CN101993593A

CN101993593A - Composition for packaging optical semiconductor

Info

Publication number: CN101993593A
Application number: CN2010102607792A
Authority: CN
Inventors: 田崎太一; 根本哲也; 元成正之
Original assignee: JSR Corp
Current assignee: JSR Corp
Priority date: 2009-08-21
Filing date: 2010-08-20
Publication date: 2011-03-30
Also published as: JP2011063799A; KR20110020203A; TW201113330A

Abstract

The present invention relates to a composition for packaging an optical semiconductor. The invention provides the composition for packaging the optical semiconductor and a light-emitting element made by using the composition, the composition is characterized by comprising: (A) polysiloxane containing an epoxy group and a phenyl group which contains or does not contain a substituent group; and (B) a curing agent for epoxy resin, wherein a content of the phenyl group is 8-30% by mass relative to the (A) polysiloxane. The composition can be used for forming the condensate without damage to thermal stability and light stability, and with improved crack resistant, sealing, and color change resistance to an electrode.

Description

Optical semiconductor encapsulation composition

Technical field

The present invention relates to a kind of optical semiconductor encapsulation composition, in more detail, relate to and a kind ofly contain polysiloxane, can obtain having thermotolerance and the photostabilization optical semiconductor encapsulation composition of the cured article of the patience excellence of anti-crackle, adaptation and counter electrode variable color simultaneously with epoxy group(ing) and phenyl.

Background technology

In the past, ended material, generally used Resins, epoxy as the envelope of photodiode (LED) element.

On the other hand, in the process that led light source short wavelength (high-output power) changes, produce in the actual use of the epoxy packages material be not considered as problem so far under hot environment or under the effect of UV-light etc. xanthochromia takes place or follow the increase of heat dissipation capacity and problem such as crack, tackling these problems becomes the task of top priority.

For this reason, at present, the thermotolerance and the transparency are excellent, and are widely used as the LED packaged material in properties not easy to change, that also be difficult for taking place the physical property deterioration than the silicone resin of other organic resin material excellences.

But when using silicone resin as packaged material, can appear following new problem in one's mind: poor with the adaptation of other organic components that use among the LED, gas-premeable and steam breathability height can make the electrode variable color so see through the gaseous constituent of packaged material.

Therefore, in recent years, in silicone resin, imported organic group, organic inorganic hybridization type packaged material gazed at.As the organic group that is used for such packaged material,, mainly adopt these two kinds of groups (with reference to patent documentation 1 and 2) of epoxy group(ing) and phenyl from thermotolerance and sunproof viewpoint.

Such organic inorganic hybridization packaged material is along with organic content increases, and the electrode variable color suppresses effect and the adaptation of LED parts is improved.

But, addition reaction solidified type epoxy-the silicone resin of high organic content has although it is so brought the raising of adaptation and the variable color of electrode to suppress effect really, yet resulting cured article is hard and crisp, so have the tendency that is easy to generate crackle in the evaluation of cold cycling (40 ℃～100 ℃).

In addition, in silicone resin, in skeleton, have under the situation of addition reaction curing phenyl organosilicon resin composition of phenyl with high-content, intensity, particularly flexural strength and the hardness of cured article improve under aromatic nucleus π-π each other interacts, thereby cold cycling can not cause cured article to crack.But, so in order to improve intensity or in order to suppress the electrode variable color, must be to contain phenyl at high proportion in resin matrix, so, the photostabilization of cured article worsens, thereby causes briliancy to reduce.

Patent documentation 1: TOHKEMY 2002-265787

Patent documentation 2: TOHKEMY 2004-186168

Summary of the invention

The purpose of this invention is to provide a kind of optical semiconductor encapsulation composition, it can form the cured article that the patience of not damaging thermotolerance and photostabilization and anti-crackle, adaptation, counter electrode variable color has improved.

The inventor finds, a part of epoxy group(ing) of the polysiloxane by will containing epoxy group(ing) is replaced into phenyl, can reach above-mentioned purpose, so that finished the present invention.

That is, the present invention relates to a kind of optical semiconductor encapsulation and use composition, it is characterized in that, comprise: (A) polysiloxane, it contains epoxy group(ing) and has or do not have substituent phenyl; (B) hardener for epoxy resin, with respect to above-mentioned (A) polysiloxane, the described content that has or do not have substituent phenyl is 8～30 quality %.

Above-mentioned optical semiconductor encapsulation is with in the composition, the epoxy equivalent (weight) of preferably above-mentioned (A) polysiloxane is 100～10000g/eq., and preferably above-mentioned (A) polysiloxane has the structural unit of following formula (1) expression, the structural unit of following formula (2) expression and the structural unit of following formula (3) expression.

R ¹ ₂SiO _2/2 (1)

R ¹ _aR ^E _b(OR ²) _cSiO _(4-a-b-c)/2 (2)

R ¹ _aR ^P _b(OR ²) _cSiO _(4-a-b-c)/2 (3)

(in formula (1)～(3),

R ¹Represent that independently of one another carbonatoms is 1～3 non-replacement or 1 valency alkyl of replacement,

R ²Represent that independently of one another hydrogen atom or carbonatoms are 1～3 non-replacement or 1 valency alkyl of replacement,

R ^EThe carbonatoms that expression has an epoxy group(ing) is 3～20 1 valency organic group,

R ^PIt is 6～20 1 valency organic group that expression contains the carbonatoms that has or do not have substituent phenyl,

A is 1 or 2, and b is 1 or 2, and c is 0 or 1, and a+b+c is 2 or 3.〕

Above-mentioned (A) polysiloxane preferably has at least 1 group in the group shown in following general formula (4)～(7).

(in the general formula (4), R ⁵The carbonatoms of expression methylene radical or divalent is that 2～10 straight chain shape alkylidene group or carbonatoms are a chain alkylidene group of 3～10.〕

(in the general formula (5), R ⁶The carbonatoms of expression methylene radical or divalent is that 2～10 straight chain shape alkylidene group or carbonatoms are a chain alkylidene group of 3～10.〕

(in the general formula (6), R ⁷The carbonatoms of expression methylene radical or divalent is that 2～10 straight chain shape alkylidene group or carbonatoms are a chain alkylidene group of 3～10.〕

(in the general formula (7), R ⁸The carbonatoms of expression methylene radical or divalent is that 2～10 straight chain shape alkylidene group or carbonatoms are a chain alkylidene group of 3～10.〕

In addition, the encapsulation of above-mentioned optical semiconductor is with in the composition, and preferably above-mentioned (A) polysiloxane is the polysiloxane that the compound (a3) by compound (a2) that makes polydimethylsiloxane (a1) that end has a silanol group and following formula (8) expression and following formula (9) expression reacts, next its reaction product hydrolysis obtained.

R ^E _mR ¹ _4-m-nSi(OR ³) _n (8)

(in the formula (8), R ^EExpression contains the organic group of epoxy group(ing), R ¹And R ³Represent 1 valency alkyl of non-replacement or replacement independently of one another, m is 1 or 2, and n is 2 or 3, and m+n≤4.)

R ^P _lR ¹ _4-l-kSi(OR ³) _k (9)

(in the formula (9), R ^PExpression contains the organic group that has or do not have substituent phenyl, R ¹And R ³Represent 1 valency alkyl of non-replacement or replacement independently of one another, l is 1 or 2, and k is 2 or 3, and l+k≤4.)

Preferably above-mentioned (A) polysiloxane is to be that 1/0.6～1/10 scope is reacted the polysiloxane that obtains by making polydimethylsiloxane (a1), above-claimed cpd (a2) and above-claimed cpd (a3) with (mole number of polydimethylsiloxane (a1))/(total mole number of compound (a2) and compound (a3)).

Preferably above-mentioned (A) polysiloxane is to be that 90/10～10/90 scope is reacted the polysiloxane that obtains by making above-claimed cpd (a2) and above-claimed cpd (a3) with (mole number of compound (a2))/(mole number of compound (a3)).

Above-mentioned optical semiconductor encapsulation preferably contains acid anhydrides as above-mentioned (B) hardener for epoxy resin with in the composition, preferably further contains silica dioxide granule.

In addition, other inventions relate to luminous element, and it is to use above-mentioned optical semiconductor encapsulation with composition the optical semiconductor encapsulation to be obtained.

Optical semiconductor of the present invention encapsulation with composition by containing polysiloxane, can form the cured article that the patience of not damaging thermotolerance and photostabilization and anti-the crackle anti-crackle of thermal cycling test (particularly to), adaptation and counter electrode variable color is improved with epoxy group(ing) and specified quantitative phenyl.Particularly, can make the adaptation of cured article and electrode variable color suppress the effect raising by increasing the content of epoxy group(ing) and phenyl.By increasing the amount of phenyl, can seek the raising of the strength of materials of cured article, and, can seek to improve patience to by crackle due to reduction of crosslinking group density and/or the stress alleviation effects by further making end have reactive polydimethylsiloxane and octadecyloxy phenyl TMOS generation coupling.And,, can improve the photostabilization of cured article by reducing the amount of phenyl.By with containing of phenyl and epoxy group(ing) of the proportional certain limit that is set in, can make the LED packaged material that all satisfies above-mentioned characteristic.

Description of drawings

Fig. 1 is the synoptic diagram of LED.

Fig. 2 is the synoptic diagram with LED of fluorescence portion.

Nomenclature

50 luminous element portions, 51 packaged materials, 52 fluorescence portions, 53 tackiness agents, 54 fluor

Embodiment

＜optical semiconductor encapsulation composition 〉

Optical semiconductor of the present invention encapsulation comprises (A) with composition and contains epoxy group(ing) and have or do not have the polysiloxane of substituent phenyl and (B) hardener for epoxy resin, with respect to above-mentioned (A) polysiloxane, the above-mentioned content that has or do not have substituent phenyl is 8～30 quality %, and said composition can contain silica dioxide granule etc. as required.

(A) polysiloxane

(A) polysiloxane contains epoxy group(ing).(A) polysiloxane can solidify by the ring-opening polymerization of this epoxy group(ing).(A) epoxy equivalent (weight) of polysiloxane is 100～10000g/eq., is preferably 200～8000g/eq., more preferably 300～5000g/eq..Above-mentioned epoxy equivalent (weight) is during less than 100g/eq., cause the transparency of gained cured film to reduce and cured film in crack, when above-mentioned epoxy equivalent (weight) surpasses 10000g/eq., have the bad tendency of curing take place.

(A) polysiloxane preferably has at least 1 group in the group shown in following general formula (4)～(7) as the group that contains epoxy group(ing).If (A) polysiloxane has such group, then can form the thick film of the mm order of magnitude of cured article.

As the group of general formula (4) expression, specifically can enumerate 2-(3 ', 4 '-epoxycyclohexyl) ethyl etc.

As the group of general formula (5) expression, specifically can enumerate 3-glycidoxy etc.

As the group of general formula (6) expression, specifically can enumerate 3-epoxypropoxy etc.

As the group of general formula (7) expression, specifically can enumerate 2-(4 '-methyl-3 ', 4 '-epoxycyclohexyl) ethyl etc.

(A) polysiloxane contains epoxy group(ing) and has or do not have substituent phenyl.Contain epoxy group(ing) and have or do not have a substituent phenyl by (A) polysiloxane, optical semiconductor encapsulation of the present invention can form the cured article that does not damage thermotolerance and photostabilization and the patience of anti-crackle, adaptation and counter electrode variable color has been improved with composition.

What is called has or does not have substituent phenyl, is meant phenyl and an above hydrogen atom of phenyl is replaced with the group that other substituting groups form.As phenyl the substituting group that can have, can to enumerate carbonatoms be 1～12, be preferably the monovalence alkyl about 1～9, specifically can enumerate alkyl such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, neo-pentyl, hexyl, cyclohexyl, octyl group, nonyl, decyl; Aryl such as tolyl, xylyl, naphthyl; Aralkyl such as benzyl, styroyl, hydrocinnamyl; Thiazolinyls such as vinyl, allyl group, propenyl, pseudoallyl, butenyl, hexenyl, cyclohexenyl, octenyl etc.

Have or do not have the content of substituent phenyl with respect to above-mentioned (A) polysiloxane, just should (A) quality ratio that has or do not have substituent phenyl that polysiloxane contained when the quality settings with above-mentioned (A) polysiloxane is 100 quality % be 8～30 quality %, be preferably 10～28 quality %, 12～26 quality % more preferably.Above-mentioned content can not obtain the cured film of desired intensity during less than 8 quality %, cracks in the resin in cold cycling, and when above-mentioned content surpassed 30 quality %, photostabilization significantly worsened.Above-mentioned content when in addition, phenyl has substituting group is the content of only removing the atomic group that the hydrogen atom of substituting group number forms from phenyl.

Above-mentioned (A) polysiloxane preferably has 3 kinds of structural units of following formula (1)～(3) expression.

R ¹ ₂SiO _2/2 (1)

R ¹ _aR ^E _b(OR ²) _cSiO _(4-a-b-c)/2 (2)

R ¹ _aR ^P _b(OR ²) _cSiO _(4-a-b-c)/2 (3)

(in formula (1)～(3),

R ^PIt is 6～20 1 valency organic group that expression contains the carbonatoms that has or do not have substituent phenyl;

A is 1 or 2, and b is 1 or 2, and c is 0 or 1, and a+b+c is 2 or 3.〕

As R ¹, specifically can enumerate methyl, ethyl, propyl group etc., wherein special preferable methyl.

As R ², specifically can enumerate hydrogen atom, methyl, ethyl, propyl group etc., wherein preferred especially hydrogen atom and methyl.

As R ¹And R ²The substituting group that can have, can enumerate for example halogen atoms such as fluorine atom, bromine atoms, iodine atom etc.

As R ^ESpecifically can enumerate the group of above-mentioned general formula (4)～(7) expression etc., more particularly, can enumerate γ-epoxypropoxy and 3,4-oxirane ring amyl group, 3, oxirane ring alkyl such as 4-epoxycyclohexyl, 2-(3 ', 4 '-oxirane ring amyl group) ethyl and 2-(3 ', 4 '-epoxycyclohexyl) ethyl etc.

As R ^P, specifically can enumerate aryl such as phenyl, tolyl, xylyl; Aralkyl such as benzyl, styroyl, hydrocinnamyl etc.R ^PIn the phenyl that contains the substituting group that can have and above-mentioned phenyl the substituting group that can have identical.

Above-mentioned (A) polysiloxane has the structural unit of representing above-mentioned formula (1)～(3) can be by for example carrying out ¹H-NMR and ²⁹The two-dimentional NMR that Si-NMR measures measures and confirms.

(A) polysiloxane by gel permeation chromatography by the weight-average molecular weight of polystyrene conversion preferably 100～1,000,000 scope, more preferably 200～500,000 scope.If (A) weight-average molecular weight of polysiloxane is in above-mentioned scope, then when using the present composition to make the optical semiconductor encapsulation, operate easily with material, and the cured article that is obtained by the present composition has the sufficient strength of materials and characteristic as optical semiconductor sealing material.

With respect to the quality of composition in its entirety, it is desirable to contain (A) polysiloxane 50～100 quality %, preferred 60～100 quality %.

Manufacture method for (A) polysiloxane is not particularly limited, for example can obtain in the following way: the operation (hereinafter referred to as " operation (i) ") of reacting at the compound (a3) of the compound (a2) of the polydimethylsiloxane (a1) that makes end have a silanol group and following formula (8) expression and following formula (9) expression is carried out the operation (hereinafter referred to as " operation (ii) ") with its reaction product hydrolysis afterwards.

R ^E _mR ¹ _4-m-nSi(OR ³) _n (8)

R ^P _lR ¹ _4-l-kSi(OR ³) _k (9)

Below, each operation is described.

(operation (i))

(polydimethylsiloxane (a1))

Polydimethylsiloxane (a1) provides the compound of the structural unit of above-mentioned formula (1) expression.Polydimethylsiloxane (a1) has at least 1, preferred 2 above hydroxyls at the end of its molecular backbone and/or side chain.Such C-terminal polydimethylsiloxane for example can be made by making dimethyl dialkoxy silicane or dimethyldichlorosilane(DMCS) hydrolysis and condensation.

As above-mentioned dimethyl dialkoxy silicane, can enumerate dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyl diisopropoxy silane, dimethyl two n-butoxy silane etc.These dimethyl dialkoxy silicanes can use a kind or mix more than 2 kinds and to use separately.

In addition, as polydimethylsiloxane (a1), two commercially available ends such as the FM9915 that XC96-723, YF-3800, YF-3802, YF-3897, the Chisso company that also can use Momentive Performance Materials company to make makes (above be trade(brand)name) contain the polydimethylsiloxane of silanol group.In addition, polydimethylsiloxane (a1) also can have branch's structures such as star-like, comb type.

Above-mentioned C-terminal polydimethylsiloxane by gel permeation chromatography by the weight-average molecular weight of polystyrene conversion usually in 300～5000 scope, more preferably 300～2000, preferred especially 500～1000.If use C-terminal polydimethylsiloxane with above-mentioned scope weight-average molecular weight, then when making cured article, can obtain necessary strength, be preferred in this.

(compound (a2))

Compound (a2) provides the compound of the structural unit of above-mentioned formula (2) expression.Compound (a2) is to have organic group and the organoalkoxysilane 2 or 3 alkoxyl groups, that contain epoxy group(ing) that contains epoxy group(ing) shown in above-mentioned formula (8).

In the above-mentioned formula (8), R ^EBe the organic group that contains epoxy group(ing), as such R ^E, can enumerate with above-mentioned formula (2) in R ^ESame group.In these organic groups,, preferably contain the organic group of oxirane ring alkyl, more preferably contain the organic group of epoxycyclohexyl ethyl from the stable aspect of operation described later (ii) the time.

R ¹And R ³Be 1 valency alkyl of non-replacement or replacement independently of one another, for example can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl etc., be preferably methyl, ethyl.

As R ¹And R ³The substituting group that can have can be enumerated the R to above-mentioned formula (1)～(3) ¹And R ²Illustrative substituting group.

M is 1 or 2, and n is 2 or 3, and m+n is below 4.

In the above-claimed cpd (a2), preferred γ-Huan Yangbingyangbingjisanjiayangjiguiwan and 2-(3 ', 4 '-epoxycyclohexyl) ethyl trimethoxy silane are from operation described later stable aspect (ii), preferred especially 2-(3 ', 4 '-epoxycyclohexyl) ethyl trimethoxy silane.

(other organosilane)

In operation (i),, can suitably add compound (a2) organoalkoxysilane in addition in order to adjust the hardness of cured article.As such organoalkoxysilane, can enumerate for example trimethylammonium methoxy silane, trimethylethoxysilane, triethyl methoxy silane, triethyl-ethoxy-silicane alkane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyltrimethoxy silane, ethyl trimethoxy silane, Union carbide A-162, ethyl triethoxysilane, tetramethoxy-silicane, tetraethoxysilane etc.

(compound (a3))

Compound (a3) provides the compound of the structural unit of above-mentioned formula (3) expression.Compound (a3) is to have to contain organic group and the organoalkoxysilane 2 or 3 alkoxyl groups, that contain phenyl that has or do not have substituent phenyl shown in above-mentioned formula (9).

In the above-mentioned formula (9), R ^PBe to contain the organic group that has or do not have substituent phenyl, as such R ^P, can enumerate with above-mentioned formula (2) in R ^PSame group.In these organic groups, from thermotolerance and sunproof viewpoint, preferred phenyl, tolyl, styroyl, wherein more preferably phenyl.

For R ¹And R ³, respectively with above-mentioned formula (8) in R ¹And R ³Identical.

L is 1 or 2, and k is 2 or 3, and l+k is below 4.

In the above-claimed cpd (a3), monobasic octadecyloxy phenyl TMOSs such as preferred phenyltrimethoxysila,e, phenyl methyl dimethoxy silane, phenyl dimethyl methyl TMOS; Dibasic phenylbenzene organoalkoxysilanes such as dimethoxydiphenylsilane, diphenylmethyl methoxylsilane, aspect the reaction stability of linked reaction, preferred especially phenyltrimethoxysila,e and dimethoxydiphenylsilane.

(polydimethylsiloxane (a1) and the reaction of compound (a2)) with compound (a3)

In this operation, in the presence of at least a compound in being selected from basic cpd and metallo-chelate (below be also referred to as " specific compound "), make polydimethylsiloxane (a1) and compound (a2) and compound (a3) reaction, mainly form siloxane bond by the dealcoholysis linked reaction.This operation is preferably implemented under the state that does not as far as possible have water.When having water, comprise hydrolysis and dehydrating condensation process in the reaction process, this process is balanced reaction, so be difficult to the reactivity of raising system integral body.

In the above-mentioned reaction, as polydimethylsiloxane (a1) and the mix mol ratio of compound (a2) with compound (a3), (mole number of polydimethylsiloxane (a1))/(total mole number of compound (a2) and compound (a3)) is preferably 1/0.6～1/10 scope.If mix mol ratio in above-mentioned scope, then reaction is efficiently carried out, and can obtain the polymkeric substance in the above-mentioned epoxy equivalent (weight) scope, can access the cured article of excellent heat resistance.In addition, the mole number of polydimethylsiloxane (a1) is the value that the quality of blended polydimethylsiloxane (a1) is calculated divided by weight-average molecular weight.

And then as the mix mol ratio of compound (a2) with compound (a3), (mole number of compound (a2))/(mole number of compound (a3)) is preferably 90/10～10/90 scope.If mix mol ratio in above-mentioned scope, then reaction is efficiently carried out, and can obtain the polymkeric substance in the above-mentioned epoxy equivalent (weight) scope, can access the cured article of excellent heat resistance.

The temperature of above-mentioned reaction is preferably 10～100 ℃, more preferably 10～80 ℃, is preferably 15～70 ℃ especially.Reaction times is preferably 1～48 hour, more preferably 1～24 hour, is preferably 2～12 hours especially.Reaction both can will be carried out in the disposable adding reaction vessel of each composition, also can or add other one-tenth continuously and assign to carry out on composition discontinuous ground.

Remaining in the organoalkoxysilane residue that contains epoxy group(ing) that polysiloxane contained that generates by above-mentioned reaction have an alkoxyl group (below, this polysiloxane is called " polysiloxane that contains alkoxyl group ").

(basic cpd)

As above-mentioned basic cpd, can enumerate the alkali alcoholate such as oxyhydroxide, sodium methylate, sodium ethylate of basic metal such as ammonia (comprising ammonia soln), organic amine compound, sodium hydroxide, potassium hydroxide or alkaline-earth metal.Wherein, preferred ammonia and organic amine compound.

As organic amine, can enumerate alkylamine, alkoxylamine, alkanolamine, arylamine etc.

As alkylamine, can enumerate methylamine, ethamine, propylamine, butylamine, hexylamine, octylame, N, N-dimethyl amine, N, N-diethylamide, N, it is alkylamine of 1～4 alkyl etc. that N-dipropylamine, N, N-dibutylamine, Trimethylamine, triethylamine, tripropylamine, tributylamine etc. have carbonatoms.

As alkoxylamine, can enumerating methoxyl group methylamine, methoxyethyl amine, methoxy propanamine, methoxybutyl amine, oxyethyl group methylamine, ethoxy ethyl amine, ethoxy propylamine, oxyethyl group butylamine, propoxy-methylamine, propoxy-ethamine, propoxypropylamine, propoxy-butylamine, butoxy methylamine, butoxy ethamine, butoxy propyl amine, butoxy butylamine etc., to have carbonatoms be alkoxylamine of 1～4 alkoxyl group etc.

As alkanolamine, can enumerate carbinolamine, thanomin, Propanolamine, butanolamine, N-carbinol methine amine, N-ethyl carbinol amine, N-propyl carbinol amine, N-butyl carbinol amine, the N-Mono Methyl Ethanol Amine, the N-ehtylethanolamine, N-propyl group thanomin, the N-butylethanolamine, N-methyl-prop hydramine, the N-ethylpropanolamine, N-propyl group Propanolamine, N-butyl Propanolamine, N-methyl butanol amine, N-ethyl butanol amine, N-propyl group butanolamine, N-butyl butanolamine, N, N-dimethyl methyl hydramine, N, N-diethyl carbinol amine, N, N-dipropyl carbinolamine, N, N-dibutyl carbinolamine, N, the N-dimethylethanolamine, N, the N-diethylethanolamine, N, N-dipropyl thanomin, N, N-dibutyl thanomin, N, the N-dimethyl propanol amine, N, the N-diethylpropanolamine, N, N-dipropyl Propanolamine, N, N-dibutyl Propanolamine, N, N-dimethyl butyrate hydramine, N, N-diethyl butanolamine, N, N-dipropyl butanolamine, N, N-dibutyl butanolamine, N-methyl dimethoxy hydramine, N-ethyl dimethanolamine, N-propyl group dimethanolamine, N-butyl dimethanolamine, N methyldiethanol amine, the N-ethyldiethanolamine, N-propyl group diethanolamine, N butyl diethanol amine, N-methyl dipropanolamine, N-ethyl dipropanolamine, N-propyl group dipropanolamine, N-butyl dipropanolamine, N-methyl two butanolamines, N-ethyl two butanolamines, N-propyl group two butanolamines, N-butyl two butanolamines, N-(amino methyl) carbinolamine, N-(amino methyl) thanomin, N-(amino methyl) Propanolamine, N-(amino methyl) butanolamine, N-(amino-ethyl) carbinolamine, N-(amino-ethyl) thanomin, N-(amino-ethyl) Propanolamine, N-(amino-ethyl) butanolamine, N-(aminopropyl) carbinolamine, N-(aminopropyl) thanomin, N-(aminopropyl) Propanolamine, N-(aminopropyl) butanolamine, N-(amino butyl) carbinolamine, N-(amino butyl) thanomin, N-(amino butyl) Propanolamine, N-(amino butyl) butanolamine etc. has the alkanolamine that carbonatoms is 1～4 alkyl.

As arylamine, can enumerate aniline, methylphenylamine etc.

And then, as the organic amine beyond above-mentioned, also can enumerate tetraalkylammonium hydroxide such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium; Tetraalkyl quadrols such as Tetramethyl Ethylene Diamine, tetraethylethylenediamine, tetrapropyl quadrol, tetrabutyl quadrol; Alkylamino alkylamines such as methylamino methylamine, methylamino ethylamine, methylamino propyl group amine, methylamino butylamine, ethylamino methylamine, ethylamino ethylamine, ethylamino propyl group amine, ethylamino butylamine, propyl group amino methyl amine, propyl group amino ethyl amine, propyl group aminopropyl amine, the amino butylamine of propyl group, butyl amino methyl amine, butyl amino ethyl amine, butyl aminopropyl amine, the amino butylamine of butyl; Pyridine, pyrroles, piperazine, tetramethyleneimine, piperidines, picoline, morpholine, methylmorpholine, diazabicyclo octane, diazabicyclo nonane, diazabicyclo undecylene etc.

Such basic cpd can use a kind separately, also can mix more than 2 kinds and use.Wherein, preferred especially triethylamine, tetramethyleneimine, tetramethyl ammonium hydroxide, pyridine, diazabicyclo nonane, diazabicyclo undecylene.

(metallo-chelate)

As metallo-chelate, can enumerate zirconium chelates such as three n-butoxy ethyl acetoacetate zirconiums, two (methyl aceto acetate) zirconiums of two n-butoxies, n-butoxy three (methyl aceto acetate) zirconium, four (etheric acid n-propyl) zirconium, four (ethanoyl etheric acid) zirconium, four (methyl aceto acetate) zirconiums; Titanium chelates such as two (methyl aceto acetate) titaniums of diisopropoxy, two (etheric acid) titaniums of diisopropoxy, two (methyl ethyl diketone) titaniums of diisopropoxy; Two (methyl aceto acetate) aluminium of diisopropoxy methyl aceto acetate aluminium, diisopropoxy acetyl acetone aluminium, isopropoxy, isopropoxy two (methyl ethyl diketone) close that aluminium, three (methyl aceto acetate) aluminium, tri acetylacetonato close aluminium, single acetyl acetone closes two (methyl aceto acetate) aluminium or their aluminum chelates such as partial hydrolystate; Or organo-tin compound etc.

As organo-tin compound, can enumerate and on 1 tin atom, be combined with the organometallic compound that 1～2 carbonatoms is 4 valency tin of 1～10 alkyl.Specifically for example can enumerate:

(C ₄H ₉) ₂Sn(OCOC ₁₁H ₂₃) ₂、

(C ₄H ₉) ₂Sn(OCOCH＝CHCOOCH ₃) ₂、

(C ₄H ₉) ₂Sn(OCOCH＝CHCOOC ₄H ₉) ₂、

(C ₈H ₁₇) ₂Sn(OCOC ₈H ₁₇) ₂、

(C ₈H ₁₇) ₂Sn(OCOC ₁₁H ₂₃) ₂、

(C ₈H ₁₇) ₂Sn(OCOCH＝CHCOOCH ₃) ₂、

(C ₈H ₁₇) ₂Sn(OCOCH＝CHCOOC ₄H ₉) ₂、

(C ₈H ₁₇) ₂Sn(OCOCH＝CHCOOC ₈H ₁₇) ₂、

(C ₈H ₁₇) ₂Sn(OCOCH＝CHCOOC ₁₆H ₃₃) ₂、

(C ₈H ₁₇) ₂Sn(OCOCH＝CHCOOC ₁₇H ₃₅) ₂、

(C ₈H ₁₇) ₂Sn(OCOCH＝CHCOOC ₁₈H ₃₇) ₂、

(C ₈H ₁₇) ₂Sn(OCOCH＝CHCOOC ₂₀H ₄₁) ₂、

(C ₄H ₉)Sn(OCOC ₁₁H ₂₃) ₃、

(C ₄H ₉)Sn(OCONa) ₃

Deng the carboxylic acid type organo-tin compound;

(C ₄H ₉) ₂Sn(SCH ₂COOC ₈H ₁₇) ₂、

(C ₄H ₉) ₂Sn(SCH ₂CH ₂COOC ₈H ₁₇) ₂、

(C ₈H ₁₇) ₂Sn(SCH ₂COOC ₈H ₁₇) ₂、

(C ₈H ₁₇) ₂Sn(SCH ₂CH ₂COOC ₈H ₁₇) ₂、

(C ₈H ₁₇) ₂Sn(SCH ₂COOC ₁₂H ₂₅) ₂、

(C ₈H ₁₇) ₂Sn(SCH ₂CH ₂COOC ₁₂H ₂₅) ₂、

(C ₄H ₉)Sn(SCOCH＝CHCOOC ₈H ₁₇) ₃、

(C ₈H ₁₇)Sn(SCOCH＝CHCOOC ₈H ₁₇) ₃、

Deng thiolate type organo-tin compound;

(C ₄H ₉) ₂Sn＝S、(C ₈H ₁₇) ₂Sn＝S、

Sulfides type organo-tin compound;

(C ₄H ₉)SnCl ₃、(C ₄H ₉) ₂SnCl ₂、

(C ₈H ₁₇) ₂SnCl ₂、

Deng the chloride type organo-tin compound;

(C ₄H ₉) ₂SnO, (C ₈H ₁₇) ₂The reaction product of ester cpds such as organotin oxides such as SnO, these organotin oxides and silicon ester, dimethyl maleate, ethyl maleate, dioctyl phthalate (DOP); Deng.

In basic cpd and the metallo-chelate, in operation (i) and operation arbitrary operation (ii) its reactive and epoxy group(ing) stability aspect, preferred basic cpd.

In the operation (i), with respect to total amount 100 mass parts of polydimethylsiloxane (a1), compound (a2) and compound (a3), specific compound adds 0.01～50 mass parts, preferred 0.1～30 mass parts, more preferably 0.5～20 mass parts usually.

When particularly stating metallo-chelate in the use, add 0.01～10 mass parts, preferred 0.01～5 mass parts, more preferably 0.01～2 mass parts.

In addition, when using basic cpd, add 1～50 mass parts, preferred 2～30 mass parts, more preferably 2～20 mass parts.

(organic solvent)

In operation (i), can be with an organic solvent.

As organic solvent, for example can enumerate alcohols, aromatic hydrocarbon based, ethers, ketone, ester class etc.As above-mentioned alcohols, can enumerate methyl alcohol, ethanol, n-propyl alcohol, Virahol, isopropylcarbinol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, n-hexyl alcohol, n-Octanol, ethylene glycol, glycol ether, triglycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate (プロピレ Application モノメチ Le エ one テ Le アセテ one ト), diacetone alcohol etc.In addition, as aromatic hydrocarbon based, can enumerate benzene,toluene,xylene etc., can enumerate tetrahydrofuran (THF), dioxane etc. as ethers, as ketone, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), diisobutyl ketone etc. can be enumerated,, ethyl acetate, propyl acetate, butylacetate, Texacar PC, methyl lactate, ethyl lactate, lactic acid n-propyl ester, isopropyl lactate, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate etc. can be enumerated as the ester class.These organic solvents can use a kind separately, also can mix more than 2 kinds and use.In these organic solvents, from promoting the viewpoint of reaction, the organic solvent beyond the preferred use alcohol, for example methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene, dimethylbenzene etc.

To control above-mentioned reaction etc. is purpose, can suitably use above-mentioned organic solvent.With an organic solvent the time, its consumption can suitably be set according to desired condition.

(operation (ii))

In this operation, in the presence of specific compound, make the product and the water reaction that obtain in the above-mentioned operation (i).Think by this reaction, contain the alkoxyl group that is contained in the polysiloxane of alkoxyl group and be converted into hydroxyl, generate silanol group, its result, generation (A) polysiloxane (below, will be called by the polysiloxane that this reaction obtains " polysiloxane that contains the silanol group epoxy group(ing)).This reaction is preferred to be carried out in the presence of as the specific compound of catalyzer in organic solvent.In addition, among the present invention, above-mentioned alkoxyl group needn't all be converted into silanol group, can be remaining with the state of a part of alkoxyl group.In addition, condensation also can take place in the above-mentioned a part of silanol group that contains the polysiloxane of silanol group epoxy group(ing).

When the total mass of the polydimethylsiloxane (a1) in the operation (i), compound (a2) and compound (a3) was set at 100 mass parts, the amount of the water that operation is added (ii) the time was generally 10～500 mass parts, is preferably 20～200 mass parts, 30～100 mass parts more preferably.If the addition of water is in above-mentioned scope, then operation is (ii) fully carried out, and the water yield of removing after reaction is few, so be preferred.

Above-mentioned operation temperature (ii) is preferably 10～100 ℃, more preferably 10～80 ℃, is preferably 15～70 ℃ especially.Reaction times is preferably 0.3～48 hour, more preferably 0.5～24 hour, is preferably 1～12 hour especially.

Above-mentioned operation (ii) in, with respect to total amount 100 mass parts of polydimethylsiloxane (a1), compound (a2) and compound (a3), specific compound adds 0.01～50 mass parts, preferred 0.1～30 mass parts, more preferably 0.5～20 mass parts usually.

In addition, after operation (i), then carry out operation (ii) the time, both can directly use the specific compound that in operation (i), uses, also can append again with kind or different types of specific compound.

As the organic solvent that operation is used in (ii), can enumerate the organic solvent in operation (i), enumerated etc.

From the storage stability aspect of the above-mentioned polysiloxane that contains the silanol group epoxy group(ing) that obtains, preferably wash as Tudor after (ii) and decide the compound operation in operation.Particularly when using basic cpd, more preferably after reaction, utilize acidic cpd to neutralize, and wash as specific compound.

As being used for the neutral acidic cpd, can enumerate organic acid and mineral acid.As organic acid, can enumerate for example acetate, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, oxalic acid, toxilic acid, maleic anhydride, Methylpropanedioic acid, hexanodioic acid, sebacic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, shikimic acid (ミキミ acid), 2 ethyl hexanoic acid, oleic acid, stearic acid, linolic acid, linolenic acid, Whitfield's ointment, phenylformic acid, para-amino benzoic acid, tosic acid, Phenylsulfonic acid, monochloro acetate, dichloro acetic acid, trichoroacetic acid(TCA), trifluoroacetic acid, formic acid, propanedioic acid, methylsulfonic acid, phthalic acid, fumaric acid, citric acid, tartrate etc.As above-mentioned mineral acid, can enumerate for example hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid etc.

With respect to the basic cpd that 1 equivalent uses in dealcoholization and hydrolysis reaction, the consumption of acidic cpd is generally 0.5～2 equivalent, is preferably 0.8～1.5 equivalent, 0.9～1.3 equivalent more preferably.For acidic cpd, extract the viewpoint of water layer during from washing easily, preferably use water miscible acidic cpd.Be dissolved in when using in the water,, add 0.5～100 mass parts, preferred 1～50 mass parts, the more preferably acidic cpd of 2～10 mass parts usually with respect to 100 mass parts water.

After the neutralization, fully mix, leave standstill, after confirming water and organic solvent being separated mutually, remove the moisture of sub-cloud.

With respect to total amount 100 mass parts of polydimethylsiloxane (a1), compound (a2) and compound (a3), the water that uses in the washing after neutralization is generally 10～500 mass parts, is preferably 20～300 parts, more preferably 30～200 parts.

Washing is carried out in the following way: after adding water and fully stirring, leave standstill, confirm water and after organic solvent is separated mutually, remove the moisture of sub-cloud.Washing times is preferably more than 1 time, more preferably more than 2 times.

In addition, organic solvent extraction also can be used in order to remove impurity in the washing back.As extracting required organic solvent, can use above-mentioned organic solvent.The kind of organic solvent and use level thereof can suitably be selected.

(B) hardener for epoxy resin

(B) hardener for epoxy resin is to make (A) polysiloxane solidified material.

As (B) hardener for epoxy resin, can enumerate acid anhydrides, secondary amine and tertiary amine, metallo-chelate etc.Wherein, special preferred anhydrides.

(acid anhydrides)

As acid anhydrides, be not particularly limited ester ring type acid anhydrides such as preferred ester ring type carboxylic acid anhydride.

As above-mentioned ester ring type acid anhydrides, can enumerate for example compound of following formula (3)～(13) expression:

4-methyl tetrahydrophthalic anhydride, methyl norbornene dioic anhydride, dodecenyl succinic anhydride and α-terpinene, alloocimene etc. have ester ring type compound and the diels-Alder reaction product of maleic anhydride or their hydride etc. of conjugated double bond.In addition, as above-mentioned diels-Alder reaction product or their hydride, can use constitutional isomer and geometrical isomer arbitrarily arbitrarily.

In addition, also can use through silicone-modified acid anhydrides.Such acid anhydrides is by for example 5-norbornylene-2, and 3-dicarboxylic anhydride etc. contains acid anhydrides and two keys in a part compound obtains with the hydrosilication that contains the polysiloxane of hydrogen base (hydride group).In addition, as above-mentioned hydrosilylation reaction product, can use constitutional isomer and geometrical isomer arbitrarily arbitrarily.

In addition, as long as substantially do not hinder curing reaction, also above-mentioned ester ring type acid anhydrides suitably can be used after the chemical modification.

In these ester ring type acid anhydrides, from the flowability of composition, transparent aspect, the compound of preferred formula (3), formula (5), formula (7), formula (8), formula (9) or formula (13) expression etc.Be preferably the compound of formula (3), formula (5), formula (8) or formula (13) expression especially.

Among the present invention, the ester ring type acid anhydrides can use separately or mix more than 2 kinds and use.

And,, also can use aliphatic anhydride, aromatic anhydride more than a kind as acid anhydrides.These acid anhydrides preferably share with the ester ring type acid anhydrides.

As long as substantially do not hinder curing reaction, above-mentioned aliphatic anhydride and aromatic anhydride also suitably use after the chemical modification.

Total usage ratio of aliphatic anhydride and aromatic anhydride is with respect to the total amount of they and ester ring type acid anhydrides, be preferably 50 quality % following, more preferably below the 30 quality %.

With respect to the quality of composition in its entirety, (B) content of hardener for epoxy resin be generally 0.01～10 quality %, be preferably 0.05～5 quality %, 0.1～1 quality % more preferably.

When using acid anhydrides as (B) hardener for epoxy resin, its consumption is 0.2～1.7, is preferably 0.3～1.5, more preferably 0.5～1.3, most preferably is 0.6～0.8 in the equivalence ratio (anhydride equivalent/epoxy equivalent (weight)) of anhydride group with respect to 1 mole of epoxy group(ing) in the polysiloxane that contains the silanol group epoxy group(ing) ((A) polysiloxane).Unfavorable conditions such as in this case, this equivalence ratio is less than 0.2 or surpass at 1.7 o'clock, and the glass transition point (Tg) that might produce the gained cured article reduces, painted.

(curing catalyst)

Optical semiconductor encapsulation of the present invention can contain curing catalyst with composition.Curing catalyst is to promote (A) polysiloxane and (B) composition of the curing reaction of hardener for epoxy resin.

