JPH11236508A - Organopolysiloxane composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain excellent shelf stability by employing an organopolysiloxane, an organohydrodienepolysiloxane, a compound having an active hydrogen atom- containing group, a first platinum group element catalyst, a second platinum group element catalyst, an addition reaction inhibitor and a filler. SOLUTION: A composition comprises 100 pts.wt. organopolysiloxane represented by formula I, 0.1-50 pts.wt. organohydrodienepolysiloxane represented by formula II as a crosslinking agent, 0-20 pts.wt. compound having an active hydrogen atom-containing group, a thermoplastic resin having a melting point or a softening point of 40-200 deg.C, 1-1,000 ppm first platinum group element embedded in a thermoplastic silicone resin or a heat melting compound having a molecular weight of 1,000 or less, a second platinum group element in an amount of one tenth of the first platinum group element, 0.001-20 pts.wt., addition reaction inhibitor and 0-1,000 pts.wt. filler. In the formulas, R' and X are each a 1-10C alkyl or aryl, a hydroxyl group or the like; R<2> is a 1-10C alkyl or aryl, or the like; Y is H or a monovalent group; K is 4 or more, m is 1 or more; and n is 0 or more.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an organopolysiloxane composition having excellent storage stability and curability.

[0002]

2. Description of the Related Art Conventionally, the addition reaction of an aliphatic unsaturated group and a hydrosilyl group with a platinum group metal catalyst has been utilized in many fields, and among them, platinum compounds have been used in these fields. In addition to being used as the most versatile catalyst compound in organic synthesis reactions such as synthesis of silalkane bonds, it is also used as a means of crosslinking addition-added resins or rubber, especially in the silicone industry. As specific applications, it is used for applications such as adhesives, coatings, potting agents, gels, foams, extrusion with liquid or millable rubber, compression molding or injection molding.

In recent years, in the field of silicone industry,
From the viewpoints of workability and workability, a material that has a long storage period and that cures quickly is required. Therefore, many compositions using an addition reaction using a platinum group metal catalyst as a crosslinking system have been proposed. Accordingly, many techniques for controlling the shelf life and pot life of the platinum group metal catalyst have been disclosed, and examples thereof include benzotriazole compounds (JP-B-40-25069) and acetylene alcohol compounds. (JP-B-44-31476), vinyl group-containing polysiloxane compounds (JP-B-48-10947), and hydroperoxides (JP-B-57-2034).
No. 0), amine compounds (JP-A-63-56563).
And the like have been proposed.

[0004] However, such a method by chemical control has a limitation in the balance between the pot life and the curing speed, and cannot meet the market demand for longer storage stability and sharp curing. Is coming.

Accordingly, a platinum group metal catalyst is embedded in a thermoplastic resin or silicone resin having a specific melting point, encapsulated and blended in a composition, and the platinum is melted by heating or dissolved by a solvent. A method has been proposed for releasing the group metal catalyst into the silicone composition. Prior art documents relating to this technology include, for example,
No. 134786, JP-A-58-37053,
JP-A-64-51140, JP-A-2-9448, JP-A-2-14244, JP-A-5-202
193 and JP-A-7-196921.

[0006] However, the microencapsulation method has a problem that partial hardening is apt to occur because the platinum group metal catalyst is unevenly distributed in the composition.

In order to solve this problem, a method has been proposed in which acetylene alcohol or the like is used as a reaction inhibitor (Japanese Patent Application Laid-Open No. 4-46962, etc.). Are listed.

However, it has been found that this composition also has some disadvantages when it is developed for various uses.

For example, when an adhesive component is added to these compositions to be used as a heat-curable silicone rubber adhesive,
If the temperature setting in the continuous production line is relatively low and it takes a certain amount of time for the thermoplastic resin etc. that embeds the platinum group metal catalyst to melt, curing and adhesion in the production line will be incomplete. Sometimes occur. Also, when a foam is obtained in a heating line by blending a hydroxyl group supply source such as alcohol or water into the composition, foaming due to a small amount of dehydrogenation at the beginning of the reaction becomes a core of the foam, and a good foam is obtained. However, there is a problem that the above-mentioned reaction inhibitor also suppresses this initial foaming, and a good foam cannot be obtained. Furthermore, when used as a millable type addition-curing material, if vulcanization is performed at high speed to mold electric wires and tubes, tack (stickiness) remains on the surface, and a molded body with a smooth surface can be obtained. There is no problem.

Accordingly, an object of the present invention is to provide an organopolysiloxane composition which has solved the above-mentioned problems.

[0011]

Means for Solving the Problems and Embodiments of the Invention The present inventors have made intensive studies to achieve the above object, and as a result, have found that an organopolysiloxane containing an alkenyl group or a hydroxyl group and an organohydrogenpolysiloxane can be used. (D) a thermoplastic organic resin having a melting point or softening point of 40 to 200 ° C., a thermoplastic silicone resin, and a molecular weight of 1,
Platinum group metal catalyst embedded by any one selected from heat-fusible compounds of 000 or less.
00 ppm, (E) Platinum group metal catalyst not embedded in thermoplastic resin, etc. Used together in an amount to supply platinum group metal atom in an amount of 1/10 weight or less of platinum group metal atom supplied from component (D). In addition, by further adding an addition reaction inhibitor, excellent storage stability, long pot life, good curability, cures quickly upon heat curing, and furthermore, the above-mentioned problems, namely, the adhesive component In addition, when used as a heat-curable silicone rubber adhesive, if the temperature setting in the continuous production line is relatively low and it takes a certain amount of time for the thermoplastic resin, etc. that embeds the platinum group metal catalyst to melt, The problem is that the curing and adhesion are incomplete in the production line, and the above composition is used together with a hydroxyl group source such as alcohol or water to form a foam as well in the heating line. When trying to obtain a foam, disadvantages such as not being able to obtain a good foam because it also suppresses initial foaming, furthermore, when molding electric wires and tubes with a millable type addition-cured material, high speed It has been found that when vulcanization is performed, it is possible to solve difficulties such as tackiness (stickiness) remaining on the surface and a smooth surface cannot be obtained.

That is, according to the present invention, at least 90% by weight (as platinum group metal atomic weight) of the platinum group metal catalyst in an amount that completes the addition reaction within a certain period of time by design is protected by a thermoplastic resin or the like, In addition to suppressing changes during storage, a reaction suppression system by chemical coordination that has been conventionally used without embedding 10% by weight or less (as platinum group metal atomic weight) of the platinum group metal catalyst in a thermoplastic resin or the like is used. As a result, it was possible to achieve both storage stability and curability.

Accordingly, the present invention provides: (A) 100 parts by weight of an organopolysiloxane represented by the following general formula (1); and (B) the following general formula having a hydrogen atom bonded to at least three silicon atoms in a molecule. 0.1 to 50 parts by weight of an organohydrogenpolysiloxane represented by (2), (C) 0 to 20 parts by weight of a compound having an active hydrogen group, (D) thermoplastic having a melting point or softening point of 40 to 200 ° C. Platinum group metal catalyst embedded with one selected from an organic resin, a thermoplastic silicone resin, and a heat-fusible compound having a molecular weight of 1,000 or less. (E) Platinum group metal catalyst An amount to supply platinum group metal atoms in an amount of 1/10 weight or less of the platinum group metal atoms supplied from the component (D), (F) Addition reaction suppression An organopolysiloxane composition comprising 0.001 to 20 parts by weight of an additive and (G) 0 to 1,000 parts by weight of a filler.

[0014]

Embedded image (However, in the formula, R ¹ and X are an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, an alkenyl group, and a part of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms. Groups, and groups selected from hydroxyl groups,
k represents an integer of 4 or more, R ¹ and X of the in a total volume of alkenyl and / or hydroxyl containing 0.001 mol%. )

[0015]

Embedded image (However, in the formula, R ² represents an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, and a hydrogen atom in which a part of the hydrogen atoms bonded to the carbon atoms of these groups is substituted with a halogen atom.
A group selected from a valence group, Y is an atom selected from a hydrogen atom and R ² or a monovalent group, m is an integer of 1 or more, n is an integer of 0 or more, and m + n is an integer of 3 to 500. )

Now, the present invention will be described in further detail. As described above, the organopolysiloxane composition of the present invention uses an organopolysiloxane as the component (A). This component (A) is the base polymer of the present composition and is essentially a linear organopolysiloxane,
It is represented by the following general formula (1).

[0017]

Embedded image

Here, the above R ¹ and X each have 1 to 1 carbon atoms.
0, preferably 1 to 8 alkyl groups, aryl groups, aralkyl groups, alkenyl groups, groups in which some of the hydrogen atoms on the carbon atoms of these groups have been replaced by halogen atoms, and groups selected from hydroxyl groups. is there. Specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl,
Hexyl, cyclohexyl, octyl, nonyl, alkyl such as decyl, vinyl, allyl, alkenyl such as propenyl, isopropenyl, butenyl, hexenyl, aryl such as phenyl, tolyl, etc. Groups, aralkyl groups such as benzyl group and phenylethyl group, halogenated hydrocarbon groups such as chloromethyl group, bromoethyl group and 3,3,3-trifluoropropyl group, and hydroxyl groups, but are not limited thereto. It is not something to be done. In this case, R ¹ and X may be the same or different from each other, but the total amount of R ¹ and X is 0.001.
〜1 mol%, especially 0.02-0.8 mol%, must be alkenyl groups and / or hydroxyl groups. Alkenyl groups and hydroxyl groups are functional groups that contribute to the crosslinking reaction, and if the amount is less than 0.001 mol%, the strength of the cured product is weak, lacks strength, and does not function as a rubber elastic body. If it exceeds 1 mol%, the crosslink density is high and the cured product becomes brittle. As a functional group contributing to the crosslinking reaction, the hydroxyl group is preferably bonded only to silicon atoms at both ends of the molecular chain, and the alkenyl group is bonded to any silicon atom at both ends of the molecular chain or in the middle of the molecular chain. May be bonded to both, or may be bonded to both, but in view of the physical properties of the cured product, etc., those containing at least an alkenyl group bonded to silicon atoms at both ends of the molecular chain. It is preferred that In addition, from the viewpoint of availability, cost, etc., X represents a vinyl group or a hydroxyl group, and R ¹
Is preferably selected from a methyl group, a phenyl group, a 3,3,3-trifluoropropyl group, and a vinyl group.

K is 4 or more, preferably 50 or more;
More preferably, it is an integer of 100 or more, and when k is 3 or less, the cured product becomes brittle and cannot be used as a molded product.
Although the upper limit of k is not particularly limited, it is usually 15,000.
0, preferably about 8,000, and the organopolysiloxane of the present invention may be in the form of a liquid, a paste, or a raw rubber.

The component (B) of the present invention has the following general formula (2)
An organohydrogenpolysiloxane represented by
It acts as a cross-linking agent or as a cross-linking and foaming agent.

[0021]

Embedded image

Here, R ² is an alkyl group, an aryl group, an aralkyl group having 1 to 10, preferably 1 to 8 carbon atoms, and a part of hydrogen atoms on carbon atoms of these groups is a halogen atom. Y is a hydrogen atom and an atom or a monovalent group selected from R ² . Here, an alkyl group for R ² or Y,
As the aryl group, aralkyl group and halogenated hydrocarbon group, the same ones as those exemplified for R ¹ can be exemplified, but R ² or Y which does not contain an aliphatic unsaturated group Preferably, the organohydrogenpolysiloxane has a hydrogen atom bonded to at least three silicon atoms in the molecule (ie,
(SiH group). N is 0 or more, preferably 0 to 499, more preferably 0 to 199.
M is an integer of 1 or more, preferably 3 to 500, more preferably 4 to 200, and the value of n + m is 3
To 500, preferably an integer of 4 to 200.

The component (B) is a crosslinking agent that reacts with the component (A) (that is, whether the alkenyl group in the component (A) and the SiH group in the component (B) are added by hydrosilylation, Alternatively, a silanol group in the component (A) and (B)
(The SiH group in the component is added by a dehydrogenation reaction), and also acts as a foaming agent by causing a dehydrogenation reaction with an optional component (C) to be described later. For 100 parts by weight of the polymer,
It is necessary to add 0.1 to 50 parts by weight, especially 1 to 25 parts by weight. When the amount is less than 0.1 part by weight, crosslinking cannot be sufficiently performed, and when the amount is more than 50 parts by weight, weather resistance is poor, and crosslinking cannot be performed again.

The component (A) does not contain a hydroxyl group (ie, a silanol group) bonded to a silicon atom, and does not contain the component (C) described later (the composition is foamed to form a foam or sponge). You don't need to do that)
The component (B) may be blended such that the molar ratio of the SiH group in the component (B) is 0.5 to 10, particularly about 1 to 5 per mole of the alkenyl group in the component (A). it can.

Next, the component (C) of the present invention is a compound having active hydrogen and is a necessary component when the composition of the present invention is used as a composition for a foam. If it is not necessary to form a foam or sponge, the formulation can be omitted. Here, the compound having active hydrogen refers to S in component (B) in the presence of a platinum group metal catalyst.
It means a compound having at least one hydrogen atom (for example, hydroxy group) in a molecule which can be dehydrogenated by reacting with iH group. As the compound having active hydrogen, a known compound can be used, but the compound must not deactivate the catalytic activity of the platinum group metal catalyst as the components (D) and (E) described later. Specifically, water, an alcohol compound having one or two or more OH groups in one molecule and having 1 to 20 carbon atoms, preferably about 1 to 12 carbon atoms, a silane containing a silanol group or 2 to 50 silicon atoms. , Preferably 2 to 20
Examples of such compounds include siloxane and the like, such as methanol, ethanol, n-propanol, iso-propanol, butanol, ethylene glycol, diethylene glycol, glycerin, trimethylsilanol, diphenylsilanediol, and those represented by the following formulas. These can be used alone or in combination of two or more.

