JPH09310024A - Curable organopolysiloxane composition and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable organopolysiloxane composition capable of suppressing the exudation of a low-viscosity liquid organopolysiloxane contained in order to impart adhesion thereto in the course of curing and provide a semiconductor device comprising a semiconductor element coated with a cured product of the composition. SOLUTION: This curable organopolysiloxane composition comprises (A) a liquid organopolysiloxane, having two alkenyl groups and one alkoxy group and prepared by thickening (a) a liquid organopolysiloxane having two alkenyl groups, (b) a low-viscosity liquid organopolysiloxane having one alkenyl group and one alkoxy group in an amount so as to provide 0.1-20 pts.wt. thereof based on 100 pts.wt. component (a) and (c) a liquid organopolysiloxane having 2 hydrogen atoms in an amount so as not to cure the component A in the presence of (d) a metallic catalyst for a hydrosilylating reaction in an amount so as to afford 0.01-1000ppm metallic atoms on the weight bases based on the composition by a hydrosilylating reaction and (B) a liquid organopolysiloxane having two hydrogen atoms in a sufficient amount so as to cure the composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable organopolysiloxane composition and a semiconductor device. More specifically, during the course of curing, exudation of a low-viscosity liquid organopolysiloxane contained to impart adhesiveness is suppressed. The present invention relates to a curable organopolysiloxane composition and a semiconductor device having excellent reliability, which is obtained by coating a semiconductor element with a cured product of this composition.

[0002]

Liquid organopolysiloxanes having at least two alkenyl groups bonded to silicon atoms per minute, liquid organopolysiloxanes having at least two hydrogen atoms bonded to silicon atoms in one molecule, and hydrosilanes. The curable organopolysiloxane composition composed of a metal catalyst for a cation reaction cures to form a cured product having excellent electrical insulation properties.
It is used as a potting agent and a protective coating agent, and particularly as a protective coating agent for semiconductor devices. Generally, as a component for improving the adhesiveness of the cured product, the curable organopolysiloxane composition contains at least one silicon atom-bonded alkoxy group and silicon atom-bonded alkenyl group per molecule. A low-viscosity liquid organopolysiloxane having each of these is used.

However, such a curable organopolysiloxane composition has a problem that during curing, the low-viscosity liquid organopolysiloxane oozes out to contaminate the periphery of the cured product. For this reason, when a semiconductor element is coated with a cured product of such a curable organopolysiloxane composition, the bondability of the semiconductor element with the bonding wire is reduced, and the reliability of the obtained semiconductor device is reduced. There was a problem of becoming scarce.

[0004]

The present inventors have arrived at the present invention as a result of extensive studies on the above problems. That is, an object of the present invention is to provide a semiconductor containing a curable organopolysiloxane composition in which exudation of a low-viscosity liquid organopolysiloxane contained for imparting adhesiveness is suppressed during curing, and a cured product of this composition. An object of the present invention is to provide a highly reliable semiconductor device formed by coating an element.

[0005]

The curable organopolysiloxane composition of the present invention comprises (A) (a) a liquid organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule; ) A low-viscosity liquid having at least one (b) alkenyl group bonded to silicon atom and at least one alkoxy group bonded to silicon atom in one molecule in an amount of 0.1 to 20 parts by weight with respect to 100 parts by weight of the component). In the present composition, an organopolysiloxane and a liquid organopolysiloxane having at least two hydrogen atoms bonded to a silicon atom in one molecule (c) which does not cure the component (A) are used. 0.01 by weight
˜1,000 ppm of (d) at least two alkenyl groups bonded to silicon atom, which are thickened by hydrosilation reaction in the presence of a metal catalyst for hydrosilation reaction, in one molecule. A liquid organopolysiloxane having at least one silicon-bonded alkoxy group in each molecule, and (B) a silicon atom-bonded hydrogen atom in one molecule sufficient to cure the composition. It is characterized in that it comprises at least two liquid organopolysiloxanes. The semiconductor device of the present invention is characterized in that a semiconductor element is coated with a cured product of the curable organopolysiloxane composition.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION First, the curable organopolysiloxane composition of the present invention will be described in detail. The liquid organopolysiloxane as the component (A) is the main component of the present composition and has at least two alkenyl groups bonded to silicon atoms in one molecule and at least alkoxy groups bonded to silicon atoms in one molecule. It is characterized by having one.
The component (A) is composed of (a) a liquid organopolysiloxane having at least two alkenyl groups bonded to a silicon atom in one molecule, (b) an alkenyl group bonded to a silicon atom and an alkoxy bonded to a silicon atom. (D) Hydrosilation of a low-viscosity liquid organopolysiloxane having at least one group in each molecule and (c) a liquid organopolysiloxane having at least two hydrogen atoms bonded to silicon atoms in each molecule. It is prepared by increasing the viscosity by a hydrosilation reaction in the presence of a metal catalyst for reaction.

