DE3207847A1 - DETERGENT COMPOSITION - Google Patents

Description

Cleaning agent composition

The invention relates to a detergent composition. In particular, the invention relates to a detergent composition for fabrics or cloths, which as necessary components a specific surfactant Has agents and a specific cellulase as essential components.

Recently, related to washing clothes remarkable progress has been made. In other words, have the development of input materials, which are suitable as cleaning agents, the improvement of the water quality, the improvement and spread of washing machines as well as the improvement of fibers made washing clothes very easy. Particularly noteworthy is the improvement of input materials for detergents. The improvement of surfactants, organic detergent additives, dispersants, fluorescent paints and bleach can make the impression convey that the detergent compositions for Garments practically reached a perfection to have. The development of detergents for garments, however, is based on the technical ideas that follow summarized have been held up. (1) The effort physicochemically separating the dirt from the fibers by causing the dirt and / or fiber surface surfactant and an organic detergent additive to absorb, to reduce the interfacial tension between the dirt and / or the fiber and the Water. (2) The effort to keep the dirt in a surfactant and an inorganic detergent additive to disperse and solubilize. (3) The dirt chemically decomposed with an enzyme such as a protease. (4) The effort to remove stains using a bleach

to bleach. (5) The effort to create a whitening effect to achieve by causing the fiber surface absorb a fluorescent paint. (6) An effort to prevent it through a chelating agent, that the components used for the washing process are precipitated by divalent metal ions.

Traditionally, the basic idea was to create a cleaning agent for garments aimed at the way in which one can effectively use a detergent with an additive could unite, which attacks the dirt directly, or alternatively supports the additive to attack the dirt. Currently, detergent compositions based on this basic idea have come to a point at which an improvement in terms of the washing process is no longer possible and great efforts would have to be made to further improve the washing power.

To create a new detergent composition based on a new point of view that is free from the conventional ideas washing clothes is to develop, A number of intensive studies have been carried out that surprisingly found that when a detergent composition is brought into contact with a specific cellulase in combination with a specific surfactant has an extraordinary effect Soil detergency results that do not seem to have anything to do with the enzyme activity of cellulase.

As mentioned above, it is with detergents known to use enzymes. However, only those enzymes are known that are effective on a specific dirt act. For example, protase acts on dirt caused by protein, and amylase works on dirt caused by protein caused by starch, and a lipase on dirt, caused by oil and fat. These enzymes attack the dirt directly, while the cellulose according to the invention

read works in different ways. Although the washing mechanism of the cellulase is not yet complete
has been detected, it is likely to act on the fiber surface, especially of cotton or cotton blends, rather than on the dirt, causing the fiber to swell,
or a thin layer of skin which covers the fiber and comes off along with the dirt. In addition, it is believed that
the new fiber surface, which is removed with the dirt, is covered by the specific surface-active
Means, whereby it is then protected from WJader contamination.

The dirt that adheres to the garments includes inorganic ones Solids such as sludge, as well as various

Types of dirt that are derived from proteins, oils and fats, starches, dyes, sweat, etc. combined with each other. An oxidation and another change the dirt occurs in different stages. In particular, a remarkable dirt variation »n observed the clothes of babies and children. aside from that

the dirt on collars, cuffs and socks has its own characteristic properties. With regard to this issue there is a strong need for an all-purpose cleaning agent that has particularly good washing power

shows.

Accordingly, the invention is aware of this
Prior art, the object of which is to provide a powerful all-purpose cleaner for clothes.

This object is achieved according to the invention by the features specified in the characterizing part of the main claim, wherein with respect to preferred embodiments to the features of Subclaims is referenced. The cleaning agent according to the invention is based on the fact that the combination of a specific cellulase and a specific surface-active Agent shows an extremely good cleaning effect for all types of cotton-containing clothing.

The invention comprises a detergent composition for garments, which essentially contains the following ingredients, namely (a) at least one surfactant selected from the group of anionic surfactants, nonionic surfactants and ampholytic surfactants, and (b) a bacteria - and / or fungus-derived cellulase with an enzyme activity of at least 100 units for cotton fabrics (one unit is the activity for one g of the IQ sample to produce 1 m / U mol of reducing sugar from one cotton fabric in one minute).

The cellulase as an essential component of the invention Detergent composition is limited to one those which have an activity on insoluble cellulose, especially cotton fabrics. After the present The level of knowledge is represented by the enzyme activity of the cellulase merely by the ability to hydrolyze water-soluble cellulose (for CMCase) and the ability to be insoluble

2u cellulose (for Avicelase) to hydrolyze. This is not enough from for representing the characteristics of the enzyme activity of the cellulase according to the invention. It is now managed to create the aforementioned unique method to represent the activity. However, it is not clear such as such a representation of activity related to CMCase and Avicelase. In each case it was found that a certain type of cellulase, which has an enzyme activity higher than a certain level, for cotton fabrics successfully acts on the dirt of clothes.

The cellulase, which is used as an essential component according to the invention, is limited to such, derived from bacteria or fungi. As is well known, cellulase exists in nature and is wide common in fungi, bacteria, animals and plants. It has been found, however, that those separated from animals and plants

did not successfully conduct cellulase for the present invention Purpose can be used as the cellulase which is derived from bacteria and fungi.

Preferably, the detergent composition according to the invention should contain the bacterial or fungal derived cellulase in such an amount that the enzyme activity for cotton fabrics is 100 units per g or more, more preferably 500 units Iu p _ro g or more at the optimum pH -Value.

The enzyme activity of cellulase on cotton fabrics was measured in determined in the following manner: a test liquid, composite from 200 mg cotton cloth, which was cut into small pieces to facilitate stirring, 10 mg of a cellulase sample and 10 cm of an aqueous buffer solution with a pH optimal for cellulase activity was at 40 ° C Stirred for 20 hours, after which the freed, reducing sugar was determined according to the DNS method. the Activity for 1 g of the cellulase sample to produce 1 m / U Moles of reducing sugar in one minute was defined as one unit. (The cotton cloth sample had one viscometric degree of polymerization of at least 1000 and a crystalline structure of cellulose I, accordingly the determination by the X-ray method.) Accordingly The DNA process will determine the color that is produced when you add 3,5-dinitrobesalicylic acid with the reducing group of a sugar reacts in an alkali during boiling, determined calorimetrically. (For further details Reference is made to "Experiments on Biochemistry, Part I, Determination of Reducing Sugar" by Sakuzo Fukui, P. 19, 1969, edited by the Gakkai Shuppan Center.)

The term "optimal pH" as used in the determination process is used represents the pH range at which the respective cellulase is at its maximum activity shows.

In the case of the specific surfactant that a Another essential component of the detergent composition according to the invention is one anionic surfactant, one not ionic surfactant or an ampholytic surfactant. Cationic surfactants and long chain fatty acid salts are not preferred. It was found within the scope of the invention that the activity der zellulase (for insoluble cellulase with a viscometric degree of polymerisation greater than 1000 and an X-ray crystallographic structure of cellulose I) is hindered by cationic surface-active substances and long chain fatty acid salts. However, it was also found that the combination of a specific surfactant By means of a specific cellulase, I already know mentioned above, does not lead to a deterioration in cellular activity, or shows a synergistic effect, the goes beyond a worsening of the deviation. Based on the above-described facts, the present invention has been completed.

A great advantage of the detergent composition according to the invention is that it has both detergency of the detergent compositions having a Phoa- ■ contain phat builders, as well as detergent compositions, which contain no or only a small amount of phosphate builder, significantly improved. A Phosphate was generally used for its effect of removing dirt in the form of small particles of sludge, which had entered the space between the fibers. In order to avoid eutrophication, one leans to reduce the content of phosphate in detergents, or the production of detergents that Containing phosphate are restricted by law.

Thus, it has become very difficult to wash out mud dirt using the cleaning agent after the

conventional production. It is well known that such cleaning agents are hardly able to remove sludge dirt to wash out that has penetrated a cotton cloth. Accordingly, the waxing of shoes made of cotton cloth often gives housewives a headache. The detergent composition according to the invention dissolves this problem. The detergent composition according to the invention exhibits detergency which is equal to or better is than the detergency of a weak alkali powder detergent containing a sufficient amount of phosphate, when washing mud-soiled cotton clothing or mixed cotton clothing when it is used (1) in combination with an alkali cleaning agent that contains little or no phosphate, or

(2) in combination with a weak alkali or neutral liquid detergent that does not contain phosphate.