Curing catalyst as such is not particularly limited, but for example can enumerate:

Benzyldimethylamine, 2,4,6-three (dimethylamino methyl) phenol, cyclohexyl dimethylamine, the such tertiary amine of trolamine; The so special amine of UCAT410 (San-Apro Co., Ltd.);

Glyoxal ethyline, 2-n-heptyl imidazoles, 2-n-undecane base imidazoles, the 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, 1-benzyl-2-phenylimidazole, 1, the 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyano ethyl)-glyoxal ethyline, 1-(2-cyano ethyl)-2-n-undecane base imidazoles, 1-(2-cyano ethyl)-2-phenylimidazole, 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole, 2 phenyl 4 methyl 5 hydroxy methylimidazole, 2-phenyl-4,5-two (methylol) imidazoles, 1-(2-cyano ethyl)-2-phenyl-4,5-two ((2 '-cyano group oxyethyl group) methyl) imidazoles, 1-(2-cyano ethyl)-2-n-undecane base imidazoles Trimellitate, 1-(2-cyano ethyl)-2-phenylimidazole

Trimellitate, 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole

Trimellitate, 2,4-diamino-6-(2 '-methylimidazolyl-(1 ')) ethyl s-triazine, 2,4-diamino-6-(2 '-n-undecane base imidazolyl) ethyl s-triazine, 2,4-diamino-6-(2 '-ethyl-4 '-methylimidazolyl-(1 ')) ethyl s-triazine, the isocyanuric acid affixture of glyoxal ethyline, the isocyanuric acid affixture, 2 of 2-phenylimidazole, the such imidazoles of isocyanuric acid affixture of 4-diamino-6-(2 '-methylimidazolyl-(1 ')) ethyl s-triazine;

Diphenylphosphine, triphenylphosphine, the such organo phosphorous compounds of triphenyl phosphite;

Benzyl triphenyl phosphonium chloride

Tetran-butylphosphonium bromide

Methyltriphenylphospbromide bromide

The ethyl triphenyl bromination

Normal-butyl triphenyl bromination

Tetraphenylphosphonibromide bromide

Ethyltriphenylphosphiodide iodide Ethyl triphenyl

Acetate, the tetrabutyl

Acetate, tetra-n-butyl O, o-diethyl phosphorothioate, methyl tributyl

Dimethyl phosphate, tetra-n-butyl

Benzotriazole salt, tetra-n-butyl

A tetrafluoro borate, tetra-n-butyl

Tetraphenyl borate salts, tetraphenyl Tetraphenyl borate salts, triphenyl benzyl

Tetraphenyl borate salts, tetra-n-butyl

A tetrafluoro borate is such

Salt;

1,8-diazabicyclo [5.4.0] undecylene-7, the such Diazabicycloalkene of its organic acid salt;

Zinc octoate, stannous octoate, the such organometallic compound of methyl ethyl diketone aluminum complex;

Tetraethylammonium bromide, tetra-n-butyl ammonium bromide, UCAT18X (San-Apro Co., Ltd.) or the such quaternary ammonium salt of following formula (19);

Boron trifluoride, the such boron compound of triphenyl borate; Zinc chloride, the such metal halide of tin chloride;

High-melting-point decentralized latent curing promotor such as amine add-on type promotor such as the affixture of Dyhard RU 100 or amine and Resins, epoxy; Be covered above-mentioned imidazoles, organo phosphorous compounds, season with polymkeric substance

The surface of curing catalysts such as salt and the microcapsule-type latent curing promotor that obtains; Amine salt type latent curing promotor; The latent curing promotor such as hot cationic polymerization type latent curing promotor of lewis acid, the contour temperature dissociative type of Bronsted hydrochlorate etc.

In these curing catalysts, even can obtain aspect the cured article that the water white transparency long-time heating also is difficult to variable color preferred imidazoles, season

Salt, Diazabicycloalkene, organometallic compound and quaternary ammonium salt.

Above-mentioned curing catalyst can use separately or mix more than 2 kinds and use.

Optical semiconductor of the present invention encapsulation is with in the composition, and with respect to 100 mass parts (A) polysiloxane, the consumption of curing catalyst is 0.005～6 mass parts, be preferably 0.01～5 mass parts, 0.05～4 mass parts more preferably.If the consumption of curing catalyst is less than 0.005 mass parts, then the facilitation effect of curing reaction has the tendency of reduction, and on the other hand, if the consumption of curing catalyst surpasses 6 mass parts, unfavorable conditions such as painted might take place then resulting cured article.

(other compositions)

Optical semiconductor encapsulation of the present invention can further contain inorganic particle, the organic compound that contains epoxy group(ing) as the driving fit auxiliary agent, the polysiloxane that contains epoxy group(ing) or oxetane compound, mercaptan compound, the compound with isocyanuric acid ring structure, organoalkoxysilane or its hydrolyzate or the antiaging agents such as condenses, antioxidant and photostabilizer etc. beyond (A) polysiloxane such as silica dioxide granule with composition.In addition, optical semiconductor encapsulation of the present invention can further contain fluor with composition, and the optical semiconductor encapsulation that contains fluor uses the cured article of composition can be used as the LED packaged material.

[inorganic particle]

When optical semiconductor encapsulation of the present invention contains silica dioxide granule as inorganic particle with composition, be preferred aspect raising curing film strength and the hardness.

When cooperating silica dioxide granule as inorganic particle, also can be or be dispersed in forms such as the colloidal sol of the solvent system that forms in the non-polar solvents such as Virahol isopolarity solvent, toluene or colloid and use with powder.Under the colloidal sol or colloidal situation of solvent system, after the cooperation solvent heated up in a steamer and get final product.In order to improve the dispersiveness of silica dioxide granule, can carry out using after the surface treatment.

The primary particle size of these silica dioxide granules be generally 0.0001～1 μ m, more preferably 0.001～0.5 μ m, be preferably 0.002～0.2 μ m especially.

Under colloidal sol or colloidal situation for silica dioxide granule solvent system, its solid component concentration surpass 0 quality % usually and below 50 quality %, be preferably 0.01 quality %～40 quality %.

As used in the present invention, the untreated Powdered silicon-dioxide in surface, can enumerate OX50, #50, #150, #200, #300 that NIPPON AEROSIL company makes, as the Powdered silicon-dioxide of handling through hydrophobization, can enumerate SS50A, the SS30V that R972, R974 that NIPPON AEROSIL company makes, R976, RX50, RX200, RX300, RY50, RY200S, RY300, R106, eastern Cao company make, Sylophobic100, the Sylophobic200 etc. that Silysia chemical company of Fuji makes.

In addition, as the colloidal silica of solvent dispersion, can enumerate the non-polar solvent dispersive colloidal silicas such as ketone series solvent dispersive colloidal silica, toluene such as pure series solvent dispersive colloidal silica, methyl iso-butyl ketone (MIBK) such as Virahol of daily output chemical industrial company manufacturing etc.Silica dioxide granule can add when above-mentioned optical semiconductor encapsulates with preparation of compositions, also can add after the optical semiconductor encapsulation is with preparation of compositions.

With respect to 100 mass parts (A) polysiloxane and (B) total amount of hardener for epoxy resin, the consumption of inorganic particle surpasses 0 mass parts usually and below 80 mass parts, is preferably 0.1 mass parts～50 mass parts.

[driving fit auxiliary agent]

Optical semiconductor encapsulation of the present invention also can contain the following material of enumerating as the driving fit auxiliary agent with composition.

(organic compound that contains epoxy group(ing))

As the molecular weight that contains at least 2 epoxy group(ing) in the molecule is 100～1500 organic compound, and preferred oxirane ring alkyl etc. contains the compound of ester ring type epoxy group(ing) or has the compound of epoxy third oxyalkyl.The organic compound that especially preferably has the oxirane ring alkyl.Specifically can enumerate following such compound.

(polysiloxane that contains epoxy group(ing) beyond (A) polysiloxane)

As the polysiloxane that contains epoxy group(ing) beyond (A) polysiloxane, the hydrolytic condensate of the organoalkoxysilane that the organoalkoxysilane that contains epoxy group(ing) that can enumerate above-mentioned formula (1) expression and following formula (III) are represented or do not contain the polydimethylsiloxane that contains epoxy group(ing) etc. of silanol group.

R ⁵ _pSi(OR ⁶) _4-p (III)

(in the formula (III), R ⁵And R ⁶Represent 1 valency alkyl of non-replacement or replacement independently of one another, p is 0～2 integer.)

As the organoalkoxysilane of so above-mentioned formula (III) expression, specifically can enumerate tetraalkoxysilane classes such as tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane (p=0 in the formula (III));

Methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, the n-propyl Trimethoxy silane, the n-propyl triethoxyl silane, the sec.-propyl Trimethoxy silane, the sec.-propyl triethoxyl silane, the normal-butyl Trimethoxy silane, ne-butyltriethoxysilaneand, the n-pentyl Trimethoxy silane, the n-hexyl Trimethoxy silane, the n-heptyl Trimethoxy silane, the n-octyl Trimethoxy silane, vinyltrimethoxy silane, vinyltriethoxysilane, cyclohexyl trimethoxy silane, the cyclohexyl triethoxyl silane, phenyltrimethoxysila,e, phenyl triethoxysilane, the 3-r-chloropropyl trimethoxyl silane, the 3-chloropropyl triethoxysilane, 3,3,3-trifluoro propyl Trimethoxy silane, 3,3,3-trifluoro propyl triethoxyl silane, the 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, 2-hydroxyethyl Trimethoxy silane, 2-hydroxyethyl triethoxyl silane, 2-hydroxypropyl Trimethoxy silane, 2-hydroxypropyl triethoxyl silane, 3-hydroxypropyl Trimethoxy silane, 3-hydroxypropyl triethoxyl silane, 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane, 3-isocyanate group propyl trimethoxy silicane, 3-isocyanate group propyl-triethoxysilicane, 3-(methyl) acryloyl-oxy propyl trimethoxy silicane, 3-(methyl) acryloyl-oxy propyl-triethoxysilicane, 3-urea groups propyl trimethoxy silicane, trialkoxysilanes such as 3-urea groups propyl-triethoxysilicane (p=1 in the formula (III)); Dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethyl dimethoxy silane, the diethyl diethoxy silane, di dimethoxy silane, the di diethoxy silane, diisopropyl dimethoxy silane, the di-isopropyl diethoxy silane, di-n-butyl dimethoxy silane, the di-n-butyl diethoxy silane, two n-pentyl dimethoxy silane, two n-pentyl diethoxy silanes, di-n-hexyl dimethoxy silane, the di-n-hexyl diethoxy silane, two n-heptyl dimethoxy silane, two n-heptyl diethoxy silanes, di-n-octyl dimethoxy silane, the di-n-octyl diethoxy silane, two positive cyclohexyl dimethoxy silane, two positive cyclohexyl diethoxy silanes, dimethoxydiphenylsilane, dialkoxy silicane classes such as phenylbenzene diethoxy silane (p=2 in the formula (III)).

(oxetane compound)

As oxetane compound, can enumerate the compound of following formula (O-1)～(O-10) expression.

Wherein n represents 1～5 integer

Wherein

Wherein n represents 1～5 integer

Wherein n represents 1～8 integer

(mercaptan compound)

As mercaptan compound, can enumerate 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane, 3-sulfydryl propyl group three positive propoxy silane, 3-sulfydryl propyl group three isopropoxy silane, 3-sulfydryl propyl group three n-butoxy silane, 3-sulfydryl propyl group three sec-butoxy silane etc.

