PH26642A - Granular detergent composition containing cellulase - Google Patents

Description

DELERGAN_CHANUL (8 COMPOSI LOS

CU nd BiG CGLLULAS b, lechnical Field

Ihe present invention is related to srapular detergent compositions which Are useful for leaning and soltenin of ichricz, and for giving other tabric-core benefirae sri an apprarauce irprovements : aud rejuvenation, ‘ - The compositious lierein coutain a fa wic-sof Lor tug clay material, oo co Cl .aud a cellulase enzyme, whici. is in She form 1 gravulates coutain -

Co ‘ing calcium carbonate, co 10

BN . Background of the Invention it has been the onjeclive of wan, dosergent sanufactores to forru- late laundry delergent compositions waieh provide the good cleaning ceriorrance expected -! them, and which al:o exhibit fabrie-care properties, inclusive of sofhness.

Representative of suck deterpent cospositious are the onee which have been disclosed in Hritish peters 3,500 205 J ho0,cun, or

EFA O 026 528. BAD ORIGINAL

J elo}

Cellulase enzymes have already been used in detergent compositions for their cleaning abilities, as dis~losed in British latent Appli- cation GB-A 2,095,275, U3-2,0M, 26, or lapenese ratent 57108-1u9,

Cellulage have also been found Ln give softness beweflts to fabrles, as in U.S. 4,035,307;

Ki'-A 0 120 5°0 teaches alkalive softening detervant comoositions cowr- . prising a synergistic -ivture of a water-insoluble “rats tertinry snine and cellulase.

EP-A QO 177 165 dire) wes nlkalioe sc fitening deterpent compositions containing a mixture of crectite clry and eellniase, : EP-A 0 220 016 disclnecs the fate eoloreelariiication effect deri- vable from the use of ueiiniare in = celeyeen! ake-b,

When such detergent and;or softening compositions are in granular forms, the cellulase cuzywes are useally iacoriorated in the com- position in the form of gramulates, also identified as marumes, or prills, which are supplied by tie epzyme wnnufrcturer.

U.5. h,h35,307, which relatas Lo a hardness reducing agent for de- tergent compositions, distloses the nee of cellulase granulates, and mentions certain Ingredients which need to ie incorporated te the granulates durirg lheir sraking, for e.q. son-dusting and coler . purposes.

It has been discovered, nowever, that certain of these ingredients are detrimental to the softness/tebvic care vrcrerties of the com- position, when celluls:ie grenulates corbaining these ingredients are incorporated into » detergent corunsition. } when looking for a reunlncement Lo theme undecirable ingredients, it has now been discovers’ that water-insoluble salts of caleinr, sur- prisingly substantially enharee the softness /f=hrie care performance :

BAD O of the detergent com sitions containing the enzume granulates. RIGINAL - Pp -

Dw?

It is therefore tie object of the present invention to provide deter- gent compositions which possess excellent softness /fabric care pro- perties, due to tte use of cellulase granulates containing a water- insoluble salt of calcium.

Summary of the luvention

The present invention relates to grenvlar detergent ccupositions con- taining a febric-softening clay material, and cellulase granulates containing from 1% to 5%, by weight, preferably 9F to 15% of tue granulates, of calcium carbonate.

Calcium carbonate is .referably coated onto the cellulmse granulates.

The invention also relates to the above-described cellulase granu- lates per-se.

Detaiied Description of the Invention . The compositions herein are capable of cleaning and softening the . 15 treated fabrics, as well as giving benefits in terms of fabric appear- . ance improvements and rejuvenation.

This is achieved by the presence, in the granular compositions herein, of surface active agents, of fabric-softening clay materials, and of cellulase granulates containing calcium carbonate.

In the following, these compulsory, as well as optional ingredients are described in detail:

The Cellulase

The c ellulase usable in the present tnvention may he any bacterial or fungal cellulase Laving a pH optimum of between 5 and 9.5.

Suitable cellulases are disclosed in U.S. 4,435,307, GB-A-2.0Y5.275,

DE-08-2.247,832, and kP-A © 220 016.

BAD ORIGINAL

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Examples of such cellulases are cellulases produced by a strain of

Humicola insolens {(Jlumicola grisea ~ar. thermoidea), particularly : by the llumicola strain DSL 1400, and cellulases produced by a fungus of Baclllus N or a cellulase 212-preducing fungus belonging to tue genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusc (Uolmbetia Auricula Solander).

Activity determination for the cellulase herein is based on the hy- drolysis of carboxyrehhyi cellulose. (eperated low molecular redu-- cing carbohydrates are colorimetricelly determined by the ferrocya- nide reaction as described by W.S. Hoffman "4. Biol. Chem.” 120,51 (1973). Key conditions of incubation are pH = {.0, temperature of 40° C and incubation lime of 20 minutes.

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

A useful range of cellulase activity in the present context 1s from 5 to 1360, preferably from 60 to 140 CMCase activity units/gram of detergent composition. :

The Cellulase Granulates

Cellulase enzynes for use in granular detergent compositions are typically supplied in the form of granulates, e.g. marunes or prills.

Buch granulates contain a majority of crude cellulase enzyme, toge- ther with additional ingredients, such as polyethylene glycol, at . typical levels of from 5% to 7%, and cellulose at tvpical levels of about 10%. The polyethylene glycol for use herein ean have a mole- cular weight in the range from 500 to 8000.

The amount of cellulase in the granules is determined by the totel cellulase activity of the composition, which has to be in the limits set up hereinabove. BAD UHIGINAL ee .

It has been discovered that certain waterlals which have been used ~~

Pt §2 by enzyme manufacturers as dustness-preventing and whitening agents, which are Titanium dioxide and Magnesium silicate, interact negatively with the softness perfornance of the compositious herein.

Tre compositions of the invention should, therefore, ;referably by free of Titanium dioxide and Magnesium silicate. it has now been found that calcium carbonate possesses the dustness- preventing function when added to the cellulase granulates, aud also gives unexpected softness/fabric care benefits as shown heréinafter.

The caleium carbonate should be present in the cellulase granulates, at levels of from 1% tu 1Uj, wreferably 5x to 13% by weight, of tie granulates.

Calcium carbonates of a particle size range from 1 to 10 microus have been found to be particularly suitable for the purpose of the present invention.

The calcium carbonate used herein may be used as is or in coated form, typically coated with stearic acid. In a preferred execution - of the present invention, ealcium carbonate, either as is or already coated with e.g. stearic acid, is coated onto tie cellulase granu-

EE lates. .

Cellulase granulates can be prepared in a number of different ways, for example by means of a "Marumerizer" as described in British fat.

Nos. 1,362,365 and 1,301,367 or by weans of a granulating machine, as described in Aufbereitungs-Technik Mo. 3/1970, pp. 147-153 and

No. 5/1970, pp. 262-274, or can be prilled granulates as described e5 in Belgian Patent Specification No. 760.135. lun all cases, the granulates mst have low dusting properties. }

The calcium cerbonate herein is eitner mixed with the other ingre- dients during the making of the granulates, or mixed with cellu- lase before granulation, or, preferably, coated onto the granulates

Cs. “AD ORIGINAL

Der 2 which have been prepared as described hereinsbove, by conventional coating methods.

The cellulase granulates eccording tec the present invention are present at levels of from 1% to 50p by weight of the deterzent com- position herein, preferably 1.5% to 1Uh by weight.

The surface-active agent

The surface active agent useful herein may be selected from anienic, nonionic, zwitterionic surfactants end is present sat levels of from 1% to 50% by weight of the composition, preferably from 10% to 30%.

Suitable anionic surfactents are water-soluble selts of alkyl ben- zene sulphonates, alkyl sulphates, alkyl polyethoxy ether sulphates, paraffin sulphonates, alpha-olefin suiphonates, alpha-sulphocarhbo- xylates and their esters, alkyl glyceryl ether sulphonates, fatty acid monoglyceride sul hates and sulphonates, alkyl phenol polyethoxy either sulphates, 2-acyloxt-alkane-l-sulphonates, and beta-alkyl- oxy alkane sulphonates.,

Especially preferred alkyl benzene sulphonates have 4 to 15 carbon / atoms in a linear or branched alkyl chain, especially from 11 to 13 carbon atoms. Suitable alkyl sulphates have from 10 to 22 carbon ; atoms in the alkyl chaln, more especially from 12 to 18 carbon atoms.

Buitable alkyl polyethoxy ether sulplintes have from 10 to 18 carbon atoms in the alkyl chain and have an average of from 1 to 12 - CH,,- t

CH,0- groups per molecule, especially from 10 to 16 cerbon atoms in the alkyl chain and an average of from 1 to 6 -CH,CH,0- groups per molecule,

Sultsble paraffin sulphonates are essontially linear and contain . "from # to 24 carbon atoms, more especially from 14 to 18 carbon atoms.

Suitable alpha-olefir sulphonates have from 10 to 24 carbon atoms, more especially from 1M to 16 carbon rtoms; alpba-clefin sulphonates can be made by reaction with sulphur trioxide, followed by neutrsli- -6 - 2 = ORIGINAL

2 (re 7 zation under conditions such that eny rultones prcseut are hydrolyzed to the corresponding hydroxy alkane sulphonntez. tultable alpba-sul- phocarboxylates contain from 6 to 20 carbon atoms; included herein are not only the salts of alnha-snlphoaated tatty acids but also their esters made from alcohols eontaining 1 to 1 entbon atoms.

Suitable alkyl glyceryl etier sulphates nue ethers of alcohols heving from 10 to 1% carbon atoms, more espec tally thnae derived from nroco- put oil and tallow. &ullnble alkyl prtennl polretlioxy ether sutvhaters have from 8 to 1¢ carbon ators in the alkyl chaiv aod an average of from 1 to 6 -CH,CIL,0-grours ner molecule. Guitable 2-pecyloxyalikane . -l-sulphonates contain from 2 to 9 cetbon elome in the acyl group and from 9 to 23 carbon atoms Ln the nlkane molety. tuitable beta- alkyloxy alkane sulphonates contain from 1 to 3 carben atoms in the alkyl group and from {, to 20 garbon atoms in the alkane moiety. do } : .

The alkyl chains of the foregoing anionic surfactants can be derived = from natural sources Buch as coconut oil to tallow, or can be made synthetically as for example hy using the Ziegler or Oxo processes.

Water-solubility can te achieved by nsing alkali metal, ammonium, or alkanolammonium cations. sodium is preferred. Ilixtures of anionic surfactants are contemplated by this invention: a satisfactory mix- ture contains alkyl benzene sulphonate having 11-13 carbon atoms in the alkyl group snd alkyl sulphate having 12 to 15 carbon atoms in the alkyl group.

Suitable nonionic surfactants to be ineorporated in the c ompositions . herein, are water-s>luble ethoxylated materials of HLB 11.5-17.0 and include (but are mot 1imited to) C3020 vrimary and secondary alcohol ethoxylates and C.-%0 alkylphenol ethoxylates. Cini linear primary alcohols condensed with from seven to thirty moles of ethylene oxide per mole of alcohol ere preferred, examples being

Cpy=Cyg (EO)gs CygCy (FOJpg And eipecially Cye-Cyy (B0)p) ~ 7 - _AIGINAL nantes cmt.

Zeuy

Cationie co-surfactants which can be used herein, include water-solu- ble quaternary ammonium compounds of the form RyRgRgR NX", wherein

Ry, is alkyl having from 10 to 20, preferably from 12-18 carbon atoms, and Re, R and R are each C, to Cs alkyl preferably methyl; X~ is an enlon, e.g. chloride. Examples of such trimethyl ammcnium com- pounds include Cio-Cay alkyl trimethyl ammonium chloride and cocoa- alkyl trimethyl ammonium methosulfate.

The compositions of the invention are essentially free of water-in- soluble long-chain alkyl amine softening agents, and derivatives thereof, since it has been discovered that they interact negatively with cellulase, in the pH conditions of the present invention. Deri- vatives of the amine softening agents include the corresponding amine compounds. Such amine softening agents are disclosed in e.g. EP.A 0.026.528 and EP.1 0.120.528. and include in particular amines of ‘ oo 0.15 the formula RRR HN where R, and R, are Cc to so alkyl chains, and Ce

Ry is ¢ to Co alkyl chain or hydrogen.

The compositions herein are formulated at a pH in the range of from 6.5 to 9.5, measured as a 1% solution of the compodtion in distilled water. At this pH-range, the cellulases for use herein have their optimum performance.

The fabric-softening clay material

The c ompositions herein must contain a clay softening agent.

Such clay softening agents are well-known in the détergency patent literature and are in broad commeréial use, both in Europe and in the United States. Included among such clay softeners are various heat-treated kaolins and various multi-leyer smectites. Preferred clay softeners are smectite softener clays that are described in

German patent document 23 34 899 end in U.K. patent 1,400,898, whith can be referred to for details.

BAD ORIGINAL

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DG

The most preferred clay fabric softening materials include those materials of bentonitic origin, bentonites being primarily montmo- rillonite type clays together with various impurities, the level and nature of which depends on the source of the clay material.

Softener clays are used in the preferred compositions at levels of at least 1%, generally 1-2, prefershly 2-1}.

Optional ingredients

The compositions herein may contin, in addition Lo Lhe essential ingredients, certain optional ingredients,

For instance, it is preferred that throngh-the-wash detergent com- positions 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, water-

Mme ap soluble phosphates such a8 tri-polyphosphate. and sodium ortho- snd oyro-phosphates, ood mixtures thereof. Metal ion sequestrantd (A: A clude all of the above, plus materials lke ethylenediaminetetra- acetate, the smino-polyphosphonates and a wide variety of other / poly-funchkional organic acids and salts too numerous to mention in ’ detail here. See U.S. batent 3,579,454 for typical examples of © 20 the use of such materials in various cleaning compositions. Pre- ferred polyfunctional organic acids species for use herein are citric acid, ethylene diamine tetrauwethylenephosphonic acid, and ‘ . diethylene triaminepentamethylenephosphonic acid. '

A further class of detergency builder materials useful in the pre- gent invention are insoluble sodium aluminosilicates. The 1-10 micron size zeolite (e.g., zeolite A) builders disclosed in German patent oly.22.655 are especially preferred for use in low-phosphate or non-phosphate compositions. In general, the builder/sequestrant will comprise from 0.5% to U5% of the composition. £:AD ORIGINAL

The compositions herein can also contain fatty acids, saturated or

ER unsaturated, and the corresponding soaps. Sultehly fatty acids, saturated or unseturated, have from 10 to 18 carhon atoms in the allyl chain. Preferred are unsaturated species having from ih to 18 cerbon ato s in the alkyl chain, mest preferebly oleic acid. . 5 The correspotding soaps can also be used. The optional fatty acid/socaps are used in levels uu to 2h.

The compositions herein can also contain compounds of the general formula R-CH(COOH JCI, (COOH) i.e. derivatives of suceinic aéid, vherein R is ©10"%0 elkyl or alkenyl, preferably “127% or 10 wherein R may be substituted with hydroxyl, sultv, sulfoxy or sul- fone substituents.

The succinate builders are preferably used in the form of their water-soluble salts, including the scdium, votessium, ammonium and alksnolammonium salts.

Specific examples of succinate builders include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (pre- ferred), 2-pentadecenyl succinate, and the like,

Also useful as builders in the present context are the compounds described in U.S. patent 4.663.071, i.e. mixtures of tartrate mono- i 20 succinic acid and tartrate disuccinic acid in a weight ration of monosuceinic to disuccinle of from 97:3 to 20:80, preferably 95:5 to 40:60.

Another optional ingredient is a bleaching agent. Ireferred are peroxygen bleaching agents such as sodium perborate, commercially available in the form of mono- and tetra-hydrstes, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate and urea peroxy- hydrate.

Bleach activators my be used in combination with the above pero- : xygen bleaching agents. Classes of bleach activators include esters, imides, imidazoles, oximes, and carbonates. In those classes, pre- wD ORIGINAL

Du 42 ferred materials Include methyl n-aceloxy benzoates; scdium-p-acetoxy benzene sulfonates such as sodium Y-octanoyloxyvenzene sulfonate; sodium-lU-octanoyloxybenzene sullcnate, ard sodiun-l-decanoyloxyben- zenesulfonate : biophenol diacetate; tetra acebty) ethylene diamine; tetra acetyl hexamethylens diowmine; tc tra peety! cethylene diamine.

Other highly preferred pevowypen blearn activat-ns «hich are dis- closed in U.S. Fatents h,ut:3,77 and ',534,130, are alpho-substitu- ted alkyl or alkenyl esters, su~h as codium=b(2-chiLorenctenoylory )- benzene sulfonate, sodium %-(3, 5, 5-lriwethyl hexanny Loxy )benzene sulfonate. Suitable peroxyacids are nlsn peroxyren bleach sctivatore such as deseribed in published turopern batenl agnlieation O 166 571, l.e., compounds of the general Lvpe it AQUI aud {XAL, wherein R is a hydroxcarbyl group, X is a heteroatom, A is a carbonyl bridging group and L is a leaving group, especlnlly -xybenzenatulfonnte. vee, 15 Enzymes other than cellulases, such as proteolytic, amylolytic, or Lo lipolytic enzymes cen be used in addition to the cellulase herein,

Soil-release/soil-susyending agents cru be present in the composition herein at levels typically frow 0.1% to 10} by weight. In particular : alkoxylated polyamines suitable as clny-soil removal/anti-redeposition agents can be used. These components, as well as their preparation, are disclosed in EP-tA 0 112 5y3, the disclosures of which are incor- porated herein by reference.

It is to be understood tbat the term “polyamines” as used herein re- presents generically tle alkoxylated iolyamines, both in their amine form and in their guaternarized form. Such materials can conveniently be represented as molecules of the empirical structures with repeat- ing units: - 11 - ww ORIGINAL ‘ mm een tim ered \

July? ~t BN ~~ R 1- Amine form (Alkoxy ) and f —+t v aan rom mame 1 1 x untornized form

AL xy ) 1

To wherein R is a hydroenrcbyl oronp, usaally of 2-6 carbon atoms; R ray be a C,-v nydrocariban; toe alloxy groups ore othory, propoxy, 20 and the like, and y is 2-30, most pveferably 1-20: u is an integer of at least 2, preferably 2-20, most preferahbl; 3-Y: and X is an anion such as halide or metnylsulfale, resuiting trom the quater- nization reaction. . The most highly oreferred polyamines for use herein are the so-called

Cone ethoxylated polyethylene imines, i.e., the pdlyrerized redttioh fos duct of ethylene oxide with ethylins-imine, having t'c geueral for- mula: (640) —]- H— Cl — ut J Bi —— (EtO) 2 2 mn | y (EtO), (tO) wherein n is an integer of 3 to 5 and y is an integer of 10 to 20.

Soll suspending agents cau also be selected from polyethylene gly- ) ] cols, of molecular weight LOD to 1000, jolyacrjlates, or copolymers of acrylic acid and naleic anhydride/acid.

The detergent compositions herein are preferably free of carboxy- methylcellulose.

Moreover, the compositions herein cnn contain, in addition to ing- redients already mentioned, various other ontioral ingredients typi- cally used in commercial products to provire aesthetic or additional ? _ te hos bie ORIGINAL te Cey2 product performance benefits. Typicnl ingredients include pH regu- lants, perfumes, dyes, optical brighteners, hydrotropes and gel- control agents, freeze-thaw steuilizers, heclericides, uvreservativen, suds control agents, blercn stabilizing sgents.

EXPERIMENTAL PART

A granular detergent composition vee -~repaved, =scerrding to the fol- lowing table:

Ingredients ony weight

Sodium Linear ys alkyl benzene ull nale LL. <. \

Sodium Tallow alkyl sulfate 5.0

Tallow alcohol ethoxylate (&O0L1l) : 0.3

Sodium tripolyphosphat: 2h. 0

Bentonite clay 6.9 doil suspending agent * 2.0

Proteolytic enzyme 0.9

Sodium sulfate, water, minors un to balance * copolymer of acrylic and maleic acid, IW 60,000 (sodium salt).

From the basic composition hereinabove, two compositions were prepared:

Composition A, to be vred rs veleren:e, where cellulase granulates (1.79% by weight of total composition) conteining crude cellulase enzymes and cellulose, were dry-mixe?l with the rest of the composition.

Composition B, a composition aceprding to the present invention, where cellulase gramulates (1.79% by weigh! of total composition) contain- . ing crude cellulase enzyme, cellulos~, and 8 coating of polyethylene glycol (5% weight level of granulates, MW 1500) and of calcium car * bonate (104 weight level of granulat-s).

In both compositions A and B, the cellulase was of thie type described in U.S. 435,307 and its amounts were auch as to give an activity £.\3 ORIGINAL - 17 a -

2 ele y2 to the presence of the calcium carbonate.

CIAIMS

1. In a perticulate composition for cleaning end softening of fabs fics comprising a surface-active sgeut, a fabric-softening clay mate~ rial and cellulase granules; the ing: ovement wherein the said granules contain calcium carbonate in an amonni trom 17 to 50% by weight of said granules. 2. A composition in accordance with claim 1, wherein the calcium carbonate 1s present at levels of from 5p to 157 by weight of the cellulase grannlates. 3. A composition in rcccordauce with claim 1, wherein the calcium carbonate is coated onto the cellula-e granulates.

Lb, A compogition in accordance with claim 1, wherein the cellulase i is bacterial or fungal cellulase having a pH optimum of between 5 and 9.5. , 5. A composition in accordance with claim 1, wherein the cellulase is an alkali cellulase having an optimum pH from 6.5 to 9.5, 6. A composition in accordance with c¢leim 1, wherein the composition has a cellulase activity of from 5 tn 1360 Cllaste activity unit/gram of composition. 7. A composition in accordance with claim 1, which contains from 1% to 50% by weight of the cellulase granulates, and from 1% to 20% by weight of the fabric-softening clny material. 8. A composition in accordance with claim 1, wherein the cellulase granulates are present at a level of from 1.5% to 10% by weight, and the fabric-softening clay material is present at a level from 2% to 10L by weight.

Ls Ni ORIGINAL - 10 _ dem te enamel

Claims (1)

1. Lwd2 9, A composition in accordance with claim 1, wherein the fa..y, softening clay material is a bentonite ¢lay.

   10. A composition in accordance with claim 1, vherein the cellulase granulates are free of titanium dioxide and magnesium silicate.

   11. Cellulase granulates tor use ip the composition of claim 1, wherein they contain from 1% to 50h, by weight, ~f calcium carbo- nate.

   12. Cellulas~ prannlates according to claim 11, wherein the cal- cium carbonete is present ol levels »f from DF to 15% by weight

   13. Cellulase granulnten according toy olan 1) whicli have #-- caleium carbonate coated wntC them,

   14. Cellulase grarulates according to claim 11, «herein the cellu- lase is hacterisl or fungal cellulase having a pli optimum of bhet- ween 5 and 9.5. Co Cone he : 15, Cellulase granulates anceording to claim 5, wherelu the cellu- lase is an alkall cellulase having an optimum pl from 6.5 to 9.9.

   16. Cellulase granulates according to claim 11 which are free of titanium oxide and magnesium silicate. ¥ * »* * % »’ x ¥ Al . + ki * * x * » Dirk Le MARTELAERE Inventors ] + ORIGINAL . 15 am