CA1177765A - Process for cleaning clothes - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

When soiled parts of clothes are rub-coated with an enzyme-containing liquid detergent by means of coating-type liquid container, the coating portion of which is composed of a porous body made of synthetic plastics material, the enzymatic reaction be speeded up to finish the soiled clothes in an efficient clean manner.

Description

1 ~77765 This invention relates to a process for cleaning clothes using an enzyme-containing liquid detergent and a special container therefor. More particularly it relates to a process for cleaning clothes which comprises the step of applying the enzyme-containing liquid detergent to soiled necks and wristbands as well as various spots by means of a specific coating-type container therefor, thereby to remove the stains and to finish the clothes in a very clean manner.
It is well known that especially persistent stains in worn clothes are those soaking into the necks and wristbands thereof.
Further stains e.g., spots due to split foods and proteinic blots on baby clothes are very unremovable. Heretofore, several methods have been designed for removing these stains, including smearing a solid soap thereon followed by crumpling the clothes; transferring a liquid detergent from a container to a cap thereof and coating them with a cap of the detergent; and spraying a liquid detergent thereonto.
These methods show a certain beneficial effect compared with a usual washing method and are often practiced in home. However they are still insufficient to remove the stains completely.
In order to enhance an effect of removing pro~ einiC stains, it is known to add the proteolytic enzyme protease to a powdered detergent. An enzyme has a temperature suitable for the enzymatic action thereof (the temperature being hereinafter referred to as "optimal temperature") and shows a maximum effect at the optimal temperature, which is usually from 40 to 60 C.
An object of one aspect of this invention is to provide a process for cleaning clothes which is especially effective for removing persistent stains soaking into the necks and wristbands thereof as well as spots due to split foods and proteinic blots thereon.
An object of another aspect of this invention is to provide an enzyme-containing liquid detergent and a special container for containing said detergent therein which are used in the above process.
In order to further these objects, applicants have made various studies on whether an effect of removing stains on the necks and wristbands, spot stains, etc. can be improved remarkably for utilizing the temperature dependence of the enzymatic action. As a result, it has unexpectedly been found that by rub-coating soiled clothes with an enzyme-containing liquid detergent by means of a special coating-type container therefor, the surface temperature of the clothes increases due to frictional heat and the enzymatic reaction proceeds rapidly so that the soiled clothes can be finished in a very clean manner.
A process for cleaning clothes according to one broad aspect of the present invention therefore comprises the step of rub-coating soiled parts oE the clothes with an enzyrne-conlaining ]iquid detergent by means of a coating-Zype ]iquid container, Zhe coating portion of which is composed of porous body made of a synthetic plastics material.

By a variant thereof, the enzyme-containing liquid detergent is composed of an enzyme-conZ:aining liquid detergent composition containing 10 - 40% of anionic surfactant, lO - 40% of nonionic sur-factant, 0.05 - 10% of enzyme and l - 10% of solubilizing agent.
By another variant, the enzyme contained in the liquid detergent is one or more enzymes selected from the group consisting of protease, lipase, amylase and cellulase.

I X 777~5 By still anothcr variant, the sub-coating of the clothes with the enzyme-containing liquid detergent is carried out at a rate of 20 - 50 cm/sec under a load of 0.2 - l0 kg/cm , the amount of the detergent applied on the clothes being 0.1 - 5 g/100 cm .
By a still further variant, the coating face of the porous body is convex shaped.
By a further variant, the raw synthetic plastics material for the porous body is selected from the group consisting of poly-propylene, polyethylene, ethylene-vinylacetate copolymer, acrylonitrile-styrene copolymer and acrylonitrile-butadiene-styrene copolymer.

By yet a further variant, the enzyme-containing liquid detergent has a viscosity of 50 - 500 cp.
By another aspect of this invention, a liquid detergent composition is provided which comprises: 10-40% of anionic surfactant;
10 - 40% of nonionic surfactant; 0.05 - 10% of enzyme; and 1 - 10%
of solubilizing agent; the liquid detergent composition being contained in a coating-type liquid container, the coating portion of which is composed of a porous body made of synthetic plàstics material, the liquid detergent being adapted to be rub-coclted on soiled parts of clothes by means of the coating portion.

In the accompanying drawings, Fig. l shows the outline of essential parts of various coat-ing type l;quid containers.
Fig. l(a) shows a longitudinally sectional view of a coating portion having a convex shaped coating face used in an aspect of the present invention.

Figure l(b) shows a longitudinally sectional view of another coating portion having a planar shaped coating facc used in an aspect of Lhe present invention.
Fig. l(c) shows a longitudinally sectional view of a con-ventional sponge lype coating portion.
Fig. l(d) shows a longitudinally sectional view of a con-ventional roll-on type coating portion.
Fig. 2 shows the outline of another embodiment of an aspect of this invention.
According to a broad aspect of the present invention, frictional heat is produced in the above-rnentioned rub-coating step to increase t:he surface temperature of the clothes, whereby an enzymatic reaction proceeds rapidly so that the stains on c]othes can be removed very cleanly. Subsequent to the rub-coating step, whole clothes are conventionally washed by conventional means, e.g., by means of a washing machine or the like.
In order to produce frictional heat during the rub-coating step in process of an aspect of the present invention, it is preferable to scrub the clothes with a coating portion of a container and apply an enzyme-containing detergent cont-ained in the ont~-lincr onto the clothes repeatedly. An increasc in t(m~)er;lLurc duc~ co the frictional heat has been measured by means of a thermotape which was laid under the cloLhes. A a result, it has been observed that the temperature .ncreased easily by two or three dcgrees centigrade by using a coating-typc liquid ccnt~ainer having a coating portion of which is composed of a porous body rnadc of synthetic plastics material. It has also been found that it is also possible to increase the temperature by 10 C.
The rub~coating is a preferable washing method because of the production ~ 17776~

of frictional heat as well as the penetration of the liquid detergent into the fibrous structure of the clothes. Since the tenperature dependence of the enzymatic action is great, even a slight increase in temperature can bring about favorable results.
The porous body made of synthetic plastics material used as the coating portion of the container in aspects of the present inver-tion is usually produced by heating and sintering granules of synthetic plastics material having a fixed particle size in a mold. The porous body thus obtained is an oper cell foam having suitable firmness and strength. Therefore wher, it is used as a coating portion o the container, it is possible to rub the clothes to such an extent that they are not damaged but yet to hasten a reaction of enzyme contained in the liquid detergent. ~urther since the pore size and distribution of open cells are highly uniform, the ]iquid detergent can be fa~iorably passed Lherethrough and d wide and uniform coa~ing locus can be stably obtained.
A roll-on type container which is known as a liquid coating container cannot produce friction because of its struclure. Anotller known coating container has a coating portion composed of a spor,ge or plastic foam which is different from an open cell foam having suitable firmness and strength, and therefore it cannot exhibit a temperature increasing effect.
In the practice of or,e aspect of the presellt invention, the enzyme-coating ]iquid detergent is rub-coatcd preferably at a rate of 20 - 50 cm/sec under a ]oad of preferably 0.2 - 10 kg/cm , more preferably 0.5 - 3 k&/cm . An amount of the cnzyme-containing liquid detergent applied is preferably 0.1 -- 5 g/100 cm , more preferably 0.2 - 2 g/100 cm . The preferable porous body which is used is one - 4a -1 1 777B~

having such a structure that makes it possible to app]y the above-mentioned amount of the liquid detergent when this aspect of the present invention is practiced under the above-mentior.ed conditions.
Those having a mean pore size cf 50 to 1,000 microns preferably 300 to 700 microns are preferably used. Further, it is preferred that the porous body have a flow rate of the enzyme-ccntaining liquid detergent of 5 to 30 g/min. The flow rate is defined as the amount per unit time (minute) of the enzyme-containing liquid detergent flowing cut through the coating portion of the liquid container wl.en the liquid container, the bottom of which has been cut off is placed so that the coa~:ing portion thereof composed cf the pcrous body points downward and then it is filled with the liquid detergent in an amcunt correspond-ing to 12 crr, of liquid level per cm of the surface area of the porous body (the cross-sectional area in case that the porous body is conve~
shaped) at 20 C.
When the above-mentioned flow rate is toc much or too little, wide and uniform coating locus cannot be obtained stably. In case of too little flow rate, it is needless to say that t~e function of the coating type container cannot bt ful]y exllibit.td. On the other hand, it is self-evidenr that toc rnuch flow late is not preferable in view of the friction effect and unecc.nomical.
Examples of the raw synthetic plastics materials for the orous body, i.nc]ude various high molecular materials, among which po]ypropylene, polyethylere, ethylene-vinyl acetate copolymer, acryl-onitrilt-styrene copolymer and acrylor.itrile-c~utadiene-~.tyrtnt copolymtr are preferable bccause they can give porous bcdies which are not damaging to the clothes and have suitable firmness and strt-ngth 1 ~777~5 enough to enhance the friction effect.
According to an aspect of the present invention, it is desirable that the diameter of the ccating portion in the coating-type container be 1 crr, or more in order to enhance the friction effect. Further it is desirable that the ccntainer part of the co~ting-type cortain~r have such a cap~city that it can be hand-held. Further-more with respect to t~e shape of the coating pc,rtion, a convex shaped one is more Freferable than the planar one because of good workability and enhanced friction effect.
As shown in Fig. l(a) and (b), the coating-type container used in one aspect of the present invention is composed of a cap part 2 having a coating portion 1 of the porous body, and the container part 10 (shown in Fig. 2) in which the enzyme-con-taining liquid detergent is filled up, both of wllich are connected with a screw. More particularly the coating portion 1 is fixed by a holding means 3 at the top of the cap part 2 and the back side thereof is supported with a supporting plate 4 having a plural of holes 4'.
As shown in Fig. 2,, keeping the coating face of the coat:ing means 1 in touch wit:h a sc~i]ed part of clothc~s ]1, orlc~ rub-coats the soiled part with the erlzylne-coatirlg liquid dctel-gent in the container pert 10.

