JPH10139614A - Dental coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a dental coating composition that does not cause discoloration, and excels in performance maintenance of prosthetic materials by combining a fluorine-containing elastomer, (meth)acrylic monomer, and a polymerization initiator, with or without an organic solvent to set its viscosity to a specific range. SOLUTION: This dental coating composition, which can prevent rebasing materials, mucous adjusting materials, artificial tooth bases from odorization, discoloration, bacterial proliferation, etc., comprises a combination of (a) a fluorine-containing elastomer, preferably vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, pentafluoropropylene, etc., in a quantity of 2-40wt.%, (b) a (meth)acrylic monomer in a quantity of 60-98wt.%, (c) a polymerization initiator in a quantity of 0.05-5wt.%, and furthermore, if desired, (d) an organic solvent in a quantity of up to 95wt.% of component (b) to adjust the viscosity of the composition to 1cP or more and 10,000cP or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a dental coating composition. More specifically, it is a composition used for coating of denture base, orthodontic base, denture rebase agent, temporary crown, mucosal conditioner, denture stabilizer and the like.

[0002]

2. Description of the Related Art At present, in dental treatment, a denture base made of a polymerizable resin composition for a floor (hereinafter sometimes referred to as resin) is worn on a patient who has lost teeth due to age or the like. . In general, the denture base wearer gradually increases the density of the oral cavity even if the denture base is made with high accuracy due to the thinning of the mucous membrane, which absorbs the ridge and is responsible for cushioning, and the alveolar bone collapses due to bone resorption. It has been pointed out that the compatibility with is reduced. When the compatibility between the denture base and the oral cavity is reduced, it is difficult to maintain the denture in the oral cavity or to avoid pain during occlusion. Remodeling has been performed to restore compatibility with the oral cavity. The material used for the rebase varies from a material having the same hardness as the denture base to a soft material having a cushioning property. In recent years, a soft material having properties close to the mucous membrane has been frequently used. Various materials such as a fluorine resin, an acrylic soft material, a silicon soft material, and a polyolefin soft material are used as the soft rebase material. Also, a mucosal conditioner mainly composed of polyethyl methacrylate is preferably used as a temporary soft material.

On the other hand, Japanese Patent Application Laid-Open No. 60-97911 discloses a non-adhesive coating agent for a denture base comprising (a) a powder of a non-adhesive substance and (b) a resin curable by ultraviolet rays. JP-A-61-161207 discloses a denture base coating material composition comprising (a) a fluoroolefin, (b) an alkyl vinyl ether, and (c) a hydroxyalkyl vinyl ether.
Further, JP-A-4-169509 discloses a method for producing a photocurable coating agent for dentures comprising (a) a photocurable resin, (b) a solvent, and (c) a dispersion of finely divided polytetrafluoroethylene. It has been disclosed.

[0004]

By the way, materials such as a soft rebase material and a mucosal conditioner are prolonged when used in the oral cavity for a long time.
There are problems such as odor, discoloration, and abnormal oral mucosa. In addition, there is a problem that some components of the mucous membrane adjusting material are eluted into the oral cavity and the performance is reduced. On the other hand, JP-A-60-97911, JP-A-61-161207
And JP-A-4-169509, the fluororesin is a particle, so that the surface cannot be covered and the odor and discoloration are not sufficiently prevented, or the transparency of the coating agent is low. There is a problem that the aesthetics are reduced due to a decrease in gloss and gloss, and the tongue feeling is reduced. Further, there is a problem that the coating agent is hard and impairs the cushioning properties of the mucous membrane adjusting material and the soft rebase material.

The present invention has been made in view of the above-mentioned prior art, and there is no change in color tone due to coating, and odor, discoloration, and bacteria of dental prostheses such as rebase, mucosal conditioner, and denture base. An object of the present invention is to provide a coating agent composition for suppressing propagation and maintaining the performance of a prosthesis.

[0006]

The present invention comprises (a) a fluorine-containing elastomer, (b) a (meth) acrylic monomer, and (c) a polymerization initiator, and has a viscosity at 25 ° C. of 1 centipoise or more, It is a dental coating composition characterized by being not more than 000 centipoise.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION As the fluorine-containing elastomer (a) used in the present invention, vinylidene fluoride-
Hexafluoropropylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, vinylidene fluoride-pentafluoropropylene copolymer, vinylidene fluoride-pentafluoropropylene-tetrafluoroethylene copolymer, vinylidene fluoride Fluoro rubbers such as a ride-perfluoromethylvinyl ether-tetrafluoroethylene copolymer and a vinylidene fluoride-chlorotrifluoroethylene copolymer are exemplified.

