CA2230651A1 - Enzyme-containing detergent formulation - Google Patents
Enzyme-containing detergent formulation Download PDFInfo
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- CA2230651A1 CA2230651A1 CA 2230651 CA2230651A CA2230651A1 CA 2230651 A1 CA2230651 A1 CA 2230651A1 CA 2230651 CA2230651 CA 2230651 CA 2230651 A CA2230651 A CA 2230651A CA 2230651 A1 CA2230651 A1 CA 2230651A1
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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Abstract
The invention concerns an enzyme-containing detergent formulation which is characterized in that it contains a compound of general formula (I) H3C(CH2)m-A-(CH2)nCOB, in which A stands for a group of formula (a), (b) or -CH=CH-, B
stands for NR1R2, (C1-C8) alkoxy, OH or OM1; and R1, R2 M, M1, m and n are defined as in claim 1.
stands for NR1R2, (C1-C8) alkoxy, OH or OM1; and R1, R2 M, M1, m and n are defined as in claim 1.
Description
CA 022306~1 1998-02-27 t - . WO 98/01526 t~ PCT/EP97/03429 3 ~N THIS A~ED
1~ TRANSLATION
Description Enzyme-containing detergent formulation The present invention relates to an enzyme-containing detergent formulation which comprises a compound of the formula 1.
Enzyme-containing detergent formulations are formulations which, in 10 addition to the customary basic substances, such as, for example, anionic, nonionic and cationic surfactants, builders, bleaching systems, etc., comprise enzymes, such as, for example, proteases, amylases, lipases, etc. The purpose of these enzymes is to remove proteinaceous, starchy or fatty soil from the fabric to be washed. Enzyme-containing detergents of 15 this type are already known and are described, for example, in WO 92/06160.
A disadvantage of these enzyme-containing detergent formulations is that their ability to remove bloodstains is only poor.
EP-A 496 315 describes stable and homogeneous aqueous formulations of surfactants having an HLB of less than or equal to 13, which additionally comprise compounds obtainable by reaction of unsaturated fatty acids with amines and subsequent sulfonation.
The object of the present invention is to provide a dletergent formulation which is also satisfactorily able to remove bloodstains. Surprisingly, this object is achieved by adding a compound of the formula I to an enzyme-containing detergent formulation.
Accordingly, the present invention relates to an enzyme-containing detergent formulation which comprises a compound of the formula I
H3C(CH2)m-A-(CH2)nCOB ~1) CA 022306~1 1998-02-27 , in which A is a group of the formula -C~2-CH-; -CH-CH2- or CH=cH- ;
S l l B is NR'R2, (C1-C8)-alkoxy, OH or OM';
R' is (C,-C8)-alkyl, (C2-C8)-alkenyl, phenyl, alkylphenyl or phenalkyl, each having from 1 to 4 carbon atoms in the alkyl chain or cyclohexyl;
10 R2 is hydrogen or has one of the meanings of R', or in which R' and R2, together with the nitrogen atom to which they are bonded, form a heterocyclic radical; M and M', independently of one another, are an alkali metal cation, triethanolammonium cation or ammonium cation or an equivalent of an alkaline earth metal cation or aluminum cation; and m and n, independently of one another, are each a number from 0 to 22.
A is preferably a group of the formula -CH2-CH-; -CH-CH2- or CH=CH-l l B is preferably NR'R2.
25 (C1-C8)-alkyl R' or R2 can be straight-chain or branched and is, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl. The same applies to (C2-C8)-alkenyl.
30 Alkylphenyl having from 1 to 4 carbon atoms in the alkyl chain is, for example, methyl, ethyl, propyl or butylphenyl. Phenalkyl having from 1 to 4 carbon atoms in the side chain is, for example, benzyl or phenethyl.
A heterocyclic radical formed by R', R2 and the nitrogen atom to which they CA 022306~1 1998-02-27 ~ , , are bonded is, in particular, 5- or 6-membered and can be saturated, unsaturated or partially saturated. Furthermore, it can also contain further hetero members from the series consisting of N, O and S. Examples of heterocyclic radicals of this type are the piperidine, morpholine, thiophene, tetrahydrofuran and tetrahydrothiophene radicals.
In preferred compounds of the formula 1, R1 and R2 are methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butvl, n-pentyl, n-hexyl, n-heptyl, n-octyl, i-octyl, vinyl, allyl, methallyl or crotyl, or R1 and R2, together with the nitrogen atom to which they are bonded, form a piperidine ring or morpholine ring. In particularly preferred compounds of the formula 1, R' and R2 are n-butyl, R' is methyl and R2 is phenyl, or R' and R2, together with the nitrogen atom to which they are bonded, form a morpholine ring.
An alkali metal cation M or M' can, for example, be the cation of lithium, sodium or potassium. An equivalent of an alkaline earth metal cation M or M' can, for example, be derived from magnesium, calcium or barium.
M and M', independently of one another, are preferably the ammonium cation, sodium cation or potassium cation. Particular preference is given to the sodium cation.
m and n, independently of one another, are each preferably a number from 2 to 12, particularly preferably a number from 6 to 8.
The detergent formulations according to the invention preferably comprise the compounds of the formula I in amounts of from 0.1 to 6% by weight, particularly preferably in amounts of from 1 to 5% by weight, based on the 30 total amount of detergent.
The enzymes present in the detergent formulations according to the invention are, for examp!e, commercially available proteases, amylases, lipases, cellulases or peroxidases. It is also possible to use mixtures of the _ CA 022306~1 1998-02-27 , WO 98/01~26 4 PCT/EP97/03429 specified enzymes.
These enzymes are preferably present in amounts of from 0.5 to 2.0% by weight, particularly preferably in amounts of from 0.8 to 1.2% by weight, based on the total amount of detergent.
The detergent formulations according to the inventi~n are based on commercially available ingredients which are known to the person skilled in the art. Suitable ingredients are, for example, anionic surfactants, such as, for example, alkylsulfates, alkyl ether sulfates, linear alkylbenzene sulfonates, secondary alkanesulfonates, C8-C24-oleflnsulfonates, phosphates, as are customarily used in detergents, and further anionic surfactants, such as are described, for example, in WO 92/06160, nonionic surfactants, such as, for example, fatty alcohol poly~lycol ethers, fatty acid amide polyglycol ethers, alkylphenol polyglycol ethers, and cationic, zwitterionic or amphoteric surfactants, such as, for example, alkylbetaines, alkylaminobetaines, sulfobetaines and aminoglycinates.
The ingredients are preferably present in pulverulent detergent formulations in amounts of from 92 to 99.4% by weight, particularly preferably in amounts of from 93 to 97% by weight, based on the total amount of detergent. In liquid detergent formulations, the ingredients are preferably present in amounts of from 35 to 60% by weight, particularly preferably in amounts of from 40 to 50% by weight, based on the total amount of detergent.
In addition, the detergent formulations according to the invention may also comprise further customary auxiliaries and additives. Examples thereof include perfumes, dyes, disinfectants, corrosion inhibitors, bleaches/activators, dye transfer inhibitors etc.
The basis used for the detergent formulations according to the invention is preferably any of the customary detergent formulations known to the person skilled in the art. These can be pulverulent or liquid and may differ CA 022306~1 1998-02-27 from the product according to the invention only by virtue of the fact that they do not contain the compound of the formula 1.
The compounds of the formula I can be prepared, ~or example, by reaction 5 of unsaturated fatty acids of the formula ll H3C(CH2)m-CH=CH-(CH2)nCOOH (Il) in which m and n are as defined above, with amines of the formula lll HNR'R2 (111) in which R' and R2 are as defined above, and sulfuric acid.
15 Suitable examples of fatty acids of the formula ll are, in particular, oleic acid, ricinenic fatty acids and elaidic acids.
The specified synthesis of the compounds of the formula I usually produces mixtures of compounds of the formula 1, which, in addition, may 20 also comprise still unreacted fatty acid of the formula ll. The individual compounds of the formula I can be obtained in pure form from these mixtures by methods known to the person skilled in the art. This is, however, as a rule unnecessary since said mixtures can be used directly in the detergent formulations according to the invention.
The detergent formulations according to the invention can be prepared, for example, by simply mixing the individual constituents, which can be followed by spray drying, agglomeration or extrusion. The person skilled in ~; the art is familiar with these techniques.
The detergent formulations according to the invention achieve the desired object in an excellent manner. Surprisingly, it has been found that the compounds of the formu!a I also have a softening effect and greatly improve the handle of test fabrics, for example of a terry hand towel.
CA 022306~1 1998-02-27 .
Example 1 95% by weight of a commercially available pulverulent detergent comprising Na C,2-alkylbenzenesulfonate, Na C16"8-alkylsulfate and ethoxylated fatty alcohols, 2% by weight of an enzyme mixture comprising protease, lipase and cellulase and 3% by weight of a product of the reaction of elaidic acid with dimethylamine and sulfuric acid are mixed to give a pulverulent detergent formuiation which is able to remove bloodstains in a satisfactory manner.
Example 2 Use of a product of the reaction of ricinenic fatty acid with dipropylamine and sulfuric acid instead of the product of the reaction of elaidic acid with dimethylamine and sulfuric acid, as in Example 1, produces an equally good detergent formulation.
Example 3 A spray-dried detergent comprising 7.5% by weight of Na C12-alkyl benzenesulfonate, 3.0% by weight of Na C,6"8-alkylsulfate, 6.0% by weight of an ethoxylated fatty alcohol, 7.0% by weight of soda, 11.0% by weight of sheet silicate SKS 6, 17.0% by weight of zeolite A, 5.0% by weight of l~la citrate, 5.0% by weight of borax, 20.0% by weight o~ percarbonate, 5.0 % by weight of TAED, 0.5 % by weight of phosphonate, 6.0% by weight of polymers, 1.0% by weight of enzymes (protease, lipase, celllllA~e), 0.2 %
by weight of a commercially available optical brightener and 5.8 % by weight of a product of the reaction of oleic acid, methylphenylamine and sulfuric acid. The product was able to remove bloodstains in a satisfactory manner.
Example 4 11.0% by weight of a secondary Na alkanesulfonate, 16.0% by weight of soap, 12.0 % by weight of an ethoxylated fatty acid ~Icohol, 5.0% by weight of Na citrate, 1.0% by weight of phosphonate, 0.5% by weight of polymers, 1.1% by weight of enzymes (protease, lipase, cellulase), 0.2 % by weight of a commercially available optical brightener, 3.0% by weight of ethanol, CA 022306~1 1998-02-27 5.0% by weight of 1,2-propylene glycol and 2.0% by weight of a product of the reaction of elaidic acid with dipropylamine and sulfuric acid are mixed and subsequently made up to 100% by weight with water to give a liquid detergent which is able to remove bloodstains in a satisfactory manner.
Examples 5 to 7 below investigated the effectiveness of the compounds of the formula I in the form of approximately 40% strength aqueous solutions as regards blood removal in washing experiments in various washing machines in the one-bath process using a variety of detergents. The load 10 in each experiment was 2.5 kg of ballast fabric comprising bed linen, barley corn and cotton terry twist crepe fabric. An Empa 103 combined fabric strip was attached to each of two bed sheets.
The lightening of the test soilings was determined post-wash in each case 15 from reflectance measurements made using an Elrepho 2000.
Example 5:
Investigation of the blood-removing effect using freshly added enzymes at 60~C:
20 The base detergent used for the experiments in a l\lliele 918 washing machine was 100 g of a commercially available pul~erulent detergent having customary ingredients, but without added enzymes. The following comparisons were made in a triplicate determination:
CA 022306~1 1998-02-27 , Type Base detergent Added enzyme Prodwct of the reaction of [9] (1)oleic acid, di-n-butylamine and sulfuric acid a 100 no no b 100 no 5% tq c 100 yes no d 100 yes 3% tq e 100 yes 5% tq (1): Added enzyme:0.2% of Esperase~
+ 0.2% of Lipolase~
+ 0.3% of Termamyl~ 300 + 0.5% of Savinase~
(Al14 of the enzymes used were obtained from Det~rgent Enzyme Division, Bioindustrial Group, Novo Nordisk AJS, Novo Allé, DK-2880 Bagsvaerd).
Reflectance values (R46) Soiling/100 9 a b c d e Detergent +
Blood 79.2 80.4 79.6 80.3 85 Blood/milk/ink48.8 59.1 55.3 56.3 59.8 Example 6 Investigation of the blood-removing effect in commercialiy available detergents at 40~C and 60~C:
The base detergents used for the experiments in a il\/liele W 723 washing machine were commercially available liquid detergents or washing powders having customary ingredients. The following were compared:
a) 95 9 of liquid detergent b) 95 9 of liquid detergent + 5 g of a product of the reaction of oleic acid, di-n-butylamine and sulfuric acid, as a 40% strength aqueous solution CA 022306~1 1998-02-27 c) 95 g of washing powder d) 95 g of washing powder + 5 g of the reaction product as in b), as a 40% strength aqueous solution.
5 Reflectance values (R46) after washing at 40~C
Soiling Liquid Liquid Washing Wash'ng detergent detergent powder powder as in a) as in b) as in c) as in d) Blood 74.4 81.1 82.5 84.1 (test strip 103) Blood/milk/ink 51.8 52.4 48.4 50.5 1 0 (test strip 103) Blood 63.0 68.9 58.5 60.4 (individual swatches) Blood/milk/ink 37.9 39.8 38.0 38.8 (individual swatches) Reflectance values (R46) after washing at 60~C
Soiling Liquid Liquid Washing Wd:.h ,9 detergent detergent powder powder as in a) as in b) as in c) as in d) Blood 70.3 80.1 82.4 87.5 (test strip 103) 20 Blood/milk/ink 54.9 59.6 61.'1 63.0 (test strip 103) Blood 61.4 67.7 66.2 76.5 (individual swatches) Blood/milk/ink 42.5 47.5 50.2 59.7 25 (individual swatches) Example 7:
Handle test: Investigation of the softening effect 30 Example 6 was repeated using a terry hand towel as the test fabric and about 2.3 kg of cotton fabric as ballast. The following were compared:
a) 100 g of liquid detergent , b) 95 g of liquid detergent + 5 g of a product of the reaction of oleic acid, di-n-butylamine and sulfuric acid, as a 40% strength aqueous solution.
5 Assessment of the terry towels by experts after the third and fifth washes revealed a clear improvement in the handle.
1~ TRANSLATION
Description Enzyme-containing detergent formulation The present invention relates to an enzyme-containing detergent formulation which comprises a compound of the formula 1.
Enzyme-containing detergent formulations are formulations which, in 10 addition to the customary basic substances, such as, for example, anionic, nonionic and cationic surfactants, builders, bleaching systems, etc., comprise enzymes, such as, for example, proteases, amylases, lipases, etc. The purpose of these enzymes is to remove proteinaceous, starchy or fatty soil from the fabric to be washed. Enzyme-containing detergents of 15 this type are already known and are described, for example, in WO 92/06160.
A disadvantage of these enzyme-containing detergent formulations is that their ability to remove bloodstains is only poor.
EP-A 496 315 describes stable and homogeneous aqueous formulations of surfactants having an HLB of less than or equal to 13, which additionally comprise compounds obtainable by reaction of unsaturated fatty acids with amines and subsequent sulfonation.
The object of the present invention is to provide a dletergent formulation which is also satisfactorily able to remove bloodstains. Surprisingly, this object is achieved by adding a compound of the formula I to an enzyme-containing detergent formulation.
Accordingly, the present invention relates to an enzyme-containing detergent formulation which comprises a compound of the formula I
H3C(CH2)m-A-(CH2)nCOB ~1) CA 022306~1 1998-02-27 , in which A is a group of the formula -C~2-CH-; -CH-CH2- or CH=cH- ;
S l l B is NR'R2, (C1-C8)-alkoxy, OH or OM';
R' is (C,-C8)-alkyl, (C2-C8)-alkenyl, phenyl, alkylphenyl or phenalkyl, each having from 1 to 4 carbon atoms in the alkyl chain or cyclohexyl;
10 R2 is hydrogen or has one of the meanings of R', or in which R' and R2, together with the nitrogen atom to which they are bonded, form a heterocyclic radical; M and M', independently of one another, are an alkali metal cation, triethanolammonium cation or ammonium cation or an equivalent of an alkaline earth metal cation or aluminum cation; and m and n, independently of one another, are each a number from 0 to 22.
A is preferably a group of the formula -CH2-CH-; -CH-CH2- or CH=CH-l l B is preferably NR'R2.
25 (C1-C8)-alkyl R' or R2 can be straight-chain or branched and is, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl or n-octyl. The same applies to (C2-C8)-alkenyl.
30 Alkylphenyl having from 1 to 4 carbon atoms in the alkyl chain is, for example, methyl, ethyl, propyl or butylphenyl. Phenalkyl having from 1 to 4 carbon atoms in the side chain is, for example, benzyl or phenethyl.
A heterocyclic radical formed by R', R2 and the nitrogen atom to which they CA 022306~1 1998-02-27 ~ , , are bonded is, in particular, 5- or 6-membered and can be saturated, unsaturated or partially saturated. Furthermore, it can also contain further hetero members from the series consisting of N, O and S. Examples of heterocyclic radicals of this type are the piperidine, morpholine, thiophene, tetrahydrofuran and tetrahydrothiophene radicals.
In preferred compounds of the formula 1, R1 and R2 are methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butvl, n-pentyl, n-hexyl, n-heptyl, n-octyl, i-octyl, vinyl, allyl, methallyl or crotyl, or R1 and R2, together with the nitrogen atom to which they are bonded, form a piperidine ring or morpholine ring. In particularly preferred compounds of the formula 1, R' and R2 are n-butyl, R' is methyl and R2 is phenyl, or R' and R2, together with the nitrogen atom to which they are bonded, form a morpholine ring.
An alkali metal cation M or M' can, for example, be the cation of lithium, sodium or potassium. An equivalent of an alkaline earth metal cation M or M' can, for example, be derived from magnesium, calcium or barium.
M and M', independently of one another, are preferably the ammonium cation, sodium cation or potassium cation. Particular preference is given to the sodium cation.
m and n, independently of one another, are each preferably a number from 2 to 12, particularly preferably a number from 6 to 8.
The detergent formulations according to the invention preferably comprise the compounds of the formula I in amounts of from 0.1 to 6% by weight, particularly preferably in amounts of from 1 to 5% by weight, based on the 30 total amount of detergent.
The enzymes present in the detergent formulations according to the invention are, for examp!e, commercially available proteases, amylases, lipases, cellulases or peroxidases. It is also possible to use mixtures of the _ CA 022306~1 1998-02-27 , WO 98/01~26 4 PCT/EP97/03429 specified enzymes.
These enzymes are preferably present in amounts of from 0.5 to 2.0% by weight, particularly preferably in amounts of from 0.8 to 1.2% by weight, based on the total amount of detergent.
The detergent formulations according to the inventi~n are based on commercially available ingredients which are known to the person skilled in the art. Suitable ingredients are, for example, anionic surfactants, such as, for example, alkylsulfates, alkyl ether sulfates, linear alkylbenzene sulfonates, secondary alkanesulfonates, C8-C24-oleflnsulfonates, phosphates, as are customarily used in detergents, and further anionic surfactants, such as are described, for example, in WO 92/06160, nonionic surfactants, such as, for example, fatty alcohol poly~lycol ethers, fatty acid amide polyglycol ethers, alkylphenol polyglycol ethers, and cationic, zwitterionic or amphoteric surfactants, such as, for example, alkylbetaines, alkylaminobetaines, sulfobetaines and aminoglycinates.
The ingredients are preferably present in pulverulent detergent formulations in amounts of from 92 to 99.4% by weight, particularly preferably in amounts of from 93 to 97% by weight, based on the total amount of detergent. In liquid detergent formulations, the ingredients are preferably present in amounts of from 35 to 60% by weight, particularly preferably in amounts of from 40 to 50% by weight, based on the total amount of detergent.
In addition, the detergent formulations according to the invention may also comprise further customary auxiliaries and additives. Examples thereof include perfumes, dyes, disinfectants, corrosion inhibitors, bleaches/activators, dye transfer inhibitors etc.
The basis used for the detergent formulations according to the invention is preferably any of the customary detergent formulations known to the person skilled in the art. These can be pulverulent or liquid and may differ CA 022306~1 1998-02-27 from the product according to the invention only by virtue of the fact that they do not contain the compound of the formula 1.
The compounds of the formula I can be prepared, ~or example, by reaction 5 of unsaturated fatty acids of the formula ll H3C(CH2)m-CH=CH-(CH2)nCOOH (Il) in which m and n are as defined above, with amines of the formula lll HNR'R2 (111) in which R' and R2 are as defined above, and sulfuric acid.
15 Suitable examples of fatty acids of the formula ll are, in particular, oleic acid, ricinenic fatty acids and elaidic acids.
The specified synthesis of the compounds of the formula I usually produces mixtures of compounds of the formula 1, which, in addition, may 20 also comprise still unreacted fatty acid of the formula ll. The individual compounds of the formula I can be obtained in pure form from these mixtures by methods known to the person skilled in the art. This is, however, as a rule unnecessary since said mixtures can be used directly in the detergent formulations according to the invention.
The detergent formulations according to the invention can be prepared, for example, by simply mixing the individual constituents, which can be followed by spray drying, agglomeration or extrusion. The person skilled in ~; the art is familiar with these techniques.
The detergent formulations according to the invention achieve the desired object in an excellent manner. Surprisingly, it has been found that the compounds of the formu!a I also have a softening effect and greatly improve the handle of test fabrics, for example of a terry hand towel.
CA 022306~1 1998-02-27 .
Example 1 95% by weight of a commercially available pulverulent detergent comprising Na C,2-alkylbenzenesulfonate, Na C16"8-alkylsulfate and ethoxylated fatty alcohols, 2% by weight of an enzyme mixture comprising protease, lipase and cellulase and 3% by weight of a product of the reaction of elaidic acid with dimethylamine and sulfuric acid are mixed to give a pulverulent detergent formuiation which is able to remove bloodstains in a satisfactory manner.
Example 2 Use of a product of the reaction of ricinenic fatty acid with dipropylamine and sulfuric acid instead of the product of the reaction of elaidic acid with dimethylamine and sulfuric acid, as in Example 1, produces an equally good detergent formulation.
Example 3 A spray-dried detergent comprising 7.5% by weight of Na C12-alkyl benzenesulfonate, 3.0% by weight of Na C,6"8-alkylsulfate, 6.0% by weight of an ethoxylated fatty alcohol, 7.0% by weight of soda, 11.0% by weight of sheet silicate SKS 6, 17.0% by weight of zeolite A, 5.0% by weight of l~la citrate, 5.0% by weight of borax, 20.0% by weight o~ percarbonate, 5.0 % by weight of TAED, 0.5 % by weight of phosphonate, 6.0% by weight of polymers, 1.0% by weight of enzymes (protease, lipase, celllllA~e), 0.2 %
by weight of a commercially available optical brightener and 5.8 % by weight of a product of the reaction of oleic acid, methylphenylamine and sulfuric acid. The product was able to remove bloodstains in a satisfactory manner.
Example 4 11.0% by weight of a secondary Na alkanesulfonate, 16.0% by weight of soap, 12.0 % by weight of an ethoxylated fatty acid ~Icohol, 5.0% by weight of Na citrate, 1.0% by weight of phosphonate, 0.5% by weight of polymers, 1.1% by weight of enzymes (protease, lipase, cellulase), 0.2 % by weight of a commercially available optical brightener, 3.0% by weight of ethanol, CA 022306~1 1998-02-27 5.0% by weight of 1,2-propylene glycol and 2.0% by weight of a product of the reaction of elaidic acid with dipropylamine and sulfuric acid are mixed and subsequently made up to 100% by weight with water to give a liquid detergent which is able to remove bloodstains in a satisfactory manner.
Examples 5 to 7 below investigated the effectiveness of the compounds of the formula I in the form of approximately 40% strength aqueous solutions as regards blood removal in washing experiments in various washing machines in the one-bath process using a variety of detergents. The load 10 in each experiment was 2.5 kg of ballast fabric comprising bed linen, barley corn and cotton terry twist crepe fabric. An Empa 103 combined fabric strip was attached to each of two bed sheets.
The lightening of the test soilings was determined post-wash in each case 15 from reflectance measurements made using an Elrepho 2000.
Example 5:
Investigation of the blood-removing effect using freshly added enzymes at 60~C:
20 The base detergent used for the experiments in a l\lliele 918 washing machine was 100 g of a commercially available pul~erulent detergent having customary ingredients, but without added enzymes. The following comparisons were made in a triplicate determination:
CA 022306~1 1998-02-27 , Type Base detergent Added enzyme Prodwct of the reaction of [9] (1)oleic acid, di-n-butylamine and sulfuric acid a 100 no no b 100 no 5% tq c 100 yes no d 100 yes 3% tq e 100 yes 5% tq (1): Added enzyme:0.2% of Esperase~
+ 0.2% of Lipolase~
+ 0.3% of Termamyl~ 300 + 0.5% of Savinase~
(Al14 of the enzymes used were obtained from Det~rgent Enzyme Division, Bioindustrial Group, Novo Nordisk AJS, Novo Allé, DK-2880 Bagsvaerd).
Reflectance values (R46) Soiling/100 9 a b c d e Detergent +
Blood 79.2 80.4 79.6 80.3 85 Blood/milk/ink48.8 59.1 55.3 56.3 59.8 Example 6 Investigation of the blood-removing effect in commercialiy available detergents at 40~C and 60~C:
The base detergents used for the experiments in a il\/liele W 723 washing machine were commercially available liquid detergents or washing powders having customary ingredients. The following were compared:
a) 95 9 of liquid detergent b) 95 9 of liquid detergent + 5 g of a product of the reaction of oleic acid, di-n-butylamine and sulfuric acid, as a 40% strength aqueous solution CA 022306~1 1998-02-27 c) 95 g of washing powder d) 95 g of washing powder + 5 g of the reaction product as in b), as a 40% strength aqueous solution.
5 Reflectance values (R46) after washing at 40~C
Soiling Liquid Liquid Washing Wash'ng detergent detergent powder powder as in a) as in b) as in c) as in d) Blood 74.4 81.1 82.5 84.1 (test strip 103) Blood/milk/ink 51.8 52.4 48.4 50.5 1 0 (test strip 103) Blood 63.0 68.9 58.5 60.4 (individual swatches) Blood/milk/ink 37.9 39.8 38.0 38.8 (individual swatches) Reflectance values (R46) after washing at 60~C
Soiling Liquid Liquid Washing Wd:.h ,9 detergent detergent powder powder as in a) as in b) as in c) as in d) Blood 70.3 80.1 82.4 87.5 (test strip 103) 20 Blood/milk/ink 54.9 59.6 61.'1 63.0 (test strip 103) Blood 61.4 67.7 66.2 76.5 (individual swatches) Blood/milk/ink 42.5 47.5 50.2 59.7 25 (individual swatches) Example 7:
Handle test: Investigation of the softening effect 30 Example 6 was repeated using a terry hand towel as the test fabric and about 2.3 kg of cotton fabric as ballast. The following were compared:
a) 100 g of liquid detergent , b) 95 g of liquid detergent + 5 g of a product of the reaction of oleic acid, di-n-butylamine and sulfuric acid, as a 40% strength aqueous solution.
5 Assessment of the terry towels by experts after the third and fifth washes revealed a clear improvement in the handle.
Claims (9)
1. An enzyme-containing detergent formulation which comprises a compound of the formula H3C(CH2)m-A-(CH2)nCOB (I) in which A is a group of the formula B is NR 1R 2, (C1-C8)-alkoxy, OH or OM 1;
R 1 is (C1-C8)-alkyl, (C2-C8)-alkenyl, phenyl, alkylphenyl or phenalkyl, each having from 1 to 4 carbon atoms in the alkyl chain or cyclohexyl;
R 2 is hydrogen or has one of the meanings of R 1, or in which R 1 and R 2, together with the nitrogen atom to which they are bonded, form a heterocyclic radical; M and M 1, independently of one another, are an alkali metal cation or ammonium cation or an equivalent of an alkaline earth metal cation or aluminum cation; and m and n, independently of one another, are each a number from 0 to 22.
R 1 is (C1-C8)-alkyl, (C2-C8)-alkenyl, phenyl, alkylphenyl or phenalkyl, each having from 1 to 4 carbon atoms in the alkyl chain or cyclohexyl;
R 2 is hydrogen or has one of the meanings of R 1, or in which R 1 and R 2, together with the nitrogen atom to which they are bonded, form a heterocyclic radical; M and M 1, independently of one another, are an alkali metal cation or ammonium cation or an equivalent of an alkaline earth metal cation or aluminum cation; and m and n, independently of one another, are each a number from 0 to 22.
2. The formulation as claimed in claim 1, wherein A is a group of the formula or
3. The formulation as claimed in claim 1 and/or 2, wherein B is NR 1R 2.
4. The formulation as claimed in one or more of claims 1 to 3, wherein R 1 and R 2 are methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, i-octyl, vinyl, allyl, methallyl or crotyl, or R 1 and R 2, together with the nitrogen atom to which they are bonded, form a piperidine ring or morpholine ring.
5. The formulation as claimed in one or more of claims 1 to 4, wherein R 1 and R 2 are n-butyl, R 1 is methyl and R 2 is phenyl, or R 1 and R 2, together with the nitrogen atom to which they are bonded, form a morpholine ring.
6. The formulation as claimed in one or more of claims 1 to 5, wherein the compounds of the formula I are present in amounts of from 0.1 to 6% by weight, particularly preferably in amounts of from 1 to 5%
by weight, based on the total amount of detergent.
by weight, based on the total amount of detergent.
7. The formulation as claimed in one or more of claims 1 to 6, wherein the enzymes present are proteases, amylases, lipases, cellulases, peroxidases or mixtures thereof.
8. The formulation as claimed in one or more of claims 1 to 7, wherein the enzymes are present in amounts of from 0.5 to 2.0% by weight, particularly preferably in amounts of from 0.8 to 1.2% by weight, based on the total amount of detergent.
9. The formulation as claimed in one or more of claims 1 to 8, which is based on anionic surfactants, such as, for example, alkylsulfates, alkyl ether sulfates, linear alkylbenzenesulfonates, secondary alkanesulfonates, C8-C24-olefinsulfonates, phosphates, nonionic surfactants, such as, for example, fatty alcohol polyglycol ethers, fatty acid amide polyglycol ethers, alkylphenol polyglycol ethers and cationic, zwitterionic or amphoteric surfactants, such as, for example, alkylbetaines, alkylaminobetaines, sulfobetaines and aminoglycinates.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19626620.3 | 1996-07-03 | ||
| DE1996126620 DE19626620A1 (en) | 1996-07-03 | 1996-07-03 | Enzyme-containing detergent formulation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2230651A1 true CA2230651A1 (en) | 1998-01-15 |
Family
ID=7798712
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2230651 Abandoned CA2230651A1 (en) | 1996-07-03 | 1997-07-01 | Enzyme-containing detergent formulation |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0847439A1 (en) |
| JP (1) | JPH11512145A (en) |
| BR (1) | BR9706536A (en) |
| CA (1) | CA2230651A1 (en) |
| DE (1) | DE19626620A1 (en) |
| WO (1) | WO1998001526A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2732016A1 (en) * | 2011-07-12 | 2014-05-21 | Clariant International Ltd. | Use of secondary paraffin sulfonates for increasing the cleaning capacity of enzymes |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2279314A (en) * | 1939-01-26 | 1942-04-14 | Lever Brothers Ltd | Detergent composition |
| DE2659696C3 (en) * | 1976-12-31 | 1980-08-21 | Hoechst Ag, 6000 Frankfurt | Agent for the finishing of textile material |
| EP0019315B1 (en) * | 1979-05-16 | 1983-05-25 | Procter & Gamble European Technical Center | Highly concentrated fatty acid containing liquid detergent compositions |
| EP0095205B1 (en) * | 1982-05-24 | 1986-10-15 | THE PROCTER & GAMBLE COMPANY | Fatty acid containing detergent compositions |
| DE4034840A1 (en) * | 1990-11-02 | 1992-05-07 | Henkel Kgaa | ENZYMATIC LIQUID DETERGENT |
| TW204366B (en) * | 1991-01-19 | 1993-04-21 | Hoechst Ag | |
| RU2000320C1 (en) * | 1991-05-20 | 1993-09-07 | Научно-исследовательский и проектный институт химической промышленности | Laundry detergent |
| US5474701A (en) * | 1994-01-21 | 1995-12-12 | Buckman Laboratories International, Inc. | Enzymes for recreational water |
-
1996
- 1996-07-03 DE DE1996126620 patent/DE19626620A1/en not_active Withdrawn
-
1997
- 1997-07-01 JP JP10504727A patent/JPH11512145A/en active Pending
- 1997-07-01 WO PCT/EP1997/003429 patent/WO1998001526A1/en not_active Application Discontinuation
- 1997-07-01 EP EP97930465A patent/EP0847439A1/en not_active Withdrawn
- 1997-07-01 BR BR9706536A patent/BR9706536A/en not_active Application Discontinuation
- 1997-07-01 CA CA 2230651 patent/CA2230651A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| MX9801689A (en) | 1998-08-30 |
| EP0847439A1 (en) | 1998-06-17 |
| BR9706536A (en) | 1999-07-20 |
| WO1998001526A1 (en) | 1998-01-15 |
| DE19626620A1 (en) | 1998-01-08 |
| JPH11512145A (en) | 1999-10-19 |
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