CN102512334B - Preparation method of oral care composition - Google Patents
Preparation method of oral care composition Download PDFInfo
- Publication number
- CN102512334B CN102512334B CN 201210005775 CN201210005775A CN102512334B CN 102512334 B CN102512334 B CN 102512334B CN 201210005775 CN201210005775 CN 201210005775 CN 201210005775 A CN201210005775 A CN 201210005775A CN 102512334 B CN102512334 B CN 102512334B
- Authority
- CN
- China
- Prior art keywords
- oral care
- copolymer
- zinc citrate
- methyl ether
- maleic anhydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000203 mixture Substances 0.000 title abstract description 40
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 claims abstract description 38
- 239000011746 zinc citrate Substances 0.000 claims abstract description 38
- 235000006076 zinc citrate Nutrition 0.000 claims abstract description 38
- 229940068475 zinc citrate Drugs 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims description 16
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 abstract description 27
- 230000000694 effects Effects 0.000 abstract description 25
- 229940034610 toothpaste Drugs 0.000 abstract description 21
- 239000000606 toothpaste Substances 0.000 abstract description 21
- 210000000214 mouth Anatomy 0.000 abstract description 14
- -1 poly(vinyl methylether) Polymers 0.000 abstract description 7
- 208000002064 Dental Plaque Diseases 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 5
- 230000002401 inhibitory effect Effects 0.000 abstract description 5
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 abstract 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 37
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical class C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 13
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 description 12
- 229960003500 triclosan Drugs 0.000 description 12
- 208000006558 Dental Calculus Diseases 0.000 description 10
- 230000000844 anti-bacterial effect Effects 0.000 description 10
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 10
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 102000004190 Enzymes Human genes 0.000 description 7
- 108090000790 Enzymes Proteins 0.000 description 7
- 239000000080 wetting agent Substances 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 6
- 206010044029 Tooth deposit Diseases 0.000 description 6
- 230000001580 bacterial effect Effects 0.000 description 6
- 239000000600 sorbitol Substances 0.000 description 6
- 235000010356 sorbitol Nutrition 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 5
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 5
- 230000003385 bacteriostatic effect Effects 0.000 description 5
- 235000015165 citric acid Nutrition 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 229940041616 menthol Drugs 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 208000007565 gingivitis Diseases 0.000 description 4
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 4
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 4
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 4
- 239000009637 wintergreen oil Substances 0.000 description 4
- 239000000230 xanthan gum Substances 0.000 description 4
- 235000010493 xanthan gum Nutrition 0.000 description 4
- 229920001285 xanthan gum Polymers 0.000 description 4
- 229940082509 xanthan gum Drugs 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 229920002907 Guar gum Polymers 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 3
- 239000001506 calcium phosphate Substances 0.000 description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 description 3
- 235000011010 calcium phosphates Nutrition 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 210000004195 gingiva Anatomy 0.000 description 3
- 239000000665 guar gum Substances 0.000 description 3
- 235000010417 guar gum Nutrition 0.000 description 3
- 229960002154 guar gum Drugs 0.000 description 3
- 125000001165 hydrophobic group Chemical group 0.000 description 3
- 239000010977 jade Substances 0.000 description 3
- 235000016709 nutrition Nutrition 0.000 description 3
- 230000035764 nutrition Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 3
- FTLYMKDSHNWQKD-UHFFFAOYSA-N (2,4,5-trichlorophenyl)boronic acid Chemical compound OB(O)C1=CC(Cl)=C(Cl)C=C1Cl FTLYMKDSHNWQKD-UHFFFAOYSA-N 0.000 description 2
- QCZAWDGAVJMPTA-RNFRBKRXSA-N ClC1=CC=CC(=N1)C1=NC(=NC(=N1)N[C@@H](C(F)(F)F)C)N[C@@H](C(F)(F)F)C Chemical compound ClC1=CC=CC(=N1)C1=NC(=NC(=N1)N[C@@H](C(F)(F)F)C)N[C@@H](C(F)(F)F)C QCZAWDGAVJMPTA-RNFRBKRXSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 208000032843 Hemorrhage Diseases 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 102000045595 Phosphoprotein Phosphatases Human genes 0.000 description 2
