KR20140006811A - Curable resin composition and cured article - Google Patents

Abstract

The curable resin composition of the present invention is hydrosilylation with a ladder-like silsesquioxane (A) capable of reacting with each other to form a carbon-silicon bond by hydrosilylation and a straight chain polysiloxane (B) having a molecular weight of 100 to 9000. Catalyst (C). The curable resin composition of the present invention is an isocyanuric acid compound (D) capable of reacting with the ladder silsesquioxane (A) and / or the linear polysiloxane (B) to form a carbon-silicon bond by hydrosilylation. It may also include more. According to the curable resin composition of this invention, the hardened | cured material which has physical properties, such as high temperature heat resistance, flexibility, transparency, heat yellowing resistance, and photoyellowing resistance, can be obtained.

Description

Curable resin composition and hardened | cured material {CURABLE RESIN COMPOSITION AND CURED ARTICLE}

The present invention relates to a curable resin composition and a sealant comprising the same, a cured product thereof, an LED, and an optical semiconductor device.

As a material which coat | covers a semiconductor element in the high heat resistance and high withstand voltage semiconductor device, the material which has heat resistance of 150 degreeC or more is calculated | required. In particular, as a material for coating optical materials such as LED devices, in addition to heat resistance, it is required to have physical properties such as flexibility, transparency, heat yellowing resistance, and light yellowing resistance. In the conventional epoxy type and modified silicone resin, when using as a sealing agent, when Tj = 180 degreeC energization test was performed, there existed a problem that the element top burns black. Moreover, in dimethyl silicone resin, although it has heat resistance up to 150 degreeC, embrittlement advances when it heats to 180 degreeC, As a result, when Tj = 180 degreeC energization test, a crack generate | occur | produces and also the barrier property, such as water vapor, is low and reliable There was a problem of low.

As a material having high heat resistance and good heat dissipation, at least one first organosilicon polymer having a crosslinked structure by siloxane (Si-O-Si binder) and at least one second having a linear connection structure by siloxane Synthetic high molecular compounds containing at least one of a third organosilicon polymer having a molecular weight of 20,000 to 800,000, in which an organosilicon polymer is linked by a siloxane bond, have been reported (Patent Document 1). However, the specific synthesis method of these synthetic high molecular compounds is not described, and the physical property of these materials is still not satisfactory.

A resin composition for sealing an optical device having excellent transparency, UV resistance, and thermal coloring property, wherein the liquid silsesquioxane is a cage structure containing aliphatic carbon-carbon unsaturated bonds and no H-Si bonds, and H-Si. Resin composition for optical element sealing containing at least one silsesquioxane selected from the group consisting of a liquid silsesquioxane which is a cage-like structure containing a bond and not containing an aliphatic carbon-carbon unsaturated bond. Is disclosed (patent document 2). However, the hardened | cured material of cage silsesquioxane is comparatively hard, and since it lacks flexibility, it is easy to produce a crack and a crack.

Moreover, (A) organic compound, such as triallyl isocyanurate, which contains at least 2 carbon-carbon double bonds which have reactivity to SiH group, and (B) contains at least 2 SiH groups in 1 molecule, A curable composition containing a compound such as a chain and / or cyclic polyorganosiloxane, and (C) a hydrosilylation catalyst as an essential component is disclosed (Patent Document 3). However, physical properties such as crack resistance of these materials are not satisfactory yet.

Japanese Patent Laid-Open No. 2006-206721 Japanese Patent Publication No. 2007-31619 Japanese Patent Laid-Open No. 2002-314140

An object of the present invention is to provide a curable resin composition that gives a cured product having physical properties such as high temperature heat resistance, flexibility, transparency, heat yellowing resistance, and light yellowing resistance.

Another object of the present invention is to provide a sealant for an optical semiconductor obtained after physical curing such as high temperature heat resistance, flexibility, transparency, heat yellowing resistance, light yellowing resistance.

In addition, another object of the present invention is to provide a cured product having physical properties such as high temperature heat resistance, flexibility, transparency, heat yellowing resistance, and light yellowing resistance.

In addition, another object of the present invention is to provide an LED having physical properties such as high temperature heat resistance, flexibility, transparency, heat yellowing resistance, light yellowing resistance.

Still another object of the present invention is to provide an optical semiconductor device having excellent physical properties such as high temperature heat resistance, flexibility, transparency, heat yellowing resistance, and light yellowing resistance.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, when hardening the composition containing ladder type silsesquioxane, the linear polysiloxane which has a specific molecular weight, and a hydrosilylation catalyst, high temperature heat resistance, flexibility, transparency, heat resistance It discovered that hardened | cured material excellent in physical properties, such as yellowing and light yellowing, was obtained and completed this invention.

That is, the present invention is a ladder-type silsesquioxane (A) capable of reacting with each other to form a carbon-silicon bond by hydrosilylation, a straight chain polysiloxane (B) having a molecular weight of 100 to 9000, and a hydrosilylation catalyst (C It provides a curable resin composition comprising a).

The curable resin composition of the present invention is an isocyanuric acid compound (D) capable of reacting with the ladder silsesquioxane (A) and / or the linear polysiloxane (B) to form a carbon-silicon bond by hydrosilylation. It may also include more.

This invention also provides the sealing agent for optical semiconductors containing the said curable resin composition.

The present invention also provides a cured product obtained by curing the curable resin composition.

The present invention also provides an LED including the cured product and an optical semiconductor device including the same.

According to the present invention, since the curable resin composition includes a ladder-type silsesquioxane, a straight chain polysiloxane having a specific molecular weight, and a hydrosilylation catalyst, when it is thermoset, the hydrosilylation reaction proceeds and the transparency is excellent. Hardened | cured material excellent in high temperature heat-resistant yellowing and flexibility is obtained. This hardened | cured material does not yellow even if it is exposed for a long time under the high temperature of 150 degreeC or more, and since it is excellent in flexibility, it is hard to produce a crack and a crack. Therefore, curable resin composition of this invention is useful as a sealing agent for light sources of the next generation. Further, according to the present invention, LEDs and optical semiconductor devices excellent in various physical properties such as high temperature heat resistance, flexibility, transparency, heat yellowing resistance, and light yellowing resistance are obtained.

1 is a graph showing the light transmittance of the cured product 1 obtained in Example 1. FIG.

[Curable resin composition]

The curable resin composition of the present invention is hydrosilylation with a ladder-like silsesquioxane (A) capable of reacting with each other to form a carbon-silicon bond by hydrosilylation and a straight chain polysiloxane (B) having a molecular weight of 100 to 9000. Catalyst (C) is included. As ladder type silsesquioxane (A) which can react with each other and form a carbon-silicon bond by hydrosilylation, and linear polysiloxane (B) of molecular weight 100-9000, a ladder which has an aliphatic carbon-carbon double bond in a molecule | numerator A combination of a type silsesquioxane (hereinafter referred to as vinyl ladder silsesquioxane) and a linear polysiloxane having a Si-H bond in the molecule (hereinafter referred to as Si-H type linear polysiloxane), or Si-H in the molecule A combination of a ladder-type silsesquioxane having a bond (hereinafter referred to as Si-H ladder ladder silsesquioxane) and a straight chain polysiloxane having an aliphatic carbon-carbon double bond in the molecule (hereinafter referred to as vinyl straight chain polysiloxane) Can be mentioned.

[Ladder type silsesquioxane (A)]

In general, ladder type silsesquioxanes are polysiloxanes having a crosslinked three-dimensional structure. Polysiloxane is a compound having a main chain composed of siloxane bonds (Si-O-Si), the basic structural unit of the formula (M), (D), (T), (Q) (hereinafter, M unit, D unit, respectively) , T units, and Q units).

In said formula, R represents the atom or atom group couple | bonded with the silicon atom. The M unit is a unit containing a monovalent group in which a silicon atom is bonded to one oxygen atom, and the D unit is a unit containing a divalent group in which a silicon atom is bonded to two oxygen atoms, and the T unit is a 3 in which a silicon atom is bonded to three oxygen atoms. It is a unit containing a valent group, and a Q unit is a unit containing the tetravalent group which the silicon atom couple | bonded with four oxygen atoms.

Silsesquioxane is a polysiloxane of the T unit to the main unit, its empirical formula (Basic Structure) is represented by RSiO _3/2. As a structure of the Si-O-Si skeleton of silsesquioxane, a random structure, a ladder structure, and a basket structure are known. The ladder silsesquioxane contained in the curable resin composition of this invention is silsesquioxane which has the Si-O-Si frame | skeleton of a ladder structure.

The ladder silsesquioxane can be represented by the following general formula (L), for example.

In the said general formula (L), p is an integer of 1 or more (for example, 1-5000, Preferably 1-2000, More preferably, 1-1000). Each R is the same or different and is a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a hydroxyl group, an alkoxy group, an alkenyloxy group, an aryloxy group, an aralkyloxy group, an acyloxy group, a mercapto group (thiol group), Alkylthio group, alkenylthio group, arylthio group, aralkylthio group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, amino group or substituted amino group (such as mono or dialkylamino group, acylamino group), epoxy group, halogen Atom, group etc. which are represented by following General formula (1) are mentioned.

Each R in the said General formula (1) may be same or different, and is the same as R in the said General formula (L).

As said hydrocarbon group, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, the group which these couple | bonded two or more is mentioned. As an aliphatic hydrocarbon group, an alkyl group, an alkenyl group, and an alkynyl group are mentioned. As the alkyl group, such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, isooctyl, decyl, dodecyl group, etc. C _{1 -20} alkyl group (preferably, C _{1 -10} is an alkyl group, more preferably C _{1 -4} alkyl group), and the like. As the alkenyl group, for example, vinyl, allyl, metalyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3- pen, and the like butenyl, 4-pentenyl, 5-hexenyl group and the like of C _{2 -20} alkenyl groups (preferably, C _{2 -10} alkenyl group, more preferably C _{2 -4} alkenyl group). As the alkynyl group, for example, such as, ethynyl propynyl group containing C _{2 -20} alkynyl group and the like (preferably made to have, C _{2 -10} alkynyl groups, more preferably C _{2 -4} alkynyl group).

As the alicyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, C _{3 -12} cycloalkyl group such as a dodecyl group; C _3-12 cycloalkenyl groups such as a cyclohexenyl group; And the like can be mentioned bicyclo heptanyl, bicyclo heptenyl group such as C _{4 -15} crosslinked cyclic hydrocarbon group.

The aromatic hydrocarbon group, and examples thereof include a phenyl group, a naphthyl group such as C _{6 -14} aryl group (in particular, C _{6 -10} aryl group).

As a group which the aliphatic hydrocarbon group and the alicyclic hydrocarbon group couple | bonded, a cyclohexyl methyl, a methylcyclohexyl group, etc. are mentioned, for example. A combination of aliphatic hydrocarbon group and aromatic hydrocarbon group, a benzyl, phenethyl group of C _{7 -18} aralkyl group (particularly, C _{7 -10} aralkyl groups), such as thinner or pushing of C _{6 -10} aryl -C _{2 -6} alkenyl group, Tall C _{2 -4} alkenyl substituted, such as such as C _{1 -4} alkyl-substituted aryl group, a styryl group-there may be mentioned aryl group, and the like.

The hydrocarbon group may have a substituent. Carbon number of a substituent is 0-20, Preferably it is 0-10. As said substituent, For example, Halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom; A hydroxyl group; Alkoxy groups such as methoxy and ethoxy groups; Alkenyloxy groups such as allyloxy group; An aryloxy group such as a phenoxy group; Aralkyloxy groups such as benzyloxy group; Acyloxy groups such as acetyloxy, propionyloxy, (meth) acryloyloxy and benzoyloxy groups; A mercapto group; Alkylthio groups such as methylthio and ethylthio groups; Alkenylthio groups such as allylthio group; Arylthio groups such as phenylthio group; Aralkylthio groups such as benzylthio group; A carboxyl group; Alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl group; Aryloxycarbonyl groups such as phenyloxycarbonyl group; Aralkyloxycarbonyl groups such as benzyloxycarbonyl group; An amino group; Mono or dialkylamino groups such as methylamino, dimethylamino and diethylamino groups; Acylamino groups such as acetylamino and benzoylamino groups; Epoxy group-containing groups such as glycidyloxy group; An oxetanyl group-containing group such as an ethyloxetanyloxy group; Acyl groups such as acetyl, propionyl and benzoyl groups; Oxo group; These two or more, as needed, and the like groups bonded via an alkylene-C _{1 -6.}

As the alkoxy group in the above R, for example, methoxy, ethoxy, propoxy, isopropyloxy, butoxy, isobutylene oxide is the preferred C _{1 -6} alkoxy group (such as time, C _{1 -4} alkoxy And the like). As the alkenyloxy group, such as allyl (preferably, C _{2 -4} alkenyloxy group) C _{2 -6} alkenyloxy group such as oxy, and the like. As the aryloxy group, such as phenoxy, tolyloxy, naphthyloxy group, etc., the aromatic ring C _{1 - 4} have a substituent such as alkyl group, C _{2 -4} alkenyl group, a halogen atom, C _{1 -4} alkoxy group and the like can be also C _{6 -14} aryloxy group which. As the aralkyl oxy group, for example benzyloxy, and the like, C _7-18 aralkyl-oxy group such as a phenethyl tilok time. As the acyl oxy group, for example, and the like can be mentioned C _{1 -12} acyloxy group such as acetyloxy, propionyloxy, benzoyloxy group.

As the alkylthio group, for example methylthio and the like, ethyl tee or omissions C _{1 -6} alkylthio group (preferably, C _{1 -4} alkylthio group). Examples of alkenyl nilti get, there may be mentioned allyl, such as coming T C _{2 -6} alkenyl nilti come (coming preferably, C _{2 -4} alkenyl nilti), and the like. As the arylthio group, for example, have a substituent such as phenylthio, alkylthio-tolyl, naphthyl tilti, C _{1 -4} alkyl group to the aromatic ring, such as importing, C _{2 -4} alkenyl group, a halogen atom, C _{1 -4} alkoxy group and the like may be C _{6 -14} arylthio that. As the import are alkylthio, for example benzylthio, and the like, such as a phenethyl tilti import of C _{7 -18} aralkyl thio group. As an alkoxycarbonyl group, _C1-6 alkoxy-carbonyl groups, such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl group, etc. are mentioned, for example. As the aryloxy group, for example phenoxycarbonyl, tolyloxy-carbonyl, naphthyloxy group, etc. C _{6 -14} aryloxy-carbonyl group, and the like. As the alkyloxycarbonyl group are, for example, a benzyloxycarbonyl group such as a C _{7 -18} aralkyloxy-carbonyl group, and the like. Examples of mono- or di-alkylamino group, and the like can be mentioned methylamino, ethylamino, dimethylamino, diethylamino group, such as the mono- or di -C _{1 -6} alkylamino group. As the acylamino group, for example, and the like can be mentioned C _{1 -11} acylamino group such as acetylamino, propionylamino, benzoylamino group. As a halogen atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

In groups represented by the above formula (1), examples of each of R, each represent a hydrogen atom, C _{1 -10} alkyl groups (particularly, C _{1 -4} alkyl group), C _{2 -10} alkenyl groups (especially, C _{2 -4} alkyl group), C _{3 -12} cycloalkyl, C _3-12 cycloalkenyl group, to the aromatic ring C _{1 -4} alkyl, C _{2 -4} alkenyl group, a halogen atom, C ₆ which may have a substituent such as a C _{1 -4} alkoxy group _{- 14} aryl group, C _{7 -18} aralkyl groups, C _{6 -10} aryl -C _{2 -6} alkenyl group, a hydroxyl group, C _{1 -6} is preferably an alkoxy group, a halogen atom.

