CN102686633A - Epoxy resin composition - Google Patents

Abstract

The invention aims to provide an epoxy resin composition containing a siloxane structure, which has excellent corrosive gas resistance. The epoxy resin composition comprises an organopolysiloxane (A) and a polycarboxylic acid (B), wherein the organopolysiloxane (A) is an epoxy resin having at least a glycidyl group and/or an epoxycyclohexyl group in the molecule and the polycarboxylic acid (B) is a polycarboxylic acid having at least two carboxyl groups and also having an aliphatic hydrocarbon group as the main skeleton.

Description

Composition epoxy resin

Technical field

The present invention relates to be fit to the composition epoxy resin and the cured article thereof of electric and electronic material applications, particularly photosemiconductor purposes.

Background technology

In the past, as the sealing material of optical semiconductors such as LED goods, considered to use composition epoxy resin from the balance aspect of performance and economy.Especially, be that the glycidyl ether type composition epoxy resin of representative is widely used with the good bisphenol A type epoxy resin of the balance of thermotolerance, the transparency and mechanical characteristics.

But; The short wavelengthization of LED goods emission wavelength (mainly representing the situation below the 480nm in the LED goods of blue light-emitting) result of development is pointed out; Because receive the influence of short-wavelength light, said sealing material is painted on led chip, the illumination decrease of final LED goods.

At this; With 3 '; 4 ' epoxycyclohexyl formic acid-3,4-epoxycyclohexyl methyl esters is the alicyclic epoxy resin of representative, compares with the glycidyl ether type composition epoxy resin with aromatic ring; Better aspect transparent, therefore carried out positive research (patent documentation 1,2) as the LED sealing material.

In addition; In recent years LED goods carry out more high brightnessization towards the backlight etc. of illumination or TV, and LED becomes with a large amount of heat releases during bright lamp, therefore; Even use the resin combination of this alicyclic epoxy resin also to be pointed out to exist in to cause on the led chip painted; The problem of the illumination decrease of final LED goods, (patent documentation 3) in addition, also has problems aspect weather resistance.

Patent documentation 1: japanese kokai publication hei 9-213997 communique

Patent documentation 2: No. 3618238 communique of Japanese Patent

Patent documentation 3: Japanese spy is the 2005-100445 communique again

Summary of the invention

Carried out following research in view of the endurance issues of aforementioned epoxy resins: uses with polyorganosiloxane resin or polysiloxane-modified epoxy resin etc. to resin representative, that introducing has siloxane backbone (skeleton that has the Si-O key specifically) as sealing material (patent documentation 3).

Generally speaking, known introducing resin that siloxane backbone arranged is superior to epoxy resin to the stability of light and heat.Therefore, when being applied to the sealing material of LED goods, we can say that the painted viewpoint from led chip considers that weather resistance is also good than epoxy resin.But this introducing has the gasproof body perviousness of resene of this siloxane backbone than epoxy resin difference.Therefore, when using polyorganosiloxane resin or polysiloxane-modified epoxy resin as the LED sealing material, although painted being out of question on the led chip,, the problem of generation is the deterioration that causes inner member of formation, painted.Under the situation about particularly in living environment, using, have all cpds floating, compound is penetrated into inside like this, becomes the beginning that has problems thus.For example; Be used under the situation of lighting use; Gas in the environment etc. see through the LED sealing material; Therefore there are the silver-colored composition that plated on the die-attach area that makes as the member of formation in the LED encapsulation (implement in order to improve reflectivity silver-plated) variable color or melanism, finally make the problem of the degradation of LED goods.

Be desirably in the no problem composition epoxy resin that contains siloxane structure in said gasproof body perviousness aspect on the market.

The inventor has carried out research extensively and profoundly in view of aforesaid present situation, and the result has accomplished the present invention.

That is, the present invention relates to:

(1) a kind of composition epoxy resin contains organopolysiloxane (A) and polycarboxylic acid (B), at this, and the condition below organopolysiloxane (A) and polycarboxylic acid (B) satisfy,

Organopolysiloxane (A):

The epoxy resin that in its molecule, has glycidyl and/or epoxycyclohexyl at least,

Polycarboxylic acid (B):

Have two above carboxyls, and be the polycarboxylic acid of main framing with the aliphatic alkyl;

(2) like above-mentioned (1) described composition epoxy resin, it is characterized in that, contain acid anhydrides (C);

(3) like above-mentioned (1) or (2) described composition epoxy resin, it is characterized in that the compound that polycarboxylic acid obtains for the reaction through 2 ~ 6 functional polyvalent alcohols and the representative examples of saturated aliphatic cyclic acid anhydride of carbonatoms more than 5;

(4) a kind of cured article obtains through each described composition epoxy resin in above-mentioned (1) to (3) is solidified; With

(5) a kind of optical semiconductor device, it contains optical semiconductor and above-mentioned (4) described cured article.

The invention effect

The corrosion-resistant gas property of composition epoxy resin of the present invention is good, and is therefore exceedingly useful as adhesive material, the sealing material of the photosemiconductor (LED goods etc.) that particularly in living environments such as illumination, uses in the optical material etc.

Embodiment

Below, composition epoxy resin of the present invention is described.

Composition epoxy resin of the present invention contains organopolysiloxane (A) and polycarboxylic acid (B) as neccessary composition.

Organopolysiloxane (A) to be being characteristic as the epoxy resin that in its molecule, has glycidyl and/or epoxycyclohexyl at least, generally through using trialkoxy silane with glycidyl or epoxycyclohexyl to obtain as the sol gel reaction of raw material.

As concrete example, can enumerate: the cancellated silsesquioxane type organopolysiloxane with three-dimensional extended of records such as TOHKEMY 2004-256609 communique, TOHKEMY 2004-346144 communique, WO2004/072150 communique, TOHKEMY 2006-8747 communique, WO2006/003990 communique, TOHKEMY 2006-104248 communique, WO2007/135909 communique, TOHKEMY 2004-10849 communique, TOHKEMY 2004-359933 communique, WO2005/100445 communique, TOHKEMY 2008-174640 communique.

The not special restriction of the structure of organopolysiloxane, because the silicone compounds of pure tridimensional network is really up to the mark, so desired hardness demulcent structure.Among the present invention, has the block structure body (below be called block type silicone compounds (D)) of ZGK 5 segment and the aforementioned silsesquioxane alkyl structure that obtains through sol gel reaction in the preferred especially molecule.

Block type silicone compounds (D) is not the compound that in straight chain, has repeating unit that resembles the common segmented copolymer; But become reticulated structure with three-dimensional extended; With the silsesquioxane alkyl structure is core, catenate ZGK 5 segment stretch and with the structure of next silsesquioxane structure bonding.This structure is effective on the equilibrated meaning of the cured article of giving curable compositions with hardness and flexibility.

Block type silicone compounds (D); For example can be described below; With the alkoxysilane compound containing trialkylsilyl group in molecular structure (a) of general formula (1) expression and the silicone oil (b) of general formula (2) expression is that raw material is made, and also can use the alkoxysilane compound containing trialkylsilyl group in molecular structure (c) of general formula (3) expression to be raw material as required.The chain ZGK 5 segment of block type silicone compounds (A) is formed by silicone oil (b), and three-dimensional netted silsesquioxane segment is formed by organoalkoxysilane (a) (also having organoalkoxysilane (c) as required).Below, each raw material is elaborated.

Alkoxysilane compound containing trialkylsilyl group in molecular structure (a) is represented by following formula (1).

XSi(OR ₂) ₃ (1)

As the X in the general formula (1), so long as have the then not special restriction of the organic group of epoxy group(ing).For example can enumerate: by the alkyl of the substituted carbonatoms 1 ~ 4 of glycidoxy, like beta epoxide propoxy-ethyl, γ-glycidoxy propyl group, γ-glycidoxy butyl etc.; Glycidyl; Alkyl by the carbonatoms 1 ~ 5 of the cycloalkyl substituted of the carbonatoms with Oxyranyle 5 ~ 8; Like β-(3, the 4-epoxycyclohexyl) ethyl, γ-(3, the 4-epoxycyclohexyl) propyl group, β-(3; 4-oxirane ring heptyl) ethyl, β-(3; The 4-epoxycyclohexyl) propyl group, β-(3, the 4-epoxycyclohexyl) butyl, β-(3, the 4-epoxycyclohexyl) amyl group etc.In these groups; Preferably by the alkyl of the substituted carbonatoms 1 ~ 3 of glycidoxy, by the alkyl of the carbonatoms 1 ~ 3 of the cycloalkyl substituted of the carbonatoms with epoxy group(ing) 5 ~ 8; For example beta epoxide propoxy-ethyl, γ-glycidoxy propyl group, β-(3; The 4-epoxycyclohexyl) ethyl, preferred especially β-(3, the 4-epoxycyclohexyl) ethyl.

As the R2 in the general formula (1), straight chain, side chain or the cyclic alkyl of expression carbonatoms 1 ~ 10.For example can enumerate: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl etc.These R ₂, consider preferable methyl or ethyl, special preferable methyl from the viewpoint of reaction conditionss such as consistency, reactivity.

Preferred concrete example as organoalkoxysilane (a); Can enumerate: beta epoxide propoxy-ethyl trimethoxy silane, beta epoxide propoxy-ethyl triethoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, β-(3; The 4-epoxycyclohexyl) ethyl trimethoxy silane, β-(3; The 4-epoxycyclohexyl) ethyl triethoxysilane etc., preferred especially β-(3，4-Huan Yanghuanjiji)Yi Jisanjiayangjiguiwan.These alkoxysilane compound containing trialkylsilyl group in molecular structure (a) can use or use two or more separately, also can with after organoalkoxysilane (c) combination stated use.

Silicone oil (b) has the chain silicone oil of silanol base for the end of structure with following formula (2) expression,

(in the formula, m representes repeat number.）

The a plurality of R that exist in the general formula (2) ₃Can be identical or different each other, alkyl, the aryl of carbonatoms 6 ~ 14 or the thiazolinyl of carbonatoms 2 ~ 10 of expression carbonatoms 1 ~ 10.

Alkyl as carbonatoms 1 ~ 10; Can enumerate straight chain, side chain or the cyclic alkyl of carbonatoms 1 ~ 10, for example can enumerate: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec.-butyl, the tertiary butyl, n-pentyl, isopentyl, amyl group, n-hexyl, cyclopentyl, cyclohexyl, octyl group, 2-ethylhexyl, nonyl, decyl etc.In these groups, when considering photostabilization, preferable methyl, ethyl, cyclohexyl.

As the aryl of carbonatoms 6 ~ 14, for example can enumerate: phenyl, o-tolyl, a tolyl, p-methylphenyl, xylyl etc.

As the thiazolinyl of carbonatoms 2 ~ 10, can enumerate: thiazolinyls such as vinyl, 1-methyl ethylene, allyl group, propenyl, crotonyl, pentenyl, hexenyl etc.

Consider R from photostabilization, stable on heating viewpoint ₃Be preferably methyl, phenyl, cyclohexyl, n-propyl, special preferable methyl, phenyl.

