JPH06509122A - Detergent composition containing highly active cellulase and softening clay - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Detergent composition technology containing highly active cellulases and softening clays The present invention provides a detergent containing highly active cellulase in combination with softening clay (softening clay). Regarding the composition. In this detergent composition, cellulase is determined by the C14CMC method. Contains highly active cellulases determined by Preferably, the detergent composition comprises softened clay. together with a clay flocculant and, in the case of a liquid composition, an anti-settling agent for the clay.

Background of the invention In this field, not only good cleaning properties, but also good fabric softening performance, and other There is a need for detergent compositions that also exhibit textile protective properties.

Cellulolytic enzymes, or cellulases, are used in textile cleaning agents and to reduce the roughness of textiles. Its effectiveness as a depressant has long been recognized, and GB-A-2,075, 028, GB-A-2,095,275 and GB-A-2°094.826 , discloses detergent compositions containing cellulases for improved cleaning performance, and GB -A-1,368,599 Cellular for reducing roughness of fabrics containing cotton U.S. Pat. No. 4,435.307 describes the use of zeolite to reduce roughness. As a detergent additive, l1usicola In5 with the symbol ACX I in white olens and the use of cellulolytic enzymes derived from parts thereof. Ru.

EP-A-0269168 describes optimized detergent compositions containing cellulases. However, this is a mild alkaline pl! It is formulated in the area for cleaning and weaving of textiles. It combines the softening properties of materials and the protective properties of textiles.

WO39109259 has a high endoase activity and a parent for cellulose. Contains endoglucanases that have a soothing effect and are effective in reducing the roughness of cotton-containing fabrics. describes effective cellulase compositions.

However, cellulase compositions such as those described in the above-mentioned prior art documents are complex. Since it is a mixture and only certain parts are effective in protecting textiles, cellulase The commercialization of cellulases for the detergent industry has been delayed, and therefore the economical industrial production of cellulases for the detergent industry has cellulase composition is difficult to produce and requires large amounts of cellulase composition to obtain the desired effect on textiles. Is it necessary to use ?

The production of cellulases has also not been sufficiently improved for detergent applications. cellular The criteria for selecting C for detergent applications are as described in EP-A-350098. 14CM　It became possible to clearly do this using the C method. Highly active cellulases are immobilized remove at least 10% of the radiolabeled carboxymethyl cellulose. It is known that Preferred cellulases that fall under the definition of high activity according to the present invention The group is under examination for Chinmark Patent Application No. 1159/90 filed May 5, 1990. listed in the number.

In particular, essentially 1lus + 1cola 1nsolens DM 18 A model made against a partially purified approximately 43 kD cellulase derived from A cell consisting of a homogeneous endoglucanase component that is immunoreactive with noclonal antibodies. Lulase compositions are described.

This particular endoglucanase component of cellulase is useful for processing cellulose-containing materials. The discovery that it is advantageous to use cellulases, for example by recombinant DNA technology, This means that it can be manufactured economically, using only a small amount of cellulase composition, and can be applied to textiles. The desired effect can be obtained.

EP-A-381397 discusses the effects of low ionic strength on enzyme performance, especially for lipoproteins. Disclosure regarding

However, surprisingly, the tight matrices for selected enzymes of the present invention The effect of cellulases of the prior art as described in EP-A-381397 much larger than expected.

EP-A-177165 describes the use of softened clays together with cellulases in detergent compositions. It describes how to use it.

The invention of this patent discloses that the prior art has two major softening or roughness reducing detergent compositions. This is based on the fact that the combination of EP-A-177165 is Excluding clay or cellulose from detergent compositions containing their respective other components He admits there is no reason. However, EP-A-177165 For a selected group of highly active cellulases, the combination with clay do not recognize that the additive performance is superior to that expected from chemical feedstocks.

Therefore, the object of the present invention is to provide an optimal softening agent containing highly active cellulase and softening clay. It is an object of the present invention to provide a detergent composition that exhibits chemical properties. Another purpose is to detergent compositions in liquid or granule form.

Another object of the invention is a fabric comprising highly active cellulase together with softening clay. Provides excellent color recovery and white retention, especially for textiles containing cellulose fibers An object of the present invention is to provide a detergent composition. Another object of the invention is furthermore particularly about Provided is a detergent composition that exhibits good stain removal and cleaning performance at temperatures below 60°C. That's true.

Another object of the invention is to provide such detergent compositions with a relatively high density and an inorganic salt loading. It should be provided in a dense form with a low filler content and exhibiting optimal softening performance.

Yet another object of the invention is to provide, in addition to the essential compounds of the invention, storage-stable creams. Provides a liquid detergent composition containing an anti-settling agent to form a ray-dispersed matrix It is to be. Yet another object of the invention is that in addition to the essential compounds, further A liquid or An object of the present invention is to provide a granular detergent composition.

Summary of the invention The present invention is a detergent composition comprising a surfactant, a builder system and a cellulase. , the cellulase is fixed by the C1.4 CM method described in detail below. at least 10% of the radiolabeled carboxymethyl cellulose and further characterized in that the detergent composition also includes a softening clay. The present invention relates to a detergent composition.

or highly purified endoglucana, a homologue of approximately 43 kD cellulase. It consists of a homogeneous endoglucanase that is immunoreactive with antibodies made against the enzyme. Detergent compositions are preferred. Furthermore, softened clay, and Table ID No. 2 and Endoglucanase enzyme having the amino acid sequence shown in ID No. 4 or its equivalent Detergent compositions containing cellulase family members can be used in synergistic textile treatments according to the invention, especially in soft It turned out to be advantageous for the transformation.

definition Unless otherwise indicated, the following definitions are used below.

-Percentages are in % by weight.

- Softening refers to areas of fabric treatment other than washing, particularly softening, color restoration and whitening. Including maintenance, anti-wrinkle, anti-static, and ease of ironing.

Detailed description of the invention The detergent composition may be in granular or liquid form. Its form can be softened by washing, for example. the desired application, such as detergent, low or high temperature, automatic washing machine or semi-automatic manual washing. It varies depending on the destination.

Detergent forms include surfactants, builders, cellulases, softening clays and will greatly influence the selection and amount of raw materials for the particular composition used. liquid Preferably an anti-settling agent for softened clays, liquid or granular compositions. is consistent with flocculants used to facilitate clay deposition on fibers. death However, the detailed description of all the individual compounds and examples will enable those skilled in the art to understand the invention. Bright detergent compositions can be formulated.

surfactant A variety of surfactants can be used in detergent compositions. Anionic, nonionic, amphoteric and representative list of zwitterionic surfactants and species of these surfactants. No. 3,664,961 issued to Norris on May 23, 1972. listed in the number.

This includes mixtures of anionic surfactants, especially sulfonate endoglucanases. and a sulfate surfactant in a weight ratio of 5:1 to 1:2, preferably 3:1 to 2:3, More preferably '3:1-1. ] Particularly suitable are mixtures of the following.

Preferred sulfonates have 9 to 15, especially 11 to 13 carbons in the alkyl group. an alkylbenzenesulfonate having an atom, and a fatty acid containing 01□ to C18 fat. Alpha sulfonated methyl fat derived from a fat source, preferably a CI6-C18 fat source There are fatty acid esters. In each case the cation is an alkali metal, preferably a It is thorium. Preferred sulfate surfactants have 12 to 18 in the alkyl group. 10 to 20, preferably 10 to 20, optionally in the alkyl group of the alkyl sulfate having carbon atoms. or ethoxylates having 10 to 16 carbon atoms and an average degree of ethoxylation of 1 to 6. It is a mixture with oxysulfate. An example of a preferred alkyl sulfate is tallow alkyl sulfate. acid salts, coconut alkyl sulfates, and C14-C15 alkyl sulfates. . The cation in each case is again an alkali metal cation, preferably sodium. Ru.

The nonionic surfactant suitable for the present invention is a condensation agent of ethylene oxide and a hydrophobic moiety. with an average hydrophilicity-lipophilic balance (HLB) of 8 to 17, preferably 9.5 to 13.5, more preferably 10 to 12.5. hydrophobic (parent) The oily) moiety may be aliphatic or aromatic in nature, and may contain a polymer that condenses with a specific hydrophobic group. The length of the lyoxyethylene group can be adjusted to accommodate the desired length between the hydrophilic and hydrophobic moieties. It is possible to obtain a water-soluble compound having a degree of balance.

Particularly preferred nonionic surfactants of this type are C''-Cts primary alcohol ethoxylate containing 3 to 8 moles of ren oxide, In particular, C14 to C1 containing 6 to 8 moles of ethylene oxide per molecule of alcohol 5 primary alcohol, and 3 to 5 moles of ethylene oxide per molecule of alcohol. It is a C12-C14 primary alcohol containing.

Another type of nonionic surfactant has the general formula %) (In the formula, 2 is a moiety derived from glucose, and R has 12 to 18 carbon atoms. H is a saturated hydrophobic alkyl group, t is O to 10, and number is 2 or 3. and X is 1.3 to 4. ) of alkyl polyglucoside compounds, these compounds contain less than 1096 unreacted Contains modified fatty alcohols and less than 50% short chain alkyl polygel compounds. this Species compounds and their use in detergents are listed under El'-B 0070077.00 75996 and 0094118.

In addition, as nonionic surfactants, formulas such as hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, and R2 is C 5-31 hydrocarbyl, Z is a straight hydrocarbyl chain with at least three hydroxyls directly attached to the chain or its alkoxylated derivatives. Ru. ) polyhydroxy fatty acid amide surfactants are also suitable.

Preferably RI is methyl and R2 is a straight chain 011 such as coconut alkyl. -15 alkyl or alkenyl chain or mixtures thereof, and Z is a reducing In the amination reaction, glucose, fructose, maltose, lactose derived from various reducing sugars.

Other types of surfactants are semipolar surfactants such as amine oxides.

Suitable amine oxides are monoc-c, preferably clo-c14N-al methyl or alkenylamine oxide and propylene-1,3-diaminedio oxide, where the remaining N positions are methyl, hydroxyethyl or is substituted with a hydroxypropyl group.

Another type of surfactant is amphoteric surfactants, such as polyamine-based compounds.

Cationic surfactants can also be used in the detergent compositions of the invention, with preferred The grade ammonium surfactant is monoC8~Cie, preferably 010""c1 selected from 4N-alkyl or alkenylammonium surfactants; where the remaining N positions are replaced by methyl, hydroxyethyl or hydroxypropyl groups. has been replaced.

Mixtures of various surfactants, more specifically anionic-nonionic and anionic Preferred are non-ionic and cationic mixtures. A particularly preferred mixture is Described in patent no. 2040987 and published European patent application no. 0087914 has been done. The detergent composition may contain 1 to 701m96 surfactants. However, the surfactant is usually present in the composition in an amount of 1 to 30% by weight, more preferably 10 to 2% by weight. Contains 5% by weight of melon.

builder The builder material is generally included here in an amount of 10 to 60% by weight of the detergent composition. Ru. The compositions of the present invention are free of or substantially free of phosphate-containing α-builders ( Substantially free is defined here as comprising less than 1% of the total detergent builder system. builder systems are water-soluble builders and water-insoluble builders. , or a mixture thereof. Water-insoluble builders are inorganic ion exchange + 4 materials, generally inorganic hydrated aluminosilicate materials, especially hydrated zeolites A, X , B or ~5.

The preferred aluminosilicate ion exchange material is a unit cell type %formula% (where ~1 is a calcium exchange cation, and 2 and y are at least 6. and the molar ratio of 2 to y is from 1.0 to 0.5, and X is at least 5, preferably The number is preferably 7.5 to 276, more preferably 10 to 264. ) has. The aluminosilicate material is in hydrated form, preferably between 10% and 2 It is crystalline, containing 8% water, more preferably 18% to 22% water.

The above aluminosilicate ion exchange material further has a particle size of 0.1 to 10 microns. It is characterized by a diameter of 0.2 to 4 microns, preferably 0.2 to 4 microns. Here the term “particle size ” by conventional analytical techniques such as microscopic measurements using a scanning electron microscope. is the average particle diameter of a given ion exchange material as determined. aluminosilicate Salt ion exchange materials also have calcium ion exchange capacity calculated in anhydrous state. at least 200 mg equivalent of CaCOa water hardness/g aluminosilicate; Generally, it is characterized by 300 g　eq, /g ~ 352　B eq, /g. Ru. The aluminosilicate ion exchange material used here is further GB-1°42 It is characterized by a calcium ion exchange rate, which is described in detail in 9.143.

Aluminosilicate ion exchange materials useful in the particles of the present invention are commercially available and Natural materials may be used, but synthetic materials are preferred. Made of aluminosilicate ion exchange material The manufacturing method is described in US Pat. No. 3,985,669. useful for the present invention , a preferred synthetic crystalline aluminosilicate ion exchange material is zeolite A1 zeola Products marketed under the symbol Zeolite B1 Zeolite X5 Zeolite H8 and mixtures thereof It is a thing. In particularly preferred embodiments, crystalline aluminosilicate ion exchange materials is zeolite A and has the formula %formula% (wherein X is 20 to 30, particularly 27). 2Na [(AIO) (SiO) 186 2 813 2 10B -10,276HO of zeolite X and Naa[(AIO)(Sin 2) Zelite HS of 617.5H20 is also suitable.

Another suitable water-soluble inorganic builder material is a layered silicate, such as 5KS-6 (Hexyl strike). 5KS-6 is a crystalline material made of sodium silicate (Na2S1205). It is a crystalline layered silicate. The high binding ability of Ca “7Mg” + is mainly due to cations. This is due to the on-exchange mechanism. The solubility of this material increases in hot water.

Water-soluble builders are monomeric or oligomeric carboxylate chelators. stomach.

Suitable carboxylic acid salts containing one carboxyl group include Hergi Patent No. 831, No. 368, No. 821.369, and No. 821,370. Among these are lactic acid, glycolic acid, and their ether derivatives. 2 carbo Polycarboxylic acid salts containing xyl groups include succinic acid, malonic acid, c) water-soluble salts of diacetic acid, maleic acid, diglycolic acid, tartaric acid and fumaric acid; and German Patent Nos. 2,446,686 and 2,446,687, and and the ether carboxylate salts described in U.S. Pat. No. 3,935,257; The sulfinyl carboxylate salt described in Belgian Patent No. 840,623 be. Polycarboxylic acid salts containing three carboxyl groups are particularly suitable for water-soluble quenchants. aconitate and citraconate and British Patent No. 1.379 ．． Coatings such as carboxymethyloxysuccinate as described in No. 241 Huccinic acid derivatives, lactoxy as described in Dutch Application No. 7205873 succinate, and the 2-oxychloride described in British Patent No. 1,387°447. Oxypolycarboxylate salts such as cer-1,1,3-propanetricarboxylate Ru. Polycarboxylic acid salts containing four carboxyl groups are described in British Patent No. 1,261 , 1,1,2,2-ethanetetracarbo salt, 1,1.3.3-propanetetracarboxylic acid salt and 1,1,2.3- There is a propanetetracarboxylate salt. Polycarboxylic acid salts containing sulfo substituents include , British Patent Nos. 1,398,421 and 1,398,422 and U.S. Pat. 3,936,448 and British Patent No. No. 1,082,179, there is a sulfonated pyrolyzed citrate salt, Polycarboxylic acid salts containing substituents are described in British Patent No. 1.439.000. Ru.

Alicyclic and heterocyclic polycarboxylate salts include cyclopentane-cis, cis, Su-tetracarboxylate, cyclopentanoene pentacarboxylate, 2,3,4 ．． 5-tetrahydrofuran-cis, cisone-sutetracarboxylate, 2,5- Tetrahydrofuran-cis-dicarboxylate, 2,2,5.5-tetrahydrofuran Ran-tetracarboxylate, 1,2,3,4,5.6-hexane-hexacarbo salts and polyalcohols such as sorbitol, mannitol and quinlitol. There is a carboxymethyl derivative of Aromatic polycarboxylic acid salts include British time 5 Mellitic acid, pyromellitic acid and lids described in No. 1 No. 1,425,343 There are derivatives of fluoric acid.

Among the above, preferred polycarboxylate salts have up to 3 carboxylic acids per molecule. A hydroxycarboxylic acid salt containing a group, more specifically a citrate.

Preferred builder systems for use in the present compositions include water-soluble amines such as Zeolite A. Luminosilicate builders and water-soluble carboxylate chelates such as citric acid It is a drug. In addition, builder systems that also include polycarboxylate polymers are - system, but also beneficial in imparting softening performance to the detergent composition of the present invention. Do you get it.

Polycarboxylate polymers are described in detail in the prior art, e.g. EP-A-137669. is explained in.

Other builder materials that can form part of the builder system for the compositions of the invention include Inorganic materials such as potassium metal carbonates, bicarbonates, and silicates, and organic phosphonic acids salts, aminopolyalkylene phosphonates and aminopolycarboxylates. There are machine materials.

cellulase The activity of enzymes and in particular the activity of cellulase enzymes can be differentiated differently for various applications. It is measured using an analytical method.

All of these methods provide a practical evaluation of performance in expected use, or at least In both cases, we are attempting to perform m-determination that correlates with performance during use. european patent As described in detail in application EP-A-350098, a number of methods, especially se Methods frequently used by lulase manufacturers include cleaning detergent formulations. There is no sufficient correlation between the performance of cellulase in the product and its performance in use. This includes various other It depends on the conditions of use, and these activity meter 1 determination methods are not applicable to the conditions of use. It was uttered.

The method described in EP-A-350098 describes the use of It has been developed to have a promising correlation for quantifying cellulase activity. Therefore, the present invention uses the method disclosed in EP-A-350098. Cellulases for H use in the present invention were screened using Distinguish from cellulases that are not compatible. As disclosed in EP-A-350098: This screening method, hereinafter referred to as the C14CMC method, is described below.

principle The principle of the C14CMC method for sieving is that limited cellular At this concentration, immobilized carboquine methylcellulose was removed from the fabric substrate. The goal is to measure the rate at which CMC removal uses C14 radiocarbon and CM 1lF1 is determined by radioactively labeling a portion of C. Before and after cellulase treatment Cellulase activity can be evaluated by simply counting the amount of radioactive C14 on the cloth wrapping material. can do.

Sample preparation CM C preparation, radioactive CM CIFA solution is prepared according to Table 1. hk episodic CMC, by the method described in EP-A-350098.

Textile base material: The textile base material is a muslin cotton fabric with a size of 5 cm x 5 cm. child 0.35 ml of radioactively labeled CMC stock solution is dropped onto the center of each of these substrates.

The muslin cotton/+i fabric is then air dried.

Immobilization of CMC: To immobilize radioactively labeled CMC on muslin cotton fabric. First, the original Haunau, Germany-made rhondrometer device "Rinitest" Use the original Haunara. 400 in the metal container of the launderometer 1 of hard water (45 sol/liter Ca++ ions). per container Up to 13 pieces of fabric can be used. The container is then placed in a rhondrometer apparatus for 4 hours. Heat treatment with a heating cycle of 20°C to 60°C for 0 minutes. After heat treatment, the fabric Rinse with tap water for 1 minute. Wring the fabric and air dry for at least 30 minutes. EP - According to A-350098, fabrics with radioactive CMC fixed thereon can be treated without washing. Cleaning test solution: Cleaning test solution is prepared according to the composition shown in Table 11. Adjust pll to 7.5. cleaning test The test solution is the stock solution to which the cellulase test sample is added. Amount of cellulase to add Be careful not to dilute the cleaning test solution by adding 100% water before determining the mean. The amount of cellulase used in this sieve is determined by the amount of cellulase used in the cleaning test solution. The cellulase protein in the solution was 25xlO-6% by weight (0.25 ml at 14.5°C). (Ligram/Little).

Washing procedure 2 The swatches thus inoculated with radiolabeled CMC were then subjected to a washing simulation. Process using the ration method. The washing method is based on the original Haunala from Germany's Haunau. Lone zolometer type device [Linitest, original)\Unau (1,1n Itest, Original l1aunau) Simulate with J. individual swatches into a 20c x 3 glass vial. Fill the vial with washing test liquid 101. and then seal liquid-tight. Hold up to 5 vials in each Lawn Zolometer - put it in a jar. Jar filled with water as heat transfer medium for washing simulation do. Washing simulation involves increasing temperature from 20℃ to 60℃ over 40 minutes Do it as a cycle.

After processing the sample, the vial is placed in purified water, and then the valley sample is removed from the vial. Rinse in a beaker under running soft water, squeeze and air dry for at least 30 minutes. .

DI fixed: To determine radiolabeled CM C removal, a scintillation counter, For example, if you use the LKB1210 Ultra Beta Anti-Tillation Counter Ru. i for the most accurate results! Ideal for specific scintillation counters The operating instructions manual should be followed. For example, LKB 1210 Ultra For beta scintillation counters, the following method should be followed. measurement The sample to be determined is prepared using a scintillator liquid (e.g., a scintillator from Bara card). -299) Place in a plastic vial filled with 12 ml. Then look Allow the book to stabilize for at least 30 minutes. Next, the vial is LKB 121 0 ultrabeta scintillation counter and measure the radioactivity of each sample. You can get the count.

In order to determine the amount of CMC removed by cellulase alone, the cells were inoculated at the same time. The 1lFI determination of samples treated in a wash test solution without cellulase is necessary. It is essential. Cellulase activity is then expressed as radiolabeled CMC removal rate. Ru. This percentage is calculated by the following formula: (where XO is the wash without cellulase) Radioactive scintillation counts of samples treated with test solution, XC is the evaluation Radioactive scintillation of samples treated with wash test solution containing cellulase ).

Statistical considerations, method confirmation: To give statistically robust results, standard statistical analysis should be used. . For the given example, the LKB1210 ultrabeta scintillation counter Three sample sample sizes for each radioactive scintillation count were prepared using a It has been found that it is possible to use

To confirm the method with internal cross-checks, see EP-A No. 350098. "Blank sample" measurements and calculations according to the specification are recommended. this thing would be to detect and eliminate errors.

Interpretation of results: The screening tests described are comparable to cellulases which do not form part of the present invention. rapid and unique confidence to identify cellulases that meet the activity criteria of the present invention by comparing I'll give you a way to do it.

Removal of 1006 or more immobilized radiolabeled CMC according to the C14CM C method were found to indicate that the respective cellulases meet the requirements of the present invention. .

It will be appreciated by those skilled in the art that removal rates higher than 10% indicate high activity of the respective cellulase. It should be obvious. Therefore, the protein in the washing test solution according to CI4CM C method provides greater than 25% or preferably greater than 50% removal of radiolabeled CMC at high quality concentrations. cellulases with improved performance for use in laundry detergents. It is expected that he will give some pointers.

Also, the use of a higher concentration of C14CM C cellulase results in a higher removal rate. It was expected that it would give However, cellulase concentration and There is therefore no proven linear correlation between the resulting removal rates.

Also, the use of a higher concentration of C14CM C cellulase results in a higher removal rate. It was expected that it would give

Table ■: Radioactive C14-labeled CMC stock solution (all weight % of total solution) is sufficient. Non-radioactive CMC and radioactive to give radioactivity allowing unambiguous reading Including CMC. For example, radioactive CMC has an activity of 0.7 milliquiries/g. It can be mixed with non-radioactive CMC in a ratio of 1:6.7.

Table 11: Washing test liquid (All weight % of total solution) According to the invention, the preferred cellulase is Danish Patent Application No. 1159/9 This is as described in the specification of No. 0. For example, cellulose useful in the compositions of the invention The preparation is essentially l1usicola 1nsolcns, DSK1 Antibodies and immune reactions raised against high-precision 43KD cellulase derived from 800 a homogeneous endoglucanase that is homologous to the 43KD endoglucanase. It can consist of a zeolite component.

All cellulase enzymes according to the present invention meet the criteria of the above screening test. It should be emphasized that However, Tenmark patent In Application No. 1159/90, additional criteria have been established and are Allows identification of preferred cellulase enzymes in combination with cleaning tests Make it.

Cellulase preparations that are particularly useful in the compositions of the present invention include, in addition to screening tests, The endoglucanase component is at least about 50 per total protein IB, preferably has a CMC of at least about 60, especially at least about 90 CMC-endase units. - exhibits endoase activity. Particularly preferred endoglucanase components of at least 100 100 C endoase units per 11 g of total protein. Shows CMC-endase activity.

In this context, the term "CMC-endase activity" refers to Carboxymethyl cellulose after incubation of the cellulase preparation of the present invention cellulose (CMC) as determined by the viscosity decrease of a solution of , endoglucanase component due to its ability to degrade into cellobiose and triose endoglucanase activity.

CMC-endoglucanase activity reduces the viscosity of CMC as follows: It can be measured from a small amount. CMC 35g/l in 0.1M 1-Lys buffer at pH 9.0 A substrate solution containing ()\-Cures7LFD) is prepared. Analyze The desired enzyme sample is dissolved in the same buffer. Substrate solution 10-1 and enzyme solution 0, 51 is mixed and the temperature is adjusted to 40°C using a viscometer [e.g. ) VT 181, NV sensor, 181 rps]. viscosity reading Mix and do this as soon as possible after 0 minutes have elapsed. These viscosity The amount of enzyme that is reduced by half under the conditions is 1 unit of CMC-endase activity or Defined as CEVu/su sotol.

SDS-polyacrylamide gel electrophoresis (SDS-PAGE) and Isoelectric focusing on labeled proteins using known methods is used in this context to perform cellulase production. Measure the molecular weight and isopoint (pI) of each endoglucanase component in the drug. used to. In this way, molecules of a particular endoglucanase component - When the amount was measured, it was 43KD. The isoelectric point of this endoglucanase is A l1 constant (, it was found to be about 5.1.

Cellobiohydrolase activity is the activity against cellobiose p-nitrophenyl. May be defined. The activity is nitrates released per minute at 37°C and pH 7,0 Lophenyl is determined to be 10=mol. This endoglucanase component is essentially a cellulose It was found that it had no biohydrolase activity.

The endoglucanase component in the cellulase formulations of the present invention was initially purified using a number of purification methods. That is, the crude H,1nsoles cell according to U.S. Pat. No. 4,435.307. It was isolated by a method involving reverse-phase HPLC purification of the Rase mixture.

This method is surprisingly effective due to its surprisingly high endoglucanase activity. Isolation of 43KD endoglucanase as a single component with unexpectedly favorable properties occurred.

In addition to screening tests, the cellulase enzymes useful in the present compositions are An enzyme that exhibits doglucanase activity (hereinafter referred to as "endoglucanase enzyme") (These enzymes have the amino acid sequence shown in the attached sequence list ID #2), and can be further defined as those homologues that exhibit endoglucanase activity.

In the present context, the term "homologue" refers to Breathe soaked in SSC and 5x Denhardt's solution with 20% formamide at 40°C. Sonicate denatured orchid thymus DNA with sodium phosphate 50mM (pH 6,8) and 50mM (pH 6,8). After 1 h prehybridization in solution with 0 μg, 100 μM ATP was added. This amino acid configuration (hybridizes for 18 h at 40 °C in the same solution supplied) DNA coding for the endoglucanase enzyme with the same probe We attempt to show polypeptides coated by hybridizing DNA.

The term refers to one or more amino acid residues at either the C-terminus or the N-terminus of a native sequence. is added to both, one or more amino acid residues at one or more sites in the native sequence. Substitution of groups at either or both ends of the native amino acid sequence or native Deletion of one or more amino acid residues at one or more sites within the sequence, or the native sequence the above obtained by insertion of one or more amino acid residues at one or more sites in It is intended to encompass derivatives of sequences.

The provisions of the Budapest Treaty on the International Recognition of the Deposit of Microorganisms (Budapest Treaty) According to FRG's D-3300 Braunschhaig's Matscher Order Hege I 107 in 1981 in B's Teiche Samlung Phono Microorganismemen. -It may be produced by the strain DSM1800 deposited on the 11th. stomach.

In other aspects of history, the cellulase enzymes useful here are In addition to the sequencing test, the enzyme having the amino acid sequence shown in the attached sequence list ID #4 Doglucanase enzymes or their homologues exhibiting endoglucanase activity (top can be defined as: According to the above, FRG's D-3300 brown Baigu's Matssha Order Begu IB's Toiche Samlung Fono Miku by strain DSM 2672, deposited on June 6, 1983, at Loorganismen. It may also be something that can be produced by

Furthermore, it is noted that homologous endoglucanases may be derived from cellulose degradation. Illustrated.

However, in the case of industrial production of the cellulase preparation of the present invention, recombinant DNA technology, or microbial fermentation involving to ensure overproduction of the desired enzyme activity Alternatively, it is preferred to use other techniques involving mutagenic control. like this Methods and techniques are known in the art and can be readily practiced by those skilled in the art.

In this way, the endoglucanase component is the endoglucanase component or a DNA sequence encoding the precursor of the endoglucanase component and the endoglucanase component; Allows expression of a DNA sequence encoding a lucanase component or its precursor transformed with a recombinant DNA vector carrying a DNA sequence encoding a function. host cells capable of expressing the endoglucanase component or its precursor in the culture medium. The endoglucanase component is collected from the culture by culturing it under conditions of It may be possible to produce it by any method.

A DNA sequence encoding an endoglucanase or a precursor form of the enzyme as described above. The DNA construct (consLruct) containing the sequence is attached with the attached sequence list ID #1 or or D　N　A　l having the NA sequence as shown in ID#3, or its modification l constructs. An example of a suitable modification of the DNA sequence is another modification of the endoglucanase. does not result in an amino acid sequence, but is compatible with the codon usage of the host organism into which the DNA construct is introduced. It is a native enzyme because it does not result in corresponding nucleotide substitutions or different amino acid sequences. Different types of endoglucanases can result in endoglucanase mutants with properties different from Nucleotide substitutions that sometimes result in a protein structure that Possible modifications Other examples include the insertion of one or more nucleotides at either end of the sequence, or Deletion of one or more nucleotides at either end or within the sequence.

DNA constructs encoding endoglucanase enzymes useful herein have been established. Standard methods such as S, L.

Tel rahedran by Beaucage and M.H. Caruthers 1. ctLcrs　22. 1981, pp, 1859-1.869 EMBOTournal 3,198 by the sphoamidite method or Matthes et al. 4. may be produced synthetically by iJ) as described in pp. 801-805. . According to the phosphoramidite method, oligonucleotides are e.g. synthesized, purified, annealed, ligated and cloned in a suitable vector. become

A DNA construct encoding an endoglucanase enzyme or its precursor may be Ba Huslcola! Cellulases such as n5oless D S M23C6 Establish a cDNA or genome library of the producing microorganism, and use standard methods to For example, if the endoglucanase is fully or partially amino acid Hybridization using oligonucleotide probes synthesized based on acid sequences or by appropriate enzymatic activity (i.e. CMC-endo as defined above). by selecting for clones expressing the enzyme activity) or by selecting for clones expressing native cellular produce proteins that are reactive with antibodies against enzymes (endoglucanases) Simply select for positive clones by selecting for clones. You can let go.

Finally, DNA constructs can be derived from synthetic, genomic or cDNA sources according to standard techniques. (as appropriate) fragments (fragments correspond to various parts of the total DNA construct) Mixed synthesis/genome, mixed synthesis/cDNA or may have a mixed genomic/cDNA origin. In addition, the DNA construct is Certain primers, such as those described in U.S. Pat. No. 4,683,202 or R. , Saiki et al., 5science 239. 1988. p p.

by polymerase chain reaction using those described in 487-491. May be produced.

The recombinant expression vector into which the DNAtA construct is inserted is conveniently a recombinant Any vector that may be subjected to the DNA method may also be mentioned, and the selection of the vector may be , Lff will depend on the host cell into which the vector is to be introduced. in this way , the vector exists as an autonomously replicating vector, i.e., an extrachromosomal entity. a vector whose replication is independent of chromosomal replication, e.g. a plasmid. You can. Alternatively, the vector may be inserted into the host cell genome when introduced into the host cell. integrate, replicate together with one or more chromosomes (into which the vector has integrated) It may be something like that.

In the vector, the DNA sequence encoding the endoglucanase is operationally , should be linked to suitable promoter and terminator sequences. promo The target can be any DNA sequence that exhibits transcriptional activity in the host cell of choice. and a gene encoding a protein that is either homologous or heterologous to the host cell. It may be derived from endoglucanase, promoter and terminus, respectively. for combining DNA sequences coding for inators and for combining them into suitable vectors. The methods used to insert the (See Ku et al., supra).

Transformation or black mold (^spe. rgllus niger).

Fungal cells formed protoplasts and transformed protoplasts in a manner known per se. Thereafter, the cells may be transformed by methods that involve regenerating the cell wall. Kouji The use of fungi as host microorganisms is described in EP 238023 (Novo ・Industry A/S), the contents of which are included here as a reference. Transfer. The host cell may also be a yeast cell, such as Saccharomyccs It may be a strain of P. cercvisiae.

Alternatively, host cells have recently been developed, particularly from B. treptoyces and Bacillus (B. aci I Ius) and Escherichia coli (E coli) good. Transformation of bacterial cells is carried out according to conventional methods, for example, Samprutsuk et al., Mo1 ecular Clonlng: ^Laboratory Manual ( Cold Spring (1989).

Screening for suitable NA sequences and construction of vectors are performed by standard methods. You can. See Samprutsuk et al., supra.

The medium used to culture transformed host cells must be compatible with the host cell in question. Any conventional medium suitable for growth may be used. expressed endogluca The enzyme may be conveniently secreted into the culture medium and subjected to centrifugation or filtration of the cells. The protein components of the medium are separated from the medium using salts such as ammonium sulfate. After precipitation, ion exchange chromatography, affinity chromatography by well-known methods including subjecting it to chromatographic methods such as It may be collected from

Recombinant DNA techniques, protein purification techniques, fermentation and mutagenesis techniques as described above. high-purity endoglucan It is possible to provide lucanase.

The amount of cellulase in the composition is such that the amount of enzyme protein to be delivered to the wash solution is 0.005-40B/1 liter of washing liquid, preferably 0.01-10mg/washing The volume should be such that it is 1 liter of liquid.

softened clay One essential ingredient of the present detergent composition is a softening clay.

Any clay or mixture thereof used in the art can be used in the present invention.

A preferred example is British Patent No. No. 5,019°292.

Among these types of viscosity are various heat-treated kaolins and six types of multilayer smectas. is included. As known from the art, preferred smectite clays are Cation exchange capacity fi of at least 50 meq/viscosity 100 g (layer current of 0.2 to 0.6) (corresponding to the load).

Clays having a particle size within the range of 5 to 50 μm are further preferred and additionally preferred smectas. The clay has the general formula (where y is 0; or if y is not 0, MeI II is A　1　s　F　e or B, Mn+ is monovalent (n-1) or divalent (n=2) is a metal ion, for example, selected from Na5K, Mg, Cu, Sr. It is a hectorite clay. The value of (x+y) is the layer electric potential of hectorite clay. It is a load. The hectorite clay suitable for the detergent composition of the present invention is at least 50% has a layer charge distribution such that is within the range of 0.23 to 0.31.

having a layer charge distribution such that at least 65% is within the range 0.23-0.31 Hectorite clays of natural origin are preferred.

Specific non-limiting examples of fabric softening smectite clay minerals are: sodium montmorillonite Volclay B C"" Gclwbl Le) CP “” Thixo-Jel (R) Pen・ Ben-A-Gel (R) Laponite te) SP” Sodium saponite Balan l, ([arasym) N A S], OO"" Calciummon morinite 7, 'y -y -'l (Soft C1ark) (+?) Kimouro The amount of C5M-clay (1?) from the detergent composition It depends on the shape of r1. Generally, it is 5% from the lower limit of (], 5%, 1% or 8%. [Can be up to an upper limit of 10o, 20% or 15%.

Preferred optional ingredients Clay flocculants are not commonly used in fabric treatment compositions. On the other hand, people are clay stains Try using a clay dispersant to help remove it from the fabric. However, the viscosity Soil flocculants are very useful in other industries such as oil well drilling and for ore flotation in metallurgy. well known. Most of these substances are ethylene oxide, acrylamine Acrylic acid, dimethylaminoethyl methacrylate, vinyl alcohol, vinyl Nylpyrrolidone, a fairly long chain derivative derived from monomers such as ethyleneimine Polymers and copolymers. Gums such as guar gum are also suitable. .

Polymers of ethylene oxide, acrylamide or acrylic acid are preferred. this These polymers have molecular weights (weight average) ranging from 100,000 to 10 million. It has been discovered that if it is within the range, it dramatically increases clay deposition.

Such polymers preferably have a molecular weight of 150,000 to 5 million, more preferably 15 million ,000 to 800,000 (weight average) molecular weight.

The most preferred polymer is poly(ethylene oxide). The molecular weight distribution is narrow Gel permeation chromatography against molecular weight distribution poly(ethylene oxide) standards The container can be inspected using a

The amount of clay flocculant ranges from 0 to 21, ) 96 when expressed as % of clay. . For clay flocculants having a weight average) molecular weight of 800,000 or less, preferred The amount of clay is 2-20% of the clay. with a (weight average) molecular weight of more than 800,000 In this case, the preferred amount is 0.005-2% of the clay.

Another preferred optional component is a substituted polysiloxane, where the amount of siloxane is 0-50% by weight of clay, preferably 0.1-20%, most preferably 1.0-20% It is in the range of 10%.

Polymeroxanes useful in the present invention include softened linear or branched organic functional groups having the general formula: Can be described as a functional polydiC alkylsiloxane: ” In the two formulas, R is C alkyl; R' is a polyether of R or (C oxide), and capping of H or R Has a group: R' is branched or straight chain C alkyl: ■-4 ql and ql are integers; m and (ql, +q2) are integers from 4 to 1700: n is an integer from 0 to 6 ; Y is a (C oxide) polyether of k (k has an average value of 7 to 100) has a capping group of H or C alkyl; or Y is: In the above, X and V are -H, -C alkyl, 10-aryl, -C cycloalkyl selected from nitrogen, -CNH-COR; can be quaternized to represent: ■ In the above, W can be selected from X and V; or Y is: H-C-T H--C--H In the above, T and P are -H, -COOH.

-coo-c selected from alkyl or epoxy-C cycloalkyl.

” Preferred Nroxanes of the general formula 2 are those in which (ql+q2) is an integer of 50 to 1500. , m is an integer from 4 to 100.

The most preferred Nroxanes of the above general formula are characterized by any of the following:

-RSR- is methyl, R' is propyl, (ql+q2) is 329, m is 21, n is 1, Y is 12, polyether consisting of ethyl oxide and acetic acid capping groups is: or -RSR- is methyl, R' is propyl, (ql+q2) is 485, m is 15, n is 1, Y is 12, polyether consisting of ethyl oxide and acetic acid capping groups is; or -R, R- are methyl, R' is methyl-2-propyl, (ql + ql) is 14 70, m is 30, n is 1, and Y is -(aminoethyl)amine.

The detergent composition of the present invention can be provided in liquid form as an aqueous dispersion. If it is in liquid form , detergent compositions contain softening clays, siloxanes and clay flocculants along with anti-settling agents. It is preferable to include it in

A suitable antisettling agent is one that is sufficiently activated to suspend the particles within the liquid detergent composition. A supporting matrix shall be provided.

Particles in this sense are particles that can be suspended for desirable properties in liquid detergent compositions. granules or droplets.

The particle size is usually less than 200 μm. Individual particles may be essential or optional in detergent compositions. It can contain one or more kinds of compounds.

Finally, acceptable antisettling agents must not adversely affect the viscosity, elasticity, or aesthetics of the product. No.

These anti-settling agents or mixtures thereof may be used at a level of rt 10.25 to 5% of the composition of the present invention. used in bells.

Parents such as clays of the Bentone group and humid silicas. Organic quaternized ammonium clay compounds are examples of antisettling agents suitable for use in the present invention. be. Bentone rheology additives are cationic and have at least 10 carbon atoms. a clay product containing an organic compound containing at least one alkyl group and a delaminated lattice It is listed as. Bentone ■ has the property of swelling in certain organic liquids.

Organophilic quaternized ammonium clay compounds are disclosed in U.S. Pat. No. 4,287,086. The preferred anti-settling agent is as described in the book.

Fumed silica also imparts excellent anti-settling properties to the compositions of the present invention. Huyum Dosilica is a colloidal form of silica obtained by combustion of silicon tetrachloride in a hydrogen-oxygen furnace. Usually defined as a mosquito. Humtonlica is used for ink, resin, rubber, paint and It is commonly used as a thickener, thixotrope and reinforcing agent in cosmetics and cosmetics. CAD- 0-3IL Heamtosilica is a suitable anti-settling agent for use in the present invention. ben Mixtures of clay, humid silica or cellulosic suspending agents are also suitable for sedimentation. It is an inhibitor.

The rheological properties of the resulting liquid composition are critical for commercially acceptable products. It is. Liquids that can be described as stringy (i.e. elastic), thick or clumpy are preferred. do not have.

The above-mentioned anti-sedimentation IL agents avoid these undesirable rheological properties, while Maintains a fluid, uniform product with good consumer appeal. Approx. 100 to approx. A viscosity within the range of 1000 kg/(ms) is desirable.

It is also desirable that the liquid composition exhibit plastic rheology.

Materials exhibiting plastic flow properties flow after the applied shear stress exceeds a critical minimum value. Only.

Optional ingredients The composition typically contains optional ingredients that normally form part of detergent compositions. Re Anti-deposition and soil suspending agents, fluorescent brighteners, bleaching agents, bleach activators, foam inhibitors , anticoagulants, dyes and pigments are examples of such optional ingredients, and various Can be added in quantities.

Suitable anti-redeposition and soil suspending agents here include methyl cellulose, carboxylic Cellulose derivatives such as dimethylcellulose and hydroxyethylcellulose There is. These substances usually constitute 0.5 to 10% by weight of the composition, more preferably 0.5% to 10% by weight of the composition. It is used at a level of 75-8% by weight, most preferably 1-6% by weight. They are Used not only in granular detergent compositions but also in liquid detergent compositions to supplement the suspending agent. can.

Preferred fluorescent brighteners are anionic in nature, examples of which include 4,41-bis(2 -jetanolamino-4-anilino-5-)riazin-6-ylamino)sti Rubene-2: 21-disulfonic acid disodium, 4.4” bis(2-morpholino -4-anilino-s-triazin-6=ylamino)stilbene-2:21-di Disodium sulfonate, 4,41-bis(2,4-dianilino-5-triazid) (6-ylamino)stilbene-2; 21-disulfonic acid disodium, 4, 41 11-,,.

(2,4-dianilino-8-triazin-6-ylamino)stilben-2-su Sodium sulfonate, 4.41-bis[2-anilino-4-(N-methyl-N -2-hydroxyethylamino)-S-triazin-6-ylaminocostilbe N-2: 21-disulfonic acid dinatriram, 4,4 bis(4-phenyl-2, 1,3-triazol-2-yl)stilbene-2:21-disulfonic acid dinato 4,4 bis[2-anilino-4-(1-methyl-2-hydroxyethyl Ruamino)-S-triazin-6-ylaminocostilbene-2:21-disul Disodium phonate and 2-stilbyl-411-(naphtho-11,2,4,5 )-1,2,34s1.

Sodium azole-211-sulfonate.

Any particulate inorganic superhydrated bleach contains 3 to 40% by weight of the composition, more preferably 8 It can be used in amounts of ~25% by weight, most preferably 12-20mff1%. This way Preferred examples of bleaching agents include sodium perborate hydrate and tetrahydrate, percarbonate. and a mixture thereof.

Another preferred separately mixed ingredient is bleach activator, commonly referred to as a bleach activator. Oxycarboxylic acid bleach precursor, which is present in globular or aggregated form in granular detergents. It is preferable that it be added in . An example of a suitable compound of this type is British Patent No. 15 No. 86769 and No. 2143231 and their shape into small spheres. A method for the preparation is described in European Published Patent Application No. 0062523. This way Preferred examples of such compounds are tetracetylethylenediamine and 3,5,5-tritriamine. Sodium methylhexanoyloxybenzenesulfonate.

The bleach activator usually comprises 0.5 to 10% by weight of the composition, more often 1 to 8%, preferably Preferably, it is used at a level of 2 to 6% by weight.

Another optional ingredient is exemplified by silicones and silica-silicone mixtures. It is a foaming inhibitor. Silicones are usually represented by alkylated polysiloxane materials. silica, while silica can be found in various types of silica aerogels, xerogels and hydrophobic silicas. It is usually used in the microscopic form shown below. These substances have foam suppressants that are water-soluble or is water-dispersible and virtually non-surfactant, allowing for advantageous release in detergent-impermeable carriers Can be formulated as blended particles. On the other hand, the foam suppressant is used as a liquid carrier. It may also be applied by dissolving or dispersing and spraying onto one or more other ingredients.

As mentioned above, useful silicone suds control agents include alkylated siloxanes of the type mentioned above. silica and solid silica. Such a mixture is a solid silicon It is manufactured by adding silicone to the surface of the mosquito. Preferred silicone foam system The control agent has a silicone to silanized silicone weight ratio of about 1:1 to about 1=2 and a weight ratio of about 500 to about 1:2. Thoroughly mixed with dimethyl silicone fluid with molecular weight in the range of 200,000 Hydrophobic silicone having a particle size in the range of 10 to 20 mμ and a specific surface area of 50 rrr/g or more It is typified by lanated (most preferably trimethylsilanated) silica.

A preferred silicone suds control agent is Bartol Iota et al., U.S. Pat. No. 3.9. No. 33,672.

Other particularly useful suds suppressants include a German patent published April 28, 1977. The self-emulsifying silicone material described in Application DTO 3 No. 2,646,126 It is a foam suppressant. An example of such a compound is Dow Corning. DC-544, commercially available from Ing. It is a copolymer.

The foam suppressor L is usually 0.001 to 2% by weight of the composition, preferably [7 or 001 to 1% by weight]. Used at the level of % by weight.

The formulation of the foam control agent is preferably obtained as separate particles, thereby High MW copoly of fatty acids, microcrystalline wax, ethylene oxide and propylene oxide Other foam control substances such as polymers can be included therein, and these If not, the dispersibility of the matrix will be affected by 1j. This kind of foaming Techniques for forming modulating particles are described in Bartol Iota et al., U.S. Pat. No. 3,933. It is disclosed in the specification of No. 672.

Other useful polymeric materials have molecular weights specifically between 1,000 and 10,000, and more specifically Target Ni+, t 2000-8000.

Most preferred are about 4000 polyethyl non-glycols. These are 0. 20-50-5 weight preferably at a level of 0.25-2.5fffffi96 used. These polymers and the homo or copolymer polycarboxylate The polymer remains white in the presence of transition metal impurities, fabric ash deposits and clay, protein It is beneficial to improve the quality and cleaning efficacy of oxidative spills.

Soil release agents useful in the compositions of the invention conventionally include terephthalate under various configurations. Copolymers of acid and ethylene glycol and/or propylene glycol units or is a terpolymer. Examples of such polymers are generally assigned U.S. Pat. No. 116885 and No. 4711730 and European Published Patent Application No. 0272033 Disclosed in the specification. Particularly preferred in European Patent A 0272033 The polymer has the following formula: (CIl (PEG)) (POI+) [(T -PO) (T-PEG) 3 430.75 0,25 2.8 °, 4]T(POI+) ((PEG)43el+3). , 750.25 In the above formula, PEG is -(QCH)O-1po is COC3H60) and Ti;i (pc OC6H4CO) There is.

Typical +:: MW5000-20000. Preferably 10,000 to 15,000 Certain polymeric materials, such as polyvinylpyrrolidones, can also be mixed between fabrics during the cleaning process. forms a useful agent in inhibiting the migration of labile dyes.

In other /+i fabric softener inventions, it can be incorporated into detergent compositions. These agents are It may be inorganic or organic in type. British patent for fT machine fabric softener As disclosed in No. A 1514276 and European Patent No. B 0011340. Water-insoluble tertiary amines, European Patent B 0026527 and European Patent B 0 026528 and the mono-C-C quaternary ammonium salt combinations and di-long chain amides as disclosed in EP B 0242919. There are types. Other useful organic components for fabric softening systems include European Patent A 029957. 5 and 0313146. There is an oxide substance.

Organic fabric softeners such as water-insoluble tertiary amines or di-long chain amide materials range from 0.5 to Formulated at a level of 5% by weight, usually 1-3% by weight, -blade high molecular weight polyethylene The content of oxide substances and water-soluble cationic substances is 0.1 to 2% by weight, usually 0.15 to 1. Added at a level of 5% by weight. In the case of granular detergents, these substances are present in the spray of the composition. are usually added to the dry part, but in some cases they are combined with dry mixed particles. or spray them as a molten liquid onto other solid components of the composition. That would be more convenient.

Here certain cellulase preparations such as proteases, lipases and amylases Other enzymes can also be present in the composition.

manufacturing process The compositions according to the invention, depending on whether they are liquids or granules, are suitable for temperature and p. Liquid mixing, melting, dissolving, drying mixing, spray drying according to H time distribution Manufactured by various methods including drying, agglomeration, granulation and combinations of all these techniques be able to.

Preferred method for producing granular detergent compositions, especially the present compositions with high density (compact) The method consists of a combination of spray drying, flocculation in a high speed mixer and dry mixing. .

The first granule component containing a relatively insoluble anionic surfactant is spray dried. A portion of the spray-dried product is repurposed and reduced to low levels before being reblended with the remainder. sprayed with a nonionic surfactant. The second granule component is Lodigi (Lodige). jge) Sodium carbonate as a neutralizing agent in a continuous high-speed blender such as a KM mixer. Produced by dry neutralization of anionic surfactant acids using chlorine. Then, The first and second components are carboxyl chelating agents and inorganic peroxygen bleaching agents. , bleach activators, soil suspending agents, silicates, polycarboxylate polymers and It is fed to a conveyor belt along with other dry mix ingredients like enzymes, where it They are then transferred to a horizontal rotating drum where the fragrance and silicone suds suppressant are manufactured. Sprayed on the product. In highly preferred compositions, low (approximately 2%) levels of Microcrystalline aluminosilicate is introduced to increase density and improve granule flow properties. A drum mixing step is also used.

Regarding the preferred method of manufacturing a liquid detergent composition according to the invention, the liquid detergent composition comprises p Useful when H and temperature are always kept constant or reduced during the production of liquid detergents. It was discovered that it can be manufactured to advantage.

Example The following examples illustrate the invention and facilitate its understanding.

The abbreviations for the individual components have the following meanings.

LAS: Sodium salt of linear dodecylbenzenesulfonic acid TAS: 1 Sodium salt of fatty alcohol sulfuric acid AS/alkyl (CF4 ~C,5) Sodium salt of liK acid A O: C12-C14 alkyl dimethyl Amine oxide FA25E7 Ethoxylated with about 7 moles of ethylene/oxide (CI2-C15) Fatty alcohol CAT: C12-C14 trimethyl (also is dimethyl (hydroxyethyl) ammonium chloride clay, Montmorillo night clay Zeolite I-4A: Sodium zeolite 4A with an average particle size of 1 to 10 μm salt 5KS-6 crystalline multilayer silicate (Ilockst) AA/MA: Acrylic Copolymerizable polycarboxylate polymer of lylic acid and maleic acid PAP: Polyacrylic acid polymer, molecular weight 1000 → CMC: Carboxy Methylcellulose phosphonate: Ethylenediaminetetramethylenephosphonic acid sodium salt of AO5+ A-olefin (CI2-Cl8) sulfonic acid, sodium salt NMN: N-methyl N-1-deoxyglycityl (CI2-018) alkyl Amide EDTA: Ethylenediaminetetraacetate Nato P B 4: N a B O-H0・3 H20TAED-tetraacetylethylenediamine N0B S+ Sodium nonanoyloxybenzenesulfonate P, A,: Sulfonated phthalocyanine zinc silicate (R-n): SiO/ Na20-n amylase: Termasyl OUT (Novo-Nord lsk) Lipase: Lipolasc LOOT (Novo-Nordls k) Protease: 5avinase 4T (Novo-Nordlsk) SP 300: Celluzyme 5P300 (Novo-Nord prior art cellulase manufactured by lsk) 43kD. Approximately 43kD cellulase by cellulase defined in the present invention SSS Foam control system (silica/silicone mixture) NTA: Nitrilotriacetic acid Sodium salt TAE-1,1: Ethoxylated with about 11 moles of ethylene oxide tallow alcohol DTMA Two tallow methylamine CFA・Yang oil fatty acid HFA: Hydrogenated C fatty acid ■6～22 To facilitate comparison of softness, the following test treatment method was used.

Automatic drum type washing machine 1v1ieleR42 can wash 3.5 kg of clean canned food. Wash at 60℃ for 1.5 hours in 3.2 + 2 + Ta. The hardness of water is 25 moles of Ca/Mg per liter, and this composition concentration The concentration was 0.7% in the cleaning solution. To evaluate softness, pile towel softness training rliI and yI were added. Light a softness tracer before evaluating softness. and dried.

The test results were evaluated using two methods.

Softness J・1 value for comparison was determined by expert judgment using a panel scoring unit scale from O to 4. Sadone went. In this scale, 0 is given as 1-7 when there is no difference, and 4 is given as maximum difference. given to.

The softness is determined by the softness of worn-out pile (+i cut) after 8 washing cycles as shown in F. evaluated.

The other softness evaluation is performed using Kawabata KES, a laboratory softness measuring device. - FBI equipment, Kat.

It was carried out using Tech Corporation Ltd, Japan.

In this device, the softness tracer is placed between two mutually movable lamps. be done. Comparison softness is 8 with shear hysteresis at a 5 degree angle (2HG5). Jl was determined after two wash cycles. Reducing shear hysteresis increases softness performance. reflected the addition of ? 1#j constant value is the average value of 3 worn pile cloth pieces.

Aged usage is defined by a minimum of 10 regular washes.

Examples I-1v When evaluating detergent compositions as bases, EP-A- The composition selected for No. 177165 exhibits higher softening performance than the additive. vinegar.

Examples ① and 11 are obtained by combining softening clay and cellulase. Supports the prior art theory that no adverse effects occur. However, this conclusion The result is shown by the fact that even the profit of (=1) cannot be obtained.In fact, this prior technique The same benefits cannot be obtained from the combination of surgically disclosed clay and cellulase. This has not been commercially successful due to the ecological and economic burden it poses. It is thought that there is no.

In Examples Il+ and +V, 1v is according to the invention, but with a softening clay. clearly show that the performance of cellulase provides benefits for the use of additives. There is.

From Example 11, the benefit of clay is 0.3 °C in cellulase environment according to the prior art. Becomes a PSU. On the other hand, in Example 1v, where the test is conducted in a 43kD cellulase environment, , the result is increased by 6 times the amount -L and the number reaches 2 PSU.

All test results of Examples I to 1v are shown in the 11th! Shown in the table. The detergent compositions used are shown in Table V. The composition is based on composition 1. In the last two columns of Table 1II, softening clays and Overall superiority of the present invention for selected cellulases can be seen. However, this is clearly explained in history in the example of F. .

Example V-Vllll Composition 11 of Table V, which is a detergent composition as a base, was evaluated by the test method described above. Then, Al1 was determined using a Kawabata apparatus.

The decrease in the 4-1 constant value without softening was 5% with clay alone, and with high activity cellulase ring. In border-Germany, it is 15%. Therefore, the expected values for these combinations are approximately Surprisingly, this combination exceeded this expected value and r. It reached 39%, about twice the expected value.

Compositions 111-Xl+ of Table V contain a softening clay and a highly active cellulase, and In the embodiments found to be carried out in accordance with the objectives of the present invention, fabric processing performance is extremely high. It is in good condition.

The clay in these compositions is montmorillonite or hectorite clay; 10% for compositions 111-1v, 12% for compositions Vll, Vllll and X , the concentration was 8.6% for compositions x1 and Xl+. Composition IX is based on Ben Lone Contains R type anti-sedimentation agent 11 to prevent sedimentation of viscous 1 +t- It has become. Cellulase is generally added at a concentration of 0.01 to 1 per liter of wash solution. 0.0, preferably 0.1 to 0.5 mg is added.

Table 111 Compositions and Results of Examples 1-1v The test cleaning solutions were prepared using the detergents ( DI) contained 0.7% by weight.

When the clay of the present invention is added at 0.0875% by weight of the cleaning solution, SP10 For 0 cellulase protein, 2200X10' weight of wash solution? 0 and For 4'3kD, the cellulase will be 24X10% of the wash solution. Cellulase was added as shown.

These concentrations have equal CMC-endoase activity per liter of wash solution. It was selected to be 105 EVU.

Table 1v Synergistic effect material between clay and cellulase Cleaning solution IO’fftm96 Protein Table V Detergent composition Table V continued Table V Composition of detergents Table v continued Array SEQ ID NO:1: C(+AAATGACA (TCCCAATCA CTCTATTAGT TC TTGTACAT AATTTCGTCA TCCCTCC`G 1024 GATTGTCACA TAAATGCAAT GAGGAACAAτGAGT AC1060 array: SEQ ID NO: 2+ Iu Array: SEQ ID NO: 3: AAAAAAAMA AAAAAAAAA 147] Array/SEQ ID No. ・4; AsrIτ″hr Gly Gly Asp Leu G)y Asp Asr + Has Phi Asp Leu Met Met Pchichi B +30 135 140 Asp Ser Tyr Pro Glu Leu Shieu Lys Aso Gly Cys His Trp Arq Phe AsnTroPhe Gl u Asn Alx Asp Asn140 AS9 Phe Thr Phe Glu Gin Vil G1nCys Pr@uys Ala ueu eu Aso 11e Ser C1y Cys Lys Arg Aso Asp As.

2+0 215 220 Pro Gln Lys Thr Lys Asp Sfr Ala Pro Val　Vat　Glr+　Lys　Sfr　Sar　Th■ Lys Pro ATm Ala Gin Pro Glu Proτhr L ys Pro Ala Aso Lys Pro G1nIhr ASGI L ys Pro Val Ala Thr Lys Pro Ala Ala T hr Lys Pro Vat G1■ 290 295 Ko0O Pro Vat Asn Lys Pro Lys Thr Thr Gin Lys Val Arg Gly Thr Lys Thr305 310 3 15 ko20 ＾rg Gly Ser Cys Pro Ala Lys Thr ASGI Ala Thr Ala Lys Ala Ser VaP 325:l]0 3ko5 Val Pro Ala Tyr Tyr Gln Cys Gly Gly Sir Lys Sur Ala Tyr Pro Asn140 1345 Ko5O Gly Asn Leu ALa Cys Ali Thr C11Y Set Lys Cys Val Lys G1r+ Asn G attack■ Ko55 360 365 Director General of the Patent Office 1 Display of incident 1992 Patent Application No. 506597 PCT/MaJS 92100190 2 Name of the invention Detergent composition containing highly active cellulase and softening clay ３　Those who correct the truth Relationship to the incident: Patent applicant Shipping date: March 8, 1994 6 Target of correction Power of attorney, translation of specification and claims, translation of abstract Continuation of front page (51) Int, C1,5 identification symbol Internal office reference number (C12N 15156 C12R1:645) (72) Inventor: Beek, Andre Cesar, Belgium, Ponheiden, Patose Steenbeek, 273 I

Claims (24)

[Claims] 1. A detergent composition comprising a surfactant, a builder system, a softening clay and a cellulase. a composition in which the cellulase contains 25x the cellulase protein of the washing test solution. Radiolabeled carboxylic acid immobilized by C14CMC method at 10-6% by weight. A detergent composition characterized in that it removes at least 10% of methylcellulose. 2. The cellulase compound is Humicoia insolens, DSM180 Immune reactions with antibodies raised against highly purified approximately 43 kD cellulase derived from or homologous to the approximately 43 kD endoglucanase described above. A detergent set according to claim 1, consisting essentially of an endoglucanase component. A product. 3. The endoglucanase component of the cellulase has an isoelectric point of about 5.1. A detergent composition according to item 2 of the claimed scope. 4. said endoglucanase component or before said endoglucanase component The DNA sequence encoding the precursor and the endoglucanase component or its precursor A host cell transformed with a recombinant DNA vector carrying the encoding DNA sequence is It is possible to express the endoglucanase component or its precursor in the medium. The endoglucanase component can be recovered from the culture. producing said endoglucanase component by a method comprising cultivating said endoglucanase component; The detergent composition according to claim 2 or 3, which can be used as a detergent composition. 5. The cellulase compound is shown in the attached document ID No. It has the amino acid sequence shown in 2. is an endoglucanase enzyme or exhibits endoglucanase activity. A detergent composition according to claim 1, which is a homologous sequence. 6. The endoglucanase enzyme is a type of Humicolainsolens. A detergent composition according to claim 5, produced by. 7. The cellulase compound is shown in the attached document ID No. It has the amino acid sequence shown in 4. is an endoglucanase enzyme or exhibits endoglucanase activity. A detergent composition according to claim 1, which is a homologous sequence. 8. The endoglucanase enzyme is a type of Fusarium, such as Fusarium. Produced by Rium oxysporum, according to claim 7 Detergent composition. 9. The enzyme is produced by a DNA construct containing a DNA sequence encoding the enzyme. 9. A detergent composition according to any one of claims 5 to 8, which is produced by: 10. The DNA sequence is shown in the attached sequence document ID=1 or ID=3. The detergent composition according to claim 9. 11. The host cell is Triclodeluca or Aspergillus. A strain of mold such as Asperigillus oryzae, preferably Asperigillus oryzae. or Aspergillus niger, or Hansenula or S Yeast cells belonging to a strain of Saccharomyces, such as Saccharomyces Any of claims 5 to 10, which is a strain of Yces cerevisiae. The detergent composition according to item 1. 12. Where the host cell is a strain of bacteria, such as Bacillus, Streptococcus myces or E. Any of claim clauses 5 to 10, which is a strain of E.coli The detergent composition according to item 1. 13. The amount of oxygen protein released into the wash solution is determined by the cellulases mentioned above. 0.005 to 40 mg per liter of washing solution, preferably per liter of washing solution. Any of claims 1 to 12, which is contained in an amount of 0.01 to 10 mg. The detergent composition according to item 1. 14. The amount of softening clay ranges from 0.5% to 50%, preferably 5% by weight of the detergent composition. % to 20%, most preferably 8% to 15%. The detergent composition according to any one of the above. 15. The softening clay may be smectite, preferably montmorillonite or or hectorite clay with a cation exchange capacity of at least 50 meq/10 The detergent composition according to any one of claims 1 to 14, which is Og. 16. A polymeric clay flocculant may be present in up to 20% by weight of said clay in said detergent composition. The detergent composition according to any one of claims 1 to 15, further comprising: . 17. The substituted polysiloxane is preferably added up to 50% by weight of the clay of the detergent composition. or 1.1% to 20% by weight. . 18. The detergent according to any one of claims 1 to 17, which is a granular detergent. Composition. 19. The above composition contains only 15% by weight of inorganic filler salt and has a density of 1 liter of the composition. Detergent composition according to claim 18, which is from 550 to 950 g per liter. . 20. The inorganic filler salts mentioned above are alkali and alkaline earth metals of sulfuric acid and chloride. 20. A detergent composition according to claim 19, wherein the detergent composition is selected from the group salts. 21. Claim 19 also contains no inorganic filler salt in an amount exceeding 10% by weight. is the detergent composition according to item 20. 22. Claim 21, which does not contain an inorganic filler in an amount exceeding 5% by weight. detergent composition. 23. Claims 19 to 22, having a density of 650 to 850 g/liter The detergent composition according to any one of the items. 24. The builder is substantially free of phosphate compounds and the builder is substantially free of phosphate compounds. In addition to boxylate polymers, aluminosilicate ion exchangers, citrate, Claims also comprising compounds selected from carbonates and mixtures thereof The detergent composition according to any one of items 1 to 23.