As the ladder silsesquioxane, in the general formula (L), a substituted or unsubstituted hydrocarbon group is preferably occupied by 50 mol% or more (more preferably 80 mol% or more, particularly preferably 90 mol% or more). Do. In particular, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (particularly, an alkyl group having 1 to 4 carbon atoms such as methyl or ethyl group), an aryl group having 6 to 10 carbon atoms (particularly a phenyl group), and an aralkyl group having 7 to 10 carbon atoms ( In particular, it is preferable that benzyl group) occupies 50 mol% or more (more preferably 80 mol% or more, Especially preferably, 90 mol% or more).

Ladder silsesquioxane can be manufactured by a well-known method. For example, the ladder type silsesquioxane represented by the said general formula (L) is 1 type, or 2 or more types of the hydrolyzable silane compound represented by the following general formula (2), or the valence represented by the said general formula (1) It can obtain by hydrolyzing and condensation reaction (sol-gel reaction) of 1 type, or 2 or more types of a decomposable silane compound, and 1 or 2 types or more of the silane compound represented by following General formula (3) or (3 ').

(In formula, R is the same as the above, and three X is the same or different, and represents a hydrolysable group or a hydroxyl group.)

(In formula, R and X are the same as the above, and some R may be same or different.)

In addition, the hydrolyzable silane compound represented by the formula (2) is used for the formation of the T unit of the ladder silsesquioxane, and the silane compound represented by the formula (3) or (3 ') functions as a terminal sealant, Used to form M units of ladder silsesquioxane.

As a hydrolysable group in X, what is necessary is just a group which can form a siloxane bond by hydrolysis and silanol condensation, For example, Halogen atoms, such as a chlorine atom, a bromine atom, an iodine atom; C _{1 -10} alkoxy group such as methoxy, ethoxy, propoxy on; Acetyloxy, there may be mentioned C _{1 -10} acyloxy group such as propionyloxy, benzoyloxy group. Of these, a chlorine atom, preferably a C _{1 -4} alkoxy.

The hydrolysis-condensation reaction is, for example, in the presence of a silanol condensation catalyst, condensing the silane compound with silanol in water or a mixed solvent of water and an organic solvent, and during the reaction or after the reaction, the solvent and / or by-products. It can carry out by distilling off (alcohol etc.). The reaction temperature is -78 ° C to 150 ° C, preferably -20 ° C to 100 ° C. The usage-amount of water is 1 mol or more (for example, 1-20 mol, Preferably 1-10 mol) with respect to 1 mol of total of a silane compound.

As said organic solvent, For example, aliphatic hydrocarbons, such as hexane, heptane, an octane; Alicyclic hydrocarbons such as cyclohexane; Aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; Halogenated hydrocarbons such as chloroform, dichloromethane and 1,2-dichloroethane; Ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Esters such as methyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate; Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; Nitriles such as acetonitrile, propionitrile, and benzonitrile; Alcohols such as methanol, ethanol, isopropyl alcohol and butanol; A mixed solvent thereof, and the like. The usage-amount of an organic solvent is 0.5-30 volume parts with respect to a total of 1 volume part of a silane compound, for example.

As the silanol condensation catalyst, an acid catalyst or a base catalyst can be used. As an acid catalyst, For example, inorganic acids, such as hydrochloric acid, a sulfuric acid, nitric acid, phosphoric acid, a boric acid; Phosphate esters; Carboxylic acids such as acetic acid and trifluoroacetic acid; Sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid and p-toluenesulfonic acid; Solid acids such as activated clay; Lewis acids, such as iron chloride, etc. are mentioned. As a base catalyst, For example, alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide; Hydroxides of alkaline earth metals such as barium hydroxide and magnesium hydroxide; Alkali metal carbonates such as sodium carbonate; Alkaline earth metal carbonates such as barium carbonate and magnesium carbonate; Alkali metal hydrogencarbonates such as sodium hydrogencarbonate; Alkali metal alkoxides such as sodium methoxide and sodium ethoxide; Alkaline earth metal alkoxides such as barium methoxide; Alkali metal phenoxides such as sodium phenoxide; Quaternary ammonium hydroxides such as tetraalkylammonium hydroxides such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide; Quaternary phosphonium hydroxides such as tetraalkylphosphonium hydroxides such as tetramethylammonium hydroxide and tetrabutylphosphonium hydroxide; Amines such as tertiary amines such as triethylamine, N-methylpiperidine, 4-dimethylaminopyridine, and 1,8-diazabicyclo [5.4.0] -7-undecene (DBU); Nitrogen containing aromatic heterocyclic compounds, such as a pyridine, etc. are mentioned. As the silanol condensation catalyst, fluorine compounds such as tetrabutylammonium fluoride, potassium fluoride and sodium fluoride can also be used.

The reaction product can be separated and purified by, for example, separation means such as washing with water, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination thereof.

<Vinyl type ladder silsesquioxane>

The vinyl ladder silsesquioxane is not particularly limited as long as it is a compound having a group having an aliphatic carbon-carbon double bond at the terminal or side chain in the ladder silsesquioxane, and is represented by the general formula (L), for example. In ladder type silsesquioxane, the compound in which at least 1 of terminal R and / or at least 1 of side chain R has an aliphatic carbon-carbon double bond is mentioned.

Examples of the group having an aliphatic carbon-carbon double bond include, for example, vinyl, allyl, metalyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 5-hexenyl group and the like of C _{2 -20} alkenyl groups (preferably C _{2 -10} alkenyl group, more preferably C _{2 -4} alkenyl group) ; Cyclohexenyl group, and the like of the cycloalkenyl group in the C _{3 -12;} C _{4 -15} crosslinked cyclic unsaturated hydrocarbon group such as bicyclo heptenyl group; C _{2 -4} alkenyl optionally substituted aryl group such as a styryl group; Thinner and the like. Further, the aliphatic carbon-in groups represented by the Formula (1) groups having the carbon-carbon double bond, C _{2 -20} at least one of three R aforementioned alkenyl group, a cycloalkenyl group of C _{3 -12,} C _4-15 crosslinked cyclic unsaturated hydrocarbon group, and includes C _{2 -4} alkenyl substituted aryl group, or the like thinner push airway.

As molecular weight of vinyl ladder silsesquioxane, it is 100-800,000, Preferably it is 200-100,000, More preferably, it is 300-20,000, Especially preferably, it is 500-4000. When the molecular weight of vinyl ladder silsesquioxane exists in this range, it is a liquid and low viscosity, and since it is compatible with the linear polysiloxane of Si-H type molecular weight 100-9000, it is easy to handle. The vinyl ladder silsesquioxane may be a mixture having various molecular weights in the above ranges. The content of the aliphatic carbon-carbon double bond in the vinyl ladder silsesquioxane is, for example, 0.0010 to 0.0040 mmol / g, preferably 0.0012 to 0.0030 mmol / g. In addition, the ratio (weight basis) of the aliphatic carbon-carbon double bond contained in vinyl ladder silsesquioxane is 3.0 to 9.0% in conversion of vinyl group, Preferably it is 3.7 to 5.7%.

