JPH0565414A - Thermosetting silicone rubber composition, rubber laminate using the same composition and its production - Google Patents

Abstract

PURPOSE:To obtain the resin composition useful for a field of automobile, etc., having adhesive power by blending a specific polyorganosiloxane, etc., with a specific polyrganohydrogen siloxane, a filler, a platinum-based catalyst and an organic peroxide in a specific ratio. CONSTITUTION:(A) 100 pts.wt. polyorganosiloxane of formula I [R<1> is (substituted) monofunctional hydrocarbon and 0-50 mol% of the R<1> is vinyl; (n) is 1,900-2,004] having 500-12,000 average degree of polymerization, is blended with (B) 10-200 pts.wt. filler, (C) 0.1-20 pts.wt. polyorganosiloxane shown by formula II [R<2> is (substituted) monofunctional hydrocarbon and 5-50 mol% R<2> is vinyl; (m) is 1-3] having 3-500 average-degree of polymerization, (D) 0.1-20 pts.wt. polyorganohydrogen silioxane having two or more hydrogens bonded to a silicon atom on the average in one molecule, (E) 0.01-5,000 ppm (calculated as platinum-base metal) platinum-based catalyst and (F) 0.1-20 pts.wt. organic perioxide to give the objective composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting silicone rubber composition, a rubber laminate using the same, and a method for producing the same. More specifically, the silicone rubber and the organic rubber are intermediate layers or adhesives. TECHNICAL FIELD The present invention relates to a thermosetting silicone rubber composition useful for producing a laminated body that is firmly bonded regardless of the above, a rubber laminated body using the same, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, the demands on the performance of rubber materials have become stricter year by year, and the types of rubber materials used have changed. Among rubber, silicone rubber is
It has outstanding performance in heat resistance, cold resistance and weather resistance compared to other rubbers, and its demand is increasing year by year in industrial fields, automobiles, aircraft, medical fields and the like.

However, since silicone rubber is more expensive and mechanical strength is slightly inferior to organic rubber,
The fields used were limited. Therefore, it has been attempted to compound the silicone rubber and the organic rubber in order to make full use of the advantages of the silicone rubber and to supplement the drawbacks.

For example, Japanese Patent Laid-Open No. 63-72745 and Japanese Patent Laid-Open No.
In JP-A 1-103636, JP-A 1-272648, and the like, in order to improve the drawbacks of silicone rubber, it has been studied to combine silicone rubber with various organic rubbers to form a composite.

However, when considering various rubber parts, it cannot be said that the performance is sufficient yet only by mixing and compounding silicone rubber and organic rubber, and it is necessary to laminate with other materials. ..

Further, it has been studied to laminate silicone rubber and organic rubber to form a composite, but since silicone rubber and organic rubber are difficult to co-crosslink, a laminate in which silicone rubber and organic rubber are firmly adhered is used. It was difficult to get.

Therefore, studies have been conducted to increase the adhesive strength. For example, Japanese Patent Publication No. 57-26233 and Japanese Patent Publication No. 61-25544.
The publication discloses a method of placing a blend of the organic rubber and the silicone rubber in the middle of a plurality of layers when the silicone rubber and the organic rubber are bonded. However,
These methods have drawbacks such as the need to manufacture the intermediate layer and the complicated bonding operation.

On the other hand, Japanese Patent Application No. 2-18186 discloses a method of directly bonding silicone rubber and organic rubber by vulcanization adhesion. Although this method does not require an intermediate layer, it has a problem in vulcanization adhesion in the presence of air. That is, in order to vulcanize silicone rubber in the presence of air, it is necessary to use an acyl-based organic peroxide or a hydrosilylation reaction. However, the acyl-based peroxide has a low decomposition temperature, and therefore, it cannot be molded before vulcanization. There is a problem that it is difficult to use because it causes early vulcanization in the process, and the hydrosilylation reaction is difficult to react with the organic rubber, resulting in poor adhesion.

[0009]

As described above, conventionally, there is a demand for compounding with an organic rubber in order to improve the drawbacks of the silicone rubber, and various studies have been made. However, only mixing the silicone rubber and the organic rubber is required. However, the effect of compounding is not sufficient, and in the case of stacking, the method of providing an intermediate layer has a drawback that the manufacturing process becomes complicated. There was a problem that I could not.

The present invention has been made in view of the above problems of the prior art, and is a thermosetting silicone rubber composition which is laminated with an organic rubber and exhibits a good adhesive force even by heat vulcanization in the presence of air. It is an object of the present invention to provide a product, a laminate in which a silicone rubber and an organic rubber are firmly bonded using the product, and a method for producing the same.

[0011]

Means for Solving the Problems As a result of intensive studies by the present inventors, the thermosetting silicone rubber composition was blended with a specific amount of siloxane containing a vinyl group, and a platinum-based catalyst and organic peroxide were used. It was found that a thermosetting silicone rubber composition intended to solve the above problems can be obtained by using these substances together, and the present invention has been completed.

That is, the present invention provides (A) an average composition formula R ¹ _n SiO _{(4-n) / 2} (I) (wherein R ¹ is a substituted or unsubstituted monovalent hydrocarbon group and 100 parts by weight of a polyorganosiloxane having an average degree of polymerization of 500 to 12000 represented by 0 to 5 mol% of vinyl groups and n being a number of 1.900 to 2.004, (B) 10 to 200 parts by weight of a filler, (C ) Average composition formula R ² _m SiO _{(4-m) / 2} (II) (wherein, R ² is a substituted or unsubstituted monovalent hydrocarbon group, and 5 to 50 mol% thereof is a vinyl group, m Is an integer of 0 <m <4) 0.1 to 20 parts by weight of a polyorganosiloxane having an average degree of polymerization of 3 to 500, and (D) at least two hydrogen atoms bonded to silicon atoms are contained in one molecule on average. 0.1 to 20 parts by weight of polyorganohydrogensiloxane having a number exceeding (E) Platinum catalyst (as platinum metal amount) 0.01 to 5000 The present invention relates to a thermosetting silicone rubber composition, which comprises 0.1 to 20 parts by weight of (F) organic peroxide as a component.

A silicone rubber layer made of the thermosetting silicone rubber composition and an organic rubber layer made of an organic rubber composition containing an organic peroxide as a vulcanizing agent are laminated and integrally formed. Laminate characterized by being vulcanized and bonded, and an unvulcanized silicone rubber layer comprising the thermosetting silicone rubber composition, and an organic rubber composition containing an organic peroxide as a vulcanizing agent. And a non-vulcanized organic rubber layer made of a solid material, and then heated to integrally vulcanize and bond the silicone rubber layer and the organic rubber layer to produce a laminate. It is about the method. Hereinafter, the present invention will be described in more detail.

The polyorganosiloxane of the component (A) which constitutes the thermosetting silicone rubber composition of the present invention is generally used as a base polymer of silicone rubber, and in the formula (I), R ¹ is methyl. Groups, alkyl groups such as ethyl group and propyl group; alkenyl groups such as vinyl group and allyl group; cycloalkyl groups such as cyclohexyl group; aralkyl groups such as β-phenylethyl group; aryl groups such as phenyl group; A substituted or unsubstituted monovalent hydrocarbon group as exemplified by a 1,3-trifluoropropyl group and the like, based on the total amount of the substituted or unsubstituted monovalent hydrocarbon group bonded to the silicon atom. A group is contained in the range of 0 to 5 mol%. When the vinyl group exceeds 5 mol%, the strength of the vulcanized silicone rubber decreases.

The terminal unit of this polyorganosiloxane may be a triorganosiloxy group, a hydroxy group or an alkoxy group. Examples of the triorganosiloxy group include a trimethylsiloxy group, a dimethylvinylsiloxy group, a methylphenylvinylsiloxy group, a methyldiphenylsiloxy group and the like, and the like.

The average degree of polymerization of the polyorganosiloxane is in the range of 500 to 12000, preferably 1000 to 7000. If the average degree of polymerization is less than 500, good mechanical properties cannot be obtained, and if it exceeds 12000, it becomes difficult to disperse the filler.

The polyorganosiloxane may be used alone or as a mixture of two or more, if necessary.

The filler as the component (B) imparts mechanical strength to the silicone rubber, and is a known reinforcing or non-reinforcing filler which is usually used for silicone rubber.

Examples of the reinforcing filler include fumed silica, precipitated silica, calcined silica and silica airgel. Among them, fumed silica and calcined silica having a low water content are suitable.

These reinforcing fillers may be those whose surface has not been treated, those which have been surface-treated in advance with an organosilicon compound such as organochlorosilane, polydiorganosiloxane and hexaorganodisilazane, or which may be hexahydrated during kneading. It may be surface-treated with an organosilicon compound such as organodisilazane. Such surface treatment can be performed by any known method.

Further, examples of the non-reinforcing filler include ground quartz, diatomaceous earth, carbon black, ferrite, calcium carbonate and the like.

These fillers can be used alone or
Two or more kinds can be used in combination, and the compounding ratio when they are used in combination can be arbitrarily selected.

The amount of the component (B) blended is 10 to 200 parts by weight, preferably 20 to 150 parts by weight, more preferably 30 to 100 parts by weight, based on 100 parts by weight of the polyorganosiloxane of the component (A).
100 parts by weight. If it is less than 10 parts by weight, sufficient mechanical strength cannot be obtained, and if it exceeds 200 parts by weight, extrusion processability is deteriorated.

The polyorganosiloxane of component (C) is
In the above formula (II), R ² is an alkyl group such as a methyl group, an ethyl group, a propyl group or the like; an alkenyl such as a vinyl group or an allyl group, like R ¹ in the formula (I) when the component (A) is used. Group; cycloalkyl group such as cyclohexyl group; aralkyl group such as β-phenylethyl group; aryl group such as phenyl group; substituted or unsubstituted 1 as exemplified by 3,3,3-trifluoropropyl group 5 to 50 mol% of a vinyl group, based on the total amount of the substituted or unsubstituted monovalent hydrocarbon group bonded to the silicon atom.
It is preferably contained in the range of 10 to 50 mol%.
If the amount of vinyl groups is too large or too small, sufficient adhesive force cannot be obtained.

The average degree of polymerization of this polyorganosiloxane is in the range of 3 to 500, preferably 3 to 200.
If the average degree of polymerization is less than 3, volatilization is likely to occur and handling becomes difficult, and if it exceeds 500, sufficient adhesive force cannot be obtained.

The component (C) polyorganosiloxane is
Although it is mainly linear or cyclic, a part of it may be branched, and it may be a copolymer or a mixture thereof.

The compounding amount of the component (C) is 0.1 to 20 parts by weight, preferably 0.3 to 15 parts by weight, more preferably 0.5, based on 100 parts by weight of the polyorganosiloxane of the component (A).
The range is up to 10 parts by weight. If the amount is less than 0.1 parts by weight, sufficient adhesive force cannot be obtained, and if the amount exceeds 20 parts by weight, the strength and heat resistance of the vulcanized silicone rubber are impaired.

The component (D), a polyorganohydrogensiloxane, acts as a cross-linking agent for the silicone rubber composition and has an average of at least 2 hydrogen atoms bonded to silicon atoms per molecule in order to form a network structure. There must be a number.

As the organic group bonded to the silicon atom,
Examples are the same as the organic group bonded to the silicon atom of the polyorganosiloxane of the component (A) or the component (C).
Although the average degree of polymerization of this polyorganohydrogensiloxane is not particularly limited, it is difficult to synthesize one having two or more hydrogen atoms bonded to the same silicon atom.
It is preferably composed of one or more siloxy units.

The siloxane skeleton of the component (D) may be linear, cyclic or branched. In addition, the compounding amount is 100% of the polyorganosiloxane of the component (A).
0.1 to 20 parts by weight, preferably 0.2
-15 parts by weight, more preferably 0.3-10 parts by weight. 0.
If it is less than 1 part by weight or more than 20 parts by weight, a rubber elastic body having excellent physical properties cannot be obtained.

The platinum-based catalyst as the component (E) may be a known catalyst usually used in addition reaction compositions, and examples thereof include chloroplatinic acid and alcohol-modified chloroplatinic acid (US Pat. No. 3220).
972), a complex of chloroplatinic acid and olefin (see US Pat. Nos. 3159601 and 3159662),
L ₄ Pt (where L is PR ′ ₃ , where R ′ is the same or different monovalent substituted or unsubstituted organic group), vinyl group-containing polysiloxane-Pt complex, platinum black or alumina, silica Examples of such carriers include solid platinum supported on a carrier. This platinum-based catalyst is alcohol-based, polysiloxane-based, ketone-based, ether-based,
It may be used by dissolving it in a solvent such as a hydrocarbon type.

The blending amount of the component (E) may be appropriately adjusted according to the desired curing rate, but from the economical viewpoint and from the viewpoint of obtaining a good cured product, chloroplatinic acid or the like is used. For those which are compatible with siloxane, the amount of platinum-based metal is 0.1 to 30 ppm with respect to the polyorganosiloxane of component (A), and for solid catalysts such as platinum black, the range is 20 to 500 ppm.

Examples of the organic peroxide as the component (F) include acyl peroxides such as dibenzoyl peroxide, dicumyl peroxide, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane. , 2,5-dimethyl-2,5-
Alkyl peroxides such as di (putylperoxy) hexyne-3, α, α'-bis (t-butylperoxy) -p-diisopropylbenzene, t-butylperoxyacetate, t-butylperoxyisopropylcarbonate, t Examples include peroxyesters such as -butylperoxybenzoate, but among them, alkyl peroxides are preferable. These may be used alone or in combination of two or more, and the amount thereof is based on 100 parts by weight of the polyorganosiloxane of the component (A).
The amount is in the range of 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, more preferably 0.5 to 10 parts by weight. If the amount of the component (F) is less than 0.1 parts by weight or more than 20 parts by weight, a rubber elastic body having excellent adhesive strength and physical properties cannot be obtained.

In addition to the above components, the thermosetting silicone rubber composition of the present invention may optionally contain at least one alkenyl group and / or at least one alkenyl group per molecule.
Such as alkoxysilanes having one methacryloxy group or its hydrolyzed condensates, polyorganosiloxanes containing at least one epoxy group, alkenyl group, methacryloxy group and methoxy group in one molecule and having a degree of polymerization of 2 to 50. Characteristic improver, heat resistance additive, antioxidant,
Various additives such as a processing aid, a flame retardant, a pigment, a hydrosilylation reaction inhibitor and the like can be appropriately added.

In the thermosetting silicone rubber composition of the present invention, the above components (A) to (F) and other additives to be blended as necessary are added to a Banbury mixer, a plastomill, a kneader and a two roll roll. It can be obtained by uniformly mixing with any kneader such as. Although the addition method and the addition order of each component are not particularly limited,
It is preferable that the platinum catalyst as the component (E) and the organic peroxide as the component (F) be added last. It is also possible to apply heat history such as heating and kneading.

Next, the rubber laminate and the method for producing the same according to the present invention will be described.

The thermosetting silicone rubber composition used in the rubber laminate of the present invention is the thermosetting silicone rubber composition described above.

The organic rubber composition constituting the organic rubber layer laminated with the silicone rubber layer made of such a thermosetting silicone rubber composition is based on (a) organic rubber, and (B) It is a mixture of an organic peroxide and other components to be blended, if necessary.

The organic rubber as the component (a) may be any one that can be vulcanized with an organic peroxide, and therefore, an unsaturated group, a tertiary carbon atom, a bromine atom, an iodine atom, an active hydrogen group, or the like is included in the molecule. A polymer having a group that is easily abstracted by a radical, such as IR, BR, SBR, NBR, and C.
R, diene rubber such as natural rubber and its hydrogenated product, butyl rubber and / or its halide, ethylene / α-olefin copolymer rubber, acrylic rubber, ethylene and / or vinyl acetate and an acrylic ester Polymerized rubber, copolymer rubber of epihalohydrin and unsaturated group-containing monomer such as allyl glycidyl ether,
Halogenated or chlorinated polyethylene
Copolymer of ethylene and vinyl acetate (EVA), bromine,
Examples thereof include iodine, tertiary carbon and / or fluororubber having an unsaturated double bond. These are one or two
A mixture of two or more species can be used. It is also possible to mix silicone rubber as a rubber component used in combination with such an organic rubber.

The organic peroxide as the component (b) may be the same as the organic peroxide in the thermosetting silicone rubber composition, but it is not always necessary to use the same one. The amount of this organic peroxide added is
The amount is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the component (a) organic rubber. In addition, when silicone rubber is used in combination with organic rubber, 0.1 to 20 per 100 parts by weight of these total amounts is used.
Parts by weight are preferred.

Further, as another component to be blended as necessary, a crosslinking aid for improving the adhesiveness can be mentioned.
Examples of the crosslinking aid include polyorganosiloxanes similar to the polyorganosiloxane of the component (C) in the thermosetting silicone rubber composition, polyfunctional allyl compounds such as triallyl isocyanurate and triallyl cyanurate, ethylene. Polyfunctional polymers such as glycol dimethacrylate, trimethylolpropane trimethacrylate, polyfunctional acrylic or methacrylic acid esters such as polyethylene glycol diacrylate, m-phenylene bismaleimide, oxime compounds, sulfur compounds, 1,2-polybutadiene Etc., but vinyl group-containing polyorganosiloxane is preferable. When the vinyl group-containing polyorganosiloxane is used, it is not always necessary to use the same one used in the thermosetting silicone rubber composition.

In addition, in order to improve the characteristics, at least one alkenyl group and / or at least one alkenyl group in one molecule.
Alkoxysilanes having one methacryloxy group, or their hydrolysis-condensation products, and organopolysiloxanes containing at least one methacryloxy group, an epoxy group, an alkenyl group, and a methoxy group in a molecule and having a degree of polymerization of 2 to 50. It can be blended.

Further, various additives generally used as additives for organic rubber can be blended. Such additives include carbon black, silica, calcium carbonate, magnesium carbonate, zinc carbonate, aluminum silicate, calcium silicate, magnesium silicate,
Reinforcing agents such as metal oxides, glass flakes, glass fibers, granules, discs or fibrous inorganic and organic fillers, fillers, paraffin oils, naphthenic oils, aroma oils, softening of liquid polymers Agents, phthalates, adipates, maleates, fumarates, phosphates and other plasticizers,
Examples thereof include processing aids such as stearic acid, sodium stearate, fatty acid esters and fatty acid amides, lubricants, pigments, coupling agents, flame retardants, foaming agents, activators such as diethylene glycol, and hygroscopic agents such as calcium oxide. When vulcanizing in a non-pressurized system, it is preferable to use a filler having a low hygroscopic property in order to prevent foaming due to water.

The rubber laminate of the present invention comprises the thermosetting silicone rubber composition and the organic rubber composition as described above, at the same time or separately by a molding machine such as press, transfer, injection or extrusion. It can be manufactured by stacking the molded products and then simultaneously heating and vulcanizing them.

As the vulcanization method, steam vulcanization, press vulcanization, HAV (hot air vulcanization), UHF (high frequency vulcanization), L
Various conventionally known methods such as CM (liquid immersion vulcanization), PCM (fluidized bed vulcanization) and far infrared vulcanization are used, but steam vulcanization, press vulcanization and HAV are preferable.

The vulcanization conditions are not particularly limited, and the vulcanization temperature and vulcanization time are determined by the type of organic peroxide used, but are usually 100 to 400 ° C., preferably 100 to 300. It is carried out under conditions of 1 to 60 minutes at ℃.

In the present invention, if necessary,
By heat-treating the rubber laminate, it is possible to shorten the primary vulcanization time and improve the adhesive strength. In this case, heat treatment conditions of 40 to 100 ° C. and 0.1 to 120 minutes are suitable. It is more effective to carry out post-vulcanization at 50 to 200 ° C for 1 minute to 50 hours.

In the rubber laminate thus obtained, the drawbacks of silicone rubber are complemented by organic rubbers, for example, for water supply, automobiles, air, wicking, high pressure, oxygen / acetylene oil resistance. Two-layer, three-layer rubber hoses, conveyor belts for transportation, rubber belts such as transmission belts for transmitting power, automobiles, railway vehicles, industrial machinery, aircraft, electric / electronic devices, ship ports, etc. Anti-vibration rubber, steel making, paper making, printing, spinning, dyeing, office equipment, electro-acoustic products, agricultural machinery, rubber rolls for plastic manufacturing, blanket, chemical industry, water treatment equipment, air pollution control, food industry etc. Rubber linings, materials for packing and gaskets, roofing, rubber plates for floor materials, general housing, construction, civil engineering, vehicles, automobiles, aircraft,
Sealing materials for ships, packing, oil seals, diaphragms, valves, molded rubber products such as cushion rubber, rubber pipes, tubes for gas, water, medical, etc.
Extruded rubber products such as weather strips for automobiles, rubber drains, door window frames, trunk seals, wiper rubbers and wire coverings, other athletic equipment, rubberized cloth products, flexible containers, rubber gloves, sponge rubber products. It can be widely used for

The laminated structure is not limited to two layers, and a multilayer structure of three layers or more (including reinforcing fibers) is also possible.

[0050]

As described above, in the thermosetting silicone rubber composition of the present invention, the rubber laminate in which the silicone rubber and the organic rubber are firmly adhered to each other without using the intermediate layer or the adhesive is prepared by a special vulcanization method or a vulcanization method. It can be manufactured regardless of the sulfurization conditions.

[0051]

The present invention will be described in more detail with reference to Examples and Comparative Examples. In the following text, "part" means "part by weight".

Example 1 100 parts of a polyorganosiloxane (polymerization degree of about 6000 siloxane A) abbreviated with trimethylsilyl groups at the end and consisting of 99.8 mol% of dimethylsiloxy units and 0.2 mol% of methylvinylsiloxy units was used as a filler. Containing 40 parts of fumed silica surface-treated with hexamethyldisilazane, 3 parts of linear polyorganosiloxane containing 25 mol% of vinyl groups (polymerization degree 20 siloxane C-1) and 20 mol% of methylhydrogensiloxy groups 3 parts of linear polyorganohydrogensiloxane (abbreviated as polymerization degree 20 hydrogensiloxane D-1) are kneaded with a kneader until uniform, and TC-2 as a platinum catalyst is added to this.
0A (Platinum amount 100-1000ppm, Toshiba Silicone Co., Ltd.) 0.3
, TC-8 (2,5-dityl-2,5-di (t-
1 part of butylperoxy) hexane 50%, manufactured by Toshiba Silicone Co., Ltd.) was kneaded with a roll to obtain a thermosetting silicone rubber composition (I).

The following characteristics of the obtained silicone rubber composition (I) were evaluated. That is, the silicone rubber composition (I) was prepared into a sheet piece having a size of 5 cm x 4 cm x 4 mm, subjected to HAV at 250 ° C for 5 minutes, and the surface of the obtained vulcanized product was rubbed with a nail. The presence or absence of surface abrasion (HAV property) was visually observed. Further, a sheet piece prepared in the same manner was subjected to press vulcanization at 170 ° C. for 10 minutes and then subjected to a physical property test based on JIS K 6301. The results are shown in Table 1 together with the composition.

Example 2 In Example 1, the methyl hydrogensiloxy group 20
Instead of the straight-chain polyorganohydrogensiloxane containing 20 mol% of the mol%, a straight-chain polyorganohydrogensiloxane containing 50 mol% of a methylhydrogensiloxy group (degree of polymerization 10 Hydrogen siloxane D-2 and (Abbreviation), and the blending amount of fumed silica surface-treated with hexamethyldisilazane as a filler and a linear polyorganosiloxane (polymerization degree 20) containing 25 mol% of vinyl groups is shown in Table 1. A thermosetting silicone rubber composition was obtained in the same manner as in Example 1 except for changing as shown to obtain a silicone rubber composition (II).

The silicone rubber composition (II) thus obtained was evaluated for the same characteristics as in Example 1. The results are shown in Table 1 together with the composition.

Example 3 Instead of the linear polyorganosiloxane containing 25 mol% of vinyl group (polymerization degree of 20) in Example 1, a vinyl group was used.
5 parts of linear polyorganosiloxane containing 10 mol% (polymerization degree 100 siloxane C-2) was used, and fumed silica surface-treated with hexamethyldisilazane as a filler, methylhydrogensiloxy group 20 Other than changing the compounding amounts of the linear polyorganohydrogensiloxane (polymerization degree 20), the platinum-based catalyst TC-20A, and the organic peroxide TC-8 contained in mol% as shown in Table 1. Was obtained in the same manner as in Example 1 to obtain a thermosetting silicone rubber composition, which was used as a silicone rubber composition (III).

The silicone rubber composition (III) thus obtained was evaluated for the same characteristics as in Example 1. The results are shown in Table 1 together with the composition.

Example 4 In place of the linear polyorganosiloxane containing 25 mol% of vinyl groups (polymerization degree of 20) in Example 1, Example 3 was used.
Linear polyorganosiloxane containing 10 mol% of vinyl group (polymerization degree of 100) used in Step 7 and linear polyorganohydrogensiloxane containing 20 mol% of methylhydrogensiloxy group (polymerization degree of 20) Instead of
A fumed silica obtained by using 3 parts of the linear polyorganohydrogensiloxane (polymerization degree: 10) containing 50 mol% of methylhydrogensiloxy group used in Example 2 and further surface-treating it with hexamethyldisilazane as a filler. A thermosetting silicone rubber composition was prepared in the same manner as in Example 1 except that the compounding amounts of platinum catalyst TC-20A and organic peroxide TC-8 were changed as shown in Table 1. To obtain a silicone rubber composition (IV).

The silicone rubber composition (IV) thus obtained was evaluated for the same characteristics as in Example 1. The results are shown in Table 1 together with the composition.

Example 5 In Example 1, instead of the linear polyorganosiloxane containing 25 mol% of vinyl group (polymerization degree: 20), a vinyl group was used.
Cyclic polyorganosiloxane containing 50 mol% (degree of polymerization
4 Siloxane C-3)) and 4 parts of fumed silica surface-treated with hexamethyldisilazane as a filler, and TC-20A as a platinum-based catalyst are blended in Table 1.
A thermosetting silicone rubber composition was obtained in the same manner as in Example 1 except that the silicone rubber composition (V) was changed to a silicone rubber composition (V).

With respect to the obtained silicone rubber composition (V), the same characteristic evaluation as in Example 1 was carried out. The results are shown in Table 1 together with the composition.

Example 6 In place of the linear polyorganosiloxane containing 25 mol% of vinyl groups (polymerization degree of 20) in Example 1, Example 5 was used.
6 parts of the cyclic polyorganosiloxane containing 50 mol% of vinyl group (polymerization degree 4) used in step 2 and replacing with the linear polyorganohydrogensiloxane containing 20 mol% of methylhydrogensiloxy group (polymerization degree of 20) 50 mol% of the methyl hydrogensiloxy group used in Example 2
Using 2 parts of linear polyorganohydrogen siloxane (polymerization degree 10) contained, fumed silica surface-treated with hexamethyldisilazane as a filler and TC-20A as a platinum catalyst A thermosetting silicone rubber composition was obtained in the same manner as in Example 1 except that the composition was changed as shown in Table 1 to obtain a silicone rubber composition (VI).

The silicone rubber composition (VI) thus obtained was evaluated for the same characteristics as in Example 1. The results are shown in Table 1 together with the composition.

Comparative Example 1 A fumed silica obtained in Example 1 without using linear polyorganosiloxane containing 25 mol% of vinyl group (polymerization degree of 20) and surface-treated with hexamethyldisilazane as a filler, And a silicone rubber composition in the same manner as in Example 1 except that the compounding amount of a linear polyorganohydrogensiloxane containing 20 mol% of methylhydrogensiloxy group (polymerization degree of 20) was changed as shown in Table 1. Got
The silicone rubber composition (VII) was used.

The silicone rubber composition (VII) thus obtained was evaluated for the same characteristics as in Example 1. The results are shown in Table 1 together with the composition.

Comparative Example 2 In Example 1, the methyl hydrogensiloxy group 20 was used.
Table 1 shows the blending amount of the linear polyorganohydrogensiloxane (polymerization degree: 20) contained in mol%, and the fumed silica surface-treated with the filler hexamethyldisilazane without using the platinum catalyst. Except that
A silicone rubber composition was obtained in the same manner as in Example 1 to obtain a silicone rubber composition (VIII).

The silicone rubber composition (VIII) thus obtained was evaluated for the same characteristics as in Example 1. The results are shown in Table 1 together with the composition.

Comparative Example 3 In Example 1, instead of the linear polyorganosiloxane containing 25 mol% of vinyl group (polymerization degree: 20), a vinyl group was used.
5 parts of linear polyorganosiloxane containing 10 mol% (polymerization degree 100) and linear polyorganohydrogensiloxane containing 20 mol% of methylhydrogensiloxy group (polymerization degree 20), and platinum catalyst , Fumed silica surface-treated with hexamethyldisilazane as a filler, and TC-8 as an organic peroxide
A silicone rubber composition was obtained in the same manner as in Example 1 except that the compounding amount was changed as shown in Table 1 to obtain a silicone rubber composition (IX).

With respect to the obtained silicone rubber composition (IX), the same characteristic evaluation as in Example 1 was carried out. The results are shown in Table 1 together with the composition.

COMPARATIVE EXAMPLE 4 In Example 1, instead of the linear polyorganosiloxane containing 25 mol% of vinyl group (polymerization degree of 20), a vinyl group was used.
Cyclic polyorganosiloxane containing 50 mol% (degree of polymerization
4) 5 parts, and instead of the linear polyorganohydrogensiloxane containing 20 mol% of methylhydrogensiloxy group (degree of polymerization 20), the linear polyorganogroup containing 50 mol% of methylhydrogensiloxy group. 3 parts of organohydrogensiloxane (polymerization degree 10) were used, no platinum catalyst was used, and the blending amount of fumed silica surface-treated with hexamethyldisilazane as a filler was changed as shown in Table 1. Was obtained in the same manner as in Example 1 to obtain a silicone rubber composition (X).

The silicone rubber composition (X) thus obtained was evaluated for characteristics in the same manner as in Example 1. The results are shown in Table 1 together with the composition.

Comparative Example 5 In Example 1, a linear polyorganosiloxane containing 25 mol% of vinyl groups (degree of polymerization: 20) and an organic peroxide were not used, and the surface was filled with hexamethyldisilazane as a filler. Treated fumed silica and platinum based catalysts
A silicone rubber composition was obtained in the same manner as in Example 1 except that the compounding amount of TC-20A was changed as shown in Table 1 to obtain a silicone rubber composition (XI).

The silicone rubber composition (XI) thus obtained was evaluated for the same characteristics as in Example 1. The results are shown in Table 1 together with the composition.

[0074]

[Table 1]

Examples 7 to 27 The silicone rubber compositions (I) to (VI) obtained in Examples 1 to 6 and the organic rubber compositions having the compositions shown in Tables 2-1 and 2-2 Using (A) to (P), laminated sheets and laminated pipes were produced in the combinations shown in Table 3 and subjected to the characteristic evaluation test described later. The organic rubber compositions (A) to (P) are the organic peroxides α, α'-
After kneading each component except bis (t-butylperoxy) -p-diisopropylbenzene in a Banbury mixer until uniform, the organic peroxide α, α'-bis (t-butylperoxy)- It was prepared by adding p-diisopropylbenzene with a roll and kneading until uniform.

[Preparation of Laminated Sheet] The silicone rubber composition was formed into a sheet having a thickness of about 2 mm, and the organic rubber composition was formed into a sheet having a thickness of about 4 mm.
Press vulcanization was performed for 0 minutes to prepare a laminated sheet having a thickness of 6 mm. When the base polymer of the organic rubber composition was a diene rubber, a sheet having a thickness of about 2 mm was prepared, and a saturated rubber layer was brought into contact with the outside of the sheet for press vulcanization.

Each of the obtained laminated sheets was punched out into a width of 1 cm, and a T-type peeling test (peeling speed was 50 mm / min) was conducted according to JIS K 6854 to examine the adhesiveness. Further, it was tested whether both rubber layers were separated by hand and peeled at the interface. Further, each laminated sheet was left in a gear oven at 150 ° C. for 24 hours for heat aging, and then the same test was conducted. The results are shown in Table 3-1 and Table 3-2.

[Production of Laminated Pipe] Using a two-layer extruder, a silicone rubber composition having an inner diameter of about 15 mm and an inner layer of about 0.5 mm and an outer rubber composition of about 2 mm were simultaneously extruded (extruder). Head temperature of 60 ° C.), and then HAV was performed at 250 ° C. for 5 minutes to produce a laminated pipe. When the base polymer of the organic rubber composition is a diene rubber,
After extruding 1 mm of saturated rubber layer on the outside, HA
V was done.

The obtained laminated pipe was cut into a width of 5 mm, the interface between the inner silicone rubber layer and the outer organic rubber layer was cut out with a knife, and both layers were separated by hand and tested for peeling at the interface. Also, each laminated pipe was left in a gear oven at 150 ° C. for 24 hours for heat aging, and then the same test was performed. Furthermore, each laminated pipe cut into a width of 5 mm was subjected to a sunshine weather meter based on JIS K 6328, and after 1,000 hours, the presence or absence of cracks on the surface was visually observed to examine the weather resistance. The results are shown in Table 3-1 and Table 3-2.

Comparative Examples 6 to 10 Each of the silicone rubber compositions (VI
I) to (XI) and the organic rubber composition (D) shown in Table 2-1.
Using the above, a laminated sheet and a laminated pipe were produced in the same manner as in the above example. Then, the obtained laminated sheets and laminated pipes were subjected to the same characteristic evaluation as in the above-mentioned examples. The results are shown in Table 3-3.

Reference Example A pipe obtained by molding and vulcanizing the organic rubber composition (A) shown in Table 2 in the same manner as in the above example was examined for weather resistance in the same manner as in the above example. However, cracks were observed on the surface as shown in Table 3-3.

[0082]

[Table 2-1]

[0083]

[0084]

[Table 2-2]

[0085]

* 1 JSR EP87 (product name of Japan Synthetic Rubber Co., Ltd.) * 2 JSR AR102 (product name of Japan Synthetic Rubber Co., Ltd.) * 3 JSR Aflas 150E (product name of Japan Synthetic Rubber Co., Ltd.) * 4 JSR N230S (Japan Synthetic Rubber Co., Ltd.) Rubber Co., Ltd. product name) * 5 JSR 1502 (Nippon Synthetic Rubber Co., Ltd. product name) * 6 Zet Pole 2010 (Nippon Zeon Co., Ltd. product name) * 7 Epichromer CG (Daiso Co., Ltd. product name) * 8 Skyprene B-30 (Product name manufactured by Tosoh Corporation) * 9 JSR Chlorobutyl 1066 (Product name manufactured by Japan Synthetic Rubber Co., Ltd.) * 10 JSR JENIX E2170 (Product name manufactured by Japan Synthetic Rubber Co., Ltd.) * 11 Aerosil R972 (Product name manufactured by Nippon Aerosil Co., Ltd.) * 12 White gloss flower cc (Product name of Shiroishi Industry Co., Ltd.) * 13 Idemitsu PW-380 (Product name of Idemitsu Kosan Co., Ltd.) * 14 Linear polyorganosiloxane (vinyl group content 25
Mol% degree of polymerization 20) * 15 Linear polyorganosiloxane (vinyl group content 10
Mol% polymerization degree 200) * 16 Cyclic polyorganosiloxane (vinyl group content 50 mol% polymerization degree 4)

[0087]

[Table 3-1]

[0088]

[0089]

[Table 3-2]

[0090]

[0091]

[Table 3-3]

[0092]

As is clear from the above Examples and Comparative Examples, the silicone rubber composition of the present invention exhibits an excellent degree of surface cross-linking even by HAV and is firmly vulcanized and bonded to an organic rubber. And its excellent adhesion is retained after heat aging. The laminate with the organic rubber obtained by using this has good weather resistance.

[0094]

As described above, according to the present invention, a thermosetting silicone rubber composition is blended with a specific amount of a siloxane having a vinyl group, and an organic peroxide and a human silylation reaction are used in combination. A thermosetting silicone rubber composition with adhesive strength can be obtained without restrictions on the vulcanization method and vulcanization conditions. By using this thermosetting silicone rubber composition, the silicone rubber and the organic rubber are firmly bonded. The rubber laminate can be obtained without any limitation on the vulcanization method and vulcanization conditions.

[0095]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location // (C08L 83/04 83:06 83:05) B29K 19:00 B29L 9:00 4F (72 ) Inventor Koichi Tokuyama, 2-11-24 Tsukiji, Chuo-ku, Tokyo, Japan Synthetic Gom Co., Ltd. (72) Inventor, Yuki Umeda, 2-11-24, Tsukiji, Chuo-ku, Tokyo, Japan

Claims (3)

[Claims] 1. (A) Average composition formula R ¹ _n SiO _{(4-n) / 2} (I) (wherein, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group, and 0 to 5 thereof). 100% by weight of a polyorganosiloxane having an average degree of polymerization of 500 to 12000 represented by the formula: (m) is a vinyl group, and n is a number of 1.900 to 2.004, (B) a filler of 10 to 200 parts by weight, and (C) an average composition formula R ² _m SiO _{(4-m) / 2} (II) (In the formula, R ² is a substituted or unsubstituted monovalent hydrocarbon group, 5 to 50 mol% of which is a vinyl group, and m is 0 <m. <Number of 4) 0.1 to 20 parts by weight of polyorganosiloxane having an average degree of polymerization of 3 to 500, and (D) the number of hydrogen atoms bonded to silicon atoms exceeds at least 2 on average in one molecule. 0.1 to 20 parts by weight of polyorganohydrogensiloxane, (E) platinum catalyst (as platinum metal amount) 0.01 to 5000 ppm, and (F) The thermosetting silicone rubber composition characterized by comprising a peroxide from 0.1 to 20 parts by weight as component. 2. A silicone rubber layer made of the thermosetting silicone rubber composition according to claim 1 and an organic rubber layer made of an organic rubber composition containing an organic peroxide as a vulcanizing agent are laminated. And a rubber laminate which is integrally vulcanized and bonded. 3. In producing the rubber laminate according to claim 1, an unvulcanized silicone rubber layer comprising the thermosetting silicone rubber composition according to claim 1 and an organic peroxide as a vulcanizing agent. An unvulcanized organic rubber layer composed of an organic rubber composition contained is closely laminated and then heated to integrally vulcanize and bond the silicone rubber layer and the organic rubber layer. And a method for producing a rubber laminate.