CN1708278A - Cosmetics excellent in texture and oil-dispersibility - Google Patents

Cosmetics excellent in texture and oil-dispersibility Download PDF

Info

Publication number
CN1708278A
CN1708278A CN 200380102353 CN200380102353A CN1708278A CN 1708278 A CN1708278 A CN 1708278A CN 200380102353 CN200380102353 CN 200380102353 CN 200380102353 A CN200380102353 A CN 200380102353A CN 1708278 A CN1708278 A CN 1708278A
Authority
CN
China
Prior art keywords
gamma
glutamic acid
poly
cross
linking products
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.)
Granted
Application number
CN 200380102353
Other languages
Chinese (zh)
Other versions
CN100358490C (en
Inventor
宫山哲夫
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
KK
Original Assignee
Idemitsu Technofine Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Idemitsu Technofine Co Ltd filed Critical Idemitsu Technofine Co Ltd
Publication of CN1708278A publication Critical patent/CN1708278A/en
Application granted granted Critical
Publication of CN100358490C publication Critical patent/CN100358490C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Abstract

A cosmetic excellent in texture which contains a crosslinked poly-gamma-glutamic acid compound and/or a crosslinked poly-gamma-glutamic acid salt having a particle size of from 0.1 to 100 mum and an average particle size of from 1 to 50 mum. This cosmetic shows no stickiness in using, is highly compatible with the skin and hair, exerts a moistening effect and has a favorable moist feeling and improved texture such as smoothness and oil-free feeling. A cosmetic excellent in oil-dispersibility which comprises an oily component selected from among vegetable oils, higher alcohols, esters thereof, higher fatty acid esters and liquid paraffin together with a crosslinked poly-gamma-glutamic acid compound and/or a crosslinked poly-gamma-glutamic acid salt as an oil-dispersibility improving agent. This cosmetic shows no stickiness in using, is highly compatible with the skin and hair and yet shows well dispersion of the oily component even though the content of a surfactant is zero or lessened.

Description

Cosmetics in quality and oil-dispersibility excellence
Technical field
The present invention relates to be used to comprise the cosmetic material of the cosmetic applications of cosmetics such as cosmetics for skin material, cosmetic hair material and cosmetic cosmetic material, the cosmetic material of using with the washing product that are used to comprise bath shampoo etc. and relate more particularly at various sensations such as smooth feeling and neatly feel and be improved aspect (neat feeling) and keep the cosmetic material of good water retention property simultaneously.
The present invention also relates to be used to comprise the cosmetic material of the cosmetic applications of cosmetics such as cosmetics for skin material, cosmetic hair material and cosmetic cosmetic material, the cosmetic material of using with the washing product that are used to comprise bath shampoo etc., with relate more particularly to such cosmetic material, promptly even when the surfactant that do not use surfactant or usage quantity to reduce therein still can disperse oiliness improver well.
Background technology
Require cosmetics for skin material such as lotion, emulsus lotion, emulsifiable paste and facial film, cosmetic hair material such as shampoo, irrigation, hair emulsifiable paste and hairspray and cosmetic cosmetic material such as foundation cream, lipstick and eye shadow cream and bath shampoo show good water conservation effect.Extensively be known that the lotion, cosmetic emulsifiable paste, hair emulsifiable paste, hair irrigation and the bath shampoo blending wetting agent that apply to skin or hair being used for.In addition, various wetting agents have been used for skin and cosmetic hair material such as skin lotion and emulsifiable paste, hair shampoo and irrigation etc., to prevent withered sense or loose sense and to keep moisture simultaneously and give damp to skin and hair.
Known many organic and inorganic substances with high-hydroscopicity energy.Yet, have good safety and the formation stability of product is had less adverse effect owing to require to be used for the wetting agent of cosmetic material, have only the applicable wetting agent of making cosmetic material of these materials of limited kinds.In addition, require wetting agent not only to show the ability of water absorbing capacity but also the anti-sealing evaporation of demonstration.Therefore, if wish, must use wetting agent with the form of its composite in many cases by using common wetting agent to reach above-mentioned various performance.Yet high-hydroscopicity material such as sodium lactate are electrolyte, so it has for product and prepare undesirable performance such as emulsifying suppresses effect, and this causes the limited quantity of employed material and limited application thereof.On the other hand, known polyhydric alcohol such as glycerol, sorbitol and propylene glycol show relative good water retention property.Yet,, therefore use the cosmetics etc. of polyhydric alcohol to tend in use sensation aspect deterioration because the product that comprises polyhydric alcohol tends to have viscosity.
In cosmetic material in the method for blending poly-aspartate or amino-acid ester (with reference to unsettled open clear 61 (1986)-33107 peace 10 (1998)-251402 of Nos. of Japanese patent application), cosmetic material shows good water conservation effect, but the damp deficiency, this causes it to have the sensation of viscosity.Therefore, need be provided at the cosmetic material that sensation is improved as smooth feeling and clean and tidy sense aspect.
In addition with cosmetics for skin material such as lotion, emulsus lotion, emulsifiable paste and facial film, cosmetic hair material such as shampoo, irrigation, hair emulsifiable paste and hairspray, cosmetic cosmetic material such as foundation cream, lipstick and eye shadow cream and bath shampoo shared oil type and non-oil type.The oil type cosmetic material contains the oiliness improver (for example, with reference to the unsettled open No.2000-38314 of Japanese patent application) that is dispersed in wherein.
Under oiliness improver is dispersed in situation in the cosmetic material, usually to the dispersant that comprises synthetic material such as non-ionic surface active agent that wherein adds as effective ingredient, to improve the dispersibility of oiliness improver.Yet, comprise the zest of the cosmetic material demonstration of non-ionic surface active agent to skin.In addition, from reducing the viewpoint of environmental pressure, natural fat and oil just by being used as oiliness improver with increasing.Yet, if wish sensation such as smooth feeling and the clean and tidy sense that acquisition is good, must under high concentration, use natural fat and oil, therefore cause the viscosity of problem as the product of acquisition.
In these cases, the purpose of this invention is to provide viscosity when not only showing less use, with the good intimate property of skin or hair, good water conservation effect and good damp, and at smooth feeling and the cosmetic material that neatly is improved aspect the sense.
In addition, another object of the present invention provides such cosmetic material, although be its when showing less use viscosity and still can in this cosmetic material, disperse oiliness improver well with the good intimate property of skin or hair and the surfactant that does not use surfactant or usage quantity to reduce therein.
Disclosure of the Invention
Because for finishing the broad research of above purpose, the inventor finds when being that 0.1-100 μ m and particle mean size are that the cross-linking products of poly-gamma-glutamic acid of 1-50 μ m and/or the cross-linking products of poly-gamma-glutamic acid salt add fashionable as wetting agent with granularity, viscosity when the cosmetic material that obtains can show less use and good water conservation effect and can be at various sensations such as smooth feeling and neatly be improved aspect the sense.That is, under the situation of common cosmetic material, if use therein wetting agent has coarsegrain, then cosmetic material shows good damp (water retention property), but shows harsh feeling.Yet if wetting agent has small grain size, cosmetic material shows less harsh feeling and good clean and tidy sense, but tends to deterioration aspect water retention property.In the present invention, when finding the cross-linking products when the cross-linking products of the poly-gamma-glutamic acid of use particle mean size in above particular range and/or poly-gamma-glutamic acid salt, the cosmetic material that obtains can be improved aspect smooth feeling and clean and tidy sense in sensation, and keep simultaneously good stable and good water retention property, these performances in acid range is that the cross-linking products of the cross-linking products of poly-gamma-glutamic acid and/or poly-gamma-glutamic acid salt is inherent.Finish the present invention according to above discovery.
In addition, the inventor finds when adding fashionable as the diffusing modifier of oil content the cross-linking products of poly-gamma-glutamic acid and/or the cross-linking products of poly-gamma-glutamic acid salt, viscosity when the cosmetic material that obtains can show less use and the good result of disperseing oiliness improver are not therein particularly being tied sheet (flaking) (the non-effect that bleaches when sprawling) on hair under the situation of cosmetic hair material.Also finish the present invention according to above discovery.
Therefore, the invention provides following cosmetic material:
[1] a kind of cosmetic material, it comprises granularity is that 0.1-100 μ m and particle mean size are the cross-linking products of poly-gamma-glutamic acid of 1-50 μ m and/or the cross-linking products of poly-gamma-glutamic acid salt.
[2] cosmetic material of project [1], wherein the quantity with 0.001-20 quality % comprises the cross-linking products of this poly-gamma-glutamic acid and/or the cross-linking products of this poly-gamma-glutamic acid salt.
[3] cosmetic material of project [1], wherein be used for its crosslinked radiation and produce the cross-linking products of this poly-gamma-glutamic acid or the cross-linking products of this poly-gamma-glutamic acid salt by at least a solution that is selected from aqueous solution, methanol solution and the alcoholic solution of poly-gamma-glutamic acid or poly-gamma-glutamic acid salt is exposed to, described solution comprises the poly-gamma-glutamic acid that quantity is 2-30 quality %.
[4] cosmetic material of project [1], wherein this radiation is gamma-radiation or electron beam.
[5] each cosmetic material in project [1]-[4], wherein this cosmetic material is as cosmetic hair material, cosmetics for skin material or nail cosmetic material.
[6] a kind of cosmetic material, it comprises the oiliness improver that is selected from vegetable oil, higher alcohol or its ester, senior fatty ester and liquid paraffin and as oil content the loose cross-linking products of poly-gamma-glutamic acid of modifier and/or the cross-linking products of poly-gamma-glutamic acid salt.
[7] cosmetic material of project [6], wherein the granularity of the cross-linking products of the cross-linking products of this poly-gamma-glutamic acid or this poly-gamma-glutamic acid salt is that 0.1-100 μ m and particle mean size are 1-50 μ m.
[8] cosmetic material of project [6] or [7], wherein the quantity that comprises of the cross-linking products that comprises cross-linking products that quantity is 0.01-80 quality % and this poly-gamma-glutamic acid and/or this poly-gamma-glutamic acid salt of this oiliness improver is 0.1-30 quality %.
[9] each cosmetic material in project [6]-[8], wherein be used for its crosslinked radiation and produce the cross-linking products of this poly-gamma-glutamic acid or the cross-linking products of this poly-gamma-glutamic acid salt by at least a solution that is selected from aqueous solution, methanol solution and the alcoholic solution of poly-gamma-glutamic acid or poly-gamma-glutamic acid salt is exposed to, described solution comprises the poly-gamma-glutamic acid that quantity is 1-30 quality %.
[10] cosmetic material of project [9], wherein this radiation is gamma-radiation or electron beam.
[11] according to each cosmetic material in project [6]-[10], wherein this cosmetic material is as cosmetic hair material, cosmetics for skin material or nail cosmetic material.
Implement best mode of the present invention
Restriction is not used as the raw-material poly-gamma-glutamic acid of wetting agent in the cosmetic material that has excellent sensation according to the present invention and can uses those poly-gamma-glutamic acids that obtained by various production methods especially.The example of production method comprises the use method for culturing microbes as the cultural method that uses bacillus subtilis (Bacillus subtilis), the cultural method of use genetically modified microorganism and the cultural method of being controlled by Bafillus natt (Bacillus natto), and chemical synthesis process.By using method for culturing microbes to produce under the situation of poly-gamma-glutamic acid, can use any bacterial strain that can beyond fungus body, produce poly-gamma-glutamic acid.In these bacterial strains, particularly preferably be Bacillus funguses.The object lesson of bacterial strain comprises bacillus subtilis, Bacillus anthracis (Bacillus anthracis) and Bafillus natt.Especially, preferred use produce by microorganism such as bacillus subtilis, molecular weight is millions of or bigger poly-gamma-glutamic acid (the unsettled open No. flat 1 (1989)-174397 of Japanese patent application).
In using method for culturing microbes, can use any bacterial strain or culture medium, as long as can produce poly-gamma-glutamic acid suitably thus.For example, can adopt any synthetic medium or any natural medium, as long as these culture medium comprise carbon source, nitrogenous source, inorganic substances and other nutrient aptly.The amino acid whose example that joins in the culture medium comprises L-glutamic acid, aspartic acid, alanine, leucine, phenylalanine, histidine and salt thereof.In these aminoacid and salt thereof, L-glutamic acid preferably.Can adopt the quantity of 2-12% and preferred 3-10% to add aminoacid or its salt.
The example of carbon source comprises glucose, sucrose, citric acid and xylose.In these carbon sources, preferably citric acid and glucose.The example of nitrogenous source comprises organic nutrient source such as peptone and yeast extract and inorganic nutrients source such as ammonium sulfate.
Cultivation can be carried out as vibrating under cultivation and the stir culture at aerobic condition.Cultivation temperature be 25-45 ℃ and preferred 30-40 ℃ and when cultivating the pH value of culture medium be 5-9 and preferred 6-8.Can be by being controlled at culture medium pH value when cultivating to wherein adding sodium hydroxide, potassium hydroxide etc.
Incubation time is generally 48-72 hour, wherein at the outside accumulation of fungus body poly-gamma-glutamic acid.After cultivation is finished, can be by the poly-gamma-glutamic acid in the common known method recovery culture solution.More specifically, filter and fungus body is removed from culture solution, then the solution that obtains is carried out ultrafiltration, reclaim poly-gamma-glutamic acid thus by centrifugalize or the filter that uses filtration adjuvant or contain micropore.Selecting as another kind, can be that solution quantity 3-4 ethanol doubly mixes to be settled out poly-gamma-glutamic acid from solution with culture solution and quantity.The precipitate that obtains is water-soluble with from wherein removing water-msoluble ingredients.Subsequently, with the solution that obtains dialyse, ultrafiltration etc., with from wherein removing low molecular weight substance, carry out the alcoholic acid redeposition process of multiple employing etc. then, with from wherein reclaiming poly-gamma-glutamic acid.
Can use poly-gamma-glutamic acid to obtain poly-gamma-glutamic acid salt by known response.The example of poly-gamma-glutamic acid salt comprises alkali metal salt such as sodium, potassium and lithium salts, ammonium salt, ethanolamine salt, diethanolamine salt, triethanolamine salt and the basic amine salt of poly-gamma-glutamic acid.
The cross-linking products that is used as the poly-gamma-glutamic acid of wetting agent in the cosmetic material that has excellent sensation according to the present invention can be produced by following mode: the poly-gamma-glutamic acid that dissolving obtains by above-mentioned use method for culturing microbes or chemical synthesis process in solvent, containing quantity with preparation is 2-30 quality %, preferably 2-20 quality % and the more preferably solution of the poly-gamma-glutamic acid of 5-15 quality %, the solution that obtains is exposed to radiation, then the cross-linking products that separation and purification obtain from solution.The example of solvent comprises water, alcohol, acetone, methyl acetate and ethyl acetate.In these solvents, preferably water, methanol and ethanol and be more preferably water.Can produce the cross-linking products of poly-gamma-glutamic acid salt by the method identical with the above.
The solution that has wherein dissolved poly-gamma-glutamic acid or poly-gamma-glutamic acid salt put into to see through radiating container, for example in glass vial etc.Restriction not can be used for radiation of the present invention especially.Radiating example comprises α-ray, beta rays, gamma-radiation, electron beam, neutron and X ray.In these radiation rays, preferably gamma-radiation and electron beam.Radiating electron beam quantity depends on the water absorption of condition such as target cross-linking products and changes and 20kGy or bigger preferably.Radiated time less than 1s tends to be not enough to obtain cross-linking products in some cases.Therefore, radiated time 1s or longer preferably.
Use the above method of such electron beam irradiation can produce the cross-linking products of poly-gamma-glutamic acid or the cross-linking products of poly-gamma-glutamic acid salt with required gelatine rate.Gelatine rate as the cross-linking products of the cross-linking products of the poly-gamma-glutamic acid of wetting agent or poly-gamma-glutamic acid salt is 20-100% in the present invention, preferred 40-100% and more preferably 60-100%.If the gelatine rate of cross-linking products is less than 20%, cross-linking products tends to aspect water retention property deficiency and its efficient and tends to descend.
Simultaneously, the gelatine rate is represented the numerical value that the dry mass by the wetting agent that will be made up of the cross-linking products of poly-gamma-glutamic acid obtains divided by the quantity of the poly-gamma-glutamic acid of experience electron beam irradiation as used herein, promptly based on the quantity of the poly-gamma-glutamic acid of initial adding, the percent of the dry mass of the wetting agent of forming by the cross-linking products of poly-gamma-glutamic acid.The gelatine rate of the cross-linking products of poly-gamma-glutamic acid salt has implication same as described above.
, cross-linking products carried out lyophilization etc. from wherein remove to anhydrate, obtain the cross-linking products of poly-gamma-glutamic acid of solid form or the cross-linking products of poly-gamma-glutamic acid salt thus thereafter.The cross-linking products of the cross-linking products of the poly-gamma-glutamic acid of Huo Deing or poly-gamma-glutamic acid salt is colourless and transparent and shows excellent water absorbing properties and favorable biological degradability like this.
Can be by using for example broken processing of fine powder of air-flow grinder, roll squeezer, ball mill etc. from the cross-linking products of wherein having removed water, control the granularity of the cross-linking products of the cross-linking products of poly-gamma-glutamic acid or poly-gamma-glutamic acid salt.The broken processing of fine powder is preferably carried out in the environment of cyclic drying air therein, to prevent particulate condensing.If desired, can be by the granularity of control cross-linking products such as ultrasonic classification.
In the cosmetic material that has excellent sensation according to the present invention, requiring the granularity of the cross-linking products of the cross-linking products of poly-gamma-glutamic acid or poly-gamma-glutamic acid salt is that 0.1-100 μ m and particle mean size are 1-50 μ m and preferred 5-30 μ m.If the granularity of the cross-linking products of the cross-linking products of poly-gamma-glutamic acid or poly-gamma-glutamic acid salt is less than 0.1 μ m, the cosmetic material of Huo Deing tends to deterioration aspect water retention property so.On the other hand, if the granularity of the cross-linking products of the cross-linking products of poly-gamma-glutamic acid or poly-gamma-glutamic acid salt greater than 100 μ m, the cosmetic material of Huo Deing tends to deterioration aspect clean and tidy sense so.
Being used as the cross-linking products of poly-gamma-glutamic acid of wetting agent or the cross-linking products of poly-gamma-glutamic acid salt in the cosmetic material that has excellent sensation according to the present invention can be widely used in lotion, emulsus lotion, cold emulsifiable paste, hand cream, lipstick, eye shadow cream, hair jelly, hair growth promoter, hair finishing agent, shampoo, irrigation, hair-waving solution, remove diaphoretic, bath shampoo etc.
The cosmetic material that has excellent sensation according to the present invention comprises quantity and is generally 0.001-20 quality %, preferred 0.001-10 quality %, more preferably 0.01-5 quality % and the cross-linking products of the poly-gamma-glutamic acid that is more preferably 0.1-2.5 quality % or the cross-linking products of poly-gamma-glutamic acid salt.If the quantity of the cross-linking products that adds is less than 0.001 quality %, then the cosmetic material of Huo Deing tends to deficiency aspect the water conservation effect.If the quantity of the cross-linking products that adds is greater than 20 quality %, then the cosmetic material of Huo Deing tends to show undesirable viscosity sense.
In the cosmetic material that has excellent sensation according to the present invention, be used as the cross-linking products of poly-gamma-glutamic acid of wetting agent and/or poly-gamma-glutamic acid salt cross-linking products can with other wetting agent for example propylene glycol, sorbitol, formic acid, sodium lactate etc. be used in combination, and can not produce infringement to its effect.
On the other hand, the oiliness improver that is used for having according to the present invention the cosmetic material of excellent oil-dispersing property can be selected from vegetable oil, higher alcohol or its ester, senior fatty ester and liquid paraffin.The example of vegetable oil comprises olive oil, Jojoba oil, Semen pruni armeniacae oil, Oleum Vitis viniferae, Flos Rosae Multiflorae fruit oil, American Avocado Tree oil, Oleum sesami, Semen Tritici aestivi germ oil, Radix Oenotherae erythrosepalae oil, Camellia oil and Camellia sasanqua Thunb. oil.
The example of higher alcohol comprises octyldodecanol, hexyl dodecanol and oleyl alcohol.The example of the ester of higher alcohol comprises Cetiol, octyl stearate, the adipic acid butyl ester, sad different cetyl, the different cetyl of isostearic acid, isononyl isononanoate, the isostearic acid isopropyl ester, the isostearyl isostearate ester, different n-nonanoic acid isotridecyl ester, oleyl erucate, (caprylic/capric) cocos nucifera oil Arrcostab, two capric acid DOPCP, dicaprylyl ether, tetramethylolmethane four-2-ethylhexanoate, pentaerythritol tetraoctyl stearate, hexyldecanol/hexyl decyl laurate, Adeps Bovis seu Bubali resin (shea fats), the dioctyl cyclohexane extraction, squalane, 2 ethyl hexanoic acid (2-ethylhexacenoate) cetyl, different n-nonanoic acid hexadecanol octadecanol ester, the trimethylolpropane tris caprylate, the trimethylolpropane tris stearate, Standamul 7061 and myristic acid octyl group dodecyl ester.
The example of senior fatty ester comprises monoesters, diester or three esters of glycerol such as polyoxyethylene coconut oil fat acid glyceride, three different tripalmitins and three (sad or capric acid) glyceride, lauric acid isooctadecanol ester, lauric acid hexyl ester, decyl oleate, isopropyl myristate and isopropyl palmitate.
These oiliness improvers can use separately or two or more be used in combination with it.
Restriction is not used as the raw-material poly-gamma-glutamic acid of the diffusing modifier of oil content in the cosmetic material that has excellent oil-dispersing property according to the present invention and can uses those poly-gamma-glutamic acids that obtained by various production methods especially.The example of production method comprises the use method for culturing microbes as the cultural method that uses bacillus subtilis, the cultural method of use genetically modified microorganism and the cultural method of being controlled by Bafillus natt, and chemical synthesis process.Can adopt mode same as described above to carry out the method for producing poly-gamma-glutamic acid by the use method for culturing microbes.
The cross-linking products that is used as the poly-gamma-glutamic acid of the diffusing modifier of oil content in the cosmetic material that has excellent oil-dispersing property according to the present invention can be produced by following mode: the poly-gamma-glutamic acid that dissolving obtains by above-mentioned use method for culturing microbes or chemical synthesis process in solvent, containing quantity with preparation is 1-30 quality %, preferably 2-20 quality % and the more preferably solution of the poly-gamma-glutamic acid of 5-15 quality %, adopt mode same as described above that the solution that obtains is exposed to radiation, then the cross-linking products that separation and purification obtain from solution.
Being used as the loose gelatine rate of cross-linking products of the cross-linking products of poly-gamma-glutamic acid of modifier or poly-gamma-glutamic acid salt of oil content in the cosmetic material that has excellent oil-dispersing property according to the present invention is 20-100%, preferred 40-100% and more preferably 60-100%.If the gelatine rate of cross-linking products is less than 20%, cross-linking products tends to aspect water retention property deficiency and its efficient and tends to descend.Simultaneously, the definition of gelatine rate is same as described above.
Can control the granularity of the cross-linking products of the cross-linking products of poly-gamma-glutamic acid or poly-gamma-glutamic acid salt by the method identical suitably with the method that the cosmetic material with excellent sensation is made an explanation.
In the cosmetic material that has excellent oil-dispersing property according to the present invention, from water retention property and sensation as smooth feeling with the viewpoint of the well balanced performance between neatly feeling, the granularity of the cross-linking products of the cross-linking products of poly-gamma-glutamic acid or poly-gamma-glutamic acid salt is preferably 0.1-100 μ m and particle mean size is 1-50 μ m.Particle mean size is 5-30 μ m more preferably.If the granularity of cross-linking products is less than 0.1 μ m, the cosmetic material of Huo Deing tends to deterioration aspect water retention property so.On the other hand, if the granularity of cross-linking products greater than 100 μ m, the cosmetic material of Huo Deing tends to deterioration aspect clean and tidy sense so.
Being used as the loose cross-linking products of poly-gamma-glutamic acid of modifier or the cross-linking products of poly-gamma-glutamic acid salt of oil content in the cosmetic material that has excellent oil-dispersing property according to the present invention can be widely used in lotion, emulsus lotion, cold emulsifiable paste, hand cream, lipstick, eye shadow cream, hair jelly, hair growth promoter, post-treatment agent, hair finishing agent, shampoo, irrigation, hair-waving solution, remove diaphoretic, bath shampoo etc.In addition, cross-linking products can be as the scavenger of cosmetic cosmetic material such as lipstick, eye shadow cream and buccal kermes.
Except the cross-linking products of the cross-linking products of above poly-gamma-glutamic acid and/or poly-gamma-glutamic acid salt; the scavenger compositions that is used for the cosmetic cosmetic material also can comprise the various components that are used for common cosmetic material; for example surfactant, oil, solvent, gelatine agent, medicine, water swelling clay mineral matter, polymer, pigment, antiseptic, viscosity modifier, antioxidant, spice and water are unless its interpolation influences effect of the present invention unfriendly.
As surfactant, can use various surfactants.The object lesson of anion surfactant comprises based on sulfate with based on the surfactant of sulfonate such as alkyl sulfate, laureth sulfate, based on the surfactant of 2-Sulfosuccinic acid, based on the surfactant of taurate, based on the surfactant of isethionate with based on the surfactant of alpha-olefin sulfonic acid; Based on the surfactant of carboxylate such as fatty acid soaps, based on the surfactant of ether carboxylic acid with based on the surfactant of acylated amino acid; With based on phosphatic surfactant as surfactant based on alkylphosphonic.
The object lesson of amphoteric surfactant comprises based on the surfactant of carbon-betanin (carbo-betaine), based on the surfactant of phospho-betanin, based on the surfactant of sulfo group-betanin with based on the surfactant of imidazoles-betanin.
The object lesson of non-ionic surface active agent comprises the surfactant of polyoxyalkylene addition type, the surfactant of polyoxypropylene/polyoxyethylene addition type, surfactant based on amine oxide, based on the surfactant of single ethanol amide with based on the surfactant of diglycollic amide, and based on the surfactant such as the anhydrosorbitol fatty ester of polyhydric alcohol, polyoxyethylene hardened castor oil and its fatty ester, the polyethylene glycol fatty ester, the glycerin fatty ester, the sucrose fatty ester, based on the surfactant of alkyl saccharide with based on the sugar of N-polyhydroxy alkyl fatty acid amide.
In these surfactants, from the viewpoint of good emulsifying dispersivity, preferably non-ionic surface active agent.
In the cosmetic material that has excellent oil-dispersing property according to the present invention, the content of the cross-linking products of the cross-linking products of above-mentioned oiliness improver and above-mentioned poly-gamma-glutamic acid and/or poly-gamma-glutamic acid salt can be determined according to the kind of cosmetic material suitably.The content of the cross-linking products of the cross-linking products of above-mentioned oiliness improver and above-mentioned poly-gamma-glutamic acid or poly-gamma-glutamic acid salt is respectively 0.01-80 quality % and 0.1-30 quality % usually, preferably be respectively 0.05-30 quality % and 0.1-10 quality % and more preferably be respectively 0.1-10 quality % and 0.1-5 quality %.If the quantity of the cross-linking products that adds is less than 0.1 quality %, the cosmetic material of Huo Deing tends in the oil-dispersibility deficiency so.If the quantity of cross-linking products is greater than 30 quality %, the cosmetic material of Huo Deing tends to occur the viscosity sense so.
In the cosmetic material that has excellent oil-dispersing property according to the present invention, be used as oil content loose the cross-linking products of poly-gamma-glutamic acid of modifier and/or poly-gamma-glutamic acid salt cross-linking products can with other wetting agent for example propylene glycol, sorbitol, formic acid, sodium lactate etc. be used in combination, and can not have a negative impact to effect of the present invention.In addition, cosmetic material of the present invention can with the additive that can be used for common cosmetic material, for example antiseptic such as nipagin and 1,3 butylene glycol are mixed, unless its interpolation influences effect of the present invention unfriendly.
Below, by describing the present invention in more detail with reference to following embodiment and Comparative Examples.Yet, should be noted that these embodiment only are illustrative, do not wish the present invention is limited to these embodiment.
Production example 1
With Meiji g-PGT (available from Meiji Seika Kaisha Co., the poly-gamma-glutamic acid of Ltd) 10 quality % aqueous solutions are put into the glass pallet, and use Cockcroft-Walton type electron beam irradiation equipment, from the distance of 10cm total time, thereby make that radiating electron beam quantity is 30kGy with the electron beam irradiation 12s of the intensity of 2.5kGy/s.The treated material that obtains is immersed in the water week down with from wherein removing uncrosslinked poly-gamma-glutamic acid at 4 ℃.The swollen poly-gamma-glutamic acid gel of water is separated by filtering through 80 purpose metallic sieves, then lyophilization and obtain the gelatine rate be 91% and particle mean size be the cross-linking products of the poly-gamma-glutamic acid of 200 μ m.It is broken that the cross-linking products of the poly-gamma-glutamic acid that obtains is like this carried out fine powder with ball mill and air-flow grinder, and obtaining particle mean size thus is the cross-linking products granule of the poly-gamma-glutamic acid of 10 μ m.The granule that obtains is further carried out the broken processing of fine powder, and obtaining particle mean size thus is the cross-linking products fine grained of the poly-gamma-glutamic acid of 0.1 μ m.
Simultaneously, with the poly-gamma-glutamic acid Drying of gels quality that obtains the percent of the quality of the poly-gamma-glutamic acid of initial adding is determined the gelatine rate.In addition, use available from SeishinKigyo Co., the type of laser particle size distribution measurement equipment " LMS-3 " of Ltd adopts the principle of fraunhofer (Fraunhofer) diffraction to measure above-mentioned particle mean size.
Embodiment 1 and 2, reference example 1 and 2, and Comparative Examples 1-3
The cross-linking products of the poly-gamma-glutamic acid that production example 1 is obtained mixes with water, ethanol and spice with the mass ratio shown in the table 1, produces the cosmetics for skin material thus.Simultaneously, as the cross-linking products of poly-gamma-glutamic acid, in embodiment 1 and 2, using particle mean size is the cross-linking products of 10 μ m; Reference example 1 and 2 and Comparative Examples 1 in, using particle mean size is the cross-linking products (it does not carry out the broken processing of fine powder) of 200 μ m; With in Comparative Examples 3, using particle mean size is the cross-linking products of 0.1 μ m.
Above cosmetics for skin material is applied on the application on human skin, dry then, to estimate its damp, neat sense (tidy feeling) and clean and tidy sense according to following opinion rating.The results are shown in Table 1.
Damp: A: good; B: poor
Neat sense: A: inviscid; B: be clamminess
Clean and tidy sense: A: good; B: poor
Comparative Examples 4
Repeat with embodiment 1 in identical process, distinguish and be to use Meiji γ-PGA to replace the cross-linking products of poly-gamma-glutamic acid as uncrosslinked poly-gamma-glutamic acid.The results are shown in Table 1.
Table 1-1
Embodiment Reference example
The quantity of blending (quality %) ????1 ????2 ????1 ????2
Water ????89.4 ????89.0 ????89.4 ????89.0
Ethanol ????10.0 ????10.0 ????10.0 ????10.0
Spice ????0.5 ????0.5 ????0.5 ????0.5
The cross-linking products of poly-gamma-glutamic acid
Particle mean size: 200 μ m ????0.1 ????0.5
Particle mean size: 10 μ m ????0.1 ????0.5
Particle mean size: 0.1 μ m
Uncrosslinked poly-gamma-glutamic acid
Evaluation result
Damp ????A ????A ????A ????A
Neat sense ????A ????A ????A ????A
Clean and tidy sense ????A ????A ????B ????B
Table 1-2
Comparative Examples
The quantity of blending (quality %) ????1 ????2 ????3 ????4
Water ????64.5 ????89.5 ????89.0 ????89.4
Ethanol ????10.0 ????10.0 ????10.0 ????10.0
Spice ????0.5 ????0.5 ????0.5 ????0.5
The cross-linking products of poly-gamma-glutamic acid
Particle mean size: 200 μ m ????25.0
Particle mean size: 10 μ m
Particle mean size: 0.1 μ m ????0.5
Uncrosslinked poly-gamma-glutamic acid ????0.1
Evaluation result
Damp ????A ????B ????B ????B
Neat sense ????B ????A ????A ????A
Clean and tidy sense ????B ????B ????B ????B
Embodiment 3-7
The cross-linking products of the poly-gamma-glutamic acid of acquisition in the production example 1 is mixed with oiliness improver, water and antiseptic with the mass ratio shown in the table 2, produce cosmetic hair material (post-treatment agent) thus.Simultaneously, as the poly-gamma-glutamic acid cross-linking products, in embodiment 3-5, using particle mean size is the cross-linking products of 10 μ m; With in embodiment 6 and 7, use the cross-linking products of particle mean size as 1mm, it does not carry out the broken processing of fine powder.
Above cosmetic hair material is applied on the hair, dry then, with the generation (what cause when sprawling on hair bleaches) of estimating oil-dispersing property, level and smooth sense, knot sheet according to following opinion rating with to the zest of skin.The results are shown in table 2.Simultaneously, estimate oil-dispersing property by visual observations.
Oil-dispersing property: A: good; B: omit; C: poor
Clean and tidy sense: A: good; B: omit; C: poor
Knot sheet: A: do not have; B: take place
Zest to skin: A: do not have; B: take place
Comparative Examples 5
Repeat with embodiment 3 in identical process, distinguish and be to use Meiji γ-PGA to replace the cross-linking products of poly-gamma-glutamic acid as uncrosslinked poly-gamma-glutamic acid.The results are shown in Table 2.
Comparative Examples 6
Repeat with embodiment 3 in identical process, distinguish and be to use polyoxyethylene (40) hardened castor oil to replace the cross-linking products of poly-gamma-glutamic acid as non-ionic surface active agent.The results are shown in Table 2.
Comparative Examples 7
Repeat with embodiment 3 in identical process, distinguish and be to use polyvinylpyrrolidone to replace the cross-linking products of poly-gamma-glutamic acid.The results are shown in Table 2.
Comparative Examples 8
Repeat with embodiment 3 in identical process, distinguish the cross-linking products that is not use poly-gamma-glutamic acid.The results are shown in Table 2.
Table 2-1
Embodiment
The quantity of blending (quality %) ????3 ????4 ????5 ????6 ????7
Water ????91.0 ????91.0 ????91.0 ????91.0 ????91.0
Cetyol??ISL ????5.0 ????5.0
Cetyol?PEEH4 ????5.0 ????5.0
Cetyol?S ????5.0
Nipagin ????0.2 ????0.2 ????0.2 ????0.2 ????0.2
1,3 butylene glycol ????1.8 ????1.8 ????1.8 ????1.8 ????1.8
The cross-linking products of poly-gamma-glutamic acid
Particle mean size: 10 μ m ????2.0 ????2.0 ????2.0
Particle mean size: 1mm ????2.0 ????2.0
Uncrosslinked poly-gamma-glutamic acid
NIKKOL?HCO-40
PVP?K-90
Evaluation result
Oil-dispersing property ????A ????A ????A ????B ????B
Clean and tidy sense ????A ????A ????A ????B ????B
The knot sheet ????A ????A ????A ????A ????A
Zest to skin ????A ????A ????A ????A ????A
Table 2-2
Comparative Examples
The quantity of blending (quality %) ????5 ????6 ????7 ????8
Water ????91.0 ????91.0 ????92.0 ????93.0
Cetyol?ISL ????5.0 ????5.0 ????5.0 ????5.0
Cetyol?PEEH4
Cetyol?S
Nipagin ????0.2 ????0.2 ????0.2 ????0.2
1,3 butylene glycol ????1.8 ????1.8 ????1.8 ????1.8
The cross-linking products of poly-gamma-glutamic acid
Particle mean size: 10 μ m
Particle mean size: 1mm
Uncrosslinked poly-gamma-glutamic acid ????2.0
NIKKOL?HCO-40 ????2.0
PVP?K-90 ????1.0
Evaluation result
Oil-dispersing property ????C ????C ????A ????C
Clean and tidy sense ????C ????C ????C ????C
The knot sheet ????A ????A ????C ????A
Zest to skin ????A ????C ????C ????A
Remarks:
Cetyol ISL: available from Cognis Japan Co., the lactic acid isooctadecanol ester of Ltd;
Cetyol PEEH4: available from Cognis Japan Co., tetramethylolmethane four 2 ethyl hexanoic acids of Ltd;
Cetyol S: available from Cognis Japan Co., the dioctyl cyclohexane extraction of Ltd;
NIKKOL HCO-40: available from Nikko Chemicals Co., the polyoxyethylene of Ltd (40) hardened castor oil; With
PVP K-90: available from the polyvinylpyrrolidone of BASF.
Embodiment 8
With the water of 96 quality %, the particle mean size of 2.0 quality % is 1,3 butylene glycol uniform dissolution and the dispersion of nipagin and the 1.8 quality % of the cross-linking products of the poly-gamma-glutamic acid of 30 μ m, 0.2 quality %, thereby obtains cosmetics scavenger compositions.Simultaneously, coming the production particle mean size by the following method is the cross-linking products of the poly-gamma-glutamic acid of 30 μ m, and promptly adopting the method identical with production example 1 is that the cross-linking products fine powder of the poly-gamma-glutamic acid that obtains during the production technology of production example 1 of 200 μ m is broken into the cross-linking products that particle mean size is the poly-gamma-glutamic acid of 30 μ m with particle mean size.
The cosmetics scavenger compositions of Huo Deing is used to remove the lipstick by the usual method preparation with following composition like this, and carries out following evaluation.The results are shown in Table 3.
The composition of lipstick:
Three (caprylic/capric) glyceride, 15.0 quality %
Oleum Ricini 32.6 quality %
Tetramethylolmethane four caprylates 5.0 quality %
Microwax 5.0 quality %
Neopentyl glycol dicaprate 5.0 quality %
Candelilla wax 11.0 quality %
Ceresin 5.0 quality %
Sucrose stearate 3.0 quality %
Glycerin fatty ester 2.0 quality %
Squalane 2.0 quality %
Tocopherol 2.0 quality %
BHT 1.0 quality %
Butyl Chemosept 0.1 quality %
Propyl parabene 0.1 quality %
Citric acid 1.0 quality %
Barium sulfate 1.0 quality %
Titanium dioxide 2.0 quality %
Muscovitum 1.0 quality %
Red #202 2.0 quality %
Red #204 1.0 quality %
Red #218 0.5 quality %
Blue #204 1.5 quality %
Yellow #205 1.2 quality %
<evaluation methodology 〉
(1) cleaning capacity
Five women group members are coated in above lipstick on their lip, after 2 hours, use the Cotton Gossypii wiper lip by above cosmetics scavenger compositions dipping in the past.Visual observations and estimate the effect of removing of cosmetics according to following opinion rating.
A: very well remove
B: remove well
C: remove great majority
D: almost do not remove
(2) to the zest of skin
Five women group members use their lip of Cotton Gossypii wiping and the surrounding skin thereof that is flooded by above cosmetics scavenger compositions.According to the zest of following grade evaluation to skin.
A: the imperceptible zest of all five group members to their skin
B: imperceptible zest on skin but some senses of discomfort are physically arranged
C: one or several group member feel to the zest of skin
Sensation when (3) using
When estimating above cleaning capacity, according to the sense of touch (viscosity) of following opinion rating evaluation after making the scavenger compositions that applies some make up.
A: clean and tidy sense and good sense of touch
B: inviscid
C: omit toughness
D: tangible viscosity
Embodiment 9
With with method evaluation identical described in the embodiment 8 cosmetics scavenger compositions that in embodiment 8, obtains and the cosmetics scavenger compositions for preparing of the liquid paraffin of 1 mass parts by blending 99 weight portions each other.The results are shown in Table 3.
Embodiment 10
With with method evaluation identical described in the embodiment 8 cosmetics scavenger compositions that in embodiment 8, obtains and the cosmetics scavenger compositions for preparing of the liquid paraffin of 5 mass parts by blending 95 weight portions each other.The results are shown in Table 3.
Comparative Examples 9
The use liquid paraffin replaces the cosmetics scavenger compositions of acquisition among the embodiment 8 and estimates with the same procedure described in the embodiment 8.The results are shown in Table 3.
Comparative Examples 10
Use is estimated by the cosmetics scavenger compositions of acquisition among the cosmetics scavenger compositions replacement embodiment 8 that comprises following component of usual method preparation with the same procedure described in the embodiment 8.The results are shown in Table 3.
<cosmetics scavenger compositions 〉
Liquid paraffin 52.0 quality %
Isopropyl palmitate 2.0 quality %
Sorbes-30 four oleates 5.0 quality %
Sorbitan sesquioleate 2.0 quality %
Olive oil 2.0 quality %
Tocopherol 2.0 quality %
Soybean oil 4.0 quality %
Spice 0.5 quality %
Water 30.5 quality %
Table 3
Assessment item Embodiment Comparative Examples
????8 ????9 ????10 ????9 ????10
Cleaning capacity ????B ????B ????A ????C ????A
Zest to skin ????A ????A ????A ????C ????C
Sensation during use ????A ????A ????B ????D ????C
Industrial applicibility
According to the present invention, by use granularity as 0.1-100 μ m and average granularity as the cross-linking products of the cross-linking products of the poly-gamma-glutamic acid of 1-50 μ m and/or poly-gamma-glutamic acid salt as wetting agent, can produce easily the cosmetic material with excellent sensation, this cosmetic material shows damp, less viscosity and clean and tidy sense.
In the cosmetic material that has excellent sensation according to the present invention, be used as wetting agent poly--cross-linking products of γ-glutamic acid or the cross-linking products of poly-gamma-glutamic acid salt even when the water conservation effect that also shows excellence when joining on a small quantity in the cosmetic material, and show good and intimate property skin and hair and good biodegradation, therefore can be widely used in lotion, emulsus lotion, cold emulsifiable paste, hand cream, lipstick, eye shadow cream, hair jelly, preparation for baldness, hair arrangement agent, shampoo, irrigation, hair-waving solution, perspiration removing agent, bath agent etc.
In addition, in the present invention, when the cross-linking products of the cross-linking products of poly-gamma-glutamic acid and/or poly-gamma-glutamic acid salt during as the loose modifier of oil content, can produce easily and have excellent oil dispersiveness, less viscosity, the less excitant to skin, and the cosmetic material of neatly feeling.
In have the dispersed cosmetic material of excellent oil according to the present invention, be used as the cross-linking products of the cross-linking products of poly-gamma-glutamic acid of the loose modifier of oil content or poly-gamma-glutamic acid salt even when also showing the excellent oil content effect of faling apart when joining on a small quantity in the cosmetic material, and show sense of touch after good and intimate property skin and hair, good biodegradation and excellent cleaning capacity and the good use, and the less excitant to eyes, therefore can be widely used in lotion, emulsus lotion, cold emulsifiable paste, hand cream, lipstick, eye shadow cream, hair jelly, preparation for baldness, post-treatment agent, hair arrangement agent, shampoo, irrigation, hair-waving solution, perspiration removing agent, bath agent etc., and further also can be used as the removing agent of making up with cosmetic material such as lipstick, eye shadow cream and cheek kermes.

Claims (11)

1. cosmetic material, it comprises granularity is that 0.1-100 μ m and particle mean size are the cross-linking products of poly-gamma-glutamic acid of 1-50 μ m and/or the cross-linking products of poly-gamma-glutamic acid salt.
2. according to the cosmetic material of claim 1, wherein the quantity with 0.001 quality %-20 quality % comprises the cross-linking products of this poly-gamma-glutamic acid and/or the cross-linking products of this poly-gamma-glutamic acid salt.
3. according to the cosmetic material of claim 1, wherein be used for its crosslinked radiation and produce the cross-linking products of this poly-gamma-glutamic acid or the cross-linking products of this poly-gamma-glutamic acid salt by at least a solution that is selected from aqueous solution, methanol solution and the alcoholic solution of poly-gamma-glutamic acid or poly-gamma-glutamic acid salt is exposed to, described solution comprises the poly-gamma-glutamic acid that quantity is 2-30 quality %.
4. according to the cosmetic material of claim 1, wherein this radiation is gamma-radiation or electron beam.
5. according to each cosmetic material among the claim 1-4, wherein this cosmetic material is as cosmetic hair material, cosmetics for skin material or nail cosmetic material.
6. cosmetic material, it comprises the oiliness improver that is selected from vegetable oil, higher alcohol or its ester, senior fatty ester and liquid paraffin and as oil content the loose cross-linking products of poly-gamma-glutamic acid of modifier and/or the cross-linking products of poly-gamma-glutamic acid salt.
7. according to the cosmetic material of claim 6, wherein the granularity of the cross-linking products of the cross-linking products of this poly-gamma-glutamic acid or this poly-gamma-glutamic acid salt is that 0.1-100 μ m and particle mean size are 1-50 μ m.
8. according to the cosmetic material of claim 6, wherein the quantity that comprises of the cross-linking products that comprises cross-linking products that quantity is 0.01-80 quality % and this poly-gamma-glutamic acid and/or this poly-gamma-glutamic acid salt of this oiliness improver is 0.1-30 quality %.
9. according to the cosmetic material of claim 6, wherein be used for its crosslinked radiation and produce the cross-linking products of this poly-gamma-glutamic acid or the cross-linking products of this poly-gamma-glutamic acid salt by at least a solution that is selected from aqueous solution, methanol solution and the alcoholic solution of poly-gamma-glutamic acid or poly-gamma-glutamic acid salt is exposed to, described solution comprises the poly-gamma-glutamic acid that quantity is 1-30 quality %.
10. according to the cosmetic material of claim 9, wherein this radiation is gamma-radiation or electron beam.
11. according to each cosmetic material among the claim 6-10, wherein this cosmetic material is as cosmetic hair material, cosmetics for skin material or nail cosmetic material.
CNB2003801023532A 2002-10-31 2003-10-30 Cosmetics excellent in texture and oil-dispersibility Expired - Fee Related CN100358490C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP317556/2002 2002-10-31
JP2002317556A JP2004149467A (en) 2002-10-31 2002-10-31 Cosmetics excellent in hair touch feeling
JP340359/2002 2002-11-25

Publications (2)

Publication Number Publication Date
CN1708278A true CN1708278A (en) 2005-12-14
CN100358490C CN100358490C (en) 2008-01-02

Family

ID=32460924

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2003801023532A Expired - Fee Related CN100358490C (en) 2002-10-31 2003-10-30 Cosmetics excellent in texture and oil-dispersibility

Country Status (2)

Country Link
JP (1) JP2004149467A (en)
CN (1) CN100358490C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108078796A (en) * 2017-12-28 2018-05-29 珠海伊斯佳科技股份有限公司 A kind of no silicone oil moistens submissive hair film and preparation method thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101096868B1 (en) * 2004-10-26 2011-12-22 가부시키가이샤 시세이도 Skin preparation for external use

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001072764A (en) * 1999-09-02 2001-03-21 Mitsui Chemicals Inc Base material
JP2001354542A (en) * 2000-06-09 2001-12-25 Yamada Bee Farm Moisturizer and toiletry goods containing the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108078796A (en) * 2017-12-28 2018-05-29 珠海伊斯佳科技股份有限公司 A kind of no silicone oil moistens submissive hair film and preparation method thereof

Also Published As

Publication number Publication date
CN100358490C (en) 2008-01-02
JP2004149467A (en) 2004-05-27

Similar Documents

Publication Publication Date Title
CN1319508C (en) Semitransparent cosmetics
CN1226997C (en) Foamable oily gel composition
CN1188108C (en) Cosmetic product containing enzymes
CN1165287C (en) Compositions contg. antifungal and cationic agent
CN1211068C (en) Cosmetic preparation containing plant extracts
CN1365293A (en) Agents promoting the formation of skin basement, agents promoting the formation of artificial skin and process for producing artificial skin
CN1805728A (en) Shampoo and body detergent composition
CN1264294A (en) Liquid antimicrobial cleansing compositions
CN1615118A (en) Water-in-oil emulsion preparation for external use on skin
CN110317840B (en) Method for preparing sphingolipid
CN1280486A (en) Use of substantially amorphous cellulose nanofibrils associated with a polyhydroxylated compound in cosmetic formulations
CN1117558C (en) Compositions containing an antifungal and a sulfur compound
CN1723872A (en) Oil-in-water emulsified composition
CN1155359C (en) Compositions contg. antifungal and phospholipid
CN1144475A (en) Polyamino salts of alpha-hydroxyacids, alpha-ketoacids and related compounds
CN1202797C (en) Revitalising active complex for the skin
CN1853607A (en) Emulsifying compositions based on fatty alcohol and alkylpolyglycosides
CN1744879A (en) Whitening agent, skin preparation for external use and cosmetic
CN1265020A (en) Decorative cosmetic O/W emulsion containing no emulsion
CN1870969A (en) Climate-resistant cosmetic complex
CN1155357C (en) Emulsifide cosmetic face pack
CN1708278A (en) Cosmetics excellent in texture and oil-dispersibility
CN1568927A (en) Water soluble combination with elution preventing function and its application in cosmetics
CN1296404A (en) Agents promoting laminin production in skin cells
CN1134249C (en) Face pack

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
ASS Succession or assignment of patent right

Owner name: HATZ RATS CO., LTD.

Free format text: FORMER OWNER: IDEMITSU TECHNOFINE CO., LTD.

Effective date: 20140721

C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20140721

Address after: Miyagi Prefecture in Japan

Patentee after: KK

Address before: Tokyo, Japan

Patentee before: Idemitsu Technofine Co., Ltd.

CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20080102

Termination date: 20171030