JP2000178113A - Adhesion kit for dentine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an adhesion kit for dentine having high bond strength to both enamel and dentine by one pretreatment. SOLUTION: This adhesion kit for dentine comprises a combination of a dental primer containing an acid such as an inorganic acid or an organic acid, a metal compound such as cupric chloride and water and a dental-adhesive containing a polymerizable monomer containing an acidic group such as a phosphate group or a carboxylate group, an aryl borate compound and a filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a dental adhesive kit. More specifically, the present invention relates to a primer, an adhesive, and a kit comprising the same, which are used for obtaining a high adhesive strength between a crown restorative material and a tooth material in a dental restoration in the field of dental care.

[0002]

2. Description of the Related Art To restore teeth damaged by dental caries or accidents, a method of bonding a dental restoration material such as a composite resin or a metal or ceramics to a tooth material with an adhesive has been used. At present, there are light-curable adhesives and chemically-curable adhesives depending on the type of crown material as adhesives for bonding the tooth material and the crown restorative material. For restoration using a resin, a light-curing type bonding material is used, and for restoration using a metal casting or ceramics, a resin cement, which is a chemical polymerization type adhesive, is used.

[0003] Such an adhesive is required to firmly adhere the tooth material and the restoration to the crown for a long period of time under the harsh environment of the oral cavity. If the adhesive strength of the adhesive is low or the durability is insufficient, the restoration may fall off, or a gap may be formed between the tooth material and the restoration, and bacteria may enter through the gap and cause a 2
This is because there is a risk of causing secondary caries.

[0004] The hard tissue of a tooth is composed of enamel and dentin and clinically required to adhere to both. Conventionally, for the purpose of improving the adhesiveness, a method has been used in which the surface of the teeth is pre-treated prior to application of the adhesive and then washed with water. As such a pretreatment material, an aqueous acid solution for demineralizing the tooth surface is generally used. For this purpose, an aqueous acid solution such as phosphoric acid, maleic acid, or citric acid has been used. In the case of enamel, the mechanism of adhesion to the treated surface is a macromechanical engagement force that allows the adhesive to penetrate and harden the surface roughened by the demineralization of the acid aqueous solution, and is clinically sufficient for adhesion Strength had been obtained. On the other hand, in the case of dentin, the adhesive is permeated into fine voids of sponge-like collagen fibers that are exposed on the tooth surface after demineralization, and the adhesive is hardened by micro mechanical engagement. However, since it is not easy for the adhesive to penetrate into the exposed collagen layer, a method of applying a penetration enhancer called a primer after treatment with an acid aqueous solution and drying without washing with water is generally used. Was complicated.

[0005] In order to solve this complication, attempts have been made to omit pretreatment with an aqueous acid solution and washing with water. That is, a method of obtaining a high adhesive strength to both enamel and dentin only by applying and drying the primer on the tooth surface has been attempted, and JP-A-3-240712 discloses an acidic group-containing polymerizable monomer. Body, hydroxyl-containing polymerizable monomer,
Primer composition comprising water and curing agent
No. 8368 describes a primer composition containing an acidic group-containing polymerizable monomer, a hydroxyl group-containing polymerizable monomer, water, and an amino compound having an acid group.
JP-A-6-192030 discloses a pretreatment material comprising a vinylphosphonic acid, a metal salt of a vinylphosphonic acid, a carboxylic acid having a hydrophobic group, water and an alcohol, and JP-A-6-192030 discloses a metal salt of an organic sulfonic acid and a hydrophobic group. A pretreatment material comprising an organic carboxylic acid having water, an alcohol and water, and a primer composition comprising a vinyl compound having an acidic group, a vinyl compound having a hydroxyl group, water, aromatic sulfinic acid and an amine in JP-A-7-82115 Product, JP-A-7
No. 89820 discloses a polymerizable monomer having an acidic group,
In Japanese Patent Application Laid-Open No. 7-97306, water and a primer composition comprising a compound having an amide group and a hydroxyl group in water, a primer composition comprising a polymerizable monomer having an acidic group, an organic solvent, and water An adhesive system using a curable composition comprising a polymerizable monomer having an acidic group, a polymerizable monomer having a hydroxyl group, and a polymerization initiator is disclosed.

[0006] However, any of the primer compositions can provide an adhesive force to both enamel and dentin when a photopolymerizable adhesive such as a bonding material for a composite resin is used. When a chemically polymerizable adhesive such as that described above was used, a sufficient adhesive strength had not yet been obtained. Chemically polymerizable adhesives generally have a lower polymerization rate than photopolymerizable adhesives, and therefore have poor adhesive strength. Among the chemically polymerized adhesives, when a trialkylboron (or a partial oxide thereof) having a high activity as a catalyst is used, a high adhesive strength can be obtained, but since the catalyst is chemically unstable, packaging is not possible. This has the disadvantage that the operation is complicated, such as the necessity to perform the operation.

[0007] Therefore, there has been a demand for the development of an adhesive kit comprising a primer and an adhesive which can obtain excellent adhesive strength even when a chemical polymerization type adhesive is used.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide an adhesive kit comprising a primer and an adhesive having a high adhesive strength to both enamel and dentin in one pretreatment. .

[0009]

Means for Solving the Problems The present inventors have made intensive studies to overcome the above technical problems, and as a result, have found that at least one metal selected from the group consisting of acids, copper compounds, iron compounds, and cobalt compounds. After treating the tooth surface with a dental primer comprising the compound and water, the enamel is obtained by bonding using a dental adhesive comprising an acidic group-containing polymerizable monomer, an aryl borate compound and a filler. It has been found that high adhesive strength can be obtained for both dentin and dentin.

That is, the present invention relates to a dental primer comprising (A) an acid, (B) at least one metal compound selected from the group consisting of a copper compound, an iron compound and a cobalt compound, and (C) water. And (D) an acid group-containing polymerizable monomer, (E) an aryl borate compound, and (F) a dental adhesive comprising a filler. .

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The acid which is the component (A) used in the dental primer of the present invention includes inorganic acids, organic acids and polymerizable monomers containing an acidic group.

As the inorganic acid, for example, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, perchloric acid and the like are used.

The organic acids include, for example, acetic acid, citric acid,
Examples include organic carboxylic acids such as malonic acid and oxalic acid, and sulfonic acids such as benzenesulfonic acid and toluenesulfonic acid.

The acidic group-containing polymerizable monomer is not particularly limited as long as it has at least one acidic group and at least one polymerizable unsaturated group in one molecule.
Known compounds can be used. As the acidic group, a phosphinico group, a phosphono group, a carboxyl group and an anhydride thereof, a sulfonic acid group and the like are preferable, and a polymerizable monomer having a typical phosphinico group, a phosphono group, a carboxyl group and an anhydride thereof, and a sulfonic acid group Is represented by the following general formula (2).

[0015]

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Wherein R ⁶ is a hydrogen atom or a methyl group;
Represents an oxycarbonyl group (—COO—), an amide group (—C
ONH-), or a phenylene group (-C ₆ H ₄ -) represents, R ⁷ is a bond or an ether bond and / or 1 to 30 carbon atoms may also be divalent to hexavalent, which have an ester bond,
X represents a phosphinico group, a phosphono group, a carboxyl group and an anhydride thereof, or a group containing a sulfonic acid group, l is an integer of 1 to 4, m and n are 1 or 2
Represents an integer. However, when R ⁷ is divalent, 1 is 1,
m and n represent an integer of 1 or 2, when R ⁷ is trivalent, l, m and n represent an integer of 1 or 2, and when R ⁷ is tetravalent, l is 2 or 3, m and n represents an integer of 1 or 2, in the case of R ⁷ is 5-valent is, l is 3 or 4, m and n represents an integer of 1 or 2, when R ⁷ is a hexavalent Is l
Represents 4, m represents 2, and n represents an integer of 1 or 2. Furthermore, W
Is a oxycarbonyl group or an amide group, R ⁷ is not a bond. Ｘ In the general formula (2), X is a group containing a phosphinico group, a phosphono group, a carboxyl group and an anhydride thereof, and a sulfonic acid group, and the structure thereof is not particularly limited. It is as follows.

[0017]

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In the general formula (2), the structure of R ⁷ is not particularly limited, and may have a bond or a known divalent to hexavalent carbon atom which may have an ether bond and / or an ester bond. Although 1 to 30 organic residues can be employed, specific examples are as follows. The case where R ⁷ 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 amide group, R ⁷ does not become a bond and the above organic residue Becomes

[0019]

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Preferred specific examples of the acidic group-containing polymerizable monomer represented by the general formula (2) are as follows.

[0021]

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[0022]

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[0023]

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[0024]

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(However, R ⁶ is a hydrogen atom or a methyl group.) In addition, vinyl phosphonic acids having a phosphoric acid group directly bonded to a vinyl group, acrylic acid, methacrylic acid, vinyl sulfonic acid and the like are also polymerized with an acidic group. Specific examples of the hydrophilic monomer are mentioned.

Among the above acids, an acidic group-containing polymerizable monomer is particularly preferable from the viewpoint of adhesiveness.

The amount of the acid is preferably 1 to 50 parts by weight, more preferably 2 to 30 parts by weight, most preferably 2 to 30 parts by weight, when the total of all the components constituting the primer is 100 parts by weight. Is 3 to 20 parts by weight. If the amount of the acid is small, the adhesion to enamel tends to decrease, and if it is too large, the adhesion to dentin tends to decrease.

The above acids may be used as a mixture of a plurality of types as necessary.

The metal compound as the component (B) used in the dental primer of the present invention is selected from a copper compound, an iron compound and a cobalt compound. In particular,
Halides such as chlorides and fluorides of the above metals; salts of inorganic acids such as nitrates and sulfates; salts of acetates, acrylates, methacrylates and other organic acids; organic complexes such as complexes with acetylacetone Are preferred. These metal compounds may have any valence.

Examples of copper compounds include copper (I) chloride, copper (II) chloride, copper (I) fluoride, copper (II) fluoride, salts of inorganic acids such as copper nitrate and copper sulfate, copper acetate And salts of organic acids such as copper citrate, copper acrylate and copper methacrylate, and complex salts such as copper acetylacetone.

Examples of iron compounds include salts of inorganic acids such as iron (I) chloride, iron (II) chloride, iron nitrate and iron sulfate, and organic acids such as iron acetate, iron acrylate and iron methacrylate. And complex salts such as iron acetylacetone.

Examples of cobalt compounds include salts of inorganic acids such as cobalt (I) chloride, cobalt (II) chloride, cobalt nitrate and cobalt sulfate, and organic acids such as cobalt acetate, cobalt acrylate and copper methacrylate. And complex salts such as cobalt acetylacetone.

Among these metal compounds, copper halide and iron halide are preferred from the viewpoint of adhesive strength.

The amount of the metal compound is preferably in the range of 0.001 to 5 parts by weight, more preferably 0.01 to 1 part by weight, when the total of all the components constituting the primer is 100 parts by weight. It is in the range of parts by weight. If the amount of the metal compound is less than 0.001 part by weight, the adhesive strength to dentin tends to decrease, and if it exceeds 5 parts by weight, the adhesive force to both enamel and dentin tends to decrease.

The above metal compounds can be used as a mixture of a plurality of types as necessary.

The water used as the component (C) used in the dental primer of the present invention is preferably substantially free from impurities harmful to storage stability, biocompatibility and adhesion.
Examples include deionized water, distilled water, and the like.

The amount of the water is preferably 5 to 90 parts by weight, more preferably 20 to 80 parts by weight, when the total of all components constituting the primer is 100 parts by weight, An addition amount of 75 parts by weight is most preferred.
When the amount is less than 5 parts by weight, the adhesive strength to both dentin and enamel tends to be insufficient.
When the amount is more than the weight part, the adhesive strength to dentin tends to be insufficient.

The dental primer of the present invention includes the above acid,
In addition to the metal compound and water, various optional components described below can be contained as needed within a range that does not impair the effects of the present invention.

Examples of such optional components include radical polymerizable monomers other than the acidic group-containing polymerizable monomer, polymerization inhibitors, inorganic or organic fine particles, and organic solvents.

The other radically polymerizable monomers are not particularly limited, and known monofunctional or polyfunctional radically polymerizable monomers can be used.

In the other radical polymerizable monomer, examples of the group having a radical polymerizable unsaturated bond include a methacryloyloxy group, an acryloyloxy group, a methacrylamide group, an acrylamide group, a styryl group, an allyl group and the like. Can be Among them, a (meth) acrylate polymerizable monomer having a methacryloyloxy group or an acryloyloxy group is preferable in terms of polymerizability, adhesiveness, and ease of handling.

Specific examples of monofunctional radically polymerizable monomers generally preferably used include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl methacrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl methacrylate , Monofunctional (meth) acrylate monomers such as 2-hydroxypropyl methacrylate and methoxydiethylene glycol (meth) acrylate; N
Monofunctional (meth) acrylic amide monomers such as methylol (meth) acrylamide; and monofunctional styrene monomers such as styrene and α-methylstyrene.

Specific examples of the polyfunctional radically polymerizable monomer generally preferably used include 2,2-bis (4-
(Meth) acryloyloxyphenyl) propane, 2,
2-bis (4- (3- (meth) acryloyloxy-2
-Hydroxypropoxy) phenyl) propane, 2,2
-Bis (4- (meth) acryloyloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxytetraethoxyphenyl) ) Propane, 2,2-bis (4- (meth) acryloyloxypentaethoxyphenyl) propane,
2-bis (4- (meth) acryloyloxydipropoxyphenyl) propane, 2- (4- (meth) acryloyloxyethoxyphenyl) -2- (4- (meth) acryloyloxydiethoxyphenyl) propane,
(4- (meth) acryloyloxydiethoxyphenyl) -2- (4- (meth) acryloyloxytriethoxyphenyl) propane, 2- (4- (meth) acryloyloxydipropoxyphenyl) -2- (4- ( (Meth) acryloyloxytriethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxydipropoxyphenyl) propane, 2,2-bis (4-
(Meth) acryloyloxyisopropoxyphenyl)
Propane, 1- (meth) acryloyloxymethyl-2
-Aromatic difunctional (meth) acrylate monomers such as (meth) acryloyloxyethyl hydrogen malate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, butylene Glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butanediol di (meth)
Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, di-2-
Aliphatic difunctional (meth) acrylate monomers such as (meth) acryloyloxyethyl-2,2,4-trimethylhexamethylene dicarbamate; bifunctional (meth) acrylates such as N, N'-methylenebis (meth) acrylamide Acrylic acid amide monomers; bifunctional styrene monomers such as divinylbenzene and α-methylstyrene dimer; bifunctional allylic monomers such as diallyl phthalate and diallyl carbonate; trimethylolpropane tri (meth) acrylate; Trifunctional (meth) acrylate monomers such as trimethylolethane tri (meth) acrylate; and tetrafunctional (meth) acrylate monomers such as pentaerythritol tetra (meth) acrylate.

When a polymerizable monomer is added to the dental primer of the present invention, the polymerization inhibitor has a remarkable effect on the adhesive strength in order to prevent gelation during storage and improve storage stability. It is preferable to add a small amount. Specific examples of such a polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, 2,6-ditert-butylphenol, and the like.

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

Specific examples of such fine particles include polyethylene, polypropylene, 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 above-mentioned 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 will occur.

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.

When a water-insoluble polymerizable monomer or other water-insoluble optional components are added to the dental primer of the present invention, the organic solvent is used to dissolve these components to form a uniform solution. Useful for

Specific examples of such organic solvents include methanol, ethanol, 1-propanol, 2-propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol and 2-methyl-2.
-Propanol, 2-methyl-2-butanol, 2-propen-1-ol, 2-propyn-1-ol, 1,
2-ethanediol, 1,2-propanediol, 1,
3-propanediol, 1,3-butanediol, 1,
4-butanediol, 2,3-butanediol, 1,5
-Pentanediol, hexylene glycol, glycerol, 1,2,6-hexanetriol, trimethylolpropane, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 2-methoxyethanol, -Ethoxyethanol, 2- (methoxyethoxy) ethanol, 2- (ethoxyethoxy) ethanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, 2-isopropoxyethanol, 2-butoxyethanol, 1-methoxy-2- Propanol, 1-
Ethoxy-2-propanol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, 1,3-dioxolan, tetrahydrofuran, dioxane, propylene oxide, dimethoxymethane, 1,2-dimethoxyethane, 1,2-diethoxyethane, bis Alcohol compounds or ether compounds such as (2-methoxyethyl) ether and bis (2-ethoxyethyl) ether, ketone compounds such as acetone and methyl ethyl ketone, and phosphoric ester compounds such as hexamethylphosphoric triamide , Dimethylformamide,
Water-soluble organic solvents such as acid amide compounds such as dimethylacetamide, carboxylic acid compounds such as acetic acid and propionic acid, and sulfur oxide compounds such as dimethyl sulfoxide and sulfolane.

Among these water-soluble organic solvents, it is most preferable to use ethanol, isopropanol or acetone from the viewpoint of harmful effects on living organisms.

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

The method for preparing the dental primer of the present invention is not particularly limited, and the above components may be weighed, placed in a container, stirred, mixed, and made into a uniform solution.

The packaging form of the dental primer of the present invention is as follows:
What is necessary is just to determine suitably considering storage stability, and it does not specifically limit. For example, when an easily hydrolyzable component is contained, the easily hydrolyzable compound, water, and a compound that serves as a catalyst for hydrolysis such as an acid may be divided into two in an arbitrary combination and used. It may be mixed just before.

The dental primer of the present invention must be used in combination with the following adhesive.

The acidic group-containing polymerizable monomer which is the component (D) used in the dental adhesive of the present invention is specifically exemplified as a kind of the acid component (A) in the section of the dental primer. And the same acidic group-containing polymerizable monomer as mentioned above. These acidic group-containing polymerizable monomers can be used alone or as a mixture of two or more as necessary.

The aryl borate compound as the component (E) used in the dental adhesive of the present invention is necessary because it reacts with the above-mentioned acid to form a radical initiator. The following general formula (1)

[0058]

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(Provided that R ¹ , R ² and R ³ each independently represent a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, A substituted or unsubstituted aralkyl group having 2 to 6 carbon atoms, or a substituted or unsubstituted alkenyl group having 2 to 6 carbon atoms, wherein the substituent is an alkyl group, a halogen atom,
At least one substituent selected from an alkoxyl group; the carbon number does not include the carbon number of these substituents; R ⁴ and R ⁵ each independently represent a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted group; A substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted alkoxyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted phenyl group, wherein the substituent is selected from an alkyl group, a halogen atom and an alkoxyl group. And the carbon number does not include the carbon number of these substituents, and L ⁺ is a metal cation, a quaternary ammonium ion, a quaternary pyridinium ion, a quaternary quinolinium ion, or It is a phosphonium ion. ), At least one in one molecule
Is a compound having a boron-aryl bond.

A borate compound having no boron-aryl bond has an extremely poor storage stability and is not preferred because it readily reacts with oxygen in the air and decomposes.

Specific examples of suitably used aryl borate compounds include borate compounds having one aryl group per molecule, such as trialkylphenylboron, trialkyl (p-chlorophenyl) boron, trialkyl ( p-fluorophenyl) boron, trialkyl (3,5-bistrifluoromethyl) phenylboron,
Trialkyl [3,5-bis (1,1,1,3,3,3
-Hexafluoro-2-methoxy-2-propyl) phenyl] boron, trialkyl (p-nitrophenyl) boron, trialkyl (m-nitrophenyl) boron, trialkyl (p-butylphenyl) boron, trialkyl (m- Butylphenyl) boron, trialkyl (p-butyloxyphenyl) boron, trialkyl (m-butyloxyphenyl) boron, trialkyl (p-octyloxyphenyl) boron, trialkyl (m-octyloxyphenyl) boron Groups are n-butyl group, n-octyl group, n-dodecyl group, etc.) sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt,
Examples thereof include tetraethylammonium salt, triethanolamine salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt, butylquinolinium salt and the like.

The borate compounds having two aryl groups in one molecule include dialkyldiphenylboron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron, dialkyldi (3,5-bistrifluoro). Methyl) phenylboron, dialkyldi [3,5-bis (1,1,1,3,3,3-
Hexafluoro-2-methoxy-2-propyl) phenyl] boron, dialkyldi (p-nitrophenyl) boron, dialkyldi (m-nitrophenyl) boron, dialkyldi (p-butylphenyl) boron, dialkyldi (m-butylphenyl) boron, Dialkyldi (p-butyloxyphenyl) boron, dialkyldi (m-butyloxyphenyl) boron, dialkyldi (p-octyloxyphenyl) boron, dialkyldi (m-octyloxyphenyl) boron (the alkyl group is the same as above)
Sodium, lithium, potassium, magnesium, tetrabutylammonium, tetramethylammonium, tetraethylammonium, triethanolamine, methylpyridinium, ethylpyridinium, butylpyridinium, methylquinolinium, Ethyl quinolinium salt, butyl quinolinium salt and the like can be mentioned.

Further, borate compounds having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) boron, monoalkyltriphenylboron Tri (3,5-bis (trifluoromethyl) phenylboron, monoalkyltri [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, mono Alkyl tri (p-nitrophenyl) boron, monoalkyl tri (m-nitrophenyl) boron, monoalkyl tri (p
-Butylphenyl) boron, monoalkyltri (m-butylphenyl) boron, monoalkyltri (p-butyloxyphenyl) boron, monoalkyltri (m-butyloxyphenyl) boron, monoalkyltri (p-octyloxyphenyl) ) Boron, monoalkyltri (m
Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, triethanolamine salt, methylpyridinium salt of -octyloxyphenyl) boron (the alkyl group is as defined above); Ethyl pyridinium salts, butyl pyridinium salts, methyl quinolinium salts, ethyl quinolinium salts, butyl quinolinium salts and the like.

The borate compounds having four aryl groups in one molecule include tetraphenylboron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, 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, tetrakis (p-octyloxyphenyl) boron, tetrakis (m-octyloxyphenyl) boron, (p-fluorophenyl) triphenylboron, (3,5-bistrifluoromethyl) phenyl Triphenylboron, (p-
(Nitrophenyl) triphenylboron, (m-butyloxyphenyl) triphenylboron, (p-butyloxyphenyl) triphenylboron, (m-octyloxyphenyl) triphenylboron, (p-octyloxyphenyl) triphenylboron , Sodium, lithium, potassium, magnesium, tetrabutylammonium, tetramethylammonium, tetraethylammonium, triethanolamine, methylpyridinium, ethylpyridinium, butylpyridinium, methylquinolinium , Ethyl quinolinium salts, butyl quinolinium salts and the like.

In consideration of storage stability, it is more preferable to use a borate compound having three or four aryl groups in one molecule.

The borate compounds may be used alone or in combination of two or more.

These aryl borate compounds are used in an amount of 0.01 to 2 parts by weight per 100 parts by weight of the acidic group-containing polymerizable monomer.
It is preferable to add it in the range of 0 parts by weight. More preferably, it is in the range of 0.05 to 15 parts by weight. If the amount is less than 0.01 part by weight, the polymerizability decreases, and if the amount is more than 20 parts by weight, various physical properties of the cured product, for example, weather resistance, are undesirably reduced. In the case where a radical polymerizable monomer (described later) other than the acidic group-containing polymerizable monomer is further added, the total polymerizable monomer is calculated as 100 parts by weight.

The filler as the component (F) used in the dental adhesive of the present invention is necessary to give a cured product of the adhesive a strength that can withstand clinical use. Organic fillers are used without any restrictions.

Specific examples of the inorganic filler include quartz, silica, silica-alumina, silica-titania, silica-zirconia, silica-magnesia, silica-calcia, silica-barium oxide, silica-strontium oxide, and silica-titania. Sodium oxide, silica-titania-potassium oxide, silica-zirconia-sodium oxide, silica-zirconia-potassium oxide, titania, zirconia,
Alumina and the like can be mentioned.

An ion-eluting filler that elutes a cation under an acidic solution is also preferably used. Specific examples of the ion-eluting filler include calcium hydroxide,
Examples include hydroxides such as strontium hydroxide, zinc oxide, silicate glass, fluoroaluminosilicate glass, barium glass, and strontium glass. Among them, fluoroaluminosilicate glass is the most excellent and preferable in view of the coloring resistance of the cured product. As the fluoroaluminosilicate glass, a known material used as a dental cement can be used. Commonly known compositions of fluoroaluminosilicate glass include, by weight percent ion, silicon, 10-33; aluminum, 4-3.
0; alkaline earth metal, 5-36; alkali metal, 0
10; phosphorus, 0.2 to 16; fluorine, 2 to 40 and residual oxygen are preferably used. It is also preferable that part or all of the alkaline earth metal is substituted with magnesium, strontium, or barium. In particular, strontium is often suitably used because it gives radiopaque and high strength to the cured product.

These inorganic fillers may be preferably treated with a surface treatment agent represented by a silane coupling agent, and the surface treatment may be performed by a known method. Ring agents are preferably used.

Specific examples of the organic filler include polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer,
Ethyl methacrylate-butyl methacrylate copolymer, methyl methacrylate-trimethylolpropane trimethacrylate copolymer, polyvinyl chloride, polystyrene, chlorinated polyethylene, nylon, polysulfone,
Polyether sulfone, polycarbonate and the like can be mentioned.

An inorganic-organic composite filler obtained by pulverizing a composite of an inorganic oxide and a polymer is also preferably used.

The shape of these fillers is not particularly limited.
It may be pulverized particles as obtained by ordinary pulverization or spherical particles. The particle size of the filler is not particularly limited, but is preferably 100 μm or less, more preferably 30 μm or less in terms of coating thickness for obtaining good compatibility of the prosthesis. You.

The addition amount of these fillers is preferably in the range of 50 to 900 parts by weight based on 100 parts by weight of the acidic group-containing polymerizable monomer. More preferably, it is 100 to 800 parts by weight. If the amount is less than 50 parts by weight, the physical strength of the material is reduced, and if it is more than 900 parts by weight, the fluidity of the cement is reduced and the operability is reduced. In the case where a radical polymerizable monomer (described later) other than the acidic group-containing polymerizable monomer is further added, the total polymerizable monomer is calculated as 100 parts by weight.

The dental adhesive of the present invention comprises (D) an acidic group-containing polymerizable monomer, (E) an aryl borate compound,
And (F) other than the filler, other than the acidic group-containing polymerizable monomer (G) other than the acidic group-containing polymerizable monomer, for the purpose of adjusting the viscosity or adjusting other physical properties, as long as the effects of the present invention are not impaired. It is also useful to incorporate a monomer.

Specific examples of the other radical polymerizable monomers as the component (G) include the radical polymerizable monomers specifically exemplified as optional components in the dental primer.

The addition amount of these other radical polymerizable monomers is 1 to 100 parts by weight of the acidic group-containing polymerizable monomer.
The range is preferably from 0 to 2000 parts by weight, more preferably from 20 to 1500 parts by weight.

Further, the dental adhesive of the present invention contains (H) other than the aryl borate compound for the purpose of controlling physical properties and the like.
It is also useful to incorporate a polymerization initiator.

The polymerization initiator (H) is not particularly limited, and known chemical polymerization initiators and photopolymerization initiators can be used without limitation.

As the chemical polymerization initiator, organic peroxides /
An amine compound or a redox-type polymerization initiator composed of an organic peroxide / amine compound / sulfinate, an organometallic-type polymerization initiator that reacts with oxygen or water to initiate polymerization,
And a polymerization initiator composed of (thio) barbituric acid derivative / cupric ion / halogen compound.

Examples of the organic peroxide include t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, acetyl peroxide, lauroyl peroxide, benzoyl peroxide and the like.

The amine compound is preferably a secondary or tertiary amine having an amino group bonded to an aryl group.
Specifically, N, N-dimethyl-p-toluidine, N, N-dimethylaniline, N- (2-hydroxyethyl) aniline, N, N-di (2-hydroxyethyl) -p-toluidine, N -Methylaniline, N-methyl-p-toluidine and the like are preferred.

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

Further, examples of the organometallic polymerization initiator include:
Boron compounds such as triphenylborane, tributylborane, and tributylborane partial oxide are exemplified.

The (thio) barbituric acid derivatives include 5
-Butyl (thio) barbituric acid, 1,3,5-trimethyl (thio) barbituric acid, 1-benzyl-5-phenyl (thio) barbituric acid, 1-cyclohexyl-5-methyl (thio) barbituric acid, 1-cyclohexyl And -5-butyl (thio) barbituric acid.

Examples of the halogen compound include dilauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride, benzyltrimethylammonium chloride, tetramethylammonium chloride, benzyldimethylcetylammonium chloride,
Dilauryl dimethyl ammonium bromide and the like.

Examples of the photopolymerization initiator include those composed of a photosensitizer alone, those composed of a photosensitizer / photopolymerization accelerator, dyes / photoacid generators / sulfinates, and dyes / photoacid generators / And those made of borate.

Examples of the photosensitizer include camphorquinone, benzyl, α-naphthyl, acetonaphthene, naphthoquinone, p, p′-dimethoxybenzyl, p, p′-dichlorobenzylacetyl, 1,2-phenanthrenequinone,
Α-diketones such as 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, thioxanthones such as 2,4-diethylthioxanthone, 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-
Α-aminoacetophenones such as morpholinophenyl) -pentanone-1, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-
Acylphosphine oxide derivatives such as dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide.

As photopolymerization accelerators, 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, ethyl p-dimethylaminobenzoate, amyl p-dimethylaminobenzoate, N, N-dimethylanthranilic Acid methyl ester, N, N-dihydroxyethylaniline, N, N
-Dihydroxyethyl-p-toluidine, p-dimethylaminophenethyl alcohol, p-dimethylaminostilpene, 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 amines such as N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, 2,2 '-(n-butylimino) diethanol And barbituric acids such as 5-butyl barbituric acid and 1-benzyl-5-phenyl barbituric acid.

Specific examples of preferably used 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 the photoacid generator include 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-
Halomethyl-substituted-s-triazine derivatives such as trimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 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, etc. Diphenyliodonium salt compounds are exemplified.

As the sulfinates, those specifically exemplified in the section of the redox type polymerization initiator can be used similarly, and the borates can be similarly used as those exemplified in the general formula (1). .

These polymerization initiators can be added alone or in combination as necessary.

When the dental adhesive of the present invention is used as a dental resin cement by adding the above-mentioned inorganic filler, organic filler and the like, in addition to the aryl borate compound which is an essential component as a polymerization catalyst, Addition of a peroxide such as benzoyl peroxide and an amine such as dimethyl-p-toluidine is preferred from the viewpoint of controlling the polymerization rate and the like so that coloring does not become a problem. Further, by adding α-diketones such as camphorquinone and amines such as dimethylaminobenzoic acid ethyl ester, the resin cement is suitably used as a dual-curing chemical cement or light cement.

The addition amount of these polymerization initiators is preferably in the range of 0.01 to 20 parts by weight based on 100 parts by weight of the total of the acidic group-containing polymerizable monomer and other polymerizable monomers.

In the dental adhesive of the present invention, an organic solvent, a thickener and the like can be added in order to adjust the viscosity of the adhesive within a range that does not deteriorate the performance.

Examples of the organic solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, and 2-methyl-2.
-Butanol, 2-propen-1-ol, 2-propyn-1-ol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,3-
Butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, ethylene glycol, propanediol, butanediol, pentanediol, butenediol, glycerin, trimethylolpropane, hexanetriol, allyl alcohol , Diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 2-methoxyethanol, 2-ethoxyethanol, 2- ( Methoxyethoxy) ethanol, 2-isopropoxyethanol, 2-butoxyethanol, 1-methoxy -2-propanol, 1-ethoxy-2-propanol, alcohols or ethers such as dipropylene glycol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, glycerin ether, ketones such as acetone and methyl ethyl ketone, hexane, heptane, octane, toluene , Dichloromethane, chloroform, ethyl acetate, propyl acetate, dimethyl sulfoxide and the like.

Among them, those having little harmful effect on the living body are desirable, and ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, -Methyl-2-butanol, 2-propene-1-
All, 2-propyn-1-ol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butane Diol, 1,5-pentanediol, ethylene glycol, propanediol, butanediol, pentanediol, glycerin, trimethylolpropane, hexanetriol, allyl alcohol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol, triethylene Glycol monomethyl ether, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, dipropylene glycol, dipropylene glycol Bruno methyl ether, tripropylene glycol monomethyl ether, glycerine ether,
Acetone and the like are preferred, and particularly, ethanol, propanol, ethylene glycol, propanediol, acetone and the like are most preferably used.

The above organic solvents can be used as a mixture of two or more if necessary.

To the dental adhesive of the present invention, if necessary, a small amount of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, 2,6-ditert-butylphenol is added to improve the storage stability and environmental light stability. Is preferred.

[0102] The packaging form of the dental adhesive in the present invention can be appropriately determined on condition that storage stability is not impaired. For example, acidic group-containing polymerizable monomer, a liquid mainly containing another polymerizable monomer, and a powder mainly containing an aryl borate compound and a filler are separately packaged,
It is possible to mix at the time of use. It is also possible to separately package a paste composed mainly of an acidic group-containing polymerizable monomer and a filler, and another paste composed of a polymerizable composition, an aryl borate compound and a filler, and mix them at the time of use.

A typical method of using a dental adhesive kit comprising the dental primer and the dental adhesive of the present invention will be described below. The dental primer of the present invention is applied to the tooth surface using a sponge or a small brush, left standing for several seconds to several minutes, and then dried by blowing air. Then, after applying the dental adhesive of the present invention onto the pretreated tooth surface, various restorative materials are brought into contact with each other, and then the adhesive is polymerized and cured to adhere. According to this method, the restoration material, the crown material, and the like can be firmly bonded to the tooth material.

[0104]

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. The abbreviations or structures of the compounds used in the examples are shown below.

(1) Abbreviation or structure PM: 2-methacryloyloxyethyl dihydrogen phosphate PM2: bis (2-methacryloyloxyethyl) hydrogen phosphate MAC-10: 11-methacryloyloxy-1,1-
Undecanedicarboxylic acid AMPS: 2-acrylamide-2-methylsulfonic acid Bis-GMA: 2,2-bis (4- (2-hydroxy-3-methacryloyloxypropoxy) phenyl) propane D-2.6E: 2,2- Bis (4- (methacryloxyethoxy) phenyl) propane HEMA: hydroxyethyl methacrylate 3G: triethylene glycol dimethacrylate MMA: methyl methacrylate BPO: benzoyl peroxide DMPT: N, N-dimethyl-p-toluidine PTSNa: p-toluenesulfin Acid sodium PBNa: sodium salt of tetraphenylboron IPA: isopropyl alcohol

[0106]

Embedded image

[0107]

Embedded image

[0108]

Embedded image

[0109]

Embedded image

F1: A filler obtained by surface-treating quartz powder (non-spherical pulverized product) having an average particle size of 9 μm with 1% by weight of γ-methacryloxypropyltrimethoxysilane.

F2: Filler obtained by subjecting spherical silica-zirconia having an average particle size of 0.2 μm to surface treatment with 2% by weight of γ-methacryloxypropyltrimethoxysilane.

F3: Fluoroaluminosilicate glass (Tokusoh Glass Ionomer Cement Powder (manufactured by Tokuyama Co., Ltd.)) F4: A mixture of 60 parts by weight of Bis-GMA and 40 parts by weight of 3G in F2 to form a paste was used as a catalyst. An inorganic-organic composite filler having an average particle size of 20 μm obtained by heating and polymerizing azobisisobutyronitrile and pulverizing the obtained cured product.

F5: Organic filler obtained by pulverizing polymethyl methacrylate and having an average particle size of 50 μm (2) Enamel and dentin adhesive strength Within 24 hours after slaughter, the bovine anterior teeth were removed, 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. The dental primer of the example or the comparative example was applied to the simulated cavity, left for 30 seconds, and then blown with compressed air for about 5 seconds. Thereafter, the dental adhesive of the example or the comparative example was filled in the simulated cavity, and then a stainless steel attachment having a diameter of 8 mmφ was pressed on the simulated cavity to produce an adhesive test piece. In addition, when the photopolymerization initiator was added (Examples 39, 43, and 48), after the attachment was pressed, light irradiation was performed for 30 seconds from each of four directions around the attachment to obtain an adhesion test piece.

After immersing the adhesive test piece in water at 37 ° C. for 24 hours, 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).

Example 1 A dental primer A was prepared consisting of 1.0 g PM, 0.5 g PM2, 0.005 g cupric chloride, 3.5 g IPA and 5 g water. Also, 2g of PM2 and 1
g MAC-10, 0.3 g PBNa and 7
A powder composed of g of F1 was separately prepared in advance, and the liquid and the powder were kneaded immediately before use to obtain a dental adhesive. The adhesive strength was measured using the prepared primer A and the adhesive. As a result, a high adhesive strength of 18.9 MPa to enamel and 15.4 MPa to dentin was obtained.

Example 2-16 A dental primer having the composition shown in Table 1 and a dental adhesive having the composition shown in Table 2 were prepared in the same manner as in Example 1. As a result of measuring the adhesive strength using the primer and the adhesive prepared in the same manner as in Example 1, a high adhesive strength was obtained with any composition.

[0117]

[Table 1]

[0118]

[Table 2]

Example 17 A solution consisting of 0.4 g of MAC-10 and 3.0 g of MMA as a radical polymerizable monomer other than the polymerizable monomer having an acidic group, 0.1 g of PBNa and 6.5 g of A powder consisting of F5 was separately prepared in advance, and the liquid and the powder were kneaded immediately before use to prepare a dental adhesive, and the adhesive strength was measured (primer A was used as a dental primer). As a result, 20.3 MPa for enamel and 1 for dentin
A high adhesive strength of 7.1 MPa was obtained.

Examples 18-30 In the same manner as in Example 17, a dental adhesive having the composition shown in Table 3 was prepared, and the adhesive strength was measured. As a result, high adhesive strength was exhibited in all compositions. Further, by adding a polymerizable monomer other than the acidic group-containing polymerizable monomer and a polymerization initiator, a further improvement in the adhesive strength to dentin was observed.

[0121]

[Table 3]

Example 31 A paste consisting of 1 g of MAC-10 and 3.0 g of F1, 0.3 g of FPBNa, 3.0 g of F1, 2 g of 3
A paste consisting of G and 1 g of D-2.6E was separately prepared in advance, and the two pastes were kneaded immediately before use to form a dental adhesive, and the adhesive strength was measured (using primer A as a dental primer). did). As a result, 20.2 MPa for enamel and 17.3 M for dentin
A high adhesive strength of Pa was obtained.

Examples 32-48 Dental adhesives having the compositions shown in Table 4 were prepared in the same manner as in Example 31, and the adhesive strength was measured. In addition, two pastes were prepared by dividing the amount of the filler in half. As a result, all the examples showed high adhesive strength. When a photopolymerization initiator was added (Examples 39, 43, and 48)
It was also possible to adjust the curing time by light irradiation.

[0124]

[Table 4]

Comparative Example 1 A dental primer M consisting of 0.01 g of cupric chloride, 3 g of IPA and 7 g of water was prepared. In addition, a liquid composed of 3 g of MAC-10, a powder composed of 0.3 g of PBNa and 7 g of F1 were separately prepared in advance, and the liquid and the powder were kneaded immediately before use to obtain a dental adhesive. The adhesive strength was measured using the prepared dental primer M and dental adhesive. As a result, it was 0.6 MPa for enamel and 4.3 MPa for dentin. This is an example in which no acid was added to the primer, and particularly the adhesion strength to enamel was greatly reduced.

Comparative Example 2-4 A dental primer having the composition shown in Table 5 and a dental adhesive having the composition shown in Table 6 were prepared in the same manner as in Comparative Example 1. Using the prepared primer and the adhesive, the adhesive strength was measured in the same manner as in Comparative Example 1. As a result, in Comparative Example 2, since no acid was added to the primer, the adhesive strength particularly to enamel was greatly reduced. Comparative Example 3 was an example in which the metal compound was not added, and the adhesive strength to dentin was reduced. Comparative Example 4 is an example in which a solvent containing water was not added to the primer, and MA was used in which the metal compound was an acid.
It did not dissolve in C-10, a uniform solution was not obtained, and the adhesion test could not be performed because the primer did not have an appropriate viscosity.

Comparative Example 5 0.3 g of a liquid composed of 2 g of 3G and 1 g of D-2.6E
Of m-C4PBNa and 7 g of F1 were separately prepared in advance, and the liquid and the powder were kneaded immediately before use to obtain a dental adhesive. The adhesive strength was measured using the prepared adhesive and the previously prepared dental primer A. as a result,
0.7MPa for enamel, 6.1M for dentin
Pa. This is an example in which no acidic group-containing polymerizable monomer was added to the adhesive, and particularly the adhesive strength to enamel was reduced.

Comparative Example 6-8 A dental adhesive having the composition shown in Table 6 was prepared in the same manner as in Comparative Example 5, and the adhesive strength was measured. As a result, in Comparative Example 6, since no filler was added, the strength of the composition was low and the bonding strength was low. In Comparative Examples 7-8, the aryl borate compound was not added, and the polymerizability was poor and the adhesive strength was reduced.

[0129]

[Table 5]

[0130]

[Table 6]

[0131]

The adhesive kit comprising the dental primer and the dental adhesive of the present invention has high adhesive strength to both enamel and dentin in one pretreatment. Therefore,
It is effective as an adhesive kit for tooth material, and is particularly effective for bonding tooth restoration with a crown restoration such as metal or ceramics.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4C081 AB06 AC04 BB04 CA081 CA082 CA272 CA282 CB021 CE08 CE11 CF122 CF132 DA14 DC12 4C089 AA11 BA04 BA05 BA13 BA14 BA19 BA20 BC08 BC13 BD01 BD02 BD09 BD10 BD11 BE02 BE03 CA03 CA09

Claims (4)

[Claims] (1) an acid, (B) a copper compound, an iron compound,
And at least one metal compound selected from the group consisting of: and a cobalt compound; (C) a dental primer comprising water; (D) an acidic group-containing polymerizable monomer;
An adhesive kit for a dentin, comprising a combination of an aryl borate compound and a dental adhesive comprising (F) a filler. 2. An acid (A), a copper compound (B), an iron compound,
And at least one metal compound selected from the group consisting of: and a cobalt compound; (C) a dental primer comprising water; (D) an acidic group-containing polymerizable monomer;
An adhesive kit for a dentin, comprising a combination of an aryl borate compound, (F) a filler and (G) a radically polymerizable monomer {excluding the component (D)} with a dental adhesive. 3. An acid (A), a copper compound (B), an iron compound,
And at least one metal compound selected from the group consisting of: and a cobalt compound; (C) a dental primer comprising water; (D) an acidic group-containing polymerizable monomer;
A dental adhesive comprising an aryl borate compound, (F) filler, (G) radically polymerizable monomer {excluding component (D)} and (H) polymerization initiator {excluding component (E)} An adhesive kit for dentin, comprising a combination of: 4. The (B) metal compound in the dental primer is an iron halide or a copper halide, and the (E) aryl borate compound in the dental adhesive is represented by the following general formula (1). 4. A borate compound.
The adhesive kit for dentin according to the above. Embedded image (Provided that R ¹ , R ² and R ³ each independently represent a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted carbon group; An aralkyl group having 2 to 6 carbon atoms, or a substituted or unsubstituted alkenyl group having 2 to 6 carbon atoms, wherein the substituent is at least one substituent selected from an alkyl group, a halogen atom, and an alkoxyl group; The carbon number does not include the carbon number of these substituents, and R ⁴ and R ⁵ each independently represent a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted group. A substituted or unsubstituted phenyl group, wherein the substituent is at least one selected from an alkyl group, a halogen atom and an alkoxyl group Is a substituent, the carbon number of substituents on the carbon atoms are not included, L ⁺ is a metal cation, quaternary ammonium ion, a quaternary pyridinium ion, quaternary quinolinium ion or phosphonium ion. )