CN109833214B - Mild oil-in-water type pickering sunscreen skin care product and preparation method thereof - Google Patents
Mild oil-in-water type pickering sunscreen skin care product and preparation method thereof Download PDFInfo
- Publication number
- CN109833214B CN109833214B CN201910193114.5A CN201910193114A CN109833214B CN 109833214 B CN109833214 B CN 109833214B CN 201910193114 A CN201910193114 A CN 201910193114A CN 109833214 B CN109833214 B CN 109833214B
- Authority
- CN
- China
- Prior art keywords
- sunscreen
- oil
- skin care
- care product
- water
- 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.)
- Expired - Fee Related
Links
- 230000000475 sunscreen effect Effects 0.000 title claims abstract description 76
- 239000000516 sunscreening agent Substances 0.000 title claims abstract description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229940104261 taurate Drugs 0.000 claims abstract description 20
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 19
- 239000011734 sodium Substances 0.000 claims abstract description 19
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 19
- -1 dimethyl taurate Chemical compound 0.000 claims abstract description 17
- 239000011787 zinc oxide Substances 0.000 claims abstract description 16
- 239000002562 thickening agent Substances 0.000 claims abstract description 15
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 12
- 239000003974 emollient agent Substances 0.000 claims abstract description 10
- 239000003906 humectant Substances 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 230000037307 sensitive skin Effects 0.000 claims abstract description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- 239000003921 oil Substances 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 12
- 229920002545 silicone oil Polymers 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 9
- 235000011187 glycerol Nutrition 0.000 claims description 8
- UIVPNOBLHXUKDX-UHFFFAOYSA-N 3,5,5-trimethylhexyl 3,5,5-trimethylhexanoate Chemical compound CC(C)(C)CC(C)CCOC(=O)CC(C)CC(C)(C)C UIVPNOBLHXUKDX-UHFFFAOYSA-N 0.000 claims description 7
- BQMNFPBUAQPINY-UHFFFAOYSA-N azane;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound [NH4+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C BQMNFPBUAQPINY-UHFFFAOYSA-N 0.000 claims description 7
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N benzoic acid ethyl ester Natural products CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 7
- 229940100554 isononyl isononanoate Drugs 0.000 claims description 7
- 239000006210 lotion Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 230000001804 emulsifying effect Effects 0.000 claims description 6
- 239000006071 cream Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 239000003755 preservative agent Substances 0.000 claims description 3
- 230000002335 preservative effect Effects 0.000 claims description 3
- 230000002421 anti-septic effect Effects 0.000 claims description 2
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims 3
- IEKHISJGRIEHRE-UHFFFAOYSA-N 16-methylheptadecanoic acid;propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O.CC(C)CCCCCCCCCCCCCCC(O)=O IEKHISJGRIEHRE-UHFFFAOYSA-N 0.000 claims 2
- 241000221095 Simmondsia Species 0.000 claims 2
- 235000004433 Simmondsia californica Nutrition 0.000 claims 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims 2
- 239000000463 material Substances 0.000 claims 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims 2
- 229960003493 octyltriethoxysilane Drugs 0.000 claims 2
- 229940089951 perfluorooctyl triethoxysilane Drugs 0.000 claims 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims 2
- AVYKQOAMZCAHRG-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AVYKQOAMZCAHRG-UHFFFAOYSA-N 0.000 claims 2
- FJVWEMXTRKQOPG-NRFANRHFSA-N (2s)-2-(octadecylamino)pentanedioic acid Chemical compound CCCCCCCCCCCCCCCCCCN[C@H](C(O)=O)CCC(O)=O FJVWEMXTRKQOPG-NRFANRHFSA-N 0.000 claims 1
- QEYATHUQKXAPIM-NRFANRHFSA-N (4s)-4-amino-5-octadecoxy-5-oxopentanoic acid Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)[C@@H](N)CCC(O)=O QEYATHUQKXAPIM-NRFANRHFSA-N 0.000 claims 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 238000012216 screening Methods 0.000 abstract description 12
- 239000003995 emulsifying agent Substances 0.000 abstract description 10
- 239000000843 powder Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 230000037072 sun protection Effects 0.000 abstract description 2
- 210000004243 sweat Anatomy 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 48
- 238000012360 testing method Methods 0.000 description 20
