JP5796916B2 - Production method of epoxy resin - Google Patents

Description

  The present invention relates to a novel diolefin compound and an epoxy resin suitable for use in electrical and electronic materials.

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. 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, especially in recent years, advanced information technology, in order to smoothly transmit and process a huge amount of information, technology that utilizes optical signals will be developed instead of conventional signal transmission using electrical wiring. In particular, in the field of optical components such as optical waveguides, blue LEDs, and optical semiconductors, development of resins having excellent transparency is desired. In response to these demands, alicyclic epoxy compounds have attracted attention.

Alicyclic epoxy compounds are superior in terms of electrical insulation and transparency compared to glycidyl ether type epoxy compounds, and are used in a variety of transparent sealing materials. In the field where optical properties are required, compounds having sufficient heat resistance and light resistance are required (Patent Documents 1, 2, and 3).

JP 2006-52187 A Japanese Patent Laid-Open No. 2007-510772 JP 2007-16073 A

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

（式中、複数存在するＲ^１、Ｒ^２はそれぞれ独立して存在し、Ｒ^１は炭素数１〜６のアルキル基を表し、Ｒ^２は水素原子、もしくはメチル基を表す。（P）は＊位でSiと結合している。）
で表されることを特徴とするジオレフィン樹脂、
（３）前項（１）又は（２）いずれか一項に記載のジオレフィン化合物を酸化することにより得られるエポキシ樹脂、
（４）過酸化水素、過酸のいずれかを用いてエポキシ化することを特徴とする前項（３）に記載のエポキシ樹脂、
（５）前項（３）又は（４）のいずれか一項に記載のエポキシ樹脂と硬化剤および／または硬化触媒を含有する硬化性樹脂組成物、
（６）前項（５）に記載の硬化性樹脂組成物を硬化してなる硬化物、
に関する。 As a result of intensive studies in view of the above-described actual situation, the present inventors have completed the present invention.
That is, the present invention
(1) Diolefin resin obtained by reaction of alkylsiloxane having two Si—H bonds with dicyclopentadiene and / or methyldicyclopentadiene (2) Formula (1)

(In the formula, a plurality of R ¹ and R ² exist independently, R ¹ represents an alkyl group having 1 to 6 carbon atoms, R ² represents a hydrogen atom or a methyl group. (P) represents * Bonded to Si at the position.)
A diolefin resin characterized by being represented by:
(3) An epoxy resin obtained by oxidizing the diolefin compound according to any one of (1) or (2) above,
(4) The epoxy resin as described in (3) above, which is epoxidized using either hydrogen peroxide or peracid,
(5) A curable resin composition containing the epoxy resin according to any one of (3) and (4) above, a curing agent and / or a curing catalyst,
(6) A cured product obtained by curing the curable resin composition according to (5) above,
About.

  The olefin resin of the present invention is a raw material for an epoxy resin (epoxy resin of the present invention) that provides a cured product having excellent transparency and optical properties. The curable fat composition of the present invention containing the epoxy resin of the present invention is extremely useful for a wide range of applications such as electric / electronic materials, molding materials, casting materials, laminate materials, paints, adhesives, resists, etc., especially optical materials. It is.

  The present invention is a diolefin resin obtained by reacting an alkylsiloxane having two Si-H bonds with dicyclopentadiene and / or methyldicyclopentadiene. Moreover, it is related with the epoxy resin obtained by oxidizing this.

  Examples of alkylsiloxanes having two Si-H bonds include 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetraethyldisiloxane, 1,1,3,3-tetrapropyldisiloxane, Examples include 1,3-dimethyl-1,3-diphenylpropanedisiloxane.

A hydrosilylation reaction can be used as the reaction between the alkylsiloxane having two Si—H bonds and dicyclopentadiene and / or methyldicyclopentadiene. Generally known as a hydrosilylation reaction is a reaction using a Speier catalyst (H ₂ PtCl ₆ ) and a Karstedt catalyst (prepared from H ₂ PtCl ₆ and vinyl siloxane). (Reference Document ODOOS: Online Database of Organic Synthesis http://www.chem-station.com/odos/) In the present invention, any catalyst may be used. Chloroplatinic acid, chloroplatinic acid alcohol solution, platinum olefin complex, platinum alkenylsiloxane complex, platinum carbonyl complex and the like. (Reference patent document: JP-A-2001-139688)

  Examples of the compound thus obtained include the following compounds. Following formula (2)

（式中、複数存在するＲ^１、Ｒ^２はそれぞれ独立して存在し、Ｒ^１は炭素数１〜６のアルキル基を表し、Ｒ^２は水素原子、もしくはメチル基を表す。ｎはくり返し数であり、平均値を示し、通常０〜２．５であり、好ましくは０〜１．７、さらに好ましくは０〜１．０である。（P）又は（Q）は＊位でSiと結合している。）
で表される。
本発明においては特にくり返し数ｎが０である前記式（１）の構造が好ましい。
ここで、式（２）の化合物の分子量分布は仕込みの比率と温度で制御をすることが可能である。

(In the formula, a plurality of R ¹ and R ² are independently present, R ¹ represents an alkyl group having 1 to 6 carbon atoms, R ² represents a hydrogen atom or a methyl group, and n is a number of repetitions. The average value is usually 0 to 2.5, preferably 0 to 1.7, and more preferably 0 to 1.0. (P) or (Q) is bonded to Si at the * position. doing.)
It is represented by
In the present invention, the structure of the above formula (1) in which the repetition number n is 0 is particularly preferable.
Here, the molecular weight distribution of the compound of the formula (2) can be controlled by the charging ratio and temperature.

The diolefin resin of the present invention represented by the formulas (1) and (2) 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 JP-A-2006-52187.
Various methods can be applied to the method of epoxidation with hydrogen peroxide solution. Specifically, JP-A-59-108793, JP-A-62-234550, JP-A-5-213919, Techniques such as those disclosed in JP-A-11-349579, JP-B-1-33471, JP-A-2001-17864, JP-B-3-57102 and the like can be applied.

Hereinafter, a particularly preferable method for obtaining the epoxy resin of the present invention will be exemplified.
First, the diolefin resin, polyacids and quaternary ammonium salt of the present invention are reacted in a suspended state of organic matter and hydrogen peroxide water.

The polyacid used in the present invention is not particularly limited as long as it is a compound having a polyacid structure, but is preferably a polyacid containing tungsten or molybdenum, more preferably a polyacid containing tungsten, and particularly preferably a tungstate. Typical polyacids include tungsten acids such as tungstic acid, 12-tungstophosphoric acid, 12-tungstoboric acid, 18-tungstophosphoric acid, 12-tungstosilicic acid, and molybdenum acids such as molybdic acid and phosphomolybdic acid. Examples include salts.
Examples of counter cations 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, and 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 0.5 to 20 mmol in terms of metal element (tungstenic acid is tungsten atom, molybdic acid is molybdenum atom) with respect to 1 mol (functional group equivalent) of the olefin of the present invention, preferably It is 1.0-20 mmol, More preferably, it is 2.5-15 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. Particularly preferred are those having 25 to 100 carbon atoms.
There are no particular limitations on the anionic species of these salts, and specific examples include halide ions, nitrate ions, sulfate ions, hydrogen sulfate ions, acetate ions, carbonate ions, and the like, but are not limited thereto.
When the number of carbon atoms exceeds 100, the hydrophobicity becomes too strong, and the solubility of the quaternary ammonium salt in the organic layer may deteriorate. When the number of carbon atoms is 10 or less, the hydrophilicity is increased, and the compatibility of the quaternary ammonium salt with the organic layer is similarly deteriorated.
The amount of quaternary ammonium salt used is preferably 0.01 to 0.8 times equivalent, or 1.1 to 10 times equivalent to the valence of the tungstic acid used. More preferably, it is 0.05 to 0.7 times equivalent, or 1.2 to 6.0 times equivalent, and 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 it is trivalent in the case of tungstophosphoric acid, it is similarly 0.03 to 2.4 mol, or 3.3 to 20 mol, and in the case of silicotungstic acid, it is tetravalent, so 0.04 to 3.2 mol. Or 4.4 to 40 mol is preferable.
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 equivalent, not only is the post-treatment difficult, but there is a function of suppressing the reaction, which is not preferable.

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 4 or less, the hydrolysis reaction and polymerization reaction of the epoxy group easily proceed. On the other hand, if the pH is higher than 10, the reaction becomes extremely slow and the reaction time is too long.
In particular, in the present invention, when the tungstic acid as a catalyst is dissolved, the pH is preferably adjusted to be between 5 and 9.
For example, in the case of a phosphoric acid-phosphate aqueous solution, which is a preferable buffer, 0.1 to 10 mol% equivalent of phosphoric acid (or a phosphate such as sodium dihydrogen phosphate) is used. And a method of adjusting pH with a basic compound (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, etc.). Here, it is preferable that the pH is added so that the above-mentioned pH is obtained when hydrogen peroxide is added. It is also possible to adjust using sodium dihydrogen phosphate, disodium hydrogen phosphate, or the like. The preferred phosphate concentration is 0.1 to 60% by weight, more preferably 1 to 45% by weight. In this reaction, a buffer solution is not used, but disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, sodium tripolyphosphate, etc. (or hydrates thereof) are directly added without adjusting pH. It doesn't matter. In the sense of simplifying the process, there is no troublesome pH adjustment, and direct addition is particularly preferable. The amount of phosphate used in this case is usually 0.1 to 5 mol% equivalent, preferably 0.2 to 4 mol% equivalent, more preferably 0.3 to 3 mol% equivalent to hydrogen peroxide. is there. 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 compound hydrolyzate is likely to proceed or the reaction is slow. The harmful effect of becoming.

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

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

As a specific reaction operation method, for example, when the reaction is performed in a batch-type reaction kettle, diolefin resin, hydrogen peroxide (aqueous solution), polyacids (catalyst), buffer solution, quaternary ammonium salt and organic solvent are used. 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. At this time, after adjusting the pH by adding a buffer solution (or water and phosphate) and tungstic acid, a quaternary ammonium salt, an organic solvent and a diolefin resin were added, and the mixture was stirred in two layers. Is used.
Alternatively, while stirring water, an organic solvent, and a compound having a carbon-carbon double bond, tungstic acid and phosphoric acid (or phosphates) are added, pH is adjusted, and a quaternary ammonium salt is added, It is also possible to use a method of dropping hydrogen peroxide when stirring in two layers.

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

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

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

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

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

After the hydrogen peroxide quench (or before quenching), if the organic layer and the aqueous layer are not separated, or if no organic solvent is used, the above-mentioned organic solvent is added and the operation is performed. The reaction product is extracted from the layer. The organic solvent used at this time is 0.5 to 10 times, preferably 0.5 to 5 times in weight ratio to the raw material diolefin compound. This operation is repeated several times as necessary, and the separated organic layer is purified by washing with water as necessary.
The obtained organic layer may be an ion exchange resin, a metal oxide (especially, silica gel, alumina, etc. are preferred), activated carbon (especially, preferably a chemical activated carbon), 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 the like, 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 compound thus obtained has the formula (3)

（式中、複数存在するＲ^１、Ｒ^２はそれぞれ独立して存在し、Ｒ^１は炭素数１〜６のアルキル基を表し、Ｒ^２は水素原子、もしくはメチル基を表す。ｎはくり返し数であり、平均値を示し、通常０〜２．５であり、好ましくは０〜１．７、さらに好ましくは０〜１．０である。（P）又は（Q）は＊位でSiと結合している。）
で表される分子を主成分とするが、エポキシが開環した加水分解体、未反応のオレフィン体、さらにはエポキシ基同士の重合した高分子量体や、その他副反応物が反応条件によっては生成する。

(In the formula, a plurality of R ¹ and R ² are independently present, R ¹ represents an alkyl group having 1 to 6 carbon atoms, R ² represents a hydrogen atom or a methyl group, and n is a number of repetitions. The average value is usually 0 to 2.5, preferably 0 to 1.7, and more preferably 0 to 1.0. (P) or (Q) is bonded to Si at the * position. doing.)
The main component is a hydrolyzate in which epoxy is ring-opened, an unreacted olefin, and a high molecular weight polymer obtained by polymerizing epoxy groups, and other by-products depending on the reaction conditions. To do.

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

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

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

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

When using especially the curable resin composition of this invention for an optical use, combined use with an alicyclic epoxy resin or an epoxy resin of a silsesquioxane structure is preferable. Particularly in the case of an alicyclic epoxy resin, a compound having an epoxycyclohexane structure in the skeleton is preferable, and an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure is particularly preferable.
These epoxy resins include esterification reaction of cyclohexene carboxylic acid and alcohols or esterification reaction of cyclohexene methanol and carboxylic acids (Tetrahedron vol.36 p.2409 (1980), Tetrahedron Letter p.4475 (1980), etc.) Described), or Tyschenko reaction of cyclohexene aldehyde (method described in 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. Diol, 1,6-hexanediol, cyclohexanedimethanol, 2,4-diethylpentanediol, 2-ethyl-2-butyl-1.3-propanediol, neopentyl glycol, tricyclodecane dimethanol, norbornenediol, etc. Diols, glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane, triols such as 2-hydroxymethyl-1,4-butanediol, tetraols such as pentaerythritol, ditrimethylolpropane, etc. It is below. 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, examples of the compound having a cyclohexene structure include an acetal compound obtained by an acetal reaction between a cyclohexene aldehyde derivative and an alcohol. 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. Thermal curing with a curing agent (curable resin composition A)
Examples of the curing agent contained in the curable resin composition A of the present invention include amine compounds, acid anhydride compounds, amide compounds, phenol compounds, and carboxylic acid compounds. Specific examples of the curing agent that can be used include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and nitrogen-containing compounds such as polyamide resins synthesized from linolenic acid and ethylenediamine (amine, Amide compounds); 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-1,3,4-tricarboxylic acid-3,4-anhydride; carboxylic acid resins obtained by addition reaction of various alcohols, carbinol-modified silicones and the above-mentioned 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, 1,4'-bis (methoxymethyl) benzene, etc. And their modified products, polyphenols such as halogenated bisphenols such as tetrabromobisphenol A, condensates of terpenes and phenols; imidazole, trifluoroborane-amine complexes, guanidine derivative compounds, etc. Limited to is not. These may be used alone or in combination of two or more.
In the present invention, a compound having an acid anhydride structure and / or a carboxylic acid structure represented by the aforementioned acid anhydride and carboxylic acid resin is particularly preferable.

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

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

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

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

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

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

  In the curable resin composition A of the present invention, a curing accelerator may be used in combination with the curing agent. Specific examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza- Tertiary amines such as bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, etc. Quaternary phosphonium salts such as quaternary ammonium salt, triphenylbenzylphosphonium salt, triphenylethylphosphonium salt, tetrabutylphosphonium salt (counter ion of quaternary salt is halogen, organic acid ion, hydroxide ion, etc. No, but especially organic acids Emissions, a hydroxide ion.) Include metal compounds such as tin octylate. When using a hardening accelerator, 0.01-5.0 weight part is used as needed with respect to 100 weight part of epoxy resins.

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

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

  Examples of the antioxidant include phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants. Specific examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio)- Monophenols such as 6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,4-bis [(octylthio) methyl] -o-cresol; 2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-thiobis (3- 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-tert-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-hydroxybenzylphosphonate-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 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, distearyl-3,3′-thiodipropionate, and the like. The

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

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

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

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

  An inorganic filler can be added to the curable resin composition A of the present invention as necessary. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These may be used alone or in combination of two or more. The content of these inorganic fillers is 0 to 95% by weight in the curable resin composition of the present invention. Furthermore, the curable resin composition of the present invention includes various release agents such as silane coupling agents, stearic acid, palmitic acid, zinc stearate, calcium stearate, surfactants, dyes, pigments, ultraviolet absorbers, and the like. And various thermosetting resins can be added.

When using the curable resin composition 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 using these fluorescent substance, the addition amount is 1-80 weight part with respect to 100 weight part with respect to the resin component, Preferably, it is 5-60 weight part.

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

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

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

  Next, the case where the epoxy resin composition of the present invention is used as an optical semiconductor sealing material or die bonding material will be described in detail.

  When the epoxy resin composition of the present invention is used as a sealing material for an optical semiconductor such as a high-intensity white LED, or a die bond material, a curing agent (curing agent composition) containing the polyvalent carboxylic acid of the present invention, Prepare an epoxy resin composition by thoroughly mixing additives such as curing accelerators, coupling materials, antioxidants, light stabilizers, etc., in addition to epoxy resins, and seal them as sealing materials or die bond materials. Used for both materials. As a mixing method, a kneader, a three-roll, a universal mixer, a planetary mixer, a homomixer, a homodisper, a bead mill or the like is used to mix at room temperature or warm.

  Optical semiconductor elements such as high-intensity white LEDs are generally GaAs, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, InN, AlN, InGaN laminated on a substrate of sapphire, spinel, SiC, Si, ZnO or the like. Such a semiconductor chip is bonded to a lead frame, a heat sink, or a package using an adhesive (die bond material). There is also a type in which a wire such as a gold wire is connected to pass an electric current. The semiconductor chip is sealed with a sealing material such as an epoxy resin in order to protect it from heat and moisture and play a role of a lens. The epoxy resin composition of the present invention can be used as this sealing material or die bond material. From the viewpoint of the process, it is advantageous to use the curable resin composition of the present invention for both the die bond material and the sealing material.

As a method of adhering a semiconductor chip to a substrate using the curable resin composition of the present invention, the epoxy resin composition of the present invention is applied by a dispenser, potting, or screen printing, and then the semiconductor chip is placed and heat cured. The semiconductor chip can be bonded. For the heating, methods such as hot air circulation, infrared rays and high frequency can be used.
The heating condition is preferably about 80 to 230 ° C. and about 1 minute to 24 hours, for example. For the purpose of reducing internal stress generated during heat curing, for example, after pre-curing at 80 to 120 ° C. for 30 minutes to 5 hours, post-curing is performed at 120 to 180 ° C. for 30 minutes to 10 hours. it can.

As a molding method of the sealing material, as described above, an injection method in which the sealing material is injected into the mold frame in which the substrate on which the semiconductor chip is fixed is inserted and then heat-cured and molded, and the sealing material is formed on the mold. A compression molding method or the like in which a semiconductor chip fixed on a substrate is immersed therein and heat-cured and then released from a mold is used.
Examples of the injection method include dispenser, transfer molding, injection molding and the like. For the heating, methods such as hot air circulation, infrared rays and high frequency can be used.
The heating condition is preferably about 80 to 230 ° C. and about 1 minute to 24 hours, for example. For the purpose of reducing internal stress generated during heat curing, for example, after pre-curing at 80 to 120 ° C. for 30 minutes to 5 hours, post-curing is performed at 120 to 180 ° C. for 30 minutes to 10 hours. it can.

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

As the acidic curing catalyst, a cationic polymerization initiator is preferable, and a photocationic polymerization initiator is particularly preferable. Examples of the cationic polymerization initiator include those having an onium salt such as an iodonium salt, a sulfonium salt, and a diazonium salt, and these can be used alone or in combination of two or more. Examples of active energy ray cationic polymerization initiators include metal fluoroboron complex salts and boron trifluoride complex compounds (US Pat. No. 3,379,653), bis (perfluoroalkylsulfonyl) methane metal salts (US Pat. No. 3,586,616), aryldiazonium Compound (US Pat. No. 3,708,296), aromatic onium salt of group VIa element (US Pat. No. 4,058,400), aromatic onium salt of group Va element (US Pat. No. 4069055), dicarbonyl chelate of group IIIa to Va element (US Pat. No. 4068091), thiopyrylium salts (US Pat. No. 4,139,655), group VIb elements in the form of MF ₆ -anions (US Pat. No. 4,161,478; M is selected from phosphorus, antimony and arsenic). Arylsulfonium complex salts (US Pat. No. 4,231,951), Aromatic iodonium and aromatic sulfonium complexes (US Pat. No. 4,256,828), and bis [4- (diphenylsulfonio) phenyl] sulfide-bis-hexafluorometal salts (Journal of Polymer Science, Polymer Chemistry, Volume 2, 1789 (1984)). In addition, mixed ligand metal salts of iron compounds and silanol-aluminum complexes can also be used.
As specific examples, “Adekaoptomer SP150”, “Adekaoptomer SP170” (all manufactured by Asahi Denka Kogyo Co., Ltd.), “UVE-1014” (manufactured by General Electronics Co., Ltd.), “CD-1012” (Sartomer Company) Product), “RP-2074” (manufactured by Rhodia), and the like. The amount of the cationic polymerization initiator used is preferably 0.01 to 50 parts by weight and more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the epoxy resin component.

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

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

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

  The curable resin composition B of the present invention can be obtained by uniformly mixing each component. It is also possible to dissolve in an organic solvent such as polyethylene glycol monoethyl ether, cyclohexanone, or γ-butyrolactone and make it uniform, and then use it after removing the solvent by drying. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition B of the present invention and the solvent. The curable resin composition B of the present invention can be cured by irradiating with ultraviolet rays, but the amount of ultraviolet irradiation varies depending on the curable resin composition, and therefore is determined by the respective curing conditions. What is necessary is just the irradiation amount which a photocurable curable resin composition hardens | cures, and should just satisfy | fill the hardening conditions with which the adhesive strength of hardened | cured material is favorable. Since it is necessary for light to be transmitted through the details during the curing, the epoxy resin and the curable resin composition B of the present invention are highly transparent. Moreover, it is difficult for these epoxy resin-based photocuring to be completely cured only by light irradiation, and in applications where heat resistance is required, it is necessary to complete reaction curing by heating after light irradiation.

  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. Although it changes depending on the blending of the curable resin composition B, the higher the temperature range, the more effective the curing is after light irradiation, and the short heat treatment is effective. Further, the lower the temperature, the longer the heat treatment. By performing such heat after-curing, an effect of aging treatment is obtained.

  Moreover, since the shape of the cured product obtained by curing these curable resin compositions B can be variously selected depending on the application, it is not particularly limited. For example, it may be a film shape, a sheet shape, a bulk shape, or the like. . 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, or the like can be applied. Although it is mentioned, it is not limited to these. As the mold, polishing glass, hard stainless steel polishing plate, polycarbonate plate, polyethylene terephthalate plate, polymethyl methacrylate plate, or the like can be applied. In addition, a polyethylene terephthalate film, a polycarbonate film, a polyvinyl chloride film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a polyimide film, or the like can be applied in order to improve releasability from the mold.

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

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

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

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

  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 a printed circuit board, wire coating, etc.), sealants, additives to other resins, and the like. Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives. Among these, adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).

  EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified. The present invention is not limited to these examples. In the examples, the epoxy equivalent was measured using an E-type viscometer at JIS K-7236 and the viscosity at 25 ° C. The analysis conditions in gas chromatography (hereinafter referred to as “GC”) were as follows: HP5-MS (0.25 mm ID x 15 m, film thickness 0.25 μm) was used for the separation column, and the column oven temperature was set to the initial temperature 100. The temperature was set at 0 ° C., the temperature was raised at a rate of 15 ° C. per minute, and held at 300 ° C. for 60 minutes. Helium was used as a carrier gas. Furthermore, the measurement in gel permeation chromatography (hereinafter referred to as “GPC”) is as follows. The column is a Shodex SYSTEM-21 column (KF-803L, KF-802.5 (× 2), KF-802), the linking eluent is tetrahydrofuran, and the flow rate is 1 ml / min. The column temperature was 40 ° C., detection was performed by RI, and a standard polystyrene manufactured by Shodex was used for the calibration curve.

Example 1
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen while adding 79.3 parts dicyclopentadiene, 40.3 parts 1,1,3,3-tetramethyldisiloxane, and 200 parts toluene. In addition, 10 mg of 1% hexachloroplatinic acid / THF solution was added, and the reaction was carried out at 50 ° C. Every 8 hours of reaction, 10 mg of 1% hexachloroplatinic acid / THF solution was added, and the reaction was carried out for a total of 40 hours. Thereafter, washing with water was repeated 5 times, and toluene was distilled off under reduced pressure by heating with a rotary evaporator, thereby obtaining the following formula (4).

で表されるジオレフィン樹脂（Ｄ１）１０５部を得た。

105 parts of diolefin resin (D1) represented by these were obtained.

Example 2
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen while adding 79.3 parts dicyclopentadiene, 53.9 parts 1,1,3,3-tetramethyldisiloxane, and 200 parts toluene. In addition, 10 mg of a 1% hexachloroplatinic acid / THF solution was added, reacted at 50 ° C. for 5 hours, and at 60 ° C. for 2 hours, and then reacted by raising the temperature to 80 ° C. In addition, 10 mg of 1% hexachloroplatinic acid / THF solution was added every time the reaction was performed for 8 hours, and the reaction was performed for a total of 40 hours. Thereafter, washing with water is repeated 5 times, and toluene is distilled off under reduced pressure by heating with a rotary evaporator, whereby the following formula (5)

で表されるジオレフィン樹脂（Ｄ２）を１１９部得た。ゲルパーエーションクロマトグラフィー（以下ＧＰＣ）により、くり返し数ｎは０．３７であることを確認した。

119 parts of a diolefin resin (D2) represented by It was confirmed by gel permeation chromatography (hereinafter referred to as GPC) that the repetition number n was 0.37.

Example 3
A flask equipped with a stirrer, a reflux condenser, and a stirrer was charged with 15 parts of water, 0.95 parts of 12-tungstophosphoric acid, 0.78 parts of disodium hydrogen phosphate, and di-tallow alkyldimethylammonium acetate while purging with nitrogen. After adding 7 parts (50% by weight lion solution manufactured by Lion Akzo, Acquard 2HT acetate) to produce a tungstic acid catalyst, 120 parts of toluene, 81 parts of the diolefin compound D1 obtained in Example 2, Furthermore, it was set as the liquid of a suspension state by stirring again. The temperature of this solution was raised to 50 ° C., and while stirring vigorously, 55 parts of 35% hydrogen peroxide solution was added and stirred as it was at 50 ° C. for 15 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. Next, after neutralizing with a 1% by weight aqueous sodium hydroxide solution, 25 parts of a 20% by weight aqueous sodium thiosulfate solution was added, stirred for 30 minutes, and allowed to stand. The organic layer separated into two layers was taken out, 15 parts of activated carbon (CP2 manufactured by Ajinomoto Fine-Techno) and 5 parts of silica gel were added thereto, and the mixture was stirred at room temperature for 3 hours and then filtered. The obtained filtrate was washed with 100 parts of water three times, and the organic solvent was distilled off from the obtained organic layer to obtain the following formula (6).

を主成分とする化合物（ＥＰ１）を７８部得た。ＧＰＣの測定結果より、式（６）の骨格の化合物を９８％含有していることを確認した。さらに、またエポキシ当量は１９０ｇ／ｅｑ．であり、室温で液状であった。エポキシ樹脂ＥＰ１をポリ容器で５℃で１週間保管するとＥＰ１は結晶化しており、その融点は９８℃（示唆熱分析）であった。構造の同定はＧＣ−ＭＳ、核磁気共鳴法（^１Ｈ−ＮＭＲ）により行った。^１Ｈ−ＮＭＲデータを以下に示す。

78 parts of a compound (EP1) containing as a main component was obtained. From the measurement results of GPC, it was confirmed that 98% of the compound having the skeleton of formula (6) was contained. Furthermore, the epoxy equivalent was 190 g / eq. And was liquid at room temperature. When the epoxy resin EP1 was stored in a plastic container at 5 ° C. for 1 week, EP1 was crystallized and its melting point was 98 ° C. (suggested thermal analysis). The structure was identified by GC-MS and nuclear magnetic resonance ( ¹ H-NMR). ¹ H-NMR data is shown below.

Example 4
9.5 parts of the epoxy resin (EP1) of the present invention obtained in Example 3, alicyclic epoxy resin A (3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, manufactured by Nippon Kayaku Co., Ltd. 6.6 parts of SEJ-01R), 8.4 parts of methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd., Ricacid MH700G) as a curing agent, 1,3,4-cyclohexanetricarboxylic acid-3,4 -4.9 parts of anhydride (H-TMAn) and 0.2 part of hexadecyltrimethylammonium hydroxide (25% methanol solution manufactured by Tokyo Chemical Industry Co., Ltd.) as a curing accelerator were blended and degassed for 20 minutes. The curable composition B of the present invention was obtained.

Example 5
Except that the alicyclic epoxy resin A in Example 4 was changed to 9.7 parts of the alicyclic epoxy resin C (bis (3,4-epoxycyclohexylmethyl) adipate, ERL-4299 manufactured by Dow Chemical) in the same manner, The curable composition D of this invention was obtained.

(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. Using these test pieces, a dynamic viscoelasticity test was performed under the conditions shown below. The cured product of the curable composition B had a Tg of 176 ° C., and the cured product of the curable resin composition D had a Tg of 96 ° C. Measurement conditions Dynamic viscoelasticity measuring instrument: manufactured by TA-instruments, DMA-2980 Measurement temperature range: -30 ° C to 280 ° C Temperature rate: 2 ° C / min Specimen size: 5 mm x 50 mm Is about 800 μm). Analysis condition Tg: Tan-δ peak point in DMA measurement was defined as Tg.

Claims (4)

An epoxy resin is obtained by oxidizing a diolefin resin obtained by reacting an alkylsiloxane having two Si—H bonds with dicyclopentanediene and / or methyldicyclopentadiene at 50 ° C. or lower. Production method of epoxy resin. The following formula (7) obtained by oxidizing a diolefin resin obtained by reacting an alkylsiloxane having two Si—H bonds with dicyclopentadiene and / or methyldicyclopentadiene.

(In the formula, a plurality of R ¹ and R ² exist independently, R ¹ represents an alkyl group having 1 to 6 carbon atoms, R ² represents a hydrogen atom or a methyl group. (P) represents * Bonded to Si at the position.)
Method for producing an epoxy resin according to claim 1 compound represented by characterized that you containing more than 98%. Epoxy equivalent is 190 g / eq. It is the following, The manufacturing method of the epoxy resin as described in any one of Claim 1 or 2 characterized by the above-mentioned . Following formula (1)

(In the formula, a plurality of R ¹ and R ² exist independently, R ¹ represents an alkyl group having 1 to 6 carbon atoms, R ² represents a hydrogen atom or a methyl group. (P) represents * Bonded to Si at the position.)
The epoxy as described in any one of Claims 1-3 obtained by epoxidizing the diolefin resin characterized by these using either hydrogen peroxide or a peracid. Manufacturing method of resin.