(compound) with isocyanuric acid ring structure

As compound, can enumerate isocyanuric acid three (3-trimethoxysilyl n-propyl) ester, isocyanuric acid three (2-hydroxyethyl) ester, triglycidyl isocyanurate, isocyanuric acid three (2-carboxy ethyl) ester etc. with isocyanuric acid ring structure.

(organoalkoxysilane or its hydrolyzate or condenses)

As organoalkoxysilane or its hydrolyzate or condenses, can enumerate organoalkoxysilane or its hydrolyzate or its condenses of above-mentioned formula (III) expression.Condenses for formula (III), as the independent condenses of above-mentioned illustrative organoalkoxysilane or the condenses of organoalkoxysilane more than 2 kinds, can enumerate the condenses of tetramethoxy-silicane oligopolymer, tetraethoxysilane oligopolymer, methyltrimethoxy silane oligopolymer, methyltrimethoxy silane and dimethyldimethoxysil,ne.When using the condenses of organoalkoxysilane, from the consistency aspect to (A) polysiloxane, the Mw of preferred condenses is below 3000.

These silica dioxide granules, the organic compound that contains epoxy group(ing), the above-mentioned polysiloxane polysiloxane that contains epoxy group(ing) or oxetane compound, mercaptan compound, compound, organoalkoxysilane or its hydrolyzate or the condenses in addition that contains the silanol group epoxy group(ing) with isocyanuric acid ring structure, both can when synthetic (A) polysiloxane, add, also can when forming cured article, add.Good in order to make with the consistency of (A) polysiloxane, more preferably interpolation when synthetic.

[antiaging agent]

(antioxidant)

From improving the thermotolerance aspect, with respect to 100 mass parts (A) composition and (B) total amount of composition, can cooperate the antioxidant of 0.1～5 mass parts, preferred hindered phenol in the composition of the present invention is antioxidant.As antioxidant, the compound of preferred following formula (C1) expression.

(in the formula (C1), R ^C1Be that carbonatoms is 1～15 m valency alkyl, part or all hydrogen atom can be substituted base and replace, between the carbon-to-carbon of alkyl, can have Sauerstoffatom, sulphur atom, nitrogen-atoms or-COO-.R ^C2Be that singly-bound or carbonatoms are 1～10 divalent alkyl independently of one another.R ^C3And R ^C4Represent that independently of one another carbonatoms is 1～10 1 valency alkyl.m _CIt is 2～10 integer.X be independently of one another singly-bound ,-O-,-COO-,-CO-,-NH-or their combination.)

As such compound, [3-(3 can to enumerate tetramethylolmethane four, 5-di-t-butyl-4-hydroxyphenyl) propionic ester], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester, [3-(3 for the sulfo-di ethylene bis, 5-di-t-butyl-4-hydroxyphenyl) propionic ester], N, N '-hexane-1, two [the 3-(3,5-di-t-butyl-4-hydroxyphenyl propionic acid amide) of 6-two bases, 2,4-dimethyl-6-(1-methyl pentadecyl) phenol, diethyl [[3,5-two (1, the 1-dimethyl ethyl)-and the 4-hydroxyphenyl] methyl] phosphonic acid ester, 3,3 ', 3 "; 5; 5 ', 5 "-six tertiary butyls-a, a '; a "-(Three methyl Benzene-2,4,6-three bases) three p-cresol, 4, two (hot sulfenyl the methyl)-ortho-cresols of 6-, ethylenebis (ethylene oxide) two [3-(a 5-tertiary butyl-4-hydroxy-tolyl) propionic esters], hexa-methylene is two, and [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester], 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-triketone, 2, and 6-di-t-butyl-4-(4, two (the hot sulfenyls)-1 of 6-, 3,5-triazine-2-base is amino) phenol etc.

(photostabilizer)

From improving sunproof aspect, with respect to 100 mass parts (A) composition and (B) total amount of composition, composition of the present invention can contain 0.1～5 mass parts photostabilizer, for example hindered amine is a photostabilizer.As photostabilizer, the compound of preferred following formula (C2) expression.

(in the formula (C2), R ^C5For carbonatoms is 1～15 n valency alkyl, part or all hydrogen atom can be substituted base and replace, between the carbon-to-carbon of alkyl, can have Sauerstoffatom, sulphur atom, nitrogen-atoms or-COO-.R ^C6Represent that independently of one another singly-bound or expression carbonatoms are 1～10 divalent alkyl.R ^C7～R ^C10Represent that independently of one another carbonatoms is 1～10 1 valency alkyl.n _CIt is 2 to 10 integer.Y be independently of one another singly-bound ,-O-,-COO-,-CO-,-NH-or their combination.)

As such compound, but illustration 2,2,4,4-tetramethyl--7-oxa--3,20-diaza two spiral shells [5.1.11.2]-heneicosane-21-ketone, 2,2,4,4-tetramethyl--21-oxo-7-oxa--3,20-diaza two spiral shells [5.1.11.2]-heneicosane-20-propionic acid dodecyl ester, 2,2,4,4-tetramethyl--21-oxo-7-oxa--3,20-diaza two spiral shells [5.1.11.2]-heneicosane-20-propionic acid tetradecyl ester, two (1,2,2,6,6-pentamethyl--4-piperidyl) [[3,5-two (1, the 1-dimethyl ethyl)-and the 4-hydroxyphenyl] methyl] the butyl malonic acid ester, two (2,2,6,6-tetramethyl--4-piperidyl) sebate, it is poly-that [{ 6-(1,1,3, the 3-tetramethyl butyl) amino-1,3,5-triazine-2,4-two bases } { (2,2,6,6-tetramethyl--4-piperidyl) imino-} hexa-methylene { (2,2,6,6-tetramethyl--4-piperidyl) imido }], 2-(2H-benzotriazole-2-yl)-4, two (1-methyl isophthalic acid-phenylethyl) phenol of 6-, 2-(2H-benzotriazole-2-yl)-4,6-di-tert-pentyl phenol etc.

＜luminous element 〉

Luminous element of the present invention obtains with the composition encapsulating optical semiconductor by using above-mentioned optical semiconductor encapsulation.When using the above-mentioned composition encapsulating optical semiconductor, can above-mentioned composition be solidified by known method.For example, behind the coating present composition,, can form cured article by making its curing in 3～13 hours 100～180 ℃ of heating.Solidify also and can implement by carrying out the interim process (step curing (step cure)) that heats up.As luminous element, can enumerate LED (Light Emitting Diode, photodiode) and LD (Laser Diode, laser diode) etc.

Fig. 1 and Fig. 2 are the synoptic diagram of LED.Among Fig. 1 and Fig. 2, as luminous element portion 50 usefulness packaged materials, 51 encapsulation of optical semiconductor.Among Fig. 1, luminous element portion 50 usefulness are dispersed with packaged material 51 encapsulation of fluor 54.Luminous element portion 50 has the fluorescence portion 52 of containing tackiness agent 53 and fluor 54 sometimes as shown in Figure 2.Optical semiconductor encapsulation can be enough of the present invention forms packaged material 51 among the LED illustrated in figures 1 and 2 with composition.

And, by with the encapsulation of above-mentioned optical semiconductor with luminous elements such as composition packaged LED elements, and composition is solidified, can obtain light-emitting device.As the LED element, can use blue-led element, ultraviolet LED element etc.And then, also can make and contain fluor in the cured article, will change from the light that the LED element sends.

(embodiment)

Below, by embodiment the present invention is described, but the present invention is not subjected to any qualification of this embodiment.Should illustrate that " part " in embodiment and the comparative example and " % " are only otherwise specify just expression " mass parts " and " quality % ".

Various mensuration in embodiment and the comparative example are undertaken by following method.

(1) weight-average molecular weight

The weight-average molecular weight of the polysiloxane that obtains (Mw) is measured under the following conditions by gel permeation chromatography (GPC), and obtains as the polystyrene conversion value.

Device: HLC-8120C (eastern Cao company make)

Post: TSK-gel MultiporeH _XL-M (eastern Cao company make)

Elutriant: THF, flow 0.5mL/min, lifting capacity 5.0%, 100 μ L

(2) epoxy equivalent (weight)

According to JIS C2105, measure the epoxy equivalent (weight) of resulting polysiloxane.

(3) content of phenyl

With respect to above-mentioned (A) polysiloxane in the resultant composition, the content of phenyl (quality %) is measured according to following method.

In 100 mass parts deuterated dimethyl sulfoxides, add 10 mass parts compositions, 10 mass parts trieline, be prepared into solution, use this solution to carry out as interior mark reagent ¹H-NMR measures.

By observe near the 6.2ppm to 6.6ppm from the peak of trieline with at the peak intensity ratio that observes between 6.8ppm to 8.0ppm from the phenyl in the composition, obtain phenyl in the composition with respect to the content of above-mentioned (A) polysiloxane.

(4) thermotolerance

Be coated on the composition that obtains on the silica glass and make that dry film thickness is 1mm,, next,, make cured article 150 ℃ of dry solidifications 5 hours then 100 ℃ of dry solidifications 1 hour.This cured article was preserved 500 hours at 150 ℃, and the outward appearance of the cured article after visual observation is preserved is with following benchmark evaluation thermotolerance.

(colour-change)

A: do not change

B: variable color is arranged slightly

C: xanthochromia takes place

(5) photostabilization

Be coated on the composition that obtains on the silica glass and make that dry film thickness is 1mm, then,, next, make cured article 150 ℃ of dry solidifications 5 hours 100 ℃ of dry solidifications 1 hour.Use has ended pointolite UV irradiating unit (the USHIO motor company manufacturing: SP-VII), this cured article is shone illumination 5000mW/cm of the light below the wavelength 350nm ²Ultraviolet ray 500 hours.The outward appearance of visual observation uviolizing after fixing thing is with following benchmark evaluation photostabilization.

A: do not change

B: xanthochromia takes place

C: burn blackening

(6) anti-separability and the anti-crackle when moisture absorption and Reflow Soldering

The composition that obtains is injected LED packaged piece (surface installing type, overlook pattern),, next,, make the cured article sample 150 ℃ of dry solidifications 5 hours 100 ℃ of dry solidifications 1 hour.With resulting sample in constant temperature and humidity cabinet (PL-3KP of Espec system) after preserving 5 hours and 8 hours under 85 ℃ of 85%RH, use desk-top reflow soldering apparatus (STR-2010 that Senju Metal Industry Co., Ltd makes), carry out the Reflow Soldering operation of 260 ℃ of 10 seconds kinds of 2 MAX.With peeling off between cured article in the packaged piece after the observation by light microscope reflow process and the packaging resin.To each sample, per 10 are carried out same observation, with anti-separability of following benchmark evaluation and anti-crackle.

