CA1328283C - Cleaning compositions containing a colorant stabilized against fading - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

An aqueous cleaning composition comprising a surfactant; up to about 50% of a higher boiling solvent, typically an alkyl ether of an alkylene glycol, said solvent introducing impurities into the composition in an amount and of a nature normally chemically incompatible with oxidizable dye chromophores; a dye in an amount to provide a desired tinctorial value, and a stabilizer selected from the group consisting of salts suitable to provide iodide and thiosulfate anions in an amount effective to retard fading of the dye, said composition having a basic pH
when the stabilizer is the thiosulfate salt. In another aspect of the invention, the stabilizer incorporated into composition containing a solvent, a surfactant, and water, and optionally a dye provided a beneficial cleaning result. In yet another aspect of the invention, the stabilizer beneficially retards the development of malodors when the compositions of the prevent invention are contained in a PVC container. Broadly, the incorporation of the stabilizer in said solvent can be employed to neutralize said impurities.

Description

- ~. DR-517 1 32828~

CLEANING COMPOSITIONS CONTAINING A
COI,OR~NT STABILIZ~D AGAINST FI~DINÇ

by Laura A. Ciolino and Chaun F. Clàncy ield oX Invention $his ~nventio~ relates to clsaning compositions i~cluding ~oth ready-to-use a~d water-dllutable concentrate t~pe com~
position~, ~uitable ~or 6pray-and-wips cleaning o~ hard cur-~aces, ~or example, glas~, countertop~, tile, and the like.
More ~peci~ically, th~ pr~6ent invention rel~te~ to ~uch co~-positions comprising ~ ~urfactant, a ~olvent, and ~.colorant, there al~o being pre~ent in tha composition materials ~uch as s~lvent impuritles ln such conoentration that the colorant has a tendency to fade over ti~e~ said compoe~tion further co~prlsin~
a colorant stab~lizer pre~ent ~ n an a~ount e~f~ctiv~ to reduce ~ubstantially the rat~ at whlch the coloxan~ ~ades. In addi-tion, it has been found that the stab~lizer provide~ a col~
lateral cleaning bene~it ~nd also reduces the ~ormatlon of Dlalodors when the compoAition ~ g contained in a pla~tic container.
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Backqround of the Invention Spray-on-and-Wipe-off cleaning compositions are well known in the art. See, for example, U.S. Patents 3,463,735 to Stonebraker; 4,302,348 to Requejo, and 4,606,842 to Keyes, et al. The spray on-and-wipe-off compo6itions o~ the prior art typically include a ~olvent, for example, a mixture of isopropyl alcohol and ethylene ~lycol mono~utyl ether, a surfactant, for example, sodium lauryl sulfatet a builder, ~or example, tetra-sodium polypho~phate or a water soluble polyacrylic acid resin;
an alkalinity agent, for example, ammonium hydrox$de and mor~
pholine, or an acidity agent ~or example, acetic acid: ad~uvants su~h as a dye and ~ perfume; and water. Composltions includin~
the al~alinity agent typically have a pH of betwsen about 8.5 to about 11.~, wh$1e compo~itions incorporating th9 acldity agent typ~cally have a pH o~ from about 2.5 to about 6.5.

It has been ~ound that there is a tendency of the colorant, most typically a water soluble dye, present in these known com-positions to fade in ~uch composltion6. It 15 believed that ~he tendency for the colorant to fade ls attributable to impurities present in th~ composition/ pr~marily impuritle~ associated with -~
the glycol ether-type ~olvent, e~pecially when 8uch solvents are incorporated at higher concentrations. Concentrates of such 1 3~8283 compositions intended for dilution with water prior to use are especially susceptible to this dye fading problem. Fading o~
the colorant is not only unattractive to purchasers of the prod-uct, but makes the product less visible when applied to the sur-face to be cleaned. Accordingly, there i6 a defin~te need to at least substantially reduce the rate at which the colorant ~ades. It has been found that incorporation of iodide and thiosulfate anions in effective amount is satisfactory to stabilize the colorant in such compositions, the thio~ulfate an~ons being suitable when the pH of the composition is neutral or basic.

~ ccordingly, it i~ an ob~ect of the present lnvention to provids a ~pra~-on-and-wipe-off hard ~urface cleaning composi-tlon containing a colora~t ~tabllized ~gain~t color ~adlng.

It ls a further ob~ect of the present inventlon to provid~
such ha~d ~urface cleaning compo~itions, in concentrate or ready-to-u5e form, containin~ a level of a glycol ether ~olvent having a destabilizing concentration of dye-interaative impuritles.

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1 32~283 It ~s a further ob~ec~ o~ the pre~ent invention to provide such ~tabllized dys hard ~urface cleaning composltions where~n the stabilizer for the colorant ls an alkali metal iodlde.

It is yet another ob~ect o~ ~he lnvention herein de~crlbed to provide 6uch stabilized dye hard surface cleaning compo~i-tion~ wherein the stabilizer for the colorant i~ an alkali meta thlosulfate, the composition pH being neutral or basic.

Yet another ob~ect of the present inventlon 16 to provlde hard surface cleaning composition compatible wlth PVC
containers.

An additionAl ob~ect of the present invention i~ to prov~de hard Eurfac~ clean~ng compositions exhlbiting improved cleani~g performancs.

The~9 and other ob~ectg and advantages of the prese~t lnven-t~on will be apparent upon ~ readlng of the entire di9clo6ure, a ~ummary of which appear~ below.

Summary o~ the Invention The cleaning compositions o~ tho present ~nvent~ on comprise on a weight basi~ up ~o about 50% of a hlgher boiling ~olv~nt, , . . .
.

1 3282~3 preferably a Cl-C4 ~l~yl ethar o~ a glycol havlng a total o~
from 3 to about 12 carbon atom5 in the molecule, ~aid ~olvent introducing impurities i~to the composition in an amount and of a nature normally chemlcally incompatible wi~h oxidlzable dye chromophores; a dye present in an amount to provide a desired tinctorial value and including oxidizablQ dye chromophoress a stabillzer ~elected from th~ yroup oonsisting of an iodid~ or thlosulfate salt ~uitable to provide said anion in ~olution in ~he composition in an amount effectiv~ to retard ~ading of the dye; a sur~actant, and water. ~he compos~tion has an acld, neutral or basic pH, a pH modlfying agent being includable ~f needed to provid~ a predet~rmined compo~tion pH, compos$tions contalning the thiosulfat~ anion as the ~tabllizer, however, having a ba~ic or neutr~l pH.

In another aep~ct o~ the present inventlon, th~ ~tabiliz~r i~ incorporat0d $nto co~positions containing a ~olv~nt, pr~fer-ably a hlgh9r boiling solvent or a solvent 8y5tem containlng a higher boiling and a lower boillng solvent: a sur~actant, and water, and option~lly ~ dye, the concentration o~ th~ 6tabilizQr being ef~ective to provide ~ cleaning benefit a~ ~o~pared to such compo~ition not contalning the stabilizer. Preferably in this aspeat o~ t~Q invent~on, the stabllizer conGentration i~
from about 0.001 to about 0.10~ by w~ight o~ the total compo6ition.

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1 32~283 In yet another aspect of the present invention, lt has been ~ound that the stabilizer beneficially retards th~ formation o~
malodors when the compositions of the present invent~o~ are con-tairled ln poly~rinylchloride container~.

Detailed Descripkion of the Preferred Embodiment The ~pray-on-and-wipe-of~ hard ~urface clean~ng ¢omposition~
of the present inve~tion comprise an organic 601vent; a ~ur~
factant or surfactant mixture; a colorant, ~oct typically a water ~oluble dy~; a colorant 8tabilizsr~ and water. ~h~ com-posit~on~ ~ay have ~n acidic, neutral or ba~ir pH, and may furth~r include a~ opkional ingredlent~ one or more o~ the rollowlng: p~ modi~yin~ agents, perfumes, builders, hydrotrope~, chelating or ~eque~ter$ng agents, vlsco~ity ~odi~lors, and ~he llke.

Organic 801vent~ suitable ~or inclus~on in hard ~ur~aoe cleanlng compo~itions of tho type under consideratlon herein include monohydric alcohol~ having 2 to 8 carbons~ polyhydrio alcohols, especially gl~cols having 2 to about 10 carbons; and Cl to C4 al~yl ethers o~ alkylene glycols and polyalkylene glycols, said glyool ether~ having a total o~ ~rom 3 to about .

1 3~283 12 carbons. In many ~n~tances, lt 15 preferred to incorporate a ~ixture o~ the lower boillng monohydric alcohols, e6pecially 6uch alcohols having ~ro~ 2 to 6 carbons, and the hlgher bo~llng polyhydric ~lcohol~ or glycol ethers, to achlevo a de~ired rate of evaporat~on o~ the cc~po~ltion from the work ~urface. In other instances a higher boiling solvent ~y be used singly or in comblnation with on~ or more other higher boiling ~olvent~.
Preferably, the higher boilln~ polyhydric alcohol or glycol ~ther 601vent5 have a bo~l~ng point between about 120~ to about 2SO-C.

Sultable monohydr$c (lower bolling) ~olventa include methyl ~lcohol, ethyl alcohol, nopropyl and isopropyl alcohol~, n-butyl ~lcohol, etcO Typically, ~uch ~olvent~ ~re not incorporated ~lngly or in ad~ixtur3 .on~ with the oth~r, but rather are ~d- :
~ixed with one or ~ore high~r bo~llng solvent~ ~ prsviously indicated, Suitable polyhydric alcohol ~olvente include ~thy-lene glycol; propylen~ ~lycol, 1,2-b~tanedlol; 1,3-but~nsdiol;
tetramathylene glycol, 1,2-pentanedlol, pentamethylene glycol;
and 1,6-hQxaned~ol, wh~lQ of the glycol ether ~olvent~ mention may be ~ade of ethyl~ne glycol monomethyl ether; ethylenQ glycol monoethyl ether; ethylene glycol monobuty~ ether; propylene glycol monoethyl ether; propylene glycol tertiary butyl ether;
diethylene glycol monoethyl ether; diethylene glycol monobutyl . . ~ . . .

~ 328283 ether; tripropylene glycol monomethyl ether: tetraethylene glycol dimethyl ether: B,B-dihydroxydiethyl ethsr (l.e., diethylene glycol); ethylene glycol di-(B-hydroxyethyl) ether (i.e., triethylene glycol); ethylene glycol ~onophenyl ethsr;
and cyclohexyl ethyl ether. Especially ~uitable are glycol ethers having ~rom 5 to 8 carbon~ ln the molecule.

Preferred are s~hylene glycol monobutyl ether; propylena glycol monobutyl ether; propylene glycol tertlary butyl ether, and tripropylene ~lycol ~onomethyl ether.

The 601vent ln ready- 0-U8e compositions ~ay be present in an amount o~ up to about 30% by w~ight o~ ths co~po~ition, ~1-though ~olvent conc~ntratlon~ more typlcally range ~rom about 2 to about 15t by weight o~ the compo~itlon, pre~erably ~ro~ about 5 to about 15%, most pre~er~bly ~rom ~bout 7 to 12~ ~n concentrate compo~ition intend2d to b~ diluted with watQr prior to use, tho solvent ~ay bo pr~sent in an a~ount o~ up to about 50% by weight, the composition a~ter dllution having a 801v9nt concentration ~imilar to that o~ the ready-to-use verGion. Ths concentrate compositions ~ay bo applied ~ull strength ~or problem 60il~. The ready-to-use or the concentrate compositions subsequent to dilution should not contain in exces3 o~ the solubility li~it of the solvent in the compositlon as a whole, as shaking o~ the compositlon ~8 then necessary during u6e by the consumer. By blending o~ the low boillng, D~ore watQr soluble ~olvents, concentratlons of the higher boillng solvent~ in excess o~ thelr water 801ubility may be achieved, Observations o~ composlt~ ons contalning a qlycol ether as the ~olvent or one ~olvant in a ~olvent ~y~tem hava shown that colorant~, e.g., dyes, included ~n the composition~ have a ten-dency to :Eade o~rer 'cime, which ~adlng tendency i~ aggravated as the concentration of the glycol eth~r in the compo~ition~ in-creases. ~Soreover, thls fading problem i8 ~ox~ mani~e~t at elevated temperature conditions, such as may be encountered during warehouse ~torage at 6u~er temperatures.

Consideration oX pos~ible oau~ativ~ ~actor~ ~or dye de-colorization led to th~ b~lie~ that there ~lght be l~puritie~
as~oclated with the glycol ether typa ~olvents which would react or otherwi~e interact with chromophore 01tes pre6ent in the dye~. 5uch ~echani6a~ ~3 upported by the observation of more rapid fading o~ the dye a~ the concerl'cration o~ the glycol ether ~;olvent~ increased and by the ~ading rate increase as tempera- :
tur~ increased.

Analysi~ of a commercial 6a~11pl9 of~ ethylene glycol monobutyl ether 1 ndlcated tha'c varlous impurlties wer2 present, namely, _ g _ :, 1 32~283 butanol, butyl butal, 2-ethylhexene-2-ol, dlethylene glycol mono-butyl ether, 2-hydroxyethyl butyrate, and butoxyace~ic acid.
These material~ ar~ a-trlbutable to reactant~ ln the manufacture oi~ th~ solvent by reactlon o~ ~utanol with ethylene oxlde; to byproduct~ o~ tha reaction, ~nd to easily form~d alr degrada-tion impurities. Treatment o ~thylen~ ~lycol monobutyl ether with air ~t 100C to accelerate aging resulted in the ~orma-tion of n-butyraldehyde, butylformate, 2 butoxy-acetaldehyde, 2-i60butoxyethanol and butyl butyrate. It i~ also believed that highly react~ve p~roxide specles ar~ also ~ormed, ~o~t llk81y as a result of a~r degradat~on o~ ths ~olvent. The peroxides ~ay undergo ~urther reactlon to ~orm other oxidiz~ng ~pecies~
Likely p~roxide ~paci~ includ8 1~ hydroperoxy-2-hydroxy ethoxy)~utana; l-butoxy-2-hydro~y-1-athyl peroxlde~
1- (2-hydroxy~thoxy) -l-hydroparoxy ~utan~; ænd 1- (2-hydroxy-Qthoxy)-~-butyl p~roxide. In z~ddltlorl it ie bel~etr~d that ~milar class~s of lmp~ariti~s Dlay be present in the polyhydric alcohol ~olv~nt, ~p~c~ally sUch i~purit~ ormed by air degradation. Flnally~ additional 601vent-associated impuritles ~ay be ~or~ed BUbSegUant to compo~ition ~anufacture, for ex-ample, upon expo~ure o~ th~ co~po~tlon to tAe catalyzing e~fect o~ W light, lnteraction with other components and impurities thareo~, and at temperatures encountered during long-ter~ ~u~mer ~torage.

1 32~283 Such lmpuritles can be present ln an amount o~ up to about 0.5% by weight o~ the ~olvent. Thus, the compo~itlons of the present invention unavoidably include up to about 0.~5% o~ these impuxlt~e3, usually ~rom about OoOOl to about 0.1%, by total weigh~ o~ the compos~tion, one or ~ore of whloh ara bel~0ved to be reactiv~ or otherwisa intQractive with chromophore~ presant in dye~ commonly used in the compositions of the present inventlon.

Quits clearly, the concentration of tbe impurit~es reactive with ~he dye to occasion color loss does not need to bP
great, in view of the low concentration of the dye included generally in th~ co~position, and the potentially protr cted period of ti~e between manufacture and us~ by the consumer.

,, , By way o~ exa~ple, the lnitial t~nctorial value o~ the com~
positions of the present inventlon i~ preferably not redu~ed by . ~ore than about 50~ withln ~bout three ~onth~' BtOrage at 100F, ~06t prefe~ably, by not ~ore than about 25% wlthin about three months at 100F. It i~ al~o de~irable that t~e compo~ition o~ the present invention retain at lea~t about 50 :~ o~ thelr orlginal tlnetorlal value ~or about one month at .l 125Fo .,, , ~ .
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- ~ . -, , The dyas included in th~ composition of the present inven-tion are those which ara sub~ect to ~ading in the composltions of th~ pre~ent invsntion and which may be ~tabilized by the in-clu~ion o~ the stabilizer o~ the pre~ent inv~ntion, as herein-a~ter consid~red. The dye is present in the composition in an amount ef~ectiv~ to prov~de the compositlon with a desixed color intensity ox tinctorlal valus~ Typically, the compositlons of the present lnvention w~ll have a dye concentration of ~rom about o.OOOl to a~out 0.1%, preferably ~rom about 0.0005 to about 0.01%, and most pre~erably ~rom about 0.001 to about 0,005~, on an ac~lve dye ~a5is. Generally, the dye level would be greater ln th~ concentrate composition, or when the tlnc-torial value of the dy~ moleculs is low, Dy~s ~ound to fade ~n compo~ltlon~ of the pr~sent inv~ntion ln the absence o~ the ~ta~llizer const~tuent ar~ FD~C Yellow No.
5 (~old Yellow 23; Colour Index No. 19,140)s Sandolan Y~llow P5G
(Ac~d Yellow 40:1; Colour Ind~x No. 18,950:1); H~dacid Fast Light Yellow 2G (Acld YQ110W 17; Colour Index No. 18,g65);
Nylosan Yellow N-7G~ (Ac~d Yellow 218); Drimarsn~ Brllllant Green X3G (~eactive Green 12)~ Cibacron Yellow GA (Reactiv~
Y~llow No. 6)~ Pyrazol*Fast Tur~ulose GLL (Direct Blue 8~;
Colour Index No. 74,180), and Basantol Green 910 (Ac~d Green 26).
* Trademarks ~,.

- ' 1 32~283 Dyes fadable in the oompositions of the presen lnvention but no~ specif~cally mentioned herein may easily be ~creened for stabilization suitabllity in the compo5itions of th~ pre~ent in-vention. Other suitabl8 dye~ includa FD&C Blue No. 1 (Colour Index No. 42,090~ and H~dacid Aqua Blue (Colour Index No.
52,035).

It ha~ been ~ound that th~ inclusion o~ a small yet effec-tive amount generally le~g than 1,000 ppm, especlally less than 100 ppm, of an iodide or a thlosulfate anion reduce6 tho a~orement~oned tendency of dye8 present ln th~ composition to fade and eventually decolorize the thlosulfate anion9 how~ver, being sultabl~ onl~ in co~po~tlon~ having a neu~ral or basic pH. Su~table ~lts whlch ~ay be inoorporated that provlde the requisits anion are the iod$des of sodium~ potas~lum, lithium, ammoniu~, calciu~, magneslu~, iron (II), barium, ~anganese (II), tin (IV), and zinc, ~specially sodium or potasium iodide.
Suitabl~ 3alt~ which may be incorporated that providQ ths th~osul~ate anion includ~ the thiosulfates o~ sodium, potas~ium, ammonium, calcium~ ~ar~ ~agne51~, and ~ron (II~, especially sodium and potas~lum.

~ n addition to its utility a~ a dye stabilizer, ~t ha~ also been found that the ~tabilizer~ of th~ present invention also ~ 7j2~283 reduce the dev~lopment of of~-odor~. It i8 believed that the off-odors are due to interaction between the ~olvent and tha polyvlnyl chloride container for said aomposit~on or with a PVC
additive such as a heat stabllizer, and secondarlly to perfume degradat~on. Secondly, it ha5 been found that th~ stabilizers also provide an lmprovement in cleaning performance on certain surfaces includ~ng glass and baked enamel, although th~ reason ~or the improved performance i5 not fully understood, Between about 0.001 to about 0.1%, preferably fro~ about 0.001 to about 0.01~, is ~ff~ctive or thls ut~lity. If too much is pr~sent, a residue can occur on the ~urface being cleaned.

Anlonic, nonionlc, cat~onic, amphoterlc, and zwltt~rlonic surfactant~ are &uitable in the co~po~ition o~ the pr~sent ~nvention, and ars pre5ent in an a~ec~v~ cleanlng a~ount, typically ~rom about O.001 to about 5%, preferably 1~ an amount of rom ~bout 0.01 to about 1.0%, most prefera~ly from about 0.01 to ~bout 0,1~ by weight o~ the composition. Anionic ~nd nonion~c ~urSactant~ are e~pecially pr~erred.

Broadly, the anionic sUrfaCtants ar~ water-soluble ~lkyl or alkylaryl compound~, tho alkyl hav~ng from about 8 to about 22 carbons, inaluding a sulfate or ~ulfonate substituent group thak ~as been bas~-neutralized, typically to provide an alkali metal, e.g., sodium or potassiu~, or an ammonlum cat~on, lncluding, or example: (1) alkyl and alkylaryl ~ul~ates and ~ulfo~ates having preferably 8 to 18 carbon~ in th~ alkyl group, which may ba ~tralght or branched cha~nl e.g., eodium l~uryl ~ul~at~ ~nd ~odium dodecylbenzen~ ~ulfonate: (2) alpha-olefln ~ryl ~ul-fonates preferably having ~rom about 10 to 18 carbons ln the olef$n~ e.g., sodium C14_16 olefin ~ulfonatç, which ~ a ~ix-ture of long-chain sulfonate 6alt6 prepared by ul~onation o~
C14_16 alpha-olefins and chiefly compri~ing eodium alkens Aul-fonates and ~odium hydroxyal~an2 ~ul~onates; (3~ 6ulfated and sul~onated monoglyceride~, especially thoss derived ~rom coconut oil f~tty acids; (4) ~ulfate esters of ~thoxylated ~atty alco-hols having 1-10 ~ol~ ethylene oxlde, e.g., BodiUm polyoxy-~thyl~n~ (7 mol E0) lauryl ~ther aul~ate, ~nd o~ ~thoxylated al~yl phenol~ having 10 ~ol~ ethylen~ oxide and 8 to 12 carbons in the ~lkyl, ~.g., ammontum p~lyoxyethylene (~ mol E0) nonyl phenol ether sulfate; (5) base-neutralized esters of Patty acids and isethionic acid, e.g., sodium laur~yl isethionate: (6) ~atty acid amldes o~ a ~thyl taurid~, e.g., ~odium methyl cocoyl taurat~; ~7) ~-acetoxy- or B-acetamido-alkane sul~onatea, and (8) sarco~inates having ~rom 8 to 22 carbon~, ~.g~, sodium lauroyl sarcosinate.

, ' , 1 32~283 ~he nonionics include (1) ~atty alcohol alkoxylate~, es-pecially the ethoxylates, wherein the al~yl group ha~ ~rom 8 to22, pre~erably 12 to 18~ carbon~, and typically 6 to 15 ~ol alkoxide per molecule, e.g., coconut alcohol condensed with about nina mols ethylene oxlde; (2) fatty ac~d alkoxylates haviny from about 6 to about 15 ~ols alkoxylat~, espe~ially the ~thoxylateJ (3) alkylphenoxy alkoxylates, especially the ethoxy-lates, containing 6 to 12 carbons, preferably octyl or nonyl, in the alkyl, and having about 5 to 25, preferably 5 to 15 mols alkylen~ oxlde per molecule, ~.~., nonyl phenol ethoxylated with about 9.5 mols ethylene oxlde ~Igepal C0-630), (4) condensat~s o~ sthylen~ oxide with a hydrophobic ba~a formed by conden~atlon o~ propylane oxlde w1th propylene glycol, e.g., nonlonlc ~ur-~actants o~ the Pluronic seris~ ~anu~actured by BASF Wyandotte, (5) eondensates o~ ethylene oxid~ wlth an amlna or ~m1dQs t6) ~atty amine oxides, e.g., et~axyl dlm~thyl amine ox1d~ and (7) alkylolamides.

~ 180 suitable, alone or ln comb$nation with one or more other ~ur~actant~, are the ~pecialty ~urfactant~, e.g., sllicone surfactant~ and ~luorocarbon 6ur~actants. 0~ the latter, men-tion may be ~ade o~ the Fluorad FC ~eries manu~actured ~y 3M
Company and th~ Zonyl series manufaatured by E.I. duPont. These ~urfacta~ts are available in anlonic, nonionic, cat10nic, and * Trademarks ~;'.
~Y'i . . ~ . . : . . , . . :

amphoteric form. A urther dl~cussion of these sur~actants ap pear~ in U.S. Patents 4,302,348 and 4,511,489, both to ~eque~o.
However these surfactants are typically ~ncorporated at low concentration~ in the composition, usually at a level of less than about 0.1~ by weight of the composition, in view of their power~ul sur~ace-active effect. Preferred in neutral and acidic media is Fluorad FC-171, a nonionic fluorosur~actant. Pre~err~d in basic media is FC~129, an anonic fluoxosurfactant. Of the ~ilicone sur~actants, mention may be made o~ Masil 280 manufactured by Mazer Chemicals and tha S$1wet series manufactured by Union Carbid~, e.g., Sllwets L-720 and L-7607, the silicone sux~actants being lncorporated at about the sam~ levels as convsntional surfactants.

Preferr~d anionics are the alkyl and alkylaryl 3ul~ates and th~ alpha-olefin ~ryl 5ulfonat~s, while pre~erred nonionlc~ are the ~atty alcohol ethoxylate~.

As prQviously mentioned, optional adjuvanta may be lncor-porated in the compositions o~ the present invention in an amount ef~ective to obtain the intended function, typically in an amount of less than about 1%. Such ad~vants includ~ acidi-~ying agents ~uch as acetic acid, cit~ie acid, and other mono-and dicarboxylic acid~, and ~ineral acids such as hydrochloric ac~d and phosphoric acid, pre~erably in an amount to provide a * Trademarks ' , ,. ; . .
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1 3~8283 pH betwee~ about 2.5 and 5.5; alkallnity agent~ such a~ ammonium hydroxida, morpholine, ~odlum hydroxlde, ~nd alkanolamine~, preferably in an amount to provide a p~ between about 8 and 11:
builders such a~ tetra~odium, pyrophosphata and low molecular wei~ht polyacrylic acid and ~a~ts thereof; sequesterlng ~gente such a~ E~A and NTA; hydrotropes, ~or example, ~odium xylene sulfonate and C~l dicarboxylic acids sold under the DiacidTM
trade name by Westvaco, and visco~ity ~odi~ier~ ~uch as cellulose d~rivatives, clays and gums.

The composition of the present invention ars made by a ~x-tur~ o~ th~ varloua ingredient~. How~ver, it is pre~erred to di6solve the stabilizer in th~ aqueous portion prior to addition of the organic ~olvent.

Th~ present l~vent~on 1~ ~urther illustrat~d by th~ examples which follow.

Xxam~le ~

The ~ollowing composition~ A to H and AA to ~H were prepared:

TABL~ ~

Con~tituent _ C~centration. wt. %
A ~o H AA to HH
EthylenG glycol n-butyl ether(l) 10.0 10.0 Sod~um dodQcyl ~nzene ~ulfonat~ 0,047 0,047 Fluorad FC 171~ 0.01 0.01 Acetic acid 0.05 0,05 Dy8 ~ Per Table II >
Potassium Iodide 0.003 o Perfume 0.01 0.01 Water Q.S. Q.S.

(1) Ektasolve*EB manufactured by Eastman Chemicals Company.
(2) 100~ activ~ nonionic ~luorocarbon surfactant manufactured by 3M Company.

The dyes included ~n the compositions of Table I are identi-~ied below ln ~abl~ II. The pH o~ these compositions was about 4.

~A~
~QmposltlQn ~ye I.~. No. Concentration. wt.
A, AA 1 0.00083 B, BB 2 0.002 C, CC 3 0.002 D, DD 4 0.00026 ~, E~ 5 0.0043 F, FF 6 0.0008 a, GG 7 0.002 ~, HH 8 ~.002 1. Hidacid Fast Light Yellow 2G manu~actured by ~lton-Davis ~ompany (C.I. No. 18,965~ Acid Yellow 17).
2. Nylosan YQ110W N-7G~ manu~aatured by Sandoz Chemicals, Inc.
~Acid Yellow 218).
* Trad2marks ,i : ' . , .

.
"' ~

': ~ ' ' ' .

3, Sandolan Yellow P5G manufactured by Sandoz Chemicals, Inc. ~Acid Yellow 40:1).

4. FD&C Yellow No. 5 manufactured by Hilton Davis Company (C.I. No. 19,140: Acid Yellow 23~.

5. Drimarene Brilliant Green X-3G manufactured by Sandoz Chemicals, Inc. (Reactive Green 12).

6. Pyrazol Fast Turquoise GLL manufactured by Sandoz Chemlcals, Inc. ~C.I. No. 74,180; Direct Blue 86).

7. Basantol Green 910 manufactured by BASF Wyandotte Corp.
~Acid Green 26).

8. Cibaoron Yellow GA manufactured by Ciba-Geigy Corp~
(Reactive Yellow No. 6).

From Tables I and II, it is seen that compositions A, AA: B, BB;
C, CC: etc., are paire~ sets, each composition in a ~et incorporating the same dye at ~he same concentratio~, tha compositions A to H
within the scope of the present invention including 30 ppm of the pota~3ium iodide and the co~position~ AA to H~ out~ide the scope of th8 present invention being potas~ium iodide ~reQ for~ula~.

Tha paired compositions A, AA; B, BB; C, CC; etc., were evalu-ated ~or dye stability. 5amples o~ each composition were placed in polyvinyl chloride bottles, two samples of each compo~itlon being stor~d at lOO'F ~or 90 days and two of each compo~ition belng stored at 125'F ~or 28 day9. Absorbance measurement~ were made initi~lly and at thQ end of the storage period. The result~ o~ these evalua-tion~ are reported in Table III, as an average o~ the two samples for each test composition.
* Trade~arks , : , ! . ;; : . , " ' ' ` :'., : '' : ` '' `, ~` ' ~ ', : ' , :

1 328~83 Storag~ in PVC --Inltial Percent Ab.sorbance Remainina Com~Q~t~on ~bsorbance* A~ter gO D~y~ ~t~r 28 Days A 0.312 81.1 92.0 AA 0.30S 1.31 14.4 B 0.314 77.1 ~3.6 BB 0.310 1.29 14.2 C 0.41g ~6.6 ~3.8 CC 0.412 5.B3 11.9 D 0 .167 76 . 6 87 . 4 DD 0.173 2707 14.5 E 1.151 34 . 8 26 . 9 EE 1.185 0.25 1.43 F 0.166 5.42 6.63 F~ 0 .161 0 . ~2 3 . 73 G 0.463 28.3 34.6 GG 0.435 2.76 3.91 0 . 385 85 . 7 89 . 1 H~ O . 376 1 . 33 4 . 52 .

*Absorbanc~ measurementE~ were ~ad~ at 410 ns~ ~or co~position~ A
to D; M to DD; H and HH. A~sorbance ~easur~ments for compos~tion~ ~ to G and ~SE to GG were mad~s a~ 660 n~.

81TQilar evaluations o~ dye stability were conducted ~n glass contalner~, th~ re~ult~ being 6et forth in Tabls IV below.

l 32~3 TABLE IV

Stora~e in Çlass _ Percent Absorbance Remain~n~
Çomposition Absorbance* ~fter 90 Day~ A~ter 28 Days i A 0.312 93.3 85.6 '~ AA 0.305 69.5 10.8 , .
0.314 92.4 ~Ç.9 I B~ 0.310 ~8.4 10.6 3 ~ 0.419 9403 89.3 CC 0.412 67.~ 8.9 i D 0.167 99.4 82.6 i! DD C.173 20.8 17.3 d, E 1~51 34.7 34.3 i EE ~ 5 1.7 2.53 J, :i F 0.166 19.3 21.1 EF 0.161 1204 lB.6 G 0.463 32.2 40.2 ~i eG ~.435 6~ 9.2 `~ X 0.385 97.1 91.2 HH 0.376 11.1 10.4 .

~Absorba~ce measurements were mad~ at the same wavelengths a~ ln Tabl~ III.

.. . .

,, "

i, .
.. ..
;

~xamP-le 2 The following compositions* were prepared.

Constituent _ _ _ Concent~a~ion, wt. ~b J ~J

Ethylene glycol n-butyl ether(l) 22.0 22.0 ~sopropyl alcohol 8.0 8.0 Sodium lauryl ~ulfats 0,45 o.45 Ammonia as NH~ 0.13 0.13 Pyrazol Fast ~urquoise ~LL 0.0032 0.0032 Potassium iodide 0.0068 0 Perfume 0.0~ 0c08 Water Q.S. Q.S.

(l)Ektasolve E~

The palred composltions J, JJ were tested ~o~ 8tability in P~C and glas~ conta1ners, in accordance wtth ~xample 1~ Absorb-ance readings were ~ade at 660 nm. It i8 noted that in this ex-ample, in vtew o~ th2 hi~h ehtylsne glyool n-butyl ether level, peak absorbance occur~ at 670 n~. ~Iowever, th~ data 6et forth in Table VI is suitable to assess the 6tability o~ th~ dy~
following ~torag2 ~ compared to th~ initial absorbanc~ v~lue~.
The pH o~ khesQ co~po6itions wa~ about 11.

, -~ 3 ~

TABLE VI

Percent Absorb.a~ce Reaminin~
Com~osition _ Absorbance _ _ After_90 DaY~ After 28 Days PVC -J 1.68 90.5 83.9 J~ 1.6~ 51.7 51.3 Glass:
J 1.6~ 88.7 98.7 JJ 1.68 82.1 50.5 :

~he letter I has not been u6ed to ldentify compositions, to avoi~ con~uslon.

~ .

- . ~ .. . . . . - .. ... .

~ 328~83 Example 1 Compo~ition~ K and K~C wer~ prepar~d. Composition K was the ~ame as composit~on J, except 0.0065% 60diu~ thlosul~ata wae incorporated in lleu o~ 0 . 0068% potassium lodlde. In both compositions ~ and KX, the amount o~ water wa~ Q. S ~ 100% .

Stablllty test~ were conducted in accordanca with Examples 1 and 2, wlth absorbance measurement~ taken at 660 nm, except that storage wa~ conducted only ~t 125F ~or 28 day~ in Pt'C
~nd gla~s container~ . In PVC containars 75 . 8~ ab~orbance remained for compos~t~on R ver~u~ 51.3~6 ab~orbance re~alnlng for compoE~ition KK. Sl~llarly, in glas~ containers 75.1% ab~orbance ramained ~or composition ~ ver~u~ 50.5% absorbancs re~ainlng Por compo~i~lon XK.

~ca~pl~ 4 The compositions o~ the present invention were evaluat~d for their abillty to control ~he for~atlon of of~E-odor~ wherl contained ln a PVC ~ontalner. ~h~ i~ollowing compo~ition~ ware prepared:

.
.1 :

. :
.~

:; .. :

1 3~8283 TAB~ VI I

Constituent _ Concentration. wt_%

Ethylene qlycol n-butyl ether ( 1) 10 . 0 10 . 0 Sodium dodecyl benzene sulfonate 0. 047 o. 047 Fluorad FC-171 0 . 01 0 . 01 Acetic acid 0. 05 0. 05 Dye:
Drimarene Brilliant Gxeen X-3G 0. 0043 0. 0043 Pyrazol Fast Turquoise GLL 0. 0002 0. 0002 Potassium Iodide o . 003 o Perfume <~ Per Table VIII >~>
Water QO ~ Q. S .

(1) Ektasolve EB

TABL 3 ~II

o~Po~1tlon . Per~u~e onoentration, wt. %
~, ~ ~ ~
~, ~SM P~rfume No. 1 . 0.01 ~, NN Perfume No. 2 O. ûl rhe compo~ition~ L to N and IL to NN were placed in PVc con-tainer~ asld ~tored at 140-F for one week, after which pan~list~ wer4 required, in blind comparison~, to ~el~ct the paire~ te~t cor~tainer with the mo~t off-odor. ~he results are ~et forth in ~able IXo ;

~ 3~283 ~ost o~-odors 5Qm~r~ cg No, ~ ~udo~ent~
L O
~L 40 M O
~M 4 : N
' NN 40 .
Ex~mple S.

The co~po~ltion~ ~, EE and H, H~ wer~ comparatively tested ~i~h respect to cleaning performance~

tegt ~ur~ac~ to b~ cleaned wa~ soiled unl~ormly and ~her~-~`~ a~t~r divided into equal ~ctions. One 8~ation was ~l~aned with th8 COmpOfiitiO~ 0~ the pre6ent invention; the oth~r section with :i~ the compo~ition out~ide the 8cope 0~ th~ present in:Y~nt~ on.
.~ Cl~aning wae conduct2d by applyin~ a uni~orm spray of the ~ cl~aner to the ~ection, allowing the cleaner to contact the 80il .: for 30 ~econds, and th~n wiping th~ section with a lint ~ree cloth ~or 10 cycle~ and c~anging to a dry cloth Por 10 addi-'.~ tional ayale~ on a Garden~r Washability ~achin~. Paneli~t~ were `~ ~ then required to ~el2c~ th~ aleaner ~ection o~ thæ palr in a blind aompari~on. ~hQ re~ult6 are tabulated in Tabl~ X.
* Trademark . 2 7 :
1 32~283 T~L~ X

~leaner 81de co~t)o6ition ~ur~ac~ No. Q~ Jud$lments ~: ~las~ Fed. Spec. So~ 1 41 131~ P-G~406D* 19 ~I Gla~s Fed. Spec:O Soil 38 40~ 3~
~I ~alced En~mel ~ed. SE~ec. Sc~il 46 H~ P-G-406D 14 *CS1~A De~ignation DDC-09, l~ay 1983.

The ~bov~ datailed descrlption i~ not lntended to b~
li~lting o~ . cop~3 o~ ths inventiorl as provided in ~e clai~s app~nded belowO wherein all recited concentrationE ~re on an ~cti~rs constituent 3~a~is.

Claims (58)

1. A cleaning composition comprising on a weight basis up to about 50% of a higher boiling glycol ether solvent, said solvent introducing impurities into the composition in an amount and of a nature normally chemically incompatible with oxidizable dye chromophores; a dye present ill an amount of at least 0.0001% to provide a desired tinctorial value and including an oxidizable dye chromophore; a stabilizer selected from the group consisting of salts of iodide and thiosulfate anions in an amount effective to retard fading of the dye; from about 0.001 to about 5% of a surfactant, and water, said composition having a basic or neutral pH when the stabilizer is the thiosulfate salt.

2. The composition of Claim 1 wherein the stabilizer is a salt of a sodium, potassium, ammonium, calcium, magnesium, barium, or iron (II) cation.

3. The composition of Claim 1 wherein the higher boiling solvent is present in an amount of from about 2 to about 30% by weight of the composition.

4. The composition of Claim 3 wherein the impurities are present in an amount of from about 0.001 to about 0.25% by weight of the composition.

5. A cleaning composition comprising on a weight basis from about 2 to about 50% of a C1-C4 alkyl ether of alkylene and polyalkylene glycols, said glycol ethers having a total of from 3 to about 12 carbons and introducing impurities into the composition in an amount and of a nature normally chemically incompatible with oxidizable dye chromophores; from about 0.0001 to about 0.1% of a dye to provide a desired tinctorial value and including oxidizable dye chromophores; a stabilizer selected from the group consisting of salts of iodide and thiosulfate anions in an amount effective to retard fading of the dye; from about 0.001 to about 5% of a surfactant, and water, said composition having a basic or neutral pH when the stabilizer is the thiosulfate salt.

6. The composition of Claim 5 wherein the stabilizer is a salt of a sodium, potassium, ammonium, calcium, magnesium, barium or iron (II) cation.

7. The composition of Claim 5 wherein the glycol ether is present in an amount of from about S to about 30% by weight of the composition.

8. The composition of Claim 7 wherein the impurities are present in an amount of from about 0.001 to about 0.1% by weight of the composition.

9. The composition of Claim 7 wherein the glycol ether is selected from the group consisting of ethylene glycol monobutyl ether; propylene glycol monoethyl ether; diethylene glycol monoethyl ether; diethylene glycol monobutyl ether; tripropylene glycol monomethyl ether; tetraethylene glycol dimethyl ether; .beta.,.beta.-dihydroxydiethyl ether, and ethylene glycol di-.beta.-hydroxyethyl ether.

10. The composition of Claim 5 wherein the dye is selected from the group consisting of Colour Index Nos. 19,140; 18,950:1; 18,965; 74,180;
42,090; 52,035; Acid Yellow 218; Reactive Green 12; Reactive Yellow No. 6;
and Acid Green 26.

11. The composition of Claim 5 further comprising a pH modifying agent in an amount effective to provide a desired pH.

12. The composition of Claim 11 wherein the pH modifying agent is an acidifying agent which is a low molecular weight carboxylic acid.

13. The composition of Claim 12 wherein the acid is acetic acid.

14. The composition of Claim 11 wherein the pH is between about 2.5 to about 5.5

15. The composition of Claim 11 wherein the pH modifying agent is an alkalizing agent which is a hydroxide base.

16. The composition of Claim 15 wherein the base is ammonia.

17. The composition of Claim 15 wherein the pH is between about 8.5 to about 11.

18. A cleaning composition comprising on a weight basis from about 5 to about 15% of a C1-C4 alkyl ether of alkylene and polyalkylene glycols, said glycol ethers having a total of from 3 to 12 carbons and introducing impurities into the composition in an amount and of a nature normally incompatible with oxidizable dye chromophores; from about 0.0001 to about 0.10% dye, said dye including oxidizable dye chromophores; an iodide salt in an amount of less than about 1000 ppm, the iodide being in an amount effective to retard fading of the dye; from about 0.001 to about 5%
of a surfactant selected from the group consisting of anionic and nonionic surfactants, and water.

19. The composition of Claim 18 wherein the iodide is a salt of a sodium, potassium, or ammonium cation.

20. The composition of Claim 18 wherein the glycol ether is present in an amount of from about 7 to about 12% by weight of the composition.

21. The composition of Claim 18 wherein the impurities are present in an amount of from about 0.001 to about 0.1% by weight of the composition.

22. The composition of Claim 18 or 21 wherein the C1-C4 alkyl ether of a glycol is selected from the group consisting of ethylene glycol monobutyl ether; propylene glycol monoethyl ether; diethylene glycol monoethyl ether; diethylene glycol monobutyl ether; tripropylene glycol monomethyl ether; tetraethylene glycol dimethyl ether; .beta.,.beta.-dihydroxydiethyl ether; and ethylene glycol di(.beta.-hydroxyethyl) ether.

23. The composition of Claim 18 wherein the dye is present in an amount of from about 0.0005 to about 0.01 by weight of the composition, the dye being on an active basis.

24. The composition of Claim 23 wherein the dye is selected from the group consisting of Colour Index Nos. 19,140; 18,950:1; 18,965; 74,180;
42,090; 52,035; Acid Yellow 218; Reactive Green 12; Reactive Yellow No. 6;
and Acid Green 26.

25. The composition of Claim 18 further comprising a pH
modifying agent in an amount effective to provide a desired pH.

26. The composition of Claim 25 wherein the pH modifying agent is an acidifying agent.

27. The composition of Claim 26 wherein the acid is acetic acid.

28. The composition of Claim 18 or 27 wherein the pH is between about 2.5 to about 5.5

29. The composition of Claim 25 wherein the pH modifying agent is an alkalizing agent.

30. The composition of Claim 29 wherein the alkalizing agent is ammonia.

31. The composition of Claim 18 or 30 wherein the pH is between about 8.5 to about 11.

32. The composition of Claim 4, 8, 18, 21 or 24 wherein the impurities include one or more of the following: butyl butal; 2-hydroxyethyl butyrate; butoxyacetic acid; n-butraldehyde; butyl formate; 2-butoxyacetaldehyde; 1-(1-hydroperoxy-2-hydroethoxy)butane; 1-butoxy-2-hydroxy-1-ethyl peroxide; 1-(2-hydroethoxy)-1-hydroperoxy butane; and 1-(2-hydroxyethoxy)-1-butyl peroxide.

33. The composition of Claim 18 wherein the surfactant is present in an amount of from about 0.01 to about 1%.

34. The composition of Claim 18 wherein the surfactant is a fluorocarbon surfactant present in an amount of less than about 0.1%.

35. The composition of Claim 18 wherein the surfactant is a surfactant mixture including a fluorocarbon surfactant present in an amount of less than about 0.1%.

36. The composition of Claim 33 or 35 wherein the surfactant is selected from the group consisting of sodium dodecyl benzene sulfonate and sodium lauryl sulfate.

37. The composition of Claim 1,5 or 18 in ready-to-use form.

38. The composition of Claim 1,5 or 18 in concentrate form.

39. In a cleaning composition comprising on a weight basis up to about 50% of a glycol ether solvent, from about 0.001 to about 5% of a surfactant, and water, said composition further comprising an amount of one or more chemical species causing a malodor, the improvement comprising a stabilizer selected from the group consisting of salts of iodide and thiosulfate anions in an amount effective to substantially neutralize said malodor, said compositions having a basic pH when the stabilizer is a thiosulfate salt.

40. The composition of Claim 39 wherein the stabilizer is an iodide salt selected from the group consisting of sodium iodide, potassium iodide, ammonium iodide, lithium iodide, calcium iodide, and magnesium iodide.

41. The composition of Claim 40 wherein the solvent is present in an amount of from about 5 to about 15% by weight of the composition.

42. The composition of Claim 41 wherein the solvent is a C1-C4 alkyl ether of alkylene and polyalkylene glycols, said glycol ethers having a total of from 3 to about 12 carbons.

43. The composition of Claim 42 wherein the glycol ether is selected from the group consisting of ethylene glycol monoethyl ether;
ethylene glycol monobutyl ether; propylene glycol monoethyl ether; diethylene glycol monoethyl ether; diethylene glycol monobutyl ether; tripropylene glycol monomethyl ether; tetraethylene glycol dimethyl ether; .beta.,.beta.-dihydroxydiethyl ether; and ethylene glycol di-.beta.-hydroxyethyl ether.

44. The composition of Claim 39 or 43 further comprising one or more of the following adjuvants: dye, perfume, builder, hydrotrope, and pH
modifying agent, said one or more adjuvants being present in an amount effective to provide its intended function.

45. The composition of Claim 39 or 43 wherein the stabilizer is in an amount of less than about 100 ppm.

46. The composition of Claim 1, 5, 18 or 39 contained in a polyvinylchloride container.

47. In a cleaning composition suitable for use on hard surfaces comprising on a weight basis up to about 50% of a glycol ether solvent, from about 0.001 to about 5% of a surfactant, and water, the improvement comprising a stabilizer selected from the group consisting of salts of iodide and thiosulfate anions in an amount of less than about 0.1% by weight of the composition, said compositions having a basic pH when the stabilizer is the thiosulfate salt, whereby cleaning performance of the composition is enhanced.

48. The composition of Claim 47 wherein the stabilizer is an iodide salt selected from the group consisting of sodium iodide, potassium iodide, amrnonium iodide, lithium iodide, calcium iodide, and magnesium iodide.

49. The cvmposition of Claim 48 wherein the solvent is present in an amount of from about 2 to about 15% by weight of the composition.

50. The composition of Claim 49 wherein the solvent is a C1-C4 alkyl ether of alkylene and polyalkylene glycols.

51. The composition of Claim 47 or 50 wherein the stabilizer is present in an amount of less than 100 ppm.

52. A process to counteract the destabilizing effect of impurities present in a glycol ether solvent which is an alkyl ether of alkylene and polyalkylene glycols includable in compositions containing a destabilizable constituent comprising adding to said glycol ether an impurity-neutralizing stabilizer selected from the group consisting of salts of iodide and thiosulfate anions, the compositions being basic when the stabilizer is a thiosulfate salt.

53. The process of Claim 52 wherein the stabilizer is an iodide salt.

54. A process to counteract the malodorous effect of an interaction of impurities present in a glycol ether solvent which is an alkyl ether of alkylene and polyalkylene glycols with polyvinylchloride containers comprising including with said glycol ether contained in the polyvinylchloride container a malodor-neutralizing stabilizer selected from the group consisting of salts of iodide and thiosulfate anions, the contents of the container being basic when the stabilizer is a thiosulfate salt.

55. The process of Claim 54 wherein the stabilizer is an iodide salt.

56. The process of either one of claims 39 or 54 in which the stabilizer is less than 1000 ppm.

57. The process of claim 51 in which the stabilizer is less than 1000 ppm.

58. The composition of any one of claims 1, 5 or 18 in which the stabilizer is from about 0.001 to about 0.1%.