Another advantage of the detergent composition according to the invention is that it has the whitening effect a fluorescent colorant increases in addition to the enzyme activity the cellulase. A fluorescent paint is a highly effective whitener, and the use of this expensive component is proposed in various forms been. Among other things, the use of a wide variety of chemicals has been suggested to reduce the adsorption of the fluorescent Increase the colorant of clothing in the wash bath. One such attempt at the adsorption of a amplifying fluorescent dye is successful in a simple system consisting of a fluorescent Dye and an adsorption promoter, but it is not as successful in a complex, multicomponent system. Indeed, effective adsorption promoters are not currently available. The whiteness of clothes that go through a fluorescent whitening treatment has been transferred is gradually lost, as is the fluorescent color home washing is lost. To such a loss again

to balance, a fluorescent dye is put in brought in the detergents for clothes. A component that improves the coloring ability of a fluorescent dye with repeated washing cycles is very important from the practical point of view. However, such a component has not yet been found. The detergent composition according to of the invention shows a synergistic whitening effect, the ZeHulase and the fluorescent dye «.

The mechanism of such a synergistic effect

is not yet fully understood. It is believed that the cellulase acts on the cellulose fibers to thereby reduce the To make the fiber surface more receptive to fluorescent dyes.

Another great advantage of the detergent composition according to the invention is that when cellulase is used in combination with a bleaching agent the washing and bleaching effect is synergistically improved in the multi-purpose washing process.

As mentioned above, the use of an enzyme in the field of detergents and bleaches is known, but the known enzymes are limited to those that are based on specific types of dirt work. For example, you know that a protease acts on stains caused by protein, an amylase acts on stains caused by starch, and one Lipase on stains caused by oils and fats. These enzymes attack the dirt and stains immediately.

The cellulase that is in the detergent composition

used according to the invention is one of the hydrolases) such as protease and amylase, but they are nonetheless shows a remarkable washing effect for dirt that has nothing to do with the enzyme activity of the cellulase. it is particularly suitable for washing out inorganic solid dirt.

Dirt and stains in clothes are not easy These are complex mixtures of inorganic compounds Solid dirt, food-derived proteins as well as oils and fats, as well as excretions, which are often oxidized over time. Accordingly, they will not necessarily completely washed out even if a cellulase is added to the washing liquid.

When studying the improvement of washability through the Use of cellulase was found to be the target is achieved when you use the cellulase with a bleach combined. Such a combination shows a synergistic washing-bleaching effect.

Another great advantage of the cleaning agent composition according to the invention is that it removes dirt and stains complex type economically and effectively washed out can be, if the cellulase is combined with at least one kind of an enzyme selected from the group, consisting of carboxylate ester hydrase, glucoside hydrase and petptidyl peptide hydrase, which are hydrolases other than cellulase.

Dirt and stains of a complex nature on collars, cuffs and Socks adhere firmly to the fibers and it has been difficult to wash them out with conventional detergents. It it has now been found that when cellulase is combined with other enzymes (in particular protase, amylasβ and lipase), dirt and stains of a complex nature can be washed out economically and effectively with outstanding washing power. This is because the protease, Amylase and lipase represent proteins, oils and fats and starches, respectively attack immediately while the cellulase exerts its own washing effect. 35

Another great advantage of the detergent compositions according to the invention is that the implementation of the

The washing process of inorganic dirt is not influenced by the pH of the detergent composition. As is well known, an enzyme shows its maximum enzyme activity at its optimal pH. Using the detergent composition according to the invention the cellulase with an optimal pH value in the acid range, however, shows sufficient washing activity also in the alkaline range. The detergent composition according to the invention did not differ from conventional ones Detergents with regard to their influence on the Strength of the fibers to be washed.

Another great advantage of the detergent composition according to the invention is that it can be used in any form a cleaning agent can be used, i.e., in a spray-dried powder, a spray-cooled powder, a mixed powder, tablet or liquid.

As mentioned above, any cellulase is widespread in bacteria and fungi, and it can be purified Fractions of this are used as cellulase, which is an essential part of the detergent composition according to the invention.

Examples of bacteria and fungi that produce cellulase are the following:

(a) bacteria

(1) Bacillus hydrolyte icu: rs,

(2) Cellulobacillus mucosus,

(3) Cellu.lobaci.llus myxoqt · ner ,,

(4) CelluJomonas sp.,

(5) Cellvibrio fulvus,

(6) Celluvibrio vulgaris,

(7) Clostridium thermo «.:!. ·]! .U la se um,

(8) Clostridium thermocfl. him,

(9) Corynobactor ium sp.,

(10) Cytophaga globulor; a,

(11) Pseudomnnas fluorcscens var. Cellolosa,

(12) Pseudomonas solanncearum,

(13) Bactericides succinocjenes,

(14) Ruminococcus albus,

(15) Ruminococcus flavofaciens,

(16) Sorandium compositum,

(17) butyrivibrio,

(18) Clostridium sp.,

(19) Xanthomonas cyamopsidis,

(20) Sclerotium bataticola,

(21) Bacillus sp.,

(22) Thermoactinomyces sp.,

(23) Actinobifida sp., (BI) mushrooms ^ Ac tinomycetes)

(1) Act) nomy c e t; e r; sp. ,

(2) Streptomycins sp.,

(b-II) fungi (mold: Deuteromycetes, Phycomycetes, Ascomycetes)

(1) Arthrobotrys superha,

(2) Aspergillus aureus,

(3) Aspergillus flavipes, • (4) Aspergillus flavus,

(5) Aspergillus fumigatus,

(6) Aspergillus luchuenir ;,

(7) Aspergillus nidulan.s,

(8) Aspergillus niger,

(9) Aspergillus oryzae,

(10) Aspergillus rugulosus,

(11) Asp ** rcj i 1 I us aydwi,

(12) AspergilLus tamarii,

(13) As pe rg i11u s t cr to u s,

(14) Asperyillus uncjui:;, dZU / O4 /

(15) Aspurcji 1 lus us do,

(16) Takamine Cellulaso,

(17) Aspergillus saitoi,

(18) Botrytis cinerea,

(19) Botryodiplodia thi-ohromae,

(20) Cladosporium cucummcrinum,

(21) Cladosporium horbnrum,

(22) Coccospora agricola,

(23) Curvularia lunata,

(24) Chaetomium thermophile vat ¹ , coprophile,

(25) Chaetomium tehrmophile var. Dissitum,

(26) Sporotrichum thermophile,

(27) Taromyces emersonii,

(28) Thermoascus aurantiacus,

(29) Humicola grisea veir. thermoidea,

(30) Humicola insolens,

(31) Malbranchea pulcholla var. Sulfurea,

(32) Myriococcum albomycos,

(33) Stilbella thermophi. 1 e,

(34) Torula thermophila,

(35) Chaotomium globosum,

(36) Dictyostelium discoidoum,

(37) Fusarium sp.,

(38) Fusarium bulbigenum,

(39) Fusarium equiseti,

(40) Fusarium lateritium,

(41) Fusarium 'lini,

(42) Fusarium oxysporum,

(43) Fusarium vasinfoctum,

(44) Fusarium dimerum,

(45) Fusarium japonicum,

(46) Fusarium scirpi,

(47) Funariuni solani, (40) Fusarium moniIiI ormo,

(49) Pusarium roseurn,

(50) flelminthosporium sp. ,

(51) Memnoniella echinata,

(52) Humicoia fucoatra,

(53) Humicoia grisea,

(54) Monilia si tophi la,

(55) Monotospora brevis,

(56) Mucor pusillus,

(57) Mycosphaerella citrulline,

(58) Myrothecium verrcaria,

(59) Papulaspora sp.,

(60) Penicillium sp.,

(61) Penicillium capsulatum,

(62) Penicillium chrysogenum,

(63) Penicillium frcquentans,

(64) Penicillium janthinellum,

(65) Penicillium luteum,

(66) Penicillium piscarium,

(67) Penicillium soppi,

(60) Penicillium spinulosum,

(69) Penicillium turbatum,

(70) Penicillium digitatum,

(71) Penicillium expansum,

(72) Penicillium pusillum,

(73) Penicillium rubrum,

(74) Penicillium wortmanii,

(75) Penicillium variabile,

(76) Pestalotia palmarum,

(77) Pestalotiopsis westercli jkii,

(78) Phoma sp.,

(79) Schizophyllum commune,

(80) Scopulariopsis brevicaulis,

(81) Rhizopus sp.,

(82) Sporotricum carfiis,

(83) Sporotricum pruinoaum,

(84) Stachybotrys alra, (05) Tcu-ula sp. , (ti 6) Trichoderina ν i r icJ ι>,

(87) Trichuru «cylindricu; ·.,

(88) Vert icil 1 i.um albo iitniin,

(89) Aspergillus collu J. oh tie,

(90) Fenicil 1 ium glaiicum,

(91) Cunninghamella sp.,

(92) Mucor mucedo,

(93) Rhyzopus chinone ir ;,

(94) Coremiella sp.,

(95) Katrlingia rosea,

(96) Phytophthora cacLoruiii /

(97) 'Phytophthora ciLti co J a,

(98) Phytophthora parasit ica,

(99) Pythium sp.,

(100) Saprolegn iaceae,

(101) Ceratocystis ulnii,

(102) Chaetornium globosum,

(103) Chaetomium indicum,

(104) Neurospora crassa,

(105) Sclerotium rolfsii,

(106) Aijpergillus sp.,

(107) Chrysosporium H (j no rum,

(108) Penicillium no ta turn, . (109) Pyricularia oryz <ie,

(b-III) mushrooms (Bar.idiomycetns)

