DE3207825A1 - DETERGENT COMPOSITION - Google Patents

Description

Cleaning agent composition

The invention relates to a detergent composition. More particularly, the invention relates to a detergent composition containing an alkali cellulase showing high activity under alkaline conditions.
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Recently, the methods of washing towels and clothes have been remarkably developed, Washing clothes has been made much easier by the development of detergent materials, water pretreatment, Improvement and expansion of the washing machines as well as the aeration of the fibers. Among these is the improvement of the raw materials for detergents are particularly noteworthy. Due to the improvement in surface active Agents, builders, dispersants, fluorescent dyes and bleaches, the detergent compositions have almost one Completion stage reached. The development The cleaning agents for clothes are essentially based on the following basic ideas:

1) A surfactant or builder is applied the dirt and / or fiber surface adsorbed to the surface tension between the dirt and / or the fiber and the water, thereby reducing the Dirt is physicochemically separated from the fiber.

2) The dirt is dispersed and loosened with the help of a surfactant ^ agent, or an inorganic one Builders.

3) The dirt is chemically broken down by an enzyme such as protease.

4) The stains are bleached with a bleaching agent.

5) A fluorescent dye will appear on the fiber surface adsorbed to lighten them.

6) The precipitation of active ingredients in the detergent a divalent metal ion is prevented with the help of a gelling agent.

The basic idea of the conventional clothes washing process lies in the effective introduction of a component, the attacks the dirt directly, or a component that the attack power of the active ingredient of the composition supports »Currently, the detergency of detergent compositions based on this reason has idea, in a sense near saturation, and an extraordinarily great effort is required to further strengthen the cleaning power.

Due to intensive research from various points of view, which differ fundamentally from the conventional ideas of clothes washing processes, it was found that in a surprising way excellent washing effects on dirt can be achieved without this is related to the enzymatic activity of an alkaline cellulase (one of the cellulases of enzymes), when the alkali ze? .iu.lase i ^ a cleaning agent is introduced will. The present knowledge is essentially based on this knowledge Invention »

It is customary for Hendels to have v / ertücoarE and generally known cellulases an optimal pH value in the acid range or in the new

BATH ORIGINAL

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in an alkaline area was not used because the cellulase activity is reduced in the alkaline range.

According to the invention there is provided a detergent composition which is characterized in that it contains an alkaline cellulase, which contains an optimal pH value in the alkaline range as a component. According to the invention, the detergent has a joint solution setting a remarkable cleaning effect, in particular on inorganic soiling, which is generally not related to the alkali cellulase activity.

As has been described above, one knows in this area the use of an Ensym as part of a cleaning agent. The only known enzymes were those that had an active effect on dirt. In particular, proteases were only for Protein dirt known and amylase for saccharide dirt, and lipase for dirt, consisting of oils and fats. Such enzymes attack the dirt directly. Through the Mechanisms of the cleaning effects of alkali cellulases according to the invention has not yet been fully explained, although it is known that the effects are not only due to the expansion of the fibers are based, unlike a phenomenon observed with the use of surfactants.

Great advantages of the invention are that the detergent is particularly effective in removing inorganic solid dirt, such as fine sludge particles, which cannot be adequately removed with conventional detergents, as well as in removing other dirt, such as stains on shirt collars or cuffs of clothing as well a Ölf.lecker on clothes, while a special benefit in _r lie-t to increase the cleaning power phosphorus-free detergent, which also

Cleaning agents with a very low phosphorus content apply. Phosphate salts were very effective at removing fine sludge particles that get into the fibers was. Recently, however, there has been a push to reduce the amount of phosphate salts in detergents, because of the problem of eutrophication. The requirement for the use of phosphate-free detergents makes removal extremely difficult to remove sludge particles. In particular, the removal of sludge particles in tree vaulted fabrics penetrated is extremely difficult, which is well known. It has also been shown that the removal of muddy stains from cotton shoes creates great difficulties for users when washing the shoes prepared.

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The present invention sheds new light on these problems. According to the invention, it becomes excellent in detergency achieved that is equal to or even better than that of a weakly alkaline powder detergent, which is a sufficient Contains amount of sulfate salt by 1) applying the invention to sin alkaline detergent, which contains no phosphates or only small amounts of phosphates, or 2) the invention to a weakly alkaline one liquid, phosphorus-free cleaning agent used for cleaning muddy stains in cellulose fibers, or cloths made of mixed fibers, the celluloae - contains fibers and other fibers.

[Another great advantage of the invention is that

30 it is applicable to detergents in any form.

j The alkali cellulase can be introduced into a feed

composition in the form of a spray-dried powder,

! a powdery powder mixture, tablets or a liquid

; speed, taking into account the composition of the cleaning

by means of the invention

COPY BAD ORIGfNAL

Have the alkali cellulases used according to the invention an optimal pH of 8.0 to 11.5, preferably from 8.1 to 11.0. Under alkaline conditions these enzymes show an activity equivalent to that under acidic or neutral conditions demonstrate. The alkali cellulose is obtained from cellulase culture fluids of various origins Refining and fractionation after a salting out, precipitation, Dialysis or gel permeation processes. The alkali cellulases is also obtained by fractionation of crude or refined enzymes by electroforesis or by heat treatment thereof (for example at 40 to 90 ° C for 5 minutes to 3 hours).

^ ⁵ The following enzymes can be specified as particularly preferred alkali cellulases according to the invention:

In the case of the specific cellulase used according to the invention is preferably a cellulase produced by a fungus of the Bacillus N or a cellulase-212-producing one Mushroom belonging to the Aeromonas tribe. Bacillus N is disclosed in Japanese Patent Publication No. 28515/75 and available On The Fermentation Research Institute, the Agency of Industrial Science and Technology, at 1-1-3, Higashi, Tsukuba-Yatabe-machi, Ibaraki, Japan. He was in the enduring Collection of microorganisms recorded under the numbers FERM Nos. 1138, 1139, 1140 and 1141. The Aeromonas Fungus has also been included in the permanent collection of microorganisms at the Fermentation Research Institute, the Agency of Industrial Science and Technology, as FERM No. 2306 and is in Japanese Patent Publication (unaudited) No. 76287/75, now published after the Examination as Japanese Patent Publication 39191/81 disclosed.

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The cell nozzle used according to the invention comprises a Cellulase extracted from the hepatopancreas of sea mollusks (Dolabella Auricula Solander), which is described in Biochem. J. (1966) 99: 214-221.

Every cellulase produced by these fungi is a special cellulase, the one maintains high activity even under alkaline conditions and has alkali resistance.

The detergent composition according to the invention is characterized in that this particular cellulase is included as an essential ingredient therein. In particular the invention provides a detergent composition created, which has a special detergency with respect to inorganic stains, regardless of the internal activity of the cellulase, in particular on collar stains that result from mixtures consist of inorganic stains and oils that are released from the surface of the skin and spread over you Change period.

If the detergent composition has a specific Cellulase which has high activity under alkaline conditions and also has alkali resistance which is produced from a fungus selected from the Bacillus N (deposited at FRI under the numbers 1138 to 1141) and a cellulase 212-producing fungus belonging to the strain Aeromonas, an excellent one can be obtained Achieve a washing effect over a wide pH range of the wash floor.

This excellent effect makes the reduction by far the washing power makes up for that on the reduction Alkali capacity of the builder on the reduction of the pH value of the wash bath is based.

The enzymatic «activity of the cellulase, which according to the invention is used is determined by the following procedure.

50 mg of Avicel (for chromatography) or carboxymethyl cellulose (CMC) are placed in 4 ml of a glycine-NaCl-NaOH buffer solution (pH 8.3) and the suspension is preheated to 37 ° C Minutes after which 1 ml of an enzyme liquid is added to the suspension. The suspension is sufficiently mixed and the reaction is carried out for one hour. After the reaction has ended, the amount of reduced sugar is determined by the 3,5-dinitrosalicylic acid method. Specifically, the liquid reaction mixture is filtered and 3 ml of 3,5-dinitrosalicylic acid is added to one ml of the filtrate, whereupon the mixture is heated at 100 ° C. for 10 minutes to cause coloring. The mixture is cooled and then mixed with deionized water so that the total volume increases to 25 ml. The resulting liquid is subjected to a colorimetric at a wavelength of 500 m / u .

When one mg of the enzyme as a solid produces sugar in an amount equal to 1 vu mole of glycose, one hour long under the above conditions, the enzymatic activity is defined as one unit / mg of the solid .

The present invention is achieved by making this 3ü alkaline cellulases with known detergent compositions combined. Regarding the alkali cellulase content It is preferred that the composition contain from 0.01 to 70% by weight and in particular from 0.1 to 10% by weight of an alkali cellulase with an enzymatic activity of at least 0. UOL units / mg solids contains' jjsine unit / mg Solids forms l, u / u moles of glucose from cellulose in

-IU-

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one hour at 37 C and a pH of 8.3 /. The amount of alkaline cellulase is so great that the enzymatic cellulase Activity of the alkali cellulase in the bath is preferably 0.1 to 1000 units / l, especially 1 to luü units / 1.

Although the detergent composition according to the invention can be used in an unlimited pH range from an acidic to an alkaline pH can, preferably, to the cleaning effect of the alkali cellulase Sufficiently emphasize that the cleaning bath is alkaline (in particular that a pH of 7 to 11).

In the detergent composition according to the invention, the ingredients used in addition to the cellulase are not particularly restricted. For example, the following ingredients can be included in the composition according to the invention, can be used according to their essential properties.

j fl ~] Surface active agents:

I ¹ y

(1) Straight or branched chain alkylbenzenesulfonate salts having an alkyl group of 10 to 16 carbon atoms on average.

(2) alkyl or alkenyl ether sulfate salts with a straight chain or branched alkyl or alkenyl group

2Q with Iu to 2o carbon atoms on average,

u, 5 to 8 moles on average of ethylene oxide, propylene oxide in the molecule and an addition ratio of ethylene oxide / propylene oxide of 0.1 / 9.9 to 9.9 / 0.1 or ethylene oxide / 8utylene oxide from 0.1 / 9.9 to 9.9 / 0.1.

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(3) Alkyl or A ¹ ko-.yi ₃ sulfate salts having an alkyl or alkenyl group of 10 to 20 carbon atoms on average.

(4) Olefin sulfonate salts having 10 to 20 carbon atoms on average in the molecule.

(5) alkanesulfonate salts having 10 to 20 carbon atoms on average in the molecule.

(6) Saturated or unsaturated fatty acid salts, with 10 to 24 carbon atoms on average in the molecule.

(7) Alkyl or alkenyl ether carboxylate salts having an alkyl or alkenyl group of 10 to 20 carbon atoms on average, 0.5 to 8 moles on average of Ätatylenoxod, propylene oxide or butylene oxide in the molecule and an additional ratio of ethylene oxide /

2u propylene oxide from 0.1 / 9.9 to 9.9 / 0.1 or ethylene oxide / butene oxide from 0.1 / 9.9 to 9.9 / 0.1.

(8) ώί-sulfo fatty acid salts or esters of the general Formula:

₂ c H-CfICU ₀ Y

I ^ ÜO -.Z

■ J?

where Y represents an alkyl group having 1 to 3 carbon atoms or a counterion, while Z represents a 3ö counterion and K is an alkyl or alkenyl group with represents up to 20 carbon atoms.

As Geqenionen of anionic surface-active Means are to be mentioned, for example, ions of alkali metals. like sodium and potassium, alkaline earth

metals such as calcium and magnesium, ammonium, alkanolamides with a content of 1 to 3 alkanol groups with 2 or Carbon atoms, such as monoethanolamine, diethanolamine, Triethanolamine and triisopropanolamine. 5

(9) Amino acid type surface active agents of the general one Formula:

No. 1 H ₁ -Cu-M-CH-CUOX

¹ I \

^R 2 ^R 3

where R is an alkyl or alkenyl group with 8 to carbon atoms, R _? Hydrogen or an alkyl group with 1 to 2 carbon atoms, R- an amino acid residue

and X represents an alkali metal or an alkaline earth metal ion.

_no . ₂ R ₁ -CO-N- (CHp ₁₁

where R, Rp and X have the same meanings as above have, while η represents an integer from 1 to 5.

^{No. 3 Ri} y N- (CIi ₂ ) _m -COOX

- ^R l

where R has the same meaning as above and m is a

represents an integer from 1 to 8. 3ü

_No. 4 H. -N-CIl-COOX

,1 \

where R, R- and X have the c, meaning as above ba-

sit while R ₃ Wass ^ 'scotf or an alkyi- or

BATH ORIGINAL

Represents a hydroxyalkyl group with 1 or 3 2 carbon atoms.

R ₁ -N-CH-COOX

No. 5 * ^.

^; -

where R ^, R, and X are qleiche meaning as above and R _r a fa hydroxyalkyl or /?> hydroxy

represents alkenyl group having 6 to 28 carbon atoms. 10

No. 6 5 \ _n _ _C h_c00X

FL- ' I

where R_, R ₅ and X have the same meaning as above.

(10) Phosphate ester surfactants:

No. 1 Acid alkyl (or alkenyl) phosphates 0

where R ^{1 represents} an alkyl or alkenyl group having 8 to 24 carbon atoms, while n '+ m ¹ 3 and n ^{1 means} a number from 1 to 2.

No. 2 alkyl-C or alkenyl) phosphates:

(K0) _nll l

where R 'has the same meaning as above, while n "+ m" 3 and n' ^! represents a number from 1 to 3.

No. _s 3 alkyl (or alkenyl) phosphate salts

where R ¹ , η ¹¹ and m ¹ 'have the same meaning as above, while M, Na, K or Ca represents.

(11) Amphoteric sulfonic acid type surface active agent represented by the following formula
number 1

Ϊ ¹³ '

where R is an alkyl or alkenyl group with 8 to 24

Carbon atoms, R ~ an alkenyl group with 1 to 4

Carbon atoms, R _{3 is} an alkyl group with 1 to 5

Carbon atoms, R _{14 is} an alkylene or hydroxyalkyl

represents a group having 1 to 4 carbon atoms.

No. 2 ¹ J ¹ It /

Ι C-)

where R and R _{14 have} the same meanings as above, while R. ^ and R _g each represent an alkyl or alkenyl group having 8 to 24 or 1 to 5 carbon atoms

represents-30

No. 3 ^li lcf ^lH ur ' ^U l

where R and R ^^ have the same meaning as above, while nl represents a qanze Zar \ l from 1 to 20.

(12) Betaine type amphoteric surfactants the general * ■ '«_» rniel:

¹ ^

^No

wherein R ₂₁ is an alkyl, alkenyl, / 1? hydroxyalkyl or / δ-hydroxyalkenyl group having 8 to 24 carbon atoms, R * 22 is an alkyl group having 1 to 4 carbon atoms, and ^R 23 ^e i ^ne alkylene or hydroxyalkylene group having from 1 to Represents carbon atoms.

No. 2

- (C ₂ H ₄ O) ₁₁₂ H

where R_ and R _{23 have} the same meaning as above, while n2 represents an integer from 1 to 20.

No. 3, 24

H ^

where R ₂ and R _{23 have} the same meaning as above, while R _{24 represents} a carboxyalkyl or hydroxyalkyl group having 2 to 5 carbon atoms.

(13) Polyoxyethylene alkyl or alkenyl ethers with an alkyl or / akenyl group of 10 to 20 carbon atoms in the

Average and 1 to 20 moles of ethylene oxide added. 3O

(14) Polyoxyethylene alkyl vinyl ether with an alkyl group from 6 to 12 carbon atoms on average and 1 to 20 moles of ethylene oxide added.

(15) Polyoxypropylene alkyl or alkenyl ethers with an alkyl or alkenyl group of Iu to 20 carbon atoms im Average and 1 to 20 moles of propylene oxide added.

· - J Ö - ·

(16) t'olyoxybutylene alkyl or alkenyl ether with an alkyl or alkenyl group of Iu to 20 carbon atoms in Average and 1 to 20 moles of butylene oxide added.

(17) Nonionic surfactants with an alkyl or alkenyl group of 10 to 20 carbon atoms in the Average and 1 to 30 moles in total of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide added (The ratio of ethylene oxide to propylene oxide or butylene oxide is, 1 / 9.9 to 9.9 / 0.1).

(18) Higher fatty acid alkanolamides or alkylene oxide adducts thereof of the general formula:

- ' _N

(CtICH 0) , H.

where R ¹ ^ _{11 is} an alkyl or alkenyl group with 10 to 10 carbon atoms, R _{'12 is} ^H or CH ₃ , n3 is an integer from 1 to 3 and m3 is a whole number from 0 to 3.

(19) Sucrose / fatty acid esters with fatty acids that are ic up to 20 Have carbon atoms on average and sucrose,

(2o) fatty acid / G 1ycolmonoester with fatty acids, the 10 to Have 2o carbon atoms on average and glycerol.

(21) Alkylamine oxides of the general formula:

^ Copy

BATH ORIGINAL

where R ' _{l3 is} an alkyl or alkenyl group with 10 to 2u carbon atoms and R ^: and R ^ ₁ - each represent an alkyl group with 1 to 3 carbon atoms.

£ 22) Cationic surfactants of general Formula:

Number 1 .

where at least one of R ¹ , R ' _? , R'o and R% represent an alkyl or alkenyl group having 8 to 24 carbon atoms and the remainder an alkyl group having 1 to 5 carbon atoms, while X 'represents a halogen.

No. 2 ^l \ 2

R'v

^J

where R ^, R ' ₂ » ^R * 3 ^{and χι have the} same meaning as mentioned above.

No. 3 · "'■

[ K \ - ^ ^V - \ V ₂ ] X '

where R%, R ¹ . and X 'have the same meaning as above, while R' represents an alkylene group having 2 to 3 carbon atoms and n4 represents an integer of 1 to 20.

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The composition preferably includes at least one the above surfactants in an amount of at least 10% by weight.

