DE2533795A1 - DETERGENT COMPOSITIONS - Google Patents

Description

The invention relates to detergent compositions having improved ability to remove soil particles. In particular, compositions containing certain ethoxylated compounds are unexpected remove loamy dirt well.

Zwitterionic surfactants, i.e., electrically neutral compounds with both positive and negative Charge centers in the same molecule are known. For example, U.S. Patents 3,668,240 and 3,764,568 describe zwitterionic surfactants with a 2,3-butene residue between the charge centers. U.S. Patent 3,332 describes mixtures of certain olefin sulfonates with zwitterionic surfactants in which the charge centers are separated from one another by a 2-hydroxypropane group. U.S. Patents 3 ^ 52-66 and 2,78I disclose zwitterionic surfactants optionally substituted by numerous oxygen-containing groups substituted between the negative and positive charge centers could be. U.S. Patent 3,769,311 describes

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Carboxyl compounds with Kthylenoxidgruppen between the Charge centers, however, does not give any indication of the effect of the various structural parameters in terms of the ability to remove dirt, especially dirt particles.

In contrast, the present invention relates to detergent compositions containing certain zwitterionic surfactants having a polyethyleneoxy group Such a size that not only the molecule is adsorbed onto the particles and other dirt from an aqueous system and then the dirt is removed by means of emulsification or dispersion, but also the dirt that is removed constantly is kept in suspension in the aqueous solution.

Accordingly, the present invention is based on the discovery that a wide range of zwitterionic compounds can be used in conjunction with certain detergent builders has unexpectedly good properties in terms of removal of solid and oily dirt from hard surfaces and textile materials. The ethoxylated ones used according to the invention Zwitterionic compounds have the ability to remove dirt particles regardless of the hardness of the water to remove wide range of Ca and Mg concentrations. This property is hardly influenced by temperatures in the range of 20 - 60 ° C, at which washing processes normally take place in the household.

The importance of the invention is obvious, since it allows a high degree of soil removal with a wide Range of detergent formulations. The nature and amount of the other components of the formulation can vary be selected according to the efficiency of the selected ethoxylated zwitterionic substance.

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The present invention thus relates to ethoxylated zwitterionic ones Detergent compositions containing compounds which have good properties with respect to the removal of

which have soil particles and oily soil, wherein / detergent compositions can be in both liquid and granular form.

The invention relates to a detergent composition

containing:

A.) 1 - 99 Ge \ i .-% (based on the composition) of a

water soluble compound of the formula

I ²

i) R ₁ - H + - (C ₂ H ₄ 0) _y R ₄ X-

^R 3

in which the symbols have the following meanings:

R ₁ = straight or branched chain alkyl or alkenyl radicals with 8-30 carbon atoms or alkaryl radicals with 10-24 carbon atoms in the alkyl group;

Rp = straight or branched chain alkyl or alkenyl radicals with 8-21 carbon atoms, alkaryl radicals with 6-16 carbon atoms in the alkyl group or alkyl or hydroxyalkyl radicals with 1-4 carbon atoms;

R-, = straight or branched chain alkyl or alkenyl radicals with 8-21 carbon atoms, alkaryl radicals with 6-16 carbon atoms in the alkyl group, alkyl or hydroxyalkyl radicals with 14 carbon atoms or the group - (C ₂ H ^ O) _x H, where χ is a number from about 3 to about 50;

Ri | = C ₁ -Cg -alkylene, C-7-Cg-alkenylene, 2-hydroxyalkylene radicals with 3 carbon atoms, 2- or 3-hydroxyalkylene radicals with 4 carbon atoms or alkarylene radicals with 1-4 carbon atoms, where Rh is of -CH ₂ -CH _{2 '- when R 1 is} the group - (C 2 H ₄ O) _x H;
+) in the alkyl group

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X ~ = sulfate or sulfonate anion;

y = a number from 2-100, where χ + y2ilO, when R, has the meaning -. (C ₂ H ₂ JO) _x H;
or the formula

\ -f- < ^C 2 ^H 4 ^O) yl- ^CH 2 ^CH 2 - ^X < ^C 2 ^H 4 ° ' _X -1- ^CH 2 ^CH 2 " ^X "

in which the symbols have the following meanings:

R. = straight or branched chain alkyl or alkenyl radicals with 8-30 carbon atoms;

Rp = straight or branched chain alkyl or alkenyl

radicals with 8 - 30 carbon atoms or alkyl or hydroxyalkyl

residues with 1 - ^ C atoms;

X ~ = sulfate or sulfonate;

χ and y = numbers from 2 - 100, where χ + y> 12;

M = alkali metal, ammonium or alkanolammonium cation; B.) of 99 - 1 wt -.% (Based on the composition) of an organic or inorganic detergency builder.

Ethoxylated zwitterionic compounds with hydroxyl groups on carbon atoms which are immediately adjacent to the nitrogen atom and / or the X radical are not preferred, because they are unstable in water, especially at non-neutral pH levels, and because they are compared to others Hydroxy compounds are extremely difficult to make.

Preferably, the ethoxylated zwitterionic compound is either ιυ- (NC. G_, galky 1, NC _1- , alkyl, N-polycäthenoxyammonio) -2-polyäthenoxyäthan-l-sulphonate, wherein the total number of

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Ethylene oxide groups between 15 and 25 ', or uy- (NC ₁₂ _ ₁ galkyl _i N, N-diC ₁ _C, alkylammonio) -2-polyethenoxyethane-1-sulphonate, in which the number of ethylene oxide groups in the polyethylene chain is between 6 and 12 .

Effect tests

The removal of particle dirt and oily dirt is determined, both with regard to the detergent formulations according to the invention and with regard to comparative formulations,
a.) Removal of particle dirt

One works in either an automatic mini washing machine (AMVJ) with a capacity of 4700 ml and one

Tissue / liquid ratio of 1:30 or in one

+)
"Tergotometer" with a capacity of 1000 ml and a tissue / liquid ratio of 1: I ² IO. In both cases the machines are equipped with a horizontally rotating paddle stirrer, whereby the AMVi has a speed of 100 revolutions per minute (RPM) and the Tergotometer a speed of 80 RPM.

The AMW-washing method is a twelve minute wash cycle at 40 ⁰ C in water with 6.7 ° dH (calculated as CaCO _3), wherein a Ca: Mg-salt ratio of 2: 1 is used. The first two minutes of the cycle are used to dissolve the product; the fabric load is then added and washing is carried out for the remaining 10 minutes. This is followed by a five-minute rinse cycle, of which 2 minutes run with stirring, while the remaining 3 minutes are allowed to rotate in order to remove the excess moisture. The tissues are then drum dried prior to examination.

A similar washing process is used for the tergotometer, with the exception that V / water of 4.8 ° dH +) see "Surfactant Science Series ¹ ', Vol. 5, Part I ₃ 1972, pages 417-418, M. Dekker, Inc., New York

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with a Ca: Mg salt ratio of 3: 1 (calculated as CaCCU) chooses. The laundry is followed by a three-minute rinse at 27 ° in water of the same hardness and composition and kind of like for laundry, on. The fabric swatches are then machine dried before being examined.

The fabric loading for the removal of dirt particles is a mixture of white cotton, "Polycotton" (65 % DACRON® / 35 % cotton) and polyester (KODEL®); it is contaminated with a standardized illite clay. In the AMW process, three 13 13 cm specimens of each fabric are used in each batch; in the tergotometer the pieces are 6.5 x 6.5 cm.

The results (expressed as a relative soil removal index) represent a percentage of the whiteness value of a commercial synthetic for each formulation Standard detergent is achieved at the same time under identical conditions. This standard formulation is hereinafter referred to as "A" and has the following weight composition:

Sodium C ₁₂ alkyl benzene sulphonate 7.55

Sodium Tallow Alkyl Sulphate 9.25

Coconut alcohol + 6 moles of ethylene oxide 0.60 diethanolamide 1.60

Sodium tripolyphosphate 50.00

Sodium Silicate Solids 5.90

Sodium sulfate lh , 20

Humidity 10.00

Miscellaneous 0.30

100.00

Assessment of the effect

The fabric samples are means of before and after washing a Gardner whiteness meter by reading off the L, a, and b coordinates. The whiteness (W) is calculated

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W = 7L ² - iJOLb 700

The effect is determined by finding the difference of whiteness (/ 1W) before and after VJaschen as:

- W after before

It is compared to the commercial control product A by calculating Δ \ ί as a percentage of the EW value of the control product for each batch.

Relative soil removal index = Δ W for test product χ

A W for control product A \

b.) grease and oil removal tests

The same equipment and washing conditions are used for this used. The loading with tissues exists

(R) made from a blend of green polycotton (65% DAC RON ^ / 3 5 %

Cotton) and polyester (KODED ^{£ y} ); be of any type

4 pieces of 6.5 x 6.5 cm each used in the Tergotometer.

You use two triglyceride contaminants, namely bacon fat and vegetable oil, and two hydrocarbon spills, namely dirty motor oil and simulated lipid pollution.

After washing and drying, the test pieces are visually assessed, on a scale with the following values:

SO 9 θ 87/1063

5 = complete removal
h = noticeable dirt remaining 3 = moderate amount of dirt remaining 2 = large amount of dirt remaining 1 = very large amount of dirt remaining 0 = no changes, original amount of dirt remains.

in terms of
As in the soil particle action test, the results are also expressed here as a percentage of the soil removal achieved by standard formulation A under the same conditions.

The compositions of the invention contain two essential components, namely the ethoxylated zwitterionic compound and a detergent builder, the can be inorganic or organic in character. The zwitterionic compound and detergent builder may be present in the ratio of 99: 1 to 1:99 (by weight), preferably in the ratio of 20: 1 to 1:10 and more preferably in a ratio of 5: 1 to 1: 5. The exact proportions of zwitterionic The substance and builder depend on the nature of the zwitterionic compound and the type of product that is being formulated shall be. E.g. you will be using a product intended for prewash that has specific soiling Direct application on the fabric should remove it, formulate it so that it contains a lower proportion of zwitterionic Contains joint and other optional ingredients as a product intended for home wash.

For a detergent intended for the main wash, the proportion of ethoxylated zwitterionic compound is in the range from about 5 to 35% by weight, preferably 10 to 25% by weight and very particularly preferably 15 to 20% by weight; the proportion of builder is from 10 to 70 wt -.%, preferably 10 to 60 wt -.%, and most preferably from 20 to I5

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% By weight . Such a laundry detergent can be formulated as conventional granules or as a liquid, paste, flake, strip, noodle, ball or tablet. As will be shown below, the flexibility in formulation is due, at least in part, to the ability of the zwitterionic surfactants of the present invention to develop soil removal properties equivalent to commercial heavy duty laundry detergents when mixed with detergent builders.

The ethoxylated zwitterionic compounds according to the invention can be used have the following formulas:

R- I ²

(i) R ₁ -N ⁺ - (C ₂ H ₄ O) - R ₄ -X

^R 3

a.) Long-chain mono-derivatives

In this derivative, R. is a hydrocarbon radical which can be a straight or branched chain alkyl or alkenyl radical with 8-30 carbon atoms or an alkaryl group in which the alkyl radical has 10-24 carbon atoms; R ₂ and R are alkyl or hydroxyalkyl groups with 1 to ¹ C atoms; _{R | j is C 1} -C 6 alkylene, C 1 -C 6 alkenylene, 2-hydroxypropylene or 2- or 3-hydroxybutylene or a C _{1 -C 1 alkarylene group;}

X is a sulfonate or sulfate radical; y has a value between 2 and 100.

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Preferred groups for R ,. are C. ^ - C ^ g -alkyl, in particular ^C 14 ~ ^C 16 ~ ^{alkyl; for R} 2 ^{and R} 3 ^c i ~ ^C 3 ~ ^alk y ^{1 and} C ₂ -C, -hydroxyalkyl, the particularly preferred groups being ethyl and hydroxyethyl radicals. The preferred range of values for y is 6-50, more preferably 6-25 and particularly preferably 9-12.

The above compounds can be synthesized using readily available commercial starting materials. Such a representation is as follows: Sodium hydride is slowly and stoichiometrically (molar Ratio 2: 1) with polyethylene glycol in a solution of tetrahydrofuran under an atmosphere of inert gas, e.g. argon. The reaction lasts 4-10 hours; one works on an ice bath to avoid the exothermic reaction to cool off. The polyethylene glycol used is commercially available and contains a mixture of compounds with Chain lengths from about 4 to about 100. The product obtained is the sodium salt of the formula

(I) Na ⁺ O ^- (CH ₃ CH ₂ O) CH ₂ CH ₂ D ^- Na ⁺

where y can have the values 3, 21, 32, 67 or 99, for example.

Then a stoichiometric amount of in tetrahydrofuran dissolved tosyl chloride slowly added to the reaction product (I), it is cooled in an ice bath and the obtained The mixture is stirred for about 12-20 hours. The polyethylene glycol ditosylate of the formula is formed

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Pyridine or another suitable base is added to the mixture; added and the solution is then poured into ice water and acidified to pH 2-3 with HCl. The aqueous solution is then extracted with chloroform ir.it, with
Washed with water and the chloroform extract is dried over sodium sulfate. The purified polyethylene glycol ditosylate (II) is obtained in this way.

The ditosylate (II) is then reacted with a tertiary amine of the formula

I ²

(III) R.-N

^R 3

in which R ^, P ^ and R ^ have the meanings given above. The reaction of (III) with (II) can be carried out without additives or with a suitable solvent, such as, for example, Ν, Ν-dimethylformamide or CIUCN at temperatures
between about 80 and 100 ⁰ C, and thus a mixture of

R ₂

N ⁺

XIV) R ₁ -N ⁺ - < ^C 2 ^H 4 ^O) yil ° 2 ^S

^R 3

^tH 3 -

(V) Dicationic ammonium by-products.

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The mixture of (IV) and (V) is then dissolved in methanol and then refluxed for 20 to ^ O hours with a treated aqueous solution of sodium sulfite. The unreacted (V) and other ionic substances are removed, by mixing the above solution with a mixed bed ion exchange resin brings into contact, then the solution filtered and the solvent evaporated. One then receives as principal zwitterionic product

CKLSO, ""

The compound (VI) can optionally be further purified and checked for purity by using the mixed-bed resin can be examined by thin-layer chromatography.

The zwitterionic compounds of general formula (VI) can be selected from any of the large number of tertiary amines (III) can be produced. Furthermore, zwitterionic compounds can be used to any specific degree desired Ethoxylation (y) can be prepared by fractionating the polyethylene glycol used in the reaction and the The desired fraction is used in the synthesis. There can also be relatively narrowly defined "distillation cuts" of the Polyoxyethylene glycol with any desired average degree of ethoxylation and with an individual content Compounds having various degrees of ethoxylation within the desired range are used in the reaction will. Likewise, the sodium salt (I) with a variety of epoxy compounds (e.g. butylene epoxide) or Halohydrins (e.g. 6-chlorohexanol or 8-bromooctanol) are converted to obtain zwitterionic products,

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which have different R ^ groups.

A specific representation of a long chain mono-ethoxylated zwitterionic connection proceeds as follows:

Preparation of 26-dimethyloctadecylammonio-3? 6,9,12,15,18, -21,24-octaoxahexacosane-1-sulfonate

Manufacture of nonethylene glycol (A)

Under nitrogen, 46 g (2 mol) of sodium beads are carefully added to 2.664 ml (20 mol) of previously dried and distilled triethylene glycol. The temperature is kept below 10O ⁰ C. When all the sodium has reacted to, the temperature is set to 100 ⁰ C and 187 g (1 mole) of 1,2-bis (2-chloroethoxy) -ethane are added in a slow stream. The mixture is ^{heated overnight at 100 °} C. (still under nitrogen) and then filtered hot in order to remove most of the sodium chloride, excess triethylene glycol is stripped off in vacuo, and the mixture is filtered hot again. The product is purified by molecular distillation and has a boiling point of 170-175 ° C at 0.001 mm.

Preparation of Nonoathylenglycolditosylat (B) 300 g (0.72 mol) of the Nonaäthylenglycol (A) are dissolved in 800 ml (10.3 moles) of dry pyridine and cooled to 0 ⁰ C. 420 grams (2.2 moles) of tosyl chloride (ie, p-toluenesulfonyl chloride) are added in small portions with stirring. When the addition is complete, the temperature is increased to 10 ^° C., the reaction mixture becoming cloudy. The mixture is stirred at 0-10 ° C. for a further 3 hours, then poured into an equal volume of ice water and acidified to pH 2-3 with 6N HCl. The aqueous solution is then extracted three times with CHCl- *. The extract is washed with water, sodium bicarbonate solution and again with water and then dried over anhydrous sodium sulfate. The evaporation of the

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CHCl, gave 520 g of a light yellow oil. Thin layer chromatography showed an impurity that remained at the point of application. The oil was dissolved in warm benzene (40 ^° C.) and extracted with warm water in order to remove the polar contamination. The benzene solution was dried, filtered and concentrated; M23 g of a yellowish oil (B) were obtained.

Production of dimethyloctadecyl-26-tosyloxy-3 _? 6.9? 12.15? ~ 18.21.2 ^ -octaoxahexacosylammonium tosylate (C) 86.7 g (0.12 mol) of the ditosylate (B) and 35.8 g of distilled dimethyloctadecylamine were refluxed for 5 hours in 400 ml of acetonitrile heated. The solvent was then removed; 120 g of a mixture of monoquaternary tosylate (C), di-quaternary ammonium by-product (D) and some unreacted ditosylate (B) were obtained.

Production of 26-Dimethyloctadecylammonio-3,6,9,12,15 _? - 18,21,24-octaoxahexacosane-1-sulfonate The mixture of mono-quaternary compound (C) and diquaternary compound (D) was dissolved in one liter of methanol. Sodium sulfite (100 g, 0.79 mol) was added and the reaction mixture was refluxed with stirring for 5 hours. More methanol was added and the insoluble salts were filtered off. The solvents were removed and a solid product was obtained.

cleaning

The above solid reaction product was dissolved in one liter of methanol and mixed with 386 g of a mixed bed resin for 5 hours (REXYN® 300 H-OH, commercially available from Fisher Scientific Co.). The solution was then through a column with fresh resin (350 g REXYInp ^ 300) with a Speed of 2 liters happened in 7 hours. The methanol solution was then concentrated to give 31.8 g

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of a slightly yellow oil. Recrystallization from acetone gave a white, crystalline, hygroscopic product. This product has been identified as the desired one End product (designated E in the following scheme).

The following abbreviated reaction scheme serves to illustrate the structures of the compounds in question. In the reaction scheme, the dimethyloctadecylamine can be replaced by dimethylhexadecylamine, dimethylnonadecylamine, dimethyleicosylamine or dimethyldocosylamine, and the corresponding compounds are obtained in which R _{1 has} the meaning of C ^ g, C ₁ Q, C ₂₀ or C ₂₂ .

EO (C ₂ H ₄ O) ₃ H Na ⁺ O "(C ₂ H ₄ O) ₃ H ' (ClCH ₂ CH ₂ O) ₂ C ₂ H ₄

(A) HO (C ₀ H ₄ O) _Q H

C ₅ H ₅ N

CH ₃

(C) ^C 18 ^H 37 Ψ " ^(C 2 ^H 4 ^O) 9

• CH ₃

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(D) Diquaternary ammonium by-product

< ^{E} C} 18 ^H 37 Ψ - ^(C 2 ^H 4 ^O) 8 ^C 2 ^H 4 ^SO 3 *

CH ₃

b.) Long-chain di-derivatives

In these derivatives, R. and R _{2 are} hydrocarbon radicals which can be straight or branched chain Cg-Cp ^ -alkyl or alkenyl groups; R- ,, R ^ and X have the same meaning as in (i), as shown above under (a); y has an average value between 6 and 100. Preferably, R and R p are identical and comprise alkyl groups, each of which has 10 to 16 carbon atoms, preferably alkyl groups each having 10 to 24 carbon atoms. The preferred range for y is between 9 and 50, very particularly preferably between 12 and 25.

A specific representation of such a connection took place as follows:

The methylation of the di-n-octylamine was accomplished by slowly mixing 50 g of the secondary amine with first formic acid (30.03 g) and then with formaldehyde at Ö ° C. The reaction mixture was maintained at 80 ⁰ C 2 ^ 4 hours and then washed with lO ^ NaOH to a pH of 8 is set up. 9 The tertiary amine obtained was extracted with CHCl, and _{dried over Na 2} SOh. The tertiary amine (25.6 g, 0.10 mol) was then mixed with 72 g (0.10 hol) of nonethylene glycol ditosylate (Compound B) in acetonitrile for 6 hours

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treated at reflux. The solvent was evaporated and the resulting mixture of mono- and diquaternary compounds was dissolved in methanol and in 100 g of sodium sulfite (pre-dissolved in water) refluxed for 16 hours. Excess sulfite and other salts were used filtered off and the filtrate was stirred for 16 hours with 500 g of a mixed-bed resin (REXYNr ^ 300). A second Treatment with fresh resin was required to remove any impurities to remove. The solvents were evaporated to complete dryness. The product, 22 g a slightly yellow viscous oil was identified as

fs

^C 8 ^H 17 - f - ^(CH 2 ^CH 2 ^O) 8 ^CH 2 ^CH 2 ^SO 3 '

^C 8 ^H 17

namely 26-dioctylmethylammonio-3,6,9jl2,15 ₃ l8,21,2 ^ -octaoxahexacosane-1-sulfonate

c.) Long-chain tri-derivatives

In these derivatives, R ₁ , R ₂ and R 3 are all hydrocarbon radicals which can be straight or branched chain Cg-Cg-alkyl or alkenyl groups; R ^ and X have the same meaning as in (i), as above under (a) and (b); y has a value between 6 and 100. R ₁ , R ₂ and R 1 are preferably identical and represent an alkyl group with 8-16 carbon atoms in the chain. Most preferably, each chain contains 8-12 carbon atoms, y has a preferred range between 9 and 50 and very particularly preferably between 12 and 50.

A specific preparation of such a connection went as follows:

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Tri-n-octylamine was distilled to ensure purity. 42 g of the purified product (0.12 mol) were reacted with 87 g (0.12 mol) of the ditosylate of nonoethylene glycol (compound B in the representation of the mono-compound), and indeed in dry Ν, Ν-dimethylformamide at 100 ° C for 2 hours. The dimethylformamide was removed and the mixture of mono- and diquaternary material was dissolved in methanol. This mixture was refluxed for 16 hours with 100 g of Na ₃ SO ₅ (pre-dissolved in water). The insoluble salts were filtered off and the piltrate was stirred with 5OO g mixed-bed resin (REXYN® 3OO H-OH) for 24 hours. A further treatment with 500 g of fresh resin was carried out for further purification. Thin layer chromatography still indicated an impurity which was then removed by dissolving the product in HpO, acidifying to pH 4 and extracting with CHCl-,. The CHCl -, extract was washed with sodium bicarbonate, dried and then evaporated; a light yellow oil was obtained, which as

f8 ^H 17 ₇ - f - (CH ₂ CH ₂ O) ₈ CH ₂ CH ₂ SO ₃ "

^C 8 ^H 17

sulfonate was identified.

il) R ₁ - N - (C ₂ H ₄ O) ^ ₁ - CH ₂ CH ₂ X (I)

(C Η _Λ 0) H * 2 4 'χ

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In this structural formula, R _{1 is} a linear or branched chain C _{6 -C 22} alkyl or alkenyl group, preferably a C 1 -C 4 alkyl or alkenyl group; R ₂ is a Cg-C ^ _Q -alkyl or alkenyl group or a C - ^ - C ^ -alkyl or hydroxyalkyl group, preferably a methyl group; X ~ is a sulfonate or sulfate residue.

The number of ethylene oxide groups in each chain can lie between 1 and 100, but their sum should be greater than 10. In general, each chain will approximate the same number, the sum of the groups in both chains preferably having a value between 12 and 50 and very particularly preferably between 12 and has.

The preparation of the zwitterionic compounds of this type is carried out using commercially available starting materials. A typical starting material is called "ETHOQUAD" by the Armak Company under the trade name "ETHOQUAD" Company distributed. "ETHOQUAD" is a mixture of quaternary ammonium compounds whose predominant Component of a diethoxylate of the formula

Cl

is. In this formula, y and χ are integers greater than 0, the average sum of which is, for example, 5> 10, 15 or 50, depending on the selected "cut"; P ₁ and R_ represent C 1 -C 4 alkyl and Cj-C ^, respectively

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These compounds are made by dissolving "ETHOQUAD" in pyridine or another suitable base. The mixture is cooled to about 0 ⁰ C. Tosyl chloride is slowly added to the "ETHOQUAD" mixture in a stoichiometric ratio of 1: 1 while the reaction mixture is kept at about 0-5 ° C in the ice bath. The mixture is then stirred at this temperature for about 2k hours. The reaction mixture is then poured into water and acidified to pH 2 to 3 with HCl.

The above acidified reaction mixture is then extracted with chloroform, and the extract is first mixed with sodium bicarbonate solution and then washed with water. The extract is then dried over anhydrous sodium sulfate. To Evaporation of the chloroform extract gives an oily residue. This is the mono-tosylate ester of the formula

(CAO) ,, -P ₉ S- _

Cl

in which y and χ have the meanings given above.

This tosylate ester is then dissolved in methanol and refluxed for about 24 hours with about a 10 molar excess of sodium sulfite (pre-dissolved in H ₃ O). The reaction mixture is cooled and excess sodium sulfite and sodium tosylate are removed by filtration. The filtrate is stirred with a mixed-bed resin (anion-cation) in order to purify the product. A second resin treatment can optionally be followed by essentially

1Π63

all traces of cationic and anionic impurities to remove. The purified monosulfonate, accordingly (I) is obtained by evaporation of the solvent. The product can optionally be recrystallized from acetone four den.

iii)

CH ₂ CH ₂

- ^CH 2 ^CH 2 - ■ *

^H 2 ^CH 2

(XI).

In this formula, R 1, R ₂ and X have the same meanings as in (ii); y and χ each have a value between 1 and 100, where y + x ~ 10. Preferred values for the sum y + χ are in the range from ^{12-50 and very particularly preferably in the range from 15-25. The cation M +} is an alkali metal, ammonium or alkanolammonium, such as ethanolammonium or methanolammonium, but preferably sodium.

The disulfonate (II) is prepared in the same way as the monosulfonate (I), but using an excess of tosyl chloride (molar ratio about 3: 1 or greater) in the first step and a larger excess of sodium sulfite (molar ratio 20: 1) in the second step. If there is any other cation M than sodium in the final product if desired, the corresponding sulfite can be used in the second step. It can also take the natural form of Compound (II) converted into any other cation form by ion exchange. A cleaning treatment with resin is not necessary when making the disulfonate.

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The sulfates of type (I) and (II) are prepared in a simple manner by adding one or two moles of the chlorosulfonic acid implemented with "ETHOQUADS". The same applies to the selection of the cation M for the sulfates and the sulfonates Considerations.

A wide variety of diethoxylated amino feedstocks can be used in the above reaction scheme. For example, "ETHOQUAD" derivatives with variations in groups R ₁ and R ₂ are commercially available, such as compounds in which R ^ has an average "cut" of C ^ ₂ . In addition, intermediate products with different sums of y and χ within the specified range can be selected. Compounds in which y and χ have approximately the same fourth, the sum of y and χ being between 12 and 25, particularly preferably between 15 and 25, are particularly useful.

A large number of other starting compounds can also be used in order to produce the numerous diethoxylated precursors of the zwitterionic compounds according to the invention. For example, the "ETHOMEENS" (trade name of a class of compounds sold by the Armak Company, a division of the Armor Company) can be quaternized in order to obtain modifications of the commercially available "ETHOQUADS". So "ETHOMEENS" of the general formula RN (C ₂ Hjj0) _x H (C ₂ H _{i {} 0) H, in which R is an alkyl radical, with an excess of alkyl iodide or hydroxy-substituted alkyl iodide (CH-, Ι, C ₂ Ht -I) are converted to a quaternary ammonium compound which can be sulfated or sulfonated on one or both ethylene oxide groups in the manner described above.

In the compositions of the invention, mixtures of any of these zwitterionic compounds can be used in each

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Ratio used v / earth. Such mixtures can be done on purpose can be produced by mixing individual species, or can emerge as a result of selection of the starting materials or as a result of the selected manufacturing process.

The ethoxylated zwitterionic compounds of the present invention exhibit remarkable solubility in aqueous media. In order to achieve a satisfactory removal of dirt particles, a water solubility of at least 50 ppm, preferably more than 75 ppm, is required at 25 ° C .; however, the preferred materials have solubilities in water of 10-30% by weight .

The second essential component of the composition of the invention is a detergent builder. This can be present in proportions of 1-99 wt .- # (based on the composition); the actual proportion depends on the particular use of the composition and its desired physical form.

Inorganic detergent builders which can be used according to the invention are alkali metal, ammonium and alkanolammonium polyphosphates (e.g. tripolyphosphates, pyrophosphates and glass-like polymeric meta-phosphates), phosphonates, silicates, Carbonates (including bicarbonates and sesquicarbonates), sulphates, borates and aluminosilicates.

Specific examples of polyphosphates that can be used according to the invention are the alkali tripolyphosphates, sodium, Potassium and ammonium pyrophosphates, sodium and potassium orthophosphates, Sodium polymetaphosphates in which the degree of polymerization is between about 6 and about 21. In particular The alkali tripoly- and pyro-phosphates are preferred.

509887/1063

Examples of suitable phosphonate framework salts are the water-soluble salts of kthane-1-hydroxy-1,1-diphosphonate, in particular sodium and potassium salts; the water-soluble salts of methylenediphosphonic acid, ζ.E. the trisodium and tripotassium salts and the water-soluble salts of substituted methyldiphosphonic acid, such as, for example, trisodium and tripotassium ethylidene, isopropylidene-benzylmethylidene and halomethylidene phosphonates. Phosphonate framework salts of the types described above are described in U.S. Patents 3,159,581 _} 3,213,030, 3,422,021, 3,000,148, and 3,422,137, which are incorporated herein by reference.

Preferred silicate builders are the alkali silicates, especially those with a SiOp: NapO ratio of 1.6: 1 to 3.2: 1. However, other silicates are also useful, such as magnesium silicate used in granular formulations as a curling agent, as a stabilizer for oxygen bleaching (e.g. sodium perborate) and as a component of foam control agents can serve.

Examples of preferred carbonate builders are sodium carbonate and sesquicarbonate and their mixtures with ultrafine calcium carbonate, as described in DOS 2 321 001, to which reference is hereby made.

Alkali borates suitable for the purposes of the invention are e.g. sodium tetraborate decahydrate and potassium pentaborate tetrahydrate.

Aluminosilicate builder salts used in accordance with the invention can be used have the following general formula

(SiO ₂ ) _y ]

Π 9 B 8 7/1 0 6 3

In this formula ζ and y are integers of at least 6, the molar ratio of ζ to y is in the range of 1.0 up to about 0.5 and χ is an integer from about 15 to about 264. Such aluminum silicates expediently have a particle diameter from 0.1 to 100 microns, a calcium ion exchange capacity of at least about 200 milligram equivalents / gram and a calcium ion exchange rate of at least about 1.9 ° dH (2 grains / US gallon) / minute / gram Detergent compositions containing aluminosilicate builder salts of these types are described in BE Patent 814474, which is incorporated herein by reference.

Organic detergent builders suitable according to the invention are, for example, although this list is not exhaustive, alkali, Ammonium and alkanolammonium salts of ethylenediaminetetraacetic acid, Nitrilotriacetic acid, phytic acid, mellitic acid and mixtures thereof with benzene pentacarboxylic acid, benzene-1,3,5-tricarboxylic acid and 1,3> 5-trihydroxybenzene-2,4,6-trisulphonic acid, Citric acid, itaconic acid, oxydisuccinic acid, carboxy-methyloxysuccinic acid, polymaleic acid and Copolymers of maleic anhydride with ethylene or vinyl methyl ether. These and other suitable organic detergent builders are disclosed in U.S. Patent 3,308,667, published Japanese Patent Application 73,703, U.S. Patents 3,699,159, 3,758,420, 3,812,044, and 3,635,830 which are hereby incorporated by reference Is referred to.

Any mixtures of the above detergent builders can also be used be used. Some particularly advantageous blends are disclosed in US patents 3 356 613 and 3 392 121.

The following tables illustrate the soil removing effect of the compositions of the invention composed of ethoxylated zwitterionic compounds and numerous Detergent builders.

$ 09887/1063

Table I shows the effect of a number of inorganic ones and organic builders on the clay soil removal effect of two ethoxylated zwitterionic compounds, which alone have a good effect. At a stake zwitterionic compound of 250 ppm becomes an improvement achieved by adding each substance, with special advantages with cotton and polyester. With a proportion of zwitterionic compound of 125 ppm, the Addition of the builder in most cases an improvement in the effect on the degree that is ethoxylated by 250 ppm zwitterionic connection is achieved alone, and in some cases even exceeds it.

Table II shows similar results for two ethoxylated zwitterionic compounds, the particles of dirt removal effect is not good in the absence of a builder particularly i. It has been shown that certain detergent builders can raise the screen-removing effect of these "poorer" materials to the level attained by those ethoxylated synthetic compounds which are already good per se; in some cases they even match the effect of control product A, which is used in a much higher concentration (1400 ppm).

The effect of the combination between builder and ethoxylated zwitterionic compound is shown for a range of different zwitterionic compounds by Table III. It can be seen that a composition containing C _{6 alkyl dimethyl derivative (Run No. 4) does not have good soil removing properties (see the C 12} "alkyl and C 1-4 alkyl compounds in Table II); however, the effect improves somewhat with the Di-Cg derivative (experiment no. 5) and is then noticeably better for that derivative in which the methyl side chain is completely replaced by Ch-

509887 / 10R3

alkyl groups is substituted (Experiment No. 6). Experiments 9 and 10 show that it may be desirable to have a given Exceed water solubility; it can be seen that the prior dissolution of a compound with low water solubility (approx. 50 ppm) in methanol slightly improved the effect, however, it is not essential to obtain a sufficient soil removing effect.

Table IV shows the influence of the proportions of builder and ethoxylated zwitterionic compound. It can be seen that the use of a builder combination which reduces the mineral hardness makes it possible to reduce the proportion of ethoxylated zwitterionic compound considerably (tests 8 and 9). The use of less efficienten builders allows not have the same flexibility for the formulation, since then the soil removal effect on the proportion of ethoxylated zwitterionic compound depends more (Experiments 3 _S ^ and 5).

The soil removal results show that those ethoxylated zwitterionic compounds that have a inherently good performance, in combination with a detergent builder, a substantial reduction in the Part of the zwitterionic compound allowed ^ where the Reduction goes hand in hand with the ability of the builder to reduce mineral hardness. In those ethoxylated zwitterionic compounds that do not have as good soil removal properties combine with detergent builders at a level of zwitterionic Compound of 125 ppm in solution an improvement found in In most cases, the effect of the control product is the same or even superior at the recommended concentrations.

^ 09987/1 (J 63

Table V shows the results for the removal of grease and oil soils. Compositions containing C ^ gdimethyl-octaäthenoxy -verbindungen, the C. ^ homologous and containing 1: 1 mixtures of these two all show one Improvement in grease and oil removal when using a detergent builder; however, the effect varies depending on the type of fabric and the type of dirt. In general, a remarkable improvement can be seen in polyester for both types of soiling, but the effect is very different with polycotton, especially with soiling of the triglyceride type.

In summary, it can be said that the addition of a detergent builder to the ethoxylated zwitterionic compounds according to the invention, the oil and grease removal properties on synthetic fibers improved, while the effect on cotton of the type of pollution and the Type of builder combination depends.

509887/1063

OO OO OO

CD CTi CO

No,

10
11
12th

Table I Clay Soil Removal: Ethoxylated

Combination with detergent builder

Conditions: 10 minute wash in Tergotometer; 6.7

Builder

Ethoxylated zwitterionic compound

zwitterionic compounds in ffen
° dH (Ca: Mg = 2: 1); Temp .: 40 ⁰ C

Relative dirt

N
]

11
ti
11
11

dd

Il
Il
11

dd

11

dd

11
ti
It

It

, Ν-bisCH, ammonio)

CH ₂ CH ₂ SO

(NC ₂₁ H ₂₁ , Ν, Ν-bisCH, ammonio) (CH ₂ CH ₂ O) ₅ CH ₂ CH ₂ SO ₃

Proportions of ppm in solution

250

125 250 125 250 125 250 125 250

125 250 125 250 250 125 250 250

25O

Na ₅ P ₃ O ₁₀

It

CaCO * / Na "CO, 3 2

It

Sodium NTA

It

Sodium citrate CH (COONa) ₂ OCH ₂ COONa

11 Na ₂ CO ₃ VNa ₂ SiO ₃ *

SiO ₂ : Na ₂ O = 3.2: 1 CaCO ₃ surface proportions
ppm in
solution

25O

25O

25O

25O

500

500

100/200
100/200

I80

I8O

300

300

300
200/200

200/200

distance index

cotton

• 75

62 104 100 111

92 104

65

93

'63

117

98

111

104

92

90

94

Polycotton

96

100

97

102

90

94

93

95

93

98

97

94

103

101

106

95

107

polyester

95

77 101

105

112 106 107

93 104

99 122 116 101 106 104 109

U & 01

U)

U)

-0115

CJI

m / gram (<= * 0.02 ji)

ο co

-4

CJ

o ζ

co TI

rn D

Table II Clay Soil Removal: Ethoxylated Zwitterionic Compounds in

Combination with detergent builders Conditions: 10 minute wash in Tergotometer; 6.7 ° dH (Ca: Mg = 2: 1); Temp .: 40 ⁰ C

No. Ethoxylated zwitterionic
link Shares
ppm in
solution Builder Shares
ppm in
solution Ternun
tree
wool gindex
Poly- _λ .
cotton Poly
ester 1 (NC ₁ JlH ₂ - N, N-bisCH ₃ ammonio) 25O - ■. ; - 53 69. 46 2 It 125 - 41 52 24 3 250 Na ₅ P ₃ O ₁₀ 250 94 90 98 4th Il 125 250 62 73 39 5 dd 250 Na ₄ P ₃ O ₇ 25O 94 88 99 6th ti 125 dd 250 77 80 80 7th dd 250 Na ₁₂ (AlO ₂ .SiO _2. ) ₁₂ 27H ₂ O 25O 85 92 88 8th dd 125 Il
* 250 61 75 44 9 Il 250 CaCO ₃ VNa ₂ CO ₃ 100/200 92 96 84 10 It 125 ti 100/200 70 78 44 11 t! 250 Sodium NTA 180 100 94 109 12th dd 125 It 180 55 65 33 13th dd 25O CH (COONa) ₂ OCH ₂ COONa 300 98 103 99 14th dd 125 1! 300 86 84 55 15th ti 250 Na ₂ CO ₃ ZNa ₂ SlO ₃ 200/200 80 92 75 16 (NC ₀ HJ. NN-bisCH, ammonio) 25O - 50 46 ³³ ! S> (CH ₂ CH ₂ O) ₅ CH ₂ CH ₂ SO ₃ _ cn 17th ti 25Ö 200/200 68 67 4ΐ ^ω
41 CO

SiO ₂ : Na ₂ O = 3-2: 1

CaCO ₃ surface 100 m'Vgram («= * 0.02 μ)

CD cn

'S) OO 30

Table II I soil removal effect on a number ethoxylated zv, ^r itterionischer compounds in combination with a carbonate / silicate builder system (silicate ratio SiO ₂ INa O ₃ = 3.2: 1)

Conditions: 10 minute wash in Tergotometer; 6.7 ° dH (Ca: Mg = 2: 1); Temp .: 4O ⁰ C

No. Xthoxylated zwitterionic
link Shares
ppm in
solution Builder Shares
ppm in
solution Relati ¹
fernun
tree
wool vev Schm
gindex
Poly-
cotton useful
Poly-
ester 1 (NC ₁₈ H ₃₇ Ν, Ν-bisCH, ammonio). 25O __ - 94 98 98 2 (CH ₂ CH ₂ O) ₈ CH ₂ CH ₂ SO ₃
Il 250 Na CO / Na SiO 200/200 104 103 113 3 (N-CrIi, -, Ν, Ν-bisCH-, ammonio)
16 33 3 250 ! I Il 200/200 91 99 109 4th (CH ₂ CH ₂ O) ₅ CH ₂ CH ₂ SO ₃
(N-CgH ₁₇ Ν, Ν-bisCH, ammonio) 250 11 Il 200/200 46 53 39 VJl (CH ₂ CH ₂ O) ₈ CH ₂ CH ₂ SO ₃
(N, N-bisC ₈ H ₁₇ N-CH ₃ ammonio) 250 Il II 200/200 52 62 33 6th
7th (CH ₂ CH ₂ O) ₈ CH ₂ CH ₂ SO ₃
(N, N, N-trisCgK ₁₇ ammonio)
(CH ₂ CH ₂ O) ₈ CH ₂ CH ₂ SO ₃
(N, N-bisC ₁ QH ₂₁ N-CH ₃ ammonio) OO
LP, LPi
CM CM It Il
Il Il 200/200
200/200 82
101 92
95 101
109 8th (CH ₂ CH ₂ O) ₈ CH ₂ CH ₂ SO ₃
ZN-C ₁₈ H ₃₇ N _5-CH, N (CH ₂ CH ₂ O) H
ammonio7 (CHpCH ₂ O) CHpCH ₂ SO, 25O tt It 200/200 73 87 95 where x + y = 15 9 (NC ₁₈ H ₃₇ N, N-bisCH ₃ ammonio) 25O ti Il 200/200 58 93 112 10 (CH ₂ CH ₂ O) ₈ CH ₂ CH ₂ <G2> S0 ₃ .
"" (pre-dissolved in methanol) 25O It Il 200/200 104 109 114

fs) cn co, co -J CD cn

Table IV Effect of changing the proportions of ethoxylated zwitterionic
Compound and builder on the soil removal effect

Conditions: 10 minute wash in Tergotometer; 6.7 ° dH (Ca: Mg = 2: 1); Temp .: 40 ⁰ C

ro cn co co —J

cn • EthoxyIiert e second e- Proportions ppm in • Builder Aaateile \ pp.m ^; : Relative dirt-- • roiy-.
cotton jfoiy-
ester ■ 107 ^: O ₂ ; rioiiische connection Solution - ■. - ι.η · Solution. ■ removiang's'index. 98- ^: No. °° 3 N-C, _H "_ N, N-to CH, 250 · _ ·,., '■■ -. . tree
wool 1 (ilU) _ CxI-CrL. ο U-
X ^^ Φ Q ^ ^^ 5 O
ϋ MMO * 94 103 113 II 250 Na ₃ CO ₃ ZNa ₂ SiO ₃ * 200/200 - i 42 Λ Il 13th NaPO ₁ . '■ 250/200 / 20C 104 'CM
«A 5 Na ₂ CO ₃ .51 I. 6th Na ₃ SiO ₃ * ■ - ■ 81 7th M. . 50 ii. . . . 250/200 / 20C 103 106 8th Il 125 'Il 250/200 / 20C 63 108 125 Il 125/200/200 85 - 104 9 Il 125 11 ■ ' ^: · 50/200 / 20C 73 101 106 ti ■ 63 Na ^ ₂ (AlO ₂ SiO ₂ ) ₁₂ 27H ₂ O 600 75 Na ₂ CO ₃ / Na ₂ SiO ₃ * ■ 200/200 75 109 Il 125 11 ii • 600 .M 'Il 200/200 90 ·

3 · 2: 1

Table V Removal of fat and oil by combinations of ethoxylated
zwitterionic compounds and detergent builders

Conditions: 10 minute wash in Tergotometer at 38 ⁰ C and 5.3 ° dH- (Ca: Mg _ =. 3: 1)

cn co co

co cn '

No. Ethoxylated zwitterionic
link Shares
ppm in
solution Builder. ^Na 5 ^P 3 ° 10 Shares
ppm in
solution Polyco
^x) TG % tton
*
"^ HC % Poly «
TC ⁰ Zo 5th
HC % cn ———
O
co 1
£ * Ö (NC. .H-- N, N ~ bisCH, ammonio)
Io JJ J ■ 250 mm mm Na ₁₂ (AlO ₂ .SiO _2. ) ₁₂ 27H ₂ O - 91 132 75 102 Il 2 (CH CH O) CH CH SO
2 2 8 2 2 3
Il 250 250 97 143 98 109 ο 3
σ> Il 500 H. P 0 ' 500 88 121 99 115 u> 4 (NC. "Η_ _Λ Ν, Ν-bisCH- ammonio)
14 'ώ 3 -5 250 Na ₁₂ (AlO ₂ .SiO _2. ) _X2 27H ₂ O 100 75 80 99 5 (CH-CH ₀ O) CH CH SO
Δ Δ Ο Δ Δ ■ j
Il 250 250 76 · 122 100 126 6th Il 250 ^Na S ^P 3 ° 10. '5QO 63 93 88 111 7th C ₁ -ZC ₁ ^ mixture 125/125 Ha ₁₂ (AlO ₂ .SiO ₂ .J ₁ ^ VH ₂ O - ■ 91 121 77 21 8th Il 125/125 ' • 250 127 86 112 123 9 Il · 125/125 500 78 121 104 117

■ +) triglyceride

'++) "hydrocarbon

Optional components ,

In addition to the ethoxylated zwitterionic compounds and detergent builder, the compositions of the present invention can contain other conventional ingredients as commonly used in such products. The main optional ingredient is a second surfactant (cosurfactant) which can be non-ionic, zwitterionic, ampholytic, anionic or cationic. Nonionic, zwitterionic and ampholytic cosurfactants can be present in amounts between 5 and 95% by weight , based on the composition of ethoxylated zwitterionic compound and builder. Cationic surfactants with a hydrophilic residue in the molecule (e.g. hydroxy, hydroxyalkyl and ethenoxy groups) can also be used in the amounts indicated, but cationic surfactants that do not have these groups reduce the soil removing properties of the ethoxylated zwitterionic compounds. Anionic Cosurfactanten are preferably employed in amounts which 100 wt -.% Not exceed the ethoxylated zwitterionic compounds.

Special mixtures of cosurfactant and ethoxylated zwitterionic compound are described in of the German patent application filed at the same time (our no. 20 048.)

Another optional ingredient is an enzyme for removing protein or carbohydrate stains. Enzymes for protein stain removal are proteolytic in nature, such as those under the tradenames "Alcalase" and "Esterase" from Novo Industries A / S (Denmark) or the one under the trade name "Maxtase" and "AZ Protease" from Gist-Brocades N.V. (Holland)

509 8 87/10 63

sold. These substances are usually in proportions up to 1% by weight added, preferably 0.25 to 0.75% by weight; they are preferably coated or spray crystallized with inert additives to reduce dust formation and improve shelf life. One a large number of such enzyme substances and means for their incorporation into the synthetic detergent granules are disclosed in US Pat U.S. Patent 3,553,139.

Another ingredient that can be used to improve product properties is a halogen or oxygen-containing bleach. Examples are trichloroisocyanuric acid, sodium and potassium dichloroisocyanurates and the N-chloro- and N-bromoalkanesulfonamides. These substances are usually used in an amount of 0.5 to 10 wt -% of the final product is added, preferably in an amount of 1 to 5 wt .- / ?..

Examples of oxygen-containing bleaches are sodium perborate , Sodium percarbonate and potassium non-persulphate; they are added in proportions of 5 to 30, preferably 10 to 25 wt .- # of the end product. The usage of organic bleach activators such as phthalic anhydride, tetraacetylethylenediamine, tetraacetylmethylenediamine or Tetraacetylglycouril, causes during the washing process in situ the corresponding organic peroxy selurates which develop good bleaching properties at low temperatures. Activators of this type are used normally used with sodium perborate, and indeed in an amount of 5 to 15% by weight (based on the end product).

Substances to improve or modify the foam properties of the composition can also be added. Examples are coconut and tallow mono- and di-alkanolamides, in particular ethanolamides and C ₁ pC. _ς -

509887/1 (163

alkyl-di-lower-alkyl-amine oxides. Ker typical Schaumunterdrük are long-chain fatty acids such as disclosed in U.S. Patent hard 2 95 ¹⁾ 5 ^ 7 and combinations of these with certain non-ionic substances, in US Patent 2 95 J ¹ 3 ^ 8 as described.

-Other optional ingredients of granular products are hydrotropic and anti-caking additives, such as salts of lower alkaryl sulphonic acids, salts of ot.-sulphosuccinic acid, oC-sulphobenzoic acid and urea; they are usually used in proportions of 0.5 to 5 wt .- # (based on the end product), preferably with proportions of 1 to 3 wt. In approximately equal proportions, C ^ -C.g-alkyl acid phosphates and their Condensation products with ethylene oxide used to control viscosity for crutcher mixing v / earth. Antifouling agents such as carboxymethyl cellulose, hydroxyethyl cellulose and theirs Derivatives can also be added.

Anti-fog and anti-corrosive agents, fragrances and colors can also be added, the latter conveniently as a general color or in the form of sprinkles applied to a granular fraction of the entire formulation or to the granular of one or more of the ingredients.

The pH of the detergent compositions according to the invention can vary between 5 and 12, but is preferably in the range of 8.0 to 10.5 as this is somewhat Way is beneficial for dirt removal on synthetic Fibers. However, the choice of certain optional components, such as enzymes, may dictate the choice of one Make pH necessary, which ensures an optimal effect of the composition in question.

509867/106

Granular formulations of the compositions according to the invention can be made by any of the conventional techniques, e.g., by slurrying the individual components in water, subsequent comminution and spray drying, or by pan or drum granulation of the components.

The liquid formulations of the compositions according to the invention can be provided with or without builders. When the compositions do not have builders, they generally contain about 30 to 50 % total surfactants, about 1 to 10 % organic base such as mono-, di- or tri-alkanolamines, solubilizers such as alkali halide, and a lower one primary alcohol, such as ethanol or isopropanol, and about 30 to 10% v / water. Such compositions are generally homogeneous, single phase liquids of low viscosity (about 100 to 150 centipoise at

Liquid detergent compositions provided with builders can also be single phase liquids, provided that the builder can be dissolved in the amount employed. Such liquids generally contain 10 to 25 % total surfactants, 10 to 20 % builder (organic or inorganic), 5 to 10 % hydrotropes and 50 to 60 % water. The liquids of this type also have a low viscosity (100 _; to 150 centipoise at 24 ° C). The present invention also includes liquid detergents which have been provided with builders and which contain constituents which form heterogeneous mixtures or which contain builders that are not entirely soluble. Such fluids generally contain viscosity modifiers.

509887/1063

The following examples serve to illustrate the present invention.

Example I.

A concentrated detergent formulation with the consistency a thick paste was made from the following ingredients (wt. ~ #):

u / - (hexadecyl-dimethyl-ammonio) -. 38.4% 2-octaethenoxyethane-1-sulphonate sodium carbonate 30.8

Na-silicate (SiO ₃ : Ma ₃ O = 3.2: 1) 30.8

100.0%

Viaren provided tissue samples of cotton, polycotton and polyester, with a standardized illite clay Verschrcutzung, were treated with the above product for 10 minutes in a Tergotometer at 40 ⁰ C in V / ater of 6.7 dH (Ca: Hg = 2 : 1) washed. The concentration of the product was adjusted so that there were 250 ppm of the zwitterionic compound in solution. After rinsing and drying, the fabric swatches were then instrumentally examined for soil removal using a Hunter Color Difference Meter. . The results, expressed as a percentage of that effect of the Standard Formulation A at a concentration of 0.10 weight -% was obtained under the same conditions, were as follows:

Cotton polycotton polyester

9255 106 $ IO955

Example II

It became a solid, powdery formulation of the following Composition made:

609667/1063

w- (ii-Octadecy 1, N-methyl-iJ-polyäthenoxyamrconio) -2-polyäthenoxyäthan-l-sulphonat, wherein the total number of ethylene oxide groups in molecule 14 is $ 27.8 Na tripolyphosphate 27.8 Na carbonate 22.2

Na-silicate (SiO _p : Na "O = 3.2: 1) x 22.2

^ 100.0%

Under the same conditions as in Example I, the following results were obtained:

Cotton polycotton polyester

5098R7 / mf5

Claims (11)

- 40 patent claims :, Detergent composition containing: A.) 1 to 99% by weight (based on the composition) one Compound of formula i) B ₁ - H * .-. in which the symbols have the following meanings: R ₁ = straight or branched chain alkyl or alkenyl radicals with 8-30 carbon atoms or alkaryl radicals with 10-24 C atoms in the Älky! Group; R ₂ = straight or branched chain alkyl or alkenyl radicals with 8-21 carbon atoms, alkaryl radicals with 6-16 carbon atoms in the alkyl group or alkyl or hydroxyalkyl group with 1 - 4 carbon atoms; R, = straight or branched chain alkyl or alkenyl radicals with 8-21 carbon atoms, alkaryl radicals with 6-16 carbon atoms in the alkyl group, alkyl or hydroxyalkyl radicals with 1-4 carbon atoms or the group - (C ₂ H ^ O) _x H, where χ is a number is from about 3 to about 50; Rj ₁ = C ^ -Cg -alkylene, C ^ -Cg-alkenylene, 2-hydroxypropylene, 2- or 3-Hydrojtybutylen or alkarylene radicals with 1-4 C atoms j where Rj. Has the meaning of -CH ₂ -CHp- if R ^ is the group - "(C ₂ -HjIjO) _x H; X ~ = sulfate or sulfonate ions; y = a number for 2 - 100, where χ + y -10, if P-, the Meaning - (C ₂ H ^ O) _x Ii; or the formula +) in the alkyl group 50-9887 / 1063 ii) R ₁ -N ⁺ - (C ₂ H ₄ O) - CH ₂ CH ₂ - X - M ⁺ in which the symbols have the following meanings: R ₁ = straight or branched chain alkyl or alkenyl residues with 8 to 30 carbon atoms; R ₂ = straight or branched chain alkyl or alkenyl radicals with 8 to 30 carbon atoms or alkyl or hydroxy alkyl radicals with 1-4 carbon atoms; X ~ = sulfate or sulfonate; _x > ^ ⁿ y = numbers from 2 - 100, where χ + y ^ l2; M = alkali metal, ammonium or alkanolammonium cation; B.) 99-1% by weight (based on the composition) of a detergent builder. 2. detergent composition according to claim 1, characterized in, that it contains an inorganic builder, namely alkali metal, ammonium or alkanolammonium polyphosphates, carbonates, bicarbonates, silicates, aluminosilicates, borates or sulfates. In that it contains 3- detergent composition according to claim 1, characterized in that an organic builder, namely Alkalimetallammonium- or Alkanolammoniurcsalze the fithylendiamintetraessigsäure, nitrilotriacetic acid, citric acid, oxy ^ succinic acid, carboxymethoxysuccinic acid, benzene-penta- or Hexacarboxylsäure, 1.3 ₃ 5- ■ 5 Ό 9 8 «7/1 Π 6 3 Trihydroxybenzene-2,4,6-trisulfonic acid or copolymers of maleic anhydride with vinyl methyl ether and ethylene. 4. Detergent composition according to claim 1, characterized in that the zwitterionic compound is the formula in which the symbols have the following meanings: R ^ = straight or branched chain alkyl or alkenyl residues with 16 to 22 carbon atoms; R ₂ = alkyl group with 1 to 3 carbon atoms; χ + y = 12 to 50. 5. Detergent composition according to claim 4, characterized characterized in that R ^ is a straight or branched chain Is alkyl or alkenyl radical with 16 to 18 carbon atoms and χ + y has a value from 15 to 25. 6. Detergent composition containing: A.) 1 to 99 wt -.% (Based on the composition) of a compound of the formula i - N ⁺ - (CH, 0) RX 1 ι · 2 4 y 4 ^R 3 609887 / 1Π63 in which the symbols have the following meanings: R ₁ , R ₂ and R ₃ = straight or branched chain Cg-C ^ g- alkyl or alkenyl radicals; R ₁₁ = C ₁ -Cg -alkylene, C ^ -Cg-alkenylene, 2-hydroxypropylene, 2- or 3-hydroxybutylene or alkarylene radicals with 1 - 4 carbon atoms in the alkyl group; X ~ = sulfate or sulfonate; y (average value) = 6 - 100 and B.) 99 to 1 wt .- $ (based on the composition) a detergent builder. 7. detergent composition according to claim 6, characterized characterized in that y has a value of at least 9. 8. Detergent composition containing: A.) 1 to 99 Ge \ 'i .-% (based on the composition) of a compound of the formula I ² R ₁ -H ⁺ - (C ₂ H ₄ O) ^R 3 in which the symbols have the following meanings: R ₁ and Rp = straight or branched chain alkyl or Alkenyl radicals with 6 to 21 carbon atoms; Rz = C ₁ -C _i | -alkyl or hydroxyalkyl radicals; R ₁ J = C ^ -Cg -alkylene, C - ^ - Cg-alkenylene, 2-hydroxypropylene, or 2- or 3-hydroxybutylene or alkarylene radicals with 1 to H C atoms in the alkyl group; X ~ = sulfate or sulfonate; y (average value) = 6 to 100. B.) 99 to 1 % by weight (based on the composition) of a detergent builder. 9. Detergent composition according to claim 1, characterized in that the compound has the following formula I ² R ₁ -N- in which the symbols have the following meanings: R ^ = straight or branched chain alkyl or alkenyl residues with 8 to 30 carbon atoms; R ₂ and R-, = C 1-4 alkyl or hydroxyalkyl radicals; Rjj = C ₁ -Cg -alkylene, Cz-Cg-alkenylene, 2-hydroxypropylene, 2- or 3-hydroxybutylene or alkarylene radicals with 1 to 4 carbon atoms in the alkyl group; y = 6 to 20. according to claim 9 10. Detergent composition, characterized in _f that the symbols have the following meanings: R ₁ = alkyl radical with 12 to 18 carbon atoms; Rp and R = alkyl or hydroxyalkyl radicals with 1 to 3 carbon atoms;
Rl ₁ = -CH ₂ CH ₂ -;
y = 6 to 12. 11. Composition according to claim 1, characterized in that it is anionic, non-ionic, ampholytic S 0 9 8 R 7/10 6 3 see or contain zwitterionic surfactants . For: The Procter & “Gamble Company Cincinnati, (fthio, V.St.A. Lawyer 509887/1063