CN1107509A - Acid microemulsion composition - Google Patents
Acid microemulsion composition Download PDFInfo
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- CN1107509A CN1107509A CN94107561A CN94107561A CN1107509A CN 1107509 A CN1107509 A CN 1107509A CN 94107561 A CN94107561 A CN 94107561A CN 94107561 A CN94107561 A CN 94107561A CN 1107509 A CN1107509 A CN 1107509A
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- acid
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- alpha
- hydroxy fatty
- fatty acid
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/50—Perfumes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/0017—Multi-phase liquid compositions
- C11D17/0021—Aqueous microemulsions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/36—Organic compounds containing phosphorus
- C11D3/364—Organic compounds containing phosphorus containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
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- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Abstract
An acidic thickened microemulsion composition which contains alpha hydroxy aliphatic acids and is effective in removing soap scum.
Description
The present invention relates to a kind of scale remover that is used for as crusts such as bathtub, tank, ceramic tile, porcelain and enamel ware, this scale remover can be removed soap-film from these surfaces, lime scale and greasy and do not damage the surface.More particularly, the present invention relates to a kind of acid microemulsion, this milk sap can be sprayed on the surface to be cleaned, wipes then and does not need common flushing, and still can make the surface that is cleaned bright and glossy.The invention still further relates to a kind of using method of this composition.
Hard surface cleaner, as the bathroom scale remover with wash away scale remover, people have known many years.Wash away scale remover and generally include a kind of soap or synthetic organic detergent or tensio-active agent and abrasive material.This series products can abrade relatively softer surface and finally make the surface look the color and luster dimness.These products can not be removed lime scale (normally incrustive lime carbonate and magnesiumcarbonate) effectively in routine is used.Because lime scale can be removed by carrying out chemical reaction with acidic medium, so produced various acidic descaling agents and obtained success in various degree.Because used acid is too strong and destroyed the surface that is cleaned, and is unsuccessful at this scale remover of some occasion.In some other occasions, the acidic component in the scale remover make us offensively with product in other composition reaction, this can influence washing composition or spices very unfriendly.Some scale remover stays disagreeable precipitation on needing to wash with the surface of avoiding being cleaned after the use.As in order to overcome the achievement in research that above-mentioned shortcoming is carried out, made a kind of improved liquid descaling composition recently, said composition exists with stable microemulsion form and is a kind of from removing the effective scale remover of soap-film, lime shell as the crust of bathroom surfaces and do not need flushing after use.This product is by Loth, and the U.S. Patent application S.N.120 about stable microemulsion descaling composition that Blanvalet and Valenge submitted on November 12nd, 1987 describes in 250 to some extent, and this article is for referencial use in this merging.Particularly, the embodiment 3 of this application discloses a kind of tart, limpid, the oil-in-water-type microemulsion, and this emulsion is described as being successfully used to remove lime shell and the soap film that adheres on the shower wall ceramic tile in the text.By scale remover is applied on the wall, wipe then or wash on a small quantity and implement this cleaning, very bright after the wall drying.
The described microemulsion scale remover of this patent application is effectively and is easy to use removing from crust delime shell and the soap film, but found its acid reagent (succsinic acid, pentanedioic acid and hexanodioic acid) mixture can damage the surface of some hard fixture, as the fixture of those acid nonfast materials.One of this class material is the enamel that is widely used as the bathtub coating in Europe, is called European enamel at this.It is described to zirconium white enamel or zirconium white powder enamel and has detergent-resistant advantage, and this its is suitable for being used in bathtub, and tank is on shower ceramic tile and the bathroom enamel ware.Yet this enamel is responsive to acid and can be subjected to badly damaged in the use based on the microemulsion scale remover of aforementioned three kinds of organic carboxyl acids.
This problem is solved by EPO patent 0336878A2, and wherein additional acid material mixes with organic acid in scale remover and problem is increased the weight of, and additional acid material has prevented the infringement of these organic acids to this enamel surface, class Europe.In addition, the mixture of this additional acid (phosphonic acids and phosphoric acid) has shockingly further improved the cost that scale remover water liquid is used in the lip-deep security of this European enamel and has reduced scale remover.
Composition of the present invention can be used for the cleaning on European enamel surface, also can be used for arbitrarily other acidproof bathtub surface and the cleaning of other bathroom surfaces.This product can be used on various other materials that are subject to the acidic medium infringement especially, as marble.Said composition has used alpha-hydroxy fatty acid to replace succsinic acid used in aforementioned acid microemulsion, the mixture of pentanedioic acid and hexanodioic acid.The composition of this use alpha-hydroxy fatty acid and succsinic acid, the mixture of pentanedioic acid and hexanodioic acid compare European enamel or other sensitivity to acid surface is littler as marmorean infringement.In addition, estimate that composition of the present invention can be by xanthan gum (as described in the United States serial the 07/950th, 370 of filing an application to subject to approval in September, 1992) multiviscosisty.
According to the present invention, a kind of acid proof or acidic aqueous solution scale remover of zirconium white enamelled bathtub and other crust article of being used for, wherein the pH of scale remover is that 1-4 and scale remover can remove the delime shell from the surface of these article, soap film and greasy and do not damage these surfaces comprises: at least a washing part that can remove the synthetic organic detergent of oily from these surfaces; A kind of lime shell and soap film with alpha-hydroxy fatty acid of 3-5 carbon atom removed part; A certain proportion of amino alkylidenyl phosphonic acids damages the zirconium white enamel surface of article to be cleaned to prevent alpha-hydroxy fatty acid; Phosphoric acid and washing composition, alpha-hydroxy fatty acid, phosphoric acid and amino alkylidenyl phosphonic aqueous medium.
