FR2501227A1 - DETERGENT COMPOSITION CONTAINING ALKALINE CELLULASE - Google Patents

Abstract

THE INVENTION RELATES TO A DETERGENT COMPOSITION CONTAINING AN ALKALINE CELLULASE: THE COMPOSITION WHICH MAY IF NECESSARY CONTAIN OTHER CLASSICAL ACTIVE INGREDIENTS, HAS A DETERGENT EFFECT ON MINERAL SOIL.

Description

The present invention relates to a composition

  detergent containing an alkaline cellulase.

  More particularly, the invention relates to a detergent composition characterized in that it contains an alkaline cellulase which has a high activity in

alkaline conditions.

  Recently the techniques of debridement of clothes

  have made remarkable progress. Washing clothes

  has been greatly facilitated by the progress of the

  gentes, the conditioning of water, the improvement and

  diffusion of washing machines and fiber improvement.

  Among other things, the improvement of the raw materials

  tergents is remarkable. As a result of the improvement of surfactants, adjuvants, dispersants,

  fluorescent dyes and bleaching agents,

  detergent positions for clothes have almost reached the

  perfection. However, the evolution of detergents for clothing

  X (1) A surfactant or adjuvant is adsorbed on the surface of dirt and / or fibers to reduce the surface tension between dirt and / or fibers and water so that the dirt is separated from the fibers by

a physico-chemical phenomenon.

  (2) Scattered dirt is solubilized by means of an agent

  surfactant or mineral adjuvant.

  (3) The dirt is chemically decomposed by an enzyme such as

that a protease.

  (4) The stains are discolored by a bleaching agent.

  (5) A fluorescent dye is adsorbed on the surface of

to whiten it.

  (6) Precipitation of the active ingredients of the detergent by

  a divalent metal ion is prevented by a

latant.

  The fundamental principle of the detoxification of

  in the prior art is the efficient incorporation of a

  component that directly attacks dirt or a compound

  which increases the attack of this active ingredient in the

  composition. Currently the detergent powers of

  This fundamental principle has almost reached a maximum and considerable efforts have been

  necessary to further increase this detergency.

  After graduation from points of view

  differing from the classical principles of the detoxification of

  We have discovered that, unexpectedly, excellent detergent effects are obtained on dirt.

  on which the enzymatic activity of an alkaline cellulase

  This enzyme is generally ineffective when incorporating such an alkaline cellulase.

  a detergent. The invention is based on this discovery.

  Cellulases begin or cellvlases

  usually have an optimum pH in an acidic or neutral range and it is preferred not to use them in a

  alkaline domain because the cellulase activity is altered.

  The invention provides a detergent composition

  characterized in that it contains as a component a

  Alkaline alkaline having an optimum pH in an alkaline range.

  The invention provides a detergent composition having an ef-

  a remarkable detergent especially in the case of

  on which an alkaline cellulase is not

all active.

  As previously described, the use of an enzyme

  as a component of a detergent is known in the art.

  As enzymes we know only those that actually act

  on dirt. In particular, we do not know

  proteases against proteinaceous dirt, amylase

  its against saccharidic dirt and lipases against

  dirt consisting of oils and fats. These enzymes

  they attack the dirt directly. Although the mechanism

  detergent effects of alkaline cellulase in the invention.

  tion is not fully understood, it seems that it is

  simply about the expansion of the fibers as opposed to

; 01227

  phenomena observed when using surfactants

  assets. Important advantages of the invention are that the detergent is particularly effective in removing solid inorganic dirt, such as fine particles of sludge, which can not be sufficiently removed with conventional detergents and also to remove other dirt, such as stains on the collar and wrist of clothes and oily stains on clothes, and is very useful for increasing the detergency of detergents without phosphorus and detergents with low phosphorus content. Phosphate salts have been effective in removing fine particles of sludge having penetrated

  fibers. Recently, however, it has been necessary to reduce

  the amount of phosphate-type salts incorporated in the

  tergents as a result of an eutrophication problem. The need

  to use phosphate-free detergents makes the removal of

  sludge particles extremely difficult. In part-

  In particular, it is well known that it is very difficult to eliminate

  the mud particles having penetrated into the textures of

  cotton. Plus the muddy spots of the shoes

  canvas are difficult to remove by washing.

  The invention sheds new light on the problems

  my aforementioned. According to the invention, it is possible to obtain a

  see excellent detergent equivalent to or superior to a weakly alkaline powder detergent containing a sufficient amount of a phosphate salt, for example, (1) applying the invention to an alkaline detergent containing

  phosphate or with a low phospha-

  or (2) apply the invention to a liquid detergent,

  alkaline, phosphate free to clean mud stains of cellulose fibers or mixed fiber

  made of cellulose fibers and other fibers.

  Another important advantage of the invention is that it can be applied to detergents of all shapes. Alkaline cellulase can be incorporated into a

  form of a spray-dried powder, of metal powders

  diapers, tablets or liquids to obtain the

detergent section of the invention.

  The alkaline cellulases used in the invention

  are those with an optimum pH of 8.0 to 11.5 and

  preferably from 8.1 to 11.0. Under alkaline conditions, these enzymes

  show an activity equivalent to that observed in

  acidic or neutral conditions 4 OE obtains cellulases

  calines from culture fluids containing cel-

  lulase of various origins by purification and fractionation

  according to a method of release, precipitation, di-

  lysis or gel permeation. We also obtain

  alkaline lulases by fractionation of crude enzymes or purified enzymes by electrophoresis or by treatment with

  heat (for example at 40-90 OC for 0.5 min at 3 hrs).

res).

