DE3026090A1 - LIQUID DETERGENT WITH A CONTENT OF DISABLING-INHIBITING - Google Patents

Abstract

1. A liquid detergent containing a) from 5 to 18 % by weight of an alkyl polyglycol ether corresponding to the following formula see diagramm : EP0044003,P5,F1 in which R**1 is a straight-chain alkyl group and from 20 to 75 % by weight of R**2, based on the alcohol on which the alkyl polyglycol ether is based, is a C1 -C4 alkyl group and the remainder is hydrogen, the total number of carbon atoms in R**1 and R**2 amounting to between 11 and 15, and n has a value of from 5 to 9, n being selected in such a way that the ethylene oxide content of the alkyl polyglycol ether amounts to between 50 and 65 % by weight, b) from 5 to 18 % by weight of an alkyl polyglycol ether corresponding to formula I, in which R**1 is a straight-chain alkyl group and R**2 is either hydrogen of from 20 to 75 % by weight of R**2, based on the alcohol on which the alkyl polyglycol ether is based, is a C1 -C4 alkyl group and the remainder is hydrogen, the total number of carbon atoms in R**1 and R**2 amounting to between 6 and 10, and n has a value of from 3 to 8, n being selected in such a way that the ethylene oxide content of the alkyl polyglycol ether amounts to between 55 and 70 % by weight, c) from 1 to 10 % by weight and preferably from 2 to 6 % by weight of a fabric-softening quaternary ammonium salt selected from the derivatives of ammonia and/or imidazoline preferably containing 2 long-chain aliphatic radicals in the molecule, the weight ratio of a) to b) preferably amounting to between 2:1 and 1:2, characterized in that it additionally contains d) up to 50 % by weight, based on the quantity of components a) and b), of a cationic starch ether containing ammonium groups, the quantitative ratio of c) to d) preferably amounting to between 3:1 and 1:3.

Description

HENKEL KGaA

ZR-FE / Patents Düsseldorf, July 8, 1980 ~ ,, _ _o ,

Henkelstrasse 67

Patent application

D 6127

"Liquid detergent with a content of discoloration-inhibiting additives"

The present invention is a liquid detergent and Cleaning agent based on nonionic surfactants and laundry / calibrating quaternary ammonium compounds contains cationic starch ethers, which causes the transfer of color from colored textiles to white or light-colored textiles during washing together is counteracted.

The transfer of dye when washing colored and white or light-colored textiles together has been known for a long time Problem for which there are already some suggested solutions, but all of which cannot be fully satisfied because they are opposite to one A number of colorations or textiles have only a minor effect. For example, from DE-AS 22 32 353 a means is known whose discoloration-inhibiting additive is polyvinylpyrrolidone. The DE-OS 24 20 561 describes a detergent with a combination of alkali metal percarbonate and polyethylene glycol of a certain molecular weight or polyvinylpyrrolidone. DE-OS 23 09 099 relates to a Means containing two different organic compounds, which contain basic nitrogen atoms in the molecule. In the DE-OS 28 28 619 is a detergent made from nonionic surfactants, zwitterionic or semipolar surfactants and cationic surfactants in certain proportions described. Agents containing per compounds are described in U.S. Patents 4,005,029 and 4,006,092.

130067/0032

Patent application η ^ γιη --g- / HENKEL KGaA

- L. ZR-FE / Patento

It has now been found that a liquid detergent based on nonionic surfactants, which contain common quaternary ammonium compounds as a fabric softening component, by adding cationic starch ethers have very good discoloration-inhibiting properties having. Cationic starch ethers are well-known commercially available substances that are used as additives to improve the quality of the Paper and cardboard manufacture are used. The production of the starch ethers can be carried out in a manner known per se, for example by reaction starch, for example potato starch, with ethyleneimine (cf.

U.S. Patent 3,303,184) and then in part or in full Quaternization of the amino group take place. Preferably, however such ethers as discoloration inhibitors are only added in combination with textile softening quaternary ammonium compounds used that for example by reacting starch with 2,3-epoxypropyltrialkylammonium salts or 3-chloro-2-hydroxypropyltrimethylammonium salts, especially with 2,3-epoxypropyltrimethylammonium chloride can be obtained. Such reaction products are described in GB-PS 1,136,842, for example. The quaternary salts can as halides, in particular chlorides, sulfates, alkyl sulfates, nitrates, phosphates and as salts of organic acids, e.g. as Acetates, citrates or lactates are present. A typical product is Empresol N from Emsland-Starke GmbH, Emiichheim, Federal Republic Germany. This is a cationic potato starch derivative with tertiary and quaternary nitrogen atoms, its cationic charge is evenly distributed over the entire starch chain.

The concentration of the starch ether additive in the detergent is between 5 and 50% by weight, based on the amount of nonionic substances used Surfactants, and the ratio of the starch ether to the softening quaternary ammonium compound is between 3: 1 and 1: 3.

The quaternary ammonium compounds are in particular to derivatives of ammonia, i.e. to the quaternary salts obtainable by alkylation of long-chain secondary amines, such as the Compounds distearyldimethylammonium chloride and ditallow alkyldimethylammonium chloride. In addition to the chloride, there are also anions

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Patent application _D ^ ₁₂₇ -? - HENKEL KGaA

. H,. ZR-FE / F'atente

Bromide, methyl sulfate, ethyl sulfate, methane, ethane or toluene sulfonate into consideration. Other possible quaternary ammonium compounds are those obtained by reacting 1 mole of an aminoalkylethylenediamine or Hydroxyalkylethylenediarnins with 2 mol of a long chain, C 1 -C ", - fatty acid or their esters obtainable iniidazoline compounds, which are then converted into the quaternary imidazolinium compounds by alkylation be transferred.

Typical preferred textile softeners are, for example, the commercial products "Präpagen WK" and "Präpagen WKT" (Hoechst), "Adogen 442" (Ashland) which are ditallow alkyl dimethyl ammonium salts acts. These compounds are 1 to 10, preferably 2 to 6% by weight in the detergent according to the invention.

The nonionic surfactant component consists of a combination of two different nonionic surfactants, as described in DE-OS 28 17 834. The liquid detergent according to the invention is therefore characterized in that it

a) 5-18% by weight of an alkyl polyglycol ether of the formula

HI)

/ i. L · L Il

R ²

/ l ~ * I f wl * c \ ^ -JV ν OO /

1 2

in which R is a straight-chain alkyl group and R to 20 to , 75 wt .-? (5 - based on that of the alkyl polyglycol ether

underlying alcohol - a C, -C.-alkyl group and

otherwise mean hydrogen, the total number

1 is 2 of the carbon atoms in R and R 11 to 15, and η denotes a value from 5 to 9, and where η is selected so that the ethylene oxide content of the alkyl polyglycol

ethers is about 50 to 65 wt .-? o,

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Patent application q 6127 - ^ J - * - 4} HENKEL KGaA

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b) 5-18% by weight of an alkyl polyglycol ether of the formula I in which

1 2

R is a straight-chain alkyl group and R is either hydrogen, or 20 to 75 wt .- ϊί - based on the dem Alkyl polyglycol ethers are the alcohol on which they are based - a C 1 -C 4 -alkyl group and the rest are hydrogen,

12 where the total number of carbon atoms in R and R

Is 6 to 10 and η is a value from 3 to 8, and where η is selected so that the ethylene oxide content of the alkyl polyglycol ether is about 55 to 70 K by weight,

c) 1-10, preferably 2 to 6 wt .-? i of a textile softening agent quaternary ammonium salt, selected from the derivatives of ammonia and / or imidazoline with preferably 2 long-chain aliphatic radicals in the molecule, d) 5-50% by weight of a cationic starch ether, based on the Mixture of nonionic surfactants consisting of a) + b),

contains, the quantitative ratio of a): b) preferably 2: up to 1: 2 and the quantitative ratio of c): d) is preferably 3: 1 to 1: 3.

The alkyl polyglycol ethers suitable according to the invention as constituent a) of the formula I are derived from alcohols obtained by reacting linear olefins with carbon monoxide and hydrogen after known .oxo process by hydroformylation and subsequent Hydrogenation can be produced. Commercially available oxo-alcohol mixtures, which are suitable for the production of the surfactant component a) are, for example, those available under the trade name “Dobanol” Oxo alcohols from the Deutsche Shell Chemie Gesellschaft, the have about 25 weight percent of 2-alkyl branches. Other suitable Oxo alcohols are under the name "Synprol" of the Imperial Chemical Industries Ltd. Available alcohol mixtures with approx. 50 to 70% by weight of 2-alkyl branches. Other suitable products based on of oxo alcohols are, for example, various "Lutensol" types from BASF with about 30 to 35 wt .-? o branched alcohols and some "Lial" types of Liquichimica S.p.A. with about 60 wt .-? o branched alcohols.

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Patent application q ₆₁₂ 7 5 - /) HENKEL KGaA

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Particularly preferred as constituent a) are alkyl polyglycol ethers which are ethylene oxide condensates of the oxo alcohols mentioned with 13 to 15 carbon atoms and an average ethylene oxide content of approx. 55 to 65% by weight. Typical preferred products are, for example, "Dobanol 45-7", which consists of at least 95% C ,, / C, - oxo oxo alcohol with an average of 7 moles of ethylene oxide, and "Lutensol AO-8", which is a Cjj / Cj ^ -oxo alcohol etnoxylate with an average of 8 moles of ethylene oxide represents.

Preferred as constituent b) are alkyl polyglycol ethers whose alcohol base is natural or synthetic primary fatty alcohols or oxo alcohols which contain 9 to 12 carbon atoms and have an ethylene oxide content of approx. 60 to 70% by weight. Typical preferred products are, for example, the commercial product "Marlipal KF" (Chemische Werke Hüls), which is a C ₁₀ / C ₁₂ fatty alcohol F; thoxylate with an average of 6 moles of ethylene oxide, and "Lutensol ON-70", which has a C " / Represents C -oxo-alcohol ethoxylate with an average of 7 moles of ethylene oxide. Suitable fatty alcohols as the basis for preferred alkyl polyglycol ethers are also the commercial products "Lorol C-8 to 12" (Henkel).

The ratio of the amount of component a) used to the amount used The amount of component b) essentially determines the parameters of detergency, foaming behavior and softening effect. Optimal ■ Results are obtained when the ratio of a): b) is between about 2: 1 and 1: 2.

In general, constituent a) and constituent b) are amounts from a total of 10 to 30 wt .-? i, based on the total weight of the Detergent, used, an amount of 15 to 30 wt .-? O is preferred.

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Patent application η. ζ \ 2Ί £ -. HENKELKGaA

, // (/ ZR-FE / Patents

The preferred solvent for the detergents according to the invention is V / ater used. However, organic solvents can also be used in amounts of up to 20, preferably up to 16,% by weight of the total Liquid detergent can also be used. Such additional solvents are either lower alkanols or lower diols or Polyols such as ethanol, isopropyl alcohol, ethylene glycol, Propylene glycol or glycerin. Optionally, polyols can also be used Ether compounds such as methyl, ethyl, butyl or diethylene glycol or their acetates (for example products of the "Cellosolve" type from Union Carbide Corp.) are used.

To improve the solubility of the surfactants, it is often expedient to use solubilizers, so-called hydrotropes, in addition to or instead of the aforementioned organic solvents. The preferred hydrotropes are non-surfactant organic sulfonates, such as C - C, _n -alkanesulfonates, and the salts of toluene, xylene

O J.U

and cumene sulfonic acid, preferably its alkanolamine and alkali metal salts, especially their potassium salts. Urea is also suitable as a hydrotrope. Hydrotropes are used in amounts of 2 to 12, preferably 3 up to 9 Geu .-? o, based on the total liquid detergent, added.

To improve certain properties, the invention Other auxiliary substances, also usually effective in small amounts, are added to detergents; these are, for example, turbidity and Viscosity adjusting agent, which is usually about 0.05 to 2 wt .-? O in the Detergents are included. These are, for example, esters of alkanols or partial esters of polyols with longer-chain fatty acids, such as palmitic or stearic acid. A typical product is ethylene glycol stearate.

Formalin is usually used as a preservative in an amount of 0.05 to 1% by weight.

To avoid discoloration of the detergents during long periods of storage, Complexing agents are used, which can be caused by contamination e.g. with heavy metal ions during production for heavy metal ions too. Common complexing agents are

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Patent application ρ £ _i2 7 - * -? - * t HENKEL KGaA

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the sodium, potassium or triethanolamine salts of aminopolycarboxylic acids, such as ethylenediaminetetraacetic acid or nitrilotriacetic acid. They are used in amounts of 0.1 to 1% by weight.

For example, substances with flowery / fresh or come as fragrances fruity or as cosmetic or creamy fragrance note in question.

Suitable dyes are e.g. water-soluble red xanthene dyes, like Rhodamine B extra.

A particularly preferred one in terms of balanced product properties Means has the following composition:

a) 10-12.5 wt .-? o of an alkyl polyglycol ether of the formula I in which

1 2
R and R together have 11 to 13 carbon atoms

and wherein the average ethylene oxide content of the alkyl polyglycol ether is 55 to 65% by weight;

b) 10-12.5 wt .-? o 'of an alkyl polyglycol ether of the formula I in which

1 2

R has 7 to 10 carbon atoms, R = H and

wherein the average ethylene oxide content of the alkyl polyglycol ether Is 60 to 70 wt%;

c) 2-6 weight percentages of a ditallow alkyldimethylammonium salt, preferably of chloride and / or methyl sulfate;

d) 2-6% by weight of a cationic starch ether;

e) Remainder water and organic solvents and optionally

other common additives present in small quantities such as dyes and fragrances, hydrotropes, Complexing agent for heavy metal traces as well as

Serving agents, opacifiers and viscosity regulators.

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Patent application D 6127 - «- θ-— A * t HENKELKGaA

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The detergents according to the invention can be used for washing together and at the same time improving the handle of colored and light-colored or white textiles made of cotton, linen, wool, cellulosic Man-made fibers, synthetic fibers such as polyester, polyacrylonitrile, Polyamide and blends of cotton, wool, linen, cellulosic man-made fibers and synthetic fibers are used, whereby the dye transfer is largely suppressed .. The washing and the softening process can take place at washing temperatures of up to about 60 C. The use concentration of the agents is generally 2 to 20 ml per liter of washing liquor, preferably around 3 to 8 ml per liter. The textiles are not only flawless cleaned, but also get a comfortable grip. The good foaming behavior allows the use of the agent both in the Washing machine as well as washing by hand.

130067/0032

Patent application ρ gj27 - "* 9 ' A 1 " HENKEL KGsA

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At s pie], ο

Example 1

A detergent with the following composition was prepared:

11.0% by weight o 0.1 / C _{1 r} ~ oxo-alcohol ethoxylate with an average of 58% by weight 5K ethylene oxide ("Dobanol 45-7", Shell); 11.0 Gev /.-? O C ₁₀ / C ₁₂ -Fettalküliol-Ethoxylnt with average

60 Geu /. -% ethylene oxide ("Marlipal KF", Chemische Werke Hüls); 2.8 wt .-? O Ditalgalkyldiriiethylammoniu: nchlorid (lüO ^ ig), used as 75? Oige paste, remainder isopropanol and water, ("Prepagen ViK", Hoechst);

1.2 Ge \! /.-? A cationic potato starch ether ("Empresol N",

Emsland-Starke GmbH);
7.0 % by weight ethanol / 1,2-propylene glycol;

Remainder water and small amounts of preservatives, coloring agents, fragrances.

Example 2

An agent with the composition of Example 1 was used as a comparison with the exception of the potato starch ether, which was replaced by the same amount of ditallow alkyldimethylammonium chloride. This detergent corresponds to an agent of the prior art.

Example 3

Another agent was prepared having a composition like the agent of Example 2, except that the Ditallowalkyldimethylammonium chloride was replaced by the same amount of water.

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Patent application D 6127

Example 4

HENKEL KGaA ZR-FE / Pateiite

With the detergents of Examples 1 to 3, washing tests were carried out in a commercially available drum washing machine. In the process, cotton pale nettle, white, at a liquor ratio of 1:20, was washed without contamination in the presence of an approx. 20 g heavy section of fabric which was dyed with 3.5% Sirius light red F 4 BL, 154 %. 84 g of the detergents from Examples 1 to 3 were placed on a drum and, after washing, the reflectance values were measured using the Zeiss Elrepho RFC3, R 560 filter.

The result is shown in Table 1. Table 1

Detergent off Reflection values example 1
Example 2
Example 3 79.1
73.1
57.9

The results show the superior discoloration inhibiting effect of the detergent according to the invention from Example 1.

Similar results are obtained with textile samples made of terry cloth, Lycra, Cotton, Polyester / Cotton, Dralon, Nylon, etc.

/ 11

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Claims (10)

Patent application η "Liquid detergent with a content of anti-discoloration additives" ___ Claims 1. Liquid detergent, characterized in that it a) 5-18% by weight of an alkyl polyglycol ether of the formula R ¹ CHCH ₂ O (CH ₂ CH ₂ O) _n H R ^ 1 2 in which R is a straight-chain alkyl group and R to 20 to 75 Geu /.- Λ - based on that of the alkyl polyglycol ether underlying alcohol - a C, -C.-alkyl group and otherwise mean hydrogen, the total number 1 2 the carbon atoms in R and R is 11 to 15, and η means a value from 5 to 9, and where η is so selected is that the ethylene oxide content of the alkyl polyglycol ether is about 50 to 65 Geu /.-? o, b) 5-18% by weight of an alkyl polyglycol ether of the formula I ₁ in the 1 2 R is a straight-chain alkyl group and R is either hydrogen, or 20 to 75 Geu /.- 5o - based on the Alkyl polyglycol ethers underlying alcohol - a C, -C.-alkyl group and the rest are hydrogen, 12 where the total number of carbon atoms in R and R 6 to 10 and η denotes a value from 3 to 8, and where η is selected such that the ethylene oxide content of the alkyl polyglycol ether is about 55 to 70 wt. SS, 130067/0032 ORIGINAL INSPECTED Patent application _π £ ^ 7 -12-. HENKEL KGaA . ZR-FE / Patentö 'ft' c) 1-10, preferably 2 to 6 % by weight of a fabric softening agent quaternary ammonium salt selected from the derivatives of ammonia and / or imidazoline with vorzugsueise 2 long-chain aliphatic residues in the molecule, d) 5 - 50 wt. Si of a cationic starch ether, based on the Mixture of nonionic surfactants consisting of a) + b), contains, the quantitative ratio of a): b) preferably 2: 1 up to 1: 2 and the quantitative ratio of c): d) is preferably 3: 1 to 1: 3. 2. Liquid detergent according to claim 1, characterized in that component a) and component b) together 10 to 30 Geu .-? O, preferably 15 to 30% by weight, based on the total weight of the detergent. 3. Liquid detergent according to claim 1 and 2, characterized in that R ¹ + R ²
contain atoms of matter " 1 2
shows that R + R of component a) together 11 to 13 carbon 4. Liquid detergent according to claim 1 to 3, characterized in that that the ethylene oxide content of component a) about 55 to 60 wt. Si. 5. Liquid detergent according to claim 1 to 4, characterized 1 2
draws that R + R Contain material atoms. 1 2
shows that R + R of component b) together 8 to 10 carbon 6. Liquid detergent according to claim 1 to 5, characterized in that that the ethylene oxide content of component b ~) is about 55 to 65 wt .-? o. 130067/0032 Patent application ρ ₆₁ 27 13 HENKELKGaA 3ZR-FE / patents 7. Liquid detergent according to claim 1 to 6, characterized in that that component c) is a quaternary ammonium salt, whose anion is selected from the group comprising chloride, bromide, methyl sulfate, ethyl sulfate, methane, ethane or toluenesulfonate is. 8. Liquid detergent according to claim 1 to 7, characterized in that that component c) is a ditallow alkyldimethylammonium salt. 9. Liquid detergent according to claim 1 to G, consisting of a) 10-12.5 % by weight of an alkyl polyglycol ether of the formula I in which 1 2 R and R together have 11 to 13 carbon atoms and wherein the average ethylene oxide content of the alkyl polyglycol ether is 55 to 65% by weight; b) 10-12.5 Geu /. ~ So of an alkyl polyglycol ether of the formula I, in which 1 2 R has 7 to 10 carbon atoms, R = H and wherein the average ethylene oxide content of the alkyl polyglycol ether 60 to 70 Geu .-? O; c) 2-6 wt .-? o of a ditallow alkyldimethylammonium salt preferably the chloride and / or methyl sulfate; d) 2-6% by weight of a cationic starch ether; e) remainder 'water and organic solvents and optionally other common additives present in small quantities such as dyes and fragrances, hydrotropes, Complexing agent for traces of abrasive metal as well as preservatives, Opacifiers and viscosity regulators. 13 0 0 6 7/0032 Patent application _{D 612} j - 14 - ^ HENKELKGaA l, ZR-FE / patents 10. Liquid detergent according to claim 1 to 9, characterized
by a content of cationic starch ether, obtainable by reacting starch with 2,3-epoxypropyltrimethylammonium salts. 130067/0032