- 108700019535 Phosphoprotein Phosphatases Proteins 0.000 description 2
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 2
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 2
- 244000269722 Thea sinensis Species 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 239000000022 bacteriostatic agent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 210000004268 dentin Anatomy 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000007937 lozenge Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 210000004379 membrane Anatomy 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 210000002200 mouth mucosa Anatomy 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229940085605 saccharin sodium Drugs 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 description 2
- RUVINXPYWBROJD-ONEGZZNKSA-N trans-anethole Chemical compound COC1=CC=C(\C=C\C)C=C1 RUVINXPYWBROJD-ONEGZZNKSA-N 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 244000166124 Eucalyptus globulus Species 0.000 description 1
- 235000004692 Eucalyptus globulus Nutrition 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- 206010018276 Gingival bleeding Diseases 0.000 description 1
- 208000024283 Gingival haemorrhages Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000699670 Mus sp. Species 0.000 description 1
- 208000025157 Oral disease Diseases 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 239000005844 Thymol Substances 0.000 description 1
- AUYYCJSJGJYCDS-LBPRGKRZSA-N Thyrolar Chemical group IC1=CC(C[C@H](N)C(O)=O)=CC(I)=C1OC1=CC=C(O)C(I)=C1 AUYYCJSJGJYCDS-LBPRGKRZSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229940011037 anethole Drugs 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000000170 anti-cariogenic effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 206010003119 arrhythmia Diseases 0.000 description 1
- 230000006793 arrhythmia Effects 0.000 description 1
- 230000037358 bacterial metabolism Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000227 bioadhesive Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 1
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 1
- 239000000679 carrageenan Substances 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 229940113118 carrageenan Drugs 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000013066 combination product Substances 0.000 description 1
- 229940127555 combination product Drugs 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 208000002925 dental caries Diseases 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001647 drug administration Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229960005150 glycerol Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid group Chemical group C(\C=C/C(=O)O)(=O)O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 229940044600 maleic anhydride Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013521 mastic Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 208000030194 mouth disease Diseases 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- RUVINXPYWBROJD-UHFFFAOYSA-N para-methoxyphenyl Natural products COC1=CC=C(C=CC)C=C1 RUVINXPYWBROJD-UHFFFAOYSA-N 0.000 description 1
- 208000028169 periodontal disease Diseases 0.000 description 1
- 201000001245 periodontitis Diseases 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229960000790 thymol Drugs 0.000 description 1
- 239000005495 thyroid hormone Substances 0.000 description 1
- 229940036555 thyroid hormone Drugs 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 229940091251 zinc supplement Drugs 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
Images
Abstract
The invention discloses a preparation method of the oral care product. The oral care composition is composed of a poly(vinyl methylether)/malaic anhydride copolymer and zinc citrate, wherein the mass ratio of the poly(vinyl methylether)/malaic anhydride copolymer to the zinc citrate is in a range from 1:5 to 1:3.According to the composition provided by the invention, the efficacy of the zinc citrate is doubled and the efficacies of the zinc citrate on nourishing gingva and inhibiting dental plaques can be slowly released through a biological film which is formed on the surfaces of the teeth by the copolymer, so that the oral cavity is in a protected state for a long time; and the two components are safe and moderate and have no toxic or side effects on human bodies. The oral care composition can be applied to toothpaste formulas with different efficacies so that the action time of functional components can be prolonged.
Description
Technical field
The present invention relates to field of oral care, be specifically related to a kind of preparation method of oral care product.
