JPS6116998A - Detergent composition - 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]

[Industrial Field of Application] The present invention relates to a cleaning composition. 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. [Prior Art] In recent years, there has been significant progress in washing clothes. That is, washing clothes has become much easier due to the development of raw materials suitable for detergents, improvements in water quality, improvements and spread of washing machines, improvements in fibers, etc. Among these, the improvement of raw materials for detergents has been remarkable, especially surfactants. With the modification of builders, dispersants, fluorescent dyes, bleaching agents, etc., the composition of laundry detergents seems to have reached a level of perfection. However, the philosophy behind the development of laundry detergent is
+11 By adsorbing surfactants and builders on the surface of dirt and/or fibers, the interfacial tension between dirt and/or fibers is lowered and the dirt and fibers are physicochemically separated. (2) Dispersing and solubilizing stains with surfactants and inorganic builders, (3) Chemically decomposing stains with enzymes such as protease, (4) Bleaching colored stains with bleach, etc., (5) This method can be summarized as whitening by adsorbing a fluorescent dye or the like on the fiber surface, and (6) using a chelating agent to prevent precipitation caused by divalent metal ions of ingredients effective in cleaning. In other words, the basis of conventional clothing cleaning has been how to effectively incorporate ingredients that directly attack stains or ingredients that assist in the attack power of these ingredients as components of detergent compositions. . [Problems to be solved by the invention 1 to 1] However, at present, the cleaning performance of cleaning compositions based on the above basics has almost reached a saturation point in a sense, and there is a need for cleaning agents with even higher cleaning power. The development of a composition has been desired. [Another means to solve the problem] The present inventors discovered that the activity of cellulase produced by a specific cellulase-producing bacterium decreases slowly even in an alkaline region, and has superior cleaning power compared to conventional cellulase-containing products. The present invention was completed based on the discovery that this is significantly superior. The special cellulase used in the present invention is produced by an alkalophilic actinomycete belonging to the genus Streptomyces, and is a special cellulase that maintains high activity even in an alkaline region and has alkaline tolerance. The microorganism used to produce the enzyme used in the present invention is an alkalophilic actinomycete belonging to the genus St. 1/Butomyces, and may be any microorganism or mutant strain thereof that has the ability to produce the cellulase of the present invention. As a strain of the alkalophilic actinomycetes belonging to the genus Streptomyces, Streptomyces axsubii (S
treptomyces sp, ) K S M −
2 (Feikoken Bibori No. 7621) and Streptomyces sp. These two strains were isolated by the present inventor from soil in Haga District, Tochigi Prefecture, and have the mycological properties shown in Tables 1 and 2 below. The KSM-2 strain and the KSM-9 strain have morphological characteristics of actinomycetes. Also, it is classified into the genus Streptomyces because its cell wall contains L-L-diaminopimelic acid. The KSM-2 strain belongs to the yellow series of strains based on the color of aerial mycelia on various agar media, the surface of the spores is smooth, the spore chains are slightly curved or generally straight, and they have a melanin-like appearance. Based on the fact that no pigment is produced and the results of a carbon source assimilation test, we searched for a similar flavor to this strain among known strains according to the Purging Manual, 8th Edition, and found that Streptomyces canescens
omyaes Canescens) is mentioned as a similar strain. However, whereas the KSM-2 strain produces alkaline-resistant cellulase, Streptomyces
The two differ in that Canescens does not produce alkaline-resistant cellulase. In addition, KSM-9 is also available in Virginie's Manual No. 8.
Search according to edition: Streptomyces x-Puniceus
is mentioned as a similar strain. However, whereas Streptomyces puniceus is characterized by producing purple to red pigments, KSM-9 does not have this property, and only KSM-9 is capable of producing alkaline-resistant cellulase. The two are different. Therefore, the present inventor developed the KSM-9 strain and KSM-2 strain.
The strain was identified as a new bacterial species and deposited at the Institute of Microbiology, Agency of Industrial Science and Technology as described above. Isolation of this bacterial strain from soil as an isolation source can be carried out by a conventional method using an agar medium, for example, as shown in Reference Example 1 below. The culture medium may be any medium as long as it is utilized by the strain used and contains carbon sources, nitrogen sources, organic nutrient sources, inorganic salts, etc. necessary for the successful production of alkaline cellulase. As a carbon source, for example, carboxymethyl cellulose (
Cellulose, such as soluble cellulose derivatives such as CMC), pulp powder, mouthpiece powder, and solid fibers such as Avicel; carbohydrates such as glucose, fructose, sucrose, or sorbitol; organic acids such as citric acid and succinic acid; n-
Any hydrocarbon that can be assimilated, such as dodecane, n-hexadecane, etc., can be used. Among these carbon sources, a medium using a soluble fiber derivative such as callose is preferable because it produces a large amount of alkaline cellulase. Examples of nitrogen sources or organic nutrient sources include nitrates such as sodium nitrate, potassium nitrate, and ammonium nitrate;
Examples include yeast extract, meat extract, and peptone. Examples of inorganic salts include carbonates such as carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, and potassium birophosphate. , phosphates such as sodium pyrophosphate, sodium tripolyphosphate, and sodium hexametaphosphate, and inorganic salts such as magnesium sulfate. Among these, a medium containing 0.1 to 1.5% by weight of carbonate is suitable because it produces a large amount of alkaline cellulase. In addition, trace amounts of heavy metal salts are used, but their addition is not necessarily required in media containing natural products. Furthermore, when using a mutant strain that requires nutritional sources other than those mentioned above, a substance that satisfies the nutritional requirements must be added to the medium. For culture, after sterilizing the medium by heating etc., inoculate the bacteria and inoculate it for 25 minutes.
