JPS6258638B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides a two-component non-mixable adhesive that can quickly cure at room temperature by applying the two components separately to each adherend and then bonding the adherends together without pre-mixing the two components. This invention relates to an adhesion method using. Conventionally, two-component non-mixable adhesives containing radically polymerizable acrylic monomers, elastomers, and polymerization catalysts have been known, and they exhibit excellent adhesive performance even at room temperature. It is attracting attention because there is no need to apply it to the adherend after applying it. However, there are various combinations of the compositions of the two components. For example, one component contains an acrylic monomer, an airstomer, and a polymerization catalyst that cannot polymerize the acrylic monomer by itself, and the other component contains an acrylic monomer and an air atomer. In addition to the main agent-primer type, which polymerizes acrylic monomers in the presence of a catalyst and contains a curing agent, for example, both liquids contain an acrylic monomer and an elastomer, and one contains a polymerization catalyst. Also known is a so-called two-component base type, in which the other side contains the above-mentioned curing agent. In either case, however, the acrylic monomer polymerizes and the entire adhesive is cured only when the two liquids come into contact in the presence of air. Therefore, when applying each of the two liquids separately to an adherend and then contacting and bonding the two adherends, if the liquid containing the acrylic monomer protrudes from the bonded area, it will harden slightly. Otherwise, dust etc. may adhere to it.
There were cases where liquid dripped on vertical sections. The purpose of the present invention is to provide an adhesive method that eliminates the drawbacks of the above-mentioned two-component non-mixing agent. A containing a radically polymerizable monomer and a photosensitizer of a non-mixable adhesive
After applying the component to adherend a and the B component to adherend b, irradiate light onto the A component that protrudes from the corresponding contact area when the coated surfaces of adherends a and b are brought into contact. The present invention provides an adhesive method characterized in that the protruding portion is cured. The radically polymerizable monomers contained in component A of the adhesive used in the present invention include methyl methacrylate, ethyl methacrylate, acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, butyl methacrylate, cyclohexyl methacrylate, hexyl methacrylate, -Ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, butyl acrylate, cyclohexyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, decyl acrylate,
In addition to lauryl acrylate, trimethylolproban triacrylate, trimethylolproban methacrylate, methacrylic acid, acrylic acid, glycyldyl methacrylate, itaconic acid, acrylate and methacrylate of ethylene glycol and higher glycol, general formula (In the formula, R ₁ and R ₂ are each H or CH ₃ , and n
is 0 or 1. ), i.e. dicyclopentenyl acrylate

[Formula] Dicyclopentenyl methacrylate, 2-dicyclopentenoxyethyl acrylate Examples include 2-dicyclopentenoxyethyl methacrylate, which may be used alone or in appropriate combinations. Monomers represented by the above general formula, isodecyl methacrylate, etc. can provide excellent adhesives in that they have very little odor and are highly reactive; If it protrudes from the surface, it will remain sticky for a long time without evaporating, so it is effective to use the method of the present invention. Suitable examples of the photosensitizer used in component A in the present invention include organic carbonyl compounds such as benzoin, benzoin alkyl ether, α-phenylbenzoin, benzyl, benzophenone, acetophenone, diacetyl, anthraquinone, anthraquinone derivatives, Michler's ketone; Azo compounds such as bisisobutyronitrile, azodibenzoyl, azomethane, azo-2-4-dimethyl-4-methoxyvaleronitrile, 1-azobis-1-cyclohexanecarbonitrile, 2,2'-azobisproban; dibenzothia zonyl sulfide,
Decyl phenyl sulfide, disulfide, 1-
or 2-naphthalenesulfonyl chloride,
Sulfur-containing compounds such as 2,5-naphthalenedisulfonyl chloride; halogen compounds such as carbon tetrabromide and carbon tetrachloride; peroxides such as 2,4-dichlorobenzoyl peroxide, 1- or 2-naphthoyl peroxide substances; eosin, erythrosin,
Examples include dyes such as acridine; uranyl nitrate; and these may be used alone or in appropriate combinations. If the amount of photosensitizer used is too small, the graft polymerization of the radically polymerizable monomer to the elastomer described below or the homopolymerization of the monomer will be extremely slow, which is disadvantageous in practice, and if it is too large, the Since it does not increase the sensitization effect and is uneconomical, it is usually preferably 0.005 to 5% of the total composition.
It is used within the range of 0.05 to 1%. Conventionally known synthetic rubbers and natural rubbers are widely used as the elastomer used in the present invention. Elastomers that easily generate radicals by the action of a catalyst are preferred, and these elastomers are often contained only in component A, which contains the above polymerizable monomer, but in component B, which does not contain polymerizable monomers. It may also be included. Alternatively, an elastomer and a polymerizable monomer may be used in combination as both the A component and the B component. Examples of elastomers include fluoroelastomers such as vinylidene fluoride/hexafluoropropene polymers; chlorinated polyethylenes; chloroprene polymers such as polychloroprene, methyl methacrylate/chloroprene polymers; bisphenol A/fumaric acid polyesters. , polyester polymers such as polyesters based on maleic acid terephthalate; vinyl chloride polymers such as vinyl chloride/vinyl acetate copolymers; polyethyl acrylate, styrene/ethyl acrylate polymers, n-butyl methacrylate/methacrylate Acrylic acid ester polymers such as acid isobutyl polymers; hydrocarbon polymers such as polyisoprene, polystyrene, styrene/butadiene rubber; polyalkylene ethers such as polyepichlorohydrin; such as ethylene/vinyl acetate polymers. acetic acid polymers; polyurethane polymers such as polytetramethylene ether glycol/2,4-toluene diisocyanate polyurethane; acrylonitrile polymers such as butadiene/acrylonitrile; chlorosulfonated polymers such as chlorosulfonated polyethylene, etc. can be mentioned. However, these elastomers usually have a
Those with a molecular weight range of 1,000,000 and soluble in the above polymerizable monomers are used alone or in combination,
The amount used is 5 to 100 parts by weight of the polymerizable monomer.
It is preferable to use 150 parts by weight in terms of maintaining a suitable viscosity and obtaining excellent adhesive strength, especially peel strength. If elastomer is contained in component B,
It needs to be dissolved in an appropriate solvent.
As the solvent, conventionally known solvents such as aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as dichloroethane and trichloroethylene, and ketone hydrocarbons such as acetone and methyl ethyl ketone can be used alone or in combination. It will be done. Examples of the polymerization catalyst used in the present invention include (a) organic hydroperoxides such as cumene hydroperoxide, butyl hydroperoxide, and P-methane hydroperoxide;
Benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide,
Organic peroxides such as t-butyl perbenzoate; peroxides such as peracids (b) aldehyde-amine condensates such as condensation products of butyraldehyde and aniline or butyramide; (c) cobalt, nickel, manganese or iron Organic acid salts of transition metals such as naphthenate, copper octonate, iron hexonate, etc. (d) Tertiary amines such as N,N-dimethylaniline, N,N-dimethyltoluidine, etc. (e) Thiourea, acetylthiourea, tetramethylthiourea , diethylthiourea, ethylenethiourea, and the like, and these may be used alone or in appropriate combinations depending on the reactivity of the polymerizable monomer or elastomer. Suitable examples include (b), (c), (d), (a) + (b), (a) + (b) + (c), (a) + (
c),
(a) + (d) (so-called redox catalyst), (a) + (d) + (c),
Examples include (a)+(e), (a)+(e)+(c), (c)+(d), etc. Peroxide (a) is most commonly used, and the amount used is usually 0.01 to 5 parts by weight per 100 parts by weight of the above polymerizable monomer.
It is expressed as parts by weight, and is often contained together with an elastomer, a polymerizable monomer, and a polymerization inhibitor to constitute component A, and other polymerization catalysts constitute component B. When the aldehyde-amine condensate (b) is used alone, it is preferably contained in component B, which does not contain a polymerizable monomer. The polymerization catalysts (b) to (e) are usually used in an amount of 10% by weight or less in the adhesive composition, and include methylene chloride,
It is used after being dissolved in an appropriate solvent such as chloroform, carbon tetrachloride, methyl ethyl ketone, methyl isobutyl ketone, acetone, xylene, benzene, toluene, ethyl acetate, n-hexane, cyclohexane, or the like. In the present invention, usually together with the above peroxide (a), A
Polymerization inhibitors contained in the ingredients include hydroquinone, methylhydroquinone, hydroquinoquinone monomethyl ether, 2.6-z-t-butyl-4-methylphenol, and 2.5-diphenyl-P.
In addition to benzoquinone, mono-t-butyl-P-benzoquinone, and the like, commonly known radical polymerization inhibitors are widely used. The amount of these polymerization inhibitors used is 0.05 to 100 parts by weight of the above polymerizable monomer.
2 parts by weight is suitable. If the amount is too small, the storage stability will be poor, and if the amount is too large, the adhesive performance will be adversely affected. In the present invention, if chlorosulfonated polyethylene or chloroprene is used as the elastomer and there is a risk of free chlorine being generated, an epoxy compound (for example, Epicote #828 manufactured by Ciel Co., Ltd.) or diethylthiocarbamine may be used as a chlorine atom capture agent. Acid salts (Noxela EZ, manufactured by Kiuchi Shinkosha, etc.)
It is preferable to add 0.1 to 5 parts by weight per 100 parts by weight of rubber. Further, an ester of dimethacrylic acid having good compatibility with the above elastomer, such as 1,3-butylene dimethacrylate, is included in component A or B in an amount of about 20 parts by weight or less per 100 parts by weight of the above acrylic monomer. This further increases the heat resistance of the adhesive. In order to bond adherends according to the present invention, one liquid containing a radically polymerizable monomer and a photosensitizer of a two-component non-mixable adhesive is called component A, and the other liquid is called component B.
In terms of components, for example, reactive elastomers such as chlorosulfonated polyethylene,
A component A containing a polymerization inhibitor and a polymerization catalyst that cannot polymerize the polymerizable monomer in the presence of the polymerization inhibitor is applied to the adherend a, while when it comes into contact with the component A, the polymerizable monomer Component B containing a polymerization catalyst capable of polymerizing and curing the entire adhesive is applied to adherend b. Next, when the coated surfaces of adherends a and b are brought into contact with each other, the polymerizable monomer is graft-polymerized onto the reactive elastomer by the action of the curing agent of component B and the polymerization catalyst of component A, thereby curing the entire adhesive. urge When component A protruding from the adherend is irradiated with actinic rays, the photosensitizer generates radicals, and the reactive polymerizable monomer undergoes graft polymerization onto the elastomer to harden the protruding portion. Active light with a wavelength of 1,500 to 7,000 Å is generally used, and the light source used depends on the type of photosensitizer, but it is usually a mercury lamp, an ultraviolet fluorescent lamp, a carbon arc lamp, a tungsten lamp, or a solar lamp. Rays of light etc. are used. Although the light irradiation time depends on the composition of component A, it is generally several seconds to several tens of seconds, and several minutes at the longest is sufficient. When using the above-mentioned main component-primer type adhesive, even if the B component, that is, the primer, protrudes from the adherend, in most cases the polymerization catalyst itself does not have viscosity, so if the primer contains a solvent. However, if the solvent dries over time, this will not be a particular problem. When using a two-component type adhesive, the B component contains a polymerizable monomer and/or an elastomer; If extrusion is expected, add a sensitizer to component B in advance (that is, in this case, according to the definition of component A above, both components are component A), and adherend a, After contact with b, the protruding portion is cured in the same manner as in the case of the base material-primer type. In addition, when using, for example, the above-mentioned peroxide as the polymerization catalyst used in the present invention, even if the above-mentioned photosensitizer is not included in the A component, the A component can be irradiated with active light for a long time, for example, several hours. There may be cases where the polymerizable monomers in the components are polymerized. However, if the above-mentioned photosensitizer is used, the light irradiation time required for curing is on the order of several seconds to several minutes, depending on the type and amount of photosensitizer and the type and intensity of actinic light. In the present invention, only compounds that have the effect of curing component A with light irradiation for a short period of time are referred to as photosensitizers. The method of the present invention has the above-mentioned structure, and consists of a two-component non-mixable adhesive consisting of both components A and B, which react and cure when they come into contact with each other, and a radically polymerizable monomer and a photosensitizer. After applying component A containing the following to adherend a and applying component B to adherend b,
The component A that protrudes from the contact area when the coated surfaces of coating materials and b are brought into contact with each other can be easily and rapidly cured by irradiation with light. Therefore, depending on the structure, shape, etc. of the adherend, the present invention
Although it is difficult to wipe off the protruding component A, it is effective when applied in cases where light irradiation is easy.
In this case, especially if component A contains a radically polymerizable monomer with a high boiling point, the part protruding from the adherend will remain sticky for a long time without evaporating. The invention becomes even more useful. Examples of the present invention will be shown below. The term "parts" simply means parts by weight. Example 1

[Table] Compound
B component〓

Claims (1)

[Scope of Claims] 1 A two-component non-mixable adhesive consisting of both components A and B, which react and cure when they come into contact with each other, is coated with component A containing a radically polymerizable monomer and a photosensitizer. After applying component B to adherend a and applying it to adherend b, when the coated surfaces of adherends a and b are brought into contact, the component A that protrudes from the corresponding contact area is irradiated with light. An adhesive method characterized by hardening the protruding parts. 2 The radically polymerizable monomer has the general formula (In the formula, R ₁ and R ₂ are each H or CH ₃ , and n
is 0 or 1. ) The adhesion method according to item 1, which is an acrylic monomer represented by: