CH648344A5 - DETERGENT COMPOSITION WITH LOW PHOSPHATE CONTENT FOR WASHING TEXTILES. - Google Patents

Description

The present invention relates to detergent compositions which have greatly improved ability to remove greasy and oily dirt and body dirt. The compositions can be phosphate-free; however, they can also contain small amounts of phosphate materials, but generally no amounts above about 20% by weight. These detergent compositions provide an unexpectedly high degree of removal of greasy and oily dirt (such as motor oil, triolein, animal fat and lipstick); they also provide excellent removal of particulate dirt, especially clayey dirt, as well as fabric care effects such as Softening of textiles, combating static electricity and inhibiting dye transfer.

Nonionic surfactants are generally included in laundry detergent compositions because of their ability to attack greasy and oily soils. Cationic surfactants are also primarily used in detergent compositions to provide additional fabric care effects and not for the purpose of improving cleaning performance. Certain cationic surfactants have a germicidal or disinfectant effect on washed surfaces; see e.g. the U.S. patent

2,742,434 of Kopp, issued April 17, 1956; the U.S. patent

3,539,520 to Cantor et al., Issued November 10, 1970; and Lancz U.S. Patent 3,965,026, issued June 22, 1976. Other cationic surfactants, such as ditallow alkyl dimethyl ammonium chloride, are included in detergent compositions to provide a fabric softening effect as disclosed in that U.S. Patent 3,607,763 to Salmen et al., Issued September 21, 1971; and U.S. Patent 3,644,203 to Lamberti et al., issued February 22, 1972. Such components are also used to combat static and to soften laundered fabrics, such as e.g. in U.S. Patent 3,951,879 to Wixon, issued April 20, 1976; and U.S. Patent 3,959,157 to Inamorato, issued May 25, 1976.

The compositions according to the invention have an exceptional cleaning power. In normal substance wash tests, these compositions were found to be three to four times as effective in removing some typical greasy and oily stains as conventional laundry detergents, including commercially available high performance liquid detergents that contain a high level of nonionic surfactants. The same detergent compositions with or without phosphate components or other builder components are also at least as effective as and, in some cases, much more effective than conventional granular laundry detergent compositions with full builder content and also lend the washed textiles a number of textile-caring, advantageous for removing clay soiling Effects such as softening the textiles, controlling static electricity and inhibiting dye transfer. The compositions according to the invention thus offer the consumer a rounded cleaning and textile care performance. These results, which are far better than those achieved so far, especially when removing greasy and oily dirt, are the result of an as yet unknown cleaning potential of certain selected cationic surfactants when used in the presence of certain selected nonionic surfactants according to the Cloud point and reduced cationic monomer concentration requirements herein are used.

It is an object of the invention to provide laundry detergent compositions which provide excellent removal of greasy and oily dirt and body dirt.

It is another object of the invention to provide laundry detergent compositions which, in the presence or absence of builder components, have excellent particulate soil removal and fabric finishing effects in addition to excellent greasy and oily soil and body soil removal performance.

It is a further object of the invention to provide detergent compositions which can be used in a wide variety of physical forms, such as liquid, paste, granulate, solid, powder, or in conjunction with a carrier, such as a substrate.

The present invention relates to a detergent composition which has a pH of at least 6.5 at a concentration of 0.05% by weight in the aqueous wash solution and which is free of oily hydrocarbon materials and cation-active materials which have an average of 13 or contain more ethylene oxide groups; these compositions are preferably phosphate-free or contain amounts of phosphate which are not greater than 20% by weight and are characterized in that they have 5 to 100% by weight of a surface-active mixture which has the following components:

(a) a biodegradable, non-ionic surfactant of the formula:

R (OC2H4) "OH

wherein R is a primary or secondary alkyl chain having 8 to 22 carbon atoms and n is an average number from 2 to 12 and which has an HLB value of 5 to 17; and

(b) a cationic surfactant free of hydrazinium groups and the formula:

R'mR2xYLZ

where each R1 is an organic group that contains a straight or branched alkyl or alkenyl group.

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holds, which is optionally substituted by up to 3 phenyl or hydroxyl groups and is optionally interrupted by up to 4 structures selected from the group consisting of

-C-N-,

0 u

-c-o-

-0-,

-o-c-,

0 FT

u i

-C-N-

Rc i

-N-

0 OH HO

II Hfl »

-0-C-0-, -0-C-N-, -N-C-0-

and mixtures thereof, where each R1 contains 8 to 22 carbon atoms and R1 can additionally contain an average of up to 12 ethylene oxide groups; m is a number from 1 to 3; each R1 containing no more than 14 carbon atoms when m = 2 and each R1 containing no more than 11 carbon atoms when m = 3; each R2 represents an alkyl or hydroxyalkyl group containing 1 to 4 carbon atoms or a benzyl group, with no more than one R2 in a molecule being benzyl; x represents zero to 11; Y is selected from the group consisting of

(1)

(2)

(3) (1)

(5)

(6)

-N ±

/

\ / +!

N —C-

-PI

_N ±

(7)

(8th)

(C2HilO) pH (C2H1.0) pH

-N *

I.

«Wv

À +

-C N-

4 c-V

/ C \ +

N N - C C-

where p is 1 to 12,

wherein each p represents 1 to 12.

and

V

(9) their mixtures; L stands for 1 or 2, the Y groups being separated from one another by a grouping selected from the group consisting of R1 and R2 groups with 1 to 22 C atoms and two free carbon single bonds, if L is 2, there is; Z is an anion in a number sufficient to impart electrical neutrality to the molecule; wherein the cationic surfactant is dispersible in water in admixture with the nonionic surfactant; wherein the weight ratio of the nonionic surfactant to the cationic surfactant is in the range of 5.1: 1 to 100: 1 and wherein the "cloud point" of the surfactant mixture described below is 0 to 95 ° C.

Preferred cationic surfactants are water soluble and have a critical micelle concentration (CMC) of more than 10 parts per million parts. The conventional cationic textile softening materials with two alkyl chains each having 18 carbon atoms are essentially insoluble and cannot form the only cationic component of the compositions according to the invention.

The compositions according to the invention are formulated in such a way that they have a pH of at least 6.5 in the aqueous washing solution at the conventional use concentrations in order to optimize the cleaning performance on greasy and oily dirt; Acidic pH values of the wash solution tend to reduce performance on such contaminants. The compositions are preferably alkaline in nature after they have been introduced into the wash solution and have a pH of more than 7.5, in particular at least 8. Some of the surface-active mixtures achieve the optimum removal of greasy / oily soiling at these higher pH values. With such mixtures, the overall performance can be improved by varying the pH of the washing solution during the washing process.

The compositions are free from oily hydrocarbon materials, like many dry cleaning solvents, mineral oil, paraffin oil and kerosene, because these materials (which are themselves oily in nature) burden the wash liquor with excessive oily material, which reduces the cleaning action of the compositions according to the invention.

The cationic component is free of hydrazinium groups because of its relatively high degree of toxicity, which makes it unsuitable for use in the compositions according to the invention.

Preferred compositions contain a weight ratio of nonionic surfactant to cationic surfactant from 5.1: 1 to 50: 1, preferably from 6: 1 to 40: 1, especially from 6: 1 to 20: 1. The removal of greasy and oily dirt is greatly improved at ratios of 8: 1 to 20: 1, and the improvement in performance is generally most noticeable when the amount of nonionic surfactant is increased so that the ratio from nonionic to cationic surfactant becomes greater than 5.1: 1 and approaches 8: 1.

Preferred compositions may contain mixtures of cationic and / or mixtures of nonionic surface active agents. The cationic surfactants must all fall within the definition of cationic surfactants set forth above, although small amounts of other cationic materials can be added. The mixtures of nonionic surfactants may contain nonionic surfactants that do not fall under the definition given above (such as alcohol ethoxylates with an average of more than 12 ethylene oxide groups per molecule) as long as at least one of the nonionic surfactants in the mixture falls under the definition of the nonionic surfactants falls and this nonionic surfactant is included in an amount such that it falls within the required ratio of 65 nonionic to cationic surfactants. If the mixture of nonionic surfactants contains a nonionic surfactant (or surfactant) that is not below that

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If the definition of the nonionic surfactants falls, the ratio of the surfactant (or surfactants) within the above definition to that which does not fall under the definition is preferably in the range of 1: 1 to 5: 1.

The compositions according to the invention contain, on a weight basis, 5 to 100%, in particular 10 to 95%, and most preferably 20 to 90% of a mixture or non-ionic and cationic surface-active agents defined above in the ratios indicated. It is preferred that the detergent compositions contain at least 1% by weight of the cationic component; otherwise there may not be enough cationic surfactant in the wash solution to achieve the desired cleaning and finishing effects. Furthermore, preferred compositions do not contain more than 10% by weight of the cation-active component for reasons of cost and commercial availability.

The compositions of the invention can contain up to 60% by weight of an electrolyte (although low levels of about 1 to 20% by weight are preferred) such as a detergency builder, as well as other additional materials conventionally found in detergent compositions. included, as explained in more detail below. The compositions can be phosphate-free, although small amounts of a phosphate builder, less than 20% by weight, based on the overall composition, can be tolerated. For reasons of environmental protection, it is preferred that the compositions are phosphate-free. To the extent that phosphate or other electrolytes are present in these compositions, they primarily affect cleaning performance by modifying the cloud point temperature of the surfactant mixture, as described below.

The main use of the compositions according to the invention is that in conventional household laundry operations. The compositions can also be used for other detergency purposes, including pretreatment of greasy and oily stains and in commercial laundry operations.

This describes processes for washing textiles with the compositions according to the invention, which have a superior effect in removing greasy and oily dirt and textile care. In these processes, the detergent compositions are used under such temperature conditions that the aqueous wash solution either at the cloud point (i.e. the temperature at which a phase rich in nonionic surfactant separates in the wash solution) or in its vicinity (ie within a distance of approximately 20 ° C thereof). This is achieved by formulating these surface-active mixtures in such a way that their cloud point falls between 0 and 95 ° C, in particular from 10 to 70 ° C, especially between 20 and 70 ° C, very particularly from 30 to 50 ° C. During the washing operation, the temperature of the washing solution is preferably kept in this temperature range and within a distance of 20 ° C from the cloud point temperature. Performance is further improved if the temperature of the aqueous wash solution is within 15 ° C, more preferably within 10 ° C, of the cloud point temperature of the surfactant mixture.

Non-ionic component

The nonionic surfactants used in the compositions according to the invention are biodegradable and have the formula:

R (OC2H4) nOH

wherein R is a primary or secondary alkyl chain with 8 to 22, preferably 10 to 20 C atoms and n is an average value from 2 to 12, in particular from 2 to 9. Although primarily linear alcohol ethoxylates from the performance point of view (e.g. alcohol ethoxylates made from organic alcohols containing about 20% branched 2-methyl isomers and commercially available from the Shell Chemical Company under the trade name Neodol) are preferred, it is possible, using secondary alcohol ethoxylates, to formulate compositions which, with approximately the same ratio of nonionic to cationic surfactant (ratio of nonionic to cationic surfactant equal to 5.1: 1 to 15: 1), provide an optimal removal result from both clay and fat / oil. Compositions using these secondary alcohol ethoxylates, however, tend to require higher use concentrations in the wash solution to perform best than compositions containing primary alcohol ethoxylates.

