CN115485033A - 抗细菌组合物 - Google Patents
抗细菌组合物 Download PDFInfo
- Publication number
- CN115485033A CN115485033A CN202180032439.0A CN202180032439A CN115485033A CN 115485033 A CN115485033 A CN 115485033A CN 202180032439 A CN202180032439 A CN 202180032439A CN 115485033 A CN115485033 A CN 115485033A
- Authority
- CN
- China
- Prior art keywords
- silver
- cleaning composition
- surfactant
- sodium
- nitrate
- 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.)
- Pending
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- 239000000203 mixture Substances 0.000 title claims abstract description 154
- 230000000844 anti-bacterial effect Effects 0.000 title description 4
- 239000004094 surface-active agent Substances 0.000 claims abstract description 90
- 238000004140 cleaning Methods 0.000 claims abstract description 70
- 239000000344 soap Substances 0.000 claims abstract description 48
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 36
- 239000000194 fatty acid Substances 0.000 claims abstract description 36
- 229930195729 fatty acid Natural products 0.000 claims abstract description 36
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 33
- 239000003755 preservative agent Substances 0.000 claims abstract description 27
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 23
- 229940100890 silver compound Drugs 0.000 claims abstract description 23
- 150000003379 silver compounds Chemical class 0.000 claims abstract description 23
- 239000002562 thickening agent Substances 0.000 claims abstract description 21
- 150000002823 nitrates Chemical class 0.000 claims abstract description 12
- 230000002335 preservative effect Effects 0.000 claims abstract description 12
- -1 alkyl ether sulfates Chemical class 0.000 claims description 99
- 239000004332 silver Substances 0.000 claims description 77
- 229910052709 silver Inorganic materials 0.000 claims description 77
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 18
- 230000008901 benefit Effects 0.000 claims description 16
- 229910002651 NO3 Inorganic materials 0.000 claims description 14
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 13
- 229910052708 sodium Inorganic materials 0.000 claims description 13
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 12
- 230000000845 anti-microbial effect Effects 0.000 claims description 11
- 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 description 10
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003945 anionic surfactant Substances 0.000 claims description 9
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 9
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 claims description 8
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 8
- SMVRDGHCVNAOIN-UHFFFAOYSA-L disodium;1-dodecoxydodecane;sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC SMVRDGHCVNAOIN-UHFFFAOYSA-L 0.000 claims description 7
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 7
- 239000004317 sodium nitrate Substances 0.000 claims description 7
- 235000010344 sodium nitrate Nutrition 0.000 claims description 7
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- 239000005711 Benzoic acid Substances 0.000 claims description 5
- 150000008051 alkyl sulfates Chemical group 0.000 claims description 5
- 235000010233 benzoic acid Nutrition 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001923 silver oxide Inorganic materials 0.000 claims description 5
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 5
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 4
- 229940071536 silver acetate Drugs 0.000 claims description 4
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 4
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 4
- 239000004599 antimicrobial Substances 0.000 claims description 3
- 229940040102 levulinic acid Drugs 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 claims description 3
- 229940082004 sodium laurate Drugs 0.000 claims description 3
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 2
- 229920006318 anionic polymer Polymers 0.000 claims description 2
- 229960004365 benzoic acid Drugs 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- 230000003115 biocidal effect Effects 0.000 description 67
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 65
- 238000009472 formulation Methods 0.000 description 46
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 35
- 239000011780 sodium chloride Substances 0.000 description 32
- 210000003491 skin Anatomy 0.000 description 31
- 239000000047 product Substances 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 239000002253 acid Substances 0.000 description 25
- 241000191967 Staphylococcus aureus Species 0.000 description 22
- 230000000694 effects Effects 0.000 description 21
- 150000003839 salts Chemical class 0.000 description 19
- 125000000217 alkyl group Chemical group 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 18
- 230000009467 reduction Effects 0.000 description 18
- 150000007513 acids Chemical class 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 15
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical class [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 238000001514 detection method Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 239000002054 inoculum Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000002736 nonionic surfactant Substances 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 239000004615 ingredient Substances 0.000 description 10
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 229920001223 polyethylene glycol Polymers 0.000 description 9
- 230000002195 synergetic effect Effects 0.000 description 9
- 229920002472 Starch Polymers 0.000 description 8
- 239000003093 cationic surfactant Substances 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 8
- 235000010980 cellulose Nutrition 0.000 description 8
- 229920002678 cellulose Polymers 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 230000001965 increasing effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 235000019198 oils Nutrition 0.000 description 8
- 235000019698 starch Nutrition 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000001913 cellulose Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 235000013399 edible fruits Nutrition 0.000 description 7
- 244000005700 microbiome Species 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000002252 acyl group Chemical group 0.000 description 6
- 230000001580 bacterial effect Effects 0.000 description 6
- 229960003237 betaine Drugs 0.000 description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 description 6
- 210000002421 cell wall Anatomy 0.000 description 6
- 239000003599 detergent Substances 0.000 description 6
- 239000003974 emollient agent Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 230000000813 microbial effect Effects 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 239000008107 starch Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000002888 zwitterionic surfactant Substances 0.000 description 6
- 241000192125 Firmicutes Species 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- 235000020971 citrus fruits Nutrition 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 241000282372 Panthera onca Species 0.000 description 4
- 229920002873 Polyethylenimine Polymers 0.000 description 4
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 4
- 239000013504 Triton X-100 Substances 0.000 description 4
- 229920004890 Triton X-100 Polymers 0.000 description 4
- 235000010443 alginic acid Nutrition 0.000 description 4
- 229920000615 alginic acid Polymers 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 239000002280 amphoteric surfactant Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 4
- 239000000693 micelle Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 235000010199 sorbic acid Nutrition 0.000 description 4
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- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 3
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- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
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- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- BORJONZPSTVSFP-UHFFFAOYSA-N tetradecyl 2-hydroxypropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)C(C)O BORJONZPSTVSFP-UHFFFAOYSA-N 0.000 description 1
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- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
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- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229960000790 thymol Drugs 0.000 description 1
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- 210000001519 tissue Anatomy 0.000 description 1
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- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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Abstract
公开了一种清洗剂组合物,其包含硫酸盐表面活性剂;脂肪酸皂;银化合物;增稠剂;和硝酸盐。清洁组合物的pH为5至10。公开了另一种清洁组合物,包含硫酸盐表面活性剂;银化合物;增稠剂;硝酸盐;和防腐剂。该清洁组合物的pH为4至5.5。
Description
技术领域
本文公开了清洁组合物。该清洁组合物可包含5至25重量%的硫酸盐表面活性剂;0至5重量%的脂肪酸皂;0.03至3ppm的银化合物;0.05至1重量%的增稠剂;和1至10重量%的硝酸盐。清洁组合物的pH为5至10。清洁组合物还可包含5%至25重量%的硫酸盐表面活性剂;0.03至3ppm的银化合物;0.05至1重量%的增稠剂;1至10重量%的硝酸盐;和0.05至1重量%的防腐剂。清洁组合物的pH为4.5至5.5。还公开了制备清洁组合物的方法。
背景技术
作为人体最大的器官,皮肤执行几个主要功能。它用作边界层,帮助维持体温并保留必需的液体。它还针对毒性剂和有害的太阳辐射提供保护。人类皮肤每天暴露于各种微生物污染物(通过暴露于体液)和各种环境因素。这些污染物包括革兰氏阴性和革兰氏阳性细菌、酵母、真菌、霉菌、原生动物和病毒。一旦在皮肤上建立,这些生物体可引起炎症、刺激和/或感染。刺激可以引发免疫事件的复杂级联。因此,适当的皮肤保养对良好的健康是必要的,因而对许多人来说,从每日清洁开始。定期的皮肤清洁可以降低皮肤上微生物污染物的水平,并因此也可以预防或最小化皮肤刺激和炎症(D.W.Koenig等人,―Skin cleansingcomposition incorporation anionic particles”,US6,764,988)。
传统上,皮肤清洁包括杀死、结合或去除皮肤表面上的污染物的任何活动,并且通常使用由液体清洁产品或清洁固体如皂条产生的基于溶液的“液体”来实现。虽然由于这些活动确实发生微生物污染物的去除,但污染水平通常仅降低10至100倍(1至2个log10降低)。微生物的残留水平然后通常足以快速重建微生物污染。为此,在清洁产品中应用杀生物活性成分以实现微生物群体的更显著减少通常是更有吸引力的。
抗微生物剂的作用机制与生物体对药剂产生抗性的风险有关。作用在生物体上/生物体内的单一、相对隐蔽的关键位点上的药剂更容易规避,从而仅需要单个突变来产生抗性。另一方面,靶向多个位点从而干扰基本的和不可缺少的细胞过程的药剂不太可能被一些随机突变所废除(D.G.Romero-Urbina等人,―Ultrastructural change inmethicillin-resistant Staphylococcus aureus induced by positively chargedsilver nanoparticles”,Beilstein Journal of Nanotechnology 6,2396-2405(2015))。
先前已经讨论了银作为杀生物剂的使用(R.E.Burrell,―A scientificperspective on the use of topical silver preparations”,Ostomy/WoundManagement 49,19-24(2003);A.B.G.Lansdown和A.Williams,―How safe is silver inwound care”,J.Wound Care 13,131-136(2004))并且认为其涉及多个攻击线,包括破坏细菌膜和细胞壁、细胞组分的凝结、DNA的结合和缩合,以及通过与硫醇基团结合而使关键的膜结合蛋白质和酶失活(Q.L.Feng等人,―A mechanistic study of the antibacterialeffect of silver ions on Escherichia coli and Staphylococcus aureus”,J.Biomedical Materials Research 52,662-668(2000))。因此,银离子不太可能被生物体中的随机突变阻碍。然而,单独银离子的抗微生物作用的时间尺度实际上不适于手洗应用。与洗手相关的条件限制了活性成分的浓度和与被污染表面的接触时间。个人经验表明,洗手通常花费的时间的上限为约30秒至约60秒(P.Chandar等人,“Liquid soap havingenhanced antibacterial activity”,US 2016/0053206A1)。然而,银离子的杀生物作用的大多数研究在数分钟至数小时的时间尺度上进行(C.P.Randall等人,―The silvercation(Ag+):anti-staphylococcal activity,mode of action and resistancestudies”,J.Antimicrobial Chemotherapy 68,131-138(2013))。这种相对测量的步调对于革兰氏阳性细菌尤其如此,如金黄色葡萄球菌,其中含有带负电荷的结合位点的厚肽聚糖层被认为减缓银离子通过细菌细胞壁的作用。以某种方式加速银的杀生物作用是有利的,使得其可能可用于清洁产品中。如果使用的银含量也可以降低,则将使由于形成银氧化物而引起的变色的问题最少(Agarkhed等人,―Cleansing composition containingoligodynamic metal and efficacy enhancing agent”,US 2016/0362646 A1)。
最近公开了一种解决具有最小银离子含量的快速杀生物作用的挑战的解决方案,其包括将脂肪酸皂与银离子组合。所得混合物在杀生物作用方面显示出比单独采用的两种成分显著增强(Chandar等人,US 2016/0053206A1)。然而,以前认为这种协同作用限于脂肪皂与银的组合(在10-11范围内的皂类pH下),并且不扩展到非皂表面活性剂和较低的pH范围。
持续需要提供一种清洁组合物,其在较低pH下提供所需的杀生物作用,并具有使用非皂表面活性剂的可能性。
发明内容
在各个方面,公开了清洁组合物。清洁组合物包含:5至25重量%的硫酸盐表面活性剂;0至5重量%的脂肪酸皂;0.03至3ppm的银化合物;0.05至1重量%的增稠剂;和1至10重量%的硝酸盐。清洁组合物的pH为5至10。
清洁组合物包含:5至25重量%的硫酸盐表面活性剂;0.03至3ppm的银化合物;0.05至1重量%的增稠剂;1至10重量%的硝酸盐;和0.05-1重量%的防腐剂。清洁组合物的pH为4至5.5。
通过以下详细描述举例说明上述的和其它的特征和特性。
具体实施方式
本文公开了各种清洁组合物。本公开的清洁组合物公开了硫酸盐类表面活性剂还显示出使用银的增强的杀生物作用,并且在约pH 4至约pH 10的宽得多的pH范围内表现出增强的杀生物作用,例如5至10,例如4至5.5,例如4.5至5.5。在该pH范围的下限,相应的皮肤清洁制剂与各种防腐剂相容,如有机酸,包括但不限于苯甲酸、山梨酸或其组合。不希望受理论的限制,很可能这种增强的杀生物作用的有效性以前没有被认识到,因为通常在这种皮肤清洁制剂中发现的高水平的氯离子倾向于将银离子沉淀为氯化银。这样的高含量可以作为表面活性剂合成的副产物存在于制剂中或有意地加入以调节制剂流变学。用本文公开的组合物出乎意料地发现,用硝酸盐替代氯化物盐将保持银离子的溶解度和功效,同时仍允许流变控制。硝酸盐还将提供与银的协同作用,具有一定程度的抗氯离子和抗聚羧酸的保护作用。
图1很好地描述了上述的协同作用,其显示了时间-杀伤实验的结果,在该实验中金黄色葡萄球菌接种物暴露于一系列药剂高达60秒,并分离存活的生物体和计数。图1显示了当表面活性剂SLES-1EO与银离子组合时增强的杀生物作用。从琼脂平板上的24小时培养物制备约107.5菌落形成单位/毫升(CFU/mL)的金黄色葡萄球菌接种物。测试条件为pH 7和25℃。
将(存活细胞数(CFU/mL)/初始细胞数)的log10相对暴露时间作图。符号大小与误差棒的大小匹配或超过误差棒的大小,且在SLES+银离子的情况下,存活细胞数处于2000CFU/mL的检测限。暴露时间限制于仅60s,因为该时间范围是用于洗手的时间量的实际估计。观察到用水的对照洗涤在这些条件下没有杀生物作用,并且用通常含量的阴离子表面活性剂(用水1:1稀释的模型10% SLES-1EO-基制剂)也没有杀生物作用。还示出了用从硝酸银溶液递送的1ppm银离子的洗涤,使用稀释的NaOH和HNO3溶液将该溶液和前述溶液的pH调节至7。而且,银溶液对这种短时间尺度的暴露没有显示出杀生物作用。最后,用水以1:1稀释的10% SLES和1ppm银离子的组合在少至10s的暴露时间后显示存活生物体的4log10降低。注意到该降低水平代表在这些实验条件下的检测极限。
虽然阴离子表面活性剂可对某些微生物具有杀生物作用,并且银离子被公认为具有广谱、多维的杀生物作用,但它们在图1中测试的水平和时间尺度上的单个功效并不显著。然而,可以看出它们的组合引起在用于身体清洁的时间尺度上发挥作用的真正显著的、协同的杀生物作用。
本文所公开的清洁组合物可包含硫酸盐表面活性剂、脂肪酸皂、银化合物、增稠剂和硝酸盐。该清洁组合物的pH可为4.5至10.5,例如5至10,例如6至9。清洁组合物可包含硫酸盐表面活性剂、银化合物、增稠剂、硝酸盐和防腐剂。该清洁组合物的pH可为4至5.5,例如4.5至5.5。
用于清洁组合物的组分可以各种不同量存在。例如,硫酸盐表面活性剂可以以2至35重量%,例如3至30重量%,例如5至25重量%,例如10至20重量%的量存在。银化合物可以以0.01至5ppm,例如0.02至4ppm,例如0.03至3ppm的量存在。硝酸盐可以以硝酸盐的0.5至25重量%,例如0.75至15重量%,例如1至10重量%,例如2.5至7.5重量%的量存在。增稠剂可以以0至15重量%,例如0.001至10重量%,例如0.005至5重量%,例如0.075至2.5重量%,例如0.01至5重量%的量存在。脂肪酸可以以0至5重量%,例如0.01至4重量%,例如0.05至3重量%,例如0.1至2.5重量%的量存在。防腐剂可以以0.01至5重量%,例如0.03至3重量%,例如0.05至1重量%,例如0.07至0.9重量%的量存在。
硫酸盐表面活性剂可以是阴离子表面活性剂。硫酸盐表面活性剂可以含有C8-C18烷基,例如C12-C16烷基,例如C10-C14烷基,或其混合物。例如,硫酸盐表面活性剂可包含C10烷基基团、C12烷基基团、C14烷基基团或其任何组合。硫酸盐表面活性剂可以含有部分不饱和的烷基。例如,硫酸盐表面活性剂可含有C18:1或C18:2烯基。例如,表面活性剂可以选自烷基硫酸盐、烷基醚硫酸盐或其组合。表面活性剂可优选为月桂基醚硫酸钠,或更优选地,表面活性剂可为具有0、1、2或3个乙氧基的月桂基醚硫酸钠。SLES-1EO一般指具有(平均)1个乙氧基基团的月桂基醚硫酸钠,SLES-2EO一般指具有(平均)2个乙氧基基团的月桂基醚硫酸钠,SLES-3EO一般指具有(平均)3个乙氧基基团的月桂基醚硫酸钠。
关于本文所公开的清洁组合物中存在的阴离子表面活性剂,所用的阴离子表面活性剂可包括脂族磺酸盐,如伯烷烃(例如C8-C22)磺酸盐、伯烷烃(例如C8-C22)二磺酸盐、C8-C22烯烃磺酸盐、C8-C22羟基烷烃磺酸盐或烷基甘油醚磺酸盐(AGS);或芳族磺酸盐如烷基苯磺酸盐。阴离子也可以是烷基硫酸盐(例如,C12-C18烷基硫酸盐)或烷基醚硫酸盐(包括烷基甘油醚硫酸盐)。烷基醚硫酸盐是具有下式的那些:
RO(CH2CH2O)nSO3M
其中R是具有8至18个碳,优选12至18个碳的烷基或烯基,n具有至少1.0,优选小于5,并且最优选1至4的平均值,并且M是增溶阳离子,如钠、钾、铵或取代的铵。
阴离子表面活性剂还可以是烷基磺基琥珀酸盐(包括单烷基和二烷基,例如C6-C22磺基琥珀酸盐);烷基和酰基牛磺酸盐(通常为甲基牛磺酸盐)、烷基和酰基肌氨酸盐、磺基乙酸盐、C8-C22烷基磷酸盐和膦酸盐、烷基磷酸酯和烷氧基烷基磷酸酯、酰基乳酸盐、C8-C22单烷基琥珀酸盐和马来酸盐、磺基乙酸盐、烷基葡糖苷和酰基羟乙基磺酸盐等。
磺基琥珀酸盐可以是具有下式的单烷基磺基琥珀酸盐:
R1OC(O)CH2CH(SO3M)CO2M;
和下式的酰胺-MEA磺基琥珀酸盐:
R1CONHCH2CH2OC(O)CH2CH(SO3M)CO2M
其中R1范围为C8-C22烷基。
肌氨酸盐通常由下式表示:
R2CON(CH3)CH2CO2M,其中R2范围为C8-C20烷基,
牛磺酸盐通常由下式表示:
R3CONR4CH2CH2SO3M
其中R3是C8-C20烷基,R4是C1-C4烷基。
M是如前所述的增溶阳离子。
本文公开的清洁组合物可含有C8-C18酰基羟乙基磺酸盐。这些酯通过碱金属羟乙基磺酸盐与具有6至18个碳原子且碘值小于20的混合脂族脂肪酸之间的反应制备。至少75%的混合脂肪酸具有12至18个碳原子,至多25%具有至10个碳原子。
酰基羟乙基磺酸盐可以是烷氧基化的羟乙基磺酸盐,例如1995年2月28日授权的Ilardi等人的标题为“Fatty Acid Esters of Polyalkoxylated isethonic acid”的美国专利第5,393,466号中所描述的;在此通过引用并入本文。该化合物具有以下通式:
R5C—(O)O—C(X)H—C(Y)H—(OCH2—CH2)m—SO3M
其中R5是具有8至18个碳的烷基基团,m为1至4的整数,X和Y各自独立地为氢或具有1至4个碳的烷基基团,并且M为如前所述的增溶阳离子。
在清洁组合物的一个方面中,所用的阴离子表面活性剂是2-丙烯酰胺基-2-甲基丙烷磺酸、月桂基硫酸铵、全氟壬酸铵、月桂基硫酸钾、烷基硫酸钠、十二烷基硫酸钠、月桂酸钠、月桂醇聚醚硫酸钠、月桂酰肌氨酸钠、硬脂酸钠、磺基琥珀酸酯钠或其组合。这类阴离子表面活性剂可从供应商如Galaxy Surfactants、Clariant、Sino Lion、Stepan Company和Innospec商购获得。
任选地,两性表面活性剂可包括在本文公开的清洁组合物中。两性表面活性剂(其根据pH可以是两性离子的)包括酰基两性乙酸钠、酰基两性丙酸钠、酰基两性二乙酸二钠和酰基两性二丙酸二钠,其中酰基(即烷酰基)可以包含C7-C18烷基部分。两性表面活性剂的说明性实例包括月桂酰两性基乙酸钠、椰油酰两性基乙酸钠、月桂酰两性基乙酸钠或其组合。
至于本发明清洁组合物中使用的两性离子表面活性剂,此类表面活性剂包括至少一个酸性基团。这样的酸性基团可以是羧酸或磺酸基团。它们通常包括季氮,因此可以是季胺酸(quaternary amino acid)。它们通常应包括7至18个碳原子的烷基或烯基,并且通常符合总体结构式:
R6—[—C(O)—NH(CH2)q—]r—N+(R7)(R8)-A—B
其中R6是7至18个碳原子的烷基或烯基;R7和R8各自独立地为1至3个碳原子的烷基、羟烷基或羧烷基;q为2至4;r为0至1;A为任选被羟基取代的1-3个碳原子的亚烷基,且B为-CO2-或-SO3-。
用于本文所公开的清洁组合物中并且在上述通式内的所需两性离子表面活性剂包括下式的简单甜菜碱:
R6—N+(R7)(R8)-CH2CO2 -
和下式的酰氨基甜菜碱:
R6—CONH(CH2)t—N+(R7)(R8)-CH2CO2 -
其中t是2或3。
在两个式中,R6、R7和R8如先前所定义。特别地,R6可以是衍生自椰子油的C12和C14烷基的混合物,使得基团R6的至少一半,优选至少四分之三具有10-14个碳原子。R7和R8优选为甲基。
另一种可能性是两性离子表面活性剂是下式的磺基甜菜碱:
R6—N+(R7)(R8)-(CH2)3SO3 -或
R6—CONH(CH2)u—N+(R7)(R8)-(CH2)3SO3 -
其中u是2或3,或这些的变体,其中-(CH2)3SO3 -被替换为-CH2C(OH)(H)CH2SO3 -。
在这些式中,R6、R7和R8如前面所定义。
所需使用的两性离子表面活性剂的示例性实例包括甜菜碱,例如月桂基甜菜碱、柠檬酸甜菜碱、椰油二甲基羧甲基甜菜碱、椰油酰胺丙基甜菜碱、椰油烷基二甲基甜菜碱和月桂酰胺丙基甜菜碱。适用的另外的两性离子表面活性剂包括椰油酰氨基丙基磺基甜菜碱,例如椰油酰氨基丙基羟基磺基甜菜碱。优选的两性离子表面活性剂包括月桂基甜菜碱、柠檬酸甜菜碱、羟甲基甘氨酸钠、(羧甲基)二甲基-3-[(1-氧代十二烷基)氨基]丙基氢氧化铵、椰油烷基二甲基甜菜碱、(羧甲基)二甲油烯基氢氧化铵、椰油酰胺丙基甜菜碱、(羧甲基)二甲油烯基氢氧化铵、椰油酰胺丙基甜菜碱、(羧酸甲基)二甲基(十八烷基)铵、椰油酰胺丙基羟基磺基甜菜碱或其组合。此类表面活性剂可从供应商如Stepan公司、Solvay、Evonik等商购获得,并且使用前述表面活性剂的混合物在本文所公开的清洁组合物的范围内。
非离子表面活性剂可任选地用于清洁组合物中。当使用时,非离子表面活性剂通常以低至0.5重量%、1重量%、1.5重量%或2重量%的含量并且以高至6重量%、8重量%、10重量%或12重量%的含量使用。可以使用的非离子表面活性剂特别包括具有疏水基团和反应性氢原子的化合物(例如脂族醇、酸、酰胺或烷基酚)与环氧烷(特别是单独的环氧乙烷或与环氧丙烷一起)的反应产物。具体的非离子表面活性剂化合物是烷基(C6-C22)酚、环氧乙烷缩合物、脂族(C8-C18)伯或仲直链或支链醇与环氧乙烷的缩合产物和通过环氧乙烷与环氧丙烷和乙二胺的反应产物缩合制备的产物。其它非离子表面活性剂包括长链叔胺氧化物、长链叔膦氧化物、二烷基亚砜等。
在一个方面,非离子表面活性剂可包括具有以下结构的脂肪酸/醇乙氧基化物:a)HOCH2(CH2)s(CH2CH2O)cH或b)HOOC(CH2)v(CH2CH2O)dH;其中s和v各自独立地为至多18的整数;并且c和d各自独立地为1或更大的整数。在一个方面中,s和v可各自独立地为6至18;并且c和d可以各自独立地为1至30。非离子表面活性剂的其它选择包括具有式HOOC(CH2)i—CH=CH—(CH2)k(CH2CH2O)zH的那些,其中i、k各自独立地为5至15;并且z为5至50。在另一方面,i和k各自独立地为6至12;并且z为15至35。
非离子表面活性剂还可以包括糖酰胺,如多糖酰胺。具体地,表面活性剂可以是1995年2月14日授予Au等人的标题为“Compositions Comprising Nonionic GlycolipidSurfactants”的美国专利第5,389,279号中所述的乳糖酰胺之一;其通过引用并入本文,或者其可以是1991年4月23日授予Kelkenberg等人的标题为“Use of N-Poly HydroxyalkylFatty Acid Amides as Thickening Agents for Liquid Aqueous Surfactant Systems”的美国专利第5,009,814号中所述的糖酰胺之一;在此通过引用并入本申请。
可任选地用于本文所公开的清洁组合物中的非离子表面活性剂的示例性实例包括但不限于多糖苷、鲸蜡醇、癸基葡糖苷、月桂基葡糖苷、八乙二醇单十二烷基醚、正辛基β-d-硫代吡喃葡糖苷、辛基葡糖苷、油醇、聚山梨醇酯、脱水山梨糖醇、硬脂醇或它们的组合。
在一个方面中,阳离子表面活性剂可任选地用于本申请的清洁组合物中。
一类阳离子表面活性剂包括杂环铵盐,如鲸蜡基或硬脂基氯化吡啶、烷基酰胺乙基吡啶(pyrrylinodium)甲基硫酸盐和拉匹氯铵。
四烷基铵盐是另一类有用的阳离子表面活性剂。实例包括鲸蜡基或硬脂基三甲基氯化铵或溴化铵;氢化棕榈或牛脂三甲基卤化铵;山嵛基三甲基卤化铵或甲基硫酸铵;癸基异壬基二甲基卤化铵;二牛油基(或二硬脂基)二甲基卤化铵,和山嵛烷基二甲基氯化铵。
可以使用的其它类型的阳离子表面活性剂是各种乙氧基化季胺和酯季铵盐。实例包括PEG-5硬脂基乳酸铵(例如,由Clariant制造的Genamin KSL)、PEG-2椰油氯化铵、PEG-15氢化牛脂氯化铵、PEG15硬脂基氯化铵、二棕榈酰基乙基甲基氯化铵、二棕榈酰基羟乙基甲基硫酸盐和硬脂基酰胺丙基二甲基胺乳酸盐。
其它有用的阳离子表面活性剂还包括丝、小麦和角蛋白的季铵化水解产物,并且使用上述阳离子表面活性剂的混合物在清洁组合物的范围内。
如果使用的话,阳离子表面活性剂将占清洁组合物的不超过1.0重量%。当存在时,阳离子表面活性剂通常占清洁组合物的0.01重量%至0.7重量%,更通常0.1重量%至0.5重量%,包括其中包含的所有范围。
银化合物可包含银离子,例如,银离子可选自硝酸银、乙酸银、氧化银、硫酸银或其组合。优选地,银化合物是硝酸银。
更具体地讲,在本发明制剂和组合物中使用的银化合物是一种或多种水溶性银(I)化合物,其具有至少1.0×10-4mol/L的银离子溶解度(在25℃的水中)。如本文所提及,银离子溶解度是衍生自25℃水中的溶度积(Ksp)的值,所述溶度积是在许多来源中报导的公知参数。更具体地,银离子溶解度[Ag+],以mol/L给出的值,可以使用下式计算:
[Ag+]=(Ksp·x)(1/(x+1),
其中Ksp是目标化合物在25℃水中的溶度积,并且x表示每摩尔化合物的银离子的摩尔数。已发现具有至少1×10-4mol/L的银离子溶解度的银(I)化合物适用于本文。各种银化合物的银离子溶解度值在表1中给出。
表1:银离子溶解度
在本文所需使用的银化合物中为氧化银、硝酸银、乙酸银、硫酸银、苯甲酸银、水杨酸银、碳酸银、柠檬酸银和磷酸银,特别感兴趣的是硝酸银、乙酸银、氧化银、硫酸银或其组合。在至少一个优选的实施方案中,银化合物包含硝酸银。
在至少一个实施方案中,银化合物不是柠檬酸二氢银。在另一个实施方案中,银化合物不是藻酸或基本上解聚的藻酸的盐。在一个优选的实施方案中,银化合物不是纳米颗粒的形式,附着于纳米颗粒或是插层的硅酸盐(例如膨润土)的部分。
在一个或多个实施方案中,本发明方法中使用的水性皂组合物中的银化合物与表面活性剂的重量比为1:5000至1:6,500,000,优选1:10,000至1:2,500,000,更优选1:12,000至1:2,000,000。
本文所公开的清洁组合物还可包含增稠剂。特别优选的增稠剂包括基于阴离子聚合物的增稠剂,优选例如基于聚丙烯酸酯的聚合物或共聚物,或其组合。可以使用多糖。实例包括纤维、淀粉、天然/合成树胶和纤维素制品。淀粉的代表是化学改性的淀粉,如羟丙基淀粉磷酸钠和辛烯基琥珀酸淀粉铝。通常优选木薯淀粉,如麦芽糖糊精。合适的树胶包括黄原胶、菌核、果胶、刺梧桐树胶、阿拉伯树胶、琼脂、瓜尔胶(包括阿拉伯胶)、角叉菜胶、藻酸盐及其组合。合适的纤维素类包括羟丙基纤维素、羟丙基甲基纤维素、乙基纤维素、羧甲基纤维素钠(纤维素胶/羧甲基纤维素)和纤维素(例如纤维素微纤维、纤维素纳米晶体或微晶纤维素)。
纤维素微纤维的来源包括次生细胞壁材料(例如木浆、棉花)、细菌纤维素和初生细胞壁材料。优选地,初生细胞壁材料的来源选自来自果实、根、球茎、块茎、种子、叶及其组合的薄壁组织;更优选选自柑橘果实、番茄果实、桃果实、南瓜果实、猕猴桃果实、苹果果实、芒果果实、甜菜、甜菜根、萝卜、欧防风、玉米、燕麦、小麦、豌豆及其组合;且甚至更优选选自柑橘水果、番茄果实及其组合。初生细胞壁材料的最优选来源是来自柑橘果实的薄壁组织。柑桔纤维,如由以AQPlus获得的那些也可用作纤维素微纤维的来源。纤维素来源可以通过任何已知的方法进行表面改性,包括在Colloidal Polymer Science,Kalia等人,―Nanofibrillated cellulose:surface modification and potentialapplications”(2014),Vol 292,5-31页中描述的那些。
如所述的,合成聚合物是有效的增稠剂。该类别包括交联聚丙烯酸酯如Carbomers、聚丙烯酰胺如305和牛磺酸盐共聚物如EG和AVC,该共聚物通过相应的INCI命名法确定为丙烯酸钠/丙烯酰基二甲基牛磺酸钠和丙烯酰基二甲基牛磺酸盐/乙烯基吡咯烷酮共聚物。另一种优选的适合于增稠的合成聚合物是基于丙烯酸酯的聚合物,其由Seppic市售并以名称Simulgel INS100销售。也可以使用碳酸钙、气相二氧化硅和硅酸镁铝。
羟丙基淀粉磷酸钠、辛烯基琥珀酸淀粉铝、木薯淀粉、麦芽糖糊精、黄原胶、琼脂胶、瓜尔胶、角叉菜胶、藻酸盐胶、羟丙基纤维素、羟丙基甲基纤维素、乙基纤维素、羧甲基纤维素钠、纤维素、聚乙二醇(例如聚乙二醇二酯硬脂酸)或其组合是用于本发明清洁组合物的增稠剂的另外的实例。这种增稠剂可商购自Dow化学公司或Hallstar公司。
硝酸盐可以包含硝酸钠、硝酸钾或其组合,优选地,硝酸盐包含硝酸钾。
术语“脂肪酸皂”或更简单地“皂”在此以其普遍含义使用,即优选具有6至22个碳原子,并且优选8至18个碳原子的脂肪族烷烃或烯烃单羧酸脂肪酸的盐。
脂肪酸皂占本发明清洁制剂的0至5重量%。所提及的脂肪酸含量是针对通常提供给消费者的形式的制剂,而不考虑使用中的稀释。在使用中,通常用水稀释在该范围内含有较高含量的脂肪酸皂的制剂,使得施用于皮肤上的经稀释的组合物含有5%或更少,更特别地0.2至5%或更少的脂肪酸皂。
典型的皂盐是这类脂肪酸的碱金属盐或链烷醇铵盐,尽管也可以应用它们的其它金属盐,例如镁盐。这类酸的钠、钾、镁、单乙醇铵、二乙醇铵和三乙醇铵盐属于用于本文的期望的皂类。在本文公开的清洁组合物中最优选是钠皂,特别优选的是衍生自十二烷酸钠、月桂酸钠、油酸钠或其组合的钠皂。
如前所述,皂盐由其衍生的脂肪酸可以含有不饱和度。不饱和度水平应符合商业上可接受的标准。通常避免过度不饱和以最小化颜色和气味问题。通常,由其形成皂盐的脂肪酸中不超过40重量%是不饱和的。在一个或多个实施方案中,由其形成皂盐的脂肪酸中10至40重量%,更特别地20至40重量%是不饱和的。
防腐剂可理想地掺入清洁组合物中以防止潜在有害微生物的生长。防腐剂是为了保持产品的微生物安全性而添加的抗微生物成分。它们起到抑制微生物生长的作用,从而降低微生物污染的水平。由于个人洗涤制剂含有可生物降解的成分,如果不控制微生物分解,它们可能变得令人不快和不安全。微生物生长是依赖水的,因此防腐剂必须在一定程度上分配到制剂的水相中。常用防腐剂可分为以下五类:
1)对羟基苯甲酸酯类(如对羟基苯甲酸甲酯、对羟基苯甲酸丙酯和对羟基苯甲酸丁酯)和Germaben II衍生自对羟基苯甲酸。这些材料对真菌和一些革兰氏阴性菌是经济且有效的,但需要第二种成分以控制革兰氏阳性菌。在含乳液的制剂中它们也更倾向于向油相分配。它们以0.01-0.3重量%的水平被广泛应用,并且通常被认为是安全的,尽管对可能的雌激素活性和与癌症的联系存在担忧。
2)甲醛释放剂如Germall Plus、DMDM乙内酰脲和咪唑啉或二唑啉脲。这类材料对细菌有效,但只提供弱的抗真菌活性。它们在pH 3-8范围内以0.1-0.5%重量的含量使用。释放的低含量的游离甲醛确保微生物抑制,但引起潜在致癌物的担忧。
3)异噻唑啉酮如甲基氯异噻唑啉酮(MCI)、甲基异噻唑酮(MI)和Kathon。异噻唑啉酮在宽pH范围内提供广谱效力,但它们可能对一些消费者造成皮肤刺激。这类材料以约几十ppm的低含量使用。
4)苯氧乙醇,以Optiphen或Optiphen Plus和Neolone PH 100销售。通常认为苯氧乙醇是对羟基苯甲酸酯或甲醛供体的更温和的替代物,但对革兰氏阴性菌具有窄适用性谱。其通常与辛酰基二醇、山梨酸/山梨酸钾或EDTA组合以产生广谱功效。它适用于宽的pH范围,通常使用含量为1%或更低。然而,对可能的致癌活性存在一些担忧。
5)有机酸如苯甲酸/苯甲酸钠、山梨酸/山梨酸钾、水杨酸/水杨酸钠和乙酰丙酸或茴香酸。这些酸的使用限于pH范围为2-6的水性应用。它们通常以高于一些上述替代物的含量使用,并且对细菌具有较弱的效率(其可通过与二偶氮烷基脲组合而增加),尽管它们对真菌功效非常好。通常认为这类防腐剂是天然的。
用于本文公开的清洁组合物中的防腐剂优选包括基于有机酸的防腐剂,优选苯甲酸、水杨酸、乙酰丙酸、茴香酸(ansic acid)或其组合。使用的传统防腐剂包括乙内酰脲衍生物和丙酸盐。
使用的其它防腐剂是碘代丙炔基丁基氨基甲酸酯、苯氧乙醇、1,2-辛二醇、羟基苯乙酮、乙基己基甘油、己二醇、对羟基苯甲酸甲酯、对羟基苯甲酸丙酯、咪唑烷基脲、脱氢乙酸钠、二甲基-二甲基(DMDM)乙内酰脲和苄醇,及其混合物。其它防腐剂包括苯甲酸钠、脱氢乙酸钠、氯苯甘醚和癸二醇。防腐剂的选择应考虑组合物的用途和防腐剂与清洁组合物中其它成分之间可能的不相容性。还优选具有单独羟基苯乙酮或与其它防腐剂混合的防腐剂体系。特别优选的是苯甲酸钠。
基于制剂的总重量,本文公开的清洁组合物通常包含20重量%至90重量%,更具体地50重量%至85重量%的量的水。这样的水含量代表相对宽范围的制剂,包括浓缩和非浓缩产品,其中水含量为20重量%至小于50重量%水的制剂是浓缩产品的典型代表。
在使用中,清洁组合物通常用水稀释。稀释程度取决于具体的产品形式。不太常见但也预期用于本文的是发泡而不稀释的制剂,其通常通过使用泵分配器,其中产品通过泵中的筛网。
清洁组合物可另外包括各种添加剂,包括但不限于着色剂、润肤剂、去头皮屑剂、皮肤感觉剂、染发剂、定型聚合物、硅油、阳离子聚合物或它们的组合。这些物质中的每一种可以为液体和组合物总重量的约0.03至约5%重量,优选0.1至3%重量,包括其中包含的所有范围。例如,着色剂可以以5ppm至15ppm,例如约15ppm的量存在。
可存在于本发明个人清洁制剂中的其它任选成分为例如:芳香剂;多价螯合剂和螯合剂,例如乙二胺四乙酸四钠(EDTA)、乙烷羟基二膦酸(EHDP)和羟乙磷酸,也称为1-羟基亚乙基二膦酸(HEDP);着色剂;遮光剂和珠光剂,例如硬脂酸锌、硬脂酸镁、TiO2、乙二醇单硬脂酸酯(EGMS)、乙二醇二硬脂酸酯(EGDS)或Lytron 621(苯乙烯/丙烯酸酯共聚物)等;pH调节剂;抗氧化剂,例如丁基化羟基甲苯(BHT)等;稳定剂;增泡剂,例如椰油酰基单乙醇酰胺或二乙醇酰胺;离子化盐,例如氯化钠和硫酸钠,以及其它成分,例如常规用于液体皂制剂中的那些。基于个人清洁制剂的总重量,此类附加的任选成分的总量通常为0至10重量%,更具体地为0.1至5重量%。
组合物通常包括一种或多种皮肤有益剂。术语“皮肤有益剂”被定义为通过增加皮肤(角质层)的含水量,添加或替代脂质和其它皮肤营养素或二者来软化或改善皮肤(角质层)的弹性、外观和年轻度,并通过延缓其含水量的降低来保持其柔软的物质。合适的皮肤有益剂包括润肤剂,包括例如疏水性润肤剂、亲水性润肤剂或其共混物。
有用的皮肤有益剂包括以下:(a)硅油及其改性物如直链和环状聚二甲基硅氧烷;氨基、烷基、烷基芳基和芳基硅油;(b)脂肪和油,包括天然脂肪和油,如霍霍巴油、大豆油、向日葵油、米糠油、鳄梨油、杏仁油、橄榄油、芝麻油、桃仁油、蓖麻油、椰子油和貂油;可可脂;牛油和猪油;通过氢化上述油获得的硬化油;以及合成的单、二和三甘油酯如肉豆蔻酸甘油酯和2-乙基己酸甘油酯;(c)蜡,例如巴西棕榈蜡、鲸蜡、蜂蜡、羊毛脂及其衍生物;(d)疏水和亲水的植物提取物;(e)烃类如液体石蜡、矿脂、微晶蜡、地蜡、角鲨烯、降植烷(pristan)和矿物油;(f)高级脂肪酸,例如月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、山嵛酸、油酸、亚油酸、亚麻酸、羊毛脂酸、异硬脂酸、花生四烯酸和多不饱和脂肪酸(PUFA);(g)高级醇,例如月桂醇、鲸蜡醇、硬脂醇、油醇、二十二醇、胆固醇和2-己基癸醇;(h)酯,例如辛酸鲸蜡酯、乳酸肉豆蔻酯、乳酸鲸蜡酯、肉豆蔻酸异丙酯、肉豆蔻酸肉豆蔻酯、棕榈酸异丙酯、己二酸异丙酯、硬脂酸丁酯、油酸癸酯、异硬脂酸胆固醇酯、单硬脂酸甘油酯、单月桂酸甘油酯、二硬脂酸甘油酯、三硬脂酸甘油酯、乳酸烷基酯、柠檬酸烷基酯和酒石酸烷基酯;(i)精油及其提取物,例如薄荷、茉莉花、樟脑、白雪松、苦橙皮、ryu、松节油、肉桂、佛手柑、柑橘、菖蒲、松树、薰衣草、月桂、丁香、罗汉柏、桉树、柠檬、星花、百里香、辣薄荷、玫瑰、鼠尾草、芝麻、姜、罗勒、杜松子、柠檬草、迷迭香、迷迭香木、鳄梨、葡萄、葡萄籽、没药、黄瓜、水田芥、金盏花、接骨木花、天竺葵、菩提花、苋菜、海藻、银杏、人参、胡萝卜、瓜拉那、茶树、霍霍巴、紫草、燕麦、可可、橙花、香草、绿茶、薄荷(penny royal)、芦荟、薄荷醇、桉叶醇、丁香酚、香茅醛、香茅、冰片、芳樟醇、香叶醇、月见草、樟脑、百里酚、盘龙参酚(spirantol)、蒎烯(penene)、柠檬烯和萜烯油;(j)多羟基醇,例如甘油、山梨醇、丙二醇等;和多元醇如聚乙二醇,其实例为:Polyox WSR-205PEG 14M、Polyox WSR-N-60K PEG 45M,或Polyox WSR-N-750,和PEG 7M;(k)脂质如胆固醇、神经酰胺、蔗糖酯和假神经酰胺,如欧洲专利说明书第556957号中所述的;(l)维生素、矿物质和皮肤营养素,例如牛奶、维生素A、E和K;维生素烷基酯,包括维生素C烷基酯;镁、钙、铜、锌和其它金属组分;(m)防晒剂如辛基甲氧基肉桂酸酯(Parsol MCX)和丁基甲氧基苯甲酰基甲烷(Parsol 1789);(n)磷脂;和(o)抗老化化合物,例如α-羟基酸和β-羟基酸。皮肤有益剂通常占液体皂制剂的至多30重量%,其中0至25重量%,更特别地0至20重量%的含量是通常称为“润肤剂”的那些皮肤有益剂在许多主题制剂中使用的典型含量。优选的皮肤有益剂包括脂肪酸、烃、多羟基醇、多元醇及其混合物,在一个或多个实施方案中,特别感兴趣的是包括至少一种C12-C18脂肪酸、凡士林、甘油、山梨醇和/或丙二醇的润肤剂。
其它任选成分包括水溶性/水分散性聚合物。这些聚合物可以是阳离子型、阴离子型、两性型或非离子型,分子量高于100,000道尔顿。已知它们增加液体个人清洁制剂的粘度和稳定性,增强使用中和使用后的皮肤感觉特性,并增强泡沫乳脂性和泡沫稳定性。当存在时,这些聚合物的总量通常为个人清洁制剂的0.1-10重量%。
水溶性或分散性聚合物的实例包括糖胶,例如纤维素胶、微晶纤维素、纤维素凝胶、羟乙基纤维素、羟丙基纤维素、羧甲基纤维素钠、甲基纤维素、乙基纤维素、瓜尔胶、刺梧桐树胶、黄蓍胶、阿拉伯胶、金合欢胶、琼脂胶、黄原胶及其混合物;改性和非改性淀粉颗粒和预胶化冷水可溶性淀粉;乳液聚合物如28、22或AquaSF1;阳离子聚合物,如改性多糖,包括以商品名Jaguar C13S、Jaguar C14S、Jaguar C17或Jaguar C16获自Rhone Poulenc的阳离子瓜尔胶;阳离子改性纤维素如来自Amerchol的UCARE Polymer JR 30或JR 40;来自Hercules的3000、3196、GPX 215或GPX 196;合成阳离子聚合物如由Nalco销售的100、280、281和550;阳离子淀粉,例如由Staley公司销售的100、200、300和400;阳离子半乳甘露聚糖,如Henkel公司的800系列;LM-200;和聚季铵盐-24。高分子量聚乙二醇如WSR-205(PEG 14M)、WSR-N-60K(PEG45)和WSR-301(PEG90M)也是合适的。
清洁组合物在25℃的温度下在约1s-1的剪切速率下的粘度可为约1帕斯卡秒。清洁组合物在25℃的温度下在约4s-1的剪切速率下的粘度可为约0.1帕斯卡秒至约50帕斯卡秒。
本文公开的清洁组合物被配制成提供抗微生物益处。本发明的个人清洁制剂在抗革兰氏阳性菌(特别包括金黄色葡萄球菌)的杀生物活性方面是令人感兴趣的。皂制剂所关注的其他革兰氏阳性(革兰阳性)细菌是表皮葡萄球菌和/或棒状杆菌,特别是负责将腋窝分泌物水解成异味化合物的棒状杆菌菌株。理想地,所述制剂在30秒的接触时间提供对金黄色葡萄球菌ATCC 6538的生物活性的至少2.5,优选至少3的log10降低,并且甚至更优选在20秒的接触期间提供对金黄色葡萄球菌ATCC 6538的至少1.5,甚至更优选至少2的log10降低。
本文所述的清洁组合物可通过制备技术生产。在一种非常通用的方法中,向加热的水相中加入熔融的脂肪酸,随后加入苛性碱(以中和脂肪酸并形成皂)、合成洗涤剂和助溶剂;当产物冷却至室温时,视情况添加剩余成分。
清洁组合物可以以各种不同的产品形式提供,包括例如手、脸和身体洗涤剂、淋浴凝胶、皂条等,例如抗微生物产品形式,包括例如手、脸和身体洗涤剂、淋浴凝胶、皂条等。制剂可以以瓶、泵分配器、管、小袋或适于产品形式的其它包装提供。
本文所公开的清洁组合物可用于脂肪酸皂/游离脂肪酸条中,所述脂肪酸皂/游离脂肪酸条包含低含量的合成表面活性剂(7至25重量%)、高含量的皂和/或高含量的游离脂肪酸,如Farrell等人的美国专利第6,846,787号、Farrell等人的美国专利第6,849,585号和Moaddel等人的美国专利第7,351,682号中所述,所有这些专利以全文引用的方式并入本文中。在与合成皂条和其它皂条组分组合之前,使用含有不超过一定量的不饱和物并且基本上不含较低链长脂肪酸(例如小于C14)的脂肪酸/皂原料或脂肪酸皂来制备前体皂条组合物,可以制备加工和起泡良好的皂条。
条可通过将混合器加热至约80℃至约90℃,添加脂肪酸,随后添加苛性碱以形成前体,接着添加表面活性剂和其它条材料来制造。将混合物干燥至目标水分,然后冷却。然后将冷却的材料挤出,制成坯料,并压制成条。
在使用中,根据需要将清洁组合物稀释以形成水性清洁组合物,将该组合物施用至皮肤上的接触时间小于1分钟,更具体地为30秒或更少(对于中等至相对长的持续时间的接触时间,10至30秒的接触时间是令人感兴趣的,且对于短至中等持续时间的接触时间,10秒或更少的接触时间是令人感兴趣的),然后通常通过用水冲洗将其从皮肤上除去。可在将清洁组合物置于皮肤上之前、之后或同时将其稀释,其中稀释通常通过将制剂在手中或在施用器(诸如面巾、海绵或泡肤)上加工成泡沫来进行。
附图说明
以下是附图的简要说明,其中相同的元件用相同的数字表示,并且它们是为了举例说明本文公开的清洁组合物的目的而不是为了限制本文公开的清洁组合物的目的。
图1是金黄色葡萄球菌的时间-杀伤研究的图示说明,其显示当表面活性剂SLES-1EO与银离子组合时增强的杀生物作用。
图2是SLES制剂随盐变化的粘度的图解说明。
除了在操作实施例和对比例中,或另外明确指出的情况,本说明书中表示材料的量或反应条件、材料的物理性质和/或用途的所有数字应理解为由词语“约”修饰。除非另外指明,否则所有量均按最终组合物的重量计。
应注意,在指定浓度或量的任何范围时,任何特定的上限浓度可与任何特定的下限浓度或量以及其中包含的任何子范围相关联。就此而言,应注意,本文所公开的所有范围均包括端点,并且端点可独立地彼此组合(例如,“至多25重量%,或更具体地5重量%至20重量%的范围”,包括端点和5重量%至25重量%范围的所有中间值等)。“组合”包括共混物、混合物、合金、反应产物等。此外,本文中的术语“第一”、“第二”等不表示任何顺序、数量或重要性,而是用于区分一个要素与另一个要素。本文中的术语“一个”和“一种”和“所述”不表示数量的限制,并且应解释为涵盖单数和复数,除非本文中另有说明或与上下文明显矛盾。如本文所用的后缀“(s)”旨在包括其修饰的术语的单数和复数两者,从而包括一个或多个该术语(例如,膜包括一个或多个膜)。在整个说明书中对“一个实施方案”、“一个方面”、“另一实施方案”、“另一方面”、“实施方案”、“方面”等的引用意味着结合该实施例或方面描述的特定要素(例如,特征、结构和/或特性)被包括在本文描述的至少一个实施方案或方面中,并且可以存在或可以不存在于其他实施方案或方面中。此外,应当理解,所描述的要素可以以任何合适的方式组合在各种实施方案或方面中。
所有引用的专利、专利申请和其它参考文献通过整体引用并入本文。然而,如果本申请中的术语与所并入的参考文献中的术语相矛盾或冲突,则本申请中的术语优先于所并入的参考文献中的冲突术语。虽然已经描述了特定方面,但是申请人或本领域的其他技术人员可以想到目前无法预料或可能无法预料的替代、修改、变化、改进和实质等同物。因此,提交的和可能修改的所附权利要求旨在包括所有这些替代、修改、变化、改进和实质等同物。
为了避免疑问,词语“包含”旨在表示“包括”,但不一定是“由...组成”或“由...构成”。换言之,所列出的步骤、选项或替代方案不需要是穷举的。
本文发现的本发明的公开内容被视为涵盖了在权利要求中发现的,作为彼此多重从属的所有方面,而与权利要求可以在没有多重从属或冗余的情况下存在的事实无关。
所提供的实施例是为了便于理解清洁组合物,而不是为了限制权利要求的范围。
实施例
体外时间-杀伤方案
表面活性剂溶液制备-溶液制备包括将表面活性剂溶液与等体积的适当缓冲剂混合以形成含有50%原始制剂浓度的测试溶液。制备碳酸钠/碳酸氢盐缓冲剂(0.1M)以分别在pH 10和7下使用,而乙酸钠缓冲液在pH 5下使用。然后添加硝酸银溶液和盐溶液的等分试样以达到这些组分的所需含量。使用稀NaOH和HNO3代替指定的缓冲剂以控制测试pH而进行的一系列实验产生了等同的实验结果,但是更加繁琐。
细菌-本研究中用于表示革兰氏阳性细菌的金黄色葡萄球菌ATCC 6538获自美国典型培养物保藏中心(Rockville,Md)。将细菌储存在-80℃下,并且通过在胰蛋白酶大豆琼脂平板上在37℃下划线接种24小时来制备新鲜的工作培养物,然后在每次实验之前以相同的方式制备第二传代培养物。
体外时间-杀伤试验-时间-杀伤试验根据欧洲标准EN 1040:2005,标题为“Chemical Disinfectants and Antiseptics–Quantitative suspension test forevaluation of basic bactericidal activity of chemical disinfectants andantiseptics–Test method and requirements(Phase 1)”进行,其通过引用并入本文,并进行了微小的修改。按照该程序,在25℃下,而不是在标准中规定的20℃下,用表面活性剂溶液(如上所述)处理约3×108菌落形成单位(CFU)/mL的静止期细菌培养物。在构建测试样品时,将8重量份的表面活性剂溶液与1重量份的培养物和1重量份的水混合。在暴露10、20、30和60秒后,中和样品以抑制表面活性剂溶液的抗菌活性。这些选择的时间间隔短于标准中规定的5分钟,以便更能代表消费者通常用于手洗的时间范围。将测试溶液连续稀释,接种在固体培养基上,并孵育24小时。然后计数存活的细胞。杀菌活性定义为在0秒时相对于初始细菌浓度的CFU的log10降低。未暴露于表面活性剂溶液的培养物作为未处理对照。使用下式计算log10降低:
log10降低=log10(未处理对照中的CFU)-log10(处理样品中的CFU)
实施例1.在pH 5-10范围内SLES/SDS与Ag的协同作用
收集了25℃下制剂的所有数据。所有结果均为暴露20/30秒后从初始接种物的约为7.5log10的存活金黄色葡萄球菌的log10降低,为3次试验的平均值,标准偏差为0.3log10单位。所有情况下的检测限为3log10。
表2
*SLES-1EO是指具有1个乙氧基基团的月桂基醚硫酸钠
**SLES-3EO是指具有3个乙氧基的月桂基醚硫酸钠
该实施例证明了表面活性剂/银制剂的杀生物活性在宽的pH范围内是有活性的。硫酸盐表面活性剂SLES-1EO在7-10的pH范围内给出约0.5单位的log10降低,但在银离子存在下此降低显著增加至约4单位。在pH 5下,SLES本身是杀生物的,具有约2的log10降低。即使在这种情况下,在添加银时仍有额外的1至2log降低的空间。
对于癸酸钠皂和该皂与SLES-1EO或与SLES-3EO的50/50共混物,在pH 10下观察到类似水平的益处。由于相应脂肪酸的不溶性,皂在5-7的pH范围内不是用于该测试的合适的表面活性剂。
可以得出结论,在本文公开的清洁组合物的精神内与银离子组合的硫酸盐表面活性剂在5-10的pH范围内显示出增强的杀生物作用。此外,皂表面活性剂和与硫酸盐表面活性剂组合的皂在皂合适的pH下也显示出这种增强的杀生物作用。在低pH限度下,这些制剂将与作为防腐剂使用的有机酸相容。例如,在pH 5下保持未解离(和活性)的有机酸防腐剂的百分比对于苯甲酸是13%,对于山梨酸是37%(G.Hill,―Preservation of cosmeticsand toiletries”,Handbook of Bioicides and Preservatives Use,H.W.Rossmoore编辑,Springer Science and Business,1995)。
实施例2.硫酸盐的独特性
在实施例2中,测试了通常用于个人洗涤的表面活性剂在pH 5和pH 7下与银离子的协同作用。
表3中的所有结果均记录为在pH值为5的条件下暴露20/30秒后从初始接种物的约7.5log10的存活金黄色葡萄球菌的log10降低,为3次试验的平均值,标准偏差为0.3log10单位。所有情况下的检测限为3log10。
表3
表3(所有实施例均在pH 5下)表明,适用于个人洗涤应用并且能够在该pH下溶解的大多数表面活性剂本身或与阴离子组合不是杀生物的。这类无效表面活性剂的实例包括非离子表面活性剂如Triton X-100(辛基苯酚乙氧基化物)。这种商业上可获得的去污剂广泛用于裂解细胞为提取蛋白质或细胞器的目的和用于渗透细胞膜(―Triton X-100concentration effects on membrane permeability of a single HeLa cell byscanning electrochemical microscopy(SECM)”,D.Koley和A.J.Bard,PNAS 107,16783-16787(2010);―Classifying surfactants with respect to their effect on lipidmembrane order”,M.Nazari等人,Biophysical Journal 102,498-506(2012))。高于其CMC(临界胶束浓度)(=0.015%)的去污剂浓度破坏细胞脂质双层内的氢键并破坏脂质膜的完整性。这种情况可能在约几分钟的暴露时间下对细胞致死。略低于CMC的浓度充分渗透细胞膜以允许高度带电的亲水性离子(其通常被完全排除)通过活细胞膜。尽管具有这些性质,但即使在10重量%的升高水平下,在10-60秒的适合于洗手的时间范围内,Triton X-100也不是杀生物的,并且明显不促进银离子在金黄色葡萄球菌细胞中的渗透。
甲基椰油酰基牛磺酸钠是N-甲基牛磺酸的椰油脂肪酸酰胺的钠盐。它被分类为磺酸盐洗涤剂而不是硫酸盐洗涤剂,并且在宽的pH范围内是可溶的,显示出发泡和表面张力降低的典型的表面活性剂性能。然而,它不具有固有的杀生物性质,也不增强银离子在pH 5下的杀生物作用。
相反,硫酸盐SDS和SLES在pH 5下显示出与银离子的强协同作用。(尽管SDS在该pH下本身是相当杀生物的)。
表4显示了通常用于个人洗涤应用的表面活性剂在pH 7下与银的协同杀生物作用的实例。所有结果均为暴露20/30秒后从初始接种物的约为7.5log10的存活金黄色葡萄球菌的log10降低,为3次试验的平均值,标准偏差为0.3log10单位。所有情况下的检测限为3log10。
表4
表4(所有样品在pH 7下)表明适合于个人洗涤应用并且能够在该pH下溶解的大多数表面活性剂本身或与阴离子的组合不是杀生物的。这类无效表面活性剂的实例还包括非离子表面活性剂如Triton X-100和磺化洗涤剂甲基椰油酰基牛磺酸钠。另外的无效表面活性剂包括阴离子氨基酸基表面活性剂椰油酰基甘氨酸钠、椰油酰基谷氨酸钠和两性表面活性剂月桂酰两性乙酸钠。这些无效表面活性剂可能含有从它们的制造中留下的作为杂质的相当含量的NaCl(按固体重量计高达20%的盐-―Sodium Lauroamphoacetate”M.J.Fevola,Cosmetics&Toiletries 126,844-848(2011)),其预期会使所添加的银离子无效。为了消除这种复杂性,表面活性剂都通过从冷水中反复重结晶进行处理,直到它们的氯离子浓度低于10ppm的离子色谱检测极限。
在要求保护的整个pH区间内,硫酸化脂肪醇(SDS)和硫酸化聚氧乙烯化醇(SLES-1EO和SLES-3EO)具有有限的固有杀生物作用,但显示出与银离子的强协同作用。
实施例3.氯离子对表面活性剂/银制剂的杀生物活性的影响
氯离子由于溶解的矿物质如NaCl、KCl和CaCl2或由于使用控制雪和冰的氯化物盐而存在于天然水中(―Guidelines for drinking-water quality”,第2期,第2卷.Healthcriteria and other supporting information,World Health Organization,Geneva,1996)。英国河流中的平均氯离子浓度为11至42毫克/升mg/L(3×10-4-1.2×10-3M),而美国的含水层可含有超过100mg/L(2.8×10-3M)的氯离子。此外,氯离子作为杂质或作为有意添加的添加剂存在于个人洗涤产品中。通常向这些产品中添加辅助表面活性剂以增强它们的皮肤相容性并优化它们在清洁和起泡方面的总体性能(S.Herrwerth等人,―Highlyconcentrated Cocamidopropyl betaine–The latest developments for improvedsustainability and enhanced skin care”,Tenside 45,304-308(2008))。最重要的一类次级表面活性剂是酰胺丙基甜菜碱,其在两步法中制备,其第二步涉及与氯乙酸反应并导致作为副产物的氯化钠的形成。实际上,市售甜菜碱的氯化钠含量可以为4-9%,使得即使当这些次级表面活性剂在产品中以百分之几的含量使用时,它们提供约0.03M的氯离子。此外,通常将氯化物盐如氯化钠添加到液体个人洗涤产品中以提高其粘度。通常添加1-2%NaCl,其提供额外的0.1-0.3M氯离子。
该实施例说明了氯离子如何由于氯化银的低溶解度而对含银制剂的杀生物性能具有有害影响。
表5示出制剂在pH 7.0和25℃下的所有数据。所有结果均报告为暴露20/30秒后从初始接种物的约7.5log10的存活金黄色葡萄球菌的log10降低,为3次试验的平均值,标准偏差为0.3log10单位。所有情况下的检测限为3log10。
表5
在表5的上半部分中,在pH 7下单独的1至10ppm Ag+没有杀生物作用。1%的表面活性剂SLES给出≤1log10单位降低的弱杀生物作用。SLES和银的组合产生强的杀生物作用(4log10降低),但该作用在NaCl存在下受到影响。
表5的后半部分(涉及10% SLES的较高表面活性剂含量)显示出以下结果:在pH 7下单独的1ppm Ag+没有杀生物作用。10%的表面活性剂SLES产生≤1log10单位降低的弱杀生物作用,其通过添加至多0.5M NaCl没有显著改善。SLES和银的组合产生强的杀生物作用(4log10降低),但该作用在NaCl存在下受到影响。当NaCl以至多0.5M的含量存在时,将银离子的含量从1ppm增加到3ppm对于恢复杀生物作用是无效的。
总之,1-10%范围的表面活性剂含量不是固有杀生物的,但在存在ppm水平的银离子时变成杀生物的。然而,在如在个人洗涤产品中通常发现的高水平氯离子(>0.01M)的存在下,杀生物活性大大降低。
实施例4.盐对粘度的影响
作为增加产品粘度的手段,向液体个人洗涤产品中添加盐是非常普通的程序。消费者已经开始预期一定水平的产品稠度,他们将其与产品的丰富性和有效性相关联。水稀产品给出不充实的和劣质的印象。
广泛理解的是,盐如NaCl对粘度的影响与它们增加由去污表面活性剂形成的胶束的大小的作用相关联(B.Jonsson等人,―Surfactants and Polymers in AqueousSolution”,John Wiley&Sons,1998)。R.Ranganathan等人,―Surfactant-and salt-induced growth of normal sodium alkyl sulfate micelles well above theircritical micelle concentrations”,J.Phys.Chem B 104,2260-2264(2000)研究了NaCl对一系列烷基硫酸钠中胶束大小的影响,发现胶束大小在添加0.1-1M范围内的NaCl盐时显示幂律增长。因此,希望在皮肤清洁制剂中添加NaCl,而当表面活性剂和银组合时,这种添加大大降低了所观察到的杀生物增强,这是一个特别的缺点。
表6显示了10% SLES-1EO制剂的粘度随盐含量的变化。使用具有4cm平板几何形状和1000m间隙的TA Instruments Discovery HR-2混合流变仪在25℃的温度下进行测量。对测量表面进行喷砂以避免壁滑,并且报告剪切速率4s-1时的结果。
表6
表6和图2证明了通过添加0.1-1M NaCl获得的强的粘度增强。在剪切速率为4s-1,温度为25℃下记录粘度,其为传统上用于评价皮肤清洁制剂的变形速率。用类似于NaCl的硝酸盐,NaNO3,可以实现非常相似的增强程度。还值得注意的是,给出强的粘度增强的硝酸钠含量(0.4M和更高)是恢复与在杂质水平的NaCl存在下损失的表面活性剂与银之间的协同作用所必需的含量相同(参见实施例6)。
实施例5.聚合物的影响
已报道(US 2016/0362646 A1)具有含一个或多个孤对电子的重复单元的聚合物对银离子具有强亲和力,并因此降低其团聚倾向。因此,增强了金属离子的抗微生物效力。这类聚合物的优选实施方案是以总组合物的0.002-2%使用的聚乙烯吡咯烷酮。V.Sambhy,M.M.MacBride,B.R.Peterson和A.Sen,―Silver bromide nanoparticle/polymercomposites:Dual action tunable antimicrobial materials”,J.Am.Chem.Soc.128,9798-9808(2006)报道了聚(4-乙烯基吡啶)共聚物充当银的稳定剂。此外,明胶已经作为银胶体的稳定剂用于摄影产业中多年,从而防止它们团聚(M.Yang,J.-G.Zhao,J.-J.Li,―Synthesis of porous spherical AgBr nanoparticles in the presence of gelatinusing AgCl as the precursor”,Colloids and Surfaces A 295,81-84(2007))。
在US 2011/0224120A1中对在pH 7.5和8.5之间以0.01至10重量%的含量使用的未中和的聚羧酸和在US 2012/0034314A1中对以0.1-2%的含量和在pH 6-9下由聚丙烯酸酯聚合物螯合的银进行了单独的主张。这些聚羧酸声称用作银离子的稳定剂,从而防止沉淀和颜色变化而不影响杀生物作用。聚羧酸的另一个益处是它们通常作为增粘剂添加到个人洗涤产品中,以提供消费者从这些产品中预期的外观和实质感觉。
以下实施例证明了上述引证的实施例实际上给出与本发明要求保护的组合物相反的教导。
表7示出了与银离子相互作用的聚合物对表面活性剂和银的协同杀生物作用的影响。PVPi是聚(4-乙烯基吡啶),PVPo是聚乙烯吡咯烷酮,PAAn是聚烯丙胺,PEI是聚乙烯亚胺。所有结果均为在25℃下暴露20/30秒后从初始接种物的约7.5log10的存活金黄色葡萄球菌的log10降低,且为3次试验的平均值,标准偏差为0.3log10单位。所有情况下的检测限为3log10。
表7
表7表明添加明胶、聚(4-乙烯基吡啶)、聚乙烯吡咯烷酮、聚(4-乙烯基吡啶)、聚乙烯吡咯烷酮、聚烯丙胺或聚乙烯亚胺不能充分保护SLES/Ag体系免于在0.03-1M NaCl存在下杀生物活性的损失。因此,PVPi、PVPo、PAAn和PEI,其全部为如US2016/0362646A1中声称的对银离子具有强亲和力的具有孤对电子的聚合物,不保护SLES/Ag体系免受NaCl的有害影响。因此,US 2016/0362646给出了与本发明的清洁组合物相反的教导。
表8示出与银离子相互作用的聚丙烯酸酯对表面活性剂和银的协同杀生物作用的影响。所有结果均为在25℃下暴露20/30秒后从初始接种物的约7.5log10的存活金黄色葡萄球菌的log10降低,且为3次试验的平均值,标准偏差为0.3log10单位。所有情况下的检测限为3log10。
表8
表8表明,尽管添加0.2-1ppm的银离子产生针对金黄色葡萄球菌的协同杀生物作用,1%聚丙烯酸显著地降低了表面活性剂和0.2ppm银之间的协同作用,该发现从参考US2011/0224120A1对于在pH 7.5和8.5之间以0.01%至10%重量的含量使用的未中和的多元羧酸是无法预测的。在该参考文献中,聚羧酸声称作为银离子的稳定剂,防止沉淀和颜色变化而不影响杀生物作用。类似地,US2012/0034314A声称在0.1-2%的水平和6-9的pH下与聚丙烯酸酯聚合物结合的银离子保持稳定的、持久的抗微生物益处。表8的第6和7行(样品81和82)表明在0.4和1ppm Ag+下也存在一定程度的协同作用降低。不是稳定银离子而不干扰杀生物作用,而是表现出聚羧酸络合银离子。这种络合作用的证据是以下事实:在固定的聚羧酸水平下,当总的银水平从0.2ppm增加至1ppm时,协同作用得到改善。
表8的第8-13行(样品83-88)探究了聚羧酸可能干扰氯化银的沉淀并且因此保护在添加的NaCl存在下通过表面活性剂对银的杀生物增强的可能性,如US 2011/0224120A1所提议的。添加0.03和0.1M氯化钠因氯化银沉淀而逐渐降低表面活性剂产生的增强作用。但是添加0.1%聚羧酸使其略微更差,而不是改善情况,因此也没有迹象表明这些聚合物充当结晶抑制剂。
实施例6.硝酸盐的益处
天然水可以含有宽范围的氯化钠。淡水含有近乎零的盐,而世界海洋中的平均盐度为约35份/千份(3.5%或0.6M)(https://ww2.health.wa.gov.au/Articles/S_T/Sodium-in-drinking-water)。海水和淡水经常在河口和江口混合,从而产生咸水,其盐度范围可超过千分之0.5。澳大利亚的卫生部已经确定,超过0.18份/千份(0.018%或3mM)的盐含量将赋予水咸味。然而这种水虽然不适合饮用,但仍可用于个人洗涤。实际上,如果可行的话,使用这种非饮用水进行洗涤将优于“浪费”可能供应不足的淡水。
通常由于溶解的氯化钠而进入水中的氯离子可对银的抗菌作用具有有害影响。表9中的第二行(样品90)显示出制剂对金黄色葡萄球菌在暴露20/30秒后的优异杀生物活性,具有活微生物4log10降低。第三行(样品91)说明在悬浮试验中向抗菌制剂(20% SLES和0.3ppm Ag+)中添加0.5M NaCl的效果。添加NaCl显著地消除了杀生物作用,并且不可能通过添加过量的银离子来恢复活性。
表9显示了将电解质从NaCl改变为NaNO3对在表面活性剂和银组合时杀生物作用提高的影响。所有数据均为pH 7.0和25℃下的制剂。所有结果均为暴露20/30秒后从初始接种物的约7.5log10的存活金黄色葡萄球菌的log10降低,且为3次试验的平均值,标准偏差为0.3log10单位。所有情况下的检测限为3log10。
表9
表9的第6-8行(样品94-96)表明,虽然添加NaCl很大程度上消除了杀生物作用,硝酸钠代替氯化钠作为电解质使其完全恢复。因为硝酸钠显示出与氯化钠类似的与SLES的增稠趋势,所以它可以用作增稠剂而不牺牲杀生物作用。
表10示出在pH 7.0和25℃下制剂的所有数据。所有结果均为暴露20/30秒后从初始接种物的约7.5log10的存活金黄色葡萄球菌的log10降低,且为3次试验的平均值,标准偏差为0.3log10单位。所有情况下的检测限为3log10。
表10
表10也表明,当将表面活性剂与银组合时发现的协同杀生物作用受到低至0.03MNaCl的严重影响。这些水平的NaCl可以作为出于增加制剂粘度的目的而添加的表面活性剂的杂质存在于制剂中,或者可以经由微咸水供应进入洗涤液。可以得出结论,在存在0.03MNaCl(0.175% NaCl)的情况下,需要0.3M或更高的NaNO3才能恢复金黄色葡萄球菌的一个单位log10降低。由于这一盐水平是水尝出咸味的水平的十倍,显然,即使这样的非饮用水仍可在本发明中考虑用于杀生物清洁。
实施例7.在硝酸钠存在下表面活性剂/银协同作用的银离子要求
在表11中,制剂的所有数据均为在pH 7.0和25℃下。所有结果均为暴露20/30秒后从初始接种物的约为7.5log10的存活金黄色葡萄球菌的log10降低,且为3次试验的平均值,标准偏差为0.3log10单位。所有情况下的检测限为3log10。
表11
该实施例表明,在pH 7和25℃的条件下,在10% SLES和0.5M NaNO3的存在下,观察到增强的杀生物作用所需的最低银离子水平为≥0.03ppm。
实施例8.表面活性剂/银/硝酸盐体系更耐受聚羧酸
据称聚羧酸充当银离子的稳定剂,从而防止沉淀和颜色变化而不影响杀生物作用。聚羧酸的另一个益处是它们通常作为增粘剂添加到个人洗涤产品中,以提供消费者从这些产品中预期的外观和实质感觉。
下面的实施例证明聚羧酸干扰表面活性剂加银的杀生物作用,这与现有技术公开的清洁组合物相反。然而,在表面活性剂/银/硝酸盐体系中的杀生物作用比不存在硝酸盐时更耐受聚羧酸,因此更适于添加聚羧酸以控制粘度。
表12示出与银离子相互作用的聚羧酸对表面活性剂和银的协同杀生物作用的影响。所有结果均为3次试验的平均值,标准差为0.5log10单位。所有情况下的检测限为3log10。
表12
添加1%聚羧酸PAA时,10% SLES在0.1-1ppm Ag+下的杀生物效力降低3至1个log10单位。然而,包含NaNO3部分地恢复了该杀生物效力。不受理论束缚,很可能硝酸根离子成功地与多元羧酸竞争银离子。该假设的证据是以下事实:在固定的聚羧酸水平下,当银的总含量增加时,协同作用改善(更大的log降低)。
实施例9.在pH空间中硝酸盐益处的广度
表13提供了硝酸盐在维持表面活性剂加银离子的增强的杀生物作用方面的益处的另外的实施例。
表13示出25℃下制剂的所有数据。所有结果均为暴露20/30秒后从初始接种物的约7.5log10的存活金黄色葡萄球菌的log10降低,且为3次试验的平均值,标准偏差为0.5log10单位。所有情况下的检测限为3log10。
表13
Claims (13)
1.一种清洁组合物,其包含:
5至25重量%的硫酸盐表面活性剂;
0至5重量%的脂肪酸皂;
0.03至3ppm的银化合物;
0.05至1重量%的增稠剂;以及
1至10重量%的硝酸盐;
其中所述清洁组合物的pH为5至10。
2.一种清洁组合物,其包含:
5至25重量%的硫酸盐表面活性剂;
0.03至3ppm的银化合物;
0.05至1重量%的增稠剂;
1至10重量%的硝酸盐;以及
0.05至1重量%的防腐剂;
其中所述清洁组合物的pH为4至5.5。
3.如权利要求1或2所述的清洁组合物,其中所述硫酸盐表面活性剂为阴离子表面活性剂。
4.如权利要求3所述的清洁组合物,其中所述表面活性剂选自烷基硫酸盐、烷基醚硫酸盐或其组合,优选地其中所述表面活性剂为月桂基醚硫酸钠,更优选地其中所述表面活性剂为具有0、1、2或3个乙氧基的月桂基醚硫酸钠。
5.如前述任一项权利要求所述的清洁组合物,其中所述银化合物为银离子,优选地其中所述银离子选自硝酸银、乙酸银、氧化银、硫酸银或其组合,更优选地其中所述银化合物为硝酸银。
6.如前述任一项权利要求所述的清洁组合物,其中所述增稠剂为基于阴离子聚合物的增稠剂,优选地其中所述增稠剂为基于聚丙烯酸酯的聚合物或共聚物,或其组合。
7.如前述任一项权利要求所述的清洁组合物,其中所述硝酸盐包含硝酸钠、硝酸钾或其组合,优选地其中所述硝酸盐包含硝酸钠。
8.如前述任一项权利要求所述的清洁组合物,其中所述清洁组合物在25℃的温度下在约1s-1的剪切速率下的粘度为约1帕斯卡秒。
9.如权利要求1和3至8中任一项所述的清洁组合物,其中所述脂肪酸皂为钠皂,优选地其中所述脂肪酸皂为衍生自十二烷酸钠、月桂酸钠、油酸钠或其组合的钠皂。
10.如权利要求2至8中任一项所述的清洁组合物,其中所述防腐剂包含基于有机酸的防腐剂,优选地其中所述基于有机酸的防腐剂选自苯甲酸、水杨酸、乙酰丙酸、茴香酸或其组合。
11.如前述任一项权利要求所述的清洁组合物,其中所述清洁组合物被配制成提供抗微生物益处。
12.如权利要求1-10中任一项所述的组合物在身体清洁或毛发清洁应用中的非治疗用途。
13.如权利要求1-10中任一项所述的组合物在抗微生物身体清洁或毛发清洁应用中的非治疗用途。
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CN102159176A (zh) * | 2008-09-23 | 2011-08-17 | 荷兰联合利华有限公司 | 采用高含量多元醇的、包含具有大于10重量%的脂肪酸/脂肪皂含量的脂肪酰基羟乙基磺酸盐表面活性剂产品的稳定的清洁组合物及其方法 |
WO2011120780A2 (en) * | 2010-03-31 | 2011-10-06 | Unilever Plc | Personal wash cleanser with mild surfactant systems comprising defined alkanoyl compounds and defined fatty acyl isethionate surfactant product and optional skin or hair benefit agent |
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US20230124634A1 (en) | 2023-04-20 |
WO2021224114A1 (en) | 2021-11-11 |
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EP4146350A1 (en) | 2023-03-15 |
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