JPH0675593B2 - Adhesive for ceramics and method for adhering ceramics using this adhesive - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to an adhesive used for adhering ceramics, particularly medical ceramics, and a method for adhering ceramics, particularly medical ceramics, using the adhesive.

Technical Background of the Invention and Problems Thereof In recent years, ceramics have been used for various purposes. Among them, medical ceramics are particularly expected to be used in fields such as artificial bones and dental treatments. . In the field of dental treatment, such ceramics for medical use are mainly composed of silica and alumina, and a dental porcelain containing a modified oxide for improving melting point, sinterability, color tone and the like ( Hereinafter sometimes referred to as porcelain) is used. This porcelain is ceramic tooth,
In addition to being used as a baked porcelain crown, jacket crown, etc., its use as an artificial tooth root is being considered.

Dental treatment using such porcelain is, for example, after shaving a tooth that has been affected by caries and the like, preparing a metal crown (crown) to be fitted to this, and baking porcelain on this metal crown. It has been done by wearing a porcelain baked crown on the teeth. However, since porcelain is hard and brittle, it may be broken, or due to the low adhesiveness between porcelain and metal, porcelain is separated from the metal. In particular, when the porcelain is broken, the porcelains cannot be firmly adhered to each other, so that there is a problem that a new expensive porcelain baking crown has to be manufactured again.

In order to solve such a problem, an adhesive having an adhesive property to porcelain has been proposed. For example, in Dental Materials and Instruments, Vol. 3, No. 6, pp. 739-746, (a) silane coupling agent, (b) 4- as polymerizable monomer.
Methacryloxyethyl trimellitic anhydride (hereinafter 4-
(Sometimes abbreviated as META), (c) methyl methacrylate as a polymerizable monomer (hereinafter sometimes abbreviated as MMA), and (d) trialkylboron as a polymerization catalyst (hereinafter sometimes abbreviated as TBB). It is disclosed that the adhesive consisting of (1) has adhesiveness to porcelain.

This adhesive has a certain degree of excellent adhesiveness as compared with the conventionally proposed adhesive for porcelain, but its adhesive strength largely changes depending on use conditions and lacks reliability.
Moreover, it is not sufficiently satisfactory in terms of water resistance, and therefore it has been strongly desired to further improve the adhesiveness.

The present inventors have diligently studied to solve the above problems and obtain an adhesive for ceramics, which has excellent adhesiveness, its adhesive strength does not change depending on the use conditions, and is also excellent in water resistance. However, they have found that it is sufficient to add a specific acidic compound to a conventionally known adhesive for ceramics and to greatly increase the amount of the silane coupling agent used, and have completed the present invention.

An object of the present invention is to solve the problems associated with the above-mentioned conventional techniques, and has excellent adhesiveness to ceramics such as porcelain and also excellent water resistance. The first purpose is to provide an agent.

The present invention also provides a method for adhering ceramics such as porcelain using the adhesive as described above.
The purpose is.

SUMMARY OF THE INVENTION The first adhesive for ceramics according to the present invention is a group consisting of (a) a silane coupling agent, (b) an organic carboxylic acid, an organic carboxylic acid anhydride, an inorganic acid, an organic sulfonic acid and an organic phosphoric acid. At least one acidic compound selected from the group consisting of (c) a polymerizable monomer and (d) a polymerization catalyst, wherein the silane coupling agent is the above-mentioned component (a),
At least 5 of the total weight of (b), (c) and (d)
It is characterized by being present in an amount of% by weight.

The first ceramic bonding method according to the present invention is characterized by including the following steps.

A liquid containing (a) a silane coupling agent and (b) the above-mentioned acidic compound is added to the surface of the ceramic so that the amounts of the silane coupling agent are components (a), (b), (c) and (d).
The amount of which is at least 5% by weight with respect to the total weight of the above, the step of drying the applied material applied to the surface of the adherend as described above, and the polymerizable monomer (c) on the applied material. And (d) a step of applying a polymerization catalyst, and a step of joining an adherend to the surface of the ceramic thus treated.

The second ceramic bonding method according to the present invention is characterized by including the following steps.

On the surface of the adherend, (a) a silane coupling agent, (b)
The acidic compound, the polymerizable monomer (c) and the polymerization catalyst (d) are mixed in the amount of the silane coupling agent of the component (a),
(B) A step of applying an amount of at least 5% by weight based on the total weight of (c) and (d), and a step of joining an adherend to the surface of the ceramic thus treated.

The ceramic adhesive according to the present invention, in addition to the silane coupling agent, the polymerizable monomer and the polymerization catalyst, contains an acidic compound such as an organic carboxylic acid, because the silane coupling agent is used in a specific amount, Excellent adhesiveness, reliability and water resistance.

DETAILED DESCRIPTION OF THE INVENTION The adhesive for ceramics according to the present invention and the method for bonding ceramics using this adhesive will be specifically described below.

The adhesive for ceramics according to the present invention is at least one selected from the group consisting of (a) silane coupling agent, (b) organic carboxylic acid, organic carboxylic acid anhydride, inorganic acid, organic sulfonic acid and organic phosphoric acid. Acidic compounds,
It comprises (c) a polymerizable monomer and (d) a polymerization catalyst.

Each component will be described in detail below.

(A) Silane Coupling Agent In the present invention, an organic silane coupling agent is preferably used. Specifically, for example, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltri (trimethylsiloxy) silane, γ-methacryloxypropyl pentamethyldisiloxane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, mercaptopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, etc. Used. Of these, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltri (trimethylsiloxy) silane, and γ-methacryloxypropylpentamethyldisiloxane are particularly preferably used.

This silane coupling agent is composed of the components described below including the silane coupling agent, that is, (a) silane coupling agent, (b) acidic compound, (c) polymerizable monomer and (d) total weight of the polymerization catalyst. It is desirable to be present in an amount of at least 5% by weight, preferably 5 to 15% by weight.

When the amount of the silane coupling agent is less than 5% by weight, the adhesive strength of the obtained adhesive is small, which is not preferable.

Such a silane coupling agent is preferably used after being dissolved or dispersed in an alcohol such as methanol or ethanol, a ketone such as acetone or methyl ethyl ketone, or an organic solvent such as methyl methacrylate which is a polymerizable monomer described later. .

(B) Acidic Compound As the acidic compound, at least one compound selected from organic carboxylic acids, organic carboxylic acid anhydrides, inorganic acids, sulfonic acids and organic phosphoric acids is used.

As the organic carboxylic acid, both unsaturated carboxylic acid and saturated carboxylic acid can be used. Examples of such an organic carboxylic acid include chromenoic acid, linoleic acid, undecenoic acid, cinnamic acid, sorbic acid, coumaric acid, maleic acid, citraconic acid, p-vinylbenzoic acid, 4-methacryloxyethyltrimellitic acid and the like. Can be raised.

Further, for example, aliphatic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, stearic acid, pyruvic acid, methoxyacetic acid and acetoacetic acid, aromatic carboxylic acids such as benzoic acid, phenylacetic acid and salicylic acid. Hydroxycarboxylic acids such as glycolic acid and lactic acid;
Dicarboxylic acids such as oxalic acid, succinic acid, adibic acid, tartaric acid, maleic acid, fumaric acid, and phthalic acid; vinylcarboxylic acids such as acrylic acid, methacrylic acid, and vinylacetic acid can also be used.

Furthermore, the above-mentioned organic carboxylic acid anhydrides can also be used.

As the inorganic acid, sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, hydrogen fluoride, hydrogen bromide, hydrogen iodide, nitric acid, tripolyphosphoric acid, phosphonic acid or the like is used.

Examples of the organic sulfonic acids include alkylsulfonic acids such as methanesulfonic acid and ethanesulfonic acid, arylsulfonic acids such as benzenesulfonic acid, toluenesulfonic acid and naphthalenesulfonic acid, polysulfonic acids such as benzenedisulfonic acid and toluenedisulfonic acid, and styrene sulfone. Acid, vinyl sulfonic acid such as 2-acrylamido-2-methylpropane sulfonic acid, and the like are used.

As the organic phosphoric acid, alkylphosphoric acid such as methylphosphonic acid and ethylphosphonic acid, arylphosphoric acid such as phenylphosphonic acid and naphthylphosphonic acid, polyphosphoric acid,
Acidic phosphoric acid esters such as methylphosphoric acid, ethylphosphoric acid and phenylphosphoric acid, and vinylphosphoric acid such as methacryloxyethylphosphoric acid and methacryloxyethylphenylphoric acid are used.

Such an acidic compound is preferably used after being dissolved or dispersed in an alcohol such as methanol or ethanol, a ketone such as acetone or methyl ethyl ketone, or an organic solvent such as methyl methacrylate which is a polymerizable monomer described later.

(C) Polymerizable Monomer In the ceramic adhesive according to the present invention, a polymerizable monomer is used, and as the polymerizable monomer, a polymerizable vinyl compound is widely used.

The following compounds are specifically used as such a polymerizable monomer.

Vinyl halides such as vinyl chloride and vinyl bromide; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and isoptyl vinyl ether; styrene, vinyltoluene, α-methylstyrene, chloro Alkenylbenzenes such as methyl styrene and stilbene; alkyl or glycidyl esters of acrylic acid or methacrylic acid such as methyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate. : Ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene Diacrylic acid esters or dimethacrylic acid esters such as glycol and butylene glycol; Triacrylic acid esters or trimethacrylic acid esters such as trimethylolpropane and trimethylolethane; Triacrylic acid esters or trimethacrylic acid esters of tetramethylolethane Tetramethylolethane tetraacrylate or tetramethacrylate; bisphenol-A-dimethacrylate, bisphenol-A-diglycidylmethacrylate, 2,2-bis (4-methacryloxyethoxyphenyl) propane; acrylic acid, methacryl Acid, methacrylic anhydride, itaconic acid, maleic acid, maleic anhydride, p-methacryloxybenzoic acid, N
-2-Hydroxy-3-methacryloxypropyl-N-
Phenylglycine, 4-methacryloxyethyl trimellitic acid, 4-methacryloxyethyl trimellitic anhydride, etc.

Of these, alkyl esters of acrylic acid or methacrylic acid such as methyl methacrylate are particularly preferable.

Further, it is also preferable to use such methyl methacrylate in combination with 4-mecryloxyethyl trimellitic anhydride.

(D) Polymerization catalyst As the polymerization catalyst, those that can be cured at room temperature by polymerizing the above polymerizable monomers are preferably used.

The following compounds are specifically used as such a polymerization catalyst.

Trialkylboron and its analogs As the trialkylboron, specifically, triethylboron, tripropylboron, triisopropylboron,
Tri-n-butylboron, triisopropylboron, tri-n-amylboron, triisoamylboron, tri-
sec-amylboron or the like is used. Also, a trialkylboronic acid analog in which a part of these is oxidized can be used.

Organic Peroxide-Amine Mixed System As the organic peroxide, any one which is usually used as a polymerization initiator can be used without particular limitation. For example,
Dibenzoyl peroxide, dilauroyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, ter
t-Butyl hydroperoxide, tert-butyl peroxybenzoate and the like are preferably used.

Aromatic amines are preferably used as the amines used in combination with such an organic peroxide. The aromatic amine has at least one aryl group bonded to the nitrogen atom, and any of primary amine, secondary amine, and tertiary amine can be used. preferable. Specifically, aniline,
Toluidine, xylidine, phenylenediamine, N, N-
Dimethylaniline, N, N-diethylaniline, N, N-di (β-hydroxyethyl) aniline, N, N-dimethyltoluidine, N, N-diethyltoluidine, N, N-dimethylanisidine, N, N-- Diethylanisidine, N, N-dimethyl-t-butylaniline, N, N-diethyl-t-butylaniline, N, N-dimethyl-p-chloroaniline, diphenylamine, N, N- (β-hydroxyethyl)- Examples thereof include p-toluidine. Among these, N, N-dimethyl-p-toluidine, N, N-dimethyl-
pt-butylaniline, N, N-dimethylanisidine,
A tertiary amine having an electron donating substituent at least at the p-position of the benzene ring such as N, N-dimethyl-p-chloroaniline and N, N-di (β-hydroxyethyl) -p-toluidine is preferable.

Visible Light Polymerization Initiator This visible light polymerization initiator comprises an α-ketocarbonyl compound and an amine or aromatic nitrogen-containing condensed ring compound.

As the α-ketocarbonyl compound, α-diketone, α-
Examples thereof include ketoaldehyde, α-ketocarboxylic acid and α-ketocarboxylic acid ester. More specifically, diacetyl, 2,3-pentadione, 2,3-hexadione, benzyl, 4,4'-dimethoxybenzyl, 4,4 '
-Diethoxybenzyl, 4,4'-oxybenzyl, 4,4 '
-Α-diketones such as dichlorobenzyl, 4-nitrobenzyl, α-naphthyl, β-naphthyl, camphorquinone and 1,2-cyclohexanedione, α-ketoaldehydes such as methylglyoxal and phenylglyoxal, pyruvic acid, benzoyl Examples thereof include formic acid, phenylpyruvic acid, methyl pyruvate, ethyl benzoylformate, methyl phenylpyruvate and butyl phenylpyruvate. Of these α-ketocarbonyl compounds, α-diketones are preferably used from the viewpoint of stability and the like. Among the α-diketones, diacetyl, benzyl and camphorquinone are particularly preferable.

The amines used as one component of the visible light polymerization initiator are preferably aliphatic amines or aromatic amines.
Particularly suitable aromatic amines have the general formula [I] [In the formula, R ₁ represents a hydrogen atom, an alkyl group or a hydroxyalkyl group, R ₂ represents a hydrogen atom, an alkyl group, a hydroxyalkyl group or an aryl group, and R ₃ represents an acyl group, a carboxy group or an alkoxycarbonyl group. , A hydroxyacyl group, a carbamoyl group which may have a substituent, a cyano group, a nitro group, and a halogen atom are shown]. Specific examples of such a substituted aromatic amine include 4-dimethylaminobenzaldehyde, 4-diethylaminobenzaldehyde, and 4-diethylaminobenzaldehyde.
-(Methylphenylamino) benzaldehyde, 4-
(Β-hydroxyethylmethylamino) benzaldehyde, 4-dimethylaminobenzoic acid, 4-diethylaminobenzoic acid, 4- (methylphenylamino) benzoic acid, 4
-(Β-Hydroxyethylamino) benzoic acid, methyl 4-dimethylaminobenzoate, methyl 4-diethylaminobenzoate, methyl 4- (methylphenylamino) benzoate, 4- (β-hydroxyethylmethylamino) benzoate Acid propyl, 4-dimethylaminobenzoic acid phenyl, 4
-Dimethylaminophthalic acid, dimethyl 4-dimethylaminoisophthalate, N, N-dimethyl-cyanoaniline, N, N
-Dimethyl-chloroaniline, N, N-dimethyl-bromoaniline, N, N-dimethyl-bromoaniline, N, N-dimethyl-o-iodoaniline, N, N-diethyl-cyanoaniline, N, N-diethyl- p-chloroaniline, N, N-dipropyl-p-cyanoanilino, N, N-methylphenyl-p-cyanoaniline, N, N-β-hydroxyethylmethyl-p-chloroaniline, N, N-dimethyl-2, Examples thereof include 4-dicyanoaniline, N, N-dimethyl-2,4-dinitroaniline, N, N-dimethyl-2,4-dichloroaniline. Among these substituted aromatic amines, 4-dialkylaminobenzaldehyde, 4-dialkylaminobenzoic acid, 4-dialkylaminobenzoic acid ester and N, N-dialkyl-p-cyanoaniline are preferable, and 4-diethylaminobenzoic acid is preferable. Particularly preferred.

Further, as the aromatic nitrogen-containing condensed ring compound used as one component of the visible light polymerization initiator, a compound represented by the general formula [II] [Wherein X represents> NR ² , an oxygen atom or a sulfur atom, and Y
Represents a hydrogen atom, -SR ³ or a monovalent to trivalent metal, R
¹ represents an alkyl group, an aryl group, an aralkyl group, a halogen atom, n represents an integer of 0 to 4, and when n is 2 or more, R ¹ may be different groups, and R ² is hydrogen. Represents an atom, an alkyl group, an aryl group or an aralkyl group, and R ³ represents an alkyl group, an aryl group or the general formula [III] (In the formula, X, R ¹ and n are the same as above), which is an aromatic nitrogen-containing condensed ring compound. Specific examples of such an aromatic nitrogen-containing fused ring compound include 2-
Mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-
Mercaptomethylbenzimidazole, 2-mercaptomethylbenzoxazole, 2-mercaptomethylbenzothiazole, dibenzooxazyl disulfide, dibenzothiazyl disulfide, 2- (phenylthio) benzothiazole, and metal salts thereof such as sodium salt, zinc (II) Examples thereof include salts, copper (II) salts, nickel salts, 2-mercaptodimethylbenzimidazole, 2-mercaptodimethylbenzoxazole and 2-mercaptodimethylbenzothiazole. Among these sulfur compounds, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercaptomethylbenzothiazole, dibenzothiazyldisulfide, and zinc (II) of 2-mercaptobenzimidazole. Salts, 2-mercaptobenzothiazole zinc (II) salts, and 2-mercaptomethylbenzothiazole zinc (II) salts are preferable, and 2-mercaptobenzothiazole, 2-mercaptomethylbenzothiazole, and 2-mercaptobenzothiazole zinc (II ) Salt and 2-mercaptomethylbenzothiazole zinc (II) salt are preferred.

In addition to the above components, a polymer, a filler, a stabilizer, and the like may be added as constituent components to the ceramic adhesive according to the present invention, if necessary. Examples of the polymer added to reduce the polymerization shrinkage or adjust the viscosity include polymers or copolymers of monofunctional monomers such as polymethyl (meth) acrylate and polyethyl (meth) acrylate. As an example of the filler, glass beads having a particle size of about 1 to 100 μm,
Examples thereof include alumina oxide, α-quartz powder, colloidal silica and the like. As the stabilizer, hydroquinone monomethyl ether, t-butyl-p-cresol, hydroxymethoxybenzophenone, etc. are used.

Further, an aromatic sulfinate may be added to the ceramic adhesive according to the present invention. As such an aromatic sulfinate, a salt of an alkali metal, an alkaline earth metal, an amine or the like is used, and specific examples thereof include sodium benzelsulfinate, calcium benzenesulfinate, strontium benzenesulfinate and benzenesulfinate. Acid, benzenesulfinic acid triethylammonium salt, benzenesulfinic acid salts such as benzenesulfinic acid / N, N-dimethyl-p-toluidine salt, or p-toluenesulfinic acid,
Salts such as β-naphthalene sulphinic acid and styrene sulfinic acid are used.

By the way, in the present invention, each component (a) as described above,
(B), (c) and (d) are preferably used in the following quantitative relationship.

(A) Silane coupling agent The silane coupling agent is the above-mentioned (a), (b), (c).
It is preferably used in an amount of 5% by weight or more, preferably 5 to 15% by weight, based on the total weight of (d).

(B) Acidic Compound The acidic compound is preferably used in an amount of 0.01 to 2% by weight based on the total weight of (a), (b), (c) and (d).

(C) Polymerizable Monomer The polymerizable monomer is preferably used in an amount of 95 to 43% by weight based on the total weight of (a), (b), (c) and (d).

(D) Polymerization catalyst The polymerization catalyst is the above-mentioned (a), (b), (c) and (d).
It is preferably used in an amount of 0.01 to 43% by weight, based on the total weight of

In addition, in the present invention, the addition of a metal salt in addition to the above components improves the adhesiveness of the resulting ceramic adhesive. Examples of such metal salts include ferric chloride, magnesium chloride, zinc chloride, aluminum chloride, stannous chloride, stannic chloride, zirconium chloride, molybdenum chloride, nickel chloride, cupric chloride, or cupric chloride. Monocobalt is used.

When used, the metal salt as described above is used in an amount of 0.01 to 2% by weight based on the total weight of the components (a), (b), (c) and (d). Is preferred.

Next, a method of bonding ceramics using the above-described ceramic adhesive will be described.

The first ceramic bonding method according to the present invention is characterized by including the following steps.

A liquid containing (a) a silane coupling agent and (b) the acidic compound is added to the surface of the ceramic, and the amount of the silane coupling agent is the total weight of the components (a), (b), (c) and (d). The amount of which is at least 5% by weight, the step of drying the coating material applied to the surface of the adherend as described above, (c) the polymerizable monomer and ( d)
A step of applying a polymerization catalyst, and a step of bonding an adherend to the surface of the ceramic thus treated.

More specifically, in the step of, for example, a solution obtained by mixing a methyl methacrylate solution containing a silane coupling agent and an acetone solution containing an acidic compound such as 4-methacryloxyethyltrimet acid or phosphoric acid is subjected to silane coupling. The amount of the agent is applied to the ceramic surface in such an amount that it is at least 5% by weight based on the total weight of the components (a), (b), (c) and (d).

The ceramic surface is preferably polished and cleaned prior to applying the liquid containing the silane coupling agent and the acidic compound. The ceramic surface is cleaned by ultrasonic cleaning in an organic solvent such as acetone.

The other step is performed by, for example, air-drying the coating material applied to the surface of the ceramic and then blowing it with air.

The step of, on the coating material containing a silane coupling agent and an acidic compound formed on the ceramic surface,
It is carried out by applying a liquid material comprising a mixture of (c) a polymerizable monomer and (d) a polymerization catalyst.

The step (1) is carried out by pressure-bonding or placing an adherend on the ceramic surface that has been subjected to the above-mentioned treatment to bond the adherend. The adherend adhered to the ceramic surface is preferably a metal such as stainless steel or iron, or a ceramic such as porcelain.

The second ceramic bonding method according to the present invention is characterized by including the following steps.

On the ceramic surface, (a) silane coupling agent,
A liquid material containing (b) the acidic compound, (c) a polymerizable monomer, and (d) a polymerization catalyst is added in an amount of the silane coupling agent of components (a), (b), (c) and (d). A step of applying an amount of at least 5% by weight based on the total weight, and a step of joining an adherend to the surface of the ceramic thus treated.

This method of bonding ceramics consists of preparing a liquid by mixing all the components in advance, applying this liquid to the surface of the ceramic, and then drying the resulting coating if necessary, It is carried out by pressure-bonding or placing an adherend such as ceramics or metal on the substrate and bonding them.

Advantageous Effects of Invention The first adhesive for ceramics according to the present invention is the first adhesive such as 4-methacryloxyethyltrimet acid in addition to the silane coupling agent, the polymerizable monomer and the polymerization catalyst.
Since the silane coupling agent containing an acidic compound is present in an amount of at least 5% by weight, preferably 5 to 15% by weight, based on the total weight of components (a), (b), (c) and (d), Excellent in reliability and water resistance.

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 1 powdered dental ceramic (trade name VMK68) manufactured by Vita
After molding into a block of 0 mm x 10 mm x 5 mm, its surface was ground to emery paper # 600 under water injection. This sample was washed with water for 1 minute and then dried by air blow. A 0.1 mm thick cellophane tape in which a hole having a diameter of 5 mm was formed was quickly attached to this surface to form an adhesive surface having a defined area.

Then, an MMA solution containing 6% by weight of γ-methacryloxypropyltrimethoxysilane as a silane coupling agent and an ethanol solution containing 0.5% by weight of 4-methacryloxyethyltrimetic acid as an acidic compound in a ratio of 1: 1. The mixture was applied to the ceramic surface to form a coating film.
Immediately after coating, an air blow treatment was applied to the ceramic surface to uniformly spread the coating film on the surface, remove the excess coating film, and dry the coating film.

A solution in which MMA solution as a polymerizable monomer and its polymerization catalyst TBB solution were mixed on this adhesive surface at a ratio of 12.5: 1 (volume ratio) and MMA polymer at a ratio of 1 to 1.5: 1 (parts by weight). It was applied by a stacking method, and then the tip of a stainless steel rod (SUS304) having a tip diameter of 6 mm was butt-bonded to this adhesive surface. The adhesion test piece was left for 30 minutes, then immersed in 37 ° C water for 24 hours, then kept at 4 ° C for 1 minute, and then 60 minutes.
After performing 60 cycles of heat cycle treatment for 1 minute at ℃, using Shimadzu tensile tester Autograph IM-500, 2
The adhesion between stainless steel and ceramics was measured at a speed of mm / min. The measurement was performed at 6 points under the same conditions, and the average value was taken as the adhesive strength. The adhesive strength was 247 kg / cm ² .

In this way, the silane coupling agent is present in an amount of 6% by weight, based on the total weight of each component (a), (b), (c) and (d).

Example 2 In Example 1, an MMA solution in which 4-META (4-methacryloxyethyltrimellitic anhydride) was dissolved at a concentration of 5% by weight was used instead of the MMA solution as the polymerizable monomer. In the same manner as in Example 1, stainless steel and ceramics were adhered and the adhesive force was measured.

The average value of adhesive strength was 314 kg / cm ² .

Example 3 In Example 1, 0.5% by weight of H ₃ P was used as the acidic compound.
In the same manner as in Example 1, except that an ethanol solution containing 0 ₄ was used and an MMA solution in which 4-META was dissolved at a concentration of 5 wt% was used instead of the MMA solution as the polymerizable monomer. Was adhered to ceramics, and the adhesive force was measured.

The average value of the adhesive strength was 300 kg / cm ² .

Example 4 In Example 1, 0.5% by weight of HCl was used as the acidic compound.
Was used, and instead of the MMA solution as the polymerizable monomer, an MMA solution in which 4-META was dissolved at a concentration of 5% by weight was used, and stainless steel and ceramics were bonded in the same manner as in Example 1. , Its adhesive strength was measured.

The average value of adhesive strength was 296 kg / cm ² .

Example 5 In Example 1, 0.5% by weight of H ₂ S was used as the acidic compound.
Stainless steel and ceramics were prepared in the same manner as in Example 1 except that O ₄ was used and an MMA solution in which 4-META was dissolved at a concentration of 5% by weight was used instead of the MMA solution as the polymerizable monomer. It was made to adhere and the adhesive force was measured.

The average value of adhesive strength was 328 kg / cm ² .

Comparative Example 1 Stainless steel and ceramics were adhered in the same manner as in Example 1 except that the ethanol solution containing 4-methacryloxyethyltrimetic acid as an acidic compound was not used in Example 1, and the adhesion thereof was performed. The force was measured.

The average value of adhesive strength was 79 kg / cm ² .

Comparative Example 2 In Example 1, the ethanol solution containing 4-methacryloxyethyltrimetic acid as the acidic compound was not used, and instead of the MMA solution as the polymerizable monomer,
Stainless steel and ceramics were adhered in the same manner as in Example 1 except that an MMA solution in which 4-META was dissolved at a concentration of 5% by weight was used, and the adhesive force was measured.

The average value of adhesive strength was 69 kg / cm ² .

Comparative Example 3 In Example 1, as the silane coupling agent, an MMA solution containing 1 wt% γ-methacryloxypropyltrimethoxysilane instead of the MMA solution containing 6 wt% γ-methacryloxypropyltrimethoxysilane. In the same manner as in Example 1 except that the stainless steel was bonded to the ceramic, and the adhesive force was measured.

The average value of adhesive strength was 150 kg / cm ² .

In this case, the silane coupling agent is present in an amount of 1% by weight of the total weight of each component.

Claims (24)

[Claims] 1. An (a) silane coupling agent, (b) at least one acidic compound selected from the group consisting of organic carboxylic acids, organic carboxylic anhydrides, inorganic acids, organic sulfonic acids and organic phosphoric acids, c) a polymerizable monomer and (d) a polymerization catalyst, wherein the (a) silane coupling agent is at least 5% by weight of the total weight of components (a), (b), (c) and (d). An adhesive for ceramics characterized by being present in. 2. A silane coupling agent is γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltri (trimethylsiloxy) silane or γ-
The adhesive for ceramics according to claim 1, which is methacryloxypropyl pentamethyldisiloxane. 3. The adhesive for ceramics according to claim 1, wherein the acidic compound is 4-methacryloxyethyl trimellitic acid. 4. The adhesive for ceramics according to claim 1, wherein the acidic compound is phosphoric acid. 5. The adhesive for ceramics according to claim 1, wherein the polymerizable monomer is methyl methacrylate. 6. The adhesive for ceramics according to claim 1, wherein the polymerizable monomer comprises methyl methacrylate and 4-methacryloxyethyl trimellitic anhydride. 7. The adhesive for ceramics according to claim 1, wherein the polymerization catalyst is a trialkylboron or its oxide, or a mixed system of an organic peroxide and amines. 8. A silane coupling agent is present in an amount of 5 to 15% by weight, based on the total weight of the components (a), (b), (c) and (d). The adhesive for ceramics according to claim 1. 9. A method for adhering ceramics, which comprises the following steps: (a) a silane coupling agent and (b) an organic carboxylic acid, an organic carboxylic acid anhydride, an inorganic acid or a sulfonic acid on the surface of the ceramics. And a liquid containing at least one acidic compound selected from the group consisting of organic phosphoric acids, and the amount of the silane coupling agent is the components (a), (b), (c).
And a step of applying an amount of at least 5% by weight based on the total weight of (d), a step of drying the applied material applied to the surface of the adherend as described above, and a polymerizable monomer on the applied material. And a step of applying a polymerization catalyst, and a step of bonding an adherend to the surface of the ceramic thus treated. 10. The method according to claim 9, wherein the adherend is a metal or a ceramic. 11. A silane coupling agent is γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltri (trimethylsiloxy) silane or γ.
A method according to claim 9 which is methacryloxypropyl pentamethyldisiloxane. 12. The method according to claim 9, wherein the acidic compound is 4-methacryloxyethyl trimellitic acid. 13. The method according to claim 9, wherein the acidic compound is phosphoric acid. 14. The method according to claim 9, wherein the polymerizable monomer is methyl methacrylate. 15. The method according to claim 9, wherein the polymerizable monomer comprises methyl methacrylate and 4-methacryloxyethyl trimellitic anhydride. 16. The method according to claim 9, wherein the polymerization catalyst is a mixed system of trialkylboron or an oxide thereof, or an organic peroxide and amines. 17. A method for adhering ceramics, which comprises the following steps: (a) a silane coupling agent on the surface of the ceramics;
And (b) an organic carboxylic acid, an organic carboxylic acid anhydride,
At least one acidic compound selected from the group consisting of inorganic acids, sulfonic acids and organic phosphoric acids, (c) a polymerizable monomer, and (d) a polymerization catalyst, the amount of the silane coupling agent is the component (a), (B), (c) and (d)
And a step of bonding an adherend to the surface of the ceramic thus treated. 18. The method according to claim 17, wherein the adherend is a metal or a ceramic. 19. The silane coupling agent is γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltri (trimethylsiloxy) silane or γ.
A method according to claim 17, which is methacryloxypropyl pentamethyldisiloxane. 20. The method according to claim 17, wherein the acidic compound is 4-methacryloxyethyl trimellitic acid. 21. The method according to claim 17, wherein the acidic compound is phosphoric acid. 22. The method according to claim 17, wherein the polymerizable monomer is methyl methacrylate. 23. The method according to claim 17, wherein the polymerizable monomer comprises methyl methacrylate and 4-methacryloxyethyl trimellitic anhydride. 24. The method according to claim 17, wherein the polymerization catalyst is a trialkylboron or an oxide thereof, or a mixed system of an organic peroxide and amines.