The m of the compound of general formula (2) is a MV, and expression 3 ~ 200 is preferred 3 ~ 100, more preferably 3 ~ 50.M was less than 3 o'clock, and it is really up to the mark that cured article becomes, and the low elastic modulus characteristic descends.M had the tendency of the mechanical characteristics deterioration of cured article greater than 200 o'clock, and is therefore not preferred.

The weight-average molecular weight (Mw) of silicone oil (b) is preferably in the scope of 300 ~ 18000 (measured values of GPC (GPC)).In these silicone oil, when considering the following Young's modulus of low temperature, the silicone oil of preferred molecular weight 300 ~ 10000, when further considering the consistency when making up materialization, more preferably 300 ~ 5000 silicone oil, preferred especially 500 ~ 3000 silicone oil.Weight-average molecular weight is lower than at 300 o'clock, and the characteristic of characteristic segmental chain ZGK 5 part is difficult to performance, might be impaired as the characteristic of block type, and surpass at 18000 o'clock, and having violent layered structure, transmissivity variation when being used for optical material is difficult to use.Among the present invention,, can use GPC, calculate the weight-average molecular weight (Mw) of the polystyrene conversion of under following condition, measuring as the molecular weight of silicone oil (b).

The various conditions of GPC

Manufacturers: Shimadzu Seisakusho Ltd.

Post: guard column SHODEX GPC LF-G LF-804 (3)

Flow velocity: 1.0ml/ minute

Column temperature: 40 ℃

The solvent that uses: THF (THF)

Detector: RI (differential refraction detector)

The dynamic viscosity of silicone oil (b) is preferably in the scope of 10 ~ 200cSt, more preferably in the scope of 30 ~ 90cSt.When being lower than 10cSt, the viscosity of block type silicone compounds (D) is low excessively, is not suitable for sometimes as the optical semiconductor sealing agent; In addition, when surpassing 200cSt, the viscosity of block type silicone compounds (D) rises; Have tendency to operation property generation obstacle, therefore not preferred.At this, dynamic viscosity is meant the value of using Ubbelohde (Ubbelohde) viscometer determining according to JIS Z 8809.

As the preferred concrete example of silicone oil (b), can enumerate following goods name.For example; PRX413, the BY16-873 of east レ ダ ウ コ one ニ Application グ シ リ コ one Application manufactured; X-21-5841, KF-9701 that chemical industrial company of SHIN-ETSU HANTOTAI makes; XC96-723, TSR160, YR3370, YF3800, XF3905, YF3057, YF3807, YF3802, the YF3897 of モ メ Application テ イ Block manufactured; YF3804, XF3905, the DMS-S12 of Gelest manufactured, DMS-S14, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S42, DMS-S45, DMS-S51, PDS-0332, PDS-1615, PDS-9931 etc.In above-mentioned, consider preferred PRX413, BY16-873, X-21-5841, KF-9701, XC96-723, YF3800, YF3804, DMS-S12, DMS-S14, DMS-S15, DMS-S21, PDS-1615 from the viewpoint of molecular weight, dynamic viscosity.In the middle of these,, consider preferred especially X-21-5841, XC96-723, YF3800, YF3804, DMS-S14, PDS-1615 from the viewpoint of molecular weight in order to have the flexibility characteristic of ZGK 5 segment.These silicone oil (b) can use separately or two or more combination is used.

Below, the organoalkoxysilane (c) that uses as required is elaborated.Organoalkoxysilane (c) has the structure of following formula (3).

R ₄(OR ₅) ₃ (3)

(in the formula, R ⁴The expression methyl or phenyl.）

As the R in the general formula (3) ₅, straight chain, side chain or the cyclic alkyl of expression carbonatoms 1 ~ 10.For example can enumerate: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, n-hexyl, cyclopentyl, cyclohexyl etc.These R ₅, consider preferable methyl or ethyl from the viewpoint of reaction conditionss such as consistency, reactivity.

As the preferred concrete example of organoalkoxysilane (c), can enumerate: methyltrimethoxy silane, phenyltrimethoxysila,e, Union carbide A-162, phenyl triethoxysilane etc.In the above-mentioned substance, preferable methyl Trimethoxy silane, phenyltrimethoxysila,e.

Among the present invention; For the molecular weight of regulating block type silicone compounds (D), the thermotolerance, photostabilization, low-moisture permeability, low gas-premeable etc. of consistency, cured article when forming compsn, organoalkoxysilane (c) can use with organoalkoxysilane (a) combination.

When using organoalkoxysilane (c), in the total mole of organoalkoxysilane (a) and organoalkoxysilane (c), organoalkoxysilane (c) is preferably with the scope use of 5 ~ 70 moles of %, more preferably 5 ~ 50 moles of %, preferred especially 10 ~ 40 moles of %.When surpassing 70 moles of %, the cross-linking density of cured article descends, and physical strength descends, and is therefore not preferred.

Reactive ratio as organoalkoxysilane (a), silicone oil (b), organoalkoxysilane (c); Preferably with respect to silanol base 1 equivalent of silicone oil (b); Alkoxyl group in the organoalkoxysilane (a) (and the organoalkoxysilane (c) that uses as required) representes to be preferably 1.5 ~ 200 with equivalent value; More preferably 2 ~ 200, preferred especially 2 ~ 100 are reacted.

Equivalent value surpasses at 200 o'clock, uses the cured article of block type silicone compounds (D) really up to the mark, and the low elastic modulus characteristic of target descends.

Below, the preferable production process of block type silicone compounds (D) is specified.

As the method for manufacture of block type silicone compounds (D), the manufacturing process that preferably pass through following (i), (ii) representes.

Manufacturing process (i): the operation of dealcoholysis condensation of carrying out the end capped silicone oil of silanol (b) and organoalkoxysilane (a) (and organoalkoxysilane (c)) with alkoxyl group.

Manufacturing process is (ii): the operation of adding the hydrolytic condensation between the alkoxyl group that water carries out organoalkoxysilane (a) (and organoalkoxysilane (c)).

About manufacturing process (i), (ii), as long as via each operation, can react with random order.

As preferable production process, can enumerate following three kinds of method of manufacture particularly.

< method of manufacture (1) >

At first,, carry out dealcoholization condensation reaction through silicone oil (b) and organoalkoxysilane (a) (and organoalkoxysilane (c)) and the silicone oil end carried out alkoxysilane-modified, obtain the operation of alkoxysilane-modified thing (d) thus as manufacturing process (i),

Then; As manufacturing process (ii); The operation of carrying out in the alkoxysilane-modified thing (d) of organoalkoxysilane (a) (and organoalkoxysilane (c)) and the silicone oil that in manufacturing process (i), obtains, adding water and carrying out the hydrolytic condensation between the alkoxyl group is through making the method for block type silicone compounds (D) via these operations.

< method of manufacture (2) >

At first, as manufacturing process (ii), carry out in organoalkoxysilane (a) (and organoalkoxysilane (c)) adding water and carry out the hydrolytic condensation between the alkoxyl group, obtain the operation of the silsesquioxane (e) that intramolecularly has alkoxyl group thus,

Then; As manufacturing process (i); Carry out carrying out the operation of the dealcoholization condensation reaction of alkoxyl group residual in the silsesquioxane alkyl structure and silanol, through make the method for block type silicone compounds (D) via these operations through the silicone oil (b) and the reaction of silsesquioxane (e).

< method of manufacture (3) >

At first; As manufacturing process (i); Dealcoholization condensation reaction through silicone oil (b) and organoalkoxysilane (a) (and organoalkoxysilane (c)) carries out the silicone oil end alkoxysilane-modified, obtains alkoxysilane-modified thing (d) thus, in system, adds water then; And in one pot; As manufacturing process (ii), carry out the hydrolysis-condensation reaction between the alkoxyl group of residual organoalkoxysilane (a) (and organoalkoxysilane (c)) and alkoxysilane-modified thing (d), make the method for block type silicone compounds (D) thus.

Among the present invention, consider the preferred aforesaid method of manufacture (3) of in a pot, reacting one by one of using from the viewpoint that shortens manufacturing process.

Below, method of manufacture (3) further is described particularly.

When in one pot, reacting; With with the opposite order of aforesaid method of manufacture (3) be that manufacturing process is when carrying out manufacturing process (i) after (ii); The silsesquioxane oligopolymer with alkoxyl group through manufacturing process (ii) forms is incompatible with silicone oil (b); In the manufacturing process (i) of back, do not carry out the dealcoholysis polycondensation, the possibility height that silicone oil is residual.On the other hand; Use resembles method of manufacture (3) when in one pot, carrying out (ii) method of manufacturing process like this in manufacturing process (i) back; So silicone oil (b) is higher with organoalkoxysilane (a) or consistency (c), therefore can avoid incompatible as previously mentioned the problem of not reacting.In addition, there are a large amount of unreacted lower molecular weight organoalkoxysilanes, therefore consider it also is preferred from reactive viewpoint with respect to the silanol base.When in one pot, reacting; At first in manufacturing process (i); Carry out the dealcoholysis condensation of silicone oil (b) and organoalkoxysilane (a) (and organoalkoxysilane (c)), the end of silicone oil is carried out the alkoxysilyl modification, obtain alkoxysilane-modified thing (d).Therefore in manufacturing process (i), do not add water, do not cause the hydrolytic condensation between the alkoxyl group, when using alkoxyl group more than 3 equivalents to react, think that alkoxysilane-modified thing (d) exists with the structure of following formula (4) expression with respect to 1 equivalent silanol base.

(in the formula (4), R ₂, R ₃Represent the implication identical, R with m with the front ₆Represent aforesaid X or R ₄）

In manufacturing process (i); With respect to 1 equivalent silanol base; When reacting less than 1.0 normal amounts, there is not alkoxyl group when finishing, therefore can not proceed to manufacturing process (ii) in manufacturing process (i) with alkoxyl group; When reacting between 1.0 ~ 1.5 equivalents with alkoxyl group in addition; Two the above alkoxyl groups in the organoalkoxysilane (a) (and organoalkoxysilane (c)) and the silanol radical reaction of silicone oil (b), thus when finishing in manufacturing process (i) the molecule quantitative change get too high, thereby produce gelation.Therefore, with respect to 1 equivalent silanol base, need make alkoxyl group to react more than 1.5 equivalents.Consider from the viewpoint of reaction control, more than preferred 2.0 equivalents.

Manufacturing process (i) directly adds water and carries out the hydrolytic condensation (manufacturing process (ii)) between the alkoxyl group after finishing.In addition, manufacturing process (ii) in, cause the reaction of (I) ~ (III) as follows.

(I) condensation reaction between the alkoxyl group of residual organoalkoxysilane (a) (and organoalkoxysilane (c)) in the system.

Condensation reaction between the alkoxyl group of alkoxysilane-modified thing (d) that (II) in manufacturing process (i), obtains and organoalkoxysilane (a) (and organoalkoxysilane (c)).

(III) the alkoxysilane-modified thing (d) that in manufacturing process (i), obtains and (I) in condensation reaction between the alkoxyl group of partial condensate of the organoalkoxysilane (a) (and organoalkoxysilane (c)) that generates.

Manufacturing process (ii) in, above-mentioned reaction takes place compoundly, the silsesquioxane segmental generates and further carries out simultaneously with the condensation of the chain ZGK 5 segment that derives from silicone oil.

The manufacturing of block type silicone compounds (D) also can not use catalyzer to carry out, and still, reaction is carried out slowly during catalyst-free, considers from the viewpoint that shortens the reaction times, preferably in the presence of catalyzer, carries out.As operable catalyzer, just can use so long as show acidity or alkaline compound.As the example of an acidic catalyst, can enumerate: mineral acid, example hydrochloric acid, sulfuric acid, nitric acid etc.; Organic acid is like formic acid, acetate, oxalic acid etc.In addition,, can use as the example of basic catalyst: mineral alkali, like alkali metal hydroxides such as sodium hydroxide, Pottasium Hydroxide, Lithium Hydroxide MonoHydrate, cesium hydroxides, alkaline carbonates such as yellow soda ash, salt of wormwood, sodium hydrogencarbonate, saleratus etc.; Organic bases is like ammonia, triethylamine, two inferior second triamines, n-Butyl Amine 99, dimethylaminoethanol, trolamine, TMAH etc.In these catalyzer, particularly consider preferred mineral alkali, preferred especially sodium hydroxide, Pottasium Hydroxide from the viewpoint of from resultant, removing catalyzer easily.The addition of catalyzer is generally 0.001 ~ 7.5 weight % with respect to the total weight of the organoalkoxysilane in the reaction system (a) (and organoalkoxysilane (c)), preferred 0.01 ~ 5 weight %.

About the addition means of catalyzer, can directly add or state use down that can be in the solvent that is dissolved into solubility etc.Wherein, preferably in advance the state of catalyst dissolution in alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols added down.At this moment; So that the aqueous solution form of water etc. is when adding, as previously mentioned, folk prescription is to the condensation of carrying out organoalkoxysilane (a) (and organoalkoxysilane (c)); The silsesquioxane oligopolymer that generates thus is incompatible with silicone oil (b), might produce white casse.

The manufacturing of block type silicone compounds (D) can perhaps be carried out in solvent down solvent-free.In addition, in the process of manufacturing process, also can append solvent.Solvent during as the use solvent is so long as the then not special restriction of the solvent of dissolvane TMOS (a), organoalkoxysilane (c), silicone oil (b), alkoxysilane-modified thing (d).As such solvent, can illustration for example: aprotic polar solvent, like N, N,N-DIMETHYLACETAMIDE, THF etc.; Ketone is like methylethylketone, MIBK, ketopentamethylene etc.; The ester class is like ETHYLE ACETATE, butylacetate, ethyl lactate, isopropyl butyrate etc.; Alcohols is like methyl alcohol, ethanol, propyl alcohol, butanols etc.; Hydrocarbon is like hexane, hexanaphthene, toluene, YLENE etc.; Deng.Among the present invention, consider the preferably reaction in alcohols, more preferably methyl alcohol, ethanol from the viewpoint of reaction control.The usage quantity of solvent is as long as then not special restriction in the smooth and easy scope of carrying out of reaction, with respect to 100 parts of the total weight of the compound of organoalkoxysilane (a) (and organoalkoxysilane (c)), silicone oil (b), uses about 0 ~ about 900 weight parts usually.Temperature of reaction depends on catalytic amount, is generally 20 ~ 160 ℃, preferred 40 ~ 140 ℃, and preferred especially 50 ~ 150 ℃.In addition, the reaction times is generally 1 ~ 40 hour respectively in each manufacturing process, preferred 5 ~ 30 hours.

When reaction finishes, through cancellation and/or washing catalyzer is removed as required.Under the situation of washing, preferably according to employed solvent types add can with the solvent of water sepn.As preferred solvent, can illustration for example: ketone, like methylethylketone, MIBK, ketopentamethylene etc.; The ester class is like ETHYLE ACETATE, butylacetate, ethyl lactate, isopropyl butyrate etc.; Hydrocarbon is like hexane, hexanaphthene, toluene, YLENE etc.; Deng.

This reaction can only be carried out removing of catalyzer through washing; But, owing to react under any condition in acidity, alkalescence, therefore; Preferably carry out washing after the cancellation, perhaps use behind the adsorbents adsorb catalyzer through removing by filter sorbent material through neutralization reaction.

In the neutralization reaction, just can use so long as show acidity or alkaline compound.As the example that shows the tart compound, can enumerate: mineral acid, example hydrochloric acid, sulfuric acid, nitric acid etc.; Organic acid is like formic acid, acetate, oxalic acid etc.In addition; Example as the compound that shows alkalescence; Can use mineral alkali; Like alkali metal hydroxides such as sodium hydroxide, Pottasium Hydroxide, Lithium Hydroxide MonoHydrate, cesium hydroxides, alkaline carbonates such as yellow soda ash, salt of wormwood, sodium hydrogencarbonate, saleratus, phosphoric acid salts such as phosphoric acid, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate, dibasic, sodium phosphate, polyphosphoric acid, tripoly phosphate sodium STPP; Organic bases is like ammonia, triethylamine, two inferior second triamines, n-Butyl Amine 99, dimethylaminoethanol, trolamine, TMAH etc.In these materials, particularly consider from the viewpoint of from resultant, removing easily, preferred mineral alkali or mineral acid, further preferred easily with near the phosphoric acid salt of pH regulator neutral etc.

As sorbent material, can illustration: atlapulgite, gac, zeolite, inorganic/the organic type synthetic adsorbent, ion exchange resin etc., can enumerate following goods as concrete example.

As atlapulgite; For example can enumerate: east newly changes into atlapulgite SA35, SA1, T, R-15, E, ニ Star カ Na イ ト G-36, G-153, the G-168 of manufactured, ガ レ オ Application ア one ス that marshy land chemical industrial company makes, ミ ズ カ エ one ス etc.As gac; For example can enumerate: CL-H, Y-10S, the Y-10SF of aginomoto Off ア イ Application テ Network ノ manufactured, the S that Off タ system ラ chemical company makes, Y, FC, DP, SA1000, K, A, KA, M, CW130BR, CW130AR, GM130A etc.As zeolite, for example can enumerate: the clear molecular sieve 3a, 4A, 5A, 13X with manufactured of コ ニ オ Application etc.As synthetic adsorbent; For example can enumerate: キ ヨ one ワ one De 100,200,300,400,500,600,700,1000,2000 that consonance chemical company makes; ア Application バ one リ ス ト 15JWET, 15DRY, 16WET, 31WET, A21, ア Application バ one ラ イ ト IRA400JCl, IRA403BLCl, the IRA404JCl of rom Haas (ロ one system ア Application De Ha one ス) manufactured, the ダ ウ エ Star Network ス 66 of DOW Chemical (ダ ウ ケ ミ カ Le) manufactured, HCR-S, HCR-W2, MAC-3 etc.

Sorbent material is added in the reaction solution, stir, processing such as heating, adsorptive catalyst, Filtration Adsorption agent then again with washing residue, can be removed catalyzer, sorbent material thus.

Reaction finishes can carry out purifying through the separation and purification means of washing, filtering and other is habitual after back or the cancellation.As means of purification, for example can enumerate: column chromatography, concentrating under reduced pressure, distillation, extraction etc.These means of purification can be carried out separately, also can multiple combination be used.

Use when reacting as reaction solvent with the miscible solvent of water, preferably after cancellation through distillation or concentrating under reduced pressure from system, remove with the miscible reaction solvent of water after, use can be washed with the solvent of water sepn.

Washing back is removed through concentrating under reduced pressure etc. and is desolvated, and can obtain block type silicone compounds (D) thus.

The outward appearance of the block type silicone compounds (D) that obtains like this is generally water white transparency and under 25 ℃, has mobile liquid state.In addition, its molecular weight is preferably 800 ~ 20000 to measure the weight-average molecular weight obtain through GPC, and more preferably 1000 ~ 10000, preferred especially 1500 ~ 6000.Weight-average molecular weight is lower than at 800 o'clock, and thermotolerance might descend, and surpasses at 20000 o'clock, and viscosity rises, and operation property is caused obstacle.Addition, reaction times, the temperature of reaction of water are regulated when the equivalence ratio that in addition, molecular weight can be through organoalkoxysilane (a) (and organoalkoxysilane (c)) and silicone oil (b), the molecular weight of silicone oil (b), reaction.

Weight-average molecular weight is to use the weight-average molecular weight (Mw) of the polystyrene conversion that GPC measures under following condition.

The various conditions of GPC

Manufacturers: Shimadzu Seisakusho Ltd.

Post: guard column SHODEX GPC LF-G LF-804 (3)

Flow velocity: 1.0ml/ minute

Column temperature: 40 ℃

The solvent that uses: THF (THF)

Detector: RI (differential refraction detector)

In addition, the epoxy equivalent (weight) of this block type silicone compounds (D) (method through JIS K-7236 record is measured) is preferably 300 ~ 1600g/eq, more preferably 400 ~ 1000g/eq, preferred especially 450 ~ 900g/eq.When epoxy equivalent (weight) is lower than 300g/eq, have its cured article as hard as firmly, the tendency that Young's modulus is too high when surpassing 1600g/eq, has the tendency of the mechanical characteristics deterioration of cured article, and is therefore not preferred.

The viscosity of block type silicone compounds (D) (E type viscometer, 25 ℃ measure down) is preferably 50 ~ 20000mPas, more preferably 500 ~ 10000mPas, preferred especially 800 ~ 5000mPas.When viscosity was lower than 50mPas, viscosity was low excessively, might be not suitable for as the optical semiconductor encapsulating material purposes, and when viscosity surpassed 20000mPas, viscosity was too high, the deterioration of operation property sometimes.

Derive from the block type silicone compounds (D) silsesquioxane, with the Siliciumatom of three Sauerstoffatom bondings ratio with respect to whole Siliciumatoms, be preferably 5 ~ 50 moles of %, more preferably 8 ~ 30 moles of %, preferred especially 10 ~ 20 moles of %.Derive from silsesquioxane, when being lower than 5 moles of % with respect to the ratio of whole Siliciumatoms with the Siliciumatom of three Sauerstoffatom bondings, as the characteristic of chain ZGK 5 segment, cured article has the tendency that became soft, might produce surface viscosity or cut.In addition, when surpassing 50 moles of %, as silsesquioxane segmental characteristic, it is really up to the mark that cured article becomes, therefore not preferred.In addition, this ratio can recently be confirmed by the organoalkoxysilane (a) (and organoalkoxysilane (c)) and the equivalent of silicone oil (b).

The ratio of the Siliciumatom that exists can be passed through block type silicone compounds (D) ¹H-NMR, ²⁹Si-NMR, ultimate analysis wait and obtain.

Polycarboxylic acid (B) is to have at least two carboxyls, is that main framing is the compound of characteristic with the aliphatic alkyl.

As polycarboxylic acid (B), preferred 2 ~ 6 functional carboxylic acids, the more preferably compound that obtains of the reaction through 2 ~ 6 functional polyvalent alcohols and the acid anhydrides of carbonatoms more than 5.The poly carboxylic acid that further preferred above-mentioned acid anhydrides is the representative examples of saturated aliphatic cyclic acid anhydride.

As 2 ~ 6 functional polyvalent alcohols, so long as, can enumerate: glycols as the then not special restriction of compound alcohols, that have alcoholic extract hydroxyl group; Like terepthaloyl moietie, 1,2-Ucar 35,1, ammediol, 1; 2-butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, 1; 6-pinakon, cyclohexanedimethanol, 2,4-diethylammonium pentanediol, 2-ethyl-2-butyl-1, ammediol, NSC 6366, tristane dimethanol, norbornylene glycol etc.; Three alcohols are like glycerine, trimethylolethane, TriMethylolPropane(TMP), tri hydroxy methyl butane, 2-methylol-1,4-butyleneglycol etc.; The tetrol class is like tetramethylolmethane, two (TriMethylolPropane(TMP)) etc.; Six alcohols are like Dipentaerythritol etc.; Deng.

As preferred especially alcohols,, preferred especially: 1 for the alcohol of carbonatoms more than 5; 6-pinakon, 1,4 cyclohexane dimethanol, 1,3-cyclohexanedimethanol, 1; 2-cyclohexanedimethanol, 2,4-diethylammonium pentanediol, 2-ethyl-2-butyl-1, compounds such as ammediol, NSC 6366, tristane dimethanol, norbornylene glycol; Wherein, more preferably has the alcohols of branched structure or ring texture, like 2-ethyl-2-butyl-1; Ammediol, NSC 6366,2,4-diethylammonium pentanediol, 1,4 cyclohexane dimethanol, tristane dimethanol, norbornylene glycol etc.

As acid anhydrides, preferred especially: methyl tetrahydrophthalic anhydride, methyl carbic anhydride, carbic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylene-dimalonic acid acid anhydride, dicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, methyl bicycle [2.2.1] heptane-2; 3-dicarboxylic acid anhydride, hexanaphthene-1,3,4-tricarboxylic acid-3; 4-acid anhydrides etc., wherein preferable methyl hexahydrophthalic anhydride, hexanaphthene-1,3; 4-tricarboxylic acid-3, the 4-acid anhydrides.

As the condition of addition reaction, not special restriction as one of concrete reaction conditions, is that acid anhydrides, polyvalent alcohol are reacted heating down at 40 ~ 150 ℃ under catalyst-free, solvent-free condition, and reaction finishes the directly method of taking-up of back.But, be not limited to this reaction conditions.

As polycarboxylic acid (B), the compound of preferred especially following formula (5) expression.

(in the formula (5), a plurality of Q of existence represent more than one in Wasserstoffatoms, methyl, the carboxyl, and P is aforesaid chain, the cyclic aliphatic group that derives from the carbonatoms 2 ~ 20 of polyvalent alcohol, and n representes the valence mumber of polyvalent alcohol.）

Composition epoxy resin of the present invention preferably contains acid anhydrides (C).As acid anhydrides (C); Can enumerate particularly: Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, PMA acid anhydride, maleic anhydride, Tetra Hydro Phthalic Anhydride, methyl tetrahydrophthalic anhydride, methyl carbic anhydride, carbic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylene-dimalonic acid acid anhydride, dicyclo [2.2.1] heptane-2; 3-dicarboxylic acid anhydride, methyl bicycle [2.2.1] heptane-2; 3-dicarboxylic acid anhydride, hexanaphthene-1; 3,4-tricarboxylic acid-3, acid anhydrides such as 4-acid anhydrides.

Preferred especially: methyl tetrahydrophthalic anhydride, methyl carbic anhydride, carbic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylene-dimalonic acid acid anhydride, dicyclo [2.2.1] heptane-2; 3-dicarboxylic acid anhydride, methyl bicycle [2.2.1] heptane-2; 3-dicarboxylic acid anhydride, hexanaphthene-1; 3,4-tricarboxylic acid-3,4-acid anhydrides etc.

Preferred especially following formula (6)

(in the formula, R ³In expression Wasserstoffatoms, methyl, the carboxyl more than one) hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, the hexanaphthene-1,3 of expression, 4-tricarboxylic acid-3; 4-acid anhydrides, wherein preferable methyl hexahydrophthalic anhydride, hexanaphthene-1,3; 4-tricarboxylic acid-3, the 4-acid anhydrides.

When using acid anhydrides (C), be preferably following scope with the usage rate of polycarboxylic acid (B).

W1/(W1+W2)=0.05~0.70

Wherein, W1 representes the cooperation weight part of polycarboxylic acid (B), and W2 representes the cooperation weight part of acid anhydrides (C).As the scope of W1/ (W1+W2), more preferably 0.05 ~ 0.60, further preferred 0.10 ~ 0.55, preferred especially 0.15 ~ 0.4.Be lower than at 0.05 o'clock, the tendency that the acid anhydrides volatilization increases during curing is strong, and is therefore not preferred.Surpass at 0.70 o'clock, become HV, be difficult to operation.

Composition epoxy resin of the present invention; Contain as epoxy resin organopolysiloxane (A) and as the polycarboxylic acid (B) of solidifying agent as neccessary composition; And contain acid anhydrides (C) as optional component, in addition, also can contain other epoxy resin or other solidifying agent.

Combination is used under the situation of other epoxy resin, and epoxy resin of the present invention shared ratio in whole epoxy resin is preferably more than the 60 weight %, more than the preferred especially 70 weight %.

As operable other epoxy resin, can enumerate: phenolic resin varnish type epoxy resin, bisphenol A type epoxy resin, biphenyl type epoxy resin, triphenyl methane type epoxy resin, phenol aralkyl-type epoxy resin etc.Can enumerate particularly: dihydroxyphenyl propane, bisphenol S, sulphur bis-phenol, fluorenes bis-phenol, terpene diphenol, 4,4 '-xenol, 2,2 '-xenol, 3; 3 ', 5,5 '-tetramethyl--[1; 1 '-biphenyl]-4; 4 '-diphenol, Resorcinol, Resorcinol, naphthalenediol, three (4-phenylor) methane, 1,1,2; 2-four (4-phenylor) ethane, phenols (phenol, the substituted phenol of alkyl, naphthols, the substituted naphthols of alkyl, dihydroxy-benzene, dihydroxy naphthlene etc.) and formaldehyde, acetaldehyde, phenyl aldehyde, PARA HYDROXY BENZALDEHYDE, salicylaldhyde, parahydroxyacet-ophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4; 4 '-two (chloromethyl)-1,1 '-biphenyl, 4,4 '-two (methoxymethyl)-1; 1 '-biphenyl, 1; Two (chloromethyl) benzene, 1 of 4-, polycondensate of two (methoxymethyl) benzene of 4-etc. and their modifier, by solid-state or liquid-state epoxy resins such as halogenation bisphenols such as tetrabromo-bisphenol and alcohols deutero-glycidyl ether thing, alicyclic epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resins, but be not limited to these.These materials can use separately or two or more combination is used.

Especially, composition epoxy resin of the present invention being used for optical applications is main purpose.Be used under the situation of optical applications, preferably use with the alicyclic epoxy resin combination.Under the situation of alicyclic epoxy resin, the compound that has the epoxy cyclohexane structure in the preferred skeleton, the especially preferably epoxy resin that obtains of the oxidizing reaction of the compound through having the tetrahydrobenzene structure.

As these epoxy resin, can enumerate: will be through the esterification of cyclohexene carboxylate and alcohols or the esterification of tetrahydrobenzene methyl alcohol and carboxylic-acid (Tetrahedron, the 36th volume, the 2409th page (1980); Tetrahedron Letter, the method for the 4475th page of records such as (1980)) or the compound oxidation that can make of the transesterification reaction (methods of records such as TOHKEMY 2006-052187 communique) of the Di Senke (テ イ シ エ Application コ) of hexamethylene olefine aldehydr reaction (methods of records such as TOHKEMY 2003-170059 communique, TOHKEMY 2004-262871 communique) and cyclohexene carboxylate ester and the material that obtains.

As alcohols,, can enumerate: glycols so long as have the then not special restriction of the compound of alcoholic extract hydroxyl group; Like terepthaloyl moietie, 1,2-Ucar 35,1, ammediol, 1; 2-butyleneglycol, 1,4-butyleneglycol, 1,5-pentanediol, 1; 6-pinakon, cyclohexanedimethanol, 2,4-diethylammonium pentanediol, 2-ethyl-2-butyl-1, ammediol, NSC 6366, tristane dimethanol, norbornylene glycol etc.; Three alcohols are like glycerine, trimethylolethane, TriMethylolPropane(TMP), tri hydroxy methyl butane, 2-methylol-1,4-butyleneglycol etc.; The tetrol class is like tetramethylolmethane, two (TriMethylolPropane(TMP)) etc.; Deng.In addition,, can enumerate as carboxylic-acid: oxalic acid, toxilic acid, fumaric acid, phthalic acid, m-phthalic acid, hexanodioic acid, cyclohexane cyclohexanedimethanodibasic etc., but be not limited to these.

In addition, can enumerate the acetal compound that obtains through tetrahydrobenzene aldehyde derivatives and pure aldolization.

As these epoxy resins Specific examples include: ERL-4221, UVR-6105, ERL-4299 (all trade names, are double ウ · Kelly mini-Cal system), Center ro キ thermal イ cloth 2021P, Oh, poly a cloth GT401, EHPE3150, EHPE3150CE (all trade names, are DAICEL chemical industries, Ltd.), and dicyclopentadiene diepoxide, etc., but not limited to (reference: Total Epokey Shin said resin base series I, pages 76-85).

These epoxy resin can use separately or two or more combination is used.

As solidifying agent, combination is used under the situation of other solidifying agent, and polycarboxylic acid (B) is preferably more than the 30 weight % with total amount shared ratio in whole solidifying agent of acid anhydrides (C), more than the preferred especially 40 weight %.

As the solidifying agent that can make up use, for example can enumerate: aminated compounds, anhydrides compound, amides, phenolic cpd, carboxylic acid compound etc.As the concrete example of operable solidifying agent, can enumerate: amine or polyamide compound (diaminodiphenyl-methane, two inferior second triamines, Sanya second tetramine, diaminodiphenylsulfone(DDS), isophorone diamine, Dyhard RU 100, by linolenic dipolymer and quadrol synthetic polyamide resin etc.); The reactant of acid anhydrides and ZGK 5 type alcohols (Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, PMA acid anhydride, maleic anhydride, Tetra Hydro Phthalic Anhydride, methyl tetrahydrophthalic anhydride, methyl carbic anhydride, carbic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylene-dimalonic acid acid anhydride, dicyclo [2.2.1] heptane-2; 3-dicarboxylic acid anhydride, methyl bicycle [2.2.1] heptane-2; 3-dicarboxylic acid anhydride, hexanaphthene-1; 3; 4-tricarboxylic acid-3, reactant of the ZGK 5 type alcohols such as ZGK 5 of acid anhydrides such as 4-acid anhydrides and Trivalin SF modification etc.); Polyatomic phenol (dihydroxyphenyl propane, Bisphenol F, bisphenol S, fluorenes bis-phenol, terpene diphenol, 4,4 '-xenol, 2,2 '-xenol, 3; 3 ', 5,5 '-tetramethyl--[1; 1 '-biphenyl]-4,4 '-diphenol, Resorcinol, Resorcinol, naphthalenediol, three (4-phenylor) methane, 1,1; 2; 2-four (4-phenylor) ethane, phenols (phenol, the substituted phenol of alkyl, naphthols, the substituted naphthols of alkyl, dihydroxy-benzene, dihydroxy naphthlene etc.) and formaldehyde, acetaldehyde, phenyl aldehyde, PARA HYDROXY BENZALDEHYDE, salicylaldhyde, parahydroxyacet-ophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4 '-two (chloromethyl)-1,1 '-biphenyl, 4; 4 '-two (methoxymethyl)-1; 1 '-biphenyl, 1, the condenses of halogenation bisphenols, terpenes and phenols such as the polycondensate of 4 '-two (chloromethyl) benzene, 1,4 '-two (methoxymethyl) benzene etc. and their modifier, tetrabromo-bisphenol etc.); Other (imidazoles, trifluoroboranes-amine complex, guanidine derivative etc.), but be not limited to these.These materials can use separately also can use two or more.

Epoxy resin with the ratio that cooperates of solidifying agent is in the composition epoxy resin of the present invention, preferably uses 0.7～1.2 equivalent solidifying agent with respect to epoxy group(ing) 1 equivalent of whole epoxy resin., all might solidify under arbitrary situation not exclusively, thereby can not obtain good curing rerum natura when under the quantity not sufficient 0.7 normal situation, with respect to epoxy group(ing) 1 perhaps above under the 1.2 normal situation.

In the composition epoxy resin of the present invention, can curing catalysts be used with solidifying agent.Concrete example as operable curing catalyst; Can enumerate: glyoxal ethyline, 2-phenylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazoles, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1 benzyl 2 methyl imidazole, 1-1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecyl imidazole, 2; 4-diamino--6 (2 '-Methylimidazole (1 ')) ethyl s-triazine, 2; 4-diamino--6 (2 '-undecyl imidazole (1 ')) ethyl s-triazine, 2; 4-diamino--6 (2 '-ethyl; 4-methylimidazole (1 ')) ethyl s-triazine, 2; 4-diamino--6 (2 '-Methylimidazole (1 ')) ethyl s-triazine isocyanuric acid affixture, the 2:3 affixture of glyoxal ethyline isocyanuric acid, 2-phenylimidazole isocyanuric acid affixture, 2-phenyl-3; 5-hydroxymethyl-imidazole, 2-phenyl-4-methylol-5-Methylimidazole, 1-cyanoethyl-2-phenyl-3; Amidess, 1 such as the salt of polycarboxylic acids such as various imidazoles such as 5-dicyano ethoxyl methyl imidazoles and these imidazoles and phthalic acid, m-phthalic acid, terephthalic acid, trimellitic acid, PMA, naphthalic acid, toxilic acid, oxalic acid, Dyhard RU 100; Ammonium salt, triphenylphosphine, three (tolyl) phosphine, tetraphenylphosphonibromide bromide

tetraphenyl boric acid tetraphenyl phosphine class or compounds, 2 such as

such as the salt of diaza compound such as 8-diaza-dicyclo [5.4.0] 11 carbon-7-alkene and their tetraphenyl borate, phenol phenolic varnish etc., salt, Tetrabutyl amonium bromide, cetyl trimethylammonium bromide, trioctylphosphine methyl brometo de amonio with aforementioned polycarboxylic acid class or Hypophosporous Acid, 50 class; 4, metallic compounds such as phenols such as 6-triamino cresols, amine affixture, stannous octoate etc. and microcapsule-type curing catalysts that these curing catalysts microencapsulations are obtained etc.Use any in these curing catalysts, for example can according to the desired characteristic of transparent resin composition that will obtain suitably select like the transparency, curing speed, operating condition etc.Curing catalysts uses with the scope of 0.001 ~ 15 weight part with respect to epoxy resin 100 weight parts usually.

In the composition epoxy resin of the present invention, also can contain P contained compound and give composition as flame retardant resistance.As P contained compound, can be response type also can be the compound of addition type.Concrete example as P contained compound; Can enumerate: phosphoric acid ester; Like trimethyl phosphite 99, triethyl phosphate, Tritolyl Phosphate, tricresyl phosphate (xylyl) ester (ト リ キ シ リ レ ニ Le ホ ス Off エ one ト), cresyl phosphate diphenyl ester, cresyl phosphate-two (2, the 6-xylyl) ester, 1,3-phenylene two (di(2-ethylhexyl)phosphate (xylyl) ester), 1; 4-phenylene two (di(2-ethylhexyl)phosphate (xylyl) ester), 4,4'-biphenyl (di(2-ethylhexyl)phosphate (xylyl) ester) etc.; The phosphine class, as 9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound, 10-(2, the 5-dihydroxy phenyl)-10H-9-oxa--10-phospho hetero phenanthrene-10-oxide compound etc.; The reactive with active hydrogen of epoxy resin and said phosphine class and the phosphorous epoxy compounds that obtains, red phosphorus etc.; Preferably phosphoric acid ester class, phosphine class or phosphorous epoxy compounds; Preferred especially 1; 3-phenylene two (di(2-ethylhexyl)phosphate (xylyl) ester), 1,4-phenylene two (di(2-ethylhexyl)phosphate (xylyl) ester), 4,4'-biphenyl (di(2-ethylhexyl)phosphate (xylyl) ester) or phosphorous epoxy compounds.The preferred P contained compound of the content of P contained compound/whole epoxy resin=0.1 ~ 0.6 (weight ratio).Be 0.1 when following, flame retardant resistance is insufficient, and is 0.6 might water absorbability, the dielectric characteristics of cured article to be had a negative impact when above.

In addition, also can cooperate adhesive resin as required in the composition epoxy resin of the present invention.As adhesive resin; Can enumerate: butyral resinoid, acetal resin, acrylics, epoxy-nylon-based resin, NBR-phenolic resinoid, epoxy-NBR resinoid, polyamide-based resin, polyimide based resin, ZGK 5 resinoid etc., but be not limited to these.The use level of adhesive resin is used 0.05 ~ 50 weight part, preferred 0.05 ~ 20 weight part with respect to total 100 weight parts of epoxy resin and solidifying agent preferably in the flame retardant resistance of not damaging cured article, stable on heating scope usually as required.

Can add inorganic filler as required in the composition epoxy resin of the present invention.As inorganic filler; For example can enumerate: the microballoon that the powder of crystalline silica, fused silica, aluminum oxide, zirconium, Calucium Silicate powder, lime carbonate, silit, silicon nitride, SP 1, zirconium white, forsterite, steatite, spinel, titanium oxide, talcum etc. perhaps obtains their spheroidizations etc., but be not limited to these.These inorganic fillers can use separately, also can use two or more.The content of these inorganic fillers uses with the amount that in composition epoxy resin of the present invention, accounts for 0～95 weight %.In addition, in the composition epoxy resin of the present invention, can add various Synergist S-421 95s, various thermosetting resins such as releasing agents such as silane coupling agent, Triple Pressed Stearic Acid, palmitinic acid, Zinic stearas, calcium stearate, pigment.

Composition epoxy resin of the present invention is used under the situation of optical material, particularly optical semiconductor sealing agent; Particle diameter as aforementioned employed inorganic filling material; Through using the packing material of nano-scale, can under the situation that does not hinder the transparency, replenish physical strength.As the benchmark of nano-scale, from the viewpoint of the transparency consider preferably to use below the median size 500nm, the packing material below the median size 200nm particularly.

Composition epoxy resin of the present invention is used for to add fluor as required under the situation of optical material, particularly optical semiconductor sealing agent.Fluor for example is the material with following effect: the sodium yellow after absorbing the part of the blue light that sends from blue-led element and sending wavelength conversion forms white light thus.Fluor is distributed in the curable resin composition in advance, then with optical semiconductor sealing.As the not special restriction of fluor, can use existing known fluor, can illustration for example: the aluminate of REE, sulfo-gallate, orthosilicate etc.More specifically, can enumerate: fluor such as YAG fluor, TAG fluor, orthosilicate fluor, thiogallate fluor, sulphide phosphor, can illustration: YAlO ₃: Ce, Y ₃Al ₅O ₁₂: Ce, Y ₄Al ₂O ₉: Ce, Y ₂O ₂S:Eu, Sr ₅(PO ₄) ₃Cl:Eu, (SrEu) OAl ₂O ₃Deng.As the particle diameter of said fluor, can use the fluor of the particle diameter of this known, median size is preferably 1 ~ 250 μ m, preferred especially 2 ~ 50 μ m.Use under the situation of these fluor, its addition is preferably 1 ~ 80 weight part with respect to resinous principle 100 weight parts, more preferably 5 ~ 60 weight parts.

Composition epoxy resin of the present invention is used under the situation of optical material, particularly optical semiconductor sealing agent; Sedimentation when preventing that various fluor from solidifying, can add with fine silica powder end (being also referred to as gas gel or aerosol) is the thixotropy imparting agent of representative.As such fine silica powder end, for example can enumerate: Aerosil 50, Aerosil 90, Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT600, Aerosil R972, Aerosil R974, Aerosil R202, Aerosil R812, Aerosil R812S, Aerosil R805, RY200, RX200 (Japanese ア エ ロ ジ Le corporate system) etc.

Composition epoxy resin of the present invention is used under the situation of optical material, particularly optical semiconductor sealing agent; In order to prevent painted purpose, can contain amine compound, or as the phosphorus compound and the phenolic cpd of anti-oxidant material as photostabilizer.

As said amine compound, for example can enumerate: four (1,2,2,6,6-pentamethyl--4-piperidyl)-1,2,3,4-ethylene-dimalonic acid ester, four (2; 2,6,6-tetramethyl--4-piperidyl)-1,2,3,4-ethylene-dimalonic acid ester, 1,2,3; 4-ethylene-dimalonic acid and 1,2,2,6,6-pentamethyl--4-piperidines alcohol and 3, two (2-hydroxyl-1, the 1-dimethyl ethyls)-2,4 of 9-; 8, the mixed ester compound of 10-four oxaspiros [5.5] hendecane, two (2,2,6, the 6-tetramethyl--4-piperidyl) esters of sebacic acid, two (1-hendecane oxygen base-2,2,6, the 6-tetramethyl piperidine-4-yl) esters of carbonic acid, methylacrylic acid 2; 2,6,6 ,-tetramethyl--4-piperidyl ester, two (2,2,6, the 6-tetramethyl--4-piperidyl) esters of sebacic acid, sebacic acid two (1,2; 2,6,6-pentamethyl--4-piperidyl) ester, 4-benzoyloxy-2,2,6,6-tetramethyl piperidine, 1-[2-[3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyloxy] ethyl]-4-[3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyloxy]-2; 2,6,6-tetramethyl piperidine, methylacrylic acid 1,2,2,6,6-pentamethyl--4-piperidyl ester, [[3,5-two (1; The 1-dimethyl ethyl)-and the 4-hydroxy phenyl] methyl] two (1,2,2,6, the 6-pentamethyl--4-piperidyl) esters of butyl malonic acid, two (2,2,6,6-tetramethyl--1 (the octyloxy)-4-piperidyl) esters of sebacic acid; 1, the resultant of reaction of 1-dimethyl ethyl hydrogen peroxide and octane, N, N ', N ", N " and '-four-(4, two (butyl-(N-methyl-2,2,6 of 6-; 6-tetramethyl piperidine-4-yl) amino)-and triazine-2-yl)-4,7-diaza decane-1,10-diamines, dibutylamine 1,3,5-triazines N, N '-two (2,2,6; 6-tetramethyl--4-piperidyl-1, gathers that [[6-(1,1,3, the 3-tetramethyl butyl) amino-1 at the polycondensate of 6-hexanediamine and N-(2,2,6,6-tetramethyl--4-piperidyl) butylamine; 3,5-triazine-2,4-two bases] [(2,2,6,6-tetramethyl--4-piperidyl) imino-] hexa-methylene [(2,2,6; 6-tetramethyl--4-piperidyl) imino-]], Succinic acid dimethylester and 4-hydroxyl-2,2,6,6-tetramethyl--1-piperidines alcoholic acid polymkeric substance, 2,2,4,4-tetramethyl--20-(β-lauryl oxygen carbonyl) ethyl-7-oxa--3,20-diaza two spiral shells [5.1.11.2] heneicosane-21-ketone, N-(2; 2,6,6-tetramethyl--4-piperidyl)-and Beta-alanine dodecyl ester/tetradecyl ester, N-ethanoyl-3-dodecyl-1-(2,2,6,6-tetramethyl--4-piperidyl) tetramethyleneimine-2,5-diketone, 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-oxa--3,20-diazabicyclo-[5.1.11.2]-heneicosane-20-propionic acid dodecyl ester/tetradecyl ester, [(4-p-methoxy-phenyl)-methylene radical] propanedioic acid two (1,2; 2,6,6-pentamethyl--4-piperidyl) ester, 2,2,6, high-grade aliphatic ester, the N of 6-tetramethyl--4-piperidines alcohol, N '-two (2,2; 6,6-tetramethyl--4-piperidyl)-1, hindered aminess such as 3-benzenedicarboxamide, [2-hydroxyl-3-(3,4,5 for UV-531 benzophenone compound, 2-(2H-benzotriazole-2-yl)-4-(1,1,3, the 3-tetramethyl butyl) phenol, 2-(2-hydroxy-5-methyl base phenyl) benzotriazole, 2-such as (オ Network タ ベ Application ゾ Application); 6-tetrahydric phthalimide-methyl)-and the 5-aminomethyl phenyl] resultant of reaction, the 2-(2H-benzotriazole-2-yl)-6-dodecyl-benzotriazole compounds, 3 such as 4-methylphenol of benzotriazole, 2-(the 3-tertiary butyl-2-hydroxy-5-methyl base phenyl)-5-chlorobenzotriazole, 2-(2-hydroxyl-3,5-di-tert-pentyl-phenyl) benzotriazole, 3-(3-(2H-benzotriazole-2-yl)-5-tert-butyl-hydroxy phenyl) methyl propionate and polyoxyethylene glycol, 5-di-tert-butyl-4-hydroxybenzoic acid 2, benzoates such as 4-di-t-butyl phenyl ester, 2-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-compound in triazine class such as 5-[(hexyl) oxygen base] phenol etc., preferred especially hindered amine compound.

As the amine compound of aforementioned lights stable material, can use following commercially available article.

As the not special restriction of commercially available aminated compounds, for example can enumerate: the LA-52 that the TINUVIN765 that チ バ ス ペ シ ヤ リ テ イ ケ ミ カ Le ズ makes, TINUVIN770DF, TINUVIN144, TINUVIN123, TINUVIN622LD, TINUVIN152, CHIMASSORB944, ア デ カ make, LA-57, LA-62, LA-63P, LA-77Y, LA-81, LA-82, LA-87 etc.

As the not special restriction of aforementioned phosphorus compound, for example can enumerate: 1,1; 3-three (2-methyl-4-two (tridecyl) phosphorous acid ester-5-tert-butyl-phenyl) butane, distearyl pentaerythrityl diphosphite, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphites, phenyl dihydroxyphenyl propane pentaerythritol diphosphites, dicyclohexyl pentaerythritol diphosphites, tricresyl phosphite (diethylammonium phenyl) ester, tricresyl phosphite (diisopropyl phenyl) ester, tricresyl phosphite (di-n-butyl phenyl) ester, tricresyl phosphite (2; The 4-di-tert-butyl-phenyl) ester, tricresyl phosphite (2, the 6-di-tert-butyl-phenyl) ester, tricresyl phosphite (2, the 6-di-tert-butyl-phenyl) ester, 2; 2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, 2; 2 '-methylene-bis (4, the 6-di-tert-butyl-phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) phosphorous acid ester, 2,2 '-methylene-bis (4-methyl-6-tert butyl phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) phosphorous acid ester, 2; Two (4-methyl-6-tert butyl phenyl) (the 2-tertiary butyl-4-aminomethyl phenyl) phosphorous acid esters, four (2 of 2 '-ethylidene; The 4-di-tert-butyl-phenyl)-4,4 '-biphenylene, two phosphinates, four (2, the 4-di-tert-butyl-phenyl)-4; 3 '-biphenylene, two phosphinates, four (2; The 4-di-tert-butyl-phenyl)-3,3 '-biphenylene, two phosphinates, four (2, the 6-di-tert-butyl-phenyl)-4; 4 '-biphenylene, two phosphinates, four (2; The 6-di-tert-butyl-phenyl)-4,3 '-biphenylene, two phosphinates, four (2, the 6-di-tert-butyl-phenyl)-3; 3 '-biphenylene, two phosphinates, 4-phenyl-phenyl-phosphonite two (2; The 4-di-tert-butyl-phenyl) ester, two (2, the 4-di-tert-butyl-phenyl) esters of 3-phenyl-phenyl-phosphonite, two (2, the 6-di-n-butyl phenyl) esters of 3-phenyl-phenyl phosphorous acid, 4-phenyl-phenyl-phosphonite two (2; The 6-di-tert-butyl-phenyl) ester, 3-phenyl-phenyl-phosphonite two (2; The 6-di-tert-butyl-phenyl) ester, four (2,4-di-t-butyl-5-aminomethyl phenyl)-4,4 '-biphenylene, two phosphinates, tributyl phosphate, trimethyl phosphite 99, Tritolyl Phosphate, triphenylphosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl phosphate toluene ester, the adjacent biphenyl ester of diphenyl phosphate list, tributoxyethyl phosphate, dibutyl phosphate, dioctylphosphoric acid ester, diisopropyl phosphate etc.

Above-mentioned phosphorus compound can use commercially available article.As the not special restriction of commercially available phosphorus compound, for example can enumerate: the ア デ カ ス タ Block PEP-4C that ア デ カ makes, ア デ カ ス タ Block PEP-8, ア デ カ ス タ Block PEP-24G, ア デ カ ス タ Block PEP-36, ア デ カ ス タ Block HP-10, ア デ カ ス タ Block 2112, ア デ カ ス タ Block 260, ア デ カ ス タ Block 522A, ア デ カ ス タ Block 1178, ア デ カ ス タ Block 1500, ア デ カ ス タ Block C, ア デ カ ス タ Block 135A, ア デ カ ス タ Block 3010, ア デ カ ス タ Block TPP etc.

As the not special restriction of phenolic compound, for example can enumerate: 2,6 di tert butyl 4 methyl phenol, 3-(3; The 5-di-tert-butyl-hydroxy phenyl) propionic acid Octadecane base ester, four [methylene radical-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] methane, 2,4-di-t-butyl-6-methylphenol, 1; 6-pinakon-two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], isocyanuric acid three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) ester, 1; 3,5-trimethylammonium-2,4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, tetramethylolmethane four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], 3; Two [2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl)-propionyloxy]-1, the 1-dimethyl ethyls]-2,4 of 9-; 8,10-four oxaspiros [5.5] hendecane, triethylene glycol-two [3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic ester], 2,2 '-Ding fork two (4; The 6-DI-tert-butylphenol compounds), 4,4 '-Ding fork two (3 methy 6 tert butyl phenol), 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), 2; 2 '-methylene-bis(4-ethyl-6-t-butyl phenol), the 2-tertiary butyl-6-(the 3-tertiary butyl-2-hydroxy-5-methyl base benzyl)-4-methylphenol propenoate, 2-[1-(2-hydroxyl-3,5-di-tert-pentyl-phenyl) ethyl]-4,6-di-tert-pentyl-phenyl propenoate, 4; 4 '-sulphur two (3 methy 6 tert butyl phenol), 4,4 '-Ding fork two (3 methy 6 tert butyl phenol), the 2-tertiary butyls-4-methylphenol, 2,4-DI-tert-butylphenol compounds, 2; 4-di-tert-pentyl phenol, 4,4 '-sulphur two (3 methy 6 tert butyl phenol), 4,4 '-Ding fork two (3 methy 6 tert butyl phenol), two [3; Two (4 '-hydroxyl-3 '-the tert-butyl-phenyl)-butyric acid of 3-] diol ester, 2,4-DI-tert-butylphenol compounds, 2,4-di-tert-pentyl phenol, 2-[1-(2-hydroxyl-3; The 5-di-tert-pentyl-phenyl) ethyl]-4,6-di-tert-pentyl-phenyl propenoate, two [3, two (4 '-hydroxyl-3 '-tert-butyl-phenyl) butyric acid of 3-] diol ester etc.

Above-mentioned phenolic cpd can use commercially available article.As the not special restriction of commercially available phenolic cpd; For example can enumerate: IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1135, IRGANOX245, IRGANOX259, IRGANOX295, IRGANOX3114, IRGANOX1098, IRGANOX1520L that チ バ ス ペ シ セ リ テ イ ケ ミ カ Le ズ makes; ア デ カ ス タ Block AO-20, ア デ カ ス タ Block AO-30, ア デ カ ス タ Block AO-40, ア デ カ ス タ Block AO-50, ア デ カ ス タ Block AO-60, ア デ カ ス タ Block AO-70, ア デ カ ス タ Block AO-80, ア デ カ ス タ Block AO-90, ア デ カ ス タ Block AO-330 that ア デ カ makes, the Sumilizer GA-80 that Sumitomo Chemical is made, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer GM, Sumilizer GS (F), Sumilizer GP etc.

In addition, can use as the commercially available interpolation material of the anti-coloring agent of resin.For example can enumerate: the TINUVIN328 that チ バ ス ペ シ セ リ テ イ ケ ミ カ Le ズ makes, TINUVIN234, TINUVIN326, TINUVIN120, TINUVIN477, TINUVIN479, CHIMASSORB2020FDL, CHIMASSORB119FL etc.

Preferably contain more than at least a in above-mentioned phosphorus compound, amine compound, the phenolic cpd, the not special restriction of its use level with respect to composition epoxy resin of the present invention, is the scope of 0.005 ~ 5.0 weight %.

Composition epoxy resin of the present invention obtains through each composition is mixed equably.Composition epoxy resin of the present invention can be through easily obtaining its cured article with the existing same method of known method.For example; Can enumerate: with epoxy resin composition and curing agent component and curing catalyst as required, P contained compound, adhesive resin, inorganic filling material and Synergist S-421 95 etc.; As required with thorough mixing such as forcing machine, kneader, cylinder, planetary-type mixers to evenly obtaining composition epoxy resin; At resulting composition epoxy resin is under the situation of liquid state; Through pouring into or pouring into a mould said composition is impregnated in the base material, perhaps is injected into and carries out injection molding in the mould, and be cured through heating.In addition, under resulting composition epoxy resin was solid-state situation, injection molding or use transmitted forming mill etc. and forms after the fusion, is cured through heating again.Solidification value, time are 80 ~ 200 ℃, 2 ~ 10 hours.As curing, can be cured reaction but preferably heat up stage by stage at high temperature quickly with its curing.Particularly, between 80 ℃ ~ 150 ℃, carry out initial cure, and between 100 ℃ ~ 200 ℃, carry out after fixing.As the solidified stage, preferably be divided into 2 ~ 8 stages to heat up, more preferably 2 ~ 4 stages.

In addition; Composition epoxy resin of the present invention is dissolved in toluene, YLENE, acetone, methylethylketone, MIBK, N, N,N-DIMETHYLACETAMIDE, the N-Methyl pyrrolidone equal solvent obtains curable resin composition varnish; Be impregnated in the base materials such as spun glass, thomel, trevira, tynex, sapphire whisker, paper and carry out heat drying and obtain prepreg; With resulting prepreg hot compacting, can obtain the cured article of composition epoxy resin of the present invention thus.The solvent of this moment uses with the amount that accounts for 10 ~ 70 weight %, preferred 15 ~ 70 weight % in the mixture of composition epoxy resin of the present invention and this solvent usually.In addition, fluid composition can directly obtain containing the epoxy resin cured product of thomel through the RTM mode.

In addition, can composition epoxy resin of the present invention be used as the film-type composition for sealing.When obtaining such pellicular resin compsn, can enumerate: composition epoxy resin of the present invention is processed aforesaid varnish, it is applied on the stripping film, carry out B stageization after adding the heat extraction solvent, obtain the sheet tackiness agent thus.This sheet tackiness agent can be used as the interlayer insulating film in the MULTILAYER SUBSTRATE etc., a diaphragm seal of photosemiconductor is used.

Below, to composition epoxy resin of the present invention is elaborated as the sealing material of photosemiconductor or the situation of chip join material use.

Composition epoxy resin of the present invention as the sealing material of photosemiconductors such as high brightness White LED, or situation about using as the chip join material under; Thereby, use as sealing material or as chip join material and sealing material through additives such as epoxy resin, solidifying agent, coupling agent, inhibitor, photostabilizer being mixed fully the preparation composition epoxy resin.As blending means, use kneader, three-roller (three ロ one Le), universal mixer, planetary-type mixer, high-speed mixer (ホ モ ミ キ サ one), homogenizer (ホ モ デ イ ス パ one), ball mill etc., in the normal temperature or the mixing down of heating.

Optical semiconductors such as high brightness White LED generally are will be layered in semi-conductor chips such as GaAs on the substrates such as sapphire, spinel, SiC, Si, ZnO, GaP, GaAlAs, GaAsP, AlGa, InP, GaN, InN, AlN, InGaN and be glued on lead frame or heating panel, the package and obtain through sticking with glue agent (chip join material).For inflow current, also can be for being connected with the type of metal wires such as gold thread.In order to avoid heat or moisture, and the effect of performance lens function, with sealing materials such as epoxy resin with this semi-conductor chip sealing.Composition epoxy resin of the present invention can be used as sealing material or chip join material and uses.On technology, easily composition epoxy resin of the present invention is used for chip join material and sealing material both sides.

As using composition epoxy resin of the present invention that semi-conductor chip is glued to the method on the substrate; Can be coated with composition epoxy resin of the present invention through adhesive dispensing device (デ イ ス ペ Application サ one), perfusion or silk screen printing; Carry then and put semi-conductor chip and be heating and curing, can semi-conductor chip is gluing.Heating can be used methods such as heated air circulation type, infrared rays, high frequency.

The heating condition preference is as heating about 1 minute～about 24 hours down at 80～230 ℃.The internal stress that produces when being heating and curing in order to reduce, for example, can 80～120 ℃ of Procuring after 30 minutes～5 hours under 120～180 ℃, 30 minutes～10 hours condition after fixing.

As the forming mode of sealing material, can use: injecting sealing material is heating and curing and the injection mode that is shaped then in the mould that is inserted with the substrate that is fixed with semi-conductor chip as stated; In advance sealing material is injected on the mould and therein dipping be fixed in the semi-conductor chip on the substrate, the back that is heating and curing is from the compression molding mode of mold releasability etc.

As method for implanting, can enumerate adhesive dispensing device, transmit shaping, injection forming etc.

Heating can be used methods such as heated air circulation type, infrared rays, high frequency.The heating condition preference is as heating about 1 minute～about 24 hours down at 80～230 ℃.The internal stress that produces when being heating and curing in order to reduce, for example, can 80～120 ℃ of Procuring after 30 minutes～5 hours under 120～180 ℃, 30 minutes～10 hours condition after fixing.

In addition; Can enumerate the general use of using curable resins such as epoxy resin; Particularly, can enumerate: the cyanate resin composition that tackiness agent, lacquer, coating agent, shaped material (comprising sheet, film, FRP etc.), insulating material (comprising printing plate, electric wire coating etc.), sealing material and sealing material, substrate are used, as resist with additive in acrylic resin of solidifying agent etc., other resin etc. etc.

As tackiness agent, can enumerate the tackiness agent that building is used with, therapeutic medical tackiness agent and electronic material with, general affairs with, for building, automobile.In these tackiness agent; As the tackiness agent that electronic material is used, can enumerate: adhesive for semiconductor, BGA such as the folded interlaminated adhesive that increases MULTILAYER SUBSTRATE such as (PVC Le De ア Star プ) substrate, chip join agent, underfill strengthen and stick with glue agent etc. with underfill, anisotropic conducting film (ACF), anisotropic conductive paste actual installation such as (ACP).

As sealing material, can enumerate: the sealing (comprise strengthening and use underfill) during IC such as the underfill of usefulness such as the perfusion sealing of usefulness such as the COB of the perfusion of usefulness such as electric capacity, transistor, diode, photodiode, IC, LSI, dipping, transmission form seal, IC, LSI class, COF, TAB, flip-chip, QFP, BGA, CSP encapsulation class actual installation etc.

It is the various uses of representative that the cured article that obtains among the present invention can be used for the optics material.Optics generally is meant the material that in making the purposes of light through this material such as visible light, infrared rays, ultraviolet ray, X ray, laser, uses with material.More specifically, can enumerate: LED such as lamp type, SMD type are with the material of sealing material and the following stated.Liquid crystal such as the substrate material in the field of liquid crystal, light guiding plate, prismatic lens, polarization plates, polarizer, viewing angle compensation film, tackiness agent, polarizer protective film are with the peripheral material of liquid crystal indicators such as film.Various film-substrate, the protective film of front glass, front glass equivalent material, tackiness agent in protective film, front glass equivalent material, tackiness agent and the Field Emission Display (FED) of the front glass in substrate material, light guiding plate, prismatic lens, polarization plates, polarizer, viewing angle compensation film, tackiness agent, polarizer protective film and organic EL (electroluminescent) indicating meter in protective film, front glass equivalent material, tackiness agent and plasma addressed liquid (PALC) indicating meter of the moulding material of the LED that uses in protective film, front glass equivalent material, tackiness agent and the LED display unit of the sealing material of the color PDP of expecting in addition, (plasma display), antireflective film, optical compensating film, case material, front glass, the sealing material of LED, front glass as flat-panel monitor of future generation.In the optical recording field, the optical disc substrate material of using for VD (optic disk), CD/CD-ROM, CD-R/RW, DVD-R/DVD-RAM, MO/MD, PD (phase transition optical disk), light-card, pickup lens, protective film, sealing material, tackiness agent etc.

In the optical device field, as the camera lens of still camera with material, range finder prism, target prism, view finder cover, optical receiving sensor portion.In addition, as photographic lens, the view finder of Kamera.In addition, as the projection lens of projection television, protective film, sealing material, tackiness agent etc.As the lens of lighting apparatus with material, sealing material, tackiness agent, film etc.In the optics field, as the sealing material of the peripheral filamentary material of the optical switch in the optical communication system, lens, guided wave road, element, tackiness agent etc.As the peripheral fiber optic materials of optical conenctor, lasso, sealing material, tackiness agent etc.In light passive components, optical circuit parts, as the sealing material of the sealing material of lens, waveguide, LED, CCD, tackiness agent etc.As the sealing material of the peripheral substrate material of optoelectronic integrated circuit (OEIC), filamentary material, element, tackiness agent etc.In field fiber, as decorate the transmitter class of indicating meter with illuminated light guide etc., industrial use, explicit identification class etc. and the communications infrastructure with and family in digital equipment connect the optical fiber of usefulness.In the SIC peripheral material, resist (the レ ジ ス ト) material that the microlithography of using as LSI, ultra LSI material is used.In automobile conveyor field, the lamp reflector of using as automobile, retainer, gear parts, anti-corrosion coating, switch sections, headlight, engine interior spare, electric component, various inside and outside portion article, drive engine, braking fuel tank, automobile with Rustproof Steel Plate, trim panel, interior packing material, protect and tie up with wire harness, fuel hose, auto lamp, glass replacement.In addition, the multiple glazing of using as rail vehicle.In addition, tie up with wire harness, anti-corrosion coating as toughner, mover peripheral member, the protection of the structured material of flyer.In building field, as interior packing factorial lumber material, electrical equipment cover (electric mood カ バ one), sheet material (シ one ト), glass intermediate coat, glass replacement, solar cell peripheral material.In agriculture field, film is used in covering as booth.As follow-on optoelectronic function organic materials, the sealing material of the substrate material of organic EL peripheral material, organic photorefractive element, light amplification element, optical operation element, organic solar batteries periphery, filamentary material, element, tackiness agent etc. as light-light conversion element.

As sealing agent, can enumerate: the sealing (strengthen and use underfill) during IC such as the underfill of usefulness such as the perfusion sealing of usefulness such as the COB of the perfusion of usefulness such as electric capacity, transistor, diode, photodiode, IC, LSI, dipping, transmission form seal, IC, LSI class, COF, TAB, flip-chip, BGA, CSP encapsulation class actual installation etc.

As optics other purposes with material; Can enumerate the general use of using composition epoxy resin, for example can enumerate: the additive in tackiness agent, lacquer, coating agent, shaped material (comprising sheet, film, FRP etc.), insulating material (comprising printing plate, electric wire coating etc.), sealing material and other resin etc. etc.As tackiness agent, can enumerate the tackiness agent that building is used with, therapeutic medical tackiness agent and electronic material with, general affairs with, for building, automobile.In these tackiness agent; As the tackiness agent that electronic material is used, can enumerate adhesive for semiconductor, BGA such as the folded interlaminated adhesive that increases MULTILAYER SUBSTRATE such as (PVC Le De ア Star プ) substrate, chip join agent, underfill and strengthen and stick with glue agent etc. with underfill, anisotropic conducting film (ACF), anisotropy conductiving glue actual installation such as (ACP).

Embodiment

Below, through synthetic example, embodiment the present invention is described more specifically, in addition, the invention is not restricted to these synthetic examples, embodiment.In this specification sheets, if do not specify that " part ", " % " and ratio etc. all are weight basis.In addition, each physics value among the embodiment is measured through following method.

(1) molecular weight:, calculate the weight-average molecular weight of the polystyrene conversion of under following condition, measuring through the GPC method.

The various conditions of GPC

Manufacturers: Shimadzu Seisakusho Ltd.

Post: guard column SHODEX GPC LF-G LF-804 (3)

Flow velocity: 1.0ml/ minute

Column temperature: 40 ℃

The solvent that uses: THF (THF)

Detector: RI (differential refraction detector)

(2) epoxy equivalent (weight): the method through putting down in writing among the JIS K-7236 is measured.

(3) viscosity: the E type viscometer (TV-20) that uses Toki Sangyo Co., Ltd. to make is measured down at 25 ℃.

Synthetic example 1

As manufacturing process (i); With 106 parts of β-(3; The 4-epoxycyclohexyl) the end capped methyl phenyl silicone oil of silanol (the silanol equivalent 850 of ethyl trimethoxy silane, 234 parts of weight-average molecular weight 1700 (GPC measured value); Calculate as 1/2 of the weight-average molecular weight of using GPC to measure) and 18 part of 0.5% Pottasium Hydroxide (KOH) methanol solution put in the reaction vessel, will bathe temperature and be set at 75 ℃ and heat up.After the intensification, reaction is 8 hours under refluxing.

As manufacturing process (ii), append 305 parts of methyl alcohol, use 86.4 parts of 60 minutes Dropwise 5 0% zero(ppm) water methanol solutions then, and reacted 8 hours at 75 ℃ down refluxing.Reaction neutralizes with 5% biphosphate sodium water solution after finishing, and reclaims 80 ℃ of distillations of carrying out methyl alcohol then.Add 380 parts of MIBKs (MIBK), and the triplicate washing.Then, under reduced pressure the solvent in the organic phase is removed, obtained 300 parts of organopolysiloxane compounds (A-1) thus with reactive functional groups at 100 ℃.The epoxy equivalent (weight) of gained compound is 729g/eq., and weight-average molecular weight is 2200, and outward appearance is a water white transparency.

Synthetic example 2

In flask with whisking appliance, reflux condensing tube, whipping appts; When implementing nitrogen purging, add 20 parts of tristane dimethanols, 100 parts of methylhexahydrophthalic anhydrides (New Japan Chem Co., Ltd's manufacturings; リ カ シ Star De MH; Below be called acid anhydrides (C-1)); 40 ℃ of reactions 3 hours,, (utilize GPC to confirm the disappearance (below the 1 area %) of tristane dimethanol) thus and obtain 120 parts of curing agent compositions (H-1) that contain polycarboxylic acid (B-1) and acid anhydrides (C-1) then 70 ℃ of heated and stirred 1 hour.Gains are the colorless liquid resin, measure purity, polycarboxylic acid (B-1 through GPC; Following formula (7)) be 55 area %, methylhexahydrophthalic anhydride is 45 area %.In addition, functional group's equivalent is 201g/eq..

Synthetic example 3

In flask with whisking appliance, reflux condensing tube, whipping appts; When implementing nitrogen purging, add 15 parts of tristane dimethanols, 70 parts of acid anhydrides (C-1), 15 parts of hexanaphthenes-1,2,4-tricarboxylic acid-1; The 2-acid anhydrides (make by Mitsubishi's gas chemistry; H-TMAn below is called acid anhydrides (C-2)), 40 ℃ of reactions 3 hours; 70 ℃ of heated and stirred 1 hour, (utilize GPC to confirm the disappearance (below the 1 area %) of tristane dimethanol) thus and obtain 100 parts of curing agent compositions (H-2) that contain polycarboxylic acid (B-2) and acid anhydrides (C-2) then.Gains are the colorless liquid resin, measure purity, polycarboxylic acid (B-2 through GPC; Following formula (8)) be 37 area %, acid anhydrides (C-2) is 11 area %, and acid anhydrides (C-1) is 52 area %.In addition, functional group's equivalent is 171g/eq..

R is CH ₃Or COOH

Synthetic example 4

In flask with whisking appliance, reflux condensing tube, whipping appts; When implementing nitrogen purging, add 20 part 1; 4-cyclohexanedimethanol, 100 parts of methylhexahydrophthalic anhydrides and hexahydrophthalic anhydride (New Japan Chem Co., Ltd makes, and リ カ シ Star De MH-700 below is called acid anhydrides C-3); 40 ℃ of reactions 3 hours; 70 ℃ of heated and stirred 1 hour, (utilize GPC to confirm the disappearance (below the 1 area %) of 1,4 cyclohexane dimethanol) thus and obtain 120 parts of curing agent compositions (H-3) that contain polycarboxylic acid (B-3) and acid anhydrides (C-3) then.Gains are the colorless liquid resin, measure purity, polycarboxylic acid (B-3 through GPC; Following formula (9)) be 57 area %, acid anhydrides (C-3) is 43 area %.In addition, functional group's equivalent is 200g/eq..

R is H or CH ₃

Synthetic example 5

In flask with whisking appliance, reflux condensing tube, whipping appts; When implementing nitrogen purging, add 20 part 1; 6-pinakon, 100 parts of acid anhydrides (C-3) are 40 ℃ of reactions 3 hours, then 70 ℃ of heated and stirred 1 hour; (utilize GPC to confirm 1, the disappearance of 6-pinakon (below the 1 area %)) thus and obtain 120 parts of curing agent compositions (H-4) that contain polycarboxylic acid (B-4) and acid anhydrides (C-3).Gains are the colorless liquid resin, measure purity, polycarboxylic acid (B-4 through GPC; Following formula (11)) be 65 area %, acid anhydrides (C-3) is 35 area %.In addition, functional group's equivalent is 200g/eq..

R is H or CH ₃

Synthetic example 6

In flask with whisking appliance, reflux condensing tube, whipping appts; When implementing nitrogen purging, add 20 part 2; 4-diethylammonium pentanediol, 100 parts of acid anhydrides (C-3) are 40 ℃ of reactions 3 hours, then 70 ℃ of heated and stirred 1 hour; (utilize GPC to confirm 2, the disappearance of 4-diethylammonium pentanediol (below the 1 area %)) thus and obtain 120 parts of curing agent compositions (H-5) that contain polycarboxylic acid (B-5) and acid anhydrides (C-3).Gains are the colorless liquid resin, measure purity, polycarboxylic acid (B-5 through GPC; Following formula (12)) be 50 area %, acid anhydrides (C-3) is 50 area %.In addition, functional group's equivalent is 201g/eq..

R is H or CH ₃

Embodiment 1,2,3,4,5, comparative example 1

The organopolysiloxane compound (A-1) that the synthetic example 1 of use obtains is as epoxy resin; The curing agent composition (H-1), (H-2), (H-3), (H-4), (H-5) that use synthetic example 2,3,4,5,6 to obtain use solidifying agent as embodiment; Use acid anhydrides (C-3) to use solidifying agent, use curing catalyst (Japanese chemical industry manufacturing, ヒ シ コ one リ Application PX4MP as comparative example; Below be called catalyst I-1) as curing catalyst; Proportioning shown in the following table 1 (weight part) cooperates, and carries out deaeration in 20 minutes, obtains the present invention or the composition epoxy resin of usefulness relatively.

(test of etchant gas perviousness)

Use resulting curable resin composition; Fill it in the barrel, use accurate discharger to be injection molded into to be equipped with in the square surface mounting LED encapsulation (internal diameter 4.4mm, outer wall height 1.25mm) of the external diameter 5mm of chip of center emission wavelength 465nm.This injection molding thing is put in the process furnace, carried out 1 hour solidification treatment, carry out 3 hours solidification treatment at 150 ℃ again, process the LED encapsulation at 120 ℃.Under following condition, LED encapsulation is placed in the corrosive gases, observes the colour-change of the silver plated lead frame portion of sealed inside.The result is as shown in table 1.

Condition determination

Etchant gas: ammonium sulfide 20% aqueous solution (the sulphur composition becomes black when reacting with silver)

Contact method: in wide neck flask, make the container of ammonium sulfide solution and said LED encapsulation mix existence, cover the lid of wide-mouth vial, evaporable ammonium sulfide gas is contacted with the LED encapsulation.

Corrosive is judged: the lead frame of observing LED encapsulation inside turns black the time of (being called melanism), and this variable color time is long more, judges that then corrosion-resistant gas property is good more.

In the observation, confirm taking out after 10 minutes, after 30 minutes, after 1 hour, after 2 hours.About estimating, no variable color thing is evaluated as zero, and dark brown ~ brown thing is evaluated as *, complete melanism thing is evaluated as * *.

Table 1

Can find out through The above results; Composition epoxy resin of the present invention (compsn that contains organopolysiloxane compound and polycarboxylic acid) is compared with the composition epoxy resin (containing silicone compounds and acid anhydrides) of comparative example; The silvering nondiscoloration of lead frame, corrosion-resistant gas property is good.

With reference to specific embodiment the present invention has been described at length, still, has it will be apparent to one skilled in the art that under the situation that does not break away from the spirit and scope of the present invention, can carry out various changes and correction.

In addition, the application is based on the Japanese patent application that proposed on November 10th, 2009 (Japan special be willing to 2009-256810), all the quoting by reference of this application.In addition, whole documents of quoting in this specification sheets etc. are incorporated this specification sheets in this integral body into the mode of reference.

Claims (5)

1. a composition epoxy resin contains organopolysiloxane (A) and polycarboxylic acid (B), at this,

Organopolysiloxane (A) is the epoxy resin that in its molecule, has glycidyl and/or epoxycyclohexyl at least,

Polycarboxylic acid (B) is for having at least two above carboxyls, and is the polycarboxylic acid of main framing with the aliphatic alkyl.

2. composition epoxy resin as claimed in claim 1 is characterized in that, contains acid anhydrides (C).

3. according to claim 1 or claim 2 composition epoxy resin is characterized in that, the compound that polycarboxylic acid obtains for the reaction through 2 ~ 6 functional polyvalent alcohols and the representative examples of saturated aliphatic cyclic acid anhydride of carbonatoms more than 5.

4. a cured article obtains through each described composition epoxy resin in the claim 1 to 3 is solidified.

5. optical semiconductor device, it contains optical semiconductor and the described cured article of claim 4.