JP2891680B2 - Tooth adhesive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a dental adhesive composition. More specifically, the present invention relates to a dental adhesive composition having excellent adhesive properties to tooth materials such as enamel and dentin.

[0002]

2. Description of the Related Art As adhesives for orthodontic or restoring teeth, a large number of adhesives comprising a radical polymerizable monomer such as a vinyl (meth) acrylate monomer and a catalyst have been proposed. A curable composition comprising a (meth) acrylic ester-based vinyl monomer, a (meth) acryloyloxy group-containing aromatic carboxylic acid (anhydride), an amine and a sulfinic acid (salt) (JP-A-60-44508) ) Or an adhesive consisting of (meth) acrylic acid ester, amine, sulfinic acid (salt) and peroxide which is liquid at normal temperature (JP-A-53-3
9,331). However, it has been difficult for conventional adhesives and curable compositions to obtain sufficient adhesive strength and conformity to tooth material.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a dental adhesive composition having excellent adhesiveness to tooth materials such as enamel and dentin.

[0004]

The above object is achieved by the following general formula (1)

[0005]

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(Wherein, 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, Y is a linear or substituted alkylene group having 3 to 5 carbon atoms) This is achieved by a dental adhesive composition comprising a compound represented by the formula (1), a radical polymerizable monomer and a polymerization initiator. The present invention is also a dental adhesive composition wherein the concentration of the compound represented by the general formula (1) is 0.1 to 50% by weight. The present invention is further a tooth adhesive composition wherein the concentration of the compound represented by the general formula (1) is 0.5 to 20% by weight.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The dental adhesive composition of the present invention is a mixture comprising a compound represented by the following general formula (1), a radical polymerizable monomer, and a polymerization initiator.

[0008]

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(Wherein, 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, preferably 2 to 4 carbon atoms, and Y is a 3 to 5 carbon atoms. , Preferably 3 linear or substituted alkylene groups.) Examples of the compound of the general formula (1) include N- (meth) acryloyloxymethyl-2-pyrrolidone and N- (meth) acryloyloxymethyl-2-pyrrolidone.
(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) acryloyl Oxypentyl) -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) acryloyl Oxybutyl) -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) acryloyloxyethoxybuty) ) -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 and the like.
The moiety corresponding to -pyrrolidone is substituted pyrrolidone such as -5-methyl-2-pyrrolidone, -5-ethyl-2-pyrrolidone, -4,5-dimethyl-2-pyrrolidone, 2-piperidone, -6-methyl- Examples of the compound include piperidones such as 2-piperidone and -5-methyl-2-piperidone, and compounds converted into -ε-caprolactam. In particular, N- (2-
(Meth) acryloyloxyethyl) -2-pyrrolidone (each represents a chemical formula, wherein R represents hydrogen or a methyl group),

[0010]

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

[0012]

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

[0014]

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

[0016]

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

[0018]

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

[0020]

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

[0022]

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

[0024]

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

[0026]

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

[0028]

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N- (meth) acryloyloxymethyl-
ε-caprolactam

[0030]

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And the like.

As the radical polymerizable monomer, methyl (meth) acrylate, ethyl (meth) acrylate,
There are alkyl (meth) acrylates such as isopropyl (meth) acrylate and butyl (meth) acrylate, and esters of (meth) acrylic acid having a carboxyl group or a phosphoric acid group in a side chain. Radical polymerizable monomer,
In addition, as a crosslinking agent, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate,
Diacrylic acid or dimethacrylic acid esters of diols such as hexanediol di (meth) acrylate,
There are trimethylolpropane di (meth) 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 0.1 to 100 parts by weight of the radical polymerizable monomer.
It is 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,
A combination of 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, -Alkyl (thio) barbituric acid and the like.

The compound represented by the general formula (1) can be used as a pretreatment agent for bonding to teeth, which promotes adhesion to teeth. The pretreatment agent for bonding to teeth is used as a solution of the compound represented by the general formula (1) in water or a water-miscible organic solvent such as methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran. The concentration of the compound of the general formula (1) in the pretreatment agent for dentin bonding is 1 to 50% by weight, preferably 5 to 35% by weight. After applying the pretreatment agent to a predetermined location, the pretreatment agent is adhered by applying an adhesive.

[0036]

Next, the present invention will be described in more detail with reference to Reference Examples and Examples.

Reference Example 1 Synthesis of N- (3-methacryloyloxypropyl) -2-pyrrolidone 500 m capacity with thermometer, stirrer and dropping funnel
l in a three-necked flask, 51 g of N- (3-hydroxypropyl) -2-pyrrolidone and 40 g of triethylamine.
And 400 ml of dehydrated benzene, and 41 g of methacrylic acid chloride was further added from the dropping funnel.
The solution was dropped as follows. After dropping, 1 at 5 ° C
Stirring was continued for another hour at room temperature. Then, the reaction solution was washed with water and a 5% by weight aqueous solution of sodium hydrogen carbonate, and then benzene was removed.
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 were 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 were 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 were 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 were obtained. (Yield 20.1%). Purification was performed by column chromatography.

Evaluation Method of Adhesive Strength (1) In the case of a room temperature polymerization type adhesive The cow front teeth frozen and stored immediately after withdrawal were thawed immediately before use,
The crown was cut in the axial direction with a low-speed cutter, and the dentin on the lip side was used as it was. Treated with 10% citric acid, 3% ferric chloride solution for 30 seconds, washed with water, dried,
A polyester pressure-sensitive adhesive tape having a hole having a diameter of mm was adhered thereto, and the adhered area was defined. The pretreatment agent described in Examples or Comparative Examples was applied and dried, and then added to methyl methacrylate.
An acrylic rod was adhered by applying a curable composition in which the same amount of polymethyl methacrylate-based powder was mixed with a liquid component to which 0% of a polymerization initiator, tributyl borane oxide, was added. After leaving 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 performed at room temperature at a pulling rate of 2 mm / min. The results were expressed as an average value for five test pieces.

(2) In the case of a visible light-polymerizable adhesive The dentin was treated in the same manner as (1) except that the dentin was treated with a 0.5 M aqueous sodium ethylenediaminetetraacetate solution having a pH of 7.4 for 60 seconds. After applying and drying the pretreatment agent, a bonding agent “Clear Fill Photo Bond” manufactured by Kuraray Co., Ltd. was applied and irradiated with a light irradiator for 20 seconds. A silicone rubber spacer having a thickness of 1 mm and a diameter of 6 mm and having a hole attached thereto was filled with a composite resin “Photoclear Fill” manufactured by Kuraray Co., Ltd., and irradiated with light for 40 seconds. An acrylic rod was adhered to the cured resin with an instant polymerization resin, immersed in water at 37 ° C. for 24 hours, and subjected to a tensile test under the same conditions as (1).

Examples 1 to 7 N- (3-methacryloyloxypropyl) -2-pyrrolidone was mixed with water and / or an organic solvent to prepare a pretreatment agent as shown in Table 1. A pretreatment agent is applied to dentin according to the method described in the evaluation method (1) of the adhesive strength,
The curable composition was applied to prepare a test piece for evaluating adhesive strength.
Table 1 shows the results of the tensile test.

Examples 8 to 14 N-2- (2-methyl-1-methacryloyloxypropyl) -2-pyrrolidone was mixed with water and / or an organic solvent to prepare a pretreatment agent as shown in Table 2. Then, a tensile test was performed in the same manner as in Examples 1 to 7. Table 2 shows the results.

Examples 11 to 13 N- (2-methacryloyloxyethyl) -5-methyl-2-pyrrolidone was mixed with water and / or an organic solvent to prepare a pretreatment agent as shown in Table 3. Examples 1 to 7
A tensile test was performed in the same manner as described above. Table 3 shows the results.

Comparative Example 1 The same evaluation as in Examples 1 to 13 was performed without using a pretreatment agent. Table 1 shows the results.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

[Table 3]

Examples 14 to 20 Up to the treatment with the pretreatment agent, the same procedures as in Examples 1 to 7 were performed, and then test specimens were prepared and evaluated according to the method described in Evaluation Method (2) for Adhesive Strength. Table 4 shows the composition and results of the pretreatment agent.
Shown in

Examples 21 to 23 The same procedures as in Examples 8 to 10 were performed until the treatment with the pretreatment agent, and then test pieces were prepared and evaluated according to the method described in Evaluation Method (2) for Adhesive Strength. Table 5 shows the composition and results of the pretreatment agent.
Shown in

Examples 24 to 26 After the treatment with the pretreatment agent was performed in the same manner as in Examples 11 to 13, test pieces were prepared and evaluated according to the method described in Evaluation Method (2) of Adhesive Strength. Table 6 shows the composition of the pretreatment agent and the results.

Comparative Example 2 The same evaluation as in Examples 14 to 26 was performed without the pretreatment agent. Table 4 shows the results. Comparative Example 3 The same evaluation as in Examples 14 to 26 was performed using a pretreatment agent using 2-hydroxyethyl methacrylate (HEMA). Table 4 shows the results.

[0057]

[Table 4]

[0058]

[Table 5]

[0059]

[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 in the method (1) for evaluating adhesive strength without using a pretreatment agent. The test was performed. Table 7 shows the results.

[0061]

[Table 7]

Example 34 The same procedure as in Example 17 was carried out except that a bonding agent obtained by adding 1% of 1,3,5-trimethylbarbituric acid and 0.8% of camphorquinone to triethylene glycol dimethacrylate was used. 8.
An adhesive strength of 4 MPa was obtained.

Example 35 The same procedure as in Example 34 was carried out except that the pretreatment agent was further added with 1% of dimethylaminoethyl methacrylate, whereby an adhesive strength of 6.5 PMa was obtained.

Example 36 After the treatment up to the pretreatment agent was performed in the same manner as in Example 17,
A liquid in which 1% camphorquinone and 1% 1,3,5-trimethylbarbituric acid are added to methyl methacrylate and a polymethyl methacrylate-based powder mixed at a weight ratio of 1: 1 is placed on the treated surface and is transparent. An acrylic plate having 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% of dimethylaminoethyl methacrylate was further added to the pretreatment agent, whereby 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 and 0.0005% by weight of copper acetylacetone and 0.04% by weight of vinylbenzenetetradecyldimethylammonium chloride are added to methyl methacrylate, and 2% by weight of polymethyl methacrylate-based powder is added. 1,3,3
When the same procedure was performed except that 5-trimethyl-2-thiobarbituric acid was used, the result was 14.2 MPa.
Was obtained.

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

[0068]

As described above, the adhesive composition according to the present invention comprises a compound represented by the general formula (1), a radical polymerizable monomer and a polymerization initiator.
Compared with the conventional product, there is an advantage that the adhesive strength to the tooth is remarkably high.

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Claims (3)

(57) [Claims] 1. A compound of the general formula (1) (Wherein, R represents a hydrogen atom or a methyl group, X represents a linear or substituted alkylene group or alkylene ether group having 1 to 6 carbon atoms, and Y represents a linear or substituted alkylene group having 3 to 5 carbon atoms. A dental adhesive composition comprising a compound represented by the formula (1), a radical polymerizable monomer and a polymerization initiator. 2. A compound of the general formula (1) (Wherein, R represents a hydrogen atom or a methyl group, X represents a linear or substituted alkylene group or alkylene ether group having 1 to 6 carbon atoms, and Y represents a linear or substituted alkylene group having 3 to 5 carbon atoms. )) Is 0.
The dental adhesive composition according to claim 1, which is 1 to 50% by weight. 3. General formula (1) (Wherein, R represents a hydrogen atom or a methyl group, X represents a linear or substituted alkylene group or alkylene ether group having 1 to 6 carbon atoms, and Y represents a linear or substituted alkylene group having 3 to 5 carbon atoms. )) Is 0.
The dental adhesive composition according to claim 1, which is 5 to 20% by weight.