JPS6069008A - Dental composition - Google Patents

Abstract

PURPOSE:A dental composition having improved performances of cured material, obtained by using both an organic combined filler prepared by polymerizing a specific sulfonic acid monomer with another polymerizable vinyl monomer in a polymerization system having dispersing an inorganic compound and vinyl compound. CONSTITUTION:A dental composition consisting of (A) an organic combined filler obtained by polymerizing a monomer shown by the formula I (R1 is H, 1-20C alkyl, phenyl, its derivative, halogen; X is CONH, group shown by the formula II, or COO(CH2)m, or (CH2)N; R2 and R3 are H, or 1-10C alkyl; R4 is 1-15C alkylene; m is 1-20 integer; n is 0-20 integer; Y is H, NH4, or alkali metal) with at least one other radically polymerizable vinyl monomer in a polymerization system having dispersed an inorganic compound, and (B) a vinyl compound is used to improve extremely performances such as hardness, mechanical strength, appearance, etc. of dental molded cured material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a dental composition containing an organic composite filler.

For dental materials whose main component is organic resin,
Various physical properties such as hardness, compressive strength, abrasion resistance, and water absorption are important, and in order to improve these properties, composite resins have been developed in which inorganic fins are blended with resin. ing. However, in this case, since the properties of the inorganic filler and the organic resin are significantly different from each other, interfacial compatibility such as compatibility and adhesion is poor, and a sufficient improvement effect cannot often be exhibited. In order to improve this point, for example, dental materials have been proposed in which a filler treated with a silane coupling agent is added to the glass surface, but a sufficient improvement has not yet been achieved.

The present invention solves the above-mentioned problems and has the following general formula: derivative or halogen atom, X is -CONH, -CONH-C-R4-1-CO
O(CH, Karasu, 3 and tl (CR2) n is 69, R1, 1% Id each H or an alkyl group having 1 to 15 carbon atoms, R4fi an alkylene group having 1 to 15 carbon atoms, m is an integer of 1 to 20 , n
is an integer from 0 to 20, Y represents H, NH4 or an alkali metal atom) and at least one radically polymerizable vinyl monomer and an inorganic compound are dispersed therein. The object of the present invention is to provide a dental composition comprising an organic composite filler obtained by polymerization in a polymerization system and a vinyl compound.

The composition of the present invention is characterized by an inorganic compound obtained by polymerizing a sulfonic acid monomer or a sulfonate monomer represented by the general formula (1) and a vinyl monomer in the presence of an inorganic compound, and an organic polymer. This method is characterized by the fact that the hardness, mechanical strength, appearance, and other properties of the dental molded cured product obtained by using the organic composite filler, which is strongly integrated with the vinyl compound, can be significantly improved.

The organic composite filler constituting the composition of the present invention is obtained by polymerizing a sulfonic acid monomer or a sulfonate monomer and one or more other polymerizable vinyl monomers in a polymerization system in which an inorganic compound is dispersed. It can be obtained by
There is no particular limitation on the manufacturing normal. preferable! An example of the IF method is to suspend and disperse a vinyl monomer and an inorganic compound in an aqueous medium under temperature conditions that do not cause a thermal polymerization reaction, and then add a sulfonic acid monomer or a sulfonate monomer. , by stirring, water-based
It is possible to use a method in which a subpolymerization reaction occurs and polymerization is carried out for a predetermined period of time.

The specific sulfonic acid monomer or sulfonate monomer represented by the general formula CI) used to form the organic composite filler of this @mei has a sulfonic acid group as an active side that brings about polymerization activity, and The presence of a double bond as an active side is essential for strong conjugation between the produced polymer and the inorganic compound, and any compound having a structural formula containing these functional groups can be applied. 2-acrylamido-2-methylpropanesulfonic acid (hereinafter abbreviated as F, AMps), sodium 2-methacrylicunesulfonate (hereinafter referred to as SgM-Na
), sodium 3-methacrylpropanesulfonate (hereinafter abbreviated as SPS), sodium 2-propenesulfonate (hereinafter abbreviated as NaAS), 2-methyl-2
- Examples include sodium propenesulfonate (hereinafter abbreviated as NaMS), but especially AMP containing an amide bond.
S, SEM-Na, SPS, etc., which are ester bond-depriving agents, are preferred because they exhibit remarkable secondary aggregation performance and have extremely high polymerization activity.