What is necessary is just to shake or aerate and stir at ~35°C for 2 to 4 days. p
Good results can be obtained by adjusting H to about 8 to 11. When using a carbon source that is poorly soluble in water, it is also possible to add various surfactants such as polyoxyethylene sorbitan to the medium. As the cellulase used in the present invention, the above-mentioned culture solution itself may be used, or a crude enzyme solution obtained by removing bacterial cells by centrifuging the culture solution or the like may be used. Alternatively, an enzyme powder obtained by purifying the enzyme by ammonium sulfate fractionation or precipitation with an organic solvent such as acetone or ethanol may be used. As described above, Streptomyces sp. KSM-
The alkaline cellulase KSM-2 obtained by Streptomyces sp. KSM-9 and the alkaline cellulase KSM-9 obtained by Streptomyces sp. KSM-9 have the following physicochemical properties. In addition, in the table, the physicochemical properties such as the optimum pH showed similar results when Avicel was used as the substrate. In the present invention, cellulase activity was measured by the following method. <Cellulase activity measurement method> (1) CMC decomposition activity CMc2.5% m solution, glycine Na (4-NaOH buffer (500mM, pII9.o), and ion-exchanged water were mixed in a ratio of 2:1:1. Use as substrate. Add 0.1 ml of enzyme solution to 0.4 ml of substrate,
℃ for 20 minutes. After the reaction is completed, the amount of reducing sugar is determined by the 3.5-dinitro-salicylic acid method (DNS method). That is, add 1 s of DNS reagent to 0, s ml of the reaction solution.
ml, heated at 100℃ for 5 minutes to develop color, and after cooling, 4.5
Dilute by adding ml of deionized water. Wavelength 5
Colorimetric determination at 35 mμ. The control is 0.4 ml of substrate and 0.1 ml of enzyme solution 1% DN.
Add 0.5 ml of S reagent at the same time and immediately incubate for 5 minutes.
Color is developed by heating at 00°C' and colorimetrically determined in the same manner. (11) Avicel decomposition activity In the above method for measuring CMC decomposition activity, the reaction system was
1, add 50 μm of Avicel instead of CMC, react for several hours, and quantify the resulting reducing sugar colorimetrically in the same manner. In addition, unless otherwise specified, the enzyme activity is 1 under the above conditions.
The amount of reducing sugar produced by mg of enzyme per minute was determined as the glucose equivalent amount and evaluated. The content of the specific cellulase in the cleaning composition of the present invention is such that the enzyme activity of the cellulase is O1O former unit).
/ my solid content in the composition from 0.01 to
Preferably it contains 70 wt&%, more preferably 0
．． It is 1 to 10% by weight. Alternatively, the content of cellulase is preferably such that the enzyme activity of cellulase in the bath is 0.1 to 1000 units/e, more preferably 1 to 1000 units/e.
100 units/p. However, the unit of enzyme activity is 1r under the above-mentioned CMC decomposition activity measurement conditions.
1 unit/1 m when the n9 solid enzyme produces reducing sugar equivalent to 1 μmole of glucose per hour
9 Solid content. 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 cannot sufficiently remove, as well as stains on collars, cuffs, etc.