Background technology
Vinyl methyl ether/copolymer-maleic anhydride is called for short the PVM/MA copolymer, is a kind of effective inhibitor of alkali phosphatase, and is harmless to the human body totally nontoxic.This high-molecular copolymer can come the activity of inhibitory enzyme by the metal ion (as zinc, magnesium etc.) of chelatase active site.Naturally the calcium phosphate that forms in the oral cavity generally can form the crystal seed of dental calculus and tartar at dental surface, when growing up to about 50nm, crystal seed will become ripe tartar, if in the oral cavity, use the combination of PVM/MA copolymer/pyrophosphate/sodium fluoride, it can attack the crystal seed of tartar, make its dissolving, and recovery calcium phosphate, help remineralization of teeth.The technical staff of Colgate-Palmolive company has at first reported triclosan and high molecular polymer and has constituted effective system antibacterial in the toothpaste, sterilization together in scientific research, plays the effect for the treatment of and prevention in the oral cavity.Nineteen ninety, Nabi and Gaffar have obtained U.S. Patent number about the technology that pure as jade pure and mild PVM/MA is used for oral-cavity article: 4,894,220.Colgate-Palmolive company should antibiotic system be successfully used in the products such as the full effective toothpaste of Colgate-Palmolive.
Zinc citrate is white powder, and is water-soluble slightly, is soluble in dilute hydrochloric acid and the alkaline solution.Geometric configuration is: center zinc atom and the middle hydroxyl of two citric acids and a terminal carboxyl group phase bonding of middle carboxyl and each citric acid constitute new octahedral structure.Bibliographical information the has been arranged absorbing state of zinc citrate.Citric acid is the good chelating body of bivalent cation, and zinc exists very name to have preferably with the form of zinc citrate to absorb.Zinc citrate has been proved to be naturally occurring physiologically substance in the human body, and many physiological activities and the growth of children of human body had very important effect; And characteristics such as having the zinc content height, absorb fast, free from extraneous odour, be without any side effects are comparatively ideal organic zinc supplement agent at present.The anion of citrate more can produce the nonionic complex with the cation calcium on dentin and skeleton crystalloid surface; this citric acid complex has played the effect of protective agent and sealer; be used for formulation of tooth-paste; play promotion citric acid anion-permeable membrane simultaneously in dentin with the polyhydric alcohol wetting agent, lengthened the time of staying of nutrition.The toothpaste (addition is about 0.5%～1.0%) that adds zinc citrate can suppress the generation of dental plaque effectively, control gingivitis, dental calculus, dental hemorrhage and dental caries.
At present the oral care composition of report all is that copolymer reaches purpose antibacterial, that sterilize with triclosan or fluoride combined effect, though pointed out to suppress biological enzyme activity with some metal ion-chelant, but depended on composite long-acting bacteriostatic or the anticariogenic effect of realizing with triclosan or fluoride mostly.There are a lot of documents also to report simultaneously and pointed out that zinc salt has the excellent antibiotic performance, zinc energy bacteria growing inhibiting, the destruction bacterial plaque forms, influence antibacterial to the transhipment of sucrose, thereby reduce the ability of Production by Bacteria acid, the effect of zinc mainly is by disturbing the bacterial enzyme system, influencing due to the bacterial metabolism, another characteristics of zinc are to be stranded in oral mucosa and the bacterial plaque long period, keep Mlc.But a lot of technology all are that zinc salt is auxiliary effective component, with fluoride and pure as jade composite use such as pure.
Triclosan not only can act on gram positive bacteria but also can act on gram negative bacteria as a kind of spectrum antibacterial.The endochylema film that the antimicrobial main site of action of triclosan is antibacterial.Under Mlc, the energy tissue bacterial in the bacteriocidal concentration scope, can make antibacterial endochylema membrane structure destroy necessary amino acid whose picked-up, and cellular content leaks.But there is certain threat in triclosan to human body, about the side effect of triclosan, the professor of Virginia, US Polytechnics found through experiments, after containing the product of triclosan and chloride tap water and reacting, can form the material of a kind of being called as " chloroform ", just chloroform.And chloroform once was used as anesthetis, and animal experiment finds that this material can cause damage to heart and liver, has slight teratogenecity, can induce white mice that hepatocarcinoma takes place, and also can cause arrhythmia.U.S. food Drug Administration just announces that as far back as in April, 2010 startup is to the assessment of triclosan safety.Research worker finds that this sterilization component might disturb thyroid hormone function, even can make the part bacterial antibiotic produce repellence.But aspect its one's work " sterilization " may not than soap add clear water strong what.In the end of the year 2010, there is the Congressman in the U.S. even urges the U.S. to list triclosan in the forbidding list.Based on these drawbacks that triclosan exists, my department is devoted to development of new to the long-acting bacteriostatic combination product of human body safety.
