CN1036402A - The cleaning composition of cellulose granulates - Google Patents
The cleaning composition of cellulose granulates Download PDFInfo
- Publication number
- CN1036402A CN1036402A CN88108833A CN88108833A CN1036402A CN 1036402 A CN1036402 A CN 1036402A CN 88108833 A CN88108833 A CN 88108833A CN 88108833 A CN88108833 A CN 88108833A CN 1036402 A CN1036402 A CN 1036402A
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- Prior art keywords
- cellulase
- composition
- particle
- weight
- agent
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Classifications
-
- 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
- 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
- C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
Abstract
Require the cleaning composition of washing and soft fabric, wherein add and contain a kind of water-fast calcium salt, the preferably cellulase particle of lime carbonate.To soft fabric with to appearance of fabrics extraordinary effect is arranged all.Also require cellulase particle itself.
Description
The present invention relates to granular detergent compositions, it is used for cleaning and soft fabric, have other protection fabric for example outward appearance improve and make its multiple new benefit.
The present composition contains the clay material and the particulate cellulosic enzyme calciferous of soft fabric.
The purpose of many washing composition productions is that preparation has desirable good scourability and can protect the fabric cleaning composition of (comprising softening) again.
The representative of this cleaning composition is an English Patent 1,514,275-1,400,898 or EPA0026528 in disclosed cleaning composition.
Because cellulase has washability, in cleaning composition, used cellulase, as UK Patent Application GB-A 2,095,275, GB-2,094,826 or Japanese Patent 57108-199 in disclosed.
People find that also cellulase can soft fabric, and are as U.S.4, disclosed in 435,307.
EP-A0120528 points out that alkaline softening washing composition contains water-fast C
10-C
26Tertiary amine and the synergistic mixt of cellulase.
EP-A0177165 discloses the mixture that contains smectic clays and cellulase in the alkaline softening washing composition.
EP-A0220016 points out to use in the washing composition cellulase can obtain making the fabric color to act on clearly.
When this washing and/or softnessization composition are particulate state, the particle form that cellulase provides with enzyme manufactory usually, also the form of (marume) or bead adds composition.
U.S.4,435,307 have set forth the hardness depressant that is used for cleaning composition, disclose the use cellulase particle, and have narrated to reaching for example ashless and purpose no color, add some component when making in particle.
But, have been found that some in these components are deleterious to the performance of the softness/protection fabric of cleaning composition when containing the plain enzyme granulates of these component fibers and join in the cleaning composition.
When seeking the alternative of these undesirable components, find that now water-fast calcium salt can unexpectedly significantly improve the performance of the softness of the cleaning composition of enzyme containing granule/protection fabric.
Thereby the purpose of this invention is to provide cleaning composition, owing to used the cellulase particle that contains water-fast calcium salt, make it have the performance of good softness/protection fabric.
The present invention relates to granular detergent compositions, it contain the clay material of soft fabric and contain account for particle 1～50%(weight), preferably contain 5～15%(weight) the cellulase particle of lime carbonate.
Lime carbonate preferably wraps on the cellulase particle.
The invention still further relates to above-mentioned cellulase particle itself.
Composition of the present invention can wash the fabric of crossing with mellowing, and has and appearance of fabrics is improved and multiple new benefit.
This effect is owing to exist the clay material of tensio-active agent, soft fabric and cellulase particle calciferous to obtain in granular composition.
Be described in detail these necessity and selectable component below.
Cellulase
The plain enzyme of useful fiber of the present invention can be that to have best pH value be bacterium between 5 to 9.5 or the cellulase of fungi.
At U.S.4,435,307, GB-A-2,095,275, DE-05-2,247,832 and EP-A0220016 in the plain enzyme of useful fiber is disclosed.
The example of these cellulases has the var.thermoidea by Humicola insolens(Eumicola grisea) bacterial strain produces, particularly the cellulase of producing with Humicola strain DSM 1800 and with the fungi of Bacillus N or belong to the production of cellulose enzyme 212 that Aeromonas belongs to fungi production cellulase and from the cellulase of the hepatopancreas extraction of sea mollusk (Dolabella Auricula Solander).
Determine the activity of cellulase according to the hydrolysis of carboxymethyl cellulose.At " J.Biol.Chem. " 120, narrated the low molecule reduced carbohydrate that relies on the yellow prussiate reaction to produce in 51(1973) with colorimetric method for determining as W.S.Hoffman.The key condition of cultivating is PH=7.0, and temperature is 40 ℃, and the cultivation time is 20 minutes.
CMCase unit definition is equivalent to 10 for per minute under these conditions forms
-6The amount of the enzyme of the reduced carbohydrate amount of mole glucose.
Within the scope of the present invention, useful cellulase activity scope is 5 to 1360, and preferably 60 to 140CMCase activity units/gram cleaning composition.
Cellulase particle
The typical shape of the cellulase that uses in granular detergent compositions is with particle, obtains as the form of piller (marumes) or bead.
These particles contain a large amount of natural cellulose enzymes, annexing ingredient in addition together, for example polyoxyethylene glycol (general content is 5～7%) and Mierocrystalline cellulose (general content is about 10%).Use therein molecular weight polyethylene glycol scope is 500～8000.
The amount of cellulase determines that by the total activity of cellulase in the composition it must be within above-mentioned restriction in the particle.
Have been found that some is used as the material of dust-proofing agent and SYNTHETIC OPTICAL WHITNER by the enzyme preparation station-service, titanium dioxide and Magnesium Silicate q-agent, inconsistent with the soft effect of composition.
So composition of the present invention does not preferably contain titanium dioxide and Magnesium Silicate q-agent.
Have been found that now lime carbonate has dustproof effect when lime carbonate adds in the cellulase particle.As mentioned below, the benefit of its intentionally unimaginable softness/protection fabric.
Lime carbonate is in cellulase particle, and content accounts for particulate 1-10%(weight), 5-15%(weight preferably).
Have been found that granular size is that 1 to 10 micron lime carbonate is particularly suitable for purpose of the present invention.
Lime carbonate used herein can be or in covering, coat with stearic acid typically.In the present invention preferably among the embodiment, lime carbonate or so perhaps coats with for example stearic acid earlier, is coated on the cellulase particle again.
Cellulase particle can prepare with many diverse ways; for example use English Patent 1; 362; No. 365 and 1,361, in No. 387 " Marumerizer " of narration or be used in Aufbereitungs-Technik3 number/1970; 147-153 page or leaf and No. 5/1970; the granulation machine of narrating in the 262-278 page or leaf is perhaps used the shotting preparation of 760, No. 135 narrations of belgian patent specification sheets.In all cases, particle must have low one-tenth mealiness.
Here the lime carbonate of usefulness or mix with other component when making particle, or mix with cellulase before granulation perhaps is more preferably according to traditional method for coating and is coated on the particle of preparation as mentioned above.
Cellulase particle content of the present invention accounts for 1～50%(weight of cleaning composition), preferably account for 1.5～10%(weight).
Tensio-active agent
With here tensio-active agent anions selected type, non-ionic type and zwitterionics, its content accounts for 1～50%(weight of composition), best 10～30%.
Suitable anion surfactant is water miscible alkylbenzene sulfonate, alkyl-sulphate, alkyl polyethoxy vitriol, alkane sulfonate, sulfonated, α-sulphur carboxylate salt and ester thereof, alkyl glyceryl ether sulfonate, lipid acid monoglyceride vitriol and lipid acid monoglyceride sulfonate, alkylphenol polyethoxye ether sulfate, 2-acyloxy-paraffinic hydrocarbons-1-sulfonate and β-oxyalkyl chain alkane sulfonate.
9 to 15 carbon atoms are preferably arranged on the straight or branched alkyl chain, the alkylbenzene sulfonate of 11 to 13 carbon atoms is particularly arranged.Suitable alkyl-sulphate has 10 to 22 carbon atoms on alkyl chain, particularly 12 to 18 carbon atoms.Suitable alkyl polyethoxy vitriol has 10 to 18 carbon atoms on alkyl chain, each molecule on average has 1 to 12-CH
2CH
2The O-group particularly has 10 to 16 carbon atoms on alkyl chain, each molecule on average has 1 to 6-CH
2CH
2The O-group.
Suitable alkane sulfonate be basically straight chain and contain 8 to 24 carbon atoms, particularly contain 14 to 18 carbon atoms.Suitable sulfonated has 10 to 24 carbon atoms, and 14 to 16 carbon atoms are particularly arranged; Sulfonated can be by after the sulphur trioxide reaction, and then neutralizing under any condition that exists sultones to be hydrolyzed into corresponding hydroxyl alkane sulfonate makes.Suitable α-sulphur carboxylate salt contains 6 to 20 carbon atoms, not only comprises alpha-sulfonated fatty acid here but also has and the ester that alcohol became that contains 1 to 14 carbon atom.
Suitable alkyl glycerol ether sulfate is the ether that contains 10 to 18 carbon atom alcohols, particularly those that get from Oleum Cocois and Tallow, beef.Suitable alkylphenol polyethoxye ether sulfate has 8 to 12 carbon atoms and each molecule that 1 to 6-CH is on average arranged on alkyl chain
2CH
2The O-group.Suitable 2-acyloxy paraffinic hydrocarbons-1-sulfonate contains 2 to 9 carbon atoms on acyl group, partly contain 9 to 23 carbon atoms at alkane.Suitable β-oxyalkyl chain alkane sulfonate contains 1 to 13 carbon atom on alkyl, partly contain 8 to 20 carbon atoms at alkane.
The alkyl chain of above-mentioned anion surfactant can for example obtain from the Oleum Cocois to the Tallow, beef from natural matter, and perhaps synthetic obtaining for example used Ziegler or Oxo technology.Water-soluble can obtaining by using basic metal, ammonium or alkanolamine positively charged ion, and preferably use sodium.The present invention has noticed the mixture of anion surfactant; Satisfied mixture contains at the alkylbenzene sulfonate that 11-13 carbon atom arranged on the alkyl group and the alkyl-sulphate of 12 to 18 carbon atoms is arranged in alkyl group.
The suitable nonionic surface active agent that is added in the present composition is that HLB is 11.5～17.0 water-soluble ethoxylate matter and includes, but is not limited to C
10-C
20Primary alconol and secondary alcohol ethoxyl compound and C
6-C
10Alkylphenol ethoxylate.Preferably by every mole of C
14-C
18Straight chain primary alcohol and the condensation of 7-30 moles of ethylene oxide obtain, for example C
14-C
15(EO)
7, C
16-C
18(EO)
25, C particularly
16-C
18(EO)
11
Operable positively charged ion cosurfactant comprises R
4R
5R
6R
7N
+X
-The water-soluble quaternary ammonium compound of form, R in the formula
410 to 20 carbon atoms are arranged, the alkyl of 12-18 carbon atom is particularly arranged, R
5, R
6And R
7All are C
1To C
7Alkyl, methyl preferably; X
-Be negatively charged ion, chlorion for example.The example of these trimethyl ammonium compounds comprises chlorination C
12-C
14Alkyl trimethyl ammonium and cocoa alkyl trimethyl ammonium methyl sulfate (cocoalkyl trimethyl ammonium methosulfate).
The present composition is substantially free of water-fast chain alkyl amine softening agent and derivative thereof, and this is owing to have been found that under pH value condition of the present invention they and cellulase the conflict effect to be arranged.The derivative of amine softening agent comprises corresponding amine compound.For example at EP.A 0,026, these amine softening agents are disclosed in 528 and EP.A0,120,528, particularly comprise formula R
1R
2R
3The amine of N, R in the formula
1And R
2Be C
6To C
20Alkyl chain, R
3Be C
1To C
10Alkyl chain or hydrogen.
The present composition is prepared by pH value scope 6.5 to 9.5, and pH value is by 1% measured in solution of said composition in aquae destillata.In this pH value scope, the cellulase of use has best performance.
The clay material of soft fabric
The present composition must the argillaceous softening agent.
These clay softening agents are known by people in washing class patent documentation, and all are widely used in the industry in the Europe and the U.S..These clay softening agents comprise various heat treated kaolin and various multilayer terre verte.Preferred clay softening agent is the terre verte softening agent clay of narration in Germany Patent document 2334899 and the English Patent 1,400,898, and these documents can give particulars.
Best clay fabric sofetening material comprises that those are the material of raw material with the wilkinite, and wilkinite is the montmorillonite type clay with various impurity at first, and its grade and character depend on the source of clay material.In composition preferably, the amount of the softening agent clay of use preferably at least 1%.Be generally 1-20%, preferably 2-10%.
Optional component
Except that basal component, the present composition can contain some optional components.
For example, preferably contain detergent builder compound and/or metal ion sequestering agent through the washing detergent composition.Comprise nitrilotriacetate, polycarboxylate, citrate, water-soluble phosphate as the compound of in technology, knowing, for example tri-polyphosphate, sodium orthophosphate, trisodium phosphate and composition thereof with being divided into detergent builder compound.The metal ion sequestering agent comprises above-mentioned all compounds, adds the material of picture edetate, amino poly-phosphate and other various multifunctional organic acids and salt, owing to can not be described in detail too much.In various cleaning composition, use the exemplary of these materials to see United States Patent (USP) 3,579,454.The preferred multifunctional organic acid that uses is citric acid, ethylenediamine tetramethylene phosphonic acid and diethylenetriamine pentamethylenophosphonic acid(DTPP).
Other kind of the detergent builder compound material that the present invention uses is the sodium silicoaluminate of indissoluble.The disclosed size of German Patent 24.22.655 is that zeolite (for example zeolite A) washing assistant of 1-10 micron uses best in hypophosphate or nonphosphate composition.Generally, washing assistant/sequestering agent accounts for 0.5% to 45% of composition.
The present composition also can contain saturated or unsaturated lipid acid and corresponding soap.Suitable saturated or unsaturated fatty acids has 10 to 18 carbon atoms on alkyl chain.Be preferably the unsaturated acid that 14 to 18 carbon atoms are arranged on alkyl chain, preferably oleic acid.Corresponding soap also can use.The content of used optional lipid acid/soap can be high to 20%.
It is R-CH(COOH that the present composition also can contain general formula) CH
2(COOH) compound, i.e. the derivative of succsinic acid, R is C in the formula
10-C
20Alkyl or alkenyl, C preferably
12-C
16, perhaps R replaces with hydroxyl, sulfo group, sulfino (sulfoxy) or sulfone substituent in the formula.
The succinate washing assistant preferably uses its water-soluble salt, comprises sodium, potassium, ammonium and alkanol ammonium salts.
The specific example of succinate washing assistant comprises: succsinic acid lauryl, succsinic acid myristin, succsinic acid palm ester, 2-dodecenyl succinic succinate (best), 2-15 carbene base succinate and analogues.
The washing assistant of Shi Yonging is a United States Patent (USP) 4 within the scope of the present invention, 663,071 compound of describing, it is the mixture of tartrate (ester) monosuccinic acid and the two succsinic acids of tartrate (ester), monosuccinic acid is 97: 3 to 20: 80 to the weight ratio of two succsinic acids, preferably 95: 5 to 40: 60.
Another kind of selectable component is a SYNTHETIC OPTICAL WHITNER.Peroxide bleaching agent preferably, Sodium peroxoborate for example, it is commercial that what sell is Sodium peroxoborate, yellow soda ash peroxyhydrate, trisodium phosphate peroxyhydrate and the urea peroxyhydrate of monohydrate and tetrahydrate form.
Bleach-activating agent can share with above-mentioned peroxide bleaching agent.The kind of bleach-activating agent comprises ester, imide, imidazoles, oxime and carbonate.Wherein preferred material comprises neighbour-acetoxy-benzoic acid methyl esters, hot acyloxy benzene sulfonic acid sodium salt of right-the acetoxyl benzene sulfonic acid sodium salt, for example 4-and 4-acyloxy in last of the ten Heavenly stems benzene sulfonic acid sodium salt; Bisphenol diacetate; Tetraacetyl ethylene diamine; Tetrem acyl hexamethylene-diamine; Tetrem acyl methylene diamine.
United States Patent (USP) 4,483, disclosed other best peroxide bleaching activator is alpha-substitution alkyl or alkenyl ester in 778 and 4,539,130, for example the hot acyloxy of 4(2-chlorine) benzene sulfonic acid sodium salt, 4-(3,5,5-trimethyl acetyl oxygen base) benzene sulfonic acid sodium salt.Suitable peroxy acid also is the peroxide bleaching activator, described in for example disclosed Europe patent application 0166571, promptly is generally the compound of RXAOOH and RXAL type, R is a hydrocarbyl group in the formula, and X is a heteroatoms, and A is a carbonyl bridge chain group, L is a leavings group, particularly hydroxy benzene sulfonate.
Enzyme except that cellulase, for example proteolytic enzyme, amylolytic enzyme or lipolytic enzyme also can use except that cellulase.
Soil separating agent/native suspension agent also can be present in the present composition, and general content is 0.1～10%(weight).Particularly can use the alkoxyl group polyamine that is suitable for doing clay-native remover/anti redeposition agent.Disclose these compounds and preparation thereof in EP-PA0112593, these disclosed contents here are used in combination as a reference.
Be appreciated that term used herein " polyamine " represents the alkoxyl group polyamine amine form and quaternary ammoniated form on kind.Such material is usually with the experience structure that repeating unit is arranged
Divide subrepresentation:
R is a hydrocarbyl group in the formula, and 2-6 carbon atom arranged usually; R
1Can be C
1-C
20Hydrocarbon; Alkoxy grp is oxyethyl group, propoxy-and analogue thereof.Y equals 2-30, is preferably 10-20; N equals 2 integer at least, and 2-20 is better, is preferably 3-5; X
-Be a negatively charged ion, halogenide or the methyl-sulfate that produces by quaternary ammonium reaction for example.
Used most preferred polyamine is so-called ethoxylation polymine, and promptly oxyethane is with the product of ethylin imines polyreaction, and general formula is:
N is 3 to 5 integer in the formula, and y is 10 to 20 integer.
The soil suspension agent also can be selected from polyoxyethylene glycol, and molecular weight is 400 to 1000, the multipolymer of polyacrylic ester or vinylformic acid and maleic anhydride/acid.
Cleaning composition of the present invention does not preferably contain carboxymethyl cellulose.
In addition, except that the component of having narrated, the present composition can contain various in commodity normally used other optional component, to obtain artistic effect or other good product performance.Typical component comprises that PH adjusts agent, spices, dyestuff, optional whitening agent, hydrotropic agent and gel control agent, freeze-thaw stabilizer, sterilant, sanitas, Foam Control, bleaching stibilizer.
Experimental section
According to the form below prepares granular detergent compositions
Composition weight %
Straight chain C
12Sodium alkyl benzene sulfonate 11.0
Tallow, beef alkyl sodium sulfonate 5.0
Tallow, beef alcohol ethoxylate (Eoll) 0.3
Tripoly phosphate sodium STPP 24.0
POLARGEL NF 8.5
The soil suspension agent
*2.0
Proteinase-10 .9
Sodium sulfate, water, other non-important composition are until balance
*The multipolymer of vinylformic acid and toxilic acid, molecular weight 60,000(sodium salt).
By two kinds of compositions of above-mentioned basic preparation of compositions:
Composition A is as reference, and wherein plain enzyme of cellulase particle (accounting for composition gross weight 1.79%) including natural fibers and Mierocrystalline cellulose mix it with other dry component of composition.
Composition B, composition of the present invention, the coating of the plain enzyme of cellulase particle (accounting for composition gross weight 1.79%) including natural fibers, Mierocrystalline cellulose and polyoxyethylene glycol (account for 5% of particle weight, molecular wt is 1500) coating and lime carbonate (account for particle weight 10%) wherein.
In composition A and composition B, cellulase all is U.S.4, the type of narration in 435,307, and its amount wants to provide the activity of 68CMCase activity units/gram composition.
The softness of comparative composition A and B/and the protection fabric performance.
Experiment design is like this washed the flexibility of 4,8 and 12 (repeatedly circulation) back textiles sheets to compare the textiles sheet, at every turn all respectively with of the present invention and reference composition washing.
Experiment condition is as follows:
-product uses: 92 grams=0.75% concentration
-wash temperature: 40 ℃
-18/gallon (0.31 grams per liter), the water hardness (the Ca/Mg ratio is 3: 1)
Relatively wash back air dried cloth sheet by two panels that two expert statement people are arranged that work alone with 9 Schelle chi paired comparison technology.Write down difference with evaluation tally (PSU), the main schedule expressivity can be better.(
*) the important result of expression, the confidence level with 95% is calculated minimum effective difference (LSD).
Experimental result is as follows:
A) flexibility cycle number composition B and composition A are relatively
(bath towel) 4+0.38PSU
8 +1.00
＊PSU
12 +0.75
＊PSU
B) appearance of fabrics (improving color and anti-pilling)
(being mainly the mean value of cotton goods)
Cycle number composition B and composition A are relatively
4 +0.69
＊PSU
8 +0.75
＊PSU
12 +0.75
＊PSU
Also measured the effect of independent polyoxyethylene glycol layer, the result shows negative effect.What this proof played positive interaction to flexibility and appearance of fabrics is because the existence of lime carbonate.
Claims (16)
1, a kind ofly be used to wash and the granular composition of soft fabric, contain a kind of tensio-active agent, a kind of clay material of soft fabric and cellulase particle is characterized in that containing in the cellulase particle lime carbonate that accounts for this particle weight 1～50%.
2, according to the composition of claim 1, wherein calcium carbonate content is 5～15% of a cellulase particle weight.
3, according to the composition of claim 1, wherein lime carbonate is coated on the cellulase particle.
4, according to the composition of claim 1, wherein cellulase is that to have best pH value be bacteria cellulose enzyme or fungal cellulase between 5～11.5.
5, according to the composition of claim 1, wherein cellulase is that to have best pH value be 6.5～9.5 alkali cellulose enzyme.
6, according to the composition of claim 1, wherein the cellulase activity of composition is 5～1360CMCase activity units/gram composition.
7, according to the composition of claim 1, wherein composition contains 1～50%(weight) cellulase particle and 1～20%(weight) the clay material of soft fabric.
8, according to the composition of claim 1, wherein cellulase particle content is 1.5～10%(weight), the clay material content of soft fabric is 2～10%(weight).
9, according to the composition of claim 1, wherein the clay material of soft fabric is a POLARGEL NF.
10, according to the composition of claim 1, wherein do not contain titanium dioxide and Magnesium Silicate q-agent in the cellulase particle.
11, the cellulase particle that uses in the composition of claim 1 is characterized in that it contains 1～50%(weight) lime carbonate.
12, according to the cellulase particle of claim 11, wherein calcium carbonate content is 5～15%(weight).
13, according to the cellulase particle of claim 11, wherein lime carbonate is coated on above them.
14, according to the cellulase particle of claim 11, wherein cellulase is that to have best pH value be bacteria cellulose enzyme or fungal cellulase between 5～11.5.
15, according to the cellulase particle of claim 15, wherein cellulase is that to have best pH value be 6.5～9.5 alkali cellulose enzyme.
16, according to the cellulase particle of claim 11, wherein it does not contain titanium dioxide and Magnesium Silicate q-agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB878727081A GB8727081D0 (en) | 1987-11-19 | 1987-11-19 | Granular detergent compositions |
| GB8727081 | 1987-11-19 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94100297A Division CN1092101A (en) | 1987-11-19 | 1994-01-07 | Fabric washing and soft with the cellulase particle that uses in the composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1036402A true CN1036402A (en) | 1989-10-18 |
| CN1026124C CN1026124C (en) | 1994-10-05 |
Family
ID=10627204
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88108833A Expired - Fee Related CN1026124C (en) | 1987-11-19 | 1988-11-19 | Detergent compositions containing cellulase granulates |
| CN94100297A Pending CN1092101A (en) | 1987-11-19 | 1994-01-07 | Fabric washing and soft with the cellulase particle that uses in the composition |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94100297A Pending CN1092101A (en) | 1987-11-19 | 1994-01-07 | Fabric washing and soft with the cellulase particle that uses in the composition |
Country Status (19)
| Country | Link |
|---|---|
| EP (1) | EP0383828B1 (en) |
| JP (1) | JP2735663B2 (en) |
| KR (1) | KR950013920B1 (en) |
| CN (2) | CN1026124C (en) |
| AT (1) | ATE84818T1 (en) |
| AU (1) | AU634705B2 (en) |
| BR (1) | BR8807805A (en) |
| CA (1) | CA1336894C (en) |
| DE (1) | DE3877768T2 (en) |
| DK (1) | DK164708C (en) |
| FI (1) | FI92496C (en) |
| GB (1) | GB8727081D0 (en) |
| HK (1) | HK143896A (en) |
| IE (1) | IE61734B1 (en) |
| IN (1) | IN183413B (en) |
| MX (1) | MX169695B (en) |
| MY (1) | MY103481A (en) |
| NZ (1) | NZ227025A (en) |
| WO (1) | WO1989004862A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE219136T1 (en) * | 1991-01-16 | 2002-06-15 | Procter & Gamble | COMPACT DETERGENT COMPOSITIONS WITH HIGHLY ACTIVE CELLULASES |
| US5443750A (en) * | 1991-01-16 | 1995-08-22 | The Procter & Gamble Company | Detergent compositions with high activity cellulase and softening clays |
| US5520838A (en) * | 1991-01-16 | 1996-05-28 | The Procter & Gamble Company | Compact detergent compositions with high activity cellulase |
| ES2127769T3 (en) * | 1992-07-17 | 1999-05-01 | Benckiser Nv | DELICATE DISHWASHING AGENT WITH MACHINES. |
| US6723549B2 (en) | 1995-10-17 | 2004-04-20 | Ab Enzymes Oy | Cellulases, the genes encoding them and uses thereof |
| US6184019B1 (en) | 1995-10-17 | 2001-02-06 | Röhm Enzyme Finland OY | Cellulases, the genes encoding them and uses thereof |
| GB0124307D0 (en) | 2001-10-10 | 2001-11-28 | Unilever Plc | Detergent compositions |
| GB0124308D0 (en) | 2001-10-10 | 2001-11-28 | Unilever Plc | Detergent compositions |
| DE10202390A1 (en) * | 2002-01-23 | 2003-09-25 | Henkel Kgaa | Combination of cellulases and special cellulose in detergents |
| CN103816884B (en) * | 2014-02-24 | 2015-09-09 | 钟春燕 | A kind of nanometer activated carbon fiber preparation method of carried titanium dioxide |
| CN117377745A (en) * | 2021-05-25 | 2024-01-09 | 联合利华知识产权控股有限公司 | Laundry method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK263584D0 (en) * | 1984-05-29 | 1984-05-29 | Novo Industri As | ENZYMOUS GRANULATES USED AS DETERGENT ADDITIVES |
| GB8421802D0 (en) * | 1984-08-29 | 1984-10-03 | Unilever Plc | Detergent composition |
| JPS6192570A (en) * | 1984-10-12 | 1986-05-10 | Showa Denko Kk | Enzyme granulation |
| NZ230842A (en) * | 1988-10-21 | 1992-05-26 | Colgate Palmolive Co | Nonionic heavy duty particulate detergent containing protease, amylase and cellulase |
-
1987
- 1987-11-19 GB GB878727081A patent/GB8727081D0/en active Pending
-
1988
- 1988-11-17 IN IN1001DE1988 patent/IN183413B/en unknown
- 1988-11-18 AU AU26117/88A patent/AU634705B2/en not_active Ceased
- 1988-11-18 JP JP1500029A patent/JP2735663B2/en not_active Expired - Lifetime
- 1988-11-18 EP EP89900022A patent/EP0383828B1/en not_active Expired - Lifetime
- 1988-11-18 CA CA000583568A patent/CA1336894C/en not_active Expired - Fee Related
- 1988-11-18 BR BR888807805A patent/BR8807805A/en not_active IP Right Cessation
- 1988-11-18 WO PCT/DK1988/000189 patent/WO1989004862A1/en active IP Right Grant
- 1988-11-18 AT AT89900022T patent/ATE84818T1/en not_active IP Right Cessation
- 1988-11-18 IE IE346588A patent/IE61734B1/en not_active IP Right Cessation
- 1988-11-18 DE DE8989900022T patent/DE3877768T2/en not_active Expired - Fee Related
- 1988-11-18 KR KR1019890701353A patent/KR950013920B1/en not_active IP Right Cessation
- 1988-11-19 CN CN88108833A patent/CN1026124C/en not_active Expired - Fee Related
- 1988-11-19 MY MYPI88001320A patent/MY103481A/en unknown
- 1988-11-21 MX MX013871A patent/MX169695B/en unknown
- 1988-11-21 NZ NZ227025A patent/NZ227025A/en unknown
-
1990
- 1990-05-04 DK DK110890A patent/DK164708C/en not_active IP Right Cessation
- 1990-05-17 FI FI902446A patent/FI92496C/en not_active IP Right Cessation
-
1994
- 1994-01-07 CN CN94100297A patent/CN1092101A/en active Pending
-
1996
- 1996-08-01 HK HK143896A patent/HK143896A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DK164708B (en) | 1992-08-03 |
| JPH03503775A (en) | 1991-08-22 |
| IN183413B (en) | 1999-12-25 |
| DK110890A (en) | 1990-05-04 |
| EP0383828A1 (en) | 1990-08-29 |
| FI92496C (en) | 1994-11-25 |
| CA1336894C (en) | 1995-09-05 |
| KR950013920B1 (en) | 1995-11-18 |
| AU634705B2 (en) | 1993-03-04 |
| BR8807805A (en) | 1990-10-23 |
| IE61734B1 (en) | 1994-11-30 |
| NZ227025A (en) | 1992-08-26 |
| DE3877768T2 (en) | 1993-05-27 |
| EP0383828B1 (en) | 1993-01-20 |
| DK110890D0 (en) | 1990-05-04 |
| HK143896A (en) | 1996-08-09 |
| AU2611788A (en) | 1989-06-14 |
| MY103481A (en) | 1993-06-30 |
| KR890701719A (en) | 1989-12-21 |
| MX169695B (en) | 1993-07-19 |
| FI902446A0 (en) | 1990-05-17 |
| GB8727081D0 (en) | 1987-12-23 |
| CN1092101A (en) | 1994-09-14 |
| JP2735663B2 (en) | 1998-04-02 |
| FI92496B (en) | 1994-08-15 |
| DE3877768D1 (en) | 1993-03-04 |
| ATE84818T1 (en) | 1993-02-15 |
| IE883465L (en) | 1989-05-19 |
| CN1026124C (en) | 1994-10-05 |
| DK164708C (en) | 1992-12-21 |
| WO1989004862A1 (en) | 1989-06-01 |
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