CN1129422C - Liquid anitmicrobial clansing compositions which provide residual benefit versus gram negative bacterial - Google Patents

Liquid anitmicrobial clansing compositions which provide residual benefit versus gram negative bacterial Download PDF

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Publication number
CN1129422C
CN1129422C CN98807394A CN98807394A CN1129422C CN 1129422 C CN1129422 C CN 1129422C CN 98807394 A CN98807394 A CN 98807394A CN 98807394 A CN98807394 A CN 98807394A CN 1129422 C CN1129422 C CN 1129422C
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acid
floats
cleansing compositions
compositions
antimicrobial cleansing
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CN98807394A
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CN1264293A (en
Inventor
P·W·彼尔斯
J·M·摩根
K·G·拜尔
R·G·巴托罗
T·A·拜肯
M·E·凯尔瑟斯
M·R·塞恩
M·L·克莱普
P·瓦尔仑
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Procter and Gamble Co
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Procter and Gamble Co
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Priority claimed from US08/969,077 external-priority patent/US6214363B1/en
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/005Antimicrobial preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • A61K8/347Phenols
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • A61K8/442Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof substituted by amido group(s)
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • A61K8/463Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur containing sulfuric acid derivatives, e.g. sodium lauryl sulfate
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00Drugs for dermatological disorders
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61PSPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00Drugs for dermatological disorders
    • A61P17/10Anti-acne agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin

Abstract

The present invention relates to a rinse-off antimicrobial cleansing composition comprising from about 0.001 % to about 5 % of an antimicrobial active, from about 1 % to about 80 % of an anionic surfactant, from about 0.1 % to about 12 % of a proton donating agent; from about 0.1 % to about 30 % of a deposition aid; and from about 3 % to about 98.8 % of water, wherein the composition is adjusted to a pH of from about 3.0 to about 6.0, wherein the rinse-off antimicrobial cleansing composition has a Gram Negative Residual Effectiveness Index of greater than about 0.3, and wherein the rinse-off antimicrobial cleansing composition has a Mildness Index of greater than 0.3. The invention also encompasses methods for cleansing skin and providing residual effectiveness versus Gram negative bacteria using these products.

Description

The liquid antimicrobial cleansing compositions of anti-gram negative bacteria time-delay effect is provided
Technical field
The present invention relates to the gentle type personal cleaning compositions that floats, it has the antimicrobial efficacy of enhancement.Unknown time-delay antibiotic effect before specifically, Cleasing compositions of the present invention has temporary gram negative bacteria.
Background technology
Human health can be subjected to the influence of multiple microorganism entity.Virus and infecting of antibacterial can cause multiple disease.Medium have improved the understanding of the public to microorganism problem to the concern of situations such as alimentary toxicosis, streptococcal infection.
Known employing antimicrobial or non-medicine soap clean crust, food (for example fruit or vegetable) and skin (particularly hands) can remove multiple virus and antibacterial from the surface that is cleaned.The removal of virus and antibacterial is to be reached by the surface activity effect of soap and the mechanism of washing process.Therefore, known and suggestion people often reduce virus and the propagation of antibacterial by cleaning.
Find that the antibacterial on the skin can be divided into two classes: that retain and temporary antibacterial.Retaining antibacterial is gram positive bacteria, and it can form fixedly bacterium colony at the surface and the outermost layer of skin, to preventing the living important and useful effect that has of moving of other more deleterious antibacterial and fungus.
Temporary antibacterial does not belong on the skin the conventional bacterium colony that retains, but can be deposited on the skin when airborne pollutant touch on the skin or keep in antibacterial when pollutant contact with skin generation physics.Temporary antibacterial generally is divided into two groups: gram positive bacteria and gram negative bacteria.Gram positive bacteria comprises that pathogen is as staphylococcus aureus, streptococcus pyogenes and Clostridium botulinum.Gram negative bacteria comprises pathogen, as Salmonella, escherichia coli, Klebsiella pneumoniae, haemophilus, bacillus pyocyaneus, Bacillus proteus and shigella dysenteriae.The difference of gram negative bacteria and gram positive bacteria generally is additional protection sexual cell film, and like this, gram negative bacteria generally is not subject to the influence of topical anti-microbial active component.
The antibiotic cleaning product certain hour that gone on the market in a variety of forms.Its form comprises deodorant soap, hard surface cleaner and surgery disinfectant.These tradition of being prepared are floated the type antimicrobial products can remove antibacterial in washing process.Find that also antimicrobial soap can provide the time-delay effect of resisting gram-positive bacteria, but the time-delay effect of its anti-gram negative bacteria is limited.The time-delay effect is meant and cleaning/growth of antibacterial on the surface is suppressed in a period of time after floating step.The liquid antimicrobial cleansing agent sees US4847072 (people such as Bissett, 1989.7.11 authorize), 4939284 (Degenhardt, 1990.7.3 authorizes) and 4820698 (Degenhardt, 1989.4.11 authorize), all the elements all be combined in the present invention this as a reference.
Commercially available in the past compositions Head ﹠amp; Shoulders  (Head﹠Shoulders) dandruff removing shampoo is in listing in 1994, wherein contains anion surfactant, antimicrobial acivity composition and as the citric acid of pH regulator agent.Head ﹠amp; Shoulders  (Head﹠Shoulders) can suppress to cause the pityrosporum ovale (Pityrosorum ovale) of dandruff generation.PCT application WO92/18100 (people such as Keegan, 1992.10.29 it is open, " Keegan ") and PCT application WO95/32705 (people such as Fujiwara, 1995.12.7 it is open, " Fujiwara ") in the liquid skin cleaning agent has been proposed, wherein contain gentle surfactant, antibacterial and be used to regulate the acid compound of pH, it has improved antibiotic property.Provide anti-gram negative bacteria time-delay effect required not disassociation acid but adopt wherein the formed compositions of acid compound of low content not discharge.This class situation that comprises in Keegan and Fujiwara is preferably to have adopted gentle surfactant, comprises non-ionic surface active agent.
Some antimicrobial products has particularly adopted high-load alcohol and/or surfactant in hard surface cleaner and the surgery disinfectant, and can make the skin histology mummification and produce stimulates.Ideal personal cleanser is cleaning skin leniently, does not have or do not have substantially zest, and frequent the use can not make the excessive mummification of skin yet, preferably tackles skin and has the effect of moistening.
US3141821 (Compeau, 1964.7.21 authorize), and Ciba-Giegy, Inc. the technical literature of the Irgasan DP 300 (triclosan Triclosan ) of relevant " basic formulations 89/42/01 that is used for hand disinfection " has proposed skin antibiotic cleaning compositions, and it adopts some anion surfactant, antimicrobial acivity composition and acid to reach anti-gram negative bacteria time-delay effect.But the high active surfactant of wherein selecting for use can make this personal cleaning compositions cause xerosis cutis and stimulation.
Gram negative bacteria such as Salmonella, escherichia coli and shigella can have a strong impact on health, need preparation badly and have to the time-delay antibacterial action of gram negative bacteria and to the antimicrobial cleansing compositions of skin gentleness.Existing product can not have mildness and anti-gram negative bacteria time-delay effect concurrently.
The applicant finds: with known antimicrobial acivity composition with as the specific organic and/or mineral acid of giving proton reagent and specific anion surfactant shared make have that this mildness and anti-gram negative bacteria delay time effect float the type antimicrobial cleansing compositions, more than each component all be deposited on the skin.Sedimentary effect of can promote selected active component for proton reagent and anion surfactant makes it have the antibacterial action of new height with contact skin the time.
Summary of the invention
The present invention relates to float the type antimicrobial cleansing compositions, wherein contain the about 5% antimicrobial acivity composition of the 0.001-that has an appointment; About 80% anion surfactant of about 1-; About 0.1-about 12% gives proton reagent; The deposition aid of about 0.1%-about 30%; With about 98.8% water of about 3-.The pH regulator of compositions is to about 3.0-about 6.0.This gram negative bacteria time-delay antibiotic effect index that floats the type antimicrobial cleansing compositions is greater than about 0.3; The mildness index is greater than 0.3.
The invention still further relates to the method for floating type antimicrobial cleansing compositions cleaning and reducing temporary gram positive bacteria propagation of the present invention that adopts.
Of the present invention to float the type antimicrobial cleansing compositions very effective to clean surface, particularly skin, and anti-gram negative bacteria time-delay effect is provided, and to the skin gentleness.
Here the term of Cai Yonging " floats type " and be meant in the context present composition that adopted finally needs from processed surface (for example skin or crust) to go up rinsing or wash in use or with the back.
Here the term of Cai Yonging " antimicrobial cleansing compositions " is meant and is suitable for coating from the teeth outwards, is used to remove the compositions of dust, oil stain etc., the growth of the gram positive bacteria that it can also suppress to keep in and viability.Embodiment preferred is the Cleasing compositions that is applicable to human body skin among the present invention.
Compositions of the present invention also is applicable to the processing of acne.Term used herein " acne treatment " is meant prevention, stops and/or suppresses acne formation on the mammal skin.
Compositions of the present invention is used for also can having basic instant (that is, emergent) improvement to skin appearance behind the skin.More specifically say, the present composition also is applicable to adjusts skin matter, comprises and adjusts visible on skin and/or tactile discontinuity, comprises vision and/or tactile discontinuity on skin texture and/or the color, particularly relevant discontinuity with skin aging, but be not limited only to this.This discontinuity may or cause by inside and/or external factor initiation.External factor comprises ultraviolet radiation (for example sun exposure), environmental pollution, wind, high temperature, low humidity, potent surfactant, abrasive material etc.Internal factor comprises that chronic biochemistry aging and other skin inside changes.
Adjustment skin matter comprises the preventing and/or treating property adjustment to skin matter.Here said preventative adjustment skin matter comprises and delays, reduces and/or prevent vision and/or tactile discontinuity.Here said therapeutic is adjusted skin matter and is comprised: improve and for example reduce, reduce and/or eliminate these discontinuities.Adjust skin matter and comprise and improve skin appearance and texture, for example make skin more smooth, evenly and/or texture better.Here said adjustment skin matter comprises the adjustment aging character." adjust skin aging feature " comprises that preventative adjustment and/or therapeutic adjust one or more these category features (promptly adjust the signal of skin aging, for example microgroove, wrinkle or pore comprise that preventative adjustment and/or therapeutic adjust these features).
" skin aging feature " comprises the performance that all are outside visible and can touch, and other macroscopic view or microcosmic effect that is caused by skin aging, but is not limited only to this.These features may be caused or caused by inside or external factor (for example chronic aging and/or environmental nuisance).This feature may be caused by the evolution of following structure discontinuity, as wrinkle, comprise appearance microgroove and thick dark stricture of vagina, the skin lines, the crack, lump, big pore is (for example with sweat duct, accessory structure such as sebaceous gland or hair follicle is relevant), peeling, the skin of decortication and/or other form is inhomogeneous or coarse, skin lack flexibility (functional skin elasticity loss of proteins and/or inactivation), sagging (comprising ocular and lower jaw edema), lax, the skin loss in toughness, skin recovery loss to distortion, variable color (comprising eyelet down), form speckle, xanthoderma, skin part hyperpigmentation such as senile plaque and freckle, keratinization, unusual differentiation, hyperkeratosis, elastosis, collagen destroys, and other is at horny layer, corium, epidermis, the tissue that occurs in particularly adjacent with the skin tissue of skin heart system (for example blood capillary) and subcutaneous tissue changes, but is not limited only to this.
Unless otherwise indicated, all percentage ratios and ratio all by weight, and unless otherwise indicated, it is all measured under 25 ℃.The present invention can comprise following neccessary composition and other described optional member, or by or form by them substantially.1. composition
The type antimicrobial cleansing compositions that floats of the present invention contains antimicrobial acivity composition, anion surfactant, gives proton reagent and deposition aid.These components are selected, thereby made the present composition satisfy the following effect and the requirement of mildness.Need be to each components selection on other components selection is decided.For example, if select weak acid as giving proton reagent, for realizing the effect of compositions,, necessary surfactant and/or interior high-load acid of prescribed limit and/or specific effective active composition and/or the interior high-load deposition aid of prescribed limit that adopts higher biological activity (but the possibility mildness reduces).Equally, when not having the surfactant of effect, then must adopt stronger acid and/or high-load acid and/or high-load deposition aid for the effect that realizes compositions if employing is gentle.If adopt potent surfactant, then should adopt mildness composition or lipophile skin moisturizing composition as deposition aid.As follows to each components selection standard: A. The antimicrobial acivity composition
Of the present invention float to contain in the type antimicrobial cleansing compositions account for about 5% (weight) of the about 0.001-of compositions, about 2% (weight) of preferably about 0.01-, more preferably from about about 1.5% (weight) of 0.05-, the antimicrobial acivity composition of about 1.0% (weight) of 0.1-more preferably from about.The definite consumption of antimicrobial composition will be decided on concrete active component in the compositions, because the different activities composition has different effectiveness intensity.For avoiding interacting, should adopt the non-cationic active component with anion surfactant of the present invention.
Classify the example that is applicable to non-cationic antimicrobial reagent of the present invention down as:
Pyrithione, particularly Zn complex (ZPT)
Octopirox (Octopirox )
Dimethylformamide dimethyl base alcohol allantoin (Glydant )
Methylchloroisothiazandnone/Methylisothiazolinone (Kathon CG )
Sodium sulfite
Sodium sulfite
Imidazolidinyl urea (Germall 115 ) diazacyclo pentyl urea (Germall II ) benzylalcohol 2-bromo-2-nitropropane-1,3-glycol (Bronopol ) formalin (formaldehyde) iodopropylene base butyl carbamate (Polyphase P100 ) chloroacetamide Methanamide methyl dibromo nitrile glutaronitrile (1,2-two bromo-2,4-dicyanobutane or Tektamer ) glutaraldehyde 5-bromo-5-nitro-1,3-diox (Bronidox ) phenethanol neighbour-phenyl phenol/neighbour-phenyl phenol sodium sodium hydroxy methyl glycinate (Suttocide A ) polymethoxy Er Huan oxazolidine (Nuosept C ) acetyl Er Jia diox (dimethoxane) thiomersalate (thimersal) dybenal captan adermykon dichlorophen methaform glyceryl laurate ester halogenated diphenyl ether
2,4,4 '-three chloro-2 '-hydroxyl-diphenyl ether (triclosan  or TCS)
2,2 '-dihydroxy-5,5 '-two bromo-diphenyl ether phenolic compounds
Phenol
The 2-methylphenol
The 3-methylphenol
The 4-methylphenol
The 4-ethyl-phenol
2, the 4-xylenol
2, the 5-xylenol
3, the 4-xylenol
2, the 6-xylenol
4-n-pro-pyl phenol
4-normal-butyl phenol
4-n-pentyl phenol
The 4-tert-amyl phenol
4-n-hexyl phenol
4-n-heptyl phenol list or many alkyl and aryl halide substituting phenol
Parachlorophenol
The methyl parachlorophenol
The ethyl parachlorophenol
The n-pro-pyl parachlorophenol
The normal-butyl parachlorophenol
The n-pentyl parachlorophenol
The sec-amyl parachlorophenol
The n-hexyl parachlorophenol
The cyclohexyl parachlorophenol
The n-heptyl parachlorophenol
The n-octyl parachlorophenol
O-chlorphenol
The methyl o-chlorphenol
The ethyl o-chlorphenol
The n-pro-pyl o-chlorphenol
The normal-butyl o-chlorphenol
The n-pentyl o-chlorphenol
The tertiary pentyl o-chlorphenol
The n-hexyl o-chlorphenol
The n-heptyl o-chlorphenol
Adjacent benzyl parachlorophenol
Methyl parachlorophenol between adjacent benzyl
Between adjacent benzyl, a dimethyl parachlorophenol
Adjacent phenethyl parachlorophenol
Methyl parachlorophenol between adjacent phenethyl
3-methyl parachlorophenol
3,5-dimethyl parachlorophenol
6-ethyl-3-methyl parachlorophenol
6-n-pro-pyl-3-methyl parachlorophenol
6-isopropyl-3-methyl parachlorophenol
2-ethyl-3,5-dimethyl parachlorophenol
6-sec-butyl-3-methyl parachlorophenol
2-isopropyl-3,5-dimethyl parachlorophenol
6-diethylmethyl-3-methyl parachlorophenol
6-isopropyl-2-ethyl-3-methyl parachlorophenol
2-sec-amyl-3,5-dimethyl parachlorophenol
2-diethylmethyl 3,5-dimethyl parachlorophenol
6-secondary octyl-3-methyl parachlorophenol
Parachlorometacresol
P bromophenol
The methyl p bromophenol
The ethyl p bromophenol
The n-pro-pyl p bromophenol
The normal-butyl p bromophenol
The n-pentyl p bromophenol
The sec-amyl p bromophenol
The n-hexyl p bromophenol
The cyclohexyl p bromophenol
Adjacent bromophenol
The adjacent bromophenol of tertiary pentyl
The adjacent bromophenol of n-hexyl
N-pro-pyl-,-the adjacent bromophenol of dimethyl
The 2-phenylphenol
4-chloro-2-methylphenol
4-chloro-3-methylphenol
4-chloro-3, the 5-xylenol
2,4-two chloro-3,5-xylenol
3,4,5,6-tetrabromobisphenol-methylphenol
5-methyl-2-amyl phenol
4-isopropyl-3-methylphenol
Parachlorometaxylenol (PCMX)
Chlorothymol
Phenyl phenol
The phenoxy group isopropyl alcohol
5-chloro-2-hydroxyl diphenyl methane resorcinol and derivant thereof
Resorcinol
Methylresorcinol
Ethyl resorcinol
The n-pro-pyl resorcinol
N-butyl resorcinol
The n-pentyl resorcinol
The n-hexyl resorcinol
The n-heptyl resorcinol
The n-octyl resorcinol
The n-nonyl resorcinol
The phenyl resorcinol
The benzyl resorcinol
The phenethyl resorcinol
The phenylpropyl resorcinol
The p-chlorobenzyl resorcinol
5-chloro-2,4-dihydroxy diphenyl methane
4 '-chloro-2,4-dihydroxy diphenyl methane
5-bromo-2,4-dihydroxy diphenyl methane
4 '-bromo-2,4-dihydroxy diphenyl methane bisphenol compound
2,2 '-di-2-ethylhexylphosphine oxide (4-chlorophenol)
2,2 '-di-2-ethylhexylphosphine oxide (3,4, the 6-trichlorophenol, 2,4,6,-T)
2,2 '-di-2-ethylhexylphosphine oxide (4-chloro-6-bromophenol)
Two (2-hydroxyl-3,5-chlorophenesic acid) thioether
Two (2-hydroxyl-5-benzyl chloride base) thioether benzoate (p-Hydroxybenzoate)
Methyl parahydroxybenzoate
Propyl p-hydroxybenzoate
Butyl p-hydroxybenzoate
Ethylparaben
P-Hydroxybenzoic acid isopropyl ester
P-Hydroxybenzoic acid isobutyl ester
Benzyl p-hydroxybenzoate
Sodium Methyl Hydroxybenzoate
Sodium Propyl Hydroxybenzoate halogenation carbanilide
3,4,4 '-trichloro-symmetrical diphenyl urea (triclocarban Triclocarban  or TCC)
3-trifluoromethyl-4,4 '-the dichloro carbanilide
3,3 ', the 4-trichloro-symmetrical diphenyl urea
Be applicable to that other antibacterial of the present invention is known as " natural " antimicrobial acivity composition, is also referred to as natural essence oil.The title of these active component comes from its natural former plant.Typical natural plant essence oil antimicrobial acivity composition comprises Pimpinella anisum Linn., Fructus Citri Limoniae, Citrus, Herba Rosmarini Officinalis, Ilicis Purpureae, Herba thymi vulgaris, Garden lavender, Flos Caryophylli, Flos lupuli (Flos Humuli Lupuli), Camellia sinensis, Herba Cymbopogonis Citrari, Semen Tritici aestivi, Fructus Hordei Vulgaris, lemon grass (Cymbopogon citratus), cedar leaf, cedar wood, Cortex cinnamomi japonici (Ramulus Cinnamomi), Flos Inulae flowers and plants (fleagrass), Herba Erodii, sandalwood, violet, Pericarpium Citri tangerinae, Eucalyptus, Herba Verbenae, Herba Menthae, Resin benzoin, basil, Fructus Foeniculi, fir, balm, menthol, ocmea origanum (Adeps Bovis seu Bubali), Hydastiscarradensis, berberidaceae daceae (Berberidaceae), the oil of plant such as ratanhia and Rhizoma Curcumae Longae.The main chemical compositions that wherein also comprises plants essential oil with antibacterial action.This class chemical constituent comprises anethole, catechol, camphene, thymol, eugenol, eucalyptole, ferulic acid, farnesol, chamenol, tropolone, limonene, menthol, methyl salicylate, carvacrol, terpinol, verbenone, berberine, ratanhia extract, oxidation caryophyllene, citronellic acid, curcumin, nerolidol and geraniol.
Other active component has antibacterial metal salts.This constituents generally comprises 3b-7b, 8 and 3a-5a family slaine.Specifically be aluminum, zirconium, zinc, silver, gold, copper, lanthanum, stannum, hydrargyrum, bismuth, selenium, strontium, scandium, yttrium, cerium, praseodymium, neodymium, hard iron, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutecium and their mixture.
The antibacterial that preferably is applicable to this is the broad-spectrum anti-microbial activity composition, is selected from triclosan , triclocarban , Octopirox, PCMX, ZPT, natural essence oil and main component thereof, and their mixture.Most preferably being used for antimicrobial acivity composition of the present invention is triclosan .B. Anion surfactant
The present invention floats and contains about 1 one about 80% (weight) of accounting for personal cleaning compositions weight, preferably about 50% (weight) of about 3-, the anion surfactant of 5-about 25% (weight) more preferably from about in the liquid embodiment of type antimicrobial cleansing compositions.Preferably contain about 70% (weight) of the 10-that has an appointment, the anion surfactant of 20-about 60% (weight) more preferably from about in the solid soap bar embodiment of the present invention.Although there is no particular determination in theory, it is generally acknowledged that anion surfactant can destroy the lipid in the bacterial cell membrane.Be applicable to that this specific acid can reduce the negative charge of bacteria cell wall, penetrate the cell membrane that is weakened by surfactant, make the Cytoplasm acidify of antibacterial.So the easier cell wall that penetrates reduction of antimicrobial acivity composition, and more effectively kill antibacterial.
The non-limiting example that is applicable to present composition anion foaming surfactant sees McCutcheon work " detergent and emulsifying agent " North America version (1990, ManufacturingConfectioner Publishing Co. publishes); McCutcheon work " functional components " North America version (1992); And US3929678 (people such as Laughlin, 1975.12.30 authorizes), all be incorporated herein by reference.
Various anion surfactants all may be applicable to the present invention.The non-limiting example of anion foaming surfactant comprises: alkyl sulfate and alkyl ether sulfate; the sulphation monoglyceride; sulfonation alkene; alkylaryl sulfonates; uncle or secondary alkyl sulfonate; alkyl sulfo succinate; acyl taurine salt; acyl-hydroxyethyl sulfonate; alkyl glycerol ether sulfonate; methylmesylate; alpha-sulfonated fatty acid; alkylphosphonic; acyl glutamate; acyl sarcosinates; alkyl sulfoacetate; acylated peptide; the alkyl ether carboxy acid salt; acyl-lactate; anion fluoro surfactants and their mixture.Anionic surfactant mixture can be effective to the present invention.
The anion surfactant that is applicable to this Cleasing compositions comprises alkyl sulfate and alkyl ether sulfate.The representative formula of this constituents is R 1O-SO 3M and R 1(CH 2H 4O) x-O-SO 3M, wherein R 1Be the saturated or unsaturated straight or branched alkyl that contains about 24 carbon atoms of about 8-, x is 1-10, and M is a water-soluble cationic, as ammonium, sodium, potassium, magnesium, triethanolamine, diethanolamine and monoethanolamine.Alkyl sulfate generally carries out sulphation by single hydroxyl alcohol (containing about 24 carbon atoms of about 8-) through sulfur trioxide or other sulphation technology and makes.Alkyl ether sulfate is generally made through sulphation by the condensation product of oxirane and single hydroxyl alcohol (containing about 24 carbon atoms of about 8-).This class alcohol can be made as cocos nucifera oil or Adeps Bovis seu Bubali by fat, also can be through synthetic.The instantiation that is applicable to the alkyl sulfate of this Cleasing compositions has lauryl or myristyl sodium sulfate salt, ammonium salt, potassium salt, magnesium salt or triethanolamine salt.The example of the alkyl ether sulfate that is suitable for comprises lauryl ether-3 ammonium sulfate, sodium salt, magnesium salt or triethanolamine salt.
Other anion surfactant that is suitable for has the sulphation monoglyceride, and its form is R 1CO-O-CH 2-C (OH) H-CH 2-O-SO 3M, wherein R 1Be the saturated or undersaturated straight or branched alkyl that contains about 24 carbon atoms of about 8-, M is water-soluble cationic such as ammonium, sodium, potassium, magnesium, triethanolamine, diethanolamine and monoethanolamine.They are generally formed monoglyceride, are made through the sulfur trioxide sulphation then by glycerol and fatty acid (containing about 24 carbon atoms of about 8-) reaction.The example of sulphation monoglyceride is a cocos nucifera oil monoglyceride sodium sulfate.
Other anion surfactant that is suitable for comprises alkene sulfonate, and its form is R 1SO 3M, R 1Be the monoene that contains about 24 carbon atoms of about 12-, M is water-soluble cationic such as ammonium, sodium, potassium, magnesium, triethanolamine, diethanolamine and monoethanolamine.This compounds can be made by following method, and alpha-olefin is SO 3 sulfonated through what do not cooperate, this acid reaction chemical compound that neutralizes then, and formed sultone obtains corresponding hydroxyl alkane sulfonate through hydrolysis in the reaction.The example of sulfonation alkene is C 14-C 16The alpha-olefin sodium sulfonate.
Other anion surfactant that is suitable for is a linear alkylbenzene sulfonate (LAS), and its form is R 1-C 6H 4-SO 3M, wherein R 1Be the saturated or undersaturated straight or branched alkyl that contains about 24 carbon atoms of about 8-, M is water-soluble cationic such as ammonium, sodium, potassium, magnesium, triethanolamine, diethanolamine and monoethanolamine.This chemical compound can be by linear alkylbenzene (LAB) and SO 3 sulfonated making.The example of this anion surfactant is a dodecylbenzene sodium sulfonate.
Other anion surfactant that is applicable to this Cleasing compositions comprises uncle or secondary paraffin sulfonate, and its form is R 1SO 3M, wherein R 1Be the saturated or undersaturated straight or branched alkyl that contains about 24 carbon atoms of about 8-, M is water-soluble cationic such as ammonium, sodium, potassium, magnesium, triethanolamine, diethanolamine and monoethanolamine.It is generally made through the sulfur dioxide sulfonation by alkane in the presence of chlorine and ultraviolet, or is made by other known method of sulfonating.Sulfonation can take place on the secondary of alkyl chain or uncle position.The example of alkane sulfonate is C among the present invention 13-17Alkane sulfonic acid alkali metal salts or ammonium salt.
Other anion surfactant that is suitable for has alkyl sulfo succinate, comprising N-octadecyl sulfosuccinamic acid disodium; Lauryl 2-Sulfosuccinic acid diammonium; N-(1,2-two carboxyethyls)-N-octadecyl 2-Sulfosuccinic acid four sodium; The sodium sulfosuccinate diamyl ester; The sodium sulfosuccinate dihexyl; And sodium sulfosuccinate dioctyl ester.
Taurate based on taurine also is suitable for, and the former is also referred to as the 2-aminoethane sulphonic acid.The example of taurine comprises the N-alkyl taurine, and it is made by the reaction of lauryl amine and sodium isethionate, referring to US2658072, in conjunction with in the present invention as a reference.Other example based on taurine comprises the acyl group taurine, and it is made by n-N-methyltaurine and fatty acid (containing about 24 carbon atoms of about 8-) reaction.
The another kind of anion surfactant that is applicable to this Cleasing compositions has acyl isethinate.This acyl isethinate is suc as formula R 1CO-O-CH 2CH 2SO 3Shown in the M, R wherein 1Be the saturated or undersaturated straight or branched alkyl that contains about 30 carbon atoms of about 10-, M is a cation.It is generally made by the alkali metal salt reaction of fatty acid (containing about 30 carbon atoms of about 8-) with isethionic acid.The non-limiting example of acyl isethinate comprises cocoyl isethionic acid ammonium, cocoyl hydroxyethyl sulfonate, lauroyl hydroxyethyl sulfonate, and their mixture.
Other anion surfactant that is suitable for also has alkyl glyceryl ether sulfonate, and its form is R 1-OCH 2-C (OH) H-CH 2-SO 3M, wherein R 1Be the saturated or undersaturated straight or branched alkyl that contains about 24 carbon atoms of about 8-, M is water-soluble cationic such as ammonium, sodium, potassium, magnesium, triethanolamine, diethanolamine and monoethanolamine.It can be made by epoxychloropropane and sodium sulfite and aliphatic alcohol (containing about 24 carbon atoms of about 8-) reaction, or is made by other method.One of example is a cocoyl glycerin ether sodium sulfonate.
Other anion surfactant that is suitable for comprises formula R 1CH (SO 4The alpha-sulfonated fatty acid of)-COOH and and formula R 1CH (SO 4)-CO-O-CH 3Sulfonated formate, R wherein 1It is the saturated or undersaturated straight or branched alkyl that contains about 24 carbon atoms of about 8-.It can be made through SO 3 sulfonated by fatty acid or alkyl methyl ester (containing about 24 carbon atoms of about 8-), or is made by other known sulfonation technology.The example comprises α-sulfonation fatty acid distribution of coconut oil and lauryl methyl ester.
Other anionic species comprises phosphate, and as monoalkyl, dialkyl group and trialkyl phosphate, it is made by five phosphorous oxide and monohydroxy side chain that contains about 24 carbon atoms of about 8-or straight chain alcohol reaction.Also can make by other known phosphorylation method.The example of this class surfactant is singly-or two-lauryl sodium phosphate.
Other anionic species comprises acyl glutamate, and corresponding formula is R 1CO-N (COOH)-CH 2CH 2-CO 2M, wherein R 1Be the saturated or undersaturated straight or branched alkyl that contains about 24 carbon atoms of about 8-, M is a water-soluble cationic.Its non-limiting example comprises sodium lauroyl glutamate, and the cocoyl sodium glutamate.
Other anion component comprises the alkanoyl sarcosinate, and corresponding formula is R 1CON (CH 3)-CH 2CH 2-CO 2M, wherein R 1Be the saturated or undersaturated straight or branched alkyl or alkenyl that contains about 20 carbon atoms of about 10-, M is a water-soluble cationic.Its non-limiting example comprises sodium N-lauroyl sarcosinate, cocoyl sodium sarcosinate and lauroyl sarcosine ammonium.
Other anion component comprises the alkyl ether carboxy acid salt, and corresponding formula is R 1(OCH 2CH 2) X-OCH 2-CO 2M, wherein R 1Be the saturated or undersaturated straight or branched alkyl or alkenyl that contains about 24 carbon atoms of about 8-, x is 1-10, and M is a water-soluble cationic.Its non-limiting example comprises the lauryl ether carboxylic acid sodium.
Other anion component comprises acyl-lactate, and corresponding formula is R 1CO-[O-CH (CH 3)-CO] X-CO 2M, wherein R 1Be the saturated or undersaturated straight or branched alkyl or alkenyl that contains about 24 carbon atoms of about 8-, x is 3, and M is a water-soluble cationic.Its non-limiting example comprises the cocoyl sodium lactate.
Other anion component comprises carboxylate, and its non-limiting example comprises the lauroyl carboxylic acid sodium, cocoyl carboxylic acid sodium, and lauroyl carboxylic acid ammonium.Anionic fluorosurfactants also is suitable for.
Any counter cation M is applicable in the anion surfactant.Preferred counter cation is selected from sodium, potassium, ammonium, monoethanolamine, diethanolamine and triethanolamine.More preferably counter cation is an ammonium.
When being used for the surfactant of antimicrobial cleansing compositions of the present invention, selection should consider 3 factors: the activity of (1) surfactant molecule in bacterial cell membrane; (2) dissolubility of Xuan Ding active component in surfactant; And the mildness of (3) surfactant, it can influence the mildness index (seeing below) of bactericidal composition. The mildness of biological activity/surfactant
In general, the biological activity of surfactant is high more, and the time-delay activity of compositions that contains this surfactant is big more.But in general, the biological activity of surfactant and its mildness are inversely proportional to; The biological activity of surfactant is high more, and its zest is high more, and the biological activity of surfactant is low more, and it is soft more.No matter be biologically active but the surfactant that stimulates, the still active but surfactant of gentleness of inanimate object all depends on certainly or influences other components selection.
Can directly measure the biological activity/mildness of the pure surfactant that characterizes by the microcytotoxicity index by microcytotoxicity reaction test (analytical method that sees below part).Wherein " pure surfactant " is meant the chemical composition that is made of a kind of surfactant entity substantially, and wherein this entity has only a chain length, end group and salify counter ion basically.For the viewpoint of high bioactivity, it is about 150 that the microcytotoxicity index of Response that is preferred for the anion surfactant of antimicrobial cleansing compositions of the present invention is lower than, and more preferably less than about 100, most preferably is lower than about 50.For the viewpoint of mildness, the microcytotoxicity index of Response of anion surfactant that is preferred for antimicrobial cleansing compositions of the present invention is greater than about 25, more preferably greater than about 50, most preferably greater than about 100.The microcytotoxicity index of Response generally has medium biological activity and medium mildness for the surfactant of about 25-about 150.
Surface activator composition generally is a surfactant mixture, rather than pure surfactant (comprises " technical grade " surfactant, wherein generally comprise the mixture of the entity of different chain length, wherein also may contain high-load impurity), be difficult for measuring biological activity or mildness by the microcytotoxicity index of Response of each surface active agent composition.When said composition is mixture, can measure the microcytotoxicity index of each independent component, if all components in the compositions all is known, then its weighted mean can be used as index.If each component is not known in the compositions, the more suitable index of the chain end group of surfactant and chain length then as biological activity/mildness.
For the viewpoint of high bioactivity, the chain length of anion surfactant or surfactant mixture is about 24 carbon atoms of about 8-substantially, is preferably about 18 carbon atoms of about 10-, most preferably is about 16 carbon atoms of about 12-.Here used term " substantially " refers to be at least about 50%.For the viewpoint of mildness, preferably reduce to C 12
For bioactive viewpoint, the end group of preferred anionic surfactant is lower than about 15 dusts, preferably is lower than about 10 dusts, more preferably less than about 7 dusts." end group " is meant hydrophilic (nonhydrocarbon) part of anion surfactant, counts molecular chain-end from first polarity atom.The size of end group will be predicted according to the van der Waals radius of atom and the configuration of surfactant molecule.The end group that size is lower than about 7 dusts comprises sulfate radical, sulfonate radical and phosphate radical.For the viewpoint of mildness, preferred end group is preferably greater than about 10 dusts greater than about 7 dusts.End group greater than about 10 dusts comprises ethoxylation sulfate radical, glyceryl ether sulfonic acid root and isethionic acid root.Size that it is generally acknowledged end group is big more, prevents in the cell wall that the destructive stearic class blockage of surfactant is many more, and biological activity will reduce, and mildness increases.
The mildness of surfactant or surfactant mixture also can be measured through many conventional methods that become known for measuring the surfactant mildness.For example " Dermatology research impurity " ( J.Invest.Dermatol., 1975,64,190-195 page or leaf) and the sealing coat failure test that in US4673525 people such as (, 1987.6.16 authorizes) Small, proposes, described content all is combined in herein as a reference.In general, surfactant is gentle more, and the destructiveness of skin sealing coat is low more in the sealing coat failure test.Enter in the detected solution of the diffuser casing that contains physiologic buffer through the respective amount of radiolabeled water by measuring, measure the destruction of skin sealing coat by epidermis.Skin sealing coat osmotic value has suitable mildness near the surfactant of 0-about 75 relatively.Relative skin sealing coat osmotic value has zest greater than about 75 surfactant.Cloudy in the plane surface activating agent dissolubility slope of antimicrobial acivity composition
Being chosen in of preferred anionic surfactants surfactant also depended on the antimicrobial acivity composition to a certain extent from surfactant sedimentary ability on skin.Be applicable to that surfactant of the present invention should have enough dissolubilities to active component, but dissolubility again can not be too high, active component is retained in the solution and can not deposits on the skin in preventing to use.We find can measure optimum balance by antimicrobial acivity composition dissolubility with respect to the slope of curve of surfactant concentration in water.The mensuration of this slope (being called the dissolubility slope) K is seen the analytical method part.
The dissolubility slope K of preferred anionic surfactants surfactant of the present invention is lower than 0.60, preferably is lower than 0.40, more preferably less than about 0.25, most preferably is lower than about 0.10.
The preferably about 0.01 μ g/cm of deposition on skin of type antimicrobial cleansing compositions that floats of the present invention 2-Yue 100 μ g/cm 2Anti-microbial active, 0.1 μ g/cm more preferably from about 2-Yue 50 μ g/cm 2, 1 μ g/cm most preferably from about 2-Yue 20 μ g/cm 2
For making this personal cleaning compositions effective, must take into account the dissolubility of used given activity composition in the biological activity of surfactant and the surfactant simultaneously.
For example, ammonium lauryl sulfate (ALS) has high biological activity (microcytotoxicity index=1.0), but dissolubility slope higher (K=0.3).Because the activity of ALS, though with the antibacterial activity composition of low content and shared to proton reagent, the compositions that contains ALS still has extremely effective antimicrobial acivity.But for making active component DepositionOn skin (to satisfy above-mentioned requirement to effect), the high-dissolvability slope will require high-load active matter.In addition, contain in the compositions of ALS and also need add cosurfactant or polymer (seeing non-essential component portion) to reach the most preferred mildness of the present invention.
Select for use lauryl ether-3 ammonium sulfate (microcytotoxicity index=120, and K=0.5) can make compositions as mild as a dove, but, need to adopt high-load proton reagent and the antimicrobial acivity composition given for reaching the present invention's effect of delaying time as surfactant.
The alkane sulfonate that has little end group, average chain length and be 15.5 (K=0.1) is active higher surface activity agent, and the deposition degree of active component is very high, and it is purchased grade product is the Hastapur SAS  by name that is produced by Hoechst Celanese.The active component and the sour compositions that contain low content can be shared with high-load alkane sulfonate, and wherein surfactant plays most of effect to the time-delay effect of compositions.Also can the alkane sulfonate of low content is shared with more high-load active component in the compositions, to obtain gentleness and effective composition.Can the active component and the alkane sulfonate of moderate content is shared, because its dissolubility index shows that the deposition degree of active component in the said composition is very high.
The non-limiting example that is applicable to preferred anionic surfactants surfactant of the present invention comprises that chain length is mainly the alkylsurfuric acid ammonium and the alkyl sodium sulfate of 12-14 carbon atom, and alkyl ether ammonium sulfate and sodium alkylether sulphate, chain length is mainly the olefin sulphates of 14-16 carbon atom, and chain length is the alkane sulfonate of 13-17 carbon atom and their mixture.What especially preferably be applicable to this is ammonium lauryl sulfate and sodium lauryl sulfate; Myristyl ammonium sulfate and Semen Myristicae sodium sulfate; The ammonium sulfate and the sodium salt of lauryl ether-1, lauryl ether-2, lauryl ether-3 and lauryl ether-4; C 14-16Alkene sulfonic acid ammonium and sodium salt, C 13-17Alkane sulfonate and their mixture.
Have found that, with high-load non-anion surfactant and the shared effect that in fact can reduce delay feature of high-load anion surfactant that constitutes by non-ionic surface active agent, cationic surfactant, amphoteric surfactant and their mixture.This is the most obvious for cationic surfactant and amphoteric surfactant, it is generally acknowledged that these surfactants can hinder the destruction of lipid in (interaction between electric charge) anion surfactant cell membrane.The amount ratio of these non-anion surfactants and anion surfactant should be lower than 1: 1, preferably is lower than about 1: 2, more preferably less than about 1: 4.
Of the present inventionly float the salt that the type antimicrobial cleansing compositions does not preferably contain hydrotropy sulfonate, particularly terpenoid, or monokaryon or binuclear aromatic chemical compound, as the sulfonate of Camphora, toluene, dimethylbenzene, cumene and naphthalene.C. Give proton reagent
The type antimicrobial cleansing compositions that floats of the present invention contains the proton reagent of giving that accounts for about 12% (weight) of the about 0.1-of personal cleaning compositions, and preferred about 0.5% to about 10%, and about 7.5% (weight) of more preferably about 1-most preferably is about 5% (weight) of about 2.5-." to proton reagent " is meant can be at the acid compound or its mixture that keep non-dissociated acid after the use on skin.Giving proton reagent can be organic acid, comprises polymeric acid, mineral acid or their mixture. Organic acid
At least can partly keep not dissociating in clean compositions as the organic acid of giving proton reagent, and remain to compositions wash and rinse cycle in diluted after.Organic acid should be lower than 5.5 for the pKa value of proton reagent at least.This class is organic directly adds in the compositions for the form that proton reagent can acid, or the enough strong separate acid of conjugate base by adding required acid and capacity is to be formed non-dissociated acid by conjugate base. Organic acid biological activity index
To decide for the selection of proton reagent on their biological activity to preferred organic.Biological activity is characterized by biological activity index Z, and it is defined as follows:
Z=1+0.25pKa 1+0.42logP
This biological activity index combines the disassociation characteristic and the hydrophobicity of acid.Key is that the non-dissociated proton reagent of giving is depositing on the skin to reduce the negative charge on the cell wall among the present invention.Acid dissociation constant pKa 1Be chemical constituent with respect to adding medium pH give the proton ability.Since there is more not disassociation acid in the preferred composition, for the pH of given product, the general more preferably higher acid of pKa.The partition coefficient P of capryl alcohol-water represents that the composition in the solution more is soluble in water or oil phase.It is the standard of composition hydrophobic property in the solution basically: the partition coefficient of composition is high more, and oil-soluble is high more, and water solublity is low more.Because the acid that needs to be dissolved in the compositions in use discharges from the aqueous cleaning agent, be deposited on the butyraceous skin, and after rinsing, still keep, therefore the more preferably higher organic acid of octanol-water partition coefficient.
The present invention floats in the type antimicrobial cleansing compositions preferred organic biological activity index of giving proton reagent greater than about 0.5, is preferably greater than approximately 1.0, more preferably greater than about 1.5, most preferably works energetically about 2.0. Mineral acid
As the mineral acid of giving proton reagent in clean compositions or washing and rinse cycle in can not keep the state of not dissociating after diluted.However, find that still mineral acid can be in the present invention as effectively giving proton reagent.There is no particular determination in theory, but think that strong inorganic acid can make in the Skin Cell proteinic carboxyl and phosphatidyl protonated, thereby form the original position acid that do not dissociate.This class can only directly add in the compositions for proton reagent with the form of acid. pH
A key that reaches beneficial characteristics of the present invention is that the non-dissociated acid that forms (deposition or original position form) to proton reagent is retained on the skin with protonated form.Therefore, the pH that floats the type antimicrobial cleansing compositions of the present invention should be transferred to enough low so that on skin, form or deposit a large amount of not disassociation acid.It is about 6.0 that the pH of compositions should be adjusted to, more preferably be buffered to about 3.0-, and it is about 5.0 to be preferably about 3.0-, more preferably about 3.5-about 4.5.
The organic acid non-exclusionism example that can be used as to proton reagent has: adipic acid, tartaric acid, citric acid, maleic acid, malic acid, succinic acid, glycolic, 1,3-propanedicarboxylic acid, benzoic acid, malonic acid, salicylic acid, gluconic acid, polymeric acid, their salt and their mixture.The non-exclusionism example that is used for this mineral acid has hydrochloric acid, phosphoric acid, sulphuric acid and their mixture.
Owing to compare with other acid, polymeric acid is low to the zest of skin, they press down a little less than the bubble property and have the viscous sense that the certain user likes when rinsing, based on these viewpoints, especially preferably uses it for the present invention.Term " polymer " acid used herein " be meant the acid that on a chain, is connected with the carboxyl repetitive.The polymeric acid that is suitable for comprises homopolymer, bipolymer and terpolymer, but wherein should contain 30% (mol) carboxyl at least.The particular instance that is applicable to this polymeric acid comprises poly-(acrylic acid), with the copolymer of they and ion and nonionic composition (for example, maleic acid-acrylic acid, sulfonic acid-acrylate and styrene-propene acid copolymer), the molecular weight of these cross linked polyacrylates is lower than about 250,000, preferably be lower than poly-(Alpha-hydroxy) acid of about 100,000, poly-(methacrylic acid), with natural polymeric acid such as chondrus ocellatus Holmes acid, carboxymethyl cellulose and the alginic acid of existing.Here especially preferred straight chain gathers (acrylic acid).D. Deposition aid
The present invention floats type liquid anitmicrobial personal cleaning compositions and comprises about 30% (weight) of about 0.1-, is preferably about 30% (weight) of about 1-, and about 25% (weight) of more preferably about 3-most preferably is the deposition aid of about 5-about 25% (weight).Compare with the compositions that does not contain deposition aid, find that the compositions that contains deposition aid has improved biocidal efficacies.Be used for that deposition aid of the present invention can with the antimicrobial acivity composition or to improve for the deposition of proton reagent on skin at least about 20%, preferably improve approximately 30% at least, more preferably improve about 50% at least.
The deposition aid that is applicable to this for example comprises the agent of lipophile skin moisturizing, cationic polymer, non-ionic polymers, zeolite, clay and their mixture.Think that cationic polymer is that one of reason of effective deposition aid is that it can form coacervate with anion surfactant.
Be suitable for cation and the non-ionic polymers of making deposition aid among the present invention and comprise Polyethylene Glycol, polypropylene glycol, hydrolyzed silk protein, hydrolysis milk proem, hydrolysis of keratin, guar gum hydroxypropyl-trimethyl ammonium chloride, polyquaternary ammonium salt, siloxane polymer and their mixture.When cation or non-ionic polymers during as deposition aid, its consumption accounts for about 1% (weight) of about 0.1-of compositions, is preferably about 0.8% (weight) of about 0.15-, about 0.6% (weight) of more preferably about 0.2-.
The agent of lipophile skin moisturizing is particularly preferably in being used as deposition aid among the present invention.Compare it with the compositions that does not conform to the lipidosis auxiliary agent and not only have improved antimicrobial property, when the agent of lipophile skin moisturizing was deposited on user's skin, also the user to this personal cleansing product had humidification.When the agent of lipophile skin moisturizing was used as deposition aid at this, its consumption accounted for about 30% (weight) of about 1-of compositions, is preferably about 25% (weight) of about 3-, most preferably is about 25% (weight) of about 5-.
Adopt two class rheological parameters to limit the agent of lipophile skin moisturizing among the present invention.The viscosity of lipophile skin moisturizing agent is characterized by denseness (k) and shearing index (n).Adopt hereinafter the described denseness of analytical method part (k) assay method to measure, be applicable to that the denseness (k) of this lipophile skin moisturizing agent is generally about 5,000 pools of about 5-, be preferably about 3,000 pools of about 10-, more preferably about 50-about 2,000 moors.The shearing index (n) of lipophile skin moisturizing agent that is applicable to this is about 0.9 for about 0.01-, and it is about 0.5 to be preferably about 0.1-, and more preferably about 0.2-is about 0.5, and the shearing assessment of indices method of employing analytical method described in partly measured.
Although in theory and indefinite, think that lipophile skin moisturizing agent that rheological properties exceeds above limited range is not to be easy to very much emulsifying and to be difficult for deposition, be exactly too " stiff ", be difficult for adhering to or be deposited on the skin inaccessible humidification.In addition, the rheological properties of lipophile skin moisturizing agent is also very important for user's impression.Some lipophile skin moisturizing agent that is deposited on the skin is too sticky, is not got by the user.
Under some situation, also wish to limit the agent of lipophile skin moisturizing, see " cosmetics and toilet articles " 103 volumes with its solubility parameter, and the 47-69 page or leaf (in October, 1988, Vaughan).The Vaughen solubility parameter (VSP) that is applicable to the lipophile skin moisturizing agent in the liquid personal cleansing composition of the present invention is 5-10, is preferably 5.5-9.
Various lipid components and their mixture all are suitable for being used as carrier in antimicrobial personal cleaning compositions of the present invention.Preferred lipophile skin condition composition is selected from: hydrocarbon ils and wax, polysiloxanes, derivative of fatty acid, cholesterol, cholesterin derivative, two-and the Three-glycerol ester, vegetable oil, vegetable oil derivatives, the liquid nondigestible oil, see US3600186 (Marrson, on August 17th, 1971 authorized), 4005195 and 4005196 (people such as Jandacek, all authorize) on January 25th, 1977, all in conjunction with in the present invention as a reference, or be selected from the mixture that liquid easily digests oil or nondigestible oil and solid polyalcohol polyester, see US4797300 (Jandacek, on January 10th, 1989 authorized); US 5306514,5306516 and 5306515 (Letton; All authorize on April 26th, 1994), all in conjunction with in the present invention as a reference, and be selected from acetyl group glyceride, Arrcostab, alkenyl esters, lanoline and derivant thereof, newborn triglyceride, wax ester, Cera Flava derivant, sterol, phospholipid and their mixture.Fatty acid, fatty acid soaps and water-soluble polyol do not belong to the limited range of the present invention to the agent of lipid skin moisturizing.
Hydrocarbon ils and wax: some example has vaseline, mineral oil, microwax, polyolefin (for example hydrogenation and not hydrogenated polybutene and poly decene), paraffin, ceresin, ceresine, polyethylene and perhydro-squalene.The blend of vaseline and hydrogenation and not hydrogenation high molecular polybutene also is suitable for being used as the agent of lipid skin moisturizing in the present composition, wherein the amount ratio of vaseline and polybutene is 90: 10-40: 60.
Silicone oil: some example has dimethicone copolyol, dimethyl polysiloxane, diethyl polysiloxanes, high molecular dimethyl polysiloxane, C 1-C 30Pure and mild their mixture of mixed alkyl polysiloxanes, phenyl dimethyl polysiloxane, dimethyl polysiloxane.Preferred non-volatile polysiloxanes is selected from dimethyl polysiloxane, dimethyl polysiloxane alcohol, C 1-C 30Mixed alkyl polysiloxanes and their mixture.Be applicable to the nonlimiting examples US 5011681 (people such as Ciotti, on April 30th, 1991 authorized) of this polysiloxanes, in conjunction with in the present invention as a reference.
Two and triglyceride: some example is Oleum Ricini, soybean oil, soybean oil derivative such as maleinization soybean oil, safflower oil, Oleum Gossypii semen, Semen Maydis oil, walnut oil, Oleum Arachidis hypogaeae semen, olive oil, cod-liver oil, almond oil, American Avocado Tree oil, Petiolus Trachycarpi oil and Oleum sesami, vegetable oil and vegetable oil derivatives; Oleum Cocois and coconut oil derivative, Oleum Gossypii semen and Oleum Gossypii semen derivant, simmondsia oil, cocoa butter etc.
Aceto-glycerideAlso be suitable for, the example has acetylated monoglyceride.
The preferred employing LanolineAnd derivant, example comprises lanoline, lanolin oil, lanolin wax, lanolin alcohol, lanolin fatty acid, isopropyl lanolate, acetylated lanolin, Acetylated lanolin alcohols., linoleic acid lanoline alcohol ester, castor oil acid lanoline alcohol ester.
Most preferably have at least 75% to be selected from following lipid component in the lipophile skin conditioning agent: the blend of vaseline, vaseline and polyphosphazene polymer butylene, mineral oil, liquid nondigestible oil (for example liquid Oleum Gossypii semen sucrose octaester), or liquid easily digests the mixture of oil or nondigestible oil and solid polyalcohol polyester (for example by C 22The sucrose octaester of fatty acid preparation), wherein easily to digest the amount ratio of oil or nondigestible oil and solid polyalcohol polyester be about 96 to liquid: about 80: 20 of 4-, hydrogenation or not hydrogenated polybutene, microwax, polyolefin, paraffin, ceresin, ceresine, polyethylene, perhydro-squalene, dimethyl polysiloxane, alkylsiloxane, polymethyl siloxane, methyl phenyl silicone and their mixture.When using the mixture of vaseline and other lipid, carat be preferably about 10: about 1: 2 of 1-, more preferably about 5: about 1: 1 of 1-with the amount ratio of other lipid of selecting for use (hydrogenation or not hydrogenated polybutene or poly decene or mineral oil).E. Water
The water that preferably contains the 35-that has an appointment about 98.8% (weight) in the type antimicrobial liquid cleansing compositions that floats of the present invention is preferably about 98% (weight) of about 45-, and about 97.5% (weight) of more preferably about 55-most preferably is about 95.99% (weight) of about 65-.The water that preferably contains about 2-about 25% (weight) in the solid soap scheme of the present invention, about 20% (weight) of more preferably about 3-most preferably is about 15% (weight) of about 5-.
Of the present invention float the type antimicrobial liquid cleansing compositions under 26.7 ℃ apparent viscosity or clean viscosity to be preferably about 500-about 60,000cps is preferably approximately 5,000-is about 30,000cps.Unless otherwise indicated, being used for term of the present invention " viscosity " adopts Brookfield RVTDCP, CP-41 rotor to measure through 3 minutes under 1 rev/min of condition." only " viscosity is meant the viscosity of undiluted liquid cleaner.F. Preferred non-essential composition Mildness promoter
For reaching mildness of the present invention, can add the non-essential composition that to promote the skin mildness.These compositions comprise cation and non-ionic polymers, cosurfactant, humidizer and their mixture.The polymer that is applicable to this comprises Polyethylene Glycol, polypropylene glycol, hydrolyzed silk protein, hydrolysis milk proem, hydrolysis of keratin, guar gum hydroxypropyl-trimethyl ammonium chloride (trimonium chloride), polyquaternary ammonium salt, siloxane polymer and their mixture.During use, mildness promotes the consumption of polymer to account for about 1% (weight) of the about 0.1-that floats the type antimicrobial cleansing compositions, is preferably about 1% (weight) of about 0.2-, about 0.6% (weight) of more preferably about 0.2-.The cosurfactant that is applicable to this comprises ethoxylated alcohol, POE (20) Isosorbide Dinitrate monoleate (Tween  80), Polyethylene Glycol cocos nucifera oil ester and the Pluronic  propylene oxide/ethylene oxide block copolymer of non-ionic surface active agent such as Genapol  24 series, and amphoteric surfactant such as alkyl betaine, alkyl sulfobetaines, alkyl both sexes acetas, alkyl both sexes diacetate esters, alkyl both sexes propionic ester and alkyl both sexes dipropionate.During use, cosurfactant accounts for about 70% (weight) of about 20-of Cleasing compositions weight, is preferably about 20-about 50% (weight) anion surfactant. Stabilizing agent
In the liquid anitmicrobial compositions of the present invention with the agent of lipophile skin moisturizing when the deposition aid, also contain the stabilizing agent that accounts for the about 0.1-of compositions about 10% (weight) in the compositions, be preferably about 8% (weight) of about 0.1-, about 5% (weight) of more preferably about 0.1-.
Stabilizing agent is used for forming the crystal stability network structure at liquid cleansing composition, prevents that the drop cohesion or the product of lipophile skin moisturizing agent is separated.Network structure has time dependent viscosity recovery characteristic (for example thixotropy) after the shearing strain effect.
The stabilizing agent that is applicable to this is not a surfactant.Stabilizing agent can improve to be stored and stress stability, separates but can make personal cleaning compositions produce when bubbling, thereby promotes the deposition of lipid skin moisturizing agent on skin.Cleansing emulsion of the present invention and polymeric diamond sponge network structure (see US 5144744, Campagnoli, JIUYUE in 1992 was authorized on the 8th, in conjunction with in the present invention as a reference) this advantage is obvious especially when being used in combination.
In one embodiment of the invention, used stabilizing agent comprises the crystal stabilizer of hydroxyl in the personal cleaning compositions.This stabilizing agent can be fatty acid, fatty ester or the water-insoluble wax shape fat soap etc. of hydroxyl.
The crystal stabilizer of hydroxyl is selected from:
Figure C9880739400291
Wherein
R 1Be
R 2Be R 1Or H
R 3Be R 1Or H
R 4Be C 0-20Alkyl
R 5Be C 0-20Alkyl
R 6Be C 0-20Alkyl
R 4+R 5+R 6=C 10-22
1≤x+y≤4 wherein;
R wherein 7Be-R 4(CHOH) xR 5(CHOH) yR 6
M is Na +, K +Or Mg ++, or H; And
(iii) their mixture.
Some preferred hydroxyl stabilizing agent comprises 12-hydroxy stearic acid, 9,10-dihydroxystearic acid, three-9,10-dihydroxystearic acid glyceride and three-12-hydroxy stearic acid glyceride (mainly containing three-12-hydroxy stearic acid glyceride in the castor oil hydrogenated).Three-12-hydroxy stearic acid glyceride most preferably is used for emulsion composition of the present invention.
When using the hydroxyl crystal stabilizer in the personal cleaning compositions, its consumption accounts for about 10% (weight) of about 0.1-of liquid personal cleansing composition, is preferably about 8% (weight) of about 0.1-, about 5% (weight) of more preferably about 0.1-.Stabilizing agent at room temperature or be water-fast under the condition near room temperature.
Perhaps, the stabilizing agent of personal cleaning compositions employing of the present invention can comprise polymer viscosifier.When adopting polymer viscosifier as stabilizing agent in the personal cleaning compositions, its consumption generally accounts for about 5% (weight) of about 0.01-of compositions, is preferably about 3% (weight) of about 0.3-.Polymer viscosifier is anion preferably, nonionic, cation or hydrophobically modified polymer, being selected from molecular weight is 1,000-3,000,000 guar gum class cationic polysaccharide, by acrylic acid and/or the deutero-anion of methacrylic acid, cation and nonionic homopolymer, anion, cation and non-ionic cellulose resin, dimethyl dialkyl ammonium chloride and acrylic acid cation copolymer, the cationic homopolymer of dimethyl alkyl ammomium chloride, cation polyolefin and ethoxylation polyalkyleneimine, molecular weight are 100,000-4,000,000 Polyethylene Glycol and their mixture.Preferred polymers is selected from sodium polyacrylate, hydroxyethyl-cellulose, cetyl hydroxyethyl cellulose and polyquaternary ammonium salt-10.
Perhaps, used stabilizing agent can comprise C in the personal cleaning compositions of the present invention 10-22Glycol fatty acid ester.C 10-22Glycol fatty acid ester also can be shared with above-mentioned polymer viscosifier.This ester is diester preferably, is more preferably C 14-18Diester most preferably is a diglycol stearate.In personal cleaning compositions, use C 10-22During the glycol fatty acid ester used as stabilizers, its consumption is generally about 10% (weight) of about 3-of personal cleaning compositions, is preferably about 8% (weight) of about 5-, about 8% (weight) of more preferably about 6-.
The another kind of stabilizing agent of personal cleaning compositions of the present invention that is applicable to comprises the dispersibility amorphous silica, is selected from fumed silica and precipitated silica, and their mixture.Used term " dispersibility amorphous silica " is meant little, the noncrystal silicon dioxide of micronization, average coalescent granularity is less than about 100 microns.
Fumed silica is also referred to as arc silicon dioxide, Silicon chloride. is hydrolyzed into gas phase makes under the oxyhydrogen flame condition.It is generally acknowledged that the silicon dioxide molecules that firing method makes can condense the formation granule, these granules can be through collision, adhere to sintering and be in the same place.Can obtain three-dimensional side chain aggregation by this method.When aggregation is cooled to the fusing point (about 1710 ℃) of silicon dioxide when following, further collision can cause the mechanical interlocking of chain, forms aggregate.Precipitated silica and silica dioxide gel generally make in aqueous solution.Referring to the article (in March, 1992) that is entitled as " the CAB-O-SIL  fumed silica in cosmetics and the personal cleanliness's care product " among article (in October, 1993) that is entitled as " characteristic and the function of the undressed fumed silica of CAB-O-SIL  " among the Cabot technical data handbook TD-100 and the Cabot technical data handbook TD-104, described content combination in the present invention as a reference.
The average aggregation size of fumed silica is preferably about 100 microns of about 0.1-, is preferably about 50 microns of about 1-, about 30 microns of more preferably about 10-.Aggregate by particle mean size be about 10 microns of about 15 microns of about 0.01-, about 0.05-, more preferably from about about 5 microns of 0.1-, aggregation that most preferably from about 0.2-is about 0.3 micron constitute.The surface area of silicon dioxide is preferably greater than about 50 meters squared per gram, more preferably greater than about 130 meters squared per gram, most preferably greater than about 180 meters squared per gram.
When amorphous silica was used used as stabilizers, it is about 10% that its consumption in emulsion composition is generally about 0.1-, and it is about 8% to be preferably about 0.25-, about 5% (weight) of more preferably about 0.5-.
The 4th class stabilizing agent that is applicable to personal cleaning compositions of the present invention is the dispersibility smectic clays, is selected from bentonite, hectorite and their mixture.Bentonite is a colloidal state aluminum sulfate clay.Referring to Merck indexThe 11st edition (1989) 1062 (164 pages) are in conjunction with in the present invention as a reference.Hectorite is the clay that contains sodium, magnesium, lithium, silicon, oxygen, hydrogen and fluorine.Referring to Silent The gram indexThe 11st edition (1989) 4538 (729 pages) are in conjunction with in the present invention as a reference.
When using the smectic clays used as stabilizers in the personal cleaning compositions of the present invention, it is about 10% that its consumption is generally about 0.1-, and it is about 8% to be preferably about 0.25-, more preferably about 0.5-about 5%.
Other known stabilizing agent such as fatty acid and aliphatic alcohol also are applicable to the present composition.Lauric acid and Palmic acid especially preferably are applicable to this.G. Other non-essential composition
Also can contain various non-essential compositions in the present composition." the international cosmetic composition handbook of CTFA has been described various indefinitenesses beauty treatment and the medicinal ingredients that are usually used in the skin care industry field in (nineteen ninety-five the 6th edition, combination in the present invention as a reference in full), all be applicable to the present composition.The 537th page of non-limiting example of listing the function class composition.These function class compositions comprise: abrasive material, anti-acne agents, anticaking agent, antioxidant, binding agent, bio-additive, extender, chelating agen, chemical addition agent, toner, the beauty treatment astringent, the beauty treatment Biocide, denaturant, medicinal astringent, emulsifying agent, external-use analgesic, film former, fragrance component, wetting agent, opacifier, plasticizer, antiseptic, propellant, Reducing agent, skin whitener, skin conditioning agent (softening agent, wetting agent, multi-functional composition and covering agent), shielding medicine for skin, solvent, short infusion, hydrotropic solvent, solubilizing agent, suspending agent (non-surface-active agent class), sunscreen, UV absorbent and viscosifier (moisture or anhydrous).The function class composition that is suitable for that other those of ordinary skills know comprises solubilizing agent, sequestering agent and keratolytic etc.II. Characteristic
The type antimicrobial cleansing compositions that floats of the present invention has following characteristic.A. Time-delay antibiotic effect index to gram negative bacteria
Of the present invention float the type antimicrobial cleansing compositions to the time-delay antibiotic effect index of gram negative bacteria greater than about 0.3 (sterilization 50%), be preferably greater than about 1.0 (sterilizations 90%), more preferably greater than about 1.3 (sterilizations 95%), most preferably greater than about 2.0 (sterilizations 99%).Adopt that analytical method part hereinafter is described measures time-delay antibiotic effect index to gram negative bacteria to the antibiotic time-delay efficacy test of colibacillary live body method.This exponential representation be the denary logarithm difference of bacterial concentration between sample and matched group.For example index is that the logarithm value of 0.3 expression sterilization number is 0.3 (Δ log=0.3), represents that promptly bacterial number reduces by 50%.B. The mildness index
The mildness index that floats the type antimicrobial cleansing compositions of the present invention is greater than about 0.3, be preferably greater than about 0.4, more preferably greater than about 0.6.Measure the mildness index by forearm contrast coating test of the present invention (FCAT).III. Float the manufacture method of type antimicrobial cleansing compositions
The method that can adopt art-recognized being used to prepare various forms of personal cleaning compositions prepares the type antimicrobial personal cleaning compositions that floats of the present invention.IV. Float the application process of type antimicrobial cleansing compositions
The type antimicrobial personal cleaning compositions that floats of the present invention is applicable to the personal cleanliness, particularly clean hands.General Cleasing compositions with dosage or effective dose is coated in is washed the position.Also can be coated on towel, sponge, liner, cotton balls, bubble husband wiping or other applying device through the Cleasing compositions of centre coating with dosage.As needs, drenched but wash the position water in advance.Compositions of the present invention combines with water in washing process, and rinses from skin.The effective dose of product generally will be decided on a human needs and use habit.The present composition is generally the about 10mg/cm of about 0.1-at the cleaning dosage of being washed skin part 2, the about 5mg/cm of 0.6-more preferably from about 2
The analytical test method The microcytotoxicity reaction testList of references: Microcytotoxicity handbook (Microtox Manual): toxicity test handbook, 1992
The I-IV volume; Microbics company.Device: microcytotoxicity M500 toxicity test device; Microbics company
Adopt computer to carry out the described data collection and analysis of above-mentioned document.Step: 1. Preparation (the normal concentration: 1000ppm) of sample liquid storage
The sample liquid storage for preparing tested anion surfactant is as the liquid storage of all dilute solutions.Standard " initial concentration " is the highest tested concentration, is 500ppm.If (but adopt the initial concentration of 500ppm can't obtain value of calculation, for example active surfactant has been killed the whole reagent in all diluents, then can be according to the known range adjusting initial concentration of the EC50 value of the surfactant of previous mensuration).The concentration of prepared liquid storage is the twice of initial concentration.
(a) in beaker, add 0.1g (or aequum of regulating on demand) anion surfactant (considering the activity of raw material).
(b) microcytotoxicity diluent (2% sodium chloride, Microbics company) is added to the 100g total amount.
(c) agitating solution is guaranteed abundant mixing.2. The reconstruct of microcytotoxicity reagent and the preparation of measured object
(a) start assay device, make the reagent wells temperature be equilibrated at 5.5 ℃, interrupt cultivating, read Kong Wenzhi and be equilibrated at 15 ℃.
(b) in reagent wells, insert clean tube (Microbics company), add 1.0ml microcytotoxicity reconstituted solutions (distilled water, Microbics company), cooled off 15 minutes.
(c) by in the reagent bottle, adding the standard vial (Fei Shi vibrio, Microbics company) of the refrigerative reconstituted solutions reconstruct of 1.0ml microcytotoxicity acute toxicity reagent rapidly.
(d) the solution 2-3 second in the moving reagent bottle of whirlpool, then reconstruct reagent is refunded in the refrigerative test tube, bottle is put back to reagent wells.Stablized 15 minutes.
(e) 8 test tubes that will fill 500 μ l microcytotoxicity diluent are put into the culture hole of test set as measured object, cool off 15 minutes.3. The measured object diluent
By 7 parts of measured object diluents of sample liquid storage preparation.Final volume in all test tubes should be 1.0ml.
(a) 8 empty test tubes are placed test tube rack.
(b) in test tube 1-7, add 1.0ml microcytotoxicity diluent solution.
(c) in test tube 8, add 2.0ml sample liquid storage (1000ppm).
(d) solution with 1.0ml test tube 8 adds in the test tube 7, and mixes the solution in the test tube 7.
(e) continuously the new solution that forms of 1.0ml is changed in next test tube (7 to 6,6 to 5 etc.).From test tube 2, take out 1.0ml solution and abandon.Test tube 1 is the blank phase that only contains the microcytotoxicity diluent.Test tube is put into the test set culture hole by concentration order from low to high to be preserved.These test tubes are answered 8 test tubes of preparation in the corresponding above-mentioned steps 2.Cooled off 15 minutes.4. Measured object and sample bioluminescence test
(a) 10 μ l reconstruct reagent are added in 8 pre-cooled test tubes that fill the measured object (containing 500 μ l diluent) of preparation in the step 2.With stable reagent 15 minutes.
(b) open microcytotoxicity data collection and report software (Microbics company), selected " beginning test ", initial concentration (in ppm, being 500ppm when adopting normal concentration) and matched group number (1) and diluent group number (7) are revised in import file name and explanation.Time 1 should be selected 5 minutes, and the time 2 should be selected " nothing ".Press enter key, begin test by space bar then.
(c) will place the reading hole corresponding to the measured object test tube that contains reagent of the blank phase of test, and by " setting ".Treat that test tube appears the back by " reading ", then computer can be collected data.
(d) for test tube correct in the reading hole, by by " reading " key and as calculated machine prompting can carry out reading to remaining 7 test tubes that contain reagent equally.
(e) carried out 8 times all initial readings after, the diluted measured object of 500 μ l is changed in the test tube that contains reagent accordingly.Culture hole is put back in moving or whirling motion mixing again through whirlpool.Computer was through 5 minutes countings, and prompting beginning final reading.
(f) the correct test tube that will fill the measured surface activating agent of reagent and dilution places the reading hole, by " reading ", carries out final reading behind the computer prompted.5. Data analysis
The linear regression (with respect to the logarithmic sterilization percent of concentration) that adopts " operation of the data file statistics " option (suggestion is used) in the microcytotoxicity software or make data can calculate the bioluminescence of the microcytotoxicity acute toxicity reagent concentration (in ppm) (EC50 value) by the measured object of initial value reduction by 50%.Can adopt following formula to calculate sterilization percent:
Figure C9880739400351
Wherein x refers to be in corresponding concentration
Figure C9880739400353
The microcytotoxicity index is EC50 value (in ppm). The dissolubility slope KDevice: add the liquid scintillation counter (Ultima Gold, Packard Instrument company) that is used for liquid scintillation fluid usefulness correction quenching (quench) curve.1. Warp 14 The preparation of the triclosan  of C labelling
(a) always add 5.00g triclosan (TCS) powder commonly used at the 20ml tubule.
(b) add 10 μ Ci 14C TCS and 1ml acetone.
(c) agitating solution is 3 minutes, or extremely all triclosans dissolve fully.
(d) be blown into nitrogen, remove most solvents, solidify once more until solution.
(e) with the solid abrasive powdered, and in the presence of nitrogen dried overnight, make lay-by material through labelling.
(f) activity of mensuration triclosan (in DPM/g) is as the conversion factor of back sample.
1. the above-mentioned e step of 0.1g powdery triclosan (record weight) is added in the liquid scintillation vial.
2. add 10ml liquid scintillation fluid (Ultima Gold).
3. insert liquid scintillation counter, calculate the per minute decay (DPM) of sample.
4. with the weight of per minute decay, determine conversion factor (DPM/g triclosan) divided by triclosan in the 1-f-1 step.2. The dissolubility scheme
(a) adopting in 7-9 grain tap water concentration is the liquid storage that 16% anion surfactant preparation does not contain triclosan.
(b) on test tube rack, place 8 empty test tubes.
(c) in flicker bottle 1, add the 3ml liquid storage.
(d) preparation is contained in 55 parts of 3ml solution in the flicker bottle, is respectively 1: 2,1: 4,1: 8,1: 16 and 1: 32 diluent (ultimate density is 8%, 4%, 2%, 1% and 0.5%) of liquid storage.
(e) in each bottle, add 0.05g respectively through radiolabeled triclosan (seeing above-mentioned steps 1-e), and magnetic stirring bar.This group bottle stirred through 2 hours at least.If the triclosan solid phase disappeared adds triclosan again, guarantee to balance each other.
(f) from each diluent, take out 1.0ml, place the little centrifuge tube of 1.5ml, under 1500rpm centrifugal 5 minutes.
(g) take out 0.1-0.4g (record weight) from the upper strata of centrifugal sample, place clean liquid scintillation vial.
(h) in bottle, add 10ml liquid scintillation mixed liquor (Ultima Gold).
(i) adopt the per minute of liquid scintillation counter record bottle to decay.
(j) conversion factor of the above-mentioned 1-f step of employing converts the per minute decay to the weight of triclosan.
(k) divided by the weight number of step 2-g, calculate triclosan percentage ratio (maxima solubility in the sample).
(l) diluent to each group anion surfactant repeats above-mentioned steps g-l.3. The calculating K value
Do the linear regression of triclosan maxima solubility according to following restriction, calculate dissolubility efficient K surfactant concentration.
(a) nearly all surfactant is all represented with K with respect to the slope of the solubility curve of 1-2% surfactant.
(b) the triclosan maxima solubility of some surfactant is outside the 1-2% surfactant range of linearity.Then must be by whole ranges of linearity calculating K value, as calculating from 0-4%, 1-4% or 0.5-2% concentration level.
The calculating K value is very important near the scope of 2% surfactant, because this concentration is about the concentration of surfactant in the Cleasing compositions of dilution. To colibacillary live body time-delay antibiotic effectList of references: Aly, R; Maibach, H.I.; Aust, L.B.; Corbin, N.C.; Finkey, M.B.1994.
1. contain the live body antibacterial action of the antimicrobial soap of 1.5% and 0.8% trichloro-symmetrical diphenyl urea to two kinds of pathogen bacterial strains." cosmetic chemistry association magazine " (J.Soc.Cosmet.Chem.), 35,351-355,1981.
2. measure the intravital method of local antimicrobials." cosmetic chemistry association magazine ", 32,317-323.1. Testing program
Adopt following method to measure the time-delay antibiotic effect of liquid and solid soap antimicrobial product.The forearm that is used for the measured is no longer handled through other, adopts the blank soap that does not contain antibacterial to organize in contrast and reports bactericidal action.Antibiotic blank group should not have the time-delay antibacterial action in test.2. Stage before the test
Testing in preceding 7 days requires the measured must not use antimicrobial product.Check the measured before tested, hand skin have wound/breakage can not participate in test, 3. Washing methods
(a) wash the both sides forearm once with contrasting to soap, remove dirt or temporary antibacterial.The rinsing forearm is also dry.
(b) laboratory technician is drenched glove both hands, and 1.0ml liquid test product (handling with soap bar according to above-mentioned list of references) is coated on measured's forearm, and it foamed 45 seconds on measured's palmar forearm with personal order.
(c) with 90-100 tap water with the speed rinsing of 1GPM 15 seconds.
(d) adopt test product repeating step b-c 2 times (washing altogether 3 times).
(e) pat dry forearm with napkin, (using rubber-stamp) marks tested position (about 8.6cm 2Scope).
(f) repeat overall process (step a-e), another forearm of measured is used reference product.4. Cultural method
(a) escherichia coli inoculum (growth is 18-24 hour under 10536,37 ℃ of the ATCC, in Semen sojae atricolor-casein broth bouillon lyophilizing liquid storage) is adjusted to 10 8Organism/milliliter (transmittance with respect to the blank phase of TSB in the spectrometer is 0.45).
(b) use inoculating loop at the about 3cm in tested position 2Scope in inoculation 10 μ l escherichia coli inoculums, cover Hilltop Chamber (Hilltop Research Inc. product).
(c) repeat this method at the tested position of each forearm.5. Bacterial sampling (extraction steps)
(a) in water, use 0.04%KH 2PO 4, 1.01%Na 2HPO 4, 0.1% trinitrotoluene X-100,1.5% Polysorbate80 (Spheron MD 30/70), 0.3% lecithin preparation sampling solution, with the HCl of 1N with pH regulator to 7.8.
(b) after the inoculation just in time 60 minutes the time, remove Hilltop Chamber down from sampling point.With 8.6cm 2Sampling cup place on this position.
(c) in cup, add 5ml sampling solution.
(d) gently scrape tested position 30 seconds with the glass policeman, extract antibacterial.
(e) remove sampling solution with pipet, place aseptic label test tube.
(f) with the repeated sampling of 5ml sampling liquid.Back 60 minutes of cultivation this sampling procedure is repeated at each position.6. Measure bacterial population
(a) use 0.117%Na 2HPO 4, 0.022%Na 2HPO 4Prepare sulfate buffer solution with 0.85% sodium chloride, and with 1N hydrochloric acid with the pH regulator of solution to 7.2-7.4.
(b) sterilely from test tube, take out 1.1ml sampling solution, this solution of coating 0.1ml on the trypticase-soy agar that contains 1.5% Polysorbate80.1ml is placed 9ml sterile phosphate buffer agent, make 1: 10 sampling solution dilution liquid.Repeat this method again and (respectively organize diluent) more than 3 times.
(c) reversing counting chamber was cultivated 24 hours down at 35 ℃.
(d) clump count that forms on the count plate, bacterial population multiply by dilution gfactor (initial sample=10, diluent=100 first, secondary dilution liquid=1000, the rest may be inferred) calculate the result, final result forms bacterium colony unit number (CFU ' s/ml) in every milliliter.7. Gauge index
Gram negative bacteria time-delay antibiotic effect index=log 10(CFU ' at blank phase position s/ml)-log 10(CFU ' at test product position s/ml) Forearm contrast coating test (FCAT)List of references: Ertel, people such as K.D. " are used to assess the forearm contrast coating technology of the relative mildness of personal cleansing product " " cosmetic chemistry association magazine " 46 (1995) 67-76
Forearm contrast coating test or title FCAT differentiate the controlled trial of product to the difference of skin mildness.Contrast with the cleansing soap matched group and the test product that contain the standard soap. Tested group of restriction
The tested group membership who is adopted comprises 20-30 people, and the age is 18-55 year, washes one's hands by rule with soap.Have should getting rid of of following situation among the selected measured: (1) is in initial trial, the initial degree of drying of forearm is 3.0 or higher, (2) suffer from skin carcinoma, eczema or psoriasis on the forearm, (3) just accepting injection of insulin, (4) be in trimester of pregnancy or age of sucking, or (5) are just being accepted the dermatopathy treatment or are suffering from contact hypersensitive.The measured should avoid hot bath, swimming, Exposure to Sunlight during development test, must not use any soap class, cleaning product, cream frost or gel on its forearm.In at least 2 hours, measured's forearm must not get wet before the classification process.Research adopts double blinding, product order form at random to carry out.Clinical assistants all should be confirmed its nursing order and record before each measured washs.
Products applied 9 times on forearm altogether: use 2 every day in preceding four days, and last day is with 1 time.The supervision detection means, washroom should be 3 hours every minimum.
In the washing process, clinical assistants all wears disposable glove, and rinsing glove in the middle of the nursing need be changed glove for different measured. Reference product
Reference product is the compacting soap bar, wherein contains:
56.1% tallow acid sodium
18.7% coconut oil sodium
0.7% sodium chloride
24% water
0.5% submember (essence, impurity) The product application program
Test product and reference product are tested on same arm.Adopt following method of testing.
1. arm is placed under the faucet, drench the whole palmar forearm of measured with 95-100 tap water.
2. clinical assistants is drenched 1/4 Masslinn  towel (about 8 " * 6 ") with tap water, extracts towel gently and removes excessive water.
3. clinical assistants, is coated in product on the forearm near the position of ancon from, and process is as follows:
Fluid product
A. the 0.10cc test product is coated on the center that suitably marks the position with syringe.
B. drench two fingers (forefinger and middle finger) of wearing (latex) glove with the tap water that flows.
C. looping at coating part with the finger that drenches makes product bubble for 10 seconds.
D. the foam of coating part kept 90 seconds, then with the tap water rinsing 15 seconds of flowing, noted the not foam of eccysis adjacent regions.After the rinsing 10 seconds, clinical assistants is cleaned this position gently with glove two fingers in residue 5 seconds.
Soap bar products
A. drench two fingers (forefinger and middle finger) of wearing (latex) glove with the tap water that flows.
B. soap bar is simply placed under the tap water that flows and drench.Must when begin to test every day, drench tested soap bar with mobile tap water.
C. looped for 15 seconds with the finger friction of drenching on the soap bar surface, make foaming between soap bar and the finger.
D. will be with foamy finger to loop and rub for 10 seconds, on skin, foam at application site.
E. foam kept for 90 seconds at application site, then with the tap water rinsing 15 seconds of flowing, noted the not foam of eccysis adjacent regions.After the rinsing 10 seconds, clinical assistants is cleaned this position gently with glove two fingers in residue 5 seconds.
Wipe product
A. with the cleaning wiping cloth doubling, intersect, carry out wiping gently through looping at suitable position.
B. air-dry this position 90 seconds.Not rinsing.
Retention type product
A. the 0.10cc test product is coated on the center that suitably marks the position with syringe.
B. looped for 10 seconds at coating part with glove finger.
C. air-dry this position 90 seconds.Not rinsing.
4. after waiting stop for 90 seconds, the residue coating part on arm repeats above process, implements this process to the wrist direction.
5. at suitable test position repeating step 1-4, apply product 2 times in tested zone.
6. after all coating parts all applied twice product, clinical assistants patted dry measured's arm gently with disposable tissues.
Assessment
The classification expert assesses the skin through every processing after initial and final research is cleaned 3 hours.At controllable light (General Electric Cool White, 22 watts, 8 " Circuline fluorescent lamp), 2.75 x magnifications (the KFM-1A type Luxo enlarger lamp that throws light on, MarshallIndustries, Dayton, OH) assessment nursing position under the condition.
By the drying property of classification expert assessment and evaluation skin, by following standard grading.
Table 1
Forearm position grade classificationRank xerosis cutis 0 moist 1.0 visible slight efflorescence speckle and accidental visible small pieces peeling position.2.0 generalized slight efflorescence.Existence is chapped in early days or accidental visible small pieces rise
The skin zone position.3.0 generalized medium efflorescence and/or severe is chapped and peeling.4.0 generalized severe efflorescence and/or severe is chapped and peeling.5.0 generalized height is chapped and peeling.Exist eczema to change.There is efflorescence,
But it is not obvious.Can find that hemorrhagic chaps.6.0 generalizedly seriously chap.Eczema occurring changes.Hemorrhagic occurring chaps.
Peeling begins to disappear on a large scale.
Forearm contrast coating test (FCAT) generally only is gentle to the moderate zest to skin; But in process of the test,, should end the processing at this tested position of measured any time if tested position reaches 5.0 or more high-grade.
Data
After the evaluation test end to all measured, determine following numerical value:
Rc o=rank the meansigma methods at the tested position of reference product when initial
Rc fThe rank meansigma methods at the tested position of reference product during=off-test
Rt o=rank the meansigma methods at the tested position of test product when initial
Rt fThe rank meansigma methods at the tested position of test product during=off-test
Many external conditions can influence forearm contrast coating test (FCAT), as relative humidity and hardness of water.This test is just effective when only can be observed enough dermoreactions by reference product.Control reaction should be greater than 1.0 (that is Rc, f-Rc o〉=1.0) test is just effective the time.
For efficiency test, what the mildness index of product was a skin to two kinds of products reactions is poor.
Mildness index=(Rc f-Rc o)-(Rt f-Rt o) The denseness (k) of lipophile skin moisturizing agent and shearing index (n)
Adopt Carrimed CSL100 controlled stress rheometer measurement to be applicable to this lipophile skin moisturizing agent shearing index n and denseness k.Adopt 2 ° of cones of 4cm to measure system (51 microns gaps are generally arranged) down at 35 ℃, measure by certain time dependent shear stress scheme (being generally 0.06-5,000 dynes/cm).If stress causes sample deformation, i.e. the strain of measurement geometry is at least the 10-4 radian per second, and then strained speed is called shear rate.These data are used to do the flow curve of the viscosity (μ) of material with respect to shear rate γ '.This flow curve can be through modelling to form the mathematic(al) representation of the characteristic of described composition under specific shear stress and shear rate.These results satisfy the model (for example referring to " Chemical Engineering ", Coulson and Richardson, Pergamon work, 1982 or " transfer phenomena ", Bird, Stewart and Lightfoot, Wiely work, 1960) of following generally accepted power law:
Viscosity, mu=k (γ ') N-1 The viscosity of liquid personal cleansing composition
Adopt the viscosity of Wells-Brookfield awl/plate DV-II+ type viscometer determining liquid personal cleansing composition of the present invention.Under 25 ℃, adopt 2.4cm ° of cone (rotor CP-41) mensuration system to measure, the gap between two little points on each awl and the plate is 0.013mm.Inject the 0.5ml sample and be used for analyzing between awl and plate, the cone speed setting is 1rpm.Cone rotary resistance meeting forms torque, and torque is directly proportional with shear stress to liquor sample.Read and write down torque value (in centipoise (mPa)) by viscometer according to geometric constant, rotating speed and the torque relevant of cone with stress.
Specific embodiments
Adopt following examples explanation and describe the interior specific embodiments of the scope of the invention.In following examples, listed all the components is all in active matter content.Embodiment only is used for explanation, the present invention is not constituted any qualification, has multiple version under the condition that does not deviate from spirit and scope of the invention.
Composition is chemical name or CTFA name.
The liquid hand soaps % (weight)
Composition Embodiment 1 Embodiment 2 Embodiment 3
Other water of lauryl ether-3 ammonium sulfate Texapon Special lauroyl both sexes sodium acetate anhydrous citric acid polyacrylate * triclosan vaseline trihydroxy tristerin laurate JR30M Polyquaternium-10 NaOH natrium citricum 9.5 3.2 5.4 6.3 0.00 0.6 16.5 0.15 1.0 0.6 0.0 0.0 to pH3.9 2.2 is an amount of 5.5 2.9 5.6 6.3 0.00 0.5 12.0 0.15 1.5 0.1 0.0 0.0 to pH3.9 1.2 is an amount of 6.6 3.1 5.0 0.00 8.00 0.50 12.0 0.25 1.5 0.0 0.1 to pH4.0 0.0 1.33 is an amount of
The biological activity (Z) of the microcytotoxicity acid of the K value anion surfactant of anion surfactant <0.4 1/150 1.29 <0.4 1/150 1.29 <0.4 1/150 -
* polyacrylate is the K7058 that B.F.Goodrich sells
All greater than about 0.3, the mildness index is greater than 0.3 for the gram negative bacteria of shown liquid hand soaps time-delay antibiotic effect index.
The bath gel % (weight)
Composition 1 2 3
NaLS or Texapon Special lauryl ether-3 sodium sulphate or lauryl ether-3 ammonium sulfate lauroyl both sexes sodium acetate or other composition water of lauroyl both sexes ammonium acetate coconut oleoyl amine MEA citric acid triclosan  natrium citricum soybean oil vaseline dimethyl polysiloxane emulsion trihydroxy tristerin laurate palmitic acid Polyquaternium-10 PEG6 caprylic/capric glyceride 6.30 4.20 5.25 2.80 6.50 1.00 to pH4 8.00 0.00 0.00 0.00 0.00 2.20 0.30 1.50 8.28 is an amount of 3.15 9.45 5.40 0.00 6.50 0.60 to pH3.5 0.00 16.50 0.00 1.0 1.0 0.00 0.60 0.00 1.61 is an amount of 3.15 9.45 5.40 0.00 6.50 0.8 to pH3.9 0.00 16.5 1.00 1.0 1.0 0.00 0.30 0.00 1.98 is an amount of
The biological activity (Z) of the microcytotoxicity acid of the K value anion surfactant of anion surfactant <0.4 1/150 1.29 <0.40 1/150 1.29 <0.40 1/150 1.29
Greater than about 0.3, the mildness index is greater than 0.3 with the gram negative bacteria time-delay antibiotic effect index of gel for shown bath. Prepare the liquid hand soaps and bathe the method for using gel
1. hand soaps embodiment 1 and 2 and bathe with gel embodiment 2 and 3
Will be except that vaseline, the outer all the components of active component and essence is put together, and is heated to the temperature (being about 190 for the trihydroxy tristerin) that makes the stabilizing agent fusing.Be cooled to be lower than 115 °F, add active component, vaseline and essence.Regulate final pH with NaOH or buffer salt.Remaining water is added final products.
2. Bathe with gel embodiment 1
Add humidification oil and cosurfactant, composition is heated to 130-140 °F, until dissolving.In another container, add main surfactant, acid, buffer salt, antiseptic, viscosity modifier (salt) and polymer.Be heated to 130-140 °F until dissolving.In 130-140 down mixed two mixture when oil-containing constituents (not only be a mixture), cooling then.When mixture temperature is lower than 115 °F, add antibacterial activity composition and essence.Regulate final pH with sodium hydroxide or remaining buffer salt.Add remaining water and make product.

Claims (21)

1. one kind is floated the type antimicrobial cleansing compositions, it is characterized in that wherein containing:
(a) 0.001-5% antimicrobial acivity composition;
(b) 1-80% anion surfactant;
(c) 1-12% gives proton reagent;
(d) 0.1-30% deposition aid; With
(e) 3-97.5% water;
Wherein the pH regulator of compositions is to 3.0-6.0;
This gram negative bacteria time-delay antibiotic effect index that floats the type antimicrobial cleansing compositions is greater than 0.3;
This mildness index that floats the type antimicrobial cleansing compositions is greater than 0.3.
2. the described type antimicrobial cleansing compositions that floats of claim 1, wherein the antimicrobial acivity composition is selected from triclosan , triclocarban , Octopirox, PCMX, ZPT, natural essential oil and main component thereof and their mixture.
3. the described type antimicrobial cleansing compositions that floats of claim 1, wherein the dissolubility slope K of anion surfactant is less than 0.60, and the microcytotoxicity index is less than 150.
4. the described type antimicrobial cleansing compositions that floats of claim 1 is biological activity index Z greater than 0.5 organic acid to proton reagent wherein.
5. the described type antimicrobial cleansing compositions that floats of claim 1, wherein the pH regulator of compositions is to 3.5-5.0.
6. the described type antimicrobial cleansing compositions that floats of claim 1 is wherein to proton reagent select oneself diacid, tartaric acid, citric acid, maleic acid, malic acid, succinic acid, glycolic, 1,3-propanedicarboxylic acid, benzoic acid, malonic acid, salicylic acid, gluconic acid, polyacrylic acid, their salt and their mixture.
7. the described type antimicrobial cleansing compositions that floats of claim 1, the amount ratio of wherein non-anion surfactant and anion surfactant is lower than 1: 1.
8. the described type antimicrobial cleansing compositions that floats of claim 1, wherein anion surfactant is selected from: chain length is mainly alkyl sodium sulfate, the alkylsurfuric acid ammonium of 12-14 carbon atom, with sodium alkylether sulphate, alkyl ether ammonium sulfate, chain length is mainly the olefin sulphates of 14-16 carbon atom, average chain length is the alkane sulfonate of 13-17 carbon atom and their mixture.
9. the described type antimicrobial cleansing compositions that floats of claim 1, wherein be selected from poly-(propylene) acid of straight chain and copolymer thereof to proton reagent, molecular weight is less than 250, crosslinked poly-(propylene) acid of 000, poly-(Alpha-hydroxy) acid and copolymer thereof, poly-(methacrylic acid) and copolymer thereof, chondrus ocellatus Holmes acid, carboxymethyl cellulose, and alginic acid.
10. the described type antimicrobial cleansing compositions that floats of claim 1, it is used to handle acne.
11. one kind is floated the type antimicrobial cleansing compositions, it is characterized in that wherein containing:
(a) 0.001-5% antimicrobial acivity composition;
(b) 1-80% anion surfactant;
(c) 1-12% gives proton reagent; With
(d) 1-30% lipophilic skin humidizer;
(e) 0.1-10% stabilizing agent;
(f) 3-95.99% water;
Wherein the pH regulator of compositions is to 3.0-6.0;
This gram negative bacteria time-delay antibiotic effect index that floats the type antimicrobial cleansing compositions is greater than 1.0;
This mildness index that floats the type antimicrobial cleansing compositions is greater than 0.4.
12. the described type antimicrobial cleansing compositions that floats of claim 11, wherein the antimicrobial acivity composition is selected from triclosan , triclocarban , Octopirox, PCMX, ZPT, natural essential oil and main component thereof and their mixture.
13. the described type antimicrobial cleansing compositions that floats of claim 11, wherein the dissolubility slope K of anion surfactant is less than 0.61, and the microcytotoxicity index is less than 150.
14. the described type antimicrobial cleansing compositions that floats of claim 11 is biological activity index Z greater than 0.5 organic acid to proton reagent wherein.
15. the described type antimicrobial cleansing compositions that floats of claim 11, wherein the pH regulator of compositions is to 3.5-5.0.
16. the described type antimicrobial cleansing compositions that floats of claim 11 is wherein to proton reagent select oneself diacid, tartaric acid, citric acid, maleic acid, malic acid, succinic acid, glycolic, 1,3-propanedicarboxylic acid, benzoic acid, malonic acid, salicylic acid, gluconic acid, polyacrylic acid, their salt and their mixture.
17. the described type antimicrobial cleansing compositions that floats of claim 11, the amount ratio of wherein non-anion surfactant and anion surfactant is lower than 1: 1.
18. the described type antimicrobial cleansing compositions that floats of claim 11, wherein the agent of lipophile skin moisturizing is selected from hydrocarbon ils and wax, polysiloxanes, fatty acid ester, cholesterol, two-and Three-glycerol ester, liquid nondigestible oil, acetyl group glyceride, Arrcostab, alkenyl esters, lanoline, sterol, phospholipid and their mixture.
19. the described type antimicrobial cleansing compositions that floats of claim 11, wherein anion surfactant is selected from: chain length is mainly alkyl sodium sulfate, the alkylsurfuric acid ammonium of 12-14 carbon atom, with sodium alkylether sulphate, alkyl ether ammonium sulfate, chain length is mainly the olefin sulphates of 14-16 carbon atom, average chain length is the alkane sulfonate of 13-17 carbon atom and their mixture.
20. the described type antimicrobial cleansing compositions that floats of claim 11, wherein be selected from poly-(propylene) acid of straight chain and copolymer thereof to proton reagent, molecular weight is less than 250, crosslinked poly-(propylene) acid of 000, poly-(Alpha-hydroxy) acid and copolymer thereof, poly-(methacrylic acid) and copolymer thereof, chondrus ocellatus Holmes acid, carboxymethyl cellulose, and alginic acid.
21. the described type antimicrobial cleansing compositions that floats of claim 11, it is used to handle acne.
CN98807394A 1997-06-04 1998-05-29 Liquid anitmicrobial clansing compositions which provide residual benefit versus gram negative bacterial Expired - Fee Related CN1129422C (en)

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US08/969,077 US6214363B1 (en) 1997-11-12 1997-11-12 Liquid antimicrobial cleansing compositions which provide residual benefit versus gram negative bacteria

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AU7704698A (en) 1998-12-21
PE77499A1 (en) 1999-10-06
EP0996419A1 (en) 2000-05-03
CN1264293A (en) 2000-08-23
JP2002501542A (en) 2002-01-15

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