JPH03281614A - Curable composition - Google Patents

Abstract

PURPOSE:To provide a curable composition which is excellent in adhesiveness to dentin, can give a cured product from which any substance scarcely dissolves in water and is desirable as, e.g. a dental backing material by mixing a specified polymerizable oligomer with a polyvalent metal ion releasing filler, water and a polymerization initiator in a specified weight ratio. CONSTITUTION:A curable composition is produced by mixing 100 pts.wt. polymerizable oligomer having a carboxyl content of 5X10<-3>-1.5X10<-2> equivalent/g, an ethylenically unsaturated group content of 5X10<-4>-3X10<-3> equivalent/g and a weight-average mol.wt. of 1000-6000 (e.g. glycidyl methacrylategrafted acrylic acid/maleic acid copolymer) with 50-800 pts.wt. polyvalent metal ion-releasing filler (e.g. fluoroaminosilicate glass), 10-100 pts.wt. water and 0.1-10 pts.wt. polymerization initiator (e.g. benzoyl peroxide).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention provides a curable composition that produces less elution from the cured product. Specifically, we will discuss the curable composition that is most suitable as a dental lining material.

[Prior art and its problems]

Composite resin is often used to repair missing parts of teeth caused by dental caries. Composite resin is made by filling an acrylic monomer with inorganic filler, and its cured product has an appearance similar to teeth and has sufficient mechanical strength for practical use.

However, composite resins have various clinical problems. In particular, damage may occur to the nerve or pulp of the treated tooth, sometimes leading to pulp necrosis. The cause of this toxicity to the dental pulp is currently unknown, but
It is also said that this is due to the elution of substances that are irritating to living organisms, such as unpolymerized monomers, from the composite resin after curing.

In order to prevent such pulp stimulation, a surgical technique in which a backing layer is prepared using glass ionomer cement before filling the tooth cavity with composite resin has rapidly become popular in recent years. Glass ionomer cement is composed of an aqueous solution of polycarboxylic acid and a powder of polyvalent metal ion-eluting glass, and is cured by a crosslinking reaction between the carboxylic acid and polyvalent metal ions.

Therefore, its major feature is that it does not contain monomeric components and does not elute substances that are irritating to the dental pulp.

However, glass ionomer cement has a relatively low cured strength, and in order to achieve practical strength, the crosslinking reaction must proceed rapidly in the early stage of curing. It has problems such as not necessarily being easy to handle.

Furthermore, since final curing takes time, clinicians have to wait for a certain period of time before filling the composite resin, resulting in a loss of valuable clinical time. Furthermore, since the adhesive strength of the glass ionomer cement to the tooth structure is not high, the composite resin filled thereon may sometimes peel off from the tooth structure due to polymerization shrinkage.

Recently, in order to control the hardening of glass ionomer cement, a technology has been developed in which polymerizable monomers are further added to polycarboxylic acid and polyvalent metal ion-eluting glass to promote polymerization and hardening at the same time as ionic crosslinking. has appeared. Currently, such compositions are called photocurable glass ionomer cements because they cure by irradiation with visible light, and while the initial crosslinking by ionic reaction is relatively slow and provides sufficient operating time, Rapid curing by polymerization reaction is possible.

However, there is a problem in that polymerizable monomers are eluted from the hardened cement.

[Means for solving problems]

The present inventors have conducted extensive research in order to overcome the above technical problems. As a result, a composition consisting of a specific polymerizable oligomer multivalent metal ion-eluting filler, water, and a polymerization initiator has excellent adhesion to tooth structure and strength of the cured product, and has very low elution from the cured product. The present invention was completed based on the discovery of the phenomenon that

That is, in the present invention, (A) carboxyl group content is 5X10-3 to 1.5X
10-2 equivalents/g, ethylenically unsaturated group content is 5X
10-4 to 3 x 10-3 x 10-3 equivalent/g, polymerizable oligomer 100 having a weight average molecular weight of 1000 to 6000
Part by weight (B) Polyvalent metal ion eluting filler 50-800! i
The present invention relates to a curable composition containing (C) 10 to 100 parts by weight of water and (D) 1 to 10 parts by weight of a polymerization initiator (o, i).

The polymerizable oligomer used in the present invention has a carboxyl group and an ethylenically unsaturated group in the same molecule.

The carboxyl group content contained in the above polymerizable oligomer is from 5X10"3 equivalents/g to 1.5X10-2 equivalents/g
It is. If the content is smaller than the above range, the adhesive strength with tooth structure will decrease. Moreover, if it is larger than the above range, curing due to polymerization of ethylenically unsaturated groups will be insufficient.

The content of ethylenically unsaturated groups contained in the above polymerizable oligomer is 5 x 10-' equivalents 7 to 3 x 103 equivalents/g
It is. If the content is smaller than the above range, polymerization will be insufficient, and if the content is larger than the above range, the adhesive strength with tooth structure will decrease.

Furthermore, the weight average molecular weight of the polymerizable oligomer is 1000.
~6000. If the molecular weight is smaller than this range, there will be a lot of elution from the cured product, and if it is larger than this range, the viscosity will be too high when mixed with other components as a curable composition, and the mixing will be uneven, resulting in a poor cured product. can't get it.

The structure of the polymerizable oligomer of the present invention is not particularly limited as long as it satisfies the conditions described above, but preferred examples include an acrylic acid polymer or a combination of acrylic acid and maleic acid, itaconic acid, allylmalonic acid, etc. Examples include polymers in which a compound having an ethylenically unsaturated group is grafted onto a copolymer. As the above-mentioned compound having an ethylenically unsaturated group, glycidyl methacrylate, hydroxyethyl methacrylate, isocyanatoethyl methacrylate, etc. can be used.

If necessary, it is also possible to mix and use two or more of the above polymerizable oligomers.

The polyvalent metal ion eluting filler used in the present invention is
It is not particularly limited as long as it elutes ions that crosslink carboxylic acids such as calcium, strontium, aluminum, etc., but the amount is 50 to 800 parts by weight, more preferably 100 to 6 parts by weight, based on 100 parts by weight of the polymerizable oligomer.
00 parts by weight. If the amount of the polyvalent metal ion-eluting filler is smaller than the above range, there will be a large amount of elution from the cured product, and if it is larger than the above range, the filler and other components will not be sufficiently mixed, making it difficult to form a uniform curable composition. can't get it.

Preferred examples of the polyvalent metal ion-eluting filler include hydroxides such as calcium hydroxide and strontium hydroxide, phosphates such as tricalcium phosphate, tetracalcium phosphate, and hydroxyapatite, zinc oxide, silica alumina,
There are oxides such as fluoroaluminosilicate glass.

Among them, fluoroaluminosilicate glass is most preferred in consideration of elution from the cured product and adhesive strength with tooth structure.

The above-mentioned fluoroaluminosilicate glass is a well-known glass used for dental cements, such as glass ionomer cements. The composition of commonly known fluoroaluminosilicate glasses is, in ionic weight percent, silicon, 1O~33; aluminum, 4~3
0; alkaline earth metal, 5-36: alkali metal,
0-10: Phosphorus, 0.2-16: Fluorine, 2-40
and residual oxygen are preferably used. Further, more preferable composition ranges are as follows: silicon, 15-25; aluminum, 7-20; alkaline earth metal, 8-28.
: Alkali metal, 0-IO: Phosphorus, 0.5-8;
Fluorine, 4-40 and residual oxygen. It is also preferable to replace some or all of the alkaline earth metals with magnesium, strontium, or barium, and strontium is particularly preferably used because it imparts X-ray opacity to the cured product. The most common alkali metal is sodium, but some or all of it can be replaced by lithium,
Substituting potassium or the like is also suitable. If necessary, part of the aluminum may be replaced with titanium, yttrium, zirconium, hafnium, tantalum, lanthanum, or the like. If necessary, the above-mentioned components may be replaced with other components as long as the physical properties of the resulting cured product are not significantly impaired.

The polyvalent metal ion eluting filler has a weight of 2 milliequivalents/g.
It is preferable to use one that elutes polyvalent metal ions of up to 60 meq/g, and more preferable to elute 5 to 30 meq/g. If the elution amount is smaller than the above range, crosslinking between carboxyl groups and polyvalent metal ions will not occur sufficiently, resulting in a decrease in adhesive strength with tooth structure. Moreover, if the elution amount is larger than the above range, it becomes impossible to obtain a practically sufficient operating time. In addition, in the present invention, the elution amount of the polyvalent metal ion-eluting filler is determined by adding 1 g of the filler at a temperature of 37°C and a pH of
It refers to the amount of polyvalent metal ions eluted when a sample is immersed in an aqueous solution of 2,2 acrylic acid 501 for 24 hours.

The shape of the polyvalent metal ion-eluting filler used in the present invention is not particularly limited, and may be crushed particles such as those obtained by ordinary pulverization, or spherical particles, and may be plate-shaped, fibrous, etc. as necessary. It is possible to mix the particles of

The particle size of the polyvalent metal ion-eluting filler described above is not particularly limited, but it is desirable that the powder and liquid components can be easily mixed during use, and it is preferable that particles that are too large are present.・No. Therefore, particles with an upper limit of particle diameter of 50 μm, preferably 20 μm are suitably used. In addition, if the particle size is too small, the surface area of the inorganic oxide becomes large,
Difficult to mix with other ingredients. Therefore, the lower limit of the preferable particle size of the inorganic oxide is 0.1 μm.

The amount of water used in the present invention is 10 to 100 parts by weight, preferably 10 to 7 parts by weight, per 100 parts by weight of the polymerizable oligomer.
0! It is a quantity part. Below the above range, the viscosity of the mixture of polymerizable oligomer and water becomes too high, making it impossible to obtain a uniform cured product. Moreover, if it exceeds the above range, the adhesive strength with the tooth structure will be insufficient.

The polymerization initiator used in the present invention is not particularly limited, and any known radical generator may be used without any limitations. For example, henzoyl peroxide, baracrocohenzoyl peroxide, 2,4-dichlorohenzoyl peroxide, acetyl peroxide, lauroyl peroxide, tertiary-butyl peroxide, cumene hydroperoxide, 2,5-dimethyl hexane 2.5
- Organic peroxides such as dihytroperoxide, methyl ethyl ketone peroxide, tertiary butyl peroxyhenzoate, azo compounds such as azobisisobutyronitrile, organic acid compounds such as tributylboric acid, etc. suitable.

It is also possible to carry out polymerization at room temperature by using the above organic peroxide and amine in combination, but such amines include secondary or tertiary amines in which an amino group is bonded to an aryl group. Amines are preferably used because of their ability to accelerate curing. For example, hl, N'-dimethyl-P-)cyidine, N
, N'-dimethylaniline, No-β-hydroxyethyl-aniline, ~, N'-di(β-hydroxyethyl)
-Aniline, N,N'-di(β-hydroxyethyl)
-P-toluidine, N-methyl-aniline, N-methyl-P-1 luidine and the like are preferred.

It is also a preferred embodiment to use a photosensitizer that generates radicals upon irradiation with light as the polymerization initiator.

Examples of photosensitizers for ultraviolet light include Hengein,
Examples include hengeine methyl ether, hengeine ethyl ether, acetoine hensifhenone, P-chlorohensifhenone, and P-methoxyhensifhenone. Photosensitizers that initiate polymerization with visible light are more preferably used because they do not require ultraviolet rays that are harmful to the human body. Examples of these include camphorquinone, hensyl, α-naphthyl, acetonaphthene, p. , p'-dimethoxyhensyl, p
, p'-dichlorohensylacetyl, pentanedione,
Examples include α-diketones such as 1°2-phenanthrenequinone, 3,4-phenanthrenequinone, 9.10-phenanthrenequinone, and naphthoquinone. Among them, camphorquinone is most preferably used. It is also preferable to use a photopolymerization accelerator in combination with a photosensitizer.

Such photopolymerization accelerators include N,N-dimethylaniline, N,IJ-diethylaniline, N,N-di-n-butylaniline, N,N-dihenzylaniline, N,N-
Dimethyl-p-)cyidine, N, diethyl-ρ-toluidine, ~, ~dimethyl-toluidine, ρ-bromo N, N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminohenzoic acid Ethyl ester, ρ-dimethylaminobenzoic acid amino ester, p-dimethylaminoacetophenone, p-dimethylaminohenzoic acid, N, N
-dimethyl anthranic acid methyl ester, N,
N-dihydroxyethylaniline, N,)l-dihydroxyethyl-p-)shiidine, p~dimethylaminophenethyl alcohol, ρ-dimethylaminostilbene, N
, N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N,N-dimethyl-α-naphthylamine, trabutylamine, tripropylamine, triethylamine, N-methyljetanolamine, N-ethyljetanolamine, N,N-dimethylhexylamine, N,N-dimethyldodecylamine, N,N-dimethylstearylamine, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, 2.2'-(n-butylimino ) Tertiary amines such as jetanol, barbylic acids such as 5-butylbarbylic acid and ]-hensyl-5-phenylbarbylic acid are preferably used. At least one of these photopolymerization accelerators can be selected and used. Furthermore, two or more types can be used in combination.

The amount of the polymerization initiator added may be selected from the range of 0.1 to 10 parts by weight per 100 parts by weight of the polymerizable oligomer.

Furthermore, if necessary, it is also possible to add compatible components to the mixture of the polymerizable oligomer of the present invention and water.

Examples include nonionic or anionic surfactants (including polycarboxylic acids) to improve the compatibility of polymerizable oligomers with water, tartaric acid to promote the elution of polyvalent metal ions, Examples include sodium hydrogen phosphate. For example, substances such as succinic acid monoacryloyloxyethyl ester, succinic acid monomethacryloyloxyethyl ester, phthalic acid monoacryloyloxyethyl ester, and phthalic acid monomethacryloyloxyethyl ester, that is, substances in which the carboxylic acid and the ethylenically unsaturated group are the same Adding a compound contained in the molecule is a preferable embodiment from the viewpoint of adhesive strength with tooth structure.

The packaging form of the curable composition of the present invention is usually a two-bag type, since it is not preferable to store water and the polyvalent metal ion-eluting filler in the same container, but the packaging is not limited to this. Combinations of other components can be determined as appropriate.

Specifically, a liquid component consisting of a polymerizable oligomer and water and a polyvalent metal ion eluting filler are packaged separately, and water, a polymerizable oligomer and a polyvalent metal ion eluting filler are packaged separately. Any of the embodiments is possible, and the polymerization initiator can be added in a convenient manner in consideration of storage stability and the like.

〔effect〕

The curable composition of the present invention has a feature that it has higher adhesive strength to tooth structure than conventional glass ionomer cements and composite resins, and that less substances are leached into water from the cured product.

Due to these features, the curable composition of the present invention can be used not only as a dental backing material but also as a bonding material for composite resins and a dental sealant.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples. still,
The definitions of various quantities related to the properties of materials shown in the text and in the examples and the methods for measuring them are as follows.

(1)! Take 1 ml of the ethanol solution of the carboxyl group content sample of the synthetic oligomer, add 1 ml of 0.275 M hydroxylamine perchlorate and 0.5 ml of 0.5 M N,N'-dichlorohexyl chloride F, and incubate at 60°C.
was heated for 30 minutes. 00 after cooling, IMFe(III)
Add 1 ml of the solution and add IMHCIO to make a total volume of 5 ml.
Absorbance was measured at 525 nm using a blank test solution as a control.

(2> Ethylenically unsaturated group content of polymerizable oligomer Sample 0.02 gCHCh5ml Dissolved in 5ml,
10 ml of bromine-11tl acid pyridine solution was added, shaken well, and left at room temperature. After 5 minutes, dissolve 10% Klff
(3) Weight average molecular weight of polymerizable oligomer The molecular weight of the sample was determined from the retention time by GPC measurement (column: 5hodex/manufactured by Showa Denko, solvent: tetrahydrofuran).
The relative molecular weight was determined using polyethylene glycol of known molecular weight as a reference.

Note that hereinafter, the weight average molecular weight will be simply referred to as molecular weight.

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

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

(6) Filler polyvalent metal ion elution amount 1 of acrylic acid
1 g of filler was added to 50 ml of 0% by weight aqueous solution (pH = 2.2), and after stirring at 37°C for 24 hours, the amount of polyvalent metal ions eluted was measured using an atomic absorption spectrophotometer (manufactured by Shimabara Seisakusho Co., Ltd.). .

(7) Operation time and curing time A predetermined amount of the curable composition is weighed out using a balance, kneaded for 30 seconds, and then divided into three equal parts. When one side is lifted with a spatula, the time when the thread stops coming out is called the operation time, and when the other side is pressed with a spatula, the time when no marks are left is called the curing time.

All operations are performed at a constant temperature of 23°C.

Note that it was difficult to measure the operating time of the composite resin due to its high viscosity.

(8> Adhesive strength with tooth structure: Polish the natural tooth with #800 emery vapor under water injection,
The dentin plane was carved out. A double-sided tape with a hole of 4 mm in diameter was pasted on this flat surface, and a piece of paraffin wax with a thickness of 3 mm and a hole of 3 mm in diameter was pasted on top of it, with the center aligned with the double-sided tape. After filling the compound, it was cured by irradiating it with visible light for 30 seconds using a white light (manufactured by Takara Helmont), and then placed in water at 37℃ for 2 hours.
After soaking for 4 hours, a diameter of 8 mm and a length of 18 m was formed on the surface of the cured product.
m stainless steel rods were fixed with instant adhesive.

Then, using an autograph, a tensile load was applied between the natural tooth and the stainless steel rod (crosshead speed 10 mm/m1).
By adding n), the adhesive strength between the tooth substance and the hardened material was measured.

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

(9> Eluate from the cured product After curing the curable composition in a mold with holes of 3 mm x 6 mm diameter, it was held at 37°C for 1 hour. Visible light irradiation with a light was performed for 30 seconds.

Next, the cured body was taken out of the mold and immersed in ethanol at 37°C for 2 weeks, followed by liquid chromatography column: Nucleosil/manufactured by Nagel, solvent:
The organic components eluted with acetonitrile-water were quantified. The elution amount was expressed as weight % based on the cured product.

Example 1 300 ml of isopropyl alcohol was placed in a four-way flask equipped with a thermometer, stirring rod, reflux condenser, and nitrogen inlet tube.
, acrylic acid 24g, azobisisobutyronitrile 1.
8 g was added and mixed at 82° C. for 6 hours while introducing nitrogen gas. Thereafter, the reaction vessel was depressurized to distill off isopropyl alcohol and unreacted acrylic acid, and the resulting translucent solid was washed with Hensen's water and dried. The yield of product is 15.
It was 8g.

100 ml of dry dioxane, 10 g of the above-mentioned product, 8 g of isocyanatoethyl methacrylate, and 0.4 g of dibutyltin dilaurate were placed in a four-way flask equipped with a thermometer, stirring rod, reflux condenser, and nitrogen inlet tube, and the mixture was heated at 60°C.
The solution stirred for 4 hours was mixed with a 1=2 solution of water/methanol (
The resulting precipitate was filtered to obtain 14.1 g of a polymerizable oligomer. This polymerizable oligomer (hereinafter referred to as polymerizable oligomer A) had a molecular weight of 2,700, a carboxyl group content of 8×10 −3 equivalents/g, and an ethylenically unsaturated group content of 2.3×10 −3 equivalents/g.

6 g of polymerizable oligomer A, 2.4 g of succinic acid monoacryloyloxyethyl ester, 1.6 g of water, and 0.08 g of camphorquinone were combined to obtain a cured liquid.

On the other hand, powders consisting 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 56 g of calcium fluoride were mixed in a ball mill for 3 hours.The resulting mixed powder was placed in a platinum crucible. It was then heated at 1400°C for 30 minutes. The melt was then rapidly cooled in a water bath and the resulting glass was ground in a vibrating ball mill. The powder obtained by pulverization was passed through a 400-mesh nylon sieve, and 150 g of the powder that passed through the sieve was dispersed in 11 methanol. Those that did not settle within 1 hour were collected and the polyvalent metal ion eluting filler was collected. Obtained. The filler had a particle size of 0.2 to 2.7 μm, an average particle size of 1.0 μm, and an elution amount of polyvalent metal ions of 19 milliequivalents/g, and was amorphous.

The above curing liquid and the above polyvalent metal ion eluting filler are mixed into 2 parts:
The operation time was 9 minutes and 20 seconds, and the curing time was 18 minutes and 10 seconds.When irradiated with white light for 30 seconds after kneading, it was found that any amount within the above curing time was I was able to finish curing on time. Moreover, the adhesive strength with the tooth substance was 75 kg/crt+2, and the amount eluted from the cured product was 0.07 wt%.

Example 2 300 ml of isopropyl alcohol was placed in a four-way flask equipped with a thermometer, stir bar, reflux condenser, and nitrogen inlet tube.
, acrylic acid 15g, azobisisobutyronitrile 1.
1 g was added and mixed at 82°C for 6 hours without introducing nitrogen gas. Thereafter, the pressure in the reaction vessel was reduced to distill off isopropyl alcohol and unreacted acrylic acid, and the resulting translucent solid was washed with Hensen's water and dried. The yield of adult organisms is 10.
It was 5g.

Put 100 ml of dry dioxane, 8 g of the above product, and 4 g of glycidyl methacrylate into a four-way flask equipped with a thermometer, stirring rod, reflux condenser, and nitrogen inlet tube, and add 60 g of glycidyl methacrylate.
The solution stirred for 8 hours at °C was poured into a 1:2 solution (volume ratio) of water/methanol, and the resulting precipitate was filtered to obtain 7.1 g of a polymerizable oligomer. This polymerizable oligomer (hereinafter referred to as polymerizable oligomer B) had a molecular weight of 1200, a carboxyl group content of 8×10 −3 equivalents/g, and an ethylenically unsaturated group content of 1.3×10”3 equivalents/g.

Add 300ml of isopropyl alcohol to a four-way flask equipped with a thermometer, stirring rod, reflux condenser, and nitrogen inlet tube.
, acrylic acid 30g, azobisisobutyronitrile 2,
3 g was added and the mixture was crushed at 82°C for 6 hours without introducing nitrogen gas. Thereafter, the reaction vessel was depressurized to distill off isopropyl alcohol and unreacted acrylic acid, and the resulting translucent solid was washed with heshizene and dried. The yield of adult organisms is 26.
It was 2g.

Put 100 ml of dry dioxane, 10 g of the above product, and 5 g of glycidyl methacrylate into a four-way flask equipped with a thermometer, stirring rod, reflux condenser, and nitrogen inlet tube, and add 6 g of glycidyl methacrylate.
The solution stirred at 0° C. for 8 hours was poured into a 1:2 solution (by volume) of water/methanol, and the resulting precipitate was filtered to obtain 8.8 g of a polymerizable oligomer. The molecular weight of this polymerizable oligomer (hereinafter referred to as polymerizable oligomer ○) was 4300, the carboxyl group content was 1Xl0-2 equivalent/g, and the ethylenically unsaturated group content was 8XlO-' equivalent jl/g.

5 g of the above polymerizable oligomer B, 5 g of polymerizable oligomer C
, 5 g of water, and 0.10 g of camphorquinone were mixed to obtain a hardening liquid.

When the above curing liquid and the polyvalent metal ion eluting filler obtained in Example I were mixed at a weight ratio of 2:1 and various properties were measured, the operating time was 5 minutes 30 seconds, and the curing time was 9 minutes 10 seconds. When white light was irradiated for 30 seconds after kneading, the curing could be completed within the specified curing time. Moreover, the adhesive strength with the tooth substance was 69 kg/crn2, and the amount eluted from the cured product was 0-.t%.

Comparative Example 1.2.3 Test results using the dental composite resin Palficrite (manufactured by Tokuyama Soda Co., Ltd.) and the attached bonding material,
and GC Lining Cement (Menshi Dental Industry W), a glass ionomer cement for dental backing, and Vitrabont (3), a light-curable glass ionomer cement for dental backing.
Company M! As a comparison, the operation time, curing time, adhesive strength with tooth structure, and amount eluted from the cured product were measured.

Example 3 87 g of the polymerizable oligomer obtained in Example 2, 3 g of polymerizable oligomer C, 3.3 g of water, and 0.30 g of camphorquinone
g was mixed to obtain a hardening liquid.

When the above cured jα and the polyvalent metal ion eluting filler obtained in Example 1 were mixed at a weight ratio of 1.4:1 and various properties were measured, the operation time was 6 minutes and 10 seconds, and the curing time was 10 minutes. The curing time was 50 seconds, and by irradiating white light for 30 seconds after kneading, curing could be completed at any time within the above curing time. In addition, the adhesive strength with tooth structure is 63kg/crn2
The amount eluted from the cured product was 0 wt%.

Example 4 83 g of the polymerizable oligomer obtained in Example 2, 7 g of polymerizable oligomer, 6 g of water, and 0.10 g of camphor-7-quinone
were mixed to obtain a curing solution.

When the above curing liquid and the polyvalent metal ion eluting filler obtained in Example 1 were mixed at a weight ratio of 2.5:1 and various sesames were measured, the operation time was 8 minutes 40 seconds, and the curing time was 14 minutes. By irradiating white light for 30 seconds after kneading, curing could be completed at any time within the above curing time. Furthermore, the adhesive strength with the tooth substance was 59 kg/crn2, and the amount eluted from the cured product was 0 wt%.

Comparative Example 4 400 ml of 77 tons and 100 g of maleic acid were placed in a Mitsuro flask equipped with a thermometer, a stirring rod, and a reflux condenser, and mixed. 200 ml of pyridine was added dropwise to the reaction vessel. After stirring for 122 hours while keeping the reaction temperature at about 20°C, chloroform was added to the solution and the resulting precipitate was removed. It was separated by filtration. After adding acetone to this precipitate and removing the resulting precipitate, chloroform was added to the solution and the resulting precipitate was separated by filtration to obtain 15.1 g of product.

Put 100 ml of dry dioxane, 10 g of the above product, and 2 g of glycidyl methacrylate into a four-way flask equipped with a thermometer, stirring rod, reflux condenser, and nitrogen inlet tube, and add 6 g of glycidyl methacrylate.
The solution stirred at 0°C for 8 hours was diluted with water/methanol (1:2).
The resulting precipitate was poured into a solution (volume ratio) and the resulting precipitate was filtered to obtain 7.1 g of a polymerizable oligomer. This polymerizable oligomer (
The molecular weight of polymerizable oligomer E) is 5600,
Carboxyl group content is 1.7X I O-2 equivalent 11/
g, ethylenically unsaturated group content is lXl0-' equivalent/g
was.

5 g of the polymerizable oligomer E, 4 g of water, and 0.05 g of camphorquinone were mixed to obtain a hardening liquid.

When the above curing liquid and the polyvalent metal ion eluting filler obtained in Example 1 were mixed at a weight ratio of 2:1 and various properties were measured,
The operation time was 3 minutes 50 seconds, the curing time was 6 minutes 10 seconds,
After kneading, irradiation with white light for 30 seconds did not promote curing. In addition, the adhesive strength with tooth structure is 31kg/c.
m2, the amount eluted from the cured product was 0-t%.

Comparative Example 5 300 ml of isopropyl alcohol was placed in a Yotsuro flask equipped with a thermometer, stirring rod, reflux condenser, and nitrogen inlet tube.
, 11,115 g of acrylic, and 1.1 g of azohisisobutyronitrile were added and mixed at 82° C. for 6 hours while introducing nitrogen gas. Thereafter, the pressure in the two returned containers was reduced to distill off isopropyl alcohol and unreacted acrylic acid, and the resulting translucent solid was washed with Hensen's water and dried. The yield of adult organisms is 10
．． It was 5g.

Put 100 ml of dry dioxane, 8 g of the above product, and 10 g of glycidyl methacrylate into a four-way flask equipped with a thermometer, stirring rod, reflux condenser, and nitrogen inlet tube,
The solution stirred at 60°C for 8 hours was diluted with water/methanol (1:2).
solution (volume ratio) and the generated precipitate is 1! 13.3 g of polymerizable oligomer was obtained. The molecular weight of this polymerizable oligomer (hereinafter referred to as polymerizable oligomer 〇) is 260
0, the carboxyl group content was 2X10-3 equivalents/g, and the ethylenically unsaturated group content was 4.3X10'' equivalents/g.

8 g of polymerizable oligomer D, 3 g of water, and 0.08 g of camphorquinone were mixed to obtain a hardening liquid.

The above curing liquid and the polyvalent metal ion eluting filler obtained in Example 1 were mixed at a weight ratio of 2:1 and various properties were determined.The operating time was 12 minutes and 40 seconds, and the curing time was 31. The curing time was 50 seconds, and by applying white light for 30 seconds after kneading, curing could be completed at any time within the above curing time. The adhesive strength with the tooth substance was 20 kg/cm2, and the amount eluted from the cured product was 0-1%.

Comparative Example 6 5 g of polymerizable oligomer B obtained in Example 2, 5 g of polymerizable oligomer C, 5 g of water, and 0.10 g of camphorquinone were mixed to obtain a hardening liquid.

When the above curing liquid and the polyvalent metal ion eluting filler obtained in Example 1 were mixed at a weight ratio of 0.3:1 and various properties were measured, the operating time was 19 minutes and 10 seconds, and the curing time was 48 minutes. By irradiating white light for 30 seconds after kneading, curing could be completed at any time within the above curing time. Furthermore, the adhesive strength with the tooth substance was 17 kg/Cm2, and the amount eluted from the cured product was 0-.t%.

Comparative Example 7 85 g of the polymerizable oligomer obtained in Example 2, 5 g of polymerizable oligomer C, 15 g of water, and 0.10 g of camphorquinone
were mixed to obtain a curing solution.

When the above curing liquid and the polyvalent metal ion eluting filler obtained in Example 1 were mixed at a weight ratio of 2=1 and various properties were measured,
The operating time was 22 minutes and 30 seconds, and the curing time was over 60 minutes.

Comparative Example 8 The molecular weight of the carboxyl group-containing monomer with the following structure is 21
6, and the carboxyl group content is 4 x 10-3 equivalent/
g, and the ethylenically unsaturated group content was 4.1xlO-3 equivalent/g.

10 g of this monomer, 5 g of water and 0.0 g of camphorquinone.
10 g were mixed to obtain a hardening liquid.

When various properties were measured by mixing the above curing liquid and the polyvalent metal ion eluting filler obtained in Example 1 at a weight ratio of 2=1, the operation time was 6 minutes 40 seconds, and after kneading, white light was 3
When irradiated for 0 seconds, curing could be completed at any time. However, curing was not completed without light irradiation. The adhesive strength with the tooth substance was 39 kg/cm2, and the amount eluted from the cured product was 2.13 wt%.

The results of the above Examples and Comparative Examples are summarized in Table 1.

Claims (1)

[Claims] (A) Carboxyl group content is 5×10^-^3 to 1.
100 polymerizable oligomers having an ethylenically unsaturated group content of 5×10^-^2 equivalents/g, an ethylenically unsaturated group content of 5×10^-^4 to 3×10^-^3 equivalents/g, and a weight average molecular weight of 1000 to 6000. Part by weight (B) 50 to 800 parts by weight of a polyvalent metal ion eluting filler, (C) 10 to 100 parts by weight of water, and (D) 0.1 to 10 parts by weight of a polymerization initiator. Curable composition.