Summary of the invention
The object of the present invention is to provide a kind of oral care composition and the oral care product and the method for making thereof that contain said composition, existing long-acting bacteriostatic agent is to obtain by copolymer and pure as jade pure synergism, and there is certain hazardness in human body.Zinc citrate is as a kind of safe and effective antibacterial, and at the control dental calculus, suppressing the dental plaque aspect has good effect.The present invention forms complex with copolymer and zinc citrate; as long-acting bacteriostatic combination agent (NFD active factors); the effect of zinc citrate is doubled; the biomembrane that copolymer forms at dental surface; the effect of zinc citrate nutrition gingiva, antibacterial dental plaque is slowly discharged; make the oral cavity be in long guard mode, and two kinds of compositions are all safe, gentle, and human body is had no side effect.This oral care composition is applied in the formulation of tooth-paste of different efficacies, can increase the action time of functional component.
The object of the invention is achieved through the following technical solutions.
The invention provides a kind of oral care composition:
Oral care composition is made up of vinyl methyl ether/copolymer-maleic anhydride and zinc citrate, and the mass ratio of therein ethylene base methyl ether/copolymer-maleic anhydride and zinc citrate is 1:5～1:3.
Vinyl methyl ether/copolymer-maleic anhydride and its preparation method are disclosed by prior art,
The application of described oral care composition in oral care products such as toothpaste, gel, collutory, powder, confectionery or lozenge.
The present invention also provides a kind of oral care product that contains oral care composition:
The colloid that the raw material of described oral care product also comprises, wetting agent and oral care product are used; The percentage by weight of oral care composition is 0.001%～12% in the described oral care product.
Described oral care product also comprises tetrasodium pyrophosphate.
Described wetting agent is more than one in Polyethylene Glycol, glycerol, water or the sorbitol.
The present invention also provides a kind of preparation method that contains the oral care product of oral care composition:
The preparation method of described oral care product may further comprise the steps:
The first step: vinyl methyl ether/copolymer-maleic anhydride is scattered in the wetting agent, stirs;
Second step: zinc citrate is added in the above-mentioned solution, stir;
The 3rd step: the colloid that the adding oral care product is used stirs into gel;
The 4th step: above-mentioned gel is carried out drying, pulverize, sieve.
Described wetting agent is more than one in Polyethylene Glycol, glycerol, water or the sorbitol.
In the colloid preferably carboxymethyl cellulose sodium that described oral care product is used, xanthan gum, guar gum, the carrageenan one or more.
Also be included in the described the 3rd and go on foot the step that adds tetrasodium pyrophosphate before.
Stabilizing agent tetrasodium pyrophosphate commonly used in this oral care composition and the toothpaste is used simultaneously, can suppress the deposition of calcium phosphate, suppress alkali phosphatase, can effectively control the generation of tartar.
Oral care composition of the present invention can be applied to comprise toothpaste, gel, and collutory, powder, confectionery, lozenge can make functional component slowly discharge at interior oral care product, reach the effect that doubles than common product effect.
The invention provides a kind of compositions of effective inhibitor and the oral care implement that novel nourishing antibacterial zinc citrate is formed of alkali phosphatase; product of the present invention adopts the original and advanced technology of high-quality; in the oral care product that adds; can help the functional component of product to continue long-acting; form one deck thin layer protecting film at dental surface; discharge effective ingredient slowly; reach long-acting bacteriostatic; effectively suppress dental plaque, alleviate periodontal disease, gingivitis, red swelling of gingiva, symptom such as hemorrhage,
The present invention has the following advantages: the first, the safety in utilization of oral care implement compositions provided by the invention, and biocompatibility has certain synergism for the stability of product; The second, two effective ingredient in the compositions provided by the invention, PVM/MA copolymer and zinc citrate have good synergisticing performance, and copolymer can improve the retention time of zinc citrate in the oral cavity, improves the absorbance of zinc citrate; Three, compositions provided by the invention is used in prescription, can strengthen the effect of product on the one hand, and the effect of existing product is doubled.And the utilization in oral care implement is more extensive.Four, the compositions scope of application of oral care implement provided by the invention is extensive, is applicable to multiple oral diseases such as periodontitis, gingivitis, gingival hemorrhage, dental calculus.
The copolymer that described oral cavity composition adopts, can be bonded on the avtive spot of enzyme, and with metal ion such as the chelatings such as zinc and magnesium on this avtive spot, thereby the activity of inhibitory enzyme, for alkali phosphatase the good restraining effect is arranged especially, have the effect that prevents dental calculus, the raw material tetrasodium pyrophosphate commonly used of this copolymer and toothpaste has good synergism, more effective removal tartar.This copolymer and antibacterial or essence and surfactant are made up, result of study shows, the PVM/MA copolymer can transmit and keep essence very effectively, so said composition can effectively keep and transmission as essence, freshener, flavorants and medicine etc. acting on the active component in oral cavity in prescription.
The PVM/MA copolymer that adds is added in basic toothpaste and the collutory prescription, observation is to active component and intake and the reservation amount of flavor component in the oral cavity of different essence and indissoluble, as: wintergreen oil, anethole, menthol, thymol, Folium eucalypti globueli (Eucalyptus globulus Labill.) wet goods, in vitro study shows, with the recipe ratio that does not contain polymer, the PVM/MA copolymer can improve essence in toothpaste and the collutory prescription and intake and the reservation amount of active component effectively, and then effectively control the generation of tooth stain and bacterial gingivitis, can also strengthen the durable aroma in oral cavity.This is the structures shape that PVM/MA is arranged, and has hydrophilic group and hydrophobic group in its chemical constitution simultaneously, and hydrophilic group is maleic acid functional group (or its hydrolysis derivative), and hydrophobic group is polymer backbone and vinyl methyl ether side-chain structure.Hydrophilic group provides chelating and coordination ability, has also strengthened the bioadhesive to oral mucosa and tooth excellence simultaneously; Hydrophobic group then increases insoluble compound at the bioavailability in oral cavity by hydrophobic interaction, so uses in oral care product in the PVM/MA copolymer and essence, surfactant can be sticked to oral mucosal surface and form the effect that bank reaches slow release.
With zinc citrate and the composite use of PVM/MA copolymer, compare with the mastic of independent interpolation zinc citrate, copolymer can prolong the residence time of zinc citrate in the oral cavity.Copolymer can be bonded on the avtive spot of enzyme, and with this avtive spot on the metallic zinc ion chelating, the effective activity of inhibitory enzyme prolongs action time of zinc ion.The zinc citrate of composite different proportion and PVM/MA copolymer are chosen zinc citrate time of staying proportioning more of a specified duration.
Advantage and beneficial effect that the present invention has with respect to prior art:
The present invention has excellent biological compatibility, stable, long-acting compared with prior art, with the raw material in the formulation of tooth-paste system good synergism is arranged, such as: wetting agent, pyrophosphate, Chinese medicine extract etc., prolong the residual and action time of zinc citrate in the oral cavity, better bring into play the effect of nutrition gingiva and long-acting bacteriostatic.NFD active factors of the present invention is as a kind of long-acting bacteriostatic agent, the safety that increases than the combination of existing triclosan and effectively.
Description of drawings
Fig. 1 for the toothpaste that uses toothpaste that oral care composition is arranged and no oral care composition brush teeth before and after dish go up the luminosity (L* value) that tea steeps.
The specific embodiment
Embodiment 1
Oral care product of the present invention consists of: vinyl methyl ether/copolymer-maleic anhydride, Polyethylene Glycol, zinc citrate and sodium carboxymethyl cellulose; The mass ratio of therein ethylene base methyl ether/copolymer-maleic anhydride and zinc citrate is 1:3.The weight average relative molecular weight of vinyl methyl ether/copolymer-maleic anhydride is 12000.
The preparation method that contains the oral care product of this oral care composition is:
The first step: take by weighing PVM/MA copolymer 0.1g and be scattered in evenly to be stirred in the 3g Polyethylene Glycol and disperse fully.
Second step: take by weighing the 0.3g zinc citrate and add in the above-mentioned mixed liquor, stir and form even mixed liquor.
The 3rd step: add the 0.1g sodium carboxymethyl cellulose and stir into even gel.
The 4th step: with above-mentioned gel carry out drying, pulverize, sieving obtains powder or granular oral care product.
Dissolving in wintergreen oil, solubilizing agent, the antiseptic adding ethanol is obtained water, oral care product is added the aqueous phase of collutory, and add the saccharin sodium stirring fully, add sorbitol and glycerol wetting agent, oil phase is added aqueous phase, and mix homogeneously obtains collutory.
The effect of collutory is as follows:
Contain that the active component wintergreen oil is 1.7 μ g in reservation amount on the hydroxyapatite dish in the collutory of oral care composition, and do not contain oral care composition in the contrast collutory, wintergreen oil reservation amount on the hydroxyapatite dish is 0.7 μ g,
Embodiment 2
Oral care product of the present invention consists of: vinyl methyl ether/copolymer-maleic anhydride, glycerol, zinc citrate and guar gum; The mass ratio of therein ethylene base methyl ether/copolymer-maleic anhydride and zinc citrate is 1:5.
The preparation method that contains the oral care product of this oral care composition is:
The first step: take by weighing PVM/MA copolymer 0.01g and be scattered in evenly to be stirred in the 100g glycerol and disperse fully.
Second step: take by weighing the 0.05g zinc citrate and add in the above-mentioned mixed liquor, stir and form even mixed liquor.
The 3rd step: add the 5000g guar gum and stir into even gel.
The 4th step: with above-mentioned gel carry out drying, pulverize, sieving obtains powder or granular oral care product.
Effect is as follows:
Contain add menthol in the oral care product of oral care composition after, menthol reservation amount on the hydroxyapatite dish is 40 μ g, menthol reservation amount on the hydroxyapatite dish only is 27 μ g in the oral care product of oral care composition (PVM/MA copolymer and zinc citrate) and Comparative Examples does not contain
Embodiment 3
Oral care product of the present invention consists of: vinyl methyl ether/copolymer-maleic anhydride, sorbitol, zinc citrate, tetrasodium pyrophosphate and xanthan gum; The mass ratio of therein ethylene base methyl ether/copolymer-maleic anhydride and zinc citrate is 1:4.
The preparation method that contains the oral care product of this oral care composition is:
The first step: take by weighing PVM/MA copolymer 0.1g and be scattered in evenly to be stirred in the 5g sorbitol and disperse fully.
Second step: take by weighing the 0.4g zinc citrate and add in the above-mentioned mixed liquor, stir and form even mixed liquor, add the 0.1g tetrasodium pyrophosphate;
The 3rd step: add the 0.2g xanthan gum and stir into even gel.
The 4th step: with above-mentioned gel carry out drying, pulverize, sieving obtains powder or granular oral care product.
Oral care product is dispersed in the Polyethylene Glycol, adds xanthan gum, the preparation colloid stirs; Sorbitol, saccharin sodium aqueous phase system is soluble in water, add toothpaste with abrasive material, foaming agent, stir; Colloid is added in the mixed system of water and powder and stir, menthol is dissolved in adds mixed system in the essence and stir, make toothpaste.
Effect is as follows:
Contrast contains the toothpaste of no oral care composition of tetrasodium pyrophosphate, with the whitening effect of the toothpaste that oral care composition is arranged that contains tetrasodium pyrophosphate, adopts the simulation experimental technique of brushing teeth, the luminosity (L* value) that dish was gone up the tea stain before and after test was brushed teeth as shown in Figure 1:
Can be drawn by experiment, the toothpaste and the tetrasodium pyrophosphate that contain oral care composition have good synergism, are more clear than the effect of the removal tartar of the whitening toothpaste of common tetrasodium pyrophosphate.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also change and revise above-mentioned embodiment.Therefore, the specific embodiment that discloses and describe above the present invention is not limited to also should fall in the protection domain of claim of the present invention modifications and changes more of the present invention.In addition, although used some specific terms in this description, these terms do not constitute any restriction to the present invention just for convenience of description.
Claims (1)
1. the preparation method of an oral care product is characterized in that, may further comprise the steps:
The first step: take by weighing vinyl methyl ether/copolymer-maleic anhydride 0.1g and be scattered in evenly to be stirred in the 3g Polyethylene Glycol and disperse fully;
Second step: take by weighing the 0.3g zinc citrate and add in the above-mentioned mixed liquor, stir and form even mixed liquor;
The 3rd step: add the 0.1g sodium carboxymethyl cellulose and stir into even gel;
The 4th step: with above-mentioned gel carry out drying, pulverize, sieving obtains powder or granular oral care product;
The mass ratio of therein ethylene base methyl ether/copolymer-maleic anhydride and zinc citrate is 1:3; The weight average relative molecular weight of vinyl methyl ether/copolymer-maleic anhydride is 12000;
Wherein described above-mentioned mixed liquor of second step refers to take by weighing vinyl methyl ether/copolymer-maleic anhydride 0.1g and is scattered in evenly to be stirred in the 3g Polyethylene Glycol and disperses the mixed liquor that is completed into.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210005775 CN102512334B (en) | 2012-01-10 | 2012-01-10 | Preparation method of oral care composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210005775 CN102512334B (en) | 2012-01-10 | 2012-01-10 | Preparation method of oral care composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102512334A CN102512334A (en) | 2012-06-27 |
| CN102512334B true CN102512334B (en) | 2013-07-17 |
Family
ID=46283599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210005775 Active CN102512334B (en) | 2012-01-10 | 2012-01-10 | Preparation method of oral care composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102512334B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104027913B (en) * | 2014-06-06 | 2017-02-15 | 中国矿业大学(北京) | Composite oxidation inhibitor for preventing spontaneous combustion of coal gangue and application amount thereof |
| CN105213211A (en) * | 2014-06-30 | 2016-01-06 | 北京斯利安制药有限公司 | A kind of collutory containing folic acid and preparation method thereof |
| CN104257544B (en) * | 2014-09-17 | 2017-05-31 | 名臣健康用品股份有限公司 | A kind of linkage of tetrad method is dispelled halitosis composition toothpaste |
| CN106619187B (en) * | 2017-01-24 | 2019-07-16 | 广州薇美姿实业有限公司 | A kind of composition of pre- dental calculus preventing and application |
| CN107028784A (en) * | 2017-03-13 | 2017-08-11 | 广州薇美姿实业有限公司 | A kind of oral care implement of fresh breath and preparation method thereof |
| CN111346023A (en) * | 2020-04-15 | 2020-06-30 | 广州立白企业集团有限公司 | Plant bacteriostatic composition, mouthwash containing composition and preparation method of mouthwash |
| CN111803401A (en) * | 2020-08-03 | 2020-10-23 | 广州佩奇生物科技有限公司 | Oral care composition, tooth powder, toothpaste and mouthwash |
| CN115463043A (en) * | 2022-08-25 | 2022-12-13 | 克劳丽化妆品股份有限公司 | Oral care composition and mouthwash |
-
2012
- 2012-01-10 CN CN 201210005775 patent/CN102512334B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| 中国广播网(北京).舒客NFD活性因子 全民口腔健康益起来.《http://news.163.com/11/0923/21/7ELRBVOT00014JB5.html》.2011,第1-2页. |
| 舒客NFD活性因子 全民口腔健康益起来;中国广播网(北京);《http://news.163.com/11/0923/21/7ELRBVOT00014JB5.html》;20110923;第1-2页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102512334A (en) | 2012-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102512334B (en) | Preparation method of oral care composition | |
| AU2019200755B2 (en) | Oral care compositions | |
| TWI556834B (en) | Surfactant systems for zinc containing compositions | |
| US11813342B2 (en) | Oral care compositions and methods of use | |
| TWI507211B (en) | Two component compositions containing tetrabasic zinc-amino acid halide complexes and cysteine | |
| CN102176890B (en) | Containing the oral care composition of capsule | |
| CN101123936B (en) | Oral compositions containing oxidized camellia | |
| TWI515016B (en) | Oral care compositions | |
| US20080031831A1 (en) | Oral anti-calculus compositions and methods of use thereof | |
| TW201803546A (en) | Oral care compositions and methods of use | |
| JP2011526245A (en) | Oral composition and use thereof | |
| CN105120959A (en) | Oral care compositions containing polyorganosilsesquioxane particles | |
| CN105101945A (en) | Oral care compositions containing polyorganosilsesquioxane particles | |
| US6861048B2 (en) | Dentifrice compositions having reduced abrasivity | |
| AU2009212339B2 (en) | Tooth sealant | |
| CA2408776C (en) | Process for making personal care compositions comprising titanium dioxide and personal care compositions made by the process | |
| RU2739381C1 (en) | Compositions for oral care | |
| AU2015419238B2 (en) | Oral care product and methods of use and manufacture thereof | |
| CA3164657A1 (en) | Oral care compositions and methods of use | |
| CN114096225B (en) | Oral care compositions comprising Jiang Erchun and methods of making the same | |
| JP2007091737A (en) | Oral composition | |
| JPH05117157A (en) | Preventive and therapeutic agent for hyperesthesia of dentin and composition for oral cavity containing the same preventive and therapeutic agent | |
| JP2015178462A (en) | Oral rinsing agent of ibuprofen | |
| CA3213370A1 (en) | Oral care compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Preparation method of oral care composition Effective date of registration: 20131213 Granted publication date: 20130717 Pledgee: Guangzhou first pawn Co., Ltd. Pledgor: Guangzhou Weimeizi Personal Care Supplies Co., Ltd. Registration number: 2013990000969 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| ASS | Succession or assignment of patent right |
Owner name: GUANGZHOU WEIMEIZI INDUSTRIAL CO., LTD. Free format text: FORMER OWNER: GUANGZHOU WEIMEIZI PERSONAL CARE PRODUCTS CO., LTD. Effective date: 20150511 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 510665 GUANGZHOU, GUANGDONG PROVINCE TO: 510655 GUANGZHOU, GUANGDONG PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20150511 Address after: 510655, 64, 66, West 704 and 705, Jianzhong Road, Guangzhou, Guangdong, Tianhe District Patentee after: Guangzhou Weimeizi Industrial Co., Ltd. Address before: 510665 Guangdong city of Guangzhou province Tianhe District Road 51 new science and Technology Building 1 building 402 room Patentee before: Guangzhou Weimeizi Personal Care Supplies Co., Ltd. |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20150407 Granted publication date: 20130717 Pledgee: Guangzhou first pawn Co., Ltd. Pledgor: Guangzhou Weimeizi Personal Care Supplies Co., Ltd. Registration number: 2013990000969 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210430 Address after: 510555 room 922, No.2, Tengfei 1st Street, Zhongxin Guangzhou Knowledge City, Huangpu District, Guangzhou City, Guangdong Province (office only) Patentee after: Guangzhou Shuke Industrial Co.,Ltd. Address before: 510655 rooms 704 and 705, West, No.64 and 66 Jianzhong Road, Tianhe District, Guangzhou City, Guangdong Province Patentee before: GUANGZHOU WEIMEIZI INDUSTRIAL Co.,Ltd. |
|
| TR01 | Transfer of patent right |