The liquid organopolysiloxane as the component (a) is a main raw material for preparing the component (A) and is characterized by having at least two alkenyl groups bonded to silicon atoms in one molecule. Examples of the molecular structure of this component (a) include linear, partially branched linear, branched, and network structures, and the linear structure is particularly preferable.
Examples of the alkenyl group bonded to the silicon atom in the component (a) include vinyl group, allyl group, butenyl group, pentenyl group,
A hexenyl group is exemplified, and a vinyl group is particularly preferable. Examples of the bonding position of the alkenyl group include the molecular chain end and / or the molecular chain side chain. Also,
Examples of the group bonded to a silicon atom other than the alkenyl group in the component (a) include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group; a phenyl group, a tolyl group, Aryl groups such as xylyl group and naphthyl group; aralkyl groups such as benzyl group and phenethyl group; chloromethyl group, 3-chloropropyl group, 3,
A substituted or unsubstituted monovalent hydrocarbon group such as a halogenated alkyl group such as a 3,3-trifluoropropyl group is exemplified, and a methyl group and a phenyl group are particularly preferable. The viscosity of the component (a) at 25 ° C. is 100 to
Preferably it is in the range of 1,000,000 centipoise.

The component (b), a low-viscosity liquid organopolysiloxane, is a component for imparting adhesiveness to the present composition, and contains an alkenyl group bonded to a silicon atom and an alkoxy group bonded to a silicon atom in one molecule. It is characterized by having at least one each. Examples of the molecular structure of the component (b) include straight-chain, partially branched straight-chain, branched-chain, cyclic, and net-like, and particularly straight-chain, branched-chain, and net-like. preferable. Examples of the alkenyl group bonded to the silicon atom in the component (b) include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group.
It is preferably a vinyl group. Examples of the alkoxy group bonded to the silicon atom in the component (b) include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a methoxyethoxy group, and a methoxy group is particularly preferable. Examples of the group bonded to the silicon atom other than the alkenyl group and the alkoxy group in the component (b) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group,
Alkyl group such as heptyl group; aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group; aralkyl group such as benzyl group, phenethyl group; chloromethyl group, 3-chloropropyl group, 3,3,3-tri Substituted or unsubstituted monovalent hydrocarbon group such as halogenated alkyl group such as fluoropropyl group; glycidoxyalkyl group such as 3-glycidoxypropyl group and 4-glycidoxybutyl group; 2-
(3,4-epoxycyclohexyl) ethyl group, 3-
(3,4-epoxycyclohexyl) alkyl group such as (3,4-epoxycyclohexyl) propyl group; 4-
Examples include epoxy group-containing monovalent organic groups such as oxiranylalkyl groups such as oxiranylbutyl groups and 8-oxiranyloctyl groups, which can impart good adhesiveness to various substrates. Since it is possible, at least 1 in one molecule
It is preferable that the individual is this epoxy group-containing monovalent organic group. The component (b) is a low-viscosity liquid, and the viscosity at 25 ° C. is preferably within the range of 1 to 500 centipoise.

Among the components (b), a low viscosity having at least one alkenyl group bonded to a silicon atom, an alkoxy group bonded to a silicon atom, and an epoxy group-containing monovalent organic group bonded to a silicon atom in each molecule. As the liquid organopolysiloxane, the average unit formula: (R ¹ SiO _3/2 ) _a (R ² ₂ SiO _2/2 ) _b (R ² ₃ SiO _1/2 ) _c (R
An example is a low-viscosity liquid organopolysiloxane represented by ³ O _1/2 ) _d . R ¹ in the above formula is a monovalent organic group containing an epoxy group, and is a glycidoxyalkyl group such as 3-glycidoxypropyl group or 4-glycidoxybutyl group; 2- (3,4-epoxycyclohexyl) (3,4-Epoxycyclohexyl) alkyl group such as ethyl group and 3- (3,4-epoxycyclohexyl) propyl group; oxiranylalkyl group such as 4-oxiranylbutyl group and 8-oxiranyloctyl group In particular, a glycidoxyalkyl group is preferable, and a 3-glycidoxypropyl group is more preferable. R ² in the above formula is a substituted or unsubstituted monovalent hydrocarbon group, a methyl group,
Alkyl groups such as ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group; alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group; phenyl group, tolyl group, xylyl group, Aryl groups such as naphthyl group; aralkyl groups such as benzyl group and phenethyl group; chloromethyl group, 3-chloropropyl group,
Substituted or unsubstituted monovalent hydrocarbon groups such as halogenated alkyl groups such as 3,3,3-trifluoropropyl group are exemplified, and it is necessary that at least one of the components (b) is an alkenyl group. is there. Further, R ³ in the above formula is an alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a methoxyethyl group, and a methyl group and an ethyl group are particularly preferable. In the above formula, a is a positive number, b is a positive number, c is 0 or a positive number, and d
Is a positive number.

The amount of the component (b) is required to be 0.1 to 20 parts by weight with respect to 100 parts by weight of the component (a), and particularly, the amount is 0.1 to 10 parts by weight. Is preferred. This is because if the amount of the component (b) is less than 0.1 parts by weight with respect to 100 parts by weight of the component (a), the adhesiveness of the obtained cured product will be poor.
This is because if the amount exceeds 20 parts by weight, the storage stability of the resulting curable organopolysiloxane composition becomes poor.

The liquid organopolysiloxane as the component (c) is a component for chemically bonding the component (a) and the component (b), and contains at least two hydrogen atoms bonded to silicon atoms in one molecule. It is characterized by having. Examples of the molecular structure of the component (c) include linear, partially branched linear, branched, cyclic, and network structures, and the linear structure is particularly preferable. Further, the bonding position of the hydrogen atom bonded to the silicon atom in the component (c) is exemplified by the molecular chain terminal and / or the molecular chain side chain, and particularly preferably both molecular chain terminals. Examples of the group bonded to a silicon atom other than a hydrogen atom in the component (c) include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group; a phenyl group, a tolyl group, Aryl group such as xylyl group and naphthyl group; Aralkyl group such as benzyl group and phenethyl group; Substitution of halogenated alkyl group such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group and the like, or An unsubstituted monovalent hydrocarbon group is exemplified, and a methyl group and a phenyl group are particularly preferable. The viscosity of the component (c) at 25 ° C. is 1
It is preferably in the range of 100,000 centipoise.

It is necessary to use the component (c) in an amount that does not cure the component (A). Specifically, the total amount of the alkenyl groups bonded to silicon atoms in the components (a) and (b) is 1 total. It is preferable that the amount of hydrogen atoms bonded to silicon atoms in the component (c) is 0.01 to 0.95 mol per mol. This is because the total of 1 mol of the alkenyl groups bonded to the silicon atom in the components (a) and (b) is (c)
When the hydrogen atom bonded to the silicon atom in the component is less than 0.01 mol, the components (a) and (b) cannot be chemically bonded sufficiently, and the object of the present invention cannot be achieved. This is because, when it exceeds 0.95 mol, the component (A) is cured by the hydrosilylation reaction,
This is because the viscosity becomes so high that it cannot be used.

The metal-based catalyst for the hydrosilation reaction of the component (d) comprises a alkenyl group bonded to the silicon atom in the components (a) and (b) and a hydrogen atom bonded to the silicon atom in the component (c). Is a catalyst for the hydrosilation reaction, and examples thereof include a platinum-based catalyst, a rhodium-based catalyst, and a palladium-based catalyst, and a platinum-based catalyst is particularly preferable. Examples of the platinum-based catalyst include platinum-based powder such as platinum fine powder, platinum black, platinum-supported silica fine powder, platinum-supported activated carbon, chloroplatinic acid, alcohol solution of chloroplatinic acid, olefin complex of platinum, alkenylsiloxane complex of platinum, and the like. Is exemplified.

In the present composition, the component (d) comprises 0.01 to 1,000 ppm by weight of metal atoms in the catalyst.
The amount must be within the range. this is,
When the addition amount of the component (d) is such that the metal atom in the catalyst is 0.01 ppm in weight unit in the present composition, the hydrosilylation reaction does not proceed sufficiently. This is because the component (A) cannot be thickened, and further, the composition cannot be cured by a hydrosilation reaction. This is because the ration reaction is not significantly promoted, but rather uneconomical. It is also possible to add the remaining (d) component after thickening the (A) component by a hydrosilation reaction with a part of the (d) component.

The hydrosilation reaction, which is carried out by uniformly mixing the components (a) to (d), proceeds at room temperature or by heating, but the hydrosilation reaction can be carried out rapidly by heating. You can The heating temperature is preferably in the range of 50 to 200 ° C, and particularly preferably in the range of 80 to 180 ° C. In this hydrosilation reaction, stirring is not particularly required as long as components (a) to (d) are uniformly mixed, but it is also preferable to perform the stirring under heating. (a)
When the components (1) to (d) are uniformly mixed to carry out the hydrosilation reaction, other components such as precipitated silica, fumed silica, calcined silica, titanium oxide, alumina, glass, quartz, aluminosilicate, iron oxide, Fillers such as zinc oxide, calcium carbonate, and carbon black; these fillers can be used as organohalosilanes, organoalkoxysilanes,
Fillers treated with organosilicon compounds such as organosilazanes; fine powders of organic resins such as silicone resins and fluororesins;
Conductive powder such as silver and copper; other dyes, pigments, flame retardants,
A solvent or the like can be added. Also, in order to control the rate of this hydrosilation reaction, 3-methyl-1
Alkyne alcohols such as -butyn-3-ol, 3,5-dimethyl-1-hexyne-3-ol, phenylbutynol; 3-methyl-3-penten-1-yne, 3,5
-Enyne compounds such as -dimethyl-3-hexen-1-yne; 1,3,5,7-tetramethyl-1,3,5,7-
Tetravinylcyclotetrasiloxane, 1,3,5,7
-Addition reaction inhibitors such as tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane and benzotriazole may be added. The amount of addition reaction inhibitor added is 0.000 per 100 parts by weight of component (A).
It is preferably 1 to 5 parts by weight.