One example of an cnzymc-contailling liquid dctergent used in an aspect of the pr-esent in~ent-ion is an cnzyme-containing liquid dctergent cornposition colltdinirlg the rcllow;ng comporlents.

(1) .i~nionic slll-f~ctant 10 - 40o (2J ~'onionic SU1 factant 10 - 40~
nz~me O . 05 - 10%
(4~ Solubilizing agent 1 - 10%

1 177~65 In order to per~orm the abov~-m~ntioned rub-coating more effectively further to increase the cleaning effect of the clothes, the viscosity of the enzyme-containing liquid detergent is also to be consider~d. In addition to the viscosity, vario~ls factors, e.g., washing power and safety should be conside~ed. With regard to these factors, it is preferable to use as the enzyme-containing ~iquid detergent those ha~ing a viscosity of 50 - 500 cp.
Examples of anionic surfactant ~, include the following especially preferable ones:

Polyoxyethylene alkyl ether sulfate ~hich has a linear or branched alXyl gl'Ollp }-~aving an average carbon number of 10 -16 and in \~hicll an average mole number of ethylene ox-ide added in a molecule is ~ - 6 in case that the al~yl group is linear and 2 - 4 in case that it is bra-lched.

Other examples of the anionic surfactant, include at least one of anionic surfactants selected from (1) - (9) mentioned helo~ togethel with or instead of the abo~e-me]ltioned anionic surfactant. ~mong them, the particullrl) preferred are those sho-.~n in (1) (2) (~), (4) alld (5).

(1) l.ine.ll or hrlnclled alk~lbellzelleslllfonates ~ith an alk)~l group ha~ing an avera~e carbon numher of 10 - 20.

(2) .~1~)1 or alkenyl ethel sulfltes ~]lic]l has a linear or l)ranclled alkyl group havillg an avera~e cal-bon number of 10 - 20 and in ~hich avelagel\ 0.5 to 8 moles of either ethylene oxide (E0) or plol)!lene oxide(l'0) or butylelle oxide(B0) is added in a molecule; or averagely 0.5 to 8 moles of E0 and P0 are added in a molecule in a proportion of E0/P0 of 0.1/9.9 to 9.9/0.1; or l 17776~
a~ el-agcly O . 5 - 8 mol es of IEO alld BO arc addcd in il molecule in a propoltion of lO/BO of 0.1/9.9 - 9.9/0.1.

(3) Alk~l or alkenyl sulfates havirlg an alkyl or alkenyl group of l~hich an average carbon number is 10 - 20.

(4) Olefin sulfonates having average carbon atoms of 10 -70 ill a molecule.

(5) Al~ane snlfollatcs ha~ing a~'el-;lgC carl)on atoms of 10 -20 in a molecule.

(6) Saturated or unsaturated fatty acid salts having average carbon atoms of 10 - 24 in a molecule.

(7) Alkyl or alkenyletller carboxylic acid salts ~hich have an alkyl or al~enyl group of average carbon atoms of 10 to 20 and iJI ~;hicll averagely O . 5 to 8 moles of either ethylene oxide(EO) or prop)lelle oxide(PO) or butyle]le oxide(BO) is added in a molecule;
or averageiy 0. 5 to 8 moles of EO and PO are added in a molecule in a proportion of EO/PO of 0.1/9.9 to 9.9/0.1; or averagely 0.5 to 8 moles of EO and BO are added in a molccule in a proportion of EO/BO of 0.1/9.9 to 9.9/0.1.

(8) ~-sulfofatty acid sales Ol esters rcprcsclltcd by the follol.~ing formula:

R--C~CO2 Y
~0 ~Z

(~hel Cill ~' is a]l 31~)'1 group of 1 to ~ carlon atoms or a pailed ion, Z is a pailcd ion~ and R is an al~yl or al~envl group of 10 to 20 carbon atoms.) Ex~mpl~s o~ paired ions in the anionic surfactant, include alkali m~tal ions, e.g., sodium and po~assium ions; alkaline earth metal ions, e.g., calcium and magnesium ions; ammonium ion; and alkanolamines having 1 to 3 alkanol gro~ps of 2 or 3 carbon atoms, e.g., monoethanolamine, diethanolamine, tri-ethanolaminc and triisopanolamine or ~he like.

(9) Amino acid type surfactants rcpresented hy the followinggenelal formulac:

lo '~ C 0 - N -C ~-C ~0 X
R2 R~

(~herein Rl is an alkyl or alkenyl group of 8 - 24 carbon atoms, R2 is hydrogen or an alkyl group of 1 or 2 carbon atoms, R3 is a residual group of the amino acid, and X is alkali metal or alkaline earth metal ion.) ~; 2 R 1--CO--N--( CH2 ) n--COOX

(whercin Rl, R2 alld X are thc samc as those mentioned ahovc alld n is .3n integcr of 1 to 5.) 3 Rl > N--( C~2 )m--COOX

(wherein Rl is the same as mentioned above and m is ;~; an integer of 1 to 8.) ~

.1 ~1 ~ N--C~ COOX
~4 ~

(-herein Rl R2 and ~ are thc same as mentioned above and R4 is hydrogen or an al~yl or hydroxyalkyl group of 1 or 2 carbon atoms.) K 5 Ks--N - C~ - C OOX

1~2 t~

(~heleiJI R2 R3 and ~ are the s.lme as mcntioned above and R5 is ~-h~dlox)alkyl or ~-h droxyalkenyl of 6 to 8 carl-on atoms.) ~5 > N-- CH - CQOX

1~

~ hcreirl R R5 a~ rc thc S;lllIC as mcnt;ollecl al-ove.) Examp]es of nonionic surfactant C~ ~ include the following particu~arly preferab]e nes:
(a) Po]!o~ctll~lcnc sec-.llk)l cthcr \~hicll l~as arl alkyl ~roup h.lvillg an average carboll nulnl-er of 10 - 14 and in ;hicll ~n avcrage molc nurnber of ethylclle oxide added in a molecule is 5 - 12.

- 10 -1 ~7~765 (b) Polyoxyprol)ylene polyoxytthylcllc lincar alkyl ether hich llas an alkyl group havillg an average carbon number of 8 or lO and in \~hich an avcr3gc mole number of propylene oxide added in a molecule is 1 - 5 preferably 1 - 3 and an a~erage mole number of ethylene oxide added in a mole-cule is l - 20 preferably S - 10.

Examples of nonionic su~factant ~ , inc]ude at least one of those selected from (lO) - (17) mentioned belo-.
together with or instead of the above mentioned surfactants (a) and (b). .~mong them particularly preferl-ed are those sho~n in (10) (ll) and (14).
(10) Polvoxyct]lylene alkyl or alkenyl et]lers ~lhich llave an alkyl or alkenyl glOUp of average carbon atoms of lO to 20 and in ~.~hich 1 to 20 moles of ethylene oxide is added.

(11) Polyoxyet]lylelle alkyl l~henyl ethers ~hich have an alkyl group of average carbon atoms of 6 to 12 and in ~hich 1 to 20 moles of ethylene oxide is added.

(12) Polyoxyl-lol)yltnt alkyl or ialkcllyl etlltrs ~h;ch havc an alkyl or alkenyl grt)up of avtrage Carl)OI'l atollls of 10 to 20 and in ~hich 1 to 20 molts of propylene oxide is added.
~ 13) Polyoxybutylene alkyl or alkenyl ethcrs which have an alkyl or alkenyl group of average carbon atoms of lO to 20 and in ~hich ] to 20 moles of butylcne oxi(le is added.

1 1777~;~

(14) ~OniOIliC surfactants ~}liCil have an alkyl or alkenyl group of average carbon atoms of 10 to 20 and in w!lich totally l to 30 moles of ethylene o~ide(EO) and propylene oxide(PO) or EO and butylene o~ide(BO) are added in a proportion of EO/PO or ~:O/BO of 0.1/9.9 to 9.9/0.1.
(15) Higher fatty acid alkanol amides or their alkylene o~ide adducts represellted by the follol~ing general formula:
l12 ( C HC llz (:) ) n Kll CON<
( CH C~I2 O }m~ II
Rl2 (l~herein R ll is an alkyl or alkenyl group of carbon atoms of lO to 20 R12 is hydrogen or methyl n3 is an integer of l to 3 ancl m3 is an integer of 0 to 3.) (16) Sucrose fatty acid esters obtained from a fatty acid of average carbon atoms of lO to 20 and sucrose.
(17) Fatty acid glycerol monoesters obtained from a fatty acid of a~erage carl)on atoms of lO to 0 alld ~Iycelol.

Examp]es of enzyme ~ , preferably include at least one of hydrolases, e.g., protease, lipase, amylase and cellulase, the origins of whi.ch are listed be]ow. Eurther the amount of the enzyme ~
i.n the liqui.d dctergent is preferably 0.05 to 10% by weight. Preferred cnzymes inc]ude protease, decomposing proteinic soils, and cellulase, 5wclling the ~ibcr to make ~he soils easily rimovable.

