TW201533162A - Addition-curable silicone resin composition, addition-curable silicone resin cured product, and optical semiconductor element sealed body - Google Patents

Abstract

The purpose of the present invention is to provide an addition-curable silicone resin composition having excellent interface adhesion and transparency. The purpose of the present invention is also to provide an addition-curable silicone resin cured product comprising said addition-curable silicone resin composition and to provide an optical semiconductor element sealed body. This addition-curable silicone resin composition contains an addition-curable silicone resin mixture and an adhesiveness-imparting agent. The adhesiveness-imparting agent contains a compound having a structural unit indicated by formula (1-3) and/or a structural unit indicated by formula (1-4), between a structural unit indicated by formula (1-1) and a structural unit indicated by formula (1-2). Each R1a in formula (1-1) and formula (1-2) independently indicates a C1-18 alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a C2-9 alkenyl group, or a C1-4 alkoxy group. Each R1b in formula (1-3) and formula (1-4) independently indicates a C1-18 alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a C2-9 alkenyl group, or a C1-4 alkoxy group. m in formula (1-3) indicates an integer 1-50 and n in formula (1-4) indicates an integer 1-1,500. Each A in formulas (1-1)-(1-3) independently indicates a C1-18 alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a C2-9 alkenyl group, a C1-4 alkoxy group, or a group indicated by formula (2). However, at least one A in formulas (1-1)-(1-3) indicates a group indicated by formula (2). R2a in formula (2) indicates a C1-8 alkylene group having some carbon atoms, excluding carbon atoms bonded to silicon atoms, substitutable by oxygen atoms. Each R2b independently indicates a C1-3 alkylene group and each R3 independently indicates a C1-18 alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a group including a sulfonyl group, an acyl group, a (meth) acryloyl oxyalkl group, or a silyl group. In formula (2), x is an integer 0-2 and Y is an oxygen atom or NH.

Description

Addition-hardening polyphthalocyanine resin composition, addition-hardening type polyoxymethylene resin cured product, and optical semiconductor element sealing body

The present invention relates to an addition-curable polydecane resin composition excellent in interfacial adhesion and transparency. Moreover, the present invention relates to an addition-curable polyphthalocyanine cured product and an optical semiconductor element sealing body which are obtained by using the addition-curable polyoxyxylene resin composition.

In an LED or optical semiconductor device, a transparent resin is generally used as a sealing material for a light-emitting element. Examples of the transparent resin include an epoxy resin, a polyoxygen resin such as an addition curing type, a condensation curing type, and a UV curing type. Among them, the addition-hardening polyphthalocyanine resin is used for white LEDs by hydrogenation reaction of a vinyl fluorenyl group and a hydroquinone group to form a cured product excellent in weather resistance and heat resistance without forming by-products. The use of sealing materials for high-intensity, high-output optical semiconductor components. However, these addition-hardening type polyoxyxylene resins have low adhesion to constituent members of semiconductor materials. For example, in recent years, PCT (poly(tert-butylene terephthalate)) which is excellent in weather resistance or moisture resistance has been used in place of PPA (polymerization) which has problems in long-term stability such as weather resistance or moisture resistance. The phthalamide resin is used as a reflector material, but PCT does not have a hydrogen bonding property in the molecule, and therefore the general polyoxyxene resin has poor adhesion to PCT. Further, the polyoxyxene resin is insufficient in adhesion to a noble metal such as silver which is widely used as an electrode.

Further, there is a problem that the adhesiveness is further lowered by heat generation or temperature cycle from the light-emitting element, and it is easy to cause peeling between the substrate of PCT or the like and the noble metal electrode and the polyoxyn resin.

In order to solve such problems, it is possible to improve the adhesion by adding an adhesion imparting agent such as various decane coupling agents, but the effect is not sufficient, and further, defects such as decrease in durability due to significant moisture absorption and the like are lacking in durability. .

Patent Document 1 discloses an addition-curable polydecane resin composition in which an isomeric cyanurate having an epoxy group is blended as an adhesion imparting agent other than a decane coupling agent, and Patent Document 2 discloses As a polyfluorene resin having an adhesive property, a reactive modified polyoxyxylene resin containing a urethane group having a functional group terminal hydroxyl group is disclosed.

Patent Document 1: Japanese Laid-Open Patent Publication No. 2006-137797

Patent Document 2: International Publication No. 2012/108609

However, the method of blending isomeric cyanurate as disclosed in Patent Document 1 is insufficient in improving the adhesion to the substrate. Further, since the isomeric isocyanate is difficult to be dissolved in the polyoxynoxy resin, transparency may not be sufficiently obtained.

Further, in the addition-hardening polyoxyxene resin which is subjected to hydrogenation reaction with a vinyl group, the modified polyoxymethylene resin disclosed in Patent Document 2 has the following defects: in the case of hardening, the hydroquinone group is modified. The hydroxyl group in the polyoxygenated resin produces a dehydrogenation reaction as a side reaction, causing the formation of impurities or a decrease in the physical properties of the resin.

An object of the present invention is to provide an addition-curable polydecane resin composition which is excellent in interfacial adhesion and transparency. Moreover, an object of the present invention is to provide an addition-curable polyphthalocyanine cured product and an optical semiconductor element sealing body which are obtained by using the addition-curable polyoxyxylene resin composition.

The present invention relates to an addition-curable polyfluorene-oxygen resin composition containing an addition-curable polyphthalocyanine resin mixture and an adhesion imparting agent, and the adhesion imparting agent is contained in the following formula (1-1) The structural unit represented by the following formula (1-2) has a structural unit represented by the following formula (1-3) and/or a structural unit represented by the following formula (1-4).

In the formulae (1-1) and (1-2), R ^1a each independently represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group having 2 to 9 carbon atoms. Or an alkoxy group having 1 to 4 carbon atoms. In the formulae (1-3) and (1-4), R ^1b each independently represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group having 2 to 9 carbon atoms. Or an alkoxy group having 1 to 4 carbon atoms. In the formula (1-3), m is an integer of 1 to 50, and in the formula (1-4), n is an integer of 1 to 1500. In the formulae (1-1) to (1-3), A is independently an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group having 2 to 9 carbon atoms, and a carbon number of 1 Alkoxy group of ~4 or a group represented by the following formula (2). Among them, at least one of the formulae (1-1) to (1-3) is a group represented by the formula (2).

In the formula (2), R ^2a represents an alkylene group having 1 to 8 carbon atoms which may be substituted with an oxygen atom in addition to a carbon atom bonded to a halogen atom, and R ^2b independently represents carbon. a 1-3 alkyl group, and R ³ independently represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, a sulfonyl group-containing group, a fluorenyl group, and a (meth) propylene group. Alkoxyalkyl, or fluorenyl. In the formula (2), x is an integer of 0 to 2, and Y is an oxygen atom or NH.

The invention is described in detail below.

The inventors of the present invention have found that by adding a compound having a specific structure to an addition-curable polyoxyxene resin mixture as an adhesion imparting agent, an addition-hardening type polymerization having extremely excellent interfacial adhesion and transparency can be obtained. The epoxy resin composition, thereby completing the present invention.

The addition-hardening polyphthalocene resin composition of the present invention is contained in the above formula The structural unit represented by (1-1) and the structural unit represented by the above formula (1-2) have a structural unit represented by the above formula (1-3) and/or a structural unit represented by the above formula (1-4). The compound (hereinafter also referred to as "the adhesion imparting agent of the present invention") is used as an adhesion imparting agent. Further, the structural unit represented by the formula (1-1) and the formula (1-2) means a molecular terminal. The adhesion imparting agent of the present invention may be a block copolymer or a random copolymer.

The adhesiveness imparting agent of the present invention may be used singly or in combination of two or more.

In the above formula (1-1) and the above formula (1-2), R ^1a each independently represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, and an alkene having 2 to 9 carbon atoms. a base or an alkoxy group having 1 to 4 carbon atoms. Furthermore, in the present specification, the phrase "separately independent" means "may be the same or different".

Examples of the alkyl group having 1 to 18 carbon atoms represented by the above R ^1a include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tertiary butyl group, and a n-pentyl group. , neopentyl, tertiary amyl, n-hexyl, n-heptyl, 2,2,4-trimethylpentyl, n-octyl, isooctyl, n-decyl, n-decyl, n-dodecyl Wait. Among them, a methyl group is preferred.

Examples of the cycloalkyl group represented by the above R ^1a include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a methylcyclohexyl group.

Examples of the aryl group represented by the above R ^1a include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, and a naphthyl group. Among them, a phenyl group is preferred.

Examples of the aralkyl group represented by the above R ^1a include a benzyl group, an α-phenethyl group, and a β-phenethyl group.

Examples of the alkenyl group having 2 to 9 carbon atoms represented by R ^1a include a vinyl group, an allyl group, a butenyl group, and a (meth)acryloxyalkyl group.

In the present specification, the above "(meth)acryloyl group" means an acryloyl group or a methacryl group.

Examples of the alkoxy group having 1 to 4 carbon atoms represented by the above R ^1a include a methoxy group, an ethoxy group, a n-propoxy group, and a n-butoxy group.

Among these, R ^{1a is} preferably an alkyl group or an aryl group having 1 to 18 carbon atoms, more preferably a methyl group or a phenyl group.

In the above formula (1-3) and the above formula (1-4), R ^1b each independently represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, and an alkene having 2 to 9 carbon atoms. Alkoxy group having 1 or 4 carbon atoms.

Examples of the alkyl group having 1 to 18 carbon atoms represented by the above R ^1b include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tertiary butyl group, and a n-pentyl group. , neopentyl, tertiary amyl, n-hexyl, n-heptyl, 2,2,4-trimethylpentyl, n-octyl, isooctyl, n-decyl, n-decyl, n-dodecyl Wait. Among them, a methyl group is preferred.

Examples of the cycloalkyl group represented by the above R ^1b include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a methylcyclohexyl group.

Examples of the aryl group represented by the above R ^1b include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, and a naphthyl group. Among them, a phenyl group is preferred.

Examples of the aralkyl group represented by the above R ^1b include a benzyl group, an α-phenethyl group, and a β-phenethyl group.

Examples of the alkenyl group having 2 to 9 carbon atoms represented by the above R ^1b include a vinyl group, an allyl group, a butenyl group, and a (meth)acryloxyalkylene group.

Examples of the alkoxy group having 1 to 4 carbon atoms represented by the above R ^1b include a methoxy group, an ethoxy group, a n-propoxy group, and a n-butoxy group.

Among these, R ^{1b is} preferably an alkyl group having 1 to 18 carbon atoms, an aryl group, an alkenyl group having 2 to 9 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, more preferably a methyl group or a benzene group. base.

In the above formula (1-3), m is an integer of from 1 to 50, preferably an integer of from 2 to 45. In the above formula (1-4), n is an integer of from 1 to 1,500, preferably an integer of from 2 to 1400.

In the case where the adhesion imparting agent of the present invention has a structural unit of both the above formula (1-3) and the above formula (1-4), the ratio of m to n is preferably m: n = 1: 0.5~ 1:160, more preferably m:n=1:1~1:120.

Further, when m and/or n is 2 or more, each of R ^1b in the repeating unit may be the same or different.

In the above formulae (1-1) to (1-3), A is independently an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group having 2 to 9 carbon atoms, and a carbon number. An alkoxy group of 1 to 4 or a group represented by the above formula (2).

The alkyl group having 1 to 18 carbon atoms represented by the above A, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group having 2 to 9 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms may be respectively listed. The above R ^1a or the above R ^{1b is the} same.

In the case where the adhesion imparting agent of the present invention does not have the structural unit represented by the above formula (1-3), the effect of improving the adhesion is excellent, and the like, and the above formula (1-1) and the above formula (preferably) A in 1-2) is a group represented by the formula (2).

In the above formula (2), R ^2a represents an alkylene group having 1 to 8 carbon atoms which may be substituted with an oxygen atom in addition to a carbon atom bonded to a halogen atom.

Examples of the alkylene group having 1 to 8 carbon atoms represented by the above R ^2a include a methylene group, an ethylidene group, an exo-propyl group, an exo-butyl group, a di-n-pentyl group, a hexyl group, a decyl group, and A group in which a part of carbon atoms of the alkyl group are substituted by an oxygen atom. Among them, a group in which an ethyl group, an exo-propyl group, an exo-butyl group, a pentyl group, a hexyl group, and a carbon atom of one of the alkyl groups are substituted with an oxygen atom is preferred.

In the above formula (2), R ^2b each independently represents an alkylene group having 1 to 3 carbon atoms. Examples of the alkylene group having 1 to 3 carbon atoms represented by the above R ^2b include a methylene group, an ethylidene group, a stretched propyl group, and an extended isopropyl group.

Furthermore, in the case where x in the formula (2) is 2, the two R ^2b may be the same or different.

In the above formula (2), R ³ each independently represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, a sulfonyl group-containing group, a fluorenyl group, or a (meth) propylene oxy group. Alkyl, or fluorenyl.

Examples of the alkyl group having 1 to 18 carbon atoms represented by R ³ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tertiary butyl group, and a n-pentyl group. , neopentyl, tertiary amyl, n-hexyl, n-heptyl, 2,2,4-trimethylpentyl, n-octyl, isooctyl, n-decyl, n-decyl, n-dodecyl , n-octadecyl and the like. Further, the hydrogen atom of the alkyl group may be substituted, and specifically, one or more hydrogen atoms may be substituted with a halogen group such as a chloro group or a bromo group. Further, the carbon atom at the alkyl terminal may be substituted with a triethoxyindenyl group. The alkyl group having 1 to 18 carbon atoms represented by the above R ³ is preferably an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a n-hexyl group, a n-heptyl group or an n-dodecyl group. The octadecyl group is more preferably ethyl, n-propyl, n-butyl, n-hexyl or n-heptyl.

Examples of the cycloalkyl group represented by the above R ³ include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a methylcyclohexyl group. Among them, a cyclopentyl group and a cyclohexyl group are preferred, and a cyclohexyl group is more preferred.

Examples of the aryl group represented by the above R ³ include a phenyl group, a naphthyl group, and a biphenyl group. These aryl groups may also have a substituent. In the case where the aryl group has a substituent, examples of the substituent include a halogen group such as a fluoro group, a chloro group or a bromo group; a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and the like. An alkyl group having 1 to 4 carbon atoms such as n-butyl group; a halogenated alkyl group in which at least one or more hydrogen atoms of the alkyl group are substituted with a halogen group such as a fluoro group, a chloro group or a bromo group; An alkoxy group such as an oxy group or an ethoxy group; a halogenated alkoxy group obtained by substituting one or more hydrogen atoms of the alkoxy group with a halogen group such as a fluoro group, a chloro group or a bromo group; or Base. The aryl group represented by the above R ³ is preferably a phenyl group, a naphthyl group or a biphenyl group, more preferably a phenyl group.

Examples of the aralkyl group represented by the above R ³ include a benzyl group, a methylbenzyl group, an isopropenyldimethylbenzyl group, a phenethyl group, and a naphthylethyl group. Among them, a benzyl group or a phenethyl group is preferred, and a phenethyl group is more preferred.

Examples of the sulfonyl group-containing group represented by the above R ³ include a benzenesulfonyl group and a p-toluenesulfonyl group.

Examples of the thiol group represented by the above R ³ include a trichloroethenyl group and the like.

Examples of the (meth)acryloxyalkyl group represented by the above R ³ include a methacryloxyethyl group and the like.

Examples of the fluorenyl group represented by the above R ³ include a trimethyl fluorenyl group and the like.

Among these, R ^{3 is} preferably an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, more preferably an aralkyl group, and still more preferably a phenethyl group.

Further, when x in the formula (2) is 1 or more, each R ³ may be the same or different.

In the above formula (2), x is an integer of 0 to 2, and Y is an oxygen atom or NH.

The above x is preferably an integer of 0 or 1.

Furthermore, the case where x is 0 means that R ^2a is directly bonded to Y.

It is preferable that R ³ in the formula (2) is independently carbon as the adhesion imparting agent of the present invention, from the viewpoint of compatibility with the addition-curable polyoxyxene resin mixture or the availability of raw materials. A number of 1 to 18 alkyl, cycloalkyl, aryl, or aralkyl groups.

The functional group of the adhesion imparting agent of the present invention is a urea group (N-CO-NH) and/or a urethane group (N-CO-O). More specifically, the functional group equivalent of the adhesion imparting agent is defined by (the molecular weight of the adhesion imparting agent) / (the total number of moles of the urea group and the urethane group) and corresponds to m and n. The ratio. The lower limit of the functional group equivalent of the above formula (2) of the adhesion imparting agent of the present invention is preferably 100, and the upper limit is preferably 12,000. When the functional group equivalent of the above formula (2) of the adhesion imparting agent of the present invention is less than 100, it may not exhibit an adhesion commensurate with the functional group equivalent of the group represented by the above formula (2), or may be added to hardenability. The compatibility of the type of polyoxyxene resin mixture is poor. When the functional group equivalent of the above formula (2) of the adhesive agent of the present invention exceeds 12,000, the adhesion of the obtained addition-curable polydecane resin composition may be insufficient.

The lower limit of the functional group equivalent of the above formula (2) of the adhesion imparting agent of the present invention is preferably 200, more preferably 9000, and still more preferably 300, and further preferably 8000.

