JP3439719B2 - Curable organopolysiloxane composition, cured product thereof and integrated product with substrate - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable organopolysiloxane composition, a cured product thereof and an integrated product with a substrate. More specifically, it relates to a curable organopolysiloxane composition having excellent curability, an organopolysiloxane cured product that can be well adhered to various substrates, and an integrated product of the cured product and the substrate.

[0002]

BACKGROUND OF THE INVENTION Consisting of alkenyl group-containing organopolysiloxane and organohydrogenpolysiloxane,
An organopolysiloxane composition that cures in the presence of a platinum-based catalyst is called an addition reaction-curable organopolysiloxane composition and is used in various industrial fields.
However, since the surface of the cured product obtained by curing this composition is inactive and has releasability, after curing, phenol resin, epoxy resin, melamine resin, urea resin, polyurethane resin, polyimide resin, etc. It was extremely difficult to adhere the thermosetting organic resin of (3). For this reason, there has been attempted a method in which the surface of a cured product of an addition reaction-curable organopolysiloxane composition is treated with ozone, and then an organic resin is brought into contact with the surface to cure the surface, thereby integrating the two (Japanese Patent Application Laid-Open No. Hei 10 (1999) -242242). 2 -27756 gazette). However, this method has a drawback that the adhesiveness is deteriorated with time and is not satisfactory in practice. In order to solve this, the present inventors have previously proposed a curable composition comprising an alkenyl group-containing organopolysiloxane, an organohydrogensiloxane, a hydroxyphenyl group-containing methacryl-functional siloxane and a hydrosilylation reaction catalyst ( Japanese Patent Application No. 10-278538
Specification). However, when this curable composition is applied to the surface of various base materials to be cured, a small amount of silicone component is thinly diffused and exudes around the composition before or during the curing, and the exuded portion However, there is a problem in that it does not adhere to the substrate. When a semiconductor chip is bonded to a substrate or a package using a silicone-based adhesive based on such a composition, a slight amount of the silicone component diffused from the silicone-based adhesive before heat curing is spread around the semiconductor chip. Exudation, which contaminates the surface of the semiconductor chip, substrate, package, lead frame, etc., reduces wire bondability and causes poor adhesion with the sealing resin, and reduces the moisture resistance of the semiconductor. There was a problem that caused it. From these facts, a curable organopolysiloxane composition has been desired in which the silicone component diffused and exuded from the composition is cured well and can be adhered to various substrates. On the other hand, an addition reaction-curable organopolysiloxane composition comprising an organopolysiloxane having a silicon-bonded hydrogen atom and an alkenyl group in the same molecule and a hydrosilylation reaction catalyst is known (Patent Publication No. 2,519,563). Japanese Patent Laid-Open No. 1-213363). These compositions are
It has been reported that the amount of uncured product in the cured product after heat curing is reduced as compared with the composition comprising the alkenyl group-containing organopolysiloxane and the organohydrogensiloxane. However, since these compositions have a small molar ratio of silicon-bonded hydrogen atoms to alkenyl groups, only a gel-like cured product can be obtained, and the gel-like cured product has too low physical strength to be used for adhesive applications. There was a flaw.

[0003]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, use an organopolysiloxane having a silicon atom-bonded hydrogen atom and an alkenyl group in the same molecule as the main agent. As a result, the silicone component that has diffused and exuded from the composition is cured well, and by blending a compound containing an alkenyl group and a hydroxyphenyl group in one molecule as an adhesion promoter, the exuded silicone component is The present inventors have completed the present invention by finding that they can bond well to various substrates. That is, an object of the present invention is to provide a curable organopolysiloxane composition which can be rapidly cured on the surface of various base materials, and can also be satisfactorily cured on a portion that has diffused and exuded before or during curing to adhere to various base materials. The object is to provide an article, a cured product obtained by curing the composition, and an integrated product of the cured product and a substrate.

[0004]

The present invention provides (A) an organopolysiloxane having on average two or more alkenyl groups and two or more silicon-bonded hydrogen atoms in the same molecule, and (B) one molecule. A compound containing an alkenyl group and a hydroxyphenyl group, and (C) a catalyst for hydrosilylation reaction, a curable organopolysiloxane composition, a cured product obtained by curing the composition,
It also relates to an integrated product of a cured product obtained by integrating a cured product of the composition and a substrate.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION To explain this, the component (A) used in the composition of the present invention comprises, on average, two or more alkenyl groups and two or more silicon-bonded hydrogen atoms in one molecule. Is an organopolysiloxane having However, the organopolysiloxane does not contain a hydroxyphenyl group. Its chemical structure may be linear, cyclic or reticulated, and oligomers to high molecular weight compounds can be used. Among them, since it is easy to work with the component (B), it has a linear or branched molecular structure and
Viscosity at 5 ° C is 100 to 1,000,000 mPa
It is preferably a liquid organopolysiloxane having a range of s. Further, the alkenyl group and the silicon atom-bonded hydrogen atom in the organopolysiloxane of the component (A) may be bonded to the terminal of the molecular chain or may be bonded to the side chain. Examples of the alkenyl group include vinyl group, allyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group and decenyl group. In addition to these, groups containing an alkenyl group such as a methacryloxypropyl group and an acryloxypropyl group can be mentioned. The position of the double bond in the alkenyl group is preferably at the end opposite to the silicon atom bonded to the alkenyl group, from the viewpoint of high addition reactivity. In the organopolysiloxane as the component (A), the content of silicon atom-bonded alkenyl groups is preferably in the range of 0.025 to 5 mol%, more preferably 0.1 to 1.2 mol%. The content of silicon atom-bonded hydrogen atoms is preferably in the range of 0.025 to 5 mol%, more preferably 0.15 to 2.5 mol%. The molar ratio of silicon atom-bonded hydrogen atoms to alkenyl groups is usually in the range of 0.1 to 200, 0.3
It is preferably in the range of -20, more preferably in the range of 1-10, and even more preferably in the range of 2-7. This is because if the ratio is less than 0.1, the curability of the composition of the present invention decreases, and if it exceeds 200, the physical properties of the obtained cured product deteriorate. In the organopolysiloxane of component (A), the alkenyl group and the organic group bonded to the silicon atom other than the silicon atom-bonded hydrogen atom are preferably monovalent hydrocarbon groups. In particular,
Examples thereof include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group; aryl groups such as phenyl group, tolyl group and xylyl group; aralkyl groups such as benzyl group and phenethyl group. In addition to this, a small amount of a hydroxyl group, an alkoxy group, a haloalkyl group or the like may be contained as long as the object of the present invention is not impaired. Among these, it is preferable that more than half of the organic groups bonded to the silicon atom are methyl groups from the viewpoint of economy and availability. The organopolysiloxane as the component (A) can be produced by a known equilibrium polymerization reaction using an acid catalyst.

Specific examples of the organopolysiloxane as the component (A) include siloxanes represented by the following formula. In the following formulae, Me represents a methyl group.

[Chemical 3]

[Chemical 4]

The component (B) used in the composition of the present invention is
It is a compound containing an alkenyl group and a hydroxyphenyl group in one molecule. Such compounds include 2-allylphenol, eugenol, orthoeugenol,
Examples include phenol compounds containing an aliphatic unsaturated bond such as 4-allyl-2,6-dimethoxyphenol and organosilicon compounds represented by the following formula.

[Chemical 5] In the above formula, X is an alkenyl group, and examples thereof include a vinyl group, an allyl group, an isopropenyl group, and a hexenyl group. Z
Is the formula:

[Chemical 6] Is an ester group or a phenylene group represented by, and as the phenylene group, o-phenylene group, m-phenylene group,
A p-phenylene group is exemplified. A is a divalent hydrocarbon group having 1 or more carbon atoms or a formula: —R ² —O—R ² — (wherein R ²
Is a divalent hydrocarbon group, and examples thereof include an alkylene group and an arylene group. ) Is a group represented by. Specific examples of A include ethylene group, propylene group, butylene group, hexylene group, ethyleneoxypropylene group, and phenyleneoxypropylene group. Y is a substituted or unsubstituted hydroxyphenyl group, and examples of the substituted hydroxyphenyl group include an alkyl group-substituted hydroxyphenyl group and an alkoxy group-substituted hydroxyphenyl group. Examples of the alkyl group which is a substituent include a methyl group, an ethyl group, a propyl group and a butyl group, and examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group and a butoxy group. The bonding positions of the hydroxyl group, alkyl group and alkoxy group in these hydroxyphenyl groups are not particularly limited. Examples of such an unsubstituted hydroxyphenyl group for Y include a 2-hydroxyphenyl group, a 4-hydroxyphenyl group, a 3,4-dihydroxyphenyl group, and a 3,5-dihydroxyphenyl group. As the alkyl group-substituted hydroxyphenyl group, 3,
5-ditert-butyl-4-hydroxyphenyl group, 3-
A methyl-4-hydroxyphenyl group is exemplified, and an alkoxy group-substituted hydroxyphenyl group is 4-hydroxy.
Examples thereof include a 3-methoxyphenyl group and a 3,5-dimethoxy-4-hydroxyphenyl group. Of these, Y is a 2-hydroxyphenyl group or 4-hydroxy-
It is preferably a 3-methoxyphenyl group. R ¹ is the same or different divalent hydrocarbon group having 2 or more carbon atoms that does not contain an aliphatic unsaturated bond, and is an alkylene group such as an ethylene group, a propylene group, a butylene group or a hexylene group;
An arylene group such as a phenylene group is exemplified. R is a monovalent hydrocarbon group of the same kind or different kinds that does not contain an aliphatic unsaturated bond, and is an alkyl group such as methyl group, ethyl group, butyl group, pentyl group, hexyl group; phenyl group, tolyl group, xylyl group, etc. And an aralkyl group such as a benzyl group and a phenethyl group. m, p, r and s are 0 or 1. n is 0-2, but 1-2
Is preferred. q is an integer from 0 to 7, but 0 to
It is preferably 4.

Specific examples of the compound as the component (B) include compounds represented by the following formula.

[Chemical 7]

[Chemical 8]

[Chemical 9]

[Chemical 10]

[Chemical 11]

[Chemical 12]

[Chemical 13]

[Chemical 14]

[Chemical 15]

[Chemical 16]

[Chemical 17]

[Chemical 18]

The amount of the component (B) used in the composition of the present invention is preferably 0.01 to 50 parts by weight, and more preferably 1 to 20 parts by weight, per 100 parts by weight of the component (A). Is more preferable. This is because if the amount of component (B) is less than 0.01 parts by weight, the adhesiveness of the composition of the present invention to various substrates such as thermosetting organic resins, metals and glass after curing will decrease, and thus 50 parts by weight. This is because the physical properties of the cured product deteriorate if it exceeds the range.

The catalyst for the hydrosilylation reaction of the component (C) used in the composition of the present invention is a component for initiating the hydrosilylation reaction between the alkenyl group and the silicon atom-bonded hydrogen atom in the component (A). . As such a catalyst, conventionally known catalysts can be used. Specifically, chloroplatinic acid and its alcohol solution, platinum olefin complex, platinum diketone complex, platinum acetylacetate complex, platinum and vinyl group-containing siloxane are used. Examples thereof include platinum compounds. In addition to platinum compounds, rhodium compounds such as rhodium triphenylphosphine complexes, palladium compounds such as tetrakis (triphenylphosphine) palladium complexes, ruthenium, iridium, iron,
Examples thereof include compounds such as cobalt, manganese, zinc, lead, aluminum and nickel, and radical generators such as peroxides and azo compounds. These catalysts can be used alone or in combination of two or more, if necessary. Among these, platinum compounds are particularly preferably used because they have excellent reaction activity. The amount of the component (C) added is a catalytic amount, which is the minimum amount required for causing an addition reaction. However, when a platinum compound is used, the amount of the component (A) is 1 million weight. The amount of platinum metal is preferably 0.01 to 1,000 parts by weight, more preferably 0.1 to 100 parts by weight, based on parts.

The composition of the present invention comprises the above-mentioned components (A) to (C). In addition to these components, a compound which inhibits the hydrosilylation reaction in order to improve the storage stability of the composition of the present invention. May be added. As such compounds, conventionally known compounds can be used, and examples thereof include phosphorus compounds such as triphenylphosphine, nitrogen-containing compounds such as tributylamine and tetramethylethylenediamine and benzotriazole, sulfur-containing compounds, acetylene compounds, and alkenyl groups. Examples thereof include compounds having two or more, alkynyl group-containing compounds, hydroperoxy compounds, and maleic acid derivatives. Among these, 1,3-divinyl-1,
Compounds having two or more alkenyl groups such as 1,3,3-tetramethyldisiloxane, two alkynyl groups in one molecule
In addition to compounds having two or more groups, compounds having an alkynyl group and an alcoholic hydroxyl group in one molecule, maleic acid diesters are preferably used. If the addition amount of these compounds is too small, the hydrosilylation reaction inhibition effect cannot be obtained,
Conversely, if it is too much, the curing itself will be hindered,
It is preferably in the range of 0.1 to 50,000 parts by weight with respect to 1 million parts by weight of the total of the components (A) and (B). In addition to the above, a conventionally known adhesion promoter can be added to the composition of the present invention in order to improve the adhesion to metal or glass. Furthermore, in the composition of the present invention,
In order to supplement the silicon atom-bonded hydrogen atoms for the alkenyl group in the component (B), an organohydrogensiloxane having two or more silicon atom-bonded hydrogen atoms can be added. Its chemical structure is linear, cyclic, reticulated,
It may be star-shaped, and oligomers to high molecular weight compounds can be used. Further, in this organohydrogensiloxane, the group bonded to a silicon atom other than the silicon atom-bonded hydrogen atom is preferably a monovalent hydrocarbon group containing no aliphatic unsaturated bond, such as a methyl group, an ethyl group, Examples thereof include alkyl groups such as propyl group, butyl group, pentyl group and hexyl group; aryl groups such as phenyl group, tolyl group and xylyl group; aralkyl groups such as benzyl group and phenethyl group. In addition to this, the organohydrogensiloxane may contain a small amount of a hydroxyl group, an alkoxy group, a haloalkyl group or the like within a range not impairing the object of the present invention, but it is economical and available. From the standpoint of ease, it is preferable that at least half of the groups bonded to the silicon atom are methyl groups. Examples of such an organohydrogensiloxane include trimethylsiloxy group-blocked methylhydrogenpolysiloxane at both ends, trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer at both terminals, and trimethylsiloxy group-blocked diphenylsiloxane / methylhydrogen at both terminals. Gen Siloxane Copolymer, Dimethylsiloxy Group-Capped Dimethyl Siloxane / Methyl Hydrogen Siloxane Copolymer, Cyclic Methyl Hydrogen Polysiloxane, Formula: Siloxane unit represented by SiO _4/2 and formula:

[Chemical 19] A resin copolymer comprising a siloxane unit represented by
Formula: Siloxane unit represented by SiO _4/2 , Formula: (CH ₃ ) ₃ SiO
Siloxane unit and formula represented by _1/2 :

[Chemical 20] An example is a resin copolymer having a siloxane unit represented by In addition to these, the composition of the present invention includes a pigment for coloring, a reinforcing filler for improving strength, a plasticizer for improving workability and melting property during heating, and a thermal conductivity for improving thermal conductivity. Additives or fillers for improving conductivity can be blended.

Such a composition of the present invention is rapidly cured by, for example, applying it to the surface of various substrates and heating it in the temperature range of 50 to 250 ° C., preferably 110 to 230 ° C. And becomes a rubber-like or resin-like cured product. The hardness of the thus obtained cured product is usually in the range of 1 to 100, and preferably in the range of 10 to 90, according to the JIS A rubber hardness meter.

The integrated product of the cured product of the present invention and the substrate is obtained by integrating the cured product of the curable organopolysiloxane composition of the present invention with various substrates. Examples of the base material include organic resins such as phenol resin, epoxy resin, polybutylene terephthalate resin and polycarbonate resin; metals such as copper, aluminum and stainless steel; glass, carbon fiber and metal oxide. The integrated product of the present invention is obtained by applying the composition of the present invention to the surface of various base materials.
It can be produced by heating and curing under a temperature condition of up to 250 ° C., or by applying an organic resin or the like to the cured product of the composition of the present invention and curing it. Examples of the form include an integrated product in which a cured product of the composition of the present invention is adhered to the surface of a substrate, and an integrated product in which two types of substrates are joined by the cured product of the composition of the present invention.

When the curable organopolysiloxane composition of the present invention as described above is applied to the surface of various base materials and heated, the silicone component diffused in a slight amount from the composition is also satisfactorily cured, and The feature is that an integrated product that is firmly adhered to the material can be obtained. Taking advantage of such characteristics, the composition of the present invention is suitably used, for example, as a silicone adhesive.

[0015]

EXAMPLES The present invention will be described in detail below with reference to examples. In the examples, the viscosity is a measured value at 25 ° C.

[0016]

[Reference Example 1] A 1-liter flask equipped with a stirrer, a thermometer, and a cooling tube had an average molecular formula:

[Chemical 21] 25.6 g (36.9 mmol) of polydimethylsiloxane with vinyl dimethylsiloxy groups blocked at both ends, octamethylcyclotetrasiloxane 880.2 g (2.97 mol), and 1,3,5,7-tetramethylcyclotetrasiloxane 8.8 g (36.8 mmol) ) And 0.54 g (3.6 mmol) of trifluoromethanesulfonic acid,
These were heated and stirred under a temperature condition of 80 to 90 ° C. for 9 hours.
In this reaction mixture, the molar ratio of silicon atom-bonded hydrogen atoms to vinyl groups was 2. After completion of stirring, the mixture was cooled to room temperature and 0.54 g (7.3 mmol) of diethylamine was added to neutralize. Then, the low boiling point substances were distilled off from the reaction mixture by heating at 100 ° C. under reduced pressure, the by-produced salts were filtered off, and 767
Grams of a colorless transparent polymer were obtained. This polymer was further subjected to removal of low-boiling substances with a thin-film distillation apparatus under the conditions of 200 ° C./1 mmHg to obtain 740 g of a colorless transparent polymer. This is gel permeation chromatography (GP
When analyzed by C), the number average molecular weight of the obtained polymer was 17,842, the polydispersity was 2.00, and the peak area ratio was 100%. In addition, the presence of low molecular weight siloxane was not confirmed in this polymer. Furthermore, when analyzed by silicon-nuclear magnetic resonance spectrum ( ²⁹ Si-NMR), it was found that the obtained polymer was an organopolysiloxane having a vinyl group and a silicon atom-bonded hydrogen atom represented by the following average molecular formula. . In this organopolysiloxane, the molar ratio of silicon atom-bonded hydrogen atoms to vinyl groups was 1.9.

[Chemical formula 22]

[0017]

[Reference Example 2] Organopolysiloxa synthesized in Reference Example 1
To 720 g of water, add 1500 ml of acetone and stir for 30 minutes.
After stirring, the mixture was allowed to stand for 1 hour and the upper layer was extracted. This operation
Repeat the above two times to heat the low boiling point substances from the remaining lower layer.
Evaporation under reduced pressure gave 669 g of a colorless transparent polymer. this
Analysis by GPC revealed that
The average molecular weight is 30491, the polydispersity is 1.50, and the peak
The area ratio was 100%. In this polymer, low molecular weight
The presence of a quantity of siloxane was not confirmed. further ²⁹Si−
When analyzed by NMR, the obtained polymer was
Vinyl group and silicon atom-bonded hydrogen source represented by average molecular formula
Was found to be an organopolysiloxane with a child
It was In addition, in this organopolysiloxane,
The molar ratio of hydrogen atoms bonded to silicon atoms was 2.2.

[Chemical formula 23]

[0018]

[Reference Example 3] In a 1 liter flask equipped with a stirrer, a thermometer, and a condenser tube, 6.86 g (36.9 mmol) of 1,3-divinyltetramethyldisiloxane, 908.7 g (3.07 mol) of octamethylcyclotetrasiloxane and hydroxylation were added. 0.18 g (3.2 mmol) of potassium was added, and these were heated and stirred under the temperature condition of 150 to 160 ° C. for 10 hours. After completion of stirring, the mixture was cooled to room temperature and 0.88 g (7.3 mmol) of vinyldimethylchlorosilane was added to neutralize. Next, the low boiling point substance was distilled off from this reaction mixture at 150 ° C. under reduced pressure, and the by-produced salt was filtered off to obtain a colorless transparent polymer. This polymer is further 200
Low boiling point substances were removed under the condition of ° C / 1 mmHg to obtain 740 g of a colorless transparent polymer. When analyzed by GPC, the number average molecular weight of the obtained polymer was 24125, the dispersity was 1.67, and the peak area ratio was 100%. In addition, the presence of low molecular weight siloxane was not confirmed in this polymer. Further, since the vinyl group content by the titration method using iodine monochloride was 0.22% by weight, it was found that the obtained polymer was a vinyl group-containing organopolysiloxane represented by the following average molecular formula.

[Chemical formula 24]

[0019]

[Reference Example 4] Using 720 g of the organopolysiloxane synthesized in Reference Example 3, acetone extraction was carried out in the same manner as in Reference Example 2 to obtain 660 g of a colorless transparent polymer. When this was analyzed by GPC, the number average molecular weight of the obtained polymer was 27471, the dispersity was 1.50, and the peak area ratio was 100%. In addition, the presence of low molecular weight siloxane was not confirmed in this polymer. Further, since the vinyl group content by the titration method using iodine monochloride was 0.20% by weight, it was found that the obtained polymer was a vinyl group-containing organopolysiloxane represented by the following average molecular formula.

[Chemical 25]

[0020]

Example 1 31.59 g of organopolysiloxane synthesized in Reference Example 2 (content of silicon atom-bonded hydrogen atoms: 4.2 mmol, content of silicon atom-bonded vinyl groups: 1.9 mmol),
Fumed silica treated with hexamethyldisilazane [Nippon Aerosil Co., Ltd., trade name Aerosil 200B
X] 4.01 g, phenylbutynol 5.5 mg,
0.121 g (vinyl group content 0.3 mmol) of the reaction product of a dimethylsiloxane / methylvinylsiloxane copolymer capped with silanol groups at both ends and 3-glycidoxypropyltrimethoxysilane, formula:

[Chemical formula 26] Hydroxyphenyl group-containing organosilicon compound represented by
4.42 g (vinyl group content 15.8 mmol), both ends trimethylsiloxy group blocked methyl hydrogen polysiloxane 1.11 g (silicon atom-bonded hydrogen atom content 17.5
Mmol) and chloroplatinic acid and 1,3-divinyltetramethyldisiloxane complex are added in an amount such that the platinum metal content is 1.7 ppm with respect to the total composition to prepare a curable organopolysiloxane composition. did. In this composition, the molar ratio of silicon atom-bonded hydrogen atoms in the trimethylsiloxy group-blocked methylhydrogenpolysiloxane at both ends to the aliphatic unsaturated bonds in the hydroxyphenyl group-containing organosilicon compound was 1.2. The obtained curable organopolysiloxane composition was applied to a silicon chip.
(10 mm × 10 mm × 1 mm) was applied in a loop on the plate, and this was left to cure in an oven at 180 ° C. for 30 minutes.
The rubber hardness of the thus obtained organopolysiloxane cured product was 37 when measured with a JIS A type rubber hardness meter. Then, a curable epoxy resin composition [Toto Kasei Co., Ltd., trade name Epototo YDF8170: 50 parts, Asahi Kasei Kogyo Co., Ltd., trade name Novacure
HX-3721: 20 parts and Ouchi Shinko Chemical Industry Co., Ltd., trade name Nocrac NS5: 30 parts composition] and place it in an oven at 180 ° C for 1 hour to cure, An integrated product of a siloxane cured product, a silicon chip and an epoxy resin was manufactured. Observation of this integrated product with an ultrasonic flaw detector revealed that the interfaces between the epoxy resin, the organopolysiloxane cured product, and the silicon chip and the interface where the three were in contact (interface D in FIG. 1; the exudation portion of the silicone component). No peeling was observed in). Than this,
The organopolysiloxane cured product adheres firmly,
In particular, it was found that the silicone component that diffused and oozes out also exhibits good adhesiveness. The results are shown in FIG. 1 and Table 1.

[0021]

Comparative Example 1 110.54 g of the organopolysiloxane synthesized in Reference Example 4, fumed silica treated with hexamethyldisilazane [manufactured by Nippon Aerosil Co., Ltd .; trade name Aerosil 200BX] 14.03 g, phenylbutynol 4
2 mg, reaction product of silanol-capped dimethylsiloxane / methylvinylsiloxane copolymer at both ends and 3-glycidoxypropyltrimethoxysilane 0.419
Gram, formula:

[Chemical 27] Hydroxyphenyl group-containing organosilicon compound represented by
With 15.48 g, 4.57 g of methylhydrogenpolysiloxane blocked with trimethylsiloxy groups at both ends (silicon atom-bonded hydrogen atom content 72.2 mmol) and chloroplatinic acid
A curable organopolysiloxane composition was prepared by adding and mixing 1,3-divinyltetramethyldisiloxane complex in an amount such that the amount of platinum metal was 1 ppm with respect to the entire composition. In this composition, the molar ratio of the silicon atom-bonded hydrogen atoms in the methylhydrogenpolysiloxane blocked with trimethylsiloxy groups at both ends to the vinyl groups in the hydroxyphenyl group-containing organosilicon compound was 1.1. This composition was cured in the same manner as in Example 1, and the obtained organopolysiloxane cured product had a rubber hardness of JIS A.
It was 37 as measured by a rubber hardness tester. Further, in the same manner as in Example 1, an integrated product of an organopolysiloxane cured product, a silicon chip and an epoxy resin was produced and observed with an ultrasonic flaw detector. Although no peeling was observed at the interface between the chip and the cured product of organopolysiloxane (interfaces A and C in FIG. 1),
Peeling was observed at the interface where the three come into contact (interface D in FIG. 1; the exudation portion of the silicone component). From this, it was found that the adhesiveness at the exuded portion was insufficient. The results are shown in FIG. 1 and Table 1.

[0022]

[Comparative Example 2] Reaction of 9.90 g of organopolysiloxane synthesized in Reference Example 1, 1.00 mg of phenylbutynol, silanol group-capped dimethylsiloxane / methylvinylsiloxane copolymer at both ends with 3-glycidoxypropyltrimethoxysilane A curable organopolysiloxane composition was prepared by adding 45 mg of the product and a complex of chloroplatinic acid and 1,3-divinyltetramethyldisiloxane in an amount such that the platinum metal content was 5 ppm with respect to the entire composition. Was prepared. This composition was cured in the same manner as in Example 1 to produce an integrated product of an organopolysiloxane cured product, a silicon chip and an epoxy resin, which was observed with an ultrasonic flaw detector. Peeling was not observed at the interface between the siloxane cured products (interface C in FIG. 1), but at the interfaces between the epoxy resin and the organopolysiloxane cured product and at the three contact points (interfaces A and D in FIG. 1). Admitted. From this, it was revealed that the obtained composition had insufficient adhesion.
The results are shown in FIG. 1 and Table 1.

[0023]

[Example 2] 31.59 g of the organopolysiloxane synthesized in Reference Example 2 (content of silicon atom-bonded hydrogen atoms: 4.2 mmol, content of silicon atom-bonded vinyl groups: 1.9 mmol),
Fumed silica treated with hexamethyldisilazane [Nippon Aerosil Co., Ltd., trade name Aerosil 200B
X] 4.01 g, phenylbutynol 5.5 mg,
0.121 g (vinyl group content 0.3 mmol) of a reaction product of a silanol group-capped dimethyl siloxane / methyl vinyl siloxane copolymer having both ends blocked with 3-glycidoxypropyltrimethoxysilane, 4.00 g eugenol (vinyl group content 24.4 mmol ), 1.73 g of methylhydrogenpolysiloxane capped with trimethylsiloxy groups at both ends (silicon atom-bonded hydrogen atom content 27.2 mmol), and platinum metal chloroplatinic acid complex with 1,3-divinyltetramethyldisiloxane as the entire composition of platinum metal. A curable organopolysiloxane composition was prepared by adding and blending it in an amount of 1.8 ppm. In this composition, a reaction product of the above-mentioned dimethylsiloxane / methylvinylsiloxane copolymer capped with silanol groups at both ends and 3-glycidoxypropyltrimethoxysilane and trimethylsiloxy groups at both terminals for an aliphatic unsaturated bond in eugenol The molar ratio of silicon atom-bonded hydrogen atoms in the blocked methyl hydrogen polysiloxane was 1.1. The obtained curable organopolysiloxane composition was treated with a silicon chip (10 mm × 1
(0 mm x 1 mm) and apply it in a circle, and apply this to 150
It was left to cure in an oven at 30 ° C. for 30 minutes. The rubber hardness of the thus obtained organopolysiloxane cured product was 39 as measured by a JIS A type rubber hardness meter. Then, a curable epoxy resin composition [manufactured by Tohto Kasei Co., Ltd., trade name Epotote YDF8170:
50 parts, Asahi Kasei Kogyo Co., Ltd., trade name Novacure HX-3721: 20
Part and Ouchi Shinko Chemical Industry Co., Ltd., trade name Nocrac NS
5:30 parts of the composition] was placed and allowed to stand in an oven at 180 ° C. for 1 hour to be cured to produce an integrated product of a cured organopolysiloxane, a silicon chip and an epoxy resin. Observation of this integrated product with an ultrasonic flaw detector revealed that the interfaces between the epoxy resin, the organopolysiloxane cured product, and the silicon chip and the interface where the three were in contact (interface D in FIG. 1; the exudation portion of the silicone component). No peeling was observed in). From this, it was found that the cured product of the organopolysiloxane strongly adhered, and particularly the silicone component that had diffused and exuded also exhibited good adhesion. The results are shown in FIG. 1 and Table 1.

[0024]

[Table 1]

[0025]

The curable organopolysiloxane composition of the present invention is excellent in curability because it comprises the above-mentioned components (A) to (C), and in particular, a slight amount diffuses from the composition before or during curing. The silicone component exuded as a result is also cured well, and the obtained cured product has the characteristics of being able to adhere well to various substrates.

[Brief description of drawings]

FIG. 1 is an enlarged cross-sectional view of a portion of an integrated product of an organopolysiloxane cured product, a silicon chip, and an epoxy resin, which is in contact with each other.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C08K 3/40 C08K 3/40 C08L 101/00 C08L 101/00 C09D 183/07 C09D 183/07 C09J 183/07 C09J 183/07 (72) Inventor Kazuki Nakayoshi 2-2 Chikusaigan, Ichihara-shi, Chiba Toray Dow Corning Silicone Co., Ltd. Research and Development Headquarters (72) Osamu Mitani 2-2 Chikusaigan, Ichihara-shi, Chiba Toray Dow Corning Silicone Co., Ltd. Research and Development Division (56) Reference JP 56-49754 (JP, A) JP 58-89650 (JP, A) JP 3-252458 (JP, A) JP Hei 7-11141 (JP, A) JP 2000-169715 (JP, A) JP 2000-281686 (JP, A) JP 46-28190 (JP, B1) (58) Fields investigated (Int.Cl . ^7, B name) C08L 83/00 - 83/16 CAPLUS (STN) REGISTRY (STN)

Claims (7)

(57) [Claims] 1. (A) An organopolysiloxane having an average of two or more alkenyl groups and two or more silicon-bonded hydrogen atoms in the same molecule, (B) an alkenyl group and a hydroxyphenyl group in one molecule. A curable organopolysiloxane composition comprising a compound containing C and a catalyst for hydrosilylation reaction (C). 2. The component (A) has a silicon atom-bonded alkenyl group content and a silicon atom-bonded hydrogen atom content ratio, respectively.
The curable organopolysiloxane composition according to claim 1, wherein the organopolysiloxane is 0.025 to 5 mol% and the molar ratio of silicon-bonded hydrogen atoms to alkenyl groups is 0.1 to 200. 3. The curable organopolysiloxane composition according to claim 1, wherein the component (B) is an organosilicon compound containing an alkenyl group and a hydroxyphenyl group in one molecule. 4. The component (B) has the formula: [Chemical 1] [Wherein X is an alkenyl group and Z is a formula: [Chemical 2] Is an ester group or a phenylene group represented by
A divalent hydrocarbon group having 1 or more carbon atoms or a formula: -R²−
O-R²− (Where R²Is a divalent hydrocarbon group. )
Y is a substituted or unsubstituted hydroxy group.
Is a phenyl group and R ¹Is the same kind of having 2 or more carbon atoms
Is a different divalent hydrocarbon group, R is an aliphatic unsaturated bond
The same or different monovalent hydrocarbon groups containing no
m, p, r and s are 0 or 1 and n is 0-2
And q is an integer from 0 to 7. ] Organosiliconization
The curable organopolysiloxane according to claim 3, which is a compound.
Sun composition. 5. A cured product obtained by curing the curable organopolysiloxane composition according to claim 1. 6. An integrated product of a cured product obtained by integrating the cured product of the curable organopolysiloxane composition according to any one of claims 1 to 4 with a substrate. 7. The integrated product of the cured product and the substrate according to claim 6, wherein the substrate is an organic resin, metal or glass.