JP2001200230A - Silicone-based contact adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a moisture curable, silicone-based contact adhesive which has a large tack strength, a fast tack-developing speed and a long tack-retaining time. SOLUTION: The silicone-based contact adhesive contains as the effective components, (A) a silicone-based resin which has the main chain structure of a polyoxyalkylene and in which two alkoxy groups and one hydrocarbyl group are bonded directly to a silicon atom; (B) a silicone-based resin which has the main structure of a polyoxyalkylene and in which three alkoxy groups are bonded directly to a silicon atom; and (C) an acrylic resin which is an alkyl(meth)acrylate polymer and has a silicon-reactive group, with a content ratio of the silicone-based resin (A) and the silicone-based resin (B) being 50-99% of the silicone-based resin (A) to 50-1% of the silicone-based resin (B), and with a content of the polymer (C) being 5-200 pts. relative to 100 pts. of the sum total of the silicone-based resin (A) and the silicone-based resin (B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicone-based contact adhesive, and more particularly, to a moisture-curable silicone adhesive having an excellent tack force, exhibiting the tack force quickly and maintaining it for a long time. The present invention relates to a contact type adhesive.

[0002]

2. Description of the Related Art Contact-type adhesives in which an adhesive is applied to both surfaces of an adherend and pasted after a predetermined open time have been used in practice, including solvent-based rubber adhesives. Due to the problem of toxicity of the solvent-type rubber adhesive to the human body due to the solvent, a moisture-curable contact adhesive composed of a modified silicone-based polymer compound without using a solvent has been disclosed in JP-A-3-263478. It has been suggested that

The modified silicone polymer composing the contact adhesive described in the above publication comprises a (meth) acrylate copolymer having a substantially reactive silicon group and a modified silicone resin. The (meth) acrylate copolymer is a copolymer of two (meth) acrylates having different carbon numbers and an alkoxysilane. But,
The adhesive containing the modified silicone-based polymer as a component requires a long time to develop tack, and cannot be used as a substitute for the current rubber-based contact adhesive.

Further, according to the present invention, there is provided a resin composition containing a silicone resin in which the silicone-reactive group at the molecular end is a polyalkoxysilyl group and whose main chain is substantially a polyoxyalkylene structure. Wherein the silicone resin comprises (1) 10 to 90% by weight of a silicone resin in which the silicone-reactive group is a trialkoxysilyl group and (2) 90 to 10% by weight of a silicone resin in which the silicone-reactive group is an alkyldialkoxysilyl group. Mixture (JP-A-10
SUMMARY OF THE INVENTION An object of the present invention is to develop an instant adhesive approaching a low molecular adhesive such as an α-cyanoacrylate adhesive.

[0005] Furthermore, polymers having three hydrolyzable hydrolyzable silicon group group is bonded directly to a silicon atom (A), the curing catalyst (B), and is represented by the formula R ² ₃ -Si- have that group, room-temperature-curable composition containing a silicon compound that produces R ² ₃ SiOH through hydrolysis (C) (JP-a-11
In this composition, the polymer (A) has a hydrolyzable group in which two or one hydrolyzable groups whose hydrolyzable groups are substantially methoxy groups are directly bonded to silicon atoms. It is disclosed that the polymer can be used in combination with a polymer having a decomposable silicon group. However, the purpose of this proposed invention is
It is intended to provide a room temperature curable composition which cures quickly and has no tackiness after curing, and this composition is not suitable for a contact adhesive.

Further, (a) a silicone resin in which the silicone-reactive group is a trimethoxy group and / or a triethoxy group and the main chain has a polyoxypropylene structure, and (b) a silicone-reactive group is methyl A dimethoxy group and / or a methyldiethoxy group, a silicone resin having a polyoxypropylene main chain and (c) a silicone reactive group obtained by polymerizing a (meth) acrylic ester containing a polyalkoxysilyl group; Comprising an acrylic resin (Japanese Patent Laid-Open No. 10-25155)
No. 2) has been proposed, which is excellent in storage stability, quick-curing, and has an adhesive function excellent in internal curability.

However, when this is used as a contact adhesive, the tack strength, tack development speed, tack duration, and the like required as a superior contact adhesive are still insufficient. In particular, when bonding an adherend having a large area, it takes time to apply the adhesive to the adherend.Therefore, if the tack duration is short, there is a problem in work, and the tack development speed is low. This causes a problem that the adhesive strength becomes uneven between the first and last parts of the coating and between the central part and the outer edge of the adherend.

[0008]

SUMMARY OF THE INVENTION The present invention relates to a moisture-curable silicone-based contact adhesive which has a short time to the onset of tack, a large adhesive strength immediately after tack, a long tack range, and a long bonding time. The purpose is to provide.

[0009]

Means for Solving the Problems In order to achieve the above-mentioned object, the present inventors have made intensive studies and as a result, have found that
A composition comprising the silicone resin (1) and the silicone resin (2) described in JP-A-245484, the silicone resin (a) described in JP-A-10-251552, and As in the composition comprising the silicone resin (b), a silicone-based polymer having a silicon-containing organic group in which three alkoxy groups are directly bonded to a silicon atom, two alkoxy groups, and one hydrocarbon group By using a combination of two kinds of silicone polymers having a silicon-containing organic group directly bonded to a silicon atom and an acrylic resin having a silicon-reactive group, that is, three alkoxy groups are directly The reaction of the silicon-containing organic group of the silicone polymer having a silicon-containing organic group bonded to a silicon atom secures the initial contact, and Of the concept of contacts extend the time available for other components, has reached the Heading out the present invention that can achieve the object of the present invention.

That is, according to the present invention, the main chain structure is a polyoxyalkylene, and the molecular terminal of the formula is -Si
(OR ¹ ) ₂ (R ² ) (R ¹ is an alkyl group having 1 to 8 carbon atoms, and R ² is an alkyl group having 1 to 8 carbon atoms.) The silicone resin (A), whose main chain structure is polyoxyalkylene, and whose molecular terminal is represented by the formula —Si (OR ¹ ) ₃ (R ¹ is an alkyl group having 1 to 8 carbon atoms). Silicone resin (B) composed of alkoxysilyl groups
And a polymer of one or two or more polymerizable vinyl group-containing monomers selected from the group consisting of acrylic esters, methacrylic esters, styrene and acrylonitrile, and is effective in using an acrylic resin (C) having a silicon-reactive group. The silicone resin (A) and the silicone resin (B) are contained in an amount of 50 to 99% by weight of the silicone resin (A).
Is 50 to 1% by weight, and the content of the acrylic resin (C) is 5 to 200 parts by weight per 100 parts by weight of the total of the silicone resin (A) and the silicone resin (B). The gist is a silicone-based contact-type adhesive.

The silicone-based contact adhesive according to the present invention has a silicone resin (A) content of more than 90% by weight and 99% by weight or less, and a silicone resin (B) content of 1% or less. It is characterized by being at least 10% by weight and less than 10% by weight. The silicone-based contact adhesive of the present invention is characterized in that the polymerizable vinyl group-containing monomer is methyl methacrylate, n-butyl methacrylate, isobornyl methacrylate, tetrahydrofuran methacrylate, glycidyl methacrylate, styrene or acrylonitrile. And In addition, in the silicone-based contact adhesive according to the present invention, the acrylic resin (C) may contain the polymerizable vinyl group in the presence of the silicone resin (A) and / or the silicone resin (B). It is obtained by copolymerizing a monomer with a comonomer having a silicon-reactive group, or by polymerizing the polymerizable vinyl group-containing monomer in the presence of a chain transfer agent having a silicon-reactive group. .

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The adhesive of the present invention has a main chain structure
Is a polyoxyalkylene, and the molecular terminal of the formula is
Si (OR¹)_Two(R^Two) (R¹Is a group having 1 to 8 carbon atoms.
Alkyl group, R ^TwoIs an alkyl group having 1 to 8 carbon atoms
You. ) Which is composed of an alkoxysilyl group
Silicone resin (A) whose main chain structure is polyoxyal
Is a compound of the formula —Si (OR¹)_Three
(R¹Is an alkyl group having 1 to 8 carbon atoms. )
Silicone tree composed of alkoxysilyl groups
Fat (B), acrylic acid ester, methacrylic acid ester
Selected from the group of ter, styrene and acrylonitrile
Polymerization of one or more polymerizable vinyl group-containing monomers
Acrylic resin (C) having a silicon reactive group
As an active ingredient, the silicone resin (A) and the silicone resin
When the content of the silicone resin (B) is
Fat (A) is 50 to 99% by weight, the silicone resin
(B) is 50 to 1% by weight, and the acrylic resin
(C) is contained in the silicone resin (A) and the silicone resin (A).
5 to 200 per 100 parts by weight of the total amount of the corn resin (B)
It is characterized by parts by weight.

The silicone resin (A) has a main chain structure of polyoxyalkylene and a molecular terminal of the formula —Si (OR ¹ ) ₂ (R ² ) (R ¹ is a group having 1 to 8 carbon atoms). An alkyl group, R ² is an alkyl group having 1 to 8 carbon atoms).
The oxyalkylene of the polyoxyalkylene is represented by the formula -OR ^3- , wherein R ³ has 2 to 2 carbon atoms.
Six alkylene groups. Examples of the alkylene group include ethylene, propylene, butylene and the like, preferably ethylene and propylene, particularly preferably propylene. Of course, as the polyoxyalkylene, R ³
May be composed of different oxyalkylenes.
Examples of the alkyl group having 1 to 8 carbon atoms represented by R ¹ and R ² include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, te
Examples thereof include rt-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl and the like, preferably methyl and ethyl, particularly preferably methyl. The two alkyl groups may be the same or different.

The silicone resin (B) has a main chain structure of polyoxyalkylene and a molecular terminal of the formula —Si (OR ¹ ) ₃ (R ¹ is an alkyl group having 1 to 8 carbon atoms). .)). The oxyalkylene of the above polyoxyalkylene is represented by the formula —O—R ³ —, wherein R ³ is an alkylene group having 2 to 6 carbon atoms. Examples of the alkylene group include ethylene, propylene, butylene and the like, preferably ethylene and propylene, particularly preferably propylene. Of course, as the polyoxyalkylene, R ³ may be composed of different oxyalkylenes. Examples of the alkyl group having 1 to 8 carbon atoms represented by R ¹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and t-butyl.
Examples include tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl and the like, preferably methyl and ethyl, particularly preferably methyl. The three alkyl groups may be the same or different.

The above-mentioned silicone resin (A) and silicone resin (B) are both known, for example, Japanese Patent Publication No. 45-36319, Japanese Patent Publication No. 46-12154, Japanese Patent Publication No. 49-32673, JP-A-50-15
It can be produced by the methods described in JP-A-6599, JP-A-51-73561, JP-A-54-6096, JP-A-3-160022 and the like.

Specifically, the silicone resin (A) is
(1) A method in which hydroxyalkyldialkoxysilanes such as hydroxymethyldimethoxysilane are added to a polyoxyalkylene having an allylated molecular terminal by Michael addition, and (2) A polyisocyanate having a molecular terminal isocyanated. For oxyalkylene, an amino-substituted alkyldialkoxysilane such as N-phenyl-γ-aminopropylmethyldimethoxysilane or a mercapto-substituted alkyldialkyl such as γ-mercaptopropylmethyldimethoxysilane capable of reacting with the terminal isocyanate group A method of synthesizing by adding an alkoxysilane, (3) for a polyoxyalkylene having a hydroxyl group at a molecular end,
a method of adding and synthesizing an isocyanate group-substituted alkyldialkoxysilane such as γ-isocyanatopropylmethyldimethoxysilane, and (4) a method of adding γ-mercaptopropylmethyldimethoxysilane to a polyoxyalkylene having a terminal allyl group. Examples include those produced by a method of adding a mercapto group-substituted alkyldialkoxysilane for synthesis.

In the above synthesis method, a polymerization initiator such as a radical generator may be used. As the polymerization initiator, peroxide-based, azo- or redox-based polymerization initiators, metal compound catalysts and the like can be used. Specifically, 2,2′-azobis-2-isobutyronitrile, 2,2′-azobis-2-isobutyronitrile, 2'-azobis-2-
Methylbutyronitrile, benzoyl peroxide, t-
Alkyl peroxyester, acetyl peroxide,
Diisopropyl peroxycarbonate and the like.

The silicone-based resin (B) is obtained by replacing the hydroxyalkyldialkoxysilanes in the above-mentioned method (1) for synthesizing the silicone-based resin (A) with a hydroxytrimethoxysilane or hydroxytriethoxysilane. A method using trialkoxysilanes,
In the above (2), instead of the amino-substituted alkyldialkoxysilane, amino-substituted trialkyl such as N-phenyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, etc. A method in which a mercapto group-substituted trialkoxysilane such as γ-mercaptopropyltrimethoxysilane or γ-mercaptopropyltriethoxysilane is used in place of the mercapto group-substituted alkyldialkoxysilane, Instead of a substituted alkyldialkoxysilane, γ
A method using an isocyanate group-substituted trialkoxysilane such as isocyanatepropyltrimethoxysilane and γ-isocyanatopropyltriethoxysilane. In the above (4), instead of the mercapto group-substituted alkyldialkoxysilane, γ-mercaptopropyltrimethoxysilane is used. And those manufactured by a method using a mercapto group-substituted trialkoxysilane such as γ-mercaptopropyltriethoxysilane.

The silicone resin (A) and the silicone resin (B) have a number average molecular weight of 500 to 3 respectively.
It is preferable to use those having a molecular weight of 0000, especially 2,000 to 20,000. Further, as the silicone resin (A), a commercially available silicone resin called a modified silicone resin is suitably used. Examples of the commercially available products include, for example, MS Polymer S203, S303, 1
5A, Cyril SAT030, SAT200, SAX4
00, manufactured by Asahi Glass Co., Ltd., Exeter S2410, S
2420 and S3430.

The acrylic resin (C) is a polymer of one or more polymerizable vinyl group-containing monomers selected from the group consisting of acrylic acid ster, methacrylic acid ester, styrene and acrylonitrile. It has.

The acrylate and methacrylate of the polymerizable vinyl group-containing monomer (hereinafter referred to as (meth) acrylate) include methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl. (Meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, dodecyl (meth)
Acrylate, tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate or the like, wherein the alkyl group has 1 to 20 carbon atoms and is an alkyl ester of acrylic acid or methacrylic acid;
Cyclohexyl acrylate, cyclohexyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate,
Isobornyl acrylate, isobornyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, tert-butylaminoethyl acrylate, tert-butylaminoethyl methacrylate, cyclohexylaminoethyl acrylate,
Cyclohexylaminoethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, tetrahydrofuran acrylate, tetrahydrofuran methacrylate, allyl acrylate, allyl methacrylate,
2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, trimethylolpropane triacrylate, trimethylolpropane triacrylate Methacrylate, trade name M-1 manufactured by Toa Gosei Co., Ltd.
10 and M-111, trade names Beova 9 and Beova 10, manufactured by Shell Chemical Company, and trifluoroethyl methacrylate.

Among the above polymerizable vinyl group-containing monomers, methyl methacrylate, n-butyl methacrylate, isobornyl methacrylate, tetrahydrofuran methacrylate, glycidyl methacrylate, styrene and acrylonitrile are particularly preferred, and these polymerizable vinyl group-containing monomers are polymerized. In the case of a polymer obtained by
This shows a further effect that the adhesive strength immediately after the contact becomes larger and the tack range becomes longer.

The acrylic resin (C) is obtained by copolymerizing the above-mentioned monomer having a polymerizable vinyl group with a comonomer having a silicon-reactive group such as a polyalkoxysilyl group, or by copolymerizing a silicon-reactive group such as a polyalkoxysilyl group. Is a polymer having a silicon-reactive group such as a polyalkoxysilyl group obtained by polymerization in the presence of a chain transfer agent having

Examples of comonomers having a polyalkoxysilyl group (hereinafter, acryloxy and methacryloxy are referred to as (meth) acryloxy), γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth)
Γ- such as acryloxypropyltrimethoxysilane and γ- (meth) acryloxypropyltriethoxysilane
(Meth) acryloxy (alkyl) polyalkoxysilane and the like can be mentioned. Examples of chain transfer agents having a polyalkoxysilyl group include γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ
-Aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)
-Γ-aminopropyltrimethoxysilane, N- (β-
Aminoethyl) -γ-aminopropylmethyldimethoxysilane.

The above polymerizable vinyl group-containing monomer is copolymerized with a comonomer having a silicon-reactive group such as a polyalkoxysilyl group or in the presence of a chain transfer agent having a silicon-reactive group such as a polyalkoxysilyl group. The method of producing the acrylic resin (C) is preferably carried out in the presence of a polymerization initiator, a chain transfer agent having no silicon-reactive group, and / or a solvent. As the polymerization initiator, azobisisobutyronitrile, trade name VA-046 manufactured by Wako Pure Chemical Industries, Ltd.
B, VA-057, VA-061, VA-601, VA
-085, VA-086, VA-096 and VAm-1
Azo compounds such as 10, peroxides such as benzoyl peroxide, as a chain transfer agent having no silicon-reactive group, lauryl mercaptan, thio-β-naphthol, thiophenol, n-butyl mercaptan, ethyl thioglycolate, Isopropyl mercaptan, t-butyl mercaptan, etc., as a solvent xylene, toluene, acetone,
Examples include methyl ethyl ketone, ethyl acetate, butyl acetate and the like. These solvents can be removed by a method such as distillation under reduced pressure as needed after completion of the polymerization.

The adhesive of the present invention contains the above silicone resin (A), the above silicone resin (B) and the above polymer (C) as active ingredients. The silicone resin (A) and the silicone resin (B) The content of the silicone resin (A) is 50 to 99% by weight, preferably more than 90% by weight and 99% by weight or less, and the content of the silicone resin (B) is 50 to 1% by weight, preferably 1% by weight. More than 10
% By weight, and the content of the acrylic resin (C) is 5 to 200 parts by weight, preferably 8 to 1 part by weight per 100 parts by weight of the total of the silicone resin (A) and the silicone resin (B).
It is characterized in that it is 50 parts by weight, particularly preferably 10 to 80 parts by weight.

The content ratio of the silicone resin (A) to the silicone resin (B) is 50% for the silicone resin (A).
If the amount is less than 99% by weight, the tack duration time and the bonding time will be short, and if it exceeds 99% by weight, the tack development speed will be low. When the content of the acrylic resin (C) is less than 5 parts by weight per 100 parts by weight of the total of the silicone resin (A) and the silicone resin (B), the tack development strength becomes weak and exceeds 200 parts by weight. And insufficient adhesive strength.

The adhesive of the present invention can be prepared by blending at least the silicone resin (A), the silicone resin (B) and the acrylic resin (C) in the proportions shown above. As described below, in the presence of the silicone resin (A) and / or the silicone resin (B), the polymerizable vinyl group-containing monomer is copolymerized with a comonomer having a silicon reactive group such as a polyalkoxysilyl group. Polymerizing or using the acrylic resin (C) comprising a polymer obtained by polymerizing the polymerizable vinyl group-containing monomer in the presence of a chain transfer agent having a silicon-reactive group such as a polyalkoxysilyl group. The adhesive of the present invention is prepared by using the above-mentioned silicone resin (A) and / or the above-mentioned silicone resin (B) used at times as the adhesive component of the present invention. It is particularly preferable to that.

Specifically, (1) a polymer obtained by polymerizing the polymerizable vinyl group-containing monomer in the presence of the silicone resin (A) as described above to obtain the acrylic resin (C); (2) a method of mixing the above-mentioned silicone resin (B) with the above-mentioned acrylic resin (C) by polymerizing the above-mentioned polymerizable vinyl group-containing monomer in the presence of the above-mentioned silicone resin (B) as described above; (3) a method of mixing the above-mentioned silicone resin (A) and the above-mentioned silicone resin (A), (3) the above-mentioned acrylic resin by polymerizing the above-mentioned polymerizable vinyl group-containing monomer in the presence of the above-mentioned silicone resin (A). A mixture of the resin (C) and the acrylic resin (C) obtained by polymerizing the polymerizable vinyl group-containing monomer in the presence of the silicone resin (B) as described above. how to,( ) The presence of the silicone-based resin (A) and the silicone-based resin (B), the polymerizable vinyl group-containing monomer and polymerized as described above is a method to the acrylic resin (C).

In the above methods (1) to (4), the above-mentioned polymerization initiator and silicon-reactive group preferably used in producing an acrylic resin (C) by polymerizing a polymerizable vinyl group-containing monomer are used. It goes without saying that chain transfer agents and / or solvents which do not have can be present. They can be selected from the compounds described above. Further, the solvent used in the polymerization can be removed by a method such as distillation under reduced pressure, if necessary, after the completion of the polymerization.

The adhesive of the present invention contains each of the above-mentioned active ingredients. The adhesive may contain a curing catalyst,
Various additives can be included. As the curing catalyst,
Organotin compounds, metal complexes, basic substances, organophosphorus compounds and water (moisture in the air) can be used. As the curing catalyst, an organic tin, a metal complex, a base such as an amine, an organic phosphate compound, and water (moisture in the air) can be used.

Specifically, as the organic tin, dibutyltin dilaurate, dioctyltin dimaleate, dibutyltin phthalate, stannous octylate, dibutyltin methoxide,
Examples thereof include dibutyltin diacetyl acetate, dibutyltin diversate, and dibutyltin oxide. Examples of the metal complex include titanate compounds such as tetrabutyl titanate, tetraisopropyl titanate, and triethanolamine titanate; metal carboxylate such as lead octylate, lead naphthenate, nickel naphthenate, and cobalt naphthenate; and aluminum acetylacetonate complex. And metal acetylacetonate complexes such as vanadium acetylacetonate complex. Examples of the base include aminosilanes such as γ-aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane; quaternary ammonium salts such as tetramethylammonium chloride and benzalkonium chloride; DABCO (registered trademark) manufactured by Sankyo Air Products Trademark) series, DABCO BL series, linear or cyclic tertiary amines and quaternary ammonium salts containing a plurality of nitrogen atoms, such as 1,8-diazabicyclo [5.4.0] undec-7-ene. Can be
Examples of the organic phosphoric acid compound include monomethyl phosphoric acid, di-n-butyl phosphoric acid, and triphenyl phosphate. The mixing ratio of the curing catalyst is 0.01 to 10 parts by weight per 100 parts by weight of the active ingredient of the adhesive.

Examples of the various additives include fillers, plasticizers, various additives, solvents, dehydrating agents and the like. Examples of the filler include fumed silica, calcium carbonate, magnesium carbonate, clay, talc, silica, various balloons, and the like.

Examples of the plasticizer include phthalic acid esters such as dioctyl phthalate and dibutyl phthalate, aliphatic carboxylic acid esters such as dioctyl adipate and dibutyl sebacate, various polyols and derivatives thereof, and liquid polyolefins. . Antioxidants, thixotropic agents, ultraviolet absorbers,
Pigments, various tackifiers, silane coupling agents,
Titanate coupling agents, aluminum coupling agents and the like can be mentioned. Any solvent may be used as long as it has good compatibility with the adhesive or the like and a water content of 500 ppm or less. Examples of the dehydrating agent include quicklime, orthosilicate, anhydrous sodium sulfate, zeolite,
Examples include methyl silicate, ethyl silicate, various alkylalkoxysilanes, various vinylalkoxysilanes, and the like.

[0035]

The present invention will be described below in more detail with reference to examples. The polymerizable vinyl group-containing monomer, the chain transfer agent, the silicone resin (A) and the silicone resin (B) used in the following synthesis examples, and the silicone resin used when preparing the adhesive composition ( B), a tin catalyst, a silane coupling agent and calcium carbonate are as follows. Other than these, reagents were used.

The polymerizable vinyl group-containing monomer acrylic ester S (octadecyl methacrylate, manufactured by Mitsubishi Rayon Co., Ltd.) (mixed alkyl methacrylate C ₁₂ and C _13, manufactured by Mitsubishi Rayon Co., Ltd.) acrylic ester SL comonomers having silicon reactive groups KBM503 (gamma -Methacryloxypropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.) Chain transfer agent KBM803 (γ-mercaptopropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.) Silicone resin (A) S303 (Methyl dimethoxysilyl modified silicone) resin, Kaneka Corporation) S203 (molecular terminal methyldimethoxysilyl type modified silicone resins, Kaneka Corp.) ES-S2420 (molecular terminal methyldimethoxysilyl type modified silicone resin, manufactured by Asahi Glass Co., Ltd.) silicone resin( ) ES-X3440-ST (molecular terminal trimethoxysilyl type modified silicone resin, manufactured by Asahi Glass Co., Ltd.) ES-GX3406a (vinyl group-containing monomer (a mixture of acrylonitrile and styrene) polymer molecular terminal trimethoxysilyl type modified silicone resins, vinyl Group-containing monomer Polymer molecule content: about 23% by weight, manufactured by Asahi Glass Co.) Tin catalyst: An equivalent mixed solution of dibutyltin oxide and dioctyl phthalate Silane coupling agent KBM603 (N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane) , Shin-Etsu Chemical Co., Ltd.) Calcium carbonate white luster CCR (Surface treated calcium carbonate, Shiraishi calcium) NS2300 (Untreated calcium carbonate, Nitto Powder Chemical)

(Synthesis Examples 1 to 5) Table 1 heated to 110 ° C.
The amount of the polymerizable vinyl group-containing monomer, the comonomer having a silicon reactive group, the azobisisobutyronitrile (AIBN) as the chain transfer agent and the polymerization initiator shown in Table 1 are shown in Table 1 in the amount of xylene shown in Table 1. After dripping the solution dissolved in the ratio over 6 hours, polymerization was carried out for 2 hours, and synthetic products 1 to 5 were obtained.
I got The amounts of the components shown in Table 1 are parts by weight (the same applies to Table 5).

(Synthesis Examples 6 to 10) Silicone resin (A) and / or silicone resin (B) were added to the synthetic products 1 to 5 obtained in Synthesis Examples 1 to 5 heated to 50 to 60 ° C. 2
Then, xylene was removed by distillation under reduced pressure, and synthetic products 6 to 10 were obtained.

(Synthesis Examples 11 to 15) In the amount of the silicone resin (A) and / or silicone resin (B) shown in Table 3 heated to 110 ° C., a polymerizable vinyl group-containing monomer shown in Table 3 A solution prepared by dissolving a comonomer having a silicon-reactive group, a chain transfer agent, and AIBN at the ratios shown in Table 3 was used.
After dropping over a period of time, polymerization was carried out for 2 hours to obtain a synthesized product 11
~ 15.

(Examples 1 to 8) Compounds 6 to 15 obtained in the above synthesis examples, a tin catalyst, calcium carbonate, or further a silicone resin (B), and a silane coupling agent were blended in the proportions shown in Table 4. Thus, a contact adhesive composition was prepared. These compositions are applied to the surface of two pieces of Asada material and stretched thinly. At a temperature of 23 ° C. and a relative humidity of 65%, tack development time, tack range, tack strength, tightness development time, bonding time, The initial setting strength was examined as follows, and the results are shown in Table 6. Also, after applying to the surface of two Asada materials, they are pasted together and crimped,
After curing for 7 days at a temperature of 23 ° C. and a relative humidity of 65%,
Tensile shear bond strength was measured by Shimadzu Autograph (AGS-G
(Type), and the results are shown in FIG.

Tack onset time: Time from application to tack onset examined by finger touch Tack range: Time from onset of tack to disappearance of tack Tack strength: A; Bond G10 (solvent type chloroprene contact type manufactured by Konishi Co.) Adhesive) Strong tack ○: Tack slightly weaker than Bond G10 △: Tack considerably weaker than Bond G10 (no practicality) Settling time: After application, after application time (open time), Coating time to prevent slippage by hand Bonding time: From the time of the appearance of the settling property, the part that is not in contact (the part that is not substantially bonded at the bonding interface between the adhesive layers when peeled) is 30% or less. Time to keep Initial setting strength: Fixing property when laminating at setting time ◎: Easily displaced by hand There ○; there is considerable when shifting manually resistance △; a little resistance when shifting by hand (without practicability) ×; easily displaced by hand (without practicability)

(Comparative Examples 1 to 7) The silicone resin (A), the silicone resin (B), the composite 9, the composite 10, the composite 12, or the composite 10 and the composite 12, shown in Table 5,
In addition, a contact type adhesive composition was prepared by blending a tin catalyst, a silane coupling agent and calcium carbonate in the proportions shown in Table 5. The physical properties of the obtained composition were examined in the same manner as in Examples 1 to 8, and the results are shown in Table 7 and FIG.

(Reference Example) The physical properties of Bond G10 were examined in the same manner as in Examples 1 to 8, and shown in Table 7.

[0044]

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

From the results shown in Tables 6 and 7, the composition according to the present invention retains various physical properties required for the contact type adhesive which is insufficient with the corresponding synthetic product according to the comparative example and the conventional silicone resin. You can see that it is. In addition, it can be seen from FIG. 1 that the composition according to the present invention hardly changes in the adhesive strength even by the difference in the open time.

[0046]

The contact adhesive of the present invention has the same or better performance than the conventional solvent-type contact adhesive despite the moisture-curable silicone adhesive.

[Brief description of the drawings]

FIG. 1 is a view showing a change in adhesive strength due to a difference in open time.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J040 DB041 DB042 DF041 DF042 DF051 DF052 DF061 DF062 DF081 DF082 EC231 EC232 EE021 EE022 EE051 EE052 GA05 GA08 GA11 GA13 GA31 JB04 LA01 LA05 LA06 QA01

Claims (4)

[Claims] The main chain structure is polyoxyalkylene, and the molecular terminal of the formula is -Si (OR ¹ ) ₂ (R ² )
(R ¹ is an alkyl group having 1 to 8 carbon atoms, and R ² is an alkyl group having 1 carbon atom.
８8 alkyl groups. A) a silicone resin (A) composed of an alkoxysilyl group represented by the formula ( ¹ ), in which the main chain structure is polyoxyalkylene, and the molecular terminal of which is of the formula -Si (OR1) ₃ (R1 has ^{1 to 1} carbon atoms). And at least one selected from the group consisting of an acrylic ester, a methacrylic ester, styrene and acrylonitrile. A polymer of a polymerizable vinyl group-containing monomer, which contains an acrylic resin (C) having a silicon-reactive group as an active ingredient, and the content ratio of the silicone resin (A) and the silicone resin (B) is 50 to 99% by weight of the silicone resin (A),
The silicone resin (B) is 50 to 1% by weight, and the content of the acrylic resin (C) is 5 to 5 parts by weight per 100 parts by weight of the total of the silicone resin (A) and the silicone resin (B). A silicone-based contact adhesive characterized by being 200 parts by weight. 2. The content of the silicone resin (A) is more than 90% by weight and not more than 99% by weight, and the content of the silicone resin (B) is 1% by weight or more and less than 10% by weight. The silicone-based contact adhesive according to claim 1, wherein 3. The method according to claim 1, wherein the polymerizable vinyl group-containing monomer is methyl methacrylate, n-butyl methacrylate, isobornyl methacrylate, tetrahydrofuran methacrylate, glycidyl methacrylate, styrene or acrylonitrile. Silicone contact adhesive. 4. A comonomer wherein said acrylic resin (C) is obtained by converting said polymerizable vinyl group-containing monomer to a silicon-reactive group in the presence of said silicone resin (A) and / or said silicone resin (B). 4. A polymer obtained by copolymerizing the polymerizable vinyl group-containing monomer in the presence of a chain transfer agent having a silicon-reactive group with the polymerizable vinyl group-containing monomer.
Item 7. The silicone-based contact adhesive according to item 1.