Multiviscosisty of the present invention, acid microemulsion composition approximately contains by weight:
(a) a kind of anion surfactant of 1-9% such as a kind of C
14-17Basic metal or the sulfonate of ammonium; C
8-C
18Basic metal or the alkyl-sulphate or the C of ammonium
8-C
18Basic metal or the sulfated alkyl ether of the ethoxylation of ammonium;
(b) a kind of nonionogenic tenside of 0-5% such as a kind of C
13-15Fatty Alcohol(C12-C14 and C12-C18) EO7: 1/PO4: 1;
(c) a kind of sanitas of 0-0.7% such as basic metal benzoate Sodium Benzoate for example;
(d) a kind of molecular weight of 0-1.0% is approximately 1,000,000-10, and 000,000 xanthan gum viscosifying agent is as by Merck﹠amp; Co. the Kelzan T of Xiao Shouing;
(e) a kind of alkali metal hydroxide of 0-0.3%;
(f) phosphoric acid of 0-1.0% is more preferably 0.05-1.0%;
(g) a kind of amino trimethylammonium phosphonic acids of 0-0.5% is more preferably 0.01-0.3%;
(h) a kind of dyestuff of 0-0.1%;
(i) a kind of spices of 0-2.0%;
(j) 2-9% at least a has 2 alpha-hydroxy fatty acids to about 6 carbon atoms; With
(k) the trim thing is a water, and wherein composition pH is about 1 to about 4, is about 2.7 to about 3.3 and the about 5-1 of Brookfield viscosity better, and 000cps is about 30 to about 600cps(room temperature better, uses #2 spindle and 50 rev/mins).
In composition of the present invention, the synthetic organic detergent can be any suitable negatively charged ion, nonionic, zwitter-ion or cationic detergent or their mixture, but negatively charged ion and nonionic detergent and their mixture are preferred.
The amount of operable nonionogenic tenside is about 0-5% in liquid composition as scale remover of the present invention, is 0.5-4.5% preferably, is that 1-4%(is by composition weight meter best), it has good performance in removing crude removal.
Employed in the present invention water soluble nonionic surfactant is commercially to know, comprise uncle's fatty alcohol ethoxylate, secondary fatty alcohol ethoxylate, alkylphenol ethoxylate and the epoxy ethane-epoxy propane condenses on primary alkanol is as Plurafacs(BASF) and the condenses such as the tween (ICI) of oxyethane and sorbitan fatty acid esters.The condensation product of the synthetic normally organic aliphatic series of organic detergent of nonionic or alkyl aromatic hydrophobic compound and hydrophilic ethylene oxide group.In fact has carboxyl, hydroxyl, amido or on nitrogen, be connected with free hydrogen amino any hydrophobic compound can both with oxyethane or with its many hydrated product, the polyoxyethylene glycol condensation forms water miscible nonionic detergent, in addition, be the length of the hydrophobic and hydrophilic segment of polyethylene oxygen.
The nonionic detergent class (for example comprises a kind of higher alcohols, a kind of alkanol that contains the straight or branched configuration of about 8-18 carbon atom) with the about condensation product of the ethylene oxide condensation of 5-30 mole, for example, lauryl alcohol or tetradecyl alcohol and about 16 moles oxyethane (EO) condensation, tridecyl alcohol and about 6 moles ethylene oxide condensation, the condensation product of tetradecyl alcohol and about 10 moles ethylene oxide condensation, oxyethane and a collection of alkyl chain length that contains are 10 condensation products to the coconut Fatty Alcohol(C12-C14 and C12-C18) of the fatty alcohol mixture of about 14 carbon atoms, and wherein condenses contains about 6 moles of ethylene oxide (every mole of total alcohol) or contains about 9 moles of ethylene oxide (every mol of alcohol) and the Tallow, beef alcohol ethoxylate contains the every mol of alcohol of 6-11EO().
One group of preferred aforementioned nonionogenic tenside is Neodol ethoxylate (Shell Co), and they are the higher primary aliphatic alcohols that contain about 9-15 carbon atom, as with the C of 8 moles of ethylene oxide condensations
9-C
11Alkanol (Neodol91-8) is with the C of 6.5 moles of ethylene oxide condensations
12-C
13Alkanol (Neodol23-6.5) is with the C of 12 moles of ethylene oxide condensations
12-C
15Alkanol (Neodo25-12) is with the C of 13 moles of ethylene oxide condensations
14-C
15Alkanol (Neodol45-13), etc.The hydrophobic lipophilic balance of the HLB(of these ethoxylates) value is about 8-15 and produce good O/W emulsifying effect, and the HLB value is lower than 8 ethoxylate and contains and be less than 5 ethylene oxide groups and be easy to become bad emulsifying agent and bad washing composition.
Gratifying water-soluble alcohol ethylene oxide condensate in addition is the condensation product that contains the oxyethane of the aliphatic secondary alcohol of straight or branched configuration of 8-18 carbon atom and 5-30 mole.The example of the commercial available nonionic detergent of aforementioned type be by Union Carbide that sell with the C 9EO condensation
11-C
15Secondary alcohol (Tergitol15-S-9) or with the C of 12EO condensation
11-C
15Secondary alcohol (Tergitol15-S-12).
Other nonionic detergent that is suitable for comprises 1 mole the alkylphenol that contains about 8-18 carbon atom in the alkyl of straight or branched and the condenses of the polyethylene oxide of the oxyethane of about 5-30 mole.The specific examples of the ethoxylate of alkylphenol comprises the nonyl phenol of every moles of phenol and about 9.5 moles ethylene oxide condensation, the binonylphenol of every moles of phenol and about 12 moles epoxy ethoxy condensation, the binonylphenol of every moles of phenol and about 15 moles ethylene oxide condensation and the diisooctyl phenol of every moles of phenol and about 15 moles of ethylene oxide condensations.Commercial available such ionic surfactant pack is drawn together the Igepal CO-630(nonyl phenol ethoxylate of being sold by GAF company).
In gratifying nonionic detergent, also comprise C
8-C
20The water-soluble condensation product of the mixture of alkanol and oxyethane and propylene oxide, wherein the weight ratio of oxyethane and propylene oxide is 2.5: 1-4: 1, be 2.8 preferably: 1-3.3: 1, total oxyethane and propylene oxide in the condenses (comprising terminal ethanol or propyl alcohol group) are 60-85%, be preferably 70-80%(by weight).Such washing composition is commercial available from BASF-Wyandotte, and particularly preferred washing composition is the C with oxyethane and propylene oxide condensation
10-C
16The alkanol condenses, the weight ratio of oxyethane and propylene oxide is 3: 1, total alkoxy group content be about 75%(by weight).
HLB is the oxyethane of 2-30 mole of 8-15 and sorbitan list-and three-C
10-C
20The condenses of alkanoates also can be used as the nonionic detergent composition in described washing composition.These tensio-active agents be know and can obtain with trade(brand)name " tween " from Imperial Chemical Industries (Imperial Chemical Industries).Suitable tensio-active agent comprises polyoxyethylene (4) sorbitan monolaurate, polyoxyethylene (4) sorbitan monostearate, polyoxyethylene (20) sorbitan trioleate and polyoxyethylene (20) sorbitan tristearate.
Other a little bit poorer slightly preferred suitable water-soluble nonionic washing composition is sold with trade(brand)name " Pluronics ".These compounds are to carry out condensation by oxyethane with the hydrophobic group that is formed by propylene oxide and propylene glycol condensation to be produced.The molecular weight of the hydrophobic part in the molecule is 950-4000, is 2000-2 preferably, 500.To the polyoxyethylene groups of hydrophobic part addition from first and last being tending towards increasing the water-soluble of molecule, thereby it is water miscible that tensio-active agent is become.The molecular weight of block polymer is 1,000-15,000, the content of polyethylene oxide be 20%-80%(by weight).Preferably, these tensio-active agents should be liquid, and satisfied tensio-active agent is available L62 level and L64 level.
Employed anion surfactant accounts for 1%-9% greatly in microemulsion composition, is preferably 2%-8%, is preferably 2%-7%(by weight).
The anion surfactant that can be used for microemulsion washing composition of the present invention is water miscible as triethanolamine salt, comprises C
8-C
18The alkylsurfuric acid sodium salt, sylvite, ammonium salt and alcohol salt such as lauryl sulfate, myristyl vitriol etc.; C
8-C
18The sulfated alkyl ether of ethoxylation; Linear C
8-C
16Alkylbenzene sulfonate; C
10-C
20Paraffin sulfonate; The alpha-olefin sulfo group salt that contains about 10-24 carbon atom; C
8-C
18Alkyl sulfoacetate; C
8-C
18The alkyl sulfosuccinic ester; C
8-C
18Acyl isethinate; And C
8-C
18Acyl taurine salt.The preferred anionic surfactants tensio-active agent is water miscible alkyl-sulphate.
Paraffin sulfonate can be monosulfonate or stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate and their mixture normally, and paraffin sulfonate is to make by the paraffin sulfonation with 10-20 carbon atom.Preferably those have C
12-C
18The paraffin sulfonate of carbon atom chain is more preferably and has C
14-C
17The paraffin sulfonate of carbochain.The paraffin sulfonate that sulfonic group distributes along the paraffin chain is in United States Patent (USP) 2,503,280; 2,507,088; 3,260,744; With 3,372,188 and German Patent 735,096 in describe to some extent.Can be made into such compound by patent specification, desirablely be C
14-C
17The content of the paraffin sulfonate outside the scope should be less and should minimize, any two-or the content of many-sulfonate also should be like this.
The example of the sulfonated anionic detergent that other is suitable is the senior alkyl monokaryon aromatic sulphonate of knowing, as in the senior alkyl of straight or branched, containing 9-18 or contain 9 or the senior alkyl benzene sulfonate of 10-15 or 16 carbon atoms preferably, or C
8-15Alkyl toluene sulfonate.Preferred alkylbenzene sulfonate is to have 3-phenyl (or higher) isomer of high level and the linear alkyl benzene sulfonate salt of 2-phenyl (or lower) isomer of lower aq (being preferably lower than 50%) correspondingly.As those phenyl ring overwhelming majority is to be connected on the position of 3 or higher (for example 4,5,6 or 7) of alkyl and phenyl ring is connected the corresponding lower alkylbenzene sulfonate of content of the isomer on 2 or 1.Preferable material is at United States Patent (USP) 3,320, narration to some extent in 174, and particularly those alkyl wherein have the material of 10-13 carbon atom.
Employed in the present invention senior alkyl ether sulfate is expressed from the next:
RO（C
2H
4O）
nSO
3M
Wherein R has 10-18 carbon atom, better is the uncle or the secondary alkyl of 12-15, particularly 12-14 and the straight or branched that is preferably 12-13 carbon atom.M is that a basic metal or ammonium cation and n are 1-10, is 1-6 preferably, particularly 2 or 3 number.These washing composition are by with corresponding ether alcohol sulfation, and their sulfuric ester that produced of neutralization prepares then.Ether vitriolic sodium salt and ammonium salt are particularly preferred.
Useful in the present invention alkyl-sulphate anionic detergent immunomodulator compounds on alkyl, have 6-18 carbon atom and available below general formula represent:
R
2SO
4M
R wherein
2Be that alkyl and the M with straight or branched of 6-18, particularly 8-14 carbon atom chain length is a basic metal or ammonium cation, particularly sodium.Straight chained alkyl is preferred.
Active acidic components in acid emulsion are that a kind of its acidity is strong to the alpha-hydroxy fatty acid that is enough to the pH of microemulsion is reduced to the scope of 1-4.These different class carboxylic acids all have this function, can be effectively remove soap film and lime shell from bathroom surfaces but those have been found, and don't to make the unsettled carboxylic acid of emulsion be the alpha-hydroxy fatty acid with following structure:
Wherein to be selected from hydroxyl or COOH base and X be (CH to Y
2)
nW, wherein W is selected from CH
3Or COOH and n are 0,1 or 2.Preferred alpha-hydroxy fatty acid is a citric acid, lactic acid and oxysuccinic acid, and wherein the mixture of lactic acid and oxysuccinic acid is preferred, wherein the weight ratio of lactic acid and oxysuccinic acid is preferably about 5: about 1: 1 of 1-is more preferably about 4: about 1: 1 of 1-.The amount of at least a alpha-hydroxy fatty acid of institute's blended is the about 9%(weight of about 2%-in composition), be more preferably the about 7%(weight of about 2%-).
For the purpose of bringing into play its validity and safety to greatest extent, after in acid emulsion, mixing, alpha-hydroxy fatty acid partly can be neutralized in emulsion, to produce needed pH.
Phosphoric acid is a kind of acid that helps to protect with in the additional acid on the acid sensitivity surface of milk sap scale remover cleaning of the present invention.As a kind of triprotic acid, it also can partly be neutralized so that the pH of milk sap in needed scope.For example, it can partly be neutralized to dihydrogen phosphate, for example NaH
2PO
4Or NH
4H
2PO
4
The another kind of acid of two kinds of additional acid of the solvency action of the di-carboxylic acid of the emulsion that is used for protecting the acid sensitivity surface to avoid multiviscosisty of the present invention; phosphonic acids; clearly just exist in theory, but its derivative is stable and is useful in an embodiment of the present invention.Such derivative is considered to phosphonic acids, uses this term in this manual.Phosphonic acids has following array structure
Wherein Y is any suitable substituting group, but preferred Y is the alkylamino that alkylamino or N-replace.For example, the acidic emulsion of multiviscosisty of the present invention preferred phosphonic acids component is to have formula N(CH
2PH
xO
3) amino three (methylene radical phosphine) acid, other useful phosphonic acids is ethylene diamine four-(methylene radical phosphine) acid, hexamethylene-diamine four-(methylene radical phosphine) acid and diethylenetriamine five-(methylene radical phosphine) acid.This compounds can be described to the amino alkylidenyl phosphonic acids, it contains 1-3 amino nitrogen separately, 3 or 4 low-grade alkylidene phosphonate groups (wherein low-grade alkylidene has 1 or 2 carbon atom) and 0-2 have the alkylidene group of 2-6 carbon atom, when a plurality of such amino nitrogens are present in the amino alkylidenyl phosphonic acids alkylidene group be existence and be connected with amino nitrogen.Have now found that this amino alkylidenyl phosphonic acids (it also can partly be neutralized) has needed stable and provide protection in scale remover of the present invention under the needed pH of microemulsion scale remover; particularly when existing, can prevent that alpha-hydroxy fatty acid component in the scale remover is to the infringement on European enamel surface with phosphoric acid.
The viscosifying agent that selectively is used for acid microemulsion is to be called KelzanT and by Merck﹠amp; Co. the xanthan gum of Xiao Shouing, xanthan gum is a kind of molecular weight about 1,000,000 to 10,000,000 extracellular mixed polysaccharide, its working concentration is the about 1%(weight of 0-), be more preferably the about 0.7%(weight of about 0.1-), 0.2-0.6%(weight preferably).When using, so assemble the characteristics that composition keeps its microemulsion owing to kept necessary micellar with these concentration.Composition remains sprayable and can adhere to well on the vertical wall.In addition, the composition that wherein is mixed with xanthan gum is shear thinning, and this means does not need a lot of mechanical effects just can remove composition from the surface that is cleaned at an easy rate.Other Mierocrystalline cellulose, hydroxypropylcellulose, polyacrylamide and polyvinyl alcohol will produce the composition of shear-thickening.
Employed water can be tap water in the preparation of microemulsion of the present invention, but is preferably the tap water than soft, and its hardness is less than 150ppm usually.But up to 3, the tap water of 000ppm still can make useful scale remover with hardness.Employed water is distilled water or deionized water preferably, and wherein the content of hardness ions is less than 25ppm.
Various other compositions that can be present on demand in the scale remover of the present invention comprise sanitas such as Sodium Benzoate, antioxidant or inhibiter, cosolvent, cosurfactant, polyvalent metal ion, spices, tinting material and terpenes (with the terpin alcohols), but conventionally in liquid washing agent and hard surface cleaner employed various other auxiliarys also can be used in the scale remover of the present invention, condition is that they do not influence the cleaning of scale remover and the removal function of soap film and lime shell.In various auxiliarys (although they may be the in demand compositions of scale remover, but because of they are not that the effective scale remover of production is necessary, so these auxiliarys are easy to identification) the most important thing is spices, they can with larpenes, terpenes and hydro carbons (they can substitute spices or it is joined in the spices) be together as to the greasy very effective solvent on the crust that is cleaned, and form the disperse phase of oil-in-water (O/W) type microemulsion.More importantly cosurfactant and polyvalent metal ion on the another kind of function, cosurfactant helps to make the microemulsion stabilization, add polyvalent metal ion and can improve detergency, particularly for rarer scale remover and when a polyvalent salt of used anionic detergent be during to the greasy more effective washing composition that run in using.
In the disperse phase of the acid microemulsion scale remover that forms multiviscosisty, the useful various spices that have been found that can be those spices that are generally used in the cleaning product, preferably the spices that exists with liquid state usually.They are included in ester used in the perfume, ether, and aldehyde, pure and mild hydrocarbon, but the most important thing is to be rich in terpenic volatile oil.Except the stable disperse phase that forms microemulsion, seem that terpenes (and terpinol) has changed the detergency of the present composition with the detergent ingredients acting in conjunction of microemulsion.Have now found that in the present invention particularly that when using pine tree spices people can reduce the ratio of relatively expensive this spices and can come it is compensated by enough α-terpinols, also are like this in using some examples of other terpenic.For example, for each spices of 1%, people can substitute the 60%-90% of its weight with α-terpinol, as about 80%, and obtain same basically pine tree fragrance, have the good scale removal and the stability of microemulsion.Similarly, also can use terpenes and other similar terpenic compound and derivative, but α-terpinol is considered to best.
Contained polyvalent metal ion can be any suitable ion in scale remover of the present invention, includes but is not limited to magnesium (normally preferred), aluminium, copper, nickel, iron or calcium.Can any suitable mode add ion or their mixture, be their oxide compound or oxyhydroxide sometimes, but normally water miscible salt.Seem that reaction (or replaced the washing composition positively charged ion, or formed identical solution in milk sap), other character that this has improved detergency and has also improved product have usually taken place for negatively charged ion in polyvalent metal ion and the anionic detergent.If polyvalent metal ion and washing composition anionic reactive form a kind of insoluble product, then this polyvalent ion should be avoided using.For example, calcium and paraffin sulfonate anionic reactive form insoluble salt, so calcium ion as can obtaining from calcium chloride, will omit from any microemulsion scale remover that contains the paraffin sulfonate washing composition of the present invention.Similarly, polyvalent ion or other component in those present compositions that energy is unfavorable and other component is reacted also should be omitted.As previously mentioned, polyvalent metal ion is magnesium preferably, and it will join in other milk sap composition with the water-soluble salt form.Preferred this salt is sal epsom, typically use its heptahydrate (Epson salt), but its other hydrate or anhydride also is available.Usually, use the vitriol of polyvalent metal, because its sulfate anion also is the negatively charged ion of some anionic detergent and finds it is the by product of neutralization reaction in some washing composition.
The auxiliary surface activeconstituents of acidic descaling agent makes the oleophylic droplet and continuously the interfacial tension between water medium or surface tension are reduced to and approach 10
-3The value of dyne/cm, this cannot see with regard to causing the division automatically of disperse phase droplet to become little naked eyes to the people up to them, forms limpid microemulsion.The surface-area of disperse phase has increased and its dissolving power and grease are removed ability and also strengthened widely in this microemulsion, so acid microemulsion is more effective when to remove the oily scale remover be common milk sap size than disperse phase droplet significantly.Cosurfactant useful in scale remover of the present invention is: the water-soluble low-level chain triacontanol of a per molecule 2-4 carbon atom (being 3 or 4 carbon atoms sometimes preferably); 2-18 the unitary polypropylene glycol of propoxy-; Likes RO(X)
nThe monoalkyl lower glycol ether of H, wherein R is C
1-4Alkyl, x are CH
2CH
2CH
2O or CH(CH
3) CH
2O, n are 1-4; R
1Be C
2-4Acyl group and x and n are as preceding described mono alkyl ester; The alkanol that the aryl of 1-4 carbon atom replaces; Carbonic acid propylene ester; The alpha-hydroxy fatty acid of 2-6 carbon atom as single-, two-and the fat list of 2-6 carbon atom replacing of three-hydroxyl-, two-and tri-carboxylic acids; The low alkyl group list of phosphoric acid-, two-and three esters, wherein low alkyl group has 1-4 carbon atom; With their mixture.
Obviously, the cosurfactant of pointing out previously can be used in combination with the alpha-hydroxy fatty acid as cosurfactant.Concentration according to the alpha-hydroxy fatty acid cosurfactant, these non-sour cosurfactants are usually with the about 5%(weight of about 0.1%-), be the about 4.0%(weight of about 0.5%-better) amount be used in combination with the alpha-hydroxy fatty acid cosurfactant.
Representational this cosurfactant is a lactic acid, oxysuccinic acid and citric acid, and the Diethylene Glycol single-butyl ether, dipropylene glycol single-butyl ether and Diethylene Glycol list isobutyl ether, these are considered to the most effective.
By the discussion of front to cosurfactant useful in scale remover of the present invention, can obviously find out oxysuccinic acid, lactic acid and citric acid, with these mixture of ingredients be useful for the pH that reduces product, therefore it can remove soap film and lime shell at an easy rate from surface to be cleaned, and they have played the effect of cosurfactant simultaneously, have improved the outward appearance of product and have made product more effectively remove degrease from such surface.In described scale remover, have active other the specified acid material of cosurfactant by use and can obtain similar double effects.
The ratio of component is very important in the scope of determining in scale remover of the present invention, so that product can be most effectively removes greasy, lime shell and soap film from treated crust, and other settling, and in this processing, protect crust.Washing composition should be to be enough to removing degrease and the greasy ratio of cleaning surfaces that makes exists as previously mentioned; The ratio of alpha-hydroxy fatty acid should can be removed soap film and lime shell enough; Phosphonic acids or phosphoric acid and phosphonic mixture should can make the acid sensitivity surface avoid the infringement of alpha-hydroxy fatty acid enough; Water medium should be the solvent and the suspension medium of required composition and any auxiliary that may exist.Usually, this percentages of component is the xanthan gum of 0-1.0%, the synthetic anionic organic detergent of 1-9%, synthetic organic nonionic detergent of 0-5%, the alpha-hydroxy fatty acid of 2-9%, the phosphoric acid of 0.05-6% or its single salt and the phosphonic acids of 0.005-2%, the amino alkylidenyl phosphonic acids of 0-0.6%, or its mono phosphonic acid salt; The trim thing is water and auxiliary (if existence).Preferably use the mixture of lactic acid and oxysuccinic acid for alpha-hydroxy fatty acid.
Alpha-hydroxy fatty acid is about 5 with the ratio of amino alkylidenyl phosphonic acids in the present composition: about 250: 1 of 1-is about 2 better: about 10: 1 of 1-; Alpha-hydroxy fatty acid is about 5 with the ratio of phosphoric acid: 2-25: 1.
Usually will contain in scale remover is the polyvalent ion (particularly when the content of anion surfactant is 0.05-5%) of 0.1-3.0% preferably, preferably magnesium or aluminium and be more preferably magnesium.In addition, the per-cent of spices is generally 0.2-2%, 0.5-1.5% preferably, and at least 0.1% is terpenes or terpinol in this spices.Terpinol is α-terpinol and is preferably added to reduce the consumption of spices that the 50-90% in total spices (comprising α-terpinol) is a terpinol, better is about 80% terpinol.
The pH of various preferred microemulsion scale removers is 1-4 normally, 1.5-3.5 preferably, for example 3.The normally about 75%-90% of the content of water is that about 80%-85% and auxiliary content are 0-5% preferably in the microemulsion, usually about 1-3%.If pH is not in needed scope, usually will adjust with sodium hydroxide or suitable acid such as sulphuric acid soln, but pH normally is raised, rather than reduces, if pH will reduce when a lot, can replace sulphuric acid soln with the mixture of alpha-hydroxy fatty acid.
The liquid scale remover can mix by the various compositions with it to be made, and it is not really strict that it adds order.But the xanthan gum that selectivity is added at first need be mixed with water, various water miscible compositions are sneaked in the xanthan gum solution, the oil soluble composition mixes in independent operation, under agitation the molten part of oil is joined in the water-soluble part (in water), and two mixtures are mixed.
In some cases, in order to prevent that carrying out this step of unwanted chemical reaction between component can change, for example, people can directly not join strong phosphoric acid in sal epsom or the dyestuff, but this interpolation process should be carried out in the aqueous solution, preferably Xi Shi component.
During scale remover can be packed manually operated spraying dispersion cup on demand, these containers were made with the plastic material of preferably using synthetic organic polymer usually, as polyethylene, and polypropylene or polyvinyl chloride (PVC).This class container also can preferably include nylon or other non-reacted plastic seal, nozzle, inclined tube and banded dispenser part, the packing of generation scale remover be ideally suited for very much in the application of " spraying and obliterating ".Yet, in some cases, when lime shell and soap film deposition is very serious, scale remover can be stayed on the settling up to settling dissolving or loose, it can be wiped then, or can be rinsed, maybe can repeatedly use, repeatedly remove then, be removed up to settling.
The following example has illustrated the present invention but has not limited the present invention.Unless stated otherwise, at embodiment, all umbers in specification sheets and claims, ratio and per-cent all by weight, all temperature all are centigradetemperatures ℃.
Embodiment 1
| Component | %(weight) | ||
| A | B | C | |
| Sodium Lauryl Sulphate BP/USP C 13- 15Amino trimethyl-phosphine acid phosphoric acid spices (containing about 40% terpenes) the dyestuff pH Brookfield viscosity of Sodium Benzoate magnesium sulfate 7 hydrate malolactic acid citric acid RT, No. 2 spindle Sorpins (cps) | 4.00 0.30 1.50 2.0 2.0-0.25 0.425 0.8 0.002 trim, 3.0 10 trims 100.00 | 3.0 0.3 1.5 2.0 3.0-0.25 0.425 0.8 0.002 trims 3.0 10 | 4.0 0.3 1.5--4.0 0.25 0.425 0.8 0.002 trims 3.0 10 |
Follow these steps to make the microemulsion scale remover: optionally xanthan gum and benzoate are soluble in water, dissolving detergent then, after this under agitation will join in the detergent solution except the surplus water soluble materials spices and the conditioning agent (sodium hydroxide solution), pH is adjusted to 3.0, under agitation spices is joined in the aqueous solution subsequently, generate the needed microemulsion of limpid blueness at once.
Acidic descaling agent is installed in the polyethylene that polypropylene nozzle (this nozzle is adjustable to and closes spraying and flow out gear) is housed and extrudes in the bottle.In use microemulsion is sprayed on " bathtub dirt ring " on the bathtub, wherein except soap film and greasy also comprise the lime shell.Rate of application is approximately per 5 meters rings (approximately 3cm is wide) and uses 5ml.Used back etc. about 2 minutes, and wiped the dirt on the ring and clean with sponge immersion with sponge, can see greasy, soap film, even the lime shell is removed effectively.May need to use second time under the situation of or adhesion thick especially at the lime shell, but this is considered to standard.
Because flushing bathtub (or shower cabinet) is easy to, thus also can the rinsing bath cylinder surfaces, but this flushing is not absolutely necessary.
Sometimes xerotripsis also is enough, but used water is wiped with the sponge wipe surfaces or with wet cloth when removing any acid residuum if desired, but there is no need to use the water that surpasses ten times of used scale remover weight in this case.In other words, the surface does not need to be soaked in water up hill and dale or to wash, and it is still clean and glossiness (supposing that it was glossiness originally).In other of scale remover used, it can be used for clean shower stall ceramic tile, bathroom floor ceramic tile, kitchen tile, tank and enamel ware, do not injure their surface usually.Can recognize many this surfaces is acid proof, but a kind of commodity must in use not damage the relatively poor surface of acid resistance, as European enamel (often being fixed in cast iron or the steel plate substrate), is referred to as zirconium white powder enamel sometimes.A feature of above-mentioned scale remover (with other scale remover of the present invention) is their cleaning of hard surfaces effectively, but they contain the Ionized acid of energy really, therefore they should be used for the acid sensitivity surface.But, have now found that they do not damage European white enamel bathtub, in this example, when preparation closely similar with the composition of example therewith but that therefrom removed phosphonic acids or phosphonic acids-phosphate mixture cleaned, this enamel had been subjected to seriously influencing.
Claims (8)
1, a kind of acid microemulsion composition that is used for acid proof zirconium white enamel bathtub and other crust article, its pH is 1-4, can remove the delime shell from the surface of these class article, soap film and greasy and do not damage such surface, said composition comprises the synthetic organic detergent of washing composition ratio, can remove greasy from such surface; Remove the alpha-hydroxy fatty acid of lime shell and soap film ratio, amino alkylidenyl phosphonic acids, water and spices.
2, according to the composition of claim 1, wherein said alpha-hydroxy fatty acid has 2-6 carbon atom, the amino alkylidenyl phosphonic acids contains 1-3 amino nitrogen, 3 or 4 low-grade alkylidene phosphonate groups and 0-2 low-grade alkylidene that respectively has 2-6 carbon atom, when in the amino alkylidenyl phosphonic acids, having a plurality of amino nitrogen, alkylidene group be exist and be connected with amino nitrogen.
3, according to the composition of claim 2, wherein said alpha-hydroxy fatty acid is 5 with the ratio of said amino alkylidenyl phosphonic acids: 1-250: 1.
4, according to the composition of claim 3, synthetic organic detergent wherein is a kind of C
8-18Alkyl sulfate surfactant.
5, according to the composition of claim 1; wherein also there is phosphoric acid; it can improve the amino alkylidenyl phosphonic acids and not be subjected to role in the alpha-hydroxy fatty acid infringement on the be cleaned zirconium white enamel surface of article of protection; wherein phosphoric acid is 2 with the ratio of amino alkylidenyl phosphonic acids: 1-10: 1, and alpha-hydroxy fatty acid is 5 with the ratio of phosphoric acid: 2-25: 1.
6, according to the composition of claim 5, it contains the synthetic organic anion washing composition of 1-9%; Synthetic organic nonionic detergent of 1-6%; The alpha-hydroxy fatty acid of 2-9%, the amino alkylidenyl phosphonic acids of the phosphoric acid of 0.05-1% and 0.01-0.3%.
7, according to the composition of claim 1, wherein said alpha-hydroxy fatty acid is the mixture of oxysuccinic acid and lactic acid.
8, according to the composition of claim 1, wherein said alpha-hydroxy fatty acid is a citric acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US8063493A | 1993-06-24 | 1993-06-24 | |
| US080,634 | 1993-06-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1107509A true CN1107509A (en) | 1995-08-30 |
Family
ID=22158619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94107561A Pending CN1107509A (en) | 1993-06-24 | 1994-06-24 | Acid microemulsion composition |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0630963A3 (en) |
| JP (1) | JPH07305100A (en) |
| KR (1) | KR950000852A (en) |
| CN (1) | CN1107509A (en) |
| AU (1) | AU6337694A (en) |
| BR (1) | BR9402493A (en) |
| CA (1) | CA2126626A1 (en) |
| HU (1) | HUT68690A (en) |
| NZ (1) | NZ260608A (en) |
| PL (1) | PL177789B1 (en) |
| PT (1) | PT101531B (en) |
| ZA (1) | ZA944078B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107057875A (en) * | 2017-04-12 | 2017-08-18 | 佛山市德可为装饰材料有限公司 | Cleaning agent for cleaning ceramic tile back side attachment |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5707952A (en) * | 1996-04-24 | 1998-01-13 | Colgate-Palmolive Company | Thickened acid composition |
| US6268330B1 (en) * | 1999-05-21 | 2001-07-31 | Colgate-Palmolive Company | Clear microemulsion acidic light duty liquid cleaning compositions |
| KR100419752B1 (en) * | 1999-12-28 | 2004-02-21 | 주식회사 하이닉스반도체 | Manufacturing method of semiconductor device |
| JP2004075764A (en) | 2002-08-13 | 2004-03-11 | Takasago Internatl Corp | Composition for liquid detergent for hard object surface |
| KR20020070250A (en) * | 2002-08-20 | 2002-09-05 | 홍성칠 | Washing agent composition for a building structure |
| JP4884768B2 (en) * | 2005-12-28 | 2012-02-29 | 花王株式会社 | Hard surface cleaner |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT951279B (en) * | 1971-07-01 | 1973-06-30 | Benckiser Gmbh Joh A | PROCESS TO PREVENT THE FORMATION OF DEPOSITS THAT PRODUCE CROSSING IN AQUEOUS SYSTEMS |
| DE2507156A1 (en) * | 1975-02-20 | 1976-09-02 | Hoechst Ag | ACID, ALL-PURPOSE DETERGENTS |
| US4246030A (en) * | 1978-12-08 | 1981-01-20 | The Mogul Corporation | Corrosion inhibiting compositions and the process for using same |
| FR2466500A1 (en) * | 1979-10-04 | 1981-04-10 | Produits Ind Cie Fse | METHOD OF CLEANING VEHICLES AND COMPOSITION IMPLEMENTED |
| JPH075907B2 (en) * | 1987-04-01 | 1995-01-25 | 花王株式会社 | Bathroom cleaner composition |
| US5108643A (en) * | 1987-11-12 | 1992-04-28 | Colgate-Palmolive Company | Stable microemulsion cleaning composition |
| US5192460A (en) * | 1988-02-10 | 1993-03-09 | Colgate-Palmolive Company | Safe acidic hard surface cleaner |
| DE3910042A1 (en) * | 1989-03-28 | 1990-10-04 | Sebastian Reinhardt | Composition for long-lasting cleaning of metal surfaces |
-
1994
- 1994-05-26 NZ NZ260608A patent/NZ260608A/en unknown
- 1994-05-26 AU AU63376/94A patent/AU6337694A/en not_active Abandoned
- 1994-06-09 ZA ZA944078A patent/ZA944078B/en unknown
- 1994-06-15 PT PT101531A patent/PT101531B/en not_active IP Right Cessation
- 1994-06-21 EP EP94304492A patent/EP0630963A3/en not_active Withdrawn
- 1994-06-22 BR BR9402493A patent/BR9402493A/en not_active Application Discontinuation
- 1994-06-23 PL PL94303966A patent/PL177789B1/en not_active IP Right Cessation
- 1994-06-23 CA CA002126626A patent/CA2126626A1/en not_active Abandoned
- 1994-06-23 HU HU9401898A patent/HUT68690A/en unknown
- 1994-06-23 KR KR1019940014504A patent/KR950000852A/en not_active Application Discontinuation
- 1994-06-24 CN CN94107561A patent/CN1107509A/en active Pending
- 1994-06-24 JP JP6142989A patent/JPH07305100A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107057875A (en) * | 2017-04-12 | 2017-08-18 | 佛山市德可为装饰材料有限公司 | Cleaning agent for cleaning ceramic tile back side attachment |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0630963A2 (en) | 1994-12-28 |
| NZ260608A (en) | 1995-02-24 |
| PT101531A (en) | 1995-03-31 |
| HUT68690A (en) | 1995-07-28 |
| PL177789B1 (en) | 2000-01-31 |
| PT101531B (en) | 1999-12-31 |
| HU9401898D0 (en) | 1994-09-28 |
| ZA944078B (en) | 1995-12-11 |
| BR9402493A (en) | 1995-01-24 |
| PL303966A1 (en) | 1995-01-09 |
| EP0630963A3 (en) | 1995-05-10 |
| JPH07305100A (en) | 1995-11-21 |
| CA2126626A1 (en) | 1994-12-25 |
| AU6337694A (en) | 1995-01-05 |
| KR950000852A (en) | 1995-01-03 |
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