JPH10251115A - Dental primer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a dental primer capable of providing both an enamel and a dentin with high bond strength without carrying out pretreatment with an aqueous solution of an acid, by using a mixture of a phosphoric acid monoester of a specific structure and a phosphoric acid diester as a phosphate group- containing polymerizable monomer. SOLUTION: This dental primer comprises (A) 0.5-50 pts.wt., based on 100 pts.wt. of the total, of the components A to C of a phosphate group-containing polymerizable monomer, (B) 1-50 pts.wt. of a polyfunctional carboxylic acid group-containing polymerizable monomer and (C) 5-90 pts.wt. of water as main components. The component A is composed of a mixture of a compound of formula I and a compound of formula II (R1 to R3 are each a polymerizable unsaturated group-containing organic group; Z is 0 or S; X1 to X3 are each OH or a group to form an OH group by reaction with water) in the blending ration of the compounds of formula I and formula II of 1:0.75 to 1:35 by molar ratio.

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 a tooth surface to realize a high adhesive strength between a filling material and a tooth material when restoring a 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 restoring a tooth damaged by caries or the like. However, since the composite resin itself does not have adhesiveness, it has been conventionally used an acid aqueous solution on the tooth surface. After treatment, washing and drying, followed by application and drying of a primer, the dentin and the composite resin were adhered using an adhesive. However, such operations of treatment with an acid aqueous solution, treatment with a primer, and application of an adhesive are complicated and time-consuming, so that a burden is placed on the dentist and patient as an operator, and there is a possibility that an operation error may be made. Not a few.

[0003] In recent years, attempts have been made to omit the treatment and washing with an acid aqueous solution and to obtain a high adhesive strength to tooth material only with a primer. For example, A just before use
・ Mix a primer consisting of two liquids of B and apply it to the tooth surface
Several simplified systems of drying and subsequent application and light curing of adhesives have been provided, but these systems include primers that adhere to soft tissues such as the gingiva in the oral cavity. Conventional acid solution treatment / primer treatment /
There are problems that have not been observed with systems consisting of adhesive application.

As a system comprising a primer and an adhesive, Japanese Patent Application Laid-Open No. 8-319209 discloses a primer using a polymerizable monomer containing a phosphate group and a polymerizable monomer containing a polycarboxylic acid group in combination. Thus, high adhesive strength is obtained by using 2-methacryloyloxyethyl phenyl phosphate (hereinafter, referred to as phenyl-P) as a phosphoric acid group-containing polymerizable monomer. However, this phenyl-P substance significantly whitens the soft tissue in the oral cavity, so that the use of this substance as a component of the primer causes the same problem as described above. On the other hand, when 2-methacryloyloxyethyl dihydrogen phosphate or bis (2-methacryloyloxyethyl) hydrogen phosphate is used, whitening of the oral soft tissue is unlikely to occur, but the adhesive strength to dentin is 15 to 50%. 18MPa
And inferior to phenyl-P. In recent years, in order to obtain high reliability, the demand for bonding strength to dentin has been increasing, and a pressure of 20 MPa or more has been required. However, 2-methacryloyloxyethyl dihydrogen phosphate or bis (2 -Methacryloyloxyethyl) When hydrogen phosphate is used, there is a concern that the bonding strength is insufficient.

[0005] Inoue et al. 2-acryloyloxyethyl
A primer using hydrogen malate (hereinafter referred to as 2AEM) has been proposed (40th JADR).
General Meeting and the 24th and 25th Annual Meeting of the Japanese Society of Dental Science and Technology)
The 2AEM also whitens soft tissue and requires a long processing time of 60 seconds. Japanese Patent Application Laid-Open No. 6-24928 discloses a primer containing a metal salt and a polymerizable monomer having an acidic group. This primer uses an adhesive having a trialkylborane as a polymerization initiator. It is necessary to mix a polymerization initiator and a polymerizable monomer immediately before use, and the pot life is relatively short. is there.

[0006]

In view of the above, the complicated operation of applying both the acid aqueous solution and the primer as the pretreatment in the cavity repair technique of pretreatment, adhesive application and restoration material filling is simplified. It is desired to develop a material that gives a high adhesive strength of 20 MPa or more to both enamel and dentin in a single pretreatment of only the primer and does not show harm to the soft tissue in the oral cavity due to whitening etc. I was

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to overcome the above technical problems, and as a result, have found that a polymerizable monomer containing a phosphoric acid group and a polymerizable monomer containing a polycarboxylic acid group are obtained. In a composition containing water as a main effect component, a mixture of a phosphoric acid monoester and a phosphoric acid diester having a specific structure having a specific structure as a phosphoric acid group-containing polymerizable monomer is used to prepare an acid aqueous solution. It has been found that a dental primer which gives a high adhesive strength of not less than 20 MPa to both enamel and dentin without treatment and which hardly causes whitening of oral soft tissues is obtained.

That is, the present invention provides (A) a phosphoric acid group-containing polymerizable monomer, (B) a polyvalent carboxylic acid group-containing polymerizable monomer,
And (C) water as a main component, and the component (A) is 0.1% based on a total of 100 parts by weight of (A), (B) and (C).
5 to 50 parts by weight, component (B) 1 to 50 parts by weight, (C)
The component occupies 5 to 90 parts by weight, the component (A) is a mixture of compounds represented by the following general formulas [I] and [II], and the mixing ratio of [I] and [II] is 1: 0. .75-1: 1.3
A dental primer characterized in that the molar ratio is 5 mol.

[0009]

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(Wherein 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 groups or groups which react with water to generate OH groups.) Other inventions include (A) a phosphoric acid group-containing polymerizable monomer, (B)
A polycarboxylic acid group-containing polymerizable monomer, (C) water, and (D) a water-soluble organic solvent as main components;
Component (A) is 0.5 to 50 parts by weight and component (B) is 1 to 100 parts by weight in total of (B), (C) and (D).
５０50 parts by weight, component (C) occupies 5 to 90 parts by weight, component (D) occupies 1 to 80 parts by weight, and component (A) is a compound represented by the following general formulas [I] and [II]. It consists of a mixture, and the mixing ratio of [I] and [II] is 1: 0.75 to 1: 1.3.
A dental primer characterized in that the molar ratio is 5 mol.

[0011]

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(Wherein, 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 It is an OH group or a group which reacts with water to generate an OH group.) (A) The phosphoric acid group-containing polymerizable monomer used in the present invention includes:
A phosphate monoester represented by the above general formula [I] (hereinafter abbreviated as phosphate monoester [I]);
It is not particularly limited as long as it is a compound having a specific ratio with the phosphoric diester represented by the formula (I) (hereinafter abbreviated as phosphoric diester [II]) and each satisfying the above structure.

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

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, and —X in the structure of ＝ P (Z) —OR. OR group (however,
R represents any of R ₁ , R ₂ and R ₃ )
It is a group that can be converted into an H group, and specifically, it is a halogen atom, a phosphoryloxy group, an acyloxy group, or the like.

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

[0016]

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(Wherein R ₁ , R ₂ and R ₃ are as described above.
R ₄ , R ₅ , and R ₆ are each independently the same organic group as R ₁ , R ₂ , or R ₃ , or an organic group having 15 or less carbon atoms having and / or not having a polymerizable unsaturated group. Among the compounds listed in the above general formula, monoester phosphate [I] in consideration of the ease of synthesis or availability, and the stability and adhesion during storage when prepared as a dental composition, etc.
Of the compounds represented by the general formulas (1) and (2) and the compound represented by the general formula (4), it is more preferable to use a compound in which R ₁ and R ₄ are the same. The use of the compounds of formula (I) is most preferred. Similarly, among the compounds represented by the general formulas (6) and (7) and the compound represented by the general formula (9), the phosphoric diester [II] includes R ₂ and R ₄ , and R ₃ It is preferable to use a compound in which R ₅ is the same, and it is most preferable to use a compound represented by the general formula (6).

In the 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 may be any known organic group without any particular limitation.

The polymerizable unsaturated group possessed by R ₁ , R ₂ and R ₃ is not particularly limited as long as it is an unsaturated group capable of being polymerized by a radical. Specific examples include a (meth) acryloyloxy group, a (meth) acryloylamino group, a (meth) acryloylthio group, a thio (meth) acryloyloxy group, a styryl group, and an allyl group. Among these polymerizable unsaturated groups, a (meth) acryloyloxy group or a (meth) acryloyl group is preferred because of good polymerizability, relatively low harm to living organisms, and relatively easy synthesis. An amino group is preferred, and a (meth) acryloyloxy group is most preferred.

As for the part of the organic group other than the polymerizable unsaturated group, a known divalent organic residue can be used, and the organic residue has an ether bond, an ester bond, or an aromatic bond in its structure. It may have a ring or the like, and may further have a side chain, but is preferably an organic residue having 1 to 20 carbon atoms from the viewpoint of ease of synthesis and ease of 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 organic residues are as follows.

[0022]

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

[0024]

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[0025]

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

[0027]

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[0028]

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[0029]

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[0030]

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(In the formula, R ₉ and R ₁₀ each independently represent a hydrogen atom or a methyl group.) Among the above-mentioned phosphoric diesters [II], 2 is preferred because of the ease of synthesis and the ease of adjusting the 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 phosphate monoester [I] and phosphate diester [II] are mixed in two or more kinds, and a mixture of three or more phosphate esters (A ) It can be used as a phosphoric acid group-containing polymerizable monomer component, but due to the ease of synthesis and the ease of adjusting the molar ratio, both the phosphoric acid monoester [I] and the phosphoric acid diester [II] are used. The use of a mixture comprising a single compound is preferred, and one organic group of the phosphate monoester (R ₁ in the general formula [I]) and two organic groups of the phosphate diester [II] (the general formula [II] I
It is more preferable to use a mixture of compounds in which R ₂ and R ₃ ) in I] are all the same as the component (A).

The (A) phosphoric acid group-containing polymerizable monomer of the present invention comprises a phosphoric acid monoester [I] and a phosphoric 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 1: 1.35.
A mixture of 1: 1.30, most preferably a mixture having a molar ratio of 1: 0.80 to 1: 1.25. When the molar ratio of the phosphoric acid diester [II] is smaller than 0.70, the dentin adhesive strength decreases, and the adhesive durability also deteriorates.
Conversely, if the molar ratio of the phosphoric diester [II] is greater than 1.35, the bond strength of both dentin and enamel decreases,
Furthermore, the adhesion durability to enamel also deteriorates.

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

In the present invention, the compounding amount of (A) the phosphoric acid group-containing polymerizable monomer is determined based on the amount of component (A) constituting the composition,
With respect to the total of 100 parts by weight of the component (B), the component (C), and the component including the component (D) blended as necessary (hereinafter referred to as a total of 100 parts by weight of the main component), the amount of 0.1% is added. 5-5
0 parts by weight, preferably 5 to 50 parts by weight, more preferably 7 to 40 parts by weight. If the amount is less than 0.5 parts by weight, the adhesive strength to both dentin and enamel, especially to the enamel, will be reduced. Conversely, if the amount exceeds 50 parts by weight, both dentin and enamel, especially dentin Adhesive strength to the adhesive decreases.

The polycarboxylic acid group-containing polymerizable monomer (B) of the present invention has a plurality of carboxyl groups in one molecule or easily reacts with water which is an essential component of the present invention to have a plurality of carboxyl groups. It is a polymerizable monomer having an acid derivative group such as an acid anhydride or an acid halide which can be generated and having at least one polymerizable unsaturated group.

As such a compound, the following general formula (1)
Trimellitic acid derivative represented by 1) and their anhydrides or halides, pyromellitic acid derivative represented by the following general formula (11) or (12) and their anhydrides or halides, Malonic acid derivatives represented by the formula (13) and anhydrides or halides thereof, 6- (meth) acryloxyethylnaphthalene-1,2,6-tricarboxylic acid, N- (meth) acryloyl aspartic acid, and the like. Can be

[0038]

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(Wherein, R ₉ represents a hydrogen atom or a methyl group, and R ₁₁ represents a divalent to hexavalent 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, n ₁ represents an integer of ₁ to 5, and n ₂ represents 1 or 2. Preferred specific examples of the polyvalent carboxylic acid group-containing polymerizable monomer represented by the general formula (11) are as follows.

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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

[0046]

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

[0048]

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[0049]

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

These polyvalent carboxylic acid group-containing polymerizable monomers can be used in combination as necessary.

The compounding amount of the polycarboxylic acid group-containing polymerizable monomer (B) in the present invention accounts for 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.
Occupies part by weight. When the amount is less than 1 part by weight, the adhesive strength to dentin decreases, and when the amount exceeds 50 parts by weight, the adhesive strength to both dentin and enamel decreases.

The above components (A) and (B) are summed up
It preferably accounts for at least 10 parts by weight of the total 100 parts by weight of the main components, and more preferably at least 15 parts by weight.

The water (C) used in the present invention is necessary for decalcification of hydroxyapatite in tooth material. This water preferably does not substantially contain impurities harmful to storage stability, biocompatibility and adhesiveness, and examples include deionized water and distilled water. The amount of the water (C) in the present invention is 5 to 90 parts by weight based on 100 parts by weight of the total of the main components,
Preferably, it occupies 20 to 80 parts by weight. If the amount is less than 5 parts by weight, the demineralization of the dentin becomes insufficient, so that the adhesive strength of the enamel is insufficient and the adhesive strength to the dentin is insufficient. 9
If the amount exceeds 0 parts by weight, the adhesive strength of both dentin and enamel decreases.

The (D) water-soluble organic solvent 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) ) Improving the solubility of various polymerizable monomers such as polyfunctional polymerizable monomers and (F) a polymerization accelerator in water, dissolving each component to a uniform solution, or to the extent that there is no problem in use. It is preferable to blend the emulsion in order to obtain a stable emulsion 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, 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-isopropoxyethanol, 2-butoxyethanol, 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; Having a hydroxyl group such as 2,2-dimethoxyethane, 1,2-diethoxyethane, bis (2-methoxyethyl) ether and bis (2-ethoxyethyl) ether; 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 and sulfur oxide compounds such as dimethyl sulfoxide and sulfolane.

Among these water-soluble organic solvents, use of ethanol, propanol or acetone is preferred from the viewpoint of harmful effects on the living body, and hydroxyl groups are preferred from the viewpoint of storage stability of the dental composition and tooth adhesion. The use of unbranched linear ether compounds or ketones is preferred.

A plurality of the above water-soluble organic solvents can be used as a mixture, if necessary.

The amount of the water-soluble organic solvent (D) in the present invention accounts for 1 to 80 parts by weight, more preferably 5 to 70 parts by weight, particularly preferably 10 to 50 parts by weight, per 100 parts by weight of the main component. If the amount is less than 1 part by weight, the effect of dispersing and dissolving (A) the polymerizable monomer containing a phosphate group or (B) the polymerizable monomer containing a polycarboxylic acid group in water tends to be insufficient. If it exceeds 80 parts by weight, the adhesive strength of both dentin and enamel tends to decrease.

The dental composition of the present invention preferably further contains (E) a polyfunctional polymerizable monomer. By blending the polyfunctional polymerizable monomer, the margin sealing property is improved.

The (E) polyfunctional polymerizable monomer of the present invention comprises:
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 compounds 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-methacryloyloxyethoxyethoxyphenyl) -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 difunctional 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-methylenebismethacrylamide and their acrylates, trimethylol Trifunctional monomers such as pantrimethacrylate, trimethylolethanetrimethacrylate, trimethylolpropanetrimethacrylate, tri (2-methacryloyloxyethyl) phosphate and acrylates thereof, and pentaerythritol tetramethacrylate and pentaerythritol tetraacrylate Functional monomers and the like.

Among the above-mentioned polyfunctional polymerizable monomers, the use of an aliphatic difunctional monomer or a tri- or tetra-functional monomer is preferable in consideration of the effect of improving marginal sealing. Further, in consideration of harmful effects on living bodies 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.

These polyfunctional polymerizable monomers can be used as a mixture of two or more if necessary.

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

It is preferable that the dental composition of the present invention further contains (F) a polymerization accelerator for further improving the adhesiveness to the tooth substance, and particularly for improving the marginal sealing property. By adding a polymerization accelerator, it becomes possible to increase the polymerization rate at the interface between the tooth material and the adhesive material or to start the polymerization reaction from the interface.

In the present invention, a substance capable of initiating polymerization by itself (hereinafter referred to as a polymerization initiator) does not have the ability to initiate polymerization by itself, but can be used in combination with a polymerization initiator. A substance that improves the polymerization initiation ability of a polymerization initiator and a substance that has little ability to initiate polymerization by itself but initiates polymerization when a plurality thereof are combined are collectively referred to as a polymerization accelerator.

In the present invention, the term “polymerization” (and the related polymerization rate, polymerization reaction, and the like) also refers to radical polymerization.

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

The above-mentioned organic peroxide is exemplified as a specific example.
t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, acetyl peroxide, lauroyl peroxide, benzoyl peroxide and the like.

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

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

Examples of the above borates include aryl borate compounds having three or four aryl groups in one molecule. Specifically, borate compounds having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) boron, monoalkyl Tri (3,5-bistrifluoromethyl) phenylboron, monoalkyltri [3,5
-Bis (1,1,1,3,3,3-hexafluoro-2-
Methoxy-2-propyl) phenyl] boron (alkyl group is n-butyl group, n-octyl group, n-dodecyl group, etc.) sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium Salts, tetraethylammonium salts, methylpyridinium salts, ethylpyridinium salts, butylpyridinium salts, methylquinolinium salts, ethylquinolinium salts, butylquinolinium salts, and the like.
Aryl borate compounds having two aryl groups 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, Butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt and the like.

Among the above-mentioned aryl borates, tetraaryl borates in which four 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 in which an amino group is 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 compounds such as N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, and 2,2 ′-(n-butylimino) diethanol 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, and 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 as α-aminoacetophenones are 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2
6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like are mentioned as acylphosphine oxides.

Specific examples of barbituric acids include:
5-butyl barbituric acid, 1-ethyl-5-methyl barbituric acid, 1-hexyl-5-ethyl barbituric acid, 1-benzyl-5-phenyl barbituric acid, etc., dodecyl mercaptan, penta Erythritol tetrakis (thioglycolate) and the like are mentioned as mercapto compounds.

As the quaternary ammonium halide, use of chloride is preferred in view of its polymerization promoting ability.
Specific examples include dilauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride, tetrabutyl ammonium chloride, trioctyl ammonium chloride and the like.

Examples of the pigments include coumarin-based pigments. Particularly preferred coumarin dyes include 400-5
What has the maximum absorption wavelength in the visible light region of 00 nm,
High sensitivity to irradiators commonly used for dental applications.

Specific examples of typical coumarin dyes include 3-thienoylcoumarin, 3- (4-methoxybenzoyl) coumarin, 3-benzoylcoumarin, and 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,
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 photoacid generator, any known photoacid generators can be used as long as they generate a Bronsted acid or a Lewis acid upon irradiation with light. Particularly, a halomethyl group-substituted -s-triazine derivative or a diphenyliodonium derivative can be used. When the salt compound is used in combination with the coumarin dye and the sulfinates and / or borates, the energy transfer is performed with the coumarin dye and the acid is generated efficiently under irradiation with visible light, and the sulfinic acids and / or borates are generated. The efficiency of generating radicals in the class is high.

The following are specific examples of typical halomethyl-substituted -s-triazine derivatives: 2,4,6-tris (trichloromethyl) -s-triazine and 2,4,6-triazine.
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-
(Trimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine and the like.

Further, specific examples of the diphenyliodonium salt compound are as follows: diphenyliodonium, bis (p-chlorophenyl) iodonium, ditolyliodonium, bis (p-tert-butylphenyl) iodonium, bis (m-nitrophenyl) Iodonium, p
Chlorides such as -tert-butylphenylphenyliodonium, methoxyphenylphenyliodonium, p-octyloxyphenylphenyliodonium, bromide, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, trifluoromethanesulfonate salt In particular, from the viewpoint of the solubility of the compound, a salt of tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate or trifluoromethanesulfonate is preferably used.

Examples of the organic boron type polymerization accelerator include triphenyl borane, tributyl borane, and tributyl borane partial oxide.

Examples of the transition metal compounds include transition salts of transition metals such as iron, cobalt, nickel, copper, zinc, titanium, zirconium, and cerium, hydrochloride, hydrofluoride, sulfate, nitrate, phosphate, acetate, and the like. Citrate, oxalate, EDTA
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 amount of these polymerization initiators is 10
0.001 to 30 parts by weight with respect to 0 parts by weight is preferable,
The amount is more preferably 0.05 to 10 parts by weight, and most preferably 0.1 to 5 parts by weight. When the amount is too small, the improvement of the adhesiveness is not often observed, and when the amount is too large, the adhesive strength may be undesirably reduced.

These polymerization accelerators are used alone or in combination of two or more in the dental composition of the present invention. When a plurality is combined, there is no particular limitation, and any combination can be used. Examples of preferred combinations include hydrogen peroxide / transition metal compounds, organic peroxides / amines, and organic peroxides. Combinations that start polymerization by mixing, such as compounds / amines / sulfinic acids, organic peroxides / amines / borates, barbituric acids / quaternary ammonium halides / copper compounds, and the compounds themselves Are decomposed with light irradiation to produce polymerizable radical species α-diketones, thioxanthones,
a combination of α-aminoacetophenones, acylphosphine oxide derivatives, and tertiary amines, barbituric acids, mercapto compounds for improving the polymerization initiation ability of the compound, or dyes / photoacid generators / Examples include combinations in which polymerization is initiated by light irradiation of borates, dyes / photoacid generators / sulfinic acids. When the above-mentioned polymerization accelerator is blended, it is necessary to determine the packaging state in consideration of the combination itself and the storage stability when combined with other blended components.

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

Examples of such optional components include polymerizable monomers containing a monocarboxylic acid group, polymerizable monomers containing a sulfonic acid group, and polymerizable monomers containing an acidic group such as a polymerizable monomer containing a phosphonic acid group. And a non-acidic monofunctional polymerizable monomer, a water-insoluble organic solvent, 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; Addition of an acidic monofunctional polymerizable monomer may further improve tooth adhesion.

Examples of the polymerizable monomer having a monocarboxylic acid group include (meth) acrylic acid, 2- (meth) acryloyloxyethyl hydrogen malate, 2- (meth) acryloyloxyethyl hydrogen succinate, and 2- (meth) acryloyloxyethyl hydrogen succinate. (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. Examples of the sulfonic acid group-containing polymerizable monomer include:
2- (meth) acrylamido-2-methylpropanesulfonic acid, 3- (meth) acryloyloxypropanesulfonic acid, N- (meth) acryloylsulfanilic acid and the like are vinyl phosphonic acid as the phosphonic acid group-containing polymerizable monomer. And the like.

The non-acidic monofunctional polymerizable monomer can be classified into a water-soluble monomer and a non-water-soluble monomer. In many cases, the use of the body improves the tooth adhesion.

Specific examples of such non-acidic monofunctional polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate,
Examples of water-insoluble, non-acidic monofunctional polymerizable monomers such as 2-ethylhexyl (meth) acrylate include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, and 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) acrylates of polyhydric alcohols such as acrylates or polyethylene glycols,
Amino alcohol (meth) acrylamides such as N-methylol methacrylamide and N-methylol acrylamide, diacetone (meth) acrylamide, N-
(Meth) acryloylmorpholine and the like are mentioned as water-soluble non-acidic monofunctional polymerizable monomers.

The non-water-soluble organic solvent is used in combination with the water-soluble organic solvent to dissolve the above-mentioned various polymerizable monomers, whereby the storage stability of the dental primer of the present invention can be improved. It may be. Examples of 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, Butyl acetate, vinyl acetate, diethyl ether and the like.

The viscosity and fluidity of the dental primer can be adjusted by adding inorganic or organic fine particles.

Specific examples of such fine particles include polyethylene, polypropylene, polymethyl methacrylate, polyamides, polyesters, polystyrenes, and the like.
Polymer fine particles such as silicones, single or composite oxides of metals such as silicon, aluminum, titanium, zirconium, nickel, cobalt, strontium, iron, copper, zinc, tin, magnesium, calcium, potassium, and sodium; Inorganic fine particles such as nitrides such as silicon nitride, aluminum nitride, titanium nitride and boron nitride; silicon carbide and carbides such as boron carbide; and metal oxides, metal nitrides and metal carbides thereof. Inorganic fine particles can be obtained from 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 (3,4 epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, hexamethyldisilazane , Isopropyl triisostearoyl titanate, isopropyl trioctanoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl dimethate 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 having the surface of inorganic fine particles coated with a polymer such as polyethylene, polypropylene, polymethyl methacrylate, polyamides, polyesters, polystyrenes and silicones.

The method for producing the inorganic fine particles is not particularly limited, and existing coprecipitation methods, thermal spraying methods, sol-gel methods, bulk pulverization-classification methods and the like can be used. Existing methods such as spray drying, dry mixing, and wet mixing can be used without limitation. The primary particle system of the fine particles is preferably from 0.001 μm to 1 μm.
Obtaining particles of 0.001 μm or less is practically difficult,
On the other hand, if the particle size is too large, sedimentation is likely to occur and problems such as difficulty in uniform dispersion are caused. Therefore, the particle size is preferably 0.5 μm or less, and more preferably 0.1 μm or less.

The above-mentioned fine particles can be used by mixing a plurality of particles having different compositions, shapes, manufacturing methods, surface treatment methods and particle systems.

In some cases, by adding an acid, the dental primer can be improved in demineralizing ability of the dental primer and its adhesiveness, particularly its adhesiveness to enamel, can be improved.

Examples of such an acid 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; Organic sulfonic acids such as sulfonic acid are exemplified.

Further, a coloring matter can 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) a polymerizable monomer containing a phosphate group, (B) a polymerizable monomer containing a polyvalent carboxylic acid group, C) Water, (D) a water-soluble organic solvent, and optional components to be blended as necessary may be weighed in a desired ratio into a container and stirred and mixed to form a uniform solution or emulsion.

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

The dental primer of the present invention is usually used 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 any particular limitation.

The above-mentioned dental adhesive material usually comprises a polymerizable monomer, a polymerization catalyst for polymerizing the polymerizable monomer, and other optional components.

The polymerizable monomer includes a phosphate group-containing polymerizable monomer, a polyvalent carboxylic acid group-containing polymerizable monomer, and a polyfunctional polymerizable monomer described in the section of the dental composition. Mers,
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, a plurality of combinations are shown. Further, as the phosphoric acid group-containing polymerizable monomer, those having a molar ratio outside the range specified in the dental composition or a polymerizable monomer represented by the following general formula may be used. You.

[0108]

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Wherein 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 are as follows. This is as follows.

[0110]

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[0111]

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(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 tooth adhesion 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, and a sulfonic acid group-containing polymerizable More preferably contains a polymerizable monomer having an acidic group such as a monomer, a polymerizable monomer having an acidic group and a polyfunctional polymerizable monomer and a water-soluble non-acidic polymerizable monomer More preferably, both are included.

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

As the polymerization catalyst blended in the adhesive material, known compounds can be used without particular limitation as long as they are compounds that 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 and curing. Combinations of polymerization catalysts can be broadly classified into combinations that initiate polymerization by mixing (chemical polymerization catalysts) and combinations that initiate polymerization by light irradiation (photopolymerization catalysts).

Examples of combinations of chemical polymerization catalysts include organic peroxides / amines, organic peroxides / amines / sulfinic acids, organic peroxides / amines / borates, barbiturates / quaternary acids. Grade ammonium halides / metal compounds, etc., and sulfinic acids and borates react with the polymerizable monomer having an acidic group among the polymerizable monomers to start polymerization, and the organic boron compound is air or the like. It can react with oxygen and water on the tooth surface to initiate polymerization.

As the combination of photopolymerization initiators, α-diketones, thioxanthones, α-diketones, which themselves decompose upon irradiation with light to produce polymerizable radical species
-A combination of aminoacetophenones, acylphosphine oxide derivatives and tertiary amines, barbituric acids, mercapto compounds for improving the polymerization initiation ability of the compound, or dyes / photoacid generators / borates And combinations of dyes / photoacid generators / sulfinic acids.

Among the above polymerization catalysts, the use of a photopolymerization catalyst is preferable because the adhesive material can be stored in one liquid and an arbitrary search allowance time can be set, and polymerization with visible light is possible. It is more preferable to use a suitable photopolymerization catalyst.

The dental primer of the present invention is generally used as a primer in a filling repair technique such as primer application to a tooth surface, drying, application of an adhesive, curing of an adhesive, filling of a filling material, and curing of a filling material. Is done. By applying the primer to the tooth surface, the inorganic components of the tooth are dissolved, and at the same time, a permeation layer of the polymerizable monomer is formed in the tooth, and the permeation, diffusion, and polymerization of the adhesive applied thereafter are easy. Assuming a mechanism whereby a strong adhesive layer is formed, the phosphoric acid group-containing polymerizable monomer dissolves the inorganic component due to the acid supply capability of the phosphoric acid group, and further dissolves the tooth material at the phosphate group site. It is easy to penetrate into the dentin due to the affinity, and is advantageous for forming a permeation layer of the polymerizable monomer in the dentin. Further, it is presumed that a monomer having a plurality of carboxylic acid groups has a high affinity for dentin, and thus it is more advantageous to form a permeation layer of a polymerizable monomer in the dentin. In this case, it is necessary that the phosphoric acid group-containing polymerizable monomer has a specific molar ratio because the phosphoric acid monoester [I]
It is presumed that there is a difference between the acid supply capacity and the dentin affinity of the phosphoric acid group portion between the and phosphoric diester [II]. Probably the most favorable dentin affinity for dentin is presumed to be intermediate between the two, with a molar ratio of 1: 0.7 to
In the case of a mixture of 1: 1.35, we believe that we will approach the most favorable properties. Further, since the phosphoric acid monoester [I] has too high hydrophilicity, it facilitates water penetration into the dentin bonding interface when a bonding durability test is performed,
For this reason, durability deteriorates, and conversely, the phosphoric diester [I
I] has relatively low hydrophilicity so that water intrusion is relatively unlikely to occur, and furthermore, the crosslinkability is high, so that the dentin adhesion durability is high, but the acid supply capacity is poor, and the enamel demineralization tends to be insufficient. It is presumed that this appears as a clear difference when the adhesion durability test is performed.

[0119]

According to the present invention, the primer of the present invention is used for pretreatment of the tooth surface prior to the adhesive when bonding the tooth and the filling material with the adhesive, so that only one pretreatment operation is required. As a treatment, the complicated operation of applying both the acid aqueous solution and the primer is simplified, and a single pretreatment of only the primer provides 20 MPa for both enamel and dentin.
A material having the above-mentioned high adhesive strength and showing no harm to the soft tissue in the oral cavity due to whitening or the like can be obtained.

[0120]

The composition of the present invention will be specifically described below by way of examples, but the present invention is not limited to these examples. The abbreviations shown in the text and in the examples,
The abbreviations, the method of measuring the adhesive strength, and the method of preparing the adhesive 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 by a conventional method. It was synthesized as a mixture of acid diester and other impurities, and purified by solvent extraction / washing, column chromatography, HPLC fractionation and the like. This was mixed at a predetermined ratio and used as a phosphoric acid group-containing polymerizable monomer. After mixing, HPLC analysis (column used: Inertsyl ODS2, manufactured by GL Sciences, detection: UV
(210 nm). At this time, the molar extinction coefficient of the polymerizable unsaturated group is determined by the phosphoric acid monoester [I]
And phosphoric diester [II].

(2) Abbreviations and abbreviations [Primer component] (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 '-(3,4-dicarboxybenzoyloxy) 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-toluenesulfin 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: sodium tetraphenylborate -TAZ101: a compound represented by the following structural formula

[0127]

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NKX653: a compound represented by the following structural formula

[0129]

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CQ: camphorquinone DMBE: N, N-dimethyl-p-aminobenzoic acid ethyl ester (3) Enamel, dentin adhesive strength Within 24 hours after slaughter, the bovine anterior teeth were removed, and water was injected. 80
The enamel or dentin plane was cut out so as to be parallel to the lips with water-resistant abrasive paper. Next, compressed air is blown onto these surfaces for about 10 seconds to dry them.
Fix the double-sided tape with a hole of
A simulated cavity was formed by fixing paraffin wax having a hole having a diameter of 6 mm and a diameter of 6 mm so as to be at the same center on the above-mentioned hole. The primer of the present invention prepared immediately before use was thinly applied to the simulated cavity, allowed to stand for 20 seconds, and then dried by blowing compressed air for about 10 seconds. Next, an adhesive was applied, and light was irradiated for 10 seconds with a visible light irradiator (White Light, manufactured by Takara Labelmont) to cure the adhesive.
Further, a dental composite resin (Palphic Light Posteria, manufactured by Tokuyama Co., Ltd.) was filled thereon, and light was irradiated with a visible light irradiator for 30 seconds to prepare an adhesion test piece.

After immersing the above adhesive test piece in water at 37 ° C. for 24 hours, the crosshead speed was 10 mm / min using a tensile tester (Autograph, manufactured by Shimadzu Corporation).
, And the tensile adhesive strength between the teeth and the composite resin was measured.

In each test, the tensile strength of four pieces was measured by the above method, and the average value was defined as the adhesive strength.

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

(4) Adhesive Durability An adhesive test piece was prepared by the same method as the above-mentioned adhesive strength measurement.
After immersion in water at 37 ° C. for 24 hours, they were alternately immersed in water at 4 ° C. and 60 ° C. for 1 minute each 3000 times. afterwards,
Using a tensile tester (Autograph, manufactured by Shimadzu Corporation), the resin was pulled at a crosshead speed of 10 mm / min, and the tensile bond strength between the teeth and the composite resin was measured.

For each test, the tensile strength of four pieces was measured by the above method, and the average value was defined as the adhesive strength after endurance.
The smaller this value is compared to the initial value, the better the adhesion durability.

(5) Marginal sealing property Within 24 hours after sacrifice, the bovine anterior teeth were removed, and under water injection, # 80
The enamel plane was cut out with water-resistant abrasive paper 0 so as to be parallel to the lips. Then, under water injection, using a carborundum point (HP35, manufactured by Shofu Co., Ltd.), the inner system was 4.5 mm to
A cavity was formed that extended to dentin with a depth of 4 mm to 5 mm. The primer of the present invention was thinly applied in the cavity, allowed to stand for 20 seconds, and then dried by blowing compressed air for about 10 seconds. Next, an adhesive was applied, and light was irradiated for 10 seconds with a visible light irradiator (White Light, manufactured by Takara Labelmont) to cure the adhesive. Furthermore, a dental composite resin [Palphique Esterite, Inc.
Manufactured by Tokuyama Co., Ltd.] and irradiated with light for 30 seconds using a visible light irradiator to prepare a marginal sealing test piece.

After the adhesive test piece was immersed in water at 37 ° C. for 24 hours, it was polished with water-resistant abrasive paper of # 800 to remove excess composite resin, and the root portion was immediately polymerized with resin. Socure Fast, manufactured by Tokuyama Corporation]. This was alternately added to a 4 ° C. and 60 ° C. dye aqueous solution (0.1% basic fuchsin, manufactured by Tokyo Chemical Industry),
The immersion was repeated 60 times for 1 minute each. After the immersion, the test piece was ground with # 120 water-resistant abrasive paper so that a cross section from the cervical direction to the crown direction could be seen, and the state of dye penetration into the interface between the dentin and the filled composite resin Observed and evaluated. The evaluation was performed by observing a total of 12 cross sections of six test pieces, that is, six places on the cervical part side and the crown part side, and counted the number of 12 minutes for whether the dye had penetrated. That is, the larger the number, the better the marginal sealing properties.

(6) Storage stability A primer was prepared by dividing into two solutions, Primer A and Primer B, and mixed at a predetermined ratio at the time of use. These primer solutions were mixed immediately after preparation and at 37 ° C.
After storing for a week, the enamel and dentin adhesive strength were measured by the above method. The adhesive strength immediately after the adjustment (initial tensile adhesive strength in the table) was compared with the adhesive strength after storage (in the table, tensile adhesive strength after storage) to evaluate the storage stability.

(7) Gingival whitening test A small amount of the prepared primer was applied to the gingiva of a healthy adult male, and after 20 seconds, it was visually observed whether or not gingival whitening had occurred. The case where no whitening occurred was evaluated as “「 ”, and the case where whitening occurred occurred was evaluated as“ x ”.

(8) Preparation of Adhesives Adhesives A and B were stirred and mixed in the following composition under light shielding to obtain viscous liquids. Adhesive C is a bonding agent attached to ToksoMac Bond (Tokuyama Corporation) which is a commercially available adhesive, adhesive D is a bonding agent attached to Clearfill Liner Bond 2 (Kuraray), and adhesive E is Multipurpose (3
(Company M) The attached adhesive was used as it was.

[0141] Example 1 1. PM-C2 prepared so that the molar ratio was 0.72
6 g and 0.8 g of MAC-10 are dissolved in 3.1 g of ethanol, and 4.5 g of water are mixed with 4.5 g of water as a primer. Using adhesive A, dentin and enamel adhesive strength,
The adhesive durability and the presence or absence of gingival whitening were evaluated. Table 1 shows the results.

Examples 2 to 7 Evaluations were carried out in accordance with the method of Example 1 except that the used PM-C2 was changed to a molar ratio shown in Table 1. Table 1 shows the results.

Comparative Examples 1 to 4 Evaluations were carried out in accordance with the method of Example 1 except that the molar ratio shown in Table 1 was used instead of PM-C2. Table 1 shows the results.

[0144]

[Table 1]

In Examples 1 to 7, the component (A), PM-C
This is a result when the composition ratio of No. 2 was changed within the range of the present invention. In each case, good initial tensile adhesive strength was exhibited.
Adhesive durability is good except that the dentin durability tends to be low in Example 1 where the molar ratio is close to the lower limit, and the enamel durability tends to be low in Example 7 where the molar ratio is close to the upper limit. Indicated. On the other hand, Comparative Examples 1 and 2 are the results when the molar ratio is smaller than the range of the present invention. However, although the adhesion to enamel is good, the initial tensile adhesion to dentin is low and the durability is good. Did not. Comparative Examples 3 and 4
Conversely, the results were obtained when the molar ratio was larger than the range of the present invention. At this time, both the enamel and the dentin had low initial tensile adhesion, and the enamel adhesion durability was extremely poor. No gingival whitening 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, primers having the compositions shown in Table 2 were prepared, and evaluation was performed using the adhesive A. The PM-C2 used at this time had a molar ratio of 1.08. Table 2 shows the compositions of the primers and the results.

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

[0148]

[Table 2]

Examples 8 to 15 show the components (A) and (B) constituting the dental composition used as a primer.
This is a result when the mixing ratio of the component (C) and the component (D) is changed. In each case, good adhesive strength was shown to both dentin and enamel. Comparative Example 5 was a result when the component (A) was not included, and the adhesive strength was low in both dentin and enamel. Comparative Example 6 shows the results when the component (B) was not contained. In this case, although the adhesive strength to enamel was good, the adhesive strength to dentin was insufficient. Comparative Example 7 is a case where the component (A) is above the range of the present invention, Comparative Example 8 is a case where the component (B) is above the range of the present invention, and Comparative Example 9 is a case where the component (C) is below the range of the present invention. In all cases, the adhesive strength to both dentin and enamel was low.

Examples 16 to 23 In accordance with the method of Example 1, primers having the compositions shown in Table 3 were prepared and evaluated using 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 each case, good adhesive strength was exhibited, and it was found that no adhesive was selected when the primer of the present invention was used.

Examples 24 to 30 According to the method of Example 1, primers having the compositions shown in Table 4 were prepared, and evaluation was performed using the adhesive B. The PM-C2 used at this time had a molar ratio of 1.03. Table 4 shows the compositions of the primers and the results.

[0154]

[Table 4]

Examples 24 to 30 show the results when the types of the components (B) and (D) used were changed. The comparison between Examples 24 to 26 and the comparison between Examples 27 and 28 are representative of the results obtained when the type of the component (D) used was changed.
The comparison of 7, 29, 30 and the comparison of Examples 26 and 28 represent the results when the component (B) used was changed.
In each case, good adhesive strength was shown to both dentin and enamel.

Examples 31 to 34 Primers were prepared according to the method of Example 1 using PM-Cl of various molar ratios as the component (A), and evaluation was performed using the adhesive B. Table 5 shows the molar ratio of PM-Cl used and the results.

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

[0158]

[Table 5]

Examples 31 to 34 and Comparative Examples 10 and 11 show the results when the component (A) used was PM-Cl and the molar ratio was changed. Within the scope of the present invention, both the dentin and the enamel exhibited good initial bond strength and bond durability. On the other hand, Comparative Example 10 was a result 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 the durability was not good. . On the contrary, Comparative Example 11 is a result when the molar ratio is larger than the range of the present invention. At this time, both the enamel and the dentin have low initial tensile adhesion and extremely poor enamel adhesion durability. Was. No gingival whitening 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, primers having the compositions shown in Table 6 were prepared and evaluated using the adhesive B. Table 6 shows the composition of the primer used, the molar ratio of the component (A), and the results.

[0161]

[Table 6]

Examples 35 to 40 and Comparative Example 12 show the results when the type of the component (A) to be blended in the dental composition used as the primer was changed. In each case of the examples, good adhesive strength was shown to both dentin and enamel.
Comparative Example 12 is a result 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 PM-C2 prepared so that the molar ratio was 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 so as to have a ratio shown in Table 7 to obtain a primer, and the tooth surface was treated. The quality, enamel bond strength, and edge sealability were evaluated. Table 7 shows the results.

Examples 42 to 48 Primers were prepared according to the method of Example 41, and evaluation was performed using the adhesive B. The composition of the primer used,
Table 7 shows the results.

Comparative Examples 13 and 14 Primers were prepared according to the method of Example 41, and evaluation was performed using the adhesive B. The composition of the primer used,
Table 7 shows the results.

[0166]

[Table 7]

In Examples 41 to 48, the edge blocking property when the primer of the present invention was used was evaluated.
Examples 41 to 48, which are within the scope of the present invention, show clearly better results compared to Comparative Example 13 without the component (A) and Comparative Example 14 without the component (C). Furthermore, (E) Examples 42 and 47 in which the polyfunctional polymerizable monomer is blended show better margin blocking properties as compared with Examples 41 and 46 in which the polyfunctional polymerizable monomer is not blended. (F) Examples 43 to 45 and 48 in which the polymerization accelerator is blended show better margin blocking properties.

Examples 49 to 51 With the compositions shown in Table 8, a primer A solution and a primer B solution were prepared, and the storage stability was evaluated using the adhesive B. Table 8 shows the results.

[0169]

[Table 8]

Examples 49 to 51 are the results of evaluating the 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 the storage, and the storage stability was good.

Claims (5)

[Claims] (A) a phosphate group-containing polymerizable monomer,
(B) a polyvalent carboxylic acid group-containing polymerizable monomer, and (C)
Water is a main component, and 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). , The component (C) is 5
Occupies 90 parts by weight, and the component (A) comprises a mixture of compounds represented by the following general formulas [I] and [II], and [I]
And a mixing ratio of [II] to 1: 0.75 to 1: 1.35 in molar ratio. Embedded image (Wherein, 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 or a group which reacts with water to generate an OH group. ) 2. (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,
(A) Component is 0.5 to 50 parts by weight, component (B) is 1 to 50 parts by weight, and (C) is 100 parts by weight in total of (A), (B), (C) and (D). 5) 90 parts by weight of the component,
The component (D) accounts for 1 to 80 parts by weight, the component (A) is a mixture of compounds represented by the following general formulas [I] and [II], and the mixing ratio of [I] and [II] is 1: 0.75-
A dental primer characterized by a molar ratio of 1: 1.35. Embedded image (Wherein, 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 or a group which reacts with water to generate an OH group. ) 3. A dental primer further comprising (E) 0.1 to 30 parts by weight of a polyfunctional polymerizable monomer with respect to 100 parts by weight of the dental primer according to claim 1 or 2. 4. The polymerization promoter (F) is used in an amount of 0.001 to 100 parts by weight of the dental primer according to claim 1 or 2.
Dental primer further blended at 30 parts by weight. 5. The polyfunctional polymerizable monomer (E) in an amount of 0.1 to 30 parts by weight and the polymerization accelerator (F) in an amount of 0.1 to 30 parts by weight per 100 parts by weight of the dental primer according to claim 1 or 2. 001-001
Dental primer further blended at 30 parts by weight.