JP2732955B2 - Curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel curable composition. Specifically, it gives a cured product having high tensile strength, and has a hydrophilic surface such as a living hard tissue such as a tooth material, a metal material, or a ceramic material even under wet conditions, and has a high adhesion to an object containing a metal element. It is a curable composition having strength.

[0002]

2. Description of the Related Art In recent years, composite resins, glass ionomer cements, amalgams, and the like have been used for repairing relatively small defective portions of teeth formed by dental caries. Among these, composite resins and glass ionomer cements have been used. Since it has a color tone and transparency similar to teeth, it is frequently used as an aesthetic material.

However, these two types of dental filling materials have been pointed out with various clinical problems.

[0004] For example, although a composite resin has high mechanical strength, it does not itself have an adhesive property with tooth material, and therefore, it is necessary to use an adhesive called a bonding material at the time of filling. However, the use of such a bonding material not only complicates the clinical operation, but also has the disadvantage that if water in the oral cavity enters during use, the adhesive strength is significantly reduced. Furthermore, even if a bonding material is used, there is a problem that the bonding strength between the composite resin and the teeth, particularly the dentin thereof, is insufficient. For this reason, at the boundary between the tooth and the gingiva, which is called the cervical region, since the dentin is exposed on the tooth surface, the detachment of the composite resin is often a problem.

On the other hand, glass ionomer cement is a material that is more hydrophilic than composite resin and adheres to tooth without using a bonding material. Therefore, although a complicated bonding operation like a composite resin is not required, there is a disadvantage that the mechanical strength of the material itself is low and the material cannot be applied to a portion where stress is applied.

Accordingly, various types of dentin-adhesive monomers have been developed as an attempt to improve the adhesion of the composite resin to the dentin. For example, JP-A-57-3
No. 8749 discloses 2- (3,4-dicarboxybenzoyloxy) -1,3-dimethacryloyloxypropane. However, a curable composition using this monomer has disadvantages such as easy adsorption of a coloring component on the surface of the cured product and insufficient mechanical strength. See also
JP-A-1-127717 discloses poly (meth) acrylates and poly (meth) acrylates of bisphenol polyepoxy compounds.
Acryloyloxyl group-containing aromatic polycarboxylic acid or its anhydride, (meth) acrylate compound,
A curable composition comprising an inorganic filler and a curing agent is disclosed. However, this composition has the disadvantage that when used as a filling material, the adhesive strength with the teeth is insufficient. The present inventors have previously proposed a curable composition comprising a vinyl monomer having an acidic group, an ion-eluting filler, and a polymerization initiator, but the composition may adsorb a coloring component on the surface of the cured product, Also, the mechanical strength was not always sufficient.

[0007]

As described above, there has been a demand for a filling material which does not require complicated operations, adheres firmly to the dentin even under wet conditions, has little coloring, and has sufficient strength. .

[0008]

Means for Solving the Problems The present inventors have intensively studied to overcome the above technical problems. As a result, a composition comprising an acidic group-containing vinyl monomer having a specific structure, a specific ion-eluting filler and a polymerization initiator, adheres firmly to teeth even when cured under moist conditions, has little coloration and The cured product was found to have sufficient strength, and the present invention was completed.

That is, the present invention provides: (A) the following general formula [1]

[0010]

Embedded image (Wherein, R ₁ and R ₄ represent a hydrogen atom or a methyl group, and R ₂ and R ₃ represent an alkylene group having 1 to 4 carbon atoms). 100 parts by weight of monomer, (B) 2 mgeq / g to 60
30 to 500 parts by weight of an ion-eluting filler that elutes polyvalent metal ions of mgeq / g, and (C) a polymerization initiator 0.1
It is a curable composition containing up to 3 parts by weight.

In the above general formula [1], R ₂ and R ₃ are an alkyl group having 1 to 4 carbon atoms, and specific examples of R ₂ include those having the following structures: Specific examples of R3 include those having the following structures.

--CH ₂ CH _2- , --CH ₂ CH ₂ CH ₂
-, -CH ₂ CH ₂ CH ₂ CH _2- Preferred specific examples of the acidic group-containing vinyl monomer represented by the general formula [1] are as follows.

[0013]

Embedded image

[0014]

Embedded image

[0015]

Embedded image

[0016]

Embedded image (However, R ₁ and R ₄ are as defined above) The method for producing the acidic group-containing vinyl monomer represented by the general formula [1] is not particularly limited, and any method may be employed. An example of an industrially suitable method is specifically described below.

That is, the following general formula [2]

[0018]

Embedded image (However, R ₁ is a hydrogen atom or a methyl group, R ₂ is a carbon atom 1
And represents alkyl groups 4 to 4. ) And the following general formula [3]

[0019]

Embedded image (However, R ₃ represents an alkylene group having 1 to 4 carbon atoms.)
Is reacted with a dicarboxylic acid or an anhydride thereof to obtain a monocarboxylic acid vinyl monomer, and then represented by the following general formula [4]

[0020]

Embedded image (However, R ₄ represents a hydrogen atom or a methyl group.) By reacting an epoxy compound represented by the formula (1) to obtain a monohydroxyl vinyl monomer, and then adding a trimellitic acid compound to obtain an acidic group represented by the general formula [1]. A vinyl monomer containing is obtained.

As the vinyl compound represented by the general formula [2], known compounds can be used without any limitation. For example, 2-
Hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, and the like are preferably used.

As the vinyl compound represented by the general formula [3], known compounds can be used without any limitation. For example, succinic acid, glutaric acid, adipic acid or anhydrides thereof are preferably used.

Glycidyl methacrylate is preferred as the epoxy compound represented by the general formula [4], and trimellitic anhydride chloride is suitably used as the trimellitic acid compound in the above reaction.

[0024] The reaction molar ratio of the dicarboxylic Bonn acids of general formula (3) with respect to the vinyl compound of the general formula (2) At a above reaction is preferably be reacted in the range of 1 to 2, 1.0
The range of -1.5 is more preferable. As the reaction catalyst used at this time, known catalysts can be used, and examples thereof include aliphatic amines such as triethylamine and trimethylamine, and pyridine. The range of 0.1 to 1 mole is suitable. Examples of the solvent used in this reaction include tetrahydrofuran, dioxane, dimethyl sulfoxide and the like. The reaction temperature can be selected from the range of 30 to 80 ° C, and preferably is in the range of 40 to 70 ° C. The reaction time is not particularly limited and can be generally selected from a range of about 1 to 50 hours, but may be determined within a range where the reactants do not polymerize in relation to the reaction temperature. It is also preferable to add a small amount of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, and butylhydroxytoluene. After the reaction, the solvent is removed under reduced pressure, then dissolved in a water-insoluble solvent such as benzene, and washed with an acid such as hydrochloric acid to remove the reaction catalyst. After washing, the product is extracted into the aqueous layer with a weak alkali such as sodium carbonate, washed with an organic solvent such as ether, and then formed again in an organic layer using an acid such as dilute hydrochloric acid and a water-insoluble solvent such as ethyl acetate. The product is extracted and then the solvent is removed under reduced pressure to obtain a highly pure product.

The reaction mole of epoxy compound of the general formula (4) with respect to monocarboxylic acid vinyl monomers obtained by reaction of a dicarboxylic Bonn acid vinyl compound and the general formula [3] of the general formula (2) At a the reaction The reaction is preferably performed in a ratio of 1 to 2, but more preferably in a range of 1.0 to 1.5. What is known as the time the reaction catalyst used is can in a <br/> used, To exemplify them, p- toluenesulfonic acid, pyridine, triethylamine, trimethylamine,
Among them, p-toluenesulfonic acid is preferably used. The addition amount of these reaction catalysts is preferably in the range of 0.1 to 1 mol per mol of the vinyl monocarboxylate monomer. This reaction may not require the addition of a solvent, but if necessary, benzene, toluene, xylene, chloroform, diethyl ether,
Tetrahydrofuran, dioxane, dimethyl sulfoxide and the like can be used. The reaction temperature is between room temperature and 8
The temperature can be selected from the range of 0 ° C, but is preferably in the range of room temperature to 50 ° C. The reaction time is not particularly limited and can be generally selected from a range of about 1 to 30 hours, but may be determined within a range where the reactants do not polymerize in relation to the reaction temperature. It is also preferable to add a small amount of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, and butylhydroxytoluene. When a water-insoluble solvent is used as the reaction solvent, the reaction solution can be purified by washing with water or a weak alkali such as an aqueous sodium carbonate solution, and when the reaction solvent is soluble in water, the solvent can be purified. Can be replaced with a water-insoluble substance, such as benzene, and then purified by the above washing.

The reaction molar ratio of a trimellitic acid compound such as trimellitic anhydride chloride to a monohydroxyvinyl monomer obtained by reacting a vinyl monocarboxylate monomer with an epoxy compound of the general formula [4] is 0.5 to 5.0.
The reaction can be performed in the range of 1.5,
A range of 1.2 is more preferred. As the reaction catalyst used at this time, known catalysts can be used, and examples thereof include pyridine, triethylamine, trimethylamine and the like. The addition amount of these reaction catalysts is in the range of 1 to 2 moles, preferably 1 to 1.5 moles relative to the above monohydroxyvinyl monomer. Further, as a solvent used in this reaction, benzene, toluene, xylene, chloroform, diethyl ether, tetrahydrofuran, dioxane, dimethyl sulfoxide and the like can be used. The temperature of the reaction can be selected from the range of 0 ° C. to 40 ° C., but is preferably in the range of 0 ° C. to 30 ° C. to avoid polymerization of the reactants since this reaction is quite exothermic. The reaction time is not particularly limited and can be generally selected from the range of about 30 minutes to 3 hours.
It is also preferable to add a small amount of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, and butylhydroxytoluene. After the reaction, if the catalyst hydrochloride or the like precipitates as a solid, it can be removed by filtration, and if it does not precipitate, it can be removed by washing with water. When trimellitic acid chloride is used as the trimellitic acid compound, the anhydride can be hydrolyzed to dicarboxylic acid by adding water to the reaction solution after vigorously stirring at around room temperature after removing the catalyst. At this time, the rate of hydrolysis can be increased by the coexistence of a water-soluble solvent such as tetrahydrofuran. The temperature of the hydrolysis reaction may be selected from the range of 10 to 40 ° C, and the time required for the reaction is about 3 to 50 hours. After the hydrolysis reaction, the desired vinyl monomer having an acidic group can be obtained by dehydrating the solution and removing the solvent.

In addition to the acidic group-containing vinyl monomer,
It is also a preferable embodiment to use another vinyl monomer. Representative examples of the vinyl monomer preferably used include those having an acryl group and / or a methacryl group. Specific examples thereof are as follows.

A) Monofunctional monomers Methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, and their acrylates, acrylic acid, methacrylic acid,
p-methacryloxybenzoic acid, N-2-hydroxy-3
-Methacryloxypropyl-N-phenylglycine, 4
-Methacryloxyethyl trimellitic acid and its anhydride, 6-methacryloxyhexamethylenemalonic acid, 10
-Methacryloxydecamethylene malonic acid, 2-methacryloxyethyl dihydrogen phosphate, 10-methacryloxydecamethylene dihydrogen phosphate, 2-hydroxyethyl hydrogen phenyl phosphate.

B) Bifunctional vinyl monomer (i) Aromatic compound 2,2-bis (methacryloxyphenyl) propane
2,2-bis [4- (3-methacryloxy) -2-hydroxypropoxyphenyl) propane, 2,2-bis (4-methacryloxyethoxyphenyl) propane,
2,2-bis (4-methacryloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloxytetraethoxyphenyl) propane, 2,2-bis (4-methacryloxypentaethoxyphenyl) propane, 2,
2-bis (4-methacryloxydipropoxyphenyl)
Propane, 2 (4-methacryloxyethoxyphenyl)
-2 (4-methacryloxydiethoxyphenyl) propane, 2 (4-methacryloxydiethoxyphenyl) -2
(4-methacryloxytriethoxyphenyl) propane, 2 (4-methacryloxydipropoxyphenyl)-
2 (4-methacryloxytriethoxyphenyl) propane, 2,2-bis (4-methacryloxydipropoxyphenyl) propane, 2,2-bis (4-methacryloxyisopropoxyphenyl) propane and their acrylates (ii) Aliphatic compound ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, butylene glycol dimethacrylate,
Neopentyl glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate and their acrylates b) Trifunctional vinyl monomer trimethylol Propane trimethacrylate, trimethylol ethane trimethacrylate, pentaerythritol trimethacrylate, trimethylol methane trimethacrylate and their acrylates and monomers represented by the following structural formula

[0030]

Embedded image (However, the definition of R ₁ is as described above.) C) Tetrafunctional vinyl monomers pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate, and urethane monomers represented by the following structural formula

[0031]

Embedded image The above-mentioned other vinyl monomers can be used alone or, if necessary, in combination of two or more.

The preferable addition amount of the other vinyl monomer to the acidic group-containing vinyl monomer is from 0 to 70% by weight, more preferably from 5 to 50% by weight, based on the total amount of the mixed monomers. If no other vinyl monomer is added, the viscosity of the monomer increases and the operability deteriorates.
If it is more than 0% by weight, the adhesiveness of the curable composition to the tooth tends to decrease.

The ion-eluting filler used in the present invention is:
2 mgeq / g to 60 mgeq / g, preferably 5 mgeq / g to 3
It elutes 0 mgeq / g of polyvalent metal ions. The polyvalent ion elution amount of the ion eluting filler is 60 mgeq / g
If it is larger, most of the filler will be dissolved, and the tensile strength of the cured product will be low. If the polyvalent metal ion elution amount is less than 2 mgeq / g, the coloring component tends to be adsorbed on the surface of the cured product. In the present invention, the ion elution amount of the filler refers to the amount of ions eluted when 1 g of the filler is immersed in 50 ml of an aqueous acrylic acid solution at a temperature of 37 ° C. and a pH of 2.2 for 24 hours. Further, the polyvalent metal ion is a divalent or higher valent metal ion capable of binding to the acidic group of the acidic group-containing vinyl monomer, and typical examples include calcium, strontium, barium, aluminum,
Metal ions such as zinc and lanthanoids.

The ion-eluting filler is not particularly limited as long as it satisfies the above conditions. Preferred examples thereof include hydroxides such as calcium hydroxide and strontium hydroxide, zinc oxide and fluoroaluminosilicate glass. And the like. Among them, fluoroaluminosilicate glass is the most excellent and preferable in view of the coloring resistance of the cured product.

The fluoroaluminosilicate glass may be a dental cement, for example, a known one used for a glass ionomer cement. Commonly known compositions of fluoroaluminosilicate glasses are, in terms of ion weight percent, silicon, 10 to 33; aluminum, 4 to 30; alkaline earth metals, 5 to 36;
Alkali metals, 0 to 10; phosphorus, 0.2 to 16; fluorine, 2 to 40 and residual oxygen are preferably used.
Illustrating a more preferable composition range, silicon, 15 to 2
5; aluminum, 7 to 20; alkaline earth metal, 8 to
28; alkali metal, 0 to 10; phosphorus, 0.5 to 8; fluorine, 4 to 40 and residual oxygen. Part or all of the alkaline earth metal is magnesium, strontium,
Barium-substituted ones are also preferred, and strontium is particularly often used because it gives the cured product X-ray opacity and high strength. The most common alkali metal is sodium, but it is also preferable that the alkali metal is partially or entirely replaced with lithium, potassium, or the like. If necessary, part of the aluminum can be replaced with titanium, yttrium, zirconium, hafnium, tantalum, lanthanum, or the like. Other, if necessary,
Replacing the above components with other components can be selected as long as the properties of the obtained cured product are not significantly impaired.

The amount of the ion-eluting filler used in the present invention is 30 to 500 parts by weight, more preferably 50 to 400 parts by weight, based on 100 parts by weight of the total vinyl monomer used.
Parts by weight. If the amount of the ion-eluting filler is less than 30 parts by weight, the adhesive strength of the curable composition at the interface with the tooth becomes insufficient, and if it is more than 500 parts by weight, the acidic group-containing vinyl monomer and the ion-eluting filler Is difficult to mix uniformly.

The shape of the ion-eluting filler used in the present invention is not particularly limited, and may be pulverized particles or spherical particles obtained by ordinary pulverization, and if necessary, plate-like or fibrous particles. Can also be mixed.

The particle size of the ion-eluting filler is as follows:
Although not particularly limited, for example, when filling teeth, it is desirable that the surface of the cured body is smooth,
μm or less, preferably 20 μm or less is suitably used. On the other hand, if the particle size is too small, the surface area of the ion-eluting filler becomes large, and it becomes difficult to mix the filler in the acidic group-containing vinyl monomer in a large amount, which tends to cause a decrease in the tensile strength of the cured product. Therefore, the preferable lower limit of the particle size of the ion-eluting filler is 0.01 μm.

The polymerization initiator used in the present invention is not particularly limited, and a known radical generator can be used without any limitation. For example, benzoyl peroxide, parachlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, acetyl peroxide, lauroyl peroxide, tertiary butyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane 2,5- Organic peroxides such as dihydroperoxide, methyl ethyl ketone peroxide, tertiary butyl peroxybenzoate, azo compounds such as azobisisobutyronitrile, and organic acid compounds such as tributyl boric acid are preferable. . It is also possible to carry out the polymerization at room temperature by using a combination of the organic peroxide and an amine, but such amines include secondary or tertiary amines in which an amino group is bonded to an aryl group. It is preferably used from the viewpoint of curing acceleration. For example,
N, N'-dimethyl-p-toluidine, N, N'-dimethylaniline, N'-β-hydroxyethyl-aniline, N, N'-di (β-hydroxyethyl) -aniline, N, N'-di (Β-hydroxyethyl) -p-toluidine, N-methyl-aniline, N-methyl-p-toluidine and the like are preferred.

In a preferred embodiment, a photosensitizer which generates a radical upon irradiation with light is used as the polymerization initiator. Examples of photosensitizers for ultraviolet light include benzoin, benzoin methyl ether, benzoin ethyl ether, acetoin benzophenone, p-chlorobenzophenone, and p-methoxybenzophenone.
Further, a photosensitizer which initiates polymerization by visible light is more preferably used because it does not require ultraviolet rays harmful to the human body. Examples of these are benzyl, camphorquinone, α-naphthyl, acetonaphthene, p, p′-dimethoxybenzyl, p, p′-dichlorobenzylacetyl, pentanedione, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,
Α-diketones such as 10-phenanthrenequinone and naphthoquinone; Among them, camphorquinone is most preferably used. It is also preferable to use the photosensitizer in combination with a photopolymerization accelerator.

Examples of such a photopolymerization accelerator include N, N-dimethylaniline, N, N-diethylaniline, N, N-
Di-n-butylaniline, N, N-dibenzylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-dimethyl-m-toluidine, p-bromo-N , N-dimethylaniline, m-chloro-N, N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p
-Dimethylaminobenzoic acid amino ester, N, N-dimethylanthranilic acid methyl ester, N, N-dihydroxyethylaniline, N, N
-Dihydroxyethyl-p-toluidine, p-dimethylaminophenethyl alcohol, p-dimethylaminostilpene, N, N-dimethyl-3,5-xylidine, 4-
Dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β-naphthylamine,
Tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine,
Tertiary amines such as N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, 2,2 '-(n-butylimino) diethanol And the like. Valpituric acids such as 5-butylvalpituric acid and 1-benzyl-5-phenylvalpituric acid can be suitably used. At least one of these photopolymerization accelerators can be selected and used, and two or more can be used as a mixture.

The amount of the polymerization initiator to be added may be appropriately determined. Generally, 0.1 to 0.1
It may be selected from the range of 3% by weight.

The packaging form of the curable composition of the present invention is not particularly limited, and the acidic monomer-containing vinyl monomer, the ion-eluting filler and the polymerization initiator (in the case of a photosensitizer) are packaged in one pack, Any of the forms in which the group-containing vinyl monomer and the ion-eluting filler are divided into two packs and the polymerization initiator is added to either one of them is possible, and can be appropriately selected depending on the application.

[0044]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. In addition, the properties of the materials shown in the text and in the examples,
The measuring method of the physical properties is as follows.

(1) Particle Size Distribution of Filler A filler is dispersed in water, and a particle size distribution analyzer (MALVER) is used.
N Company). The measurement principle is based on measurement of a scattered diffraction image by a laser beam.

(2) Crystal Structure of Filler The crystal structure (morphology) of the filler was examined using an X-ray diffraction measuring device (manufactured by JEOL Ltd.).

(3) Amount of polyvalent metal ion eluted from filler 50 ml of 10% by weight aqueous solution of acrylic acid (pH = 2.2)
1 g of a filler was added to the mixture, and the mixture was stirred at 37 ° C. for 24 hours, and the amount of eluted ions was measured with an atomic absorption spectrophotometer (manufactured by Shimadzu Corporation).

(4) Compressive Strength of Cured Body After the curable composition was cured in a mold having a hole of 3 mm × 4 mmφ, it was kept at 37 ° C. for 1 hour. For curing, irradiation with a visible light irradiator and white light (manufactured by Takara Labelmont Co.) was performed for 30 seconds as necessary.

Next, the cured product is removed from the mold and
After immersing in water at 70 ° C for 71 hours, the crosshead speed was 1 mm / cm with Tensilon (Toyo Baldwin).
The compressive strength of the cured product was measured in min.

(5) Adhesive strength to tooth substance Bovine teeth are polished with # 800 emery paper under water pouring.
The dentin plane was carved out. On this flat surface, a double-sided tape having a hole of 4 mm in diameter was attached, and a paraffin wax having a thickness of 3 mm and a hole of 6 mm in diameter was attached thereon so that the center of the double-sided tape coincided with the center. The curable composition was filled in the circular hole, cured and immersed in water at 37 ° C. for 24 hours, and a stainless steel rod having a diameter of 8 mm and a length of 18 mm was fixed to the surface of the cured body with an instant adhesive. Then, using Tensilon, a tensile load (crosshead speed 10
mm / min), the adhesive strength between the tooth material and the cured product was measured. In addition, the adhesive strength under wet conditions was measured by the same method as described above after applying water thinly to the dentin plane using a sponge before filling the curable composition in the above method.

(6) Coloring test A cured product was prepared in the same manner as in the tensile strength measurement. This cured product was immersed in a 7.4% aqueous solution of instant coffee (Nescafe Excella) at 37 ° C. for 24 hours, and the color tone change (ΔE *) before and after immersion was measured with a color difference meter (manufactured by Nippon Denshoku Co., Ltd.). The smaller the ΔE * value, the smaller the change in color tone, that is, the smaller the coloring.

Incidentally, the adhesive strength of the composite resin and the glass ionomer cement was measured by the same method after filling and curing according to each method of use.

Production Example 1 55 g of β-methacryloyloxyethyl hydrosuccinate (trade name: HOMS, manufactured by Kyoeisha Yushi Kagaku Kogyo), 28 g of glycidyl methacrylate (manufactured by Wako Pure Chemical Industries), and p-toluenesulfonic acid in a 300 ml eggplant-shaped flask 1
1.4 g and chloroform (100 ml) were added.
Stirred for hours. After adding 200 ml of chloroform to the reaction solution, 300 ml of water and 300 ml of a 1N aqueous solution of sodium carbonate were added.
and then again 300 ml of water. The organic layer was dried by adding 10 g of anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure to obtain 73 g of a colorless liquid.

A 500 ml eggplant-shaped flask was charged with 32 g of trimellitic anhydride chloride, 13 g of pyridine and 200 ml of benzene, and a solution prepared by dissolving 57 g of the above colorless liquid in 100 ml of benzene was added dropwise over 1 hour while stirring under ice cooling. After the temperature of the reaction solution was returned to room temperature, the mixture was stirred for 1 hour. The solution was filtered to remove the pyridine hydrochloride, and the solvent was removed from the filtrate under reduced pressure. 250 ml of tetrahydrofuran and 250 ml of water were added to the obtained product, and 1
Stirred overnight. 300 ml of chloroform was added to this solution to extract the product, which was washed twice with 400 ml of water. After separating the organic layer, 10 g of anhydrous sodium sulfate was added and dried. After filtration, the product was formed by column chromatography using activated alumina, and the solvent was removed under reduced pressure to obtain 49 g of a colorless viscous liquid. The product was confirmed to be a compound represented by the following structure [5] from the results of infrared spectroscopy, nuclear magnetic resonance analysis, and elemental analysis.

Infrared spectroscopy 1500, 1580, 1610 cm ^-1 (absorption based on aromatic ring) 1640 cm ^-1 (absorption based on C = C double bond) 1730 cm ^-1 (absorption based on carbonyl group of carboxylic acid) Nuclear magnetism Resonance analysis 1.9 ppm, singlet, 6 protons (absorption based on methyl of methacryl) 2.6 ppm, singlet, 4 protons (absorption based on methylene derived from succinic acid) 3.4 to 3. 9 ppm, multiplet, 4 protons (absorption based on methylene on both sides of methine bound to trimellitate) 4.1-4.3 ppm, multiplet, 1 proton (bonded to trimellitate) 4.3 ppm, singlet, 4 protons (absorption based on methylene derived from hydroxyethyl methacrylate) 5.6, 6.2 ppm, doublet 4 protons (absorption based on methylene of methacryl) 7.8 to 8.5 ppm, quintuple, 3 protons (absorption based on benzene ring) 10.3 ppm, singlet, 2 protons (carboxylic acid Absorption based on

[0056]

Embedded image Production Example 2 Tetrahydrofuran 20 was placed in a 500 ml three-necked flask.
0 ml, hydroxypropyl acrylate (Kyoeisha Yushi Kagaku Kogyo) 38 g, succinic anhydride (Wako Pure Chemical Industries, Ltd.)
34 g, 30 g of pyridine (manufactured by Wako Pure Chemical Industries) and a small amount of hydroquinone monomethyl ether (manufactured by Wako Pure Chemical Industries)
The reaction was carried out for 24 hours while stirring at 55-60 ° C. After completion of the reaction, the solvent was removed under reduced pressure, and the remaining
Dissolved in benzene. Then, a 5% hydrochloric acid solution was added to the solution until the pH became 3 to 4. Then, the separated organic layer was washed with diluted hydrochloric acid and distilled water, and then extracted with a diluted sodium carbonate solution. Next, the extract is washed with ether and then 5%
A hydrochloric acid solution was added until the pH became 3 to 4, and the reaction product was extracted with ethyl acetate. After the extract was dried over anhydrous sodium carbonate, the solvent was removed under reduced pressure to obtain 65 g of a colorless liquid.

57 g of the above colorless liquid, glycidyl methacrylate (manufactured by Wako Pure Chemical Industries) in a 300 ml eggplant-shaped flask
28 g, p-toluenesulfonic acid 11.4 g, and chloroform 100 ml were added, and the mixture was stirred at room temperature for 2 hours. After adding 200 ml of chloroform to the reaction solution, 300 m of water was added.
1, 300 ml of 1N aqueous sodium carbonate solution and 30 ml of water again
Washing was performed in the order of 0 ml. Anhydrous sodium sulfate 1 in organic layer
0 g was added and dried, and after filtration, the solvent was removed under reduced pressure to obtain 59 g of a colorless liquid.

A 500 ml eggplant-shaped flask was charged with 32 g of trimellitic anhydride chloride, 13 g of pyridine and 200 ml of benzene, and a solution prepared by dissolving 57 g of the above colorless liquid in 100 ml of benzene was added dropwise over 1 hour while stirring under ice cooling. After the temperature of the reaction solution was returned to room temperature, the mixture was stirred for 1 hour. The solution was filtered to remove the pyridine hydrochloride, and the solvent was removed from the filtrate under reduced pressure. 250 ml of tetrahydrofuran and 250 ml of water were added to the obtained product, and 1
Stirred overnight. 300 ml of chloroform was added to this solution to extract the product, which was washed twice with 400 ml of water. After separating the organic layer, 10 g of anhydrous sodium sulfate was added and dried. After filtration, the product was formed by column chromatography using activated alumina, and the solvent was removed under reduced pressure to obtain 40 g of a viscous liquid. From the results of infrared spectroscopic analysis, nuclear magnetic resonance analysis, and elemental analysis of the product, it was confirmed that the product was a compound represented by the following structure [6].

Infrared spectroscopy 1500, 1580, 1610 cm ^-1 (absorption based on aromatic ring) 1640 cm ^-1 (absorption based on C = C double bond) 1730 cm ^-1 (absorption based on carbonyl group of carboxylic acid) Nuclear magnetism Resonance analysis 1.9 ppm, singlet, 3 protons (absorption based on methyl of methacryl) 0.9, 1.0 ppm, doublet, 3 protons (absorption based on methyl of butyl) 2.6 ppm, Singlet, 4 protons (absorption based on methylene of succinic acid) 3.4 to 3.9 ppm, multiplet, 4 protons (absorption based on methylene on both sides of methine bound to trimellitate) 4.1-4.3 ppm, multiple lines, 3 protons (absorption of methine and butyl bonded to trimellitate based on methylene) 4.7-5.2 ppm, multiple lines, 1 proton (Absorption based on butyl methine) 5.6 to 6.4 ppm, multiple lines, 5 protons (absorption based on methacrylic methylene and acrylic methylene, methine) 7.8 to 8.5 ppm, quintuple, proton 3 (absorption based on benzene ring) 10.3 ppm, singlet, 2 protons (absorption based on carboxylic acid)

[0060]

Embedded image Production Example 3 Tetrahydrofuran 20 was placed in a 500 ml three-necked flask.
0 ml, 39 g of hydroxyethyl methacrylate (manufactured by Kyoeisha Yushi Kagaku Kogyo), 39 g of glutaric anhydride (manufactured by Wako Pure Chemical Industries), 30 g of pyridine (manufactured by Wako Pure Chemical Industries), and a small amount of hydroquinone monomethyl ether (manufactured by Wako Pure Chemical Industries) The reaction was carried out for 24 hours while stirring at 55-60 ° C.
After completion of the reaction, the solvent was removed under reduced pressure, and the remaining reactant was removed for 300 minutes.
Dissolved in ml of benzene. Then, a 5% hydrochloric acid solution was added to the solution until the pH became 3 to 4. Then, the separated organic layer was washed with diluted hydrochloric acid and distilled water, and then extracted with a diluted sodium carbonate solution. Next, the extract is washed with ether,
A 5% hydrochloric acid solution was added until the pH became 3 to 4, and the reaction product was extracted with ethyl acetate. After the extract was dried over anhydrous sodium carbonate, the solvent was removed under reduced pressure to obtain 66 g of a colorless liquid.

In a 300 ml eggplant-shaped flask, 61 g of the above colorless liquid, glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
28 g, p-toluenesulfonic acid 11.4 g, and chloroform 100 ml were added, and the mixture was stirred at room temperature for 2 hours. After adding 200 ml of chloroform to the reaction solution, 300 m of water was added.
1, 300 ml of 1N aqueous sodium carbonate solution and 30 ml of water again
Washing was performed in the order of 0 ml. Anhydrous sodium sulfate 1 in organic layer
0 g was added and dried, and after filtration, the solvent was removed under reduced pressure to obtain 81 g of a colorless liquid.

A 500 ml eggplant-shaped flask was charged with 32 g of trimellitic anhydride chloride, 13 g of pyridine and 300 ml of benzene, and 57 g of the above colorless liquid was added dropwise over 1 hour while stirring under ice-cooling. After returning, the mixture was stirred for 1 hour. The solution was filtered to remove the pyridine hydrochloride, and the solvent was removed from the filtrate under reduced pressure. 250 ml of tetrahydrofuran, 25
0 ml was added and the mixture was stirred overnight. 300 ml of chloroform was added to this solution to extract the product, which was washed twice with 400 ml of water. After separating the organic layer, anhydrous sodium sulfate 10
g, dried, filtered, and the product was formed by column chromatography using activated alumina. The solvent was removed under reduced pressure to obtain 40 g of a viscous liquid. From the results of infrared spectroscopy, nuclear magnetic resonance analysis and elemental analysis of this product, it was confirmed that the product was a compound represented by the following structure [7].

Infrared spectroscopy 1500, 1580, 1610 cm ^-1 (absorption based on aromatic ring) 1640 cm ^-1 (absorption based on C = C double bond) 1730 cm ^-1 (absorption based on carbonyl group of carboxylic acid) Nuclear magnetism Resonance analysis: 1.9 ppm, singlet, 6 protons (absorption based on methyl of methacryl) 1.3 to 1.8 ppm, multiplet, 2 protons (absorption based on methylene in the center of glutaric acid) 2 to 2.4 ppm, quadruple, 4 protons (absorption based on the left and right methylene of glutaric acid) 3.4 to 3.9 ppm, multiplet, 4 protons (methine binding to trimellitate) 4.1-4.3 ppm, multiple lines, one proton (absorption based on methine binding to trimellitate) 4.3 ppm, singlet, pro 4 (the absorption based on methylene in the hydroxyethyl methacrylate portion) 5.6, 6.2 ppm, doublet, 4 protons (the absorption based on methylene in methacrylic) 7.8 to 8.5 ppm, quintuple , 3 protons (absorption based on benzene ring) 10.3 ppm, singlet, 2 protons (absorption based on carboxylic acid)

[0064]

Embedded image Example 1 A powder composed of 120 g of silica, 42 g of aluminum hydroxide, 28 g of artificial cryolite, 78 g of aluminum phosphate, 24 g of aluminum fluoride, and 76 g of calcium fluoride mixed in a ball mill for 3 hours was used as a platinum crucible. The mixture was heated and melted at 1400 ° C. for 30 minutes. Subsequently, the melt was quenched in a water bath, and the obtained glass was crushed by a vibration ball mill. The powder obtained by the pulverization is passed through a 400 mesh nylon sieve, and the powder 150 having passed through the sieve
g was dispersed in 1 liter of methanol, and those which did not settle within 1 hour (hereinafter referred to as filler A) were collected.
Filler A was amorphous with a particle diameter of 0.2 to 2.7 μm, an average particle diameter of 1.0 μm, and a polyvalent metal ion elution amount of 16 mgeq / g.

A mixture of 80 parts by weight of an acidic group-containing vinyl monomer of structural formula [5] and 20 parts by weight of hydroxyethyl methacrylate (HEMA) synthesized according to Preparation Example 1 was mixed with camphorquinone (CQ) and p-dimethylaminobenzoic. Acid ethyl ester (DMBE) 10 g in which 0.5% by weight was dissolved, and filler A15
g were mixed under light shielding, followed by vacuum degassing to prepare a curable composition.

The adhesive strength of the above-mentioned curable composition to tooth substance is 8
^{5kg / cm 2, 83kg / cm} 2 in the humid, tensile strength 312kg
/ Cm ² , compressive strength 2670 kg / cm ² , coffee coloring amount is Δ
E * = 8.4.

Example 2 A mixture of 50 parts by weight of an acidic group-containing vinyl monomer having the structural formula [6] and 50 parts by weight of hydroxyethyl methacrylate synthesized according to Preparation Example 2 was added with camphorquinone and p
-10 g of dimethylaminobenzoic acid ethyl ester each dissolved at 1.0% by weight and filler A
After mixing 15 g under light shielding, the mixture was vacuum defoamed to prepare a curable composition.

The adhesive strength of the above curable composition to the tooth substance is 7
^{3kg / cm 2, 69kg / cm} 2 in the humid, tensile strength 331kg
/ Cm ² , compression strength 2910 kg / cm ² , coffee coloring amount is Δ
E * = 9.1.

Example 3 A mixture of 80 parts by weight of an acidic group-containing vinyl monomer having the structural formula [7] and 20 parts by weight of triethylene glycol dimethacrylate synthesized according to Preparation Example 3 was mixed with camphorquinone and p-dimethylaminobenzoic acid. After mixing 10 g of a solution in which 0.5% by weight of each ethyl ester was dissolved and 15 g of Filler A under light shielding, the mixture was vacuum defoamed to prepare a curable composition.

The adhesive strength between the curable composition and the tooth substance is 7
^{1kg / cm 2, 74kg / cm} 2 in the humid, tensile strength 348kg
/ Cm ² , compressive strength 3230 kg / cm ² , coffee coloring amount is Δ
E * = 6.5.

Examples 4 to 6 Tests were conducted in the same manner as in Example 1 except that the fluoroaluminosilicate glass shown in Table 1 was prepared and used as an ion-eluting filler. Examples 1, 4 to 6
Table 1 shows the results.

Comparative Examples 1 and 2 Commercially available dental composite resin, trade name: PALFIKE LIGHT (manufactured by Tokuyama Soda Co., Ltd.) (polyfunctional vinyl monomer having no acidic group, silica filler, α-diketone polymerization initiator Comparative Example 1, glass ionomer cement for dental filling, trade name: Fudiaionomer II (manufactured by Jushi Dental Industry Co., Ltd.) (polycarboxylic acid aqueous solution, fluoroaluminosilicate) Table 1 shows the results of a test using glass as a main component) as Comparative Example 2.

[0073]

[Table 1] Example 7 0.5% by weight of camphorquinone and 0.5% by weight of p-dimethylaminobenzoic acid ethyl ester were added to a mixture of 80 parts by weight of the acidic group-containing vinyl monomer of the above structural formula [5] and 20 parts by weight of neopentyl glycol dimethacrylate.
Was dissolved and 20 g of filler A were mixed under light shielding, followed by vacuum defoaming to prepare a curable composition.

The adhesive strength of the curable composition to tooth material is 7
^{2kg / cm 2, 68kg / cm} 2 in the humid, tensile strength 320kg
/ Cm ² , compressive strength 2990 kg / cm ² , coffee coloring amount is Δ
E * = 5.9.

Example 8 60 parts by weight of an acidic group-containing vinyl monomer represented by the above structural formula [5], 20 parts by weight of a difunctional vinyl monomer trade name D-2.6E (manufactured by Shin-Nakamura Chemical Co., Ltd.), triethylene glycol dimethacrylate (Shin Nakamura Chemical Co., Ltd.) 15 g of a mixture of 20 parts by weight of camphorquinone and p-dimethylaminobenzoic acid ethyl ester dissolved in 0.5% by weight and 12 g of filler A were mixed under light shielding, and then vacuum degassing was performed. A curable composition was prepared.

The adhesive strength between the curable composition and the tooth substance is 6
^{5kg / cm 2, 69kg / cm} 2 in the humid, tensile strength 292kg
/ Cm ² , compressive strength 2730 kg / cm ² , coffee coloring amount is Δ
E * = 5.2.

Example 9 A monomer solution was prepared by mixing 80 parts by weight of an acidic group-containing vinyl monomer represented by the above structural formula [5] and 20 parts by weight of hydroxyethyl methacrylate. N,
10 g of N′-di (β-hydroxyethyl) -p-toluidine dissolved at 1.0% by weight and 15 g of filler A were mixed (hereinafter referred to as paste I). Next, 10 g of 1.2% by weight of benzoyl peroxide dissolved in the above monomer solution and 15 g of filler A were mixed (hereinafter referred to as paste II). Paste I and paste II are weight ratio 1
As a result of mixing and testing at a ratio of one to one, the adhesive strength to the tooth substance was 71 kg / cm ² , 68 kg / cm ² under wet conditions, and the tensile strength was 28.
3kg / cm ^2, compression strength 2640kg / cm ^2, coffee colored amount was ΔE * = 9.2.

Example 10 In the process of producing a filler of Example 1, powder precipitated in methanol within one hour was collected, and this powder was supplied from a burner having a large volume tube at a feed rate of 20 g / min with hydrogen (2.3 Nm ³ / h) and oxygen (0.90 Nm ³ / h) together with the mixture and supplied to the combustion chamber, dispersed in a flame and melted. The particles were instantaneously melted in the flame and then cooled and solidified upon exiting the flame. The particles were collected in a cyclone.
Further, 10 g of this powder was kneaded with 0.4 g of ammonium fluoride and a small amount of water, dried at 100 ° C. for 3 hours, and then heated at 600 ° C. for 1 hour. The powder thus obtained (referred to as filler B) is 100% spherical, has a particle diameter of 3.7 to 18.1 μm, an average particle diameter of 7.8 μm, and a polyvalent metal ion elution amount of 11 meq / g. It was a crystal.

50 parts by weight of the acidic group-containing vinyl monomer of the above structural formula [5] and 50 parts of hydroxyethyl methacrylate
To 0.5 parts by weight of the mixture, 0.5% each of camphorquinone and p-dimethylaminobenzoic acid ethyl ester were added.
After mixing 8 g of a weight% solution, 11 g of Filler A and 17 g of Filler B under light shielding, the mixture was vacuum defoamed to prepare a curable composition.

The adhesive strength of the curable composition to the tooth substance is 6
9 kg / cm ² , wet 72 kg / cm ² , tensile strength 309 kg
/ Cm ² , compression strength 3360 kg / cm ² , coffee coloring amount is Δ
E * = 8.8.

Comparative Example 3 Camphorquinone and p-dimethylaminobenzoic acid ethyl ester were added to a vinyl monomer having an acidic group having the following structure (M-5500, manufactured by Toagosei Co., Ltd.) in an amount of 0.1% each.
After 10 g of a solution containing 5% by weight and 20 g of filler A were mixed under light shielding, the mixture was vacuum defoamed to prepare a curable composition.

[0082]

Embedded image The adhesive strength of the curable composition to the tooth substance was 83 kg / cm ² ,
77 kg / cm ² under wet conditions, tensile strength 213 kg / cm ² , compressive strength 1220 kg / cm ² , coffee coloring amount ΔE * = 2
It was 5.1.

Comparative Example 4 48 parts by weight of a difunctional vinyl monomer (trade name: D-GMA, manufactured by Shin-Nakamura Chemical Co., Ltd.)
A mixture of 24 parts by weight of 2.6E, 4 parts by weight of a vinyl monomer having an acidic group having the following structure, and 24 parts by weight of a bifunctional vinyl monomer having a urethane bond, Art Resin SH-400 (manufactured by Shin-Nakamura Chemical Co., Ltd.) , Camphor quinone,
After mixing 10 g of p-dimethylaminobenzoic acid ethyl ester in which 0.5% by weight of each was dissolved and 20 g of filler A under light shielding, the mixture was vacuum defoamed to prepare a curable composition.

[0084]

Embedded image The adhesive strength of the curable composition to the tooth substance was 19 kg / cm ² ,
10 kg / cm ² under wet conditions, tensile strength 342 kg / cm ² , compressive strength 3580 kg / cm ² , coffee coloring amount ΔE * = 5.
It was eight.

Comparative Example 5 A mixture of 20 parts by weight of an acidic group-containing vinyl monomer represented by the above structural formula [5] and 80 parts by weight of neopentyl glycol dimethacrylate was added with camphorquinone and p-dimethylaminobenzoic acid ethyl ester in an amount of 0% each. .
After mixing 10 g of 5 wt% dissolved and 15 g of filler A under light shielding, the mixture was vacuum defoamed to prepare a curable composition.

The adhesive strength of the above curable composition to the tooth substance is 2
^{3kg / cm 2, 18kg / cm} 2 in the humid, tensile strength 263
kg / cm ^2, compression strength 2570kg / cm ^2, the coffee colored amount was Delta] E * = 5.9. Comparative Example 6 To a mixture of 80 parts by weight of an acidic group-containing vinyl monomer represented by the above structural formula [5] and 20 parts by weight of hydroxyethyl methacrylate, 0.5% by weight of each of camphorquinone and p-dimethylaminobenzoic acid ethyl ester.
And 10 g of cristobalite powder
Was mixed under light shielding, followed by vacuum defoaming to prepare a curable composition.

The adhesive strength of the above-mentioned curable composition to tooth material is 5
^{0 kg / cm 2, 62kg /} cm 2 in humid, tensile strength 231k
g / cm ² , compressive strength 1920 kg / cm ² , and coffee coloring amount ΔE * = 13.1. Comparative Example 7 To a mixture of 80 parts by weight of an acidic group-containing vinyl monomer represented by the above structural formula [5] and 20 parts by weight of hydroxyethyl methacrylate, 0.5% by weight of each of camphorquinone and p-dimethylaminobenzoic acid ethyl ester was added.
And 10g that were lysed and the filler A 2 g, was mixed in the dark, to prepare a vacuum degassed curable compositions.

The adhesive strength of the above-mentioned curable composition to tooth substance is 4
1 kg / cm ² , 35 kg / cm ² under wet conditions, tensile strength 223
kg / cm ^2, compression strength 1940kg / cm ^2, the coffee colored amount was Delta] E * = 10.6.

[0089]

As described above, the curable composition of the present invention exhibits high adhesive strength even in the presence of water, so that it is possible to expect the development of reliable adhesive strength in clinical applications such as tooth restoration.

When the cured product is used as a dental filler, it has a higher tensile strength than glass ionomer cement, so that not only does the adhesive strength not decrease due to its destruction, but also hardly occur abrasion and fracture. . In addition, the composite resin does not require an indispensable bonding material, is capable of excellent molding and restoration, and has the advantage of a simple clinical technique. Furthermore, there is little coloring due to food and drink in the mouth.

Due to these features, the curable composition of the present invention can be used not only as a dental filling material, but also as a bonding material and a lining material for a composite resin, a dental sealant, and other filling materials and adhesive materials. You can do it.

Claims (1)

(57) [Claims] (A) The following general formula: Wherein R ₁ and R ₄ represent a hydrogen atom or a methyl group, and R ₂ and R ₃ represent an alkylene group having 1 to 4 carbon atoms. 100 parts by weight of a monomer, (B) 30 to 500 parts by weight of an ion-eluting filler for eluting 2 mgeq / g to 60 mgeq / g of a polyvalent metal ion, and (C) 0.1 to 3 parts by weight of a polymerization initiator. Curable composition.