(1) Collybia veltipcs,

(2) CoprinuH sclerot icpTuis,

(3) Hydnum henningsii,

(4) Irpex lacteus,

(5) Polyporus sulphrcus,

(6) Polyporus supervisor.,

(7) Polystictus hirCutu ;; ,, (U) TrameLes vita ta,

(9) Irpex consolus, (lü) Lentinur. lepidous,

(11) Poria vaporatria,

(12) Fomes pinicola,

(13) Lenzites styracina,

(14) Merulius lacryman.s,

(15) Polyporus palstri «,

(16) Polyporus annosus,

(17) Polyporus versicolor,

(10) Polystictus sanguinoun,

(19) Poria vailantii,

(20) Puccinia graminis,

(21) Tricholoma fumosum,

(22) Tricholoma nudum,

(23) Trametes sanguinea,

(24) Polyporus schweini t / .i i FR.,

(25) Coniciiophora cerebella,

According to the Erfindunq the folqenden commercial cellulases can be einqesetzt which are abqeleitet of the above bacteria and fungi for Reiniqunqsmittelzusammensetzunq.

(1) Cellulose ΛΡ (Amano Pliarmaceut ical Co., Ltd.)

(2) Celluloiiin ΛΡ (Ueda Chemical Co., Ltd.)

(3) Cellulofjin AC (Ueda Chemical Co., Ltd.)

(4) Cellulase onozuka (Kinki Yakult Seizo Co., Ltd.)

(5) Pancellase (Kinki Yakult Seizo Co., Ltd.) • (6) Macerozyme (Kinki Yakult Seizo Co., Ltd.)

(7) Meicelase (Meiji Seika Kaisha, Ltd.)

(8) Celluzyme (Nagase Co., Ltd.)

(9) Soluble bubble (Sankyo Co., Ltd.) (lü) Sanzyme (Sankyo Co., Ltd.)

(11) Cellular ^ A-12-C (Tcikeda Chemical Industries, Ltd.)

(12) Toyo celli lase (Toyo Jozo Co ,, Ltd.)

(13) Driserase (Kyowa Hakko Kogyo Co., Ltd.)

(14) Luizyme (Luipf> ld Werk)

(15) Takamine-Cellulasf (Chemical Factory)

(16) Wii 1 1 c-Tütcin-Ce J I u J .ι:; ι · (Siqin.i Chomicals)

(17) Ce 11.ulane Type 1 (Sirjma Chemicals)

(18) Cellulase Scrvii (i-icrva Laboratory)

(19) Cellulose 36 (Nolnn beef hair;) (20) MiJes Cellulase 4,000 / Miles)

(21) Ri-H cellulase 35,36,30 cone (Philip Morris)

(22) Combizym (Nysco Labora tory)

(23) Cellulase (Makor Chomicals)

(24) Cellucrust (NOVO Iri «iustry)
^ q (25) CellulasG (Gist-Hrucades)

The anionic, nonionic and amphoIytic surfactants that are useful for the present invention Cleaning agent composition are used, can be exemplified as follows:

(1) Linear or branched alkyl benzene sulfonates with alkyl groups having an average carbon number of 10-16.

(2) Alkyl or alkenyl ether sulfates with linear or branched alkyl groups or alkenyl groups with one another average carbon number of 10 - 20 and with 0.5-8 moles on the average of ethylene oxide, porpylene oxide, butylene oxide, ethylene oxide / propylene oxide ■ 0.1 / 9.9 up to 9.9 / 0.1 or ethylene oxide / butylene oxide «0.1 / 9.9 to 9.9 / 0.1 added in one molecule.

(3) Alkyl or alkenyl sulfates with alkyl groups or alkenyl groups with an average carbon number of 10-20.

(4) Olefinsulfonate with 10 to 20 carbon atoms in the Average in a molecule.

(5) Alkanaulfonate with 10 to 2ü carbon atoms in Average in a molecule.

The counter ions of the anionic surfactants Agents are exemplified by alkali metal ions such as sodium and potassium; Alkaline earth metal ions such as calcium and magnesium; Amonium ions as well Alkanolamines (for example monoethanolamine, diethanoiamine, triethanolamine and triisopropanolamine) with 1 to 3 alkanol groups of carbon number 2 or 3.

(6) Sulfonate type ampholytic surfactants represented by the following formula

^{No. 1}

¹ O θ

R ₁₁ CONH-R ₁ 2 ~ ^NR 14 " ^SO 3

«13

wherein R is an alkyl or alkenyl group of carbon number 8 to 24, R ₁₂ is an alkenyl group of carbon number 1 to 4, R ₁₃ is an alkyl group of carbon number 1 to 5 and R. is an alkylene or hydroxyalkylene group of carbon number 1-4.

No. 2

«16 30th

where R ₁ ^ and R _{14 have} the aforementioned meaning, while R ₁₅ and R _{16 are} an alkyl or an alkenyl group with a

Carbon number is 8 to 24 and 1 to 5, respectively. 35

(C ₂ H ₄ O) ₀₁ II

where R and R _{4 have} the aforementioned meaning, while nl is an integer from 1 to 20.

(7) Betaine type ampholytic surfactants represented by the following formulas:

number 1

R ₂₂

I ²¹

R22

where R _{2 is} an alkyl, alkenyl, / I -hydroxyalkyl, or A-hydrolxyalkenyl _{group with a carbon number of up to 24, R 22 is an} alkyl group with a carbon number of 1 to 4 and R _{23 is} an alkylene or hydroxyalkylene group with a carbon number is from 1 to 6.

No. 2
^25th

(C ₂ M ₄ OJn ₂ H

• ^ where Rp. "And Rp ^ have the aforementioned meaning, while n2 is an integer from 1 to 20.

No. 3

«24 _R _n <B_ _h

^C 2 4

where Rg ^ and R- have the aforementioned meaning, while R _{34 is} a carboxyalkyl or hydroxyalkyl group with a carbon number of 2 to 5.

(8) Polyoxyethylene alkyl or alkenyl ethers with alkyl or alkenyl groups having an average carbon number of 10 to 20 and 1 to 20 moles added ethylene oxide.

(9) Polyoxyäthylenalkylphenyläther with an alkyl group average carbon number from 6 to 12 and with 1 to 20 moles of ethylene oxide added.

(10) Polyoxypropylene alkyl or alkenyl ethers with alkyl groups or alkenyl groups of a transparent Carbon number from 10 to 20 and with 10 to 20 moles of propylene oxide added.

(11) polyoxybutylene alkyl or atenyl ethers with alkyl

groups or alkenyl groups of an average Carbon number from 10 to 20 and with 1 to 20 moles of butylene oxide added.

(12) Nonionic surfactants with alkyl groups or alkenyl groups an average carbon number of 10 to 20 and with 1 to 30 moles in total of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide added (with a molar ratio of ethylene oxide to propylene oxide or butylene oxide of C, 1 / 9.9 to 9.9 / O ₁ I).

(13) Higher fatty acid alkanolamides or alkylene oxide adducts thereof represented by the formula:

K ¹ 12

R'iiCON

R'12

where R ¹ ^ _{1 is} an alkyl group or alkenyl group with a carbon number from 10 to 20, R » _{12 is} H or CH ₃ , n3 is an integer from 1 to 3 and m3 is an integer from 0 to 3 ·

(14) Sugar fatty acid esters composed of sugar and ' Fatty acid with an average carbon number of 10 to 20.

(15) Fatty acid glycerol monoester composed of glycerol

and fatty acid having an average carbon number of 10-20.

(16) Alkylamine oxides represented by the formula:

R ¹ 14 R- ₁₃ - H - 0

R ¹ 15 25

where R '13 _has an alkyl group or an alkenyl group a carbon number of 10 to 20 and R * ₁₄ and R'c are alkyl groups of a carbon number of 1 to 3.

The detergent composition according to the invention can

optionally contain the following ingredients as deemed necessary.

I. cellulase derived from animals and plants such as them are listed below:

(a) Protozoa (ciliate, hostage, amoeba, etc.)

(1) Kndoplodinum negated

(2) Trichomonn's termop:; idus

(b) Mollusks (snails, soft clams, tapworms , etc.)

{ 1 ) Helix ponaLia

( λ) Stromoririr »cj igan

(3) Dol.abc.11n auricula iiolander

(4) My ti-Iu £ 3 Outera

(5) Xylopliaga dorsalis

(6) Cryptochiton stelleri

(7) Pterocera crocata

(8) Caelatura hautecoouri ruellani

(9) Melanoides tuberculata

(10) Mya arenaria

(11) Mactra solidissima

(12) Bankia setacea

(13) Bankia indica

(14) Teredo

(15) Modiola modiolus

(16) Cryptoplax japonica

(17) Heliotis japonica

(18) Turbo CornutuG

(19) Tegula phoifferi

(20) Lemintina imbricata

(21) Fasciolaria trapezium

(22) Dolabella auricula

(23) Bcmoiodoris jaf) onica

(24) Dendrodoris ruba var. Nigromaculata

(25) Onchidium verruculatuni

(26) Euhadra peliomphala

(27) Mytilus edulis

(2ö) Meretrix meretrix lusoria

(29) Venerupis philippinarum

(30) Octopus sp. (c) nematodes

(1) Ditylenchus destructor

(2) Ditylenchus dipsaci

(d) Anne I id en

(L) Kunice aphrodi to is

(2) TyLorrhynchus heterochaetus

(J) Glycera chirori

(4) rjOLmi a moclusa

(5) Be hol lastarte indica

(6) Rhizodrilus πp.

(7) Pho ret inn r, p.

(e) Hchinoduriiiat en (seeiqel etc.)

(1) Anthocidaris crassispina

(2) Pseudocentrotus depressus

(3) flcmicentrotus pulcherrimus

(4) P.'iammochinue milianr,

(f) crustaceans

(1) Mitella mi toila

(2) Megaligia exotica

(3) Calappa lophus

(4) Gaetice depres.sur;

(5) Pachygrap from cra.s.sipes

(6) Plagusia dentipes

(7) Charybdi.s miles

(8) Careinoplax longimanus

(9) Tiarinia cornigcra

(10) Leptomi t hrax e <Jwat'dsi

(11) Naxioidos hystrix

(12) Hepa locj.isher don ».ata (lj)> Ariiculuii anicului;

(14) Dardanur. cra.ss iuianus

(15) U po ge b ia m a j ο r

(J6) Panulirus japonicus

(17) Penaeus japonicus

(18) Scyllarides Sieboldi

(19) Procambrirus clarkii

(g) Insects (ants, beetles, etc.)

(1 1 Tot ; ■ ''<■; ·. OPtV-US

(2) Ctenolupisma iinnata

(1) Cerambyx cerdo

(4) Xestobium rofovi Ho :; around

( ^r j) Na:; u I. it harvest «exi tioKU.s

(6) Copl. Otermes lactous

(7) Strorniitium fulvum (H) Dixippun mo ro η UFi ( ¹ J) Limnorin lignotrum

(h) Alqen

(1) Cladophora rupestris

(2) Ulva lactuca

(3) Laminaria digitata

(4) Rhodymenia palmata (i) Lichines or lichens

(1) Usneaceao

(2) Cladoniaceae

(3) Parineliaceae

(4) Umbilicariaceae

(j) Terrestrial chlorophyll carriers

(1) tobacco plant

(2) pineapple stalks

(3) Acer pseudoplatanus stalks

(4) French bean leaves

(5) Artichoke leaf stalks

6. Spinach

(70 Solanum Dulcamara root

8. Pumpkin

(9) Asparagus tip

(10) barley

(11) malt

II. Hydrolase other than ZeXlulase

Carboxylate ester hydrolase, thioester hydrolase, phosphate " monoester hydrolase and phosphate diester hydrolase based on the ester linkage act; Glycoside hydrolase acting on the Glycosyl Compound acts, an enzyme that hydrolyzes N-glycosyl compounds; Tiijo ether hydrolase acting on the Ether binding acts and ^ -aminoacyl-peptide hydrolase, peptidyl-amino acid hydrolase, acyl-amino acid hydrolase, Dipeptide hydrolase as well as peptidyl peptide hydrolase, the act on the peptide bond. Among these, · are preferred Carboxylate ester hydrolase, glycoside hydrolase and peptidyl peptide hydrolase.

These preferred hydrolases are given by way of example as follows:

(1) Proteases belonging to peptidyl peptide hydrolase

Pepsin, pepsin B, rennin, trypsin, chymotripsin A,

Chymotripsin B, Elastase, Enterokinase, Cathepsin C, . Papain, chymopapain, ficin, thrombin, fibrinolysin, Renin, Subtilisin, Aspergillopeptidase A, Collagenase, Clostridiopeptidase B, Kallikreln, Gasteisin, Cathepsin D, bromelin, keratinase, chymotripsin C, pepsin C, Aspergill opeptidase B, urokinase, carboxypeptidase A and B as well Aminopeptidase.

(2) glycoside hydrolases 30th

Cellulase, which is an essential component, is excluded from this group.

^ -Amylase, / Ci-amylase, glucoamylase, invertase, lysozyme, pectinase, chitinae and dextranase. Preferred of these a- and -Amyläse / i -Amyläse are, they cause a neutralization in acid system, but

that obtained from bacteria shows high activity in an alkaline system.

(3) carboxylate ester hydrolase 5

Carboxylesterase, lipase, pectinesterase and chlorophyllase. Of these, lipase is particularly effective.

The trademarks of the commercial products are

indicated below, with the manufacturers also listed in brackets: "Alkalase", "Esperase", "Sabinase", ¹¹ AMG "," BAN "," Fungamill ",» Seetzyme ··, "Termamill" (Novo Industry, Copenhagen, Denmark); "Maksatase", "Highalkaline ft-otease""," Amylase THC ' ¹ , "Lipase" (Gist Brocades,

N.V. Delft, Holland)! "Protease B-400", "Protease B-4000",

"Protease AP", "Protease AG 2100" (Swiss Ferment AG, Basel, Switzerland); "CRD Protase" (Monsanto Company, St. Loius, Missouri, V.St.Α.); "Piocase" (Piopin Corporation, Monticello, Illinois, V.St.A.); "Pronase P", "Pronase AS", "Pronase AF" (Kaken Chemical Co., Ltd. Japan); "Lipadase P-2000 "(Lapidas, Secran, France);" Protease Products "(a grain size of 100 % between 0.991 mm and 0.104 mm) (Clington Corn Products, a division of Standard Brands Corporation, New York, V.St.A. ); "Takamine", "Bromelain 1:10", "HT Protease 200", "Enzyme L-W" (obtained from fungi, not bacteria) (Miles Chemical Company, Elkhart, Ind. V.St.A.); "Rozyme P-Il Cone", "Pectinoiy" Lipase B "," Rozyme PF "," Rozyme J-25 "(Rohm & Haas, Philadelphia, V. St. S.); "Ambrozyme 200" (Jack Wolf & Co., Ltd. a division of Nopco Chemical Company, Newark, N.J. V.St.A.); "ATP 40", "ATP 120", "ATP 160" (Lapidas, Secran, France); "Oripase" (Nagase & Co., Ltd, Japan).

-28- : j ~ r : ./. "-:" -_ .: "

The hydrolas "besides the cellulas" is brewed into the detergent composition in such an amount as this is necessary for the respective purpose. Preferably it should be in an amount of 0.001 to 5 parts by weight and more are preferably introduced in an amount of 0.02 to 3% by weight, based on the purified material. This enzyme should be used in the form of granules made from crude enzyme alone or in combination with others Ingredients of the detergent composition. Granules of the crude enzyme are used in such an amount that the purified enzyme is present in an amount from 0.001 to 1/2 weight percent. Purified enzyme is diluted so that the granules are used in an amount of 0.002 to 10% by weight and preferably 0.01 to 5% by weight.

III. Cationic surfactants and long chain Fatty acid salts

(1) Saturated or unsaturated fatty acid salts with a average carbon number from 10 to 24 in the molecule.

2) alkyl or alkenyl ether carboxylic acid salts, the one Contain alkyl or alkenyl group, with an average carbon number of 10 to 20 and with 0.5 to 8 moles on an average of ethylene oxide, Propylene oxide, butylene oxide, xethylene oxide / propylene oxide in a ratio of 0.1: 9.9 to 9.9: 0.1 or Ethylene oxide / butylene oxide in a ratio of 0.1 : 9.9 to 9.9: 0.1 added in one molecule.

3) cZ-sulfofetta acid salts or esters of the following formula:

R - CHCO-.Υ

I '

SO ₃ Z

where Y is an alkyl group having a carbon number of 1 to 3 or a counterion, Z is a counterion and R is an alkyl or alkenyl group with a Carbon number from 10 to 20. 5

4) Amino acid type surface active agents of the following general formula:

number 1

R _n - CO - N - CU - COOX

L R

2 "3

where R is an alkyl or alkenyl group with a carbon number of 8 to 24, R _{2 is} hydrogen or an alkyl group of carbon number 1 to 2, R _{3 is} an amino acid residue and X is an alkali metal or alkaline earth metal ion,

No. 2

- CO - N - < ^CH 2 ⁾ n " ^C00X K2 '

where R, R ₂ and X have the same meaning given above, while η is an integer from 1 to 5,

No. 3

> N - (CF! -.) - COOX R "

where R. and X have the same meaning as mentioned above, have, while m represents an integer from 1 to 8, 35

No. 4

R ₁ - N - CI! - COOX

¹ II

^R 4 ^R 3

_15th

₃₅

where R ^, R «and X have the meaning given above, while R. is hydrogen or an alkyl- or hydroxyalkyl with a carbon number of · 1 to 2 is,

No. 5 ^R 5 -

^R 2 ^R 3

where R ₉ , R, and X have the same meaning as above

ΊΟ λ

wrote, have, while R _{5 is} a ρ -hydroxyalkyl or p-hydroxyalkenyl group with a carbon number of 6 to 28 and

- CH - COOX

where R ₃ , Rc and X have the same meaning as above.
20th

5) Phosphate ester surfactants:

No. 1 alkyl (or alkenyl) acid phosphates of the general formula:
0

. (KO) _n . - P - ^(On) m '

where R ^{1 is} an alkyl or alkenyl group with a carbon number of 8 to 24, n '+ m'<- 3 and n '«1 to 2.

No. 2 alkyl (or alkenyl) phosphates of the general formula

where R 'has the same meaning as above, while n' ^ m ¹¹ ^ and n '' »l-3 and

No. 3 alkyl- (or alkenyl-OPhosphates of the general Formula:

(R ¹ O) _n ,, - ί · "

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

6) Cationic surfactants all of the following ge · my formula:

No.

R'-

R '

..Θ

where at least one of R ¹ - »R * ₂ » ^R * 3 ^{and RI} 4 represent an «alkyl or alkenyl group with a carbon number from 8 to and the others represent an alkyl group with a carbon number from 1 to 5, while X ^{1 is} a halogen is.

No.

RV

.e

where R ·, R ' ₂ , R · and X ^{1 have} the same meaning as above.

No.

(R 5 ° ',, H
A. I. 4th ^R1 i - N
[ '*> - η '?
4th

-Θ

where R '->R' ₂ and X ^{1 have} the same meaning as above, R ' _{5 is} an alkenyl group with a carbon number from 2 to 3, while n. represents an integer from 1 to 20.

IV. Builder

Bivalent sequestering agents
The composition may contain 0-50% by weight of one or more builder components selected from the group consisting of alkali metal salts and alkanolamine salts of the following compositions:

1) phosphates such as orthophosphate, pyrophosphate, tripolyphosphate, Metaphosphate, hexametaphosphate and phytic acid,

2) phosphates such as ethane-1,1-diphosphanate, ethane-l, l, 2-triphosphonate, Ethane-l-hydroxy-1,1-diphosphonate and its derivatives, Ethane hydroxy-1,1,2-triphosphonate, ethane-1,2-dicarboxy-1,2-diphosphonate and methane hydroxyphosphate,

3) Phosphonocarboxylates such as 2-phosphonobutane-1,2 -dicarboxylate, l-phosphonobutane-2,3,4-tricarboxylate and jC -methylphosphonosuccinate,

4) salts of amino acids such as aspartic acid, glutamic acid and glycine, '

5) amino polyacetates such as nitrile triacetate, ethylenediaminetetraacetate, Diethylenetriamine pentaacetate, iminodiacetate, glycol ether diamine tetraacetate, Hydroxylethyliminodiacetate and diene colate,

6) high molecular electrolytes such as polyacrylic acid, polyaconitic acid, Polyitaconic acid, polycitraconic acid, polyfumaric acid, Polymaleic acid, polymesaconic acid, poly - / - hydroxyacrylic acid, Polyvinylphosphonic acid, sulfonated polymaleic acid, maleic anhydride / diisobutylene copolymer, maleic anhydride

drid / styrene copolymer, maleic anhydride / methyl vinyl ether copolymer, maleic anhydride / ethylene copolymer, maleic anhydride / ethylene crosslinked copolymer, maleic anhydride / vinyl acetate copolymer, Maleic anhydride / acrylonitrile copolymer, malelic anhydride / acrylic ester copolymer, maleic anhydric / autadiene copolymer, maleic anhydride / Isoprene copolymer, poly-ketocarboxylic acid derived from Maleic anhydride and carbon monoxide, itaconic acid / ethylene copolymer, itaconic acid / aconltic acid copolymer, itaconic acid / maleic acid copolymer, itaconic acid / acrylic acid copolymer, malonic acid / Methylene copolymer, mesaconic acid / fumaric acid copolymer, ethylene glycol / ethylene terephthalate copolymer, vinylpyrrolldone / vinyl acetate copolymer, l-butene-2,3,4-trocarboxylic acid / itaconic acid / Acrylic acid copolymer, polyester polyaldehyde carboxylic acid, the contains a quaternary ammonium group, the cis isomer of

Epoxysuccinic acid, poly CNjN-bisiCarboxymethyDAcrylamidJ,

PolyCHydroxycarboxylic acid), starch / succinic acid or maleic acid or terephthalic acid ester, starch / phosphoric acid ester, Dicarboxy starch, dicarboxymethyl starch and cellulose / succinic acid ester,

7) non-dissociating polymers 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, oxalacetic acid, hydroxydisuccinic acid, carboxymethylhydroxysuccinic acid and Carboxymethyl tartronic acid; salts of hydroxycarboxylic acids, such as glycolic acid, maleic acid, hydroxypivalic acid, tartaric acid, citric acid, lactic acid, gluconic acid, mucic acid, glucuronic acid and dialdehyde starch oxide; Salts of Itaconic 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-l, 2,3-tricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, Ethane tetracarboxylic acid, ethenetetracarboxylic acid, n-alkenylaconitinsmure, 1,2,3,4-cyclopentanetetracarboxylic acid, Phthalic acid, trimesanoic acid, hemimellitic acid, pyromellitic acid, benzene hexacarboxylic acid, Tetrahydrofuran-1,2, 3,4-tetracarboxylic acid and Tetrahydrofuran-2,2,5,5-tetracarboxylic acid salts of sulfonated carboxylic acids, such as sulfoitaconic acid, sulfotricarballylic acid, Cysteic acid, sulfoacetic acid and sulfosuccinic acid; Carboxymethylated sucrose, lactose and raffinose, carboxymethylated pentaerythritol, carboxymethylated Gluconic acid, condensates of polyhydric alcohols or sugars with maleic anhydride or succinic anhydride, condensates of hydroxycarboxylic acids with maleic anhydride or succinic anhydride, CMOS and salts of organic acids from Builder M and similar,

9) aluminosilicate salts:

No. 1 Crystalline aluminosilicate salts of the formula: Χ · (Μ · ₂ 0 or MO) · Al ₂ O ₃ - y {Si0 ₂ > · W (H ₂ O)

where M · an alkali metal atom, M · «an alkaline earth metal

atom interchangeable with calcium, x ', y' and w 'represent the number of moles of the respective components, where generally x between 0.7 and 1.5, y between 0.8 and 6, while w ^{1 is} a positive number,

No. 2 compounds of the following general formula are preferred as detergent builders:

where η is a number from 1.8 to 3.0 and w is a number from 1-6 represents

No. 3 Amorphous aluminosilicate salts of the formula:

X (M ₂ O) -Al ₂ O ₃ -Y (SiO ₂ ) -W (H ₂ O) -

where M represents a sodium and / or potassium atom and x »y and w are molar numbers of the respective components, in the following areas:

0.7 <χ <1.2
1.6 <y S 2.8
10

w: any positive number including 0, and

No. 4 Amorphous aluminosilicate salts of the formula: X (M ₂ O) -Al ₂ O ₃ -Y (SiO ₂ ) -Z (P ₂ O ₅ ) -OJ (H ₂ O)

where M represents Na or K and X, Y, Z and ν are the number of moles of the respective components in the following ranges:
20th

o.2O <; χ <l.io

0.20 <Y <4.00 0.001 1 Z <0.80

4j: any positive number including 0.

Alkali or inorganic electrolytes

The composition can be 1 to 50% by weight, preferably 5 to 30% by weight, based on the composition, of one or more alkali metal salts of the following compounds contain as alkali or inorganic electrolytes: silicates, carbonates and sulfates, as well as organic ones Alkali such as triethanolamine, diethanolamine, monoethanolamine and triisopropanolamine.

V. Antiredeposition Agents

The composition can contain 0.1 to 5 % of one or more of the following ingredients as anti-redeposition agents: polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone and carboxymethal cellulose.

Among these shows a combination of carboxylmethyl cellulose and / or polyethylene glycol with the cellulase according to the invention a synergism in the removal muddy dirt.

To prevent the carboxymethyl cellulose from being decomposed by the cellulase in the detergent is it is desirable that the carboxymethyl cellulose be granulated or coated before it is incorporated into the composition.

VI. Bleach 20th

A further improvement in the cleaning effect will be achieved by using the cellulase according to the invention in combination with a bleaching agent such as Sodium percarbonate, sodium perborate, sodium sulfate / hydrogen peroxide adduct and sodium chloride / hydrogen peroxide

adduct and / or a light-sensitive bleach colorant, such as zinc or aluminum salt of sulfonated) phthalcyanine.

VII. Bluing agents and fluorescent dyes 30th

Various bluing agents and fluorescent colors can be incorporated into the composition if necessary. For example, connections recommended with the following structure: 35

-M-

Vnh -, * ^N Y-NH-

GH

GO ₃ Well

SO ₃ Na

SO ₃ ITa

SOjNa

SO ₃ Na

Blueing agent of the following formula

D-Na-O I N

C-Y

(30, H)

D denotes a residue of a blue or purple monoazo-diazo or anthraquinone dye _t X and Ϊ each denotes a hydroxyl group, an amino group, an aliphatic amino group which can be substituted by a hydroxyl, sulfonic acid, or carboxylic acid Alkoxyl group or an aromatic or alicyclic group Amino group which can be substituted with a hydrogen atom or hydroxyl, sulfonic acid, carboxylic acid, lower alkyl or lower alkyl group, R represents Hydrogen atom or a lower alkyl group excluding cases in which (1) R is hydrogen and both X and Y represent hydroxyl or alkanolamino group at the same time and (2) R is hydrogen and one of X and Y is Hydroxyl group and the other is an alkanolamino group and η is an integer of at least 2,

D-NII-C C-X

Il I

N N

D denotes a residue of a blue or purple azo or anthraquinone dye, X and Y is the same or a different alkanolamino group or hydroxyl group.

VIII. Caking Prevention Agents.

The following anti-caking agents can be used in the powder detergent are introduced: p-toluenesulfonic acid salts, xylenesulfonic acid salts, acetic acid salts, sulfosuccinic acid salts, talc, finely powdered silica, clay, calcium ciumate (such as Micro-Cell from Johns Manvill Co.), Calcium carbonate and magnesium oxide.

IX. Covering agent for factors affecting cellulase activity hinder.

The cells are deactivated in some cases the presence of copper, zinc, chromium, mercury, Lead, manganese or silver ions or their compounds. Various metal gelling agents and metal precipitating agents act against this «inhibitors. They embrace for example divalent metal ion sequestrants, as listed above under the paragraph CO, with reference to the optional additives, as well Magnesium silicate and magnesium sulfate. ^., _

Celllobiose, glucose, and gluconol acetone sometimes work as inhibitors. It is preferable to avoid the presence of these saccharides together with the cellulase as far as possible. When the common presence is unavoidable, it becomes necessary that to prevent direct contact of the saccharides with the cellulase, for example by coating.

Long chain fatty acid salts and cationic surfactants act as inhibitors in some cases. However, the co-presence of these substances with the cellulase is permissible if there is direct contact this prevents what can happen by tabletting or coating.

The covering means and methods described above can be used in accordance with the invention, if necessary will.

X. Cellulase Activators

The activators depend on the particular cellulase difference. In the presence of proteins Cobalt and its salts, magnesium and its salts,

-4U-

Calcium and its salts, potassium and its salts, sodium and its salts, or monosaccharides, such as Mannose and xylose activate the cellulases and their cleaning power is remarkably improved.

XI. Antioxidants

The antioxidants include, for example, tert-butylhydroxytoluene, 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 2,2'-butylidenebis (6-tert-butyl-4-methylphenol), hionostyrenated cresol, distyrenated cresol, monostyrenated phenol, distyrenated phenol and 1,1-bis (4-hydroxyphenyl) cyclohexane.

XiI. Solubilizer

the solubilizers include, for example, lower alcohols such as ethanol, benzenesulfonate salts, lower ones Alkylbenzyl sulfonate salts, such as p-toluenesulfonate salts, Glycols such as propylene glycol, acetylbenzenesulfonate salts, acetamides, pyridinedicarboxylic acid amides, benzoate salts and ureas.

The detergent composition according to the invention can be used in a wide pH range of one acidic to an alkaline pH value can be used.

The following examples further illustrate the invention. Unless otherwise stated, the Percentages of the following examples on weights.

example 1

There were cleaning attempts of different combinations of surfactant and cellulase passed through

/ - ■■

22 ΰ 78 47 "

leads to · pieces of cotton cloth that are artificially carried along Stains of oil, grease and charcoal.

l) detergent composition: 5

Surface active agent 20 % Beef tallow soap 2 % Sodium tripolyphosphate 20 % Sodium silicate 10 % Sodium carbonate 10 % Polyethylene glycol 1 %

(average molecular weight: MW 6000)

fluorescent dye 0.4%

Water 10% enzyme 3%

Glauber's salt 23.6%

total 100 %

2) A cloth artificially stained with oil and fat:

A Baumwo11 calico stained with the following oil, Fat and coal:

The oil composition (colored with carbon black)

used for the manufacture of artificially stained cloth :

Cotton seed oil 60% Cholesterol IO % Oleic acid 10 % Palmitic acid 10 % Liquid and solid paraffins 10 %

3) Washing conditions and procedures as well as evaluation:

A detergent was dissolved in water by 4 ° DH hardness to form one liter of a 0.133 36% aqueous cleaning agent solution. Five pieces of one Cotton cloth that has been artificially stained with oily dirt were immersed in the detergent aqueous solution. After standing at 40 ° for two hours, the detergent solution and the Pieces of the artificially stained cloth transferred to a stainless steel beaker and stirred at a Turgotometers 1OQ revolutions per minute at 20 ⁰ C for 10 minutes in the Turgotometer. After washing them in running water, they were ironed with an iron and theirs Reflectivity was measured. The cleaning level was calculated according to the following formula:

The reflectance of the original cloth before washing and that of the stained cloth before and after washing were measured at 550 m u by means of an automatic recording colorimeter (a product of Shimadzu Seisaku-sho), and the washing amount (%) was calculated from of the following formula:

__ Power of reflection Power of reflection

"(after) - (before)

_{Degree of} cleaning - washing _{χ 1QQ}

(%) Reflectivity Reflectivity (of the original) - (before) washing the cloth

An average of five samples is shown in Table I.

4) Enzymes used:

(1) Cellulase-onozuka (Kinki Yakult Co., Ltd | derived von Trichöderma viridej 4000 units / g)

(2) Cellulosin AP (Ueda Kagaku Co., Ltd. derived from Asperqillus Nigerf 860 units / g),

(3) Meicelase (Meiji Seika Co., Ltd .; derived from Trichoderma honingl; 1100 units / g),

(4) Bacterial e6 amylase (NOVO Co.,; Termamyl 60 G; 60 KNU / g)

(5) amyloglucoeidase (NOVO Co .; ANG; 200 AG / ml),

(6) ^ - glucanase (NOVO Co .; Celleflo 200L; 200 BGU / g), (7) dextranase (NOVO Co .; DN25L; 25KDU / g),

(8) Galactomannase (NOVO Co .; Gamanase 1.5L; 1500 KVHCU / g),

(9) Glucose Isomerase (NOVO Co., Sweetzyme Type A), 15th

(10) Bacterial Protease (NOVO Co .; Alkalas «2.0 M, 2AU / g),

(11) Bacterial Portease £ Gist Brocades Co., jMaxatase P; 330,000 DU / g),

(12) Mold lipase (Nagase Sangyo Co .; olipase)

5) Surfactants:

(a) Sodium n-Dodecylbenzenesulfonate

(b) Sodium alkyl sulfate of oxo alcohol series (C ₁₄ ^ ₁ S)

(c) Sodium alkylethoxy (P «3) sulfate of the oxo alcohol series

^iC 14-15 ⁾

(d) Sodium / olefin sulfate (C _{1 c Λα} )

(e) Sodium alkene _{(C 16) sulfonate}

(f) lake. Alcohol (C-13.5) ethoxylate (Average number of moles of added Ä

oxides: EO-7)

(g) Lauryl betaine

(h) lauryl amine oxide

(i) Beef suet soap

(j) mono (long chain alkyl (from beef tallow)) trimethylammonium chloride id.

6) Results:

Cleaning supplies
No. Enzyme no. surfaces
active agent
No. a Cleaning
measure (%) 1 not turned
sets (ex
matched with
Na ₂ SO ₄ ) a 70 2 · 1 a 85 3 · 2 a 80 4 · 3 a 82 5 4th a 70 6th 5 a 70 7th 6th a 69 8th 7th a 70 9 8th a 70 IO 9 a 70 11 10 a
not used
(balanced with
Na ₂ SO ₄ ) 70 12th 11 b 70 13th
14th 12th
1 C. 70
40 15 · 1 d 85 16 · 1 e 87 17 · 1 f 86 18 · 1 G 86 19 · 1 H 90 20 · 1 i 80 21 · 1 J 85 22nd 1 65 23 1 68

Footnote) The symbol "· indicates the examples according to the invention, while the others are reference examples.

From the above results it can be seen that the specific combinations of surfactants (anionic, not ionic or ampholytic) labeled with cellulase Have washing properties.

Example 2

1) detergent compositions:

The same compositions as in Example 1 were used except that surfactant (a) was used and none

Enzyme was used (balanced by Glauber's salt)

2) Cloth artificially stained with oil and grease, cleaning conditions, cleaning method and evaluation:

They were the same as in Example 1.

3) Cellulase used:

Snail cellulase (Driserase) (13) :

A cellulase extracted from the digestive tract of the Helix Polatia according to the method according to F.L. Mayers and D.H. Northcote, Biochem. J. 71, 749 (1959) were subjected to the test. The cellulase was like follows prepared: The digestive tract of the Helix Pomatia including the contents were cut into lengths of 1 to 2 cm while cooling with ice. The same Amount of cold water was added. The whole was using a homogenizer at 200 revolutions / minute Treated five times at 2 minute intervals for 30 seconds. After a centrifugal precipitation with

4O ° C for 3ü minutes (19üOü g) the resulting, Above floating liquid in a dialysis cellophane tube dialyzed for 16 hours and then freeze-dried, whereupon the cellulase was obtained. 5

The thus obtained snail cellulase had a carboxymethyl cellulose decomposing activity (CMCase activity) of 0.08 Units / mg solid (one unit / mg solid shows one Capacity to form 1, o, u moles of glucose from CMC in one hour at 37 ° C and a pH value of 5) as well as a

Cotton cloth decomposition activity of 5 units / g · solid. Cellulosin AP (2) (shown in Example 1) ;

Cellulosin AP (2) had a CMCaae activity of 0.8 units / g solid.

4) Results:

cleaning supplies
No. Enzyme no. lot
<*> Cotton cloth
decomposing
activity
(Unit / kg Cleaning
measured 24. not ver
turns O O 70 25 · 2 0.1 860 73 26 · 2 3 25800 80 27 · 2 20th 172000 90 28 13th 17.2 860 70 29 13th 25th 1250 70

Footnote) The symbol * indicates that this is the Invention, while the remaining are reference examples.

From the above results it can be presumed that a cellulase produced by an animal is not used for cleaning

effect that a cellulase produced by a Bacterium or fungi, should have an enzymatic activity that is higher than a specified value, to illustrate the cleaning effect, and that the latter Cellulase should be contained in at least a predetermined amount in one kg of the cleaning agent.

Example 3

l) Detergent composition:

Sodium n-dodecylbenzenesulfonate 10% by weight Sodium «C olefin sulfonate (C _14-18 ) 3 Sodium alkyl sulfate (C _14-15 ) 3

Sodium alkyl (C, .. " _c ) ethoxy (1.5 mol) sulfate ¹⁴ ~ ^lb

Alkyl (C _16-18 ) ethoxylate (15MoI) Soap (sodium salt of sebum fatty acid)

Non-phosphate type builder or sodium tripolyphosphate 0 or

2Q cellulase Lcellulase (1) as used in Example 1j 0 or

Sodium silicate 10

Sodium carbonate 10 carboxymethyl cellulose 1

Polyethylene glycol 1

fluorescent dye 0.4

Sodium p-toluenesulfonate 2

Water '5

Glauber's salt compensation

total ■

2) Mud stained clothing (artificially stained clothing): Kanuma Sekigyoku soil was made for use in horticulture dried at 120 ° C - 5 ° C for four hours and then pulverized. The earth particles that have a sieve with a

Orifice size of 100 / µm were passed at 120 ° C-5 ° C dried for two hours. 150 g of the earth particles were dispersed in 1000 ml of pearls. A calico No. 2023 cloth was brought into contact with the dispersion and brushed. After removing the dispersion, the excess sludge, that remained on the cloth, removed. (Japanese Patent Application Laid-Open No. 26473/1980).

Test pieces with a size of 10 cm × 10 cm were prepared and subjected to the tests.

3) Washing conditions and procedures as well as evaluation:

The reflective power of the original cloth and that of the mud-soiled cloth before and after washing were measured at 460 m / u.

The rest were the same as those in Example 1.

4) Non-phosphate builders and sodium tripolyphosphate used:

(a) sodium nitrile triacetate

(b) sodium ethylenediaminetetraacetate
(c) sodium diglycolate

(d) sodium hydroxydisuccinate

(e) sodium carboxymethyl hydroxysuccinate

(f) sodium carboxymethyl tartronate

(g) sodium malate
(h) sodium tartrate

(i) sodium citrate

(j) Type 4A of crystalline zeolite 4.5 hydrate

(k) sodium polyacrylate (MW-3000)

(1) hydrolyzed and neutralized maleic anhydride / methyl vinyl ether polymer JjGantretz AN 169 (GAF) J

(m) Hydrolyzed and neutralized maleic anhydride / Diisobutylene copolymer CDemol EP (a product from Kao Soap Co., LtdOj

(η) Hydrolyzed and neutralized maleic anhydride / pentene copolymer (MW »2üuü)

(ο) sodium carbonate and
Cp) sodium tripolyphosphate.

5) Results:

Relnigunqseinheit

Cleaning agent
No. ttel Builder Cellulase (
not used
(balanced with
Na ₂ SO ₄ )
(Reference example) 81 1 )
used
(Invention) 30th do not use 60 78 80 31 d | t 71 92 32 b 71 88 33 C. 72 79 34 d 72 79 35 e 71 82 36 f 72 82 37 G 76 80 38 H 78 79 39 i 76 87 40 j 77 88 41 k 77 88 42 1 75 87 43 m 72 87 44 1
η 80 82 45 O 82 46 P. -

From the results, it is found that the composition has improved detergency when applied to a phosphate Builder free detergent is applied.

Example 4

1) detergent composition:

(A)

Triethanolamine salt of n-dodecylbenzolafonate

(B) 15

(3 moles) sulfate "-.'-. 25th - Lake. Alcohol (C-13.5) ethoxylate
(Eo-7) 25th 10 Coconut fatty acid diethanolamide - 2 Polyethylene glycol 3 1 Sodium citrate - 10 Sodium m-xylene sulfonate - 5 Triethanolamine 5 2 fluorescent dye
(Tinopal CBS-X; a product
of the company Ciba-Geigy Co.) O or 0.5 0.5 Blueing agent 0.05 _ Ethyl alcohol 8th 8th water compensation compensation Perfume 0.1 0.1 Cellulase £ "cellulase (l) in
Example tj 0 or 2 0 or 2 all in all 100 100

2) Cleaner tests using fluorescent Dye-containing detergent compositions A and B:,

2-1) Naturally stained collar fabric:

Cotton fabrics were attached to the collar area Shirts sewn. Adult males were asked to wear the shirts for two days. The fabrics with a symmetrical stain distribution across the central area of the fabric were selected and split in half cut in the middle. The halves were subjected to the test.

2-2) Washing conditions and procedures:

In the cleaning test the naturally stained Cloths, each of these cloths was cut in half along the axis of symmetry with a size of 9 3µ cm. Each of a pair of stained cloths (9 × 15 cm) was washed using a cellulase-free detergent (standard), while the other half was washed with the ^ O inventive cleaning agent (comparison). Ten Pieces of the naturally stained fabrics were immersed in 1 liter of the detergent solution and in one Turgotometer treated at 100 revolutions / minute for 1 minute, dried and subjected to evaluation.

2-3) Evaluation procedure:

A pair of the above right and left halves obtained from the same symmetrically stained sample and Washed with the standard detergent and the comparative detergent, respectively, became macroscopic judged. These cloths treated in this way were classified based on 10 standard stain levels. the Cleaning power of the standard detergent became

given as 100.
25th

(A difference of 1 in the values indicates that there is a marked difference macroscopically between the samples is recognized.)

3) Whitening Tests Using Composition A: 3-1) Washing conditions:

Clothing : 10 new knitted undergarments made of 100% cotton or 4 new shirts with mixed fibers made of polyester / cotton.

3
Washing method ; 2 µm of a liquid detergent was dissolved in 5 liters of tap water, and the clothing was immersed in it at an original temperature of 4 ° C. Two hours later, tap water was added at room temperature, up to a total of 30 liters. The washing process was carried out using a conventional washing machine equipped with a stirring pulsator for a period of 10 minutes. After completing the washing process, the clothes were drained for 1 minute using a dehydrator. The clothes thus dehydrated were washed with 30 liters of tap water for 3 minutes in the washing machine. The washing with 30 liters of fresh tap water was repeated once. The clothes were dried in an electric dryer. The washing cycle described above was repeated 5 times, and the lightness (whiteness) of the clothes was evaluated.

3-2) Assessment of the brightness (whiteness):

Fluorescent dyes contained in the detergents for clothes were generally absorbed Light of 380 nm, and they emit a fluorescent one Light with a peak value at 430 to 440 nm.

Accordingly, if a xenon lamp is used as the light source, including UV radiation, the fluorescent strength (whiteness) can be represented by Z, with the maximum emission at 44Onm in the distribution coefficients of X, Y and Z. Accordingly

3Q were the amounts of the fluorescent dye, which adhered to the clothes, determined by measuring the Z value with the aid of a xenon digital colorimetric color difference measuring device (a product of Suga Shiken-ki Co., Ltd).

4) Results:

4-1) Cleaner for shirt collars: Composition A (cellulase-free): Composition A (containing cellulase) "100: 103

Composition B (cellulase free): Composition B (containing cellulase) - 100: 103

1 · ^υ From the results of Examples 1, 3 and 4-1 it can be seen that the present composition has a cleaning effect on cellulose fabric, regardless of the type of soiling.

4-2) Whiteness of the cloths after washing 50 times (composition A):

before washing cellulase-free cellulase-

containing

made of cotton ge 10.5 ^ u, 05 7.4Ϊθ, 1 8.2-0.1 acted underwear

Shirts, made 7,4Ϊθ, 1 6, O-O, l 7.1 + 0.1 exhibits from ~

mixed fibers
or made of polyester /

Cotton (65/35)

The result of Example 4-2) shows that the composition according to the invention is improved with respect to

their whitening effect through a fluorescent dye.

Example 5

1) Cleaning agent] compositions: A B

(powder detergent)

Sodium n-dodecv- ¹ benzene sulfonate 10 % 10

Sodium alkyl sulfate (C "" ".-,

14-rlD J

Sodium alkyl ethoxyl sulfate (C _14-15 , Eü-1.5)

Sodium oC-olefin sulfonate

^(C 16-18 ⁾

Soap (tallow fatty acid sodium salt) sodium tripolyphosphate

crystalline sodium aluminosilicate (type 4A)

Sodium Silicate Sodium Carbonate Carboxymethyl Cellulose Polyethylene glycol (MW-6000) fluorescent dye Sodium p-toluenesulfonate Water Glauber's salt

Enzyme bleach

3 - 2 "32 0 7847"
AWAY
(powdery cleaning
middle) 5 3 2 2 10 5 10 2 10 10 10 10 1 10 1 10 0.4 1 2 1 10 0.4 compensation CVJ 3 10 0.005 10.6 3 10

all in all

100 %

100 %

2) Using Artificially Stained Clothing:

EMPA

Cotton test pieces (10 cm χ 10 cm) stained with cocoa, were prepared and subjected to the examinations.

3) Cleaning and bleaching conditions and procedures:

The cleaning of the bleach was done in four water
Degree of DH hardness dissolved, for the preparation of 1 1 0.5 % aqueous solution. Five pieces of EMPA 112 cotton cloth, provided with artificial spots, were placed in the above

* "" * ^: '32G7847

Written aqueous solution introduced. After you get them Left at 40 ° C for 2 hours (when composition B was used, if they were left under the irradiation with natural light), the solution and the artificially stained pieces of fabric were transferred directly to a stainless steel cup of a turgotometer, being in the turgotometer was stirred at 100 revolutions / minute at 20 ° C for 10 minutes. After washing them in running water they were using flattened a bit and their reflectivity was measured The degree of cleaning was calculated using the following formula:

The reflectance of the original cloth before washing and bleaching and that of the stained cloth before and after washing and bleaching were measured at 460 m ax using an automatic recording colorimeter (a product of Shimadzu company seisaku-sho) measured, and the cleaning and Degree of whiteness (4) was calculated according to the following formula:

Reflectivity Reflectivity

(after washing) - (before washing) Cleaning and and bleaching and bleaching

Degree of whiteness (%) " x

Reflective power Reflective power (of the original) (before washing) cloth - and bleaching

The penetration rates of the five samples are shown in the table below.

4) Enzymes used:

(1) not used

(2) Cellulosin AP (a product of Uead Kagaku Co., Ltd.)

(3) Cellulase-onozuka enzyme (1) in Example 1

5) Bleach used:

(a) not used (balanced with Glauber's salt)

(b) Sodium percarbonate (a product from Nihon peroxide Co.,)

(c) sodium perborate (a product of Mitsubishi Gas Kagaku)

(d) aluminum salt of sulfonated! Phthalocyanine (a product of Ciba-Geiqy Co.) and

(e) Thioura Dioxide (a product of Tokai Denka Co.)

6) Results of the measurement of the cleaning and bleaching power on artificially stained EMPA 112 cloth:

Table 1

Enzyme and bleach cleaning and bleaching power

in detergent Composition A Composition

a 4υ

^{b 5υ}

c 50

d -

e 46

2a 46

b 58

c 58

d -

^ ⁵ ^

a '48

b ¹ "6o

c 60

d -

e * 56

Footnote) The symbol indicates the invention while it the rest are reference examples.

From the above results, it can be seen that the present composition has a synergistic effect in in terms of cleaning and bleaching effects, through the use of cellulase and a bleaching agent.

Example 6
lü

1) detergent composition:

Composition A in Example 5, containing sodium percarbonate 5) - (b).

2) clothes stained with a complex dirt:

The naturally stained collar scarves (example 4) -2) -l)

3) Cleaning conditions and methods:

The cleaning conditions and cleaning procedure were the same as in Example 4-2-2), except that the cloths were immersed in a 0.5% detergent solution at 40 ° C for two hours, after which tap water was added to the solution, to adjust the detergent concentration to 0.133 % before washing with the turgotometer.

4) Evaluation procedure:

The evaluation procedure was the same as that in Example 4-2-3).

5) Enzymes used:

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

(2) cellulase l__cellulase-Onozuka; Example 1- (1) _ /

(3) via cellulase (2) / lipase (a product from Gist Brocades Co .; manufactured by R. oryzae) «1: 1

(4) cellulase (2) / amylase (Termamyl 60 G; a product

from NüVO Industries Co.) »1: 1 35

(5) cellulase (2) / protease (alkalase 2.0 M; a product from NüVü Industries Co.,) -1: 1

(6) Cellulase (2) / Protease / Lipase - 2: 1: 1

(7) Cellulase (2) / Protease / Amylase - 2: 1: 1

(8) Cellulase (2) / protease / lipase / amylase «3: 1: 1: 1

6) Results:

Enzyme in the detergent

1 2 3 4 5 6 7 8

not used

Clean power index

100

102

103.5

103.5

105

105

105

105

Footnote) The symbol indicates the invention, while the other is a reference example.

The above results show that the combination of the cellulase with other enzymes such as protease, lipase or amylase effectively removes complex dirt.

Claims (3)

I »ATHN '' Λ N WÄLT Ü 320 78Λ7 DR. KARL TU. HHGHL DIPL-ING. KLAUS DICKEL HAI HMONI) SWI- (I -O 2UUU IIAMHUKd ·>. '11 III ON ((14Ul «« () (, ·) ο I JIIUUS-KKItSSTKASSI-: 11 8UUU MLJNCIIIiN 6U TLLIiION (UBV; K8521U / Ut. 1.1.AShI N 111 IM | -1> ΚΟΙ'ΛΙ-SC'III N I1AII NIAMI Il LLGRAMM Al) RLSSl I) C) LLlNIiR-PATlNI 'MUNCHLN 1-1'.KNSCHKl UILK UIA71V dpul il IHR / fcltHhN UNShR ZhICHLN H 3233 8UUU MUNICH. I) KN Kao Soap Co., Ltd. 14-10, Nihonbashi-Kayabacho 1-chome, Chuo-ku, Tokyo J ept »n detergent composition Patent claims 1. Cleaning agent composition set for garments, characterized in that it essentially contains the following components, namely: a) at least eir. surfactant selected from the group consisting of anionic surfactants, nonionic surfactants and POMSt 111 IKkONlO HAMIlURt ₁ IVIllO-iln BANK DKIbI) NhKBANKAi. llAMBIiKli KUl SK <Ki> K '"till / .'IHmiKltHII I ¹ OSISt HK KKONIO MUNCHLN m-iO2 HANK Dl HISt Hl-. BANK Au, MUNICH KIn NK (JdKI (Hl] IHl / / W) 7 (NIIIII ampho Iy ti sham surfactants, as well b) a bacteria- and / or fungus-derived cellulase with an enzyme activity of at least 100 units for cotton fabrics (one unit is the activity for 1 g of the sample for the formation of 1 m, u mole of reducing sugar from a cotton fabric in one minute). 2. Composition according to claim 1, characterized in that - lü indicates that the content of surface-active agent in the composition is at least 5% by weight amounts to. 3. Composition according to claim 1, characterized in that the content of cellulase in of the composition is so large that 1 kg of the composition has an enzyme activity on a cotton fabric of owns at least 100 units.