[0026]

Embedded image (Me represents a methyl group.)

The amount of the component (C) is from 0 to 20 parts by weight based on 100 parts by weight of the base polymer of the component (A).
20 parts by weight, especially 0.1 to 15 parts by weight are blended.

The component (D) of the present invention is a microencapsulated platinum group metal catalyst. In the present invention, the platinum group metal catalyst is a platinum group metal atom such as platinum, palladium, and rhodium as a catalyst metal, and preferably contains a platinum atom. Means a complex.

The component (D) of the present invention acts as a catalyst for causing an addition reaction between the components (A) and (B).
A thermoplastic organic resin having a melting point or softening point of 0 to 200 ° C., a thermoplastic silicone resin, and a molecular weight of 1,000
A platinum group metal catalyst embedded (that is, microencapsulated) with any of 0 or less thermally fusible compounds. The component (D) exhibits the activity of the platinum group metal catalyst at or above the melting point (or softening point) of the compound to be embedded, and can contribute to curing and / or foaming of the composition. Accordingly, the melting point or softening point of the thermoplastic organic resin, the thermoplastic silicone resin, and the heat-fusible compound having a molecular weight of 1,000 or less is selected depending on the use of the composition of the present invention and storage conditions. Is 40-2
It needs to be 00 ° C, especially 50 to 150 ° C. 40
If the temperature is lower than ℃, storage stability at room temperature is not sufficient.
If the temperature is higher than 00 ° C., the storage stability is sufficient, but it takes a long time to cure.

In this case, as the thermoplastic organic resin, polyolefin resin, polystyrene resin, acrylic resin,
Non-silicone organic resins such as cellulosic resins, and thermoplastic silicone resins (ie, organopolysiloxane resins having a three-dimensional network structure containing a branched structure such as trifunctional siloxane units and / or SiO ₂ units)
Various types are selected and used, and fatty acids such as phenyl group or perfluoroalkyl group (eg, 3,3,3-trifluoropropyl group) and alkenyl group (eg, vinyl group, allyl group, propenyl group) are used. Silicone resins having group unsaturated groups are preferred. In addition, the molecular weight is 1,0
The heat-fusible compound having a molecular weight of 00 or less is a heat-fusible compound other than the thermoplastic organic resin and the thermoplastic silicone resin, and the heat-fusible compound is 2-butyne-1,4.
-Diol, diphenylacetylene, 4-hexylresorcinol, 2-vinylnaphthalene, 2-acetyl-1-tetralone, 2,5-diphenyloxazole, 3,6-
Dichloropyridazine, 2,5-toluquinone, 3,6-dimethyl-4-octyne-3,6-diol, bis (2
2,6,6-tetramethyl-4-piperidinyl) sebacate, di-n-octadecyl 3,3'-thiodipropionate, 2,4,7,9-tetramethyl-5-decyne-
4,7-diol, 2,5-dimethyl-3-hexyne-
2,5-diol, 1,3-bis (trimethylsilylethynyl) benzene, thiocoumaron-4-ol and the like can be used.

On the other hand, as the platinum group metal catalyst embedded in the resin or the heat-fusible compound, platinum, rhodium,
A catalyst containing a platinum group metal such as palladium, particularly preferably platinum.Examples include conventionally known addition reaction catalysts such as platinum black, chloroplatinic acid, and various complexes derived therefrom. Black, chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid and olefins, aldehydes, vinylsiloxane, acetylene,
Complexes with acetylene alcohols and the like can be mentioned.

Such a component (D) is disclosed in
Examples thereof include platinum group metal catalysts embedded in a silicone resin as described in JP-A-9-134786 and JP-A-4-46962. The silicone resin used here is a phenyl group or The compound preferably has both a perfluoroalkyl group and an aliphatic unsaturated group. Another example is disclosed in JP-A-64-474.
No. 42, a platinum group metal catalyst embedded with a thermoplastic organic resin such as polystyrene or polyolefin, and further, a heat-fusible material having a molecular weight of 1,000 or less not belonging to the above-mentioned thermoplastic organic resin. Platinum group compounds embedded with compounds can be mentioned.

In particular, the method for producing the platinum group metal catalyst embedded in the heat-fusible compound may be a known method such as the method described in the above-mentioned publications, and is not particularly limited. For example, it can be obtained by bringing a heat-fusible compound and a platinum group compound into contact with each other in a molten or dissolved state of the heat-fusible compound. Here, in the case of performing thermal melting, the compound is heated to a temperature equal to or higher than the melting point of the compound, and in the case of performing dissolution, a platinum group metal catalyst is supported in a state of being homogenized or dispersed in a solvent, and then cooled or evaporated. Then, a solid catalyst in which the platinum group metal catalyst is uniformly dispersed is obtained. In addition, these are sprayed and solidified by spraying them in a liquid state in melting or dissolving, or a solvent is removed, and a method by spray drying to obtain fine particles,
A method of emulsifying with an emulsifier in water to obtain a solid catalyst,
A method in which a solid catalyst is obtained by a so-called freeze-drying method in which the solvent is cooled to a temperature lower than the solidification temperature of the solvent while being dissolved in the solvent, and the solvent is removed under reduced pressure. The solid catalyst thus obtained may be used as a powder, or may be used by dispersing it in a slurry or paste again with silicone oil.

The amount of the component (D) is such that the platinum group metal atom is supplied in an amount of 1 to 1,000 ppm, preferably 5 to 200 ppm, based on the total amount of the composition.

The component (E) of the present invention is a platinum group metal catalyst,
This has the above-mentioned meaning, and uses a platinum group metal catalyst itself which is not embedded in a thermoplastic organic resin, a thermoplastic silicone resin, or a heat-fusible compound. This complements the function of the component (D) as an addition reaction catalyst. Specifically, it improves initial curing and initial foaming, and is particularly useful when molding electric wires and tubes that are subjected to high-speed vulcanization. The problem of surface tack (stickiness) or the like which is a problem can be solved.

As the component (E), a conventionally known platinum group metal catalyst can be used. Unlike the component (D), the platinum group metal catalyst is a thermoplastic resin,
The thermoplastic silicone resin, which is not embedded in the heat-fusible compound and is directly incorporated into the composition, specifically, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, chloride Complexes of platinic acid with olefins, aldehydes, vinylsiloxanes, acetylenes, acetylene alcohols and the like can be exemplified.

The amount of the component (E) is such that the amount of platinum group metal atoms in the component (E) is 1/10 by weight of the amount of platinum group metal atoms supplied from the component (D). Or less, preferably 1/20 or less, and the lower limit is 1 / 100,000 (0.001%), preferably 1 in the above weight ratio.
/ 1,000 (0.1%), especially 1/100 (1%). If the amount is too large, the balance between the storability and the curability cannot be maintained. On the other hand, if the amount is too small, the effect of the combined use of the component (D) and the component (E) may not be obtained.

The addition reaction inhibitor which is the component (F) of the present invention is used for the purpose of controlling the reaction by the platinum group metal atom supplied from the above-mentioned component (E). Specific examples thereof include benzotriazole compounds (JP-B-40-25069) and acetylene alcohol-based compounds (JP-B-44-3).
1476), vinyl group-containing polysiloxane compounds (JP-B-48-10947), hydroperoxides (JP-B-57-20340), amine compounds (JP-A-63-56563) and the like. And preferably from acetylene or an acetylene alcohol-containing compound.
More specifically, 3-methyl-1-butyn-3-ol,
3-methyl-1-pentyn-3-ol, ethynylcyclohexanol, 3,5-dimethyl-1-hexyne-3
-All.

The amount of the component (F) varies depending on the structure and molecular weight of the component (F). Is in the range of 0.002 to 5 parts by weight,
Basically, the amount is preferably about 1 to 1,000 equivalents, particularly preferably 2 to 500 equivalents to the platinum group metal atom supplied as the component (E).

The filler as the component (G) of the present invention is an optional component added for increasing the amount of the composition or reinforcing the physical strength, and further for flame retardancy, heat conductivity, and electrical conductivity.
Specifically, fumed fumed silica, precipitated silica, crystalline crushed silica, colloidal calcium carbonate, precipitated calcium carbonate, heavy calcium carbonate, acetylene black, furnace carbon, titanium oxide, metal, metal oxide and silane And those treated with a siloxane compound. The amount of the component (G) is
0 to 1,000 parts by weight, particularly 1 to 1,000 parts by weight, preferably 1 to 400 parts by weight, per 100 parts by weight of the component (A).
If the amount exceeds 1,000 parts by weight, the compounding becomes difficult, the cured product becomes brittle, and the mechanical properties become extremely poor.

The composition of the present invention comprises the above (A) to
The component (G) can be compounded, but if necessary, known additives can also be compounded. Specific examples of these additives include a thixotropic agent used in the art, Resin as a plasticizer, a silicone resin as a plasticizer, a silicone resin containing R ₃ SiO _1/2 units and a SiO ₂ unit as a basic structure for reinforcing the strength, or a silicone resin containing a structure having a basic structure of RSiO _3/2 units And the like can be added as long as the object of the present invention is not impaired (here, R represents a monovalent hydrocarbon group having 1 to 8 carbon atoms such as an alkyl group, an alkenyl group, and an aryl group).

In this case, a carbon functional silane or siloxane having a reactive group is effective as an adhesion improver, for example, γ-glycidoxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ -(Tri) alkoxysilane having an epoxy functional group such as methacryloxypropyltrimethoxysilane and a reactive group such as an acrylic functional group, and a partially hydrolyzed condensate thereof, and a methylhydrogenpolysiloxane having a terminal trialkoxysilyl group blocked. , Trimethoxysilylpropyl-modified cyclic methyl hydrogen polysiloxane, triallyl isocyanurate, etc., in an amount of 0 to 50 parts by weight, preferably 0.1 to 50 parts by weight, per 100 parts by weight of component (A). 01 to 50 parts by weight, more preferably 0.0 It may be about 10 parts by weight.

The curing conditions of the composition of the present invention can be appropriately selected depending on the application.
This is performed for about 120 minutes.

[0044]

As described above, the organopolysiloxane composition of the present invention has both preservability and curability.

[0045]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to synthesis examples, examples, and comparative examples of catalysts, but the present invention is not limited to the following examples. In addition, the part in the following examples shows a weight part.

[Synthesis example 1 of catalyst]
In a toluene solution of 0 ppm of a siloxane-modified platinum complex, a phenyl group containing C ₆ H ₅ SiO _3/2 units and (CH ₂ ＣＨCH) SiO _3/2 units having the same melting point as toluene and a melting point of 78 ° C. Add vinyl group-containing silicone resin,
Stir until uniform, and spray-dry the resin powder platinum catalyst (Catalyst 1, platinum atomic weight: 5,000p
pm) was prepared.

[Catalyst Synthesis Example 2] 3,6-dimethyl-4-
5 g of octin-3,6-diol (melting point: 54 ° C.) was added to a siloxane complex containing vinyl group 5 derived from chloroplatinic acid.
g, heat-treated at 80 ° C. for 1 hour, stripped, and then cooled to prepare a solid hydrosilylation catalyst (catalyst 2, platinum atomic weight: 5,000 ppm).

Catalyst Synthesis Example 3 Vinyl group-containing siloxane complex 5 derived from chloroplatinic acid was added to 5 g of 1,3-bis (trimethylsilylethynyl) benzene (melting point 58 ° C.).
g, and heat-treated at 80 ° C. for 1 hour. To this, 0.5 g of a polyglycerin-based surfactant was added, emulsified in water, and then filtered and dried to obtain a fine powdery hydrosilylation catalyst (Catalyst 3, (Atomic weight of platinum: 5,000 ppm).

[Example 1] Both ends of the molecular chain were blocked with a vinyldimethylsilyl group and the viscosity at 25 ° C was 30,000 c
100 parts of p-dimethylpolysiloxane and 10 parts of fumed silica having a specific surface area of 130 m ² / g, the surfaces of which were treated with dichlorosilane, were put into a universal mixer and mixed until uniform to prepare a base compound.

To 100 parts of this base compound, 2.0 parts of the catalyst 1 obtained in Catalyst Synthesis Example 1 (100 pp in terms of platinum with respect to the base compound)
m), 0.1 part of a toluene solution of the same siloxane-modified platinum complex as used in Catalyst Synthesis Example 1 (5.0 ppm in terms of platinum with respect to the base compound),
And 0.002 parts of 2-ethylhexanol and stirred with a universal mixer until uniform, and then both ends were further reduced to 0.005 m of SiH groups blocked with trimethylsilyl groups.
ol / g of methyl hydrogen polysiloxane is added and mixed, and the weight ratio of the platinum atom in the component (E) to the platinum atom in the composition 1 is 0.0.
5%).

[Example 2] Both ends of a molecular chain were blocked with a vinyldimethylsilyl group, and the viscosity at 25 ° C was 30,000 c.
100 parts of p-dimethylpolysiloxane and 10 parts of fumed silica having a specific surface area of 130 m ² / g, the surfaces of which were treated with dichlorosilane, were put into a universal mixer and mixed until uniform to prepare a base compound.

0.2 parts of water and 1.0 part of catalyst 1 (50 ppm in terms of platinum with respect to the base compound) based on 100 parts of the base compound, the same siloxane as used in Catalyst Synthesis Example 1 After adding 0.01 part of a toluene solution of the modified platinum complex (0.5 ppm in terms of platinum with respect to the base compound) and 0.002 part of 2-ethylhexanol, and stirring the mixture with a universal mixer until uniform. And methylhydrogenpolysiloxane (SiH group content: 0.016 mol / g) having a viscosity of 40 cp at 25 ° C., both ends of which are blocked with trimethylsilyl groups.
Parts and phenylsilane were added and mixed to obtain composition 2 (the weight ratio of platinum atoms in component (E) to platinum atoms in component (D) was 0.01%).

Example 3 Both ends of the molecular chain were blocked with a vinyldimethylsilyl group and the viscosity at 25 ° C. was 30,000 c.
100 parts of p-dimethylpolysiloxane and 10 parts of fumed silica having a specific surface area of 130 m ² / g, the surface of which was treated with dichlorosilane, were placed in a universal mixer and stirred until uniform to prepare a base compound.

0.2 parts of water and 1.0 part of catalyst 2 (50 ppm in terms of platinum with respect to the base compound) based on 100 parts of the base compound, the same siloxane as used in Catalyst Synthesis Example 1 After adding 0.01 part of a toluene solution of the modified platinum complex (0.5 ppm in terms of platinum with respect to the base compound) and 0.002 part of 2-ethylhexanol, and stirring the mixture with a universal mixer until uniform. And methylhydrogenpolysiloxane (SiH group content: 0.016 mol / g) having a viscosity of 40 cp at 25 ° C., both ends of which are blocked with trimethylsilyl groups.
And 0.3 part of phenylsilane were added and mixed to obtain composition 3 (weight ratio of platinum atoms in component (E) to platinum atoms in component (D) was 0.01%).

COMPARATIVE EXAMPLE 1 Both ends of the molecular chain were blocked with a vinyldimethylsilyl group and the viscosity at 25 ° C. was 30,000 c.
100 parts of p-dimethylpolysiloxane and 10 parts of fumed silica having a specific surface area of 130 m ² / g, the surface of which was treated with dichlorosilane, were placed in a universal mixer and stirred until uniform to prepare a base compound.

To 100 parts of this base compound, 2.1 parts of catalyst 1 (105 ppm in terms of platinum with respect to the base compound) was added, and the mixture was stirred with a universal mixer until the mixture became uniform. 16 parts of methyl hydrogen polysiloxane having 0.005 mol / g of SiH groups blocked with trimethylsilyl groups were added and mixed to obtain Composition 4.

Comparative Example 2 Both ends of the molecular chain were blocked with a vinyldimethylsilyl group and the viscosity at 25 ° C. was 30,000 c.
100 parts of p-dimethylpolysiloxane and 10 parts of fumed silica having a specific surface area of 130 m ² / g, the surface of which was treated with dichlorosilane, were placed in a universal mixer and stirred until uniform to prepare a base compound.

To 100 parts of the base compound, 2.1 parts of a toluene solution of the same siloxane-modified platinum complex as used in Catalyst Synthesis Example 1 (105 ppm in terms of platinum with respect to the base compound), and 2- After adding 0.002 parts of ethylhexanol and stirring with a universal mixer until uniform, 16 parts of methylhydrogenpolysiloxane having 0.005 mol / g of SiH groups whose both ends are blocked with trimethylsilyl groups are further added. In addition, mixing was performed to obtain Composition 5.

Comparative Example 3 Both ends of the molecular chain were blocked with vinyldimethylsilyl groups and the viscosity at 25 ° C. was 30,000 c.
100 parts of p-dimethylpolysiloxane and 10 parts of fumed silica having a specific surface area of 130 m ² / g, the surface of which was treated with dichlorosilane, were placed in a universal mixer and stirred until uniform to prepare a base compound.

To 100 parts of this base compound, 2.1 parts of catalyst 1 (105 ppm in terms of platinum relative to the base compound) and 0.002 parts of 2-ethylhexanol were added, and the mixture was uniformly mixed with a universal mixer. Then, 16 parts of methylhydrogenpolysiloxane having 0.005 mol / g of SiH groups whose both ends were blocked with a trimethylsilyl group were added and mixed to obtain Composition 6.

Comparative Example 4 Both ends of the molecular chain were blocked with vinyldimethylsilyl groups, and the viscosity at 25 ° C. was 30,000 c.
100 parts of p-dimethylpolysiloxane and 10 parts of fumed silica having a specific surface area of 130 m ² / g, the surface of which was treated with dichlorosilane, were placed in a universal mixer and stirred until uniform to prepare a base compound.

To 100 parts of the base compound, 0.2 parts of water, 1.01 part of catalyst 2 (50.5 ppm in terms of platinum with respect to the base compound), and 2-
After adding 0.002 parts of ethylhexanol and stirring with a universal mixer until uniform, methylhydrogenpolysiloxane (viscosity of 40 cp at 25 ° C, both ends of which are blocked with trimethylsilyl groups, having a SiH group content of 40 cp) was added. 0.0
16 mol / g) and 5 parts of phenylsilane were added and mixed to obtain a composition 7.

Example 4 100 parts of dimethylpolysiloxane having a viscosity of 20,000 cp at 25 ° C., both ends of which are blocked by a hydroxyl group, and a fume having a specific surface area of 130 m ² / g treated with dichlorosilane 10 parts of silica in a state was placed in a universal mixer and stirred until uniform, thereby preparing a base compound.

For 100 parts of the base compound, 0.2 parts of water and 1.0 part of the catalyst 3 (50 ppm in terms of platinum with respect to the base compound) were obtained by using the same siloxane as used in Catalyst Synthesis Example 1. After adding 0.01 part of a toluene solution of the modified platinum complex (0.5 ppm in terms of platinum with respect to the base compound) and 0.002 part of 2-ethylhexanol, and stirring the mixture with a universal mixer until uniform. And methylhydrogenpolysiloxane (SiH group content: 0.016 mol / g) having a viscosity of 40 cp at 25 ° C., both ends of which are blocked with trimethylsilyl groups.
Part 8 and mixed, and the composition 8 (the weight ratio of the platinum atom in the component (E) to the platinum atom in the component (D) is 0.01%)
I got

The following experiments were performed on the obtained compositions 1 to 8. First, for Example 1 and Comparative Examples 1, 2, and 3, a difference in curability was confirmed with a curastometer.
Table 1 shows the measurement results.

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[Table 1]

As shown in Table 1, in the case of the ordinary microencapsulated platinum catalyst of Comparative Example 1 (that is, only the component (D)), it took three minutes or more from the start of curing to the end of curing. Further, in the system of Comparative Example 2 in which a small amount of a control agent was added to the untreated platinum catalyst (that is, the component (E)), a sufficient pot life at room temperature was obtained because the time until the start of curing was short. When stored at room temperature, it gelled in 3 hours. In the system in which the control agent was added to the microencapsulated platinum catalyst (component (D)) of Comparative Example 3, the 10% torque time was longer than that of Comparative Example 1, but the 10% torque time to 90% torque time was lower. The time is extremely long and it takes too long to complete the curing. On the other hand, Embodiment 1
Then, while the pot life is longer than that of Comparative Example 1,
It can be seen that the time until the completion of curing is short, and that a long pot life and rapid curing characteristics are obtained. In this case, depending on the concentration of the microencapsulated platinum catalyst (component (D)), the amount of the control agent (component (F)) added later, and the amount of the platinum catalyst (component (E)) added, the desired pot life and curing can be achieved. A composition having both speed can be obtained.

Next, Examples 2, 3, and 4 and Comparative Example 4 were compared in a cell state after being foamed by curing into a sponge-like foam under curing conditions of 120 ° C. and 20 minutes. Table 2 shows the results.

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[Table 2]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 83:05) (72) Inventor Hironobu Muramatsu 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture 10 Shin-Etsu Chemical Co., Ltd. Silicone electronic materials Inside the Technical Research Institute

Claims (1)

[Claims] (A) 100 parts by weight of an organopolysiloxane represented by the following general formula (1): (However, in the formula, R ¹ and X are an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, an alkenyl group, and a part of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms. Groups, and groups selected from hydroxyl groups,
k represents an integer of 4 or more, R ¹ and X of the in a total volume of alkenyl and / or hydroxyl containing 0.001 mol%. (B) 0.1 to 50 parts by weight of an organohydrogenpolysiloxane represented by the following general formula (2) having at least three hydrogen atoms bonded to silicon atoms in the molecule: (However, in the formula, R ² represents an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group, and a hydrogen atom in which a part of the hydrogen atoms bonded to the carbon atoms of these groups is substituted with a halogen atom.
A group selected from a valence group, Y is an atom selected from a hydrogen atom and R ² or a monovalent group, m is an integer of 1 or more, n is an integer of 0 or more, and m + n is an integer of 3 to 500. (C) a compound having an active hydrogen group in an amount of 0 to 20 parts by weight, (D) a thermoplastic organic resin having a melting point or a softening point of 40 to 200 ° C., a thermoplastic silicone resin, and heat having a molecular weight of 1,000 or less. Platinum group metal catalyst embedded by any one selected from fusible compounds Platinum group metal atom 1 to 1,000 ppm with respect to the total amount of the composition, (E) Platinum group metal catalyst Supplied from component (D) (F) addition reaction inhibitor 0.001 to 20 parts by weight, (G) filler 0 to 1,000 parts by weight An organopolysiloxane composition comprising: