JPS6036240B2 - cleaning composition - Google Patents

Description

[Detailed description of the invention]

The present invention relates to cleaning compositions. More specifically, the present invention relates to a cleaning composition characterized by containing a special cellulase produced from a specific cellulase-producing bacterium and having high enzymatic activity even in alkaline conditions.
・In recent years, there has been significant progress in washing clothes. That is, washing clothes has become significantly easier due to the development of raw materials that can be used in detergents, improvements in water quality, improvements and spread of washing machines, and improvements in fibers. Among these, improvements in raw materials for detergents, such as surfactants, builders, dispersants, crab light dyes, and bleaching agents, have made it seem as though the composition of laundry detergents has almost reached perfection. be. However, the idea behind the development of laundry detergent is that by absorbing dirt and/or surfactants and builders on the fiber surface,
Lowering the interfacial tension between dirt and/or fibers and water and separating dirt and fibers physically and chemically {2} Dispersing and solubilizing dirt with surfactants and inorganic builders, t3
}Chemical decomposition of dirt with enzymes such as protease, {
4) Bleaching colored stains with a bleaching agent, etc.; 5) Adsorbing crab light dye, etc. to the fiber surface to brighten it; (6) Using a chelating agent to remove precipitation caused by divalent metal ions, which are effective ingredients for cleaning. In other words, the basics of conventional clothing cleaning are how to effectively incorporate ingredients that directly attack stains or ingredients that assist in the attack power of these ingredients as a component of a detergent composition. Currently, in a sense, the cleaning performance of cleaning compositions based on this basic principle has almost reached a saturation point, and great efforts are required to further increase the cleaning power. We have been actively investigating whether it is possible to understand the various phenomena related to washing clothes from a completely new perspective without being bound by conventional preconceived notions, but it was completely unexpected that one enzyme, cellulase, has the enzyme activity of its main ingredient. He discovered that unexpected effects could be produced by acting on substances other than the one in question, and filed a patent application (Samurai Kai No. 57-10819, Tokkyo Sho 55-
No. 181879). However, the cellulase used in the invention disclosed in JP-A No. 57-108199 has an extremely low pH in acidic or neutral pH, and its cellulase activity decreases in the alkaline pH region, and even in the alkaline region there is a certain level of cellulase activity. Although it is effective, the original activity is not fully demonstrated, so further improvements have been made. Under these circumstances, the present inventors have discovered that cellulase produced by a specific cellulase-producing bacterium exhibits a slow decline in activity even in an alkaline region, and has significantly superior cleaning power compared to conventional cellulose-containing products. I also saw that
The present invention was completed. The special cellulase used in the present invention is a cellulase 212-producing bacterium belonging to the genus Aeromonas (Choken Bacteria Deposit No. 2306, Japanese Patent Publication No. 56-391).
All of these are special cellulases that maintain high activity even in alkaline regions and have alkaline tolerance. The present invention is characterized in that this special cellulase is used as a component of a cleaning composition, in which inorganic dirt, particularly inorganic dirt and oil secreted on the skin surface are mixed, which has nothing to do with cellulase activity. There is also a cleaning composition that exhibits remarkable cleaning properties against collar stains that change over time. As mentioned above, the use of enzymes in the technical field of detergents is known, but only enzymes that are particularly effective against dirt are known. That is, protease is known for protein stains, amylase is known for starch stains, and lipase is known for oil stains, and all of these enzymes attack stains directly. The cleaning mechanism of cellulase in the present invention has not yet been completely elucidated, but it is not based on the mere swelling action of fibers whose essence can be seen in surfactants. The great advantage of the present invention is that it is particularly effective in cleaning inorganic solid stains, such as fine mud stains, which conventional cleaning agents could not sufficiently remove.
It is also effective against stains such as stains on collars and cuffs, oil stains, etc. Furthermore, it is phosphorus-free and is extremely useful in improving the cleaning power of low-phosphorus detergents. Phosphate was effective in removing fine scale dirt that got between the fibers. However, due to the problem of eutrophication, the amount of phosphate added has been decreasing, and some fish have been forced to use phosphorous, making it extremely difficult to remove muddy dirt. It is well known that it is difficult to remove muddy dirt that has penetrated cotton cloth, especially dirt from areas where oil stains coexist. Housewives are also troubled by the muddy dirt that clings to canvas canvas made from a cotton blend. The cleaning agent of the present invention brings light to the solution of these problems. That is, when cleaning muddy stains on cellulose fibers and blended fabrics with other types of fibers, for example, by applying the present invention to an alkaline phosphorus-free or low-phosphorus detergent, By applying the present invention to a weakly alkaline liquid phosphorous detergent, it is possible to obtain excellent cleaning power equivalent to or better than that of a weakly alkaline powder detergent containing sufficient phosphates. Furthermore, this does not preclude the use of these special cellulases in neutral to weakly acidic detergents. Another great advantage of the present invention is that it can be applied to any form of cleaning agent. The product of the present invention can be obtained by adding cellulase to various forms such as mist-dried powder, powder blend powder, tablet, and liquid. There are no particular limitations on the components other than cellulase in the cleaning composition of the present invention, and they may be optionally blended, for example, depending on the need for the inherent effects of the following components. [1] Surfactant {1} A straight or branched alkylbenzene sulfonate having an alkyl group having an average of 10 to 16 carbon atoms. ■ It has a linear or branched alkyl group or alkenyl group with an average of 10 to 20 carbon atoms, and an average of 0.5 to 8 carbon atoms per molecule.
moles of ethylene oxide, propylene oxide, butylene oxide, ethylene oxide/f. . Pyrene oxide = o. 1 no 9.9
The ratio of ethylene oxide/butylene oxide is 0.1/9.9 to 9.9/0.1.
Alkyl or alkenyl ether sulfates added in a ratio of 1:1. '3' An alkyl or alkenyl sulfate having an alkyl or alkenyl group having an average carbon number of 10 to 20. [41 Olefin sulfonate having an average of 10 to 20 carbon atoms in one molecule. 5 Alkanesulfonate having an average of 10 to 20 carbon atoms in one molecule. 6 Saturated or unsaturated fatty acid salt having an average of 10 to 24 carbon atoms in one molecule. '7} Having an alkyl group or alkenyl group with an average carbon number of 10 to 20, and an average of 0.5 to 8 moles of ethylene oxide or propylene oxide in one molecule,
is butylene oxide, is ethylene oxide/
Propylene oxide = 0.1/9.9 to 9.9/0.
Alkyl or alkenylene carboxylate added in a ratio of 1 or ethylene oxide/butylene oxide in a ratio of 0.1/9.9 to 9.9/0.1. Q-sulfo fatty acid salt or ester represented by the following formula [wherein Y is an alkyl group having 1 to 3 carbon atoms or a counter ion, and Z is a counter ion. R represents an alkyl group or alkenyl group having 10 to 20 carbon atoms. ] Here, the counter ions of the anionic surfactant include alkali metal ions such as sodium and potassium, alkali metal ions such as calcium and magnesium,
Examples include ammonium ions and alkanolamines having 1 to 3 alkanol groups having 2 or 3 carbon atoms (eg, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.). {9} Amino acid type surfactant represented by the following general formula (where R. is an alkyl or alkenyl group having 8 to 24 carbon atoms, R2 is hydrogen or an alkyl group having 1 to 2 carbon atoms, and R3 is an amino acid residue) group, and X represents an alkali metal or alkali metal ion.) (R,, R2 and X are as described above, n represents an integer of 1 to 5.) R, is as described above. m represents an integer of 1 to 8. ) (R,, R3 and 6-hydroxyalkyl or 8
- indicates a hydroxyalkenyl group. ) (R3, R5 and X are as described above.) Rigid phosphate ester activator No. 1 Alkyl (or alkenyl) acidic phosphate ester (R' is an alkyl group having 8 to 24 carbon atoms or an alkenyl group, n'10m'=3, n'=1 to 2) No. 2 Alkyl (or alkenyl) phosphate ester (R' is as mentioned above, n''0m'' = 3, n'' = 1 to 3) No. 3 Alkyl (or alkenyl) phosphate ester salt (R, n'', m'
′ is as described above. M is Na, K, Ca) (11) A sulfonic acid type amphoteric surfactant represented by the following general formula (where R, . is a carbon number of 8 to
24 alkyl or alkenyl group, R, 2 has 1 to 1 carbon atoms
In the alkylene group of 4, R,3 represents an alkyl group having 1 to 5 carbon atoms, and R,4 represents an alkylene or hydroxyalkylene group having 1 to 4 carbon atoms. ) (Here, R, . and R, 4 are as described above. R, 5, R, 6 represent an alkyl or alkenyl group having 8 to 24 carbon atoms or 1 to 5 carbon atoms.) (Here, R, cicada R, , 4 are as described above. n represents an integer of 1 to 20.
~24 alkyl or alkenyl, 3-hydroxyalkyl or 8-hydroxyalkenyl group, R22 represents an alkyl group having 1 to 4 carbon atoms, and R spots represent an alkylene or hydroxyalkylene group having 1 to 6 carbon atoms. ) (Here, R2 and R23 are as mentioned above. Buddha is 1 to 2
Indicates an integer of 0. ) (Here, R2 and R23 are as described above. R24 represents a carboxyalkyl or hydroxyalkyl group having 2 to 5 carbon atoms.) (13) Average carbon number 10 to 2
A polyoxyethylene alkyl or alkenyl ether having 0 alkyl or alkenyl groups and to which 1 to 20 moles of ethylene oxide is added. (IQ has an alkyl group with an average carbon number of 6 to 12, and 1 to
Polyoxyethylene alkyl phenyl ether with 20 moles of ethylene oxide added. (15) Polyoxypropylene alkyl or alkenyl ether having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and to which 1 to 20 mol of propylene oxide is added. (16) Polyoxybutylene alkyl or alkenyl ether having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and to which 1 to 20 mol of butylene oxide is added. (17) A nonionic compound having an alkyl group or alkenyl group with an average carbon number of 10 to 20 and a total of 1 to 30 moles of ethylene oxide and propylene oxide, or ethylene oxide and butylene oxide added. Sexual activator (
The ratio of ethylene oxide to propylene oxide or butylene oxide is 0.1/9.9 to 9.9/0.1
). (18) Higher fatty acid alkanolamide or its alkylene oxide adduct represented by the following general formula [in the formula R', . is an alkyl group or alkenyl group having 10 to 20 carbon atoms, R',2 is H or CH3, n3 is an integer of 1 to 3, and m3 is an integer of 0 to 3. ] (19) A tung sugar fatty acid ester consisting of a fatty acid having an average carbon number of 10 to 20 and sucrose. (20) A fatty acid glycerin monoester consisting of a fatty acid having an average carbon number of 10 to 20 and glycerin. (2) Alkylamine oxide represented by the following general formula [wherein R', 3 is an alkyl group or alkenyl group having 10 to 20 carbon atoms, and R', 4, R', 5 is a carbon number 1 to (22) A cationic surfactant represented by the following general formula (
Here, at least one of R',, R'2, R'3, R'4 is an alkyl or alkenyl group having 8 to 24 carbon atoms,
Others represent an alkyl group having 1 to 5 carbon atoms. X' represents halogen. ) (where R',,R'2,R
'3 and X' are as described above. ) (Here, R', .R'2 and X' are as described above. R'5 is an alkylene group having 2 to 3 carbon atoms, and ~ represents an integer of 1 to 20.) One of the above surfactants The above components are preferably contained in the composition in an amount of 1% by weight or more. Preferred surfactants include 1), 2), 3), 4)
, 5), 6), 11) shame. 2, 12) M. 1, 13
), 14), 15), 17), and 18). [2] Divalent metal ion scavenger The divalent metal ion scavenger may contain 0 to 50% by weight of one or more of the following various alkali metal salts and alkanolamine salts. 1 Phosphates such as orthophosphate, biroIJ phosphate, tripolyphosphate, metaphosphate, hexametaphosphate, phytate, etc. 2 Ethane-1,1-diphosphonic acid, Ethane-1,1,
2-triphosphonic acid, ethane-1-hydroxy-1,1
-diphosphonic acid and its derivatives, ethane hydroxy-1
, 1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid and the like. 3 Salts of phosphonocarboxylic acids such as 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, and Q-methylphosphonosuccinic acid. 4 Salts of amino acids such as aspartic acid, glutamic acid, and glycine. 5 Nitrilotriacetate, imi/diacetate, ethylenediaminetetraacetate, jethylenetriaminepentaacetate, glycol etherdiaminetetraacetate, hydroxyethyliminodiacetate, triethylenetetraminehexaacetate, Aminopolyacetates such as genkolate. 6 polyacrylic acid, polyaconitic acid, polytaconic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, polymethaconic acid, poly-Q-hydroxyacrylic acid,
Polyvinylphosphonic acid, sulfonated polymaleic acid, maleic anhydride-diisobutylene copolymer, maleic anhydride-styrene copolymer, maleic anhydride-methyl vinyl ether copolymer, maleic anhydride-ethylene copolymer, maleic anhydride -Ethylene crosslink copolymer, maleic anhydride-vinyl acetate copolymer, maleic anhydride-acrylonitrile copolymer, maleic anhydride-acrylic acid ester copolymer, maleic anhydride-butadiene copolymer, maleic anhydride- Isoprene copolymer, poly 3-ketocarboxylic acid derived from maleic anhydride and carbon monoxide, itaconic acid-ethylene copolymer, itaconic acid-
aconitic acid copolymer, itaconic acid-maleic acid copolymer, itaconic acid-acrylic acid copolymer, malonic acid-methylene copolymer, methaconic acid-fumaric acid copolymer, ethylene glycol-ethylene terephthalate copolymer, Vinylpi. Lydone-vinyl acetate copolymer, 1-butene-2,3,4
-tricarboxylic acid-itaconic acid-acrylic acid copolymer,
Polyester aldehyde carboxylic acid with quaternary ammonium groups, cis-isomer of epoxysuccinic acid, poly[
N,N-bis(carboxymethyl)acrylamide],
Polymer electrolytes such as poly(oxycarboxylic acid), starch succinic acid or maleic acid, terephthalate ester, starch phosphate ester, dicarboxylate starch, dicarboxymethyl starch, cellulose succinate ester, etc. 7. Non-dissociable polymers such as polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, and cold water-soluble urethanized polyvinyl alcohol. 8 Salts of dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, t-glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decane-1,10-dicarboxylic acid; diglycolic acid, thiodiglycolic acid, Salts such as oxalacetic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, carboxymethyltartronic acid; glycolic acid, malic acid, hydroxypivalic acid, tartaric acid, citric acid, lactic acid, gluconic acid, mucic acid, glucuronic acid, dialdehyde Salts of hydroxycarboxylic acids such as starch oxide; itaconic acid, methylsuccinic acid, 3-methylglutaric acid, 2,2-dimethylmalonic acid, maleic acid, fumaric acid, glutamic acid, 1,2,3-propanetricarboxylic acid, aconite acid, 3-butene-1,2,3-tricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, ethanetetracarboxylic acid, ethenetetracarboxylic acid, n-
Alkenyl aconitic acid, 1,2,3,4-sic. Pentanetetracarboxylic acid, phthalic acid, trimesic acid,
Salts of hemimellitic acid, pyromellitic acid, benzenehexacarboxylic acid, tetrahydrofuran-1,2,3,4-tetracarboxylic acid, and tetrahydrofuran-2,2,5,5-tetracarboxylic acid: sulfitaconic acid, sulfotricarballylic acid , salts of sulfonated carboxylic acids such as cysteic acid, sulfoacetic acid, and sulfosuccinic acid; carboxymethylated products such as sucrose, lactose, and raffinose;
Carboxymethylated products of bentaerythritol, carboxymethylated products of gluconic acid, polyhydric alcohols,
are condensates of sugars and maleic anhydride or succinic anhydride; condensates of oxycarboxylic acids and maleic anhydride or succinic anhydride; organic acid salts such as CMOS and Builder M; 9 Aluminosilicate shame. Crystalline aluminosilicate x′(
M'20 or M''○)・Mountain 203・y′(Si02)・
w′ (ratio 0) (where M is an alkali metal atom, M″ is an alkali metal atom exchangeable with calcium, x, y,
w' represents the number of moles of each component, generally 0.7Sx
′≦1. 0.8≦y'≦6, w' is any positive number. ) No. 2. As the detergent builder, those represented by the following general formula are particularly preferred. Na20・AI203・nSi02・wH20 (here, n represents a number from 1.8 to 3.0, and w represents a number from 1 to 6.)M. Amorphous aluminosilicate x (
M20). AI203・y(Si02). w (ratio○) (
In the formula, M represents a sodium and/or potassium atom, and x, y, and w represent the number of moles of each component within the following range of values. 0.7SxSI. 2 1.6≦y≦2.8 w is any integer including 0) Ship. Amorphous aluminosilicate X (M
20)・AI203・Y(Si02)・Z(P2Q),
(day 20) (where M is Na or K, X, Y, Z,
represents the number of moles of each component within the following numerical range. 0.20SXSI. l0 0.20mi Ymi 4.00 0.001mi ZSO. (80: Any positive number including 0) [3] An alkaline agent or an inorganic electrolyte. Furthermore, as an alkaline agent or an inorganic electrolyte, one or more of the various alkali metal salts shown below are added to the composition. It can contain from 5 to 5% by weight, preferably from 5 to 30% by weight. Silicates, carbonates, sulfates. In addition, as an organic alkali agent, triethanolamine, diethanolamine, monoethanolamine, triisopropanolamine, etc. [
4] Anti-restaining agent Furthermore, one or more of the following compounds can be contained in the composition in an amount of 0.1 to 5% as an anti-restaining agent. Polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethylcellulose, etc.
Among these, the combined use of carboxymethyl cellulose or polyethylene glycol and the alkaline cellulase of the present invention has a synergistic effect in removing mud stains. In order to avoid decomposition of carboxymethylcellulose by alkaline cellulase in detergents, it is desirable to blend carboxymethylcellulose in the form of granulation or coating. [5] Bleach agents such as sodium percarbonate, sodium perborate, sodium sulfate hydrogen peroxide adduct, sodium chloride hydrogen peroxide adduct, and/or photosensitive agents such as sulfonated phthalocyanine zinc salt or aluminum salt. The combined use of a bleaching dye or the like with the alkaline cellulase of the present invention further improves the cleaning effect. [6] Enzymes (enzymes that perform their original enzymatic action during the washing process) Classified based on their reactivity, they include hydrozes, hydrolases, oxidoreductases, desmolases, transferases, and isomerases. However, any of these can be applied to the present invention. Particularly preferred are hydrases. Includes o-teases, esterases, hydrolubohydrases and nucleases. Specific examples of proteases include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, sptilisin, BPN, papain, promelin, carboxybeptidase A and B, aminobeptidase, As/Gooky, robeptidase A and B.
It is. Specific examples of esterases include gust IJ lipase, pancreatic lipase, plant lipases, phospholipases, cholinesterases, and phosphotases. Examples of carpohydrases other than the special cellulases featured in the present invention include conventional general cellulases, maltase, satucarase, amylase, vectinase, lysozyme, Q-glycosidase, and 8-glycosidase. [7] Blue tinting agents and halo dyes Various blue tinting agents and halo dyes can be added as necessary. For example, the following structure is recommended; (in the formula, D represents a blue to purple monoazo, disazo, or anthraquinone dye residue, and
May be substituted with a sulfonic acid group, carboxylic acid group, or alkoxy group. May be substituted with an aliphatic amino group, halogen atom, hydroxyl group, sulfonic acid group, carboxylic acid group, lower alkyl group, or lower alkoxy group. It is an aromatic amino group or a cycloaliphatic amino group. R is a hydrogen atom or a lower alkyl group. However, when R represents a hydrogen atom, (1) when X and Y simultaneously represent a hydroxyl group or an alkanolamine group, and (2) when either one of X and Y is a hydroxyl group and the other is an alkanolamine group, except. n represents an integer of 2 or more.
) (In the formula, D represents a blue to purple azo or anthraquinone dye residue, and x and Y represent the same or different alkanolamine residues or hydroxyl groups.) [8] In the case of anti-caking agent powder detergent The following anti-caking agents can also be added. paratoluene sulfonate, xylene sulfonate, acetate, sulfosuccinate, talc, finely divided silica, clay, calcium-silicate (e.g. Tohns-Man
Vill's Microcell, etc.), calcium carbonate, magnesium oxide, etc.

[9] Cellulase activity may be inactivated by the presence of ions and compounds such as copper, zinc, chromium, mercury, lead, manganese, and silver. Various metal chelating agents and metal precipitating agents are effective against these inhibitory factors. Examples thereof include the divalent metal ion total scavenger mentioned in optional component [2], magnesium silicate, magnesium sulfate, and the like. Cerbiose,
Glycols and gluconolactone are also sometimes inhibitors. It is necessary to avoid the coexistence of this type of bran and cellulase as much as possible, or, if coexistence cannot be avoided, to avoid direct contact between the bran and cellulase, such as a method of coating each of them. Strong chelating agents such as ethylenediaminetetraacetate, anionic surfactants, and cationic surfactants can also be inhibitors in some cases. The coexistence of these substances and cellulase is also possible by devising manufacturing techniques such as tableting and coating methods. The above-mentioned rice, agent, or method may be combined or applied depending on the case. [10] Cellulase activator Although it depends on the type of cellulase, when proteins, cobalt and its salts, calcium and its salts, potassium and its salts, sodium and its salts, monosaccharides such as mannose and xylose are allowed to coexist, Cellulase is activated and the cleaning effect is dramatically improved. [11] Antioxidant tert-butylhydroxytoluene, 4,4'-butylidenebis-(6-tert-butyl-3-methylphenol), 2
, 2-butylidene bis-(6-tert-butyl-4-methylphenol), monostyrenated cresol, distyrenated cresol, monostyrenated phenol, distyrenated phenol, 1,1'-bis(4-hydroxyphenyl) ) Antioxidants such as cyclohexane. [12] Solubilizers Lower alcohols such as ethanol, lower alkylbenzenesulfonates such as benzenesulfonates and p-toluenesulfonates, glycols such as propylene glycol, acetylbenzenesulfonates, acetamides , pyridine dicarboxylic acid amides, benzoates or urea. Thus, by using the cleaning composition of the present invention containing a special cellulase produced by cellulase 212-producing bacteria belonging to the genus Aeromonas, which has high activity in the alkaline region and has alkali resistance,
Excellent cleaning effects can be obtained over a wide range of areas. Furthermore, this effect provides an effect that more than compensates for the decrease in cleaning power due to the decrease in alkaline ability among the builder effects accompanying the decrease in the pH of the cleaning agent during cleaning. The enzymatic activity of cellulase applied to the present invention is measured as follows. That is, 50 pieces of Avicel (for chromatography) or carboxymethylcellulose (CMC) were mixed with 4'
After suspending in glycine NaCI-NaOH buffer (pH 8.3) and incubating at 37°C for 5 minutes, enzyme solution 1' was added, mixed well, and reacted for 1 hour. After the reaction is completed, the amount of reducing sugar is determined by the 3,5-dinitrosalicylic acid method. That is, after filtering the reaction solution, 1 part of the filtrate should be mixed with 3
, 5-dinitrosalicylic acid reagent 3' was added, heated at 100 oo for 10 minutes to develop color, and after cooling, 2' was added with ion-exchanged water.
5' and colorimetrically quantify it with a wavelength of 500. The unit of enzyme activity was defined as 1 unit/1 female enzyme when 1 of 9 solid enzymes produced reducing sugar equivalent to 1 French mole of glucose per hour under the above conditions. The content of the specific cellulase in the cleaning composition of the present invention is such that the cellulase has an enzyme activity of 0.001 unit/o solid content or more in the composition.
% by weight, more preferably 0.0% by weight.
It is 1 to 10% by weight. Alternatively, the content of cellulase is preferably such that the enzymatic activity of cellulase is 0.1 to 1000 units/sleeve, more preferably 1 to 100 units/sleeve.
Next, the present invention will be specifically explained using examples. Note that an example of the production of cellulase is shown as a reference example. % in example
are based on weight unless otherwise specified. Reference Example 1 Bacillus N4, a new bacterial species of the genus Bacillus (Choken Bacteria Deposit No. 1141) isolated from the soil of Hirosawa, Wako City, Saitama Prefecture, was mixed with 1.0% beptone, 1.0% meat extract, and carboxylic acid. Methyl cellulose (CMC) 1.0%, sodium chloride 0.5%,
Potassium dihydrogen phosphate 0.1%, anhydrous sodium carbonate 1
．． It was inoculated into a medium (Book 10) containing 0% and cultured at 370°C. After culturing for 7 hours, the bacterial cells were removed by centrifugation to obtain crude enzyme, which was then dried with ethanol by a conventional method to obtain cellulase powder. Ten cellulase enzyme preparations (enzyme activity at pH 6; 0.6 units/cloth solid content) were obtained per 1 culture solution (
(hereinafter referred to as Cellularsee N4). The enzyme obtained by this method maintained 85% of the enzyme activity at pH 9 at -6. In addition, commercially available cellulases such as Asparagillus niger showed 0% at pH 9, that is, no enzyme activity. Reference example Ammonium sulfate 0.5%, pulp block 1.5%
, glucose 0.02%, yeast extract 0.1%, M list 0
4 and 7 days 9M of medium containing 200.02% and K2HP040.2% was placed in a flask and sterilized for 120°C for 20 minutes.
0.7% NaHC03 aqueous solution low' separately sterilized after cooling
37q.
Shaking culture was carried out at 0. After culturing for 7 hours, the bacterial cells were centrifuged and cellulase 212
After obtaining the crude enzyme solution, it was dried with ethanol by a conventional method to obtain cellulase powder. The enzyme activity of this product was 0.55 units/9 solids at pH 6 (hereinafter referred to as cellulase 212). The enzyme obtained by this method has an enzyme activity at pH 6.
It was maintained at 70% in 9. The following examples were investigated under the following experimental conditions. 1. Multi-stain contaminated cloth, natural collar cloth contaminated cloth: Cotton gold cloth #2023 is sewn onto the collar of a dress shirt and made to be worn by an adult male for 2 days. After wearing, the degree of staining was divided into three levels, and from among the most heavily soiled fabrics, a fabric with stains that were symmetrical about the center point was selected, and the fabric was cut in half at the symmetrical point of staining and used for experiments.
2. Cleaning conditions and methods When cleaning naturally contaminated cloth, cut the naturally contaminated cloth (9 skins x 30 skins) in half at symmetrical positions, and use one of the pair of contaminated cloths (9 skins x 15 skins) with the standard detergent (no enzyme added). One side was washed with a comparative detergent, the detergent of the present invention. One piece of naturally contaminated cloth was placed in a 0.133% detergent solution, soaked at 400°C for 2 hours, washed with a tergotometer for 10000min, dried, and used for evaluation. A half-cut fabric washed with the standard detergent and a half-cut fabric washed with the detergent of the present invention were evaluated by pairwise comparison by visual judgment. The cleaning cloths were ranked based on standard soiling, which was ranked on a 10-level scale representing the degree of soiling. The detergency was expressed as a score for the detergency of the detergent of the present invention, with the detergency of the reference detergent set at 100. A difference in detergency index of 0.5 or more can be considered a significant difference. 3 Enzymes used ■ Cellulase N4 ■ Cellulase 212 ■ Cellulase (SIGMA, Origin Aspergllusnl bag r, 1.35 units/pair 9) ■ Lipase (Gist Brocades NV, Origin R. 0ryzae) ■ Amylase (Novo Industries) Inc., Termamil 6) ■Protease (Novo・
Industries, Inc., Alcalase 2.0M) Example 1 A highly alkaline powder laundry detergent was prepared using the following detergent formulation. Note that the pH of the 0.133% aqueous detergent solution was 11.2. Straight-chain sodium dodecylbenzenesulfonate 2% by weight Soap (soda of beef tallow fatty acid) 2 Sodium orthophosphate 20 Sodium metasilicate
10 carbonated soda 15
Ruboxymethylcellulose 1 Polyethylene glycol 1 Crab light dye 0.4 Reed Sulfur
Balance Enzyme 0 or 2 Moisture 5 Table 1 shows the results of the cleaning tests using the various detergents obtained. The detergent numbers in the table are expressed as Example number minus Enzyme number used. (However, for those that do not use enzymes, Example number - ■
is displayed. Table 1. Example 2 A weakly alkaline powder laundry detergent was prepared using the following formulation. The pH of a 0.133% aqueous detergent solution was 10.3. Sodium alpha olefin sulfonate 20% by weight Soap 1 Sodium tripolyphosphate 20 Sodium silicate (JIS No. 2 Keiso) 10 Sodium carbonate
5-force ruboxymethyl cellulose
1 Polyethylene glycol 1 Crab light dye 0.4 Ramie Glass
Balance enzyme 0 or 2 Water 10 Similar to Example 1, the results of the cleaning test are shown in Table 2.
Shown below. Table 2 Example 3 A neutral powder laundry detergent was prepared using the following formulation. The pH of the 0.133% aqueous detergent solution was 6.8. Straight chain alcohol (C=14) sulfate soda 3% by weight
Polyethylene glycol monophosphate sodium phosphate
1 Crab light dye 0.2E nitrate
Balance Enzyme 0 or 2 Moisture 5 The results of the cleaning test for each detergent are shown in Table 3. Table 3 Example 4 A phosphorus-free, weakly alkaline detergent was prepared using the following formulation. Straight mirror sodium dodecylbenzenesulfonate 15% by weight
Sodium alkylethoxy sulfate (C,4 to C,5,E. 23 moles) 5 builders and enzymes (see No. 4)
20 Sodium silicate 15 Sodium carbonate 15 Ruboxymethyl cellulose 1.5 Polyethylene glycol 1.5 Crab light dye
0.5 main salt balance moisture
5 The results of the cleaning test are shown in Table 4. Table 4 Builder - Enzyme Detergency index Sodium tripolyphosphate 20% - 100 (Standard detergent) Sodium citrate 20% - 984A type zeolite 20% - 98.5 Sodium citrate 15*■5
*98.54A type zeolite 15*■5* 98.5
Sodium citric acid 15 x 5 x 102 (invention)
〃 ■5% 102.5 ( 〃 ) 4A type zeolite 15% ■ 5% 101.5 ( 〃 )〃 〃
■5 many 102. (〃) Example 5 In the formulation of Example 2, detergents were prepared using various combinations of enzymes. Table 5 shows the results of the sedimentation test for each detergent obtained. Table 5 Example 6 A weakly alkaline powder laundry detergent was prepared using the following formulation. Sodium alkyl sulfate (C=14.5) 15%
Sodium alkylethoxy sulfate (D=14.5, Kan6
=3) 5 Soap (beef tallow-based)
2 Sodium pyrophosphate 1
8 Sodium silicate 13 Sodium carbonate 5 Polyethylene glycol 2 Crab light dye
0.2% trinitrate Balanced magnesium silicate 1 Water 5 Enzyme 2 Sodium percarbonate 15 Table 6 shows the results of the cleaning test for each detergent obtained. Table 6

Claims (1)

[Claims] 1 Cellulase 212-producing bacteria belonging to the genus Aeromonas (
A cleaning composition containing alkaline cellulase produced by Microtechnological Research Institute Deposit No. 2306).