CN115569084B - 一种液晶悬浮组合物及其制备方法与应用 - Google Patents
一种液晶悬浮组合物及其制备方法与应用 Download PDFInfo
- Publication number
- CN115569084B CN115569084B CN202210036871.3A CN202210036871A CN115569084B CN 115569084 B CN115569084 B CN 115569084B CN 202210036871 A CN202210036871 A CN 202210036871A CN 115569084 B CN115569084 B CN 115569084B
- Authority
- CN
- China
- Prior art keywords
- parts
- surfactant
- weight ratio
- liquid crystal
- polysaccharide
- 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
- 239000000725 suspension Substances 0.000 title claims abstract description 40
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims description 6
- -1 hydroxyl compound Chemical class 0.000 claims abstract description 49
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 20
- 239000005017 polysaccharide Substances 0.000 claims abstract description 20
- 239000004094 surface-active agent Substances 0.000 claims abstract description 14
- 239000003381 stabilizer Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000077 silane Inorganic materials 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000003945 anionic surfactant Substances 0.000 claims description 13
- 150000004676 glycans Chemical class 0.000 claims description 13
- 239000002736 nonionic surfactant Substances 0.000 claims description 11
- 239000002280 amphoteric surfactant Substances 0.000 claims description 10
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 10
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 10
- 239000002453 shampoo Substances 0.000 claims description 10
- 239000002738 chelating agent Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000003755 preservative agent Substances 0.000 claims description 8
- 230000002335 preservative effect Effects 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- WCOXQTXVACYMLM-UHFFFAOYSA-N 2,3-bis(12-hydroxyoctadecanoyloxy)propyl 12-hydroxyoctadecanoate Chemical group CCCCCCC(O)CCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCC(O)CCCCCC)COC(=O)CCCCCCCCCCC(O)CCCCCC WCOXQTXVACYMLM-UHFFFAOYSA-N 0.000 claims description 6
- GHBFNMLVSPCDGN-UHFFFAOYSA-N caprylic acid monoglyceride Natural products CCCCCCCC(=O)OCC(O)CO GHBFNMLVSPCDGN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229930182478 glucoside Natural products 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229940057400 trihydroxystearin Drugs 0.000 claims description 6
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 claims description 5
- 229960004551 cotton seed extract Drugs 0.000 claims description 5
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- RGUVUPQQFXCJFC-UHFFFAOYSA-N n-hydroxyoctanamide Chemical compound CCCCCCCC(=O)NO RGUVUPQQFXCJFC-UHFFFAOYSA-N 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- 229940045944 sodium lauroyl glutamate Drugs 0.000 claims description 4
- IWIUXJGIDSGWDN-UQKRIMTDSA-M sodium;(2s)-2-(dodecanoylamino)pentanedioate;hydron Chemical group [Na+].CCCCCCCCCCCC(=O)N[C@H](C([O-])=O)CCC(O)=O IWIUXJGIDSGWDN-UQKRIMTDSA-M 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229920001661 Chitosan Polymers 0.000 claims description 3
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 3
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 2
- 230000001815 facial effect Effects 0.000 claims description 2
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 230000000087 stabilizing effect Effects 0.000 abstract description 8
- 229920002545 silicone oil Polymers 0.000 abstract description 7
- 238000011010 flushing procedure Methods 0.000 abstract description 6
- 239000004519 grease Substances 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 3
- 239000010445 mica Substances 0.000 abstract description 3
- 229910052618 mica group Inorganic materials 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 239000000843 powder Substances 0.000 abstract description 3
- 238000009825 accumulation Methods 0.000 abstract description 2
- 150000004756 silanes Chemical class 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 239000000375 suspending agent Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 210000004761 scalp Anatomy 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229940043810 zinc pyrithione Drugs 0.000 description 7
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 208000003251 Pruritus Diseases 0.000 description 3
- 102100021227 TGF-beta-activated kinase 1 and MAP3K7-binding protein 2 Human genes 0.000 description 3
- 101710178681 TGF-beta-activated kinase 1 and MAP3K7-binding protein 2 Proteins 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000007803 itching Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000002421 anti-septic effect Effects 0.000 description 2
- 230000003766 combability Effects 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 230000007794 irritation Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- KZRXPHCVIMWWDS-AWEZNQCLSA-N (4S)-4-amino-5-dodecanoyloxy-5-oxopentanoic acid Chemical compound CCCCCCCCCCCC(=O)OC(=O)[C@@H](N)CCC(O)=O KZRXPHCVIMWWDS-AWEZNQCLSA-N 0.000 description 1
- 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 1
- 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 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 206010019049 Hair texture abnormal Diseases 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 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
- 229930006000 Sucrose Natural products 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000000022 bacteriostatic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009960 carding Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- MRUAUOIMASANKQ-UHFFFAOYSA-N cocamidopropyl betaine Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC([O-])=O MRUAUOIMASANKQ-UHFFFAOYSA-N 0.000 description 1
- 229940073507 cocamidopropyl betaine Drugs 0.000 description 1
- 229940031728 cocamidopropylamine oxide Drugs 0.000 description 1
- 229940065856 cocoyl glycinate Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000003648 hair appearance Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229940071085 lauroyl glutamate Drugs 0.000 description 1
- 229940071145 lauroyl sarcosinate Drugs 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 210000004894 snout Anatomy 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
- A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0295—Liquid crystals
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/26—Aluminium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/37—Esters of carboxylic acids
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
- A61K8/4933—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having sulfur as an exocyclic substituent, e.g. pyridinethione
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/60—Sugars; Derivatives thereof
- A61K8/602—Glycosides, e.g. rutin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
- A61K8/922—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof of vegetable origin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/96—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution
- A61K8/97—Cosmetics or similar toiletry preparations characterised by the composition containing materials, or derivatives thereof of undetermined constitution from algae, fungi, lichens or plants; from derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/12—Preparations containing hair conditioners
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/59—Mixtures
- A61K2800/592—Mixtures of compounds complementing their respective functions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Chemical & Material Sciences (AREA)
- Dermatology (AREA)
- Emergency Medicine (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Biotechnology (AREA)
- Botany (AREA)
- Microbiology (AREA)
- Mycology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Cosmetics (AREA)
Abstract
本发明提供了一种液晶悬浮组合物,按照重量份计,包括以下原料:表面活性剂15‑22份、悬浮稳定剂4‑30份、羟基化合物0.1‑10份、多糖类化合物0.1‑10份、硅烷化合物0.05‑5份、水补足至100份。本发明制备的悬浮组合物具有较高的悬浮稳定能力,较低添加量能有效对ZPT、硅油、植物颗粒和云母粉等有很好的悬浮稳定作用,同时还能明显改善湿冲的涩感,具有优异的梳理性;且促进了体系中油脂和硅烷化合物的有效吸附和积聚,减少20‑30%的油脂用量;此外还提高了高屈服值,兼容性和配伍性较好,且在宽温范围内,有很好的流变性,对pH值、强离子和电解质体系不敏感。
Description
技术领域
本发明涉及日化技术领域,具体涉及一种液晶悬浮组合物及其制备方法与应用。
背景技术
洗发护发类产品作为人们生活中的必需的日化用品,一般人们通过清洁头皮和头发,同时希望具有调理发质的功效,市面上大多数的洗发产品可以清洁头发和头皮上产生的油脂和污垢,也能赋予头皮和头发一定的营养。
但是在由于洗发水中添加了性质不同的多种物质,而其中物质间的不相容性会导致体系的稳定性较差,从而严重影响使用感受和效果。
为了解决稳定性问题,现有技术常采用卡波、TAB-2和SF-1等传统的悬浮剂,中国专利CN105473125A公开了一种头发处理组合物,通过采用卡波类化合物作为悬浮剂,使得该组合物具有优异的稳定性。然而这些高分子化合物所具有的网络结构,在洗发过程中与发丝产生缠绕,抑制了洗发水中有效物质的作用,同时也会使得头发产生严重的涩感,导致湿梳和干梳性较差。
发明内容
针对现有技术中存在的不足,本发明一方面提供了一种液晶悬浮组合物,按照重量份计,包括以下原料:表面活性剂15-22份、悬浮稳定剂4-30份、羟基化合物0.1-10份、多糖类化合物0.1-10份、硅烷化合物0.05-5份、水补足至100份。
在一些实施方式中,所述表面活性剂包括阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂、两性表面活性剂中的一种或多种。
在一些实施方式中,所述表面活性剂包括阴离子表面活性剂、非离子表面活性剂和两性表面活性剂,重量比为1:(0.3-0.7):(0.4-0.6)。
优选地,所述表面活性剂包括阴离子表面活性剂、非离子表面活性剂和两性表面活性剂,重量比为1:0.5:0.5。
在一些实施方式中,所述阴离子表面活性剂包括氨基酸盐、肪醇醚磺基琥珀酸酯盐,脂肪酰甲基牛磺酸盐、N-脂肪酰氨基酸盐、单烷基磷酸酯盐、单烷基羧酸盐中的一种或多种。
优选地,所述阴离子表面活性剂为氨基酸盐,所述氨基酸盐包括月桂酰谷氨酸盐、椰油酰甘胺酸盐、椰油酰丙胺酸盐、月桂酰肌氨酸盐中的一种或多种,其中的盐包括钠盐、钾盐、三乙醇胺盐中的一种。
更加优选地,所述阴离子表面活性剂为月桂酰谷氨酸钠。
在一些实施方式中,所述非离子表面活性剂包括烷基葡糖苷、椰油酰胺丙基氧化胺,十八烷基二羟乙基氧化胺,N,N-双羟乙基烷基酰胺,N-羟乙基椰油烷基酰胺中的至少一种。
优选地,所述非离子表面活性剂为烷基葡糖苷。
更加优选地,所述非离子表面活性剂为C12-14烷基葡糖苷。
在一些实施方式中,所述两性表面活性剂包括椰油酰胺丙基甜菜碱、椰油酰两性基二乙酸二钠、月桂酰两性基二乙酸二钠中的一种或多种。
优选地,所述两性表面活性剂为椰油酰两性基二乙酸二钠。
在一些实施方式中,所述悬浮稳定剂包括三羟基硬脂精。
优选地,所述三羟基硬脂精的固含量≥95%。
固含量是乳液或涂料在规定条件下烘干后剩余部分占总量的质量百分数。
在一些实施方式中,所述羟基化合物包括甘油、二丙二醇、丙二醇、丁二醇、聚甘油、聚丙二醇、聚乙二醇、山梨醇、癸二醇、戊二醇、蔗糖中的一种或多种。
在一些实施方式中,所述羟基化合物包括二丙二醇和聚乙二醇,且重量比为1:(1-2)。
优选地,所述羟基化合物包括二丙二醇和聚乙二醇,且重量比为1:1.5。
在一些实施方式中,所述多糖类化合物包括多糖聚合物和水解多糖,重量比为(1-10):1。
在一些实施方式中,所述多糖聚合物包括羟甲基壳聚糖。
在一些实施方式中,所述水解多糖包括水解麦芽提取物和水解棉籽提取物的混合,重量比为(0.8-1.2):1。
更加优选地,所述水解多糖包括水解麦芽提取物和水解棉籽提取物的混合,重量比为1:1。
在一些实施方式中,所述硅烷化合物包括聚硅氧烷类物质。
优选地,所述聚硅氧烷类物质包括聚二甲基硅氧烷和氨基聚二甲基硅氧烷,且重量比为1:(0.75-1)。
更加优选地,所述聚硅氧烷类物质包括聚二甲基硅氧烷和氨基聚二甲基硅氧烷,且重量比为1:0.85。
在制备洗护用品的过程中,常加入一定的悬浮剂来提高整个体系的稳定性,在现有技术中常用的悬浮剂包括卡波、TAB-2(邻苯二甲酸烷基酰胺)和SF-1(丙烯酸脂类共聚物),然而这些聚合物具有一定的网络结构,在使用过程中会与头发丝发生缠绕,从而抑制洗护产品中有效物质的释放,并且还会使得头发产生严重的涩感,导致湿梳和干梳性均较差,申请人在研究中意外发现在本体系中加入特定比例的三羟基硬脂精和特定种类的表面活性剂能够制备出的悬浮组合物具有较高的悬浮稳定能力,较低添加量能有效对ZPT(吡啶硫酮锌)、硅油、植物颗粒和云母粉等有很好的悬浮稳定作用,同时还能明显改善湿冲的涩感,具有优异的梳理性,申请人认为可能的原因体系中形成了独特的三维液晶网状结构,显著提高了体系的屈服值,从而提供了优异的悬浮稳定作用,同时本发明加入的表面活性剂包括特定比例的氨基酸型阴离子表面活性剂、非离子表面活性剂以及两性表面活性剂,可以与三羟基硬脂精一直存在物理作用,二者相互协同和依附,赋予该组合物优异的铺展性,能够积聚于头发的毛鳞片上,赋头发丝滑滋润的清爽感,解决了传统悬浮剂容易发涩的问题,此外还可以促进体系中油脂和硅烷化合物的有效吸附和积聚,减少20-30%的油脂用量。
在现有技术中经常使用月桂醇硫酸酯钠和月桂醇聚醚硫酸酯盐阴离子表面活性剂,具有较好的起泡性能和清洗效果,然而申请人发现这种阴离子表面活性剂的去脂力太大,会对头皮产生很强的刺激作用,进一步导致头皮发痒、头发干燥的问题,申请人在研究中发现采用重量比为1:(0.3-0.7):(0.4-0.6)的阴离子表面活性剂、非离子表面活性剂和两性表面活性剂进行复配,尤其是阴离子表面活性剂为月桂酰谷氨酸钠,非离子表面活性剂为C12-14烷基葡糖苷,两性表面活性剂为椰油酰两性基二乙酸二钠时可以提高产品的易冲洗性,降低在皮肤上的残留,同时还明显降低对头皮和头发的刺激和头痒率。
在一些实施方式中,所述制备原料还包括0.015-0.65重量份的助剂,所述助剂包括防腐剂、抑菌剂、螯合剂中的一种或多种。
优选地,按照重量份计,所述助剂包括防腐剂0.01-0.5份、螯合剂0.005-0.15份。
在一些实施方式中,所述防腐剂包括辛酰羟肟酸和甘油辛酸酯,重量比为(1.5-2.5):1。
优选地,所述防腐剂包括辛酰羟肟酸和甘油辛酸酯,重量比为2:1。
在一些实施方式中,所述螯合剂包括柠檬酸钠或乙二胺四乙酸二钠。
优选地,所述螯合剂为柠檬酸钠。
本发明的第二方面提供了一种液晶悬浮组合物的制备方法,包括以下步骤:用水将悬浮稳定剂分散好,加热至65-75℃,投入余料,搅拌均质分散好,冷却降温出料。
优选地,所述液晶悬浮组合物的制备方法,包括以下步骤:用水将悬浮稳定剂分散好,加热至70℃,投入余料,搅拌均质分散好,降温至50℃下,加入防腐剂后搅拌均匀,冷却降温至40℃以下,出料即得。
本发明的第三方面提供了一种液晶悬浮组合物在个人护理产品中的应用,包括洗发水、洗面奶、沐浴露、护发产品。
有益效果:
在本体系中加入特定比例的三羟基硬脂精和特定种类的表面活性剂能够制备出的悬浮组合物具有较高的悬浮稳定能力,较低添加量能有效对ZPT、硅油、植物颗粒和云母粉等有很好的悬浮稳定作用,同时还能明显改善湿冲的涩感,具有优异的梳理性;且促进了体系中油脂和硅烷化合物的有效吸附和积聚,减少20-30%的油脂用量;此外还提高了高屈服值,耐离子和电解质,兼容性和配伍性好,在宽温范围内,有很好的流变性,对pH值、强离子和电解质体系不敏感;并且通过各成分的协同作用提高了产品的易冲洗性,降低在皮肤上的残留,明显降低对头皮和头发的刺激和头痒率。
附图说明
图1是悬浮稳定性测试中编号1的样品在48℃下放置60天后的状态图;
图2是悬浮稳定性测试中编号2的样品在48℃下放置60天后的状态图;
图3是悬浮稳定性测试中编号3的样品在48℃下放置60天后的状态图;
图4是不同类型的悬浮剂分别加入到洗发水中的效果评价的结果。
具体实施方式
实施例1
本实施例一方面提供了一种液晶悬浮组合物,按照重量份计,包括以下原料:表面活性剂20份、悬浮稳定剂16份、羟基化合物4.5份、多糖类化合物5份、硅烷化合物2.5份、防腐剂0.2份、螯合剂0.1份、水补足至100份。
所述表面活性剂包括阴离子表面活性剂、非离子表面活性剂和两性表面活性剂,重量比为1:0.5:0.5。
所述阴离子表面活性剂为月桂酰谷氨酸钠,所述非离子表面活性剂为C12-14烷基葡糖苷,购自上海洪帆生物科技有限公司,型号为APG1214;所述两性表面活性剂为椰油酰两性基二乙酸二钠。
所述悬浮稳定剂为三羟基硬脂精,购自鞍山创业生物新材料科技有限公司,固含量为98%。
所述羟基化合物包括二丙二醇和聚乙二醇,且重量比为1:1.5。
所述聚乙二醇购自链集化工有限公司,型号为PEG400。
所述多糖类化合物包括多糖聚合物和水解多糖,重量比为4:1。
所述多糖聚合物为羟甲基壳聚糖,购自南通添香生物工程有限公司。
所述水解多糖包括水解麦芽提取物和水解棉籽提取物的混合,重量比为1:1;所述水解麦芽提取物购自陕西夏州生物科技有限公司,型号为AJ-04;所述水解棉籽提取物购自斯诺特生物。
所述硅烷化合物包括聚二甲基硅氧烷和氨基聚二甲基硅氧烷,且重量比为1:0.85。
所述聚二甲基硅氧烷购自广州恒广复合材料有限公司,型号为所述氨基聚二甲基硅氧烷购自广州恒广复合材料有限公司,型号为/>
所述防腐剂包括辛酰羟肟酸和甘油辛酸酯,重量比为2:1。
所述螯合剂为柠檬酸钠。
本发明的第二方面提供了一种液晶悬浮组合物的制备方法,包括以下步骤:用水将悬浮稳定剂分散好,加热至70℃,投入余料,搅拌均质分散好,降温至48℃,加入防腐剂后搅拌均匀,冷却降温至35℃,出料即得。
对比例1
本对比例为卡波2020悬浮剂。
对比例2
本对比例为TAB-2悬浮剂。
对比例3
本对比例为SF-1悬浮剂。
性能测试
1.悬浮稳定性测试
取3个试剂瓶,分别编号1、2、3;
编号1:将实施例1制备的液晶悬浮组合物、ZPT、道康宁7137硅油以0.5:1:3的重量比加入到试剂瓶中混合均匀,然后置于48℃的条件下放置60天;
编号2:将实施例1制备的液晶悬浮组合物、ZPT、道康宁7137硅油以0.5:2:3的重量比加入到试剂瓶中混合均匀,然后置于48℃的条件下放置60天;
编号3:将ZPT、道康宁7137硅油以1:3的重量比加入到试剂瓶中混合均匀,然后置于48℃的条件下放置60天。
60天后,观察编号1、2、3样品是否有分层现象,将结果记录在表1。
表1
编号 | 样品状态 |
1 | 均一分布,无分层 |
2 | 均一分布,无分层 |
3 | 明显分层 |
结合表1和图1-3可得出结论:实施例1制备的液晶悬浮组合物较低的添加量对ZPT、硅油有很好的悬浮稳定作用。
2.不同类型的悬浮剂效果对比
分别将实施例1制备的悬浮组合物和对比例1-3提供的悬浮剂加入到其他成分均相同的洗发水中,得出四种洗发水,随机选取10名志愿者分别使用这4种洗发水,对以下指标进行打分:湿梳理性、湿冲滑感、易冲水、干后梳理性、清爽度,满分为10分,分数结果见表1-4。
表1
志愿者编号 | 湿梳理性 | 湿冲滑感 | 易冲水 | 干后梳理性 | 清爽度 |
1 | 10 | 8 | 10 | 10 | 10 |
2 | 9 | 9 | 10 | 8 | 10 |
3 | 10 | 8 | 10 | 10 | 10 |
4 | 7 | 6 | 10 | 9 | 10 |
5 | 8 | 7 | 10 | 9 | 10 |
6 | 9 | 10 | 10 | 8 | 10 |
7 | 9 | 9 | 10 | 7 | 10 |
8 | 10 | 8 | 10 | 10 | 10 |
9 | 8 | 7 | 10 | 9 | 10 |
10 | 10 | 8 | 10 | 10 | 10 |
平均分 | 9 | 8 | 10 | 9 | 10 |
表2
志愿者编号 | 湿梳理性 | 湿冲滑感 | 易冲水 | 干后梳理性 | 清爽度 |
1 | 8 | 9 | 9 | 6 | 9 |
2 | 7 | 7 | 7 | 7 | 8 |
3 | 8 | 6 | 6 | 7 | 8 |
4 | 6 | 7 | 8 | 8 | 7 |
5 | 10 | 8 | 9 | 8 | 9 |
6 | 7 | 7 | 8 | 7 | 7 |
7 | 9 | 6 | 8 | 6 | 8 |
8 | 8 | 5 | 8 | 7 | 8 |
9 | 9 | 7 | 9 | 8 | 7 |
10 | 8 | 8 | 8 | 6 | 9 |
平均分 | 8 | 7 | 8 | 7 | 8 |
表3
表4
志愿者编号 | 湿梳理性 | 湿冲滑感 | 易冲水 | 干后梳理性 | 清爽度 |
1 | 7 | 8 | 5 | 7 | 5 |
2 | 9 | 7 | 6 | 6 | 6 |
3 | 8 | 8 | 7 | 7 | 5 |
4 | 6 | 7 | 6 | 5 | 4 |
5 | 8 | 7 | 6 | 8 | 3 |
6 | 8 | 7 | 5 | 9 | 5 |
7 | 9 | 6 | 5 | 6 | 7 |
8 | 8 | 6 | 7 | 7 | 5 |
9 | 9 | 7 | 8 | 8 | 6 |
10 | 8 | 7 | 5 | 7 | 4 |
平均分 | 8 | 7 | 6 | 7 | 5 |
将实施例1和对比例1-3针对各项指标得到的平均分汇总,结果见图4。
由图4可得出结论:实施例1和对比例1-3相比,其实施例1的清爽度、湿梳理性、干后梳理性、湿冲滑感、易冲水性都具有明显的优势。
以上所述仅为本发明的优选实施例,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对本领域的技术人员来说,可根据上述说明加以改进和变换,所有这些改进和变换都应属于本发明所附权利要求的保护范围。
Claims (3)
1.一种液晶悬浮组合物,其特征在于,按照重量份计,包括以下原料:表面活性剂20份、悬浮稳定剂16份、羟基化合物4.5份、多糖类化合物5份、硅烷化合物2.5份、防腐剂0.2份、螯合剂0.1份、水补足至100份;
所述表面活性剂包括阴离子表面活性剂、非离子表面活性剂和两性表面活性剂,重量比为1:0.5:0.5;
所述阴离子表面活性剂为月桂酰谷氨酸钠,所述非离子表面活性剂为C12-14烷基葡糖苷;所述两性表面活性剂为椰油酰两性基二乙酸二钠;
所述悬浮稳定剂为三羟基硬脂精,固含量为98%;
所述羟基化合物包括二丙二醇和聚乙二醇,且重量比为1:1.5;
所述聚乙二醇型号为PEG400;
所述多糖类化合物包括多糖聚合物和水解多糖,重量比为4:1;
所述多糖聚合物为羟甲基壳聚糖;
所述水解多糖包括水解麦芽提取物和水解棉籽提取物的混合,重量比为1:1;
所述硅烷化合物包括聚二甲基硅氧烷和氨基聚二甲基硅氧烷,且重量比为1:0.85;
所述防腐剂包括辛酰羟肟酸和甘油辛酸酯,重量比为2:1;
所述螯合剂为柠檬酸钠。
2.一种根据权利要求1所述的液晶悬浮组合物的制备方法,其特征在于,包括以下步骤:用水将悬浮稳定剂分散好,加热至65-75℃,投入余料,搅拌均质分散好,冷却降温出料。
3.一种根据权利要求1所述的液晶悬浮组合物在制备个人护理产品中的应用,其特征在于,包括洗发水、洗面奶、沐浴露、护发产品。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210036871.3A CN115569084B (zh) | 2022-01-12 | 2022-01-12 | 一种液晶悬浮组合物及其制备方法与应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210036871.3A CN115569084B (zh) | 2022-01-12 | 2022-01-12 | 一种液晶悬浮组合物及其制备方法与应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115569084A CN115569084A (zh) | 2023-01-06 |
CN115569084B true CN115569084B (zh) | 2024-03-08 |
Family
ID=84579654
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210036871.3A Active CN115569084B (zh) | 2022-01-12 | 2022-01-12 | 一种液晶悬浮组合物及其制备方法与应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115569084B (zh) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996025144A1 (en) * | 1995-02-15 | 1996-08-22 | The Procter & Gamble Company | Crystalline hydroxy waxes as oil in water stabilizers for skin cleansing liquid composition |
CN1568174A (zh) * | 2001-10-18 | 2005-01-19 | 宝洁公司 | 具有阴离子表面活性剂、两性表面活性剂及阳离子聚合物的洗发剂组合物 |
CN101160154A (zh) * | 2005-02-16 | 2008-04-09 | 荷兰联合利华有限公司 | 具有独特感官性质的液体清洁组合物 |
CN107625658A (zh) * | 2017-09-29 | 2018-01-26 | 澳宝化妆品(惠州)有限公司 | 一种洗护发组合物及其制备方法 |
CN112022728A (zh) * | 2020-08-26 | 2020-12-04 | 澳宝化妆品(惠州)有限公司 | 一种护发抗污染的结构化表面活性剂组合物 |
-
2022
- 2022-01-12 CN CN202210036871.3A patent/CN115569084B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996025144A1 (en) * | 1995-02-15 | 1996-08-22 | The Procter & Gamble Company | Crystalline hydroxy waxes as oil in water stabilizers for skin cleansing liquid composition |
CN1568174A (zh) * | 2001-10-18 | 2005-01-19 | 宝洁公司 | 具有阴离子表面活性剂、两性表面活性剂及阳离子聚合物的洗发剂组合物 |
CN101160154A (zh) * | 2005-02-16 | 2008-04-09 | 荷兰联合利华有限公司 | 具有独特感官性质的液体清洁组合物 |
CN107625658A (zh) * | 2017-09-29 | 2018-01-26 | 澳宝化妆品(惠州)有限公司 | 一种洗护发组合物及其制备方法 |
CN112022728A (zh) * | 2020-08-26 | 2020-12-04 | 澳宝化妆品(惠州)有限公司 | 一种护发抗污染的结构化表面活性剂组合物 |
Also Published As
Publication number | Publication date |
---|---|
CN115569084A (zh) | 2023-01-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2415450B1 (en) | Aqueous hair cleansing agent | |
CN102895151B (zh) | 一种不含硫酸盐的毛发清洁剂及其制备方法 | |
JP3819765B2 (ja) | ふけ形成抑制効果を有する毛髪化粧料組成物 | |
US20130045961A1 (en) | Personal Care Compositions Having Dried Zinc Pyrithione | |
CN107898654A (zh) | 氨基酸洗发露组合物及其制备方法 | |
CN110327282A (zh) | 一种可改善头皮表皮微生物菌群的去屑洗发水及制备工艺 | |
US20130045263A1 (en) | Personal Care Compositions Having Dried Zinc Pyrithione-Polymer Aggregates | |
US6312675B1 (en) | Hair cleaner | |
CN106420407A (zh) | 一种以植物油脂替代硅油的儿童无硅油洗发水 | |
KR100289842B1 (ko) | 알킬폴리글리코시드기초한케라틴기질컨디셔닝조성물및모발세정과컨디셔닝을위한이것의용도 | |
EP0627216A2 (en) | Stable conditioning shampoo containing an anionic surfactant, a fatty alcohol, a silicone conditioner and polyethyleneimine | |
CN1167778C (zh) | 清洁剂组合物 | |
EP2934138A1 (en) | Cationic pyrithione dispersion | |
US20140303135A1 (en) | Personal Care Compositions Having Dried Zinc Pyrithione-Polymer Aggregates | |
CN115569084B (zh) | 一种液晶悬浮组合物及其制备方法与应用 | |
CN104688634A (zh) | 一种无患子祛屑止痒洗发露 | |
CN113425624A (zh) | 去屑控油组合物及其制备方法和应用 | |
CN102180829B (zh) | 一种表面改性的吡啶硫酮盐及其应用 | |
CN111249167A (zh) | 一种海盐清洁磨砂膏及其制备方法 | |
KR102500882B1 (ko) | 라멜라 구조를 갖는 컨디셔닝 샴푸 조성물 | |
CN108578350A (zh) | 一种含螺旋藻提取物的护理组合物及其制备方法 | |
CN108403461A (zh) | 一种调理剂组合物及其应用 | |
CN108498393B (zh) | 一种抗污染组合物及含有该抗污染组合物的洗发产品及其制备方法 | |
EA039052B1 (ru) | Композиция для ухода за волосами | |
CN116035935B (zh) | 去屑止痒组合物及其制备方法、洗发水及其制备方法、药剂 |
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 |