AU595401B2 - Softening detergent compositions containing cellulase - Google Patents

Abstract

The compositions disclosed herein clean well and at the same time act as textile softeners. They contain a cellulase enzyme and are formulated at a mild alkaline pH range.

Description

f

AUSTRALIA

Patents Act COMPLETE SPECIFICATION

(ORIGINAL)

Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: 954 0 Priority Lelated Art: 0 p 0* APPLICANT'S REFERENCE: CM-236M Name(s) of Applicant(s): The Procter Gamble Company S Address(es) of Applicant(s): One Procter Gamble Plaza, Cincinnati, Ohio 45202, UNITED STATES OF AMERICA.

i* Address for Service is: PHILLIPS ORMONDE FITZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne 3000 AUSTRALIA Complete Specification for the invention entitled: SOFTENING DETERGENT COMPOSITIONS CONTAINING CELLULASE Our Ref 75628 POF Code: 44135/44135 The following statement is a full description of this invention, including the best method of performing it known to applicant(s): 6003q/l 1 i ATTACHE I v ~aRnu B~E RED U u l SLLA 6012q/1

I.

-2- Background Numerous attempts have been made to formulate laundry detergent compositions which provide the good cleaning performance expected of them and which also have textile 5 softening properties. Thus, attempts have been made to incorporate cationic textile softeners in anionic surfactant-based built detergent compositions employing various 7eans of overcoming the natural antagonism between the anionic and cationic surfactant species. For instance, in British Patent specification 1.518.529, drtergent compositions are described comprising organic surfactant, builders, and, in particulate form, a quaternary ammonium softener combined with a poorly water-soluble dispersion inhibitor which inhibits 15 premature dispersion of the cationic in the wast liquor.

Even in these compositions some compromise between cleaning and softening effectiveness has to be accepted.

Another approach to providing built detergent compositions with softening ability has been to employ nonionic surfactants, instead of anionic, with cationic softeners, and compositions of this type have been described in, for example, British patent specification 1,079,388, German V Auslegeschrift 12 20 956 and US patent 3,607.763.

However, it is found that if enough nonionic surfactant is employed to provide good cleaning, it impairs the softening effect of the cationic softener, so that, once again, a compromise between cleaning and softening effectiveness must be accepted.

~7 P18/7/7" PHILLIPS ORMONDE FITZPATRICK Patent and Trade Mark Attorneys 367 Colliris Street Melbourne, Australia STUANT IAYLOW 3 Recently it has been disclosed in British patent specification 1,514,276 that certain tertiary amines with two long chain alkyl or alkenyl groups and one short chain alkyl group are effective fabric softeners in detergent compositions.

Another approach to providing detergent compositions with textile softening ability has been the use of smectite-Lype clays, as described in British patent specification 1,400,898.

European Patent Application 0,026,528 describes the use of waterinsoluble long chain tertiary amines in conjunction with a watersoluble cationic quarternary ammonium compound and/or a water-soluble aliphatic amine, optionally with clays, in alkaline detergent compositions to provide fabric softening properties.

Another approach has been to use cellulolytic enzymes, i.e.

cellulase, as a harshness reducing agent in fabric softening compositions, as taught in British Patent 1,368,599.

The use of cellulase in detergent compositions has been further *disclosed in GB-A-2,075,028 GB-A-2,095,275 GB-A-2,094,826 and Jap. Patent 57108-199.

EP-A 0,120,528 teaches alkaline softening detergent compositions comprising a synergistic mixture of a water-insoluble C 0-C26 10 26 tertiary amine and cellulase.

s** EP-A 0,177,165 discloses alkaline softening detergent compositions containing a mixture of smectite clay and cellulase.

*W

WD

*1 LI~--I L a ~L II -_YL- PATENT'OFFICE

I

IFIY(

-4- To date however, detergent cellulases have not found wide acceptance in the detergent industry in particular in softeningthrough-the-wash executions. One reason is that the interaction of cellulase and other, more conventional detergent ingredients is poorly understood.

Another reason is that compositions formulated according to artdisclosed recipes do not use cellulase at their optimum pH-range.

To date as well, the tendency in the formulation of softeningthrough-the-wash detergent compositions has been to increase the pH of the compositions (clearly above 10) in order to boost cleaning performance, especially on cotton fabrics, which otherwise would be impaired by depositing softening ingredients.

However, at such alkaline pH ranges, fabric care problems such as, e.g. fabric harshening, fabric damage, or dye fading are encountered there is, consequently, a standing need for compositions formulated at pH below 10, which show good fabric-care performance, excellent softeness, while having good cleaning properties.

The present invention answers the above need, and provides efficient mild-alkaline softening detergent compositions, which exhibit good fabric-care performance and softeness, and good cleaning properties, especially on cotton fabrics.

The present invention also addresses standing prior-art issues by using a cellulase enzyme at a pH range where its activity is optimum and by the surprising discovery that water-insoluble long chain amines scch as described in EPA 0,026,528 or EPA 0,120,528, give softeness negatives in presence of cellulase, upon cumulative washes, under the mild alkaline conditions of the invention.

.9 9.

0 0o 5555 9 9 *0 5 0 *0* i~ -L1If- It has also been found that a high level of anionic surfactant is necessary in order to get the benefits of the compositions herein.

It is therefore an object of the present invention to provide anionic-rich, cellulase-containing softening detergent compositions which a'e formulated at mild-alkaline pH (below It is another object of the present invention to provide cellulasecontaining softening detergent compositions which are essentially free of water-insoluble long-chain amine softening agents or derivatives.

It is a further object of the present invention to provide softening detergent compositions which provide good softness and cleaning benefits and exhibit good fabric-care performance.

SUMMARY OF THE INVENTION The present invention relates to detergent compositions for the cleaning and softening of fabrics, comprising a surface-active agent, of which at least 50% by weight is an anionic surface active agent, and a cellulase.

S.

The compositions herein have a pH, 1% solution in distilled water, of from 6.5 to 9.5 and are essentially free of water-insoluble longchain alkyl amine softening agents, or derivatives thereof.

Perferred compositions include in addition a clay softening material.

***snt s o

WD

Dl The' surface-a The surf least 50% by an anionic su present conte encompass soa be used in th Suitable of alkyl benz 15 polyethoxy et S alpha-olefin their esters, monoglyceride polyethoxy et 2-acyloxy-alk sulphonates.

Especial to 15 carbon especially fr sulphates haw Suitable alky 18 carbon &to from I to 12 especially fr and an averag molecule -6 ETAILED DESCRIPTION OF THE INdUENTION ,ctive 3qent ace-active agent useful herein contains at weight, preferably 60% to 100% by weight of rface-active agent (salt form). In the xt, anionic surface-active agents do not ps. A wide range of anionic surfactants can P compositions of the present invention.

anionic surfactants are water-soluble salts ene sulphonates, alkyl sulphates, alkyl her sulphates, paraffin sulphonates, sulphonates, alpha-sulphocarboxylates and, alky2 glycery2 ether sulphonates, fatty acid sulphates and suiphonates, alkyl phenol her sulphates, anc'-l-sulphonates, and beta-alkyloxy alkane ly preferred alkyl benzene sulphonates have 9 atoms in a linear or branched alkyl chain, om 11 to 13 carbon atoms. Stzjitable alkyl e from 10 to 22 carbon atoms in the alkyl specially from 12 to 18 carbon atoms.

I polyethoxy ether sulphates have from 10 to ms in the alkyl chain and have an average of

CH

2 CH t2 0- groups per molecule, om 10 to 16 carbon atoms in the alkyl chain e of from I to 6 -CH 2 CH 2 O-groups per

CC-

7 S. *r 6

S

S

5* 5

S

*5 S

S

S.

Suitable paraffin sulphonates are essentially linear and contain from 8 to 24 carbon atoms, more especially from 14 to 18 carbon atoms. Suitable alpha-olefin sulphonates have from 10 to 24 carbon atoms, more especially from 14 to 16 carbon atoms; alpha-olefin sulphonates can be made by reaction with sulphur trioxide, followed by neutralization under conditions such that any sultones present are hydrolyzed to the corresponding hydroxy alkane sulphonates. Suitable alpha-sulphocarboxylates contain from 6 to 20 carbon atoms; included herein are not only the salts of alpha-sulphonated fatty acids but also their esters made from alcohols containing 1 to 14 carbon atoms.

15 Suitable alkyl glyceryl ether sulphates are ethers of alcohols having from 10 to 18 carbon atoms, more especially those derived from coconut oil and tallow.

Suitable alkyl phenol polyethoxy ether sulphates have from 8 to 12 carbon atoms in the alkyl chain and an average of 20 from 1 to 6 -CH2CH20-groups per molecule. Suitable 2-acyloxyalkane- l-sulphonates contain from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety. Suitable beta-alkyloxy alkane sulphonates contain from 1 to 3 carbon atoms in the alkyl 25 group and from 8 to 20 carbon atoms in the alkane moiety.

The alkyl chains of the foregoing anionic surfactants can be derived from natural sources such as coconut oil or tallow, or can be made synthetically as for example by using the Ziegler or Oxo processes. Water-solubility can be achieved by using alkali metal, ammonium, or alkanol-ammonium cations; sodium is preferred. Mixtures of anionic surfactants are -1 contemplated by this invention; a satisfactory mixture contains alkyl benzene sulphonate having 11-13 carbon atoms in the alky'l group and alkyl sulphate having 12 to 18 carbon atoms in the alkyl goup.

N~onionic surfactants may be incorporated in the compositions herein, in limited amounts (less than Suitable nonionics are water-soluble ethoxylated materials of tILB 11.5-17.0 and include (but are not limitei to) C 10 20 primary and secondary alcohol ethoxylates and 6 10C alkylphenol ethoxylates. C 4

C

1 linear g primary alcohols condensed with from seven to thirty moles of ethylene oxide per mole of alcohol are preferred, 0:0examples being C 4

C

1

(EO)

7

C

1 6

C

1

(E)

000141.7' 161.(0 2 0 66 15 and especially C 16

C

18 (EQ) 11 *S Other types of surfactants can be used in limited amounts, in combination with the anionic surface-active agent. They include zwitterdonic amphoteric, as well as cationic su-factants.

Cationic co-surfactents which can be used herein, include water-soluble quaternary ammonium compounds of the *form R 4 R 5

R

6 R 7 N 4 wherein R4is alkyl 25 having from 10 to 20, preferably from 12-18 carbon atoms, and R. R 6 and R 7 are each C 1 I to C 7 alkyl to: preferably methyl; X_ is an anion, e.g. chloride.

Examples of such trimethyl ammonium compounds include C12- 14 alkyl trimethyl ammonium chloride and cocoalkyl trimethyl ammonium methosulfate.

The total level of surface-active agent can range from about to about 95%, prefeirably from about 10% to about 40%, and more preferably from 15% to 30%, by weight.

-9- The Cellulase The cellulase usable in the present invention may be any bacterial or fungal cellulase having a pH optimum of between 5 and Suitable cellulases are disclosed in GB-A-2.07S.028; GIE-A-2.095.275 and DE-OS-2.247.832.

Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea uar.

thcerroidea), particularly the Humiccrla strain DSM 1800, and cellulases produced by a fungus of Bacillus N or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mullosc (Dolabella Auricula Solander).

The cellulase added to the composition of the inve~ntion may be' in the form of a non-dusting granulate, e.g. "marumes" or. "prills", or in the form of a liquid in which the cellulase is provided as a cellulase concentrate suspended in e.g. a nonionic surfactant or dissolved in an $@s aqueous mvdiun.

Activity determination for the cellulase herein is based on the hydrolysis of carboxymethyl cellulose.

Generated low molecular reducing carbohydrates are colorimetrically determined by the ferrocyanide reaction at. described by W.S. Hoffman Biol. Chem." 120,51 (1973). Key conditions of incubation are temperature of 40 0 C and incubation time of 20 minutes.

One.CMCase unit is defined as the amount of enzyme which forms per minute an amount of reducing carbohydrate equivalent to 10-6 mole of glucose, in the above-described conditions.

10 A highly preferred range of cellulase activity in the present context is from 5 to 100 CMCase activity units/grams of composition.

The compositions of the invention are essentially free of waterinsoluble long-chain alkyl amine softening agents, and derivatives thereof, since it has surprisingly been discovered that they interact negatively with cellulase, in the pH conditions of the present invention. Derivatives of the amine softening agents include the corresponding amide compounds. Such amine softening agents are disclosed in e.g. EP.A 0,026,528 and EP.A 0,120,528 and include in particular amines of the formula R R2R3N where R 1 and R 2 are C 6 to C20 alkyl chains and R 3 is C 1 to C10 alkyl chain or hydrogen.

The compositions herein are formulated ata pH in the range of from 6.5 to 9.5, measured as a 1% solution of the composition in distilled water.

At this pH-range, the cellulases for use herein have their optimum performance.

S

OPTIONAL INGREDIENTS The compositions herein may contain, in addition to the essential ingredients, optional ingredients, which can be highly desirable.

For example, it is preferred that the compositions herein contain a clay softening agent, in combination with the cellulase.

Such clay softening agents are well-known in the detergency patent literature and are in broad commercial use, both in Europe and in the United States. Included among such clay softeners are various *r 0

WD

-1 11 heat-treated kaolin; and various multi-layer smectites.

Preferred clay softeners are smectite softener clays that are described in German patent document 23 34 399 and in U.K. patent 1,400,898, which can be referred to for details.

The most preferred clay fabric softening materials include those materials of bentonitic origin, bentonites being primarily montmorillonite type clays together with various impurities, the level and nature of which depends on the source of the clay material. Softener clays are 0o used in the preferred compositions at levels of at least generally 1-20%, preferably 2-10%.

0* 15 It .s preferred as well that through-the-wash detergent compositions contain a detergent builder and/or metal ion sequestrant. Compounds classifiable and well-known in the art as detergent builders include the nitrilotriacetates, polycarboxylates, citrates, oat 20 water-soluble phosphates such as tri-polyphosphate and sodium ortho- and pyro-phosphates, and mixtures thereof.

Metal ion sequestrants include all of the above, plus materials like ethylenediaminetetraacetate, the amino-polyphosphonates and a wide variety of other 25 poly-functional organic acids and salts too numerous to mcntion in detail here. See U.S. Patent 3.579.454 for typical examples of the use of such materials in various cleaning compositions. Preferred polyfunctional organic acids species for use herein are citric acid, ethylene 30 diaminc tetramethylenephosphonic acid, and diethylene triaminepentamethylenephosphonic acid.

A further class of detergency builder materials useful in the present invention are insoluble sodium aluminosili.cates. The 1-10 micron size reolite zeolite A) builders disclosed in German Parent 24.22.655 r--S*P 12 are especially preferred for use in low-phosphate or non-phosphate compositions. In general, the builder/sequestrant will comprise from 0.5% to 45% of the composition.

The compositions herein can also contain fatty acids, saturated or unsaturated, and the corresponding soaps.

Suitable fatty acids, saturated or unsaturated, have from to 18 carbon atoms in the alkyl chain. Preferred are unsaturated species having from 14 to 18 carbon atoms in the alkyl chain, mtost preferably oleic acid. The corresponding soaps can also be used. The optional fatty acid/soaps are used in levels up to 15 The compositions herein can also contain compounds of the general formula R-CH(COOH)CH (COOH) i.e. derivatives of succinic acid, wherein R is C10-C alkyl or alkenyl, preferably C 12-C16 or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone 20 substituents.

The succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts.

Specific examples of succinate builders include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate, and the like.

Also useful as builders in the present context are the compounds described in US patent 4.663.071, i.e.

mixtures of tartrate monosuccinic acid and tartrate disuccinic acid in a weight ratio of monosuccinic to disuccinic of from 97:3 to 20:80, preferably 95:5 to 40:60.

p I 1 13 of the ty acids, oaps.

ave from red are toms in al fatty pounds of vatives one 0 00 0 0 00

S

S.

S.

SO

*50 0*

S

0r Another optional ingredient is a bleaching agent.

Preferred are peroxygen bleaching agents such as sodium perborate, commercially available in the form of mnono- and tetra-hydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate and urea peroxyhydrate.

Bleach activators may be used in combination with the above peroxygen bleaching agents. Classes of bleach activators include esters, imides, imidazoles, oximes, and 10 carbonates. In those classes, preferred materials include methyl o-acetoxy benzoates; sodium-p-acetoxy benzene sulfonates such as sodium 4-octanoyloxybenzene sulfonate; sodium-4-octanoyloxybenzene sulfonate, and sodium-4-decanoyloxybenzenesulfonate biophenol 15 diacetate; tetra acetyl ethylene diamine; tetra acetyl hexamethylene diamine; tetra acetyl methylene diamine.

Other highly preferred peroxygen bleach activators which are disclosed in U.S. Patents 4,483,778 and 4,539,130, are aipho-substituted alkyl or alkenyl esters, such as sodium-4(2-chlorooctanoyloxy) benzene sulfonate, sodium 4-(3,5,5-trimethyl hexanoyloxy)benzene sulfonate.

Suitable peroxyacids are also peroxygen bleach activators such as described in published European Patent Application 25 0 166 571, compounds of the general type RXAOOH and RXAL, wherein R is a hydroxcarbyl group, X is a hetero-atom, A is a carbonyl bridging group and L is a leaving group, especially oxybenzenesulfonate.

Enzymes other than cellulases, such as proteolytic, amylolytic, or lipolytic enzymes can be used in combination with the cellulase herein. All generally known enzyme stabilizing systems can be used in the liquid executions of the compositions herein, at the art 35 established level. Examples of suitable stabilizing systems include short chain carboxylic acid, particularly formic acid in combination with a low level of calcium, boric acid and the water-soluble salts thereof possibly in combination with polyols.

n the sodium, ude ccinate xt are .e.

te to to 40:60.

6. A composition in accordance with claim 1, which further contains a fabric-softening clay material.

14 Moreover, the compositions herein can contain, in addition to ingredients already mentioned, various other optional ingredients typically used in commercial products to provide aesthetic or additional product performance benefits. Typical ingredients include pH regulants, perfumes, dyes, optical brighteners, soil suspending agents, hydrotropes and gel-control agents, freeze-thaw stabilizers, bactericides, preservatives, suds control agents, bleach stabilizing agents.

Form and Preparation of the compositions The detergent compositions of this invention can be present in any suitable physical state inclusive of granular, liquid, pasty, or sheet-like form. They may be prepared in any 15 way, as appropriate to their physical form, by mixing the components, co-agglomerating them, micro-encapsulating them, dispersing them in a liquid carrier, and releasably adsorbing or coating them onto a non-particulate substrate, such as a non-woven or paper sheet.

The following examples illustrate the present invention, but are not intended to limit its scope.

25 Example I S. A granular detergent composition was prepared by using the following ingredients in the stated proportions ingredients by weight Sodium Linear C12 alkyl benzene sulfonate 11.0 Sodium Tallow alkyl sulfate Tallow alcohol ethoxylate (EO11) 0.3 Sodium tripolyphosphate 24.0 Bentonite clay the best method of performing it known to applicant(s): 6003q/1 -1 15 Cellulase Proteolytic enzyme Sodium Sulfate minors and water 3 .0* 0.9 40.0 up to 100 pH, 1% concentration in distilled water 8.7 *represents 40 CMCase units per g of composition The above composition showed good cleaning performance as well as good softeness benefits, while exhibiting good fabric-care properties (no fabric damage dye fading, or fabric harshening observed) 0* .4 4 S. *e Ge V 044*

S

.5

S.

S 0 *5 *0

S

V..

04

S

S.

S

0

S

0 0*O0

S

ObSO

S

4 5* a *a The following granular cornhpcsitions were also prepared: ingredient by weight Example II Example I Sodium Linear C 12alkyl benzene sulfonate C 13 -15 fatty alcohol/li ethylene oxide condensate 25 Sodium sulfate Sodium tripolyphosphate Zeolite A Sodium nitrilotriacetate Bentonite clay Cellulase Proteolytic enzyme Sodium Perborate tetrahydrate

TAED*

Boric acid Optical brightener minors and water pH, 1% concentration in distilled water 7,0 1.0 15.0 1! 24.

6. 5 20.02 1.2 0.3 up to 100 9.0 5 .0 t.0 mwTirTrii IIII~-.~I I 11111 II I 16 *tetra acetyl ethylene diamine **represents 47CMCase units per g of composition The compositions of Example II and II showed good cleaning, softening, and fabric-care performance.

Example IU 10 The following liquid detergent composition was also prepared ~j a, 8 a ga a a 0.*S p *8q**B

S.

P 8

S.

a'

P

*4~4 a a a p pG a eja..

a .8mpg.

a 3* *a a a a a *a ingredient 15 Linear C12 alkyl benzene sulphonic acid Coconut alkyl sulphate (TEA salt) Tallow C,_11 5 alcohol ethoxylate (E07) Coconut fatty acid Oleic acid 20 Citric acid Trethanolamine Ethanol Propanediol Sodium hydroxide 25 Sodium formate Cellulase Proteolytic enzyme minors, water pH, 1% concentration in distilled water by weight 11.0 10.0 10.0 0.6 up to 100 *represents 34CMCase units per g of composition

Claims (7)

1. A detergent composition for the cleaning and softening of fabric containing, a surface active agent containing at least 50% by weight of anionic surface-active agent; a detergent cellulase; said composition being essentially free of water-insoluble long-chain-alkyl amine softening 1 agents, or derivatives thereof,and the pH of a 1% 10 solution of the detergent composition in distilled water being from 6.5 to

2. A composition in accordance with claim 1, wherein the cellulase is bacterial or fungal cellulase having a pH optimum of between 5 and 11.5.

3. A composition in accordance with claim 1, wherein the cellulase is an alkali cellulase having an optimum pH from 6.5 to j

4. A composition in accordance with claim 1, wherein the composition has a cellulase activity of from 5 to 100 CMCase activity unit/gram of composition.

A composition in accordance with claim 1, wherein the surface-active agent contains from 60% to 100% by weight of anionic surface-actije agent.

6. A composition in accordance with claim 1, which further contains a fabric-softening clay material.

7. A composition in accordance with claim 6 wherein the fabric-softening clay material is a bentonite clay. DATED: 19th November, 1987 PHILLIPS ORMONDE FITZPATRICK Attorneys for: THE PROCTER GAMBLE C M