JP2015163661A - Condensation curable silicone resin composition, condensation curable silicone resin cured article, and optical semiconductor element sealing body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a condensation curable silicone resin composition excellent in adhesiveness, a condensation curable silicone resin cured article and an optical semiconductor element sealing body each obtained by using the condensation curable silicone resin composition.SOLUTION: The condensation curable silicone resin composition contains: a condensation curable silicone resin mixture; and an adhesiveness application agent. The adhesiveness application agent contains a compound which has two kinds of specific structural units and further has a specific structural unit between the two kinds of specific structural units.

Description

The present invention relates to a condensation curable silicone resin composition having excellent adhesiveness. Moreover, this invention relates to the condensation curable silicone resin hardened | cured material and optical semiconductor element sealing body which use this condensation curable silicone resin composition.

Condensation-curable silicone resins are widely used as electronic materials such as potting materials and as sealants for construction, and these react with moisture in the air and become rubbery by condensation-curing reaction, so that they contact during curing. The adhesiveness with the substrate is expressed.
However, the conventional condensation-curable silicone resin has a problem of low adhesion to the constituent members of the semiconductor material. For example, in recent years, instead of PPA (polyphthalamide resin), which has been a problem in long-term stability such as weather resistance and moisture resistance, as a reflector material in optical semiconductor device applications, PCT (polyester with excellent weather resistance and moisture resistance) (1,4-cyclohexyldimethylene terephthalate)) is employed, but since PCT does not have a hydrogen bonding donor in the molecule, the silicone resin is inferior in adhesion to PCT. In addition, the silicone resin has insufficient adhesion to noble metals such as silver, which are widely used as electrodes.

In order to solve such an adhesive problem, an adhesiveness imparting agent such as a silane coupling agent is usually blended. For example, Patent Documents 1 and 2 disclose a method of blending a silane coupling agent having an amino group or a glycidyl group, and Patent Document 3 uses a silane coupling agent having a urea bond as a base material. A method for improving the adhesiveness is disclosed. Patent Document 4 discloses a method of performing primer treatment on a base material in order to improve adhesiveness.

However, the method of blending the silane coupling agent as disclosed in Patent Documents 1 to 3 is not sufficient in improving the adhesion to the base material, and further, the adhesiveness decreases due to significant moisture absorption. It has the disadvantage of poor durability. Moreover, the method of performing primer treatment as disclosed in Patent Document 4 is not economical because the number of steps increases.

JP-A-5-194857 JP 2012-219113 A JP 2011-251936 A JP 2001-040286 A

An object of the present invention is to provide a condensation curable silicone resin composition having excellent adhesiveness. Another object of the present invention is to provide a condensed curable silicone resin cured product and an optical semiconductor element encapsulant formed using the condensation curable silicone resin composition.

The present invention is a condensation curable silicone resin composition containing a condensation curable silicone resin mixture and an adhesion promoter, wherein the adhesion promoter is a structural unit represented by the following formula (1-1): And a structural unit represented by the following formula (1-2) and / or a structural unit represented by the following formula (1-4) It is a condensation curable silicone resin composition containing a compound.

In formulas (1-1) and (1-2), R ^1a is each 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, Alternatively, an alkoxy group having 1 to 4 carbon atoms is represented. In formula (1-3) and formula (1-4), R ^1b is each 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, Alternatively, an alkoxy group having 1 to 4 carbon atoms is represented. In formula (1-3), m is an integer of 1-50, and in formula (1-4), n is an integer of 1-1500. In formulas (1-1) to (1-3), each A independently represents 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, or a carbon number. It is a group represented by 1-4 alkoxy groups or the following formula (2). However, in formulas (1-1) to (1-3), at least one A is a group represented by formula (2).

In the formula (2), R ^2a represents an alkylene group having 1 to 8 carbon atoms in which some of the carbon atoms excluding the carbon atom bonded to the silicon atom may be substituted with an oxygen atom, and R ^2b represents carbon Each represents an alkylene group having 1 to 3 carbon atoms, and each 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, an acyl group, a (meth) acryloyloxyalkyl group, Or a silyl group is represented. In formula (2), x is an integer of 0 to 2, and Y is an oxygen atom or NH.
The present invention is described in detail below.

The present inventor is able to obtain a condensation curable silicone resin composition having extremely excellent adhesiveness by blending a compound having a specific structure as an adhesion promoter in the condensation curable silicone resin mixture. The headline and the present invention have been completed.

The condensation curable silicone resin composition of the present invention includes, as an adhesiveness-imparting agent, between the structural unit represented by the formula (1-1) and the structural unit represented by the formula (1-2), Contains a compound having a structural unit represented by the formula (1-3) and / or a structural unit represented by the formula (1-4) (hereinafter also referred to as “adhesion imparting agent according to the present invention”). . In addition, the structural unit represented by Formula (1-1) and Formula (1-2) means a molecular end. The adhesiveness imparting agent according to the present invention may be a block copolymer or a random copolymer.
The adhesiveness imparting agent according to the present invention may be used alone or in combination of two or more.

