CA1109753A - Storage-stable laundry detergent compositions having enhanced performance - Google Patents
Storage-stable laundry detergent compositions having enhanced performanceInfo
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- CA1109753A CA1109753A CA318,450A CA318450A CA1109753A CA 1109753 A CA1109753 A CA 1109753A CA 318450 A CA318450 A CA 318450A CA 1109753 A CA1109753 A CA 1109753A
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Abstract
STORAGE-STABLE LAUNDRY DETERGENT
COMPOSITIONS HAVING ENHANCED PERFORMANCE
Abstract of the Disclosure Laundry detergent compositions offering improved removal of particulate and greasy/oily soils, containing mixtures of selected nonionic and hydrolyzable cationic surfactants, together with specifically defined alkalinity sources, are disclosed. This invention permits the for-mulation of compositions which are alkaline in the laundry solution, and in which hydrolyzable cationic surfactants are stable during long periods of storage.
COMPOSITIONS HAVING ENHANCED PERFORMANCE
Abstract of the Disclosure Laundry detergent compositions offering improved removal of particulate and greasy/oily soils, containing mixtures of selected nonionic and hydrolyzable cationic surfactants, together with specifically defined alkalinity sources, are disclosed. This invention permits the for-mulation of compositions which are alkaline in the laundry solution, and in which hydrolyzable cationic surfactants are stable during long periods of storage.
Description
---` 11!19753 Background of the Invention This invention relates to storage-stable, alkaline laundry detergent compositions, preferred embodiments of which exhibit excellent particulate and greasy/oily soil removal performance, as well as fabric softening, static control and dye transfer inhibition benefits, to fabrics laundered therewith.
It is taught in Canadian Patent Application Serial No. 306,456, Cockrell, filed June 29, 1978, and Canadian Patent Application Serial No. 306,474, Murphy, filed June 29, 1978, that by selection and combination of specific types of nonionic and cationic surfactants, excellent particulate and greasy/oily soil removal laundering performance can be obtained. In preferred embodiments of those compositions, by choosing specific types of cationic surface-active agents, biodegradable laundry detergent c~mpositions can be formulated which exhibit particulate and grease/oil removal benefits as well as fabric softening, static control, and dye transfer inhibition benefits. Detergent compositions containing these specific biodegradable surfactants are described in Canadian Patent Application Serial No. 306,513, Letton, filed June 29, 1978, and Canadian Patent Application Serial No. 306,517, Letton, filed June 29, 1978.
It is further taught in the above applications that it is desirable that the detergent compositions form alkaline laundry solutions in order to improve the removal of oily body soils. However,because these preferred cationic sur-factants contain a biodegradable linkage, such as an ester or amide linkage, they tend to hydrolyze upon storage and use, when included in such alkaline detergent compositions, r~
1~9753 thereby reducing their effectiveness during the launder-ing operation. It has now been found that by using the specific types of alkalinity sources defined herein, alkaline detergent compositions may be formulated which - ;
minimize the hydrolysis of hydrolyzable linkage-containing cationic surfactants, and particularly the preferred bio-degradable cationic surfactants discussed above, during storage and use.
It is, therefore, an object of the present invention to provide alkaline laundry detergent compositions, containing cationic surfactants including hydrolyzable linkages, which are storage-stable.
9~S3 It is a further object of the present invention to provide laundry detergent compositions which yield excellent removal of particulate and greasy~oily soils, as well as fabric softening, static control, and dye transfer inhibition, to fabrics laundered therewith.
lt is a still further object of the present invention to provide laundry detergent compositions, yielding the above cleaning and fabric care benefits, which are biodegradable.
It is yet another.object of the present invention to - -provide a process for laundering fabrics, yielding excellent removal of oily body soils, clay and g~easy/oily soils, utilizing detergent compositions which contain selected cationic and nonionic surfactants.
Summary of the I-nvention The present invention relates to storage and wash solution-stable laundry detergent compositions comprising:
(a) from about 2% to about 95% of a cationic surfactant which contains at least one hydrolyzable linkage selected from the group consisting of:
O O O O O H
-C-, -C-O-, -O-C-, -O-, -O-C-O-, -~-N-, H O O H H O
1 11 11 ~ I 11 -~-C-, -O-C-N-, -N-C-O-, and mixtures thereof; and (b) from about l~ to about 25~ of an inorganic alkaline component which is insoluble in said cationic surfactant, and which is present in an amount such that the detergent composition forms a solution having a pH of from about 8 to about lO within 3 .
minutes after it is placed in 100F water at a concentration of about 0.15~.
A preferred aspect of the present invention en~ompasses alkaline, laundry detergent compositions, which provide excellent cleaning of particulate and greasy/oily soils, together with a range of fabric care benefits, comprising:
(a) from about 2~ to about 95% of a surfactant mixture consisting essentially of:
(1) a nonionic surfactant having an HLR of from about 5 to about 17; and
It is taught in Canadian Patent Application Serial No. 306,456, Cockrell, filed June 29, 1978, and Canadian Patent Application Serial No. 306,474, Murphy, filed June 29, 1978, that by selection and combination of specific types of nonionic and cationic surfactants, excellent particulate and greasy/oily soil removal laundering performance can be obtained. In preferred embodiments of those compositions, by choosing specific types of cationic surface-active agents, biodegradable laundry detergent c~mpositions can be formulated which exhibit particulate and grease/oil removal benefits as well as fabric softening, static control, and dye transfer inhibition benefits. Detergent compositions containing these specific biodegradable surfactants are described in Canadian Patent Application Serial No. 306,513, Letton, filed June 29, 1978, and Canadian Patent Application Serial No. 306,517, Letton, filed June 29, 1978.
It is further taught in the above applications that it is desirable that the detergent compositions form alkaline laundry solutions in order to improve the removal of oily body soils. However,because these preferred cationic sur-factants contain a biodegradable linkage, such as an ester or amide linkage, they tend to hydrolyze upon storage and use, when included in such alkaline detergent compositions, r~
1~9753 thereby reducing their effectiveness during the launder-ing operation. It has now been found that by using the specific types of alkalinity sources defined herein, alkaline detergent compositions may be formulated which - ;
minimize the hydrolysis of hydrolyzable linkage-containing cationic surfactants, and particularly the preferred bio-degradable cationic surfactants discussed above, during storage and use.
It is, therefore, an object of the present invention to provide alkaline laundry detergent compositions, containing cationic surfactants including hydrolyzable linkages, which are storage-stable.
9~S3 It is a further object of the present invention to provide laundry detergent compositions which yield excellent removal of particulate and greasy~oily soils, as well as fabric softening, static control, and dye transfer inhibition, to fabrics laundered therewith.
lt is a still further object of the present invention to provide laundry detergent compositions, yielding the above cleaning and fabric care benefits, which are biodegradable.
It is yet another.object of the present invention to - -provide a process for laundering fabrics, yielding excellent removal of oily body soils, clay and g~easy/oily soils, utilizing detergent compositions which contain selected cationic and nonionic surfactants.
Summary of the I-nvention The present invention relates to storage and wash solution-stable laundry detergent compositions comprising:
(a) from about 2% to about 95% of a cationic surfactant which contains at least one hydrolyzable linkage selected from the group consisting of:
O O O O O H
-C-, -C-O-, -O-C-, -O-, -O-C-O-, -~-N-, H O O H H O
1 11 11 ~ I 11 -~-C-, -O-C-N-, -N-C-O-, and mixtures thereof; and (b) from about l~ to about 25~ of an inorganic alkaline component which is insoluble in said cationic surfactant, and which is present in an amount such that the detergent composition forms a solution having a pH of from about 8 to about lO within 3 .
minutes after it is placed in 100F water at a concentration of about 0.15~.
A preferred aspect of the present invention en~ompasses alkaline, laundry detergent compositions, which provide excellent cleaning of particulate and greasy/oily soils, together with a range of fabric care benefits, comprising:
(a) from about 2~ to about 95% of a surfactant mixture consisting essentially of:
(1) a nonionic surfactant having an HLR of from about 5 to about 17; and
(2) a cationic surfactant selected from the group consisting of:
(i) R2-(Zl)a~(R3)n-Z2-(CH2)m-N -Rl X
R
wherein each Rl is Cl to C~ alkyl or hydroxy-alkyl; R2 is C5 to C30 straigh~ or branched chain alkyl, alkenyl, alky].benzyl, or alkyl phenyl group or X Rl- N-(CH2)s-, wherein s is from 0 to S;
Rl R3 is Cl to C20 alkylene or alkenylene, a is 0 or 1, n is 0 or 1, and a is 1 only when n is l; m is f~om 1 to 5; zl and z2 are each selected from the group consisting of:
~ ~J9753 O O O ~ H
It 11 11 11 l -C -O -, -O -C -, -O-, -O-C -O -, -C -N-, H O O H H O
--N--C--, --O--C--N--, --N--C-O--and wherein at least one of said groups is selected from the group consisting of ester, reverse ester, amide and reverse amide; and X
is an anion which makes the surfactant at least water-dispersible;
R2 Rl (ii) R3-ot(c~)noly-(zl)a-lR4)~-z2-(cH2)m N -Rl X
R
wherein each Rl is Cl to C~ alkyl or hydroxyalkyl;
each R2 is either hydrogen or Cl to C3 alkyl; R3 is C4 to C3~ straight or branched chain alkyl~ alkenyl or alkylbenzyl; R4 is Cl to C10 alkylene or alkenylene; n is rom 2 to 4; y is from 1 to 2Q; a is O or 1, t is O o~
1, and a can be 1 only when t is 1; m is from 1 to 5; z2 is selected from the group consisting of O O O O H
-C-O-, -C-, -O-, -O-C-O-, -C-N -, H O O H H O
1 11 11 1 ( 11 -N-~-, -O-C-N-, -N-C-O--97~;3 r-~
Z is selected from the group consisting of O O O H H O H O
Il 11 11 1 1 il I 11 -C-O-, -C-, -C-N-, -N-C-, -N-C-O-, and wherein at least one of said zl and z2 groups is selected from the group consisting of ester, reverse ester, amide, and reverse amide; and X is an anion which makes the surfactant at least water-dispersible; and (iii) mixtures thereof;
wherein the ratio of said nonionic surfactant to said cationic surfactant is in the range of from about 1:1 to about 100:1; and (b) from about 1% to about 25% of an inorganic alkaline component which is insoluble in said cationic/
nonionic surfactant mixture, and which is present in an amount such that the detergent composition forms a solution having a pH of from about 8 to about 10 within about 3 minutes after addition to 100F water at a concentration of about 0.15% by weight.
Preferred nonionic surfactants are biodegradable and have the formula R(OC2H4)nOH wherein R is a primary or secondary alkyl chain of from about 8 to about 22 carbon atoms and n is an average of from about 2 to about 12.
Preferred alkalinity sources for use in the compositions of the present invention include borax pentahydrate, borax decahydrate, sodium carbonate and mixtures of these components.
.~r~
11~)9753 The compositions herein may also contain various optional adjunct materials commonly employed in laundry detergent compositions.
A method of laundering fabrics, yielding the cleaning and fabric care benefits described herein, utilizing the detergent compositions of the present invention, is also taught.
Detailed Description of the Invention The compositions of the present invention contain a hydrolyzable cationic surfactant, or preferably a mixture of selected nonionic and cationic surfactants, together with specific types of inorganic alkalinity-producing components. The compositions contain from about 2% to about 95%, preferably from about 10% to about 90%, and most preferably from about 15% to about 85%, of the cationic or nonlonic/cationic surfactant components.
The preferred mixtures are disclosed in detail and claimed in Canadian Patent Applications Serial Nos~
306,513 and 306,517, Letton, filed June 29, 1978, and provides excellent cleaning of particulate and greasy/oily soils, together with a range of fabric care benefits.
The specific nonionic and cationic surfactants disclosed therein, and which are also described below, may be combined in ratios of nonionic surfactant to cationic surfactant by weight of from about 1:1 to about 100:1, preferablv from about 5:3 to about 50:1, most preferably from about 5:3 to about 20:1. Particularly preferred ratios are from about 5:3 to about 10:1, preferably from about 5:3 to about 5:1, particularly about 5:2. The specific components useful in the compositions of the present invention are described below.
Preferred compositions of the present invention are formulated based on their cloud points and/or reduced cationic monomer concentrations; these concepts are described in detail in Canadian Patent Application Serial No. 306,456, Cockrell, filed June 29, 1978 and Canadian Patent Application Serial No. 306,474, Murphy, filed June 29, 1978. In optimizing greasy/oily soil removal, the compositions should be formulated to have a cloud point of from about 0 to about 95 C, preferably from about 10 to about 70 C, most preferably from about 20 to about 70 C, and a reduced cationic monomer concentration of from about 0.002 to about 0.2, especially from about 0.002 to about 0.15, particularly from about 0.002 to about 0.08.
In optimizing particulate soil removal, the compositions should be formulated to have a reduced cationic monomer concentration of from about 0.005 to about 0.2, preferably from about 0.008 to about 0.15, and particularly from about 0.01 to about 0.1.
_nionic Surfactant Nonionic surfactants, having an HLB of from about 5 to about 17, well-known in the detergency arts, may be included in the compositions of the present invention together with the cationic surfactants defined herein-after. They may be used singly or in combination with one or more of the preferred alcohol ethoxylate nonionic surfactants, described below, to form nonionic surfactant mixtures useful in combination with the cationic surfac-tants. Examples of such surfactants are listed in U.S.
Patent 3,717,630, Booth, issued February 20, 1973, and U.S. Patent 3,332,880, Kessler et al, issued July 25, 1967. Nonlimiting examples of suitable nonionic ~A
1~)9753 surfactants which may be used in the present invention are as follows:
(1) The polyethylene oxide condensates of alkyl phenols.
These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide, said ethylene oxide being present in an amount equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds can be derived, for example, from polymerized propylene, di-isobutylene, and the like. Examples of compounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol; dodecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol;
dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol; and di-isooctyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol.
Commercially available nonionic surfactants of this type include Igepal* C0-630, marketed by the GAF Corporation, and Triton* X-45, X-114, X-100, and X-102, all marketed by the Rohm & Haas Company.
(2) The condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Examples of such ethoxylated alcohols include the condensation product of myristyl alcohol condensed with about 10 moles * Trade Marks ~1~'97S3 of ethylene oxide per mole of alcohol; and the conden-sation product of about 9 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with alkyl chains varying in length from 10 to 14 carbon atoms).
Examples of commercially available nonionic surfactants of this type include Tergitol* 15-S-9, marketed by Union Carbide Corporation, Neodol* 45-9, marketed by Shell Chemical Company, and Kyro* EOB, marketed by The Procter & Gamble Company.
(i) R2-(Zl)a~(R3)n-Z2-(CH2)m-N -Rl X
R
wherein each Rl is Cl to C~ alkyl or hydroxy-alkyl; R2 is C5 to C30 straigh~ or branched chain alkyl, alkenyl, alky].benzyl, or alkyl phenyl group or X Rl- N-(CH2)s-, wherein s is from 0 to S;
Rl R3 is Cl to C20 alkylene or alkenylene, a is 0 or 1, n is 0 or 1, and a is 1 only when n is l; m is f~om 1 to 5; zl and z2 are each selected from the group consisting of:
~ ~J9753 O O O ~ H
It 11 11 11 l -C -O -, -O -C -, -O-, -O-C -O -, -C -N-, H O O H H O
--N--C--, --O--C--N--, --N--C-O--and wherein at least one of said groups is selected from the group consisting of ester, reverse ester, amide and reverse amide; and X
is an anion which makes the surfactant at least water-dispersible;
R2 Rl (ii) R3-ot(c~)noly-(zl)a-lR4)~-z2-(cH2)m N -Rl X
R
wherein each Rl is Cl to C~ alkyl or hydroxyalkyl;
each R2 is either hydrogen or Cl to C3 alkyl; R3 is C4 to C3~ straight or branched chain alkyl~ alkenyl or alkylbenzyl; R4 is Cl to C10 alkylene or alkenylene; n is rom 2 to 4; y is from 1 to 2Q; a is O or 1, t is O o~
1, and a can be 1 only when t is 1; m is from 1 to 5; z2 is selected from the group consisting of O O O O H
-C-O-, -C-, -O-, -O-C-O-, -C-N -, H O O H H O
1 11 11 1 ( 11 -N-~-, -O-C-N-, -N-C-O--97~;3 r-~
Z is selected from the group consisting of O O O H H O H O
Il 11 11 1 1 il I 11 -C-O-, -C-, -C-N-, -N-C-, -N-C-O-, and wherein at least one of said zl and z2 groups is selected from the group consisting of ester, reverse ester, amide, and reverse amide; and X is an anion which makes the surfactant at least water-dispersible; and (iii) mixtures thereof;
wherein the ratio of said nonionic surfactant to said cationic surfactant is in the range of from about 1:1 to about 100:1; and (b) from about 1% to about 25% of an inorganic alkaline component which is insoluble in said cationic/
nonionic surfactant mixture, and which is present in an amount such that the detergent composition forms a solution having a pH of from about 8 to about 10 within about 3 minutes after addition to 100F water at a concentration of about 0.15% by weight.
Preferred nonionic surfactants are biodegradable and have the formula R(OC2H4)nOH wherein R is a primary or secondary alkyl chain of from about 8 to about 22 carbon atoms and n is an average of from about 2 to about 12.
Preferred alkalinity sources for use in the compositions of the present invention include borax pentahydrate, borax decahydrate, sodium carbonate and mixtures of these components.
.~r~
11~)9753 The compositions herein may also contain various optional adjunct materials commonly employed in laundry detergent compositions.
A method of laundering fabrics, yielding the cleaning and fabric care benefits described herein, utilizing the detergent compositions of the present invention, is also taught.
Detailed Description of the Invention The compositions of the present invention contain a hydrolyzable cationic surfactant, or preferably a mixture of selected nonionic and cationic surfactants, together with specific types of inorganic alkalinity-producing components. The compositions contain from about 2% to about 95%, preferably from about 10% to about 90%, and most preferably from about 15% to about 85%, of the cationic or nonlonic/cationic surfactant components.
The preferred mixtures are disclosed in detail and claimed in Canadian Patent Applications Serial Nos~
306,513 and 306,517, Letton, filed June 29, 1978, and provides excellent cleaning of particulate and greasy/oily soils, together with a range of fabric care benefits.
The specific nonionic and cationic surfactants disclosed therein, and which are also described below, may be combined in ratios of nonionic surfactant to cationic surfactant by weight of from about 1:1 to about 100:1, preferablv from about 5:3 to about 50:1, most preferably from about 5:3 to about 20:1. Particularly preferred ratios are from about 5:3 to about 10:1, preferably from about 5:3 to about 5:1, particularly about 5:2. The specific components useful in the compositions of the present invention are described below.
Preferred compositions of the present invention are formulated based on their cloud points and/or reduced cationic monomer concentrations; these concepts are described in detail in Canadian Patent Application Serial No. 306,456, Cockrell, filed June 29, 1978 and Canadian Patent Application Serial No. 306,474, Murphy, filed June 29, 1978. In optimizing greasy/oily soil removal, the compositions should be formulated to have a cloud point of from about 0 to about 95 C, preferably from about 10 to about 70 C, most preferably from about 20 to about 70 C, and a reduced cationic monomer concentration of from about 0.002 to about 0.2, especially from about 0.002 to about 0.15, particularly from about 0.002 to about 0.08.
In optimizing particulate soil removal, the compositions should be formulated to have a reduced cationic monomer concentration of from about 0.005 to about 0.2, preferably from about 0.008 to about 0.15, and particularly from about 0.01 to about 0.1.
_nionic Surfactant Nonionic surfactants, having an HLB of from about 5 to about 17, well-known in the detergency arts, may be included in the compositions of the present invention together with the cationic surfactants defined herein-after. They may be used singly or in combination with one or more of the preferred alcohol ethoxylate nonionic surfactants, described below, to form nonionic surfactant mixtures useful in combination with the cationic surfac-tants. Examples of such surfactants are listed in U.S.
Patent 3,717,630, Booth, issued February 20, 1973, and U.S. Patent 3,332,880, Kessler et al, issued July 25, 1967. Nonlimiting examples of suitable nonionic ~A
1~)9753 surfactants which may be used in the present invention are as follows:
(1) The polyethylene oxide condensates of alkyl phenols.
These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide, said ethylene oxide being present in an amount equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds can be derived, for example, from polymerized propylene, di-isobutylene, and the like. Examples of compounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol; dodecylphenol condensed with about 12 moles of ethylene oxide per mole of phenol;
dinonyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol; and di-isooctyl phenol condensed with about 15 moles of ethylene oxide per mole of phenol.
Commercially available nonionic surfactants of this type include Igepal* C0-630, marketed by the GAF Corporation, and Triton* X-45, X-114, X-100, and X-102, all marketed by the Rohm & Haas Company.
(2) The condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Examples of such ethoxylated alcohols include the condensation product of myristyl alcohol condensed with about 10 moles * Trade Marks ~1~'97S3 of ethylene oxide per mole of alcohol; and the conden-sation product of about 9 moles of ethylene oxide with coconut alcohol (a mixture of fatty alcohols with alkyl chains varying in length from 10 to 14 carbon atoms).
Examples of commercially available nonionic surfactants of this type include Tergitol* 15-S-9, marketed by Union Carbide Corporation, Neodol* 45-9, marketed by Shell Chemical Company, and Kyro* EOB, marketed by The Procter & Gamble Company.
(3) The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds has a molecular weight of from about 1500 to 1800 and exhibits water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain of the commercially available Pluronic*
surfactants, marketed by Wyandotte Chemical Corporation.
surfactants, marketed by Wyandotte Chemical Corporation.
(4) The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine. The hydrophobic moiety of these products consists of the reaction product of ethylene diamine ands excess propylene oxide, said moiety having a molecular weight of from about 2500 to about 3000. This * Trade Marks A
~ 1~)97S3 hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40~ to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic*
compounds, marketed by Wyandotte Chemical Corporation.
A preferred group of nonionic surfactants useful herein comprises a mixture of "surfactant" and "cosur-factant", containing at least one nonionic surfactantfalling within the definition of nonionic surfactants useful in the present invention, as described in Canadian Patent No. 1,059,8~5, Collins, issued on August 7, 1979.
Preferred alcohol ethoxylate nonionic surfactants for use in the compositions of the present invention are bio-degradable and have the formula R(OC2H4)nOH, wherein R is a primary or secondary alkyl chain of from about 8 to about 22, preferably from about 10 to about 20, carbon atoms and n is an average of from about 2 to about 12, particularly from about 2 to about 9. The nonionics have an HLB (hydrophilic-lipophilic balance) of from about 5 to about 17, preferably from about 6 to about 15. HLB is defined in detail in Nonionic Surfactants, by M. J. Schick, Marcel Dekker, Inc., 1966, pages 607-613.
In preferred nonionic surfactants, n is from 4 to 7.
Primary linear alcohol ethoxylates (e.g., alcohol ethoxy-lates produced from organic alcohols which contain about 20~ 2-methyl branched isomers, commercially available from Shell Chemical Company under the trademark Neodol) are Ipreferred from a performance standpoint.
* Trade Mark A
Particularly preferred nonionic surfactants for use in the compositions of the present invention include the condensation product of C10 alcohol with 3 moles of ethylene oxide; the condensation product of tallow alcohol with 9 moles of ethylene oxide; the condensation product of coconut alcohol with 5 moles of ethylene oxide; the condensation product of coconut alcohol with 6 moles of ethylene oxide;
the condensation product of C12 alcohol with 5 moles of ethylene oxide; the condensation product of C12 13 alcohol -with 6.5 moles of et~lylene oxi.de, and the same condensatinnproduct which is stripped so as to r~move substantially all lower ethoxylate and nonethoxylated fractions; the condensation product of C12 13 alcohol with 3 moles of ethylene oxide, and the same condensation product which i5 stripped so as to remove substantially all lower ethoxylate.and nonethoxylated fractions; the condensation product of C12 ]3 alcohol with 9 moles of ethylene oxide; the condensation product of Cl~ 15 alcohol with 2.25 moles of ethylene oxide; the condensati.on product of Cl~ 15 alcohol with 4 moles of ethylene oxide;
the condensation product of C14 15 alcohol with 7 moles of ethylene oxide; and the condensation product of Cl~ 15 alcohol with 9 moles of ethylene oxide.
The compositions of the present invention may contain mixtures of the preferred alcohol ethoxylate nonionic surfactants together with other types of nonionic surfactants.
Preferred nonionic surfactant mixtures contain at least one of the preferred alcohol ethoxylate nonionics, and have a ratio of the preferred alcohol ethoxylate surfactant (or surfactants) to the other nonionic surfactant ~or surfactants) of from about 1:1 to about 5:1. Specific examples of surfactant mixtures useful in the present invention include a mixture 1 1~9753 of the condensation product of C14 15 alcohol with 3 moles of ethylene oxide (Neodol* 45-3) and the condensation product of C14 15 alcOhol with 9 moles of ethylene oxide (Neodol* 45-9), in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from about 1:1 to about 3:1;
a mixture of the condensation product of C10 alcohol with 3 moles of ethylene oxide together with the condensation product of a secondary C15 alcohol with 9 moles of ethylene oxide (Tergitol 15-S-9), in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from about 1:1 to about 4:1; a mixture of Neodol* 45-3 and Tergitol* 15-S-9, in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from about 1:1 to about 3:1; and a mixture of Neodo~* 45-3 with the condensation product of myristyl alcohol with 10 moles of ethylene oxide, in a ratio of lower ethoxylate to higher ethoxylate of from about 1:1 to about 3:1.
Preferred nonionic surfactant mixtures may also contain alkyl glyceryl ether compounds together with the preferred alcohol ethoxylate surfactants. Particularly preferred are glyceryl ethers having the formula R-O(CH2CH2O)nCH2CHCH2OH
OH
wherein R is an alkyl or alkenyl group of from about 8 to about 18, preferably about 8 to 12, carbon atoms or an alkaryl group having from about 5 to 14 carbons in the alkyl chain, and n is from 0 to about 6, together with the pre-ferred alcohol ethoxylates, described above, in a ratio of alcohol ethoxylate to glyceryl ether of from about 1:1 to about 4:1, particularly about 7:3. Glyceryl ethers of the type useful in the present invention are disclosed in * Trade Marks 'A~
11~9~S3 , ~ ~
Canadian Patent Application Serial No. 266,629, Jones, filed November 26, 1976; and U.S. Patent 4,098,713, Jones, issued July 4, 1978.
Cationic Component The compositions of the present invention contain a cationic surfactant, or a mixture of such surfactants, which undergo degradation, through hydrolysis, when they are placed in an alkaline, aqueous environment. Such surfactants con-tain one or more linkages which are subject to attack by hydroxide ions in solution. Examples of such linkages include O O O O O H H O
ll 11 11 11 . Ii I I i1 -C-, -C-O-, -O-C-, -O-, -O-C-O-, -C-N-, -N-C -, O H H O
Il l l 11 -O-C-N-, and -N-C-O-Preferred surfactants are those containing ester,reverse ester, amide, or reverse amide linkages.
Preferred compositions include the cationic surfactants which are described in Canadian Patent Application Serial Nos. 306,513 and 306,517, Letton, both filed June 29, 1978.
These surfactants exhibit excellent biodegradability char-acteristics, as long as they do not contain highly-branched substituents. One type of surfactant useful in the present invention has the formula `A
)a (R )n Z ~(CH2)m-1 -R X
Rl wherein R1 is Cl to C4 alkyl or hydroxyalkyl; R is C5 to C30 straight or branched chain alkyl or alkenyl/ alkyl phenyl, or X Rl- N-(CH2)-S ; wherein s is from 0 to 5;
Rl R is Cl to C20 alkyl or alkenyl; a is 0 or 1, n is 0 or 1, and a is 1 only when n is 1; m is from 1 to 5; zl and z2 are each selected from the group consisting of O O O O H H O o H H o I o, o c, o, o ll o, c w, 1 11, _o_l~ l;! o, and wherein at least one of said groups is an ester, reverse ester, amide or reverse amide; and X is an anion which makes the compound at least water-dispersible, preferably selected from the group consisting of halide, methyl sulfate, sulfate, and nitrate, preferably methyl sulfate, chloride, bromide or iodide.
Particularly preferred cationic surfactants of this type are the choline ester derivatives having the following formula:
~ .
:11)97S3 O CH
R -C-O-CH2CH2-~ -CH3 X
as well as those wherein the ester linkage in the above formula is replaced with a reverse ester, amide or reverse amide linkage.
Particularly preferred examples of this type of cat-ionic surfactant include stearoyl choline ester quaternary ammonium halides (R2 = C17 alkyl), palmitoyl choline ester quaternary ammonium halides (R2 = C15 alkyl), myristoyl choline ester quaternary ammonium halides (R2 = C13 alkyl), lauroyl choline ester ammonium halides (R = Cll alkyl), and tallowyl choline ester quaternary ammonium halides (R = C15-C17 alkyl).
Additional preferred cationic components of the choline ester variety are given by the structural formulas below, wherein p may be from O to 20 O O CH
R -O-C-(CH2)P~-O-CH2CH2- -CH3 X
X CH3- F_CH2_CH2-O-C-(CH2)P-C-O-CH2-CH2-F -CH3 X
il 11~9753 The preferred choline-derivative cationic substances, discussed above, may be prepared by the direct esterification of a fatty acid of the desired chain length with dimethyl-aminoethanol, in the presence of an acid catalyst. The reaction product is then ~uaternized with a methyl halide, forming the desired cationic material. The choline-derived cationic materials may also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2-haloethanol, in the presence of an acid catalyst material. The reaction product is then used to quaternize trimethylamine, forming the desired cationic component.
Another type of cationic surfactant, useful in the compositions of the present invention, has the formula R Rl R -O[(CH)nO]y~(Z )a~(R )t-Z -(CH2)m-N -R X
Rl In the above formula, each Rl is a Cl to C4 alkyl or hydroxy-alkyl group, preferably a methyl ~roup. Each R2 is either hydrogen or Cl to C3 alkyl, preferably hydrogen. R3 is a C4 to C30 straight or branched chain alkyl, alkenylene, alkyl phenyl, or alkyl benzyl group, preferably a C8 to C18 alkyl group, most preferably a C12 alkyl group. R4 is a Cl to C10 alkylene or alkenylene group. n is from 2 to 4, preferably 2; y is from l to 20, preferably from about 1 to lO, most preferably about 7; a may be 0 or l, t may be 0 or l, and a can ~e l only when t is l; and m is from l to 5, preferably 2. z2 is selected from the group consisting of:
O O O O H ~I O O H ~I O
Il 11 il 1~ 1 1 11 11 1 1 ~1 -C-O-, -C-, -O-, -O-C-O-,-C-N~ C~ O-C~ -N-C--O- , zl is selected from the group consisting of , O O O H H O H O
Il 11 11 1 1 11 1 11 -C~O-, -C-, -C-N-, -N-C-, -N-C-o-r and wherein at least one of said zl and z2 groups is selected from the group consisting of ester, revers~ ester, ~mide and reverse amide. X is an anion which w.ill make the compound at least water-dispersible, and is selected from the group consisting of halides, methyl sulfa~e, sulfate, and nitrate, particularly methyl sulfate, chloride, bromide and iodide.
Mixtures of the above structures can also be used Preferred embodiments of th~s type of ca~ionic component are the choline ester derivatives ~Rl is a methyl group and z2 is an ester or reverse ester group), particular ormulas of which are given below, in which t is 0 or l, y is from l to 20 and R3 and X are defined a~ove.
O CIl ~3-o~c~2cH~o)y-~cEl2)t-c-o-cE~2-cEI~-N -Ci~3 X
CEl~
.
975;~
O CH
R -O(CH2CH20)y~C~CH2~N -CH3 X
R3 O(IHCH O) _II_CH2_~1+_CH3 X
R3-o(CHCH20)y~(CH2)t~C~~CH2~CH2~~ -CH3 X
2 2 y ( 2)t ~--C~l2cH2-N -CH3 X-O H H a CH
R -O(CH2CH20)y~C~C=C~C~O~CH2CH2~N -CH3 X
R -o(cH2cH2cH2cH2o)y-c-cH2-~ -CH3 X
.. ~ .
o CH
R3-o(cH2cH2cH2cH2o)y-(cH2~t 1 2 2 1 3 Mixtures of any of the above cationic surfactants may also be used in the compositions of the present invention.
The preferred choline derivatives, described above, may be prepared by the reaction of a lony chain alkyl poly-alkoxy (preferably polyethoxy) carboxylate, having an alkyl chain of desired length, with oxalyl chloride, to form the corresponding acid chloride. The acid chloride is then reacted with dimethylaminoethanol to form the appropriate amine ester, which is then quaternized with a methyl halide to form the desired choline ester compound. Another way of preparing these compounds is by the direct esterification of the appropriate long chain ethoxylated carboxylic acid together with 2-haloethanol or dimethyl aminoethanol, in the presence of heat and an acid catalyst. The reaction product formed is then quaternized with methylhalide or used to quaternize trimethylamine to form the desired choline ester compound.
Alkaline Component The compositions of the present invention also contain from about 1% to about 25%, preferably from about
~ 1~)97S3 hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40~ to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic*
compounds, marketed by Wyandotte Chemical Corporation.
A preferred group of nonionic surfactants useful herein comprises a mixture of "surfactant" and "cosur-factant", containing at least one nonionic surfactantfalling within the definition of nonionic surfactants useful in the present invention, as described in Canadian Patent No. 1,059,8~5, Collins, issued on August 7, 1979.
Preferred alcohol ethoxylate nonionic surfactants for use in the compositions of the present invention are bio-degradable and have the formula R(OC2H4)nOH, wherein R is a primary or secondary alkyl chain of from about 8 to about 22, preferably from about 10 to about 20, carbon atoms and n is an average of from about 2 to about 12, particularly from about 2 to about 9. The nonionics have an HLB (hydrophilic-lipophilic balance) of from about 5 to about 17, preferably from about 6 to about 15. HLB is defined in detail in Nonionic Surfactants, by M. J. Schick, Marcel Dekker, Inc., 1966, pages 607-613.
In preferred nonionic surfactants, n is from 4 to 7.
Primary linear alcohol ethoxylates (e.g., alcohol ethoxy-lates produced from organic alcohols which contain about 20~ 2-methyl branched isomers, commercially available from Shell Chemical Company under the trademark Neodol) are Ipreferred from a performance standpoint.
* Trade Mark A
Particularly preferred nonionic surfactants for use in the compositions of the present invention include the condensation product of C10 alcohol with 3 moles of ethylene oxide; the condensation product of tallow alcohol with 9 moles of ethylene oxide; the condensation product of coconut alcohol with 5 moles of ethylene oxide; the condensation product of coconut alcohol with 6 moles of ethylene oxide;
the condensation product of C12 alcohol with 5 moles of ethylene oxide; the condensation product of C12 13 alcohol -with 6.5 moles of et~lylene oxi.de, and the same condensatinnproduct which is stripped so as to r~move substantially all lower ethoxylate and nonethoxylated fractions; the condensation product of C12 13 alcohol with 3 moles of ethylene oxide, and the same condensation product which i5 stripped so as to remove substantially all lower ethoxylate.and nonethoxylated fractions; the condensation product of C12 ]3 alcohol with 9 moles of ethylene oxide; the condensation product of Cl~ 15 alcohol with 2.25 moles of ethylene oxide; the condensati.on product of Cl~ 15 alcohol with 4 moles of ethylene oxide;
the condensation product of C14 15 alcohol with 7 moles of ethylene oxide; and the condensation product of Cl~ 15 alcohol with 9 moles of ethylene oxide.
The compositions of the present invention may contain mixtures of the preferred alcohol ethoxylate nonionic surfactants together with other types of nonionic surfactants.
Preferred nonionic surfactant mixtures contain at least one of the preferred alcohol ethoxylate nonionics, and have a ratio of the preferred alcohol ethoxylate surfactant (or surfactants) to the other nonionic surfactant ~or surfactants) of from about 1:1 to about 5:1. Specific examples of surfactant mixtures useful in the present invention include a mixture 1 1~9753 of the condensation product of C14 15 alcohol with 3 moles of ethylene oxide (Neodol* 45-3) and the condensation product of C14 15 alcOhol with 9 moles of ethylene oxide (Neodol* 45-9), in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from about 1:1 to about 3:1;
a mixture of the condensation product of C10 alcohol with 3 moles of ethylene oxide together with the condensation product of a secondary C15 alcohol with 9 moles of ethylene oxide (Tergitol 15-S-9), in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from about 1:1 to about 4:1; a mixture of Neodol* 45-3 and Tergitol* 15-S-9, in a ratio of lower ethoxylate nonionic to higher ethoxylate nonionic of from about 1:1 to about 3:1; and a mixture of Neodo~* 45-3 with the condensation product of myristyl alcohol with 10 moles of ethylene oxide, in a ratio of lower ethoxylate to higher ethoxylate of from about 1:1 to about 3:1.
Preferred nonionic surfactant mixtures may also contain alkyl glyceryl ether compounds together with the preferred alcohol ethoxylate surfactants. Particularly preferred are glyceryl ethers having the formula R-O(CH2CH2O)nCH2CHCH2OH
OH
wherein R is an alkyl or alkenyl group of from about 8 to about 18, preferably about 8 to 12, carbon atoms or an alkaryl group having from about 5 to 14 carbons in the alkyl chain, and n is from 0 to about 6, together with the pre-ferred alcohol ethoxylates, described above, in a ratio of alcohol ethoxylate to glyceryl ether of from about 1:1 to about 4:1, particularly about 7:3. Glyceryl ethers of the type useful in the present invention are disclosed in * Trade Marks 'A~
11~9~S3 , ~ ~
Canadian Patent Application Serial No. 266,629, Jones, filed November 26, 1976; and U.S. Patent 4,098,713, Jones, issued July 4, 1978.
Cationic Component The compositions of the present invention contain a cationic surfactant, or a mixture of such surfactants, which undergo degradation, through hydrolysis, when they are placed in an alkaline, aqueous environment. Such surfactants con-tain one or more linkages which are subject to attack by hydroxide ions in solution. Examples of such linkages include O O O O O H H O
ll 11 11 11 . Ii I I i1 -C-, -C-O-, -O-C-, -O-, -O-C-O-, -C-N-, -N-C -, O H H O
Il l l 11 -O-C-N-, and -N-C-O-Preferred surfactants are those containing ester,reverse ester, amide, or reverse amide linkages.
Preferred compositions include the cationic surfactants which are described in Canadian Patent Application Serial Nos. 306,513 and 306,517, Letton, both filed June 29, 1978.
These surfactants exhibit excellent biodegradability char-acteristics, as long as they do not contain highly-branched substituents. One type of surfactant useful in the present invention has the formula `A
)a (R )n Z ~(CH2)m-1 -R X
Rl wherein R1 is Cl to C4 alkyl or hydroxyalkyl; R is C5 to C30 straight or branched chain alkyl or alkenyl/ alkyl phenyl, or X Rl- N-(CH2)-S ; wherein s is from 0 to 5;
Rl R is Cl to C20 alkyl or alkenyl; a is 0 or 1, n is 0 or 1, and a is 1 only when n is 1; m is from 1 to 5; zl and z2 are each selected from the group consisting of O O O O H H O o H H o I o, o c, o, o ll o, c w, 1 11, _o_l~ l;! o, and wherein at least one of said groups is an ester, reverse ester, amide or reverse amide; and X is an anion which makes the compound at least water-dispersible, preferably selected from the group consisting of halide, methyl sulfate, sulfate, and nitrate, preferably methyl sulfate, chloride, bromide or iodide.
Particularly preferred cationic surfactants of this type are the choline ester derivatives having the following formula:
~ .
:11)97S3 O CH
R -C-O-CH2CH2-~ -CH3 X
as well as those wherein the ester linkage in the above formula is replaced with a reverse ester, amide or reverse amide linkage.
Particularly preferred examples of this type of cat-ionic surfactant include stearoyl choline ester quaternary ammonium halides (R2 = C17 alkyl), palmitoyl choline ester quaternary ammonium halides (R2 = C15 alkyl), myristoyl choline ester quaternary ammonium halides (R2 = C13 alkyl), lauroyl choline ester ammonium halides (R = Cll alkyl), and tallowyl choline ester quaternary ammonium halides (R = C15-C17 alkyl).
Additional preferred cationic components of the choline ester variety are given by the structural formulas below, wherein p may be from O to 20 O O CH
R -O-C-(CH2)P~-O-CH2CH2- -CH3 X
X CH3- F_CH2_CH2-O-C-(CH2)P-C-O-CH2-CH2-F -CH3 X
il 11~9753 The preferred choline-derivative cationic substances, discussed above, may be prepared by the direct esterification of a fatty acid of the desired chain length with dimethyl-aminoethanol, in the presence of an acid catalyst. The reaction product is then ~uaternized with a methyl halide, forming the desired cationic material. The choline-derived cationic materials may also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2-haloethanol, in the presence of an acid catalyst material. The reaction product is then used to quaternize trimethylamine, forming the desired cationic component.
Another type of cationic surfactant, useful in the compositions of the present invention, has the formula R Rl R -O[(CH)nO]y~(Z )a~(R )t-Z -(CH2)m-N -R X
Rl In the above formula, each Rl is a Cl to C4 alkyl or hydroxy-alkyl group, preferably a methyl ~roup. Each R2 is either hydrogen or Cl to C3 alkyl, preferably hydrogen. R3 is a C4 to C30 straight or branched chain alkyl, alkenylene, alkyl phenyl, or alkyl benzyl group, preferably a C8 to C18 alkyl group, most preferably a C12 alkyl group. R4 is a Cl to C10 alkylene or alkenylene group. n is from 2 to 4, preferably 2; y is from l to 20, preferably from about 1 to lO, most preferably about 7; a may be 0 or l, t may be 0 or l, and a can ~e l only when t is l; and m is from l to 5, preferably 2. z2 is selected from the group consisting of:
O O O O H ~I O O H ~I O
Il 11 il 1~ 1 1 11 11 1 1 ~1 -C-O-, -C-, -O-, -O-C-O-,-C-N~ C~ O-C~ -N-C--O- , zl is selected from the group consisting of , O O O H H O H O
Il 11 11 1 1 11 1 11 -C~O-, -C-, -C-N-, -N-C-, -N-C-o-r and wherein at least one of said zl and z2 groups is selected from the group consisting of ester, revers~ ester, ~mide and reverse amide. X is an anion which w.ill make the compound at least water-dispersible, and is selected from the group consisting of halides, methyl sulfa~e, sulfate, and nitrate, particularly methyl sulfate, chloride, bromide and iodide.
Mixtures of the above structures can also be used Preferred embodiments of th~s type of ca~ionic component are the choline ester derivatives ~Rl is a methyl group and z2 is an ester or reverse ester group), particular ormulas of which are given below, in which t is 0 or l, y is from l to 20 and R3 and X are defined a~ove.
O CIl ~3-o~c~2cH~o)y-~cEl2)t-c-o-cE~2-cEI~-N -Ci~3 X
CEl~
.
975;~
O CH
R -O(CH2CH20)y~C~CH2~N -CH3 X
R3 O(IHCH O) _II_CH2_~1+_CH3 X
R3-o(CHCH20)y~(CH2)t~C~~CH2~CH2~~ -CH3 X
2 2 y ( 2)t ~--C~l2cH2-N -CH3 X-O H H a CH
R -O(CH2CH20)y~C~C=C~C~O~CH2CH2~N -CH3 X
R -o(cH2cH2cH2cH2o)y-c-cH2-~ -CH3 X
.. ~ .
o CH
R3-o(cH2cH2cH2cH2o)y-(cH2~t 1 2 2 1 3 Mixtures of any of the above cationic surfactants may also be used in the compositions of the present invention.
The preferred choline derivatives, described above, may be prepared by the reaction of a lony chain alkyl poly-alkoxy (preferably polyethoxy) carboxylate, having an alkyl chain of desired length, with oxalyl chloride, to form the corresponding acid chloride. The acid chloride is then reacted with dimethylaminoethanol to form the appropriate amine ester, which is then quaternized with a methyl halide to form the desired choline ester compound. Another way of preparing these compounds is by the direct esterification of the appropriate long chain ethoxylated carboxylic acid together with 2-haloethanol or dimethyl aminoethanol, in the presence of heat and an acid catalyst. The reaction product formed is then quaternized with methylhalide or used to quaternize trimethylamine to form the desired choline ester compound.
Alkaline Component The compositions of the present invention also contain from about 1% to about 25%, preferably from about
5% to about 20%, and most preferably from about 8% to about 16%, of an inorganic alkalinity-producing component, pre-ferably as the compositions' sole alkalinity-producing component. These components must be chosen such that they are relatively insoluble in the cationic or nonionic/cationic surfactant component included in the composition. Thus, alkalinity sources such as monoethanolamine and triethanolamine, which are often used as alkalinity sources in detergent compositions, are not useful in the compositions of the present invention, since they tend to be too soluble in cationic/nonionic surfactant mixtures. The particular alkaline component used must also be selected and included in an amount such that the detergent composition forms a solution having a pH of from about 8 to about lO, preferably from about 8.5 to about 9.5, within about 3 minutes, preferably within about 2 minutes, most preferably within about 1 minute, after it is placed in 100F water at a concentration of about 0.15% by weight. Thus, anhydrous borax is not useful in the compos-itions of the present invention since it dissolves too slowly to give the desired pH within the required time period.
Preferred alkaline com~onents for use in the compos-itions of the present invention include sodium tetraborate decahydrate (Na2B4O7'10H2O; borax decahydrate), sodium tetraborate pentahydrate (Na2B4O7'5H2O; borax pentahydrate), sodium carbonate, and mixtures of these components.
Particularly preferred alkalinity-producing components are borax pentahydrate \,.~`' ~1~)97S3 and borax decahydrate and mixtures thereof.
Preferred embodiments of the present invention add-itionally contain from about 2 to about 25%, preferably from about 2 to about 16~, and most preferably from about 3 to about 10~, of a fatty amide surfactant. The ratio of the total cationic and nonionic surfactant components contained in the composition to the amide component is from about 5:1 to about 50:1, preferably from about 8:1 to about 25:1. These preferred embodiments yield excellent particulate soil removal performance, as well as improved soil anti-redeposition characteristics, and the develop-ment is described in Canadian Patent Application, Serial No. 306,559, Cambre, filed June 29, 1978.
The compositions of the present invention may also contain additional ingredients generally found in laundry detergent compositions, at their conventional art-established levels, as long as these ingredients are compatible with the nonionic and cationic components.
For example the compositions may contain up to about 15%, preferably up to about 5%, and most preferably from about 0.1% to about 2% of a suds suppressor component. Typical suds suppressors include long chain fatty acids, such as those described in U.S. Patent 2,954,347, issued September 27, 1960, St. John, and combinations of certain nonionics therewith as disclosed in U.S. Patent 2,954,348, issued September 27, 1960, Schwoeppe. Other suds suppressor components useful in the compositions of the present invention include, but are not limited to, those described below.
'.~
Preferred suds suppressing additives are described in U.S. Patent 3,933,672, issued January 20, 1976, Bartolotta et al., relative to a silicone suds controll-ing agent. The silicone material can be represented by alkylated polysiloxane materials such as silica aerogels and xerogels and hydrophobic silicas of various types.
The silicone material can be described as a siloxane having the formula:
~ 5 ~, t R~
wherein x is from about 20 to about 2,000, and R and R' are each alkyl or aryl groups, especially methyl, ethyl, propyl, butyl and phenyl. The polydimethylsiloxanes (R
and R' are methyl) having a molecular weight within the range of from about 200 to about 200,000, and higher, are all useful as suds controlling agents. Additional suitable silicone materials wherein the side chain groups R and R' are alkyl, aryl, or mixed alkyl and aryl hydrocarbyl groups exhibit useful suds controlling properties. Examples of such ingredients include diethyl-, dipropyl-, dibutyl-, methyl- ethyl-, phenyl-methyl-polysiloxanes and the like. Additional useful silicone suds controlling agents can be represented 7~3 by a mixture of an alkylated siloxane, as referred to hereinbefore, and solid silica. Such mixtures are pre-pared by affixing the silicone to the surface of the solid sil ca. A preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethylsilanated) silica having a particle size in the range from about 10 millimicrons to 20 millimicrons and a specific surface area above about 50 m2/gm~ intimately admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about 19:1 to about 1:2. The silicone suds suppressing agent is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent-impermeable carrier.
Particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in U.S.
Patent No. 4,136,045, Gault et al, issued January 23, 1979. An example of such a compound is DB-544*, commer-cially available from Dow Corning, which contains a siloxane/glycol copolymer together with solid silica and a siloxane resin.
Microcrystalline waxes having a melting point in the range from 35C-115C and a saponification value of less than 100 represent additional examples of a preferred suds regulating component for use in the subject compositions, and are described in detail, in U.S. Patent 4,056,481, Tate, issued November 1, 1977.
* TRADE MARK
~1~9'753 The microcrystalline waxes are substantially water-insoluble, but are water-dispersible in the presence of organic surfact-ants. Preferred microcrystalline waxes have a melting point from about 65C to 100C, a molecular weight in the range from 400-1,000; and a penetration value of at least 6, measured at 77F by ASTM-D1321. Suitable examples of the above waxes include: microcrystalline and oxidized micro-crystalline petrolatum waxes; Fischer-Tropsch and oxidized Fischer-Tropsch waxes; ozokerite; ceresin; montan wax;
beeswax; candelilla; and carnauba wax.
Alkyl phosphate esters represent an additional preferred suds suppressant for use herein. These preferred phosphate esters are predominantly monostearyl phosphate which, in addition thereto, can contain di- and tristearyl phosphates and monooleyl phosphates, which can contain di-and trioleyl phosphates.
The alkyl phosphate esters frequently contain some trialkyl phosphate. Accordingly, a preferred phosphate ester can contain, in addition to the monoalkyl ester, e.g.
monostearyl phosphate, up to about 50 mole percent of di-alkyl phosphate and up to about 5 mole percent of trialkyl phosphate.
Other adjunct components which may be included in the compositions of the present invention, in their conventional art-established levels for use (i.e., from O to about 40%), include anionic, zwitterionic and ampholytic cosurfactants, detergency builders, bleaching agents, bleach activators, soil-suspending agents, corrosion inhibitors, dyes, fillers, optical brighteners, germicides, pH adjusting agents, enzymes, enzyme-stabilizing agents, perfumes, fabric soEtening components, static control agents, and the like. How-ever, because of the numerous and diverse performance advantages of the preferred compositions of the present invention, certain types of adjunct components, such as detergency builders, static control agents, fabric softening agents and germicides, will not usually be necessary.
Examples of cosurfactants and detergency builders, which may be used in the compositions of the present invention, are found in U.S. Patent 3,717,630, Booth, Ca "O~
issued February 20, 1973, and U.S. Patent Application 306, 't7'f 19 7"
Serial No. 311,~ O, Murphy, filed June 29, ~g~.
The compositions of the present invention may be manufactured and used in a variety of forms, such as solids, powders, granules, pastes, or liquids. The compositions are particularly well suited for incorp-oration into substrate articles for use in the home laundering process. Examples of such articles are described in U.S. Patent No. 4,170,565, Flesher et al., issued October 9, 1979; U.S. Patent 4,095,946, ~1~9753 Jones et al., issued June 20, 1978; U.S. Patent 4,118,525, Jones,issued October 3, 1978; and U.S.
Patent 4,113,630, Hagner et al, issued September 12, 1978. These articles consist of a water-insoluble substrate which releasably incorporates an effective amount, preferably from about 3 to 120 grams, particu-larly from about 20 to 80 grams, of the detergent compositions of the present invention. When the compositions of the present invention are used in substrate articles it may be advantageous to include the solubilization aids, described in U.S. Patent No.
4,199,464, Cambre, issued April 22, 1980, and the anti-bleeding components, described in U.S. Patent No.
4,199,465, Rodriguez, issued April 22, 1980.
The compositions of the present invention are used in the laundering process by forming an aqueous solution containing from about 0.01 (100 parts per million) to 0.3~ (3,000 parts per million), preferably from about 0.02 to 0.2%, and most preferably from about 0.03 to about 0.15%, of the compositions of the present inven-tion, and agitating the soiled fabrics in that solution.
The fabrics are then rinsed and dried. When used in this manner, the preferred compositions of the present invention yield exceptionally good particulate soil, oily body soil and greasy/oily soil removal performance, as well as fabric softening, static control, and dye transfer inhibition benefits to the fabrics A
.
laundered therewith. Further, the compositions are stable upon storage, and exhibit a minimum of hydrolysis of the - cationic component when placed in laundry solution.
All percentages, parts, and ratios used herein are by S weight unless o~herwise specified.
The following nonlimiting examples illustrate the compositions and method of the present invention.
' . '.
....
....
, EXAMPLE I
The storage and wash solution stability of detergent compositions containing various types of alkalinity-producing components were tested in the following manner.
The detergent compositions tested contained the cationic surfactant having the formula:
Il +l H35 C O CH2CH2- ~-CH3 Cl present in an amount yielding a concentration of 143 ppm in the test wash solution, together with the condensation product of coconut alcohol with 5 moles of ethylene oxide~
present in an amount yielding a concentratioll o~ 357 ppm in the test wash solution. The compositions additionally contained the alkalinity-producing components, given in ~he table below, in the amounts specified. Each composition was added to a four liter beaker, containing abou~ three liters o water at 100F (i grains per gallon of mixed calciurn and magnesium hardness). The solutions were s~irred for ~bout ten minutes and samples were taken at the end o~ tha~ ~ime_ For each solution, the pH and the percent loss o~ the cationic component was determined. The percent los~ of the cationic component in the wash solution was determined by mixed indicator titration.
In the mixed indicator titration, a wash solution sample, containing the cationic surfactant (some of which , j,,~, i, .
9~53 had been hydrolyzed), was combined with a mixed indica-tor of cationic- and anionic-complexing dyes, in a water-chloroform system. A known amount of 0.00400N
Cll 8 linear alkylbenzene sulfonate was added to provide an excess of anionic surfactant. A complex of anionic surfactant, hydrolysis ragment and cationic dye was formed; this complex was soluble in the chloro-form layer, giving it a red-pink color. The solution was then titrated with an approximately 0.00400N
lQ solution of Hyamine* 1622 (di-isobutyl phenoxy ethoxy ethyl dimethylbenzyl ammonium chloride, available from Rohm and Haas), destroying the dye/surfactant complex and the pink color. A color change to grey in the chloroform layer indicated the end point, and the amount of the hydrolysis fragment present was calcula-ted, based on the amount of Hyamine* used in the titration.
The percent loss of the cationic component during storage was determined by taking a sample (approximately
Preferred alkaline com~onents for use in the compos-itions of the present invention include sodium tetraborate decahydrate (Na2B4O7'10H2O; borax decahydrate), sodium tetraborate pentahydrate (Na2B4O7'5H2O; borax pentahydrate), sodium carbonate, and mixtures of these components.
Particularly preferred alkalinity-producing components are borax pentahydrate \,.~`' ~1~)97S3 and borax decahydrate and mixtures thereof.
Preferred embodiments of the present invention add-itionally contain from about 2 to about 25%, preferably from about 2 to about 16~, and most preferably from about 3 to about 10~, of a fatty amide surfactant. The ratio of the total cationic and nonionic surfactant components contained in the composition to the amide component is from about 5:1 to about 50:1, preferably from about 8:1 to about 25:1. These preferred embodiments yield excellent particulate soil removal performance, as well as improved soil anti-redeposition characteristics, and the develop-ment is described in Canadian Patent Application, Serial No. 306,559, Cambre, filed June 29, 1978.
The compositions of the present invention may also contain additional ingredients generally found in laundry detergent compositions, at their conventional art-established levels, as long as these ingredients are compatible with the nonionic and cationic components.
For example the compositions may contain up to about 15%, preferably up to about 5%, and most preferably from about 0.1% to about 2% of a suds suppressor component. Typical suds suppressors include long chain fatty acids, such as those described in U.S. Patent 2,954,347, issued September 27, 1960, St. John, and combinations of certain nonionics therewith as disclosed in U.S. Patent 2,954,348, issued September 27, 1960, Schwoeppe. Other suds suppressor components useful in the compositions of the present invention include, but are not limited to, those described below.
'.~
Preferred suds suppressing additives are described in U.S. Patent 3,933,672, issued January 20, 1976, Bartolotta et al., relative to a silicone suds controll-ing agent. The silicone material can be represented by alkylated polysiloxane materials such as silica aerogels and xerogels and hydrophobic silicas of various types.
The silicone material can be described as a siloxane having the formula:
~ 5 ~, t R~
wherein x is from about 20 to about 2,000, and R and R' are each alkyl or aryl groups, especially methyl, ethyl, propyl, butyl and phenyl. The polydimethylsiloxanes (R
and R' are methyl) having a molecular weight within the range of from about 200 to about 200,000, and higher, are all useful as suds controlling agents. Additional suitable silicone materials wherein the side chain groups R and R' are alkyl, aryl, or mixed alkyl and aryl hydrocarbyl groups exhibit useful suds controlling properties. Examples of such ingredients include diethyl-, dipropyl-, dibutyl-, methyl- ethyl-, phenyl-methyl-polysiloxanes and the like. Additional useful silicone suds controlling agents can be represented 7~3 by a mixture of an alkylated siloxane, as referred to hereinbefore, and solid silica. Such mixtures are pre-pared by affixing the silicone to the surface of the solid sil ca. A preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethylsilanated) silica having a particle size in the range from about 10 millimicrons to 20 millimicrons and a specific surface area above about 50 m2/gm~ intimately admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about 19:1 to about 1:2. The silicone suds suppressing agent is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent-impermeable carrier.
Particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in U.S.
Patent No. 4,136,045, Gault et al, issued January 23, 1979. An example of such a compound is DB-544*, commer-cially available from Dow Corning, which contains a siloxane/glycol copolymer together with solid silica and a siloxane resin.
Microcrystalline waxes having a melting point in the range from 35C-115C and a saponification value of less than 100 represent additional examples of a preferred suds regulating component for use in the subject compositions, and are described in detail, in U.S. Patent 4,056,481, Tate, issued November 1, 1977.
* TRADE MARK
~1~9'753 The microcrystalline waxes are substantially water-insoluble, but are water-dispersible in the presence of organic surfact-ants. Preferred microcrystalline waxes have a melting point from about 65C to 100C, a molecular weight in the range from 400-1,000; and a penetration value of at least 6, measured at 77F by ASTM-D1321. Suitable examples of the above waxes include: microcrystalline and oxidized micro-crystalline petrolatum waxes; Fischer-Tropsch and oxidized Fischer-Tropsch waxes; ozokerite; ceresin; montan wax;
beeswax; candelilla; and carnauba wax.
Alkyl phosphate esters represent an additional preferred suds suppressant for use herein. These preferred phosphate esters are predominantly monostearyl phosphate which, in addition thereto, can contain di- and tristearyl phosphates and monooleyl phosphates, which can contain di-and trioleyl phosphates.
The alkyl phosphate esters frequently contain some trialkyl phosphate. Accordingly, a preferred phosphate ester can contain, in addition to the monoalkyl ester, e.g.
monostearyl phosphate, up to about 50 mole percent of di-alkyl phosphate and up to about 5 mole percent of trialkyl phosphate.
Other adjunct components which may be included in the compositions of the present invention, in their conventional art-established levels for use (i.e., from O to about 40%), include anionic, zwitterionic and ampholytic cosurfactants, detergency builders, bleaching agents, bleach activators, soil-suspending agents, corrosion inhibitors, dyes, fillers, optical brighteners, germicides, pH adjusting agents, enzymes, enzyme-stabilizing agents, perfumes, fabric soEtening components, static control agents, and the like. How-ever, because of the numerous and diverse performance advantages of the preferred compositions of the present invention, certain types of adjunct components, such as detergency builders, static control agents, fabric softening agents and germicides, will not usually be necessary.
Examples of cosurfactants and detergency builders, which may be used in the compositions of the present invention, are found in U.S. Patent 3,717,630, Booth, Ca "O~
issued February 20, 1973, and U.S. Patent Application 306, 't7'f 19 7"
Serial No. 311,~ O, Murphy, filed June 29, ~g~.
The compositions of the present invention may be manufactured and used in a variety of forms, such as solids, powders, granules, pastes, or liquids. The compositions are particularly well suited for incorp-oration into substrate articles for use in the home laundering process. Examples of such articles are described in U.S. Patent No. 4,170,565, Flesher et al., issued October 9, 1979; U.S. Patent 4,095,946, ~1~9753 Jones et al., issued June 20, 1978; U.S. Patent 4,118,525, Jones,issued October 3, 1978; and U.S.
Patent 4,113,630, Hagner et al, issued September 12, 1978. These articles consist of a water-insoluble substrate which releasably incorporates an effective amount, preferably from about 3 to 120 grams, particu-larly from about 20 to 80 grams, of the detergent compositions of the present invention. When the compositions of the present invention are used in substrate articles it may be advantageous to include the solubilization aids, described in U.S. Patent No.
4,199,464, Cambre, issued April 22, 1980, and the anti-bleeding components, described in U.S. Patent No.
4,199,465, Rodriguez, issued April 22, 1980.
The compositions of the present invention are used in the laundering process by forming an aqueous solution containing from about 0.01 (100 parts per million) to 0.3~ (3,000 parts per million), preferably from about 0.02 to 0.2%, and most preferably from about 0.03 to about 0.15%, of the compositions of the present inven-tion, and agitating the soiled fabrics in that solution.
The fabrics are then rinsed and dried. When used in this manner, the preferred compositions of the present invention yield exceptionally good particulate soil, oily body soil and greasy/oily soil removal performance, as well as fabric softening, static control, and dye transfer inhibition benefits to the fabrics A
.
laundered therewith. Further, the compositions are stable upon storage, and exhibit a minimum of hydrolysis of the - cationic component when placed in laundry solution.
All percentages, parts, and ratios used herein are by S weight unless o~herwise specified.
The following nonlimiting examples illustrate the compositions and method of the present invention.
' . '.
....
....
, EXAMPLE I
The storage and wash solution stability of detergent compositions containing various types of alkalinity-producing components were tested in the following manner.
The detergent compositions tested contained the cationic surfactant having the formula:
Il +l H35 C O CH2CH2- ~-CH3 Cl present in an amount yielding a concentration of 143 ppm in the test wash solution, together with the condensation product of coconut alcohol with 5 moles of ethylene oxide~
present in an amount yielding a concentratioll o~ 357 ppm in the test wash solution. The compositions additionally contained the alkalinity-producing components, given in ~he table below, in the amounts specified. Each composition was added to a four liter beaker, containing abou~ three liters o water at 100F (i grains per gallon of mixed calciurn and magnesium hardness). The solutions were s~irred for ~bout ten minutes and samples were taken at the end o~ tha~ ~ime_ For each solution, the pH and the percent loss o~ the cationic component was determined. The percent los~ of the cationic component in the wash solution was determined by mixed indicator titration.
In the mixed indicator titration, a wash solution sample, containing the cationic surfactant (some of which , j,,~, i, .
9~53 had been hydrolyzed), was combined with a mixed indica-tor of cationic- and anionic-complexing dyes, in a water-chloroform system. A known amount of 0.00400N
Cll 8 linear alkylbenzene sulfonate was added to provide an excess of anionic surfactant. A complex of anionic surfactant, hydrolysis ragment and cationic dye was formed; this complex was soluble in the chloro-form layer, giving it a red-pink color. The solution was then titrated with an approximately 0.00400N
lQ solution of Hyamine* 1622 (di-isobutyl phenoxy ethoxy ethyl dimethylbenzyl ammonium chloride, available from Rohm and Haas), destroying the dye/surfactant complex and the pink color. A color change to grey in the chloroform layer indicated the end point, and the amount of the hydrolysis fragment present was calcula-ted, based on the amount of Hyamine* used in the titration.
The percent loss of the cationic component during storage was determined by taking a sample (approximately
6 grams) of each detergent composition, placing the sample in a closed Petri dish, and storing the dishes, for a four week period, under conditions of 80F/60%
relative humidity; 80F/80% relative humidity; and 120F/60% relative humidity. The percent loss of the cationic component was determined at various stages dur-ing storage by the mixed indicator titration technique, described above. The data obtained are summarized in the table belo~:
* TRADE MARK
11~9753 o a~
, ~ r h O
0 Ul _ I,!C O I I ~
0 3 o 'I ~ I t _I I V V V V V
er U') o _ dP--t`
q~ In o --~ ~
0 ~,1 0~ ~n ~ c~
O ~ ~D ~ r~ I ~ I ~n co ' ~D ~ t` r`
~r h ~: _ u) n I
w ~-,~ ~ n o~ ~ r~
rl O
Q~ E3 0 u7 r~ ~~ .
o n ~ o o ~ ~n o L-~ ~D O n , ~ ~r ~D O ~ ~` ~r cn ,1 ~ ~r o O
0 C~
Ei ~ 0 ,1 ~ ~ m Q
O ~1 m o ~, O
S ~ . .
a) ~ ~ x x o a~
O S~ O O O O
m m u~
U~
.. ..
.... ,.~ , ..... .
39'7~3 The above data demonstrate that acceptable wash and storage stability of the cationic component is obtained when the alkalinity-producing components defined herein are, included in'the detergent compo~itions in the,required amounts~
Similar results are obtained where the nonionic component.
used above is replaced by the condensation product of C10 alcohol with three moles of ethylene oxide, the condensation product of coconut alcohol with six mole~ of ethylene oxid~, the condensation product of coconut alcohol with 7 moles o~
ethylene oxide, the condensation product o C12 13 alcohol with 6.5 moles of ethylene oxide, the condensation p~oduc~
of C14 15 alcohol with 7 moles of ethylene oxide, or th~
condensation product of C12 13 alcohol with three moles of ethylene oxide stripped so as to remove the lower ethoxylate and unethox~lated fractions.
Excellent stability results are also obtained where th2 detergent composition includes nonionic to cationic surfactant weight ratios of about 100:1, 50:1, 35:1, 25:1, 15:1, 10:1,
relative humidity; 80F/80% relative humidity; and 120F/60% relative humidity. The percent loss of the cationic component was determined at various stages dur-ing storage by the mixed indicator titration technique, described above. The data obtained are summarized in the table belo~:
* TRADE MARK
11~9753 o a~
, ~ r h O
0 Ul _ I,!C O I I ~
0 3 o 'I ~ I t _I I V V V V V
er U') o _ dP--t`
q~ In o --~ ~
0 ~,1 0~ ~n ~ c~
O ~ ~D ~ r~ I ~ I ~n co ' ~D ~ t` r`
~r h ~: _ u) n I
w ~-,~ ~ n o~ ~ r~
rl O
Q~ E3 0 u7 r~ ~~ .
o n ~ o o ~ ~n o L-~ ~D O n , ~ ~r ~D O ~ ~` ~r cn ,1 ~ ~r o O
0 C~
Ei ~ 0 ,1 ~ ~ m Q
O ~1 m o ~, O
S ~ . .
a) ~ ~ x x o a~
O S~ O O O O
m m u~
U~
.. ..
.... ,.~ , ..... .
39'7~3 The above data demonstrate that acceptable wash and storage stability of the cationic component is obtained when the alkalinity-producing components defined herein are, included in'the detergent compo~itions in the,required amounts~
Similar results are obtained where the nonionic component.
used above is replaced by the condensation product of C10 alcohol with three moles of ethylene oxide, the condensation product of coconut alcohol with six mole~ of ethylene oxid~, the condensation product of coconut alcohol with 7 moles o~
ethylene oxide, the condensation product o C12 13 alcohol with 6.5 moles of ethylene oxide, the condensation p~oduc~
of C14 15 alcohol with 7 moles of ethylene oxide, or th~
condensation product of C12 13 alcohol with three moles of ethylene oxide stripped so as to remove the lower ethoxylate and unethox~lated fractions.
Excellent stability results are also obtained where th2 detergent composition includes nonionic to cationic surfactant weight ratios of about 100:1, 50:1, 35:1, 25:1, 15:1, 10:1,
7:1, 5:1, 4:1, 10:3, 20:7, 20:9, 2:1, or 5:3.
Excellent results are also obtained where the nonionic component, used above, is replaced by a mixture of ~he condensation product of C14 15 alcohol with three moles o~
ethylene oxide together with the condensation product of C14 15 alcohol with 7 moles of ethylene oxi.de, in a ratio o lower ethoxylate nonionic to higher etlloxylate nonionic o~
about 2:1; a mixture of the condensation product of C14 15 alcohol with 3 moles of ethylene oxide together with the condensation product o~ myristyl alcohol with 10 moles of of ethylene oxide, in a ratio or lower ethoxylate nonionic to higher ethoxylate nonionic of about 1:1; or a mixture o~
the condensation product of coconut alcohol with 5 moles of ethylene oxide together with an alkyl glyceryl ether havi.ng the formula OH
in a ratio o~ alcohol ethoxylate to gl~ceryl ether o abou~
7:3.
Substantially similar stability results are also ob~ained where the cationic component is replaced by those havinc3 the formulae given below, or mixtures of those surfac~ants:
O CH
Il 1 3 C16H33 C O-CH2CH2- N-CH3 Br O o CH3 i2 25 C CH2CH2_c_o_cH2cH2-N~-C~3 Cl-CH Ol CH3 . Br CH3- I_cH2cH2_0 C (C 2)12 2 2 j 3 o fH3 10 21 (CH2cx2o)lo-c~cH2-N -CH3 Cl S C13H27--(CHCH2)11-C CH2 ll CH3 B
EX~MPLE II
A heavy-duty liquid laundry detergen~ composition, having the formula given below, is produced by mixing together the following components in the stated proportions.
Component Weight %
Il 1 3 17H35 C -CH2cH2- N-CH3 Cl 26.1 Condensation product of coconut alcohOl with 5 moles of ethylene oxide 51,5 Borax 10 H2O 11~5 Ethanol ~,o Minors (suds suppressor, perfume, brighteners, etc.) balance ~o 100 This composition provides excellent removal of both clay and greasy/oily soils, as well as stora~e and wash solution stability o the cationic component.
EX~LE III
A paste-form laundry detergent composition, having the formula given below, is prepared by mixing together the following components in the stated proportions~
Component ~eight %
O CH
ll 1 3 C17E135-C-O-CH2CH2-+N-CH3 Cl 26.0 Csndensation product of coconut lo alcohol with 5 moles of ethylene oxide 5~5 C12_16 fatty acid ammonia amide 7~0 Borax 5 H20 13.0 Minors tsuds suppressor, perfume, brightener, etc.) balance to .lOO
This composition, when used as a paste or in a substrate article, as described hereinafter, prov.i.des excel:Len~ remova~
of both clay and greasy/oily soils, as well as storage and wash solution stability of the cationic component~
..... .. .
11~)9~53 EXAMPLE IV
A substrate article, for use in the automatic machine laundering of fabrics, is made by coating one side of an 8" x ll" sheet of a Scott 8050* Industrial Towel, having an air permeability o, about 130 cu. ft./
min./sq. ft., a basis weight of about 77.5 grams per square yard, and a thickness of 44 mils, with about 50 grams of the detergent composition having the formula-tion given below. The composition is made by intimately mixing the nonionic and cationic surfactants together, at a temperature of about 80 C, to form a thick paste, and then mixing in the remaining components.
Component Weight %
o CH3 C17H35-C-O-CH2CH2- N~CH3 Cl 21.4 Condensation product of coconut alcohol with 5 moles of ethylene oxide 42.2 C12-16 fatty acid ammonia amide 5.9 Borax 5 H2O 10.8 Choline chloride 10.6 Zeosyl* 200 (a silica material having an average particle size of about 2 microns, commercially available from J. M. Huber Corp.) 9.1 An identical sheet of the paper towel is placed over the coated side of the original sheet, and the edges of the two sheets are sewn together so as to enclose the composition. This article provides a convenient method for introducing the compositions of the present invention into the laundering * TRADE MARKS
A' solution, as well as providing excellen~ cleaning performance, and wash solution and storage stability of the cationic component.
A substrate article may also be made by coating one side of an 11" x 11" sheet of melt-blown polypropylene, having a thickness of about 29 mils, a basis weight of about 58.5 grams per square yard, and an air permeability of about 66 cubic ft./min./sq. ft., with about 60 grams of the detergent composition described above, placing an identical substrate sheet over the coated sheet, and heat sealing together the edges of the two substrates, enclosing the detergent composition within the article.
EXAMPLE V
A heavy-duty liquid laundry detergent composition, having the formula given below, is prepared by mixing to-gether the following components in the stated proportions.
Component Wt. %
O CH
Il ~ I _ Condensation product of C14 15 alcohol with 7 moles of ethylene oxide 47.7 , Borax-5 H20 12.0 Lauramide 7.0 Ethanol 10.0 Minors (suds suppressor, perfume, brightener, etc.) balance to 100 This product, when used in an automatic laundering operation, at a concentration of about 0.05%, provides excellent removal of both particulate and greasy/oily soils, while exhibit-ing stability of the cationic component in the wash solution and during storage.
EXAMPLE VI
A substrate article, for use in the automatic launder-ing operation, having the composition given below, is made using the procedure outlined in Example IV, above, with Scott 8050* Industrial Towels as the substrate material.
Component Weight ~
o CH3 Il I
C17H3s-C-0 CH2CH2 1 3 24.6 Condensation product of coconut alcohol with 5 moles of ethylene oxide 61.6 C12_16 fatty acid ammonia amide 7.8 Borax 10 H20 4.2 Minors (suds suppressor, perfume, brightener, etc.) balance to 100 * TRADF~ MARK
~ g753 - - . ~
This article provides a convenient method for introducing the compositions of the present invention into the laundering solution, and, in addition, exhibits excellent storage and wash solution stability for the S cationic component.
~A
Excellent results are also obtained where the nonionic component, used above, is replaced by a mixture of ~he condensation product of C14 15 alcohol with three moles o~
ethylene oxide together with the condensation product of C14 15 alcohol with 7 moles of ethylene oxi.de, in a ratio o lower ethoxylate nonionic to higher etlloxylate nonionic o~
about 2:1; a mixture of the condensation product of C14 15 alcohol with 3 moles of ethylene oxide together with the condensation product o~ myristyl alcohol with 10 moles of of ethylene oxide, in a ratio or lower ethoxylate nonionic to higher ethoxylate nonionic of about 1:1; or a mixture o~
the condensation product of coconut alcohol with 5 moles of ethylene oxide together with an alkyl glyceryl ether havi.ng the formula OH
in a ratio o~ alcohol ethoxylate to gl~ceryl ether o abou~
7:3.
Substantially similar stability results are also ob~ained where the cationic component is replaced by those havinc3 the formulae given below, or mixtures of those surfac~ants:
O CH
Il 1 3 C16H33 C O-CH2CH2- N-CH3 Br O o CH3 i2 25 C CH2CH2_c_o_cH2cH2-N~-C~3 Cl-CH Ol CH3 . Br CH3- I_cH2cH2_0 C (C 2)12 2 2 j 3 o fH3 10 21 (CH2cx2o)lo-c~cH2-N -CH3 Cl S C13H27--(CHCH2)11-C CH2 ll CH3 B
EX~MPLE II
A heavy-duty liquid laundry detergen~ composition, having the formula given below, is produced by mixing together the following components in the stated proportions.
Component Weight %
Il 1 3 17H35 C -CH2cH2- N-CH3 Cl 26.1 Condensation product of coconut alcohOl with 5 moles of ethylene oxide 51,5 Borax 10 H2O 11~5 Ethanol ~,o Minors (suds suppressor, perfume, brighteners, etc.) balance ~o 100 This composition provides excellent removal of both clay and greasy/oily soils, as well as stora~e and wash solution stability o the cationic component.
EX~LE III
A paste-form laundry detergent composition, having the formula given below, is prepared by mixing together the following components in the stated proportions~
Component ~eight %
O CH
ll 1 3 C17E135-C-O-CH2CH2-+N-CH3 Cl 26.0 Csndensation product of coconut lo alcohol with 5 moles of ethylene oxide 5~5 C12_16 fatty acid ammonia amide 7~0 Borax 5 H20 13.0 Minors tsuds suppressor, perfume, brightener, etc.) balance to .lOO
This composition, when used as a paste or in a substrate article, as described hereinafter, prov.i.des excel:Len~ remova~
of both clay and greasy/oily soils, as well as storage and wash solution stability of the cationic component~
..... .. .
11~)9~53 EXAMPLE IV
A substrate article, for use in the automatic machine laundering of fabrics, is made by coating one side of an 8" x ll" sheet of a Scott 8050* Industrial Towel, having an air permeability o, about 130 cu. ft./
min./sq. ft., a basis weight of about 77.5 grams per square yard, and a thickness of 44 mils, with about 50 grams of the detergent composition having the formula-tion given below. The composition is made by intimately mixing the nonionic and cationic surfactants together, at a temperature of about 80 C, to form a thick paste, and then mixing in the remaining components.
Component Weight %
o CH3 C17H35-C-O-CH2CH2- N~CH3 Cl 21.4 Condensation product of coconut alcohol with 5 moles of ethylene oxide 42.2 C12-16 fatty acid ammonia amide 5.9 Borax 5 H2O 10.8 Choline chloride 10.6 Zeosyl* 200 (a silica material having an average particle size of about 2 microns, commercially available from J. M. Huber Corp.) 9.1 An identical sheet of the paper towel is placed over the coated side of the original sheet, and the edges of the two sheets are sewn together so as to enclose the composition. This article provides a convenient method for introducing the compositions of the present invention into the laundering * TRADE MARKS
A' solution, as well as providing excellen~ cleaning performance, and wash solution and storage stability of the cationic component.
A substrate article may also be made by coating one side of an 11" x 11" sheet of melt-blown polypropylene, having a thickness of about 29 mils, a basis weight of about 58.5 grams per square yard, and an air permeability of about 66 cubic ft./min./sq. ft., with about 60 grams of the detergent composition described above, placing an identical substrate sheet over the coated sheet, and heat sealing together the edges of the two substrates, enclosing the detergent composition within the article.
EXAMPLE V
A heavy-duty liquid laundry detergent composition, having the formula given below, is prepared by mixing to-gether the following components in the stated proportions.
Component Wt. %
O CH
Il ~ I _ Condensation product of C14 15 alcohol with 7 moles of ethylene oxide 47.7 , Borax-5 H20 12.0 Lauramide 7.0 Ethanol 10.0 Minors (suds suppressor, perfume, brightener, etc.) balance to 100 This product, when used in an automatic laundering operation, at a concentration of about 0.05%, provides excellent removal of both particulate and greasy/oily soils, while exhibit-ing stability of the cationic component in the wash solution and during storage.
EXAMPLE VI
A substrate article, for use in the automatic launder-ing operation, having the composition given below, is made using the procedure outlined in Example IV, above, with Scott 8050* Industrial Towels as the substrate material.
Component Weight ~
o CH3 Il I
C17H3s-C-0 CH2CH2 1 3 24.6 Condensation product of coconut alcohol with 5 moles of ethylene oxide 61.6 C12_16 fatty acid ammonia amide 7.8 Borax 10 H20 4.2 Minors (suds suppressor, perfume, brightener, etc.) balance to 100 * TRADF~ MARK
~ g753 - - . ~
This article provides a convenient method for introducing the compositions of the present invention into the laundering solution, and, in addition, exhibits excellent storage and wash solution stability for the S cationic component.
~A
Claims (38)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A laundry detergent composition which comprises:
(a) from about 2% to about 95% of a cationic surfactant, containing at least one hydrolyzable linkage selected from the group consisting of , , , -O-, , , , , , and mixtures thereof; and (b) from about 1% to about 25% of an inorganic alkaline component which is insoluble in said cationic sur-factant, and which is present in an amount such that the detergent composition forms a solution having a pH of from about 8 to about 10 within about 3 minutes after it is placed in 100°F water at a concentration of about 0.15%.
(a) from about 2% to about 95% of a cationic surfactant, containing at least one hydrolyzable linkage selected from the group consisting of , , , -O-, , , , , , and mixtures thereof; and (b) from about 1% to about 25% of an inorganic alkaline component which is insoluble in said cationic sur-factant, and which is present in an amount such that the detergent composition forms a solution having a pH of from about 8 to about 10 within about 3 minutes after it is placed in 100°F water at a concentration of about 0.15%.
2. The composition according to Claim 1 wherein the hydro-lyzable linkage is selected from the group consisting of , , , , and mixtures thereof.
3. The composition according to Claim 1 wherein the cationic surfactant is selected from the group consisting of:
(i) wherein each R1 is C1 to C4 alkyl or hydroxyalkyl;
R2 is C5 to C30 straight or branched chain alkyl, alkenyl, alkylbenzyl, or alkyl phenyl group or , wherein s is from 0 to 5;
R3 is C1 to C20 alkylene or alkenylene; a is 0 or 1, n is 0 or 1, and a is 1 only when n is 1; m is from 1 to 5; Z1 and Z2 are each selected from the group consisting of:
, , -O-, , , , , , and wherein at least one of said groups is selected from the group consisting of ester, reverse ester, amide and reverse amide; and X is an anion which makes the surfactant at least water-dispersible;
(ii) wherein each R1 is C1 to C4 alkyl or hydroxyalkyl; each R2 is either hydrogen or C1 to C3 alkyl; R3 is C4 to C30 straight or branched chain alkyl, alkenyl or alkylbenzyl; R4 is C1 to C10 alkylene or alkenylene; n is from 2 to 4; y is from 1 to 20; a is 0 or 1, t is 0 or 1, and a can be only 1 when t is l; m is from 1 to 5; Z2 is selected from the group consisting of , , -O-, , , , , , Z1 is selected from the group consisting of , , , , , and wherein at least one of said Z1 and Z2 groups is selected from the group consisting of ester, reverse ester, amide, and reverse amide; and X is an anion which makes the surfactant at least water-dispersible; and (iii) mixtures thereof.
(i) wherein each R1 is C1 to C4 alkyl or hydroxyalkyl;
R2 is C5 to C30 straight or branched chain alkyl, alkenyl, alkylbenzyl, or alkyl phenyl group or , wherein s is from 0 to 5;
R3 is C1 to C20 alkylene or alkenylene; a is 0 or 1, n is 0 or 1, and a is 1 only when n is 1; m is from 1 to 5; Z1 and Z2 are each selected from the group consisting of:
, , -O-, , , , , , and wherein at least one of said groups is selected from the group consisting of ester, reverse ester, amide and reverse amide; and X is an anion which makes the surfactant at least water-dispersible;
(ii) wherein each R1 is C1 to C4 alkyl or hydroxyalkyl; each R2 is either hydrogen or C1 to C3 alkyl; R3 is C4 to C30 straight or branched chain alkyl, alkenyl or alkylbenzyl; R4 is C1 to C10 alkylene or alkenylene; n is from 2 to 4; y is from 1 to 20; a is 0 or 1, t is 0 or 1, and a can be only 1 when t is l; m is from 1 to 5; Z2 is selected from the group consisting of , , -O-, , , , , , Z1 is selected from the group consisting of , , , , , and wherein at least one of said Z1 and Z2 groups is selected from the group consisting of ester, reverse ester, amide, and reverse amide; and X is an anion which makes the surfactant at least water-dispersible; and (iii) mixtures thereof.
4. A laundry detergent composition which comprises:
(a) from about 2% to about 95% of a surfactant mixture consisting essentially of:
(1) a nonionic surfactant having an HLB of from about 5 to about 17; and (2) a cationic surfactant selected from the group consisting of:
(i) wherein each R1 is C1 to C4 alkyl or hydroxyalkyl;
R2 is C5 to C30 straight or branched chain alkyl, alkenyl, alkylbenzyl, or alkyl phenyl group or , wherein s is from 0 to 5;
R3 is C1 to C20 alkylene or alkenylene; a is 0 or 1, n is 0 or 1, and a is 1 only when n is 1;
m is from 1 to 5; Z1 and Z2 are each selected from the group consisting of:
, , -O-, , , , , , and wherein at least one of said groups is selected from the group consisting of ester, reverse ester, amide and reverse amide; and X is an anion which makes the surfactant at least water-dispersible;
(ii) wherein each R1 is C1 to C4 alkyl or hydroxyalkyl; each R2 is either hydrogen or C1 to C3 alkyl; R3 is C4 to C30 straight or branched chain alkyl, alkenyl or alkylbenzyl; R4 is C1 to C10 alkylene or alkenylene; n is from 2 to 4; y is from 1 to 20; a is 0 or 1, t is 0 or 1, and a can be 1 only when t is 1;
m is from 1 to 5; Z2 is selected from the group consisting of , , -O-, , , , , , Z1 is selected from the group consisting of , , , , , and wherein at least one of said Z1 and Z2 groups is selected from the group consisting of ester, reverse ester, amide, and reverse amide; and X is an anion which makes the surfactant at least water-dispersible; and (iii) mixtures thereof;
wherein the ratio of said nonionic surfactant to said cationic surfactant is in the range of from about 1:1 to about 100:1;
and (b) from about 1% to about 25% of an inorganic alkaline component which is insoluble in said cationic/nonionic surfactant mixture, and which is present in an amount such that the detergent composition forms a solution having a pH of from about 8 to about 10 within about 3 minutes after it is placed in 100°F water at a con-centration of about 0.15%.
(a) from about 2% to about 95% of a surfactant mixture consisting essentially of:
(1) a nonionic surfactant having an HLB of from about 5 to about 17; and (2) a cationic surfactant selected from the group consisting of:
(i) wherein each R1 is C1 to C4 alkyl or hydroxyalkyl;
R2 is C5 to C30 straight or branched chain alkyl, alkenyl, alkylbenzyl, or alkyl phenyl group or , wherein s is from 0 to 5;
R3 is C1 to C20 alkylene or alkenylene; a is 0 or 1, n is 0 or 1, and a is 1 only when n is 1;
m is from 1 to 5; Z1 and Z2 are each selected from the group consisting of:
, , -O-, , , , , , and wherein at least one of said groups is selected from the group consisting of ester, reverse ester, amide and reverse amide; and X is an anion which makes the surfactant at least water-dispersible;
(ii) wherein each R1 is C1 to C4 alkyl or hydroxyalkyl; each R2 is either hydrogen or C1 to C3 alkyl; R3 is C4 to C30 straight or branched chain alkyl, alkenyl or alkylbenzyl; R4 is C1 to C10 alkylene or alkenylene; n is from 2 to 4; y is from 1 to 20; a is 0 or 1, t is 0 or 1, and a can be 1 only when t is 1;
m is from 1 to 5; Z2 is selected from the group consisting of , , -O-, , , , , , Z1 is selected from the group consisting of , , , , , and wherein at least one of said Z1 and Z2 groups is selected from the group consisting of ester, reverse ester, amide, and reverse amide; and X is an anion which makes the surfactant at least water-dispersible; and (iii) mixtures thereof;
wherein the ratio of said nonionic surfactant to said cationic surfactant is in the range of from about 1:1 to about 100:1;
and (b) from about 1% to about 25% of an inorganic alkaline component which is insoluble in said cationic/nonionic surfactant mixture, and which is present in an amount such that the detergent composition forms a solution having a pH of from about 8 to about 10 within about 3 minutes after it is placed in 100°F water at a con-centration of about 0.15%.
5. The composition according to Claim 4 wherein the nonionic surfactant is biodegradable and has the formula R(OC2H4)nOH
wherein R is a primary or secondary alkyl chain of from about 8 to about 22 carbon atoms and n is an average of from about 2 to about 12.
wherein R is a primary or secondary alkyl chain of from about 8 to about 22 carbon atoms and n is an average of from about 2 to about 12.
6. The composition according to Claim 5 which contains from about 5% to about 20% of said inorganic alkaline com-ponent.
7. The composition according to Claim 6 wherein said alkaline component is contained in an amount such that the composition forms a solution having a pH of from about 8.5 to about 9.5, within about 2 minutes, when placed in 100°F
water at a concentration of about 0.15%.
water at a concentration of about 0.15%.
8. The composition according to Claim 7 wherein said alkaline component is selected from the group consisting of borax decahydrate, borax pentahydrate, sodium carbonate, and mixtures thereof.
9. The composition according to Claim 8 which contains from about 8% to about 16% of said alkaline component.
10. The composition according to Claim 5 which contains from about 10% to about 90% of said cationic/nonionic surfactant mixture.
11. The composition according to Claim 10 which contains from about 15% to about 85% of a said cationic/nonionic surfactant mixture.
12. The composition according to Claim 11 wherein the ratio of nonionic surfactant to cationic surfactant is from about:
5:3 to about 50:1.
5:3 to about 50:1.
13. The composition according to Claim 12 wherein, in the nonionic surfactant, R is a C10-C20 alkyl group.
14. The composition according to Claim 13 wherein, in the nonionic surfactant, n is from 2 to 9.
15. The composition according to Claim 14 wherein the ratio of nonionic surfactant to cationic surfactant is from about 5:3 to about 20:1.
16. The composition according to Claim 15 wherein the cationic surfactant has the formula wherein Z2 is selected from the group consisting of ester, reverse ester, amide, and reverse amide.
17. The composition according to Claim 16 wherein Z2 is .
18. The composition according to Claim 17 wherein n is 0 and a is 0.
19. The composition according to Claim 18 wherein R2 is a C8-C20 alkyl group.
20. The composition according to Claim 19 wherein m is 2.
21. The composition according to Claim 15 wherein the cationic surfactant has the formula and wherein Z2 is selected from the group consisting of ester, reverse ester, amide, and reverse amide.
22. The composition according to Claim 21 wherein Z2 is .
23. The composition according to Claim 22 wherein n is 2 and R2 is hydrogen.
24. The composition according to Claim 23 wherein a is 0, m is 2, R4 is methylene, t is 1, y is from 1 to 10, and R3 is a C8-C18 alkyl group.
25. The composition according to Claim 21 wherein the ratio of nonionic surfactant to cationic surfactant is from about 5:3 to about 5:1.
26. The composition according to Claim 15 which contains from about 5% to about 20% of said inorganic alkaline component.
27. The composition according to Claim 26 wherein said alkaline component is contained in an amount such that the composition forms a solution having a pH of from about 8.5 to about 9.5 within about 2 minutes, when placed in 100°F
water at a concentration of about 0.15%.
water at a concentration of about 0.15%.
28. The composition according to Claim 27 wherein said alkaline component is selected from the group consisting of borax decahydrate, borax pentahydrate, sodium carbonate, and mixtures thereof.
29. The composition according to Claim 16 which contains from about 5% to about 20% of said inorganic alkaline component.
30. The composition according to Claim 29 wherein said alkaline component is included in an amount such that said composition forms a solution having a pH of from about 8.5 to about 9.5, within about 2 minutes, when placed in 100°F
water at a concentration of about 0.15%.
water at a concentration of about 0.15%.
31. The composition according to Claim 30 wherein the ratio of said nonionic surfactant to said cationic surfactant is from about 5:3 to about 5:1.
32. The composition according to Claim 31 wherein said alkaline component is selected from the group consisting of borax decahydrate, borax pentahydrate, sodium carbonate, and mixtures thereof.
33. The composition according to Claim 32 wherein said alkaline component is selected from the group consisting of borax decahydrate, borax pentahydrate, and mixtures thereof.
34. The composition according to Claim 33 which contains from about 8% to about 16% of said alkaline component.
35. The composition according to Claim 34 wherein, in said cationic component, R1 is CH3, R2 is C17alkyl, and X is a chlorine anion.
36. The composition according to Claim 35 wherein the ratio of said nonionic component to said cationic component is about 5:2.
37. The composition according to Claim 17 wherein n is 0, a is 0, m is 2, R2 is C17 alkyl, R1 is CH3, and X is chlorine anion.
38. A process for laundering fabrics comprising the agitation of said fabrics in an aqueous solution containing from about 0.01 to about 0.3% of the detergent composition of Claim 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US86413577A | 1977-12-23 | 1977-12-23 | |
| US864,135 | 1977-12-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1109753A true CA1109753A (en) | 1981-09-29 |
Family
ID=25342607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA318,450A Expired CA1109753A (en) | 1977-12-23 | 1978-12-21 | Storage-stable laundry detergent compositions having enhanced performance |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS54129010A (en) |
| CA (1) | CA1109753A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5254271A (en) * | 1991-04-03 | 1993-10-19 | Rewo Chemische Werke Gmbh | Ammonium compounds, preparation thereof and use thereof as cleaning agent, cosmetic raw material and softener, in particular as final-rinse fabric softner |
| GB2564736A (en) * | 2017-03-30 | 2019-01-23 | Innospec Ltd | Composition, method and use |
-
1978
- 1978-12-21 CA CA318,450A patent/CA1109753A/en not_active Expired
- 1978-12-23 JP JP16096878A patent/JPS54129010A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5254271A (en) * | 1991-04-03 | 1993-10-19 | Rewo Chemische Werke Gmbh | Ammonium compounds, preparation thereof and use thereof as cleaning agent, cosmetic raw material and softener, in particular as final-rinse fabric softner |
| GB2564736A (en) * | 2017-03-30 | 2019-01-23 | Innospec Ltd | Composition, method and use |
| US11015137B2 (en) | 2017-03-30 | 2021-05-25 | Innospec Limited | Composition, method and use |
| GB2564736B (en) * | 2017-03-30 | 2021-08-04 | Innospec Ltd | Quaternary ammonium salts and their use in fuel and lubricating compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS54129010A (en) | 1979-10-06 |
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