JP3487389B2 - Dental composition - Google Patents

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dental composition suitable as a pretreatment material for the surface of a tooth in order to realize high adhesion between the filling material and the tooth when repairing the filling of the tooth in the field of dentistry. .

2. Description of the Related Art A filling material called a composite resin is mainly used for repairing a tooth damaged by caries or the like. This composite resin is generally used by filling the cavity of the tooth and then polymerizing and hardening. However, since this material itself does not have adhesiveness to tooth structure, a dental adhesive is used together. The adhesive material is required to have an adhesive force sufficient to overcome the internal stress generated during curing of the composite resin, that is, the tensile stress generated at the interface between the composite resin and the tooth structure. Otherwise, it may fall off due to long-term use in a harsh oral environment, and there may be a gap at the interface between the composite resin and the dentin, from which bacteria may invade and adversely affect the pulp. This is because. The hard tissue of teeth consists of enamel and dentin, and clinically requires adhesion to both. Conventionally, for the purpose of improving the adhesiveness, a method of pretreating the surface of the tooth before applying the adhesive has been used. As such a pretreatment material,
An aqueous acid solution that decalcifies the tooth surface is common, and phosphoric acid,
Aqueous acid solutions such as citric acid and maleic acid have been used.
In the case of enamel, the mechanism of adhesion to the treated surface is macro mechanical fitting in which the adhesive penetrates and hardens on the rough surface by decalcification of the acid aqueous solution, whereas in the case of dentin Is said to be micro mechanical fitting in which the adhesive penetrates into the minute voids of the sponge-like collagen fiber exposed on the tooth surface after decalcification and hardens. However, permeation into collagen fibers is not as easy as on enamel surface,
A permeation enhancer called a primer is generally used after the treatment with the acid aqueous solution, which causes complicated operation. In order to obtain a high adhesive strength to dentin only by treatment with an acid aqueous solution, JP-A-62-33109 discloses a tooth surface treating material using a sulfonic acid group-containing polymer.
231652 discloses a tooth surface treatment material containing a metal halide, and JP-A-63-279851 discloses a tooth surface treatment material containing an amphoteric amino compound.
JP-A-279815 discloses a tooth surface treatment material which is a combination of an organic carboxylic acid and a metal chloride. However, the adhesive strength to dentin was not sufficient even when these compositions were used. In addition, JP-A-6-93
No. 27, JP-A-6-24928 and the like disclose a primer composition in which dentin does not need to be pretreated with an aqueous acid solution. However, although these compositions show a certain degree of adhesion when used on dentin, when they are used on enamel, the content of acidic polymerizable monomers is low and deashing does not occur. Since it is weak, the adhesive strength is insufficient. Inoue et al. Have also proposed a primer composition using 2-acryloxyethyl hydrogen malate or the like (40th JADR General Assembly,
And the 24th and 25th Annual Meeting of the Japanese Society of Dental Science and Engineering). However, the treatment with this composition requires a long time, and the simplification of the operation was not sufficient.

From the above points, in the procedural method of cavity repair such as pretreatment, application of adhesive, and filling of restoration material,
It has been desired to develop a material that simplifies the complicated operation of applying both an aqueous acid solution and a primer as a pretreatment and gives a high adhesive force to both enamel and dentin with a single pretreatment.

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to overcome the above technical problems, the use of a phosphoric acid group-containing polymerizable monomer as a primer improves dentin adhesion. The present invention has been completed based on the finding that it can be used as a primer that gives a high adhesive force to enamel and dentin without pretreatment with an aqueous acid solution. That is,
The present invention comprises (A) a phosphoric acid group-containing polymerizable monomer, (B) a polyvalent carboxylic acid group-containing polymerizable monomer, and (C) water as main components, and A) component is 5 ~
50% by weight, 1 to 50% by weight of component (B), component (C)
Of the dental composition of the present invention
Sometimes it is a dental composition).

BEST MODE FOR CARRYING OUT THE INVENTION The first dental composition of the present invention can preferably further contain (D) a water-soluble organic solvent and / or (E) a polyfunctional polymerizable monomer. still,
In the first dental composition of the present invention, (A), (B),
The weight content of each of the components (C), (D), and (E) is the sum of all the components constituting the dental composition, and thus the optional components, if any, that is, per composition. % By weight. Used in the first dental composition of the present invention (A)
The phosphoric acid group-containing polymerizable monomer has at least 1 in one molecule.
Easily reacts with one ═P (O) —OH group or water, which is an essential component of the present invention, to obtain at least one ═P (O) —OH group.
There is no particular limitation as long as it is a polymerizable monomer which is a phosphoric acid ester having a functional unsaturated group (O) -OH group and a polymerizable unsaturated group. Furthermore, it is also possible to use a thiophosphoric acid group in which 1 to 2 of the oxygen atoms bonded to the phosphorus atom are substituted with a sulfur atom, or a derivative thereof. Examples of typical phosphoric acid group-containing polymerizable monomers include phosphoric acid monoesters represented by the following general formula (1) and diesters represented by general formulas (2) and (3). Furthermore, two of these compounds are linked to -P via an oxygen atom.
Pyrophosphate ester derivatives that are condensed in the -OP-bonded form are also exemplified.

[Chemical 3] (However, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and R ₃ and R ₄ each independently have 1 to 3 carbon atoms which may have an ether bond and / or an ester bond.
0 is a divalent to hexavalent organic residue, R ₅ is a hydrogen atom or an alkyl group or an alkoxy group having 1 to 5 carbon atoms, Z is an oxygen atom or a sulfur atom, and X ₁ and X ₂ are independently a hydroxyl group. ,
Represents a mercapto group or a halogen atom, and n ₁ and n ₂ are 1 to
It is an integer of 5. ) In the general formulas (1), (2) and (3),
R ₃ and R ₄ are divalent to hexavalent organic residues having 1 to 30 carbon atoms, which may have an ether bond and / or an ester bond. The structure is not particularly limited, but specific examples are as follows.

[Chemical 4] (In the formula, m ₁ , m ₂ and m ₃ each represent an integer of 1 or 2) Preferred specific examples of the phosphoric acid group-containing polymerizable monomer represented by the general formula (1) are as follows. Is. Less than,
In the specific examples shown by the structural formulas, R _1's each independently represent a hydrogen atom or a methyl group.

[Chemical 5]

[Chemical 6] Specific preferred examples of the phosphoric acid group-containing polymerizable monomer represented by the general formula (2) are as follows.

[Chemical 7] In the general formula (3), R ₅ is a hydrogen atom, or an alkyl group or an alkoxy group having 1 to 5 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group. , A methoxy group, an ethoxy group, a propoxy group and the like. Preferred specific examples of the phosphoric acid group-containing polymerizable monomer represented by the general formula (3) are as follows.

[Chemical 8]

[Chemical 9] Specific examples of the pyrophosphoric acid derivative in which two of the compounds represented by the general formulas (1), (2), and (3) are condensed by taking a bond form of -P-O-P- via an oxygen atom. An example is as follows.

[Chemical 10] Among the above-mentioned phosphoric acid group-containing polymerizable monomers, from the viewpoint of tooth adhesiveness, the phosphoric acid group-containing polymerizable monomers represented by the general formulas (2) and (3), particularly the general formula (3) A phosphoric acid group-containing polymerizable monomer in which one of the esters represented by (1) is an aromatic ester is preferable. A plurality of these phosphoric acid group-containing polymerizable monomers can be mixed and used as necessary. The compounding amount of the (A) phosphoric acid group-containing polymerizable monomer used in the first dental composition of the present invention is 5 to 5 in all the constituent components of the composition.
It is 0% by weight, more preferably 7 to 40% by weight. If the blending amount is too small, the adhesive strength to both dentin and enamel, especially enamel, will decrease, and conversely, if the blending amount is too large, the adhesive strength to both dentin and enamel, especially dentin, will decrease. Used in the first dental composition of the present invention (B)
The polyvalent carboxylic acid group-containing polymerizable monomer has in one molecule a plurality of groups such as a carboxyl group, or an anhydride or acid halide thereof , which easily reacts with water to form a carboxyl group, and at least 1 It is a polymerizable monomer having a number of polymerizable unsaturated groups and satisfies the structure. Examples of such a compound include a trimellitic acid derivative represented by the following general formula (4) and an anhydride or halide thereof:
Pyromellitic acid derivatives represented by the following general formula (5) and their anhydrides or halides, malonic acid derivatives represented by the following general formula (6) and their anhydrides or halides, or 6- (meth) acryl Roxyethylnaphthalene-1,2,6-tricarboxylic acid, N- (meth) acryloyl aspartic acid and the like can be mentioned.

[Chemical 11] (However, R _1's each independently represent a hydrogen atom or a methyl group, and R _3's each independently have 2 to 6 carbon atoms having 1 to 30 and / or an ester bond and / or an ester bond.
A valent organic residue, R ₆ represents a hydrogen atom or a carboxyl group, n ₁ represents an integer of ₁ to 5, and n ₃ represents 1 or 2. ) Preferred specific examples of the polyvalent carboxylic acid group-containing polymerizable monomer represented by the general formula (4) are as follows.

[Chemical 12]

[Chemical 13]

[Chemical 14]

[Chemical 15]

[Chemical 16] Preferred specific examples of the polyvalent carboxylic acid group-containing polymerizable monomer represented by the general formula (5) are as follows.

[Chemical 17] Preferred specific examples of the polyvalent carboxylic acid group-containing polymerizable monomer represented by the general formula (6) are as follows.

[Chemical 18]

[Chemical 19] Among the above polyvalent carboxylic acid group-containing polymerizable monomers, a polymerizable monomer having two carboxyl groups or a group generating a carboxyl group on the same carbon or adjacent carbons from the viewpoint of tooth adhesiveness. Is preferable, and a polyvalent carboxylic acid group-containing polymerizable monomer such as a trimellitic acid derivative or a malonic acid derivative is more preferably used. It is also possible to use a plurality of these polyvalent carboxylic acid group-containing polymerizable monomers as a mixture. The content of the (B) polyvalent carboxylic acid group-containing polymerizable monomer in the first dental composition of the present invention is 1 to 50% by weight, preferably 5 to 25% by weight, based on all components of the composition. is there. If it is less than 1% by weight, the adhesion to dentin is insufficient. If it exceeds 50% by weight, the adhesive strength of both dentin and enamel decreases. The components (A) and (B) described above are preferably contained in a total amount of 10% by weight or more, and more preferably 15% by weight or more, in all the constituent components. The water (C) used in the first dental composition of the present invention is necessary for demineralization of tooth structure. This water is preferably substantially free of impurities that are detrimental to storage stability, biocompatibility and adhesiveness. Examples include deionized water and distilled water. The blending amount of the (C) water is
5 to 90% by weight, preferably 20, based on the total components of the composition
~ 80% by weight. If the amount is less than 5% by weight, demineralization of the tooth structure becomes insufficient, so that the adhesive force of the enamel tends to be insufficient and the adhesive force to the dentin tends to be insufficient. If it exceeds 90% by weight, the adhesive strength tends to be low in both dentin and enamel. The water-soluble organic solvent (D) used in the first dental composition of the present invention is a phosphoric acid group-containing polymerizable monomer,
To improve the solubility of the polyvalent carboxylic acid group-containing polymerizable monomer, and various polymerizable monomers that are optional components described below in a solvent, dissolve each component into a uniform solution, or to the extent that there is no problem in use It is preferable to mix them in order to form an emulsion that is stable for a long time. Specific examples of such a water-soluble organic solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol and 2-methyl-2-.
Propanol, 2-methyl-2-butanol, 2-propen-1-ol, 2-propyn-1-ol, 1,2
-Ethanediol, 1,2-propanediol, 1,3
-Propanediol, 1,3-butanediol, 1,4
-Butanediol, 2,3-butanediol, 1,5-
Pentanediol, hexylene glycol, glycerol, 1,2,6-hexanetriol, trimethylolpropane, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 2-methoxyethanol, 2- Ethoxyethanol, 2- (methoxyethoxy) ethanol, 2- (ethoxyethoxy) ethanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, 2-isopropoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol. , 1-
Ethoxy-2-propanol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, 1,3-dioxolane, tetrahydrofuran, dioxane, propylene oxide, dimethoxymethane, 1,2-dimethoxyethane, 1,2-diethoxyethane, bis Alcohol compounds or ether compounds such as (2-methoxyethyl) ether and bis (2-ethoxyethyl) ether, ketone compounds such as acetone and methylethylketone, and phosphate ester compounds such as hexamethylphosphoric triamide. , Dimethylformamide,
Examples thereof include acid amide compounds such as dimethylacetamide, carboxylic acid compounds such as acetic acid and propionic acid, and sulfur oxide compounds such as dimethyl sulfoxide and sulfolane. Further, those having a polymerizable functional group such as acrylic acid, methacrylic acid, and 2-hydroxyethyl methacrylate may be used. Among the above water-soluble organic solvents, alcohol compounds and ether compounds are preferable. In particular, those having less harmful effects on the living body are desirable, and ethanol, 1-propanol, 2-propanol, 1-butanol, 2-
Butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2-methyl-2-butanol,
2-propen-1-ol, 2-propyn-1-ol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol , 2,3-butanediol, 1,5-pentanediol, hexylene glycol, glycerol, 1,2,6-hexanetriol,
Trimethylolpropane, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 2-methoxyethanol, 2-ethoxyethanol, 2- (methoxyethoxy) ethanol, 2- (ethoxyethoxy) ethanol. , Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, 2-isopropoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol monomethyl ether, tripropylene glycol Monomethyl ether, dimethoxymethane, 1,
2-dimethoxyethane, 1,2-diethoxyethane, bis (2-methoxyethyl) ether, bis (2-ethoxyethyl) ether, alcohol compound or ether compound such as 2-hydroxyethylmethacrylate and acetone It is preferably used. The use of ethanol and propanol is most preferable from the viewpoint of harmful effects on the living body,
From the viewpoint of storage stability of the dental composition, it is preferable to use an ether compound having no hydroxyl group. If necessary, a plurality of the water-soluble organic solvents may be mixed and used.
The content of the water-soluble organic solvent (D) is preferably 1 to 80% by weight, and more preferably 5 to 5% by weight of all the constituent components of the composition.
70% by weight, particularly preferably 10 to 40% by weight.
If it is less than 1% by weight, the effect of promoting the dispersion and dissolution of the polyvalent carboxylic acid group-containing polymerizable monomer in water tends to be insufficient,
If it exceeds 80% by weight, the adhesive strength tends to decrease for both dentin and enamel. The first dental composition of the present invention comprises:
Further, it is preferable to add (E) a polyfunctional polymerizable monomer. By blending the polyfunctional polymerizable monomer, the marginal sealing property when the first dental composition of the present invention is used as a primer is improved. The (E) polyfunctional polymerizable monomer is not particularly limited as long as it is a polymerizable monomer having a plurality of polymerizable unsaturated groups in one molecule, and known compounds can be used. Specific examples of such compounds include 2,2-bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl) propane, 2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloyloxytetraethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propane, 2 (4-methacryloyloxyethoxyphenyl) -2 (4-methacryloyloxydiethoxyphenyl) propane, 2 (4-methacryloyl oki Diethoxyphenyl) -2 (4-methacryloyloxytriethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2 (4-methacryloyloxytriethoxyphenyl) propane, 2,2-bis (4-methacryloyloxy) Dipropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane, 1-methacryloyloxymethyl-2-methacryloyloxyethyl hydrogenmalate, and aromatic bifunctional monomers such as acrylates thereof. Body, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, Russia propylene glycol dimethacrylate,
1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, glycerin dimethacrylate,
Di-2-methacryloyloxyethyl-2,2,4-trimethylhexamethylene dicarbamate and aliphatic bifunctional monomers such as acrylates, trimethylolpropane trimethacrylate, trimethylolethanetrimethacrylate, trimethylolpropane Examples thereof include trifunctional monomers such as trimethacrylate and acrylates thereof, and tetrafunctional monomers such as pentaerythritol tetramethacrylate and pentaerythritol tetraacrylate. Among the above polyfunctional polymerizable monomers, it is preferable to use an aliphatic bifunctional monomer or a tri- or tetra-functional monomer. A plurality of these polyfunctional polymerizable monomers can be mixed and used as necessary. The blending amount of the (E) polyfunctional polymerizable monomer is preferably 0.1 to 30% by weight, and more preferably 0.5 to 20% by weight, based on all the constituent components of the composition. If it is less than 0.1% by weight, the effect of improving the marginal sealing property tends not to be recognized, and if it exceeds 30% by weight, the adhesive force to dentin tends to decrease. The first dental composition of the present invention is particularly preferably (A) a phosphoric acid group-containing polymerizable monomer, (B) a polyvalent carboxylic acid group-containing polymerizable monomer, and (C).
Water, (D) water-soluble organic solvent and (E) polyfunctional polymerizable monomer as main components, and the component (A) is 5 to 50% by weight, and the component (B) is 1 to 1% by weight relative to the composition. 50% by weight,
The component (C) accounts for 5 to 90% by weight, the component (D) accounts for 1 to 80% by weight, and the component (E) accounts for 0.1 to 30% by weight. On the other hand, in the first dental composition of the present invention, when the amount of the (A) phosphoric acid group-containing polymerizable monomer is small, the adhesive strength to the enamel may not always be sufficient. By blending (F) a strong inorganic acid and / or a non-polymerizable organic sulfonic acid or (G) a sulfonic acid group-polymerizable monomer, it is possible to improve the adhesive strength to enamel. Therefore, according to the present invention, further, (A) a phosphoric acid group-containing polymerizable monomer, (B) a polyvalent carboxylic acid group-containing polymerizable monomer, (C) water, (D) a water-soluble organic compound. The solvent and (F) an inorganic strong acid and / or a non-polymerizable organic sulfonic acid as a main component, and to the composition,
Component (A) is 0.5 to 7% by weight, component (B) is 3 to 50
% By weight, 5 to 90% by weight of component (C), 1% of component (D)
To 80% by weight and component (F) occupy 0.01 to 3% by weight (hereinafter sometimes referred to as the second dental composition of the present invention), and (A). Phosphoric acid group-containing polymerizable monomer, (B) polyvalent carboxylic acid group-containing polymerizable monomer, (C) water, (D) water-soluble organic solvent, and (G) sulfonic acid-containing polymerizable monomer And (A) component is 0.5 to 7% by weight, (B) component is 3 to 50% by weight, and (C) component is 5 to 9%, based on the composition.
0% by weight, 1 to 80% by weight of the component (D) and 0.01 to 12% by weight of the component (G) (hereinafter referred to as the third dental composition of the present invention) May be provided). In the second and third dental compositions of the present invention, the above (A), (B), (C) and (D)
Regarding the components, the above-mentioned ones are directly applied here. In the second dental composition of the present invention, as the inorganic strong acid (F), known substances are used without particular limitation as long as the pKa value in the aqueous solution is 1 or less. However, in the case of polybasic acid, the value obtained from the dissociation constant in the first step, that is, pK
It is sufficient that the a ₁ value is 1 or less. Specific examples of such an acid include hydrohalic acids such as hydrochloric acid and hydrobromic acid, nitric acid, sulfuric acid, chloric acid, perchloric acid, bromic acid, oxo acids such as perbromic acid, methylsulfuric acid and ethyl. Examples thereof include acidic esters of sulfuric acid such as sulfuric acid. Further, in the second dental composition of the present invention, the non-polymerizable organic sulfonic acid (F) easily reacts with at least one —SO ₃ H group in one molecule or with water which is an essential component of the present invention. There is no particular limitation as long as it is a compound having a functional group that produces a —SO ₃ H group, and known compounds are used. Specific examples of such compounds include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, dodecylbenzenesulfonic acid, chlorobenzenesulfonic acid, and bromobenzene. Sulfonic acid, biphenylsulfonic acid, naphthalenesulfonic acid, anthracenesulfonic acid, phenolsulfonic acid, naphtholsulfonic acid, sulfoacetic acid, sulfobenzoic acid, sulfosalicylic acid, anthraquinonesulfonic acid, benzenedisulfonic acid, naphthalenedisulfonic acid, naphtholdisulfonic acid, biphenyl Each positional isomer such as disulfonic acid may, for example, be mentioned. The above inorganic strong acid and /
Alternatively, it is preferable that the non-polymerizable organic sulfonic acid has a smaller formula weight and a higher volatility from the viewpoint of adhesiveness to the tooth.
Further, those having a pKa value of 0 or less are more preferable, and nitric acid and hydrochloric acid are most preferably used. A plurality of these inorganic strong acids and / or non-polymerizable organic sulfonic acids can be mixed and used as necessary. The amount of the strong inorganic acid (F) and / or the non-polymerizable organic sulfonic acid (F) in the present invention is 0.01 to 3% by weight, preferably 0.5 to 2.5% by weight, based on all the components of the composition. . If it is less than 0.01% by weight, the effect of improving the adhesive force to enamel tends to be insufficient, and if it exceeds 3% by weight, the adhesive force to dentin tends to decrease. When the above inorganic strong acid and / or non-polymerizable organic sulfonic acid is an aqueous solution such as hydrochloric acid or nitric acid or contains crystal water such as p-toluenesulfonic acid monohydrate, those Water shall be calculated as the component (C). Among the compounds having a sulfonic acid group, the compound having a polymerizable unsaturated group can be blended in a larger amount than the non-polymerizable organic sulfonic acid. In the third dental composition of the present invention, the (G) sulfonic acid group-containing polymerizable monomer is at least one -S in one molecule.
It is particularly limited as long as it is a polymerizable monomer having at least one polymerizable unsaturated group and an O ₃ H group or a group which easily reacts with water, which is an essential component of the present invention, to form a —SO ₃ H group. Instead, known compounds can be used. Examples of representative sulfonic acid group-containing polymerizable monomers include sulfonic acid (meth) acrylate derivatives, (meth) acrylamide derivatives, vinyl sulfonic acid, and styrene sulfonic acid as shown in the following general formula (7). Etc. are illustrated.

[Chemical 20] (However, R ₁ represents a hydrogen atom or a methyl group, R ₃ represents a C ₂ to C ₃ divalent organic residue which may have an ether bond and / or an ester bond, and Z represents An oxygen atom or an imino group (-NH-), n ₁ is an integer of ₁ to 5, n ₃
Represents 1 or 2. The preferred specific examples of the sulfonic acid group-containing polymerizable monomer represented by the general formula (7) are as follows.

[Chemical 21] These sulfonic acid group-containing polymerizable monomers may be added as needed.
It is also possible to use a mixture of numbers. In the present invention
(G) The compounding amount of the sulfonic acid group-containing polymerizable monomer is the composition
It is preferably 0.01 to 12% by weight in all the constituents of the product, and
5 to 10% by weight is more preferable. Less than 0.01% by weight
If so, the effect of improving the adhesive strength to enamel may be insufficient.
If more than 12% by weight
Adhesive strength tends to decrease. Containing these sulfonic acid groups
The polymerizable monomer is a non-polymerizable monomer exemplified as the component (F).
For use by mixing with strong acid and / or non-polymerizable organic sulfonic acid
It is possible to stay. In this case, the polymerizable unsaturated group
Inorganic strong acid and / or non-polymerizable organic sulfonic acid
Is preferably 3% by weight or less.
Strong acid and / or non-polymerizable organic sulfonic acid and sulfonic acid
The total addition amount of the group-containing polymerizable monomer is 12% by weight or less.
Preferably there is. In the second dental composition of the present invention
Ke (F) Inorganic strong acid and / or non-polymerizable organic sulfone
Acid or (G) sulfone in the third dental composition
The acid group-containing polymerizable monomer is at least one hydrogen cation.
It must be added in a state that can supply
When neutralized with amine etc. and added as a neutral salt
If it is not included in the component (F) or the component (G). same
Similarly, as an optional component, such as metal hydroxides and amines
When a basic substance is added to neutralize all or part of the acid
In this case, the neutralized acid is the component (F) or the component (G).
Not included in. The second and third dental compositions of the present invention include
Further, it is preferable to add (E) a polyfunctional polymerizable monomer.
Good By blending a polyfunctional polymerizable monomer,
Edge blocking when these compositions are used as primers
The property is improved. In the second and third dental compositions of the present invention
The above-mentioned component (E) is
Also applies as is. The dental composition of the present invention has the above
(A) component, (B) component, (C) component, (D) component,
In addition to the components (E), (F) and (G),
Various optional components described below, within the range that does not impair the effects of Ming
Can be included. In that case, (A) above
Min, (B) component, (C) component, (D) component, (E) composition
The content of each of the component (F) and the component (G) is
(A) component, (B) component, (C) component, (D) component,
(E) component (F) component and (G) component and other components
Each composition when all the optional components are added up to 100% by weight
It is the weight content of minutes. As mentioned above, the dental of the present invention
The composition has a monofunctional polymerization to the extent that its performance is not impaired.
Monomer, water-insoluble organic solvent, polymerization initiator, metal salt,
It is possible to add inorganic or organic fine particles or the like. this
Specific examples of such monofunctional polymerizable monomers include
Rumethacrylate, ethylmethacrylate, tetrahydr
Rofurfuryl methacrylate, 2-ethylhexyl meta
Acrylate, 2-hydroxyethyl methacrylate, guar
Lysidyl methacrylate, N-methylol methacrylic acid
Mido, diacetone methacrylamide and their acrylates
Monofunctional polymerizable monomers having no acidic group such as rate,
Acrylic acid, methacrylic acid, 2- (meth) acryloyl
Oxyethyl hydrogen malate, 2- (meth)
Acryloyloxyethyl Hydrogen Succine
G, N- (meth) acryloyl-5-aminosalicylic acid
Monocarboxylic acid group-containing monofunctional polymerizable monomers such as
can give. Examples of the water-insoluble organic solvent include hexa
, Heptane, octane, toluene, dichloromethane,
Chloroform, carbon tetrachloride, dichloroethane, trichloro
Loethane, pentanone, hexanone, ethyl formate, formic acid
Propyl, butyl formate, ethyl acetate, propyl acetate, vinegar
Butyl acid, vinyl acetate, diethyl ether, etc.
It As the polymerization initiator, a thermal polymerization initiator and a photopolymerization initiator
Any of Examples of the thermal polymerization initiator include t-
Butyl hydroperoxide, cumene hydroperoxy
, Di-t-butyl peroxide, dicumyl peroxide, aceto peroxide
Organics such as chill, lauroyl peroxide, benzoyl peroxide
Peroxides 2,2'-azobis-2-methylbutyroni
Tolyl, methyl azobisisobutyrate, azobiscyanovaler
Azo compounds such as acids are preferably used. Also, above
Using a combination of organic peroxides and amine compounds
Can accelerate the polymerization. Polymerization like this
As the amine compound used as the accelerator, amino
Secondary or tertiary amines in which the group is bound to an aryl group
Preferable and specifically illustrated, N, N-dimethyl-p
-Toluidine, N, N-dimethylaniline, N- (2-
Hydroxyethyl) aniline, N, N-di (2-hydro)
Xyethyl) -p-toluidine, N-methylaniline,
N-methyl-p-toluidine and the like are preferable. The above organic excess
In addition to the combination of oxide and amine compound, sulfinic acid
It is also suitable to combine salts or borates. Scarecrow
The sulfinic acid salts include benzenesulfinic acid
Thorium, lithium benzenesulfinate, p-toluene
Sodium sulfinate, p-toluenesulfinic acid
Lithium, potassium p-toluenesulfinate, m-ni
Sodium trobenzenesulfinate, p-fluorobe
And sodium borate.
Trialkylphenylboron, trialkyl
(P-chlorophenyl) boron, trialkyl (p-phenyl)
Lorophenyl) boron, trialkyl (3,5-bisto
Lifluoromethyl) phenylboron, dialkyldipheny
Ruboron, dialkyldi (p-chlorophenyl) boro
Elementary, dialkyldi (p-fluorophenyl) boron, dia
Rukildi (3,5-bistrifluoromethyl) phenylpho
Arsenic, monoalkyltriphenylboron, monoalkyl
Tri (p-chlorophenyl) boron, monoalkyl tri
(P-Fluorophenyl) boron, monoalkyltri
(3,5-bistrifluoromethyl) phenyl boron (a
The alkyl group is an n-butyl group, an n-octyl group, an n-dodecyl group.
Sodium salt, lithium salt, potassium salt,
Gnesium salt, tetrabutylammonium salt, tetrame
A chill ammonium salt etc. are mentioned. Also, these
Finates and borates should be reacted with acidic compounds.
The polymerization can also be initiated by Also photopolymerization
It is also preferable to use an initiator (also called a photosensitizer).
Examples of camphorquinone, benzyl, α-naphth
Chill, acetonaphthene, naphthoquinone, p, p'-dime
Toxybenzyl, p, p'-dichlorobenzyl acetyl
Le, 1,2-phenanthrenequinone, 1,4-phenane
Trenquinone, 3,4-phenanthrenequinone, 9,1
Α-diketones such as 0-phenanthrenequinone, 2,4
-Thioxanthones such as diethylthioxanthone, 2-
Benzyl-dimethylamino-1- (4-morpholinov
Phenyl) -butanone-1,2-benzyl-diethylami
No-1- (4-morpholinophenyl) -butanone-
1,2-benzyl-dimethylamino-1- (4-morph
Olinophenyl) -propanone-1,2-benzyl-di
Ethylamino-1- (4-morpholinophenyl) -p
Ropanone-1,2-benzyl-dimethylamino-1-
(4-morpholinophenyl) -pentanone-1,2-
Benzyl-diethylamino-1- (4-morpholinov
Α-aminoacetopheno such as (phenyl) -pentanone-1
And the like. Furthermore, in combination with the above photosensitizer
It is also preferable to use a photopolymerization accelerator. Light weight
As a compounding accelerator, N, N-dimethylaniline, N, N-
Diethylaniline, N, N-di-n-butylaniline,
N, N-dibenzylaniline, N, N-dimethyl-p-
Toluidine, N, N-diethyl-p-toluidine, N,
N-dimethyl-m-toluidine, p-bromo-N, N-
Dimethylaniline, m-chloro-N, N-dimethylaniline
Phosphorus, p-dimethylaminobenzaldehyde, p-dime
Cylaminoacetophenone, p-dimethylaminobenzoic acid
Acid, p-dimethylaminobenzoic acid ethyl ester, p-
Dimethylaminobenzoic acid amyl ester, N, N-dime
Chill anthranilic acid methyl ester, N, N
-Dihydroxyethylaniline, N, N-dihydroxye
Tyl-p-toluidine, p-dimethylaminophenethyl
Alcohol, p-dimethylaminostilpen, N, N-
Dimethyl-3,5-xylidine, 4-dimethylaminopi
Lysine, N, N-dimethyl-α-naphthylamine, N,
N-dimethyl-β-naphthylamine, tributylami
Amine, tripropylamine, triethylamine, N-methyl
Ludiethanolamine, N-ethyldiethanolamine
N, N, N-dimethylhexylamine, N, N-dimethyl
Rudecylamine, N, N-dimethylstearylami
N, N, N-dimethylaminoethyl methacrylate,
N, N-diethylaminoethyl methacrylate, 2,
Tertiary amines such as 2 '-(n-butylimino) diethanol
Mines, 5-butylbarbituric acid, 1-benzyl-5
-List of barbiturates such as phenyl barbituric acid
You can do it. Also, due to the reaction with oxygen and water,
Generating tributylborane, tributylborane part
Organoboron compounds such as oxides can be used to develop organometallic polymerization.
It can be given as an initiator. The thermal polymerization initiator, photosensitizer,
Sulfinates, borates, polymerization accelerators, organic metals
The type of polymerization initiator may be used alone or in combination as required.
Can be used in combination. As metal salt
For magnesium, aluminum, calcium, iron,
Cobalt, nickel, copper, zinc, strontium, tin,
Polyvalent metal such as barium, hydrochloride, hydrofluoride, sulfate,
Nitrate, phosphate, acetate, citrate, oxalate, ED
TA salt etc. are mentioned. Incorporate inorganic or organic fine particles
By adjusting the viscosity and fluidity of the dental composition.
You can A specific example of such fine particles is po
Polyethylene, polypropylene, polymethylmethacrylate
, Polyamides, polyesters, polystyrenes,
Polymeric fine particles such as silicones, silicon, aluminum
Um, titanium, zirconium, nickel, cobalt, sulfur
Trontium, iron, copper, zinc, tin, magnesium, cal
Metals such as sium, potassium and sodium, alone or
Complex oxides, silicon nitride, aluminum nitride, nitrogenChemical
Tantalum, nitrides such as boron nitride, silicon carbide, borocarbide
Inorganic fine particles such as carbides such as elementary metals and their metal oxidation
Inorganic fine particles such as materials, metal nitrides, metal carbides, etc.
Methyltrimethoxysilane, methyltriethoxysila
, Methyltrichlorosilane, dimethyldichlorosila
Amine, trimethylchlorosilane, vinyltrimethoxysila
Vinyl triethoxysilane, vinyl trichlorosilane
Vinyl triacetoxysilane, vinyl tris (β-
(Methoxyethoxy) silane, γ-methacryloxypropyi
Lutrimethoxysilane, γ-methacryloxypropylate
Lis (β-methoxyethoxy) silane, γ-chloropro
Pyrtrimethoxysilane, γ-chloropropylmethyldi
Methoxysilane, γ-glycidoxypropyltrimethoxy
Cysilane, γ-glycidoxypropylmethyldiethoxy
Silane, β (3,4 epoxycyclohexyl) ethyl
Limethoxysilane, N-phenyl-γ-aminopropyl
Sila such as trimethoxysilane and hexamethyldisilazane
Coupling agents, isopropyl triisostealoy
Lucitanate, isopropyl trioctanoyl titane
G, isopropyl isostearoyl diacrylic titanate
Isopropyl tridodecylbenzene sulfonyl tita
Ne, isopropyl dimethacryl isostearoyl titanate
Of isopropyl tricumyl phenyl titanate, etc.
Titanate coupling agents, acetoalkoxy al
Aluminum-based cups such as minium diisopropylate
The thing surface-treated with the ring agent is mentioned. further,
Polyethylene, polypropylene, polymethylmethacrylate
Sheet, polyamides, polyesters, polystyrene
The surface of the inorganic fine particles is coated with a polymer such as
The use of fine particles is also preferable. Above, how to produce inorganic fine particles
The method is not particularly limited, and existing coprecipitation method, thermal spraying
Method, sol-gel method, bulk grinding-classification method, etc. can be used
In addition, the surface treatment method is spray dry method or dry blend method.
Existing methods such as legal method and wet mixing method can be used without limitation.
The primary particle diameter of the fine particles is 0.001 μm to 1 μm.
preferable. It is practically difficult to obtain particles of 0.001 μm or less
Difficult, on the other hand, if the particle size is too large, sedimentation easily occurs
Since problems such as difficulty in uniform and uniform dispersion occur, 0.
It is preferably 5 μm or less, more preferably 0.1 μm or less.
More preferable. The above-mentioned fine particles are the composition, shape, and production of the particles.
A mixture of multiple manufacturing methods, surface treatment methods, and different particle systems.
It is also possible to use them together. Also, as a coloring material
A dye can also be added. The dental composition of the present invention
There is no particular limitation on the method of preparation, and for example, the above
Phosphoric acid group-containing polymerizable monomer, polyvalent carboxylic acid group-containing polymerization
Monomer, water, water-soluble organic solvent, strong inorganic acid and / or non-
Polymerizable organic sulfonic acid or sulfonic acid group-containing polymerizable
The monomer, as well as any optional ingredients that are blended as necessary
Weigh it into a container at the desired ratio, mix with stirring to obtain a uniform solution,
Alternatively, an emulsion may be used. Packaging of the composition of the invention
The morphology is appropriately determined on condition that the storage stability is not impaired.
You can For example, phosphoric acid group-containing polymerizable monomer, poly
Divalent carboxylic acid group-containing polymerizable monomer, and water-soluble organic solvent
Liquid containing as a main component, strong inorganic acid and / or non-polymerizable organic
Sulfonic acid or sulfonic acid group-containing polymerizable monomer, average
Liquid containing water and water as the main component is separately packaged and mixed when used.
It is possible to do The dental composition of the present invention has the above-mentioned properties.
The maximum is to contain a phosphoric acid group-containing polymerizable monomer.
This is characterized by the fact that it is
It is essential to contain a monomer and water. Ours
Studies have shown that from the above dental composition polyvalent carboxylic acid groups are
A dental composition having a composition excluding the contained polymerizable monomer.
However, when used in combination with a specific adhesive,
It was also revealed that it has excellent adhesiveness to. It
Therefore, according to the present invention, further, (A) phosphoric acid group-containing polymerization
Primer group consisting mainly of water-soluble monomer and (C) water
0.5 to 5 of the phosphoric acid group-containing polymerizable monomer based on the composition.
A dental primer composition containing 0% by weight;
(H) Polyfunctional carboxylic acid group-containing polyfunctional polymerizable monomer and
(I) Dental comprising an adhesive containing a polymerization initiator
Adhesive kit (hereinafter referred to as the first kit of the present invention), average
And (C) water as the main component of (b) phosphoric acid group-containing polymerizable monomer
Of the phosphate group to the primer composition.
Dental containing 0.5 to 50% by weight of a polymerizable monomer
Primer composition and (J) polyvalent carboxylic acid group-containing unit
Functional polymerizable monomer, (K) Water-soluble hydroxyl group-containing polymerizable monomer
Polymer, (E) polyfunctional polymerizable monomer and (I) initiation of polymerization
Dental adhesive kit consisting of adhesive containing
Hereinafter, the second kit of the present invention) is provided. (A)
Main component is a phosphoric acid group-containing polymerizable monomer and (C) water
(A) Phosphate Group-Containing Weight Used in Dental Primer Composition
The compatible monomer is (A) described above for the dental composition.
Similar to the ingredients. Such a phosphoric acid group-containing polymerizable monomer
Among them, the general formulas (2) and (3) are used from the viewpoint of tooth adhesion.
A phosphoric acid group-containing polymerizable monomer represented by
One of the esters represented by (3) is an aromatic ester
Phosphoric acid group-containing polymerizable monomer is preferred. These phosphorus
If necessary, mix multiple acid group-containing polymerizable monomers.
It is possible to stay. (B) Dental implant containing no component
(A) Phosphate Group-Containing Polymerizable Monomer Used in Limer Composition
The blending amount of the monomer is 5 to 50% by weight in the primer composition,
It is preferably 7 to 40% by weight. Too little compounding amount
Adhesion to both dentin and enamel decreases,
Too much dentin and enamel, especially elephant
Adhesion to dentin is reduced. The above dental primer
The water (C) used in the composition is the same as in the above dental composition.
It is the same as the component (C) described. The dental primer
The composition further comprises (D) a water-soluble organic solvent and (E)
Functional polymerizable monomer, (F) strong inorganic acid and / or non-polymerized
Organic Sulfonic Acid and (G) Sulfonic Acid Group-Containing Polymerizable
It is preferable to add a monomer as necessary. the above
(D) component, (E) component, (F) component and (G) component
Preferred specific examples and blending amounts are for the dental composition
It is the same as described above. In addition, in the above dental composition
And other polymerizable monomers exemplified as optional components.
Or water-insoluble organic solvent, polymerization initiator, metal salt, inorganic or
It is also possible to add organic fine particles and the like. The above dental implant
Regarding the method for preparing the lymer composition and the packaging form,
There is no particular limitation, and the adjustment method described in the above dental composition section
It is possible by the method similar to the method and the packaging form. For dental
The adhesive used in combination with the primer composition is included in the first kit.
And (H) polyvalent carboxylic acid group-containing polyfunctional polymerizable monomer
And (I) a polymerization initiator. The (H) polyvalent mosquito
The rubonic acid group-containing polyfunctional polymerizable monomer is a monomer in one molecule.
Ruboxyl group, or its anhydride or acid halide
Groups that easily react with water to form carboxyl groups, such as
A polymerizable monomer having a plurality of polymerizable unsaturated groups
It is a quantity. Examples of such compounds include (B) polyvalent
Specific examples of the carboxylic acid group-containing polymerizable monomer
Of the compounds that have multiple polymerizable unsaturated groups,
Can be mentioned. These polyfunctional carboxylic acid group-containing polyfunctional polymers
Of the compatible monomers, two carboxyl groups or
Groups that give rise to silyl groups are on the same or adjacent carbons
Is preferably a polymerizable monomer having the formula (4)
N of the trimellitic acid derivatives represented by_ThreeIs 2 to 4
Those used more preferably. These polycarboxylic acids
Group-containing polyfunctional polymerizable monomers can be mixed as needed.
It is also possible to use it. The adhesive will be
It contains various other polymerizable monomers described as optional components.
Can be made. In that case, the polyvalent carboxylic acid group-containing
The content of polyfunctional polymerizable monomer is a polyvalent carboxylic acid group.
Containing polyfunctional polymerizable monomer and other optional components
The total amount of the polymerizable monomers contained is 100 parts by weight (hereinafter
Below, the total of 100 parts by weight of all polymerizable monomers)
Is the weight content rate. Other optional components such as
When a polymerizable monomer is added, (H) polyvalent carvone
The amount of the polyfunctional polymerizable monomer containing an acid group depends on the adhesiveness of the tooth structure.
From the viewpoint, it is preferably 5 to 95 parts by weight, and 10 to 9
It is more preferably 0 part by weight. Contained in the adhesive
The above polyfunctional carboxylic acid group-containing polyfunctional polymerizable monomer
Is usually a highly viscous liquid or solid.
From the viewpoint of properties, various other polymerizable monomers described below are optional components.
It is preferable to use as a mixture. In addition, the above
A polyfunctional polymerizable monomer containing a carboxylic acid group is usually expensive.
Therefore, other inexpensive polymerizable monomers can be used as an optional component.
It is also preferable to use it after it is diluted. Other polymerizable monomers such as
The polyfunctional carboxylic acid group-containing monofunctional polymerization described below
Monomer, water-soluble hydroxyl group-containing polymerizable monomer and polyfunctionality
Specific examples of polymerizable monomer and dental composition
Phosphoric acid group-containing polymerizable monomers, as an optional component
Polymerizable monofunctional monomers and models that do not have the indicated acidic groups
Use polymerizable monofunctional monomers containing nocarboxylic acid groups
You can These polymerizable monomers may be added as needed.
It is possible to use a mixture of numbers. The dental plastic
Other adhesives used with the Immer composition are included in the second kit.
And (J) polyfunctional carboxylic acid group-containing monofunctional polymerizable monomer
Body, (K) water-soluble hydroxyl group-containing polymerizable monomer, (E) multi-functional
Not containing a functional polymerizable monomer and (I) a polymerization initiator
It The (J) polyfunctional carboxylic acid group-containing monofunctional polymerizable monomer
The body is a carboxyl group or its anhydride in one molecule
Or an acid halide, etc. that easily reacts with water
Having a plurality of groups giving rise to a radical group and having one polymerizable unsaturated group
It is a polymerizable monomer having. As such a compound,
The above-mentioned (B) polyvalent carboxylic acid group-containing polymerizable monomer
Of the physically exemplified compounds, one polymerizable unsaturated group
And a compound having These polyvalent carboxylic acid groups
Of the monofunctional polymerizable monomers contained, it is represented by the general formula (5).
N of malonic acid derivatives₁It is preferable to use one with
Used. Monofunctional polymerization containing these polycarboxylic acid groups
It is also possible to mix multiple polymerizable monomers if necessary.
Is. The polyvalent carboxylic acid group-containing group contained in the adhesive.
Content of monofunctional polymerizable monomer is 100 weight of adhesive
From 5 to 60 parts by weight is preferable from the point of adhesiveness of tooth material.
More preferably, it is more preferably 10 parts by weight to 50 parts by weight.
(K) The water-soluble hydroxyl group-containing polymerizable monomer is small in one molecule.
At least one hydroxyl group and at least one polymerizable unsaturated
It is a water-soluble polymerizable monomer having a group and has such a structure.
Any known material can be used without limitation.
However, under a temperature condition of 25 ° C, a hydroxyl group-containing polymerizable monomer
When 10 grams and 100 grams of water are mixed,
When mixed uniformly, the hydroxyl group-containing polymerizable monomer is
It is assumed to be water-soluble. As such a compound, 2-hi
Droxyethyl methacrylate, 2-hydroxypropyi
Lumethacrylate, 3-hydroxypropyl methacrylate
, 2,3-dihydroxypropyl methacrylate,
2,3-dihydroxybutyl methacrylate, 2,4-
Dihydroxybutyl methacrylate, 2-hydroxyme
Tyl-3-hydroxypropyl methacrylate, 2,
3,4-trihydroxybutyl methacrylate, 2,2
-Bis (hydroxymethyl) -3-hydroxypropyl
Methacrylate, 2,3,4,5-tetrahydroxype
Ethyl methacrylate, diethylene glycol monometa
Crylate, triethylene glycol monomethacrylate
G, tetraethylene glycol monomethacrylate,
Ethylene glycol monomethacrylate and these
Polyhydric alcohols such as acrylates
(Meth) acrylic acid esters of ethylene glycols,
N-methylol methacrylamide, N-methylol acrylate
(Meth) acrylic acid of aminoalcohol such as rilamide
Examples include amides. Water-soluble hydroxyl group-containing polymerizable monomer
Among the polymers, 2-hydro is advisable in terms of adhesiveness to teeth and cost.
Xyethyl methacrylate, 2,3-dihydroxy pro
The use of pill methacrylate is preferred. These water soluble
If necessary, mix multiple hydroxyl-containing polymerizable monomers.
It is also possible to use. The above contained in the adhesive
The content of the water-soluble hydroxyl group-containing monofunctional polymerizable monomer is
In 100 parts by weight of the total amount of polymerizable monomers, is it a point of adhesiveness to tooth structure?
5 to 50 parts by weight is preferable, and 10 to 40 parts by weight are preferable.
More preferably parts by weight. (E) Polyfunctional polymerizable monomer
Is a polymerizable monomer having multiple polymerizable unsaturated groups in one molecule
The body is not particularly limited as long as it is a known compound.
Be done. Examples of such compounds include the above-mentioned dental composition section.
Examples of the (E) polyfunctional polymerizable monomer specifically exemplified in
You can In addition, the above-mentioned polyfunctional carboxylic acid group-containing polyfunctional
Of the polymerizable monomers and the (A) phosphoric acid group-containing polymerizable monomer
Of these, it is also preferable to use a polymerizable monomer having multiple polymerizable unsaturated groups.
It is suitable. These polyfunctional polymerizable monomers may be used as needed.
It is possible to mix and use two or more. Adhesion of the present invention
Of the above-mentioned (E) polyfunctional polymerizable monomer contained in the material
The amount of all polymerizable monomers in the adhesive material is from the viewpoint of adhesiveness to the tooth structure.
20 parts by weight to 90 parts by weight is preferable in 100 parts by weight in total.
30 to 80 parts by weight is more preferable. Of the present invention
The above-mentioned polyfunctional carboxylic acid group-containing monofunctional polymerizable monomer is used for the adhesive material.
Polymer, water-soluble hydroxyl group-containing polymerizable monomer and polyfunctional polymerization
In addition to the polymerizable monomer, the operability can be improved by adjusting the viscosity of the adhesive.
Other polymerizable monomers are included for the purpose of cost reduction and cost reduction.
You can have it. With other polymerizable monomers like this
The phosphate groups specifically exemplified in the above-mentioned dental composition section
Containing polymerizable monomers, acidic groups exemplified as optional components
Free Monofunctional Polymerizable Monomers and Monocarboxylic Acid Groups
Containing monofunctional polymerizable monomers etc. can be used
It If necessary, mix a plurality of these polymerizable monomers.
It can be used. For the above two kinds of adhesives of the present invention
Contains (I) a polymerization initiator for polymerizing and curing.
Be done. Such a polymerization initiator is not particularly limited, and known ones
Is used without limitation. As such a polymerization initiator
Is an organic compound exemplified as an optional component in the dental composition.
Thermal polymerization initiators such as peroxides and azo compounds, α-dike
Tons, thioxanthones, α-aminoacetophenone
Include photosensitizers such as compounds and organometallic polymerization initiators
You can If necessary, a plurality of these polymerization initiators may be mixed.
Can be used. Addition amount of these polymerization initiators
Is particularly limited as long as it exhibits the effect.
However, the total amount of all polymerizable monomers is 100 parts by weight.
However, addition of 0.01 to 20 parts by weight is preferable, and
The addition of 10 to 10 parts by weight is more preferable. Start thermal polymerization
Agents and photosensitizers are used in combination with suitable polymerization accelerators.
It is preferable. Examples of such a polymerization accelerator include the above-mentioned teeth.
Secondary and third exemplified as optional components in the pharmaceutical composition
Primary amines, sulfinates, borates, barbits
Acid, etc. These polymerization accelerators may be used if necessary.
It is possible to mix and use a plurality of the same. These polymerization
The amount of the accelerator added is not particularly limited as long as the effect is exhibited.
The total amount of all polymerizable monomers is not limited to 1
It is preferable to add 0.01 to 20 parts by weight to 100 parts by weight.
Therefore, the addition of 0.05 to 10 parts by weight is more preferable. Book
In the adhesive of the invention, if necessary, hydroquinone,
Hydroquinone monomethyl ether, butyl hydroxy
It is preferable to add a small amount of a polymerization inhibitor such as toluene.
Yes. If necessary, a filler may be further added to the adhesive of the present invention.
It is also suitable to add. To add filler
Can improve mechanical strength, control viscosity, fluidity, etc.
Becomes As a specific example of such a filler,
Specific examples of the optional components in the dental composition
Polymer particles, metal oxides, metal nitrides, metals
Inorganic fine particles such as carbides and silane cups
Ring agents, titanate coupling agents, aluminum
Examples include those surface-treated with um-based coupling agents.
It In addition, the viscosity of the adhesive is usually relatively high,
Since the possibility of sedimentation is reduced,
Large particles can be used, and
It is also possible to use particles of 1 to 200 μm with inorganic compounds
It It is also possible to disperse organic or inorganic particles in a polymerizable monomer.
Then, the particle-dispersed high-molecular polymer obtained by polymerizing this is pulverized.
Then, a filler having a size of 200 μm or less is used.
It is also suitable to use it. Generally, the filler diameter is
The use of particles from 0.001 μm to 200 μm is preferred,
The use of particles of 0.001 μm to 100 μm is more preferable.
Yes. Above, the filler, the composition of the particles, shape, manufacturing method
Method, surface treatment method, multiple particle systems
It is also possible to use. Addition amount of these fillers
Is not particularly limited as long as it does not impair the effects of the present invention.
Total weight of all polymerizable monomers is not 100%
It is preferable to add 300 parts by weight or less to 100 parts by weight,
The addition of less than or equal to parts by weight is more preferred. Prepare the adhesive of the present invention
There are no particular restrictions on the manufacturing method, and for example, the above
Valent carboxylic acid group-containing polyfunctional polymerizable monomer or polyvalent carboxylic acid
Containing boric acid group-containing monofunctional polymerizable monomer, water-soluble hydroxyl group
Polymerizable monomers and polyfunctional polymerizable monomers and polymerization initiators
And optional ingredients that are blended as needed in the desired ratio
It may be weighed out and mixed with stirring to make it uniform.

The dental composition of the present invention is generally used in a method of filling and repairing a tooth surface such as applying a pretreatment material, drying, applying an adhesive, curing an adhesive, filling a filling material, and curing a filling material. Used as a pretreatment material. By applying the pretreatment material to the tooth surface, the inorganic components of the tooth structure are dissolved, and at the same time, the permeation layer of the polymerizable monomer is formed in the tooth structure, and then the permeation / diffusion / polymerization of the applied adhesive material. Assuming a mechanism that facilitates the formation of a strong adhesive layer, the phosphoric acid group-containing polymerizable monomer dissolves the inorganic component due to the acid supply ability of the phosphoric acid group, and It is easy to penetrate into the tooth due to the affinity for the tooth, and it is advantageous for forming a penetrating layer of the polymerizable monomer in the tooth. Moreover, since a monomer having a plurality of carboxylic acid groups has a high dentin affinity, it is presumed that the formation of the permeation layer of the polymerizable monomer in the dentin will be more advantageous. Furthermore, it is considered that the strong inorganic acid and / or the non-polymerizable organic sulfonic acid or the sulfonic acid group-containing polymerizable monomer makes the dissolution of the inorganic component more reliable due to its acid supply capacity.

By using the dental composition of the present invention as a pretreatment agent for the surface of the tooth structure prior to the adhesive agent when the tooth and the filling material are adhered by the adhesive agent, only one pretreatment operation is required. As a result, the complicated pretreatment operation for the dentin surface, which requires two treatments of applying a primer after the treatment with an aqueous acid solution, which has been conventionally performed, is simplified. Furthermore, a high adhesive strength is obtained for both enamel and dentin.

EXAMPLES Hereinafter , the composition of the present invention will be specifically shown by examples, but the present invention is not limited to these examples. The abbreviations and abbreviations used in the text and examples, the adhesive strength measuring method, and the adhesive preparation method are as follows. (1) Abbreviations and abbreviations (A) component PM: 2-methacryloyloxyethyl dihydrogen phosphate Phenyl-P: 2-methacryloyloxyethyl phenyl hydrogen phosphate PM2: bis (2-methacryloyloxyethyl)
Hydrogen phosphate (B) component-MTS: 2-methacryloyloxyethyl-3'-methacryloyloxy-2 '-(3,4dicarboxybenzoyloxy) propyl succinate-MAC-10: 11-methacryloyloxy-1,1
-Undecanedicarboxylic acid-4-META: 4-methacryloyloxyethyl trimellitate anhydride (D) component-IPA: isopropyl alcohol-DME: 1,2-dimethoxyethane-BMEE: bis (methoxyethyl) ether-HEMA: 2 -Hydroxyethyl methacrylate (E) component-3G: triethylene glycol dimethacrylate-NPG: neopentyl glycol dimethacrylate-Bis-GMA: 2,2-bis (4- (2-hydroxy-3-methacryloyloxypropoxy) phenyl)
Propane / D-2.6E: the following compounds

[Chemical formula 22] (F) component-DBS: dodecylbenzenesulfonic acid (G) component-AMPS: 2-acrylamido-2-methylpropanesulfonic acid (H) component-MTS: 2-methacryloyloxyethyl-3'-methacryloyloxy-2'- (3,4 dicarboxybenzoyloxy) propyl succinate.4-TAPT: 4- (3-acrylooxy-2,2-
Bis (acrylooxymethyl) propyl) dihydrogen trimellitate (I) component-CQ: camphorquinone-DMBE: N, N-dimethyl-p-aminoethyl benzoate-DAAP: N, N-dimethyl-p-amino Acetophenone (J) component / MAC-10: 11-methacryloyloxy-1,1
-Undecanedicarboxylic acid 4-META: 4-methacryloyloxyethyl trimellitate anhydride (K) component-HEMA: 2-hydroxyethyl methacrylate-GM: 2,3-dihydroxypropyl methacrylate and other optional components-HOMS: 2-methacryloyl Oxyethyl hydrogen succinate / MMA: methylmethacrylate. (2) Adhesion of enamel and dentin Within 24 hours after slaughter, bovine anterior teeth are removed, and under water injection, # 80
The enamel or dentin plane was carved so as to be parallel to the labial surface with 0 emery paper. Next, compressed air is blown onto these surfaces for about 10 seconds to dry, and then a double-sided tape having a hole with a diameter of 4 mm is fixed on this surface, and then paraffin wax with a hole having a thickness of 1.5 mm and a diameter of 6 mm is opened. Were fixed so as to be in the same center on the circular hole to form a simulated cavity. The dental composition of the present invention prepared immediately before use was thinly applied in the simulated cavity, left for 20 seconds, and then compressed air was blown for about 10 seconds to dry. Next, the adhesive was applied and irradiated with a visible light irradiator (white light, manufactured by Takara Belmont Co., Ltd.) for 10 seconds to cure the adhesive. Further, a dental composite resin (Palfikh Lite Posteria, manufactured by Tokuyama Corp.) was filled on it, and light was irradiated for 30 seconds with a visible light irradiator to prepare an adhesive test piece. The adhesion test piece was immersed in water at 37 ° C. for 24 hours, and then a tensile tester (autograph,
Crosshead speed 10mm using Shimadzu Corporation)
The tensile adhesion strength between the tooth and the composite resin was measured. The tensile adhesion strength of four pieces per test was measured by the above method, and the average value was taken as the adhesive strength. The adhesive force is generated by the gap between the filling material and the tooth surface,
17MP for enamel to prevent the filling material from falling off
About a and about 15 MPa or more for dentin. (3) The bovine anterior teeth were removed within 24 hours after slaughter of the marginal blockage, and under water injection, # 80.
The enamel plane was carved so as to be parallel to the labial surface with 0 emery paper. Then the water injection under carborundum point (HP35, manufactured by Matsukazesha) with the inner diameter 4.5m
A cavity was formed which reached m to 5 mm and a depth of 4 mm to 5 mm and which reached the dentin. The primer composition of the present invention was thinly applied in this cavity, and after leaving it for 20 seconds, compressed air was applied to about 5
Spray for seconds to dry. Next, an adhesive is applied, and a visible light irradiator (white light, manufactured by Takara Belmont Co.)
Then, the adhesive was cured by irradiating with light for 10 seconds. Further, a dental composite resin (Palfique Esterite, manufactured by Tokuyama Corp.) was filled on it, and light was irradiated for 30 seconds by a visible light irradiator to prepare a marginal sealing test piece.
After immersing the adhesion test piece in water at 37 ° C. for 24 hours,
Under water, the excess composite resin was removed by polishing with # 800 emery paper, and the root portion was covered with a resin (Tokuso Cure Fast, manufactured by Tokuyama Corp.) manufactured by Immediate Polymerization. This is an aqueous solution of dye (4.
1% basic fuchsin, alternately Tokyo Kasei) was repeated, not a One 60 dips each 1 minute. After soaking, make sure that the test piece can be seen in a cross-section from the neck direction to the crown direction #
After grinding with 120 emery paper, the state of penetration of the dye into the interface between the tooth substance and the filled composite resin was observed and evaluated. For the evaluation, 6 test pieces, that is, 6 sections each on the tooth neck side and the crown side, 12 sections in total were observed, and the number of 12 minutes was counted to see if the dye had penetrated. That is, the larger the number, the better the edge sealing property. (4) Storage stability A component, B component and E component are dissolved in D component, and this mixed solution is mixed with a predetermined amount of C component immediately after preparation and after storage at 37 ° C. for 2 weeks under airtightness. Was used as a primer and the adhesive strength was measured. (5) Preparation of Adhesives Adhesives A to V were obtained as a viscous liquid by mixing and agitating with the compositions shown in Table 1 under shading. As the adhesive material W, the bonding agent attached to the clear fill liner bond 2 which is a commercially available adhesive material was used as it was.

[Table 1] Adhesives A and B are adhesives containing neither the (H) component nor the (J) component. Adhesives C to K are adhesives containing component (H), adhesive L is an adhesive containing both components (H) and (J), and adhesives N to V are components (J) and (K). component,
The adhesive material contains all the components (E), and the adhesive material M contains the components (J) and (E) but does not contain the component (K). Example 1 5.0 g of 3.5 g of PM and 1.5 g of MAC-10 were dissolved in distilled water. The tooth surface was treated with this as a primer and bonded using the adhesive material A, and the adhesive force of enamel and dentin was measured. The results are shown in Table 2. Examples 2 to 14 A primer was prepared according to the method of Example 1, and the adhesive material A was used.
Was evaluated using. The composition of the primer and the results are shown in Table 2. Comparative Examples 1 to 7 A primer was prepared according to the method of Example 1, and the adhesive material A was used.
Was evaluated using. The composition of the primer and the results are shown in Table 2.

[Table 2] From Example 1, it is clear that if the components (A), (B) and (C) are contained, sufficient adhesive strength can be obtained for both enamel and dentin, and the object of the present invention can be achieved. Is. In Examples 2 to 7, phenyl- was used as the component (A).
It is a result when P is used, MAC-10 is used as a (B) component, EtOH is used as a (D) component, and each compounding amount is changed. Examples 8 and 9 are the results when different (A) components are used, and Examples 10 and 11 are the results when different (B) components are used, and Example 12 uses a plurality of (B) components. As a result, in Example 13, different (D) components are used, and in Example 14, a plurality of (D) components are used. In all of the above cases, good adhesive strength was exhibited for both enamel and dentin. On the other hand, Comparative Example 1 is the result when the component (A) was not contained, and the adhesive strength was low in both dentin and enamel. Comparative Example 2 is a result of using phosphoric acid having no polymerizable unsaturated group in place of the component (A), but the adhesive strength to dentin was low. Comparative Example 3 was a case where the amount of the component (A) was above the range, and in this case as well, the adhesive strength was low in both dentin and enamel. In Comparative Example 4, when the component (B) was not included, Comparative Example 6
Shows the results when HOMS having only one carboxyl group was used in place of the component (B), but the adhesive strength to dentin was low in all cases. In Comparative Example 5, the amount of the component (B) was above the range, and in Comparative Example 7, the amount of the component (C) was below the range. Examples 15 to 23 A primer is prepared according to the method of Example 1 and the adhesive M
Or it evaluated using N. The composition of the primer and the results are shown in Table 3. Comparative Examples 8 to 17 A primer was prepared according to the method of Example 1 and the adhesive M
Or it evaluated using N. The composition of the primer and the results are shown in Table 3.

[Table 3] In Examples 15 to 19, using the adhesive material M, Examples 20 to 2 were used.
3 is the component (A), the component (B), and the component (D) using the adhesive material N.
It is a result when the kind and amount of components are changed. Examples 15 and 20 and 21 show the results when different (A) components are used, Example 16 shows the results when a plurality of (D) components are blended, and Example 17 shows the blending amount of the (C) component. Examples 15 and 18, 19 represent the results when the component (B) and the component (D) were changed, and Examples 22 and 23 contain a plurality of the components (A). Represents the result of Both have sufficient adhesive strength to both enamel and dentin. Comparative Examples 8 and 14 are (A)
This is the result when no components were contained, and the adhesive strength was low in both dentin and enamel. Comparative Examples 9 and 15 show the results when phosphoric acid having no polymerizable unsaturated group was used in place of the component (A), but the adhesive strength to dentin was low. Comparative Examples 10 and 16 are cases where the amount of the component (A) is above the range,
Also in this case, the adhesive strength was low for both dentin and enamel.
Comparative Examples 11 and 17 are results when the component (B) was not included, and Comparative Example 12 was results when HOMS having only one carboxyl group was used instead of the component (B). Poor adhesion to quality. Examples 24 to 36 Primers were prepared according to the method of Example 1 and evaluated using different adhesives. The composition of the primer, the adhesive used, and the results are shown in Table 4.

[Table 4] In Examples 24 to 36, phenyl-P was used as the component (A),
After treating with MTS as the component (B) and a primer using IPA as the component (D), the adhesive strength is measured using adhesives of various compositions. It is clear that in both cases, good adhesive strength is exhibited for both dentin and enamel, and the composition of the adhesive is not limited. Examples 37 to 53 A primer was prepared according to the method of Example 1 and the adhesive G
Was evaluated using. Table 5 shows the composition of the primers and the results. Comparative Examples 18-23 A primer was prepared according to the method of Example 1 and the adhesive G
Was evaluated using. Table 5 shows the composition of the primers and the results.

[Table 5] Examples 37 to 53 are the results when the components (E), (F) and (G) were further added in addition to the components (A), (B), (C) and (D). is there. Example 37
The components (F) to (44) are blended. Examples 37-39
When the blending amount of the (F) component and the (C) component is changed,
Example 40 is different from Example 40 in the case of using a different component (A).
1 and 42 are the results when different (B) components are used, and the blending amount of the (B) component is further changed, and Examples 43 and 44 are results when different (F) components are used. In all cases, good adhesion was shown to both dentin and enamel.
Examples 45 and 46 are the results when the component (G) was contained, and also at this time, good adhesive strength was exhibited. Example 47-
49 is the result when the component (E) was blended. Examples 47 and 48 are representative of the results when different (E) components are used, and Examples 48 and 49 are representative of the results when different (D) components are used. Examples 50 and 51 are the results when both the component (E) and the component (F) were blended, and Examples 52 and 53 are the results when both the component (E) and the component (G) were blended. In all of the above cases, good adhesive strength was exhibited. Comparative Example 18 is the result when the component (A) was not contained, and the adhesive force to dentin was low. Comparative Example 1
No. 9 was the case where the amount of the component (B) exceeded the range of the present invention, and the adhesive strength was low in both dentin and enamel. Comparative Example 20 is the result when the component (C) was not included, and the adhesive strength was low in both dentin and enamel. Examples 54 to 63 Primers were prepared according to the method of Example 1 and evaluated using different adhesives. The composition of the primer, the adhesive used, and the results are shown in Table 6.

[Table 6] Examples 54 to 63 were treated with a primer containing a component (A), a component (B), a component (C) and a component (D), and further a component (E), a component (F) and a component (G). After that, the adhesive force is measured using adhesives having various compositions. It is clear that in both cases, good adhesive strength is exhibited for both dentin and enamel, and the composition of the adhesive is not limited. Examples 64 to 71 A primer was prepared according to the method of Example 1, and the edge sealing property was evaluated using different adhesives. The composition of the primer, the adhesive used, and the results are shown in Table 7. Comparative Examples 21 and 22 A primer was prepared according to the method of Example 1 and the adhesive N
The edge sealing property was evaluated using. The composition of the primer and the results are shown in Table 7.

[Table 7] All of Examples 64 to 71 showed obviously better marginal edge blocking properties as compared with Comparative Example 21 not containing the component (A) and Comparative Example 22 not containing the component (C). Further, Examples 67 to 71 containing the component (E) showed better edge blocking properties as compared with Examples 64 to 66 not containing the component (E). Examples 72-74 1.0 g phenyl-P and 0.8 g MAC-10,
1. An ether type water-soluble organic solvent having no hydroxyl group.
7 g of DME (Example 72) or BMEE (Example 7)
It was dissolved in 3). In addition to 0.2 g in Example 74
NPG was also dissolved. A storage stability test was performed using these solutions. Adhesive G was used for the test. The primer composition and the results are shown in Table 8.

[Table 8] The primers of Examples 72 to 74 showed the same adhesive strength as that before storage after storage at 37 ° C., and had good storage stability. Reference Examples 1 to 16 A primer was prepared according to the method of Example 1 and the adhesive C
Alternatively, the adhesive strength was evaluated using R. The composition of the primer, the adhesive used, and the results are shown in Table 9. Comparative Examples 23 to 28 A primer was prepared according to the method of Example 1 and the adhesive C
Alternatively, the adhesive strength was evaluated using R. The composition of the primer, the adhesive used, and the results are shown in Table 9.

[Table 9] Reference Examples 16 to 39 A primer was prepared according to the method of Example 1, and the adhesive strength was evaluated using different adhesives. Table 10 shows the composition of the primer, the adhesive used, and the result. Comparative Examples 29 to 31 Primers were prepared according to the method of Reference Example 1 and the adhesive strength was evaluated using different adhesives. Table 10 shows the composition of the primer, the adhesive used, and the result.

[Table 10] Reference Examples 40 to 50 A primer was prepared according to the method of Example 1 and the adhesive strength was evaluated using different adhesive materials. Table 10 shows the composition of the primer, the adhesive used, and the result.

[Table 11] Reference Examples 1 to 39 and Comparative Examples 26 to 34 are results when the compositions containing no component (B) were used as the primer. Reference Examples 1 to 8 are adhesive materials C which are compositions containing (H) component as adhesive materials, and Reference Examples 9 to 16 are all (J) component, (K) component, and (E) component as adhesive materials. It is a result when using the adhesive material R which is a composition containing. Reference Examples 1 to 3 and 9 to 11 are results when different (A) components are used. All showed good adhesion. Reference example 2
6 to 8 and Reference Examples 10 and 14 to 16 represent the results when the amounts of the components (A), (D) and (C) in the primer were changed. Reference Examples 5 and 12 are the results when different component (D) was used, and Reference Examples 5 and 13 replaced part of the component (D) with HEMA which is a water-soluble alcohol having a polymerizable unsaturated group. It is the result of the case. In all of the above cases, good adhesion was obtained for both dentin and enamel. Comparative Examples 23 and 24 are the results when phosphoric acid containing no polymerizable unsaturated group was used in place of the component (A) in the primer, and Comparative Examples 25 and 26 had a blending amount of the component (A) within the range. This is the case. The dentin adhesion was low in all cases. Comparative Examples 27 and 28 are the results when the component (C) was not included, and the adhesive strength to both dentin and enamel was low. Reference Examples 17 to 39
Is an adhesive material D to L which is a composition containing the component (H) as an adhesive material, or an adhesive material N to V which is a composition containing all the components (J), (K) and (E). (Excluding R)
It is a result when using. In each case dentin,
It can be seen that there is no problem if an adhesive having a composition satisfying the above conditions is exhibited, showing a good adhesive strength to both enamel. Comparative Example 29 contains the component (K) and the component (E),
The results are obtained when an adhesive containing neither component (H) nor component (J) was used, and Comparative Example 30 is a polymerizable monomer having only one carboxyl group in place of component (J). HO
As a result of using MS, Comparative Example 31 is a result of using an adhesive containing the (J) component and the (E) component but not the (H) component or the (K) component. In each case, the adhesive strength to enamel was low, and the results were obtained in Examples 2, 15 and 2
From the comparison with No. 4, it can be seen that when the component (B) is not contained in the primer, a specific adhesive satisfying the above conditions is required. Reference Examples 40 to 50 are the results when HOMS was added to the primer composition in addition to the components (A), (C), and (D), or the component (E) or an optional component. In each case, good adhesive strength was exhibited for both dentin and enamel, and it can be seen that the addition of these has no problem.

By using the dental composition of the present invention as a pretreatment agent for the surface of the tooth structure prior to the adhesive agent when the tooth and the filling material are adhered by the adhesive agent, only one pretreatment operation is required. As a result, the complicated pretreatment operation for the dentin surface, which requires two treatments of applying a primer after the treatment with an aqueous acid solution, which has been conventionally performed, is simplified. Furthermore, a high adhesive strength is obtained for both enamel and dentin.

Continuation of the front page (31) Priority claim number Japanese Patent Application No. 7-63862 (32) Priority date March 23, 1995 (March 23, 1995) (33) Priority claim country Japan (JP) (56) References JP-A-6-192029 (JP, A) JP-A-6-24928 (JP, A) JP-A-3-240712 (JP, A) JP-A-62-149707 (JP, A) JP-A-3 -133912 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) A61K 6/00 C08F 222/20 C08L 35/02

Claims (7)

(57) [Claims] 1. (A) a phosphoric acid group-containing polymerizable monomer,
(B) Polycarboxylic acid group-containing polymerizable monomer, and (C)
Water as a main component, and 5 to 50% by weight of the component (A) and 1 to 50% by weight of the component (B) with respect to the composition,
A dental composition in which the component (C) accounts for 5 to 90% by weight. 2. The water-soluble organic solvent (D) is contained in an amount of 1 to 80% by weight.
The dental composition according to claim 1 , further comprising: 3. The ( E) polyfunctional polymerizable monomer is added in an amount of 0.1 to 0.1.
The dental composition according to claim 1 or 2, further containing 30% by weight . 4. The (A) phosphoric acid group-containing polymerizable monomer is
General formula (1) (2) or (3) (However, R ₁ and R ₂ are each independently a hydrogen atom or a
Represents a chill group, and R ₃ and R ₄ are each independently an ether bond.
1 to 3 carbon atoms which may have a compound and / or an ester bond
The divalent to hexavalent organic residue 0, _{R 5} is a hydrogen atom or a carbon atoms
1 to 5 alkyl or alkoxy groups, Z is an oxygen atom
Or hydroxyl sulfur _atom, in X 1, _{X 2} are each independent,
Represents a mercapto group or a halogen atom, and n ₁ and n ₂ are 1 to
It is an integer of 5. ) Is a polymerizable monomer represented by
Item 1. A dental adhesive composition according to items 1 to 3 . 5. (B) Polyvalent carboxylic acid group-containing polymerizable monomer
The body is represented by the following general formula (4) or (6) (However, each R ₁ is independently a hydrogen atom or a methyl group.
And each R ₃ independently represents an ether bond and / or
2 to 2 having 1 to 30 carbon atoms which may have an ester bond
Hexavalent organic residue, R ₆ is hydrogen atom or carboxyl group
, N ₁ represents an integer of ₁ to 5, and n ₃ represents 1 or 2.
You ) Is a polymerizable monomer represented by
5. The dental composition of claims 1-4 . 6. (A) a phosphoric acid group-containing polymerizable monomer,
(B) polyvalent carboxylic acid group-containing polymerizable monomer, (C) water,
(D) Water-soluble organic solvent, and (F) Strong inorganic acid and / or
Is based on non-polymerizable organic sulfonic acid, and
0.5 to 7% by weight of the component (A) relative to the composition, (B)
3 to 50% by weight of component, 5 to 90% by weight of component (C),
The component (D) is 1 to 80% by weight, and the component (F) is 0.0.
Dental composition , characterized in that it accounts for 1 to 3% by weight . 7. ( A) a phosphoric acid group-containing polymerizable monomer,
(B) polyvalent carboxylic acid group-containing polymerizable monomer, (C) water,
(D) Water-soluble organic solvent, and (G) Sulfonic acid group-containing
It is based on polymerizable monomers and is compatible with the composition.
The component (A) is 0.5 to 7% by weight, and the component (B) is 3 to
50% by weight, 5 to 90% by weight of component (C), component (D)
Is 1 to 80% by weight, and the component (G) is 0.01 to 12% by weight.
A dental composition comprising: