JP2019064937A - Novel reactive organic silane compound as well as medical and dental hardening composition containing the same - Google Patents

Abstract

To provide medical and dental hardening compositions having adhesiveness of firmly adhering to biogenic hard tissue, capable of expressing adhesion durability even in severe intraoral environment, additionally storable in one liquid type packaging form that is excellent in storage stability and is difficult to be degraded and degenerated by hydrolysis caused by the temperature of environment and the acidity of solution, and the like.SOLUTION: Provided is a medical and dental hardening composition which has at least one radical polymeric group, and in which an organic silane compound containing alkylene strand that may contain a Cto Clinear or branched phenyl group binding to a silicon atom and contains an unsaturated bond between from the silicon atom to the β-position carbon.SELECTED DRAWING: Figure 2

Description

In the present invention, an alkylene chain having at least one or more radically polymerizable groups and capable of containing a C _{3 to} C ₄₀ linear or branched phenyl group bonded to a silicon atom is a silicon atom to a β-position carbon And an organosilane compound characterized by containing an unsaturated bond. Furthermore, the present invention relates to porcelains, metals, resins, composite resins, medical dental materials such as restorative materials, dental crown materials, prosthetic materials, cosmetic materials, corrective materials, preventive materials, abutment construction materials, root canal materials, etc. The present invention relates to a medical dental hardenable composition used for bonding to glass ionomer cement, living hard tissue (natural enamel and dentin of natural teeth) and the like.

In recent years, composite resin has dramatically improved long-term durability and mechanical properties, and it also has properties such as fluorine release and X-ray contrast properties, so tooth loss due to the onset of caries It has come to be used for functional and aesthetic restoration of dentin in the case where dental crown restoration occurs or fracture or omission of dental restoration. In addition, the use of this composite resin has been extended to applications such as tooth surface coating materials, weather sealants, orthodontic adhesives, resin core materials and the like. However, since these composite resins themselves do not have adhesion to not only dentin but also to ceramics and metals, it is essential to use various adhesives in combination. In particular, the adhesive material is required to have excellent adhesiveness to both dentin, which is mainly composed of inorganic component such as hydroxyapatite and dentin mainly composed of organic component such as collagen. It has been Furthermore, in recent years, it has become an issue to firmly adhere to ceramics, metals, resins, composite resins, glass ionomer cements and the like, and to have adhesion durability.

In the conventional adhesive, after the tooth surface is treated with a strong etching material such as phosphoric acid, a bonding material is applied to bond the tooth to the composite resin. However, in the method of treating the tooth surface with acid etching material, it is necessary to sufficiently remove the acid applied to the tooth surface by washing with water, and it is also necessary to dry it thereafter, and complicated operation steps are considered to be disadvantageous. . The adhesion method using an acid etching material is sufficient for enamel by forming a rough surface by deashing the acid etching material and macro mechanical fitting based on sufficient penetration and hardening of the bonding material. It showed adhesion. On the other hand, for dentin, since the sponge-like collagen fibers are exposed by deashing of the acid etching material, the bonding material does not sufficiently penetrate the collagen fibers, and it is difficult to obtain sufficient adhesion. there were. Therefore, in order to obtain high adhesion to dentin, an acid tooth surface treatment material has been proposed as an alternative to the phosphoric acid etching material. 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 texture surface treatment material containing a metal halide, A tooth surface treatment agent containing an amphoteric amino compound is disclosed in JP-279851, a tooth surface treatment member containing an organic carboxylic acid and a metal chloride is disclosed in JP-A-1-279815, and JP-A-5-163111 is disclosed. Examples thereof include tooth surface treatment materials containing an organic carboxylic acid and iron phosphate. However, even with the use of these acid tooth surface treatment materials, it has been difficult to obtain sufficient adhesion to dentin.

In Japanese Patent No. 2865794, as a polymerizable compound containing an acid group, (a) the following [Chemical formula 1] (wherein, R1 is a hydrogen atom or a methyl group, R2 is a C5-C10 group) An alkylene group, R 3 represents an alkylene group having 1 to 6 carbon atoms]] (meth) acrylic acid ester derivative containing a phosphonic acid group represented by (b) at least one radically polymerizable monomer and (c) An adhesive composition containing at least one polymerization initiator is disclosed: When a phosphonic acid group contained in a (meth) acrylic acid ester derivative is applied to a tooth, the phosphonic acid group is a component of the calcium component and the chemistry of the tooth. It is possible to attach a polymerizable group to the dentine surface as a result of bonding, and then it is announced that the primer is effective for penetration of collagen fibers exposed by the acid tooth surface treatment applied on the tooth surface. Journal of Dental Research Vol. 63, P 1087-1089, 1984: Primer composition consisting of glutaraldehyde / 2-HEMA / water] so that a three-step procedure consisting of acid treatment material / primer / bonding material will be performed As a proposal of an adhesion method involving this three-step technique, the methods described in Japanese Patent No. 3399573 and Japanese Patent No. 2926628 etc. can be mentioned, and the water-soluble polymerizable single substance contained in the primer can be mentioned. There is also disclosed a primer composition containing another water-soluble polymerizable monomer instead of 2-HEMA, since the dimeric 2-HEMA has mucosal irritant properties. No. 137211 discloses a primer composition containing polyethylene glycol or polyethylene glycol monomethacrylate, and Japanese Patent No. 278 2694 discloses a primer composition containing glyceryl mono (meth) acrylate. However, although these adhesion techniques have a large number of steps and are complicated to operate, and the adhesion to enamel is high, the adhesion to dentin still reaches a sufficient level. It was not.

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 capable of simultaneously performing an acid treatment to decalcify the tooth surface and a primer treatment to penetrate collagen fibers It has been proposed. In the case of using this primer, it is not necessary to treat the tooth surface with an acid, and a self-etching primer is applied to the tooth surface (applied / leaved), dried, and then the bonding material is applied. That is, by treating the cavity-formed tooth surface with a self-etching primer, it penetrates the dentin (enamel / dentin) while dissolving the smear layer generated by the cavity formation. After drying, by applying a bonding material thereto, the self-etching primer and the bonding material are integrated and cured to obtain a strong adhesive layer.

A number of proposals have been made for these self-etching primer compositions. For example, JP-A-1-13057 discloses a primer composition comprising a water / water-soluble film-forming agent / acid salt, and JP 2634276 discloses a water / hydroxyl-containing polymerizable compound / polymerizable compound having an acid group. No. 3480654 and Japanese Patent No. 3487389 disclose dental primers comprising a water / phosphoric acid 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 acid group / water-soluble vinyl compound having a hydroxyl group / water / aromatic sulfinate salt / aromatic amine,
JP-223289 discloses a primer composition consisting of 2-HEMA / water containing an organic acid or an inorganic acid, JP-A-4-8368 describes a water / polymerizable compound having an acid group / polymerizable compound having a hydroxyl group / The primer composition etc. which consist of an amino compound which has an acidic radical are mentioned. Although these compositions exhibit a certain degree of adhesion to dentin, they have not achieved sufficient adhesion to enamel due to their poor demineralizing action on inorganic components. In addition, since the primer composition contains an acid group-containing polymerizable monomer, a water-soluble polymerizable monomer and the like which have poor polymerizability, curing after application of the bonding material is insufficient, resulting in severe oral cavity Problems have arisen in adhesion durability under the environment. Furthermore, since these primer compositions are basically under an acidic atmosphere in which a water / acid group-containing polymerizable monomer coexists, the intramolecular main chain or functional group in the components contained in the primer composition Deterioration or deterioration occurs due to hydrolysis, and there are 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 by combining the primer and the bonding material to improve the tooth adhesion. For example, in JP-A-2000-212015 and JP-A-2000-16911, a bonding material containing an acylphosphine oxide compound as a photopolymerization initiator and a primer composition (polymerizable monomer having an acidic group / having a hydroxyl group / hydroxyl group) Dental adhesive system comprising polymerizable monomer / water, JP-A 2004-26838 discloses a primer composition containing a phosphoric acid group-containing polymerizable monomer / water and polyvalent rubonic acid A dental adhesion 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 an acid anhydride thereof A novel adhesion method comprising an adhesive composition comprising a primer solution and a vinyl monomer having an acidic group, JP-A-2000-204010 discloses a sulfonic acid group-containing polymerizable monomer / water-soluble polymerizable monomer / water Including Dental adhesive kit comprising a primer composition and an adhesive containing an acidic phosphoric acid ester-based polyfunctional polymerizable monomer, and in JP-A-9-295313, a sulfonic acid group-containing polymerizable monomer / water solubility A dental adhesion kit comprising a primer composition containing a polymerizable monomer / water and an adhesive containing a polyvalent carboxylic acid group-containing polyfunctional polymerizable monomer, JP-A-11-180814 discloses an acidic group-containing adhesive kit A tooth consisting of a self-etching primer containing (meth) acrylate / water-soluble organic solvent / water and a tooth adhesive containing an acid group and a hydroxyl-free (meth) acrylate / photopolymerization initiator / photopolymerization accelerator / filler Adhesive set, JP-A-6-24928 polymerizes a primer solution composition containing a specific metal compound / acidic group-containing polymerizable monomer / polymerizable monomer and trialkylboron or its partial oxide Contain as initiator No. 3449755 discloses an acidic group-containing vinyl polymer compound / hydroxyl group-containing water-soluble vinyl compound / primer composition containing water / aromatic amine and an acidic group-containing acrylic monomer / acidic group The adhesive agent kit etc. which consist of an acrylic adhesive containing a non-containing acrylic type monomer / polymerization initiator are mentioned.

All these proposals are used in combination with a specific bonding material in order to improve the curability of the primer composition containing the poorly polymerizable acid group-containing polymerizable monomer and the water-soluble polymerizable monomer. And adhesion to dentin (enamel and dentin). However, the low hardenability attributed to the components of the primer composition can not be fundamentally improved, and therefore the adhesion durability to both the enamel and the dentin as well as the adhesion durability is not sufficient. 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 monomer and (C) water is disclosed. According to this dental primer, high bond strength of 20 MPa or more can be obtained on 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 there are problems in storage stability and adhesion durability. For adhesion to inorganic materials such as ceramics, silane coupling agents such as 3-methacryloxypropyltrimethoxysilane are useful. However, as described above, since the adhesive properties to bones and teeth such as enamel and dentin are simultaneously required in the medical dental hardenable composition, the compound exhibiting acidity and water coexist. Therefore, silane coupling agents such as 3-methacryloxypropyltrimethoxysilane of the prior art, which are susceptible to acid hydrolysis, can not coexist.
That is, as shown in FIG. 1, the silane coupling agent having an alkoxy group such as 3-methacryloxypropyltrimethoxysilane causes dealcoholation from the silane coupling agent in both acid and alkali. As a result, since the generated silanol group (HO-Si) is unstable, dehydration condensation is repeatedly caused to become a polymer and to be inactivated (gelation / precipitation).

Therefore, it was a situation where it could not but be forced to supply in individual packaging form. That is, for adhesion to an inorganic material such as ceramics, first, silane coupling treatment with 3-methacryloxypropyltrimethoxysilane or the like is performed, and then, the curable composition for medical and dental applications is applied again. Techniques have been required.

Japanese Patent Application Laid-Open No. 62-33109 Japanese Patent Application Laid-Open No. 62-231652 Japanese Patent Application Laid-Open No. 63-279851 Unexamined-Japanese-Patent No. 1-279815 gazette JP-A-5-163111 Patent No. 2865794 Patent No. 3399573 Patent No. 296 2628 JP 2004-137211 A Patent No. 278 2694 Japanese Patent Application Laid-Open No. 1-113057 Patent No. 2634276 Patent No. 3480654 Patent No. 3487389 Japanese Patent Application Laid-Open No. 7-82115 Japanese Patent Application Laid-Open No. 62-223289 Japanese Patent Laid-Open No. 4-8368 Japanese Patent Laid-Open No. 2000-212015 Japanese Patent Laid-Open No. 2000-16911 Unexamined-Japanese-Patent No. 2004-26838 Patent No. 3236030 Japanese Patent Laid-Open No. 2000-204010 JP-A-9-295913 Japanese Patent Application Laid-Open No. 11-180814 JP 6-24928 A Patent No. 3449755 gazette Japanese Patent Application 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 the adhesiveness which firmly hardens after removal of the volatile component and firmly adheres to living hard tissues such as ceramics, bone, enamel and dentin, and the severe oral cavity. It is an object of the present invention to provide a medical / dentinary curable composition capable of developing adhesion durability that can withstand even in an internal environment. A further problem to be solved by the present invention is to enable a one-pack type packaging form excellent in storage stability which is not susceptible to deterioration or deterioration due to hydrolysis of the component due to environmental temperature, acidity of solution, etc. It is providing a medical dental hardenable composition.

As a result of repeated investigations, the present inventors have found that an alkylene chain having at least one or more types of radically polymerizable groups and which may contain a C _{3 to} C ₄₀ linear or branched phenyl group bonded to a silicon atom It has been found that the above-mentioned problems can be solved by using an organosilane compound, which comprises an unsaturated bond from the silicon atom to the β-position carbon, in a curable composition for medical and dental use. More specifically, the medical dental curing composition containing the organosilane compound, the phosphonic acid group-containing polymerizable monomer, and the polyvalent carboxylic acid group-containing polymerizable monomer has an acidic atmosphere in which water is allowed to coexist. Also in the lower part, it has excellent storage stability which is not susceptible to deterioration or deterioration due to hydrolysis of the component.

The medical dental curing composition using the organosilane compound of the present invention is considered to be less susceptible to degradation or deterioration due to hydrolysis by the reaction mechanism described below. That is, as shown in FIG. 2, the organosilane compound to which the allyl group is bonded deprives hydrogen from the silanol group on the surface of the porcelain, and the generated oxygen anion covalently bonds by attacking the silicon atom of the organosilane compound. At that time, for example, propene is detached. Therefore, the reaction mechanism of the organosilane compound of the present invention is largely different from the reaction mechanism with the silane coupling agent having an alkoxide group as shown in FIG.

The organosilane compound of the present invention can be firmly adhered to any of dentin such as porcelain ceramics, bone, enamel and dentin by using it in a medical dental curing composition, and It also has adhesion durability that can withstand even under severe oral environment. In addition, the medical dental curing composition containing the organosilane compound, 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 allowed to coexist. It also has excellent storage stability that is resistant to degradation or deterioration due to hydrolysis of the components.

Reaction scheme of silane coupling agent having alkoxy group Reaction scheme of the organic silane compound of the present invention Schematic diagram (1) showing the hydrogen bond between the organosilane compound of the present invention and the binder resin Schematic diagram (2) showing the hydrogen bond between the organosilane compound of the present invention and the binder resin

The alkylene chain of the present invention which can have a C _{3 to} C ₄₀ linear or branched phenyl group having at least one or more radically polymerizable groups and bonded to a silicon atom is from the silicon atom to the β-position carbon The molecular structure of the organosilane compound characterized in that it contains an unsaturated bond is, for example, the structure shown in the following general formula (1), and may be used alone or in combination. When the structure shown in the general formula (1) will be described in more detail, A _{is, H 2 C = CH-, H} 2 C = C (CH 3) -, H 2 C = CH-C 6 H 4 - represents a 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 a -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-, -OC (O) -NH-, -NH-C (O) -NH- , -C (O) -S-, -C (O) -O-, represents a _{-CH (OH) -CH 2 -S-,} -CH (OH) -CH 2 -O- group, R ¹ is C _A C ₃ -C ₄₀ linear or branched phenyl group containing an unsaturated bond from the silicon atom to the β-position carbon in the alkylene chain which may contain a phenyl group, R ² is a C ₁ -C ₄₀ linear or branched alkyl group R ³ is a C _{1 to} C ₃₀ linear or branched alkylene group, and is —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 include a -C (O) -O-, -O- group. Here, a is 1 to 6, and n is 1 to 3.

Below, a representative chemical structure of R ¹ is described.

Some representative chemical structures of the general formula (1) are specifically described below.

The alkylene chain of the present invention which can have a C _{3 to} C ₄₀ linear or branched phenyl group having at least one or more radically polymerizable groups and bonded to a silicon atom is from the silicon atom to the β-position carbon The molecular structure of the organosilane compound characterized in that it contains an unsaturated bond is, for example, a structure represented by the following general formula (2), and may be used alone or in combination. When the structure shown in the general formula (2) will be described in more detail, A _{is, H 2 C = CH-, H} 2 C = C (CH 3) -, H 2 C = CH-C 6 H 4 - represents a group (C ₆ H ₄ represents a phenylene group), B represents —C (O) —O—, —C (O) —S—, —C (O) —NH—, —NH—C (O) — NH—, —NH—C (O) —S—, —NH—C (O) —O— represents a group, and Z represents a C _{1 to} C ₆₀ linear or branched alkylene group, OH) -CH ₂ -S-, comprise a -CH (OH) -CH ₂ -O- group, D is a divalent tetravalent straight or branched chain alkylene group of C ₂ -C ₆₀ , -C (O) -O-, -C (O) -S-, -C (O) -NH-, -NH-C (O) -NH-, -S-, -NH-C (O) -S-, -NH-C (O) -O-, and / or having a trivalent triazine molecule skeleton or a bivalent barbituric acid molecule skeleton, E is -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- represents a group, wherein R ¹ is a C ₃ -C ₄₀ linear or branched phenyl group and an alkylene chain which may contain a silicon atom to β Unsaturated bond on carbon See, R ² represents a linear or branched alkyl group of C ₁ ~C _40, R ³ is a linear or branched alkylene group of _{C 1 ~C 30, -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 obtain. 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.

Some representative chemical structures of the general formula (2) are specifically described below.

The alkylene chain of the present invention which can have a C _{3 to} C ₄₀ linear or branched phenyl group having at least one or more radically polymerizable groups and bonded to a silicon atom is from the silicon atom to the β-position carbon The molecular structure of the organosilane compound characterized in that it contains an unsaturated bond is, for example, a structure shown by the following general formula (3), and may be used alone or in combination. When the structure shown in the general formula (3) will be described in more detail, A _{is, H 2 C = CH-, H} 2 C = C (CH 3) -, H 2 C = CH-C 6 H 4 - represents a group (C ₆ H ₄ represents a phenylene group), B represents —C (O) —O—, —C (O) —S—, —C (O) —NH—, —NH—C (O) — R ¹ represents an NH-, -NH-C (O) -S-, -NH-C (O) -O- group, Z represents a C _{1 to} C ₆₀ linear or branched alkylene group, R ¹ Is an alkylene chain which may contain a C _{3 to} C ₄₀ linear or branched phenyl group, containing an unsaturated bond from a silicon atom to a β carbon, and R ² is a C _{1 to} C ₄₀ linear or branched alkyl Represents a group. Here, a is 1 to 6, and n is 1 to 3.

Some representative chemical structures of the general formula (3) will be specifically described below.

The alkylene chain of the present invention which can have a C _{3 to} C ₄₀ linear or branched phenyl group having at least one or more radically polymerizable groups and bonded to a silicon atom is from the silicon atom to the β-position carbon The molecular structure of the organosilane compound characterized in that it contains an unsaturated bond is, for example, a structure represented by the following general formula (4), and may be used alone or in combination. When the structure shown in the general formula (4) will be described in more detail, A _{is, H 2 C = CH-, H} 2 C = C (CH 3) -, H 2 C = CH-C 6 H 4 - represents a group (C ₆ H ₄ represents a phenylene group), R ¹ is an alkylene chain which may contain a C _{3 to} C ₄₀ linear or branched phenyl group, containing an unsaturated bond from silicon atom to β carbon, R ² Represents a C _{1 to} C ₄₀ linear or branched alkyl group. Here, n is 1 to 3.

Some representative chemical structures of the general formula (4) will be specifically described below.

The alkylene chain of the present invention which can have a C _{3 to} C ₄₀ linear or branched phenyl group having at least one or more radically polymerizable groups and bonded to a silicon atom is from the silicon atom to the β-position carbon When an organosilane compound characterized by containing an unsaturated bond is used in a medical dental curing composition, it is preferable to use a medical dental curing composition containing the following components.

(A) an alkylene chain having at least one or more radically polymerizable groups and capable of containing a C _{3 to} C ₄₀ linear or branched phenyl group bonded to a silicon atom from the silicon atom to the β-position carbon An organosilane compound characterized by containing an unsaturated bond;
(B) a phosphonic acid group-containing polymerizable monomer;
(C) polyvalent carboxylic acid group-containing polymerizable monomers;
(D) polymerizable monomers;
(E) water;
(F) Water-soluble organic solvent; and (g) Polymerization initiator The details of each component are shown below.

(A) an alkylene chain having at least one or more radically polymerizable groups and capable of containing a C _{3 to} C ₄₀ linear or branched phenyl group bonded to a silicon atom from the silicon atom to the β-position carbon Organosilane compounds characterized by containing unsaturated bonds:
The alkylene chain of the present invention which can have a C _{3 to} C ₄₀ linear or branched phenyl group having at least one or more radically polymerizable groups and bonded to a silicon atom is from the silicon atom to the β-position carbon When using an organosilane compound characterized in that it contains an unsaturated bond in a curable composition for medical and dental use, it is preferable to contain 1 part by weight to 10 parts by weight in 100 parts by weight of the curable composition for medical and dental use, More preferably, it is 4 parts by weight to 6 parts by weight. When the amount of the organosilane compound is less than 1 part by weight, sufficient adhesive strength can not be obtained because the amount of the organosilane compound is too small relative to the silanol group on the adherend surface. On the other hand, if the amount is more than 10 parts by weight, sufficient bonding strength can not be obtained because fragile bonds between the organosilane compounds (increase of uncondensed sites in the xerogel structure) are increased.

(B) phosphonic acid group-containing polymerizable monomer
The phosphonic acid group-containing polymerizable monomer contained in the curable composition for medical and dental use of the present invention is, for example, one (-PO (OH) 2) or phosphonic acid monoester directly linked to at least a carbon atom in the molecule. A polymerizable monomer having a group (-PO (OH) (OR)) and at least one polymerizable unsaturated group is meant. That is, any functional group may be used in the molecule without any limitation as long as it satisfies these conditions. In addition, the phosphonic acid group-containing polymerizable monomer has a number of phosphonic acid groups or phosphonic acid monoester groups in the molecule, and (meth) acryloyl group, styryl group, vinyl group, allyl group etc. The type and number of groups are not particularly limited. By containing the phosphonic acid group-containing polymerizable monomer in the medical dental curing composition of the present invention, compared with the polymerizable monomer having a phosphoric acid monoester group or a phosphoric acid diester group, In particular, it is possible to exhibit excellent tooth adhesion to enamel. In addition, since the phosphonic acid group-containing polymerizable monomer is not bonded to the oxygen atom by the ester bond, the phosphonic acid group is less susceptible to hydrolysis in the molecule even under an acidic atmosphere in the presence of water, and thus is storage stable. It is excellent in sex. Therefore, it is also possible to use a one-pack packaging as well as a two-pack packaging divided into two.

Among these phosphonic acid group-containing polymerizable monomers, those having excellent tooth adhesion and storage stability [Formula 11] [wherein, R 1 is a hydrogen atom or a methyl group, and R 2 is 5 to 10 carbon atoms] An alkylene group and R3 show a C1-C6 alkylene group. It is preferable to use the phosphonic acid group containing polymerizable monomer shown by these.

Specific examples of the phosphonic acid group-containing polymerizable monomer shown in Chemical formula 18 include the following compounds and the like, but are not limited thereto.

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) acryloyloxyhexyl phosphonoacetate, 6- (meth) acryloyloxyhexyl-3-phosphonopropionate, 10- (meth) acryloyloxy It is more preferable to use decyl-3-phosphonoacetate, 10- (meth) acryloyloxydecyl phosphonopropionate, 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 use application or purpose of use of the medical dental curable composition and the method of use, but preferably the medical dental cure is preferred. The amount is in the range of 0.1 to 40.0 parts by weight in 100 parts by weight of the sex composition. When the content of the phosphonic acid group-containing polymerizable monomer exceeds 40.0 parts by weight, the curing property due to the polymerization property is reduced, 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 adhesion to enamel.

(C) Polyvalent carboxylic acid group-containing polymerizable monomer
The (c) polyvalent carboxylic acid group-containing polymerizable monomer contained in the medical / dental hardenable composition of the present invention can easily react, for example, with at least two or more carboxylic acid groups in the molecule, or with water. It means a polymerizable monomer having at least one polymerizable unsaturated group and a group generating two or more carboxylic acid groups. That is, as long as these conditions are satisfied, any functional group can be used without any limitation even if it has any functional group. Further, the type and number of radically polymerizable unsaturated groups such as (meth) acryloyl group, styryl group, vinyl group and allyl group in the molecule are also not particularly limited. . By containing the polyvalent carboxylic acid group-containing polymerizable monomer in the medical dental curing composition of the present invention, it is possible to exhibit excellent dentin bonding performance to dentin.

Specific examples of polyvalent carboxylic acid group-containing polymerizable monomers 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 1,3 2,3-Tricarboxylic acid, 4- (meth) acryloyloxyethyl trimellitic acid and its anhydride, 4- (meth) acryloyloxybutyltrimellitic acid and its anhydride, β- (meth) acryloyloxyethyl hydrogen sulfate Synate, β- (meth) acryloyloxyethyl hydrogen maleate, 11- (meth) acrylo Ryoxy-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 thereof include acryloyloxy-1,1-octanedicarboxylic acid, 10- (meth) acryloyloxy-1,1-decanedicarboxylic acid, 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid and the like. In what is limited There. 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 according to the use application or purpose of use of the curable composition for medical and dental use and the method of use, but preferably the medical and dental equipment is preferably used. The amount is in the range of 0.1 to 40.0 parts by weight in 100 parts by weight of the curable composition for use. When the content of the polyvalent carboxylic acid group-containing polymerizable monomer exceeds 40.0 parts by weight, the curing property 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 adhesiveness to dentin.

In the case of further enhancing the adhesion to hard tissues in the medical or dental hardenable composition of the present invention, or in the case of imparting adhesion to various adherends including noble metals, etc., the phosphonic acid group-containing polymerizable monomer Acidic group-containing polymerizable monomers other than monomers and polyvalent carboxylic acid group-containing polymerizable monomers, and polymerizable monomers containing a sulfur atom in the molecule can be included in combination. As acidic group-containing polymerizable monomers other than phosphonic acid group-containing polymerizable monomers and polyvalent carboxylic acid group-containing polymerizable monomers, those having at least one or more acidic groups in the molecule In particular, the type of the acidic group is not limited, and any acidic group-containing polymerizable monomer having any acidic group can be used. When the acidic group which those acidic group containing polymerizable monomers have is specifically illustrated, a phosphoric acid group (monoester or diester), a monocarboxylic acid group, a pyrophosphoric acid group, a sulfonic acid group, a thiophosphoric acid group etc. will be mentioned. Although it is not limited to these. Moreover, it can be used without any restriction also in the number (monofunctional group or polyfunctional group) of the radically polymerizable unsaturated group which the polymerizable monomer containing these acidic groups has, and its kind. Specific examples of the unsaturated group possessed by 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 group is mentioned. It is preferable that it is an acidic group-containing polymerizable monomer having a group. Furthermore, these acidic group-containing polymerizable monomers can 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 acid group-containing polymer having a (meth) acryloyl group as an unsaturated group are as follows. As the acidic group-containing polymerizable monomer having a phosphoric acid group, (meth) acryloyloxymethyl dihydrogen phosphate, 2- (meth) acryloyloxyethyl dihydrogen phosphate, 3- (meth) acryloyloxypropyl dihydro Gen phosphate, 4- (meth) acryloyloxybutyl dihydrogen phosphate, 5- (meth) acryloyl oxypentyl dihydrogen phosphate, 6- (meth) acryloyl oxyhexyl dihydrogen phosphate, 7- (meth) acryloyl oxyheptyl Dihydrogen phosphate, 8- (Meth) acryloyloxyoctyl dihydrogen phosphate, 9- (Meth) acryloyl oxynonyl dihydrogen phosphate, 10- (Meth) ac Royloxydecyl dihydrogen phosphate, 11- (meth) acryloyloxyundecyl dihydrogen phosphate, 12- (meth) acryloyl oxydodecyl dihydrogen phosphate, 16- (meth) acryloyl oxyhexadecyl dihydrogen phosphate, 20 -(Meth) acryloyloxyeicosyl dihydrogen phosphate, di (meth) acryloyl oxyethyl hydrogen phosphate, di (meth) acryloyl oxy butyl hydrogen phosphate, di (meth) acryloyl oxyhexyl hydrogen phosphate, di (meth) Acryloyloxyoctyl hydrogen phosphate, di (meth) acryloyl oxynonyl hydrogen phosphate, di (meth) acrylic Loyyloxydecyl hydrogen phosphate, 1,3-di (meth) acryloyloxypropyl-2-dihydrogen phosphate, 2- (meth) acryloyloxyethyl phenyl hydrogen phosphate, 2- (meth) acryloyloxyethyl 2'- Examples include, but are not limited to, bromoethyl hydrogen phosphate, (meth) acryloyloxyethyl phenyl phosphonate and the like.

Moreover, as an acidic-group containing polymerizable monomer which has a monocarboxylic acid group, (meth) acrylic acid, 2-chloro (meth) acrylic acid, 3-chloro (meth) acrylic acid, 2-cyano (meth) acrylic acid Acid, N- (meth) acryloyl-p-aminobenzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, 2- (meth) acryloyloxybenzoic acid, p-vinylbenzoic acid, 5- (meth) acryloylamino acid Although pentyl carboxylic acid etc. are mentioned, it is not limited to these.

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

Further, as the acidic group-containing polymerizable monomer having a sulfonic acid group, 2- (meth) acrylamido-2-methylpropane sulfonic acid, styrene sulfonic acid, 2-sulfoethyl (meth) acrylate, 4- (meth) And acryloyloxybenzenesulfonic acid, 3- (meth) acryloyloxypropanesulfonic acid, etc., but not limited thereto.

In addition, examples of the acidic group-containing polymerizable monomer having a thiophosphoric acid group include, but are not limited to, 10- (meth) acryloyloxydecyl dihydrogen dithiophosphate and the like.

Although the acidic group-containing polymerizable monomer is described above, the present invention is not limited to these, and the polymerizable monomers having these acidic groups can be used singly or in combination of two or more. Furthermore, as these acidic group-containing polymerizable monomers, not only monomers having a short main chain, but oligomers, prepolymers, polymers and the like having a long main chain can be used without any limitation. Metal salts partially neutralized with an acidic group contained in these acidic group-containing polymerizable monomers, derivatives of acidic group-containing polymerizable monomers such as ammonium salts or acid chlorides are also applicable to various adherends It can be used as long as it does not adversely affect the adhesion of

It is also effective for the present invention to use a polymerizable monomer containing a sulfur atom in the molecule in order to impart adhesiveness to a noble metal to the medical dental curing composition of the present invention. As long as it is a polymerizable monomer containing a sulfur atom in the molecule, it can be used regardless of the kind and number of unsaturated groups and the presence or absence of other functional groups. Specific examples of a polymerizable monomer containing a sulfur atom in a molecule having a (meth) acryloyl group as an unsaturated group are (meth) acrylate having a triazine thiol group, (meth) acrylate having a mercapto group, (Meth) acrylate having polysulfide group, (meth) acrylate having thiophosphoric acid group, (meth) acrylate having disulfide cyclic group, (meth) acrylate having mercaptodiathiazole group, (meth) acrylate having thiouracil group, thiirane Although the (meth) acrylate etc. which have group are mentioned, it is not limited to this. These polymerizable monomers containing a sulfur atom in their molecule can be used singly or in combination of two or more.

(D) Polymerizable Monomer The polymerizable monomer contained in the medical dental curing composition of the present invention is either monofunctional or multifunctional regardless of the type of radically polymerizable unsaturated group. Can be used without any restrictions. Examples of the kind of radically polymerizable unsaturated group possessed by the polymerizable monomer include (meth) acryloyl group, (meth) acrylamido group, styryl group, vinyl group, allyl group and the like, but in particular (meth) It is preferable to use a polymerizable monomer having an acryloyl group or a (meth) acrylimido 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 esters such as cyclohexyl (meth) acrylate, benzyl (meth) acrylate, allyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, isobonyl (meth) acrylate, Silane compounds such as γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, 2- (N, N-dimethylamino) ethyl (meth) Nitrogen-containing compounds such as acrylates, 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- (meth) ) Acryloyloxyethoxyphenyl) -2 (4- (meth) acryloyloxydiethoxypheny) ) Propane, 2 (4- (meth) acryloyloxydiethoxyphenyl) -2 (4- (meth) acryloyloxytriethoxyphenyl) propane, 2 (4- (meth) acryloyloxydipropoxyphenyl) -2 (4- (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 Rate, 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. As a hydrophobic polymerizable monomer containing an aliphatic tetrafunctional group, pentaerythritol tetra (meth) acrylate, pentaerythritol tetraacrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3 -Polymerizable monomers having a hydroxyl group such as -chloro-2-hydroxypropyl (meth) acrylate and methylcyclohexanediisocyanate, methylenebis (4-cyclohexylisocyanate), hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, diisocyanate methyl methyl Difunctional or trifunctional or higher polymerization derived from adducts with benzene, diisocyanate compounds such as 4, 4-diphenylmethane diisocyanate Group, and urethane bond such as di (meth) acrylate, 2,2-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 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) acrylic , 2,3-dihydroxypropyl (meth) acrylate, 2-hydroxypropyl-1,3-di (meth) acrylate, 3-hydroxypropyl-1,2-di (meth) acrylate, pentaerythritol di (meth) Acrylate, 2-trimethylammoniumethyl (meth) acryl chloride, (meth) acrylamide, 2- hydroxyethyl (meth) acrylamide, polyethylene glycol di (meth) acrylate (the number of oxyethylene groups is 9 or more), 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 (meta) acrylic Although over bets (the number of oxyethylene groups those 23), and the like, but is not limited thereto.

The (e) water contained in the medical / dental hardenable composition of the present invention is the phosphonic acid group-containing polymerizable monomer contained in the medical / dental hardenable composition or the polyvalent carboxylic acid group-containing polymerizability By activating the acid group possessed by the monomer or the like, it has the function of promoting the decalcification action on the living hard tissue and promoting the penetration of the living hard tissue. Therefore, water can be used without any limitation as long as it does not contain an impurity that adversely affects storage stability, biocompatibility, polymerizability, and adhesion to biological hard tissues. Preferably, distilled water or ion exchange water is used. The water content can be selected as appropriate depending on the use application or purpose of use of the medical dental hardenable composition of the present invention and the use method, but preferably 100 parts by weight of the medical dental hardenable composition , 0.1 to 80.0 parts by weight. If the water content exceeds 80.0 parts by weight, the storage stability such as separation of the composition without maintaining a uniform state is adversely affected. On the other hand, when the content of water is less than 0.1 parts by weight, sufficient adhesiveness can not be obtained with respect to various adherends including hard tissues.

(F) Water-soluble organic solvent The water-soluble organic solvent contained in the medical dental hardenable composition of the present invention (f) is a phosphonic acid group-containing polymerizable unit contained in the medical dental hardenable composition. Has a role as a dissolution accelerating agent to compatibilize various polymerizable monomers including water, polyvalent carboxylic acid group-containing polymerizable monomer, water, polymerization initiator and other compounding components in any ratio. In addition, it has the function of promoting the penetration of a dental hardenable composition for dental care. Moreover, the liquid viscosity of the curable composition for medical dentistry can be reduced, and the operativity, such as application | coating to the site | part which drips from a container, and adhere | attaches, can be improved. Specific examples of this 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 may be mentioned, but the organic solvents are not limited thereto and can be used without any limitation. Moreover, 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 according to the use application or purpose of use of the medical dental hardenable composition of the present invention and the use method, but preferably 100 parts by weight of the medical dental hardenable composition , 0.1 to 80.0 parts by weight. When the content of the organic solvent exceeds 80.0 parts by weight, the adhesion to the dentin decreases. On the other hand, when the content of the organic solvent is less than 0.1 parts by weight, the storage stability such as separation of the composition without maintaining the uniform state is adversely affected.

(G) Polymerization initiator The polymerization initiator (g) contained in the medical dental curing composition of the present invention is not particularly limited, and known radical generators may be used without any limitation. As a kind of a polymerization initiator, what makes polymerization start by mixing generally immediately before use (chemical polymerization initiator), what makes polymerization start by heating or heating (thermal polymerization initiator), makes polymerization by light irradiation These are roughly classified into initiators (photopolymerization initiators), but any of them can be used alone or in combination.

As the above-mentioned chemical polymerization initiator, a redox type polymerization initiator system consisting of organic peroxide / amine compound or organic peroxide / amine compound / sulfinate, organic peroxide / amine compound / borate compound, oxygen And organic boron compounds which react with water to initiate polymerization, polymerization systems such as perborates, permanganates, persulfates, etc., and also sulfinates, borate compounds and barbituric acids The 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 Examples thereof include, but are not limited to, 5-dimethylhexane, 2,5-dihydroperoxide, methyl ethyl ketone peroxide, and tertiary butyl peroxybenzode. Moreover, the said organic peroxide can also be used individually or in combination of several types.

As the amine compound, secondary or tertiary amines in which an amine group is bonded to an aryl group are preferable, and 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 thereto. 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. Further, the sulfinates may be used alone or in combination of several kinds.

Specific examples of borate compounds include sodium salts and lithium salts of trialkylphenylboron, trialkyl (p-fluorophenyl) boron (wherein the alkyl group is n-butyl, n-octyl, n-dodecyl, etc.) Although a potassium salt, magnesium salt, tetrabutyl ammonium salt, tetramethyl ammonium salt etc. are mentioned, it is not limited to this. Moreover, the said borate compound can also be used individually or in combination of several types.

Specific examples of barbituric acids include barbituric acid, 1,3-dimethyl barbituric acid, 1,3-diphenyl barbituric acid, 1,5-dimethyl barbituric acid, 5-butyl barbituric acid, 5- Ethylbarbituric acid, 5-isopropylbarbituric acid, 5-cyclohexylbarbituric 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-phenyl barbituric acid, 1-cyclohexyl-5-ethyl barbituric acid, 1- N-disil-5-phenylbarbituric acid and thiobarbituric acids, and salts thereof (especially, alkali metals or alkaline earth metals are preferred), for example, sodium 5-butylbarbiturate, 1,3,5-trimethylbarbi Examples include, but are not limited to, sodium tungstate, calcium 1,3,5-trimethylbarbiturate and sodium 1-cyclohexyl-5-ethylbarbiturate. Further, the above barbituric acids can be used alone or in combination of several kinds.

When the medical dental curing composition of the present invention is used alone, these chemical polymerization initiators need to be divided and contained in at least two or more packaging forms. In addition, when the medical dental hardenable composition of the present invention is used together with another composition, a chemical polymerization initiator is initiated so that the medical dental hardenable composition starts chemical polymerization upon contact with the other composition. Can be included in both the medical dental hardenable composition of the present invention and other compositions. Among these chemical polymerization initiators, sulfinates, barbituric acids, organic peroxides and tertiary amines are preferably used singly or in combination, and more preferably organic peroxides and tertiary amines Organic peroxide-tertiary amine-barbituric acids, 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 0.1 to 10.0 parts by weight, with respect to 100 parts by weight of the medical dental curing composition. Is to contain.

As a photoinitiator, what consists of a system only of a photosensitizer, and what consists of a combination of a photosensitizer / photopolymerization accelerator etc. is mentioned. The photosensitizers are roughly classified into those in which polymerization is initiated by ultraviolet light and those in which polymerization is initiated by visible light.

Specific examples of photosensitizers that can be used as a photopolymerization initiator include benzyl, camphorquinone, α-naphthyl, acetonaphthene, p, p'-dimethoxybenzyl, p, p'-dichlorobenzylacetyl, pentanedione 1, 2-phenanthrenequinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9, 10-phenanthrenequinone, α-diketones such as naphthoquinone, benzoin alkyl such as benzoin, benzoin methyl ether and benzoin ethyl ether Ethers, thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 2-methoxy thioxanthone, 2-hydroxy thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthate Thioxanthones such as benzophenone, acetoin benzophenone, p-chloro benzophenone, p-methoxy benzophenone such as p-methoxy benzophenone, 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, bis (2, 6- dimethoxy benzoyl) 2, 4 Acyl phosphine oxides such as 2,4-trimethylpentyl phosphine oxide, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-diethylamino-1- (4-morpholino) Α) aminoacetophenones such as phenyl) -propanone-1, etc., ketals such as benzyl dimethyl 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 include titanocenes such as fluoro-4-disiloxyphenyl) -titanium and the like, but are not limited thereto. 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 Benzyl aniline, 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 Anthranilic acid methyl ester, N, N-dihydroxyethyl aniline, N, N-dich 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 5-phenyl barbituric acid, 1,3,5-trimethyl barbituric acid, sodium 1,3,5-trimethyl barbiturate, barbituric acids such as calcium 1,3,5-trimethyl barbituric acid, dibutyltin diacetate , Tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin diversatate, dioctyltin bis (mercaptoacetic acid isooctyl ester) salt, tetramethyl-1,3-diacetoxydistanoxane, lauryl aldehyde, terephthalaldehyde, etc. And aldehyde compounds, and sulfur-containing compounds such as dodecyl mercaptan, 2-mercaptobenzoxazole, 1-decanethiol, thiosalicylic acid and the like, but not limited thereto. Moreover, the said photopolymerization promoter can also be used individually or in combination of several types.

Furthermore, in addition to the photopolymerization accelerator, citric acid, malic acid, tartaric acid, glycolic acid, gluconic acid, α-oxyisobutyric acid, 2-hydroxypropanoic acid, 3-hydroxypropane, in addition to the above-mentioned photopolymerization accelerators, for the improvement of photopolymerization accelerating ability. It is effective to add an oxycarboxylic acid such as an acid, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid, and dimethylolpropionic acid.

Moreover, when using a photoinitiator, even if it is a package form or the package form divided | segmented into two or more, there is no restriction | limiting in particular. Among these photopolymerization initiators, a combination of an α-diketone and a tertiary amine or an α-diketone and a tin compound is preferable, and more preferably aminos such as camphorquinone and ethyl pN, N-dimethylaminobenzoate and the like Combination of an aliphatic tertiary amine having a double bond in the molecule such as aromatic tertiary amine or N, N-dimethylaminoethyl methacrylate in which the group is directly linked to a benzene ring, and further, 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, and more preferably 0.1 to 10.0 parts by weight with respect to 100 parts by weight of each of the medical dental curing compositions. It is to contain in the range of part. Most preferably, the content is in the range of 0.1 to 8.0 parts by weight.

Moreover, as a thermal polymerization initiator by heating or heating, azo compounds such as azobisisobutyronitrile, azobisisobutyric acid methyl, azobiscyanovaleric acid and the like are suitably used in addition to the above organic peroxides. It is not limited to Moreover, these thermal polymerization initiators can also be used individually or in combination of several types. Furthermore, depending on the intended use, Brensted acid or Lewis acid can be obtained by light irradiation of coumarin-, cyanine-, thiazoline-based sensitizing dyes, halomethyl-substituted s-triazine derivatives, diphenyliodonium salt compounds, etc. The photoacid generator to be produced, quaternary ammonium halides, transition metal compounds and the like can also be suitably used.

A curable composition for medical and dental purposes with the purpose of thickening the curable composition for medical and dental use of the present invention to improve operability, or for imparting mechanical strength to the adhesive interface layer to improve adhesion. Can contain fillers. The filler is not particularly limited, and those known as dental fillers can be used. For example, an inorganic filler and / or an organic filler and / or an organic-inorganic composite filler may, for example, be mentioned, and these may be used alone or in combination of several types without any limitation. In addition, the shape of these fillers may be any particle shape such as spherical, needle, plate, crushed, and scaly, and is not particularly limited. Furthermore, the particle diameter 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, from the viewpoint of problems such as sedimentation and separation. Among these fillers, silica-zirconia oxide particles and the like formed from a solution such as Aerosil produced by the vapor phase method which is an ultrafine particle or an ultrafine particle silica composite particle and sol-gel reaction which is an ultrafine particle are curable compositions for medical and dental use. It is effective for the present invention to act as a thickener by being incorporated 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. In addition, there is no problem even if a cohesive inorganic filler or the like in which those ultrafine particles are purposely agglomerated is used.

In addition, among medical-dental hardenable compositions, ultraviolet absorbers such as 2-hydroxy-4-methylbenzophenone, hydroquinone, hydroquinone monomethyl ether, 2,5-di-tert-butyl-4-methylphenol, etc. The components such as polymerization inhibitors, discoloration inhibitors, antibacterial agents, color pigments, and other conventionally known additives can be optionally added as needed.

The method of use of the curable composition for medical and dental use of the present invention is not particularly limited, and is not limited to use alone, but may be etching material, primer, bonding material, self-etching primer, ceramic primer, metal primer, noble metal primer etc. It can be used in combination with other compositions as appropriate.

The medical dental hardenable composition of the present invention is characterized by having 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, depending on the proportion of components to be mixed with the medical dental hardenable composition of the present invention, the type of polymerization initiator, the method of use, the purpose of use, etc., two or more packaging forms can be selected and selected appropriately. 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 hardenable composition prepared in the following examples is as follows.

(1) Adhesion test Evaluation purpose: Evaluation of adhesion to dentin and tooth enamel, and adhesion to porcelain using a hardenable dental dental composition.

Evaluation method: After slaughtering, after removing frozen extract of bovine incisor mandibular permanent incisors which had been removed within 24 hours, thawing, removal of tooth root and cutting of coronal part are performed to prepare bovine tooth chips, Embed the bovine tooth chips in epoxy resin. Under water injection, the embedded bovine tooth is exposed to enamel or dentin with # 600 water-resistant abrasive paper, and then washed with water and dried. A 4 mm diameter perforated double-sided tape is applied to the exposed enamel or dentin to define the adhesive surface. The curable composition for medical and dental use prepared by applying examples or comparative examples to the prescribed adhesive surface is applied, light irradiation is performed for 30 seconds using a photopolymerization irradiator (Griplight II, manufactured by Matsukaze Co., Ltd.), and curing is performed. Did. Thereafter, a plastic mold (inner diameter: 4 mm, height: 2 mm) is fixed to the adhesive-treated surface, and a photopolymerizable composite resin (Beauty Fill II, made by Shofu Co., Ltd.) is filled inside the mold, and a photopolymerization irradiator Light is applied for 30 seconds using (Grip Light II, manufactured by Matsukaze Co., Ltd.) for curing. After curing, the mold is removed and it is taken as an adhesion test. This adhesion test body is immersed in distilled water at 37 ° C. for 24 hours, and then the tooth adhesion test with shear adhesion strength at a crosshead speed of 1 mm / min using an Instron universal tester (Instron 5567, Instron Co., Ltd.) I do. In addition, in place of the incisors of the lower permanent dentition of the bovine tooth, an adhesion test to a ceramic material disk-shaped flat plate (diameter 15.0, height 5.0 mm: vintage halo, manufactured by Matsukaze Co., Ltd.) was performed. That is, the ceramic adherend (# 600 polished) was subjected to sandblasting (0.2 MPa), and the sample which was naturally dried after ultrasonic cleaning was subjected to the same test as that for the tooth quality.

(2) Adhesion Durability Test Evaluation Purpose: Evaluation of dental adhesiveness to enamel and dentin and adhesiveness to porcelain using a curable composition for medical and dental use.

Evaluation method: After preparing an adhesion test body in the same manner as the adhesion test, the adhesion test body is immersed in 37 ° C. distilled water for 24 hours. Thereafter, 2000 cycles of thermal cycles are carried out by alternately immersing each in a constant temperature water bath at 4 ° C. and 60 ° C. for 1 minute. After completion of the thermal cycle, this adhesion test specimen is subjected to a tooth adhesion test and a porcelain adhesion test with a shear adhesion 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: The prepared various medical dental hardenable compositions were stored for 4 weeks in an environment of 50 ° C., and evaluation of adhesion to enamel and dentin using the compositions.

Evaluation method: Conduct adhesion test by shear adhesion strength in the same manner as the adhesion test.

Abbreviations of the silane coupling agent and the organic silane compound used in Examples and Comparative Examples of the present invention are as follows.
SC1: 3- (Triallylsilyl) propyl methacrylate
SC2: 3- (tri ((E) -hept-2-en-1-yl) silyl) propyl methacrylate
SC3: 3- (Tricinnamylsilyl) propyl methacrylate
SC4: 2-((((11- (Triallylsilyl) undecyl) oxy) carbonyl) amino) ethyl methacrylate
SC5: 2-((((11- (tricinnamylsilyl) undecyl) oxy) carbonyl) amino) ethyl methacrylate
SC_C1: 3- (trimethoxysilyl) propyl methacrylate
SC_C2: 3- (trimeethoxysilyl) propyl methacrylate

Abbreviations of materials used for the medical dental hardenable compositions of the examples of the present invention and the comparative examples are as follows.

(B) phosphonic acid group-containing polymerizable monomer
MHPA: 6-methacryloyloxyhexyl phosphonoacetate
MHP: 6-methacryloyloxyhexyl dihydrogen phosphate
MDP: 10-methacryloyloxydecyl dihydrogen phosphate

(C) Polyvalent carboxylic acid group-containing polymerizable monomer
AET: 4-acryloyloxyethyl trimellitic acid and other (d) polymerizable monomers
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 (meth) methacrylate (f) water soluble organic solvent
EtOH: ethanol (g) polymerization initiator
CQ: camphor quinone
DMBE: p-Dimethylaminobenzoic acid ethyl ester other
BHT: dibutyl hydroxytoluene
DW: Distilled water

Preparation of curable composition for medical and dental use The composition shown in Table 1 was used to prepare a one-component type medical curable composition for medical and dental use (Preparation Examples 1 to 7) and used in Examples and Comparative Examples.

Evaluation Results Tables 2 to 4 show alkylene having at least one or more radically polymerizable groups of the present invention and capable of containing a C _{3 to} C ₄₀ linear or branched phenyl group bonded to a silicon atom. The evaluation result of the adhesiveness to the tooth substance and porcelain of the medical dental curing composition containing the organosilane compound characterized by the chain | strand containing an unsaturated bond from (beta) atom to (beta) carbon is shown. As can be seen from these results, the medical dental curing composition containing the organosilane compound of the present invention is found to have good adhesion performance to dentin and porcelain. In particular, as shown in FIGS. 3 and 4, since Examples 4 and 5 have a urethane bond in the organic silane compound molecule, polar groups (-OH, -NH of the binder resin Bis-GMA, UDMA) It showed higher adhesion strength to form intermolecular hydrogen bond with -CO-O-, -O-CO-NH-). In addition, the silane coupling agents (Comparative Examples 1 and 2) conventionally used in the medical and dental fields have lower values compared to the Examples, but the adhesion is lower in comparison between immediately after preparation and after 2000 thermal cycles. It showed good adhesion performance without much difference. The reason why Comparative Example 1 showed a high value as compared with Comparative Example 2 is considered to be derived from the activity of the alkoxide group bonded to the silicon atom. That is, since the methoxy group of Comparative Example 1 exhibits high hydrolyzability compared to the ethoxy group of Comparative Example 2, it is considered that more radically polymerizable groups are introduced onto the adherend surface. Moreover, in the adhesion test after the storage stability test at 40 ° C. for four weeks, all the adherends in the comparative example were dropped off. This is considered to be because the dealcoholization (hydrolysis reaction) and condensation of the silane coupling agent proceeded during the storage test, and the adhesive activity was lost by forming a gel body of the silane coupling agent itself. In contrast, in the examples using the organosilane compound of the present invention, no statistically significant difference was found immediately after preparation, after 2000 thermal cycles and after storage stability test. Here, it can be considered as follows that the test results of the example showed significantly different values from the comparative example. That is, as shown in FIG. 1, the silane coupling agent conventionally used in the medical and dental fields has an alkoxy group which is a hydrolyzable group. The alkoxy group is easily decomposed by an acid and converted to a silanol group. After the conversion, dehydration condensation proceeds between silanol groups (between the silane coupling agent and between the silane coupling agent and the silanol group on the surface of the porcelain) to form a siloxane bond. Thus, the silane coupling agent having an alkoxy group forms a siloxane bond in a two-step reaction. In contrast, as shown in FIG. 2, it may have at least one or more radically polymerizable groups of the present invention, and may contain a C _{3 to} C ₄₀ linear or branched phenyl group bonded to a silicon atom. An organosilane compound which is characterized in that the alkylene chain contains an unsaturated bond from the silicon atom to the β-position carbon is considered to be highly reactive because it forms a siloxane bond in a one-step reaction. Moreover, in order to maintain a chemical structure, without hydrolyzing even after a storage stability test, in order to have high acid stability compared with an alkoxy group, it is considered to have a favorable storage stability. From the above evaluation results, the organic silane compound of the present invention is high in acid resistance, and can be stably present even under acidic conditions that are difficult to store in the prior art. This made it possible to produce a one-component curable composition for medical and dental care.

According to the present invention, an alkylene chain having at least one or more kinds of radically polymerizable groups and capable of containing a C _{3 to} C ₄₀ linear or branched phenyl group bonded to a silicon atom from a silicon atom to β carbon The organosilane compounds characterized by containing unsaturated bonds have become able to coexist with the organosilane compounds under acidity, which was difficult to liquefy in the prior art. As a result, adhesion to bone, dentin and porcelain etc. has become possible with a one-pot composition. This technological development is considered to greatly contribute to the development of one-component medical dental hardenable compositions which have been considered difficult, and it can be said that the industrial utility value is high.

Claims (8)

An alkylene chain having at least one or more radically polymerizable groups and capable of containing a C _{3 to} C ₄₀ linear or branched phenyl group bonded to a silicon atom is unsaturated from the silicon atom to the β-position carbon An organic silane compound characterized by containing a bond.
The organosilane compound according to claim 1, wherein the molecular structure of the organosilane compound is the following formula.


A _{is, H 2 C = CH-, H} 2 C = C (CH 3) -, H 2 C = CH-C 6 H 4 - represents a group (C ₆ H ₄ represents a phenylene group), B is -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-, -OC (O) -NH-, -NH-C (O) -NH-, -C (O) -S-, -C (O) _{-O-, -CH (OH) -CH 2} -S-, represents -CH (OH) -CH ₂ -O- group, R ¹ is includes a straight-chain or branched-chain phenyl groups of the C ₃ -C ₄₀ R ² is a C _{1 to} C ₄₀ linear or branched alkyl group, R ³ is a C _{1 to} C ₃₀ linear or an alkylene group of ^{branched, -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. Here, a is 1 to 6, and n is 1 to 3.
The organosilane compound according to claim 1, wherein the molecular structure of the organosilane compound is the following formula.

A _{is, H 2 C = CH-, H} 2 C = C (CH 3) -, H 2 C = CH-C 6 H 4 - represents a group (C ₆ H ₄ represents a phenylene group), B is -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) - comprise a CH ₂ -O- group, D is represents a tetravalent straight or branched chain alkylene group having from divalent _{C 2 ~ C 60, -C (} O) -O-, -C (O) -S-, -C (O) -NH-, -NH-C (O) -NH-, -S-, -NH-C (O) -S-, -NH-C (O) -O- wherein obtain, 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), -O-, -S-, -NH-C (O) -S-, -NH-C (O) -NH-, -C (O) -S-, -NH-C (O) -O-, -C (O And R ¹ is an alkylene chain which may contain a C ₃ -C ₄₀ linear or branched phenyl group and contains an unsaturated bond from a silicon atom to the β-position carbon, and R ² is a C ₁ to C _{1 group} . Table a straight or branched chain alkyl group having C ₄₀ , R ³ is a linear or branched alkylene group of _{C 1 ~C 30, -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 include a -C (O) -O-, -O- 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 organosilane compound according to claim 1, wherein the molecular structure of the organosilane compound is the following formula.

A _{is, H 2 C = CH-, H} 2 C = C (CH 3) -, H 2 C = CH-C 6 H 4 - represents a group (C ₆ H ₄ represents a phenylene group), B is -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 phenyl group of R ¹ is C ₃ -C ₄₀ And R ² represents a C _{1 to} C ₄₀ linear or branched alkyl group containing an unsaturated bond from the silicon atom to the β carbon in the alkylene chain which may contain Here, a is 1 to 6, and n is 1 to 3.
The organosilane compound according to claim 1, wherein the molecular structure of the organosilane compound is the following formula.

A _{is, H 2 C = CH-, H} 2 C = C (CH 3) -, H 2 C = CH-C 6 H 4 - represents a group (C ₆ H ₄ represents a phenylene group), R ¹ is The C ₃ -C ₄₀ linear or branched phenyl group may contain an unsaturated bond from the silicon atom to the β-position carbon, and R ² is a C ₁ -C ₄₀ linear or branched alkyl group Represents Here, n is 1 to 3.
The organosilane compound according to any one of claims 1 to 5, wherein the alkylene chain R ¹ bonded to the silicon atom is
3λ ³ -prop-1-ene, (E)-(3λ ³ -prop-1-en-1-yl) benzene, (E) -5λ ³ -penta-1,3-diene, (E) -1λ ³ -but-2-ene, (E ) -1λ 3 -pent-2-ene, (E) -4-methyl-1λ 3 -pent-2-ene, 2-methyl-4λ 3 -but-2-ene, (Z) -2- (λ ³ -methyl) but-2-ene, 2- (λ ³ -methyl) -3-methylbut-2-ene, (E) -1λ ³ -hex-2-ene, (E ) -4-methyl-1λ ³ -hex-2-ene, (E) -5-methyl-1λ ³ -hex-2-ene, (E) -4,5-dimethyl-1λ ³ -hex-2-ene , (Z) -2- (λ ³ -methyl) hex-2-ene, (E) -3-methyl-1λ ³ -hex-2-ene, (Z) -2- (λ ³ -methyl) hex- 2-ene, (Z) -2- (λ ³ -methyl) -3-methylhex-2-ene, (Z) 2- (λ ³ -methyl) -3,4-dimethylhex-2-ene, (Z The organosilane compound according to any one of claims 1 to 5, characterized in that it is selected from -2- (λ ³ -methyl) -3,4,5-trimethylhex-2-ene.
The medical dental hardenable composition containing the organosilane compound of any one of Claims 1-6.
The curable composition for medical and dental use according to claim 7, comprising a phosphonic acid group-containing polymerizable monomer, a polyvalent carboxylic acid group-containing polymerizable monomer, a polymerizable monomer, water, a water-soluble organic solvent, The medical dental curing composition characterized by including a polymerization initiator.