The liquid organopolysiloxane as the component (B) is a curing agent for the present composition and is characterized by having at least two hydrogen atoms bonded to silicon atoms in one molecule. Examples of the molecular structure of the component (B) include linear, partially branched linear, branched, cyclic, and net-like, and particularly,
It is preferably linear. Examples of the bonding position of the hydrogen atom bonded to the silicon atom in the component (B) include the molecular chain terminal and / or the molecular chain side chain. Examples of the group bonded to a silicon atom other than a hydrogen atom in the component (B) include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group; a phenyl group, a tolyl group, Aryl group such as xylyl group and naphthyl group; Aralkyl group such as benzyl group and phenethyl group; Substitution of halogenated alkyl group such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group and the like, or An unsubstituted monovalent hydrocarbon group is exemplified, and in particular, a methyl group,
It is preferably a phenyl group. The viscosity of the component (B) at 25 ° C. is preferably in the range of 1 to 100,000 centipoise. This (B) component is (A)
It may be the same as or different from the component (c) used as a raw material for preparing the components.

The component (B) is required to be used in an amount sufficient to cure the composition, and specifically, to 1 mol of the alkenyl group bonded to the silicon atom in the component (A). , The hydrogen atom bonded to the silicon atom in the component (B) is 0.
The amount is preferably in the range of 5 to 10 mol.
This is sufficient if the amount of hydrogen atoms bonded to the silicon atom in the component (B) is less than 0.5 mol with respect to 1 mol of the alkenyl group bonded to the silicon atom in the component (A). This is because it does not cure, and when it exceeds 10 mol, foaming occurs during curing or the physical properties of the obtained cured product deteriorate.

The composition is prepared by uniformly mixing the component (A) and the component (B). When the composition is prepared, other optional components may be used as long as the object of the present invention is not impaired. The above-mentioned fillers, dyes, pigments, flame retardants, solvents, addition reaction inhibitors and the like can be added. When the addition reaction inhibitor is blended, it is preferable to mix it with the component (A) in advance and then mix the component (B) with it.
Further, when the component (A) and the component (B) are mixed, a part of the component (d) may be blended.

The curable organopolysiloxane composition of the present invention is a cured product in which the exudation of a low-viscosity liquid organopolysiloxane contained for imparting adhesiveness during curing is suppressed and the composition is cured to have excellent adhesiveness. Since it can be formed, it can be used as an electric / electronic adhesive, a potting agent, or a protective coating agent, and in particular, can be used as a protective coating agent for semiconductor elements.

Next, the semiconductor device of the present invention will be described in detail. A semiconductor device of the present invention is characterized in that a semiconductor element is coated with a cured product of the above-mentioned curable organopolysiloxane composition. Examples of this semiconductor element include a diode, a transistor, a thyristor, a monolithic IC, and a semiconductor element in a hybrid IC. Further, such semiconductor devices include diodes, transistors, thyristors, monolithic I
Examples include C, hybrid IC, LSI, and VLSI.

A hybrid IC (cross-sectional view) which is an example of the semiconductor device of the present invention is shown in FIG. In the semiconductor device of FIG. 1, a semiconductor element 1 is mounted on a circuit board 2, and the semiconductor element 1 and a circuit wiring 3 connected to an external lead are electrically connected by a bonding wire 4.
A cured product 5 of a curable organopolysiloxane composition is formed on the surface of the semiconductor element 1 so as to cover the semiconductor element 1. Further, the semiconductor element 1 covered with the cured product 5 is formed. Is resin-sealed with the sealing resin 6. Examples of the material of the circuit board 2 include organic resins such as glass fiber reinforced epoxy resin, Bakelite resin, and phenol resin; ceramics such as alumina; metals such as copper and aluminum. Examples of the material of the circuit wiring 3 include copper and silver-palladium. Further, examples of the material of the bonding wire 4 include gold, copper, and aluminum. In addition to the semiconductor element 1, electronic components such as resistors, capacitors and coils may be mounted on the circuit board 2. Further, examples of the material of the sealing resin 6 include epoxy resin, phenol resin, and polyphenylene sulfide resin.

As a method of manufacturing the semiconductor device of the present invention, the semiconductor element 1 is mounted on the circuit board 2, and then the semiconductor element 1 and the circuit wiring 3 are bonded by the bonding wire 4.
After electrically connecting by the above, the above-mentioned curable organopolysiloxane composition is applied to the surface of the semiconductor element 1. As a method of curing the curable organopolysiloxane composition on the semiconductor element 1, a method of allowing it to stand at room temperature or heating it to 50 to 200 ° C. is exemplified. After curing the curable organopolysiloxane composition, the semiconductor element 1 covered with the cured product 5 can be resin-sealed with a sealing resin 6 if necessary.

[0023]

EXAMPLES The curable organopolysiloxane composition and semiconductor device of the present invention will be described in detail with reference to examples. In addition, the viscosity in an Example is a value measured at 25 degreeC. The leaching of the low-viscosity liquid organopolysiloxane during the curing of the curable organopolysiloxane composition and the reliability of the semiconductor device were evaluated as follows.

[Evaluation Method of Exudation of Low Viscosity Liquid Organopolysiloxane] The exudation of low viscosity liquid organopolysiloxane was evaluated by the method shown in FIG. That is, the curable organopolysiloxane composition was applied to the glass fiber reinforced epoxy plate A (5 cm × 5 c by screen printing method).
m) was coated on the m) so as to have a size of 1 cm × 1 cm × 1 mm to prepare 10 test bodies. Five of these test specimens were tested 1 immediately after applying the curable organopolysiloxane composition.
The composition was cured by heating in a hot air circulation oven at 50 ° C. for 2 hours. In addition, the remaining test bodies were coated with the curable organopolysiloxane composition, allowed to stand at 25 ° C. for 6 hours, and then heated in a hot air circulation oven at 150 ° C. for 2 hours to cure the composition. It was And
The average length (a + b) of the low-viscosity liquid organopolysiloxane C exuded from the cured product B on the epoxy plate A
+ C + d) / 4 was obtained, and comparison was made with the average value of these five test bodies.

[Method for Evaluating Reliability of Semiconductor Device] The semiconductor device shown in FIG. 1 was prepared. In this semiconductor device, the semiconductor element 1 is mounted on a circuit board 2 made of glass fiber reinforced epoxy resin having circuit wirings 3 formed by printing on the surface and external leads at ends, and then the semiconductor element 1 is mounted.
A curable organopolysiloxane composition was applied to the surface of the above by a screen printing method to prepare 40 semiconductor devices. Immediately after applying the curable organopolysiloxane composition, 20 of these semiconductor devices were heated for 2 hours in a hot air circulation oven at 150 ° C. to cure the composition. The remaining semiconductor device was left at 25 ° C. for 6 hours and then heated in a hot air circulation type oven at 150 ° C. for 2 hours to cure the composition. Next, the semiconductor element 1 of these semiconductor devices and the circuit wiring 3 were electrically connected by the bonding wire 4. Then, the semiconductor device was resin-sealed with a curable liquid epoxy resin. This epoxy resin is cured by heating it in a hot air circulation oven at 80 ° C for 1 hour and then heating it in a hot air circulation oven at 150 ° C for 2 hours.
It was carried out by heating for an hour. The semiconductor device manufactured in this way is stored under the conditions of 85 ° C. and 85% relative humidity for 10 minutes.
After leaving it for 00 hours, an electrical continuity test between external leads was performed to determine the number of defective semiconductor devices (defective rate).

Example 1 As the component (a), the viscosity was 1
A dimethylpolysiloxane capped with dimethylvinylsiloxy groups at both ends of the molecular chain of 10,000 centipoise (content of vinyl groups bonded to silicon atoms = 0.12% by weight) 64
15 parts by weight of a dimethylsiloxane-methylvinylsiloxane copolymer (capacity of vinyl group bonded to silicon atom = 0.84% by weight) with dimethylvinylsiloxy group blocked at both ends of a molecular chain having a viscosity of 6,000 centipoise. ,
As the component (b), the average unit formula having a viscosity of 20 centipoise:

Embedded image 1 part by weight of an organopolysiloxane represented by (content of vinyl group bonded to silicon atom = 16% by weight), and as component (c), a dimethyl-capped dimethylhydrogensiloxy group-capped dimethyl molecule having a viscosity of 15 centipoise. Polysiloxane (content of hydrogen atoms bonded to silicon atoms =
0.13% by weight), and as the component (d), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (in the composition, the platinum metal in the complex is An amount of 5 ppm by weight), 16 parts by weight of fumed silica having a specific surface area of 200 m ² / g, the surface of which has been hydrophobically treated with hexamethyldisilazane as an optional component, are uniformly mixed to obtain a viscosity. A mixture of 4,100 poise was prepared, and then the mixture was heated at 150 ° C. for 30 minutes to carry out a hydrosilation reaction to prepare a grease-like organopolysiloxane having a viscosity of 8,300 poise.

