CN1048059A - The light-duty liquid or the colloid dish washing detergent compositions that contain a kind of alkyl ethoxy carboxylate surfactant - Google Patents

The light-duty liquid or the colloid dish washing detergent compositions that contain a kind of alkyl ethoxy carboxylate surfactant Download PDF

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Publication number
CN1048059A
CN1048059A CN90103082A CN90103082A CN1048059A CN 1048059 A CN1048059 A CN 1048059A CN 90103082 A CN90103082 A CN 90103082A CN 90103082 A CN90103082 A CN 90103082A CN 1048059 A CN1048059 A CN 1048059A
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composition
alkyl
contain
surfactant
mixture
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罗德尼·马龙·怀斯
托马斯·安东尼·克里普
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Procter and Gamble Co
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Procter and Gamble Co
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21D—TREATMENT OF THE MATERIALS BEFORE PASSING TO THE PAPER-MAKING MACHINE
    • D21D1/00—Methods of beating or refining; Beaters of the Hollander type
    • 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
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C11D1/04—Carboxylic acids or 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
    • 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
    • C11D1/143—Sulfonic acid esters
    • 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
    • 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
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • 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
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/38—Cationic compounds
    • 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
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/521—Carboxylic amides (R1-CO-NR2R3), where R1, R2 and R3 are alkyl or alkenyl groups
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Abstract

The present invention relates to a kind of a kind of alkyl ethoxy carboxylate surfactant that contains, contain on a small quantity or do not contain the light-duty liquid or the colloid dish washing detergent compositions of fatty alcohol ethoxylate and soap class byproduct pollutent again.This composition exhibiting goes out good detergency ability, and is gentle to skin.A kind of preferred type of dish washing detergent compositions is a liquid form.The high pH value and the magnesium ion that contain such composition can improve the degreasing performance, and keep mildness.

Description

The light-duty liquid or the colloid dish washing detergent compositions that contain a kind of alkyl ethoxy carboxylate surfactant
The application is that await the reply when being 354,967 part of application of the application number submitted on May 22nd, 1989 is applied for continuously.
The present invention relates to contain the light-duty liquid or the colloid dish washing detergent compositions of alkyl ethoxy carboxylate surfactant, such tensio-active agent is disclosed in United States Patent (USP) NOS.2,183,853,2,653,972,3,003,954,3,038,862,3,741, in 911 and 3,941,710; English Patent NOS.456,517 and 1,169,496; Canadian Patent NO.912,395; French Patent NOS.2,014,084 and 2,042,793; Netherlands patent applications specification sheets 7,201,735-Q and 7,406,336; And among Japanese patent application specification sheets 96,579/71 and 99,331/71, these tensio-active agents selectively are labeled as many oxyethyl groups of alkyl carboxymethyl salt, many ethoxyacetic acids of alkyl salt, alkyl polyether carboxylate salt etc.
People propose heavy demand to light-duty liquid or the colloid dish washing detergent that possesses good ability of cleaning greasy dirt.These detergent composition have been known in the present technique field and are on the books, for example, at United States Patent (USP) NOS.4,316,824(Pancheri), 4,681, people such as 704(Bernardino), 4,133, people such as 779(Hellyer) and 4,615, people such as 819(Leng) introduction is arranged.Although these compositions are purificants of good greasy and dirt, make pachylosis in some cases, especially use winter at exsiccant.
The abundant detergent composition suitable to the skin peptide arranged in the prior art again.These mild compositions contain the vitriol of highly ethoxylatedization Fatty Alcohol(C12-C14 and C12-C18) usually, referring to the United States Patent (USP) 3,743,233 as Rose and Thiele.Existing suggestion garden beet alkali (betaine) improves a kind of gentle performance of liquid tableware cleaning composition.Example is seen United States Patent (USP) 4,555, people such as 360(Bissett).It is known that alkyl ethoxy carboxylate is used for liquid detergent compositions as the mild tensio-active agent.Referring to Japanese patent application specification sheets 48-60706 and 48-64102.Yet, be bad aspect the ability of cleaning greasy dirt according to these alkyl ethoxy carboxylate surfactants of record, need to use other tensio-active agent to reach required clean effect.
Almost mildness and this two specific character of ability of cleaning greasy dirt are not combined in a kind of product.It has been generally acknowledged that obtaining a specific character must lose another kind of characteristic.Thereby one object of the present invention just provides a kind of detergent composition, and it shows good ability of cleaning greasy dirt and demonstrates mildness to skin again.
The present invention relates to the dish washing detergent compositions of a kind of light-duty liquid or colloid (preferably liquid), this composition contains a kind of surfactant mixture of about 5%～70%, and this mixture contains:
(a) about 80%～100% alkyl ethoxy carboxylate, its chemical general formula is:
Wherein R is C 12To C 16Alkyl, X is from 0 to about 10; The composition of various ethoxylates distributes following (by weight), and the ethoxylate proportion of X=0 is less than 20%, and X greater than 7 ethoxylate proportion less than 25%, as R average out to C 13Or more hour, the mean value of X is 2-4, when R on average greater than C 13The time, the mean value of X is 3-6, and M is a kind of positively charged ion;
(b) 0 to about 10% fatty alcohol ethoxylate, its chemical formula is:
RO（CH 2CH 2O） XH
Wherein R is C 12To C 16Alkyl, X is from 0 to about 10, and the mean value of X is approximately less than 6; And
(c) the soap class of chemical formula below 0% to about 10% have:
RCOO -M +
Wherein R is a C 11To C 15Alkyl, M is a kind of positively charged ion.Wherein, contain 10%(weight) the pH value of the aqueous solution of above-mentioned composition be about 7 to 11.
Light-duty liquid of the present invention or colloid (being preferably liquid) dish washing detergent compositions contain a kind of surfactant mixture, this surfactant mixture contains a kind of alkyl ethoxy carboxylate surfactant that accounts for main amount and a small amount of or do not have fatty alcohol ethoxylate and a soap class by product pollutent.Being present in liquid or the colloid dish washing detergent compositions typical these and other auxiliary selectable compositions exemplifies as follows.
The surfactant mixture that contains alkyl ethoxy carboxylate
This liquid composition of the present invention contains about 5% to 50%(weight ratio), be preferably approximately 10% to 40%, the best is a kind of surfactant mixture of about 12% to 30%, its content is to determine according to the degree of dirt.Colloidal compositions of the present invention contains has an appointment 20% to about 70%, is preferably about 25% to about this surfactant mixture of 45%, preferably about 28% to about 35%.
This surfactant mixture contains has an appointment 80% to 100%, is preferably approximately 85% to 95%, and preferably about chemical general formula of 90% to 95% is RO(CH 2CH 2O) XCH 2COO -M +Alkyl ethoxy carboxylate, wherein R is C 12To C 16Alkyl, the scope of X from 0 to about 10, and the composition of various ethoxylates distributes following (by weight), the ethoxylate proportion of X=0 is lower than about 20%, preferable be lower than approximately 15%, be preferably lower than approximately 10%, X is lower than about 25% greater than 7 ethoxylate proportion, preferablely be lower than approximately 15%, be preferably lower than about 10%; As R average out to C 13Or more hour, the mean value of X is 2-4, when R on average greater than C 13The time, the mean value of X is 3-6, and M is a kind of positively charged ion, preferably is selected from basic metal, alkaline-earth metal, ammonium,, two or triethanol ammonium, preferably be selected from sodium, potassium, ammonium and with the mixture of magnesium ion.Preferable alkyl ethoxy carboxylate be those wherein R be C 12To C 14Alkyl.
The precursor of the suitable alcohol of alkyl ethoxy carboxylate of the present invention is to contain 12 aliphatic primary alcohols to about 16 carbon atoms of having an appointment.Other suitable primary aliphatic alcohols is a straight chain primary alcohol, these straight chain primary alcohols are by obtaining carrying out hydrogenization such as Oleum Cocois, palm-kernel oil and beef fat this class plant of acid or tallow fatty acid, or by obtaining as Ziegler-type method (Ziegler) ethene building-up reactions and hydrolysis subsequently.Preferable alcohol is n-Octanol, nonanol-, nonylcarbinol, n-undecane alcohol, n-dodecane alcohol, n-tridecane alcohol, n-tetradecanol, the pure and mild cetyl alcohol of Pentadecane.Other suitable pure precursors comprise having in the β position or say on the 2-carbon atom position that the certain proportion side chain is arranged, and this alkyl branches is the primary alconol with 1 to 4 carbon atom.In this class alcohol, what meet the requirements is that to have the alcohol of 30% various certain chain lengths at least are straight chains, and side chain is preferably and contains about 50% methyl group and a spot of ethyl, propyl group and butyl.These alcohol can make with carbon monoxide and H-H reaction by the normal olefine that will have about 11 to 17 carbon atoms easily.These straight chains and branched fatty alcohol can form by these reactions, and this mixture both can use like this and also be separable into single component, and then mix again and obtain required mixture.
" OXo " halid typical process that production is used to prepare alcohol is disclosed in United States Patent (USP) NOS.2, and in 564,465 and 2,587,858, the direct carbonylation of alkene is disclosed in United States Patent (USP) 2,504 with the technology that produces alcohol, in 682 and 1,581,988.All these patents are by being incorporated herein with reference to its method.
The secondary alcohol of equivalence also can use.Obviously,, obtain the long alcohol of corresponding strand, yet both economical method is to use and has the alkene mixture that a carbon chain lengths scope is arranged around required mean chain length usually if use the long alkene of a kind of strand to make raw material.Certainly, this just obtains having around the mean chain length mixture of an identical chain length distribution alcohol.
The primary aliphatic alcohols that makes from have alkyl or alkylidene group other petroleums as its part-structure from vegetables oil or fat neutralization also contains the scope of a chain length.Because the chain length scope is C 8-C 20Perhaps exceed, thereby standard practice is to be separated into the product with different chain length scope from such raw material that this product can be selected according to end-use.
Required average oxyethyl chain length can obtain by the catalysis ethoxylation process on this fatty alcohol ethoxylate.The molar weight of the oxyethane thing of normal Fatty Alcohol(C12-C14 and C12-C18) reaction is corresponding with the number of average ethoxy group on this fatty alcohol ethoxylate with each in this reaction.Knownly can promote oxyethane to be added to the reaction on the alkanol by catalyzer, the catalyzer with strong acid or highly basic characteristic is the most commonly used.The basic catalyst that is suitable for is the alkali-metal basic salt of I main group in the periodictable, for example, and the basic salt of some alkaline-earth metal of II main group in sodium, potassium, rubidium and caesium and the periodictable, for example, calcium, strontium, barium and available in some cases magnesium.The proper acidic catalyzer comprises, in a broad sense, and Louis (Lewis) acid of Friedel-Craft (Friedel-Crafts) type catalyzer.The object lesson of these catalyzer is fluorochemical, muriate and the bromide of boron, antimony, tungsten, iron, nickel, zinc, tin, aluminium, titanium and molybdenum.These halogenide also have report with the purposes of for example complex compound of alcohol, ether, carboxylic acid and ammonia.Other examples of known acid oxyalkylation catalyzer are sulfuric acid and phosphoric acid; The perchlorate of perchloric acid and magnesium, calcium, manganese, nickel and zinc; Metal oxalate, vitriol, phosphoric acid salt, carboxylate salt and acetate; The alkali metal fluosilicate borate, the titanate of zinc; The metal benzene sulfonate.Employed catalyst type will be determined the distribution of ethoxy group range.Stronger catalyzer will produce round the distribution of the very close or narrow ethoxy group of mean value.More weak catalyzer will cause the distribution of relative broad range.
This surfactant mixture also contains 0% to about 10%, is preferably to be lower than approximately 8%, and the best is that to be lower than about 5% chemical general formula be RO(CH 2CH 2O) XThe fatty alcohol ethoxylate of H, wherein R is a C 12To C 16Alkyl, the X scope is 0 to about 10, and X mean value is lower than 6.This surfactant mixture also contains 0% to about 10%, is preferably to be lower than approximately 8%, and preferably being lower than about 5% chemical formula is RCOO -M +The soap class, wherein R is a C 11To C 15Alkyl, and M is a kind of aforesaid positively charged ion.
The fatty alcohol ethoxylate of not carboxylation as noted above is disadvantageous to this alkyl ethoxy carboxylate surfactant mixture, is disadvantageous to the performance advantage that provides thus especially.Thereby it is very strict using the surfactant mixture contain this alkyl ethoxy carboxylate in the present invention, contains in this mixture by this mixture deutero-less than about 10% fatty alcohol ethoxylate.Although the alkyl ethoxy carboxylate of commercial use contains 10% or greater than 10% fatty alcohol ethoxylate, there is known method can make required high purity alkyl ethoxy carboxylate.For example, United States Patent (USP) 4,098, that introduces 818(embodiment 1) can remove unreacted fatty alcohol ethoxylate by vapor distillation, or as English Patent 1,027,481(embodiment 1) in point out pass through this alkyl ethoxy carboxylate carry out recrystallizationization.Other methods that obtain required carboxylate salt be with sodium hydroxide or sodium Metal 99.5 and chloracetic acid or their salt with fatty alcohol ethoxylate chemosynthesis under specific pressure and temperature, these are at United States Patent (USP) 3,992,443 and 4,098,818; And explanation is all arranged among the Japanese patent application 50-24215, these methods are incorporated herein by reference.
Another kind method is, uses a kind of hindered base, and for example uncle's fourth potassium oxide replaces the sodium hydroxide in the above-mentioned patent that exemplifies, and the result not too obtains highly purified alkyl ethoxy carboxylate under harsh temperatures and the pressure at needs.Especially use a kind of chemical formula to be RO -M +A kind of hindered base of (promptly it is by an alkyl usually, and the oxygen center of a reaction and a positively charged ion constitute).The structure of this hindered base is secondary or three grades, and contains a non-straight chained alkyl that at least one side chain position is arranged in 3 carbon atoms of reactive center, also contains a Sauerstoffatom and basic metal or alkaline earth metal cation.This preparation process comprises with this fatty alcohol ethoxylate reacts with above-mentioned hindered base and anhydrous chloracetic acid, and wherein the molar ratio of this hindered base and anhydrous chloracetic acid is 2: 1; Perhaps use an alkali metal salt or the alkaline-earth metal reactant salt of this fatty alcohol ethoxylate with above-mentioned hindered base and a kind of anhydrous chloracetic acid, wherein the molar ratio of an alkali metal salt of this hindered base and chloracetic acid or alkaline earth salt is 1: 1, in this reaction, the mol ratio of the anhydrous therewith chloracetic acid of the Fatty Alcohol(C12-C14 and C12-C18) of this ethoxylation or its basic metal or alkaline earth salt is from about 1: 0.7 to about 1: 1.25, temperature range is from about 20 to 140 ℃, and pressure range is about 1 to 760mmHg.
The additive method for preparing high-purity alkyl ethoxy carboxylate is with fatty alcohol ethoxylate, and with the oxygen reaction, these methods are at United States Patent (USP) NO.4 under the condition that platinum, palladium or other precious metals exist, 223,460(embodiment 1-7), NO.4,214,101(embodiment 1) and NO.4,348,509; German Patent NO.3 has explanation in 446,561 and Japanese patent application NO.62,198,641.One of by product of this class reaction is the soap class, and as above-mentioned, it should be limited the quantity of in order to avoid the clean power that composition of the present invention is brought and the advantage of mildness produce adverse effect.This qualification can contain the fatty alcohol ethoxylate raw material of the non-ethoxylated Fatty Alcohol(C12-C14 and C12-C18) of low amount by use, and select for use the catalyzer of the end position methylene radical that has in this fatty alcohol ethoxylate of oxidation according to qualifications to realize, this catalyzer probability of oxidation end position methylene radical according to qualifications reaches 90% at least, and preferable is at least about 95%.The methylene radical of the non-end position in this fatty alcohol ethoxylate of oxidation will produce the soap class from the Fatty Alcohol(C12-C14 and C12-C18) component of ethoxylation.
The pH value of composition of the present invention is from about 7 to 11, and reasonable measuring method is with the PH meter, uses 10%(weight) determination of aqueous solution as pH value.Preferable detergent composition PH scope approximately from 8 to 10.5 is preferably from about 8.5 to 10.Usually, liquid dishwashing cleaning combination pH value is about 7.Have been found that for detergent composition of the present invention the pH value (being that about PH is 9) that relatively shows alkalescence is that 7 product has the clean power of the greasy dirt that improves more than PH.The composition that this clean advantage seemingly contains alkyl ethoxy carboxylate of the present invention is peculiar.Amazingly be, composition of the present invention is being 7 bigger alkaline ph value scopes than PH, and its adversary is more gentle.
If a kind of have pH value to be higher than 7 composition be very effectively to talk about improving aspect of performance, it should contain a kind of buffer reagent so, and the sort buffer agent has the ability of (being about aqueous solution of 0.1% to 0.2%) maintenance alkaline ph value in the diluent of this composition and this composition.The PKa value of sort buffer agent should be lower than about 0.5 to 1.0 the PH unit of the required pH value of this composition (measuring method as previously mentioned).
Dish washing detergent of the present invention combination is promptly diluted and when being used for dirty plate, be born the acidity effect that is produced by the food dirt in use.For keeping composition of the present invention feature performance benefit in use, composition of the present invention should contain a kind of have be lower than the buffer reagent of required pH value about 0.5 to the PKa value of 1.0PH unit.In this case, this buffer reagent is controlled pH value the most effectively, and the consumption of this composition is minimum.
This buffer reagent can be a kind of activated detergent from himself, perhaps can be a kind of low-molecular-weight organic or inorganic thing, and they are used in the application's the composition only is for keeping alkaline ph value.Preferable buffer reagent for the present composition is a nitrogenous substances.For example, be glycine or other amino acid, or as list, two or the lower aliphatic hydramine of trolamine class.Other preferable nitogen-contained buffer agents are 2-amino-2-ethyls-1, ammediol, three-(methylol) ammonia methane and disodium glutamate salt.Boric acid also is preferable.These buffer reagents are typically with about 0.1 to 10% weight percent, are preferably from about 1% to 7%, and the best is to be present in this composition from about consumption of 1.5 to 5%.
For the positively charged ion in this alkyl ethoxy carboxylate can be basic metal, alkaline-earth metal, ammonium and low-level chain triacontanol ammonium ion.Positively charged ion in this alkyl ethoxy carboxylate comes this alkyl ethoxy carboxylic acid reaction of self-neutralization and from additional ingredients, and that for example adds contains bivalent ions salt.
The preferable positively charged ion that is used for the present composition is ammonium ion, sodium and potassium ion.Concerning having the composition of pH value between about 7 and 8, ammonium ion is best, if but pH value is higher than 8, then do not use ammonium ion, and because producing the deprotonation reaction, the ammonium ion in the composition discharges a spot of ammonia.For liquid composition of the present invention, potassium is more preferred than sodium, and this is because potassium makes composition of the present invention more can suppress throw out formation at low temperatures, and this composition dissolves degree is improved.On the other hand, for colloidal compositions of the present invention, sodium is more preferred than potassium, and this is because sodium makes the composition gelling than potassium is easier.These cationic mixtures can be used in any composition of the present invention.
And then find again will improve ability of cleaning greasy dirt greatly when having divalent cation in the alkyl ethoxy carboxylate of the present invention.When this composition is used for containing a small amount of bivalent ions softening water, the way it goes for this situation.And contain with the strict tableware liquid composition that limits inconsistent alkyl ethoxy carboxylate of the present invention in add divalent ion and do not have benefit, and in many cases, practical manifestation goes out because the interpolation divalent cation reduces clean performance.Can it is believed that divalent ion has improved alkyl ethoxy carboxylate of the present invention the gathering of oil/water termination, therefore reduce interfacial tension, improve ability of cleaning greasy dirt.
Preferable situation be composition of the present invention used in a kind of highly basic and after, these divalent ions are joined in the composition of the basic metal that contains a kind of this alkyl ethoxy carboxylate or ammonium salt (preferably sodium salt) with muriate or sulphate form.Bivalent ions content is 0% to about 1.5% in this composition, is preferably from about 0.2% to 1.0%, preferably from about 0.3 to 0.8%(weight).Highly preferred divalent ion is a magnesium ion.
When these two was used in combination in surfactant mixture of the present invention with divalent ion and alkaline ph value, the ability of cleaning greasy dirt that is reached was better than using separately alkaline PH or divalent ion.Under the preferable situation, this divalent ion is a magnesium, and its amount in this composition is about 0.1% to 1%, and the best is about 0.3%～about 0.8%(weight), and this pH value is preferably from about 8～9.5, preferably 8.5～9.5.Contain the magnesium of high level and pH value and be higher than 9.5 composition and not preferred, this is because the sedimentary trend of generation is arranged.
The consumption of magnesium ion depends on the total amount of the anion surfactant that wherein has in the present composition, comprises the amount of alkyl ethoxy carboxylate.When magnesium ion is present in the composition of the present invention, be from about 0.25: 1 to about 0.5: 1 for the mol ratio of the anion surfactant of composition magnesium ion of the present invention and total amount.
Synergistic surfactant
Composition of the present invention preferably contains some synergistic surfactant to help foaming, clearing power and/or mildness.
Being included in such tensio-active agent is several anion surfactants that are generally used for liquid or colloid dish washing detergent.The positively charged ion that combines with these anion surfactants can be foregoing those positively charged ions that are suitable for this alkyl ethoxy carboxylate.The example that is used for the present invention's negatively charged ion synergistic surfactant is following type:
(1) alkylbenzene sulfonate, wherein alkyl contains 9 to 15 carbon atoms in the straight or branched configuration, preferably 11 to 14 carbon atoms.A kind of particularly preferred linear alkyl Phenylsulfonic acid contains 12 carbon atoms of having an appointment.United States Patent (USP) NO.2,220,099 and 2,477,383 have detailed introduction for these tensio-active agents.
(2) alkyl-sulphate, it is by 8 to 22 carbon atoms being arranged with one, preferably the Fatty Alcohol(C12-C14 and C12-C18) of 12 to 16 carbon atoms carries out sulfation and obtains.The chemical general formula of this alkyl-sulphate is ROSO - 3M +, wherein R is C 8～C 22Alkyl, and M is the positively charged ion of a kind of monovalence and/or divalence.
(3) paraffinic base sulfonate, its alkyl contain 8～22 carbon atoms, preferably 12～16 carbon atoms.These tensio-active agents can have been bought with the trade mark of Hostapur SAS from Hoechst Celanese.
(4) alkene sulfonate, it has 8～22 carbon atoms, is preferably 12～16 carbon atoms.United States Patent (USP) NO.3, in 332,880 relevant for the explanation of suitable alkene sulfonate.
(5) sulfated alkyl ether, it be by will containing 8～22 carbon atoms, preferablely contain 12～16 carbon atom alcohols with being lower than 30, be preferably lower than 12 moles oxyethane and carry out the ethoxylation process and produce.This sulfated alkyl ether has following chemical formula:
RO（C 2H 4O）xSO - 3M +
Wherein R is C 8～C 22Alkyl, X is 1～30, M is monovalence or divalent cation.
(6) alkyl glycerol ether sulfonate, wherein alkyl contains 8～22 carbon atoms, is preferably 12～16 carbon atoms.
(7) dialkyl sulfosuccinates, its chemical formula is
Wherein, the R of each 1And R 2Can be identical or different, represent that separately one has 4～10 carbon atoms, is more preferably the straight or branched alkyl of 6～8 carbon atoms, M +The positively charged ion of expression monovalence or divalence.Can be for the more complete explanation of suitable dialkyl sulfosuccinates at English Patent NO.2, find in 105,325 and NO.2,104,913.
(8) have the fatty sulfonate of following chemical formula:
R 1-CH（SO - 3M +）CO 2R 2
R wherein 1Be C 8～C 18, C preferably 12～C 16The alkyl of straight or branched, R 2Be C 1～C 6, C preferably 1The straight or branched alkyl, M +The positively charged ion of expression monovalence or divalence.
(9) their mixture.
Above-mentioned anion surfactant can have been bought.To the pH value situation that shows alkalescence slightly good effect is arranged in neutrality although should be noted that dialkyl sulfosuccinates and fatty sulfonate, be higher than at about 8.5 o'clock at pH value, they are not chemically stable in this composition.
Other effective synergistic surfactants that can use in this composition are the adipose alkyl polyglucosides of those non-ionic types.These tensio-active agents contain the C of straight or branched 8～C 15, be preferably from about C 12～C 14Alkyl, and have mean value and be about 1～5 glucose unit, be that 1～2 glucose unit is best and have mean value.With United States Patent (USP) 4,393, disclosed these tensio-active agents in 203 and 4,732,704 are by with reference to being incorporated herein.
These synergistic surfactants that are used for composition of the present invention also can contain the aniorfic surfactant mixture that has alkyl polyglucoside.The consumption of the synergistic surfactant in this composition is 0% to about 35%(weight), be preferably from about 5%～25%, the best is about 7%～20%.
Suds booster
Other components that can add in the present composition are a kind of tensio-active agents (suds booster) of stable foam, and its consumption should be less than 15%, preferably between about 0.5～12%, more preferably between about 1%～10%.The tensio-active agent that can be used for the alternative stable foam of composition of the present invention has following 5 kinds of base types: trimethyl-glycine, ethylene oxide condensate, fatty acid amide, semi-polarity non-ionic type amine oxide and cationic surfactant.
Composition of the present invention can comprise the betaine type detersive surfactant with following general formula, and its general formula is:
（+）????????（-）
R-N（R 1） 2-R 2COO
Wherein R is a kind of hydrophobic grouping, this group is selected from following several group, they are: contain 10～22 carbon atoms of having an appointment, be preferably the alkyl of about 12～18 carbon atoms, alkaryl and aralkyl with identical carbon atoms, phenyl ring wherein can be regarded as and be equivalent to 2 carbon atoms, and has by the similar structures of amido or ether disconnection; Each R 1Be all and contain 1 alkyl, R to about 3 carbon atoms 2Be to contain 1 alkylidene group to about 6 carbon atoms.
The example of preferable trimethyl-glycine is Varion CDG-K, hexadecyldimethyl benzyl ammonium trimethyl-glycine, dodecyl amido third dimethyl betaine, tetradecyl dimethyl betaine, tetradecyl amido third dimethyl betaine and dodecyl dimethyl caproic acid ammonium.
Other suitable amidoalkyl trimethyl-glycines have been disclosed in the following patent literature, and they are U.S. Pat 3,950, and 417; US4,137,191; US4,375,421; And English Patent GB2,103,236; Be incorporated herein by reference at this.
As everyone knows, the alkyl (and acyl group) that is used for above-mentioned beet alkali surface activator can obtain from natural or synthetic raw material, and for example, they can obtain from following several materials, and these materials are: naturally occurring lipid acid; Such as a class alkene with Ziegler process or oxo synthesis preparation; Or from process cracking or the last alkene of through the cracked oil, separating.
So-called ethylene oxide condensate is defined as widely by ethylene oxide group (hydrophilic nmature) and a kind of organic hydrophobic compound (can be aliphatic series or alkane aromatic substance) and carries out the compound that condensation reaction generates.In this compound, carry out the hydrophilic radical of condensation or the carbon chain lengths of polyalkylene oxide groups can be regulated at an easy rate, have required balanced water-soluble cpds between wetting ability and the hydrophobic group to produce a kind of being in any specific hydrophobic grouping.
The example that is suitable as the ethylene oxide condensate of suds-stabilizing agent is the condenses of fatty alcohol and oxyethane.Alkyl chain in the said fatty alcohol can be a straight or branched, usually contain 8～18 carbon atoms in this alkyl chain, in order to obtain best foam stabilization performance, said carbonatoms preferably is about 8～14, and concerning every mole Fatty Alcohol(C12-C14 and C12-C18), the consumption of oxyethane is about the 8-30 mole, the preferable 8-14 mole that is about.
The example of above-mentioned suitable amide surfactants comprises the single ethanol amide and the diglycollic amide of lipid acid ammonium, lipid acid, and carboxyl groups wherein contains 8～18 carbon atoms of having an appointment, and this class tensio-active agent can be represented with following general formula:
R 1-CO-N（H） m-1（R 2OH） 3-m
R wherein 1Can be one and have about 7-21 carbon atom preferably have about 11-17 carbon atom, saturated or unsaturated aliphatic hydrocarbyl; R 2Represent a methylene radical or ethylidene; M is 1,2 or 3, preferably 1.The object lesson of said acid amides has the monoethanolamine acid amides of cocoanut fatty acid and the diethanolamine acid amides of ten difatty acids.These carboxyl groups both can be made by naturally occurring glyceryl ester, and its example has: Oleum Cocois, plam oil, soybean oil and animal grease; Also can make, for example by making to the oxidation of oil or by using Fischer-Tropsch process (Fischer-Tropsch) that carbon monoxide is carried out hydrogenation reaction by the synthetic method.Preferably C wherein 12- 14The single ethanol amide of lipid acid and diglycollic amide.
Semi-polarity non-ionic type amine oxide surfactant comprises that those have the compound of following general formula or the mixture of several compounds, and said general formula is
R wherein 1Be an alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl or 3-alkoxyl group-2-hydroxypropyl, alkyl wherein and alkoxyl group respectively contain 8-18 the carbon atom of having an appointment; R 2And R 3Can be methyl, ethyl, propyl group, sec.-propyl, 2-hydroxyethyl, 2-hydroxypropyl or 3-hydroxypropyl independently of one another; And n is 0 to about 10 number.Particularly preferably be amine oxide with following general formula:
Figure 901030821_IMG3
R wherein 1Be a C 12-16Alkyl, R 2And R 3Be methyl or ethyl.Above-mentioned ethyl oxide condenses, amides and oxidation amine be in U.S. Pat 4,316, detailed introduction arranged in 824(Pancheri), this with reference to and be incorporated herein.
Composition of the present invention also can contain some general formula
The tensio-active agent or the general formula of cationic quaternary ammonium class be
The amine tensio-active agent, R wherein 1Be a kind of alkyl or alkane benzyl that on its alkyl chain, has about 6～16 carbon atoms; Each R 2All be selected from-CH 2CH 2-,-CH 2CH(CH 3)-,-CH 2CH(CH 2OH)-,-CH 2CH 2CH 2-and their mixture; When y is not equal to 0, each R 3All be selected from C 1-C 4Alkyl, C 1-C 4Hydroxyalkyl, benzyl and hydrogen; R 4Can with R 3Identical, perhaps can be such alkyl chain, wherein R 1Add R 4The total number of carbon atoms be about 8-16; Each y is all a number of 0 to about 10, and the summation of two y values is 0 to about 15, and X can be any suitable negatively charged ion.
In above-mentioned situation, the preferably tertiary ammonium surfactant of alkyl, particularly those R wherein that represent with above-mentioned general formula 4With R 3The alkyl surfactants of identical long strand.Wherein most preferred tertiary ammonium surfactant is C 8-16Alkyltrimethylammonium, C 8-16Alkyl two (hydroxyethyl) ammonium methyl, C 8-16Alkyl hydroxyethyl dimethylammonium, C 8-16Alkoxyl group propyl group TMA (TriMethylAmine) and C 8-16Muriate, bromide and the Methylsulfate of alkoxyl group propyl group dihydroxy ethyl ammonium methyl.In some above-mentioned quaternary ammoniums, preferably C 10-14Alkyltrimethylammonium salt, for example decyl TMA (TriMethylAmine) Methylsulfate, dodecyl TMA (TriMethylAmine) muriate, tetradecyl TMA (TriMethylAmine) bromide and cupraol base TMA (TriMethylAmine) muriate and Methylsulfate thereof.
The suds booster that is used for the present composition can contain any or any several mixture in the above-mentioned various suds booster.
Optional interpolation component
Except said components, composition of the present invention can also comprise other and be applicable to usual component in liquid or the colloidal dish washing detergent compositions.
Optional interpolation component is included in U.S. Pat 4,316,824 Pancheri(1982,2,23) disclosed that class promotes the ethoxylate nonionic surface active agent of draining, this with reference to and be incorporated herein.
Other interpolation component comprises the decontamination builder of organic class or mineral-type.The example of the water-soluble inorganic builder that is suitable for has: alkali-metal carbonate, phosphoric acid salt, polyphosphate and silicate, they itself can be separately their mixture itself or with the builder salt of organic basic sequestrant as the interpolation component.The object lesson of these salts has: tripoly phosphate sodium STPP, yellow soda ash, salt of wormwood, trisodium phosphate, potassium pyrophosphate, Potassium tripolyphosphate and Sodium hexametaphosphate 99.The example of the organic synergistic builder salts that is suitable for has: alkali-metal multi-carboxylate, for example, resemble the water-soluble citrate of Trisodium Citrate and potassium one class, sodium tartrate and potassium, sodium ethylene diamine tetracetate and potassium, the N-(2-hydroxyethyl)-ethylene amine triacetic acid sodium and potassium, nitrilotriacetic acid(NTA) (NTA) sodium and potassium, the N-(2-hydroxyethyl) a nitrilo sodium diacelate and a potassium, oxygen di-sodium succinate and potassium, tartrate list and two sodium succinate and potassium etc., these organic compound can be separately or their itself mix or with above-mentioned inorganic alkaline synergy salt as adding component, these organic constituents are in U.S. Pat 4,663,071(1987.5.5 day is authorized people such as Bush) in introduce to some extent, at this with reference to being incorporated herein.Other organic decontamination builder as water miscible phosphoric acid salt, also can be used in the composition of the present invention.Yet, under normal conditions, the effect of decontamination builder in dish washing detergent compositions is so unimportant, and owing to will consider solubleness and phase stability, so the formulation flexibility of liquid or colloidal compositions is restricted.
In order to make product reach required phase stability and required viscosity, can use aliphatic alcohols, for example ethanol and propylene glycol, hydrotropic agent, reach the compound relevant (as US3 as toluenesulfonic acid sodium salt with potassium, sodium xylene sulfonate and potassium, sulfo-succsinic acid trisodium with it, 915,903 is described, is incorporated herein in this reference); And urea.The optimum consumption of additive therefor is as follows in liquid composition of the present invention: the consumption as aliphatic alcohols such as ethanol and propylene glycol is 0%-about 15%, the consumption of the toluene of sodium and potassium, dimethylbenzene or cumene sulfonate is 0%～about 10%, the consumption of urea is 0%～about 10%, and the consumption of sulfo-succsinic acid trisodium is 0%-about 15%.
The generally not fatty alcohols of colloidal compositions of the present invention.But these colloidal compositions can contain potassium or toluene, dimethylbenzene or the cumene sulfonate of sodium and the urea of more amount of more amount, and promptly its consumption can be between about 10% to about 30%, and they are to use (referring to US4 as peptizing agent, 615,819 and GB2,179,054A).
Other required component comprises thinner and solvent.Thinner can be inorganic salt, and as sodium sulfate, ammonium chloride, sodium-chlor, sodium bicarbonate etc., and solvent can be water, low-molecular-weight Fatty Alcohol(C12-C14 and C12-C18), as ethanol, Virahol etc.Water content is up to about 80%, preferably about 30% usually to about 70% in the said herein composition, and most preferred is about 40 to about 65%.
Percentage ratio used herein, umber and ratio, dated especially as not having, generally be all by weight.
The following example explanation also helps to understand this explanation.
Embodiment 1
Prepare three kinds of liquid compositions of the present invention according to following method.
The preparation method of composition A adds these several reagent of ethanol, sodium-chlor and sodium xylene sulfonate to contain in the surfactant mixture of alkyl ethoxy carboxylate.Then remaining tensio-active agent is added and mixed.Then add glycine and pH value is adjusted to about 10 with sodium hydroxide.Add magnesium chloride at last, will make that at this moment pH value is reduced to about 9.5.Regulate at last the viscosity and the pH value of product this moment, and then add essence and tinting material.The rest part of product is a water.
The preparation method of composition B is added to ethanol, sodium-chlor and sodium xylene sulfonate in the alkyl ethoxy carboxylic acid sodium, and the listed order of remaining composition components according to the form below adds one by one.
The preparation method of composition C is added to ethanol, sodium-chlor and sodium xylene sulfonate in the alkyl ethoxy carboxylic acid sodium.Then alkyl glucoside is added and mixed, and the temperature of mixture is brought up to 40 ℃.The cocoanut fatty acid single ethanol amide is heated to 65 ℃ and fusion enters.Transfer to slightly low numerical value with PH and viscosity this moment, then adds tinting material, essence and water so that the composition sum of composition reaches 100%.
%(weight)
The combination of compositions compositions
Component A B C
C 12-13Alkyl ethoxy (average 2.8) carboxylic acid sodium *15 15 15
C 12-13Alkyl ethoxy (average 2.8) alcohol *0.97 0.97 0.97
C 12-13Alkyl ethoxy (average 0.8) sodium sulfate 15--
C 12-14Sodium soap α-methylmesylate-15-
C 12-13Alkyl polyglucoside (average 1.4)--15
C 12-14Alkyl dimethyl trimethyl-glycine 4.0--
C 12-14-16Alkyl dimethyl amine oxide-4.0-
C 12-C 14Lipid acid monoethanolamine acid amides--4.0
Magnesium ion is (with MgCl 26H 2The O form adds) 0.76 0.76-
Glycine 4.0--
Sodium xylene sulfonate 2.0 2.2 2.0
Ethanol 7.5 7.0 7.0
Sodium-chlor 1.5＜1 2.25
Product P H 9.5 7.55 7.05
Essence and tinting material 0.15 0.15 0.15
Water surplus surplus surplus
*The preparation method of tensio-active agent who contains alkyl ethoxy carboxylic acid sodium and alkyl ethoxy alcohol is as follows:
1. with a kind of C 12-13Alkyl ethoxy (average 3.0) alcohol reacts in 1: 1.1: 1.1 ratio with tertiary butyl potassium oxide and sodium chloroacetate.Reactions steps is as follows: at first alkylethoxylate and tertiary butyl potassium oxide were reacted 1 hour under about 60 ℃ and about 20mmHg column pressure condition.Then, by distillation the trimethyl carbinol is removed from reaction mixture continuously.Then, remove vacuum, add sodium chloroacetate and its mixing.Then be depressurized to 18～20mmHg again, reaction is proceeded about 3 hours.Charge into nitrogen subsequently so that reaction pressure returns to normal atmosphere, and close the steam-heated cal(l)andria coiled pipe.With this understanding reaction product is placed and spend the night.Raise the temperature of reaction mixture and the decompression of finding time next day again, to remove the trimethyl carbinol in this system.Then this reaction mixture is added the tertiary butyl potassium oxide to neutralize and to add at first in the saliferous aqueous acid, the consumption of hydrochloric acid is 105% of a reaction theory amount.With the acidic aqueous solution heating of reaction product, to impel organic phase and aqueous phase separation.Collect organic phase at last.
2. use C 12-13Alkyl ethoxy (average 2.7) alcohol comes repetition above-mentioned steps 1, be this ethoxy alcohol to the ratio of tertiary butyl potassium oxide and sodium chloroacetate is 1: 1.3: 1.3.Tertiary butyl potassium oxide is added temperature be about in 32.2 ℃ the alkylethoxylate, reaction mixture is heated to 76.7 ℃ then.Start vacuum pump to set up reduced pressure.Temperature of reaction is increased to 104.4 ℃ again, extracts the trimethyl carbinol and collection out, this collects step and continues about 30 minutes.Reaction product is cooled off a little, made its temperature slow cooling, then sodium chloroacetate is added in the above-mentioned reactant to about 66 ℃.With about 1.5 hours of this mixture stirring reaction, with its cooling and add an amount of aqueous hydrochloric acid so that solution reaches PH3.4.Add entry so that the volume of reaction mixture increase about 50%, then with mixture heating up to about 49 ℃.Collect upper organic phase, and the repeated washing step.
With the surfactant mixture that obtained in above-mentioned steps 1 and the step 2 correspondingly by 40.4 pairs 59.6 mixed.From the surfactant mixture of these comparatively large vols that after mixing, obtain, get a part, sodium hydroxide solution with 50% is neutralized to PH with it and is about about 8, use the water and the alcoholic acid mixture of 25/75 volume ratio then, the consumption by 50% dilutes above-mentioned neutralized reaction product.Then obtaining solution is at room temperature used about 4 days of hexane continuous extraction.Collect lower floor's water,, so just obtained a kind of paste product that contains alkyl ethoxy carboxylate and surfactant mixture as described below by adding heat extraction part second alcohol and water.
In aforesaid method, it is RO(CH that the tensio-active agent of said mixture partly contains 93.9% general formula of having an appointment 2CH 2O) XCH 2COO -Na +Alkyl ethoxy carboxylate, wherein, R is a C who on average contains 12.5 carbon atoms 12-13Alkyl; The X scope is 0 to about 10, and various ethoxylate shared share in alkyl ethoxy carboxylate is such, and promptly the shared umber of the ethoxylate of X=0 is about 2.8%(weight), X is about less than 2% greater than the shared umber of 7 ethoxylate.X mean value in this general formula is 2.8.Also containing 6.1% general formula in the surfactant mixture is RO(CH 2CH 2O) XThe fatty alcohol ethoxylate of H, R wherein are a C who on average contains 12.5 carbon atoms 12-13Alkyl, X mean value are 2.8.Saponified matter content in this surfactant mixture is 0%.
Above-mentioned composition combines the advantage of degreasing result and mildness with flying colors.By the surfactant mixture that contains alkyl ethoxy carboxylate this several prods as main component, the peci-order of its oil removal ability is composition A＞composition B＞composition C.And the precedence of the advantage that its mildness brings is composition C＞composition B＞composition A.
Embodiment 2
Liquid composition in embodiment 1 also can replace the original surfactant mixture that contains alkyl ethoxy carboxylate and successfully makes with a kind of surfactant mixtures (as described below), wherein said surfactant mixture makes by a kind of method for oxidation, and said method for oxidation is that fatty alcohol ethoxylate is reacted with oxygen having in the presence of the noble metal catalyst.This method for oxidation is in U.S. Pat 4,223,460; US4,214,101; And US4,348,509; And German patent DE 3,446,561; With Japanese patent application JP62, general introduction is all arranged in 198,641.It is RO(CH that this surfactant mixture contains 92.4% general formula 2CH 2O) XCH 2COO -Na +Alkyl ethoxy carboxylate, R wherein is the C that on average contains 12.7 carbon atoms 12-C 14Alkyl, X are 0 to about 12.The shared umber of various ethoxylates is in this ethoxylate mixture: wherein the component of X=0 accounts for 10%(weight), X greater than 7 component approximately less than 3%(weight).In this species distribution, the mean value of X is 2.5.It is RO(CH that this surfactant mixture also contains 6.4% general formula of having an appointment 2CH 2O) XThe fatty alcohol ethoxylate of H, R wherein is on average containing the C of 12.7 carbon atoms 12-14Alkyl, the mean value of X is about 3.7.In addition, also to contain 1.2% general formula of having an appointment be RCOO to surfactant mixture -Na +The soap class, wherein R is the C of average out to C11.7 11-13Alkyl.This composition will contain 15%(weight) alkyl ethoxy carboxylate, 1.04%(weight) fatty alcohol ethoxylate and 0.2%(weight) the soap class.And other components in said composition with before identical.Can change slightly the content of ethanol in the composition and sodium xylene sulfonate, so as with the viscosity of said composition and stability be adjusted to embodiment 1 in several compositions have the numerical value that is close.
The ability of cleaning greasy dirt of these compositions that obtained and the advantage of mildness almost with coming to the same thing shown in the embodiment 1.
Embodiment 3
Following liquid composition contains surfactant mixture used among the embodiment 1, wherein contain identical alkyl ethoxy carboxylate, this composition have good especially ability of cleaning greasy dirt and to the staff action temperature and characteristics, and its foam is slightly less than composition A, B and C.
Components composition D
(weight %)
C 12-13Alkyl ethoxy (average 2.8) carboxylic acid sodium 28
C 12-13Alkyl ethoxy (average 2.8) alcohol 1.8
Magnesium ion is (with MgCl 26H 2The O form adds) 0.6
Glycine 4.0
Sodium xylene sulfonate 2.0
Ethanol 7.5
Sodium-chlor 1.5
Product P H 9.0
Essence and tinting material 0.15
Water surplus
Embodiment 4
A kind of colloidal compositions of the present invention can use U.S. Pat 4,615, and 819 general methods of being introduced prepare.Said composition contains 35.0%(weight) C 12-14Alkyl ethoxy (average 3.0) carboxylic acid sodium and 2.3%(weight) C 12-14Alkyl ethoxy (average 3.0) alcohol.If with urea as gelling " additive ", then in 10%(weight) the aqueous solution in must to keep its pH value to be lower than about 8.0, emit the ammonia flavor to prevent composition, this ammonia flavor is that the hydrolysis owing to urea generates.
The colloidal compositions that obtains with prior art (for example US4,615,819) is compared, and this composition of the present invention has the character of good ability of cleaning greasy dirt and outstanding hand contact action gentleness.
Embodiment 5
Following three kinds of fluid compositions of the present invention have been prepared according to following method.
Ethanol is added in the alkyl ethoxy carboxylate mixture of acid.Add the sodium hydroxide that surpasses required stoichiometric quantity a little then and neutralize, and stir the mixture with the acid of inciting somebody to action wherein.If necessary, can add alkyl-sulphate, cumene sulfonate, sulfo-succsinic acid trisodium, trimethyl-glycine and amine oxide hereinto with after the step, then, for composition X and y, when its aqueous solution when equaling or surpass the desired pH value of composition slightly, add suitable buffer reagent (glycine and/or three (methylol) ammonia methane).If necessary, then at this moment can in the composition of PH between 9.5 to 10, add magnesium chloride.If add magnesium toward pH value above in 10 the mixture, then can produce the precipitation of magnesium.Add essence and tinting material again, regulate viscosity, add entry at last, promptly obtain final composition with ethanol.
Weight %
Components composition X composition Y composition Z
C 12-13Alkyl ethoxy (average 3.5) 30 22 24
Carboxylic acid sodium *
C 12-13Alkyl ethoxy (average 3.5) alcohol *1.8 1.3 1.5
C 12-13Sodium alkyl sulfate-6.0 4.0
C 12-14-16Alkyl dimethyl amine oxide 2.0 3.0 3.0
C 12-14Alkylamidoalkyl propyl-dimethyl 2.0 3.0 3.0
Trimethyl-glycine
Magnesium ion is (with MgCl 26H 2O 0.6 0.76-
Form adds)
Glycine 4.0 4.0-
Three (methylol) ammonia methane 3.3 3.3 4.0
Cumene sodium sulfonate 5.0--
Sulfo-succsinic acid trisodium-4.5 4.5
Sodium-chlor＜2＜2＜2
Ethanol 7.5 7.5 7.5
Product P H 9.3 9.3 8.9
Essence and tinting material 0.15 0.15 0.15
Water surplus surplus surplus
*During the surfactant mixture that contains alkyl ethoxy carboxylic acid sodium and fatty alcohol ethoxylate can come with sodium hydroxide and the method for acid alkyl ethoxy carboxylate mixture prepare.After neutralization, it is RO(CH that the tensio-active agent in the mixture partly contains 94.3% general formula of having an appointment 2CH 2O) XCH 2COO -Na +Alkyl ethoxy carboxylate, wherein R is a C who on average contains 12.5 carbon atoms 12-13Alkyl, the scope of X are from 0 to about 10, and various ethoxylates shared umber in whole alkyl ethoxy carboxylates is: X is that the umber of 0 ethoxylate is a 0.5%(weight), X greater than the umber of 7 ethoxylate less than about 6%(weight).In this composition distributed, the mean value of X was 3.5.It is RO(CH that this surfactant mixture also contains 5.7% general formula of having an appointment 2CH 2O) XThe fatty alcohol ethoxylate of H, wherein R is on average containing the C of 12.5 carbon atoms 12-13Alkyl, X mean value are 3.5.The saponified matter content of surfactant mixture is 0%.
Above-mentioned composition combines the advantage of ability of cleaning greasy dirt and gentle performance with flying colors. Use contains the product that the alkyl ethoxy carboxylate surfactant mixture makes as key component, the peci-order of the ability of cleaning greasy dirt that they have be composition X＞composition Y＞＞composition Z. And the precedence of the mildness advantage of these compositions is composition X＞composition Z＞composition Y, and the peci-order of their foaming capacity be composition Y＞composition Z＞＞composition X.

Claims (7)

1, a kind of light-duty liquid or colloid dish washing detergent compositions, said composition contains the surfactant mixture of 5%-70% (weight), it is characterized in that, and said surfactant mixture contains (weight):
(a) 80% to 100%, be preferably 90% to 95% general formula and be
RO(CH 2CH 2O) XCH 2COO -M +
Alkyl ethoxy carboxylate, wherein, R is C 12To C 16, be preferably C 12To C 14Alkyl, the scope of X from 0 to 10, the composition of various ethoxylates distributes following (by weight), X be the shared ratio of 0 ethoxylate less than 20%, X greater than the shared ratio of 7 ethoxylate less than 25%, as R average out to C 13Or more hour, the mean value of X is 2-4, when R on average greater than C 13The time, the mean value of X is 3-6, and M is a kind of positively charged ion;
(b) 0% to 10%, the general formula that is preferably less than 5% is
RO(CH 2CH 2O) XH
Fatty alcohol ethoxylate, wherein, R is C 12To C 16Alkyl, the scope of X from 0 to 10, and the mean value of X is less than 6; And
(c) 0% to 10%, the general formula that is preferably less than 5% is
RCOO -M +
The soap class, wherein, R is a kind of C 11To C 15Alkyl, M is a kind of positively charged ion; Wherein the pH value of 10% of said composition (weight) aqueous solution is 7 to 11.
2,, wherein contain 12% to 30% surfactant mixture as the liquid composition in the claim 1.
3,, wherein contain 28% to 35% surfactant mixture as the colloidal compositions in the claim 1.
4, according to any one composition in preceding claim, wherein the pH value of said composition is 8.5 to 10.
5, according to any one composition in preceding claim, wherein said composition contains 0.3% to 0.8% magnesium ion.
6, according to any one composition in preceding claim, wherein said composition also contains a kind of synergistic surfactant, and this synergistic surfactant is selected from: the mixture of alkylbenzene sulfonate, alkyl-sulphate, paraffinic base sulfonate, alkene sulfonate, sulfated alkyl ether, fatty sulfonate, alkyl polyglucoside and above-mentioned substance.
7, according to any one composition in preceding claim, wherein said composition also contains suds booster, and this suds booster is selected from: the amine oxide of trimethyl-glycine, ethylene oxide condensate, fatty acid amide, semi-polarity non-ionic type and the mixture of cationic surfactant and above-mentioned substance.
CN90103082A 1989-05-22 1990-05-22 The light-duty liquid or the colloid dish washing detergent compositions that contain a kind of alkyl ethoxy carboxylate surfactant Pending CN1048059A (en)

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CN101426892B (en) * 2006-04-21 2011-09-14 陶氏环球技术有限责任公司 Formulations incorporating a biodegradable chelant

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MA21850A1 (en) 1990-12-31
JPH0331398A (en) 1991-02-12
DE69031193D1 (en) 1997-09-11
TR25117A (en) 1992-11-01
ATE156514T1 (en) 1997-08-15
EP0399752B1 (en) 1997-08-06
EP0399752A3 (en) 1991-05-08
EP0399752A2 (en) 1990-11-28
FI902495A0 (en) 1990-05-21
NZ233747A (en) 1993-04-28
KR900018471A (en) 1990-12-21
DE69031193T2 (en) 1998-03-12

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