In the method for producing the adhesion imparting agent of the present invention, for example, the structural unit represented by the following formula (3-1) and the structural unit represented by the following formula (3-2) have the following formula (3). -3) a structural unit represented by a structural unit represented by the following formula (3-4) (hereinafter, also referred to as "a polyoxyl compound having an amine group and/or a hydroxyl group") and The isocyanate compound (hereinafter, also referred to simply as "isocyanate compound") represented by the formula (4) is inversely The method should be the same.

In the formulae (3-1) and (3-2), R ^1a each independently represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group having 2 to 9 carbon atoms. Or an alkoxy group having 1 to 4 carbon atoms. In the formula (3-3) and the formula (3-4), R ^1b each independently represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group having 2 to 9 carbon atoms. Or an alkoxy group having 1 to 4 carbon atoms. In the formula (3-3), m is an integer of 1 to 50, and in the formula (3-4), n is an integer of 1 to 1500. In the formula (3-1) to the formula (3-3), B is independently an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group having 2 to 9 carbon atoms, and a carbon number. An alkoxy group of 1 to 4 or a group represented by the following formula (5). Among them, at least one of the formulae (3-1) to (3-3) is a group represented by the formula (5).

Further, R ^1a in the formula (1-1) and (1-2) in the formula (3-1) and (3-2) each of R ^1a becomes the same group, the formula (3-3) R ^1b of the formula and the formula (1-3) (3-4) and the formula R (1-4) in the group ^1b respectively become the same.

In the formula (4), R ³ represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, a sulfonyl group-containing group, a fluorenyl group, a (meth) propylene decyloxyalkyl group, Or 矽基.

Further, the formula R (4) and in ³ of the formula R (2) in each of the ^three groups be the same.

In the formula (5), R ^2a represents an alkylene group having 1 to 8 carbon atoms which may be substituted by an oxygen atom in addition to a carbon atom bonded to a halogen atom, and R ^2b independently represents a carbon number of 1~. 3 alkylene. In the formula (5), x is an integer of 0 to 2, and Y represents an oxygen atom or NH.

In the case where x in the formula (5) is 2, the two R ^2b may be the same or different.

Further, the formula R (5) in the formula R ^2a (2) of the respective group ^2a become the same, the formula (5) (2) of R in the formula R ^2b and ^2b, respectively, be the same group.

In the case of production by the above production method, the amine group equivalent and the hydroxyl group equivalent of the above-mentioned amine group and/or hydroxyl group-containing polyoxo compound correspond to the functional group equivalent of the above-mentioned binder of the present invention. In addition, the functional group of the adhesion imparting agent of the present invention is a urea group (N-CO-NH) when a polyfluorene oxide compound having an amine group is used as a raw material to produce an adhesion imparting agent. In the case where a polyoxonium compound having a hydroxyl group is used as a raw material, it is a urethane group (N-CO-O).

In addition, as a method of measuring the amine group equivalent of the above-mentioned amine group-containing polyoxo compound, for example, a method such as non-aqueous titration using perchloric acid may be mentioned. Further, the hydroxyl equivalent of the above polyoxyalkylene compound having a hydroxyl group can be calculated from the hydroxyl value of the polyoxyalkylene compound having a hydroxyl group. The method of obtaining the hydroxyl value of the polyoxosiloxane having a hydroxyl group is, for example, a method described in JIS K 5601-2-1.

As a method for synthesizing the above-mentioned amine group-containing polyoxo compound, a method disclosed in the specification of U.S. Patent No. 3,355,424, the specification of U.S. Patent No. 2,947,771, the specification of U.S. Patent No. 3,890,269, etc., The polyalkylene oxide unit of the amino group is inserted into the polycondensation reaction in the chain of the decane. This reaction is usually carried out in the presence of an acidic or basic catalyst. This reaction can also be carried out in the form of a polymerization reaction of a dialkoxyalkyl decane and a cyclic siloxane. Further, the cyclic organopolyoxane and the aminoalkyl dioxane can be heated in the presence of a basic catalyst and a cyclic polyether disclosed in JP-A-03-095227. A method of reacting a cyclic organopolysiloxane and an aminoalkyl polyoxyalkylene in the presence of a basic catalyst as disclosed in JP-A-2005-043695, and the like. .

Further, as a method for synthesizing the polyoxosiloxane having a hydroxyl group, a polyorganosiloxane having a hydrogen atom bonded to a ruthenium atom and having an aliphatic group can be used as disclosed in JP-A-2004-88024. A method of adding an organic sulfonium compound having a saturated hydrocarbon group in the presence of a platinum-based catalyst. In this method, first, a polyorganosiloxane having a hydrogen atom bonded to a ruthenium atom is added to an organic ruthenium compound having an aliphatic unsaturated hydrocarbon group by hydrogenation using a platinum-based catalyst. Next, the trialkylsulfonyl group at the end of the molecular chain of the polyorganosiloxane which is formed by the addition reaction is removed by deuteration, and the terminal of the molecular chain is converted into a hydroxyl group to obtain a hydroxyl group. Polyorganosiloxane.

As a commercially available one of the above-mentioned amine group-containing polyoxo compounds, for example, KF-864, KF-865, KF-868, KF-857, KF-8001, KF-862 (monoamine type), KF -859, KF-393, KF-860, KF-880, KF-8004, KF-8002, KF-8005, KF-867, KF-869, KF-861 (diamine type), X-22-1660B- 3, X-22-9409 (both terminal amine, side chain phenyl type), PAM-E, KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008 (both terminal amine Type) (all manufactured by Shin-Etsu Chemical Co., Ltd.), BY16-205, BY16-849, FZ-3785, BY16-872, BY16-213, FZ-3705 (side chain amine type) (all manufactured by Dow Corning Toray) , AMS-132, AMS-152, AMS-162 (side chain amine type), DMS-A11, DMS-A12, DMS-A15, DMS-A21 (both terminal amine type) (all manufactured by Gelest, Inc.), etc. .

As a commercial one of the above-mentioned polyoxyl compounds having a hydroxyl group, for example, X-22-4039, X-22-4015 (side chain methanol type), X-22-160AS, KF-6001, KF-6002 can be cited. , KF-6003 (both end methanol type), X-22-170BX, X-22-170DX (single-end methanol type) (all manufactured by Shin-Etsu Chemical Co., Ltd.), SF8428 (side chain methanol type), SF8427, BY16- 201, BY16-004 (both terminal methanol type) (all manufactured by Dow Corning Toray Co., Ltd.), DMS-C15, DMS-C21 (both terminal methanol type) (all manufactured by Gelest, Inc.) and the like.

Examples of the above isocyanate compound include ethyl isocyanate, n-propyl isocyanate, n-butyl isocyanate, n-hexyl isocyanate, n-heptyl isocyanate, and n-dodecyl isocyanate. Ester, n-octadecyl isocyanate, isopropyl isocyanate, butyl isocyanate, 2-chloroethyl isocyanate, trichloromethyl isocyanate, isocyanate 3-( Triethoxymercapto)propyl ester, cyclopentyl isocyanate, cyclohexyl isocyanate, trans-4-methylcyclohexyl isocyanate, phenyl isocyanate, isocyanate Phenyl ester, m-toluene isocyanate, p-toluene isocyanate, 4-ethylphenyl isocyanate, 4-n-butylphenyl isocyanate, 2,6-dimethylphenyl isocyanate , 3,5-dimethylphenyl isocyanate, 2,6-diisopropylphenyl isocyanate, 3-chloro-4-methylphenyl isocyanate, 2-methoxy isocyanate Phenyl ester, 3-methoxyphenyl isocyanate, 4-methoxyphenyl isocyanate, 2-(trifluoromethoxy)phenyl isocyanate, 4-(trifluoromethoxy) isocyanate Phenyl ester, 4-ethoxyphenyl isocyanate, 2-(trifluoromethyl)phenyl isocyanate, 3-(trifluoromethyl)phenyl isocyanate, isocyanate 4-( Trifluoromethyl)phenyl ester, 3,5-bis(trifluoromethyl)phenyl isocyanate, 2-fluorophenyl isocyanate, 3-fluorophenyl isocyanate, 4-fluorobenzene isocyanate Ester, 2,4-difluorophenyl isocyanate, 2,5-difluorophenyl isocyanate, 3,4-difluorophenyl isocyanate, 2-chlorophenyl isocyanate, isocyanic acid 3-Chlorophenyl ester, 4-chlorophenyl isocyanate, 2-chloro-5-(trifluoromethyl)phenyl isocyanate, 4-chloro-3-nitrophenyl isocyanate, isocyanic acid 2,3-dichlorophenyl ester, 2,4-dichlorophenyl isocyanate, 2,5-dichlorophenyl isocyanate, 2,6-dichlorophenyl isocyanate, isocyanic acid 3, 4-dichloro Ester, 3,5-dichlorophenyl isocyanate, 2,4,6-trichlorophenyl isocyanate, 2-bromophenyl isocyanate, 3-bromophenyl isocyanate, isocyanic acid 4 -bromophenyl ester, 4-nitrophenyl isocyanate, 1-naphthyl isocyanate, 2-biphenyl isocyanate, benzyl isocyanate, phenylethyl isocyanate, (R)-( +)-α-methylbenzyl isocyanate, (S)-(-)-α-methylbenzyl isocyanate, (R)-(-)-1-(1-naphthyl)ethyl isocyanate, (S) -(+)-1-(1-naphthyl)ethyl isocyanate, 3-isopropenyl-α,α-dimethylbenzyl isocyanate, phenylsulfonyl isocyanate, p-toluenesulfonate isocyanate , trichloroacetic acid isocyanate, 2-methylpropenyloxyethyl isocyanate, trimethyl decyl isocyanate, and the like. Among them, from the viewpoints of economy or availability, ethyl isocyanate, n-propyl isocyanate, n-butyl isocyanate, n-hexyl isocyanate, n-heptyl isocyanate, and the like are preferred. Cyclohexyl cyanate, phenyl isocyanate, benzyl isocyanate, phenylethyl isocyanate.

