JPH08169806A - Dental adhesive composition - Google Patents

Abstract

PURPOSE: To obtain an adhesive composition capable of providing sure adhesive dental treatment and having good operability to repair dental quality. CONSTITUTION: This dental adhesive composition contains (A) 98-60 pts.wt. of a polymerizable monomer containing 2-20wt.% of an acidic group-containing monomer, (B) 2-40 pts.wt. polymer which brings about the viscosity of a mixture solution obtained by dissolving or dispersing 10 pts.wt. of the polymer into 90 pts.wt. of methyl methacrylate of <=100cps at 25 deg.C and (C) 0.01-35 pts.wt. of a polymerization initiator, with the proviso that total amount of the components A, B and C is 100 pts.wt.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention relates to a dental adhesive composition. More specifically, the present invention uses a composition containing (A) a polymerizable monomer mixture containing an acidic group-containing monomer, (B) a specific polymer, (C) a polymerization initiator, or (D) a filler. The present invention relates to a dental adhesive composition that has good operability for dental treatment and exhibits excellent adhesive performance and a restoration effect when adhering a tooth substance and a restorative material.

[0002]

2. Description of the Related Art In the field of dental treatment, it is necessary to strongly bond a tooth substance with a material for repairing the tooth substance (for example, a polymer substance, metal, porcelain, etc.). Various things have already been proposed.

Such an adhesive composition comprises (1) a polymerizable monomer, (2) an adhesion-promoting monomer or a monomer having an affinity for teeth, (3) a polymerization catalyst or a polymerization initiator, and (4) It is generally composed of four components, an inorganic filler or an organic filler. A typical example of such an adhesive composition is a photopolymerization initiation system in which a polymerization catalyst or a polymerization initiator is a mixture of a diketone photosensitizer and an amine reducing agent, benzoyl peroxide and an aromatic compound. A chemical polymerization system has been proposed which is a mixture with a group III tertiary amine system or tributylborane partial oxide (TBBO). Among such conventionally known adhesive compositions, those adhesive compositions using TBBO as a polymerization initiator have been clinically confirmed to have high adhesive strength and little biotoxicity.

As described above, among the conventional techniques, the adhesive composition using TBBO is the most excellent, but the form of this adhesive composition has three parts, that is, a polymer powder, a monomer solution and a catalyst solution. When the adhesive composition is prepared before use, the viscosity of the composition rapidly rises, and the time interval during which the composition can be applied to the tooth surface and restorative material after mixing, that is, the operable time. Is quite short, and the inconvenience in operation is pointed out. Further, in the preparation, it is necessary to first carry out an operation of a procedure of separating and mixing a predetermined amount of the monomer liquid and the polymer powder, and then further mixing a predetermined amount of the catalyst. Therefore, development of an adhesive composition having good operability and exhibiting reliable adhesive performance has been earnestly desired.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an adhesive composition which has good operability in adhering a tooth material and a restorative material and can exhibit excellent adhesive performance.

[0006]

The above objects and advantages of the present invention are achieved by using the following adhesive composition. (A) 98-60 parts by weight of a polymerizable monomer mixture containing 2 to 20% by weight of an acidic group-containing monomer, (B) a polymer of 2 to 40 parts by weight, and (C) a polymerization initiator.
The dental adhesive composition is characterized by containing 01 to 35 parts by weight, but the total amount of (A), (B) and (C) is 100 parts by weight.

By using the adhesive composition of the present invention, when the tooth material and the restorative material are adhered, the operation is easy, the adhering performance and the restorative effect are greatly improved, and the above-mentioned problems are solved. be able to.

In the adhesive composition of the present invention, the component (A) is a polymerizable monomer mixture containing 2 to 20% by weight of an acidic group-containing monomer. Monomers other than the acidic group-containing monomer are not particularly limited, and generally known monofunctional monomers or polyfunctional monomers can be used. A (meth) acrylate-based monomer having relatively low irritation to the human body is particularly preferably used.

Specific examples of the monofunctional monomer in the component (A) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, etc. An alkyl ester of (meth) acrylic acid;

2-hydroxyethyl (meth) acrylate, 2 or 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 5
-Hydroxyalkyl of (meth) acrylic acid such as hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 1,2- or 1,3-dihydroxypropyl mono (meth) acrylate, erythritol mono (meth) acrylate ester;

Polyethylene glycol mono (meth) acrylates such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate;

Fluoroalkyl esters of (meth) acrylic acid such as perfluorooctyl (meth) acrylate and hexafluorobutyl (meth) acrylate;

Silane compounds having a (meth) acryloxyalkyl group such as γ- (meth) acryloxypropyltrimethoxysilane and γ- (meth) acryloxypropyltri (trimethylsiloxy) silane;

Examples include (meth) acrylates having a heterocycle such as tetrafurfuryl (meth) acrylate. These monofunctional monomers can be used alone or in combination. The monofunctional monomer is used in an amount of usually 20 to 80% by weight, preferably 30 to 70% by weight, based on the polymerizable monomer mixture.

Specific examples of the polyfunctional monomer in the component (A) include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth). Poly (meth) acrylates of alkane polyols such as acrylate, hexylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate,

Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate,
Poly (meth) acrylates of polyoxyalkane polyols such as dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate,

2,2-bis {4- (meth) acryloxyphenyl} propane, 2,2-bis {4- (meth) acryloxyethoxyphenyl} propane, 2,2-bis {4- (meth) acryl Roxydiethoxyphenyl} propane, 2,2-bis {4- (meth) acryloxytriethoxyphenyl} propane, 2,2-bis {4- (meth) acryloxypolyethoxyphenyl} propane, 2,
An aromatic di (meth) acrylate such as 2-bis {4- [3- (meth) acryloxy] -2-hydroxypropoxyphenyl} propane,

The following equation (1)

[0019]

Embedded image

An aliphatic or aromatic di (meth) acrylate represented by:

The following equation (2)

[0022]

Embedded image

An aliphatic or aromatic epoxy di (meth) acrylate represented by:

Further, the following equation (3)

[0025]

Embedded image

Examples include polyfunctional (meth) acrylates having a urethane bond in the molecule represented by

In the above examples, as the monofunctional monomer, alkyl (meth) acrylate such as methyl (meth) acrylate and ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 1,
3-dihydroxypropyl mono (meth) acrylate,
Hydroxyl group-containing (meth) acrylate such as erythritol mono (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, (meth) acrylate having an ethylene glycol chain in the molecule such as triethylene glycol mono (meth) acrylate Are particularly preferably used. Among these monomers,
The hydroxyl group-containing (meth) acrylate or (meth) acrylate having an ethylene glycol chain in the molecule is preferably used in an amount of 5 to 30% by weight, more preferably 8 to 25% by weight, based on the polymerizable monomer mixture.

As the polyfunctional monomer, di (meth) acrylate having an ethylene glycol chain in the molecule such as triethylene glycol di (meth) acrylate and polyethylene glycol di (meth) acrylate,

The following equation (4)

[0030]

[Chemical 4]

A compound represented by

The following equation (5)

[0033]

Embedded image

A compound represented by

The following equation (6)

[0036]

[Chemical 6]

The compound represented by the formula (1) and the like are particularly preferably used. The polyfunctional (meth) acrylate monomer is used in an amount of preferably 10 to 50% by weight, more preferably 20 to 45% by weight, based on the polymerizable monomer mixture. These monofunctional and polyfunctional (meth) acrylate monomers can be used alone or in combination of two or more. Further, other vinyl monomers such as styrene, α-methylstyrene, p-methylstyrene and the like can be used as long as the object of the present invention is not impaired.

Specific examples of the polymerizable monomer having an acidic group in its molecule include (meth) acrylic acid and its anhydride, 1,4-di (meth) acryloxyethylpyromellitic acid, 6- (Meth) acryloxyethylnaphthalene 1,2,6-tricarboxylic acid, N- (meth) acryloyl-p-aminobenzoic acid, N- (meth) acryloyl-o-aminobenzoic acid, N- (meth) acryloyl-m
-Aminobenzoic acid, N- (meth) acryloyl-5-aminosalicylic acid, N- (meth) acryloyl-4-aminosalicylic acid, 4- (meth) acryloxyethyltrimellitic acid and its anhydride, 4- (meth) Acryloxybutyl trimellitic acid (4-MET) and its acid anhydride (4-META), 4- (meth) acryloxyhexyl trimellitic acid and its anhydride, 4- (meth) acryloxydecyl trimellitic acid and Its anhydride, 2-
(Meth) acryloyloxybenzoic acid, 3- (meth) acryloyloxybenzoic acid, 4- (meth) acryloyloxybenzoic acid, β- (meth) acryloyloxyethyl hydrogen succinate, β- (meth) acryloyloxyethyl hydro Monomers containing carboxylic acid groups such as gen maleate, β- (meth) acryloyloxyethyl hydrogen phthalate, 11- (meth) acryloyloxy-1,1-undecanedicarboxylic acid and p-vinylbenzoic acid, or anhydrides thereof. ;

Monomers containing phosphoric acid groups such as (2- (meth) acryloxyethyl) phosphoric acid, (2- (meth) acryloxyethylphenyl) phosphoric acid and 10- (meth) acryloxydecylphosphoric acid;

Further, a monomer having a sulfonic acid group such as p-styrenesulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid can be used.

These acidic group-containing monomers can be used alone or in combination. Among these acidic group-containing monomers, 4-MET and 4-META
Is preferred. The compounding amount of the monomer containing these acidic groups is preferably 2 to 20 parts by weight when the total polymerizable monomer component is 100 parts by weight.

The compounding amount of the (A) polymerizable monomer in the adhesive composition of the present invention is usually 98 to 60 parts by weight based on 100 parts by weight of the total amount of (A), (B) and (C). Within range. It is preferably in the range of 95 to 70 parts by weight.

In the adhesive composition of the present invention, the polymer of the component (B) has a viscosity of a mixed solution obtained by dissolving or dispersing 10 parts by weight of 90 parts by weight of methyl methacrylate,
Usually 100 cps or less at 25 ° C., preferably 70
It is a polymer showing cps or less, particularly preferably 50 cps or less. Since such a polymer does not significantly increase the viscosity of the mixed solution when dissolved or dispersed in the polymerizable monomer (A), it does not hinder the adhesive composition from penetrating into the tooth structure, and thus a good adhesive effect can be obtained. To be

As the polymer of the component (B), for example, a copolymer of an alkyl (meth) acrylate, a styrene monomer and a hydroxyalkyl (meth) acrylate having at least one hydroxyl group in the molecule (hereinafter referred to as M
SH copolymer), a copolymer consisting of an alkyl (meth) acrylate and a styrene monomer (hereinafter, MS copolymer), a copolymer consisting of an alkyl (meth) acrylate, a styrene monomer and butadiene (hereinafter, MSB copolymer), polyalkylmethacrylate, polyvinyl acetate and the like.

Examples of the alkyl (meth) acrylate in the copolymer as the component (B) include methyl (meth).
Acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate,
Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like can be mentioned. Among them, methyl (meth) acrylate, ethyl (meth) acrylate and the like are particularly preferably used. These alkyl (meth) acrylates can be used alone or in combination.

Examples of the styrene monomer in the copolymer as the component (B) include styrene, α-methylstyrene and para-methylstyrene. Of these, styrene and para-methylstyrene are particularly preferably used. These styrene monomers can be used alone or in combination.

Examples of the hydroxyalkyl (meth) acrylate in the copolymer of the component (B) include 2-hydroxyethyl (meth) acrylate, 2 or 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate. , 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 1,2- or 1,3-dihydroxypropane (meth) acrylate and the like. Among them, 2-hydroxyethyl (meth) acrylate, 2 or 3-hydroxypropyl (meth) acrylate and the like are particularly preferably used. These hydroxyalkyl (meth) acrylates can be used alone or in combination.

The content of the alkyl (meth) acrylate, the styrene monomer and the hydroxyalkyl (meth) acrylate in the MSH copolymer (b1) as the component (B) is 30 to 70% by weight for the alkyl (meth) acrylate,
The styrene monomer is in the range of 20 to 60% by weight and the hydroxyalkyl (meth) acrylate is in the range of 5 to 30% by weight.

The content of the alkyl (meth) acrylate and styrene monomer in the MS copolymer (b2) of the component (B) is 30 to 70 for the alkyl (meth) acrylate.
Weight percent and styrenic monomers are in the range of 70-30 weight percent.

In the MSB copolymer (b3) as the component (B), the content of alkyl (meth) acrylate, styrene monomer and butadiene is 5 to 30% by weight for alkyl (meth) acrylate and 15 to 40 for styrene monomer.
Weight percent and butadiene are in the range of 40-70 weight percent. Also, the MSB copolymer is an elastomer and forms a dispersion in methylmethacrylate.

In the alkyl (meth) acrylate polymer (b5) as the component (B), the content of methyl (meth) acrylate and other alkyl (meth) acrylate is 50 to 100% by weight for methyl (meth) acrylate, Alkyl (meth) acrylate is 0 to 50% by weight
Is in the range.

The blending amount of the (B) polymer in the adhesive composition of the present invention is such that the total amount of (A), (B) and (C) is 100.
It is usually in the range of 2 to 40 parts by weight with respect to parts by weight.
It is preferably in the range of 5 to 30 parts by weight.

The above MSH in the adhesive composition of the present invention
Polymers exemplified by copolymers, MS copolymers, MSB copolymers, alkyl (meth) acrylate polymers, polyvinyl acetate polymers and the like may be used alone or in combination of two or more thereof to prepare a polymerizable monomer solution of the composition. When dissolved and / or dispersed in, it is possible to form a stable storable mixed solution that does not cause a significant increase in viscosity, and it is possible to maintain the ability of the composition to penetrate into the tooth structure. Furthermore, by allowing a polymer to coexist in the composition, it is possible to reduce the content of the polyfunctional monomer without impairing the curing performance such as the curing rate of the composition, improve the operability of the composition, and improve the tooth quality. When adhering to a restoration material, it can exhibit excellent adhesion performance and restoration effect.

In the adhesive composition of the present invention, the component (C) is a polymerization initiator. Generally known peroxides, photopolymerization initiators, trialkylboron or partial oxides thereof can be used.

Examples of the peroxide in the component (C) include diacetyl peroxide, dipropyl peroxide, dibutyl peroxide, dicapryl peroxide,
Examples thereof include benzoyl peroxide (BPO), p, p'-dichlorobenzoyl peroxide, p, p'-dimethoxybenzoyl peroxide, and p, p'-dimethylbenzoyl peroxide. Of these, BPO is preferred. Further, there may be mentioned inorganic peroxides such as ammonium persulfate, potassium persulfate, potassium chlorate, potassium bromate and potassium perphosphate. The amount of oxides mixed is (A), (B), (C)
It is usually in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the total amount. It is preferably in the range of 0.1 to 5 parts by weight.

The photopolymerization initiator in the component (C) is not particularly limited as long as it can be polymerized by irradiation with ultraviolet rays or visible rays. For example, benzyl, 4,4'-dichlorobenzyl, Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzophenone, diacetyl, d, l-camphaquinone (CQ), camfaquinone-10-sulfonic acid, camfaquinone-10-carboxylic acid, 2,4-diethylthioxanthone 2, 4, 6-
Examples thereof include ultraviolet or visible light sensitizers such as trimethylbenzoyldiphenylphosphine oxide. These photopolymerization initiators can be used alone or in combination. The blending amount of these photopolymerization initiators is (A),
It is usually in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the total amount of (B) and (C). Preferably 0.1
Within the range of 5 parts by weight.

In order to improve the polymerization initiation effect of the above-mentioned peroxide or photopolymerization initiator, it is preferable to use a polymerization accelerator such as a reducing compound in combination. For example, N, N-dimethylaniline,
N, N-dimethyl p-toluidine (DMPT), N, N-
Diethyl p-toluidine, N, N-diethanol p-toluidine (DEPT), N, N-dimethyl p-tert
-Butylaniline, N, N-dimethylanisidine, N, N
-Dimethyl p-chloroaniline, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminobenzoic acid and its alkyl ester, N, N-diethylaminobenzoic acid (DEABA) and its alkyl ester, N, N-dimethylaminobenzaldehyde (DMABAd), N-phenylglycine (NPG),
Organic reducing compounds such as N-tolylglycine (NTG), N, N- (3-methacryloyloxy-2-hydroxypropyl) phenylglycine (NPG-GMA) and glutaraldehyde,

Sulfite, bisulfite, metasulfite, metabisulfite, pyrosulfite, thiosulfate, 2thionate, hyposulfite,
Inorganic reducing compounds such as hydrosulfite and salts thereof,

Aromatic sulfinic acids such as benzenesulfinic acid, o-toluenesulfinic acid, p-toluenesulfinic acid, ethylbenzenesulfinic acid, decylbenzenesulfinic acid, dodecylbenzenesulfinic acid, chlorobenzenesulfinic acid, and naphthalenesulfinic acid, or The salts and the like can be used together.

The compounding amount of the reducing compound and the polymerization accelerator such as aromatic sulfinic acid or a salt thereof is (A),
It is usually in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the total amount of (B) and (C). Preferably 0.1
Within the range of 5 parts by weight.

Examples of the trialkylboron or its partial oxide include triethylboron, tripropylboron, triisopropylboron, tri-n-butylboron, triisobutylboron, tri-sec-butylboron, tri-n-amylboron, It is possible to use tri-3-amylboron, triisoamylboron, tri-sec-amylboron, or a trialkylboron oxide obtained by partially oxidizing these. Among these, tri-n-butylboron or its partial oxide is preferably used. The compounding amount of the trialkylboron or the partial oxide thereof is usually in the range of 2 to 35 parts by weight with respect to 100 parts by weight of the total amount of (A), (B) and (C). It is preferably in the range of 5 to 30 parts by weight.

Of these polymerization initiators, trialkylboron, partial oxides thereof and photopolymerization initiators are preferably used.

In the adhesive composition of the present invention, the component (D) is a filler. Generally known inorganic or organic fillers can be used.

As the inorganic filler in the component (D),
For example, zirconium oxide, bismuth oxide, titanium oxide, zinc oxide, metal oxides such as aluminum oxide, calcium carbonate, bismuth carbonate, calcium phosphate, zirconium phosphate, metal salts such as barium sulfate, silica glass, barium-containing glass, Glass containing strontium,
Examples thereof include glass fillers such as zirconia silicate glass, and organic composite fillers. These inorganic fillers can be used alone or in combination.

In order to reduce the film thickness of the adhesive composition and improve the repair effect, the average particle size of the above-mentioned inorganic filler is usually 0.1.
001 to 50 μm. Preferably 0.005
˜30 μm.

Further, in order to obtain a strong bond between the filler and the resin, it is preferable to use the above-mentioned filler subjected to surface treatment such as silane treatment and polymer coating.

As the organic filler in the component (D),
For example, an organic bismuth compound, an organic zirconium compound,
Examples thereof include metal organic compounds such as organic titanium compounds. These organic fillers can be used alone or in combination.

These inorganic fillers and organic fillers can be used alone or in combination. In order to improve the mechanical properties of the cured product of the adhesive composition, an inorganic filler is preferably used.

The blending amount of these fillers is (A),
25-based on 100 parts by weight of the total amount of (B) and (C)
It is preferably in the range of 400 parts by weight. More preferably, the range is 30 to 300.

When the composition comprises (A) and (B) or (A), (B) and (C), the viscosity of the adhesive composition of the present invention is preferably 1000 cps or less at 25 ° C., and 500 cps. The following is more preferable, and 200 cp
s or less is more preferable. Even when the composition further contains the component (D), the composition comprising (A), (B) and (C) can be used without any limitation as long as it has the above viscosity. In this case, the composition is preferably in paste form.

The adhesive composition of the present invention comprises the above (A),
(B), (C) component, or (A), (B), (C),
The components (D) are preliminarily combined in any desired ratio, for example, ((A) + (B)) and (C); ((A) + (B) +
(D)) and (C); or ((A) + (B) + (C))
And ((A) + (B) + polymerization accelerator) can be divided and stored in two or more liquid or pasty compositions.

If necessary, the adhesive composition of the present invention may contain an appropriate amount of components such as a colorant, a hydroquinone polymerization inhibitor, or a solvent.

[0073]

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

Examples 1 to 10 The polymerizable monomers and polymer powders shown in Table 1 were weighed in predetermined amounts, mixed and dissolved or dispersed, and then the viscosity of the polymer-monomer mixed solution was measured. The measurement was carried out at 25 ° C. using a Utsuvelod viscometer and at 25 ° C. using an E-type viscometer (EHD type, Tokimec Co.) in Examples 6 to 10. The results are shown in Table 1.

[0075]

[Table 1]

The compounds represented by the symbols in Table 1 are shown below. MMA: methyl methacrylate, HEMA: 2-hydroxyethyl methacrylate, 2.6E: 2,2-bis [(4-methacryloxyethoxy) phenyl] propane, 4-META: 4-methacryloxyethyl trimellitic anhydride, MSH : Methylmethacrylate / styrene / 2-hydroxyethylmethacrylate (weight ratio, in this order, 4
8: 46: 6) Copolymer powder, PMS: Methyl methacrylate / styrene copolymer powder (Hypal, D-1955MSL, Negami Kogyo Co., Ltd.), MSB: Methyl methacrylate / Budadiene / styrene copolymer powder (BTA705, Kureha), PVAc: polyvinyl acetate powder (Sakunol DR-11)
7, Electrochemistry (Co., Ltd.), PMMA: Polymethylmethacrylate (Hyper D
250ML, Negami Industry Co., Ltd.

Examples 11 to 17 and Comparative Examples 1 to 2 Liquid and paste-like or powder-like compositions shown in Table 2 were quantitatively taken out and mixed at room temperature, and the time until the mixture gelled (pot life) The operability was evaluated by measuring the time (curing time) until the needle (φ: 0.5 mm) was not penetrated. The results are shown in Table 2.

[0078]

[Table 2]

The compounds represented by the symbols in Table 2 are shown below. TBBO: tributylboron partial oxide (catalyst, Sun Medical Co., Ltd.), GBa: barium-containing glass powder (8235G, Shot Japan Co., Ltd.), and others are the same as in Table 1.

In Examples 18 to 27, the labial surface side of the bovine anterior tooth was cut to remove enamel (E) or dentin surface (D).
Then, it was polished with No. 600 emery paper to form an adhesive surface. This adhesive surface is washed with water, dried, treated with an etching aqueous solution containing 3% iron chloride and 10% citric acid for 30 seconds, washed with water for 20 seconds and air blow dried for 15 seconds, and then a circle having a diameter of 4 mm. A cellophane tape with holes was attached to the adhesive surface to define the adhesive area. In Example 18,
The adhesive composition of the present invention shown in Table 3 was applied to this adhesive surface, and a SUS rod was adhered to obtain a sample for adhesion test.

In Examples 19 to 24, the adhesive composition of the present invention shown in Table 3 was applied to the adhesive surface having the defined area and lightly air-blown to uniformly form a coating film of the adhesive composition. After spreading and leaving it for about 30 seconds, a Teflon mold with a diameter of 5 mm and a thickness of 1 mm is attached to the adhesive surface, and the composite resin for dental treatment (3M
Co., Ltd., Silax Plus) is filled and the composite resin is cured by irradiating visible light from a distance of 5 mm for 40 seconds using a visible light irradiation device for dental treatment (Translux, manufactured by Kurzer Co., Ltd.). It was A PMMA rod was adhered onto the cured composite resin using a quick-hardening instant polymerization resin for dental treatment (manufactured by Sun Medical Co., Ltd., Metafast) to prepare an adhesion test sample.

In Examples 25 to 27, 4-META was applied to the adhesive surface formed by polishing with No. 600 emery paper.
1.5 g, polyethylene glycol dimethacrylate (23 G, Shin Nippon Kagaku Co., Ltd.) 1.5 g, ethanol 7
g, 10 g of water, 0.01 g of camphorquinone, and 0.01 g of N, N'-dimethylaminobenzoic acid were applied, and after 40 seconds, air blow was performed with an air gun to dry. Then, a cellophane tape with a hole having a diameter of 4 mm was attached to the adhesive surface to define the adhesive area. On this primer, the adhesive composition of the present invention shown in Table 3 was applied, and a visible light irradiator for dental treatment (Kurzer Co., Ltd.,
After irradiating visible light from a distance of 5 mm for 20 seconds using Translux, a 1 mm thick Teflon mold with a hole having a diameter of 5 mm is attached to the adhesive surface, and a composite resin for dental treatment (in the hole). 3M Co., Ltd., Silax Plus) was filled and visible light was irradiated from a distance of 5 mm for 40 seconds using a visible light irradiator for dental treatment to cure the composite resin. A PMMA rod was adhered onto the cured composite resin using a quick-hardening instant polymerization resin for dental treatment (manufactured by Sun Medical Co., Ltd., Metafast) to prepare an adhesion test sample.

The adhesion test sample was left at room temperature for 30 minutes, further immersed in distilled water at 37 ° C. for 24 hours, and then subjected to a tensile test to measure the adhesion strength between the acrylic rod and the tooth structure. The adhesive strength is an average value of the values measured on five test pieces.

The adhesive strength measured as described above is shown in Table 3.
Shown in

[0085]

[Table 3]

The compounds represented by the symbols in the table are shown below. 3G: triethylene glycol dimethacrylate, CQ: camfaquinone, DEABA: N, N'-dimethylaminobenzoic acid, 4-MET: 4-methacryloxyethyl trimellitic acid.

Examples 28 to 33 The polymerizable monomers and polymer powders shown in Table 4 were weighed in predetermined amounts, mixed and dissolved or dispersed, and then stored in a thermostatic box at 45 ° C. for 1 week to change the fluidity of the mixed liquid. Was visually observed to evaluate the storage stability of the mixed solution. In all of the examples, no clear change in fluidity was observed with the naked eye, indicating good storage stability.

[0088]

[Table 4]

[0089]

EFFECTS OF THE INVENTION According to the present invention, it is possible to provide an adhesive composition having good operability for restoration of tooth structure and having a good restoration effect, and a reliable adhesive dental treatment can be obtained.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Takeshi Baba 571-2 Furutakacho, Moriyama City, Shiga Prefecture Sun Medical Co., Ltd.

Claims (10)

[Claims] 1. A polymerizable monomer mixture containing (A) an acidic group-containing monomer in an amount of 2 to 20% by weight, 98 to 60 parts by weight, (B) a polymer in an amount of 2 to 40 parts by weight, and (C) a polymerization initiator. 01-35 parts by weight, provided that the total of (A), (B) and (C) is 100 parts by weight. 2. The polymer (B) is a copolymer comprising (b1) an alkyl (meth) acrylate, a styrene monomer and a hydroxyalkyl (meth) acrylate having at least one hydroxyl group in the molecule, (b2). A copolymer composed of an alkyl (meth) acrylate and a styrene monomer, (b3) a copolymer composed of an alkyl (meth) acrylate, a styrene monomer and butadiene,
It is at least one polymer selected from the group consisting of a combination of (b4) polyvinyl acetate and (b5) alkyl (meth) acrylate polymer and a polymer selected from the above (b1) to (b4). 1. The adhesive composition of 1. 3. The adhesive property according to claim 1, wherein the polymer has a viscosity of a mixed solution obtained by dissolving or dispersing 10 parts by weight with respect to 90 parts by weight of methyl methacrylate at 100 ° C. or less at 25 ° C. Composition. 4. The dental adhesive composition according to claim 1, wherein the polymerizable monomer contains 5 to 30% by weight of a hydroxyl group-containing (meth) acrylate and / or an acrylate having an ethylene glycol chain in the molecule. 5. The dental adhesive composition according to claim 1, wherein the polymerizable monomer contains 10 to 50% by weight of a polyfunctional acrylate. 6. The dental adhesive composition according to claim 1, wherein the acidic group-containing monomer is 4- (meth) acryloxyethyl trimellitic acid and its acid anhydride. 7. The polymerizable monomer (A) is (a1) 4-
2 to 20% by weight of (meth) acryloxyethyl trimellitic acid and its acid anhydride, 5 to 25% by weight of (a2) 2-hydroxyalkyl acrylate, (a3) (meth) acrylate having a urethane bond, aromatic-containing diester 3. At least one di (meth) acrylate selected from (meth) acrylate and dimethacrylate having an ethylene glycol chain, and 10 to 60% by weight of (a4) alkyl (meth) acrylate. Dental adhesive composition. 8. The method according to claim 1, wherein the polymerization initiator is a photopolymerization initiator, trialkylborane or a partial oxide thereof.
Adhesive composition of. 9. In addition to the components (A), (B) and (C) described above, a filler (D) is further contained, and the blending amount of the filler (D) is (A), (B). ) And (C), based on 100 parts by weight, 25 to 400 parts by weight of the adhesive composition according to claim 1. 10. The combination of (A) to (C) or the combination of (A) to (D) is divided and stored in two or more liquid or pasty compositions, and mixed before use. The dental adhesive composition according to claim 1 or claim 9.