JP3449378B2 - Dental filling and restoration material and denture base resin composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tooth preparation comprising a polyfunctional acrylate monomer (hereinafter referred to as a polyfunctional monomer) and an inorganic filler as basic components. about the visible light curable dental filling restoration materials for filling repair or repair the entire crown of the defect <br/> a shall. 2. Description of the Related Art To repair a tooth defect caused by dental caries or fracture, in recent years, a polymerizable monomer and an inorganic filler have been used because of the aesthetics and easiness of operation similar to natural teeth. Dental filling and restoration materials are widely used. [0003] Conventional polymerization curing methods for dental filling and restorative materials often involve the reaction of a peroxide such as benzoyl peroxide with a co-catalyst such as an amine, each of which is incorporated into a separate paste. The two pastes were polymerized and cured by mixing and kneading. However, recently, a type that polymerizes and cures by irradiating light, especially visible light, has been developed, so that kneading of the paste is unnecessary, there is no fear of bubbles being involved during kneading, and it does not cure until it is irradiated with light This type is mainly used because the morphology of the tooth is easily provided. On the other hand, for denture base compositions such as dentures, denture bases, and lining materials for restoring the form, a method of performing polymerization and curing by light has been attracting attention for the same reason. Conventional photoinitiators used for dental filling / restoring materials and denture base resin compositions which are polymerized and cured by light include camphorquinone, benzyl and α-
Naphthyl, biacetyl, pentanedione, 1,2-phenanthrenequinone, 9,8-phenanthrenequinone, β
Α-diketones represented by naphthoquinone and 2,4-
Thioxanthones such as diethylthioxanthone, 2-isopropylthioxanthone and 2,4-dichlorothioxanthone have been used in combination with a tertiary amine as a reducing agent. [0006] However, the conventional dental filling and restorative material lacks mechanical strength such as surface hardness and bending strength. There are problems such as a limited pod form, and further improvement in strength has been desired. Another problem to be solved is that the aesthetic property of such materials is deteriorated due to discoloration due to adsorption of coloring components contained in food and drink over time after restoration. [0007] In order to improve the mechanical strength, the solution has generally been achieved by increasing the filling rate of the filler. However, the filling rate of the filler is limited, and in applications where the fluidity of the filler is required, the filling rate cannot be increased unconditionally. Therefore, it is necessary to further improve the strength without using the filler. There has not been any effective means for preventing aging discoloration due to adsorption of coloring components, that is, for improving coloring resistance. [0008] [0009] Thus, the present invention, the mechanical strength of the surface hardness and bending strength, etc. of the dental filling restoration materials of cured polymer to the polyfunctional monomer and the inorganic filler as a main component, and The purpose is to improve coloring resistance. [0010] The present inventors have SUMMARY OF THE INVENTION The intensive research to improve the mechanical strength and discoloration resistance of the visible light curable dental filling restoration materials, resulting photoinitiator As α
-Dental curable material using an aminoacetophenone-based photoinitiator has been found to be superior in mechanical strength and coloring resistance to a cured product of a conventional photocurable composition, and has completed the present invention. I came to. By the way, a composition using the α-aminoacetophenone-based initiator has already been disclosed in JP-A-4-3661.
No. 12 discloses a composition used as a coating material for coating the surface of a filling restoration, a denture, or a denture base resin. However, such a composition is composed of the photoinitiator, a hexafunctional acrylate monomer and a volatile solvent, and its use is only described as being used as a coating material. The effect expected by using the photoinitiator is that when the camphorquinone, benzyl or fluorenone is used, the color of the initiator itself reduces the yellowing of the composition itself and its cured product, and does not cause stickiness. It is intended to obtain a cured film having a smooth surface, and to prevent mechanical strength and aging of the cured product of the composition obtained by filling the acrylate monomer with a filler as in the present invention, that is, to prevent discoloration in the oral cavity, i.e., to resist discoloration. It was not intended to improve the performance. That is, the present invention relates to (A) 100 parts by weight of a polyfunctional acrylate monomer and (B) 100 to 90 inorganic fillers.
0 parts by weight, and (C) Na contain α- aminoacetophenone photoinitiator 0.01 to 10 parts by weight is, and Tankan
30% by weight or less of the total acrylate monomer
A dental filling restorative material, characterized in bottom der Rukoto. As the polyfunctional monomer used in the dental restoration material of the present invention, those generally used in dental restoration materials are used without any limitation. Specific examples include: a bifunctional acrylate monomer; (a) an aromatic compound; 2,2-bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-
(Methacryloyloxy) -2-hydroxypropoxyphenyl] propane, 2,2-bis (4-methacryloyloxyethoxyphenyl) propane, 2,2-bis (4
-Methacryloyloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloyloxytetraethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypentaethoxyphenyl) propane,
2,2-bis (4-methacryloyloxydipropoxyphenyl) propane, 2 (4-methacryloyloxyethoxyethoxyphenyl) -2 (4-methacryloyloxydiethoxyphenyl) propane, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxytriethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2 (4-methacryloyloxytriethoxyphenyl) propane,
2,2-bis (4-methacryloyloxydipropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane and their acrylates, divinylbenzene, diallyl phthalate (b) aliphatic compounds; ethylene Glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, propylene glycol dimethacrylate,
Propylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate trifunctional acrylate monomer; trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate , Trimethylolpropane trimethacrylate, and their acrylate tetrafunctional acrylate monomers; pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate, and urethane monomers having the following structure: (However, A is the following: R ¹ , R ² , R ³ , and R ^{4 each} represent a hydrogen atom or a methyl group). Such polyfunctional monomers can be used alone or as a mixture of two or more as needed. For the purpose of adjusting the viscosity and the like, methyl methacrylate, ethyl methacrylate, hydroxyethyl methacrylate, butyl methacrylate, 2-methacryloxypropionate, tridecyl methacrylate and their acrylates, methacrylic acid, acrylic acid, or molecules Dicarboxylic acids such as 7-methacryloxy-1,1-heptanedicarboxylic acid, 11-methacryloxy-1,1-undecanedicarboxylic acid, and 13-methacryloxy-1,1-tridecanedicarboxylic acid having an acidic group in the structure; Methacryloxyethyl trimellitate, 4-methacryloxyethyl trimellitate anhydride,
Methacryloxyphenyl acid phosphate, 10-
It is also possible to use a mixture of methacryloxydecyl dihydroxy decyl dihydrodiene phosphate and a monofunctional acrylate monomer such as acrylate (hereinafter referred to as a monofunctional monomer). In this case, the mixing amount is 30% by weight of all the monomers to prevent a decrease in strength.
The following is preferred. As the filler for the dental restoration material of the present invention, generally used inorganic fillers can be used without any limitation. Specific examples include quartz, silica, silica-alumina, silica-titania, silica-zirconia, aluminosilicate glass, barium glass, strontium glass, silicate glass, titania, zirconia, and alumina. Organic-inorganic composite fillers obtained by pre-filling the monomer with the inorganic filler and polymerizing and curing the same, and then pulverizing the same can also be used as a kind of the inorganic filler of the present invention. Further, for the purpose of obtaining a preferable paste property, an organic filler such as PMMA particles can be filled to such an extent that the mechanical strength is not affected. As the shape of the filler, an irregular shape and a spherical shape are adopted without any limitation, but for the purpose of increasing the filling rate, a spherical shape is preferable. Such an inorganic filler is usually kneaded with a polyfunctional monomer after a surface treatment with a silane coupling agent. As the surface treatment method, a known method is applied without any limitation, typically, a method of directly spraying a solution of a silane coupling agent onto an inorganic filler, water, alcohol such as methanol, ethanol or the like. A method is used in which an inorganic filler is dispersed in an organic solvent such as benzene, toluene, methylene chloride or the like, and a silane coupling agent is reacted in the solution. As the silane coupling agent, γ-methacryloxypropyltrimethoxysilane, ε-methacryloxyoctyltrimethoxysilane, κ-methacryloxydecyltrimethoxysilane, vinyltrimethoxysilane and the like are used. γ-methacryloxypropyltrimethoxysilane is preferably used. The dental restoration material of the present invention is usually obtained by mixing and kneading an inorganic filler in a polyfunctional monomer in which a photoinitiator to be described later is uniformly dissolved in advance. The filling amount of the inorganic filler is suitably in the range of 100 to 900 parts by weight based on 100 parts by weight of the monomer. When mechanical strength is required, the range of 200 to 900 parts by weight is preferable. If the amount is less than 100 parts by weight, sufficient mechanical strength cannot be obtained. The feature of the present invention is that α-
That is, an aminoacetophenone-based photoinitiator is used.
Specific examples of the α-aminoacetophenone-based photoinitiator include 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl-
Diethylamino-1- (4-morpholinophenyl)-
Butanone-1,2-benzyl-2-dimethylamino-1
-(4-morpholinophenyl) -propanone-1,2
-Benzyl-2-diethylamino-1- (4-morpholinophenyl) -propanone-1,2-benzyl-2-
Dimethylamino-1- (4-morpholinophenyl)-
Pentanone-1,2-benzyl-2diethylamino-1
-(4-morpholinophenyl) -pentanone-1 is exemplified, among which 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 shows high polymerization activity by irradiation with visible light. This is preferred. The concentration of the photoinitiator is usually in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the monomer. When no less than this sufficient strength can not be obtained, not only can not be obtained more excellent effect also often used, the aesthetics of the case where the color tone of the polymerized and cured body is used as a yellowed dental filling restorative material descend. Although the above-mentioned effects can be obtained by using the α-aminoacetophenone-based photoinitiator, light such as camphorquinone, which is generally used for polymerization and curing by light irradiation (hereinafter referred to as curing depth), is used. It tends to decrease as compared with the initiator. Therefore, in order to increase the curing depth, a combination with other known photoinitiators is also a preferable embodiment. Other photoinitiators to be combined include camphorquinone, benzyl, α-naphthyl, acenaphthoquinone, p, p′-dimethoxybenzyl, p, p′-dichlorobenzylacetyl, pentanedione, 1,2-phenanthrenequinone , 1,4-phenanthrenequinone,
Α-diketones such as 3,4-phenanthrenequinone, 9,10-phenanthrenequinone and naphthoquinone;
Thioxanthone-based photoinitiators such as -diethylthioxanthone, 2,4-dichlorothioxanthone and 2-isopropylthioxanthone. Further, such photoinitiators may be used alone or in combination of two or more. In the case where the addition of a pigment results in a filling restoration material having low transparency or a case where a higher curing depth is required, 4
An α-diketone having an absorption wavelength of 00 nm or more is effective. Among them, camphorquinone is preferably used because it has a particularly high curing depth and consequently improves the compressive strength. The amount of the other photoinitiator to be used is preferably in the range of 5 to 50 mol% of the α-aminocetophenone-based photoinitiator and in the range of 0.05 to 5.0 wt% based on the monomer. .
If the amount is less than the ranges satisfying both conditions, the expected curing depth cannot be obtained, and if the amount is too large, the color tone of the cured product not only becomes stronger yellow but also lowers the strength. In order to balance the curing depth with the strength and the color tone, the content is preferably in the range of 0.1 to 0.5% by weight based on the monomer. When another photoinitiator is used in combination, it is preferable to combine it with a secondary or tertiary amine, aldehyde or thiol as a reducing agent. Among them, tertiary amines are preferred, and specifically, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4-dimethylaminobenzoic acid n-butoxyethyl ester, 4-dimethylaminobenzoic acid Dialkylaminobenzoic acid ester derivatives such as 2-ethylhexyl ester; dialkylaminophenylalkyl ketones such as 4-dimethylaminoacetophenone and 4-diethylaminoacetophenone; N, N-dimethyl-p-toluidine; N, N-diethanol-p-toluidine , N, N-dimethylminoethyl methacrylate and the like. Particularly preferred are dialkylaminobenzoic acid ester derivatives and dialkylaminophenylalkylketones. In the dental restoration material of the present invention, a pigment, an ultraviolet absorber, an antioxidant and the like for adjusting the color tone may be appropriately added in addition to the above components. [0034] [0035] [0036] [0037] [0038] [0039] [0040] As a light source for curing dental filling restorative material composition of the present invention are photoinitiators, of α- aminoacetophenone Any material containing a wavelength in the range of 250 to 600 nm that is effective for photocleavage may be used, and preferred examples include a high-pressure mercury lamp, a low-pressure mercury lamp, a xenon lamp, and a halogen lamp. EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples. Various physical properties in the present invention were measured as follows. <Micro Brinell surface hardness> 10 mmΦ
After filling the paste into a Teflon split mold having a hole of 2 mm and pressing it with a polypropylene sheet, the sheet was pressed from the top of the sheet with a light irradiator white light manufactured by Takara Labelmont for 30 seconds. Remove the cured body from the split mold,
After being immersed in water at 37 ° C. for 24 hours, the pressure contact surface was measured using a Micro Brinell hardness tester manufactured by Micro Testing Machine Co., Ltd. <Knoop hardness> A test piece was prepared in the same manner as in the case of the microbrinell surface hardness, and a microhardness system manufactured by Matsuzawa Seiki Co., Ltd. was used. <Bending strength> The paste was filled into a stainless steel split mold having a hole of 25 mm x 2 mm x 2 mm, and pressed with a polypropylene sheet. Irradiation was performed for 30 seconds each for three places on one surface. The cured product was taken out of the split mold, immersed in water at 37 ° C. for 24 hours, and then measured at a crosshead speed of 0.5 mm / min using a Shimadzu Autograph testing machine. <Compressive strength> The paste was filled in a stainless steel split mold having a hole of 4 mmΦ × 3 mm, pressed with a polypropylene sheet, and then irradiated with light from the top of the sheet for 30 seconds using a light irradiator white light manufactured by Takara Labelmont. The cured product was taken out of the mold, immersed in water at 37 ° C. for 24 hours, and measured at a crosshead speed of 10 mm / min using a Shimadzu testing machine autograph. <Curing Depth> A 4 mm Φ × 20 mm Teflon split mold was filled with the paste-like composition, and the sheet was sweated from above with a polypropylene sheet. Irradiated for 2 seconds. The cured product was taken out of the split mold, the unpolymerized portion was removed with a plastic spatula, and then immersed in a methanol solution to further remove the unpolymerized monomer, and then the curing depth was measured using a micrometer. <Coloring resistance test> After filling the paste-like composition into a stainless steel split mold having a hole of 6 mm Φ x 3 mm and pressing it with a polypropylene sheet, the light irradiation machine made by Takara Labelmont Co., Ltd. White light for 30 seconds from the top of the sheet. Light irradiation was performed. Remove the cured product from the mold and place it in water at 37 ° C.
After immersion for 4 hours, it was immersed in a coffee solution of 80 ° C. and 7.4 wt% for 72 hours to perform a coloring test. The amount of coloring can be measured using a color difference meter (Tokyo Denshoku)
ΔE was obtained by measurement using a model. Examples 1 to 10 and Comparative Examples 1 to 5 Photocurable compositions were prepared at the composition ratios shown in Table 1. First, the photoinitiator and the reducing agent were changed to 2,2-bis [4- (3-
(Methacryloxy-2-hydroxypropoxy) phenyl] propane (hereinafter abbreviated as bis-GMA) 60 parts by weight and triethylene glycol dimethacrylate (hereinafter 3G
40 parts by weight) were uniformly dissolved in the mixed polyfunctional monomer. As the inorganic filler, silica having a particle size of 0.2 μm
A filler obtained by surface-treating zirconia-based spherical particles with 2% by weight of γ-methacryloxypropyltrimethoxysilane with respect to the powder, and the filler is previously filled in the above-mentioned monomer, and azobisisobutyronitrile is used as a catalyst. A cured product was obtained by heat polymerization, and then a mixture obtained by mixing the cured product with an organic-inorganic composite filler obtained by pulverizing the cured product at a weight ratio of 30/70 was used. The filler was mixed with the above monomer to obtain a dental restoration material. The repair material was measured for surface hardness, flexural strength, compressive strength, curing depth and coffee coloring test, and the results are shown in Table 1. The compounds used in Tables 1 and 2 are abbreviated as follows. I-1; 2-benzyl-dimethylamino-
1- (4-morpholinophenyl) -butanone-1 1-2; 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -pentanone-1 CQ; camphorquinone DETX; 2,4-diethylthioxanthone DMBI N, N'-dimethylaminobenzoic acid isoamyl ester DMBE; N, N'-dimethylaminobenzoic acid ethyl ester DMAP; 4-dimethylaminoacetophenone BZ; benzyl The dental curable composition obtained by the present invention is polymerized and cured by irradiating light having a wavelength region of 250 to 600 nm. The obtained cured product is excellent not only in mechanical strength typified by bending strength and surface hardness but also in resistance to discoloration due to adsorption of coloring components.

Continuation of front page (56) References JP-A-4-366112 (JP, A) JP-A-4-366111 (JP, A) JP-A-63-183905 (JP, A) JP-A-62-86003 (JP) JP-A-62-22804 (JP, A) JP-A-57-183706 (JP, A) JP-A-61-15807 (JP, A) JP-A-62-48610 (JP, A) 62-201806 (JP, A) JP-A-3-206011 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) A61K 6/00-6/10

Claims (1)

(57) [Claims 1] (A) Polyfunctional acrylate monomer 10
0 parts by weight, (B) 100 to 900 parts by weight of an inorganic filler, and (C) an α-aminoacetophenone-based photoinitiator 0.0
Ri Na contain 1 to 10 parts by weight, and monofunctional acrylates
Dental filling repairing material preparative monomer is characterized der Rukoto 30 wt% or less of the total monomers.