JP2002265312A - Dental primer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a primer for developing sufficient adhesiveness to any of dentin, base metal alloy, noble metal alloy and ceramic. SOLUTION: This dental primer composition is characterized in that the primer comprises a polymerizable compound such as 6-methacryloyloxyhexyl-2- thiouracil-5-carboxylate, etc., containing at least one radically polymerizable group and a sulfur atom in the molecule, a coupling agent such as γ- methacryloyloxypropyltrimethoxysilane, etc., a polymerizable monomer containing an acidic group-containing polymerizable monomer such as 2- methacryloyloxy dihydrogen phosphate, etc., a volatile organic solvent such as acetone, etc., and water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a primer composition used as a pre-treatment material for improving adhesiveness when performing an adhesive operation in the dental field.

[0002]

2. Description of the Related Art In the field of dental treatment, a tooth damaged by caries or an accident and a material for restoring the tooth (for example, a composite resin, a metal such as a base metal alloy or a noble metal alloy, a crown made of a ceramic or the like). Repair materials and the like), and various adhesives have been proposed for this purpose. Generally, when bonding is performed using an adhesive, various surface treatment agents (primers) are used as a pretreatment material in order to enhance the adhesiveness. For example,
For pretreatment of dentin (dentin, enamel), a primer for dentin is used. In addition, a surface treatment agent containing a phosphate ester monomer or a carboxylic acid monomer is used for pretreatment of a crown restoration made of a base metal alloy containing a base metal such as iron, nickel, chromium, cobalt, tin, aluminum, copper, and titanium as a main component. (Base metal primer) is used.
The pretreatment of a crown restoration made of a noble metal alloy containing gold, platinum, palladium, silver or the like as a main component includes a compound having a thiophosphate group (JP-A-1-138282) and a dithiochloride group. Compound (JP-A-5-11759)
No. 5), a triazinedithione derivative (Japanese Unexamined Patent Publication No.
No. 83254), a surface treatment agent containing a polymerizable compound having a specific functional group such as a mercaptothiadiazole derivative (Japanese Patent Application Laid-Open No. Hei 8-113376) and a thiouracil derivative (Japanese Patent Application Laid-Open No. 10-1409). Primer). Further, when the crown restoration is made of ceramics, a surface treatment agent (primer for ceramics) containing a silane coupling agent as a main component is used.

[0003] As described above, conventionally, a surface treatment agent (primer) is selected according to an adherend to be bonded, and appropriate pretreatment is carried out, so that dental materials or various materials are combined with dental polymerization. This enabled adhesion with the hydrophilic composition.

[0004] However, it is troublesome to use different surface treatment agents clinically. For example, in the case of bonding a precious metal alloy adhesive bridge to the posterior region, a primer for the dentin is used for the tooth surface and a primer for the noble metal is used for the precious metal alloy surface, and the clinical technique was complicated. . For this reason, there has been a demand for the development of a surface treatment agent (primer) that exhibits sufficient adhesion to any adherend regardless of the adherend.

[0005] As a primer meeting such a demand, a primer capable of exhibiting sufficient adhesiveness to both metals (base metals and noble metals) and ceramics is required to have at least one radical polymerizable group in the molecule. A primer composition containing a polymerizable compound having a sulfur atom, a coupling agent, a polymerizable monomer containing an acidic group-containing polymerizable compound, and an organic solvent as components is known (Japanese Patent Application Laid-Open No. 2000-248201). Gazette).

[0006]

However, the above primer composition exhibits good adhesion to metals (base metals, noble metals) and ceramics, but does not exhibit sufficient adhesion to teeth. However, another primer had to be used for the tooth material. Therefore, an object of the present invention is to provide a primer composition that exhibits sufficient adhesiveness to any of dentin, metals (base metals, noble metals) and ceramics.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, it has been found that when water is added to the above-mentioned primer composition, adhesiveness to tooth substance may be exhibited. Obtained. Further, based on the findings, further investigations have revealed that the intended purpose can be achieved when the mixing ratio of each component is specific, and the present invention has been completed.

That is, the present invention provides (A) a polymerizable compound having at least one radical polymerizable group and a sulfur atom in a molecule, (B) a coupling agent, and (C) an acidic group-containing polymerizable monomer. The polymerizable monomer containing (A) does not include the polymerizable compound (A). }, (D) a volatile organic solvent, and (E) water, and each component based on the total weight of (A), (B), (C), (D), and (E). The proportion is (A) 0.01 to 5% by weight,
(B) 0.1 to 10% by weight, (C) 10 to 45% by weight,
(D) 15 to 60% by weight, and (E) 10 to 60% by weight.
It is a dental primer composition characterized by these.

