CN1121354A - High active enzyme granulates - Google Patents
High active enzyme granulates Download PDFInfo
- Publication number
- CN1121354A CN1121354A CN94191792A CN94191792A CN1121354A CN 1121354 A CN1121354 A CN 1121354A CN 94191792 A CN94191792 A CN 94191792A CN 94191792 A CN94191792 A CN 94191792A CN 1121354 A CN1121354 A CN 1121354A
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- China
- Prior art keywords
- composition
- detergent composition
- enzyme
- acid
- washing
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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
- C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
-
- 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
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
-
- 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
- C11D3/38672—Granulated or coated enzymes
Abstract
The invention concerns the use of a concentrated granular detergent composition having a density of about 800 g/L or more comprising enzyme granulates characterised in that said enzyme granulates are present at a level of less than 20 g/L detergent composition, wherein said enzyme granulates have no negative impact on the whiteness of the detergent composition. Furthermore the invention relates to a concentrated granular detergent composition comprising enzyme granulates characterized in that the concentration of high alkaline protease in the enzyme granulate is at least 2 %.
Description
Recently, detergent industry to produce bulk density the detergent powder of big (for example more than the 600g/l) entertain sizable interest.Equally, highly spissated detergent powder composition is also had a preference in human consumer and point of sale.And in the art, it is high to require detergent composition not only clean to render a service already, and softening fabrics and other performances of safeguarding fabric also will be got well.Selling detergent composition of new generation at present, can describe rightly with " closely washing composition (compact detergent) " speech.People have played various trade names for this tight washing composition, resemble " surpassing ", micro-or the like.It is higher that the special character of this class detergent composition is to compare its density with traditional detergent composition, can use " closely " detergent composition of much less to reach with the same effect of traditional detergent composition.This singularity is reflected on the composition of washing composition best, and the content of mineral filler salt is smaller.The effectiveness of this " closely " detergent composition is by the cancellation pre-wash cycle and adopt diverting device and dispersion device to realize best, and this class device directly adds in the washing machine drum when begin main wash(ing)cycle.This trend of beginning develops along with environment protection and concentrated cleaning synchronized development since nearly 4 years in detergent industry.
Some advantage of concentrated cleaning powder composition has:
A. container or pack little, so be easy to transport,
B. small packages has been vacateed the space, thereby can put more packaging final prod in unit space,
C. used wrapping material are few, help protecting environment.
In order to reach the purpose of dwindling packing, following possibility is arranged in principle by spissated powder detergent:
A. use active bigger composition,
B. avoid adding inoperative composition,
C. reduce the air capacity in the packing as far as possible.
The basal component of high duty detergent composite formula is now,
A. tensio-active agent,
B. washing assistant,
C. enzyme,
D. SYNTHETIC OPTICAL WHITNER.
Specifying of these compositions can be seen in hereinafter described.
Except that composition above-mentioned, detergent composition can also contain white dyes, anti redeposition agent, polycarboxylate polymkeric substance, stablizer, oxidation inhibitor, suds suppressor, spices or the like.
The concentrated cleaning powder composition for example can be seen in EP 340,013 (Unilever) and EP 509,787 (Unilever).
EP 340,013 discloses a kind of granular detergent composition, preferably not phosphorous hydrochlorate washing assistant, and its bulk density is at least every liter of 650g, comprises:
A) 17～35% (weight) on-soap laundry active (forming by the anionic detergent active substance to small part) and
B) 28～45% (butt weight) crystallization or amorphous silicon sodium aluminates are 0.9: 1～2.6: 1 with (a) weight ratio (b).Particle porosity is preferably less than 0.20.This composition can be in high-speed mixer or tablets press granulation and densification prepare.
EP 509,787 have disclosed a kind of concentrated cleaning powder composition, its bulk density is more than 600g/1, preferred 610g/l at least, 850g/l more preferably from about, shown in EXAMPLE III～VII, and comprise the specific manganese complex of tensio-active agent, washing assistant, enzyme, peralcohol SYNTHETIC OPTICAL WHITNER and the effective bleaching catalyst of a kind of conduct.Adopt this class catalyzer can make washing composition tightr, promptly reduce packaging volume.
Because current powdered detergent composition becomes more and more denseer system simultaneously also tight more (described) as two pieces of documents above-mentioned this just cause its recommend consumption (each washing adds the gram number of washing composition) than non-closely or moderate closely detergent composition lack.Less product consumption also must have been given play to the same at least washing effect simultaneously.So the consumption of the content of some composition, especially enzyme must increase substantially just unlikely reduction effectiveness in the finished product.
The enzyme dosage of describing in above-mentioned two pieces of patent applications is all quite high.For example in EP 509,787, according to the active difference of used protease, its consumption is in 0.001%～10% (weight), preferably in 0.01%～5% (weight) scope.
Owing to contain the technical problem that quantity like this (protease) brings in this tight type final finished is negative impact how to avoid enzyme granulate that the detergent composition whiteness is produced.This is that prior art is unwitnessed so far to detergent composition from spending tangible negative impact.
Closely combine thing and concentrate, then recommend consumption few more, simultaneously for guaranteeing that reaching same washing effect just must add more enzyme granulate.But enzyme granulate content height as described below has tangible negative impact to the whiteness of finished product.
In order to show, the quantity of required enzyme containing granule must increase when adopting same volume, non-closely, in closely and height carried out following comparison closely between the different densities powder.Closely high closely density d=600g/l density d=700g/l density d=850g/l recommends consumption in the non-tight washing composition: recommend consumption recommendation consumption 180g/ time (washing) 126g/ time 95g/ time in order to keep in every liter of washing water protease concentration constant, when using Savinase 4T particle, to finished product require as follows:
Savinase 4T1g/100g washing composition 1.4g/100g washing composition 1.9g/100g washing composition or restrain number/rise detergent composition to represent with enzyme granulate: 6g/L washing composition 9.8g/L washing composition 15.8g/ rises washing composition and can be clear that thus, under the situation in equal volume when changing to washing composition (d is at least 800) very closely from " bulk ", enzyme granulate content is how to improve 2.6 times.Yet aspect the tight type washing composition, density from 700 bring up to 800 and higher while require recommending consumption to drop to the each washing of 95g/ that enzyme granulate content increases to 1.6 times every liter of washing composition from 126.
Form about Hunter L, a, b value clearly reflects enzyme granulate and the washing composition difference on whiteness below, thereby has shown that enzyme granulate is to the tangible negative impact of detergent composition whiteness:
Savinase 4T Savinase 10T contrast is with tight
Washing composition (d=850) L 73.8 71.3 88.0 a 2.1 1.5 1.7 b 2.8 1.6-1.6
(
*) whiteness=L-3b
| Whiteness ( **) | 62.4 | 66.5 | 92.8 |
Result of the above problems is to use efficient enzyme granulate, no longer can be discovered in its negative impact to the outward appearance of detergent powder.For above-mentioned negative impact to whiteness is maintained below the threshold value that can aware, must be by viewpoint of the present invention the about 800g/L of density, enzyme granulate content is limited in and is no more than every liter of detergent composition 20g at most in the powder detergent composition of preferred 850g/L at least.Enzyme granulate content is preferably 15g in every liter of detergent composition, and most preferably in every liter of detergent composition enzyme granulate content be 10g.
" enzyme granulate content " used herein speech means the various enzymes that use in the washing composition, the i.e. total content of proteolytic enzyme, lipase, amylase, cellulase, peroxidase, oxydase etc.Wherein also comprise single enzyme granulate and single mixture and so-called composite particles (for example both contained proteolytic enzyme in particle and also contained lipase) of planting enzyme granulate of planting.
" high active enzyme granulates " means a kind of enzyme and adds with particulate forms, and its quantity makes every liter of finished product of final detergent composition have high enzymatic activity.When using high alkaline proteases, Savinase for example
TM, Maxacal
TM, Opticlean
TM, Durazym
TMOr Maxapem
TMDeng, the protease concentration in the particle must be more than 2%.Preferred examples comprises proteolytic enzyme particle Savinase 8T and Savinase 10T, such as Savinase 8T means 8KNPU/g, promptly every gram particle 8000 Novo proteolytic enzyme units.Savinase
TMSpecific activity be 395 KNPU/g.
According to the present invention, further improve the whitening agent TiO for example by in preferred enzyme granulate, adding additional quantity
2Reach.Like this, Hunter L, a, b value (referring to use Savinase10T) are respectively 78.9,0.0 and-0.01.Therefore, being expressed as whiteness value (L-3b) is to be 78.9.
Use another advantage of high active enzyme to be TiO in the finished product as stated above
2Total content reduce greatly.For example, TiO in high active enzyme granulates
2Quantity be 9.1%, and be 5.2% in the low activity particle, press TiO in the finished product
2The percentage composition meter, then be respectively 0.094% and 0.155%.
For obtaining identical enzyme granulate whiteness effect, can use few so many TiO
2As use painted enzyme granulate, and resemble green and/or blue particle, resemble few like this TiO at present
2Add-on can also further reduce, and does not even use.
Detergent composition of the present invention can be made any form easily, preferably makes Powdered.Detergent composition of the present invention can also contain other detergent ingredients known in the art, for example washing assistant, SYNTHETIC OPTICAL WHITNER, bleach-activating agent as mentioned above; Anti-dust is deposition agent, spices or the like again.
Detergent component also comprises tensio-active agent, can be anionic, non-ionic, amphoteric, cationic or amphoteric ion type, and above-mentioned mixture.
United States Patent (USP) U.S.3,664,961 (authorizing Norris on May 23rd, 1972) have been listed the tensio-active agent of this quasi-representative.
In the present invention, the mixture of anion surfactant is especially suitable, the sulfonate and the sulfate surfactant mixture of special 5: 1 to 1: 2 (weight), preferred 3: 1 to 2: 3, more preferably 3: 1 to 1: 1 mixture.Preferred sulfonate comprises that wherein alkyl has 9～15, the especially alkylbenzene sulfonate of 11～13 carbon atoms, and α-Sulfonated fatty acid methyl ester class, and wherein fatty acid derived is from C
12～C
18Fat source is preferably derived from C
16～C
18Fat source.Under each situation, positively charged ion is basic metal, is preferably sodium.Preferred sulfate surfactant is that wherein alkyl contains the alkyl-sulphate of 12～18 carbon atoms, and optional and wherein alkyl contain 10～20, preferred 10～16 carbon atoms and average degree of ethoxylation are in 1～6 ethoxy sulfate fusion.The example of the preferred alkyl-sulphate of the present invention has animal tallow alkyl-sulphate, coconut alkyl-sulphate and C
14～C
15Alkyl-sulphate.The example of preferred ethoxy sulfate is so-called AE3S (C
12～C
15The vitriol of alkyl triethoxyization).Positively charged ion in each example or alkali metal cation are preferably sodium.
Can be used for a class nonionogenic tenside of the present invention is the condenses of ethylene oxide with the hydrophobic nature part, and the average hydrophile-lipophile balance value (HLB) of such tensio-active agent is preferably 9.5～13.5, more preferably 10～12.5 scopes 8～17.This hydrophobic (oleophylic) part can be an aliphatic series or aromatic, and can regulate easily with the length of the polyoxyethylene of any specific hydrophobic group condensation, has the water-soluble cpds of desirable hydrophilic-lipophilic constituent quality of balance with generation.
Especially preferred this type nonionogenic tenside is the C that every mol of alcohol contains 3～8 mole ethylene oxides
9～C
15The primary alconol ethoxy compound, especially every mol of alcohol contains the C of 6～8 molecular oxidation ethene
14～C
15Primary alconol and every mol of alcohol contain the C of 3～5 mole ethylene oxides
12～C
14Primary alconol.
Another kind of ionic surfactant pack is drawn together the alkyl polyglucoside compound of following general formula:
RO (C
nH
2nO)
tZ
xWherein Z is the part derived from glucose; R is the saturated hydrophobic alkyl that contains 12～18 carbon atoms; T=0～10, n=2 or 3; X is 1.3 to 4, and this compound comprises unreacted Fatty Alcohol(C12-C14 and C12-C18) that is less than 10% and the short-chain alkyl polyglucoside that is less than 50%.This compounds and can be seen in EP-BO070077,0075996 and 0094118 in detergent application.
The molecular formula that also has that is suitable as nonionogenic tenside is
Polyhydroxy fatty acid amide surfactant, R wherein
1Be H, C
1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture; R
2Be C
5-31Alkyl; Z is a polyhydroxy alkyl, comprises a line style hydrocarbon chain and at least 3 hydroxyls that directly link to each other with this chain, the alkoxy derivative of perhaps this poly-hydroxy hydrocarbon.Preferred R
1It is methyl; R
2It is straight chain C
11～C
15Alkyl or resemble the such alkenyl of coconut alkyl, perhaps their mixture; Z is derived from reducing sugar, for example glucose, fructose, maltose, the lactose in the reductive amination reaction.
A class tensio-active agent is semi-polarity tensio-active agent, for example amine oxide again.Suitable amine oxide is selected from single C
8～C
20, preferred C
10～C
14The oxide compound of N-alkyl or alkenyl amine and propylene-1, the dioxide of 3-diamines, wherein remaining N position is replaced by methyl, hydroxyethyl or hydroxypropyl.
A class tensio-active agent is an amphoterics again, for example is main component with the polyamine.
Cats product also can be used for this detergent composition, and suitable quaternary ammonium surfactant is selected from single C
8～C
16, preferred C
10～C
14N-alkyl or alkenyl ammonium surfactant, wherein remaining N position is replaced by methyl, hydroxyethyl or hydroxypropyl.
Preferred all kinds surfactant mixtures, especially negatively charged ion-nonionic also have negatively charged ion-nonionic-cationic mixture.English Patent 2040987 and Europe apply for that openly 0087914 has described particularly preferred mixture.Detergent composition can contain the tensio-active agent of 1%～70% (weight), but in composition of the present invention, the quantity of tensio-active agent is generally 1%～30% (weight), and more preferably 10%～25%.
Washing assistant
The quantity of washing assistant typically is 10%～60% in detergent composition of the present invention.Composition of the present invention does not contain or is substantially free of and comprises phosphatic washing assistant (do not contain substantially be meant account for below 1% of whole builder system), builder system of the present invention is by water soluble detergency promoter, and water-fast washing assistant or their mixture are formed.
Water-fast washing assistant can be an inorganic ion exchange material, is generally a kind of inorganic hydrated aluminosilicate material, especially a kind of hydration synthetic zeolite, for example Zeolite A, X, B or the HS of hydration.
Preferred aluminosilicate ion exchange material has unit structure cell molecular formula:
M
2[(AlO
2)
2(SiO
2)
y] XH
2O wherein M is the calcium exchange cation; Z and y are at least 6; The mol ratio of z and y is between 1.0～0.5; X is at least 5, and is preferred 7.5～276, and more preferably 10～264.Alumino-silicate materials is hydrated form and is preferably and contains 10%～28%, more preferably contains the crystal of 18%～22% water.
The feature of above-mentioned aluminosilicate ion exchange material also is its particle diameter at 0.1～10 μ m, preferably at 0.2～4 μ m.The median size of a known ion exchange material represented in the term here " particle diameter ", measure by conventional art, the micro-mensuration of making of scanning electronic microscope for example, the feature of this aluminosilicate ion exchange material is that also its calcium ion exchange capacity is at least the normal CaCO of every gram silico-aluminate 200mg
3The water hardness (pressing anhydrous substrate calculates), and generally should be worth between 300 milligramequivalents/g～352 milligramequivalents/g.The feature of aluminosilicate ion exchange material also is its calcium ion-exchanged rate, sees GS-1 for details, 429,143.
Can be used for implementing aluminosilicate ion exchange material of the present invention can buy, and can be natural materials, but preferred synthetic obtaining.U.S.3,985,669 have discussed a kind of method of producing aluminosilicate ion exchange material.Can be used for preferred synthetic, crystal aluminosilicate ion-exchange material of the present invention can buy by the following trade mark: Zeolite A, Zeolite B, Zeolite X, Zeolite HS with and composition thereof.In an especially preferred embodiment, the crystal aluminosilicate ion-exchange material is Zeolite A, and has following molecular formula:
Na
12[(AlO
2)
12(SiO
2)
12] XH
2O wherein X is 20～30, especially is 27.Molecular formula is Na
86[(AlO
2)
86(SiO
2)
106] 10.276H
2The Zeolite X of O also is suitable, and also having molecular formula is Na
6[(AlO
2)
6(SiO
2)
6] 7.5H
2The Zeolite HS of O.
Another kind of suitable water-fast inorganic builders material is a layered silicate, for example SKS-6 (Hoechst).SKS-6 is a kind of by water glass (Na
2Si
2O
5) crystallization, the layered silicate formed.Its high Ca
++/ Mg
++Binding ability mainly belongs to cation exchange mechanism.In hot water, the easier dissolving that becomes of this material.
Water soluble detergency promoter can be carboxy acid salt chelator monomeric form or oligomerisation.
The suitable carboxylate salt that contains a carboxyl comprises lactic acid, oxyacetic acid and ether derivative thereof, and is disclosed as belgian patent 831,368,821,369 and 821,370.The multi-carboxylate of containing two carboxyls comprises the water-soluble salt of following carboxylic acid: succsinic acid, propanedioic acid, (ethylenedioxy) two acetic acid, toxilic acid, bi oxyacetate, tartrate, tartronic acid and fumaric acid; and German Patent 2; 446; 686 and 2,446,687 reach and United States Patent (USP) 3; 935; 257 described ether carboxylates, the sulfinyl carboxylate salt that also has belgian patent 840,623 to describe.The multi-carboxylate of containing three carboxyls comprises, particularly water-soluble citrate, aconitate, citraconate, and succinate derivative, for example English Patent 1,379,241 described carboxy methoxy-succinic acid salt, the newborn oxygen base succinate that Netherlands patent applications 7205873 is described, with oxygen Quito carboxylate salt material, for example English Patent 1,387, the 447 2-oxa-s of describing-1,1,3-tricarballylic acid salt.
The multi-carboxylate of containing 4 carboxyls comprises English Patent 1,261, the 829 oxygen base disuberates of describing, 1,1,2,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent multi-carboxylate of sulfo group and comprise English Patent 1,398,421 and 1,398,422 and United States Patent (USP) 3,936, the 448 sulfo-succinic acid salt derivatives that disclose, with English Patent 1,082,179 sulfonation, the pyrolysis Citrate trianions of describing, simultaneously, contain the substituent multi-carboxylate of phosphono and be disclosed in English Patent 1,429, in 000.
Alicyclic ring and heterocycle multi-carboxylate comprise pentamethylene-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, cyclopentadiene, pentacarboxylic acid salt, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, 2,5-tetrahydrofuran (THF)-suitable-two carboxylate salts, 2,2,5,5-tetrahydrofuran (THF)-tetracarboxylic acid hydrochlorate, 1,2,3,4,5,6-hexane-hexacarboxylic acid salt, and the carboxymethyl derivant of polyhydroxy-alcohol resemble sorbyl alcohol, mannitol and Xylitol.Aromatic multi-carboxy acid's salt comprises mellitic acid and 1,2,4, the phthalic acid derivatives that 5-pyromellitic acid and English Patent 1,425,243 disclose.
Wherein preferred multi-carboxylate is that per molecule contains the hydroxycarboxylate of 3 carboxyls, especially Citrate trianion at the most.
Be used for the mixture that the preferred builder system of the present composition comprises the water-soluble silicon aluminate washing assistant that resembles Zeolite A and resembles the water-soluble carboxylate sequestrant of citric acid.
Other builder materials that can form a part that is used for builder system of the present invention comprise inorganic materials, resemble alkaline carbonate, supercarbonate, silicate, and organic materials, resemble organophosphate, amino polyalkylene phosphoric acid salt and aminopolycanboxylic acid's salt.
Other suitable water-soluble organic salts are homopolymerization or co-polymer acid or its salt, and wherein poly carboxylic acid comprises that at least two intermediate phase are every the carboxyl that is no more than two carbon atoms.
This base polymer is disclosed in GB-A-1, in 596,756.The example of this class salt is that weight-average molecular weight is 2000～5000 polyacrylate and they multipolymer with maleic anhydride, the molecular weight of this type of interpolymer from 20,000 to 70,000, especially about 40,000.
Preferred composition
The present composition will comprise the optional member of a common formation detergent composition part.Anti redeposition agent and dust suspension agent, white dyes, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, suds suppressor, anti-caking agent, dyestuff and pigment are several examples of this kind optional member, and can add various quantity as requested.
Be applicable to that anti redeposition agent of the present invention and dust suspension agent comprise derivatived cellulose, weevil base Mierocrystalline cellulose, carboxymethyl cellulose and Natvosol, and homopolymerization or copolymerization poly carboxylic acid and salt thereof.This base polymer comprises polyacrylate and the copolymer of maleic anhydride and acrylic acid of above mentioning as washing assistant, and the multipolymer of the same ethene of maleic anhydride, ethylene methacrylic ether or methacrylic acid, wherein maleic anhydride accounts for 20% (mole) of multipolymer at least.The consumption of these materials is generally 0.5%～10% of composition weight, and is preferred 0.75%～8%, and most preferably 1%～6%.
Preferred white dyes is an anion characteristic, and example has 4,4
1-two (2-diethanolamino-4-anilino-S-triazine-6-base-amino) stilbene-2:2
1-disulfonic acid disodium, 4,4
1-two (morpholino-4-anilino-S-triazine-6-base is amino) stilbene-2:2
1-disulfonic acid disodium, 4,4
1-two (2,4-hexichol amido-S-triazine-6-base-amino) stilbene-2:2
1-disulfonic acid disodium, 4
1, 4
11-two (2,4-hexichol amido-S-triazine-6-base is amino) stilbene--2-sodium sulfonate, 4,4
1-two (2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-S-triazine-6-base is amino) stilbene-2,2
1-disulfonic acid disodium, 4,4
1-two (4-phenyl-2,1,3-triazole-2-yl)-stilbenes-2,2
1-disulfonic acid disodium, 4,4
1-two (2-anilino-4-(1-methyl-2-hydroxyethylamino)-S-triazine-6-base is amino) stilbene-2,2
1-disulfonic acid disodium and 2-(stilbene radicals-4
11-(naphtho--1
1, 2
1: 4,5)-1,2,3-triazoles-2
11-sodium sulfonate.
Any particulate inorganic hydrate SYNTHETIC OPTICAL WHITNER all can be used, and its consumption is 3%～40% of a composition weight, and is preferred 8%～25%, and more preferably 12%～20%.The preferred embodiment of this class SYNTHETIC OPTICAL WHITNER is Sodium peroxoborate monohydrate and tetrahydrate, percarbonate and composition thereof.
Other are preferred, and the blended composition is peroxycarboxylic acid SYNTHETIC OPTICAL WHITNER and salt thereof separately, preferably add with granular or aggregate form.
Peroxide bleaching agent is preferably united use with bleach-activating agent, so that (being in the washing process) produces in the aqueous solution and the corresponding peroxy acid of bleach-activating agent on the spot.The example of this class suitable compound is disclosed among English Patent 1586769 and 2143231, and European publication application 0062523 has then been described and a kind of it made a kind of method of particle form.The preferred example of this compounds has tetra-acetylated ethylene diamine and 3,5,5-trimethyl acetyl oxygen base benzene sulfonic acid sodium salt.
The consumption of bleach-activating agent is generally 0.5%～10% of composition weight, and more commonly used is 1%～8%, and is preferably 2%～6%.
Another kind of optional ingredients is a suds suppressor, and its example is the mixture of siloxanes and silicon oxide-siloxanes.Usually, representational siloxanes is the alkylation silicone materials, and silicon-dioxide then uses with the fine dispersion form usually, for example silica acrogel and silica xerogel and various types of hydrophobic silica.These materials can add with particulate state, and in particle, the suds suppressor quilt advantageously releasably is incorporated into a kind of water-soluble or water dispersible property, is essentially in the carrier of on-surface-active and washing composition impermeable.Another kind of way is, can be dissolved or dispersed in suds suppressor then it to be sprayed onto one or more other compositions in a kind of liquid carrier and to get on.
As mentioned above, useful silicone suds suppressor can comprise a kind of mixture that is made of the alkylation siloxanes and the solid silica of the above-mentioned type.This mixture can be by being attached to siloxanes the solid silica surface preparation.The representative of preferred silicone suds suppressor is a kind of hydrophobicity, silanization (preferably trimethyl silicone hydride) silicon-dioxide, and between the 20 μ m, specific surface area is at 50m at 10 μ m for its granularity
2More than/the g, with the weight ratio of about 1: 1～1: 2 (siloxanes is than silanized silica) with about 500～about 200,000 the dimethyl silicone fluids fusion of molecular weight.
People's such as Bartollota United States Patent (USP) 3,933,672 has disclosed a kind of preferred silicone suds suppressor.German patent application DTOS2,646,126 (on April 28th, 1977 is open) have been described another kind of useful especially suds suppressor, and it is the silicone suds suppressor that emulsifying capacity is arranged itself.An example of this compounds is DC-544 (by the commercially available prod of Dew Corning production), and this is a kind of siloxanes/glycol copolymer.
The general consumption of above-mentioned suds suppressor is 0.001%～2% of a composition weight, and is preferred 0.01%～1%, and the adding mode of this foam properties-correcting agent is preferably made independent particle, can sandwich other foam control materials therein more like this, resembles C
20～C
24Lipid acid, the high molecular weight copolymer of Microcrystalline Wax and ethylene oxide and propylene oxide, otherwise these materials can exert an adverse impact to the dispersiveness of matrix.Manufacturing this class improves in the United States Patent (USP) 3,933,672 that the particulate technology of foam properties-correcting agent is disclosed in people such as Bartolotta above-mentioned.
Other useful polymeric materials have polyoxyethylene glycol, and especially molecular weight is 1000～10,000, and more preferably 2,000～8,000, most preferably 4,000.Its consumption is 0.20%～5% (weight), more preferably 0.25%～2.5%.Homopolymerization that these polymkeric substance and front have been mentioned or copolymerization multi-carboxylate, for improve protecting white property, dust on fabric deposition and to clay, protein and the oxidisability dust clean effect in the presence of transition metal impurity is valuable.
The dust release agent that is used for the present composition is traditional terephthalic acid with ethylene glycol and/or propylene glycol binary or the terpolymer by various arrangement modes.The example of this base polymer be disclosed in common transfer United States Patent (USP) 4116885 and 4711730 and European publication application 0272033 in.According to EP-A-0272033, especially preferred polymkeric substance has following molecular formula:
[CH
3(PEG)
43)
0.75(POH)
0.25(T-PO)
2.8(T-PEG)
0.4]
T (PO-H)
0.25((PEG)
43CH
3)
0.75Wherein PEG is-(OC
2H
4) O-, PO is (OC
3H
6O), and T be
(PcOC
6H
4CO)。
Some polymer materials is polyvinylpyrrolidone for example, and molecular weight is usually 5,000～20, and 000, preferably 10,000～15, between 000, also can be as useful composition to prevent that unsettled dyestuff shifts in the washing process between fabric.
By the present invention, can also in detergent composition, add fabric softener.This constituents can be inorganic also can be organic type.The example of inorganic softening agent is GB-A-1,400, the 898 green clays that disclose.The organic fabric softening agent comprises the water-fast tertiary amine of GB-A-1514276 and EP-B-0011340 disclosure and above-mentioned tertiary amine and single C of EP-B-0026527 and EP-B-0026528 disclosure
12～C
14The mixture of quaternary ammonium salt, and resemble two long-chain acid amides that EP-B-0242919 discloses.Other organic compositions that are used for the fabric sofetening system comprise the high molecular polyoxyethylene material that resembles EP-A-0299575 and 0313146 disclosure.
The add-on of green clay is generally 5%～20%, more preferably between 8%～15% (weight), joins in the rest part in the prescription with the component form of dry mixed.
The organic fabric softening agent, the add-on that resembles water-fast tertiary amine or two long-chain acid amides materials is between 0.5%～5% (weight), generally between 1%～3% (weight), and the add-on of high molecular polyoxyethylene and water-soluble cationic material is between 0.1%～2%, generally in 0.15%～1.5% (weight) scope.These materials generally join in the middle of the dried part of composition spray, although in some cases, also can be added in the composition with the composite grain form of doing more easily, perhaps its form with fused solution are sprayed onto the surface of other solids components.
The preparation method
Composition of the present invention can pass through prepared in various methods, comprises do mixing, spraying drying, condensing and the arbitrary combination of granulation and above-mentioned technology.
Preferred manufacturing procedure
A kind of preparation method of the present composition comprises spraying drying, condenses in high-speed mixer and dry blending.
To contain first kind of particulate component spraying of being difficult for molten anion surfactant and dry, take out the spray-dired product of part then, spray in its surface a spot of nonionogenic tenside again with the rest part blending.For example in the Lodige KM mixing machine, is neutralizing agent at yellow soda ash at a high-speed and continuous mixing roll, by the dry neutralization of anion surfactant, makes second kind of granular composition.Subsequently, with first kind and second kind of composition, together with other dry blending compositions, resembling carboxy acid salt chelator, inorganic peroxide SYNTHETIC OPTICAL WHITNER, bleach-activating agent, dust suspension agent, silicate and enzyme is added on the transport tape together, material is admitted in the revolving horizontal drum thus, in drum, spices and silicone suds suppressor are directed onto in the material.In composition very preferably, also to carry out further rotary drum mixing step, the crystal aluminosilicate that grinds very carefully that adds a small amount of (about 2%) during this is to improve density and to improve the particulate flow characteristics.
Described a kind of preferred method for preparing composition of the present invention in the applicant's common unsettled european patent application 92.870.138.2, this application is collected herein by reference.
Detergent composition of the present invention is a particle form, it is characterized in that density, and its density is big than conventional washing agent composition.The density that the present composition records under 20 ℃ of temperature is preferably 850～1000g/l between 800～1100g/l.
" closely " form of the present composition is reflected on the content of mineral filler salt in its composition best; Mineral filler salt is traditional composition of powdered detergent composition; In conventional washing agent composition, this filling salt exists with considerable quantity, typically is 17～35% (weight) of whole composition.
In composition of the present invention, the amount of contained filling salt is no more than 15% (weight) of whole composition, preferably is no more than 10%, is most preferably not exceeding 5% of composition.
Mineral filler salt resembles that class in the present invention's combination, is selected from the vitriol or the muriate of alkalies and alkaline earth.
Preferred filling salt is a sodium sulfate.
Washing methods
The tight detergent composition of the present invention when the master at washing machine washes consumption in the cycle and is less than conventional washing agent composition greatly, can reach identical with it effect.
Correspondingly, in another embodiment of the present invention, provide method, wherein used 15～170g detergent composition of the present invention in the cycle main washing with the washing machine laundering of textile fabrics.
Typically, under the condition in Europe, be used for that main to wash the recommendation consumption in cycle be 80～140g detergent composition when not needing prewashing.
Detergent composition of the present invention preferred directly rather than the shell by machine add in the bucket indirectly.This point can be easily by putting into said composition in bag or container, then in stirring, heat up or be immersed in the bath water in the bucket when begin this wash(ing)cycle composition just be released.Such container is put in the bucket together with fabric to be washed.Another kind of way is that washing machine itself is made and can directly be added form in the bucket to composition, for example establishes a reinforced structure on washing machine takes, puts the door of clothes.
Be enclosed in the general such design of the product that contains detergent composition in sack or the container, container its complete performance when drying regime obtains keeping that content leaks outside when preventing dry state, and once being exposed to wash environment, generally be after being dipped in the aqueous solution, just can discharge container contained object material.
This container is softish normally, for example sack.This sack can be a fibrous structure, scribbles waterproof protecting materials to contain to live material, for example resembles the sort of that European publication application 0018678 discloses.It also can be made with water-fast synthesizing polymeric material, have a kind of when being intended in being dipped in water-bearing media disruptive seal or outer cover, disclose as European publication application 0011500,0011501,0011502 and 0011968.A kind of not water-fast easily encapsulation comprises one side configuration of the sack of making along water opacity polymeric film (for example polyethylene or polypropylene) and the water-soluble binder of sealing.
In the variant form of a kind of sack or container products, can use laminated flaked product, dipping and/or be coated with composition on a slice intermediate flexible layer wherein, and then laminatedly one or more skins, produce a kind of appearance effect like fabric.These layers can seal and be integral so that in use still keep combination, also can emanate so that impel the release of dipping or coating material after contact water.
Another kind of laminated thing form comprises that a slice provides the layer of a series of bag-like containers through mold pressing or deformation processing, in each container, put into the detergent composition of metered amounts, covering the second layer on the first layer and two layers of contacted regional involution between bag-like container then.Each component can be inserted with granular, lotion or fusion form, and each laminated layer guarantees that the material in the bag-like container does not leak before should be in dropping into water.Each layer can be emanated after touching water and also can be kept integrally combining, and unique requirement is that this structure allows to discharge rapidly the interior material of bag-like container in solution.The number of bag-like container can be selected arbitrarily on the unit area basis, but general every square metre 500～25, between 000.
With regard to this respect of the present invention, the material that is fit to be used as the flexible laminate layer comprises sponge, paper, woven cloths or non-woven.
But the preferred means of implementing washing methods of the present invention comprises the reusable powder adding device of use energy, and the outer wall energy of it each sees through liquid, but does not allow solids composition to see through.
This class device is disclosed in european patent application communique 0343069 and 0344070.A kind of device that back one application discloses comprises the bag shape flexible sheet material that extends out from a support ring, and this ring forms an aperture, from this aperture can add enough one wash(ing)cycle required product.The part washing medium flows in the bag by aperture, and with the product dissolving, solution outflow aperture enters washing medium then.Support ring has and prevents to be drenched but the excessive shielding structure of still undissolved product, and this structure generally comprises the many washers that extend from center hub along radial direction, thereby constitutes the shape of band width of cloth bar wheel, and perhaps a kind of washer is spiral like configurations.
The following examples explanation the present invention also helps to understand.
Example I and II
Prepare following composition.
Tight granulated detergent: example I and II
Example I
Linear alkylbenzene sulphonic acid salt 8.0
C
45Alkylsurfuric acid sodium salt 2.5
C
45Alcohol is with 7 oxyethyl groups 6.0
The animal lipidol, 11 oxyethyl groups 2.0
Layered silicate 15.0
Trisodium citrate 5.0
Sodium carbonate salt 6.5
Zeolite (zeolite) 15.0
Maleic acid-acrylic acid copolymer 5.0
DETMPA 0.3
Savinase
TM?10T 0.8
Lipolase
TM?100T 0.25
Water glass 2.0
Sodium sulfate 3.5
PVP 1.0
Perborate 15.0
TAED 6.0
Minor constituent to 100
Example II
Tensio-active agent
C
45Alkylsurfuric acid sodium salt 8.0
C
12-15Straight chain alcohol is with 3 oxyethyl groups 6.0
Washing assistant
Zeolite (zeolite) 20.0
Citrate trianion 6.0
Buffer reagent
Carbonate 16.0
Polymkeric substance
CMC 0.4
Toxilic acid acrylic copolymer 5.0
Enzyme
Savinase?10T 1.2
Lipolase?150T 0.10
Other
Perborate 20.0
TAED 6.0
Minor constituent to 100
Claims (7)
1. more than the about 800g/l of density, contain the application of the concentrated granular detergent composition of enzyme granulate, described detergent composition is characterised in that the content of enzyme granulate described in every liter of detergent composition is less than 20g, and wherein said enzyme granulate does not have negative impact to the whiteness of detergent composition.
2. according to the application of the enzyme containing granule granular detergent composition of claim 1, wherein the content of enzyme granulate is less than 15g in every liter of detergent composition.
3. according to the application of the granular detergent composition of claim 1 or 2, enzyme wherein is a high alkaline proteases.
4. according to the application of the granular detergent composition of claim 3, wherein the concentration of high alkaline proteases in high active enzyme granulates is at least 2%.
5. according to the application of the granular detergent composition of any one in the claim 1～4, wherein enzyme granulate is colored.
6. according to the application of the granular detergent composition of any one in the claim 1～5, wherein in composition, add TiO
2
7. the concentrated granular detergent composition that contains enzyme granulate is characterized in that the concentration of high alkaline proteases in enzyme granulate is at least 2%.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP93870035.8 | 1993-02-26 | ||
| EP93870035 | 1993-02-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1121354A true CN1121354A (en) | 1996-04-24 |
| CN1071786C CN1071786C (en) | 2001-09-26 |
Family
ID=8215325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94191792A Expired - Fee Related CN1071786C (en) | 1993-02-26 | 1994-02-10 | High active enzyme granulates |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | USH1653H (en) |
| EP (1) | EP0686186B1 (en) |
| JP (1) | JPH08507098A (en) |
| CN (1) | CN1071786C (en) |
| AU (1) | AU6267694A (en) |
| CA (1) | CA2156829C (en) |
| CZ (1) | CZ214795A3 (en) |
| DE (1) | DE69409797T2 (en) |
| ES (1) | ES2115246T3 (en) |
| MA (1) | MA23121A1 (en) |
| PE (1) | PE11295A1 (en) |
| WO (1) | WO1994019444A1 (en) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2156829C (en) * | 1993-02-26 | 1999-06-08 | Paul Amaat R. G. France | High active enzyme granulates |
| EP0628624A1 (en) * | 1993-06-09 | 1994-12-14 | The Procter & Gamble Company | Protease containing dye transfer inhibiting compositions |
| US5883064A (en) * | 1993-12-21 | 1999-03-16 | The Procter & Gamble Company | Protease containing dye transfer inhibiting composition |
| EP1807498B2 (en) † | 2004-11-02 | 2019-02-20 | Henkel AG & Co. KGaA | Process for the preparation of granulates / agglomerates for detergent compositions |
| DE102015217816A1 (en) | 2015-09-17 | 2017-03-23 | Henkel Ag & Co. Kgaa | Use of highly concentrated enzyme granules to increase the storage stability of enzymes |
| CN112368375A (en) | 2018-04-26 | 2021-02-12 | 巴斯夫欧洲公司 | Lipase enzyme |
| WO2019211143A1 (en) | 2018-05-03 | 2019-11-07 | Basf Se | Amylase enzymes |
| CN114096676A (en) | 2019-02-20 | 2022-02-25 | 巴斯夫欧洲公司 | Bacillus industrial fermentation process using defined medium and magnesium supplement |
| MX2021010109A (en) | 2019-02-20 | 2021-09-21 | Basf Se | Industrial fermentation process for bacillus using defined medium and trace element feed. |
| EP3947664A2 (en) | 2019-03-25 | 2022-02-09 | Basf Se | Amylase enzymes |
| US20220162576A1 (en) | 2019-03-25 | 2022-05-26 | Basf Se | Amylase enzymes |
| WO2020193532A1 (en) | 2019-03-25 | 2020-10-01 | Basf Se | Cleaning composition having amylase enzymes |
| EP3983425A1 (en) | 2019-06-13 | 2022-04-20 | Basf Se | Method of recovering a protein from fermentation broth using a divalent cation |
| WO2021001297A1 (en) | 2019-07-02 | 2021-01-07 | Basf Se | Method for preparing a fermentation medium |
| WO2021004830A1 (en) | 2019-07-05 | 2021-01-14 | Basf Se | Industrial fermentation process for microbial cells using a fed-batch pre-culture |
| US20220267748A1 (en) | 2019-08-22 | 2022-08-25 | Basf Se | Amylase variants |
| US20230323329A1 (en) | 2020-09-04 | 2023-10-12 | Basf Se | Method for removing antifoaming agents from a fermentation broth |
| WO2022063770A1 (en) | 2020-09-22 | 2022-03-31 | Basf Se | Method for recovering a protein from a fermentation broth comprising a high degree of lysed cells |
| JP2024508766A (en) | 2021-02-22 | 2024-02-28 | ベーアーエスエフ・エスエー | amylase variant |
| EP4047088A1 (en) | 2021-02-22 | 2022-08-24 | Basf Se | Amylase variants |
| WO2024028338A1 (en) | 2022-08-02 | 2024-02-08 | Basf Se | Stabilized protein production process using bacillus host cells |
| WO2024033134A1 (en) | 2022-08-11 | 2024-02-15 | Basf Se | Enzyme compositions comprising protease, mannanase, and/or cellulase |
| WO2024033133A2 (en) | 2022-08-11 | 2024-02-15 | Basf Se | Enzyme compositions comprising an amylase |
| WO2024033135A2 (en) | 2022-08-11 | 2024-02-15 | Basf Se | Amylase variants |
| WO2024033136A1 (en) | 2022-08-11 | 2024-02-15 | Basf Se | Amylase variants |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1120819A (en) * | 1977-06-01 | 1982-03-30 | Jurgen W.K. Gromer | Detergent tablet |
| US4406808A (en) * | 1977-10-06 | 1983-09-27 | Colgate-Palmolive Company | High bulk density carbonate-zeolite built heavy duty nonionic laundry detergent |
| DE3434854A1 (en) * | 1984-09-22 | 1986-04-03 | Henkel KGaA, 4000 Düsseldorf | METHOD FOR PRODUCING A GRAINY, FREE-FLOWING DETERGENT COMPONENT |
| JPS6192570A (en) * | 1984-10-12 | 1986-05-10 | Showa Denko Kk | Enzyme granulation |
| DE3768509D1 (en) * | 1986-01-17 | 1991-04-18 | Kao Corp | HIGH DENSITY GRANULATED DETERGENT. |
| JP2787941B2 (en) * | 1986-09-12 | 1998-08-20 | 花王株式会社 | High density granular detergent composition containing enzymes |
| DK435687D0 (en) * | 1987-08-21 | 1987-08-21 | Novo Industri As | ENZYM containing granules and processes for their preparation |
| US4992198A (en) * | 1988-01-19 | 1991-02-12 | Kao Corporation | Detergent composition containing clathrate granules of a perfume-clathrate compound |
| GB8811447D0 (en) * | 1988-05-13 | 1988-06-15 | Procter & Gamble | Granular laundry compositions |
| JPH0633439B2 (en) * | 1988-07-28 | 1994-05-02 | 花王株式会社 | High-density granular concentrated detergent composition |
| GB8826110D0 (en) * | 1988-11-08 | 1988-12-14 | Unilever Plc | Enzyme-containing detergent compositions |
| GB8902009D0 (en) * | 1989-01-30 | 1989-03-22 | Unilever Plc | Particulate detergent compositions and their use |
| CA2017921C (en) * | 1989-06-09 | 1995-05-16 | John Michael Jolicoeur | Formation of detergent granules by deagglomeration of detergent dough |
| GB8924294D0 (en) * | 1989-10-27 | 1989-12-13 | Unilever Plc | Detergent compositions |
| ATE94206T1 (en) * | 1989-12-21 | 1993-09-15 | Novo Nordisk As | ENZYME-CONTAINING PREPARATION AND DETERGENTS CONTAINING SUCH PREPARATION. |
| JP2918991B2 (en) * | 1990-05-25 | 1999-07-12 | 三菱瓦斯化学株式会社 | Bleach detergent composition |
| ATE219136T1 (en) * | 1991-01-16 | 2002-06-15 | Procter & Gamble | COMPACT DETERGENT COMPOSITIONS WITH HIGHLY ACTIVE CELLULASES |
| SK278834B6 (en) * | 1992-01-17 | 1998-03-04 | Unilever Nv | Detergent whitening mixture containing particles |
| CA2156829C (en) * | 1993-02-26 | 1999-06-08 | Paul Amaat R. G. France | High active enzyme granulates |
-
1994
- 1994-02-10 CA CA002156829A patent/CA2156829C/en not_active Expired - Fee Related
- 1994-02-10 DE DE69409797T patent/DE69409797T2/en not_active Revoked
- 1994-02-10 ES ES94923580T patent/ES2115246T3/en not_active Expired - Lifetime
- 1994-02-10 EP EP94923580A patent/EP0686186B1/en not_active Revoked
- 1994-02-10 JP JP6519045A patent/JPH08507098A/en active Pending
- 1994-02-10 AU AU62676/94A patent/AU6267694A/en not_active Abandoned
- 1994-02-10 WO PCT/US1994/001528 patent/WO1994019444A1/en not_active Application Discontinuation
- 1994-02-10 CN CN94191792A patent/CN1071786C/en not_active Expired - Fee Related
- 1994-02-10 CZ CZ952147A patent/CZ214795A3/en unknown
- 1994-02-24 PE PE1994237365A patent/PE11295A1/en not_active Application Discontinuation
- 1994-02-24 MA MA23428A patent/MA23121A1/en unknown
-
1995
- 1995-08-21 US US08/507,354 patent/USH1653H/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| CZ214795A3 (en) | 1996-02-14 |
| PE11295A1 (en) | 1995-05-18 |
| MA23121A1 (en) | 1994-10-01 |
| EP0686186B1 (en) | 1998-04-22 |
| USH1653H (en) | 1997-06-03 |
| EP0686186A4 (en) | 1995-09-19 |
| ES2115246T3 (en) | 1998-06-16 |
| DE69409797D1 (en) | 1998-05-28 |
| CA2156829A1 (en) | 1994-09-01 |
| CN1071786C (en) | 2001-09-26 |
| DE69409797T2 (en) | 1998-12-10 |
| EP0686186A1 (en) | 1995-12-13 |
| WO1994019444A1 (en) | 1994-09-01 |
| CA2156829C (en) | 1999-06-08 |
| JPH08507098A (en) | 1996-07-30 |
| AU6267694A (en) | 1994-09-14 |
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