JP3183041B2 - Hydrosilylation reaction catalyst for silicone composition and addition-curable silicone composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to various fields such as extruded products, potting agents, adhesives, coating agents, and liquid injection molding systems, which have excellent storage stability at room temperature and can be quickly cured by heating. The present invention relates to an addition-curable silicone composition and a hydrosilylation reaction catalyst for an addition-curable silicone composition that can be suitably used for the present invention.

[0002]

2. Description of the Related Art An addition-curable silicone composition which is heat-cured by a hydrosilylation reaction using a platinum compound as a catalyst can perform a curing reaction in an extremely short time, and also has a reaction by-product. It has advantages such as lack of objects and is used for many purposes.

However, this silicone composition has poor storage stability at room temperature, and is stored in two components during storage.
Even if consideration was given to mixing during use, there was a drawback that it could not withstand actual use.

[0004] To solve the above-mentioned drawbacks, many compounds have been proposed which control the hydrosilylation reaction. For example, U.S. Pat. No. 3,188,300 discloses an organic phosphorus compound, U.S. Pat. No. 3,445,420 (JP-B-44-314).
No. 76), acetylene alcohols, U.S. Pat. No. 3,882,083 (JP-B-55-41626) discloses triallyl isocyanurate, U.S. Pat.
No. 09 (JP-B-57-20340) includes hydroperoxides, U.S. Pat. No. 3,690,073 (JP-B-48-10947) and U.S. Pat.
No. 5 (Japanese Patent Publication No. 63-56563) proposes a high vinyl siloxane or the like.

[0005] However, when these control agents are used in the above-mentioned silicone composition, a sufficient pot life and curability can be obtained by the conventional use method, but the demand in the market in recent years has become more severe. As a result, more satisfactory preservability and quick curing properties are required.

[0006] As a technology that can cope with these, Japanese Patent Publication No. Sho 5
JP-A-3-41707 discloses a platinum catalyst having a melting point of 40 to 20.
A method of obtaining a protected catalyst powder by mixing with a silicone resin at 0 ° C. and performing pulverization or spray drying, U.S. Pat. No. 4,481,341 (JP-A-64-474).
Nos. 42 and 64-45468) disclose a microencapsulation technique by including a platinum catalyst with a thermoplastic resin.

[0007] However, the former method (described in Japanese Patent Publication No. 53-41707) does not sufficiently improve the preservability of the silicone composition, and the latter method (US Pat. No. 448).
In the case of microencapsulation with an organic resin as described in No. 1341), the storage stability of the silicone composition is satisfactory, but it is difficult to obtain the quick curing properties required in the market. .

[0008] Therefore, there has been a demand for the development of a technique capable of further improving the storage stability and curing characteristics of an addition-curable silicone composition.

The present invention has been made in order to meet the above-mentioned demand, and has excellent storage stability and excellent curing properties.
It is an object of the present invention to provide an addition-curable silicone composition that cures quickly by heating and a hydrosilylation reaction catalyst for an addition-curable silicone composition.

[0010]

The present inventors have made intensive studies to achieve the above object, and as a result, the following general formula (1): R ¹ _a R ² _b (CH ₃ ) _c SiO _{[4- ( a + b + c)] / 2} (1) (wherein R ¹ is an aliphatic unsaturated group having 2 to 8 carbon atoms, R ²
Is an unsubstituted or substituted monovalent hydrocarbon group other than an aliphatic unsaturated group and a methyl group, and a, b, and c are each c / (a
+ B + c) ≧ 0.95, 0.0001 <a <0.05,
It is a number that satisfies 1.8 <a + b + c <2.205. )
Wherein at least 95 mol% of organic groups (excluding silicon-oxygen bonds) bonded to silicon atoms contains at least two aliphatic unsaturated groups in one molecule and is a methyl group. siloxane, the following general formula _{^{(2) R 3 d H e}} SiO [4- (d + e)] / 2 (2) ( provided that wherein R ³ is an unsubstituted or substituted monovalent hydrocarbon group, d , E are 0.002 ≦ e ≦ 1.0 and 1.8, respectively.
This is a number that satisfies 1.8 <d + e ≦ 3.0 when <d <2.2. An organohydrogenpolysiloxane having a hydrogen atom bonded to at least three silicon atoms in one molecule, and the following general formula (3): R ⁴ _f R ⁵ _g (CH ₃ ) _h SiO _{[4- (f + g + h)] / 2} (3) (wherein, R ⁴ is an aliphatic unsaturated group having 2 to 8 carbon atoms,
R ⁵ is an unsubstituted or substituted monovalent hydrocarbon group other than an aliphatic unsaturated group and a methyl group, and f, g, and h are each (f +
g) / (f + g + h) ≧ 0.10, 0.0001 <f ≦
2.0, 1.8 <f + g + h <2.205. Wherein at least two aliphatically unsaturated groups are present in one molecule and at least 10 mol% of all organic groups (excluding silicon-oxygen bonds) bonded to silicon atoms are groups other than methyl groups. in a platinum group stabilized by an organopolysiloxane compound, further R ⁶ ₃ SiO _1/2 units, R ⁶ ₂ Si
O _2/2 unit, R ⁶ SiO _3/2 unit, SiO _4/2 unit (however,
In the formula, R ⁶ is an unsubstituted or substituted monovalent hydrocarbon group. ) _Contains at least R ⁶ SiO _3/2 units or SiO _4/2 units, and at least 10 mol% of all organic groups (excluding silicon-oxygen bonds) bonded to silicon atoms in the above formula (3) By blending with a hydrosilylation reaction catalyst comprised of a silicone resin having the same group as R ⁵ and having a melting point or softening point of 30 to 200 ° C., its quality can be maintained for a long time at room temperature. Is stable, it is not necessary to store each component separately at the time of storage, and it has high storage stability, excellent curing characteristics, and is cured quickly by heating to give a cured product with good physical properties. The present inventors have found that an addition-curable silicone composition whose properties hardly change under environmental conditions such as storage under storage can be obtained, and have accomplished the present invention.

That is, in the silicone composition of the present invention, a siloxane complex of a platinum metal compound is formed by coordinating and stably fixing a platinum group compound with the aliphatic unsaturated group-containing organopolysiloxane of the above formula (3). The stabilized platinum group compound is basically incompatible with the diorganopolysiloxane of the above formula (1) at room temperature, and the formula (3)
In the storage state, the platinum group compound which is a hydrosilylation reaction catalyst is removed from the reaction system by assimilation and inclusion in the above-mentioned specific silicone resin which has a structure similar to that of the organopolysiloxane and is compatible therewith. Placed,
By heating, the platinum group compound is uniformly diffused into the system to promote the reaction. In this case, in the present invention, the point that the platinum group compound is compatible with and integrated with the silicone resin containing the same during storage is described in JP-B-53-41707.
No. 4,481,341, a catalyst powder in which a platinum catalyst is protected by a silicone resin described in US Pat.
This method is clearly different from the method of encapsulating platinum element in microcapsules described in, for example, Japanese Patent No. 5063, and the difference is surprisingly surprising. It is possible to obtain excellent curing characteristics.

Further, the silicone composition of the present invention overcomes the drawbacks of the conventional microencapsulation method, such as shortening the storage time once heated to a temperature higher than the melting point, and furthermore, reduces the physical high shear force during production. It has many advantages such that the performance is not impaired at all, and the drawback that the storage stability is impaired immediately or over time is eliminated.

Accordingly, the present invention relates to (1) an organic group (silicon-oxygen) represented by the above general formula (1) which contains at least two aliphatic unsaturated groups in one molecule and is bonded to a silicon atom. At least 9 of
Diorganopolysiloxane in which 5 mol% is a methyl group (2) Organohydrogenpolysiloxane represented by the above general formula (2) and having at least three hydrogen atoms bonded to one silicon atom in one molecule (3) In the molecule represented by the general formula (3), at least two aliphatic unsaturated groups are present in one molecule, and at least 10 mol% of all organic groups (excluding silicon-oxygen bonds) bonded to silicon atoms are present. platinum group compound which is stabilized by the organopolysiloxane is a group other than a methyl group, further R ⁶ ₃ SiO _1/2
Unit, R ⁶ ₂ SiO _2/2 unit, R ⁶ SiO _3/2 unit, SiO
_At least R ⁶ SiO _3/2 units or S among _4/2 units (wherein R ⁶ is an unsubstituted or substituted monovalent hydrocarbon group)
At least 10 mol% of all organic groups (excluding silicon-oxygen bonds) containing iO _4/2 units and bonded to silicon atoms are the same groups as R ⁵ in the formula (3), and have a melting point or A silicone composition comprising a hydrosilylation reaction catalyst contained in a silicone resin having a softening point of 30 to 200 ° C., and hydrosilyl for an addition-curable silicone composition comprising the component (3). The present invention provides a conversion reaction catalyst.

Now, the present invention will be described in further detail. The organopolysiloxane, which is the first essential component of the silicone composition of the present invention, is a known organopolysiloxane used as a main raw material of an addition-curable silicone rubber composition. A siloxane represented by the following general formula (1): R ¹ _a R ² _b (CH ₃ ) _c SiO _{[4- (a + b + c)] / 2} (1) (where R ¹ is a carbon atom having 2 to 2 carbon atoms) An aliphatic unsaturated group of 8, R ²
Is an unsubstituted or substituted monovalent hydrocarbon group other than an aliphatic unsaturated group and a methyl group, and a, b, and c are each c / (a
+ B + c) ≧ 0.95, 0.0001 <a <0.05,
It is a number that satisfies 1.8 <a + b + c <2.205. )
Wherein at least 95 mol% of organic groups (excluding silicon-oxygen bonds) bonded to silicon atoms contains at least two aliphatic unsaturated groups in one molecule and is a methyl group. Siloxane.

