JPH04178461A - Curable organopolysiloxane composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent transparency and bond durability under hot and humid condition by compounding a specific organopolysiloxane, an organic silicon compound, an organic metal compound, etc., at specific ratios. CONSTITUTION:The objective composition is produced by compounding (A) 100 pts.wt. of an organopolysiloxane having >=2 units of formula I [R<1> is alkenyl; R<2> is (substituted) univalent hydrocarbon group free from aliphatic unsaturated bond; a is 1 or 2; b is 0-2; a+b is 1-3] in one molecule with (B) an organopolysiloxane having >=2 units of formula II [R<3> is (substituted) univalent hydrocarbon group; c is 0-2; d is 1-3; c+d is 1-3] in one molecule (the Si-bonded H atom in the component B is 0.5-5 mol per 1 mol of alkenyl group in the component A), (C) 0.1-20 pts.wt. of an organic silicon compound composed of the units of formula III, formula IV and formula V (R<4> is alkenyl; R<5> is alkyl, etc.; R<6> is 1-4C alkoxy; e is 0 or 1; f+g+h is 2; etc.), (D) 0.01-2 pts.wt. of an organic metal compound selected from organic titanium compound, etc., and (E) a catalyst for hydrosilylation reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a curable organopolysiloxane composition,
Specifically, the present invention relates to a curable organopolysiloxane composition that has excellent transparency and adhesive durability under high temperature and high humidity conditions.

[Prior Art] Curable organopolysiloxane compositions that cure in the presence of hydrosilylation catalysts are used in all fields. However, this composition has poor self-adhesive properties, and when using this composition for adhesive purposes, it has been necessary to contain various adhesion promoters in the composition. Therefore, the transparency of the composition was extremely poor. Therefore, the present inventors
In Japanese Patent Application No. 2-114178, an adhesion promoter was proposed for producing a curable organopolysiloxane composition having excellent transparency and self-adhesion.

[Problems to be Solved by the Invention] However, although the curable organopolysiloxane composition containing an adhesion promoter proposed in Japanese Patent Application No. 2-114178 has excellent transparency and self-adhesiveness, Adhesive durability under humid conditions was not satisfactory. For example, when the composition is used as a protective coating material for a semiconductor device, although the composition has excellent self-adhesion to the semiconductor device immediately after curing, it is heated to 120°C,
In addition, the adhesive durability was poor under high temperature and high humidity conditions of 100% relative humidity, resulting in a problem that the reliability of the semiconductor element deteriorated due to peeling at the interface between the composition and the semiconductor element.

As a result of intensive studies on curable organopolysiloxane compositions that have excellent transparency and adhesive durability under high temperature and high humidity conditions, the present inventors have discovered the adhesion promoter and specific The present invention was achieved by confirming that by blending an organometallic compound, a curable organopolysiloxane composition with excellent transparency and adhesive durability under high temperature and high humidity conditions can be obtained.

That is, an object of the present invention is to provide a curable organopolysiloxane composition that has excellent transparency and adhesive durability under high temperature and high humidity conditions.

[Means for Solving the Problems and Their Effects] The purpose of the present invention is to: ``(A) In one molecule, the general formula: % formula % (wherein R1 is an alkenyl group and R2 is an aliphatic unsaturated group) A substituted or unsubstituted monovalent hydrocarbon group containing no bond, a is 1 or 2, b is an integer of O to 2, and a+b is an integer of 1 to 3.) 100 parts by weight of an organopolysiloxane having at least two (B) in one molecule,
General formula: %Formula% (wherein R'' is a substituted or unsubstituted monovalent hydrocarbon group, C is an integer from 0 to 2, d is an integer from 1 to 3, and C+d is an integer from 1 to 3. Organopolysiloxane having at least two units represented by ), (C)-, units 1 to 20 represented by the general formula: R'aR6++-a+Slog.
mol%, General formula: R' r R5g R6h SIQ 20 to 80 mol% of units represented by g, and 20 to 60 mol% of units represented by general formula: R'lR' r R' h S 101 (in the formula N R4 is an alkenyl group, R6 is an alkyl group or an alkoxyalkyl group, R6 is an alkoxy group having 1 to 4 carbon atoms, e is O or an integer of 1, and 19g.

h is an integer satisfying f + g + h = 2, and f is an integer of O or 1, g is an integer of 0 to 2, h is an integer of 0 or 1, I, j, k
are integers that satisfy l+J+=3, and
1 is O or an integer of 1, j is an integer of O to 3, and k is an integer of O to 2. In addition, the content of R4 with respect to all silicon-bonded organic groups in component (C) is 2 mol% or more, and the content of R6 with respect to all silicon-bonded organic groups in component (C) is 5 mol% or more. . ) 0.1 to 20 parts by weight of an organosilicon compound consisting of (D) o, oi to 2 parts by weight of an organometallic compound selected from organotitanium compounds, organozirconium compounds and organoaluminum compounds, and (E) for hydrosilylation reaction. A curable organopolysiloxane composition comprising a catalyst. ” is achieved.

The curable organopolysiloxane composition of the present invention will be explained in detail.

The organopolysiloxane as component (A) of the present invention is the main component of the present invention, and has at least two units represented by the general formula % in one molecule. In the above formula, R+
is an alkenyl group, specifically a vinyl group.

Examples include allyl group and hexenyl group. R2 is a substituted or unsubstituted monovalent hydrocarbon group containing no aliphatic unsaturated bond, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group; a phenyl group, a tolyl group, etc. Aryl group; Examples include substituted alkyl groups such as chloromethyl group and perfluoroalkyl group. Also, a is 1
or 2, b is an integer from 0 to 2, and a+b is 1
It is an integer of ~3. Such organopolysiloxanes as component (A) include dimethylpolysiloxane in which both ends of the molecular chain are capped with dimethylvinylsiloxy groups, and dimethylsiloxane-methylvinylsiloxane in which both ends of the molecular chain are capped with dimethylvinylsiloxy groups. Copolymer 9 Dimethylsiloxane-methylvinylsiloxane copolymer with both ends of the molecular chain blocked with trimethylsiloxy groups Methylvinylpolysiloxane with both ends of the molecular chain blocked with hydroxyl groups, Methylvinylpolysiloxane with both ends of the molecular chain blocked with hydroxyl groups Examples include dimethylsiloxane-methylvinylsiloxane copolymers, branched dimethylpolysiloxanes having three or more dimethylvinylsiloxy groups in one molecule, and the like. The viscosity of component (A) is not particularly limited, but is 100 to 10. It is preferable that it is in the range of Oo o and o o o poise.

Component (B) of the present invention is expressed as a crosslinking agent in the composition of the present invention, and is an organopolysiloxane having at least two units represented by the general formula % in one molecule. In the above formula, R3 is a substituted or unsubstituted monovalent hydrocarbon group, specifically an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group; an aryl group such as a phenyl group or a tolyl group; Examples include substituted alkyl groups such as chloromethyl group and perfluoroalkyl group.

Further, C is an integer of O to 2, d is an integer of 1 to 3, and C+d is an integer of 1 to 3. Such organopolysiloxanes (B3 component) include dimethylpolysiloxane in which both ends of the molecular chain are blocked with dimethylhydrogensiloxy groups, and dimethylsiloxane-methyl in which both ends of the molecular chain are blocked with dimethylhydrogensiloxy groups. Hydrodiene siloxane copolymer 9 Methylhydrogenpolysiloxane with both ends of the molecular chain blocked with trimethylsiloxy groups, Methylhydrogensiloxane with both ends of the molecular chain blocked with trimethylsiloxy groups - Branched with 3 or more dimethylsiloxanes The blending amount of component (B) is such that the number of silicon-bonded hydrogen atoms in component (B) is 0.5 to 5 per mole of alkenyl group in component (A). .0 mol.

This is based on 1 mole of alkenyl group in component (A),
If the amount of silicon-bonded hydrogen atoms in component (B) is less than 0.5 mol, the resulting curable organopolysiloxane composition will not be sufficiently cured, while if it exceeds 5.0 mol, the obtained This is because the heat resistance of the curable organopolysiloxane composition after curing deteriorates.

Component (C) of the present invention acts as an adhesion promoter in the composition of the present invention, and has units 1 to 1 represented by the general formula: R 4 , R grow@) S101.
20 mol%, general formula: R'+R'. Units 20 to 80 represented by R6hS101
It is an organosilicon compound consisting of 20 to 60 mol% of units represented by the general formula: R'IR'R8bS101. In the above formula, R' is an alkenyl group, and specific examples thereof include a vinyl group, an allyl group, a hexenyl group, and the like. R5 is an alkyl group or an alkoxyalkyl group, specifically an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, or an alkoxyalkyl group such as a methoxyethyl group, a methoxypropyl group, or an ethoxypropyl group. be. R6 is an alkoxy group having 1 to 4 carbon atoms, specifically a methoxy group, ethoxy group, propoxy group, or butoxy group, and the resulting curable organopolysiloxane composition has good self-adhesive properties. From this point of view, R6 is preferably a methoxy group. Also, e is an integer of 0 or 1, f,
g and h are integers that satisfy f+g+h=2, and f is an integer of 0 or 1, g is an integer of O to 2, h is an integer of O or 1, and I, J
, k are integers satisfying I+J+=3, I is an integer of O or 1, j is an integer of O to 3, and k is an integer of O to 2.

Also, R for all silicon-bonded organic groups in component (C)
The content of Ra is 2 mol % or more, and the Ra content is 5 mol % or more relative to all silicon-bonded organic groups in component (C). In the present invention, the blending amount of component (C) is (
The amount is 0.1 to 20 parts by weight per 100 parts by weight of the organopolysiloxane component A). This is (A) component 10
If component (C) is less than 0.1 part by weight relative to 0 parts by weight, the self-adhesiveness of the resulting curable organopolysiloxane composition will deteriorate, while if it exceeds 20 parts by weight, the resulting curable organopolysiloxane composition will deteriorate. This is because the storage stability of the curable organopolysiloxane composition deteriorates. Such component (C) is
It can be easily produced by the method disclosed in Japanese Patent No. 114178. Specifically, an organoalkoxysilane having an alkyl group or an alkoxyalkyl group and an organopolysiloxane having an alkenyl group are subjected to equilibrium polymerization in the presence of an alkali metal hydroxide such as potassium hydroxide, sodium hydroxide, or lithium hydroxide. It can be produced by reaction.

Component CD) of the present invention, when used in combination with the organosilicon compound of component (C), improves the adhesive durability of the resulting curable organopolysiloxane composition under high temperature and high humidity conditions. Such component (D) is an organochin compound,
An organic metal compound selected from organic zirconium compounds and organic aluminum compounds, specifically organic titanium compounds such as tetrabutoxytitanium, tetraisopropoxytitanium, titanium diimpropoxy diethyl acetoacetate; tetrakis(10-undecylate)zirconium , zirconium tetrakis(laurate).

Organic zirconium compounds such as zirconium tetrakis(2-ethylhexanoate); organic aluminum compounds such as trimethoxyaluminum, triethoxyaluminum, aluminum triacetylacetonate, and aluminum salts such as stearic acid or benzoic acid. Among these, tetrabutoxytitanium is preferred because the resulting curable organopolysiloxane composition has excellent transparency, and tetrakis(2-titanium) is preferred because the resulting curable organopolysiloxane composition has excellent storage stability. Zirconium ethylhexanoate is preferred, and aluminum triacetylacetonate is preferred because the resulting curable organopolysiloxane composition has excellent transparency and storage stability. These component (D) may be used in combination with other organometallic compounds mentioned above. The blending amount of component (D) is 0.01 parts by weight per 100 parts by weight of component (A).
~2 parts by weight.

This is because if component (D) is less than 0.01 part by weight relative to 100 parts by weight of component (A), the resulting curable organopolysiloxane composition will have poor adhesive durability under high temperature and high humidity conditions. On the other hand, if the amount exceeds 2 parts by weight, the transparency of the resulting curable organopolysiloxane composition and the heat resistance after curing will decrease.

Component (E) of the present invention is a hydrosilylation reaction catalyst for causing an addition reaction of a silicon-bonded hydrogen atom in component (B) to an alkenyl group in component (A).

Such a catalyst for hydrosilylation reaction may be a commonly known catalyst, and specifically, chloroplatinic acid.

Platinum-based compounds such as platinum-olefin complexes, platinum-vinylsiloxane complexes; palladium-based compounds such as tetrakis palladium, or rhodium-based compounds can be used, but the curability and storage of the resulting curable organopolysiloxane composition may be Platinum-based compounds are preferred because of their excellent stability. The blending amount of component (E) may be a commonly used catalyst amount, and specifically, it is in the range of 0.1 to 500 ppm based on 100 parts by weight of component (A). This is (A
) component (E) is 0. lppm
If it is less than 500 ppm, the curing of the obtained curable organopolysiloxane composition will be insufficient, while if it exceeds 500 ppm, the heat resistance of the obtained curable organopolysiloxane composition after curing will decrease. be.

The curable organopolysiloxane composition of the present invention may contain inorganic fillers such as fumed silica and quartz powder, as long as the purpose of the present invention is not impaired.

[Example] Hereinafter, the present invention will be explained with reference to an example. In progress, “department”
is "parts by weight", where rMeJ represents a methyl group,
rVIJ represents a vinyl group. The transparency of the curable organopolysiloxane composition is measured using water as a control.
It was measured by light transmittance at 589 nm. In addition, to evaluate the adhesive durability under high temperature and high humidity conditions, a curable organopolysiloxane composition was applied to a glass plate, a gold plate (glass epoxy resin coated with gold), and a polyimide resin. This product was heated to 121°C and left in an atmosphere of 100% relative humidity for 24 hours to observe the adhesive durability. ○ indicates that the bond is adhered, △ indicates that the bond is firmly adhered but some peeling is observed, and × indicates that the bond completely peels off.

Reference Example 1 100 parts of tetramethyltetravinylcyclotetrasiloxane, 70 parts of 3-methoxypropyltrimethoxysilane, and 0214 parts of potassium hydroxide were placed in a four-bottle flask equipped with a stirrer, a thermometer, and a reflux condenser, and the mixture was stirred. while heating.

After a polymerization reaction at a temperature of 120°C for 3 hours, the mixture was neutralized with dimethyldichlorosilane. After that, 5 m at 110℃
Low boilers were removed by vacuum distillation of aHg.

When the obtained product was analyzed by Fourier transform nuclear magnetic resonance analysis, it was found to be an organosilicon compound having the structural formula shown in Table 1.

Table 1 Reference Example 2 In a four-bottle flask equipped with a stirrer, a thermometer, and a reflux condenser, 100 parts of methylvinylpolysiloxane (average molecular weight 700), which has both molecular chain ends blocked with hydroxyl groups, and 3-
140 parts of methoxypropyltrimethoxysilane and 0.14 parts of potassium hydroxide were added and heated while stirring. After reacting for 3 hours at a temperature of 120"C, it was neutralized with dimethyldichlorosilane. Then, it was reacted at a temperature of 110"C for 5 hours.
Low boilers were removed by vacuum distillation at mmHg. When the obtained product was analyzed by Fourier transform nuclear magnetic resonance analysis, it was found to be an organosilicon compound having the structural formula shown in Table 2.

Table 2 Example 1 Dimethylpolysiloxane (average molecular weight 11.000) 1 in which both ends of the molecular chain are blocked with dimethylvinylsiloxy groups
00 parts, 1.2 parts of methylhydrodiene polysiloxane (average molecular weight 2,300) with both ends of the molecular chain capped with trimethylsiloxy groups, 1.5 parts of the organosilicon compound produced in Reference Example 1, 0 parts of tetrabutoxytitanium .2 parts of a 2% by weight solution of chloroplatinic acid in isopropyl alcohol 0.15
0.005 part of 3-methyl-1-butyn-3-ol was thoroughly mixed in order to adjust the volume and reaction rate to obtain a curable organopolysiloxane composition (I) of the present invention.

The resulting curable organopolysiloxane composition (I) was evaluated for transparency and adhesive durability under high temperature and high humidity conditions. The results are shown in Table 1.

Further, a curable organopolysiloxane composition was prepared by removing tetrabutoxytitanium from the above-mentioned curable organopolysiloxane composition, and this composition was also evaluated for transparency and adhesive durability under high temperature and high humidity conditions. The results are also listed in Table 3.

Table 3 Example 2 Dimethylpolysiloxane (average molecular weight 11.000) 1 in which both ends of the molecular chain are blocked with dimethylvinylsiloxy groups
00 parts, 1.2 parts of methylhydrodiene polysiloxane (average molecular weight 2,300) with both molecular chain ends capped with trimethylsiloxy groups, 1.5 parts of the organosilicon compound produced in Reference Example 1, tetrakis (2- ethylhexanoic acid)
2 parts of a 10% hexane solution of zirconium, 0.15 parts of a 2% by weight solution of chloroplatinic acid in isopropyl alcohol, and 3-methyl-1-butyne-3- to adjust the reaction rate.
A curable organopolysiloxane composition (n) of the present invention was obtained by thoroughly mixing 0.005 part of alcohol.

Obtained curable organopolysiloxane composition (IF)
The transparency and adhesive durability under high temperature and high humidity conditions were evaluated. The results are shown in Table 4 below.

Example 3 Dimethylpolysiloxane (average molecular weight 11.000) 1 in which both ends of the molecular chain are blocked with dimethylvinylsiloxy groups
00 parts, 1.2 parts of methyl hydrogen polysiloxane (average molecular weight 2,300) with both ends of the molecular chain capped with trimethylsiloxy groups, 1.5 parts of the organosilicon compound produced in Reference Example 2, aluminum triacetylaceto 0.2 parts of a 10% toluene solution of chloroplatinic acid, 0.15 parts of a 2% by weight inpropyl alcohol solution of chloroplatinic acid, and 0.005 parts of 3-methyl-1-butyn-3-ol to adjust the reaction rate. By mixing, a curable organopolysiloxane composition (I) of the present invention was obtained.

The resulting curable organopolysiloxane composition (III
) was evaluated for its transparency and adhesive durability under high temperature and high humidity conditions. The results are also listed in Table 4.

Table 4 [Effects of the invention] The curable organopolysiloxane composition of the present invention has (A
) to (E), and especially contains both an organosilicon compound as a component (C) and an organometallic compound as a component (D), so it has excellent transparency and adhesive durability under high temperature and high humidity conditions. Excellent in

Claims (1)

[Claims] (A) In one molecule, the general formula: R^1_aR^2_bSiO_(_4_-_(_a_+
_b_)_)_/_2 (wherein R^1 is an alkenyl group, R^2 is a substituted or unsubstituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond, and a is 1 or 2 and
b is an integer from 0 to 2, and a+b is an integer from 1 to 3. 100 parts by weight of an organopolysiloxane having at least two units represented by
_)_)_/_2 (wherein R^3 is a substituted or unsubstituted monovalent hydrocarbon group, c is an integer from 0 to 2, d is an integer from 1 to 3, and c+d is An organopolysiloxane having at least two units represented by (an integer from 1 to 3) The amount of silicon-bonded hydrogen atoms is 0.5 to 5.0 moles. }, (C) General formula: R^4_eR^5_(_1_-_e_)SiO_3_/
1 to 20 mol% of units represented by the general formula: R^4_fR^5_gR^6_hSiO_2_/_2, and units represented by the general formula: R^4_iR^5_jR^6_kSiO_1_/_2 20 to 60 mol% (in the formula, R^4 is an alkenyl group, R^5 is an alkyl group or an alkoxyalkyl group, R^6 is an alkoxy group having 1 to 4 carbon atoms, e
is an integer of 0 or 1, and f, g, h are each f+
An integer that satisfies g+h=2, and f is 0 or 1
g is an integer of 0 to 2, h is an integer of 0 or 1, and i, j, k are each i+j+k=3
i is an integer of 0 or 1, j is an integer of 0 to 3, and k is an integer of 0 to 2. In addition, the content of R^4 with respect to all silicon-bonded organic groups in component (C) is 2 mol% or more, and the content of R^6 with respect to all silicon-bonded organic groups in component (C) is 5 mol%. % or more. ) 0.1 to 20 parts by weight of an organosilicon compound consisting of (D) 0.01 to 2 parts by weight of an organometallic compound selected from organotitanium compounds, organozirconium compounds and organoaluminum compounds, and (E) for hydrosilylation reaction. A curable organopolysiloxane composition comprising a catalyst.