The nonionic surfactants have an HLB (hydrophilic-lipophilic balance) of 5 to 17, preferably 6 to 15. Optimal fat / oil removal is achieved if the nonionic surfactant has an HLB of 9 to 13. in particular from 10 to 12. To achieve optimal fat / oil removal, it is preferred to use cationic surfactants that are relatively soluble in such compositions, such as long chain quaternary ammonium compounds (e.g., cio to cis alkyl) or quaternary ammonium compounds, all of which are not contain more than 28 carbon atoms in their R1 and R2 molecule parts. The HLB value is described in detail in “Nonionic Surfactants” by M.J. Schick, Marcel Dekker, Inc., 1966, pp. 607-613. In preferred nonionic surfactants, n is 2 to 7, most preferably 4 to 7.

Nonionic surfactants that are within the definition of the nonionic component include a secondary cis alcohol polyethoxylate containing an average of 5 moles of ethylene oxide, a Ci2 alcohol polyethylenedoxate containing an average of 5 moles of ethylene oxide, a co-alcohol polyethoxylate which is im Contains an average of 4 moles of ethylene oxide, a Ci4 alcohol polyethoxylate that contains an average of 4 moles of ethylene oxide. This last surfactant is particularly useful for washing textiles with cold water. Preferred nonionic surfactants which are useful in the compositions of the invention include a Cio-Alcohol Polyäthoxylat, which contains an average of 3 moles of ethylene oxide, a C12 to Ci3 alcohol polyethoxylate, which contains an average of 3 moles of ethylene oxide, and the same product that is stripped to remove substantially all of the lower ethoxylate and non-ethoxylated fractions, a C14 to cis alcohol polyethoxylate containing an average of 7 moles of ethylene oxide, a C12 to Cn alcohol polyethoxylate containing an average of 6.5 moles of ethylene oxide Ci2 alcohol polyethoxylate, which contains an average of 5 moles of ethylene oxide, a coconut alcohol polyethoxylate, which contains an average of 5 moles of ethylene oxide, a C12 to Cn alcohol polyethoxylate, which contains an average of 9 moles of ethylene oxide, a C14 to Ci5 alcohol polyethoxylate, the contains an average of 3 moles of ethylene oxide, one cm to cis-alcohol polyethoxylate, which contains on average 4 moles of ethylene oxide contains, and a C14 to 15 alcohol polyethoxylate, which contains an average of 9 moles of ethylene oxide.

Specific examples of mixtures of nonionic

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Surfactants in which both components are within the definition of the non-ionic component include: a mixture of a Cm to Cis alcohol poly-ethoxylate containing an average of 3 moles of ethylene oxide (Neodol 45-3) and a Ci4 to Ci5 alcohol polyethoxylate, 5 which contains an average of 7 moles of ethylene oxide (Neodol 45-7), with a ratio of nonionic lower ethoxylate to nonionic higher ethoxylate of 1: 1 to 3: 1, a mixture of a cio-alcohol polyethoxylate containing an average of 3 moles of ethylene oxide, along with 10 a secondary cis alcohol polyethoxylate containing an average of 9 moles of ethylene oxide (Tergitol 15-S-9), with a ratio of nonionic lower ethoxylate to nonionic higher ethoxylate from 1: 1 to 4: 1, and a mixture of Neodol 45-3 and Tergitol 15-S-9, with an is ratio of nonionic lower ethoxylate to nonionic higher ethoxylate of 1: 1 to 3: 1.

Preferred mixtures of nonionic surfactants contain alkyl glyceryl ether compounds in addition to the required nonionic surfactants. Particularly preferred glyceryl ethers have the formulas:

R / -OCH2-ÇH-CH2OH and R'-0 (CH2CH20) nCH2CHCH20H

OH

I.

OH

wherein R 'is an alkyl or alkenyl group with 8 to 18, preferably 8 to 12, C atoms or an alkaryl group with 5 to 14 C atoms in the alkyl chain and n is 1 to 6. These materials can be used in compositions with the non-ionic surface-active component according to the invention in a ratio of non-ionic surface-active agent to glyceryl ether of 1: 1 to 4: 1, in particular 7: 3.

Preferred compositions according to the invention are essentially free of fatty acid polyglycol ether diester compounds, e.g. Polyethylene glycol 600 dioleate or poly ethylene glycol 800 distearate. Such additives have no advantage and may even lead to a disadvantage with regard to the dirt removal and textile processing potential according to the present invention.

Other nonionic surfactants well known in the detergent art can be used in combination with one or more of the nonionic surfactants that fall within the definition of nonionic surfactants useful for the invention to provide useful mixtures of nonionogenic to form surfactants. Examples of such surfactants are listed in Booth U.S. Patent 3,717,630, issued February 20, 1973 and U.S. Patent 3,332,180 issued to Kessler et al., Issued July 25, 1967. Nonlimiting examples of suitable nonionic surfactants that can be used in conjunction with the necessary nonionic surfactants defined 55 include the condensation products of aliphatic alcohols with ethylene oxide that differ in alkyl or ethylene oxide chain length (e.g., more) as 12 ethylene oxide groups per molecule) so that they do not fall under the definition given above. 60

These complementary nonionic surfactants can also be of the semi-polar type, including water-soluble amine oxides, which contain 1 alkyl group with 10 to 28 carbon atoms and 2 groups selected from the group consisting of alkyl groups and hydroxyalkyl groups. A preferred amine oxide is C12 to 14-alkyldimethylamine oxide. In addition to their surface-active properties, these compounds can also be used in

Amounts of 3 to 20% of the composition are included to modify the foaming properties of the detergent compositions to make them compatible with specific types of washing conditions. Other semipolar surfactants include water-soluble phosphine oxides containing 1 alkyl group containing 10 to 28 carbon atoms and 2 groups selected from the group consisting of alkyl groups and hydroxyalkyl groups containing 1 to 3 carbon atoms and water-soluble sulfate oxides containing 1 alkyl group with 10 to 28 carbon atoms and 1 grouping selected from the group consisting of alkyl and hydroxyalkyl groups with 1 to 3 carbon atoms.

Cation active component

The cationic surfactants used in the compositions according to the invention correspond to the formula defined above:

R'mR2xYLZ

The particular cationic component to be incorporated into a given system largely depends on the particular nonionic component to be used. The cationic component is chosen so that when mixed with the nonionic surfactant, it is water dispersible. The cationic surfactant is chosen in the light of the particular nonionic surfactant used to meet the requirements for the cloud point of the detergent composition discussed below. Mixtures of these cation-active materials can also be used in the compositions according to the invention. Preferred cationic surfactants are those with critical micelle concentrations of less than 500 ppm, especially less than 100 ppm.

In preferred cationic materials, L is 1, p is 1 to 12, preferably 1 to 10, and Y is

-N-

'X,

-c-

!

'-f

(CgHjjO) H (CjHjjOjpH

-N-

or mixtures thereof. However, L can also be 2, which results in cation-active components which contain two cationic charge centers. An example of a di-cationic component is given below:

£

CH "

, oH — N —CH “—CH0 — CH_ — N —CH, lo 35 I 2 2 2 I 3

CH,

CH,

Other cationic materials suitable for the compositions according to the invention include phosphonium and sulfonium materials.

In preferred cation active materials described above, wherein m is 1, it is preferred that x is 3 and R2 is a methyl group. Preferred compositions of this type with a long chain include those

wherein R 'is a C10 to Cis alkyl group. Particularly preferred components of this class include Ci6- (palmitylal-ky l-) trimethylammonium halide, tallow alkyl trimethyl ammonium halide and coconut alkyl trimethyl ammonium halide. In preferred systems, tallow alkyl trimethyl ammonium or coconut alkyl trimethyl ammonium materials are combined with a nonionic surfactant selected from the condensation pro

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products of C12 to Cu alcohol with 4 to 10 moles of ethylene oxide or the condensation product of Cm to Cis alcohol with 6 to 10 moles of ethylene oxide, such as the condensation product of Ci2 alcohol with 5 moles of ethylene oxide, the condensation product of C12 to Cn- Alcohol with 6.5 mol of ethylene oxide, the condensation product of Cm to cis-alcohol with 7 mol of ethylene oxide or mixtures thereof in nonionic ratios: cationic from 5.1: 1 to 30: 1, in particular from 7: 1 to 20: 1, most preferably about 10: 1. When using the condensation product of Cu to Cn alcohol 10 with 2 to 4 moles of ethylene oxide or the condensation product of Cm to Cis alcohol with 3 to 6 moles of ethylene oxide in nonionic: cationic ratios from 5.1: 1 to about 10: 1 In addition to excellent fat / oil removal, excellent removal of particulate dirt 15 is achieved. These compositions can also contain up to 15% alkanolamine, preferably monoethanolamine, as a source of alkalinity and to increase the removal of body dirt. For example, coconut alkyl trimethyl ammonium chloride with the condensation product of 20

Ci2 alcohol with 5 moles of ethylene oxide, the condensation product of C12 to Cu alcohol with 6.5 moles of ethylene oxide or mixtures thereof in nonionic ratios: cationic from 5.1: 1 to 20: 1, in particular 5.1: 1 to 9: 1, can be combined. In another composition, coconut alkyltrimethylammonium chloride is combined with the condensation product from Cm to Ci5-alcohol with 7 moles of ethylene oxide in nonionic: cationic ratios of 5.1: 1 to 15: 1.

Another preferred composition uses cationic surfactants of the formula: 30

35

excellent removal of particulate dirt can be obtained for excellent removal of greasy / oily dirt.

When using materials with three long chains (m = 3), it is preferred that x is 1 and that R2 is a methyl group. In these compositions, R1 represents a Cs to Cn alkyl group. Particularly preferred three-chain long chain cationic materials include trioctylalkyl (Cs) methylammonium halide and tridecylalkyl (Cio) methylammonium halide.

Another type of preferred cationic surfactant for use in the compositions of the invention are quaternary, alkoxylated alkyl compounds. Examples of such connections are given below:

CH,

I-

CH,

R-N + - (C2H1 (0) pH and HCOCgH ^) p-N + - (C2H40) pH z "

R

R

1 '+ 2 R -N -R

wherein R1, R2 and Z are as defined above, in combination 40 with the condensation product of C12 to Ci3 alcohols with 5 to 10 moles of ethylene oxide or the condensation product of Cm to Cis alcohol with 5 to 10 moles of ethylene oxide, such as the condensation product of Ci2 alcohol with 5 moles of ethylene oxide, the condensation product of Ci2 to 45

Ct3 alcohol with 6.5 moles of ethylene oxide, the condensation product of Cm to cis alcohol with 7 moles of ethylene oxide and mixtures thereof in nonionic: cationic ratios from 5.1: 1 to 15: 1, in particular about 7: 1.

When m is 2, it is preferred that x is 2 50 and R2 is a methyl group. In this case, R1 must not have more than 14 carbon atoms. A preferred cationic material of this class is dicoconut alkyl (Ci2 to Ci4) dimethylammonium halide.

Preferred compositions of this type use coconut alkyl dimethylammonium halide together with the condensation product of C12 to Cn alcohol with 6 to 10 moles of ethylene oxide or the condensation product of C14 to C15 alcohol with 5 to 9 moles of ethylene oxide, such as the condensation product of C12 to Ci3 alcohol with 6.5 mol of 60 ethylene oxide, the condensation product of Cu to cis alcohol with 7 mol of ethylene oxide and mixtures thereof in nonionic ratios: cationic from 5.1: 1 to 15: 1, in particular from 6: 1 to 12 :1. When using the condensation product of C12 to Ci3 alcohol with 4 to 8 moles of 65 ethylene oxide or the condensation product of C to Cis alcohol with 4 to 8 moles of ethylene oxide in nonionic: cationic ratios of 5.1: 1 to 15: 1 additionally wherein each p is 1 to 12, preferably 1 to 10 (with the total ethylene oxide groups not exceeding 13 in one molecule) and each R is a C10 to C20 alkyl group. For best removal of greasy and oily dirt, it is preferred that these compounds contain no more than 10, preferably no more than 7, ethylene oxide groups in total.

The surface-active mixtures in the compositions according to the invention must be free from cation-active compounds which contain 13 or more ethylene oxide groups. These compounds tend to be relatively non-biodegradable, they do not improve the cleaning and fabric finishing properties of the compositions, and in some circumstances may even reduce the overall wash performance that they provide. It should be noted that polyethoxylated cationic surfactants with a relatively low degree of ethoxylation, such as the ones described above, have better biodegradability properties and can advantageously be incorporated into the compositions according to the invention.

A particularly preferred type of cationic component has the formula:

R1

R2- (Z1) a- (R3) n-Z2- (CH2) m -N + -R1 X ~

wherein R1 is Ci to Cf-alkyl or hydroxyalkyl, R2 is unbranched or branched chain Cs to C39-alkyl, alkenyl, alkylphenyl or

R1

1 o_ I

X represents R - N- (CH-) -I, 2 s; wherein s is zero to 5; R3 is Ci to C2o alkylene or alkylene; a is zero or 1; n is zero or 1; and n is 1 when a is 1; m is 1 to 5; Z1 and Z2 are each selected from the group consisting of

0 0

u u

-c-o-, -o-c-, -0-

0

II

-O-C-O-. H O

OH HO OH

u 1 1 u 11 1 1 »

-C-N-, -N-C-, -0-C-N-, -N-C-O-

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and wherein at least one of said groups is an ester, reverse ester, amide and reverse amide; and X represents an anion that makes the compound dispersible at least in water, preferably selected from the group consisting of halide, methyl sulfate, sulfate and nitrate, more preferably chloride, bromide, iodide, methyl sulfate and sulfate.

In addition to the advantages of the other cationic surfactants disclosed herein, this particular cationic component is desirable from an environmental standpoint because it is biodegradable, providing environmentally safe compounds, both in terms of its long alkyl chain and in terms of its nitrogenous content Segment. These preferred cationic components are useful in mixtures of nonionic / cationic surfactants that have a nonionic to cationic ratio of from about 1: 1 to about 100: 1. However, if they are used in the compositions according to the invention, they are used in mixtures of surfactants, the ratios of nonionic to cationic surfactant from 5.1: 1 to 100: 1, in particular from 5.1: 1 to 50: 1, most preferably from 6: 1 to 40: 1, especially from 6: 1 to 20: 1.

Particularly preferred cationic surfactants of this type are the choline ester derivatives of the following formula:

0 -CH,

R -C-0-CH2CH2-

-iI + -CH, X ~

I J

CH

have concentrations in the range of 0.002 to 0.2, preferably 0.002 to 0.15, most preferably 0.002 to 0.08. If non-ionic and cation-active components of greater purity are used, the narrower CR ranges are more preferred.

The concept of reduced monomer concentration in a one-component system as a quantity that standardizes the extent of the adsorption of a surface-active agent on a textile surface (the element critical for the removal of greasy / oily dirt) is described in Tamamushi and Tamaki, Proceedings of the Second International Congress of Surface Activity, III, 449, Academic Press, Inc. (1957). The equations below extend this concept of reduced monomer concentration to multi-component systems using the concentrations of the monomeric surfactants. The term of the concentration of the monomeric surfactant (surfactant monomer concentration) is from the discussion in Clint, J. Chem. Soc. Far. Trans. I, 71, 1327 (1975) in connection with an ideal solution and is based on the following quadratic equation [Equation (11) in Clint]:

as well as those compounds in which the ester bond in the above formula is replaced by a reverse ester, amide or reverse amide bond.

Particularly preferred examples of this type of cationic surface-active agent are quaternary stearoylcholinester ammonium halides (R2 = Cn-AlkyI), quaternary palmitoylcholinester ammonium halides (R2 = Ci5-alkyl), quaternary myristoylcholinester ammonium halides (R2 = Cn-alkylates) and R2 = Cn-alkylates Talgoylcholinesterammoni umhalogenide (R2 = Cis to Cn alkyl).

Formulation criteria

Preferred compositions according to the invention can be formulated using the non-ionic and cation-active components defined above, taking into account the reduced monomer concentration (CR) of the action-active component in the washing solution as a guide. In particular, the selection of a CR value for a given nonionic and cationic surfactant determines the ratio in which these surfactants are to be combined. The reduced monomer concentration of a surfactant is obtained by dividing the concentration of monomeric surfactant present in the wash solution by the critical micelle concentration (CMC) of the surfactant in question. Unless otherwise stated, the CMC values used are determined at 40.6 ° C. in water which contains 120 ppm mixed Ca / Mg hardness. The reduced cationic monomer concentration of the mixture of nonionic and cationic surfactants is defined by equations (1) to (3) below. The preferred mixtures of nonionic / cationic surfactants for the present invention are those that have reduced monomer concentrations.

60

(c ™) 2

, m

+ c1 (C-c2 + c1)

aCc * = O

where in the above and the following equations:

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C = total analytical concentration of surfactant in the solution (mol / liter) = sum of the concentrations of the cationic and nonionic surfactant = Ci + C2 (where "1" denotes nonionic surfactant and "2" denotes cationic surfactant), cî = critical micelle concentration (CMC) of the nonionic surfactant (mol / liter),

C2 = critical micelle concentration of the cationic surfactant (mol / liter), a = total mole fraction of the nonionic surfactant in the solution = Ci / (Ci + C2),

ß = a constant based on the heat of the mixture = -2.8,

c ™ = concentration of the nonionic monomer, c ™ = concentration of the cationic monomer, e = basis of Napier's logarithmic system = 2.71828,

x = mole fraction of the nonionic surfactant in the micelle at concentration C, = coefficient of nonionic activity in the mixed micelle = eWi-x) :,

= Coefficient of cationic activity in the mixed micelle = e'k \

= f2C2 - flCl,

= reduced cationic monomer concentration, = molecular weight of the nonionic surfactant,

= Molecular weight of the cationic surfactant,

= total analytical concentration of surfactant in the solution (ppm) = sum of the concentrations (ppm) of cationic and nonionic surfactant = Wi + W2 (where «1» nonionic surfactant

A

Cr

MI

M2

W

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Labeled agent and “2” called cationic surfactant) = weight fraction of nonionic surfactant in the composition.

The above equation is solved by pulling its positive root after the concentration of the nonionic monomer [Equation (12) at Clint].

m _

[.- (C-Cc'-c *)) ± [(c- (c £ -c *)) 2 + i) aC (c £ -c *)] 17f

By modifying this equation based on the assumption of a real rather than an ideal solution, the CR range for optimal performance was derived from the following equation:

(C-A) +

l / 7c-

A) + HaCA

2 A

15 (1 - x) elk: = CR

using conventional numerical iteration methods to an error of x of less than 0.001;

(b) Finding the range of Y from the equation:

(1)

Y (l-x) Mi x (l-Y) M2

1000

w

• [x (x— 1) A]

For a given purification test for a nonionic / cationic system, x was determined by inserting the values known from the test (ie cî, C2, a, C and ß) into equation (1) and iteratively resolving to x, so that the error of x is less than 0.001. This procedure was repeated for a large number of such tests with varying conditions of use. The values obtained for x were then used to calculate using the following equation:

C2 = (1 - X) f2C2

(2)

to dissolve according to the concentrations of the cationic monomers.

The value for Cr was then calculated using equation (3):

Cr = c5Vc2

(3)

The values obtained for CR include a large number of combinations and ratios of different nonionic and cationic surfactants at different concentrations and temperatures, which were evaluated for their cleaning ability for greasy / oily dirt. Examination of the resulting data showed that the optimal greasy / oily dirt cleaning for a given system was found to have a CR of 0.002 to 0.2.

This range of CR (ie, 0.002 to 0.2) can then be used to, for any given combination of nonionic surfactant and cationic surfactant, the range of optimal nonionic / cationic ratios for the desired wash concentration within the entire range of wash concentrations Determine 100 parts per million (ppm) to 10,000 ppm surfactant. This calculation is done in the following manner, where β, CR, cî, C2, Mi and M2 are known for a given pair of nonionic / cationic surfactants:

(a) for a given nonionic surfactant, cationic surfactant, and for each end of the CR region, dissolve by x using the equation:

using 100 ppm and 10,000 ppm as limits for W for each end of the CR range;

(c) the range for the non-ionic / cationic ratio (NCR) for optimal performance is then within the range given by inserting the limits for Y in the formula:

NCR =

1 - Y

35

is obtained.

In other words, stages (b) and (c) can be combined into a single equation that can be solved directly after NCR.

1

- (1000 / W) A +

NCR =

• Y 1-Y

Mg (x-1)

(1000 / W) A +

1 xM,

The above procedure is only relevant for concentrations of the washing solution above the critical micelle concentration of the nonionic / cationic mixture. For concentrations as high as about five times the critical micelle concentration, CR is essentially independent of the concentration. This means that for usual laundry use concentrations (e.g. 100 ppm to 10,000 ppm and in particular about 250 ppm to about 3000 ppm) the CR value of most commercial mixtures of cation-55 active / non-ionic surface-active agents (in which the cation-active component is a CMC of less than about 100 ppm measured in 40.6 ° C water containing 120 ppm mixed Ca / Mg hardness) is independent of the actual use concentration, so using such a concentration of about 1000 ppm in the calculation above satisfactory approach for the whole area. If no concentration range is specified here, the CR value of 1000 ppm is meant.

As an example, the optimal fat / oil removal ratio for Composition A of Example 1 herein, given CR, is calculated below. The following values are either known for this system or are selected in the specified manner:

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w

= 1000 ppm (chosen as representative of

Conditions of use)

d

= 1.967 x 10_5ppm

* C2

= 2.1875 x 10_5ppm

ß

= -2.8

Wed

= 406.7

Wed

= 320

Cr

= 0.0073 (selected for optimal performance at the

Removal of greasy / oily dirt, but could be any value between 0.002 and 0.2)

Insert the values for ß and CR in equation (a):

(l-x) e --- s *; = 0.0073

Iterative resolution according to x shows that x = 0.922.

Using this value for x one finds that fi = 0.983 f2 = 0.0925

A = (0.0925) - (2.1875 x IO-5) - (0.983) - (1.967 x IO-5) = -1.73 x IO "5

By inserting these values into equation (b) one finds that

Y (1-0.922) _ 0.922 (1-Y)

406.7 320

= -Yyyyyy- (0.922). (0.922-1). (- 1.73x 10-5)

Y = 0.938

By inserting this value for Y in equation (c), the nonionic / cationic ratio is determined:

It will be noted that this ratio corresponds to the ratio actually found in Example 1, Composition A.

In addition to these criteria of reduced cationic monomer concentration, the nonionic / cationic surfactant mixture must meet the specific cloud point requirements set out below. The cloud point of the nonionic / cationic mixture (and in preferred embodiments of the nonionic / cationic mixture plus any electrolytes present in the composition) falls between 0 and 95 ° C, preferably between 10 and 70 ° C, more preferably between 20 and 65 ° C , especially between 30 and 50 ° C. For cold water washing power, the surface-active mixture should have a cloud point between 0 and 25 ° C. The fact that a composition has a cloud point within these temperature ranges ensures that the composition can be used under washing temperature conditions to achieve excellent removal of greasy / oily dirt. If a composition does not have a cloud point within the specified temperature range, it does not result in excellent cleaning within this temperature range. The compositions show their best fat / oil removal performance when the temperature of the wash solution in which they are used is in the range of about 20 ° C, preferably about 15 ° C and most preferably about 10 ° C above or below that The cloud point of the mixture of nonionic / cationic surfactant falls. In other words, the temperature range of the wash solution in which the preferred compositions provide optimal fat / oil removal is between the cloud point temperature of the system in the absence of the cationic component and about 30 ° C, preferably about 25 ° C, most preferably about 20 ° C above this cloud point temperature.

As used herein, the term "cloud point" means the temperature at which a curve plotting the light scattering intensity of the composition against the temperature of the wash solution begins to steeply increase to its maximum value under the following experimental conditions:

The light scattering intensity is measured using a model VM-12397 photogoniodiffusometer manufactured by Société Française d'instruments de contrôle et d'analyses, France (the instrument is hereinafter referred to as Sofica). The Sofica sample cell and its lid are washed with hot acetone and left to dry. The surface-active mixture is prepared and brought into solution with distilled water at a concentration of 1000 ppm. A sample of approximately 15 ml of the solution is added to the sample cell using a syringe with a 0.2 µ nucleopore filter. The needle of the syringe passes through the cover of the sample cell so that the interior of the cell is not exposed to atmospheric dust. The sample is kept in a variable temperature bath and both the bath and the sample are stirred continuously. The bath temperature is heated using the Sofica heating device and cooled by adding ice (heating speed approx. 1 ° C / min); the temperature of the sample is determined by the bath temperature. The light scattering intensity of the sample (scattering angle 90c) is then determined at different temperatures, a green filter and no polarizer being used in the Sofica.

The preferred nonionic and cationic components used in the present compositions are selected, combined and used on the basis of three basic criteria:

(1) the finished composition must meet the cloud point criteria set forth above and should be such that the cloud point temperature of the surfactant mixture is within a range of about 20 CC around the normal temperatures of the wash solution,

(2) the reduced concentration of the cationic monomer in the surfactant mixture preferably falls within the range defined above; and

(3) the concentration of the detergent composition in the washing solution should be sufficient to give the desired cleaning performance at normal washing temperatures.

Particularly desirable for use in the present invention are biodegradable nonionic surfactants that have relatively low CMC values and low cloud points (i.e., the temperature at which an aqueous solution of the surfactant exhibits haze). These surfactants can be used to make detergent compositions whose wash solutions at lower temperatures provide the desired cloud point of the nonionic / cationic mixture without the need to add other ingredients such as electrolytes or anionic surfactants. Such detergent compositions make it easier to meet the cloud point conditions set forth herein and result in one

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excellent removal of greasy and oily dirt from textiles.

For the formulation and use of the compositions according to the invention, it is preferred for typical American conditions for automatic washing that the nonionic surface-active agent, the cationic surface-active agent and any additional components are selected and used in such amounts that the temperature at which the detergent composition is used in the aqueous washing solution has a cloud point as defined above, between about 30 and 50 ° C, preferably at about 45 CC. If the compositions are used under different washing conditions, the compositions are preferably formulated in such a way that, at the desired concentration of use, they show their cloud point 15 at a temperature which is within a range of approximately 20 ° C. from the desired washing temperature. For example, in Japan (where wash temperatures are generally lower than those used in the United States), the compositions are conveniently formulated to have a cloud point close to about 15 ° C.

For a given composition, the cloud point temperature in the wash solution depends on the physical and chemical properties (such as CMC and solubility) 25 of the cationic, nonionic and additional components in that composition and can be reduced by increasing the alkyl chain lengths of the nonionic or cationic components, by reducing the degree of ethoxylation of the nonionic component or by adding electrolytes such as phosphates, polyphosphonates, perborates, carbonates or sulfates, especially in relatively low amounts (such as from about 1 to about 15% of a given composition). More specifically, it is preferred that the detergent compositions of the invention, 33 when used in the aqueous wash solution, have cloud points that range from about 15 ° C, preferably about 10 ° C, and most preferably about 5 ° C around temperature the wash solution. It has been found that the ability of the wash solution to remove greasy and oily dirt increases dramatically when these relationships between wash solution temperature and cloud point are satisfied.

Although not wishing to be bound by theory, it is believed that the cationic component will be adsorbed on the fabric if an inventive detergent composition is present in a wash solution with oil-soiled fabrics, thereby neutralizing the negative charge on the fabric. This neutralization of the charge favors the adsorption of the non-ionic surfactant on the textile material, which causes the oily dirt to "roll up". The dirt can then be easily removed by movement. This mechanism and thus the removal of greasy / oily dirt is optimized precisely by formulating mixtures of cationic / nonionic surface-active agents which meet the requirements for the cloud point and the preferred reduced concentration of the cationic monomer.

60

Fatty acid amide component

In a particular embodiment of the present invention, the nonionic surfactant / cationic surfactant mixture contains 2 to 25 ° C, preferably 2 to 16 ° C, and most preferably 65 3 to 10 ° C, of a fatty acid amide surfactant. However, the compositions contain the nonionic surfactants defined above to optimize the cleaning effect obtained. In the case of nonionic / cationic systems, the ratio of the total cationic and nonionic components to the amide component included can be in the range from 5: 1 to 50: 1, preferably from 8: 1 to 25: 1. These compositions give excellent performance in removing particulate dirt as well as improved anti-graying properties.

Amides useful in these preferred compositions include, but are not limited to, carboxylic acid amides, sulfonic acid amides, phosphonic acid amides, and boronic acid amides. Preferred amides include those of the formulas:

O

l "/ R -C-N

V

and

R1-S-N.

XR2

// * .0 0

wherein R1 is Cs to C: o-alkyl, alkenyl, alkylphenyl or alkyl-benzyl, preferably Cio to Cis alkyl and most preferably Cn alkyl; and each R2 is hydrogen or Ci to Cs alkyl or hydroxyalkyl, preferably hydrogen. Specific examples of these compositions include a mixture of stearoylcholine bromide (present at 120 ppm in the wash solution), coconut alcohol polyethoxylate, which contains an average of 5 moles of ethylene oxide (present at about 357 ppm in the wash solution), and a mid-cut coconut alkylammonium amide (at about 50 ppm present); and a mixture of stearoylcholine bromide (100 ppm), coconut alcohol polyethoxylate, which contains an average of 5 moles of ethylene oxide (357 ppm), and lauramide (R1 = Cn and R2 = hydrogen; at 45 ppm).

Optional additional components

The compositions according to the invention can also contain additional constituents, which are generally found in laundry detergent gene compositions, in their customary amounts known to the person skilled in the art. These additional components are selected so that the composition as a whole meets the cloud point criteria described above.

The compositions according to the invention can contain up to 15 ° / o, preferably up to 5 ° / o and most preferably 0.1 to 2 ° o, of a foam-inhibiting component. Typical anti-foam agents include long chain fatty acids such as those described in U.S. Patent 2,954,347 to St. John, issued September 27, 1960, and combinations of certain nonionic compounds therewith, as in U.S. Patent 2,954,348 to Schwoeppe,

issued September 27, 1960, both disclosures of which are incorporated herein by reference. Other foam-inhibiting components that are useful in the compositions of the present invention include, but are not limited to, those described below.

Preferred foam-inhibiting silicone additives are described in U.S. Patent 3,933,672 to Bartolotta et al. issued January 20, 1976, which is incorporated herein by reference. The silicone material can be represented by alkylated polysiloxane materials such as silica aerogels and xerogels and hydrophobic silica of various types. The silicone material can be a siloxane of the formula:

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12

are described in which x is 20 to 2000 and R and R 'are each alkyl or aryl groups, in particular methyl, ethyl, propyl, butyl and phenyl. The polydimethyl siloxanes (R and R '= methyl) with a molecular weight in the range of 200 to 200,000 and higher are all useful as foam control agents. Additional suitable silicone materials, wherein the side chain groups R and R 'are alkyl, aryl or mixed alkyl and aryl hydrocarbon groups, show useful foam control properties. Examples of such ingredients are diethyl, dipropyl, dibutyl, methyl, ethyl, phenylmethyl polysiloxanes and the like. Additional useful silicone foam control agents can be represented by a mixture of an alkylated siloxane of the type mentioned above and solid silicon dioxide. Such mixtures can be made by attaching the silicone to the surface of the solid silica. A preferred silicone foam control agent is a hydrophobic silanized (most preferably trimethylsilanated) silica with a particle size in the range of about 10 to 20 nm and a specific surface area above about 50 m2 / g, which is coated with a dimethyl silicone fluid with a molecular weight in the range of about 500 to about 200,000 with a weight ratio of silicone to silanized silicon dioxide of about 19: 1 to about 1: 2 is intimately mixed. The silicone foam retardant is advantageously incorporated in a detachable manner into a water-soluble or water-dispersible, essentially non-surface-active, impermeable to detergent carrier.

Particularly useful anti-foaming agents are the self-emulsifying silicone anti-foaming agents, such as DB-544, commercially available from Dow Corning, which contains a siloxane / glycol copolymer together with solid silica and a siloxane resin.

Microcrystalline waxes, which have a melting point in the range of 35 to 115 ° C and a saponification number of less than 100, are additional examples of a preferred foam control component for use in the present compositions and are described in detail in U.S. Patent 4,056,481 by Tate, issued November 1, 1977, incorporated herein by reference. The microcrystalline waxes are essentially water-insoluble, but are dispersible in water in the presence of organic surface-active agents. Preferred microcrystalline waxes have a melting point of about 65 to 100 ° C, a molecular weight in the range of 400 to 1000; and a penetration value of at least 6, measured at 25.0 ° C according to ASTM-D1321. Suitable examples of the above waxes include: microcrystalline and oxidized microcrystalline petroleum waxes; Fischer-Tropsch and oxidized Fischer-Tropsch waxes; Ozokerite; Ceresin; Montan wax; Beeswax; Candelilla wax; and carnauba wax.

Alkyl phosphoric acid esters represent an additional preferred foam retardant for the use according to the invention. These preferred phosphoric acid esters are predominantly monostearyl phosphate, which can additionally contain di- and tri-stearyl phosphates; and monooleyl phosphates, which may contain di- and tri-oleyl phosphates.

The alkyl phosphoric acid esters often contain some tri-alkyl phosphate. Accordingly, a preferred phosphoric acid ester can be used in addition to the monoalkyl ester, e.g. Monostearyl phosphate, up to 50 mol% dialkyl phosphate and up to 5 mol% trialkyl phosphate.

The detergent compositions of the invention may also contain 1 to 60%, preferably small amounts of 1 to 15%, electrolyte components such as conventional detergency builders, especially alkaline, polyvalent anionic builder salts, subject to the phosphate restrictions discussed above. The alkaline salts primarily serve to maintain the pH of the cleaning solution in the range of 7 to 12, preferably 8 to 11, in order to modify the cloud point of the detergent composition and to provide a source of ionic strength. However, it is important to emphasize that the compositions according to the invention can provide excellent cleaning even in the complete absence of such builder materials.

Suitable detergent builder salts useful herein may be of the polyvalent inorganic or polyvalent organic type or mixtures of these varieties. Non-limiting examples of suitable water-soluble, inorganic alkaline detergent builder salts include: alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates, silicates and sulfates. Specific examples of such salts include sodium and potassium tetraborate, perborate, bicarbonate, carbonate, tripolyphosphate, orthophosphate, pyrophosphate and hexametaphosphate.

Examples of suitable organic alkaline detergency builder salts include:

(1) Water soluble aminopolyacetates, e.g. Sodium and potassium ethylenediaminetetraacetate, nitrilotriacetate and N- (2-hydroxyethyl) nitrilotriacetate;

(2) water soluble salts of phytic acid, e.g. Sodium and potassium phytate; and

(3) water-soluble polyphosphonates, including sodium, potassium and lithium salts of ethane-1-hydroxy-1,1-diphosphonic acid; Sodium, potassium and lithium salts of ethylene diphosphonic acid and the like.

Additional organic builder salts useful herein include the polycarboxylate materials described in U.S. Patent 3,364,103, which is incorporated herein by reference, including the water-soluble alkali salts of mellitic acid. The water soluble salts of polycarboxylate polymers and copolymers, such as those described in U.S. Patent 3,308,067, which is incorporated herein by reference, are also useful herein as builders.

Another class of detergency builder materials useful in the present invention are insoluble sodium aluminosilicates, particularly those described in Belgian Patent 814,874, issued November 12, 1974, which is incorporated herein by reference. This patent describes and claims detergent compositions containing sodium aluminosilicates of the formula:

Naz (A102) z (Si02) y • XH2O

where z and y are integers at least equal to 6, the molar ratio of z to y is in the range of 1.0: 1 to 0.5: 1 and X is an integer from 15 to 264, the Alumosilicates have a calcium ion exchange capacity of at least 200 milligram equivalent / gram and a calcium ion exchange rate of at least 120 parts per million parts, per minute and per gram. A preferred material is

Nai2 (Si02 • A102) i2 • 27H2O.

Mixtures of organic and / or inorganic builders can be used here. Such a mixture of builders is disclosed in Canadian Patent 755 038 and consists of a ternary mixture of sodium tripolyphosphate, trisodium nitrilotriacetate and trinetriumethane-1-hydroxy-1,1-diphosphonate.

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Other preferred builder materials that can be used in the compositions of the invention include alkali metal carboxymethyl tartronates, which are commercially available, with about 76% active together with about 7% ditartronate, about 3% diglycolate, about 6% sodium carbonate and about 8% water; and anhydrous sodium carboxymethyl succinate, commercially available, with about 76% active along with about 22.6% water and a mixture of other organic materials such as carbonates.

In addition to the cationic and nonionic surfactants discussed above, the detergent compositions according to the invention can additionally contain up to 50%, preferably 5 to 30%, anionic surfactants, zwitterionic surfactants or mixtures of such surfactants. Surfactants of these types which are useful in the compositions of the invention are described in Booth U.S. Patent 3,717,630, issued February 20, 1973 and Kessler et al. U.S. Patent 3,332,880 '. issued on July 27, 1967. Specific, non-limiting examples of surfactants suitable for use in the present compositions are as follows: These surfactants are chosen so that the composition as a whole meets the criteria described above for the cloud point and the reduced concentration of the cationic monomer .

Water soluble salts of higher fatty acids, i.e. "Soaps" are useful herein as an anionic surfactant. This class of surfactants includes common alkali metal soaps, such as sodium, potassium, ammonium and alkanolammonium salts of higher fatty acids, which contain 8 to 24 carbon atoms and preferably 10 to 20 carbon atoms. Soaps can be made by direct saponification of fats and oils or by neutralizing free fatty acids. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e. Sodium or potassium tallow and coconut soaps.

Another class of anionic surfactants includes water-soluble salts, especially the alkali metal, ammonium and alkanolammonium salts, of organic sulfuric acid reaction products which contain in their molecular structure an alkyl group containing 8 to 22 carbon atoms and a sulfonic acid or sulfuric acid ester group. (The term "alkyl" includes the alkyl group of acyl groups.) Examples of these groups of synthetic surfactants that can be used in the present detergent compositions are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (8 to 18 carbon atoms), which are produced by reducing the glycerides of tallow or coconut oil; and sodium and potassium alkylbenzenesulfates, in which the alkyl group contains 9 to 15 carbon atoms in a straight-chain or branched-chain configuration, e.g. those of the type described in U.S. Patents 2,220,099 and 2,477,383, which are incorporated herein by reference.

Other anionic surfactants useful herein include the sodium alkyl glyceryl ether sulfonates, especially those ethers or higher alcohols derived from tallow and coconut oil; Sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; and sodium or potassium salts of alkylphenol polypropylene oxide ether sulfate, which contains 1 to 10 units of ethylene oxide per molecule and in which the alkyl groups contain 8 to 12 carbon atoms.

The alkaline earth metal salts of synthetic anionic surfactants are useful in the present invention. In particular, the magnesium salts of linear alkylbenzenesulfonic acids in which the alkyl group contains 9 to 15, in particular 11 to 13, carbon atoms are useful.

Other anionic surfactants useful herein include the water-soluble salts of esters of a-sulfonated fatty acids containing 6 to 20 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids which contain 2 to 9 C atoms in the acyl group and 9 to 23 C atoms in the alkane radical; Alkyl ether sulfates containing 10 to 20 carbon atoms in the alkyl group and 1 to 30 moles of ethylene oxide; water-soluble salts of olefin sulfonic acids containing 12 to 24 carbon atoms; and β-alkyl-oxyalkanesulfonates which contain 1 to 3 C atoms in the alkyl group and 8 to 20 C atoms in the alkane radical.

Preferred water soluble anionic organic surfactants for use herein include linear chain alkyl benzene sulfonates containing 10 to 16 carbon atoms in the alkyl group; Alkyl sulfates containing 10 to 20 carbon atoms; the coconut range alkyl glyceryl sulfonates; and alkyl ether sulfates, in which the alkyl radical contains 10 to 20 carbon atoms and in which the average degree of ethoxylation varies between 1 and 6.

Specific preferred anionic surfactants that can be used herein include: sodium linear Cio to Ci2 alkyl benzene sulfonate; Triethanolamine-Cio to Ci2-alkylbenzenesulfonate; Sodium tallow alkyl sulfate; Sodium coconut alkyl glyceryl ether sulfonate; and the sodium salt of a sulfated condensation product of C m to cis alcohol with 1 to 10 moles of ethylene oxide.

It must be clearly recognized that any of the above anionic surfactants can be used either separately or in mixtures.

Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds in which the aliphatic radicals can be straight or branched chain, in which one of the aliphatic substituents contains 8 to 18 C atoms and one contains an anionic, water-solubilizing group contains. Particularly preferred zwitterionic materials are the ethoxylated ammonium sulfonates and sulfates disclosed in U.S. Patent 3,925,262 and U.S. Patent 3,929,678. The inclusion of these surfactants in the compositions complements the excellent performance in removing greasy and oily dirt with excellent performance in removing clay dirt.

Particularly preferred ethoxylated zwitterionic surfactants have the formulas:

ch3

Cl6H33- + f- (C2H40) 9W ° 4 "

The above compounds containing 8 moles of ethylene oxide are also preferred. Additional preferred zwitterionic surfactants include those of the formula:

Cl6H33 | "(C2Hl) 0) yC2HltS04 (Ò2h4 °) xh

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14

Although the compositions may advantageously contain electrolytes, anionic surfactants, and zwitterionic surfactants, as described above, which are selected to meet the cloud point requirements, a preferred class of compositions is essentially free of interfering anions associated with the cation-active component can interact and thereby hinder the cleaning and textile finishing performance. What constitutes a “disruptive anion” depends on the non-ionic and cation-active components contained in a detergent composition and on the properties of the special anion, such as structure, volume and dissociation constant. In these compositions, the anionic materials should be present in amounts small enough that no more than 10 mole percent, preferably no more than 5 mole percent, of the cationic surfactant contained in the wash solution is complexed by the anionic material is transferred. For example, in preferred compositions, if an anionic material has a dissociation constant of at least 1 x 10-3 (such as sodium toluenesulfonate), it may be present in an amount up to 40% by weight of the cationic surfactant; if the anionic material has a dissociation constant of at least I x 10_5 but less than 1 x 10-3, it can be included in an amount up to 15% by weight of the cationic surfactant, and if the anionic material has a dissociation constant of less than 1 x 10-5 (such as sodium C, 18 linear alkylbenzenesulfonate), it can only be present in amounts up to 10% by weight of the cationic surfactant. Particularly preferred compositions of this type are those that are substantially free of phosphate, polyphosphate, silicate and polycarboxylate builder anions, carboxymethyl cellulose and anionic surfactants.

Other compatible additional components which can be included in the compositions according to the invention in their conventional use amounts introduced in the art include bleaching agents, bleach activators, dirt-suspending agents, corrosion inhibitors, dyes, fillers, optical brighteners, germicides, pH adjusting agents, enzymes, enzyme stabilizers, Perfumes, fabric softening components, anti-static agents and the like. Buffer can also be added to control the pH of the compositions, with low molecular weight amino acids, especially glycine, being preferred when the composition is in the form of a clear liquid. Because of the numerous and various performance advantages of the compositions according to the invention, however, many components, such as builders, agents for controlling static electricity, fabric softening agents and germicidal agents, are generally not required. The compositions according to the invention can additionally contain monoethanolamine, diethanolamine or triethanolamine components in amounts of up to 30%, preferably 5 to 20%. These components are useful as sources of alkalinity and in the formulation of clear, homogeneous liquid products that meet the cloud point requirements when placed in an aqueous wash solution.

Compositions according to the invention can be produced and used in a variety of physical forms, such as solid, powder, granulate, paste or liquid. The compositions are particularly well suited for incorporation into substrate objects for use in household washing processes. These objects consist of a water-insoluble substrate which removably contains an effective amount, preferably 20 to 80 g, of the detergent composition according to the invention. A particularly preferred substrate article contains a bleaching component and a bleach activator incorporated on the substrate together with the nonionic / cationic surface-active mixture.

A particularly preferred composition according to the invention is an aqueous liquid heavy-duty wash composition which contains 10 to 50%, preferably 15 to 40%, of the nonionic surfactant, 1 to 10%, preferably 1 to 6%, of the cationic surfactant; and which additionally contains 5 to 30%, preferably about 10%, monoethanolamine, diethanolamine, triethanolamine or mixtures thereof. These compositions can also contain 3 to 20% of an anionic surface-active agent, in particular one of the ethoxylated or non-ethoxylated alkyl sulfate variety. One embodiment of such a composition contains monoethanolamine, coconut trimethylam monium chloride as at least part of the cation-active component and a mixture of the condensation product of secondary Cn alcohol with an average of 7 moles of ethylene oxide together with the condensation product of secondary Cn alcohol with an average of 5 moles of ethylene oxide in a ratio of higher ethoxylated nonionic compound to lower ethoxylated nonionic compound of about 3: 1 as a nonionic surfactant. In these compositions, the amounts and proportions of the components can be varied so that a clear, homogeneous product is produced which has the required cloud point properties in the aqueous washing solution.

Washing processes

In its most general aspect, this invention enables a method for cleaning solid surfaces contaminated with greasy and / or oily materials using an aqueous washing solution containing 0.01 to 0.3% by weight of the detergent composition according to the invention, wherein the decreased monomer concentration of the cationic surfactant is 0.002 to 0.2, preferably 0.002 to 0.15 and most preferably 0.002 to 0.08; wherein the temperature of the solution is within a range of 20 ° C, preferably within a range of 15 ° C, more preferably within a range of 10 ° C, around the cloud point of the mixture of nonionic / cationic surfactant. In general, a given system performs best at removing greasy / oily dirt just at the point where the temperature of the wash solution equals the cloud point. The weight ratio of the nonionic surfactant to the cationic surfactant is 5.1: 1 to 100: 1, in particular 5.1: 1 to 50: 1, very particularly 6: 1 to 40: 1, especially 6: 1 to 20: 1.

Prior to this invention, it was completely unexpected that combinations of nonionic and cationic surfactants, even in the presence of a builder, could provide cleaning of either greasy and oily soils or particulate soils that would be competitive with commercially available full builder anionic detergents. Furthermore, there was no evidence that the reduced concentration of the cationic monomer and the cloud point were critical elements in obtaining the removal of greasy and oily contaminants. It was therefore completely unexpected that such combinations could be used to provide superior performance even in systems with little or no phosphate, as well as in systems that did not contain a builder or relatively ineffective builder.

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This performance is obtained when the newly discovered criteria set forth herein regarding the cloud point and reduced concentration of the cationic monomer in the wash process are met. The preferred method requires the wash solution to be near the cloud point temperature of the detergent composition, which is generally well above the CMC of the nonionic component. The concentration of the cationic surfactant should not be too low or too high above the CMC of the cationic component for optimal performance in removing greasy / oily dirt. These criteria, and the numerous other limitations based on considerations such as environmental desirability and safety, help define the preferred compositions set forth herein.

With the method described above, it is also possible to achieve superior removal of particulate soil if there is sufficient cationic surfactant in the wash solution.

It may be necessary to balance the need for a relatively high concentration of cationic surfactant (e.g. at least 50 ppm) with other factors, and it will be clearly seen that for very high ratios it may not be possible to be cationic at the present use concentrations, to achieve the best removal of particulate dirt. However, the particulate soil removal and greasy / oily soil removal achieved by these methods are superior to those provided by any known commercial detergent, while allowing the detergent formulator to address today's environmental and safety concerns.

In addition to the cleaning benefits noted, the present invention provides an impressive array of secondary but extremely desirable benefits that are almost unknown in the conventional anionic detergent compositions and methods of the prior art. E.g. depending on the identity and concentration of the cationic component, it is possible to obtain the advantages known for such cationic compounds from the prior art, e.g. antibacterial effect, antistatic effects, softening effects on textiles, and a previously undetected effect, namely the prevention or minimization of the transfer of certain dyes from one textile material to the other in the cleaning process.

In general, the compositions according to the invention are used in the washing process by forming an aqueous solution which is 0.01 (100 ppm) to 0.3% (3000 ppm), preferably 0.02 to 0.2%, most preferably 0, 03 to 0.15%, which contains the detergent composition within the above restrictions regarding the cloud point and the reduced monomer concentration, and moves the soiled textiles in this solution. The textiles can then be rinsed and dried. If the compositions according to the invention are used in this way, they provide extremely good removal of greasy and oily dirt as well as removal of particulate dirt and textile finishing performance. When the compositions according to the invention are used in foreign washing, industrial washing or hard surface cleaning operations, concentrations as high as about 2% can be used.

All percentages, parts and ratios used herein are by weight unless otherwise specified.

The following, non-limiting examples illustrate the compositions and the method according to the present invention.

Example I

Two compositions according to the invention were formulated by mixing together the components indicated below in the 10 quantities indicated. The cationic surfactants were chosen to be water dispersible when the compositions were used in the wash solution.

15 composition A:

Component weight%

Ci2 alcohol polyethoxylate, which contains an average of 5 moles of ethylene oxide (CuEs) HLB = 11 20 CMC (determined experimentally under the conditions of use specified herein) = 8 ppm 93.78

Palmitylalkyltrimethylammonium chloride (commercially available as Adogen 444)

25 CMC (determined experimentally under the conditions of use specified herein) = 7 ppm 6.22

Composition B:

30 component% by weight

C12E5 53.6 coconut alkyl trimethyl ammonium chloride

(commercially available as Adogen 461) 6.8

Sodium carbonate 33.8

35 sodium silicate (2.0 r) 5.8

Using the equations found in this description, it was found that the reduced concentration of the cationic monomer of Composition A 40 was about 0.0073 and that of Composition B was found to be about 0.023. The cloud point of composition A is about 45 ° C, while that of composition B is about 35 ° C.

The cleaning performance of these compositions was tested against that of a granular standard detergent composition with the following formulation:

Comparison 1

Component weight%

so sodium salt of sulfated tallow alcohol which has been ethoxylated with 3 moles of ethylene oxide 5.5 sodium tallow alkyl sulfate 5.5

Sodium C 1 | -8-linear alkylbenzenesulfonate 7.0

Silicate solids (2.0 r) 12.0

55 sodium tripolyphosphate 24.4

Sodium sulfate 36.8

Polyethylene glycol 6000 0.9

Moisture and minor components 100 (e.g. brightener, perfume etc.) rest until

60

For each of the above detergent compositions, a group of three 27.9 x 27.9 cm samples (one made from double-knit polyester, a 65/35 polyester / cotton blend and a cotton) were stained with four "separate soils (dirty motor oil, lipstick, triolein, and a clay-in-water suspension.) The three samples were then made into a load of clean mixed fabrics weighing an average of 2.7 kg, the tree

648 344

16

wool, polyester and cotton / polyester textiles were given, and the load was washed using one of the compositions described above in a Kenmore washing machine on a 1: 1 scale. Each of the compositions was added to the wash solution at a use concentration of about 0.1%. Composition A had a pH of 8 in the wash solution and Composition B had a pH of about 9.7. The wash water was at a temperature of 40 ° C and contained 154 ppm natural hardness. After washing was completed, each of the samples was rated for the removal of any soil on a scale of 1 to 10, with 0 meaning complete removal and 10 meaning no removal at all. For each treatment, the total of the clay removal ratings was added and the sum of the fat / oil removal ratings was added. Thus, for each treatment, the tone devaluation censorship could range from 0 for complete removal to 30 for no removal; and for the grease and oil stains, the grades could range from 0 for complete removal to 90 for no removal. The results obtained are summarized in the following table.

Detergent composition

Fat / oil removal

Sound removal

Comparison 1

78

18th

A

24th

14

B

24th

12

These data demonstrate the excellent performance in the removal of grease and oil dirt as well as the excellent performance in the removal of particulate dirt, which are obtained by using the compositions according to the invention even in the absence of any builder components.

Substantially similar results are obtained when the nonionic components in compositions A and B above are replaced by a C | 4_ | 5 alcohol polyethoxylate containing on average 4 moles of ethylene oxide (HLB = 8.9), a Ci2_i3- Alcohol polyethoxylate, which contains an average of 6.5 moles of ethylene oxide, a C] 4. 5-alcohol alcohol polyethoxylate, which contains an average of 7 moles of ethylene oxide (HLB = 11.5), a Cl2_i3 alcohol polyethoxylate, which contains an average of 3 moles of ethylene oxide contains (HLB = 7.9), and the same product, which is stripped so that essentially all of the lower ethoxylate and non-ethoxylated fractions are removed, a secondary cis alcohol polyethoxylate containing an average of 9 moles of ethylene oxide (HLB = 12.7), a coconut alcohol polyethoxylate, which contains an average of 5 moles of ethylene oxide, a Cio-alcohol polyethoxylate, which contains an average of 3 moles of ethylene oxide, a Ci4-alcohol poly-10 lyethoxylate, which contains an average of 6 moles of ethylene oxide, a Cn- Alcohol polyethoxylate, which contains an average of 4 moles of ethylene oxide, a C | 2_i3 alcohol polyethoxylate, which contains an average of 9 ethylene oxides (HLB = 13.3), a C] 4_i5 alcohol polyethoxylate, which contains an average of 3 moles of 15 ethylene oxide (HLB = 8 , 9), a Cj4_i5 alcohol poly-ethoxylate, which contains an average of 9 moles of ethylene oxide (HLB = 12.8), and mixtures of these surfactants.

Excellent cleaning results are also obtained when the ratio of nonionic surfactant to cationic surfactant in compositions A and B above 6: 1, 7: 1, 9: 1, 10: 1.12: 1, 17: 1 , 20: 1 or 25: 1.

Similar results are also obtained when the 25 sodium carbonate and sodium silicate components of the above composition B are replaced in whole or in part by other alkali metal tetraborates, perborates, bicarbonates or carbonates in comparable amounts.

Substantially similar results are also obtained if the cationic surfactants of compositions A and B are replaced in whole or in part by decyltrimethylammonium chloride, decyltrimethylammonium hydroxide, Ci4-alkyltrimethylammonium chloride, tri-decylmethylammonium chloride, a mixture of methyl-35 (1 ) -talgalkylamidoethyl- (2) -talgalkylimidazoliniummethylsul-fat (Varisoft 475) together with coconut alkyltrimethylammonium chloride (Adogen 461) in a ratio of Varisoft to Adogen of about 1: 1.3: 3.3: 1.2: 3 or 1 : 3 or a mixture of palmityltrimethylammonium chloride with coconut-40-nut alkyltrimethylammonium chloride in a palmityl to coconut compound ratio of about 3: 1.2: 1.3: 2, 1: 1, 1: 2 or 1: 3, or surfactants of the following Formulas:

CH,

HOH ^ -N -C ^ OH C12H25

Cl

0 CHt

1 l + 3

Cn _H -C-0-CH_CHo-M -CH, Br i-l io 2 2 | 3rd

ch3

(CMC = 50 ppm)

■ î î ÏÏ3

29 "0_C" CH2CH2 ~ C "°" CH2CH2 | ~ CH3

CH,

Cl

CH,

CH.

Cl

CH - N-CH -CH -0-C- (CH) -C-O-CH CH -N -CH Cl 3 I 2 2 2 10 22 | 3rd

CH CH

17th

648 344

CH-7

| 3rd

C12H2 5 ~ (CH2 CH2 °} 7 "CH2" C- 0- CH2 CH2 -N + - CH3 Br "

t »3

Q CH,

C12H21 "°" (CH2 '° H2 0) 10 ~ ö "CH2"? + "CH3 C1 ~

ch3

Example II Example III

The following two detergent compositions according to the invention were formulated.

Positions were formulated by listing those described below, combining the components described below in the components in the amounts specified, amounts and ratios. The cationic surfactants became 15. Each of these detergent compositions appeared cloudy when chosen to be at least water dispersible, was added to a wash solution at 40.6 ° C, which was when the compositions were used in wash solution. Presence of separate phases in the wash solution indicated.

Composition composition composition

Component CD E F

% By weight% by weight component% by weight% by weight

C12E5 95 91

Palmityltrimethylammonium chloride 3 6

Coconut alkyl trimethyl ammonium 2 3 umchloride

Composition C had a reduced concentration of the cationic monomer of about 0.006 and a cloud point of about 45 ° C, while Composition D had a reduced concentration of the cationic monomer of about 0.0135 and a cloud point of about 55 ° C.

The performance of each composition in removing 35 grease / oil and particulate soil was then tested using the method described in Example I above. Both compositions were used at a product concentration of about 0.1% in the wash solution in water at a temperature of 40 ° C. Composition 40 had a pH of 8 and Composition D had a pH of 7.9 in the wash solution. Composition C was used in water that had 120 ppm natural hardness, while Composition D was used in water that had 120, 240 and 360 ppm natural hardness. The performance of these compositions in removing dirt is summarized in the following table.

Detergent

hardness

Fat / oil

Volume-

composition

(ppm)

distance

distance

C.

120

16

8th

D

120

30th

7

D

240

22

8th

D

360

21st

12

C12E5 75

C12-13 alcohol polyethoxylate, which in

An average of 6.5 moles of ethylene oxide contains (C i2- [3C6> 5) - 80

Coconut alkyl trimethyl ammonium chloride 4.2 5

Distearyldimethylammonium chloride

(commercially available as Arosurf

TA-100) CMC = 1 ppm

Methyl (1) tallow alkylamidoethyl

(2) -talgalkylimidazoliniummethylsul-

fat (commercially available as Varisoft '

475) CMC = 8.5 ppm 4.2 15

Monoethanolamine 16.6

Cloud point (° C) 40 45

reduced concentration of the cationic monomer 0.011 0.030

The performance of compositions E and F in removing grease / oil and particulate soil was then tested using the test method described in Example I above against the comparative composition of Example I. All washes were done using water at 40 ° C containing 120 ppm natural hardness. Compositions E and F were used at a use concentration of about 0.1% in the wash solution, while the comparative composition was used at a use concentration of 0.14%. Composition E had a pH of 10.2 in the wash solution. The dirt removal results obtained are summarized in the following table:

The above compositions provided excellent grease and oil soil removal, as well as 60 advantages in removing particulate dirt and textile finishing even in the presence of increased hardness concentrations in the wash solution, without the need for builder components.

Excellent cleaning results are also obtained when the ratio of nonionic surfactant to cationic surfactant in compositions C and D above is about 10: 1, 15: 1.20: 1, 25: 1.30: 1.40: 1 or 50: 1.

Detergent composition fat / oil removal clay removal

Comparison 1

73

14

E

20th

8th

F

33

7

These data demonstrate the excellent performance in removing greasy / oily dirt and the excellent performance in removing particulate dirt obtained by using the detergent compositions according to the invention.

648 344

18th

Example IV

A composition according to the invention was formulated by combining the components specified below in the specified ratios.

Composition H

Component weight%

C12E5 46

Coconut alkyl trimethyl ammonium chloride 8

Sodium carbonate 34.5

Sodium silicate (2.0 r) 11.5

Cloud point (° C) 30 ° C decreased concentration of the cationic

Monomers 0.037

The performance of this soil removal composition was tested using the test method described in Example I against that of a standard low phosphate granular laundry detergent composition with the formulation below.

Comparison 2

Component weight%

Sodium Ci3 linear alkyl benzo sulfonate 20.0

Silicate solids (2, Or) 19.5

Sodium carbonate 20.8

Trisodium sulfosuccinate 2.0

Sodium metaphosphate 0.4

Sodium sulfate 31.5 moisture and minor components

(e.g. brightener, perfume etc.) rest up to 100

Both compositions were added to the aqueous wash solution at use concentrations of 0.14%. The composition H had a pH of 9 in the wash solution. The wash solution had a temperature of 40 ° C. and contained 120 ppm of natural hardness. The cleaning results obtained are summarized in the following table.

Detergent composition

Fat / oil removal

Sound removal

Comparison 2

75

4th

H

37

4th

These data show the excellent performance in the removal of greasy / oily dirt and the excellent performance in the removal of particulate dirt which are obtained by using the compositions according to the invention.

Example V

The relationship between the performance in removing greasy / oily dirt and cloud point / washing solution temperature was demonstrated in the following manner. The detergent composition tested was a mixture of the condensation product of Ci2-alcohol with 5 moles of ethylene oxide and Ci6-alkyltrimethylammonium chloride in a non-ionic / cationic ratio of 19: 1. The composition was used at a concentration of 1000 ppm in distilled water.

The performance of this composition in removing greasy / oily dirt as a function of wash water temperature was tested using a tergotometer with a 10 minute wash cycle and two 2 minute rinse cycles. For each test, two desized samples of 7.5 cm square polyester fabric were weighed. The samples were then stained with 200 mg technical triolein (containing 0.0083% Oil Red-O for visualization) and weighed again. The samples were aged for about 2 hours and were washed in the tergotometer (1000 ml water; 1000 ppm detergent composition), air dried and weighed again. The percent triolein removal was calculated using the formula: 100 x [weight (soiled) - weight (washed)] / [weight (soiled) - weight (clean)]. This procedure was repeated at a number of wash water temperatures.

The light scattering intensity of the detergent composition as a function of the solution temperature was determined as follows.

The light scattering intensity was measured using a model VM-12397 photogoniodiffusometer manufactured by the Société Française d'instruments de contrôle et d'analyses, France (the instrument is hereinafter referred to as Sofica). The Sofica sample cell and its lid were washed with hot acetone and allowed to dry. The surface active mixture was prepared and dissolved with distilled water at a concentration of 1000 ppm. A sample of approximately 15 ml of the solution was added to the sample cell using a syringe with a 0.2 ji NucIeopore filter. The needle of the syringe passed through the lid of the sample cell so that the interior of the cell was not exposed to atmospheric dust. The sample was held in a variable temperature bath and both the bath and the sample were stirred continuously. The bath temperature was heated using the Sofica heating device and cooled by adding ice (heating rate approx. 1 ° C./min); the temperature of the sample was determined by the bath temperature. The light scattering intensity of the sample was then determined at different temperatures, using a green filter and no polarizer in the Sofica.

The results of these tests are summarized in the following table.

Temperature (° C)

% Triolein removal

Scattering intensity

22

52

2nd

26

-

2nd

30th

90

-

32

-

3rd

36

-

4th

40

92

-

45

-

5

48

-

8th

50

97

13

52

-

16

56

-

25th

58

-

35

60

70

48

62

-

60

63

-

82

65

-

100

70

58

-

These data show that the optimal triolein removal for this detergent composition occurs in a wash solution that is at a temperature of about 50 ° C; this is approximately the same temperature at which the light

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

19th

648 344

Scattering of the solution in its movement to its maximum value (i.e. the cloud point of the mixture of nonionic / cationic agent) begins to increase too steeply. It can therefore be seen that by using this detergent composition in a wash solution that is at a temperature close to (i.e. within a range of about 20 ° C around) the cloud point of the composition, the maximum triolein removal for this composition is achieved.

Example VI

A liquid heavy-duty detergent composition having the formula given below is formulated by mixing the following components together in the proportions given.

Component weight%

Cu-alcohol polyethoxylate, which contains an average of 5 moles of ethylene oxide (CizEs) 85.15

Palmityltrimethylammonium chloride 5.65

Ethanol 8.0

Water, fluorescent, brightener, perfume and other minor components 1,2

This product has a cloud point that falls between 30 and 50 ° C, has a pH of about 7.5 when used in an automatic washing operation at a concentration of about 0.05%, and is excellent in removal of both particulate and greasy / oily contaminants.

Example VII

A substrate article for use in the automatic washing operation is made by using a 20.3 x 27.9 cm sheet of a Scott 8050 Industriai Towel that has an air permeability of about 39.6 m3 / min / m2 and a basis weight of about 77. 5 g per square and a thickness of 1.1 mm, impregnated with about 50 g of the composition described in Example VI above. The sheet is then dried to remove excess moisture. This subject provides a convenient method for introducing the compositions of the invention into the wash solution and also provides excellent performance in cleaning, static control, fabric softening and dye transfer inhibition.

A substrate article can also be made by molding one side of a 27.9 x 27.9 cm sheet of meltblown polypropylene, which is about 0.7 mm thick, has a basis weight of about 58.5 g per 0.836 m2 and has an air permeability of about 20 m3 per minute and per m2, coated with about 60 g of the detergent composition described in Example VI, arranging an identical substrate sheet over the coated sheet and hot welding the edges of the two substrates together, whereby the detergent composition within of the object is enclosed.

Example VIII

A solid, particulate detergent composition according to the invention with the formulation given below is produced in the following manner.

Component weight%

Cu alcohol polyethoxylate, which contains an average of 5 moles of ethylene oxide (C12E5) 39

Coconut alkyl trimethyl ammonium chloride 5

Urea 25

Sodium carbonate 15

Sodium silicate (2, Or) 15

subordinate components (anti-foaming agents, brighteners etc.) remainder up to 100

The nonionic and cationic components are mixed together and then mixed with the solid urea while being heated. The resulting product is then mixed with the carbonate, the silicate and the minor components. When used in an automatic washing operation at conventional use concentrations, this product has a pH of about 9 and provides excellent removal of particulate and greasy / oily dirt.

Example IX

A solid, particulate detergent composition according to the invention with the formulation given below is produced in the manner described in Example VIII above.

Component weight%

C12E5 39

Coconut alkyl trimethyl ammonium chloride 5

Urea 30

Sodium tripolyphosphate 15 subordinate components (anti-foaming agents, brighteners, moisture, etc.) balance up to 100

When used in an automatic washing machine at conventional use concentrations, this product has a pH of about 9 and provides excellent performance in removing particulate and greasy / oily dirt.

Example X

A liquid heavy-duty detergent composition having the formula given below is formulated by mixing the following components together in the proportions given. If the composition is formulated, it has a cloudy appearance.

Component weight%

Sodium Cn linear alkyl benzene sulfonate 14.4

C12E5 37.4

Coconut alkyl trimethyl ammonium chloride 5.8

Sodium sulfate 13.5 water and minor components (e.g. foam retardant, perfume, brightener)

Rest to 100

When used in an automatic washing operation at a concentration of about 0.05%, this product has a pH of about 9.5 and provides excellent removal of both particulate and greasy / oily stains. The product can also be used as a pretreatment by rubbing it on greasy / oily stains before the washing operation.

Example XI

A liquid heavy-duty detergent composition according to the invention having the formula given below is formulated by mixing the following components together in the ratios indicated.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

648 344

20th

component

% By weight

Ci: -I:, E65

50

Tallow alkyl trimethyl ammonium chloride

5

Monoethanolamine

5.5

Ethanol

5

Sodium chloride

2nd

Water and minor components

Rest until

100

When used in an automatic washing operation at a concentration of about 0.05%, this product has a pH of about 9 and provides excellent removal of greasy / oily, body and particulate contaminants and gives to those washed with them Textiles also have advantages in terms of combating static electricity and inhibiting dye transfer.

Substantially similar results are obtained when the cationic component is replaced in whole or in part by palmityltrimethylammonium chloride or hydrogenated tallow alkyltrimethylammonium chloride; and the nonionic component is wholly or partly replaced by the condensation product of Cn-alcohol with 5 moles of ethylene oxide, the condensation product of Ci4_i5-alcohol with 7 moles of ethylene oxide or mixtures thereof.

Example XII

A liquid heavy-duty detergent composition having the formula given below is formulated by mixing the following components together in the proportions given. When formulated, the composition has a clear, homogeneous appearance.

Component weight%

secondary Cn alcohol polyethoxylate containing an average of 7 moles of ethylene oxide (commercially available as Softanol 70 from Hippon Shokubai Kogyo K.K.) 30

secondary Ci2-alcohol polyvlate containing an average of 5 moles of ethylene oxide (commercially available as Softanol 50) 10

Coconut alkyl trimethyl ammonium chloride 5 monoethanolamine 15

Water and minor components 40

This product has a cloud point at around 15 ° C and provides excellent removal of particulate, greasy / oily and body contaminants when used under common Japanese laundry conditions, which generally use lower water temperatures than American washing conditions.

Example XIII

A liquid heavy-duty detergent composition having the formula given below is formulated by mixing the following components together in the proportions given. When formulated, the composition has a clear, homogeneous appearance.

Component weight%

secondary Ci2 alcohol polyethoxylate containing an average of 7 moles of ethylene oxide (commercially available as Softanol 70 from Nippon Shokubai Kogyo K.K.) 30.0

secondary Cn alcohol polyethoxylate containing an average of 5 moles of ethylene oxide (commercially available as Softanol 50) 10.0

Monoethanolamine 3.0

Coconut alkyltrimethylammonium chloride 0.7 5 methyl-1-tallowalkylamidoethyl-2-tallowalkylimi-

dazolinium methyl sulfate 0.75

Ethanol 2.0

Foam retardant 0.3

Water, brightener, perfume rest

This product provides excellent removal of particulate, greasy / oily and body contaminants when used under standard Japanese washing conditions that generally use lower water temperatures than American washing conditions.

Example XIV

A heavy duty laundry detergent composition of the formula given below is formulated by mixing the following components together in the proportions indicated. When formulated, the composition has a clear, homogeneous appearance.

Component weight%

secondary Cn alcohol polyethoxylate containing an average of 7 moles of ethylene oxide (commercially available as Softanol 70 from Nippon Shokubai Kogyo K.K.) 15.0

Cn secondary alcohol polyethoxylate containing an average of 5 moles of ethylene oxide (commercially available as Softanol 50) 5.0

Monoethanolamine 8.0

Coconut alkyl trimethyl ammonium chloride 1.13 ditallow alkyl dimethyl ammonium chloride 0.37

Isopropanol 1.5

Glycine 1.5

C12-14 alkyldimethylamine oxide 10.0

Water and minor ingredients (including perfume and colorants)

Rest to 100

This product has desirable foaming properties and provides excellent removal of particulate, greasy / oily and body contaminants when used under standard Japanese washing conditions which generally use lower water temperatures than American washing conditions.

Example XV

A liquid heavy-duty detergent composition of the formula given below is formulated by combining the following components in the stated proportions - a clear, homogeneous appearance.

Component wt .-% sodium sulfate of C12-15 alcohol, with the 3rd

Mole of ethylene oxide is ethoxylated 5.0

Cl2-I3E6, J 20.0

Coconut alkyl trimethyl ammonium chloride 3.5

Glycine 8.0

Sodium toluenesulfonate 10.0 water and minor components

Rest to 100

This product has desirable foaming properties and provides excellent removal of particulate, greasy / oily and body contaminants when used under normal Japanese wash conditions5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

21 648 344

saturated fatty acid with 16 to 22 carbon atoms in the alkyl chain 0.75 proteolytic enzyme (maxatase 15% pure

Enzyme) 0.4 5 minor auxiliaries and water remainder to 100

conditions that generally use lower water temperatures than American washing conditions.

Example XVI

A liquid coarse detergent composition of the formula given below was prepared by mixing the components listed together in the ratios indicated.

10th

Component weight%

Condensate of Ci4. | 5-fatty alcohol with an average of 7 moles of ethylene oxide 28.5

Triethanolamine salt of linear

Alkylbenzenesulfonic acid, in which the alkyl chain 15

an average of 11.9 carbon atoms has 20.0

C8_i8-Alkyldihydroxyäthylmethylammonium- 1.5 chloride

Ethanol 10.0

Diethylenetriaminepentamethylenephosphon 20

acid 0.3

Citric acid 0.2

9: 1 mixture of dimethylpolysiloxane and airgel silica, emulsified in highly ethoxylated fatty acid (commercially available 25

available as DB 31 from Dow Corning) 0.3

The above composition was homogeneous and stable over long periods of time. In addition, based on prior art compositions, it provided unexpectedly superior performance in removing greasy stains.

Substantially similar results are obtained when the cationic component is replaced in whole or in part by a comparable amount of a quaternized nitrogen-containing component selected from the group consisting of coconut alkyl trimethyl ammonium chloride, coconut alkyl trimethyl ammonium bromide, benzyl dihydroxy ethyl methyl ammonium chloride quaternary coconut alkyl ammonium compounds in which 2 to 8 moles of ethylene oxide are condensed from the nitrogen, and mixtures thereof.

Claims (12)

648 344 (1) 2. Composition according to claim 1, characterized in that it also contains up to 20 wt .-% phosphate materials. (2) , 2nd 0 ti -c-o- 0 II -o-c-. 0 R " u i -C-N- 0 R2 i u -N-C 20th 25th 30th -0-, -o-c-o- 0 H HO u i i u -O-ü-N-, -N-C-0- and mixtures thereof, where each R1 contains 8 to 22 carbon atoms and R1 can additionally contain an average of up to 12 ethylene oxide groups; m is a number from 1 to 3, each R1 containing no more than 14 carbon atoms if m - 2 and each R1 containing no more than 11 carbon atoms if m = 3; each R2 represents an alkyl or hydroxyalkyl group containing 1 to 4 carbon atoms or a benzyl group, with no more than one R2 in a molecule being benzyl; x represents zero to 11; Y is selected from the group consisting of 2nd PATENT CLAIMS 1. Detergent composition which has a pH of at least 6.5 at a concentration of 0.05% by weight in the aqueous wash solution and which is free from oily hydrocarbon materials and cation-active materials which contain an average of 13 or more ethylene oxide groups, characterized in that it has 5 to 100% by weight of a surface-active mixture which contains the following components: (a) a biodegradable, non-ionic surfactant of the formula: 3rd 648 344 ven surfactants are contained, is not greater than 28. 3. Composition according to claim 1 or 2, characterized in that the surface-active mixture has a cloud point of 10 to 70 ° C. (3) (1) 4. Composition according to one of claims 1 to 3, characterized in that L is 1. -4 N ± II , c- V A- + N N-II I -C C- V and R (OC2H4) nOH wherein R is a primary or secondary alkyl chain having 8 to 22 carbon atoms and n is an average number from 2 to 12 and which has an HLB value of 5 to 17; and (b) a cationic surfactant free of hydrazinium groups and the formula: R'mR \ YLZ wherein each R1 is an organic group containing an unbranched or branched alkyl or alkenyl group which is optionally substituted by up to 3 phenyl or hydroxyl groups and is optionally interrupted by up to 4 structures selected from the group, from 5. Composition according to one of claims 1 to 4, characterized in that n stands for 2 to 9 in the nonionic surface-active agent. (5) 6. Composition according to one of claims 1 and 3 to 5, characterized in that it is free of phosphate materials. (6) -N ± -C. \ / + i yW — c- v_i -p ± -s ± -N- <W> pH (? 2W -N- I. <W> pH wherein p is 1 to 12. where j eaes p is 1 to 12, 40 7. Composition according to one of claims 1 to 6, characterized in that Y is selected from the group consisting of 45 55 60 -N- -N ± (c2H4o) pH and -N- (C2H ,, 0) pH where p is 1 to 10. (7) 8. Composition according to claim 7, characterized in that Y , m is 1, x is 3, R1 is a Cio to Cis alkyl group and each R2 is a methyl group. (8th) / \ 9. Composition according to one of claims 1 to 8, characterized in that it additionally contains up to 50 wt .-% of a component selected from the group consisting of anionic surfactants, zwitterionic surfactants and mixtures thereof 65 exists. 9. Composition according to one of claims 1 to 8, characterized in that the weight ratio of nonionic surfactant to cationic surfactant is 6: 1 to 20: 1. (9) their mixtures; L stands for 1 or 2, the Y groups being separated from one another by a grouping selected from the group consisting of R! And R2 groups with 1 to 22 C atoms and two free carbon single bonds, if L is 2; Z is an anion in a number sufficient to impart electrical neutrality to the molecule; wherein the cationic surfactant is dispersible in water in admixture with the nonionic surfactant; wherein the weight ratio of the nonionic surfactant to the cationic surfactant is in the range of 5.1: 1 to 100: 1 and the mixture has a cloud point of 0 to 95 ° C. 10. Composition according to one of claims 1 to 9, characterized in that the total number of carbon atoms in the R1 and R2 groups of the cationic 11. Composition according to one of claims 1 to 3, characterized in that the nonionic surfactant is selected from the group consisting of C12 to Cu alkanols which are condensed with 4 to 10 moles of ethylene oxide, C14 to Cis alkanols which are condensed with 6 to 10 moles of ethylene oxide and mixtures thereof; and which contains the nonionic surfactant and the cationic surfactant in a weight ratio of 5.1: 1 to 30: 1. 12. Composition according to one of claims 1 to 3, characterized in that the nonionic surfactant is selected from the group consisting of the condensation product of C12- to Cn-alkanol with 6 to 10 moles of ethylene oxide, the condensation product of C14- to cis -Alkanol with 5 to 9 moles of ethylene oxide and mixtures thereof; wherein in the cationic surfactant x is 2, m is 2 and each R1 is a coconut alkyl group; and the weight ratio of nonionic surfactant to cationic surfactant is 5.1: 1 to 15: 1.