The vinyl ladder silsesquioxane is a hydrolyzable silane compound represented by the formula (2) in the above-described method of producing a ladder silsesquioxane, wherein at least a compound in which R has an aliphatic carbon-carbon double bond is used And, as the silane compound represented by the formula (3) or (3 '), at least one of R can be produced by using at least a compound having an aliphatic carbon-carbon double bond.

The vinyl ladder silsesquioxane is a ladder-type silsesquioxane (A1) having one or more hydrolyzable groups or hydroxyl groups as R in the ladder silsesquioxanes represented by the general formula (L). (Hereinafter, it may be simply called "ladder type silsesquioxane (A1)"), and it can manufacture by making 1 type, or 2 or more types of silane compound (S1) represented by following General formula (4) react. .

Wherein R is the same as above, and three R may be the same or different, provided that at least one of R is an aliphatic carbon-carbon double bond and X is a hydrolyzable group or hydroxyl I show a practical skill)

The hydrolyzable group in R of ladder type silsesquioxane (A1), the hydrolyzable group in X of silane compound (S1) represented by General formula (4), and the aliphatic carbon-carbon double bond in R The group which has the same thing as the group which has a hydrolysable group and an aliphatic carbon-carbon double bond mentioned above is mentioned. As the hydrolyzable group in the R of the ladder-type silsesquioxane (A1), methoxy, C _{1 -4} alkoxy, such as ethoxy group is particularly preferred.

In the silane compound (S1) represented by the above formula (4), the remaining R except for the group having an aliphatic carbon-carbon double bond is the same or different, and a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (particularly, An alkyl group having 1 to 4 carbon atoms such as methyl or ethyl group), an aryl group having 6 to 10 carbon atoms (especially a phenyl group), or an aralkyl group having 7 to 10 carbon atoms (especially a benzyl group).

As the silane compound (S1) represented by the general formula (4), more specifically, monohalogenated vinylsilane, monohalogenated allylsilane, monohalogenated 3-butenylsilane, monoalkoxyvinylsilane, monoalkoxyallylsilane, monoalkoxy3- Butenylsilane etc. are mentioned.

Representative examples of the monohalogenated vinylsilanes include chlorodimethylvinylsilane, chloroethyl methylvinylsilane, chloromethylphenylvinylsilane, chlorodiethylvinylsilane, chloroethylphenylvinylsilane, and chlorodiphenylvinylsilane.

Representative examples of the monohalogenated allylsilane include allylchlorodimethylsilane, allylchloroethylmethylsilane, allylchloromethylphenylsilane, allylchlorodiethylsilane, allylchloroethylphenylsilane, allylchlorodiphenylsilane, and the like.

Representative examples of the monohalogenated 3-butenylsilane include 3-butenylchlorodimethylsilane, 3-butenylchloroethylmethylsilane, 3-butenylchloromethylphenylsilane, 3-butenylchlorodiethylsilane, and 3-butenylchloro Ethylphenylsilane, 3-butenylchlorodiphenylsilane, and the like.

Representative examples of the monoalkoxy vinyl silane include methoxy dimethyl vinyl silane, ethyl methoxy methyl vinyl silane, methoxy methyl phenyl vinyl silane, diethyl methoxy vinyl silane, ethyl methoxy phenyl vinyl silane, methoxy diphenyl vinyl silane and ethoxy dimethyl. Vinyl silane, ethoxy ethyl methyl vinyl silane, ethoxy methyl phenyl vinyl silane, ethoxy diethyl vinyl silane, ethoxy ethyl phenyl vinyl silane, etc. are mentioned.

Representative examples of the monoalkoxy allylsilane include allylmethoxydimethylsilane, allylethylmethoxymethylsilane, allylmethoxymethylphenylsilane, allyldiethylmethoxysilane, allylethylmethoxyphenylsilane, allylmethoxydiphenylsilane and allylethoxy. Dimethyl silane, allyl ethoxy ethyl methyl silane, allyl ethoxy methyl phenyl silane, allyl ethoxy diethyl silane, allyl ethoxy ethyl phenyl silane, etc. are mentioned.

Representative examples of the monoalkoxy3-butenylsilane include 3-butenylmethoxydimethylsilane, 3-butenylethylmethoxymethylsilane, 3-butenylmethoxymethylphenylsilane, 3-butenyldiethylmethoxysilane, and 3-butenyl Ethylmethoxyphenylsilane, 3-butenylmethoxydiphenylsilane, 3-butenylethoxydimethylsilane, 3-butenylethoxyethylmethylsilane, 3-butenylethoxymethylphenylsilane, 3-butenylethoxydi Ethyl silane, 3-butenyl ethoxy ethyl phenyl silane, 3-butenyl ethoxy diphenyl silane, etc. are mentioned.

Reaction of ladder type silsesquioxane (A1) and the silane compound (S1) represented by General formula (4) is normally performed in a solvent. As a solvent, For example, Aliphatic hydrocarbons, such as hexane, heptane, an octane; Alicyclic hydrocarbons such as cyclohexane; Aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; Halogenated hydrocarbons such as chloroform, dichloromethane and 1,2-dichloroethane; Ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Esters such as methyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate; Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; Nitriles such as acetonitrile, propionitrile, and benzonitrile; Alcohol, such as methanol, ethanol, isopropyl alcohol, butanol, etc. are mentioned. These solvents may be used alone or in combination of two or more.

The amount of the silane compound (S1) represented by the formula (4) is, for example, 1 to 20 based on 1 mole of the total of the reactive groups (hydrolyzable group, hydroxyl group) in the ladder-type silsesquioxane (A1). Moles, preferably 2 to 10 moles, more preferably about 5 to 9 moles.

The reaction of the ladder-type silsesquioxane (A1) and the silane compound (S1) represented by the formula (4) is carried out in the presence of a silanol condensation catalyst. As a silanol condensation catalyst, the thing of the said illustration can be used. As a silanol condensation catalyst, it is preferable to use a base catalyst.

The amount of the silanol condensation catalyst used is, for example, 0.1 to 10 moles, preferably 0.1 to 1.0 to 1 mole of the total of the reactive groups (hydrolyzable group, hydroxyl group) in the ladder-type silsesquioxane (A1). It's a mole. The amount of silanol condensation catalyst used may be a catalytic amount.

The reaction may be carried out in the presence of a polymerization inhibitor. Although reaction temperature can be suitably selected according to the kind of reaction component, a catalyst, etc., Usually, it is 0-200 degreeC, Preferably it is 20-100 degreeC, More preferably, it is 30-60 degreeC. The reaction may be carried out at ordinary pressure or may be carried out under reduced pressure or pressure. The atmosphere of the reaction is not particularly limited as long as it does not inhibit the reaction, and may be any one of air atmosphere, nitrogen atmosphere, argon atmosphere and the like, for example. In addition, reaction can also be performed by either method of a batch type, a semi batch type, and a continuous type.

In the said method, reactive groups (hydrolyzable groups, such as an alkoxy group, hydroxyl group, etc.) in ladder type silsesquioxane (A1), and reactive groups (alkoxy groups, etc.) in the silane compound (S1) represented by General formula (4) Hydrolyzable group and hydroxyl group) hydrolyze and condense (or condensate), and the vinyl ladder silsesquioxane which has an aliphatic carbon-carbon double bond in the corresponding molecule | numerator is produced | generated.

After completion of the reaction, the reaction product can be separated and purified by, for example, separation means such as washing with water, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination thereof. Can be.

<Si-H type ladder silsesquioxane>

The Si-H type ladder silsesquioxane is not particularly limited as long as it has a Si-H bond in the terminal or side chain of the ladder silsesquioxane, and is, for example, a ladder type silses represented by the general formula (L). In the quoxane, at least one of the terminal R and / or at least one of the side chains R is a group having a hydrogen atom or a Si—H bond. As group which has a Si-H bond, the group etc. which are at least 1 of 3 R in a group represented by the said General formula (1) are hydrogen atoms, etc. are mentioned, for example.

As a molecular weight of Si-H type ladder silsesquioxane, it is 100-800,000, Preferably it is 200-100,000, More preferably, it is 300-20,000, Especially preferably, it is 500-4000. When the molecular weight of Si-H type | mold ladder silsesquioxane exists in this range, since it is excellent in compatibility with the linear polysiloxane of the molecular weight of 100-9000 of a vinyl type, it is preferable. Si-H type | mold ladder silsesquioxane may be a mixture which has the various molecular weight of the said range. The content of the Si-H bond in the Si-H ladder silsesquioxane is, for example, 0.0001 to 0.005 mmol / g, preferably 0.0005 to 0.002 mmol / g. In addition, the ratio (weight basis) of the Si-H group contained in Si-H type | mold ladder silsesquioxane is 0.01 to 0.30%, Preferably it is 0.1 to 0.2%.

Si-H type ladder silsesquioxane is the hydrolyzable silane compound represented by General formula (2) in the manufacturing method of the said ladder type silsesquioxane, At least the compound whose R is a hydrogen atom is used, or General formula (3) ) Or (3 ') can be produced by using at least a compound in which at least one of R is a hydrogen atom.

The Si-H type ladder silsesquioxane is a ladder type silsesquioxane having one or more hydrolyzable groups or hydroxyl groups as R in the ladder silsesquioxanes represented by the general formula (L) ( A1) [ladder-type silsesquioxane (A1)] can be manufactured by making 1 type (s) or 2 or more types of silane compounds (S2) represented by following General formula (5) react.

(Wherein R is the same as above, and three R may be the same or different, provided that at least one of R is a hydrogen atom and X represents a hydrolyzable or hydroxyl group)

The hydrolyzable group in R of ladder type silsesquioxane (A1), and the hydrolyzable group in X of the silane compound (S2) represented by General formula (5) are the same as the hydrolyzable group mentioned above. . As the hydrolyzable group in the R of the ladder-type silsesquioxane (A1), methoxy, C _{1 -4} alkoxy, such as ethoxy group is particularly preferred.

In the silane compound (S2) represented by the above formula (5), the remaining R except for the hydrogen atom is the same or different, and a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (particularly, methyl, ethyl group, etc.) An alkyl group having 1 to 4 carbon atoms), an aryl group having 6 to 10 carbon atoms (particularly a phenyl group), or an aralkyl group having 7 to 10 carbon atoms (particularly a benzyl group).

As a silane compound (S2) represented by General formula (5), a monohalogenation silane, a monoalkoxy silane, etc. are mentioned more specifically.

Representative examples of the monohalogenated silane include chlorodimethylsilane, chloroethylmethylsilane, chloromethylphenylsilane, chlorodiethylsilane, chloroethylphenylsilane and chlorodiphenylsilane.

Representative examples of monoalkoxysilanes include methoxydimethylsilane, ethylmethoxymethylsilane, methoxymethylphenylsilane, diethylmethoxysilane, ethylmethoxyphenylsilane, methoxydiphenylsilane, ethoxydimethylsilane, and ethoxyethylmethylsilane , Ethoxymethylphenylsilane, ethoxydiethylsilane, ethoxyethylphenylsilane, and the like.

Reaction of ladder type silsesquioxane (A1) and silane compound (S2) represented by General formula (5) is normally performed in a solvent. As a solvent, the thing similar to the solvent used for reaction of the said ladder-type silsesquioxane (A1) and the silane compound (S1) represented by General formula (4) can be used.

The usage-amount of the silane compound (S2) represented by General formula (5) is 1-30 with respect to 1 mol of the sum total of the reactive group (hydrolyzable group, hydroxyl group) in ladder type silsesquioxane (A1), for example. Moles, preferably 1 to 10 moles, more preferably about 5 to 9 moles.

The reaction of the ladder type silsesquioxane (A1) and the silane compound (S2) represented by the formula (5) is performed in the presence of a silanol condensation catalyst. As the silanol condensation catalyst, an acid catalyst is usually used among the silanol condensation catalysts. The basic catalyst is not preferred because it reacts with the silane compound (S2) represented by the formula (5).

The amount of the silanol condensation catalyst used is, for example, 0.001 to 1 mole, preferably 0.002 to 0.01 to 1 mole of the total of the reactive groups (hydrolyzable group, hydroxyl group) in the ladder-type silsesquioxane (A1). It's a mole. The amount of silanol condensation catalyst used may be a catalytic amount.

The reaction may be carried out in the presence of a polymerization inhibitor. Although reaction temperature can be suitably selected according to the kind of reaction component, a catalyst, etc., it is usually -78 degreeC-120 degreeC, Preferably it is -30 degreeC-60 degreeC, More preferably, it is -10 degreeC-30 degreeC. The reaction may be carried out at ordinary pressure or may be carried out under reduced pressure or pressure. The atmosphere of the reaction is not particularly limited as long as it does not inhibit the reaction, and may be any one of air atmosphere, nitrogen atmosphere, argon atmosphere and the like, for example. The reaction may be carried out by any method such as batch type, semi-batch type, or continuous type.

In the said method, reactive groups (hydrolyzable groups, such as an alkoxy group, hydroxyl group, etc.) in ladder type silsesquioxane (A1), and reactive groups (alkoxy groups, etc.) in the silane compound (S2) represented by General formula (5) Hydrolyzable group and hydroxyl group) hydrolyze and condense (or condensate), and the Si-H type | mold ladder silsesquioxane which has Si-H bond in the corresponding molecule | numerator is produced | generated.

After completion of the reaction, the reaction product can be separated and purified by, for example, separation means such as washing with water, acid washing, alkali washing, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination thereof. Can be.

As ladder type silsesquioxane, what has aliphatic carbon-carbon double bond or Si-H bond in the terminal is preferable because it has the tendency which is excellent in compatibility in manufacture of a composition. In addition, having an aliphatic carbon-carbon double bond or a Si-H bond in the side chain is preferable because it tends to be inexpensive.

[Straight chain polysiloxane (B) of molecular weight 100-9000]

The linear polysiloxane (B) having a molecular weight of 100 to 9000 contained in the curable resin composition of the present invention is a linear siloxane compound having a molecular weight of 100 to 9000 having a main chain composed of siloxane bonds (Si-O-Si), and contains aliphatic carbon in the molecule. -Straight chain polysiloxane (vinyl type linear polysiloxane) which has a carbon double bond, and straight chain polysiloxane (Si-H type linear polysiloxane) which has Si-H bond in a molecule | numerator is mentioned.

The linear polysiloxane (B) having a molecular weight of 100 to 9000 can be represented by, for example, the following general formula (6).

In the said General formula (6), R is the same as the above. Provided that at least one of R is a group or hydrogen atom having an aliphatic carbon-carbon double bond. q is an integer of 1 or more (for example, 1 to 15, preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3). When q exceeds 15, compatibility with a ladder-type silsesquioxane (A) may worsen, and it is not preferable.

In groups represented by the above formula (6), examples of each of R, each represent a hydrogen atom, C _1-10 alkyl group (particularly, C _{1 -4} alkyl group), C _{2 -10} alkenyl groups (especially, C _{2 -4} alkyl group), C _{3 -12} cycloalkyl group, C _{3 -12} cycloalkenyl group, to the aromatic ring C _{1 -4} alkyl, C _{2 -4} alkenyl group, a halogen atom, C ₆ which may have a substituent such as a C _{1 -4} alkoxy group _{- 14} aryl group, C _{7 -18} aralkyl groups, C _{6 -10} aryl -C _{2 -6} alkenyl group, a hydroxyl group, C _{1 -6} is preferably an alkoxy group, a halogen atom.

Specific examples of the linear polysiloxane (B) include 1,1,3,3-tetramethylsiloxane, 1,1,3,3-tetramethyl-1,3-divinylsiloxane, 1,1,3,3,5, 5-hexamethyltrisiloxane, 1,1,3,3,5,5-hexamethyl-1,5-divinyltrisiloxane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, 1,1,1,3,5,5,5-heptamethyl-3-vinyltrisiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1,1,3, 3,5,5,7,7-octamethyl-1,7-divinyltetrasiloxane, 1,1,1,3,5,5,7,7,7-nonamethyltetrasiloxane, 1,1,1 , 3,5,5,7,7,7-nonamethyl-3-vinyltetrasiloxane, 1,1,1,3,5,7,7,7-nonamethyl-3,5-divinyltetrasiloxane, 1,1,3,3,5,5,7,7,9,9-decamethylheptasiloxane, 1,1,3,3,5,5,7,7,9,9-decamethyl-1, 9-divinylheptasiloxane, 1,1,1,3,5,5,7,7,9,9,9-undecamethylheptasiloxane, 1,1,1,3,5,5,7,7 , 9,9,9-undecamethyl-3-vinylheptasiloxane, 1,1,3,3,5,5,7,7,9,9-decamethyl-1,9-divinylheptasiloxane , Si-H or vinyl type having 1 to 10 (preferably 1 to 5) (Si-O) units Of, and the like can be mentioned straight-chain polydimethylsiloxane, a straight chain poly dialkyl siloxane (preferably a straight-chain poly-di C _{1 -10} alkyl siloxane), such as dimethyl silicone.

As said linear polysiloxane (B), the compound by which all or one part of alkyl groups, such as a methyl group, of the said compound of the said example was substituted by aryl groups, such as a phenyl group (preferably _C6-20 aryl group), for example, Si-H type or poly diaryl siloxane (preferably poly-di C _{6 -20} aryl siloxane) such as poly-diphenylsiloxane straight chain of the vinyl-type; Si-H type or the straight chain of the vinyl type, such as polyphenyl methyl siloxane poly alkylaryl siloxanes (preferably poly-C _{1 -10} alkyl, C _{6 -20} aryl siloxane); Copolymers composed of the above polyorganosiloxane units [dimethylsiloxane-methylvinylsiloxane copolymer, dimethylsiloxane-methylphenylsiloxane copolymer, dimethylsiloxane-methyl (3,3,3-trifluoropropyl) siloxane copolymer, dimethylsiloxane -Methyl vinylsiloxane-methylphenylsiloxane copolymer, etc.] etc. can be illustrated further.

The molecular weight of said linear polysiloxane (B) is 100-9000, Preferably it is 100-7000, More preferably, it is 100-5000, Especially preferably, it is 100-4000. When molecular weight exists in this range, the hardened | cured material excellent in compatibility with the said ladder-type silsesquioxane (A), and excellent in crack resistance will be obtained. The said linear polysiloxane (B) can be used individually or in combination of 2 or more types.

Curable resin composition of this invention may contain polysiloxanes other than the said ladder-type silsesquioxane (A) and linear polysiloxane (B) of molecular weight 100-9000.

Hydrosilylation Catalyst (C)

As a hydrosilylation catalyst (C) contained in curable resin composition of this invention, well-known catalysts for hydrosilylation reactions, such as a platinum type catalyst, a rhodium type catalyst, a palladium type catalyst, are illustrated. Specifically, platinum fine powder, platinum black, platinum supported silica fine powder, platinum supported activated carbon, complex of chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone and the like, olefin complex of platinum, platinum such as platinum-carbonylvinylmethyl complex, etc. Platinum-based catalysts such as platinum vinylmethylsiloxane complexes such as carbonyl complexes, platinum-divinyltetramethyldisiloxane complexes and platinum-cyclovinylmethylsiloxane complexes, platinum-phosphine complexes and platinum-phosphite complexes; Palladium type catalyst or rhodium type catalyst which contains a palladium atom or a rhodium atom instead of a platinum atom in a catalyst is mentioned. These may be used alone or in combination of two or more. Especially, a platinum vinylmethylsiloxane complex is preferable at the point with favorable reaction rate.

[Isocyanuric Acid Compound (D)]

The curable resin composition of the present invention is an isocyanuric acid compound (D) capable of reacting with the ladder silsesquioxane (A) and / or the linear polysiloxane (B) to form a carbon-silicon bond by hydrosilylation. It may also include. As such an isocyanuric acid compound (D), the isocyanuric acid compound which has an aliphatic carbon-carbon double bond in a molecule | numerator is mentioned, Specifically, Diallyl isocyanuric acid; Triallyl isocyanuric acid; And di-allyl methyl include SOCCIA press acid, diallyl ethyl group is SOCCIA press acid, diallyl methyl these diallyl C _{1 -10} alkyl, such as press SOCCIA acid SOCCIA press acid allyl containing isocyanuric acid . An isocyanuric acid compound (D) may be used by 1 type, and may use 2 or more types together. In particular, diallyl the SOCCIA acid are preferable press acid and diallyl C _{1 -10} alkyl SOCCIA press.

In curable resin composition of this invention, content of ladder type silsesquioxane (A) is 45-98 weight%, Preferably it is 50-95 weight%, More preferably, 60-90 weight%, Especially preferably, it is 65 to 85 weight%. By setting it as such a range, hardened | cured material excellent in the crack resistance can be obtained especially when it hardens.

As a ratio of ladder type silsesquioxane (A) and linear polysiloxane (B) of the molecular weight 100-9000, it is a Si-H type linear polysiloxane with respect to 1 mol of aliphatic carbon-carbon double bonds in vinyl ladder silsesquioxane. Aliphatic carbon- in vinyl straight-chain polysiloxane with Si—H bonds ranging from 0.2 to 2 moles, especially 0.3 to 1.5 moles, especially 0.8 to 1.2 moles, or 1 mole of Si—H bonds in a Si-H ladder silsesquioxane Preference is given to a proportion in which the carbon double bonds are 0.2 to 2 moles, especially 0.3 to 1.5 moles, especially 0.8 to 1.2 moles. As the weight ratio, the linear polysiloxane (B) is, for example, 3 to 200 parts by weight, preferably 5 to 150 parts by weight, more preferably 10 to 100 parts by weight of the ladder silsesquioxane (A). To 100 parts by weight.

In curable resin composition of this invention, as content of an isocyanuric-acid compound (D), it is 0-10 weight part with respect to 100 weight part of ladder-type silsesquioxanes (A), for example, Preferably it is 0-weight. 8 parts by weight, more preferably 0.1 to 6 parts by weight. When content of an isocyanuric acid compound (D) exists in such a range, the hardened | cured material which is excellent in the compatibility of especially curable resin composition, and excellent in crack resistance, when hardened | cured can be obtained.

In curable resin composition of this invention, the total amount of ladder type silsesquioxane (A) and linear polysiloxane (B) is 20 weight% or more, for example with respect to the total amount of polysiloxane contained in curable resin composition, Preferably It is 50 weight% or more, More preferably, it is 80 weight% or more, It is especially preferable that it is 90 weight% or more. If the total amount of ladder type silsesquioxane (A) and linear polysiloxane (B) exists in this range, the hardened | cured material excellent in especially softness can be obtained. Moreover, in the curable resin composition of this invention, the ratio which the total amount of polysiloxane containing a ladder silsesquioxane (A) and a linear polysiloxane (B) occupies is 50 weight% or more, Preferably it is 80 weight % Or more, More preferably, it is 90 weight% or more. When the ratio which the total amount of polysiloxane occupies exists in this range, especially hardened | cured material with high heat resistance can be obtained.

In curable resin composition of this invention, it is preferable that content of the said hydrosilylation catalyst (C) is the amount which platinum, palladium, or rhodium in a catalyst exists in the range of 0.01-1,000 weight ppm by weight unit, and is 0.1-500 weight More preferably, it is in the range of ppm. When content of a hydrosilylation catalyst (C) exists in such a range, a crosslinking speed does not become remarkably slow and there is little possibility that a problem, such as coloring, may arise in a crosslinked material, and it is preferable.

Moreover, in order to adjust the speed | rate of a hydrosilylation reaction, curable resin composition of this invention may contain the hydrosilylation reaction inhibitor. As this hydrosilylation reaction inhibitor, Alkyne alcohols, such as 3-methyl-1- butyn-3-ol, 3, 5- dimethyl- 1-hexyn-3-ol, and phenyl butynol; Enyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane , Thiazole, benzothiazole, benzotriazole and the like are exemplified. Although content of this hydrosilylation reaction inhibitor differs according to the crosslinking conditions of the said composition, in practical use, content in curable resin composition has the preferable range of 0.00001-5 weight%.

The curable resin composition of the present invention also contains precipitated silica, wet silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, zinc oxide, calcium carbonate and carbon. Inorganic fillers such as black, silicon carbide, silicon nitride, and boron nitride, and inorganic fillers treated with organosilicon compounds such as organohalosilanes, organoalkoxy silanes, and organosilazane; Organic resin fine powders such as silicone resins, epoxy resins, and fluororesins; Fillers, solvents, stabilizers (antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, etc.), flame retardants (phosphorus-based flame retardants, halogen-based flame retardants, inorganic flame retardants, etc.), flame retardants, crosslinking agents Reinforcing materials (other fillers), nucleating agents, coupling agents, silane coupling agents, lubricants, waxes, plasticizers, mold release agents, impact modifiers, color improvers, rheology modifiers, colorants (dyes, pigments, etc.), dispersants, antifoaming agents, antifoaming agents, antibacterial agents Ordinary additives, such as a preservative, a viscosity modifier, and a thickener, may be contained. These additives may be used alone or in combination of two or more.

Curable resin composition of this invention is obtained by stirring and mixing each said component at room temperature, for example. Curable resin composition of this invention also contains the composition of a multi-liquid system, may be a 1-liquid system, may be stored separately as a 2-liquid system or a multi-liquid system, and may be mixed before use.

[Sealing agent]

The sealing agent of this invention contains the said curable resin composition. The sealant of the present invention is excellent in physical properties such as high temperature heat resistance, flexibility, transparency, heat yellowing resistance, and light yellowing resistance, and can be suitably used as a sealant for an optical semiconductor element.

[Cured goods]

Curable resin composition of this invention can be hardened by the hydrosilylation reaction using the said hydrosilylation catalyst (C). The conditions of the hydrosilylation reaction are not particularly limited and may be performed under conventionally known conditions using the catalyst. However, in order to perform defoaming efficiently and to further reduce surface irregularities, the temperature is preferably 40 to 100 ° C. [preferably, 60 to 100 It is preferable to carry out prebaking at 1 to 5 hours, and to harden at 100 to 180 ° C (preferably 120 to 150 ° C) for about 3 to 10 hours. The obtained hardened | cured material does not change transparency and a crack does not produce | generate even if it carries out a Tj = 180 degreeC energization test, and it is excellent in physical properties, such as high temperature heat resistance, flexibility, transparency, heat yellowing resistance, and light yellowing resistance. In addition, the water vapor barrier property is also superior to about 1/3 compared with the conventional dimethylsilicone resin.

[LED and optical semiconductor device]

Since the LED of the present invention is sealed by the cured product having excellent physical properties such as high temperature heat resistance, flexibility, transparency, heat yellowing resistance, and light yellowing resistance, the LEDs of the present invention have high temperature heat resistance, flexibility, transparency, heat yellowing resistance, and light yellowing resistance. Excellent physical properties In addition, since the optical semiconductor device of the present invention includes an LED having excellent physical properties such as high temperature heat resistance, flexibility, transparency, heat yellowing resistance, and light yellowing resistance, the optical semiconductor device of the present invention has high temperature heat resistance, flexibility, transparency, heat yellowing resistance, and light sulfur resistance. It is excellent in physical properties such as denaturation.

[Example]

Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples. In addition, ¹ H-NMR analysis was performed by JEOL ECA500 (500 MHz).

Synthesis Example 1 [Synthesis of ladder-type vinylphenylmethylsilsesquioxane]

In a 300 ml four-necked flask, 10 g of a ladder-type terminal ethoxy group phenylmethylsilsesquioxane (weight average molecular weight is Mw2200, content of ethoxy group per molecule is 1.5wt%, phenyl / methyl (molar ratio) = 1/1) and 3.0 g of 10% by weight tetramethylammonium hydroxide, 200 g of methyl isobutyl ketone, and 5.5 g of dimethylethoxy vinylsilane were added thereto. It heated at 45 degreeC for 1 hour, and reaction was complete | finished. After adding 100 g of ethyl acetate, water washing was performed 5 times with 500 g of water. The upper layer after washing was concentrated by an evaporator, and then triturated under reduced pressure with a vacuum pump for 30 minutes. In 7.8 g of yield, a liquid ladder type vinylphenylmethylsilsesquioxane (compound which corresponds to vinyl type ladder silsesquioxane) was obtained. As for the weight average molecular weight, content (average) of Mw 1700 and the vinyl group per molecule was 4.6 wt%.

[ ¹ H-NMR Spectrum of Ladder-type Vinylphenylmethylsilsesquioxane]

¹ H-NMR (CDCl ₃ ) δ: 0.1 (br), 5.4-6.2 (br), 6.8-7.8 (br)

Moreover, the ladder type terminal ethoxy group phenylmethyl silsesquioxane used as a raw material was manufactured by hydrolyzing and condensing triethoxymethylsilane and triethoxy phenylsilane (molar ratio 1: 1) by a conventional method.

Example 1 [Preparation of Ladder Silsesquioxane-containing Curable Resin Composition 1 Containing Isocyanuric Acid and Its Cured Product 1]

6.00 g of ladder type vinylphenylmethylsilsesquioxane obtained by Synthesis Example 1, 0.30 g of diallyl methyl isocyanuric acid (Shikoku Kasei) and 1,1,3,3,5,5-hexamethyltrisiloxane 1.41 g (manufactured by Gelest) was weighed into a 6 ml screw tube and stirred at room temperature for 2 hours to obtain a good compatibility and a transparent and uniform solution. 3 microliters of platinum vinylmethylsiloxane complex (Wakko Chemical Co., Ltd .; 1.6 wt% of platinum) was thrown into the obtained liquid mixture, and it stirred again, and obtained curable resin composition 1.

The obtained curable resin composition 1 was apply | coated to the glass plate, and the colorless transparent hardened | cured material 1 was obtained when heating in oven at 60 degreeC for 1 hour and 150 degreeC for 5 hours. The physical property of the hardened | cured material 1 was shown in Table 1, and the light transmittance is shown in FIG.

Example 2 [Preparation of Ladder Silsesquioxane-containing Curable Resin Composition 2 Containing Isocyanuric Acid and Its Cured Product 2]

0.60 g of ladder type vinylphenylmethylsilsesquioxane obtained by Synthesis Example 1, 0.030 g of diallyl methyl isocyanuric acid (Shikoku Kasei) and 1,1,3,3,5,5,7,7- 0.14 g of octamethyltetrasiloxane (manufactured by fluorochem) was weighed into a 6 ml screw tube, and stirred at room temperature for 2 hours, whereby a good compatibility and a transparent and uniform solution were obtained. 0.6 microliter of platinum vinylmethylsiloxane complex (Wakko Chemical Co., Ltd .; 1.6 wt% of platinum) was thrown into the obtained liquid mixture, and it stirred again, and obtained curable resin composition 2.

The obtained curable resin composition 2 was apply | coated to the glass plate, and the colorless and transparent hardened | cured material 2 was obtained when heating in oven at 60 degreeC for 1 hour and 150 degreeC for 5 hours.

Example 3 [Production of Ladder Silsesquioxane-containing Curable Resin Composition 3 and Its Cured Product 3]

6 ml of ladder vinyl phenylmethylsilsesquioxane (6.00 g) and 1,1,3,3,5,5,7,7-octamethyltetrasiloxane (1.53 g, fluorochem) obtained in Synthesis Example 1 Weighing was added to a screw tube of and stirred at room temperature for 2 hours, whereby a good compatibility and a transparent and uniform solution were obtained. 6 microliters of platinum vinylmethylsiloxane complex (Wakko Co., Ltd .; 1.6 wt% of platinum) was thrown into the obtained liquid mixture, and it stirred again, and obtained curable resin composition 3.

Obtained curable resin composition 3 was apply | coated to the glass plate, and the colorless and transparent hardened | cured material 3 was obtained when it heated at 60 degreeC for 1 hour and 150 degreeC in oven.

Example 4 [Production of Ladder Silsesquioxane-containing Curable Resin Composition 4 and Its Cured Product 4]

Ladder-shaped vinylphenylmethylsilsesquioxane (0.60g) and 0.10g (1,1,3,3-tetramethyldisiloxane) obtained by the synthesis example 1 were weighed into a 6 ml screw tube, and 2 When the mixture was stirred at room temperature for a time, a good compatibility and a transparent and uniform solution were obtained. 0.6 microliter of platinum vinylmethylsiloxane complex (Wakko Chemical Co., Ltd .; 1.6 wt% of platinum) was thrown into the obtained liquid mixture, and it stirred again, and obtained curable resin composition 4.

The obtained curable resin composition 4 was apply | coated to the glass plate, and the colorless transparent hardened | cured material 4 was obtained when heating in oven at 60 degreeC for 1 hour and 120 degreeC for 3 hours.

Example 5 [Production of Ladder Silsesquioxane-containing Curable Resin Composition 5 and Its Cured Product 5]

The ladder-type phenylmethylsilsesquioxane derivative A (0.60 g) obtained in Synthesis Example 1 and 0.28 g of Si-H-terminated polysiloxane (Gelest, molecular weight 400 to 500) were weighed into a 6 ml screw tube. And it stirred at room temperature for 2 hours, and the compatibility was favorable and the transparent and uniform solution was obtained. 0.6 microliter of platinum vinylmethylsiloxane complex (made by Wako Pure Chemical Industries; 1.6 wt% of platinum) was thrown into the obtained liquid mixture, and it stirred again, and obtained curable resin composition 5.

The obtained curable resin composition 5 was apply | coated to the glass plate, and the colorless and transparent hardened | cured material 5 was obtained when heating in oven at 60 degreeC for 1 hour and 120 degreeC for 3 hours.

Example 6 [Manufacture of Ladder Silsesquioxane-containing Curable Resin Composition 6 and Its Cured Product 6]

Ladder-type terminal trimethylsilyl group phenylmethylvinylsilsesquioxane (0.60 g) and 0.14 g of 1,1,3,3-tetramethyldisiloxane (manufactured by Tohsei Chemical Co., Ltd.) were weighed into a 6 ml screw tube, followed by room temperature for 2 hours. The mixture was stirred at to obtain a good, compatible, transparent and uniform solution. 0.6 microliter of platinum vinylmethylsiloxane complex (made by Wako Pure Chemical Industries; 1.6 wt% of platinum) was thrown into the obtained liquid mixture, and it stirred again, and obtained curable resin composition 6.

The obtained curable resin composition 6 was apply | coated to the glass plate, and the colorless and transparent hardened | cured material 6 was obtained when heating in oven at 60 degreeC for 1 hour and 120 degreeC for 3 hours.

In addition, the ladder-type terminal trimethylsilyl group phenylmethylvinyl silsesquioxane used as a raw material of Example 6 was triethoxymethylsilane, triethoxyphenylsilane, and triethoxy vinylsilane (molar ratio 35:35:30). It produced by hydrolyzing and condensing and terminal-protecting with chlorotrimethylsilane (vinyl group content average 8.0wt%, molecular weight Mw4200).

[Tj = 180 ℃ LED energization test]

Example 7

3 × 2Al2O3 package (made by Kyocera) for the package, OBL-CH2424 (made by Generite) for the LED element, KJR-3000M2 (made by Shin-Etsu Silicone) for the die bond material, and SR-30 (made by Tanaka Kikinjo) for the gold wire To assemble the LED package.

Curable resin compositions 1 to 6 obtained in Examples 1 to 6 were cured in the package (1 hour at 60 ° C., 5 hours at 150 ° C.), fixed with solder on the lead wires of the universal substrate, and the samples for the electricity supply test (resin 1 to 6) were produced.

Comparative Example

Except having changed the curable resin composition into the epoxy resin (CELVENUS W0910, Daicel Chemical Industries, Ltd. make), it carried out similarly to Example 7, and produced the sample (epoxy resin) for an electricity supply test.

Evaluation conditions were made into the environmental temperature (90 degreeC) and electric current conditions (150 mA) which assumed Tj = 180 degreeC, the constant current power supply is attached to a circuit, and the epoxy obtained by resins 1-6 obtained by the said Example 7, and the comparative example Continuously energized the resin. Discoloration of resin after 1 week (after 168 hours), change in light output, Vf (deterioration level of the device), cracking of the cured product (resin), and the presence or absence of peeling were visually confirmed. The results are shown in Table 2.

Resins 1 to 6 did not generate cracks or peelings even when energized for one week. Epoxy resin became a boiling point for 52 hours.

Industrial Applicability

When thermosetting the curable resin composition of this invention, a hydrosilylation reaction advances and the hardened | cured material excellent in transparency and excellent in high temperature heat-yellowing resistance and flexibility is obtained. This hardened | cured material does not yellow even if it is exposed to long term under high temperature, and since it is excellent in flexibility, it is hard to produce a crack and a crack, and therefore it is useful as a sealing material for next-generation light sources.

Claims (6)

Comprising a ladder-like silsesquioxane (A) capable of reacting with each other to form a carbon-silicon bond by hydrosilylation (A), a straight chain polysiloxane (B) having a molecular weight of 100 to 9000, and a hydrosilylation catalyst (C) Curable resin composition characterized by the above-mentioned. The isocyanuric acid compound (D) according to claim 1, wherein the isocyanuric acid compound (D) capable of reacting with the ladder silsesquioxane (A) and / or straight-chain polysiloxane (B) to form a carbon-silicon bond by hydrosilylation Curable resin composition containing further. The sealing agent for optical semiconductors containing curable resin composition of Claim 1 or 2. Hardened | cured material obtained by hardening | curing curable resin composition of Claim 1 or 2. An LED containing the hardened | cured material of Claim 4. The optical semiconductor device containing the LED of Claim 5.

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