As the above polyoxonium compound having an amine group and/or a hydroxyl group, and the above isocyanide The amount of the above-mentioned isocyanate compound used in the reaction of the acid ester compound is such that when x of the above formula (5) is 0 and Y is NH, it is relative to the amine group 1 mole of the polyoxonium compound having an amine group. Good is 0.8~5 moles, more preferably 0.9~3 moles. Further, when x in the above formula (5) is 0 and Y is an oxygen atom, it is preferably 0.8 to 5 m, more preferably 0.9 to the hydroxyl group of the polyoxonium compound having a hydroxyl group. 3 Mo Er. In the case where x of the above formula (5) is 1 or 2 and Y is NH, it is preferably 0.8 to 5 moles, more preferably 0.9, with respect to the amine group 1 mole of the polyoxonium compound having an amine group. ~3 moles. Further, when x in the formula (5) is 1 or 2 and Y is an oxygen atom, the total of the amine group and the hydroxyl group relative to the polyoxymethane compound having an amine group and a hydroxyl group is 1 mole, preferably 0.8 to 5 moles, more preferably 0.9 to 3 moles. The amine group referred to herein is an amine group which is reactive with the above isocyanate compound, and is specifically a primary amine group and a secondary amine group.

The reaction of the above polyoxosiloxane having an amine group and/or a hydroxyl group with the above isocyanate compound can also be carried out in the presence of a solvent. The solvent to be used is not particularly limited as long as the polyoxonium compound having an amine group and/or a hydroxyl group is easily dissolved and does not inhibit the reaction of the above polyoxo compound having an amine group and/or a hydroxyl group with the above isocyanate compound. Particularly, for example, hexane, heptane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, cyclohexane, dichloromethane, chloroform, diethyl ether, diisopropyl ether, acetone, methyl ethyl Ketone, methyl isobutyl ketone, and the like.

The reaction of the above polyamine oxide having an amine group and/or a hydroxyl group with the above isocyanate compound is preferably carried out at a temperature in the range of -20 to 150 ° C, more preferably in the range of 0 to 140 ° C, depending on the solvent to be used. The temperature inside is carried out without using a solvent.

The lower limit of the content of the adhesion-imparting agent of the present invention in the addition-curable polyoxyxylene resin composition of the present invention is preferably 0.01% by mass, and the upper limit is preferably 15% by mass. If this hair When the content of the adhesion imparting agent is less than 0.01% by mass, the effect of improving the adhesion may not be sufficiently exhibited. When the content of the adhesion imparting agent of the present invention exceeds 15% by mass, the hardness of the cured product may be adversely affected. The lower limit of the content of the adhesion imparting agent of the present invention is preferably 0.05% by mass, more preferably 10% by mass, still more preferably 0.1% by mass, and still more preferably 5% by mass.

In addition, the content of the adhesion imparting agent of the present invention is preferably 0.01 parts by mass, and preferably 20 parts by mass, based on 100 parts by mass of the addition-curable polyoxirane resin mixture. When the content of the adhesion imparting agent of the present invention is less than 0.01 parts by mass, the effect of improving the adhesion may not be sufficiently exhibited. When the content of the adhesion imparting agent exceeds 20 parts by mass, the hardness of the cured product may be adversely affected. A more preferred lower limit of the content of the adhesion imparting agent of the present invention is 0.1 part by mass, more preferably an upper limit of 13 parts by mass, still more preferably a lower limit of 0.3 part by mass, and still more preferably an upper limit of 6 parts by mass.

The addition-curable polydecane resin composition of the present invention may contain other adhesion imparting agents in addition to the adhesion imparting agent of the present invention, within a range not inhibiting the object of the present invention.

The addition hardening type polyoxyxylene resin composition of the present invention contains an addition hardening type polyoxyxylene resin mixture.

The addition-hardening polyoxynoxy resin mixture contains a mixture of addition-curable polyoxynoxy resins which are hardened by hydrogenation reaction of a mercapto group having a carbon-carbon double bond with a hydroquinone group.

The addition-hardening type polyoxyxene resin mixture preferably contains a polyorganosiloxane having at least two substituents having a carbon-carbon double bond bonded to a ruthenium atom (hereinafter, also referred to as "carbon-containing" a polyorganosiloxane having a carbon double bond"), a polyorganic having at least two hydrogen atoms bonded to a deuterium atom Hydroquinone (hereinafter also referred to as "polyorganohydroquinone") and a hydrogenation catalyst.

The molecular structure of the polyorganosiloxane containing the carbon-carbon double bond may, for example, be a linear or cyclic structure, or may have a branch in the structure. Among them, a linear structure in which the main chain is composed of repeating units of diorganomoperoxane and the both ends are blocked by triorganosalkoxy groups is preferred.

The substituent having a carbon-carbon double bond bonded to a ruthenium atom among the polyorganosiloxane containing the carbon-carbon double bond is preferably a carbon number of 2 to 8, and specifically, for example, Vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, propylene fluorenyl, methacryl fluorenyl and the like. Among them, a vinyl group, an acrylonitrile group, a methacryl fluorenyl group is preferred, and a vinyl group is more preferred.

In the case where the molecular structure of the above-mentioned polyorganosiloxane containing a carbon-carbon double bond is linear, a substituent having a carbon-carbon double bond may be bonded to only one of the terminal and the middle of the molecular chain. An atom may also be bonded to a ruthenium atom at both the end and the middle of the molecular chain.

The organic group bonded to the ruthenium atom other than the substituent having a carbon-carbon double bond in the above-mentioned polyorganosiloxane containing a carbon-carbon double bond, for example, the following unsubstituted or halogen-substituted 1 Valence hydrocarbon group: methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl, n-decyl, and the like, an alkyl group having 1 to 12 carbon atoms; a aryl group having 6 to 14 carbon atoms such as a benzyl group, a tolyl group, a xylyl group or a naphthyl group; an aralkyl group such as a benzyl group, a phenethyl group or a phenylpropyl group; or a chloromethyl group, a 3-chloropropyl group or a bromoethyl group; a halogenated alkyl group such as a 3,3,3-trifluoropropyl group or the like. Among them, an alkyl group or an aryl group is preferred, and a methyl group or a phenyl group is more preferred, and a methyl group is further preferred.

A preferred lower limit of the viscosity of the above-mentioned polyorganosiloxane containing a carbon-carbon double bond is 100 mPa‧s, and a preferred upper limit is 100,000 mPa‧s. Viscosity of polyorganosiloxanes containing carbon-carbon double bonds In the case of being in this range, the workability of the addition-hardening type polyoxyxylene resin composition obtained is good, and the physical properties of the cured product obtained from the addition-hardening type polyoxymethylene resin composition are good. A lower limit of the viscosity of the polyorganosiloxane containing a carbon-carbon double bond is 500 mPa‧s, and a more preferred upper limit is 10,000 mPa‧s.

In the present specification, the above "viscosity" means a value measured using a rotational viscometer (BM type) at 25 °C.

Specific examples of the polyorganosiloxane having a carbon-carbon double bond include a dimethyl methoxy oxane-methyl vinyl decane terminated by a trimethyl decyloxy group at both ends of the molecular chain. a copolymer, a methyl vinyl polyoxyalkylene terminated by a trimethyldecaneoxy group at both ends of the molecular chain, and a dimethyl methoxy alkane-methylethylene terminated at the two ends of the molecular chain by a trimethyldecyloxy group a quinone oxo-methylphenyl decane copolymer, a dimethylpolysiloxane having a dimethyl vinyl alkoxy group terminated at both ends of the molecular chain, and a dimethyl vinyl decane at both ends of the molecular chain Oxy-terminated methyl vinyl polyoxyalkylene, dimethyl methoxy alkane-methyl vinyl siloxane copolymer terminated by dimethyl vinyl decyloxy at both ends of the molecular chain, molecular chain two a dimethyl methoxy alkane-methylvinyl oxime-methyl phenyl siloxane copolymer terminated with a dimethylvinyl decyloxy group, and the two ends of the molecular chain are sealed by a trivinyl decyloxy group. the end of the dimethylpolysiloxane silicone siloxane by ^{_{(R 4) 3 SiO 0.5 (}} R 4 having the non-substituted alkenyl group or substituted monovalent hydrocarbon group of 1, hereinafter the same) table Silicon alkoxy UNIT silicon alkoxy ^{_{units, (R 4) 2 R 5}} SiO 0.5 (R 5 is an alkenyl group or comprises alkenyl group, the same applies hereinafter) represented by the, (R ⁴⁾ ₂ SiO represented by the silicon-alkoxy a polyorganosiloxane copolymer composed of a unit and a decyloxy unit represented by SiO ₂ , a decyloxy unit represented by (R ⁴ ) ₃ SiO _0.5 , and (R ⁴ ) ₂ R ⁵ SiO _0.5 a polyorganooxyalkylene copolymer composed of a decyloxy unit and a decyloxy unit represented by SiO ₂ , a decyloxy unit represented by (R ⁴ ) ₂ R ⁵ SiO _0.5 , and (R ⁴ ) ₂ SiO a polyorganosiloxane copolymer represented by a decyloxy unit and a decyloxy unit represented by SiO ₂ , a decyloxy unit represented by R ⁴ R ⁵ SiO, and a decane represented by R ⁴ SiO _1.5 a polyorganosiloxane copolymer composed of an oxy unit or a decyloxy unit represented by R ⁴ SiO _1.5 , a decyloxy unit represented by (R ⁴ ) ₃ SiO _0.5 , and (R ⁴ ) ₂ SiO a decyloxy unit, a decyloxy unit represented by R ⁴ R ⁵ SiO, a decyloxy unit represented by R ⁴ SiO _1.5 , and (R ⁴ ) ₄ Si ₂ R ⁶ O (R ⁶ is a diorganohydrocarbyl group, the same as the above), a polyorganosiloxane copolymer represented by a decyloxy unit, a decyloxy unit represented by (R ⁴ ) ₂ SiO, and a decyloxy unit represented by R ⁴ R ⁵ SiO And a polyorganosiloxane copolymer composed of a decyloxy unit represented by (R ⁴ ) ₄ Si ₂ R ⁶ O. These may be used alone or in combination of two or more.

Examples of the above R ⁴ include a carbon number of 1 or more such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-decyl or n-decyl. Alkane having a carbon number of 3 to 8 such as a cyclopentyl group, a cyclohexyl group or a cycloheptyl group; an aryl group having a carbon number of 6 to 14 such as a phenyl group, a tolyl group, a xylyl group or a naphthyl group; An aralkyl group such as phenethyl or phenylpropyl; or a halogenated alkyl group such as chloromethyl, 3-chloropropyl, bromoethyl or 3,3,3-trifluoropropyl. Among them, the above R ^{4 is} preferably an alkyl group or an aryl group, more preferably a methyl group or a phenyl group.

The above R ^{5 is} preferably a carbon number of 2 to 8, and examples thereof include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, a propylene group, and a methacryl group.醯基等. Among them, a vinyl group, an acrylonitrile group, a methacryl fluorenyl group is preferred, and a vinyl group is more preferred.

Examples of the above R ⁶ include a phenyl group, an ethyl group, a hexyl group, and an octyl group. Among them, a phenyl group is preferred.

As a commercially available one of the above-mentioned polyorganosiloxane containing a carbon-carbon double bond, for example, DMS-V21, DMS-V22, DMS-V25, DMS-V31, DMS-V33, DMS-V35, DMS-V41, DMS-V42, DMS-V46, DMS-V25R, DMS-V35R (dimethyl polyoxyalkylene terminated by dimethyl vinyl alkoxy group at both ends of the molecular chain), PDV -0325, PDV-0331, PDV-0341, PDV-0346, PDV-0525, PDV-0535, PDV-0541, PDV-1625, PDV-1631, PDV-1635, PDV-1641, PDV-2331 (molecular chain two a dimethyl methoxy alkane-diphenyl decane copolymer terminated with a dimethylvinyl alkoxy group, VDT-123, VDT-127, VDT-131, VDT-431, VDT-731 ( a dimethyl methoxy alkane-methylvinyl fluorene copolymer terminated by a trimethyl decyloxy group at both ends of the molecular chain, PMV-9925 (both ends of the molecular chain are sealed by dimethyl vinyl decyloxy) Phenylmethyl polyoxane at the end, PVV-3522 (vinyl phenyl methoxy oxane-phenylmethyl decane copolymer terminated by a vinyl phenylmethyl group at both ends of the molecular chain) For the manufacture of Gelest, Inc.) and the like.

The polyorganohydroquinoxane is reacted with the above-mentioned polyorganosiloxane having a carbon-carbon double bond to function as a crosslinking component.

As the polyorganohydrohalosiloxane, for example, various polyorganohydrohalosiloxanes having a molecular structure such as a linear, a cyclic, a branched, or a three-dimensional network structure (resin) can be used.

The polyorganohydroquinone has 2 or more, preferably 3 or more, hydrogen atoms bonded to a halogen atom, that is, a hydroquinone group (Si-H group) in one molecule. In the case where the molecular structure of the polyorganohydroquinone is linear, the Si-H groups may be located only at either the end of the molecular chain and the intermediate portion, or both.

The number (degree of polymerization) of the ruthenium atoms in one molecule of the above polyorganohydroquinone is preferably from 2 to 1,000, more preferably from 3 to 100.

As the above polyorganohydroquinone oxyalkylene, for example, R ⁷ _a H _b SiO _{(4 ab / 2)} (R ⁷ -based unsubstituted or substituted monovalent hydrocarbon group having 1 to 14 carbon atoms; R ⁷ carbon can be used. The number is preferably from 1 to 10. a and b are preferably 0.7 ≦ a ≦ 2.1, 0.001 ≦ b ≦ 1.0, and satisfy a positive number of 0.8 ≦ a + b ≦ 3.0, more preferably satisfying 1.0 ≦ a + b ≦ 2.5 A polyorganohydroquinone represented by a positive number.

Examples of the above R ⁷ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-octyl. a carbon number of 1 to 12 such as a fluorenyl group or a fluorenyl group; a cycloalkyl group having a carbon number of 3 to 8 such as a cyclopentyl group, a cyclohexyl group or a cycloheptyl group; a phenyl group, a tolyl group, a xylyl group, and a naphthyl group; An aryl group having 6 to 14 carbon atoms; an aralkyl group such as a benzyl group, a phenethyl group or a phenylpropyl group; an alkenyl group such as a vinyl group or an allyl group; or a part or all of a hydrogen atom in the hydrocarbon group; A group substituted with a halogen atom, for example, a chloromethyl group, a 3-chloropropyl group, a bromoethyl group, a 3,3,3-trifluoropropyl group or the like. Among them, the above R ^{7 is} preferably an alkyl group or an aryl group, more preferably a methyl group or a phenyl group, and still more preferably a methyl group.

Further, the above R ⁷ may be the same hydrocarbon group or different.

Specific examples of the polyorganohydrohalosiloxane represented by R ⁷ _a H _b SiO _{(4 ab / 2)} in the above polyorganohydroquinoxane include, for example, a trimethyldecyloxy group at both ends of the molecular chain. a blocked methyl hydrogen polyoxyalkylene, a dimethyl methoxy alkane-methylhydrooxane copolymer terminated at the two ends of the molecular chain by a trimethyl decyloxy group, and a trimethyl decane at both ends of the molecular chain Oxy-terminated dimethyloxane-methylhydroquinone-methylphenyl decane copolymer, dimethylpolyoxyl terminated by dimethylhydrohaloalkoxy at both ends of the molecular chain a dimethylpolyoxyalkylene-methylhydrooxane copolymer terminated by a dimethyl hydralkoxy group at both ends of the molecular chain, and a terminal end of the molecular chain terminated by a dimethylhydrogen alkoxy group a methyl oxoxane-methylphenyl decane copolymer, a methylphenyl polyoxyalkylene terminated at both ends of the molecular chain by dimethylhydrohaloalkoxy, and (R ⁴ ) ₃ SiO _0.5 (R polyorganohydrogen siloxane copolymer consisting of silicon ⁴ described above) represents an alkoxy group of the silicon units, (R ⁴⁾ ₂ HSiO _0.5 units alkoxy silicon represented by silicon and an alkoxy group of units of SiO ₂ represented by (R ⁴ ) ₂ a polyorganohydrohalosiloxane copolymer composed of a decyloxy unit represented by HSiO _0.5 and a decyloxy unit represented by SiO ₂ , a decyloxy unit represented by R ⁴ HSiO, and a decane represented by R ⁴ SiO _1.5 A polyorganohydrohalosiloxane copolymer composed of an oxy unit or a decyloxy unit represented by HSiO _1.5 .

Specific examples of the polyorganohydrohalosiloxane other than the polyorganohydrohalosiloxane represented by R ⁷ _a H _b SiO _{(4 ab / 2)} include, for example, (R ⁴ ) ₃ SiO _0.5 a decyloxy unit, a decyloxy unit represented by (R ⁴ ) ₂ HSiO _0.5 , a decyloxy unit represented by (R ⁴ ) ₂ SiO, a decyloxy unit represented by R ⁴ SiO _1.5 , and (R ⁴ ₄ Si ₂ R ⁶ O (R ⁶ as described above) represents a polyorganohydrohydroxane copolymer composed of a decyloxy unit; a decyloxy unit represented by (R ⁴ ) ₃ SiO _0.5 , (R ^{4 )} a decyloxy unit represented by ₂ HSiO _0.5 , a decyloxy unit represented by (R ⁴ ) ₂ SiO, a decyloxy unit represented by R ⁵ SiO _1.5 (R ⁵ as described above), and (R ⁴ ) ₄ a polyorganohydrohydroxane copolymer composed of a decyloxy unit represented by Si ₂ R ⁶ O; a decyloxy unit represented by (R ⁴ ) ₃ SiO _0.5 and a decane oxygen represented by (R ⁴ ) ₂ SiO A base unit, a decyloxy unit represented by R ⁴ HSiO, and a polyorganohydrohalosiloxane copolymer composed of a decyloxy unit represented by (R ⁴ ) ₄ Si ₂ R ⁶ O. These may be used alone or in combination of two or more.

As a commercially available one of the above polyorganohydroquinones, for example, DMS-H03, DMS-H11, DMS-H21, DMS-H25, DMS-H31, DMS-H41 (both ends of the molecular chain are dimethyl groups) Hydroquinoloxy-terminated dimethyl polyoxane), HMS-013, HMS-031, HMS-064, HMS-071, HMS-082, HMS-151, HMS-301, HMS-501 (molecular chain) a dimethyl methoxy alkane-methylhydroioxane copolymer terminated by a trimethyl decyloxy group, HMS-991, HMS-992, HMS-993 (trimethyl decane at both ends of the molecular chain) Oxy-terminated methylhydrogen polyoxyalkylene), HMS-H271 (dimethyl methoxy oxane-methylhydroioxane copolymer terminated at both ends of the molecular chain by dimethylhydrogenoloxy), HPM-502 (minutes a phenylmethyl methoxy-methane hydroxane copolymer terminated by a dimethylhydroquinoloxy group at both ends of the sub-chain, HDP-111 (both ends of the molecular chain are blocked by dimethylhydroperoxyloxy group) Phenyl (dimethylhydroquinoloxy) decane (all manufactured by Gelest, Inc.) and the like.

The content of the polyorganohydroquinone is a hardening effective amount of the above-mentioned polyorganosiloxane containing a carbon-carbon double bond, and particularly preferably a ratio such that the polyorganohydrohalosiloxane has a Si-H group relative thereto. The substituent having a carbon-carbon double bond in the polyorganosiloxane containing a carbon-carbon double bond is 0.1 to 4.0. When the Si-H group is less than 0.1 per one substituent having a carbon-carbon double bond, the curing reaction does not proceed, and it is difficult to obtain a cured product. When the Si-H group has more than 4.0 substituents per carbon-carbon double bond, the unreacted Si-H group remains in the cured product in a large amount, so that the physical properties of the cured product change with time. Hey. More preferably, the Si-H group is in a ratio of 1.0 to 3.0 per one substituent having a carbon-carbon double bond.

As the above-mentioned hydrazine hydrogenation catalyst, those previously known can be used. Specific examples thereof include platinum (including platinum black), platinum group metal such as rhodium and palladium; H ₂ PtCl ₄ ‧nH ₂ O, H ₂ PtCl ₆ ‧nH ₂ O, NaHPtCl ₆ ‧nH ₂ O, KHPtCl ₆ ‧nH ₂ O, Na ₂ PtCl ₆ ‧nH ₂ O, K ₂ PtCl ₄ ‧nH ₂ O, PtCl ₄ ‧nH ₂ O, PtCl ₂ , Na ₂ HPtCl ₄ ‧nH ₂ O (wherein n is An integer of 0 to 6, preferably an integer of 0 or 6, such as platinum chloride, chloroplatinic acid, and chloroplatinate; an alcohol modified chloroplatinic acid (refer to US Pat. No. 3,220,972); chloroplatinic acid and olefin The composite (refer to the specification of U.S. Patent No. 3,159,601, the specification of U.S. Patent No. 3,159,662, and the specification of U.S. Patent No. 3,775,452); the carrier of alumina, yttrium oxide, carbon, etc. is supported by a platinum group metal such as platinum black or palladium. ; 铑-olefin complex; tris(triphenylphosphine) ruthenium chloride (Wikinson catalyst); complex of platinum chloride, chloroplatinic acid or chloroplatinate with vinyl-containing decane Platinum (II); (Japanese Unexamined Patent Publication No. Hei 09-165453); Pt ₂ {[(CH ₂ =CH)Me ₂ Si] ₂ O} ₃ , HPt ₂ {[(CH ₂ =CH) )Me ₂ Si ₂ ]O} ₂ , PtCO(CH ₂ =CH(Me)SiO) ₄ , P _{t (CH 2 = CH (Me} ) SiO) 4 Si, etc. platinum vinyl siloxane complexes (see Japanese Patent Laid-Open Publication No. 11-152337), and other platinum group metal-based catalyst and the like.

The content of the ruthenium hydrogenation catalyst is not particularly limited as long as it is effective as a catalyst for the hydrazine hydrogenation reaction, and it is preferably 0.1 to 0.1% of the metal element such as platinum in the addition-curable polyoxirane resin mixture. 1000ppm. When the content of the above-mentioned rhodium hydrogenation catalyst is in this range, the addition reaction is sufficiently promoted, so that the obtained addition-curable polydecane resin composition can be sufficiently hardened and economically advantageous. The content of the above-mentioned rhodium hydrogenation catalyst is more preferably from 1 to 500 ppm, still more preferably from 1 to 20 ppm.

As the addition-curable polydecane resin mixture, a known one can be used, and in view of ease of availability, a two-component thermosetting type is preferable.

As a commercial item of the thermosetting type addition hardening type polyoxyxene resin mixture of the above two liquid type, for example, IVS4312, XE14-C2042, IVS4542, IVS4546, IVS4622, IVS4632, IVS4742, IVS4752, XE14-C2860, XE14 are mentioned. -C3450, IVS5854 (both manufactured by Momentive Performance Materials), KER-2500, KER-2500N, KER-2600, KER-2700, KER-6150, KER-6075F, KER-6020F, SCR-1011, SCR-1012, SCR-1016, KER-6000, KER-6100, KER-6110, KER-6200, ASP-1031, ASP-1111, ASP-1120 (all manufactured by Shin-Etsu Chemical Co., Ltd.), OE-6351, OE-6336, OE -6370M, EG-6301, JCR-6125, JCR-6140, 0E-6450, OE-6520, OE-6550, OE-6631, OE-6636, OE-6635, OE-6630, OE-6665N, SR7010 (both Manufactured for Dow Corning Torav).

The addition-hardening type polyoxyxylene resin composition of the present invention may contain an additive as needed in addition to the addition-hardening type polyoxyxylene resin mixture and the adhesion imparting agent of the present invention, without impairing the object or effect of the present invention. .

Examples of the above additives include inorganic fillers, antioxidants, inorganic phosphors, lubricants, ultraviolet absorbers, thermo-light stabilizers, dispersants, antistatic agents, polymerization inhibitors, antifoaming agents, and hardening accelerators. , solvent, anti-aging agent, free radical inhibitor, adhesion improver, flame retardant, surfactant, storage stability improver, ozone aging agent, tackifier, plasticizer, radiation blocker, A nucleating agent, a coupling agent, a conductivity imparting agent, a phosphorus-based peroxide decomposing agent, a pigment, a metal inerting agent, a physical property adjusting agent, and the like.

The inorganic filler is not particularly limited, and examples thereof include those having no fine optical properties. Specific examples thereof include alumina, aluminum hydroxide, fused cerium oxide, crystalline cerium oxide, ultrafine powder amorphous cerium oxide, hydrophobic ultrafine powder cerium oxide, talc, calcium carbonate, barium sulfate, and the like.

Examples of the inorganic phosphor include a YAG-based phosphor, an ZnS-based phosphor, a Y ₂ O ₂ S-based phosphor, and a red-emitting phosphor which are widely used for LEDs, aluminum, and garnet. , blue luminescent phosphor, green luminescent phosphor, etc.

The method for producing the addition-curable polydecane resin composition of the present invention can be produced, for example, by mixing an addition-curable polydecane resin mixture, an adhesion-imparting agent of the present invention, and an additive as needed. .

The addition-hardening polyphthalocyanine resin composition of the present invention can be a one-liquid type or a two-liquid type.

The addition-hardening polyphthalocyanine resin composition of the present invention can be applied, for example, to an optical semiconductor element or the like. The substrate is hardened and used.

The method of applying the addition-curable polydecane resin composition of the present invention to a substrate includes, for example, a method using a dispenser, a potting method, screen printing, transfer molding, and injection molding.

The addition hardening type polyoxymethylene resin composition of the present invention can be hardened by room temperature or heating. The addition-curable polyanthracene resin cured product obtained by curing the addition-curable polyoxyxylene resin composition of the present invention is also one of the inventions.

The final heating temperature when the addition-curable polydecane resin composition of the present invention is heated and hardened is usually 100 ° C or higher, preferably 120 ° C or higher, more preferably 120 to 200 ° C, and still more preferably 120. ~180 °C.

The use of the composition of the addition-hardening type polyoxyxylene resin of the present invention is, for example, a sealing material composition for an electronic material, a sealant composition for a building, a sealant composition for an automobile, an adhesive composition, and the like.

Examples of the electronic material include a lead frame, a wound tape substrate, a wiring board, a support member such as a glass or a germanium wafer, an optical semiconductor element, a semiconductor wafer, a transistor, a diode, a thyristor, and the like. Active components, or passive components such as capacitors, resistors, and coils. Among them, it can be preferably used as a sealing material for an optical semiconductor element.

The optical semiconductor element sealing body in which the optical semiconductor element is sealed by the addition hardening type polyoxymethylene resin of the present invention is also one of the inventions.

Further, the addition-hardening polyphthalocyanine resin composition of the present invention can be used, for example, for display materials, optical recording medium materials, optical machine materials, optical component materials, optical fiber materials, photo-electron functional organic materials, and semiconductor integrated circuit peripheral materials. And other uses.

According to the present invention, it is possible to provide an addition-curable polydecane resin composition which is excellent in interfacial adhesion and transparency. Moreover, according to the present invention, it is possible to provide an addition-curable polyphthalocyanine cured product and an optical semiconductor element sealing body which are obtained by using the addition-curable polyoxyxylene resin composition.

Hereinafter, the present invention will be described in detail by explaining the examples, but the invention is not limited to the examples.

(Manufacturing Example 1)

(Reaction of an amine group-containing polyoxo compound with phenylethyl isocyanate (preparation of adhesion imparting agent A))

To a four-necked flask of 500 mL capacity equipped with a magnetic rotor, a thermometer, and a cooler, an amine group-containing polyoxo compound (X-22-6060-3, amine, manufactured by Shin-Etsu Chemical Co., Ltd., amine) was added under a nitrogen atmosphere. Base amount: 2200 g/mol) 50.1 g (amino group 22.8 mmol) and phenylethyl isocyanate (molecular weight: 147.18) 3.61 g (24.5 mmol) were stirred at 20 ° C for 5 hours using a magnetic stirrer. It was confirmed by neutralization titration that the residual amine group was less than 1%. Thereafter, 207 g of toluene and 50 g of water were added to separate the layers, and the organic layer was concentrated to obtain 40.34 g of a transparent liquid (adhesive imparting agent A).

When the adhesion-promoting agent A was measured by ¹ H-NMR, it was confirmed that the adhesion-imparting agent A has the structural unit represented by the above formula (1-1) (R ^1a is a methyl group, and A is represented by the formula (2). a group, R ^2a is an exo-propyl group, x is 0, Y is NH, R ³ is a phenethyl group, and the structural unit represented by the above formula (1-2) (R ^1a is a methyl group, and A is a formula (2) Further, R ^2a is an epi-propyl group, x is 0, Y is NH, R ³ is a phenethyl group, and a structural unit represented by the above formula (1-4) (R ^1b is a methyl group or a phenyl group).

(Manufacturing Example 2)

(Reaction of an amine group-containing polyoxo compound with phenylethyl isocyanate (preparation of adhesion imparting agent B))

To a four-necked flask equipped with a magnetic rotor, a thermometer, and a cooler in a volume of 100 mL, a polyoxyl compound having an amine group ("X-22-9409", an amine equivalent, was added under a nitrogen atmosphere). 670 g/mol) 7.24 g (amine group 10.8 mmol) and phenylethyl isocyanate (molecular weight 147.18) 1.75 g (11.9 mmol) were stirred at 20 ° C for 5 hours using a magnetic stirrer. It was confirmed by neutralization titration that the residual amine group was less than 1%. Thereafter, 50 g of toluene and 10 g of water were added to separate the layers, and the organic layer was concentrated to obtain 2.55 g of a transparent liquid (adhesive imparting agent B).

When the adhesion-imparting agent B was measured by ¹ H-NMR, it was confirmed that the adhesion-imparting agent B has the structural unit represented by the above formula (1-1) (R ^1a is a methyl group, and A is represented by the formula (2). a group, R ^2a is an exo-propyl group, x is 0, Y is NH, R ³ is a phenethyl group, and the structural unit represented by the above formula (1-2) (R ^1a is a methyl group, and A is a formula (2) Further, R ^2a is an epi-propyl group, x is 0, Y is NH, R ³ is a phenethyl group, and a structural unit represented by the above formula (1-4) (R ^1b is a methyl group or a phenyl group).

(Manufacturing Example 3)

(Reaction of a polyoxyl compound having a hydroxyl group with phenylethyl isocyanate (preparation of an adhesion-imparting agent C))

In a four-necked flask equipped with a magnetic rotor, a thermometer, and a cooler in a volume of 50 mL, in nitrogen A polyoxonium compound having a hydroxyl group ("X-22-4015", hydroxyl group equivalent: 1867 g/mol), 4.99 g (hydroxyl 2.67 mmol) and phenylethyl isocyanate (molecular weight: 147.18) were added under a gas atmosphere. 0.52 g (3.53 mmol) was heated to 120 ° C and stirred for 10 hours using a magnetic stirrer. It was confirmed by titration that the residual hydroxyl group was less than 1%. Thereafter, 25 g of heptane and 5 g of water were added to separate a liquid, and the organic layer was concentrated, whereby 3.0 g of a transparent liquid (adhesive imparting agent C) was obtained.

When the adhesion-promoting agent C was measured by ¹ H-NMR, it was confirmed that the adhesion-imparting agent C has the structural unit represented by the above formula (1-1) (R ^1a is a methyl group, A is a methyl group), and the above formula (1-2) The structural unit (R ^1a is a methyl group, A is a methyl group), the above formula (1-3) (R ^1b is a methyl group, A is a group represented by the formula (2), and R ^2a is a positive 4-oxahexyl group, x is 0, Y is an oxygen atom, R ³ is a phenethyl group, and a structural unit represented by the above formula (1-4) (R ^1b is a methyl group).

(Manufacturing Example 4)

(Reaction of a polyoxyl compound having a hydroxyl group with phenylethyl isocyanate (preparation of an adhesion-imparting agent D))

To a four-necked flask equipped with a magnetic rotor, a thermometer, and a cooler in a volume of 50 mL, a polyoxonium compound having a hydroxyl group ("KF-6003", a hydroxyl equivalent of 2545 g/mol) was added under a nitrogen atmosphere. 5.00 g (hydroxyl 1.96 mmol) and phenylethyl isocyanate (molecular weight: 147.18), 0.44 g (2.99 mmol), and the mixture was heated to 120 ° C, and stirred for 15 hours using a magnetic stirrer. It was confirmed by titration that the residual hydroxyl group was less than 1%. Thereafter, 26 g of heptane and 5 g of water were added to separate liquid, and the organic layer was concentrated, whereby 4.1 g of a transparent liquid (adhesion imparting agent D) was obtained.

When the adhesion-imparting agent D was measured by ¹ H-NMR, it was confirmed that the adhesion-imparting agent D has the structural unit represented by the above formula (1-1) (R ^1a is a methyl group, and A is represented by the formula (2). a group, R ^2a is a 4-isohexyl group, x is 0, Y is an oxygen atom, R ³ is a phenethyl group, and the structural unit represented by the above formula (1-2) (R ^1a is a methyl group, and A is a formula) (2) a group represented by R ^2a is a 4-isohexyl group, x is 0, Y is an oxygen atom, R ³ is a phenethyl group, and a structural unit represented by the above formula (1-4) (R ^1b is methyl).

(Examples 1 to 12, Comparative Examples 1 to 6)

Each component was uniformly mixed in the blending amount shown in Table 1, and then sufficiently degassed to prepare an addition-curable polydecane resin composition.

Further, as the addition-hardening type polyoxymethylene resin mixture A in Table 1, OE-6630 (manufactured by Dow Corning Toray Co., Ltd.) A liquid and B liquid (1:4 mixture) were used. The addition-hardening polyxanthene resin mixture A is a mixture of a polyorganosiloxane component containing a carbon-carbon double bond and a polyorganohydroquinone component. As the addition-hardening type polyoxymethylene resin mixture B in Table 1, OE-6370M (Dow Corning Toray Co., Ltd.) A liquid and B liquid (1:1 mixture) were used. The addition-hardening polyoxyxene resin mixture B is a mixture of a polyorganosiloxane component containing a carbon-carbon double bond and a polyorganohydroquinone component. As the adhesion imparting agent E in Table 1, glycidoxypropyltrimethoxydecane ("Z-6040", manufactured by Dow Corning Toray Co., Ltd.) was used, and as the adhesion imparting agent F, isomeric cyanuric acid was used. Glycidyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.).

<evaluation>

Each of the addition-curable polyphthalocyanine resin compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 6 was subjected to the following evaluation. The results are shown in Table 1.

(1) Hardness (D type, A type)

Each of the addition-curable polydecane resin compositions (Examples 1 to 6 and Comparative Examples 1 to 3) containing the addition-curable polyoxyxylene resin mixture A was poured into a resin mold, and heated at 150 ° C for 2 hours. The addition hardening type polyoxymethylene resin composition is hardened. The obtained hardened material is released from the mold, A cured product having a radius of 20 mm and a thickness of 6 mm was prepared and used as a test piece for hardness measurement. The obtained hardness test piece was measured for hardness (D type) using a rubber hardness meter (manufactured by ASKER, Model D).

Further, each of the addition-curable polydecane resin compositions (Examples 7 to 12 and Comparative Examples 4 to 6) containing the addition-curable polyoxyxylene resin mixture B was poured into a resin mold and heated at 150 ° C. In an hour, the polyoxymethylene resin composition is hardened. The obtained cured product was released from the mold to obtain a cured product having a radius of 20 mm and a thickness of 6 mm, and was used as a test piece for hardness measurement. The obtained hardness test piece was measured for hardness (type A) using a rubber-plastic hardness meter ("KR-24A" manufactured by Guri Seiki Co., Ltd.).

(2) Tensile shear strength to PPA

Each of the addition-curable polyxanthoxy resin compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 6 was poured into two PPA sheets so that the adhesive portion became a rectangular shape of 20 × 25 mm (manufactured by Kuraray Co., Ltd., "GENESTAR TA112", size 2 × 25 × 100 mm) was 2 mm thick and heated (Examples 1 to 6 and Comparative Examples 1 to 3 were heated at 150 ° C for 2 hours, Examples 7 to 12 and Comparative Example 4 The 6-series was heated at 150 ° C for 4 hours to cure the addition-curable polydecane resin composition, thereby producing a tensile shear test piece. As the PPA board which is a base material, it is used for drying for 1 hour at 150 degreeC. The obtained test piece was subjected to tensile shear test and then subjected to tensile shear test using a tensile tester (manufactured by Shimadzu Corporation, "AGS-X") at a distance of 100 mm between the jigs and a test speed of 5 mm/min. Stretch the shear and then the strength.

(3) Tensile shear strength to PCT

Each of the addition-curable polydecane resin compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 6 was flowed into two PCT plates in a rectangular shape having a 20 × 25 mm follow-up portion (Mitsui Chemicals Co., Ltd.) Manufactured, "PROVEST C101LW", size 2 × 25 × 100 mm) was heated to 2 mm thick (Examples 1 to 6 and Comparative Examples 1 to 3 were heated at 150 ° C for 2 hours, Examples 7 to 12) And Comparative Examples 4 to 6 were heated at 150 ° C for 4 hours to cure the addition-curable polydecane resin composition, thereby producing a tensile shear test piece. The PCT board which is a base material was used for drying at 150 ° C for 1 hour. The obtained test piece was subjected to tensile shear test and then subjected to tensile shear test using a tensile tester (manufactured by Shimadzu Corporation, "AGS-X") at a distance of 100 mm between the jigs and a test speed of 5 mm/min. Stretch the shear and then the strength.

(4) Tensile shear strength of silver plated copper plate

Each of the addition-curable polyphthalocyanine compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 6 was poured into two silver-plated copper plates in a rectangular shape of 20 × 25 mm (the size was 2 × 25). ×100 mm) was heated to a thickness of 2 mm (Examples 1 to 6 and Comparative Examples 1 to 3 were heated at 150 °C for 2 hours, Examples 7 to 12 and Comparative Examples 4 to 6 were heated at 150 °C) The addition-hardening type polyoxymethylene resin composition was hardened to prepare a tensile shear test piece. As a copper plated silver plate which is a base material, it is used for drying for one hour at 150 degreeC. The obtained test piece was subjected to tensile shear test and then subjected to tensile shear test using a tensile tester (manufactured by Shimadzu Corporation, "AGS-X") at a distance of 100 mm between the jigs and a test speed of 5 mm/min. Stretch the shear and then the strength.

(5) Transparency

Each of the addition-curable polyphthalocyanine resin compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 6 was poured into PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) so as to have a thickness of 1 mm. The disk was heated and the addition-hardening type polyoxymethylene resin composition was hardened to prepare a total light transmittance test piece. For the total light transmittance test piece obtained, use a haze meter (Japan Electric Color) Manufactured by an industrial company, "NDH 2000") measures the total light transmittance.

For the measurement results, the case where the total light transmittance was 90% or more was set to "○", and the case where the total light transmittance was less than 90% was set to "x", and the transparency was evaluated.

[Industrial availability]

According to the present invention, it is possible to provide an addition-curable polydecane resin composition which is excellent in interfacial adhesion and transparency. Moreover, according to the present invention, it is possible to provide an addition-curable polyphthalocyanine cured product and an optical semiconductor element sealing body which are obtained by using the addition-curable polyoxyxylene resin composition.

Claims (7)

The addition-hardening type polyoxyxylene resin composition containing the addition-hardening type polyoxy-oxy-resin-resin mixture and the adhesiveness imparting agent, and the adhesiveness imparting agent contains the structure represented by following formula (1-1). The unit and the structural unit represented by the following formula (1-2) have a structural unit represented by the following formula (1-3) and/or a compound represented by the following formula (1-4); In the formulae (1-1) and (1-2), R ^1a each independently represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group having 2 to 9 carbon atoms. Or an alkoxy group having 1 to 4 carbon atoms; in the formulae (1-3) and (1-4), R ^1b independently represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. a base, an alkenyl group having 2 to 9 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms; in the formula (1-3), m is an integer of 1 to 50, and in the formula (1-4), n is 1~ An integer of 1500; in the formula (1-1) to (1-3), A is independently an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group having 2 to 9 carbon atoms. And an alkoxy group having 1 to 4 carbon atoms or a group represented by the following formula (2); wherein, in the formulae (1-1) to (1-3), at least one A is a group represented by the formula (2) ; In the formula (2), R ^2a represents an alkylene group having 1 to 8 carbon atoms which may be substituted with an oxygen atom in addition to a carbon atom bonded to a halogen atom, and R ^2b independently represents carbon. a 1-3 alkyl group, and R ³ independently represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, a sulfonyl group-containing group, a fluorenyl group, and a (meth) propylene group. a decyloxy group or a fluorenyl group; in the formula (2), x is an integer of 0 to 2, and Y is an oxygen atom or NH. The addition hardening type polyoxyxylene resin composition according to the first aspect of the invention, wherein, in the formula (2), R ³ is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. base. The addition-hardening type polyoxyxylene resin composition according to claim 1 or 2, wherein the content of the adhesion imparting agent is 0.01 to 15% by mass. The addition hardening type polyoxyxene resin composition of claim 1, wherein the addition hardening type polyoxyxene resin mixture comprises: having at least two carbon-carbons bonded to a germanium atom A polyorganosiloxane having a substituent of a double bond, a polyorganohydrohalosiloxane having at least two hydrogen atoms bonded to a halogen atom, and a hydrogenation reaction catalyst. For example, the additive hardening type polyoxymethylene resin composition of claim 4, wherein The substituent having a carbon-carbon double bond bonded to a ruthenium atom in the oxime is a vinyl group. An addition hardening type polyoxymethylene resin cured product obtained by hardening an addition hardening type polyoxymethylene resin composition of the first, second, third, fourth or fifth aspect of the patent application. An optical semiconductor element sealing body whose optical semiconductor element is sealed by an addition hardening type polyoxymethylene resin cured material of claim 6 of the patent application.