EP0847439A1

EP0847439A1 - Enzyme-containing detergent formulation

Info

Publication number: EP0847439A1
Application number: EP97930465A
Authority: EP
Inventors: Werner Antwerpen; Fritz Engelhardt; Manfred Müller; Alexander Lerch
Original assignee: Clariant GmbH
Current assignee: Clariant Produkte Deutschland GmbH
Priority date: 1996-07-03
Filing date: 1997-07-01
Publication date: 1998-06-17
Also published as: MX9801689A; JPH11512145A; CA2230651A1; BR9706536A; WO1998001526A1; DE19626620A1

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 OM?1; and R1, R2 M, M1¿, m and n are defined as in claim 1.

Description

description

Enzyme-containing detergent formulation

The present invention relates to an enzyme-containing detergent formulation which is characterized by a content of a compound of the general formula I.

Enzyme-containing detergent formulations are formulations that are used in addition to usual ones

Basic materials such as anionic, nonionic and cationic surfactants, builders, bleaching systems etc. Enzymes such as proteases, amylases,

Contain lipases, etc. The function of these enzymes is to remove protein, starch or fatty stains from the fabric to be washed.

Enzyme-containing detergents of this type are already known and, for example, in

WO92 / 06160.

A disadvantage of these detergent formulations containing enzymes is that they

Are unable to remove blood stains sufficiently.

EP-A 496315 describes stable and homogeneous aqueous formulations of surfactants with an HLB value of less than or equal to 13, which additionally contain compounds obtainable by reacting unsaturated fatty acids with amines and subsequent sulfonation.

The object of the present invention is to provide a detergent formulation which can also remove blood stains in a satisfactory manner. This object is surprisingly achieved by adding a compound of the general formula I to an enzyme-containing detergent formulation.

The present invention accordingly relates to an enzyme-containing detergent formulation, characterized in that it is a compound of the general Formula I.

H ₃ C (CH ₂ ) _m -A- (CH ₂ ) _n COB (I)

wherein

A for a group of the formula

-CH ₂ -CH-; -CH-CH ₂ - or CH = CH-

II OS0 ₃ M OS0 ₃ M

stands;

B represents NR ¹ R ² , (C _r C ₈ ) alkoxy, OH or OM ¹ ; R ^{1 is} (C ₁ -C ₈ ) alkyl, (C ₂ -C ₈ ) alkenyl, phenyl, alkylphenyl or phenalkyl, each with

1 to 4 carbon atoms on the alkyl chain or cyclohexyl; R ^{2 represents} hydrogen or has one of the meanings of R ¹ or in which R and R ² together with the N atom carrying them form a heterocyclic radical; M and M ¹ independently of one another for an alkali metal, triethanolammonium or ammonium cation or an equivalent of an alkaline earth metal or

Aluminum cations stand; and

m and n each independently represent a number from 0 to 22; contains.

A preferably represents a group of the formula

-CH ₂ -CH-; -CH-CH ₂ - or CH = CH-

II OS0 ₃ M OS0 ₃ M

B preferably represents NR ¹ R ² R ¹ or R ² (C _r C ₈ ) -alkyl 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 (C ₂ -C ₈ ) alkenyl.

Alkylphenyl with 1 to 4 carbon atoms in the alkyl chain is, for example, methyl, ethyl, propyl or butylphenyl. Phenalkyl with 1 to 4 carbon atoms in the side chain is, for example, benzyl or phenethyl.

A heterocyclic radical formed by R ¹ , R ² and the N atom carrying them is in particular 5- or 6-membered and can be saturated, unsaturated or partially unsaturated. In addition, it can also contain further hetero elements from the series N, 0 and S. Examples of such heterocyclic radicals are the piperidine, morpholine, thiophene, tetrahydrofuran or tetrahydrothiophene radical.

In preferred compounds of the general formula I, R ¹ and R ² denote 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 N atom carrying them form a piperidine or morpholine ring. In particularly preferred compounds of the general formula 1, 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 N atom carrying them form a morpholine ring.

An alkali indication for M or M ¹ can be, for example, the cation of lithium, sodium or potassium. An equivalent of M or M ^{1 of} an alkaline earth metal cation can be derived, for example, from magnesium, calcium or barium.

M and M ¹ preferably independently of one another represent the ammonium, sodium or potassium cation. The sodium cation is particularly preferred.

m and n preferably each independently represent a number from 2 to 12, particularly preferably a number from 6 to 8. The detergent formulations according to the invention preferably contain the compounds of the general formula 1 in amounts of 0.1 to 6% by weight, particularly preferably in amounts of 1 to 5% by weight, based on the total amount of detergent.

The enzymes contained in the detergent formulations according to the invention are, for example, commercially available proteases, amylases, lipases, cellulases or peroxidases. Mixtures of the enzymes mentioned can also be used.

These enzymes are preferably present in amounts of 0.5 to 2.0% by weight, particularly preferably in amounts of 0.8 to 1.2% by weight, based on the total amount of detergent.

The detergent formulations according to the invention are based on commercially available ingredients known to those skilled in the art. Suitable ingredients are, for example, anionic surfactants, such as, for example, alkyl sulfates, alkyl ether sulfates, linear alkylbenzenesulfonate, secondary alkanesulfonate, C ₈ -C ₂₄ -olefin sulfonates, phosphates, as are usually used in detergents, and other anionic surfactants, as described, for example, in WO92 / 06160 are 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.

The ingredients in powder detergent formulations are preferably present in amounts of 92 to 99.4% by weight, particularly preferably in amounts of 93 to 97% by weight, based on the total amount of detergent. In liquid detergent formulations, the ingredients are preferably present in amounts of 35 to 60% by weight, particularly preferably in amounts of 40 to 50% by weight, based on the total amount of detergent. In addition, the detergent formulations according to the invention can also contain other customary auxiliaries and additives. Examples are fragrances, dyes, disinfectants, corrosion inhibitors, bleach / activators, dye transfer inhibitors, etc.

All of the customary detergent formulations known to those skilled in the art are preferably used as the basis for the detergent formulations according to the invention. These may be powdery or liquid and may differ from the product according to the invention only in the absence of a compound of the general formula I.

The compounds of general formula I can be prepared, for example, by reacting unsaturated fatty acids of general formula II

H ₃ C (CH ₂ ) _m -CH = CH- (CH ₂ ) _n COOH (II)

wherein m and n are as defined above, with amines of the general formula III

HNR ¹ R ² (III)

wherein R ¹ and R ^{2 are} as defined above and sulfuric acid.

Suitable examples of fatty acids of the general formula II are in particular oleic acid, ricin fatty acids and elaidic acid.

The synthesis of the compounds of the general formula I mentioned generally gives rise to mixtures of compounds of the general formula I, which may also contain unreacted fatty acids of the general formula II. The individual compounds of the general formula I can be obtained in pure form from these mixtures by methods known to the person skilled in the art. As a rule, however, this is not necessary since the mixtures mentioned 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 components, which can be followed by spray drying, agglomeration or extrusion. Those skilled in the art are familiar with these procedures.

The detergent formulations according to the invention achieve the stated object in an outstanding manner. Surprisingly, it was found that the compounds of the general formula I also have a softening effect and sustainably improve the feel of test fabrics, for example a terry towel.

example 1

By mixing 95% by weight of a commercial powder detergent containing Na-C ₁₂ -alkylbenzenesulfonate, Na-C _16/18 -alkyl sulfate and ethoxylated fatty alcohols, 2% by weight of an enzyme mixture of protease, lipase and cellulase and 3% by weight of a reaction product A powder detergent formulation is obtained from elaidic acid with dimethylamine and sulfuric acid, which can remove blood stains in a satisfactory manner.

Example 2

If a reaction product of ricinoleic acid with dipropylamine and sulfuric acid is used in Example 1 instead of the reaction product of elaidic acid with dimethylamine and sulfuric acid, an equally good detergent formulation is obtained.

Example 3

Spray-dried detergent made from 7.5% by weight Na-C ₁₂ alkylbenzenesulfonate, 3.0% by weight Na-C _16/18 alkyl sulfate, 6.0% by weight of an ethoxylated fatty alcohol, 7.0% by weight soda, 11 , 0% by weight layered silicate SKS 6, 17.0% by weight zeolite A, 5.0% by weight Na citrate, 5.0% by weight Borax, 20.0% by weight percarbonate, 5.0% by weight TAED, 0.5

% By weight phosphonates, 6.0% by weight polymers, 1.0% by weight enzymes (protease, lipase, cellulase), 0.2% by weight of a commercially available optical brightener and 5.8% by weight of a reaction product from oleic acid, Methylphenylamine and sulfuric acid. The product can remove blood stains satisfactorily.

Example 4

By mixing 11.0% by weight of a secondary Na alkanesulfonate, 16.0% by weight of soap, 12.0% by weight of an ethoxylated fatty acid alcohol, 5.0% by weight of Na citrate, 1.0% by weight Phosphonates, 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, 5.0% by weight 1, 2-propylene glycol and 2.0% by weight of a reaction product of elaidic acid with dipropylamine and sulfuric acid and subsequent filling with water to 100% by weight, a liquid detergent is obtained which can remove blood stains in a satisfactory manner.

In the following Examples 5 to 7, the effectiveness of the compounds of the general formula I in the form of about 40% aqueous solutions with regard to blood removability was tested in washing tests in different washing machines in a one-bath process with different detergents. The loading was carried out in each experiment with 2.5 kg of ballast fabric consisting of bed linen, barley grain and cotton twisted terry crepe. A combined laundry strip 103 from Empa was attached to two bed sheets.

The lightening of the test stains was determined after washing by reflectance measurements using Elrepho 2000.

Example 5:

Examination of the blood-removing effect with freshly added enzymes

60 ° C:

The basic detergent for the tests in a Miele 918 washing machine was used

100 g of a commercially available powder detergent with usual ingredients, but without the addition of enzymes. The following were compared in a triple determination:

(1): Enzyme addition: 0.2% ®Esperase,

+ 0.2% ®Lipolase + 0.3% ®Termamyl 300 + 0.5% ®Savinase

(All 4 enzymes used were obtained from Detergent Enzyme Division, Bioindustrial Group, Novo Nordisk A / S, Novo Alle, DK -2880 Bagsvaerd).

Remission values (R46)

Soiling / 100 g a b c d e detergent +

Blood 79.2 80.4 79.6 80.3 85

Blood-milk-ink 48.8 59.1 55.3 56.3 59.8

Example 6

Examination of the blood-removing effect in commercially available detergents

40 and 60 ° C:

As a basic detergent for the tests in a Miele W 723 washing machine, commercially available liquid detergents or washing powder were used with the usual

Ingredients used. The following were compared: a) 95 g of liquid detergent b) 95 g of liquid detergent + 5 g of a reaction product of oleic acid, di-n-butylamine and sulfuric acid as a 40% aqueous solution c) 95 g of washing powder d) 95 g of washing powder + 5 g of reaction product according to b ) as a 40% aqueous solution. Remission values (R46) after washing at 40 ° C

Soiling liquid-liquid washing powder washing powder detergent detergent according to c) according to d) according to a) according to b)

Blood 74.4 81, 1 82.5 84.1 (test strips 103)

Blood-milk-ink 51.8 52.4 48.4 50.5 (test strips 103)

Blood 63.0 68.9 58.5 60.4 (single lobules)

Blood-milk-ink 37.9 39.8 38.0 38.8 (single lobes)

Remission values (R46) after washing at 60 ° C

Blood 70.3 80.1 82.4 87.5

(Test strips 103)

Blood-milk-ink 54.9 59.6 61, 1 63.0

(Test strips 103)

Blood 61,467.7 66.2 76.5

(Single lobes)

Blood-milk-ink 42.5 47.5 50.2 59.7

(Single lobes) Example 7:

Finger test: Examination of the softening effect

The procedure was analogous to Example 6, with a terry towel as the test fabric and about 2.3 kg of cotton fabric as ballast. The following was compared: a) 100 g of liquid detergent b) 95 g of liquid detergent + 5 g of a reaction product of oleic acid, di-n-butylamine and sulfuric acid as a 40% aqueous solution.

When the towels were checked by experts after the third and fifth wash, there was clearly an improvement in the handle.

Claims

claims

1. enzyme-containing detergent formulation, characterized in that it is a compound of general formula I.

H ₃ C (CH ₂ ) _m -A- (CH ₂ ) _n COB (I)

wherein

A for a group of the formula -CH ₂ -CH-; -CH-CH ₂ - or -CH = CH-

I I

OS0 ₃ M OS0 ₃ M

stands; B represents NR ¹ R ² (C _r C ₈ ) alkoxy, OH or OM ¹ ;

R ^{1 is} (C _r C ₈ ) -alkyl, (C ₂ -C ₈ ) -alkenyl, phenyl, alkylphenyl or phenalkyl, each having 1 to 4 C atoms on the alkyl chain or cyclohexyl;

R ^{2 represents} hydrogen or has one of the meanings of R ¹ or in which

R ¹ and R ² together with the N atom carrying them form a heterocyclic radical; M and M ¹ independently of one another for an alkali or

Ammonium cation or an equivalent of an alkaline earth metal or aluminum cation; and m and n each independently represent a number from 0 to 22; contains.

2. Formulation according to claim 1, characterized in that A for a

Group of the formula

-CH ₂ -CH- or -CH-CH ₂ -

II OS0 ₃ M OSO3M stands.

3. Formulation according to claim 1 and / or 2, characterized in that B represents NR ¹ R ² .

4. Formulation according to one or more of claims 1 to 3, characterized in that 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 one they carry N atom form a piperidine or morpholine ring.

5. Formulation according to one or more of claims 1 to 4, characterized in that 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 N atom carrying them is a morpholine ring form.

6. Formulation according to one or more of claims 1 to 5, characterized in that the compounds of general formula 1 in amounts of 0.1 to 6% by weight, particularly preferably in amounts of 1 to 5% by weight, based on the Total amount of detergent included.

7. Formulation according to one or more of claims 1 to 6, characterized in that proteases, amylases, lipases, cellulases, peroxidases or mixtures thereof are contained as enzymes.

8. Formulation according to one or more of claims 1 to 7, characterized in that the enzymes in amounts of 0.5 to 2.0% by weight, particularly preferably in amounts of 0.8 to 1.2% by weight, based on the total amount of detergent included.

9. Formulation according to one or more of claims 1 to 8, characterized in that it is based on anionic surfactants, such as alkyl sulfates, alkyl ether sulfates, linear alkyl benzene sulfonates, secondary alkane sulfonates, C ₈ -C ₂₄ olefin sulfonates, 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, alkyl betaines, alkylaminobetaines, sulfobetaines and aminoglycinates.