JP2010229078A - Curable dental composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable dental composition which has excellent storage stability even when it is in the form of a water-containing constitution. <P>SOLUTION: What is provided is a dental composition constituted from a pasty first component comprising (a) 20-80 wt.% water, (b) 50-80 wt.% acid-reactive filler, and (c) 1-30 wt.% water-soluble thickener and a second component comprising (d) 15-100 wt.% polymer of an α, β-unsaturated monocarboxylic acid or of an α, β-unsaturated dicarboxylic acid. Also, the dental composition may be one wherein the first component further contains 1-50 wt.% acid group-free (meth)acrylate and the first component and/or the second component contain 0.01-5 wt.% polymerization initiator. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a curable dental composition used for a dental prosthesis, a cavity or a root canal filling material, and the like.

  Some dental compositions for reacting and curing an acid-reactive filler and an α-β unsaturated carboxylic acid polymer contain water (for example, see Patent Documents 1 to 3). Since such materials may be altered by evaporation of water during storage, to avoid this, the joint between the container body and lid can be improved to improve sealing or vent the container itself. It was necessary to devise such as selecting a low-quality material. However, there is a problem that such a method is costly and increases the price of the container. Moreover, when the sealing property of the container is increased, in the case of a curable dental composition using a (meth) acrylate compound in combination, the (meth) acrylate compound gels during the storage period when the supply of oxygen is interrupted. There was a problem that. Accordingly, it is very difficult to ensure storage stability especially in a composition in which water and a (meth) acrylate compound coexist.

JP 11-228327 A JP 2007-091607 A JP 2007-091689 A

  Then, this invention makes it a subject to provide the hardenable dental composition excellent in storage stability in the hardenable dental composition containing water.

  As a result of intensive studies to solve the above problems, the present inventors have a) water 20-80% by weight, b) acid-reactive filler 50-80% by weight, c) water-soluble thickener 1-30%. And a second component containing 15 to 100% by weight of a polymer of α-β unsaturated monocarboxylic acid or α-β unsaturated dicarboxylic acid. The present invention has been completed by finding that the above-mentioned problems can be solved by using a composition for use. Further, the curable dental composition according to the present invention contains 1 to 50% by weight of (meth) acrylate having no acid group in the first component, and a polymerization initiator in the first component and / or the second component. When 0.01 to 5% by weight is contained, the strength after curing can be improved, and when the second component is further pasty containing 10 to 85% by weight of water and / or (meth) acrylate, the first component And the second component can be mixed easily.

  The curable dental composition according to the present invention is an excellent curable dental composition having a high storage stability without using an expensive high-sealing container even though the composition contains water. Even in the presence of a meth (acrylate) compound, excellent storage stability can be obtained.

  Since the curable dental composition according to the present invention is configured to react and cure the acid-reactive filler and the α-β unsaturated carboxylic acid polymer, the first component contains 20 to 80% by weight of water. If it is less than 20% by weight, the curing reaction is insufficient, and if it exceeds 80% by weight, the cured product becomes brittle.

As the acid-reactive filler used in the present invention, the acid-reactive filler conventionally used in dental cement can be used. For example, fluoroaluminosilicate glass powder used for dental glass ionomer cement and metal for dental cement There are oxide powders. The fluoroaluminosilicate glass powder is preferably an aluminosilicate glass powder containing Al ³⁺ , Si ⁴⁺ , F ⁻ , O ²⁻ as main components, and further containing Sr ²⁺ and / or Ca ²⁺ . It is desirable that Al ³⁺ : 10 to 21% by weight, Si ⁴⁺ : 9 to 21% by weight, F ⁻ : 1 to 20% by weight, and the total of Sr ²⁺ and Ca ²⁺ : 10 to 34% by weight based on the total weight. . The surface of the oxide powder that can react with the polyacid may be modified with alkoxysilane.

  The acid-reactive filler is contained in the first component in an amount of 50 to 80% by weight. If it is less than 50% by weight, sufficient strength and X-ray contrast properties cannot be imparted to the curable dental composition, and if it exceeds 80% by weight, the water content is reduced and the storage stability is lowered.

  A water-soluble thickener is blended for moisturizing. Examples of the water-soluble thickener include sodium carboxymethylcellulose, starch, sodium starch glycolate, sodium starch phosphate ester, methylcellulose, sodium polyacrylate, alginic acid, sodium alginate, propylene glycol ester alginate, casein, sodium caseinate, polyethylene Examples include glycol, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, gluten, locust bean gum, gelatin and the like. Of these, sodium carboxymethylcellulose is preferred. Two or more of these water-soluble thickening materials may be mixed and used.

  The water-soluble thickening material is blended in the first component in an amount of 1 to 30% by weight. If it is less than 1% by weight, the moisturizing effect by the water-soluble thickener cannot be obtained, and if it exceeds 30% by weight, the physical properties of the curable dental composition are lowered.

  The curable dental composition according to the present invention comprises a polymer of α-β unsaturated monocarboxylic acid or α-β unsaturated dicarboxylic acid as a component that reacts with the acid-reactive filler and cures as the second component. Contains ~ 100% by weight. If it is less than 5% by weight, the adhesiveness of the hardenable dental composition is lowered. Polymers of α-β unsaturated monocarboxylic acid or α-β unsaturated dicarboxylic acid are, for example, acrylic acid, methacrylic acid, 2-chloroacrylic acid, aconitic acid, mesaconic acid, maleic acid, itaconic acid, fumaric acid, glutacone. A homopolymer or copolymer of acid, citraconic acid or the like. These copolymers may be a copolymer of α-β unsaturated carboxylic acids, or a copolymer with a component copolymerizable with α-β unsaturated carboxylic acid. In the case of a copolymer, the proportion of α-β unsaturated carboxylic acid is preferably 50% or more. Examples of the copolymerizable component include acrylamide, acrylonitrile, methacrylic acid esters, acrylates, vinyl chloride, allyl chloride, and vinyl acetate. Among these α-β unsaturated carboxylic acid polymers, particularly preferred are acrylic acid or maleic acid homopolymers or copolymers having a weight average molecular weight of 5,000 to 40,000. . When a polymer having a weight average molecular weight of less than 5,000 is used, the strength of the cured product is lowered. Moreover, the adhesive force to a tooth substance also falls. When a polymer having a weight average molecular weight exceeding 40,000 is used, the consistency at the time of kneading of the cement composition is too firm, and kneading becomes difficult. Therefore, the average molecular weight of the α-β unsaturated carboxylic acid polymer used in the present invention is preferably in the range of 5,000 to 40,000.

  The curable dental composition according to the present invention further comprises 1 to 50% by weight of a (meth) acrylate having no acid group in the first component, and a polymerization initiator in the first component and / or the second component. It may be a curable dental composition containing 0.01 to 5% by weight. In this case, it is possible to increase the strength after curing of the curable dental composition, and it is possible to freely set the timing of curing of the curable dental composition by further using a polymerization reaction. . When the amount of (meth) acrylate having no acid group is less than 1% by weight, there is no effect of blending (meth) acrylate, and when it exceeds 50% by weight, an acid-reactive filler and an α-β unsaturated carboxylic acid polymer are used. The adhesiveness of the hardened body resulting from the reaction with the tooth will be reduced.

  The (meth) acrylate compound having no acid group in the present invention means various monomers, oligomers and prepolymers of acrylate or methacrylate having no acid group. Specific examples of the (meth) acrylate compound used in the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and hydroxypropyl. (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-methoxyethyl (Meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxy- , 3-Di (meth) acryloxypropane, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane Tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polybutylene glycol di (meth) Acrylate, include bisphenol A diglycidyl (meth) acrylate, these monomers or oligomers or prepolymers can be suitably used. Moreover, as a (meth) acrylate having a urethane bond, di-2- (meth) acryloxyethyl-2,2,4-trimethylhexamethylene dicarbamate, 1,3,5-tris [1,3-bis {( (Meth) acryloyloxy} -2-propoxycarbonylaminohexane] -1,3,5- (1H, 3H, 5H) triazine-2,4,6-trione, 2,2-bis-4- (3- (meta ) Acrylicoxy-2-hydroxypropyl) -phenylpropane, etc., and consists of 2,2'-di (4-hydroxycyclohexyl) propane, 2-oxypanone, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate. Urethane oligomer (meth) acrylate, 1,3-butanediol and hexamethylene diisocyanate When 2-hydroxyethyl (meth) urethane oligomer consisting of acrylates (meth) acrylate. These can be used individually or in mixture of 2 or more types.

  When a (meth) acrylate compound is used in the curable dental composition according to the present invention, a polymerization initiator for initiating polymerization of the (meth) acrylate compound in at least one of the first component and the second component Need to be used together. As the polymerization initiator, a polymerization initiator conventionally used for the polymerization of (meth) acrylate compounds can be used without limitation. The blending amount of the polymerization initiator is preferably 0.01 to 5% by weight in the first component and / or the second component. If it is less than 0.01% by weight, the polymerization reaction of the (meth) acrylate compound does not occur sufficiently, and if it exceeds 5% by weight, the polymerization is too early and the operation time is shortened.

  The curable dental composition according to the present invention may contain a filler that does not react with a polymer of α-β unsaturated monocarboxylic acid or α-β unsaturated dicarboxylic acid in the presence of water. This filler component improves the strength of the cured body. Fillers include silicic anhydride, barium glass, alumina glass, potassium glass, fluoroaluminosilicate glass, synthetic zeolite, calcium phosphate, feldspar, fumed silica, aluminum silicate, calcium silicate, magnesium carbonate, hydrous silicic acid , Powders of hydrous calcium silicate, hydrous aluminum silicate and quartz. These fillers can be combined with (meth) acrylate compounds, such as γ-methacryloxypropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, vinyltri (methoxyethoxy) silane, etc. It may be surface-treated with a silane coupling agent. In addition, an organic-inorganic composite filler prepared by previously mixing the above filler with a monomer or oligomer and curing it, and then pulverizing it can also be used. These fillers can be used alone or in admixture of two or more. Among these, anhydrous silicic acid, hydrous silicic acid, hydrous calcium silicate, and hydrous aluminum silicate can prevent gelation of the liquid component before polymerization even when stored for a long period of time.

  In addition, a fluorescent agent, an antibacterial agent, a pigment and the like that are usually used can be appropriately blended in the curable dental composition according to the present invention as necessary.

  The first component and the second component were prepared according to the formulations (% by weight) shown in Tables 2 to 4, and the storage stability test was performed.

The meanings of the symbols in the table are as follows.
TEGDMA: Triethylene glycol dimethacrylate UDMA: Di-2-methacryloxyethyl-2,2,4-trimethylhexamethylene dicarbamate HEMA: 2-hydroxymethacrylate

CMCNa: Sodium carboxymethyl cellulose PANa: Sodium polyacrylate (Molecular weight: 5,000 to 20,000)
PG: Polyethylene glycol (molecular weight: 5,000 to 100,000)

Aerosil: Fumed silica (trade name R812, manufactured by Nippon Aerosil Co., Ltd.)

BHT: Butylhydroxytoluene p-DE: p-Dimethylaminobenzoate ethyl
CQ: Camphorquinone

  Table 1 shows the composition of the fluoroaluminosilicate glass powder.

  Regarding the fluoroaluminosilicate glass powders I and III, the raw materials were sufficiently mixed and held in a high-temperature electric furnace at 1200 ° C. for 5 hours to melt the glass. After melting, the mixture was cooled, pulverized for 10 hours using a ball mill, and the powder after passing through a 200 mesh (ASTM) sieve was used as a fluoroaluminosilicate glass powder. The fluoroaluminosilicate glass powder II was prepared in the same manner as the fluoroaluminosilicate glass powders I and III except that it was melted at 1100 ° C.

"Storage test (stability)"
The first component of each example and comparative example was filled into a container of an extruding tool (trade name: GC Fuji Routing S cartridge: manufactured by GC Corporation), and the weight of each container was measured. The container was stored at a constant temperature of 50 ° C., and the weight was measured again after 12 weeks. The case where the weight decreased by 3% by weight or more in 12 weeks was evaluated as unacceptable (x), and the case where the weight loss was less than 3% by weight was evaluated as acceptable (O).

"Preservation test (confirmation of extrudability)"
The first component of each example and comparative example was filled into a container of an extruding tool (trade name GC Sea Routing S Cartridge: manufactured by GC Corporation) and stored at a constant temperature of 50 ° C. for 12 weeks. After storage, the container was attached to a dedicated extrusion tool (trade name GC CD Dispenser II: manufactured by GC Corporation) to extrude the first component. The case where it was able to extrude without a problem was evaluated as possible ((circle)), and the case where it was not able to be extruded was evaluated as impossible (x), and the result was shown to Tables 2-4.

Claims (3)

a) a paste-like first component comprising 20) 80% by weight of water, b) 50-80% by weight of an acid-reactive filler, c) 1-30% by weight of a water-soluble thickener, and d) α-β unsaturation. A dental composition comprising a second component containing 15 to 100% by weight of a polymer of monocarboxylic acid or α-β unsaturated dicarboxylic acid. The first component further comprises 1 to 50% by weight of (meth) acrylate having no acid group, and the first component and / or the second component further comprises 0.01 to 5% by weight of a polymerization initiator. The dental composition as described. The dental composition according to claim 1 or 2, wherein the second component is a paste containing 10 to 85% by weight of water and / or (meth) acrylate.