CA2104728A1 - Use of polyvinyl alcohols as a detergent additive - Google Patents
Use of polyvinyl alcohols as a detergent additiveInfo
- Publication number
- CA2104728A1 CA2104728A1 CA002104728A CA2104728A CA2104728A1 CA 2104728 A1 CA2104728 A1 CA 2104728A1 CA 002104728 A CA002104728 A CA 002104728A CA 2104728 A CA2104728 A CA 2104728A CA 2104728 A1 CA2104728 A1 CA 2104728A1
- Authority
- CA
- Canada
- Prior art keywords
- compound
- detergent
- tho
- weight
- mpa
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3753—Polyvinylalcohol; Ethers or esters thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
Abstract Use of polyvinyl alcohols as a detergent additive The present invention relates to the use of polyvinyl alcohols containing the recurring structural unit of the formula I
Description
" 2~0~728 HOECEIST ARTIENGISSE~LSCE~AFT EiOE 92/F 267 Dr. ~l/rh DQscript~ on Uoe of polyvlnyl alcohol~ a~ dot-rg~nt addltlve The laundry wa~hod nowadays $n th- homo and lndu~try compric-s unlform or, ~p-clally ln tho home, mo~tly dlff-r-nt typ-~ of flbor, ln partlcular raturally occurrlng flb-re, chi-fly cotton or wool, r-gon-rat-d c-llulo~- flb-r~, for xampl- vi~co~ ynth-tlc flb-rc, for exampl- poly-stor, polyamide nd polyacrylonltrll-, and mlxtur-~ of ~uch flb-r~ In contra~t to tho ~o-call-d ~white wa~hn, which compri~e~ undyod t xtilos, tho co-call-d ~colorod wa~h~ i~ compo~od of dy-d t-xtil-~, u~ually ln var~ous color ~hades and depth~ of color, from pale or pastel to dar~ It goQ~ wlthout ~aylng that t-xtil-s havlng th- ~t dlv-r~- color-fa~tn-~e~ can be pre~ont ln a wa~h~ng op-ratlon on a dom ~tlc color-d wash If tho dy-ing~ are not ad-guately fa~t to wa~h~ng, dy-~tuff~ or dy-~tuff d-gradation product~ are det-ch-d durlng th- wa~hlng proc-~ nd bl--d off lnto the waah llguor R-ab~orptlon of th-~- dotach-d (bl-d-off) constltuents onto th- other t-xtll-~ wa~h-d at the ~ame tlme results ln ~talning~, a ~hlft ln ~hade and/or the formatlon of ~pot~ du- to tho r-absorbod dye~tuff or dyo~tuff d-grad-tlon product- whlch hav- bl-d off and may bo dlstrlbutod non-unlformly Th- detachmont and/or decompositlon of dye~tuff from an lnad-guat-ly fa~t dyoing 1~ promotod, for xamplo, by hlgh-r tomporatur-s, r-poat-d washing op-ratlons, tho llguor ratlo of wash llguor to laundry, the compo~itlon of the dotorg-nt mployed and the conc-ntratlon th-reof ~n tho wa~h llguor, and tho typo of wa~hlng machln-s and washlng programs used can also have an influonce on the detachment of dyostuff or dy-~tuff degradatlon products from a dy~ing whlch 18 not adeguatoly ~ult~blo for domestic washingn, for xample bocauso of the mochanical ~trese on the laundry during wa~hing and the li~e Other ' .
.
21047~8 rea~ons which may bo mentloned for a drop in fastne-s are al~o the quality of the water u~ed (for examplo duo to the chlorine content), the composition of certain additives for oasy-care handling and the guality and structure of the toxtile matorial or fibero An oxamplo of thio wh$ch may bo m~ntioned ic laundry compris$ng cellulooe fibero, abov- all cotton; thio io usually dy-d with direct dyootuffo, reactive dyeotuffo, ~ulfur dyestuff 8, vat dy-otuffo or naphthol dyootuff 8, mainly with direct dyo~tuff~ or roactive dy-otuff~ Both dyolngo with direct dyestuffo and dyelng~ wlth r-active dyootuffs on cellulose tond to ~bl-ed off~ into the waoh liquoro to a greater or leoser dogroe during r-peatod waohing - and the wash llquors conoequontly contain, for xample, non-lS fixed dyeotuff, hydrolyzed dyeotuff nd/or dy~otuff whichha~ been opl$t off - leadlng to tho problem~ described above The color tran~fer roact$on 1~ often divided into two component stepo - dotachment of the dyostuff particlo~ from tho textil- flber - redepooitlon eloewhere on the laundry Variou~ propooalo have boen do~cribod in the lit-rature tQ prevent thlo reactlon On the one hand, lt i8 pos-ible to destroy the dy otuff by ox$dation whilo ~t i8 preoont $n th- waoh liquor in di~solved form If convontional heavy-duty dot-rgont~ are used, thi~ pr-oent~ no problem, olnce thooe u~ually comprioe a bleaching yatom compooed of porborato and a persalt activator, ouch ao tetraacetylothylonodl~mino, TAED The poracotlc acld formod thorofrom destroyo the di~solved dye~tuffs completely bofore absorptlon onto the fiber io po~sible A disadvantage io, howover, that reactive perborat- aotivatoro can al~o cauoe color damage due to bleaching out o the textile color~
, ~ : . .': ".
, .
-`` 21~7~8 In addition to bloaching activators, nzym c having p-roxida~e propertl-~ aro al~o ~ultable for thoso appllcation~ (CA-A-2 067 748) Anoth-r pos~ibllity for prov-nting oolor tr ~f-r i~
incorporation of polymoric color tran~for inhibitor~ into th- dotergent formulation In thl~ ca~o, th- d tachod dy-~tuff particlo~ aro complexod ~nd etabillz-d by th-polymor ln th- wa~h llguor and r-ab-orptlon onto tho fib-r io thu~ pr-v-nted Homopolym r~ of vlnyll~dazol- nd vlnylpyrrolldon- aro mploy-d a~ pr-f-rr-d inh~bltor~
CA~A-0 094 63S d-~crib-~ det-rg-nt formulatlon~ whlch havo a r-ducod color tran~f-r durlng th- wa~hlng oporation and comprl~o polyvinylpyrrolidone (PVP) D-t-rgent additiv-~ for avolding color tran~for durlng wa~hlng, whlch comprl~- polym ro ba~-d on N-vinylpyrrolldono, N-vinyllmldazole or N-v~nyloxazolidon-ar- known from DE-A-A 38 03 630 DE-A-37 11 299 di~clo~-~ polyvlnylpyrrolldonoc graft-d wlth vlnyl st-r~ ao graylng lnhlbltorc for t-xtllo~
compri~ing ~ynthotlc fibor~
A di~advantag- of th-~- polymoric color transf-r inhibitors i~ thoir ofton low olubillty, o~p-cially ln the ca~o of modlflod polyvlnylpyrrolldone~, whlch mak-~
lncorporatlon lnto llquld d-t-rg-nt formulatlons dlfflcult, and tho lnad-quat- b~od-gradablllty It hao now b--n found that the-- probl-ms can b- b-tt-r ~olvod u~ing the compound- d-fln-d bolow durlng wa~hing or a~ d-t-rgent additiv-~, i - color tran~f-r lnhibltor~
wh$ch can be lncorporated lnto pulvorul-nt and al~o llguid cleanlng agent~ w$thout problem~ and furthormore are al~o biodegradable ar- provided The invention relate~ to the use of polymer~ containing ~` 2lo~728 the recurring ~tructural unit of the formula I
~ CH2 Cll OH
and if appropr~at- other rocurring ~tructural unit~ which aro derived by hydroly~i~/alcoholy~i~ from monomer~ whlch S can bo copolymorlz-d with vinyl acetato, a8 a d-torgont additive for provontion of r-ab~orption of d-tachod dyestuff~ and dyestuff products ~Partly" and/or "compl-t-ly hydrolyzod" polyvinyl alcohols of tho formulae II and III
_--CH CH2 CH--CH2 CH - CH2----~ I H OH O --C --Cll, (II) _--CH CH2--CH CH2 - CH Cl12--_ l l l (III) OH OH o~
are preforably used Polyvinyl alcohols are polymor6 of vlnyl alcohol, which i~ not capablo of exi~t-nce in tha fro~ form, and aro prepared by polymerization of ~t~ble vinyl acQtate and sub~oguent alcoholy~is of the r~ulting polyvinyl acetate The polym~rization is carri-d out in accordance with tho princlple Or froe radical chain poly~rizat~on . ~ . .
: . ~ , .