It is also effective against dirt such as oil stains, and is also very useful for improving phosphorus-free or low-phosphorus detergency. 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 products have had to be made phosphorus-free, making it extremely difficult to remove muddy dirt. Furthermore, it is well known that it is difficult to remove muddy dirt that has penetrated into cotton cloth, especially from areas where oil stains coexist. Housewives were also troubled by the stains that stuck to the cotton-blend canvas canvases. The cleaning agent of the present invention provides a solution to these problems. That is, when cleaning muddy stains on cellulose fibers and blended fabrics with other types of fibers, for example, (2) weak By applying the present invention to alkaline liquid phosphorus-free detergents, it is possible to obtain superior cleaning power equivalent to or better than weak alkaline powder detergents containing sufficient phosphate. Another great advantage of the present invention is that it can be applied to any form of cleaning agent. There are no particular limitations on the components other than cellulase in the cleaning composition of the present invention. [1] Surfactant (1) A straight or branched chain alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 16. (2) A straight or branched chain alkylbenzene sulfonate having an average carbon number of 10 to 20. Contains a branched alkyl group or alkenyl group, with an average of 0.5 to 1 molecule
8 moles of ethylene oxide, or propylene oxide, or butylene oxide, or ethylene oxide/propylene oxide = 0.1/9.9
~9.910.1 or ethylene oxide/
Butylene oxide-〇, 1/9.9-9.91
Alkyl or alkenyl ether sulfate added in a ratio of 0.1. (3) An alkyl or alkenyl sulfate having an alkyl group or alkenyl group having an average carbon number of 10 to 20. (4) 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) A saturated or unsaturated fatty acid salt having an average of 10 to 24 carbon atoms in one molecule. (7) Contains 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, propylene oxide, butylene oxide, or ethylene oxide/propylene in one molecule oxide in the ratio of 0.1/9.9 to 9.970.1 or ethylene oxide/butylene oxide
〇, alkyl or alkenyl ether carboxylate added in a ratio of 1/9.9 to 9.970.1. (8) α-sulfo fatty acid salt or ester R-CHCO2Y 5O1Z represented by the following formula (wherein, Y is an alkyl group having 1 to 3 carbon atoms or a counter ion,
2 is a counter ion. R represents an alkyl group or alkenyl group having 10 to 20 carbon atoms. ) Here, counter ions of anionic surfactants include alkali metal ions such as sodium and potassium, calcium,
Alkaline earth metal ions such as magnesium, ammonium ions, alkanolamines having 1 to 3 alkanol groups having 2 or 3 carbon atoms (e.g. monoethanolamine, jetanolamine, triethanolamine, triisopropanolamine, etc.) can be mentioned. (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,
R3 represents an amino acid residue, and X represents an alkali metal or alkaline earth metal ion. ) A 2 R, -CO-N-(CH2) n-C00X
(R+, R2 and
+, Rs and X are as described above. R4 represents hydrogen or an alkyl or hydroxyalkyl group having 1 to 2 carbon atoms. ) (R2, Rs and X are as described above. R5 has 6 to 2 carbon atoms
8 represents a β-hydroxyalkyl group or a β-hydroxyalkenyl group. ) (R3, R11 and Alkyl group or alkenyl group having 8 to 24 carbon atoms, n'+
m'= 3, n'= 1-2)ya2 Alkyl (or alkenyl) phosphate ester (R'O)n"-P-(OH)m'(R'ldAs mentioned above, n"+m"=3 .n”=1~3
) Section 3 Argyl (father is alkenyl) phosphate ester salt (R'0) n1LP-(OM)m〃 (R', n", rn'/ are as described above. M is Na,
K, indicates Ca. ) (11) A sulfonic acid type amphoteric surfactant represented by the following general formula (where R11 is an alkyl or alkenyl group having 8 to 24 carbon atoms, R□ is an alkylene group having 1 to 4 carbon atoms, and R13 is a carbon number 1 to 5 alkyl group, R1° represents an alkylene or hydroxyalkylene group having 1 to 4 carbon atoms. (R11 and RI4 are as described above. R, , R,
. represents an alkyl or alkenyl group having 8 to 24 carbon atoms or 1 to 5 carbon atoms. ) (C, H40) n, H (Here, RII and R14 are as described above. n is 1 to 2
Indicates an integer of 0. ) Betaine type amphoteric activator R12 represented by the following general formula of group, R2
, represents an alkylene or hydroxyalkylene group having 1 to 6 carbon atoms.
Indicates an integer of 0. (Here, R3 and R23 are as described above. R2 represents a carboxyalkyl or hydroxyalkyl group having 2 to 5 carbon atoms.) Polyoxyethylene alkyl or alkenyl ether to which 1 to 20 moles of ethylene oxide are added. 04) having an alkyl group with an average carbon number of 6 to 12, and 1 to 2
0 mo〃 of ethylene oxide is added to produce tapolyoxyethylene alkylphenyl ether. Of9 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. (g) Polyoxybutylene alkyl/L4U, fulkenyl ether having an alkyl group or alkenyl group having an average carbon number of 10 to 20 and to which 1 to 20 moles of butylene oxide are added. Q71 A nonionic activator having an alkyl group or alkenyl group with an average carbon number of 10 to 20 and adding a total of 1 to 30 moles of ethylene oxide and propylene oxide, or ethylene oxide and butylene oxide (
The ratio of ethylene oxide to propylene oxide or butylene oxide is 0.1/9.9 to 9.910
81). (To) Higher fatty acid alkanolamide or its alkylene oxide adduct represented by the general formula below, with spaces R', 2 R'12 [in the formula R'7. is an alkyl group or alkenyl group having 10 to 20 carbon atoms, and R' and 2 are H or CH. , n is an integer of 1 to 3, and ml is an integer of θ to 3. ] Moe A sucrose fatty acid ester consisting of a fatty acid with an average carbon number of 10 to 20 and sucrose. A fatty acid glycerin 7-ester consisting of a fatty acid with an average carbon number of 10 to 20 and glycerin. (21) Alkylamine oxide R' represented by the following general formula. R', 3- N→0 R', l+ [In the formula, R'13 is an alkyl group or alkenyl group having 10 to 20 carbon atoms, and % R'+4 1 '''+5 is an alkyl group having 1 to 3 carbon atoms. ] (2'IJ Cationic surfactant R' represented by the following general formula. (Here, at least one of R', , R', , R'3. R'4 has 8 to 24 carbon atoms. Alkyl or alkenyl group, others indicate an alkyl group having 1 to 5 carbon atoms. X/ indicates halogen) R'3 (where R/, , R%, R', and ) (R'IO) n4H (where R', , R'! and X' are as described above. R'l
is an alkylene group having 2 to 3 carbon atoms % n4ij: 1 to 2
Indicates an integer of 0. ) Preferably one or more of the above surfactants are included in the composition.
