JPH04217905A - Dentinal bonding promoting compound, pretreating agent and bonding composition containing the same - Google Patents

Abstract

PURPOSE:To obtain a compound capable of imparting excellent adhesion to dentins such as enamel or ebur dentis and a pretreating agent for dentinal bonding capable of enhancing bonding strength of an adhesive used employing the aforementioned compound and a dentinal bonding composition having a high bonding strength to the dentin. CONSTITUTION:A compound, e.g. N-(3-methacryloyloxypropyl)-2-pyrrolidine expressed by the formula (R is H or CH3; X is 1-6C straight-chain or substituted alkylene or alkylene ether; Y is 3-5C straight-chain or substituted alkylene) and capable of promoting bonding to dentins, a pretreating agent composed of a solution containing the above-mentioned compound at 1-50wt.%, preferably 5-35wt.% concentration thereof in water and/or a water-miscible organic solvent for dentinal bonding and a dentinal bonding composition composed of the aforementioned compound, a radically polymerizable monomer and a polymerization initiator at 0.1-50wt.%, preferably 0.5-20wt.% concentration of the above- mentioned 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, R is a hydrogen atom or a methyl group, X is a straight chain or substituted alkylene group having 1 to 6 carbon atoms or an alkylene ether group, and Y is a straight chain or substituted alkylene group having 3 to 5 carbon atoms. This is achieved using a dentin adhesion-promoting compound that promotes adhesion to the 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, R is a hydrogen atom or a methyl group, X is a linear or substituted alkylene group or alkylene ether group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and Y is a C 3 to 5 , preferably 3 straight chain or substituted alkylene groups. Examples of the compound of general formula (1) include N-(meth)acryloyloxymethyl-2-pyrrolidone, N-(2-(meth)acryloyloxyethyl)
-2-pyrrolidone, N-(3-(meth)acryloyloxypropyl)-2-pyrrolidone, N-(2-(meth)
Acryloyloxypropyl)-2-pyrrolidone, N-
(2-(meth)acryloyloxybutyl)-2-pyrrolidone, N-(3-(meth)acryloyloxybutyl)-2-pyrrolidone, N-(4-(meth)acryloyloxybutyl)-2-pyrrolidone, N -2-(2-methyl-1-(meth)acryloyloxypropyl)-2-
Pyrrolidone, N-2-(2-methyl-1-(meth)acryloyloxybutyl)-2-pyrrolidone, N-2-(
2-Methyl-1-(meth)acryloyloxypentyl)-2-pyrrolidone, N-2-(1-methyl-1-(meth)acryloyloxybutyl)-2-pyrrolidone, N
-2-(2-ethyl-1-(meth)acryloyloxybutyl)-2-pyrrolidone, N-3-(2-methyl-1
-(meth)acryloyloxybutyl)-2-pyrrolidone, N-3-(2-ethyl-1-(meth)acryloyloxybutyl)-2-pyrrolidone, N-3-(3-methyl-1-(meth) acryloyloxybutyl)-2-pyrrolidone, N-3-(3-methyl-1-(meth)acryloyloxypentyl)-2-pyrrolidone, N-(2-
Methyl-4-(meth)acryloyloxybutyl)-2
-pyrrolidone, N-(3-methyl-4-(meth)acryloyloxybutyl)-2-pyrrolidone, N-((meth)acryloyloxymethoxymethyl)-2-pyrrolidone, N-((meth)acryloyloxymethoxyethyl) )-2-pyrrolidone, N-((meth)acryloyloxymethoxypropyl)-2-pyrrolidone, N-((meth)acryloyloxymethoxybutyl)-2-pyrrolidone, N-((meth)acryloyloxymethoxypentyl)- 2-pyrrolidone, N-((meth)acryloyloxyethoxymethyl)-2-pyrrolidone, N-((meth)acryloyloxyethoxyethyl)-2-pyrrolidone, N-((meth)acryloyloxyethoxypropyl)-2- Pyrrolidone, N-((meth)acryloyloxyethoxybutyl)-2-pyrrolidone, N-((meth)acryloyloxypropoxymethyl)-2-pyrrolidone, N-((meth)acryloyloxypropoxyethyl)-2-pyrrolidone, N-((meth)acryloyloxypropoxypropyl)-2-pyrrolidone, N-(
(meth)acryloyloxybutoxymethyl)-2-pyrrolidone, N-((meth)acryloyloxybutoxyethyl)-2-pyrrolidone, N-((meth)acryloyloxypentoxymethyl)-2-pyrrolidone, N-(
(meth)acryloyloxymethoxymethoxymethyl)
-2-pyrrolidone, N-((meth)acryloyloxymethoxymethoxyethyl)-2-pyrrolidone, N-((
(meth)acryloyloxyethoxyethoxyethyl)-
2-pyrrolidone, etc., and the moiety corresponding to -2-pyrrolidone is -5-methyl-2-pyrrolidone, -5-ethyl-2-pyrrolidone, -4,5-dimethyl-2-pyrrolidone, etc. Substituted pyrrolidone, -2-piperidone, -6-methyl-2-piperidone, -5-methyl-2
-Piperidone such as -piperidone, -ε-caprolactam, and other compounds are mentioned. Especially N-(2-(meta)
(acryloyloxyethyl)-2-pyrrolidone (the chemical formulas are shown below, in which R represents hydrogen or a methyl group),

0012

[Chemical formula 10]

N-(3-(meth)acryloyloxypropyl)-2-pyrrolidone,

[0014]

[Chemical formula 11]

N-(2-(meth)acryloyloxybutyl)-2-pyrrolidone,

[0016]

[Chemical formula 12]

N-(3-(methacryloyloxybutyl)-2-pyrrolidone,

[0018]

[Chemical formula 13]

N-(4-(methacryloyloxybutyl)-2-pyrrolidone,

[0020]

[Chemical formula 14]

N-2-(2-methyl-1-(meth)acryloyloxypropyl)-2-pyrrolidone,

002
2]

[Chemical formula 15]

N-((meth)acryloyloxyethoxyethyl)-2-pyrrolidone,

[0024]

[Chemical formula 16]

N-((meth)acryloyloxyethoxyethoxyethyl)-2-pyrrolidone,

[0026]

[Chemical formula 17]

N-(2-(meth)acryloyloxyethyl)-5-methyl-2-pyrrolidone,

[0028]

[Chemical formula 18]

N-(2-(meth)acryloyloxyethyl)-4,5-dimethyl-2-pyrrolidone,

003
0]

[Chemical formula 19]

N-(meth)acryloyloxymethyl-
ε-caprolactam

[0032]

[C20]

[0033] etc. are preferred.

[0034] As the pretreatment agent for dentin adhesion that promotes adhesion to dentin of the present invention, compounds represented by general formula (1) such as water or methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, tetrahydrofuran, etc. 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) relative to 100 parts by weight of the radically polymerizable monomer 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. .1 to 15 parts by weight, preferably 0.5 to 10 parts by weight.

As a 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.

[0039]

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

Reference Example 1 Synthesis of N-(3-methacryloyloxypropyl)-2-pyrrolidone. Capacity 500m with thermometer, stirrer and dropping funnel
51 g of N-(3-hydroxypropyl)-2-pyrrolidone, 40 g of triethylamine, and 400 ml of dehydrated benzene were fed into a three-neck flask, and then 41 g of methacrylic acid chloride was added from the dropping funnel until the temperature of the reaction system was below 5°C. It was dripped like this. 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 N-(
60 g of 3-methacryloyloxypropyl)-2-pyrrolidone was obtained (yield 79.8%).

Reference Example 2 Synthesis of N-2-(2-methyl-1-methacryloyloxypropyl)-2-pyrrolidone. N-2-(1-hydroxy-2-methylpropyl)-2
- The reaction was carried out in the same manner as in Reference Example 1 except that 15 g of pyrrolidone was used. 6.0 g of N-2-(2-methyl-1-methacryloyloxypropyl)-2-pyrrolidone was obtained (yield 27.9%).

Reference Example 3 Synthesis of N-(2-methacryloyloxyethyl)-5-methyl-2-pyrrolidone. The reaction was carried out in the same manner as in Reference Example 1 except that 18 g of N-(2-droxyethyl)-5-methyl-2-pyrrolidone was used. 8.1 g of N-(2-methacryloyloxyethyl)-5-methyl-2-pyrrolidone was obtained (yield 30.5%)
.

Reference Example 4 Synthesis of N-(3-methacryloyloxybutyl)-2-pyrrolidone. N-3-(4-hydroxybutyl)-2-pyrrolidone 1
The reaction was carried out in the same manner as in Reference Example 1 except that 5 g was used. N-
(4.5 g of 3-(methacryloyloxybutyl)-2-pyrrolidone was obtained (yield 20.9%).

Reference Example 5 Synthesis of N-(2-methacryloyloxybutyl)-2-pyrrolidone. N-2-(4-hydroxybutyl)-2-pyrrolidone 2
The reaction was carried out in the same manner as in Reference Example 1 except that 0 g was used. N-
6.9 g of (2-methacryloyloxybutyl)-2-pyrrolidone was obtained (yield 24.0%).

Reference Example 6 Synthesis of N-(2-methacryloyloxyethyl)-4,5-dimethyl-2-pyrrolidone. N-(2-hydroxyethyl)-4,5-dimethyl-2
- The reaction was carried out in the same manner as in Reference Example 1 except that 20 g of pyrrolidone was used. N-(2-methacryloyloxyethyl)-
5.2 g of 4,5-dimethyl-2-pyrrolidone was obtained. (Yield 18.1%).

Reference Example 7 Synthesis of N-(methacryloyloxyethoxyethyl)-2-pyrrolidone. The reaction was carried out in the same manner as in Reference Example 1 except that 20 g of N-(2-hydroxyethoxyethyl)-2-pyrrolidone was used. 5.6 g of N-(methacryloyloxyethoxyethyl)-2-pyrrolidone was obtained. (Yield 20.1%). Purification was performed by column chromatography.

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 treatment was carried out 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 N-(3-methacryloyloxypropyl)-2-pyrrolidone and water and/or an organic solvent were mixed to prepare pretreatment agents as shown in Table 1. Adhesive strength evaluation method (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.

Examples 8 to 14 Pretreatment agents as shown in Table 2 were prepared by mixing N-2-(2-methyl-1-methacryloyloxypropyl)-2-pyrrolidone and water and/or an organic solvent. Then, a tensile test was conducted in the same manner as in Examples 1 to 7. The results are shown in Table 2.

Examples 11 to 13 N-(2-methacryloyloxyethyl)-5-methyl-2-pyrrolidone and water and/or an organic solvent were mixed to prepare pretreatment agents as shown in Table 3. Examples 1-7
A tensile test was conducted in the same manner. The results are shown in Table 3.

Comparative Example 1 Evaluations similar to Examples 1 to 13 were conducted without using a pretreatment agent. The results are shown in Table 1.

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

[Table 3]

Examples 14 to 20 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 the adhesive strength evaluation method (2). The composition and results of the pretreatment agent are shown in Table 4.

Examples 21 to 23 After carrying out the same procedure as in Examples 8 to 10 up to the treatment with the pretreatment agent, test pieces were prepared and evaluated according to the method described in the method (2) for evaluating adhesive strength. Table 5 shows the composition and results of the pretreatment agent.
Shown below.

Examples 24 to 26 After carrying out the same procedure as in Examples 11 to 13 up to the treatment with the pretreatment agent, test pieces were prepared and evaluated according to the method described in the method (2) for evaluating adhesive strength. The composition and results of the pretreatment agent are shown in Table 6.

Comparative Example 2 Evaluations similar to Examples 14 to 26 were conducted without using a pretreatment agent. The results are shown in Table 4.

Comparative Example 3 Evaluations similar to Examples 14 to 26 were conducted using a pretreatment agent using 2-hydroxyethyl methacrylate (HEMA). The results are shown in Table 4.

[0061]

[Table 4]

[0062]

[Table 5]

[0063]

[Table 6]

Examples 27 to 33 A curable composition was prepared by adding the compound shown in Table 7 to methyl methacrylate at a concentration of 3% by weight according to the adhesive strength evaluation method (1) without using a pretreatment agent. The test was conducted. The results are shown in Table 7.

[0065]

[Table 7]

Example 34 In Example 17, 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 8.
An adhesive strength of 4 MPa was obtained.

Example 35 Example 34 was repeated except that 1% dimethylaminoethyl methacrylate was added to the pretreatment agent, and an adhesive strength of 6.5 PMa was obtained.

Example 36 After the treatment up to the pretreatment agent was carried out in the same manner as in Example 17,
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 13.9 MPa.

Example 37 The same procedure as in Example 36 was carried out except that 1% dimethylaminoethyl methacrylate was further added to the pretreatment agent, and an adhesive strength of 10.1 MPa was obtained.

Example 38 In Example 3, instead of tributylborane oxide,
2% by weight of 2-hydroxyethyl methacrylate, 0.0005% by weight of copper acetylacetone and 0.04% by weight of vinylbenzenetetradecyldimethylammonium chloride were added to the methyl methacrylate, and 2% by weight of the polymethyl methacrylate based powder was added. 1, 3,
The same procedure was performed except that 5-trimethyl-2-thiobarbituric acid was added, and the result was 14.2 MPa.
An adhesive strength of 100% was obtained.

Example 39 In Example 38, no pretreatment agent was used and 2% by weight of 2-hydroxyethyl methacrylate was replaced by 2-hydroxyethyl methacrylate.
Weight % N-(3-methacryloyloxypropyl)-
When the same procedure was performed except that 2-pyrrolidone was used, 1
An adhesive strength of 3.9 MPa was obtained.

[0072]

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, R is a hydrogen atom or a methyl group, X is a linear or substituted alkylene group having 1 to 6 carbon atoms or an alkylene ether group, and Y is a carbon A dentin adhesion-promoting compound represented by the following formula (representing a linear or substituted alkylene group of numbers 3 to 5). Claim 2: General formula (1) [Formula 2] (wherein, R is a hydrogen atom or a methyl group, X is a linear or substituted alkylene group having 1 to 6 carbon atoms or an alkylene ether group, and Y is a carbon A pretreatment agent for dentin adhesion, which is a solution of a compound represented by (representing a linear or substituted alkylene group of numbers 3 to 5) 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, R is a hydrogen atom or a methyl group, X is a linear or substituted alkylene group having 1 to 6 carbon atoms or an alkylene ether group, and Y is a carbon represents a linear or substituted alkylene group of numbers 3 to 5).
The pretreatment agent for tooth bonding according to claim 2, which is 50% by weight. [Claim 4] General formula (1) [Formula 4] (wherein, R is a hydrogen atom or a methyl group, X is a linear or substituted alkylene group having 1 to 6 carbon atoms or an alkylene ether group, and Y is a carbon represents a linear or substituted alkylene group of numbers 3 to 5).
The pretreatment agent for tooth bonding according to claim 2, which contains 35% by weight. [Claim 5] General formula (1) [Formula 5] (wherein, R is a hydrogen atom or a methyl group, X is a linear or substituted alkylene group having 1 to 6 carbon atoms or an alkylene ether group, and Y is a carbon A tooth adhesive composition comprising a compound represented by (representing a linear or substituted alkylene group of 3 to 5), a radically polymerizable monomer, and a polymerization initiator. [Claim 6] General formula (1) [Formula 6] (wherein, R is a hydrogen atom or a methyl group, X is a linear or substituted alkylene group having 1 to 6 carbon atoms or an alkylene ether group, and Y is a carbon represents a linear or substituted alkylene group of numbers 3 to 5).
The tooth adhesive composition according to claim 5, wherein the content is 1 to 50% by weight. [Claim 7] General formula (1) [Formula 7] (wherein, R is a hydrogen atom or a methyl group, X is a linear or substituted alkylene group having 1 to 6 carbon atoms or an alkylene ether group, and Y is a carbon represents a linear or substituted alkylene group of numbers 3 to 5).
The tooth adhesive composition according to claim 7, wherein the content is 5 to 20% by weight.