JP2009143865A - Pretreatment material for oxide ceramic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pre-treatment material having a lasting adhesivity which is applied on the joining surface of an oxide ceramic in advance, when it is joined with an adherend via an adhesive composition. <P>SOLUTION: The pre-treatment material contains polymerizable monomers expressed by the general formula (1) such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and dimethylaminoethyl acrylate (wherein, Z represents an oxygen atom or a nitrogen atom; R<SP>1</SP>represents a hydrogen atom or a methyl group; R<SP>2</SP>represents an alkylene group; R<SP>3</SP>and R<SP>4</SP>each independently represents a 1-6C alkylgroup; and m represents 0 or 1). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a pretreatment material for oxide ceramics.

  In dentistry, a ceramic dental prosthesis mainly composed of silica is bonded to a tooth with a dental cement such as a resin cement for the purpose of repairing carious or missing teeth. In this case, a pretreatment material (primer for ceramics) containing a silane coupling agent as a main component is generally used in order to enhance the adhesion between the ceramic containing the silica as a main component and dental cement.

  For example, a dental pretreatment material comprising a silane coupling agent and an acidic organophosphorus compound having at least one radically polymerizable olefinic double bond in the molecule has been proposed (Patent Document 1). 2). In this dental pretreatment material, the acidic organophosphorus compound acts as a catalyst that activates the silane coupling agent and promotes condensation of silanol groups on the ceramic surface.

  Focusing on the field of dental ceramics, high-strength all-ceramic dental prosthetic materials made of oxide ceramics such as zirconium oxide or aluminum oxide are becoming widespread. With respect to these oxide ceramic materials, the treatment with a silane coupling agent, which is a general pretreatment material for all ceramics, does not provide sufficient adhesive strength in the long term in a severe oral environment. This is because a generally used dental ceramic material is composed mainly of silica, and has a large number of silanol groups on its surface, so that it reacts well with the silane coupling agent. In contrast, oxide ceramics such as zirconium oxide or aluminum oxide have little or no such silanol groups. There has been a demand for a novel pretreatment material for oxide ceramics that has an appropriate mechanism of action.

  As a pretreatment material for such novel oxide ceramics, a dental adhesive composition containing a phosphonic acid group-containing (meth) acrylate monomer (Patent Document 3) or a (meth) acrylate ester polymerizable monomer A pretreatment material for ceramics containing a polymer (Patent Document 4) is disclosed, but when the inventor measured the adhesive strength after a thermal shock test to test the durability of the adhesive strength, sufficient adhesive strength was obtained. It became clear that it did not have.

  On the other hand, polymerizable compounds having an aminoalkyl group are used in the fields of dental adhesives (Patent Document 5) and dental pretreatment materials (Patent Document 6). This was intended to improve adhesion to the tooth or storage stability (adjustment of pH), and was used for a completely different use from the pretreatment material for the oxide ceramic of the present invention. .

JP 63-51308 A Japanese Patent Application Laid-Open No. 07-277913 JP 2006-045179 A JP 2007-238498 A Japanese Patent Laid-Open No. 06-227935 JP 2004-043427 A

  Accordingly, the present invention provides a pretreatment material that is applied in advance to the joining surface of the oxide ceramic when the oxide ceramic is joined to an object to be joined via the adhesive composition. The aim is to develop long-term sustainable high adhesiveness with the composition.

  As a result of extensive investigations to overcome the above-mentioned problems, the present inventors have previously applied a pretreatment material composition containing a polymerizable monomer having a specific structure to the joint surface of oxide ceramics. As a result, it has been found that the oxide ceramics and the adhesive composition can be firmly bonded, and the present invention has been completed.

That is, the present invention is a pretreatment material that is preliminarily applied to the bonding surface of the oxide ceramic when the oxide ceramic is bonded to the workpiece through the adhesive composition,
General formula (1)

(In the formula, Z represents an oxygen atom or a nitrogen atom, R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group, and R ³ and R ⁴ each independently represents an alkyl group having 1 to 6 carbon atoms. M represents 0 or 1.)
A pretreatment material for oxide ceramics comprising a polymerizable monomer represented by

  By preliminarily applying the pretreatment material of the present invention to the bonding surface of the oxide ceramic, the oxide ceramic and the adhesive composition can be firmly bonded and maintained for a long period of time. I can do it. Therefore, the dental prosthesis made of the oxide ceramic can be suitably used for joining to a tooth using a dental cement such as a resin cement. In that case, the dental prosthesis and the dental cement The long-term adhesive force can be greatly improved, and as a result, the dental prosthesis and the tooth substance can be bonded for a long time.

  The pretreatment material of the present invention has the general formula (1)

(In the formula, Z represents an oxygen atom or a nitrogen atom, R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group, and R ³ and R ⁴ each independently represents an alkyl group having 1 to 6 carbon atoms. M represents 0 or 1.)
It is essential to contain a polymerizable monomer represented by

  The polymerizable monomer of the general formula (1) has a feature that it has a polymerizable group capable of radical polymerization and an amino group or an aminoalkyl group. Although the causal relationship between this structure and good adhesion to oxide ceramics is not clear, good adhesion is expressed by the interaction between the surface acid sites on the oxide surface and amino groups or aminoalkyl groups. There is a possibility. The aminoalkyl group in this specification refers to a disubstituted aminoalkyl group having two hydrocarbon groups.

  Z in the general formula (1) is an oxygen atom or a nitrogen atom, and more preferably an oxygen atom from the viewpoint of adhesive strength.

R ¹ in the general formula (1) is a hydrogen atom or a methyl group.

R ² in the general formula (1) is an alkylene group. Examples of the alkylene group include methylene group, ethylene group, ethylidene group, trimethylene group, propylene group, tetramethylene group, 1-methyltrimethylene group, 1,2-dimethylethylene group, and hexamethylene group for the same reason as above. It is preferably an alkylene group having 1 to 6 carbon atoms such as methylene group, ethylene group, ethylidene group, trimethylene group, propylene group, tetramethylene group, 1-methyltrimethylene group, 1,2-dimethyl. It is more preferably an alkylene group having 1 to 4 carbon atoms such as an ethylene group.

R ³ and R ⁴ in the general formula (1) each independently represent an alkyl group having 1 to 6 carbon atoms, more preferably a carbon number such as a methyl group, an ethyl group, a propyl group, or a butyl group. Particularly preferred are 1-4 alkyl groups, and further 1-2 alkyl groups such as methyl group and ethyl group.

  Further, m in the general formula (1) is 0 or 1, and 1 is particularly preferable in view of the performance required as a pretreatment material, that is, the influence on the adhesive force.

  Here, as a preferable thing among general formula (1), general formula (2)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group, and R ³ and R ⁴ each independently represents an alkyl group having 1 to 6 carbon atoms.)
The polymerizable monomer which has an amino group shown by these is mentioned.

  Specific examples of the polymerizable monomer represented by formula (1) or (2) that are particularly preferably used in the present invention are as follows.

  The polymerizable monomer having an amino group represented by the general formula (1) may be commercially available, but is not particularly limited, and a known compound can be used without limitation.

  The polymerizable monomer having an amino group represented by the general formula (1) can also be easily produced by the following method.

  That is, when Z in the general formula (1) is an oxygen atom, an aminoalkyl (meth) acrylate can be produced by a transesterification reaction between the corresponding alkyl (meth) acrylate and amino alcohol. For example, when methyl (meth) acrylate and dimethylaminoethanol are used as raw materials, dimethylaminoethyl (meth) acrylate and methanol are produced by these ester exchange reactions. As the catalyst for the transesterification reaction, alkali metal alcoholates, alkaline earth metal alcoholates, organotin compounds such as dibutyltin oxide, and β-diketone metal compounds such as acetylacetone iron (Japanese Patent Laid-Open No. 2-17155) are used. Yes.

Further, when Z in the formula of the general formula (1) is a nitrogen atom, the general formula (3)
CH ₂ = CRCOOR '(3)
(In the formula, R represents a hydrogen atom or a methyl group, and R ′ represents a lower alkyl group.)
An amine, cyclopentadiene, alcohol or the like is added as a protecting group to the double bond of the (meth) acrylic acid ester represented by general formula (4)
NH ₂ -Q (4)
(In the formula, Q represents an N, N-dialkylaminoalkyl group.)
The target product can be produced by reacting with a primary amine represented by the formula (1) and removing the protecting group by heating. For example, the method described in JP-B-54-9170 or the like using cyclopentadiene as a protecting group and USP 3,914,303 or the like using alcohol as a protecting group can be used.

  Furthermore, as an amine-protecting group, for example, in USP 2,451,436, an acrylic ester and one kind of mono- or dialkylamine are reacted to convert to N-alkyl-β-alkylaminopropionic amide. Then, a method for producing N-alkylacrylamide by thermally decomposing it in the presence of an acid is disclosed in Japanese Patent Application Laid-Open No. 4-154499. Thus, it is disclosed that dimethylacrylamide can be produced in good yield, and those methods can also be used.

  As the polymerizable monomer represented by the general formula (1) or (2) of the present invention, one compound can be used alone, but two or more compounds can be used in combination. .

  In the present invention, the polymerizable monomer represented by the above general formula (1) or (2) can be used alone as the polymerizable monomer component. If the content of the polymerizable monomer component is 60% by mass or less, preferably 30% by mass or less, other polymerizable monomers can be blended. As other components, other than the polymerizable monomer represented by the general formula (1) or (2), which can be copolymerized with the polymerizable monomer represented by the general formula (1) or (2). A radical polymerizable monomer is mentioned.

  The other polymerizable monomer is other than the polymerizable monomer represented by the general formula (1), and is compatible with the polymerizable monomer and polymerizable. Although it can be used without any limitation, examples of the polymerizable monomer that can be suitably used include polymerizable polymerizable monomers having an acryloyl group and / or a methacryloyl group, and such polymerizable monomers. Specific examples of these include the monomers shown in the following [A-1] to [A-4].

[A-1] Monofunctional vinyl monomer Methacrylate such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, and acrylates corresponding to these methacrylates; or acrylic acid, methacrylic acid, p-methacryloyloxybenzoic acid, N-2-hydroxy-3-methacryloyloxypropyl-N-phenylglycine, 4-methacryloyloxyethyl trimellitic acid and its anhydride, 6-methacryloyloxyhexamethylenemalonic acid, 10-methacryloyl Oxydecamethylenemalonic acid, 2-methacryloyloxyethyl dihydrogen phosphate, 10-methacryloyloxydecame Chilene hydrogen phosphate, 2-hydroxyethyl hydrogen phenyl phosphonate, etc.

[A-2] Bifunctional vinyl monomer [A-2-1] Aromatic compound type 2,2-bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy)- 2-hydroxypropoxyphenyl] propane, 2,2-bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxy) Phenyl) propane), 2,2-bis (4-methacryloyloxytetraethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) ) Propane, 2 (4-methacryloyloxydiethoxy) Nyl) -2 (4-methacryloyloxydiethoxyphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxyditriethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2 Corresponding to-(4-methacryloyloxytriethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane; and these methacrylates Acrylate; methacrylates such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, or polymers corresponding to these methacrylates Diaducts obtained from addition of a vinyl monomer having an —OH group such as acrylate and a diisocyanate compound having an aromatic group such as diisocyanate methylbenzene or 4,4′-diphenylmethane diisocyanate.

[A-2-2] Aliphatic compound type ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butanediol Dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate; and acrylates corresponding to these methacrylates; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl Vinyl monomers having —OH groups such as methacrylates such as methacrylates or acrylates corresponding to these methacrylates And diadducts obtained from the addition of diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, methylenebis (4-cyclohexyl isocyanate); acrylic anhydride, methacrylic anhydride, 1,2 -Bis (3-methacryloyloxy-2-hydroxypropoxy) ethyl, di (2-methacryloyloxypropyl) phosphate and the like.

[A-3] Trifunctional vinyl monomer Trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, methacrylates such as pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate, acrylates corresponding to these methacrylates, and the like.

[A-4] Tetrafunctional vinyl monomer Pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate and diisocyanate methylbenzene, diisocyanate methylcyclohexane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, methylenebis (4-cyclohexyl isocyanate), 4 Diadducts obtained from the addition of diisocyanate compounds such as 1,4-diphenylmethane diisocyanate and tolylene-2,4-diisocyanate and glycidol dimethacrylate.

  In addition, it is also possible to suitably employ a precious metal adhesive monomer described in JP-A-10-1409, JP-A-10-1473, JP-A-8-113763, or the like.

  These other polymerizable monomers may be used alone, or a plurality of polymerizable monomers may be used at the same time depending on the required physical properties.

  In the present invention, it is not necessary to use an organic solvent, but it is preferable to use an organic solvent in combination in order to improve the operability for application to the tooth surface. The organic solvent is not particularly limited as long as it can dissolve the polymerizable monomer represented by the general formula (1) or (2), and a known organic solvent having such properties can be used. Specifically, alcohols such as methanol, ethanol, isopropyl alcohol and butanol; ketones such as acetone and methyl ethyl ketone; ethers such as ethyl ether, 1,4-dioxane and tetrahydrofuran; ethyl acetate and ethyl formate Esters such as toluene; Aromatic solvents such as toluene, xylene and benzene; Hydrocarbon solvents such as pentane, hexane, heptane and octane; Chlorine solvents such as methylene chloride, chloroform and 1,2-dichloroethane; Trifluoroethanol Fluorinated solvents such as Among these, acetone, toluene, ethanol, and the like are particularly preferably used for reasons such as high solubility and volatility.

  Said organic solvent can also be used 1 type or in combination of 2 or more types.

  In the pretreatment material composition of the present invention, the blending amount of the organic solvent is 100 parts by mass of a polymerizable monomer containing a polymerizable monomer having an amino group of the general formula (1) or (2). When used, it is generally from 0.0001 to 999900 parts by mass, particularly preferably from 100 to 9900 parts by mass. When the blending amount of the organic solvent is 100 parts by mass or more, the coating thickness when applied is appropriately reduced. Moreover, since the ratio of the polymerizable monomer which has an amino group of General formula (1) or (2) becomes appropriate in the case of 9900 mass parts or less, adhesive force improves.

  Moreover, it is possible to mix | blend things other than an above-described component with the pretreatment material of this invention in the range which does not impair the performance as a pretreatment material for various purposes. Such components include coupling materials, polymerization initiators, polymerization inhibitors, polymerization regulators, UV absorbers, metal salts, inorganic or organic acids, water, fillers, thickeners, dyes, pigments, acid growth Examples include agents, base proliferating agents, antibacterial agents and the like.

  As the coupling agent blended as an optional component in the present invention, known ones can be used without limitation. Here, the coupling agent is a surface treatment agent capable of chemically bonding an organic material and an inorganic material, and is composed of a compound having an organic functional group and a hydrolyzable group in the molecule.

  Such coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris (β-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ -(Meth) acryloyloxypropyltris (β-methoxyethoxy) silane, γ- (meth) acryloyloxypropyltri (trimethylsiloxy) silane, ω- (meth) acryloyloxydecyltrimethoxysilane, γ- (meth) acryloyloxy Propylpentamethyldisiloxane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane , Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, Silane coupling agents such as mercaptopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, hexamethyldisilazane, isopropyltriisostearoyl titanate, isopropyltrioctanoyl titanate, isopropylisostearoyldi Acrylic titanate, isopropyl tridodecyl benzene sulfonyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tricumyl phenyl titanate, etc. Titanate coupling agents, aluminum coupling agents such as acetoalkoxyaluminum diisopropylate and the like.

  Among these coupling agents, a silane coupling agent having a polymerizable group is particularly preferably used from the viewpoints of adhesiveness and handleability. Here, examples of the polymerizable group include a vinyl group and a (meth) acryloyloxy group, and a (meth) acryloyloxy group is particularly preferable because of high polymerizability.

  Specific examples of the silane coupling agent having a polymerizable group that can be suitably used include γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltri (trimethylsiloxy) silane, and ω-methacryloyloxydecyltri. Examples include methoxysilane and γ-methacryloyloxypropylpentamethyldisiloxane.

  Said coupling agent can also be used 1 type or in combination of 2 or more types.

  In the pretreatment material of the present invention, the concentration of the coupling agent is not particularly limited, but from the viewpoint of adhesive strength, the polymerizable monomer component having an amino group represented by the general formula (1) is 100 parts by mass. When it is, it is preferable that it is 150 mass parts or less, Furthermore, it is the range of 40 mass parts or less.

  There is no restriction | limiting in particular about the method of preparing the pre-processing material of this invention, What is necessary is just to stir-mix until each said component is mixed and it becomes uniform.

  The pretreatment material of the present invention can be used without limitation when the oxide ceramic is bonded to an object to be bonded via an adhesive composition, and in that case, by applying the oxide ceramic to the bonding surface of the oxide ceramic in advance. Thus, the long-term adhesion between the oxide ceramic and the adhesive composition is greatly improved, and as a result, the oxide ceramic and the article to be joined can be joined for a long time.

  As the oxide ceramics to be pretreated, a compound composed of oxygen and a metal element containing oxygen in an oxidation number-2 state can be given. The metal element constituting the oxide is not particularly limited, and any metal element can be selected. These metal elements can be used alone, but can also contain a plurality of metal elements.

  Examples of suitable metal elements include Group 1A such as lithium, sodium and potassium; Group 2A such as magnesium, calcium, strontium and barium; Group 3A such as yttrium and lanthanum; Group 4A such as titanium, zirconium and hafnium. And 3B group such as aluminum and indium, 4B group such as silicon and germanium, and 5B group such as phosphorus and arsenic. Among them, those mainly composed of 4A group metal elements such as titanium, zirconium and hafnium, and 3B group metal elements such as aluminum and indium, are less toxic and have a high effect of the pretreatment material composition of the present invention. Zirconium and aluminum are the most preferable in terms of high strength when used as an oxide.

  The object to which the pretreatment material of the present invention is applied can be applied without limitation as long as it is made of the above-mentioned oxide ceramics, but restorations for crowns such as inlays, onlays, and crowns are most practical.

  Further, the adhesive composition is a polymerizable composition mainly composed of a polymerizable monomer and a polymerization initiator, and as the polymerizable monomer, known ones can be applied without limitation, for example, vinyl A polymerizable monomer, a styrene polymerizable monomer, an allyl polymerizable monomer, or the like may be used, but a (meth) acrylic polymerizable monomer is most preferable because of its high adhesiveness. As the (meth) acrylic polymerizable monomer used in this polymerizable composition, known ones such as those shown in the above [A-1] to [A-4] are not limited. Can be used. When the oxide ceramic to which the pretreatment material of the present invention is applied is the above-described dental prosthesis, dental cement is used as the (meth) acrylic polymerizable composition. As the dental cement, known ones such as resin-reinforced glass ionomer cement, resin ionomer cement, and resin cement can be used without limitation. The dental cement contains a (meth) acrylic polymerizable monomer, a polymerization initiator, and a filler, and the filler content is 100 mass of the (meth) acrylic polymerizable monomer. It is common that it is 1-10000 mass parts with respect to a part, and it is more preferable that it is 10-2000 mass parts. As for the usage-amount of a polymerization initiator, it is common that it is 0.01-20 mass parts with respect to 100 mass parts of (meth) acrylic-type polymerizable monomers.

  The method of using the pretreatment agent is to apply an organic solvent to the surface of the oxide ceramics made of the dental prosthesis, and then volatilize the organic solvent, and then apply an adhesive composition such as dental cement to the surface of the oxide ceramics. In addition, a method of joining this to an article to be joined such as a tooth can be suitably employed. The amount of application is not particularly limited, but it may be usually carried out by applying one layer using an applicator such as a sponge.

  In the aspect in which the dental prosthesis is joined to the tooth, it is efficient that the pretreatment material of the present invention is combined with the dental cement to form a kit for bonding the dental prosthesis to the tooth. is there.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the examples.

Next, the abbreviations or structures of the compounds used in the examples are shown below.
(1) Abbreviation or structure a) Polymerizable monomer represented by the general formula (1) or (2) DMEM: Dimethylaminoethyl methacrylate DEEM: Diethylaminoethyl methacrylate DMEA: Dimethylaminoethyl acrylate b) Other polymerizable properties Monomer GMA: 2,2-bis [4 (2-hydroxy-3-methacryloxypropoxy) phenyl] propane PM: PM; 2-methacryloyloxyethyl dihydrogen phosphate and bis (2-methacryloyloxyethyl) hydrogen Mixture of phosphate c) Organic solvent EtOH: Ethanol AC: Acetone d) Other MPS: γ-Methacryloyloxypropyltrimethoxysilane (2) Adhesive strength to oxide ceramics using pretreatment material Using Miniumu and zirconium oxide, which was polished with waterproof abrasive paper # 1500 was adhered an adhesive tape with a hole of 3mmφ to secure the bonding area on the treated surface. Each of the pretreatment materials of Examples and Comparative Examples was applied to the joint surface with a brush, and the solvent was air-dried (when the solvent was included), and then the dental adhesive resin cement (Bistite II, Co., Ltd.) ), A previously polished 8 mmφ × 18 mm round bar made of SUS304 was adhered. All 12 test specimens were immersed in 37 ° C. water for 24 hours, 6 test specimens were in that state, and the remaining 6 test specimens were each in 4 ° C. cold water and 60 ° C. warm water. After applying a thermal cycle of immersing 3000 minutes, the tensile adhesive strength was measured using an autograph (crosshead speed 2 mm / min) manufactured by Shimadzu Corporation. The measurement values of 6 test pieces were averaged to obtain measurement results.

Example 1
1 g of polymerizable monomer DMEM was dissolved in 9 g of organic solvent acetone, and this was used as a pretreatment material. According to the above test method, the adhesion strength of the pretreatment material to the oxide ceramics was examined. As a result, an adhesive strength of 22.4 MPa (cement cohesive failure rate of 100%) with respect to aluminum oxide and 23.5 MPa (cement cohesive failure rate of 100%) with respect to zirconium oxide was exhibited. Further, after the thermal cycle test, the adhesive strength was 17.8 MPa (cement cohesive failure rate 100%) with respect to aluminum oxide and 17.5 MPa (cement cohesive failure rate 100%) with respect to zirconium oxide.

Examples 2-13
Pretreatment materials having the compositions shown in Table 1 were prepared, and the adhesion effects to the oxide ceramics were examined according to the test methods described above. It became clear that each had good adhesiveness.

Comparative Example 1
The adhesion strength to the oxide ceramic was measured in the same manner as in Example 1 except that the pretreatment material was not used. The adhesion strength was 15.2 MPa (cement cohesive failure rate of 30%) for aluminum oxide and 14.4 MPa (cement cohesive failure rate of 20%) for zirconium oxide. In addition, after the thermal cycle test, the adhesive strength was 4.6 MPa (cement cohesive failure rate 0%) for aluminum oxide and 6.8 MPa (cement cohesive failure rate 0%) for zirconium oxide.

Comparative Examples 2-5
The adhesive strength to the oxide ceramics was measured in the same manner as in Example 1 except that the polymerizable monomer having an amino group represented by the general formula (1) or (2) was not used. In each case, the adhesive strength was low compared to the Examples.

Example 14
The pretreatment material described in Example 1 was applied to the joint surface of an aluminum oxide dental prosthesis produced according to a conventional method, and the solvent was completely dried. On the other hand, a tooth surface primer attached to a dental adhesive resin cement (Bistite II, manufactured by Tokuyama Dental Co., Ltd.) was applied to the tooth structure as an object to be bonded, and then dried well. After applying dental adhesive resin cement (Bistite II, manufactured by Tokuyama Dental Co., Ltd.) to the joint surface of aluminum oxide dental prosthesis coated with pretreatment material, it is joined to the tooth surface treated with tooth surface pretreatment material I let you. It showed good bonding properties and good clinical results.

Example 15
Except that the dental prosthesis was made of zirconium oxide, the bondability to the tooth was tested in the same manner as in Example 14. The results showed good adhesion and good clinical results.

Claims (5)

When the oxide ceramic is bonded to an object to be bonded via the adhesive composition, a pretreatment material is applied in advance to the bonding surface of the oxide ceramic,
General formula (1)

(In the formula, Z represents an oxygen atom or a nitrogen atom, R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group, and R ³ and R ⁴ each independently represents an alkyl group having 1 to 6 carbon atoms. M represents 0 or 1.)
An oxide ceramic pretreatment material comprising a polymerizable monomer represented by When joining oxide ceramics to an object to be joined via an adhesive composition, a pretreatment material that is applied in advance to the joining surface of the oxide ceramics,
General formula (2)

(In the formula, R ¹ , R ² , R ³ and R ⁴ are the same as those in the general formula (1).)
An oxide ceramic pretreatment material comprising a polymerizable monomer represented by   The pretreatment material for oxide ceramics according to claim 1 or 2, further comprising an organic solvent. The oxide ceramics pretreatment material according to any one of claims 1 to 3, wherein the oxide ceramic is a dental prosthesis, the adhesive composition is dental cement, and the article to be joined is a tooth. . A kit for adhering a dental prosthesis comprising the pretreatment material according to claim 4 and dental cement to a tooth.