In the formula (1-1) and the formula (1-2), R ^1a is independently an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl having 2 to 9 carbon atoms. Represents a group or an alkoxy group having 1 to 4 carbon atoms.
In the present specification, “independently” means “may be the same or different”.

Examples of the alkyl group having 1 to 18 carbon atoms represented by R ^1a include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, and an n-pentyl group. Group, neopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, 2,2,4-trimethylpentyl group, n-octyl group, isooctyl group, n-nonyl group, n-decyl group, n- A dodecyl group etc. are mentioned. Of these, a methyl group is preferable.

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

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

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

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) acryloyloxyalkyl group.
In the present specification, the “(meth) acryloyl” means acryloyl or methacryloyl.

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

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

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

Examples of the alkyl group having 1 to 18 carbon atoms represented by R ^1b include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, and an n-pentyl group. Group, neopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, 2,2,4-trimethylpentyl group, n-octyl group, isooctyl group, n-nonyl group, n-decyl group, n- A dodecyl group etc. are mentioned. Of these, a methyl group is preferable.

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

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

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

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

Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ^1b include a methoxy group, an ethoxy group, an n-propoxy group, and an 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, or an alkoxy group having 1 to 4 carbon atoms, and more preferably a methyl group or a phenyl group.

In said formula (1-3), m is an integer of 1-50, Preferably it is an integer of 2-45. In said formula (1-4), n is an integer of 1-1500, Preferably it is an integer of 2-1400.

In the formulas (1-1) to (1-3), each A independently represents 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, or carbon. It is group represented by the alkoxy group of number 1-4, or the said Formula (2).
The alkyl group having 1 to 18 carbon atoms, the cycloalkyl group, the aryl group, the aralkyl group, the alkenyl group having 2 to 9 carbon atoms, and the alkoxy group having 1 to 4 carbon atoms represented by A are each represented by R The thing similar to ^1a and said ^R1b is mentioned.
When the adhesiveness imparting agent of the present invention does not have the structural unit represented by the above formula (1-3), the above formula (1-1) and the above formula ( It is preferable that A in 1-2) is a group represented by the formula (2).

In the formula (2), R ^2a represents a portion of the alkylene group having 1 to 8 carbon atoms which may be carbon atoms substituted with an oxygen atom, except carbon atoms bonded to the silicon atom.
Examples of the alkylene group having 1 to 8 carbon atoms represented by R ^2a include methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, and n-octylene. And groups in which some carbon atoms of these alkylene groups are substituted with oxygen atoms. Of these, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, and a group in which some carbon atoms of these alkylene groups are substituted with an oxygen atom are preferable. .

In said formula (2), R ^<2b> represents a C1-C3 alkylene group.
Examples of the alkylene group having 1 to 3 carbon atoms represented by R ^2b include a methylene group, an ethylene group, an n-propylene group, and an isopropylene group.
In addition, when x in Formula (2) is 2, two R <^2b> may be the same and may differ.

In the formula (2), each R ³ is independently an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, a sulfonyl group, an acyl group, a (meth) acryloyloxyalkyl group, or a silyl group. Represents a group.

Examples of the alkyl group having 1 to 18 carbon atoms represented by R ³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, and an n-pentyl group. Group, neopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, 2,2,4-trimethylpentyl group, n-octyl group, isooctyl group, n-nonyl group, n-decyl group, n- A dodecyl group, n-octadecyl group, etc. are mentioned. In these alkyl groups, hydrogen atoms may be substituted. Specifically, one or more hydrogen atoms may be substituted with a halogeno group such as a chloro group or a bromo group. The carbon atom at the terminal of the alkyl group may be substituted with a triethoxysilyl group. Examples of the alkyl group having 1 to 18 carbon atoms represented by R ³ include ethyl group, n-propyl group, isopropyl group, n-butyl group, n-hexyl group, n-heptyl group, and n-dodecyl. Group and n-octadecyl group are preferable, and ethyl group, n-propyl group, n-butyl group, n-hexyl group and n-heptyl group are more preferable.

Examples of the cycloalkyl group represented by R ³ include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a methylcyclohexyl group. Of these, a cyclopentyl group and a cyclohexyl group are preferable, and a cyclohexyl group is more preferable.

Examples of the aryl group represented by R ³ include a phenyl group, a naphthyl group, and a biphenyl group. These aryl groups may have a substituent. Examples of the substituent that the aryl group may have include a halogeno group such as a fluoro group, a chloro group, and a bromo group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. Alkyl groups having 1 to 4 carbon atoms, halogenoalkyl groups in which at least one hydrogen atom of these alkyl groups is substituted with a halogeno group such as a fluoro group, a chloro group, or a bromo group, a methoxy group, an ethoxy group, or the like Alkoxy groups, halogenoalkoxy groups obtained by substituting one or more hydrogen atoms of these alkoxy groups with halogeno groups such as fluoro groups, chloro groups, and bromo groups, and nitro groups. Among them, the aryl group represented by R ³ is preferably a phenyl group, a naphthyl group, or a biphenyl group, and more preferably a phenyl group.

Examples of the aralkyl group represented by R ³ include a benzyl group, a methylbenzyl group, an isopropenyldimethylbenzyl group, a phenethyl group, and a naphthylethyl group. Of these, a benzyl group and a phenethyl group are preferable, and a phenethyl group is more preferable.

Examples of the sulfonyl group represented by R ³ include a benzenesulfonyl group and a paratoluenesulfonyl group.

Examples of the acyl group represented by R ³ include a trichloroacetyl group.

Examples of the (meth) acryloyloxyalkyl group represented by R ³ include a methacryloyloxyethyl group.

Examples of the silyl group represented by R ³ include a trimethylsilyl group.

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.

In said formula (2), x is an integer of 0-2, Y is an oxygen atom or NH.
The x is preferably an integer of 0 or 1.
The case where x is 0 means the case where R ^2a and Y are directly bonded.

As the adhesiveness imparting agent according to the present invention, R ³ in the formula (2) is an alkyl group having 1 to 18 carbon atoms from the viewpoint of compatibility with the condensation curable silicone resin mixture, availability of raw materials, and the like. What is a cycloalkyl group, an aryl group, or an aralkyl group is preferable.

The minimum with a preferable functional group equivalent of the said Formula (2) of the adhesiveness imparting agent concerning this invention is 100, and a preferable upper limit is 12000. When the functional group equivalent of the formula (2) of the adhesion-imparting agent according to the present invention is less than 100, the adhesive property corresponding to the functional group equivalent of the group represented by the formula (2) is not exhibited or condensed. The compatibility with the curable silicone resin mixture may be inferior. When the functional group equivalent of the formula (2) of the adhesiveness imparting agent according to the present invention exceeds 12,000, the resulting condensation curable silicone resin composition may have insufficient adhesion. The more preferable lower limit of the functional group equivalent of the formula (2) of the adhesiveness imparting agent according to the present invention is 200, the more preferable upper limit is 9000, the still more preferable lower limit is 300, and the more preferable upper limit is 8000.

As a manufacturing method of the adhesiveness imparting agent according to the present invention, for example, the following formula is used between the structural unit represented by the following formula (3-1) and the structural unit represented by the following formula (3-2). Silicone compound having a structural unit represented by (3-3) and / or a structural unit represented by the following formula (3-4) (hereinafter also referred to as “silicone compound having an amino group and / or a hydroxy group”) And an isocyanate compound represented by the following formula (4) (hereinafter, also simply referred to as “isocyanate compound”).

In formulas (3-1) and (3-2), R ^1a is each 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, Alternatively, an alkoxy group having 1 to 4 carbon atoms is represented. In formulas (3-3) and (3-4), R ^1b is each 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, Alternatively, an alkoxy group having 1 to 4 carbon atoms is represented. In formula (3-3), m is an integer of 1 to 50, and in formula (3-4), n is an integer of 1 to 1500. In formulas (3-1) to (3-3), each B independently represents 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, or carbon. It is group represented by the alkoxy group of number 1-4, or following formula (5). However, in formulas (3-1) to (3-3), at least one B is a group represented by formula (5).
Note that the ^{R 1a} of the formula (3-1) and (3-2) in ^{R 1a} and formula (1-1) and formula (1-2), respectively be the same group, the formula (3-3 ) and a ^{R 1b} of the formula (3-4) in the ^{R 1b} and formula (1-3) and formula (1-4), respectively at the same group.

In 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, an acyl group, a (meth) acryloyloxyalkyl group, or a silyl group.
Note that the ^{R 3} of ^{R 3} and the formula (2) in formula (4), respectively at the same group.

In Formula (5), R ^2a represents an alkylene group having 1 to 8 carbon atoms in which some of the carbon atoms excluding the carbon atom bonded to the silicon atom may be substituted with an oxygen atom, and R ^2b represents carbon Represents an alkylene group of 1 to 3; In formula (5), x is an integer of 0 to 2, and Y represents an oxygen atom or NH.
Note that the ^{R 2a} in the formula (5) in ^{R 2a} and Equation (2), respectively be the same group, the ^{R 2b} of ^{R 2b} and equation (2) in formula (5), respectively the same group It becomes.

The amino group equivalent and the hydroxy group equivalent of the silicone compound having an amino group and / or a hydroxy group correspond to the functional group equivalent of the adhesion-imparting agent according to the present invention. In addition, the functional group of the adhesiveness imparting agent according to the present invention is a ureido group (NHCONH) and a silicone having a hydroxy group when an adhesiveness imparting agent is produced using a silicone compound having an amino group as a raw material. When a compound is used as a raw material, it is a carbamate group (OCONH).
In addition, as a method of measuring the amino group equivalent of the silicone compound which has the said amino group, methods, such as nonaqueous neutralization titration using perchloric acid, are mentioned, for example. The hydroxy group equivalent of the silicone compound having a hydroxy group can be calculated from the hydroxyl value of the silicone compound having a hydroxy group. Examples of the method for obtaining the hydroxyl value of the silicone compound having a hydroxy group include the method described in JIS K 5601-2-1.

As a method for synthesizing the silicone compound having an amino group, dialkoxy having an alkylamino group disclosed in US Pat. No. 3,355,424, US Pat. No. 2,947,771, US Pat. No. 3,890,269, etc. A method using a polycondensation reaction that leads to an alkylsilane unit being inserted into the siloxane chain can be used. This reaction is usually carried out in the presence of an acidic or alkaline catalyst. This reaction can also be carried out as a polymerization reaction using dialkoxyalkylsilane and cyclic siloxane. In addition, as a method for synthesizing the silicone compound having a hydroxy group, polyorganosiloxane having a silicon atom-bonded hydrogen atom and organosilicon having an aliphatic unsaturated hydrocarbon group disclosed in Japanese Patent Application Laid-Open No. 04-88024 are disclosed. A method of adding a compound in the presence of a platinum-based catalyst can be used. In this method, first, polyorganosiloxane having a silicon atom-bonded hydrogen atom is added to an organosilicon compound having an aliphatic unsaturated hydrocarbon group by hydrosilylation using a platinum-based catalyst. Next, the trialkylsilyl group at the molecular chain end of the polyorganosiloxane produced by the addition reaction is removed by desilylation, and the molecular chain terminal is converted to a hydroxy group to obtain a hydroxy group-containing polyorganosiloxane.

Examples of commercially available silicone compounds having an amino group include KF-864, KF-865, KF-868, KF-857, KF-8001, KF-862 (monoamine type), and 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 end amine, side chain phenyl type), PAM-E, KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008 (both end amine type) (any Manufactured by Shin-Etsu Silicone), BY16-205, BY16-849, FZ-3785, BY16-872, BY16-213, FZ-370 (Both manufactured by Dow Corning Toray Co., Ltd.), and the like.

Examples of commercially available silicone compounds having a hydroxy group include X-22-4039, X-22-4015 (side chain carbinol type), X-22-160AS, KF-6001, and KF-. 6002, KF-6003 (both ends carbinol type), X-22-170BX, X-22-170DX (single end carbinol type) (all manufactured by Shin-Etsu Silicone), SF8428 (side chain carbinol type), SF8427 , BY16-201, BY16-004 (both ends carbinol type) (both manufactured by Toray Dow Corning) and the like.

Examples of the isocyanate compound include ethyl isocyanate, n-propyl isocyanate, n-butyl isocyanate, n-hexyl isocyanate, n-heptyl isocyanate, n-dodecyl isocyanate, n-octadecyl isocyanate, isopropyl isocyanate, tert-butyl isocyanate, 2 -Chloroethyl isocyanate, trichloromethyl isocyanate, 3- (triethoxysilyl) propyl isocyanate, cyclopentyl isocyanate, cyclohexyl isocyanate, trans-4-methylcyclohexyl isocyanate, phenyl isocyanate, o-tolyl isocyanate, m-tolyl isocyanate, p-tolyl isocyanate 4-ethylphenyl isocyanate, 4-n-buty Phenyl isocyanate, 2,6-dimethylphenyl isocyanate, 3,5-dimethylphenyl isocyanate, 2,6-diisopropylphenyl isocyanate, 3-chloro-4-methylphenyl isocyanate, 2-methoxyphenyl isocyanate, 3-methoxyphenyl isocyanate, 4 -Methoxyphenyl isocyanate, 2- (trifluoromethoxy) phenyl isocyanate, 4- (trifluoromethoxy) phenyl isocyanate, 4-ethoxyphenyl isocyanate, 2- (trifluoromethyl) phenyl isocyanate, 3- (trifluoromethyl) phenyl isocyanate 4- (trifluoromethyl) phenyl isocyanate, 3,5-bis (trifluoromethyl) phenyl isocyanate, 2-fluoro Phenyl isocyanate, 3-fluorophenyl isocyanate, 4-fluorophenyl isocyanate, 2,4-difluorophenyl isocyanate, 2,5-difluorophenyl isocyanate, 3,4-difluorophenyl isocyanate, 2-chlorophenyl isocyanate, 3-chlorophenyl isocyanate, 4 -Chlorophenyl isocyanate, 2-chloro-5- (trifluoromethyl) phenyl isocyanate, 4-chloro-3-nitrophenyl isocyanate, 2,3-dichlorophenyl isocyanate, 2,4-dichlorophenyl isocyanate, 2,5-dichlorophenyl isocyanate, 2 , 6-dichlorophenyl isocyanate, 3,4-dichlorophenyl isocyanate, 3,5-dichlorophenyl isocyanate 2,4,6-trichlorophenyl isocyanate, 2-bromophenyl isocyanate, 3-bromophenyl isocyanate, 4-bromophenyl isocyanate, 4-nitrophenyl isocyanate, 1-naphthyl isocyanate, 2-biphenyl isocyanate, benzyl isocyanate, phenethyl 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, benzenesulfonyl isocyanate, p-toluenesulfonyl isocyanate, trichloroacetylisocyanate Over DOO, 2-methacryloyloxyethyl isocyanate, trimethylsilyl isocyanate. Of these, ethyl isocyanate, n-propyl isocyanate, n-butyl isocyanate, n-hexyl isocyanate, n-heptyl isocyanate, cyclohexyl isocyanate, phenyl isocyanate, benzyl isocyanate, and phenethyl isocyanate are preferable from the viewpoints of economy and availability.

The amount of the isocyanate compound used in the reaction of the silicone compound having an amino group and / or hydroxy group with the isocyanate compound is such that when x in the formula (5) is 0 and Y is NH, amino The amount is preferably 0.8 to 5 mol, more preferably 0.9 to 3 mol, based on 1 mol of the amino group of the silicone compound having a group. Further, when x in the formula (5) is 0 and Y is an oxygen atom, it is preferably 0.8 to 5 mol with respect to 1 mol of the hydroxy group of the silicone compound having a hydroxy group, More preferably, it is 0.9-3 mol. When x in the formula (5) is 1 or 2 and Y is NH, it is preferably 0.8 to 5 mol with respect to 1 mol of the amino group of the silicone compound having an amino group. More preferably, it is 9-3 mol. Further, when x in Formula (5) is 1 or 2 and Y is an oxygen atom, the amount of O.O is 0.1 with respect to 1 mol in total of the amino group and hydroxy group of the silicone compound having an amino group and a hydroxy group. It is preferable that it is 8-5 mol, and it is more preferable that it is 0.9-3 mol.
An amino group here is an amino group which can react with the said isocyanate compound, and is a primary amino group and a secondary amino group in detail.

The reaction between the silicone compound having an amino group and / or hydroxy group and the isocyanate compound may be performed in the presence of a solvent. The solvent used is not particularly limited as long as the silicone compound having the amino group and / or hydroxy group is easily dissolved and does not inhibit the reaction between the silicone compound having the amino group and / or hydroxy group and the isocyanate compound. Examples thereof include hexane, heptane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, cyclohexane, dichloromethane, chloroform, diethyl ether, diisopropyl ether, acetone, ethyl methyl ketone, and methyl isobutyl ketone.

The reaction between the silicone compound having an amino group and / or hydroxy group and the isocyanate compound is preferably performed at a temperature in the range of -20 to 150 ° C depending on the solvent used, but in the range of 0 to 140 ° C. It is more preferable to carry out without using a solvent at the inner temperature.

The minimum with preferable content of the adhesiveness imparting agent concerning this invention in the condensation-curable silicone resin composition of this invention is 0.01 mass%, and a preferable upper limit is 15 mass%. When the content of the adhesiveness imparting agent according to the present invention is less than 0.01% by mass, the effect of improving the adhesiveness may not be sufficiently exhibited. If the content of the adhesion-imparting agent according to the present invention exceeds 15% by mass, the hardness of the cured product may be adversely affected. The more preferable lower limit of the content of the adhesiveness imparting agent according to the present invention is 0.05% by mass, the more preferable upper limit is 10% by mass, the still more preferable lower limit is 0.1% by mass, and the still more preferable upper limit is 5% by mass.

The condensation curable silicone resin composition of the present invention may contain other adhesiveness-imparting agents in addition to the adhesion-imparting agent according to the present invention as long as the object of the present invention is not impaired.

The condensation curable silicone resin composition of the present invention contains a condensation curable silicone resin mixture.
The condensation-curable silicone resin mixture means a silicone resin that is in a liquid state before being cured and becomes a rubber elastic body by being cured while generating a reaction by-product. Specifically, hydrolyzable groups such as alkoxysilyl groups and acetoxysilyl groups exist in the polysiloxane, and these groups are hydrolyzed to silanol groups by moisture in the air, and the silanol groups are condensed with each other. As a result, a stable siloxane bond is formed and crosslinked.
For example, an addition-curable silicone resin mixture hardly generates a by-product, but a platinum catalyst usually used as a crosslinking agent may cause curing inhibition when it comes into contact with a compound containing sulfur, nitrogen, or phosphorus atoms. It is necessary to strictly control the curing conditions. On the other hand, the condensation curable silicone resin mixture can be cured without strictly controlling the curing conditions.

As the condensation-curable silicone resin mixture, a generally known one-component type or two-component type can be used. Examples of the one-component type include an oxime type, an alcohol type, an acetone type, and an acetic acid type. Among these, an alcohol type and an acetone type that do not corrode metal are preferable.
Examples of the two-component type include an alcohol type and an acetone type.

In the condensation curing reaction of the condensation curable silicone resin mixture, tin, titanium, or an amine compound may be used as a catalyst, if necessary.

Among the condensation curable silicone resin mixtures, those commercially available include, for example, KE-3490, KE-3493, KE-3494, KE-3497, KE-3466, KE as one-component condensed acetone type. -3412, KE-3421, KE-3423, KE-3495 (all manufactured by Shin-Etsu Silicone), KE-4806-W, KE-4901-W, KE-4920T, KE- 4920, KE-4921-B, KE-4921-W (all manufactured by Shin-Etsu Silicone), KE-200, KE-210 (all manufactured by Shin-Etsu Silicone) and the like as the two-component condensed acetone type. .

In addition to the condensation curable silicone resin mixture and the adhesiveness-imparting agent according to the present invention, the condensation curable silicone resin composition of the present invention contains additives as necessary within a range that does not impair the purpose and effect of the present invention. You may contain.

Examples of the additive include an inorganic filler, an antioxidant, an inorganic phosphor, a lubricant, an ultraviolet absorber, a thermal light stabilizer, a dispersant, an antistatic agent, a polymerization inhibitor, an antifoaming agent, a curing accelerator, and a solvent. Anti-aging agent, radical inhibitor, adhesion improver, flame retardant, surfactant, storage stability improver, ozone anti-aging agent, thickener, plasticizer, radiation blocking agent, nucleating agent, coupling agent, Examples include conductivity imparting agents, phosphorus peroxide decomposing agents, pigments, metal deactivators, and property modifiers.

The inorganic filler is not particularly limited, and examples thereof include fine particles that do not deteriorate optical properties. Specific examples include alumina, aluminum hydroxide, fused silica, crystalline silica, ultrafine powder amorphous silica, hydrophobic ultrafine silica, talc, calcium carbonate, barium sulfate and the like.

Examples of the inorganic phosphor include yttrium, aluminum, garnet-based YAG phosphor, ZnS phosphor, Y ₂ O ₂ S phosphor, red light-emitting phosphor, and blue light emission, which are widely used in LEDs. Examples thereof include phosphors and green light emitting phosphors.

As a method for producing the condensation curable silicone resin composition of the present invention, for example, a condensation curable silicone resin mixture, an adhesiveness imparting agent according to the present invention, and an additive used as necessary are mixed. Can be manufactured by.

The condensation-curable silicone resin composition of the present invention can be a one-component type or a two-component type.
The condensation curable silicone resin composition of the present invention can be used after being applied to a substrate such as an optical semiconductor element and cured.

Examples of the method for applying the condensation curable silicone resin composition of the present invention to a substrate include a method using a dispenser, a potting method, screen printing, transfer molding, injection molding, and the like.

The condensation curable silicone resin composition of the present invention can be cured at room temperature or by heating. The condensation curable silicone resin cured product obtained by curing the condensation curable silicone resin composition of the present invention is also one aspect of the present invention.

The final heating temperature when the condensation curable silicone resin composition of the present invention is heated and cured is usually 100 ° C or higher, preferably 120 ° C or higher, and more preferably 120 to 200 ° C. Preferably, it is 120-180 degreeC.

Examples of the use of the condensation curable silicone resin composition of the present invention include a sealing material composition for electronic materials, a sealing agent composition for buildings, a sealing agent composition for automobiles, and an adhesive composition.
Examples of the electronic material include a lead frame, a wired tape carrier, a wiring board, glass, a support member such as a silicon wafer, an optical semiconductor element, an active element such as a semiconductor chip, a transistor, a diode, and a thyristor, and a capacitor. And passive elements such as resistors and coils. Especially, it can use suitably as a sealing material of an optical semiconductor element.
A sealed optical semiconductor element in which the optical semiconductor element is sealed with the cured product of the condensation curable silicone resin of the present invention is also one aspect of the present invention.

The condensation curable silicone resin composition of the present invention is used for, for example, display materials, optical recording medium materials, optical equipment materials, optical component materials, optical fiber materials, optical / electronic functional organic materials, semiconductor integrated circuit peripheral materials, etc. Can be used for

ADVANTAGE OF THE INVENTION According to this invention, the condensation curable silicone resin composition excellent in adhesiveness can be provided. Moreover, according to this invention, the condensation curable silicone resin hardened | cured material and optical semiconductor element sealing body which use this condensation curable silicone resin composition can be provided.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited only to these examples.

(Production Example 1)
(Reaction of silicone compound having amino group and phenethyl isocyanate (Preparation of adhesion promoter A))
In a 500 mL four-necked flask equipped with a magnetic rotor, a thermometer and a cooler, under a nitrogen atmosphere, a silicone compound having an amino group (“X-22-1660B-3”, amino group, manufactured by Shin-Etsu Silicone Co., Ltd.) Equivalent 2200 g / mol) 50.1 g (amino group 22.8 mmol) and phenethyl isocyanate (molecular weight 147.18) 3.61 g (24.5 mmol) were charged and stirred at 20 ° C. using a magnetic stirrer for 5 hours. . The residual amino group was confirmed to be less than 1% by neutralization titration. Thereafter, 207 g of toluene and 50 g of water were added for liquid separation, and the organic layer was concentrated to obtain 40.34 g of a transparent liquid (adhesion imparting agent A).
As a result of measuring (adhesion imparting agent A) by ¹ H-NMR, (adhesion imparting agent A) is a structural unit represented by the formula (1-1) (R ^1a is a methyl group, A is a formula ( 2), R ^2a is an n-propylene group, x is 0, Y is NH, and R ³ is a phenethyl group) and a structural unit (R ^1a ) represented by the formula (1-2) Is a group represented by the formula (2), R ^2a is an n-propylene group, x is 0, Y is NH, and R ³ is a phenethyl group, and in the formula (1-4) It was confirmed that the structure unit represented (R ^1b is a methyl group, a phenyl group).

(Production Example 2)
(Reaction of silicone compound having amino group with phenethyl isocyanate (Preparation of adhesion promoter B))
In a 100 mL four-necked flask equipped with a magnetic rotor, thermometer and cooler, under a nitrogen atmosphere, a silicone compound having an amino group (“X-22-9409” manufactured by Shin-Etsu Silicone Co., Ltd.), an amino group equivalent of 670 g / Mol) 7.24 g (amino group 10.8 mmol) and phenethyl isocyanate (molecular weight 147.18) 1.75 g (11.9 mmol) were charged, and the mixture was stirred at 20 ° C. using a magnetic stirrer for 5 hours. The residual amino group was confirmed to be less than 1% by neutralization titration. Thereafter, 50 g of toluene and 10 g of water were added for liquid separation, and the organic layer was concentrated to obtain 2.55 g of a transparent liquid (adhesion imparting agent B).
As a result of measuring (adhesion imparting agent B) by ¹ H-NMR, (adhesion imparting agent B) is a structural unit represented by the formula (1-1) (R ^1a is a methyl group, A is a formula ( 2), R ^2a is an n-propylene group, x is 0, Y is NH, and R ³ is a phenethyl group) and a structural unit (R ^1a ) represented by the formula (1-2) Is a group represented by the formula (2), R ^2a is an n-propylene group, x is 0, Y is NH, and R ³ is a phenethyl group, and in the formula (1-4) It was confirmed that the structure unit represented (R ^1b is a methyl group, a phenyl group).

(Production Example 3)
(Reaction of silicone compound having hydroxy group and phenethyl isocyanate (Preparation of adhesion promoter C))
In a 50 mL four-necked flask equipped with a magnetic rotor, thermometer and cooler, under a nitrogen atmosphere, a silicone compound having a hydroxy group (“X-22-4015” manufactured by Shin-Etsu Silicone Co., Ltd., hydroxy group equivalent 1867 g) / Mol) 4.99 g (hydroxy group 2.67 mmol) and phenethyl isocyanate (molecular weight 147.18) 0.52 g (3.53 mmol) were charged, and the temperature was raised to 120 ° C., then 10 using a magnetic stirrer. Stir for hours. The residual hydroxy group was confirmed to be less than 1% by titration. Thereafter, 25 g of heptane and 5 g of water were added for liquid separation, and the organic layer was concentrated to obtain 3.0 g of a transparent liquid (adhesion imparting agent C).
As a result of measuring (adhesion imparting agent C) by ¹ H-NMR, (adhesion imparting agent C) is a structural unit represented by formula (1-1) (R ^1a is a methyl group, and A is a methyl group). Group), a structural unit represented by the formula (1-2) (R ^1a is a methyl group, A is a methyl group), the formula (1-3) (R ^1b is a methyl group, and A is a formula (2) R ^2a is an n-4-oxahexylene group, x is 0, Y is an oxygen atom, and R ³ is a phenethyl group), and the structure represented by the formula (1-4) And having a unit (R ^1b is a methyl group).

(Production Example 4)
(Reaction of silicone compound having hydroxy group and phenethyl isocyanate (Preparation of adhesion promoter D))
In a 50 mL four-necked flask equipped with a magnetic rotor, thermometer and condenser, under a nitrogen atmosphere, a silicone compound having a hydroxy group (“KF-6003” manufactured by Shin-Etsu Silicone Co., Ltd., hydroxy group equivalent: 2545 g / mol) ) 5.00 g (hydroxyalkyl group 1.96 mmol) and phenethyl isocyanate (molecular weight 147.18) 0.44 g (2.99 mmol) were charged, the temperature was raised to 120 ° C., and 15 hours using a magnetic stirrer. Stir. The residual hydroxy group was confirmed to be less than 1% by titration. Thereafter, 26 g of heptane and 5 g of water were added for liquid separation, and the organic layer was concentrated to obtain 4.1 g of a transparent liquid (adhesion imparting agent D).
As a result of measuring (adhesion imparting agent D) by ¹ H-NMR, (adhesion imparting agent D) is a structural unit represented by formula (1-1) (R ^1a is a methyl group, and A is a formula). (2), R ^2a is an n-4-oxahexylene group, x is 0, Y is an oxygen atom, and R ³ is a phenethyl group), and is represented by the formula (1-2). A structural unit (R ^1a is a methyl group, A is a group represented by the formula (2), R ^2a is an n-4-oxahexylene group, x is 0, Y is an oxygen atom, and R ³ is a phenethyl group. And a structural unit represented by the formula (1-4) (R ^1b is a methyl group).

(Examples 1 to 12, Comparative Examples 1 and 2)
Condensation-curable silicone resin compositions were prepared by uniformly mixing the components in the amounts shown in Table 1 and then thoroughly degassing.
In addition, as the condensation curable silicone resin mixture in Table 1, a two-component condensed acetone type silicone resin mixture (“KE-200” manufactured by Shin-Etsu Silicone Co., Ltd.) was used.
Moreover, as the adhesion-imparting agent E in Table 1, glycidoxypropyltrimethoxylane (manufactured by Dow Corning Toray, “Z-6040”) was used.

<Evaluation>
The following evaluation was performed about each condensation-curable silicone resin composition obtained in Examples 1 to 12 and Comparative Examples 1 and 2. The results are shown in Table 1.

(1) Hardness (Type A)
Each condensation-curable silicone resin composition obtained in Examples 1 to 12 and Comparative Examples 1 and 2 was poured into a resin mold and allowed to stand at room temperature for 1 week to cure the condensation-curable silicone resin composition. 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, which was a test piece for hardness measurement. The hardness (type A) of the obtained test piece for hardness measurement was measured using a rubber / plastic hardness meter (manufactured by Furusato Seiki Seisakusho, “KR-24A”).

(2) Tensile Shear Adhesive Strength for PCT Each of the condensation curable silicone resin compositions obtained in Examples 1 to 12 and Comparative Examples 1 and 2 was subjected to two PCTs so that the adhesion part was a 20 × 25 mm rectangle. Poured to a thickness of 2 mm between the plates (Mitsui Chemicals Co., Ltd., “Provest C101LW”, size 2 × 25 × 100 mm), left at room temperature for 1 week to cure the condensation curable silicone resin composition, A tensile shear test piece was obtained. As the PCT plate as an adhesive substrate, one that was dried at 150 ° C. for 1 hour was used. About the obtained adhesion test piece, the tensile shear adhesive strength was measured on the conditions of the distance between grips of 100 mm and the test speed of 5 mm / min using the tensile tester (Shimadzu Corp. make, "AGS-X").

(3) Tensile shear adhesive strength to silver-plated copper plate 2 pieces of each of the condensation curable silicone resin compositions obtained in Examples 1 to 12 and Comparative Examples 1 and 2 so that the adhesion part is a rectangle of 20 × 25 mm The silver-plated copper plate (size 2 × 25 × 100 mm) was poured so as to have a thickness of 2 mm, and allowed to stand at room temperature for 1 week to cure the condensation-curable silicone resin composition, thereby obtaining a tensile shear test piece. The silver-plated copper plate that is the adhesive substrate was dried at 150 ° C. for 1 hour. About the obtained adhesion test piece, the tensile shear adhesive strength was measured on the conditions of the distance between grips of 100 mm and the test speed of 5 mm / min using the tensile tester (Shimadzu Corp. make, "AGS-X").

ADVANTAGE OF THE INVENTION According to this invention, the condensation curable silicone resin composition excellent in adhesiveness can be provided. Moreover, according to this invention, the condensation curable silicone resin hardened | cured material and optical semiconductor element sealing body which use this condensation curable silicone resin composition can be provided.

Claims (5)

A condensation curable silicone resin composition comprising a condensation curable silicone resin mixture and an adhesion promoter,
The adhesiveness imparting agent is represented by the following formula (1-3) between the structural unit represented by the following formula (1-1) and the structural unit represented by the following formula (1-2). A condensation curable silicone resin composition comprising a compound having a structural unit and / or a structural unit represented by the following formula (1-4).

In formulas (1-1) and (1-2), R ^1a is each 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, Alternatively, an alkoxy group having 1 to 4 carbon atoms is represented. In formula (1-3) and formula (1-4), R ^1b is each 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, Alternatively, an alkoxy group having 1 to 4 carbon atoms is represented. In formula (1-3), m is an integer of 1-50, and in formula (1-4), n is an integer of 1-1500. In formulas (1-1) to (1-3), each A independently represents 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, or a carbon number. It is a group represented by 1-4 alkoxy groups or the following formula (2). However, in formulas (1-1) to (1-3), at least one A is a group represented by formula (2).

In the formula (2), R ^2a represents an alkylene group having 1 to 8 carbon atoms in which some of the carbon atoms excluding the carbon atom bonded to the silicon atom may be substituted with an oxygen atom, and R ^2b represents carbon Each represents an alkylene group having 1 to 3 carbon atoms, and each 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, an acyl group, a (meth) acryloyloxyalkyl group, Or a silyl group is represented. In formula (2), x is an integer of 0 to 2, and Y is an oxygen atom or NH. The condensation curable silicone resin composition according to claim 1, wherein in formula (2), R ³ is an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group. The condensation-curable silicone resin composition according to claim 1 or 2, wherein the content of the adhesion-imparting agent is 0.01 to 15% by mass. A condensation curable silicone resin cured product obtained by curing the condensation curable silicone resin composition according to claim 1, 2 or 3. An optical semiconductor element encapsulant in which the optical semiconductor element is encapsulated with the condensation-cured silicone resin cured product according to claim 4.