CN104758192A - 含有季铵盐的聚合物微胶囊及其制造方法 - Google Patents
含有季铵盐的聚合物微胶囊及其制造方法 Download PDFInfo
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- CN104758192A CN104758192A CN201510062486.6A CN201510062486A CN104758192A CN 104758192 A CN104758192 A CN 104758192A CN 201510062486 A CN201510062486 A CN 201510062486A CN 104758192 A CN104758192 A CN 104758192A
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- quaternary ammonium
- ammonium salt
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- polymer
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- 150000003242 quaternary ammonium salts Chemical class 0.000 title abstract description 35
- 238000000034 method Methods 0.000 title abstract description 34
- 239000003094 microcapsule Substances 0.000 claims abstract description 90
- 229960001927 cetylpyridinium chloride Drugs 0.000 claims abstract description 54
- YMKDRGPMQRFJGP-UHFFFAOYSA-M cetylpyridinium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 YMKDRGPMQRFJGP-UHFFFAOYSA-M 0.000 claims abstract description 54
- 229920000642 polymer Polymers 0.000 claims description 47
- 229920001661 Chitosan Polymers 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 7
- -1 arginine ester Chemical class 0.000 claims description 7
- 239000004475 Arginine Substances 0.000 claims description 4
- INVGWHRKADIJHF-UHFFFAOYSA-N Sanguinarin Chemical compound C1=C2OCOC2=CC2=C3[N+](C)=CC4=C(OCO5)C5=CC=C4C3=CC=C21 INVGWHRKADIJHF-UHFFFAOYSA-N 0.000 claims description 4
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 claims description 4
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 4
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- 230000003213 activating effect Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- DTOUUUZOYKYHEP-UHFFFAOYSA-N 1,3-bis(2-ethylhexyl)-5-methyl-1,3-diazinan-5-amine Chemical compound CCCCC(CC)CN1CN(CC(CC)CCCC)CC(C)(N)C1 DTOUUUZOYKYHEP-UHFFFAOYSA-N 0.000 claims description 2
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- LDOKREMYSOOJMZ-UHFFFAOYSA-N 4-ethyl-1-tetradecyl-2H-pyridine Chemical compound C(CCCCCCCCCCCCC)N1CC=C(C=C1)CC LDOKREMYSOOJMZ-UHFFFAOYSA-N 0.000 claims description 2
- ANAAMBRRWOGKGU-UHFFFAOYSA-M 4-ethyl-1-tetradecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+]1=CC=C(CC)C=C1 ANAAMBRRWOGKGU-UHFFFAOYSA-M 0.000 claims description 2
- 108010062877 Bacteriocins Proteins 0.000 claims description 2
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- GHXZTYHSJHQHIJ-UHFFFAOYSA-N Chlorhexidine Chemical compound C=1C=C(Cl)C=CC=1NC(N)=NC(N)=NCCCCCCN=C(N)N=C(N)NC1=CC=C(Cl)C=C1 GHXZTYHSJHQHIJ-UHFFFAOYSA-N 0.000 claims description 2
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- OJIYIVCMRYCWSE-UHFFFAOYSA-M Domiphen bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CCOC1=CC=CC=C1 OJIYIVCMRYCWSE-UHFFFAOYSA-M 0.000 claims description 2
- FCEXWTOTHXCQCQ-UHFFFAOYSA-N Ethoxydihydrosanguinarine Natural products C12=CC=C3OCOC3=C2C(OCC)N(C)C(C2=C3)=C1C=CC2=CC1=C3OCO1 FCEXWTOTHXCQCQ-UHFFFAOYSA-N 0.000 claims description 2
- NVNLLIYOARQCIX-MSHCCFNRSA-N Nisin Chemical compound N1C(=O)[C@@H](CC(C)C)NC(=O)C(=C)NC(=O)[C@@H]([C@H](C)CC)NC(=O)[C@@H](NC(=O)C(=C/C)/NC(=O)[C@H](N)[C@H](C)CC)CSC[C@@H]1C(=O)N[C@@H]1C(=O)N2CCC[C@@H]2C(=O)NCC(=O)N[C@@H](C(=O)N[C@H](CCCCN)C(=O)N[C@@H]2C(NCC(=O)N[C@H](C)C(=O)N[C@H](CC(C)C)C(=O)N[C@H](CCSC)C(=O)NCC(=O)N[C@H](CS[C@@H]2C)C(=O)N[C@H](CC(N)=O)C(=O)N[C@H](CCSC)C(=O)N[C@H](CCCCN)C(=O)N[C@@H]2C(N[C@H](C)C(=O)N[C@@H]3C(=O)N[C@@H](C(N[C@H](CC=4NC=NC=4)C(=O)N[C@H](CS[C@@H]3C)C(=O)N[C@H](CO)C(=O)N[C@H]([C@H](C)CC)C(=O)N[C@H](CC=3NC=NC=3)C(=O)N[C@H](C(C)C)C(=O)NC(=C)C(=O)N[C@H](CCCCN)C(O)=O)=O)CS[C@@H]2C)=O)=O)CS[C@@H]1C NVNLLIYOARQCIX-MSHCCFNRSA-N 0.000 claims description 2
- 108010053775 Nisin Proteins 0.000 claims description 2
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- 229960003121 arginine Drugs 0.000 claims description 2
- 229960000686 benzalkonium chloride Drugs 0.000 claims description 2
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 2
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- QSFOWAYMMZCQNF-UHFFFAOYSA-N delmopinol Chemical compound CCCC(CCC)CCCC1COCCN1CCO QSFOWAYMMZCQNF-UHFFFAOYSA-N 0.000 claims description 2
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- SMGTYJPMKXNQFY-UHFFFAOYSA-N octenidine dihydrochloride Chemical compound Cl.Cl.C1=CC(=NCCCCCCCC)C=CN1CCCCCCCCCCN1C=CC(=NCCCCCCCC)C=C1 SMGTYJPMKXNQFY-UHFFFAOYSA-N 0.000 claims description 2
- WKEDVNSFRWHDNR-UHFFFAOYSA-N salicylanilide Chemical compound OC1=CC=CC=C1C(=O)NC1=CC=CC=C1 WKEDVNSFRWHDNR-UHFFFAOYSA-N 0.000 claims description 2
- 229950000975 salicylanilide Drugs 0.000 claims description 2
- 229940084560 sanguinarine Drugs 0.000 claims description 2
- YZRQUTZNTDAYPJ-UHFFFAOYSA-N sanguinarine pseudobase Natural products C1=C2OCOC2=CC2=C3N(C)C(O)C4=C(OCO5)C5=CC=C4C3=CC=C21 YZRQUTZNTDAYPJ-UHFFFAOYSA-N 0.000 claims description 2
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 claims description 2
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 20
- 239000004141 Sodium laurylsulphate Substances 0.000 description 20
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 11
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- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
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- 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 4
- 239000000600 sorbitol Substances 0.000 description 4
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- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 4
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- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
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- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 2
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
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- 241000195940 Bryophyta Species 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
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- 230000003232 mucoadhesive effect Effects 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 210000003296 saliva Anatomy 0.000 description 1
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 1
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- 239000000230 xanthan gum Substances 0.000 description 1
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Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
-
- 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
- A61K8/11—Encapsulated compositions
-
- 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
- A61K8/4926—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having six membered rings
-
- 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
- A61K8/73—Polysaccharides
- A61K8/736—Chitin; Chitosan; Derivatives thereof
-
- 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
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
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)
- Oral & Maxillofacial Surgery (AREA)
- Cosmetics (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
描述了被聚合物微胶囊包封的季铵盐和制造这类微胶囊的方法。该季铵盐可以是氯化十六烷基吡啶鎓。该包封季铵盐的聚合物微胶囊可用作洁齿剂中的成分。
Description
本申请为分案申请,原申请的申请日为2008年3月12日,申请号为200880018078.9(PCT/US2008/056654),发明名称为“含有季铵盐的聚合物微胶囊及其制造方法”。
发明背景
聚合物微胶囊可以通过本领域中已知的几种方法之一制造。这类方法包括单和复乳化溶剂蒸发技术。
聚合物微胶囊具有广泛用途,如用在给药体系和个人护理产品,包括洁齿剂(即用于清洁牙齿的物质,如膏或粉)中。但是,聚合物微胶囊通常不在提供活性成分(如构成洁齿制剂的活性成分)的长效缓释的同时为该微胶囊包封的活性成分提供良好保护以抵御其外部环境。
氯化十六烷基吡啶鎓(CPC)是可用于口腔护理用途的阳离子型、表面活性剂类、广谱抗菌剂。但是,由于其正电荷,CPC与例如洁齿剂中常用的各种常见成分,如十二烷基硫酸钠(SLS)(一种阴离子型表面活性剂)形成稳定络合物。这些类型的反应阻碍在例如常用洁齿制剂中使用CPC实现有效抗菌益处。
在洁齿剂用途中,为使微胶囊在牙膏制造和储存过程中保持完整,微胶囊应具有下列性质:1)良好机械性质以承受混合和高速填充过程中高达大约1000/s的剪切力;2)使该胶囊在高达大约71℃的温度下保持完整的良好温度稳定性;3)使胶囊在具有最多大约2%浓度和大约5-8pH值的十二烷基硫酸钠存在下和在各种水/润湿剂比率下稳定的良好化学稳定性。此外,在刷牙时,该微胶囊应破裂和在不形成非活性络合物的情况下直接将CPC释放到口腔中。
许多因素触发微胶囊在刷牙过程中破裂,如:1)归因于牙刷毛的摩擦和剪切的机械触发因素;2)归因于从洁齿基料到口腔环境的pH变化的pH触发因素;3)归因于洁齿剂在刷牙过程中被口中的唾液稀释的渗透触发因素;和4)归因于口中的酶造成的聚合物键断裂的酶触发因素。
最近在文献中也已经报道,已经经由油包水乳状液法形成具有粘膜粘附性聚合物的聚合物微胶囊。
相应地,仍然需要在相当长时期,如24小时内提供活性成分的长效缓释模式的同时为活性成分提供良好保护以抵御其外部环境的聚合物微胶囊。此外,洁齿剂中所用的这类聚合物微胶囊应具有能够实现活性成分在相当长时期内的长效缓释模式的粘膜粘附性质。特别地,仍然需要防止活性成分(如CPC)接触不相容成分(如SLS)的包囊技术。
发明概述
本发明提供了包含被聚合物微胶囊包封的季铵盐的组合物,其中该季铵盐包含下列结构所示的阳离子:
其中R1、R2和R3各自独立地为烷基或氢原子,或其中R1和R2可以一起形成环结构;
和选自卤素离子、氯离子、溴离子和氟离子的阴离子。
本发明进一步提供制造抗菌洁齿剂的方法,包括(a)将季铵盐包封在聚合物微胶囊内,和(b)将洁齿剂与被包囊的季铵盐混合。
本发明的另一方面是制造被平均直径大约5微米至大约50微米的聚合物微胶囊包封的季铵盐的方法,包括(a)将该季铵盐溶解在水相中,(b)将该水相分散在含有溶解的聚合物的疏水有机溶剂内以形成溶液,(c)将该溶液分散在外水相中,和(d)从步骤(c)的外水相中除去溶剂以形成包封季铵盐的聚合物微胶囊。
本发明的再一方面包括制造被平均直径大约5微米至大约50微米的聚合物微胶囊包封的季铵盐的方法,包括(a)将聚合物和季铵盐溶解在水相中,(b)以油包水乳状液滴形式分散该水相,和(c)在升高的温度下搅拌步骤(b)的乳状液以使水相蒸发和形成包封季铵盐的聚合物微胶囊。
附图简述
在联系附图阅读时,会更好地理解上述概述以及本发明的实施方案的下列详述。但是,应该理解的是,本发明不限于所示确切布置和工具。在附图中:
图1a是壳聚糖微胶囊在pH 7的水中在时间=0时的荧光图像;
图1b是壳聚糖微胶囊在pH 7的水中在时间=24时的荧光图像;
图2是壳聚糖微胶囊在十二烷基硫酸钠存在下的荧光图像;
图3a是壳聚糖微胶囊在pH 4的水中在时间=0时的荧光图像;
图3b是壳聚糖微胶囊在pH 4的水中在时间=24时的荧光图像;
图4a是壳聚糖微胶囊在pH 9的水中在时间=0时的荧光图像;
图4b是壳聚糖微胶囊在pH 9的水中在时间=24时的荧光图像;
图5a至5c是壳聚糖微胶囊在水中分别在0/s、100/s和500/s剪切速率下的荧光图像。
图6a是聚合物微胶囊在氯化十六烷基吡啶鎓存在下的荧光图像;且
图6b是聚合物微胶囊在不存在氯化十六烷基吡啶鎓的情况下的荧光图像。
发明详述
本发明提供了包括包封在聚合物微胶囊内的季铵盐的组合物。该组合物任选还包括各种活性剂。活性剂可以是亚锡离子试剂、三氯生、单磷酸三氯生、洗必泰、阿来西定、海克替啶、血根碱、苯扎氯铵、水杨酰苯胺、精氨酸酯、乙基十二烷基精氨酸酯、双酚、度米芬、氯化十四烷基吡啶鎓(TPC)、氯化N-十四烷基-4-乙基吡啶鎓(TDEPC)、奥替尼啶、地莫匹醇、辛哌醇、乳酸链球菌肽、锌离子试剂、铜离子试剂、香精油、呋喃酮、细菌素、其盐、其混合物、和类似的已知活性剂。
一方面,本发明提供了包括被聚合物微胶囊包封的季铵盐的组合物。该季铵盐包括阳离子和阴离子。阳离子可以如下列结构(I)所示:
其中R1、R2和R3各自独立地为直链或支链的、取代或未取代的烷基或氢原子,或其中R1和R2可以一起形成环结构。阴离子可以是各种卤素离子,如氯离子、溴离子、氟离子和与预期用途相符的其它类似离子或其盐,如PO4 -、SO4 -等中的任一种。
阳离子也可以如下列结构(II)所示:
其中R3是具有5至25个碳原子的烷基;R3也可以是具有10至20个碳原子的直链或支链的、取代或未取代的烷基。阳离子结构(II)可以包括至少三个未取代的键。
本实施方案的季铵盐可以是氯化十六烷基吡啶鎓。此外,可以在单一聚合物微胶囊中包封一种以上的季铵盐。
本发明的聚合物微胶囊可以包括各种标准微胶囊材料。这类微胶囊材料包括但不限于,几丁质、壳聚糖、聚己酸内酯、聚丙烯酸及其衍生物和共聚物。壳聚糖特别可具有如下优点,即其在生理pH值附近表现出依赖于pH值的性能,其在较低pH值下具有提高的溶解度。因此,可以在洁齿制剂中利用这种性质,因为CPC从聚合物微胶囊中扩散出来的速率在大约8-9的pH值下比在大约7的pH值下慢。
本文中用于描述聚合物微胶囊的术语“聚合”是指构成该微胶囊的至少一种成分是聚合材料,但应该理解的是,在微胶囊形成中也可以使用非聚合物形式的其它成分,如树胶、明胶等。
该聚合物微胶囊可具有大约5微米至大约50微米的直径,该尺寸可以更大或更小,只要用途与该尺寸变化相符。
该组合物也可以包括任选氟离子源。氟离子源被认为是可以在含水环境中释放氟离子的任何材料。这类氟离子源的实例描述在美国专利Nos.3,538,230;3,689,637;3,711,604;3,911,104;3,935,306;和4,040,858中,它们都经此引用并入相关部分中。但是,应该理解的是,可以向该组合物提供本领域中已知的或待开发的任何合适的氟离子源。
本发明的第二方面提供了制造包封季铵盐的聚合物微胶囊的方法。这种方法包括(a)将季铵盐(如上所述)溶解在水相,如MilliQ水或蒸馏水中,(b)将该水相分散在含有溶解的聚合物(如几丁质、壳聚糖、聚己酸内酯或聚丙烯酸)的疏水有机溶剂中以形成溶液,(c)将该溶液分散在外水相(即第二水相)中,和(d)例如通过蒸发或本领域中已知的任何其它方法从步骤(c)的外水相中除去溶剂。
本发明还提供了制造被具有大约5微米至大约50微米微胶囊直径的聚合物微胶囊包封的季铵盐的方法。这种方法包括(a)将聚合物(如上所述)和季铵盐(如上所述)溶解在水相中,(b)(例如通过吸移)以油包水乳状液滴形式分散该水相,和(c)在升高的温度下搅拌步骤(b)的乳状液以蒸发该水相,由此形成包封季铵盐的聚合物微胶囊。
该方法的所述升高的温度优选为大约95℃至大约100℃。
该方法的季铵盐可以是上述任何季铵盐并优选是氯化十六烷基吡啶鎓。
根据该方法制成的聚合物微胶囊可以以各种形状和形式,如微球、微粒等制造。
本发明中还包括制造抗菌洁齿剂的方法。该洁齿剂可以是,但不限于,膏、凝胶、粉等。该方法包括使用本公开的方法将季铵盐,如本文所述的那些包封在聚合物微胶囊内并将洁齿剂与该包封的季铵盐混合。
该方法的季铵盐优选为氯化十六烷基吡啶鎓。
本发明中还包括制造被平均直径大约5微米至大约50微米的聚合物微胶囊包封的季铵盐的方法。这种方法包括(a)将季铵盐溶解在水相(如MilliQ水或蒸馏水)中,(b)将该水相分散在含有溶解的聚合物(例如几丁质、壳聚糖、聚己酸内酯或聚丙烯酸)的疏水有机溶剂中以形成溶液,(c)将该溶液分散在外水相中,和(d)(例如通过蒸发)从该外水相中除去溶剂,由此形成包封季铵盐的聚合物微胶囊。
本发明中还包括包含包封季铵盐的聚合物微胶囊的个人护理产品。该个人护理产品可进一步包括氟离子源。这类个人护理产品例如是牙膏、漱口水、慕思、喷雾剂、薄膜和其它便携形式。
本发明可以制造具有下列性质的微胶囊:1)纳米级至毫米级的微胶囊尺寸(通常该微胶囊的尺寸越小,机械稳定性越好);2)尺寸分布;3)纳米级至微米级的微胶囊壳厚度;和4)壳和/或双重壳层结构的不可透性。
本发明还可以使用阳离子型表面活性剂类化合物(如CPC)作为乳液稳定剂以提高聚合物微胶囊形成过程中的包囊效率。这类胶囊可以防止CPC接触该聚合物微胶囊外部的其它成分,如洁齿剂中的那些成分,因此可以在刷牙过程中在胶囊破裂后作为有效抗菌剂释放CPC。
CPC包囊的益处包括防止CPC和洁齿制剂之间的不利相互作用以使有效CPC(即非稳定络合物形式的CPC)的给药最大化且CPC本身可充当乳液稳定剂以防止水或油滴在油包水或水包油乳状液中聚结。
例如,但非限制地,在下列实施例中例证本发明的具体实施方案。
实施例1
如下制造和评测具有180毫克CPC的壳聚糖氯化十六烷基吡啶鎓(CPC)微胶囊(10重量%CPC的组合物(1%的CPC是若丹明标记的))。
使用下列材料由油包水乳状液制备壳聚糖微胶囊:
壳聚糖(>85%脱乙酰化,Aldrich 417963),
MilliQ水,
冰醋酸,
FD&C blue #1食品着色染料,
氯化十六烷基吡啶鎓(CPC),
矿物油(白油、重油),和
单油酸失水山梨糖醇酯(司班-80)表面活性剂
通过将9克壳聚糖与600毫升水/1%(体积)乙酸溶液混合,制备壳聚糖溶液。通过搅拌和将该混合物加热至大约60℃大约1天,使壳聚糖溶解在该600毫升水/1%(体积)乙酸溶液中。然后将3.3毫升含10重量%CPC和10克蓝色染料(预溶解)的水溶液添加到200毫升壳聚糖溶液中。
然后通过添加乳化剂(IKA RE162/P)以及800毫升矿物油和8毫升司班-80,制备混合物,以100rpm搅拌5分钟以混合。使该混合物静置20分钟以使气泡上升和爆裂。然后在大约20分钟期间内通过两个带有16gauge针头的60毫升注射器将壳聚糖溶液添加到该混合物中。然后在壳聚糖溶液添加完成后将所得乳状液再搅拌30分钟。
然后将该乳状液转移到在磁搅拌板上的2升Pyrex烧杯中。在搅拌的同时,将该乳状液加热至大约70℃并放置过夜(大约14-16小时)以蒸发乙酸和大部分水。该乳状液从极乳状的浅蓝色变成混浊的更深蓝色。然后在连续搅拌下将该乳状液加热至大约95℃-100℃直至第二天(大约24小时)。该乳状液的颜色从蓝色变成浅绿色。
然后将该乳状液收集到50毫升离心管中并各自以3,500rpm旋转10分钟。大多数粒子在离心后沉降,但大部分的最小粒子(尺寸为几微米或更小)保持悬浮。滗析弃置该溶液。在显微镜下,看出离心出的粒子相当致密堆积,甚至略微变形,表明可能仍有一些残留水使粒子保持柔软。
在一半的离心管中,使用玻璃吸管将粒子再悬浮在小的余量矿物油中。将所有残留粒子/油浆料从这些管转移到玻璃管瓶中(总体积大约15毫升),并再以3,500rpm离心1小时。再滗析弃置该溶液,并用吸管尽可能除去残留油。
在另一半管中,在各管中通过涡旋将粒子再悬浮在大约10毫升己烷中。将所有管中的液体收集到两个管中,然后以3,500rpm离心10分钟。滗析弃置溶液,并在各管中将粒子再悬浮在大约10毫升己烷中。最后,通过重力过滤法经由定性滤纸过滤该溶液,并在通风橱中放置干燥。
方法 物理和化学稳定性表征:通过机械稳定性评测进行包封CPC的壳聚糖微胶囊的表征。如下进行包封CPC的壳聚糖微胶囊的化学表征:1)水合实验,和2)在SLS存在下的化学稳定性实验。
机械稳定性表征:在100/s和500/s的各种剪切强度下在连续剪切条件下评测包封CPC的壳聚糖微胶囊的机械稳定性。
化学稳定性表征:
水合实验:使用显微技术在水中在各种pH条件下评测包封CPC的壳聚糖微胶囊。使用荧光光谱技术评测悬浮中的包封CPC的壳聚糖微胶囊的上清液部分中的荧光变化
在SLS存在下的稳定性实验:将包封CPC的壳聚糖微胶囊悬浮在1% SLS中并评测与SLS的相互作用。
结果:根据该方法制成的包封CPC的壳聚糖微胶囊相当稳定并由于该聚合物基质的亲水性而能够迅速释放CPC。此外,据发现,在水相中加入10重量%CPC由于能够在给定剪切速率下形成更小的乳状液滴而简化加工。
收集的壳聚糖微胶囊的荧光图像显示在图1a和1b中。荧光来自十八烷基若丹明-B,其以CPC的1%的浓度掺入以充当示踪剂。图1a显示了在0时间的壳聚糖微胶囊。图1b显示了在24小时时间的壳聚糖微胶囊。在pH 7下直到24小时才观察到壳聚糖微胶囊的形状和尺寸的极小变化。此外,在室温下表征从壳聚糖微胶囊中释放出的若丹明染料的量长达12周。从包封CPC的壳聚糖微胶囊中释放出少于0.1%若丹明染料。
图2显示了包封CPC的壳聚糖微胶囊在1%十二烷基硫酸钠(SLS)存在下的化学稳定性。在1% SLS中,少于0.1%的壳聚糖微胶囊在4周时间后破裂。此外,没有观察到由SLS-CPC相互作用引起的沉淀。
图3和4显示了包封CPC的壳聚糖微胶囊在酸性和碱性pH条件下的化学稳定性。图3表明该壳聚糖微胶囊在含水环境中在pH 4下稳定长达24小时。图4表明该壳聚糖微胶囊在含水环境中在pH 9下稳定长达24小时。
图5a-5c显示了包封CPC的壳聚糖微胶囊在各种剪切速率下的机械稳定性。图5a显示了暴露在0/s剪切速率(即无剪切)下的壳聚糖微胶囊,即对照物。图5b显示了暴露在100/s剪切速率下的壳聚糖微胶囊。图5c显示了暴露在500/s剪切速率和CPC活性释放态下的壳聚糖微胶囊。
图6a和6b显示了用和不用CPC制成的聚合物微胶囊的尺寸。图6a显示了单独用FD&C blue #1且不用CPC制成的聚合物微胶囊的尺寸。图6b显示了用FD&C blue #1和CPC制成的聚合物微胶囊的尺寸。在将CPC添加到该乳状液中时,其防止水滴聚结,这随后产生更小胶囊。
因此,除提供更简单的加工外,这种方法提供了可能使用各种水溶性、生物相容性和甚至粘膜粘附性聚合物的优点。
实施例2
各种洁齿制剂的实施例进一步例证本发明并且不是要以任何方式限制本发明。用根据本发明制成的包封CPC的微胶囊制造这类制剂。
表1提供了含磷酸盐的洁齿剂组合物。表2提供了含Gantrez共聚物的洁齿剂组合物。表3提供了含PCC的洁齿剂组合物。表4提供了使用液体制剂的洁齿剂组合物。
表1
成分 | % Wt/Wt |
水 | 18.46 |
NaF | 0.24 |
糖精钠 | 0.45 |
山梨糖醇 | 28 |
甘油 | 12 |
Gantrez-97 | 1 |
NaOH(50%溶液) | 2 |
焦磷酸四钠(TSPP) | 1 |
三聚磷酸钠(STPP) | 7 |
角叉菜胶 | 0.35 |
羧甲基纤维素(CMC) | 0.8 |
二氧化硅 | 25 |
十二烷基硫酸钠(SLS) | 1.2 |
香料 | 1.0 |
CPC微胶囊 | 1.5 |
表2
成分 | % Wt/Wt |
水 | 27.26 |
NaF | 0.24 |
糖精钠 | 0.3 |
TiO2 | 0.5 |
山梨糖醇 | 21 |
甘油 | 20 |
聚乙二醇(PEG) | 0.5 |
Gantrez-97 | 2 |
NaOH(50%溶液) | 1.2 |
角叉菜胶 | 0.4 |
羧甲基纤维素(CMC) | 1.1 |
二氧化硅 | 21.5 |
十二烷基硫酸钠(SLS) | 1.5 |
香料 | 1.0 |
CPC微胶囊 | 1.5 |
表3
成分 | % Wt/Wt |
水 | 31.89 |
单氟化物磷酸盐 | 0.76 |
糖精钠 | 0.35 |
山梨糖醇 | 21 |
NaOH(50%溶液) | 0.5 |
苏打灰 | 0.75 |
黄原胶 | 0.2 |
羧甲基纤维素(CMC) | 0.65 |
角叉菜胶 | 0.2 |
PCC | 29.4 |
二氧化硅 | 10 |
十二烷基硫酸钠(SLS) | 1.6 |
香料 | 1.2 |
CPC微胶囊 | 1.5 |
表4
成分 | % Wt/Wt |
水 | 4.68 |
NaF | 0.26 |
糖精钠 | 0.37 |
山梨糖醇 | 67.1 |
甘油 | 7.46 |
聚乙二醇PEG 600 | 1.5 |
焦磷酸四钠(TSPP) | 0.53 |
角叉菜胶 | 0.23 |
羧甲基纤维素(CMC) | 0.8 |
二氧化硅 | 12.5 |
十二烷基硫酸钠(SLS) | 1.6 |
椰油甜菜碱 | 0.37 |
香料 | 1.1 |
CPC微胶囊 | 1.5 |
Claims (2)
1. 一种包封氯化十六烷基吡啶鎓的聚合物微胶囊,其中聚合物微胶囊具有5-50微米直径并且包含壳聚糖,进一步包含选自亚锡离子试剂、三氯生、单磷酸三氯生、洗必泰、阿来西定、海克替啶、血根碱、苯扎氯铵、水杨酰苯胺、精氨酸酯、乙基十二烷基精氨酸酯、双酚、度米芬、氯化十四烷基吡啶鎓(TPC)、氯化N-十四烷基-4-乙基吡啶鎓(TDEPC)、奥替尼啶、地莫匹醇、辛哌醇、乳酸链球菌肽、锌离子试剂、铜离子试剂、香精油、呋喃酮、细菌素、其盐及其混合物的活性剂。
2. 权利要求1的聚合物微胶囊,其中该聚合物微胶囊进一步包含氟离子源。
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CN113558047A (zh) * | 2020-04-28 | 2021-10-29 | 埃立坦株式会社 | 杀菌性纳米胶囊、葡萄状微粒集合体、消毒杀菌过滤器和它们的制造方法 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110037023A (zh) * | 2019-04-19 | 2019-07-23 | 广州佳伲斯防霉抗菌科技有限公司 | 一种用于集装箱的防霉杀菌剂及其制备方法 |
CN113558047A (zh) * | 2020-04-28 | 2021-10-29 | 埃立坦株式会社 | 杀菌性纳米胶囊、葡萄状微粒集合体、消毒杀菌过滤器和它们的制造方法 |
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