' 2~04728 in an organic olvont, u~ually mothanol The froe radical~ r-gulred ar- provld-d by lnltlator~ havlng poroxy or azo group~ by d-compo~ltlon in tho r-actlon mlxturo The polyvlnyl ac-tate, d~olvod ln moth nol, le conv-rt-d into polyvinyl alcohol by tran~-~t-rlf$catlon wlth m thanol (alcoholy~l~) Bae-~, ln particular ~od~um hydroxid-, ar- prof-rably u~-d a~ ¢ataly~t~
Th- contont of r-~ldual ac-tyl group~ can b- d~u~t-d by varying th- cataly~t oonc-ntration, r-actlon t mporaturo and r-actlon tlm A dl~tinctlon i~ th-reforo mado b-twoon ¢ompl-t-ly" and partly hydrolyz-d" polyvlnyl alcohols Th- partly hydrolyz-d polyvinyl alcohol~ of tho formula II aro to b- int-rpr-t-d th-orotlcally a~ a copolymer of vlnyl alcohol wlth vlnyl ac-tat-, tho vinyl alcohol content pr-dominating to th- oxt-nt that the ov-rall molocule i~ wat-r-~olublo Tho ac-tyl contont 18 ln g-noral about 11% by wolght, corr-~ponding to a d-gr-o of hydroly~l~ of th- und-rlylng polyvinyl ac-tato of 88 mol% and an ~t-r nu~b-r of about 140 mg of ~O~/g The acotyl contont can al~o b- ignlflcantly hlgh-r~ d-gr--~
of hydroly~l~ up to about 45 to 50 mol% ar- thu~ in u~e ln practlc-Th- r-sldual ac-tyl group~ can b- dl~trlbutod lrrogularly, regularly or ~n accumulation/in block form over a polyvinyl alcohol chaln Th- natur- of tho dlatrlbutlon 18 d-t-rmln-d by the choic- of cataly~t and, lf ~olvent~ are u~-d, by th- natur- th-r-of Th- r-~idual acotyl group- ar- thue dl~trlbutod larg-ly ln tho form of block~ in the ca~o of alkalino alcoholy~i~ and prodom~nantly randomly ln tho ca~e of acid alcoholy~1~
In the case of tho partly hydrolyz-d polyvlnyl alcohols of the formula II, the compounds u~ed preferably havo a residual acetyl content of less than 50% by we$ght, particularly preferably less than 30% by welght ~.
21~4728 The weight-ba~o~ molocular wolght M~ 1~ ln tho r nge from 5000 to 300,000, proferably 20,000 to 200,000, part$cularly preferably 60,000 to 160,000 Tho determination mothods $n oach ca~o roeult in dlfforont numbers, and valu-s aft-r roacetylation of tho polyvinyl alcohol $n pyridine ar- ~tatod hero Tho degro- of polym-rization P~ i8 betwoon 200 and 5000, pr-f-rably 400 to 3000 The vi~co~lty (4~ ~trongth by weight aqu-ou~ ~olutlon at 20C (DIN 530 15)) 1~ ln tho rango botweon 2 and 50 mPa ~, pr-f-rably 10 to 30 mPa o Tho degr-o of hydrolysl~ (d-groo of ~aponlfication) iB
preferably ln tho rango b-tweon 70 and 95 mol%
Completely hydrolyzod polyvlnyl alcohole of the formula III aro to bo und-r~tood as m~aning polyvlnyl alcohols havlng a dogr-e of hydroly~l~ of about 97 to 100 mol%
In th- ca~o of compl-t-ly hydrolyz-d polyvinyl alcohol~, the compounds whlch aro pr-for bly ~mployod havo a re~ldual acetyl contont of 1-~ than 5% by wolght, partlcularly pr-forably 1-~ than 2% by w-lght Tho welght-ba~-d molocular w lght M~ 1~ ln tho rango betw-on 5000 and 300,000, prof-rably 30,000 to 200,000, partlcularly preferably 60,000 to 120,000 The dogreo of polym rlzatlon P~ 1~ b-tw-on 100 and 5000, preferably b-tweon 600 and 3000 The vl~co~lty (4% tr-ngth by w-lght aguoou~ ~olut~on at 20C, DIN 530 15) 1~ u~ually botwoon 0 1 ~nd 100 mPa ~, pr-forably 6 to 30 mPa ~, particularly prof-rably 10 to 50 mPa 8 Tho dogroo of hydrolysls (t-groo of saponiflcatlon) 1B
proferably in the reg$on abovo 98 mol%
The polyvinyl alcohols u~ed accordlng to the invontion are water-~oluble and have a good biod-gradablllty Tho diB8olving characteriBtic8 of a polyvinyl alcohol can be detormined (dissolving curve) by tho amount of product dis~olved at a certaln temperature (for example at 90, 60, 40 and 20C) in a given period of tlme under .
, ~ , . - . .
~: ' :
- . ,. :, .
.:
2~0~728 eomparable apparatue conditlone The relativ- rato of colution ic d-t-rminod by eu~tomary laboratory m thodc The duration of the d$~colv$ng oporatlon varl-~ aeeording to tho vieeocity (R valu-) and d-gree of hydrolyeis Quite g-n-rally, how v-r, lt ean b- ~aid that polyvinyl aleohol~ whieh have a ~olublllty of at l-aet 10% by weight, preferably at l-act 50~ by welght, partleularly prof-rably at l-a~t 90% by woight, at t~mperatur-~ ln the range from 30 to 90C aro ue-d, th- dieeolving tim b-ing not mor- than 45 minut-e It has b-en found that in the eae- of low-viseooity partly hydrolyz~d polyvlnyl aleoholc havlng a v$~eo~1ty ln the rango from 2 to 10 mPa c, approximately 96~ of th polymor has diccolv-d aft-r a p-riod of 30 minut-s How-ver, the eonstitu-ntc whieh hav- not y-t d~colv-d di~olve without r-~idue at approximat-ly 90C
During dl~olving of th- eompl-t-ly hydrat-d polyvinyl aleohol~, it ha~ b-en found that only r-lativ-ly cmall amount~ of polyvlnyl aleohol dlecolv Only wh-n thl~
t mperature ic exe--ded do-c clgnlfleant dl~olving tako plaee, guantitativ-, el-ar ~olutionc whleh ar- fr-- from epoek~ finally b-lng obtaln-d at 90C
Th- rate of ~olutlon of polyvinyl aleohol~ ie aleo very groatly influene-d by the pre~-ne- and the natur- and amount of other produet- of a d-terg-nt In partieular, if perborate/borat- or ionio eompoundc are pro~-nt in a relatively high eone-ntration, th- polyvlnyl aleohole proferr-d h r- wlth a d-gr-- of hydroly-i- of c about 80 mol% prov- to b- partieularly euitable for the intended use Copolym rie polyvlnyl leohol type~ (for examplo internally pla~tieiz-d produetc, ~ueh a~ Mowiol GE 4-86) furth-rmor- li~-wi~- r- found to hav- f-w-r problems/bo ~uitable in thi~ r-~peet The polyvinyl aleohol~ u~ed aecording to the invention can be employod in various way~
When u~ed in detorgont powder~, the polyvinyl alcohol~
~-` 2~0~728 are ueually employ-d ln the form of granul-~, the particle eize boing 200 to 1500 ~m, lt boing poeciblo for the emalloot particle ~iz- to bo 200 ~m Wh-n u~od ln liguid det-rgent~, tho polyvlnyl alcohols are omploy-d in diccol~-d form In thi~ ca-o, the polyv~nyl alcoholc can be added to the l~guid det-rg-nt ac a colutlon, pref-rably an agu-ouc eolution, or they are incorporatod ae a powder whil- dle~olving The partly and completoly hydrolyzed polyvinyl ~lcohole deecrib-d whlch are uoed accord~ng to th lnv-ntlon aro obtalnablo undor tho trad-n ~- Mowiol (Ho-oh~t aG~ DE) In addition to the polyvinyl alcohole d-~crlbod abov-, lt ia aleo poeeiblo, ourprielngly, to ueo polyv$nyl alcohol-~tabillz-d ~ynth-tic r-~in di~poreionc baeed on homo- or copolymeric diop-r-ion~ and, in partlcular, tho redlep-reible powd-re pr-par-d by epray drylng ao the color tranof-r lnhlbltor Such dieporelon~ or dl~p-relblo powd-ra pr-par-d th-rofrom pr-ferably comprle- ho - or oopolymere, pr-f-rably bae-d on vlnyl c-tato or vlnyl ac-tat-/-thyl-ne, vlnyl acetato/-thyl-n-/acryllc acld d-rlvatlv-e and vlnyl acetat-/v-r~atlc acid vlnyl etor The li~uid and eolid product~ roferrod to ueually compriee 3 to 20~ by weight of PVAL, in addltlon to polyvinyl acetat- or copolym re bae-d on vlnyl acotato and the lik- Tho abovomontion-d di~p-r~ione pr~par-d by the known omuleion polym rlzatlon m thod and dlep-relble powdors prepar-d thorofrom co~prl-o polyvinyl alcohol, whlch ie on tho ono hand pro~ont ln aqueou~ ~olutlon a~
a protectivo colloid and on tho oth-r hand hae boon grafted on in tho wator-lneoluble polymor partlcle by tho method of fr-o radical polym rlzatlon The proceeee~ for the preparatlon of euch di~pereibls powdere from the aqu-ou~ ~ynthetic re~in dispsrelone are known and do not need to be explained in more detail The additives described above thus offer the advantage of - . . .
, .. , ' . , ' ..