In the above-mentioned dental primer composition of the present invention, the proportion of each component with respect to the total weight of (A) to (E) is (A) 0.05 to 3% by weight, and (B) 0. 5-
8% by weight, (C) 15 to 40% by weight, (D) 20 to 55%
% By weight, and (E) 20 to 50% by weight, each component being contained in such a ratio, and (F) a polymerization accelerator in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the total weight. Those containing are preferred because they have a particularly high adhesive effect.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION A polymerizable compound having at least one radical polymerizable group and a sulfur atom in a molecule used as the component (A) in the dental primer composition of the present invention (hereinafter also referred to as compound A). ) Is not particularly limited as long as it contains at least one radically polymerizable group and a sulfur atom in the molecule, and a compound represented by the following general formula can be used.

That is, a polymerizable compound represented by the following general formulas A1 to A5 and capable of forming a mercapto group by tautomerism; a disulfide compound represented by the following general formulas A6 to A9; a chain represented by the following general formulas A10 to A11 Alternatively, a cyclic thioether compound may be used.

[0012]

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Wherein R ₁ is a hydrogen atom or a methyl group; R ₂ is a divalent saturated hydrocarbon group having 1 to 12 carbon atoms;
—CH ₂ —C ₆ H ₄ —CH ₂ — group, — (CH ₂ ) _o —Si (C
H ₃ ) ₂ OSi (CH ₃ ) _2- (CH ₂ ) _p -group (where o and p are each an integer of 1 to 5), or —CH ₂
A CH ₂ OCH ₂ CH ₂ — group, wherein Z is —OC (＝ O) —
A —OCH ₂ — group or —OCH ₂ —C ₆ H ₄ — group (however, in any of these groups Z, the rightmost carbon atom is bonded to unsaturated carbon, and the leftmost oxygen atom is a group R ₂ ) and Z ′ is a —OC (＝ O) — group (provided that the rightmost carbon atom is bonded to unsaturated carbon and the leftmost oxygen atom is bonded to the group R ₂ ). , A —C ₆ H ₄ — group or a bond (here, the case where the group Z ′ is a bond means a state where the group R ₂ and the unsaturated carbon are directly bonded), and Y is —S—. ,
—O— or —N (R ′) — (where R ′ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). ｝ Specific examples of these compounds A include those represented by the general formula A1
Examples of the polymerizable compound capable of generating a mercapto group due to tautomerism represented by -A5 include the following compounds.

[0014]

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[0015]

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[0016]

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Examples of the disulfide compounds represented by the general formulas A6 to A9 include the following compounds.

[0018]

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Further, as the chain or cyclic thioether compound represented by the general formulas A10 to A11,
The following compounds are exemplified.

[0020]

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Compound A can be used alone or in combination of two or more.

As the compound A, among these, a polymerizable compound or a disulfide compound capable of generating a mercapto group by tautomerism is preferably used from the viewpoint of storage stability when a primer composition is used. From the viewpoint of strength, a polymerizable compound capable of generating a mercapto group by tautomerism is most preferably used.

The amount (content) of the compound A used in the primer composition of the present invention may be determined according to the above (A), (B),
0.01% by weight based on the total weight of the components (C), (D) and (E) (hereinafter, also referred to as reference weight).
５5% by weight. When the content of the compound A is outside the above range, the adhesiveness to the noble metal tends to decrease, and the effect of the present invention cannot be obtained. From the viewpoint of adhesiveness to noble metals, the content of compound A is preferably 0.05 to 3% by weight of the reference weight.

As the coupling agent (B) used in the present invention, known compounds can be used without limitation. Such coupling agents include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris (Β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltris (β-methoxyethoxy) silane,
γ-methacryloxypropyltri (trimethylsiloxy) silane, ω-methacryloxydecyltrimethoxysilane, γ-methacryloxypropylpentamethyldisiloxane, γ-chloropropyltrimethoxysilane, γ-
Chloropropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-phenyl-γ-aminopropyl Trimethoxysilane, γ-
Silane cups such as aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, mercaptopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, hexamethyldisilazane Ring agents, isopropyl triisostearoyl titanate, isopropyl trioctanoyl titanate,
Isopropyl isostearyl diacryl titanate,
Titanate coupling agents such as isopropyl tridodecylbenzenesulfonyl titanate, isopropyl dimethacrylisostearoyl titanate, and isopropyl tricumyl phenyl titanate; and aluminum coupling agents such as acetoalkoxy aluminum diisopropylate.

Among these coupling agents, in particular,
A silane coupling agent having a polymerizable group is preferably used from the viewpoints of adhesiveness and handleability.

Specific examples of preferably used silane coupling agents having a polymerizable group include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltri (trimethylsiloxy) silane, ω-methacryloxydecyltrisilane. Examples include methoxysilane and γ-methacryloxypropylpentamethyldisiloxane.

The above coupling agents may be used alone or in combination of two or more.

(B) in the primer composition of the present invention
The amount of the coupling agent used must be 0.1 to 10% by weight, expressed in terms of% by weight with respect to the reference weight. When the content of the coupling agent is outside the above range, the adhesiveness to ceramics tends to decrease, and the effect of the present invention cannot be obtained. From the viewpoint of adhesion to ceramics, the content of the coupling agent is preferably 0.5 to 8% by weight of the reference weight.

In the dental primer composition of the present invention, (C)
The polymerizable monomer used as a component needs to contain at least one type of acidic group-containing polymerizable monomer. When the polymerizable monomer component does not contain any acidic group-containing polymerizable monomer, good adhesiveness cannot be obtained. Here, the acidic group-containing polymerizable monomer refers to a phosphinico group {= P (= O) OH} and a phosphono group {-P (= O) (O
H) _2}, a carboxyl group {-C (= O) OH} , sulfo group (-SO ₃ H), and acid anhydride skeleton {-C (= O)
A group (acidic group) that is acidic in an aqueous solution such as an organic group having —OC (＝ O)-｝, and a polymerizable non-polymerizable group such as an acryloyl group, a methacryloyl group, an acrylamide group, a methacrylamide group, and a styryl group. A compound having one or more saturated groups is meant.

The acidic group-containing polymerizable monomer is not particularly limited as long as it is a compound as described above. However, from the viewpoint of adhesion strength to tooth or base metal, the following general formula (1) or (2) is used. The compounds shown can be suitably used.

[0031]

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Wherein R ₃ and R ′ ₃ each independently represent a hydrogen atom or a methyl group, and W and W ′ each independently represent an oxycarbonyl group (—COO—) or an iminocarbonyl group ( —CONH—) or a phenylene group (—C ₆ H ₄ —), wherein R ₄ and R ′ ₄ each independently may have a bond or an ether bond and / or an ester bond. Represents an organic residue having 1 to 30 carbon atoms, and when W is an oxycarbonyl group or an iminocarbonyl group, R ₄ is not a bond, and W ′ is an oxycarbonyl group or an iminocarbonyl group. In this case, R ′ ₄ does not become a bond, X represents a monovalent acidic group,
X ′ represents a divalent acidic group, m and m ′ each independently represent an integer of 1 to 4, m + n represents a valence of R ₄ ,
m '+ n' represents the valence of R _'4.中 In the general formulas (1) and (2), the structure is not particularly limited as long as X and X ′ are acidic groups according to the above definition, but preferred specific examples are as follows.

[0033]

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In the general formulas (1) and (2), the structure of R ₄ is not particularly limited, and may have a bond or a known ether bond and / or ester bond. Although an organic residue having a valence of 1 to 30 carbon atoms can be adopted, preferable groups are specifically exemplified as follows.
The case where R ₄ is a bond means a state where the group W and the group X are directly bonded. When W is an oxycarbonyl group or an iminocarbonyl group, R ₄ is not a bond. This is the same for R ′ ₄ and W ′.

[0035]

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(In the formula, m1, m2, and m3 are each independently an integer of 0 to 10, and m1 + m2 + m3 is 1 or more.) The acidic group represented by the general formulas (1) and (2) Preferred specific examples of the contained polymerizable monomer are as follows.

[0037]

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(In the formula, R ₃ represents a hydrogen atom or a methyl group.)

[0039]

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(Wherein, R ₃ represents a hydrogen atom or a methyl group. In the compounds at the bottom, l, m, and n are each independently an integer of 0 to 2. , M, and n are often obtained as a mixture of different compounds, and the average of the sum of l, m, and n in the mixture is 3.5.)

[0041]

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(In the formula, R ₃ represents a hydrogen atom or a methyl group.)

[0043]

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(However, R ₃ is a hydrogen atom or a methyl group.) In addition, vinyl phosphonic acids, acrylic acid, methacrylic acid, vinyl sulfonic acid and the like are also included in the acidic group-containing polymerizable monomer.

The above acidic group-containing polymerizable monomers can be used alone or in combination of two or more.

Among the acidic group-containing polymerizable monomers specifically exemplified above, from the viewpoint of tooth adhesion, a phosphinico group {= P (= O) OH} and a phosphono group {-P
(= O) (OH) ₂ }, carboxyl group {-C (= O)
It is particularly preferable to use one having OH｝ from the viewpoint of adhesive strength.

The component (C) in the dental adhesive composition of the present invention may be composed only of the above-mentioned acidic group-containing polymerizable monomer, but from the viewpoint of the adhesion to the tooth material and the adhesion durability. It is preferable to further include a polymerizable monomer having no acidic group. In particular, from the viewpoint of the adhesive strength to both enamel and dentin, the content ratio of the acidic group-containing polymerizable monomer in the total polymerizable monomer as the component (C) is 50 to 50%.
Suitably, it is 90% by weight, especially 60-85% by weight. If the amount of the acidic group-containing polymerizable monomer is small, the adhesive strength to enamel tends to decrease, and if it is too large, the adhesive strength to dentin tends to decrease.

The polymerizable monomer having no acidic group used at this time has at least one polymerizable unsaturated group in the molecule and is a polymerizable monomer other than the above-mentioned acidic group-containing polymerizable monomer. As long as it is a body, known compounds can be used without any limitation. Examples of the polymerizable unsaturated group of such a polymerizable monomer include the same as those described above for the acidic group-containing polymerizable monomer, such as an acryloyl group, a methacryloyl group, an acrylamide group, and a methacrylamide group. Is preferred from the viewpoint of adhesiveness.

Specific examples of the polymerizable monomer other than the acidic group-containing polymerizable monomer that can be suitably used in the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate. , Glidizyl (meta)
Acrylate, 2-cyanomethyl (meth) acrylate, benzyl methacrylate, polyethylene glycol mono (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3
Monofunctional polymerizable monomers such as hydroxypropyl (meth) acrylate and glyceryl mono (meth) acrylate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, nona Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, 2,2′-bis [4- (meth)
Acryoyloxyethoxyphenyl] propane, 2,
2′-bis [4- (meth) acryloyloxyethoxyethoxyphenyl] propane, 2,2′-bis [4-
(Meth) acryloyloxyethoxyethoxyethoxyethoxyethoxyphenyl] propane, 2,2′-bis {4- [2-hydroxy-3- (meth) acryloyloxypropoxy] phenyl} propane, 1,4-butanediol di (meth) ) Acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-bis (Methacrylethyloxycarbonylamino) -2,2,4-trimethylhexane, 1,6-bis (methacrylethyloxycarbonylamino) -2,4,4-trimethylhexane, urethane (meth) acrylate, epoxy (meth) acrylate , Trimethylo Lupropane trimethacrylate,
Polyfunctional polymerizable monomers such as pentaerythritol tetramethacrylate; fumaric acid ester compounds such as monomethyl fumarate, diethyl fumarate and diphenyl fumarate;
Styrene, divinylbenzene, α-methylstyrene, α
Styrene such as -methylstyrene dimer; α-methylstyrene derivatives; and allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl carbonate, and allyl diglycol carbonate.

Among these polymerizable monomers other than the acidic group-containing polymerizable monomer, a polyfunctional polymerizable monomer is preferably used particularly from the viewpoint of adhesion to tooth material and adhesion durability. You. Specific examples of preferably used polyfunctional polymerizable monomers include 2,2′-bis {4- [2-hydroxy-3- (meth) acryloyloxypropoxy] phenyl} propane and triethylene glycol. Methacrylate, 2,2-bis [(4- (meth) acryloyloxypolyethoxyphenyl) propane], 1,6-bis (methacrylethyloxycarbonylamino) -2,2,4
-Trimethylhexane, 1,6-bis (methacrylethyloxycarbonylamino) -2,4,4-trimethylhexane and trimethylolpropane trimethacrylate.

The above-mentioned polyfunctional polymerizable monomers may be used alone or in combination.
A combination of more than one species can also be used.

(C) in the primer composition of the present invention
The compounding amount of the polymerizable monomer containing the acidic group-containing polymerizable monomer as a component is represented by weight% with respect to a reference weight,
It must be 10-45% by weight. When the content of the component (C) is out of the above range, the adhesiveness to the dentin and the base metal tends to decrease, and the effect of the present invention cannot be obtained. From the viewpoint of adhesion to tooth and base metal, (C)
The content of the component is preferably 15 to 40% by weight of the reference weight.

The volatile organic solvent (D) used in the present invention includes the polymerizable compound (A), the coupling agent (B), and the acidic group-containing polymerizable component (C). A known organic solvent can be used without any limitation as long as the polymerizable monomer containing the monomer is dissolved and has volatility at room temperature.

Specific examples of the above-mentioned organic solvents that can be suitably used in the present invention include alcohols such as methanol, ethanol, isopropyl alcohol and butanol; ketones such as acetone and methyl ethyl ketone; ethyl ether and 1,4-dioxane. Ethers such as ethyl acetate and ethyl formate; aromatic solvents such as toluene, xylene and benzene; hydrocarbon solvents such as pentane, hexane, heptane and octane; methylene chloride, chloroform, 1, Chlorinated solvents such as 2-dichloroethane; and fluorinated solvents such as trifluoroethanol. Among these, acetone, toluene, ethanol, isopropyl alcohol and the like are particularly preferably used for reasons such as solubility and storage stability.

The above-mentioned organic solvents can be used alone or in combination of two or more.

In the primer composition of the present invention, the amount (content) of the volatile organic solvent (D) needs to be 15 to 60% by weight in terms of% by weight with respect to the reference weight. When the content of the component (D) is outside the above range, the solubility and the adhesiveness tend to decrease, and the effect of the present invention cannot be obtained. From the viewpoint of solubility and adhesiveness,
The content of the component (D) is preferably 20 to 55% by weight of the reference weight.

The water used as the component (E) in the primer composition of the present invention preferably contains substantially no impurities harmful to storage stability, biocompatibility and adhesion.
Examples include deionized water, distilled water, and the like. The amount of the water is 10 to 10% by weight based on the reference weight.
It must be 60% by weight. When the content of the component (E) is out of the above range, the adhesiveness to the tooth tends to decrease, and the effect of the present invention cannot be obtained. From the viewpoint of adhesion to the tooth substance, the content of the component (E) is 2% of the reference weight.
It is preferably 0 to 50% by weight.

In the dental primer composition of the present invention, from the viewpoint of storage stability and adhesive strength, compound (A)
A polymerizable compound capable of generating a mercapto group by tautomerism, (B) a silane coupling agent having a polymerizable group as a coupling agent, and (C) an acid group-containing polymerizable compound represented by the general formula ( It is particularly preferable to use the compound represented by 1) or (2), (D) acetone, toluene, ethanol or isopropyl alcohol as a volatile organic solvent, and (E) distilled water as water. It is.

Further, the dental primer of the present invention has the following properties in order to further improve the adhesiveness to the tooth substance.
It is preferable to further blend (F) a polymerization accelerator. By adding a polymerization accelerator, it becomes possible to increase the polymerization rate at the interface between the tooth substance and the adhesive composition, or to start the polymerization reaction from the interface.

The above-mentioned polymerization accelerator is a substance which acts alone as a polymerization initiator, does not itself act as a polymerization initiator, but has an effect of improving the polymerization initiation ability when used in combination with a polymerization initiator. It is a concept including a substance and a substance which has little ability to initiate polymerization by itself but acts as a polymerization initiator when used in combination with another substance, and is a generic term for these substances.

Known polymerization accelerators can be used without limitation. Examples of such polymerization accelerators include organic peroxides, azo compounds, sulfinic acids, borates, amines, α-diketones, thioxanthones, α-aminoacetophenones, acylphosphine oxides, barbituric acids , Dyes, photoacid generators, organic borons, transition metal compounds and the like.

Specific examples of the above-mentioned organic peroxides include:
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, and azobiscyanovaleric acid.

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, and monoalkyltrialkylboron. Tri (3,5-bistrifluoromethyl) phenylboron, monoalkyltri [3,
5-bis (1,1,1,3,3,3-hexafluoro-
2-methoxy-2-propyl) phenyl] boron, monoalkyltri (p-nitrophenyl) boron, monoalkyltri (m-nitrophenyl) boron, monoalkyltri (p-butylphenyl) boron, monoalkyltri (m -Butylphenyl) boron, monoalkyltri (p
-Butyloxyphenyl) boron, monoalkyltri (m-butyloxyphenyl) boron, monoalkyltri (p-octyloxyphenyl) boron, monoalkyltri (m-octyloxyphenyl) boron (the alkyl group is an n-butyl group , N-octyl group, n-dodecyl group, etc.) sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, tributylamine salt, triethanolamine salt, methylpyridinium Salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt and the like.

Examples of borate compounds having four aryl groups in one molecule include tetraphenylboron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, and tetrakis (3,5-bistrifluoromethyl) Phenylboron, tetrakis [3,
5-bis (1,1,1,3,3,3-hexafluoro-
2-methoxy-2-propyl) phenyl] boron, tetrakis (p-nitrophenyl) boron, tetrakis (m
-Nitrophenyl) boron, tetrakis (p-butylphenyl) boron, tetrakis (m-butylphenyl) boron, tetrakis (p-butyloxyphenyl) boron, tetrakis (m-butyloxyphenyl) boron,
Sodium salt, lithium salt, potassium salt, magnesium salt of tetrakis (p-octyloxyphenyl) boron, tetrakis (m-octyloxyphenyl) boron (alkyl group is n-butyl group, n-octyl group, n-dodecyl group, etc.) Salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, tributylamine salt, triethanolamine salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt,
Butylquinolinium salts and the like.

Among the above-mentioned aryl borates, from the viewpoint of long-term storage stability and availability, 4 boron atoms are particularly preferred.
Tetraaryl borates having two aryl groups bonded thereto are preferred.

As the amines, secondary or tertiary amine compounds in which an amino group is bonded to an aryl group are preferable, and specific examples include N- (2-hydroxyethyl) aniline, N-methylaniline, N-methyl-p-
Secondary amines such as toluidine, N, N-dimethylaniline, N, N-diethylaniline, N, N-dibutylaniline, N, N-dimethyl-p-toluidine, N, N-
Diethyl-p-toluidine N, N-dimethyl-m-toluidine, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, ethyl p-dimethylaminobenzoate, N, N-dihydroxyethylaniline,
Tertiary amines such as N, N-diethanol-p-toluidine, 4-dimethylaminopyridine, tributylamine, tripropylamine, triethylamine and N, N-dimethylaminoethyl methacrylate.

Also, 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 (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like are mentioned as acylphosphine oxides.

Specific examples of barbituric acids include:
Examples thereof include 5-butyl barbituric acid, 1-ethyl-5-methyl barbituric acid, and 1-hexyl-5-ethyl barbituric acid.

As the pigments, coumarin pigments can be mentioned. Particularly preferred coumarin-based tones are 400 to 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) -7-diethylaminocoumarin, 3- ( 2'-benzthiazoyl) -7-diethylaminocoumarin, 3,
3'-carbonylbis (4-cyano-7-diethylamino) coumarin and the like can be mentioned.

Examples of photoacid generators include 2,4,6-tris (trichloromethyl) -s-triazine, 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-bromophenyl) -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
Halomethyl-substituted-s-triazine derivatives such as 4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, diphenyliodonium, bis (p-chlorophenyl) iodonium, ditolyliodonium, Bis (p-tert-butylphenyl) iodonium, bis (m-nitrophenyl) iodonium, p-tert-butylphenylphenyliodonium, methoxyphenylphenyliodonium, p-
Chloride such as octyloxyphenylphenyliodonium, bromide, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, trifluoromethanesulfonate and the like can be mentioned.

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

Examples of the transition metal compounds include transition salts of transition metals such as iron, cobalt, nickel, copper, zinc and titanium, such as hydrochloride, sulfate, nitrate, phosphate, acetate, citrate, and the like.
Oxalates, EDTA salts or acetylacetone complex salts and the like, specifically, iron chloride, copper chloride, cobalt chloride, zinc chloride, iron nitrate, copper nitrate, iron acetate, copper acetate, iron citrate, copper citrate, Iron oxalate, copper oxalate, iron acetylacetone, copper acetylacetone and the like can be suitably used.

The amount of these polymerization accelerators is 0 parts by weight based on 100 parts by weight of the total of the components (A), (B), (C), (D) and (E) from the viewpoint of the adhesive strength to the dentin. .001-
It is preferably 30 parts by weight, particularly preferably 0.05 to 10 parts by weight, and most preferably 0.1 to 5 parts by weight.

These polymerization accelerators may be used alone or in combination of two or more in the dental primer composition of the present invention. There is no particular limitation in the case of combining two or more, and any combination can be used.However, it is necessary to determine the packaging state in consideration of the storage stability when the combination itself and other components are combined. is there.

The dental primer composition of the present invention may further contain, if necessary, a polymerization inhibitor such as hydroquinone monomethyl ether, hydroquinone, and 4-tert-butylphenol in addition to the above-mentioned components.

In the dental primer composition of the present invention, not all the components need to be present in the same package. For example, the components (A), (B) and (D)
The solution composed of the components and the solution composed of the components (C), (D) and (E) can be separately packaged and mixed at the time of use.

The method of using the dental primer composition of the present invention is not particularly limited. However, in order to satisfactorily bond tooth materials, metals or ceramics to a dental adhesive such as resin cement, the dental primer composition of the present invention is used. After the primer composition is applied to the surface of the tooth, metal or ceramic, a dental adhesive is applied to the applied surface, and then the adhesive present between the adherends is cured. it can.

In the above method, a known dental adhesive can be used without any limitation as the adhesive.
Considering ease of handling and the like, it is preferable to use a polymer adhesive containing an acrylic or methacrylic polymerizable monomer and a polymerization initiator.

Specific examples of the acrylic or methacrylic polymerizable monomer include monofunctional polymer such as methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and methacryloxyethyl propionate. Water-soluble monomer; triethylene glycol di (meth) acrylate, 2,2-bis (4- (3- (meth) acryloyloxy-2-hydroxypropoxy)
Phenyl) propane, 2,2-bis (4- (meth) acryloyloxyethoxyphenyl) propane, 1,6-
Polyfunctional polymerizable monomers such as hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylhexamethylene diisocyanate, and pentaerythritol tri (meth) acrylate;
Methacryloxyethoxycarbonylphthalic anhydride, 1
Adhesive polymerizable monomers such as 0-methacryloxydecyl dihydrodiene phosphate and 10-methacryloxydecamethylene malonic acid are exemplified. These are used alone or in combination of two or more depending on desired physical properties and operability.

Specific examples of the polymerization initiator include a redox initiator such as benzoyl peroxide / N, N-diethanol-p-toluidine; an alkyl metal compound such as a partial oxide of tributylborane; and n-butyl barbituric acid. / Barbituric acid-based initiators such as copper chloride; and photopolymerization initiation catalysts such as camphorquinone / N, N-dimethylaminoethyl methacrylate.

[0084]

EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

The substances used in the examples and comparative examples, their abbreviations, and the adhesion test method are shown below.

(1) Compound A (used as component (A))

[0087]

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(2) Coupling agent {used as component (B)}

[0089]

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(3) Polymerizable monomer containing an acidic group {used as component (C)}

[0091]

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(4) Polymerizable monomers other than the acidic group-containing polymerizable monomer {used as component (C)} BisGMA; 2,2-bis (4- (2-hydroxy-3-methacryloyloxypropoxy) Phenyl) propane 3G; triethylene glycol dimethacrylate D26E; 2,2-bis [(4-methacryloyloxy polyethoxyphenyl) propane] TMPT; trimethylolpropane trimethacrylate UDMA; 1,6-bis (methacrylethyloxycarbonylamino) -A mixture of 2,2,4-trimethylhexane and 1,6-bis (methacrylethyloxycarbonylamino) -2,4,4-trimethylhexane. HEMA; 2-hydroxyethyl methacrylate.

(5) Volatile organic solvent (used as component (D)) IPA; isopropyl alcohol MMA; methyl methacrylate.

(6) Polymerization accelerator {used as component (F)} PTSNa; sodium p-toluenesulfinate PhBNa; sodium tetraphenylboron PhBTEOA; tetraphenylboron triethanolamine salt DEPT; N, N-diethanol-p- Toluidine.

(7) Adhesion test method for dentin The bovine anterior tooth was removed within 24 hours after sacrifice, and water was injected under # 80.
The enamel or dentin plane was cut out with emery paper No. 0 so as to be parallel to the lips. Next, after compressed air was blown onto these surfaces for about 10 seconds to dry them, a double-sided tape having a hole having a diameter of 3 mm was fixed to the flat surfaces to form simulated cavities. An appropriate amount of each of the dental primer compositions of Examples and Comparative Examples was applied to each of the simulated cavities with a sponge, left for 30 seconds, and then blown with compressed air for about 5 seconds. Then, methyl methacrylate (80 parts by weight), 2
-Hydroxyethyl methacrylate (20 parts by weight),
An adhesive resin cement consisting of N, N-dimethyl-p-toluidine (3 parts by weight), polymethyl methacrylate (130 parts by weight), and benzoyl peroxide (2 parts by weight) was filled into the simulated cavity, and then placed on the cavity. An adhesion test piece was prepared by pressing a stainless steel attachment having a diameter of 8 mm, which was previously treated with "MR Bond (manufactured by Tokuyama)". Then, the adhesive test piece was immersed in water at 37 ° C. for 24 hours, and the adhesive strength with the tooth was measured at a crosshead speed of 1 mm / min using a tensile tester (Autograph, manufactured by Shimadzu Corporation). The performance was evaluated.

(8) Adhesion test method for metal Dental cobalt-chromium alloy “Wachrome” (10 × 10 × 3 mm, manufactured by Towa Giken Co., Ltd.), and a dental gold-silver-palladium alloy “Gold Para 12” as an adherend (10 × 10 × 3 mm, manufactured by Towa Giken Co., Ltd.) was polished with # 1500 water-resistant abrasive paper, and then subjected to sandblasting, and an adhesive tape having a 3 mmφ hole was attached to the treated surface to fix the adhesive area. . An appropriate amount of each of the dental primer compositions of Examples and Comparative Examples was applied to each of the simulated cavities with a sponge, left for 30 seconds, and then blown with compressed air for about 5 seconds. Then, methyl methacrylate (80 parts by weight),
2-hydroxyethyl methacrylate (20 parts by weight),
An adhesive resin cement consisting of N, N-dimethyl-p-toluidine (3 parts by weight), polymethyl methacrylate (130 parts by weight), and benzoyl peroxide (2 parts by weight) was filled into the simulated cavity, and then placed on the cavity. A stainless steel attachment having a diameter of 8 mm, which was previously treated with "MR Bond (manufactured by Tokuyama)", was pressed into contact to produce an adhesion test piece. Then, the adhesive test piece was immersed in water at 37 ° C. for 24 hours, and the adhesive strength with the tooth was measured at a crosshead speed of 1 mm / min using a tensile tester (Autograph, manufactured by Shimadzu Corporation). The performance was evaluated.

(9) Adhesion test method for ceramics Dental porcelain “Gee Cosmo Tech II” to be adhered
(10 × 10 × 3 mm, manufactured by GC Corporation) was polished with # 1500 water-resistant abrasive paper, and an adhesive tape having a 3 mmφ hole was attached to the treated surface to fix the adhesive area.
An appropriate amount of each of the dental primer compositions of Examples and Comparative Examples was applied to each of the simulated cavities with a sponge, left for 30 seconds, and then blown with compressed air for about 5 seconds. Thereafter, methyl methacrylate (80 parts by weight), 2-hydroxyethyl methacrylate (20 parts by weight), N, N-dimethyl-p-toluidine (3 parts by weight), polymethyl methacrylate (130 parts by weight), benzoyl peroxide (2 parts by weight) Parts by weight)
After filling the simulated cavity with the adhesive resin cement made of, a stainless steel attachment having a diameter of 8 mmφ, which was previously treated with “MR Bond (manufactured by Tokuyama)”, was pressed into contact with it to produce an adhesion test piece. afterwards,
After immersing the adhesive test piece in water at 37 ° C. for 24 hours,
Using a tensile tester (Autograph, manufactured by Shimadzu Corporation), the adhesive strength with the teeth was measured at a crosshead speed of 1 mm / min, and the adhesive performance was evaluated.

Example 1 0.04 g of MTU-6, 0.3 g of A-174, 2 g
PM2, 0.5 g UDMA, 4.16 g acetone and 3 g distilled water were prepared,
Dentin, enamel, dental precious metal alloy "Gold Para 1
2 ", the adhesive strength to the dental base metal alloy" Wachrome "and the dental porcelain" Gesera Cosmotech II "were measured. As a result, 14MPa for "dentin", 18MPa for "enamel" and 24M for "gold para 12"
The adhesive strength obtained was 26 MPa for Pa and “Wachrome” and 24 MPa for “Gesera Cosmotech II”.

Examples 2 to 32 In the same manner as in Example 1, primer compositions having the compositions shown in Tables 1, 2 and 3 were prepared. The adhesive strength to dentin, enamel, dental precious metal alloy “Gold Para 12”, dental base metal alloy “Wachrome” and dental porcelain “Gysera Cosmotech II” was measured. As a result, as shown in Table 1, Table 2, and Table 3, high adhesive strength was obtained in any of the compositions.

[0100]

[Table 1]

[0101]

[Table 2]

[0102]

[Table 3]

Comparative Examples 1 to 6 In the same manner as in Example 1, the primer compositions shown in Table 4 were prepared, and dentin, enamel, and a dental precious metal alloy “Gold Para 1” were prepared.
2 ", the adhesive strength to the dental base metal alloy" Wachrome "and the dental porcelain" Gesera Cosmotech II "were measured.

[0104]

[Table 4]

As a result, as shown in Table 4, in the case where the sulfur atom-containing polymerizable compound was not added (Comparative Example 1) and the case where the amount of addition was out of the range (Comparative Examples 2 and 3), the dental Adhesion strength to "gold para 12" which is a precious metal alloy for use decreased. Furthermore, the case where the coupling agent was not added (Comparative Example 4) and the case where the addition amount was out of the range (Comparative Example 5,
6) In “Gesera Cosmotech I”
The adhesive strength to "I" decreased. An example in which the acidic group-containing polymerizable compound was not added (Comparative Example 7), an example in which the acidic group-containing polymerizable monomer was not added (Comparative Example 8), and the amount added was Examples outside the range (Comparative Example 9,
In 10), the bond strength to dentin and enamel was reduced, and the bond strength to "wachrome", which is a dental base metal alloy, was also reduced. In the case where the organic solvent was not added (Comparative Example 11), the adhesion test was impossible because the primer did not become a uniform solution. In the examples in which distilled water was not added (Comparative Examples 13 and 15), the adhesive strength to dentin and enamel was significantly reduced. In the case where the amount of the organic solvent added is out of the range (Comparative Example 12), dentin,
The bond strength to enamel decreased. In the case where the amount of distilled water added was out of the range (Comparative Example 14), the adhesion test was not possible because the primer did not become a uniform solution.

[0106]

EFFECT OF THE INVENTION By using the dental primer composition of the present invention, it is possible to easily prepare various dental resins and the like with a simple pretreatment for any of dentin, metals (both base metal alloys and precious metal alloys), and ceramics. Adhesion can be improved. For example, when bonding a noble metal alloy adhesive bridge to a molar part, it is possible to improve the adhesiveness to the resin by performing the primer treatment on the noble metal alloy surface and the tooth surface, thereby simplifying the clinical technique. Also leads to

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Hideki Kazama 1-1, Mikage-cho, Tokuyama-shi, Yamaguchi F-term in Tokuyama Co., Ltd. (reference) FA212 GA13 HA156 HA476 JA02 JA05 JA08 JA18 JA23 JA26 JA32 JA56 JA66 JA68 JB01 JB08 JB16 JC18 JC23 JC31 JC32 JC35 JC36 JC37 KA03 KA04 KA06

Claims (3)

[Claims] 1. A polymerizable compound having (A) at least one radical polymerizable group and a sulfur atom in a molecule, (B)
Coupling agent, (C) polymerizable monomer containing acidic group-containing polymerizable monomer {However, the component does not include the polymerizable compound (A). }, (D) volatile organic solvents,
And (E) water, and (A)
(B), (C), (D), and (E), the ratio of each component to the total weight of (A) 0.01 to 5% by weight, (B)
0.1 to 10% by weight, (C) 10 to 45% by weight, (D)
A dental primer composition comprising 15 to 60% by weight and (E) 10 to 60% by weight. 2. The dental primer composition according to claim 1, further comprising (F) a polymerization accelerator. 3. The polymerizable monomer according to claim 1, wherein (C) the polymerizable monomer containing an acidic group-containing polymerizable monomer contains a polyfunctional polymerizable monomer. Dental primer composition.