Preferred surfactants are as follows to mention 1), 2), 3), 4), 5), 6), H) no. 2, 12) no. 1, 13), 14), 15, 17) and 18).

Γ2Ι Bivalent Me'tallionaquestrant: 10

The composition can ο up to 50% by weight or contain several builder components selected from the group consisting of alkali metal salts or alkanolamine salts of the following connections: 15

1) salts of phosphoric acids, such as orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, metaphosphoric acid, Hexametaphosphoric acid and phytic acid.

2) salts of phosphonic acids, such as ethane-1,1-diphosphonic acid, Ächan-1,1,2-triphosphonic acid, athan-1-hydroxy-1, i-diphosphonic acid and their derivatives, xthane-hydroxy-1, l, 2-triphosphonic acid, Ethane-1,2-dicarboxy-1,2-diphosphonic acid and metanhydroxyphosphonic acid.

3) salts of phosphonocarboxylic acids, such as-2-phosphonobutn-1,2-dicarboxylic acids, l-phosphonobutane-2,3,4-tricarboxyic acids and ^ -methylphosphonosuccinic acid. 30th

4) Salts of amino acids such as aspartic acid, glutamic acid and glycine.

5) salts of aminopolyessic acids, such as nitrile triacetic acid, Imine diacetic acid, eti ^ ylenediamine tatraacetic acid, diet hylenetriaminepentaespic acid, glycol ether diamine tetraacetic acid, Hydroxyethyliminodiacetic acid, triethylene

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tetraminhexaessigsMure and diencolic acid.

5) High molecular electrolytes, such as polyacrylic acid, polyaconitic acid, Polyitaconic acid, pulycitraconic acid, polyfumaric acid, Polymaldic acid, polymesaconic acid, poly-Tj6-hydroxyacrylic acid, Polyvinylphosphonic acid, sulfonated polymaleic acid, maleic anhydride / disiobufcylene copolymer, maleic anhydride / Styrene copolymer, maleic anhydride / methyl vinyl ether copolymer, Maleic anhydride / ethylene copolymer, maleic anhydride / ethylene mixed polymer, Maleic anhydride / vinyl acetate copolymer, maleic anhydride / acrylonitrile copolymer, maleic anhydride / acrylate ester copolymer, Maleic anhydride / butadiene copolymer, malainic anhydride / isoprene copolymer, Poly-A-ketocarboxylic acid derived of maleic anhydride and carbon monoxide, itacona acid /

Ί5 ethylene copolymer, itaconic acid / acetonic acid copolymer, itacona acid / maleic acid copolymer, Itaconic acid / acrylic acid copolymer, malonic acid / methylene copolymer, mesaconic acid / fumaric acid copolymer, Ethylene glycol / ethylene terephthalate copolymer, vinyl pyrrolidone / vinyl acetate copolymer, l-butene-2,3,4-tricarboxylic acid / Itaconic acid / acrylic acid copolymer, quaternary ammonium groups containing polyester polyaldehyde carboxylic acids, cis-isomar of epoxysuccinic acid, poly [n, N-bis (carboxymethyl) acrylamideJ, Poly (hydroxycarboxylic acid), starch succinate, starch maleate, Starch terephthalate and starch phosphate esters, dicarboxy starch, dicarboxymethyl starch and cellulose succinate esters.

7) Non-dissociating, high-molecular components, such as polyethylene glycol, Polyvinyl alcohol, polyvinylpyrrolidone and lime water-soluble urethanated polyvinyl alcohol.

8) salts of dicarboxylic acids, such as oxalic acid, malonic acid, Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and decane-1.10-dicarboxylic acid; Salts of diglycolic acid, thiodiglycolic acid, oxaloacetic acid,

Hydroxydisuccinic acid, carboxymethylhydroxysuccinic acid and Carboxy.tiethyltatronic acid; Salts of hydroxycarboxylic acids, such as glycolic acid, malic acid, hydroxypivalic acid, tartaric

acid, citric acid, lactic acid, guluconic acid, mucic acid, ε- ^D glucuronic acid, as well as galdehyde starch oxides salts of the Itacon

acid, methylsuccinic acid, 3-methylglutaric acid, 2,2-dimethylmalonic acid, Maleic acid, fumaric acid, glutamic acid, 1,2,3-propane tricarboxylic acid, aconitic acid, 3-butene ~ j 1,2,3-tricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid,

Xthantetracarboxylsau.ee, ethentetracarboxylic acid, n-alkenyl aconitic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, Phthalic acid, trimesic acid, hemimellitic acid, pyrromellitic acid, Benzene hexacarboxylic acid, tetrahydrofuran-1,2,3,4-tetracarboxylic acid and tetrahydrofuran-2,2,5,5-tetracarboxyl-

Ί5 acid; Salts of sulfonated carboxylic acids, such as sulfoitaconic acid, Sulfotricarbaylic acid, cysteic acid, sulfoacetic acid and sulfosuccinic acid; Carboxy methylated sucrose, lactos " and raffinose, carboxymethylated pentaerythritol, carboxymethylated Glyconic acid, condensates of polyvalent

^2ü alcohols or accharides with maleic anhydride or succinic anhydride, condensates of hydroxycarboxylic acids with maleic anhydride or succinic anhydride and organic acid salts such as CMuS and Builder M.

9) aluminosilicates:

No. 1 Crystalline aluminosilicates of the formula

3ü

or · h "Ü) • Αίν, Ο., - γ ¹ (MjO ₂ ): - w '(H ₂ O)

where M "is an Alke..li metal latom, M ^{11 is} an alkaline earth atom

interchangeably with calcium, x ", y ¹ and w ^{1 represent the} number of moles of the respective components, whereby the following order of magnitude generally applies:

0.7 - 'x · < \. ¹ j, 0.8 <y ^! · 6 and w ¹ equals a positive number.

BATH ORIGINAL

No. 2 detergent builders having the following general form] are particularly preferred:

_Well? Ü · A-ß., 0.,. nSiO ₂ . WH ₂ O where η is a number from 1.8 to 3.0 and w is a number from 1 to 6.