As the (meth) acrylate monomer (b), either a monofunctional (meth) acrylate or a polyfunctional (meth) acrylate can be used. As the monofunctional (meth) acrylate, for example, alkyl (meth) acrylate (alkyl group having 1 to 20 carbon atoms) and other (meth) acrylates can be used. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth)
Alkyl (meth) acrylates such as acrylate, hexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate and stearyl (meth) acrylate (alkyl groups having 1 to 25 carbon atoms), methoxy Ethyl (meth) acrylate, 2-phenoxyethyl (meth)
Acrylate, methoxypolyethylene glycol (meth) acrylate (degree of polymerization 2 to 10), tetrahydrofurfuryl (meth) acrylate, isobornyl (meth)
Examples include acrylate, undecenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate (HEMA), and dimethylaminoethyl (meth) acrylate.

Examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate,
Neopentyl glycol di (meth) acrylate, 1,
Alkylene glycol di (meth) acrylates (1 to 20 carbon atoms in the alkylene group), such as 6-hexanediol di (meth) acrylate and 1,10-decanediol di (meth) acrylate; diethylene glycol di (meth) acrylate; Polyalkylene glycol di (meth) acrylates having 2 to 2 carbon atoms such as ethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate and polyethylene glycol di (meth) acrylate
4, and a degree of polymerization of 2 to 200), glycerin di (meth) acrylate, 2,2′-bis [p- (γ-methacryloxy-β-hydroxypropoxy) phenyl] propane (Bis-GMA), bisphenol A Dimethacrylate, 2,2′-di (4-methacryloxypolyethoxyphenyl) propane (an ethoxy group having 2 to 1
0), 1,2-bis (3-methacryloxy-2-hydroxypropoxy) butane, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, urethane (meth) acrylate and the like.

[0010] These (meth) acrylate monomers are used alone or in combination of two or more. Among them, alkyl (meth) acrylate and alkylene glycol di (meth) acrylate have particularly high compatibility with the thermoplastic elastomer (a) used in the present invention and are suitable.

Examples of the polymerization initiator (c) include a photopolymerization initiator, a thermal polymerization initiator, and a room temperature polymerization initiator. Examples of the photopolymerization initiator include α-diketones such as camphorquinone, diacetyl, 2,3-pentanedione, benzyl, acenaphthenequinone and phenanthraquinone, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Acyl phosphine oxide,
Benzoin methyl ether, benzyl dimethyl ketal, benzophenone, 2-ethylthioxanthone and the like can be mentioned.

These photopolymerization initiators are suitably used as a photopolymerization initiator system in combination with a reducing agent such as a tertiary amine, aldehyde or mercaptan. Examples of such tertiary amines include N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminoethyl benzoate, bis-N, N-dimethylaminobenzophenone,
N, N-dimethylaminobenzaldehyde, N-phenylglycine, morpholino methacrylate, triethanolamine, N-methyldiethanolamine, 2-n-butoxyethyl N, N-dimethylaminobenzoate, isoamyl N-dimethylaminobenzoate, and the like. be able to.

Examples of the aldehyde include citronellal, lauryl aldehyde, o-phthaldialdehyde,
p-octyloxybenzaldehyde and the like can be mentioned. Examples of the mercaptan include 1-decanethiol, thiosalicylic acid, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 4-mercaptoacetophenone, 4-t-butylthiophenol, and the like. it can. Further, a system in which an organic peroxide such as benzoyl peroxide is added to the photopolymerization initiator is also preferably used.

Examples of the thermal polymerization initiator include peroxides such as benzoyl peroxide, di-t-butyl peroxide and cumene hydroperoxide, azo compounds such as azobisisobutyronitrile, and teramethylthiuram disulfide. An initiator such as is used.
Further, room temperature polymerization initiators include organic peroxides / aromatic tertiary amines, and organic peroxides / aromatic tertiary amines /
Redox initiators such as aromatic sulfinic acids are used. When a combination of an oxidizing agent and a reducing agent is contained as the polymerization initiator (c), it is necessary to form a separate package so that they are not mixed, and to mix them immediately before use from the viewpoint of storage stability. is there.

As the organic solvent (d), methyl acetate, ethyl acetate, butyl acetate, methylene chloride, chloroform,
Examples thereof include relatively volatile substances such as acetone, methyl ethyl ketone, toluene, ethyl alcohol, methyl alcohol, and ethyl ether.

