JP3480654B2 - Dental primer - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a primer used for treating the surface of a tooth in order to achieve high adhesion between the filling material and the tooth in the restoration of the tooth in the field of dentistry.

[0002]

2. Description of the Related Art A filling restoration material called a composite resin is usually used for restoration of tooth material damaged by dental caries etc. However, since the composite resin itself does not have adhesiveness, it is conventionally treated with an aqueous acid solution on the tooth surface. After treatment, washing with water, and drying, followed by application and drying of the primer, we have used an adhesive to bond the dentin and the composite resin. However, such treatment with an acid aqueous solution, treatment with a primer, and application of an adhesive material are complicated and time-consuming, which imposes a heavy burden on the dentist who is the operator and the patient, and may cause an operational error. Not a few.

Therefore, in recent years, attempts have been made to obtain a high adhesive force to the tooth structure only with the primer, omitting the treatment with the aqueous acid solution and the washing with water. For example, just before use
・ Mix the primer consisting of two solutions of B and apply it to the tooth surface.
There are several systems with a simplified operation method of drying, followed by application of adhesive and photo-curing, and these systems include the part where the primer adheres to soft tissues such as gums in the oral cavity. Conventional acid aqueous solution treatment / primer treatment
There are problems that have not been seen with adhesive-based systems.

As a system composed of a primer and an adhesive, Japanese Patent Application Laid-Open No. 8-319209 discloses a primer in which a phosphoric acid group-containing polymerizable monomer and a polyvalent carboxylic acid group-containing polymerizable monomer are used in combination. Therefore, 2-methacryloyloxyethyl phenyl phosphate (hereinafter referred to as phenyl-P) is used as the phosphoric acid group-containing polymerizable monomer to obtain high adhesive strength. However, since this substance phenyl-P remarkably whitens soft tissues in the oral cavity, the same problem as described above occurs when this substance is used as a component of a primer. On the other hand, when 2-methacryloyloxyethyl dihydrogen phosphate or bis (2-methacryloyloxyethyl) hydrogen phosphate is used, whitening of oral soft tissue is unlikely to occur, but the adhesive strength to dentin is 15 to 18 MPa
And inferior to phenyl-P. In recent years, in order to obtain high reliability, the demand for adhesive strength to dentin is increasing more and more, and 20 MPa or more is required. However, the above-mentioned 2-methacryloyloxyethyl dihydrogen phosphate or bis (2 -Methacryloyloxyethyl) When hydrogen phosphate is used, there is a fear of insufficient adhesive strength.

Inoue et al. 2-Acryloyloxyethyl
A primer using hydrogen malate (hereinafter referred to as 2AEM) is proposed (40th JADR
General Assembly and the 24th and 25th Annual Meeting of Japan Dental Science and Engineering Society)
This 2AEM also causes whitening of soft tissue and requires a long treatment time of 60 seconds. Further, JP-A-6-24928 discloses a primer containing a metal salt and an acidic group-containing polymerizable monomer. This primer is an adhesive containing a trialkylboron as a polymerization initiator. Therefore, this adhesive requires mixing of a polymerization initiator and a polymerizable monomer immediately before use, and since the pot life is relatively short, it is not sufficient from the viewpoint of improving operability. is there.

[0006]

In view of the above points, in the procedure of cavity repair such as pretreatment, application of adhesive, and filling of restoration material, the complicated operation of applying both the acid aqueous solution and the primer as pretreatment is simplified. Therefore, it is desired to develop a material that gives a high adhesive strength of 20 MPa or more to both enamel and dentin with a single pretreatment of only the primer and does not show harm due to whitening of soft tissues in the oral cavity. Was there.

[0007]

Means for Solving the Problems As a result of intensive studies to overcome the above technical problems, the present inventors have found that a phosphoric acid group-containing polymerizable monomer and a polyvalent carboxylic acid group-containing polymerizable monomer. , And in a composition containing water as a main effect component, by using a mixture of a phosphoric acid monoester having a specific structure and a phosphoric acid diester in a specific ratio as a phosphoric acid group-containing polymerizable monomer It has been found that it can be used as a dental primer which gives a high adhesive strength of 20 MPa or more to both enamel and dentin without treatment and is less likely to cause whitening of soft tissues in the oral cavity.

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. ), (B)
And 0.5 to 50 parts by weight of the component (A) and 1 to 50 parts by weight of the component (B) with respect to 100 parts by weight of the total of (C).
The component (C) accounts for 5 to 90 parts by weight, the component (A) comprises a mixture of compounds represented by the following general formulas [I] and [II], and the mixing ratio of [I] and [II] is: 1: 0.7 0 ~
A dental primer characterized by a molar ratio of 1: 1.35.

[0009]

[Chemical 3]

(In the formula, R ₁ , R ₂ and R ₃ are each independently an organic group having a polymerizable unsaturated group, Z is an oxygen atom or a sulfur atom, and X ₁ , X ₂ and X ₃ are each independently. OH
Group , halogen atom, phosphoryloxy group or acyloxy group
It is Shi group . ) Other inventions include (A) a phosphoric acid group-containing polymerizable monomer, (B) a polyvalent carboxylic acid group-containing polymerizable monomer,
(C) Water and (D) a water-soluble organic solvent as a main component, and (A), (B), (C) and (D) are 100 parts by weight in total, and the (A) component is 0. 5 to 50 parts by weight,
The component (B) is 1 to 50 parts by weight, the component (C) is 5 to 90 parts by weight, the component (D) is 1 to 80 parts by weight, and the component (A) is represented by the following general formulas [I] and [II]. And a mixture ratio of [I] and [II] is 1: 0.
7 0-1: a dental primer that features that 1.35 molar ratio.

[0011]

[Chemical 4]

(In the formula, R ₁ , R ₂ and R ₃ are each independently an organic group having a polymerizable unsaturated group, Z is an oxygen atom or a sulfur atom, and X ₁ , X ₂ and X ₃ are each independently. OH
Group , halogen atom, phosphoryloxy group or acyloxy group
It is Shi group . The phosphoric acid group-containing polymerizable monomer (A) used in the present invention is a phosphoric acid monoester represented by the above general formula [I] (hereinafter abbreviated as phosphoric acid monoester [I]).
And a phosphoric acid diester represented by the general formula [II] (hereinafter abbreviated as phosphoric acid diester [II]) in a specific ratio, each of which is not particularly limited as long as it is a compound satisfying the above structure.

In the above general formulas [I] and [II], Z
Is an oxygen atom or a sulfur atom, but an oxygen atom is preferable in view of storage stability and odor.

In the above general formula, X ₁ , X ₂ and X ₃ each independently react with an OH group or water, which is an essential component of the present invention, in the = P (Z) -OR structure. OR group (however,
R is more easily O than R is R ₁ , R ₂ or R _3.
It is a group that can be converted into an H group, and specifically includes a halogen atom, a phosphoryloxy group, an acyloxy group and the like.

Examples of compounds having such an atomic group include compounds represented by the following general formula.

[0016]

[Chemical 5]

(Wherein R ₁ , R ₂ and R ₃ are as described above,
R ₄ , R ₅ and R ₆ each independently have the same organic group as R ₁ , R ₂ and R ₃ or a polymerizable unsaturated group; and / or
Or an organic group having 15 or less carbon atoms which does not have. ) Among the compounds listed in the above general formula, the ease of synthesis or availability,
Considering the stability and adhesiveness during storage when used as a dental composition, the phosphoric acid monoester [I] is a compound represented by the general formula (1) or (2), and the general formula (4) )
Of the compounds represented by, it is more preferable to use the compound having the same R ₁ and R _4, and it is most preferable to use the compound represented by the general formula (1). Similarly, as the phosphodiester [II], among the compounds represented by the general formulas (6) and (7) and the compounds represented by the general formula (9), R ₂ and R 6 , and R ₃ and R _It is preferable to use the compounds in which ₅ are the same, and it is most preferable to use the compound represented by the general formula (6).

In the above general formulas [I] and [II], R
₁ , R ₂ and R ₃ are each independently an organic group having at least one polymerizable unsaturated group, and known organic groups can be applied without particular limitation.

The polymerizable unsaturated group contained in R ₁ , R ₂ and R ₃ is not particularly limited as long as it is an unsaturated group which can be polymerized by radicals, and a known group may be applied. Specific examples thereof include (meth) acryloyloxy group, (meth) acryloylamino group, (meth) acryloylthio group, thio (meth) acryloyloxy group, styryl group, and allyl group. Among these polymerizable unsaturated groups, the (meth) acryloyloxy group or the (meth) acryloyl group is preferred because of their good polymerizability, relatively low toxicity to living organisms, and relatively easy synthesis. It is preferably an amino group, and most preferably a (meth) acryloyloxy group.

Regarding the portion of the organic group other than the polymerizable unsaturated group, a known divalent organic residue can be applied, and the organic residue has an ether bond, an ester bond, an aromatic group in its structure. It may have a ring or the like, and may further have a side chain, but it is preferably an organic residue having 1 to 20 carbon atoms from the viewpoint of easiness of synthesis and handling of the compound itself, More preferably, it is an alkyl group having a main chain length of 2 to 15 atoms.

Specific examples of such an organic residue are as follows.

[0022]

[Chemical 6]

Specific examples of the preferred phosphoric acid monoester [I] are as follows.

[0024]

[Chemical 7]

[0025]

[Chemical 8]

(In the formula, R ₉ represents a hydrogen atom or a methyl group.) Specific examples of the preferable phosphoric acid diester [II] are as follows.

[0027]

[Chemical 9]

[0028]

[Chemical 10]

[0029]

[Chemical 11]

[0030]

[Chemical 12]

(In the formula, each of R ₉ and R ₁₀ independently represents a hydrogen atom or a methyl group.) Among the above phosphoric acid diesters [II], 2 is selected from the viewpoint of easiness of synthesis and preparation of molar ratio. It is preferable to use a compound in which two organic groups (R ₂ and R _{3 in the} general formula [II]) are the same.

In the present invention, one or both of the above-mentioned phosphoric acid monoester [I] and phosphoric diester [II] are mixed in a mixture of two or more, and a mixture of three or more phosphoric esters (A ) It is also possible to use as a phosphoric acid group-containing polymerizable monomer component, but both phosphoric acid monoester [I] and phosphoric acid diester [II] are combined because of ease of synthesis and preparation of molar ratio. The use of a mixture consisting of a single compound is preferable, and one organic group of the phosphoric acid monoester (R ₁ in the general formula [I]) and two organic groups of the phosphoric acid diester [II] (the general formula [I I
It is more preferable to use as the component (A) a mixture of compounds in which R ₂ and R _{3 in} I] are all the same.

The (A) phosphoric acid group-containing polymerizable monomer of the present invention comprises a phosphoric acid monoester [I] and a phosphoric acid diester [I].
I] must be a mixture having a molar ratio of 1: 0.70 to 1: 1.35, preferably a molar ratio of 1: 0.75 to
It is a mixture of 1: 1.30, most preferably a mixture with a molar ratio of 1: 0.80 to 1: 1.25. When the molar ratio of the phosphoric acid diester [II] is less than 0.70, the dentin adhesive strength is lowered and the adhesion durability is also deteriorated.
On the contrary, when the molar ratio of the phosphoric acid diester [II] is larger than 1.35, the adhesive strength of both dentin and enamel decreases,
Furthermore, the adhesion durability to enamel also deteriorates.

The term "molar ratio" used in the present invention means the molar ratio of phosphoric acid diester [II] to phosphoric acid monoester [I]. Therefore, a small molar ratio means that the amount of phosphodiester is relatively small, and a large molar ratio means that the amount of phosphodiester is relatively large.

The compounding amount of the (A) phosphoric acid group-containing polymerizable monomer in the present invention is the component (A) constituting the composition,
With respect to 100 parts by weight in total of the components including the component (B), the component (C), and the component (D) optionally blended (hereinafter referred to as total 100 parts by weight of the main components), 0. 5-5
It accounts for 0 part by weight, preferably 5 to 50 parts by weight, more preferably 7 to 40 parts by weight. If the blending amount is less than 0.5 parts by weight, the adhesive strength to both dentin and enamel, especially to enamel, will decrease, and conversely if the blending amount exceeds 50 parts by weight, both dentin and enamel, especially dentin The adhesive strength to

The polyvalent carboxylic acid group-containing polymerizable monomer (B) of the present invention has a plurality of carboxyl groups in one molecule, or a plurality of carboxyl groups by easily reacting with water which is an essential component of the present invention. It is a polymerizable monomer having an acid derivative group such as an acid anhydride or an acid halide capable of forming an individual group and having at least one polymerizable unsaturated group.

As such a compound, the following general formula (1
1) trimellitic acid derivatives and their anhydrides or halides, pyromellitic acid derivatives and their anhydrides or halides represented by the following general formula (11) or (12), and the following general formulas Examples thereof include malonic acid derivatives represented by the formula (13) and their anhydrides or halides, or 6- (meth) acryloxyethylnaphthalene-1,2,6-tricarboxylic acid and N- (meth) acryloylaspartic acid. To be

[0038]

[Chemical 13]

(In the formula, R ₉ represents a hydrogen atom or a methyl group, and R ₁₁ represents a divalent to C6 organic residue having 1 to 30 carbon atoms, which may have an ether bond and / or an ester bond. To R
₁₂ represents a hydrogen atom or a carboxyl group, and n ₁ is 1 to
And n3 represents 1 or 2. ) General formula (11)
Preferred specific examples of the polyvalent carboxylic acid group-containing polymerizable monomer represented by are as follows.

[0040]

[Chemical 14]

[0041]

[Chemical 15]

[0042]

[Chemical 16]

[0043]

[Chemical 17]

[0044]

[Chemical 18]

(In the formula, R ₁ represents a hydrogen atom or a methyl group.) Preferred specific examples of the polyvalent carboxylic acid group-containing polymerizable monomer represented by the general formula (12) are as follows. is there.

[0046]

[Chemical 19]

(In the formula, R ₁ represents a hydrogen atom or a methyl group.) Preferred specific examples of the polyvalent carboxylic acid group-containing polymerizable monomer represented by the general formula (13) are as follows. is there.

[0048]

[Chemical 20]

[0049]

[Chemical 21]

(In the formula, R ₁ represents a hydrogen atom or a methyl group.) Among the above-mentioned polyvalent carboxylic acid group-containing polymerizable monomers, two carboxyl groups or carboxyl groups are selected from the viewpoint of adhesiveness to the tooth. A polymerizable monomer having a resulting group on the same carbon or on an adjacent carbon is preferable, and a polyvalent carboxylic acid group-containing polymerizable monomer of a trimellitic acid derivative or malonic acid derivative is more preferably used. It

If necessary, a plurality of these polyvalent carboxylic acid group-containing polymerizable monomers may be mixed and used.

The compounding amount of the polyvalent carboxylic acid group-containing polymerizable monomer (B) in the present invention is 1 to 50 parts by weight, preferably 5 to 25 parts by weight, based on 100 parts by weight of the total of the main components.
Account for parts by weight. If the blending amount is less than 1 part by weight, the adhesive strength to dentin will decrease, and conversely if the blending amount exceeds 50 parts by weight, the adhesive strength to both dentin and enamel will decrease.

The above components (A) and (B) are added together to obtain
It is preferable to occupy 10 parts by weight or more, more preferably 15 parts by weight or more, out of 100 parts by weight of the main components.

The water (C) used in the present invention is necessary for decalcification of hydroxyapatite in the tooth structure. This water preferably contains substantially no impurities harmful to storage stability, biocompatibility and adhesiveness, and examples thereof include deionized water and distilled water. The blending amount of (C) water in the present invention is 5 to 90 parts by weight in 100 parts by weight of the main components in total,
It preferably accounts for 20 to 80 parts by weight. If the amount is less than 5 parts by weight, demineralization of the tooth structure becomes insufficient, resulting in insufficient adhesive strength of the enamel and insufficient adhesive strength to dentin. 9
If it exceeds 0 parts by weight, the adhesive strength of both dentin and enamel will decrease.

The water-soluble organic solvent (D) used in the present invention includes (A) a phosphoric acid group-containing polymerizable monomer, (B) a polyvalent carboxylic acid group-containing polymerizable monomer, and (E) below. ) Improving the solubility of various polymerizable monomers such as polyfunctional polymerizable monomers and (F) polymerization accelerators in water, and dissolving each component to 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 and 2-
Propanol, 1-butanol, 2-butanol, 2-
Methyl-1-propanol, 2-methyl-2-propanol, 2-methyl-2-butanol, 2-propene-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-isopropoxy ethanol, 2-butoxy ethanol, 1-methoxy-2-propanol, 1-ethoxy- Alcohol compounds such as 2-propanol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether and 2-hydroxyethyl methacrylate, cyclic ethers such as 1,3-dioxolane, tetrahydrofuran, dioxane and propylene oxide, dimethoxymethane, 1 1,2-dimethoxyethane, 1,2-diethoxyethane, bis (2-methoxyethyl) ether, bis (2-ethoxyethyl) ether, etc. Such as linear ether compounds, ketone compounds such as acetone and methyl ethyl ketone, phosphoric acid compounds such as hexamethylphosphoric triamide, acid amide compounds such as dimethylformamide and dimethylacetamide, acetic acid, propionic acid, methacrylic acid and the like. Examples thereof include carboxylic acid compounds, sulfur oxide compounds such as dimethyl sulfoxide and sulfolane.

Among these water-soluble organic solvents, ethanol, propanol or acetone is preferably used from the viewpoint of harmful effects on the living body, and hydroxyl group is also considered from the viewpoint of storage stability and dentin adhesiveness of the dental composition. Preference is given to using straight chain ether compounds or ketones.

A plurality of the above water-soluble organic solvents can be mixed and used if necessary.

The amount of the water-soluble organic solvent (D) used in the present invention is 1 to 80 parts by weight, more preferably 5 to 70 parts by weight, and particularly preferably 10 to 50 parts by weight, based on 100 parts by weight of the main component. If the amount is less than 1 part by weight, the effect of promoting the dispersion / dissolution of (A) the phosphoric acid group-containing polymerizable monomer and (B) the polyvalent carboxylic acid group-containing polymerizable monomer in water tends to be insufficient. If it exceeds 80 parts by weight, the adhesive strength tends to be low in both dentin and enamel.

The dental composition of the present invention preferably further comprises (E) a polyfunctional polymerizable monomer. By incorporating the polyfunctional polymerizable monomer, the marginal blocking property is improved.

The (E) polyfunctional polymerizable monomer of the present invention is
There is no particular limitation 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 a compound include divinylbenzene, 2,2-bis (4-methacryloyloxyphenyl) propane and 2,2-bis (4- (3-methacryloyloxy-2-hydroxypropoxy). Phenyl) propane, 2,2-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-methacryloyloxydiethoxyphenyl) -2 (4- Methacryloyloxytriethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2 (4-methacryloyloxytriethoxyphenyl) propane, 2,2-
Bis (4-methacryloyloxydipropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane, 1-methacryloyloxymethyl-2-methacryloyloxyethyl
Aromatic bifunctional monomers such as hydrogen malate and acrylates thereof, diallyl ether, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, propylene glycol Dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, glycerin dimethacrylate, di-2-methacryloyloxyethyl-2,2,4-trimethylhexa Aliphatic bifunctional monomers such as methylene dicarbamate, N, N-methylene bis methacrylamide and their acrylates, trimethylol purine Pantrimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, tri (2-methacryloyloxyethyl) phosphate and trifunctional monomers such as acrylates thereof, tetraerythritol tetramethacrylate, pentaerythritol tetraacrylate and other tetrafunctional monomers. Examples thereof include functional monomers.

Among the above-mentioned polyfunctional polymerizable monomers, it is preferable to use an aliphatic bifunctional monomer or a tri- or tetra-functional monomer in view of the effect of improving the edge blocking property. Further, in consideration of toxicity to the living body and polymerizability, it is preferable to use a compound in which the polymerizable unsaturated group is a (meth) acryloyloxy group or a (meth) acryloylamino group.

If necessary, a plurality of these polyfunctional polymerizable monomers may be mixed and used.

The compounding amount of the (E) polyfunctional polymerizable monomer in the present invention is 100 parts by weight of the total of the main components.
The amount is preferably 0.1 to 30 parts by weight, more preferably 0.2.
To 20 parts by weight, and most preferably 0.5 to 10 parts by weight. If it is less than 0.1 part by weight, the effect of improving the marginal sealing property tends not to be recognized, and if it exceeds 30 parts by weight, the adhesive strength to both dentin and enamel tends to decrease.

The dental composition of the present invention preferably further contains (F) a polymerization accelerator in order to further improve the adhesiveness to the tooth substance, particularly in order to improve the margin sealing property. By blending the polymerization accelerator, it becomes possible to increase the polymerization rate at the interface between the tooth substance and the adhesive material, or to start the polymerization reaction from the interface.

In the present invention, a substance capable of independently initiating polymerization (hereinafter referred to as a polymerization initiator), which has no ability to initiate polymerization by itself, is used in combination with a polymerization initiator. A substance that improves the polymerization initiation ability of the polymerization initiator and a substance that has little ability to initiate polymerization by itself but initiates polymerization when a plurality of them are combined are collectively referred to as a polymerization accelerator.

Further, in the present invention, when simply referred to as “polymerization (and the polymerization rate, polymerization reaction and the like related thereto”), it means all radical polymerization.

As the polymerization accelerator used in the present invention, known ones can be used without limitation. Such polymerization accelerators include hydrogen peroxide, organic peroxides, azo compounds, sulfinic acids, borates, amines, α-diketones, thioxanthones, α-aminoacetophenones,
Examples thereof include acylphosphine oxides, barbituric acids, mercapto compounds, quaternary ammonium halides, dyes, photoacid generators, organic borons, and transition metal compounds.

Illustrating the above organic peroxide as a specific example,
t-Butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, acetyl peroxide, lauroyl peroxide, benzoyl peroxide and the like can be mentioned.

Examples of azo compounds include azobisbutyronitrile, methyl azobisisobutyrate and azobiscyanovaleric acid.

As the sulfinates, sodium benzenesulfinate, lithium benzenesulfinate, sodium p-toluenesulfinate, lithium p-toluenesulfinate, potassium p-toluenesulfinate, sodium m-nitrobenzenesulfinate,
Examples thereof include sodium p-fluorobenzenesulfinate and the like.

Examples of the above borates include aryl borate compounds having 3 or 4 aryl groups in one molecule. Specifically, examples of the borate compound having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) boron, and monoalkyl. Tri (3,5-bistrifluoromethyl) phenylboron, monoalkyltri [3,5
-Bis (1,1,1,3,3,3-hexafluoro-2-
Methoxy-2-propyl) phenyl] boron (wherein the alkyl group is n-butyl group, n-octyl group, n-dodecyl group, etc.), sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt Salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, butylquinolinium salts, etc., and 4 in one molecule.
Examples of the aryl borate compound having one aryl group include tetraphenylboron, tetrakis (m-butoxyphenyl) boron, tetrakis (m-methoxyphenyl) boron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl). Boron, tetrakis (3,5-bistrifluoromethyl) phenylboron, tetrakis [3,5-bis (1,1,1,3,3,3)
3-hexafluoro-2-methoxy-2-propyl) phenyl] boron sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, Examples thereof include a butylpyridinium salt, a methylquinolinium salt, an ethylquinolinium salt, and a butylquinolinium salt.

Among the above aryl borates, tetraaryl borates in which 4 aryl groups are bonded to a boron atom are particularly preferable from the viewpoint of long-term storage stability.

As the amines, secondary or tertiary amine compounds having an amino group bonded to an aryl group are preferable, and specific examples thereof include N- (2-hydroxyethyl) aniline, N-methylaniline, N-methyl-p-
Secondary amines such as toluidine, 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, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amyl ester, N, N-dimethylanthranic acid methyl Ester, N, N-dihydroxyethylaniline, N, N
-Dihydroxyethyl-p-toluidine, p-dimethylaminophenethyl alcohol, p-dimethylaminostilbene, 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,
Tertiary such as N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, 2,2 ′-(n-butylimino) diethanol Examples include amines.

Further, camphorquinone, benzyl, α-
Naphthyl, acetonaphthene, naphthoquinone, p, p'-
Dimethoxybenzyl, p, p'-dichlorobenzylacetyl, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,
10-phenanthrenequinone and the like as α-diketones, 2,4-diethylthioxanthone and the like as thioxanthones, 2-benzyl-dimethylamino-1- (4
-Morpholinophenyl) -butanone-1,2-benzyl-diethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl-dimethylamino-
1- (4-morpholinophenyl) -propanone-1,
2-benzyl-diethylamino-1- (4-morpholinophenyl) -propanone-1,2-benzyl-dimethylamino-1- (4-morpholinophenyl) -pentanone-1,2-benzyl-diethylamino-1- ( 4-
Morpholinophenyl) -pentanone-1 and the like are α-aminoacetophenones as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,2).
Examples of the acylphosphine oxides include 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide.

Specific examples of barbituric acids include:
Examples thereof include 5-butyl barbituric acid, 1-ethyl-5-methyl barbituric acid, 1-hexyl-5-ethyl barbituric acid, 1-benzyl-5-phenyl barbituric acid, dodecyl mercaptan and penta. Examples of mercapto compounds include erythritol tetrakis (thioglycolate).

As the quaternary ammonium halide, it is preferable to use chloride because of its ability to accelerate polymerization.
Specific examples include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, tetrabutylammonium chloride, trioctylammonium chloride and the like.

Examples of the pigments include coumarin-based pigments. Particularly preferred coumarin-based dyes are 400 to 5
The one having the maximum absorption wavelength in the visible light region of 00 nm is
Highly sensitive to illuminators commonly used in dental applications.

Specific examples of typical coumarin dyes include 3-thienoylcoumarin, 3- (4-methoxybenzoyl) coumarin, 3-benzoylcoumarin, 3- (4
-Cyanobenzoyl) coumarin, 3-thienoyl-7-
Methoxycoumarin, 7-methoxy-3- (4-methoxybenzoyl) coumarin, 3-benzoyl-7-methoxycoumarin, 3- (4-cyanobenzoyl) -7-methoxycoumarin, 5,7-dimethoxy-3- (4 -Methoxybenzoyl) coumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3- (4-cyanobenzoyl) -5,
7-dimethoxycoumarin, 3-acetyl-7-dimethylaminocoumarin, 7-diethylamino-3-thienoylcoumarin, 7-diethylamino-3- (4-methoxybenzoyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 7- Diethylamino-3- (4-cyanobenzoyl) coumarin, 7-diethylamino-3- (4
-Dimethylaminobenzoyl) coumarin, 3-cinnamoyl-7-diethylaminocoumarin, 3- (p-diethylaminocinnamoyl) -7-diethylaminocoumarin, 3-acetyl-7-diethylaminocoumarin, 3-
Carboxy-7-diethylaminocoumarin, 3- (4-
Carboxybenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbiscoumarin, 3,3′-carbonylbis (7-diethylamino) coumarin, 2,
3,6,7-Tetrahydro-1,1,7,7-tetramethyl-10- (benzothiazoyl) -11-oxo-1
H, 5H, 11H,-[1] benzopyrano [6,7,8
-Ij] quinolidine, 3,3'-carbonylbis (5,5
7-) dimethoxy-3,3'-biscoumarin, 3-
(2′-benzimidazoyl) -7-diethylaminocoumarin, 3- (2′-benzoxazoyl) -7-diethylaminocoumarin, 3- (5′-phenylthiadiazoyl-2 ′)-7-diethylaminocoumarin, 3-
(2'-benzthiazoyl) -7-diethylaminocoumarin, 3,3'-carbonylbis (4-cyano-7-diethylamino) coumarin and the like can be mentioned.

As the photo-acid generators, known photo-acid generators can be used without any limitation as long as they can generate a Bronsted acid or a Lewis acid by irradiation with light. In particular, a halomethyl group-substituted-s-triazine derivative or diphenyliodonium is used. When a salt compound is used in combination with the coumarin-based dye and the sulfinates and / or borates, energy transfer is performed with the coumarin-based dye to generate an acid with high efficiency under visible light irradiation, and the sulfinic acid and / or the borate. The efficiency of generating radicals in the class is high.

Specific examples of typical halomethyl group-substituted-s-triazine derivatives are shown below, 2,4,6-tris (trichloromethyl) -s-triazine and 2,4,6-.
Tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl)
-S-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-
Triazine, 2- (p-methylthiophenyl) -4,6
-Bis (trichloromethyl) -s-triazine, 2-
(P-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-bromo Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6
-Bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (o-methoxystyryl-4,6-bis (trichloromethyl)-
s-triazine, 2- (p-butoxystyryl) -4,
6-bis (trichloromethyl) -s-triazine, 2-
(3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4,5-
Examples thereof include trimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine.

Specific examples of the diphenyliodonium salt compound include diphenyliodonium, bis (p-chlorophenyl) iodonium, ditolyliodonium, bis (p-tert-butylphenyl) iodonium and bis (m-nitrophenyl). Iodonium, p
Chlorides such as -tert-butylphenylphenyliodonium, methoxyphenylphenyliodonium, p-octyloxyphenylphenyliodonium, bromide, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, trifluoromethanesulfonate salts Among others, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate or trifluoromethanesulfonate salt is preferably used from the viewpoint of solubility of the compound.

Examples of the organic boron type polymerization accelerator include triphenylborane, tributylborane, tributylborane partial oxide and the like.

Examples of the transition metal compounds include hydrochlorides, hydrofluorates, sulfates, nitrates, phosphates and acetates of transition metals such as iron, cobalt, nickel, copper, zinc, titanium, zirconium and cerium. Citrate, oxalate, EDTA
Examples thereof include salts or acetylacetone complex salts, and specifically, iron chloride, copper chloride, cobalt chloride, zinc chloride, iron nitrate, copper nitrate, iron acetate, copper acetate, iron citrate, copper citrate, iron oxalate, oxalic acid. Copper, iron acetylacetone, copper acetylacetone and the like are preferably used.

The content of these polymerization initiators is 10
0.001 to 30 parts by weight is preferable with respect to 0 parts by weight,
It is more preferably 0.05 to 10 parts by weight, and most preferably 0.1 to 5 parts by weight. If the blending amount is too small, the improvement in the adhesiveness is often not observed, and if it is too large, the adhesive strength may be decreased, which is not preferable.

These polymerization accelerators may be used alone or in combination in the dental composition of the present invention. There is no particular limitation when combining a plurality of compounds, and any combination can be used, but examples of preferable combinations include hydrogen peroxide / transition metal compounds, organic peroxides / amines, organic peroxides. A combination of substances / amines / sulfinic acids, organic peroxides / amines / borates, barbituric acids / quaternary ammonium halides / copper compounds, etc., which start polymerization by mixing, or the compound itself Α-diketones, thioxanthones, which decompose to form a polymerizable radical species upon irradiation with light,
A combination of α-aminoacetophenones, acylphosphine oxide derivatives, and tertiary amines, barbituric acids, and mercapto compounds that improve the polymerization initiation ability of the compound, or dyes / photoacid generators / Examples thereof include a combination of borate, dyes / photoacid generators / sulfinic acid, which initiates polymerization upon irradiation with light. When the above-mentioned polymerization accelerator is compounded, it is necessary to determine the packaging state in consideration of the combination itself and the storage stability when combined with other compounding ingredients.

The dental primer of the present invention includes the above-mentioned (A) phosphoric acid group-containing polymerizable monomer, (B) polyvalent carboxylic acid group-containing polymerizable monomer, (C) water, and (D) water-soluble. In addition to the organic solvent, the (E) polyfunctional polymerizable monomer, and the (F) polymerization accelerator, various optional components shown below may be added, if necessary, within a range that does not impair the effects of the present invention. Is also possible.

Examples of such optional components include acidic group-containing polymerizable monomers such as monocarboxylic acid group-containing polymerizable monomers, sulfonic acid group-containing polymerizable monomers and phosphonic acid group-containing polymerizable monomers. Examples of the functional monomers include non-acidic monofunctional polymerizable monomers, non-water-soluble organic solvents, inorganic or organic fine particles, acids, and dyes.

Acidic group-containing polymerizable monomers such as monocarboxylic acid group-containing polymerizable monomers, sulfonic acid group-containing polymerizable monomers and phosphonic acid group-containing polymerizable monomers, and Incorporation of an acidic monofunctional polymerizable monomer may further improve the tooth adhesiveness.

As the monocarboxylic acid group-containing polymerizable monomer, (meth) acrylic acid, 2- (meth) acryloyloxyethyl hydrogen malate, 2- (meth) acryloyloxyethyl hydrogen succinate, 2- ( (Meth) acryloyloxyethyl hydrogen phthalate, 3- (meth) acryloyloxypropyl hydrogen malate, 3- (meth) acryloyloxypropyl hydrogen succinate,
N- (meth) acryloyl-5-aminosalicylic acid, N
-(Meth) acryloylglycine, N- (meth) acryloylalanine, N- (meth) acryloylproline and the like can be mentioned, and as the sulfonic acid group-containing polymerizable monomer,
2- (meth) acrylamido-2-methylpropanesulfonic acid, 3- (meth) acryloyloxypropanesulfonic acid, N- (meth) acryloylsulfanilic acid and the like are vinylphosphonic acid as the phosphonic acid group-containing polymerizable monomer. Etc.

The non-acidic monofunctional polymerizable monomer can be divided into water-soluble ones and water-insoluble ones. Generally, the water-soluble non-acidic monofunctional polymerizable monomer is used. In many cases, when the body is used, the adhesiveness to the tooth structure is improved.

Specific examples of such a non-acidic monofunctional polymerizable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate,
2-Ethylhexyl (meth) acrylate etc. are mentioned as a water-insoluble non-acidic monofunctional polymerizable monomer, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2,3-dihydroxy. Propyl methacrylate,
2,3-dihydroxybutyl methacrylate, 2,4-
Dihydroxybutyl methacrylate, 2-hydroxymethyl-3-hydroxypropyl methacrylate, 2,
3,4-trihydroxybutyl methacrylate, 2,2
-Bis (hydroxymethyl) -3-hydroxypropyl methacrylate, 2,3,4,5-tetrahydroxypentyl methacrylate, diethylene glycol monomethacrylate, triethylene glycol monomethacrylate, tetraethylene glycol monomethacrylate, pentaethylene glycol monomethacrylate and these (Meth) acrylic acid esters of polyhydric alcohols such as acrylates or polyethylene glycols,
(Meth) acrylic acid amides of amino alcohols such as N-methylol methacrylamide, N-methylol acrylamide, diacetone (meth) acrylamide, N-
(Meth) acryloylmorpholine etc. are mentioned as a water-soluble non-acidic monofunctional polymerizable monomer.

The non-water-soluble organic solvent is used together with the water-soluble organic solvent to dissolve the various polymerizable monomers described above, whereby the storage stability of the dental primer of the present invention can be improved. There is a case. Such water-insoluble organic solvents include hexane, heptane, octane, toluene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, pentanone, hexanone, ethyl formate, propyl formate, butyl formate, ethyl acetate, propyl acetate, Examples thereof include butyl acetate, vinyl acetate, diethyl ether and the like.

By blending inorganic or organic fine particles, the viscosity and fluidity of the dental primer can be adjusted.

Specific examples of such fine particles include polyethylene, polypropylene, polymethylmethacrylate, polyamides, polyesters, polystyrenes,
Fine particles of polymers such as silicones, single or complex oxides of metals such as silicon, aluminum, titanium, zirconium, nickel, cobalt, strontium, iron, copper, zinc, tin, magnesium, calcium, potassium and sodium, Silicon nitride, aluminum nitride, titanium nitride, boron nitride, and other nitrides, silicon carbide, boron carbide, and other carbides, inorganic fine particles, and their metal oxides, metal nitrides, metal carbides, etc. Inorganic fine particles such as methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris (β-
(Methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltris (β-methoxyethoxy) silane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-glycidoxypropyl Silane coupling agents such as trimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β (3,4epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and hexamethyldisilazane , Isopropyl triisostearoyl titanate, isopropyl trioctanoyl titanate, isopropyl isostearoyl diacrylic titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl dimeta Lil isostearoyl titanate, titanate coupling agents such as isopropyl tricumylphenyl titanate include those surface-treated with aluminum-based coupling agents such as acetoalkoxyaluminum diisopropylate. further,
It is also preferable to use fine particles whose surface is coated with a polymer such as polyethylene, polypropylene, polymethylmethacrylate, polyamides, polyesters, polystyrenes, and silicones.

The method for producing the above-mentioned inorganic fine particles is not particularly limited, and the existing coprecipitation method, thermal spraying method, sol-gel method, bulk pulverization-classification method and the like can be used, and the surface treatment method is also Existing methods such as a spray drying method, a dry mixing method, and a wet mixing method can be used without limitation. The primary particle system of the fine particles is preferably 0.001 μm to 1 μm.
It is practically difficult to obtain particles of 0.001 μm or less,
On the other hand, when the particle diameter is too large, problems such as easy precipitation and difficulty in uniform dispersion occur. Therefore, the particle size is preferably 0.5 μm or less, more preferably 0.1 μm or less.

It is also possible to use a mixture of a plurality of fine particles having different composition, shape, manufacturing method, surface treatment method and particle system.

In some cases, it may be possible to improve the tooth demineralizing ability of the dental primer and to improve the adhesiveness, particularly the adhesiveness to enamel, by adding an acid.

Examples of such acids include inorganic acids such as hydrochloric acid, hydrofluoric acid, nitric acid, sulfuric acid and phosphoric acid, carboxylic acids such as acetic acid, lactic acid, butyric acid, oxalic acid, citric acid and maleic acid, benzenesulfonic acid and paratoluene. Examples thereof include organic sulfonic acids such as sulfonic acid.

Further, a coloring matter may be blended as a coloring material.

The method for preparing the dental primer of the present invention is not particularly limited, and the above-mentioned (A) phosphoric acid group-containing polymerizable monomer, (B) polyvalent carboxylic acid group-containing polymerizable monomer, ( C) water, (D) water-soluble organic solvent, and optional components to be blended as necessary may be weighed in a desired ratio in a container and mixed by stirring to form a uniform solution or emulsion.

The packing form of the dental primer of the present invention is as follows:
It can be appropriately determined under the condition that the storage stability is not impaired. For example, a phosphoric acid group-containing polymerizable monomer, a polyvalent carboxylic acid group-containing polymerizable monomer, and a liquid containing a water-soluble organic solvent as a main component, and a liquid containing water as a main component are separately packaged. It is possible to mix when using.

The dental primer of the present invention is usually included for pretreatment of the tooth surface prior to application of the adhesive material to the tooth.

As such an adhesive material, a material known as a dental adhesive material is used without particular limitation.

The above-mentioned dental adhesive material usually comprises a combination of a polymerizable monomer, a polymerization catalyst for polymerizing the polymerizable monomer, and other components to be blended if necessary.

Examples of the polymerizable monomer include the phosphoric acid group-containing polymerizable monomer, the polyvalent carboxylic acid group-containing polymerizable monomer, and the polyfunctional polymerizable monomer described in the section of the dental composition. A quantity,
Monocarboxylic acid group-containing polymerizable monomer, sulfonic acid group-containing polymerizable monomer, water-insoluble non-acidic monofunctional polymerizable monomer, water-soluble non-acidic monofunctional monomer, etc. Alternatively, multiple combinations are shown. Furthermore, as the phosphoric acid group-containing polymerizable monomer, those outside the molar ratio range specified in the dental composition, or a polymerizable monomer represented by the following general formula is also used. It

[0108]

[Chemical formula 22]

(In the formula, R ₉ and R ₁₀ are as described above, and R ₁₃ is an organic group having no polymerizable unsaturated group) Specific examples of the phosphoric acid group-containing polymerizable monomer represented by the above general formula It is as shown below.

[0110]

[Chemical formula 23]

[0111]

[Chemical formula 24]

(In the formula, R ₁ represents a hydrogen atom or a methyl group.) The polymerizable monomer for constituting the adhesive material is a combination of a plurality of polymerizable monomers from the viewpoint of adhesiveness to teeth and operability. It is preferable to use, and further in the combination, a phosphoric acid group-containing polymerizable monomer, a polyvalent carboxylic acid group-containing polymerizable monomer, a monocarboxylic acid group-containing polymerizable monomer, a sulfonic acid group-containing polymerizable monomer It is more preferable to include a polymerizable monomer having an acidic group such as a monomer, a polymerizable monomer having an acidic group, a polyfunctional polymerizable monomer, and a water-soluble non-acidic polymerizable monomer. It is more preferable to include both of

Further, among the polymerizable monomers having an acidic group, it is preferable to use a polyvalent carboxylic acid group-containing polymerizable monomer.

As the polymerization catalyst compounded in the adhesive material, known compounds can be used without particular limitation as long as they are compounds which polymerize and cure the adhesive material. As such a polymerization catalyst, a combination may be selected from the polymerization accelerators described in the section of the dental composition so as to satisfy the purpose of polymerization / curing. The combination of polymerization catalysts can be roughly classified into a combination in which polymerization is initiated by mixing (chemical polymerization catalyst) and a combination in which polymerization is initiated by light irradiation (photopolymerization catalyst).

As the combination of chemical polymerization catalysts, organic peroxides / amines, organic peroxides / amines / sulfinic acids, organic peroxides / amines / borates, barbituric acids / quaternary Examples thereof include primary ammonium halides / metal compounds, and sulfinic acids and borates react with a polymerizable monomer having an acidic group to start polymerization, and an organic boron compound is an air or Polymerization can be initiated by reacting with oxygen or water on the tooth surface.

As the combination of the photopolymerization initiators, the compound itself is decomposed by irradiation of light to produce a polymerizable radical species, α-diketones, thioxanthones, α
-Aminoacetophenones, acylphosphine oxide derivatives, and a combination of tertiary amines, barbituric acids, and mercapto compounds that improve the polymerization initiation ability of the compounds, or dyes / photoacid generators / borate And combinations of dyes, dyes / photoacid generators / sulfinic acids, and the like.

Among the above polymerization catalysts, it is preferable to use a photopolymerization catalyst because the adhesive material can be stored in one solution and an arbitrary search margin time can be set. It is possible to polymerize with visible light. It is more preferable to use a different photopolymerization catalyst.

The dental primer of the present invention is generally used as a primer in the method of filling restoration such as primer application to the tooth surface, drying, adhesive application, adhesive curing, filling of filling material, and curing of filling material. To be done. By applying the primer 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 the permeation / diffusion / polymerization of the adhesive applied later is easy. Assuming the mechanism that a strong adhesive layer is formed, the phosphoric acid group-containing polymerizable monomer dissolves the inorganic component due to the acid supply ability of the phosphoric acid group, and further the tooth substance at the phosphoric acid group site. The affinity allows easy penetration into the tooth structure, which is advantageous for forming a penetrating layer of the polymerizable monomer in the tooth structure. 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. At this time, the phosphoric acid group-containing polymerizable monomer needs to have a specific molar ratio because the phosphoric acid monoester [I]
And phosphodiester [II] are presumed to be due to differences in acid supply capacity and dentin affinity of the phosphate group. Perhaps the most preferred dentin affinity for dentin is estimated to be intermediate between the two, and the molar ratio is 1: 0.7-
In the case of the mixture of 1: 1.35, it is considered that the most preferable properties are approached. Furthermore, since the phosphoric acid monoester [I] is too hydrophilic, it facilitates the infiltration of water into the dentin adhesive interface when an adhesion durability test is performed,
As a result, durability deteriorates, and conversely, phosphodiester [I
[I] has relatively low hydrophilicity, so water infiltration is relatively unlikely to occur, and since dentin adhesion durability is high due to its high crosslinkability, demineralization of enamel tends to be insufficient due to poor acid supply capacity. It is presumed that this is because a clear difference appears when performing the adhesion durability test.

[0119]

When the tooth and the filling material are adhered by the adhesive, the primer of the present invention is used for the pretreatment of the tooth surface prior to the adhesive, so that only one pretreatment operation is required. Simplifies the complicated operation of applying both the acid aqueous solution and the primer as a treatment, and 20 MPa for both enamel and dentin with a single pretreatment of the primer only.
It is possible to obtain a material having the above-mentioned high adhesive strength and showing no harm due to whitening of soft tissues in the oral cavity.

[0120]

EXAMPLES The composition of the present invention will be specifically shown by the following examples, but the present invention is not limited to these examples. The abbreviations used in the text and examples
The abbreviations, adhesive strength measurement methods, and adhesive preparation methods are as follows.

(1) Preparation of Phosphoric Acid Group-Containing Polymerizable Monomer The phosphoric acid group-containing polymerizable monomer used in the examples was prepared from the corresponding alcohol and phosphorus oxychloride according to a conventional method. It was synthesized as a mixture of acid diester and other impurities, and purified by solvent extraction / washing, column chromatogram, HPLC fractionation and the like. These were mixed in a predetermined ratio and used as a phosphoric acid group-containing polymerizable monomer. After mixing, HPLC analysis (using column: inert sil ODS2, manufactured by GL Sciences, detection: UV
The composition ratio was confirmed at 210 nm). At this time, the molar extinction coefficient of the polymerizable unsaturated group is phosphoric acid monoester [I]
And phosphodiester [II] was not different.

(2) Abbreviations and abbreviations [Primer constituents] (A) Component PM-C2: Mixture of mono (2-methacryloyloxyethyl) dihydrogen phosphate and bis (2-methacryloyloxyethyl) monohydrogen phosphate. PM-CL: A mixture of mono (1-chloromethyl-2-methacryloyloxyethyl) dihydrogen phosphate and bis (1-chloromethyl-2-methacryloyloxyethyl) monohydrogen phosphate.

PM-O: a mixture of mono {2- (2-methacryloyloxyethoxy) ethyl} dihydrogen phosphate and bis {2- (2-methacryloyloxyethoxy) ethyl} monohydrogen phosphate.

PM-C6: a mixture of mono (6-methacryloyloxyhexyl) dihydrogen phosphate and bis (6-methacryloyloxyhexyl) monohydrogen phosphate.

PM-G: mono {1- (methacryloyloxymethyl) -2-methacryloyloxyethyl}
A mixture of dihydrogen phosphate and bis {1- (methacryloyloxymethyl) -2-methacryloyloxyethyl} monohydrogen phosphate.

Component (B) -MAC-10: 11-methacryloyloxy-1,1
-Undecanedicarboxylic acid-MTS: 2-methacryloyloxyethyl-3'-methacryloyloxy-2 '-(3,4dicarboxybenzoyloxy) propyl succinate-4-META: 4-methacryloyloxyethyl trimellitate anhydride- 4-AET: 4-acryloyloxyethyl trimellitate (D) component: -EtOH: ethyl alcohol-IPA: isopropyl alcohol-DME: 1,2-dimethoxyethane (E) component-3G: triethylene glycol dimethacrylate-TMPT : Trimethylolpropane trimethacrylate (F) component-CQ: camphorquinone-DMBE: ethyl N, N-dimethyl-p-aminobenzoate-NPG: N-phenylglycine-PTSNa: p-toluenesulfinate sodium [Adhesive component] · Bis-GMA: 2,2- bis (4- (2-hydroxy-3-methacryloyloxy) phenyl)
Propane / 3G: Triethylene glycol dimethacrylate / HEMA: 2-hydroxyethyl methacrylate / MAC-10: 11-methacryloyloxy-1,1
-Undecanedicarboxylic acid-PBNa: tetraphenylborate sodium salt-TAZ101: compound represented by the following structural formula

[0127]

[Chemical 25]

NKX653: a compound represented by the following structural formula

[0129]

[Chemical formula 26]

CQ: camphorquinone DMBE: ethyl N, N-dimethyl-p-aminobenzoate (3) enamel, dentin adhesive strength The bovine anterior teeth were removed within 24 hours after slaughter and injected with water. 80
The enamel or dentin plane was carved out so as to be parallel to the labial surface with 0 water-resistant abrasive paper. Next, blow compressed air on these surfaces for about 10 seconds to dry them, then
Fix the double-sided tape with a hole of mm, then the thickness 1.5
Paraffin wax having a hole of 6 mm in diameter and 6 mm in diameter was fixed on the circular hole so as to have the same center to form a simulated cavity. The primer of the present invention prepared immediately before use was thinly applied to 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.

After the above adhesion test piece was immersed in water at 37 ° C. for 24 hours, a crosshead speed of 10 mm / min was obtained using a tensile tester (Autograph, Shimadzu Corp.).
And the tensile adhesive strength between the tooth and the composite resin was measured.

[0132] The tensile adhesion strength of four pieces per test was measured by the above method, and the average value was taken as the adhesion strength.

The adhesive strength is required to be 20 MPa or more for both enamel and dentin in order to prevent the formation of a gap between the filling material and the surface of the tooth and the dropping of the filling material.

(4) Adhesion durability Adhesion test pieces were prepared in the same manner as the above-mentioned measurement of adhesion strength,
After being immersed in 37 ° C. water for 24 hours, they were alternately immersed in 4 ° C. and 60 ° C. water for 1 minute each 3000 times. afterwards,
A tensile tester (Autograph, manufactured by Shimadzu Corporation) was used to pull at a crosshead speed of 10 mm / min, and the tensile bond strength between the tooth and the composite resin was measured.

[0135] The tensile adhesion strength of four pieces per test was measured by the above-mentioned method, and the average value was taken as the adhesion strength after endurance.
The smaller this value is compared to the initial value, the better the adhesion durability.

(5) Marginal sealing The bovine anterior teeth were removed within 24 hours after slaughter, and under water injection, # 80.
An enamel plane was carved out so as to be parallel to the lip surface with a water-resistant abrasive paper of 0. Next, while pouring water, using a carborundum point (HP35, manufactured by Shofu Co., Ltd.), the internal system was 4.5 mm to 5 mm.
A cavity having a size of 4 mm and a depth of 4 mm to 5 mm reaching the dentin was formed. The primer of the present invention was thinly applied in the 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. On top of that, a dental composite resin [Palfique Esterite Co., Ltd.
Tokuyama] and light was irradiated for 30 seconds with a visible light irradiator to prepare a marginal blocking test piece.

The above adhesion test piece was immersed in water at 37 ° C. for 24 hours, and then, while pouring water, it was polished with # 800 water-resistant abrasive paper to remove excess composite resin, and the root part was immediately polymerized with resin. Sour Cure Fast, manufactured by Tokuyama Corp.]. Alternate this to a 4 ° C and 60 ° C aqueous dye solution (0.1% basic fuchsin, manufactured by Tokyo Kasei),
The immersion was repeated 60 times for 1 minute each. After the completion of the immersion, the test piece was ground with # 120 water-resistant abrasive paper so that the cross section from the cervical direction to the crown direction could be seen, and the state of penetration of the dye into the interface between the tooth substance and the filled composite resin was examined. It 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.

(6) Storage stability A primer is prepared by dividing it into two solutions, a primer A and a primer B, and mixed at a predetermined ratio at the time of use.
After storage for a week, the enamel and dentin bond strength was measured by the above method. The adhesive strength immediately after the adjustment (in the table, initial tensile adhesive strength) and the adhesive strength after storage (in the table, tensile adhesive strength after storage) were compared to evaluate the storage stability.

(7) Gingival whitening test A small amount of the adjusted primer was applied to the gingiva of a healthy adult male, and after 20 seconds, it was visually observed whether or not whitening occurred in the gingiva. The case where whitening did not occur was rated as "○", and the case where whitening occurred was rated as "x".

(8) Preparation of Adhesives Adhesives A and B were obtained as a viscous liquid by mixing and agitating under the shade with the following compositions. Adhesive C is a bonding agent attached to Tokuso MacBond [Tokuyama Corporation] which is a commercially available adhesive, Adhesive D is a bonding agent attached to Clearfill Liner Bond 2 (Kuraray Co.), and Adhesive E is Multipurpose (3
Adhesive attached to M company) was used as it was.

[0141] Example 1 1. of PM-C2 prepared to have a molar ratio of 0.72.
6 g and 0.8 g of MAC-10 were dissolved in 3.1 g of ethanol, and this was mixed with 4.5 g of water and used as a primer, and using adhesive A, dentin and enamel bond strength,
The adhesion durability and the presence or absence of whitening of the gingiva were evaluated. The results are shown in Table 1.

Examples 2 to 7 Evaluations were carried out according to the method of Example 1 except that the PM-C2 used was changed to the one having the molar ratio shown in Table 1. The results are shown in Table 1.

Comparative Examples 1 to 4 Evaluations were carried out according to the method of Example 1 except that the used PM-C2 had a molar ratio shown in Table 1. The results are shown in Table 1.

[0144]

[Table 1]

Examples 1 to 7 are PM-C which is the component (A).
It is a result when changing the composition ratio of 2 within the range of the present invention. In all cases, good initial tensile bond strength was exhibited.
Regarding the adhesion durability, in Example 1 where the molar ratio is close to the lower limit, dentin durability tends to be low, and in Example 7 where the molar ratio is close to the upper limit, enamel durability tends to be low. Indicated. On the other hand, Comparative Examples 1 and 2 show the results when the molar ratio is smaller than the range of the present invention. Although the adhesiveness to enamel is good, the initial tensile adhesive strength to dentin is low and its durability is also good. There wasn't. Comparative Examples 3 and 4
On the contrary, the results are obtained when the molar ratio is larger than the range of the present invention. At this time, both the enamel and the dentin had a small initial tensile adhesion and the enamel adhesion durability was remarkably poor. No whitening of the gingiva was observed in any of the primers using PM-C2 as the component (A).

Examples 8 to 15 According to the method of Example 1, a primer having the composition shown in Table 2 was prepared and evaluated using the adhesive material A. The PM-C2 used at this time had a molar ratio of 1.08. The composition of the primer and the results are shown in Table 2.

Comparative Examples 5 to 9 According to the method of Example 1, primers having the compositions shown in Table 2 were prepared and evaluated using the adhesive material A. The PM-C2 used at this time had a molar ratio of 1.08. The composition of the primer and the results are shown in Table 2.

[0148]

[Table 2]

Examples 8 to 15 are the components (A) and (B) constituting the dental composition used as a primer,
It is a result when changing the compounding ratio of (C) component and (D) component. In all cases, good adhesive strength was shown for both dentin and enamel. Comparative Example 5 is the result when the component (A) was not included, and both dentin and enamel had low adhesive strength. Comparative Example 6 shows the results when the component (B) was not included. In this case, although the adhesive strength to enamel was good, the adhesive strength to dentin was insufficient. In Comparative Example 7, the component (A) is within the range of the present invention, in Comparative Example 8 the component (B) is within the range of the present invention, and in Comparative Example 9, the component (C) is within the range of the present invention. As a result, the adhesive strength to both dentin and enamel was low in all cases.

Examples 16 to 23 According to the method of Example 1, primers having the compositions shown in Table 3 were prepared and evaluated using the adhesives B, C, D and E. The PM-C2 used at this time had a molar ratio of 1.08. Table 3 shows the composition of the primer, the adhesive used, and the results.

[0151]

[Table 3]

Examples 16 to 23 show the results when the composition of the dental composition used as the primer was changed and the adhesive used was changed. In any case, good adhesive strength is exhibited, and it can be seen that no adhesive is selected when the primer of the present invention is used.

Examples 24 to 30 According to the method of Example 1, a primer having the composition shown in Table 4 was prepared, and the adhesive B was used for evaluation. The PM-C2 used at this time had a molar ratio of 1.03. The composition of the primer and the results are shown in Table 4.

[0154]

[Table 4]

Examples 24 to 30 are results when the kinds of the component (B) and the component (D) used were changed. The comparison between Examples 24 to 26 and the comparison between Examples 27 and 28 are representative of the results when the type of component (D) used is changed, and Example 2
The comparison of 7, 29 and 30 and the comparison of Examples 26 and 28 are representative of the results when the component (B) used is changed.
In all cases, good adhesive strength was exhibited for both dentin and enamel.

Examples 31 to 34 Using PM-Cl in various molar ratios as the component (A), a primer was prepared according to the method of Example 1, and the adhesive B was used for evaluation. Table 5 shows the PM-Cl molar ratio used and the results.

Comparative Examples 10 and 11 Using PM-Cl in various molar ratios as the component (A), a primer was prepared according to the method of Example 1, and the adhesive B was used for evaluation. Table 5 shows the PM-Cl molar ratio used and the results.

[0158]

[Table 5]

Examples 31 to 34 and Comparative Examples 10 and 11 are the results when the component (A) used was PM-Cl and the molar ratio was changed. Within the scope of the present invention, good initial bond strength and bond durability were exhibited for both dentin and enamel. On the other hand, Comparative Example 10 shows the results when the molar ratio was smaller than the range of the present invention. Although the adhesiveness to enamel was good, the initial tensile adhesive strength to dentin was low and its durability was also poor. . On the contrary, Comparative Example 11 is the result when the molar ratio is larger than the range of the present invention. At this time, both the enamel and the dentin show small initial tensile adhesion, and the enamel adhesion durability is remarkably poor. It was No whitening of the gingiva was observed in any of the primers using PM-C1 as the component (A).

Examples 35 to 40 According to the method of Example 1, a primer having the composition shown in Table 6 was prepared, and the adhesive B was used for evaluation. Table 6 shows the composition of the primer used, the molar ratio of the component (A), and the result.

[0161]

[Table 6]

Examples 35 to 40 and Comparative Example 12 are the results when the kind of the component (A) blended in the dental composition used as a primer was changed. In each of the examples, good adhesive strength was shown for both dentin and enamel.
Comparative Example 12 shows the results when the molar ratio of the component (A) is smaller than the range of the present invention. The adhesive strength to enamel was good, but the adhesive strength to dentin was low.

Example 41 1. of PM-C2 prepared to have a molar ratio of 1.13.
4 g and 0.8 g of MAC-10 were dissolved in 2.5 g of acetone (primer A solution). This was mixed with a primer B solution prepared by mixing 1.0 g of IPA and 4.5 g of water at a ratio shown in Table 7 to prepare a primer, the tooth surface was treated, and the ivory was prepared using the adhesive material B. The quality, enamel bond strength, and edge sealability were evaluated. The results are shown in Table 7.

Examples 42 to 48 Primers were prepared according to the method of Example 41 and evaluated using the adhesive material B. Composition of the primer used,
And the results are shown in Table 7.

Comparative Examples 13 and 14 A primer was prepared according to the method of Example 41, and the adhesive B was used for evaluation. Composition of the primer used,
And the results are shown in Table 7.

[0166]

[Table 7]

Examples 41 to 48 are those for evaluating the marginal sealing property when the primer of the present invention is used.
Compared to Comparative Example 13 containing no component (A) and Comparative Example 14 containing no component (C), Examples 41 to 48 within the scope of the present invention clearly show good results. Furthermore, Examples 42 and 47 in which the (E) polyfunctional polymerizable monomer is blended show better marginal blocking properties as compared with Examples 41 and 46 in which it is not blended, and Examples 43 to 45 and 48 in which (F) the polymerization accelerator is blended show a better edge blocking property.

Examples 49 to 51 With the composition shown in Table 8, a primer A solution and a primer B solution were prepared, and the adhesive stability was used to evaluate the storage stability. The results are shown in Table 8.

[0169]

[Table 8]

Examples 49 to 51 are results of evaluating storage stability by preparing primers having different compositions using a linear ether compound having no hydroxyl group as the component (D). In each case, good adhesive strength was obtained both at the initial stage and after storage, and the storage stability was good.

Continuation of front page (56) References JP-A-8-319209 (JP, A) JP-A-7-82115 (JP, A) JP-A-6-256131 (JP, A) JP-A-62-149707 (JP , A) JP-A-4-8368 (JP, A) JP-A-8-99815 (JP, A) JP-A-6-56618 (JP, A) JP-A-6-40838 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) A61K 6/00

Claims (5)

(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, 0.5 to 50 parts by weight of the component (A) and 1 to 50 parts by weight of the component (B) based on 100 parts by weight of the total of (A), (B) and (C). , (C) component is 5
Accounts for 90 parts by weight, (A) component consists of a mixture of the compounds represented by the following general formula [I] and [II], and the mixing ratio of [I] and [II] is 1: 0.7 0 1: 1.3
A dental primer having a 5 molar ratio. [Chemical 1] (In the formula, R ₁ , R ₂ , and R ₃ are each independently an organic group having a polymerizable unsaturated group, Z is an oxygen atom or a sulfur atom, X ₁ , X ₂ , and X ₃ are each independently an OH group , Halogen
And a phosphoryloxy group or an acyloxy group . ) 2. A polymerizable group-containing monomer (A),
(B) polyvalent carboxylic acid group-containing polymerizable monomer, (C) water,
And (D) a water-soluble organic solvent as a main component,
0.5 to 50 parts by weight of the component (A), 1 to 50 parts by weight of the component (B), and (C) based on 100 parts by weight of the total of (A), (B), (C) and (D). ) 5 to 90 parts by weight of the components,
The component (D) occupies 1 to 80 parts by weight, the component (A) comprises a mixture of compounds represented by the following general formulas [I] and [II], and the mixing ratio of [I] and [II] is: 1: 0.7 0 ~
A dental primer having a molar ratio of 1: 1.35. [Chemical 2] (In the formula, R ₁ , R ₂ , and R ₃ are each independently an organic group having a polymerizable unsaturated group, Z is an oxygen atom or a sulfur atom, X ₁ , X ₂ , and X ₃ are each independently an OH group , Halogen
And a phosphoryloxy group or an acyloxy group . ) 3. A dental primer further comprising 0.1 to 30 parts by weight of (E) a polyfunctional polymerizable monomer based on 100 parts by weight of the dental primer according to claim 1. 4. The (F) polymerization accelerator is added in an amount of 0.001 to 100 parts by weight of the dental primer according to claim 1 or 2.
A dental primer that is further compounded at 30 parts by weight. 5. 100 parts by weight of the dental primer according to claim 1, 0.1 to 30 parts by weight of (E) a polyfunctional polymerizable monomer, and (F) a polymerization accelerator of 0.1 part by weight. 001-
A dental primer that is further compounded at 30 parts by weight.