CN1227596A - Cleaning compositions - Google Patents

Cleaning compositions Download PDF

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Publication number
CN1227596A
CN1227596A CN 97197051 CN97197051A CN1227596A CN 1227596 A CN1227596 A CN 1227596A CN 97197051 CN97197051 CN 97197051 CN 97197051 A CN97197051 A CN 97197051A CN 1227596 A CN1227596 A CN 1227596A
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Prior art keywords
weight
composition
alkyl
arbitrary
water
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CN 97197051
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Chinese (zh)
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A·布罗克斯
C·M·A·杜瑞亚尤
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Procter and Gamble Co
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Procter and Gamble Co
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Publication of CN1227596A publication Critical patent/CN1227596A/en
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/10Washing or bathing 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
    • A61K8/342Alcohols having more than seven atoms in an unbroken chain
    • 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
    • A61K8/39Derivatives containing from 2 to 10 oxyalkylene groups
    • 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
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • A61K8/731Cellulose; Quaternized cellulose derivatives
    • 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
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/87Polyurethanes
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54Polymers characterized by specific structures/properties
    • A61K2800/542Polymers characterized by specific structures/properties characterized by the charge
    • A61K2800/5426Polymers characterized by specific structures/properties characterized by the charge cationic
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/02Preparations for cleaning the hair

Abstract

A liquid personal cleansing composition comprising: (a) from about 0.01 % to about 15 % by weight of a thickening system consisting essentially of associative polymer and polar oil having a required HLB of at least 12; (b) from about 1 % to about 60 % by weight of water-soluble surfactant selected from anionic surfactant, nonionic, zwitterionic and amphoteric surfactants and mixtures thereof; (c) optionally, from about 0.01 % to about 5 % by weight of cationic polymeric skin conditioning agent; and (d) water, wherein the polar oil has an average carbon chain length of from about 10 to about 18 carbon atoms and wherein the water-soluble surfactants have an average carbon chain length of from 10 to about 18 carbon atoms. The products provide excellent product thickening and rheological attributes, in storage, in dispensing and in-use, in combination with good efficacy benefits including excellent rinsibility, mildness, skin conditionning, skin moisturising, good product stability, cleansing and lathering.

Description

Cleaning compositions
Affiliated field
The present invention relates to cleaning compositions.Be specifically related to gentle personal cleaning compositions, said composition has improved thickening property and rheological properties and advantages of good skin sensorial characteristics, rinsing characteristic and foaming character, be applicable to cleaning and conditioning skin and/or hair simultaneously, and for example can foam bath with preparation, bathe with product, skin cleaner, hand with, face with and forms such as body and function clean-out system, shampoo use.
Background technology
Gentle make-up composition should satisfy following some conditions, comprises spatter property, foaminess and to the mildness/low irritant/good usability of skin, hair and eye mucous membrane.Skin is made of each cellular layer, and this counts confluent monolayer cells and coats and protection angle albumen and collegen filament albumen, and these protein constitute the skeleton of skin texture.The outermost layer of known these cellular layers (being stratum corneum) is that the protein bundle by 250 constitutes, and is the thick layers of 80 around the protein bundle.Hair has the protective skin equally, is coated on the hair fiber outside, is called cuticula.Anion surfactant can infiltrate stratum corneum and cuticula, destroys the globality of film through fat abstraction.This influence to skin and hair protective layer can make the skin roughen, and can stimulate eye, make tensio-active agent finally can and Keratin sulfate and hair proteins interact, produce hormesis, and buffer action and water retaining function can be lost.
Skin or hair should be leniently cleaned in the agent of ideal cosmetic cleansing, can not make hair and skin degreasing and/or drying, and can not stimulate the eye mucous membrane or make skin tight after frequent the use.There are deficiency in great majority foaming soap, bath in this respect with product, shampoo and soap bar.
Known some synthetic surfactant is gentle.But the main drawback of the synthetic surfactant system of most gentlenesses is: when preparation synthetic detergent system was used for hair washing or personal cleanliness, its foaminess was compared relatively poor with high foaming (highest) shampoo with the standard soap slab.Therefore the foaminess of those the gentleest tensio-active agents is very low.On the other hand, adopt known high bubble anion surfactant can reach suitable foam volume, but can lose clinical skin mildness as alkyl-sulphate with foam promoter action.These 2 facts make that the selection to suitable tensio-active agent need reach a kind of delicate balance in the process for preparation that reaches foaminess and mildness effect.
Except that the required mildness of user, spatter property and foaming character, in product storage, distribution and use, personal cleansing product has good thickening and rheological properties is also very important.
The water-soluble polymers that can reach required product thickening property in surfactant system is known, in addition, can improve its thickening usefulness to the hydrophobically modified of water-soluble polymers.But it is also known in undiluted water soluble surfactant active's system, the thickening property of the water-soluble polymers that these are hydrophobically modified can significantly reduce (as what discuss in Sau and Landoll work " polymkeric substance in the water-bearing media ", referring to " chemical progress ", No. 223, the 8th, 17,18 chapters, J.E.Glass compiles).The applicant finds that especially hydrophobically modified polymkeric substance (as hydrophobically modified Natvosol) can not make product have good thickening in undiluted water soluble surfactant active's system.Here " undiluted " of Xian Dinging is meant and contains approximately in the surfactant system greater than 1% heavy water soluble surfactant active.Here " water-soluble " of Xian Dinging is meant that the molecular weight of tensio-active agent is less than about 20000, and wherein tensio-active agent can form clarifying, isotropic solution with 0.2% (weight) when soluble in water under room temperature (25 ℃).
Also known fatty alcohol ethoxylate and Fatty Alcohol(C12-C14 and C12-C18) can make and contain water soluble surfactant active and electrolytical system thickening (for example, see Hoechst Surfactant one book, published by TradeLiterature).But fatty alcohol ethoxylate and Fatty Alcohol(C12-C14 and C12-C18) can change the micellar structure of water soluble surfactant active's system, and product performance (as the usability of foaminess, rinsing and product) is caused disadvantageous effect.The applicant also finds, so that when reaching good product thickening property, reaching the consumption of the required Fatty Alcohol(C12-C14 and C12-C18) thickening material of suitable thickening characteristic, undiluted water soluble surfactant active's system can cause foaminess and rinsing reduction by independent employing fatty alcohol ethoxylate and/or Fatty Alcohol(C12-C14 and C12-C18) thickening material.
Knownly contain other relevant difficult problem of fatty alcohol ethoxylate and/or Fatty Alcohol(C12-C14 and C12-C18) and electrolytical thickened systems and also have with adopting: the thickening power of these compositions depends on used purity of raw materials and quality greatly.This can make thickening characteristic be difficult to precognition, for example obtains having low viscous rare product that can't recover, and this tensio-active agent that is difficult to be difficult to when foreseeability makes people adopt fatty ingredient those are had the known-viscosity characteristic is mixed with thickened systems effectively.
The effective thickened systems that therefore need be used for undiluted water soluble surfactant active's system, this system should be able to make product have good product thickening property and rheological properties in storage, distribution and use, have fabulous product performance such as foaminess, spatter property, rinsing, skin mildness with seasonal product, and fabulous skin usability.
Be surprised to find that at present under storage and working conditions and had fabulous product thickening property and rheological properties personal cleaning compositions, wherein obtain, mainly contain the polymkeric substance and the polar oil of associativity in this thickened systems by thickened systems being added in undiluted water soluble surfactant active's system.Find in addition to be used in the thickened systems of the present invention of surfactant composition, the consumption of the thickening material of using before the total amount of the thickening material that adopts is starkly lower than just can reach required thickening effectiveness.
The thinning difficult problem of the product that can face when attempt adopting fatty thickening material in containing the system of high level of surfactant, the applicant also finds to adopt contains fatty thickening material and electrolytical thickened systems is difficult to make gentle water soluble nonionic surfactant (as polyhydroxy fatty acid amide and alkyl poly glucoside) thickening.
The applicant finds that also thickened systems of the present invention is particularly useful for making some gentle water soluble nonionic surfactant (as polyhydroxy fatty acid amide surfactants) thickening.
Summary of the invention
Theme of the present invention be undiluted, can foam, easily rinsing, be applicable to the cleaning compositions that the individual of skin or hair cleans, said composition has good thickening and rheological properties, and it can be used as and bathes with product, skin cleaner and shampoo etc.One aspect of the present invention provides a kind of liquid personal cleansing composition, wherein contains: (a) about 0.01-15% (weight) thickened systems, in this system mainly by the polymkeric substance of associativity and on request the HLB value be at least 12 polar oil and form; (b) about 1-60% (weight) water soluble surfactant active is selected from anion surfactant, nonionic, zwitter-ion and amphoterics and their mixture; (c) can contain the skin conditioning agent of about 0.01-5% (weight) cationic polymerization type that can not contain; And (d) water.Wherein the average carbon chain length of polar oil is about 10-18 carbon atom, and wherein water soluble surfactant active's average carbon chain length is about 10-18 carbon atom.
Another aspect of the present invention provides a kind of personal cleaning compositions, wherein contain: (a) about 0.01-15% (weight) thickened systems, in this system mainly by hydrophobically modified water-soluble nonionic polymkeric substance and on request the HLB value be at least 12 polar oil and form; (b) about 1-60% (weight) water soluble surfactant active is selected from anion surfactant, nonionic, zwitter-ion and amphoterics and their mixture; (c) can contain the skin conditioning agent of about 0.01-5% (weight) cationic polymerization type that can not conform to; And (d) water.Wherein the average carbon chain length of polar oil is about 10-18 carbon atom, and wherein water soluble surfactant active's average carbon chain length is about 10-18 carbon atom.
Another aspect of the present invention is to provide a kind of personal cleaning compositions, wherein contain: (a) about 0.01-15% (weight) thickened systems, in this system mainly by hydrophobically modified water-soluble nonionic polymkeric substance and on request the HLB value be at least 12 polar oil and form, wherein hydrophobically modified water-soluble nonionic polymkeric substance is selected from hydrophobically modified alkoxyl group urethane, hydrophobically modified hydroxy alkyl cellulose, hydrophobically modified nonionic polyvalent alcohol and their mixture; (b) about 1-60% (weight) water soluble surfactant active is selected from anion surfactant, nonionic, zwitter-ion and amphoterics and their mixture; (c) can contain the skin conditioning agent of about 0.01-5% (weight) cationic polymerization type that can not contain; And (d) water.Wherein the average carbon chain length of polar oil is about 12-14 carbon atom, and wherein water soluble surfactant active's average carbon chain length is about 12-14 carbon atom.
