JPS6315242B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention does not impair the excellent operability and physical properties of the methyl methacrylic flooring material that is generally widely used in dentistry, and furthermore, it is chemically compatible with porcelain teeth and dental cobalt chromium alloys and nickel chromium alloys. The present invention relates to a resin material for dental denture bases that also has adhesive properties, and is a new material that does not require the conventional mechanical maintenance devices for porcelain and metal. As is well known, metal base dentures are more durable and have less risk of breakage than dentures made only of methyl methacrylate resin, and because the base can be made thinner and smaller, there is less of a feeling of foreign body when worn, and there is no water absorption, resulting in high precision. Compatibility and maintainability are obtained. In addition, it has many other advantages, such as being less irritating to the floor surface, having good tissue affinity, being hygienic, having good thermal conductivity and causing less disturbance to temperature sensation and taste, and less bending of the denture when chewing. Its prevalence is increasing over the years. Examples of metal materials used for the metal floor include gold alloy, gold-silver-palladium alloy, platinum-added gold, cobalt-chromium alloy, nickel-chromium alloy, and 18-8 stainless steel alloy. Among these alloys, cobalt-chromium and nickel-chromium alloys have a specific gravity of about 1/2 compared to gold alloys, making them lighter, and their Young's modulus is about twice as high, making them extremely strong. These alloys are being used more and more every year because they have excellent color fastness and are low in price. Furthermore, artificial teeth used with metal floors such as these include porcelain teeth and resin teeth, but the hardness,
Porcelain teeth are superior in terms of wear resistance and non-toxicity, and are commonly used. Some metal base dentures are made entirely of metal without using resin, but most metal base dentures currently have resin for the alveolar part that holds the artificial teeth and the lip-buccal part that touches the outside. The structure, tongue and palate side, and connecting parts are made of metal, combining the strengths of both. The resin used for the metal base is methylmethacrylic resin, which is widely used as a resin material for denture bases. However, this methyl methacrylic resin has no chemical adhesive strength with dental metals or porcelain teeth. Therefore, various considerations have been made in the maintenance design taking into account the mechanical maintenance of resin, metal, and porcelain teeth, but the following problems have been pointed out at present. In other words, external forces such as masticatory pressure applied to the denture during use in the oral cavity create a gap at the so-called finishing line where the metal and resin join, causing the metal part and the resin part to separate, resulting in discoloration of the resin. , causing uncleanliness and denture odor. The need for mechanical maintenance makes denture design and casting operations complicated and difficult. When polishing dentures, the thin parts where they connect to the metal often break. When retention beads are used in the retention section, color tone expression is restricted. Since the bed mucosal surface must be covered with metal, it has the drawback that if the fit of the bed mucosal surface becomes poor, so-called relining, which is backed by resin, cannot be performed. In addition, when making dentures using porcelain teeth and conventional floor resin, gold pins are planted on the base of the denture and a holding device is used, since the chemical adhesion between the porcelain teeth and conventional floor resin is completely zero. Or, it relies on mechanical retention by providing a retention hole, which tends to cause the porcelain tooth to break due to stress concentration on the retention part.
It has been reported that it sometimes falls off during use in the oral cavity. Furthermore, dirt accumulates in the gap between the contact interface between the resin base and the porcelain tooth, causing bacteria to develop, causing the denture to discolor and develop a bad odor during use. In order to overcome the above-mentioned drawbacks, attempts have been made to chemically bond porcelain teeth or metals to floor resin materials. That is, the metal surface is etched with an inorganic acid,
There have been reports of a method of applying an adhesive thereon and laminating a methacrylic floor resin thereon, or a method of adhering using 4-methacryloxyethyl trimellitic acid. However, these methods significantly reduce technical efficiency and have many problems in practical use since there is a large difference in adhesion strength to both cobalt chromium and nickel chromium alloys. Furthermore, with these methods, the adhesive strength to porcelain teeth is zero. Furthermore, a method has been reported in which a silane compound is added to methyl methacrylate as a method for bonding to porcelain teeth. It is disclosed in Japanese Patent Application No. 58237/1973. This method can be expected to provide good adhesion to porcelain teeth, but the adhesion to metal is low and there is wide variation in the adhesion. As mentioned above, compositions whose purpose is to bond only cobalt chromium alloys and nickel chromium alloys, or only porcelain teeth, have been published, but they cannot be used to bond cobalt chromium alloys, nickel chromium alloys, or porcelain teeth. At the same time, a floor resin composition that also has strong chemical adhesive strength has not yet been published. The present invention enables the denture base resin to strongly chemically bond to cobalt chromium, nickel chromium alloys, and porcelain teeth by coexisting a special silane compound and unsaturated carboxylic acid in a methyl methacrylate monomer. We have found a way. Furthermore, the composition of the present invention does not impair the advantages of methacrylic flooring materials that are generally widely used in dentistry, such as aesthetics, operability, and adhesiveness between resin teeth and flooring materials. , physical and chemical properties such as fracture strength, impact resistance, and solvent resistance are also significantly improved. Also, the retention is 50ppm.
When containing hydroquinone, it did not harden even after two years or more. To explain the content of the present invention in detail, the composition of the present invention contains 0.5 to 20% by weight of methyl methacrylate monomer.
The liquid component is a mixture of a special silane compound and 0.5 to 10% by weight of unsaturated carboxylic acid, and methyl methacrylate polymer is mixed in a weight ratio of 1:3 to 3:1, which is the standard method in dentistry. The dentures are molded using this method. When making a denture containing a metal base and a porcelain tooth using a composition such as this, when the resin is placed under pressure and preheated using the conventional method, the unsaturated carboxylic acid first bonds the resin to the metal or porcelain tooth. The special silane compound molecules are oriented to the active surface by cleaning and etching the adhesive surface, and when the methyl methacrylate monomer is polymerized in the main polymerization, compounded components such as also polymerizes at the same time to form a strong bond. Furthermore, the action of these compounds is very effective because the adhesive surface is not exposed to the outside air at all. The special silane compound in the present invention has the general formula A compound represented by the following formula, where D: a hydrolyzable group n: an integer from 1 to 3 b: an integer from 0 to 2 n+b: an integer from 1 to 3 R': a monovalent hydrocarbon group A group selected from the group consisting of R: an alkylene group containing 1 to 4 carbon atoms c: an integer of 0 to 1 A:

[Formula]-CH= _CH2

【formula】

【formula】

It is a compound consisting of the following formula: (wherein, X is a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms). In the above general formula, D can be any group that can be hydrolyzed. There can be 1, 2 or 3 D groups in the compound, but the presence of 3 is preferred. By way of example, D is a group such as methoxy, ethoxy, propoxy, isopropoxy, etc. R' may be any monovalent hydrocarbon group, such as methyl, ethyl, propyl, butyl, etc., with methyl being preferred. b can be 1, 2 or 0. There may be 1, 2 or 3 ARc groups present, ie n may be 1, 2 or 3, but preferably n is 1. The R group is a divalent alkylene group bonded to a silicon atom and containing 1 to 4 carbon atoms. Examples include groups such as methylene, ethylene, trimethylene, propylene.
c is 0 or 1 and no R group may be present. A is bonded to the R group, except when c is 0 and is bonded directly to the silicon atom. A is

[Formula]-CH=CH ₂ ,

[expression] and

【formula】

[Formula] When c is 0, A is -CH=CH ₂ or

[Formula].

In the group X is a hydrocarbon group having 1 to 6 carbon atoms, in which case an ester group is present in the compound. For example,
Examples include methyl, ethyl, isopropyl, and butyl. In the above general formula, there is one D group in the compound,
The number can be 2 or 3, but the presence of 3 is preferred, and is represented by the following general formula (ARc)-Si-D ₃ where D: hydrolyzable group R: 1- Alkylene group containing 4 carbon atoms c: integer from 0 to 1 A: -C=CHz,

【formula】

[expression] or

This is a special silane compound having the following structure: (X in the formula: hydrogen atom or hydrocarbon group having 1 to 6 carbon atoms) Commercially available specific compounds according to the above definitions are γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. Ethoxysilane, vinyltriethoxysilane,
Examples include β-(3,4 epoxycyclohexyl)ethyltrimethoxysilane and vinyl tris(β-methoxyethoxy)silane. Among these, γ-methacryloxypropyltrimethoxysilane is most preferred. As the unsaturated carboxylic acid in the present invention, both unsaturated monocarboxylic acids and unsaturated polycarboxylic acids can be used. For example, acrylic acid, methacrylic acid, chromenic acid, linoleic acid, undecenoic acid, β
-2 Furyl acrylic acid, cinnamic acid, sorbic acid,
Fumaric acid, maleic acid, citraconic acid, etc. are used. Examples of the present invention and comparative examples were carried out under the following common conditions, and the results are collectively shown in the table below to facilitate comparison. Using a PMMA-based polymer [polymethyl methacrylate] (particle size 120-200 Tyler mesh) containing 0.1% BPO [benzoyl peroxide] as a powder component, the mixing ratio (weight) with the PMMA powder component was determined using the liquid formulation in the following example. A 1:2 dough was prepared and prepolymerized at 70℃ for 30 minutes according to the standard dental method, and then main polymerization was heated at 100℃ for 30 minutes.The results are summarized in the table below. Significant improvements in adhesion and physical properties were observed compared to samples made using commercially available resin monomers. For the adhesion test with metal, first, wax of 5 x 5 x 5 mm was piled up in the center of a 10 x 10 x 2 mm metal test piece that had been mirror-finished with chromium oxide abrasive, and then buried in plaster according to the standard dental practice and allowed to harden. Afterwards, the wax was poured and washed, and a resin sample was inserted into the negative mold and polymerized. In addition, an adhesion test with porcelain teeth was conducted according to the method specified in JIS T6511. If the concentration of the special silane compound is less than 0.5% by weight, the adhesion force to the porcelain tooth will be less than 5kg, which may cause the porcelain tooth to peel off during use, and if the concentration is more than 20% by weight, the adhesive force with the porcelain tooth will be less than 5kg in the anti-bending test. When the deflection of the load is 6 mm or more
It does not comply with the JIS T6501 standard and is not suitable for practical use. When the concentration of unsaturated carboxylic acid is 0.5% by weight or less, the adhesive strength with cobalt chromium alloy is 40kg/
cm ² or less, the effect of adding the unsaturated carboxylic acid will not be apparent, and if it is more than 10% by weight, the transverse bending strength will be less than 5 kg, which is unsuitable for practical use. Therefore, the concentration ranges of the special silane compound and unsaturated carboxylic acid are 0.5 to 20% by weight and 0.5 to 10% by weight, respectively.
And so. Various examples are specifically shown below, and the adhesive strength and transverse bending strength in each case are collectively displayed. However, it goes without saying that the present invention is not limited to the numerical values of these specific examples. Example 1 A composition solution was used in which 50 ppm of hydroquinone was added to a mixture of 90 parts of methyltaacrylate monomer, 6 parts of γ-methacryloxypropyltrimethoxysilane, and 4 parts of undecenoic acid. Example 2 In Example 1, methacrylic acid was used instead of undecenoic acid. Example 3 A composition solution was used in which 100 ppm of butyrate dehydroxyparatoluene was added to a mixed solution of 96 parts of methyl methacrylate monomer, 3 parts of γ-methacryloxypropyltrimethoxysilane, and 1 part of acrylic acid. Example 4 A composition solution was used in which 50 ppm of hydroquinone was added to a mixed solution of methyl methacrylate monomer 90 parts ethylene glycol dimethacrylate 1 part γ-methacryloxypropyltrimethoxysilane 6 parts citraconic acid 3 parts. Example 5 A composition solution was used in which 91 parts of methyl methacrylate, 5 parts of γ-methacryloxypropyltrimethoxysilane, and 3 parts of 4 parts of methacryloxyethylene trimellitic acid were mixed together, and 50 ppm of hydroquinone was added to the solution. Example 6 In the formulation of Example 3, γ-glycidoxypropyltrimethoxysilane was used as the silane compound. Example 7 In the formulation of Example 3, vinyltriethoxysilane was used as the silane compound. Example 8 In the formulation of Example 3, β-(3,4 epoxycyclohexyl)ethyltrimethoxysilane was used as the silane compound. Example 9 A case in which a composition solution prepared by adding 2% by weight of dimethyl para-toluidine to methyl methacrylate monomer according to the formulation of Example 3 was polymerized at room temperature without heating. Comparative Example 1 When acrylic acid was excluded from the formulation of Example 3. Comparative Example 2 In the formulation of Example 3, a silane compound (γ-
(excluding methacryloxypropyltrimethoxysilane). Comparative Example 3 Akron liquid from Jishi Dental Industry Co., Ltd. was used as the liquid.

【table】

Claims (1)

[Claims] 1 General formula (ARc)-Si-D ₃ where D: a hydrolyzable group, R: an alkylene group containing 1 to 4 carbon atoms, c: an integer of 0 to 1, A: A special silane compound having the structure -C=CHz, [Formula] [Formula] or [Formula] (X in the formula: hydrogen atom or hydrocarbon group having 1 to 6 carbon atoms) is added to a methyl methacrylate monomer. 1. A resin composition for a dental floor, characterized in that it contains 0.5 to 20% by weight of an unsaturated carboxylic acid and 0.5 to 10% by weight of an unsaturated carboxylic acid. 2. The dental floor resin composition according to claim 1, wherein the unsaturated carboxylic acid is a monounsaturated carboxylic acid. 3. The dental floor resin composition according to claim 1, wherein the unsaturated carboxylic acid is a polyunsaturated carboxylic acid. 4 0.1 to 5 to methyl methacrylate monomer
The resin composition for a dental bed according to any one of claims 1 to 3, wherein a crosslinking agent is added in an amount of % by weight. 5 0.1 to 2.0 to methyl methacrylate monomer
5. The resin composition for a dental floor according to any one of claims 1 to 4, wherein a weight percent of amines for curing at room temperature is added. 6 General formula (ARc)-Si-D _3where , D: hydrolyzable group, R: alkylene group containing 1 to 4 carbon atoms c: integer from 0 to 1 A: -C=CHz, [ Formula] [Formula] or [Formula] (X in the formula: hydrogen atom or hydrocarbon group having 1 to 6 carbon atoms) 0.5 to 20% by weight of a special silane compound having the structure in methyl methacrylate monomer A powdered methyl methacrylate polymer was added to a liquid dental resin composition containing 0.5 to 10% by weight of an unsaturated carboxylic acid in a ratio of 1:3 to 3:1.
A method of using a resin composition for a dental floor, characterized in that the resin composition is mixed at a mixing ratio of: