JPH0689050B2 - Curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel curable composition. Specifically, it provides a hardened material having high tensile strength, and has a high adhesive strength to an object containing a metal element, which has a hydrophilic surface such as a biological hard tissue such as dentin, a metal material, a ceramic material, etc. even when wet. It is a curable composition having.

[Prior art and its problems]

There are roughly two methods for repairing relatively small defects of teeth formed by caries or the like, that is, for preservation and repair.
One is a method of taking the shape of a defect, making a restoration that fits the shape outside the oral cavity, and then fixing it to the tooth with an adhesive.
It is called the inlay restoration method. The other is a method in which a moldable material is filled in the defect portion and then cured, which is called a molding restoration method.

Compared with the inlay restoration method, the above-mentioned molding restoration method has a simpler working process and can be processed on the same day, and its range of applications has been expanding in recent years due to the fact that its physical properties have been improved by the progress of materials. .

Conventionally, composite resins, glass ionomer cements and amalgams have been generally used as materials used in the molding and restoration method, but among them, composite resins and glass ionomer cements have a color tone and transparency similar to teeth, and thus have aesthetics. It has come to be frequently used as a material having.

However, various problems have been pointed out clinically in these two types of molding and restorative materials.

For example, a composite resin has high mechanical strength, but it does not have adhesiveness to the tooth substance itself, 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 will be significantly reduced. Further, even if a bonding material is used, there is a problem that the adhesive strength between the composite resin and the teeth, especially the dentin thereof, is insufficient.

On the other hand, glass ionomer cement is a material that is more hydrophilic than the composite range, and adheres to the tooth structure without using a bonding material. Therefore, unlike a composite resin, a complicated bonding operation is not required, but the tensile strength of the cured product itself is low, and therefore the adhesive strength with the tooth structure is still insufficient due to the destruction of the cured product. Further, due to the low tensile strength, there is a drawback that abrasion or breakage easily occurs after filling and the durability is poor. As described above, there is a demand for a filling material that does not require a complicated operation, and that surely adheres to the tooth structure even when wet and has sufficient strength.

[Means for solving problems]

The present inventors have conducted intensive studies to overcome the above technical problems. As a result, the composition consisting of the vinyl monomer having an acidic group, the specific ion-eluting filler and the polymerization initiator surely adheres to the teeth even when cured by moistening, and the cured product has sufficient strength. After finding out that, the present invention has been completed.

That is, the present invention provides (A) 100 parts by weight of a vinyl monomer having an acidic group (B) 30 to 500 parts by weight of an ion-eluting filler that elutes 2 mgeq / g to 60 mgeq / g of a polyvalent metal ion, and (C) initiation of polymerization. It is a curable composition comprising an agent.

The vinyl monomer having an acidic group used in the present invention is not particularly limited, and generally known vinyl monomers are used. For example, vinyl monomers having an acidic group such as carboxylic acid, phosphoric acid, sulfonic acid and having a polymerizable unsaturated group are suitable. Of these, the acidic group is preferably a carboxylic acid group.
For example, a typical vinyl monomer having a carboxylic acid as an acidic group is represented by the general formula (However, R ₁ : H or CH ₃ , R ₂ : H or R _3, R _3: an organic residue, n: 1 to 4 integer), and the like.

here, As a preferred specific example, -NHCH ₂ CH ₂ CH ₂ COOH, -NHCH ₂ CH ₂ CH ₂ CH ₂ COOH, Etc.

Among these, the most preferably used are -NHCH ₂ CH ₂ COOH, -NHCH ₃ CH ₃ CH ₃ COOH, -NHCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ COOH, Is.

Further, as preferable specific examples of -R ₄ COOH) n, CH _{2 6} CH (COOH) ₂ CH _{2 10} CH (COOH) ₂ , Etc.

In the present invention, the vinyl monomer having an acidic group may be used alone or, if necessary, as a mixture of two or more kinds.

Further, a polyfunctional vinyl monomer may be added to the above vinyl monomer having an acidic group, whereby the mechanical strength of the cured product obtained can be further improved. Representative examples that are preferably used are those having an acrylic group and / or a methacrylic group, and specific examples are as follows.

A) Bifunctional vinyl monomer (i) Aromatic compound type 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-methacryloxydipropoxy Phenyl) -2 (4-methacryloxytriethoxyphenyl) propane; 2,2-bis (4- Tacryloxydipropoxyphenyl) propane; 2,2-bis (4-methacryloxyisopropoxyphenyl) propane and acrylates thereof (ii) Aliphatic compounds based 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 monomers trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate and their acrylates and the following structural formula Having monomer (However, R; H or CH ₃ ) C) Tetrafunctional vinyl monomer pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate and urethane type monomer having the structural formula shown below. The above polyfunctional vinyl monomers can be used alone or, if necessary, as a mixture of two or more kinds.
Further, among the polyfunctional vinyl monomers, a trifunctional or tetrafunctional vinyl monomer has a large effect of improving the mechanical strength of the obtained cured product and is preferably used.

The amount of the polyfunctional vinyl monomer added to the vinyl monomer having an acidic group is preferably 2 to 30%, more preferably 5 to 20% by weight. If the amount added is less than the above range, the contribution of the polyfunctional vinyl monomer to the tensile strength is insufficient, and if the amount added is more than the above range, the adhesiveness of the curable composition to the tooth structure tends to decrease. .

The curable composition of the present invention, the tensile strength of the cured product is improved with time by immersion in water, more surprisingly, by pre-blending water to the composition before curing,
It is possible to accelerate the rate of development of the strength of the cured product. The amount of water added is preferably 1 to 30% by weight, more preferably 2 to 15% by weight, based on the vinyl monomer having an acidic group. If the amount of water is less than the above range, the improvement of strength is not promoted, and if it is more than the above range, the strength of the cured product decreases.

The ion-eluting filler used in the present invention is 2 mgeq / g to 60 m
It elutes geq / g, preferably 5 mgeq / g to 30 mgeq / g of polyvalent metal ions. In the present invention, the ion elution amount of the filler means the amount of ions eluted when 1 g of the filler is immersed in 50 ml of an aqueous acrylic acid solution having a temperature of 37 ° C. and a pH of 2.2 for 24 hours. The polyvalent metal ion is a divalent or higher valent metal ion capable of binding to the acidic group of the vinyl monomer having the acidic group. Typical examples include calcium, strontium, barium, and aluminum.
Metal ions such as zinc and lanthanoid.

If the amount of polyvalent ions eluted from the ion-eluting filler is smaller or larger than the above range, the cured product will have insufficient tensile strength. That is, when the elution amount is small, the crosslinking between the acidic group and the polyvalent metal ion does not sufficiently occur, and when the elution amount is large, most of the filler is dissolved, and in any case. The effect of improving the tensile strength of the obtained cured product cannot be exhibited.

The ion-eluting filler is not particularly limited as long as it satisfies the above conditions, but preferred examples include calcium hydroxide, hydroxides such as strontium hydroxide,
There are oxides such as zinc oxide and fluoroaluminosilicate glass. Among them, fluoroaluminosilicate glass is the most excellent in terms of the effect of improving the tensile strength of the cured product,
It is suitable.

The reason for this is that fluoroaluminosilicate glass is more ionic species that elutes than other ion-eluting fillers.
It is considered that the ion elution rate and the like have a significant influence on the development of tensile strength of the cured product.

As the fluoroaluminosilicate glass, a known one used for dental cement, for example, glass ionomer cement can be used. The composition of the commonly known fluoroaluminosilicate glass is ionic 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. If a more preferable composition range is illustrated,
Silicon, 15 to 25; 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. It is also preferable to replace a part or all of the above alkaline earth metal with magnesium, strontium or barium, and especially strontium is often preferably used because it gives a cured product radiopacity and high strength. Further, sodium is most commonly used as the above-mentioned alkali metal, but it is also preferable that a part or all of the alkali metal is replaced with lithium, potassium or the like. Further, if necessary, a part of the aluminum may be titanium, yttrium,
Substitution with zirconium, hafnium, tantalum, lanthanum, etc. is also possible. In addition, substituting the above components with other components, if necessary, can be selected as long as the physical 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, and more preferably 50 to 400 parts by weight, based on 100 parts by weight of the vinyl monomer having an acidic group. When the amount of the ion-eluting filler is smaller than the above range, the adhesive strength at the interface with the tooth substance of the curable composition becomes insufficient,
On the other hand, if it exceeds the above range, it becomes difficult to uniformly mix the vinyl monomer having an acidic group and the ion-eluting filler.

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

The particle size of the ion-eluting filler is not particularly limited, but for example, when filling a tooth, it is desirable that the surface of the hardened material is smooth, and it is 50 μm or less, preferably 20 μm or less. Those are preferably used. On the other hand, if the particle size is too small, the surface area of the ion-eluting filler becomes large, making it difficult to mix it in a large amount in the carboxylic acid monomer, which tends to cause a decrease in the tensile strength of the cured product. Therefore, the lower limit of the preferable particle size of the ion-eluting filler is 0.01 μm.

The polymerization initiator used in the present invention is not particularly limited, and known radical generators 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, etc., azo compounds such as azobisisobutyronitrile, organic acid compounds such as tributyl boric acid, etc. are suitable. .

It is also possible to carry out the polymerization at room temperature by using a combination of the above organic peroxide and an amine. As such an amine, a secondary or tertiary amine having an amino group bonded to an aryl group can be used. It is preferably used in terms of curing acceleration. For example, N, N'-dimethyl-p-toluidine, N, N '
-Dimeylaniin, 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 preferable.

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

Examples of the 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-dimethylaminohenzoic acid, p-dimethylaminohenzoic acid ethyl ester, p-dimethylaminobenzoic acid amino ester, N, N-dimethylanthranillic acid methyl ester, N, N-dihydroxetylaniline,
N, N-dihydroxyethyl-p-toluidine, p-dimethylaminophenethyl alcohol, p-dimethylaminostilpen, 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, N, N-dimethyldodecylamine, N, N-dimethylstearylamine,
Tertiary amines such as N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, 2,2 ′-(n-butylimino) diethanol; 5-butylbarpituric acid, 1-benzyl-5- Barbituric acids such as phenylbarpituric acid can be preferably used. At least one kind of these photopolymerization accelerators can be selected and used, and two or more kinds can also be mixed and used.

The addition amount of the above-mentioned polymerization initiator may be appropriately determined. Generally, it may be selected from the range of 0.1 to 3% by weight with respect to the vinyl monomer.

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

〔effect〕

Since the curable composition of the present invention exhibits a high adhesive force even in the presence of water, it can be expected to exhibit a reliable adhesive strength in clinical cases such as tooth restoration.

When the hardened product is used as a dental filler, it has a higher tensile strength than glass ionomer cement, and therefore, not only does the adhesive strength decrease due to its destruction, but also the abrasion and fracture hardly occur. In addition, there is an advantage that a bonding material, which is indispensable in the composite resin, is not required, good molding and restoration can be performed, and a clinical operation method is simple.

Due to these characteristics, the curable composition of the present invention is used not only as a dental filling material, but also as a bonding material for composite resins, a backing material, and further as a dental sealand, other filling materials, adhesive materials, etc. I can do things.

〔Example〕

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. still,
The properties and measuring methods of the physical properties of the materials shown in the present text and examples are as follows.

(1) Particle size distribution of filler Disperse the filler in water and use a particle size distribution meter ((MALVERN
Company). The measurement principle is based on the measurement of a scattered diffraction image by laser light.

(2) Structure of filler The crystal structure (morphology) of the filler was examined by an X-ray diffractometer (manufactured by JEOL Ltd.).

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

(4) Tensile Strength of Cured Body The curable composition was cured in a mold having holes of 3 mm × 6 mmφ and then kept at 37 ° C. for 1 hour. Irradiation with a visible light irradiator and white light (manufactured by Takara Belmont Co., Ltd.) was carried out for 30 seconds for curing, if necessary.

Next, the cured product was taken out of the mold and immersed in water at 37 ° C for 71 hours, and then tensile strength was measured by applying a load in the diameter direction of the cured product at a crosshead speed of 1 mm / min with Tensilon (manufactured by Toyo Baldwin). did.

The tensile strength was calculated by the following formula.

P: Breaking load (kg / cm ² ) (5) Adhesive strength with dentin Bovine teeth were ground with # 800 emery paper under water injection, and the dentin plane was cut out. A double-sided tape having a hole with a diameter of 4 mm was attached to this plane, and a paraffin wax having a thickness of 3 mm with a hole having a diameter of 6 mm was attached on the flat surface so that the center of the double-sided tape was aligned. The circular hole was filled with a curable composition and then cured, and after being immersed in water at 37 ° C. for 24 hours, a stainless 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) was applied between the bovine tooth and the stainless steel rod to measure the adhesive strength between the tooth substance and the hardened body. The adhesive strength under wet conditions is
Before filling the curable composition, a thin layer of water was applied to the dentin plane using a sponge, and then measured by the same method as above.

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 operation.

Example 1 120 g of silica, 42 g of aluminum hydroxide, 28 g of artificial cryolite,
A powder consisting of 78 g of aluminum phosphate, 24 g of aluminum fluoride and 76 g of calcium fluoride was mixed in a ball mill for 3 hours, and the obtained mixed powder was placed in a platinum crucible and heated and melted at 1400 ° C. for 30 minutes. Subsequently, the melt was rapidly cooled in a water bath, and the obtained glass was crushed with a vibrating ball mill. The powder obtained by crushing is passed through a 400-mesh nylon sieve, and 150 g of the powder that has passed through the sieve is dispersed in 1 of methanol so that it does not settle within 1 hour (designated as filler A).
Was collected. Filler A was amorphous with a particle size of 0.2 to 2.7 μm, an average particle size of 1.0 μm, and a polyvalent metal ion elution amount of 16 mgeq / g.

10 g of a vinyl monomer having an acidic group of the following structure (M-5500, manufactured by Toagosei Co., Ltd.) in which 0.5 wt% of camphorquinone and p-dimethylaminobenzoic acid ethyl ester were dissolved and 20 g of filler A were used as a light-shielding plate. A trace of mixing and vacuum defoaming were performed to prepare a curable composition.

The adhesive strength of the above-mentioned curable composition part with the tooth structure was 83 kg / cm ² , 77 kg / cm ² under infiltration, and the tensile strength was 213 kg / cm ² .

Examples 2 to 4 Tests were performed in the same manner as in Example 1 except that a fluoroaluminosilicate glass having a composition different from that of Example 1 was prepared. The results of Examples 1 to 4 are shown in Table 1.

Comparative Examples 1 and 2 A commercially available dental composite resin (having a polyfunctional vinyl monomer having no acidic group, a silica filler, and an α-diketone-based polymerization initiator as main components) and a test result using an attached bonding material were compared. Comparative Example 1, Table 1 shows Comparative Example 2 as a comparative example 2 showing the test results using a dental filling glass ionomer cement (polycarboxylic acid aqueous solution and fluoroalumino silica silicate glass as main components).

Example 5 In a three-necked flask, 17.8 g of β-alanine and 200 ml of 4% aqueous sodium hydroxide solution were placed and dissolved. This flask 1
While keeping the temperature below 0 ° C, add 18.1 g of acrylic acid chloride to 1
It dripped over time. After completion of the reaction, the solution was adjusted to pH 3 with 6N hydrochloric acid, extracted with ethyl acetate and purified to obtain a vinyl monomer having an acidic group having the following structure.

9 g of camphorquinone and 0.8% by weight of N, N-dimethyl-p-toluidine dissolved in the vinyl monomer having an acidic group were mixed with 21 g of filler A under light shielding, and then vacuum defoaming was performed to prepare a curable composition. .

The adhesive strength between the tooth of the curable composition is ^{56kg / cm 2, 61kg / cm} 2 tensile strength humid was 191kg / cm ^2.

Example 6 25 g of potassium salt of N-phenylglycine was added to ion-exchanged water 1
After dissolving in 25 ml, 18.5 g of glycidyl methacrylate was added, and the mixture was stirred at 23 ° C. for 4 hours. This solution was washed with ether to remove unreacted glycidyl methacrylate, and then hydrochloric acid was added to adjust the pH to 4 to obtain a precipitate. The precipitate was filtered and dried under reduced pressure to obtain a vinyl monomer having an acidic group having the following structure.

A mixture of this vinyl monomer having an acidic group and M-5500 (weight ratio 30/70) was added to camphorquinone, N, N-dimethyl-
A curable composition was prepared by mixing 10 g of p-toluidine each dissolved in 0.8% by weight and 20 g of filler A under light shielding, and degassing in vacuum to prepare a curable composition.

The adhesive strength of the above curable composition with the tooth structure was 64 kg / cm ² , the wet strength was 57 kg / cm ² , and the tensile strength was 142 kg / cm ² .

Example 7 10 g of a mixture of 11-methacryloxy-1,1-undecanedicarboxylic acid and M-5500 (weight ratio 10/90), each containing 0.5% by weight of camphorquinone and p-dimethylaminobenzoic acid ethyl ester dissolved therein. Filler A2
After mixing 0 g under shading, vacuum degassing was performed to prepare a curable composition.

The adhesive strength of the above curable composition with the tooth substance was 81 kg / cm ² , the wet strength was 75 kg / cm ² , and the tensile strength was 153 kg / cm ² .

Example 8 Silica 120 g, aluminum phosphate 38 g, aluminum fluoride 140, strontium fluoride 70 g, sodium fluoride
The mixed powder obtained by mixing 20 g of powder in a ball mill for 3 hours was placed in a platinum crucible and heated and melted at 1300 ° C. for 30 minutes. Subsequently, the melt was rapidly cooled in a water bath, and the obtained glass was crushed with a vibrating ball mill. 40 powders obtained by crushing
After passing through a 0-mesh nylon sieve and dispersing 150 g of the powder that passed through the sieve in 1 of methanol, a powder that does not settle within 1 hour (filler B) was collected. The filler B has a particle size of 0.1 to 2.4 μm, an average particle size of 1.1 μm,
It was amorphous with an elution amount of polyvalent metal ions of 14 mgeq / g.

A two-pack type curable composition comprising filler B and camphorquinone and p-dimethylaminobenzoic acid ethyl ester each dissolved in M-5500 in an amount of 0.5% by weight was prepared.

When the curable composition was mixed at a weight ratio of 70/30 at the time of use, the adhesive strength with the tooth structure was 74 kg / cm ² , 75 kg / cm ² under infiltration,
The tensile strength was 221 kg / cm ² .

Example 9 A polyfunctional vinyl monomer having the following structure (A (Mole ratio 1: 6: 3 mixture) -TMM-3L Shin-Nakamura Chemical Co., Ltd.) and vinyl monomer M-5500 having an acidic group (weight ratio 7/93) in camphorquinone and p-dimethylaminobenzoic acid. 9 g of acid ethyl ester in which 0.5 wt% of each was dissolved and 21 g of filler A were mixed in the dark, and then defoamed in vacuum to prepare a curable composition.

The adhesive strength of the above curable composition with the tooth substance was 54 kg / cm ² , the wet strength was 56 kg / cm ² , and the tensile strength was 253 kg / cm ² .

Example 10 Polyfunctional vinyl monomer, A-TMM-3L, was added with 6% by weight of N, N'-di (β-hydroxyethyl) -p-toluidine.
9 g of the melted mixture and 21 g of filler B were mixed (referred to as paste I). Next, 9 g of a mixture of M-5500 containing 2% by weight of benzoyl peroxide and 21 g of filler B were mixed (referred to as paste II). Weight ratio of curable composition consisting of paste II
1/9 results mixed and tested at a rate of, the adhesive strength between the tooth is ^{58kg / cm 2, 55kg / cm} 2 in humid, tensile strength 240 kg / cm ²
was.

Example 11 A polyfunctional vinyl monomer having the following structure (M -315, manufactured by Toagosei Co., Ltd.), a vinyl monomer having an acidic group, and M-5500 (weight ratio 12/88) were dissolved in camphorquinone and p-dimethylaminobenzoic acid ethyl ester at 0.5% by weight, respectively. After mixing 9 g of the product and 21 g of the filler B under light shielding, vacuum defoaming was performed to prepare a curable composition.

The contact strength of the curable composition with the tooth substance was 53 kg / cm ² , the wet strength was 49 kg / cm ² , and the tensile strength was 257 kg / cm ² .

Example 12 Powder consisting of 184 g of zinc oxide, 19 g of magnesium hydroxide and 4 g of calcium fluoride was mixed in a ball mill for 3 hours, and then 13
It was baked at 00 ° C for 2 hours. The powder obtained by grinding the fired product with a vibrating ball mill is put through a 400-mesh nylon sieve, and 150 g of the powder that has passed through the sieve is dispersed in 1 methanol, and the powder that does not settle within 5 minutes (filler C) is collected. did. The filler C had a particle diameter of 0.2 to 4.9 μm, an average particle diameter of 1.9 μm, and a polyvalent metal ion elution amount of 21 mgeq / g.

Polyfunctional vinyl monomer with the following structure (new Nakamura Chemical Co., Ltd.) and M-5500 (weight ratio 10/90) in which camphorquinone and p-dimethylaminobenzoic acid ethyl ester were dissolved in 0.5% by weight respectively 8
After mixing g with 24 g of filler C under light shielding, vacuum defoaming was performed to prepare a curable composition.

The adhesive strength of the above-mentioned curable composition with the tooth substance was 55 kg / cm ² , the wet strength was 53 kg / cm ² , and the tensile strength was 139 kg / cm ² .

Example 13 M-5500 was mixed with 8% by weight of water, camphorquinone and p-dimethylaminobenzoic acid ethyl ester, respectively.
After mixing 9 g of 5 wt% dissolved and 21 g of filler B under light shielding, vacuum defoaming was performed to prepare a curable composition.

The adhesive strength of the above-mentioned curable composition with the tooth substance was 62 kg / cm ² , 61 kg / cm ² under wet condition, and the tensile strength was 181 kg / cm ² . Table 2 shows the relationship between the immersion time in water after curing and the tensile strength for Examples 1, 10, 13 and Comparative Example 2.

Comparative Example 3 Glass beads (EGB731, manufactured by Toshiba Ballotini) were crushed with a vibrating ball mill. The powder obtained by pulverizing was passed through a 400-mesh nylon sieve, 150 g of the powder that passed through the sieve was dispersed in 1 methanol, and a powder that did not settle within 1 hour (filler D) was collected. The filler D was amorphous with a particle size of 0.2 to 2.9 μm, an average particle size of 1.3 μm, and a polyvalent metal ion elution amount of 1 mgeq / g.

A curable composition was prepared by mixing 10 g of M-5500 containing 0.5% by weight of camphorquinone and 0.5% by weight of p-dimethylaminobenzoic acid ethyl ester and 20 g of filler D under light shielding, followed by vacuum defoaming.

The adhesive strength of the above-mentioned curable composition with the tooth structure was 23 kg / cm ² , and 17 kg / cm ² under infiltration, and the tensile strength could not be measured.

Comparative Example 4 20 g of camphorquinone and 0.5 g of p-dimethylaminobenzoic acid ethyl ester each dissolved in M-5500 were mixed with 4 g of filler A under light shielding and vacuum defoaming to prepare a curable composition. did.

The adhesive strength of the above-mentioned curable composition with the tooth structure was 14 kg / cm ² , 13 kg / cm ² under infiltration, and the tensile strength was 58 kg / cm ² .

Claims (1)

[Claims] 1. A vinyl monomer 100 having (A) an acidic group.
Parts by weight (B) 30 to 500 parts by weight of ion-eluting filler that elutes 2 mgeq / g to 60 mgeq / g of polyvalent metal ions, and (C) a curable composition comprising a polymerization initiator.