JPH0564603B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to an adhesive for tooth tissue, and more particularly to a dental adhesive that strongly adheres to a tooth under moist conditions in the oral cavity. (Prior Art) Conventionally, a mixture of a methacrylic acid ester monomer mainly composed of bisphenol A diglycidyl methacrylate and an inorganic powder (for example, SiO ₂ ), and a mixture of peroxide-amine or peroxide-sulfinic acid have been conventionally used. Paste-like composite materials containing two-component redox hardeners have been used as dental filling materials (U.S. Pat. No. 3,066,112, U.S. Pat. No. 3,926,906). However, this composite material has poor adhesion to teeth. It had the disadvantage of being scarce. Therefore, attempts have been made to improve adhesion by etching the tooth surface using an acid such as an aqueous phosphoric acid solution to improve the mechanical fitting force. On the other hand, by pre-applying a liquid agent (bonding agent) with an appropriate viscosity consisting only of monomer components and then filling it with the paste-like composite material, the mechanical fitting force is improved and adhesiveness is improved. A method has been adopted. Although the above method has significantly improved the adhesiveness to enamel, which is the surface layer of the tooth, the adhesive strength to dentin, which is the inner layer of the tooth, is only 0 to 15 kg/ ^cm2 . However, the current situation is that we have not reached a level of satisfaction. Recently, the adhesion to dentin has been significantly improved by using dental adhesives using a ternary curing agent consisting of a salt of sulfuric acid, an amine, and a peroxide. Under humid conditions in the oral cavity, there is a drawback that etching is highly variable and requires etching using an aqueous phosphoric acid solution or the like, which has the problem of irritating tissue. Furthermore, conventional dental adhesives contain peroxide as a polymerization catalyst as an essential component, and must be packaged in a form in which peroxide is blended into (meth)acrylic acid ester monomer. Therefore, during long-term storage, peroxides tend to decompose, resulting in many problems such as discoloration, gelation, and loss of catalytic activity. (Problems to be Solved by the Invention) As a result of intensive research into dental adhesives, the present inventors have found that using a specific polymeric curing agent eliminates all of the above-mentioned drawbacks of existing dental adhesives. The present invention has been completed by discovering that this problem can be solved. An object of the present invention is to provide an adhesive that has excellent adhesion to tooth tissues, ie, enamel and dentin. Still another object of the present invention is to provide an adhesive that has excellent adhesion to teeth even without acid etching. Still another object of the present invention is to provide a stable dental adhesive that does not change color or gel during long-term storage after manufacture. Further objects and advantages will become apparent from the description below. (Means for Solving the Problems) The above object is to provide an adhesive composition containing a (meth)acrylic acid ester monomer and a polymeric curing agent as main components, using (a) a salt of sulfinic acid as the polymeric curing agent. , (b) an amine, and (c) an organic acid or an acidic inorganic acid ester. The (meth)acrylic acid ester monomer of the present invention is a monomer having radical polymerizability, and is preferably a monomer that can be polymerized and cured at around room temperature. Examples include the following compounds. Methyl (meth)acrylate, ethyl (meth)
Acrylate, n-propyl (meth)alrylate, n-butyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethyl-hexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl ( meth)acrylate, benzyl(meth)acrylate, lauryl(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,6
-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate,
1,10-decanediol di(meth)acrylate, bisphenol-A di(meth)acrylate, 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane (Bis-GMA), 2,2-bis[4-(3
-acryloyloxy-2-hydroxypropoxy)phenyl]propane, 2,2-bis[4-
(2-methacryloyloxy-ethoxy)phenyl]propane, urethane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, these (meth) ) Acrylic acid ester monomers may be used alone or in combination. The sulfinic acid salt of the present invention is preferably a sulfinic acid having an organic group, that is, a salt of an organic sulfinic acid. Either a salt of sulfinic acid bonded to an aryl group or an alkyl group may be used, but from the viewpoint of stability during storage, a salt of sulfinic acid bonded to an aryl group is more preferable. As the salt, an alkali metal or alkaline earth metal salt is used.
Specifically, for example, the following sulfinic acid salts may be mentioned. Namely, sodium benzenesulfinate, calcium benzenesulfinate, potassium benzenesulfinate, magnesium benzenesulfinate, magnesium p-toluenesulfinate, calcium p-toluenesulfinate,
Examples include barium p-toluenesulfinate, sodium p-toluenesulfinate, potassium p-toluenesulfinate, potassium 2-naphthalenesulfinate, potassium p-chlorobenzenesulfinate, and the like. The sulfinic acid salt of the present invention is used in an amount of 1 to 10 parts by weight, preferably 2 to 6 parts by weight, when the total amount of the (meth)acrylic acid ester monomer is 100 parts by weight. The amine used in the present invention may be any amine used in ordinary redox curing agent systems, but
Among these, amines bonded to aryl groups are preferred in terms of stability. Furthermore, secondary and even tertiary amines are more effective as catalysts than primary amines.
Specific examples of such amines include N-methylaniline, N-methyl-p-toluidine, N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N-methyl-N'-β- Hydroxyethylaniline, N-methyl-N'-β
-Hydroxyethyl-p-toluidine, N,N-
di-(β-hydroxyethyl)-p-toluidine,
Examples include N,N-di-(β-hydroxyethyl)aniline. The amine of the present invention is 0.1 to 100 parts by weight, based on the total amount of (meth)acrylic acid ester monomers.
It is used in an amount of 8 parts by weight, preferably in a range of 1 to 5 parts by weight. Examples of the organic acids used in the present invention include carboxylic acids, sulfonic acids, sulfinic acids, and thio acids. Similarly, examples of organic acidic inorganic acid esters include acidic phosphoric acid esters and acidic sulfuric acid esters. Specific examples of such organic acids include acetic acid, propionic acid, maleic acid, (meth)acrylic acid,
Carboxylic acids such as malonic acid, 2-(meth)acryloxyethyl succinic acid, aliphatic hydroxycarboxylic acids such as lactic acid and citric acid, benzoic acid, terephthalic acid, isophthalic acid, 2-(meth)acryloxyethyl terephthalic acid, etc. aromatic carboxylic acids, benzenesulfonic acid, p-toluenesulfonic acid, p-chlorobenzenesulfonic acid, aromatic sulfonic acids such as dodecylbenzenesulfonic acid, acidic isopropyl sulfate, monobutyl phosphate, dibutyl phosphate, monooctyl phosphate, dioctyl Phosphoric acid, 2-(meth)
Examples include acidic esters of inorganic acids such as acryloxyethyl phosphoric acid and 2-(meth)acryloxyethyl-1-chloropropyl phosphoric acid, among others, aliphatic carboxylic acids, aromatic sulfonic acids, and acidic phosphoric acid esters. is preferable because it has an excellent adhesion promoting effect. Among these preferred compounds, those having a methacryloyl group are more preferred because they exhibit remarkable water resistance in addition to adhesion promoting effects. The organic acid or acidic inorganic acid ester of the present invention preferably contains 1 to 20 parts by weight, more preferably 5 to 15 parts by weight, when the total amount of the (meth)acrylic acid ester monomer is 100 parts by weight. Used in range. In addition to the above-mentioned essential components, additives such as fillers and stabilizers can be added to the dental adhesive of the present invention. As the filler, polymethyl methacrylate powder, quartz powder, glass powder, alumina powder, etc. can be used. In addition, as a stabilizer, hydroquinone, hydroquinone monomethyl ether, 2,6-di-t-
Butyl-4-methylphenol, 2-hydroxy-4-methoxybenzophenone, etc. can be used. Furthermore, if necessary, for the purpose of improving operability, each component of the present invention is dissolved in a volatile solvent in advance, and before use, it is applied to the tooth surface and the solvent is evaporated with air etc. to form an adhesive layer. A method can be used. Any volatile solvent may be used as long as it has a low boiling point and is less harmful to the human body, such as methanol, ethanol, butanol, ethyl ether, acetone, methyl acetate,
Ethyl acetate etc. can be used. When using the dental adhesive of the present invention, the components of the present invention may be mixed immediately before use, but a simpler method of use is to mix them in advance into 2 to 3 parts (or more simply, into 2 parts). ) It is best to separate and package. For example, as part A, a solution of an organic acid or an acidic inorganic acid ester dissolved in a (meth)acrylic acid ester monomer is prepared, and as part B, an ethanol solution of a sulfinic acid salt and an amine is prepared. Prepare and form into two packages. Immediately before use, parts A and B are mixed at a fixed ratio, the mixture is applied to the tooth surface, and the ethanol is evaporated by blowing air to form an adhesive layer. (Effects of the Invention) The dental adhesive according to the present invention has strong adhesion not only to tooth enamel but also to dentin. Furthermore, strong adhesion can be obtained without the conventional acid etching. Furthermore, the packaging made of the (meth)acrylic acid ester monomer used in the present invention does not contain peroxides that easily decompose at room temperature, so it is stable over a long period of time, and has the advantage of being almost free from gelation and discoloration. has. The dental adhesive of the present invention is an adhesive mainly used in the field of dental filling resin. It is also used in the fields of filling resin for abutment tooth construction and sealant. Furthermore, the dental adhesive of the present invention includes nickel chromium alloy, gold alloy,
It strongly adheres to metals used in dentistry such as stainless steel, so it can be used as dental cement for inlays, onlays, crowns, bridges, etc., and as an adhesive for orthodontics. The present invention will be specifically explained below with reference to Examples. In addition, the tooth adhesion test and the storage stability test in the examples were conducted by the following method. (1) Tooth adhesion test A fresh extracted bovine front tooth was cut and embedded in an acrylic square rod (10 mm x 10 mm x 20 mm), and its surface was polished with #600Sic abrasive paper to obtain a smooth enamel surface or ivory. formed a textured surface. This surface was etched for 1 minute with a 40% phosphoric acid aqueous solution, washed with water, and then dried by blowing air. A liquid mixture of agent A and agent B at a ratio of 1:1 (weight ratio) was applied to a 5 mm diameter portion of the surface, and the alcohol was evaporated by blowing air. A kneaded product of a commercially available dental composite resin paste "Concise (3M)" was placed on top of this, and an acrylic square rod (10 mm x 10 mm x 20 mm) was further pressure-welded from above. After immersing this specimen in water at 37° C. for 24 hours, both ends of the acrylic square rod were pulled at a speed of 2 mm/min using an Instron tensile tester to determine the adhesive strength. (2) Storage stability test Agent A was placed in a thermostat at 45°C and changes over time were observed with the naked eye. Example 1 The compositions of Part A and Part B shown in Table 1 were mixed separately to prepare a two-part adhesive in the form of two packages consisting of Part A and Part B.

[Table] Comparative Example 1 does not contain methacrylic acid and sodium benzenesulfinate, which are the organic acid components of the present invention, and instead contains benzoyl peroxide as a peroxide to form agents A and B. and
Moreover, in Comparative Example 2, benzoyl peroxide was blended instead of using a phosphoric acid compound to form agents A and B. Furthermore, Agent A of both comparative examples contained 2,
6-di-tert-butyl-4-methylphenol and hydroquinone monomethyl ether were blended. Using a two-component adhesive consisting of Parts A and B, adhesive strength was measured and storage stability was observed in accordance with the tooth adhesion test method and storage stability test method. The results are shown in Table 2.

[Table] From the above table, the dental adhesive described in Example 1 according to the present invention was found to be more effective when etching teeth as well as when not etching, compared to those described in Comparative Examples 1 and 2. It can be seen that it also shows excellent adhesion and also has good storage stability. Examples 2 to 5 Two-component adhesives shown in Table 3 were prepared, and Example 1
An adhesion test was conducted on etched bovine tooth enamel and dentin using the same method. The results are shown in Table 4.

【table】

[Table] From the above table, it can be seen that the adhesive of the present invention has excellent adhesion to both tooth dentin and enamel. Example 6 40 parts by weight of methyl methacrylate, 20 parts by weight of neopentyl glycol dimethacrylate,
2Liquid A consisting of 30 parts by weight of HEM and 10 parts by weight of MA
agent, 100 parts by weight of polymethyl methacrylate powder,
A powder B agent consisting of 4.0 parts by weight of BS-Na and 3.5 parts by weight of DEpT was prepared. Part A and Part B were mixed at a weight ratio of 1:1, and the adhesive strength to bovine dentin etched in the same manner as in Example 1 was measured.
It was 109Kg/ ^cm2 . Example 7 35 parts by weight of 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane (Bis-GMA), 15 parts by weight of triethylene glycol dimethacrylate, 2-
A liquid A agent consisting of 40 parts by weight of HEMA and 10 parts by weight of PM, and a powder B agent consisting of 100 parts by weight of SiO ₂ powder, 1.2 parts by weight of BS-Na, and 1.0 parts by weight of DEpT were prepared. Results of measuring adhesive strength to bovine dentin etched in the same manner as Example 1 by mixing Part A and Part B at a ratio of 1:3 (weight ratio).
It was 102Kg/ ^cm2 . Example 8 Dental nickel-chromium alloy Now-Chrom()
A 7mm x 7mm x 7mm casting chip is embedded in an acrylic square rod (10mm x 10mm x 20mm), and the surface is #600Sic.
A smooth surface was obtained by polishing with abrasive paper. Furthermore, using a sandblaster "Pencil Jet (Yoshida)", sandblasting was performed with 50 micron aluminum oxide powder. Apply the adhesive of Example 6 to a 5 mmφ portion of this surface, and apply a stainless steel square bar (10 mm x 10 mm x 20 mm) from above.
mm) were pressed together and immersed in water at 37°C for 72 hours. This butt specimen was tested using an Instron tensile tester.
Results of measuring tensile strength at a speed of mm/min280
It was Kg/ ^cm2 .

Claims (1)

[Scope of Claims] 1. An adhesive composition containing a (meth)acrylic acid ester monomer and a polymeric curing agent as main components,
A dental adhesive characterized by using (a) a salt of sulfinic acid, (b) an amine, and (c) an organic acid or an acidic inorganic acid ester as a polymerization curing agent. 2. The dental adhesive according to claim 1, wherein the sulfinic acid salt is an arylsulfinic acid salt. 3. The dental adhesive according to claim 2, wherein the salt of arylsulfinic acid is an alkali metal salt of benzenesulfinic acid or an alkali metal salt of p-toluenesulfinic acid. 4. The dental adhesive according to claim 1, wherein the amine is a secondary or tertiary amine bonded to an aryl group. 5. The dental adhesive according to claim 4, wherein the secondary amine bonded to the aryl group is N-alkylaniline or N-alkyl-p-toluidine. 6 The tertiary amine bonded to the aryl group is N,
N'-dialkyl-p-toluidine, N-alkyl-N'-hydroxyalkyl-p-toluidine,
N,N'-di(hydroxyalkyl)-p-toluidine, N,N'-dialkylaniline, N-alkyl-N'-hydroxyalkyl-aniline, or N,N'-di(hydroxyalkyl)-aniline A dental adhesive according to claim 4. 7. The dental adhesive according to claim 1, wherein the organic acid is an aliphatic carboxylic acid or an aromatic sulfonic acid. 8. The dental adhesive according to claim 1, wherein the acidic inorganic acid ester is an acidic phosphoric acid ester or an acidic sulfuric acid ester.