-` 210~728 - -g boing able to be added to a detergent as a liquid dlspersion or a~ a dry redispor~iblo powder a8 roqu$rod Examplo~ whlch may be mentioned of ~uch homopolymoric polyvinyl aootato disp-rciblo powder~ aro Mowilith powder D and ^Mowilith powdor DM (Hoechst AG, DE) Copolymer~c polyvlnyl acotato disporsible powdors which may be mentioned aro Mowllith powdor DM 117 P and Mowillth powdor DM 200 P
In addition to tho ~normal polyvlnyl ~lcohols~ de~cribod above, ¢opolymeric type~ and hydrolyz-d graftod products can also advantag-ou~ly bo mploy-d 8uch copolymers contaln the recurring ~tructural unit of tho formula I
and other recurring ~tructural unlt~ whlch aro derivod from monomers which can be polym-rlzed wlth vlnyl acetato and dlsplay no adver~e lnfluonco in r-~pect of wator-~olubility and biodogradability ln the copolymor Sultable comonomers are, for oxampl-, a-olefln~, ~uch as othyleno, vlnyl laurate, vlnyl ac-tate, vor~atlc ac~d vlnyl ester and/or (meth)acryllc acld derlvatlv-s, ~u¢h as (meth)acrylic acid ~ter~
The comonomer~ ¢an be mploy-d ~ lndlvldual ~ub~tance~, 80 that copolymer~ whlch contain two dlff-rent r-currlng structural unlt~, preferably the r-currlng ~tructural unit of the formula I and the ~tructural unlt derived from the monomor ethylene, are obtalned Tho ¢omonomer~ can al~o bo employed a~ a mixtur-, ~o that copolymors whlch contaln at l-a~t three dlfforent rocurring ~tructural unit-, ono of whi¢h 1~ the ono of tho formula I, are obtalned A suitable group of ¢ompounds to be u-ed ~¢¢ording to the lnvention aro torpolymer~ ba~ed on polyvlnyl al¢ohol Su¢h terpolymer~ ¢ontaln, ln addltlon to tho re¢urring stru¢tural unit of the formula I, ln partlcular stru¢tural units whl¢h are derlved from the monomer~
ethylene and (meth)a¢rylic ac~d derivativo~
Another advantageou~ property of the polymer~ of the 210~728 formula I, in particular of th- formula- ~I and III, us-d according to th- lnv-ntlon 1~, ln atdltlon to th- water-~olubillty m ntlon-d, tholr hlod gradablllty (Zahn-Wollen te~t, ~-- N-llland-T xtllb-rlchto 59, 487, 582, 659 (1978) and 65, 269, 340 (1984)) Tho polym r~ of the formula I, ln partlcular of tho formulae II and III, de~crlb-d abov- aro uced a8 a d-t-rg-nt addltlv- for pr-v-ntlng roabsorption of d-tach-d dy-stuff~ and dy- product~
Th- d-t-rg-nt~ can b- lther lndu~trlal d-t-rg-nt~ or dom ~tic d-t-rg-nt~ Th-~- includ , ln partlcular, pulverul-nt and liguid h-avy-duty d-t-rg-nt~, pulverul-nt and llquld llght-duty d-t-rg-nt~, machln- dl~hwa~hlng ag-nt booster~, cuch a~ ccourlng ~alts and paato~, and after-tr-atm-nt ag-nt~ for waohlng (fabrlc formero and coft-ner~) Th- most ~-ntlal compon-nt of th- d-t-rg-nt~ ar- th-wa~h-actlv- curfactant~, whlch r- chl-fly (a) anlonlc, nonlonlc and/or zwltt-rlonlc wa~h-act~v-curfactant~
Th- anlonlc wa~h-actlv- ~urfact nt~ ar- chl-fly sulfonat-~, cuch a~ alkylarylculfonat-~, for ex y le dodecylb-nz-neculfonat-, al~yl~ulfonat-~ and alk-nyleulfonat-~, and ulfat-~, for x y l- alkyl sulfates, ~ulfat-~ of thoxylat-d amld-~, st-r~ of a-~ulfo fatty aclds or al-o ~oaps of naturally occurrlng, optlonally modlf~-d or ynth-tlc fatty aclds, tho anlonlc ~urfactants advantag-ou-ly b-lng ln oalt form, for xample as the alkall m tal alt (~odlum or pota~lum), as th- ammonium alt or a- the alt of organic ba~-~, ln partlcular mono-thanolamln-, di-thanolamlno or trlethanolamlne alt- The anlonlc ~urfactants furth-rmoro lnclude ~ulfosucclnates, alkyl ~ther ~ulfates, alkyl th-r carboxylat-s and fatty acid condonsation products ~uch as ars usually u~d in washing and cleaning formulatlons ' :
:. .
2~ 0~28 Possible nonion~c wash active surfactants aro chiefly polyothyleno glycol therc of hlghor alcohols or alkylphonol~, polyethylene glycol e~terc of f~tty acids and polyoxyothylation products of fatty acld u~idos The fatty radical~ or alkyl and allcyl-ne radlcals ln the abov~entioned ~urfactant~ or alcohol~ or fatty acids contain, for oxamplo, 8-20 carbon atoDus aryl 1- ch~-fly phenyl; the polyothylono glycol chaln~ can contaln, for xample, 3-80 ethylenoxy group~ nd c n optlonally con~ict of propylon-oxy unit- q~ypical nonionlc ~urfactant~ ar- allcylpoly-thoxylates, alkylpolyglyco~id-~, glucamid-~, allcylullin--N-oxid-s, alkylpho~phin- oxid-~ and condon~ation productc of fatty alcohol~ wlth ~thylen- oxid- and propyl-n~ oxide Pr-ferr~d compounds (a) among th- anionic eurfactant~ aro tho alkyl benzone ~ulfonat-s, th- alkane sulfonate~, the alkyl culfonato~ and the ~oap~, and pr-f-rr-d compounds (a) among the nonionic curfactant~ ar- the alkyl polyglycol ether~
Examplo~ of zwitt-rionic eurfactant~ ar- d-rivativos of aliphatic quatornary ammoniu~, pho~phonium and ~ulphonium compounds, ~uch as ar- Icnown from US-A-3 925 262 and Depending on the fiold of u-e and int nd-d purpo~e of the detorgent-, tho~e can con-i-t of, for xamplo, tho component~ (a) a- de-crib-d abov- by th~-lv-s (for oxamplo for $ndu-tri-1 purpo---) or al~o comprlce ono or more othor add$tive~ (for xQl- alco for lndu~trlal purpo~es or, in partlcular, for domo-tic d-t-rg-nt~), whore e~entially the following additlvo- may bo mentioned (b) ~equestoring agents (c) ~nzymes (d) bleaching agents - if appropriate together with customary bleaching addltive~, in part$cular (d,) activators and/or (d2) ~tabilizers 210~728 (o) waohing alkalis (f) anti-r-d-poeition agonts S-gu-st-ring agent~ (b) whleh may b- ~ ntion-d aro the customary eompl-xing ~ubstane-~, for oxamplo ~ino S polyaeotat-e (ln partieular nltrllotrlaeetat- or thyl-nodiamln- t-traae-tat-), minopolym-thyl-ne phosphat-s, ~odium tripho~phate, oodium trlpolyphoophat-~, eodium aluminum ~illeatee, oodium oillcat-, magn-olum ollleat-, zeolit- A, polyaerylat-o (for x Iplo ammonium polyaerylatoe), poly-~-hydroxyaorylat-o and ealts of hydroxyearboxylie eld~ (for xampl- oodlum eitrat-, oodlum tartrat- and oodium glu¢onate) Enzym~s (c) which may bo montlonod aro, for xample, ths eustomary proteases, llpao-s and amylao-~
91-aching ag-nt~ (d) whlch may b- m ntionod are tho cuetomary p-roxy eompoundo, for xampl- p-rborat-s, percarbonatoe, perphoephat-e or p-roxld-e, in particular ao alkali m-tal ealte, or, ep-clally in llguid formulatlon~, al~o hydrog-n poroxldo Pooslble ~tab~llzors for tho p-r-compoundo aro, for xamplo, the abov~m ntloned e-gu-~t-rlng ag-nts, and euotomary earboxylle aeids or am~do d-r~vatlvo- may bo m ntioned a~
aetlvators which may be pr~-nt Washing alkali- (-) whieh ean bo uo-d aro tho eu-tomary ba~-~, for oxampl- ~mmonlum or alkali m tal oilieat-e, pho~phatee, earbonat-- or hydroxldee; wh-ro approprlato, tho particular alkaline p-r-eompounde abovo ean al~o act as washing alkali~
Possiblo anti-red-position agent~ (f) which aro optionally pros~nt ar- tho ouetomary substane-~, in partlcular benzotrlazoloe, ethyl-nethiouroa, e~llulo~e othors (for oxamplo earboxymethylcellulose) or polyvinyl-pyrrolidon~
-- 210~7 2~
The detergonts oan optlonally also compri~e furth-r additlv-s, for ox~mpl- defoamers ~or foam ~tablllzers), fragrances, di~infectant~, buff-r ~alt~, compound~ which r-lease actlve chlorine, corrosion inh~bltorc, olvents, ~olub~lizing agent~, tr-atment cubctanc~c or carri-rs, preservative~ and other lectrolytoo (for oxampl- ~odium sulfate) .
The compo~ition~ of th- detergent~ can vary wldely in th-lr amount~, dep-ndlng on th- manufacturer and intended 0 UB--.
The polyvinyl alcohols u-ed according to the invontion can be added lndivldually to the wash l$quors or, lf desired, can b- lncorporat-d lnto the deterg-ntc Washing i8 carried out chl-fly und-r weakly acld to slgnificantly basic conditlon~, adv ntag-ou~ly at p~
values ln tho rang- from 6 to 12, pr-ferably 7 to 10 The additlves accordlng to the lnv-ntlon ar- advantag-ously employ-d ln concentrationc of 0 05 to 10 g/l, pr-ferably 0 5 to 4 g/l of agu-ou- wa~h llguor Th- cont-nt of the~e compound~ in the d-terg-nt formulatlon 1~ advantag-ou~ly ln the range from 0 2 to 10% by w-lght, pref-rably 1 -6% by w-lght In th- trongly al~allne rang-, products havlng a relatlv-ly hlgh ac~tyl content aro pr-ferred wh-re polyvinyl alcohol~ ar- add-d as color transfer inhibitors, b-cauce of their b-tter dl~solvlng propertles (~degree of hydroly-ls~ c 88 mol%) Washing can be carrl-d out under the cu~t~ry condltlons and as intended ln the partlcular washlng program~ of commercially available washlng machlnes, advantageou~ly ln a total washing process ln which all tho constltuents are present in, and are pr-ferably added to, tho llquor The waehing temperature can li~ewise vary in the cu~tomary range~, for xample in the range from 15 to 95C, the tomperatures in the range from 30 to 60C which are customary for a colored wash and are nowaday~
2~0~728 generally cu~tomary b-ing pr-forr-d h-re Any des~red mat-rial~ can be wa~h-d, ~ ~ ~uch as are lntend-d in lndustry and the homs for the particular wa~hing op-ration-, for xample looce fiberc, f~lam nto, thr-adc, opool~, wov-n fabr$c, ~nltt-d f brlc, non-wov-n~, op-n w b~, tubular goodc, velv-t, folt, tuftlng goodo, carpet~, ~tructurod, porou~ materlal~ of plaot~c c~m~lar to fabric (ouch a~ aro uo-d for th~ hom nd clothing) and, ln partloular, e ml-flnieh-d nd finloh-d goodo Th- oubotrat-~ can b- ad- of any de~irod cu~tomary mat-rlalo, for xampl- naturally occurrlng or r-gen-rat-d o-llulooo (for xampl- cotton, lin n, h~mp, vl~co~-), naturally occurrlng polyamide~ (for example wool, cilk) or oynth~tlc mat-rlal~ (for xample polyamid-~, poly-~t-ro, polyacrylonltrlle~, polypropyl-ne or polyur-thano~) and mlxtur-c th-r-of The c-llulo~--contalnlng cubotrate~ are to be ~lngl-d out ln partlcular, nd abov- all color-d laundry whlch contain-dy-d cellulo~- ~ub~trat-~
ao The d-t-rg-nt additiv-~ accordlng to th- lnv-ntlon are ad-guat-ly compatlble wlth th- cu~tomary d-t-rg-nto, for xampl- as li~t-d bov-, and hardly lmpair th-lr wa~hing actlon, but may v-n ao-i~t $t Th-y provont r-ab~orptlon of bled-off dy-stuffo and dy-~tuff d-gradation produot~
onto the wa~h-d material, ln particular onto th- mat-rial wa~h-d at the ame time, urpri-ingly w ll and can be rln~-d out of the wa-h-d mat-rlal nalogouely to the oth~r wa~h liguor compon-nt~ Thoy do not attac~ th-laundry Compar-d w$th th- ~nown polym~ric color tranof-r lnhibitors, th-y ar- dl-tlngul-h-d by a u-ually ~uperlor performanc-, and mor-ov-r hav~ a good biodegradability Becau~e of their wat-r--olublllty, ~pecially in th- caoe of partly hydrolyzed polyvinyl alcohol~, th-y can be incorporated into liguid wa~hing and oleaning formulations without problems . " ' ........... .. . ...... . .. ~. .
- . :
, --, --` 2104728 ~xampl-s Color tranof~r ~nhibitoro lnv~ctigatod __ CompoundViscosity~Degree of _ Residual (mPa-s) hydroly8$s g/mol acetyl (molt) Cbnytwntt)(~
Mowiol 10-7410 ~ 1.573.4 1 1.820,000 20.8 5Mowiol 15-79 15 t 2.081.5 ~ 2.2100,000 15.4 Mowiol 18-9S
I
¦Mowiol 40-8840 ~ 2.087.7 ~ 1.131,00010.8 ~) of a 4% ~tr-ngth by w~lght q uouo colution at 20C
(DIN 53 015) 2) DIN 53 401 Waohing xperim~nto ln a glaco b-ak-r Whil- ~tlrring, 1000 ml of wat-r (15 6 dH) w r- lnltlally introduc~d into a glaoo b-ak-r at 40C and 2 S g of WMP
d-t-rg-nt (Waoch-r-ifor~chung ~r-f-ld) and th-n color tranof~r inhibltor w~r- add-d Aft-r about 5 minut-o, 2 5 g of cotton fabric dy-d wlth Dlamln-Braun ~ (Dlr-ct Brown 235), 2 5 g of whlt~ cotton fabric and 2 5 g of whlt- t-rry tow-lllng w ro add~d Aftor a r-actlon tim- of 30 minut-o, th- orlginally whit- cotton fabric wa~ r~mov-d from th- waoh llquor, rln-~d out with wat-r and drled Th~ wh~t-n-oc wao th-n d-t~rmin~d with an ~lr~pho whlt-n~cc m t-r at 460 m The whit-n-o- of th cotton fabrlc b~for~ the waching proc~so wa~ 85%
.: . . . :: . : . -~, .: , . , : . : . ~ . :
: : : ,: .
--- 210~ 128 Compound Uce concontration Reflectance after wa~hing Mowiol 10-740 060 g/l 53 %
Mowiol 18-950 060 g/l 52 %
Mowiol 40-880 050 g/l 52 %
Mowiol 15-790 060 g/l 51 %
Compari~on (PVP) 0 060 g/l 50 %
No addltivo ___ 46 %
~ __ Waching experlmontc ln a Launder-o-moter The waehing xporlm~nt~ w r- carrl-d out ln a Laundor-o-met-r at 40C The wa~hlng tim- wac 40 mlnut-e The detorgent conc-ntratlon wa~ 4 g/l of WMP te~t d-torgent (Waecherelforcchung ~r-feld) Th- water hardn-~ wa~
16dH
1 25 g of cotton fabrlc dy-d with Dlamln-~raun ~R
(Hoechct AG, DE) togethor wlth 5 g of whlte cotton fabrlc woro waehed ln 400 ml of wach liguor In oach ca~e 1 3~ by w-ight, bar-d on th- t-ct d-t-rg-nt, of the compound u~ed accordlng to tho lnv-ntion wa~ addod to ths wa~h liguor and tho whlt-nocs of tho whlto fabric wa~ detormlned by rofloctanco moa~ur-m nt aft-r the washing proce-~ Polyvinylpyrrolldono (PVP) wa~ ~mployod a~ the comparl~on ~ub~tanc-Compound Refloctanco of tho whlte fabric aftor wachlng Mowlol 40-88 58 0 %
'Mowiol 10-74 57 6 %
Mowlol 18-95 57 4 %
Mowiol LP-GE 5-97 57 1 %
Comparieon PVP 56 1 %
- ,: ~ ' :
.
.
. . . :
21~72~
, No additiv~ 55 2 %
Compound Refloctancc of th~ white fabric aft-r wa~h~ng Mowilith powd~r DS 59 9 %
Mowilith powdQr DN 117 P 59 4 %
Mowillth powd~r DM 200 P 57 8 %
Mowillth powder D 56 8 %
Comparl~on PVP 56 3 %
10 No addltive 55 0 ~
The re~ult lllu~trat~o that th- compound~ claim~d accordlng to th~ lnv-ntlon clgnlfleantly cuppr-ec color tran~fer of the brown dyostuff from th~ dy~d to tho whlte fabric At comparabl~ uc~ conc-ntratlons, tho compound~
accordlng to the inv~ntion ar- eomparabl~, and ln many eace~ ~von ~up~rlor, ln actlvlty to th~ pr-vloue ~tandard polyvlnylpyrrolldon~ (PVP) .
. :....... . , . : ' .
: . ... ~ . .. . : .
.
.. . . . .. .
.
21047~8 rea~ons which may bo mentloned for a drop in fastne-s are al~o the quality of the water u~ed (for examplo duo to the chlorine content), the composition of certain additives for oasy-care handling and the guality and structure of the toxtile matorial or fibero An oxamplo of thio wh$ch may bo m~ntioned ic laundry compris$ng cellulooe fibero, abov- all cotton; thio io usually dy-d with direct dyootuffo, reactive dyeotuffo, ~ulfur dyestuff 8, vat dy-otuffo or naphthol dyootuff 8, mainly with direct dyo~tuff~ or roactive dy-otuff~ Both dyolngo with direct dyestuffo and dyelng~ wlth r-active dyootuffs on cellulose tond to ~bl-ed off~ into the waoh liquoro to a greater or leoser dogroe during r-peatod waohing - and the wash llquors conoequontly contain, for xample, non-lS fixed dyeotuff, hydrolyzed dyeotuff nd/or dy~otuff whichha~ been opl$t off - leadlng to tho problem~ described above The color tran~fer roact$on 1~ often divided into two component stepo - dotachment of the dyostuff particlo~ from tho textil- flber - redepooitlon eloewhere on the laundry Variou~ propooalo have boen do~cribod in the lit-rature tQ prevent thlo reactlon On the one hand, lt i8 pos-ible to destroy the dy otuff by ox$dation whilo ~t i8 preoont $n th- waoh liquor in di~solved form If convontional heavy-duty dot-rgont~ are used, thi~ pr-oent~ no problem, olnce thooe u~ually comprioe a bleaching yatom compooed of porborato and a persalt activator, ouch ao tetraacetylothylonodl~mino, TAED The poracotlc acld formod thorofrom destroyo the di~solved dye~tuffs completely bofore absorptlon onto the fiber io po~sible A disadvantage io, howover, that reactive perborat- aotivatoro can al~o cauoe color damage due to bleaching out o the textile color~
, ~ : . .': ".
, .
