CN101087579A - Storage of pulverulent substances having a high water content - Google Patents
Storage of pulverulent substances having a high water content Download PDFInfo
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- CN101087579A CN101087579A CN 200580044275 CN200580044275A CN101087579A CN 101087579 A CN101087579 A CN 101087579A CN 200580044275 CN200580044275 CN 200580044275 CN 200580044275 A CN200580044275 A CN 200580044275A CN 101087579 A CN101087579 A CN 101087579A
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Abstract
The invention provides a method of releasing water from powder product, which includes cosmetic, detergent, and abstergent. Wherein, the powder product contains not least than 50 wt% water and hydrophobic silicon dioxide powder, and characters in that the powder product connects to hydrophobic materials in storage process.
Description
Technical field
The present invention relates to a kind of storage means with flour of high water content.
Background technology
" solid carbon dioxide (Dry water) " is that a kind of water content reaches the powdery solid above 95%.It fully mixes formation by water with hydrophobic pyrolytic silicon dioxide.In this process, water droplet is encased by solid particle, and is prevented from flowing to together once more.Use " solid carbon dioxide " as the initial experiment of cosmetics substrate since the sixties in 20th century (DE-A-1467023, US 3393155, microgranule serial number 11, Degussa AG).In the later stage nineties 20th century, this conception of species is rebuild by Japanese cosmetic company, and is further developed (EP-A-855177, EP-A-1206928, EP-A-1235554).Yet, up to now, only have several cosmetics to have bought from the market.
Pyrolytic silicon dioxide and the water hydrophobic by abundant mixing prepare " solid carbon dioxide ".In this process, the water droplet that produces in the mixed process is encased by the non-wettable silica dioxide granule of water, and is prevented from flowing to together once more.Therefore, " solid carbon dioxide " can be considered to by the stable aerosol of solid particle (referring to the sketch map of Fig. 3).Depend on mixing condition, water droplet is of a size of 10 to hundreds of micron (referring to Fig. 4).The key that forms " solid carbon dioxide " is the hydrophobicity of pyrolytic silicon dioxide, because it does not disperse at aqueous phase, but " is adsorbed " on the water droplet surface simply.On the other hand, microgranule water-wettable solid forms suspension through being blended in the aqueous phase distribution.
Except " solid carbon dioxide ", " dried hydrogen peroxide " also is known.The hydrophobic SiO 2 powder of 5-10 weight % is enough to make thin, free-pouring powder (WO2004104154) from the hydrogenperoxide steam generator of concentration change.
About security feature, after deliberation such as the stability of products such as other peroxide and the tendency of spontaneous decomposition." dried hydrogen peroxide " but be a kind of storage substance with good handling property.By proper method release of active ingredients hydrogen peroxide optionally.Mechanical intervention such as grinding, pressure or vacuum make active component discharge fast from powder.After product being stirred in the water inlet solution, H
2O
2Flowed out in several minutes to a few hours, this depends on blended abundant degree.Liquid H can used
2O
2Be not suitable for or impossible situation under use dried hydrogen peroxide.For example, it can be used as bleach in cleaning agent and detergent, or is used for cosmetics according to maximum allowable concentration in the final cosmetics of application and cosmetics decree (German cosmetics decree) regulation.In this way, the disinfective action of hydrogen peroxide can be used in the product of cosmetics industry or is used for household products.It will also be appreciated that the application of the active component that use under proper condition delays to discharge.
The performance and the stability of " solid carbon dioxide " and " dried hydrogen peroxide " can be determined by the additive (example gel forms agent, wetting agent, solvent etc.) and the preparation method of various parameters (for example hydrophobicity of SiO 2 powder and specific surface area), water.
When preparation " solid carbon dioxide ", must make enough little water droplet and silica dioxide granule simultaneously.This needs high mixed tensor.For example operating speed is about 10, and the super mixer of 000rpm has obtained fabulous result.Conventional kitchen mixers also can provide stable powder.
Preparation " solid carbon dioxide " is used several seconds usually to maximum a few minutes.Optimum incorporation time depends on the composition and the selected blender of water basically.Therefore, must regulate for various situations.
EP-A-1386599 discloses the positive impact to " solid carbon dioxide " storage stability that takes place when a kind of vessel surface that solid carbon dioxide contacted in the solid carbon dioxide preparation process is hydrophobicity.Yet this method is not obviously improved storage stability yet.On the contrary, water separates with powder product in storing process, forms the water of additional separation.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind of method that can improve the storage stability of solid carbon dioxide and dried hydrogen peroxide.
Surprisingly, by postponing to realize this purpose from the method for powder release water, described powder comprises cosmetics, cleaning agent and detergent, wherein said powder contains the water of at least 50 weight % and hydrophobic SiO 2 powder, it is characterized in that, contact with hydrophobic material at powder described in the storing process.
The present invention is wonderful, because according to the instruction of EP-A-1386599, those skilled in the art have thought only has hydrophobic wall (hydrophobicwalling) to be correlated with when the preparation powder.
On the contrary, in the present invention, the preparation powder can carry out in having the container of non-hydrophobic wall.To what prolong that storage stability has material impact is follow-up storage in container, and wherein said powder only contacts with hydrophobic wall.
The type of hydrophobic SiO 2 powder needs only and form powder product when being added to it in water without limits.Hydrophobic SiO 2 powder preferably can be silylated.Halogenated silanes, alkoxy silane, silazane and/or siloxanes can be used for silanization.
Especially, following material can be used as halogenated silanes:
Organo-halogen-silane type X
3Si (C
nH
2n+1), wherein X=Cl, Br and n=1-20
Organo-halogen-silane type X
2(R ') Si (C
nH
2n+1), wherein X=Cl, Br and R '=alkyl, n=1-20
Organo-halogen-silane type X (R ')
2Si (C
nH
2n+1), wherein X=Cl, Br, R '=base, n=1-20
Organo-halogen-silane type X
3Si (CH
2)
m-R ', wherein X=Cl, Br, m=0.1-20, R '=alkyl, aryl (for example-C
6H
5) ,-C
4F
9,-OCF
2-CHF-CF
3,-C
6F
13,-O-CF
2-CHF
2,-NH
2,-N
3,-SCN ,-CH=CH
2,-OOC (CH
3) C=CH
2,-OCH
2-CH (O) CH
2,-NH-COO-CH
3,-NH-COO-CH
2-CH
3,-NH-(CH
2)
3Si (OR)
3,-S
x-(CH
2)
3Si (OR)
3,
Organo-halogen-silane type (R) X
2Si (CH
2)
m-R ', wherein X=Cl, Br, the R=alkyl, m=0.1-20, R '=alkyl, aryl (for example-C
6H
5) ,-C
4F
9,-OCF
2-CHF-CF
3,-C
6F
13,-O-CF
2-CHF
2,-NH
2,-N
3,-SCN ,-CH=CH
2,-OOC (CH
3) C=CH
2,-OCH
2-CH (O) CH
2,-NH-COO-CH
3,-NH-COO-CH
2-CH
3,-NH-(CH
2)
3Si (OR)
3,-NH-COO-CH
3,-NH-COO-CH
2-CH
3,-NH-(CH
2)
3Si (OR)
3,-S
x-(CH
2)
3Si (OR)
3,
Organo-halogen-silane type (R)
2XSi (CH
2)
m-R ', wherein X=Cl, Br, the R=alkyl, m=0.1-20, R '=alkyl, aryl (for example-C
6H
5) ,-C
4F
9,-OCF
2-CHF-CF
3,-C
6F
13,-O-CF
2-CHF
2,-NH
2,-N
3,-SCN ,-CH=CH
2,-OOC (CH
3) C=CH
2,-OCH
2-CH (O) CH
2,-NH-COO-CH
3,-NH-COO-CH
2-CH
3,-NH-(CH
2)
3Si (OR)
3,-S
x-(CH
2)
3Si (OR)
3,
Especially, following material can be used as alkoxy silane:
Organosilan type (RO)
3Si (C
nH
2n+1), R=alkyl wherein, n=1-20
Organosilan type R '
x(RO)
ySi (C
nH
2n+1), R=alkyl wherein, R '=alkyl, n=1-20, x+y=3, x=1,2, y=1,2
Organosilan type (RO)
3Si (CH
2)
m-R ', R=alkyl wherein, m=0.1-20, R '=alkyl, aryl (for example-C
6H
5) ,-C
4F
9, OCF
2-CHF-CF
3,-C
6F
13,-O-CF
2-CHF
2,-NH
2-N
3-SCN ,-CH=CH
2,-OOC (CH
3) C=CH
2,-OCH
2-CH (O) CH
2,-NH-COO-CH
3,-NH-COO-CH
2-CH
3,-NH-(CH
2)
3Si (OR)
3,-S
x-(CH
2)
3Si (OR)
3
Organosilan type (R ")
x(RO)
ySi (CH
2)
m-R ', wherein R "=alkyl, x+y=2, x=1,2, y=1,2, R '=alkyl, aryl (for example-C
6H
5) ,-C
4F
9,-OCF
2-CHF-CF
3,-C
6F
13,-O-CF
2-CHF
2,-NH
2,-N
3,-SCN ,-CH=CH
2,-OOC (CH
3) C=CH
2,-OCH
2-CH (O) CH
2, NH-COO-CH
3,-NH-COO-CH
2-CH
3,-NH-(CH
2)
3Si (OR)
3,-S
x-(CH
2)
3Si (OR)
3
Trimethoxyoctylsilane [(CH
3O)
3-Si-C
8H
17] (for example DYNASYLAN OCTMO, Degussa AG) can be preferably used as silanizing agent.
Especially, following material can be used as silazane:
The silazane type:
R=alkyl wherein, R '=alkyl, vinyl and for example hexamethyldisiloxane (for example DYNASYLAN HMDS).
Especially, following material can be used as siloxanes:
Cyclic polysiloxanes type D3, D4, D5, for example octamethylcy-clotetrasiloxane=D4
Polysiloxanes or silicone oil type:
R=alkyl, aryl, (CH
2)
n-NH
2, H
R '=alkyl, aryl, (CH
2)
n-NH
2, H
R "=alkyl, aryl, (CH
2)
n-NH
2, H
R =alkyl, aryl, (CH
2)
n-NH
2, H
Y=CH
3, H, C
nH
2n+1, n=1-20 wherein
Y＝Si(CH
3)
3、Si(CH
3)
2H
Si(CH
3)
2OH、Si(CH
3)
2(OCH
3)
Si (CH
3)
2(C
nH
2n+1), n=1-20 wherein
m＝0，1，2，3，...∞
n＝0，1，2，3，...∞
u＝0，1，2，3，...∞
Can spray SiO 2 powder, carry out silanization at 105～400 ℃ of following heat treated mixture 1～6h of temperature then by the silanizing agent that randomly is dissolved in organic solvent such as the ethanol.
To the SiO 2 powder of hydrophobic usefulness without limits.Can preferably use the SiO 2 powder in pyrolysis source.Herein, the term pyrolysis comprises the powder that obtains by flame oxidation or flame hydrolysis from the silicon compound that is fit to.Usually, Silicon chloride. hydrolysis in hydrogen and oxygen flame obtains silicon dioxide.
The commercially available hydrophobic SiO 2 powder that is fit to can be Aerosil R106, R202, R805, R812, R812S, R8200, R812 VV60, R812 VV90, R812S VV60, R812S VV90, R104V, R202 VV90, R805 VV90 (Degussa) or HDK H2000, H2050, H3004 (Wacker).
In the method for the invention, can contain as the powder of cosmetics and be selected from following material:
A) UV light screening filtering agent,
B) dyestuff and pigment,
C) wetting agent/emollient,
D) deodorization and antiperspirant,
E) biogenic material (biogenic substance),
F) anthelmintic,
G) hydrotropic agent,
H) dandruff removing agent,
I) bleaching or skin lightening agent (skin lightening agent) and self-tanning agent,
J) antiseptic,
K) surfactants,
L) aromatic oil and/or plant extract.
A) UV light screening filtering agent
UV light screening filtering of the present invention agent is at room temperature for liquid or crystal and can absorb ultraviolet, and with more long-wave radiation form for example the form of heat send the organic substance (agent of light screening filtering) of the energy that is absorbed.The UV filtering agent can be an oil-soluble or water miscible.The example of oil soluble material is as follows:
-3-benzylidene camphor or 3-benzal norcamphor and its derivant, for example 3-that puts down in writing among EP 0 693471 B1 (4-methyl benzal) Camphora
-4-aminobenzoic acid derivative, preferred 4-(dimethylamino) benzoic acid-2-ethyl hexyl ester, 4-(dimethylamino) benzoic acid-2-octyl group ester and 4-(dimethylamino) benzoic acid amyl group ester
The ester of-cinnamic acid, preferred 4-methoxy cinnamic acid-2-ethyl hexyl ester, 4-methoxy cinnamic acid propyl diester, 4-methoxy cinnamic acid isopentyl ester, 2-cyano group-3,3-phenyl-cinnamic acid-2-ethyl hexyl ester (the two cinnamic acid butyl esters (octocrylene) of cyanogen)
-salicylic ester, preferred salicylic acid-2-ethyl hexyl ester, salicylic acid-4-isopropyl benzyl ester, the high menthyl ester of salicylic acid (salicylic acid homomenthyl ester)
The derivant of-benzophenone, preferred 2-hydroxyl-4-methoxy benzophenone, 2-hydroxyl-4-methoxyl group-4 '-methyldiphenyl ketone, 2,2 '-dihydroxy-4-methoxy benzophenone
The ester of-benzal malonic acid, preferred 4-methoxyl group benzal malonic acid two-2-ethyl hexyl ester
-pyrrolotriazine derivatives, for example put down in writing among EP 0 818 450 A1 2,4,6-triphen amido-(to carbonyl-2 '-ethyl-1 '-hexyloxy)-1,3,5-triazines and octyl triazone, or Uvasorb HEB (Uvasorb TM HEB)
-propane-1,3-diketone, 1-(4-tert-butyl-phenyl)-3-(4 '-methoxyphenyl) propane-1 for example, 3-diketone
-ketone group three ring (5.2.1.0) decane derivatives are documented among EP 0 694 521 B1.The water-soluble substances that is fit to comprises:
-2-Phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline-earth metal, ammonium, alkylammonium, alkanol ammonium and glucose ammonium salt
The sulfonic acid of-benzophenone, preferred 2-hydroxyl-4-methoxy benzophenone-5-sulfonic acid and its salt
The sulfonic acid of-3-benzylidene camphor, for example 4-(the bornenyl methyl of 2-oxo-3-) benzenesulfonic acid and 2-methyl-5-(2-oxo-3-is bornenyl) sulfonic acid and its salt.
The exemplary of UV-A filtering agent particularly is documented in the derivant of the benzoyl methane among DE 191 12 033 A1 (BASF); 1-(4 '-tert-butyl-phenyl)-3-(4 '-methoxyphenyl) propane-1 for example; 3-diketone, the 4-tert-butyl group-4 '-methoxy dibenzoyl methylmethane (Parsol TM1789), 1-phenyl-3-(4 '-isopropyl phenyl)-propane-1,3-diketone and enamine compound.UV-A and UV-B filtering agent certainly use with mixture.Particularly advantageous compositions by the derivant of benzoyl methane (for example the 4-tert-butyl group-4 '-methoxy dibenzoyl methylmethane (ParsolTM1789) and 2-cyano group-3; 3-phenyl-cinnamic acid-2-ethyl hexyl ester (octocrylene); with the ester of cinnamic acid, preferred 4-methoxy cinnamic acid-2-ethyl hexyl ester and/or 4-methoxy cinnamic acid propyl diester and/or the combination of 4-methoxy cinnamic acid isopentyl ester.Advantageously, for example 2-Phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline-earth metal, ammonium, alkylammonium, alkanol ammonium and the combination of glucose ammonium salt of this compositions and water solublity filtering agent.
Can be particularly advantageous in aqueous phase dissolving or emulsive UV filtering agent.
Except described solable matter, insoluble light shielding pigment, promptly finely divided metal oxide powder, preferably hydrophobic form or salt also are suitable for this purpose.The example of metal oxide powder that is fit to or hydrophobic metal oxide powder can be titania powder, alumina powder, Zinc oxide powder and/or with the mixed oxide powder of elements Si, Ti, Al, Zn, Fe, B, Zr and/or Ce.
By the hydrophobic SiO 2 powder and the summation meter of metal oxide powder, the ratio of metal oxide powder is preferably less than 50 weight %, especially preferably less than 30 weight %.
Can also use silicate (Talcum), barium sulfate or zinc stearate.
So-called micron pigment or nano dye also preferably are used in the sunscreen.Particulate average diameter should be less than 100nm, preferred 5～50nm, particularly 15～30nm.They also can be spherical in shape, has elliposoidal or depart from spheric other forms of granule but also can use.
Exemplary is the titanium dioxide of coating, UV-titanium M212 for example, M262 and X111 (Kemira), AEROXIDE TiO
2P25, PF2, T805 and T817 (Degussa), little titanium dioxide MT-150W, MT-100AQ, MT-100SA, MT-100HD, MT-100TV (Tayca), Eusolex TM T2000 (Merck), the neutral H﹠amp of zinc oxide; R and zinc oxide NDM (Haarmann ﹠amp; Reimer) and Z-Cote and Z-Cote HP1 (BASF).Can also use dispersion such as TEGO Sun TAQ40, the aqueous dispersion (Degussa) of the titanium dioxide of 40 weight % hydrophobizations.Other UV light screening filtering agent that are fit to can be at the S of P.Finkel FW-Journal122, and 543 (1996) and Parf.Kosm.3, find in 11 (1999) the summary.Can also use Optical Bleaching Agent, for example 4,4 '-diaminobenzil-2,2 '-disulfonic acid and its derivant.
Except above-mentioned two groups of one-level light screeners, can also use the secondary light screener of antioxidant type, it can interrupt the photochemical reaction chain that causes when UV ray transdermal.Its exemplary is an aminoacid (glycine for example; histidine; tyrosine; tryptophan) and its derivant; imidazoles (for example urocanic acid) and its derivant; peptide class such as D; the L-carnosine; the D-carnosine; L-carnosine and its derivant (for example anserine); carotenoid; carotin (α-carotin for example; solatene; lycopene) and its derivant; chlorogenic acid and its derivant; thioctic acid and its derivant (for example dihydrolipoic acid); aurothioglucose; propylthiouracil and other mercaptan (sulfur oxygen cyclase protein for example; glutathion; cysteine; cystine; cystamine and its glycosyl; the N-acetyl group; methyl; ethyl; propyl group; amyl group; butyl and lauryl; palmityl; oil base; γ-Ya oil base; cholesteryl and its glyceryl ester) and its salt; thiodipropionate dilauryl; the thio-2 acid distearate; thio-2 acid and its derivant (ester; ether; peptide; matter fat; nucleotide; nucleoside and salt) and the sulfoxide amines of very little tolerant dose (for example pmol-mu mol/kg) (buthionine sulfoximine for example; homocysteine sulfoxide amine; fourth methyllanthionine sulfone; five-; six-, seven methyllanthionine sulfoxide amine); (metal) chelating agen (alpha-hydroxy fatty acid for example; Palmic acid; phytic acid; lactoferrin); 'alpha '-hydroxy acids (citric acid for example; lactic acid; malic acid); humic acid; cholic acid; bile extract; bilirubin; biliverdin; EDTA; EGTA and its derivant; unsaturated fatty acid and its derivant (gamma-Linolenic acid for example; linoleic acid; oleic acid); folic acid and its derivant; ubiquinone and ubiquinol and its derivant; vitamin C and derivant (ascorbyl palmitate for example; magnesium ascorbyl phosphate; the ascorbic acid acetas); tocopherols and derivant (for example vitamin e acetate); the coniferyl benzoate of vitamin A and derivant (vitamin A palmitate) and benzoic acid resin; rutinic acid and its derivant; the alpha-glycosyl rutin; ferulic acid; the furfurylidene glucitol; carnosine; butylated hydroxytoluene; Butylated hydroxyanisole; nordihydroguaiaretic acid (nordihydroguaiac acid); nor-dihydroguaiaretic acid; trihydroxy fourth phenyl ketone; uric acid and its derivant; mannose and its derivant; superoxide dismutase; zinc and its derivant (ZnO for example; ZnSO
4), the derivant (salt, ester, ether, sugar, nucleotide, nucleoside, peptide and matter fat) of selenium and its derivant (for example SLM), diphenylethylene and its derivant (for example stilbene oxide, trans-the stilbene oxide) and these described active component of being suitable for according to the present invention.
B) dyestuff and pigment
Operable dyestuff is natural, plant or animal dye, for example betanin, annatto, carmine, carotin, chlorophyll, Ink sepiellae seu sepiae etc. and derivant thereof, and synthetic organic dye, for example azo, anthraquinone, triphenhlmethane dye etc.Special preferred water dissolubility or can be in water dispersive dyestuff.
Powder can also contain inorganic pigment, as Haematitum, umber, Haematitum, loess, Chalk etc. and synthetic inorganic pigment, and as ferrum oxide, ultramarine, titanium dioxide, zinc oxide, mica-based pigment, pearlescent pigment for example.Special preferred water-wettable pigment.
C) wetting agent/emollient
Powder can also contain wetting agent.They are used for the organoleptic properties of further optimum organization thing and are used to regulate the moisture of skin.The low-temperature stability of goods of the present invention is increased simultaneously, especially under the situation of emulsion.The wetting agent routine accounts for 0.1～15 weight %, preferred 1～10 weight %, particularly 5～10 weight %.
The example that is fit to is aminoacid especially, the 2-pyrrolidone-5-carboxylic acid, lactic acid and its salt, lactose, urea and urea derivative, uric acid, glycosamine, kreatinin, the catabolite of ossein, chitosan or chitosan salts/derivant, polyhydric alcohol and polyol derivative (glycerol for example particularly, diglycerol, triglycerin, ethylene glycol, propylene glycol, butanediol, red algae alcohol, 1,2, the 6-hexanetriol, polyethylene glycols such as PEG-4, PEG-6, PEG-7, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14, PEG-16, PEG-18, PEG-20), saccharide and sugar derivatives (fructose especially, glucose, maltose, maltose alcohol, mannitol, inositol, Sorbitol, sorbose base silane glycol, sucrose, trehalose, xylose, xylitol, glucuronic acid and its salt), Sorbitol (the Sorbeth-6 of ethoxylation, Sorbeth-20, Sorbeth-30, Sorbeth-40), Mel and hydrogenant Mel, the mixture of hydrogenant starch hydrolysate and hydrogenant wheat protein and PEG-20-acetate copolymer.Goods of the present invention especially preferably contain glycerol, diglycerol, triglycerin and butanediol.
D) deodorization and antiperspirant
Deodorization and antiperspirant also can be added in the powder.These active component comprise any combination of convergence slaine (antiperspirant), bacterial inhibitor, enzyme inhibitor, odor absorbent, stink screening agent or these active component.Deodorization/antiperspirant can account for 0.1～30 weight % of powder, preferred 5～25 weight %, particularly 10～25 weight % (by product amount).
For example, aluminium chlorohydrate, hydration zirconium chloride aluminum and zinc salt can be used as antiperspirant.Except aluminium chlorohydrate, goods of the present invention can also contain aluminium hydroxyacetate (aluminiumhydroxylactate) and acid aluminum/zirconates, for example Locron TM (formula [Al
2(OH)
5Cl] * 2.5H
2O, Clariant GmbH) or Rezal TM 36G (tetrachloro benzthiazide ZAR complex (aluminium zirconium tetrachlorohydrex glycine complex), Reheis).
Can add enzyme inhibitor for example esterase inhibitor as extra deodorizer.They are the citric trialkyl ester preferably, as citric acid trimethyl ester, citric acid tripropyl ester, citric acid triisopropyl ester, citric acid tributyl ester, particularly citric acid triethyl group ester (Hydagen TM C.A.T., Cognis Deutschland GmbH).These materials suppress the enzymatic activity of antiperspirant decomposer, thereby reduce the formation of abnormal flavour.Other materials that can be used as esterase inhibitor are sterol sulfuric ester or phosphate ester, for example lanosterol, cholesterol, campesterol, stigmasterol and sitosterol sulfuric ester or phosphate ester, dicarboxylic acids and its ester, for example 1,3-propanedicarboxylic acid, 1,3-propanedicarboxylic acid mono ethyl ester, ethyl glutarate, adipic acid, monoethyl adipatee, diethylene adipate, malonic acid and diethyl malonate, hydroxy carboxylic acid and its ester, for example citric acid, malic acid, tartaric acid or diethyl tartrate..Influence microorganism species and kill or the antibacterial that suppresses antiperspirant decomposer growth also can be included in the goods of the present invention.Their example be chitosan, phenyl phenol, gluconic acid chlorhexidine (chlorohexidine gluconate) or 5-chloro-2-(2, the 4-dichlorophenoxy) phenol (Irgasan TM, Ciba-Geigy, Basle/CH).
The material of all resisting gram-positive bacterias all is suitable for basically as bacterial inhibitor, for example 4-hydroxy benzoic acid and its salt and ester, N-(4-chlorphenyl)-N '-(3, the 4-Dichlorobenzene base) urea, 2,4,4 '-three chloro-2 '-hydroxy diphenyl ether (triclosan), 4-chloro-3, the 5-xylenol, 2,2 '-methylene-two-(6-bromo-4-chlorophenol), 3-methyl-4-(1-Methylethyl) phenol, 2-benzyl-4-chlorophenol, 3-(4-chlorophenoxy)-1, the 2-propylene glycol, 3-iodo-2-propine butyl carbamate, chlorhexidine, 3,4,4 '-trichloro-symmetrical diphenyl urea (TTC), antibiotic spice, thymol, thyme oil, acetaminol, cloves oil, menthol, Oleum menthae, farnesol, phenyl phenol, monocaprin, Monooctamoin, glyceryl monolaurate (GML), DMC (DMC), salicylic acid-N-alkylamide, for example salicylic acid-n-octyl group amide or salicylic acid-n-decyl amide.
The material that can absorb and greatly keep generate the chemical compound of stink is suitable for as the abnormal flavour absorbent.They reduce the dividing potential drop of each composition, thereby also reduce their spread speed.Importantly spice there is not adverse effect.As its main component, for example, they contain complexation zinc salt or specific, a large amount of abnormal flavour-neutral aromatic substance of ricinoleic acid, and those skilled in the art are called " fixer ", for example the extract of frostweed or Styrax or some rosin acid derivative.
Spice or aromatic oil except as the abnormal flavour screening agent, also make deodorizer emit abnormal smells from the patient as the abnormal flavour screening agent.The aromatic oil example that can example goes out is the mixture of natural perfume material and synthetic perfume.Natural perfume material has extract and the resin and the face cream of flower, stem and leaf, fruit, peel, root, timber, medicinal herbs and grass, needle and twig sprout.Animal material also is fit to, for example Zibethum and castoreum.Typical case's synthetic perfume chemical compound is ester, ether, aldehyde, ketone, alcohol or hydrocarbon product.The flavor compounds of ester type for example is which ester, formic acid benzyl ester, propanoic acid pi-allyl cyclohexyl ester, styralyl propionate and a salicylic acid benzyl ester in acetic acid benzyl ester, acetic acid p-tert-butylcyclohexyl ester, linalyl acetate, acetic acid phenylethylester, the benzoic acid.Ether comprises for example benzylisoeugenol, aldehyde comprises straight chain alkanal, citral, citronellal, citronellyl oxygen acetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilestralis and the clean big vast aldehyde of ripple (bourgeonal) that for example has 8～18 carbon atoms, ketone comprises ionone and methyl Cupressus funebris Endl. base ketone, alcohol comprises anethole, citronellol, acetaminol, isoeugenol, geraniol, linalool, the pure and mild terpinol of phenylethyl, and hydrocarbon mainly comprises terpenoid and face cream class.Yet, preferably use the mixture of various spice, they generate euosmia together.The main ether oil that is used as the relative low volatility of fragrance ingredient also is suitable as aromatic oil, for example sage oil, chamomile oil, cloves oil, melissa oil, Oleum menthae, Cortex Cinnamomi leaf oil, limette caul-fat, Juniperus oxycedrus fruit oil, vetiver oil, Olibanum oil, ancient fluffy Oleum sesami, labdanum oil and lavandin oil.Preferably be used alone or as a mixture oleum bergamottae, dihydromyrcenol, lilestralis, LYRAL (lyral), citronellol, phenylethyl alcohol, jasmonal H, geraniol, benzylacetone, cyclamen aldehyde, linalool, boisambrene forte, dragon saliva furan, indole, MDJ (hedione), sandelice, Fructus Citri Limoniae oil, mandarin oil, citrus seed oil, Allyl amyl glycolate., cyclovertal, lavandin oil, sage oil, β-damascone, geranium oil Bourbon, the salicylic acid cyclohexyl, Vertofix Coeur, Iso-E-Super, Fixolide NP, synthetic oak moss (evernyl), iraldein γ, phenylacetic acid, geranyl acetate, the acetic acid benzyl ester, rose oxide, romilat, irotyl and floramat.
E) biogenic material
The biogenic active component that is fit to for example be tocopherol, tocopherol acetas, tocopherol cetylate, ascorbic acid, (deoxidation) ribonucleic acid and its fragment product, beta glucan, retinal, bisabolol, allantoin, phytantriol (phytanetriol), pantothenylol, pantothenic acid (panthotenic acid), fruit acid, 'alpha '-hydroxy acids, aminoacid, ceramide, false vitalility through amide, quintessence oil, plant extract, for example Prunus extract, Ban Bala berry extract and vitamin complex.
F) anthelmintic
Powder can also contain at least a anthelmintic or these combination of agents.The anthelmintic that is fit to comprises for example N, N-diethyl-m-toluamide, 1,2-pentanediol or 3-(N-n-butyl-N-acetyl-amino) propanoic acid ethyl ester) (Insect Repellent3535, Merck KGaA) and butyl acetyl-amino propionic ester.Their conventional amounts are 0.1-10 weight % by goods, preferred 1-8 weight %, preferred especially 2-6 weight %.
G) hydrotropic agent
Powder can contain hydrotropic agent, for example ethanol, isopropyl alcohol or polyhydric alcohol.Described polyhydric alcohol preferably contains 2～15 carbon atoms and has at least two hydroxyls.Polyhydric alcohol can also contain other functional groups, and is particularly amino, maybe can modify with nitrogen.Exemplary is:
-glycerol
-alkane glycol, for example ethylene glycol, diethylene glycol, propylene glycol, butanediol, hexanediol and mean molecule quantity are 100～1000 daltonian Polyethylene Glycol
-intrinsic concentration degree is 1.5～10 industrial oligomeric glycerol mixture, and for example diglycerol content is the industrial diglycerol mixture of 40～50 weight %
-methylol compound is as particularly trimethylolethane, trimethylolpropane, tri hydroxy methyl butane, tetramethylolmethane and Bis(pentaerythritol)
-short-chain alkyl glucoside particularly has those glucosides of 1～8 carbon atom, for example methyl and butyl glucoside in alkyl
-have the sugar alcohol of 5～12 carbon atoms, as Sorbitol or mannitol
-have the sugar of 5～12 carbon atoms, as glucose or sucrose
-amino sugar is as glycosamine
-glycol amine is as diethanolamine or 2-amino-1, ammediol.
H) dandruff removing agent
The dandruff removing agent that is fit in the powder comprises pyridone ethanolamine (piroctoneolamine) (1-hydroxy-4-methyl-6-(2; 4; the 4-tri-methyl-amyl)-2-(1H)-pyridone monoethanolamine salt); Baypival TM (climbazole); Ketoconazol TM; (4-acetyl group-1-4-[2-(2; the 4-Dichlorobenzene base)-r-2-(1H-imidazoles-1-ylmethyl)-1; 3-dioxylan-c-4-ylmethoxy phenylpiperazine; ketoconazole; elubiol; selenium sulfide; colloid sulfur; sulfo-Polyethylene Glycol sorbitan monooleate; the poly-b-oxide of sulfo-Semen Ricini alcohol; the sulfur tarry distillate; salicylic acid (or with hexachlorophene combination); undecylenic acid monoethanolamine sulfenyl succinic acid sodium salt, Lamepon TM UD (albumen undecylenic acid condensation substance); Zinc Pyrithione (zinc pyrithione); pyrithione aluminum (aluminium pyrithione) and pyrithione magnesium (magnesium pyrithione)/two pyrithione magnesium sulfate (dipyrithione magnesium sulfate).
I) bleaching or skin lightening agent and self-tanning agent
Powder can contain bleaching or skin lightening agent, the chemical compound of for example alkaline bismuth salt, hydroquinone, removal oxygen, for example zinc peroxide, urea peroxide, hydrogen peroxide and/or organic peroxide.Powder especially preferably contains hydrogen peroxide, and it can use with the aqueous solution form.The suitable example that is used for preventing the tyrosinase inhibitor that forms melanin and be used in depigmenting agent comprises arbutin, ferulic acid, kojic acid, coumaric acid and ascorbic acid (vitamin C, sodium ascorbyl phosphate, magnesium ascorbyl phosphate).Particularly suitable is the Cosmocair C250 of Degussa AG.
Dihydroxy acetone for example is suitable as self-tanning agent.
J) antiseptic
The antiseptic that is fit to for example is phenyl phenol, formalin, p-Hydroxybenzoate, pentanediol or sorbic acid, with the known silver complex of title Surfacine TM, and the part A of the adnexa 6 of German cosmetics decree and other class materials that B lists.
K) surfactants
Powder can contain surfactants.Yet the amount of these materials in goods is crucial, because when adding hydrophobic SiO 2 powder, their wetting behavior can prevent to form powder, thereby can not obtain powder.Therefore, powder does not contain surfactants usually.To surfactant/emulsifier type without limits.Therefore, powder can contain the surfactant of nonionic, amphoteric ion type, amphoteric, cationic and anionic.
L) aromatic oil and plant extract
Powder can contain aromatic oil.They can be natural flavoring, plant perfume and animal perfume material and synthetic perfume or their mixture.Natural perfume material especially can extract from flower, stem, leaf, fruit, peel, root and the resin of plant.Animal material also is fit to, for example Zibethum and castoreum.Typical case's synthetic perfume chemical compound is ester, ether, aldehyde, ketone, alcohol or hydrocarbon product.The preferred mixture that uses various spice, they generate pleasant abnormal smells from the patient together.
Operable plant extract for example comprises the extract of arnica montana, birch, Chamomile, bur root (burr root), lichens palpus (beard lichen), Cortex Populi dividianae, Herba Urticae Cannabinae and Endocarpium Juglandis.
M) active component
Powder can contain hormone, for example oxytocin, thyroliberin, vassopressin, secretin, Gastrin..
Powder also can contain the hydrophobic organic dust of polystyrene, polyethylene, organopolysiloxane, poly methyl silsesquioxane, N-acyl group-lysine, polyflon, acrylic resin, epoxy resin, polymethyl methacrylate, Acrylonitrile metry1 methacrylate copolymer, vinylidene chloride-methacrylic acid copolymer and/or nylon powder.
Powder can contain hydrophobic inorganic, metal oxide powder, for example titanium dioxide or aluminium oxide, and wherein these metal oxide powders can be the pyrolysis sources.By the total amount of hydrophobic SiO 2 powder and hydrophobic metal oxide powder, the ratio of the metal oxide powder that these are hydrophobic is preferably less than 50 weight %, especially preferably less than 30 weight % in each case.
Can also use the powder that contains viscosity modifier in the method for the present invention.They are preferably:
Hydrogel precursor or hydrocolloid (hydrocolloid), the polysaccharide of modification for example, as cellulose ether and cellulose esters, for example carboxymethyl cellulose, methylcellulose, hydroxyethyl-cellulose, methyl hydroxyethylcellulose, methylhydroxypropylcellulose, xanthan gum, guar gum, agar, alginate and fine plain sodium acetate;
Inorganic hydrocolloid, as bentonite, Magnesiumaluminumsilicate, silicon dioxide; And the synthetic water colloid, as polyacrylate (for example the Carbopole TM of Goodrich and Pemulen class; The Synthalene TM of Sigma; The Keltrol class of Kelco; The Sepigel class of Seppic; The Salcare class of Allied Colloids), uncrosslinked and polyhydric alcohol-crosslinked polyacrylic, polyacrylamide, polyvinyl alcohol and polyvinylpyrrolidone.
Can also use surfactant to carry out viscosity adjustment, described surfactant is fatty glyceride, fatty acid and the polyhydric alcohol ester of tetramethylolmethane or trimethylolpropane for example of for example ethoxylation, have alcohol ethoxylate, oligomeric alkyl glucoside and electrolyte that dense homologue distributes, for example Sal and ammonium chloride.
Be suitable for is anionic as viscosity modifier, amphoteric ion type, amphoteric and non-ionic copolymer, for example vinyl acetate/.beta.-methylacrylic acid copolymer, vinylpyrrolidone/vinyl acrylate copolymer, vinyl acetate/maleic acid butyl ester/isobornyl acrylate copolymer, methyl vinyl ether/copolymer-maleic anhydride and its ester, acrylamido oxypropyl trimethyl ammonium chloride/acrylate copolymer, octyl acrylamide/methyl methacrylate/t-butylaminoethyl methacrylate/methacrylic acid 2-hydroxypropyl ester copolymer, vinylpyrrolidone/vinyl acetate copolymer, vinylpyrrolidone/dimethylaminoethyl acrylate methyl base amino-ethyl ester/caprolactam trimer and randomly deutero-cellulose ether and silicones.Other polymer and thickening agents that are fit to are listed in Cosm.Toil.108, in 95 (1993).
Viscosity modifier ratio in the powder can not be higher than 20 weight %, preferred 1～5 weight %.
Goods of the present invention also can contain at least a oil body.Oil body should be understood as that finger is following for liquid and at 25 ℃ of following and the immiscible material of water or mixture of substances at 20 ℃.Mix the oil body permission and optimize the organoleptic properties of goods.
The example of oil body comprise based on have 6～18, the Guerbet (guerbet) of the aliphatic alcohol of preferred 8～10 carbon atoms alcohol (for example Eutanol TM G), straight chain C
6-C
22Fatty acid and straight or branched C
6-C
22The ester of aliphatic alcohol or collateralization C
6-C
13Carboxylic acid and straight or branched C
6-C
22The ester of aliphatic alcohol, for example myristyl alcohol myristinate, the myristyl alcohol cetylate, the myristyl alcohol stearate, the myristyl alcohol isostearate, the myristyl alcohol oleate, the myristyl alcohol behenate, the myristyl alcohol eruciate, the spermol myristinate, the spermol cetylate, the spermol stearate, the spermol isostearate, the spermol oleate, the spermol behenate, the spermol eruciate, the stearyl alcohol myristinate, the stearyl alcohol cetylate, the stearyl alcohol stearate, the stearyl alcohol isostearate, the stearyl alcohol oleate, the stearyl alcohol behenate, the stearyl alcohol eruciate, the isooctadecanol myristinate, the isooctadecanol cetylate, the isooctadecanol stearate, the isooctadecanol isostearate, the isooctadecanol oleate, the isooctadecanol behenate, the isooctadecanol oleate, the oleyl alcohol myristinate, the oleyl alcohol cetylate, the oleyl alcohol stearate, the oleyl alcohol isostearate, the oleyl alcohol oleate, the oleyl alcohol behenate, the oleyl alcohol eruciate, the behenyl alcohol myristinate, the behenyl alcohol cetylate, the behenyl alcohol stearate, the behenyl alcohol isostearate, the behenyl alcohol oleate, the behenyl alcohol behenate, the behenyl alcohol eruciate, myristic acid docosene base ester, Palmic acid docosene base ester, stearic acid docosene base ester, isostearic acid docosene base ester, oleic acid docosene base ester, mountain Yu acid docosene base ester and erucic acid docosene base ester.What also be fit to is straight chain C
6-C
22The ester of fatty acid and branched-chain alcoho, particularly 2-Ethylhexyl Alcohol, C
3-C
38Alkyl hydroxy carboxylic acid and straight or branched C
6-C
22Ester of malic acid diethylhexyl ester, straight chain and/or collateralization fatty acid and polyhydric alcohol (for example propylene glycol, dimer diol (dimerdiol) or trimerization triol (trimertriol)) of the ester of aliphatic alcohol-particularly and/or Guerbet alcohol, based on C
6-C
10The triglyceride of fatty acid, based on C
6-C
18The liquid list-/two of fatty acid-/mixture of triglyceride, C
6-C
22The particularly benzoic ester of aliphatic alcohol and/or Guerbet alcohol and aromatic carboxylic acid, C
2-C
12Dicarboxylic acids and straight or branched alcohol or have ester, vegetable oil, the branched-chain primary alcohol of the polyhydric alcohol of 2～10 carbon atoms and 2～6 hydroxyls, cyclohexane extraction, straight chain and the side chain C of replacement with 1～22 carbon atom
6-C
22The aliphatic alcohol carbonic ester, for example dicaprylyl carbonate (Cetiol TM CC), based on have 6～18, Guerbet carbonic ester, benzoic acid and straight chain and/or the side chain C of the aliphatic alcohol of preferred 8～10 carbon atoms
6-C
22The ester (for example Finsolv TM TN) of alcohol, straight or branched, symmetry or the asymmetric dialkyl ether that each alkyl has 6～22 carbon atoms; for example open-loop products (HydagenTM HSP, Sovermol TM750, Sovermol TM1102) and/or aliphatic or cycloalkane, for example mineral oil, vaseline, vaseline, squalane, Squalene, dialkyl ether, dialkyl carbonate and/or the dialkyl cyclic hexane of two caprylyl ethers (Cetiol TM OE), epoxidised fatty acid ester and polyhydric alcohol.
The powder that contains silicon resin compound also can be used for method of the present invention.They can be cyclohexyl methyl siloxanes, polydimethylsiloxane, dimethyl polysiloxane, methyl phenyl silicone, ring-type silicone, amino-, fatty acid-, alcohol-, polyethers-, epoxy-, fluoro-, glucosides-and/or the silicone compounds of alkyl-modification.What also be fit to is dimethicone, and it is the polydimethylsiloxane of 200～300 dimethyl siloxane units of average chain length degree and the mixture of silicon dioxide or hydrogenated silicate.
Depend on application form, the oil body amount in total composition can be 0.1～10 weight %.Its amount is preferably 0.5～3 weight % especially.
In the method for the invention, the powder of cleaning agent or detergent form can contain hydrogen peroxide.As mentioned above, can use hydrophobic SiO 2 powder of the same race.Their particular methanol degree of wettings are at least 40.Content of hydrogen peroxide can be preferably 10～50 weight %.By total mixture, the ratio of hydrophobic SiO 2 powder can be preferably less than 9 weight %.Hydrogen peroxide uses with the aqueous solution form, and preferred hydrogen peroxide ratio is 5～70 weight %.Usually use H
2O
2Content is the solution of 35 and 50 weight %.Advantageously, solution is stabilized to prevent decomposition.The property quality and quantity of stabilizing agent depends primarily on the hydrogen peroxide ratio in the aqueous solution.
The hydrophobic substance that powder contacted in storing process preferably can be polyethylene, polypropylene, polyethylene terephthalate and/or politef.
The specific embodiment
Embodiment:
Embodiment 1～6: the cosmetics goods
88.92g deionized water and 5.0g propylene glycol (Caelo) are placed beaker, with adding 0.8g LCW Covagel (LCW Sensient) under the magnetic stirrer, then with mixture restir 15 minutes at room temperature.Clear solution is poured in the suitable 500-ml rustless steel beaker, added the mixture of hydrophobic SiO 2 powder of 5.0g or hydrophobic SiO 2 powder and hydrophobic metal oxide powder, and use super mixer (DISPERMAT ; VMA-Getzman, disk diameter 5cm) with 10,000rpm mixed each composition 60 seconds.Then products obtained therefrom is packed in the threaded bottle of making by glass or polyethylene in 250-ml top, and at room temperature in hermetic container, stored 3 months.After 3 months, according to the listed standard visual assessment of table 1 goods.Table 2 illustrates the visual assessment result.
Embodiment 7～11: cleaning agent/detergent
In 500-ml rustless steel beaker, use super mixer (DISPERMAT ; VMA-Getzman, disk diameter 5cm) with 10, the 000rpm speed SiO 2 powder that 93.0g10% hydrogenperoxide steam generator (commercially available stable) and 7.0g is hydrophobic mixes.Products obtained therefrom is packed in the threaded bottle of being made by glass or polyethylene in 250-ml top, and at room temperature in hermetic container, stored 3 months.After 3 months, according to the listed standard visual assessment of table 1 goods.Table 3 illustrates the visual assessment result.
Each embodiment shows that its storage stability obviously improves when powder contacts with the hydrophobic surface of container.
Table 1: storage stability evaluation
| A | No change does not promptly have separated form water |
| B | Several drop of liquid appear on lid, bottom and/or the wall of container |
| C | The water slight separation |
| D | Water separates to a large extent |
Table 2: the storage stability of cosmetics goods
| Embodiment | SiO 2 powder | The storage container material | |
| Glass | Polyethylene | ||
| 1 | AEROSILR812S | C | A |
| 2 | AEROSILR812S VV75 | C | A |
| 3 | AEROSILR812S VV90 | C | A |
| 4 | AEROSILR805 | D | A |
| 5 | AEROSILR202 | C | A |
| 6 | 2 parts of AEROXIDE of 8 parts of AEROSIL R812S VV90 TiO 2 T805 | D | A |
Table 3: the storage stability of cleaning agent/detergent
| Embodiment | SiO 2 powder | The storage container material | |
| Glass | Polyethylene | ||
| 7 | AEROSIL R812S | C | A |
| 8 | AEROSIL R812S VV75 | C | A |
| 9 | AEROSIL R812S VV90 | C | A |
| 10 | AEROSIL R805 | D | A |
| 11 | AEROSIL R202 | C | A |
Claims (4)
1. a delay discharges the method for water from powder, described powder comprises cosmetics, cleaning agent and detergent, wherein said powder contains the water of at least 50 weight % and hydrophobic SiO 2 powder, it is characterized in that, contact with hydrophobic material at powder described in the storing process.
2. the method for claim 1, it is characterized in that, contain as the powder of cosmetics and be selected from following material: the agent of UV light screening filtering, dyestuff and pigment, wetting agent/emollient, deodorization and antiperspirant, biogenic material, anthelmintic, hydrotropic agent, dandruff removing agent, bleaching or skin lightening agent and self-tanning agent, antiseptic, surfactants, aromatic oil and/or plant extract.
3. the method for claim 1 is characterized in that, contains hydrogen peroxide as the powder of cleaning agent or detergent.
4. as the described method of claim 1～3, it is characterized in that described hydrophobic substance is polyethylene, polypropylene, polyethylene terephthalate and/or politef.
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| DE102004062652.9 | 2004-12-24 | ||
| DE102004062652 | 2004-12-24 | ||
| DE102005055226.9 | 2005-11-19 |
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| CN100579503C CN100579503C (en) | 2010-01-13 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102686207A (en) * | 2009-12-26 | 2012-09-19 | 赢创德固赛有限公司 | Water containing powder composition |
| CN103945821A (en) * | 2011-11-04 | 2014-07-23 | 荷兰联合利华有限公司 | Cosmetic composition |
| CN105362086A (en) * | 2015-11-02 | 2016-03-02 | 江南大学 | Solid perfume based on liquid marble and preparation method thereof |
| CN105560070A (en) * | 2015-11-02 | 2016-05-11 | 江南大学 | Multifunctional sun cream based on liquid beads and preparation method of multifunctional sun cream |
| US9539190B2 (en) | 2010-05-07 | 2017-01-10 | Conopco, Inc. | Skin conditioning compositions containing 12-hydroxystearic acid |
-
2005
- 2005-12-23 CN CN200580044275A patent/CN100579503C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102686207A (en) * | 2009-12-26 | 2012-09-19 | 赢创德固赛有限公司 | Water containing powder composition |
| US8647653B2 (en) | 2009-12-26 | 2014-02-11 | Evonik Degussa Gmbh | Water containing powder composition |
| CN102686207B (en) * | 2009-12-26 | 2014-05-28 | 赢创德固赛有限公司 | Water containing powder composition |
| US9539190B2 (en) | 2010-05-07 | 2017-01-10 | Conopco, Inc. | Skin conditioning compositions containing 12-hydroxystearic acid |
| CN103945821A (en) * | 2011-11-04 | 2014-07-23 | 荷兰联合利华有限公司 | Cosmetic composition |
| CN103945821B (en) * | 2011-11-04 | 2017-01-18 | 荷兰联合利华有限公司 | Cosmetic composition |
| CN105362086A (en) * | 2015-11-02 | 2016-03-02 | 江南大学 | Solid perfume based on liquid marble and preparation method thereof |
| CN105560070A (en) * | 2015-11-02 | 2016-05-11 | 江南大学 | Multifunctional sun cream based on liquid beads and preparation method of multifunctional sun cream |
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| CN100579503C (en) | 2010-01-13 |
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