(peeling off patience)

AA: also do not peel off even preserve after 8 hours

A: preserve after 5 hours and do not peel off, preserve and peel off after 8 hours

B: preserving had 1～2 to peel off in 10 after 5 hours

C: preserve to have more than 3 in 10 after 5 hours and peel off

(7) cold-resistant thermal shocking

To obtain composition and in surface installing type (overlooking pattern) packaged piece, be coated with, and,, be made into thus to estimate and use sample then 150 ℃ of heating 3 hours 100 ℃ of heating 1 hour.

Use cold shock testing device (TOM17 that ESPEC company makes),, be warmed up to 100 ℃ and be cooled to-40 ℃ from 100 ℃ from-40 ℃ with the speed of 1 ℃/min to above-mentioned evaluation sample, as 1 circulation, 1000 circulations of enforcement cold shock testing.After the off-test, with the crackle with resin inside peeled off between opticmicroscope visual observation packaged piece and the resin.A sample is carried out 10 same observations,, estimate cold-resistant thermal shocking according to following benchmark.

(7-1) (peel off)

A: do not peel off

There is 1 to 4 between packaged piece and resin, to produce and peel off among the B:10

Have between packaged piece and resin, to produce more than 5 in C:10 and peel off

(7-2) (crackle)

A: do not crack

There is 1 to crack in resin inside among the B:10 to 4

Have more than 5 in C:10 and crack in resin inside

(8) ability of inhibition electrode blackization

The composition that obtains is coated with in surface installing type (overlooking pattern) packaged piece,,, uses sample thereby be made into to estimate then 150 ℃ of heating 3 hours 100 ℃ of heating 1 hour.

Above-mentioned evaluation is rested in the pressure vessel with sample, then, in container, send into the hydrogen sulfide of 10 volume % after, carry out hydrogen sulfide exposure test in 24 hours at 80 ℃.After the off-test, use opticmicroscope that the variable color situation of the silver electrode in the packaged piece is carried out Visual Confirmation, suppress the ability of electrode blackization according to following benchmark evaluation.

(the electrode variable color suppresses energy)

A: electrode does not have variable color

B: the slight flavescence of electrode part

C: the serious blackening of electrode part

[embodiment 1]

(Momentive Co., Ltd. makes, trade(brand)name: XC96-723), 8 parts of 2-(3 ' as the organoalkoxysilane that contains epoxy group(ing) with the C-terminal polydimethylsiloxane of 20 parts of Mw=700,4 '-epoxycyclohexyl) ethyl trimethoxy silane, 13 parts of conducts contained the phenyltrimethoxysila,e of the organoalkoxysilane of phenyl, 3 parts of diazabicyclo undecylenes mixing as catalyzer, in 25 ℃ of reactions 8 hours.In this reaction, (mole number of polydimethylsiloxane (a1))/(total mole number of compound (a2) and compound (a3)) is 1/3.4, and (mole number of compound (a2))/(mole number of compound (a3)) is 33/67.

In this reaction product, add 94 parts of methyl iso-butyl ketone (MIBK), 33 parts of methyl alcohol, 33 parts of water, in 25 ℃ carry out 1 hour hydrolysis reaction after, add 38 part of 6% oxalic acid aqueous solution, carry out 1 hour neutralization reaction in room temperature., separate water layer, organic phase is cleaned with 34 parts of water thereafter.After carrying out 3 these washings operation, distillation removes and desolvates, and obtains the polysiloxane that contains epoxy group(ing) and phenyl (1) (hereinafter referred to as " polysiloxane (1) ") of Mw=1900.By aforesaid method, estimate the epoxy equivalent (weight) of this polysiloxane (1), the result is 1100.Weight-average molecular weight and epoxy equivalent (weight) the results are shown in table 1.

And, adding acid anhydrides MH-700G (mixture of hexahydro phthalic anhydride and methyl hexahydro phthalic anhydride, new Japanese natural sciences Co., Ltd. make) and make the ratio of anhydride equivalent/epoxy equivalent (weight) in polysiloxane (1) is 0.7, fully stir, preparation thermoset composition 1 is implemented the evaluation of above-mentioned thermotolerance etc. to said composition.The results are shown in table 1.

[embodiment 2]

(Momentive Co., Ltd. makes, trade(brand)name: XC96-723), 5 parts of 2-(3 ' as the organoalkoxysilane that contains epoxy group(ing) with the C-terminal polydimethylsiloxane of 20 parts of Mw=700,4 '-epoxycyclohexyl) ethyl trimethoxy silane, 16 parts of conducts contained the dimethoxydiphenylsilane of the organoalkoxysilane of phenyl, 3 parts of diazabicyclo undecylenes mixing as catalyzer, in 25 ℃ of reactions 8 hours.In this reaction, (mole number of polydimethylsiloxane (a1))/(total mole number of compound (a2) and compound (a3)) is 1/3.0, and (mole number of compound (a2))/(mole number of compound (a3)) is 24/76.

In this reaction product, add 107 parts of methyl iso-butyl ketone (MIBK), 33 parts of methyl alcohol, 33 parts of water, in 25 ℃ carry out 1 hour hydrolysis reaction after, add 38 part of 6% oxalic acid aqueous solution, carry out 1 hour neutralization reaction in room temperature., separate water layer, organic phase is cleaned with 34 parts of water thereafter.After carrying out 3 these washings operation, distillation removes and desolvates, and obtains the polysiloxane that contains epoxy group(ing) and phenyl (2) (hereinafter referred to as " polysiloxane (2) ") of Mw=2200.Estimate the epoxy equivalent (weight) of this polysiloxane (2) by aforesaid method, the result is 1700.Weight-average molecular weight and epoxy equivalent (weight) the results are shown in table 1.

And, carry out 1 identical operations with embodiment, prepare thermoset composition 2 thus, said composition is implemented the evaluation of above-mentioned thermotolerance etc.The results are shown in table 1.

[embodiment 3]

(Momentive Co., Ltd. makes, trade(brand)name: XC96-723), 14 parts of 2-(3 ' as the organoalkoxysilane that contains epoxy group(ing) with the C-terminal polydimethylsiloxane of 20 parts of Mw=700,4 '-epoxycyclohexyl) ethyl trimethoxy silane, 8 parts of conducts contained the phenyltrimethoxysila,e of the organoalkoxysilane of phenyl, 4 parts of diazabicyclo undecylenes mixing as catalyzer, in 25 ℃ of reactions 8 hours.In this reaction, (mole number of polydimethylsiloxane (a1))/(total mole number of compound (a2) and compound (a3)) is 1/3.4, and (mole number of compound (a2))/(mole number of compound (a3)) is 58/42.

In this reaction product, add 98 parts of methyl iso-butyl ketone (MIBK), 34 parts of methyl alcohol, 34 parts of water, in 25 ℃ carry out 1 hour hydrolysis reaction after, add 39 part of 6% oxalic acid aqueous solution, carry out 1 hour neutralization reaction in room temperature., separate water layer, organic phase is cleaned with 34 parts of water thereafter.After carrying out 3 these washings operation, distillation removes and desolvates, and obtains the polysiloxane that contains epoxy group(ing) and phenyl (3) (hereinafter referred to as " polysiloxane (3) ") of Mw=1700.Estimate the epoxy equivalent (weight) of this polysiloxane (3) by aforesaid method, the result is 600.(mole number of polydimethylsiloxane (a1))/(total mole number of compound (a2) and compound (a3)) is 1/3.4, and (mole number of compound (a2))/(mole number of compound (a3)) is 58/42.Weight-average molecular weight and epoxy equivalent (weight) the results are shown in table 1.

And by carrying out 1 identical operations with embodiment, preparation thermoset composition 3 is implemented the evaluation of above-mentioned thermotolerance etc. to said composition.The results are shown in table 1.

[embodiment 4]

The thermoset composition 1 that relative 100 mass parts obtain in embodiment 1 disperses 10 mass parts powder silica dioxide granules (RX300, Japanese AEROSIL Co., Ltd. make), preparation thermoset composition 4.Said composition is implemented the evaluation of above-mentioned thermotolerance etc.The results are shown in table 1.

[embodiment 5]

(Momentive Co., Ltd. makes, trade(brand)name: XC96-723), 9 parts of γ-Huan Yangbingyangbingjisanjiayangjiguiwans as the organoalkoxysilane that contains epoxy group(ing), 12 parts of phenyltrimethoxysila,e as the organoalkoxysilane that contains phenyl, 4 parts of diazabicyclo undecylenes as catalyzer mixed, in 25 ℃ of reactions 8 hours with the C-terminal polydimethylsiloxane of 20 parts of Mw=700.In this reaction, (mole number of polydimethylsiloxane (a1))/(total mole number of compound (a2) and compound (a3)) is 1/3.4, and (mole number of compound (a2))/(mole number of compound (a3)) is 58/42.

In this reaction product, add 98 parts of methyl iso-butyl ketone (MIBK), 34 parts of methyl alcohol, 34 parts of water, in 25 ℃ carry out 1 hour hydrolysis reaction after, add 39 part of 6% oxalic acid aqueous solution, carry out 1 hour neutralization reaction in room temperature., separate water layer, organic phase is cleaned with 34 parts of water thereafter.After carrying out 3 these washings operation, distillation removes and desolvates, and obtains the polysiloxane that contains epoxy group(ing) and phenyl (4) (hereinafter referred to as " polysiloxane (4) ") of Mw=2400.Estimate the epoxy equivalent (weight) of this polysiloxane (4) by aforesaid method, the result is 900.(mole number of polydimethylsiloxane (a1))/(total mole number of compound (a2) and compound (a3)) is 1/3.4, and (mole number of compound (a2))/(mole number of compound (a3)) is 58/42.Weight-average molecular weight and epoxy equivalent (weight) the results are shown in table 1.

And by carrying out 1 identical operations with embodiment, preparation thermoset composition 5 is implemented the evaluation of above-mentioned thermotolerance etc. to said composition.The results are shown in table 1.

[embodiment 6]

In possessing the reactor of stirrer, add 21.2 parts of acid anhydrides (Wako Pure Chemical Industries, Ltd.'s manufacturing, trade(brand)names: 5-norbornylene-2 with norbornylene skeleton, the 3-dicarboxylic anhydride), 78.8 parts of polydimethylsiloxane (manufacturing of Gelest company, goods names: DMS-H11), stir that have hydrogen-silicon key endways with 200 parts of toluene.In this solution, add 0.71 part of 0.3% aqueous isopropanol of platinum-divinyl tetramethyl disiloxane title complex, carry out addition reaction in 96 hours in 65 ℃.With ¹After H-NMR confirmed to be incorporated in the acid anhydrides hydrogen atom on the double key carbon and is consumed, distillation removed and desolvates, and obtained having the silicone compounds (below be also referred to as " silicone-modified acid anhydrides (1) ") (weight-average molecular weight=1400) of acid anhydride structure.

And, the ratio that adds the above-mentioned silicone-modified acid anhydrides (1) that obtains and make anhydride equivalent/epoxy equivalent (weight) in the polysiloxane (1) that embodiment 1 obtains is 0.7, fully stir, preparation thermoset composition 6 is implemented the evaluation of above-mentioned thermotolerance etc. to said composition.The results are shown in table 1.

[comparative example 1]

(Momentive Co., Ltd. makes, trade(brand)name: XC96-723), 2 parts of 2-(3 ' as the organoalkoxysilane that contains epoxy group(ing) with the C-terminal polydimethylsiloxane of 20 parts of Mw=700,4 '-epoxycyclohexyl) ethyl trimethoxy silane, 19 parts of conducts contained the dimethoxydiphenylsilane of the organoalkoxysilane of phenyl, 4 parts of diazabicyclo undecylenes mixing as catalyzer, in 25 ℃ of reactions 8 hours.In this reaction, (mole number of polydimethylsiloxane (a1))/(total mole number of compound (a2) and compound (a3)) is 1/3.0, and (mole number of compound (a2))/(mole number of compound (a3)) is 10/90.

In this reaction product, add 98 parts of methyl iso-butyl ketone (MIBK), 33 parts of methyl alcohol, 33 parts of water, in 25 ℃ carry out 1 hour hydrolysis reaction after, add 39 part of 6% oxalic acid aqueous solution, carry out 1 hour neutralization reaction in room temperature., separate water layer, organic phase is cleaned with 34 parts of water thereafter.After carrying out 3 these washings operation, distillation removes and desolvates, and obtains the polysiloxane that contains epoxy group(ing) and phenyl (7) (hereinafter referred to as " polysiloxane (7) ") of Mw=1800.By aforesaid method, estimate the epoxy equivalent (weight) of this polysiloxane (7), the result is 4100.Weight-average molecular weight and epoxy equivalent (weight) the results are shown in table 2.

And by carrying out 1 identical operations with embodiment, preparation thermoset composition 7 is implemented the evaluation of above-mentioned thermotolerance etc. to said composition.The results are shown in table 2.

[comparative example 2]

(Momentive Co., Ltd. makes, trade(brand)name: XC96-723), 17 parts of 2-(3 ' as the organoalkoxysilane that contains epoxy group(ing) with the C-terminal polydimethylsiloxane of 20 parts of Mw=700,4 '-epoxycyclohexyl) ethyl trimethoxy silane, 6 parts of conducts contained the phenyltrimethoxysila,e of the organoalkoxysilane of phenyl, 4 parts of diazabicyclo undecylenes mixing as catalyzer, in 25 ℃ of reactions 8 hours.In this reaction, (mole number of polydimethylsiloxane (a1))/(total mole number of compound (a2) and compound (a3)) is 1/3.5, and (mole number of compound (a2))/(mole number of compound (a3)) is 29/71.

In this reaction product, add 99 parts of methyl iso-butyl ketone (MIBK), 34 parts of methyl alcohol, 34 parts of water, in 25 ℃ carry out 1 hour hydrolysis reaction after, add 39 part of 6% oxalic acid aqueous solution, carry out 1 hour neutralization reaction in room temperature., separate water layer, organic phase is cleaned with 34 parts of water thereafter.After carrying out 3 these washings operation, distillation removes and desolvates, and obtains the polysiloxane that contains epoxy group(ing) and phenyl (8) (hereinafter referred to as " polysiloxane (8) ") of Mw=2000.Estimate the epoxy equivalent (weight) of this polysiloxane (8) by aforesaid method, the result is 530.Weight-average molecular weight and epoxy equivalent (weight) the results are shown in table 2.

And by carrying out 1 identical operations with embodiment, preparation thermoset composition 8 is implemented the evaluation of above-mentioned thermotolerance etc. to said composition.The results are shown in table 2.

[comparative example 3]

Use commercially available LED with methylsiloxane packaged material (" KER-2600 ", organosilicon Co., Ltd. of SHIN-ETSU HANTOTAI make, hydrogenation silyl addition curable methylsiloxane), carry out the evaluation identical with embodiment 1.The results are shown in table 2.

[comparative example 4]

Use commercially available LED with phenyl siloxane packaged material (" KER-6100 ", organosilicon Co., Ltd. of SHIN-ETSU HANTOTAI make, hydrogenation silyl addition curable phenyl siloxane), carry out the evaluation identical with embodiment 1.The results are shown in table 2.

[comparative example 5]

(Momentive Co., Ltd. makes, trade(brand)name: XC96-723), 1 part of 2-(3 ' as the organoalkoxysilane that contains epoxy group(ing) with the C-terminal polydimethylsiloxane of 20 parts of Mw=700,4 '-epoxycyclohexyl) ethyl trimethoxy silane, 19 parts of conducts contained the dimethoxydiphenylsilane of the organoalkoxysilane of phenyl, 4 parts of diazabicyclo undecylenes mixing as catalyzer, in 25 ℃ of reactions 8 hours.In this reaction, (mole number of polydimethylsiloxane (a1))/(total mole number of compound (a2) and compound (a3)) is 1/3.0, and (mole number of compound (a2))/(mole number of compound (a3)) is 10/90.

In this reaction product, add 98 parts of methyl iso-butyl ketone (MIBK), 33 parts of methyl alcohol, 33 parts of water, in 25 ℃ carry out 1 hour hydrolysis reaction after, add 39 part of 6% oxalic acid aqueous solution, carry out 1 hour neutralization reaction in room temperature., separate water layer, organic phase is cleaned with 34 parts of water thereafter.After carrying out 3 these washings operation, distillation removes and desolvates, and obtains the polysiloxane that contains epoxy group(ing) and phenyl (9) (hereinafter referred to as " polysiloxane (9) ") of Mw=20000.Estimate the epoxy equivalent (weight) of this polysiloxane (9) by aforesaid method, the result is 11000.Weight-average molecular weight and epoxy equivalent (weight) the results are shown in table 2.

And by carrying out 1 identical operations with embodiment, preparation thermoset composition 9 is implemented the evaluation of above-mentioned thermotolerance etc. to said composition.The results are shown in table 2.

[table 1]

[table 2]

Claims

1. composition is used in an optical semiconductor encapsulation, it is characterized in that,

Comprise A composition and B composition:

A: polysiloxane, it contains epoxy group(ing) and has or do not have substituent phenyl,

B: hardener for epoxy resin,

With respect to described A polysiloxane, the described content that has or do not have substituent phenyl is 8～30 quality %.

2. composition is used in optical semiconductor encapsulation as claimed in claim 1, it is characterized in that the epoxy equivalent (weight) of described A polysiloxane is 100～10000g/eq..

3. composition is used in optical semiconductor encapsulation as claimed in claim 1 or 2, it is characterized in that, described A polysiloxane has the structural unit of following formula (1) expression, the structural unit of following formula (2) expression and the structural unit of following formula (3) expression,

R ¹ ₂SiO _2/2 (1)

R ¹ _aR ^E _b(OR ²) _cSiO _(4-a-b-c)/2 (2)

R ¹ _aR ^P _b(OR ²) _cSiO _(4-a-b-c)/2 (3)

In formula (1)～(3),

A is 1 or 2, and b is 1 or 2, and c is 0 or 1, and a+b+c is 2 or 3.

4. use composition as each described optical semiconductor encapsulation in the claim 1～3, it is characterized in that described A polysiloxane has at least one group in the group shown in following general formula (4)～(7),

In the general formula (4), R ⁵The carbonatoms of expression methylene radical or divalent is that 2～10 straight chain shape alkylidene group or carbonatoms are a chain alkylidene group of 3～10;

In the general formula (5), R ⁶The carbonatoms of expression methylene radical or divalent is that 2～10 straight chain shape alkylidene group or carbonatoms are a chain alkylidene group of 3～10;

In the general formula (6), R ⁷The carbonatoms of expression methylene radical or divalent is that 2～10 straight chain shape alkylidene group or carbonatoms are a chain alkylidene group of 3～10;

In the general formula (7), R ⁸The carbonatoms of expression methylene radical or divalent is that 2～10 straight chain shape alkylidene group or carbonatoms are a chain alkylidene group of 3～10.

5. as each described optical semiconductor encapsulation composition in the claim 1～4, it is characterized in that, described A polysiloxane is to make end have the compound a 2 of the polydimethylsiloxane a1 of silanol group and following formula (8) expression and compound a 3 reactions of following formula (9) expression, the polysiloxane that next its reaction product hydrolysis is obtained

R ^E _mR ¹ _4-m-nSi(OR ³) _n (8)

In the formula (8), R ^EExpression contains the organic group of epoxy group(ing), R ¹And R ³Represent 1 valency alkyl of non-replacement or replacement independently of one another, m is 1 or 2, and n is 2 or 3, and m+n≤4;

R ^P _lR ¹ _4-l-kSi(OR ³) _k (9)

In the formula (9), R ^PExpression contains the organic group that has or do not have substituent phenyl, R ¹And R ³Represent 1 valency alkyl of non-replacement or replacement independently of one another, l is 1 or 2, and k is 2 or 3, and l+k≤4.

6. optical semiconductor encapsulation composition as claimed in claim 5, it is characterized in that described A polysiloxane is to be that 1/0.6～1/10 scope is reacted the polysiloxane that obtains by making polydimethylsiloxane a1, described compound a 2 and described compound a 3 with the mole number/compound a 2 of polydimethylsiloxane a1 and the total mole number of compound a 3.

7. as claim 5 or 6 described optical semiconductor encapsulation compositions, it is characterized in that described A polysiloxane is to be that 90/10～10/90 scope is reacted the polysiloxane that obtains by making described compound a 2 and described compound a 3 with the mole number of the mole number/compound a 3 of compound a 2.

8. use composition as each described optical semiconductor encapsulation in the claim 1～7, it is characterized in that, contain acid anhydrides as described B hardener for epoxy resin.

9. use composition as each described optical semiconductor encapsulation in the claim 1～8, it is characterized in that, further contain silica dioxide granule.

10. luminous element, it is to use the described optical semiconductor encapsulation of claim 9 with composition the optical semiconductor encapsulation to be obtained.