In the dental coating composition of the present invention, (a) a fluorine-containing elastomer, and (b) (meth)
The amounts of the acrylic monomer and the polymerization initiator (c) vary depending on the type and molecular weight of the elastomer used, but usually, the elastomer (a), the (meth) acrylic monomer (b) and the polymerization initiator (c) are used. ), The elastomer (a) is 2 to 40% by weight, the (meth) acrylate monomer (b) is 60 to 98% by weight, and the polymerization catalyst (c) is 0.05 to 5% by weight. When the organic solvent (d) is used, its amount is up to 95% by weight of the (meth) acrylic monomer (b).

The composition of the present invention comprises (a) a fluorine-containing elastomer, (b) a (meth) acrylic monomer,
In addition to (c) a polymerization initiator, and (d) an organic solvent, a polymer having no fluorine-containing elastomer (hereinafter abbreviated as polymer (e)) is adhered to the composition after volatilization of the organic solvent. To adjust the properties and the elasticity of the cured polymer,
It can be added in amounts not exceeding 5% by weight of the composition.

As the polymer (e), known ones can be used without any particular limitation. For example, isoprene rubber, butadiene rubber, styrene-butadiene rubber (random copolymer), hydrogenated styrene-butadiene rubber, chloroprene rubber, Nitrile rubber, butyl rubber, ethylene-propylene rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber, fluorine rubber, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, urethane rubber,
Polyolefin-based thermoplastic elastomer, styrene-based thermoplastic elastomer, polyurethane-based thermoplastic elastomer, polyester-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, 1,2-polybutadiene-based thermoplastic elastomer, ethylene-vinyl acetate-based thermoplastic elastomer and poly Elastomers such as vinyl chloride thermoplastic elastomers, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polymethyl (meth) acrylate, polyethyl (meth) acrylate,
Polybutyl (meth) acrylate, polyvinyl acetate, polycarbonate, nylon, polyurethane, polychloroprene, polyvinyl fluoride, polyethylene oxide, polyoxymethylene, polyacrylonitrile, polyvinyl alcohol, polyvinylidene chloride, polyvinylidene fluoride, cellulose, polyester, polyamide and Conventionally known polymers such as cellulose acetate are exemplified.

If necessary, a small amount of hydroquinone, hydroquinone monomethyl ether, butylhydroxyl toluene and the like may be added to the composition of the present invention as a polymerization inhibitor. Also, to increase the stability of the elastomer,
A small amount of an antioxidant or a light stabilizer can be added.
Furthermore, in order to adjust the properties of the organic solvent after volatilization and the properties of the polymerized and cured product to be more suitable, various lubricants, surfactants, inorganic fillers, and plasticizers may be added in small amounts. Pigments, dyes and fibers for mimetic blood vessels can also be added to give gingival or crown color. The composition of the present invention is usually provided as a solution by mixing the fluorine-containing elastomer (a), the (meth) acrylate-based monomer (b), the polymerization initiator (c) and the organic solvent (d).

The composition of the present invention has a viscosity at 25.degree.
It is in the range of 10,000 centipoise, and has properties such that it can be easily applied to adherends such as denture bases and artificial teeth. A more preferred viscosity is in the range of 1 to 2,000 centipoise. If the viscosity is out of the above range, it becomes difficult to apply the coating, which is not desirable.

[0021]

【Example】

(1) Viscosity of the composition The composition is measured at 25 ° C. using an E-type viscometer (manufactured by Tokimec). (2) Discoloration test Dental light irradiator α-
Light irradiation is carried out in water for 3 minutes using a light (manufactured by Kuraray) to polymerize and cure. The cured sample is immersed in a 2% by weight aqueous solution of coffee (manufactured by Nescafe) at 37 ° C. for 7 days, and the change in color tone before and after immersion is measured using a color difference meter (manufactured by Nippon Denshoku).

Example 1 30 g of a fluoro rubber, Daiel G501NK (manufactured by Daikin Industries, Ltd.), 10 g of triethylene glycol dimethacrylate (manufactured by Shin-Nakamura), camphorquinone (manufactured by Wako Pure Chemical Industries)
1.0 g of ethyl N, N-dimethylaminobenzoate (manufactured by Tokyo Kasei) was dissolved in 12 g of ethyl alcohol (manufactured by Wako Pure Chemical) and 48 g of ethyl acetate (manufactured by Wako Pure Chemical) to prepare a coating agent. Powdery liquid of tissue conditioner (made by Matsukaze) was mixed as resin paste and hardened. The cured product was coated with the above coating agent, dried, and irradiated with water in water with α-light for 3 minutes to perform coating.
Table 1 shows the viscosity of the coating agent and the results of a color change test of the resin resin cured product.

Example 2 23 g of technofuron N215 (manufactured by Zeon Corporation), a fluororubber, 7 g of triethylene glycol dimethacrylate (manufactured by Shin-Nakamura), camphorquinone (manufactured by Wako Pure Chemical Industries)
1.0 g, 0.5 g of 2-n-butoxyethyl N, N-dimethylaminobenzoate (manufactured by Tokyo Kasei) and 70 g of acetone (manufactured by Wako Pure Chemical Industries) were dissolved to form a coating agent. As a resin paste, 60 g of Hybler VS-1 and 38 g of n-lauryl methacrylate (manufactured by Kyoeisha Chemical), 1,1
0-decanediol dimethacrylate (manufactured by Kyoeisha Chemical)
2 g and 1.0 g of TMDPO were kneaded with a plastic coder (manufactured by Brabender) at 80 ° C. for 30 minutes to form a paste. The obtained composition was polymerized and cured. The cured product was coated with the above coating agent, dried, and irradiated with water in water with α-light for 3 minutes to perform coating. Table 1 shows the viscosity of the coating agent and the results of a color change test of the resin resin cured product.

Example 3 23 g of technoflon N215 (manufactured by Zeon Corporation), a fluororubber, and methyl methacrylate (Wako Pure Chemical Industries) 77
g, camphorquinone (manufactured by Wako Pure Chemical Industries) 1.0 g, N, N
0.5 g of 2-n-butoxyethyl dimethylaminobenzoate (Tokyo Kasei) was dissolved to give a coating agent. The above coating agent was applied to a polymerized and cured product of the photocurable resin paste described in Example 2, dried, and then irradiated with light with α-light for 3 minutes in water to perform coating. Table 1 shows the viscosity of the coating agent and the results of a color change test of the resin resin cured product.

Example 4 20 g of technoflon P710 (manufactured by Nippon Zeon) which is a fluororubber, 5 g of 1,6-hexanediol dimethacrylate (manufactured by Kyoeisha Chemical, hereinafter abbreviated as HD), 2,
4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF; hereinafter abbreviated as TMDPO)
1.0 g and 75 g of ethyl acetate (manufactured by Wako Pure Chemical Industries) were dissolved to prepare a coating agent. The above coating agent was applied to a polymerized and cured product of the photocurable resin paste described in Example 2, dried, and then irradiated with light with α-light for 3 minutes in water to perform coating. Table 1 shows the viscosity of the coating agent and the results of a color change test of the resin resin cured product.

Comparative Example 1 A powder liquid of a tissue tender (manufactured by Kamezu Chemical), which is commercially available as a denture base soft rebase material, was mixed and polymerized and cured. An attached top coat [solution comprising an acrylic polymer and an acrylic monomer] was applied thereon as a coating agent and dried. Table 1 shows the viscosity of the coating agent and the results of a color change test of the resin resin cured product.

Comparative Example 2 A powder solution of a commercially available tissue tender (made by Kamezu Chemical Co., Ltd.) as a denture base soft rebase material was mixed and polymerized and cured.
A commercially available dental coating agent, Clegard (Kureha Chemical Co., Ltd.), was applied thereon in accordance with the manufacturer's instructions. Table 1 shows the viscosity of the coating agent and the results of a color change test of the resin resin cured product.

[0028]

[Table 1]

[0029]

The coating composition according to the present invention comprises:
It is easy to apply to adherends such as denture base rebase material, mucosal conditioner, denture base, etc.After application, the organic solvent is volatilized and polymerized and cured by light irradiation to form a transparent and lubricious coating layer. Maintains excellent performance in pollution.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Naoto Masuhara 2-5-11 Honkomagome, Bunkyo-ku, Tokyo (72) Inventor Jiro Tarumi 2-6-21-510 Tsutsujigaoka, Akishima City, Tokyo

Claims (3)

[Claims] (1) (a) a fluorine-containing elastomer, (b)
It comprises a (meth) acrylic monomer and (c) a polymerization initiator, and has a viscosity at 25 ° C. of 1 centipoise or more,
A dental coating composition having a molecular weight of 000 centipoise or less. 2. (a) a fluorine-containing elastomer, (b)
The dental coating composition according to claim 1, comprising a (meth) acrylic monomer, (c) a polymerization initiator, and (d) an organic solvent, and having a viscosity at 25 ° C of 1 to 10,000 centipoise. . 3. The monomer according to claim 1, wherein the fluorine-containing elastomer (a) is at least one monomer selected from the group consisting of vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, pentafluoropropylene, perfluoromethylvinylether and chlorotrifluoroethylene. The dental coating composition according to claim 1 or 2, which is a copolymer of the above.