Further embodiment of the present invention is to provide a kind of personal cleaning compositions, wherein contains: (a) about 0.01-15% (weight) thickened systems, in this system mainly by the polymkeric substance of associativity and on request the HLB value be at least 12 polar oil and form; (b) the nonionic polyhydroxy fatty acid amide surfactants of about 0.1-20% (weight) shown in formula III: R wherein 8Be C 5-C 31Alkyl, R 9Be hydrogen, C 1-C 8Alkyl or hydroxyalkyl, and Z 2Be the polyhydroxy alkyl structure division; (c) the water-soluble cosurfactant the polyhydroxy fatty acid amide surfactants of about 1-60% (weight) in (b) is selected from anion surfactant, nonionic, zwitter-ion and amphoterics and their mixture; (d) water.Wherein the average carbon chain length of polar oil is about 10-18 carbon atom, and with water-soluble undiluted tensio-active agent matrix in the average carbon chain length of total polyhydroxy fatty acid amide and other gentle tensio-active agent basic identical.
In particularly preferred specific embodiments, the present invention is undiluted foaming liquid cleaning compositions, and said composition has good product thickening property and rheological properties.
Unless otherwise indicated, all concentration among the present invention and amount ratio are all in the weight of cleaning compositions.Unless otherwise indicated, the tensio-active agent chain length is also in weight average chain length.
Detailed Description Of The Invention
Liquid cleansing composition of the present invention is that thickened systems is mixed with tensio-active agent, not necessarily adds the polymeric skin conditioning agent, and wherein thickened systems mainly is made up of the polymkeric substance and the polar oil of associativity.Also can contain essence or cosmetic oil in the embodiment preferred.
Thickened systems
Liquid cleansing composition of the present invention is based on thickened systems and water miscible undiluted surfactant system, and can not necessarily contain the polymeric skin conditioning agent, wherein thickened systems mainly by associative polymer and on request the HLB value be at least about 12 polar oil and form the water-soluble nonionic polymkeric substance that associative polymer is preferably hydrophobically modified.
The total amount of associative polymer and polar oil is about 0.01~15% (weight) in the thickened systems of the present invention, preferably be about 0.01-10% (weight), be more preferably 0.05-8% (weight), be most preferably 0.1-4% (weight), particularly be about 0.1-2% (weight), the most particularly be about 0.5-1.5% (weight).Associative polymer is about 1 with the preferable amount ratio of polar oil: 5-5: 1, be more preferably 1: 3-3: and 1, be most preferably 1: 2-2: 1.
Thickened systems of the present invention helps making product to have good product thickening property and rheological properties when storing, distributing and using.
Another beneficial effect of thickened systems of the present invention is that the thickening of product is no longer dependent on the electrolytical existence in the tensio-active agent matrix.Therefore may accomplish that at present need not to use ionogen just can make has the undiluted tensio-active agent matrix of required product thickening property and rheological properties.
The applicant finds thisly to be independent of electrolytical characteristic when preparation contains the gentleness of polyhydroxy fatty acid amide surfactants, undiluted water soluble surfactant active's system, helps making product to have required thickening characteristic (will discuss hereinafter).
Associative polymer
Contain associative polymer in the thickened systems of the present invention as basal component, its consumption is about 0.01-12% (weight), preferably be about 0.01-10% (weight), be more preferably 0.05-8% (weight), be most preferably 0.1-4% (weight), particularly be about 0.1-2% (weight), the most particularly be about 0.5-1.5% (weight).In the present composition, associative polymer and HLB value on request are at least 12 polar oil mixes, and helps making undiluted water soluble surfactant active's system to have good product thickening property and rheological properties.
Preferred associative polymer is the non-ionic associative polymkeric substance in the present composition, and its molecular-weight average is about 2000-2000000, preferably is about 10000-1000000, is more preferably 20000-800000.
Associative polymer is the next scope of water-soluble polymers, and it is the water-soluble macromolecule structure normally, and this structure contains hydrophilic segment and hydrophobic part.Associative polymer can make the surfactant soln thickening, this is because the intermolecular association of various water-insoluble hydrophobic components causes, wherein hydrophobic part is the part of water-soluble polymers main chain, perhaps (directly or indirectly) (goes through in " polymkeric substance in the water-bearing media " of G.D.Shay with this main chain bonding, referring to " chemical progress ", 223, the 467 pages, compile) by J.E.Glass.
As mentioned above, known associative polymer can be at low levels (promptly, be less than about 1% (weight)) the water soluble surfactant active have down thickening, as in EP-A-0412706, describing to some extent, bibliographical information the interaction of these associative thickenerss and specific tensio-active agent (as what in Sau and Landoll work " polymkeric substance in the water-bearing media ", discuss, referring to No. 223, " chemical progress ", 343-364 page or leaf, J.E.Glass compiles).
Above-mentioned hydrophobically modified polymkeric substance is meant water-soluble (hydrophilic) associative polymer, it oneself add in pairs by hydrophobic group that it carries out modification to promote its thickening usefulness (as what discuss in Sau and Landoll work " polymkeric substance in the water-bearing media ", referring to " chemical progress ", No. 223, the 8th, 17,18 chapters, J.E.Glass compiles).The model (from the angle of hydrophobically modified water-soluble nonionic polymkeric substance) that is suitable for of product thickening be thickening power be since the intermolecular association between the hydrophobic group of polymkeric substance cause (as in Sau and Landoll work " polymkeric substance the water-bearing media ", discussing, referring to No. 223, " chemical progress ", the 343-364 page or leaf, J.E.Glass compiles).Specifically, simple anion surfactant (for example SDS) and nonionogenic tenside (for example CxEy) have effect (as what discuss to hydrophobically modified Natvosol (HMHEC) in Sau and Landoll work " polymkeric substance in the water-bearing media ", referring to No. 223, " chemical progress ", the 343-364 page or leaf, and people such as Tanaka is at " macromole " 1992,25, discuss in the 1304-1310 page or leaf), and hydrophobically modified oxyethyl group urethane (HEUR) there be effect (" colloid and the surface " of Hulden, 82 (1994), the 263-277 page or leaf).
The preferred liquid cleansing composition of the present invention is based on thickened systems and water miscible undiluted surfactant system, and not necessarily contain the polymeric skin conditioning agent, in this thickened systems mainly by hydrophobically modified water-soluble nonionic polymkeric substance and on request the HLB value be at least about 12 polar oil and form.Water-soluble, for the hydrophobically modified water-soluble nonionic polymkeric substance that the present invention limits, be meant that polymkeric substance contains a water-soluble main chain and/or water-soluble key at least.
Do not wish by specific one theory, the present invention proposes: water-soluble nonionic polymkeric substance and polar oil thickening material hydrophobically modified among the present invention react to each other in the presence of undiluted water soluble surfactant active's system, make product have fabulous product thickening characteristic.
The hydrophobically modified water-soluble nonionic polymkeric substance that is applicable to thickened systems of the present invention comprises hydrophobically modified hydroxy alkyl cellulose polymkeric substance, as hydrophobically modified Natvosol (HMHEC), hydrophobically modified alkoxylate urethane polymkeric substance, as hydrophobically modified ethoxylation urethane (HEUR), and hydrophobically modified nonionic polyvalent alcohol.Hydrophobically modified hydroxy alkyl cellulose thickening material
Be applicable to that ether of cellulose of the present invention had enough nonionic substitution values before hydrophobically modified, they are selected from methyl, ethyl, hydroxyethyl and hydroxypropyl so that it has water-soluble.Preferred nonionic substitution value is about 1-8-4.0, preferably is about 2-3, particularly is about 2.2-2.8 (by weight).Further through containing 10-24 carbon atom, preferred alkyl or the alkenyl replacement that contains 14-18 carbon atom approximately approximately, its consumption is about 0.1-1% (weight) to ether of cellulose, preferably is about 0.3-0.8% (weight), particularly is about 0.4-0.6% (weight) then.Through the ether of cellulose of modification preferably lower molecular weight promptly be lower than 800000 to intermediate molecular weight, preferably be about 20000-700000 (polymerization degree is 75-2500).The polymerization degree described here (D.P.) is meant the unitary mean number of glycosides in the polymkeric substance.
Preferably be applicable to ether of cellulose of the present invention be selected from can be commercial nonionic cellulose ether such as Natvosol, HPMC, Walocel MT 20.000PV, Type 3U and their mixture.
Be applicable to that preferably ether of cellulose material of the present invention is the Natvosol (HEC) that molecular weight is about 50000-700000.Natvosol with this molecular weight is that tool is hydrophilic in all material.Therefore adopt this material can control modification procedure more accurately and through the characteristic of modified product.The wetting ability of the most frequently used nonionic cellulose ether generally changes by following trend: hydroxyethyl>hydroxypropyl>hydroxypropylmethyl>methyl.
The long chain alkyl modifier that is used for ether of cellulose can be passed through ether, ester or urethane bond and link to each other with ether of cellulose matrix.Preferred ehter bond.Though the modified cellulose ethers composition is called as " alkyl-modified " (the term alkyl that is adopted generally also comprises alkenyl), thinks except that the situation of alkyl halide modification, properties-correcting agent is not simple chain alkyl.When adopting epoxide, this group is actually alpha-hydroxyalkyl, is urethane groups when adopting isocyanic ester, is acyl group when adopting acid or acyl chlorides perhaps.Landoll (' 277) the capable universal method that proposes the ether of cellulose modification of the 2nd hurdle 36-65.
The water ratio that especially preferably is applicable to this is that the viscosity of 1% hydrophobically modified Natvosol (HMHEC) polymkeric substance is about 8000-50000mPas (Brookfield LVT viscosity apparatus, No. 4 rotors, 4 speed).
Preferably be applicable to of the present inventionly can comprise NATROSOL PLUS Grade330 CS (TM) product by commercial composition, it is available from Aqualon company (Wilmington, hydrophobically modified Natvosol Delaware).This composition contains the C of 0.4-0.8% (weight) 16Alkyl replaces.The hydroxyethyl molar substitution of this composition is 3.0-3.7.The molecular-weight average of water soluble cellulose is about 300000 before the modification.Be applicable to this NATROSOL PLUS Grade430 CS (TM) product in addition.
Other this constituents has that (Wilmington is Delaware) with trade(brand)name NATROSOL PLUS CS Grade D-67 (TM) product sold by Aqualon company.This composition contains the C through 0.50-0.95% (weight) 16Alkyl replaces.The hydroxyethyl molar substitution of this composition is 2.3-3.7.The molecular-weight average of water soluble cellulose is about 700000 before the modification.Especially preferably be applicable to this be ethoxylation degree be about 1.8-3.2, preferably be about 2.0-3.0, be more preferably the C of 2.2-2.8 14-C 18The HEC polymer of alkyl and alkenyl modification, and alkyl and alkenyl substitution value be about 0.3-0.8, preferably is about 0.4-0.7, is most preferably 0.5-0.7, particularly is about 0.65.Particularly preferably be the hexadecyl modified hydroxyethylcellulosadsorbing polymkeric substance available from the commodity Polysurf 67 (TM) by name of Aqualon company, its molecular weight is about 700000.Hydrophobically modified alkoxylate urethane thickening material
Be applicable to that hydrophobically modified water-soluble nonionic alkoxylate urethane polymkeric substance of the present invention is particularly suitable for that (5 ℃-Yue 50 ℃) make product have fabulous stability under conventional temperature, and the matrix that order contains high level of surfactant has nearly newton's rheological properties under low shear rate, and is suitable in undiluted water soluble surfactant active's system being at least 12 polar oil with HLB value in accordance with regulations and makes product have improved products thickening property and rheological properties.
Hydrophobically modified water-soluble nonionic alkoxylate urethane polymkeric substance is to carry out prepolymerization by vulcabond and polyvalent alcohol, then through primary amine or primary alconol end-blocking.The molecule of gained generally is the straight-chain block copolymer that has inner hydrophobic base and terminal hydrophobic group, but also can obtain side chain and cross-linked polymer.
Polymerization procedure is very complicated, and as Hulden (" colloid and surface ", 82,263-277), people (Polym.Mater.Sci.Eng. such as Kaczmarski, 67,282-283) and described in people's such as Karunasena (" polymkeric substance in the water-bearing media ", referring to " chemical progress " 223,495-525 page or leaf) the document can form various polymer architectures.To hydrophobically modified water-soluble nonionic alkoxylate urethane polymkeric substance is seen that as further going through of thickening material exercise question is the paper of " polymkeric substance in the makeup ", submit to by Rohm and Haas, referring to the 29th page of the 20th Italy's international Society of Cosmetic Chemists nd Annual Meeting collection (1993).
The hydrophobically modified water-soluble nonionic alkoxylate urethane polymkeric substance that preferably is applicable to this those straight-chain block copolymers that to be those described by people such as Kaczmarski (can through progressively polymerization make), and this multipolymer has following general formula:
R 2-NHCO-NH-R 1[NH-CO-O-E n-CH 2CH 2OCONH-R 1] x-NHCO-NH-R 2
R 2-O-CONH-R 1[NH-CO-O-E n-CH 2CH 2OCONH-R 1] x-NH-CO-O-R 2E wherein nBe that general formula is (CH 2CH 2O) nPolyvalent alcohol, n can be 10-10000, is preferably 10-1000, more preferably 50-500; R 1Comprise the straight or branched alkyl, alkenyl or the aromatic base that contain side functional group (for example COOH); R 2Comprise the straight or branched alkyl, alkenyl or the aromatic base that contain side functional group (for example COOH), and R wherein 2Be preferably selected from NH 2Or OH, and wherein x represents the polymerization degree.
Preferably be applicable to hydrophobically modified water-soluble nonionic alkoxylate urethane polymkeric substance of the present invention be those by Rohm and Haas with Acrysol 44 (TM) product sold, by Berol Nobel with Bermodol 2101 (TM), 2130 (TM) and BermodolPur 2100 (TM) product sold and by Servo with Ser-Ad-FX-100 (TM) product sold.Hydrophobically modified nonionic polyvalent alcohol
Be applicable to that thickening material of the present invention also has hydrophobically modified water-soluble nonionic polyvalent alcohol.The hydrophobically modified water-soluble nonionic polyvalent alcohol that is applicable to this is the glycoside fatty acid ester, as PEG120 methylglycoside dioleate (available from Amercol, the product of commodity Glucamate DOE 120 by name), the PEG-150 pentaerythritol tetrastearate is (available from Croda, commodity are called the product of Crothix (TM)), the PEG-75 dioleate is (available from Kessco, commodity are called the product of PEG-4000 dioleate (TM)) and PEG-150 SUNSOFT Q-182S (available from Witco, the product of commodity Witconal L32 (TM) by name).Polar oil
Another essential feature of thickened systems of the present invention is that HLB is at least 12 polar oil on request.The content of cleaning compositions Semi-polarity oil of the present invention is about 0.01-3% (weight), preferably is about 0.01-2% (weight), is more preferably 0.1-1% (weight), is most preferably 0.2-0.8% (weight).
Here the polar oil of Xian Dinging is meant and is aqueous or the waxy organic oil, wherein contain one or more wetting abilities or polar functional group, and this functional group can react with associative polymer, can make product have fabulous product thickening property and rheological properties in undiluted water soluble polymer systems.
Be suitable in the present invention being at least 12, preferably be about 12-15, be more preferably 12-14 as the HLB value requirement of the polar oil of thickening material.HLB value on request described here is meant " hydrophilic of requirement ", and can be measured by standard technique as known in the art.The notion of HLB value, particularly desired HLB value, (ICI Americas Inc, Wilmington have in Delaware) more fully and describe in " HLB system ".
The typical polar oil that is applicable to the present composition comprises that average carbon chain length is about the pure and mild lipid acid of natural and synthetic fat of 10-18 carbon atom.Be applicable to that Fatty Alcohol(C12-C14 and C12-C18) of the present invention comprises decyl alcohol, lauryl alcohol, hexadecanol, stearyl alcohol and their mixture.Other polar oil comprises that average carbon chain length is about the lipid acid of 12-16 carbon atom, as lauric acid and tetradecanoic acid.
The applicant also finds: the carbon chain length of polar oil is influential to the product thickening property through undiluted water soluble surfactant active's system of thickened systems thickening of the present invention.The general preferred average carbochain of polar oil of the present invention that is applicable to often is about 10-18 carbon atom, preferably is about 12-16 carbon atom, and preferably is about 12-14 carbon atom especially.Be applicable to that especially preferably of the present invention is to contain the system that average carbon chain length is similar to the polar oil of undiluted water soluble surfactant active's system average carbon chain length substantially.Basic similarly average carbon chain length described here is meant the difference of two of carbon chain length existence, a preferred carbon unit, C promptly described here 12With C 14Average carbon chain length for similar substantially.
Cleaning compositions of the present invention preferably adopts and contains the polar oil that average carbon chain length is about the alkyl of 12-14 carbon atom, is very suitable for making product to have good foaming character because average carbon chain length is about the tensio-active agent of 12-14 carbon atom.
What as mentioned above, the spy was not applicable to thickened systems of the present invention in addition is the basic similarly polar oil of those chain lengths and selected surfactant system chain length.The polar oil that preferably is applicable to this is C 12-C 14Alcohol as lauryl alcohol (available from Albright ﹠amp; The Laurex NC (RTM) of Wilson), C 12-C 13Alcohol (available from the Dobanol 23 of Shell UK) and C 12-C 15Alcohol (available from the Dobanol 25 of Shell UK), and C 14-C 15Alcohol (available from the Dobanol 45 of Shell UK) also can be the product available from the commodity Neodol by name of Shell US Inc..
The applicant finds that also there is limited enhancement in the content of thickened systems Semi-polarity oil thickening material of the present invention (promptly to the product thickening property, along with the increase with respect to the content of the polar oil of tensio-active agent total amount, the thickening degree in the tensio-active agent matrix that is reached finally can reach maintenance level).
Also can contain auxiliary nonionic or anionic thickening polymer agent component, particularly molecular weight in the present composition approximately greater than 20000 water-soluble polymeric composition." water-soluble polymers " is meant under 25 ℃ can form basic clear soln with 1% concentration in water, and this composition can make aqueous solution thickening.Example that be suitable for to make the water-soluble polymers of auxiliary thickening component in the present composition has Natvosol, hydroxypropylcellulose, Vltra tears, polyoxyethylene glycol, polyacrylamide, polyacrylic acid, polyvinyl alcohol (for example comprise the KuraryChemical Co. available from Japan, PVA 217), Polyvinylpyrolidone (PVP) K-120, dextran (for example available from D﹠amp; The purifying crude product 2P level dextran of O Chemicals), carboxymethyl cellulose, plant transudate such as gum arabic, ghatti gum and tragacanth gum, Seaweed Extract such as sodiun alginate, alginic acid propylene glycol and angle dish glue sodium again.The supplementary thickener that is preferred for the present composition is the natural polysaccharide composition.The example of these compositions has guar gum, Viscogum BE and xanthan gum.Molecular weight is about 700000 Natvosol and also preferably is applicable to the present composition.Surfactant system
Another essential feature of the present composition is the undiluted surfactant system that comprises the water soluble surfactant active.The above-mentioned water-soluble molecular weight of tensio-active agent that is meant is less than about 20000, and wherein this tensio-active agent at room temperature can form clarifying isotropic solution with 0.2% (weight) when concentration is soluble in water.The tensio-active agent that is applicable to the present composition generally contains the oleophylic chain that chain length is about 8-22 carbon atom, and this tensio-active agent is selected from negatively charged ion, nonionic, zwitter-ion and amphoterics and their mixture.The total amount of tensio-active agent preferably is about 2-40% (weight), is more preferably 3-15% (weight).Composition preferably contains the mixture of anion surfactant and zwitter-ion and/or amphoterics.The content of negatively charged ion, zwitter-ion and amphoterics component every kind (if existence) accounts for the 1-15% (weight) of composition, particularly be about 1-10% (weight), the content of nonionogenic tenside (if existence) is about 0.1-20% (weight), preferably be about 0.5-16% (weight), be more preferably 1-12% (weight).The weight ratio of anion surfactant and zwitter-ion and/or amphoterics is about 1: 10-10: 1, preferably be about 1: 5-5: and 1, be more preferably 1: 3-3: 1.Other composition that is suitable for comprises the mixture of anion surfactant, zwitter-ion and/or amphoterics and one or more nonionogenic tenside in the scope of the invention.What preferably be applicable to this is soluble or dispersible nonionogenic tenside, is selected from ethoxylation animal-plant oil and their mixture, is sometimes referred to as " from greasy " nonionogenic tenside in the present invention.
Can comprise the water-soluble anionic tensio-active agent in the present composition, its content is about 0.1-20% (weight), is more preferably 0.1-10% (weight), is about 1-8% (weight) especially.
The water soluble anionic surfactant that is applicable to the present composition generally can be called as gentle synthesis of detergent tensio-active agent; comprising alkyl-sulphate; ethoxylated alkyl sulfates; alkyl ethoxy carboxylate; alkyl glyceryl ether sulfonate; methyl-acyl taurine salt; fat acidyl glycine salt; the N-acyl glutamate; acyl-hydroxyethyl sulfonate; alkyl sulfo succinate; the alkyl ethoxy sulfosuccinate; α-alpha-sulfonated fatty acid; their salt and/or ester; alkyl phosphate; ethoxylated alkyl phosphate ester; alkyl-sulphate; acyl sarcosinate and lipid acid/protein condenses, and their mixture.The alkyl of these tensio-active agents and/or acyl group chain length are C 12-C 22, preferred C 12-C 18, more preferably C 12-C 14
This class tensio-active agent comprises the short-chain alkyl sulfate surfactant, and wherein said " short chain " is meant that average carbon chain length is C 10Or it is lower.Short-chain alkyl sulfate surfactant of the present invention is suitable for making product have improved skin mildness and useful product wash effect in bathing with gelatinous composition, also makes product have required foaming character simultaneously.The alkyl sulfate surfactant that is applicable to the present composition is shown in logical formula II:
R-SO 3-M wherein R on average contains the straight or branched alkyl of 8-10 carbon atom, preferred about 10 carbon atoms, straight chained alkyl preferably approximately, and wherein M is selected from basic metal, ammonium or other suitable monovalent cation or their mixture.Should be understood that for the definition of particular carbon chain length C for example 8Refer to mean value, and can comprise the long and short carbochain of a certain proportion of carbon chain length in the building-up process.Can reach the content of this composition by the characteristic of change method and change initial feed.Although C 10Alkyl-sulphate is a preferred surfactants in the present composition, and the mixture of short-chain alkyl vitriol also is suitable for.Particularly preferably be in the present composition at least about containing 80% (weight) C 10, preferably at least about 90% (weight) C 10, more preferably at least about 95% (weight) C 10, particularly at least about 99% (weight) C 10The C of alkyl-sulphate 10The alkylsurfuric acid salt component.The short-chain alkyl vitriol composition that is suitable for can be available from Albright and Wilson with trade(brand)name EmpicolLC35 and Empicol 0758F product sold.
The assisted water soluble anion surfactant that is applicable to composition of the present invention also has the salt of sulfuric ester of the reaction product of 1mol high fatty alcohol and about 1-12mol oxyethane, and wherein sodium, ammonium and magnesium are preferred gegenions.Particularly preferably be the alkyl ethoxy sulfate that contains 2-6, preferred 2-4mol oxyethane approximately, as lauryl ether-2 sodium sulfate, lauryl ether-3 sodium sulfate and lauryl ether-3.6 sal epsom sodium.In the embodiment preferred, anion surfactant is at least about containing 50% (weight), especially at least about 75% (weight) ethoxylated alkyl sulfates.
Except that the ethoxylated alkyl sulfates widely that makes through conventional sodium catalysis ethoxylation technology and sulfation step thereafter, the ethoxylated alkyl sulfates that is obtained by close limit ethoxylate (NRE) also is the water soluble anionic surfactant that is applicable to the present composition.The close limit ethoxylated alkyl sulfates that is applicable to this is selected from the sulfation alkylethoxylate that on average contains 1-6, preferred 2-4, particularly 3mol oxyethane approximately, as lauryl ether-3 sodium sulfate close limit ethoxylate.Be applicable to that close limit ethoxylate of the present invention comprises the required oxyethane (EO of following partition ratio n): about 15-30% (weight) EO n, about 10-20% (weight) EO N+1And about 10-20% (weight) EO N-1Particularly preferred close limit ethoxylate contains approximately and is lower than 9% (weight) and contains 7 or greater than the ethoxylated alkyl sulfates of the oxyethane of 7mol be lower than the non-ethoxylated alkyl-sulphate of about 13% (weight).Lauryl ether-3 vitriol close limit the ethoxylate that is suitable for can be available from the product of Hoechst with trade(brand)name GENAPOLZRO Narrow Range and GENAPOL Narrow Range.
The content of water soluble anionic surfactant alkyl ethoxylated carboxylate surface active agent is about 0.5-15% (weight) in the present composition, preferably is about 1-10% (weight), is more preferably 1-6% (weight), particularly is about 1-4% (weight).Alkyl ethoxy carboxylate surfactant is particularly conducive to and makes composition of the present invention have fabulous skin mildness, has fabulous rinsing characteristic and required foaming character simultaneously.
Be applicable to that alkyl ethoxy carboxylate of the present invention is shown in logical formula I:
R 3O (CH 2CH 2O) kCH 2COO -M +R wherein 3Be C 10-C 15Alkyl or alkenyl, preferred C 11-C 15, more preferably C 12-C 14Alkyl, or C 12-C 13Alkyl, k are ethoxylation mean value, are about 2-7, preferably be about 3-6, be more preferably 3.5-5.5, particularly about 4-5, most preferably from about 4-4.5, and M is a water-soluble cationic, preferably basic metal, alkaline-earth metal, ammonium, low-grade alkane alcohol ammonium, and single-, two-and three-ethanol ammonium, more preferably sodium, potassium and ammonium salt, most preferably sodium and ammonium salt, and the mixture of they and magnesium and calcium ion.
Be applicable to that especially preferably water soluble anionic surfactant of the present invention is the alkyl ethoxy carboxylate surfactant with selected alkyl chain and/or ethoxylate distribution.Therefore, be applicable to R in the distribution of the alkyl ethoxy carboxylate that the alkyl ethoxy carboxylate surfactant of the present composition is contained 3And/or the mean value difference of k.
Work as R 3On average be C 11, C 12, C 13Or C 14The time k mean value generally be about 3-6.Being preferred for water soluble anion alkyl ethoxy carboxylate surfactant of the present invention is C 12-C 14(EO mean value is 3-6) ethoxy carboxylate and C 12-C 13(EO mean value is 3-6) ethoxy carboxylate.The material that is suitable for comprises (Houston, Texas, the salt of NEODOx 23-4 (RTM) USA) available from Shell Inc..Very preferably being used for of the present invention is alkyl ethoxy carboxylate surfactant, wherein R 3Be C 12-C 14Or C 12-C 13The mean value of alkyl and k is about 3-6, is more preferably 3.5-5.5, particularly is about 4-5, and 4-4.5 most preferably from about.
The present composition also can comprise about 0.1-20% (weight), is more preferably 0.1-10% (weight), especially preferably is about the water soluble nonionic surfactant of 1-8% (weight).This class tensio-active agent comprises C 12-C 14Lipid acid monoalkylol amide or di alkanolamide, as the cocoyl glycollic amide, the single sec.-propyl acid amides of cocoyl, cocoyl diglycollic amide and their ethoxylated derivative, sucrose polyfatty acid esters tensio-active agent, C 10-C 18Alkyl poly glucoside, and the polyhydroxy fatty acid amide surfactants shown in following logical formula III:
Figure A9719705100211
Preferred N-alkyl, N-alkoxyl group or N-aryloxy, polyhydroxy fatty acid amide surfactants are R in the formula III 8Be C 5-C 31Alkyl, preferred C 6-C 19Alkyl comprises straight or branched alkyl and alkenyl, or their mixture, and R 9Be generally H, C 1-C 8Alkyl or hydroxyalkyl, preferable methyl or formula-R 1-O-R 2Shown group, wherein R 1Be C 2-C 8Alkyl comprises straight chain, side chain and cyclic group (comprising aryl), and is preferably C 2-C 4Alkylidene group, R 2Be C 1-C 8Straight chain, side chain and cyclic hydrocarbon radical comprise aryl and oxygen-containing hydrocarbon base, preferably C 1-C 4Alkyl, particularly methyl or phenyl.Z 2It is the polyhydroxy alkyl structure division that comprises the straight-chain alkyl that contains 2 (when adopting Glycerose) or 3 (when adopting other reducing sugar) hydroxyls at least, perhaps their alkoxy derivative (preferred ethoxylated derivative or propoxylated derivative), wherein hydroxyl directly links to each other with hydrocarbyl chain.Z 2Preferably react (ammination) derived from reducing sugar, most preferably Z through reductive amination 2It is sugar alcohol base (gIycityl) part.The reducing sugar that is suitable for comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose, and wood sugar, and Glycerose.Except that each above-mentioned sugar, also can adopt following raw material, as high glucose maize treacle, high-fructose corn syrup and high Fructus Hordei Germinatus maize treacle.Can obtain being used for Z by these syrup 2The sugar component mixture.Be understood that and do not get rid of the starting material that other is suitable for.Z 2Be preferably selected from CH 2-(CHOH) n-CH 2OH ,-CH (CH 2OH)-(CHOH) N-1-CH 2H, CH 2(CHOH) 2(CHOR ') CHOH)-CH 2OH, wherein n is the integer of 1-5, comprises end value, and R ' is H or cyclic monosaccharides or ring polysaccharide, and their alkyl derivative.According to described, sugar alcohol base most preferably, wherein n is 4, specifically is-CH 2-(CHOH) 4-CH 2OH.
Most preferred polyhydroxy fatty acid amide is suc as formula R 8(CO) N (CH 3) CH 2(CHOH) 4CH 2Shown in the OH, R wherein 8Be C 6-C 19Straight chained alkyl or alkenyl.In the following formula compound, R 8-CO-N<for example can be coconut oleoyl amine, stearylamide, oleylamide, laurylamide, myristic amide, decyl amide, palmitic amide, butter acid amides etc.
The preferred method for preparing above-mentioned formula III compound comprises: replace polyhydroxy amine by fatty acid triglycercide and N-and do not have rudimentary (C substantially 1-C 4) react under the condition of alcoholic solvent, but preferred and alcohol alcoxylates or alkoxylated alkylphenol such as NEODOL, and about 50-140 ℃ down employing alcoxylates catalyzer so that desired product reaches higher productive rate (90-98%).In United States Patent (USP) A5194639 and A5380891, summarized the method for the polyhydroxy fatty acid amide compound that is applicable to that preparation is required.
The nonionogenic tenside of known gentleness such as polyhydroxy fatty acid amide and alkyl poly glucoside can make product have fabulous skin mildness, have good foaminess and sanitary characteristics simultaneously.But the applicant finds: when adopting customary thickeners (as ionogen), contain high-content (>1%w/w) undiluted water soluble surfactant active's system of this constituents can be invalid or unstable.For example in preparation improperly, contain polyhydroxy fatty acid amide surfactants and electrolytical undiluted water soluble surfactant active's system is rarer, and be difficult to thickening.
The applicant adopts conventional thickening material to exist the thinning and stable defective of product except that finding, can make it have certain thickening property when also finding to add other thickening material such as Natvosol, xanthan gum, guar gum, polymkeric substance JR30M (TM) in the undiluted water soluble surfactant active's matrix that contains polyhydroxy fatty acid amide surfactants, but can damage the foaminess and the rinsing of product.
Therefore need to develop a kind of thickened systems gentleness, undiluted water soluble surfactant active's system that contains polyhydroxy fatty acid amide and/or alkyl poly glucoside that is used to prepare, with so that product has good product thickening property, rheological properties and stability, make product have good foaminess and rinsing characteristic simultaneously.
The applicant finds that at present thickened systems of the present invention is when being used to contain undiluted water soluble surfactant active's system of gentle nonionogenic tenside (as polyhydroxy fatty acid amide and alkyl poly glucoside), help making product to have fabulous product thickening property and rheological properties, have good foaminess and skin mildness with seasonal product.
Another aspect of the present invention provides a kind of personal cleaning compositions, wherein contains: (a) about 0.01-15% (weight) thickened systems, in this system mainly by associative polymer and on request the HLB value be at least 12 polar oil and form; (b) the nonionic polyhydroxy fatty acid amide surfactants of about 0.1-20% (weight) shown in formula III:
Figure A9719705100231
R wherein 8Be C 5-C 31Alkyl, R 9Be hydrogen, C 1-C 8Alkyl or hydroxyalkyl, and Z 2It is the polyhydroxy alkyl part; (c) the water-soluble cosurfactant the polyhydroxy fatty acid amide surfactants of about 1-60% (weight) in (b) is selected from anion surfactant, nonionic, zwitter-ion and amphoterics and their mixture; (d) water.Wherein the average carbon chain length of polar oil is about 10-18 carbon atom, and with water-soluble undiluted tensio-active agent matrix in the average carbon chain length of total polyhydroxy fatty acid amide and other gentle surfactant mixture basic identical.
Be applicable to and also contain the soluble amphoteric tensio-active agent in the composition of the present invention.The amphoterics that is applicable to the present composition comprises: (a) imidazoline surfactant of formula IV:
Figure A9719705100232
R wherein 1Be C 7-C 22Alkyl or alkenyl, R 2Be hydrogen or CH 2Z, each Z are CO independently of one another 2M or CH 2CO 2M, and M is H, basic metal, alkaline-earth metal, ammonium or alkanol ammonium; And/or the ammonium derivative of formula (V): R wherein 1, R 2With the definition of Z as above; (b) the amino-alkane hydrochlorate of formula VI:
R 1NH (CH 2) nCO 2The iminodiacetic alkanoate of M formula (VII)
R 1N[(CH 2) mCO 2M] 2And the imino-multichain alkyl salt of formula (VIII)
Figure A9719705100241
Wherein n, m, p and q are the numbers of 1-4, and R 1Be independently from each other above-mentioned group with M; And (c) their mixture.
The suitable amphoterics of type (a) is commercially available with trade(brand)name Miranol and Empigen, and should be appreciated that it comprises the complex mixture of different sorts material.Traditionally, generally Miranols is described as having the material of general formula IV, though the 3rd edition " CTFA components of cosmetics dictionary (Cosmetic Ingredient Dictionary) " is indicated as non-ring structure V, the 4th edition then is indicated as another constitutional isomer, wherein R 2It is that O-connects but not the N-connection.In fact, the very possible complex mixture that has ring and acyclic kind, for the purpose of complete, this paper has provided two definition.Yet what be preferred for this paper is non-ring species class.
The example of the suitable amphoterics of type (a) comprises the compound with formula V and/or IV, wherein R 1Be C 8H 17(especially iso-octyl), C 9H 19And C 11H 23Alkyl.Particularly preferably be, wherein R 1Be C 9H 19, Z is CO 2M, R 2It is the compound of H; R wherein 1Be C 11H 23, Z is CO 2M, R 2Be CH 2CO 2The compound of M; And R wherein 1Be C 11H 23, Z is CO 2M, R 2The compound that is.
According to the CTFA nomenclature mo, the material that is suitable among the present invention comprises cocoa both sexes carboxyl propionic salt (cocoamphocarboxypropionate), cocoa both sexes carboxyl propionic acid, and especially cocoa both sexes acetate and cocoa both sexes diacetin (perhaps being called cocoa both sexes carboxyl glycinate).Concrete commerical prod comprises the material that those are sold with following trade(brand)name: Ampholak7TX (many propyl group of carboxyl methyl tallow amine sodium), Empigen CDL 60 and CDR 60 (Albright﹠amp; Wilson), Miranol H2M Conc.Miranol C2M Conc.N.P., MiranolC2M Conc.O.P., Miranol C2M SF, Miranol CM Special (Rhone-Poulenc); Alkateric 2CIB (Alkaril Chemicals); Amphoterge W-2 (Lonza, Inc.); Monateric CDX-38, Monateric CSH-32 (MonaIndustries); Rewoteric AM-2C (Rewo Chemical Group); And Schercotic MS-2 (Scher Chemicals).
Certainly, the commercially available amphoterics of some these types is with the form preparation of the electric neutrality mixture of following material with sell, for example, perhaps have anion sulfate or sulfosalt surfactant, especially those Sulfated C with the oxyhydroxide counter ion 8-C 18Alcohol, C 8-C 18The alcohol of ethoxylation or C 8-C 18The tensio-active agent of acyl glyceride type.Yet, consider the composition of preferably essentially no (not ethoxylation) Sulfated pure tensio-active agent from mildness and product stability aspect.Also should note: in this article, the concentration of amphoterics and weight ratio are based on the tensio-active agent of non-complexed forms formula, generally arbitrary aniorfic surfactant counter ion are taken as the part for total aniorfic surfactant content.
The example of the preferred amphoterics of type (b) comprise by Berol Nobel with the many trimethylenes of N-alkyl that trade(brand)name AmpholakX07 and Ampholak7Cx sell many-salt of carboxymethyl amine and salt thereof, especially tri ethanol ammonium salt and N-lauryl-β-An Jibingsuan and N-lauryl-imino--dipropionic acid.Sell such material with trade(brand)name Deriphat (by Henkel) and Mirataine (by Rhone-Poulenc).
The composition of this paper also can comprise about 0.1% to about 20%, more preferably about 0.1% to about 10%, especially is about 1% to about 8% zwitterionics.
The water-soluble auxiliary beet alkali surface activator that is suitable for being included in the composition of the present invention comprises formula R 5R 6R 7N +(CH 2) nCO 2The amido betaines of the alkyl betaine of M and following formula (IX):
Figure A9719705100251
R wherein 5Be C 11-C 22Alkyl or alkenyl, R 6And R 7Be C independently 1-C 3Alkyl, M are H, basic metal, alkaline-earth metal, ammonium or alkanol ammonium, and n, m be the number of 1-4 separately.Preferred trimethyl-glycine comprises cocoa amido propyl-dimethyl carboxymethyl betaine, lauryl amido propyl-dimethyl carboxymethyl betaine and Tego trimethyl-glycine (RTM).
Water-soluble auxiliary sultaine (sultaine) tensio-active agent that is suitable for being included in the composition of the present invention comprises the alkylamidoalkyl sultaine with following formula;
Figure A9719705100261
R wherein 1Be C 7-C 22Alkyl or alkenyl, R 2And R 3Be C independently 1-C 3Alkyl, M are H, basic metal, alkaline-earth metal, ammonium or alkanol ammonium, and m and n are the numbers of 1-4.What be preferred for this paper is cocoamide base propyl hydroxy sultaine.
The water-soluble assisted oxidation amine tensio-active agent that is suitable for being included in the composition of the present invention comprises alkyl amine oxide R 5R 6R 7NO and amido amine oxide with following formula:
Figure A9719705100262
R wherein 5Be C 11-C 22Alkyl or alkenyl, R 6And R 7Be C independently 1-C 3Alkyl, M are H, basic metal, alkaline-earth metal, ammonium or alkanol ammonium, and m is the number of 1-4.Preferred amine oxide comprises cocoa amido propyl group amine oxide, lauryl dimethyl amine oxide and myristyl dimethyl amine oxide.The polymerizing cationically amendment
Selectively comprise the polymerizing cationically amendment according to composition of the present invention.In according to composition of the present invention, the polymerizing cationically amendment is valuable for required skin sense attribute is provided.The polymerization skin conditioning agent preferably exists to the content of about 5% (weight) with about 0.01%, and more preferably about 0.01% to about 3%, especially is about 0.01% to about 2%.
Suitable polymers is high molecular weight material (the quality molecular-weight average that is recorded by for example scattering of light is generally about 2,000 to about 5,000,000, is preferably about 5,000 to about 3,000,000, more preferably about 100,000 to about 1,000,000).
Represent other polymkeric substance of level to comprise cationic polysaccharide; Derive from the cationic homopolymer and the multipolymer of vinylformic acid and/or methacrylic acid; The cationic cellulose resin; Dimethyl diallyl ammonium chloride and acrylamide are or/and acrylic acid cationic copolymer; The cationic homopolymer of dimethyl diallyl ammonia chloride; Positively charged ion polyalkylene and oxyethyl group polyalkyleneimine; Quaternised siloxanes and composition thereof.
Explanation by way of example, the cationic polymers that is suitable for this paper comprises cation guar gum, for example with the commercially available Hydroxyproyl Trimethyl ammonium guar gum of trade(brand)name Jaguar C-14-S (RTM) and Jaguar C-17 (RTM) and Jaguar C-16 (RTM) ((d.s. is about 0.11 to about 0.22) (comprising also that except that the cation group of above explanation d.s. is the hydroxypropyl substituting group of 0.8-1.1), and with trade(brand)name Ucare Polymer JR-30M, JR-400, Catanal (RTM) and the commercially available quaternised hydroxyethyl cellulose ethers of Celquat.Other suitable cation polymkeric substance is the homopolymer (commercially available with trade(brand)name Merquat 100) of dimethyl two allyl ammonium chlorides, the multipolymer of amino-ethyl methylacrylic acid dimethyl ester and acrylamide, the multipolymer of dimethyl diallyl ammonium chloride and acrylamide (commercially available) with trade(brand)name Merquat 550 and Merquat S, vinylformic acid/dimethyl diallyl ammonium chloride/acrylamide copolymer (commercially available) with trade(brand)name Merquat 3330, (for example polyquaternium 11 for the quaternised vinyl pyrrolidone acrylate of amino alcohol or methylacrylic acid ester copolymer (Gafquat is commercially available with trade(brand)name), 23 and the 28 (quaternised multipolymer-Gafquat 755N of vinyl pyrrolidone and amino-ethyl methylacrylic acid dimethyl ester, and the multipolymer of vinyl pyrrolidone and dimethyl aminoethyl methylacrylic acid acid amides-HS 100)), vinyl pyrrolidone/vinyl imidazole methochloride multipolymer is (with trade(brand)name Luviquat FC370, polyquaternium 2 is commercially available), and polyalkyleneimine (as polyethylene imine based and ethoxylation polyethylene imine based).
Composition of the present invention also preferably comprises about 0.1% oil or its mixture deutero-nonionic surface active agent to about 20% (weight), is preferably about 1% to about 15%, more preferably about 2% to about 10%.In according to composition of the present invention, oily deutero-nonionic surface active agent is in use with skin sense benefit aspect is provided is valuable after using.The oily deutero-nonionic surface active agent that is suitable for this paper comprises the water miscible plant and animal deutero-softener triglyceride level of insertion polyglycol chain wherein (as have), the mono and di-glycerides of ethoxylation, the cream derivative of the lanolin of polyethoxylated and ethoxylation.Other the oily deutero-nonionic surface active agent of a priority that is used for this paper has general formula (XII):
Figure A9719705100281
Wherein n is about 5 to about 200, is preferably about 20 to about 100, more preferably about 30 to about 85, and wherein R comprises aliphatic group, and its average carbon atom number is about 5-20, is preferably about 7-18.
The oil ﹠ fat of other suitable ethoxylation of this grade comprises theobromic acid glyceryl ester, caproin, caprylin, tallow fatty acid glyceryl ester, palmitin, stearin, laurin, olein, ricinolic acid glyceryl ester and derive from triglyceride level, as the glycerin fatty family ester of plam oil, Prunus amygdalus oil and Semen Maydis oil, be preferably the polyethyleneglycol derivative of tallow fatty acid glyceryl ester and theobromic acid glyceryl ester.
Other suitable oily deutero-nonionic surface active agent of this grade is can be by Croda Inc. (New York, the U.S.) their the Crovol series material that obtains, as Crovol EP40 (PEG 20 Oenothera glyceryl ester), Crovol EP70 (PEG 60 Oenothera glyceryl ester), Crovol A-40 (PEG 20 almond glyceryl ester), Crovol A-70 (PEG 60 almond glyceryl ester), CrovolM-40 (PEG 20 corn glyceryl ester), Crovol M-70 (PEG 60 corn glyceryl ester), Crovol PK-40 (PEG 12 palms nuclear glyceryl ester) and Crovol PK-70 (PEG 45 palms nuclear glyceryl ester), and their Solan series material is (as Solan E, and the Aqualose L-20 (PEG 24 Wool wax alcohols) and the Aqualose W15 (PEG 15 Wool wax alcohols) that can obtain by westbrook Lanolin the lanolin of E50 and X polyethoxylated).This level other more suitably tensio-active agent be tensio-active agent by the Varonic LI series of commercially available they of Sherex chemical company (Dublin, Ohio, the U.S.), and by the Rewoderm series of surfactants of commercially available they of Rewo.These tensio-active agents comprise, varouic LI 48 (polyoxyethylene glycol (n=80) tallow fatty acid glyceryl ester for example, perhaps be referred to as PEG 80 tallow fatty acid glyceryl ester), Varonic LI 2 (PEG 28 tallow fatty acid glyceryl ester), Varouic LI 420 (PEG 200 tallow fatty acid glyceryl ester) and Vatonic LI 63 and 67 (PEG 30 and PEG 80 theobromic acid glyceryl ester), RewodermLI5-20 (PEG-200 cetylate), Rewoderm 80 (the PEG-200 cetylate that PEG-7 theobromic acid glyceryl ester is arranged) and Rewoderm LIS-75 (the PEG-200 cetylate that PEG-7 theobromic acid glyceryl ester is arranged) and composition thereof.The PEG derivative that to be suitable for other oily deutero-softener herein be corn, avocado and babassu oil, and Softigen 767 (PEG (6) caprylic/capric glyceryl ester).
The tensio-active agent that also is suitable for this paper is nonionic surface active agent and the derivative thereof that derives from the mixed plant fat that extracts from the fruit of Butyrospermum Parkii (ButyrospermumKarkii Kotschy).Known this vegetation fat that is called shea butter in must arrive widely and use, its using method is varied as be used for making soap and as cold cream, this vegetation fat is sold by Sederma (78610 Le Perray En Yvelines, France).Specially suitable is by (the Columbos of Karlshamn chemical company, the Ohio, the U.S.) derivative of the ethoxylation of the shea butter that provides with Lipex series pharmaceutical chemicals, as Lipex 102 E-75 and Lipex 102 E-3 (list of the ethoxylation of shea butter-, two-glyceryl ester), and by Croda Inc. (New York, the U.S.) derivative of the ethoxylation of the shea butter that provides with their Crovol series material is as Crovol SB-70 (list of the ethoxylation of shea butter-, two-glyceryl ester).Similarly, the ethoxylated derivative of mango, cocoa and East India Sapotaceae vegetable tallow can be used for according to composition of the present invention.Though these tensio-active agents are classified as the nonionic surface active agent of ethoxylation, much less still keep the vegetables oil or the fat of a certain proportion of not ethoxylation.
Other suitable oily deutero-nonionic surface active agent comprises Prunus amygdalus oil, peanut oil, Rice pollard oil, wheat germ oil, Toenol 1140, simmondsia oil, the oil of apricot fruit stone, English walnut, palm nut, Pistacia vera fruit stone, til seed, Semen Brassicae campestris, oleum alchitri, Semen Maydis oil, peach-pit oil, seed of Papaver somniferum L. powder, pine tar, Viscotrol C, soybean oil, Lipoval A, Thistle oil, Oleum Cocois, hazelnut oil, sweet oil, the ethoxylated derivative of raisin seed oil and wunflower seed oil.
With regard to best mildness and skin sense characteristic aspect, the oily deutero-nonionic surface active agent that most preferably is used for this paper is Lipex 102-3 (RTM) (the PEG-3 ethoxylated derivative of shea butter) and Softigen767 (RTM) (PEG-6 caprylic/capric glyceryl ester).Hydrotropic solvent
Also can not necessarily comprise hydrotropic solvent in the present composition.Be applicable to that hydrotropic solvent of the present invention is well known in the art, comprise sodium xylene sulfonate, ammonium xylene sulfonate, cumene sodium sulfonate, short-chain alkyl vitriol, and their mixture.The content of hydrotropic solvent is about 0.01-5% (weight) in the present composition, preferably is about 0.1-4% (weight), more preferably 0.5-3% (weight).Aforesaid hydrotropic solvent is meant it is added in undiluted water soluble surfactant active's system and can improves the viscosity of product and the composition of rheological properties.
How undiluted water soluble surfactant active's matrix has good product thickening property and rheological properties can be a controversial process there being the hydrotropic solvent existence to order.Therefore require to develop and a kind ofly be used to make the undiluted water soluble surfactant active's matrix that contains hydrotropic solvent to have the good product thickening property and the thickened systems of rheological properties.
The applicant finds that thickened systems of the present invention can make the undiluted water soluble surfactant active's system that contains hydrotropic solvent have the good product thickening property and the thickened systems of rheological properties.The applicant also finds: when the ratio of water soluble surfactant active and the total amount of hydrotropic solvent is about 5: 1-1: 5, perhaps be about 3: 1-1: and 3, be more preferably 1.5: 1-1:, can make product have fabulous product thickening property at 1.5 o'clock.
Another aspect of the present invention provides a kind of personal cleaning compositions, wherein comprises: (a) about 0.01-15% (weight) thickened systems, in this system mainly by associative polymer and on request the HLB value be at least 12 polar oil and form; (b) about 1-60% (weight) water soluble surfactant active is selected from anion surfactant, nonionic, zwitter-ion and amphoterics and their mixture; (c) can contain about 0.01-5% (weight) hydrotropic solvent that can not contain; (d) can contain the skin conditioning agent of about 0.01-5% (weight) cationic polymerization type that can not contain; And (e) water.Wherein the average carbon chain length of polar oil is about 10-18 carbon atom, and wherein water soluble surfactant active's average carbon chain length is about 10-18 carbon atom, and the water soluble surfactant active is about 5 with the total amount ratio of hydrotropic solvent: 1-1: 5.
The present composition can comprise lipophilic emulsifier as the skin care activity composition.The lipophilicity skin care activity composition that is suitable for comprises the negatively charged ion food emulsifier, wherein contains and monoglyceride (as succinylation monoglyceride, citric acid list tristearin alcohol ester, stearic acid monoglyceride, diacetyl tartrate and their mixture) blended bisgallic acid mutually.
Also can comprise insoluble essence or cosmetic oil or wax in the composition of the present invention, or their mixture, the highest 10% (weight) that is about of its consumption, preferably the highest 3% (weight) that is about, wherein oil or wax are insoluble, insolublely are meant that be insoluble at 25 ℃ of following oil or wax in product matrix.Adding this class oil or wax can make personal cleaning compositions of the present invention have emollient, mildness and rinsing characteristic.But characteristics of the present invention are: contain in the composition be lower than about 1% (weight), when preferably being lower than 0.5% (weight) additional (except that polar oil) oil phase, said composition has fabulous emollient and mildness, has required physical property (transparency etc.) simultaneously.Preferred this based composition is optically transparent solution or microemulsified bodily form formula aspect physical property.In the composition that comprises additional essence or cosmetic oil or wax, preferably be at least about 1: 2 derived from the nonionogenic tenside of oil and the weight ratio of additional oil, more specifically be about 3: 1.
Be applicable to that insoluble cosmetic oil of the present invention and wax are selected from: the water-insoluble polysiloxane, comprising non-volatile poly-alkyl and poly-aryl siloxanes glue and the poly-alkylsiloxane of fluid, volatile cyclic and chain, poly-alkoxylation polysiloxane, through amino and quaternised modified polysiloxane, rigidity cross linking polysiloxane and through the enhanced polysiloxane, and their mixture, C 8-C 30The C of lipid acid 1-C 24Ester is as Isopropyl myristate, Tetradecyl tetradecanoate and ricinolic acid cetyl, benzoic C 8-C 30Ester, beeswax, saturated and unsaturated fatty alcohol such as behenyl alcohol, hydro carbons such as mineral oil, Vaseline, squalane and squalene, polybutene, fatty acid esters of sorbitan is (referring to US-A-3988255, Seiden, on October 26th, 1976 authorized), lanolin and oily lanolin derivative, vegetable and animals oils triglyceride level such as Prunus amygdalus oil, peanut oil, wheat germ oil, cavings oil, linseed oil, simmondsia oil, and almond, English walnut, palm-kernel, the Pistacia vera fruit, til seed, the oil of Semen Brassicae campestris, oleum alchitri, Semen Maydis oil, persic oil, seed of Papaver somniferum L. powder, pine tar, Viscotrol C, soybean oil, Lipoval A, Thistle oil, Oleum Cocois, acorn nut oil, sweet oil, raisin seed oil and sunflower seed oil, and the C of dimeracid and trimer acid 1-C 24Ester is as diacid diisopropyl ester, oxysuccinic acid diisopstearate, diacid diisopstearate and three sour three isostearates.
(Btookfield DV II, 1 rev/min of rotating speed adopt CP41 or CP52 rotor to the viscosity of final composition, 25 ℃, net phase) preferably be at least about 500 centipoises, be more preferably the 1000-50000 centipoise, especially be about the 1000-30000 centipoise, more particularly about 1000-15000 centipoise.
Also can not necessarily contain other hair that dissolves in cleaning compositions matrix or skin moisturizing agent in this cleaning compositions.The preferred content of this moisturizing agent is about 0.5-20% (weight).In preferred embodiments, moisturizing agent is selected from the natural amino acid whose compound that is present in the necessity in the keratoderma, and the non-occlusion composition (nonocclusive) and their compound of water-soluble non-polyvalent alcohol.
Some preferred example to non-occlusion moisturizing agent has: polybutene, squalane, carboxylic acid pyrrolidone sodium, D-panthenol, lactic acid, L-proline(Pro), guanidine, pyrrolidone, protolysate and other protein derived from collagen, Lu Yun gel, ethanamide MEA and lactic amide MEA, and their mixture.
Also can comprise opalizer or pearling agent in the composition of the present invention.The content of these compositions is about 0.01-5% (weight), preferably is about 0.2-1.3% (weight).The opalizer that is applicable to the present composition has available from the commodity of Morton International Lytron 621 by name; The polystyrene dispersions of 631 (RTM).
Other the opalizer/pearling agent that is applicable to the present composition comprises: titanium dioxide TiO 2EUPERLAN 810 (RTM); TEGO-PEARL (RTM); Long-chain (C 16-C 22) acyl derivative, contain the glycol or the macrogol ester of the lipid acid of 16-22 carbon atom according to appointment, wherein contain 7 ethylene oxide units at most; The fatty acid alkyl amide that contains 16-22 carbon atom, preferred 16-18 carbon atom approximately, as stearic acid monoethanolamide, Stearic acid diethanolamine salt, stearic acid list isopropanol amide and stearic acid monoethanolamide, and alkyl (C 16-C 22) dimethyl oxidation amine, as stearyl dimethyl amine oxide.
In preferred composition, opalizer/pearling agent is crystalloid.In particularly preferred composition, opalizer/pearling agent is that granularity is about the 0.05-0.45 micron, preferably is about the granular polystyrene dispersion of 0.17-0.3 micron, for the angle of best rheological properties and shear shinning performance, and preferred such dispersion.Particularly preferably be vinylbenzene PVP multipolymer and Lyton631 (RTM).
The content that can be used for other nonessential composition of majority of cleaning compositions is about 0.1-0.2% (weight) respectively.This constituents comprises protein and polypeptide, and their derivative; Water-soluble or soluble sanitas, as methyl esters, ethyl ester, propyl ester and the butyl ester of DMDM wallantoin, Germall 115, hydroxy-benzoic acid, EDTA, Euxyl (RTM) K400, natural antiseptic agent such as phenylcarbinol, potassium sorbate and Hydagen B; Sodium Benzoate and 2-phenoxyethyl alcohol; Other moisturizing agent such as hyaluronic acid, chitin and starch-grafted sodium polyacrylate, as available from CelanessSuperabsorbent Materials (Portsmith, VA, Sanwet USA) (RTM) IM-1000, IM-1500 and IM-2500, and can be referring to US-A-4076663; Solvent; The antiseptic-germicide that is suitable for, as Oxeco (phenoxy group Virahol), trichlorine carbanilide (TCC) and triclosan, and low temperature phase modifier such as ammonium ion source (for example, NH 4Cl); Viscosity modifier such as sal epsom and other ionogen; Tinting material; The mica of titanium dioxide and coated by titanium dioxide; Essence and essence solubilizing agent; And zeolite such as Valfour BV400 and derivative thereof, and Ca +/ Mg 2+Sequestering agent such as multi-carboxylate, aminopolycanboxylic acid's salt, polyphosphate, amino polyphosphate, EDTA etc., water-softening agent such as Trisodium Citrate and insoluble particle such as Zinic stearas and forging silica.The content of water preferably accounts for the 20-99.89% (weight) of the present composition, preferably is about 40-90% (weight), more preferably is at least about 75% (weight).
The pH of composition preferably is about 4-10,6-9 more preferably from about, particularly about 5-8, and 5-7 most preferably from about.
Experimental result
All viscosity are all measured down at 26.7 ℃, in centipoise.
Preferred all content are based on weight percent meter.Method:
Adopt Brookfield awl dish model DV II viscometer, the CP41 rotor.
Under being 1 rev/min or appropriate rotating speed, rotating speed measures to reach correct torque value.All measured values all ± 50 centipoises.Surfactant system
Anion surfactant (C 12-13The Pareth-5 carboxylic acid sodium), sodium decyl sulfate (EmpicolLC 35); Nonionogenic tenside (C 12-14The N-methyl glucose amide); Amphoterics (cocounut oil both sexes diacetin).Tensio-active agent total amount: 12% (weight).
The table I
Interaction between associative polymer and the polar oil
Polymer content polar oil content viscosity
(centipoise) Natrosol Plus 430 0.5 C 12-13Alcohol 0.0 350Natrosol Plus 430 0.0 C 12-13Alcohol 0.6 350Natrosol Plus 430 0.5 C 12-13Alcohol 0.6 3500Acrysol 44 0.5 C 12-13Alcohol 0.0 150Acrysol 44 0.0 C 12-13Alcohol 0.6 350Acrysol 44 0.5 C 12-13Alcohol 0.6 1000
The table II
The effect polymer content polar oil content viscosity of polar oil ethoxylation degree (X)
(centipoise) Acrysol 44 1.0 C 12-140EO (Laurex NC) 0.7 1200Acrysol 44 1.0 C 12-143EO (Genapol L3) 0.7 300Acrysol 44 1.0 C 12-147EO (Empicol KBE 7) 0.7 50
To describe the present composition by following indefiniteness embodiment.In an embodiment, all concentration are all in 100% actives, and its abbreviation has following title: anion surfactant 1:C 12-13The Pareth-4-carboxylic acid sodium is (derived from alkyl ether carboxylic acid's sodium
Salt, the NEODOX 23-4 that Shell US Inc. produces) anion surfactant 2: lauryl ether-4 carboxylic acid sodium anion surfactant 3: decyl sodium alkyl sulfate anion surfactant 4: lauryl ether-2 sodium sulfate amphoterics: cocounut oil both sexes oxalic acid disodium trimethyl-glycine: AMONYL 380LC nonionogenic tenside: the polyhydroxy fatty acid amide of formula IX, wherein R 8Be C 11-17Alkyl,
R 9Be methyl, Z 2Be CH 2(CHOH) 4CH 2OHHEUR 1:Acrysol 44HEUR 2:Bermodol 2130HMEHEC 1:Natrosol Plus 430HMHEC 2:Polysurf67HNP:Glucamate DOE polar oil 1:Dobanol 23 polar oil 2:Laurex NC/E
Embodiment I-VIII
Following personal cleaning compositions is to bathe with gel or the foam bath form of product, and is representative instance of the present invention:
I II III IV V VI VII VIII anion surfactant 1 4.0 6.0 4.0 3.0----anion surfactant 2----4.0 6.0--anion surfactants 3 2.0 3.0 1.5 2.5 3.0---anion surfactant 4-----3.0 12.0 8.0 amphoteric surfactantes 1.0 1.0 0.5 0.2 1.0 1.0--betaines------3.0 3.0 non-ionic surface active agents, 4.0 2.0 2.5 3.0 3.0 2.0--HEUR1 0.7---1.0 0.5--HEUR2---0.6--0.5-HMHEC1-0.5------HMHEC2--0.8--0.5-0 .5HNP---0.5----polar oils, 1 0.6 0.3 0.5 1.0--0.3,0.8 polar oil 2----0.4 0.6--water-------------------add to 100-------------
During preparation composition I-VIII, under paramount about 70 ℃ of conditions, in Tri-blender (TM) or through continuing to stir, water-soluble or the water miscible associative polymer of colloidal state are scattered in the water earlier, and through hydration.Stir gently down tensio-active agent is added this mixture (sustainable heating, temperature is paramount to be about 70 ℃).Preferably after adding tensio-active agent, add polar oil.Skin care ingredient (as the words that adopt) can together add with remainder water dissolubility, oily insoluble composition, adds remaining water, sanitas, opalizer and essence at last.
The viscosity of composition (Brookfield DV II, 1 rev/min of rotating speed adopt CP41 or CP52 rotor, and 25 ℃, net phase) be the 500-50000 centipoise, be preferably the 1000-15000 centipoise.
Product has fabulous product thickening property and rheological properties in storing, distribute and using, have favorable effects simultaneously, comprise fabulous rinsing characteristic, mildness, skin condition, skin moisturizing, good product stability, spatter property and foaminess.

Claims (25)

1. liquid personal cleansing composition, wherein contain: (a) about 0.01-15% (weight) thickened systems, this system mainly by associative polymer and on request the HLB value be at least 12 polar oil and form; (b) about 1-60% (weight) water soluble surfactant active is selected from anion surfactant, nonionic, zwitter-ion and amphoterics and their mixture; (c) can contain the skin conditioning agent of about 0.01-5% (weight) cationic polymerization type that can not contain; And (d) water.
Wherein the average carbon chain length of polar oil is about 10-18 carbon atom, and wherein water soluble surfactant active's average carbochain is about 10-18 carbon atom.
2. the composition in the claim 1, wherein the total amount of thickened systems is about 0.01-10% (weight), preferably is about 0.05-8% (weight), is more preferably 0.1-4% (weight), be most preferably 0.1-2% (weight), particularly be about 0.5-1.5% (weight).
3. the composition in the claim 1 or 2, wherein associative polymer is about 1 with the ratio of polar oil: 5-5: 1, preferably be about 1: 3-3: 1, be most preferably 1: 2-2: 1.
4. the composition of arbitrary claim among the claim 1-3, wherein the consumption of associative polymer is about 0.01-12% (weight), preferably be about 0.01-10% (weight), be more preferably 0.05-8% (weight), be most preferably 0.1-4% (weight), particularly be about 0.1-2% (weight), the most particularly be about 0.5-1.5% (weight).
5. the composition of arbitrary claim among the claim 1-4, wherein the molecular-weight average of associative polymer is about 2000-2000000, preferably is about 10000-1000000, is more preferably 20000-800000.
6. the composition of arbitrary claim among the claim 1-5, wherein associative polymer is hydrophobically modified water-soluble nonionic polymkeric substance, is selected from hydrophobically modified hydroxy alkyl cellulose polymkeric substance, hydrophobically modified alkoxylate urethane polymkeric substance, hydrophobically modified nonionic polyvalent alcohol and their mixture.
7. the composition of arbitrary claim among the claim 1-6, wherein the consumption of polar oil is about 0.01-3% (weight), preferably is about 0.01-2% (weight), is more preferably 0.1-1% (weight), is most preferably 0.2-0.8% (weight).
8. the composition of arbitrary claim among the claim 1-7, wherein the HLB value that requires of polar oil is about 12-15, is more preferably 12-14.
9. the composition of arbitrary claim among the claim 1-8, wherein polar oil is selected from average carbon chain length and is about 10-18 carbon atom, preferably about 12-16 carbon atom, the more preferably from about pure and mild lipid acid of natural and synthetic fat of 12-14 carbon atom.
10. the composition of arbitrary claim among the claim 1-9, wherein the average carbon chain length of the average carbon chain length of polar oil and undiluted water soluble surfactant active's system is basic identical.
11. the composition of arbitrary claim among the claim 1-10, wherein polar oil is a lauryl alcohol.
12. the composition of arbitrary claim among the claim 1-11, wherein the viscosity of composition (Brookfield DV II, 1 rev/min of rotating speed, employing CP41 or CP52 rotor, 25 ℃, net phase) is the 500-50000 centipoise, is preferably the 1000-15000 centipoise.
13. the composition of arbitrary claim among the claim 1-12, wherein water soluble surfactant active's total amount is about 2-40% (weight), preferably is about 3-15% (weight).
14. the composition of arbitrary claim among the claim 1-13; wherein water soluble anionic surfactant is selected from alkyl-sulphate; ethoxylated alkyl sulfates; alkyl glyceryl ether sulfonate; methyl-acyl taurine salt; fat acidyl glycine salt; alkyl ethoxy carboxylate; the N-acyl glutamate; acyl-hydroxyethyl sulfonate; alkyl sulfo succinate; the alkyl ethoxy sulfosuccinate; α-alpha-sulfonated fatty acid; their salt and/or ester; alkyl phosphate; ethoxylated alkyl phosphate ester; acyl sarcosinate and lipid acid/protein condenses, and their mixture.
15. the composition of arbitrary claim among the claim 1-14, wherein water soluble anionic surfactant is selected from alkyl-sulphate, ethoxylated alkyl sulfates, alkyl ethoxy carboxylate, and their mixture.
16. the composition of arbitrary claim among the claim 1-15 wherein also contains 0.1-20% (weight) water soluble nonionic surfactant approximately, is selected from C 12-C 14Fatty monoethanol amide and diglycollic amide, as the cocoyl glycollic amide, the single sec.-propyl acid amides of cocoyl, cocoyl diglycollic amide and their ethoxylated derivative, sucrose polyfatty acid esters tensio-active agent, C 10-C 18Alkyl poly glucoside, and polyhydroxy fatty acid amide surfactants.
17. the composition of arbitrary claim among the claim 1-16, wherein the soluble amphoteric tensio-active agent is selected from: (a) imidazoline surfactant of formula [IV]:
Figure A9719705100041
R wherein 1Be C 7-C 22Alkyl or alkenyl, R 2Be hydrogen or CH 2Z, each Z are CO independently of one another 2M or CH 2CO 2M, and M is H, basic metal, alkaline-earth metal, ammonium or alkanol ammonium; And/or the ammonium derivative of formula [V]:
Figure A9719705100042
R wherein 1, R 2With the definition of Z as above; (b) the amino-alkane hydrochlorate of formula [VI]:
R 1NH (CH 2) nCO 2The iminodiacetic alkanoate of M formula [VII]
R 1N[(CH 2) mCO 2M] 2And the imino-multichain alkyl salt of formula [VIII]
Figure A9719705100043
Wherein n, m, p and q are the numbers of 1-4, and R 1Be independently from each other above-mentioned group with M; And (c) their mixture.
18. the composition of claim 17, wherein the soluble amphoteric tensio-active agent is selected from the imidazolidine derivatives of formula IV and/or the ammonium derivative of formula V.
19. the composition of arbitrary claim among the claim 1-18, wherein the water soluble amphoteric ion tensio-active agent is selected from alkyl betaine, amido betaines, alkyl sultaine and their mixture.
20. the composition of arbitrary claim among the claim 1-19, it not necessarily contains the aggretion type cation opsonizing agent that molecular-weight average is about 2000-5000000, is more preferably 5000-3000000.
21. the composition of claim 20, wherein the aggretion type cation opsonizing agent is selected from the cationic homopolymer and the cationic copolymer of cationic polysaccharide, derived from propylene acid and/or methacrylic acid; The cationic cellulose resin; Dimethyl diallyl ammonium chloride and acrylic acid cationic copolymer; The cationic homopolymer of dimethyl diallyl ammonium chloride; Positively charged ion polyalkyleneimine and oxyethyl group polyalkyleneimine; Quaternary sillicones, and their mixture.
22. the composition of arbitrary claim in claim 20 and 21, wherein the content of polymerization negatively charged ion amendment is about 0.05-4% (weight), preferably is about 0.1-2% (weight), especially preferably is about 0.5-1.5% (weight).
23. the composition of arbitrary claim among the claim 1-22 wherein contains 0.1-20% (weight) nonionogenic tenside approximately, is selected from oxyethyl group carburetion or the fat shown in the formula (XII): Wherein n is about 5-200, preferably is about 20-100, is more preferably 30-85, wherein R comprise on average contain approximately 5-20 carbon atom, preferred contain approximately 9-20 carbon atom, more preferably from about contain 11-18 carbon atom, most preferably from about contain the aliphatic group of 12-16 carbon atom.
24. the composition of arbitrary claim among the claim 1-23 wherein also contains the essence or the cosmetic oil of paramount about 20% (weight).
25. the composition of arbitrary claim among the claim 1-24 wherein also contains the hydrotropic solvent of 0.01-5% (weight) approximately.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103974690A (en) * 2011-12-08 2014-08-06 花王株式会社 Skin cleansing agent composition
CN105963157A (en) * 2015-03-12 2016-09-28 科丝美诗(中国)化妆品有限公司 Cleansing cream composition comprising nonionic surfactants
CN112533575A (en) * 2018-07-30 2021-03-19 联合利华知识产权控股有限公司 Enhanced humectant deposition in cleaning solutions containing hydrophobically modified or non-hydrophobically modified anionic polymers

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW460508B (en) * 1997-05-02 2001-10-21 Rohm & Haas Aqueous composition comprising a mixed surfactant/associative thickener, its use in a formulated composition, and method for enhancing thickening efficiency of aqueous composition
FR2781370B1 (en) * 1998-07-07 2001-05-11 Oreal NOVEL COSMETIC COMPOSITIONS COMPRISING A FILM-FORMING POLYMER
DE19835239A1 (en) 1998-08-04 2000-02-24 Johnson & Johnson Gmbh Foaming oil preparation and its use
EP1088544A1 (en) * 1999-09-30 2001-04-04 The Procter & Gamble Company Hair care compositions
JP4596689B2 (en) * 2000-06-26 2010-12-08 株式会社資生堂 Cleaning composition
DE10051955A1 (en) * 2000-10-20 2002-05-02 Wella Ag Hair treatment agent in the form of a solid and dimensionally stable gel
WO2005023970A1 (en) * 2003-08-28 2005-03-17 Johnson & Johnson Consumer Companies, Inc. Methods of reducing irritation in personal care compositions

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4228277A (en) * 1979-02-12 1980-10-14 Hercules Incorporated Modified nonionic cellulose ethers
CA1273449A (en) * 1984-08-15 1990-08-28 David Farrar Stable concentrated and hydrous polymer dispersions
EP0172723B2 (en) * 1984-08-15 1997-11-05 Ciba Specialty Chemicals Water Treatments Limited Water soluble polymers
US4997641A (en) * 1990-04-09 1991-03-05 Colgate-Palmolive Company Hair conditioning shampoo containing C6 -C10 alkyl sulfate or alkyl alkoxy sulfate
US5104646A (en) * 1989-08-07 1992-04-14 The Procter & Gamble Company Vehicle systems for use in cosmetic compositions
US5100657A (en) * 1990-05-01 1992-03-31 The Procter & Gamble Company Clean conditioning compositions for hair
US5461100A (en) * 1992-05-29 1995-10-24 Union Carbide Chemicals & Plastics Technology Corporation Aircraft anti-icing fluids
US5292828A (en) * 1992-05-29 1994-03-08 Union Carbide Chemicals & Plastics Technology Corporation Polymers containing complex hydrophobic groups
US5393454A (en) * 1994-02-03 1995-02-28 Colgate Palmolive Co. Thickened composition containing polymeric thickener and aliphatic hydrocarbon
US5510452A (en) * 1994-07-11 1996-04-23 Rheox, Inc. Pourable liquid polyesteramide rheological additives and the use thererof
GB9424476D0 (en) * 1994-12-03 1995-01-18 Procter & Gamble Cleansing compositions
EP0796083A1 (en) * 1994-12-06 1997-09-24 The Procter & Gamble Company Shelf stable skin cleansing liquid with gel forming polymer and lipid

Cited By (5)

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CN103974690A (en) * 2011-12-08 2014-08-06 花王株式会社 Skin cleansing agent composition
CN103974690B (en) * 2011-12-08 2015-12-09 花王株式会社 Composition of skin cleanser
CN105963157A (en) * 2015-03-12 2016-09-28 科丝美诗(中国)化妆品有限公司 Cleansing cream composition comprising nonionic surfactants
CN112533575A (en) * 2018-07-30 2021-03-19 联合利华知识产权控股有限公司 Enhanced humectant deposition in cleaning solutions containing hydrophobically modified or non-hydrophobically modified anionic polymers
CN112533575B (en) * 2018-07-30 2023-12-01 联合利华知识产权控股有限公司 Enhanced deposition of humectants in cleaning solutions containing hydrophobically modified or non-hydrophobically modified anionic polymers

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GB9613968D0 (en) 1996-09-04
EP1019470A1 (en) 2000-07-19
CA2259453A1 (en) 1998-01-08
EP1019470A4 (en) 2002-08-14
WO1998000495A1 (en) 1998-01-08
JPH11514032A (en) 1999-11-30
BR9710139A (en) 1999-08-10

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