Next, this liquid organopolysiloxane 1
To 100 parts by weight, as an addition reaction inhibitor, 3-phenyl-
After uniformly mixing 0.01 parts by weight of 1-butyn-3-ol, the viscosity of the polymer was 20 centipoise. Both ends of the molecular chain were blocked with trimethylsiloxy groups. Methyl hydrogen polysiloxane (content of hydrogen atoms bonded to silicon atoms = 1.6
% By weight) to prepare a curable organopolysiloxane composition. The exudation of the low-viscosity liquid organopolysiloxane from the cured product of the curable organopolysiloxane composition and the reliability of the semiconductor device were evaluated by the above methods. The results of these evaluations are shown in Table 1.

[Comparative Example 1] As the component (a), the viscosity was 1
A dimethylpolysiloxane capped with dimethylvinylsiloxy groups at both ends of the molecular chain of 10,000 centipoise (content of vinyl groups bonded to silicon atoms = 0.12% by weight) 64
15 parts by weight of a dimethylsiloxane-methylvinylsiloxane copolymer (capacity of vinyl group bonded to silicon atom = 0.84% by weight) with dimethylvinylsiloxy group blocked at both ends of a molecular chain having a viscosity of 6,000 centipoise. ,
As the component (c), 2 parts by weight of a dimethylpolysiloxane endblocked by dimethylhydrogensiloxy groups at both molecular chains having a viscosity of 15 centipoise (content of hydrogen atoms bonded to silicon atoms = 0.13% by weight), (d) As a component, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (in the composition, the amount of platinum metal in the complex is 5 ppm by weight), as an optional component , A fumed silica 16 having a specific surface area of 200 m ² / g, the surface of which has been hydrophobically treated with hexamethyldisilazane 16
By mixing 1 part by weight to prepare a mixture having a viscosity of 1,700 poise, the mixture is heated at 150 ° C. for 30 minutes to carry out a hydrosilation reaction, and the viscosity is 4,000 poise. A liquid organopolysiloxane was prepared.

Next, this liquid organopolysiloxane 1
An average unit formula in which the viscosity is 20 centipoise in 00 parts by weight:

Embedded image 1 part by weight of organopolysiloxane represented by (content of vinyl group bonded to silicon atom = 16% by weight) and 0.01 part by weight of 3-phenyl-1-butyn-3-ol as an addition reaction inhibitor After uniformly mixing, 2 parts by weight of methylhydrogenpolysiloxane endblocked with trimethylsiloxy groups at both molecular chain ends having a viscosity of 20 centipoise (content of hydrogen atoms bonded to silicon atoms = 1.6% by weight) is uniformly mixed. Thus, a curable organopolysiloxane composition was prepared. The exudation of the low-viscosity liquid organopolysiloxane from the cured product of the curable organopolysiloxane composition and the reliability of the semiconductor device were evaluated by the above methods. The results of these evaluations are shown in Table 1.

[Comparative Example 2] As the component (a), the viscosity was 1
A dimethylpolysiloxane capped with dimethylvinylsiloxy groups at both ends of the molecular chain of 10,000 centipoise (content of vinyl groups bonded to silicon atoms = 0.12% by weight) 64
15 parts by weight of a dimethylsiloxane-methylvinylsiloxane copolymer (capacity of vinyl group bonded to silicon atom = 0.84% by weight) with dimethylvinylsiloxy group blocked at both ends of a molecular chain having a viscosity of 6,000 centipoise. ,
As the component (b), the average unit formula having a viscosity of 20 centipoise:

Embedded image 1 part by weight of organopolysiloxane represented by (content of vinyl group bonded to silicon atom = 16% by weight), and as component (d), 1,3-divinyl-1,1,3,3-platinum
Tetramethyldisiloxane complex (in the composition, the amount of platinum metal in the complex is 5 ppm by weight),
As an optional component, 16 parts by weight of fumed silica, the surface of which was hydrophobically treated with hexamethyldisilazane and having a specific surface area of 200 m ² / g, was uniformly mixed to prepare a mixture having a viscosity of 4,600 poises. The mixture was then heated at 150 ° C. for 30 minutes without thickening and the hydrosilation reaction did not proceed.

Next, 100 parts by weight of this mixture was uniformly mixed with 0.01 parts by weight of 3-phenyl-1-butyn-3-ol as an addition reaction inhibitor, and then a molecular chain having a viscosity of 20 centipoise. A curable organopolysiloxane composition was prepared by uniformly mixing 2 parts by weight of trimethylsiloxy group-blocked methylhydrogenpolysiloxane with both ends blocked (content of hydrogen atoms bonded to silicon atoms = 1.6% by weight). The exudation of the low-viscosity liquid organopolysiloxane from the cured product of the curable organopolysiloxane composition and the reliability of the semiconductor device were evaluated by the above methods. The results of these evaluations are shown in Table 1.

Example 2 As the component (a), the viscosity was 1
A dimethylpolysiloxane capped with dimethylvinylsiloxy groups at both ends of the molecular chain of 10,000 centipoise (content of vinyl groups bonded to silicon atoms = 0.12% by weight) 64
15 parts by weight of a dimethylsiloxane-methylvinylsiloxane copolymer (capacity of vinyl group bonded to silicon atom = 0.84% by weight) with dimethylvinylsiloxy group blocked at both ends of a molecular chain having a viscosity of 6,000 centipoise. ,
As the component (b), the average unit formula having a viscosity of 20 centipoise:

Embedded image 2 parts by weight of an organopolysiloxane represented by (content of vinyl group bonded to silicon atom = 8% by weight), and as component (c), a dimethyl-capped dimethylhydrogensiloxy group-capped dimethyl molecule having a viscosity of 15 centipoise. Polysiloxane (content of hydrogen atom bonded to silicon atom = 0.
13 parts by weight) 2 parts by weight, 1,3 of platinum as the component (d)
-Divinyl-1,1,3,3-tetramethyldisiloxane complex (in the present composition, the amount of platinum metal in this complex is 5 ppm by weight), the surface of which is hexamethyldisilazane as an optional component 16 parts by weight of hydrophobically treated fumed silica having a specific surface area of 200 m ² / g was uniformly mixed to prepare a mixture having a viscosity of 4,000 poises. Next, when this mixture was heated at 150 ° C. for 30 minutes, a hydrosilation reaction proceeded to prepare a grease-like organopolysiloxane having a viscosity of 9,300 poise.

Next, this liquid organopolysiloxane 1
To 100 parts by weight, as an addition reaction inhibitor, 3-phenyl-
After uniformly mixing 0.01 parts by weight of 1-butyn-3-ol, the viscosity of the polymer was 20 centipoise. Both ends of the molecular chain were blocked with trimethylsiloxy groups. Methyl hydrogen polysiloxane (content of hydrogen atoms bonded to silicon atoms = 1.6
% By weight) to prepare a curable organopolysiloxane composition. The exudation of the low-viscosity liquid organopolysiloxane from the cured product of the curable organopolysiloxane composition and the reliability of the semiconductor device were evaluated by the above methods. The results of these evaluations are shown in Table 1.

[Comparative Example 3] As the component (a), the viscosity was 1
A dimethylpolysiloxane capped with dimethylvinylsiloxy groups at both ends of the molecular chain of 10,000 centipoise (content of vinyl groups bonded to silicon atoms = 0.12% by weight) 64
15 parts by weight of a dimethylsiloxane-methylvinylsiloxane copolymer (capacity of vinyl group bonded to silicon atom = 0.84% by weight) with dimethylvinylsiloxy group blocked at both ends of a molecular chain having a viscosity of 6,000 centipoise. ,
As the component (c), 2 parts by weight of a dimethylpolysiloxane endblocked by dimethylhydrogensiloxy groups at both molecular chains having a viscosity of 15 centipoise (content of hydrogen atoms bonded to silicon atoms = 0.13% by weight), (d) As a component, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (in the composition, the amount of platinum metal in the complex is 5 ppm by weight), as an optional component , 16 parts by weight of fumed silica, the surface of which was hydrophobically treated with hexamethyldisilazane and having a specific surface area of 200 m ² / g, were uniformly mixed to prepare a mixture having a viscosity of 1,700 poises. Then, when this mixture was heated at 150 ° C. for 30 minutes, a hydrosilation reaction proceeded to prepare a liquid organopolysiloxane having a viscosity of 4,000 poise.

Next, this liquid organopolysiloxane 1
An average unit formula in which the viscosity is 20 centipoise in 00 parts by weight:

Embedded image 2 parts by weight of an organopolysiloxane represented by (vinyl group content = 8% by weight) and 0.01 parts by weight of 3-phenyl-1-butyn-3-ol as an addition reaction inhibitor are uniformly mixed. Then, 2 parts by weight of methyl hydrogen polysiloxane capped with trimethylsiloxy groups at both ends of the molecular chain and having a viscosity of 20 centipoise (content of hydrogen atoms bonded to silicon atoms = 1.6% by weight) are uniformly mixed and cured. A hydrophilic organopolysiloxane composition was prepared. The exudation of the low-viscosity liquid organopolysiloxane from the cured product of the curable organopolysiloxane composition and the reliability of the semiconductor device were evaluated by the above methods. The results of these evaluations are shown in Table 1.

Example 3 As the component (a), the viscosity was 1
A dimethylpolysiloxane capped with dimethylvinylsiloxy groups at both ends of the molecular chain of 10,000 centipoise (content of vinyl groups bonded to silicon atoms = 0.12% by weight) 64
15 parts by weight of a dimethylsiloxane-methylvinylsiloxane copolymer (capacity of vinyl group bonded to silicon atom = 0.84% by weight) with dimethylvinylsiloxy group blocked at both ends of a molecular chain having a viscosity of 6,000 centipoise. ,
As the component (b), the average unit formula having a viscosity of 20 centipoise:

