JPH11158454A - Adhesive and adhering method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable an adhesive layer to be formed on a wide variety of adherends by applying a soln. contg. a platinum compd. to a molded article obtd. by thermally curing a compsn. contg. a polyorganosiloxane, a polyorganohydrogensiloxane, and an org. peroxide. SOLUTION: A compsn. prepd. by compounding 100 pts.wt. substantially linear polyorganosiloxane having a degree of polymn. of 50-20,000 with 0.1-50 pts.wt. polyorganohydrogensiloxane having, on average, at least two Si-bonded hydrogen atoms per molecule, 0.05-15 pts.wt. org. peroxide (e.g. dicumyl peroxide), and 5-500 pts.wt. reinforcing filler (e.g. silica) having a particle size of 20 μm or lower or nonreinforcing filler (e.g. titanium oxide) is molded and cured to give a molded article e.g. in the form of a tape. The objective adhesive is prepd. by applying a soln. contg. a platinum compd. for addition reaction (e.g. chloroplatinic acid) and an adhesiveness-imparting agent (e.g. 3- glycidoxypropyltrimethoxysilane) to the surface of the above-obtd. molded article.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicone adhesive, and more particularly, to a silicone adhesive comprising a polyorganosiloxane composition cured in the presence of an organic peroxide and a solution of a platinum compound. It relates to a system adhesive. The present invention also relates to a simple bonding method using such a set of silicone-based adhesives.

[0002]

2. Description of the Related Art Polyorganosiloxane compositions which cure to give a silicone rubber are excellent in heat resistance, cold resistance, weather resistance, etc., and appropriately select a base polymer and a crosslinking agent, or add an adhesion promoter. By doing so, excellent adhesion can be exhibited during curing. Therefore, such a polyorganosiloxane composition is widely used as an elastic adhesive in applications requiring heat resistance, cold resistance, weather resistance, and the like.

[0003] However, an adhesive polyorganosiloxane composition using a liquid polyorganosiloxane as a base polymer may be a fluid viscous material in an uncured state or an adhesive paste. The method of filling and using containers such as tubes and cartridges is used.Tools such as a cartridge gun and masking tape are required for bonding work, and in some cases, further mixing and defoaming at the bonding site Therefore, it is not possible to perform bonding by only a simple manual operation.

[0004] On the other hand, millable silicone rubber generally has no adhesiveness, and requires a complicated work of treating the surface of an adherend with a primer in advance. It is possible to obtain an adhesive silicone rubber by blending an adhesiveness-imparting agent such as a silane coupling agent with the millable silicone rubber, but the bonding stability is not sufficient. Besides,
Molding must be performed at a high temperature, the operation is complicated, and it is not suitable for bonding a large adherend.

Japanese Patent Application Laid-Open Publication No. HEI 2 (1999) -1990 discloses that a silicone rubber molded article cured by an addition reaction is coated with an organic solvent solution of a platinum group metal and / or a compound thereof to improve the releasability of the molded article. No. 16014. However, the publication states that such a solution
There is no disclosure of an adhesion method that involves applying the composition to a molded article of a polyorganosiloxane composition cured with an organic peroxide.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to apply an elastic or plastic silicone adhesive layer to a wide range of adherends by a simple manual operation without the limitations inherent in the conventional silicone elastic adhesives. To provide an adhesive and a bonding method capable of forming the same.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted various studies to achieve the above object, and as a result, have found that the surface of a molded article of a specific polyorganosiloxane composition previously cured with an organic peroxide. By adhering a solution of a platinum-based compound to the surface of an adherend, it has been found that adhesion can be achieved by a simple method and the above object can be achieved, and the present invention has been completed. Was.

That is, the adhesive of the present invention comprises: (1) a substantially linear polydiorganosiloxane; and (2) a polyorganosiloxane having an average of more than two hydrogen atoms bonded to silicon atoms in one molecule. (3) a molded product (A) obtained by curing a polyorganosiloxane composition containing an organic peroxide at a temperature equal to or higher than the decomposition temperature of the organic peroxide; and a solution containing a platinum compound (B) is a set.

