JPH0321603A - Curable composition - Google Patents

Abstract

PURPOSE:To provide the subject composition giving a cured product having a high tensile strength and a high adhesive strength to matters containing a metal element by comprising an acidic group-containing vinylic monomer, a polyvalent ion-eluting filler and a polymerization initiator. CONSTITUTION:The objective composition comprises (A) 100 pts.wt. of a vinylic monomer having an acidic group (preferably carboxyl group) [e.g. a compound of the formula (R1 is H or CH3; R2 is H or phenyl; R3 is organic residue), (B) 30-500 pts.wt. of an ion-eluting filler eluting polyvalent metal ions in an amount of 2-60mg eq/g, preferably 5-30mg eq/g, and (C) a polymerization initiator (e.g. benzoylperoxide).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel curable composition. Details. Kuha,
Provides a cured product with high tensile strength, and has high adhesion to objects containing metal elements that have hydrophilic surfaces such as bio-hard microstructures such as teeth, metal materials, and ceramic materials even under wet conditions. It is a curable composition with strength.

[Prior art and its problems]

There are two main methods for repairing relatively small defects in teeth that have been disfigured by dental caries, that is, for conservative restoration.

One method is to take the shape of the defect, make a restoration that fits that shape outside the mouth, and then fix it to the tooth with a luting material.
This is called an inlay restoration method. The other method is to fill the defect with a moldable material and then harden it, which is called a form repair method.

In recent years, the range of application of the above-mentioned kaikata restoration method has been expanding due to the fact that the work process is simpler than that of the inlay restoration method, it can be processed on the same day, and its physical properties have improved due to advances in materials. be.

Composite resins, glass ionomer cements, and amalgams have traditionally been commonly used as materials for molded restorations, but composite resins and glass ionomer cements have color tones and transparency that are similar to those of teeth, so they are highly aesthetically pleasing. It has come to be frequently used as a bearing material.

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

For example, although composite resin has high mechanical strength, it does not itself have adhesive properties with tooth structure, so it is necessary to use an adhesive called a bonding material during filling. However, the use of such a bonding material not only complicates clinical operations, but also has the disadvantage that the adhesive strength is significantly reduced if water in the oral cavity enters during use. Furthermore, even if a bonding material is used, there is a problem in that the adhesive strength between the composite resin and the tooth, particularly the dentin, is insufficient.

On the other hand, glass ionomer cement is a more hydrophilic material than composite resin, and it adheres to tooth structure without using a bonding material. Therefore, although it does not require complicated adhesion operations like composite resins, the tensile strength of the cured product itself is low, and the adhesive strength with the tooth structure is insufficient due to breakage of the cured product. Furthermore, due to this low tensile strength, it is prone to wear and breakage after filling, and has the disadvantage of poor durability.

As described above, there is a need for a filling material that does not require complicated operations, can reliably adhere to tooth structure even under wet conditions, and has sufficient strength.

[Means for solving problems]

The present inventors have conducted extensive research in order to overcome the above technical problems. As a result, the composition, which contains vinyl monomers with acidic groups, specific ion-eluting fillers, and polymerization initiators, reliably adheres to teeth even when cured by moistening, and the cured product has sufficient strength. The present invention was completed based on the discovery that the present invention has the following properties.

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

The acidic group-containing vinyl monomer used in the present invention is not particularly limited, and generally known ones are used. For example, vinyl monomers having an acidic group such as carboxylic acid, phosphoric acid, or sulfonic acid and having a polymerizable unsaturated group are suitable. Among these, the acidic group is preferably a carboxylic acid group. A typical example of a vinyl monomer having a carboxylic acid as an acidic group is the general formula R CI12=C-C-N-R3-{-COOH), 11 0 R2 R CHZ=C-C-0- R4-←COOH)ll, 11 0 NIICIItCOOH, NHCHzCFIz
COOf{, NflCHCOOfl, C113 NHCHzCHzCHzCOOII, NtlC
IIzCHzCHzCllzCOOH,? NHCII
COOI+, CH(CH3)z -NIIC}ICOOH, CIl■CH(CH:+)z - Nll - ClfCOQ}I, CHOH f? 11 C II■CH. CH■Cl12CII2C
OOH? HCIICOOI+, -NIICHCO
OII, C I1 C II ■ CIl3 Cl
l2011CH3 -NIICHCII■COO}I, COOII scale z, R4: organic residue, n: integer from 1 to 4), and the like.

Here, as a preferable specific example R2 of -N-4,-{-COOII)n, ? can be mentioned.

Among these, the most preferably used is N II
C II■CHzCOOfl, NIICll
zClhCII+COOH ,NHCH2CHZCH2
CH2CII COOH ,CH3 Also, as a preferable specific example of "4-{-COOH),1,
-←CHz+rbCH(COOI{)zCH3Clh0 In the present invention, the vinyl monomer having an acidic group can be used alone or in combination of two or more types, if necessary.

Furthermore, a polyfunctional vinyl monomer may be added to the acidic group-containing vinyl monomer, thereby making it possible to further improve the mechanical strength of the resulting cured product. Typical examples that are preferably used include those having an acrylic group and/or a methacrylic group, and specific examples thereof are as follows.

A) Difunctional vinyl monomer (i) Aromatic compound type 2.2-bis(methacryloxyphenyl)propane; 2
,2-bis(4-(3-methacryloxy)-2-hydroxypoxyphenyl)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-methacryloxydipoxyphenyl)propane; 2(4-methacryloxyethoxyphenyl)-2(4
-methacryloxydiethoxyphenyl)propane; 2(
4-methacryloxydiethoxyphenyl)-2(4-methacryloxytriethoxyphenyl)broban; 2(4
-methacryloxydipboxyphenyl)-2(4-methacryloxytriethoxyphenyl)propane; 2,2
-Bis(4-methacryloxydipoxyphenyl)propane: 2.2-bis(4-methacryloxyisopropoxyphenyl)propane and their acrylates (i
i) Aliphatic compound-based ethylene glycol dimethacrylate; diethylene glycol dimethacrylate: triethylene glycol dimethacrylate; butylene glycol dimethacrylate;
neobentyl glycol dimethacrylate; propylene glycol dimethacrylate; 1,3-butanediol dimethacrylate; l,4-butanediol dimethacrylate; 1,6-hexanediol dimethacrylate and their acrylates) trifunctional vinyl monomers Methylolpropane trimethacrylate,? Limethylolethane trimethacrylate, pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate l and these acrylates and monomers having the following structural formula CI13CIl2C + CIlzO
(CH■)30CC=CH2]11 0 R? lhC1I■C10Cll■0 (ClI■CI1■0
) zC C = CH■ ]11 0R CI+30 II CI+,=C-C O Clh 11 CIIzCIICIlz O C C Chz
0 C-O Ni+ (CHz+rNII C=0 ?Ilff 0 0 11 CHz ””C C O CIlzCIICI
I■-0? Clh 11 C-C-CIl■ R (However, R.H or CIl:I) c) Tetrafunctional vinyl monomer pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate, and a urethane monomer having the structural formula shown below N+1 C -0? J=C C O CthCIICtl■-
0-C-C=CH2 The above-mentioned polyfunctional vinyl monomers can be used alone or in combination of two or more types as required. Further, among the polyfunctional vinyl monomers, trifunctional or tetrafunctional vinyl monomers are preferably used because they have a large effect of improving the mechanical strength of the resulting cured product.

The amount of the polyfunctional vinyl monomer added to the acidic group-containing vinyl monomer is preferably 2 to 30%, more preferably 5 to 20% by weight. If the amount added is smaller than the above range, the contribution of the polyfunctional vinyl monomer to the tensile strength will not be sufficient, and if the amount added is larger than the above range, the adhesiveness of the curable composition to the tooth structure tends to decrease. .

When the curable composition of the present invention is immersed in water, the tensile strength of the cured product improves over time.More surprisingly, by adding water to the composition before curing,
It is possible to accelerate the development speed of strength of the cured product. The amount of water added is preferably 1 to 30% by weight, more preferably 2 to 1% by weight based on the acidic group-containing vinyl monomer.
It is 5% by weight. If the amount of water is smaller than the above range, the improvement in strength will not be promoted, and if it is larger than the above range, the strength of the cured product will decrease.

The ion eluting filler used in the present invention is 2 mgeq/
g ~ 60 mgeq/g, preferably 5
It elutes polyvalent metal ions of mgeq/g to 30 Beq/g. In addition, in the present invention, the amount of ion elution from the filler is determined when 1 g of filler is heated to 37°C.
, pl12.2, acrylic acid aqueous solution at 50 mA for 24 hours. Furthermore, the polyvalent metal ion refers to a metal ion having a valence of two or more that can bond to the acidic group of the vinyl monomer having an acidic group, and representative examples thereof include calcium 1, strontium,
Metal ions such as barium, argonium, zinc, and lanthanides.

If the amount of multivalent ions eluted from the ion-eluting filler is smaller or larger than the above range, the tensile strength of the cured product will be insufficient. That is, if the elution star is small, sufficient crosslinking between acidic groups and polyvalent metal ions does not occur, and if the elution amount is large, most of the filler is dissolved, and in either case, , it becomes impossible to exhibit the effect of improving the tensile strength of the resulting cured product.

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

The reason for this is that fluoroaluminosilicate glass elutes more ionic species than other ion-eluting fillers.
It is thought that this has a significant influence on the development of the tensile strength of the cured product that provides the ion elution rate, etc.

As the above-mentioned fluoroaluminosilicate glass, known ones used for dental cements, for example, glass ionomer cements can be used.

The composition of generally known fluoroargonosilicate glasses is silicon, 10 to 3
3; aluminum, 4-30; alkaline earth metal, 5-
36; Alkali metal, 0-10; Phosphorus, 0.2-6:
Fluorine, 2-40 and residual oxygen are preferably used. Further, more preferable composition ranges include silicon, 15
~25; Aluminum, 7~20; Alkaline earth metal,
8-28; Alkali metal, 0-10; Phosphorus, 0. 5～
8: Fluorine, 4 to 40 and residual oxygen. It is also preferable to substitute some or all of the above-mentioned super-alkali metals with magnesium, strontium, or barium. In particular, strontium is often preferably used because it imparts X-ray opacity and high strength to the cured product.

The alkali metal is most commonly sodium, but it is also preferable to replace part or all of it with lithium, potassium, etc. It is also possible to replace it with hafnium, tanker, lanthanum, etc. In addition, if necessary, the above-mentioned precepts may be replaced with other preservatives as long as the physical properties of the resulting cured product are not significantly impaired.

The amount of the ion-eluting filler used in the present invention is from 30 to 100 parts by weight of the acidic group-containing vinyl monomer.
It is 500 parts by weight, more preferably 50 to 400 parts by weight. If the amount of the ion-eluting filler is smaller than the above range, the adhesive strength at the interface between the curable composition and the tooth structure will be insufficient, and if it is larger than the above range, the acidic group-containing vinyl monomer and the ion-eluting filler will be insufficient. It becomes 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 obtained by ordinary pulverization or spherical particles, and plate-shaped, fibrous, etc. particles may be mixed as necessary. You can also do it.

The particle size of the ion-eluting filler is not particularly limited, but when filling teeth, for example, it is desirable that the surface of the cured product is smooth, and the particle size is 50 μm or less, preferably 20 μm or less. are preferably used. or,
If the particle size is too small, the surface area of the ion-eluting filler increases, making it difficult to mix a large amount into 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 any known radical generator may be used without any limitations. For example, penzoyl peroxide, parachloropenzoyl peroxide, 2,4-dichloropenzoyl peroxide, acetyl peroxide, lauroyl peroxide, tertiary butyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane2. 5
-Organic peroxides such as dihydroperoxide, methyl ethyl ketone peroxide, tertiary butyl peroxybenzoate, azo compounds such as abbisisobutyronitrile, organic acid compounds such as tributylboric acid, etc. are suitable. be.

It is also possible to carry out polymerization at room temperature by using a combination of the above organic peroxide and amine, but such amines include secondary or tertiary amines in which an amino group is bonded to a ryoryl group. Ane is preferably used from the viewpoint of accelerating curing. For example, N,N'dimethyl-p-}luidine, N,N
'-Dimethylaniline, N'-β-hydroxyethylaniline, N,N'-'; (β-hydroxyethyl)-aniline N,N'-di(β-hydroxyethyl)-p-toluidine, N-methyl -aniline, N-methyl-p-toluidine, etc. 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 benzoin, benzoin methyl ether, benzoin ethyl ether, acetoin benzophenone p-chlorobenzophenone, p-methoxybenzophenone. In addition, 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 are:
Benzyl, camphorquinone, α-naphthyl, acetonaphcene, p. p'-dimethoxybenzyl, p. p'-dichloropendylacetyl, pentanedione, 1,2-phenanthrenequinone, 1,4-phenanthrenequinone,
Examples include α-diketones such as 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 the above photosensitizer. Examples of such 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-}luidine, N,N-dimethyl-m- }Luidine, p-bromo N,N-dimethylaniline, m-chloro N,N-
Dimethylaniline, p-dimethylaminobenzoic acid ξnobenzaldehyde, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid ξnoester, N. N-dimethyl anthranilic acid methyl ester, N,N-
Dihydroxyethylaniline, N,N-dihydroxyethyl-p-}luidine, p-dimethylaminophenethyl alcohol, p-dimethylaminostilpene, N,N-
Dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N,N-dimethyl-α-naphthylamine, N,
N-dimethyl-β-naphthylamine, triptylamine, triprobylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine,
N,N-dimethylhexylamine, N,N-dimethyldodecylamine, N,N-dimethylstearylamine, N
, N-dimethylaminoethyl methacrylate, N,N-
Diethylaminoethyl methacrylate, 2.2'-
Tertiary amines such as (n-butylimino)diethanol; Valpyr # such as 5-butylvalpyric acid and 1-benzy-5-phenylbarpylic acid can be preferably used. At least one type of these photopolymerization accelerators can be selected and used, and two or more types can also be used in combination.

The amount of the polymerization initiator added may be determined as appropriate. Generally 0.0% for vinyl monomer. It may be selected from the range of 1 to 3% by weight.

The packaging form of the curable M1 of the present invention is not particularly limited,
A vinyl monomer having an acidic group, an ion-eluting filler, and a polymerization initiator (in the case of a photosensitizer) are packaged in a pack, and a vinyl monomer having an acidic group and an ion-eluting filler are packaged in a two-pack to form a polymerization initiator. It is possible to add it to either one of them, and it can be selected as appropriate depending on the purpose.

〔effect〕

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

Furthermore, when the cured product is used as a dental filling material, it has a higher tensile strength than glass ionomer cement, so not only is there no decrease in adhesive strength due to its destruction, but also wear and breakage are less likely to occur. Moreover, it does not require a bonding material, which is essential for composite resin, and has the advantage that good molding restoration is possible and the clinical procedure is simple.

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 lining material for combos and 7 resins, as well as dental sealants, other filling materials, adhesive materials, etc. It can be used.

[Example D] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples. still,
The properties and physical properties of the materials shown in the text and examples are measured as follows.

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

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

(3) Amount of polyvalent metal ion elution from filler: 10% by weight aqueous solution of acrylic acid {p}I=2. 2) 50m
After adding 1 g of filler to ffi and stirring at 37°C for 24 hours, the amount of eluted ions was measured using an atomic absorption spectrophotometer (manufactured by Shimadzu Corporation).

(4) Tensile strength of cured product After curing the hardening composite in a mold having holes of 3 mm x 6 mmφ, it was held at 37°C for 1 hour.

For curing, irradiation was performed for 30 seconds using a visible light irradiator, White Light (manufactured by Takara Belmont), as necessary.

Next, the cured product was taken out of the mold, immersed in water at 37°C for 71 hours, and then heated to a crosshead speed lIIIl/I using Tensilon (manufactured by Toyo Baldwin).
The tensile strength was measured by applying a load in the diametrical direction of the cured product at lin.

The tensile strength was calculated using the following formula.

P: Breaking load (kg/cd) (5) Bond strength with tooth structure Bovine teeth were polished with #800 emery paper under water injection.
The dentin plane was carved out. Diameter 4 [0111] on this plane
Double-sided tape with holes No. 1 was pasted, and on top of that, paraffin wax No. 11 with a thickness of 3 m and with 6 holes in diameter was pasted so that the center coincided with the double-sided tape. After filling the circular hole with a curable composition, it was cured and immersed in water at 37°C for 24 hours. A stainless steel rod with a diameter of 8 mm and a length of 18 mm was fixed to the surface of the cured body using an instant adhesive. Then, by applying a tensile load (crosshead speed 10 mm/win) between the bovine tooth and the stainless steel rod using Tensilon, the adhesive strength between the tooth substance and the hardened material was measured. In addition, the adhesive strength under wet conditions was measured by the same method as above, after applying a thin layer of water to the dentin plane using a sponge before filling with the curable composition.

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.

Example 1 A powder 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 76 g of calcium fluoride was milled in a ball mill for 3 hours. The resulting mixed powder was placed in a platinum crucible and melted by heating 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 grinding is 40
150 g of the powder that passed through a 0-mesh nylon sieve was dispersed in 1 liter of methanol, and the powder that did not settle within 1 hour (referred to as filler A) was collected. Filler A has a particle size of 0. 2-2, 7 μm, average particle size 1.0 μm, polyvalent metal ion elution amount 16 mgeq/g
And it was of poor quality.

A vinyl monomer having an acidic group having the following structure (manufactured by Toagosei Co., Ltd., M-5500) was added with 0.0% camphorquinone and 0.0% p-dimethylaminohenzuinoquacid ethyl ester, respectively.
Log of 5% by weight dissolved and filler A. 2
After mixing 0 g under light shielding, the mixture was bubbled in a vacuum to prepare a curable composition.

? ,C = CIICOCH■Cll■OCCHzC
IIzCOOII1111 00 The adhesive strength of the above curable composition with tooth structure is 83 kg/c
tA, 77 kg/cflI under infiltration, tensile strength is 2 1
3 kg/ca! Met.

Examples 2-4 A test was conducted in the same manner as in Example 1, except that a fluoroaluminosilicate glass with a different Mi precept from Example 1 was prepared. The results of Examples 1 to 4 are shown in Table 1.

Comparative Examples 1 and 2 Test results using a commercially available dental composite resin (mainly containing a polyfunctional vinyl monomer without acidic groups, silica filler, and an α-diketone polymerization initiator) and the attached bonding material Table 1 shows the test results for Comparative Example 1 and glass ionomer cement for dental fillings (mainly containing polykanoleponic acid and fluoroanoleminosilicate glass) as Comparative Example 2.

Example 5 β-alanine 1 in a three neck flask 7. 8 g and 4
% sodium hydroxide aqueous solution was added and dissolved. While keeping this flask at 10°C or below, add acrylic acid chloride 1 8. 1 g was added dropwise over 1 hour.

After the reaction was completed, 6N hydrochloric acid was added to the solution to make pll3, and the mixture was extracted and purified with ethyl acetate to obtain a vinyl monomer having an acidic group having the following structure.

HtC=CIICNCHzClhCOOH11 0 Camphorquinone and N,N-dimethyl-p-toluidine are added to this vinyl monomer having an acidic group at 0.80% each.
After mixing 9 g of the weight percent dissolved material and 21 g of filler A under light shielding, the mixture was defoamed in vacuum to prepare a hardening composition. The adhesive strength of the above-mentioned curable composition with tooth substance is 56 kg/1,
61kg/cnl under wet condition, tensile strength is 191k
It was g/cal.

Example 6 After dissolving 25 g of potassium salt of N-phenylglycine in 125 m# of ion-exchanged water, glycidyl methacrylate 1
8. 5 g was added and 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. This precipitate was filtered and dried under reduced pressure to produce vinyl having an acidic group with the following structure. I got the monomer.

Clh A mixture of this acidic group-containing vinyl monomer and M-5500 (weight ratio 30/70), camphorquinone, N
, N-dimethyl-p-toluidine dissolved in an amount of 0.8% by weight, respectively, and 20 g of filler A were mixed together under light shielding, followed by vacuum defoaming to prepare a curable composition.

Teeth of the above-mentioned hardenable composition. The adhesive strength with the material is 64kg
/ cd, 57 kg/cnl under wet condition, tensile strength is 14
2kg/ell! was.

Example 7 Camphorquinone and p-dimethylaminobenzoic acid ethyl ester were added to a mixture of 11-methacryloxy-1,1-undecanedicarboxylic acid and M-5500 (weight ratio 10/90) at 0.0. After mixing 10 g of the 5% by weight solution and 20 g of filler A under light shielding, vacuum defoaming was performed to prepare a curable composition.

The adhesive strength of the above-mentioned curable composition with the tooth structure is 8 lkg/
cd, 75kg/cnl under wet condition, tensile strength is 15
It was 3kg/c-.

Example 8 Powders consisting of 120 g of silica, 38 g of aluminum phosphate, 140 g of aluminum ξ fusodide, 70 g of strontium fluoride, and 20 g of sodium fusodide were mixed in a ball mill for 3 hours, and the resulting mixed powder was placed in a platinum crucible.
The mixture was heated and melted at 00'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 to collect filler B which did not settle within 1 hour. Filler B has a particle size of 0. 1-2. 4 p m, average particle size 1.1
μm, polyvalent metal ion elution ft 1 4 mgeq/
g and was of poor quality.

Camphorquinone and p-dimethylaminobenziisoquasidoethyl ester were added to M-5500, a vinyl monomer having an acidic group, at 0. A two-back type curable composition consisting of Filler B and Filler B was prepared.

When the above-mentioned curable composition was mixed at a weight ratio of 70/30 during use, the adhesive strength with tooth structure was 74 kg/cd, 75 kg/c+J under infiltration, and the tensile strength was 221 kg/1.

Example 9 Polyfunctional vinyl monomer (A?l{
OCH ■ → Ding C-{-CI20CCI=CI+2)Z)
{O HOCH 2- C1←C}lzOccII = Ct
lz) +111 0 C +CIIzOCCII =CHz) a] I O (mixture with a molar ratio of 1:6:3) -TMM-3L manufactured by Shin Nakamura Chemical Co., Ltd.) and a mixture of vinyl monomer M-5500 having an acidic group (with a weight ratio of 7 /9 3)
After mixing 9 g of camphorquinone and p-dimethylaminobenzoin acid ethyl ester dissolved in 0.5% by weight each with 21 g of filler A under light shielding,
A curable composition was prepared by vacuum defoaming.

The adhesive strength of the above-mentioned hardenable composition with the tooth structure is 54 kg/cI.
J, 56kg/co under wet conditions! , tensile strength is 2 5 3
It was kg/d.

Example 10 Polyfunctional vinyl monomer, A-TMM-3L, NN'
-di(β-hydroxyethyl)-p-}9 g of a mixture containing 6% by weight of luidine and 821g of filler were mixed (referred to as paste I).Next, 2% by weight of henzoyl peroxide was dissolved in M-5500. ? 9 g of W compound and 821 g of filler were mixed (referred to as paste ■).As a result of testing a curable composition consisting of paste I and paste ■ mixed at a weight ratio of 1/9, the adhesive strength with tooth structure was determined. is 58 kg/cal, 55 kg/crA under wet conditions,
The tensile strength was 240 kg/cJ.

Example ■1 Polyfunctional vinyl monomer (M-3 1
5. Toagosei Co., Ltd.) and a vinyl monomer having an acidic group, M-5500 (double star ratio 12/88), camphorquinone, p~dimethylanobenzoisoquacid ethyl ester, 0.5 weight percent each. 9g of dissolved
and 821 g of filler were mixed under light shielding, followed by vacuum defoaming to prepare a curable composition.

The adhesive strength of the above-mentioned curable composition with the tooth structure is 53 kg/cI.
I1, 49 kg/cd under wet condition, tensile strength is 2 5 7
It was kg/cJ.

Example 12 A certain powder of 184 g of zinc oxide, 19 g of magnesium hydroxide, and 4 g of calcium fluoride was mixed in a Pall mill for 3 hours, and then calcined at 1300° C. for 2 hours. The powder obtained by crushing the incendiary material with a vibrating ball mill was passed through a 400 mesh nylon sieve, and the powder that passed through the sieve was 15
0 g was dissolved in 1 liter of methanol, and the filler that did not settle within 5 minutes was collected (referred to as filler C). Filler C
is particle size 0. 2-4. 9 p m, average particle size 1
．． 9,czm, polyvalent metal ion elution amount 2 1 mgeq
/ It was g.

A mixture of a polyfunctional vinyl monomer having the following structure (manufactured by Shin Nakamura Chemical Co., Ltd.) and M-5500 (weight ratio 10/90
) and 8 g of 0.5% by weight each of camphorquinone and p-dimethylaminobenzoisoquacid ethyl ester dissolved therein, and 24 g of filler C were mixed under light shielding, followed by vacuum defoaming to prepare a curable composition.

The adhesive strength of the above curable composition with tooth structure is 55 kg/c
tA, 53 kg/ci under wet condition, and tensile strength was 139 kg/cA.

Example 13 8% by weight of water, 0.0% of each of camphorquinone and p-dimethylaminobenzoic acid ethyl ester were added to M-5500. 9g of 5% by weight dissolved and filler B2
After mixing 1 g under light shielding, vacuum defoaming was performed to prepare a curable composition.

The adhesive strength of the above-mentioned hardening composite material with tooth substance is 62 kg/cj
, 61kg/cnf under wet condition, tensile strength is 1 8 1
It was kg/crl. 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 Baroti Ichini Co., Ltd.)
was ground with a vibrating ball. 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 1 liter of methanol.
Filler that did not settle within a certain period of time (referred to as filler D) was collected. Filler D has a particle size of 0. 2-2.9 μm, average particle size 1.3 μm, polyvalent metal ion elution amount 1 mgeq
/g and was of poor quality.

0.5% by weight of each of camphorquinone and p-dimethylanohenzoic acid ethyl ester dissolved in M-5500 (Tog) and 20g of Filler D were mixed together under light shielding, followed by vacuum defoaming to obtain a curable composition. I prepared something.

The adhesive strength of the above curable composition with tooth structure is 23 kg/cJ
, 17 kg/cm under infiltration, and the tensile strength was unmeasurable.

Comparative Example 4 Camphorquinone and p-dimethylaminobenzoisoquacid ethyl ester were added to M-5500 in 0.0% each. After mixing 20 g of a 5% by weight solution and 4 g of filler A under light shielding, vacuum defoaming was performed to prepare a curable composite.

The adhesive strength of the above hardenable M1 precept with the tooth structure is 14 kg/
cd, 13 kg/cal under infiltration, tensile strength 58 kg
It was /d.

table 2 hand Continued Supplementary Positive book

Claims (1)

[Claims] (1) (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 polyvalent metal ions, and (C) a polymerization initiator. A curable composition.