JPH03279308A - Dental adhesive - Google Patents

Abstract

PURPOSE:To obtain an adhesive having excellent adhesion and sealing property of side edge between tooth and repairing material by using glyceryl mono(meth) acrylate and olefinic double bond-containing acidic polymerizable monomer copolymerizable with the above-mentioned compound as structural components. CONSTITUTION:The aimed adhesive for tooth containing (A) 0.1-30wt.% glyceryl mono(meth)acrylate and (B) 0.1-30wt.% acidic polymerizable monomer being a compound copolymerizable with the compound A and having a group expressed by formula I to formula V (Z is halogen; binding hand is not bonded to OH, halogen, etc.) and acidic group such as -COOH and olefinic double bond. The adhesive has excellent adhesion to dentine as well as excellent sealing property of side edge between tooth and repair material. Therefore, the adhesive is preferably used for repair of dental neck, etc. The compound A is used by dissolving it in a volatile organic solvent having <=200 deg.C boiling point, water or mixture thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a dental adhesive which is excellent in adhesion between tooth structure and dental restorative materials and in sealing of the margins.

(Prior Art) In recent years, in the field of dental materials, various adhesives have been developed that have excellent adhesion to tooth structure, particularly dentin. Polymerizable monomers having an acidic group in the molecule are used as adhesive components of such adhesives, and known polymerizable monomers include phosphoric acid diester groups (especially JP-A No. 52-113089), phosphoric acid monoester group (JP-A No. 58-211507), carboxyl group,
Containing acid anhydride groups (JP-A-54-11149), acid halide groups (JP-A-57-151607), etc.
Meth)acrylic acid monomers are mentioned.

However, even with adhesives containing such adhesive monomers, when bonding dental restorative materials (fillers, metals, etc.) to tooth structure, gaps may be created between the tooth structure and the restorative material. .

(Problems to be Solved by the Invention) The present invention provides a dental adhesive that not only has excellent adhesion to the tooth structure but also has excellent margin sealing properties that can suppress the formation of a gap at the margin between the tooth structure and the restorative material. 0 (Means for solving the problem) The above problem is to obtain a dental agent containing glyceryl mono(meth)acrylate and a polymerizable monomer copolymerizable with the glyceryl mono(meth)acrylate. Solved by adhesive. Furthermore, the polymerizable monomer is eagle, and the bond is eagle.

hydroxyl group.

halogen or ■ p-o- H base does not combine.

) It is preferable to use an acidic polymerizable monomer having at least one acidic group and at least one olefinic double bond selected from the group consisting of:

Glyceryl mono(meth)acrylate makes it difficult for the adhesive to wet the tooth surface due to the effect of the two hydroxyl groups in the molecule, and improves the adhesion to tooth structure and margin sealing properties.

Glyceryl mono(meth)acrylate) f/j 1.3
-dihydroxyinpropyl (meth)acrylate and 2
There are isomers of ,3-dihydroxypropyl (meth)acrylate, but 2,3-dihydroxypropyl (meth)acrylate is preferable from the viewpoint of adhesiveness, and methacrylic monomer is usually better than acrylic monomer. Often used.

The adhesive of the present invention is constructed as follows using glyceryl mono(meth)acrylate and a polymerizable monomer copolymerizable with the glyceryl mono(meth)acrylate, preferably an acidic polymerizable monomer.

A system in which glyceryl mono(meth)acrylate and the polymerizable monomer, preferably the acidic polymerizable monomer, are mixed, or a third agent such as a solvent, a filler, a polymerization initiator, etc., as necessary for such a system. An adhesive consisting of a system with added ingredients.

In such adhesives, glyceryl mono(meth)acrylate is present in an amount of 0.01 to 50% by weight (based on the total weight).
(more preferably 0.1 to 30% by weight). Moreover, the acidic polymerizable monomer is 0,0
1 to 50 weight percent (more preferably 0.1 to 3
0 weight percent).

The composition includes a volatile organic solvent having a boiling point of 200°C or less at normal pressure, water, or a mixture thereof.

Copolymerizable monomers, polymerization initiators, fillers, etc. are added as necessary.

As the copolymerizable monomer used in the present invention, (meth)
Acrylic acid ester, (meth)acrylamide, maleic acid ester, fumaric acid ester, acetic acid? Vinyl compounds such as vinyl esters, styrene and its derivatives, acrylonitrile, acrolein, etc. are used, and (meth)acrylic acid esters are particularly preferred.

The following are exemplified as (meth)acrylic esters. Methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2.2-bis(4- (3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane (Bis-GMA), trimethylolethane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, N,N-dimethylamine ethyl methacrylate.

Specific examples of the acidic polymerizable monomer used in the present invention include the following compounds.
1CRzOOC OPO(OH)2 -P+Z) Things with z group -C=CHz 0 h Things with -C-OR group oon H3 H2C-C-C0NH+CHz group CoolH3) Things with -C-Z group of the present invention Solvents used in adhesives include volatile organic solvents with a boiling point of 200°C or less at normal pressure (for example, alcohols such as methanol, ethanol, allyl alcohol, Impropatol, 1-octatool, acetone, methyl ethyl ketone, , holonatectones, ethyl ether, 1,4-dioxane, diethylene glycol,
Ethers such as diethyl ether, esters of ethyl acetate, butyl acetate, 2-ethylhexyl acetate, hexane, undecane, toluene, xyleph, [
Methylene, 1,2-dichloroethane, 1,1°2.
Hydrocarbons such as 2-tetrachloroethane, water or mixtures thereof are preferably used.

Polymerization initiators used in the uninvented adhesive include benzoyl peroxide-aromatic tertiary amine type, membrane-based products such as cumene hydroperoxide, tributylborane, aromatic sulfinic acid (or its salt)-aromatic Examples include group secondary or tertiary amine-acyl peroxide systems.

Furthermore, photopolymerization initiators such as α-diketones (eg, camphorquinone, diacetyl, benzyl)-reducing agents (eg, tertiary amines, aldehydes, mercaptans), benzoin methyl ether, etc. may be mentioned.

Fillers used in non-inventive adhesives include inorganic fillers such as glass, quartz, hydroxyapatite, calcium carbonate, barium sulfate, aluminum oxide, titanium oxide, and zirconium oxide, as well as polymethyl methacrylate, polystyrene, and polystyrene. Mention may be made of polymer powders such as the salt f-hibinyl.

(Effects) The dental adhesive of the present invention has excellent adhesion to tooth structure, particularly dentin, and is excellent in sealing the margin between tooth structure and restorative material. It is used in various dental applications where such effects are required, and among these, it is suitably used for the restoration of teeth with caries, particularly for restorations involving the neck of the tooth.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 The following composition (B) was polished with #1 OOO abrasive paper to give Q, 5
It was applied to the flat dentin surface of an extracted human tooth treated with M EDTA aqueous solution for 60 seconds, irradiated with light for 20 seconds using a visible light irradiator (Quick Light, manufactured by Kuraray), and then a commercially available photocurable composite resin (Photo Clear Film) was applied. A, manufactured by Kuraray] was built up and cured by irradiating it with light for 40 seconds using a quick light.

After immersing this in water at 37° C. for 24 hours, the tensile adhesive strength was measured and found to be 141 kg/cal.

Composition (B) 2.3-dihydroxypropyl methacrylate 30 parts by weight Bis GMA 60 〃10-
Methacryloyloxydecyl dihydrodiene phosphate 10/7 camphorquinone
0.5 ethyl N,N-dimethyl-p-aminobenzoate 0.5 Example 2 The interproximal enamel of 10 extracted human molars was removed and 41
000 abrasive paper to flatten the dentin with a diameter of 3 mm and a depth of 1
．． A 5 mm cylindrical cavity was created. Then 0.5M,
The inside of the cavity was treated with an EDTA aqueous solution for 60 seconds, washed with water and dried, then 1 Composition CB) was applied to the entire cavity, and after irradiation with visible light irradiator Quick Light (manufactured by Kuraray) for 20 seconds, Photo Clear Film A was applied. It was filled into the cavity and cured by irradiating it with light for 40 seconds using a quick light.

Immediately immerse it in room temperature water, leave it for 10 minutes, mirror polish the filled part to expose the base edge, and examine the gap between the cavity and the filler interface using an optical microscope (NIKON, 0PTIPEIOTOX4).
00). There were 9 out of 10 samples in which no gaps were observed all around the window edge, which was a good result.

Example 3 A test was conducted in the same manner as in Example 2 using a composition in which 4-methacryloyloxyethyl trimellitic acid was added instead of 10-methacryloyloxydecyl dihydrogen phosphate in composition (B). The same good results as in Example 2 were obtained.

The following margin Comparative Example 1 In Example 1, an adhesion test similar to that of IFI 11 was conducted using propyl methacrylate instead of 2,3-dihydroxyglobyl methacrylate in Composition (B) K. Tensile adhesive strength g# Comparative Example 2 In Example 2, the same test as in Example 9U2 was conducted using propyl methacrylate as the base of 2,3-dihydroxyglobil methacrylate in composition (E). The samples that did not have a high-grade trap gap were lO drawstring pieces, and to

Claims (3)

[Claims] (1) A dental adhesive comprising glyceryl mono(meth)acrylate and a polymerizable monomer having at least one olefinic double bond copolymerizable with the glyceryl mono(meth)acrylate. (2) Glyceryl mono(meth)acrylate and a monomer copolymerizable with the glyceryl mono(meth)acrylate, ▲There are mathematical formulas, chemical formulas, tables, etc.▼groups, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Groups, ▲There are mathematical formulas, chemical formulas, tables, etc.▼Groups, ▲There are mathematical formulas, chemical formulas, tables, etc.▼Groups, ▲There are mathematical formulas, chemical formulas, tables, etc.▼Groups, ▲There are mathematical formulas, chemical formulas, tables, etc.▼Groups, ▲There are mathematical formulas, chemical formulas, tables, etc.▼Groups, ▲There are mathematical formulas, chemical formulas, tables, etc.▼Groups and ▲There are mathematical formulas, chemical formulas, tables, etc.▼Groups (However,
Z represents a halogen, and the bond includes a hydroxyl group, a halogen, or a ▲ mathematical formula, chemical formula, table, etc. ▼ does not bond. ) and at least one acidic group selected from the group consisting of
2. The dental adhesive according to claim 1, which comprises an acidic polymerizable monomer having olefinic double bonds. (3) The dental adhesive according to claim 1 or 2, wherein glyceryl mono(meth)acrylate is dissolved in a volatile organic solvent having a boiling point of 200°C or less at normal pressure, water, or a mixture thereof. .