CN1703185A - Dental coating kit - Google Patents
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- CN1703185A CN1703185A CN 200380101030 CN200380101030A CN1703185A CN 1703185 A CN1703185 A CN 1703185A CN 200380101030 CN200380101030 CN 200380101030 CN 200380101030 A CN200380101030 A CN 200380101030A CN 1703185 A CN1703185 A CN 1703185A
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Abstract
The invention provides a dental coating kit with high adhesiveness to teeth that contains a primer composition including an acidic group-containing polymeric monomer (a), water (b) and a water-soluble solvent (c) and a surface smoothing composition including a polyfunctional polymeric monomer (f), a volatile solvent (g) and a photopolymerization initiator (h); and a dental coating kit with high adhesiveness to teeth and minimally suffering from chipping and peeling off that contains a primer composition including an acidic group-containing polymeric monomer (a), water (b) and a water-soluble solvent (c), a coating composition including a polymeric monomer (d) and a photopolymerization initiator (e), and a surface smoothing composition including a polyfunctional polymeric monomer (f), a volatile solvent (g) and a photopolymerization initiator (h). Either dental coating kit is particularly useful as a kit for preventing stain and color return of a bleached tooth.
Description
Technical field
The present invention relates to dental coating kit, more particularly, the present invention relates to preventing useful coating kit aspect tooth staining and the variable color, particularly useful dental coating kit aspect the painted and color rollback that prevents to bleach the back tooth (the perverse り of color Hou).
Background technology
Tooth is because of painted, the variable color of breeding of the calm or bacterium that adds lustre to of the coloring matter that contains in Nicotiana tabacum L., the coffee etc.Usually, people wish to prevent the painted and variable color of tooth, expose the tooth of pure white beauty, and this hope is particularly stronger than the male in the middle of the women.For this reason, in recent years, the patient who accepts following dental bleaching treatment among the women of women, especially youth increases rapidly.
The bleaching treatment of tooth is also carried out as making painted tooth or discored tooth revert to the means of natural tooth before as a ring that makes the beauty treatment of teeth whitening beauty.Usually use with the bleach as main component such as hydrogen peroxide, urea peroxide in the bleaching treatment.Bleach has two effects: decompose the decolorization of calm pigment on tooth and make dental surface coarse (matsurfaceization), cause the light diffuse scattering, thereby produce the effect of nebulousurine sense.By these two effects, can make tooth seem pure white.The bleaching treatment is effective for improving aesthetics, but can make dental surface coarse, and therefore after the bleaching treatment, dental plaque, protein, pigment etc. are attached to tooth easily.Therefore, a period of time after the bleaching treatment, especially the bleaching back is 2-3 days, needs control to cause the picked-up and the smoking of painted coffee, curry, citrus juice easily.Even implement these dietary restrictions or smoking restriction, tooth also might be between short-term intrinsic color.In addition, dental plaque, protein, pigment etc. are accumulated on the tooth gradually, the calcification again for the treatment of the dental surface through port intracavity saliva of roughening because of bleaching obtains repairing naturally gradually, so bleaches back about 6 months to 2 years, and the most rollback of bleaching color is to bleaching the preceding color of treatment.
In the past, in order to suppress to bleach painted, the color rollback of back tooth, people had proposed the tooth after the bleaching processing is used the motion of finishing with coating composition.About this finishing coating composition, for example in TOHKEMY 2001-271009 communique, proposed to contain the compositions of the visible light polymerization initiator of the low boiling point solvent of polyfunctional acrylic ester monomer, 20 weight %-80 weight % of 10 weight %-80 weight % and 0.4 weight %-5 weight %; The compositions that also has the white inorganic micro powder of the visible light polymerization initiator of low boiling point solvent, 0.4 weight %-5 weight % of the polyfunctional acrylic ester monomer that proposed to contain 10 weight %-80 weight % in the TOHKEMY 2002-3327 communique, 20 weight %-80 weight % and 0.5 weight %-10 weight %.
But above-mentioned composition is all also bad with the caking property of tooth.In order to eliminate this shortcoming, people have proposed following motion: the phosphate ester that contains 0.1 weight %-5 weight % in each compositions again is that the caking property monomer is (with reference to claim 8, [0030] and [0031] in the TOHKEMY 2001-271009 communique; With reference to claim 10, [0039] and [0040] in the TOHKEMY 2002-3327 communique).
But the result of inventor checking shows: even contain the phosphate ester of ormal weight is the caking property monomer, does not also almost see improvement with the caking property of tooth, and surface cure significantly reduces, but therefore is difficult to obtain the coating composition of practical application.
The present invention establishes for solving above-mentioned problem, and its purpose is to provide with the caking property excellence of tooth, is preventing useful dental coating kit aspect tooth staining and the variable color.
Summary of the invention
For achieving the above object, dental coating kit of the present invention (below can be described as " the 1st test kit ") has rendering composition and surface lubrication compositions, and wherein said rendering composition contains acidic-group polymerizable monomer (a), water (b) and water-soluble solvent (c); Described surface lubrication compositions contains multi-functional polymerizable monomer (f), volatile solvent (g) and Photoepolymerizationinitiater initiater (b).
Rendering composition among the present invention is commonly referred to as the material of self-reversal type bottoming agent, on one side a scour is penetrated in the tooth, shows excellent caking property.Particularly very dark for the tooth infiltration of bleaching back roughening, show extremely excellent caking property.By rendering composition, can guarantee and the caking property of tooth that therefore, using and need not to cooperate phosphate ester in the surface lubrication compositions that re-uses behind the rendering composition is the caking property monomer.When mismatching phosphate ester in the surface lubrication compositions and being the caking property monomer, not only make and the caking property excellence of tooth, also can obtain the also excellent test kit of surface cure by rendering composition.
Rendering composition among the present invention contains acidic-group polymerizable monomer (a), water (b) and water-soluble solvent (c).
Contain acidic-group polymerizable monomer (a) and guarantee caking property with tooth.Containing acidic-group polymerizable monomer (a) is to have acidic-groups such as phosphate, pyrophosphoric acid base, D2EHDTPA base, carboxylic acid group or sulfonic group, and has the polymerizable monomer of polymerizable unsaturated groups such as acryloyl group, methacryl, vinyl, vinyl benzyl.Wherein, preferably has acryloyl group or methacryl close group as insatiable hunger polymerizable monomer.
As containing acidic-group polymerizable monomer (a), the dissolubility of its calcium salt in 25 ℃ of water is 10 weight % or following, preferred 1 weight % or following, and more preferably 0.1 weight % or following, like this, and its caking property and acid resistance excellence, thus preferred.Below provide the object lesson that contains acidic-group polymerizable monomer (a).Wherein with metering system and blanket (methyl) propylene that is designated as of propylene, with methacryl and blanket (methyl) acryloyl group that is designated as of acryloyl group.
The example of the polymerizable monomer of phosphorous acidic group has: biphosphate 2-(methyl) acryloxy ethyl ester, biphosphate 3-(methyl) acryloxy propyl ester, biphosphate 4-(methyl) acryloxy butyl ester, biphosphate 5-(methyl) acryloxy pentyl ester, the own ester of biphosphate 6-(methyl) acryloxy, biphosphate 7-(methyl) acryloxy heptyl ester, biphosphate 8-(methyl) acryloxy monooctyl ester, biphosphate 9-(methyl) acryloxy ester in the ninth of the ten Heavenly Stems, biphosphate 10-(methyl) acryloxy ester in the last of the ten Heavenly stems, biphosphate 11-(methyl) acryloxy undecyl ester, biphosphate 12-(methyl) acryloxy dodecyl ester, biphosphate 16-(methyl) acryloxy cetyl ester, biphosphate 20-(methyl) acryloxy eicosyl ester, 4-[2-(methyl) acryloxy ethyl] cyclohexyl oxygen dihydrogen phosphate, phosphoric acid hydrogen two [2-(methyl) acryloxy ethyl] ester, phosphoric acid hydrogen two [3-(methyl) acryloxy propyl group] ester, phosphoric acid hydrogen two [4-(methyl) acryloxy butyl] ester, phosphoric acid hydrogen two [5-(methyl) acryloxy amyl group] ester, phosphoric acid hydrogen two [6-(methyl) acryloxy hexyl] ester, phosphoric acid hydrogen two [7-(methyl) acryloxy heptyl] ester, phosphoric acid hydrogen two [8-(methyl) acryloxy octyl group] ester, phosphoric acid hydrogen two [9-(methyl) acryloxy nonyl] ester, phosphoric acid hydrogen two [10-(methyl) acryloxy decyl] ester, hydrogenation phosphoric acid 2-(methyl) acryloxy ethyl phenyl ester, hydrogenation phosphoric acid 2-(methyl) acryloxy ethyl hexyl ester, hydrogenation phosphoric acid 2 '-bromo octyl group 2-(methyl) acryloxy ethyl ester, hydrogenation phosphoric acid 2-(methyl) acryloxy ethyl octyl group ester, hydrogenation phosphoric acid 2-(methyl) acryloxy ethyl nonyl ester, hydrogenation phosphoric acid 2-(methyl) acryloxy ethyl decyl ester, hydrogenation phosphoric acid 2-(methyl) acryloxy butyl decyl ester, phosphonic acids (methyl) acryloxy ethyl phenyl ester; 3-phosphono propanoic acid (8-methacryloxy) monooctyl ester, 3-phosphono propanoic acid (9-methacryloxy) ester in the ninth of the ten Heavenly Stems, 3-phosphono propanoic acid (10-methacryloxy) ester in the last of the ten Heavenly stems, 3-phosphine acyl acetic acid (6-methacryloxy) monooctyl ester, 3-phosphine acyl acetic acid (10-methacryloxy) ester in the last of the ten Heavenly stems; Hydrogenation phosphoric acid (4-methoxyphenyl) 2-methacryloxyethyl ester; hydrogenation phosphoric acid (4-methoxyphenyl) 2-methacryloxypropyl ester; Japanese kokai publication sho 52-113089 communique; Japanese kokai publication sho 53-67740 communique; Japanese kokai publication sho 53-69494 communique; Japanese kokai publication sho 53-144939 communique; the phosphorous acidic group hydrophobicity polymerizable monomer and their acid chloride of Japanese kokai publication sho 58-128393 communique or the record of Japanese kokai publication sho 58-192891 communique.In addition, also can exemplify alkali metal salt (sodium salt, potassium salt, lithium salts etc.), the ammonium salt of above-mentioned each phosphorous acidic group polymerizable monomer.
The example that contains pyrophosphoric acid base polymerizable monomer has: pyrophosphoric acid two [2-(methyl) acryloxy ethyl] ester; pyrophosphoric acid two [3-(methyl) acryloxy propyl group] ester; pyrophosphoric acid two [4-(methyl) acryloxy butyl] ester; pyrophosphoric acid two [5-(methyl) acryloxy amyl group] ester; pyrophosphoric acid two [6-(methyl) acryloxy hexyl] ester; pyrophosphoric acid two [7-(methyl) acryloxy heptyl] ester; pyrophosphoric acid two [8-(methyl) acryloxy octyl group] ester; pyrophosphoric acid two [9-(methyl) acryloxy nonyl] ester; pyrophosphoric acid two [10-(methyl) acryloxy decyl] ester; pyrophosphoric acid two [12-(methyl) acryloxy dodecyl] ester and their acid chloride; alkali metal salt; ammonium salt.
The example that contains sulfo-phosphate polymerizable monomer has: phosphordithiic acid dihydro 2-(methyl) acryloxy ethyl ester; phosphordithiic acid dihydro 3-(methyl) acryloxy propyl ester; phosphordithiic acid dihydro 4-(methyl) acryloxy butyl ester; phosphordithiic acid dihydro 5-(methyl) acryloxy pentyl ester; the own ester of phosphordithiic acid dihydro 6-(methyl) acryloxy; phosphordithiic acid dihydro 7-(methyl) acryloxy heptyl ester; phosphordithiic acid dihydro 8-(methyl) acryloxy monooctyl ester; phosphordithiic acid dihydro 9-(methyl) acryloxy ester in the ninth of the ten Heavenly Stems; D2EHDTPA dihydro 10-(methyl) acryloxy ester in the last of the ten Heavenly stems and their acid chloride; alkali metal salt; ammonium salt.
The example that contains carboxylic acid group's polymerizable monomer has: 4-(methyl) acryloxy ethoxy carbonyl phthalic acid; 4-(methyl) acryloxy butoxy carbonyl phthalic acid; 4-(methyl) acryloxy carbonyl octyloxy phthalic acid; 4-(methyl) acryloxy oxygen in last of the ten Heavenly stems base carbonyl phthalic acid and their anhydride; 6-(methyl) acrylamido hexyl formic acid; 8-(methyl) acrylamido octyl group formic acid; 9-(methyl) acryloxy-1; 1-dioctyl phthalate in the ninth of the ten Heavenly Stems; 10-(methyl) acryloxy-1; 1-dioctyl phthalate in the last of the ten Heavenly stems; 11-(methyl) acryloxy-1, the 1-heneicosanedioic acid; (methyl) acrylic acid; maleic acid and their acid chloride; alkali metal salt; ammonium salt.
The example that contains the sulfonic group polymerizable monomer has: 2-(methyl) acrylamide ethylsulfonic acid, 3-(methyl) acrylamide propyl sulfonic acid, 4-(methyl) acrylamide butyl sulfonic acid, 6-(methyl) acrylamide hexyl sulfonic acid, 8-(methyl) acrylamide octyl group sulfonic acid, 10-(methyl) acrylamide decyl sulfonic acid, styrene sulfonic acid etc. contain sulfonic chemical compound and their acid chloride, alkali metal salt, ammonium salt.
The caking property that contains phosphorous acidic group polymerizable monomer in the acidic-group polymerizable monomer (a) is excellent especially, thereby preferred.Wherein, more preferably have carbon number and be 6-25 alkylidene phosphorous acidic group polymerizable monomer and have alkyl and/or the phosphorous acidic group polymerizable monomer of phenyl, most preferably having carbon number is the phosphorous acidic group polymerizable monomer of the alkylidene of 6-12.
Containing acidic-group polymerizable monomer (a) can be used alone, also can be as required with two kinds or above being used in combination.It is very few or the adhesion strength with tooth is reduced to contain acidic-group polymerizable monomer (a).Usually the use level that contains acidic-group polymerizable monomer (a) is 1 weight %-90 weight % with respect to the gross weight of rendering composition, preferred 5 weight %-70 weight %, more preferably 10 weight %-50 weight %.
Water (b) makes and contains the decalcification power enhancing of acidic-group polymerizable monomer (a) to tooth.Need to use and do not contain the water that cohesive force is produced dysgenic impurity in fact.Preferred distilled water or ion exchange water.Water (b) is very few or the adhesion strength with tooth is reduced.Usually the use level of water (b) is 0.1 weight %-90 weight % with respect to the gross weight of rendering composition, preferred 1 weight %-70 weight %, more preferably 5 weight %-50 weight %.
Water-soluble solvent (c) can improve the permeability to tooth.Use solubilized to contain acidic-group polymerizable monomer (a), the dissolubility in 25 ℃ of water is 5 weight % or above, preferred 30 weight %, more preferably all is dissolvable in water the solvent of water with ratio arbitrarily.The example of water-soluble solvent (c) has: boiling point is 150 ℃ or following, preferred 100 ℃ or following water solublity volatile solvent (c-1) under the normal pressure, boiling point surpasses 150 ℃ water-soluble solvent (c-2) under the normal pressure, has polymerisable unsaturated group, the dissolubility in 25 ℃ of water and be 10 weight % or above water-soluble solvent (c-3) (below can be described as " hydrophilic polymer monomer (c-3) ").
The example of water solublity volatile solvent (c-1) has: ethanol, methanol, 1-propanol, isopropyl alcohol, acetone, methyl ethyl ketone, 1,2-dimethoxy-ethane, 1,2-diethoxyethane, oxolane.
The example of water-soluble solvent (c-2) has: dimethyl sulfoxide, ethylene glycol, Polyethylene Glycol.
The example of hydrophilic polymer monomer (c-3) has: (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) acrylic acid 1,3-dihydroxy propyl ester, (methyl) acrylic acid 2,3-dihydroxy propyl ester, 2-trimethylammoniumethyl (methyl) acryloyl chloride, (methyl) acrylamide, 2-hydroxyethyl (methyl) acrylamide, Polyethylene Glycol two (methyl) acrylate (quantity of oxyethylene group be 9 or more than).
In the water-soluble solvent (c), preferred water dissolubility volatile solvent (c-1) and hydrophilic polymer monomer (c-3).Water solublity volatile solvent (c-1) can easily make its volatilization by the dental mobile phone, thereby preferred.Hydrophilic polymer monomer (c-3) can with contain acidic-group polymerizable monomer (a) and solidify simultaneously, thereby preferred.In the hydrophilic polymer monomer (c-3), preferred especially (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) acrylic acid 1,3-dihydroxy propyl ester, (methyl) acrylic acid 2,3-dihydroxy propyl ester, Polyethylene Glycol two (methyl) acrylate (quantity of oxyethylene group is 9).
Water-soluble solvent (c) can be used alone, also can be as required with two kinds or above being used in combination.Water-soluble solvent (c) is very few or permeability and adhesion strength to tooth are reduced.Usually the use level of water-soluble solvent (c) is 1 weight %-98 weight % with respect to the gross weight of rendering composition, preferred 5 weight %-90 weight %, more preferably 10 weight %-60 weight %.
For caking property, mechanical strength and the coating that improves rendering composition, except that containing acidic-group polymerizable monomer (a) and hydrophilic polymer monomer (c-3), can also contain dissolubility in 25 ℃ of water less than 10 weight %, be preferably 1 weight % or following hydrophobicity polymerizable monomer.The example of described hydrophobicity polymerizable monomer has: esters such as a-cyanoacrylate, (methyl) acrylate, alpha-halogen acrylate, crotonates, cinnamate, sorbate, maleate, itaconate, (methyl) acrylamide derivative, vinyl ester, vinyl ethers, list-N-ethenyl derivatives, styrene derivative.Wherein preferred (methyl) acrylate.
Below provide the object lesson of (methyl) acrylate.To have n (n=1,2,3 ...) and the monomer of olefinic double bond be expressed as the n functional monomer, be divided into three kinds of single functionality monomer, bifunctionality monomer and three-functionality-degree or above monomers.
The single functionality monomer:
(methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) benzyl acrylate, (methyl) lauryl acrylate, (methyl) acrylic acid 2,3-two bromo propyl ester, 3-methacryloxypropyl trimethoxy silane, 11-methacryloxy undecyl trimethoxy silane.
The bifunctionality monomer:
Two (methyl) acrylic acid glycol ester, 2,2'-ethylenedioxybis(ethanol). two (methyl) acrylate, propylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-hexanediol two (methyl) acrylate, 1,10-decanediol two (methyl) acrylate, bisphenol-A diglycidyl (methyl) acrylate, 2,2-two [4-(methyl) acryloxy ethoxyl phenenyl] propane, 2,2-two [4-(methyl) acryloyl-oxy Quito ethoxyl phenenyl] propane, 2,2-two [4-[3-(methyl) acryloxy-2-hydroxyl propoxyl group] phenyl] propane, 1,2-two [3-(methyl) acryloxy-2-hydroxyl propoxyl group] ethane, 1,2-two (3-methacryloxy-2-hydroxyl propoxyl group) ethane, [2,2,4-tri-methyl hexamethylene two (2-carbamoyloxy ethyl)] dimethylacrylate.
Three-functionality-degree or above monomer:
Trimethylolpropane tris (methyl) acrylate, trimethylolethane trimethacrylate (methyl) acrylate, tetramethylol methane three (methyl) acrylate, N, N '-(2,2, the 4-tri-methyl hexamethylene) two [2-(amino carboxyl) the third-1,3-glycol] four (methyl) acrylate, three (methyl) acrylic acid pentaerythritol ester, four (methyl) acrylic acid pentaerythritol ester, four (methyl) acrylic acid dipentaerythritol ester, dipentaerythritol five (methyl) acrylate, six (methyl) acrylic acid dipentaerythritol ester.
The hydrophobicity polymerizable monomer can be used alone, also can be as required with two kinds or above being used in combination.The hydrophobicity polymerizable monomer is too much, then may the permeability and the adhesion strength of tooth be reduced.Usually the use level of hydrophobicity polymerizable monomer with respect to the gross weight of rendering composition be 70% or below.Preferred 50 weight % or following, more preferably 30 weight % or following.
In order to improve caking property, can cooperate Photoepolymerizationinitiater initiater and/or chemical polymerisation initiator in the rendering composition.The example of Photoepolymerizationinitiater initiater has: α-two ketone, ketals, thioxanthene ketone, acylphosphine oxide class, alpha-aminoacetophenone class.
The example of α-two ketone has: camphorquinone, benzil, 2,3-pentanedione.
The example of ketals has: benzyldimethylketal, benzyl diethyl al 1-Phenylethanone..
The example of thioxanthene ketone has: 2-clopenthixal ketone, 2,4-diethyl thioxanthone.
The example of acylphosphine oxide class has: 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide; two (2; 4; the 6-trimethylbenzoyl) phenyl phosphine oxide; two (benzoyl) phenyl phosphine oxide; two (2; 6-dimethoxy benzoyl) phenyl phosphine oxide; three (2; the 4-dimethylbenzoyl) phosphine oxide; three (2-anisoyl) phosphine oxide; 2; 6-dimethoxy benzoyl diphenyl phosphine oxide; 2; 6-dichloro-benzoyl base diphenyl phosphine oxide; 2; 3; 5,6-durol formoxyl diphenyl phosphine oxide; benzoyl two-(2, the 6-3,5-dimethylphenyl) phosphonate ester; 2; 4,6-trimethylbenzoyl ethoxyl phenenyl phosphine oxide; disclosed water solublity acylphosphine oxide chemical compound in the special fair 3-57916 communique of Japan.
The example of alpha-aminoacetophenone class has: 2-benzyl-dimethylamino-1-(4-morpholino phenyl)-butanone-1,2-benzyl-diethylamino-1-(4-morpholino phenyl)-butanone-1,2-benzyl-dimethylamino-1-(4-morpholino phenyl)-acetone-1,2-benzyl-diethylamino-1-(4-morpholino phenyl)-acetone-1,2-benzyl-dimethylamino-1-(4-morpholino phenyl)-pentanone-1,2-benzyl-diethylamino-1-(4-morpholino phenyl)-pentanone-1.
Photoepolymerizationinitiater initiater can be used alone, also can be as required with two kinds or abovely unite use.The use level of Photoepolymerizationinitiater initiater is with respect to the preferred 0.01 weight %-10 weight % of the total weight of polymerizable monomer in the rendering composition, more preferably 0.05 weight %-7 weight %, most preferably 0.1 weight %-5 weight %.
Can only use Photoepolymerizationinitiater initiater separately,, also can be used in combination with tertiary amines, aldehydes, polymerization accelerants such as chemical compound with thiol in order to promote photo-curable.
The example of tertiary amines has: (methyl) acrylic acid 2-dimethylamino ethyl ester, N, N-two [(methyl) acryloxy ethyl]-N-methylamine, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid butyl ester, 4-dimethylaminobenzoic acid butoxy ethyl ester, N methyldiethanol amine, 4-dimethylamino benzophenone, N, N-two (2-hydroxyethyl)-para-totuidine.
The example of aldehydes has: dimethylamino benzaldehyde, terephthalaldehyde.
Example with chemical compound of thiol has: 2-mercaptobenzoxazole, decyl mercaptan, 3-sulfydryl propyl trimethoxy silicane, thiobenzoate.
Polymerization accelerant can be used alone, also can be as required with two kinds or above being used in combination.The use level of polymerization accelerant is with respect to the preferred 0.01 weight %-10 weight % of the total weight of polymerizable monomer in the rendering composition, more preferably 0.05 weight %-7 weight %, most preferably 0.1 weight %-5 weight %.
Chemical polymerisation initiator is preferably the redox system polymerization initiator that contains Oxidizing and Reducing Agents.When using the redox system polymerization initiator, the packaged form of rendering composition need be split up into 2 parts or more than, with shielding oxidizer and Reducing agent.
The example of oxidant has: the organic peroxide of diacyl peroxide class, peroxyesters, dialkyl peroxide class, peroxy ketal class, ketone peroxide class, hydroperoxide type etc.
The object lesson of diacyl peroxide class has: benzoyl peroxide, peroxidating 2,4-dichloro-benzoyl, toluoyl peroxide.The object lesson of peroxyesters has t-butyl peroxybenzoate, peroxide M-phthalic acid di tert butyl carbonate, 2,5-dimethyl-2,5-two (benzoyl peroxide) hexane, t-butyl peroxy-2-ethylhexanoate, BPIC t butyl peroxy isopropyl carbonate.The object lesson of dialkyl peroxide class has: dicumyl peroxide, di-t-butyl peroxide, lauroyl peroxide.The object lesson of peroxy ketal class has: 1, and 1-two (t-butyl peroxy)-3,3,5-trimethyl-cyclohexane.The object lesson of ketone peroxide class has: methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl acetoacetate peroxide.The object lesson of hydroperoxide type has: t-butyl hydroperoxide, cumene hydroperoxide, peroxidating are to diisopropyl benzene.
The preferred aromatic uncle amine of Reducing agent, aliphatic tertiary amine and sulfinic acid and salt thereof.
The example of aromatic uncle amine has: N, accelerine, N, N-dimethyl-para-totuidine, N, N-dimethyl-meta-aminotoluene, N, N-diethyl-para-totuidine, N, N-dimethyl-3, the 5-dimethylaniline, N, N-dimethyl-3, the 4-dimethylaniline, N, N-dimethyl-4-MEA, N, N-dimethyl-4-isopropyl aniline, N, N-dimethyl-4-tert-butyl group aniline, N, N-dimethyl-3, the 5-di-tert-butyl aniline, N, N-two (2-hydroxyethyl)-3, the 5-dimethylaniline, N, N-two (2-hydroxyethyl)-para-totuidine, N, N-two (2-hydroxyethyl)-3, the 4-dimethylaniline, N, N-two (2-hydroxyethyl)-4-MEA, N, N-two (2-hydroxyethyl)-4-isopropyl aniline, N, N-two (2-hydroxyethyl)-4-tert-butyl group aniline, N, N-two (2-hydroxyethyl)-3, the 5-diisopropyl aniline, N, N-two (2-hydroxyethyl)-3,5-dibutyl aniline, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid n-butoxy ethyl ester, 4-dimethylaminobenzoic acid (2-methacryloxy) ethyl ester.
The example of aliphatic tertiary amine has: trimethylamine, triethylamine, N methyldiethanol amine, N-ethyldiethanolamine, N-normal-butyl diethanolamine, N-lauryl diethanolamine, triethanolamine, methacrylic acid (2-dimethylamino) ethyl ester, dimethacrylate N methyldiethanol amine, dimethacrylate N-ethyldiethanolamine, monomethyl acrylic acid triethanolamine, dimethacrylate triethanolamine, trimethyl acrylic acid triethanolamine.
The example of sulfinic acid and salt thereof has: benzenesulfinic acid, benzene sulfinic acid sodium salt, benzenesulfinic acid potassium, benzenesulfinic acid calcium, the benzenesulfinic acid lithium, toluenesulfinic acid, toluenesulfinic acid sodium, toluenesulfinic acid potassium, toluenesulfinic acid calcium, the toluenesulfinic acid lithium, 2,4,6-trimethylbenzene sulfinic acid, 2,4,6-trimethyl benzene sulfinic acid sodium salt, 2,4,6-trimethylbenzene sulfinic acid potassium, 2,4,6-trimethylbenzene sulfinic acid calcium, 2,4,6-trimethylbenzene sulfinic acid lithium, 2,4,6-triethylbenzene sulfinic acid, 2,4,6-triethyl group benzene sulfinic acid sodium salt, 2,4,6-triethylbenzene sulfinic acid potassium, 2,4,6-triethylbenzene sulfinic acid calcium, 2,4,6-triisopropyl benzenesulfinic acid, 2,4,6-triisopropyl benzenesulfinic acid sodium, 2,4,6-triisopropyl benzenesulfinic acid potassium, 2,4,6-triisopropyl benzenesulfinic acid calcium.
Oxidizing and Reducing Agents can be used alone, also can be as required with two kinds or abovely unite use.The use level of Oxidizing and Reducing Agents is with respect to all preferred 0.01 weight %-10 weight % of the total weight of polymerizable monomer in the rendering composition, more preferably 0.05 weight %-7 weight %, most preferably 0.1 weight %-5 weight %.
For the coating of adjusting rendering composition, flowability etc., can be to mixed fillers wherein.It is filler, organic system filler or inorganic/organic compounded mix that filler can use inorganic.
Inorganic is the preferred silicon dioxide of filler, and Kaolin, clay, Muscovitum, Muscovitum etc. are the mineral of base material with silicon dioxide, is base material with silicon dioxide, contains Al
2O
3, B
2O
3, TiO
2, ZrO
2, BaO, La
2O
3, SrO
2, CaO, P
2O
5Deng pottery and glass.The object lesson of described glass has lanthanum glass, barium glass, strontium glass, soda-lime glass, lithium borosilicate glass, zinc glass, aluminum fluoride glass, pyrex, bio-vitric.In addition, also preferred crystal quartz, hydroxyapatite, aluminium oxide, titanium oxide, yittrium oxide, zirconium oxide, calcium phosphate, barium sulfate, aluminium hydroxide, sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, fluoridize ytterbium.
The example of organic system filler has: polymethyl methacrylate, polymethyl methacrylate, multifunctional methacrylate polymers, polyamide, polystyrene, polrvinyl chloride, chloroprene rubber, acrylonitrile-butadiene rubber, SBR styrene butadiene rubbers.
The example of inorganic/organic compounded mix has: with inorganic be fillers dispersed gained in the organic system filler filler, inorganic with the coating of various polymerizable monomers be the filler of the surperficial gained of filler.
In order to adjust the flowability of rendering composition, or improve its coating, filler can be carried out surface treatment with known surface conditioning agents such as silane couplers in advance, remix is in rendering composition.This moment, the example of employed surface conditioning agent had: vinyltrimethoxy silane, VTES, vinyl trichlorosilane, vinyl three ('beta '-methoxy ethyoxyl) silane, γ-methacryloxypropyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-An Jibingjisanyiyangjiguiwan.
Filler can be used alone, also can be as required with two kinds or above being used in combination.Usually the use level of filler is 50 weight % or following with respect to the gross weight of rendering composition, preferred 30 weight % or following.This use level surpasses 50 weight %, and then permeability or the caking property to tooth can reduce.
In addition, be to increase the decalcification power of rendering composition to tooth, it is little the pKa ratio can be contained acidic-group polymerizable monomer (a), and the acid that does not have a polymerizable group is mixed in the rendering composition.The example of described acid has mineral acids such as phosphoric acid, nitric acid, sulphuric acid, organic acid such as acetic acid, citric acid, trichloroacetic acid, p-methyl benzenesulfonic acid.But, mix the acid that these do not have polymerizable group too much, can produce infringement to dentine, meeting stripping after the use, or the cohesive force of rendering composition and tooth is reduced.Therefore, the use level of common above-mentioned acid is preferably 10 weight % or following with respect to the gross weight of rendering composition, more preferably 5 weight % or following.
Can add polymerization inhibitor, coloring agent, fluorescent agent, UV absorbent etc. in the rendering composition.In addition, in order to have antibiotic property, can mixed chlorinated cetyl pyridinium, benzalkonium chloride, (methyl) acryloxy dodecyl bromination pyridine, (methyl) acryloxy hexadecylpyridinium chloride, (methyl) acryloxy decyl ammonium chloride, trichlorine Lignum Rhamnellae antibiotic property material.
Surface lubrication compositions among the present invention contains multi-functional polymerizable monomer (f), volatile solvent (g) and Photoepolymerizationinitiater initiater (h).
Multi-functional polymerizable monomer (f) can use the hydrophobicity polymerizable monomer with two or more olefinic double bonds.Described hydrophobicity polymerizable monomer can use with rendering composition in identical as difunctionality polymerizable monomer in any blended (methyl) acrylate of having stated of composition or three-functionality-degree or above polymerizable monomer.Consider from the surface cure angle, preferred three (methyl) acrylic acid pentaerythritol ester, four (methyl) acrylic acid pentaerythritol ester, three (methyl) acrylic acid dipentaerythritol ester, four (methyl) acrylic acid dipentaerythritol ester, five (methyl) acrylic acid dipentaerythritol ester, six (methyl) acrylic acid dipentaerythritol ester etc. have the polymerizable monomer of three or above olefinic double bond, and preferred especially five (methyl) acrylic acid dipentaerythritol ester, six (methyl) acrylic acid dipentaerythritol ester etc. have the polymerizable monomer of five or above olefinic double bond.As multi-functional polymerizable monomer (f), with respect to this multi-functional polymerizable monomer (f) gross weight, preferably contain 70 weight % or above polymerizable monomer with three or above olefinic double bond, more preferably contain 80 weight % or more than.
The use level of multi-functional polymerizable monomer (f) is preferably 40 weight %-98 weight % with respect to the gross weight of surface lubrication compositions, more preferably 80 weight %-95 weight %.This use level is during less than 40 weight %, and the coating of surface lubrication compositions or operability may reduce.
Volatile solvent (g) dilutes multi-functional polymerizable monomer (f), improves the coating or the operability of surface lubrication compositions.Boiling point under the preferred normal pressure of volatile solvent (g) is 150 ℃ or following, more preferably 100 ℃ or following.When the boiling point under the use normal pressure surpassed 150 ℃ volatile solvent (g), the surface cure of surface lubrication compositions may reduce.The example of volatile solvent (g) has: alcohols such as ethanol, methanol, 1-propanol, isopropyl alcohol, ketones such as acetone, butanone, diethyl ketone, 1,2-dimethoxy-ethane, 1, ethers such as 2-diethoxyethane, oxolane, esters such as methyl formate, Ethyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, (methyl) esters of acrylic acids such as (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) acrylic acid n-propyl, (methyl) isopropyl acrylate.Wherein, from considering that preferred (methyl) esters of acrylic acid is considered from low, the low-boiling angle of toxicity again, special preferable methyl acrylic acid methyl ester. with the simultaneously solidified angle of multi-functional polymerizable monomer (f).
Volatile solvent (g) can be used alone, also can be as required with two kinds or above being used in combination.Consider that from the angle of coating or operability the use level of volatile solvent (g) is with respect to the gross weight of surface lubrication compositions, preferred 1 weight %-59 weight %, more preferably 5 weight %-50 weight %, most preferably 10 weight %-40 weight %.This use level surpasses 59 weight %, then surface lubrication compositions mobile too high, and operability or coating reduction, the abnormal smells from the patient during curing has enhanced tendency.
Photoepolymerizationinitiater initiater (h) can use with rendering composition in blended to have stated Photoepolymerizationinitiater initiater identical as any composition.Preferred α-two ketone and acylphosphine oxide class.Of light color from initiator itself, the angle that the xanthochromia after the curing is little consider, more preferably 2,4, and 6-trimethylbenzoyl diphenyl phosphine oxide.
Photoepolymerizationinitiater initiater (h) can be used alone, also can be as required with two kinds or above being used in combination.The use level of Photoepolymerizationinitiater initiater (h) is with respect to the total weight of polymerizable monomer in the surface lubrication compositions, preferred 0.01 weight %-10 weight %, more preferably 1 weight %-5 weight %.Can only use Photoepolymerizationinitiater initiater (h) separately, but, can be used in combination with polymerization accelerant in order to promote curable.Described polymerization accelerant can use with rendering composition in as any blended identical chemical compound of polymerization accelerant of having stated of composition.The use level of polymerization accelerant is with respect to the total weight of polymerizable monomer in the surface lubrication compositions, preferred 0.01 weight %-10 weight %, more preferably 0.05 weight %-7 weight %, most preferably 0.1 weight %-5 weight %.
As required, can hybrid pigment in the surface lubrication compositions.By hybrid pigment, can regulate the tone of gained coating.The example of described pigment has: iron oxide red, phthalocyanine blue, various azo pigment and titanium oxide.For example, by mixed oxidization titanium in the surface lubrication compositions, formation has opacifying property compositions, can strengthen the aesthetics of tooth.Pigment can be used alone, also can be as required with two kinds or above being used in combination.The use level of pigment can consider that the tone of coating, aesthetics suitably regulate.
As required, can mixed fillers in the surface lubrication compositions.Filler can use with rendering composition in blended to have stated filler identical as any composition.Filler can be used alone, also can be as required with two kinds or above being used in combination.The use level of filler is with respect to the gross weight of surface lubrication compositions, preferred 40 weight % or following, more preferably 20 weight % or following.This use level surpasses 40 weight %, and the coating of then surface lubrication compositions or operability may reduce.Filler can use mean diameter 0.001 μ m-50 μ m's usually, when in the surface lubrication compositions during hybrid pigment, in order to suppress the precipitation of pigment effectively, preferably uses the ultramicron filler of 0.001 μ m-0.1 μ m.The preferred colloidal silica of described ultramicron filler (for example Japanese ア エ ロ ジ Le company, trade name " ア エ ロ ジ Le ").As required, can also add polymerization inhibitor, fluorescent agent, UV absorbent etc. in the surface lubrication compositions.
During preparation surface lubrication compositions, preferred each composition of suitably selecting is regulated, and makes it have suitable viscosity.Consider that from the angle of coating, operability the surface lubrication compositions is at the preferred 30cP-3 of 30 ℃ viscosity, 000cP, more preferably 50cP-1,000cP, most preferably 80cP-500cP.This viscosity is during less than 30cP, and is mobile too high, may be penetrated into the slit between the adjacent teeth when being used for tooth; And surpass 3, and 000cP, then coating may reduce.
The 1st test kit is effective especially for the painted and color rollback that prevents to bleach the back tooth.Below, being example, the using method of the 1st test kit is described the situation that is coated with of tooth after the bleaching.
At first, rendering composition is coated the surface of bleaching the back tooth, as required, use dental mobile phone (air syringe) etc. makes the rendering composition drying, until not having flowability; Perhaps when rendering composition contains polymerization initiator (Photoepolymerizationinitiater initiater and/or chemical polymerisation initiator), make the coating layer polymerizing curable, form prime coat (step 1).
Then, coating surface lubricating oil composition on prime coat, the surface lubrication compositions with the rayed coating makes its polymerizing curable, and thus, the dental surface after bleaching forms surface layer (step 2).When rendering composition contains Photoepolymerizationinitiater initiater, can pass through rayed, make rendering composition and surface lubrication compositions polymerizing curable simultaneously.
The preferred 0.005mm-0.5mm of the coating thickness of surface lubrication compositions, more preferably 0.01mm-0.3mm.The example of the light source that is fit to when carrying out rayed has: xenon lamp, Halogen light, mercury lamp, light emitting diode.The irradiation time of light is relevant with light wavelength and light quantity.If it is use the special-purpose irradiator of dentistry, then promptly curable about 3 seconds-3 minutes.After forming coating on the tooth after the bleaching, when part or all of coating during by the surfacial spalling of tooth or because of painted etc. going wrong, use dental utensil such as dentiscalprum to peel off problematic part etc. after, use at dental surface once more.By disposing so repeatedly, can effectively prevent to bleach the color rollback of the painted of back tooth and bleaching back tooth.
The 1st test kit can be used for the part of tooth by the tooth of corona repair materials such as metal, ceramic material, pottery, composite material solidification thing reparation.The 1st test kit can use separately, also can be used in combination with facing cleaning agent such as prime material, hypochlorite etc. with commercially available dental metal prime material, ceramic material bonding.
As mentioned above, in the 1st test kit,, so can form the coating good with the caking property of tooth because rendering composition can be guaranteed and the caking property of tooth.
But, in the 1st test kit, since hard and crisp by the layer (surface layer) that the surface lubrication compositions forms, the stress during owing to interlock etc., and stripping bits (part of coating has a little damaged and peel off phenomenon) or this problem that must solve of breaking appear in coating easily.
In order to solve invent just by the problems referred to above that the 1st test kit exists for another dental coating kit of the present invention (below can be described as " the 2nd test kit ").
That is, the 2nd test kit has rendering composition, coating composition, surface lubrication compositions; Wherein, described rendering composition contains acidic-group polymerizable monomer (a), water (b) and water-soluble solvent (c); Coating composition contains polymerizable monomer (d) and Photoepolymerizationinitiater initiater (e); The surface lubrication compositions contains multi-functional polymerizable monomer (f), volatile solvent (g) and Photoepolymerizationinitiater initiater (h).
The rendering composition that the 2nd test kit is had and surface lubrication compositions and the 1st test kit of having stated had those are identical.
Therefore following to having only the exclusive coating composition of the 2nd test kit to describe.
Coating composition is the compositions that is used for forming the intermediate layer between the layer (prime coat) that is formed by rendering composition and layer (surface layer) that formed by the surface lubrication compositions.This intermediate layer as prevent by the top layer that the surface lubrication compositions forms take place that stripping is considered to be worth doing, disruptive cushion and playing a role.
Coating composition contains polymerizable monomer (d) and Photoepolymerizationinitiater initiater (e).
Polymerizable monomer (d) is not particularly limited so long as can form the polymerizable monomer in intermediate layer on the surface of prime coat and can use.Polymerizable monomer (d) can be considered viscosity, the polymerism of gained coating composition, intensity of gained coating etc., carries out suitable selection.The content of polymerizable monomer (d) is too much, and then the coating of coating composition (II), flowability, operability etc. may reduce, therefore with respect to the preferred 40-99.99 weight of the gross weight of coating composition %, and more preferably 60-99.95 weight %.
Polymerizable monomer (d) can be used alone, also can be as required with two kinds or above being used in combination.Wherein, hydrophilic polymer monomer and hydrophobicity polymerizable monomer are used in combination, then obtain wettability, permeability excellence, and be effective as the coating of the cushion that toughness is high behind the polymerizing curable tooth.
The hydrophilic polymer monomer not only makes the wettability of tooth, permeability is improved, also improved the toughness of gained coating.Improve toughness by mixing the hydrophilic polymer monomer, this is owing to contain the monomeric coating of hydrophilic polymer water absorption and swelling in intraoral moist environment behind the polymerizing curable.Hydrophilic polymer monomer described here is meant that the dissolubility in 25 ℃ of water is 10 weight % or above polymerizable monomer.The hydrophilic polymer monomer preferably this dissolubility at 30 weight % or above polymerizable monomer.
The monomeric object lesson of hydrophilic polymer has: (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 3-hydroxy propyl ester, (methyl) acrylic acid 1,3-dihydroxy propyl ester, (methyl) acrylic acid 2,3-dihydroxy propyl ester, 2-hydroxypropyl-1,3-two (methyl) acrylate, 3-hydroxypropyl-1,2-two (methyl) acrylate, two (methyl) acrylic acid pentaerythritol ester, 2-trimethyl ammonium ethyl (methyl) acryloyl chloride, (methyl) acrylamide, 2-hydroxyethyl (methyl) acrylamide, Polyethylene Glycol two (methyl) acrylate (quantity of oxyethylene group be 9 or more than).Preferable methyl acrylic acid 2-hydroxy methacrylate wherein.
The hydrophilic polymer monomer can be used alone, also can be as required with two kinds or above being used in combination.The monomeric use level of hydrophilic polymer is with respect to the preferred 5 weight %-50 weight % of the gross weight of coating composition.Less than 5 weight %, then the toughness of the wettability of coating composition and gained solidfied material has the tendency of reduction; Surpass 50 weight %, then the intensity of gained solidfied material may reduce.This use level is 5 weight %-40 weight % more preferably, most preferably 10 weight %-35 weight %.
The hydrophobic polymer monomer can improve caking property, mechanical strength and coating.Hydrophobicity polymerizable monomer described here is meant that dissolubility in 25 ℃ of water is less than the polymerizable monomer of 10 weight %.Hydrophobicity polymerizable monomer preferably this dissolubility is 1 weight % or following polymerizable monomer.
The object lesson of hydrophobicity polymerizable monomer has: esters such as (methyl) acrylate, a-cyanoacrylate, alpha-halogen acrylate, crotonates, cinnamate, sorbate, maleate, itaconate, (methyl) acrylamide derivative, vinyl ester, vinyl ethers, list-N-ethenyl derivatives, styrene derivative etc. have the chemical compound of polymerizable unsaturated group.Wherein preferred (methyl) acrylate.(methyl) acrylate can use with rendering composition in as any composition contain to state (methyl) acrylate identical.
The kind of hydrophobicity polymerizable monomer can consider that viscosity, polymerism of coating composition etc. suitably selects.The hydrophobicity polymerizable monomer can be used alone, also can be as required with two kinds or above being used in combination.Consider preferred bifunctionality or above monomer from the polymerism angle.The hydrophobicity polymerizable monomer is very few, and then the coating of coating composition, flowability, operability etc. may reduce.The use level of hydrophobicity polymerizable monomer is with respect to the preferred 20 weight %-90 weight % of the gross weight of coating composition, more preferably 40 weight %-80 weight %.
Except that hydrophilic polymer monomer and hydrophobicity polymerizable monomer; have one or acidic-groups such as above phosphate, pyrophosphoric acid base, D2EHDTPA base, carboxylic acid group or sulfonic group by mixing; and the polymerizable monomer (containing the acidic-group polymerizable monomer) with polymerisable unsaturated groups such as acryloyl group, methacryl, vinyl, styryls is further used as polymerizable monomer (d), can further improve the caking property with tooth.Consider that from the caking property angle containing the preferred dissolubility of its calcium salt in 25 ℃ of water of acidic-group polymerizable monomer is 10 weight % or following, more preferably 1 weight % or following most preferably is 0.1 weight % or following.Contain the acidic-group polymerizable monomer can use with rendering composition in to contain acidic-group polymerizable monomer (a) as stating of must composition containing identical.As containing the acidic-group polymerizable monomer, the caking property excellence of the polymerizable monomer of phosphorous acidic group, thereby preferred.Wherein, more preferably have the phosphorous acidic group polymerizable monomer of alkylidene, alkyl and/or phenyl that carbon number is 6-25, most preferably having carbon number is the phosphorous acidic group polymerizable monomer of the alkylidene of 6-12.
Containing the acidic-group polymerizable monomer can be used alone, also can be as required with two kinds or above being used in combination.It is too much to contain the acidic-group polymerizable monomer, then the polymerism of coating composition (surface cure) may reduce, therefore contain the use level of acidic-group polymerizable monomer with respect to the preferred 0.1 weight %-30 weight % of the gross weight of coating composition, more preferably 0.1 weight %-20 weight %.
The Photoepolymerizationinitiater initiater that contains in the coating composition (e) can use known Photoepolymerizationinitiater initiater.Photoepolymerizationinitiater initiater (e) for example can use with rendering composition in the identical chemical compound of Photoepolymerizationinitiater initiater that contains as any composition.Photoepolymerizationinitiater initiater can be used alone, also can be as required with two kinds or above being used in combination.The use level of Photoepolymerizationinitiater initiater (e) is with respect to the preferred 0.01 weight %-10 weight % of polymerizable monomer (d), more preferably 0.05 weight %-7 weight %, most preferably 0.1 weight %-5 weight %.
In order to promote photo-curable, Photoepolymerizationinitiater initiater (e) can be used in combination with polymerization accelerant.Polymerization accelerant for example can use with rendering composition in the chemical compound of stating tertiary amines, aldehydes, having thiol that contains as any composition.These chemical compounds can be used alone, also can be as required with two kinds or above being used in combination.The content of polymerization accelerant is with respect to the preferred 0.01 weight %-10 weight % of the gross weight of coating composition, more preferably 0.05 weight %-7 weight %, most preferably 0.1 weight %-5 weight %.
As required, Photoepolymerizationinitiater initiater (e) can be used in combination with chemical polymerisation initiator.By being used in combination, making especially and also can improve because of light is difficult to arrive the polymerism that is difficult to carry out photopolymerisable coating inside with chemical polymerisation initiator.Described chemical polymerisation initiator preferably contains the chemical polymerisation initiator of the oxidation-reduction system of Oxidizing and Reducing Agents.As previously mentioned, when using the chemical polymerisation initiator of oxidation-reduction system, the packaged form of coating composition need be split up into 2 parts or more than, Oxidizing and Reducing Agents is separated.Oxidizing and Reducing Agents can use with rendering composition in as any composition contain to state Oxidizing and Reducing Agents identical.
Oxidizing and Reducing Agents all can be used alone, also can be as required with two kinds or above being used in combination.The use level of Oxidizing and Reducing Agents is with respect to all preferred 0.01 weight %-10 weight % of the total weight of polymerizable monomer in the coating composition, more preferably 0.05 weight %-7 weight %, most preferably 0.1 weight %-5 weight %.
Can add refractive index in the coating composition and be 1.9 or above inorganic filler.Refractive index described here is meant with the light of wavelength 589.3nm surveys periodic refractive index at 20 ℃.Refractive index be 1.9 or above inorganic filler not only make not polymer layer attenuation of surface behind the polymerizing curable, improve the surface cure of coating, can also hide the variable color of tooth, the brightness that improves coating, therefore improve aspect the aesthetics extremely useful.Consider that from the effect angle of improving of surface cure and aesthetics preferred index is 2.1 or above inorganic filler.Refractive index was less than 1.9 o'clock, and surface cure may reduce.Refractive index be 1.9 or the example of above inorganic filler have: titanium oxide (refractive index: 2.49-2.90), zirconium oxide (refractive index: 2.13-2.19), zinc oxide (refractive index: 2.00-2.02).Refractive index is 1.9 or the preferred 0.01 μ m-100 μ m of mean diameter of above inorganic filler, more preferably 0.1 μ m-80 μ m.Surface behind the polymerizing curable not reason of polymer layer attenuation is not clear and definite as yet, but the inventor has following opinion.
That is, usually, when using Photoepolymerizationinitiater initiater to make the polymerizable monomer polymerization, be present in airborne oxygen and play inhibitor action, the result, the surface portion of the coating that contacts with air produces the not polymer layer of micron order thickness.But, contain refractive index in the coating on a small quantity and be 1.9 or above opaque inorganic filler (being equivalent to pigment), then this inorganic filler makes light (light that the shines during initiated polymerization) diffuse-reflectance of injecting coating, by the scattering of light effect, make the polymerism of this surface portion improve not polymer layer attenuation of the surface behind the polymerizing curable as a result.
Refractive index be 1.9 or above inorganic filler can be used alone, also can be as required with two kinds or above being used in combination.Refractive index be 1.9 or the use level of above inorganic filler with respect to the preferred 0.1 weight %-50 weight % of the gross weight of coating composition.This use level was than 0.1 weight % hour, and surface cure has the tendency of reduction; When this use level surpasses 50 weight %, only use the optical polymerism catalyst then to have curing depth to shoal, can not fully be cured to inner tendency.Preferred use level is 0.1 weight %-10 weight %, and most preferred use level is 0.1 weight %-5 weight %.
In order to suppress refractive index is 1.9 or the sedimentation of above inorganic filler, improves mechanical strength, coating, by the taking property in the container, operability etc., other filler can be used in combination.With refractive index be 1.9 or the filler that is used in combination of above inorganic filler have: refractive index less than 1.9 inorganic be filler, organic system filler and inorganic/organic compounded mix.Inorganic be filler, organic system filler and inorganic/organic compounded mix can use with rendering composition in blended to have stated inorganic be that filler, organic system filler and inorganic/organic compounded mix are identical as any composition.
With refractive index be 1.9 or the filler that is used in combination of above inorganic filler can be used alone, also can be as required with two kinds or above being used in combination.With refractive index be 1.9 or the use level of the filler that is used in combination of above inorganic filler with respect to the preferred 60 weight % or following of the gross weight of coating composition, more preferably 40 weight % or following.With refractive index is 1.9 or the preferred 0.001 μ m-50 μ m of mean diameter of the filler that is used in combination of above inorganic filler.In order to suppress refractive index is 1.9 or the sedimentation of above filler, improve coating, operability, gross weight with respect to coating composition, can preferably mix 1 weight %-40 weight %, more preferably 3 weight %-35 weight %, the most preferably colloidal silica of the mean diameter 0.001 μ m-0.1 μ m of 5 weight %-30 weight %.The example of described colloidal silica has: the silicon dioxide that the particle diameter that is obtained by spray heating decomposition is little (for example Japanese ア エ ロ ジ Le company, trade name " ア エ ロ ジ Le "), the Ludox that is obtained by wet method, the monodisperse silica that is obtained by sol-gal process.
For the mechanical strength that improves coating composition, coating, operability, flowability etc., can refractive index be 1.9 or above inorganic filler and the filler that is used in combination with it carry out surface treatment with known surface conditioning agents such as silane couplers in advance, re-use afterwards.Described surface conditioning agent can use with rendering composition in as any composition blended be used for filler to state surface conditioning agent identical.
Can hybrid pigment in the coating composition.By hybrid pigment, can regulate the tone of gained coating.The example of pigment has: iron oxide red, phthalocyanine blue, various azo pigment.Pigment can be used alone, also can be as required with two kinds or above being used in combination.The use level of pigment is not particularly limited, and can consider that the color harmony aesthetics of coating composition is suitably mixed.
Can mix fluorion release property material in the coating composition.By mixing fluorion release property material, can make dental surface have acid resistance.Described fluorion release property examples of substances has: fluorine glass such as aluminum fluoride glass, sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, fluoridize metal fluorides such as ytterbium, the fluorion emission polymers such as copolymer of disclosed methyl methacrylate and metering system acyl fluorides in the Japanese kokai publication hei 5-85912 communique, the cetylamine hydrofluoride.
Can add polymerization inhibitor, fluorescent agent, UV absorbent in the coating composition.In addition, in order to have antibiotic property, can mixed chlorinated cetyl pyridinium, benzalkonium chloride, (methyl) acryloxy dodecyl bromination pyridine, (methyl) acryloxy hexadecylpyridinium chloride, (methyl) acryloxy decyl ammonium chloride, trichlorine Lignum Rhamnellae antibiotic property material.
During the preparation coating composition, preferred each composition of suitably selecting makes it have suitable viscosity.From the coating of tooth, operability equal angles are considered, the preferred 300cP-50 of the viscosity of coating composition under 30 ℃, 000cP, more preferably 500cP-30,000cP, most preferably 1,000cP-20,000cP.This viscosity is during less than 300cP, and mobile too high, operability may reduce; And surpassing 50,000cP, coating reduce, the uniform hue reduction of coating.
Then, the using method of the 2nd test kit, the method for promptly using the 2nd test kit to apply are described.
At first, rendering composition is coated the surface of tooth, as required, use dental mobile phone etc. to make the rendering composition drying, until not having flowability; Perhaps when rendering composition contains polymerization initiator (Photoepolymerizationinitiater initiater and/or chemical polymerisation initiator), make the coating layer polymerizing curable, form prime coat (step 1).
Then, the surface coated coating composition at prime coat makes the coating layer polymerizing curable by rayed, forms intermediate layer (step 2).When rendering composition contains Photoepolymerizationinitiater initiater, can pass through rayed, make rendering composition and coating composition polymerizing curable simultaneously.
At last, the surface coated surface lubrication compositions in the intermediate layer makes the coating layer polymerizing curable by rayed, forms surface layer, forms the coating (step 3) of three-decker thus on the surface of tooth.
After step 2 finished, when there was more not polymer layer in the surface in intermediate layer, after then step 3 finished, the surface cure of surface layer was not enough sometimes.For preventing this problem, preferably after step 2 finishes, for example use cotton balls etc. to wipe not polymer layer.
The preferred 0.005mm-1mm of the coating thickness of the coating composition in the step 2, more preferably 0.01mm-0.7mm, most preferably 0.1mm-0.5mm.
Coating layer to coating composition carries out rayed, when making the coating layer polymerizing curable, preferably uses light sources such as xenon lamp, Halogen light, mercury lamp, light emitting diode.The irradiation time of light is relevant with light wavelength and light quantity, if use the special-purpose irradiator of dentistry, gets final product polymerizing curable about common 3 seconds-3 minutes.
The 2nd test kit and the 1st test kit are same, not only applicable to unbleached dental surface, also are applicable to the dental surface after the bleaching.Dental bleaching is as the means that make teeth whitening, popularized in recent years, known bleaching can make the dental surface roughening, but the 2nd test kit and the 1st test kit are same, also can preferably use for this class coarse tooth that becomes, can reach the purpose of post-bleach effect and prevent to bleach after creamy white rollback phenomenon.
The 2nd test kit and the 1st test kit are same, are not only tooth, also can use on the surface of dental repair materials such as metal, ceramic material, pottery, composite material solidification thing.
The 2nd test kit and the 1st test kit are same, can be used in combination with facing cleaning agent such as prime material, hypochlorites with commercially available dental metal prime material, ceramic material bonding.
Embodiment
Illustrate in greater detail the present invention by the following examples, but the present invention is not subjected to the qualification of following embodiment.
At first, provide the embodiment of the 1st test kit, the bleaching of tooth is all carried out according to following method among following examples 1-12 (embodiment of the 1st test kit) and the comparative example 1-4.
[method for bleaching of tooth]
In the bleach (Kerativ company, trade name " PowerGel ") of 1 packing, add the aquae hydrogenii dioxidi of 3.5ml 35%, fully mix, make gelatinous bleach.On the surface of the philtrum cutting of cleaning with brush (industrial group of Japanese tooth section, trade name " Block ラ シ コ-Application ") in advance of pulling up, be coated with this gel bleach of about 1mm thickness towards lip one side.Carry out 30 seconds rayed facing to the lip side surface of middle cutting that is coated with the gel bleach with dental radiation of visible light lamp (エ ア-テ Network ニ Network ス company, trade name " ア-Network ラ イ ト "), place after 5 minutes, with the lip side surface of cutting in the flowing water washing.To repeat 3 times by the aforesaid operations of coating gel bleach, finish bleaching to the flowing water washing.
Abbreviation shown below is as follows.
[containing acidic-group polymerizable monomer (a)]
MDP: biphosphate 10-(methyl) acryloxy ester in the last of the ten Heavenly stems
[water-soluble solvent (c)]
HEMA: 2-hydroxyethyl methacrylate
[multi-functional polymerizable monomer (f)]
DPHA: six acrylic acid dipentaerythritol ester
DPPA: five acrylic acid dipentaerythritol ester
PTA: pentaerythritol triacrylate
[volatile solvent (g)]
MMA: methyl methacrylate
[Photoepolymerizationinitiater initiater (h)]
TMDPO:2,4,6-trimethylbenzoyl diphenyl phosphine oxide
CQ: camphorquinone
[polymerization accelerant]
DMABE:4-dimethylaminobenzoic acid ethyl ester
[phosphate ester is the caking property monomer]
PMEAP: phenyl (2-methacryloxyethyl) phosphate ester acid
DPMEP: diphenyl (methacryloxyethyl) phosphate ester
(embodiment 1)
Preparation contains the rendering composition of MDP (20 weight %), distilled water (25 weight %) and HEMA (55 weight %).Also preparation contains the surface lubrication compositions of DPHA (93 weight %), MMA (5 weight %) and TMDPO (2 weight %).Obtain the viscosity of surperficial lubricating oil composition in the coating kit that contains above-mentioned rendering composition and surface lubrication compositions by the method for following (1).Method by following (2)-(4) is inquired into operability, abnormal smells from the patient and surface cure.These results are illustrated in the table 1.Viscosity, operability, abnormal smells from the patient and the surface cure obtained in following embodiment and the comparative example all are to obtain by the method for following (1)-(4).
(1) viscosity
Get 0.6cc surface lubrication compositions, measure its viscosity under 30 ℃ with E type viscometer (eastern machine industry).
(2) operability
To the rendering composition of preparation among the philtrum cutting coating embodiment 1 after the bleaching, after former state left standstill for 30 seconds, volatile ingredient is volatilized with the dental mobile phone, do not have a flowability until rendering composition.Then, the lip side flat of middle cutting is fixing up, make it parallel to the ground, then with the fine, soft fur pen by the incisxal edge of lip side to tooth neck line, the surface lubrication compositions of preparation among the coating embodiment 1, whether visual valuation liquid has hydrops between the adjacent teeth slit or the trickling of root face near the incisxal edge.Do not see fully drop down liquid and hydrops be evaluated as zero, only see the △ that is evaluated as of a little, obviously visible being evaluated as *.
(3) abnormal smells from the patient
With dental illumination shot-light (group horse ウ シ オ electric, marque " ラ イ テ Le II ") coated face of coating surface lubricating oil composition in above-mentioned (2) is carried out the rayed in 60 seconds, make the curing of surface lubrication compositions.When this solidified, the member of evaluation group was positioned its outer muzzle for the position of 3cm above the coated face, estimated the abnormal smells from the patient of surperficial lubricating oil composition.Estimate by 7 members of evaluation group, do not feel be evaluated as 3 fens of abnormal smells from the patient, feel abnormal smells from the patient but do not have be evaluated as 2 fens of unplessantness displeasure that abnormal smells from the patient makes us producing be evaluated as 1 fen of unplessantness displeasure, 7 members' of evaluation group meansigma methods is 2 minutes or above is evaluated as zero, less than 2 minutes be evaluated as *.
(4) surface cure
The surface of the surface layer after the curing that firmly obtains in the wiping above-mentioned (3) with scraper (the Network レ シ ア of Co., Ltd., marque " JK ワ イ パ-"), the visual valuation surface cure.Cut is not seen on the surface, and the surface is fully solidified to be evaluated as zero; The surface produces cut, and surface cure is inadequate to be evaluated as *.
(embodiment 2-7)
DPHA, DPPA, PTA, MMA, ethanol, TMDPO, CQ and DMABE are mixed according to the part by weight shown in the table 1, prepare 6 kinds of surface lubrication compositionss.For the coating kit that contains the rendering composition of preparation among these various surface lubrication compositionss and the embodiment 1, obtain the viscosity of its surface lubrication compositions, research operability, abnormal smells from the patient and surface cure.The result is as shown in table 1.
Table 1
| Cooperation ratio (weight %) in each compositions | ||||||||
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | ||
| Rendering composition | Contain acidic-group polymerizable monomer (a): MDP | ? ??20 | ? ??20 | ? ??20 | ? ??20 | ? ??20 | ? ??20 | ? ??20 |
| Water (b): distilled water | ? ??25 | ? ??25 | ? ??25 | ? ??25 | ? ??25 | ? ??25 | ? ??25 | |
| Water-soluble solvent (c): HEMA | ? ??55 | ? ??55 | ? ??55 | ? ??55 | ? ??55 | ? ??55 | ? ??55 | |
| The surface lubrication composition | Multi-functional polymerizable monomer (f): DPHA DPPA PTA | ? ??93 ??- ??- | ? ??88 ??- ??- | ? ??88 ??- ??- | ? ??88 ??- ??- | ? ??- ??88 ??- | ? ??- ??- ??88 | ? ??83 ??- ??- |
| Volatile solvent (g): MMA ethanol | ? ??5 ??- | ? ??10 ??- | ? ??10 ??- | ? ??- ??10 | ? ??10 ??- | ? ??10 ??- | ? ??15 ??- | |
| Photoepolymerizationinitiater initiater (h): TMDPO CQ polymerization accelerant: DMABE | ? ??2 ??- ? ??- ? | ? ??2 ??- ? ??- ? | ? ??- ??2 ? ??2 ? | ? ??2 ??- ? ??- ? | ? ??2 ??- ? ??- ? | ? ??2 ??- ? ??- ? | ? ??2 ??- ? ??- ? | |
| The viscosity of surface lubrication compositions (cP) | ??310 | ??205 | ??204 | ??198 | ??201 | ??185 | ??124 | |
| Operability | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | |
| Abnormal smells from the patient | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | |
| Surface cure | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | |
As shown in Table 1: its undesirable abnormal smells from the patient of the 1st test kit of embodiment 1-7 is very little, and the operability excellence.In addition, not phosphorous acid esters is the caking property monomer in the surface lubrication compositions in the 1st test kit of embodiment 1-7, so surface cure is also excellent.
(embodiment 8)
Preparation contains the rendering composition of MDP (10 weight %), distilled water (30 weight %) and HEMA (60 weight %).Use contains the coating kit of the surface lubrication compositions of preparation among this rendering composition and the embodiment 1, forms surface layer by the method shown in following (1), estimates its surface cure.Obtain surface layer and the adhesion strength of bleaching the back tooth by the method shown in following (2), the adhesion strength of obtaining among following examples 9-12 and the comparative example 1-4 is also obtained by following method.The result is illustrated in the table 2.
(1) formation of surface layer
The middle body of cutting sticks the adhesive tape that has diameter 3mm hole, thickness 150 μ m among the people after bleaching, and the rendering composition of preparation among the embodiment 8 is coated in this hole of adhesive tape.After leaving standstill 30 seconds, make volatile ingredient volatilization, do not have a flowability, form prime coat until rendering composition with the dental mobile phone.Then, the surface lubrication compositions of preparation is filled up in the hole in the surface coated embodiment 1 of this prime coat.With dental illumination shot-light (group horse ウ シ オ electric, marque " ラ イ テ Le II ") this coated face is carried out the rayed in 60 seconds, make its polymerizing curable, form surface layer.
(2) adhesion strength
With commercially available dental resin rubber cement (Network ラ レ, marque " パ Na PVC ア 21 "), the cylindrical rod (diameter 5mm, length 1.5cm) of the stainless steel of bonding on above-mentioned surface layer, with the end face (disc) of rod as adhesive surface.After 30 minutes, test film be impregnated in 37 ℃ the water, measure adhesion strength after 1 day.The following enforcement of the mensuration of adhesion strength: with several thickness is that the metal plate of 0.5mm supports tooth and fixes, with the excellent downward direction tractive of stainless steel, the cylindrical rod that makes stainless steel with respect to the axle of direction of draw in ± 5 ° or following scope.Adhesion strength is with tensile test apparatus (society of Shimadzu Seisakusho Ltd., trade name " オ-ト グ ラ Off "), is to measure in 2mm/ minute with the crosshead speed setting.Adhesion strength is obtained with the meansigma methods of 8 test film measured values.
(embodiment 9-12)
MDP, distilled water, HEMA, ethanol, CQ and DMABE are mixed according to the part by weight shown in the table 2, prepare 4 kinds of rendering compositions.For the coating kit that contains the surface lubrication compositions of preparation among these various rendering compositions and the embodiment 1, estimate the surface cure of its surface layer.Also obtain and bleach the adhesion strength of back tooth.The result is as shown in table 2.
(comparative example 1)
The middle body of cutting sticks the adhesive tape that has diameter 3mm hole, thickness 150 μ m among the people after bleaching, and the surface lubrication compositions of preparation among the embodiment 1 is coated in this hole of adhesive tape.Under the state in the hole of filling up adhesive tape with the surface lubrication compositions, this coated face is carried out the rayed in 60 seconds with dental illumination shot-light (electric, the marque " ラ イ テ Le II " of group horse ウ シ オ), the surface of tooth forms coating after bleaching, estimate its surface cure, obtain and bleach the adhesion strength of back tooth simultaneously.The result is as shown in table 2.
(comparative example 2-4)
With DPHA, MMA, CQ, DMABE and phosphate ester is that caking property monomer (phenyl (2-methacryloxyethyl) phosphate ester acid or diphenyl (methacryloxyethyl) phosphate ester) mixes according to the part by weight shown in the table 2, prepares 4 kinds of surface lubrication compositionss.These surface lubrication compositionss are directly used in the labiad side of the philtrum cutting after the bleaching, form coating, estimate its surface cure, obtain and bleach the adhesion strength of back tooth simultaneously.The result is as shown in table 2.
Table 2
| Cooperation ratio (weight %) in each compositions | ||||||||||
| Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | ||
| Rendering composition | Contain acidic-group polymerizable monomer (a): MDP | ? ??10 | ? ??30 | ? ??50 | ? ??20 | ? ??20 | ? ??- | ? ??- | ? ??- | ? ??- |
| Water (b): distilled water | ? ??30 | ? ??20 | ? ??15 | ? ??25 | ? ??25 | ? ??- | ? ??- | ? ??- | ? ??- | |
| Water-soluble solvent (c): HEMA ethanol | ? ??60 ??- | ? ??50 ??- | ? ??35 ??- | ? ??- ??55 | ? ??53 ??- | ? ??- ??- | ? ??- ??- | ? ??- ??- | ? ??- ??- | |
| Photoepolymerizationinitiater initiater: CQ polymerization accelerant: DMABE | ? ??- ? ??- | ? ??- ? ??- | ? ??- ? ??- | ? ??- ? ??- | ? ??1 ? ??1 | ? ??- ? ??- | ? ??- ? ??- | ? ??- ? ??- | ? ??- ? ??- | |
| The surface lubrication composition | Multi-functional polymerizable monomer (f): DPHA | ? ??88 | ? ??88 | ? ??88 | ? ??88 | ? ??88 | ? ??88 | ? ??56 | ? ??54 | ? ??54 |
| Volatile solvent (g): MMA | ? ??10 | ? ??10 | ? ??10 | ? ??10 | ? ??10 | ? ??10 | ? ??40 | ? ??40 | ? ??40 | |
| Photoepolymerizationinitiater initiater (h): TMDPO CQ polymerization accelerant: DMABE | ? ? ??2 ??- ? ??- | ? ? ??2 ??- ? ??- | ? ? ??2 ??- ? ??- | ? ? ??2 ??- ? ??- | ? ? ??2 ??- ? ??- | ? ? ??2 ??- ? ??- | ? ? ??- ??2 ? ??2 | ? ? ??- ??2 ? ??2 | ? ? ??- ??2 ? ??2 | |
| Phosphate ester is the caking property monomer: PMEAP DPMEP | ? ??- ??- | ? ??- ??- | ? ??- ??- | ? ??- ??- | ? ??- ??- | ? ??- ??- | ? ??- ??- | ? ??2 ??- | ? ??- ??2 | |
| Surface cure | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??○ | ??× | ??× | |
| Adhesion strength (MPa) | ??15.3 | ??14.8 | ??15.6 | ??15.2 | ??15.9 | ??1.5 | ??1.3 | ??3.7 | ??3.9 | |
As shown in Table 2: use the 1st test kit of embodiment 8-12, when the dental surface after bleaching forms prime coat and surface layer successively, can obtain high adhesion strength.In addition, not phosphorous acid esters is the caking property monomer in the surface lubrication compositions in the 1st test kit of embodiment 8-12, so surface cure is also excellent.Relative therewith, do not form prime coat, during tooth after directly the surface lubrication compositions being used to bleach (comparative example 1,2), though surface cure is excellent, adhesion strength is extremely low.In addition, do not form prime coat, in the time of will containing phosphate ester and be the tooth after the caking property monomer combination is directly used in bleaching, though some improvement are arranged, surface cure bad (comparative example 3,4) with the caking property of bleaching back tooth.
In the foregoing description, be illustrated as example with the situation of using the tooth after the coating of the 1st test kit is bleached, the 1st test kit also can be used for the coating of unbleached tooth.
Below, record and narrate the embodiment of the 2nd test kit.Abbreviation shown below is as follows.
MDP: biphosphate 10-(methyl) acryloxy ester in the last of the ten Heavenly stems
HEMA: 2-hydroxyethyl methacrylate
UDMA: dimethacrylate [2,2,4-tri-methyl hexamethylene two (2-carbamoyloxy ethyl)] ester
U-4TH: tetramethyl acrylic acid N, N '-(2,2, the 4-tri-methyl hexamethylene) two [2-(amino carboxyl) the third-1,3-glycol] ester
Bis-GMA: bisphenol-A diglycidyl methacrylate
3G: triethylene glycol dimethacrylate
DPHA: six acrylic acid dipentaerythritol ester
DPPA: five acrylic acid dipentaerythritol ester
MMA: methyl methacrylate
CQ: camphorquinone
DMABE:4-dimethylaminobenzoic acid ethyl ester
TMDPO:2,4,6-trimethylbenzoyl diphenyl phosphine oxide
(embodiment 13)
Preparation contains the rendering composition of MDP (20 weight %), distilled water (40 weight %) and HEMA (40 weight %) respectively; The coating composition that contains UDMA (50 weight %), U-4TH (20 weight %), 3G (29 weight %), CQ (0.5 weight %), DMABE (0.5 weight %); The surface lubrication compositions that contains DPHA (73 weight %), MMA (25 weight %) and TMDPO (2 weight %).For the coating kit that contains this rendering composition, coating composition and surface lubrication compositions (the 2nd test kit), by the adhesion strength of following cohesion test method A1 mensuration with tooth.Estimate anti-stripping bits property by following anti-stripping bits property test method B1.The result is illustrated in the table 3.
[cohesion test method A1]
(1) with brushing the enamel surface that (industrial society of Japanese tooth section, trade name " Block ラ シ コ-Application ") cleans the philtrum cutting lip side of pulling up, middle body in the enamel par sticks the hole that has diameter 3mm, the adhesive tape of thickness 150 μ m then, and the rendering composition of preparation among the embodiment 13 is coated in the hole of adhesive tape.After former state leaves standstill 30 seconds, make volatile ingredient volatilization, do not have a flowability, form prime coat until rendering composition with the dental mobile phone.The coating composition of preparation fills up in the hole in the surface coated embodiment 13 of this prime coat.With dental illumination shot-light (group horse ウ シ オ electric society, trade name " ラ イ テ Le II ") this coated face is carried out the rayed in 30 seconds, make its curing, form the intermediate layer.The surface lubrication compositions that reuse fine, soft fur pen prepares in the surface coated embodiment 13 in this intermediate layer is carried out the rayed in 60 seconds with above-mentioned dental illumination shot-light, makes its curing, forms surface layer.
(2) with on the surface of surface layer, the bond cylindrical rod (diameter 5mm, length 1.5cm) of stainless steel of commercially available dental resin rubber cement (Network ラ レ, marque " パ Na PVC ア 21 "), with the end face (disc) of rod as adhesive surface.After 30 minutes, test film be impregnated in 37 ℃ the water, measure adhesion strength after 1 day.The following enforcement of the mensuration of adhesion strength: with several thickness is that the metal plate of 0.5mm suffers tooth and fixes, with stainless steel rod downward direction tractive, the cylindrical rod that makes stainless steel with respect to the axle of direction of draw in ± 5 ° or following scope.Adhesion strength is with tensile test apparatus (society of Shimadzu Seisakusho Ltd., trade name " オ-ト グ ラ Off "), is to measure in 2mm/ minute with the crosshead speed setting.Adhesion strength is obtained with the meansigma methods of 8 test film measured values.
[anti-stripping bits property test method B1]
(1) the tongue side of people's labial teeth of pulling up is simultaneously cut,, be processed into the tabular of thickness 2mm so that parallel with the enamel par of lip side.Clean the enamel surface of lip side of the tooth of this processing with brush (industry society of Japanese tooth section, trade name " Block ラ シ コ-Application "), middle body at the enamel flat sticks the hole that has diameter 5mm, the adhesive tape of thickness 150 μ m then, the rendering composition of preparation among the coating embodiment 13.After leaving standstill 30 seconds, make volatile ingredient volatilization, do not have a flowability, form prime coat until rendering composition with the dental mobile phone.The coating composition of preparation fills up in the hole in the surface coated embodiment 13 of this prime coat.With dental illumination shot-light (group horse ウ シ オ electric society, trade name " ラ イ テ Le II ") this coated face is carried out the rayed in 30 seconds, make its curing, form the intermediate layer.The surface lubrication compositions that reuse fine, soft fur pen prepares in the surface coated embodiment 13 in this intermediate layer, carry out the rayed in 60 seconds with above-mentioned dental illumination shot-light, stripping tape then obtains being formed with on the enamel surface the tabular tooth of the surface layer of diameter 5mm.The tabular tooth that forms this surface layer is arranged at the mould middle body of vertical 3cm, horizontal 2cm, thick 2mm, make discoideus surface layer up, filling dental composite resin on every side, fixing teeth, under this state, make dental composite resin polymerizing curable, make test film.This test film is fixed on the tank bottom surface of filling water, makes toothbrush (ラ イ オ Application company, trade name " PVC ト イ-Application "; Hardness: common) hair contacts with the Surface Vertical of surface layer, under the state that applies 250g load, toothbrush is reciprocatingly slided with the amplitude of 10cm.
(2) after reciprocal 10000 times, 20000 times, 40000 times, take out test film, with the peripheral part of the discoideus surface layer of optical microscope (enlargement ratio: 10 times) observation, check that whether major diameter is arranged is 0.1mm or above stripping bits, estimates anti-stripping bits property according to following metewand.
(metewand)
Do not see the stripping bits ... zero
See the stripping bits ... *
(embodiment 14-17)
Prepare rendering composition, coating composition, the surface lubrication compositions formed shown in the table 3 respectively, make 4 kinds of dental coating kits (the 2nd test kit).For these dental coating kits, obtain adhesion strength by above-mentioned cohesion test method A1.Estimate anti-stripping bits property by above-mentioned anti-stripping bits property test method B1.The result is illustrated in the table 3.
(comparative example 5,6)
For the surface lubrication compositions (comparative example 6) of preparation in surface lubrication compositions (comparative example 5) for preparing among the embodiment 13 and the comparative example 1, obtain adhesion strength by following cohesion test method A2.Estimate anti-stripping bits property by following anti-stripping bits property test method B2.The result is illustrated in the table 3.Wherein, behind the rider-type brush 10000 times, take out test film, carry out the evaluation of anti-stripping bits property, but before the rider-type brush of anti-stripping bits property test finished for 10000 times, the coating of comparative example 5 and comparative example 6 all came off from tooth, therefore can't carry out the evaluation of anti-stripping bits property.
[cohesion test method A2]
(1) with brushing the enamel surface that (industrial society of Japanese tooth section, trade name " Block ラ シ コ-Application ") cleans the philtrum cutting labiad side of pulling up, middle body in the enamel par sticks the hole that has diameter 3mm, the adhesive tape of thickness 150 μ m then, and the surface lubrication compositions of preparation in embodiment 13 or the comparative example 1 is coated in the hole of adhesive tape.With dental illumination shot-light (group horse ウ シ オ electric society, trade name " ラ イ テ Le II ") this coated face is carried out the rayed in 60 seconds, make its curing, form coating.
(2) measure the adhesion strength of gained coating and tooth in above-mentioned (1) by above-mentioned cohesion test method A1 (2).
[anti-stripping bits property test method B2]
(1) with the tongue one side cutting of people's labial teeth of pulling up,, is processed into the tabular of thickness 2mm so that parallel with the adamantine par of lip side.Clean the lip side enamel surface of the tooth of this processing with brush (industrial society of Japanese tooth section, trade name " Block ラ シ コ-Application "), middle body in the enamel par sticks the hole that has diameter 5mm, the adhesive tape of thickness 150 μ m then, the surface lubrication compositions of preparation in coating embodiment 13 or the comparative example 1.With above-mentioned dental illumination shot-light this coated face is carried out the rayed in 60 seconds, make its curing, stripping tape then obtains being formed with on the enamel surface the tabular tooth of the coating of diameter 5mm.
(2) consider property to be worth doing by the anti-stripping of gained coating in above-mentioned anti-stripping bits property test method B1 (2) evaluations above-mentioned (1).
Table 3
| Cooperation ratio (weight %) in each compositions | |||||||||
| Embodiment 13 | Embodiment 14 | Embodiment 15 | Embodiment 16 | Embodiment 17 | Comparative example 5 | Comparative example 6 | |||
| Rendering composition | Contain acidic-group polymerizable monomer (a): MDP | ? 20 | ? 20 | ? 20 | ? 20 | ? 20 | ? - | ? - | |
| Water (b): distilled water | ? 40 | ? 40 | ? 40 | ? 40 | ? 40 | ? - | ? - | ||
| Water-soluble solvent (c): HEMA ethanol | ? 40 - | ? - 40 | ? 40 - | ? 40 - | ? 40 - | ? - - | ? - - | ||
| Coating composition | Polymerizable monomer (d): UDMA U-4TH Bis-GMA 3G HEMA | ? 50 20 ? - ? 29 ? - ? | ? 50 20 ? - ? 29 ? - ? | ? - - ? 60 ? 39 ? - ? | ? 50 20 ? - ? - ? 29 ? | ? - - ? 60 ? - ? 39 ? | ? - - ? - ? - ? - ? | ? - - ? - ? - ? - ? | |
| Photoepolymerizationinitiater initiater (e): CQ polymerization accelerant: DMABE | ? ? 0.5 ? 0.5 | ? ? 0.5 ? 0.5 | ? ? 0.5 ? 0.5 | ? ? 0.5 ? 0.5 | ? ? 0.5 ? 0.5 | ? ? - ? - | ? ? - ? - | ||
| The surface lubrication compositions | Multi-functional polymerizable monomer (f): DPHA | ? 73 | ? 73 | ? 73 | ? 73 | ? 73 | ? 73 | ? 88 | |
| Volatile solvent (g): MMA | ? 25 | ? 25 | ? 25 | ? 25 | ? 25 | ? 25 | ? 10 | ||
| Photoepolymerizationinitiater initiater (h): TMDPO | ? 2 | ? 2 | ? 2 | ? 2 | ? 2 | ? 2 | ? 2 | ||
| Adhesion strength (MPa) | 15.4 | 14.6 | 14.7 | 15.7 | 15.5 | 0.3 | 1.5 | ||
| Anti-stripping bits property | Reciprocal 10000 times reciprocal 20000 times reciprocal 40000 times | ○ ○ ○ | ○ ○ ○ | ○ ○ ○ | ○ ○ ○ | ○ ○ ○ | - - - | - - - | |
(embodiment 18-22)
Prepare rendering composition, coating composition, the surface lubrication compositions formed shown in the table 4 respectively, make 5 kinds of dental coating kits (the 2nd test kit).For these dental coating kits, obtain adhesion strength by above-mentioned cohesion test method A1.Estimate anti-stripping bits property by above-mentioned anti-stripping bits property test method B1.The result is illustrated in the table 4.
Table 4
| Cooperation ratio (weight %) in each compositions | ||||||
| Embodiment 18 | Embodiment 19 | Embodiment 20 | Embodiment 21 | Embodiment 22 | ||
| Rendering composition | Contain acidic-group polymerizable monomer (a): MDP | ? 20 | ? 20 | ? 20 | ? 20 | ? 20 |
| Water (b): distilled water | ? 40 | ? 40 | ? 40 | ? 40 | ? 40 | |
| Water-soluble solvent (c): HEMA | ? 40 | ? 40 | ? 40 | ? 40 | ? 40 | |
| Coating composition | Polymerizable monomer (d): UDMA U-4TH 3G | ? 50 ? 20 ? 29 ? | ? 50 ? 20 ? 29 ? | ? 50 ? 20 ? 29 ? | ? 50 ? 20 ? 29 ? | ? 50 ? 20 ? 29 ? |
| Photoepolymerizationinitiater initiater (e): CQ polymerization accelerant: DMABE | ? 0.5 ? ? 0.5 | ? 0.5 ? ? 0.5 | ? 0.5 ? ? 0.5 | ? 0.5 ? ? 0.5 | ? 0.5 ? ? 0.5 | |
| The surface lubrication composition | Multi-functional polymerizable monomer (f): DPHA DPPA | ? 83 ? - | ? - ? 73 | ? 73 ? - | ? 85 ? - | ? 70 ? - |
| Volatile solvent (g): MMA ethanol | ? ? 15 ? ? ? | ? ? 25 ? ? ? | ? ? - ? 25 ? | ? ? 10 ? ? ? | ? ? 25 ? ? ? | |
| Photoepolymerizationinitiater initiater (h): TMDPO CQ polymerization accelerant: DMABE | ? ? 2 ? - ? ? - ? | ? ? 2 ? - ? ? - ? | ? ? 2 ? - ? ? - ? | ? ? - ? 2.5 ? ? 2.5 ? | ? ? - ? 2.5 ? ? 2.5 ? | |
| Adhesion strength (MPa) | 15.6 | 14.9 | 15.3 | 15.8 | 14.6 | |
| Anti-stripping bits property | Reciprocal 10000 times reciprocal 20000 times reciprocal 40000 times | ○ ? ○ ? ○ | ○ ? ○ ? ○ | ○ ? ○ ? ○ | ○ ? ○ ? ○ | ○ ? ○ ? ○ |
(embodiment 23-37)
Prepare rendering composition, coating composition, the surface lubrication compositions formed shown in the table 5 respectively, make 7 kinds of dental coating kit (embodiment 23-29; The 2nd test kit).Prepare rendering composition, the surface lubrication compositions formed shown in the table 6 in addition respectively, make 8 kinds of dental coating kit (embodiment 30-37; The 1st test kit).The test kit of embodiment 32 is respectively identical test kit mutually with the test kit of embodiment 7, test kit and the test kit of embodiment 2, test kit and the test kit of embodiment 1, test kit and the test kit of embodiment 8, test kit and the test kit of embodiment 9, the test kit of embodiment 37 and the test kit of embodiment 10 of embodiment 36 of embodiment 35 of embodiment 34 of embodiment 33.For these dental coating kits, obtain adhesion strength by above-mentioned cohesion test method A1.Estimate anti-stripping bits property by above-mentioned anti-stripping bits property test method B1.Measure the variation that applies the tooth brightness that causes by the assay method of following brightness flop again.The result is illustrated in table 5 and the table 6.
[brightness flop assay method]
(1) with people's labial teeth of pulling up to the tongue side cut so that parallel, be processed into the tabular of thickness 2mm with the adamantine par of lip side.Clean the lip side enamel surface of the tooth of this processing with brush (industrial society of Japanese tooth section, trade name " Block ラ シ コ-Application "), middle body in the enamel par sticks the hole that has diameter 7mm, the adhesive tape of thickness 150 μ m then, measures the brightness index (L of bore portion
* 0).Brightness index (L
*) mensuration use colour difference meter (Japanese electric color society, ∑ 90 types, light source are D65 light source, angle of visibility 2 degree, colour examining scope 5mm φ), put standard white plate behind and measure.L described here
*Brightness index in the L*a*b* colour system of stipulating among the expression JIS-Z8729.
(2) then, the rendering composition that in the adhesive tape hole, prepares among the coating embodiment 23-37.After leaving standstill 30 seconds, make the volatile ingredient volatilization,, form prime coat until not having flowability with the dental mobile phone.
(3) then, the coating composition for preparing in the surface coated embodiment of prime coat 23-29 fills up in the hole.With above-mentioned dental illumination shot-light this coated face is carried out the rayed in 30 seconds, make its polymerizing curable, form the intermediate layer.Test kit to the embodiment 30-37 that do not have coating composition does not carry out this step (3), enters next step (4).
(4) the surface lubrication compositions for preparing among the embodiment 23-37 is coated the surface (being the surface of prime coat among the embodiment 30-37) in intermediate layer with the fine, soft fur pen, carry out the rayed in 60 seconds with above-mentioned dental illumination shot-light, stripping tape obtains the tabular tooth that enamel surface is formed with the coating of diameter 7mm then.
(5) then, similarly measure the brightness index (L of the coating part of the tabular tooth of gained with above-mentioned (1)
* 1).Calculate variation (the Δ L that applies the brightness that causes by following formula
*).
The variation of brightness (Δ L
*)=L
* 1-L
* 0
Table 5
| Cooperation ratio (weight %) in each compositions | |||||||||
| Embodiment 23 | Embodiment 24 | Embodiment 25 | Embodiment 26 | Embodiment 27 | Embodiment 28 | Embodiment 29 | |||
| Rendering composition | Contain acidic-group polymerizable monomer (a): MDP | ? 20 | ? 20 | ? 20 | ? 20 | ? 20 | ? 20 | ? 20 | |
| Water (b): distilled water | ? 40 | ? 40 | ? 40 | ? 40 | ? 40 | ? 40 | ? 40 | ||
| Water-soluble solvent (c): HEMA | ? 40 | ? 40 | ? 40 | ? 40 | ? 40 | ? 40 | ? 40 | ||
| Coating composition | Polymerizable monomer (d): UDMA U-4TH 3G HEMA | ? 50 20 21.3 | ? 50 20 20.9 | ? 50 20 20.5 | ? 50 20 18.5 | ? 80.9 - - 10 | ? 65.9 - - 25 | ? 50.9 - - 40 | |
| Photoepolymerizationinitiater initiater (e): CQ polymerization accelerant: DMABE | ? 0.5 ? 0.5 | ? 0.5 ? 0.5 | ? 0.5 ? 0.5 | ? 0.5 ? 0.5 | ? 0.5 ? 0.5 | ? 0.5 ? 0.5 | ? 0.5 ? 0.5 | ||
| Inorganic filler (i): day office's titanium dioxide powder ( *1) | ? 0.2 | ? 0.6 | ? 1.0 | ? 3.0 | ? 0.6 | ? 0.6 | ? 0.6 | ||
| Colloidal silica (j): ア エ ロ ジ Le 130 ( *2) | ? 7.5 | ? 7.5 | ? 7.5 | ? 7.5 | ? 7.5 | ? 7.5 | ? 7.5 | ||
| The surface lubrication compositions | Multi-functional polymerizable monomer (f): DPHA | ? 73 | ? 73 | ? 73 | ? 73 | ? 83 | ? 83 | ? 83 | |
| Volatile solvent (g): MMA | ? 25 | ? 25 | ? 25 | ? 25 | ? 15 | ? 15 | ? 15 | ||
| Photoepolymerizationinitiater initiater (h): TMDPO | ? 2 | ? 2 | ? 2 | ? 2 | ? 2 | ? 2 | ? 2 | ||
| Adhesion strength (MPa) | 16.0 | 15.1 | 15.7 | 14.9 | 18.5 | 17.8 | 18.2 | ||
| Anti-stripping bits property | Reciprocal 10000 times reciprocal 20000 times reciprocal 40000 times | ○ ○ ○ | ○ ○ ○ | ○ ○ ○ | ○ ○ ○ | ○ ○ ○ | ○ ○ ○ | ○ ○ ○ | |
| The variation of brightness (Δ L *) | 8.1 | 17.1 | 19.5 | 22.5 | 17.4 | 17.3 | 17.0 | ||
| ?? *1: with day office's titanium dioxide powder of γ-methacryloxypropyl trimethoxy silane processing *2: Japanese ア エ ロ ジ Le company's manufacturing (trade name) | |||||||||
Table 6
| Cooperation ratio (weight %) in each compositions | ||||||||||
| Embodiment 30 | Embodiment 31 | Embodiment 32 | Embodiment 33 | Embodiment 34 | Embodiment 35 | Embodiment 36 | Embodiment 37 | |||
| Rendering composition | Contain acidic-group polymerizable monomer (a): MDP | ? 20 | ? 20 | ? 20 | ? 20 | ? 20 | ? 10 | ? 30 | ? 50 | |
| Water (b): distilled water | ? 40 | ? 25 | ? 25 | ? 25 | ? 25 | ? 30 | ? 20 | ? 15 | ||
| Water-soluble solvent (c): HEMA | ? 40 | ? 55 | ? 55 | ? 55 | ? 55 | ? 60 | ? 50 | ? 35 | ||
| The surface lubrication compositions | Multi-functional polymerizable monomer (f): DPHA | ? 73 | ? 73 | ? 83 | ? 88 | ? 93 | ? 88 | ? 88 | ? 88 | |
| Volatile solvent (g): MMA | ? 25 | ? 25 | ? 15 | ? 10 | ? 5 | ? 10 | ? 10 | ? 10 | ||
| Photoepolymerizationinitiater initiater (h): TMDPO | ? 2 | ? 2 | ? 2 | ? 2 | ? 2 | ? 2 | ? 2 | ? 2 | ||
| Adhesion strength (MPa) | 11.2 | 12.5 | 13.7 | 14.2 | 13.9 | 15.3 | 14.8 | 15.6 | ||
| Anti-stripping bits property | Reciprocal 10000 times reciprocal 20000 times reciprocal 40000 times | ○ ○ × | ○ ○ × | ○ ○ × | ○ ○ × | ○ ○ × | ○ ○ × | ○ ○ × | ○ ○ × | |
As show shown in the 3-5, use contains the 2nd test kit of rendering composition, coating composition and surface lubrication compositions, when forming the coating of 3-tier architecture on tooth, the gained coating shows excellent adhesion strength to tooth, and anti-stripping bits property excellence (embodiment 13-29).Relative therewith, as shown in table 3, do not use rendering composition and coating composition, the surface lubrication compositions is directly coated the surface of tooth, when forming signal layer coating, the caking property of gained coating and tooth low (comparative example 5,6).In addition, as shown in table 6, do not use coating composition, be coated with rendering composition and surface lubrication compositions successively on the surface of tooth, when forming the coating of 2 layers of structure, the adhesion strength excellence, but anti-stripping bits property is poor.
(embodiment 30-37)
As shown in table 5, to use to have that to contain refractive index be 1.9 or the 2nd test kit of the coating composition of above inorganic filler, when forming the coating of 3-tier architecture on tooth, by coating, the brightness that can improve tooth makes aesthetics improve (embodiment 23-29).
Industrial applicability
Dental coating kit of the present invention is particularly useful as the kit that is used for preventing bleaching rear tooth staining and look rollback.
Claims (15)
1. dental coating kit, this test kit has rendering composition and surface lubrication compositions, wherein said rendering composition contains acidic-group polymerizable monomer (a), water (b) and water-soluble solvent (c), and described surface lubrication compositions contains multi-functional polymerizable monomer (f), volatile solvent (g) and Photoepolymerizationinitiater initiater (h).
2. the dental coating kit of claim 1, wherein above-mentioned rendering composition contains the water (b) that contains acidic-group polymerizable monomer (a), 0.1 weight %-90 weight % of 1-90 weight %, the water-soluble solvent (c) of 1 weight %-98 weight %; Above-mentioned surface lubrication compositions contain 40 weight %-98 weight % multi-functional polymerizable monomer (f), 1 weight %-59 weight % volatile solvent (g) and be the Photoepolymerizationinitiater initiater (h) of 0.01 weight %-10 weight % with respect to the total weight of the polymerizable monomer in this surface lubrication compositions.
3. claim 1 or 2 dental coating kit, wherein above-mentioned Photoepolymerizationinitiater initiater (h) is an acylphosphine oxide.
4. the dental coating kit of claim 3, wherein above-mentioned acylphosphine oxide is 2,4,6-trimethylbenzoyl diphenyl phosphine oxide.
5. each dental coating kit among the claim 1-4, wherein above-mentioned surface lubrication compositions is 30cP-3000cP 30 ℃ viscosity.
6. each dental coating kit among the claim 1-5, this test kit are the coating kits of bleaching back tooth.
7. dental coating method wherein contains the rendering composition of acidic-group polymerizable monomer (a), water (b), water-soluble solvent (c) and polymerization initiator as required in the surface coated of tooth, make its drying or polymerizing curable, forms prime coat; Contain the surface lubrication compositions of multi-functional polymerizable monomer (f), volatile solvent (g) and Photoepolymerizationinitiater initiater (h) in the surface coated of this prime coat, make its polymerizing curable, form surface layer by rayed.
8. dental coating kit, this test kit has rendering composition, coating composition and surface lubrication compositions, and wherein, described rendering composition contains acidic-group polymerizable monomer (a), water (b) and water-soluble solvent (c); Coating composition contains polymerizable monomer (d) and Photoepolymerizationinitiater initiater (e); The surface lubrication compositions contains multi-functional polymerizable monomer (f), volatile solvent (g) and Photoepolymerizationinitiater initiater (h).
9. the dental coating kit of claim 8, wherein above-mentioned rendering composition contains the water (b) that contains acidic-group polymerizable monomer (a), 0.1 weight %-90 weight % of 1 weight %-90 weight %, the water-soluble solvent (c) of 1 weight %-98 weight %; Above-mentioned coating composition contains the polymerizable monomer (d) of 40 weight %-99.99 weight % and is the Photoepolymerizationinitiater initiater (e) of 0.01 weight %-10 weight % with respect to above-mentioned polymerizable monomer (d); Above-mentioned surface lubrication compositions contain 40 weight %-98 weight % multi-functional polymerizable monomer (f), 1 weight %-59 weight % volatile solvent (g) and be the Photoepolymerizationinitiater initiater (h) of 0.01 weight %-10 weight % with respect to the total weight of the polymerizable monomer in this surface lubrication compositions.
10. claim 8 or 9 dental coating kit also contain refractive index and are 1.9 or above inorganic filler and colloidal silica in the wherein above-mentioned coating composition.
11. each dental coating kit among the claim 8-10, wherein above-mentioned coating composition is 300cP-50 30 ℃ viscosity, 000cP.
12. each dental coating kit among the claim 8-11, wherein above-mentioned polymerizable monomer (d) contains hydrophobicity polymerizable monomer and hydrophilic polymer monomer, and above-mentioned coating composition contains this hydrophilic polymer monomer of 5 weight %-50 weight %.
13. the dental coating kit of claim 12, wherein above-mentioned hydrophilic polymer monomer is a 2-hydroxyethyl methacrylate.
14. each dental coating kit among the claim 8-13, this test kit are the coating kits of bleaching back tooth.
15. the dental coating method wherein contains the rendering composition of acidic-group polymerizable monomer (a), water (b), water-soluble solvent (c) and polymerization initiator as required in the surface coated of tooth, make its drying or polymerizing curable, forms prime coat; Contain the coating composition of polymerizable monomer (d) and Photoepolymerizationinitiater initiater (e) in the surface coated of this prime coat, make its polymerizing curable, form the intermediate layer by rayed; Surface coated in this intermediate layer contains the surface lubrication compositions of multi-functional polymerizable monomer (f), volatile solvent (g) and Photoepolymerizationinitiater initiater (h), makes its polymerizing curable by rayed, forms surface layer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP294821/2002 | 2002-10-08 | ||
| JP2002294821 | 2002-10-08 | ||
| JP366253/2002 | 2002-12-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101283799A Division CN101322676B (en) | 2002-10-08 | 2003-10-06 | Dental coating kit |
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| Publication Number | Publication Date |
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| CN1703185A true CN1703185A (en) | 2005-11-30 |
| CN100415199C CN100415199C (en) | 2008-09-03 |
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| CN2008101283799A Expired - Fee Related CN101322676B (en) | 2002-10-08 | 2003-10-06 | Dental coating kit |
| CNB2003801010301A Expired - Fee Related CN100415199C (en) | 2002-10-08 | 2003-10-06 | Dental coating kit |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2008101283799A Expired - Fee Related CN101322676B (en) | 2002-10-08 | 2003-10-06 | Dental coating kit |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111297698A (en) * | 2020-03-26 | 2020-06-19 | 山东理工大学 | Dental binder, preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101322676B (en) * | 2002-10-08 | 2011-03-30 | 日本可乐丽医疗器材株式会社 | Dental coating kit |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11180814A (en) * | 1997-12-24 | 1999-07-06 | Gc:Kk | Dentine adhesive set |
| JP4176196B2 (en) * | 1998-06-29 | 2008-11-05 | 株式会社クラレ | Dental adhesive system |
| TWI262795B (en) * | 1999-05-31 | 2006-10-01 | Kuraray Co | Adhesive composition and method for producing it |
| CN101322676B (en) * | 2002-10-08 | 2011-03-30 | 日本可乐丽医疗器材株式会社 | Dental coating kit |
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- 2003-10-06 CN CN2008101283799A patent/CN101322676B/en not_active Expired - Fee Related
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111297698A (en) * | 2020-03-26 | 2020-06-19 | 山东理工大学 | Dental binder, preparation method and application thereof |
| CN111297698B (en) * | 2020-03-26 | 2023-03-21 | 山东理工大学 | Dental binder, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100415199C (en) | 2008-09-03 |
| CN101322676A (en) | 2008-12-17 |
| CN101322676B (en) | 2011-03-30 |
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