JP2016050250A - Silicone resin composition, silicone resin cured product, and optical semiconductor element sealing body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silicone resin composition having excellent adhesiveness even under high temperature and high humidity conditions, a silicone resin cured product using the silicone resin composition, and an optical semiconductor element sealing body.SOLUTION: There is provided a silicone resin composition containing a silicone resin mixture and an adhesiveness imparting agent. The adhesiveness imparting agent has a structural unit to be a ureido bond and/or carbamate bond obtained by reacting a siloxane-containing compound having amino group with an organic diisocyanate and an organic isocyanate.SELECTED DRAWING: None

Description

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

Silicone resin is a resin excellent in properties such as flexibility, heat resistance, and electrical insulation, and particularly has excellent heat resistance since a siloxane bond is thermally stable. Moreover, the silicone resin is excellent in oxidation resistance as widely used as a high-temperature heat medium. On the other hand, it is known that the surface of the silicone resin exhibits water repellency and releasability. Furthermore, the silicone resin is useful as a rubber elastic body or a cured product by crosslinking, and the molded product is used in various fields such as electric / electronic, automobile, construction / civil engineering.
However, in the composite material constituting the molded product used for these applications, the low adhesiveness of the silicone resin to other materials such as metals and other plastics is a problem, and improvement is required. In particular, the adhesion between silicone resins and difficult-to-adhere plastic materials and difficult-to-adhere metals such as copper and aluminum in members such as electric / electronic materials and automobiles is still insufficient.
Therefore, in order to solve these problems, an improvement in adhesiveness has been achieved by adding an adhesion-imparting agent such as various silane coupling agents (for example, Patent Document 1).

JP 2012-007126 A

However, even if an adhesion-imparting agent as disclosed in Patent Document 1 is added, the effect is not sufficient. In addition, there are drawbacks such as a decrease in hardness due to the addition of an adhesion-imparting agent and a decrease in adhesion due to significant moisture absorption of the alkoxysilyl group in the silane coupling agent. In particular, in members such as electric / electronic materials and automobiles, improvement of adhesiveness under high temperature and high humidity is required.
An object of this invention is to provide the silicone resin composition which has the outstanding adhesiveness also under high temperature and high humidity. Moreover, an object of this invention is to provide the silicone resin hardened | cured material and optical semiconductor element sealing body which use this silicone resin composition.

The present invention is a silicone resin composition containing a silicone resin mixture and an adhesion-imparting agent, wherein the adhesion-imparting agent comprises a structural unit represented by the following formula (1-1) and a formula (1- It is a silicone resin composition containing the compound which has a structural unit represented by following formula (1-3) between the structural units represented by 2).

In formulas (1-1), (1-2), and (1-3), R ^1a is independently an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group. Represents an alkenyl group having 2 to 9 carbon atoms, a (meth) acryloyloxyalkyl group, a (meth) acryloyloxy group, or an alkoxy group having 1 to 4 carbon atoms, and R ² is independently bonded to a silicon atom. Represents an alkylene group having 1 to 8 carbon atoms in which some carbon atoms excluding the carbon atoms may be substituted with oxygen atoms, and X is independently an oxygen atom, NH, or NR ⁹ ; R < ⁹ > represents a C1-C18 alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group each independently. In formula (1-1) and formula (1-2), 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, (meta ) Represents an acryloyloxyalkyl group or a silyl group. In formula (1-3), R ⁴ each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms.
The present invention is described in detail below.

The present inventors can obtain a silicone resin composition having excellent adhesiveness even under high temperature and high humidity by blending a compound having a specific structure as an adhesion promoter in the silicone resin mixture. As a result, the present invention has been completed.

In the present invention, the silicone resin composition is used as an adhesion promoter between the structural unit represented by the formula (1-1) and the structural unit represented by the formula (1-2). The compound which has a structural unit represented by (1-3) (henceforth "the adhesiveness imparting agent concerning this invention") is contained. 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.

The adhesiveness imparting agent according to the present invention exhibits a sufficient effect only by blending a small amount. This is because the adhesiveness imparting agent according to the present invention gradually segregates at the adhesive interface with the substrate during the curing reaction of the silicone resin composition, and the concentration of the adhesiveness imparting agent according to the present invention at the adhesive interface increases. It is thought to be due to this. Furthermore, the adhesiveness imparting agent according to the present invention has a plurality of ureido groups (N—CO—NH) and / or carbamate groups (NH—CO—O) involved in adhesiveness in the molecular structure thereof, Since these groups are also present in the main chain, it is considered that this is because they can participate in adhesion throughout the molecule. Moreover, the silicone resin composition containing the adhesiveness imparting agent according to the present invention has excellent wet heat resistance.

In Formula (1-1), Formula (1-2), and Formula (1-3), R ^1a is independently an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, or an aryl group. , An aralkyl group, an alkenyl group having 2 to 9 carbon atoms, a (meth) acryloyloxyalkyl group, a (meth) acryloyloxy group, or an alkoxy group having 1 to 4 carbon atoms. Two ^{R 1a} in the formula (1-1) in the two ^{R 1a} in the formula (1-2), and four ^{R 1a} in the formula (1-3) in each identical It may be different or different. When the adhesiveness imparting agent according to the present invention has two or more structural units represented by the formula (1-3), each R ^1a in all the structural units represented by the formula (1-3) is the same. It may be different or different.
In the present specification, “independently” means “may be the same or different”.
The “(meth) acryloyl” means acryloyl or methacryloyl.

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-phenethyl group, a β-phenethyl 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, and a butenyl group.

Examples of the (meth) acryloyloxyalkyl group represented by R ^1a include a (meth) acryloyloxymethyl group, a (meth) acryloyloxyethyl group, a (meth) acryloyloxypropyl group, and a (meth) acryloyloxybutyl group. Etc.

^Examples of the (meth) acryloyloxy group represented by R ^1a include an acryloyloxy group or a methacryloyloxy group.

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 (1-1), the formula (1-2), and the formula (1-3), R ² each independently represents a part of carbon atoms excluding a carbon atom bonded to a silicon atom. The C1-C8 alkylene group which may be substituted by the oxygen atom is represented. In addition, two R ² in the formula (1-3) may be the same or different. When the adhesiveness imparting agent according to the present invention has two or more structural units represented by the formula (1-3), each R ² in all the structural units represented by the formula (1-3) is the same. It may be different or different.

Examples of the alkylene group having 1 to 8 carbon atoms represented by R ² 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 the formula (1-1), the formula (1-2), and the formula (1-3), each X is independently an oxygen atom, NH, or NR ⁹ , and R ⁹ is Each independently represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group. Note that two Xs in the formula (1-3) may be the same or different. When the adhesiveness imparting agent according to the present invention has two or more structural units represented by the formula (1-3), each X in the structural units represented by the formula (1-3) is the same. May be different or different.

Examples of the alkyl group having 1 to 18 carbon atoms represented by R ⁹ 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 and an ethyl group are preferable.

Examples of the cycloalkyl group represented by R ⁹ include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a methylcyclohexyl group.

Examples of the aryl group represented by R ⁹ include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, and a naphthyl group.

Examples of the aralkyl group represented by R ⁹ include a benzyl group, an α-phenethyl group, a β-phenethyl group, and the like.

When X is an oxygen atom, NH, or NR ⁹ , the adhesion-imparting agent according to the present invention is a ureido group (N—CO—NH) and / or a carbamate group (NH—CO—) involved in adhesion. It is considered that it has a plurality of O), and since these groups are also present in the main chain, it can participate in adhesion throughout the molecule.
Among these, X is preferably an oxygen atom or NH, and all X are preferably the same from the viewpoints of economy and availability.

In formula (1-1) and formula (1-2), 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, (meta ) Represents an acryloyloxyalkyl group or a silyl 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. Moreover, the carbon atom at the terminal of the alkyl group may be substituted with an alkoxysilyl group such as 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, for example, (meth) acryloyloxymethyl group, (meth) acryloyloxyethyl group, (meth) acryloyloxypropyl group, and (meth) acryloyloxy. A butyl group etc. are mentioned.

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

Among these, R ³ is preferably independently an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, more preferably an n-butyl group, a cyclohexyl group or a phenethyl group.

In said formula (1-3), R < ⁴ > represents a C1-C20 bivalent hydrocarbon group each independently. When the adhesiveness imparting agent according to the present invention has two or more structural units represented by the formula (1-3), each R ⁴ in all the structural units represented by the formula (1-3) is the same. It may be different or different.
Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴ include an alkylene group, a cycloalkylene group, an arylene group, an alkylene group having a cycloalkylene, and an alkylene group having an arylene. Can be mentioned. The carbon atom in the hydrocarbon group may be substituted with an oxygen atom or a nitrogen atom, or may form a carbonyl group.

Examples of the alkylene group represented by R ⁴ include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-dodecamethylene group, and a trimethylhexamethylene group. And (methoxycarbonyl) pentylene group. Of these, an n-hexylene group is more preferable.

Examples of the cycloalkylene group represented by R ⁴ include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a methylenebiscyclohexylene group, a methylenebismethylcyclohexylene group, and the like. Of these, a methylenebiscyclohexylene group is preferred.

Examples of the arylene group represented by R ⁴ include a phenylene group, a tolylene group, a naphthylene group, a tetrahydronaphthylene group, a biphenylene group, a dimethylbiphenylene group, a dimethoxybiphenylene group, a dichlorobiphenylene group, and a methylenebisphenylene group. It is done.

Examples of the alkylene group having cycloalkylene represented by R ⁴ include a cyclohexylenedimethylene group and an isoholonylene group. Of these, an isoholonylene group is preferable.

Examples of the alkylene group having an arylene represented by R ⁴ include a xylylene group and a tetramethylxylylene group. Of these, a xylylene group is preferable.

The adhesiveness imparting agent according to the present invention preferably has 10 or less structural units represented by the formula (1-3).

The adhesiveness imparting agent according to the present invention is further represented by the following formula (2) between the structural unit represented by the formula (1-1) and the structural unit represented by the formula (1-2). It is preferable to have a structural unit.

In formula (2), R ^1b each 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, a (meth) acryloyloxyalkyl group, A (meth) acryloyloxy group or a C1-C4 alkoxy group is represented, and n is an integer of 1-1500. The two R ^1b in the formula (2) may be the same or different.

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-phenethyl group, a β-phenethyl group, and the like.

As a C2-C9 alkenyl group represented by said R ^<1b >, a vinyl group, an allyl group, a butenyl group etc. are mentioned, for example.

Examples of the (meth) acryloyloxyalkyl group represented by R ^1b include a (meth) acryloyloxymethyl group, a (meth) acryloyloxyethyl group, a (meth) acryloyloxypropyl group, and a (meth) acryloyloxybutyl group. Etc.

^Examples of the (meth) acryloyloxy group represented by R ^1b include an acryloyloxy group and a methacryloyloxy 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 or an aryl group, and more preferably a methyl group or a phenyl group.

In said Formula (2), n is an integer of 1-1500, Preferably it is an integer of 1-1400. In addition, when n is 2 or more, each R ^1b in all the structural units represented by the formula (2) may be the same or different.

As the adhesiveness imparting agent according to the present invention, the structural unit represented by the formula (1-1) and the structural unit represented by the formula (1-2) are used from the viewpoint of economy such as availability of raw materials. In between, it is preferable to contain the compound which has a structural unit represented by following formula (3).

In formula (3), each R ^1a 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, a (meth) acryloyloxyalkyl group, A (meth) acryloyloxy group or an alkoxy group having 1 to 4 carbon atoms, each R ^1b independently represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or 2 carbon atoms. Represents an alkenyl group of ˜9, a (meth) acryloyloxyalkyl group, a (meth) acryloyloxy group, or an alkoxy group having 1 to 4 carbon atoms, and each R ² independently represents a carbon atom bonded to a silicon atom. Represents a C1-C8 alkylene group in which some of the carbon atoms may be substituted with oxygen atoms, and each R ⁴ independently represents a C1-C20 divalent group. Represents a hydrocarbon group, each X is independently an oxygen atom, NH, or NR ⁹ , and each R ⁹ is independently an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group. Yes, l is an integer from 1 to 400.
Note that the ^{R 1a} in formula (3), the ^{R 1a} in the formula (1-3), respectively be the same group, and ^{R 1b} in the formula (3), and ^{R 1b} in the formula (2) is each be the same group, the formula (3) and ^{R 2} in, and the ^{R 2} in the formula (1-3), respectively be the same group, with ^{R 4} in the formula (3), formula (1-3) R ⁴ therein is the same group, and X in Formula (3) and X in Formula (1-3) are the same atom or group.

The functional group of the adhesiveness imparting agent according to the present invention is a ureido group (N—CO—NH) and / or a carbamate group (NH—CO—O). More specifically, the functional group equivalent of the adhesion-imparting agent is defined by (molecular weight of adhesion-imparting agent) / (total number of moles of ureido group and carbamate group).
The minimum with a preferable functional group equivalent of the adhesiveness imparting agent concerning this invention is 100, and a preferable upper limit is 18000. When the functional group equivalent of the adhesiveness-imparting agent according to the present invention is less than 100, the adhesive property corresponding to the functional group equivalent may not be exhibited, or the compatibility with the silicone resin mixture may be inferior. When the functional group equivalent of the adhesiveness imparting agent according to the present invention exceeds 18000, the adhesiveness of the resulting silicone resin composition may be insufficient. The more preferable lower limit of the functional group equivalent 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 further preferable upper limit is 8000.

As a manufacturing method of the adhesiveness imparting agent according to the present invention, for example, a silicone compound having a structural unit represented by the following formula (4-1) and a structural unit represented by the following formula (4-2) (hereinafter referred to as the following) , “Also called a silicone compound having an amino group and / or a hydroxy group”) and a bifunctional isocyanate compound represented by the following formula (5) (hereinafter also simply referred to as “bifunctional isocyanate compound”). Thereafter, a method of reacting a monofunctional isocyanate represented by the following formula (6) (hereinafter, also simply referred to as “monofunctional isocyanate compound”) and the like can be mentioned.

In formulas (4-1) and (4-2), 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 group having 2 to 9 carbon atoms. , A (meth) acryloyloxyalkyl group, a (meth) acryloyloxy group, or an alkoxy group having 1 to 4 carbon atoms, each R ² independently represents a part of carbon atoms excluding a carbon atom bonded to a silicon atom. Represents an alkylene group having 1 to 8 carbon atoms in which an atom may be substituted with an oxygen atom, X is independently an oxygen atom, NH, or NR ⁹ , and R ⁹ is independently a carbon An alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group represented by formulas 1 to 18 is represented.
In addition, R ^1a in Formula (4-1) and Formula (4-2), Formula (1-1), Formula (1-2), Formula (1-3), and Formula (3) R ^1a is the same group, R ² in Formula (4-1) and Formula (4-2), Formula (1-1), Formula (1-2), Formula (1-3), R ² in formula (3) is the same group, and X in formula (4-1) and formula (4-2), formula (1-1), formula (1-2), X in Formula (1-3) and Formula (3) is the same atom or group.

In formula (5), R < ⁴ > represents a C1-C20 bivalent hydrocarbon group each independently.
Note that ^{R 4} in the formula (5), and the ^{R 4} in the formula (1-3) and formula (3), respectively at the same group.

In formula (6), each R ³ independently represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aralkyl group, a sulfonyl group, an acyl group, a (meth) acryloyloxyalkyl group, or a silyl group. .
Note that ^{R 3} in the formula (6), and the ^{R 3} in the formula (1-1) and formula (1-2), respectively at the same group.

The silicone compound having an amino group and / or a hydroxy group has the following formula (7) between the structural unit represented by the formula (4-1) and the structural unit represented by the formula (4-2). It is preferable to have a structural unit represented by

In formula (7), each R ^1b 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, a (meth) acryloyloxyalkyl group, It represents a (meth) acryloyloxy group or an alkoxy group having 1 to 4 carbon atoms, and l is an integer of 1 to 400.
Note that the ^{R 1b} in ^{R 1b} and wherein in formula (7) (2) and (3), respectively the same groups. Further, l in the formula (7) and n in the formula (2) have a relationship of l <n.

When manufactured by the above manufacturing method, the adhesion-imparting agent according to the present invention is obtained in a mixture of silicone compounds represented by the following average structural formula (8). Such a mixture of silicone compounds containing the adhesion promoter according to the present invention can be suitably used as the adhesion promoter.
In the present specification, the “average structural formula” means that the adhesiveness imparting agent according to the present invention is included in a mixture of silicone compounds including those having various structures. For the silicone compounds having various structures, the structural formulas expressed when taking the average of the structures are meant.

In formula (8), each R ^1a 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, a (meth) acryloyloxyalkyl group, A (meth) acryloyloxy group or an alkoxy group having 1 to 4 carbon atoms, each R ^1b independently represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or 2 carbon atoms. Represents an alkenyl group of ˜9, a (meth) acryloyloxyalkyl group, a (meth) acryloyloxy group, or an alkoxy group having 1 to 4 carbon atoms, and each R ² independently represents a carbon atom bonded to a silicon atom. Represents an alkylene group having 1 to 8 carbon atoms in which some of the carbon atoms except that may be substituted with oxygen atoms, and each R ³ independently represents an alkyl group having 1 to 18 carbon atoms. R ⁴ represents an alkyl group, an aryl group, a cycloalkyl group, an aralkyl group, a sulfonyl group, an acyl group, a (meth) acryloyloxyalkyl group, or a silyl group, and each R ⁴ is independently a divalent group having 1 to 20 carbon atoms. Represents a hydrocarbon group, X is each independently an oxygen atom, NH or NR ⁹ , p is an integer of 0 to 400, and o is a positive number of 1 or less. R < ⁹ > represents a C1-C18 alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group each independently.
Incidentally, ^{R 1a} and formula (4-1) in the formula (8) and A ^{R 1a} in the formula (4-2), respectively be the same group, ^{R 1b} of the formula (7) in the formula (8) the of ^{R 1b,} respectively be the same group, the ^{R 2} of the ^{R 2} and formula (4-1) and formula (4-2) in the formula (8), respectively be the same group, the formula (8) in the of ^{R 3} and ^{R 3} in the formula (6), respectively be the same group, the ^{R 4} and ^{R 4} in formula (5) in equation (8), respectively be the same group, in the formula (8) X and X in Formula (4-1) and Formula (4-2) are the same group.

When produced by the production method, 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 adhesiveness-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 (N-CO-NH) when an adhesiveness imparting agent is produced using a silicone compound having an amino group as a raw material. When a silicone compound having a group is used as a raw material, it is a carbamate group (NH—CO—O).
Examples of the method for measuring the amino group equivalent of the silicone compound having an amino group include methods such as non-aqueous neutralization titration using perchloric acid. 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.

Among the silicone compounds having an amino group and / or a hydroxy group, a method for synthesizing a silicone compound having an amino group is described in US Pat. No. 3,355,424, US Pat. No. 2,947,771, US Pat. No. 3,890,269. A method using a polycondensation reaction that leads to the insertion of a dialkoxyalkylsilane unit having an alkylamino group into a siloxane chain, which is disclosed in the above, 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, a polyorganosiloxane having a silicon atom-bonded hydrogen atom and an organic compound having an aliphatic unsaturated hydrocarbon group disclosed in Japanese Patent Application Laid-Open No. 04-88024 are disclosed. A method of adding a silicon 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 X-22-1660B-3, X-22-9409 (both terminal amines, side chain phenyl type), PAM-E, and KF-8010. , X-22-161A, X-22-161B, KF-8012, KF-8008 (both end amine type) (all manufactured by Shin-Etsu Chemical Co., Ltd.), BY16-871, BY16-853U (both end amine type) ( All of them are manufactured by Toray Dow Corning).

Examples of commercially available silicone compounds having a hydroxy group include X-22-160AS, KF-6001, KF-6002, KF-6003 (both ends carbinol type) (all Shin-Etsu Chemical Co., Ltd.). Product), SF8427, BY16-201, BY16-004 (both ends carbinol type) (all manufactured by Toray Dow Corning), and the like.

Examples of the bifunctional isocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and 2,4′-diphenylmethane. Diisocyanate, 2,2'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4 '-Biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate and other aromatic diisocyanates, tetra Tylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, 1,3-cyclohexylene diisocyanate, 4-cyclohexylene diisocyanate, hydrogenated xylylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, 4,4 ' -Aliphatic diisocyanates such as -dicyclohexylmethane diisocyanate and 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate.
Of these, 1,6-hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, and 4,4′-dicyclohexylmethane diisocyanate are preferable from the viewpoints of economy and availability.

Examples of the monofunctional 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, and 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 Butylphenyl 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 Orophenyl 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 Anate, 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, trichloroacetyl ester Cyanate, 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 bifunctional isocyanate compound used in the reaction between the silicone compound having an amino group and / or hydroxy group and the bifunctional isocyanate compound is the functional group (amino group) of the silicone compound having an amino group and / or hydroxy group. Group and hydroxy group) is preferably 0.001 to 0.25 mol with respect to 1 mol in total. If the amount is less than 0.001 mol, the resulting adhesion-imparting agent may not be able to sufficiently exhibit the effect of improving the adhesion, and if it exceeds 0.25 mol, gelation tends to occur during the reaction. May be extremely difficult.
As the usage-amount of the said monofunctional isocyanate compound, it is 0.5-5 mol with respect to 1 mol in total of the functional group (amino group, hydroxy group) in the silicone compound which has the said amino group and / or a hydroxy group. It is preferable that it is 0.6-3 mol.
The total use amount of the bifunctional isocyanate compound and the monofunctional isocyanate compound is about 0.1 mol with respect to a total of 1 mol of functional groups (amino group, hydroxy group) in the silicone compound having an amino group and / or hydroxy group. It is preferable that it is 8-5 mol, and it is more preferable that it is 0.9-3 mol.
In addition, an amino group here is an amino group which can react with the said bifunctional isocyanate compound and the said monofunctional isocyanate compound, and is a primary amino group and a secondary amino group in detail.

The reaction of the silicone compound having an amino group and / or hydroxy group with the bifunctional isocyanate compound and the monofunctional isocyanate compound may be performed in the presence of a solvent. As the solvent to be used, the silicone compound having the amino group and / or hydroxy group is easily dissolved, and the reaction of the silicone compound having the amino group and / or hydroxy group with the bifunctional isocyanate compound and the monofunctional isocyanate compound is inhibited. It is not particularly limited as long as it is not, for example, hexane, heptane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, cyclohexane, dichloromethane, chloroform, diethyl ether, diisopropyl ether, acetone, ethyl methyl ketone, methyl isobutyl ketone, etc. Can be mentioned.

The reaction of the silicone compound having an amino group and / or hydroxy group with the bifunctional isocyanate compound and the monofunctional isocyanate compound is preferably performed at a temperature in the range of -20 to 150 ° C. depending on the solvent used. However, it is more preferable to carry out at the temperature within the range of 0-100 degreeC.

The minimum with preferable content of the adhesiveness imparting agent concerning this invention in the silicone resin composition of this invention is 0.01 mass%, and a preferable upper limit is 20 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 20% by mass, the hardness of the cured product may be adversely affected. The more preferable lower limit of the content of the adhesion-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.

In the range which does not inhibit the objective of this invention, the silicone resin composition of this invention may contain the other adhesive imparting agent in addition to the adhesive imparting agent concerning this invention.

The silicone resin composition of the present invention contains a silicone resin mixture. As the silicone resin mixture according to the present invention, an addition-curable silicone resin mixture or a condensation-curable silicone resin mixture is mainly used.

[Addition-curing silicone resin mixture]
The addition-curable silicone resin mixture used in the present invention is a mixture containing an addition-curable silicone resin that is cured by a hydrosilylation reaction between a silyl group having a carbon-carbon double bond and a hydrosilyl group.
The addition-curable silicone resin mixture is a polyorganosiloxane having at least two substituents having a carbon-carbon double bond bonded to a silicon atom (hereinafter also referred to as “carbon-carbon double bond-containing polyorganosiloxane”). And a polyorganohydrogensiloxane having at least two hydrogen atoms bonded to silicon atoms (hereinafter also simply referred to as “polyorganohydrogensiloxane”) and a hydrosilylation reaction catalyst.

Examples of the molecular structure of the carbon-carbon double bond-containing polyorganosiloxane include linear and cyclic structures, and the structure may have a branch. Among these, a linear structure in which the main chain is composed of repeating diorganosiloxane units and both ends are blocked with triorganosiloxy groups is preferable.

In the carbon-carbon double bond-containing polyorganosiloxane, the substituent having a carbon-carbon double bond bonded to a silicon atom is preferably one having 2 to 8 carbon atoms. Specifically, for example, a vinyl group An allyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, a (meth) acryloyloxyalkyl group, and the like. Of these, a vinyl group and a (meth) acryloyloxyalkyl group are preferable, and a vinyl group is more preferable.

When the molecular structure of the carbon-carbon double bond-containing polyorganosiloxane is linear, the substituent having a carbon-carbon double bond is bonded to a silicon atom only at either the molecular chain end or the middle. It may be bonded to the silicon atom both at the molecular chain end and in the middle.

Examples of the organic group bonded to the silicon atom other than the substituent having a carbon-carbon double bond in the carbon-carbon double bond-containing polyorganosiloxane include, for example, methyl group, ethyl group, n-propyl group, n- Alkyl groups having 1 to 12 carbon atoms such as butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopentyl group, cyclohexyl group, A cycloalkyl group having 3 to 8 carbon atoms such as cycloheptyl group, an aryl group having 6 to 14 carbon atoms such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group, phenethyl group, phenylpropyl group, etc. Non-aralkyl groups, halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group, bromoethyl group, 3,3,3-trifluoropropyl group, etc.換又 can be mentioned monovalent hydrocarbon groups of halogen-substituted. Of these, an alkyl group and an aryl group are preferable, and a methyl group and a phenyl group are more preferable.

The preferable lower limit of the viscosity of the carbon-carbon double bond-containing polyorganosiloxane is 100 mPa · s, and the preferable upper limit is 100,000 mPa · s. When the viscosity of the carbon-carbon double bond-containing polyorganosiloxane is within this range, the workability of the resulting addition-curable silicone resin composition is good and the addition-curable silicone resin composition The resulting cured product has good physical properties. The more preferable lower limit of the viscosity of the carbon-carbon double bond-containing polyorganosiloxane is 500 mPa · s, and the more preferable upper limit is 10,000 mPa · s.
In the present specification, the “viscosity” means a value measured at 25 ° C. using a rotational viscometer (BM type).

Specific examples of the carbon-carbon double bond-containing polyorganosiloxane include, for example, molecular chain both ends trimethylsiloxy group-capped dimethylsiloxane / methylvinylsiloxane copolymer, molecular chain both ends trimethylsiloxy group-capped methylvinylpolysiloxane. Molecular chain both ends trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer, molecular chain both ends dimethylvinylsiloxy group-blocked dimethylpolysiloxane, molecular chain both ends dimethylvinylsiloxy group-blocked methylvinylpolysiloxane, Dimethylsiloxane / methylvinylsiloxane copolymer with dimethylvinylsiloxy group blocked at both ends of molecular chain, dimethylsiloxane / methylvinylsiloxane / methylphenylsilane with dimethylvinylsiloxy group blocked at both ends of molecular chain Hexane copolymer, both molecular chain terminals by trimethylsiloxy blocked with dimethylvinylsiloxy _{^{groups, (R 5) 3 SiO 0.5}} (R 5 is a monovalent hydrocarbon unsubstituted or substituted non-alkenyl group or contains an alkenyl group And a siloxy unit represented by (R ⁵ ) ₂ R ⁶ SiO _0.5 (R ⁶ is an alkenyl group or a group containing an alkenyl group; the same shall apply hereinafter). A polyorganosiloxane copolymer comprising a unit, a siloxy unit represented by (R ⁵ ) ₂ SiO, and a siloxy unit represented by SiO ₂ , and a siloxy unit represented by (R ⁵ ) ₃ SiO _0.5 ^If, _(R ⁵⁾ and siloxy units represented by 2 R _{6 SiO 0.5,} polyorganosiloxane copolymer comprising a siloxy unit represented by ^{_{SiO 2, (R 5) 2}} R 6 and siloxy units represented by iO _{^0.5, (R 5)} and siloxy units represented by 2 SiO, polyorganosiloxane copolymer comprising a siloxy unit represented by SiO ^_2, with R ⁵ R 6 SiO A polyorganosiloxane copolymer composed of a siloxy unit represented by a siloxy unit represented by R ⁵ SiO _1.5 or a siloxy unit represented by R ⁶ SiO _1.5 , (R ⁵ ) ₃ SiO A siloxy unit represented by _0.5 , a siloxy unit represented by (R ⁵ ) ₂ SiO, a siloxy unit represented by R ⁵ R ⁶ SiO, and a siloxy unit represented by R ⁵ SiO _1.5 And (R ⁵ ) ₄ Si ₂ R ⁷ O (R ⁷ is a divalent hydrocarbon group. The same below), a polyorganosiloxane copolymer comprising a siloxy unit, a siloxy unit represented by (R ⁵ ) ₂ SiO, a siloxy unit represented by R ⁵ R ⁶ SiO, and (R ⁵ ) And a polyorganosiloxane copolymer composed of a siloxy unit represented by ₄ Si ₂ R ⁷ O. These may be used individually by 1 type and may be used in combination of 2 or more type.

Examples of the hydrocarbon group represented by R ⁵ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group. C1-C12 alkyl groups such as n-nonyl group and n-decyl group, C3-C8 cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, phenyl group, tolyl group, Aryl groups such as xylyl group and naphthyl group, aralkyl groups such as benzyl group, phenethyl group and phenylpropyl group, chloromethyl group, 3-chloropropyl group, bromoethyl group, 3,3,3-trifluoropropyl group, etc. And halogenated alkyl groups.

As the alkenyl group represented by R ⁶ or a group containing an alkenyl group, those having 2 to 8 carbon atoms are preferable, for example, vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, (Meth) acryloyloxyalkyl group and the like can be mentioned. Of these, a vinyl group and a (meth) acryloyloxyalkyl group are preferable, and a vinyl group is more preferable.

Examples of the divalent hydrocarbon group represented by R ⁷ include a phenylene group, an ethylene group, a hexylene group, and an octylene group. Of these, a phenylene group is preferable.

Examples of the commercially available carbon-carbon double bond-containing polyorganosiloxane include DMS-V21, DMS-V22, DMS-V25, DMS-V31, DMS-V33, DMS-V35, and DMS-V41. , DMS-V42, DMS-V46, DMS-V25R, DMS-V35R (molecular chain both ends dimethylvinylsiloxy-blocked dimethylpolysiloxane), PDV-0325, PDV-0331, PDV-0341, PDV-0346, PDV-0525 , PDV-0535, PDV-0541, PDV-1625, PDV-1631, PDV-1635, PDV-1641, PDV-2331 (a dimethylvinylsiloxy group-blocked dimethylsiloxane / diphenylsiloxane copolymer at both molecular chain ends), VDT- 123, VDT 127, VDT-131, VDT-431, VDT-731 (trimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer), PMV-9925 (molecular chain both ends dimethylvinylsiloxy group-blocked phenylmethylpolysiloxane) ), PVV-3522 (vinyl chain chain-blocked vinylphenylsiloxane / phenylmethylsiloxane copolymer) (both manufactured by Gelest, Inc.) and the like.

The polyorganohydrogensiloxane reacts with the carbon-carbon double bond-containing polyorganosiloxane and acts as a crosslinking component.

As the polyorganohydrogensiloxane, for example, various polyorganohydrogensiloxanes having a molecular structure such as linear, cyclic, branched, and three-dimensional network structure (resinous) can be used.

The polyorganohydrogensiloxane has 2 or more, preferably 3 or more, hydrogen atoms bonded to silicon atoms in one molecule, that is, a hydrosilyl group (Si-H group). When the molecular structure of the polyorganohydrogensiloxane is linear, these Si-H groups may be located only in one of the molecular chain terminal and the middle part, or in both of them. It may be.

The number (degree of polymerization) of silicon atoms in one molecule of the polyorganohydrogensiloxane is preferably 2 to 1000, and more preferably 3 to 100.

Examples of the polyorganohydrogensiloxane include R ⁸ _a H _b SiO _{(4-ab / 2)} (R ⁸ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 14 carbon atoms. R ⁸ preferably has 1 to 10 carbon atoms, a and b are 0.7 ≦ a ≦ 2.1, 0.001 ≦ b ≦ 1.0, and 0.8 ≦ a + b ≦ 3.0 is preferable, and a positive number satisfying 1.0 ≦ a + b ≦ 2.5 is more preferable). .

Examples of the hydrocarbon group represented by R ⁸ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, a neopentyl group, and an n-hexyl group. C1-C12 alkyl groups such as n-octyl group, n-nonyl group and n-decyl group; C3-C8 cycloalkyl groups such as cyclopentyl group, cyclohexyl group and cycloheptyl group; and phenyl Group, tolyl group, xylyl group, naphthyl group and other aryl groups having 6 to 14 carbon atoms, aralkyl groups such as benzyl group, phenethyl group and phenylpropyl group, alkenyl groups such as vinyl group and allyl group, etc. Groups in which some or all of the hydrogen atoms in the hydrocarbon group are substituted with halogen atoms, such as chloromethyl group, 3-chloropropyl group, bromoethyl group, 3, 3 , 3-trifluoropropyl group and the like. R ⁸ is preferably an alkyl group or an aryl group, and more preferably a methyl group or a phenyl group.

Specific examples of the polyorganohydrogensiloxane represented by R ⁸ _a H _b SiO _{(4-ab / 2)} in the polyorganohydrogensiloxane include, for example, methyl trimethylsiloxy group-blocked methyl at both molecular chains. Hydrogen polysiloxane, trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer with both ends of molecular chain, trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane / methylphenylsiloxane copolymer, both molecular chains Terminal dimethylhydrogensiloxy group-blocked dimethylpolysiloxane, molecular chain both ends dimethylhydrogensiloxy group-blocked dimethylpolysiloxane / methylhydrogensiloxane copolymer, molecular chain both ends dimethylhydrogen Proxy group dimethylsiloxane-methylphenylsiloxane copolymers, dimethylpolysiloxane with both molecular chain terminals hydro diene siloxy groups at methylphenyl polysiloxane represented by (R ⁵⁾ 3 _SiO 0.5 _(as R ⁵ is a) siloxy A polyorganohydrogensiloxane copolymer comprising a unit, a siloxy unit represented by (R ⁵ ) ₂ HSiO _0.5 and a siloxy unit represented by SiO ₂ , represented by (R ⁵ ) ₂ HSiO _0.5 A polyorganohydrogensiloxane copolymer comprising a siloxy unit and a siloxy unit represented by SiO ₂ , a siloxy unit represented by R ⁵ HSiO and a siloxy unit represented by R ⁵ SiO _1.5 , or HSiO polyorganohydrogensiloxane copolymer comprising a siloxy unit represented by _1.5 Etc. The.
Specific examples of the polyorganohydrogensiloxane other than the polyorganohydrogensiloxane represented by R ⁸ _a H _b SiO _(4-ab-2) include (R ⁵ ) ₃ SiO _0. A siloxy unit represented by ₅ , a siloxy unit represented by (R ⁵ ) ₂ HSiO _0.5 , a siloxy unit represented by (R ⁵ ) ₂ SiO, and R ⁵ SiO _1.5 A polyorganohydrogensiloxane copolymer comprising a siloxy unit and a siloxy unit represented by (R ⁵ ) ₄ Si ₂ R ⁷ O (R ⁷ is as described above), (R ⁵ ) ₃ SiO _0.5 A siloxy unit represented by: a siloxy unit represented by (R ⁵ ) ₂ HSiO _0.5 ; a siloxy unit represented by (R ⁵ ) ₂ SiO; and R ⁶ SiO _1.5 (R ⁶ is Street In a siloxy unit _{^{represented, (R 5) 4 Si 2}} R 7 O consisting of siloxy units represented by polyorganohydrogensiloxane ^copolymers, siloxy represented by _(R 5) _{3 SiO 0.5} A polyorganohydro consisting of a unit, a siloxy unit represented by (R ⁵ ) ₂ SiO, a siloxy unit represented by R ⁵ HSiO, and a siloxy unit represented by (R ⁵ ) ₄ Si ₂ R ⁷ O Examples include a gen siloxane copolymer. These may be used individually by 1 type and may be used in combination of 2 or more type.

Examples of commercially available polyorganohydrogensiloxanes include DMS-H03, DMS-H11, DMS-H21, DMS-H25, DMS-H31, DMS-H41, and dimethylhydrogen at both ends of the molecular chain. Siloxy group-capped dimethylpolysiloxane), HMS-013, HMS-031, HMS-064, HMS-071, HMS-082, HMS-151, HMS-301, HMS-501 (trimethylsiloxy group-capped dimethylsiloxane at both molecular chain ends) Methyl hydrogen siloxane copolymer), HMS-991, HMS-992, HMS-993 (trimethylsiloxy group-blocked methylhydrogenpolysiloxane blocked with molecular chain), HMS-H271 (dimethylhydrogensiloxy group with molecular chain both ends) Seal Dimethylsiloxane / methylhydrogensiloxane copolymer), HPM-502 (both ends of the molecular chain dimethylhydrogensiloxy group-blocked phenylmethylsiloxane / methylhydrogensiloxane copolymer), HDP-111 (both ends of the molecular chain dimethylhydrogen) And siloxy group-blocked phenyl (dimethylhydrosiloxy) siloxane (both manufactured by Gelest, Inc.).

The blending amount of the polyorganohydrogensiloxane is the effective amount of curing of the carbon-carbon double bond-containing polyorganosiloxane. In particular, the Si-H group of the polyorganohydrogensiloxane contains a carbon-carbon double bond. The ratio is preferably 0.1 to 4.0 per substituent having a carbon-carbon double bond in the polyorganosiloxane. When the Si—H group is less than 0.1 per substituent having a carbon-carbon double bond, the curing reaction does not proceed and it may be difficult to obtain a cured product. If the number of Si-H groups exceeds 4.0 per substituent having a carbon-carbon double bond, a large amount of unreacted Si-H groups remain in the cured product, so that the physical properties of the cured product are deteriorated over time. May change. It is more preferable that the Si—H group has a ratio of 1.0 to 3.0 per substituent having a carbon-carbon double bond.

A conventionally well-known thing can be used as said hydrosilylation reaction catalyst. Specifically, for example, platinum group metals such as platinum (including platinum black), rhodium and palladium, H ₂ PtCl ₄ · yH ₂ O, H ₂ PtCl ₆ · yH ₂ O, NaHPtCl ₆ · yH ₂ O, KHPtCl ₆ · yH ₂ O, Na ₂ PtCl ₆ · yH ₂ O, K ₂ PtCl ₄ · yH ₂ O, PtCl ₄ · yH ₂ O, PtCl ₂ , Na ₂ HPtCl ₄ · yH ₂ O , Y is an integer of 0 to 6, preferably 0 or 6, and chloroplatinic acid and chloroplatinate, and alcohol-modified chloroplatinic acid (see US Pat. No. 3,220,972) ), And a complex of chloroplatinic acid and olefin (see US Pat. No. 3,159,601, US Pat. No. 3,159,662, and US Pat. No. 3,775,452). Or a platinum group metal such as platinum black or palladium supported on a carrier such as alumina, silica or carbon, rhodium-olefin complex, chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst), platinum chloride, Complex of chloroplatinic acid or chloroplatinate and vinyl group-containing siloxane, dichlorodipyridine platinum (II) (see JP 09-165453 A), 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 , Pt (CH ₂ ═CH (Me) SiO) ₄ Platinum group metal catalysts such as a vinyl siloxane complex of platinum such as JP-A-11-152337.

The content of the hydrosilylation reaction catalyst is not particularly limited as long as it is an effective amount as a catalyst for the hydrosilylation reaction. It is preferable that When the content of the hydrosilylation reaction catalyst is within this range, the addition reaction is sufficiently accelerated, so that the resulting addition-curable silicone resin composition can be sufficiently cured and economically. It is advantageous. The content of the hydrosilylation reaction catalyst is more preferably 1 to 500 ppm, and still more preferably 1 to 20 ppm.

As the addition-curable silicone resin mixture, known ones can be used, and a two-component thermosetting type is preferable from the viewpoint of availability.
Commercially available products of the two-component thermosetting type addition-curable silicone resin mixture include, for example, IVS4312, XE14-C2042, IVS4542, IVS4546, IVS4622, IVS4632, IVS4742, IVS4752, XE14-C2860, XE14-C3450, IVS5854 (all 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 Shin-Etsu Chemical Co., Ltd.) Manufactured), OE-6351, OE-6336, OE-6370M, EG-6301, JCR-6125, JCR-6140, OE-6450, OE-6520, OE-6550, OE-6636, OE-6636, OE-6635 OE-6630, OE-6665N, SR7010 (all manufactured by Toray Dow Corning).

[Condensation-curable silicone resin mixture]
The condensation curable silicone resin mixture used in the present invention 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 byproduct. 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.
The addition-curable silicone resin mixture hardly generates by-products, but the 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 manage the 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 Chemical Co., Ltd.), one liquid condensed alcohol type, KE-4806-W, KE-4901-W, KE-4920T, KE -4920, KE-4921-B, KE-4921-W (all manufactured by Shin-Etsu Chemical Co., Ltd.), two-component condensed acetone type, KE-200, KE-210 (all manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Is mentioned.

The silicone resin composition of the present invention may contain additives as necessary within the range not impairing the purpose and effect of the present invention, in addition to the silicone resin mixture and the adhesiveness imparting agent according to the present invention.

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 silicone resin composition of the present invention, for example, it can be produced by mixing the silicone resin mixture, the adhesiveness imparting agent according to the present invention, and the additive used as necessary. .

The silicone resin composition of the present invention can be a one-component type or a two-component type.
The 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 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 silicone resin composition of the present invention can be cured at room temperature or by heating. A cured silicone resin obtained by curing the silicone resin composition of the present invention is also one aspect of the present invention.

The heating temperature when the silicone resin composition of the present invention is heated and cured is usually 100 ° C or higher, preferably 120 ° C or higher, more preferably 120 to 200 ° C, and more preferably 120 to 180 ° C. More preferably.

The use of the silicone resin composition of the present invention includes, for example, 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 silicone resin of the present invention is also one aspect of the present invention.

The silicone resin composition of the present invention is used for applications such as 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, and the like. be able to.

ADVANTAGE OF THE INVENTION According to this invention, the silicone resin composition which has the outstanding adhesiveness also under high temperature and high humidity can be provided. Moreover, according to this invention, the silicone resin hardened | cured material and optical semiconductor element sealing body which use this 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 to these examples.

(Production Example 1)
(Reaction of silicone compound having amino group with hexamethylene diisocyanate and n-butyl isocyanate (preparation of adhesion promoter A))
In a 50 mL four-necked flask equipped with a stirrer, a thermometer and a cooler, under a nitrogen atmosphere, a silicone compound having an amino group (“KF-8010” manufactured by Shin-Etsu Chemical Co., Ltd., amino group equivalent: 430 g / mol) ) 5.0 g (amino group 11.6 mmol) and 10 g of toluene were charged, stirred and dissolved. Hexamethylene diisocyanate (0.13 g, 0.7 mmol) was dissolved in 5 g of toluene, and slowly dropped into a four-necked flask containing a silicone compound having an amino group while maintaining the temperature at 25 ° C. Thereafter, 1.07 g (10.7 mmol) of n-butyl isocyanate was dropped, and the mixture was stirred at room temperature for 1 hour. After stirring, the solution was concentrated under reduced pressure to obtain 6.0 g of a colorless transparent viscous liquid (adhesion imparting agent A).
As a result of measuring the adhesion imparting agent A by ¹ H-NMR, the adhesion imparting agent A is a structural unit represented by the formula (1-1) and the formula (1-2) (R ^1a is a methyl group). , R ² is an n-propylene group, X is NH, and R ³ is an n-butyl group) and the structural unit represented by the formula (1-3) (R ^1a is a methyl group, R ² is an n-propylene group) , R ⁴ has an n-hexylene group, X is NH) and a structural unit represented by the formula (2) (R ^1b is a methyl group).

(Production Example 2)
(Reaction of silicone compound having amino group with hexamethylene diisocyanate and n-butyl isocyanate (Preparation of adhesion promoter B))
In a 50 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, under a nitrogen atmosphere, a silicone compound having an amino group (“KF-8012” manufactured by Shin-Etsu Chemical Co., Ltd., amino group equivalent: 2200 g / mol) ) 10.0 g (4.5 mmol of amino group) and 20 g of toluene were charged and stirred to dissolve. Hexamethylene diisocyanate 0.05 g (0.27 mmol) was dissolved in 5 g of toluene, and slowly dropped into a four-necked flask containing a silicone compound having an amino group while maintaining 25 ° C. Thereafter, 0.44 g (4.4 mmol) of n-butyl isocyanate was added dropwise, and the mixture was stirred at room temperature for 1 hour. After stirring, the solution was concentrated under reduced pressure to obtain 10.0 g of a colorless transparent viscous liquid (adhesion imparting agent B).
As a result of measuring the adhesion-imparting agent B by ¹ H-NMR, the adhesion-imparting agent B is a structural unit represented by the formula (1-1) and the formula (1-2) (R ^1a is a methyl group). , R ² is an n-propylene group, X is NH, and R ³ is an n-butyl group) and the structural unit represented by the formula (1-3) (R ^1a is a methyl group, R ² is an n-propylene group) , R ⁴ has an n-hexylene group, X is NH) and a structural unit represented by the formula (2) (R ^1b is a methyl group).

(Production Example 3)
(Reaction of silicone compound having amino group with hexamethylene diisocyanate and n-butyl isocyanate (Preparation of adhesion promoter C))
In a 50 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, under a nitrogen atmosphere, a silicone compound having an amino group (“X-22-1660B-3”, amino group, manufactured by Shin-Etsu Chemical Co., Ltd.) Equivalent 2200 g / mol) 10.0 g (amino group 4.5 mmol) and toluene 20 g were charged and stirred to dissolve. Hexamethylene diisocyanate 0.05 g (0.27 mmol) was dissolved in 5 g of toluene, and slowly dropped into a four-necked flask containing a silicone compound having an amino group while maintaining 25 ° C. Thereafter, 0.44 g (4.4 mmol) of n-butyl isocyanate was added dropwise, and the mixture was stirred at room temperature for 1 hour. After stirring, the solution was concentrated under reduced pressure to obtain 10.0 g of a colorless transparent viscous liquid (adhesion imparting agent C).
As a result of measuring the adhesion-imparting agent C by ¹ H-NMR, the adhesion-imparting agent C is a structural unit represented by the formula (1-1) and the formula (1-2) (R ^1a is a methyl group). , R ² is an n-propylene group, X is NH, and R ³ is an n-butyl group) and the structural unit represented by the formula (1-3) (R ^1a is a methyl group, R ² is an n-propylene group) , R ⁴ has an n-hexylene group, X is NH) and a structural unit represented by the formula (2) (R ^1b is a methyl group, a phenyl group).

(Production Example 4)
(Reaction of silicone compound having amino group with m-xylylene diisocyanate and n-butyl isocyanate (preparation of adhesion promoter D))
In a 50 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, under a nitrogen atmosphere, a silicone compound having an amino group (“X-22-1660B-3”, amino group, manufactured by Shin-Etsu Chemical Co., Ltd.) Equivalent 2200 g / mol) 10.0 g (amino group 4.5 mmol) and toluene 20 g were charged and stirred to dissolve. 0.04 g (0.23 mmol) of m-xylylene diisocyanate was dissolved in 5 g of toluene and slowly dropped into a four-necked flask containing a silicone compound having an amino group while maintaining 25 ° C. Thereafter, 0.45 g (4.5 mmol) of n-butyl isocyanate was dropped, and the mixture was stirred at room temperature for 1 hour. After stirring, the mixture was concentrated under reduced pressure to obtain 10.2 g of a colorless transparent viscous liquid (adhesiveness imparting agent D).
As a result of measuring the adhesion-imparting agent D by ¹ H-NMR, the adhesion-imparting agent D is a structural unit represented by the formula (1-1) and the formula (1-2) (R ^1a is a methyl group). , R ² is an n-propylene group, X is NH, and R ³ is an n-butyl group) and the structural unit represented by the formula (1-3) (R ^1a is a methyl group, R ² is an n-propylene group) , R ⁴ has a xylylene group, X is NH) and a structural unit represented by the formula (2) (R ^1b is a methyl group, a phenyl group).

(Production Example 5)
(Reaction of silicone compound having amino group with isophorone diisocyanate and n-butyl isocyanate (preparation of adhesion promoter E))
In a 50 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, under a nitrogen atmosphere, a silicone compound having an amino group (“X-22-1660B-3”, amino group, manufactured by Shin-Etsu Chemical Co., Ltd.) Equivalent 2200 g / mol) 10.0 g (amino group 4.5 mmol) and toluene 20 g were charged and stirred to dissolve. 0.06 g (0.27 mmol) of isophorone diisocyanate was dissolved in 5 g of toluene, and slowly dropped into a four-necked flask containing a silicone compound having an amino group while maintaining 25 ° C. Thereafter, 0.45 g (4.5 mmol) of n-butyl isocyanate was dropped, and the mixture was stirred at room temperature for 1 hour. After stirring, the solution was concentrated under reduced pressure to obtain 10.4 g of a colorless transparent viscous liquid (adhesiveness imparting agent E).
As a result of measuring the adhesion-imparting agent E by ¹ H-NMR, the adhesion-imparting agent E is a structural unit represented by the formula (1-1) and the formula (1-2) (R ^1a is a methyl group). , R ² is an n-propylene group, X is NH, and R ³ is an n-butyl group) and the structural unit represented by the formula (1-3) (R ^1a is a methyl group, R ² is an n-propylene group) , R ⁴ has an isoholonylene group, X is NH) and the structural unit represented by the formula (2) (R ^1b is a methyl group, a phenyl group).

(Production Example 6)
(Reaction of silicone compound having hydroxy group with hexamethylene diisocyanate and n-butyl isocyanate (preparation of adhesion promoter F))
In a 50 mL four-necked flask equipped with a stirrer, a thermometer and a condenser, under a nitrogen atmosphere, a silicone compound having a hydroxy group (“KF-6003” manufactured by Shin-Etsu Chemical Co., Ltd., hydroxy group equivalent: 2545 g / mol) ) 10.0 g (hydroxy group 3.9 mmol) and toluene 20 g were charged and stirred to dissolve. 0.04 g (0.24 mmol) of hexamethylene diisocyanate was dissolved in 5 g of toluene, and slowly dropped into a four-necked flask containing a silicone compound having a hydroxy group while maintaining 25 ° C. Thereafter, 0.38 g (3.8 mmol) of n-butyl isocyanate was dropped, and the mixture was stirred at room temperature for 1 hour. After stirring, the solution was concentrated under reduced pressure to obtain 10.1 g of a colorless transparent viscous liquid (adhesion imparting agent F).
As a result of measuring the adhesion-imparting agent F by ¹ H-NMR, the adhesion-imparting agent F is a structural unit represented by the above formulas (1-1) and (1-2) (R ^1a is a methyl group). , R ² is an n-4-oxahexylene group, X is an oxygen atom, R ³ is a butyl group, and the structural unit represented by the formula (1-3) (R ^1a is a methyl group, R ² is n -4-oxahexylene group, R ⁴ is n-hexylene group, X is an oxygen atom) and the structural unit represented by the above formula (2) (R ^1b is a methyl group) is confirmed. did.

(Production Example 7)
(Preparation of adhesion promoter G)
1.0 g of methacryloyltrimethoxylane and 1.0 g of glycidoxypropyltrimethoxysilane were mixed and heated at 100 ° C. for 2 hours to obtain an adhesion-imparting agent G as another adhesion-imparting agent.

(Production Example 8)
(Preparation of adhesiveness imparting agent H)
By mixing 1.0 g of methacryloyltrimethoxylane, 1.0 g of glycidoxypropyltrimethoxysilane, and 1.0 g of vinyltriethoxysilane, and heating at 100 ° C. for 2 hours, the adhesiveness as another adhesive imparting agent An imparting agent H was obtained.

(Examples 1-13, Comparative Examples 1-9)
The silicone resin composition was prepared by mixing each component of the compounding quantity described in Tables 1 and 2 uniformly, and then thoroughly degassing.
In addition, as addition curable silicone resin mixture A in Tables 1 and 2, OE-6370M (manufactured by Toray Dow Corning) A liquid and B liquid (1: 1 mixture) were used. Addition-curable silicone resin mixture A is a mixture containing a carbon-carbon double bond-containing polyorganosiloxane component and a polyorganohydrogensiloxane component. As addition-curable silicone resin mixture B in Tables 1 and 2, OE-6630 (manufactured by Dow Corning Toray) A liquid and B liquid (1: 4 mixture) were used. Addition-curable silicone resin mixture B is a mixture containing a carbon-carbon double bond-containing polyorganosiloxane component and a polyorganohydrogensiloxane component. Furthermore, as the condensation curable silicone resin mixture C in Tables 1 and 2, a two-component condensation acetone type silicone resin mixture (manufactured by Shin-Etsu Chemical Co., Ltd., “KE-200”) and a curing agent CX-200 (10: 1) Mixture).

<Evaluation>
The following evaluation was performed about each silicone resin composition obtained in Examples 1-13 and Comparative Examples 1-9. The results are shown in Tables 1 and 2.

(1) Hardness (Type A, Type D)
Each addition-curable silicone resin composition (Examples 1-4, 10 and Comparative Examples 1-3) containing the addition-curable silicone resin mixture A is poured into a resin mold and heated at 150 ° C. for 4 hours to perform addition curing. The type silicone resin composition was cured. 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”).
Moreover, each addition-curable silicone resin composition (Examples 5-9 and Comparative Examples 4-6) containing the addition-curable silicone resin mixture B is poured into a resin mold and heated at 150 ° C. for 2 hours to perform addition curing. The type silicone resin composition was cured. 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. About the obtained test piece for hardness measurement, hardness (type D) was measured using the rubber hardness meter (The product made by ASKER, D type).
Furthermore, each condensation curable silicone resin composition (Examples 11 to 13 and Comparative Examples 7 to 9) containing the condensation curable silicone resin mixture C was poured into a resin mold and allowed to stand at room temperature for 1 week, followed by condensation curing. The type silicone resin composition was cured. 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 to aluminum Each of the silicone resin compositions obtained in Examples 1 to 13 and Comparative Examples 1 to 9 was made of two aluminum plates so that the bonded portion was a rectangle of 12.5 × 25 mm. (Size 2 × 25 × 100 mm) was applied on one side, the other aluminum plate was bonded together, and the silicone resin composition was cured (obtained in Examples 1 to 4, 10 and Comparative Examples 1 to 3). Each silicone resin composition was cured by heating at 150 ° C. for 4 hours, and each silicone resin composition obtained in Examples 5-9 and Comparative Examples 4-6 was cured by heating at 150 ° C. for 2 hours, Example 11 Each silicone resin composition obtained in ˜13 and Comparative Examples 7-9 was allowed to stand for 1 week at room temperature and cured, and was used as a tensile shear test piece. The aluminum plate that is the adhesive substrate was dried at 150 ° C. for 1 hour. About the obtained tensile shear test piece, tensile shear bond strength was measured using a tensile tester (manufactured by Shimadzu Corporation, “AGS-X”) under the conditions of a distance between grips of 100 mm and a test speed of 5 mm / min. .
Comparative Examples 1 and 4 for Examples and Comparative Examples using the same silicone resin mixture as those based on the adhesive strengths of Comparative Example 1, Comparative Example 4 and Comparative Example 7 in which no adhesiveness-imparting agent was used. The adhesive strength of Comparative Example 7 was “x” when it was less than 1.1 times, “△” when it was 1.1 times or more and less than 1.2 times, and 1.2 times or more and 1 The case of less than 3 times was evaluated as “◯”, and the case of 1.3 times or more was evaluated as “「 ”.
Further, the obtained tensile shear test piece was exposed to conditions of 60 ° C. and 60% RH for 100 hours using a small environmental tester (“SH-261” manufactured by Espec Corp.), and the same method as above. Tensile shear bond strength was measured.
When the initial bond strength is less than 0.5 times, “X”, when 0.5 times or more and less than 0.8 times, “△”, when 0.8 times or more Was evaluated as “◯”.

(3) Tensile shear adhesive strength for poly (1,4-cyclohexyldimethylene terephthalate) (PCT) Each silicone resin composition obtained in Examples 1 to 13 and Comparative Examples 1 to 9 has an adhesive part of 12.5. Apply to one of two PCT plates (size 2 × 25 × 100 mm) so as to form a rectangle of × 25 mm, and bond the other PCT plate to cure the silicone resin composition (Examples 1 to 2). Each silicone resin composition obtained in 4, 10 and Comparative Examples 1 to 3 was cured by heating at 150 ° C. for 4 hours, and each silicone resin composition obtained in Examples 5 to 9 and Comparative Examples 4 to 6 was Curing was carried out at 150 ° C. for 2 hours, and the respective silicone resin compositions obtained in Examples 11 to 13 and Comparative Examples 7 to 9 were allowed to stand at room temperature for 1 week to cure), and were used as tensile shear test pieces. As the PCT plate as an adhesive substrate, one that was dried at 150 ° C. for 1 hour was used. About the obtained tensile shear test piece, tensile shear bond strength was measured using a tensile tester (manufactured by Shimadzu Corporation, “AGS-X”) under the conditions of a distance between grips of 100 mm and a test speed of 5 mm / min. .
Comparative Examples 1 and 4 for Examples and Comparative Examples using the same silicone resin mixture as those based on the adhesive strengths of Comparative Example 1, Comparative Example 4 and Comparative Example 7 in which no adhesiveness-imparting agent was used. The adhesive strength of Comparative Example 7 was “x” when it was less than 1.1 times, “△” when it was 1.1 times or more and less than 1.2 times, and 1.2 times or more and 1 The case of less than 3 times was evaluated as “◯”, and the case of 1.3 times or more was evaluated as “「 ”.
Further, the obtained tensile shear test piece was exposed to conditions of 60 ° C. and 60% RH for 100 hours using a small environmental tester (“SH-261” manufactured by Espec Corp.), and the same method as above. Tensile shear bond strength was measured.
When the initial bond strength is less than 0.5 times, “X”, when 0.5 times or more and less than 0.8 times, “△”, when 0.8 times or more Was evaluated as “◯”.

From Table 1 and 2, it turns out that the adhesiveness with respect to aluminum and PCT is improving by mix | blending the adhesiveness imparting agent concerning this invention. It can also be seen that it has sufficient adhesion even after exposure to high temperature and high humidity conditions.
On the other hand, when other adhesive imparting agents are blended, it can be seen that the adhesiveness is remarkably lowered when exposed to high temperature and high humidity conditions. Moreover, in the comparative example 5 and the comparative example 6, it understand | indicate | reveals that the hardness of a silicone resin hardened | cured material is falling significantly by mix | blending another adhesiveness imparting agent.

ADVANTAGE OF THE INVENTION According to this invention, the silicone resin composition which has the outstanding adhesiveness also under high temperature and high humidity can be provided. Moreover, according to this invention, the silicone resin hardened | cured material and optical semiconductor element sealing body which use this silicone resin composition can be provided.

Claims (9)

A silicone resin composition containing a 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 silicone resin composition comprising a compound having a structural unit.

In formulas (1-1), (1-2), and (1-3), R ^1a is independently an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group. Represents an alkenyl group having 2 to 9 carbon atoms, a (meth) acryloyloxyalkyl group, a (meth) acryloyloxy group, or an alkoxy group having 1 to 4 carbon atoms, and R ² is independently bonded to a silicon atom. Represents an alkylene group having 1 to 8 carbon atoms in which some carbon atoms excluding the carbon atoms may be substituted with oxygen atoms, and X is independently an oxygen atom, NH, or NR ⁹ ; R < ⁹ > represents a C1-C18 alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group each independently. In formula (1-1) and formula (1-2), 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, (meta ) Represents an acryloyloxyalkyl group or a silyl group. In formula (1-3), R ⁴ each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms. A compound having a structural unit represented by formula (1-3) between a structural unit represented by formula (1-1) and a structural unit represented by formula (1-2) is represented by the formula (1 The silicone resin composition according to claim 1, further comprising a structural unit represented by the following formula (2) between the structural unit represented by -1) and the structural unit represented by formula (1-2): .

In formula (2), R ^1b each 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, a (meth) acryloyloxyalkyl group, A (meth) acryloyloxy group or a C1-C4 alkoxy group is represented, and n is an integer of 1-1500. A compound having a structural unit represented by formula (1-3) between a structural unit represented by formula (1-1) and a structural unit represented by formula (1-2) is represented by the formula (1 The silicone resin composition of Claim 1 or 2 which has a structural unit represented by following formula (3) between the structural unit represented by -1) and the structural unit represented by Formula (1-2). object.

In formula (3), each R ^1a 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, a (meth) acryloyloxyalkyl group, A (meth) acryloyloxy group or an alkoxy group having 1 to 4 carbon atoms, each R ^1b independently represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or 2 carbon atoms. Represents an alkenyl group of ˜9, a (meth) acryloyloxyalkyl group, a (meth) acryloyloxy group, or an alkoxy group having 1 to 4 carbon atoms, and each R ² independently represents a carbon atom bonded to a silicon atom. Represents a C1-C8 alkylene group in which some of the carbon atoms may be substituted with oxygen atoms, and each R ⁴ independently represents a C1-C20 divalent group. Represents a hydrocarbon group, each X is independently an oxygen atom, NH, or NR ⁹ , and each R ⁹ is independently an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, or Represents an aralkyl group, and l is an integer of 1 to 400. The silicone resin composition according to claim 1, 2 or 3, wherein the adhesion-imparting agent is a mixture of silicone compounds represented by the following average structural formula (8).

In formula (8), each R ^1a 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, a (meth) acryloyloxyalkyl group, A (meth) acryloyloxy group or an alkoxy group having 1 to 4 carbon atoms, each R ^1b independently represents an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, or 2 carbon atoms. Represents an alkenyl group of ˜9, a (meth) acryloyloxyalkyl group, a (meth) acryloyloxy group, or an alkoxy group having 1 to 4 carbon atoms, and each R ² independently represents a carbon atom bonded to a silicon atom. Represents an alkylene group having 1 to 8 carbon atoms in which some of the carbon atoms except that may be substituted with oxygen atoms, and each R ³ independently represents an alkyl group having 1 to 18 carbon atoms. Represents a dialkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a sulfonyl group, an acyl group, a (meth) acryloyloxyalkyl group, or a silyl group, and each R ⁴ is independently a divalent group having 1 to 20 carbon atoms. Represents a hydrocarbon group, X is each independently an oxygen atom, NH or NR ⁹ , p is an integer of 0 to 400, and o is a positive number of 1 or less. R < ⁹ > represents a C1-C18 alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group each independently. The silicone resin composition according to claim 1, 2, 3, or 4, wherein the silicone resin mixture is an addition-curable silicone resin mixture. The silicone resin composition according to claim 1, 2, 3, or 4, wherein the silicone resin mixture is a condensation-curable silicone resin mixture. The silicone resin composition according to claim 1, 2, 3, 4, 5 or 6, wherein the content of the adhesion-imparting agent is 0.01 to 20% by mass. A cured silicone resin obtained by curing the silicone resin composition according to claim 1, 2, 3, 4, 5, 6 or 7. A sealed optical semiconductor element, wherein the optical semiconductor element is sealed with the cured silicone resin according to claim 8.