[Chemical 6] 1 part by weight of an organopolysiloxane represented by (content of vinyl group bonded to silicon atom = 16% by weight), and as component (c), a dimethyl-capped dimethylhydrogensiloxy group-capped dimethyl molecule having a viscosity of 15 centipoise. Polysiloxane (content of hydrogen atoms bonded to silicon atoms =
0.13% by weight), and as the component (d), 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum (in the composition, the platinum metal in the complex is An amount of 5 ppm by weight), 16 parts by weight of fumed silica having a specific surface area of 200 m ² / g, the surface of which has been hydrophobically treated with hexamethyldisilazane as an optional component, are uniformly mixed to obtain a viscosity. Prepare a mixture of 4,000 poise and then mix this mixture at 25 ° C. for 1 hour.
A hydrosilation reaction was carried out by leaving it for a week to prepare a grease-like organopolysiloxane having a viscosity of 8,100 poise.

Next, this liquid organopolysiloxane 1
To 100 parts by weight, as an addition reaction inhibitor, 3-phenyl-
After uniformly mixing 0.01 parts by weight of 1-butyn-3-ol, the viscosity of the polymer was 20 centipoise. Both ends of the molecular chain were blocked with trimethylsiloxy groups. Methyl hydrogen polysiloxane (content of hydrogen atoms bonded to silicon atoms = 1.6
% By weight) to prepare a curable organopolysiloxane composition. The exudation of the low-viscosity liquid organopolysiloxane from the cured product of the curable organopolysiloxane composition and the reliability of the semiconductor device were evaluated by the above methods. The results of these evaluations are shown in Table 1.

[0038]

[Table 1]

[0039]

The curable organopolysiloxane composition of the present invention is characterized in that the exudation of the low-viscosity liquid organopolysiloxane contained for imparting adhesiveness during curing is suppressed. The semiconductor device of the invention is
Since it is coated with a cured product of such a curable organopolysiloxane composition, it is characterized by having excellent reliability.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a hybrid IC that is an example of a semiconductor device of the present invention.

FIG. 2 is a top view and a side view of a test body in which the length of a low-viscosity liquid organopolysiloxane exuded from a cured product of a curable organopolysiloxane composition was measured in an example of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Semiconductor element 2 Circuit board made of glass fiber reinforced epoxy resin 3 Circuit wiring 4 Bonding wire 5 Cured product of curable organopolysiloxane composition 6 Sealing resin composed of epoxy resin A Glass fiber reinforced epoxy resin plate B Curable organopoly Cured product of siloxane composition C Low-viscosity liquid organopolysiloxane exuded from cured product a, b, c, d Length of low-viscosity liquid organopolysiloxane exuded from cured product

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Mine 2-2 Chikusaigan, Ichihara, Chiba Toray Dow Corning Silicone Co., Ltd.

Claims (4)

[Claims] 1. A liquid organopolysiloxane (A) (a) having at least two alkenyl groups bonded to a silicon atom in one molecule, and 0.1 to 100 parts by weight of component (a).
20 parts by weight of (b) a low-viscosity liquid organopolysiloxane having at least one alkenyl group bonded to a silicon atom and at least one alkoxy group bonded to a silicon atom in one molecule, and (A) component is not cured. The amount of (c) a liquid organopolysiloxane having at least two hydrogen atoms bonded to silicon atoms in one molecule is 0.01 to 1,000 in terms of the metal atom in the catalyst in the present composition.
A silicon-bonded alkenyl group having at least two alkenyl groups in one molecule, which is thickened by a hydrosilation reaction in the presence of an amount of 0 ppm (d) a metal catalyst for hydrosilation reaction, A liquid organopolysiloxane having at least one atom-bonded alkoxy group in the molecule, and at least 2 hydrogen atoms bonded to the silicon atom (B) in the molecule in an amount sufficient to cure the composition. A curable organopolysiloxane composition comprising a plurality of liquid organopolysiloxanes. 2. A low-molecular component (b) having at least one alkenyl group bonded to a silicon atom, an alkoxy group bonded to a silicon atom, and an epoxy group-containing monovalent organic group bonded to a silicon atom in each molecule. The curable organopolysiloxane composition according to claim 1, which is a liquid organopolysiloxane having a viscosity. 3. The component (b) has an average unit formula: (R ¹ SiO _3/2 ) _a (R ² ₂ SiO _2/2 ) _b (R ² ₃ SiO _1/2 ) _c (R
³ O _1/2 ) _d (wherein R ¹ is an epoxy group-containing monovalent organic group, R ² is a substituted or unsubstituted monovalent hydrocarbon group, provided that
At least one R ² in the component (b) is an alkenyl group, R ³ is an alkyl group, a is a positive number, b is a positive number, c is 0 or a positive number, and d is a positive number. Is a positive number. } The curable organopolysiloxane composition according to claim 2, which is a low-viscosity liquid organopolysiloxane represented by the following formula. 4. A semiconductor device comprising a semiconductor element coated with a cured product of the curable organopolysiloxane composition according to claim 1. Description: