JPH04327571A - Dentine adhesiveness promoting compound, pretreating agent and adhesive composition containing the same compound - Google Patents

Abstract

PURPOSE:To obtain a dentine adhesiveness promoting compound useful as a pretreating agent for dentine adhesion by providing dentine such as enamel with adhesiveness. CONSTITUTION:A compound shown by the formula (R<1> is H or methyl; R<2> is 1k-15C alkylene; R<3> is 1-12C alkyl). A pretreating agent for bonding dentine containing 1-50wt.%, preferably 5-35wt.% compound shown by the formula. A dentine bonding composition containing 0.1-50wt.%, preferably 0.5-20wt.% compound shown by the formula is used. (Methylsulfinyl)methyl (meth)acrylate may be cited as the preferable compound.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tooth adhesion promoting compound and a pretreatment agent and adhesive composition containing the same. Specifically, compounds that promote adhesion to tooth substances such as enamel and dentin, and which can provide excellent adhesive properties to these tooth substances, pretreatment agents for tooth substance adhesion, and tooth substance adhesives. The present invention relates to a tooth adhesion promoting compound used in a composition.

0002

[Prior Art] As adhesives for tooth correction or restoration, many adhesives have been proposed that are made of radically polymerizable monomers such as (meth)acrylic acid ester vinyl monomers and catalysts. Curable composition comprising a meth)acrylic acid ester vinyl monomer, an aromatic carboxylic acid (anhydride) containing a (meth)acryloyloxy group, an amine, and a sulfinic acid (salt) (JP-A-60-44,508) ) and adhesives consisting of (meth)acrylic esters, amines, sulfinic acids (salts), and peroxides that are liquid at room temperature (JP-A-53-3
9,331) etc. However, with conventional adhesives and curable compositions, it has been difficult to obtain sufficient adhesion and compatibility with tooth structure.

0003

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a dentin adhesion-promoting compound that can provide excellent adhesion to tooth substances such as enamel and dentin, and to provide a tooth substance adhesion-promoting compound that can provide excellent adhesion to tooth substances such as enamel and dentin. An object of the present invention is to provide a pretreatment agent for tooth substance adhesion and a tooth substance adhesive composition.

0004

[Means for solving the problem] The above objectives are achieved by the general formula (
1)

[0005]

[Chemical formula 8]

(In the formula, R1 represents a hydrogen atom or a methyl group, R2 represents a straight chain or substituted alkylene group having 1 to 15 carbon atoms, and R3 represents a straight chain or substituted alkyl group having 1 to 12 carbon atoms.) This is achieved by using a dentin adhesion-promoting compound that promotes adhesion to tooth structure.

[0007] The above-mentioned objects are also achieved by applying the compound represented by the general formula (1) to a pretreatment agent for dentin adhesion, which is a solution of at least one solvent selected from the group consisting of water and a water-miscible organic solvent. is also achieved. The present invention also provides a pretreatment agent for tooth bonding in which the concentration of the compound represented by the general formula (1) is 1 to 50% by weight. The present invention further provides a pretreatment agent for tooth bonding, wherein the concentration of the compound represented by formula (1) is 5 to 35% by weight.

Furthermore, the above objects can also be achieved by a tooth adhesive composition comprising a compound represented by the general formula (1), a radically polymerizable monomer, and a polymerization initiator. The present invention also provides that the concentration of the compound represented by general formula (1) is 0.
．． It is a tooth adhesive composition having a content of 1 to 50% by weight. The present invention further provides a tooth adhesive composition in which the concentration of the compound represented by general formula (1) is 0.5 to 20% by weight.

[0009]

[Action] The compound of the present invention that promotes adhesion to tooth substance has the general formula (1)

0010

[Chemical formula 9]

In the formula, R1 is a hydrogen atom or a methyl group, R2 is a linear or substituted alkylene group having 1 to 15 carbon atoms, preferably 1 to 6 carbon atoms, and R3 is a straight chain or substituted alkylene group having 1 to 12 carbon atoms, preferably 1 ~6 straight chain or substituted alkyl groups. Examples of the compound of general formula (1) include (methylsulfinyl)methyl (meth)acrylate, 2-(methylsulfinyl)ethyl (meth)acrylate, 2-(methylsulfinyl)propyl (meth)acrylate, 3
-(Methylsulfinyl)propyl (meth)acrylate, 2-(methylsulfinyl)butyl (meth)acrylate, 3-(methylsulfinyl)butyl (meth)acrylate, 4-(methylsulfinyl)butyl (meth)acrylate, 2-( Methylsulfinyl)pentyl (meth)acrylate, 3-(methylsulfinyl)pentyl (meth)acrylate, 4-(methylsulfinyl)pentyl (meth)acrylate, 5-(methylsulfinyl)pentyl (meth)acrylate, 2-(methylsulfinyl) ) hexyl (meth)acrylate, 3-
(Methylsulfinyl)hexyl (meth)acrylate, 4-(methylsulfinyl)hexyl (meth)acrylate, 5-(methylsulfinyl)hexyl (meth)
Acrylate, 6-(methylsulfinyl)hexyl (
In meth)acrylates, etc., the moiety corresponding to methylsulfinyl is ethylsulfinyl, propylsulfinyl, butylsulfinyl, pentylsulfinyl,
Examples include hexylsulfinyl. In particular (methylsulfinyl)methyl (meth)acrylate, 2-(methylsulfinyl)ethyl (meth)acrylate, 3-(methylsulfinyl)propyl (meth)acrylate, 4-(methylsulfinyl)butyl (meth)acrylate, 5- (Methylsulfinyl)pentyl (meth)acrylate, 2-(methylsulfinyl)pentyl (meth)acrylate, 6-(methylsulfinyl)hexyl (meth)acrylate, 3-(methylsulfinyl)hexyl (meth)acrylate, 2-(ethyl) sulfinyl)ethyl (meth)acrylate, 3-(
Ethylsulfinyl)propyl (meth)acrylate and the like are preferred.

[0012] The pretreatment agent for dentin adhesion that promotes adhesion to tooth substance of the present invention includes compounds represented by general formula (1) such as water, methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran. used as a solution in a water-miscible organic solvent. The concentration of general formula (1) in the pretreatment agent for tooth bonding is 1 to 50% by weight, preferably 3 to 35% by weight. After applying the pretreatment agent to a predetermined location, adhesive is applied to bond the parts.

The tooth adhesive composition of the present invention is a mixture comprising a radically polymerizable monomer, a compound represented by the general formula (1), and a polymerization initiator.

Examples of such radically polymerizable monomers include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, and butyl (meth)acrylate.
Alkyl (meth)acrylates such as meth)acrylates, having a carboxyl group or phosphoric acid group in the side chain (meth)
There are esters of acrylic acid. Examples of radically polymerizable monomers and crosslinking agents include ethylene glycol di(meth)acrylate and diethylene glycol di(meth)acrylate.
Esters of diacrylic acid or dimethacrylic acid of diols such as meth)acrylate, triethylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane di(meth)acrylate Examples include acrylate, bisphenol A-glycidyl methacrylate adduct, and the like.

The amount of the general formula (1) is 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight, and the amount of the polymerization initiator is 0 to 100 parts by weight of the radically polymerizable monomer. .1 to 15 parts by weight, preferably 0.5 to 10 parts by weight.

As the polymerization initiator, benzoyl peroxide-dimethylaniline or dimethyl-p-toluidine and a combination thereof with a salt of benzenesulfinic acid or toluenesulfinic acid, tri-n-
Butylborane and its oxides, camphorquinone and 1,3,5-trialkyl(thio)barbituric acid, 1
, 5-dialkyl(thio)barbituric acid, 5-alkyl(thio)barbituric acid, diethylaminoethyl methacrylate, ethyl dimethylaminobenzoate, (a
) cupric chloride or (b) a chloride ion-forming compound and a cupric ion-forming compound and 1,3,5-trialkyl(thio)barbituric acid, 1,5-dialkyl(thio)barbituric acid, 5-alkyl Examples include combinations of (thio)barbituric acids.

[0017]

[Examples] Next, the present invention will be explained in more detail by referring to reference examples and examples.

Reference Example 1 Synthesis of 2-(methylsulfinyl)ethyl methacrylate. First, 2-(methylthio)ethyl methacrylate is synthesized. Capacity 5 with thermometer, stirrer and dropping funnel
In a 00ml three-necked flask, add 2-(methylthio)-1
- 46 g of ethanol, 51 g of triethylamine, and 500 ml of dehydrated benzene were supplied, and 52 g of methacrylic acid chloride was added dropwise from the dropping funnel so that the temperature of the reaction system was 5° C. or lower. After the dropwise addition was completed, stirring was continued at 5° C. for 1 hour and then at room temperature for 1 hour. Next, the reaction solution was washed with water and a 5% by weight aqueous sodium bicarbonate solution, benzene was removed, and vacuum distillation was performed to obtain 43 g of 2-(methylthio)ethyl methacrylate (yield: 53.
7%).

Next, 29 g of sodium metaperiodate and 200 ml of water were fed into a 300 ml three-necked flask equipped with a thermometer, a stirrer, and a dropping funnel, and the synthesized 2-(methylthio) was added through the dropping funnel. Ethyl methacrylate was added to the reaction system at a temperature of 5°C or less.
0g was dropped. After the dropwise addition was completed, stirring was continued at room temperature for 4 hours. Then, the reaction solution was extracted with chloroform to obtain 2-
18 g of (methylsulfinyl)ethyl methacrylate was obtained (yield 45.0%).

Reference Example 2 Synthesis of 3-(methylsulfinyl)propyl methacrylate. The reaction was carried out in the same manner as in Reference Example 1 except that 50 g of 3-(methylthio)-1-propanol was used. 16 g of 3-(methylsulfinyl)propyl methacrylate was obtained (yield 47.8%).

Reference Example 3 Synthesis of 4-(methylsulfinyl)butyl methacrylate. The reaction was carried out in the same manner as in Reference Example 1 except that 45 g of 4-(methylthio)-1-butanol was used. 14 g of 4-(methylsulfinyl)butyl methacrylate was obtained (yield: 48
．． 0%).

Reference Example 4 Synthesis of 5-(methylsulfinyl)heptyl methacrylate. The reaction was carried out in the same manner as in Reference Example 1 except that 60 g of 5-(methylthio)-1-heptanol was used. 20 g of 5-(methylsulfinyl)heptyl methacrylate was obtained (yield 40.8%).

Reference Example 5 Synthesis of 6-(methylsulfinyl)hexyl methacrylate. The reaction was carried out in the same manner as in Reference Example 1 except that 40 g of 6-(methylthio)-1-hexanol was used. 15 g of 6-(methylsulfinyl)hexyl methacrylate was obtained (yield 39.8%).

Reference Example 6 Synthesis of 3-(methylsulfinyl)hexyl methacrylate. The reaction was carried out in the same manner as in Reference Example 1 except that 50 g of 6-(methylthio)-1-hexanol was used. 19 g of 3-(methylsulfinyl)hexyl methacrylate was obtained (yield 42.4%).

Reference Example 7 Synthesis of 2-(ethylsulfinyl)ethyl methacrylate. The reaction was carried out in the same manner as in Reference Example 1 except that 50 g of 2-(ethylthio)-1-ethanol was used. 14 g of 2-(ethylsulfinyl)ethyl methacrylate was obtained (yield: 43
．． 2%).

Method for evaluating adhesive strength (1) In the case of a room-temperature polymerizing adhesive, a bovine front tooth that had been frozen and stored immediately after extraction was thawed immediately before use.
The crown of the tooth was cut in the axial direction using a low-speed cutter, and the dentin on the labial surface was used as it was. After treatment with 10% citric acid and 3% ferric chloride solution for 30 seconds, washing with water and drying,
A polyester adhesive tape with a hole of mm in diameter was pasted to define the adhesion area. After applying the pretreatment agent described in Examples or Comparative Examples and drying, methyl methacrylate was added to
An acrylic rod was bonded by applying a curable composition prepared by mixing the same amount of polymethyl methacrylate powder with a liquid component containing 0% tributylborane oxide as a polymerization initiator. After being left at room temperature for 30 minutes, the test piece was immersed in water at 37° C. for 24 hours, and then a tensile test was conducted at room temperature at a tensile rate of 2 mm/min. The results were expressed as the average value for 5 test pieces.

(2) In the case of a visible light polymerizable adhesive, the dentin was treated in the same manner as in (1), except that the dentin was treated with a 0.5M aqueous solution of sodium ethylenediaminetetraacetate, pH 7.4, for 60 seconds. After applying the pre-treatment agent and drying, apply the bonding agent “Clearfil Photobond” manufactured by Kuraray Co., Ltd.
It was irradiated for 20 seconds with a light irradiator. Thickness 1mm, diameter 6m
A silicone rubber spacer with a hole of m in size was pasted on, filled with composite resin "Photo Clear Fill" manufactured by Kuraray Co., Ltd., and irradiated with light for 40 seconds. Glue an acrylic rod to the cured resin using instant polymerization resin, and place it in water at 37°C for 2 hours.
After 4 hours of immersion, a tensile test was conducted under the same conditions as in (1).

Examples 1 to 7 Pretreatment agents were prepared by mixing the compounds synthesized in Reference Examples in a 1:1 ethanol:water solution at a concentration of 30% by weight. Adhesive strength evaluation method According to the method described in (1), a pretreatment agent was applied to dentin, a curable composition was applied, and a test piece for adhesive strength evaluation was prepared. The results of the tensile test are shown in Table 1.

Comparative Example 1 Evaluations similar to Examples 1 to 7 were conducted without using a pretreatment agent. The results are shown in Table 1.

[0030]

[Table 1]

Examples 8 to 11 Pretreatment agents were prepared by mixing 2-(methylsulfinyl)ethyl methacrylate and water at concentrations shown in Table 2, and tensile tests were conducted in the same manner as in Examples 1 to 7. Ta. The results are shown in Table 2.

[0032]

[Table 2]

Examples 12 to 18 After carrying out the same procedure as in Examples 1 to 7 up to the treatment with the pretreatment agent, test pieces were prepared and evaluated according to the method described in (2) for evaluation of adhesive strength. Table 3 shows the pretreatment agent compounds and results.
Shown below.

Comparative Example 2 Evaluations similar to Examples 12 to 18 were conducted without using a pretreatment agent. The results are shown in Table 3.

Comparative Example 3 Evaluations similar to Examples 12 to 18 were conducted using a pretreatment agent using 2-hydroxyethyl methacrylate (HEMA). The results are shown in Table 3.

[0036]

[Table 3]

Examples 19 to 22 After carrying out the same procedure as in Examples 8 to 11 up to the treatment with the pretreatment agent, test pieces were prepared and evaluated according to the method described in (2) for evaluation of adhesive strength. The composition and results of the pretreatment agent are shown in Table 4.

[0038]

[Table 4]

Examples 23 to 29 A curable composition was prepared by adding the compounds shown in Table 5 to methyl methacrylate at a concentration of 3% by weight in the adhesive strength evaluation method (1) without using a pretreatment agent. We conducted a test. The results are shown in Table 5.

[0040]

[Table 5]

Example 30 In Example 12, triethylene glycol dimethacrylate with 1% 1,3,5-trimethylbarbituric acid and 0.8% camphorquinone added was used as the bonding agent, and the same procedure was carried out. I went to 7.
An adhesive strength of 9 MPa was obtained.

Example 31 The same procedure as in Example 30 was repeated except that 1% dimethylaminoethyl methacrylate was added to the pretreatment agent, and an adhesive strength of 7.6 PMa was obtained.

Example 32 After the treatment up to the pretreatment agent was carried out in the same manner as in Example 12,
A mixture of 1% camphorquinone and 1% 1,3,5-trimethylbarbituric acid to methyl methacrylate and polymethyl methacrylate powder in a 1:1 weight ratio was placed on the treated surface and a transparent An acrylic plate with a thickness of 3 mm was adhered and light irradiation was performed for 3 minutes. The adhesive strength after immersion in water at 37° C. for 24 hours was 11.4 MPa.

Example 33 The same procedure as in Example 32 was carried out except that 1% dimethylaminoethyl methacrylate was further added to the pretreatment agent, and an adhesive strength of 9.8 MPa was obtained.

Example 34 In Example 1, instead of tributylborane oxide,
2% by weight of 2-hydroxyethyl methacrylate, 0.0005% by weight of copper acetylacetone and 0.04% by weight of vinylbenzyltetradecyldimethylammonium chloride were added to the methyl methacrylate, and 2% by weight of the polymethylmethacrylate based powder was added. 1, 3,
The same procedure was performed except that 5-trimethyl-2-thiobarbituric acid was added, and the result was 13.2 MPa.
An adhesive strength of 100% was obtained.

[0046]

Effects of the Invention As described above, the pretreatment agent for tooth bonding according to the present invention has 1 to 50
Since it is made of a solution containing % by weight, it has the advantage of increasing the adhesive strength of the adhesive used. moreover,
Since the adhesive composition according to the present invention is composed of the compound represented by the general formula (1), a radically polymerizable monomer, and a polymerization initiator, it has significantly higher adhesive strength to tooth structure than conventional products. It has the advantage of being high.

Claims (7)

[Claims] Claim 1: General formula (1) [Formula 1] (wherein, R1 is a hydrogen atom or a methyl group, R2
is a straight chain or substituted alkylene group having 1 to 15 carbon atoms, R3
represents a straight chain or substituted alkyl group having 1 to 12 carbon atoms. ) is a tooth substance adhesion-promoting compound that promotes adhesion to tooth substance. Claim 2: General formula (1) [Formula 2] (wherein, R1 is a hydrogen atom or a methyl group, R2
is a straight chain or substituted alkylene group having 1 to 15 carbon atoms, R3
represents a straight chain or substituted alkyl group having 1 to 12 carbon atoms. A pretreatment agent for tooth bonding, which is a solution of a compound represented by the following formula in at least one solvent selected from the group consisting of water and a water-miscible organic solvent. Claim 3: General formula (1) [Formula 3] (wherein, R1 is a hydrogen atom or a methyl group, R2
is a straight chain or substituted alkylene group having 1 to 15 carbon atoms, R3
represents a straight chain or substituted alkyl group having 1 to 12 carbon atoms. The pretreatment agent for dentin adhesion according to claim 2, wherein the concentration of the compound represented by ) is 1 to 50% by weight. Claim 4: General formula (1) [Formula 4] (wherein, R1 is a hydrogen atom or a methyl group, R2
is a linear and substituted alkylene group having 1 to 15 carbon atoms, R3
represents a straight chain or substituted alkyl group having 1 to 12 carbon atoms. The pretreatment agent for dentin adhesion according to claim 2, wherein the concentration of the compound represented by ) is 5 to 35% by weight. [Claim 5] General formula (1) [Formula 5] (wherein, R1 is a hydrogen atom or a methyl group, R2
is a straight chain or substituted alkylene group having 1 to 15 carbon atoms, R3
represents a straight chain or substituted alkyl group having 1 to 12 carbon atoms. ), a radically polymerizable monomer, or a polymerization initiator. [Claim 6] General formula (1) [Formula 6] (wherein, R1 is a hydrogen atom or a methyl group, R2
is a straight chain or substituted alkylene group having 1 to 15 carbon atoms, R3
represents a straight chain or substituted alkyl group having 1 to 12 carbon atoms. The tooth adhesive composition according to claim 5, wherein the concentration of the compound represented by ) is 0.1 to 50% by weight. [Claim 7] General formula (1) [Formula 7] (wherein, R1 is a hydrogen atom or a methyl group, R2
is a straight chain or substituted alkylene group having 1 to 15 carbon atoms, R3
represents a straight chain or substituted alkyl group having 1 to 12 carbon atoms. 8. The tooth adhesive composition according to claim 7, wherein the concentration of the compound represented by ) is 0.5 to 20% by weight.