JP2018172334A - Novel acid resistant silane coupling agent, and curable composition for medical/dental use containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition for medical/dental use which can express adhesiveness of firmly adhering biological hard tissue and adhesion durability capable of enduring even under a severe environment inside an oral cavity, and additionally, is difficult to suffer degradation or deterioration caused by hydrolysis due to environmental temperature, acidity of solution or the like, and enables a packaging form of one-component type having excellent storage stability.SOLUTION: A curable composition for medical/dental use uses a silane coupling agent which has at least one or more kinds of radically polymerizable group, and in which at least one or more of positions of alkoxide that bonds a silicon atom is an alkyl group of Cto Cstraight chain or branched chain including unsaturated bond.SELECTED DRAWING: None

Description

The present invention provides a C _{6 to} C ₄₀ linear or branched chain having at least one kind of radical polymerizable group and at least one of the alkoxide moieties bonded to the silicon atom containing an unsaturated bond. The present invention relates to a silane coupling agent characterized by being an alkyl group. Furthermore, the present invention relates to medical and dental materials such as restoration materials, crown materials, prosthetic materials, aesthetic materials, orthodontic materials, preventive materials, abutment building materials, root canal materials, porcelain ceramics, metals, resins, composite resins, The present invention relates to a curable composition for medical and dental use that is used for bonding to glass ionomer cement, living hard tissue (natural tooth enamel and dentin) and the like.

In recent years, composite resins have drastically improved long-term durability and mechanical characteristics, and also have characteristics such as sustained release of fluorine and X-ray contrast properties. It has come to be used for the functional and aesthetic recovery of the tooth quality in the event of a rupture or a break or fall off of a restoration of a crown. In addition, the use of this composite resin has expanded to applications such as tooth surface coating materials, fee chassis lands, orthodontic adhesives, and resin core materials. However, since these composite resins themselves do not have adhesiveness with respect to not only teeth but also ceramics and metals, it is essential to use various adhesives in combination. Especially for dental materials, adhesives are required to have excellent adhesion to both enamels mainly composed of inorganic components such as hydroxyapatite and dentins composed mainly of organic components such as collagen. It has been. Furthermore, recently, it has become a problem to firmly adhere to ceramics, metals, resins, composite resins, glass ionomer cements, and the like and to have adhesion durability.

In conventional adhesives, 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 and the composite resin. However, the tooth surface treatment method using an acid etching material requires that the acid applied to the tooth surface be sufficiently removed by washing with water, and further requires subsequent drying. . In addition, the adhesion method using an acid etching material is sufficient for enamel due to the formation of a rough surface by decalcification of the acid etching material and the macro mechanical fitting based on sufficient penetration and hardening of the bonding material. It showed adhesiveness. On the other hand, for dentin, sponge-like collagen fibers are exposed by decalcification of the acid-etching material, so the penetration of the bonding material into the collagen fibers is not sufficient, and it is difficult to obtain sufficient adhesion. there were. Accordingly, an acid tooth surface treatment material has been proposed in place of the phosphoric acid etching material in order to obtain high adhesion to dentin. For example, JP-A-62-33109 discloses a tooth surface treatment material containing a sulfonic acid group-containing polymer, JP-A-62-231652 discloses a tooth surface treatment material containing a metal halide, JP-A-63. No. -279851 discloses a tooth surface treatment material containing an amphoteric amino compound, Japanese Patent Application Laid-Open No. 1-279815 discloses a tooth surface treatment material containing an organic carboxylic acid and a metal chloride, and Japanese Patent Application Laid-Open No. 5-163111 discloses Examples thereof include tooth surface treatment materials containing organic carboxylic acid and iron phosphate. However, even when these acid tooth surface treatment materials are used, it has been difficult to obtain sufficient adhesion to dentin.

Japanese Patent No. 2865794 discloses a polymerizable compound containing an acid group: (a) the following general formula (1) [wherein R1 is a hydrogen atom or a methyl group, and R2 is a carbon atom number of 5 to 10]. And R3 represents an alkylene group having 1 to 6 carbon atoms. And (b) at least one radical polymerizable monomer and (c) at least one polymerization initiator are disclosed. Yes. When the phosphonic acid group contained in the (meth) acrylic acid ester derivative is applied to the tooth, the phosphonic acid group chemically bonds with the calcium component of the tooth, and as a result, a polymerizable group can be imparted to the tooth surface. . Later, it was announced that the primer was effective in penetrating 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 then, a three-step technique consisting of an acid treatment material / primer / bonding material has been performed. As a proposal of an adhesion method involving this three-step technique, methods described in Japanese Patent No. 3939573 and Japanese Patent No. 2962628 can be cited. In addition, since 2-HEMA, which is a water-soluble polymerizable monomer contained in a primer, has mucosal irritation, a primer composition containing another water-soluble polymerizable monomer in place of 2-HEMA is also available. It is disclosed. For example, JP 2004-137211 A discloses a primer composition containing polyethylene glycol or polyethylene glycol monomethacrylate, and Japanese Patent No. 2782694 discloses a primer composition containing glyceryl mono (meth) acrylate. However, these adhesion methods have a large number of steps and are complicated to operate, and although the adhesion to enamel is high, the 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 complicated operation steps that can simultaneously perform acid treatment for demineralizing the tooth surface and primer treatment for infiltrating the collagen fibers. Has been proposed. In the case of using this primer, an acid treatment on the tooth surface is not required, and the self-etching primer is treated (applied and left) on the tooth surface, and then dried and then the bonding material is applied. That is, by treating the tooth surface formed with the cavity with the self-etching primer, the tooth layer (enamel / dentin) penetrates while dissolving the smear layer formed by the cavity formation. After drying, a self-etching primer and the bonding material are integrated and cured by applying a bonding material thereto, thereby obtaining a strong adhesive layer.

Numerous proposals have been made regarding these self-etching primer compositions. For example, JP-A 1-113057 discloses a primer composition comprising a water / water-soluble film forming agent / acid salt, and Japanese Patent No. 2634276 discloses a polymerizable compound having water / hydroxyl group / a polymerizable compound having acid group. / Primer composition comprising curing agent, Patent No. 3480654 and Patent No. 3487389 include a water / phosphate group-containing polymerizable monomer / polyvalent carboxylic acid group-containing polymerizable monomer JP-A-7-82115 discloses 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 discloses a primer composition comprising 2-HEMA / water containing an organic acid or an inorganic acid, and JP-A-4-8368 discloses a polymerizable compound having a water / acid group / a polymerizable compound having a hydroxyl group / Examples thereof include a primer composition comprising an amino compound having an acid group. Although these compositions showed a certain level of adhesion to dentin, they did not have sufficient adhesion to enamel due to poor decalcification of inorganic components. Moreover, since the primer composition contains an acidic group-containing polymerizable monomer or a water-soluble polymerizable monomer having poor polymerizability, curing after application of the bonding material is insufficient, resulting in severe oral cavity. There has been a problem in adhesion durability under the environment. Furthermore, since these primer compositions are basically in an acidic atmosphere in which water / acid group-containing polymerizable monomers coexist, the intramolecular main chain and functional groups of the components contained in the primer composition Degradation and alteration 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 for combining the primer and the bonding material to sufficiently cure the adhesive layer and improve the adhesion to the tooth. For example, JP-A-2000-212015 and JP-A-2000-16911 disclose a bonding material and a primer composition containing an acylphosphine oxide compound as a photopolymerization initiator (having a polymerizable monomer having an acidic group / hydroxyl group). A dental adhesive system comprising a polymerizable monomer / water), JP-A-2004-26838 discloses a primer composition containing a phosphate group-containing polymerizable monomer / water and a polyvalent rubonic acid A dental adhesive kit comprising 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 its acid anhydride A novel adhesion method comprising an adhesive composition comprising a primer solution and a vinyl monomer having an acidic group, Japanese Patent Application Laid-Open No. 2000-204010 discloses a sulfonic acid group-containing polymerizable monomer / water-soluble polymerizable monomer / water. Including A dental adhesive kit comprising an adhesive material containing a primer composition and an acidic phosphate-based polyfunctional polymerizable monomer, JP-A-9-295313 discloses a sulfonic acid group-containing polymerizable monomer / water-soluble A dental adhesive kit comprising a primer composition containing a polymerizable monomer / water and an adhesive material containing a polyfunctional polymerizable monomer containing a polyvalent carboxylic acid group, JP-A-11-180814 contains an acid group Tooth substance comprising (meth) acrylate / water-soluble organic solvent / self-etching primer containing water and tooth adhesive containing (meth) acrylate / photopolymerization initiator / photopolymerization accelerator / filler having no acidic group and hydroxyl group Adhesive set, JP-A-6-24928 discloses polymerization of a primer solution composition containing a specific metal compound / acidic group-containing polymerizable monomer / polymerizable monomer and trialkylboron or its partial oxide Contains as initiator Patent No. 3449755 discloses an adhesive comprising an oxidizable composition, a primer composition containing an acidic group-containing vinyl polymer compound / hydroxyl group-containing water-soluble vinyl compound / water / aromatic amine, and an acidic group-containing acrylic monomer / acid group. Examples thereof include an adhesive kit comprising an acrylic adhesive containing a non-containing acrylic monomer / polymerization initiator.

Any of these proposals can be used in combination with a specific bonding material to improve the curability of a primer composition containing an acidic group-containing polymerizable monomer or a water-soluble polymerizable monomer with poor polymerization. Adhesion to dentin (enamel and dentin) is realized. However, the low curability due to the constituents of the primer composition has not been fundamentally improved, and therefore, inadequate adhesion durability to both enamel and dentin has been observed. It was.

In JP-A-10-251115, as a polymerizable compound containing an acid group, (A) a phosphoric acid group-containing polymerizable monomer having a -COP ester bond, (B) a polyvalent carboxylic acid group-containing polymerizable compound. A dental primer based on monomers and (C) water is disclosed. According to this dental primer, 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 in this primer is susceptible to hydrolysis, and there has been a problem in storage stability and adhesion durability. For adhesion to inorganic materials such as ceramics, for example, silane coupling agents such as 3-methacryloxypropyltrimethoxysilane are useful. However, as described above, since the medical and dental curable composition is required to have adhesion to bones and teeth such as enamel and dentin at the same time, a compound showing acidity and water coexist. Therefore, a conventional silane coupling agent such as 3-methacryloxypropyltrimethoxysilane which is susceptible to hydrolysis by an acid cannot coexist. Therefore, it was a situation that had to be supplied in the form of individual packaging. In other words, for adhesion to inorganic materials such as ceramics, first, after performing a silane coupling treatment such as 3-methacryloxypropyltrimethoxysilane, the medical dentistry curable composition is applied again. Has been required.

JP 62-33109 A JP 62-231652 A JP 63-279851 A Japanese Unexamined Patent Publication No. 1-279815 Japanese Patent Laid-Open No. 5-163111 Patent No. 2865794 specification Japanese Patent No. 3939573 Japanese Patent No. 2962628 JP 2004-137211 A Japanese Patent No. 2782694 Japanese Unexamined Patent Publication No. 1-113057 Japanese Patent No. 2634276 Japanese Patent No. 3480654 Japanese Patent No. 3487389 JP-A-7-82115 JP-A-62-223289 Japanese Patent Laid-Open No. 4-8368 Japanese Unexamined Patent Publication No. 2000-212015 JP 2000-16911 JP 2004-26838 A Japanese Patent No. 3236030 JP 2000-204010 JP Japanese Unexamined Patent Publication No. 9-295913 Japanese Patent Laid-Open No. 11-180814 JP-A-6-24928 Japanese Patent No. 3449755 Japanese Patent Laid-Open No. 10-251115

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

Therefore, the problem to be solved by the present invention is that it is sufficiently hardened after removal of volatile components, and adheres firmly to biological hard tissues such as ceramics, bone, enamel and dentin, and severe oral cavity It is an object of the present invention to provide a medical / dental curable composition capable of developing an adhesive durability that can be tolerated even in an internal environment. A further problem to be solved by the present invention is to enable a one-pack type packaging form that is not susceptible to degradation or alteration due to hydrolysis of the constituent components due to the temperature of the environment, the acidity of the solution, etc., and excellent in storage stability. It is to provide a medical and dental curable composition.

As a result of repeated studies, the present inventors have found that C _{6 to} C ₄₀ has at least one kind of radical polymerizable group and at least one of alkoxide sites bonded to the silicon atom contains an unsaturated bond. It has been found that the above-mentioned problems can be solved by using a silane coupling agent characterized by being a linear or branched alkyl group in a medical and dental curable composition. More specifically, the medical / dental curable composition containing the silane coupling agent, the phosphonic acid group-containing polymerizable monomer, and the polyvalent carboxylic acid group-containing polymerizable monomer has an acidic property in the presence of water. Even under an atmosphere, it also has excellent storage stability that is less susceptible to degradation and alteration due to hydrolysis of the constituent components.

The silane coupling agent of the present invention can be firmly adhered to any of dental materials such as porcelain ceramics, bone, enamel and dentin by being used in a medical and dental curable composition, and Also, it has adhesion durability that can withstand even in severe oral environment. In addition, the medical / dental curable composition containing the silane coupling agent, the phosphonic acid group-containing polymerizable monomer, and the polyvalent carboxylic acid group-containing polymerizable monomer can be used in an acidic atmosphere in which water is present. In addition, it also has excellent storage stability that is less susceptible to degradation and alteration due to hydrolysis of the constituent components.

The C ₆ -C ₄₀ linear or branched chain of the present invention has at least one radical polymerizable group and at least one of the alkoxide moieties bonded to the silicon atom contains an unsaturated bond. The molecular structure of the silane coupling agent characterized by being an alkyl group is, for example, the structure shown in [Chemical Formula 2], and may be used alone or in combination. The structure shown in [Chemical Formula 2] will be described in more detail. A represents an H ₂ C═CH—, H ₂ C═C (CH ₃ ) —, H ₂ C═CH—C ₆ H ₄ − group ( C ₆ H ₄ represents a phenylene group), B represents -C (O) -O-, -C (O) -S-, -C (O) -NH-, -NH-C (O) -NH - represents -NH-C (O) -S-, -NH-C (O) -O- group, Z is a straight-chain or branched alkylene group of C ₁ -C _30, Y is -NH-, -S-, -NH-C (O) -S-, -NH-C (O) -O-, -NH-C (O) -NH-, -C (O) -S-, -C (O) -O-, -CH (OH) -CH ₂ -S-, -CH (OH) -CH ₂ -O- group, R ² represents a C _{1 to} C ₃₀ linear or branched group an alkylene group of ^{chain, -S-, -NH-, -NR 4 -} (R 4 represents an alkylene _{group), -CH 2 -C 6 H 4} - (C 6 H 4 represents a phenylene group), - It may contain a C (O) —O—, —O— group, X represents OR ³ , and typical chemical structures of X are shown in [Chemical Formula 3] to [Chemical Formula 5]. R ³ represents a C _{6 to} C ₄₀ linear or branched alkyl group containing at least one unsaturated bond, and R ¹ represents a C _{1 to} C ₁₆ linear or branched alkyl group or a phenyl group. Represents. Here, a is 1 to 6, and n is 1 to 3.

Below, the typical chemical structure of X is described.
In addition, in each chemical structure, it shows having couple | bonded with the silicon atom (Si) through the oxygen atom (O) of the right side in a formula.

The typical chemical structure of [Chemical Formula 2] is described below.

The C ₆ -C ₄₀ linear or branched chain of the present invention has at least one radical polymerizable group and at least one of the alkoxide moieties bonded to the silicon atom contains an unsaturated bond. The molecular structure of the silane coupling agent characterized by being an alkyl group is, for example, the structure shown in [Chemical Formula 10], and may be used alone or in combination. The structure shown in [Chemical Formula 10] will be described in more detail. A represents an H ₂ C═CH—, H ₂ C═C (CH ₃ ) —, H ₂ C═CH—C ₆ H ₄ − group ( C ₆ H ₄ represents a phenylene group), B represents -C (O) -O-, -C (O) -S-, -C (O) -NH-, -NH-C (O) -NH - represents -NH-C (O) -S-, -NH-C (O) -O- group, Z is a linear or branched alkylene group of C ₁ ~C _60, -CH (OH ) -CH ₂ -S-, -CH (OH) -CH ₂ -O- group, D represents a C ₂ to C ₆₀ divalent to tetravalent linear or branched alkylene group; -C (O) -O-, -C (O) -S-, -NH-C (O)-, -NH-C (O) -NH-, -S-, -NH-C (O)- S-, include a -NH-C (O) -O-, and / or a trivalent triazine molecule skeleton or a divalent barbituric acid molecule skeleton, E is, -NH -, - NR ⁴ - (R ⁴ represents an alkylene group), -S-, -NH-C (O) -S-, -NH-C (O) -NH-, -C (O) -S-, -NH-C ( O) -O-, -C (O) -O- group, wherein R ² is a C _{1 to} C ₆₀ linear or branched alkylene group, -S-, -NH-, -CH _{2- C 6 H 4 - (C 6} H 4 represents a phenylene group), -C (O) -O-, -O- groups Wherein resulting, R ³ represents a linear or branched alkyl group of C ₆ -C ₄₀ containing at least one unsaturated bond, a straight-chain or branched-chain alkyl group of R ¹ is C ₁ -C ₁₆ Represents a phenyl group. The sum of q and r is equal to the valence of D, r is a positive integer of 1 or more, a is 1 to 6, and n is 1 to 3.

The chemical structures of typical compounds are described below.

The C ₆ -C ₄₀ linear or branched chain of the present invention has at least one radical polymerizable group and at least one of the alkoxide moieties bonded to the silicon atom contains an unsaturated bond. The molecular structure of the silane coupling agent characterized by being an alkyl group is, for example, the structure shown in [Chemical Formula 14], and may be used alone or in combination. The structure shown in [Chemical Formula 14] will be described in more detail. A represents an H ₂ C═CH—, H ₂ C═C (CH ₃ ) —, H ₂ C═CH—C ₆ H ₄ − group ( C ₆ H ₄ represents a phenylene group), B represents -C (O) -O-, -C (O) -S-, -NH-C (O)-, -NH-C (O) -NH - represents -NH-C (O) -S-, -NH-C (O) -O- group, Z is a straight-chain or branched alkylene group of C ₁ ~C _60, R ² is C _{1 to} C _{6 represents} a linear or branched alkyl group, R ¹ represents a C _{1 to} C ₁₆ linear or branched alkyl group, a phenyl group, and R ² represents at least one or more unsaturated groups C ₆ -C ₄₀ linear or branched alkyl group containing a bond. Here, a is 1 to 6, and n is 1 to 3.

The chemical structures of typical compounds are described below.

The C ₆ -C ₄₀ linear or branched chain of the present invention has at least one radical polymerizable group and at least one of the alkoxide moieties bonded to the silicon atom contains an unsaturated bond. The molecular structure of the silane coupling agent characterized by being an alkyl group is, for example, the structure shown in [Chemical Formula 17], and may be used alone or in combination. The structure shown in [Chemical Formula 17] will be described in more detail. A represents an H ₂ C═CH—, H ₂ C═C (CH ₃ ) —, H ₂ C═CH—C ₆ H ₄ − group ( C ₆ H ₄ represents a phenylene group), R ² represents a C _{1 to} C ₆ linear or branched alkyl group, R ¹ represents a C _{1 to} C ₁₆ linear or branched alkyl group, phenyl R ² represents a C _{6 to} C ₄₀ linear or branched alkyl group containing at least one unsaturated bond. Here, a is 1 to 6, and n is 1 to 3.

Hereinafter, specific chemical structures of typical compounds are partially described.

The C ₆ -C ₄₀ linear or branched chain of the present invention has at least one radical polymerizable group and at least one of the alkoxide moieties bonded to the silicon atom contains an unsaturated bond. When a silane coupling agent characterized by being an alkyl group is used in a medical / dental curable composition, it is preferably a medical / dental curable composition containing the following components.
(A) C ₆ -C ₄₀ linear or branched alkyl having at least one kind of radical polymerizable group and at least one of the alkoxide moieties bonded to the silicon atom containing an unsaturated bond Silane coupling agent (b) Phosphonic acid group-containing polymerizable monomer (c) Polyvalent carboxylic acid group-containing polymerizable monomer (d) Polymerizable monomer (e) Water (F) Water-soluble organic solvent (g) Polymerization initiator Details of each component are shown below.

(A) C ₆ -C ₄₀ linear or branched alkyl having at least one kind of radical polymerizable group and at least one of the alkoxide moieties bonded to the silicon atom containing an unsaturated bond Silane coupling agent characterized in that it has at least one radical polymerizable group of the present invention, and at least one alkoxide moiety bonded to a silicon atom contains an unsaturated bond When a silane coupling agent, which is a C ₆ -C ₄₀ linear or branched alkyl group, is used in a medical / dental curable composition, in 1 part by weight of the medical / dental curable composition, 1 The content is preferably 10 to 10 parts by weight, more preferably 4 to 6 parts by weight. When the amount of the silane coupling agent is less than 1 part by weight, sufficient adhesion strength cannot be obtained because the amount of the silane coupling agent is too small with respect to the silanol group on the adherend surface. Conversely, when the amount exceeds 10 parts by weight, fragile bonds between the silane coupling agents (increase in non-condensed sites in the xerogel structure) increase, so that sufficient adhesive strength cannot be obtained.

(B) Phosphonic acid group-containing polymerizable monomer
The phosphonic acid group-containing polymerizable monomer contained in the medical / dental curable composition of the present invention is, for example, one (—PO (OH) 2) or phosphonic acid monoester directly bonded to at least a carbon atom in the molecule. It means a polymerizable monomer having a group (—PO (OH) (OR)) and at least one polymerizable unsaturated group. That is, as long as these conditions are satisfied, any functional group having in the molecule can be used without any limitation. In addition, the phosphonic acid group-containing polymerizable monomer is an unsaturated compound capable of radical polymerization such as the number of phosphonic acid groups or phosphonic acid monoester groups in the molecule, or (meth) acryloyl group, styryl group, vinyl group, allyl group, etc. There is no particular limitation on the type and number of groups. By containing a phosphonic acid group-containing polymerizable monomer in the medical and dental curable composition of the present invention, compared with a polymerizable monomer having a phosphoric acid monoester group or a phosphoric acid diester group, In particular, it can exhibit excellent adhesive properties for enamel. In addition, since the phosphonic acid group-containing polymerizable monomer is not bonded to an oxygen atom by an ester bond, it is less susceptible to hydrolysis in the molecule even in an acidic atmosphere in the presence of water, and is stable in storage. Excellent in properties. Therefore, the packaging form is not limited to the two-part packaging form divided into two, but can be a one-part packaging form.

Among these phosphonic acid group-containing polymerizable monomers, excellent tooth adhesion and storage stability [Chemical Formula 19] [wherein R1 is a hydrogen atom or a methyl group, and R2 has 5 to 10 carbon atoms. An alkylene group, R3 represents an alkylene group having 1 to 6 carbon atoms. It is preferable to use a phosphonic acid group-containing polymerizable monomer represented by the formula:

Specific examples of the phosphonic acid group-containing polymerizable monomer represented by [Chemical Formula 19] include the following compounds, but are not limited thereto.

These phosphonic acid group-containing polymerizable monomers can be used alone or in combination. Among these phosphonic acid group-containing polymerizable monomers, 6- (meth) acryloyloxyhexyl phosphonoacetate, 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 according to the intended use or purpose of the medical / dental curable composition and the method of use, but is preferably a medical / dental curing. 100 parts by weight of the composition is in the range of 0.1 to 40.0 parts by weight. If the content of the phosphonic acid group-containing polymerizable monomer exceeds 40.0 parts by weight, the curability due to the polymerizability is lowered, and the adhesive properties are adversely affected. 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 adhesion to enamel.

(C) Multivalent carboxylic acid group-containing polymerizable monomer
The (c) polyvalent carboxylic acid group-containing polymerizable monomer contained in the medical / dental curable composition of the present invention easily reacts with, for example, at least two carboxylic acid groups or water in the molecule. It means a polymerizable monomer having two or more carboxylic acid groups and at least one polymerizable unsaturated group. That is, any functional group can be used without any limitation as long as these conditions are satisfied. Further, the polyvalent carboxylic acid group-containing polymerizable monomer is not particularly limited in the kind and number of unsaturated groups capable of radical polymerization such as (meth) acryloyl group, styryl group, vinyl group, allyl group, etc. in the molecule. . By containing the polyvalent carboxylic acid group-containing polymerizable monomer in the medical / dental curable composition of the present invention, it is possible to exhibit excellent tooth adhesion performance to dentin.

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, 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) acryloyloxybutyl trimellitic acid and its anhydride, β- (meth) acryloyloxyethyl hydrogen sac Cine, β- (meth) acryloyloxyethyl hydrogen maleate, 11- (meth) acrylo Ruoxy-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 anhydrides thereof, 6- (meth) acryloyloxy-1,1-hexanedicarboxylic acid, 8- (meth) Examples include acryloyloxy-1,1-octanedicarboxylic acid, 10- (meth) acryloyloxy-1,1-decanedicarboxylic acid, 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid, and the like. In limited There. These polyvalent carboxylic acid group-containing polymerizable monomers can be used alone or in combination. 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 according to the use or purpose of use of the medical / dental curable composition and the method of use, but preferably the medical / dental In 100 parts by weight of the curable composition for use, it is in the range of 0.1 to 40.0 parts by weight. If the content of the polyvalent carboxylic acid group-containing polymerizable monomer exceeds 40.0 parts by weight, the curability due to the polymerizability 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 adhesion to dentin.

In the medical / dental curable composition of the present invention, when further enhancing the adhesion to a living hard tissue, or when imparting the adhesion to various adherends including a noble metal or the like, a phosphonic acid group-containing polymerizable monomer is used. An acidic group-containing polymerizable monomer other than the monomer, the polyvalent carboxylic acid group-containing polymerizable monomer, and a polymerizable monomer containing a sulfur atom in the molecule may be included in combination. As an acidic group-containing polymerizable monomer other than a phosphonic acid group-containing polymerizable monomer or a polyvalent carboxylic acid group-containing polymerizable monomer, any monomer having at least one acidic group in the molecule can be used. 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, pyrophosphoric acid groups, sulfonic acid groups, and thiophosphoric acid groups. However, it is not limited to these. In addition, the number of unsaturated groups capable of radical polymerization (monofunctional group or polyfunctional group) and the type of the polymerizable monomers containing these acidic groups can be used without any limitation. Specific examples of the unsaturated group possessed by the acidic group-containing polymerizable monomer include (meth) acryloyl group, styryl group, vinyl group, allyl group, etc. Among these unsaturated groups, (meth) acryloyl An acidic group-containing polymerizable monomer having a group is preferable. Furthermore, these acidic group-containing polymerizable monomers can also contain other functional groups such as alkyl groups, halogens, amino groups, glycidyl groups and hydroxyl groups 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) acryloyloxymethyl dihydrogen phosphate, 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydro Genphosphate, 4- (meth) acryloyloxybutyl dihydrogen phosphate, 5- (meth) acryloyloxypentyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl dihydrogen phosphate, 7- (meth) acryloyloxyheptyl Dihydrogen phosphate, 8- (meth) acryloyloxyoctyl dihydrogen phosphate, 9- (meth) acryloyloxynonyl dihydrogen phosphate, 10- (meth) acetate Royloxydecyl dihydrogen phosphate, 11- (meth) acryloyloxyundecyl dihydrogen phosphate, 12- (meth) acryloyl oxide decyl dihydrogen phosphate, 16- (meth) acryloyloxyhexadecyl dihydrogen phosphate, 20 -(Meth) acryloyloxyeicosyl dihydrogen phosphate, di (meth) acryloyloxyethyl hydrogen phosphate, di (meth) acryloyloxybutyl hydrogen phosphate, di (meth) acryloyloxyhexyl hydrogen phosphate, di (meth) Acryloyloxyoctyl hydrogen phosphate, di (meth) acryloyloxynonyl hydrogen phosphate, di (meth) actyl Royloxydecyl hydrogen phosphate, 1,3-di (meth) acryloyloxypropyl-2-dihydrogen phosphate, 2- (meth) acryloyloxyethylphenyl hydrogen phosphate, 2- (meth) acryloyloxyethyl 2′- Examples include, but are not limited to, bromoethyl hydrogen phosphate, (meth) acryloyloxyethyl phenyl phosphonate, 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-vinylbenzoic acid, 5- (meth) acryloylamino Although pentylcarboxylic acid etc. are mentioned, it is not limited to these.

In addition, examples of the acidic group-containing polymerizable monomer having a pyrophosphate group include di [2- (meth) acryloyloxyethyl pyrophosphate], di [3- (meth) acryloyloxypropyl pyrophosphate], di [pyrophosphate di [ 4- (meth) acryloyloxybutyl], di [5- (meth) acryloyloxypentyl] pyrophosphate, di [6- (meth) acryloyloxyhexyl) pyrophosphate, di [7- (meth) acryloyloxyheptyl pyrophosphate ], Di [8- (meth) acryloyloxyoctyl pyrophosphate], di [9- (meth) acryloyloxynonyl] pyrophosphate, di [10- (meth) acryloyloxydecyl pyrophosphate], di [12- pyrophosphate] (Meth) acryloyl oxide decyl], tetra [2- (meth) acryloyloxyethyl pyrophosphate ], Although pyrophosphate tri [2- (meth) acryloyloxyethyl], and the like, but is not limited thereto.

Examples of the acidic group-containing polymerizable monomer having a sulfonic acid group include 2- (meth) acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, 2-sulfoethyl (meth) acrylate, 4- (meta). ) 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) acryloyloxydecyl dihydrogendithiophosphate.

Although the acidic group-containing polymerizable monomer has been described above, the present invention is not limited thereto, and these polymerizable monomers having an acidic group can be used alone or in combination. Furthermore, as these acidic group-containing polymerizable monomers, not only monomers having a short main chain but also oligomers, prepolymers and polymers having a long main chain can be used without any limitation. Derivatives of acidic group-containing polymerizable monomers such as metal salts, ammonium salts or acid chlorides partially neutralized with acidic groups of these acidic group-containing polymerizable monomers can also be applied to various adherends. It can be used as long as it does not adversely affect the adhesion.

In order to provide the medical and dental curable composition of the present invention with adhesion to a noble metal, 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 the molecule having a (meth) acryloyl group as an unsaturated group include (meth) acrylate having a triazine thiol group, (meth) acrylate having a mercapto group, (Meth) acrylates having polysulfide groups, (meth) acrylates having thiophosphate groups, (meth) acrylates having disulfide cyclic groups, (meth) acrylates having mercaptodithiazole groups, (meth) acrylates having thiouracil groups, thiiranes Although (meth) acrylate etc. which have group are mentioned, it is not limited to this. These polymerizable monomers containing a sulfur atom in the molecule can be used alone or in combination.

(D) Polymerizable monomer The polymerizable monomer contained in the medical / dental curable composition of the present invention may be monofunctional or polyfunctional regardless of the type of unsaturated group capable of radical polymerization. Can be used without any limitation. Examples of the radical polymerizable unsaturated group of the polymerizable monomer include (meth) acryloyl group, (meth) acrylimide group, styryl group, vinyl group, allyl group, etc. It is preferable to use a polymerizable monomer having an acryloyl group or a (meth) acrylimide 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, (Meth) acrylic acid esters such as cyclohexyl (meth) acrylate, benzyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, isobornyl (meth) acrylate, Silane compounds such as γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, 2- (N, N-dimethylamino) ethyl (meth) Nitrogen-containing compounds such as acrylate, 2,2-bis (4- (meth) acryloyloxyphenyl) propane, 2,2-bis (4- (3- (meth) acryloyloxy-2-hydroxypropoxy) phenyl) propane, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxy Tetraethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypentaethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydipropoxyphenyl) propane, 2 (4- (meta ) Acryloyloxyethoxyphenyl) -2 (4- (meth) acryloyloxydiethoxypheny) ) 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- (meth) 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) acryloyloxyethyl-2 2,4-trimethylhexamethylene dicarbamate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate and the like. Examples of the hydrophobic polymerizable monomer containing an aliphatic tetrafunctional group include pentaerythritol tetra (meth) acrylate, pentaerythritol tetraacrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3 -Polymerizable monomer having a hydroxyl group such as chloro-2-hydroxypropyl (meth) acrylate and methylcyclohexane diisocyanate, methylenebis (4-cyclohexylisocyanate), hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, diisocyanate methylmethyl Bifunctional or trifunctional polymerization derived from adducts with benzene, diisocyanate compounds such as 4,4-diphenylmethane diisocyanate 2,2-bis (4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl) propane (Bis-GMA), 2,2-bis, etc. having a group and a urethane bond (4-Methacryloyloxyethoxyphenyl) propane (D-2.6E), di (methacryloyloxy) -2,2,4-trimethylhexamethylene diurethane (UDMA), triethylene glycol dimethacrylate (TEGDMA), neopentyl glycol di Methacrylate, trimethylolpropane trimethacrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1,2-dihydroxypropyl (meth) acrylate, 1, 3-dihydroxypropyl (meth) acryl 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) acryl chloride, (meth) acrylamide, 2-hydroxyethyl (meth) acrylamide, polyethylene glycol di (meth) acrylate (having 9 or more oxyethylene groups), 2- Hydroxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate (having 9 oxyethylene groups), polyethylene glycol di (meth) acrylate (having 14 oxyethylene groups), polyethylene glycol Di (meth) acryl Although over bets (the number of oxyethylene groups those 23), and the like, but is not limited thereto.

(E) Water contained in the medical / dental curable composition of the present invention is a phosphonic acid group-containing polymerizable monomer or polyvalent carboxylic acid group-containing polymerizable compound contained in the medical / dental curable composition. It has the function of activating the acidic group of the monomer and the like to promote the decalcification action on the living hard tissue and promoting 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, polymerizability, and biohard tissue adhesion. Preferably, distilled water or ion exchange water is used. The water content can be appropriately selected according to the use or purpose of use of the medical / dental curable composition of the present invention and the method of use, but preferably 100 parts by weight of the medical / dental curable composition is used. 0.1 to 80.0 parts by weight. If the water content exceeds 80.0 parts by weight, the composition will not maintain a uniform state and will have an adverse effect on storage stability such as separation. On the other hand, if the water content is less than 0.1 parts by weight, sufficient adhesion to various adherends including living hard tissues cannot be obtained.

(F) Water-soluble organic solvent (f) The water-soluble organic solvent contained in the medical / dental curable composition of the present invention is a phosphonic acid group-containing polymerizable monomer contained in the medical / dental curable composition. It has a role as a dissolution accelerator that compatibilizes various polymerizable monomers including water and polyvalent carboxylic acid group-containing polymerizable monomers, water, polymerization initiators, and other compounding components at an arbitrary ratio. And has a function of promoting penetration of the medical / dental curable composition into the tooth. In addition, the liquid viscosity of the medical / dental curable composition can be reduced, and the operability such as dropping from a container or application to a site to be adhered can be improved. Specific examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, dipropylene glycol. Water-soluble organic solvents such as ether compounds such as monomethyl ether, tetrahydrofuran and dimethoxyethane, and ketone compounds such as acetone and methyl ethyl ketone can be used, but the present invention is not limited to these and can be used without any limitation. 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, acetone and the like, 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 use or purpose of use of the medical / dental curable composition of the present invention and the method of use, but preferably in 100 parts by weight of the medical / dental curable composition. 0.1 to 80.0 parts by weight. If the content of the organic solvent exceeds 80.0 parts by weight, the adhesion to the tooth will be reduced. On the other hand, when the content of the organic solvent is less than 0.1 parts by weight, the composition does not maintain a uniform state, and the storage stability such as separation is adversely affected.

(G) Polymerization initiator The (g) polymerization initiator contained in the medical / dental curable composition of the present invention is not particularly limited, and any known radical generator may be used without any limitation. The types of polymerization initiators are generally those that start polymerization by mixing immediately before use (chemical polymerization initiator), those that start polymerization by heating or heating (thermal polymerization initiator), and polymerization by light irradiation. Although it divides roughly into what is started (photoinitiator), all can be used individually or in combination.

As the above-mentioned chemical polymerization initiator, redox type polymerization initiator system comprising organic peroxide / amine compound or organic peroxide / amine compound / sulfinate, organic peroxide / amine compound / borate compound, oxygen And polymerization initiator systems such as organoboron compounds, perborates, permanganates and persulfates that start polymerization by reacting with water and sulfinates, borate compounds and barbituric acids. Polymerization can also be initiated by coexisting with a polymerizable monomer having water and / or an acidic group.

Specific examples of the organic peroxide 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 butyl peroxybenzoate and the like, but are not limited thereto. Moreover, the said organic peroxide can also be used individually or in combination of several types.

The amine compound is preferably a secondary or tertiary amine in which an amine group is bonded to an aryl group. Specific examples thereof include N, N-dimethyl-p-toluidine, N, N-dimethylaniline, 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. Moreover, the said amine compound can also be used individually or in combination of several types.

Specific examples of sulfinates include sodium benzenesulfinate, lithium benzenesulfinate, sodium p-toluenesulfinate and the like, but are not limited thereto. Moreover, the said sulfinates can also be used individually or in combination of several types.

Specific examples of the borate compound include sodium salt, lithium salt of trialkylphenyl boron, trialkyl (p-fluorophenyl) boron (wherein the alkyl group is n-butyl group, n-octyl group, n-dodecyl group, etc.), A potassium salt, a magnesium salt, a tetrabutylammonium salt, a tetramethylammonium salt, and the like can be mentioned, but the invention is not limited thereto. Further, the borate compounds can be used alone or in combination of several kinds.

Specific examples of the barbituric acids include barbituric acid, 1,3-dimethylbarbituric acid, 1,3-diphenylbarbituric acid, 1,5-dimethylbarbituric acid, 5-butylbarbituric acid, 5- 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-isobutyl barbituric acid, 1,3-dimethyl-barbituric acid, 1,3-dimethyl-5-cyclopentyl barbituric acid, 1,3-dimethyl-5 Cyclohexyl barbituric acid, 1,3-dimethyl-5-phenylbarbituric acid, 1-cyclohexyl-5-ethylbarbituric acid, 1- Nyl-5-phenylbarbituric acid and thiobarbituric acids, and their salts (especially preferred are alkali metals or alkaline earth metals), such as sodium 5-butylbarbiturate, 1,3,5-trimethylbarbi Examples include, but are not limited to, sodium toolate, calcium 1,3,5-trimethylbarbiturate and sodium 1-cyclohexyl-5-ethylbarbiturate. Moreover, the said barbituric acid can also be used individually or in combination of several types.

When the medical / dental curable composition of the present invention is used alone, it is necessary to divide these chemical polymerization initiators into at least two packaging forms. In addition, when the medical / dental curable composition of the present invention is used together with another composition, the chemical polymerization initiator is used so that the chemical polymerization starts when the medical / dental curable composition comes into contact with the other composition. Can also be included in both the medical and dental curable composition of the present invention and other compositions. Among these chemical polymerization initiators, sulfinates, barbituric acids, organic peroxides-tertiary amines, etc. are preferably used alone or in combination, more preferably organic peroxides-tertiary amines. , Organic peroxide-tertiary amine-barbituric acid, organic peroxide-tertiary amine-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 with respect to 100 parts by weight of the medical / dental curable composition. It is to contain.

Examples of the photopolymerization initiator include those composed of a photosensitizer only system or those composed of a photosensitizer / photopolymerization accelerator combination. The photosensitizers are roughly classified into those in which polymerization is initiated by ultraviolet rays and those in which polymerization is initiated by visible light.

Specific examples of photosensitizers that can be used as photopolymerization initiators include benzyl, camphorquinone, α-naphthyl, acetonaphthene, p, p′-dimethoxybenzyl, p, p′-dichlorobenzylacetyl, pentanedione. Α-diketones such as 1,2-phenanthrenequinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, and naphthoquinone, and benzoin alkyls such as benzoin, benzoin methyl ether, and benzoin ethyl ether Ethers, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-methoxythioxanthone, 2-hydroxythioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Benzoxanthones such as benzophenone, acetoin benzophenone, p-chlorobenzophenone, p-methoxybenzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4 Acylphosphine oxides such as 1,4-trimethylpentylphosphine oxide, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-diethylamino-1- (4-morpholino Α-aminoacetophenones such as phenyl) -propanone-1, ketals such as benzyldimethyl ketal, benzyl diethyl ketal, benzyl (2-methoxyethyl ketal), bis (cyclopentadienyl) -bis [2,6- Fluoro-3- (1-pyrrolyl) phenyl] -titanium, bis (cyclopentadienyl) -bis (pentanefluorophenyl) -titanium, bis (cyclopentadienyl) -bis (2,3,5,6-tetra Examples thereof include, but are not limited to, titanocenes such as fluoro-4-disiloxyphenyl) -titanium. Moreover, the said photosensitizer can also be used individually or in combination of several types.

Specific examples of the photopolymerization accelerator that can be used as the photopolymerization initiator include 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 aminoester, N, N-dimethyl Anthranilic acid methyl ester, N, N-dihydroxyethylaniline, N, N-dihi Roxyethyl-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, Tertiary amines such as N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, 2,2 ′-(n-butylimino) diethanol, secondary amines such as N-phenylglycine, 5- Butyl barbituric acid, 1-benzyl Barbituric acids such as 5-phenylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1,3,5-trimethylbarbituric acid sodium, 1,3,5-trimethylbarbituric acid calcium acid, dibutyltin diacetate , Dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin diversate, dioctyltin bis (mercaptoacetic acid isooctyl ester) salt, tin compounds such as tetramethyl-1,3-diacetoxy distanoxane, lauryl aldehyde, terephthalaldehyde, etc. Aldehyde compounds, sulfur-containing compounds such as dodecyl mercaptan, 2-mercaptobenzoxazole, 1-decanethiol, thiosalicylic acid, and the like, but are not limited thereto. Moreover, the said photoinitiator can also be used individually or in combination of several types.

Furthermore, in order to improve the photopolymerization promoting ability, in addition to the above photopolymerization accelerator, 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.

Moreover, when using a photoinitiator, there is no restriction | limiting in particular even if it is one packaging form or the packaging form divided | segmented into two or more. Among these photopolymerization initiators, a combination of α-diketone and tertiary amine or α-diketone and tin compound is preferable, and amino acid such as camphorquinone and p-N, N-dimethylaminobenzoate is more preferable. A combination of an aromatic tertiary amine having a direct bond to a benzene ring or an aliphatic tertiary amine having a double bond in the molecule such as N, N-dimethylaminoethyl methacrylate, and camphorquinone and dibutyltin dilaurate Or a combination of tin compounds such as dioctyltin dilaurate. 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 with respect to 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.

In addition to the above organic peroxides, azo compounds such as azobisisobutyronitrile, methyl azobisisobutyrate, and azobiscyanovaleric acid are preferably used as the thermal polymerization initiator by heating or heating. It is not limited to. These thermal polymerization initiators may be used alone or in combination of several kinds. Furthermore, depending on the intended use, Bronsted acid or Lewis acid can be applied by light irradiation of sensitizing dyes such as coumarin, cyanine, and thiazine, halomethyl group-substituted s-triazine derivatives, diphenyliodonium salt compounds, etc. The photoacid generator, quaternary ammonium halides, transition metal compounds, and the like that are generated can be used as appropriate.

The medical and dental curable composition of the present invention is intended to improve the operability by increasing the viscosity of the medical and dental curable composition of the present invention, or to improve the adhesiveness by imparting mechanical strength to the adhesive interface layer. The filler may be included. The filler is not particularly limited, and any known dental filler can be used. Examples thereof include inorganic fillers and / or organic fillers and / or organic-inorganic composite fillers, and these can be used without any limitation even if they are used alone or in combination. The shape of these fillers may be any particle shape such as a spherical shape, a needle shape, a plate shape, a crushed shape, and a scale shape, 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, the silica-zirconia oxide particles produced from a solution such as aerosil produced by a vapor phase method, which is an ultrafine particle, or a sol-gel reaction, which is an ultrafine silica composite particle, are medical and dental curable compositions. Since it works as a thickener by blending in, it is effective for the present invention. 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 coherent inorganic filler or the like obtained by intentionally agglomerating those ultrafine particles is used.

In addition, in medical and dental curable compositions, ultraviolet absorbers such as 2-hydroxy-4-methylbenzophenone, hydroquinone, hydroquinone monomethyl ether, 2,5-ditertiarybutyl-4-methylphenol, etc. Ingredients such as a polymerization inhibitor, a discoloration inhibitor, an antibacterial material, a color pigment, and other conventionally known additives can be optionally added as necessary.

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

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

EXAMPLES The present invention will be specifically described below 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 / dental curable composition prepared in the following examples is as follows.

(1) Adhesion test evaluation purpose: Evaluation of adhesion to enamel and dentin, and adhesion to porcelain using a medical / dental curable composition.

Evaluation method: After slaughtering, the extracted central incisors of bovine lower jaw teeth frozen and stored within 24 hours are thawed, and then the root part is removed and the crown part is cut to produce a bovine tooth fragment. Embry the bovine tooth pieces with epoxy resin. Under water injection, the embedded bovine teeth are exposed to enamel or dentin using # 600 water-resistant abrasive paper, washed and dried. An adhesive surface is defined by applying a double-sided tape with a hole of 4 mm in diameter to the exposed enamel or dentin. The medical / dental curable composition prepared in Examples or Comparative Examples was applied to the specified adhesive surface, and cured by light irradiation for 30 seconds using a photopolymerization irradiator (Griplight II, manufactured by Matsukaze Co., Ltd.). Went. Thereafter, a plastic mold (inner diameter: 4 mm, height: 2 mm) is fixed to the bonded surface, and a photopolymerization type composite resin (Beauty Fill II, manufactured by Matsukaze Co., Ltd.) is filled into the mold, and a photopolymerization irradiator. (Griplight II, manufactured by Matsukaze Co., Ltd.) is cured by light irradiation for 30 seconds. After curing, the mold is removed and used as an adhesion test specimen. This adhesion test specimen was immersed in distilled water at 37 ° C. for 24 hours, and then the dental adhesion test by shear bond strength at a crosshead speed of 1 mm / min using an Instron universal testing machine (Instron 5567, manufactured by Instron). I do. Further, in place of the central incisor of the bovine mandibular permanent tooth, an adhesion test to a porcelain disk-shaped flat plate (diameter: 15.0, height: 5.0 mm: vintage halo, manufactured by Matsukaze Co., Ltd.) was performed. That is, the same test as the tooth was performed on a sample that was subjected to sandblasting (0.2 MPa) on a porcelain adherend (# 600 polished) and then naturally dried after ultrasonic cleaning.

(2) Evaluation of adhesion durability test Purpose: Evaluation of adhesion to enamel and dentin using a medical / dental curable composition and adhesion to porcelain.

Evaluation method: After preparing an adhesion test specimen in the same manner as the adhesion test, the adhesion test specimen is immersed in distilled water at 37 ° C. for 24 hours. Thereafter, 2000 thermal cycles of alternately immersing in a constant temperature water bath at 4 ° C. and 60 ° C. for 1 minute each are performed. After completion of the thermal cycle, this adhesion test specimen was tested for dental adhesion and porcelain adhesion by using a Instron universal testing machine (Instron 5567, manufactured by Instron) at a crosshead speed of 1 mm / min. Perform the test.

(3) Evaluation of storage stability test Purpose: The prepared medical and dental curable compositions were stored in an environment of 50 ° C. for 4 weeks, and evaluation of adhesion to enamel and dentin using the composition was performed.

Evaluation method: The adhesion test by the shear bond strength is performed in the same manner as the adhesion test.

The abbreviations of the silane coupling agents used in Examples and Comparative Examples of the present invention are as follows.
SC1: 3- (Tris (((Z) -docos-13-en-1-yl) oxy) silyl) propyl methacrylate
SC2: 3- (Tris (((Z) -tetracos-15-en-1-yl) oxy) silyl) propyl methacrylate
SC3: 3- (Tris (((11Z, 14Z) -icosa-11,14-dien-1-yl) oxy) silyl) propyl methacrylate
SC4: 3- (Tris (((5Z, 9Z, 12Z) -octadeca-5,9,12-trien-1-yl) oxy) silyl) propyl methacrylate
SC5: 3- (Tris (((8Z, 11Z, 14Z, 17Z) -icosa-8,11,14,17-tetraen-1-yl) oxy) silyl) propyl methacrylate
SC_C1: 3- (Trimethoxysilyl) propyl methacrylate
SC_C2: 3- (Tris (undecyloxy) silyl) propyl methacrylate

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

(B) Phosphonic acid group-containing polymerizable monomer
MHPA: 6-methacryloyloxyhexylphosphonoacetate (c) a polyvalent carboxylic acid group-containing polymerizable monomer
AET: 4-acryloyloxyethyl trimellitic acid and others
MHP: 6-methacryloyloxyhexyl dihydrodiene phosphate
MDP: 10-methacryloyloxydecyl dihydrodiene phosphate (d) polymerizable monomer
Bis-GMA: 2,2-bis (4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl) propane
UDMA: Di (methacryloyloxy) -2,2,4-trimethylhexamethylene diurethane
TGDMA: Triethylene glycol dimethacrylate
HEMA: 2-hydroxyethyl methacrylate (f) Water-soluble organic solvent
EtOH: Ethanol (g) Polymerization initiator
CQ: Camphorquinone
DMBE: p-dimethylaminobenzoic acid ethyl ester and others
BHT: Dibutylhydroxytoluene
DW: distilled water

Preparation of Medical / Dental Curable Composition A one-pack type medical / dental curable composition (Formulation Examples 1 to 7) having the composition shown in Table 1 was prepared and used in Examples and Comparative Examples.

Evaluation results Tables 2 to 4 show C ₆ -C having at least one radical polymerizable group of the present invention and at least one of the alkoxide sites bonded to the silicon atom containing an unsaturated bond. The adhesive evaluation result to a dentine and porcelain of the medical / dental curable composition containing the silane coupling agent characterized by being a ₄₀ linear or branched alkyl group is shown. As can be seen from these results, it can be seen that the medical / dental curable composition containing the silane coupling agent of the present invention has good adhesion performance to the tooth and porcelain. The silane coupling agents (Comparative Examples 1 and 2) that have been used in the medical / dental field have shown good adhesion performances after preparation and after 2000 thermal cycles. In the adhesion test to porcelain after the weekly storage stability test, all the adherends dropped off. This is presumably because the dealcoholization (hydrolysis reaction) of the silane coupling agent progressed during the storage test, and the adhesive activity to porcelain was lost. In contrast, since the silane coupling agent of the present invention has a C _{6 to} C ₄₀ linear or branched alkyl group containing an unsaturated bond, it has large steric hindrance, high acid resistance, and high water resistance. This is probably because the decomposition reaction was suppressed. From the above evaluation results, the silane coupling agent of the present invention has high acid resistance, and can stably exist even under acidic conditions that are difficult to store with the prior art. This made it possible to produce a one-pack type medical and dental curable composition.

C ₆ -C ₄₀ linear or branched alkyl having at least one radical polymerizable group according to the present invention and at least one of the alkoxide moieties bonded to the silicon atom containing an unsaturated bond The silane coupling agent, which is characterized by being a group, can coexist in a silane coupling agent under acidic conditions, which was difficult to make into one solution by the conventional technology. Along with this, adhesion to bone, tooth, porcelain and the like became possible with a one-pot composition. This technical development is considered to contribute greatly to the progress of one-component medical and dental curable compositions, which has been considered difficult, and can be said to have high industrial utility value.

Claims (8)

A C ₆ -C ₄₀ linear or branched alkyl group having at least one kind of radical polymerizable group and at least one of the alkoxide moieties bonded to the silicon atom includes an unsaturated bond A silane coupling agent characterized by things. The silane coupling agent according to claim 1, wherein the molecular structure of the silane coupling agent is represented by the following formula.

A represents H ₂ C═CH—, H ₂ C═C (CH ₃ ) —, H ₂ C═CH—C ₆ H ₄ − group (C ₆ H ₄ represents a phenylene group), and B represents -C (O) -O-, -C (O) -S-, -C (O) -NH-, -NH-C (O) -NH-, -NH-C (O) -S-,- represents NH-C (O) -O- group, Z is a straight-chain or branched alkylene group of C ₁ -C _30, Y is, -NH-, -S-, -NH-C (O ) -S-,-NH-C (O) -O-, -NH-C (O) -NH-, -C (O) -S-, -C (O) -O-, -CH (OH) -CH ₂ -S-, -CH (OH) -CH ₂ -O- group, wherein R ² is a C _{1 to} C ₃₀ linear or branched alkylene group, -S-, -NH-, -NR ⁴ - (R ⁴ represents an alkylene _{group), -CH 2 -C 6 H 4} - (C 6 H 4 represents a phenylene group), includes -C (O) -O-, -O- groups X represents OR ³ , R ³ represents a C ₆ -C ₄₀ linear or branched alkyl group containing at least one unsaturated bond, and R ¹ represents a C ₁ -C ₁₆ linear chain Or represents a branched alkyl group or a phenyl group. Here, a is 1 to 6, and n is 1 to 3.
The silane coupling agent according to claim 1, wherein the molecular structure of the silane coupling agent is represented by the following formula.


A represents H ₂ C═CH—, H ₂ C═C (CH ₃ ) —, H ₂ C═CH—C ₆ H ₄ − group (C ₆ H ₄ represents a phenylene group), and B represents -C (O) -O-, -C (O) -S-,-C (O) -NH-, -NH-C (O) -NH-, -NH-C (O) -S-,- It represents NH-C (O) -O- group, Z is a linear or branched alkylene group of _{C 1 ~C 60, -CH (OH} ) -CH 2 -S-, -CH (OH) - CH ₂ -O- group, and D represents a C ₂ to C ₆₀ divalent to tetravalent linear or branched alkylene group, -C (O) -O-, -C (O) -S-, -C (O) -NH-, -NH-C (O) -NH-, -S-, -NH-C (O) -S-, -NH-C (O) -O- And / or has a trivalent triazine molecular skeleton or a divalent barbituric acid molecular skeleton, and E represents —NH—, —NR ⁴ — (R ⁴ represents an alkylene group), —O—, -S-, -NH-C (O) -S-, -NH-C (O) -NH-, -C (O) -S-, -NH-C (O) -O-, -C (O ) —O— group, R ² is a C _{1 to} C ₆₀ linear or branched alkylene group, —S—, —NH—, —CH ₂ —C ₆ H ₄ — (C ₆ H ₄ represents a phenylene group), -C (O) -O-, include a -O- group, R ³ is at least one unsaturated binding Represents a linear or branched alkyl group of C ₆ -C ₄₀ containing, R ¹ represents straight-chain or branched alkyl group of C ₁ -C _16, phenyl group. The sum of q and r is equal to the valence of D, r is a positive integer of 1 or more, a is 1 to 6, and n is 1 to 3.
The silane coupling agent according to claim 1, wherein the molecular structure of the silane coupling agent is represented by the following formula.





A represents H ₂ C═CH—, H ₂ C═C (CH ₃ ) —, H ₂ C═CH—C ₆ H ₄ − group (C ₆ H ₄ represents a phenylene group), and B represents -C (O) -O-, -C (O) -S-, -C (O) -NH-, -NH-C (O) -NH-, -NH-C (O) -S-,- It represents NH-C (O) -O- group, Z is a straight-chain or branched alkylene group of C ₁ -C _60, linear or branched alkyl group of R ¹ is C ₁ -C ₁₆ Represents a phenyl group, and R ² represents a C ₆ -C ₄₀ linear or branched alkyl group containing at least one unsaturated bond. Here, a is 1 to 6, and n is 1 to 3.
The silane coupling agent according to claim 1, wherein the molecular structure of the silane coupling agent is represented by the following formula.


A represents H ₂ C═CH—, H ₂ C═C (CH ₃ ) —, H ₂ C═CH—C ₆ H ₄ − group (C ₆ H ₄ represents a phenylene group), and R ² represents C _{1 to} C _{6 represents} a linear or branched alkyl group, R ¹ represents a C _{1 to} C ₁₆ linear or branched alkyl group, a phenyl group, and R ² represents at least one or more unsaturated groups A C ₆ -C ₄₀ linear or branched alkyl group containing a bond. Here, a is 1 to 6, and n is 1 to 3.
The silane coupling agent according to any one of claims 1 to 5, wherein the alkoxide moiety bonded to the silicon atom is a condensate of alcohol obtained by reducing the carboxyl group of the unsaturated fatty acid, and the alcohol derived from the unsaturated fatty acid is (Z ) -Tetradec-9-en-1-ol, (Z) -hexadec-9-en-1-ol, (Z) -hexadec-6-en-1-ol, (Z) -octadec-9-ene- 1-ol, (Z) -octadec-11-en-1-ol, (Z) -icos-9-en-1-ol, (Z) -icos-11-en-1-ol, (Z)- Docos-13-en-1-ol, (Z) -tetracos-15-en-1-ol, (9Z, 12Z) -octadeca-9,12-dien-1-ol, (11Z, 14Z) -icosa- 11,14-dien-1-ol, (13Z, 16Z) -docosa-13,16-dien-1-ol, (9Z, 12Z, 15Z) -octadeca-9,12,15-trien-1-ol, (6Z, 9Z, 12Z)-Octadeca-6,9,12-trien-1-ol, (5Z, 9Z, 12Z)-Octadeca-5,9,12-tri -1-ol, (9E, 11E, 13Z) -octadeca-9,11,13-trien-1-ol, (9E, 11E, 13E) -octadeca-9,11,13-trien-1-ol, (5Z, 8Z, 11Z) -icosa-5,8,11-trien-1-ol, (8Z, 11Z, 14Z) -icosa-8,11,14-trien-1-ol, (11Z, 14Z, 17Z ) -Icosa-11,14,17-trien-1-ol, (6Z, 9Z, 12Z, 15Z) -octadeca-6,9,12,15-tetraen-1-ol, (5Z, 8Z, 11Z, 14Z) ) -Icosa-5,8,11,14-tetraen-1-ol, (8Z, 11Z, 14Z, 17Z) -icosa-8,11,14,17-tetraen-1-ol, (5Z, 8Z, 10E) , 12E, 14Z) -Octadeca-5,8,10,12,14-pentaen-1-ol, (5Z, 8Z, 11Z, 14Z, 17Z) -Icosa-5,8,11,14,17-pentaene- 1-ol, (4Z, 7Z, 10Z, 13Z, 16Z) -docosa-4,7,10,13,16-pentaen-1-ol, (7Z, 10Z, 13Z, 16Z, 19Z) -docosa-7, 10,13,16,19-pentaen-1-ol, (9Z, 12Z, 15Z, 18Z, 21Z) -tetracosa-9,12,15,18,21-pentaen-1-ol, (4Z, 7Z, 10Z , 13Z, 16Z, 19Z) -Docosa-4,7,10,13,16,19-hexaen-1-ol, (6Z, 9Z, 1 6. The silane cup according to claim 1, wherein the silane cup is selected from 2Z, 15Z, 18Z, 21Z) -tetracosa-6,9,12,15,18,21-hexaen-1-ol. Ring agent
A medical / dental curable composition comprising the silane or pulling agent according to claim 1.
The medical / dental curable composition according to claim 1, wherein the phosphonic acid group-containing polymerizable monomer, the polyvalent carboxylic acid group-containing polymerizable monomer, the polymerizable monomer, water, and a water-soluble organic compound are used. A medical / dental curable composition comprising a solvent and a polymerization initiator.