JP2006045179A - Dental ceramic adhesive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dental adhesive composition for bonding dental materials comprising a specific inorganic compound or an organic composite material containing the inorganic compound. <P>SOLUTION: This dental adhesive composition comprising a phosphonic acid group-containing (meth)acrylate-based monomer having a specific structure. Preferably, the dental adhesive composition for bonding a dental material whose at least one part comprises an inorganic material represented by the general formula: MOm/2 äM is one or more elements selected from Al, Zr, Ti, and Mg [(m) is the valency of M]}. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a dental adhesive composition. Dental adhesive composition having excellent adhesion to a dental material whose surface potential in water of an inorganic compound or an organic composite containing an inorganic compound is positive at the isoelectric point of silicon dioxide Related to things.

In general, ceramics is defined as a material or product obtained from inorganic and non-metal raw materials, molded and cured by heat. In other words, the meaning of ceramics originally refers to “yakimono”. This old-origin ceramic is a product that uses natural raw materials, uses refined raw materials, and manufactures products with relatively precise control of temperature and atmosphere, and then uses high-purity synthetic raw materials. It has been developed into an advanced product manufactured with strictly controlled composition.
In the dental field as well, materials based on ceramics with excellent aesthetics and mechanical properties have been used as materials and crown materials that are used to repair missing parts of affected tooth areas. At present, the process is complicated, and advanced skill is required for color adjustment and production.

Further, the ceramic crown is a brittle material and has a problem in strength that it breaks in a severe oral environment. In order to overcome such strength problems, metal ceramic systems using a metal material as a core material of the ceramic crown have become widespread, and until now, metal ceramics have occupied the majority.
Metal ceramics are widely used as representatives of aesthetic prostheses, but have aesthetic reproducibility limitations due to completely opaque metal materials. On the other hand, the development of dental ceramic materials and production systems has greatly advanced, and all the clinically sufficient strength has been established in terms of systems that are better handled by castable, pressable, glass impregnation, CAD / CAM, etc. A ceramic crown can be made. Many new ceramics have been created as the core material of this all-ceramic crown. These ceramics are special ceramics that are manufactured by highly controlled manufacturing processes to develop functions that have been designed in advance, such as mechanical properties, thermal properties, chemical compositions, shapes, and microstructures. It is a strength ceramic.

  In dentistry, aluminum oxide, zirconium oxide, and the like are generally used as high-strength ceramics having strength against high external forces. Normally, the high-strength ceramic material is used through the dental adhesive composition to be installed in the oral cavity. To achieve permanent function in a harsh oral environment, There is a need for a dental adhesive composition having a strong adhesion function to a high strength ceramic material.

According to Dental Materials Journal 6 (2), 1987, a pretreatment agent containing a carboxylic acid monomer or a carboxylic acid anhydride monomer and a silane coupling agent for adhesion to aluminum oxide in a system bonded with MMA-TBB resin Is considered effective for bonding.
However, since the reaction between the carboxylic acid (carboxylic acid anhydride) monomer and the aluminum oxide surface is unclear, knowledge about the requirements of the reactive compound, such as the characteristics of the reactive compound and the blending amount, can be obtained. Not. Furthermore, Dent. Mater. 14 (1998) suggests the effectiveness of an adhesive resin cement containing a phosphate ester monomer in adhesion to zirconium oxide, but remains a problem in the development of adhesive surface treatment methods, adhesives, and the like. . In addition, methods such as air ablation to provide irregularities on the surface and silane coating on the surface with a special machine have been proposed. It is not possible to maintain.
On the other hand, a general dental ceramic material is a material mainly composed of silicon dioxide called porcelain. A composition containing a silane coupling agent is effective as a dental adhesive composition for a dental ceramic material containing silicon dioxide as a main component, and is widely applied in the dental field.

Furthermore, detailed research results such as the reaction mechanism of silane coupling agents to silicon dioxide have been reported in Silane Coupling Agents, Plenum Press (1982), Polymer Composite, April, 5 (2), 1984, and the like. . The current situation in the dental field is that adhesive compositions that are used for general ceramic materials in bonding to high-strength ceramics, that is, adhesive compositions that contain a silane coupling agent for porcelain as an active ingredient are only being diverted. In addition, the silane coupling agent cannot obtain sufficient adhesion and durability for dental high-strength ceramics made of aluminum oxide, zirconium oxide, or the like that does not substantially contain silicon dioxide.
In Japanese Kokai 63-51308 and JP-A-7-277913, dental ceramics containing silicon dioxide by combining a silane coupling agent and a phosphate ester monomer, especially dental porcelain, and dental A dental adhesive composition for performing strong and durable adhesion to a dental restorative material such as a resin or a dental alloy is disclosed, and dental ceramics of this dental adhesive composition are disclosed. The active ingredient for is a silane coupling agent and is limited to dental ceramic materials mainly composed of silicon dioxide.

  Further, the phosphate ester monomer is a catalyst component having a function of promoting the condensation of the silane coupling agent and the silanol group on the surface of the adherend, and there is no description about adhesiveness to dental high-strength ceramics. Further, in JP-A-9-137129, a coating liquid containing a silane coupling agent and an acidic compound such as an organic carboxylic acid, and a coating solution coated on the coating surface and polymerized in the presence of a polymerization catalyst. Although the dental adhesive composition by the coating material which consists of a polymerizable monomer is disclosed, there is no description about the adhesiveness with respect to dental high-strength ceramics also in this dental adhesive composition.

JP-A-63-51308 JP-A-7-277913 JP-A-9-137129 Dental Materials Journal 6 (2), 1987 Dent. Mater. 14 (1998) Silane Coupling Agents: Plenum Press (1982) Polymer Composite, April, 5 (2), 1984

Problems to be solved by the invention

An object of the present invention is to provide a dental adhesive composition that provides an excellent adhesive effect to a dental material whose surface potential in water is positive at the isoelectric point of silicon dioxide.
Furthermore, it is providing the dental adhesive composition whose durability and operativity are simple. The surface of the inorganic compound is formed of O, OH, CO ₃ or the like bonded to silicon or a metal element, and the M—OH (or O, CO ₃ ) group on the surface of the inorganic compound is absorbed and desorbed by protons depending on the M element species. The effect mechanism with the adhesive functional compound in the dental adhesive composition is greatly affected.
Therefore, the electric potential such as the surface potential of the inorganic compound surface and the change in zeta potential is one of the most important factors governing the surface modification effect by the dental adhesive composition on the surface of the inorganic compound. It has an important influence on the adhesion strength, adhesion stability and adhesion durability.

  In the present invention, the surface potential means a zeta potential, and the zeta potential on the ceramic surface can be easily measured by a commercially available measuring apparatus based on a laser Doppler method, an ultrasonic method, or the like. Further, in the present invention, the isoelectric point means a hydrogen ion concentration at which the zeta potential becomes zero in a solution containing ions, and the measurement is performed according to JIS R 1638 "Method for measuring isoelectric point of fine ceramic powder". It shall be performed according to the above.

In the mechanism of action of the silane coupling agent on silicon dioxide, due to the dehydration reaction between the Si-OH group of the hydrolyzed silane coupling agent and the M-OH (M is silicon or metal element) group on the substrate surface. It is known that covalent bonds or hydrogen bonds are formed and chemically bonded.

  In the case of silicon dioxide, a silane coupling agent works effectively. However, in the case of aluminum oxide, zirconium oxide, mullite, spinel, etc., the Si-OH group of the hydrolyzed silane coupling agent acts on the M-OH group (M is a metal element) on the substrate surface as compared with silicon dioxide. do not do.

Means for solving the problem

As a result of intensive studies on the components and blending methods regarding the dental adhesive composition in order to solve the above-mentioned problems, the surface potential in water was measured by the measurement method of JIS R 1638, etc. The present invention has been completed by finding an adhesive composition having excellent adhesiveness to a dental material characterized by being positive in electric point.
That is, this invention is a dental adhesive composition containing the phosphonic acid group containing (meth) acrylate type monomer for adhere | attaching the dental material which consists of an organic compound containing an inorganic compound or an inorganic compound.
By adopting such a configuration, the dental material is provided with excellent adhesiveness and durability that have not been seen in the past, is easy to operate, and is excellent in storage stability.

As a preferable inorganic compound, at least a part of the composition of the inorganic compound is a general formula, MO _{m / 2} "M is Al, Zr, Ti, Mg (m represents the valence of M). It may be an organic composite containing this inorganic compound.
Particularly preferred inorganic compounds are oxide ceramics, and single oxides, composite oxides, oxyacid salts such as silicates and phosphates. Furthermore, in a preferred embodiment, the present invention provides that the phosphonic acid group-containing (meth) acrylate monomer is represented by the following general formula [1].

（式中、Ｒ１は水素原子またはメチル基を示し、Ｒ２は置換基を有していてもよい炭素原子数１〜２０のアルキレン基を示し、Ｒ３は置換基を有していてもよい炭素原子数１〜１５のアルキレン基を示す。）で表わされることを特徴とする歯科用接着性組成物であり、一般式〔１〕で表されるホスホン酸基含有（メタ）アクリレート系単量体を含むことを特徴とする歯科用接着性組成物である。
一般式〔１〕で表されるホスホン酸基含有（メタ）アクリレート系単量体を０．０１〜９９．９重量部含むことを特徴とする歯科用接着性組成物。
一般式〔１〕で表されるホスホン酸基含有（メタ）アクリレート系単量体が６−メタクリロキシヘキシル−ホスホノアセテート、６−メタクリロキシヘキシル−３−ホスホノプロピオネート、１０−メタクリロキシデシル−３−ホスホノプロピオネート、１０−メタクリロキシデシル−ホスホノアセテートからなる群から選ばれる１種または２種以上の混合物であることを特徴とする歯科用性組成物。
水を含むことを特徴とする歯科用高強度セラミックス接着性組成物。
有機溶媒、ラジカル重合性単量体、充填材および重合触媒を含む歯科用接着性組成物。
分子内にラジカル重合性基を有しない酸性化合物を含む歯科用接着性組成物。
２分割されていてもよい本質的に均一または不均一である歯科用接着性組成物。

(Wherein R1 represents a hydrogen atom or a methyl group, R2 represents an alkylene group having 1 to 20 carbon atoms which may have a substituent, and R3 represents a carbon atom which may have a substituent) A dental adhesive composition characterized by being represented by formula (1), wherein the phosphonic acid group-containing (meth) acrylate monomer represented by the general formula [1] It is a dental adhesive composition characterized by including.
A dental adhesive composition comprising 0.01 to 99.9 parts by weight of a phosphonic acid group-containing (meth) acrylate monomer represented by the general formula [1].
The phosphonic acid group-containing (meth) acrylate monomer represented by the general formula [1] is 6-methacryloxyhexyl-phosphonoacetate, 6-methacryloxyhexyl-3-phosphonopropionate, 10-methacryloxy A dental composition which is one or a mixture of two or more selected from the group consisting of decyl-3-phosphonopropionate and 10-methacryloxydecyl-phosphonoacetate.
A dental high-strength ceramic adhesive composition comprising water.
A dental adhesive composition comprising an organic solvent, a radical polymerizable monomer, a filler and a polymerization catalyst.
A dental adhesive composition comprising an acidic compound having no radically polymerizable group in the molecule.
Dental adhesive composition that is essentially uniform or non-uniform, which may be divided in two.

The invention's effect

By using the dental adhesive composition of the present invention, it is possible to bring about excellent adhesiveness and durability that are not conventionally seen with respect to dental materials composed of inorganic compounds or organic composites containing inorganic compounds. . Furthermore, excellent adhesion durability can be obtained by a simple operation.

The curable composition of the present invention may be divided into two as its embodiment, and is essentially uniform or non-uniform, and is a dental bonding agent and primer, (adhesive) composite resin, resin cement, dual cure type It can be used for resin cements, opaque agents, compomers, resin cores, front crown materials, etc.

As a phosphonic acid group-containing (meth) acrylate monomer that is a constituent component in the present invention,

で示されるホスホン酸基を含有する（メタ）アクリレート系単量体である。なお、本発明において「（メタ）アクリレート」とはアクリレートまたはメタクリレートを意味する。好ましくは下記一般式〔１〕で示されるものが挙げられる。

(Meth) acrylate monomer containing a phosphonic acid group represented by In the present invention, “(meth) acrylate” means acrylate or methacrylate. Preferred examples include those represented by the following general formula [1].

（式中、Ｒ_１は水素原子またはメチル基を示し、Ｒ_２は置換基を有していてもよい炭素原子数１〜２０のアルキレン基を示し、Ｒ_３は置換基を有していてもよい炭素原子数１〜１５のアルキレン基を示す。）アルキレン基の例としては式１につき前記したものが挙げられる。ここに、Ｒ_２またはＲ_３に結合してもよい置換基としては、アルケニル基およびアルキニル基などの不飽和基あるいはアルキル基、あるいはフェニル基と結合したアルキル基等である。

(In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an optionally substituted alkylene group having 1 to 20 carbon atoms, and R ₃ may have a substituent. A good alkylene group having 1 to 15 carbon atoms is shown.) Examples of the alkylene group include those described above for Formula 1. Here, examples of the substituent that may be bonded to R ₂ or R ₃ include an unsaturated group such as an alkenyl group and an alkynyl group, an alkyl group, or an alkyl group bonded to a phenyl group.

が挙げられ、アルキル基の例としては、−ＣＨ_３、−Ｃ_２Ｈ_５、−Ｃ_３Ｈ_７が挙げられ、フェニル基と結合したアルキル基の例としては、−ＣＨ_２ＣＨ_２ＯＣ_６Ｈ_５が挙げられる。一般式１で示される具体的化合物としては下記のものが例示される。Examples of alkenyl groups include

Examples of the alkyl group include —CH ₃ , —C ₂ H ₅ , and —C ₃ H _7. Examples of the alkyl group bonded to the phenyl group include —CH ₂ CH ₂ OC ₆ H. ₅ is mentioned. Specific examples of the compound represented by the general formula 1 include the following.

Particularly preferred phosphonic acid group-containing (meth) acrylate monomers are 6-methacryloxyhexyl-phosphonoacetate, 6-methacryloxyhexyl-3-phosphonopropionate, 10-methacryloxydecyl-3-phosphono Propionate, 10-methacryloxydecyl-phosphonoacetate, and particularly preferred phosphonic acid group-containing (meth) acrylate monomers are 6-methacryloxyhexyl-phosphonoacetate or 6-methacryloxyhexyl-3- Phosphonopropionate. The blending ratio of the phosphonic acid group-containing (meth) acrylate monomer may be appropriately changed depending on the purpose of use of the composition, but is 0.01 to 99.9 parts by weight, more preferably 0.01 to 80.0 parts by weight. More preferably, it is 0.01-50.0 weight part.

The dental adhesive composition of the present invention can be added by appropriately selecting other components, with the phosphonic acid group-containing (meth) acrylate monomer as an essential component, depending on the use, Water, organic solvent, radical polymerizable monomer, coupling agent, photopolymerization initiator, photopolymerization accelerator, thermal polymerization initiator, polymerization catalyst, acidic compound having no radical polymerizable group in the molecule, inorganic In addition, an organic filler, a polymerization inhibitor, a pigment, and the like may be appropriately blended.

In the present invention, water may be contained as a solvent, and an organic solvent can be used. As the organic solvent, not only a general organic solvent but also a polymerizable monomer can be used as the organic solvent, and a volatile solvent is preferably employed. That is, alcohols such as ethanol, methanol, 1-propanol and isopropyl alcohol, ketones such as acetone, methyl ethyl ketone, pentanone and hexanone, esters such as ethyl acetate, methyl acetate and ethyl propionate, 1,2-dimethoxyethane Ethers such as 1,2-diethoxyethane and tetrahydrofuran, hydrocarbons such as heptane, hexane, octane and toluene, and halogenated hydrocarbons such as chloroform and dichloromethane are preferably used. Of these, acetone, ethanol, isopropyl alcohol, and the like are preferably used. These organic solvents may be used alone or in combination of two or more compounds. Moreover, the compounding quantity of these organic solvents is 0.1 weight%-99.9 weight%, More preferably, it is 25.0-99.9 weight part.

A radical polymerizable monomer can be added to the dental adhesive composition in the present invention. Specific examples of the radical polymerizable monomer include (meth) acrylates such as (meth) acrylic acid, methyl (meth) acrylate, and ethyl (meth) acrylate, and alkyl side chain substitution products thereof with hydroxyl groups and halogens, methoxydiethylene glycol ( (Meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, polyethylene glycol di (Meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2, 2 -Bis {4- (meth) acryloxypropoxyphenyl} propane, 2,2'-bis {4- (meth) acryloxyethoxyphenyl} propane, 2,2'-bis {4- (meth) acryloxydiethoxy Phenyl} propane, bisphenol A di (meth) acrylate, bisphenol A diglycidyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylolethanetetra (meth) acrylate, epoxy- ( (Meth) acrylate, urethane (meth) acrylates which are reaction products of organic diisocyanate and oxyalkyl (meth) acrylate, urethane prepolymer (reaction product of organic diisocyanate and diol) and at least two carbon atoms A polymerizable prepolymer containing at least two polymerizable ethylenically unsaturated groups, a reaction product of the oxyalkanol with a (meth) acrylic acid ester, a dibasic carboxylic acid having an ethylenically unsaturated group and a divalent carboxylic acid Reaction products with alcohol (that is, polyesters generally having an ethylenically unsaturated group) and the like can be mentioned.

These radical polymerizable monomers are used alone or in appropriate combination. Among them, bisphenol A diglycidyl (meth) acrylate and triethylene glycol di (meth), which are polymerizable monomers such as di (meth) acrylate, are used. A combination with acrylate) is preferred.

Any known coupling agent can be used without limitation. Specifically, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris (γ-methoxy Ethoxy) silane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 6- (meth) acryloyloxyhexyltrimethoxysilane, 6- (meth) acryloyloxyhexyltriethoxy Silane, 10- (meth) acryloyloxydecyltrimethoxysilane, 10- (meth) acryloyloxydecyltriethoxysilane, 11- (meth) acryloyloxy Decyltrimethoxysilane, 11- (meth) acryloyloxyundecyltriethoxysilane, 3- (meth) acryloyloxypropylpentamethyldisiloxane, 3-chloropropyltrimethoxysilane, mercaptopropyltrimethoxysilane, hexamethyldisilazane, etc. Silane coupling agents such as isopropyl triisostearoyl titanate, isopropyl trioctanoyl titanate, inpropyl isostearoyl diacryl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl dimethacryloyl isostearoyl titanate, isopropyl tricumyl phenyl titanate, etc. Aluminum coupling agents such as titanate coupling agents and acetoalkoxyaluminum diisopyropyrate And the like. These coupling agents are used alone or in combination of two or more. These coupling agents are usually blended as they are when preparing the adhesive composition of the present invention. For example, in the case of a silane coupling agent or the like, it is hydrolyzed with an acid or alkali in advance and converted into a silanol group. You may mix | blend. In addition, the silyl group of the silane coupling agent may be hydrolyzed with time after preparation to be partially or entirely converted into a silanol group. The addition amount of the coupling agent can be appropriately determined.

As the polymerization initiator used in the present invention, known compounds generally used in dental compositions are used without any limitation. The polymerization initiator is generally classified into a thermal polymerization initiator and a photopolymerization initiator.

As the photopolymerization initiator, a photosensitizer that generates radicals by light irradiation can be used. Examples of photosensitizers for ultraviolet rays include benzoin compounds such as benzoin, benzoin methyl ether, and benzoin ethyl ether, benzophenone compounds such as acetoin benzophenone, p-chlorobenzophenone, and p-methoxybenzophenone, thioxanthone, and 2-chlorothioxanthone. Thioxanthone compounds such as 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone. In addition, a photosensitizer that initiates polymerization with visible light is preferably used because it does not require ultraviolet rays harmful to the human body. Examples of these are benzyl, camphorquinone, α-naphthyl, acetonaphthene, p, p′-dimethoxybenzyl, p, p′-dichlorobenzylacetyl, pentanedione, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone. , 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, α-diketones such as naphthoquinone. Preferably, camphor quinone is used.

It is also preferable to use a photopolymerization accelerator in combination with the photosensitizer. In particular, when a tertiary amine is used as a photopolymerization accelerator, it is more preferable to use a compound in which a nitrogen atom is directly substituted on an aromatic group. Such photopolymerization accelerators include N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine. N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine, p-bromo-N, N-dimethylaniline, m-chloro-N, N-dimethylaniline, p-dimethylaminobenzaldehyde, p -Dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid aminoester, N, N-dimethylanthranic acid methyl ester, N, N-dihydroxy Ethylaniline, N, N-dihydroxyethyl-p-toluic , P-dimethylaminophenyl alcohol, p-dimethylaminostyrene, N, N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β -Naphtylamine, tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N- Tertiary amines such as dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, 2,2 ′-(n-butylimino) diethanol, and 5-butyl barbituric acid, 1-benzyl-5-phenylbarbitur Barbituric acid such as acid And metal salts such as sodium salt and calcium salt thereof, dibutyl-tin-diacetate, dibutyl-tin-dimaleate, dioctyl-tin-dimaleate, dioctyl-tin-dilaurate, dibutyl-tin-dilaurate, dioctyl-tin- Tin compounds such as diversate, dioctyl-tin-S, S′-bis-inoctyl mercaptoacetate, tetramethyl-1,3-diacetoxy distanoxane and the like can also be used. Among these photopolymerization accelerators, at least one kind can be selected and used, and two or more kinds can also be mixed and used. The addition amount of the starting material and the promoter can be determined as appropriate.

Furthermore, in order to improve the photopolymerization promoting ability, in addition to tertiary amines, citric acid, malic acid, tartaric acid, glycolic acid, gluconic acid, α-oxyin butyric acid, 2-hydroxypropanoic acid, 3-hydroxypropanoic acid Addition of oxycarboxylic acids such as 3-hydroxybutanoic acid, 4-hydroxybutanoic acid, dimethylolpropionic acid and the like is effective.

Specific examples of thermal polymerization initiators include benzoyl peroxide, parachlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, acetyl peroxide, lauroyl peroxide, tertiary butyl peroxide, cumene hydroperoxide, 2 , 5-dimethylhexane-2,5-dihydroperoxide, methyl ethyl ketone peroxide, organic peroxides such as tertiary butyl peroxybenzoate, azo such as azobisisobutyronitrile, methyl azobisisobutyrate, azobiscyanovaleric acid Compounds are preferably used.

The polymerization can also be carried out at room temperature by using a combination of the above organic peroxide and an amine compound. As such an amine compound, a secondary or tertiary amine in which an amine group is bonded to an aryl group is preferably used from the viewpoint of curing acceleration. For example, N, N-dimethyl-p-toluidine, N, N-dimethylaniline, N, N-β-hydroxyethyl-aniline, N, N-di (β-hydroxyethyl) -aniline, N, N-di ( β-hydroxyethyl) -p-toluidine, N-methyl-aniline, N-methyl-p-toluidine are preferred.

It is also suitable to further combine a sulfinate or borate with the combination of the organic peroxide and the amine compound. Examples of such sulfinates include sodium benzenesulfinate, lithium benzenesulfinate, sodium p-toluenesulfinate and the like. As borate, sodium salt, lithium salt, potassium salt, magnesium salt of trialkylphenyl boron, trialkyl (p-fluorophenyl) boron (alkyl group is n-butyl group, n-octyl group, n-dodecyl group, etc.), Examples include tetrabutylammonium salt and tetramethylammonium salt. In addition, organoboron compounds such as tributylborane and tributylborane partial oxide that generate radicals by reaction with oxygen and water can also be used as organometallic polymerization initiators.

In the dental adhesive composition of the present invention, an acidic compound having no radical polymerizable group in the molecule can be blended for the purpose of etching and / or modifying the surface of the inorganic compound. Such acidic compounds are organic acids and inorganic acids, and preferred organic acids include phosphoric acid monoester, phosphoric acid diester, phosphonic acid, phosphonic acid monoester, phosphonic acid diester, oxyhalogenated phosphoric acid monoester, Organic phosphorus compounds such as oxyhalogenated phosphoric acid diester, pyrophosphoric acid monoester, pyrophosphoric acid diester, pyrophosphoric acid triester, phosphinic acid, chromenic acid, linoleic acid, undecenoic acid, cinnamic acid, sorbic acid, coumaric acid Maleic acid, citraconic acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, stearic acid, pyruvic acid, methoxyacetic acid, acetoacetic acid, benzoic acid, phenylacetic acid, salicylic acid, glycolic acid, lactic acid, oxalic acid, succinic acid Acid, adibic acid, tartaric acid, maleic acid, fumaric acid And organic carboxylic acids such as phthalic acid. Preferred inorganic acids include sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, hydrogen fluoride, hydrogen bromide, hydrogen iodide, diphosphoric acid, tripolyphosphoric acid, phosphonic acid, and the like.

The dental adhesive composition of the present invention may contain various known additives as necessary. Examples of such additives include polymerization inhibiting materials, coloring materials, anti-discoloring materials, fluorescent materials, ultraviolet absorbing materials, antibacterial materials, and the like.

Examples of inorganic and organic fillers include polymethyl methacrylate, polyethyl methacrylate, copolymers of methyl methacrylate and ethyl methacrylate, organic polymer powders such as polystyrene, thermosetting resin cured products, and thermosetting resin curing materials including inorganic fillers. Organic fillers obtained by pulverizing materials, etc., or inorganic fillers (kaolin, talc, quartz, silica, colloidal silica, alumina, aluminosilicate, silicon nitride, barium sulfate, calcium phosphate, barium sulfate, glass powder, etc.), inorganic fillers And a composite filler of organic filler and the like, and the composition is suitable for use in powder / liquid type, paste form, and slurry form. These may be coated on the surface with a coupling material (such as γ-methacryloxypropyltrimethoxysilane) containing a silanol group.

Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, butylated hydroxytoluene and the like, which are suitable for stabilizing the shelf life of the composition.

◎ Isoelectric point and zeta potential measurement method Disperse high-purity silicon dioxide powder (manufactured by Tosoh Silica Co., Ltd.) in aqueous electrolyte solution, change its pH and measure the zeta potential. Asked. In addition, a laser zeta electrometer [manufactured by Otsuka Electronics Co., Ltd., ELS-6000] was used as a measuring instrument, and the measuring method was in accordance with JIS R 1638 “Method for measuring isoelectric point of fine ceramic powder”.

Furthermore, as dental materials made of inorganic compounds, aluminum oxide [99.5%, manufactured by Nippon Fine Ceramics Co., Ltd.], partially stabilized zirconium oxide (hereinafter referred to as zirconium oxide) [containing 3% yttrium oxide, Japan Fine Ceramics] Co., Ltd.], a mullite (manufactured by Matsukaze Co., Ltd.) flat plate (20 × 40 × 0.5 mm) is immersed in an electrolyte solution, and its pH is changed to produce a laser zeta electrometer [manufactured by Otsuka Electronics Co., Ltd. ELS-6000] and the zeta potential was measured.

Abbreviations described in FIG. 1 and Table 1 are as follows.
Silicon dioxide: SiO ₂
Aluminum oxide: Al ₂ O ₃
Zirconium oxide: ZrO ₂ -3Y
Mullite: 3Al ₂ O ₃ · 2SiO ₂

The isoelectric points and zeta potential-pH diagrams of the silicon dioxide powder and the flat plates of aluminum oxide, zirconium oxide and mullite are shown in Table 1 and FIG. As is clear from Table 1 and FIG. 1, the isoelectric points of the aluminum oxide, zirconium oxide, and mullite plates are present at a higher pH than the isoelectric point of the silicon dioxide powder, and aluminum oxide, zirconium oxide, and mullite. It can be seen that the zeta potential of this flat plate has a positive zeta potential at the isoelectric point of the silicon dioxide powder.

Next, the present invention will be specifically described with reference to examples and comparative examples. In addition, this invention is not limited to these Examples at all.
(Examples 1-15 and Comparative Examples 1-3)
Abbreviations (chemical names) shown in the examples
1) Phosphonic acid group-containing (meth) acrylate monomer 6-MHPA: 6-methacryloxyhexyl-phosphonoacetate 6-MHPP: 6-methacryloxyhexyl-3-phosphonopropionate 10-MDPP: 10- Methacryloxydecyl-3-phosphonopropionate 10-MDPA: 10-methacryloxydecyl-phosphonoacetate 2) Radical polymerizable monomer Bis-GMA: Bisphenol A diglycidyl methacrylate 3G: Triethylene glycol dimethacrylate 3) Coupling agent γ-MPS: γ-methacryloxypropyltrimethoxysilane 4) Photopolymerization initiator, photopolymerization accelerator CQ: Camphorquinone DMABE: p-dimethylaminobenzoic acid ethyl ester 5) Polymerization catalyst p-TSNa: p -Toluene sulf Sodium phosphate 6) Filler R-972: Fine particulate silicic acid [manufactured by Nippon Aerosil Co., Ltd.]
7) Acidic compound n-BuPA: phosphoric acid mono-n-butyl ester, phosphoric acid di-n-butyl ester mixture

(Materials and equipment used in the experiment)
Resin cement: “Imperva Dual” (Made by Matsukaze)
Aluminum oxide flat plate: Approximately 15 x 15 x 2 mm [manufactured by Nippon Fine Ceramics Co., Ltd.]
Zirconium oxide flat plate: Approximately 15 × 15 × 2 mm [manufactured by Nippon Fine Ceramics Co., Ltd.]
Thermal cycle tester: [Tokyo Giken Co., Ltd.]
Instron universal testing machine (Instron)
Aluminum oxide powder: 1μm [Nippon Light Metal Co., Ltd.]
Zirconium oxide powder: 2 μm [Daiichi Rare Element Chemical Co., Ltd.]
Examples of dental materials made of inorganic compounds include aluminum oxide flat plates (about 15 × 15 × 2 mm [manufactured by Nippon Fine Ceramics Co., Ltd.]) and zirconium oxide flat plates (about 15 × 15 × 2 mm [Japan Fine Ceramics Co., Ltd.] )] Was used to conduct a tensile adhesive strength test. The adhesive composition was prepared by mixing at a weight ratio shown in Table 2.
A flat surface of an aluminum oxide or zirconium oxide flat plate of about 15 × 15 × 2 mm was polished under flowing water using No. 240 and then No. 600 silicon carbide paper (manufactured by Sankyo Rikagaku Co., Ltd.) to obtain a smooth surface. Then, ultrasonic cleaning and air drying were performed to obtain an adherend. The adhesive composition was applied to the adherend surface of the adherend with a mini brush, left as it was for 30 seconds, and then dried with an air syringe until the fluidity of the adhesive composition disappeared. On the other hand, the adhesion surface of a cylindrical stainless steel rod having a diameter of 5 mm × height of 10 mm is air ablated (50 μm alumina beads, 5 kgf / cm ² pressure), and then ultrasonically cleaned and air dried to obtain a bonding strength measuring jig. . Adhesion was performed by interposing “Imperva Dual” kneaded into a uniform paste between the adhesion surface of the adherend and the adhesion surface of the stainless steel bar. At this time, excess cement was removed with a mini brush, and photopolymerization was performed for 10 seconds using “Matsukaze Grip Light II” as a cement margin. All 14 test pieces were immersed in 37 ° C. water, and for 7 test pieces, the tensile bond strength was measured after immersion in 37 ° C. water for 24 hours, and the remaining 7 test pieces were immersed in 37 ° C. water for 24 hours. Thereafter, a thermal cycle of immersing in cold water at 4 ° C. and warm water at 60 ° C. for 1 minute each was loaded 2000 times, and the tensile adhesive strength was measured. For the measurement of adhesive strength, a universal testing machine (manufactured by Instron) was used, and the tensile adhesive strength was measured under the condition of a crosshead speed of 1 mm / min. All adhesion tests were performed at room temperature of 23 ° C. ± 1 ° C.

Table 2 shows Bis-GMA, 3G, CQ, DMABE, and aluminum oxide powder or zirconium oxide powder as examples of dental materials composed of an organic composite containing an inorganic compound (hereinafter referred to as an inorganic organic composite). The curable compositions 1 to 4 were prepared by blending with the described blending amounts. Next, the produced curable compositions 1 to 4 were each molded into a disk shape (diameter: 15.0 × 2.0 mm), and a photopolymerizer for technical use [trade name “Solidite” (manufactured by Matsukaze Co., Ltd.)] Each was used as a cured product, and inorganic-organic composites 1 to 4 were produced and used as adherends.

The flat surfaces of the prepared disk-like (diameter 15.0 × 2.0 mm) inorganic-organic composites 1 to 4 are used under running water using No. 600 and No. 1200 silicon carbide paper (manufactured by Sankyo Rikagaku Co., Ltd.). After polishing to obtain a smooth surface, ultrasonic cleaning and air drying were performed to obtain an adherend.
The adhesive composition was applied to the adherend surface of the adherend with a mini brush, left as it was for 30 seconds, and then dried with an air syringe until the fluidity of the adhesive composition disappeared. On the other hand, the adhesion surface of a cylindrical stainless steel rod having a diameter of 5 mm × height of 10 mm is air ablated (50 μm alumina beads, 5 kgf / cm ² pressure), and then ultrasonically cleaned and air dried to obtain a bonding strength measuring jig. . Adhesion was performed by interposing “Imperva Dual” kneaded into a uniform paste between the adhesion surface of the adherend and the adhesion surface of the stainless steel bar. At this time, excess cement was removed with a mini brush, and photopolymerization was performed for 10 seconds using “Matsukaze Grip Light II” as a cement margin. All 14 test pieces were immersed in 37 ° C. water, and for 7 test pieces, the tensile bond strength was measured after immersion in 37 ° C. water for 24 hours, and the remaining 7 test pieces were immersed in 37 ° C. water for 24 hours. Thereafter, a thermal cycle of immersing in cold water at 4 ° C. and warm water at 60 ° C. for 1 minute each was loaded 2000 times, and the tensile adhesive strength was measured. For the measurement of adhesive strength, a universal testing machine (manufactured by Instron) was used, and the tensile adhesive strength was measured under the condition of a crosshead speed of 1 mm / min. All adhesion tests were performed at room temperature of 23 ° C. ± 1 ° C.

As is clear from the results of Tables 3 and 4, the adhesion performance to the aluminum oxide flat plate and the zirconium oxide flat plate is from Examples 1 to 10 when the surface treatment with the adhesive composition is not performed as in Comparative Example 1. Furthermore, it showed a low adhesive strength, and further dropped out from the adhesive interface after 2000 thermal cycles. Moreover, when the surface treatment by the adhesive composition is not performed as in Comparative Example 1, the adhesion performance to the inorganic organic composites 1 to 4 which are dental materials made of an organic composite containing an inorganic compound is Example 2 The adhesive strength was lower than 4 and 6, and after 2000 thermal cycles, the adhesive strength was significantly reduced.

As is clear from the results in Table 5, the adhesion performance to the aluminum oxide flat plate and the zirconium oxide flat plate is a composition not containing a phosphonic acid group-containing (meth) acrylate monomer as in Comparative Examples 2-3. The adhesive strength was lower than those of Examples 11 to 13, and further dropped from the adhesive interface after 2000 thermal cycles were applied.

As is clear from the results of Table 6, the adhesion performance to the aluminum oxide flat plate and the zirconium oxide flat plate is two components of a phosphonic acid group-containing (meth) acrylate monomer and an acidic compound as shown in Examples 14-15. In the adhesive composition containing, high initial adhesive performance was exhibited, and no dropout was observed after 2000 cycles of thermal cycling.

_{SiO 2, Al 2 O 3,} ZrO 2 -3Y, zeta potential -pH view of _{3Al 2} O 3 · 2SiO 2

Claims (3)

A dental adhesive composition comprising a phosphonic acid group-containing (meth) acrylate monomer for bonding a dental material comprising an inorganic compound or an organic composite containing an inorganic compound. At least a part of the composition of the dental material is represented by the general formula MO _{m / 2} “M is one or more selected from Al, Zr, Ti, and Mg (m represents the valence of M)”. The dental adhesive composition according to claim 1, which is a dental material comprising an inorganic compound or an organic composite containing an inorganic compound. The phosphonic acid group-containing (meth) acrylate monomer is represented by the following general formula [1].

(In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an optionally substituted alkylene group having 1 to 20 carbon atoms, and R ₃ may have a substituent. The dental adhesive composition according to claim 1, which is represented by a good alkylene group having 1 to 15 carbon atoms.

Images