JPH09309811A - Adhesive composition for dental use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition causing to drop-off of its polymerization degree, and especially effective for bonding the dentine to prosthetic material such as metal or ceramic. SOLUTION: This adhesive composition for dental use comprises (A) 100 pts.wt. of an acidic group-bearing polymerizable monomer of e.g. formula I (R1 is H, methyl, etc.,; Z is oxycarbonyl group, amido group, etc.,; R2 is a lone pair, 1-30C organic residue, etc.,; X is phosphate group, etc.,; (1) is a positive number of 1-4; (m) and (n) are each positive number of 1 or 2; when Z is oxycarbonyl or amido, R2 is not a lone pair), (B) 0.01-20 pts.wt. of an aryl borate compound of formula II (R<3> , R<4> and R<5> are each an alkyl, etc.,; R<6> and R<7> are each H, a halogen, etc.,; L<+> is a metallic cation, etc.,) (e.g. a trialkylphenylboron) and (C) 50-900 pts.wt. of a filler.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composition useful as a dental material, particularly a dental adhesive material.

[0002]

2. Description of the Related Art Conventionally, for restoration of a tooth damaged by caries or the like, a prosthesis such as metal or ceramics has been bonded with zinc phosphate cement, eugenol cement or the like. However, these materials have a weak adhesive force with the tooth structure and have problems such as falling off and secondary caries, and adhesive materials such as resin cement have been developed for the purpose of improving this defect. Many of these adhesive materials contain acidic group-containing polymerizable monomers, but under such acidic conditions, polymerization of peroxide / tertiary amine which is a general redox initiator. When a catalyst is used, there are problems that the polymerizability decreases due to the quaternization of amine, clinically sufficient adhesive force cannot be obtained, and coloring occurs.

On the other hand, as an example of using an organic boron compound as a radical polymerization initiator, it is known to decompose a trialkylboron compound in the presence of oxygen to polymerize a polymerizable unsaturated compound. However, the organoboron compound is very unstable in the air and has a risk of ignition and the like, and it is generally difficult to use.

Further, JP-A-6-329712 and JP-A-8-3210 disclose a polymerizable composition comprising an acid compound, a polymerizable unsaturated compound and a borate-based polymerization initiator which is a tetracoordinated boron compound. . However, the acidic compound used here is added in order to decompose the borate and generate radicals and does not polymerize by itself, so that the strength of the cured product cannot be sufficiently obtained, and the dental adhesive material. When used as, the strength was insufficient. In addition, there is a concern that the pulp may be damaged if an acid that does not polymerize remains after the operation.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a dental adhesive composition which exhibits high adhesive strength even under acidic conditions in which an acidic group-containing polymerizable monomer is present.

[0006]

Means for Solving the Problems As a result of intensive studies to overcome the above technical problems, the present inventors have found that an acidic group-containing Z
When is an ester group or an amide group, R ₂ does not serve as a bond. It was found that the polymerizable monomer, the aryl borate compound, and the filler are combined to have high polymerizability even under acidic conditions and excellent adhesiveness to the tooth structure.

That is, the present invention comprises (A) 100 parts by weight of an acidic group-containing polymerizable monomer, (B) an aryl borate compound (0.01 to 20 parts by weight), and (C) a filler (50 to 9).
A dental adhesive composition comprising 100 parts by weight.

The acidic group-containing polymerizable monomer which is the component (A) used in the present invention is a polymerizable monomer having at least one acidic group and at least one polymerizable unsaturated group in one molecule. There is no particular limitation so long as it is a known compound.

As the acidic group, a phosphoric acid group, a carboxylic acid group,
A carboxylic acid anhydride group and a sulfonic acid group are preferable. A polymerizable monomer having a representative phosphoric acid group, carboxylic acid group, carboxylic acid anhydride group, and sulfonic acid group is represented by the following general formula (1).

[0010]

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[In the above general formula, R ₁ is a hydrogen atom or a methyl group, Z is an oxycarbonyl group (-COO-), an amide group (-CONH-), or a phenylene group (-C ₆ H
₄ −), R ₂ is a bond, or an ether bond and / or
Alternatively, a divalent to hexavalent organic residue having 1 to 30 carbon atoms, which may have an ester bond, X represents a group containing a phosphoric acid group, a carboxylic acid group, a carboxylic acid anhydride group, or a sulfonic acid group. , 1 represents a positive number of 1 to 4, and m and n represent a positive number of 1 or 2. However, when Z is an oxycarbonyl group or an amide group, R ₂ does not serve as a bond. In the general formula (1), X is a group containing a phosphoric acid group, a carboxylic acid group, a carboxylic acid anhydride group, and a sulfonic acid group, and the structure thereof is not particularly limited, but preferred specific examples are It is as follows.

[0012]

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In the above general formula (1), the structure of R ₂ is not particularly limited, and has 2 to 6 carbon atoms which may have a bond or a known ether bond and / or ester bond. Although 1 to 30 organic residues can be adopted, specific examples of the organic residues are as follows. The case where R ₂ is a bond means a state in which the group Z and the group X are directly bonded,
R ₂ when Z is an oxycarbonyl group or an amide group
Does not serve as a bond but becomes the above-mentioned organic residue.

[0014]

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Preferred specific examples of the acidic group-containing polymerizable monomer represented by the general formula (1) are as follows.

[0016]

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[0017]

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[0018]

[Chemical 6]

[0019]

[Chemical 7]

In addition, vinylphosphonic acids in which a phosphoric acid group is directly bonded to a vinyl group, acrylic acid, methacrylic acid,
Vinylsulfonic acid and the like are also mentioned as preferable specific examples of the acidic group-containing polymerizable monomer.

These acidic group-containing polymerizable monomers can be used alone or in admixture of two or more.

Typical aryl borate compounds which are the component (B) used in the present invention are represented by the following general formula (2).

[0023]

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(Provided that R ₃ , R ₄ and R ₅ are the same or different and may be substituted alkyl group, aryl group, aralkyl group and alkenyl group, respectively, and R ₆ or R ₇ is hydrogen atom, halogen An atom, an optionally substituted alkyl group or a phenyl group, and L ⁺ is a metal cation, a quaternary ammonium ion, a quaternary pyridinium ion, a quaternary quinolinium ion or a phosphonium ion.), It is a borate compound having at least one boron-aryl bond in one molecule.

A borate compound having no boron-aryl bond is not preferable because it has extremely poor storage stability and easily reacts with oxygen in the air to decompose.

Specific examples of the aryl borate compounds that are preferably used include trialkylphenylboron, trialkyl (p-chlorophenyl) boron and trialkyl (boron compounds having one aryl group in one molecule. 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 (alkyl Groups are n-butyl group, n-octyl group, n-dodecyl group, etc.), sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt,
Tetraethylammonium salt, methylpyridinium salt,
Examples thereof include ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt and butylquinolinium salt.

Examples of the borate compound having two aryl groups in one molecule include dialkyldiphenylboron, dialkyldi (p-chlorophenyl) boron, dialkyldi (p-fluorophenyl) boron and 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 (alkyl group is the same as above)
Sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinolinium salt, ethylquinolinium salt ,
Butyl quinolinium salt etc. are mentioned.

Further, examples of the borate compound having three aryl groups in one molecule include monoalkyltriphenylboron, monoalkyltri (p-chlorophenyl) boron, monoalkyltri (p-fluorophenyl) boron and monoalkyl. Tri (3,5-bistrifluoromethyl) phenylboron, monoalkyltri [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, mono Alkyltri (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, monoalkyl tri (m
-Octyloxyphenyl) boron (alkyl group is the same as above) sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butyl Examples thereof include pyridinium salts, methylquinolinium salts, ethylquinolinium salts, butylquinolinium salts and the like.

Examples of the borate compound having four aryl groups in one molecule are 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, 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 , (Alkyl groups are the same as above), sodium salt, lithium salt, potassium salt, magnesium salt, tetrabutylammonium salt, tetramethylammonium salt, tetraethylammonium salt, methylpyridinium salt, ethylpyridinium salt, butylpyridinium salt, methylquinone Examples thereof include a norinium salt, an ethylquinolinium salt, and a butylquinolinium salt.

Considering storage stability, it is more preferable to use a borate compound having 3 or 4 aryl groups in one molecule.

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

These aryl borate compounds are added in an amount of 0.01 to 2 with respect to 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 it is less than 0.01 part by weight, the polymerizability is lowered, and if it is more than 20 parts by weight, various properties of the cured product, for example, weather resistance are lowered, which is not preferable.

The filler which is the component (C) used in the present invention is necessary in order to give the cured product of the dental adhesive composition of the present invention a strength sufficient for clinical use, and it is a generally used inorganic material. Fillers and organic fillers can be used without any limitation.

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, silica-titania-sodium oxide, silica-titania-potassium oxide, silica-alumina- Examples thereof include sodium oxide, silica-alumina-potassium oxide, titania, zirconia, and alumina.

These inorganic fillers can be treated with a surface treatment agent typified by a silane coupling agent without any problem. The surface treatment may be carried out by a known method, and as the silane coupling agent, γ-methacryloxypropyltrimethoxysilane, ε-methacryloxyoctyltrimethoxysilane, vinyltrimethoxysilane and the like are preferably used.

Ion-eluting fillers that elute cations in an acidic solution are also preferably used. Specific examples of the ion-eluting filler include calcium hydroxide,
Examples thereof 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, known materials used as dental cement can be used. The composition of commonly known fluoroaluminosilicate glasses is, in ionic weight percent, silicon, 10-33; aluminum, 4-3.
0; alkaline earth metal, 5 to 36; alkali metal, 0
10; phosphorus, 0.2 to 16; fluorine, 2 to 40 and residual oxygen are preferably used. It is also preferable to replace a part or all of the above alkaline earth metal with magnesium, strontium, or barium. Particularly, strontium is often suitably used because it gives a cured product radiopaque properties and high strength.

Specific examples of the organic filler include polymethylmethacrylate, polyethylmethacrylate, methylmethacrylate-ethylmethacrylate copolymer, ethylmethacrylate-butylmethacrylate copolymer,
Methyl methacrylate-trimethylolpropane trimethacrylate copolymer, polyvinyl chloride, polystyrene, chlorinated polyethylene, nylon, polysulfone, polyether sulfone, polycarbonate and the like can be mentioned.

Inorganic / organic composite fillers obtained by pulverizing a composite of an inorganic oxide and a polymer are also preferably used.

When the above-mentioned inorganic filler or organic filler is used, it becomes a dental resin cement, and when an ion-eluting filler is used, it becomes a glass ionomer cement.

The shape of these fillers is not particularly limited, and may be pulverized particles obtained by ordinary pulverization or spherical particles.

The particle size of these fillers is not particularly limited, but those having a particle size of 100 μm or less are preferably used from the viewpoint of operability. The addition amount of these fillers is preferably in the range of 50 to 900 parts by weight with respect to 100 parts by weight of the acidic group-containing polymerizable monomer. More preferably, it is 100 to 800 parts by weight.

When the amount is less than 50 parts by weight, the physical strength of the material is lowered, and when the amount is more than 900 parts by weight, the compatibility with the acidic group-containing polymerizable monomer is deteriorated and the operability is lowered. When a polymerizable monomer other than the acidic group-containing polymerizable monomer described below is further blended, the amount of all the polymerizable monomers is 100 parts by weight for calculation.

The dental adhesive composition of the present invention is polymerized by mixing a polymerizable monomer other than the acidic group-containing polymerizable monomer in order to adjust the viscosity or other physical properties. It is also useful to do.

As the other polymerizable monomer which is the component (D) used in the present invention, known compounds can be used without any limitation.
Specific examples of preferable other polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate,
Glycidyl (meth) acrylate, 2-cyanomethyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, 3 -Hydroxypropyl (meth) acrylate,
Mono (meth) such as glyceryl mono (meth) acrylate
Acrylate monomer; ethylene glycol di (meth)
Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate,
Propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, 2,2'-
Bis [4- (meth) acryloyloxyethoxyphenyl] propane, 2,2′-bis [4- (meth) acryloyloxyethoxyethoxyphenyl] propane, 2,
2'-bis [4- (meth) acryloyloxyethoxyethoxyethoxyethoxyethoxyethoxyethoxyethoxyphenyl] propane, 2,2'-bis {4- [3- (meth) acryloyloxy-2-hydroxypropoxy]
Phenyl} propane, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane tri (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, etc. Examples thereof include (meth) acrylate-based monomers.

Further, it is possible to mix and polymerize a polymerizable monomer other than the above-mentioned (meth) acrylate type monomer. Examples of these other polymerizable monomers include fumaric acid ester compounds such as monomethyl fumarate, diethyl fumarate, and diphenyl fumarate; styrene such as styrene, divinylbenzene, α-methylstyrene, and α-methylstyrene dimer. α-Methylstyrene derivatives; allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl carbonate and allyl diglycol carbonate. These other polymerizable monomers can be used alone or in admixture of two or more.

The amount of these other polymerizable monomers added is 10 to 90 relative to 100 parts by weight of the acidic group-containing polymerizable monomer.
The range of 0 parts by weight is preferable, and more preferably 20 to 80.
The range is 0 parts by weight.

Further, the dental adhesive composition of the present invention can be used in combination with other known polymerization initiators used for thermal polymerization and photopolymerization. There is no limitation on other polymerization initiators, but if other polymerization initiators that are suitably used are illustrated,
As the thermal polymerization initiator, t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide,
Dicumyl peroxide, acetyl peroxide, lauroyl peroxide,
Examples thereof include peroxides such as benzoyl peroxide and azo compounds such as azobisisobutyronitrile.

As the photopolymerization initiator, camphorquinone, benzyl, α-naphthyl, acetonaphthene, naphthoquinone, p, p'-dimethoxybenzyl, p, p'-
Α-diketones such as dichlorobenzylacetyl, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone and 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-
Α such as (4-morpholinophenyl) -pentanone-1
Examples include acylphosphine oxide derivatives such as -aminoacetophenones, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide.

Particularly preferred are α-diketone and acylphosphine oxide type photopolymerization initiators, among which camphorquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,6-
Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide is preferred.

The above-mentioned polymerization initiators may be used alone or in combination of a plurality of types, if necessary.

When the above-mentioned inorganic filler, organic filler, etc. are added and used as a dental resin cement, in addition to the aryl borate compound which is an essential component as a polymerization catalyst, the amount after addition is such that the coloration after polymerization does not become severe. Addition of a peroxide such as benzoyl oxide and an amine such as dimethyl-p-toluidine is preferable in terms of adjusting the polymerization rate. Furthermore, by adding α-diketones such as camphorquinone and amines such as dimethylaminobenzoic acid ethyl ester, the resin is suitably used as a dual cure type resin cement of chemical and light.

When the above-mentioned ion-eluting filler is used as a dental glass ionomer cement, an aryl borate compound which is an essential component as a polymerization catalyst is added to α-diketones such as camphorquinone and ethyl dimethylaminobenzoate. It is preferred to combine amines such as esters. Polymerization of general glass ionomer cement is mainly cross-linking by a chelate bond between an acidic group-containing polymerizable monomer and an ion-eluting filler, but the above-mentioned glass ionomer cement is further provided with chemical polymerization and photopolymerization. It is preferably used as a triple cure type.

The addition amount of these polymerization initiators is 0.01 to 20 parts by weight based on 100 parts by weight of the total amount of the acidic group-containing polymerizable monomer and other polymerizable monomers to be blended as necessary. A range of parts is preferred.

In the composition of the present invention, it is possible to add an organic solvent, a thickener and the like 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, 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 Alcohols such as 2-propanol, 1-ethoxy-2-propanol, 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 which are less harmful to the living body are desirable, and ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 2 -Methyl-2-butanol, 2-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 preferable, and ethanol, propanol, ethylene glycol, propanediol, acetone and the like are most preferably used.

If necessary, a plurality of the above organic solvents may be mixed and used.

The packaging form of the dental adhesive composition of the present invention can be appropriately determined under the condition that the storage stability is not impaired. For example, a liquid containing an acidic group-containing polymerizable monomer and another polymerizable monomer as a main component, and a powder containing an aryl borate compound and a filler as a main component may be separately packaged and mixed at the time of use. It is possible. Further, a paste containing an acidic group-containing polymerizable monomer and a filler as main components,
In addition, it is also possible to separately package a paste composed of a polymerizable composition, an aryl borate compound and a filler and mix them at the time of use.

[0058]

EFFECT OF THE INVENTION The dental adhesive composition of the present invention is characterized in that the acidic group-containing polymerizable monomer can initiate the decomposition of the aryl borate compound and can itself polymerize, so that there is no decrease in the polymerizability. Excellent adhesion to quality. In addition, the cured product obtained by polymerizing the composition of the present invention has no weathering because it is not colored by the oxidation of amine. Therefore, it is effective as a dental adhesive material, and particularly effective for bonding a prosthesis such as metal and ceramics to the tooth structure.

[0059]

EXAMPLES The present invention will be specifically described below 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-acrylamido-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 3G: triethylene glycol dimethacrylate BPO: benzoyl peroxide DMPT: dimethyl-p-toluidine

[0061]

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[0062]

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[0063]

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[0064]

[Chemical 12]

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

F-2: A filler obtained by surface-treating spherical silica-zirconia having an average particle diameter of 0.2 μm with 2% by weight of γ-methacryloxypropyltrimethoxysilane.

F-3: Fluoroaluminosilicate glass (Tokuso glass ionomer cement powder (manufactured by Tokuyama Corporation)) F-4: 60 parts by weight of bis-GMA and 3G40 of F-2.
An inorganic-organic composite filler obtained by dispersing in a solution of 1 part by weight, heat-polymerizing azobisisobutyronitrile as a catalyst to obtain a cured product, and then pulverizing the cured product.

(2) Adhesive strength of enamel and dentin The bovine anterior teeth were removed within 24 hours after slaughter, and under water injection, # 80.
The enamel or dentin plane was carved so as to be parallel to the labial surface with 0 emery paper. Next, compressed air was blown onto these surfaces for about 10 seconds to dry, and then a conditioner attached to Bistit resin cement (manufactured by Tokuyama Corp.) was applied, and after leaving it for 10 seconds, it was washed with water and blown with compressed air for about 5 seconds. . Then, a double-sided tape having a hole with a diameter of 4 mm was fixed on this plane to form a simulated cavity. A primer attached to a bistitite resin cement was applied to the simulated cavity, left for 30 seconds, and then compressed air was blown for about 5 seconds. After that, the dental adhesive composition of Example or Comparative Example was filled in the simulated cavity, and then the diameter was 8 m from the top.
An attachment test piece was prepared by pressing an mφ stainless attachment under pressure.

After the above adhesion test piece was immersed in water at 37 ° C. for 24 hours, a crosshead speed of 10 mm / min was obtained using a tensile tester (Autograph, Shimadzu Corporation).
The adhesive strength with the tooth was measured by.

Example 1 Liquid consisting of 3 g of PM, 0.3 g of PBNa and 7 g of F
The powder consisting of -1 was separately prepared in advance, and the liquid and the powder were kneaded immediately before use to prepare a dental adhesive composition, and the adhesive strength was measured. As a result, 18.1M for enamel
High adhesive strength of 14.1 MPa with respect to Pa and dentin was obtained.

Example 2-34 Dental adhesive compositions having the compositions shown in Tables 1 and 2 were prepared in the same manner as in Example 1 and the adhesive strength was measured. As a result, high adhesive strength was obtained in all compositions. Was given.

Example 35 A paste consisting of 1 g of MAC-10 and 3.0 g of F-1 and 0.3 g of FPBNa, 3.0 g of F-1, 2 g of 3G and 1 g of D-2.6E. The pastes were prepared separately in advance, and immediately before use, the two pastes were kneaded to give a dental adhesive composition, and the adhesive strength was measured. As a result, a high adhesive strength of 18.7 MPa for enamel and 15.9 MPa for dentin was obtained.

Examples 36 to 46 Dental adhesive compositions having the compositions shown in Table 3 were prepared in the same manner as in Example 35, and the adhesive strength was measured. The amount of filler added was divided in half to prepare two pastes. as a result,
All compositions showed high adhesive strength.

Comparative Example 1 0.3 g of a liquid consisting of 2 g of 3G and 1 g of D-2.6E
The powder consisting of m-C4PBNa and 7 g of F-1 was separately prepared in advance, and the liquid and the powder were kneaded immediately before use to prepare a dental adhesive composition, and the adhesive strength was measured. As a result, 0.7 MPa for enamel and 5. MPa for dentin.
It was 6 MPa. This is an example in which the acidic group-containing polymerizable monomer was not added, and particularly the adhesive strength to enamel decreased.

Comparative Example 2-3 A dental adhesive composition having the composition shown in Table 3 was prepared in the same manner as in Example 1, and the adhesive strength was measured. As a result, the amount of the filler added was small, so that the strength of the composition was high. Was weak and the adhesive strength was lowered.

Comparative Example 4-6 A dental adhesive composition having the composition shown in Table 3 was prepared in the same manner as in Example 35, and the adhesive strength was measured. This was the case where the aryl borate compound was not added or the amount of the aryl borate compound was small, and the polymerizability was poor and the adhesive strength decreased.

[0077]

[Table 1]

[0078]

[Table 2]

[0079]

[Table 3]

Claims (2)

[Claims] 1. An acidic group-containing polymerizable monomer (A) 100 parts by weight, (B) an aryl borate compound 0.01 to 20.
A dental adhesive composition comprising 50 parts by weight and (C) a filler of 50 to 900 parts by weight. 2. An acidic group-containing polymerizable monomer (A) 100 parts by weight, (B) aryl borate compound 0.01 to 20.
Parts by weight, 50 to 900 parts by weight with respect to 100 parts by weight of (C) filler (A) and (D), and (D) polymerizable monomer {excluding (A) component} 10 to 900 parts by weight. A dental adhesive composition comprising a part.