Further, the bonding method of the present invention uses the above-mentioned molded product of the polyorganosiloxane composition and a solution of a platinum-based compound. That is, step (i): a step of curing the composition containing the above (1), (2) and (3) at a temperature equal to or higher than the decomposition temperature of the organic peroxide to produce a molded article (A); (Ii): a step of adhering a solution (B) containing a platinum-based compound to the surface of the molded article (A) and / or the surface of the adherend (C); and step (iii): A) a step of bringing the A) into close contact with the adherend (C).

[0010] Here, "as a set" means
As apparent from the bonding method of the present invention, component (1),
The molded article (A) obtained by curing the composition containing (2) and (3) and the solution (B) are separately stored until use, and the surface of the molded article (A) and / or Alternatively, it refers to such a combination of (A) and (B) that causes the solution (B) to adhere to the surface of the adherend (C).

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Component (1) used in the present invention
The substantially linear polydiorganosiloxane is a component serving as a base polymer of the polyorganosiloxane composition used in the present invention. The (1) is easily crosslinked by an organic peroxide to form a network molecule, and in order to form an elastic adhesive layer, one vinyl group bonded to a silicon atom is required.
Preferably, there is at least one on average in the molecule,
More preferably, two or more are present. This means
This is particularly noticeable when an organic peroxide other than an acyl-based one is used as the component (3). The vinyl group may be present in the siloxane unit at the molecular chain end of (1) or may be present in the intermediate siloxane unit.

The siloxane skeleton (1) is substantially linear as described above, and may have some branches or a three-dimensional structure. The polymerization degree of the component (1), that is, the number of siloxane units is usually 50 to 20,000, and may be a fluid liquid or a highly viscous gum.
In order to be easy to handle and to give the molded article sufficient mechanical strength, it is preferably 3,000 to 10,000, and 5,000 to 5,000.
The range of -8,000 is more preferred. If the degree of polymerization is less than 50, the cured molded article has insufficient mechanical strength. Further, those having a polymerization degree exceeding 20,000 are not only difficult to synthesize, but also difficult to mix fillers and the like.

The organic group other than the vinyl group bonded to the silicon atom in (1) includes a linear or branched alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, and dodecyl. Cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl, tolyl and xylyl; aralkyl groups such as 2-phenylethyl and 2-phenylpropyl; chloromethyl, chlorophenyl and 3,3,3-trifluoropropyl Examples thereof include a monovalent substituted hydrocarbon group. Of these, 92 mol% or more is preferably a methyl group, and substantially all may be a methyl group, since the advantages of the silicone adhesive such as heat resistance, cold resistance, and weather resistance can be favorably exhibited. Other groups such as a phenyl group when cold resistance is required for the adhesive and a 3,3,3-trifluoropropyl group when oil resistance is required can be used in combination according to required characteristics.

The terminal of the molecular chain of (1) is preferably a triorganosiloxane unit in which only a substituted or unsubstituted monovalent hydrocarbon group is bonded to a silicon atom. Such a siloxane unit is preferably a trimethylsiloxane unit. ,
Those which do not contain a vinyl group such as a dimethylphenylsiloxane unit or a methyldiphenylsiloxane unit; and those which preferably contain a vinyl group such as a dimethylvinylsiloxane unit or a methylphenylvinylsiloxane unit are exemplified. , Ethoxy, etc. may be present.

[0015] The polyorganohydrogensiloxane of the component (2) used in the present invention is present in the molded article (A), and the hydrosilyl group contained in the molecule is converted to the adherend in the presence of the platinum compound. The molded article (A) is adhered to the adherend by reacting with a reactive group such as a hydroxyl group present on the surface; a group having a carbon-carbon unsaturated bond such as a vinyl group and a (meth) acryl group. It is for. The compound (2) has an average of more than two hydrogen atoms bonded to a silicon atom in one molecule, and preferably has at least three hydrogen atoms in order to obtain particularly strong adhesion.

As the organic group bonded to the silicon atom of the siloxane unit, those similar to the organic groups other than the vinyl group in the above-mentioned component (1) are exemplified. A methyl group is most preferred in view of compatibility with 1).

The siloxane skeleton (2) may be linear, branched or cyclic. Moreover, you may use these mixtures. Although the degree of polymerization of the component (2) is not particularly limited, it is 10 to 2 because it is easy to synthesize and does not volatilize during storage or when a crosslinking reaction is performed by heating.
A range of 00 is preferred.

As a specific example of the component (2), a unit having a molecular end blocked with a triorganosiloxane unit such as a trimethylsiloxane unit and having a hydrosilyl group such as a methylhydrogensiloxane unit in the middle,
A linear polyorganohydrogensiloxane having at least three in the molecule; and a molecular end blocked with a siloxane unit having a hydrosilyl group such as a dimethylhydrogensiloxane unit, and an intermediate hydrosilyl such as a methylhydrogensiloxane unit. A linear polyorganohydrogensiloxane having at least one unit having a group in one molecule is exemplified. In these and in these, units that do not contain a hydrosilyl group, such as dimethylsiloxane units, may or may not be present.

As another specific example of the component (2), a monofunctional unit having a hydrosilyl group such as a dimethylhydrogensiloxane unit and a tetrafunctional S
Examples include a branched polyorganohydrogensiloxane composed of iO ₂ units.

In the present invention, the compounding amount of the component (2) with respect to the component (1) is (2) based on 100 parts by weight of (1).
Is usually 0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight. If (2) exceeds 50 parts by weight, sufficient physical properties cannot be given to the adhesive layer.

The organic peroxide of the component (3) used in the present invention is decomposed by heating to generate radicals, and (1)
Is crosslinked to cure the composition. Benzoyl peroxide, as an organic peroxide,
Acyl-based peroxides such as bis (p-methylbenzoyl) peroxide; di-tert-butyl peroxide, 2,
Alkyl peroxides such as 5-dimethyl-2,5-di- (tert-butylperoxy) hexane, tert-butylcumyl peroxide, dicumyl peroxide; and tert-butylperoxy-2-ethylhexanoate; ester peroxides such as tert-butylperoxy-3,5,5-trimethylhexoate, tert-butylperoxybenzoate; and 1,6-bis (tert
Examples thereof include carbonate-based peroxides such as -butylperoxycarbonyloxy) hexane, and one type may be used or two or more types may be used in combination. Also, for safe handling, mix with silicone oil to make a paste,
You may mix | blend by making it adsorb | suck to an inorganic fine powder. As such an organic peroxide, an acyl peroxide and an ester peroxide are preferable because they can be cured at a relatively low temperature, and tert-butylperoxy-2-ethylhexanoate is particularly preferable.

The amount of component (3) is 100 parts (1).
It is usually 0.05 to 15 parts by weight, preferably 0.1 to 5 parts by weight based on parts by weight. If the amount is less than 0.05 part by weight, the crosslinking is insufficient, and if it exceeds 15 parts by weight, the physical properties of the molded article are adversely affected.

The polyorganosiloxane composition used in the present invention, in an uncured state, contains the above-mentioned component (1),
(2) and (3), and if necessary,
Fillers, adhesion promoters, heat resistance improvers, flame retardants and the like can be added.

The filler is used to give the polyorganosiloxane composition an appropriate plasticity and workability, and to give the cured adhesive layer the necessary mechanical properties. As the filler, a reinforcing and / or non-reinforcing filler can be used. In order to obtain an adhesive having good workability, at least a part of the filler has a particle diameter of 20 μm.
Preferably, the silica-based filler is not more than m.

Examples of the reinforcing filler include fine silica powders such as fumed silica, silica aerogel, and precipitated silica.
It may be treated with an organosilicon compound. Examples of the organosilicon compound used for the surface treatment include dimethyldichlorosilane, trimethylchlorosilane, hexamethyldisilazane, octamethylcyclotetrasiloxane, and the like.Because the workability of the composition is excellent, hexamethyldisilazane is used. Particularly preferred. In the treatment, the organosilicon compound used for the treatment is adsorbed on the surface of the silica fine powder at room temperature or high temperature by a gas phase or a liquid phase using an inert solvent such as n-hexane, and the silica is heat-treated. It can be carried out by organosilylating silanol groups on the surface of the fine powder. Further, in the step of kneading the reinforcing filler with the component (1), the treatment may be carried out by kneading with an organosilicon compound such as hexamethyldisilazane under heating.

Examples of the non-reinforcing filler include silica such as diatomaceous earth and ground quartz, titanium oxide, alumina, magnesium oxide, zinc oxide, calcium carbonate, carbon black and the like.

The amount of the filler is not particularly limited.
The amount is preferably 5 to 500 parts by weight, more preferably 10 to 400 parts by weight, per 100 parts by weight of the component (1). If the amount is less than 5 parts by weight, the composition becomes tacky and the workability is poor.
If the amount is more than 00 parts by weight, the plasticity increases and the workability is also poor, and the adhesive layer after curing cannot obtain good mechanical strength or rubber elasticity.

Examples of the adhesion-imparting agent include epoxy groups such as 3-glycidoxypropyl, 2- (3,4-epoxycyclohexyl) ethyl, vinyl, 3-methacryloxypropyl and 3-acryloxypropyl, and olefinic compounds. Methoxy having at least one carbon functional group selected from a group having a double bond and bonded to a silicon atom,
A silane or siloxane having a substituted or unsubstituted alkoxy group such as ethoxy or 2-methoxyethoxy and / or a hydrogen atom is used. Further, as another adhesion-imparting agent, a silicon-functional isocyanurate having a substituted or unsubstituted alkoxy group such as methoxy, ethoxy, propoxy, or 2-methoxyethoxy bonded to a silicon atom is also used.

Examples of such an adhesion-imparting agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl (methyl) dimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 2
-(3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl)
Epoxy group-containing silanes such as ethyl (methyl) dimethoxysilane and their partially hydrolyzed condensates; 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyl (methyl) dimethoxysilane Such as (meth) acrylic group-containing silanes and their partially hydrolyzed condensates; vinyl tri-containing silanes such as vinyltrimethoxysilane, vinyltriethoxysilane and vinyltris (2-methoxyethoxy) silane and their partial hydrolysis Condensates: 3-glycidoxypropyl group-containing methyl hydrogen cyclic tetrasiloxane, 3-methacryloxypropyl group-containing methyl hydrogen cyclic tetrasiloxane, 3-glycidoxypropyl group-containing methyl methoxy cyclic siloxane A 3-glycidoxypropyl group 2
Methyl hydrogen cyclic siloxane having (trimethoxysilyl) ethyl group, methyl hydrogen cyclic siloxane having 3-methacryloxypropyl group and 2- (trimethoxysilyl) ethyl group, 2-[(3-trimethoxysilyl) propyl Cyclic siloxanes such as [oxycarbonyl] propyl group-containing methylhydrogen cyclic siloxane; 3-glycidoxypropyl group-containing methylmethoxysiloxane, 3-glycidoxy group and vinyl group-containing methylhydrogensiloxane, 3-glycidoxy group and 2- A chain siloxane such as methylsiloxane having a (trimethoxysilyl) ethyl group; tris (3-
Examples thereof include cyanuric ring-containing organosilicon compounds such as (trimethoxysilylpropyl) isocyanurate.

In the present invention, such a polyorganosiloxane composition is preliminarily molded and then cured by heating to a temperature not lower than the decomposition temperature of the component (3) to be used as a molded article (A). The shape of the molded article (A) is suitable for applying the solution (B) to the surface or dipping the molded article (A) in the solution (B) to be used for bonding the adherend. Any shape may be used as long as it is present, but a sheet shape, a tape shape, or a string shape is preferable because of easy molding.

Such a molded product is mixed with the component (1), for example, by a mixing means such as a two-roll mill or a kneader.
After the composition is prepared by uniformly mixing (2), (3) and other components to be blended if necessary, for example, the composition extruded from a calender roll or two rolls or extruded by an extruder is used. By heating with a mold and / or circulation of hot air at a temperature not lower than the decomposition temperature of the organic peroxide, for example, 50 to 200 ° C. for 0.1 to 60 minutes.

The solution (B) is a solution of a platinum compound and is prepared and stored separately from the above-mentioned molded article. The platinum-based compound promotes the reaction between the hydrosilyl group (2) present in the molded article (A) and the reactive group present on the surface of the adherend. Complex mixture obtained by heating and alcohol, platinum-
Olefin complex, platinum-vinylsiloxane complex, platinum-
Examples include a platinum compound such as a triphenylphosphine complex; a palladium acetic acid such as a palladium-phosphine acetic acid; a rhodium compound such as a rhodium-phosphine acetic acid.

As the solvent, those which have an affinity for polyorganosiloxane and do not adversely affect the catalytic ability of the platinum compound and the above reaction are used. Examples of such a solvent include liquid and inert low molecular weight polyorganosiloxanes such as linear methylsiloxane oligomers having a polymerization degree of 2 to 10 and cyclic dimethylsiloxane oligomers having a polymerization degree of 4 to 7; Liquid silane; n-hexane, n-heptane, cyclohexane,
Examples thereof include hydrocarbons containing no aliphatic unsaturated bond, such as toluene and xylene. One type may be used alone, or two or more types may be used in combination. Hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane,
Preferred are linear siloxane oligomers such as dodecamethylpentasiloxane; and cyclic siloxane oligomers such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane.

The amount of the platinum-based compound for the addition reaction in the solution (B) is not particularly limited, but is usually 1 ppm to 3% by weight, preferably 5 ppm to 1% by weight, as the amount of the platinum group atom based on the solvent. . If the amount is less than 1 ppm, the amount of the solvent for using an appropriate amount of the catalyst becomes excessively large, so that it did not participate in the cross-linking reaction in the molded article during coating or dipping (1) and was present in the molded article. (2) may be eluted in a solvent, and it is difficult to obtain remarkable adhesiveness. On the other hand, since the platinum-based compound is effective even in a small amount with respect to the molded body, if the amount is more than 3% by weight, it is difficult to effectively distribute the desired amount of the catalyst in an economically viable range to the bonding surface. Become.

The solution (B) is mixed with an adhesion-imparting agent, and the solution (B) is applied or immersed in the solution (B).
Adhesiveness can be developed. Examples of the adhesion imparting agent include the same as described above.

The method of developing the adhesive property of the adhesive of the present invention is arbitrary, but usually the following alone or in combination with or is used. Hydrogen atoms bonded to silicon atoms remain in the molded product (A) obtained by curing the polyorganosiloxane composition. An adhesiveness-imparting agent is added to the polyorganosiloxane composition. An adhesiveness-imparting agent is blended with the solution (B), and in step (ii) described below, a molded article and / or
Alternatively, it is attached to an adherend.

In the bonding method of the present invention, first, in the molding step of step (i), the polyorganosiloxane composition containing the above-mentioned components (1), (2) and (3) is cured to form a molded article (A). ) Is prepared. The shape of the molded body and the molding method are as described above.

Next, in the step (ii), the solution (B) is adhered to the surface of the molded article (A) and / or the surface of the adherend (C). Specifically, for example, the solution (B) is applied to the surface of the molded body (A) and / or the adherend (C).
Is applied, or the molded article and / or the adherend are immersed in the solution (B) to adhere the platinum compound to the surface of the molded article (A) and / or the adherend (C). In order to ensure adhesion, the solution (B) is preferably applied to the surface of the adherend (C). The amount of solution (B) used is arbitrary. The application method is not particularly limited, and application can be performed using a sponge, a brush, a spray, or the like. The coating or dipping may be performed at normal temperature.

Next, in step (iii), the molded body to which the solution (B) has adhered is brought into close contact with the adherend by a method such as pressure bonding. At this time, the compact may be pressed so as to keep the shape of the compact as it is, or the compact may be deformed by the compaction. The adherend is not particularly limited as long as there is no substance that inhibits the catalytic ability of the platinum compound, such as amines and sulfur compounds, on the surface. The adherend can be applied to glass, ceramics, metals, plastics, and the like. Via the adhesive layer, it is possible to adhere between adherends of the same material or between different adherends.

While maintaining the close contact state, depending on the type and amount of the platinum compound, leave it at room temperature or, for example, leave it at 50 to 12
By heating at 0 ° C. for 1 to 30 minutes, a strong adhesive layer is formed.

[0041]

According to the present invention, an adhesive and an adhesive method capable of forming an elastic adhesive layer having excellent adhesion, heat resistance, cold resistance and weather resistance can be obtained by simple manual operation and with low energy consumption. . The adhesive and the bonding method of the present invention can be applied to bonding between a wide range of adherends such as glass, ceramics, metal, and plastic.

[0042]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples. In these examples, parts are parts by weight, and percentages in the formulations are percentages by weight unless otherwise specified. The present invention is not limited by these examples.

Example 1 100 parts of a polydiorganosiloxane having a polymerization degree of 6,000 and having both ends capped with a dimethylvinylsilyl group and comprising 99.8 mol% of dimethylsiloxane units and 0.2 mol% of methylvinylsiloxane units Specific surface area 300m ²
/ g of fumed silica 60 parts, hexamethyldisilazane 12
And 6 parts of water were mixed and kneaded with a kneader at room temperature for 1 hour to trimethylsilylate the silica surface. Then, the temperature was raised to 150 ° C. and kneaded for 2 hours to remove the generated decomposition residue. Thereafter, the temperature was lowered to room temperature, and both ends were blocked with a trimethylsilyl group, and 5 parts of polymethylhydrogensiloxane having a polymerization degree of 50 and a dicumyl peroxide having an intermediate unit of methylhydrogensiloxane units of 50 were compounded. And kneaded to obtain a polyorganosiloxane composition.

The obtained polyorganosiloxane composition was separated from a two-roll mill, and a 2 mm-thick mold was used.
Press vulcanization was performed at 70 ° C. for 10 minutes to obtain a molded body. This was cut into a length of 50 mm and a width of 20 mm.

On the other hand, 1,3,5,7-tetramethyl-
A platinum-vinylsiloxane complex was synthesized from 1,3,5,7-tetravinylcyclotetrasiloxane and chloroplatinic acid. This was dissolved in octamethylcyclotetrasiloxane to obtain a solution of a platinum compound containing 100 ppm in terms of platinum atoms.

Glass, aluminum and SUS304
After applying the above-mentioned solution to the surface of an adherend of stainless steel having a length of 50 mm, a width of 10 mm and a thickness of 2 mm, the molded body is sandwiched between two adherends and allowed to adhere, and then left at room temperature. Thus, three test pieces were obtained for each adherend.

One hour after applying the solution of the platinum compound,
After 10 hours and 24 hours, the state of adhesion was observed for one test piece for each adherend. The results are as shown in Table 1 at room temperature for 10 hours (glass) or 24 hours (aluminum and SUS30).
By leaving as in 4), a silicone rubber adhesive layer having a thickness of 2 mm and excellent in adhesiveness was obtained. In addition, since the molded product of the polyorganosiloxane composition used as the adhesive layer is a cured product, it has no tackiness, and even if it is cut, immersed, and adhered to the adherend all by hand, stains are generated. Did not.

Example 2 The same experiment as in Example 1 was carried out except that 1% of 3-methacryloxypropyltrimethoxysilane was added as a tackifier to the solution of the platinum compound. The results are as shown in Table 1. As shown in Table 1, excellent adhesion was observed for all the adherends after being left at room temperature for 10 hours. As in Example 1, all the bonding operations could be performed manually.

Example 3 As polymethyl hydrogen siloxane, both ends were blocked with a trimethylsilyl group, and the intermediate unit was composed of 50 mol% of methyl hydrogen siloxane units and 50 mol% of dimethyl siloxane units and having a polymerization degree of 40. A composition was prepared in the same manner as in Example 1 except that 2 parts of siloxane was used, and the same experiment as in Example 1 was performed. The results were as shown in Table 1.

Example 4 130 parts of tert-butylperoxy-2-ethylhexanoate was used in place of dicumyl peroxide, and
The same experiment as in Example 1 was performed except that press vulcanization was performed at 10 ° C. for 10 minutes. The results were as shown in Table 1.

Comparative Example 1 Both ends were blocked with silanol groups and the degree of polymerization was 1,000.
Of 100 parts of polydimethylsiloxane, specific surface area of 200
14 parts of m ² / g fumed silica were added and mixed homogeneously to prepare a base mixture. On the other hand, 8.4 parts of methyltris (methylethylketoximato) silane and 0.1 part of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane.
Six parts and 0.1 part of dibutyltin dilaurate were mixed to prepare a crosslinker / catalyst mixture. The adhesive was prepared by mixing the above-mentioned base mixture and the cross-linking agent / catalyst mixture in an agitated mixer in which the humidity was shut off, and then defoamed, and placed in a moisture-tight container.

The same adhesive as that used in Example 1 was extruded from a container onto one of the three types of adherends, applied to a thickness of 2 mm, and the other adherend was overlaid. It was left at room temperature, and the state of adhesion was observed as in Example 1. The results were as shown in Table 1. Since the adhesive cures due to moisture in the air, a special container and extruder were required. Also, there is stickiness in the uncured state,
Masking tape is needed to keep the surrounding area clean,
During the operation, the adhesive could not be touched by hand.

Comparative Example 2 Both ends were blocked with a dimethylvinylsilyl group and the degree of polymerization was 6
A base mixture was prepared by mixing 100 parts of polydimethylsiloxane of Example No. 00 with 50 parts of titanium oxide powder having an average particle diameter of 0.2 μm and having a surface treated with polydimethylsiloxane. On the other hand, 4 parts of a polymethyl hydrogen siloxane composed of 67 mol% of (CH ₃ ) ₂ HSiO _1/2 units and 33 mol% of SiO ₂ units, and a platinum-vinyl siloxane complex 0.2 containing 0.5% as a platinum atom. Parts, 0.5 parts of triallyl isocyanurate as a curing inhibitor, and 1 part of 3-methacryloxypropyltrimethoxysilane as an adhesion-imparting agent were mixed to prepare a crosslinking agent / catalyst mixture. The mixture was mixed and defoamed to prepare an adhesive, which was stored in a container and stored in a cool and dark place.

The same adherend was adhered in the same manner as in Comparative Example 1 except that a barrier was provided so as not to flow out to the periphery using this adhesive, and the state of adhesion was observed. The results were as shown in Table 1. The adhesive was fluid and tacky in the uncured state and could not be touched by hand.

Comparative Example 3 A polyorganosiloxane composition was prepared in the same manner as in Example 1 except that no polymethylhydrogensiloxane was used. Using this, a molded article was produced in the same manner as in Example 1, and an adhesion experiment was conducted in the same manner. As a result, as shown in Table 1, no adhesiveness was obtained.

Comparative Example 4 Using the molded article obtained in Example 1, an adhesion test was performed in the same manner as in Example 1 except that the application of the platinum compound solution was not performed. As a result, as shown in Table 1, no adhesiveness was obtained.

[0057]

[Table 1]

Claims (4)

[Claims] (1) a substantially linear polydiorganosiloxane; (2) a polyorganohydrogensiloxane having an average of more than two silicon-bonded hydrogen atoms per molecule; and (3) A) a molded article (A) obtained by curing a polyorganosiloxane composition containing an organic peroxide at a temperature equal to or higher than the decomposition temperature of the organic peroxide; and a solution (B) containing a platinum compound. Glue. 2. The adhesive according to claim 1, wherein (1) has two or more vinyl groups bonded to a silicon atom in one molecule. 3. The adhesive according to claim 1, wherein the molded article (A) is in the form of a sheet, a tape, or a string. 4. Step (i): (1) a substantially linear polydiorganosiloxane; and (2) a polyorganohydrogen having an average of more than two silicon-bonded hydrogen atoms in one molecule. A siloxane; and (3) a step of curing the polyorganosiloxane composition containing an organic peroxide at a temperature equal to or higher than the decomposition temperature of the organic peroxide to produce a molded article (A); Step (ii): a molded article Adhering a solution (B) containing a platinum compound to the surface of (A) and / or the surface of the adherend (C); and step (iii): then, applying the molded article (A) to the adherend. (C) a step of adhering to the substrate.