CA2024600A1 - High molecular weight acrylic anti-stain treatment for nylon carpet - Google Patents
High molecular weight acrylic anti-stain treatment for nylon carpetInfo
- Publication number
- CA2024600A1 CA2024600A1 CA002024600A CA2024600A CA2024600A1 CA 2024600 A1 CA2024600 A1 CA 2024600A1 CA 002024600 A CA002024600 A CA 002024600A CA 2024600 A CA2024600 A CA 2024600A CA 2024600 A1 CA2024600 A1 CA 2024600A1
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- CA
- Canada
- Prior art keywords
- fiber
- nylon
- weight
- copolymer
- molecular weight
- 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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/56—Condensation products or precondensation products prepared with aldehydes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Detergent Compositions (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Cosmetics (AREA)
Abstract
ABSTRACT
Described is a method for treating fiber with a durable anti-stain agent containing a copolymer of 1-20 weight % acrylic acid and about 80-99 weight % methacrylic acid, that has a weight average molecular weight greater than 80,000, preferably above 1000,000, more preferably above 130,000, and a fiber impregnated with such an anti-stain agent. The anti-stain agent can be used in treating carpets made of nylon 6 and nylon 66 fiber and effectively withstand carper shampooing.
Described is a method for treating fiber with a durable anti-stain agent containing a copolymer of 1-20 weight % acrylic acid and about 80-99 weight % methacrylic acid, that has a weight average molecular weight greater than 80,000, preferably above 1000,000, more preferably above 130,000, and a fiber impregnated with such an anti-stain agent. The anti-stain agent can be used in treating carpets made of nylon 6 and nylon 66 fiber and effectively withstand carper shampooing.
Description
~2~
. HI~ MOLECULAR ~E~R~
ACRYLIC ANT~-ST~ REATMENT
FOR NYLON CARPE~
__ ... ..... _ The ~r~sent invention relates ta an improve~ s~ain-re~ stant composition for treatlng carpet. Specifically, thQ invention . relates to high m~l~cul~r wet~ht ~eirylio materialx ~hleh are relatively durable and resist~nt ~ ~hampooill~. In particular, th~
. 5 in~ention relat~ to A ~tain^re.si.stant carpet treatm~nt for carpets made o~' nylon or amide fibers.
~ylon carpetln~ m~ke~ up a lar~e per¢ent~e of the carpet . lndustry. Nylon 6h fib~r and nylon ~ iber are u.sed in carpet~.
. Nylon 66 .is more crystalllne than nylon 6, thus limiting th~ depth of ~hade developed durin~ dy~ln~ of nylon 66 a~ ~ell ~s beneflcially llmitlng its staining. Conver~ely, with nylon 6 an Advanta~eous depth of shadc 1~ possible; h~wever, nylon 6 suf~erg from the drawba~k that known stain-ro~i~tant tr4atmont~ ar~
ef~ctlvc on the fl~er~.
Known 3tain-re~ nt tre~tm~t~ for oarpet~ ~on~alning nylon flber inolude sulfonated naphthol/phenol ormaldehyde condensates and dihydroxy diphenyl sulfones. However, in treating fibar~ Inade . of nylon 6, relatively hi~h level~ of ~n~wn stain-resi.stance material ar~ req~ired. ~hi~ impart~ a stiffer han~ to the flber and, despite the increased level, the material~ ar~ mor~e easily removed durlng shampoolng of the carpet.
Furthermore, the known naphth~l~p~enol conden~ate~ and sulfone compounds, which a~t ag clqa~ dyes, have sig~flcant disadvantages.
202~0a 80th material~ alter the color of the treat~ carpo~ ya~n, espeoially ~n nylon 6 where higher levels are reguired.
Addltlonally, the kno~n materials yellow signifiGantly ~hen ex~o~d to ultraviolet ( W ) light, an~ are of questionable e~oloyical s~fety.
A ~tain-resi~tant treatment u~ing a ~lend o~ a methacrylic acld oligomer with a g~aft copolymer of me~ha~rylic aoid flnd . sulfonated castor oil has been found to have an adv~ntage over the . phenolias and ~ulfones in color stabili~y.
An ob~ect of the present invention is to develop an effecti~e, durable stain resistant treatment for fiber, part1cula~ly nylon fib~r.
A fur~her ob~ect of thl~ lnvention is to pro~ide ~n improved stain-resist~nt material for nylon ~arpet whlch conforms with . 15 current carpet m~nufacturin~ processe~.
. According to th~ p~esent ~nvention th~r~ provlded an ~nti-~tain ~gent for nylon c~r~et, and ~n improved method or tr~in~
nylon flber wlth an anti-st8~n a~ent, wh~r~in -the ay~n~ comprises water-solu~le copolymer ~ from ~b~lt l to about 20 wei~ht . 20 percent ac~ylic a~i~ and about 80 to abou~ 9~ ~eight p~rcent meth~rylic a~id, and pre~erably from ~bout 5-15 wei~ht ~ a~rylic acid and about 8S-9S weight ~ rne~hacrylic a~id, th~t has ~ wei~ht average mole~ular weight ~MW) between about ~0,004 and 350,000, prefeI~ably be~ween about lûO, 000 and 750r 000~ more ~eferably bstw~en ~bout 130, 000 and Z00, 000, as determlned by aqueous gel permeatlon chromatography ~PC~. The upper limitation on ~he wel~h~ average molecular weight o~ the copolymer wh~ch ~unction~
.
. HI~ MOLECULAR ~E~R~
ACRYLIC ANT~-ST~ REATMENT
FOR NYLON CARPE~
__ ... ..... _ The ~r~sent invention relates ta an improve~ s~ain-re~ stant composition for treatlng carpet. Specifically, thQ invention . relates to high m~l~cul~r wet~ht ~eirylio materialx ~hleh are relatively durable and resist~nt ~ ~hampooill~. In particular, th~
. 5 in~ention relat~ to A ~tain^re.si.stant carpet treatm~nt for carpets made o~' nylon or amide fibers.
~ylon carpetln~ m~ke~ up a lar~e per¢ent~e of the carpet . lndustry. Nylon 6h fib~r and nylon ~ iber are u.sed in carpet~.
. Nylon 66 .is more crystalllne than nylon 6, thus limiting th~ depth of ~hade developed durin~ dy~ln~ of nylon 66 a~ ~ell ~s beneflcially llmitlng its staining. Conver~ely, with nylon 6 an Advanta~eous depth of shadc 1~ possible; h~wever, nylon 6 suf~erg from the drawba~k that known stain-ro~i~tant tr4atmont~ ar~
ef~ctlvc on the fl~er~.
Known 3tain-re~ nt tre~tm~t~ for oarpet~ ~on~alning nylon flber inolude sulfonated naphthol/phenol ormaldehyde condensates and dihydroxy diphenyl sulfones. However, in treating fibar~ Inade . of nylon 6, relatively hi~h level~ of ~n~wn stain-resi.stance material ar~ req~ired. ~hi~ impart~ a stiffer han~ to the flber and, despite the increased level, the material~ ar~ mor~e easily removed durlng shampoolng of the carpet.
Furthermore, the known naphth~l~p~enol conden~ate~ and sulfone compounds, which a~t ag clqa~ dyes, have sig~flcant disadvantages.
202~0a 80th material~ alter the color of the treat~ carpo~ ya~n, espeoially ~n nylon 6 where higher levels are reguired.
Addltlonally, the kno~n materials yellow signifiGantly ~hen ex~o~d to ultraviolet ( W ) light, an~ are of questionable e~oloyical s~fety.
A ~tain-resi~tant treatment u~ing a ~lend o~ a methacrylic acld oligomer with a g~aft copolymer of me~ha~rylic aoid flnd . sulfonated castor oil has been found to have an adv~ntage over the . phenolias and ~ulfones in color stabili~y.
An ob~ect of the present invention is to develop an effecti~e, durable stain resistant treatment for fiber, part1cula~ly nylon fib~r.
A fur~her ob~ect of thl~ lnvention is to pro~ide ~n improved stain-resist~nt material for nylon ~arpet whlch conforms with . 15 current carpet m~nufacturin~ processe~.
. According to th~ p~esent ~nvention th~r~ provlded an ~nti-~tain ~gent for nylon c~r~et, and ~n improved method or tr~in~
nylon flber wlth an anti-st8~n a~ent, wh~r~in -the ay~n~ comprises water-solu~le copolymer ~ from ~b~lt l to about 20 wei~ht . 20 percent ac~ylic a~i~ and about 80 to abou~ 9~ ~eight p~rcent meth~rylic a~id, and pre~erably from ~bout 5-15 wei~ht ~ a~rylic acid and about 8S-9S weight ~ rne~hacrylic a~id, th~t has ~ wei~ht average mole~ular weight ~MW) between about ~0,004 and 350,000, prefeI~ably be~ween about lûO, 000 and 750r 000~ more ~eferably bstw~en ~bout 130, 000 and Z00, 000, as determlned by aqueous gel permeatlon chromatography ~PC~. The upper limitation on ~he wel~h~ average molecular weight o~ the copolymer wh~ch ~unction~
.
2~2~6~
in the practlce of the present inves~ti~n is det~rmlned by ~h~ wate~
~olubility, ~i~cosity and practic~l process-of-manuf~cture req~irement~.
The pre~ent inventLon al~o provide~ a f~ber impre~nate~ with the ~nti-stain agen~. Op~ion~lly, the antl-~tain Age~t of t~q present inventlon can be combined with an adJ~Ivant~, such as a surfactan~, novola~ re~in, ultravi~let-light absor~er, or~anic or ino~ganiC a~id, antioxldant, eth~xylated or ~ul.~onated fatty acid, . polymer coating, Gr a mixtur~ thereo~.
. 10 The antl-stain agent of the present lnven~ion is u~eful ln treatin~ fiber materials, e.~ ibers made from nylon and/or amide flber, particularly carpet~, to make the~ staln re~istant.
Preferably, the flber used in accordanc0 with th~ pr~n~ invention is made from nylon 6, wh~ch is a polymer of oaprolactam, or nylon . 15 ~6, which is a condensation prod~ct of adlpic aci~ and . hexamethylenedi~min~, which ~re well known in the m~n~factur~ of carpe~s such a~ dis~lo~ed in U~S. I'~s~t No~ ~,501,5~1 and . 4,780,4g9, the di~closure~ ef whieh àre incorporated her~in by reference. Other usef~l nylon ~lbor~ lnclud0 tho~ made from, e.~., nylon 11, ~hich is a polymer of ll-amlno undec~nolc acid, nylon 610, which is a polycond~nsation product of ~ebaoic acld and . hex~methylenediamine, and a copolym~r Gf nylon ~nylon 66, all of whlch are well known as disclosed in th~ aforesaid U.S. Patent No.
4,501,5~1~
Pref~rably, flber ls treAted ln accordance w$th the pr~sent invantion by lmmor~ion in an acidio aquaouR bath having a pH
. . 3 202~
between about 1.5 and 5.5, preferably between aho~t ~.1 and 4 . O, more prefarably between about 2. 5 and 3. 5, oontalnin~ th~ ~nti-staln agent, which i~ ~aintalned at a preferable temper~tl.lre between a~out 38 and 110~, more preferably between about 80 and 100C. ~o obtain the best anti-~tain effect, imm~r~lon time v~ies between abo~t 1 and 20 ~inute~, more preferably between about 5 and 15 mlnutes, most preferably between about 7 and 12 mln~tes. The amount of anti-st~in agent u~ed in th~ hath veries be~ween about . 0~ and 10 weight % of the nylon fi~e~ t~ he treated, pref~rably between about 1.0 and 4~0 weight ~, more preferahly between abou~
1.2 and 3.0 weight ~. Acidit~ of the aqu~ s bath in combination with eleva~ed temperature i~ mal~tatned to ~ss~re optimum abso~ption by the nylon fl~er. ~eidQ us~ful t.n maintainin~ the proper pH include both or~anic and lnorganiG acids, e.g., ac~tic a~id, sulfamlc a~id, citrlc acid, nitrlç ac~d, formic acld ~nd phosphori4 ~cid, which are add~d i.n sufficient amount to maintain . the pH in th0 preferr~d r~n~e. A su~factant i~ ~r~ferAbly ~dd~d to the bath to as~i~t ln w~ttin~ the nyl~n fiber at an amount between about 0.~ ~nd 1.5 wei~ht ~ of the nylon fiber to be t~eated. Useful ~urfa~tants in~.lude non-lonlc ~nd anionlc surfa~tan~s, e.~., so~l.um sulfosucclnate, dlootyl and dlnonyl sulfosuccinates, nonyl phenol ethoxalates, linear-alkyl sulfonates and ~odecylbenzene sulfoni~ aGids. O~her preferable additives, which ~ay be lntroduced into th~ bath a~ betw~en ~bo~t ~ and 3 weight ~ o~ the nylon f~ber to be treated, include anionic-acid dye levelers, novol~ res~ns, such as sulPonated naphthol~ph~nol ~ ' 2~2~
formaldehydc condensate~ an~ dihy~rox~1r~iphenyl ~,lfone~;
ultraviolet~ h~ a~sorb~r~, e~, ben~phen.on~, sllch a.s 2-. hydroxy-4-methoxybenzophenono-5-sulfonic a~d, disodlum-~,2'-dihydroxy-4,4'-~i~et~oxy-5,5'-dis~lfobenzophenone, 2,2',4,~'-tetrahydroxy4anzophenone, ~,4-dlh~droxyber;z~ph~none, ~-hydro~y-4-methoxybenzophenone, and 2,2'-~ih~droxy-4,4' dim~thoxy~enzoph~none~
~ntioxidants, such as sodiu~ ~hiocyanate, ethoxylat~d or ~ulfonat~d fatty a~id3, e.g., coconut Dil, tall o1l, casto~ oil, so~ean oi and peanut oil; and polymerio coatin~ compounds, polyvinylchlorlde,, polyviny~3cetate, pol~vinylalc~hol, acryllc.~, styrenes, and flusrochemic~l compound~ s~ch as ~rlfluo~oethan~.
A typical ca~pet proces~ preferably ~nvolves first dyein~ the carpet ~o a de~ired color, then saturating the carpe~ in the bath ~ontainin~ the antl-stain a~ent. ~ein~, howev~r, çan be perfor~ed after, or s.imultaneousl~ with, the stain~re~i~tant treat~ent. In tr~tin~ c.arpets in accordanc~ wlth the ~r~sent inv~ntlQr commerclally a~ilable d~eln~ uni.~, ~J~1a,h ~ vF~ hl~ t'~o111 thb Oting Company er Ku~te.r ~or~o~ ti.on, is advant~eo1l~ly used. ~uch unlts and their op~rati~n are we~l k1lown as dlsclos~d ln the .0 afor~id U~5. Pa~ent No~ 4,50l,59l, A pre~erred proces~ln~ sy~tem for treatin~ carpet is de~cribed. Th~ c~rpet i~ f~rst wetted, f~r ex~ple with a soiutlo~
containîn~ ~y weiyh-~ 0.~ Triton~ GR-5M ~Rehm ~ Haas) and O.l ~ ~EA
. ~Triethanolamlne~. Aft~r nax~ pas~1A~ thr~ugh nip rollæ, th~
. ~5 carpet then i~ spray-dy~d, ste~med ~nd rinsed. ~he ~tain-resist trea-tment is ~pplied in the n~xt stage, a~ ccnditlo~s o~ ~bout 160 180~F/4 sec. using a ~uster unit. The carpet i s there~fter ste~me~
a~ , e , ~ ., 2~5F~'12û sec . ~nd linsed Final ly , ths carp~ is passed throu~h a ~;pray f luorocarbo~l ~re~ment .
In tre~ting flber in ~ccurdanee with th~ pr~3~;Qn~ ;nvention -~he 5 fiber is ~mpragn~tes~ with a ~iufflcient alrlount ~f the ar~ti-~3tain a~ent to imp~t stain res~tan~e -to the fiber~ Preferah~y, the amoun~ of anti-~ain ~gent impregnatl d in~ he flber varl~s between ~bout O . ~ and ~0 . O weight ~ of the nylon f ib~r, m~r~
pr~erabl~ between abou~ O.Z and ~..O wel~ht ~i, mos~ pref~r~
between AboUt O . 3 ~Ind 0. 7S wei~ht. % .
Fiber treated in aceo~dan~3 wttl- -,he present inv~r~tion exhibits stain l~esistanc:e to a variety of ~ ri el 5, .~:u~.h as foods and beverages. M~ny such materi~l~ cont~in dye~, ~aleh ;3~ Foo~, ~ru~a and Cosmetic (FD&C) ~ed ~ye 40, th.~t coml~onl~ conle into contact with carpet~3 when such p~oduct~ ar~ .~eei dentally ~pilled on the carpet. Howeve~, such dyes are eE~sily ren)o~JP.~ f~om flt~er carpets treated in ~ccordarlce with th~ ~resent ' ;~ t i.c)~l by l,;.Lmp.1.~n rinsin~ with w~ter or usln~ ~n ~ eOu~ solut~ of a r~ fl, anion:iG, carp~t shampoo. Rinse-wat~r temper~tures ar.e preferabl.y rnainl~ained at about 15-fi54C, mor~ prefer~b:Ly at ,~bout ?.~5-38C.
To more clearly c~escrib0 the presen~ ir~vent.ion, the ~oll.-~winy non~ itlng e~c~mplss ~re provi~ed. In th~ eic~mple~, all part.~ an~l percentass~ are by wei~ht ~nl.~s~ lnd~ted oth~3rwi.se. Ir~ the examples, MW denete~ weight a-~ray~ molecu~ar w~ht determined by ~5 aqueous ~:PC, Mn denote~3 number av~ra~3 r~lolecular weLght, ~nd ~W/Mn d~3not~ the molecular w~ 3ht d~tribu~lon~
202~a Anti-stain agent3 a~c~rdin~ to tha pr~sent 1~vention w~r~
prepared as foll~ws:
~ w~ tho~sand grams o~ DI (deloni2ed) w~ter and 9~ of Q.2% .iro~
sul~ate were ~dded to 3 5-liter 4-necke~ flAsk fitt~d ~ith a $~ir~er, condense~ and nltro~en inle~. ~hls solution wa~ hea~d ~nde~ a nitrogen a~mosphere to ~0 degree~ C.
A solution of 1~.3g o SMBS ~odium ~etabisulfit~) in 22.a8g of DI water was prepared. 17.5~g (50 weisht ~) of thi.~ solution . lO waS th~n added to the flask (l~ SM~ ased on tot~l monomer). To the flask were yradually and ~3eparate.y add~.d the ~ollowi;~ d~
oJer 1.5 hours: 70g of AA ~acr~rllc ~ci~) ~nd $30g of MA.A
~methacryl1~ ~cid); O.~g ~odium pers1llfate 1~ 7~ DI w~ter, and th~
remainder o~ the SMBS/DI water solutio~ SMBS on total m~nomer~, 15 whilet malnt~ininsJ the ~emperature o~ the flask contel~t~ a~ 70 . degree~ C. The polymoriz~d raaction was continu~d for lS minut~.~
after all the above feed~ were compl.et~ At ~h~ ime w~.~ adc~d 18g of 30~ ~12~ Flftoen min~te.S l~tQr, 1.379g of Dl water w~
added. The ~lask was then allowefl to cool to room temperatura~
~he copolymer so ~orm~d (S~mp.l~ l) had a MW o~ 197,000, Mn of 29,700 a~d MW/Mn of 6.~l~
The ~W o~ the ~opolymer sample~ wa~ varie~ by repeating the ~bove process and va~ying the amo~l~t ~f $MBS ~nd ~he ratio betwe~r the initial chargo ~t~ the fla~k/kettle~ an~ the amou~t lrem~ind~r) 2S used as co-feed. A copolymer (Sample ~) with MW-~01,000, ~n=~7,300 and ~W/Mn=7.33 wa~ obtsined usln~ OL5~ SMBS ~n to~al monomQr ln the kettle (in fl~sk initially) with 1~5~ SMBS on t~tal ~o~omer a~ co-2 ~ 6 ~ ~3 f~ed. At 0. 6~ kettle SMBS an~ 1. 22% ca-f~3d .~MF~S or~ t~.~t~l mollomer, a copolymer (Sa~ e 3) with MW=~17,000, Mn=29, 000 and MWj~n-~9,000 resu1ted; at U.75~s kf~ttl~ S~S r~nd ~. ~5 co-fed SM~3~ on tot~l monomer, a copo1ymer ( Sample 4 ) with MW-94, ~300, Mn-~.4, ~00 and 5 MWf!Mn-3 . ~5 wa3 ob~ined: an~ at 0 . 33% kettle S~I~$ and 0 . 33g6 kett~.e SMBS on total monomer, ~ copo'ylner lSamp1e 5~ wi-tn MW-~.31,000, Mn-47, 100 and MW/Mn-4. 9 ~.~ produc~
E AMPLE
Arlti~stain ~ nt~ according to the pr~3~ent :iLnvention were ~sl.so proAIl¢ed by the f~ owing proce~s:
TO a S-1iter 4-neCked 1EISk was added 3000~ nI w~ter, which was heate~ to 85 degree~ ~ unAer N2. Nine ~r~qm~ of sodi~lm per~ulfcite ( 1. 5 weiclht % based on to~al manomer ~ in :~0~ DI water was then added. After two r~linutes, a mi~ture of 6(~g i~A anc~ 5~0q MAA Wci~ fed ove~ a pe~io~i of or~e hour to the fIac;k, main~ainin~ e t~r~or~ture ~t 85 de~reer; C, ~ter whi~h :lO35-~ ofi DI wEit~3r was added. l`he Ela~k wa~ al:lowed t:o c r.~o~ n room t~3mper.ltur~ r~ MW
o the resu~tinS~ copolyn~ ampl~ ~) w~.r.~ 84,000, the Mr~ was 26,300 an~l MW~Mn was 3.1.
Ad~litlon21 c~po1ymer~ WeI'e'. al;sv pre~a:rr d by this rnf3tho~ y varying the amount of sodi~nl pe~rsulfate~ ~t lr~ ~odillln p~rsul ~te based on tot~l mon~m~r, a ~o~olyrn~r (Samp1a 7) resulted havin~
MW-124, 00(~, Mn-3~, 400 and MW/Mn 3 .
2~2~
EXAMPLE ~
. As in Exar~ple 1, A co-f~ed of monomer and cat~lys~ wa used, . The catalyst solution a~ded initlally to the heated reacto~
flask wa~ l~Sg sodium per~ulfate ~n 30~ DI water (0.~5 we~gh~ ~ on total monomor).
The co-feed wa~ 4. 5g NaaS~08 ln lOOg DI water plus 60~ AA and 154û~ MhA. The co-eeds were ~dde~ separ~tely o~r~ar ene hour. Th3 temperature was ~eld at 9~ de~ree~ C for thirty minute~, and then gg o~ 0.1~% iron sul~ate solution and 0.8g of t-butylh~droperexid~
10 in 5g of D~ w~ter were add~d . Then, 1. 2g o i~o--ascorbic acid ( IA ) : in 25g ~I w~ter w~ addsd. T~n minut~ later, a second identis~l amount of IA~DI water was adde~. ~lext, 1035~ DI water was ad~ed and the reaetion flask was then allowed to ccol to room temp~rature . The resultin~ copolylner ( Sample 3 ) had a MW-~6, 400.
lSThe above process wa~ repeated under the s~me çondition.~, except for the oo-feedin~ tim~ and the lnltial an~ co-~
per~entages of sodlum per~.3ulfate ~)n~ed on tot~l monoltler:
Sample 9: 0 .167~ ~odium per~lfa~o ( basecl on total monomor ) wa~ added initi,311y to ~he fla~k, with 0.503% co-fed. The ~0molecular welght of the resultin~ copo1ymer wa~ MW~127,000.
Sampl~ 10~ Utlllzin~ ~odium p~r~ulfate as in S~mple 10, w1th the ~o-f~ed time lncreased from 1 to 1.25 hours, ylel~ed a ~opo1y~er with MW-12~ 0.
Sampls 11: Utilizing ~odium per~ulf~te ln amo~lnts a~ t ~5 ~orth ln Sample 10, but with the co-feed tlme d~creased from 1 to . 0.75 hour~, a copolymer W~-Q obtained wlth ~W-135,000.
~2~
Sample 12: 0.125% sodium persulfat~ w~.~ In~ti~lly in the ~lask, and 0.375% sc?diutn persulfat~ was co-~d. ~ha copolymer produc~ h~d ~ ~w-157,000.
Carp~t samples treate~ in accordan~e with the presellt inven~ion were tested ~or dur~ility ~nd sta1n resist~nc~ in compari~on with an untreated, un~tained ~ntrol and a ~taine~, untreatsd cor,trol. ~he carpet S~mplt?S tested were mad~ o~ undy~d, heat-set nylon ~ fi.ber.
A treatment bath was prepared cont~ining 12~1 part~ deionl~e~
water, 1.25 parts so~ium ~ fosuccinate a~ a 6ur~act~nt ~a~ail~ble . fro~ Rohm and ~as Company under the name TritonTM ~R-5M), '~.5 parts acetl~ acid, and ~5 parts of a 1% solid~ aqu~ou~ solution oÇ an 1~ anti-stain agent of the present inv~n~i.on. ~o tr~at a carp~t sample, t~e bath wa~ brou~.~ht to a b~lil anrt therl t:he .~amp.l.~ a~
ad~ed to the bat.h an~ ~olled ~ b~ elllni~ t.e~-;. Att~r t?oilin~J, the samp.l~ was centrlEuge~ ~n~t therl t.lrie~ ~t çlbo~t 1l6bC for about 8-10 minutes.
The treated ~ample was sh~po~A to demon~3trat~ th~ d~r~billty of the anti-staln tr~atm~nt. 'rhis wa~ per~crm~d by dipping tne s~mple into a 2.11~ aqueous s~luti~n of a ca~pat shampeo oontainin~
e~hylenediaminate~r~-aoetic acld t~rasodlum s~ av~ ble from Blue Luster Home Care Products, Inc., Irld~anap~lis, under the name ~5 Rinse 'n V~ at about ~C for about 15 ~erond~, fvllowed by rinslng the s~mpl~ in co~d water, centrifugin~ t~e sample, and ~hen 2 ~ ,6~
dryin~ the sample at ahout lOD~ for ahout 30 minutes.
The treated and control ~amples wer~ then stained ~y imlnersion . in a 10~ aqueous solutLon of a food pr3duct c~ntal~in~ ~itrlc a~id . ~nd about 0.1~ Food, Dru~ and C~smetio Basic Red ~40 ~ye ~herry Kool-AldlM) fo~ abo~t five minutes ~t a te~.peratur~ of a~out 41~, followed by rinslng in co~d water. The sa~ples ~.~ere then Gontrifuged followed by dryl~g ~t ~2~C.
. The s~mples w~re e~al~ated f~r staining, by te~-tln3 for brightnes~ ~on a scale of 1-50~ using a ~rlghtlme~br Model 54-M
Bri~htness Te~ter (~chnidyne ~orp.)~ ~urin~ the brightness measuremen~s, the nap of the carpet was laid in th~ same ~irection for each carpet sample. F~ ve bri~ht~ess me~surements were tak~
f~r ~ach sample (2" x ~
The result ~f the te~t~n~ o tho samples treated with anti-~ain ag~nts prepared according tc Ex~mple 1 are gi~en in Table l~ w.
..
~2 f~
TABLE~ 1 . , ~
S ~rightnes~; ( S~n~ard d~viation ~
Sample Unstat ned Staine~ Sh~mpoo ~ Stained _ 1 36.1 (2.13 1~ 3 . 10 2 44.7 (S.3) l4.5S0-7) 3 41.4 (4.~ lfi.~a (1.23 ~ . 42.8 ~1~2) 1~.~(2.6) ~0.4 ~3.5~ 17~3(2.7) Control A 48.~ (~,9) Control B 1.6 (0~) .0 Both Cor~trol A ~nd ~ontrol B w~re untxeat~ed~
EXAMPI.E_5 The procedures o~ Example 4 wsre repeated us~.n~ the antl-stain agent~ prepared in accordance with ~xamples 2. and ~ . The resul t~
~re ~hown in T~ble 2 below.
'~02~t~
TABLE ~
Brightn~s;
5 Sample Uns~a n d__ _St~ined Sham~St in~d 6 36. 4 la . 1 7 ~ 17.1 ~ ~3.~2 7~72 ~ 23.24 12.01 ~2 . ~. . 63 11 3~ 7 13. ~0 12 31~47 13,3 Contxc: 1 C 48 . 8 20~ontrol D~ 1. 6 , ~ .... ~
Both Gontrol C and ~ontrol D w~re ur~treated~
~5 The tabulated re~3ult$ given in E~amples 4 and 5 show the excellent stain re~istan~e and durability o~ stain reslstan~e of carpets tre~ted in accordar~ce w.ith the pre.~ent invent ;lon.
3o r,xAMPr.E 6 The procedure o~ Examplo 4 wa5 r~3Fl~tecl using an ~n~i-stain a~ent prepa~ed ac,co~ding to Example 3 having ~ wei~ht ~vera~e molecular welght of 135, 000, 6~xcept a commercial acid shampoo was . utillzed in place of "Rinss IN Vac" ~ alkallne shampoo) in the last samplQ. The aci~ ~hampoo ~ormulation wa~ ~59~ butyl acrylate/15 styrene~50P~ methacrylic ac~à~ neutralized ~ h ~mmonia an~
cataly~ed with zirc. The rasults are se~ for~l~ in ~able 3 below:
~3 2~2~
Si~mple B~ight ~;.s Traated Control (no ~hamE~ooJst~ined~ ~6 . 4 ~lkaline Shampoo ( stained ) 16 . ~
Acid Shampoc~ ~ stained ) ~3 . 5 The results of thi~ oxample demonstr~te the dur~bility of ~:he c~rpet after treatment aGcording to the inven~ion, comparin~ a cont~ol s~mple with no shampoo $ t;ep wlth sample~ that have been 10 shampooed using st~rldar~ alkaline and a~id sham~oos.
in the practlce of the present inves~ti~n is det~rmlned by ~h~ wate~
~olubility, ~i~cosity and practic~l process-of-manuf~cture req~irement~.
The pre~ent inventLon al~o provide~ a f~ber impre~nate~ with the ~nti-stain agen~. Op~ion~lly, the antl-~tain Age~t of t~q present inventlon can be combined with an adJ~Ivant~, such as a surfactan~, novola~ re~in, ultravi~let-light absor~er, or~anic or ino~ganiC a~id, antioxldant, eth~xylated or ~ul.~onated fatty acid, . polymer coating, Gr a mixtur~ thereo~.
. 10 The antl-stain agent of the present lnven~ion is u~eful ln treatin~ fiber materials, e.~ ibers made from nylon and/or amide flber, particularly carpet~, to make the~ staln re~istant.
Preferably, the flber used in accordanc0 with th~ pr~n~ invention is made from nylon 6, wh~ch is a polymer of oaprolactam, or nylon . 15 ~6, which is a condensation prod~ct of adlpic aci~ and . hexamethylenedi~min~, which ~re well known in the m~n~factur~ of carpe~s such a~ dis~lo~ed in U~S. I'~s~t No~ ~,501,5~1 and . 4,780,4g9, the di~closure~ ef whieh àre incorporated her~in by reference. Other usef~l nylon ~lbor~ lnclud0 tho~ made from, e.~., nylon 11, ~hich is a polymer of ll-amlno undec~nolc acid, nylon 610, which is a polycond~nsation product of ~ebaoic acld and . hex~methylenediamine, and a copolym~r Gf nylon ~nylon 66, all of whlch are well known as disclosed in th~ aforesaid U.S. Patent No.
4,501,5~1~
Pref~rably, flber ls treAted ln accordance w$th the pr~sent invantion by lmmor~ion in an acidio aquaouR bath having a pH
. . 3 202~
between about 1.5 and 5.5, preferably between aho~t ~.1 and 4 . O, more prefarably between about 2. 5 and 3. 5, oontalnin~ th~ ~nti-staln agent, which i~ ~aintalned at a preferable temper~tl.lre between a~out 38 and 110~, more preferably between about 80 and 100C. ~o obtain the best anti-~tain effect, imm~r~lon time v~ies between abo~t 1 and 20 ~inute~, more preferably between about 5 and 15 mlnutes, most preferably between about 7 and 12 mln~tes. The amount of anti-st~in agent u~ed in th~ hath veries be~ween about . 0~ and 10 weight % of the nylon fi~e~ t~ he treated, pref~rably between about 1.0 and 4~0 weight ~, more preferahly between abou~
1.2 and 3.0 weight ~. Acidit~ of the aqu~ s bath in combination with eleva~ed temperature i~ mal~tatned to ~ss~re optimum abso~ption by the nylon fl~er. ~eidQ us~ful t.n maintainin~ the proper pH include both or~anic and lnorganiG acids, e.g., ac~tic a~id, sulfamlc a~id, citrlc acid, nitrlç ac~d, formic acld ~nd phosphori4 ~cid, which are add~d i.n sufficient amount to maintain . the pH in th0 preferr~d r~n~e. A su~factant i~ ~r~ferAbly ~dd~d to the bath to as~i~t ln w~ttin~ the nyl~n fiber at an amount between about 0.~ ~nd 1.5 wei~ht ~ of the nylon fiber to be t~eated. Useful ~urfa~tants in~.lude non-lonlc ~nd anionlc surfa~tan~s, e.~., so~l.um sulfosucclnate, dlootyl and dlnonyl sulfosuccinates, nonyl phenol ethoxalates, linear-alkyl sulfonates and ~odecylbenzene sulfoni~ aGids. O~her preferable additives, which ~ay be lntroduced into th~ bath a~ betw~en ~bo~t ~ and 3 weight ~ o~ the nylon f~ber to be treated, include anionic-acid dye levelers, novol~ res~ns, such as sulPonated naphthol~ph~nol ~ ' 2~2~
formaldehydc condensate~ an~ dihy~rox~1r~iphenyl ~,lfone~;
ultraviolet~ h~ a~sorb~r~, e~, ben~phen.on~, sllch a.s 2-. hydroxy-4-methoxybenzophenono-5-sulfonic a~d, disodlum-~,2'-dihydroxy-4,4'-~i~et~oxy-5,5'-dis~lfobenzophenone, 2,2',4,~'-tetrahydroxy4anzophenone, ~,4-dlh~droxyber;z~ph~none, ~-hydro~y-4-methoxybenzophenone, and 2,2'-~ih~droxy-4,4' dim~thoxy~enzoph~none~
~ntioxidants, such as sodiu~ ~hiocyanate, ethoxylat~d or ~ulfonat~d fatty a~id3, e.g., coconut Dil, tall o1l, casto~ oil, so~ean oi and peanut oil; and polymerio coatin~ compounds, polyvinylchlorlde,, polyviny~3cetate, pol~vinylalc~hol, acryllc.~, styrenes, and flusrochemic~l compound~ s~ch as ~rlfluo~oethan~.
A typical ca~pet proces~ preferably ~nvolves first dyein~ the carpet ~o a de~ired color, then saturating the carpe~ in the bath ~ontainin~ the antl-stain a~ent. ~ein~, howev~r, çan be perfor~ed after, or s.imultaneousl~ with, the stain~re~i~tant treat~ent. In tr~tin~ c.arpets in accordanc~ wlth the ~r~sent inv~ntlQr commerclally a~ilable d~eln~ uni.~, ~J~1a,h ~ vF~ hl~ t'~o111 thb Oting Company er Ku~te.r ~or~o~ ti.on, is advant~eo1l~ly used. ~uch unlts and their op~rati~n are we~l k1lown as dlsclos~d ln the .0 afor~id U~5. Pa~ent No~ 4,50l,59l, A pre~erred proces~ln~ sy~tem for treatin~ carpet is de~cribed. Th~ c~rpet i~ f~rst wetted, f~r ex~ple with a soiutlo~
containîn~ ~y weiyh-~ 0.~ Triton~ GR-5M ~Rehm ~ Haas) and O.l ~ ~EA
. ~Triethanolamlne~. Aft~r nax~ pas~1A~ thr~ugh nip rollæ, th~
. ~5 carpet then i~ spray-dy~d, ste~med ~nd rinsed. ~he ~tain-resist trea-tment is ~pplied in the n~xt stage, a~ ccnditlo~s o~ ~bout 160 180~F/4 sec. using a ~uster unit. The carpet i s there~fter ste~me~
a~ , e , ~ ., 2~5F~'12û sec . ~nd linsed Final ly , ths carp~ is passed throu~h a ~;pray f luorocarbo~l ~re~ment .
In tre~ting flber in ~ccurdanee with th~ pr~3~;Qn~ ;nvention -~he 5 fiber is ~mpragn~tes~ with a ~iufflcient alrlount ~f the ar~ti-~3tain a~ent to imp~t stain res~tan~e -to the fiber~ Preferah~y, the amoun~ of anti-~ain ~gent impregnatl d in~ he flber varl~s between ~bout O . ~ and ~0 . O weight ~ of the nylon f ib~r, m~r~
pr~erabl~ between abou~ O.Z and ~..O wel~ht ~i, mos~ pref~r~
between AboUt O . 3 ~Ind 0. 7S wei~ht. % .
Fiber treated in aceo~dan~3 wttl- -,he present inv~r~tion exhibits stain l~esistanc:e to a variety of ~ ri el 5, .~:u~.h as foods and beverages. M~ny such materi~l~ cont~in dye~, ~aleh ;3~ Foo~, ~ru~a and Cosmetic (FD&C) ~ed ~ye 40, th.~t coml~onl~ conle into contact with carpet~3 when such p~oduct~ ar~ .~eei dentally ~pilled on the carpet. Howeve~, such dyes are eE~sily ren)o~JP.~ f~om flt~er carpets treated in ~ccordarlce with th~ ~resent ' ;~ t i.c)~l by l,;.Lmp.1.~n rinsin~ with w~ter or usln~ ~n ~ eOu~ solut~ of a r~ fl, anion:iG, carp~t shampoo. Rinse-wat~r temper~tures ar.e preferabl.y rnainl~ained at about 15-fi54C, mor~ prefer~b:Ly at ,~bout ?.~5-38C.
To more clearly c~escrib0 the presen~ ir~vent.ion, the ~oll.-~winy non~ itlng e~c~mplss ~re provi~ed. In th~ eic~mple~, all part.~ an~l percentass~ are by wei~ht ~nl.~s~ lnd~ted oth~3rwi.se. Ir~ the examples, MW denete~ weight a-~ray~ molecu~ar w~ht determined by ~5 aqueous ~:PC, Mn denote~3 number av~ra~3 r~lolecular weLght, ~nd ~W/Mn d~3not~ the molecular w~ 3ht d~tribu~lon~
202~a Anti-stain agent3 a~c~rdin~ to tha pr~sent 1~vention w~r~
prepared as foll~ws:
~ w~ tho~sand grams o~ DI (deloni2ed) w~ter and 9~ of Q.2% .iro~
sul~ate were ~dded to 3 5-liter 4-necke~ flAsk fitt~d ~ith a $~ir~er, condense~ and nltro~en inle~. ~hls solution wa~ hea~d ~nde~ a nitrogen a~mosphere to ~0 degree~ C.
A solution of 1~.3g o SMBS ~odium ~etabisulfit~) in 22.a8g of DI water was prepared. 17.5~g (50 weisht ~) of thi.~ solution . lO waS th~n added to the flask (l~ SM~ ased on tot~l monomer). To the flask were yradually and ~3eparate.y add~.d the ~ollowi;~ d~
oJer 1.5 hours: 70g of AA ~acr~rllc ~ci~) ~nd $30g of MA.A
~methacryl1~ ~cid); O.~g ~odium pers1llfate 1~ 7~ DI w~ter, and th~
remainder o~ the SMBS/DI water solutio~ SMBS on total m~nomer~, 15 whilet malnt~ininsJ the ~emperature o~ the flask contel~t~ a~ 70 . degree~ C. The polymoriz~d raaction was continu~d for lS minut~.~
after all the above feed~ were compl.et~ At ~h~ ime w~.~ adc~d 18g of 30~ ~12~ Flftoen min~te.S l~tQr, 1.379g of Dl water w~
added. The ~lask was then allowefl to cool to room temperatura~
~he copolymer so ~orm~d (S~mp.l~ l) had a MW o~ 197,000, Mn of 29,700 a~d MW/Mn of 6.~l~
The ~W o~ the ~opolymer sample~ wa~ varie~ by repeating the ~bove process and va~ying the amo~l~t ~f $MBS ~nd ~he ratio betwe~r the initial chargo ~t~ the fla~k/kettle~ an~ the amou~t lrem~ind~r) 2S used as co-feed. A copolymer (Sample ~) with MW-~01,000, ~n=~7,300 and ~W/Mn=7.33 wa~ obtsined usln~ OL5~ SMBS ~n to~al monomQr ln the kettle (in fl~sk initially) with 1~5~ SMBS on t~tal ~o~omer a~ co-2 ~ 6 ~ ~3 f~ed. At 0. 6~ kettle SMBS an~ 1. 22% ca-f~3d .~MF~S or~ t~.~t~l mollomer, a copolymer (Sa~ e 3) with MW=~17,000, Mn=29, 000 and MWj~n-~9,000 resu1ted; at U.75~s kf~ttl~ S~S r~nd ~. ~5 co-fed SM~3~ on tot~l monomer, a copo1ymer ( Sample 4 ) with MW-94, ~300, Mn-~.4, ~00 and 5 MWf!Mn-3 . ~5 wa3 ob~ined: an~ at 0 . 33% kettle S~I~$ and 0 . 33g6 kett~.e SMBS on total monomer, ~ copo'ylner lSamp1e 5~ wi-tn MW-~.31,000, Mn-47, 100 and MW/Mn-4. 9 ~.~ produc~
E AMPLE
Arlti~stain ~ nt~ according to the pr~3~ent :iLnvention were ~sl.so proAIl¢ed by the f~ owing proce~s:
TO a S-1iter 4-neCked 1EISk was added 3000~ nI w~ter, which was heate~ to 85 degree~ ~ unAer N2. Nine ~r~qm~ of sodi~lm per~ulfcite ( 1. 5 weiclht % based on to~al manomer ~ in :~0~ DI water was then added. After two r~linutes, a mi~ture of 6(~g i~A anc~ 5~0q MAA Wci~ fed ove~ a pe~io~i of or~e hour to the fIac;k, main~ainin~ e t~r~or~ture ~t 85 de~reer; C, ~ter whi~h :lO35-~ ofi DI wEit~3r was added. l`he Ela~k wa~ al:lowed t:o c r.~o~ n room t~3mper.ltur~ r~ MW
o the resu~tinS~ copolyn~ ampl~ ~) w~.r.~ 84,000, the Mr~ was 26,300 an~l MW~Mn was 3.1.
Ad~litlon21 c~po1ymer~ WeI'e'. al;sv pre~a:rr d by this rnf3tho~ y varying the amount of sodi~nl pe~rsulfate~ ~t lr~ ~odillln p~rsul ~te based on tot~l mon~m~r, a ~o~olyrn~r (Samp1a 7) resulted havin~
MW-124, 00(~, Mn-3~, 400 and MW/Mn 3 .
2~2~
EXAMPLE ~
. As in Exar~ple 1, A co-f~ed of monomer and cat~lys~ wa used, . The catalyst solution a~ded initlally to the heated reacto~
flask wa~ l~Sg sodium per~ulfate ~n 30~ DI water (0.~5 we~gh~ ~ on total monomor).
The co-feed wa~ 4. 5g NaaS~08 ln lOOg DI water plus 60~ AA and 154û~ MhA. The co-eeds were ~dde~ separ~tely o~r~ar ene hour. Th3 temperature was ~eld at 9~ de~ree~ C for thirty minute~, and then gg o~ 0.1~% iron sul~ate solution and 0.8g of t-butylh~droperexid~
10 in 5g of D~ w~ter were add~d . Then, 1. 2g o i~o--ascorbic acid ( IA ) : in 25g ~I w~ter w~ addsd. T~n minut~ later, a second identis~l amount of IA~DI water was adde~. ~lext, 1035~ DI water was ad~ed and the reaetion flask was then allowed to ccol to room temp~rature . The resultin~ copolylner ( Sample 3 ) had a MW-~6, 400.
lSThe above process wa~ repeated under the s~me çondition.~, except for the oo-feedin~ tim~ and the lnltial an~ co-~
per~entages of sodlum per~.3ulfate ~)n~ed on tot~l monoltler:
Sample 9: 0 .167~ ~odium per~lfa~o ( basecl on total monomor ) wa~ added initi,311y to ~he fla~k, with 0.503% co-fed. The ~0molecular welght of the resultin~ copo1ymer wa~ MW~127,000.
Sampl~ 10~ Utlllzin~ ~odium p~r~ulfate as in S~mple 10, w1th the ~o-f~ed time lncreased from 1 to 1.25 hours, ylel~ed a ~opo1y~er with MW-12~ 0.
Sampls 11: Utilizing ~odium per~ulf~te ln amo~lnts a~ t ~5 ~orth ln Sample 10, but with the co-feed tlme d~creased from 1 to . 0.75 hour~, a copolymer W~-Q obtained wlth ~W-135,000.
~2~
Sample 12: 0.125% sodium persulfat~ w~.~ In~ti~lly in the ~lask, and 0.375% sc?diutn persulfat~ was co-~d. ~ha copolymer produc~ h~d ~ ~w-157,000.
Carp~t samples treate~ in accordan~e with the presellt inven~ion were tested ~or dur~ility ~nd sta1n resist~nc~ in compari~on with an untreated, un~tained ~ntrol and a ~taine~, untreatsd cor,trol. ~he carpet S~mplt?S tested were mad~ o~ undy~d, heat-set nylon ~ fi.ber.
A treatment bath was prepared cont~ining 12~1 part~ deionl~e~
water, 1.25 parts so~ium ~ fosuccinate a~ a 6ur~act~nt ~a~ail~ble . fro~ Rohm and ~as Company under the name TritonTM ~R-5M), '~.5 parts acetl~ acid, and ~5 parts of a 1% solid~ aqu~ou~ solution oÇ an 1~ anti-stain agent of the present inv~n~i.on. ~o tr~at a carp~t sample, t~e bath wa~ brou~.~ht to a b~lil anrt therl t:he .~amp.l.~ a~
ad~ed to the bat.h an~ ~olled ~ b~ elllni~ t.e~-;. Att~r t?oilin~J, the samp.l~ was centrlEuge~ ~n~t therl t.lrie~ ~t çlbo~t 1l6bC for about 8-10 minutes.
The treated ~ample was sh~po~A to demon~3trat~ th~ d~r~billty of the anti-staln tr~atm~nt. 'rhis wa~ per~crm~d by dipping tne s~mple into a 2.11~ aqueous s~luti~n of a ca~pat shampeo oontainin~
e~hylenediaminate~r~-aoetic acld t~rasodlum s~ av~ ble from Blue Luster Home Care Products, Inc., Irld~anap~lis, under the name ~5 Rinse 'n V~ at about ~C for about 15 ~erond~, fvllowed by rinslng the s~mpl~ in co~d water, centrifugin~ t~e sample, and ~hen 2 ~ ,6~
dryin~ the sample at ahout lOD~ for ahout 30 minutes.
The treated and control ~amples wer~ then stained ~y imlnersion . in a 10~ aqueous solutLon of a food pr3duct c~ntal~in~ ~itrlc a~id . ~nd about 0.1~ Food, Dru~ and C~smetio Basic Red ~40 ~ye ~herry Kool-AldlM) fo~ abo~t five minutes ~t a te~.peratur~ of a~out 41~, followed by rinslng in co~d water. The sa~ples ~.~ere then Gontrifuged followed by dryl~g ~t ~2~C.
. The s~mples w~re e~al~ated f~r staining, by te~-tln3 for brightnes~ ~on a scale of 1-50~ using a ~rlghtlme~br Model 54-M
Bri~htness Te~ter (~chnidyne ~orp.)~ ~urin~ the brightness measuremen~s, the nap of the carpet was laid in th~ same ~irection for each carpet sample. F~ ve bri~ht~ess me~surements were tak~
f~r ~ach sample (2" x ~
The result ~f the te~t~n~ o tho samples treated with anti-~ain ag~nts prepared according tc Ex~mple 1 are gi~en in Table l~ w.
..
~2 f~
TABLE~ 1 . , ~
S ~rightnes~; ( S~n~ard d~viation ~
Sample Unstat ned Staine~ Sh~mpoo ~ Stained _ 1 36.1 (2.13 1~ 3 . 10 2 44.7 (S.3) l4.5S0-7) 3 41.4 (4.~ lfi.~a (1.23 ~ . 42.8 ~1~2) 1~.~(2.6) ~0.4 ~3.5~ 17~3(2.7) Control A 48.~ (~,9) Control B 1.6 (0~) .0 Both Cor~trol A ~nd ~ontrol B w~re untxeat~ed~
EXAMPI.E_5 The procedures o~ Example 4 wsre repeated us~.n~ the antl-stain agent~ prepared in accordance with ~xamples 2. and ~ . The resul t~
~re ~hown in T~ble 2 below.
'~02~t~
TABLE ~
Brightn~s;
5 Sample Uns~a n d__ _St~ined Sham~St in~d 6 36. 4 la . 1 7 ~ 17.1 ~ ~3.~2 7~72 ~ 23.24 12.01 ~2 . ~. . 63 11 3~ 7 13. ~0 12 31~47 13,3 Contxc: 1 C 48 . 8 20~ontrol D~ 1. 6 , ~ .... ~
Both Gontrol C and ~ontrol D w~re ur~treated~
~5 The tabulated re~3ult$ given in E~amples 4 and 5 show the excellent stain re~istan~e and durability o~ stain reslstan~e of carpets tre~ted in accordar~ce w.ith the pre.~ent invent ;lon.
3o r,xAMPr.E 6 The procedure o~ Examplo 4 wa5 r~3Fl~tecl using an ~n~i-stain a~ent prepa~ed ac,co~ding to Example 3 having ~ wei~ht ~vera~e molecular welght of 135, 000, 6~xcept a commercial acid shampoo was . utillzed in place of "Rinss IN Vac" ~ alkallne shampoo) in the last samplQ. The aci~ ~hampoo ~ormulation wa~ ~59~ butyl acrylate/15 styrene~50P~ methacrylic ac~à~ neutralized ~ h ~mmonia an~
cataly~ed with zirc. The rasults are se~ for~l~ in ~able 3 below:
~3 2~2~
Si~mple B~ight ~;.s Traated Control (no ~hamE~ooJst~ined~ ~6 . 4 ~lkaline Shampoo ( stained ) 16 . ~
Acid Shampoc~ ~ stained ) ~3 . 5 The results of thi~ oxample demonstr~te the dur~bility of ~:he c~rpet after treatment aGcording to the inven~ion, comparin~ a cont~ol s~mple with no shampoo $ t;ep wlth sample~ that have been 10 shampooed using st~rldar~ alkaline and a~id sham~oos.
Claims (20)
1. In a method for treating fiber with anti-stain agent, the improvement wherein the anti-stain agent comprises a copolymer of about l to 20 weight percent acrylic acid and about 80 to 99 weight percent mothacrylic acid, said copolymer having a weight average molecular weight greater between about 80,000 and 350,000.
2. A method as recited in claim 1, wherein the weight average molecular weight is between about 100,000 and 250,000.
3. A method as recited in claim 1, wherein the weight average molecular weight between about 130,000 and 200,000.
4. A method as recited in claim 1, wherein the fiber is nylon 6 fiber or nylon 66 fiber.
5. A method as recited in claim 1, wherein the fiber is in the form of a carpet.
6. A method as recited in claim 1, wherein the copolymer is of about 5 to 15 weight percent acrylic acid and about 85 to 95 weight percent methacrylic acid.
7. A method as recited in claim 1, wherein said anti-stain agent is applied in an about between about 0.8 and 10.0 weight percent of the fiber.
8. A method as recited in claim 1, wherein the fiber is nylon or amide fiber.
9. A fiber material comprising fiber impregnated with an anti-stain agent comprising a copolymer of about 1 to 20 weight percent acrylic acid and about 80 to 99 weight percent methacrylic acid, said copolymer having a weight average molecular weight between about 80,000 and 350,000.
10. A fiber material according to claim 9, wherein the weight average molecular weight is between about 100,000 and 250, 000.
11. A fiber material according to claim 9, wherein the weight average molecular weight is between about 130,000 and 200,000,
12. A fiber material according to claim 9, wherein the fiber is nylon or amide fiber.
13. A fiber material according to claim 9, wherein the fiber is nylon 6 or nylon 66 fiber.
14. A fiber material according to claim 13, wherein the fiber is in the form of a carpet.
15. A fiber material according to claim 9, wherein the fiber is in the form of a carpet.
16. A fiber material according to claim g, wherein the copolymer is of about 5 to 15 weight percent acrylic acid and about 85 to 95 weight percent methaorylic acid.
17. An anti-stain agent for fibers, comprising a copolymer of about l to 20 weight percent acrylic acid and about 80 to 99 weight percent methacrylic acid, aid copolymer having a weight average molecular weight between about 80,000 and 350,000.
18. An anti-stain agent as recited in claim 17, wherein the weight average molecular weight is between about 100,000 and 250,000.
19. An anti-stain agent as recited in claim 17, wherein the weight average molecular weight is between about 130,000 and 200,000.
20. An anti-stain agent as recited in claim 17, wherein the copolymer is of about 5 to 15 weight percent acrylic acid and about 85 to 95 weight percent methacrylic acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US40805389A | 1989-09-15 | 1989-09-15 | |
| US408,053 | 1989-09-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2024600A1 true CA2024600A1 (en) | 1991-03-16 |
Family
ID=23614667
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002024600A Abandoned CA2024600A1 (en) | 1989-09-15 | 1990-09-04 | High molecular weight acrylic anti-stain treatment for nylon carpet |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0417960A3 (en) |
| JP (1) | JPH03119186A (en) |
| KR (1) | KR910006564A (en) |
| CN (1) | CN1050417A (en) |
| AU (1) | AU6234890A (en) |
| BR (1) | BR9004610A (en) |
| CA (1) | CA2024600A1 (en) |
| NZ (1) | NZ235216A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5681620A (en) * | 1996-01-11 | 1997-10-28 | Elgarhy; Yassin M. | Enhancement of stain resistance or acid dye fixation, improved light fastness and durability of fibrous polyamide and wool substrates |
| US5952409A (en) * | 1996-01-31 | 1999-09-14 | 3M Innovative Properties Company | Compositions and methods for imparting stain resistance and stain resistant articles |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5629376A (en) * | 1990-10-31 | 1997-05-13 | Peach State Labs, Inc. | Polyacrylic acid compositions for textile processing |
| AU687343B2 (en) * | 1991-07-05 | 1998-02-26 | Feltex Modular Carpets Pty. Ltd. | New and improved backing for textiles |
| NZ243405A (en) * | 1991-07-05 | 1994-12-22 | Feltex Modular Carpets Pty Ltd | Penetrable fabric backing material comprising silica fabric and impregnated with lubricant |
| US5516337A (en) * | 1992-09-02 | 1996-05-14 | Minnesota Mining And Manufacturing Company | Chemical system for providing fibrous materials with stain resistance |
| US6524492B2 (en) | 2000-12-28 | 2003-02-25 | Peach State Labs, Inc. | Composition and method for increasing water and oil repellency of textiles and carpet |
| US20070136953A1 (en) * | 2005-12-20 | 2007-06-21 | Materniak Joyce M | Stability for coapplication |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU627711B2 (en) * | 1988-03-11 | 1992-09-03 | Minnesota Mining And Manufacturing Company | Process for providing polyamide materials with stain resistance |
-
1990
- 1990-09-04 EP EP19900309669 patent/EP0417960A3/en not_active Withdrawn
- 1990-09-04 CA CA002024600A patent/CA2024600A1/en not_active Abandoned
- 1990-09-07 NZ NZ235216A patent/NZ235216A/en unknown
- 1990-09-08 KR KR1019900014208A patent/KR910006564A/en not_active Application Discontinuation
- 1990-09-11 AU AU62348/90A patent/AU6234890A/en not_active Abandoned
- 1990-09-14 BR BR909004610A patent/BR9004610A/en not_active Application Discontinuation
- 1990-09-14 JP JP2246015A patent/JPH03119186A/en active Pending
- 1990-09-15 CN CN90107728A patent/CN1050417A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5681620A (en) * | 1996-01-11 | 1997-10-28 | Elgarhy; Yassin M. | Enhancement of stain resistance or acid dye fixation, improved light fastness and durability of fibrous polyamide and wool substrates |
| US5952409A (en) * | 1996-01-31 | 1999-09-14 | 3M Innovative Properties Company | Compositions and methods for imparting stain resistance and stain resistant articles |
Also Published As
| Publication number | Publication date |
|---|---|
| AU6234890A (en) | 1991-03-21 |
| BR9004610A (en) | 1991-09-10 |
| JPH03119186A (en) | 1991-05-21 |
| EP0417960A3 (en) | 1991-06-12 |
| EP0417960A2 (en) | 1991-03-20 |
| KR910006564A (en) | 1991-04-29 |
| NZ235216A (en) | 1992-09-25 |
| CN1050417A (en) | 1991-04-03 |
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