.

(Thermo-mechanical property test)
The curable resin composition obtained in Example 8 and Comparative Example 2 was subjected to vacuum defoaming for 20 minutes, and then cast in a Teflon (registered trademark) φ2 mm tube, and the cast was tested for heat resistance. Using the test piece obtained by curing under the same conditions as the sample used in the above, a TMA test was performed under the following conditions, and the amount of linear expansion at 50 to 220 ° C. was compared. The results are shown in Table 3.
Measurement conditions Thermomechanical measuring instrument: TM-7000, manufactured by Vacuum Riko Co., Ltd.
Measurement temperature range: 40 ° C to 250 ° C
Temperature rising rate: 2 ° C./min Test piece size: A material cut into φ2 mm × 15 mm was used.

  From the results of the reflow test and the heat cycle test, it can be seen that the epoxy resin of the present invention and the composition give a cured product having a small amount of linear expansion at high temperature and excellent in dimensional stability.

  Since the epoxy resin of the present invention gives a cured product excellent in toughness, the curable fat composition of the present invention containing the epoxy resin of the present invention is an electric / electronic material, a molding material, a casting material, a laminated material, a paint, It is extremely useful for a wide range of applications such as adhesives and resists, especially for optical materials requiring low colorability.

Claims (8)

Following formula (1)

(In the formula, a plurality of R's are present independently and each represents a hydrogen atom or a methyl group.)
The diolefin compound represented by these. The diolefin compound according to claim 1, wherein all R in the formula (1) are hydrogen atoms. The following formula (2) obtained by oxidizing the diolefin compound according to claim 1 or 2.

(In the formula, a plurality of R's are present independently and each represents a hydrogen atom or a methyl group.)
Epoxy resin represented by The epoxy resin according to claim 3, wherein hydrogen peroxide or peracid is used in the oxidation. A curable resin composition comprising the epoxy resin according to claim 3 and 4 and a curing agent or a curing catalyst as essential components. A cured product obtained by curing the curable resin composition according to claim 5. Following formula (6)

(In the formula, R represents a hydrogen atom or a methyl group.)
And a compound represented by the following formula (7)

A process for producing a diolefin compound represented by the formula (1) according to claim 1, wherein the compound represented by formula (1) is reacted. The diolefin compound obtained by the production method according to claim 7 is oxidized using hydrogen peroxide or peracid, the following formula (2)

(In the formula, a plurality of R's are present independently and each represents a hydrogen atom or a methyl group.)
The manufacturing method of the epoxy resin represented by this.