It has more than 00ij (hereinafter indicated by a circle). Preferred surfactants include +1), +21,
(3). A2 of (4), +5), (6), (11)
．． Examples include 1, (c), (]CQ[fl. (17), and (g). It is also possible to contain 0 to 50% of more than one builder component. (1) Phosphates such as orthophosphate, birophosphate, tripolyphosphate, metaphosphate, hexametaphosphate, phytate, etc. +21 Ethane -1,1-diphosphonic acid, ethane-1
, 1,2-1-lyphosphonic acid, ethane-1-hydroxy-
Salts of phosphonic acids such as 1,1-diphosphonic acid and its derivatives, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, and methanehydroxyphosphonic acid. (3) 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-)dicarboxylic acid,
Salts of phosphonocarboxylic acids such as α-methylphosphonosuccinic acid. (4) Salts of amino acids such as aspartic acid, glutamic acid, and glycine. (5) 2) IJ mouth triacetate, iminodiacetate, ethylenediaminetetraacetate, diethylenetriaminepentaacetate, glycol etherdiaminetetraacetate, hydroxyethyliminodiacetate, triethylenetetraminehexaacetate, diencholate Aminopolyacetate such as. (6) polyacrylic acid, polyaconitic acid, polyitaconic acid, polycitraconic acid, polyheptaconic acid, polymaleic acid, polymethaconic acid, poly-α-hydroxyacrylic acid, polyvinylphosphonic acid, sulfonated polymaleic acid,
Maleic anhydride-diisobutylene copolymer, maleic anhydride y[-methylene 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 ester copolymer, maleic anhydride-butadiene copolymer, maleic anhydride-isobrene copolymer, maleic anhydride Poly-β-ketocarboxylic acids derived from acid and carbon monoxide, itaconic acid-ethylene copolymers, itaconic acid-aconitic acid copolymers, itaconic acid-maleic acid copolymers, itaconic acid-acrylic acid copolymers , malonic acid-methylene copolymer, methaconic acid-fumaric acid copolymer, ethylene glycol-ethylene terephthalate copolymer, vinylpyrrolidone-vinyl acetate copolymer, 1-butene-2
, 3,4-) dicarboxylic acid-itaconic acid-acrylic acid copolymer, polyester polyaldehyde carboxylic acid with quaternary ammonium groups, eta-isomer of epoxysuccinic acid, poly(N,N-bis(carboxymethyl)) (71 Non-dissociable polymers such as polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, cold water soluble urethanized polyvinyl alcohol, etc. (8) Oxalic acid, malonic acid, succinic acid, curtaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decane Salts of dicarboxylic acids such as -1,10-dicarboxylic acid; salts of diglycolic acid, thiodiglycolic acid, oxalacetic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, carboxymethyltartronic acid; glycolic acid, malic acid, Hydroxypiparic acid, tartaric acid, citric acid, lactic acid, gluconic acid, mucic acid, glucuronic acid,
Salts of hydroxycarboxylic acids such as dialdehyde starch oxide; itaconic acid, methylsuccinic acid, 3-methylglutaric acid, 2,2-dimethylmalonic acid, maleic acid, fumaric acid, glutamic acid, 1°2,3-propanetricarboxylic acid , aconitic acid, 3-butene-1,2,3-)licarboxylic acid, butane-1,2,3,4-tetracarboxylic acid,
ethanetetracarboxylic acid, ethanetetracarboxylic acid, n
-Alkenyl aconitic acid, 1,2,3.4-cyclopentanetetracarboxylic acid, phthalic acid, trimesic acid, hemimellitic acid, pyromellitic acid, benzenehexacarboxylic acid, tetrahydrofuran-1,2°3.4-tetracarboxylic acid acid, tono salt of tetrahydrofuran-2,2,5,5-tetracarboxylic acid; salts of sulfonated carboxylic acids such as sulfoitaconic acid, sulfotricarballylic acid, cystic acid, sulfoacetic acid, sulfosuccinic acid; sucrose, lactose, Carboxymethylated products such as raffinose, carboxymethylated pentaerythritol, carboxymethylated gluconic acid, condensates of polyhydric alcohols or sugars with maleic anhydride or cono-phosphoric anhydride,
Organic acid salts such as condensates of oxycarboxylic acid and maleic anhydride or succinic anhydride, CMO8, Builder M, etc. (9) Aluminosilicate Al Crystalline aluminosilicate X/(M'0 or M〃0)・A&Os・y′(Si02
)・w'(鴇0)(In the formula, M' is an alkali metal atom, V
is an alkaline earth metal atom exchangeable with calcium, yc
/. y/, d represents the number of moles of each component, generally 0
．． 7≦x's;1.5.0.8≦y'≦6, V is any positive number. ) Ya2 As the cleaning agent builder, those represented by the following general formula are particularly preferred. Na2O・IJ, 0.・n,,SiO,-w[(,0
(Here, n represents a number from 1.8 to 3. OlW represents a number from 1 to 6.) SIO2)・w(H
, 0) (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 marginal value range: 0.7 ≦ X ≦ 1.2 1.6≦y≦2.8 W is any positive number including 0) Amorphous aluminosilicate x〃(M″20) ・Ag, 0. ・y″ (Sin,)
−z”(P2O,) +w(H2O) (where M′′
is as mentioned above. X", y"l"lω represent the number of moles of each component within the following numerical ranges: 0.20≦X"≦1.10 0.20≦y"≦4.00 0.001≦2 (≦0.80 ω: Any positive number including 0) [3] Alkaline agent or inorganic electrolyte Furthermore, as an alkaline agent or inorganic electrolyte, one or more of the various alkali metal salts shown below are used as a composition. It can contain 1 to 50 inches, preferably 5 to 30 inches. Silicates, carbonates, sulfates. In addition, as organic alkali agents, triethanolamine, jetanolamine, monoethanolamine, triisopropanolamine, etc. [4] Anti-restaining agent The composition may further contain 0.1 to 5 of one or more of the following compounds as an anti-restaining agent. Polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxymethyl cellulose. Among them, carboxymethyl cellulose or polyethylene glycol and the alkaline cell 2 according to the present invention
When used in combination with -Ze, it has a synergistic effect on removing muddy dirt. 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] Bleaching agents such as sodium percarbonate, sodium percarbonate, sodium sulfate hydrogen peroxide adduct, sodium chloride hydrogen peroxide adduct, and/or sulfonated phthalocyanine zinc salt,
Alternatively, the combined use of a photosensitive bleaching dye such as an aluminum salt and 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 enzyme reactivity, they include hydrolases, lyases, oxidoreductases, ligases, transferases, and isomerases. Any of these can be applied to the present invention. Particularly preferred are hydrolases, including proteases, esterases, carbohydrases and nucleases. Specific examples of proteases include pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, subtilisin, BPN, papain, promelin,
Carboxypeptidase A and B1 "aminopeptidase, asbergylopeptidase A and B. Specific examples of ester 2-ases include gastric lipase, pancreatic lipase, plant lipases, phospholipases, cholinesterases and Examples of carbohydrases other than the special cellulases featured in the present invention include conventional general cellulases, maltases,
Examples include saccharase, amylase, pectinase, lysozyme, α-glycosidase and β-glycosidase. [7] Blue-tinging agents and fluorescent dyes Various blue-tinging agents and fluorescent dyes can be added as necessary. For example, the following structure is recommended: A blue tinting agent represented by the following general formula (wherein represents a blue to purple monoazo, disazo or anthraquinone dye residue, X, Y, Hydroxyl group, amine group, hydroxyl group, sulfonic acid group, carboxylic acid group, aliphatic amino group which may be substituted with alkoxy group, halogen i, hydroxyl group, sulfonic acid group, carboxylic acid group, lower alkyl group, lower alkoxy It is an aromatic amine group or a cycloaliphatic amine group that may be substituted with a group.R" is a hydrogen atom or a lower alkyl group.However,
When R represents a hydrogen atom, ■When X and Y simultaneously represent a hydroxyl group or an alkanolamine group, and ■When one of X and Y is a hydroxyl group and the other is an alkanolamine group. Except in certain cases. B6 represents an integer of 2 or more. ) represents a quinone dye residue, and X2 and Y represent the same or different alkanolamine residues or hydroxyl groups. ) [8] Anti-caking agent In the case of a powdered detergent, the following anti-caking agent can also be blended. Para-toluene sulfonate, quiclene sulfonate, acetate, sulfosuccinate, talc, finely powdered silica, clay, calcium-silicate (e.g. Tohn
s-Manvi 11 microcell, etc.), calcium carbonate, magnesium oxide, etc.

[9] Inhibitor steel of a factor that inhibits cellulase activity,
Cellulase activity may be inactivated by the presence of ions and compounds such as 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 scavenger mentioned in optional component [2], magnesium silicate, magnesium sulfate, and the like. Cellbiose, gelcolate and gluconolactone are also sometimes inhibitors. It is necessary to avoid the coexistence of these types of saccharides and cellulases as much as possible, or, if their coexistence is unavoidable, to avoid direct contact between these saccharides and cellulases, such as a method of coating each of them. Strong chelating agents such as ethylenediamine/tetraacetate, anionic surfactants, and cationic surfactants may 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 anti-inflammatory agents or methods can 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 coexist, Cellulase is activated 17 and the cleaning effect is dramatically improved. [11] Antioxidant tert-butylhydroxytoluene, 4*4'-butylidenebis-(6-tert-butyl-3-methylphenol), 2
, 2'-butylidene bis-(6-37'thyl-4-methylphenol), monostyrenated cresol, cystyrenated resole, monostyrenated phenol, distyrenated phenol, 1.1'-bis-(4-hydroxy Antioxidants such as phenyl)cyclohexane. [12] Solubilizers lower alcohols such as ethanol, benzenesulfonates, lower alkylbenzenesulfonates such as p-toluenesulfonates, glycols such as propylene glycol, acetylbenzenesulfonates, acetamides, Solubilizing agents such as pyridine dicarboxylic acid amides, benzoates or urea. [Function] As described in the paper, the present invention is characterized by using a special cellulase as a component of a cleaning composition, but surprisingly, it contains inorganic dirt, especially inorganic dirt, which has nothing to do with cellulase activity. It exhibits remarkable cleaning properties for collar stains that change over time due to a mixture of dirt and oil secreted on the skin surface. 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 to be effective against protein stains, amylase is known to be effective against starch stains, and lipase is known to be effective against oil stains, all of which are enzymes that directly attack stains. The cleaning mechanism of cellulase in the present invention has not yet been completely elucidated, but it is not based on a mere swelling effect on the fibers, the essence of which can be seen in the surfactant. [Effects of the Invention] Thus, according to the present invention, the cleaning agent of the present invention contains a special cellulase having high activity in an alkaline region and having alkali resistance produced by live alkalophilic actinomycetes belonging to the genus Streptomyces. By using the agent composition, an excellent cleaning effect can be obtained in a wide range of pH ranges of the cleaning bath. Furthermore, this effect provides an effect that more than compensates for the decrease in detergency due to the decrease in alkaline ability among the builder effects accompanying the decrease in the pH of the cleaning bath during cleaning. [Reference example] Reference example 1 One cup of soil supertil (approximately 0.5 J) from Haga District, Tochigi Prefecture is 10+++A! The suspension was suspended in sterile water, thoroughly stirred, and left to stand. 0.1 ml of the soil suspension supernatant thus obtained,
It was applied to a separation agar medium having the following composition. Composition: CΔIIC2Qi peptone 1 (1 meat extract
IOP interval P0.
17NaCJ 1
0 PNa2Co310 g・Agar 7.5
J water 1000
+m! ! pH 10.5 Next, this was cultured at 30°C for 3 days, and C was added around the colony.
It was confirmed that bacteria with a clear zone based on the dissolution of MC appeared, and colonies forming a clear zone were collected and inoculated onto a slanted agar medium with the same composition as the above isolation agar medium, and incubated at 30°C for 30 minutes.
The strains on the 10 slanted media were confirmed macroscopically and microscopically to be the same strain. It was confirmed that the properties and physiological properties of these 10 strains on each medium were the same. The properties and physiological properties of the above-mentioned strains on each culture medium are as follows.
This is as shown in Table 2 and Table 2, and the present inventor has determined that Streptomyces sp.
es sp, ) KSM-2. Streptomyces e sp.
essp, ) K8M-9 was similarly isolated from soil in Haga District, Tochigi Prefecture. As a result of the above test, it was found that each of the 10 cultured bacteria was a single strain isolated from nature. Next, a loopful of the pure cultured bacterial strain on the slant medium is suspended in a cryopreservation vial containing a sterilized 10-tiglycerin aqueous solution (2 ml) and stored frozen at -80°C. After 3 months of frozen storage, a loopful of the suspension obtained by rapid thawing was resuscitated on an ordinary agar medium and examined for its properties and physiological properties on each medium under the same conditions as above. No change was observed from before. Furthermore, as a result of similarly examining the properties and physiological properties on each culture medium of the strains subjected to the above-mentioned freezing and thawing process repeated five times every month, no changes were observed. Reference Example 2 In a 500 ml Sakaro flask, 1.0% Avicel, 1.5% meat extract, 0.5% yeast extract, 0.1% potassium dihydrogen phosphate, 0.5% sodium carbonate (
Streptomyces sp, KSM-2 strain (Feikoken Deposit No. 7621) was inoculated into this liquid medium through a slant, and cultured with shaking at 30°C. After culturing for 2 days, the cells were removed by centrifugation, the resulting culture solution was fractionated with ammonium sulfate, and the resulting solid fraction was freeze-dried to obtain enzyme powder. 0.6 per culture solution? of enzyme powder was obtained. The CMC decomposition activity of the obtained enzyme was 1.84 and 1.02 at pH 7.0 and 9.0, respectively.