I $ 77765 Exa~pl~s of .~nzyme ~ which is an essential componcnt in ~h~ pr~s~nt invt~ntion, include those which are wid~ly distributed in nimals and p]ants, bacteria and fungi as w~ll as their p~rified fractions.
As t]~e origins of cellulase, thc follo-~ings are e~em-plified.
~a) Protozoa (Ciliata, Flagellata, Amoeba, etc.) (b) ~ollusc (Snail, Soft clam, Shi~ ornn, etc.) (c) ,\'ematoda (d) Annelicla (e) Ichino(]cnlllata (Sea chcstnut~ ctc.) (f) Crustacca -(g) Insect.l (Ant, Beetle, etc.) (11) Bacteria (Cellulomonas sp., Bacillus sp.) (i) Fungi; llyphomycetes (Fullgi impcrfecti, Pllycomycetes, Ascomycetes, etc.) (Aspergillus niger, Aspergillus orvzae, Takamine-cellulase, llwnicola insolclls, Rhi70pus sp., Asl-elgilllls c c~ l o ~, l c, .~ ) c (j ) Algae (li) Li chelles (1) Land gl'CCII plants In adclition, the follo~ing al~llli ccllulases can be ll ,c c cl .
(m) Cellulasc obtai]led by culturing mic]oorganislns belong-ing to Genus Bacillus of l~hic]l thc microolganism deposit nU!llb~'r~ iTl ~ 'herl (the Fe~ en~ti(-11 P~es~arch Institl~te~ in Japan) are 1138, 11~9~ 1140 and 1141, respecrive]y (See~ Japanese Patené
Publication No. 28515/1975).
(n) Cellulasc produced from Cellulase 212 - producing micro-organism belonging to Genus Aeromonas of ~.~hich the micro-organism deposit number in Bikoken is ,306.

The following commercially available cellulases originated from the above-ment:ioned origins can be used in aspects of the present invention.
(1) Cellulase Ar' from .~mallo ~l~allllaceutical K.K.
(2) CELLULOSI~ AP (T.M.) from Ueda Chemical K~K~
(3) CELL11LOSIN AP (T.M.) from Ueda Chemical K~K~
(4) Cellulase-Ono~uXa from ~inki Yakult K.~.

(5) I'ancellase froln ~inki ~akult K.~.
(6) MACEROZYME (T.M.) from Kinki Yakult K~K~
(7) ~leicelase from ~leiji Confectionely ~.K.
(8) CELLUZYME (T.M.) from Nagase K~K~
(9) Soluble Sclac.e from Sankyo Pharmaceutical (l0) SANZYME (T.M.) from Sankyo Pharmaceulical K~Ko (11) Cellulase ~-12-C fro]n ra~cd;l I'ha~ aCcut ic.ll lnd.
(12) To~o-Cellulase from loyo 13rel~illg K.K.

(13) Driserase from ~yol~a ~ermentatioll Industries K.~.
(1~) LUIZY~1E (T.M.) from l,uipald Werk Co.
(15) Takamine-Ce1lu1asc from Chemisc}1c labrik Co.
(16) I~'aller~tein-Cell~llase from Si~m;l Chcmicals Co.
(17) Cellulase Type 1 from Sigma Chemicals Co.
(1~) Cellu]ase Scrva from Serva l,aboratory Co.

~ 177~65 (19) Cellulasc 36 from Rollm ~ Haas Co.
(~0) ~liles Cellulase 4 000 from ~ilcs Co.
(~1) R ~, H Cellulase 35, 36, ~S Conc. from Philip ~lorris Co.

(~2) COMBlZYM (T.M.) from ~ysco ~aboratory ~o.

(2~) Cellulase from ~lakor Cllcmicals Co.

(~) CELLUCRUST (T.M.) from Novo Industry Co.

(25) Cellulase from Gist-~rocades Co.
It is preferred to use the cellulase having an enzymatic activity of at least 0.001 unit/mg of solid content (1 unit/mg of solid content means an enzymatic activity of cellulase when it produces ].0 u mole of glucose from cellulose at a temperature of 37 C and pH
of 5 for 1 hour). The amount of cellulase in the liquid detergent composition is preferably from 0.01 to 10% by weight, more preferably ~rom 0.1 to 10% by weight.
Examples of preferable hydrolases other than cellulase, inc]ude carboxylic acid ester hydrase acting on an ester lin~age thiol ester hydrase glycosiclc hydrase and pc?ptidyl peptide h!drllse c~amplc?s o~ ~hich are givcn as u]lder.
(1) Protease l-elollging to pcltid\] pcpticlc hy(ll.lse Subti]isi]l Collagcnase, ~eratill.lse (2) Glycos ide hydrase Cellulases \-llicll have been melltionc?d above arc e~cluded fl-om tl)e group of ~-lycc)siclc? hydlase.
I'refcrred ale cY-amyllsc l~ectill;lse cllitillase, 1 1777~

Carbo~ylic acid ester h~drase Lipase Commercially available en7yme products and their manu-facturers are listed belol~.
Alkalase, Esperase, Sabinase, AMG (T.M.)~ BAN (T.M.), FUNGAMIL (T.M.), SWEETZYME (T.M.) and TERMAMIL (T.M.) from Novo Industry Co., Copenhagen, D~nmark ~lacsatase-P, High Alkaline Protease, Amylase THC and Lipase from Delft Gist Prokeicles n.v., .~etherland Protease B-400, Protease B-4000, Protease AP and Protease AP 2100 from Sch~.~eitzlische Ferment A.C., Basel, S~itzerland CRD-Protcase frorn ~onsanto Co., St. Iouis, ~lissouri, U.S.A.
Pio~ase from Piopin Corp., ~lollticers, Illinois, U.S.A.
Pronase-AS and Pronase-AF from ~akcn Chemical K.~., Japan Lapidasc P-2000 from l,apiclas, Sckr.ln, I:lilnce Proteolytic enzyme products (a particle size of lOO~lo passing through a Tyler standard sie~e of 16 mesll and 100o rcmaining on a Tyler ~talldard sie~e of 150 mesll) from Chrinton Corn Products Co. (a di~ision of StaJIdard Brands Co., ~'e~ York) - ]6 -1 t7776~

. Ta~;lmine, Bromelein 1:10, ~ roteol~-tic l:n_~me ~00 ~ud Enz~me L-W (obtain~d not fro,ll bactc~ria but mould) irC)III ~ 'S
Ch~mical Co., Elkheart, Indiana, U.S.A.
LOZYME P-ll (T.M.) Concenlrate, P~ctinol, Lipase B, LOZYME PF (T.M.) and LOZYME J-25 (T.M.) from Phom ~ Haas Co., Philadelphia, I~.S.A.
PROZYME 200 (T.M.) from Jack Wolf & Co., a subsidiary of Novco C]lcmical CO., .\le~ Jersc?, U.S..~.

. .~TP ~0, ~TP 120 and ATP 160 from Lapidas, Se~ran, Franee . Olivase from ~agasc Industries, J.lpan The amou]lt of the above hycdrases othcr than eellulase ineorpolated into the detergent eomposition ean be determined depenclillg on eaeh pllrl)ose, but is prefelred to bc 0.001 - 5% b~
~eight, e-speeiall~ ~.0~ - 3 b~ ~eig!lt if convel-ted into the ~ieight of purified en~~me.
Exampl~s of solubilizing agcnts 4 , includc~ th~ followirlg, I.OI-'C'I' ~1](`0}~01~, lo~c~ c`~ ioll;ltc~s~ COI~;~

In addition, the i`oll01~ing .III.~i1ia1'~' collll)oncnts Ina!~ bc used .

(1) Bctain t~pe alilpllol~tie or eatiollie surfaetallts (') Di~alent mc~.ll ion scavcllgers .~t lcast one of builclcr eo~ ollcllts selcetcd from the nclelnlclltionecl s;l]tS (a]~.lli mctal salts or a]kallol amine salts) an(l pol~mel-s ma~ be contaillcd in all amoullt of less than 50o b llt.
- 17 _ 1 ~77~

Phosphates, Phosphonates, Pllosp}lonocarbox~lates, Salts of amino acids, aminopol,vacetatcs, Polyelectro-lytes, ~on-dissociati~e polvmers, Salts of organic acids, (3) Alkaline agents ~4) Resoiling prevc-~nting agents (5) Laundr,v bluing agents and fluorescent dyes Embodiments of the present invention is further explained by reference to the iollowing Examples.
Example 1 The coating type containers used in aspects of the present invention are compared with various conventional coating type con- ' tainers ~1ith respect to coating state, coating ~orkability, effect of producing a heat of frictio]l by CO;Itillg, and dcgree of cleaning soiled natural clotlls.
(1) Liquid detergent composition used Sodium sulfate of alkvl(C = 14.3) polyo~vetllylene(P = 2.5) 20%
Polyo~yl-lopylcne(li = 3)polyo~yctllvlcnc (1' = ~i) 1illc~;lr clcc~ l Ct~Cl .~0o 'I`rietllanolallline 3~0 Fluorcsccllt dye 0.3%
Ethallol 5%
l~1atc~ lallcc~
Protcol!tic cnz~me n.3%
(ESPELASE (T.M.) liquid 8.0M from ~ovo Industry Co.) _ 18 -I 1 7776~

(2) Coating portion of the containcl~ (See l:ig. 1.) ~a) Convex shaped porous body us~d in an aspect of the present in~elltion.
(b) Planar t~p~ porous b~dy used in an aspect of the p~esent invention.
(c) Sponge used for comparison (d) ~oll-on type used for comparison.
(3) Evaluation of coating state and coating ~orkability The coating-type containers mentioned in (2) ~.ere each filled l.~ith the liguid cletergent mentiolled in (1) ~hich ~as then applied to a soiled p.lrt of half-cut natural cloth at an coating rate of 0 cm/sec under a load of 2 kg/cm2. .-~ coating amount \~as 3 ml per sheet of soiled cloth and totally 21 ml l~ith respect to one .ashing system (set) consisting of seven slleets of clotll.
The coating state i.e. the uniformity of coating ~as evaluated based on the follo~iing criteria.

o ...... Ullifo3mly a~ licallc at a Collst.lllt amoullt ~ ...... Partly uncvenly appliccl x ...... Unevenly applicd Apart from the coating state the coating ~orkability i.e. the easiness of coating .as evaluated based on the follo-~-ing criteria.
o ...... The liquid deter~ent flo~s out smoothly and is easily applicable.

I ~ 7~7~;5 ?; .... '1'~1(~ CO~ltill~, ca~ ot lC 1~crfollncc3 smoot]l]y.
~ ..... Intcrmediatc bet~een o alld x (4) Effect of producing a heat of friction b~ coating The heat of friction produced cluring coating ~-as measured at a room teml~elature of ~6C using a thermistor (YEI~ TYPE 2809 digital thermometcr) placed under a soiled cloth.
(5) }'reparation of soiled cloth A mixed c]oth of cotton and TETRONE (T.M.) 9 cm x 30 cm) was scl;ed on a collar of utility shirt, ~hicll ~as then ~.~orn by an adult man for tl~o days. After having been ~orn cloths in ~hich soiling is symmctrical \~ith respect to a central point thereof ~ere selected and half-ctlt at a point of sylnmetry to submit them for e.~amination.
(6) Itas])illg con-litions Itash;ng operation .............. Use of a utility ~ashing machine (~alseta ty~e) l\ater uscd ........ .~0 ~ of cit~ ~atcr l~'ater tcm;l~el-;ltul c ........ ~()(' ltashillg timc ........ 10 IllillUtCs Rinse ........ O~erflo~ing rinse of Ci t~' ~iatcr for 5 minutes (7) E~aluation of degl-cc of clealling As mentioncd in (5!, a sheet of soilcd c]oth ~as half-Cllt so thlt soiling ~as di~ led s~!mlllctric.lll\. One of the half-cut c]oths obtained abo~e ~as ~;asllc(l after merel~ dro~-)ping the liquid deter&ent tnereon witnout usin~ the coatin~ type container. The other half-cut cloth was washed after rub-coating the liquid detergent thereon bv means of coating type container having coat-ing portion (a), (b), (c) or (d).
The de~ree of soiling of washed half-cut cloths ~as determined by a pair comparison with naXed eyes. In the determina-tion, as a reference, the standard soilin~s ~raded ct 10 levels according to the degree of soiling was used.
The de~;ree of cleanin~in case of using the coating type container was indicated by~ scores in comparison ~ith the standard score (100) indicating the degree of cleanin~ obtained without usin,~ the coatin~ t~pe container.

Table l Coating state l Degree o Coating type of Coating Temperature cleaning of container li~uid ~orkabitil~ at coating soiled detergent c1oths ~ __ ____ _ ._ ~ __ ___ ._ __ 100 Coating portion (a) o 36C l06 Coating portion (b) o ~ - x 36C 105 Coating portion (c) ~ /~ 28C l02 Coating portion (d) x o 26C l0l _._ ~ _ _ .. __ _ _ __ _ __ _ _ _.__ _ . .. ._ ._ _ ~
~ote (l): Ihc v,~ e of deglce of cleaning is thc average ~al~e cf seven sheets of c1oth The l~igl1er ~alue means thc }-~;gher c1eanil1g effect.

1 17776~

I`l-e above~ entioneci results cle.~ s11o~ tllat eleaning effeet of the e~ me-colltaining licluid detergent is optimally brought out by usingg the eoating type eon-taineIs havillg eoatino portion (a) and (b), the eoating portion of ~hich is composed of the pOI OUS body, espeeially the coating portion (a), the coating portion of l~hich is conve~ shapecl.

Exannple 2 The en7!Jne-eolltaining liquid detergent ~as applied on soiled part of eloth by means of the eoating-type eontainers and the ele~alling effect \.as me;-lsuJed.
(1) The li(~uid detergent A used as control has the follo~
ing composition.

Sodium sulfate of alkyl(C = 14.3) polyo~yethylene(P = 2.5) 20%

Polyo~plopylelle(l' = 3)polyo.~yetllylene (F' = S) linear deeyl ether 30~0 Trieth.lno]amine 3%
Fluorescent c]ye 0.3O
l-`tll~lol 5~0 l~'ater bala]lce Tlle li(luid deter(ent 13 use(l in this e~alllple is the same as tllat u.ce(l in l.~alllple ].

~ 1 777~5 (') ,~aslling method ~lethod 1 I.iquld detergent ~ t~-pe container ~lethod ' En~yme-containing ___ __~ l~iq~d detergent B _ Use of container ~lethod 3 Liquid detergent A having coating por-tion (a) used in : Example 1 ._ _ _ ._ _ ~lethod 4 Enzyme-containing (Present liquid detergent B ., Invention _ __ _______ _ _ _ __ Soiled cloths are prepared in the same manner as in E~ample 1. In addition, other conditions of coating and ~ashing as ~ell as the method for measuring the temperature at- coating were thc same as those in E~am?~le 1.
(3) Evaluation of degree of cleaning Table 2 sho~s a temperature at coating and a degree of cleaning of soiled natural cloths observed ~hen carrying out each ~ashing method.

I :~777-6~

Tablc 2 - ~ ~ ~ -Degree of I~;ashing in type Temperature cleaning of metl~oddetergentContainer at coating soiled composition natural cloth _._ __ _ . ___ _ __ ___ _____ 1 ~o .~'on-use ~8C100 (standard) ____.___ _ ____ ____ _ _ ~ _ .___ . _ _ _ . __ ~ ~s " 20C 10~
_______ ______.~. _____ _ _ _______ . __ ~ .~o Use 36C 102 4 _.__ _ _ _ _ _ _ _ ___ ~ ~ _ _ (~resent Yes _ ~ 6C 106 ___ ._. _ _ _ __ _ As is clear in Table 2, especially remarkable impro~e-nlent in enzymatic action and cleaning effect are obser~ed in the ~ashillg method l ~]-ere both thc cn-~mc-collt~-linillg liquid-type container arc used.
As mcntioned above, according to aspects of the present in~ention, sufficient frictic,na] heat can be produced in the ruh-coating step ~herein t]-e soile(l palts of clothcs are rul~-c0;3tcd ~ith the cn~yme-colltainillg lie3-lid detergent b~ mealls of the coating-t)pe liquid container, the coating portion of ~hich is composed of Ih~ poro~ls bod~ mdde of s~rlth~lic plas~:ics mater;al. Th~ frict~onal h(at produced m.3kcs iL possible tO speed up t-he erlz~matic reactioll thcl-eb~ clcalling clothes silll3)1) alld effecti-ely.

Claims (8)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A process for cleaning clothes which comprises the step of: rub-coating soiled parts of clothes with an enzyme-containing liquid detergent by means of a coating-type liquid container, the coating portion of which is composed of a porous body made of a synthetic plastics material.

2. A process for cleaning clothes according to claim 1 wherein said enzyme-containing liquid detergent is composed of an enzyme-containing liquid detergent composition containing 10 - 40%
of anionic surfactant, 10 - 40% of nonionic surfactant, 0.05 - 10%
of enzyme and 1 - 10% of solubilizing agent.

3. A process for cleaning clothes according to claims 1 or 2 wherein the enzyme contained in said liquid detergent is one or more enzymes selected from the group consisting of protease, lipase, amylase and cellulase.

4. A process for cleaning clothes according to claim 1 wherein the rub-coating of the clothes with said enzyme-containing liquid detergent is carried out at a rate of 20 - 50 cm/sec under a load of 0.2 - 10 kg/cm2, the amount of the detergent applied on the clothes being 0.1 - 5 g/100 cm .

5. A process for cleaning clothes according to claim 1 wherein the coating face of said porous body is convex shaped.

6. A process for cleaning clothes according to claim 1 wherein the raw synthetic plastics material for said porous body is selected from the group consisting of polypropylene, polyethylene, ethylene-vinylacetate copolymer, acrylonitrile-styrene copolymer and acrylonitrile-butadiene-styrene copolymer.

7. A process for cleaning clothes according to claim 1 wherein said enzyme-containing liquid detergent has a viscosity of 50 - 500 cp.

8. A liquid detergent composition which comprises: 10 - 40%
of anionic surfactant; 10 - 40% of nonionic surfactant; 0.05 - 10%
of enzyme; and 1 - 10% of solubilizing agent; said liquid detergent composition being contained in a coating-type liquid container, the coating portion of which is composed of a porous body made of synthetic plastics material, said liquid detergent being adapted to be rub-coated on soiled parts of clothes by means of said coating portion.