  As alkaline cellulases particularly pre-

  As used herein, the following enzymes may be mentioned: The particular cellulase used in the invention is preferably a cellulase produced by a Bacillus N fungus or a cellulase 212 producing fungus belonging to the genus Aeromonas. . Bacillus N is described in published patent JA-28515/75 and available

  Fermentation Research Institute, the Agency of In-

  Science and Technology 1-1-3, Higashi, Tsukuba-Ya-

  tabe-machi, Ibaraki, Japan. This organization included him in his

  permanent collection of micro-organisms under the reference

  deposit, FERM Nos. 1138, 1139, 1140 and 1141. The

  gnon of the genus Aeromonas was also included in the collection

  of micro-organisms from Fermentation Research Ins-

  the Agency of Industrial Science and Technology, under

  FERM No. 2306 and is described in the US Patent No.

  (not examined) JA-76287/75, subsequently published

under the reference JA-39191/81.

  The cellulase used in the invention

  comprises a cellulase extracted from the hepatopancreas of a mol-

  sea lobe (Dolabella Auricula Solander) which is described

  in Biochem. J. (1966) 99, 214-221.

  Each of the cellulases produced by these

  gnons is a particular cellulase which retains a high activity even under alkaline conditions and resists

with alkalis.

  The detergent composition of the invention is

  characterized in that it contains this particular cellulase

  as one of its indispensable ingredients. More by-

  particularly the invention provides a detergent composition

  having a remarkable power of washing away

  resistant mineral salts and the clean activity of cellulase,

  in particular fouling of the necks consisting of

  of mineral stains and oils secreted by the surface

  of skin, which evolve over time.

  When the detergent composition comprises a particular cellulase having a strong activity under alkaline conditions and also resistant to alkalis, produced by a fungus selected from Bacillus N (having

  deprive FRI-1138 & 1141) and a cell-producing fungus

  lase 212 belonging to the genus Aeromonas, an excellent washing effect can be obtained over a wide pH range of

washing bath.

  This excellent effect counterbalances the decrease in washing power due to the reduction of alkaline capacity

  of the adjuvant during the lowering of the pH of the wash bath.

  The enzymatic activity of the cell is determined.

  which is used in the invention according to the method

efore.

  50 mg of Avicel (for chromatin) are suspended

  tography) or carboxymethylcellulose (CMC) in 4 ml of

  Glycine-NaCl-NaOH buffer solution (having a pH of 8.3) and the suspension is preheated at 37 ° C. for 5 minutes then

  1 ml of a liquid enzyme is added to the suspension. We are

  mix the suspension sufficiently and react for one hour. After completion of the reaction, the

  amount of sugar reduced by the 3,5-di-

  nitrosalicylic. More particularly, the reaction mixture is filtered, 3 ml of 3,5-dinitrosalicylic acid is added to 1 ml of the filtrate and the mixture is heated at 100 ° C. for

  minutes to get a color. We cool the

  then mixed with deionized water to

  the total volume to 25 ml. We submit the liquid obtained &

  a colorimetric measurement at the wavelength of 500 nm.

  When one mg of the seed, in dry matter, is

  produces a reduced amount of sugar corresponding to 1 pmole

  of glucose in one hour in the cenditons cidessuss the ac-

  enzymatic activity is by definition 1 unit per

grams of dry matter.

  To achieve the purpose of the invention, these alkaline cellulases are combined with well-known detergent compositions. With regard to the alkaline cellulase content, it is preferred that the composition contain 0.01% by weight

  and in particular 0.1 to 10% by weight of an alkaline cellulase

  With an enzyme activity of at least 0.001 unit / mg dry matter, the unit / mg dry matter forms 1.0 pmol of glucose from the cellulose in one hour at

  37 C, pH 8.3 /. Also, the amount of cellulase

  caline is such that the enzymatic activity of cellulase

  alkaline in the bath is preferably from 0.1 to 1000

  tees / liter and better from 1 to 100 units / liter.

  Although the detergent composition of the invention can be used in an unlimited range of pH ranging

  from an acidic pH to an alkaline pH, it is preferred for the cell to

  alkaline solution has sufficient detergent effect, that the detergent bath is alkaline (and more particularly

has a pH of 7 to 11).

  In the detergent composition of the invention, the components other than cellulase are not particularly limited. For example, the following components can be incorporated into the composition according to their essential properties: Surfactants: (1) Linear or branched alkylbenzenesulfonate salts having an alkyl radical of 10 to 16 carbon atoms on average. (2) Alkyl or alkenyl ether sulphate salts having a linear or branched alkyl or alkenyl radical of 10 to

  carbon atoms on average, 0.5 to 8 moles on average

  ethylene oxide, propylene oxide or butylene oxide in the molecule and an ethylene oxide / propylene oxide addition ratio of 0.1: 9.9 to 9, 9 / 0.1 or ethylene oxide / butylene oxide 0.1 / 9.9

at 9.9 / 0.1.,

  (3) Alkyl or alkenyl sulphate salts having a radical

  alkyl or alkenyl of 10 to 20 carbon atoms on average

  born. (4) Olefin sulfonate salts having an average of 10 to 20

carbon atoms per molecule.

  (5) Alkanesulfonate salts having 10 to 20 carbon atoms

average bone in the molecule.

  (6) Salts of saturated or unsaturated fatty acids averaging 10

  to 24 carbon atoms in the molecule.

  (7) salts of the alkyl or alkenyl ether carboxylate type having an alkyl or alkenyl radical of 10 to 20 carbon atoms on average, 0.5 to 8 moles on average of ethylene oxide,

  propylene oxide or butylene oxide in the

  and an addition ratio of the ethylene oxide / oxy-

  of propylene from 0.1 / 9.9 to 9.9 / 0.1 or oxide of

  thylene / butylene oxide 0.1 / 9.9 to 9.9 / 0.1.

  (8) α-Sulfo-substituted fatty acid salts or esters

to the general formula:

R-CHCO 2Y

  Wherein Y represents an alkyl radical having 1 to 3 carbon atoms or a complementary ion, Z represents a complementary ion and R represents an alkyl radical.

  or alkenyl having 10 to 20 carbon atoms.

  As complementary ions of surfactants

  For example, alkali metal ions such as sodium or potassium, alkaline earth metal ions such as calcium and magnesium, ammonium, alkanolaxines containing 1 to 3 alkanol radicals having 2 or 3 carbon atoms, such as monoethanolamine, diethanolamine,

  triethanolamine and triisopropanolamine.

  (9) Amino acid-type surfactants having the general formulas: N151 R1-CO-N-CH-COOX R2 R3

  in which R 1 represents an alkyl or alkenyl radical

  nyle having 8 to 24 carbon atoms, R2 represents a

  hydrogen atom or an alkyl radical having 1 or 2 atoms

  carbon, R3 represents an amino acid residue and

  X represents an alkali metal or alkali metal ion

  No earth. N 2 R 1 -CO-f (CH 2) nCOOX R 2 in which R 1 R 2 and X have the same meanings

  than above and n is an integer from 1 to 5.

N03 R1

N- (CH2) COOX

  R1 in which R1 has the same meaning as above

  and m represents an integer of 1 to 8.

N 4 R1 -1-CH-COOX

R4 R

4 3

  wherein R 1, R 3 and X have the same meaning as above and R 4 represents a hydrogen atom or an alkyl or hydroxyalkyl radical having 1 or 2 carbon atoms. Wherein R 2, R 3 and X have the same meaning as above and R 5 represents a P-hydroxyalkyl radical

  or β-hydroxyalkenyl having 6 to 28 carbon atoms.

N 6 R5

R \> N-C-COOX

  R5R / l R3 in which R3, R5 and X have the same meaning as

above.

  (10) Phosphoric ester surfactants.

  N 1. Alkyl (or alkenyl) acid phosphates

to the formula:

(R.), I- (OH) M,

  in which R 'represents an alkyl or alkenyl radical having 8 to 24 carbon atoms, n' + m 'represents 3 and n'

represents 1 or 2.

  N 2. Alkyl (or alkenyl) phosphates in accordance with

formula: -

  in which R 'has the same meaning as above,

  n "+ m, is equal to 3 and n" represents a number from 1 to 3.

  N 3. Salts of alkyl phosphate (or dialkenyl)

In the formula: If

(R'O) - n-P- (OM) m.

  in which R ', n "and m" have the same meaning

  than above and M represents Na, K or Ca.

  (11) Amphoteric surfactants of the sulfonic acid type having the general formulas: N 1 R 1?

ORCONH-R I (+ S.

he CN-12-f <R4 3o R13

  in which R 11 represents the alkyl or alkenyl radical

  nyle having 8 & 24 carbon atoms, R2 represents im

  alkylene radical having 1 to 4 carbon atoms, R13

  has an alkyl radical having 1 to 5 carbon atoms and R14 represents an alkylene or hydroxyalkylene radical

having 1 to 4 carbon atoms.

No2

R

  R11- (+) -R14-S03-) R16 wherein R11 and R14 have the same meaning as above and R15 and R16 each represent a radical

  alkyl or alkenyl having 8 to 24 or 1 to 5 carbon atoms

bone.

  N 3 (C2H40) n1H R1 (+ IR14-3 (C2H40) n1H wherein R1 and R14 have the same meaning as

  above and n1 represents an integer from 1 to 20.

250 1227

  (12) Amphoteric surfactants general formulas of bstane type

  with general formulas: N o N22

R212N (+ R23_C00 (-)

21 1 23

  R22 wherein R21 represents an alkyl, alkenyl, 1-hydroxyalkyl or p-hydroxyalkenyl radical having 8 to 24 carbon atoms. R22 represents an alkyl radical having 1 to

  4 carbon atoms and R 23 represents an alkyl radical

  ne or hydroxyalkylene having 1 to 6 carbon atoms.

No2 (C H40) n2H (12 4) n2

R -

In which R21 and R23 have the same meaning as

  above and n2 represents an integer of 1 to 20.

N 3 R

  R1-i (+) - R23-C00 (-) R24 wherein R21 and R23 have the same meaning as above and R24 represents a carboxyalkyl radical or

  hydroxyalkyl having 2 to 5 carbon atoms.

  (13) Polyoxyethylene-alkyl- or alkenyl-ethers having a radi-

  alkyl or alkenyl carbon of 10 to 20 carbon atoms in

  medium and 1 to 20 moles of ethylene oxide added.

  (14) Polyoxyethylene alkylphenyl ethers having a radical

  kyle of 6 to 12 carbon atoms on average and 1 to 20

  moles of ethylene oxide added.

  (15) Polyoxypropylene alkyl or alkenyl ethers having a

  dical alkyl or alkenyl of 10 to 20 carbon atoms in

  medium and 1 to 20 moles of propylene oxide added.

  (16) Polyoxybutylene alkyl or alkenyl ethers having a radical

  alkyl or alkenyl carbon of 10 to 20 carbon atoms in

  medium and 1 to 20 moles of butylene oxide added.

  (17) Nonionic surfactants having a radical

  alkyl or alkenyl of 10 to 20 carbon atoms on average and 1 to 30 moles in total of ethylene oxide and propylene oxide added or of ethylene and butylene oxide added (the ratio of ethylene oxide to propylene oxide or butyl ether, not being 0, 1 / 9.9 to 9.9 / 0.1) e (18) higher fatty acid alkanolamides, or their products

  addition of alkylene oxide corresponding to the general formula

neral R'12 x (IHCHO) 3H

R CCON

(HCH20) 3H

R 12

  in which R'11 represents an alkyl or alkenyl radical

  nyl having 10 to 20 carbon atoms, R'12 is H

  or CH3, n3 represents an integer of 1 to 3 and m3

  present 0 or an integer of 1 to 3.

  (19) Esters of sucrose and fatty acid derived from fatty acids having on average 10 to 20 carbon atoms and

sucrose.

  (20) fatty acid glycerol monoesters derived from fatty acids having on average 10 to 20 carbon atoms and glycerol. (21) Alkylamine oxides having the general formula: r 14

R '13-'

RI 0 R'1

  in which R'13 represents an alkyl or alkenyl radical

  nyl having 10 to 20 carbon atoms and R'14 and R'15 having

  each have an alkyl radical having 1 to 3 carbon atoms

O01227

carbon.

  (22) Cationic surfactants according to the

the general N 1

R'2

R 1 - () RI4 I XI ()

  in which at least one of the symbols R'1, Rt2, Rt3 and R'4 represents an alkyl or alkenyl radical having 8 to

  24 carbon atoms and the remaining symbols represent

  an alkyl radical having 1 to 5 carbon atoms and

Xt represents a halogen.

N02 R

I [R'1 (+ 'CH2C6% l XT (j) R'

  in which Rt1, R'2, R3 and X 'have the same significance

as above.

N 3 (R 50) n 4 H R '-N (+ R 1 2 Xi)

2 0 1

  (R'50) n4H wherein R'1, R'2 and X 'have the same meaning v as above, R'5 represents an alkylene radical having

  2 or 3 carbon atoms and n4 represents a number

tier from 1 to 20.

  The compositions preferably contain at least one of the above surfactants at from

minus 10% by weight.

  Preferred surfactants include surfactants 1), 2), 3), 4), 5), 6), 11) - N 2, 12)

-N 1, 13), 14), 15), 17) and 18).

  [2] Sequestering agents divalent metal ions.

  The composition may contain from 0 to 50% by weight of one or more adjuvant components chosen from

  alkali metal salts or the dtalcanolamine salts of

following poses:

  1) Salts of phosphoric acids such as orthophosphoric acid

  phoric acid, pyrophosphoric acid, tripolyphosphoric acid,

  phoric, metaphosphoric acid, hexametaphos-

phoric and phytic acid.

  2) Salts of phosphonic acids such as ethane-1, l-

  diphosphonic acid, ethane-1,2-triphosphonic acid,

  ethane-1-hydroxy-1,1-diphosphonic acid and its derivatives are

  ethane-hydroxy-l: 1-2-triphosphonic acid,

  ethane-1,2-dicarboxy-1,2-diphosphonic acid and the acid

méthanehydroxyphosphonique.

  3) Salts of phosphonocarboxylic acids, such as acid

  2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphoic acid

  nobutane-2,3,4-tricarboxylic acid and methylphosphoric acid

  phonosuccinique. 4) Amino acid salts such as aspartic acid, acid

glutamic and glycine.

  ) Salts of aminopolyacetic acids such as nitric acid

  lotriacetic acid, iminodiacetic acid, ethylene

  diaminetetraacetic acid diethylenetriaminepentaacetic acid

  tick, the glycolic ether of diamine-tetracetic acid,

  Hydroxyethyliminodiacetic acid, triethylene acid,

  tetramine hexaacetic acid and dienkolic acid.

  6) Electrolytes of high molecular weight, such as

  polyacrylic acid, polyaconitic acid, poly-

  itaconic acid, polycitraconic acid, polyfunctional acid

  ric acid, polymaleic acid, polymaconic acid,

  Poly-1-hydroxyacrylic acid, polyvinylphosphoric acid,

  phonic, sulfonated polymaleic acid, a copolymer

  of maleic anhydride / diisobutylene, a copolymer of

  maleic hydride / styrene, a maleic anhydride copolymer

  leic / methyl vinyl ether, maleic anhydride / ethylene copolymer, crosslinked maleic anhydride / ethylene copolymer, maleic anhydride / vinyl acetate copolymer, maleic anhydride / acrylonitrile copolymer, maleic anhydride copolymer acrylic ester, a maleic anhydride / butadiene copolymer, a maleic anhydride / isoprene copolymer, a poly-p-ketocarboxylic acid derived from maleic anhydride

  and carbon monoxide, a copolymer of itaco-

  nique / ethylene, a copolymer of itaconic acid / acid

  aconitic, a copolymer of itaconic acid / maleic acid

  that a copolymer of itaconic acid / acrylic acid, a copolymer of malonic acid / ethylene, a copolymer

  of mesaconic acid / fumaric acid, a tere-

  ethylene glycol / ethylene glycol, a copolymer of

  nylpyrrolidone / vinyl acetate, a 1-butene-2,3,4-tricarboxylic acid / itaconic acid / acrylic acid copolymer, a quaternary ammonium-containing aldehyde-carboxylic polyester-polyacid, the cis isomer

  epoxysuccinic acid, a poly [N, N-bis (carboxymethyl)

  thyl) acrylamide /, a poly (hydroxycarboxylic acid),

  a starch succinate, a starch maleate, a terephthalate

  starch, a starch phosphate, a dicarboxy starch,

  a dicarboxymethyl starch and cellulose succinates.

  7) High Molecular Weight Compounds Not Dissociating

  such as polyethylene glycol, polyvinyl alcohol,

  Polyvinylpyrrolidone and polyvinyl urethane alcohol soluble in cold water, 8) Salts of dicarboxylic acids, such as oxalic acid

  malonic acid, succinic acid, glutaric acid,

  that adipic acid, pimelic acid,

  azelaic acid and decane-l, 10-dicarboxylic acid.

  xylique; salts of diglycolic acid, thioacetic acid

  diglycolic acid, oxalacetic acid, hydroxydic acid and

  succinic acid, carboxymethylhydroxysuccinic acid and

  carboxymethyltartronic acid; the salts of hy-

  droxycarboxylic acids, such as glycolic acid, malic acid, hydroxypivalic acid, tartaric acid, citric acid, lactic acid, gluconic acid,

  mucic acid, glucuronic acid and dialkyl ether

  d6hydoamidon; the salts of itaconic acid,

  thylsuccinic acid, 2,2-dimethylmalonic acid, 3-methylglutaric acid, maleic acid, funmaric acid, glutamic acid, 1,2,3-propanetricarboxylic acid,

  of aconitic acid, 3,3-butane-1,2,3-tricarboxylic acid,

  that of butane-1,2,3,4-tetracarboxylic acid, acid

  Ethanetetracarboxylic acid, ethylenetetracarboxylic acid

  that, from an n-alkenylaconitic acid, 1,2,3,4-

  cyclopentanetetracarboxylic acid, phthalic acid,

  of trimesic acid, hemimellitic acid, pyromelic acid

  ionic acid, benzene hexacarboxylic acid, tetra-

  hydrofuran-1s2, 3,4-tetracarboxylic acid and tetracarboxylic acid

  hydrofuranne-2,2,5,5-tetracarboxylic; acid salts

  sulfonated carboxylic acids such as sulfo-itaco-

  sodium sulfotricarballylic acid, cysteic acid, sulfoacetic acid and sulfosuccinic acid; carboxymethylated sucrose, lactose and raffinose, carboxymethylated pentaerythritol, gluconic acid

  carboxymethyl, the condensates of polyalcohols or sac-

  charides and maleic anhydride or succinic anhydride, the condensates of hydroxycarboxylic acids and maleic anhydride

  or succinic anhydride and organic acid salts such as CMOS and Builder M.

9) Aluminosilicates: -

  N 1. crystalline aluminosilicate type salts having the formula: x '(Mt20 or MSO) .A. 203.y' (SiO2) .w, (H2O) in which M 'represents an alkali metal atom,

  M "represents an alkaline earth metal atom

  able by calcium, x ', y' and w 'represent the

  moles of the corresponding components and generally: 0.7 × 0.4 1.5, 0.8 y ys 6 and w 'represents

a positive number.

  N 2. Particularly preferred are the adjuvants of

  tergence corresponding to the following general formula: Na 2 O.A. 203nSiO 2 .wH 2 O wherein n represents a number of 1.8-3.0 and w represents a number from 1 to 6, N 3. Amorphous aluminosilicates having the formula: M20). A23. y (SiO 2) w (H 2 O) in which M represents a sodium and / or potassium atom, and x, y and w represent the number of moles of the corresponding components in the following ranges: 0.7 x 1.2 1.6 to 2.8

  w is zero or any positive number.

  N 4. Amorphous aluminosilicates having the formula: X (M20) .A203.Y (SiO2) .Z (P205). (H20)

  wherein M is Na or K; and X, Y, Z and

  present the number of moles of the respective components in the following ranges: 0.20 C X i 1.10 0.20 t Y _ 4.00 0, o001 Z -L 0.80

  L: is zero or any positive number

  than. [3 / Alkalis or inorganic electrolytes The composition may also contain 1 to 50% by weight, preferably 5 to 30% by weight, relative to the composition, of one or more alkali metal salts

  of the following compounds as alkalis or electrolytes half

  minerals: silicates, carbonates and sulphates.

  In addition, the composition may contain organic alkalis

  such as triethanolandne, diethanolamine,

  monoethanolamine and triisopropanolamine.

[47 Agents antiredAéposition.

  The composition may contain from 0.1 to 5% of one or more of the following compounds as antiredeposition agents:

  polyethylene glycol, polyvinyl alcohol, poly-

  vinylpyrrolidone and carboxymethylcellulose.

  In particular a combination of carboxymethyl-

  cellulose or polyethylene glycol and cellulase al-

  caline de l'inveption pre.sente a syner-gie in eliminating

nation of muddy dirt.

  To avoid decoó: osition carboxymethyl-

  cellulose by the alkaline cellulase in the detergent composition, it is preferred to use carboxymethylcellulose

  in a granular or coated form.

  Bleaching agents The use of the alkaline cellulase of the invention in combination with a bleaching agent such as

  sodium percarbonate, sodium perborate, sulphate

  sodium fate / hydrogen peroxide adduct or sodium chloride / hydrogen peroxide adduct and / or bleaching dye

  photosensitive material, such as a zinc salt or an aluminum salt

  Sulfonated phthalocyanine further improves the detergent effects. (6j Enzymes (enzymes that exhibit their essential enzymatic effects in the debridement stage):

  As enzymes, the following enzymes may be mentioned:

  (ranked according to their enzymatic activities):

  Hydrolases, hydrases, oxydo-reductases, desmolases, trans-

  ferases and isomerases. All of these enzymes can be used in the invention. The enzymes we prefer

  particularly hydrolases, such as

  the esterases, the carbohydrolases and the nucleotides

has his.

  Examples of proteases are the pep-

  sine, trypsin, chymotrypsin, collagenase,

  keratinase, elastase, subtilisin, BPN,

  keratinase, elastase, subtilisin, BPN, pa-

  paine, bromelain, carboxypeptidases A and B,

  minopeptidase and aspergillopeptidases A and B.

  Examples of esterases are gastric lipase

  pancreatic lipase, plant lipases, phospholipases, cholinesterases and phosphatases.

  Carbohydrolases other than cellulases

  calines include maltase, saccharase, amylase and

  pectinase, lysozyme, 1 ', -glucosidase and -glucosidase.

  77 Fluorescent agents and fluorescent dyes.

  If it is necessary, it can be incorporated into the

  position various bluing agents and fluorescent dyes

  cents. For example, compounds of the following formulas are recommended:

N N 93

SO 3Na N <SQ S03Na N / N

CHN-0)

c0 NaSN

CH CH = CH-

  SO NaS O t ^ CH 3CH CHNa so S0N 3Na oNN

  and the brighteners having the following formulas:

D -NR - CC - y

I

  N C / fNO X wherein D represents a remainder of a blue dye

  or monoazolic, disazolic or anthraquid-like

  nonique, X and Y each represent a hydroxyl radical, an amino radical, an aliphatic amino radical which may be substituted by a hydroxyl radical, sulfonic acid,

  carboxylic acid or alkoxy, or an amino aromatic radical

  or alicyclic acid which may be substituted by a halogen atom or a hydroxy, sulphonic acid or

  carboxylic acid, lower alkyl or lower alkoxy, R

  has a hydrogen atom or a lower alkyl radical

  except where (1) R represents an atom of hy-

  the two symbols X and Y represent simul-

  a hydroxyl or alkanolamine radical and (2) R

  has one hydrogen atom and one of X and Y represents a hydroxy radical and the other represents an alkanolamine radical, and n represents an integer of at least 2, or

D - NH- C / N C - X

N N

  wherein D represents a remainder of azo blue or purple dye or anthraquinone, and X and Y represent alkanolamine or hydroxy radicals.

similar or different.

  / 8] Agents preventing the formation of agglomerates (anti-caking agents)

  The detergent powder can be incorporated into

  the following anti-caking agents: p-toluenesulphonic salts

  fonate, xylenesulfonate, acetate and sulfosuccinate, talc, finely pulverized silica, clay, calcium silicates (such as Johns Manvill Co.'s Micro-Cell), carbonate

calcium and magnesium oxide.

  927 Blockers of factors inhibiting the activity of the

alkaline cellulase.

  Alkaline cellulases are deactivated in some cases in the presence of copper, zinc, chromium ions,

  mercury, lead, manganese, or silver or their compounds.

  Various chelating agents metals and precipitating agents

  metals are effective against these inhibitors. They understand

  take, for example, the divalent metal ion sequestering agents indicated in I7 above relatively

  optional additives as well as magnesium silicate

sium and magnesium sulfate.

  Cellobiose, glucose and gluconolactone a-

  sometimes act as inhibitors. We prefer as much

  as possible to avoid the simultaneous presence of these saccha-

  wrinkles and alkaline cellulase. In the event that this simultaneous presence is unavoidable, it is necessary

  avoid the direct contact of the saccharides and

  alkaline lulase, for example by coating them.

  In certain cases, powerful chelating agents such as ethylene diamine tetraacetate salts,

  anionic surfactants and surfactants

  Cationic agents act as inhibitors. How-

  these substances may be present at the same time as alkaline cellulase if their contact with

  mutuel for example by tableting and coating.

  If it is necessary, the agents can be used

  and blocking methods mentioned above in the invention.

  / 10] Activators of alkaline cellulase:

  The activators vary according to the various

  alkaline solutions. In the presence of protein, cobalt and its salts, calcium and its salts, potassium and

  of its salts, of sodium and of its salts or of monosaccharide

  wrinkles, such as mannose and xyl, alkaline cellulases are activated and their detergent powers are remarkably improved

* y / lz Antioxidants.

  Antioxidants include, for example, the tert-

  butyl-hydroxytoluene, 4,4'-butylidenebis (6-tert-butyl-

  3-methylphenol), 2,2-tert-butylidenebis (6-tert-butyl-4-

  methylphenol), monostylated cresol, distyrene cresol,

  phenol monostyrene, phenol-lysine, and l, lt-bis-

(4-hydroxyphenyl) cyclohexane.

(12) Solubilizers: -

  Solubilizers include, for example,

  lower cools, such as ethanol, benzenesulphonate salts, lower alkylbenzenesulphonate salts such as ptoluenesulphonate salts, glycols, such as propylene glycol, the like salts;

  acetylbenzenesulfonate, acetamides, acid amides,

  pyridinedicarboxylic salts, benzoate and Iturea salts.

  The following examples illustrate the invention. The-

  The following reference example explains the preparation of an alkaline cellulase. Unless otherwise indicated, in

  In the following examples, the percentages are by weight.

  REFERENCE EXAMPLE 1 Alkaline Cellulase Preparation: The alkali-resistant cellulases according to the invention are obtained, for example, according to a technique described by G. Okada, T. Nishizawa and K. Nishizawa in "Biochem.J.

  99, 214 (1966). "More particularly, a solution is

  hepatopancreas crude enzyme from a marine mollusc (Dolabella sp.). The crude enzyme solution is subjected to starch zone electrophoresis and the saccharification activity of the carboxymethylcellulose of the fraction obtained is measured. The saccharification activity of carboxymethylcellulose at pH 8.3 is determined from the absorbance

  (iADO) at 660 nm with an alkaline copper reagent and an arsenic

  nomolybdate after reaction of the fraction with carboxymethyl

  methyl cellulose. Fraction N Cellulase Activity at pH 8.3 (OD)

0.05

0.55

0O47

0.40

35 0.12

  We see that fractions 15, 20 and 30 contain

  cellulases with high activity under conditions

weakly alkaline

Example 1

  The superiority of the effects of alkaline cellulase compared to those of other enzymes on cotton fabrics

  artificially soiled mud will be illustrated.

  1) Detergent compositions: (A) (%)

  Linear sodium dodecylbenzenesulfonate 10 -

  D-olefinsulfonates (C16-18) sodium 5 sodium alkylethoxysulfates (C1415, = 1.5 moles) 2

sodium alkylsulfates (C1415) 3 -

  soap (sodium salts of beef fatty acid) 2 -

  ethoxylate ('E = 7) of secondary alcohol (C = 13.5) -

sodium tripolyphosphate 10 -

  crystalline sodium aluminosilicate (type 4A) 10 -

sodium silicate 10 -

triethanolamine - 5

sodium carbonate 10 -

potassium carbonate - 5

A B

(%) (%)

  carboxymethylcellulose 1 1 polyethylene glycol (P 6 OX) 1 1 fluorescent dye 0.40 3 brightening agent, 5 p-toluenesulfonate of sodium 2 4thanol water * 'cGLemnt enzyme C Or o uT 2 perfume.2 0.1

Glauber salt complen: -

  2) Mud stain fabrics (fabrics - c) - e atifici1e..nt

  We dry at 120 - 5 OC of the land of Kanuma seki-

  gyJcku for horticualture for 4 hours then we spray it

  is. The particles are passed through the sieve.

  pm of mesh opening at 120 ° C for two hours.

  res. 100 g of soil particles are dispersed in 1000 C perclene. Calico 2C023 is placed in contact with the dispersion and brushed. When the dispersion is removed, excess sludge is removed from the fabric (patent no

Examined JA-26-4 (3)).

  Samples are taken from samples. x 10 cm

and they are subjected to testing.

  (3) Conditions and procedure for detoning and disposal.

  Dissolve a de-ergent in hard water before

  a hydrodynamic tiger of 5S85 'uz get I 1 of a so-

  aqueous solution of 0133% Detergent. We dive into the

  aqueous solution of detergent S pieces of fabric soiled with

  tificially mud. After two hours of stay at 40 C,

  the solution of detergent and the

  artificially soiled in a stainless steel beaker

  dable for Turgotometer and stirred at 100 rpm at 20 C for 10 minutes in the Turgotometer. After washing at ''

  running water1 iron with iron and measure

  stances. The detergency rate is calculated according to the following formula:

  The reflectances of the original tissue are measured a-

  washing and soiled fabric before and after washing with an automatic recording colorimeter (product of Shimadzu Seisaku-sho) and the detergency level (%) is calculated according to the following formula: (Reflectance (Reflectance after wash rate) before washing) Detergent (%) = .X 100 (Reflectance (tissue Reflectance - before wash) of origin) The results shown in Table 1 are

the average of five samples.

  The aqueous solution of detergent has, before the

vage, a pH of 10.6.

  4) Enzymes Used: (1) Nil (Compensated with Glauber Salt) (Comparative) (2) Alkaline Cellulase (Enzyme Solution) of Fraction NO 15 of Reference Example Above) (3) alkaline cellulase (crude enzyme solution Pr of fraction N 20 of the reference example

above)) Ven-

  (4) alkaline cellulase (crude enzyme solution of fraction N of Reference Example 1 above) (5) cellulase (crude enzyme solution of fraction N 35 of Reference Example above) (6) amylase (Termamyl 60G, product of NOVO Co.) (7) protease (Gist Brocades, maxatase P 330,000) (8) lipase (Olipase, product of Nagase Sangyo Co.)) Results:

TABLE 1

  Enzyme in Detergent Rate (%) Detergent Composition A Composition B

(1) 65 60

(2) 81 78

(3) 80 77

(4) 79,76

(Y Y 74 74

(6) 66 -

(7) 65 -

(8) 65

  REFERENCE EXAMPLE 2 A culture medium (having a pH of 10) containing 1.0% peptone, 100% meat extract, 1.0% carbo xymethylcellulose (CCm) OS% sodium chloride was inoculated. , Os1% potassium dihydrogen phosphate and 1.0%

  of anhydrous sodium carbonate, with Bacillus N4 a new

  species belonging to the gene Pacilus (eposec aPvc le

  deposition number FPRI 1141), isolated from the ground floor.

  picked at Hirosawa, Wakos City, Saitama Prefecture, and agitated at 37 for 72 hours. We

  separates the cells by centration or obtain a

  raw zyme. The crude enzyme is dried according to the invention.

  usual method for obtaining a cellulase powder. We ob-

  thus holds 10 g / 1 of a cellulase enzyme (having a

  Enzyme activity of 0.6 unit / mg of solid material to pfH6) hereinafter referred to as N-4! 1 cellulase. At a pH of 9.1, this enzyme thus obtained retains 85% of the activity at pH 6. It will be noted that a commercial cellulase derived from Aspergillus ier has a

  -0% at pH 9. This cellulase therefore has no activity at pH 9.

  REFERENCE EXAMPLE 3 9 ml of a culture medium containing 0.5% of ammonium sulfate, 1.5% of wood pulp, 0.02% of glucose, 0.1% of yeast extract, 0.02, of MgSO4.7H2O and 0.2% of K2HPO4 and the medium is sterilized.

  cultured at 120 ° C. for 20 minutes. We cool the half

  sterilized culture place and mixed with 10 ml of a separately sterilized 0.7% aqueous solution of NaHCO3. We

  then seed the culture medium with a

  Cellulase manufacturer 212 belonging to the genus Aeromonas (deposited with FRI number 2306) and cultured with stirring at 237 C for 72 hours. We eliminate

  cells by centrifugation to obtain an enzymatic liquid

  A crude tick consisting of cellulase 212. The crude enzyme liquid is dried with ethanol in the usual manner for

  to obtain a cellulase powder having enzymatic activity

  than 0.55 units / mg dry matter at a pH of 6 (it is

  hereinafter "cellulase 212"). At a pH of 9, the enzyme

  if obtained preserves 70% of the enzymatic activity which it

at pH 6.

  The enzymes used in Examples 2 & 7 fi-

below.

  (1) Cellulase N4 (2) Cellulase 212 (3) Cellulase (provided by Sigma Co., derived from Aspergillus niger, 1.35 units / mg) (4) Lipase (supplied by Gist Brochades NV, derived from R. oryzae (5) Amylase (Termamil 6OG supplied by Novo Industries Co.) (6) Protease (Alkalase 2, OM supplied by Novo Industries Co.)

Example 2

  A strongly alkaline powder detergent is prepared

  linen for clothing having the composition below. The pH of

  a 0.133% aqueous solution of the detergent is 11.2.

  % by weight linear dodecylbenzenesulfonate soap (sodium salt of beef tallow fatty acid) sodium orthophosphate sodium metaphosphate sodium carbonate sodium carboxymethylcellulose polyethylene glycol fluorescent dye Glauber salt enzyme water % by weight 0.4 supplement 0 or 2 The results of the washing test carried out with the detergents thus prepared are given in Table 2.

  note that in Table 2 and the tables below, each

  that detergent is identified by the association num: ro of e-

  xample - number of the enzyme (the detergent without enzyme is

  identified by the set number of example (O)).

TABLE 2

1- (O)

1- (1) 1- (2) 1- (3) 1- (4)

1- (5)

  1- (6) Detergent (reference detergent) (present invention) () invention) Washing power index tO0 103.5 104.0 lic 5

Example 3

hug of a

  a weakly powdered detergent is prepared.

  for clothing having the following composition. PH

  0.13% aqueous solution of the detergent is 10.3.

  % by weight sodium z-olefin sulphonate soap sodium tripolyphosphate sodium silicate (JIS N 2) sodium carbonate carboxymethylcellulose polyethylene glycol fluorescent dye 0.4

2'01227

  Glauber salt enzyme water supplement 0 or 2

  A washing test is carried out as in the e-

xample 1.

  The results obtained are shown in Table 3.

TABLE 3

  Detergent Washing Power Index 2- (0) (reference detergent) 2- (1) (present invention) 2- (2) (present invention) 2- (4) 2- (5) 2- (6)

Example 4

104.5, 5

  A neutral powder detergent is prepared for

  ments having the following composition. PH of a solution

  0.133% of the detergent is 6.8.

  alcohol (C14) linear sodium sulphate polyethylene glycol sodium phosphate fluorescent dye Glauber salt enzyme water% by weight 0.2 supplement 0 or 2 The results of the washing test carried out with

  the detergents thus prepared are shown in Table 4.

TABLE 4

  Detergent 3- (0) (Reference Detergent) 3- (1) (present invention) 3- (2) (present invention 3- (4)

3- (5)

  3- (6) Index of washing power 103.5

2501227!

J

Example 5

  A weakly alkaline phosphorus-free detergent having the following composition by weight sodium dodecylbenzenesulphonate alkyl ethoxysulphate (C14-15, EO = 3 mol) adjuvant and enzyme (see Table 5) sodium silicate carboxymethylcellulose polyethyleneglycol fluorescent dye Glauber water 1,5 1,5 0,5 complement s The results of the washing test appear in

Table 5.

TABLE 5

  En.me Washing index sodium tripolyphosphate, 20% sodium citrate, 20% zeolite type 4A, 20% sodium citrate, 15% zeolite type 4A, 15% sodium citrate, 15% sodium citrate, 15% zeolite type 4A, 15% zeolite type 4A, 15%

- 100 detergents of reference

ence

- 98.5

(6), 5S 98.5

(6), $ 5 98.5

(1), 5S 102 (present invention)

(2), 5% 102.5 (present invention

tion)

(1), 5% 101.5 (present invention

  (2), 5% 102 (present invention)

Example 6

  Detergents are prepared according to the formula

  in Example 5 using combinations of enzymes.

adjuvant

2501227;

  The results of the washing test carried out with these detergents

are shown in Table 6.

TABLE 6

  Detergent Enzyme combination Index (the right number of washing powers indicates the% enzyme) 2- (2) reference detergent 2- (2) / (4) (present invention) 2- (2) / (5) ) (present invention) 2- (2) / (6) (present invention) 2- (2) / (4) / (6) (present invention) 2- (2) / (5) / (6) (present) invention)

2- (4) / (5) / (6)

(2) = 2

(2) / (4) = 1/1

(2) / (5) = 1/1

(2) / (6) = 1/1

(2) / (4) / (6) = 2/1/1

(2) / (5) / (6) = 2 / l / l

(4) / (5) / (6) = 2/1/1

Example 7

  A weakly powdered detergent is prepared

  hug for clothes having the following composition.

  sodium alkylsulfate (C = 14.5) sodium alkylethoxysulfate (C = 14.5, oE = 3 soap (beef tallow type) sodium pyrophosphate sodium silicate sodium carbonate polyethylene glycol fluorescent dye Glauver salt magnesium silicate water enzyme% by weight 0.2 supplement, 5, 101.5 101.5 sodium percarbonate The results of the washing test carried out with

  the detergents thus prepared are shown in Table 7.

TABLE 7

  Detergent Enzyme Index of washing power 6- (6) (reference detergent) (6) 100 6- (1) (present invention) (1) 102.5

  6- (2) (present invention) (2)

2? O 1227

Claims (6)

R E V E N D I C A T IONS   1 - Detergent composition characterized in that   that it includes an alkaline cellulase.   2 - A detergent composition according to claim 1, characterized in that the alkaline cellulase has an optimum pH of timal from 8.0 to 11.5.   3 - detergent composition according to claim 1, characterized in that the alkaline cellulase is chosen   cellulase produced by a Bacillus-type fungus.   read N and a cellulase produced by a mushroom producer   cellulase 212 belonging to the genus Aeromonas.   4 - Detergent composition according to claim 1, characterized in that it comprises from 0.01 to 70% by weight of alkaline cellulase having an enzymatic activity   at least 0.001 unit / mg dry matter.   Detergent composition according to claim 1, characterized in that it comprises alkaline cellulase   at a rate of 0.1 & 1000 units per liter of composition.   6 - Detergent composition according to claim   1, characterized in that it further comprises one or more   components chosen from surfactants, sequestering agents of divalent metal ions,   alkaline agents, inorganic electrolytes,   tiredness, bleaching agents, enzymes,   bleaching agents, fluorescent dyes,   timotants, factor blocking agents that inhibit   alkaline cellulase, activators of   alkaline lulase, antioxidants, solubilizing agents and other conventional additives.   7 - Detergent composition according to claim   1, characterized in that the alkaline cellulase is one of   lulase extracted from the hepatopancreas of a marine mollusc.