- 235000019198 oils Nutrition 0.000 description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 229920006037 cross link polymer Polymers 0.000 description 4
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 description 4
- 239000002537 cosmetic Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 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 2
- 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 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 235000018330 Macadamia integrifolia Nutrition 0.000 description 2
- 240000000912 Macadamia tetraphylla Species 0.000 description 2
- 235000003800 Macadamia tetraphylla Nutrition 0.000 description 2
- 206010040914 Skin reaction Diseases 0.000 description 2
- 229920002385 Sodium hyaluronate Polymers 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- HDTRYLNUVZCQOY-WSWWMNSNSA-N Trehalose Natural products O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-WSWWMNSNSA-N 0.000 description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 2
- 229940048053 acrylate Drugs 0.000 description 2
- 229940114077 acrylic acid Drugs 0.000 description 2
- HDTRYLNUVZCQOY-LIZSDCNHSA-N alpha,alpha-trehalose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-LIZSDCNHSA-N 0.000 description 2
- 235000021302 avocado oil Nutrition 0.000 description 2
- 239000008163 avocado oil Substances 0.000 description 2
- 229960001631 carbomer Drugs 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229940031569 diisopropyl sebacate Drugs 0.000 description 2
- XFKBBSZEQRFVSL-UHFFFAOYSA-N dipropan-2-yl decanedioate Chemical compound CC(C)OC(=O)CCCCCCCCC(=O)OC(C)C XFKBBSZEQRFVSL-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000008169 grapeseed oil Substances 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 229940071826 hydroxyethyl cellulose Drugs 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000000845 maltitol Substances 0.000 description 2
- 235000010449 maltitol Nutrition 0.000 description 2
- VQHSOMBJVWLPSR-WUJBLJFYSA-N maltitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-WUJBLJFYSA-N 0.000 description 2
- 229940035436 maltitol Drugs 0.000 description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 235000008390 olive oil Nutrition 0.000 description 2
- 239000004006 olive oil Substances 0.000 description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000223 polyglycerol Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000035483 skin reaction Effects 0.000 description 2
- 231100000430 skin reaction Toxicity 0.000 description 2
- 229940047670 sodium acrylate Drugs 0.000 description 2
- 229940010747 sodium hyaluronate Drugs 0.000 description 2
- YWIVKILSMZOHHF-QJZPQSOGSA-N sodium;(2s,3s,4s,5r,6r)-6-[(2s,3r,4r,5s,6r)-3-acetamido-2-[(2s,3s,4r,5r,6r)-6-[(2r,3r,4r,5s,6r)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2- Chemical compound [Na+].CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 YWIVKILSMZOHHF-QJZPQSOGSA-N 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 229940032094 squalane Drugs 0.000 description 2
- LADGBHLMCUINGV-UHFFFAOYSA-N tricaprin Chemical compound CCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCC)COC(=O)CCCCCCCCC LADGBHLMCUINGV-UHFFFAOYSA-N 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000000230 xanthan gum Substances 0.000 description 2
- 229920001285 xanthan gum Polymers 0.000 description 2
- 235000010493 xanthan gum Nutrition 0.000 description 2
- 229940082509 xanthan gum Drugs 0.000 description 2
- 239000000811 xylitol Substances 0.000 description 2
- 235000010447 xylitol Nutrition 0.000 description 2
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 2
- 229960002675 xylitol Drugs 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- ZNIRCLRIYUOZJI-UHFFFAOYSA-N 2-[dodecanoyl(2-methylpropyl)amino]acetic acid Chemical compound CCCCCCCCCCCC(=O)N(CC(C)C)CC(O)=O ZNIRCLRIYUOZJI-UHFFFAOYSA-N 0.000 description 1
- KIOWXTOCDZJCBM-UHFFFAOYSA-N 2-docosoxyethyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCOCCOC(=O)C(C)=C KIOWXTOCDZJCBM-UHFFFAOYSA-N 0.000 description 1
- 206010067484 Adverse reaction Diseases 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- BACYUWVYYTXETD-UHFFFAOYSA-N N-Lauroylsarcosine Chemical compound CCCCCCCCCCCC(=O)N(C)CC(O)=O BACYUWVYYTXETD-UHFFFAOYSA-N 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 229940110830 beheneth-25 methacrylate Drugs 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 239000007933 dermal patch Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 210000000245 forearm Anatomy 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 108700004121 sarkosyl Proteins 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Images
Abstract
The invention discloses a mild oil-in-water type pickering sunscreen skin care product and a preparation method thereof. The oil-in-water pickering sunscreen skin care product comprises the following components in percentage by weight: 5-20% of zinc oxide; 0.01 to 1.5 percent of sodium polyacryloyl dimethyl taurate; titanium dioxide: 0.01-20%; 0.1 to 20 percent of humectant; 5-20% of an emollient; 0.01 to 2.5 percent of thickening agent; 0.1 to 1.5 percent of other components; the balance of deionized water. The oil-in-water pickering sunscreen skin care product provided by the invention does not add a traditional emulsifier, reduces the burden of the emulsifier on the skin, and is safe and efficient; the sodium polyacryl dimethyl taurate can form a film on the surface of skin when the product is smeared, so that the uniform coating of physical sun-screening powder is better facilitated, and the sun-screening effect of the product is obviously improved. Can realize pure physical high-efficiency sun protection, has simple preparation process, good use feeling and waterproof and sweat-resistant effects, and is particularly suitable for sun-proof skin care products for sensitive skin, pregnant women and infants.
Description
Technical Field
The invention relates to a sunscreen skin care product, belongs to the technical field of daily skin care products, and particularly relates to an emulsifier-free mild oil-in-water type pickering sunscreen skin care product and a preparation method thereof.
Background
Currently, the formulation systems of the commercially available sunscreen skin care products are roughly divided into four types: an oil-in-water emulsification system, a water-in-oil emulsification system, an oil-water separation system and a pure oil system. The emulsion system needs to be added with a large amount of emulsifier and thickening suspension stabilizer to realize the stability of the system, increase the skin load and easily cause irritation to the skin. The addition amount of an emulsifier is reduced in an oil-water separation system, but the problem that the use experience of a product is influenced because powder is easy to precipitate in the system exists; in addition, in order to improve the refreshing feeling of the product, ethanol is mostly added, so that the potential safety risk of the product is increased. The pure oil system has the problems of greasiness and poor use experience.
In the prior art, on the premise of ensuring sunscreen and skin care, a formula system which is milder and has better use experience is sought to improve the product value. Patent document CN 104127335 a provides a preparation process of a Pickering emulsion type sunscreen cream with UV controlled release of medicinal ingredients and easy cleaning, which is to prepare titanium dioxide modified by alkylsilane first, and then emulsify to prepare water-in-oil type Pickering sunscreen cream.
Sunscreens are mainly classified into physical ultraviolet screening agents and chemical ultraviolet absorbers. The physical ultraviolet screening agent plays a role in protecting skin by reflecting and scattering ultraviolet rays, and has the advantages of high stability and good safety; the chemical ultraviolet absorbent plays a role by absorbing ultraviolet rays, but has the defects of unstable structure and easy skin irritation, and is not suitable for sun-screening skin care products for sensitive skin, pregnant women and infants.
The existing sunscreen skin care product development technology mostly realizes the system stability by adding the traditional emulsifier, and the other part obtains the water-in-oil type Pickering sunscreen skin care product by carrying out hydrophobic modification on powder. In the prior art, no research report for preparing an oil-in-water pickering sunscreen skin care product by using zinc oxide exists.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a mild oil-in-water type Pickering sunscreen skin care product which is free from adding a traditional emulsifier, reduces the burden of the emulsifier on the skin and is milder; a large amount of physical sun-screening agents can be added into the formula system, so that pure physical high-power sun screening is realized; the sodium polyacryl dimethyl taurate forms a film on the surface of skin when the product is smeared, so that the uniform coating of physical sun-screening powder is better helped, and the sun-screening effect of the product is obviously improved.
The invention also aims to provide a preparation method of the mild oil-in-water type pickering sunscreen skin care product.
The present invention is realized by the following technical means.
The mild oil-in-water type pickering sunscreen skin care product comprises the following components in percentage by weight:
5-20% of zinc oxide; 0.01 to 1.5 percent of sodium polyacryloyl dimethyl taurate; 0.01 to 20 percent of titanium dioxide; 0.1 to 20 percent of humectant; 5-20% of an emollient; 0.01 to 2.5 percent of thickening agent; 0.1 to 1.5 percent of other components; the balance of deionized water.
Further, the mild oil-in-water type pickering sunscreen skin care product disclosed by the invention comprises the following components in percentage by weight:
8-18% of zinc oxide; 0.5 to 1.0 percent of sodium polyacryloyl dimethyl taurate; titanium dioxide: 5 to 15 percent; 5-15% of a humectant; 10-15% of an emollient; 0.5 to 1.5 percent of thickening agent; 0.5 to 1.0 percent of other components; the balance of deionized water.
The mild oil-in-water pickering sunscreen skin care product comprises one or more of polyglycerol, glycerol, butanediol, dipropylene glycol, propylene glycol, sorbitol, xylitol, sodium hyaluronate, polyethylene glycols, luba gum oil, biosaccharide gum, pentanediol, maltitol and trehalose.
The emollient is one or more selected from caprylic/capric triglyceride, isononyl isononanoate, squalane, fatty alcohol, silicone oil, octyl silicone oil, C12-15 alcohol benzoate, phenyl silicone oil, diisopropyl sebacate, avocado oil, macadamia nut seed oil, grape seed oil, olive oil, lauroyl sarcosine isopropyl ester, and glycerol tri (ethyl caproate).
The thickening agent is selected from one or more of sodium acrylate/sodium acryloyldimethyl taurate copolymer, ammonium acryloyldimethyl taurate/VP copolymer, ammonium acryloyldimethyl taurate/behenyl polyether-25 methacrylate cross-linked polymer, polyacrylate cross-linked polymer-6, hydroxyethyl cellulose, xanthan gum, carbomer, acrylic acid (ester)/C10-30 alkanol acrylate cross-linked polymer.
Furthermore, the sunscreen skin care product can be prepared into sunscreen milk, sunscreen lotion, sunscreen cream, sunscreen lotion, sunscreen spray, sun block cream, sun block milk or sun block lotion.
Furthermore, the sunscreen skin care product can be used for preparing a pure physical sunscreen skin care product, and is particularly suitable for sensitive skin, pregnant women and infants.
Further, the mild oil-in-water type Pickering sunscreen skin care product comprises the following raw material components in percentage by weight:
the water phase raw materials comprise: 0.5-1.0% of sodium polyacryloyl dimethyl taurate, 0.05-15% of glycerin and 0.05-5% of luba gum oil;
the oil phase comprises the following raw materials: 8-18% of zinc oxide; 5-15% titanium dioxide; 2-5% isononyl isononanoate; 2-5% of C12-15 alcohol benzoate; 1-5% of silicone oil;
0.5-1.5% of a thickener ammonium acryloyldimethyl taurate/VP copolymer;
0.5-1.0% of other components (including 0.05-0.2% of essence and 0.3-0.6% of preservative); and the balance of deionized water.
Further, the mild oil-in-water type Pickering sunscreen skin care product comprises the following raw material components in percentage by weight:
the water phase raw materials comprise: 0.8% of sodium polyacryloyldimethyl taurate, 14% of glycerol and 4% of luba gum oil;
the oil phase comprises the following raw materials: 15% of zinc oxide; 10% titanium dioxide; 5% isononyl isononanoate; 5% of C12-15 alcohol benzoate; 3% of silicone oil;
1.0% of a thickener ammonium acryloyldimethyltaurate/VP copolymer;
other ingredients (including 0.1% perfume, 0.6% preservative); and the balance of deionized water.
In addition, the preparation method of the mild oil-in-water type pickering sunscreen skin care product is prepared by the following steps:
1) putting the water phase raw materials into an emulsifying pot, mixing and heating to 75-85 ℃, and stirring for 20 minutes under the condition of heat preservation; wherein the water phase raw materials comprise: 0.5-1.0% of sodium polyacryloyl dimethyl taurate, 0.05-15% of glycerin and 0.05-5% of luba gum oil;
2) adding the oil phase into the water phase, homogenizing and stirring at 2000r/min for 10 minutes; wherein the oil phase comprises the following raw materials: 8-18% of zinc oxide; 5-15% titanium dioxide; 2-5% isononyl isononanoate; 2-5% of C12-15 alcohol benzoate; 1-5% of silicone oil;
3) adding 0.5-1.5% of thickening agent of acryloyl dimethyl ammonium taurate/VP copolymer into an emulsifying pot, and stirring for 10 minutes;
cooling to 40-45 deg.C under stirring, adding 0.5-1.0% of other components (including 0.05-0.2% of essence and 0.3-0.6% of antiseptic), cooling to 38-40 deg.C, testing, and discharging.
By means of the technical scheme, the invention has the following beneficial effects:
1) compared with the prior art, the mild oil-in-water type pickering sunscreen skin care product is prepared by innovatively utilizing zinc oxide and sodium polyacryl dimethyl taurate, has excellent sunscreen effect, is safe and mild, and is particularly suitable for sunscreen skin care products for sensitive skin, pregnant women and infants.
2) The invention has simple preparation process, fresh use feeling and waterproof and sweat-resistant effects, and is particularly suitable for sunscreen skin care products for sensitive skin, pregnant women and infants.
Drawings
FIG. 1 is a photomicrograph of the pickering sunscreen skin care product prepared in example 3.
Detailed Description
The present invention will be described in further detail below with reference to specific preferred embodiments and effect test examples.
The mild oil-in-water type pickering sunscreen skin care product is mainly obtained by mixing zinc oxide, sodium polyacryl dimethyl taurate, titanium dioxide, a humectant, an emollient, a thickener and adding other components.
Specifically, the raw material components comprise, by weight: 5-20% (preferably 8-18%) zinc oxide; sodium polyacryloyl dimethyl taurate 0.01-1.5% (preferably 0.5-1.0%); titanium dioxide 0.01-20% (preferably 5-15%); humectant 0.1-20% (preferably 5-15%); emollient 5-20% (preferably 10-15%); thickener 0.01-2.5% (preferably 0.5-1.5%); other components 0.1-1.5% (preferably 0.5-1.0%); the balance of deionized water.
The humectant is not particularly limited as long as it is a humectant commonly used in the cosmetic field, and examples thereof include polyglycerol, glycerol, butylene glycol, dipropylene glycol, propylene glycol, sorbitol, xylitol, sodium hyaluronate, polyethylene glycols, luba gum oil, biogum gum, pentanediol, maltitol, and trehalose.
The emollient is not particularly limited as long as it is a commonly used emollient in the cosmetic field, and examples thereof include caprylic/capric triglyceride, isononyl isononanoate, squalane, fatty alcohol, silicone oil, octyl silicone oil, C12-15 alcohol benzoate, phenyl silicone oil, diisopropyl sebacate, avocado oil, macadamia nut seed oil, grape seed oil, olive oil, isopropyl lauroylsarcosine, and tris (ethylhexanoate) ester.
Examples of the thickener include sodium acrylate/sodium acryloyldimethyltaurate copolymer, ammonium acryloyldimethyltaurate/VP copolymer, ammonium acryloyldimethyltaurate/beheneth-25 methacrylate crosslinked polymer, polyacrylate crosslinked polymer-6, hydroxyethylcellulose, xanthan gum, carbomer, acrylic acid (ester)/C10-30 alkanol acrylate crosslinked polymer, and the like.
Through long-term research, researchers of the invention find that the stable oil-in-water type pickering sunscreen skin care product can be prepared by utilizing the zinc oxide and the sodium polyacryl dimethyl taurate, the traditional emulsifier is not required to be added, and the texture of the final product can be changed by adjusting the dosage of the thickening agent.
The invention innovatively uses zinc oxide and sodium polyacryl dimethyl taurate to prepare the oil-in-water pickering sunscreen skin care product.
The oil-in-water pickering sunscreen skin care product provided by the invention does not add a traditional emulsifier, reduces the burden of the emulsifier on the skin, and is safe and efficient; the sodium polyacryl dimethyl taurate forms a film on the surface of skin when the product is smeared, so that the uniform coating of physical sun-screening powder is better helped, and the sun-screening effect of the product is obviously improved. The sunscreen lotion can realize pure physical high-efficiency sunscreen, has simple preparation process, good use feeling and waterproof and anti-sweat effects, has excellent sunscreen effect, is safe and mild, and is particularly suitable for sunscreen skin care products for sensitive skin, pregnant women and infants.
Examples 1 to 5 and comparative examples 1 to 2
Preparation of mild oil-in-water type pickering sunscreen skin care product formula
TABLE 1 oil-in-water pickering sunscreen skin care formulations (comparative examples 1-2)
TABLE 2 formulation of oil-in-water pickering sunscreen skin care formulations of the present invention (examples 1-5)
The preparation process of the mild oil-in-water type pickering sunscreen skin care product can be expressed as follows:
1) putting the water phase raw materials into an emulsifying pot, mixing and heating to 75-85 ℃, and stirring for 20 minutes under the condition of heat preservation;
2) adding the oil phase into the water phase, homogenizing and stirring at 2000r/min for 10 minutes;
3) adding the thickening agent into an emulsifying pot, and stirring for 10 minutes;
cooling to 40-45 deg.C under stirring, adding other components, cooling to 38-40 deg.C, testing, and discharging.
Second, evaluation of sunscreen effect and safety of oil-in-water pickering sunscreen skin care product
2.1 Effect of different amounts of Polyacryloyldimethyl taurate on Sun protection Effect
The pickering sunscreen skin care products obtained according to different preparation conditions shown in tables 1 and 2, wherein comparative example 2 cannot obtain a stable pickering sunscreen skin care product without adding zinc oxide, and thus comparative example 1 and examples 2 to 4 were compared to test the sunscreen effect. The results are shown in table 3 below:
TABLE 3 comparative sunscreen test
As can be seen from Table 3, the sunscreen effects of the test groups 2-4 are all better than those of the control group 1, and the sunscreen effect of the test group 3 is obviously better than that of the test group 2, and has no obvious difference from that of the test group 4. The addition of the sodium polyacryl dimethyl taurate can greatly improve the sun-screening effect of the product, the optimal effect can be achieved by adding 0.8 percent of sodium polyacryl dimethyl taurate, the sun-screening effect is not obviously improved by increasing the addition to 1.5 percent, and the using sticky feeling of the product is aggravated.
2.2 evaluation of safety of oil-in-water pickering sunscreen skin care products
The safety of the pickering sunscreen skin care product is evaluated by adopting a human body skin patch experiment. The pickering sunscreen skin care products of comparative example 1 and examples 1-5 were tested for safety.
The test method comprises the following steps: the test method of the patch for human skin is as follows: technical Specifications for cosmetic safety (2015 edition). Selecting a proper spot test device, selecting at least 60 qualified volunteers to test by a closed spot test method, and adding a tested sample and a blank control (without any substance) into the spot test device according to a sample random distribution table. The spot test device with the test object is applied to the inner side of the forearm of the subject, the test device is lightly pressed with the palm to be uniformly applied to the skin for 24 hours, the skin reaction is observed according to the standard of the table 4 after 30min (after the indentation disappears), 24 hours and 48 hours of removing the spot test device of the test object respectively, and the observation result is recorded. The results are shown in tables 4 and 5 below.
TABLE 4 skin reaction grading Standard for skin Enclosed Patch test
TABLE 5 Patch test results
As can be seen from Table 5, neither the control group nor the test group exhibited adverse reactions. The formula of the pickering sunscreen skin care product is safe and mild, and the pickering sunscreen skin care product is suitable for sensitive skin, pregnant women and infants.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, so that any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (4)
1. A mild oil-in-water type Pickering sunscreen skin care product is characterized by comprising the following raw material components:
the zinc oxide is surface-modified zinc oxide, and the modified material is selected from one or more of perfluorooctyl triethoxysilane, isopropyl titanium triisostearate, triethoxyoctyl silane, stearyl glutamate, jojoba ester and polydimethylsiloxane;
sodium polyacryloyl dimethyl taurate;
titanium dioxide, which is surface-modified titanium dioxide or unmodified titanium dioxide; the surface modified titanium dioxide is prepared from one or more of perfluorooctyl triethoxysilane, isopropyl titanium triisostearate, triethoxyoctyl silane, stearyl glutamic acid, jojoba ester and polydimethylsiloxane;
a humectant;
an emollient;
a thickener;
other components;
the balance of deionized water;
the preparation method of the mild oil-in-water type pickering sunscreen skin care product comprises the following steps:
1) putting the water phase raw materials into an emulsifying pot, mixing and heating to 75-85 ℃, and stirring for 20 minutes under the condition of heat preservation; wherein the water phase raw materials comprise: 0.5-1.0% of sodium polyacryl dimethyl taurate, a humectant comprising 0.05-15% of glycerin and 0.05-5% of luba gum oil;
2) adding the oil phase into the water phase, homogenizing and stirring at 2000r/min for 10 minutes; wherein the oil phase comprises the following raw materials: 8-18% of zinc oxide; 5-15% titanium dioxide; an emollient comprising isononyl isononanoate 2-5%, C12-15 alcohol benzoate 2-5%, and silicone oil 1-5%;
3) adding 0.5-1.5% of thickening agent of acryloyl dimethyl ammonium taurate/VP copolymer into an emulsifying pot, and stirring for 10 minutes; cooling to 40-45 deg.C under stirring, adding 0.5-1.0% of other components including 0.05-0.2% of essence and 0.3-0.6% of antiseptic, cooling to 38-40 deg.C, inspecting, and discharging.
2. The mild oil-in-water Pickering sunscreen skin care product according to claim 1, wherein:
the sunscreen skin care product can be prepared into sunscreen emulsion, sunscreen lotion, sunscreen cream, sunscreen lotion, sunscreen spray, sun screen or sun screen lotion.
3. The mild oil-in-water Pickering sunscreen skin care product according to claim 1 or 2, characterized in that: the sunscreen skin care product is used for preparing a pure physical sunscreen skin care product suitable for sensitive skin, pregnant women and infants.
4. The mild oil-in-water Pickering sunscreen skin care product according to claim 3, wherein: the material consists of the following raw materials in percentage by weight:
the water phase raw materials comprise: 0.8% of sodium polyacryloyldimethyl taurate, 14% of glycerol and 4% of luba gum oil;
the oil phase comprises the following raw materials: 15% of zinc oxide; 10% titanium dioxide; 5% isononyl isononanoate; 5% of C12-15 alcohol benzoate; 3% of silicone oil;
1.0% of a thickener ammonium acryloyldimethyltaurate/VP copolymer;
other components including 0.1% of essence, 0.6% of preservative; and the balance of deionized water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910193114.5A CN109833214B (en) | 2019-03-14 | 2019-03-14 | Mild oil-in-water type pickering sunscreen skin care product and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910193114.5A CN109833214B (en) | 2019-03-14 | 2019-03-14 | Mild oil-in-water type pickering sunscreen skin care product and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109833214A CN109833214A (en) | 2019-06-04 |
| CN109833214B true CN109833214B (en) | 2022-05-03 |
Family
ID=66885695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910193114.5A Expired - Fee Related CN109833214B (en) | 2019-03-14 | 2019-03-14 | Mild oil-in-water type pickering sunscreen skin care product and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109833214B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111686034A (en) * | 2020-07-30 | 2020-09-22 | 上海绵花棠生物科技有限公司 | Composition for external application to skin and external product for skin |
| CN112545906A (en) * | 2020-12-23 | 2021-03-26 | 中国医科大学 | Sun-screening and repairing day cream and preparation method thereof |
| CN114681342A (en) * | 2020-12-29 | 2022-07-01 | 上海创元化妆品有限公司 | Method for modifying hydrophobicity of powder composition and cosmetic containing powder composition |
| CN114869789A (en) * | 2021-02-05 | 2022-08-09 | 株式会社资生堂 | Scrub cream for removing cutin |
| CN114129461A (en) * | 2021-11-29 | 2022-03-04 | 广州凡岛网络科技有限公司 | Sunscreen skin care product containing composite titanium dioxide and preparation method thereof |
| CN114306133B (en) * | 2021-12-29 | 2024-03-29 | 上海运佳黄浦制药有限公司 | Ion-resistant thickener, and preparation method and application thereof |
| WO2023230955A1 (en) * | 2022-06-01 | 2023-12-07 | Nivea (Shanghai) Co. Ltd. | Silicone-free emulsion i |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102695493A (en) * | 2009-11-06 | 2012-09-26 | 花王株式会社 | Oil-in-water-type emulsion cosmetic |
| CN103974687A (en) * | 2011-11-30 | 2014-08-06 | 花王株式会社 | Oil-in-water-type emulsion cosmetic |
| CN104780900A (en) * | 2012-11-14 | 2015-07-15 | 花王株式会社 | Oil-in-water emulsion composition |
-
2019
- 2019-03-14 CN CN201910193114.5A patent/CN109833214B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102695493A (en) * | 2009-11-06 | 2012-09-26 | 花王株式会社 | Oil-in-water-type emulsion cosmetic |
| CN103974687A (en) * | 2011-11-30 | 2014-08-06 | 花王株式会社 | Oil-in-water-type emulsion cosmetic |
| CN104780900A (en) * | 2012-11-14 | 2015-07-15 | 花王株式会社 | Oil-in-water emulsion composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109833214A (en) | 2019-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109833214B (en) | Mild oil-in-water type pickering sunscreen skin care product and preparation method thereof | |
| KR100446341B1 (en) | Anti-aging cosmetic composition | |
| CN109820738B (en) | High-power oil-in-water sunscreen cosmetic | |
| EP0688559A1 (en) | Skin anti-ageing composition | |
| CN113304075B (en) | Glacier rock cleaning oil control mud film and preparation method thereof | |
| CN113181095A (en) | Anti-inflammatory repairing cosmetic composition and application thereof | |
| CN115282073B (en) | Composition and sun-screening cosmetic | |
| CN113925791A (en) | Waterproof sunscreen composition and preparation method thereof | |
| CN108542870A (en) | A kind of infant's face cream of mildly releiving | |
| CN113398016A (en) | Skin soothing and repairing composition and cosmetic composition | |
| CN113995693B (en) | Essence composition of liposome with anti-inflammatory effect, and preparation method and application thereof | |
| CN108014060B (en) | Sunscreen synergistic composition and application thereof | |
| CN112516022B (en) | Sun-screening lotion and preparation method thereof | |
| CN114053202A (en) | Sunscreen composition and sunscreen agent | |
| JP2004522765A (en) | Gel emulsions in the form of O / W emulsions containing hydrocolloids | |
| KR102247748B1 (en) | Sedum sarmentosum gel and moisturizing composition comprising the same | |
| CN110292543B (en) | Biological composition for replacing ultraviolet absorbent and application thereof | |
| CN114983841B (en) | Silicone oil-free water-in-oil peony sun-protection emulsion and preparation method thereof | |
| DE69918626T2 (en) | Composition for external use containing succinoglucan, alumina and an alkyl acrylate / methacrylate copolymer | |
| JPH09136823A (en) | Antiaging preparation for external use for skin, preparation for external use for skin capable of inhibiting cross-linking of collagen and antiultraviolet ray preparation for external use for skin | |
| CN110433092B (en) | Composition for preventing blue light and repairing blue light damage | |
| JPH09136822A (en) | Antiaging preparation for external use for skin, preparation for external use for skin capable of inhibiting cross-linking of collagen and antiultraviolet ray preparation for external use for skin | |
| KR20220150910A (en) | Topically administrable lysate of dedifferentiated cells of the plant Helichrysum stoecas for moisturizing the skin | |
| CN111658599A (en) | Liposome sunscreen cosmetic and preparation method thereof | |
| KR20210050957A (en) | Cosmetic composition of sunscreen with titanium dioxide powder dispersed in both of oil phase and water phase |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20220503 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |