JP2001220568A - Silicone contact adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a moisture-curing silicone contact adhesive showing a large tack strength, a repaid tack development and a long tack durability. SOLUTION: The silicone contact adhesive contains a silicone resin (A) wherein the main chain structure is a polyoxyalkylene and two alkoxy groups and a hydrocarbon group are directly linked to a silicon, atom, a silicone resin (B) wherein the main chain structure is a polyoxyalkylene and three alkoxy groups are directly linked to a silicon atom and a polymer (C) of a polymerizable vinyl group-containing monomer as active components. Here, the proportions of the silicone resin (A) and the silicone resin (B) contained are 50 to 99% and 50 to 1%, respectively, and the amount of the polymer (C) contained is 5 to 2,000 pts. against 100 pts. the total of the silicone resin (A) and the silicone 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 Application Laid-Open No. 10-251552)
Has been proposed, which has excellent storage stability, is fast-curing, and has an adhesive function with excellent 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 a polymer of a compound having a polymerizable unsaturated group, ie, three alkoxy groups Secures the initial settle of the contact by the reaction of the silicon-containing organic group of the silicone polymer having the silicon-containing organic group directly bonded to the silicon atom. The concept of extending the time that can contact with other components, it has reached the Heading out the present invention capable of achieving the object of the present invention.

That is, according to the present invention, the main chain structure is poly-
Oxyalkylene, the molecular end of which is of the formula -Si (O
R¹)_Two(R^Two) (R¹Is alkyl having 1 to 8 carbon atoms
Group, R ^TwoIs an alkyl group having 1 to 8 carbon atoms. )
Based on alkoxysilyl groups
Resin (A) whose main chain structure is polyoxyalkylene
And the molecular end of the formula is -Si (OR¹)_Three(R¹Is charcoal
It is an alkyl group having a prime number of 1 to 8. Arco represented by)
Average silicone resin (B) composed of xyloxy groups
And a polymer of a polymerizable vinyl group-containing monomer (excluding silicon
(Excluding polymers having reactive groups) (C) as an active ingredient
The silicone resin (A) and the silicone resin
The content of the fat (B) is 50% for the silicone resin (A).
To 99% by weight, and the amount of the silicone resin (B) is 50 to 1
%, A polymer of the polymerizable vinyl group-containing monomer.
(C) is contained in the silicone resin (A) and the silicone resin (A).
5 to 2,0 per 100 parts by weight of the corn resin (B) in total
100 parts by weight, silicone-based contour
The gist of the invention is that of a self-adhesive.

In the silicone-based contact adhesive according to the present invention, 1 to 90% by weight of the polymer (C) of the polymerizable vinyl group-containing monomer has a glass transition temperature of 0 to 200 ° C. D).
Further, the silicone-based contact adhesive of the present invention,
The content ratio of the silicone resin (A) is 70 to 97% by weight, and the content ratio of the silicone resin (B) is 30 to 97%.
3% by weight. Further, in the silicone-based contact adhesive of the present invention, the polymer (D) may be one or two selected from acrylonitrile, styrene, glycidyl methacrylate, methyl methacrylate, n-butyl methacrylate, isobornyl methacrylate and tetrahydrofuran methacrylate. It is a polymer (E) of at least one kind of polymerizable vinyl group-containing monomer. In the silicone-based contact adhesive of the present invention, the polymer (C) polymerizes the polymerizable vinyl group-containing monomer in the silicone resin (A) and / or the silicone resin (B). It is characterized by being obtained by the above.

Further, the silicone-based contact adhesive of the present invention is characterized in that it further contains calcium carbonate. The silicone-based contact adhesive of the present invention is characterized in that the calcium carbonate is untreated calcium carbonate.

[0013]

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
(B) and polymer of polymerizable vinyl group-containing monomer
(However, a polymer having a silicon reactive group is excluded)
Containing as an active ingredient the silicone resin (A) and the silicone resin.
The silicone resin (B) is contained in the silicone resin
(A) is 50 to 99% by weight, the silicone resin (B)
Is from 50 to 1% by weight, and the polymerizable vinyl group-containing monomer is
Of the silicone resin (A)
And a total of 100 parts by weight of the silicone resin (B)
5 to 2,000 parts by weight.

The silicone resin (A) has a main chain structure of polyoxyalkylene and has 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 of synthesizing a polyoxyalkylene having an allylated molecular terminal by hydrosilylating a hydroxyalkyldialkoxysilane such as hydroxymethyldimethoxysilane using a platinum group catalyst; For the isocyanated polyoxyalkylene, N- capable of reacting with the terminal isocyanate group
Amino-substituted alkyl dialkoxysilane such as phenyl-γ-aminopropylmethyldimethoxysilane, or γ
A method of adding a mercapto group-substituted alkyldialkoxysilane such as mercaptopropylmethyldimethoxysilane to synthesize (3) an isocyanate group such as γ-isocyanatopropylmethyldimethoxysilane with respect to a polyoxyalkylene having a hydroxyl group at a molecular end; A method of adding and synthesizing a substituted alkyldialkoxysilane; (4) adding a mercapto group-substituted alkyldialkoxysilane such as γ-mercaptopropylmethyldimethoxysilane to a polyoxyalkylene having an allyl group at the molecular end; Those produced by a method of synthesizing and the like can be mentioned.

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'-azobis (2
-Methylbutyronitrile), benzoyl peroxide,
Examples include t-alkyl peroxyester, acetyl peroxide, diisopropyl peroxycarbonate, and the like.

The silicone-based resin (B) is obtained by replacing the hydroxyalkyldialkoxysilanes with a hydroxytrimethoxysilane, hydroxytriethoxysilane or the like in the above (1) of the method for synthesizing the silicone-based resin (A). 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 .: Exester S2410, S
2420 and S3430.

Examples of the polymerizable vinyl group-containing monomer used in forming the polymer (C) of the polymerizable vinyl group-containing monomer include acrylic acid, methacrylic acid, acrylates and methacrylates (hereinafter, these are referred to as (meth) ) Acrylate), styrene compounds,
Acrylonitrile, α-methylacrylonitrile, 2,
4-dicyanobutene-1, vinylpyrrolidone, vinylcarbazole, 2-methacryloyloxyethyl succinate, 2-methacryloyloxyethyl maleate, 2-methacryloyloxyethyl phthalate, 2-methacryloyloxyethyl hexahydrophthalate, acrylamide, methacrylamide , Vinyl glycidyl ether, allyl glycidyl ether, methacryl glycidyl ether, vinyl chloride, vinyl acetate, vinyl propionate, butadiene, isoprene, chloroprene; other olefins, unsaturated esters, halogenated olefins,
Vinyl ether and the like.

As the (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate,
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, etc., alkyl esters of acrylic acid or methacrylic acid having 1 to 20 carbon atoms in the alkyl group; 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 trimethacrylate, trade name: M-110, manufactured by Toagosei Co., Ltd.
And M-111, trade names, manufactured by Shell Chemical Co., Ltd .: VEOBA 9 and VEOBA 10, trifluoroethyl methacrylate and the like.

Examples of the styrene compound include styrene, vinyltoluene, divinylbenzene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, p-methoxystyrene and the like. . These polymerizable vinyl group-containing monomers are not limited to one kind, and two or more kinds can be used.

The polymer (C), which is one component of the adhesive of the present invention, is a polymer obtained by polymerizing the polymerizable vinyl group-containing monomer, and the polymer (C) comprises a plurality of polymers. One or more of which are 0 to 200 ° C
(D) having a glass transition temperature of 1 to 90% by weight, the adhesive strength immediately after contact is increased and the tack range is extended. . Examples of the polymerizable vinyl group-containing monomer that can be the polymer (D) include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, n -Tetradecyl methacrylate, n-hexadecyl methacrylate,
n-octadecyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, isobornyl acrylate, isobornyl methacrylate, dimethylaminoethyl methacrylate, tert-butylaminoethyl methacrylate, cyclohexylaminoethyl acrylate, Glycidyl methacrylate, tetrahydrofuran acrylate, tetrahydrofuran methacrylate, allyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, trade names: M-110 and M-111, manufactured by Toagosei Co., Ltd., Shell Chemical Company Product name: Beova And VeoVa 10, trifluoroethyl methacrylate, styrene, alpha-methyl styrene, o
-Methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, p-methoxystyrene,
Acrylonitrile, vinylpyrrolidone, vinylcarbazole, 2-methacryloyloxyethyl succinate, 2-methacryloyloxyethyl maleate, 2-phthalic acid
Methacryloyloxyethyl, hexahydrophthalic acid 2
-Methacryloyloxyethyl, vinyl chloride and the like.

Further, among these polymerizable vinyl group-containing monomers, one or more monomers selected from acrylonitrile, styrene, glycidyl methacrylate, methyl methacrylate, n-butyl methacrylate, isobornyl methacrylate and tetrahydrofuran methacrylate are polymerized. The use of the polymer (E) obtained in this manner is particularly preferable since the adhesive strength immediately after contact is further increased and the tack range is further increased.

The method of polymerizing the polymerizable vinyl group-containing monomer to obtain a polymer thereof may be any of known methods such as radical polymerization, anionic polymerization, and cationic polymerization, which are usually performed for the polymerization of these vinyl monomers. 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), A product name: V-601, manufactured by Wako Pure Chemical Industries, Ltd .: A radical polymerization method carried out in the presence of a polymerization initiator such as benzoyl peroxide, t-alkylperoxyester, acetyl peroxide, diisopropylperoxycarbonate is particularly preferred. . At this time, polymerization is carried out in the presence of a chain transfer agent such as lauryl mercaptan, γ-mercaptopropyltrimethoxysilane, thio-β-naphthol, thiophenol, n-butyl mercaptan, ethyl thioglycolate, isopropyl mercaptan, and t-butyl mercaptan. It can be performed. Further, the polymerization can be carried out in the presence of a solvent such as xylene, toluene, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate and the like.

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 The content of (B) is 50 to 99% by weight, preferably 70 to 97% by weight for the silicone resin (A), and 50 to 1% for the silicone resin (B).
%, Preferably 30 to 3% by weight, and the content of the polymer (C) is 5 to 2,000 per 100 parts by weight of the total of the silicone resin (A) and the silicone resin (B).
It is characterized in that the amount is from 10 to 100 parts by weight, preferably from 8 to 500 parts by weight, particularly preferably from 10 to 100 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 polymer (C) is less than 5 parts by weight per 100 parts by weight of the silicone resin (A) and the silicone resin (B), the tack development strength becomes weak, and 2,000 parts by weight If it exceeds, the adhesive strength becomes insufficient. The content ratio of the silicone resin (A) and the silicone resin (B) is 70-97% by weight for the silicone resin (A),
When the content of the silicone resin (B) is 30 to 3% by weight, the adhesive strength immediately after the contact is increased, and the effect of increasing the tack range is preferred, which is preferable.

The adhesive of the present invention can be prepared by blending at least the silicone resin (A), the silicone resin (B) and the polymer (C) in the proportions described above. As described below, the polymerizable vinyl group-containing monomer is polymerized in the presence of the silicone-based resin (A) and / or the silicone-based resin (B) to use the polymer (C). It is particularly preferable to prepare the adhesive of the present invention using the resin (A) and / or the silicone resin (B) as the adhesive component of the present invention.

Specifically, (1) a polymer (C) obtained by polymerizing the polymerizable vinyl group-containing monomer in the presence of the silicone resin (A); (2) polymerizing the polymerizable vinyl group-containing monomer in the presence of the silicone resin (B) to form the polymer (C), and the silicone resin (A). (3) a method of polymerizing the polymerizable vinyl group-containing monomer in the presence of the silicone resin (A) to form the polymer (C), and a method of mixing the silicone resin (B). A method of polymerizing the polymerizable vinyl group-containing monomer in the presence thereof and mixing it with the polymer (C), (4) the silicone resin (A)
And a method of polymerizing the polymerizable vinyl group-containing monomer in the presence of the silicone resin (B) to obtain the polymer (C).

In the above methods (1) to (4), when the polymerizable vinyl group-containing monomer is polymerized in the presence of the silicone resin (A) and / or the silicone resin (B), Preferably, an initiator, a chain transfer agent and / or a solvent are present. As the polymerization initiator,
2'-azobisisobutyronitrile, trade names: VA-046B, VA-057, VA-06, manufactured by Wako Pure Chemical Industries, Ltd.
1, VA-085, VA-086, VA-096, V-
Azo compounds such as 601, V-65 and VAm-110,
Peroxides such as benzoyl peroxide, as chain transfer agents, lauryl mercaptan, thio-β-naphthol, thiophenol, n-butyl mercaptan, ethyl thioglycolate, isopropyl mercaptan, t-butyl mercaptan, etc., as a solvent Xylene, toluene, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate and the like can be mentioned. 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-mentioned active ingredients. In addition to the above-mentioned active ingredients, the adhesive may contain a curing catalyst, a filler, and various additives as required. In particular, it is more effective for the adhesive of the present invention to contain a filler due to its properties. Examples of the filler include fumed silica, calcium carbonate, magnesium carbonate, clay, talc, silica, various balloons, and the like. Among the above-mentioned fillers, it is more effective to use calcium carbonate. That is, the adhesive of the present invention is characterized in that the above-mentioned active ingredients are further combined with calcium carbonate.

Calcium carbonate includes untreated calcium carbonate whose surface is not treated at all and treated calcium carbonate whose surface is treated with fatty acids, resin acids, silane coupling agents and the like.

As untreated calcium carbonate, trade names: Shiraishi Kogyo Co., Ltd .: white glossy PZ, Tunex E, Brilliant-15, Brilliant-1500, Silver series,
Whiika series, Whiteton series, Nitto Powder Co., Ltd. Product name: NS series, Maruo Calcium Co., Ltd. Product name: R heavy coal, heavy coal N-35, super series, Nanox series, product made by Bihoku Powder Chemical Industry Co., Ltd. Name: Softon series, BF series, trade name made by Takehara Chemical Co., Ltd .: SL series, trade name made by Kamishima Chemical Co., Ltd .: Star brand series, etc.

As the treated calcium carbonate, trade names manufactured by Shiraishi Kogyo Co., Ltd .: white glossy series, carmos, homocal series, biscolite series, trade names made by Nitto Powder Chemical Co., Ltd .:
NCC series, Maruo Calcium Co., Ltd. Product name: MSK series, Calfine series, Carrex, MT-
100, MS series, MC series, Unigross series, Luminous, MC coated S series, MC coated P
Series, Esmic, Snow Light, Nano Coat S Series, Nano Coat W Series, Bihoku Koka Kogyo Co., Ltd. Product Name: Ryton Series, Takehara Chemical Co., Ltd. Product Name: WS Series, Neolite Series, Kamijima Chemical Co., Ltd. Product Name: Calcizu Series and the like.

Among the above calcium carbonates, the effect is particularly remarkable when untreated calcium carbonate is used. The amount of calcium carbonate used is determined by the amount of the active ingredient 100
5 to 1,000 parts by weight, preferably 10 to 10 parts by weight
The amount is from 500 to 500 parts by weight, particularly preferably from 15 to 300 parts by weight. If the amount of calcium carbonate used is less than 5 parts by weight, the initial setting property immediately after lamination, which is one of the effects of using calcium carbonate, is not sufficient. If it exceeds 1,000 parts by weight, tack strength and initial setting property are low. descend.

As the above-mentioned curing catalyst which can be optionally contained, an organotin compound, a metal complex, a basic compound, an organic phosphorus compound and water (moisture in the air) can be used. Specifically, as the organic tin compound, dibutyltin dilaurate, dioctyltin dimaleate, dibutyltin phthalate,
Examples thereof include stannous octylate, dibutyltin methoxide, dibutyltin diacetyl acetate, dibutyltin diversate, and dibutyltin oxide. Examples of the metal complex include tetrabutyl titanate, tetraisopropyl titanate, titanate compounds such as triethanolamine titanate, metal carboxylate such as lead octylate, lead naphthenate, nickel naphthenate, and cobalt naphthenate;
Metal acetylacetonate complexes such as aluminum acetylacetonate complex and vanadium acetylacetonate complex are exemplified. Examples of the basic compound include aminosilanes such as γ-aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane, quaternary ammonium salts such as tetramethylammonium chloride and benzalkonium chloride, and DABCO manufactured by Sankyo Air Products. (Registered 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, etc. Is mentioned.
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 a plasticizer, an additive, a solvent, a dehydrating agent and the like. Examples of the plasticizer include phthalic esters such as dioctyl phthalate and dibutyl phthalate, and aliphatic carboxylic esters such as dioctyl adipate and dibutyl sebacate. As the above additives, antioxidants, thixotropic agents, ultraviolet absorbers, pigments, various tackifiers,
Examples include a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent. As the solvent, a water content of 50 which is well compatible with the adhesive or the like is used.
Any one may be used as long as it is 0 ppm or less. Examples of the dehydrating agent include quick lime, orthosilicate, anhydrous sodium sulfate, zeolite, methyl silicate, ethyl silicate, various alkylalkoxysilanes, various vinylalkoxysilanes, and the like.

[0039]

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), tin catalyst, silane coupling agent, calcium carbonate and talc 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 KBM503 (.gamma.-methacryloxypropyl trimethoxysilane Shin-Etsu Chemical Co., Ltd.) Chain transfer agent KBM803 (γ-mercaptopropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.) Silicone resin (A) S303 (Methyl dimethoxysilyl-type modified silicone resin, Kanekachi Chemical Co., Ltd.) S203 (modified methyl resin of molecular end methyldimethoxysilyl type, manufactured by Kaneka Chemical Industry Co., Ltd.) ES-S2420 (modified silicone resin of molecular end methyldimethoxysilyl type, manufactured by Asahi Glass Co., Ltd.) Silicone resin (B) ES-X3440 −ST (min ES-GX3406a (vinyl group-containing monomer (mixture of acrylonitrile and styrene) polymerized molecular end trimethoxysilyl-type modified silicone resin, vinyl group-containing monomer polymer molecular content about 23 wt%, manufactured by Asahi Glass Co., Ltd.) tin catalyst dibutyltin oxide and dioctyl phthalate equivalent mixed solution silane coupling agent KBM603 (N- (β- aminoethyl) .gamma.-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) carbonate Calcium white luster CCR (Surface treated calcium carbonate, manufactured by Shiroishi Kogyo) MS700 (Surface treated calcium carbonate, manufactured by Maruo Calcium) NS2300 (untreated calcium carbonate, manufactured by Nitto Powder Chemical) SL2000 (untreated calcium carbonate, Takehara Chemical) company, Ltd.) barrel RF Talc (manufactured by Fuji Talc Kogyo Co., Ltd.) in xylene in the amounts shown in Table 1 was heated to (Synthesis Example 1 to 8) 110 ° C., polymerizable vinyl group-containing monomers shown in Table 1,
A solution in which 2,2'-azobisisobutyronitrile (AIBN) as a polymerization initiator and a chain transfer agent shown in Table 1 were dissolved was added dropwise over 6 hours, and then polymerization was performed for 2 hours. 8 was obtained. The amounts of the components shown in Table 1 are parts by weight (the same applies to Table 5).

(Synthesis Examples 9 to 18) The silicone resin (A) or the silicone resin (B) was added to the synthetic products 1 to 8 obtained in Synthesis Examples 1 to 8 heated at 50 to 60 ° C. in Table 2. After being added in portions at the indicated ratios and thoroughly stirred, xylene was removed by distillation under reduced pressure to obtain synthesized products 9 to 18.

(Synthesis Examples 19 to 26) In a silicone resin (A) or silicone resin (B) in an amount shown in Table 3 heated to 110 ° C., a polymerizable vinyl group-containing monomer shown in Table 3 A solution in which AIBN as an agent and the chain transfer agent shown in Table 3 were dissolved was added dropwise over 6 hours, and polymerization was performed for 2 hours to obtain synthetic products 19 to 26.

(Examples 1 to 17) Compounds 9 to 16 and 19 to 26 obtained in the above synthesis examples, tin catalyst, calcium carbonate or talc, or further a silicone resin (B), a silane coupling agent Was mixed at the ratios shown in Tables 4 and 5 to prepare a contact adhesive composition. 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 in the following manner, and the results are shown in Tables 6 and 7. or,
After applying to the surface of two Asada materials, they were pasted and pressure-bonded at the time of application. After curing for 7 days at a temperature of 23 ° C. and a relative humidity of 65%, the tensile shearing adhesive strength was measured by Shimadzu Autograph (A).
GS-G), and the results of Examples 2, 7 and 16 are shown in FIG.

Tack onset time: Time from application to tack onset determined 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 ○: considerable resistance when displaced by hand △: slight resistance when displaced by hand (no practicality) ×: easily displaced by hand (no practicality) (Comparative Examples 1 to 7) Silicone resin (A) shown,
Silicone resin (B), Synthetic 17, Synthetic 18, Synthetic 19, Synthetic 10, or Synthetic 10 and Synthetic 1
9, and a tin catalyst, a silane coupling agent, and calcium carbonate were blended in the proportions shown in Table 5 to prepare a contact adhesive composition. The physical properties of the obtained composition were determined in Examples 1 to
17 and the results are shown in Table 7 and the tensile shear shear strength of Comparative Examples 2 and 6 is shown in FIG.
It was shown to.

(Reference Example) The physical properties of the bond G10 were examined in the same manner as in Examples 1 to 17, and shown in Table 7.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7] From the results in Tables 6 and 7, the composition according to the present invention retains various physical properties required for a 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. 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.

Continuation of the front page F term (reference) 4J040 DB031 DB032 DE021 DE022 DF041 DF042 DF051 DF052 DF081 DF082 DF091 DF092 DG011 DG012 DH031 DH032 DL151 DL152 EE051 EE052 GA11 GA31 HA196 JB04 LA02 LA06

Claims (7)

[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 a polymer of a polymerizable vinyl group-containing monomer (excluding a polymer having a silicon-reactive group). (C) as an active ingredient, wherein the content ratio of the silicone resin (A) and the silicone resin (B) is 50 to 99% by weight of the silicone resin (A), and the silicone resin (B) is 50 to 1% by weight, and the content of the polymer (C) of the polymerizable vinyl group-containing monomer is 5 to 2, based on a total of 100 parts by weight of the silicone resin (A) and the silicone resin (B). 000 parts by weight Silicone based contact adhesive, characterized in that. 2. A polymer (D) having a glass transition temperature of 0 to 200 ° C. in an amount of 1 to 90% by weight of the polymer (C) of the polymerizable vinyl group-containing monomer. The silicone-based contact adhesive according to the above. 3. The content of the silicone resin (A) is 70 to 97% by weight, and the content of the silicone resin (B) is 30 to 3% by weight. The silicone-based contact adhesive according to the above. 4. The polymer (D) is acrylonitrile,
A polymer (E) of one or more polymerizable vinyl group-containing monomers selected from styrene, glycidyl methacrylate, methyl methacrylate, n-butyl methacrylate, isobornyl methacrylate and tetrahydrofuran methacrylate. Item 4. The silicone-based contact adhesive according to item 2 or 3. 5. The method according to claim 1, wherein the polymer (C) is obtained by polymerizing the polymerizable vinyl group-containing monomer in the silicone resin (A) and / or the silicone resin (B). The silicone-based contact type adhesive according to claim 1, wherein 6. The silicone-based contact adhesive according to claim 1, further comprising calcium carbonate. 7. The silicone-based contact adhesive according to claim 6, wherein the calcium carbonate is untreated calcium carbonate.