-`` 21~7~8 In addition to bloaching activators, nzym c having p-roxida~e propertl-~ aro al~o ~ultable for thoso appllcation~ (CA-A-2 067 748) Anoth-r pos~ibllity for prov-nting oolor tr ~f-r i~
incorporation of polymoric color tran~for inhibitor~ into th- dotergent formulation In thl~ ca~o, th- d tachod dy-~tuff particlo~ aro complexod ~nd etabillz-d by th-polymor ln th- wa~h llguor and r-ab-orptlon onto tho fib-r io thu~ pr-v-nted Homopolym r~ of vlnyll~dazol- nd vlnylpyrrolldon- aro mploy-d a~ pr-f-rr-d inh~bltor~
CA~A-0 094 63S d-~crib-~ det-rg-nt formulatlon~ whlch havo a r-ducod color tran~f-r durlng th- wa~hlng oporation and comprl~o polyvinylpyrrolidone (PVP) D-t-rgent additiv-~ for avolding color tran~for durlng wa~hlng, whlch comprl~- polym ro ba~-d on N-vinylpyrrolldono, N-vinyllmldazole or N-v~nyloxazolidon-ar- known from DE-A-A 38 03 630 DE-A-37 11 299 di~clo~-~ polyvlnylpyrrolldonoc graft-d wlth vlnyl st-r~ ao graylng lnhlbltorc for t-xtllo~
compri~ing ~ynthotlc fibor~
A di~advantag- of th-~- polymoric color transf-r inhibitors i~ thoir ofton low olubillty, o~p-cially ln the ca~o of modlflod polyvlnylpyrrolldone~, whlch mak-~
lncorporatlon lnto llquld d-t-rg-nt formulatlons dlfflcult, and tho lnad-quat- b~od-gradablllty It hao now b--n found that the-- probl-ms can b- b-tt-r ~olvod u~ing the compound- d-fln-d bolow durlng wa~hing or a~ d-t-rgent additiv-~, i - color tran~f-r lnhibltor~
wh$ch can be lncorporated lnto pulvorul-nt and al~o llguid cleanlng agent~ w$thout problem~ and furthormore are al~o biodegradable ar- provided The invention relate~ to the use of polymer~ containing ~` 2lo~728 the recurring ~tructural unit of the formula I
~ CH2 Cll OH
and if appropr~at- other rocurring ~tructural unit~ which aro derived by hydroly~i~/alcoholy~i~ from monomer~ whlch S can bo copolymorlz-d with vinyl acetato, a8 a d-torgont additive for provontion of r-ab~orption of d-tachod dyestuff~ and dyestuff products ~Partly" and/or "compl-t-ly hydrolyzod" polyvinyl alcohols of tho formulae II and III
_--CH CH2 CH--CH2 CH - CH2----~ I H OH O --C --Cll, (II) _--CH CH2--CH CH2 - CH Cl12--_ l l l (III) OH OH o~
are preforably used Polyvinyl alcohols are polymor6 of vlnyl alcohol, which i~ not capablo of exi~t-nce in tha fro~ form, and aro prepared by polymerization of ~t~ble vinyl acQtate and sub~oguent alcoholy~is of the r~ulting polyvinyl acetate The polym~rization is carri-d out in accordance with tho princlple Or froe radical chain poly~rizat~on . ~ . .
: . ~ , .
' 2~04728 in an organic olvont, u~ually mothanol The froe radical~ r-gulred ar- provld-d by lnltlator~ havlng poroxy or azo group~ by d-compo~ltlon in tho r-actlon mlxturo The polyvlnyl ac-tate, d~olvod ln moth nol, le conv-rt-d into polyvinyl alcohol by tran~-~t-rlf$catlon wlth m thanol (alcoholy~l~) Bae-~, ln particular ~od~um hydroxid-, ar- prof-rably u~-d a~ ¢ataly~t~
Th- contont of r-~ldual ac-tyl group~ can b- d~u~t-d by varying th- cataly~t oonc-ntration, r-actlon t mporaturo and r-actlon tlm A dl~tinctlon i~ th-reforo mado b-twoon ¢ompl-t-ly" and partly hydrolyz-d" polyvlnyl alcohols Th- partly hydrolyz-d polyvinyl alcohol~ of tho formula II aro to b- int-rpr-t-d th-orotlcally a~ a copolymer of vlnyl alcohol wlth vlnyl ac-tat-, tho vinyl alcohol content pr-dominating to th- oxt-nt that the ov-rall molocule i~ wat-r-~olublo Tho ac-tyl contont 18 ln g-noral about 11% by wolght, corr-~ponding to a d-gr-o of hydroly~l~ of th- und-rlylng polyvinyl ac-tato of 88 mol% and an ~t-r nu~b-r of about 140 mg of ~O~/g The acotyl contont can al~o b- ignlflcantly hlgh-r~ d-gr--~
of hydroly~l~ up to about 45 to 50 mol% ar- thu~ in u~e ln practlc-Th- r-sldual ac-tyl group~ can b- dl~trlbutod lrrogularly, regularly or ~n accumulation/in block form over a polyvinyl alcohol chaln Th- natur- of tho dlatrlbutlon 18 d-t-rmln-d by the choic- of cataly~t and, lf ~olvent~ are u~-d, by th- natur- th-r-of Th- r-~idual acotyl group- ar- thue dl~trlbutod larg-ly ln tho form of block~ in the ca~o of alkalino alcoholy~i~ and prodom~nantly randomly ln tho ca~e of acid alcoholy~1~
In the case of tho partly hydrolyz-d polyvlnyl alcohols of the formula II, the compounds u~ed preferably havo a residual acetyl content of less than 50% by we$ght, particularly preferably less than 30% by welght ~.
21~4728 The weight-ba~o~ molocular wolght M~ 1~ ln tho r nge from 5000 to 300,000, proferably 20,000 to 200,000, part$cularly preferably 60,000 to 160,000 Tho determination mothods $n oach ca~o roeult in dlfforont numbers, and valu-s aft-r roacetylation of tho polyvinyl alcohol $n pyridine ar- ~tatod hero Tho degro- of polym-rization P~ i8 betwoon 200 and 5000, pr-f-rably 400 to 3000 The vi~co~lty (4~ ~trongth by weight aqu-ou~ ~olutlon at 20C (DIN 530 15)) 1~ ln tho rango botweon 2 and 50 mPa ~, pr-f-rably 10 to 30 mPa o Tho degr-o of hydrolysl~ (d-groo of ~aponlfication) iB
preferably ln tho rango b-tweon 70 and 95 mol%
Completely hydrolyzod polyvlnyl alcohole of the formula III aro to bo und-r~tood as m~aning polyvlnyl alcohols havlng a dogr-e of hydroly~l~ of about 97 to 100 mol%
In th- ca~o of compl-t-ly hydrolyz-d polyvinyl alcohol~, the compounds whlch aro pr-for bly ~mployod havo a re~ldual acetyl contont of 1-~ than 5% by wolght, partlcularly pr-forably 1-~ than 2% by w-lght Tho welght-ba~-d molocular w lght M~ 1~ ln tho rango betw-on 5000 and 300,000, prof-rably 30,000 to 200,000, partlcularly preferably 60,000 to 120,000 The dogreo of polym rlzatlon P~ 1~ b-tw-on 100 and 5000, preferably b-tweon 600 and 3000 The vl~co~lty (4% tr-ngth by w-lght aguoou~ ~olut~on at 20C, DIN 530 15) 1~ u~ually botwoon 0 1 ~nd 100 mPa ~, pr-forably 6 to 30 mPa ~, particularly prof-rably 10 to 50 mPa 8 Tho dogroo of hydrolysls (t-groo of saponiflcatlon) 1B
proferably in the reg$on abovo 98 mol%
The polyvinyl alcohols u~ed accordlng to the invontion are water-~oluble and have a good biod-gradablllty Tho diB8olving characteriBtic8 of a polyvinyl alcohol can be detormined (dissolving curve) by tho amount of product dis~olved at a certaln temperature (for example at 90, 60, 40 and 20C) in a given period of tlme under .
, ~ , . - . .
~: ' :
- . ,. :, .
.:
2~0~728 eomparable apparatue conditlone The relativ- rato of colution ic d-t-rminod by eu~tomary laboratory m thodc The duration of the d$~colv$ng oporatlon varl-~ aeeording to tho vieeocity (R valu-) and d-gree of hydrolyeis Quite g-n-rally, how v-r, lt ean b- ~aid that polyvinyl aleohol~ whieh have a ~olublllty of at l-aet 10% by weight, preferably at l-act 50~ by welght, partleularly prof-rably at l-a~t 90% by woight, at t~mperatur-~ ln the range from 30 to 90C aro ue-d, th- dieeolving tim b-ing not mor- than 45 minut-e It has b-en found that in the eae- of low-viseooity partly hydrolyz~d polyvlnyl aleoholc havlng a v$~eo~1ty ln the rango from 2 to 10 mPa c, approximately 96~ of th polymor has diccolv-d aft-r a p-riod of 30 minut-s How-ver, the eonstitu-ntc whieh hav- not y-t d~colv-d di~olve without r-~idue at approximat-ly 90C
During dl~olving of th- eompl-t-ly hydrat-d polyvinyl aleohol~, it ha~ b-en found that only r-lativ-ly cmall amount~ of polyvlnyl aleohol dlecolv Only wh-n thl~
t mperature ic exe--ded do-c clgnlfleant dl~olving tako plaee, guantitativ-, el-ar ~olutionc whleh ar- fr-- from epoek~ finally b-lng obtaln-d at 90C
Th- rate of ~olutlon of polyvinyl aleohol~ ie aleo very groatly influene-d by the pre~-ne- and the natur- and amount of other produet- of a d-terg-nt In partieular, if perborate/borat- or ionio eompoundc are pro~-nt in a relatively high eone-ntration, th- polyvlnyl aleohole proferr-d h r- wlth a d-gr-- of hydroly-i- of c about 80 mol% prov- to b- partieularly euitable for the intended use Copolym rie polyvlnyl leohol type~ (for examplo internally pla~tieiz-d produetc, ~ueh a~ Mowiol GE 4-86) furth-rmor- li~-wi~- r- found to hav- f-w-r problems/bo ~uitable in thi~ r-~peet The polyvinyl aleohol~ u~ed aecording to the invention can be employod in various way~
When u~ed in detorgont powder~, the polyvinyl alcohol~
~-` 2~0~728 are ueually employ-d ln the form of granul-~, the particle eize boing 200 to 1500 ~m, lt boing poeciblo for the emalloot particle ~iz- to bo 200 ~m Wh-n u~od ln liguid det-rgent~, tho polyvlnyl alcohols are omploy-d in diccol~-d form In thi~ ca-o, the polyv~nyl alcoholc can be added to the l~guid det-rg-nt ac a colutlon, pref-rably an agu-ouc eolution, or they are incorporatod ae a powder whil- dle~olving The partly and completoly hydrolyzed polyvinyl ~lcohole deecrib-d whlch are uoed accord~ng to th lnv-ntlon aro obtalnablo undor tho trad-n ~- Mowiol (Ho-oh~t aG~ DE) In addition to the polyvinyl alcohole d-~crlbod abov-, lt ia aleo poeeiblo, ourprielngly, to ueo polyv$nyl alcohol-~tabillz-d ~ynth-tic r-~in di~poreionc baeed on homo- or copolymeric diop-r-ion~ and, in partlcular, tho redlep-reible powd-re pr-par-d by epray drylng ao the color tranof-r lnhlbltor Such dieporelon~ or dl~p-relblo powd-ra pr-par-d th-rofrom pr-ferably comprle- ho - or oopolymere, pr-f-rably bae-d on vlnyl c-tato or vlnyl ac-tat-/-thyl-ne, vlnyl acetato/-thyl-n-/acryllc acld d-rlvatlv-e and vlnyl acetat-/v-r~atlc acid vlnyl etor The li~uid and eolid product~ roferrod to ueually compriee 3 to 20~ by weight of PVAL, in addltlon to polyvinyl acetat- or copolym re bae-d on vlnyl acotato and the lik- Tho abovomontion-d di~p-r~ione pr~par-d by the known omuleion polym rlzatlon m thod and dlep-relble powdors prepar-d thorofrom co~prl-o polyvinyl alcohol, whlch ie on tho ono hand pro~ont ln aqueou~ ~olutlon a~
a protectivo colloid and on tho oth-r hand hae boon grafted on in tho wator-lneoluble polymor partlcle by tho method of fr-o radical polym rlzatlon The proceeee~ for the preparatlon of euch di~pereibls powdere from the aqu-ou~ ~ynthetic re~in dispsrelone are known and do not need to be explained in more detail The additives described above thus offer the advantage of - . . .
, .. , ' . , ' ..
-` 210~728 - -g boing able to be added to a detergent as a liquid dlspersion or a~ a dry redispor~iblo powder a8 roqu$rod Examplo~ whlch may be mentioned of ~uch homopolymoric polyvinyl aootato disp-rciblo powder~ aro Mowilith powder D and ^Mowilith powdor DM (Hoechst AG, DE) Copolymer~c polyvlnyl acotato disporsible powdors which may be mentioned aro Mowllith powdor DM 117 P and Mowillth powdor DM 200 P
In addition to tho ~normal polyvlnyl ~lcohols~ de~cribod above, ¢opolymeric type~ and hydrolyz-d graftod products can also advantag-ou~ly bo mploy-d 8uch copolymers contaln the recurring ~tructural unit of tho formula I
and other recurring ~tructural unlt~ whlch aro derivod from monomers which can be polym-rlzed wlth vlnyl acetato and dlsplay no adver~e lnfluonco in r-~pect of wator-~olubility and biodogradability ln the copolymor Sultable comonomers are, for oxampl-, a-olefln~, ~uch as othyleno, vlnyl laurate, vlnyl ac-tate, vor~atlc ac~d vlnyl ester and/or (meth)acryllc acld derlvatlv-s, ~u¢h as (meth)acrylic acid ~ter~
The comonomer~ ¢an be mploy-d ~ lndlvldual ~ub~tance~, 80 that copolymer~ whlch contain two dlff-rent r-currlng structural unlt~, preferably the r-currlng ~tructural unit of the formula I and the ~tructural unlt derived from the monomor ethylene, are obtalned Tho ¢omonomer~ can al~o bo employed a~ a mixtur-, ~o that copolymors whlch contaln at l-a~t three dlfforent rocurring ~tructural unit-, ono of whi¢h 1~ the ono of tho formula I, are obtalned A suitable group of ¢ompounds to be u-ed ~¢¢ording to the lnvention aro torpolymer~ ba~ed on polyvlnyl al¢ohol Su¢h terpolymer~ ¢ontaln, ln addltlon to tho re¢urring stru¢tural unit of the formula I, ln partlcular stru¢tural units whl¢h are derlved from the monomer~
ethylene and (meth)a¢rylic ac~d derivativo~
Another advantageou~ property of the polymer~ of the 210~728 formula I, in particular of th- formula- ~I and III, us-d according to th- lnv-ntlon 1~, ln atdltlon to th- water-~olubillty m ntlon-d, tholr hlod gradablllty (Zahn-Wollen te~t, ~-- N-llland-T xtllb-rlchto 59, 487, 582, 659 (1978) and 65, 269, 340 (1984)) Tho polym r~ of the formula I, ln partlcular of tho formulae II and III, de~crlb-d abov- aro uced a8 a d-t-rg-nt addltlv- for pr-v-ntlng roabsorption of d-tach-d dy-stuff~ and dy- product~
Th- d-t-rg-nt~ can b- lther lndu~trlal d-t-rg-nt~ or dom ~tic d-t-rg-nt~ Th-~- includ , ln partlcular, pulverul-nt and liguid h-avy-duty d-t-rg-nt~, pulverul-nt and llquld llght-duty d-t-rg-nt~, machln- dl~hwa~hlng ag-nt booster~, cuch a~ ccourlng ~alts and paato~, and after-tr-atm-nt ag-nt~ for waohlng (fabrlc formero and coft-ner~) Th- most ~-ntlal compon-nt of th- d-t-rg-nt~ ar- th-wa~h-actlv- curfactant~, whlch r- chl-fly (a) anlonlc, nonlonlc and/or zwltt-rlonlc wa~h-act~v-curfactant~
Th- anlonlc wa~h-actlv- ~urfact nt~ ar- chl-fly sulfonat-~, cuch a~ alkylarylculfonat-~, for ex y le dodecylb-nz-neculfonat-, al~yl~ulfonat-~ and alk-nyleulfonat-~, and ulfat-~, for x y l- alkyl sulfates, ~ulfat-~ of thoxylat-d amld-~, st-r~ of a-~ulfo fatty aclds or al-o ~oaps of naturally occurrlng, optlonally modlf~-d or ynth-tlc fatty aclds, tho anlonlc ~urfactants advantag-ou-ly b-lng ln oalt form, for xample as the alkall m tal alt (~odlum or pota~lum), as th- ammonium alt or a- the alt of organic ba~-~, ln partlcular mono-thanolamln-, di-thanolamlno or trlethanolamlne alt- The anlonlc ~urfactants furth-rmoro lnclude ~ulfosucclnates, alkyl ~ther ~ulfates, alkyl th-r carboxylat-s and fatty acid condonsation products ~uch as ars usually u~d in washing and cleaning formulatlons ' :
:. .
2~ 0~28 Possible nonion~c wash active surfactants aro chiefly polyothyleno glycol therc of hlghor alcohols or alkylphonol~, polyethylene glycol e~terc of f~tty acids and polyoxyothylation products of fatty acld u~idos The fatty radical~ or alkyl and allcyl-ne radlcals ln the abov~entioned ~urfactant~ or alcohol~ or fatty acids contain, for oxamplo, 8-20 carbon atoDus aryl 1- ch~-fly phenyl; the polyothylono glycol chaln~ can contaln, for xample, 3-80 ethylenoxy group~ nd c n optlonally con~ict of propylon-oxy unit- q~ypical nonionlc ~urfactant~ ar- allcylpoly-thoxylates, alkylpolyglyco~id-~, glucamid-~, allcylullin--N-oxid-s, alkylpho~phin- oxid-~ and condon~ation productc of fatty alcohol~ wlth ~thylen- oxid- and propyl-n~ oxide Pr-ferr~d compounds (a) among th- anionic eurfactant~ aro tho alkyl benzone ~ulfonat-s, th- alkane sulfonate~, the alkyl culfonato~ and the ~oap~, and pr-f-rr-d compounds (a) among the nonionic curfactant~ ar- the alkyl polyglycol ether~
Examplo~ of zwitt-rionic eurfactant~ ar- d-rivativos of aliphatic quatornary ammoniu~, pho~phonium and ~ulphonium compounds, ~uch as ar- Icnown from US-A-3 925 262 and Depending on the fiold of u-e and int nd-d purpo~e of the detorgent-, tho~e can con-i-t of, for xamplo, tho component~ (a) a- de-crib-d abov- by th~-lv-s (for oxamplo for $ndu-tri-1 purpo---) or al~o comprlce ono or more othor add$tive~ (for xQl- alco for lndu~trlal purpo~es or, in partlcular, for domo-tic d-t-rg-nt~), whore e~entially the following additlvo- may bo mentioned (b) ~equestoring agents (c) ~nzymes (d) bleaching agents - if appropriate together with customary bleaching addltive~, in part$cular (d,) activators and/or (d2) ~tabilizers 210~728 (o) waohing alkalis (f) anti-r-d-poeition agonts S-gu-st-ring agent~ (b) whleh may b- ~ ntion-d aro the customary eompl-xing ~ubstane-~, for oxamplo ~ino S polyaeotat-e (ln partieular nltrllotrlaeetat- or thyl-nodiamln- t-traae-tat-), minopolym-thyl-ne phosphat-s, ~odium tripho~phate, oodium trlpolyphoophat-~, eodium aluminum ~illeatee, oodium oillcat-, magn-olum ollleat-, zeolit- A, polyaerylat-o (for x Iplo ammonium polyaerylatoe), poly-~-hydroxyaorylat-o and ealts of hydroxyearboxylie eld~ (for xampl- oodlum eitrat-, oodlum tartrat- and oodium glu¢onate) Enzym~s (c) which may bo montlonod aro, for xample, ths eustomary proteases, llpao-s and amylao-~
91-aching ag-nt~ (d) whlch may b- m ntionod are tho cuetomary p-roxy eompoundo, for xampl- p-rborat-s, percarbonatoe, perphoephat-e or p-roxld-e, in particular ao alkali m-tal ealte, or, ep-clally in llguid formulatlon~, al~o hydrog-n poroxldo Pooslble ~tab~llzors for tho p-r-compoundo aro, for xamplo, the abov~m ntloned e-gu-~t-rlng ag-nts, and euotomary earboxylle aeids or am~do d-r~vatlvo- may bo m ntioned a~
aetlvators which may be pr~-nt Washing alkali- (-) whieh ean bo uo-d aro tho eu-tomary ba~-~, for oxampl- ~mmonlum or alkali m tal oilieat-e, pho~phatee, earbonat-- or hydroxldee; wh-ro approprlato, tho particular alkaline p-r-eompounde abovo ean al~o act as washing alkali~
Possiblo anti-red-position agent~ (f) which aro optionally pros~nt ar- tho ouetomary substane-~, in partlcular benzotrlazoloe, ethyl-nethiouroa, e~llulo~e othors (for oxamplo earboxymethylcellulose) or polyvinyl-pyrrolidon~
-- 210~7 2~
The detergonts oan optlonally also compri~e furth-r additlv-s, for ox~mpl- defoamers ~or foam ~tablllzers), fragrances, di~infectant~, buff-r ~alt~, compound~ which r-lease actlve chlorine, corrosion inh~bltorc, olvents, ~olub~lizing agent~, tr-atment cubctanc~c or carri-rs, preservative~ and other lectrolytoo (for oxampl- ~odium sulfate) .
The compo~ition~ of th- detergent~ can vary wldely in th-lr amount~, dep-ndlng on th- manufacturer and intended 0 UB--.
The polyvinyl alcohols u-ed according to the invontion can be added lndivldually to the wash l$quors or, lf desired, can b- lncorporat-d lnto the deterg-ntc Washing i8 carried out chl-fly und-r weakly acld to slgnificantly basic conditlon~, adv ntag-ou~ly at p~
values ln tho rang- from 6 to 12, pr-ferably 7 to 10 The additlves accordlng to the lnv-ntlon ar- advantag-ously employ-d ln concentrationc of 0 05 to 10 g/l, pr-ferably 0 5 to 4 g/l of agu-ou- wa~h llguor Th- cont-nt of the~e compound~ in the d-terg-nt formulatlon 1~ advantag-ou~ly ln the range from 0 2 to 10% by w-lght, pref-rably 1 -6% by w-lght In th- trongly al~allne rang-, products havlng a relatlv-ly hlgh ac~tyl content aro pr-ferred wh-re polyvinyl alcohol~ ar- add-d as color transfer inhibitors, b-cauce of their b-tter dl~solvlng propertles (~degree of hydroly-ls~ c 88 mol%) Washing can be carrl-d out under the cu~t~ry condltlons and as intended ln the partlcular washlng program~ of commercially available washlng machlnes, advantageou~ly ln a total washing process ln which all tho constltuents are present in, and are pr-ferably added to, tho llquor The waehing temperature can li~ewise vary in the cu~tomary range~, for xample in the range from 15 to 95C, the tomperatures in the range from 30 to 60C which are customary for a colored wash and are nowaday~
2~0~728 generally cu~tomary b-ing pr-forr-d h-re Any des~red mat-rial~ can be wa~h-d, ~ ~ ~uch as are lntend-d in lndustry and the homs for the particular wa~hing op-ration-, for xample looce fiberc, f~lam nto, thr-adc, opool~, wov-n fabr$c, ~nltt-d f brlc, non-wov-n~, op-n w b~, tubular goodc, velv-t, folt, tuftlng goodo, carpet~, ~tructurod, porou~ materlal~ of plaot~c c~m~lar to fabric (ouch a~ aro uo-d for th~ hom nd clothing) and, ln partloular, e ml-flnieh-d nd finloh-d goodo Th- oubotrat-~ can b- ad- of any de~irod cu~tomary mat-rlalo, for xampl- naturally occurrlng or r-gen-rat-d o-llulooo (for xampl- cotton, lin n, h~mp, vl~co~-), naturally occurrlng polyamide~ (for example wool, cilk) or oynth~tlc mat-rlal~ (for xample polyamid-~, poly-~t-ro, polyacrylonltrlle~, polypropyl-ne or polyur-thano~) and mlxtur-c th-r-of The c-llulo~--contalnlng cubotrate~ are to be ~lngl-d out ln partlcular, nd abov- all color-d laundry whlch contain-dy-d cellulo~- ~ub~trat-~
ao The d-t-rg-nt additiv-~ accordlng to th- lnv-ntlon are ad-guat-ly compatlble wlth th- cu~tomary d-t-rg-nto, for xampl- as li~t-d bov-, and hardly lmpair th-lr wa~hing actlon, but may v-n ao-i~t $t Th-y provont r-ab~orptlon of bled-off dy-stuffo and dy-~tuff d-gradation produot~
onto the wa~h-d material, ln particular onto th- mat-rial wa~h-d at the ame time, urpri-ingly w ll and can be rln~-d out of the wa-h-d mat-rlal nalogouely to the oth~r wa~h liguor compon-nt~ Thoy do not attac~ th-laundry Compar-d w$th th- ~nown polym~ric color tranof-r lnhibitors, th-y ar- dl-tlngul-h-d by a u-ually ~uperlor performanc-, and mor-ov-r hav~ a good biodegradability Becau~e of their wat-r--olublllty, ~pecially in th- caoe of partly hydrolyzed polyvinyl alcohol~, th-y can be incorporated into liguid wa~hing and oleaning formulations without problems . " ' ........... .. . ...... . .. ~. .
- . :
, --, --` 2104728 ~xampl-s Color tranof~r ~nhibitoro lnv~ctigatod __ CompoundViscosity~Degree of _ Residual (mPa-s) hydroly8$s g/mol acetyl (molt) Cbnytwntt)(~
Mowiol 10-7410 ~ 1.573.4 1 1.820,000 20.8 5Mowiol 15-79 15 t 2.081.5 ~ 2.2100,000 15.4 Mowiol 18-9S
I
¦Mowiol 40-8840 ~ 2.087.7 ~ 1.131,00010.8 ~) of a 4% ~tr-ngth by w~lght q uouo colution at 20C
(DIN 53 015) 2) DIN 53 401 Waohing xperim~nto ln a glaco b-ak-r Whil- ~tlrring, 1000 ml of wat-r (15 6 dH) w r- lnltlally introduc~d into a glaoo b-ak-r at 40C and 2 S g of WMP
d-t-rg-nt (Waoch-r-ifor~chung ~r-f-ld) and th-n color tranof~r inhibltor w~r- add-d Aft-r about 5 minut-o, 2 5 g of cotton fabric dy-d wlth Dlamln-Braun ~ (Dlr-ct Brown 235), 2 5 g of whlt~ cotton fabric and 2 5 g of whlt- t-rry tow-lllng w ro add~d Aftor a r-actlon tim- of 30 minut-o, th- orlginally whit- cotton fabric wa~ r~mov-d from th- waoh llquor, rln-~d out with wat-r and drled Th~ wh~t-n-oc wao th-n d-t~rmin~d with an ~lr~pho whlt-n~cc m t-r at 460 m The whit-n-o- of th cotton fabrlc b~for~ the waching proc~so wa~ 85%
.: . . . :: . : . -~, .: , . , : . : . ~ . :
: : : ,: .
--- 210~ 128 Compound Uce concontration Reflectance after wa~hing Mowiol 10-740 060 g/l 53 %
Mowiol 18-950 060 g/l 52 %
Mowiol 40-880 050 g/l 52 %
Mowiol 15-790 060 g/l 51 %
Compari~on (PVP) 0 060 g/l 50 %
No addltivo ___ 46 %
~ __ Waching experlmontc ln a Launder-o-moter The waehing xporlm~nt~ w r- carrl-d out ln a Laundor-o-met-r at 40C The wa~hlng tim- wac 40 mlnut-e The detorgent conc-ntratlon wa~ 4 g/l of WMP te~t d-torgent (Waecherelforcchung ~r-feld) Th- water hardn-~ wa~
16dH
1 25 g of cotton fabrlc dy-d with Dlamln-~raun ~R
(Hoechct AG, DE) togethor wlth 5 g of whlte cotton fabrlc woro waehed ln 400 ml of wach liguor In oach ca~e 1 3~ by w-ight, bar-d on th- t-ct d-t-rg-nt, of the compound u~ed accordlng to tho lnv-ntion wa~ addod to ths wa~h liguor and tho whlt-nocs of tho whlto fabric wa~ detormlned by rofloctanco moa~ur-m nt aft-r the washing proce-~ Polyvinylpyrrolldono (PVP) wa~ ~mployod a~ the comparl~on ~ub~tanc-Compound Refloctanco of tho whlte fabric aftor wachlng Mowlol 40-88 58 0 %
'Mowiol 10-74 57 6 %
Mowlol 18-95 57 4 %
Mowiol LP-GE 5-97 57 1 %
Comparieon PVP 56 1 %
- ,: ~ ' :
.
.
. . . :
21~72~
, No additiv~ 55 2 %
Compound Refloctancc of th~ white fabric aft-r wa~h~ng Mowilith powd~r DS 59 9 %
Mowilith powdQr DN 117 P 59 4 %
Mowillth powd~r DM 200 P 57 8 %
Mowillth powder D 56 8 %
Comparl~on PVP 56 3 %
10 No addltive 55 0 ~
The re~ult lllu~trat~o that th- compound~ claim~d accordlng to th~ lnv-ntlon clgnlfleantly cuppr-ec color tran~fer of the brown dyostuff from th~ dy~d to tho whlte fabric At comparabl~ uc~ conc-ntratlons, tho compound~
accordlng to the inv~ntion ar- eomparabl~, and ln many eace~ ~von ~up~rlor, ln actlvlty to th~ pr-vloue ~tandard polyvlnylpyrrolldon~ (PVP) .
. :....... . , . : ' .
: . ... ~ . .. . : .
.
.. . . . .. .
Claims (21)
1. Use of a polymer containing the recurring structural unit of the formula I
and if appropriate other recurring structural units which are derived from monomers which can be copolymerized with vinyl acetate, as a detergent additive for prevention of reabsorption of detached dyestuffs and dyestuff products.
and if appropriate other recurring structural units which are derived from monomers which can be copolymerized with vinyl acetate, as a detergent additive for prevention of reabsorption of detached dyestuffs and dyestuff products.
2. The use as claimed in claim 1 of a partly hydrolyzed polyvinyl alcohol of the formula II
(II)
(II)
3. The use of a compound as claimed in claim 2, wherein the compound has a residual acetyl content of less than 50% by weight, preferably less than 30% by weight.
4. The use of a compound as claimed in claim 2, wherein the compound has a weight-based molecular weight ?w in the range from 5000 to 300,000, preferably 20,000 to 200,000, particularly preferably 6000 to 160,000.
5. The use of a compound as claimed in claim 2, wherein the compound has a degree of polymerization ?w of between 200 and 5000, preferably 400 to 3000.
6. The use of a compound as claimed in claim 2, wherein the compound has a viscosity in the range between 2 and 50 mPa?s, preferably 10 to 30 mPa?s.
7. The use as claimed in claim 1 of a completely hydrolyzed polyvinyl alcohol of the formula III
(III)
(III)
8.The use of a compound as claimed in claim 7, wherein the compound has a residual acetyl content, measured by reacetylation of the polyvinyl alcohol in pyridine, of less than 5% by weight, preferably less than 2% by weight.
9. The use of a compound as claimed in claim 7, wherein the compound has a weight-based molecular weight ?w in the range between 5000 and 300,000, preferably 30,000 to 200,000, particularly preferably 60,000 to 120,000.
10. The use of a compound as claimed in claim 7, wherein the compound has a degree of polymerization ?w of between 100 and 5000, preferably between 600 and 3000.
11. The use of a compound as claimed in claim 7, wherein the compound has a viscosity in the range between 0.1 and 100 mPa?s, preferably 6 to 30 mPa?s, particularly preferably 10 to 50 mPa?s.
12. The use of a compound as claimed in claim 7, wherein the degree of hydrolysis is above 98 mol%.
13. The use of a compound as claimed in claim 1, wherein the compound contains the recurring structural unit of the formula I and other recurring structural units which are derived from an .alpha.-olefin, preferably ethylene, vinyl laurate, vinyl acetate, versatic acid vinyl ester and/or a (meth)acrylic acid derivative.
14. The use of a compound as claimed in claim 1, wherein the compound is employed as an aqueous solution.
15. The use of a compound as claimed in claim 1, wherein the compound is employed as a dispersible powder, the polyvinyl alcohol acting as a protective colloid.
16. The use as claimed in claim 1 as an additive for a textile detergent, detergent booster and/or after-treatment agent for washing.
17. The use as claimed in claim 16 as an additive to an industrial detergent or domestic detergent.
18. A detergent which comprises a compound as claimed in claim 1.
19. A textile detergent, detergent booster and/or after-treatment agent for washing as claimed in claim 18.
20. A detergent as claimed in claim 19, comprising - an anionic, nonionic and/or zwitterionic surfactant, - a compound as claimed in claim 1.
21. A detergent as claimed in claim 20, additionally comprising one or more of the following components - sequestering agent, - optical brightener, - enzyme, - bleaching agent and if appropriate stabilizer and activator, - washing alkali
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4228118 | 1992-08-25 | ||
| DEP4228118.0 | 1992-08-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2104728A1 true CA2104728A1 (en) | 1994-02-26 |
Family
ID=6466320
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002104728A Abandoned CA2104728A1 (en) | 1992-08-25 | 1993-08-24 | Use of polyvinyl alcohols as a detergent additive |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0584736B1 (en) |
| JP (1) | JPH06158094A (en) |
| AT (1) | ATE175993T1 (en) |
| CA (1) | CA2104728A1 (en) |
| DE (1) | DE59309323D1 (en) |
| ES (1) | ES2127771T3 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5543439A (en) * | 1994-06-02 | 1996-08-06 | International Flavors & Fragrances Inc. | Extruded fragrance-containing polyvinyl alcohol and use thereof |
| US5730760A (en) * | 1995-07-11 | 1998-03-24 | Rohm And Haas Company | Fabric washing composition and method for inhibiting deposition of dye |
| US5843192A (en) * | 1995-07-11 | 1998-12-01 | Rohm And Haas Company | Washing composition and use of polymer to clean and provide soil resistance to an article |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001007551A1 (en) * | 1999-07-26 | 2001-02-01 | Henkel Kommanditgesellschaft Auf Aktien | Use of polyvinyl alcohols as detergent additives capable of removing soiling |
| EP4296342A1 (en) * | 2022-06-22 | 2023-12-27 | The Procter & Gamble Company | Household cleaning composition |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3536530A1 (en) * | 1985-10-12 | 1987-04-23 | Basf Ag | USE OF POLYALKYLENE OXIDES AND VINYL ACETATE GRAFT COPOLYMERISATS AS GRAY INHIBITORS IN THE WASHING AND TREATMENT OF TEXTILE GOODS CONTAINING SYNTHESIS FIBERS |
| DE3803630A1 (en) * | 1988-02-06 | 1989-08-17 | Henkel Kgaa | DETERGENT ADDITIVE |
| DE69129150T2 (en) * | 1991-10-14 | 1998-10-08 | Procter & Gamble | Detergent compositions with additives to prevent dye transfer |
| WO1993022417A1 (en) * | 1992-04-29 | 1993-11-11 | Unilever N.V. | Capsule which comprises a component subject to degradation and a composite polymer |
| WO1993023444A1 (en) * | 1992-05-21 | 1993-11-25 | Unilever Plc | Copolymers and detergent compositions containing them |
| DE69230098T2 (en) * | 1992-06-02 | 2000-05-25 | Procter & Gamble | Bleaching composition for laundry |
-
1993
- 1993-08-20 AT AT93113341T patent/ATE175993T1/en not_active IP Right Cessation
- 1993-08-20 DE DE59309323T patent/DE59309323D1/en not_active Revoked
- 1993-08-20 EP EP93113341A patent/EP0584736B1/en not_active Revoked
- 1993-08-20 ES ES93113341T patent/ES2127771T3/en not_active Expired - Lifetime
- 1993-08-23 JP JP5207991A patent/JPH06158094A/en not_active Withdrawn
- 1993-08-24 CA CA002104728A patent/CA2104728A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5543439A (en) * | 1994-06-02 | 1996-08-06 | International Flavors & Fragrances Inc. | Extruded fragrance-containing polyvinyl alcohol and use thereof |
| US5730760A (en) * | 1995-07-11 | 1998-03-24 | Rohm And Haas Company | Fabric washing composition and method for inhibiting deposition of dye |
| US5843192A (en) * | 1995-07-11 | 1998-12-01 | Rohm And Haas Company | Washing composition and use of polymer to clean and provide soil resistance to an article |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0584736A1 (en) | 1994-03-02 |
| ATE175993T1 (en) | 1999-02-15 |
| EP0584736B1 (en) | 1999-01-20 |
| JPH06158094A (en) | 1994-06-07 |
| DE59309323D1 (en) | 1999-03-04 |
| ES2127771T3 (en) | 1999-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1309924C (en) | Films from pva modified with nonhydrolyzable anionic comonomers | |
| US4747976A (en) | PVA films with nonhydrolyzable anionic comonomers for packaging detergents | |
| US5650473A (en) | Methods for making styrene copolymers and uses thereof | |
| US4444561A (en) | Copolymers which contain basic groups and are used as antiredeposition agents in washing and after-treating textile goods containing synthetic fibers | |
| US5542951A (en) | Use of copolymers based on vinyl monomers and carboxylic acid amides as a detergent additive | |
| CA2443113A1 (en) | Cleaning product comprising three distinct zones | |
| CN100376634C (en) | Cassade polymer composition with trigger response | |
| JP4050202B2 (en) | Trigger response composition | |
| CN113980749B (en) | Liquid detergent composition | |
| GB2358191A (en) | Film packaged liquid detergent | |
| JP2004002672A (en) | Trigger-responsive composition | |
| CA2104728A1 (en) | Use of polyvinyl alcohols as a detergent additive | |
| CN110343580A (en) | A kind of unit dose detergent product of high-moisture | |
| CA2251380A1 (en) | Ph-sensitive modified cellulose ester | |
| JP4154310B2 (en) | Tablet coating | |
| JP2586962B2 (en) | Methods and products for improving the anti-stain redeposition properties of detergents | |
| JP2003523479A5 (en) | ||
| CA3013938A1 (en) | Use of the combination of a cationic polysaccharide polymer and an anionic non-soap surfactant | |
| US8193142B2 (en) | Composition | |
| EP2550348A1 (en) | Composition | |
| CA2739873A1 (en) | Composition | |
| JP2908600B2 (en) | Bleach composition | |
| WO2024110248A1 (en) | Aqueous polymer dispersions suitable as opacifiers in liquid formulations, process to produce, and their use | |
| JPS6128596A (en) | Laundry aid composition | |
| WO2000055290A1 (en) | Laundry prespotter |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |