CN1062371A

CN1062371A - The light-duty dishwashing detergent composition that contains alkyl ethoxy carboxylate surfactant and calcium or magnesium ion

Info

Publication number: CN1062371A
Application number: CN91111874.8A
Authority: CN
Inventors: T·A·克里普; K·奥福苏-阿桑特
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1990-11-16
Filing date: 1991-11-16
Publication date: 1992-07-01
Also published as: HUT64782A; TR26532A; JPH06502884A; CZ87393A3; PT99530A; FI932199A; FI932199A0; WO1992008777A1; NO931738D0; DK0557426T3; BR9106983A; ES2101078T3; ATE149561T1; DE69125022D1; MY131210A; MA22342A1; EP0557426A1; GR3023502T3; DE69125022T2; HU9301418D0

Abstract

A kind of light-duty liquid or gelinite dishwashing detergent composition that contains alkyl ethoxy carboxylate surfactant mixture and calcium or magnesium ion, the said composition that contains magnesium ion need magnesium chelating substances and buffer reagent with the pH value that keeps composition by about 8 to 10.The said composition of calcium ions needs calcium sequestrant, particularly at pH greater than 9 o'clock, to prevent when storing, generating CaCO ₃Precipitation.Said composition also demonstrates the good oily performance of removing demonstrating skin in the gentle performance.Said composition also has good storage stability.Preferred dishwashing detergent composition type is a liquid form, and when keeping gentle performance, high pH value in the composition and high-load calcium or magnesium ion have improved oily and removed performance.

Description

The light-duty dishwashing detergent composition that contains alkyl ethoxy carboxylate surfactant and calcium or magnesium ion

The present invention relates to be disclosed in containing alkyl ethoxy carboxylate surfactant and (also can being referred to as alkyl polyethoxye carboxyl methide, alkyl polyethoxye acetate of a following class patent, alkyl, polyether carboxylate salt etc.) the light-duty liquid or the dishwashing detergent composition of gelinite, this class patent is United States Patent (USP) U.S.2,183,853; 2,653,972; 3,003,954; 3,038,862; 3,741,911; And 3,941,710; English Patent 456,517 and 1,169,496; Canadian Patent 912,395; French Patent 2,014,084 and 2,042,793; Netherlands patent applications numbers 7,201,735-Q and 7,406,336; And Japanese patent application No. 96,579/71 and 99,331/71.

Great needs have been arranged, and requirement can provide light-duty liquid or the gelinite dishwashing washing composition that well goes unctuousness.These compositions are being well-known in the art, and are disclosed in, and for example United States Patent (USP) 4,316,824(Pancheri), 4,681, people such as 704(Bernar dino), 4,133, people such as 779(Hellyer) and 4,615, people such as 819(Leng) in.Though these compositions are washing composition of good greasy and dirt, can make pachylosis in some cases, particularly when the exsiccant winter months is used.

In addition, it is the detergent composition of mild to skin that the present technique field has a large amount of, and the composition of these milds contains the vitriol of senior ethoxylated alcohol usually, can referring to, people's such as Rose and Thiele United States Patent (USP) U.S.3 for example, 743,233.The also recommended gentle performance that is used to improve the liquid dish washing composition of trimethyl-glycine can be consulted, United States Patent (USP) U.S.4 for example, 555, people such as 360(Bissett).Alkyl ethoxy carboxylate is also known to can be used as the mild tensio-active agent and is used for liquid detergent composition.Referring to Japanese patent application 48-60706 and 48-64102.Yet, said these alkyl ethoxy carboxylate surfactants, it is poor going on the oily ability at it, the tensio-active agent that therefore need use other is to reach desirable cleaning function.These two kinds of important characteristics with the mild and the greasy ability of deoiling are difficult to be combined in the identical product.In general, must sacrifice a specific character and be beneficial to another kind of characteristic.Have been found that the detergent composition that contains certain special alkyl ethoxy carboxylate surfactant mixture provides a kind of and not only shown when well going unctuousness but also show the detergent composition that skin is mild.Serve as reasons about 7 to 11 and contain a small amount of divalent ion when said composition has pH value, for example when magnesium or calcium, this dual advantage can be enhanced.

These alkaline compositions that contain magnesium ion, when storing, it shows relatively poor stability.In alkaline environment, the precipitating action of magnesium hydroxide is a substantial problem.Therefore, the object of the present invention is to provide a kind of detergent composition, it demonstrates good go unctuousness and is mild to skin, when said composition is stored, also provides superior package stability simultaneously.

The present invention relates to the dishwashing detergent composition of light-duty liquid or gelinite, preferably liquid, it comprises following component:

(a) by about surfactant mixture of 5% to 70%, contain:

(ⅰ) by alkyl ethoxy carboxylate about 80% to 100%, that molecular formula is following:

In the formula, R is C ₁₂To C ₁₆Alkyl, the scope of X is by 0 to about 10, and the distribution of oxyethyl group is like this, promptly, weight with alkyl ethoxy carboxylate is that benchmark measures, and X is 0 o'clock, and the content of this material is less than about 20%, X is greater than 7 o'clock, and the content of material is less than 25%, when the mean value of R is C ₁₃Or when being worth less than this, then the mean value of X is by about 2 to 4, and when R be greater than C ₁₃The time, then the mean value of X is by 3 to 6, and M is a positively charged ion;

(ⅱ) by fatty alcohol ethoxylate 0% to about 10%, that molecular formula is as follows:

In the formula, R is C ₁₂To C ₁₆Alkyl, the scope of X is by 0 to about 10, the mean value of X is less than about 6; With

(ⅲ) by the following soap class of 0% to about 10% molecular formula:

In the formula, R is C ₁₁To C ₁₅Alkyl, M is a positively charged ion; With

(b) by about 0.1% to 4% calcium or magnesium ion; With

(c) certain calcium or the magnesium chelating substances of formation solubility calcium or magnesium complex, it has the logarithm that forms constant, log Kf, it is worth between about 0.5 and 5, and the amount of sequestrant is enough to prevent generate lime carbonate or magnesium hydrate precipitate in composition;

Wherein, the aqueous solution of 10% weight of said composition has pH value and serves as reasons about 7 to 11.

Light-duty liquid of the present invention or gelinite, the dishwashing detergent composition of preferably liquid contains surfactant mixture, this mixture comprises the alkyl ethoxy carboxylate surfactant of main amount and contains fatty alcohol ethoxylate on a small quantity or not and by-product impurity soap, and calcium or magnesium ion source.In comprising the composition of magnesium ion, also need magnesium chelating substances and ealkaline buffer.The composition of calcium ions also needs a kind of calcium sequestrant.These and other typical auxiliary preferred ingredient sees following liquid of stating or gelinite dish washing composition.

The surfactant mixture that contains alkyl ethoxy carboxylate

Liquid composition of the present invention contains by about 5% to 50% weight, is preferably by about 10% to 40%, is preferably by about surfactant mixture 12% to 30% and that define foreign matter content.Gelinite composition of the present invention contains by about 5% to about 70%, is preferably by about 10% to about 45%, is preferably by about 12% to about 35% surfactant mixture.

This surfactant mixture contains by about 80% to 100%, is preferably by about 85% to 95%, is preferably by about general formula of 90% to 95% to be, RO(CH ₂CH ₂O) _XCH ₂COO ^-M ⁺Alkyl ethoxy carboxylate, in the formula, R is C ₁₂To C ₁₆Alkyl, the scope of X is by 0 to about 10, the distribution of oxyethyl group is like this, that is, be that benchmark measures with the weight of alkyl ethoxy carboxylate, X is 0 o'clock, the content of this material is less than 20%, better is preferably less than about 10% less than about 15%.When X greater than 7 the time, the content of this material is less than about 25%, better less than about 15%, is preferably less than about 10%, when R on average is C ₁₃Or when being worth less than this, X on average is by about 2 to 4, and when R on average be greater than C ₁₃The time, X on average be by about 3 to 6 and M be positively charged ion, preferably be selected from basic metal, alkaline-earth metal, ammonium, list, two and triethanol ammonium, good especially is sodium, potassium, ammonium and with the mixture of magnesium ion.Best, alkyl ethoxy carboxylate is that its R is C ₁₂To C ₁₄That class of alkyl.

The pure precursor of suitable alkyl ethoxy carboxylate of the present invention is to contain by about 12 aliphatic primary alcohols to about 16 carbon atoms, other aliphatic primary alcohol that is suitable for is the resulting straight chain primary alcohol of hydrogenation by plant or tallow fatty acid (for example coconut fatty acid, palm-kernel oil lipid acid, tallow fatty acids), perhaps use ethene, carry out building-up reactions according to the method for Ziegler type and also obtain straight chain primary alcohol thereupon being hydrolyzed.Best alcohols is a positive octyl group, a positive nonyl, a positive decyl, positive 11 (carbon) alkyl, a positive dodecyl, positive 13 (alkane) base, positive 14 (alkane) base, positive 15 (alkane) base and positive 16 (alkane) base alcohol.Other suitable pure precursor is included in the primary alconol that contains the part side chain on its β position or the alpha-carbon atom, and wherein, this branched-chain alkyl contains by 1 to 4 carbon atom.In this class alcohol, the alcohol of every kind of certain chain lengths has at least 30% to be straight chain, then is desirable, and its side chain then preferably comprises about 50% methyl and more a spot of ethyl, propyl group and butyl.These alcohol usually react and prepare by having approximately by the normal olefine of 11 to 17 carbon atoms and carbon monoxide and hydrogen.Obtained straight chain and branched-chain alcoho by these reactions, and, also can use this mixture in this mixture mode, perhaps it is separated into single component, and then recombine is to obtain desirable blend.

Can be used to prepare pure " oxo " halid preparation method commonly used and be disclosed United States Patent (USP) U.S.2; 564; 456 and U.S.2; in 587,858, and the direct hydroformylation reaction of alkene is disclosed United States Patent (USP) U.S.2 with the preparation method who obtains alcohol; 504; in 682 and 1,581,988.All these patents all are incorporated into the present invention and are used as reference.

Also can use the secondary alcohol of equivalent, can see that clearly the alkene that uses single chain length then obtains the alcohol of corresponding single chain length during as parent material, but, near desired mean value, use alkene mixture general more more economical with certain carbon chain length distribution.Certainly, this will provide near the blended alcohol with identical carbon chain length distribution mean value.

In addition, that obtain by the plant oil ﹠ fat and by other the chain length that aliphatic primary alcohol that alkyl or alkenyl obtains as the petroleum of the part of its structure will contain certain limit that contains.Because the chain length scope is C ₈-C ₂₀And surpass this scope, therefore, the product that raw material is separated into the different chain length scope is practicable.The product of this different chain length scope will be selected with reference to its final should being used for.

The needed average oxyethyl group chain length of fatty alcohol ethoxylate can obtain by using the catalysis ethoxylation to handle, wherein, with whenever the molar weight of the oxyethane that reacts of amount Fatty Alcohol(C12-C14 and C12-C18) will be consistent with the mean value of oxyethyl group in fatty alcohol ethoxylate.Known, the reaction that this oxyethane adds to alkanol is next promoted with catalyzer, usually, and most catalyzer, or strongly-acid or strong basicity.The basic catalyst that is suitable for is the alkali-metal basic salt of periodic table of elements I family, for example, and some basic salt of the alkaline-earth metal of sodium, potassium, rubidium, cesium salt and periodic table of elements II family, for example, calcium, strontium, barium salt and magnesium salts in some cases.An acidic catalyst that is suitable for comprises the Lewis acid of Fu Ruide Peter Krass catalyzer widely.The concrete example of these catalyzer is boron, antimony, tungsten, iron, nickel, zinc, tin, aluminium, titanium, and fluorochemical, muriate and the bromide of molybdenum.This class halogenide with, for example, the utilization of the complex compound of alcohols, ethers, carboxylic-acid and amine has also had report.Also have, the example of other of known acid alkoxylating catalyst is sulfuric acid and phosphoric acid: the magnesium of perchloric acid and perchloric acid, calcium, manganese, nickel and zinc salt; Metal oxalate, vitriol, phosphoric acid salt, carboxylate salt and acetate; The fluoroboric acid an alkali metal salt, zinc titanate; Metal-salt with Phenylsulfonic acid.Employed this class catalyzer will determine the distribution range of alkoxyl group.Catalyzer is strong more, then causes near the distribution of alkoxyl group mean value fine and close more or narrow more, and catalyzer is weak more, then causes wide more distribution.

This surfactant mixture also contains by 0% to about 10%, better is less than approximately 8%, is preferably that to be less than about 5% molecular formula be RO(CH ₂CH ₂O) _XThe fatty alcohol alkoxy compound of H, R is C in the formula ₁₂To C ₁₆Alkyl and the scope of X be by 0 to about 10 and the mean value of X for less than 6.This surfactant mixture also contains 0% to about 10%, better is less than approximately 8%, is preferably that to be less than about 5% molecular formula be RCOO ^-M ⁺The soap class, R is C in the formula ₁₁To C ₁₅Alkyl and M be aforesaid positively charged ion.

The above-mentioned non-carboxylated fatty alcohol alkoxy compound of pointing out is prejudicial to the alkyl ethoxy carboxylate surfactant mixture, the advantageous property that special damage is provided to the alkyl ethoxy carboxylate surfactant mixture, therefore, employedly among the present invention contain that to contain the fatty alcohol ethoxylate that is less than about 10% weight (this fatty alcohol ethoxylate is by deriving in the reaction) in the alkyl ethoxy carboxylate surfactant mixture be very crucial.Though can buy on the market contain 10%(or greater than this value) the alkyl ethoxy carboxylate of fatty alcohol ethoxylate, have known certain methods can obtain needed highly purified alkyl ethoxy carboxylate.For example, can utilize the steam distillation method to remove unreacted fatty alcohol ethoxylate, (United States Patent (USP) U.S.4,098,818, embodiment 1), or alkyl ethoxy carboxylate carried out recrystallization (English Patent 1,027,481 embodiment 1), other the method that obtains needed carboxylate salt, be under the condition that specified pressure and temperature combine, sodium hydroxide or sodium Metal 99.5 and monochloroacetic acid or its salt and fatty alcohol ethoxylate are reacted, as United States Patent (USP) U.S.3,992,443 and 4,098,818 and Japanese patent application 50-24215 disclosed, this all will be incorporated into the present invention and be used as reference.

In addition, certain hindered base, for example tert.-butoxy potassium can substitute the sodium hydroxide in the above-mentioned listed patent, so, can obtain highly purified alkyl ethoxy carboxylate with undemanding temperature and pressure condition.Specifically, use generally is made up of alkyl, active oxygen center and positively charged ion, and molecular formula is RO ^-M ⁺Hindered base.The structure of this hindered base is secondary alkyl or tertiary alkyl and comprises non-linear alkyl, on this alkyl, has a side chain at least within three carbon atoms of reactive center, also contains Sauerstoffatom and basic metal or alkaline earth metal cation in this structure.This method comprises reacts fatty alcohol ethoxylate and above-mentioned hindered base and anhydrous perchloric acid, the mol ratio of hindered base and anhydrous perchloric acid is 2: 1, perhaps this method is for reacting fatty alcohol ethoxylate and above-mentioned hindered base and an alkali metal salt or the alkaline earth salt of anhydrous perchloric acid, the an alkali metal salt of hindered base and perchloric acid or the mol ratio of alkaline earth salt are 1: 1, wherein, the mol ratio of fatty alcohol ethoxylate and anhydrous perchloric acid or its an alkali metal salt or alkaline earth salt was served as reasons about 1: 0.7 to 1: 1.25, its temperature is served as reasons about 20 to 140 ℃, and pressure serves as reasons about 1 to 760mmHg.

Method for preparing the high purity alkyl ethoxy carboxylate in addition such as United States Patent (USP) U.S4,223,460(embodiment 1-7); United States Patent (USP) U.S.4,214,101(embodiment 1), U.S.4,348,509; German Patent 3,446,561; And patent such as Japanese patent application 62,198,641 is disclosed, is with fatty alcohol ethoxylate and oxygen, reacts in the presence of platinum, palladium or other precious metal.One of by product of this class reaction is a soap, and as mentioned above, for the cleaning function that prevents the excellence that composition of the present invention provides and the retroaction of gentle performance, therefore, this soap should be limited.This can finish by following manner, even raw material with the fatty alcohol ethoxylate of the Fatty Alcohol(C12-C14 and C12-C18) of not ethoxylation with low levels, and selecting catalyst, this catalyzer can be in about at least 90% time, better be at least 95% time, make it the end methylene radical of preferential oxidation fatty alcohol ethoxylate.The oxygenizement of the non-end methylene radical in fatty alcohol ethoxylate will produce soap from the fatty alcohol ethoxylate component.

The positively charged ion of alkyl ethoxy carboxylate of the present invention can be a basic metal, alkaline-earth metal, ammonium and rudimentary alkanol ammonium ion.Be used for the neutralization reaction of the cationic source of alkyl ethoxy carboxylate from the alkyl ethoxy carboxylic acid, and from the auxilliary batching that adds, that for example strengthens the property contains bivalent ions salt.

The best positively charged ion that is used for the present composition is ammonium, sodium and potassium ion.In order to make composition have pH value between about 7 and 8, ammonium ion is most preferred, if but pH value greater than 8, then, cause the deprotonation of the ammonium ion in the said composition, thereby be undesirable owing to discharge a spot of ammonia.

For liquid composition of the present invention, potassium ion is better than sodium ion, because at low temperatures, potassium ion can make composition of the present invention more can prevent to generate precipitation, and the solvability of improved composition is provided.On the other hand, for gelinite composition of the present invention, sodium ion is better than potassium ion, because sodium ion makes it more easily to make the composition gelling.Cationic mixture may reside in the composition arbitrarily of the present invention.

The pH value of composition

Generally, the pH value of liquid dish washing composition is about 7, and is well-known, and alkalescence detergent composition bigger, that contain alkyl ethoxy carboxylate with comparing of neutral pH value, has particularly greatly improved the oily cleaning function under the condition of softening water.This good cleaning function can think that the composition that only contains alkyl ethoxy carboxylate surfactant of the present invention just has.Unhoped-forly be that composition of the present invention under this alkaline ph value is being that the adversary is gentle more under 7 the situation than PH.With PH meter, it is about 7 to 11 that the pH value of the composition of the present invention that the aqueous solution of 10% weight is measured is served as reasons, and better is by 8 to 10, preferably by 8 to 9.5.

In containing the calcium ion composition, in the whole PH scope of the present composition,, almost do not have or do not generate the calcium hydroxide precipitation promptly by about 7 to 11.Calcium hydroxide is dissolved in the water than magnesium hydroxide is easier.

When pH value is between about 7 and 9, almost not or have no chance to generate precipitation of calcium carbonate, because in this PH scope, because carbonate is supercarbonate or carbonic acid, it can not generate undissolved calcium complex, does not therefore almost have or do not have effective carbonate ion source and free calcium ions to generate precipitation of calcium carbonate.

When pH value was between about 9 and 11, this supercarbonate and carbonic acid class generation deprotonation to be generating carbonate, this carbonate easily and calcium react the generation precipitation of calcium carbonate.Therefore, in order to prevent to generate these unwanted products, in these high pH values, need a kind of calcium sequestrant.

If having pH value the most effectively talks about on the improvement performance greater than about 7 composition, then should contain certain buffer reagent, this buffer reagent can keep composition and in dilute solution, the alkaline ph value in the composition solution of promptly about 0.1% to 0.2% weight.The PKa value of this buffer reagent must be lower than needed composition pH value about 0.5 to 1.0PH unit (measuring as stated above).

Dish washing composition of the present invention when using, promptly dilutes and puts in the dirty plate and use, and will stand because the effect of the acid that the food dirt is produced.In order to keep the in use good performance of said composition, what have that the PKa value is lower than desired pH value must be present in the composition for about 0.5 buffer reagent to 1.0PH unit, when under these conditions, this buffer reagent can use minimum composition and control its pH value most effectively.

This buffer reagent, with regard to itself, it can be certain activated detergent, perhaps can be certain low-molecular-weight organic or inorganic materials, this material is used in the said composition individually for keeping alkaline ph value.The buffer reagent that is suitable for that is used for the present composition is some nitrogenous materials.Some examples are glycine or other amino acid or rudimentary alcamines, as list, two, three-thanomin.Preferred nitogen-contained buffer agent is 2-amino-2-ethyl-1, ammediol, 2-amino-2-methyl propyl alcohol, 2-amino-2-methyl-1, ammediol and three-(methyl alcohol) aminomethane.(a.k.a. three) N methyldiethanol amine, 1,3-diamino-2-propyl alcohol, N, N-tetramethyl--1,3-diamino-2-propyl alcohol, two (2-ethanol) glycine (a.k.a.N-two (hydroxyethyl) glycine) imidazoles, N-three-(methyl alcohol) methylglycine (a.k.a.tricine) also is preferred.

The general content of these buffer reagents is in about 0.1% to 15% weight, is preferably about 1% to 10%, preferably by about 1.5% to 8%.

Calcium or magnesium ion

Have found that, contain the alkyl ethoxy carboxylate composition of the present invention of divalent cation, greatly improve cleaning function greasy dirt.Particularly, when said composition is used to contain in a small amount of bivalent ions softening water, be so really.But, when the dishwashing liquid composition, when the definition that the alkyl ethoxy carboxylate that it contains and the present invention are limited is inconsistent, to seldom benefit by adding divalent cation, under many circumstances, after add divalent cation, in fact will demonstrate the scourability that has reduced.It is believed that divalent cation has improved the packing effect of the alkyl ethoxy carboxylate that exists on oil/water termination, thereby has reduced interfacial tension, has improved the oily cleaning function.

In addition, have been found that because the uncompatibility of divalent ion and hydroxide ion, prepare in alkaline PH matrix therefore that to contain so bivalent ions composition be difficult.When divalent ion and these two factors of alkaline PH combine with surfactant mixture of the present invention, can realize that to the oily washing this result surpasses separately with alkaline ph value or uses bivalent ions washing effect separately.But when storing, owing to form precipitation of hydroxide, the stability of these compositions degenerates.This point contains under the situation of magnesium ion more obvious at composition especially.

At present, have been found that the composition exhibiting of the present invention that contains calcium or magnesium ion goes out good greasy removal, to the mildness of skin, and provides good storage stability.The content of calcium ion in the present composition is by about 0.1% to 4%, preferably by about 0.5% to 3.5% weight.Magnesium chelating substances (being described as follows) is incorporated into the generation that will prevent magnesium hydrate precipitate in the composition of the present invention, and make it might mix a large amount of magnesium ions, because at high pH value, needed this bivalent ions concentration is low in remollescent water scope.Therefore, the amount of magnesium ion is by about 0.1% to 3% in composition, is preferably by about 0.3% to 2%, preferably by about 0.5 to 1% weight.

Best,, again calcium or magnesium ion are joined as muriate, acetate or nitrate in the composition of an alkali metal salt that contains the alkyl ethoxy carboxylic acid or its ammonium salt (preferably sodium salt) with after the highly basic neutralization in said composition.

At pH value is between about 7 and 9, and the composition exhibiting that contains calcium or magnesium ion goes out excellent washing oily advantage.Needn't adhere to said in theory, it is believed that, calcium ion or magnesium ion and alkyl ethoxy carboxylate molecule bonded are firm more, then on water/oily interface, make that its packing effect is firm more, when containing other bivalent ions composition and compare, the composition exhibiting of calcium ions goes out lower interfacial tension (IFT) observed value.In addition, when these pH values, composition of the present invention provides than the better package stability of above-mentioned other composition.

, between 9 and 11,, calcic and magniferous composition precipitate at pH value though all needing sequestrant to prevent to generate,, the amount that contains the needed sequestrant of calcium compositions is needed lower than magniferous composition.

The composition of preparation calcium ions is easier than the composition that contains magnesium ion, can not cause that because the pH value of this composition can be regulated at an easy rate precipitation generates.And when the preparation magnesium compositions, in case generate precipitation of hydroxide, then these precipitations just are not easy to dissolving.

Using an amount of sequestrant as condition, alkaline compositions can allow to contain the amount of higher calcium ion and can not generate undesirable precipitation under high pH value.

The calcium that comprises in the present composition or the amount of magnesium will depend on amount alkyl ethoxy carboxylate, that be present in total anion surfactant wherein that comprised.For the composition of the present invention that comprises calcium ion, the mol ratio of divalent ion and total anion surfactant is by about 0.25: 1 to about 2: 1, for magniferous composition of the present invention, the mol ratio of divalent ion and total anion surfactant is by about 0.25: 1 to about 1: 1.

The sequestrant of calcium or magnesium

Composition of the present invention can comprise be present in the liquid phase compositions, with sequester the calcium or the magnesium chelating substances of calcium or magnesium ion, thereby prevented reaction between calcium or magnesium ion and the hydroxide ion, this hydroxide ion can cause generating CaCO ₃Or Mg(OH) ₂Precipitation is particularly when pH value is between about 9 and 11.

This calcium or magnesium chelate complexes must be soluble.If generate undissolved calcium or magnesium chelate complexes, then can generate ugly hazy product, and, if this complex compound sediment in the bottom of product, then when using this product, is sent to washing soln with regard to the amount that does not have competent calcium or magnesium ion.

This sequestrant need only associate with calcium or magnesium ion mutually with medium intensity, promptly, just be enough to prevent reacting to each other between calcium and carbonate ion or magnesium and the hydroxide ion, but associating intensity can not be too strong, to such an extent as to be reduced in the effective calcium in the diluting soln or the amount of magnesium ion significantly.Therefore, for sequestrant, the logarithm of its formation constant, log Kf is between about 0.5 and 5.

The amount that is present in the sequestrant in the present composition is to be enough to prevent to generate in composition CaCO ₃Or Mg(OH) ₂Sedimentary amount.This content will depend on three factors: the pH value of desired composition, calcium or the magnesium ion content in composition, the intensity of sequestrant, i.e. its log Kf.

When pH value was between about 7 and 9, the formation reaction (as mentioned above) of calcium deposit can not take place.Therefore, in having the composition of this pH value, do not need sequestrant.Yet when PH was between about 9 and 11, the possibility that generates precipitation of calcium carbonate had strengthened (as mentioned above), therefore needed a certain amount of calcium sequestrant.

When composition contained magnesium ion, needed pH value was high more in diluent, then caused the concentration of the hydroxide ion in composition high more.This just order cause the interaction of the magnesium ion in the more hydroxide ion and composition in the composition, and so bigger possibility is just arranged, generate Mg(OH therein) ₂Precipitation.To use identical sequestrant, just the sequestrant of higher dosage need be incorporated in the composition as condition.Use stronger sequestrant, promptly higher log Kf can substitute the more weak sequestrant of more consumption.

What is more important must think that the logarithm of this formation constant, log Kf have determined the consumption of the sequestrant that uses in composition.The log Kf of sequestrant is preferably between 1 and 3.5 between about 0.5 and 5.The numerical value of this log Kf is high more, and combining with calcium ion must be just firm more, and generates CaCO for preventing in composition ₃Sedimentary requirement is just more little.Sequestrant content in the composition is listed in the following table I.During the consumption of the sequestrant that uses in determining composition of the present invention, ingredients Shi Bixu measures the log Kf value of sequestrant.The measuring method of relevant these sequestrant formation constants is disclosed (A.E.Martell and K.J.Motekaitis in " mensuration of stability constant and use "; V.C.Publisher Inc.(1988, N.Y., N.Y.), the present invention will be in conjunction with being used as reference.(R.M.Smith and A.E.Martell in " neutrality constant "; Plenum Publishers(1974～81, N.Y. N.Y.) has listed the formation constant of various common mineral compound, and the present invention will be in conjunction with being used as reference.Based on the amount and the desired pH value of composition of calcium ion, ingredients teacher can determine the amount ranges of needed sequestrant in composition.

Table 1

Log Kf %(weight)

0.5 to 1.5＜10

1.5 to 3＜8

3 to 5＜3

The example of the sequestrant that is suitable for is: N-two (hydroxyethyl) glycine (two (2-ethanol) glycine), the N-(2-hydroxyethyl) iminodiethanoic acid (HIDA), N-(2, the 3-dihydroxypropyl) iminodiethanoic acid (GIDA), and their alkali-metal salt, the mixture of said components also is an acceptable.

Preferred sequestrant is N-two (hydroxyethyl) glycine

Primary amine, for example glycine is not suitable as the sequestrant of magniferous composition of the present invention, because when storing, they can trend towards causing the decolorization of composition.Therefore, best, composition of the present invention does not use primary amine as sequestrant basically.

Special sequestrant and ealkaline buffer and the magniferous composition of the present invention relatively good usefulness that combines.These components comprise: Citrate trianion and alkanolamine (comprising 2-amino-2-ethyl-1, ammediol, 2-amino-2-methyl-1, ammediol and 2-amino-2-methyl propyl alcohol); N-two (hydroxyethyl) glycine and Tutofusin tris, N-two (hydroxyethyl) glycine and N methyldiethanol amine; N-two (hydroxyethyl) glycine and diethanolamine; N-two (hydroxyethyl) glycine and 1,3-diamino-2-propyl alcohol; And N-two (hydroxyethyl) glycine and trolamine.Preferably contain the combination of N-two (hydroxyethyl) glycine.

Cosurfactant

The cosurfactant that the present invention preferably includes that purpose is to foam, use on detergency and/or the mildness.

What be included in this class is several anion surfactants that generally are used in liquid or the gelinite dishwashing washing composition.With the associating positively charged ion of these anion surfactants can be identical with the aforesaid positively charged ion that is used for alkyl ethoxy carboxylate.The example of useful in the present invention negatively charged ion cosurfactant is following said several classes:

(1) alkylbenzene sulfonate, wherein, this alkyl contains in the straight or branched configuration by 9 to 15 carbon atom, is preferably 11 to 14 carbon atoms.A kind of good especially linear alkyl benzene sulfonate contains about 12 carbon atoms.These tensio-active agents are by United States Patent (USP) U.S2, and 220,099 and 2,477,383 have done detailed explanation.

(2) carry out sulfation by the alcohol that contains 8 to 22 carbon atoms (preferably 12 to 16 carbon atoms) and the alkyl-sulphate that obtains, the molecular formula that this alkyl-sulphate has is ROSO - ₃M ⁺, in the formula, R is C _8-22Alkyl, M is monovalence and/or divalent cation.

(3) have 8 to 22 carbon atoms at moieties, be preferably the alkane sulfonate of 12 to 16 carbon atoms, these tensio-active agents are can buy on the market.(as the Hostapur SAS of Hoechst Celanese)

(4) have 8 to 22 carbon atoms, the preferably alkene sulfonate of 12 to 16 carbon atoms.United States Patent (USP) U.S.3,332,880 have comprised the explanation of the alkene sulfonate that is suitable for.

(5) sulfated alkyl ether, it is by containing 8 to 22 carbon atoms, the alcohol of best 12 to 16 carbon atoms be less than 30, carry out ethoxylation most preferably less than 12 moles oxyethane and obtain.The molecular formula of this sulfated alkyl ether is as follows:

RO（C ₂H ₂O）xSO - ₃M ⁺

In the formula, R is C _8-22Alkyl, X is 1-30, M is monovalence or divalent cation.

(6) have 8 to 22 carbon atoms at moieties, be preferably the alkyl glyceryl ether sulfonate of 12 to 16 carbon atoms.

(7) molecular formula as shown in the formula fatty sulfonate:

In the formula, R ₁Be by approximately by C ₈To C ₁₈, be preferably C ₁₂To C ₁₈The straight or branched alkyl, and R ₂Be by about C ₁To C ₆, carbon atom (C preferably ₁) the straight or branched alkyl, and M ⁺Be monovalence or divalent cation.

(8) their mixture.

Above-mentioned said anion surfactant all is can buy on the market.Should be noted that: though dialkyl group thio succinate and fatty sulfonate have good effect when neutrality arrives slight alkalinity, PH is higher than at about 8.5 o'clock, and they are exactly chemically unsettled in composition.

Other useful cosurfactant that is used in the composition is a nonionic fatty alkyl poly glucoside.These tensio-active agents contain the C of straight or branched ₈To C ₁₅, preferably by about C ₁₂To C ₁₄Alkyl and contain on average by about 1 to 5 glucose unit, be best and have average 1 to 2 glucose unit.These tensio-active agents are disclosed in United States Patent (USP) 4,393,203 and 4,732,704, at this in conjunction with the conduct reference.

Said composition also can contain structural formula polyhydroxy fatty acid amide as follows:

In the formula, R ₁Be H, C _1-4Alkyl, the 2-hydroxyethyl, the 2-hydroxypropyl, perhaps their mixture better is C ₁-C ₄Alkyl, be more preferably C ₁Or C ₂Alkyl, C preferably ₁Alkyl (being methyl); R ₂Be C ₅-C ₃₁Alkyl, better be straight chain C ₇-C ₁₉Alkyl or alkenyl, be more preferably straight chain C ₉-C ₁₇Alkyl or alkenyl, straight chain C preferably ₁₁-C ₁₇Alkyl or alkenyl, or their mixture; Z is the polyhydroxy alkyl with linear hydrocarbyl chain, (on this linearity hydrocarbyl chain, at least three hydroxyls are directly connected on the chain) or the derivative of its alkoxyl group (preferably oxyethyl group or propoxy-).It is resulting by reducing sugar reaction in reductive amination process being preferably Z; Better Z is a glycosyl.Suitable reducing sugar comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar.As raw material, high dextrose maize treacle, high-fructose corn syrup, high malt sugar maize treacle can be used as above-mentioned every kind of listed sugar.It is blended sugar component that these maize treacle can produce for Z.Should be appreciated that this does not also mean that and attempt to get rid of other suitable starting material.Z preferably is selected from :-CH ₂-(CHOH) n-CH ₂OH,

-CH（CH ₂OH）-（CHOH）n-1-CH ₂OH，

-CH ₂-(CHOH) ₂(CHOR ') (CHOH)-CH ₂OH, wherein, n is 3 to 5 integer, comprises 3,5, R ' is H or certain ring-type or aliphatics monose and their alkoxy derivative.Glycosyl preferably, wherein n is 4, particularly

-CH ₂-（CHOH） ₄-CH ₂OH。

In the molecule formula I, R ¹Can be, for example, N-methyl, N-ethyl, N-propyl group, N-sec.-propyl, N-butyl, N-2-hydroxyethyl, perhaps N-2-hydroxypropyl.

R ²-CO-

, can be, for example, coconut monoethanolamide, stearylamide, oleylamide, laurylamide, tetradecyl acid amides, decyl amide, hexadecyl acid amides, tallow acid amides etc.

Z can be 1-deoxyglucose base, 2-deoxidation fructosyl, 1-deoxidation malt-base, 1-deoxidation lactose base, 1-deoxy-galactose base, 1-deoxymannose base, 1-deoxidation Fructus Hordei Germinatus trioxy-base etc.

The method for preparing polyhydroxy fatty acid amide is being known in the art, generally, they can prepare with following method, promptly, alkylamine and reducing sugar are reacted in reductive amination process, to generate the corresponding N-alkyl polyhydroxy amine, this N-alkyl polyhydroxy amine and fatty aliphatic ester or triglyceride level react in condensation/amidation step and generate N-alkyl, N-polyhydroxy fatty acid amide product then.Be used to prepare the composition that contains polyhydroxy fatty acid amide and for example be disclosed, british patent specification 809,060(is by Thomas Hedley ﹠amp; Co., Ltd. is disclosed in February 18 nineteen fifty-nine), United States Patent (USP) U.S.2,965,576, (E.R.Wilson is published in December 20 nineteen sixty) United States Patent (USP) U.S.2,703,798, (Anthony M.Schwartz is published in March 8 nineteen fifty-five) and United States Patent (USP) U.S.1,985,424, (Piggott, be published on December 25th, 1934), above-mentioned every piece of patent all combines with the present invention and is used as reference.

Be used to prepare N-alkyl or N-hydroxyalkyl, in a kind of method preferably of N-deoxidation glycosyl fatty acid amide, wherein, this glycosyl component is to be obtained by glucose, and, this N-alkyl or N-hydroxyalkyl functionality are the N-methyl, the N-ethyl, the N-propyl group, the N-butyl, the N-hydroxyethyl, or N-hydroxypropyl, this product is to prepare in order to following method, promptly, with the N-alkyl-, or N-hydroxyalkyl-glycosamine and fatty ester (are selected from fatty methyl esters, the fat ethyl ester, and fat triglyceride) in the presence of catalyzer, reacts and prepare, catalyst component is selected from: the tricresyl phosphate lithium, tertiary sodium phosphate, Tripotassium phosphate, tetrasodium pyrophosphate, three Tripyrophosphoric acid, five potassium, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, Quilonum Retard, yellow soda ash, salt of wormwood, disodium tartrate, di-potassium tartrate, Seignette salt, trisodium citrate, citric acid tri potassium, alkali formula water glass, alkali formula potassium silicate, alkali formula sodium silicoaluminate, with alkali formula potassium aluminosilicate, and the mixture of said components.Catalyst consumption is that benchmark measures with the mole of N-alkyl or N-hydroxyalkyl-glycosamine, preferably by about 0.5 mole of % to about 50 moles of %, be preferably by about 2.0 moles of % to about 10 moles of %.This reaction is generally by about 20 and carries out to about 90 minutes condition preferably by about 138 ℃ to about 170 ℃.When utilizing triglyceride level as the fatty ester source at reaction mixture, this reaction is also preferably carried out using under the situation of about 1 to about 10 weight % consisting of phase-transferring agent.Its consumption is that the total amount with reaction mixture is that benchmark measures.This consisting of phase-transferring agent is selected from saturated poly alkyl alcohol ethoxylate, APG, linear sugared acidamide surfactant and their mixture.

Best, this method is according to following said carrying out:

(a) fatty ester is preheated to about 138 ℃ to about 170 ℃,

(b) N-alkyl or N-hydroxyalkyl glycosamine are joined in the fatty acid ester of heating, and mixed, be mixed into the needed degree of formation liquid/liquid two-phase mixture;

(c) catalyzer is blended in this reaction mixture; With

(d) in the specific reaction times, stirred.

In addition, preferably, when if this fatty ester is triglyceride level, can with as consisting of phase-transferring agent, to account for reactant weight be about 2% to about 20% to its consumption, preformed LINEAR N-alkyl/N-hydroxyalkyl, the linear glucosyl fatty acid amide of N-product joins in the reaction mixture, can activate this reaction like this, thereby improves speed of reaction.

These poly-hydroxy " lipid acid " acid amides material is returned the detergent formulation Designers provides advantageous conditions, promptly they can be all or mainly by natural, can regenerated, non-petrochemical raw material and the material that can be degraded prepare.They have also shown low toxicity to hydrobiont.

Should be realized that, except the polyhydroxy fatty acid amide of molecule formula I, be used for preparing in their method, generally also will produce a certain amount of nonvolatile by product, for example esteramides and ring-type polyhydroxy fatty acid amide.The amount of these by products is along with specific reactant and reaction conditions and can be different.Best, to being incorporated into the polyhydroxy fatty acid amide in the detergent composition of the present invention, its form is made such regulation, promptly be added into the composition that contains polyhydroxy fatty acid amide in the washing composition contain be less than about 10%, the ring-type polyhydroxy fatty acid amide most preferably less than about 4%.Above-mentioned its superior part of said better method is that it only produces the by product of the lower aq that comprises such cyclic amide by product.

The cosurfactant that is used for the present composition also can comprise the mixture of anion surfactant and alkyl polyglucoside or polyhydroxy fatty acid amide.It is by 0% to about 35% weight that this cosurfactant is present in content in the composition, better is by about 5% to 25%, preferably by about 7% to 20%.

The foam secondary accelerator

Another component that can be included in the present composition is foam stabilization tensio-active agent (a foam secondary accelerator), and its content is about 15% for being less than, and is preferably by about 0.5% to 12%, is preferably by about 1% to 10%.Arbitrarily, practical foam stabilization tensio-active agent is five kinds of basic types in the present composition: trimethyl-glycine, ethylene oxide condensate, fatty acid amide, amine oxide semi-polar nonionic surfactants, and cats product.

Composition of the present invention can contain and has the trimethyl-glycine detergent surfactant that general formula is a following formula:

In the formula, R is a hydrophobic group, this group is selected from: contain by about 10 to about 22 carbon atoms, be preferably by about 12 alkyl to about 18 carbon atoms, the alkaryl and the aralkyl that contain a phenyl ring of same carbon atoms number band, this phenyl ring is counted as the analog structure that is equal to about 2 carbon atoms and separates with amido or ehter bond; Each R ¹Be to contain by 1 alkyl to about 3 carbon atoms; R ²Be to contain by 1 alkylidene group to about 6 carbon atoms.

The example of trimethyl-glycine is a Varion CDG-K preferably, the hexadecyldimethyl benzyl ammonium trimethyl-glycine, dodecyl amido propyl-dimethyl trimethyl-glycine, tetradecyl dimethyl betaine, tetradecyl amido dimethyl betaine and dodecyl dimethyl caproic acid ammonium.

Other amidoalkyl trimethyl-glycine that is suitable for is disclosed in United States Patent (USP) U.S.3,950,417; 4,137,191; With 4,375,421 and English Patent GB2,103,236.Above-mentioned all patents all combine with the present invention and are used as reference.

Should be realized that, the alkyl of above-mentioned beet alkali surface activator (and acyl group) can or natural origin or synthetic source obtain, for example they can be obtained by following mode: by naturally occurring lipid acid; By alkene, for example use Ziegler process prepared, perhaps by carbonylic preparation method; Perhaps by oil, with or the alkene need not " cracking process " separated.

The condenses of this oxyethane is broadly defined as by ethylene oxide group (is hydrophilic in nature at it) and organo-phobicity compound (is aliphatics or alkyl aromatic in nature at it) and carries out the resulting compound of condensation reaction.The length of this wetting ability or the polyoxyalkylenes that forms through condensation with the hydrophobic grouping of any specific can be regulated at an easy rate to obtain certain water miscible compound.This compound has needed balance between wetting ability and hydrophobic parts.

Be applicable to that the example as this class ethylene oxide condensate of suds-stabilizing agent is the condensation reaction products of Fatty Alcohol(C12-C14 and C12-C18) and oxyethane.For for the top performance of suds-stabilizing agent, the alkyl chain of this fatty alcohol or can be straight chain or side chain, but contain usually by about 8 to 18, preferably by 8 to about 14 carbon atom.The content of this oxyethane, with respect to every mole alcohol, serve as reasons about 8 moles to about 30, be preferably by about 8 to about 14 moles oxyethane.

The example of useful acidamide surfactant comprises having at its acyl moiety and contains about 8 to about 18 carbon atoms with ammonia, monoethanolamine and the diglycollic amide of the represented lipid acid of following general formula among the present invention:

In the formula, R has by about 7 to 21, preferably by aliphatic hydrocarbons about 11 to 17 carbon atoms, saturated or undersaturated; R ₂Expression methylene radical or ethylidene; M is 1,2 or 3, preferably 1.The concrete example of said acid amides is monoethanolamine coconut fatty acid acid amides and diethanolamine dodecyl fatty acid amide.These acyl moieties can be obtained by naturally occurring glyceryl ester; For example, Oleum Cocois, palm-kernel oil, soybean oil, and tallow, but also can be by synthetic, the oxidizing reaction of oil for example, or prepare with the hydrogenation with carbon monoxide of Fisher-Tropsch process.Select most C _12-14The single ethanol amide of lipid acid and diglycollic amide.

Amine oxide semi-polarity cats product comprises the mixture with the following compound of structural formula and these compounds

In the formula, R ₁Be alkyl, 2-hydroxyalkyl, 3-hydroxyalkyl, perhaps 3-alkoxyl group-2-hydroxypropyl group, wherein, alkyl and alkoxyl group contain respectively by about 8 to about 18 carbon atom, R ₂And R ₃Respectively do for oneself methyl, ethyl, propyl group, sec.-propyl, 2-hydroxyethyl, 2-hydroxypropyl or 3-hydroxypropyl; N is by 0 to about 10, the preferred especially following amine oxide of molecular formula

In the formula, R ₁Be C _12-16Alkyl, and R ₂And R ₃Be methyl or ethyl.Above-mentioned ethylene oxide condensate, acid amides and amine oxide more fully are illustrated in United States Patent (USP) U.S.4,316,824(Pancheri) in, the present invention is in conjunction with being used as reference.

Composition of the present invention can also contain certain following cationic quaternary ammonium tensio-active agent of molecular formula:

Or the following amine tensio-active agent of molecular formula:

In the formula, R ¹Be in alkyl chain, to have by about 6 alkyl or alkyl benzyls to about 16 carbon atoms; Each R ²Be selected from :-CH ₂CH ₂-,-CH ₂CH(CH ₃)-,-CH ₂CH(CH ₂OH)-,-CH ₂CH ₂CH ₂-and their mixture; Each R ³Be selected from: C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl, benzyl, and hydrogen (when y is not O); R ⁴With R ³Identical, or alkyl chain, wherein, R ¹Add R ⁴The sum of carbon atom be by about 8 to about 16; Each y is by 0 to about 10, and the total value of y is by 0 to about 15; X is any compatible negatively charged ion.

Above-mentioned preferably quaternary ammonium alkyl tensio-active agent is particularly worked as R ⁴Selected and R ³Said single chain alkyl tensio-active agent in above-mentioned molecular formula when identical.Best quaternary ammonium surfactant is a chlorine, bromine and Methylsulfate C _8-16Alkyl trimethyl ammonium salt, C _8-16Alkyl two (hydroxyethyl) methyl ammonium salt, C _8-16Alkyl hydroxyethyl dimethyl ammonium salt, C _8-16Alkoxyl group propyl group leptodactyline, and C _8-16Alkoxyl group propyl group dihydroxy ethyl methyl ammonium salt.In above-mentioned described salt, preferred C _10-14Alkyl trimethyl ammonium salt, for example, decyl trimethylammonium methylsulfuric acid ammonium, Dodecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide and coconut trimethyl ammonium chloride and coconut trimethylammonium methylsulfuric acid ammonium.

Employed in the present invention foam secondary accelerator can contain the mixture of any one or they of above-mentioned listed foam secondary accelerator.

Additional any component

Except above-mentioned said various ingredients, said composition can contain other component commonly used that is applicable to liquid and gelinite dish washing composition.

Component comprises and promotes discharge opeing arbitrarily, at United States Patent (USP) 4,316, and 824(Pancheri.1982 February 23) disclosed oxyethyl group nonionic surfactants, the present invention will be in conjunction with the conduct reference.

For phase stability and the viscosity that reaches needed product, can use alcohols, for example ethanol and propylene glycol, consumption are that for example ethanol and propylene glycol are particularly useful in liquid composition of the present invention by 0% to about 15% alcohols.

Gelinite composition of the present invention does not generally contain alcohols.These gelinite compositions can contain the toluene of higher dosage, the urea of the potassium sulfonate of dimethylbenzene or isopropyl benzene or sodium and higher dosage, promptly content is about 10% to about 30%(as gelifying agent).(referring to United States Patent (USP) U.S.4,615,819 and GB2,179,054A).

The component of other hope comprises thinner and solvent.Thinner can be inorganic salt.Ammonium chloride for example, sodium-chlor, Repone K etc.Solvent comprises water, low-molecular-weight alcohols, ethanol for example, Virahol etc.Composition generally will contain up to about 80% herein, serve as reasons about 30% preferably to about 70%, be preferably by about 40% to about 65% water.

Except as otherwise noted, percentage ratio herein, umber, ratio is all represented with weight.

The following example explanation the present invention, and help the understanding of the present invention.

Embodiment 1

Explanation according to following statement prepares following liquid composition of the present invention.With alkyl ethoxy carboxylate and suitable cosurfactant, secondary accelerator, ethanol, sodium-chlor and buffer reagent blending in addition.The pH value of mixture is adjusted to about 8 with ammonium hydroxide, add calcium ion (adding with calcium chloride dihydrate) then, if desired, regulates final pH value and is about 7.2.At this moment, can carry out the adjustment of final viscosity and less pH value.Subsequently, add spices and dyestuff, equal amount is a water.

Weight %

Component

C _12-13Alkyl ethoxy (average 3.5) 20

Carboxylic acid sodium ^*

C _12-13Alkyl ethoxy (average 3.5) alcohol ^*1.23

C _12-13Alkyl ethoxy (average 1.0) 8

Sodium sulfate

C _12-14Alkyl amido propyl-dimethyl trimethyl-glycine 3

C _12-14-16Alkyl dimethyl amine oxide 3

Calcium ion is (with CaCl ₂2H ₂O adds) 1

Trolamine 6

Sodium-chlor 0.5

Ethanol 7.5

Water and minor component-equal amount-

PH value (10% aqueous solution) 9.4 9.4 8.5 9.4

* to contain about 94.2% molecular formula be RO(CH to this surfactant mixture ₂CH ₂O) _XCH ₂COO ^-Na ⁺Alkyl ethoxy carboxylate, in the formula, R is C _12-13Alkyl (average 12.5); The scope of X is by 0 to about 10, and the distribution of oxyethyl group is such, is that benchmark measures with the weight of alkyl ethoxy carboxylate, and when X was 0, the content of material was 1%, when X greater than 7 the time, the content of material is less than 2%, the distribution of X on average is 3.5.It is RO(CH that this surfactant mixture also contains 5.8% the molecular formula of having an appointment ₂CH ₂O) _XThe fatty alcohol ethoxylate of H, wherein, R is C _12-13Alkyl, (average 12.5) and X mean value are 3.5, this surfactant mixture contains 0% soap class material.

Above-mentioned prescription provide excellent properties that the greasy and mildness of washing combines and, it is stable storing down at high temperature (up to 120).Said composition is when the about 7.2-7.5 of PH, and its cleaning function is better than the similar composition that contains equivalent (based on mole) magnesium ion.Particularly, when comparing with the similar composition that contains magnesium ion, these prescriptions also provide superior especially package stability.

The embodiment II

Except the pH value of regulating composition with sodium hydroxide to about 8.5, prepare following liquid composition according to the method for embodiment 1 statement.

Weight %

Component

C _12-13Alkyl ethoxy (average 3.5) 22

Carboxylic acid sodium

C _12-13Alkyl ethoxy (average 3.5) alcohol ^*1.35

C _12-13Sodium alkyl sulfate 5

C _12-14Alkyl amido propyl-dimethyl trimethyl-glycine 3

C _12-14-16Alkyl dimethyl amine oxide 2

C _12-13Alkyl ethoxy (average 8.0) alcohol 3

Calcium ion is (with CaCl ₂2H ₂O and add) 1.2

N-two (hydroxyethyl) glycine 1.5

Ethanol 7.5

Sodium-chlor 0.5

The water of equal amount and microcomponent-equal amount-

The PH(10% aqueous solution) 8.5

This prescription of the present invention not only provides at diluent to the good cleaning function of oily but also the package stability of (120) at high temperature is provided.

The embodiment III

Except the pH value of regulating composition with sodium hydroxide arrives about 9.5, the method for being stated by embodiment 1 prepares following liquid composition

Weight %

Component

C _12-13Alkyl ethoxy (average 3.5) 22

Carboxylic acid sodium ^*

C _12-13Alkyl ethoxy (average 3.5) alcohol ^*1.35

C _12-13Sodium alkyl sulfate 6

C _12-14Alkyl amido propyl-dimethyl trimethyl-glycine 3

C _12-14-16Alkyl dimethyl amine oxide 2.5

Calcium ion is (with CaCl ₂2H ₂O adds) 1.5

N-two (hydroxyethyl) glycine 2

Ethanol 7.5

The water of equal amount and microcomponent-equal amount-

PH value (10% aqueous solution) 9.5

When comparing with the composition that contains the equivalent magnesium ion, this prescription of the present invention not only provides at diluent to greasy good especially cleaning function but also good especially prescription package stability under high temperature (120) is provided.

The embodiment IV

The method of being stated according to the embodiment I prepares following liquid composition with low relatively surfactant content and relative high calcium ion content

Weight %

Component

C _12-13Alkyl ethoxy (average 3.5) 16

Carboxylic acid sodium

C _12-13Alkyl ethoxy (average 3.5) alcohol ^*0.98

C _12-13Alkyl ethoxy (average 3.0) 4

Sodium sulfate

C _12-14Alkyl amido propyl-dimethyl trimethyl-glycine 2

C _12-14-16Alkyl dimethyl amine oxide 2

Calcium ion is (with CaCl ₂2H ₂O adds) 3.2

N-two (hydroxyethyl) glycine 1

Trolamine 1

Ethanol 8

Balance water gaging and microcomponent-equal amount-

PH value (10% aqueous solution) 8.5

When comparing with the composition that contains the equivalent magnesium ion, above-mentioned prescription of the present invention not only provides when diluent the good cleaning function of oily, and the good especially prescription package stability of (120) at high temperature is provided.This prescription in solution, use the high density product to wash the dish custom be useful especially.

The embodiment V

Explanation according to following statement prepares following four kinds of liquid compositions of the present invention.

This prescription prepares by ethanol is joined in the surfactant mixture that contains alkyl ethoxy carboxylate.Then remaining tensio-active agent is added wherein and mixed.Then, add buffer reagent and sequestrant, prescription is regulated pH value, make it reach the above 0.5PH unit of about demarcation PH with sodium hydroxide.At last, add magnesium chloride, this magnesium chloride reduces pH value to calibration value.At this moment, can carry out the adjusting of final viscosity and a small amount of pH value.Subsequently, add spices and dyestuff, equipoise is a water.

Weight %

Prescription A prescription B prescription C prescription D

Component

C _12-13Alkyl ethoxy 22 22 24 12

(average 3.5) carboxylic acid sodium ^*

C _12-13Alkyl ethoxy 1.3 1.3 1.4 0.7

(average 3.5) alcohol

C _12-13Sodium alkyl sulfate 66 3-

C _12-13Alkyl ethoxy---18

(average 0.8) sodium sulfate

C _12-14Alkyl amido 33 3.5 2.5

The propyl-dimethyl trimethyl-glycine

C _12-14-16Alkyl 33 3.5-

Dimethyl oxidation amine

C _9-10-11Alkyl ethoxy---2.5

Magnesium ion is (with MgCl ₂6H ₂O 0.6 0.6 0.9 0.6

Add)

Methyldiethanolamine 10---

Diethanolamine-5--

Trolamine--2.5-

Glycine---5

Three (hydroxymethyl) aminomethane---5

Sulfo-succsinic acid trisodium--5-

N-two (hydroxyethyl) glycine 55 2.5-

Ethanol 9991

Spices and dyestuff 0.15 0.15 0.15 0.15

Water-equal amount-

PH value (10% aqueous solution) 9.2 9.0 8.3 9.5

This surfactant mixture contains molecular formula

RO(CH ₂CH ₂O) xCH ₂COO ^-Na ⁺About 94.2% alkyl ethoxy carboxylate, in the formula, R is C _12-13Alkyl, average 12.5; The scope of X is by 0 to about 10, and the distribution of this oxyethyl group is like this, when X is 0, is that benchmark measures with the weight of alkyl ethoxy carboxylate, and the content of material is about 1.0%.And when X greater than 7 the time, the content of material is less than about 2%.The distribution average of X is 3.5.It is RO(CH that this surfactant mixture also can contain molecular formula ₂CH ₂O) about 5.8% of xH fatty alcohol ethoxylate, wherein R is C _12-13Alkyl, average out to 12.5, X mean value=3.5.This surfactant mixture contains 0% soap class material.

Above-mentioned prescription provides the excellent properties that oily cleaning function and mildness are combined, and, when its when at high temperature (up to 120 °F) are stored, do not have precipitating action.These products are directly relevant with the ability of its maintenance diluting soln alkaline washing pH value to the ability of greasy washing.According to the high ability of washing pH value of their maintenance, putting in order of these products is A＞B＞C＞D successively.Directly to contain the content of surfactant mixture of alkyl ethoxy carboxylate relevant with them for these products adversary's mildness, and with the pass of the content of alkyl-sulphate and alkyl ethoxy sulfate be inverse relationship.Based on these reasons, these products are C＞A for the putting in order of mildness of hand, B＞D.Particularly, when comparing with the similar composition that does not have buffer reagent and/or sequestrant, these prescriptions also provide excellent in storage stability.Yet prescription D contains glycine, and can make the composition exhibiting decolorization when storing.

The embodiment VI

Method according to statement in embodiment 1 prepares following four kinds of liquid compositions, and they use at the identical alkyl ethoxy carboxylate surfactant mixture of implementing statement in 1.

Weight %

Prescription A prescription B prescription C prescription D

Component

C _12-13Alkyl ethoxy 22 22 22 22

(average 3.5) carboxylic acid sodium

C _12-13Alkyl ethoxy 1.35 1.35 1.35 1.35

(average 3.5) alcohol

C _12-13Sodium alkyl sulfate 6666

C _12-14Alkyl amido 3333

The propyl-dimethyl trimethyl-glycine

C _12-14-16Alkyl 3333

Dimethyl oxidation amine

Magnesium ion is (with MgCl ₂6H ₂O 0.6 0.6 0.6-

Add)

2-amino-2-ethyl-1,36666

-propylene glycol

Citric acid (existing)-2.0 6.0 with the Citrate trianion product-

Subsidiary (solvent, hydrotropic agent ,-equal amount-

Dyestuff, spices, etc.)

PH value (0.2% aqueous solution) 9.0 9.0 9.0 9.0

Prescription of the present invention B not only provides when diluting soln the good cleaning function of oily but also the package stability of (120) prescription at high temperature is provided.This be not included in prescription A, C in the scope of the invention and D and contrast and obtain.Prescription A, because it has cooperated surfactant mixture, the magnesium ion that contains alkyl ethoxy carboxylate, and, 2-amino-2-ethyl-propylene glycol in washing dish solution, keeps alkaline ph value owing to making it, therefore it provides diluting soln to the good cleaning function of oily, even also is like this in soft water.Yet prescription A is that storage is unsettled, and will generate Mg(OH) ₂Precipitation.Prescription C is owing to the Mg(OH that prevents of Citrate trianion) ₂Precipitate the advantage that generates and good product package stability is provided.But enough washing oily abilities can not be provided in diluting soln, and this is too high the minimizing in diluent to carrying out the needed effective Mg of good cleaning function of content owing to Citrate trianion ⁺⁺Content.Similarly, prescription D provide good storage stability, but poorer than prescription A and B to the oily cleaning function.

Claims

1, a kind of light-duty liquid or gelinite dish detergent composition is characterized in that comprising the following component of calculating by weight:

(a), comprise the following component of calculating by weight by about surfactant mixture of 5% to 70%

(i) by the following alkyl ethoxy carboxylate of about molecular formula of 80% to 100%:

In the formula, R is C ₁₂To C ₁₆Alkyl, the scope of X is by 0 to about 10, and the distribution of oxyethyl group is like this, promptly, weight with alkyl ethoxy carboxylate is that benchmark measures, X wherein is 0 o'clock, and material content is that X wherein is greater than 7 o'clock less than about 20%, the weight of this material is less than about 25%, when the mean value of R is C ₁₃Or when being worth less than this, then X mean value is by about 2 to 4, when the mean value of R greater than C ₁₃The time, X mean value be by about 3 to 6 and M be positively charged ion.

(ii) by 0% to about 10% molecular formula fatty alcohol ethoxylate as follows:

R is C in the formula ₁₂To C ₁₆Alkyl, the scope of X is by 0 to about 10, and the mean value of X is less than about 6; With

(iii) by 0% to about 10% molecular formula soap as follows: RCOO ^-M ⁺

In the formula, R is C ₁₁To C ₁₅Alkyl, M is a positively charged ion.

(b) by about 0.1% to 4% calcium or magnesium ion; Wherein, the pH value that has of the aqueous solution of 10% weight of said composition serves as reasons about 7 to 11;

(c) calcium or the magnesium chelating substances of generation solubility calcium or magnesium complex, the logarithm logKf with formation constant, it is worth between about 0.5 and 5, and this numerical value can be to prevent generating lime carbonate or magnesium hydrate precipitate in composition; Wherein, the pH value that has of the aqueous solution of 10% weight of said composition serves as reasons about 7 to 11.

2, according to the said composition of claim 1, wherein, pH value is for approximately by 8 to 10.

3, according to the said composition of claim 2, wherein, pH value is by about 8 to 9.5.

4, according to the said composition of claim 1, it comprises by about 0.5% to 3% calcium or magnesium ion.

5, according to the said composition of claim 3, it comprises by about 0.5% to 3% calcium or magnesium ion.

6, according to the said composition of claim 1, it also comprises cosurfactant.This tensio-active agent is selected from: alkylbenzene sulfonate, alkyl-sulphate, alkane sulfonate, alkene sulfonate, sulfated alkyl ether, fatty acid ester sulfonate, APG, and polyhydroxy fatty acid amide, their mixture.

7, according to the said composition of claim 1, it also comprises the foam secondary accelerator, and this foam secondary accelerator is selected from: trimethyl-glycine, ethylene oxide condensate, fatty acid amide, amine oxide semi-polar nonionic surfactants, cats product and their mixture.

8, according to the said composition of claim 6, it also comprises the foam secondary accelerator.This foam secondary accelerator is selected from: trimethyl-glycine, ethylene oxide condensate, fatty acid amide, amine oxide semi-polar nonionic surfactants, cats product and their mixture.

9, according to the said composition of claim 8, wherein, pH value is by about 8 to 9.5.

10, according to the said composition of claim 8, it comprises by about 0.5% to 3% calcium or magnesium ion.

11, according to the said composition of claim 8, wherein, pH value is by about 8 to 9.5.

12, according to the said composition of claim 1, wherein, in (a), R is C ₁₂To C ₁₄Alkyl.

13, according to the said liquid composition of claim 1, it comprises by about surfactant mixture of 12% to 30%.

14, according to the said composition of claim 1, wherein, this surfactant mixture comprises by about alkyl ethoxy carboxylate of 85% to 95%.

15, according to the said composition of claim 14, wherein, this surfactant mixture comprises by about alkyl ethoxy carboxylate of 90% to 95%.

16, according to the said composition of claim 12, wherein, this surfactant mixture comprises by about alkyl ethoxy carboxylate of 85% to 95%.

17, according to the said composition of claim 16, wherein, this surfactant mixture comprises by about alkyl ethoxy carboxylate of 90% to 95%.

18, according to the said composition of claim 1, wherein, this surfactant mixture comprises and is less than about 8% fatty alcohol ethoxylate.

19, according to the said composition of claim 18, wherein, this surfactant mixture comprises and is less than about 5% fatty alcohol ethoxylate.

20, according to the said composition of claim 1, wherein, this surfactant mixture comprises and is less than about 5% soap class.

21, according to the said composition of claim 12, wherein, this surfactant mixture comprises by about alkyl ethoxy carboxylate of 90% to 95%, is less than about 5% fatty alcohol ethoxylate and is less than 5% soap class.

22, according to the said composition of claim 21, it comprises that by about 0.5% to 3% calcium or magnesium ion wherein, pH value is by about 7 to 11.

23, according to the said composition of claim 22, it comprises that by about 0.5% to 3% calcium or magnesium ion wherein, pH value is by about 8 to 9.5.

24, according to the said composition of claim 21, it also comprises cosurfactant, and this cosurfactant is selected from: sulfated alkyl ether, fatty acid ester sulfonate, alkyl-sulphate, APG, polyhydroxy fatty acid amide and their mixture.

25, according to the said composition of claim 21, it also comprises the foam secondary accelerator, and this foam secondary accelerator is selected from: trimethyl-glycine, amine oxide semi-polar nonionic surfactants, fatty acid amide and their mixture.

26, according to the said composition of claim 25, it also comprises a kind of cosurfactant, this cosurfactant is selected from: sulfated alkyl ether, fatty acid ester sulfonate, APG, polyhydroxy fatty acid amide, with their mixture, and said composition also contains by 0.5% to about 3% calcium or magnesium ion, and its pH value is by about 8 to 9.5.

27, according to the said gelinite composition of claim 1, it comprises by about surfactant mixture of 10% to 45%.

28, according to the said composition of claim 2, it also comprises enough ealkaline buffers, and the pH value that keeps said composition is between about 8 and 10.