No. 3 amorphous aluminates of the formula: X (M ₂ O) -AO ₂ O ₃ -Y (SiO ₂ ). W (H ₂ O)

where M is a sodium and / or calcium atom and x, y and w represent the number of moles of the respective components with the following ranges:

0.7 <χ <1.2

·

'· 1.6 <; y <: 2.8

w: any positive number including 0.

No. 4 amorphous aluminosilicates of the formula: "X (M ₂ O) .AS ₂ Oy Y (SiO ₂ ) .Z (P ₂ Oj ₃ ) .Uj (H ₂ O)

where M denotes Na or K, while X, Y, Z and the number of moles of the respective components in the following Represent areas:

0.20 <;

0.20 <; γ '<ς 4.00
• .o.ooi <: ζ <o.ao

[^ : any positive number including 0. 30

£ "3] Alkaline or inorganic electrolytes:

The composition also came from 1 to 50% by weight, preferably Contain 5 to 3o wt .-% of one or more alkali metal salts, selected from the following ingredients as alkali or inorganic electrolyte: SiIi-

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cate, carbonates and sulfates. In addition, the composition may contain organic alkali, such as triethanolamine, diethanolamine, monoethanolamine and triiaopropanolamine.
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f * 4] anti-redeposition agents:

The composition can be from 1 to 5% of one or more Contain the following ingredients as anti-redeposition agents: Polyethylene glycol, polyvinyl glycol, polyvinyl pyrrolidone and carboxymethyl cellulose.

In particular, shows a combination of carboxymethyl cellulose or polyethyleneglycol with the AlJcalicellulose according to the invention a synergism in the removal of muddy dirt.

To prevent the decomposition of carboxymethyl cellulose by the Alkali cellulase in the detergent composition To prevent it, it is preferable to use the carboxymethyl cellulose in the form of granules or in coated form Shape a.

L ⁵ I.

Bleach:

A combination of the alkali cellulase of the invention with

a bleach such as sodium percarbonate, ftatriur.iperborat, Sodium sulfate / hydrogen peroxide adduct or Sodium chloride / hydrogen peroxide adduct and / or a photosensitive blue dye such as zinc or The aluminum salt of sulfonated phthalocyanine further promotes the cleaning effect.

Enzymes (enzymes that have their essential enzymatic effects show in the cleaning step):

As the enzymes, the following can be mentioned

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fied in relation to their enzymatic reactivity):

Hydrolases, hydrases, oxidoreductases, desmolases, Transferases and isomerases all of these enzymes can be used according to the invention. The special preferred enzymes are hydrolases such as protease, esterase, carbohydrolase and nuclease.

Examples of proteases are pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, subtilisin, BPN, Papain, bromelin, carboxypeptidases A and B, aminopeptidase and aspergillopeptidases A and B.

Examples of esterases are gastric lipases, pancreatic lipase, vegetable lipases, phospholipases, cholinesterases and phosphotases.

Carbon hydrolases in addition to the alkali cellulases include maltase, saccharase, amylase, pectinase, lysozyme, <j (-glucosidase and A-glucosidase.

j_7j Blueing agents and fluorescent dyes:

Various blueing agents and fluorescent dyes can, if necessary, be incorporated into the composition. Here are, for example, connections recommended with the following structural formulas:

NH--

SO .Na

SO-, well

CH = CH-

CH = - CH-

<f \

SO ^ Well

SO ^ Well

H H

,. N / N ^ / Γ \

H '' H

SO ^ Well

As well as blueing agents of the following general formula

_D _ _{N {} . _ C ^ ^ C - Y

Il

BATH ORIGINAL

D represents a residue of a blue or purple, monoazo, disazo or anthraquinone dye, X and Y stand for a hydroxyl group, an amino group, an aliphatic amino group, which can be substituted by hydroxyl, sulfonic acid, carboxylic acid or alkoxyl group, or an aromatic or alicyclic amino group which can be substituted by a halogen atom or hydroxyl, sulfonic acid, a lower alkyl or lower alkoxyl group, R stands for a hydrogen atom or a lower alkyl group, but excluding those cases in which (1) R is Hydrogen atom and both X and Y represent a hydroxyl group or an alkanolamine at the same time and (2) when R represents a hydrogen atom and X or Y represents a hydroxyl group, while the other represents an alkanolamine group, and η represents an integer of at least 2 and _M.

D - NH - C ^ ^ CX

Il!

N / N

Y here, D represents a residue of a blue or purple, azo or anthraquinone dye, while X and Y can be the same or different and represent an alkanolamine residue or a hydroxyl group.

! 8J anti-scaling agent:

The following anti-scaling agents can be used in introduced the powder detergent composition are: p-toluenesulfanate salts, xylenesulfonate salts, Acetate salts, sulfosuccinate salts, talc, finely powdered Silica, clay, calcium silicates (such as Micro-Cell from Johns-Manvi11 Co.), calcium carbonate and magnesium oxide.

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\ 9 j Marking or masking agent for factors that hinder the alkali cellulase activity:

The alkali cellulases are deactivated in some cases in the presence of copper, zinc, chromium, mercury, lead, manganese or silver ions and their compounds. Various metal gelling agents and metal precipitating agents act on these inhibitors. They include, for example, divalent metal ion sequestrants as listed above under Γ ^ Ι with reference to the optimal additives, as well as magnesium silicate and magnesium sulfate.

Cellubiosis, glucose, and gluconolactone sometimes work like the inhibitors. Accordingly, preference is given to the simultaneous presence of such saccharides with the Prevent alkaline cellulase as much as possible. If the simultaneous presence is unavoidable, as necessary to prevent a direct contact of the saccharides with the alkali cellulase, for example by using them covers.

Strong surfactants such as ethylene diamine tetraacetate salts, anionic surfactants, and cationic obscure surfactants act as inhibitors in some cases. However, one can allow the simultaneous Anwesenheir of these substances with the Alkalizellulase, viznn direct contact is hereby prevented, wia about by tabletting or by Überziehungsverfahran.

The above-mentioned masking means and methods can, if necessary, be used in connection with the invention will.

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JlOj Alkalizellulaseeaktivatoreη:

The activators vary depending on the different alkali cellulases. In the presence of proteins, cobalt and its salts, calcium and its salts, potassium and its salts, sodium and its salts or monosaccharides ^ such as Manose and Xylose, the alkali cellulases are activated and their cleaning power is remarkably improved.

MLlj antioxidants:

The antioxidants include, for example, tert-butylhydroxytoluene, 4,4'-ButylidenebisCe-Tert-Butyl-S-Methylphanol), 2, 2'-butylidenebis (6-tert-butyl-4-methylphenol), Monostyrenated cresol, diatyrenated crcisol, monostyrenated phenol, distyrenated phenol, and 1,1'-bis (4-hydroxyvinyl) cyclohexane.

Γ12Ι Solution mediator:

The solubilizers include, for example, lower ones Alcohols, such as ethanol, benzenesulfonate salts, lower alkylbenzenesulfonate salts, such as p-toluenesulfonate salts, glycolse, such as propylene glycol, acetylbenzenesulfonate salts, Acetamides, pyridinedicarboxylic acid amides, benzoate salts and ureas.

The following examples illustrate the invention in more detail. In the following reference examples explains the production of an alkali cellulase. Unless otherwise stated, the percentages are in the following examples in each case wt .-%.

Reference example 1

Production of alkaline cellulase :

Alkaline-resistant cellulases according to the invention are obtained for example, by a technique as disclosed in G. Okada, T. Nishizawa and K. Nishizawa "Biochem. J. 99, 214 (1966) ". In detail, a crude enzyme solution was extracted from the hepatopancreas of sea mollusks (DoIabella sp.). The crude enzyme solution was subjected to starch zone electrophoresis, and the carboxymethyl cellulose sugar-forming one Activity of the resulting fraction was measured. The carboxymethyl cellulose-sugar-forming activity at a pH of 8.3 was determined by a decadic absorbance (AOD) at 660 m / j using a alkaline copper reactant and arsenic molybdate after the fraction reacted with carboxymethyl cellulose.

Fraction No. cellulase activity at pH 8.3 (AOD)

10 o'clock, 05

15 0.55

2u 0.47

30 0.40

35 0.12

₂ c It can be seen that fractions no. 15, 20 and 30 cellular

contain lasen that are produced under weak alkaline conditions - have a high level of activity.

example 1

As shown below, exposure to alkali cellulas « much stronger than that of other enzymes on cotton cloth that artificially licks with muddy dirt is:

COpy

1) Cleaning agent compositions:

Straight chain sodium dodecylbanzene sulfonates

Sodium // - olefinsulfonate (C " _c " _Q v

· * "Lb-la;

Sodium alkyl ethoxy sulfate (C ^ _4-1 C?

(EO-1, 5 moles')

10
5

25th

Sodium alkyl sulfates

Soap (beef fatty acid sodium salts) secondary alcohol (D »13.5) ethoxylates 25th

Sodium tripolyphosphate

Crystalline sodium aluminosilicate (Type 4A)

Sodium silicate
Triethanolamine

sodium
Potassium carbonate
Carboxymethyl cellulose polyethylene glycol iMW 6000) fluorescent dye blueing agent

Sodium p-toluenesulfonate ethanol
water
enzyme
Perfume
Glauber's salt

10 10

- 5 1 1 1 1 0.4 0.3 - 0.05 2 - - 8th 10 compensation 0 or 3 0 or 2 0.2 0.1 Compensation -

3207325

2) Dirty clothes (artificially stained clothes):

Kanuma sekigyoku-Bodan for horticultural use was dried at 12 ° C - 5 ° C for four hours and then pulverized. Soil particles that passed through a sieve with a mesh size of lüüyurn were dried at 120 ° C * 5 ° C for two hours. 150 g of the soil particles were dispersed in 1000 ml Perclan. A Kaliko # 2023 cloth was brought into contact with the dispersion and brushed. After the dispersion was removed, the excess sludge that remained on the clothes was removed. (Japanese Patent Publication No. 26473/1980)

-ς The test pieces with ainar size of 10 cm 10 cm were made prepared and used as a basis for the investigations.

3) Cleaning conditions and procedures as well as evaluation:

A detergent was used in water with a hardness of 4 ° DH solved, to achieve 1 1 of a 0.133 ^ -igen aqueous cleaning agent solution. Five pieces of the cloth artificially stained with muddy dirt were put in immersed the aqueous solution. After leaving it to stand at 40 ° C for two hours, it became the cleaning agent. !; solution and the pieces of artificially stained cloth in a stainless steel beaker of the turgotometer and at Revolutions / minute and 2ü ° C for 10 minutes in the turgotometer. After the washing process under running They were flattened with an iron in water, and their reflectivity was measured. The cleaning level was calculated according to the following formula:

The reflective power of the original cloth before dam Washing and that of the stained cloth before and after washing were automatically cleaned with the help of a

drawing colorimeter (a product of Shimadzu Seisaku-sho), and the degree of cleaning (%) was calculated from the following formula:

, Reflective power after> _, Reflective power before, cleaning measure (%) « after washing * after washing ^

(Reflectivity of the

original - (reflective power Cloth) before washing)

An average of five samples was plotted in Table 1.

The aqueous detergent solution before washing had one pH 10.6.

4) Enzymes used:

(1) Not used (balanced with Glauber's salt)

(Comparison) . ^

(2) Alkali cellulase (crude enzyme solution of fraction No. 15 in the above reference example)

(3) Alkali cellulase (crude enzyme solution of fraction No. 20 in the above reference example)

according to the

(4) Alkali cellulase (crude enzyme solution of fraction No. .. ■ _ 30 in the above reference example)

-J

£ 5) Cellulase (crude enzyme solution of fraction No. 35 in the above reference example)

(6) Amylase (Termamyl 6ü G; a product of the Company NGVO Go.)

£ 7) Protease (Gist Brocades, Maxatase P 330,000)

(8) Lipase (üüpasej a product of the company Nagase Sanqyo Co.)

5) Results:
35

Enzymes in that Cleaning level (%) A composition 60 cleaning supplies Composition B. 78 77 Θ 65 76 © 81 72 Θ 8ο - (Τ) 79 - Θ 74 © 66 Θ 65

Example 2

A culture medium (with a pH of 10) containing 1.0% peptone, 1.0% meat extract, 1.0% carboxymethyl cellulose (CMC), 0.5% sodium chloride, 0.1% potassium dihydrogen phosphate and 1.0% anhydrous Sodium carbonate was inoculated with Bacillus N4, a new species belonging to the Bacillus strain (deposited with FRI under deposit 1141), separate from the soil _{collected at Hirosawa, WaIco 1} City, Saitama Prefecture, followed by shaking 72 hours long at 37 ° C. The cells were removed by centrifugal separation to obtain a crude enzyme. The crude enzyme was dried with ethanol, according to the usual method, to obtain a cellulose powder. Thus, 10 g / l of a cellulase enzyme (having an enzymatic activity of 0.6 unit / mq of solid at a pH of 6) (hereinafter referred to as "cellulase N4") was obtained.

COPY

At pH 9, the enzyme thus obtained retained 85% activity at pH 6. As an aside a commercially available cellulase with an origin from Aspergillus Niger had an activity of 0% at pH 9. This means that the cellulase had no activity at pH 9.

Reference example 3

Iu 9 ml of a culture medium containing ½, 5% ammonium sulfate, 1.5% pulp blocking agent, ü, ü2 % glucose, 1.0 % yeast extract, 0.02% MgSO ₄ -7H ₂ O and 0.2 were placed in a bottle % K ₂ HPO ₄ , and the culture medium was sterilized at 12 ° C for 2ü minutes. The sterilized culture medium was cooled and mixed with 10 ml of a 0.7% aqueous solution of NaHCO ₃ which had been independently sterilized. The culture medium was then inoculated with a cellulase 212 producing species belonging to the strain of Aerornenas (deposited with FRI under Accession No. 2306), followed by shaking cultivation at 37 ° C for 72 hours. The cells were removed by centrifugal separation, and a crude enzyme liquid of cellulase 212 was obtained. The crude enzyme liquid was dried with ethanol according to the usual method, and a cellulase powder having an enzymatic activity of 0.55 unit / mq of solid at a pH Value of 6 C hereinafter referred to as "cellulase 212"). At a pH of 9, the enzyme obtained in this way retained 70 % of the enzymatic one

³ ^ activity it had at pH 6.

The enzymes used in Examples 2 to 7 are given below.

(1) cellulase N4

(2) cellulase 212

(3) Cellulase (supplied by Siqma Co., derived from AsperqilluH Nioer, 1.15 units / mq)

OO Π O έ U

U / d

(4; Li pas «(qe I i pi er t derived from nisL Biocades NV H - υ r γZ )

(5) Amylase (Termamil boG, supplied by Novo Industries Co)

(6) Protease (Alkalase 2, µM, supplied by Novo Ind. Co.)

Example 2

A highly alkaline powder detergent for Dresses were made according to the following recipe. The pH of a 0.133% aqueous solution of the Detergent was 11.2.

Sodium linear dodecylbenol sulfonate 20% by weight

Side (sodium salt of bovine algae

acid) 2% by weight

Sodium orthophosphate 20% by weight

Sodium metaphosphate 10% by weight

Sodium carbonate 15% by weight

Carboxymethyl cellulose 1% by weight

Polyethylene glycol 1% by weight

fluorescent dye ü, 4 wt .-%

Glauber's salt compensation

Enzyme 0 or 2% by weight

Water 5% by weight

The results of the tests performed on the thus produced Reinigungsmitte.η washing test are Ln Table 2 JOINT Asst. As an aside, in Table 2 and the tables below, each R ^ iniqunqmmitteli identified by the Example No. Enzyme No. (the enzyme-free detergent is identified by Example No. (u).

Table ?
Ixei η i gunosmi ttel Laundry index

l- (o) (Purifying agent

1- (1) (Erf iru'unq) 103.5

Copy

BATH

Re intqunqsmittel

Detergency index

l- (2) (invention) 1-C3)

1-C6)

104.0
101
lüü
IuO
IuO, 5

Example 3

A weakly alkaline, powdery cleaning agent for clothes was produced according to the following recipe. The pH value of a 1.3% strength aqueous solution of the cleaning agent was 10.3.

Sodium cC-oiefin sulfonate Soap sodium tripolyphosphate Sodium Silicate (JIS No. 2) Sodium Carbonate Carboxyme.ühylzel lulose polyethylene glycol fluorescent dye Glauber's salt enzyme water

20% by weight

1% by weight

20% by weight

10% by weight

5% by weight

1% by weight

1% by weight

u, 4% by weight

compensation

0 or 2% by weight

10% by weight

In the same way as described in Example 1, the washing test was carried out. The results obtained are shown in Table 3.

Table 3 Re i ti i qunqsmi t Lf * I Detergency index 2- (o) (related resources) IuO 2- (l) (invention) Iü4 2- (2) (invention 104.5 2-CA) 1OU 2-iS) 100 2- (6) lüu, 5 Example 4

A neutral, powdery cleaning agent for clothes was made according to the following recipe. The pH of a 0.133% aqueous solution of the cleaning agent was 6.8.

Sodium linear alcohol (C = 14) sulfate 3% by weight

2υ polyethylene glycol 1% by weight

Sodium phosphate 1% by weight

fluorescent dye 0.2% by weight

Glauber's salt compensation

Enzyme ο or 2 wt .-, b

Water 5% w / w

'' The results of the washing test on the cleaning agents produced in this way are shown in Table 4 L11.

Table 4 Relniqunqsmi tteI detergency index

3- (u) (reference level means) 100

3- (l) (invention) 103

3 - (.?; (En induiiq ^ 103.5

3- (4) 1Ou

3 - ('j; luu

320782J

Example 5

A phosphorus-free, slightly alkaline cleaning agent was made according to the following concept.

Sodium linear dodecylbenzene sulfonate Sodium alkyl ethoxysulfate ^iC 14 ~ ^C 15 ' ^Eü " ^{3 MO1)}

Builders and Enzymes (see Table 5)

Sodium Silicate Sodium Carbonate Carboxymethyl Cellulose Polyethylene glycol fluorescent dye Glauber's salt

water

15 wt% 5 wt%

20% by weight

15 % by weight

15% by weight

1.5 wt%

1.5 wt%

ü, 5 wt .-%

compensation

5% by weight

The results of the washing test are shown in Table 5,

Tabel

Builder

Sodium tripolyphosphate 20%

Sodium citrate, .2υ % '

Zeolite type 4A, 2o%

Sodium citrate, 15 %

Zeolite type 4A, 15%

Sodium citrate, 15 %

Sodium citrate, 15%

Zeolite type 4A, 15%

Zeolite type 4A, 15%

enzyme iat, - r qJ
3 fO 100 Detergency index , 5 - 3 / v (Reference cleaning , 5 - r Qi
3 / fc 98 middle) , 5 (6), 3 / o 98 (Invention) (6), 3 / ο 98 , 5 (invention) (1), 5% 98 , 5 (invention) (2), 102 (Invention) (1), 10 2 (2), 101 102

-3 m-

1!

Cleaning agents were hf; rnes LeJ I L, corresponding to that of Example 3 adopted recipe, using combinations of enzymes. The results of the washing test that have been carried out on this notification are in Table 6 shown.

Table 6

Reiniqunqsini ttel

2- (2) (reference cleaning agent) 2- (2) / (4) (invention 2- (2) / (5) (invention 2- (2) / (6) (invention

(Invention)

(E / f j.ndung 2- (4j / (5j / (b )

Combination of enzymes (the right number qibl- the% rate of the enzyme)

(2) «2

Waschicraf t-
index 5 IGO 5 100, 1Ow, C. 101 5 101, 101,

(4) / (LJ / (6) »2/1/1

Example 7

A schJbcha Ikal i sches, pu Lver ι örrr.i qes fieiniqunqsmittel for Kieidunq was made according to the following Recipe.

Sodium alkyl sulfate (C-14, j)

Nal: riumaikyiä thoxysuli dt (C- 14,!:>, Eu- 3) ropes (Kinderta 1qtyp; Sodium pyrophosphate Nti tr i ums i 1 i ca L

15% by weight

5 wt

2 wt

13 wt.

13 wt

copy

BAD ORiGiNAL

-Vj-

Sodium carboride t. 5% by weight

PolyäthylenbJyco1 2 wt .-%

fluorescent dye 0.2% by weight

Glauber's salt compensation

Magnesium! Heat 1% by weight

Water 5% by weight

Enzyme 2% by weight

Sodium percarbonate 15% by weight

The results of the washing test on the so produced
Cleaning agents are shown in Table 7.

Table 7
15th

Pure! Qungsmi L tel Enzyme detergency index

6- (b) (BezuqsreLrii qunqs-

medium) (6) luo

2 _U '-CD (Eri indunq (1) Io2,5

6- (2) (invention (2) Iü3

BATH ORIGINAL

Claims (1)

DR. KARLTK. IHGEL DIPL.-ING. KLAUS DICKEL H-UilMDNIJ.SWLCi 13 8000 MUNCHtNoO TbLHION (089) 885210 / IKiI I.ASSI N Ji! .M -I 1CJi1AiSCHI-N I1AII N! ΛΜ1 IHK /.BICHtN III KiHAMM-AUKI-SM-. IXJt-XLNkK-PATI-N Γ I i MUNCHI -itrl.i «. IiKI-IIlIiK Ί2 Κ,! Μ) ϋραι d 1U-NH 3231 JJüüO MÜNCUl-N. UUH Kao Scap Co., Ltci- 14-1Ο, Wihcnbashi -Kaycbacho 1-chome, CiUO-ku. Tok yo Reiniqunqsini ttelzusannT.ansp .zvnq f. E π t a π s; ρ ü * ü c 1. Keiniquncrsmi .r? L k e η> i 2 & ι c h η c · fc hold. 3, d 3 <1 due to
: '? β ·.-s iö- an alkaline cell lulase de- 2r Af-i mi ru> -i ^ 3m? (ti 'ρ'iSctw it "./).«} e ^! -i.2U * i «» η * χ ^{; Ί} . Claim!, thereby 5 cl · / e λ Λ / ■ & t C k ρ e. l that the alkali iiicKK "Nr '> 1.AMMUKi «p; t- ·. ·: ANK DKISDNtkHANix ■ ·. (·. LlAMHtlKCi! <! NK »(Hin ·" 1H1 / · w ,. m, BAD ORIGINAL 1'CSlS (IlK KKONIt) MlINfHIN 88S-8Ü2 HANK 011'IS (III IiSNKAd MIIN (MIN Kin NK rtrt 11K1I Uli / -iHi'iiDiiii »2- Cellulase has an optimal OH value range of 8.0 to 11, b . 3. No liquid composition according to claim 1, characterized in that it is marked. chne t that the alkaline cellulase is selected from the group consisting of cellulase produced by a fungus of the bacillus N and cellulase produced by a cellulase-212 producer Fungus belonging to the Aeromonas tribe. 4. Detergent composition according to claim!, Characterized in that it is 0.01 to Contains 70% by weight of the alkali cellulase, with an enzymatic activity of at least Ο, υυΐ units / mg solid. 5. Detergent composition according to claim 1, d a through characterized in that they contain the alkali cellulase in an amount of from ü.l to 1000 Sinheiten / 1 der Contains composition. 6. Detergent composition according to claim!, Characterized in that it contains one or more of the nachfoicenden constituents, namely surface-active agents, divalent metal ion sequestrants, alkali agents, inorganic electrolytes, anti-redeposition agents, bleaching agents. Enzymes. Bluing agents, fluorescent dyes ¹ . Anti -scaling agents, masking agents for factors hindering alkali cellulase activity, activators for alkaline cellulase, antioxidants, solvents and other conventional additives. 7. detergent composition according to claim!, Characterized in that the alkali— Zellulas * is a cellulase derived from the hepatopacreas of the Sea mollusks is extracted. BATH ORIGINAL