JP7023053B2 - Coupling organic compounds containing uretdione groups and medical and dental curable compositions containing them. - Google Patents

Description

The present invention relates to a uretdione group and a coupling organic compound having at least one kind of radically polymerizable group in the molecule. Further, the present invention uses porcelain ceramics, metals, resins, composite resins, and other medical and dental materials such as restoration materials, crown materials, prosthesis materials, aesthetic materials, orthodontic materials, preventive materials, abutment construction materials, and root canal materials. The present invention relates to a medical and dental curable composition used in the medical and dental field for adhering to glass ionomer cement, biological hard tissue (enamel and dentin of natural teeth) and the like.

In recent years, composite resins have dramatically improved long-term durability and mechanical properties, and have also had properties such as sustained-release fluorine and X-ray contrast, resulting in defects in the tooth structure due to the onset of dental caries. It has come to be used for the functional and aesthetic restoration of the tooth substance in the case of the occurrence of tooth decay or the occurrence of fracture or dropout of the crown restoration. In addition, the use of this composite resin is expanding to applications such as tooth surface coating materials, fee sealants, orthodontic adhesives, and resin core materials. However, since these composite resins themselves do not have adhesiveness not only to dentin but also to porcelain ceramics and metals, it is essential to use various adhesives together. Especially for dentin, the adhesive is required to have excellent adhesiveness to both enamel whose main component is an inorganic component such as hydroxyapatite and dentin whose main component is an organic component such as collagen. Has been done. More recently, it has become an issue to firmly adhere to porcelain ceramics, metals, resins, composite resins, glass ionomer cements and the like, and to have adhesive durability.

In the conventional adhesive material, the tooth surface is treated with a strong etching material such as phosphoric acid, and then a bonding material is applied to bond the tooth substance and the composite resin. However, the method of treating the tooth surface with an acid etching material has a drawback that it requires complicated operation steps such that the acid applied to the tooth surface needs to be sufficiently removed by washing with water and then dried. .. In addition, the bonding method using an acid-etched material is sufficient for enamel due to the formation of a rough surface by decalcification of the acid-etched material, sufficient penetration of the bonding material, and macromechanical fitting based on hardening. It showed adhesiveness. On the other hand, for dentin, sponge-like collagen fibers are exposed by decalcification of the acid etching material, so that the bonding material does not sufficiently penetrate into the collagen fibers and it is difficult to obtain sufficient adhesiveness. there were. Therefore, in order to obtain high adhesiveness to dentin, an acid tooth surface treatment material instead of a phosphoric acid etching material has been proposed. For example, Japanese Patent Application Laid-Open No. 62-33109 contains a dentin surface treatment material containing a sulfonic acid group-containing polymer, and Japanese Patent Application Laid-Open No. 62-231652 includes a dentin surface treatment material containing a metal halide. -279851 is a dentin surface treatment material containing an amphoteric amino compound, JP-A 1-279815 is a dentin surface treatment material containing an organic carboxylic acid and a metal chloride, and JP-A-5-163111 is a dentin surface treatment material. Examples thereof include dentin surface treatment materials containing organic carboxylic acid and iron phosphate. However, it has been difficult to obtain sufficient adhesive force against dentin even when these acid tooth surface treatment materials are used.

Further, in Patent No. 2865794, as a polymerizable compound containing an acid group, (a) formation 1: [in the formula, R1 is a hydrogen atom or a methyl group, and R2 is an alkylene group having 5 to 10 carbon atoms. , R3 represent an alkylene group having 1 to 6 carbon atoms. ], An adhesive composition containing a (meth) acrylic acid ester derivative containing a phosphonic acid group, (b) at least one radically polymerizable monomer and (c) at least one polymerization initiator is disclosed. There is.

When the phosphonic acid group contained in the (meth) acrylic acid ester derivative is applied to the dentin, the phosphonic acid group chemically bonds with the calcium component of the dentin, and as a result, a polymerizable group can be imparted to the dentin surface. .. After that, it was announced that the primer was effective for permeation into the collagen fibers exposed by the acid tooth surface treatment material applied to the tooth surface [Journal of Dental Research Vol.63, P1087-1089, 1984: Glutaraldehyde / 2- Since HEMA / primer composition consisting of water], a three-step surgical method consisting of an acid-treated material / primer / bonding material has been performed. As a proposal of an adhesion method accompanied by this three-step technique, the methods described in Japanese Patent No. 3397573 and Japanese Patent No. 2962628 can be mentioned. In addition, since 2-HEMA, which is a water-soluble polymerizable monomer contained in the primer, has mucosal irritation, a primer composition containing another water-soluble polymerizable monomer in place of 2-HEMA is also available. It has been disclosed. For example, Japanese Patent Application Laid-Open No. 2004-137211 describes a primer composition containing polyethylene glycol or polyethylene glycol monomethacrylate, and Japanese Patent No. 2786294 describes a primer composition containing glyceryl mono (meth) acrylate. However, although these adhesive methods have many steps and are complicated to operate, and have high adhesion to enamel, their adhesion to dentin has not yet reached a sufficient level.

In recent years, an adhesive monomer having an acidic group in the molecule has been developed, and a self-etching primer that simplifies a complicated operation step that can simultaneously perform an acid treatment for decalcifying the tooth surface and a primer treatment for infiltrating collagen fibers has been developed. It has been proposed. When this primer is used, the technique does not require acid treatment on the tooth surface, and the self-etching primer is treated (applied / left) on the tooth surface, dried, and then the bonding material is applied. That is, by treating the tooth surface formed with the cavity with a self-etching primer, the smear layer generated by the formation of the tooth cavity is dissolved and penetrates into the tooth substance (enamel / dentin). After drying, a bonding material is applied thereto, so that the self-etching primer and the bonding material are integrated and cured, so that a strong adhesive layer can be obtained.

Numerous proposals have been made for these self-etching primer compositions. For example, Japanese Patent Application Laid-Open No. 1-113057 contains a primer composition consisting of a water / water-soluble film-forming agent / acid salt, and Japanese Patent Application Laid-Open No. 2634276 contains water / a polymerizable compound having a hydroxyl group / a polymerizable compound having an acid group. / Primer composition consisting of curing agent, Japanese Patent No. 3480654 and Japanese Patent No. 3487389 include water / dental primer composed of a phosphate group-containing polymerizable monomer / a polyvalent carboxylic acid group-containing polymerizable monomer. Japanese Patent Application Laid-Open No. 7-82115 describes a primer composition comprising a vinyl compound having an acidic group / a water-soluble vinyl compound having a hydroxyl group / water / aromatic sulfinate / aromatic amine.
-223289 A primer composition consisting of 2-HEMA / water containing an organic acid or an inorganic acid, and JP-A-4-8368 A water / polymerizable compound having an acid group / a polymerizable compound having a hydroxyl group / Examples thereof include a primer composition composed of an amino compound having an acid group. Although these compositions show a certain degree of adhesiveness to dentin, they do not have sufficient adhesiveness to enamel due to their poor decalcifying action on inorganic components. Further, since the primer composition contains an acidic group-containing polymerizable monomer and a water-soluble polymerizable monomer having poor polymerizable properties, the curing after coating of the bonding material is insufficient, and as a result, the oral cavity is harsh. There was a problem in adhesive durability in the environment. Furthermore, since these primer compositions are basically in an acidic atmosphere in which water / acidic group-containing polymerizable monomers coexist, the intramolecular main chain and functional groups in the components contained in the primer composition Deterioration and deterioration due to hydrolysis occurred, and there were major problems in storage stability and material stability. Therefore, it was necessary to divide the packaging form.

In order to solve these problems, a number of proposals have been made to sufficiently cure the adhesive layer and improve the dentin adhesiveness by combining a primer and a bonding material. For example, JP-A-2000-212015 and JP-A-2000-16911 include a bonding material containing an acylphosphine oxide compound as a photopolymerization initiator and a primer composition (having a polymerizable monomer / hydroxyl group having an acidic group). Dental adhesive system consisting of polymerizable monomer / water), Japanese Patent Application Laid-Open No. 2004-26838 describes a primer composition containing a phosphate group-containing polymerizable monomer / water and a polyvalent rubon acid. Dental adhesive kit consisting of a bonding material containing a group-containing polymerizable monomer / polymerization initiator, Patent No. 3236030 includes a vinyl monomer having a specific molecular structure having a carboxyl group or an acid anhydride thereof. A novel bonding method comprising an adhesive composition composed of a primer solution and a vinyl monomer having an acidic group, Japanese Patent Application Laid-Open No. 2000-204010 describes a sulfonic acid group-containing polymerizable monomer / water-soluble polymerizable monomer / water. A dental adhesive kit comprising a primer composition containing a primer composition and an adhesive containing an acidic phosphoric acid ester-based polyfunctional polymerizable monomer. A dental adhesive kit comprising a primer composition containing a polymerizable monomer / water and an adhesive containing a polyvalent carboxylic acid group-containing polyfunctional polymerizable monomer, Japanese Patent Application Laid-Open No. 11-180814 contains an acidic group. A dentin consisting of a self-etching primer containing (meth) acrylate / water-soluble organic solvent / water and a dentin adhesive containing (meth) acrylate / photopolymerization initiator / photopolymerization accelerator / filler having no acidic group and hydroxyl group. Adhesive set, JP-A-6-24928 discloses a primer solution composition containing a specific metal compound / acidic group-containing polymerizable monomer / polymerizable monomer and trialkylboron or a partial oxide thereof. An adhesive consisting of a curable composition contained as an initiator, Patent No. 3449755 discloses an acidic group-containing vinyl polymer compound / a hydroxyl group-containing water-soluble vinyl compound / a primer composition containing water / aromatic amine and an acidic group-containing acrylic. Examples thereof include an adhesive kit made of an acrylic adhesive containing a based monomer / an acidic group-free acrylic monomer / a polymerization initiator.

All of these proposals are used in combination with a specific bonding material in order to improve the curability of a primer composition containing a poorly polymerizable acidic group-containing polymerizable monomer or a water-soluble polymerizable monomer. , Achieves adhesion to dentin (enamel and dentin). However, the low curability due to the constituents of the primer composition has not been fundamentally improved, and therefore, it is recognized that the adhesive durability to both enamel and dentin is insufficient. Was.

Japanese Patent Application Laid-Open No. 10-251115 describes, as the acid group-containing polymerizable compound, (A) a phosphate group-containing polymerizable monomer having a -COP ester bond, and (B) a polyvalent carboxylic acid group-containing polymerizable compound. Dental primers containing monomers and (C) water as main components are disclosed. According to this dental primer, a high adhesive strength of 20 MPa or more can be obtained for both dentin and enamel. However, the ester bond in the phosphoric acid group-containing polymerizable monomer used for this primer is susceptible to hydrolysis, and has problems in storage stability and adhesive durability. Further, for adhesion to an inorganic material such as porcelain ceramics, a silane coupling agent such as 3-methacryloxypropyltrimethoxysilane is useful. However, as described above, since the curable composition for medical and dental use is required to have adhesiveness to bones and dentin such as enamel and dentin at the same time, an acidic compound and water coexist. Therefore, a silane coupling agent such as 3-methacryloxypropyltrimethoxysilane of the prior art, which is easily hydrolyzed by an acid, could not coexist. Therefore, there was no choice but to supply in individual packaging form. That is, for adhesion to inorganic materials such as porcelain ceramics, first a silane coupling treatment such as 3-methacryloxypropyltrimethoxysilane is performed, and then the medical and dental curable composition is applied again. A complicated technique has been required.

Japanese Unexamined Patent Publication No. 62-33109 Japanese Patent Application Laid-Open No. 62-231652 Japanese Unexamined Patent Publication No. 63-279851 Japanese Unexamined Patent Publication No. 1-279815 Japanese Patent Application Laid-Open No. 5-163111 Japanese Patent No. 2867594 Japanese Patent No. 3397573 Japanese Patent No. 2962628 Japanese Unexamined Patent Publication No. 2004-137211 Japanese Patent No. 2782964 Japanese Unexamined Patent Publication No. 1-113057 Japanese Patent No. 2634276 Japanese Patent No. 3480654 Japanese Patent No. 3487389 Japanese Unexamined Patent Publication No. 7-82115 Japanese Patent Application Laid-Open No. 62-223289 Japanese Unexamined Patent Publication No. 4-8368 Japanese Patent Laid-Open No. 2000-212015 Japanese Unexamined Patent Publication No. 2000-16911 Japanese Unexamined Patent Publication No. 2004-26838 Patent No. 3236030 Gazette Japanese Unexamined Patent Publication No. 2000-204010 Japanese Unexamined Patent Publication No. 9-295913 Japanese Unexamined Patent Publication No. 11-180814 Japanese Unexamined Patent Publication No. 6-24928 Japanese Patent No. 3449755 Japanese Unexamined Patent Publication No. 10-251115

Journal of Dental Research Vol.63, P1087-1089, 1984

The problems to be solved by the present invention are adhesiveness and a harsh oral environment that are sufficiently cured after removal of volatile components and firmly adhere to biological hard tissues such as porcelain ceramics, bone, enamel and dentin. It is an object of the present invention to provide a medical and dental curable composition capable of exhibiting adhesive durability that can withstand even below. A further problem to be solved by the present invention is a medical department that enables a one-component packaging form having excellent storage stability, which is less susceptible to deterioration and deterioration due to hydrolysis of constituents due to environmental temperature, acidity of solution, and the like. It is also to provide a dental curable composition.

As a result of repeated studies to solve the above problems, the present inventors have obtained a coupling organic compound having a uretdione group and at least one kind of radically polymerizable group in the molecule, as a medical and dental curable composition. It was found that the above-mentioned problems can be solved by using the above-mentioned problem. More specifically, at least one polymerization with at least one phosphonic acid group (-PO (OH) 2) or phosphonic acid monoester group (-PO (OH) (OR)) directly linked to a carbon atom in the molecule. A phosphonic acid group-containing polymerizable monomer having a sex unsaturated group, and a group having at least two or more carboxylic acid groups in the molecule, or a group that easily reacts with water to form two or more carboxylic acid groups. A combination of a polyvalent carboxylic acid group-containing polymerizable monomer having at least one polymerizable unsaturated group, a uretdione group, and a coupling organic compound having at least one kind of radically polymerizable group in the molecule. By using it, it can be firmly adhered to any of biological hard tissues such as porcelain ceramics, bone, enamel and ivory, and it also has adhesive durability that can withstand even in a harsh oral environment. We found that we were doing this and completed the present invention. Further, a phosphonic acid group-containing polymerizable monomer, a polyvalent carboxylic acid group-containing polymerizable monomer, and a coupling organic compound having a uretdione group and at least one kind of radically polymerizable group in the molecule are combined. We found that the curable composition for medical and dental use also has excellent storage stability that is resistant to deterioration and deterioration due to hydrolysis of the constituents even in an acidic atmosphere of pH 2 to pH 3 in which water coexists. The present invention has been completed.

By using the uretdione group of the present invention and a coupling organic compound having at least one kind of radically polymerizable group in the molecule in a curable composition for medical dentistry, porcelain ceramics, bone, enamel and dentin can be used. It can firmly adhere to any of the biological hard tissues such as, and also has adhesive durability that can withstand even in a harsh oral environment. More specifically, the present invention has a coupling organic compound having a uretdione group and at least one kind of radically polymerizable group in the molecule, a phosphonic acid group-containing polymerizable monomer, and a polyvalent carboxylic acid group. The medical and dental curable composition containing a polymerizable monomer, a polymerizable monomer, water, a water-soluble organic solvent, a polymerization initiator and a photoacid generator exhibited excellent adhesiveness and adhesive durability. In addition, it was also found that it had excellent storage stability even in an acidic atmosphere in which water coexisted.

Here, regarding the adhesion mechanism to porcelain ceramics of the prior art and the possibility of preparing a one-component medical and dental curable composition, and the uretdione group of the present invention and at least one kind of radically polymerizable group in the molecule. The mechanism of adhesion of the coupling organic compound to porcelain ceramics and the possibility of preparing a one-component medical and dental curable composition will be described in detail.

The compound containing a primary amino group exhibits cationicity under acidic conditions and is positively charged. On the other hand, inorganic materials such as porcelain ceramics and glass have silanol groups on the surface and are anionic and negatively charged (ζ potential is negative). Therefore, compounds containing primary amino groups and inorganic materials such as porcelain ceramics and glass are bonded (adhered) by their electrostatic effects. Here, it has already been mentioned that the phosphonic acid group-containing polymerizable monomer and the polyvalent carboxylic acid group-containing polymerizable monomer are effective for adhesion to biological hard tissues such as bone, enamel and dentin. It's a street. Therefore, in order to firmly adhere to any of biological hard tissues such as porcelain ceramics, bone, enamel and ivory, a phosphonic acid group-containing polymerizable monomer and a polyvalent carboxylic acid group-containing polymerizable simple substance are used. A compound containing a weight and a primary amino group may be allowed to coexist to prepare a one-component medical and dental curable composition, but when these are coexisted, the primary amino group is contained. The compound forms a complex with a phosphonic acid group-containing polymerizable monomer or a polyvalent carboxylic acid group-containing polymerizable monomer, and the adhesive ability is lost. Therefore, it is difficult to prepare a one-component medical and dental curable composition. Further, a silane coupling agent such as 3-methacryloylpropyltrimethoxysilane forms a siloxane bond by a condensation reaction with a silanol group via dealcoholization and adheres. Coexistence of these silane coupling agents is difficult because dealcoholization and condensation easily proceed in an environment where water and acidic monomers coexist. Therefore, it is difficult to prepare a one-component medical and dental curable composition. Furthermore, radically polymerizable monomers having an isocyanato group such as 2-isocyanato ethyl methacrylate easily react with functional groups having active hydrogen such as a hydroxyl group, a thiol group, an amino group and a silanol group. Therefore, it is effective for modifying porcelain ceramics and glass surfaces. However, due to its high activity, coexistence is difficult because the reaction easily proceeds with them in the coexistence of water or alcohol. Therefore, it is difficult to prepare a one-component medical and dental curable composition. The coupling organic compound having the uretdione group and at least one kind of radical polymerizable group in the molecule of the present invention is stable in an acidic atmosphere of pH 2 to pH 3, but gives heat energy, irradiates an electromagnetic wave, and a photoacid generator. Degradation of uretdione groups proceeds with a significant decrease in pH due to the formation of isocyanato groups. This generated isocyanate group-containing compound has the effect of reacting with the silanol groups of inorganic materials such as porcelain ceramics and glass to exhibit strong adhesion. Therefore, the coupling organic compound having the uretdione group and at least one kind of radically polymerizable group in the molecule of the present invention can coexist with water and an acidic monomer, and is a one-component medical dental curable composition. Can be prepared.

The uretdione group of the present invention and the coupling organic compound having at least one kind of radically polymerizable group in the molecule can be used without any limitation as long as it has the molecular structure shown in [Chemical Formula 2]. Further, this coupling organic compound may be used not only as one kind but also as a combination of a plurality of kinds.

To explain the structure shown in [Chemical formula 2] in more detail, A in the equation has H ₂ C = CH-, H ₂ C = C (CH ₃ )-, H ₂ C = CH-C ₆ H ₄ -groups. Representation (C ₆ H ₄ indicates a phenylene group), B is -C (O) -O-, -C (O) -S-, --C (O) -NH-, -NH-C (O) Represents the -NH-, -NH-C (O) -S-, -NH-C (O) -O- groups, where R is a linear or branched alkylene group from C ₁ to C ₆₀ , -C. (O) -O-, -C (O) -S-, -C (O) -NH-, -NH-C (O) -NH-, -NH-C (O) -S-, -NH- It may contain C (O) -O-, -O-, -S- groups. Note that a is an integer from 1 to 6.
The typical chemical structures of the uretdione group of the present invention and the coupling organic compound having at least one kind of radically polymerizable group in the molecule are described below.

When the coupling organic compound of the present invention is used in a curable composition for medical dentistry, it is preferably contained in an amount of 1 part by weight to 10 parts by weight, more preferably 4 parts by weight, in 100 parts by weight of the curable composition for medical dentistry. Parts to 6 parts by weight. When the amount of the coupling organic compound is less than 1 part by weight, the amount of the coupling organic compound is too small with respect to the silanol group on the adherend surface, so that sufficient adhesive strength cannot be obtained. On the contrary, when it exceeds 10 parts by weight, the fragile bonds between the coupling organic compounds (increase in the uncondensed portion of the xerogel structure) increase, so that sufficient adhesive strength cannot be obtained.

The components other than the uretdione group and the coupling organic compound having at least one kind of radically polymerizable group in the molecule used in the medical and dental curable composition of the present invention are as follows: (a) Phosphonic acid group-containing polymerizable single amount. body;
(B) Multivalent carboxylic acid group-containing polymerizable monomer;
(C) Polymerizable monomer;
(D) Water;
(E) Water-soluble organic solvent (f) Polymerization initiator (g) Photoacid generator, and details of each component thereof are shown.

(A) Phosphonate group-containing polymerizable monomer The phosphonic acid group-containing polymerizable monomer (a) contained as an essential component in the medical and dental curable composition of the present invention is at least a carbon atom in the molecule. Means a polymerizable monomer having one (-PO (OH) 2) or phosphonic acid monoester group (-PO (OH) (OR)) directly linked and at least one polymerizable unsaturated group. That is, any functional group having any functional group in the molecule can be used without any limitation as long as it satisfies these conditions. In addition, the phosphonic acid group-containing polymerizable monomer is unsaturated with the number of phosphonic acid groups or phosphonic acid monoester groups in the molecule and radically polymerizable such as (meth) acryloyl group, styryl group, vinyl group and allyl group. The type and number of radicals are not particularly limited. By containing the phosphonic acid group-containing polymerizable monomer in the medical and dental curable composition of the present invention, as compared with the polymerizable monomer having a phosphoric acid monoester group or a phosphoric acid diester group, In particular, it can exhibit excellent dentin adhesion performance with respect to enamel. In addition, since the phosphonic acid group-containing polymerizable monomer does not have the phosphonic acid group bonded to the oxygen atom by an ester bond, it is less susceptible to intramolecular hydrolysis even in an acidic atmosphere in which water coexists, and storage is stable. Excellent in sex. Therefore, the packaging form can be not only a two-component packaging form divided into two, but also a one-component packaging form.

Among these phosphonic acid group-containing polymerizable monomers, R1 is a hydrogen atom or a methyl group, and R2 is an alkylene group having 5 to 10 carbon atoms, which has excellent dentin adhesion and storage stability. , R3 represent an alkylene group having 1 to 6 carbon atoms. ], It is preferable to use the phosphonic acid group-containing polymerizable monomer. Specific examples of the phosphonic acid group-containing polymerizable monomer represented by the general formula (I) include, but are not limited to, the compound of [Chemical Formula 21].

These phosphonic acid group-containing polymerizable monomers can be used alone or in combination of two or more. Among these phosphonic acid group-containing polymerizable monomers, 6- (meth) acryloyloxyhexylphosphonoacetate, 6- (meth) acryloyloxyhexyl-3-phosphonopropionate, 10- (meth) acryloyloxy It is more preferable to use decyl-3-phosphonoacetate, 10- (meth) acryloyloxydecylphosphonopropionate, 5- (meth) acryloyloxypentyl-3-phosphonopropionate and the like.

The content of these phosphonic acid group-containing polymerizable monomers can be appropriately selected depending on the intended use or purpose of use and the method of use of the medical and dental curable composition, but is preferably 0.1 to 40. It is in the range of 0.0 parts by weight.
When the content of these phosphonic acid group-containing polymerizable monomers exceeds 40.0 parts by weight, the curability due to the polymerizable property is lowered, which adversely affects the adhesive properties. On the other hand, when the content of the phosphonic acid group-containing polymerizable monomer is less than 0.1 parts by weight, no effect is observed in the adhesiveness to the enamel.

(B) Multivalent carboxylic acid group-containing polymerizable monomer The polyvalent carboxylic acid group-containing polymerizable monomer (b) contained as an essential component in the medical and dental curable composition of the present invention is contained in the molecule. It means a polymerizable monomer having at least two or more carboxylic acid groups, or a group which easily reacts with water to form two or more carboxylic acid groups, and at least one polymerizable unsaturated group. That is, any functional group that satisfies these conditions can be used without any limitation. Further, the polyvalent carboxylic acid group-containing polymerizable monomer is not particularly limited in the type and number of radically polymerizable unsaturated groups such as (meth) acryloyl group, styryl group, vinyl group and allyl group contained in the molecule. .. By containing the polyvalent carboxylic acid group-containing polymerizable monomer in the medical and dental curable composition of the present invention, excellent dentin adhesion performance to dentin can be exhibited.

Specific examples of the polyvalent carboxylic acid group-containing polymerizable monomer include aconitic acid, mesaconic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, glutaconic acid, citraconic acid, and utraconic acid. 1,4-di (meth) acryloyloxyethyl pyromellitic acid, 6- (meth) acryloyloxynaphthalene-1,2,6-tricarboxylic acid, 1-butene 1,2,4-tricarboxylic acid, 3-butene 1, 2,3-Tricarboxylic acid, 4- (meth) acryloyloxyethyl trimellitic acid and its anhydride, 4- (meth) acryloyloxybutyltrimellitic acid and its anhydride, β- (meth) acryloyloxyethyl hydrogensac Cineate, β- (meth) acryloyloxyethyl hydrogenmaleate, 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid, 4- (meth) acryloyloxyethoxycarbonylphthalic acid, 4- (meth) ) Acryloyloxybutyloxycarbonylphthalic acid, 4- (meth) acryloyloxyhexyloxycarbonylphthalic acid, 4- (meth) acryloyloxyoctyloxycarbonylphthalic acid, 4- (meth) acryloyloxydecyloxycarbonylphthalic acid and their Anhydrous, 6- (meth) acryloyloxy-1,1-hexanedicarboxylic acid, 8- (meth) acryloyloxy-1,1-octanedicarboxylic acid, 10- (meth) acryloyloxy-1,1-decandycarboxylic acid , 11- (meth) acryloyloxy-1,1-undecandicarboxylic acid and the like, but are not limited thereto. These polyvalent carboxylic acid group-containing polymerizable monomers can be used alone or in combination of two or more. Among these polyvalent carboxylic acid group-containing polymerizable monomers, it is more preferable to use 4-methacryloyloxyethyl trimellitic acid and its anhydride, 4-acryloyloxyethyl trimellitic acid and its anhydride, and the like.

The content of these polyvalent carboxylic acid group-containing polymerizable monomers can be appropriately selected depending on the intended use or purpose of use and the method of use of the curable composition for medical dentistry, but is preferably 0.1. It is in the range of ~ 40.0 parts by weight. When the content of these polyvalent carboxylic acid group-containing polymerizable monomers exceeds 40.0 parts by weight, the curability due to the polymerizable property is lowered, which adversely affects the adhesive properties. On the other hand, when the content of the polyvalent carboxylic acid group-containing polymerizable monomer is less than 0.1 parts by weight, no effect is observed in the adhesiveness to dentin.

Further, in the case of further enhancing the adhesiveness to the biological hard tissue in the medical and dental curable composition of the present invention, or when imparting the adhesiveness to various adherends containing noble metals and the like, a phosphonic acid group-containing polymerizable simpler is used. It can contain a combination of an acidic group-containing polymerizable monomer other than a weight or a polyvalent carboxylic acid group-containing polymerizable monomer, and a polymerizable monomer containing a sulfur atom in the molecule. The acidic group-containing polymerizable monomer other than the phosphonic acid group-containing polymerizable monomer and the polyvalent carboxylic acid group-containing polymerizable monomer is long as it has at least one acidic group in the molecule. In particular, the type of acidic group is not limited, and any acidic group-containing polymerizable monomer having an acidic group can be used. Specific examples of the acidic groups contained in these acidic group-containing polymerizable monomers include phosphoric acid groups (monoesters or diesters), monocarboxylic acid groups, pyrophosphate groups, sulfonic acid groups, and thiophosphate groups. However, it is not limited to these. Further, the number of radically polymerizable unsaturated groups (monofunctional group or polyfunctional group) and the type thereof of the polymerizable monomer containing these acidic groups can be used without any limitation. Specific examples of the unsaturated group contained in the acidic group-containing polymerizable monomer include (meth) acryloyl group, styryl group, vinyl group, allyl group and the like. Among these unsaturated groups, (meth) acryloyl It is preferably an acidic group-containing polymerizable monomer having a group. Further, these acidic group-containing polymerizable monomers may also contain other functional groups such as an alkyl group, a halogen, an amino group, a glycidyl group and a hydroxyl group in the molecule.

Specific examples of the acidic group-containing polymer having a (meth) acryloyl group as an unsaturated group are as follows. Examples of the acidic group-containing polymerizable monomer having a phosphoric acid group include (meth) acryloyloxymethyldihydrogen phosphate, 2- (meth) acryloyloxyethyl dihydrogen phosphate, and 3- (meth) acryloyloxypropyl dihydro. Genphosphate, 4- (meth) acryloyloxybutyl dihydrogenphosphate, 5- (meth) acryloyloxypentyl dihydrogenphosphate, 6- (meth) acryloyloxyhexyl dihydrogenphosphate, 7- (meth) acryloyloxyheptyl Dihydrogenphosphate, 8- (meth) acryloyloxyoctyl dihydrogenphosphate, 9- (meth) acryloyloxynonyl dihydrogenphosphate, 10- (meth) acryloyloxydecyldihydrogenphosphate, 11- (meth) acryloyl Oxyundecyldihydrogenphosphate, 12- (meth) acryloyl oxide decyldihydrogenphosphate, 16- (meth) acryloyloxyhexadecyldihydrogenphosphate, 20- (meth) acryloyloxyeicosyldihydrogenphosphate, di (Meta) Acryloyloxyethyl Hydrogen Phosphate, Di (Meta) Acryloyl Oxybutyl Hydrogen Phosphate, Di (Meta) Acryloyl Oxyhexyl Hydrogen Phosphate, Di (Meta) Acryloyl Oxyoctyl Hydrogen Phosphate, Di (Meta) Acryloyl Oxynonyl Hydrogenphosphate, di (meth) acryloyloxydecylhydrogenphosphate, 1,3-di (meth) acryloyloxypropyl-2-dihydrogenphosphate, 2- (meth) acryloyloxyethylphenylhydrogenphosphate, 2-( Examples include, but are not limited to, acryloyloxyethyl 2'-bromoethylhydrogen phosphate, (meth) acryloyloxyethylphenylphosphonate, and the like.

Examples of the acidic group-containing polymerizable monomer having a monocarboxylic acid group include (meth) acrylic acid, 2-chloro (meth) acrylic acid, 3-chloro (meth) acrylic acid, and 2-cyano (meth) acrylic. Acid, N- (meth) acryloyl-p-aminobenzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, 2- (meth) acryloyloxybenzoic acid, p-vinyl benzoic acid, 5- (meth) acryloylamino Examples thereof include, but are not limited to, pentylcarboxylic acid.

Examples of the acidic group-containing polymerizable monomer having a pyrophosphate group include dipyrophosphate [2- (meth) acryloyloxyethyl], dipyrophosphate [3- (meth) acryloyloxypropyl], and dipyrophosphate [ 4- (meth) acryloyloxybutyl], dipyrophosphate [5- (meth) acryloyloxypentyl], dipyrophosphate [6- (meth) acryloyloxyhexyl], dipyrophosphate [7- (meth) acryloyloxyheptyl] ], Dipyrophosphate [8- (meth) acryloyloxyoctyl], dipyrophosphate [9- (meth) acryloyloxynonyl], dipyrophosphate [10- (meth) acryloyloxydecyl], dipyrophosphate [12-]. (Meta) acryloyl oxide decyl], tetra pyrophosphate [2- (meth) acryloyloxyethyl], tripyrophosphate [2- (meth) acryloyloxyethyl] and the like, but are not limited thereto.

Examples of the acidic group-containing polymerizable monomer having a sulfonic acid group include 2- (meth) acrylamide-2-methylpropanesulfonic acid, styrenesulfonic acid, 2-sulfoethyl (meth) acylate, and 4- (meth). ) Acryloyloxybenzene sulfonic acid, 3- (meth) acryloyloxypropane sulfonic acid and the like, but are not limited thereto.

Examples of the acidic group-containing polymerizable monomer having a thiophosphate group include, but are not limited to, 10- (meth) acryloyloxydecyldihydrogendithiophosphate.

Although the acidic group-containing polymerizable monomers are shown above, the present invention is not limited to these, and the polymerizable monomers having these acidic groups can be used alone or in combination of two or more. Further, as these acidic group-containing polymerizable monomers, not only monomers having a short main chain but also oligomers having a long main chain, prepolymers, polymers and the like can be used without any limitation. Derivatives of acidic group-containing polymerizable monomers such as metal salts, ammonium salts or acidified compounds in which the acidic groups of these acidic group-containing polymerizable monomers are partially neutralized can also be applied to various adherends. It can be used as long as it does not adversely affect the adhesiveness of.

In order to impart adhesiveness to a noble metal to the medical and dental curable composition of the present invention, it is also effective for the present invention to use a polymerizable monomer containing a sulfur atom in the molecule. Any polymerizable monomer containing a sulfur atom in the molecule can be used regardless of the type and number of unsaturated groups and the presence or absence of other functional groups. Specific examples of the polymerizable monomer containing a sulfur atom in a molecule having a (meth) acryloyl group as an unsaturated group include a (meth) acrylate having a triazinethiol group and a (meth) acrylate having a mercapto group. (Meta) acrylate having a polysulfide group, (meth) acrylate having a thiophosphate group, (meth) acrylate having a disulfide ring-type group, (meth) acrylate having a mercaptodiathiazole group, (meth) acrylate having a thiouracil group, tiylan Examples thereof include (meth) acrylates having a group, but the present invention is not limited thereto. Polymerizable monomers containing sulfur atoms in these molecules can be used alone or in combination of two or more.

(C) Polymerizable monomer The polymerizable monomer (c) that can be used in the medical and dental curable composition of the present invention is monofunctional or monofunctional regardless of the type of radically polymerizable unsaturated group. It can be used without any limitation in any of the polyfunctionalities. Examples of the type of radically polymerizable unsaturated group contained in the polymerizable monomer include (meth) acryloyl group, (meth) acrylicmid group, styryl group, vinyl group, allyl group and the like, and in particular (meth). It is preferable to use a polymerizable monomer having an acryloyl group or a (meth) acrylicmid group as an unsaturated group. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, (Meta) acrylic acid esters such as cyclohexyl (meth) acrylate, benzyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and isobonyl (meth) acrylate, Silane compounds such as γ- (meth) acryloyloxypropyltrimethoxysilane and γ- (meth) acryloyloxypropyltriethoxysilane, nitrogen-containing compounds such as 2- (N, N-dimethylamino) ethyl (meth) acrylate, 2,2-bis (4- (meth) acryloyloxyphenyl) propane, 2,2-bis (4- (3- (meth) acryloyloxy-2-hydroxypropoxy) phenyl) propane, 2,2-bis (4) -(Meta) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxytetraethoxyphenyl) propane, 2, , 2-Bis (4- (meth) acryloyloxypentaethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydipropoxyphenyl) propane, 2 (4- (meth) acryloyloxyethoxyphenyl)- 2 (4- (meth) acryloyloxydiethoxyphenyl) propane, 2 (4- (meth) acryloyloxydiethoxyphenyl) -2 (4- (meth) acryloyloxytriethoxyphenyl) propane, 2 (4- (meth) ) Acryloyloxydipropoxyphenyl) -2 (4- (meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydipropoxyphenyl) propane, 2,2-bis (4-) (Meta) Acryloyloxyisopropoxyphenyl) Propane, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, propylene glycol Di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, di-2- (meth) acryloyl Examples thereof include oxyethyl-2,2,4-trimethylhexamethylene dicarbamate, trimethylolpropane tri (meth) acrylate, trimethylolethanetri (meth) acrylate, and trimethylolpropane tri (meth) acrylate. Examples of the hydrophobic polymerizable monomer containing an aliphatic tetrafunctional group include pentaerythritol tetra (meth) acrylate, pentaerythritol tetraacrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate, 3 -Polymeric monomer having a hydroxyl group such as chloro-2-hydroxypropyl (meth) acrylate and methylcyclohexanediisocyanate, methylenebis (4-cyclohexylisocyanate), hexamethylenediisocyanate, trimethylhexamethylene diisocyanate, isophoronediisocyanate, diisocyanatemethylmethyl 2,2, Di (meth) acrylates having a bifunctional or trifunctional or higher polymerizable group derived from an adduct with a diisocyanate compound such as benzene, 4,4-diphenylmethane diisocyanate and having a urethane bond, etc. -Bis (4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl) propane (Bis-GMA), 2,2-bis (4-methacryloyloxyethoxyphenyl) propane (D-2.6E), di (methacryloyloxy) ) -2,2,4-trimethylhexamethylene diurethane (UDMA), triethylene glycol dimethacrylate (TEGDMA), neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, 2-hydroxyethyl (meth) acrylicate, 2, -Hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1,2-dihydroxypropyl (meth) acrylate, 1,3-dihydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-Hydroxypropyl-1,3-di (meth) acrylate, 3-hydroxypropyl-1,2-di (meth) acrylate, pentaerythritol di (meth) acrylate, 2-trimethylammonium ethyl (meth) acrylic chloride, ( Meta) acrylamide, 2-hydroxyethyl (meth) acrylamide, polyethylene glycol di (meth) acrylate (with 9 or more oxyethylene groups), 2-hydroxyethyl (meth) acrylate, polyethylene glycol di (meth) Acrylate (with 9 oxyethylene groups), polyethylene glycol di (meth) acrylate (with 14 oxyethylene groups), po. Examples thereof include, but are not limited to, lithium glucol di (meth) acrylate (those having 23 oxyethylene groups).

The water (d) contained as an essential component in the curable composition for medical dentistry of the present invention is a phosphonic acid group-containing polymerizable monomer or polyvalent carboxylic acid group contained in the curable composition for medical dentistry. It has the function of activating the acidic group of the contained polymerizable monomer and the like to promote the decalcification action on the living hard tissue and to promote the penetration into the living hard tissue. Therefore, water can be used without any limitation as long as it does not contain impurities that adversely affect storage stability, biocompatibility, polymerizable property, biohard tissue adhesiveness and the like. It is preferable to use distilled water or ion-exchanged water. The content of water can be appropriately selected depending on the intended use or purpose of use and the method of use of the medical and dental curable composition of the present invention, preferably in the range of 0.1 to 80.0 parts by weight. be. If the water content exceeds 80.0 parts by weight, the composition cannot maintain a uniform state and separates, which adversely affects the storage stability. On the other hand, if the water content is less than 0.1 parts by weight, sufficient adhesiveness cannot be obtained for various adherends including biological hard tissues.

(E) Water-soluble organic solvent The water-soluble organic solvent (e) contained as an essential component in the medical dental curable composition of the present invention is a phosphonic acid group-containing polymerization contained in the medical dental curable composition. The role of a dissolution accelerator that dissolves various polymerizable monomers including sex monomers and polyvalent carboxylic acid group-containing polymerizable monomers, water, polymerization initiators and other compounding components at arbitrary ratios. In addition to having the function of promoting the penetration of the curable composition for medical and dental use into the dentin. In addition, the liquid viscosity of the curable composition for medical and dental use can be lowered, and operability such as dropping from a container or applying to a portion to be adhered can be improved. Specific examples of this water-soluble organic solvent include alcohols such as methanol, ethanol, 1-propanol, 2-propanol and 1-butanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether and dipropylene glycol. Examples thereof include ether compounds such as monomethyl ether, tetrahydrofuran and dimethoxyethane, and water-soluble organic solvents such as ketone compounds such as acetone and methyl ethyl ketone, but the solvent is not limited thereto and can be used without any limitation. In addition, these water-soluble organic solvents can be used alone or in combination of several kinds. Among these water-soluble organic solvents, methanol, ethanol, 1-propanol, 2-propanol and acetone, which are excellent in compatibility with water, are preferable, and acetone and ethanol are more preferable.

The content of the organic solvent can be appropriately selected depending on the intended use or purpose of use and the method of use of the medical and dental curable composition of the present invention, but is preferably in the range of 0.1 to 80.0 parts by weight. Is. When the content of the organic solvent exceeds 80.0 parts by weight, the adhesiveness to the dentin is lowered. On the other hand, if the content of the organic solvent is less than 0.1 part by weight, the composition cannot maintain a uniform state and separates, which adversely affects the storage stability.

(F) Polymerization Initiator The polymerization initiator (f) contained as an essential component in the medical and dental curable composition of the present invention is not particularly limited, and a known radical generator can be used without any limitation. The types of polymerization initiators are generally those that initiate polymerization by mixing immediately before use (chemical polymerization initiator), those that initiate polymerization by heating or heating (thermal polymerization initiator), and those that initiate polymerization by light irradiation. It is roughly classified into those to be initiated (photopolymerization initiator), and any of them can be used alone or in combination of two or more.

Examples of the above-mentioned chemical polymerization initiator include a redox-type polymerization initiator system consisting of an organic peroxide / amine compound, an organic peroxide / amine compound / sulfinate, and an organic peroxide / amine compound / borate compound, and oxygen. Examples thereof include polymerization initiator systems such as organic boron compounds, perborates, permanganates, and persulfates that initiate polymerization by reacting with water and water, as well as sulfinates, borate compounds, and barbituric acids. Polymerization can also be initiated by coexistence with water and / or a polymerizable monomer having an acidic group.

Specific examples of organic peroxides 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, tertiary butylperoxybenzoide, and the like, but are not limited thereto. Further, the above organic peroxides can be used alone or in combination of several kinds.

As the amine compound, a secondary or tertiary amine in which an amine group is bonded to an aryl group is preferable, and specific examples thereof include N, N-dimethyl-p-toluidine, N, N-dimethylaniline, and N-β. -Hydroxyethyl-aniline, N, N-di (β-hydroxyethyl) -aniline, N, N-di (β-hydroxyethyl) -p-toluidine, N-methyl-aniline, N-methyl-p-toluidine, etc. However, it is not limited to this. Further, the above amine compounds may be used alone or in combination of several kinds.

Specific examples of sulfinates include, but are not limited to, sodium benzenesulfinate, lithium benzenesulfinate, sodium p-toluenesulfinate, and the like. Further, the above sulfinates may be used alone or in combination of several kinds.

Specific examples of the borate compound include trialkylphenylboron, trialkyl (p-fluorophenyl) boron (alkyl group is n-butyl group, n-octyl group, n-dodecyl group, etc.), sodium salt, lithium salt, and the like. Examples thereof include, but are not limited to, potassium salt, magnesium salt, tetrabutylammonium salt, and tetramethylammonium salt. Further, the above borate compounds may be used alone or in combination of several kinds.

Specific examples of barbituric acids include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butylbarbituric acid, 5-butylbarbituric acid. Ethyl barbituric acid, 5-isopropyl barbituric acid, 5-cyclohexyl barbituric acid, 1,3,5-trimethylbarbituric acid, 1,3-dimethyl-5-ethylbarbituric acid, 1,3-dimethyl-n -Butyl barbituric acid, 1,3-dimethyl-5-isobutylbarbituric acid, 1,3-dimethyl-barbituric acid, 1,3-dimethyl-5-cyclopentyl barbituric acid, 1,3-dimethyl-5- Cyclohexylbarbituric acid, 1,3-dimethyl-5-phenylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1-benzyl-5-phenylbarbituric acid and thiobarbituric acids, and salts thereof ( Alkali metals or alkaline earth metals are particularly preferred), such as sodium 5-butylbarbiturates, sodium 1,3,5-trimethylbarbiturates, calcium 1,3,5-trimethylbarbiturates and 1-cyclohexyl. Examples include, but are not limited to, 5-ethylbarbiturate sodium. In addition, the above barbituric acids can be used alone or in combination of several kinds.

When the medical and dental curable composition of the present invention is used alone, it is necessary to include these chemical polymerization initiators in at least two or more packaging forms. Further, when the medical dental curable composition of the present invention is used together with other compositions, a chemical polymerization initiator is used so that the chemical polymerization is started when the medical dental curable composition comes into contact with the other composition. Can also be included in both the medical and dental curable compositions of the present invention and other compositions, respectively. Among these chemical polymerization initiators, sulfinates, barbituric acids, organic peroxides-tertiary amines and the like are preferably used alone or in combination, and more preferably organic peroxides-tertiary amines. , Organic peroxides-tertiary amines-barbituric acids, organic peroxides-tertiary amines-sulfinates. These chemical polymerization initiators are preferably contained in the range of 0 to 15.0 parts by weight, more preferably in the range of 0.1 to 10.0 parts by weight, based on 100 parts by weight of the medical and dental curable composition. It is to be contained in.

Examples of the photopolymerization initiator include those consisting of a photosensitizer-only system, those consisting of a photosensitizer / photopolymerization accelerator combination, and the like. Further, the photosensitizer is roughly classified into one in which polymerization is started by ultraviolet rays and one in which polymerization is started by visible light.

Specific examples of photosensitizers that can be used as photopolymerization initiators include benzyl, camphorquinone, α-naphthyl, acetonafsen, p, p'-dimethoxybenzyl, p, p'-dichlorobenzylacetyl, and pentandione. Α-Diketones such as 1,2-phenantrenquinone, 1,4-phenantrenquinone, 3,4-phenantrenquinone, 9,10-phenanthrenquinone, naphthoquinone, benzoin, benzoinmethyl ether, benzoinalkyl such as benzoinethyl ether, etc. Ethers, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and other thioxanthones, benzophenone, Benzophenones such as acetoinbenzophenone, p-chlorobenzophenone, p-methoxybenzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine Acylphosphin oxides such as oxides, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-diethylamino-1- (4-morpholinophenyl) -propanone-1 and the like. Α-Aminoacetophenones, benzyldimethylketal, benzyldiethylketal, ketals such as benzyl (2-methoxyethyl ketal), bis (cyclopentadienyl) -bis [2,6-difluoro-3- (1-pyrrolill) ) Benzyl] -titanium, bis (cyclopentadienyl) -bis (pentanfluorophenyl) -titanium, bis (cyclopentadienyl) -bis (2,3,5,6-tetrafluoro-4-disyloxyphenyl) -Includes, but is not limited to, benzenes such as titanium. Further, the above photosensitizer may be used alone or in combination of several kinds.

Specific examples of the photopolymerization accelerator that can be used as the photopolymerization initiator are N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-di. Benzylaniline, 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 amino ester, N, N-dimethyl Anthranic acid methyl ester, N, N-dihydroxyethylaniline, N, N-dihydroxyethyl-p-toluidine, p-dimethylaminophenyl alcohol, p-dimethylaminostyrene, N, N-dimethyl-3,5-xylidine , 4-Dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β-naphthylamine, tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N- Dimethylhexylamine, N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, 2,2'-(n-butylimino) diethanol, etc. Tertiary amines, secondary amines such as N-phenylglycine, 5-butylbarbituric acid, 1-benzyl-5-phenylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1,3, Barbituric acids such as sodium 5-trimethylbarbiturate, calcium 1,3,5-trimethylbarbiturate, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin diversatete, dioctyltinbis (mercaptoacetate iso) Octyl ester) salt, tin compounds such as tetramethyl-1,3-diacetoxydistanoxane, aldehyde compounds such as lauryl aldehyde and terephthalaldehyde, dodecyl mercaptan, 2-mercaptobenzoxazole, 1-decanthyl, thiosartyl acid. Examples include, but are not limited to, sulfur-containing compounds such as. stomach. Further, the above-mentioned photopolymerization accelerator may be used alone or in combination of several kinds.

Further, in order to improve the photopolymerization promoting ability, in addition to the above photopolymerization promoting agent, citric acid, malic acid, tartaric acid, glycolic acid, gluconic acid, α-oxyisobutyric acid, 2-hydroxypropanoic acid, 3-hydroxypropane. It is effective to add oxycarboxylic acids such as acid, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid and dimethylolpropionic acid.

Further, when the photopolymerization initiator is used, there is no particular limitation even if it is one package form or a package form divided into two or more. Among these photopolymerization initiators, a combination of α-diketone and a tertiary amine or α-diketone and a tin compound is preferable, and camphorquinone and amino such as p-N, N-dimethylaminobenzoate are more preferable. A combination of aromatic tertiary amines whose groups are directly linked to the benzene ring or aliphatic tertiary amines having a double bond in the molecule such as N, N-dimethylaminoethyl methacrylate, as well as camphorquinone and dibutyltin dilaurate. It is a combination of tin compounds such as dioctyltin dilaurate and dioctyltin. The content of these photopolymerization initiators is preferably in the range of 0.1 to 15.0 parts by weight, more preferably 0.1 to 10.0 parts by weight, based on 100 parts by weight of each medical and dental curable composition. It is contained in the range of parts. Most preferably, it is contained in the range of 0.1 to 8.0 parts by weight.

Further, as the thermal polymerization initiator by heating or heating, azo compounds such as azobisisobutyronitrile, methyl azobisisobutyrate, and azobiscyanovaleric acid are preferably used in addition to the above organic peroxides. Not limited to. Further, these thermal polymerization initiators can be used alone or in combination of several kinds. Further, depending on the intended use, Bronsted acid or Lewis acid can be obtained by irradiating with light such as sensitizing dyes such as coumarin, cyanine, and thiazine, halomethyl group-substituted-s-triazine derivative, and diphenyliodonium salt compound. The photoacid generator to be produced, quaternary ammonium halides, transition metal compounds and the like can also be appropriately used.

(G) Photoacid generator The photoacid generator (g) contained as an essential component in the medical and dental curable composition of the present invention is not particularly limited, and a known photoacid generator can be used without any limitation. Types of photoacid generators include bis (cyclohexylsulfonyl) diazomethane, 2-methyl-2-[(4-methylphenyl) sulfonyl] -1- [4- (methylthio) phenyl] -1-propanol, and bis (tert). -Butylsulfonyl) diazomethane, bis (4-methylphenylsulfonyl) diazomethane, diphenyl-4-methylphenylsulfonate trifluoromethanesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-p-toluenesulfonate, diphenyl (4-methoxyphenyl) ) Sulfonium-trifluoromethanesulfonate, Tris (4-methylphenyl) sulfonium nonafluorobutane sulfonate, (1R, 2S, 5R) -5-methyl-2- (propane-2-yl) cyclohexyl-4-methylbenzenesulfonate, 2 , 4,6-tris (trichloromethyl) -1,3,5-triazine, etc., but any of them can be used alone or in combination of two or more.

In addition, a photosensitizer can be used in combination with the photoacid generator (g). Specific examples of photosensitizers include benzyl, phenylquinone, α-naphthyl, acetonafsen, p, p'-dimethoxybenzyl, p, p'-dichlorobenzylacetyl, pentandione, 1,2-phenanthrenquinone, 1 , 4-Phenylentrenquinone, 3,4-Phenylanthrenquinone, 9,10-Phenylanthrenquinone, α-diketones such as naphthoquinone, Benzylalkyl ethers such as benzoin, benzoinmethyl ether, benzoinethyl ether, thioxanthone, 2-chlorothioxanthone. , 2-Methylthioxanthone, 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and other thioxanthones, benzophenone, acetoinbenzophenone, p-chlorobenzophenone, p. -Benzolphenones such as methoxybenzophenone, acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, Α-Aminoacetophenones such as 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-diethylamino-1- (4-morpholinophenyl) -propanone-1, benzyldimethyl Ketals such as ketal, benzyldiethyl ketal, benzyl (2-methoxyethyl ketal), bis (cyclopentadienyl) -bis [2,6-difluoro-3- (1-pyrrolill) phenyl] -titanium, bis (cyclo) Pentazienyl) -bis (pentanfluorophenyl) -titanium, bis (cyclopentadienyl) -bis (2,3,5,6-tetrafluoro-4-disyloxyphenyl) -titanocene such as titanium, etc. However, it is not limited to this. Further, the above photosensitizer may be used alone or in combination of several kinds. In addition, some photosensitizers also act as photopolymerization initiators, and when used in the medical and dental curable composition of the present invention, they can also be blended as a polymerization initiator.

A medical and dental curable composition for the purpose of thickening the medical and dental curable composition of the present invention to improve operability, or imparting mechanical strength to the adhesive interface layer to improve the adhesiveness. Can contain fillers. The filler is not particularly limited, and a known dental filler can be used. For example, inorganic fillers and / or organic fillers and / or organic-inorganic composite fillers may be mentioned, and these may be used alone or in combination without any limitation. Further, the shape of these fillers may be any particle shape such as spherical, needle-shaped, plate-shaped, crushed-shaped, and scaly-shaped, and is not particularly limited. Further, the particle size of these fillers is not particularly limited, but is preferably in the range of 0.001 to 10 μm, more preferably in the range of 0.01 to 5 μm, due to problems such as sedimentation and separation. Among these fillers, aerosil produced by the vapor phase method, which is ultrafine particles, or silica-zirconia oxide particles produced from a solution such as a sol-gel reaction, which is an ultrafine silica composite particle, is a medical and dental curable composition. It is effective for the present invention because it acts as a thickener when blended therein. Specific examples of Aerosil include Aerosil 200, Aerosil OX50, Aerosil R972, Aerosil R974, Aerosil R8200, Aerosil R711, Aerosil DT4, aluminum oxide C, titanium dioxide P25 and the like. Further, there is no problem even if a cohesive inorganic filler or the like in which these ultrafine particles are intentionally aggregated is used.

In addition, among the curable compositions for medical and dental use, ultraviolet absorbers such as 2-hydroxy-4-methylbenzophenone, hydroquinone, hydroquinone monomethyl ether, 2,5-di-tertiary butyl-4-methylphenol and the like are included. If necessary, components such as a polymerization inhibitor, a discoloration inhibitor, an antibacterial material, a coloring pigment, and other conventionally known additives can be arbitrarily added.

The method of use in the medical and dental curable composition of the present invention is not particularly limited, and it is not limited to use alone, but also includes etching materials, primers, bonding materials, self-etching primers, ceramic primers, metal primers, noble metal primers and the like. It can be used in combination with other compositions as appropriate.

The medical and dental curable composition of the present invention is characterized by being excellent in storage stability due to the composition of the components contained in the composition. Therefore, it can be made into one package form. Further, depending on the ratio of the components to be blended in the medical and dental curable composition of the present invention, the type of the polymerization initiator, the method of use, the purpose of use, etc., two or more packaging forms can be obtained, which are appropriately selected. be able to.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The test method for evaluating the performance of the medical and dental curable composition prepared in the following examples is as follows.

(1) Adhesiveness test Evaluation purpose: Evaluation of dentin adhesiveness to enamel and dentin and adhesiveness to porcelain using a medical and dental curable composition.

Evaluation method: After slaughter, the extracted maxillary central incisors of the mandible are thawed within 24 hours, and then the root is removed and the crown is cut to prepare a tooth fragment. Embed cow tooth fragments with epoxy resin. Under water injection, the embedded cow teeth are washed and dried by exposing the enamel or dentin with # 600 water-resistant abrasive paper. A double-sided tape with a hole with a diameter of 4 mm is applied to the exposed enamel or dentin to define the adhesive surface. The curable composition for medical and dental use prepared in Examples or Comparative Examples is applied to the specified adhesive surface, and light is irradiated for 30 seconds using a photopolymerization irradiator (Griplight II, manufactured by Matsukaze Co., Ltd.) to cure and adhere. Processing was performed. After that, a plastic mold (inner diameter 4 mm, height 2 mm) is fixed to the bonded surface, and a photopolymerization type composite resin (Beauty Fill, manufactured by Shofu Inc.) is filled inside the mold, and a photopolymerization irradiator (photopolymerization irradiator) ( Grip Light II (manufactured by Shofu Inc.) is used to irradiate light for 30 seconds to cure. After curing, the mold is removed and used as an adhesive test piece. After immersing this adhesion test piece in 37 ° C distilled water for 24 hours, a dentin adhesion test based on shear adhesion strength was performed at a crosshead speed of 1 mm / min using an Instron universal testing machine (Instron 5567, manufactured by Instron). I do. In addition, an adhesion test was conducted on a disc-shaped flat plate (diameter 15.0, height 5.0 mm: vintage halo, manufactured by Shofu Inc.), which is a ceramic material, instead of the bovine mandibular permanent tooth middle incisor. That is, a porcelain adherend (# 600 polished) was sandblasted (0.2 MPa), and a sample that was naturally dried after ultrasonic cleaning was subjected to a test similar to that of dentin.

(2) Adhesive durability test Evaluation purpose: Evaluation of dentin adhesiveness to enamel and dentin and adhesiveness to porcelain using a medical and dental curable composition.

Evaluation method: After preparing an adhesive test piece in the same manner as in the adhesiveness test, the adhesiveness test piece is immersed in 37 ° C. distilled water for 24 hours. After that, 2000 cycles of thermal cycles of alternately immersing in constant temperature water tanks at 4 ° C. and 60 ° C. for 1 minute each are carried out. After the thermal cycle is completed, this adhesive test piece is subjected to a dentin adhesiveness test and porcelain adhesiveness by shear adhesive strength at a crosshead speed of 1 mm / min using an Instron universal tester (Instron 5567, manufactured by Instron). Do the test.

(3) Storage stability test evaluation purpose: Various medical and dental curable compositions prepared were stored in an environment of 50 ° C. for 4 weeks, and the adhesiveness to enamel and dentin using the composition was evaluated.

Evaluation method: Perform an adhesive test based on shear adhesive strength by the same method as the adhesive test.

The abbreviations of the materials used in the curable compositions for medical and dental dentistry of Examples and Comparative Examples of the present invention are as follows.

A coupling organic compound having a uretdione group and at least one radically polymerizable group in the molecule.
UDN1: (2,4-dioxo-1,3-diazetidine-1,3-diyl) bis (ethane-2,1-diyl) bis (2-methacrylate)
UDN2: (2,4-dioxo-1,3-diazetidine-1,3-diyl) bis (ethane-2,1-diyl) bis (2-acrylate)
UDN: (((2,4-dioxo-1,3-diazetidine-1,3-diyl) bis (ethane-2,1-diyl)) bis (oxy)) bis (ethane-2,1-diyl) bis (2-methacrylate)
UDN4: (2,4-dioxo-1,3-diazetidine-1,3-diyl) bis (2-methylpropane-2,1,3-triyl) tetraacrylate
UDN5: 2- (3- (2- (acryloyloxy) ethyl) -2,4-dioxo-1,3-diazetidine-1-yl) -2-methylpropane-1,3-diyldiacrylate

others
SC_C1: 3-Aminopropyltrimethoxysilane
SC_C2: 3-methacryloylpropyltrimethoxysilane

(A) Phosphonate group-containing polymerizable monomer;
MHPA: 6-methacryloyloxyhexylphosphonoacetate and others
MHP: 6-methacryloyloxyhexyl dihydrodiene phosphate
MDP: 10-methacryloyloxydecyldihydrodiene phosphate (b) polyvalent carboxylic acid group-containing polymerizable monomer;
AET: 4-acryloyloxyethyl trimellitic acid (c) polymerizable monomer;
Bis-GMA: 2,2-bis (4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl) propane
UDMA: Di (methacryloyloxy) -2,2,4-trimethylhexamethylenediurethane
TGDMA: Triethylene glycol dimethacrylate
HEMA: 2-Hydroxyethyl (meth) Methacrylate (f) Polymerization Initiator
CQ: Camphorquinone
DMBE: p-dimethylaminobenzoic acid ethyl ester (e) Water-soluble organic solvent
EtOH: Ethanol (d) water;
DW: Distilled water (g) Photoacid generator
PA: 2,4,6-tris (trichloromethyl) -1,3,5-triazine and others
BHT: Dibutylhydroxytoluene

Preparation of curable composition for medical and dental table 1. Composition of Medical and Dental Curable Compositions One-component medical and dental curable compositions (Formulation Examples 1 to 7) were prepared according to the compositions shown in the table, and used in Examples and Comparative Examples.

Evaluation Results Adhesion test of the curable composition for medical and dental use containing the uretdione group of the present invention and a coupling organic compound having at least one kind of radically polymerizable group in the molecule is shown in Table 2. As a result, Table 3 shows the adhesive durability test result, and Table 4 shows the storage stability test result.
As can be seen from these results, the curable composition for medical dentistry containing the uretdione group of the present invention and a coupling organic compound having at least one radically polymerizable group in the molecule is suitable for dentin and porcelain. On the other hand, it can be seen that it has good adhesion performance. However, the silane coupling agent having a primary amino group at the end (Comparative Example 1) and the silane coupling agent conventionally used in the medical and dental field (Comparative Example 2) have already significantly low adhesive ability immediately after preparation. I understand. It is presumed that this is because, in the case of Comparative Example 1, the primary amino group loses its adhesive activity to dentin and porcelain because it forms a complex with a polymerizable monomer having a phosphonic acid group or a carboxylic acid group. Further, in the case of Comparative Example 2, it is presumed that the dealcoholization (hydrolysis reaction) of the silane coupling agent proceeds and condensation occurs, so that the adhesive activity is also lost. On the other hand, the uretdione group of the present invention and the coupling organic compound having at least one kind of radically polymerizable group in the molecule showed stable adhesiveness without decomposition even after the storage stability test. It is considered that this is because the uretdione group of the present invention and the coupling organic compound having at least one kind of radically polymerizable group in the molecule have high acid resistance and the hydrolysis reaction is suppressed. From the above evaluation results, the uretdione group of the present invention and the coupling organic compound having at least one kind of radically polymerizable group in the molecule have high acid resistance, and are under acidic conditions of pH 2 to 3 which are difficult to store by the prior art. However, it has become possible to exist stably. This made it possible to produce a one-component medical and dental curable composition.

The uretdione group according to the present invention and the coupling organic compound having at least one kind of radically polymerizable group in the molecule can coexist under acidic conditions of pH 2 to 3 which was difficult to liquefy by the prior art. rice field. Along with this, adhesion to bone, dentin, porcelain, etc. became possible with a one-pot composition. This technological development is considered to greatly contribute to the development of one-component medical and dental curable compositions, which have been considered difficult, and can be said to have high industrial applicability.

Claims (3)

A dental curable composition comprising a coupling organic compound represented by the following molecular structure.

In the formula, A represents one selected from H ₂ C = CH-, H ₂ C = C (CH ₃ )-, H ₂ C = CH-C ₆ H ₄ --group (C ₆ H ₄ is a phenylene group). ), B is -C (O) -O-, -C (O) -S-, --C (O) -NH-, -NH-C (O) -NH-, -NH-C ( Represents one selected from the O) -S- and -NH-C (O) -O- groups, where R is an independently C1-C60 linear or branched-chain alkylene group between carbon atoms. -C (O) -O-, -C (O) -S-, -C (O) -NH-, -NH-C (O) -NH-, -NH-C (O) -S-,- NH-C (O) -O-, -O-, -S- groups can be inserted. Note that a is an independent integer of 1 to 6.
The dental curable composition according to claim 1, wherein the phosphonic acid group-containing polymerizable monomer and the polyvalent carboxylic acid group-containing polymerizable monomer are contained in addition to the coupling organic compound. thing.
The dental curable composition according to claim 2, further comprising a polymerizable monomer, water, a water-soluble organic solvent, a polymerization initiator, and a photoacid generator.