Here, R ¹ in the above formula is an aliphatic unsaturated group having 2 to 8 carbon atoms, for example, a vinyl group, an allyl group, a propenyl group, a butenyl group, etc., and particularly an alkenyl group such as a vinyl group. Is preferred. R ² is an unsubstituted or substituted monovalent hydrocarbon group other than an aliphatic unsaturated group and a methyl group, preferably having 2 to 12 carbon atoms, for example, an ethyl group,
Propyl group, alkyl group other than methyl group such as butyl group,
Aryl groups such as phenyl group and tolyl group, and those in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms or the like;
3,3-trifluoropropyl group, C ₄ F ₉ CH ₂ CH
_{2 -, C 8 F 17 CH} 2 CH 2 -, perfluoroalkyl ether group and the like. A, b, and c are each c
/(A+b+c)≧0.95, 0.0001 <a <0.
05, 1.8 <a + b + c <2.205.

The diorganopolysiloxane of the above formula (1)
Is R in one molecule¹Unsaturated fatty acids having 2 to 8 carbon atoms
Containing at least two sum groups, preferably alkenyl groups
And all organic groups bonded to silicon atoms (silicon-oxygen bond
Is excluded), that is, R in the formula (1)¹ , R^Two , CH_ThreeIf
At least 95 mol% of the total 100 mol% is methyl group
It is necessary to be.

The diorganopolysiloxane of the above formula (1), even if it is linear, partially contains RSiO _3/2 units (R is an unsubstituted or substituted monovalent hydrocarbon group) or SiO _4/2 units. It may have a branched shape, but the viscosity at 25 ° C. is preferably in the range of 50 to 1000000 centipoise (cp). If the viscosity is less than 50 cp, it may become brittle and the elasticity of silicone rubber may not be obtained.
If it exceeds 0000000 cp, it may not be possible to mix the rubber.

The diorganopolysiloxane of the formula (1) can be synthesized by a known method, for example, by equilibrating an organocyclopolysiloxane and a hexaorganodisiloxane in the presence of an alkali or acid catalyst.

Next, the organohydrogenpolysiloxane of the second essential component of the present invention reacts with the diorganopolysiloxane of the first component to act as a crosslinking agent, and has the following general formula (2): R ³ _{d H e SiO [4- (d +} e)] / 2 (2) ( provided that wherein R ³ is an unsubstituted or substituted monovalent hydrocarbon group, d, e respectively 0.002 ≦ e ≦ 1. 0, 1.8
This is a number that satisfies 1.8 <d + e ≦ 3.0 when <d <2.2. ) And having a hydrogen atom bonded to at least three silicon atoms in one molecule.

In the above formula (2), R ³ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, for example, an aliphatic unsaturated group such as vinyl group, allyl group, propenyl group and butenyl group. Groups, methyl groups, ethyl groups, propyl groups, alkyl groups such as butyl groups, phenyl groups, aryl groups such as tolyl groups, and some or all of these groups in which some or all hydrogen atoms have been substituted with halogen atoms or the like. 3- trifluoropropyl _{group, C 4 F 9 CH 2 CH} 2 -, C 8 F 17 CH 2 CH 2 -, perfluoroalkyl ether group and the like. d and e are 0.002 ≦ e ≦ 1.0 and 1.8 <d <2.2, respectively.
Is a number that satisfies 1.8 <d + e ≦ 3.0.

The organohydrogenpolysiloxane of the above formula (2) needs to have at least three hydrogen atoms directly bonded to one silicon atom in one molecule.

The molecular structure of the organohydrogenpolysiloxane of the above formula (2) is not particularly limited, and various structures such as linear, cyclic and branched structures can be used. The viscosity is preferably in the range of 1 to 500 cp.

The organohydrogenpolysiloxane of the above formula (2) can be prepared by a known method, for example, octamethylcyclotetrasiloxane, tetramethylcyclotetrasiloxane and hexamethyldisiloxane or 1,1'-dihydro-2 which can be a terminal group. , 2 ', 3,3'-tetramethyldisiloxane unit and a compound containing a catalyst such as sulfuric acid, trifluoromethanesulfonic acid, methanesulfonic acid, etc. are equilibrated at a temperature of about -10 to + 40 ° C. Can be easily synthesized by a simple method.

In the present invention, the addition amount of the organohydrogenpolysiloxane of the above formula (2) as the second component is determined based on the formula (2) based on one aliphatic unsaturated group contained in the whole composition. Hydrogen atom bound to silicon atom is 0.4 ~
A range of 10 equivalents, particularly 0.8 to 5 equivalents, is suitable. If the addition amount is less than 0.4 equivalent, the crosslinking density becomes too low, which may adversely affect the heat resistance of the cured silicone rubber. If the addition amount exceeds 10 equivalents, foaming problems due to the dehydrogenation reaction may occur, May adversely affect sex.

The third essential component of the composition of the present invention is represented by the following general formula (3): R ⁴ _f R ⁵ _g (CH ₃ ) _h SiO _{[4- (f + g + h)] / 2} (3) Wherein R ⁴ is an aliphatic unsaturated group having 2 to 8 carbon atoms,
R ⁵ is an unsubstituted or substituted monovalent hydrocarbon group other than an aliphatic unsaturated group and a methyl group, and f, g, and h are each (f +
g) / (f + g + h) ≧ 0.10, 0.0001 <f ≦
2.0, 1.8 <f + g + h <2.205. )), All organic groups (excluding silicon-oxygen bonds) having at least two aliphatic unsaturated groups in one molecule and bonded to a silicon atom, that is, R ⁴ in the formula (3),
R ^5, CH ₃ total 100 mol% 10 mol% or more of the, preferably 10 to 95 mol%, more preferably 30
~ 95 mol% of a platinum group compound stabilized by an organopolysiloxane having a group other than a methyl group further comprises R
⁶ ₃ SiO _1/2 units, R ⁶ ₂ SiO _2/2 units, R ⁶ SiO _3/2 units, SiO _4/2 units (wherein, wherein R ⁶ is unsubstituted or substituted monovalent hydrocarbon group. ) At least R ⁶ SiO _3/2
And at least 10 mol% of all organic groups (excluding silicon-oxygen bonds) bonded to silicon atoms containing the same units or SiO _4/2 units are the same groups as R ⁵ in the formula (3), and It is a hydrosilylation reaction catalyst comprised of a silicone resin having a melting point or softening point of 30 to 200 ° C. The hydrosilylation reaction catalyst catalyzes the hydrosilylation reaction between the diorganopolysiloxane of the first component and the organohydrogenpolysiloxane of the second component, whereby a crosslinked structure is formed in the silicone composition and the silicone composition is elastic after curing. It can be used as a body.

In this case, as the platinum group compound, compounds such as platinum, rhodium, ruthenium and palladium can be used, but platinum compounds are preferably used in view of economy and performance. Examples of the platinum compound include conventionally known chloroplatinic acid or its alcohol complex, divinyltetramethyldisiloxane, 1,3,5,7-tetravinyl-1,3,5,7-tetrathimercyclotetrasiloxane And the like.

In the organopolysiloxane represented by the above formula (3) for stabilizing this platinum compound, R
⁴ is an aliphatic unsaturated group having 2 to 8 carbon atoms, such as a vinyl group, an allyl group, a propenyl group, a butenyl group, an alkynyl group such as an ethynyl group, a propargyl group, and the like. Alkenyl groups are preferred. R ⁵
Is an unsubstituted or substituted monovalent hydrocarbon group other than an aliphatic unsaturated group and a methyl group, preferably one having 2 to 12 carbon atoms, for example, an ethyl group, a propyl group, an alkyl other than a methyl group such as a butyl group. Groups, phenyl groups, aryl groups such as tolyl groups, 3,3,3-trifluoropropyl groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms, etc., C ₄ F ₉ CH ₂ CH ₂ — , C ₈ F ₁₇ CH ₂ CH ₂ —, a perfluoroalkyl ether group and the like, and a phenyl group and a fluorine atom-substituted hydrocarbon group are particularly preferable.
f, g, and h are respectively (f + g) / (f + g + h) ≧
0.10, 0.0001 <f ≦ 2.0, 1.8 <f + g
+ H <2.205, and h is 0 or a positive number.

The organopolysiloxane of the above formula (3) has at least two aliphatically unsaturated groups in one molecule, and has 10 organic groups (excluding silicon-oxygen bonds) bonded to silicon atoms. It is necessary that at least mol% be a group other than a methyl group, and the compound of the above formula (3) does not substantially dissolve in the first component diorganopolysiloxane of the above formula (1) at room temperature. Are poorly soluble compounds. The viscosity of the compound of the formula (3) at 25 ° C. is 1 to 500.
It is preferably 0000 cp, particularly preferably 100 to 1,000,000 cp, and the siloxane polymerization degree is preferably 1,000 or less.

As the organopolysiloxane of the above formula (3), organovinylsiloxane having a high vinyl group as described in JP-B-48-10947 and compounds having the following structure are preferably used. You.

[0030]

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The stabilization of the platinum group compound is carried out, for example, by directly reacting chloroplatinic acid with the organopolysiloxane of the above formula (3) and then neutralizing the reaction with sodium hydrogen carbonate or the like. It can be carried out by forming a siloxane complex of a platinum group compound by employing a method of aging the vinylsiloxane complex and the organopolysiloxane of the above formula (3).

Further, the stabilized platinum group compound is encapsulated.
The silicone resin contained is R⁶ _ThreeSiO_1/2Unit, R⁶ _TwoS
iO_2/2Unit, R⁶ SiO_3/2Unit, SiO_4/2Out of units
At least R⁶ SiO_3/2Unit or SiO_4/2Contains unit
All organic groups bonded to silicon atoms (excluding silicon-oxygen bonds)
10 mol% or more of R in the above formula (3)^FiveSame as
Group having a melting point or softening point of 30 to 200 ° C.
You. This silicone resin is basically stable at normal temperature
Can be compatible with the platinum group compound
It is incompatible with luganopolysiloxane. In particular, this
As the cone resin, R⁶ _ThreeSiO_1/2Unit 0-50
%, R⁶ _TwoSiO_2/2Unit 0-30 mol%, R⁶ SiO
_3/2The unit is SiO_4/270 to 100 when unit is not included
Mol%, SiO_4/20-90 mol% when unit is included
Is preferred. In addition, SiO_4/2The unit is 30 to 80
Molar% is preferred.

Here, R ⁶ in the formula is an unsubstituted or substituted monovalent hydrocarbon group, and specific examples include the same groups as R ^{3 in} the organohydrogenpolysiloxane of the above formula (2).

In the silicone resin, at least 10 mol% of all organic groups bonded to silicon atoms are the same as R ⁵ in the formula (3). In this case, R ⁵ is preferably phenyl. And a fluorine-containing group are preferred.

Further, the silicone resin must have a melting point or softening point of 30 to 200 ° C., particularly 40 to 150 ° C. If the temperature is lower than 30 ° C., the catalyst component easily oozes out of the silicone resin, and the silicone resin is stored. Problems with stability arise.
If the temperature exceeds 200 ° C., upon heating and curing, the silicone resin does not melt or soften effectively and quickly, so that it is difficult to effectively use the catalyst component.

As such a silicone resin, for example, phenyl group-containing silicone resins and fluorine silicone resins described in JP-A-5-5063 and JP-A-4-36354 are suitable. In these prior arts, a vinyl siloxane complex of platinum similar to that of the present invention is used, but in the present invention, the structure of the siloxane forming the siloxane complex of platinum is the same as that of the above-mentioned silicone resin. It has a similar structure and is different from the conventional one in that both are compatible and integrated, thereby improving the storage stability of the silicone composition to a surprising level.

In order to include the stabilized platinum compound in a silicone resin, the two components are mixed in the presence of an organic solvent, for example, dichloromethane, benzene, methyltrichlorosilane, dioxane or the like, and then spray-dried or freeze-dried. And so on. in this case,
The mixing ratio of the stabilized platinum compound and the silicone resin containing the same is preferably such that the softening point of the resulting hydrosilylation reaction catalyst is in the range of 30 to 200 ° C. It is preferred that the ratio be 80 to 99.9% of the entire hydrosilylation reaction catalyst.

In the composition of the present invention, the amount of the hydrosilylation reaction catalyst to be added is generally in the range of 1 to 2000 ppm, preferably 5 to 1000 ppm, as a platinum group metal atom in all components, and if it is less than 5 ppm, the composition is preferably used. In some cases, a sufficient curing rate cannot be obtained, and if it exceeds 2000 ppm, there is an economical problem, and furthermore, sufficient preservability may not be obtained.

[0039] In addition to the above components, an adhesive component can be added to the silicone composition of the present invention for the purpose of imparting adhesiveness. As the adhesive component, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, which is usually commercially available as carbon functional silane,
Examples thereof include compounds such as-(3,4-epoxycyclohexyl) ethyltrimethoxysilane and the following compounds having a group such as a hydrogen atom, an alkenyl group, an alkoxy group, or an epoxy group directly bonded to a silicon atom in one molecule. . The amount of the adhesive component is preferably from 0 to 20 parts by weight based on 100 parts by weight of the component of the general formula (1).

[0040]

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When it is necessary to impart strength to the composition of the present invention, it is effective to add finely divided silica having a specific surface area of 50 m ² / g or more. As the finely divided silica, specifically, Aer is used as a hydrophilic silica.
osil 130, 200, 300 (manufactured by Nippon Aerosil Co., Ltd., manufactured by Degussa), Cabosi
l MS-5, MS-7 (manufactured by Cabot), Rheosil QS-102, 103 (manufactured by Tokuyama Soda), Nipsil LP (manufactured by Nippon Silica)
Aerosil R-812 as hydrophobic silica,
R-812S, R-972, R-974 (Degussa (D
egussa), Rheosil MT-1
0 (manufactured by Tokuyama Soda Co., Ltd.) and Nipsil SS series (manufactured by Nippon Silica Co., Ltd.).

The amount of the fine silica powder is preferably 0 to 30 parts by weight based on 100 parts by weight of the first component.

Further, in the present invention, as other components, quasi-reinforcing fillers such as quartz powder, diatomaceous earth, calcium carbonate, alumina and carbon black; inorganic pigments such as cobalt blue; coloring agents such as organic dyes; Heat resistance, such as zinc carbonate, manganese carbonate, red iron oxide, titanium oxide,
It is also possible to add a flame retardant improver and the like, and the amount of these additives may be a usual amount within a range not to impair the effects of the present invention.

[0044]

Industrial Applicability The silicone composition of the present invention is stable at room temperature for a long period of time, has excellent storage stability, has excellent curing properties, and can be quickly cured by heating. It can sufficiently meet the demand and can be suitably used in various fields such as an extruded product, a potting agent, an adhesive, a coating agent, and a liquid injection molding system.

[0045]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples. All parts in each example are parts by weight.

[Synthesis Example 1] Preparation of platinum compound: chloroplatinic acid 4 was placed in a flask equipped with a stirrer.
g, an organopolysiloxane compound having the following structure: 15 g,
100 g of methyl isobutyl ketone was added, 2.6 g of sodium hydrogen carbonate was further added, and the mixture was stirred at room temperature for 1 hour.
The mixture was stirred for 4 hours while heating to 0 ° C.

[0047]

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Next, this solution was concentrated at 80 ° C. under a reduced pressure of 10 mmHg to obtain a vinylphenylsiloxane complex of chloroplatinic acid (platinum concentration: 1%) (platinum compound A). Preparation of phenylsiloxane resin: 148 g of phenyltrichlorosilane and 53 g of propyltrichlorosilane were placed in a flask equipped with a stirrer, hydrolyzed, 5 g of hexamethyldisilane was added, and the mixture was stirred at 70 ° C. for 2 hours to silylate. When the volatile components were distilled off under reduced pressure, the softening point was 83%.
A phenylsiloxane resin (Silicone Resin A) containing 0.1 mol% of Si-OH groups at ℃ was obtained. Preparation of hydrosilylation reaction catalyst: the above platinum compound A30
g, 30 g of the above silicone resin A in dichloromethane 1
The resultant was uniformly dissolved in 00 g and subjected to a spray drying method, whereby 17 g of a hydrosilylation reaction catalyst 1 contained in the silicone resin was obtained.

Synthesis Example 2 30 g of the platinum compound A and 30 g of the silicone resin A obtained in Synthesis Example 1 were mixed with benzene 10
0 g, solidified with dry ice / methanol, returned to room temperature under reduced pressure, and kept under reduced pressure until the solvent was distilled off (freeze drying method). The hydrosilylation reaction catalyst 2 contained in the silicone resin was Is 2
8 g were obtained.

Synthesis Example 3 Synthesis of 3,3,3-trifluoropropyl group-containing vinylsiloxane oil: 3,3,3-trifluoropropyl in a flask equipped with a dropping funnel, reflux condenser and stirrer at room temperature 155 g of a cyclic siloxane trimer of trimethylcyclotrisiloxane was dissolved in 200 g of tetrahydrofuran, and 1000 g of vinylmagnesium bromide was added dropwise to this solution. Distilled water was added, heated to 60 ° C., and stirred for 3 hours.

Next, the mixture is concentrated at 100 ° C. under a reduced pressure of 10 mmHg, and the concentrated liquid is poured into a 1: 1 (molar ratio) mixed solution of a 10% hydrochloric acid aqueous solution and toluene. Stirred for hours. Then, after washing with water and dehydrating the solution with sodium sulfate, 3,3,3 having the following structure was obtained.
-A trifluoropropyl group-containing vinyl siloxane oil was obtained.

[0052]

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Preparation of platinum compound: In a flask equipped with a stirrer, 4 g of chloroplatinic acid, 12 g of the 3,3,3-trifluoropropyl group-containing vinylsiloxane oil and methanol 1
Then, 2.6 g of sodium hydrogen carbonate was added, and the mixture was stirred at room temperature for 1 hour, and then stirred at 80 ° C. for 4 hours.

Next, when this solution was concentrated at 60 ° C. under a reduced pressure of 10 mmHg, a 3,3,3-trifluoropropyl group-containing vinylsiloxane complex of chloroplatinic acid (platinum concentration: 1%) (platinum compound B) was obtained. Obtained. Preparation of fluorinated siloxane resin: 185 g of trifluoropropyltrichlorosilane and 30 g of methyltrichlorosilane were placed in a flask equipped with a stirrer, hydrolyzed, 5 g of hexamethyldisilane was added, and the mixture was stirred at 70 ° C. for 2 hours to silylate. When volatiles were distilled off under reduced pressure,
A fluorine siloxane resin (silicone resin B) having a softening point of 86 ° C. and 0.2 mol% of Si—OH groups was obtained. Preparation of hydrosilylation reaction catalyst: the above platinum compound B30
g, 30 g of the above silicone resin B was added to 150 g of dioxane.
g, and the solution was subjected to a freeze-drying method. As a result, 16 g of the hydrosilylation reaction catalyst 3 contained in the silicone resin was obtained.

[Synthesis Example 4] Synthesis of vinyl group-containing 3,3,3-trifluoropropylsiloxane long-chain oil: Cyclization of methylvinylcyclotrisiloxane at room temperature in a flask equipped with a dropping funnel, reflux condenser, and stirrer Dissolve 22 g of siloxane trimer in 63 g of acetonitrile, and add 5 g of the formula shown below to this solution.
A catalytic amount of coordination silicon catalyst and distilled water were added, and the mixture was stirred for 4 hours.

[0056]

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Next, the solution was cooled to 10 ° C.
200 g of a cyclic siloxane trimer of 3,3-trifluoropropyltrimethylcyclotrisiloxane and a catalytic amount of the above-mentioned 5-coordinate silicon catalyst were dissolved and stirred for 6 hours.

Further, 20.4 g of dimethylvinylchlorosilane and pentamethyldivinyldisilazane 35 were added to this solution.
g, heated to 100 ° C. and stirred for 1 hour. Thereafter, the mixture was concentrated at 150 ° C. under a reduced pressure of 20 mmHg, allowed to cool to room temperature, and subjected to pressure filtration to obtain a vinyl group-containing 3,3,3-trifluoropropylsiloxane long-chain oil having the following structure.

[0059]

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Preparation of platinum compound: A toluene solution of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex (platinum concentration: 5%) was placed in a flask equipped with a stirrer.
g, 90 g of the above-mentioned vinyl group-containing 3,3,3-trifluoropropylsiloxane long-chain oil and 200 g of methyl isobutyl ketone, and the mixture was stirred for 4 hours while heating to 80 ° C.

Next, this solution was concentrated at 80 ° C. under a reduced pressure of 10 mmHg to obtain a vinyl group-containing 3,3,3-trifluoropropyl long-chain siloxane complex (platinum compound C) having a platinum concentration of 1%. . Preparation of Hydrosilylation Reaction Catalyst: Platinum Compound C30
g, 30 g of the above silicone resin B was added to 150 g of dioxane.
g) and mixed by freeze drying to obtain 17 g of hydrosilylation reaction catalyst 4 contained in the silicone resin.

[Synthesis Example 5] Preparation of platinum compound: chloroplatinic acid 4 in a flask equipped with a stirrer
g, 6.4 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and 100 g of ethanol,
Further, 2.6 g of sodium hydrogencarbonate was added, and the mixture was stirred at room temperature for 1 hour and then stirred at 80 ° C. for 4 hours.

Next, the solution was concentrated at 80 ° C. under a reduced pressure of 10 mmHg to obtain chloroplatinic acid (platinum concentration 0.5%).
%) Of a vinylmethylsiloxane complex (platinum compound D). Preparation of Hydrosilylation Reaction Catalyst: Platinum Compound D30
g, 30 g of the silicone resin A obtained in Synthesis Example 1 above
Was uniformly dissolved in 150 g of dichloromethane and mixed by a spray-drying method to obtain 16 g of a hydrosilylation reaction catalyst 5 contained in a silicone resin.

[Synthesis Example 6] Preparation of hydrosilylation reaction catalyst: 30 g of platinum compound D obtained in Synthesis Example 5 and 30 g of silicone resin B obtained in Synthesis Example 3 were uniformly dissolved in 150 g of dioxane, followed by freeze-drying. As a result, 16 g of a hydrosilylation reaction catalyst 6 included in the silicone resin was obtained.

Example 1 100 parts of a dimethylsiloxane polymer having a viscosity of 10,000 cp at 25 ° C. and both ends capped with a dimethylvinylsilyl group and a specific surface area of 300
A kneader was charged with 20 parts of fumed silica having a density of cm ² / g, 8 parts of hexamethyldisilazane, and 1 part of water. After stirring and mixing at room temperature for 1 hour, the mixture was heated to 150 ° C. and kept at room temperature for 2 hours. Was. Thereafter, the mixture was cooled to room temperature, and a dimethylsiloxane polymer having a viscosity of 10,000 cp at 25 ° C., both ends of which were blocked with a dimethylvinylsilyl group, was further added for 2 hours.
0 parts and 3 parts of hydrogenmethylpolysiloxane having a viscosity of about 10 cp at room temperature represented by the following formula were added and mixed uniformly.

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To 100 parts of this mixture, 1 part of 1,5-dihydrogen-1,3,5,7-tetramethyl-3-trimethoxysilylethyl-7-glycidylpropyltetrasiloxane, 0.2 part of triallylisocyanate Parts were added and mixed uniformly to obtain a silicone rubber-based compound.

This silicone rubber-based compound 1
To 00 parts, 0.5 part of the hydrosilylation reaction catalyst 1 obtained in Synthesis Example 1 was added and uniformly mixed to obtain a curable silicone composition.

Example 2 The hydrosilylation reaction catalyst 2 obtained in Synthesis Example 2 above was used in place of the hydrosilylation catalyst 1.
Was added in the same manner as in Example 1 except that 0.5 part of was added to obtain a curable silicone composition.

Example 3 To 100 parts of the same silicone rubber base compound as in Example 1, 0.5 part of the hydrosilylation reaction catalyst 3 obtained in Synthesis Example 3 was added, and the mixture was stirred and mixed until uniform. Further, the mixture was uniformly mixed with three rolls to obtain a curable silicone composition.

Example 4 To 100 parts of the same silicone rubber base compound as in Example 1, 0.5 part of the hydrosilylation reaction catalyst 4 obtained in Synthesis Example 4 was added, and the mixture was mixed uniformly to obtain a curable silicone composition. I got something.

Comparative Example 1 One part of the hydrosilylation reaction catalyst 5 obtained in Synthesis Example 5 was added to 100 parts of the same silicone rubber base compound as in Example 1, and the mixture was mixed uniformly to obtain a curable silicone composition. Obtained.

Comparative Example 2 One part of the hydrosilylation reaction catalyst 6 obtained in Synthesis Example 6 was added to 100 parts of the same silicone rubber base compound as in Example 1, and the mixture was mixed uniformly to obtain a curable silicone composition. Obtained.

The curable properties by heat and the storage stability of the curable silicone compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were measured by the following methods. Table 1 shows the results. Curing property by heat: Using a curast meter, 12
The time (It) until the hardening of the silicone composition starts at 0 ° C. and the time (T90) until the torque reaches 90% of the maximum value were determined, and were used as a measure of the curability. Storage stability: The silicone composition was left at 40 ° C., and the time until the fluidity disappeared was measured as the pot life.

From the results shown in Table 1, it was confirmed that the silicone compositions of the present invention (Examples 1 to 4) had good curing properties and excellent storage stability.

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[Table 1]

──────────────────────────────────────────────────続 き Continuing on the front page (72) Takashi Kondo, Inventor, Silicone Electronics Materials Research Laboratory, Shinjuku Chemical Co., Ltd. 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture (56) References JP-A-4-36354 ( JP, A) JP-A-5-5063 (JP, A) JP-B-53-41707 (JP, B2) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 83/07 C08L 83/04 C08L 83/05

Claims (2)

(57) [Claims] (1) The following general formula (1): R ¹ _a R ² _b (CH ₃ ) _c SiO _{[4- (a + b + c)] / 2} (1) (where R ¹ is An aliphatic unsaturated group having 2 to 8 carbon atoms, R ²
Is an unsubstituted or substituted monovalent hydrocarbon group other than an aliphatic unsaturated group and a methyl group, and a, b, and c are each c / (a
+ B + c) ≧ 0.95, 0.0001 <a <0.05,
It is a number that satisfies 1.8 <a + b + c <2.205. )
Wherein at least 95 mol% of organic groups (excluding silicon-oxygen bonds) bonded to silicon atoms contains at least two aliphatic unsaturated groups in one molecule and is a methyl group. siloxane (2) the following general formula _{^{(2) R 3 d H e}} SiO [4- (d + e)] / 2 (2) ( provided that wherein R ³ is an unsubstituted or substituted monovalent hydrocarbon group, d and e are 0.002 ≦ e ≦ 1.0 and 1.8, respectively.
This is a number that satisfies 1.8 <d + e ≦ 3.0 when <d <2.2. ), And an organohydrogenpolysiloxane having at least three hydrogen atoms bonded to one silicon atom in one molecule. (3) R ⁴ _f R ⁵ _g (CH ₃ ) _h SiO _{[4] -(f + g + h)] / 2} (3) (wherein, R ⁴ is an aliphatic unsaturated group having 2 to 8 carbon atoms,
R ⁵ is an unsubstituted or substituted monovalent hydrocarbon group other than an aliphatic unsaturated group and a methyl group, and f, g, and h are each (f +
g) / (f + g + h) ≧ 0.10, 0.0001 <f ≦
2.0, 1.8 <f + g + h <2.205. Wherein at least two aliphatically unsaturated groups are present in one molecule and at least 10 mol% of all organic groups (excluding silicon-oxygen bonds) bonded to silicon atoms are groups other than methyl groups. in a platinum group stabilized by an organopolysiloxane compound, further R ⁶ ₃ SiO _1/2 units, R ⁶ ₂ Si
O _2/2 unit, R ⁶ SiO _3/2 unit, SiO _4/2 unit (however,
In the formula, R ⁶ is an unsubstituted or substituted monovalent hydrocarbon group. ) _Contains at least R ⁶ SiO _3/2 units or SiO _4/2 units, and at least 10 mol% of all organic groups (excluding silicon-oxygen bonds) bonded to silicon atoms in the above formula (3) R ⁵ is the same group as, and melting point or softening point silicone composition characterized by comprising blending hydrosilylation catalyst formed by inclusion in silicone resin is 30 to 200 ° C.. 2. The following general formula (3): R ⁴ _f R ⁵ _g (CH ₃ ) _h SiO _{[4- (f + g + h)] / 2} (3) (where R ⁴ is a carbon atom 2 to 8 aliphatic unsaturated groups,
R ⁵ is an unsubstituted or substituted monovalent hydrocarbon group other than an aliphatic unsaturated group and a methyl group, and f, g, and h are each (f +
g) / (f + g + h) ≧ 0.10, 0.0001 <f ≦
2.0, 1.8 <f + g + h <2.205. Wherein at least two aliphatically unsaturated groups are present in one molecule and at least 10 mol% of all organic groups (excluding silicon-oxygen bonds) bonded to silicon atoms are groups other than methyl groups. in a platinum group stabilized by an organopolysiloxane compound, further R ⁶ ₃ SiO _1/2 units, R ⁶ ₂ Si
O _2/2 unit, R ⁶ SiO _3/2 unit, SiO _4/2 unit (however,
In the formula, R ⁶ is an unsubstituted or substituted monovalent hydrocarbon group. ) _Contains at least R ⁶ SiO _3/2 units or SiO _4/2 units, and at least 10 mol% of all organic groups (excluding silicon-oxygen bonds) bonded to silicon atoms in the above formula (3) A hydrosilylation reaction catalyst for an addition-curable silicone composition, comprising a silicone resin having the same group as R ⁵ and having a melting point or softening point of 30 to 200 ° C.