CN1029912C - Novel surfactants and surfactant compositions - Google Patents

Novel surfactants and surfactant compositions Download PDF

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CN1029912C
CN1029912C CN 91102024 CN91102024A CN1029912C CN 1029912 C CN1029912 C CN 1029912C CN 91102024 CN91102024 CN 91102024 CN 91102024 A CN91102024 A CN 91102024A CN 1029912 C CN1029912 C CN 1029912C
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ammonium
detergent
alkyl
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CN1055385A (en
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约瑟·A·埃尔哈特
乔治·E·德克纳
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Richardson Vicks Inc
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0094—High foaming compositions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/11—Esters of phosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/34—Derivatives of acids of phosphorus
    • C11D1/345—Phosphates or phosphites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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  • Health & Medical Sciences (AREA)
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  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Cosmetics (AREA)
  • Detergent Compositions (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Abstract

Disclosed are novel low skin irritation surfactants and surfactant compositions which are high in foaming properties containing, as an active ingredient, a diamine monoalkyl phosphate salt.

Description

Novel surfactants and surfactant compositions
The present invention relates to novel surfactant and the compositions thereof little to skin irritation, the said composition foam performance is good, and its active component is the diamidogen MAP.
People use soap, detergent and crocus to clean each position of health for a long time always.The surface active agent composition of many cleaning agent all uses anion surfactant widely, for example: alkyl sulfate, polyethylene glycol oxide alkyl sulfate, alkylbenzenesulfonate and alpha-alkene sulfonate.
People know, if these anion surfactants of life-time service just they adsorb thereby rest on skin surface, cause epidermis drying and squama, or chap with coarse.Like this, use detergent to cause easily to resemble coarse and so on the dermatosis of hands.Pachylosis can become the more tendency of serious disease (as eczema).Therefore, be badly in need of overcoming above-mentioned shortcoming.
On the other hand, non-ionic surface active agent can cause xerosis cutis or coarse hardly or not.But it does not resemble anion surfactant so good foaming and cleaning performance.Therefore, non-ionic surface active agent should not be mixed in the cleaning compositions as main detergent ingredients.
People know that phosphate ester is an anion surfactant, occur with the form of monoesters and dibasic acid esters or the form of its mixture usually.Yet their water solublity and foam performance are bad usually.
European patent No. 265702 (on May 4th, 1988 is open) discloses the transparent or semitransparent cosmetic composition that is used for skin, and it contains monoalkyl phosphoric acid esters, water, oil and pure.Use oil and alcohol can make it transparent.United States Patent (USP) the 4th, 573, No. 749 (authorize McIntosh, on June 28th, 1988 was announced) discloses the monoamine alkylphosphonic with antibacterial activity.United States Patent (USP) the 4th, 290, (authorize people such as Poper No. 904, JIUYUE in 1981 bulletin on the 22nd), British patent the 1st, 513, No. 053 (bulletin on June 7th, 1978) and European patent No. 023978 (on February 18th, 1981 is open) disclose the cosmetic formulations that contains oxyalkylated Alkylenediamine.United States Patent (USP) the 4th, 476, No. 043,4,476, No. 044 and 4,476, No. 045 (authorize O ' Lenick, all announced) on October 9th, 1984, and the 4th, 477, No. 372 (authorizing) ' Lenick of United States Patent (USP), on October 16th, 1984 bulletin) non-water surface activating agent is fully disclosed, comprise organo-sulfate, mineral oil and a kind of oxyalkylated amine, yet, the purposes of the open diamidogen alkyl phosphoric acid ester surfactant of neither one in the above-mentioned documents.
At the United States Patent (USP) the 4th of authorizing people such as Imokawa, 139, MAP is also disclosed in No. 485 (bulletins on February 13rd, 1979), but, unless (for example: solubilizing agent), the aqueous solution that these surfactants form is muddy, in addition to comprise other solvent, the rheological characteristic of these salts also limits the form kind of preparation, and the form of preparation can be given beautiful impression.
Have found that the diamidogen MAP that some is new and the surface activator composition of the transparent and stable that some contains these salt can be made stable normal pressure aerated foam at an easy rate.These foams have good washability and cleaning action, and gentle nonirritant stays residual film hardly at the skin surface that is cleaned.These compositionss are homogeneous, can be made into wet or do, and are stable or decompose fast, and are applicable to multiple skin-protection product from angle of aesthetics.
One of main purpose of the present invention is to introduce the preparation method of moisture skin cleansing compositions, described compositions is made by new diamidogen MAP of the present invention, this salt can also can spray from the aerosol device from hand held extruding foaming device and produce useful foam, in addition, it can scrap device by blocking device.
Another object of the present invention provides surfactant and foaming surfactant compositions, and it will produce the foam of metastable or collapsible package, and most preferred embodiment of the present invention provides low-density skin clean foam.
Another object of the present invention provides cream-colored foamy, and dermal sensation is good, easily rinsing, and can keep the surfactant and the composition, foam of skin elasticity.
Another object of the present invention provides a kind of surfactant and surface activator composition, and they need not to add volatilizer to skin and eyes nonirritant, thereby has also just avoided container explosion and corrosive danger.
A further object of the invention provides a kind of composition, foam, if said composition is charged in the foam device of soft shell of hand held, the foamy power of required generation is little (that is, less than about 15 pounds/inch 2) and be easy to use into ordinary person.
The conspicuous for those skilled in the art purpose of above-mentioned purpose and those can reach by chemical compound described herein and compositions.
Of the present inventionly comprise that its structural formula is as follows to the bland diamidogen MAP of application on human skin:
Figure 911020241_IMG2
Wherein R is a hydrophobic group, or the condensation product of hydrophobic group and oxirane, and R preferably has the alkyl or alkenyl of about 10～18 carbon atoms, X 1And X 2Be selected from separately: hydrogen, alkali metal, ammonium, replacement ammonium (for example: oxyalkylated ammonium, alkylammonium, oxyalkylated fatty amine, the amine of many ethoxyquins) and Alkylenediamine, but X 1And X 2In must have at least one to be the Alkylenediamine of whole hydroxyalkylations.
Disclosed compositions comprises these diamidogen MAP.
The sesquialter alkylphosphonic is not within the scope of the invention.
Unless specialize, in the literary composition all mark, percent and ratio all by weight, all mensuration is all carried out under 25 ℃.
Surfactant compounds structural formula of the present invention is as follows:
Figure 911020241_IMG3
Wherein R is a hydrophobic group, or the condensation product of hydrophobic group and oxirane, and R preferably has the alkyl or alkenyl of about 10～18 carbon atoms, X 1And X 2Be selected from following groups separately: hydrogen, alkali metal, ammonium, replacement ammonium (for example: oxyalkylated ammonium, alkylammonium, oxyalkylated fatty amine, the amine of many ethoxyquins) and Alkylenediamine, but X 1And X 2In must have at least one to be the Alkylenediamine of whole hydroxyalkylations.
MAP of the present invention can prepare with known method.For example by method with long-chain fatty alcohol (or condensation product of long-chain fatty alcohol and ethylene oxide) and phosphorus esterification reagent (for example: phosphoric anhydride or phosphoryl chloride phosphorus oxychloride) reaction.Distinguished already, a pair product that produces in this process is a dialkyl phosphate, and this ester water solublity and foam performance are poor.Its structural formula is as follows:
Wherein R is a hydrophobic group, or the condensation product of hydrophobic group and oxirane, and R preferably has the alkyl or alkenyl of about 10～18 carbon atoms, X 3Be selected from: hydrogen, alkali metal, ammonium, replacement ammonium are (for example: oxyalkylated ammonium, alkylammonium, oxyalkylated fatty amine, the amine of many ethoxyquins) and Alkylenediamine, the R condensation product of the ethylene oxide of hydrophobic group and about 1～10mol(preferably about 1～4mol) preferably.
Preferably about 99: 1～70: 30 of the phosphatic weight ratio of diamidogen MAP and dialkyl group, more preferably about 100: 0～90: 10, most preferred ratio is 100: 0 substantially, but it is different with monoamine, alkali or ammonium phosphate salt, two amine phosphates of these diester have unique water solublity, thereby conflict with device discussed here and not conference of preparation generation.
Surfactant of the present invention is specially adapted to the direct Betengent product that contacts for a long time with skin, for example, facial cleansing agent, shampoo and synthetic detergent bar fancy soap, this is because it has extremely strong foaming capacity especially, and can not cause pachylosis, this surfactant also can be used as dishwashing detergent liquid, and the composition of cleanser and toothpaste needing to be particularly useful for the occasion of transparent composition.
Saturated and the unsaturated alkyl (R) that contains 10～18 carbon atoms is a straight chain, side chain or alicyclic (as: decyl, undecyl, dodecyl, tridecyl, myristyl, pentadecyl, cetyl, heptadecyl and octadecyl) and corresponding alkene class unsaturated group, above-mentioned alkyl involved form in compositions can be single or the bonded form of several groups.The saturated hydrocarbyl and the unsaturated alkyl that contains 16 carbon atoms that especially preferably contain 10～14 carbon atoms.Here also preferentially select for use each molecule to have the saturated or unsaturated alkyl of the ethylene oxide of about 1～10 unit (preferably about 1～4 unit).
X among the present invention 1And X 2Preferred alkali-metal example has: lithium, sodium and potassium.
X among the present invention 1And X 2The alkylammonium of representative or the alkylammonium of replacement are the cationes that is produced by amine, in the process of preparation MAP of the present invention, carry out behind the neutralization procedure in the corresponding phosphoric acid and form salt.Corresponding amine is primary amine, secondary amine and the tertiary amine with alkyl of 1～4 carbon atom, and abovementioned alkyl can further be replaced, and is particularly replaced by hydroxyl.As for amine, the example of enumerating here has: dimethyl-ethanolamine, methyl diethanolamine, trimethylamine, triethylamine, dibutyl amine, butyl dimethylamine, monoethanolamine, diethanolamine, triethanolamine, isopropyl dimethylamine and isopropyl alcohol amine.Preferred amine is monoethanolamine, diethanolamine and triethanolamine.A particularly preferred amine is triethanolamine.Other useful amine comprises arginine, lysine, one, two or triisopropanolamine, N, N-three (methylol) aminomethane, diglycolamine, glycosamine, amino methyl propanol and amino methyl propane diol.(BASF AG produces, and trade name is respectively Tetronic by ethylene oxide and third alkylene oxide among the present invention With Tetronic R
Figure 911020241_IMG6
) and the amine of many ethoxylations (Armak company produces, trade name: Ethomeen
Figure 911020241_IMG7
) deutero-copolymer also is available.
Alkylenediamine general formula of the present invention is as follows:
R 1R 2N…R 3…NR 4R 5
Wherein, R 1, R 2, R 4And R 5The hydrogen of respectively doing for oneself; Contain the alkyl of 1～4 carbon atom or contain 1～4 carbon atom hydroxyalkyl or dihydroxyalkyl; Perhaps R 4And R 5Form saturated five yuan or hexa-member heterocycle together, this ring can be replaced by oxygen or hydroxyalkyl again; R 3Representative contains the alkylidene or the hydroxyl alkylidene of 2～4 carbon atoms; While R 1, R 2, R 3, R 4And R 5In must have at least a group to contain a hydroxyl at least.
These chemical compounds are in British patent the 1st, 513, and are fully open in No. 053 (on June 7th, 1978 is open).
In addition, the useful specific amine of a class is the N with following structure, N-four (hydroxyalkyl) ethylenediamine:
Wherein, R 1Be the alkylidene that contains 2～4 carbon atoms, R is hydrogen or the alkyl that contains 1～6 carbon atom, and n gets 1～4.The molecular weight of above-mentioned diamidogen is less than about 1700 for well, less than about 1200 better, less than about 800 just better, less than about 500 the bests.
Although also will provide some other example below, the preferred examples of four (hydroxyalkyl) ethylenediamine is a compound N, N, N ', N '-four (2-hydroxypropyl)-ethylenediamine, this chemical compound has sale on market, trade name be Quadrol or Neutrol TE(the two be BASF Wyandotte company and produce)
The example of the diamidogen MAP that the present invention is used comprises (but being not limited thereto):
Tetrahydroxypropyl ethylenediamine-coco group phosphate;
Tetrahydroxypropyl ethylenediamine-lauryl phosphate;
Tetrahydroxypropyl ethylenediamine (ethoxylation)-lauryl phosphate;
Tetrahydroxypropyl ethylenediamine-iso stearyl phosphate;
Tetrahydroxypropyl ethylenediamine-stearyl phosphate;
Tetrahydroxypropyl ethylenediamine (ethoxylation)-stearyl phosphate;
Tetrahydroxypropyl ethylenediamine-myristyl phosphate;
Tetrahydroxypropyl ethylenediamine (ethoxylation)-myristyl phosphate;
Tetrahydroxypropyl ethylenediamine-oleoyl phosphate;
Tetrahydroxypropyl ethylenediamine-palmityl phosphate;
Tetrahydroxypropyl ethylenediamine (ethoxylation)-palmityl phosphate;
Tetrahydroxypropyl ethylenediamine-octyl group phosphate;
Tetrahydroxypropyl ethylenediamine (ethoxylation)-octyl group phosphate;
Tetrahydroxypropyl ethylenediamine-Ya undecyl phosphate;
Tetrahydroxypropyl ethylenediamine-Ya tridecyl phosphate;
Tetrahydroxypropyl ethylenediamine-(methyl myristyl) phosphate;
Tetrahydroxypropyl ethylenediamine-(isopropyl lauryl) phosphate;
Tetrahydroxypropyl ethylenediamine-(isodecyl neopentyl) phosphate;
Tetrahydroxypropyl ethylenediamine-cetyl phosphate; With
Tetrahydroxypropyl ethylenediamine-(isopropyl myristyl) phosphate;
Compositions of the present invention comprises:
(a) about 0.1～99.0% one or more diamidogen MAP of the present invention; With
(b) about 1.0～99.0% detergent carriers
Preferred compositions comprises the mixture of diamidogen MAP, and wherein R is selected from C 12～C 14Alkyl or alkenyl and C 16～C 18Alkyl or alkenyl (the perhaps condensation product of these groups and about 1～10mol oxirane); The ratio of described corresponding salt is about 80: 20～20: 80, preferred about 60: 40～40: 60, and most preferably from about 55: 45～45: 55.
But present composition local application promptly, directly applies compositions or is sprayed on epidermal tissue or the epithelial tissue.Such compositions can be made into following form: foam, washing liquid, Emulsion, ointment, solution, gel or solid.Compositions very preferably comprises MAP in soap matrix (that is, liquid and solid).These topical compositions comprise the MAP of safe and effective amount, and are usually about 0.1～99%, preferably about 1%～10%, and the diamidogen single alkyl phosphonic acid salt content in the bar compositions is very high usually, promptly more than 80%.On the ordinary circumstance, carrier is natural Organic substance or solution or aqueous emulsion, and can make the diamidogen MAP disperse, dissolve or be suspended in wherein.Carrier can comprise pharmaceutically acceptable softening agent, skin penetration enhancer, coloring agent, spice, emulsifying agent, thickening agent and solvent.Be the detailed description of these forms below:
1. washing liquid
Washing liquid can comprise the MAP of safe and effective amount; Consumption is about 0.1～25%, preferred about 3%～15% of a softening agent; Counterbalance is a water, C 2Or C 3Alcohol, or the mixture of water and alcohol, the example of suitable softening agent has:
(1) hydrocarbon ils and chloroflo, for example: mineral oil, vaseline, paraffin, ceresin, ceresine, microwax, polyethylene and perhydrogenate squalane.
(2) silicone oil, for example: polydimethylsiloxane, methyl phenyl silicone, water solublity and pure dissolubility silicon-alcohol copolymer.
(3) triglycerides and oil, for example: from fat and oil that plant, animal and marine organisms derive and, concrete example has: Oleum Ricini, safflower oil, Oleum Gossypii semen, Semen Maydis oil, olive oil, cod liver oil, almond oil, American Avocado Tree oil, Petiolus Trachycarpi oil, Oleum sesami and Oleum Glycines.
(4) aceto-glyceride, for example: acetylation glycerol-acid esters
(5) ethoxyquin glyceride, for example ethoxyquin glycerol-stearate.
(6) here, it is particularly useful to have fatty acid alkyl esters, fatty ester methyl ester, isopropyl ester and a butyl ester of 10～20 carbon atoms.For example: lauric acid hexyl ester, lauryl dissident ester, Palmic acid dissident ester, isopropyl palmitate, decyl oleate, Ceraphyl 140A, the stearic acid hexadecyl ester, stearic acid ester in the last of the ten Heavenly stems, isostearic acid isopropyl ester, diisopropyl adipate, adipic acid two dissident's esters, adipic acid two hexadecyl esters, Dermol DIPS, Lauryl lactate, lactic acid 14 esters and cetyl lactate.
(7) has the fatty acid alkenyl esters of 10～20 carbon atoms, for example: myristic acid grease, hard ester acid grease and Cetiol.
(8) has the fatty acid of 9～22 carbon atoms.Suitable example has: n-nonanoic acid, lauric acid, myristic acid, Palmic acid, stearic acid, isostearic acid, hydroxystearic acid, oleic acid, linolenic acid, ricinoleic acid, arachidonic acid ， behenic acid and erucic acid.
(9) have the aliphatic alcohol of 10～22 carbon atoms, suitable example has: lauryl alcohol, myristyl alcohol, spermol, hexadecanol, stearyl alcohol, isooctadecanol, hydroxyl stearyl alcohol, oleyl alcohol, Semen Ricini alcohol ， behenyl alcohol, the pure and mild 2-octyl dodecanol of mustard.
(10) fatty alcohol ether, the B oxidation fat alcohol that contains 10～20 carbon atoms comprises the lauryl alcohol, spermol, stearyl alcohol, isooctadecanol, oleyl alcohol and the cholesterol that are linked with 1～50 second oxygen groups or 1～50 propylene oxygen groups or their mixture.
(11) ether-ester, for example fatty acid ester of B oxidation fat alcohol.
(12) lanoline and derivant thereof are derived and the example of the softening agent that comes has: lanoline, lanolin oil by lanoline; lanolin wax; lanolin alcohol, lanolin fatty acid, isopropyl lanolate; the ethoxyquin wool grease; the ethoxyquin lanonol, ethoxyquin cholesterol, the third oxidation lanolin alcohol; acetylated lanolin; acetylated lanolin, linolenic acid lanoline alcohol ester, ricinoleic acid lanoline alcohol ester; the acetate of ricinoleic acid lanoline alcohol ester; the acetate of ethoxyquin alcohol ester, hydrogenolysis lanoline, ethoxyquin hydrogenated lanolin; ethoxyquin sorbitol lanoline and liquid and semisolid lanoline absorption alkali.
(13) polyhydroxy-alcohol and polyether derivative, for example: propylene glycol, dipropylene glycol, polypropylene glycol (M.W.2000～4000), POA, polyoxygenated propylidene polyoxygenated ethylidene glycol, glycerol, ethoxyquin glycerol, glycerol propoxylate, sorbitol, ethoxyquin sorbitol, hydroxypropyl sorbitol, Polyethylene Glycol (M.W.200～6000), methoxyl group gathers ethanol, polyethylene glycol oxide homopolymer (M, W100,000-5,000,000), poly alkylene glycol and derivant, hexanediol (2-methyl-2,4,-pentanediol), 1,3 butylene glycol, 1,2, the 6-hexanol, ethohexadiol USP(2-ethyl-1, the 3-hexanol), C 15-C 18The polyoxygenated ethidene derivant that connects glycol and trimethyl propane.
(14) polyhydroxy alkyl ester, satisfied former polyhydroxy alkyl ester has: ethylene glycol-fatty acid ester and di fatty acid ester, diethylidene glycol-fatty acid ester and di fatty acid ester, Polyethylene Glycol (M.W.200-6000)-fatty acid ester and di fatty acid ester, propylene glycol-fatty acid ester and di fatty acid ester, polypropylene glycol 2000-oleate, polypropylene glycol 2000-stearate, ethoxyquin propylidene propylene glycol-fat acid ester, glycerol-fatty acid ester and di fatty acid ester, polyglycereol many fatty acid ester, ethoxyquin-tristerin, 1,3-butanediol-stearate, the 1,3 butylene glycol distearate, the many alcohol fatty acid esters of polyoxygenated ethylidene, Span and polyoxygenated ethylidene Span.
(15) wax ester, Cera Flava for example, spermaceti, myristic acid myristinate, stearic acid stearyl ester.
(16) Cera Flava derivant, for example: polyoxygenated ethylidene sorbitol Cera Flava.They are Cera Flava and the multiple product that contains the different ethoxyquin sorbitol of ethylene oxide amount, are the ether-ester mixture.
(17) vegetable wax comprises Brazil wax and candelilla wax.
(18) phosphide, for example lecithin and derivant thereof.
(19) sterol, for example: cholesterol, cholesterol aliphatic ester.
(20) amide, for example: fatty acid amide, ethoxyquin fatty acid amide, solid fatty acid alkanolamide.
Washing liquid still can contain the emulsifying agent of about 1%～10%(preferably about 2%～5%, and emulsifying agent can be nonionic, anion or cationic.Comparatively the example of Man Yi nonionic emulsifier comprises the fatty acid alcohol that contains 10～20 carbon atoms, have the aliphatic alcohol of 10～20 carbon atoms and the condensation substance of 2～20mol oxirane or expoxy propane, the alkylphenol of 6～12 carbon atoms and the condensation substance of 2～20mol oxirane are arranged, one and two fatty ester alcohol of oxirane in alkyl chain; One and di fatty acid ester of ethylene glycol (wherein fatty acid part contains 10～20 carbon atoms); Diethylene glycol; Molecular weight is 200～6000 Polyethylene Glycol; Molecular weight is 200～3000 propylene glycol; Glycerol; Sorbitol; Sorbitan; Polyoxygenated ethylidene Sorbitol; Polyoxygenated ethylidene sorbitan and hydrophilic wax ester.Suitable anion emulsifier comprises fatty acid soaps, for example: sodium, potassium and triethanolamine soap, wherein, fatty acid part contains 10～20 carbon atoms, other suitable anion emulsifier comprises: alkali metal, ammonium or replacement ammonium alkyl sulfate, alkylaryl sulfonates and alkyl ethoxy ether sulfonate wherein have 10～30 carbon atoms at moieties.The alkyl ethoxy ether sulfonate contains 1～50 ethylene oxide unit.But, distinguished already that some anion emulsifier can make the preparation muddiness, thereby, do not recommend to use anion emulsifier here.
The counterbalance of washing liquid is water or C 2Or C 3Alcohol, or the mixture of water and alcohol.The preparation of washing liquid mixes all components exactly simply.MAP is dissolved in the mixture, can adds selectable components commonly used, a kind of thing of dosing is a thickening agent, and the consumption in preparation is about 1%～10%.The example of suitable thickening agent comprises: crosslinked carboxy polymethylene polymer (fully neutral), and Magnesiumaluminumsilicate, carboxymethyl cellulose, hydroxyethyl-cellulose, acrylate copolymer are (for example: Rohm ﹠amp; The Acrysol ICS-1 that Hass company produces), Polyethylene Glycol, gum tragacanth, Ka Lanya glue (Kharaya gum), synthesising biological polymeric gel and Bentonite.Here do not recommend to use cationic polymer (as guar gum).
2. Emulsion
The present composition also can be made into the form of Emulsion.Emulsion comprises the MAP of safe and effective amount; About 0.1～95%(preferably about 10%～25%) softening agent; Counterbalance is a water.Softening agent mentioned above also can be used for Emulsion.As mentioned before, Emulsion can contain examples of suitable emulsifiers arbitrarily.When comprising emulsifying agent, its content is about 3%～50%, is preferably about 5%～20%.
3. solution
The present composition also can be made into the form of solution, and solution comprises the MAP of safe and effective amount, contains approximately 0.01%, about at most 50% usually at least, preferably contains about 0.1%～10%; Counterbalance is water or suitable organic solvent, and the suitable Organic substance that is used as the part of solvent or dicyandiamide solution is: propylene glycol, Polyethylene Glycol (M.W.200～1000), polypropylene glycol (M.W.425-2025), butanediol, glycerol, sorbitol ester, 1,2, the 6-hexanetriol, ethanol, isopropyl alcohol, diethyl tartrate., butanediol and their mixture.
This solution can be directly used in skin, and in the following pressurizing unit of perhaps it can being packed into, perhaps the form with aerosol is sprayed from automiser spray, perhaps is used for gargling as mouth-wash.Can also contain in the aerosol combination and have an appointment 25%～80%, preferably about 30%～50% suitable volatilizer, for example: the chloride of low molecular weight hydrocarbon, fluoride and fluorochloride.Nitrogen oxide, carbon dioxide, butane and propane can also be used as volatilizer gas.The consumption of volatilizer will be enough to discharge from container the thing of the inside.
Extrude foaming agent packing for people know, disclose example in the following patent (this paper document incorporated by reference): on January 9th, 1973 was announced, and authorized No. the 3rd, 709,437, the United States Patent (USP) of Wright; On February 10th, 1976 bulletin is authorized No. the 3rd, 937,364, the United States Patent (USP) of Wright; On May 10th, 1977 bulletin is authorized No. the 4th, 022,351, the United States Patent (USP) of Wright; On April 3rd, 1979 bulletin is authorized No. the 4th, 147,306, the United States Patent (USP) of Bennett; On January 22nd, 1980 bulletin is authorized No. the 4th, 184,615, the United States Patent (USP) of Wright; On July 8th, 1986 bulletin is authorized No. the 4th, 598,862, United States Patent (USP) and on the October 7th, 1986 of Rice and is announced, No. the 2nd, 604,622, the French Patent (FRP) of authorizing people's such as Grogan No. the 4th, 615,467, United States Patent (USP) and authorizing Verhulst on April 8th, 1988.
Need not be in the said vesse (packing) with volatilizer, thereby be safe for consumer and environment.They almost can make any surface activator composition become foam, although be not the foam adjuvant that must add stable foam, had better add.Container operate as normal foam in some compositions, use foam adjuvant even meeting real that it is anti-, because must be interrupted.Compositions is contained into container (squeeze bottle), be used for application of force squeeze receptacle, compositions is extruded by foam generation head or other foam-making apparatus, mix with air in this device place compositions, make the even more also concordance of control foam of foam by a homogenization mechanism then, discharge uniform normal pressure aerated foam then.
Making the activatory minimum pressure of extrusion pressing type foaming agent is about 1 pound/inch 2(gauge pressure) generally is about 2 pounds/inch 2The size of passage, viscosity of compositions etc. are relevant in (gauge pressure), minimum pressure and dispenser.
In general, foamy density should be at about 0.002g/cc, and between about 0.25g/cc, preferably about 0.01g/cc～0.12g/cc is preferably between about 0.02g/cc～0.07g/cc.
Carrier in the mouth-wash is the mixture of ethanol and water normally.Consumption of ethanol is carrier about 5%～60% normally, and is preferably about 5%～25%, and remainder then is a water.This gargle composition also can contain other optional member, emulsifying agent as indicated above, flavoring agent, sweetener and wetting agent.The preparation method of used other mouth-wash preparation of the present invention is open in references to U.S. patent that the present invention quotes the 4th, 323, No. 551 (April 6 nineteen eighty-two, bulletin was authorized Parran).
4. gel
The present composition can be made into gel form, just can as long as above-mentioned liquid composite mixed with suitable thickening agent.The example of suitable thickening agent is enumerated at one joint of washing liquid above.
Gel compositions contain the MAP of safe and effective amount; About 0.5%～20%(preferably about 1%～10%) thickening agent; Counterbalance is a water.
5. solid
The present composition also can be made into solid form, and for example: bar compositions, said composition contain the MAP and about 0.01%～90% of safe and effective amount) softening agent mentioned above.Said composition also can contain about 0.1%～20%(preferably about 5%～15%) suitable thickening agent, and emulsifying agent (also can not containing) and water.Aforementioned thickening agent also suits with respect to washing liquid.
6. soap
The present composition also can be made into liquid or solid (for example strip) soap matrix.This based composition comprises the MAP about 0.1%～99% of safe and effective amount and about 1%～99% previously described excipient.Can contain (also can not containing) aforesaid suitable emulsifying agent in the soap.When comprising emulsifying agent, its content approximately is 10%～50%
7. dentifrice
The present composition also can be made into dentifrice.Such dentifrice (especially toothpaste) comprises the MAP of safe and effective amount, and content is approximately 0.1%～20% of composition weight.Usually dentifrice composition contains grinding-material, saponifier, binding agent, wetting agent, flavouring agent and sweetener.Suitable dentifrice composition that the present invention is used and preparation method thereof is fully open in references to U.S. patent that the present invention quotes the 3rd, 535, No. 421 (on October 20th, 1970, bulletin was authorized people such as Briner).
8. shampoo
The present composition also can be made into the pattern of shampoo.Described shampoo comprises the diamidogen MAP (content is approximately 0.1%～99%) of safe and effective amount; About 5%～60% synthetic surfactant and equilibrium water.Also can use regenerated surfactant, still, this regenerated surfactant should be through aforesaid diamidogen neutralization.
Can contain many unsubstantiality optional members in the shampoo.These conventional optional members are well known to those skilled in the art.For example: antiseptic (as: benzylalcohol, aethyl parabenum, propyl parabene and imidazolidinyl urea); Cationic surfactant [as: cetyl trimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride and two (partially hydrogenated fat) alkyl dimethyl ammonium chloride]; Thickening agent and viscosity modifier [as: the diglycollic amide of long-chain fatty acid (as: PEG 3 lauramides), the block polymer of oxirane and expoxy propane, sodium chloride, sodium sulfate, polyvinyl alcohol and ethanol]; PH regulator (as: citric acid, succinic acid, phosphoric acid, sodium carbonate); Spice; Dyestuff; And sequestering agent (as: editic acid sodium).The common consumption of these reagent the about 0.01%～10% of composition weight that respectively do for oneself is preferably about 0.5%～5.0%.
For the attractability, the versatility that increase the present composition with shelf-life, can also add minor constituent, can add acceptable dyestuff on spice and the water solublity pharmacy or food colour attractability with enhancing composition.Thereby antibacterial and antimicrobial can be used for avoiding compositions to be shelf-lifeed by mycete or germ contamination prolongation.Conventional antibacterial can be included in the said composition, and content is approximately 0.1%～4%, is preferably about 0.2%～1%.The antibacterial that typically is applicable to the present composition has: 3, and 4-two and 3,4 ', 5-tribromo salicylaniline; 4,4 '-two chloro-3-(trifluoromethyls) carbanilide; 3,4,4 '-trichlorocarbanilide; Phenyl phenol or phenoxypropanol; Chloro hexene salt; Own amidine salt, chlorophenol DP300; Salicylic acid; To chloro-m-xylene alcohol; Octopirox and their mixture.The pH value of general purpose skin cleansing compositions about 5.0～8.0 is comparatively desirable.In case of necessity, available citric acid or lactic acid reduce its pH value, and concerning the skin cleaner that is used for sensitive skin surface (around vagina and anus), ideal pH value is about 6.5.Under the situation that does not deviate from basic conception of the present invention, can carry out above-mentioned and other some less changes.
The former character of the foam that is produced has determined the purposes of the present composition.In order to make foam can be used as skin cleaner, it must uniformity, spreadability is good and cleaning power is strong.
Foaminess and wettability depend on the surface tension of skin cleaner.Between about 20～70 dynes per centimeter of the surface tension of the present composition.For general skin cleansing compositions, be preferably about 23～50 dynes per centimeter, surface tension has wettability and spreadability preferably in this scope than the liquid composite of low value, and foaminess has also improved.The higher composition, foam of surface tension can provide more stable foam usually, but the power that also difficulty foams and exruded foams is required simultaneously is also bigger.
The outstanding advantage of foaming composition of skin cleanser of the present invention is that they only stay the minute quantity residual surfactant on skin.This is low the causing of part foam density few owing to the content of surfactant in skin cleansing compositions and that produce.Present composition foamed cleaning power is strong, only stays the residual surfactant of minute quantity when the more important thing is with its rinsing or wrinkle removing skin, thereby has kept skin elasticity, and reduced the moisture loss that sees through epidermis.
The cleaning power of above-mentioned aerated foam is directly related with the cleaning power that produces foamy surfactant solution itself.
Following limiting examples is used for illustrating the present invention, wherein includes neccessary composition and optional member.These embodiment should only regard as explanation of the present invention, are used for limiting the scope of the invention by no means.
Embodiment 1
With steam bath the 1mol monoalkyl phosphoric acid esters is heated to 50 ℃ of fusings.In another beaker with 1mol N, N, N ', N '-four (2-hydroxypropyl)-ethylenediamine (BASF AG, trade name Quadrol) is heated to 50 ℃ of one-tenth and can pours into attitude.
The phosphate ester of fusing is added N, N, N ' lentamente, in N '-four (2-hydroxypropyl)-ethylenediamine, be that 5.0～9.0(is preferably 7.0 to pH value), gained N, N, N ', N '-four (2-hydroxypropyl)-ethylenediamine-Tryfac 5573 cool off the yellow solid of clear rut.
This solid can use by the solid strip, also can be used as the raw material of producing milk or gel-like prod.
Use about 0.5g above-mentioned substance on skin the foamed cleanser with good cleaning capacity and cleaning function will be provided, there is residual film in its gentle nonirritant hardly on the surface that is cleaned of skin.
Following substances or its mixture replacing-Tryfac 5573 with equivalent obtain similar substantially result :-coco group phosphate ester;-Tryfac 5573;-iso stearyl phosphate ester;-stearyl phosphate ester;-myristyl phosphate ester;-oleoyl phosphate ester;-palmityl phosphate ester;-octyl phosphate ,-undecyl phosphate ester ,-three decene base phosphate esters;-(methyl myristyl) phosphate ester;-(isopropyl lauryl) phosphate ester ,-(isodecyl neopentyl) phosphate ester ,-cetyl phosphate ester and-(isopropyl myristyl) phosphate ester.
Embodiment 2
The following compositions combination is made the facial cleansing compositions of local application:
Component %(W/W)
N, N, N ', N '-four (2-hydroxypropyl)-second
Diamidogen-Tryfac 5573 2.500
Butanediol 2.500
Nipagin 0.250
Propyl parabene 0.150
Cortex cocois radicis potassium (hydrolyzed animal protein) (1)0.032
Glycerol 2.000
Aloe 0.500
Spice 0.050
Pigment 0.170
The synthesising biological polymeric gel (2)0.050
Water is an amount of
Annotate: (1) Henkel company produces, trade name Lamepon S
(2) Kelco company produces, trade name Keltrol T
Embodiment 3
Following composition combination is made the facial cleanser composition of local application:
Component %(W/W)
N, N, N ', N '-four (2-hydroxypropyl)-second
Diamidogen-Tryfac 5573 27.00
Lauric acid 4.000
N, N, N ', N '-four (2-hydroxypropyl)-second
Diamidogen (1)4.000
Carboxy vinyl polymer (2)0.200
Glycerol 8.000
Sorbitol 2.000
Water is an amount of
Annotate: (1) BASF-Wyandotte company produces, trade name Quadrol
(2) B.F.Goodrich company produces, and trade name Carbopol 941
Embodiment 4
Following composition combination is made the compositions of washing one's face of local application:
Component %(W/W)
N, N, N ', N '-four (2-hydroxypropyl)-second
Diamidogen-Tryfac 5573 3.000
Lauric acid 1.000
Cortex cocois radicis potassium (hydrolyzed animal protein) 0.500
Hydroxyethyl-cellulose 2.000
Nipagin 0.100
Propyl parabene 0.100
Glycerol 3.000
Spice 0.100
Pigment 0.001
Water is an amount of
Embodiment 5
Following composition combination is made the gel combination of washing one's face of local application:
Component %(W/W)
N, N, N ', N '-four (2-hydroxypropyl)-second
Diamidogen-Tryfac 5573 10.000
Aromatic acid polymer 0.500
N, N, N ', N '-four (2-hydroxypropyl)-second
Diamidogen 1.000
Glycerol 5.000
Lauric acid 2.000
Water is an amount of
Embodiment 6
Following composition combination is made the shaving foam composition of local application:
Component %(W/W)
N, N, N ', N '-four (2-hydroxypropyl)-second
Diamidogen-Tryfac 5573 7.000
N, N, N ', N '-four (2-hydroxypropyl)-second
Diamidogen-palmityl phosphate ester 7.000
Lauric acid 1.500
Palmic acid 1.500
N, N, N ', N '-four (2-hydroxypropyl)-second
Diamidogen 1.500
Spice 0.100
Aloe 2.000
Water is an amount of
Embodiment 7
The following ingredients combination is made the compositions of washing one's face of local application:
Component %(W/W)
N, N, N ', N '-four (2-hydroxypropyl)-second
Diamidogen (the 1mol ethoxyquin)
-Tryfac 5573 2.500
Butanediol 2.500
Nipagin 0.250
Propyl parabene 0.150
Cortex cocois radicis potassium (hydrolyzed animal protein) (1)0.032
Glycerol 2.000
Aloe 0.500
Spice 0.050
Pigment 0.170
The synthesising biological polymeric gel (2)0.050
Water is an amount of
Annotate: (1) Henkel company produces, trade name Lamepon S
(2) Kelco company produces, trade name Keltrol T

Claims (10)

1, the low composition of detergent of a kind of stimulating effect is characterized in that containing:
(a) one or more of 1%～30% have the surfactant compounds of the following chemical structure formula I or (II):
Figure 911020241_IMG1
Wherein R is the condensation product that contains the alkyl or alkenyl of 10～18 carbon atoms or they and 1～10mol oxirane; X 1, X 2And X 3Be selected from separately: hydrogen, alkali metal, ammonium replaces ammonium and Alkylenediamine, but X 1And X 2In to have one at least be the Alkylenediamine of complete hydroxyalkylation and (I) formula chemical compound and the ratio of (II) formula chemical compound is 100: 0～90: 10,
(b) 99%～70% detergent carrier.
2, according to the described composition of detergent of claim 1, wherein said replacement ammonium is selected from: oxyalkylated ammonium, alkylammonium, the amine of oxyalkylated fatty amine and many ethoxylations.
3, according to the described composition of detergent of claim 2, wherein R is the alkyl or alkenyl that contains 10～14 carbon atoms, and described alkali metal is sodium, potassium or lithium or their mixture.
4, according to the described composition of detergent of claim 3, wherein said alkylammonium is selected from: trimethyl ammonium, triethyl ammonium, dibutyl ammonium, butyl Dimethyl Ammonium and isopropyl Dimethyl Ammonium, or their mixture, and the alkylammonium of described replacement is the hydroxyalkyl ammonium.
5, according to the described composition of detergent of claim 4, wherein X 1And X 2Have at least one to be the Alkylenediamine of hydroxyalkylation, wherein alkylidene contains 2～6 carbon atoms; Described Alkylenediamine is by the alkylene oxide that contains two carbon atoms at least or contains the mixture o-alkylation of the alkylene oxide of two or more carbon atoms.
6, according to the described composition of detergent of claim 5, wherein X 1And X 2Have at least one to be N, N, N ', N '-four (2-hydroxypropyl)-ethylenediamine.
7, according to the described composition of detergent of claim 6, its form is soap, Emulsion, solution, mouth-wash, toothpaste or shampoo.
8, according to the described composition of detergent of claim 1, described compositions is made up of diamidogen single alkyl phosphonic acid salt mixture, and wherein R is selected from: C 12～C 14Alkyl or alkenyl, C 16～C 18Alkyl or alkenyl, and the ratio of described salt is 60: 40 to 40: 60.
9, according to the described composition of detergent of claim 1, said composition is made up of diamidogen single alkyl phosphonic acid salt mixture, and wherein, R is selected from: C 12～C 14The condensation product of alkyl or alkenyl and 1～10mol oxirane, the ratio of wherein said salt should be 60: 40 to 40: 60 mutually.
10, according to the described composition of detergent of claim 9, wherein R is the alkyl or alkenyl with 10～18 carbon atoms, perhaps R has the alkyl or alkenyl of 10～18 carbon atoms and the condensation product of 1～10mol oxirane, wherein said replacement ammonium is selected from: the amine of oxyalkylated ammonium, alkylammonium, oxyalkylated fatty amine, many ethoxylations, and X wherein 1And X 2Have at least one to be N, N, N ', N '-four (2-hydroxypropyl) ethylenediamine.
CN 91102024 1990-03-27 1991-03-27 Novel surfactants and surfactant compositions Expired - Fee Related CN1029912C (en)

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US6221822B1 (en) 1995-10-30 2001-04-24 Tomah Products, Inc. Detergent compositions having polyalkoxylated amine foam stabilizers
US5719118A (en) * 1995-10-30 1998-02-17 Tomah Products, Inc. Detergent compositions having polyalkoxylated amine foam stabilizers and method for cleaning including stabilized detergent foam
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US3954648A (en) * 1969-12-22 1976-05-04 Pennwalt Corporation Coatings removal composition containing an alkali metal hydroxide, an oxygenated organic solvent, and an amine
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