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CN1049682C - Detergent compositions - Google Patents

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Publication number
CN1049682C
CN1049682C CN93114193A CN93114193A CN1049682C CN 1049682 C CN1049682 C CN 1049682C CN 93114193 A CN93114193 A CN 93114193A CN 93114193 A CN93114193 A CN 93114193A CN 1049682 C CN1049682 C CN 1049682C
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acid
weight
enzyme
detergent composition
composition
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CN1088611A (en
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J·迪格鲁特
G·沙勒
M·F·沃尔什
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Unilever NV
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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/14—Hydrolases (3)
    • C12N9/48—Hydrolases (3) acting on peptide bonds (3.4)
    • C12N9/50—Proteinases, e.g. Endopeptidases (3.4.21-3.4.25)
    • C12N9/52—Proteinases, e.g. Endopeptidases (3.4.21-3.4.25) derived from bacteria or Archaea
    • C12N9/54—Proteinases, e.g. Endopeptidases (3.4.21-3.4.25) derived from bacteria or Archaea bacteria being Bacillus
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0069—Laundry bars
    • 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
    • C11D3/38609—Protease or amylase in solid compositions only

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  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Detergent Compositions (AREA)

Abstract

A shaped detergent corn position comprises a detergent active, water and a mutant subtilisin enzyme in which the amino acids in positions 195 and 222 in the native enzyme have been replaced with different amino acids (preferably with glutamic acid and alanine, respectively).

Description

A kind of solid detergent of moulding
The invention relates to and be directly used in fabric, the detergent composition with forms such as bar, sheet, rods on crust or any other surface.More particularly, it is about the soap of bar shaped or soap/synthetic composition, wherein also comprises proteolytic enzyme in the soap bar.
It is that people know that proteolytic enzyme is added in the soap bar, and still, because enzyme is tending towards unstable, this can make it lose activity in this class soap bar.According to English Patent 265024, this shortcoming can be by the dehydration of enzyme, so that water-content reaches 10% or lowlyer overcome in the soap bar.
As alternative another kind of method, in order to prepare water content greater than 10% soap bar, the someone advises using the proteolytic enzyme stablizer, still, many stablizers are not easy to be used for the solid phase prod of soap bar or other analogous shape, because they can have a negative impact to the structure and the soundness of product.
English Patent 2,186, boron compounds are used in 883 suggestions, polyvalent alcohol, the mixture of an alkali metal salt of the mineral acid of organic acid or its an alkali metal salt and non-boron compound is used for soap bar as the stabilising system of proteolytic enzyme such as Savinase.
Use also is known by the mutant subtilysin proteolytic enzyme that the replacement on the amino acid position improves.The claimed subtilysin mutant that aminoacid replacement is arranged on 32,155,104,222,166,64,33,169,189,217 or 157 at the amino acid position in the United States Patent (USP) (Genencor) for example.Shown in the presence of SYNTHETIC OPTICAL WHITNER, to have improved oxidative stability at the mutant proteases that methionine(Met) on the amino acid position 222 is replaced by L-Ala.
We find now to prepare with containing of bar or other shaping solid form suitable high-content water, the detergent composition that is generally 10% to 30% (weight) and contains mutant subtilysin enzyme be possible, said mutant subtilysin enzyme at the position 195 and 222 of its proteolytic enzyme through improvement.This based composition, particularly compare with the soap bar that contains proteolytic enzyme commonly used such as Savinase with the composition of the form of soap bar, even also all have improved enzyme package stability in the presence of SYNTHETIC OPTICAL WHITNER, in addition, the result of this raising enzyme stability has also improved the performance of soap bar.
Therefore, the invention provides and contain detergent active ingredients; The detergent composition of the shaping solid form of water and mutant subtilysin enzyme, in said mutant subtilysin enzyme by making aminoacid sequence that variation take place with the replacement of another kind of amino acid on 195 and 222.
Composition of the present invention preferably also contains the stabilising system of organic boron compound and polyvalent alcohol.
Said stabilising system can also contain at least a other following component that is selected from:
I) organic acid, organic acid an alkali metal salt, mineral acid and its mixture; With
The ii) an alkali metal salt of the mineral acid of non-boron compound.
Even the advantage of the present composition is that they also can be than the much longer time of similar composition stores that existed in the past under the condition of high temperature and high humidity, and enzymic activity does not have any tangible loss.This point is very important, because the detergent composition of this class strip or other solid shape normally uses in the country under mainly being in such condition.
The boron compound that is applicable to stabilising system comprises boric acid, boron oxide and alkali metal borate, particularly borax.Polyvalent alcohol can be aliphatic polyol, especially propylene glycol, glycerol and the Sorbitol Powder with 2-6 carbon atom and 2 to 6 hydroxyls.Organic acid can be aliphatic series one, two, tricarboxylic acid, formic acid particularly, succsinic acid, hexanodioic acid, pentanedioic acid, citric acid or commercially available their mixture, Sokalan DCS (trade mark) for example, sour as tallow, coconut, palm-kernel and Ba Basu lipid acid with soap, suitable organic acid an alkali metal salt comprises sodium formiate, Trisodium Citrate and Sodium Propionate.The mineral acid that is suitable for is a phosphoric acid.An alkali metal salt that is not the mineral acid of boron compound comprises sodium sulfate, sodium-chlor, yellow soda ash, sodium bicarbonate and sodium phosphate.
The preferred content of boron compound is 0.1 to 10%, and most preferred is 0.5 to 5%; The preferred content of polyvalent alcohol is 0.1 to 15%, and most preferred is 0.5 to 10%; The content of organic acid or its salt or mineral acid is 0.1 to 10%, and preferred content is 0.5 to 5%: the alkali metal salt content that is not the mineral acid of boron compound is 0.1 to 5% preferably 0.25 to 2.5%; Above-mentioned all percentage ratio all is the weight percentage with composition weight meter.
Soap bar of the present invention preferably also comprises:
I) 25 to 80%, (weight), the detergent active ingredients of 25 to 70% (weight) most preferably, they can be the mixtures of soap or soap and synthetic detergent active ingredients, said detergent active ingredients is counted as anhydrous;
Ii) 0 to 35%, (weight), most preferred is the water of 10 to 30% (weight);
Iii) 0 to 35% (weight), most preferred is the filler of 0.1 to 30% (weight).
Iv) mutant subtilysin enzyme, wherein aminoacid sequence changes as follows: replace the 195th amino acid with L-glutamic acid or aspartic acid, replace the 222nd amino acid with L-Ala or halfcystine, its content is that proteolytic activity reaches 0.1 to 100GU/mg amount in whole compositions.
When the synthetic detergent active ingredients was included in the soap bar, in the total amount of detergent active ingredients, preferably between 0.1% to 10% (weight), most preferred be 0.5 to 5% (weight) to its content.
Be applicable to that fatty acid soaps of the present invention can obtain from natural resource such as plant or Tallow, beef (for example plam oil, Oleum Cocois, babassu oil, soya-bean oil, Viscotrol C, tallow, whale or fish oil, Tallow, beef, lard and their mixture).Fatty acid soaps can also prepare (for example oxidation by oil, or the Fisher-Tropsch process by co hydrogenation) by synthetic.Those resinous acids that exist in resinous acid such as the Yatall MA also can use.Naphthenic acid also is suitable for.
Tallow fatty acids can obtain from various Animal resources, and comprises about 1% to 8% nutmeg acid usually, about 21% to 32% palmitinic acid, about 14% to 31% stearic acid, about 0% to 4% Zoomeric acid, about 36% to 50% oleic acid and about 0% to 5% linolic acid.General 2.5% nutmeg acid, 29% palmitinic acid, 23% stearic acid, 2% Zoomeric acid, 41.5% oleic acid and 3% linolic acid of being distributed as.
Oleum Cocois is meant the fatty acid mixt with following approximate carbon chain length distribution: 8%C 8, 7%C 10, 48%C 12, 17%C 14, 8%C 16, 2%C 18, 7% oleic acid and 2% linolic acid (above listed preceding 6 kinds of lipid acid are saturated).Having other resource of similar carbon chain length distribution such as palm-kernel oil and babassu oil is included in the scope of term Oleum Cocois.The unsaturated fatty acids that coco-nut oil fatty acid generally has enough low levelss can have satisfied preservation quality so that it need not further processing.But, usually by aliphatic acid hydrogenation unsaturated (particularly how unsaturated) degree with the reduction fatty acid mixt.
Babassu oil is meant the fatty acid mixt with following approximate carbon chain length: 7.8%C 8, 6.5%C 10, 44%C 12, 15.2%C 14, 7.9%C 16, 3.2%C 18, 12%C 18: 1,2.3%C 18: 2 (last two kinds is respectively single and two unsaturated).
Also may comprise nonsoap detergent active ingredient such as branch-alkylbenzene sulfonate, linear alkylbenzene sulfonate and non-ionic ethoxylated alcohol in a small amount in the composition of the present invention.
Filler preferably is selected from kaolin, wilkinite, silicate, talcum, sodium sulfate and yellow soda ash.
The mutant subtilysin enzyme that uses in the composition of the present invention is disclosed among the WO-A-89/06279 (Novo/Nordisk).They are that with the difference of natural subtilysin enzyme it contains different amino acid on 195 and 222.Natural enzyme is containing glycine residue and containing methionine residue on 222 on 195.Particularly preferred mutant enzyme is to contain glutaminic acid residue on 195, contains the enzyme of alanine residue on 222.Commercially available material through said mutation is Durazym (a Novo/Nordisk product).This enzyme can also suddenly change on the position beyond the above-mentioned position.
Usually, the amount that is included in the mutant subtilysin enzyme in the present composition is the corresponding proteolytic activity 0.1 to 100GU/mg in composition, preferably 0.5 to 20GU/mg, and most preferred is 1.0 to 10GU/mg amount, and wherein GU/mg is meant every milligram glycine unit.
The glycine unit definition is under standard conditions, is the terminal NH that is equivalent to 1 mcg/ml glycine that culture medium culturing produced in 15 minutes at 40 ℃ with N-acetyl casein 2The activity of the enzyme of-base unit weight.
Except the mutant subtilysin enzyme of above-mentioned definition, composition of the present invention can also comprise other albumen water quality enzyme.In addition, subtilysin proteolytic enzyme can be that plant, animal or microorganism come.Preferably microbe-derived, microbial source comprises yeast, fungi mould and bacterium.Particularly preferably be obtain from the special bacterial strain of withered grass and licheniformin, bacterium subtilysin type proteolytic enzyme.The example of the commercially available proteolytic enzyme that is suitable for is Alcalase, Savinase, Esperase, all proteolytic enzyme of Novo/Nordisk A/S; The Maxatase of Gist-Brocades and Maxacal; The Kazusase of Showa Denko company; Subtilysin BPN proteolytic enzyme or the like.
Composition of the present invention can also contain enzyme such as lipase, Lipolase (trade name, by Novo/Nordisk company produce) for example, the lipase that extracts from Humicolu Lanuginosa; Amylase, it is the commercially available material with trade mark Termamyl sale that Novo/Nordisk company produces; Cellulase, it is the commercially available material with Celluzyme (trade mark) sale that Novo/Nordisk company produces.
Enzyme can join in the detergent composition of the present invention with spissated forms liquid, aqueous or slurries.
Except above-mentioned these components, detergent bar of the present invention can also contain multiple optional materials.For example washing assistant such as water-soluble phosphate, water soluble carbonate and organic washing-assisting detergent be introduced in the detergent bar of the present invention.Other composition such as starch, Xylo-Mucine, tinting material, white dyes, opalizer, sterilant, spices, sanitas such as ethylenediamine tetraacetic acid (EDTA) (EDTA), 1-hydroxyl-1,1 '-ethylidene diphosphonic acid (EHDP), formaldehyde and clorox, sucrose and Sorbitol Powder also can be contained in the detergent bar of the present invention.
Soap bar of the present invention can prepare with equipment commonly used and method commonly used.Mutant subtilysin enzyme, the enzyme of any other interpolation and the component of stabilising system can any step in preparation process add.Stable component preferably added before enzyme.With method press strip commonly used, and if desired,, wait to be packaged the mixture of each component of obtaining with its embossing.
To further specify the present invention now and illustrate with the following example, percentage ratio wherein is meant weight percentage.
EXAMPLE l
From common soap (82% tallow, 18% Oleum Cocois) the preparation hard soap bar that makes by full saponification.With in 0.15% the ortho-phosphoric acid and said soap, mixed about 20 minutes down at 80 ℃ then.Then add stabilising system and remix one hour when temperature is controlled at 80 ℃.The water-content that reduces the gained mixture by vacuum-drying is to reach required water capacity and to add enzyme.Then on the soapmaking production line with the mixture press strip of common method with gained.
In each case, measure the water-content of soap bar and total fatty matter content, and find that they are respectively 17-19% and 65-70%, (weight).Soap bar is individually with glycine paper and/or polyethylene is packed and store down at 30 ℃.The certain intervals time uses 5101 Scalar automatic analyzers to measure the residual enzyme activity of soap bar in storage process.
Under each situation, some soap bar dissolving has generated rare aqueous solution.The activity of enzyme is measured by the title complex photometric detection, and said title complex is to be generated by enzyme in solution and the reaction of proteolytic enzyme substratum.Its result is as follows.
The active % of composition enzyme
Storage time (my god) i) has sodium formiate (2%), borax (2%) 14 27 41 propylene glycol (2%), sodium sulfate (1%) contain enzyme soap bar enzyme: a) Savinase * 8 GU/mg (water content 17.5%, TFM 168.7%) Durazym * * 8 GU/mg 82 83 79b)) (water content 17.4%, TFM 165.4%) 100 100 100ii) has sodium formiate (2%), borax (2%) propylene glycol (2%), sucrose (5%), sodium sulfate (1%) contain enzyme soap bar enzyme: a) Savinase 8 GU/mg 89 92 85 (water content 17.4%, TFM 164.1%) Durazym 8 GU/mg 100 100 100 (water content 17.0%, TFM b) 165.4%) iii) have borax (2%), propylene glycol (2%) sucrose (5%), sodium sulfate (1%) contain enzyme soap bar enzyme: a) Savinase 8 GU/mg 87 84 75 (water content 18.7%, TFM 164.8%) Durazym 8 GU/mg 100 100 100 (water content 18.8%, TFM b) 165.6%) 8.0 liters of 16.0 liters of (Novo/Nordisk A/S product) * * Duraxym of * Savinase (Novo/Nordisk A/S product) are containing glutaminic acid residue and containing the mutant subtilysin proteolytic enzyme of alanine residue on 222 on 195.
1 fatty substance total amount
The above results shows that the soap bar that contains mutant subtilysin enzyme Durazym is much more stable than the soap bar that contains the Savinase enzyme, that is to say that the remaining enzymic activity of this soap bar is more much higher than the remaining enzymic activity that contains Savinase enzyme soap bar after storing for some time.
Example II
Check the variation of residual enzyme activity (enzyme stability) in the present embodiment by the stabiliser system that uses different amounts.
The soap bar for preparing composition A and B according to the method for summarizing in the example I.Composition A B
Weight % citric acid 1 0.5
Sodium sulfate 1 0.5
Sodium formiate 21
Glycerine 21
16.0 liters of * * Durazym of borax 21 Durazym * * 5 GU/mg bar compositions, 0.3 0.3 soap bases (80% tallow, 20% Oleum Cocois) (Novo/Nordisk A/S product)
Soap bar is packaged in the glycine paper (glycine paper) seriatim and is to store under 70% the condition 37 ℃ and relative humidity.In storage process, periodically measure the residual enzyme activity of soap bar.Its result is as follows.
The remaining enzymic activity % of composition storage time/sky A B
0 100 100
7 - 92
21 - 82
35 - 80
42 - 78
49 - 76
50 84 -
57 89 -
64 82 -
70 - 68
71 80 -
91 - 66
92 84 -
105 - 59
106 78 -
177 76 -
Even The above results shows that enzymic activity still maintains acceptable level when the amount of stabilising system reduces.
EXAMPLE III
In the present embodiment the washing property of residual enzyme (enzyme stability) of using the mutant subtilysin enzyme soap bar with slurry preparation Savinase Durazym is compared.
The soap bar of composition C and D is to prepare according to the method for being summarized among the embodiment 1.
Composition C D
Weight %
Citric acid 11
Sodium sulfate 11
Sodium formiate 22
Glycerine 22
Borax 22
16.05 liters of * Durazym of enzyme Durazym slurries * 0.3-Savinase slurries-0.3 soap bases (80% tallow, 20% Oleum Cocois) (Novo/Nordisk A/S product)
Soap bar is packaged in the glycine paper seriatim and is to store under 70% the condition 37 ℃ and relative humidity.In storage process, periodically measure the remaining enzymic activity of soap bar.Its result is as follows.
Remaining enzymic activity % composition C D storage time/sky
0 100 100
7 - 80
14 100 60
35 98 40
70 89 37
The above results shows that the soap bar that contains mutant subtilysin enzyme Durazym has higher enzyme stability than the soap bar that contains the Savinase enzyme accordingly.
EXAMPLE IV
In the present embodiment, the washing (-)off properties to the soap bar that contains Savinase and Durazym liquid enzymes compares.
The soap bar for preparing composition E and F by the method for summarizing in the example I.
Composition E F
Weight %
Coconut fatty acid 11
Sodium sulfate 11
Sodium formiate 11
Glycerine 22
Borax 22
Enzyme Durazym liquid * * 0.12
(5GU/mg bar composition
Savinase liquid * * *-0.12
(5GU/mg bar composition) * * Durazym 16.0 liters of Savinase of 16.0 liters of (Novo/Nordisk A/S product) * * * (Novo/Nordisk A/S product)
After the preparation, but before the test, soap bar is stored to prevent enzyme liberating down at 4 ℃.Before test, soap bar is stored the time of various length.Then the soap bar of composition E and F is used to use the washing of the standard test fabric of standard method, said standard method is based on the hand washing method of use laundry soap bar commonly used.
The said test fabric of dipping in a certain amount of deionized water.The test fabric that extruding is wet is handled its extruding the dip test fabric and the second time more then with soap bar.With hand soap bar is wiped on said fabric, with the soap bar lie by and make and handle back test fabric and flood in deionized water, the test fabric is 2.8 grams per liters with the ratio of solution, and this is equivalent to the standard wash condition, washes test cloth by rubbing with the hands 30 times.To test fabric rinsing and dry in clear water.
Before washing and use the reflectivity of Micromatch reflecting spectrograph determination test fabric afterwards in 480 nanometers.Δ R is the variation of reflectivity.
Each bar composition for each storage time repeats steps outlined more than four times, and the following result who provides represents mean value.
ΔR 460
E F storage time/sky
0 17.24 19.45
6 16.87 17.07
8 16.80 16.73
10 16.77 16.38
12 16.74 16.04
20 16.60 14.68
30 16.43 12.97
The above results has shown that the stability of the soap bar that contains Durazym improves, and has only just produced benefit to overall performance after 6-8 days in the storage time.
In the following example, composition G, H, the soap bar of I and J prepare according to the method for summarizing in the example I.
EXAMPLE V
Detect the remaining enzymic activity (enzyme stability) that contains coconut fatty acid but do not contain the soap bar of sodium formiate in the present embodiment.
Composition G
Weight %
Coconut fatty acid 1
Sodium sulfate 1
Sodium formiate-
Glycerine 2
Borax 2
Durazym ≠ (5GU/mg soap bar 0.3 composition)
Soap base (80% tallow, 20% Oleum Cocois)
16.0 liters of ≠ Durazym (Novo/Nordisk A/S product)
Soap bar is packaged in the glycine paper and is to store under 70% the condition 37 ℃ and relative humidity.In storage process, periodically measure the remaining enzymic activity of soap bar.Its result is as follows.
The remaining enzymic activity % of composition
The storage time/sky
0 100
13 100
21 100
40 83
80 81
Example VI
Detect the remaining enzymic activity (enzyme stability) of the soap bar that contains phosphoric acid in the present embodiment.
Composition H
Weight %
Phosphoric acid 0.15
Sodium sulfate 1
Sodium formiate 2
Propylene glycol 2
Borax 2 Durazym ≠ (5GU/mg soap 0.3 composition) soap base (80% tallow, 20% Oleum Cocois) ≠ 16.0 liters of Durazym (Novo/Nordisk A/S product)
Soap bar is packaged in the glycine paper and is to store under 70% the condition 28 ℃ and relative humidity.In storage process, periodically measure the remaining enzymic activity of soap bar.Its result is as follows.
The remaining enzymic activity % of composition
The storage time/sky
0 100
14 100
27 100
41 100
Example VII A
Detect the remaining enzymic activity (enzyme stability) that contains and do not contain the soap bar of sodium formiate in the present embodiment.
Composition I J
Weight %
Citric acid 11
Glycerine 66
Sodium formiate 2
Borax 22 Durazym ≠ (5GU/mg 0.3 0.3 bar compositions) soap base (80% tallow, 20% Oleum Cocois) ≠ 16.0 liters of Durazym (Novo/Nordisk A/S product)
Soap bar is packaged in the glycine paper seriatim and is to store under 70% the condition 37 ℃ and relative humidity.In storage process, periodically measure remaining enzymic activity.Its result is as follows.
The remaining enzymic activity % of composition
The storage time/sky I J
0 100 100
10 100 100
24 100 100
30 100 100
71 - 89
76 - -
92 - 85
107 82 -
Do not contain sodium formiate in the soap bar even The above results shows, it also keeps good remaining enzymic activity.

Claims (11)

1. detergent composition that exists with the solid form that is shaped, it comprises:
A. the detergent active ingredients of 25-80 weight %;
B. the water of 35 weight % at the most;
C. mutant subtilysin enzyme, wherein aminoacid sequence changes as follows: replace the 195th amino acid with L-glutamic acid or aspartic acid, replace the 222nd amino acid with L-Ala or halfcystine, its content is that proteolytic activity reaches 0.1 to 100GU/mg amount in whole compositions.
2. according to the detergent composition of claim 1, it also comprises the stabilising system of enzyme, and described stabilising system comprises the boron compound of 0.1-10 weight % and the polyvalent alcohol of 0.1-15 weight %.
3. according to the detergent composition of claim 2, wherein stabilising system also comprises at least a following component that is selected from:
I) organic acid, organic acid an alkali metal salt, mineral acid and its mixture; With
It ii) not an alkali metal salt of the mineral acid of boron compound.
4. according to the detergent composition of claim 1, wherein enzyme contains glutaminic acid residue on the 195th, contains alanine residue on the 222nd.
5. the detergent composition of arbitrary claim among the claim 1-4, wherein the amount of water is 10-30 weight %.
6. the detergent composition of arbitrary claim among the claim 1-4, wherein said detergent active ingredients is a soap, or soap and account for the mixture of the synthetic detergent active ingredients of total detergent active ingredients 0.1-10 weight %.
Among the claim 1-4 arbitrary claim detergent composition, it also contains the filler of 0-35 weight %.
8. the detergent composition of claim 7, wherein the amount of filler is 0.1-30 weight %, and is selected from kaolin, wilkinite, silicate, talcum, sodium sulfate, yellow soda ash or its mixture.
9. according to the detergent composition of claim 3, wherein boron compound is a borax; Polyvalent alcohol is selected from propylene glycol, glycerol and Sorbitol Powder; Organic acid is selected from formic acid, succsinic acid, hexanodioic acid, pentanedioic acid, citric acid, soap acid or its mixture; The organic acid an alkali metal salt is selected from sodium formiate, Trisodium Citrate and Sodium Propionate; Mineral acid is a phosphoric acid; An alkali metal salt of mineral acid is selected from sodium sulfate, sodium-chlor, yellow soda ash, sodium bicarbonate and sodium phosphate.
10. according to the detergent composition of claim 3, wherein by total composition, the content of organic acid, its salt or mineral acid is 0.1-10 weight %; The content of inorganic acid alkali metal-salt is 0.1-5 weight %.
Handle soiled fabric 11. use the detergent composition of arbitrary claim among the claim 1-4.
CN93114193A 1992-09-30 1993-09-29 Detergent compositions Expired - Fee Related CN1049682C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9220669.7 1992-09-30
GB929220669A GB9220669D0 (en) 1992-09-30 1992-09-30 Detergent composition

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CN1088611A CN1088611A (en) 1994-06-29
CN1049682C true CN1049682C (en) 2000-02-23

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OA (1) OA10056A (en)
ZA (1) ZA937274B (en)

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US5733473A (en) * 1990-11-14 1998-03-31 The Procter & Gamble Company Liquid detergent composition containing lipase and protease
JP3135066B2 (en) 1991-05-14 2001-02-13 エコラボ インコーポレイテッド Two-part drug concentrate
AU5038396A (en) * 1996-03-29 1997-10-02 Procter & Gamble Company, The Low moisture laundry detergent bar with improved enzyme stability
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GB9319884D0 (en) 1993-11-10

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