JPH10158114A - Adhesive for dentistry - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an adhesive for dentistry having improved adhesiveness and storage stability with a simple operation without inducing polymerization nor gelation, comprising a solution dissolving a specific hydroxy(thio)barbituric acid derivative in a polymerizable monomer. SOLUTION: This adhesive for dentistry is composed of a solution dissolving 5-hydroxy(thio)barbituric acid derivative such as 5-hydroxy-1,3,5- trimethylbarbituric acid expressed by the formula (R1 is a 1-12C alkyl, allyl or cycloalkyl; R2 and R3 are each H, a 1-12C alkyl, allyl or cycloalkyl; X is 0 or S) preferably in an amount of 0.5-10wt.% (based on the amount of a polymerizable monomer) in a polymerizable monomer such as methyl (meth) acrylate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a dental adhesive. More specifically, the present invention relates to a one-part dental adhesive that is easy to operate.

[0002]

2. Description of the Related Art As adhesives for orthodontic or restorative teeth, many adhesives comprising radical polymerizable monomers such as (meth) acrylate vinyl monomers and catalysts have been proposed. ) A curable composition comprising an acrylic ester vinyl monomer and a (meth) acryloyloxy group-containing aromatic carboxylic acid (anhydride), an amine and a sulfinic acid (salt) (JP-A-60-44508) or at room temperature Adhesive consisting of (meth) acrylic acid ester, amine, sulfinic acid (salt) and peroxide in liquid (JP-A-53-393)
No. 31). However, it has been difficult for conventional adhesives and curable compositions to obtain sufficient adhesive strength and conformity to tooth material.

On the other hand, the present inventors have proposed a polymerization initiator composition comprising a (thio) barbituric acid derivative and a metal halide salt (JP-A-4-126703). Since those dissolved in the body have poor stability and may be polymerized during storage and hardened, it is essential to divide the (thio) barbituric acid derivative and polymerizable monomer into two. There was a problem in terms of gender. Also, quinones such as hydroquinone, which are usually used for the purpose of preventing this, have a low effect of preventing polymerization and curing, and hydroxyanilinophenol has an effect, but there is a problem in that the solution is colored.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a dental adhesive which has excellent adhesion and storage stability without causing polymerization and gelation during storage and is easy to operate. It is in.

[0005]

The present invention is achieved by the following means.

[0006] These objects are represented by the general formula (1)

[0007]

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(Wherein, R1 is an alkyl group having 1 to 12 carbon atoms, an allyl group or a cycloalkyl group, R2,
R3 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an allyl group, or a cycloalkyl group, and X is an oxygen atom or a sulfur atom), and a 5-hydroxy (thio) barbituric acid derivative represented by the following formula: This is achieved by a dental adhesive consisting of a solution dissolved in the monomer.

The present invention also provides a compound represented by the general formula (1):
R1, R of hydroxy (thio) barbituric acid derivatives
This is achieved by the above-mentioned dental adhesive wherein both R3 and R3 are an alkyl group, an allyl group or a cycloalkyl group having 1 to 12 carbon atoms.

The present invention also provides a compound represented by the general formula (1):
R1, R of hydroxy- (thio) barbituric acid derivatives
This is achieved by the dental adhesive wherein both R2 and R3 are methyl groups.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The dental adhesive of the present invention comprises a polymerizable monomer, 5-hydroxy (thio) barbituric acid, and a polymerization initiator.

As the 5-hydroxy (thio) barbituric acid, for example, the substituent R1 in the general formula (1) is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, etc. , R3 are a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group or the like, preferably R1, R2, and R3 are both alkyl groups. Hydroxy-1,3,5-alkyl (thio) barbituric acid is used, more preferably 5-hydroxy-1,
3,5-Trimethylbarbituric acid is used.

The amount of 5-hydroxy (thio) barbituric acid which is the object of the present invention is usually 0.1 to the polymerizable monomer.
The amount is 1% to 20%, preferably 0.5% to 10%. If the amount is too small, the adhesive strength is not increased, and if it is too large, the effect is impaired in actual use.

The polymerizable monomer used in the present invention is preferably a (meth) acrylate monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate There are acrylic (meth) acrylates such as, which are polymerizable monomers and crosslinkers,
Examples include acrylic acid or methacrylic acid esters of diols such as ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate, bisphenol A-glycidyl methacrylate adducts, and urethane dimethacrylate.

As the initiator, a photopolymerization initiator is often used, and a combination of a sensitizer and a reducing agent is generally used. Examples of the sensitizer include camphorquinone, benzyl, diacetyl, benzyldimethylketal, benzyldiethylketal, benzyldi (2-methoxyethyl) ketal, anthraquinone, thioxanthone,
Chlorothioxanthone, benzoin methyl ether, benzoin ethyl ether, benzophenone, bis (4-
(Dimethylaminophenyl) ketone, 4,4'-bisdiethylaminobenzophenone, etc., and are used alone or in combination.

As the reducing agent, tertiary amines, sodium sulfinate derivatives, organometallic compounds and the like are used. Specifically, dimethylaminoethyl methacrylate, dimethyl-p-toluidine, triethanolamine, diethanol-p-toluidine, benzenesulfinic acid sodium,
Sodium toluenesulfinate, etc.
It is also possible to use (thio) barbituric acid such as 3,5-trimethyl (thio) barbituric acid at the same time as a reducing agent.

When the dental adhesive of the present invention is used for a tooth material, it is necessary to apply a primer to a site to be repaired. The compound used as a primer is represented by the following general formula (2).

General formula (2)

[0019]

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(Wherein, R1 is a hydrogen atom or a methyl group, R2 is a linear or substituted alkylene or alkylene ether group having 1 to 6 carbon atoms, and R3 is a 3 to 5 carbon atoms.
Represents a linear or substituted alkylene group. The compounds of the general formula (2) include N- (2-methacryloyloxyethyl) -2-pyrrolidone, N- (3-methacryloyloxypropyl) -2-pyrrolidone,
(2-methacryloyloxypropyl) -2-pyrrolidone and the like.

The concentration of the compound represented by the general formula (2) in the primer is 1 to 50% by weight, preferably 5 to 40% by weight, and water or a water-miscible organic solvent such as methanol, ethanol, acetone or the like is used. Used as a solution.

[0022]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Synthesis of 5-hydroxy-1,3,5-trimethylbarbituric acid) In a 100 ml four-necked flask, 3 g of 1,3,5-trimethylbarbituric acid (17.6 m
mol), 75 ml of 0.02N hydrochloric acid was added and dissolved, and the mixture was heated and stirred at 60 ° C. for 98 hours.
Lyophilization gave a white solid. This was recrystallized from diethyl ether / tetrahydrofuran = 3/1 (V / V) to obtain 2.41 g of white crystals of 5-hydroxy-1,3,5, -trimethylbarbituric acid.

Example 1 A primer prepared by dissolving 0.02% by weight of cupric chloride and 40% by weight of N- (2-methacryloyloxyethyl) -2-pyrrolidone in water was used. 0.3 g of 5-hydroxy-1,3,5-trimethylbarbituric acid and 0.05 g of camphorquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed with urethane dimethacrylate (SH500S manufactured by Shin-Nakamura Chemical Co., Ltd.) and triethylene glycol dimethacrylate (Shin-Nakamura A solution dissolved in 9.65 g of a 1: 1 mixture with 3G) manufactured by Kagaku Co., Ltd. was used as a bonding agent.

Table 1 shows the results of the stability test and the adhesion test.

Example 2 A primer prepared by dissolving 0.02% by weight of cupric chloride and 40% by weight of N- (2-methacryloyloxyethyl) -2-pyrrolidone in water was used. 0.3 g of 5-hydroxy-1,3,5-trimethylbarbituric acid, 0.05 g of camphorquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.05 g of 2,2-dimethoxy-2-phenylacetophenone are mixed with urethane dimethacrylate (Shinnakamura) 1: 1 of SH500S manufactured by Chemical Co., Ltd.) and 2-hydroxyethyl methacrylate (Kanto Chemical Co., Ltd.)
The solution dissolved in 9.6 g of the mixture was used as a bonding agent.

Table 1 shows the results of the stability test and the adhesion test.

Example 3 A primer prepared by dissolving 0.01% by weight of cupric chloride and 40% by weight of N- (2-methacryloyloxyethyl) -2-pyrrolidone in water was used. 0.3 g of 5-hydroxy-1,3,5-trimethylbarbituric acid, 0.05 g of camphorquinone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.05 g of 2,2-dimethoxy-2-phenylacetophenone are mixed with urethane dimethacrylate (Shinnakamura) 1: 1 of SH500S manufactured by Chemical Co., Ltd.) and 2-hydroxyethyl methacrylate (Kanto Chemical Co., Ltd.)
The solution dissolved in 9.6 g of the mixture was used as a bonding agent.

Table 1 shows the results of the stability test and the adhesion test.

Comparative Example 0.3 g of 1,3,5-trimethylbarbituric acid, camphorquinone (manufactured by Tokyo Chemical Industry Co., Ltd.)
8. A 1: 1 mixture of 0.05 g of 2,2-dimethoxy-2-phenylacetophenone and 0.05 g of urethane dimethacrylate (SH500S manufactured by Shin-Nakamura Chemical Co., Ltd.) and 2-hydroxyethyl methacrylate (manufactured by Kanto Chemical Co., Ltd.)
A solution dissolved in 6 g was prepared.

(Test of Stability) The prepared solution was placed in an oven at 50 ° C., stored for one week, and the state of the solution was observed.

(Evaluation Method of Adhesive Strength) Dentin was exposed by cutting the lip side surface of the bovine anterior teeth and finished with No. 600 emery paper to obtain an adhesive surface. It was dried as it was and a polyester pressure-sensitive adhesive tape with a hole of 5 mmφ was stuck thereon to determine the area to be adhered. As a pre-treatment, the surface to be adhered was treated with 10% phosphoric acid for 15 seconds, washed with water and dried, coated with a primer, allowed to stand for 30 seconds, and then dried. The solution after the stability test was applied as a bonding agent, and light irradiation was performed for 20 seconds with a light irradiator Translux (manufactured by Kluzer). A silicone rubber spacer with a hole of 1 mm in thickness and 6 mm in diameter is placed, and a 3M composite resin “Silux Plu
s ", cured by irradiating light for 40 seconds, removing the spacer, immediately bonding an acrylic rod with a polymerized resin, leaving it at room temperature for 30 minutes, immersing it in water at 37 ° C for 24 hours, and then immersing it in 2 mm at room temperature. The tensile test was performed at a speed of / min. The results were expressed as an average value for five test pieces.

[0033]

[Table 1]

[0034]

As described above, according to the present invention, the general formula (1)

[0035]

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(Wherein, R1 represents an alkyl group having 1 to 12 carbon atoms, an allyl group or a cycloalkyl group, R2,
R3 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an allyl group or a cycloalkyl group, and X is an oxygen atom or a sulfur atom), and an adhesive obtained by dissolving a 5-hydroxy (thio) barbituric acid derivative represented by the following formula: Has no gelation during storage, is capable of stable storage, and has excellent adhesion.
Further, by combining with a primer, it is possible to obtain a one-pack type dental adhesive which is excellent in the adhesive performance to the tooth substance and easy to operate.

Claims (3)

[Claims] 1. A compound of the general formula (1) (Wherein, R1 is an alkyl group having 1 to 12 carbon atoms,
An allyl group or a cycloalkyl group, R2 and R3 each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an allyl group or a cycloalkyl group, and X represents an oxygen atom or a sulfur atom. A dental adhesive comprising a solution in which a thio) barbituric acid derivative is dissolved in a polymerizable monomer. 2. The 5-hydroxy (thio) barbituric acid derivative represented by the general formula (1), wherein R1, R2 and R3 are all an alkyl group having 1 to 12 carbon atoms, an allyl group or a cycloalkyl group. Item 6. The dental adhesive according to Item 1. 3. The dental adhesive according to claim 1, wherein R1, R2 and R3 of the 5-hydroxy (thio) barbituric acid derivative represented by the general formula (1) are both methyl groups.