・min, and the Avicel degrading activity is similarly 0.min, respectively.
083■, 0.056■glucose equivalent amount/mti·min. Reference Example 3 In Reference Example 2, Avicel 1. CMC1 instead of O%,
Enzyme powder was obtained from the culture solution obtained by culturing Streptomyces sp, K8M-2 strain, in the same manner as in Reference Example 2, except that 0% was used as the carbon source. CM of the obtained enzyme
The C decomposition activity was 0.90 and 0.44 Fng glucose phase equivalent/■·min at pH 7.0 and 9.0, respectively. Reference Example 4 Streptomyces sp, KSM-9 as in Reference Example 2
The strain (Feikoken Bacteria Deposit No. 7620) was cultured and enzyme powder was obtained from the culture solution. The CMC decomposition activity of the obtained enzyme was 3.851n9 and 2.85nn9 at pH 7.0 and 9.0, respectively.
50 m9 glucose equivalent -°/mg·min. Reference Example 5 Streptomyces sp, K 5M as in Reference Example 3
Enzyme powder was obtained from the culture solution obtained by culturing -9 strain. The CMC degrading activity of the obtained enzyme was 2.01 m9 and 1.49 mQ glucose equivalent/at pH 7,0 and 9.0, respectively.
It was m9·min. [Example] In the following examples, studies were conducted under the following experimental conditions. 1) Contaminated natural collar cloth; Cotton gold cloth≠2023 cloth was sewn onto the collar of a dress shirt and an adult male was allowed to wear it for 3 days. After wearing 25'C, 651R
After leaving it in H for one month, the degree of staining was divided into three levels, and from among the most heavily soiled fabrics, the fabric with the stains symmetrical to the center was selected, and the fabric was cut in half at the symmetrical point of the stains and used for experiments. did. 2) Cleaning conditions and methods When cleaning naturally contaminated cloth, cut a 9 cm x 30 crn naturally contaminated cloth in half at symmetrical positions, and cut one of the 9 cm x 15 pieces of contaminated cloth in half with a standard detergent, an enzyme-free detergent. One side was washed with a comparative detergent, the detergent of the present invention. First, 15 pieces of naturally contaminated cloth were sewn onto a 50m x 50crn cotton cloth, and in the case of powdered detergent, 0.665 pieces of 6p
% detergent solution with this contaminated cloth and cotton underwear.
After adding kQ and soaking at 30°C for 2 hours, it was transferred to a Toshiba washing machine "Galaxy", the total volume was set to 30A, and it was washed with strong inversion for 10 minutes, and after drying, it was subjected to evaluation. 2oc for liquid detergent
Apply the detergent solution in c evenly to the contaminated cloth, and after 10 minutes, combine it with cotton underwear to make a total weight of 1 kg, transfer it to a Toshiba washing machine "Ginga", adjust the total volume to 30.8, and wash on high speed for 10 minutes. After drying, it was subjected to 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. Based on standard stains ranked in 10 stages to indicate the degree of stains,
The cleaning cloths were ranked. 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) Enzyme used ■ Cellulase of the present invention (obtained in Reference Example 2, diluted 20 times with Glauber's salt and granulated) ■ Cellulase of the present invention (obtained in Reference Example 3, diluted 20 times with Glauber's salt and granulated) Cellulase of the present invention (obtained in Reference Example 4, diluted 20 times with Glauber's salt and granulated)■
Cellulase of the present invention (obtained in Reference Example 5)
Cellulase (SIG
MA Type I, Origin: Aspergillus n
iger) ■ Lipase (Gist Procides n.
7 companies, origin: R,0ryzae) ■ Amylase (Novo Industries, Termamil 60G) ■ Protease (Novo Industries, Alcalase 2.0 M) Example 1 Highly alkaline powder laundry detergent was prepared using the following detergent formulation. did. In addition, the pH of a 0.665% aqueous solution of detergent is 11.3.
Met. Composition: Linear sodium dodecylbenzenesulfonate 20
% Soap (beef tallow fatty acid soda) 2 Sodium orthophosphate 20 Sodium metasilicate 10 Sodium carbonate
15 Carboxymethyl cellulose 1 Polyethylene glycol
1 fluorescent dye
0.4 awn glass
balance enzyme
O or 2 water
5. The results of the cleaning tests using the various detergents obtained are shown in Table 1. The detergent numbers in the table are expressed as Example number minus Enzyme number used. (However, those that do not use enzymes are indicated as Example No.-〇.) Table 1 Example 2 A weakly alkaline powder laundry detergent was prepared using the following formulation. The pH of the 0.6651 aqueous detergent solution was 10.5. Composition: Sodium alpha olefin sulfonate 10
Sodium linear dodecylbenzenesulfonate
10 Soap 1 Sodium tripolyphosphate 20 Sodium silicate (JIS No. 2 Keiso) 10 Sodium carbonate
5 Carboxymethyl cellulose 1 Polyethylene glycol 1 Fluorescent dye
0.4 awn salt
balance enzyme
0 or 2 water
10 As in Example 1, a cleaning test was conducted and the results are shown in Table 2. The following is a clue table 2. Example 3 A neutral powder laundry detergent was prepared using the following formulation. The pH of the 0.665% aqueous detergent solution was 7.2. Composition: Straight chain alcohol (C-14) sulfate soda 30
% polyethylene glycol 1
Sodium phosphate 1 fluorescent dye 0.2 awn
Nitrogen Balance Enzyme 0 or 2 Water
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. Composition: Linear sodium dodecylbenzenesulfonate 15
% Alkylethoxy Sodium Sulfate (CI4~C□, Ff
) = 3 mol) Builder and enzyme (see Table 4)
20 Sodium silicate 1
5 Sodium carbonate 15 Sodium polyacrylate 1.5 Polyethylene glycol 1,5 Fluorescent dye. , 5-point glass
balance moisture
Table 4 shows the results of the 5 cleaning tests. Table 4 below: Example 5 Detergents were prepared using the formulation of Example 2 in various combinations of enzymes. Table 5 shows the results of the cleaning test for each detergent obtained. Table 5 Example 6 A weakly alkaline powder laundry detergent was prepared using the following formulation. Composition: Sodium alkyl sulfate (C-14,5)
t 5% Sodium alkyl ethoxy sulfate (C-1
4,5,EO-3) Soap (beef tallow-based)
Sodium 2-pyrophosphate
18 Sodium silicate
13 Sodium carbonate 5 Polyethylene glycol 2 Fluorescent dye 02 Sodium salt
Balanced Magnesium Silicate 1 Moisture
5 enzymes
2 Soda percarbonate
Table 6 shows the results of the cleaning test for each detergent obtained. Table 6 Example 7 A weakly alkaline liquid laundry detergent was prepared using the following formulation. The pH of the detergent stock solution was 9.5. Composition: Secondary alcohol ethoxylate (C=13.5, E
O=7.0) 10 straight chain) '7' Sodium sylbenzene sulfonate
20 Coconut fatty acid diethanolamide 3
Carboxymethyl cellulose 1 Polyethylene glycol (MW6000) 2 Potassium pyrophosphate 14 Sodium formate
calcium monochloride
0.01 Sodium metaxylene sulfonate 5 enzymes
2 water
Table 7 shows the results of the cleaning test for each detergent that achieved a balance. 1 [Margin Table 7 Example 8 A neutral liquid laundry detergent was prepared according to the following formulation. The pH of the detergent stock solution was 7.0. Composition: Sodium alkyl ethoxy sulfate (C24~C,,,Eo-
3,t) mol) 20 Secondary alcohol (C=13.5) ethoxylate (EO
-7) Triethanolamine 1
Polyethylene glycol (MW 6000)
"Carboxymethyl cellulose
1 citric acid
1 Fluorescent dye 0.
3 Blue flavoring agent 0.05
EtO1 (8 Water Balance Enzyme 2) The results of the cleaning test for each detergent obtained are shown in Table 8.

[Brief explanation of drawings]

Figures 1 and 2 are diagrams showing the pH dependence of the alkaline cellulase activity obtained in Reference Example 5, Figures 3 and 4
The figure shows the pH dependence of the alkaline cellulase activity obtained in Reference Example 3. Above... Applicant: Kao Soap Co., Ltd. Figure 1 pH Figure 2 Figure 3 pH Figure 4 Thousand Continuing Amendment (Voluntary) August 1, 1980] Case Description 1981 Patent Application No. 136932 No. 2. Name of the invention Cleaning composition 3. Relationship with the case of the person making the amendment Applicant address 1-14-14 Kayaba-cho, Nihonbashi, Chuo-ku, Tokyo Title (091) Yoshi Maruta, Representative of Kao Soap Co., Ltd. Part 4, Agent 6, "Detailed Description of the Invention" column 7 of the specification subject to amendment, Contents of the amendment (1) In the specification, page 9, line 4, "Callose" is replaced with "cellulose". correct.

Claims (1)

[Scope of Claims] 1. A cleaning composition containing alkaline cellulase produced by alkaline cellulase-producing bacteria belonging to the genus Streptomyces. 2. The alkaline cellulase-producing bacterium is Streptomyces sp. KS
The cleaning composition according to claim 1, which is M-2 (Keikoken Kyoiyori No. 7621). 3. The alkaline cellulase-producing bacterium is Streptomyces sp. KS
The cleaning composition according to claim 1, which is M-9 (Keikoken Kyoiyori No. 7620).