CN1042745C - Low PH mild personal cleaning bar - Google Patents
Low PH mild personal cleaning bar Download PDFInfo
- Publication number
- CN1042745C CN1042745C CN92101776.6A CN92101776A CN1042745C CN 1042745 C CN1042745 C CN 1042745C CN 92101776 A CN92101776 A CN 92101776A CN 1042745 C CN1042745 C CN 1042745C
- Authority
- CN
- China
- Prior art keywords
- soap
- synthetic surfactant
- cleaning bar
- personal cleaning
- mild personal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000004140 cleaning Methods 0.000 title claims description 47
- 239000000344 soap Substances 0.000 claims abstract description 236
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- 239000004094 surface-active agent Substances 0.000 claims abstract description 53
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 43
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
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- 238000000034 method Methods 0.000 claims description 48
- 239000002253 acid Substances 0.000 claims description 35
- -1 alkyl glyceryl ether Chemical compound 0.000 claims description 32
- 238000011068 loading method Methods 0.000 claims description 29
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- 239000013543 active substance Substances 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- 238000005187 foaming Methods 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 235000021588 free fatty acids Nutrition 0.000 claims description 16
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- 238000010790 dilution Methods 0.000 claims description 12
- 239000012895 dilution Substances 0.000 claims description 12
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 10
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- 239000003995 emulsifying agent Substances 0.000 description 1
- 210000002615 epidermis Anatomy 0.000 description 1
- QDPMLKBAQOZXEF-UHFFFAOYSA-N ethanesulfonic acid;sodium Chemical compound [Na].CCS(O)(=O)=O QDPMLKBAQOZXEF-UHFFFAOYSA-N 0.000 description 1
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 229930195712 glutamate Natural products 0.000 description 1
- 125000005908 glyceryl ester group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- LPTIRUACFKQDHZ-UHFFFAOYSA-N hexadecyl sulfate;hydron Chemical compound CCCCCCCCCCCCCCCCOS(O)(=O)=O LPTIRUACFKQDHZ-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000003165 hydrotropic effect Effects 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229920001206 natural gum Polymers 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 150000002942 palmitic acid derivatives Chemical class 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 235000019633 pungent taste Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 230000008591 skin barrier function Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- NGSFWBMYFKHRBD-UHFFFAOYSA-M sodium lactate Chemical compound [Na+].CC(O)C([O-])=O NGSFWBMYFKHRBD-UHFFFAOYSA-M 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HMHFERXOZSZRML-UHFFFAOYSA-M trimethyl-(3-methyloxiran-2-yl)azanium;chloride Chemical compound [Cl-].CC1OC1[N+](C)(C)C HMHFERXOZSZRML-UHFFFAOYSA-M 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 210000000707 wrist Anatomy 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- C11D9/00—Compositions of detergents based essentially on soap
- C11D9/002—Non alkali-metal soaps
-
- 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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/006—Detergents in the form of bars or tablets containing mainly surfactants, but no builders, e.g. syndet bar
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
- Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Luminescent Compositions (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
- Paper (AREA)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
- Thermotherapy And Cooling Therapy Devices (AREA)
- Bakery Products And Manufacturing Methods Therefor (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
本发明涉及软性人体清洗用香皂，它包括：约20%-50%起泡软性合成表面活性剂和约5%-50%镁皂；其中所述起泡软性合成表面活性剂与所述香皂之比率约为10∶1-0.4∶1。所述香皂在25℃的1%水溶液中的pH值约6.5-8.5。The present invention relates to soft soap for body cleansing, which comprises: about 20%-50% lathering soft synthetic surfactant and about 5%-50% magnesium soap; wherein said lathering soft synthetic surfactant is combined with said The soap ratio is about 10:1-0.4:1. The soap has a pH of about 6.5-8.5 in a 1% aqueous solution at 25°C.
Description
The present invention relates to soft human body cleans with perfumed soap and manufacture method thereof.
The body-cleansing agents made from soft surfactivity cleaning perfumed soap has become the people's attention center.The processing characteristics of this perfumed soap also becomes people's the center of interest.The smearing character even become bigger the center of interest of this perfumed soap.
Some the associated problem of soft perfumed soap that is made of synthetic detergent is the processibility of perfumed soap, solidity, smearing property and soften.The problem of preparing this perfumed soap is not limited to the performance characteristic of finished product perfumed soap.Some soft table of many usefulness and perfumed soap that promoting agent is made is difficult to make.
On the contrary, the making of purer soap but is sophisticated technical process, and it comprises grinding, mold pressing and molding.Coconut/Tallow, beef soap when when heating plasticity-fairly good, therefore easily mold pressing and molding under lower pressure.
Most synthetic detergent and washing composition filler mixture are not mouldable, and the mechanical means of making must specialized designs.Please referring to U.S. Patent No. 2,678,921, (on May 18th, 1954 was authorized J.A.V.Turck, Jr).
Ideal processing should be fast, and does not have the problem of grinding, mold pressing and the moulding of molding perfumed soap.Most soft perfumed soap production process is insufficient in this respect.
Development about synthetic soap should trace back to World War II, U.S. Patent No. 2,432,169, and Hoyt has described and has a kind ofly contained soap and as the alkylbenzene sulfonate of promoting agent with most ofly be the soap of W-Gum as tackiness agent; U.S. Patent No. 2,988,511, (authorizing Mills and Korpi on June 13rd, 1961) described non-the smearing that contains alkyl glyceryl ether sulfonate, sodium and magnesium soap and tackiness agent and used soap.U.S. Patent No. 2,982,735 (was authorized Blinka and Grounds, Jr.) is disclosed a kind of soft soap of washing composition that contains soap, anionic detergent and starch on May 2nd, 1961.
U.S. Patent No. 2,781, the embodiment 19 of 321 (authorizing February 12 nineteen fifty-seven such as Mayhew etc.) discloses a kind of general washing soap of 50% Magnesium Stearate that contains 20% natural gum etc.The table and surfactant system comprises dodecylbenzene sulfonate (embodiment 26-30), this is a kind of harder tensio-active agent.The STPP consumption is 10-15% among people's such as Mayhew the embodiment.
U.S. Patent No. 3,070,547 (authorizing Chaffee on December 25th, 1962) disclose a kind of synthetic soap of potassium synthetic that contains magnesium soap.As if do not have free fatty acids in the soap that Chaffee exemplifies, and the pH value of his used surfactant system is not open among this embodiment, but normally than higher.
U.S. Patent No. 2,987,484 (authorizing Lundberg and Blinka on June 6th, 1961) disclose a kind of laundry soap that contains the mold closing injection moulding of alkyl glyceryl ether sulfonate and 2-acyloxy esilate.Some other purposes and the method for making alkyl glyceryl ether sulfonate are disclosed in United States Patent(USP) Nos. 2,094,489 (authorizing Hulter September 28 nineteen thirty-seven), 2,427,576 (authorizing Smith September 16 nineteen forty-seven); 2,427,577 (authorizing Smith September 16 nineteen forty-seven); 2,989,547 (on June 20th, 1961 authorized to Whyte); 2,999,068 (authorizing Pilcher etc. on September 5th, 1961); With 3,024, in 273 (the authorizing Whyte etc. on March 6th, 1962); Above-mentioned patent documentation is all incorporated this paper into as a reference.
The pliability that should note tensio-active agent can use skin wall bursting test (SkinBarrier destruction test) to measure, and this test is used for the pungency of evaluation form surface-active agent.In this test, tensio-active agent is softer, and the skin wall destroys fewer.The destruction of skin wall is to enter the relative quantity of oozing out the physiological buffer in the sap cavity with isotope-labeled water (3H-H2O) by the percutaneous epidermis of testing liquid to measure.This test is referring to following document: T.J.Franz.J.Invest.Dermatol, 1975,64pp.190-195; U.S. Patent No. 4,673,525 (June 16 in 1987 was authorized Small etc.) and common pending U.S. Patent Application series No.294,832, (Small etc., on January 9th, 1989 submitted to), these documents are quoted for your guidance by this paper.
U.S. Patent No. 2,894,912 (authorize Geitz July 14 nineteen fifty-nine, name is called " 2-isethionate laundry soap ") main laundry soap composed as follows disclosed: 30-70%2-ethylenehydrinsulfonic acid and the water-soluble alkali metal salts washing composition that contains the ester that 6-18 carbon atom and the iodine number mixed fatty acid less than 20 forms, at least 75% has the 12-18 carbon atom and 25% has 6-10 carbon atom at the most in the described mixed fatty acid; The water-soluble foam that 2-10% at least a is selected from following groups increases washing composition salt, i.e. the high fatty alcohol vitriol of basic metal and organic amine, the salt of alkylaryl sulfonate and higher aliphatic lipid acid and taurine; About 1%～9% water; The water-soluble higher fatty acid soap of about 2.5%-25%; And at least a higher fatty acid with about 12-25 carbon atom of 10-40% is as tackiness agent and softening agent, and the soap of above-mentioned composition is at 35 ℃, and the PH that 10% aqueous solution is surveyed is in 6～8 scope.Do not use magnesium soap.
U.S. Patent No. 4,180,470 (authorizing Tokosh etc. on December 25th, 1979) disclose a kind of method for preparing modified version 30-70%2-acyloxy esilate laundry soap, this method has adopted 2～6% alkyl chains to contain the alkoxyl group hydroxypropionate sodium (synonym of alkyl glyceryl ether sulfonate) of 8 to 22 carbon atoms and small amount of sodium chloride.Used the 5%C18 alkyl glyceryl ether sulfonate among the embodiment.The alkyl glyceryl ether sulfonate and the salt that add are the wear-resistant rates that is used to improve soap, and can not influence its bubbling character.
U.S. Patent No. 4,234,464 (authorized Morshauser on November 18th, 1980, name is called " laundry soap composition and tackiness agent thereof "), disclosed a kind of laundry soap in embodiment 6, and it comprises 45%2-coconut oxygen base ethyl sulfonic acid sodium; 5% alkylamide, 37.5% stearic acid, 5.0% hydrogenated tallow glyceryl ester and 1% polymkeric substance JR.Morshauser points out that his laundry soap can contain the soap " and can not cause tangible infringement " up to 5%.
U.S. Patent No. 4,012,341 (authorized Orshitzer etc. on March 15th, 1977, name is called " unique complete synthesis washing shampoo soap " and discloses a kind of perfumed soap that comprises negatively charged ion and nonionic detergent mixture.These embodiment are mainly based on sodium lauryl sulphate, and this is a kind of coarse unsafty tensio-active agent for purposes of the invention.
U.S. Patent No. 3,761,418 (authorized Parran on September 25th, 1973, Jr, title " detergent composition that contains the solids precipitation toughener ") disclose that to comprise main tensio-active agent be that the washing composition of a kind of soap of alkyl-sulphate is formed, this tensio-active agent is unsafty to soft skin clean-out system of the present invention.
The main drawback of most of synthetic surfactant perfumed soap prescriptions is coarse, and foam is few, and smearing property is poor, and owing to toughness causes poor processability.Use high foaming anion surfactant can produce gratifying foam volume.Regrettably the highest blistered anion surfactant is poor aspect processibility in fact.And the gentle blend of some prior art such as coconut/Tallow, beef alkyl glycerylether sodium sulfonate (AGS) is preferably aspect whipability, but because therefore their viscosity or water absorbability are not to process so easily.Should consider that exquisite overall equilbrium is being arranged aspect processibility, soundness, smearing property, flexibility, whipability and the rinsability when being to be appreciated that the tensio-active agent of selecting to be suitable for mild personal cleaning bar.Therefore be to be appreciated that the strict more requirement of preparation mild personal cleaning bar has limited the selection of tensio-active agent, and end formulation has embodied trading off to a certain degree.When sacrificing processibility, cleaning validity, whipability or rinsability, usually can obtain flexibility, otherwise too.When smearing property of sacrifice can obtain processibility often, otherwise too.
Much less, flexibility is good, and smearing property is good, but the prescription of the mild personal cleaning bar of the high-quality that whipability is good and rinsing is good processing is difficult to obtain.
The purpose of this invention is to provide a kind of mold pressing mild personal cleaning bar that improves processibility that has.Another object of the present invention provides a kind of soft perfumed soap with good smearing property.
The 3rd purpose of the present invention is a kind of mild personal cleaning bar of preparation, and this perfumed soap has lower free fatty acid content so that improves the smearing property and the rockiness of perfumed soap.
Other purpose of the present invention may be obvious that by following detailed description.
The present invention is a kind of mild personal cleaning bar, and it comprises: about 20%～50% soft synthetic surfactant of foaming and about 5%～50% magnesium soap; The ratio of soft synthetic surfactant of wherein said foaming and described soap about 10: 1 to about 0.4: 1.Described perfumed soap its pH value in 25 ℃ 1% aqueous solution is about 6.5～8.5.
The present invention relates to a kind ofly, be preferably the mild personal cleaning bar that the mixture of about 10%～45% magnesium soap is made by about 20%～50% soft synthesis of detergent tensio-active agent and about 5%～50% that bubbles.The pH value of this mild personal cleaning bar is about 6.5～8.5.The pH value of perfumed soap is preferably 7～8, preferably regulates with carboxylic acid.Its pH value is under about 25 ℃, measures in 1% the aqueous solution.
The ratio of soft synthetic surfactant and magnesium soap of bubbling is about 10: 1 to about 0.4: 1, is preferably about 5: 1 to 0.5: 1, more preferably about 4: 1 to 0.6: 1.
Term used herein " soft synthetic surfactant bubbles " is meant that the foaming of any tensio-active agent is the same good with " the soft standard alkyl glyceryl ether sulfonate (AGS) " that define at least herein, and it contains a large amount of C
12And C
14Alkyl chain is about 68%C specifically
1225%C
14And 7%C
16AGS.
" non-blistered, non-soil loading thinner, tensio-active agent " is defined as a kind ofly having " low " foamy and being equivalent to C
16-C
18Alkyl glyceryl ether sulfonate tensio-active agent and other C
16-C
18Synthetic surfactant, for example C
16-C
18Alkyl-sulphate etc.These tensio-active agents can obviously not produce foam, but can not impair foam significantly yet.Yet they are improving perfumed soap, are making it to have in the flexing position test (Flex Test) in greater detail and special effect is but arranged aspect high-grade ability hereinafter.They also can be used for improving the characteristic of smearing of perfumed soap.
" soil loading thinner " used herein and " hydrophobic substance " are synonyms, are meant any thinner of energy load dirt, and it is free fatty acids in proper order, paraffin, Fatty Alcohol(C12-C14 and C12-C18) or triglyceride level.Wherein some material as paraffin, is being very effective aspect the raising flexing position test grade, other material, and as free fatty acids, the plasticising that can help to fill a prescription is beneficial to processibility.
Magnesium (Mg) soap can make by using the fatty substance of selecting (free fatty acids and soap class), and the iodine number of these fatty substances is about 0～50, preferably is lower than 15, more preferably is about 0～3.Congealing point (℃) can hang down reach about 15, yet the congealing point that fatty substance and free fatty acids had of preferred soap is about 60～80, preferably is about 35～75, is more preferably 50-70.
The chemical property of some preferred pure saturated acid is listed in the following pure acid table
The sour chain length acid number molecular weight congealing point of pure acid table (℃) capric acid C-10 326 170 laurate C-12 280 200 44.2 nutmegs acid C-14 246 228 54.4 pentadecanoic acid C-15 231 242 palmitic acid C-16 219 256 62.9 Heptadecanoic acide C-17 207 270 stearic acid C-18 197 284 69.6 nonadecylic acid C-19 188 298 arachidic acid C-20 180 312 behenic acid C-22 165 340
The sad C-8 3 capric acid C-10 of the sour chain length % by weight of palmitic acid table (typically) saturated acid 3 laurate C-12 50 nutmegs acid C-14 18 palmitic acid C-16 8 stearic acid C-18 2 unsaturated acids oleic acid C-18=1 14 linoleic acid C-18=2 2 iodine numbers: low 14
High 23 saponification values: low 245
High 255 congealing points, ℃ (lipid acid): low 20
High by 28
Palmitinic acid, coconut acid and tallow fatty acid table provide some chemical property of these acid.
The sad C-8 7 capric acid C-10 of the sour chain length % by weight of coconut acid table (typically) saturated acid 6 laurate C-12 50 nutmegs acid C-14 18 palmitic acid C-16 85 stearic acid C-18 3 unsaturated acids oleic acid C-18=1 6 linoleic acid C-18=2 1 leukotrienes C-18=3 0.5 iodine number: low 7.5
High 10.5 saponification values: low 250
High 264 congealing points, ℃ (lipid acid): low 20
High by 24
Animal tallow BFT table (typically) sour chain length % by weight saturated acid nutmeg acid C-14 3 pentadecanoic acid C-15 0.5 palmitic acid C-16 24 Heptadecanoic acide C-17 1.5 stearic acid C-18 20 unsaturated acids nutmeg olic acid C-14=1 1 palmitoleic acid C-16=1 2.5 oleic acid C-18=1 43 linoleic acid C-18=2 4 leukotrienes C-18=3 0.5 iodine number: low 45
High 50 saponification values: low 192
High 202 congealing points, ℃ (lipid acid): low 40
High by 45
Free fatty acids in the present invention's the mild personal cleaning bar (with other soil loading thinner) can be shockingly low.The ratio of Mg soap and FFA is about 50: 1 to 0.5: 1, preferably is about 30: 1 to 1: 1, more preferably is about 15: 1 to 2: 1.The content of FFA is about 1% to 10% in the perfumed soap, preferably is about 2% to 9%, preferredly is about 3% to 8%.
Be present in the hydrophobic substance (soil loading thinner) in the perfumed soap of the present invention, its content is about 0 to 40%, but preferable amount about 5% to 20%.Other hydrophobic substance comprises: contain 8 to 18 the carbon atom free fatty acidies of having an appointment; Single, double, three esters of glycerine; The Fatty Alcohol(C12-C14 and C12-C18) that contains 8 to 18 carbon atoms of having an appointment; And composition thereof; Wherein said composition contains the highest described paraffin and the highest described other hydrophobic substance of 15% that is about of 25% of being about.Triglyceride level (C
8-C
18Acyl chain) consumption can not influence lathering property up to about 10%.
Preferred hydrophobic substance is that fusing point (M.P) is about 120 °F～185 °F (49 °～85 ℃), is preferably the paraffin of about 125～175 (52 °～79 ℃).Preferred paraffin is fusing point abundant purified petroleum wax of process in about 130～140 (49 °～60 ℃) scopes.This paraffin odorless and tasteless, and meet the FDA requirement that is used for food coating and food Package.This paraffin is easy to buy on market.For example, can buy most suitable paraffin from the Standard Oil Company of Ohio, trade mark is called FactowaxR-133.
Other suitable paraffin is sold by National Wax Co., and trade(brand)name is 9182 and 6971, and its fusing point is respectively 131 and 130 (～55 ℃).
The paraffin amount that contains in the perfumed soap is preferably in about 5% to 20% (weight) scope.Adopting the paraffin composition in the product is in order to provide skin softness, plasticity-, rockiness and processibility.It also provides glossy outward appearance and sliding suitable sensation for perfumed soap.
The paraffin composition also can replenish Microcrystalline Wax selectively.The melting range of suitable Microcrystalline Wax for example is about 140 °F (60 ℃)～185 °F (85 ℃) preferred about 145 (62 ℃)～175 (79 ℃).Preferred paraffin should meet the FDA requirement of food grade microcrystalline wax.Can buy most suitable Microcrystalline Wax from Witco Chemical Company, trade mark is called Multiwax X-145A.Preferably about 0.5%～5% (weight) of the content range of Microcrystalline Wax in the perfumed soap.The Microcrystalline Wax composition has improved perfumed soap soft property at room temperature.
The consumption of the tensio-active agent thinner of non-soil loading can be about 0-40%, preferably about 5%-40%, more preferably from about 10%-35%.Back one content range is best to Flex Test flexibility.
The about 2%-15% of the content of water, preferably about 4%-10%.
The total content of nonsurfactant ionogen in the perfumed soap (organic and inorganic) is about 1%～10% of perfumed soap weight, and is preferred about 2%～8%, and more preferably from about 2%～5%.
Incorporate into as a reference in the patent documentation of this paper and disclose many tensio-active agent embodiment.They comprise alkyl-sulphate; anionic acyl sarcosinates, methyl-acyl taurine salt, N-acyl glutamate; alkyl sulfo succinate, phosphoric acid salt alkyl ester; the phosphoric acid salt alkyl ester of ethoxylation; tridecyl vitriol, albumen condenses, the alkyl-sulphate of ethoxylation and the mixture of alkyl amine oxide, betaine; Sultaines, with and composition thereof.Be included in the tensio-active agent is the sulfated alkyl ether with 1～12 oxyethyl group, especially Zetesol AP and Zetesol NL.
The alkyl chain of these tensio-active agents is C
8-C
22,, be preferably C for the soft tensio-active agent that bubbles
12-C
14For non-foaming non-soil loading thinner, be preferably C
16-C
18
Term used herein " alkyl glyceryl ether sulfonate " generally is meant to have 8-22 carbon atom, preferred 10-20 carbon atom, the more preferably mixture of the alkyl glyceryl ether sulfonate (AGS) of the alkane chain of 12-14 carbon atom.
Alkyl glyceryl ether sulfonate is to be derived and got by the corresponding ether that linear alkyl chain constitutes, and this linear alkyl chain is that synthetic accordingly or natural alcohol is derived and got by it.
Above-mentioned common transfer U.S. Patent No. 4,673,525, (Small etc.) disclose the surfactant based mild personal cleaning bar of a kind of soft alkyl glyceryl ether sulfonate, and it contains alkyl glyceryl ether sulfonate.The processibility that the present invention's mild personal cleaning bar demonstrates is better than the processibility of the disclosed mild personal cleaning bars of people such as Small.In other words, its processibility of improved perfumed soap of the present invention is also good than AGS perfumed soap.Perfumed soap of the present invention is also all relatively good aspect rockiness and smearing property.
Alkyl glucoside and methyl glucose ester are preferred soft nonionic, and this material can mix with at least one described soft negatively charged ion in the present invention's the composition or amphoterics.A preferred composition is a 2-acyloxy esilate.The aliphatics high-grade aliphatic ester of a kind of hydroxyethylsulfonic acid an alkali metal salt of 2-acyloxy esilate, and can be by following general formula definition: RCOOCH
2CH
2SO
3M, in the formula: R is the aliphatic group or the mixed aliphatic series group of higher fatty acid or its mixture, it has about 6-20 carbon atom, preferred about 8-18 carbon atom, for example coco group or roughly suitable chain length distribute, more preferred than long-chain (16 and 18) as thinner bubble-tight, non-soil loading, middle long-chain (C
12-C
14) more preferred as blistered synthetic surfactant; M is an alkali metal cation in the formula, for example sodium, potassium or ammonium, and perhaps organic amine alkali, as trolamine, three Virahol ammonium, diethanolamine and thanomins.Preferred cationic in AGS and the 2-acyloxy esilate is a sodium ion.
The preferred soft perfumed soap that is used for flexing position test flexibility contains: (1) about 5%-25%, the preferably C of about 10%-20%
16-C
18Alkyl (chain) vitriol and (2) about 5%-50%, preferably about 10%-30% magnesium soap (pressing perfumed soap weight).The disclosed embodiments 7 hereinafter for example.In this preferred perfumed soap, also need the soft synthetic surfactant that bubbles.The ratio of alkyl-sulphate and magnesium soap can be about 3: 1 to 1: 6, preferably about 1: 2 to 1: 4.This non-soil loading, bubble-tight synthetic surfactivity thinner is a kind of surprising good or fabulous thinner that is applicable to foaming ultra-soft synthetic surface washing composition, and for example human body cleans with alkyl glyceryl ether sulfonate and/or 2-coconut oxygen base esilate in the perfumed soap composition.The synthetic surfactant thinner provides and has made us well-content processibility, and flexibility or desirable physical property that on the other hand can the obvious damage perfumed soap.
C
16-C
18Alkyl-sulphate is to be derived and got by corresponding saturated straight chain alcohol.C
16-C
18Alkyl-sulphate as definition herein, contains described C
16-C
18Alkyl chain, its content are about 90% at least, and be preferred about 93%, more preferably from about 97%.In general, C
16With C
18Ratio can be to the scope of about 1: 4 (weight) at about 4: 1.The C that can buy on the market
16-C
18Alkyl-sulphate is SIPON
EC-111 (was SIREX in the past
EC-111), Sodium palmityl sulfate (Sodium cetearyl sulfate).It contains the 60%C that has an appointment
16And 36%C
18SIPON
EC-111 is by Alcolac Company, Baltimore, and MD21226 sells.Another sale source is Henkel Corp., Ambler, PA19002.The Sodium palmityl sulfate of Henkel, i.e. LANETTE E, estimation is a kind of 50-50%C
16-C
18Alkyl-sulphate is sold as a kind of emulsifying agent.
Percentage used herein, ratio and umber are benchmark with the weight of total composition or tensio-active agent all, except as otherwise noted.Herein all prescriptions, content and scope unless otherwise indicated, all are approximations.Some preferred percentage and ratio are in following narration.
The foaming synthetic surfactant accounts for 20% to 50% in perfumed soap weight of the present invention.Preferred perfumed soap contains: the soft synthetic surfactant of about 25%～45% foaming; About 15%～20% non-soil loading synthetic surfactant thinner, for example cetyl sulfate; About 10%-50% magnesium soap; And about 1%～10%, preferred 2%～9%, free fatty acids; About 0%～8%, preferred 0.2%～2%, polymerization skin sense auxiliary agent; And about 2%～15%, preferred 4%～10% water.
Contained soil loading thinner (FFA, paraffin etc.) is 0.1: 1 to 1: 1 with the ratio of the soft synthetic surfactant that bubbles in the perfumed soap of the present invention; Preferred 0.2: 1 to 0.9: 1.
The contained soil loading thinner and the ratio of non-soil loading thinner (comprising the Mg soap) are 0.1: 1 to 1: 1 in the perfumed soap of the present invention, are preferably 0.2: 1 to 0.9: 1, and when not having the Mg soap, its ratio is 0.4: 1 to 30: 1.
The contained foaming synthetic surface washing composition and the ratio of non-soil loading thinner (the Mg soap is arranged) are 0.2: 1 to 3: 1 in the perfumed soap of the present invention, are preferably 0.3: 1 to 2: 1; When not having the Mg soap, its ratio is 0.5: 1 to 35: 1.
Contained Mg soap is 1: 10 to 1: 0.4 with the ratio of foaming synthetic surfactant in the perfumed soap of the present invention, preferred 1: 5 to 1: 0.5, and more preferably 1: 4 to 1: 0.6.
The ratio 0.1: 1 to 3: 1 of contained Mg soap and the total face that closes tensio-active agent (pore forming material ten thinners) in the perfumed soap of the present invention, preferred 0.2: 1 to 2: 1, more preferably 0.3: 1 to 1.5: 1.
Contained magnesium soap is 50: 1 to 0.5: 1 with the ratio of free fatty acids in the perfumed soap of the present invention, preferred 30: 1 to 1: 1, and more preferably 15: 1 to 2: 1.
The contained magnesium soap and the ratio of soil loading thinner (FFA, paraffin etc.) are 0.3: 1 to 5: 1 in the perfumed soap of the present invention, preferred 0.4: 1 to 4: 1.
About smearing property of improvement, should note when magnesium soap content low, as 10% or when lower, the ratio of total synthetic surfactant and magnesium soap is greater than 5: 1 o'clock, it is about 2% to 7% that the water-content in the perfumed soap should be, preferred about 2.5% to 6%, can improve smearing property.
Can use more than one foaming synthetic surfactant.For example, about 2%～25%, preferred about 3%～20%, more preferably 4%～16% high bubble strengthens tensio-active agent, can use together with AGS as sodium N-lauroyl sarcosinate, shown in this paper embodiment.
Other perfumed soap composition is selected from following material: non-foaming dilution table surface-active agent, magnesium soap, soil loading thinner, polymerization skin feel auxiliary agent, part agent of surging, filler etc.
If mild personal cleaning bar contains polymeric skin sensation auxiliary agent, the then about 0-8% of its content, preferably 0.2-2%.
The preferred perfumed soap of the present invention can contain the 0.1%-5% that has an appointment, more preferably the cationic polymers of the appropriate fast hydration of 0.2%-2%.The molecular weight that polymkeric substance has about 1000 to 3,000,000.Preferred polymkeric substance is selected from molecular weight 2,500-350, the guar gum of 000 scope.
Cationic polymers (skin conditioning agent) is selected from following material:
(I) cationic polysaccharides;
(II) sugar and the monomeric cationic copolymer of synthesizing cationic; And
(III) is selected from the synthetic polymer of following material:
(A) positively charged ion polyalkyleneimine,
(B) cationic ethoxy polyalkyleneimine, and
(C) poly-[N-[-3-(dimethylamino) propyl group]-N '-[3-of positively charged ion
(inferior ethoxyl ethylidene dimethylamino) propyl group] urea] dichloride].
The specific examples of cationic polysaccharides comprises cationic hydroxyethyl cellulose JR400 (being produced by Union Carbide Corporation); Cationic starch Stalok
100,200,300 and 400 (by Staley, Inc produces); With the guar gum is Galactasol 800 series (by Hen1kel, Inc. produces) and the Jaguar series (being produced by Celanese Corporation) of the cationic galactomannan of base.
The specific examples of sugar and the monomeric multipolymer of synthesizing cationic comprises the material that is made of following material: derivatived cellulose (for example Natvosol) and N, the N-diallyl, N-N-dialkylammonium chloride (can buy trade name Celquet by National Starch Corporation).
Being used for cation synthesising copolymer of the present invention is the positively charged ion polyalkyleneimine, oxyethyl group polyalkyleneimine and poly-[N-[-3-(dimethylamino) propyl group]-N '-[3-(inferior ethoxyl ethylidene dimethylamino) propyl group] urea] dichloride].A kind of can the buying from Miranol Chemical Compang.Inc in back, trade mark is called MiranolA-15, CAS Reg.No.68555-36-2.
Preferred cationic polymerization skin conditioning agent of the present invention is that molecular weight is the cationic polysaccharide of 1000～3,000,000 positively charged ion guar gum class.More preferably molecular weight is 2,500～350,000.These polymkeric substance have a polysaccharide main chain that is made of following material: there is the cationic substituent of 0.04-0.8 polygalactomannan unit and each dehydration glucose unit, this cationic substituent is 2, the affixture of .3-epoxypropyl trimethylammonium chloride ammonium and natural polysaccharide main chain.Example is JAGUAR C-14-S, C-15 and C-17 (being sold by Celanese Corporation).
In order to reach the advantage described in the present invention, polymkeric substance must have the feature of structure and physical properties aspect, makes its moderately and fully aquation, and fusion advances in the soap matrix to go well subsequently.
Other composition of the present invention can be selected according to different purposes.For example, can use spices in the preparation cleansing skin product, generally its content is about 0.1%～1.5% of composition.Also can use alcohol, hydrotropic agent, tinting material, and filler, for example talcum and clay.But blending sanitas also in the cleaning products, for example, sodium ethylene diamine tetracetate (EDTA), its content is below 1% of composition usually, to prevent microorganism growth.Also can sneak into antimicrobial substance, content is up to 1.5% usually.
Preferred perfumed soap of the present invention can contain has an appointment 0.5%～4%, preferred 2%～3.5% tertiary sodium phosphate.
Following patent documentation discloses or mentions the composition and the prescription of the mild personal cleaning bar that can be used for the present invention, and these documents are incorporated this paper into as a reference.
Patent No. date of issue contriver
4,234,464 1/1980 Morshauser
4,061,602 12/1977 Oberstar etc.
4,472,297 9/1984 Bolich etc.
4,491,539 1/1985 Hoskins etc.
4,540,507 9/1985 Grollier
4,673,525 6/1987 Small etc.
4,704,224 11/1987 Saud
4,812,253 3/1989 Small etc.
4,820,447 4/1989 Medcalf etc.
Magnesium soap can in statu quo add, or on-site preparation, for example by adding a kind of alkali, as Mg (OH)
2, with the free fatty acids in the conversion composition batching.
In another kind of preferred (suitable) method of preparation perfumed soap of the present invention, with in the solution of alkali metal hydroxide or carbonate and synthetic detergent, wherein added salting-out electrolyte, if ionogen is not enough, in other step of neutralization procedure and this method, can generate ionogen, import suitable mixing machine then, in the soap crutcher.Can add some water then and improve flowability, and add a kind of soda soap, preferably contain about 30% water.These compositions are mixed, the water-soluble alkali earth metal salt of adding sufficient quantity then, as sal epsom or magnesium chloride, or calcium chloride, so that portion water dissolubility soap is changed into the water-insoluble soap, it is to form as byproduct that sodium salt is analysed ionogen.In a preferred method, in mixture, add before the synthetic surfactant, make magnesium soap earlier.Continue to mix to guarantee the balance of even magnesium soap in forming.Certainly, after forming, magnesium soap also can carry out the ideal adjusting aspect the water-soluble soap composition.
Two kinds of preferred method I that prepare preferred mild personal cleaning bar. mix-neutralize
1. in crutcher, add the AGS slurry of predetermined amount in 65 ℃ (150 °F).
2. in the outside of crutcher, in the water [75 ℃ (167)] of enough heat, add the NaCl and the Na of predetermined amount
2SO
4, make final crutcher moisture up to 50%, comprise the water in other all raw materials.Electrolyte dissolution in hot water after, mixture is added in the crutcher.
3. start agitator and recirculating pump (available can) and crutcher temperature is remained on 75-85 ℃ (167-185 °F) by regulating steam and penstock
4. in crutcher, add the TiO of predetermined amount
2Powder.
5. at room temperature add the Mg (OH) of predetermined amount to crutcher
2Powder.Also can use the slurry of this material.Mix up to powder and distribute fully significantly.
6. in crutcher, add the lipid acid of predetermined amount, make magnesium soap.It is desirable to, this acid should add with the fusion form at 75-85 ℃ (167-185 °F).If add then continuous the mixing up to the obvious fusion of powder with form of powder.
7. at room temperature in crutcher, add the solutions of sarcosine salts of predetermined amount.Make crutcher return target temperature.
8. in crutcher, add the melt paraffin of predetermined amount in 75-85 ℃ (167-185 °F).If add the paraffin sheet, then make the complete fusion of paraffin.
9. the pH value that content in the crutcher is mixed fully and react in crutcher reaches target value: 7.3～8.0, and the temperature with crutcher remains on 75-85 ℃ (167-185 °F) simultaneously.Generally need 20-40 minute.
In before lipid acid add under the corresponding to temperature, add the excess fatty acids of predetermined amount.Crutcher was mixed 10 minutes.II. mix-ion-exchange
1. in the crutcher, in the soap of 82-88 ℃ of (180-190) required amount of packing into, lipid acid and triglyceride level, and be mixed to evenly about 10 minutes.
2. solubilization MgCl in the water
2And be added in the crutcher.Continue stirring in 82-88 ℃ (180-190 °F) and finish about 10 minutes until reaction.
3. in crutcher, add liquid sodium N-lauroyl sarcosinate, coco group glyceryl ether sulfonic acid sodium and amine oxide, keeping temperature is 82-88 ℃ (180-190 °F).Mixing is until evenly, equal 10 minutes.
4. add the polyoxyethylene WSR-35 of desired amount and mixed 5 minutes.
The drying of method I and II
The mixture dual-purpose flashing chamber of crutcher and cold breakdown or cold belt carry out drying and cooling.The crutcher mixture at first with heat exchanger heats to about 132 ℃ (270), expansion drying in cold breakdown or the chamber above the cold belt then.Mixture heat, that drying is crossed from flashing chamber is extruded on cold breakdown or the cold belt.Cold breakdown or cold belt provide a kind of evenly, thin, cold 29-35 ℃, 85-95 °F), sheet or bits shape product.The typical water of flap is divided into 2-12%, preferred 6-8%.Adjust the method for moisture, better order is the vapor pressure that (1) increases or reduce heat exchanger; (2) increase or reduce the speed that the crutcher mixture enters heat exchanger; And (3) increase or reduce the temperature of the crutcher mixture that enters heat exchanger.
Mixing
These flaps are weighed and in batch mixer, mix, obtain uniform chip size.Mix claiming overweight spices to be added in the flap and in mixing tank, reach the spices level of product.Dulcet flap sent to grind in the bucket or directly send into plodder.
Grind (not essential)
First roller of arranging 3 roller French milling machines is at 38 ℃ (100 °F), about 21 ℃ of other two roller (70).With soap by roller for several times to obtain the mixture of uniform spices and exsiccant flap.
Mold pressing and punching press
About 21 ℃ (70) of tube temperature of plodder, feeding is chewed temperature and is 38-49 ℃ (100-120 °F).The ideal plodder is the twin-stage plodder, can utilize 15-25 inch Hg vacuum.Pipe close should be cut into 5 " section, and carry out punching press with the cold module that adopts mould liquid (as alcohol).
Below explanation embodiment and method do not limit the scope of the invention but these embodiment and method are plan.The preparation of generic alkyl glyceryl ether sulfonate itself and the detailed description of purification process have been disclosed in to be incorporated in this paper U.S. Patent No. 2,988,511 as a reference.As has been noted, percentage used herein, ratio and umber all are that the weight with total composition or tensio-active agent is benchmark, except as otherwise noted.All content, scope, temperature, results etc. unless otherwise indicated, all are approximations.
The mild personal cleaning bar of example 1-7 be adopt above-mentionedly preferably mix-neutralization method makes.Embodiment 8 be with synthetic surfactant mixing forward direction Na soap in add magnesium chloride, mat ion-exchange forms magnesium soap and makes.The comparative example A makes by the embodiment 1-7 method that is similar to perfumed soap, and difference is to replace Mg (OH) with sodium hydroxide
2, and be used as the standard of flexibility and smearing property.Comparative Examples B is " B " soap and is used as flexibility and second standard of smearing property.Comparative Examples C is that a kind of main merchant sells full soap, and as the typical standard of soap entirely.Embodiment 3 is examples of a kind of flexibility, foam and smearing property aspect integrated optimization.
It is as follows that two kinds of smearing property tests disclose, i.e. " smearing property of soap mud (Mush Smear) 1 " and " smearing property of soap blank feature (Bar Character Smear) 2 "
Smearing property of soap mud (Mush Smear) " 1 " testing sequence equipment 1.#2-202C Fisher trade mark hexagon polystyrene weighing pan (4 " * 3 ") is a plurality of.2.#14-366A Fisher trade mark scraper.3. can be weighed into the balance of two-decimal point.4.120 the room of temperature.5. timing register test method
To need with weighing pan carry out mark and weigh (two weighing pans of each sample, an ooze dish mark M, an immersion dish mark S).
2. former soap blank is weighed and write down weight.Soap blank is placed in the overweight dish that is labeled as S of title.
3. 30ml room temperature tap water being added in the dish of dress raw sample soap to (water being poured into the downside of weighing pan) adds 30ml room temperature tap water in the dish of dress contrast soap to.When soap blank is put into dish, must make soap blank keep off the limit of plate.
4. under room temperature, soap blank is immersed in and leaves standstill 2 hours in the weighing pan.
5. after soaking 2 hours, carefully take out soap blank and in identical dish drip-dry reached for 15 seconds.
6.15 after second, the counter-rotating soap blank is also put into the dish of preweighted mark M.
7. the soap blank and the record of weighing and soaking.
8. with the wet surface or the soap mud of a scraper scraping soap blank, put into the dish of identical preweighted mark M, weigh and record.When hold in the hand scraper than pine carefully cutter dig soap blank or scraping and cross when dark, can find out that the scraping result is best.When the soap blank surface seems no longer to seem moist or glossy, promptly finish scraping.In order to eliminate interpersonal scraping degree change, each test-results all with test in the controlled trial that is provided with report after relatively.
9. weigh and write down the soap blank of scraping.
10. with the immersion dish, the soap blank of softening the dish of soap mud and scraping is placed in the room of 120 temperature and evaporated the water 48 hours.
11.48 after hour, weigh and write down immersion dish, the dry weight of the soap blank of soft soap mud pan and scraping.
12. grow by measuring (inch) * wide, calculate soap blank by the surface-area of scraping part.
13. the dried gram number of soap mud (smearing) and the kilogram number of soak are added up, and this is the overall result of representing with gram.
All series of trials all should comprise simultaneous test, test and all samples all should be a double.Once can test 7 products (6 add 1 reference substance) at most, should have 10 minutes between per 4 samples and be used to add water at interval, thereby make any product not have the retardation time of the immersion of being longer than 2 hours.
Smearing property of soap blank feature " 2 " test
5ml smears the small-sized measurement tube of testing installation " Alathon " soap dish method
1. the surface that will soak is immersed in the distilled water and is got rid of excessive water and make that to wait to test soap blank wetting.It is more even that this program makes soap blank smear.
2. soap blank is placed on " Alathon " dish central authorities that 5ml distilled water is housed.Vibrating disk is so that destroy the tension force of water.The Alathon dish of selecting is a kind of standard, has (in the U.S.) that is easy to buy dish of low edge.
3. (27 ℃/80/80%RH) store spend the night (about 18 hours) under the condition of the standards of temperature and humidity.Because this test is to measure the restorability of soap blank and water-absorbent simultaneously, the seasonal variation that standard conditions have taken place under having avoided spending the night condition in not controlled laboratory.
4. the next morning, carefully vertically propose soap blank and reverse to be made for judge.Pass judgment on
Smearing property of soap blank-stroke and consider to smear type and applying amount by finger is made the rank of passing judgment on smearing property of soap blank.
The description of smearing property of rank
10 is extremely excellent
9 fabulous smearing property
8 smearing property good (target)
7 is poorer slightly than what wish
6 are in the edge but still can accept
Acceptable the smearing property of 5 bottom lines
4 differences and unacceptable
3 very poor smearing property
2 are commonly considered as the poorest
1 very poor smearing property
The clinical evaluation of perfumed soap
Below provide the used clinical trial method of assessment that is used for the soft several perfumed soap prescriptions of skin.
Soft forearm washing test method
Carry out washing test by an expert.Specifying every member of panel of experts, is one group cleaning to 8 products, 4 kinds of each arm Xian.The testing sequence of each arm is as follows:
Draft
1. will have 4 3M Micropore surgical operations of opening the 3.2cm diametric hole in advance are placed on forearm with adhesive tape inboard.Band is concentrated on the inboard lower of forearm makes reason district, lower leave wrist.
2. with the wetting forearm of hot water (35-40 ℃).
3. with the wetting nonwoven paper handkerchief of hot water (Masslinn Towel, Chicopee Mills, New Brunswick, New Jersey).On corresponding test products, reached for 6 seconds with circular movement friction paper handkerchief.
4. reached for 10 seconds at each test place pivoting friction paper handkerchief.
5. test products is spumed, be retained in test place and reach 90 seconds.
6. with the every place of hot water (35-40 ℃) rinsing, reached for 15 seconds.
7. with soft, disposable use (BOUNTY
) paper handkerchief is patted the test position makes it dry.
8. wait 2 minutes, repeat said procedure for the second time.
9. this program is carried out 2 times every day again, and continuous 4 days, be 1 the last day of research, washes altogether 17 times.About 3 hours intervals of each investigation in every day.Before the wash procedure and after the 5th day the last cleaning 3 hours the 3rd day the second time, visual observation is carried out in each test place.All visible ridity and flush spot are kept the score at each duration of test.
10. used following grade.Clinical trial skin grade
The skin of forearm of this paper report grade of keeping the score is expressed as follows:
Forearm grade-xerosis cutis degree 0. perfect skin 1.0 can be seen fritter and/or thin meal and the accidental stigma of seeing.Widespread distribution.2.0 the fine powder of widespread distribution.Have infant cracking or accidental little protruding spot.3.0 widespread distribution is medium less than meal and/or medium crackle and protruding spot.4.0 general serious meal and/or big crackle and protruding spot.5.0 the big crackle of widespread distribution and protruding spot.Have eczema and change, have meal but and outstanding.Can see hemorrhage crackle.6.0 the severe crack of widespread distribution.May exist eczema to change.Has hemorrhage crackle.Blotch may begin to disappear.
Forearm grade-skin erythema 0. do not have red 1.0 almost imperceptible red 2.0 slight redness 3.0 medium red 4.0 heavy or be essentially the profound redness of red 5.0 serious redness 6.0
Term used herein " widespread distribution " is meant that the forearm surf zone greater than 50% presents characteristic.Whole unit skin grade reflection widespread distribution situation.Represent middle situation with half unit.
Flexing position test is cleaned in the hot water that draft 1. is placed on a sponge 37 ℃ (95-100) wetting until drenched fully.2. the extruding sponge is removed excessive water 3-4 time.3. directly reaching 10 seconds as circular movement on the test soap bubbles wet sponge.4. clean 60 seconds of suitable test district of antetheca inboard.(being that per second is done 2-3 circle cleaning action).5. thorough drip washing washing section and pat with paper handkerchief and to make it dry (suggestion drip washing 15 seconds).6. this program is done 3 times continuous 5 days every day, totally 15 washings.Every day, each washing procedure was about 2 hours at interval.Carrying out visual inspection before the washing procedure next time.Each inspection period all keeps the score to the visible erythema.Final inspection is that in the end washing procedure carried out afterwards in 2 hours.7. used the following erythema rank of keeping the score.
0=does not have tangible erythema
The erythema (mottled and/or bottom line visible) that 1=is slight
2=moderate erythema (more even, pink)
The remarkable erythema of 3=(uniformly, relatively distincter or than scarlet)
Mediant 0.5,1.5,2.5 and 3.5 each value also can adopt as required.8. if reach " 2 " level or higher, arm just no longer stands washing procedure.For remaining test, be appointed as " 2 " level.9. by checking out 2 grades or high-grade number more, product is carried out statistics relatively.The product that these number of levels are few more is judged as more soft.
In following examples, it comprises magnesium soap, and some or all magnesium soap can replace with other alkaling earth metal base (as calcium, zinc, aluminium) and other soap, and these soaps are arranged undissolved basically successively from magnesium soap.
Table 1
Example 1 example 2 examples 3 examples 4 composition weight % weight % weight % weight % magnesium soaps (coconut hydrochlorate)-33.0--(lauroleate) 29.7--22.5 (stearate)
*--38.0-; (75 Tallow, beefs/25 palmitates)----soda soap; (50 Tallow, beefs/50 palmitates) 1.4---Sodium palmityl sulfate 11.8---coco group glyceryl ether sodium sulfonate 15.7 25.0 21.0 40.9 sodium N-lauroyl sarcosinates 6.9 7.0 12.0 7.5C
12-13Alkyl dimethyl amino-oxide---laurate 2.9-3.0 3.2 coconut acids-3.0--sodium chloride 1.0 1.0 1.5 1.5 sodium sulphate 1.5 1.5 1.85 1.5 paraffin (M.p.55 ℃) 14.7 17.0 10.0 10.7 triglycerides 1-8 expect firmly----polyoxyethylene WS R-35----titanium dioxide 0.2 0.2 0.2 0.2 spices 1.0 1.0 1.0 1.0 water 10.1 8.7 9.3 6.8 other 3.1 2.6 1.7 4.2 totals 100.0 100.0 100.0 100.0
* Emersol 132 (Emery industry) is actually that to have titre about 55 and maximum I.V. be 0.5 the stearate and the mixture of lauroleate.
(g) 0.58 0.52 1.11 0.86 average 0.62 0.98 1.31 1.40 smear 2 (following method) 5ml** 7.5 7.5 6.5 7.5PH 8.02 7.45 7.55 7.41 soaps of (g) * 0.66 1.44 1.51 1.93 drying that example 1 example 2 examples 3 examples 4 smears 1 (following soap mud smear " 1 " test) are wetting/FFA ratio 10: 1 11: 1 12.2: 17: 1* numerical value is more low more good. * numerical value is high more good more.
Embodiment 1-4's is every: soft synthetic surfactant bubbles; Magnesium soap; Non-soil loading, non-foaming tensio-active agent; Be shown in following table with soil loading thinner summation.Summation example 1 example 2 examples 3 examples 4 soft foaming synthetic surfactant 21.5 30.25 31.53 45.54 magnesium soaps 29.7 33.0 38 22.5 non-dirts, non-foaming thinner (comprising the Mg soap) 42.6 34.75 39.47 25.36 soil loading thinner (FFA, paraffin, 17.68 20 13.0 13.9 triglyceride level) Mg soap/total synthetics is 0.9: 11: 1 1.15: 1 0.5: 1
Continuous table 1
Example 5 examples 6 examples 7 examples 8 composition % by weight % by weight % by weight % by weight magnesium soaps; (coconut hydrochlorate)----; (laruate) 12.8 24.0--; (stearate) *--10.0-; (75 tallows/25 palmitates)---27.6 soda soaps; (50 tallows/50 palmitates)----sodium hexadecyl sulfate 32.1-14.0-coco group glycerin ether sodium sulfonate 17.1 35.0 32.0 13.6 sodium N-lauroyl sarcosinates 7.4 7.0 10.0 15.9C12-13Alkyl dimethyl amino-oxide---2.3 laurate, 3.2 3.0 5.0-coconut acids---7.9 sodium chloride, 1.5 1.5 1.5 3.7 sodium sulphate, 1.5 1.5 1.85 0.6 paraffin (M.P.55 ℃), 12.6 13.0 13.0-triglycerides I-8 expect firmly---, 16.1 polyoxyethylene WS R-35---0.4 titanium dioxide, 0.2 0.2 0.2 0.25 spices, 1.0 1.0 1.0 1.0 water, 7.4 10.2 7.5 9.0 other 3.2 3.6 3.9 1.6 totals 100.0 100.0 100.0 100.0
* Emersol 132 (Emerg industry).
Example 5 examples 6 examples 7 examples 8 smearing property 1 are wetting, (g) * 2.35 2.38 4.26 N/A exsiccant, (g) 1.37 1.64 2.00 N/A average 1.86 2: 01 3.10 smearing property of N/A 25ml** 7.5 7.0 6.5 8.0PH 7.97 7.57 7.59 8.00 soaps/FFA ratio are 4: 18: 12: 1 3.5: 1* numerical value is low more good more.* numerical value is high more good more.N/A=is unavailable.
The synthetic surfactant total content is 56% among the embodiment 7.Water-content is 7.5%; The Mg soap is 0.18: 1 with the ratio of total synthetics.Smearing property can be improved to being lower than 7% by reducing water-content among the embodiment 7.Please note that total synthetics amount is 56.6% among the embodiment 5, and the ratio of Mg soap and synthetics summation is 0.22: 1, yet have higher Mg soap content (12.8% pair 10%), although embodiment 5 is identical with water-content in 7, embodiment 5 has smearing property preferably.
In order to improve smearing property, should note: when magnesium soap content is low when (for example 10% or lower), and when the ratio of synthetic surfactant summation and magnesium soap content was higher than 5: 1, the water-content in the perfumed soap should be about 2%-7%, preferably is about 2.5%-6% and can improves smearing property.
Table 2 comparative example A-C example A example B example C composition weight % weight % weight % sodium C
12/ C
14/ C
16/ C
18-58/21/10/9% (AGS) 48.2--sodium N-lauroyl sarcosinate 12.5--2-coconut oxygen base esilate-49.1-sodium n-alkylbenzenesulfonate-2.0-laurate 6.5--stearic acid 9.8 25.0-sodium chloride 5.3 0.5 0.81 sodium sulphate 1.3--2-ethylenehydrinsulfonic acid sodium-6.0-soda soaps (60 stearate/4.0 laruates), 7.2 12.0-(85 tallows/15 coconut hydrochlorates)---(75 tallows/25 coconut hydrochlorates)--75.25 titanium dioxide 0.25 0.4-spices 1.0 1.0 0.16 water 3.5 4.0 23.5 other 4.4-0.28 amount to 100.0 100.0 100.0
The comparative example A is a kind of supersoft perfumed soap, and it has goodish smearing property, and is approximately identical, soft with " B " soap, can buy soap/synthetics perfumed soap on the market.As commeasurable soft perfumed soap of the present invention, for example embodiment 1-6 and 8 smearing property surpass comparative example A and standard Comparative Examples B (for " B " soap).Comparative Examples C is a kind of first-class pure mild soap, and the soft of perfumed soap that the present invention is shown surpasses it.
Wetting (g) * 3.20 3.66-exsiccant (g) 1.50 1.43-average 2.35 2.55-smearing property, 2 5ml**, 7.5 7.0 7.0 PH, 7.3 7.3 9.5 soaps of smearing property of example A example B example C 1/FFA ratio 0.4: 1 0.5: 11: 0
Numerical value is low more good more.
Numerical value is high more good more.
Among the embodiment live and give birth to agent chain length table look-up in used AGS surface
% chain length distribution %C
16-C
18Embodiment C
12C
14C
16C
18Chain length 1-8 68 25 7-7 A* 58 21 10 9 19
* comparative example A
Higher AGS alkyl chain distributes although the comparative example A has, more C
16With 9% C
18(is benchmark with AGS weight), but on average the smearing property of embodiment 1-6 still is better than the comparative example A.
Soft test-results flexing position test * erythema example C 2.42 examples 4 1.18 examples 3 0.90 examples 7 0.68 example B 0.65-1.29 examples 8 1.59 test examples A 1.09 are in advance tested in advance
In the test-results of above-mentioned flexing position, the low more expression body-cleansing agents of erythema value is soft more.Contrast soap C is a kind of first-class full soap, and its erythema level is the highest.Embodiment 4.3 can compare U.S. with " B " soap with 7 erythema grade, and the erythema grade of " B " soap is about 0.65 to 1.29, is the low value and the high value of four classes " B " soap.
Embodiment 4,3 and 7 erythema grade are respectively 1.18; 0.90 and 0.68.Embodiment 8 and comparative example A's erythema grade is better than the example C of full soap, near " B " soap.
" B " soap 0.65-1.29 as a result is example C, the low value and the high value of four kinds of flexing position tests in succession of 4,3 and 7.The flexing position test-results of embodiment 8 and A (rather than Embodiment C, 4,3 and 7 series of trials) show that embodiment 8 is good not as " B ", but than full soap, Comparative Examples C is soft.Notice: embodiment 8 has preferred fat seldom, particularly compares its titre lower (37) and iodine number higher (38) with 7 with embodiment 4,3.Embodiment 4,3, and 7 and 8 titre and I.V. are shown in following table
Example titre iodine number
4 41-44 are the highest by 1.0
3 54.5-55.5 are the highest by 0.5
7 54.5-55.5 are the highest by 0.5
8 37 38
Referring to table 1, embodiment 8, and good smearing property is arranged, and are 8 in 2 of smearing property.
Forearm clinical trial *
Red degree ridity
Example 8 1.18 1.68
Example A 1.19 1.66
Example A 1.16 1.70
Example B 1.70S 2.22S
Example 2 1.37 1.44
Example B 169 1.63S
* numerical value is low more good more
The believable virtual value of S=90-95% is remarkable
The forearm clinical test results shows embodiment 8,9 and 2 all good than " B " aspect red degree and ridity two.Enforcement 8 and A are roughly the same, and A is obviously good than B.Embodiment 2 is also obviously good than " B ".
As shown in Table 1 and Table 2, the smearing property of embodiment 2 also is better than " B ", and on average the smearing property 1 of embodiment 2 is 0.98, and " B " is 2.55, and this explanation enforcement 2 is highly beneficial.Smearing property 2 is 7.5 concerning embodiment 2, and " B " is 7.0, and this shows that embodiment 2 is good slightly.
One group of expert compares some sensorial characteristics of embodiment 2 and " B " soap.The result is: the sensorial characteristics of embodiment 2, compactness, slipperiness and flexibility can be compared U.S. with " B " soap.The aspect that 33% magnesium soap is arranged from embodiment 2, the result of its compactness is unexpected.
Claims (23)
1. be used to prepare the sheet-like composition of mild personal cleaning bar, comprising:
(A) bubble soft synthetic surfactant and 5-50% lipid acid magnesium soap of 20-50%; The soft synthetic surfactant of wherein said foaming is 5 with the ratio of described soap: 1-0.4: 1; And described soft synthetic surfactant is basically by C
12-C
14Alkyl chain is formed;
(B) the non-soil loading dilution of 5-40% synthetic surfactant, wherein said non-soil loading dilution synthetic surfactant is basically by C
16-C
22Alkyl chain is formed; With
(C) 5-20% wax;
Wherein said fatty acid soaps congealing point is that 35-75 ℃ and iodine number are that the lipid acid of 0-15 is made.
2. the preparation method of mild personal cleaning bar, its step comprises:
I. the preparation sheet-like composition, comprising:
(A) bubble soft synthetic surfactant and 5-50% lipid acid magnesium soap of 20-50%, the soft synthetic surfactant of wherein said foaming is 5 with the ratio of described soap: 1-0.4: 1; And described soft synthetic surfactant is basically by C
12-C
14Alkyl chain is formed;
(B) the non-soil loading dilution of 5-40% synthetic surfactant, wherein said non-soil loading dilution synthetic surfactant is basically by C
16-C
22Alkyl chain is formed; With
(C) 5-20% wax;
Wherein said fatty acid soaps congealing point is that 35-75 ℃ and iodine number are that the lipid acid of 0-15 is made; And described perfumed soap contains no more than 1.4% residual soda soap; And
II. make described perfumed soap, wherein with described sheet-like composition mold pressing and the stripping and slicing of described moulding compositions is struck out described human body clean and use perfumed soap.
3. the method for claim 2, wherein said mild personal cleaning bar comprises: 20-50% bubble soft synthetic surfactant and 10-50% lipid acid magnesium soap; The soft synthetic surfactant of wherein said foaming is 5 with the ratio of described soap: 1-0.4: 1; Described perfumed soap pH value in 1% aqueous solution under 25 ℃ is 6.5-8.5; And the soft synthetic surfactant of described foaming is basically by C
12-C
14Alkyl chain is formed and described perfumed soap contains no more than 1.4% residual soda soap.
4. the method for claim 3, wherein the content at magnesium soap described in the described mild personal cleaning bar of claim 3 is 10-45%; Described ratio is 5: 1-0.5: 1; The water-content of described perfumed soap is 2-15%; And described pH value is 7-8.
5. the method for claim 4, wherein the ratio at bubble described in the described mild personal cleaning bar of claim 4 soft synthetic surfactant and described Mg soap is 4: 1-0.6: 1, and described water-content is 4-10%.
6. the method for claim 3, the free fatty acids that wherein contains 1-10% at perfumed soap described in the described mild personal cleaning bar of claim 3, and described magnesium soap is 50 with the ratio of described free fatty acids: 1-0.5: 1, the congealing point of wherein said magnesium soap and lipid acid is 35-75 ℃, and iodine number is 0-15.
7. the method for claim 6 is 15 at the ratio that perfumed soap described in the described mild personal cleaning bar of claim 6 contains the free fatty acids of 2-8% and described magnesium soap and described free fatty acids wherein: 1-2: 1.
8. the method for claim 3 is wherein made by ion-exchange at magnesium soap described in the described mild personal cleaning bar of claim 3.
9. the method for claim 3 is wherein made by neutralization at magnesium soap described in the described mild personal cleaning bar of claim 3.
10. the method for claim 3 wherein contains ionogen at perfumed soap described in the described mild personal cleaning bar of claim 3, and its content is 1-10%.
11. the method for claim 10 is 2-5% at electrolytical content described in the described mild personal cleaning bar of claim 10 wherein.
12. the method for claim 3 wherein also contains other hydrophobic substance of as many as 15% at perfumed soap described in the described mild personal cleaning bar of claim 3, described other hydrophobic substance comprises: the free fatty acids that contains 8-18 carbon atom; Single, double and three esters of glycerine; The Fatty Alcohol(C12-C14 and C12-C18) that contains 8-18 carbon atom; And composition thereof; Wherein the total content of hydrophobic substance mostly is 40% most.
13. the method for claim 12 wherein contains non-soil loading dilution synthetic surfactant at perfumed soap described in the described mild personal cleaning bar of claim 12, its content is 5-40%; And described non-soil loading dilution synthetic surfactant is basically by C
16-C
18Alkyl chain constitutes.
14. the method for claim 13 wherein contains at least 90% saturated C at non-soil loading dilution synthetic surfactant described in the described mild personal cleaning bar of claim 13
16-C
18Alkyl chain.
15. the method for claim 14, wherein the content at non-dirt dilution synthetic surfactant described in the described mild personal cleaning bar of claim 14 is 10-35%.
16. the method for claim 2, wherein said mild personal cleaning bar comprises: 20-50% bubble soft synthetic surfactant and 5-50% lipid acid magnesium soap, and the soft synthetic surfactant of wherein said foaming is 5 with the ratio of described soap: 1-0.4: 1; The ionogen of 1-10%; And the water of 2-15%; Described perfumed soap pH value in 1% aqueous solution under 25 ℃ is 6.5-8.5; And the soft tensio-active agent of described foaming is selected from C
12-C
14Alkyl glyceryl ether sulfonate and C
12-C
14Sarcosinate and composition thereof.
17. the method for claim 16, wherein in the described mild personal cleaning bar of claim 16, the soft tensio-active agent that bubbles comprises the mixture of described alkyl glyceryl ether sulfonate and described sarcosinate, the content of wherein said sarcosinate is that 2-25% is counted on the basis with perfumed soap weight, and described pH value is 7-8.
18. the method for claim 16 wherein also contains other hydrophobic substance at perfumed soap described in the described mild personal cleaning bar of claim 16, described other hydrophobic substance comprises: the free fatty acids that contains 8-18 carbon atom; Single, double and three esters of glycerine; The Fatty Alcohol(C12-C14 and C12-C18) that contains 8-18 carbon atom; And composition thereof; Wherein the total content of hydrophobic substance mostly is 40% most, and the soft tensio-active agent of wherein said foaming comprises the mixture of described alkyl glyceryl ether sulfonate and described sarcosinate, and the content of described sarcosinate is 3-20%.
19. the method for claim 18 is 5-20% at paraffinicity described in the described mild personal cleaning bar of claim 18 wherein.
20. the method for claim 18, wherein the content at non-soil loading dilution synthetic surfactant described in the described mild personal cleaning bar of claim 18 is 5-40%.
21. the method for claim 20 wherein contains at least 90% saturated C at non-soil loading dilution synthetic surfactant described in the described mild personal cleaning bar of claim 20
16-C
18Alkyl chain.
22. the method for claim 21, wherein the content at non-soil loading dilution synthetic surfactant described in the described mild personal cleaning bar of claim 21 is 15-20%.
23. the method for claim 20 is that the content of 25-45% and described non-soil loading synthetic surfactant is 15-20% at the content of the soft tensio-active agent that bubbles described in the described mild personal cleaning bar of claim 20 wherein; And the content of described magnesium soap is 10-40%.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US66857891A | 1991-03-13 | 1991-03-13 | |
| US668,578 | 1991-03-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1064887A CN1064887A (en) | 1992-09-30 |
| CN1042745C true CN1042745C (en) | 1999-03-31 |
Family
ID=24682904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92101776.6A Expired - Lifetime CN1042745C (en) | 1991-03-13 | 1992-03-13 | Low PH mild personal cleaning bar |
Country Status (23)
| Country | Link |
|---|---|
| EP (1) | EP0575440B1 (en) |
| JP (1) | JPH06505764A (en) |
| CN (1) | CN1042745C (en) |
| AT (1) | ATE138411T1 (en) |
| AU (1) | AU1419092A (en) |
| BR (1) | BR9205766A (en) |
| CA (1) | CA2105090A1 (en) |
| CZ (1) | CZ190493A3 (en) |
| DE (1) | DE69210992T2 (en) |
| DK (1) | DK0575440T3 (en) |
| EG (1) | EG20454A (en) |
| ES (1) | ES2087531T3 (en) |
| FI (1) | FI934002A (en) |
| GR (1) | GR3020019T3 (en) |
| HU (1) | HUT65576A (en) |
| IE (1) | IE920803A1 (en) |
| MA (1) | MA22463A1 (en) |
| MX (1) | MX9201096A (en) |
| NO (1) | NO933256L (en) |
| PT (1) | PT100243A (en) |
| SK (1) | SK98493A3 (en) |
| TW (1) | TW198063B (en) |
| WO (1) | WO1992016609A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5387362A (en) * | 1992-10-13 | 1995-02-07 | The Procter & Gamble Company | Personal cleansing bar with tailored base soaps with mixed counterions for improved mildness and processability without lather negatives |
| ES2201107T3 (en) * | 1994-05-10 | 2004-03-16 | THE PROCTER & GAMBLE COMPANY | COMPOSITIONS FOR SYNTHETIC SOAP PAD FOR PERSONAL HYGIENE WITH LOW LEVELS OF NON-ION POLYMERS POLYETHYLENE / POLYPROPYLENE GLYCOL THAT IMPROVE SOFTENING. |
| US5496493A (en) * | 1994-05-10 | 1996-03-05 | The Procter & Gamble Company | Ultra mild personal cleansing bar containing smaller-sized particulate wax |
| US5540852A (en) * | 1995-01-31 | 1996-07-30 | The Procter & Gamble Company | Personal cleansing bar with tailored fatty acid soap |
| US20170196789A1 (en) * | 2014-06-26 | 2017-07-13 | Artin Barzgar | Reduction of oral and epidermal malodor in humans and animals |
| CN108048266A (en) * | 2018-02-08 | 2018-05-18 | 深圳天和圆实业有限公司 | A kind of Clean- faintly acid perfumed soap |
| CN108982759B (en) * | 2018-06-06 | 2021-03-09 | 上海家化联合股份有限公司 | Method for testing skin moistening capability of beauty product |
| DE102021005857A1 (en) | 2021-11-25 | 2023-03-23 | J. Rettenmaier & Söhne Gmbh + Co Kg | Personal care product and method of making same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2781321A (en) * | 1953-05-12 | 1957-02-12 | Gen Aniline & Film Corp | All purpose detergent bar |
| US3070547A (en) * | 1953-07-13 | 1962-12-25 | Procter & Gamble | Soap-synthetic bar |
| BE546418A (en) * | 1955-03-31 | |||
| BE607797A (en) * | 1960-09-05 | |||
| US4673525A (en) * | 1985-05-13 | 1987-06-16 | The Procter & Gamble Company | Ultra mild skin cleansing composition |
-
1992
- 1992-01-30 DE DE69210992T patent/DE69210992T2/en not_active Expired - Lifetime
- 1992-01-30 JP JP4506612A patent/JPH06505764A/en active Pending
- 1992-01-30 ES ES92906869T patent/ES2087531T3/en not_active Expired - Lifetime
- 1992-01-30 DK DK92906869.0T patent/DK0575440T3/en active
- 1992-01-30 HU HU9302584A patent/HUT65576A/en unknown
- 1992-01-30 SK SK984-93A patent/SK98493A3/en unknown
- 1992-01-30 CA CA002105090A patent/CA2105090A1/en not_active Abandoned
- 1992-01-30 CZ CS931904A patent/CZ190493A3/en unknown
- 1992-01-30 WO PCT/US1992/000689 patent/WO1992016609A1/en active IP Right Grant
- 1992-01-30 BR BR9205766A patent/BR9205766A/en not_active Application Discontinuation
- 1992-01-30 AT AT92906869T patent/ATE138411T1/en not_active IP Right Cessation
- 1992-01-30 EP EP92906869A patent/EP0575440B1/en not_active Expired - Lifetime
- 1992-01-30 AU AU14190/92A patent/AU1419092A/en not_active Abandoned
- 1992-02-26 TW TW081101432A patent/TW198063B/zh active
- 1992-03-11 EG EG13492A patent/EG20454A/en active
- 1992-03-12 MX MX9201096A patent/MX9201096A/en active IP Right Grant
- 1992-03-12 IE IE080392A patent/IE920803A1/en not_active Application Discontinuation
- 1992-03-12 MA MA22751A patent/MA22463A1/en unknown
- 1992-03-13 PT PT100243A patent/PT100243A/en not_active Application Discontinuation
- 1992-03-13 CN CN92101776.6A patent/CN1042745C/en not_active Expired - Lifetime
-
1993
- 1993-09-13 NO NO933256A patent/NO933256L/en unknown
- 1993-09-13 FI FI934002A patent/FI934002A/en unknown
-
1996
- 1996-05-23 GR GR960401378T patent/GR3020019T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CA2105090A1 (en) | 1992-09-14 |
| TW198063B (en) | 1993-01-11 |
| CZ190493A3 (en) | 1994-07-13 |
| IE920803A1 (en) | 1992-09-23 |
| FI934002A0 (en) | 1993-09-13 |
| PT100243A (en) | 1994-05-31 |
| DE69210992D1 (en) | 1996-06-27 |
| ATE138411T1 (en) | 1996-06-15 |
| DE69210992T2 (en) | 1996-11-28 |
| AU1419092A (en) | 1992-10-21 |
| GR3020019T3 (en) | 1996-08-31 |
| NO933256D0 (en) | 1993-09-13 |
| MA22463A1 (en) | 1992-10-01 |
| JPH06505764A (en) | 1994-06-30 |
| EP0575440A1 (en) | 1993-12-29 |
| NO933256L (en) | 1993-11-08 |
| CN1064887A (en) | 1992-09-30 |
| WO1992016609A1 (en) | 1992-10-01 |
| DK0575440T3 (en) | 1996-10-07 |
| HU9302584D0 (en) | 1993-12-28 |
| FI934002A (en) | 1993-09-13 |
| EG20454A (en) | 1999-04-29 |
| ES2087531T3 (en) | 1996-07-16 |
| HUT65576A (en) | 1994-07-28 |
| SK98493A3 (en) | 1994-02-02 |
| MX9201096A (en) | 1992-09-01 |
| EP0575440B1 (en) | 1996-05-22 |
| BR9205766A (en) | 1994-09-27 |
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| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
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Expiration termination date: 20120313 Granted publication date: 19990331 |