In addition, inorganic compounds used in the production of the organic composite filler of the present invention include Periodic Table Groups ■, ■, ■, IV, V groups, transition metals, and their oxides, hydroxides, chlorides, and sulfates. , sulfites, carbonates, phosphates, silicates, mixtures thereof, complex salts, etc. Among them, barium sulfate, silicon dioxide, aluminum oxide, titanium oxide,
Talc, quartz powder, glass powder, glass peas, glass fibers, barium salts, glass fillers containing lead salts, silica gel, carbon fibers, zirconium oxide, tin oxide can be used to activate vinyl monomers and form polymers. The strong unifying effect of is particularly remarkable and preferred. One of the major features of the present invention is that it can be applied to inorganic compounds for which ordinary coupling treatment is not effective, and the shape and size of the inorganic compound can be selected as appropriate.

Furthermore, as the vinyl monomer used in the production of the organic composite filler of the present invention, any ordinary vinyl monomer that can be radically polymerized can be used, but among them, methacrylic is uniquely polymerizable compared to methyl. It is particularly preferable because it has a high compatibility with the produced polymer and the inorganic compound. When using a mixture of two or more types of monomers, using methyl methacrylate as one component is a preferred general method, especially from the viewpoint of polymerization activity.

The degree of purity of the sulfonic acid monomer or sulfonate monomer when obtaining the organic composite filler is about 0.05 to 100% by weight, preferably 0.05 to 100% by weight, based on the total weight of the inorganic compound and vinyl monomer. 1-50% by weight, preferably 0.5-50% for bamboo
It is used in an amount of 30 times. In most cases, it is preferable to increase the amount of sulfonic acid or sulfonate monomer as the vinyl bell content increases. The weight ratio of vinyl monomers or mixtures thereof to inorganic compounds used can vary within a wide range and may range from about soo
: i to 1:5, preferably about 5021 to about 1:1
It is. The amount of water is about 1% to several hundred times, preferably about 10% to 1%, based on the total weight of the inorganic compound and vinyl monomer.
It is 0 times. The reaction is preferably carried out at a temperature of about 10-100°C, preferably 20-80°C, under an atmosphere of an inert gas, such as nitrogen. Here, it is important to select the specific reaction source rt appropriately depending on the vinyl monomer used, or to carry out the reaction at a temperature at which thermal polymerization is suppressed to a negligible level, or at a temperature at which extreme thermal polymerization may occur. When carried out at high temperatures, the integrity and uniformity of the resulting composite filler is inhibited. Reaction time is 30 minutes to about 15 hours. The resulting +3 composite filler can be dried at a temperature ranging from about 10 to 300°C, preferably from about 50 to 200°C.

Note that the interaction between the surface of the inorganic compound and the polymer applied by the method of the present invention goes beyond adhesion in a physical sense due to simple adsorption or van der Waals forces, and this fact This is clear from the fact that a large amount of unextracted polymer is observed even after extraction with a good solvent for the vinyl polymer. It may be a vinyl compound or a polyfunctional vinyl compound.

Examples of monofunctional vinylated materials include stenone, acrylonitrile, vinyl acetate, methyl acrylate and methacrylate, ethyl acrylate and methacrylate, butyl acrylate and methacrylate, hydroxyethyl acrylate and methacrylate, methoxyethyl acrylate and methacrylate, glycidyl acrylate and methacrylate, Examples include methacryloxyethyl trimellitic acid and its acid anhydride. Examples of polyfunctional vinyl compounds include ethylene glycol diacrylate and methacrylate, diethylene glycol diacrylate, and and methacrylate, triethylene glycol diacrylate and methacrylate, polyethylene glycol diacrylate and methacrylate-Fs, 1+4-butanediol diacrylate and methacrylate, 1.
3-butanediol diacrylate and methacrylate, 1,6-hexanediol diacrylate and methacrylate, glycerin diacrylate and methacrylate and the following general formula () (wherein R5 is a hydrogen atom or a methyl group, p is 1 to 20
(an integer of can be mentioned. These acrylates and methacrylates may be used alone or in combination of two or more. Further, these vinyl compounds are preferably blended in an amount of o, o o i to 100 times (by weight) relative to the above-mentioned composite filler. If the amount of the vinyl compound used is outside the above range, it will be difficult to successfully form a dental molding.

The dental composition of the present invention is a mixture of an organic composite filler obtained by using the sulfonic acid monomer or sulfonate monomer as a polymerization initiator and a vinyl compound that is a raw material for manufacturing the matrix resin. When used as a dental material to obtain a desired cured molded product, it is preferable to use a polymerization initiator for polymerizing and curing the vinyl compound, although it depends on the type of vinyl compound used.

As the polymerization initiator, any known compound can be used, but in the case of heat curing, substances that can decompose at high temperatures and initiate polymerization, N, jtf benzoyl peroxide, cumene hydroperoxide, t -butyl hydroperoxide, dicumyl peroxide, acetyl peroxide, lauroyl peroxide, azobisisobutyronitrile, etc. Further, in the case of polymerization and curing at room temperature, for example, a combination of peroxide and amines, peroxide and sulfinic acids, or peroxide and cobalt compounds can be used. When using a combination of polymerization initiators, the composition of the present invention can be divided into two parts, one containing peroxide and the other containing amines, sulfinic acids, or cobalt compounds. . When using a combination of polymerization initiators, divide the composition of the present invention into two parts, mix the peroxide in one part, and mix amines, sulfinic acids, etc. in the other part.
Alternatively, it can be used in combination with cobalt compounds.

The compositions of the present invention can also be cured by ultraviolet irradiation using photosensitizers such as benzoi dimethyl ether, benzoi diethyl ether, penzoisiglobyl ether, and the like. The amount of polymerization initiator that can be used to cure the composition of the present invention is 0.
．． 05-'10% by weight.

The composition of the present invention may also contain colorants, polymerization inhibitors, ultraviolet absorbers, oxidation stabilizers, and the like, if necessary.

The composition for dental materials according to the present invention contains an organic composite filler in which an inorganic compound and an organic polymer are strongly integrated, so that the interfacial affinity between the inorganic filler and the organic resin is improved. Due to this remarkable improvement, the cured product obtained by curing this material has high hardness, mechanical properties, and an excellent appearance that cannot be obtained with conventional dental materials.

Next, the present invention will be explained in more detail with reference to Examples. It should be noted that the parts in the examples indicate important parts.

Example 1, Comparative Examples 1 to 2 In a 500 m four-bottle flask equipped with a cooling tube, a nitrogen inlet tube, a stirring rod, and a thermocouple for internal temperature detection, silicon dioxide powder (manufactured by Masashi Davison Chemical Co., Ltd., trade name) was added as an inorganic compound. Thyroid 266) 5B, 7t was turbidly dispersed in deionized water 270- and nitrogen substitution was performed for 30 minutes. Next, methyl methacrylate 3 was used as a vinyl monomer.
002 was added with vigorous stirring under nitrogen flow.

Next, the temperature of the above reaction solution was raised to 50°C in a hot water bath, and after confirming the uniform dispersion state of the added monomer, a solution of SEM-Na6.5f as a sulfonate monomer dissolved in 10 m of deionized water was added. was gradually added, and the polymerization reaction was carried out at the same temperature for 8 hours.

After the reaction was completed, the product was vacuumed, passed through the mouth, thoroughly washed with deionized water, and then dried with hot air at 100° C. to remove moisture to obtain 67.7 t of organic composite filler. Such a composite filler has a polymer content of 4% as measured by a calcination method.
1%, and when a 50-hour Soxhlet extraction test was conducted using hot benzene as an extraction bath medium, the polymer content after extraction treatment was as high as 62%. 44 It is clear that most of the polymers composited by this method are extremely strongly integrated.
” Ivy. The thus obtained composite filler, polymethacrylic aqueous methyl powder (manufactured by Mitsubishi Rayon ■, trade name Acrycon A)
C) and methyl methacrylate monomer (weight ratio =
2; IL) Blend lyethylene glycol dimethacrylate and benzoyl peroxide at the compounding ratio shown in Table 1, mix the mixture mechanically, fill it into a plaster mold, and heat it at 60°C for 30 minutes.
It was then dry cured at 100° C. for 1 hour. After curing, it was stored in water at 67° C. for 24 hours, and then used as a sample for measuring physical properties. The compressive strength and indirect tensile strength of the cured product are
Shown in the table. For comparison, instead of the composite filler according to the present invention, silicon dioxide powder was used as a silane coupling agent (3
-Methacryloxypropyltrimethoxysilane) treated filler was blended and untreated silicon dioxide powder was blended, and the same evaluation was conducted and studied.

As is clear from the first coating, the composite filler according to the present invention has superior mechanical properties compared to the dental material containing conventionally used silane-treated fillers and untreated fillers. It can be seen that a cured product having the following properties is obtained. Also,
The composite filler according to the present invention has extremely good wettability with the liquid resin, so it is easy to composite, and the appearance of the prepared cured test piece was significantly cleaner than that of the comparative example.

Example 2, Comparative Examples 3 to 4 In Example 1, bisphenol A was used instead of the polymethacrylate-branched menal-methyl methacrylate monomer mixture.
A powder-liquid heavy alloy was prepared using the same strain as in Example 1 except that diglycidyl methacrylate was used, and the compressive strength and indirect tensile strength of the resulting composition were measured. The results are shown in Table 2.

As is clear from Table 2, the untreated filler shown in Comparative Example 4 cannot be used to produce hardened specimens, and the strength and physical properties of the conventionally used silane-treated filler shown in Comparative Example 3 It can be seen that the composite filler obtained by the method of the present invention has a remarkable strength improvement effect and provides a cured product for dental materials having excellent mechanical properties.

Example 3, Comparative Example 5 Aluminum oxide powder (reagent special grade) as an inorganic compound
58.7 f was subjected to an aqueous heterogeneous polymerization reaction in the same manner as in Example 1 to obtain 65.5 t of organic composite filler. The composite filler had a polymer content of 28% and a polymer content of 23% after the extraction process. The composite filler thus obtained was blended in the same manner as in Example 2, and the mechanical strength of the cured product was measured. The results are shown in Table 3.

As is clear from Table 3, the strength properties of the untreated filler shown in Comparative Example 5 are at an extremely low level, whereas the composite filler obtained by the method of the present invention has a remarkable strength-improving effect. This provides a cured product for dental materials having excellent mechanical properties. In addition, the composite filler according to the present invention has extremely good wettability with the liquid resin, so it is easy to form a composite, and the appearance of the prepared cured test piece was significantly cleaner than that of the comparative example.

Example 4, Comparative Example 6 Barium sulfate powder (reagent special grade) as an inorganic compound 3
B, 7f was subjected to an aqueous heterogeneous polymerization reaction in the same manner as in Example 1 to form an organic composite filler 65. Obtained O2. The composite filler had a polymer content of 29% and a polymer content of 25% after extraction.

The composite filler thus obtained was blended in the same blending ratio as in Example 6, and the mechanical strength of the cured product was determined. The results are shown in Table 4.

From Table 4, it is clear that 1. As shown, the untreated filler shown in Comparative Example B cannot produce hardened test pieces, whereas
The cured test specimens of the composite filler according to the present invention had a very clean appearance and gave a dental cured product with excellent mechanical properties.

Claims (1)

[Scope of Claims] 1. The following general formula % formula % () (wherein R3 is H1 an alkyl group having 1 to 20 carbon atoms, a phenyl group and its sieve conductor, or) \mouth 2 Mangen atom, or - 〇〇NH-5-CONH-C-R4-
13 -CO0 (CHt%, or +cH, -9H)
, R2, R, are each H or an alkyl group having 1 to 15 carbon atoms; R is an alkylene group having 1 to 15 carbon atoms;
20, n is an integer from 0 to 20, Y represents H, NH, or an alkali metal atom) and at least one other radically polymerizable vinyl An organic composite filler obtained by polymerizing a monomer in a polymerization system in which an inorganic compound is dispersed;
A dental composition consisting of a vinyl compound. 2. A patent characterized in that the sulfonic acid monomer or sulfonate monomer is 2-acrylamido-2-menalbrobanesulfonic acid, sodium 2-methacrylethanesulfonate or sodium 3-methacrylpropanesulfonate A toothpaste composition according to claim 1. 3. The dental composition according to claim 1, wherein the vinyl monomer is mainly composed of methyl methacrylate. 4. Glass filler, silica gel, carbon fiber containing inorganic compounds such as barium sulfate, silicon dioxide, aluminum oxide, titanium oxide, cruzi powder, glass powder, glass beads, glass fiber, barium salt, lead weir. , zirconium oxide, and tin oxide.
The dental composition according to claim 1, which is a seed. 5. Claim 1, wherein the vinyl compound is methyl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,6-butanediol dimethacrylate, or bispheno-, vA diglycidyl methacrylate. Dental composition.