CA1071969A - Alkaline detergent compositions - Google Patents

Abstract

Abstract of the Disclosure This invention discloses alkaline detergent compositions for cleaning solid surfaces including returnable food and beverage containers such as are used for milk, ice cream mixes, soft drinks and similar materials. The alkaline detergent compositions are particularly adapted for cleaning bottles fabricated from polycarbonate resins without damaging the polycarbonate but are also useful on glass, polypropylene and polyethylene surfaces.
Granular detergents, aqueous concentrates and aqueous use solution are described. The alkaline detergents can be used in mechanical spray or soak-tank washers.

Description

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~ ., DESCRIPTION OF INVENTION
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The deslre to use a clear glass-lllce polymer that doesn' t break has led to the development of poIycarbonates whlch can be formed Into sheet, fllm, plate or whlch can be molded Into artlcles. The preparation and propertles of these polymers are descrlbed In the Encyclopedla of Polymer Technology, Volume 10 beginnlng on page 710. Slnce polycarbonates are essentlally llnear thermoplastic polyesters of car~onlc acid, they are readlly susceptlble to chemlcal attack by free alkall.
On the other hand, glass contalners and processlng equlpment presently In use In the dalry Industry In contact wlth mLlk, Ice crean and other mllk products requLre free alkalL at a pH of ahout 13 to peptlze the fatty acld soLls whlch enables them to be removed by detergent actlon.
Another type of soll encountered Ln the daLry fleld are the usual contamlnatlng molds whlch grow on the soLled food contalner walls. Removal of soLls In the dalry Industry requlre strong alkaline detergents and cleaners whlch wlll perform satlsfactory In elther mechanlcal spray or soak-tank cleanlng operatlons.
Glass contalners such as glass mLlk bottles frequently break with resultlng Lnjury to both daky personnel and the milk consumer. Thls has let to the use of polypropylene, polyethylene and polycarbonate returnable food contalners.

.' . .: ' ~ ~ 7 ~ 96 9 The use of smooth, clear and transparent polycarbonate milk containers has, in the past, been unsuccessful due to chemical at-tack by conventional bottle cleaners employing strong alkali.
I have now discovered alkaline detergent compositions for use in aqueous solution which will clean soiled surfaces. These detergent com-positions will peptize fatty acid soils in food products such as milk at a pH of about 8 to 12. Repeated washings of 75 cycles or more have de-monstrated that these new alkaline compositions do not attack polycarbonate, polypropylene, polyethylene or glass surfaces.
The basis of my new cleaning composition is an organic dicarboxylic acid detergent represented by the formula /CH=CH

C~3( 2)5 \ /CH-~CH2)7R
fH-CH
,~ ,X ~
in which one X is hydrogen while the second X is carboxylic, in which R can be COOH and CSO4H and their.alkali metal saLts. For convenience, I use the term C-21 dicarboxylic detergent to include the free C-21 dicarboxylic acid, the sulfate derivative and their sodium or potassium salts. The preparation of C-21 dicarboxylic acid is described in U.S. 3,753,968~
The C-21 dicarboxylic ac:Ld sulfate is prepared by sulfating the C-21 dicarboxylic acid by conventional sulfating techniques. Generally, from one-half to one and one-half moles of concentrated sulfuric acid will be added to each mole of C-21 dicarboxylic acid. It is believed that most of the sulfation will take place at the terminal carboxylic group in preference _ 3 _ ,: . . , ~ ' ' , ' . :
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to the carboxyl'lc group attached to the cycllc portlon of the molecule.
However, It Is posslble that some sulfatlon will take place at each carboxyllc group. ' The alkall' metal salt's of the C-2 1 cllcarboxyllc acld wlll be formed by the substltutlon of alkall metal, preferably sodlum, for the hydrogen on the hydroxyl groups of the carboxylLc groups. The source of the alkall metal w~lll be the free alkall In the alka11ne materlals such as sodlum meta-sLllcate and sodlum carbonate. Some of the substltutlon of sodlum for .5~, hydrogen wLll take p}ace In the dry blendlng operatlon when the detergent composltlon Is formulated. The substltutlon w111 be completed when elther the aqueous concentrate or dllute use solutlons are prepared.
The alkallne cleanlng composltlons of my lnventLon are formulated as dry granular composltlons whlch are dlssolved In water for the cleanlng operatlon. Aqueous concentrates can also be prepared but are not generally ls used because of the expense of transport~ng water. l~e followlng , dsscrlptlon of my composltlons will refer to the granular concentrates unless " otherw~lse speclfled.
The C-21 dlcarboxylic dstergent wlll be prssent In my granular dete~gent composltions at from about 1 to about 9 percent by welght.
Preferably the C-21 dlcarboxyllc dstergent concentratlon wLll be about 5 to 7 percent by welght in concentrates for soak tank cleanlng and from about 1 to 2 percent by welght for spray appllcations.
The free alkali requlred to peptLze the fatty acld resldues from mllk and Ice cream soll Is'principally supplled by alkal'l bullders in my detergent composltlons~ The alkall bullders wlll be present wlthln the range of about ,",~,, ''" .

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10~96g 5 to 28 percent by weight. Preferably, the alkali builder wlll constitute from about lO to 20 percent by ~eight in concentrates for both the soak tank or spray cleaning.
The alkali builders are members of an alkali metal silicate group consisting of sodium metasilicate, potassium metasilicate, sodium ortho-silicate, potassium orthosilicate and mixtures thereof. These alkali metal silicate builders are available in either anhydrous or hydrated form.
Whenever alkali metal silicate builders are used in the specifications and claims, they are expressed in the anhydrous form unless otherwise specified.
In addition to the C-21 dicarboxylic detergent, detergent action is supplied by alkali metal phosphates which act synergistically with the C 21 dlcarboxyl:lc de~ergent in my cleaning composltlon. Additionally, t~e fl:Lkall metal phosphates wlll act ag water softenlng agents by se-ue~tering calclum nnd magneslttm ions in the cleanlng water.
The alkali metal phosphates which are used in my ~letergent composition are supplied by one or more alkali metal phosphates from the group conslsting of sodium tripolyphosphate, trisodium phosphate, tetra-sodium pyrophosphate, tetrapotassium pyrophosphate and sodlum hexa-metaphosphate. The alkali metal phosphates are used at a concentration of about 5 to 27 percent by weight. For soak tank cleaning, a preferred range oE alkali metal phosphate is about lO to 20% by weight while for spray applications the preferred concentration range is abo~tt 15 to 27% by weight of the concentrate.
Another class of ingredients often used in my detergent compositions is detergent builders. Examples of detergent builders which assist in supplying alkalinity to the composition are sodium sequicarbonate, sodium ., : : . : . . ~ . : -: , .. ... .:.: ' . .. . .
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sesquisilicate, sodium carbonate, sodium bicarbonate and urea. In addition to supplying alkalinity the detergent builders may be useful in helping to suspend, disperse or emulsify soil and in peptizing fats and greases. Certain types of detergent builders in my compositions, such as sodium chloride and sodium sulfate, function as builders due to their great solubility in water with the resulting common ion effect. One or - more of the above detergent builders may be used in my detergent con-centrates at a concentration of from zero to about 83 percent by welght.
The preferred concentration of detergent builder in my soak-tank cleaner will be about 28 to 62 percent by weight while the preferred range for my spray composition will be about 30 to 63 percent by weight of the con-centrate.
In order to assist the C-21 dlcarboxyllc detergent to penetrate the heavy solls encountered, partlcularly ln cleaning mllk and ice cream container~, t have ~ound lt necessary to use from about 1 to 15 percent by welght of a hydrotrope and penetratlng agent whlch ls a polynuclear methyl naphthalene sulfonate alkali metal salt having a molecular weight within the range of about 2~0 to 260. The methyl naphthalene sulfonate is gen-erally supplied as the sodium or potassium salt and may be a sodlum or pot-assium mono-methyl or dlmethyl naphthalene sulfonate or mixtures thereof.
The sodium salt is cheaper, more generally available and is preferred. -Thls materlal i8 commerclally avallable under the trademarks PETRO II and PETRO M sold by Pe~rochemlcals Co., Inc., TAMOL SN sold by Rohm and }laas Co. and ~EKAL N.F. sold by GAF Corporation. A preferred concentration range of alkali metal methyl naphthalene sulfonate is from about 5 to 10 percent by weight of my soak-tank detergent concentrate. For spray applications ~ .

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~) 10~1969 the preferred range Is about 2 to 5 percent by welght of the concentrates.
If addltlonal surface actlve agents are deslred In the cleanlng composLtLon conventlonal wettLng agents, emulslfylng agents and dlsperslng agent s can be added along wlth the alkall metal methyl naphthalene sulfonate~
I have used from about 0. 5 to 5 parts by we~ght of a surface actlve agent wlth 99; 5 to 95 parts by welght of my granular concentrates. The surface actlve agents can be selected from any of the hundreds of avallable materlals 3 so long as they functlon In alkallne solutlons, The surface actlve agents i3 may be present at a concentratlon of zero to flve percent by weight, Thesurface actlve agents useful In my detergent composltlons w~ll Include the nonlonlcs, the anlonlcs and the amphoterlcs. Examples of non~onIcs are octylphenoxy polyethoxy ethanol sold under the trademark TRITON X-45, ,, ~ nonyl phenoxy ethyleneoxy ethanol sold under the trademark IGEPAL CQ 850, phenoxy ethoxylated ethanol sold under the trademark EMPHOS TS-211, polyoxyethylene ester of mlxed fatty and resln acids sold under the trademark RENEX 20, glycol fatty ester sold under the trademark HALLCO-376-N, fatty acld glycol ester sold under the trademark ADVAWET 33, fatty acld alkanolamlde sold under the trademark AI~AMIDE 2110, cetyl dlmethyl amlne ox~de sold under the trademark AMMONYX CO, allphatlc polyether sold under the trademark AN CAROX LF-344, polyoxyethylenated alkyl glycol - amlde sold under the trademark ANTAROX G-200, fatty alcohol polyether sold under the trademark AROSURF ù3-PE-16, polyoxyethylene sorbl.ol esters of mlxed fatty and resln acids sold under the trademark ATI~S G-1234, , ~
modlfled oxyethylated stral~ht-chaln alcohol sold under the trademark PLURAFAC D-25 and ethoxylated nonyl phenol sold under the trademark RENEX 648.

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Examples of amphoterics are dlsodlum N-tallow betamlno dlpropionate sold ullder t~e trademark DERIPHATE 154, sodlum derlvatlve of dlcarboxyllc caprylLc acid sold under the trademark MIRANOL J2MJ leclthin sold under the trademark C:ENTROL CA, LA, lauryl amphol~tlc (syndet) sold under the . S trade~rk. ~:EERCOTERIC BASE 156, carboxyllc acld derlvatives of substLt~ted imIdazolines sold under the traclemark MONATERIC, complex coco betal~ so.l'~ ~nder the trademark ACCOBE~CAINE CL, D~ocyl am~do betalne sold url~er t~e 1:rademark CARSONAM 3 and 3147, fatty sulfobetalne sold . under ffle tr~demark LONZAINE CS, d~carboxyllc coconut dertvatLve Isopro-panol~m~e sold under the trademark MIRANOL IPA, dlcarboxyllc coconut derlvatl~.re tr~e~anolamlne sold under the trademark Ml~ANOL TE~, . dlcarhoxyllc coconut derlvatlve sodlum salt sold under the trademark MIRANOL SFJ dlcarboxyllc octola derlvatlve sodlum salt sold under the trademark. ~.IR~NOL JEM, dLcarboxyllc myrlstlc derlvatlve dlethanolamlne sold under tEIe ~trademark MIRANOL M2M-DEA, dlcarboxyllc myrlstlc derlv-! atlve monoe~E anolamlne sQld under the trademark MIRANOL M2M-MEA, : . I:~ dlcarboxyll.~ myrlstlc derLvatlve sodlum salt sold under the trademark .. MIR~OL M~M-SF, dlcarboxyllc carboxyllc caprlc derlvatlve dlethanolamlne . sold under the trademark MIRANOL S2M-DEA and dlcarboxyllc caprlc . 20 derlvatlua tr~ethanolamlne sold under the trademark MlRANOL S2M-TEA.
Examples of anlonlcs are ethoxylated (3 moles) phosphate ester sold under t~e tr.a~emark TRITON QS-44, sodlum sulfate of 2 ethyl-1-hexanol sold un~ler t~e t~demark TERGITOL 08, sodlum petroleum sulfonate sold under the tradelTIarÇ; PETRONATE K, sodlum alkyl naphthalene sulfonate sold under the trademark P~iRO AR, SELLOGEN K, NEKAI, BX-78, ALKANOI. B and others, .

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dloctyl ester of sodlum sulfosucclnLc acld sold under the trademark AEREsoL OT
sodlum alkylaryl sulfonate sold under the trademark AHCO~ET ANS sodlum salt of sulfated aL~cylphenoxy poly (ethyleneoxy) ethanol sold under the trademarkALIPAL EO-526 sodlum methyl n-oleyl-taurate sold under the trademark A~TERG T alkyl polyphosphate sold under the trademark ATCC)WE~ C2 sodlum lauryl sulfate sold under the trademar~c AVIROL 101 sodlum N-mefflyl-N-tall oll aclds taurate sold under the trademark IGEPON
TK-32 l~urlc aL~lolamlne condensate sold under the trademark NOPCC~EN
14-L fatty alcohol sulfate modLfled sold under the trademark RICHONOL
4740 and modlfled dlethanolamldes of fatty aclds sold under the trademark SHERCOMID~
Th~ comblned amounts of alkall metal methyl naphthalene sulfonate a~nd surface actlve agents wlll not exceed about 20 percent by welght of the aL~callne detergent concentra tes.
TEle C-21 dlcarboxyllc detergents and the sodlum methyl naphthalene sulfonate tend to Induce foamlng characterlstlcs In the dllute aqueous solut~ons of my detergent composltlons partLcularly when sprayed. If thls foamlng is undeslrable lt can be controlled by the use of about 2 to 6 , de ~ w~ ~cl percent by welght of a foam modlfyLng agent. The -f~mo~ agent may be used at a concentratlon rang~ng from 0 to about 6 percent by welght.
For soak-tank composltlons It wlll generally be used at a concentratlon of about 3 tCI 5 percent In the detergent concentrate whlle a preferred concentrat~on for spray cleaners Is about 4 to 6 percent by welght. The ~e~\t~
~ agent can be selected from any of a number of products avallable for thls purpose Lncludlng mLxtures thereof the only requLrement i , . ~ , .
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being that the defoaming agents be effective under the alkaline condltions in which my cleaner composition ls formulated and used. In those applications where foam is desired or can be tolerated then a defoaming agent is un-necessary.
The defoaming agents may be selected from the groups consisting of mineral oils, vegetable oils and organic defoaming agents. Suitable defoaming agents include white mineral oils sold under the trademarks DRAKEOL 5, 10, 21 and 35; fatty acid vegetable oil sold under the trade-mark PAMOLYN, and organic materials such as modified oxyethoxylated straight chain alcohols, such as the PLURA~AC* RA20, RA30, RA40, and RA43; alkyl-aryl polyether sold under the trademark TRITON CF10; trifunctional poly-oxyalkylene glycols such as PLURADOT* ~IA410 and ~IA430; diethylene glycol dloleate, polyethylene glycol recinoleate, polyethylene glycol dioleate, trldecyl alcohol, nonylphenol, and ethylene oxide condensatlon product wlth propylene oxide - propylene glycol base such as the PLURONIC* L61, L62LF, L81 and L122.
I have found it desirable in my detergent concentrates to use sodium bicarbonate as a buffering agent and I use about 5 to 15 percent by welght of this material. A preferred concentration of sodium bicarbonate is from about 5 to 10 percent in both my soak-tank cleaners and spray cleaners.
I have found it convenient to sell my detergent compositlon as granular solid compositions. They are, of course, readlly soluble in water and aqueous concentrates containing up to 40 percent by weight of the detergent are also available. The aqueous concentrates are amber colored.
The range of the above ingredients in my granular detergent compositions are shown below in Table I.

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These materials are dry blended in conventional ribbon or other type blenders. If the C-21 dicarboxylic detergent is the free dicarbo~ylic acid or a free sulfate these materials will react with the sodium present in the alkalis or detergent builders to form the sodium salts. Complete reaction at the blending stage is unimportant since the free alkali in the aqueous use solutions will reac~ with any remaining acidic groups.
My granular detergent compositions are used in water at a concentration ranging ~rom about 0.25 to 5 percent by weight.
For soalc-tank cleaning where difficult to remove soil is en-countered such as ice cream mixes and food molds, I find it desirable to use a concentration of about 3 percent by weight of my detergent in water.
Concentrations as high as 5 percent by weight can be used -If necessary for particular applications where extremely heavy 80il iS encountered. As lndicated previously, a high pH is required for peptiz:Lng fats in food and my cleanlng solutlons will have a pH of about 8 to 12. Preferably the pH of the use solutions will be about 10 to 11. For cleaning polycarbonate milk containers in a continuous soak tank cleaning operation, I have used from about 1 to 3% by weight of my granular detergent composition in water.
For spray applications, I have used my granular concentrates in solutions ranging from about 0.25 to 5 percent by weight. Because of the pressure used in spray operations I have found that for most applications, the granular concentrates can be used at concentrations lower than required for mechanical soak-tank cleaning. For example, for spray washing poly~
carbonate windows the concentration of detergent in water will be from about 0.25 to about 0.5 percent by weight. For spray washlng polycarbonate ' : , . :.:
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, ' '' .' 1~7~969 and glass mIlk bottles I have used my granular concentrates at about l, 5 to 3 percent by welght, Cl,eanlng tlme wlll vary from a few seconds requlred In washlng polycarbonate sheets used as wlndows In rallroad cars and buses to about 30 mlnutes requlred Ln soak tank cleanlng.
. 5 The temperatures requlred for my aqueous cleanlng solutlons wlllvary from amblent temperatures for wlndow washlng to about 190F, for mechanlcal washlng machLnes" For soak tank cleanlng of polycarbonate mlLlc bottles, I use temperatures of about 150DF. For spray washlng of -:~ returnable mllk contalners r have used solutlon temperatures ranglng from 120 to 160F, The detergent solutlons can be sprayed on the artLcles belng cleaned or the articles can be Immersed In the aqueous use solutlons of my C-21 dlcar} oxyllc detergent, After the cleanlng operatlon the contalners are rlnsed wlth clean water whlch can be cold or hot as deslred.
After the soll has been removed and the conta~ners have been rlnsed wlth water, they can be sanltlzed by contactlng them wl~h water containlng about 200 parts per mllllon of chlorlne, Con~act with the aqueous chlor~ne .
solutlon may vary from about 30 seconds to several mlnutes, The , temperature of the chlorine sanLtizLng solutlon generally does not exceed 120F. because of lImlted chlorlne solublllty at hLgher temperatures, Followlng sanltlzlng, the food contalners are agaln rlnsed wlth clean water.
It Is also posslble to both clean and sanltlze contalners slmultaneously by lncorporatlng a compound whlch wLll llberate actlve chlorlne In aqueous , solutlon such as chlorlnated trlsodlum phosphate and the sodium and potassium salts of dlchlorolsocyanurLc acld. These sanltlzlng materlals when used are formulated to glve from 50 to 300 parts per millLon of . ' , . . . ..
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~ 6 9 available chlorine. In the granular concentrates from about 1 to 3 parts by weight of the dichloroisocyanurates are combined with about 99 to 97 parts by weight of granular concentrates. If I use the chlorinated tri-sodium phosphate, I combine about 5 to 12 p~rts by weight with about 9S
to 88 parts by weight of the granular concentrate.
I have also found it desirable to use cm antistatic agent in my cleaning solution when my C-21 dicarboxylic detergent is used in an im-mersion cleaning operation, such as in soak tank cleaning. The antistatic agent prevents the soil removed in the cleaning operation from redepositing out of solution onto the article being cleaned. An antistatic agent is not generally required in a spray cleaning application.
From about 0.5 to 2 parts by weight of antistatic agent will generally be combined with from 99.5 to 98 parts by welght Oe my C-21 dlcarboxylLc detergent concentrates. The antistatic agent, when req~lLed, ls added to the soak cleaning tank. Alternatlvely, the antlstatic agent ln the same proportions may be formulated as part of the C-21 dicarboxylic detergent sold in granular form or as a liquid concentrate. The antistatic agent can be any one or more of a large number of available materials, the principal requirement being that it be stable in the alkaline use solutions.
The nonionic and amphoteric antistatics are generally satisfzctory.
Typical nonionic antlstatic agents are the glycol fatty ester sold under the trademark HALC0 C-376-N and HALC0 C-1047, the nonylpheno~y polyethyleneoxy ethanols sold under the trademarks IGEPAL C0-520, I~EPAL
C0-530, IGEPAL C0-430 and ICEPAL C0-850, fatty acid glycol ester sold :

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~07~g69 under the trademark KERIPON NC, polyethylene glycol ester monolaurate sold under the trademark LONGZEST PEG-4-0, ethylene oxide condensate sold under the trademark MERPOL OE, MERPOL OJ and M~RPOL OJS, polyoxy-ethylene sorbitan monolaurate sold under the trademarks HALCO CPH-37SN, HALCO CPH-377N and HALCO CPH-378N, propylene oxide condensates with hydrophillic base formed by condensing ethylene oxlde with ethylene glycol sold under the trademarks PLURONIC 10 R 8, 17 R 8, 25 R 5, 25 R 8, 31 R 4, F-38, F-68, F-77, F-87, F-88, F-98, F-108 and F-127, ethoxylated propylene oxide ethylene diamine condensate sold under the trademarks TETRONIC 304, TETRONIC 504, TETRONIC 704, TETRONIC 707, TETRONIC 904, TETRONIC 908, TETRONIC 1104, TETRONIC 1107, TETRONIC 1307 and TETRONIC 1508.
Amphoteric antistatic agents include O-cetyl betaine sold under the trademark Product BCO, o-decyl betaine sold under the trademark Product BDO, N-lauryl betalne sold under the trademark Product DD~, N~cetyl betnlne sold under the trademark Product HDN, N-stearyl betalne sold under the trademark Product ODN and N-oleyl be~aine sold under the trademark Product UDN, palmityl dimethyl ammonium carboxylic acid betaine sold under the trademark ~ELVETEX BP, polyoxyethylene alkylamine sold under the trademark ATLAS-G-3780A and reaction product of coco amlne and crotonic acid sold under the trademark ARMEEN Z.
The best mode of practicing my invention will be apparent from the followlng examples.

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One gallon Lexan polycarbonate bottles soiled by sour milk and milk molds were fed to an automatic bottle washing machine. Conveyor chains carried the bottles submerged in an upright position through the soak tank section of the bottle washing machine. The soak tank section contained 3 pounds of my detergent composition for every 100 pounds of water. The detergent composition was prepared by adding 1 pound of ARMEEN Z ( ) anti-static agent to 99 pounds of the following composition:

GRANUEAR DETERGENT
INGREDIENT PERCENT WEIGHT

C-21 dicarboxylic acid 6 trisodium phosph~te (anhydrous) 7 soda ash (light) 33 sodium metasilicate pentahydrate 30 tetrasodium pyrophosphate 7 sodium methyl na~h~halene sul~onate 7 defoaming agent B 4 sodium bicarbonate 5 wettlng agenttC) The p~l of the detergent solutlon was pH 11.8 and the temperature was about 150F. The solled milk bottles were in contact with the deter-gent solution for about 7 minutes. The bottle washing machine then with-drew the bottles from the soak tank, inverted them so that the 80il and detergent solution drained back into the soak tank after which the inverted bottle passed into a first rinse tank. In this section of the bottle washing machlne, a stream of clean water at about 140F~ was sprayed into the bottle and allowed to drain. Water rinsing was accomplished in about one minute and then the bottle moved into the sanitizing tank where a stream of water containing 200 parts per million of chlorine was sprayed .
tA) trademark for N-coco beta aminobutyric acid (B) Ethoxylated straight chain alcohol sold under the trademark (C) Primary phosphate monoester made by combining polyphosphoric acid and hydroxylic compound sold under the trademark TRITON Q~-44 -` lOql~69 into the inverted bottle. The sanitizing spray temperature was about 120F.
The bottle was in contact with the sanitizing solution for about one minute after which it was moved by the conveyor chain into the final water rinse tank. This rinse was cold potable water and was also sprayed into the inverted bottle. The cleaned milk bottles then moved by the conveyor to the milk filling station. All soils and molds were removed in the washing operation and the bottles had a clean and attractive appearance.
Swab tests showed that the cleaned bottles had a low bacteria count.
E_ample 2 One-quarter part by weight of the granular detergent used in Example 1 ~ithout the antistatic agent was dissolved in 99.75 parts by weight of clean water. This solution at ambient temperature and pH of 10.4 was then sprayed onto a flat polycarbonate surface, soiled with condensed milk which was allowed to incubate for 1 month at room temperature.
Spray was applied at 30 p.s.i.g. for about 45 seconds after which the de-tergent solutlon was rlnsed wlth clean cold water Eor about 30 seconds.
After air drying the washed resln surface was clean and free of water spots and film.
Exam~le_3 The following detergent compositions were formulated and then dissolved in tap water at three percent by weight concentration.

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', . ' . ' : , ' :. '., 1~ 969 INGREDIENT COMPOSITION
A B
C-21 dicarboxylic acid 5.0 7.0 sodium metasilicate pentahydrate 20.0 35.0 Trisodium phosphate (anhydrous) 7.0 9.0 sodium methyl naphthalene sulfonate 5.0 lO.O
tetrasodium pyrophosphate 6.0 9.0 defoaming agent (D) 3.0 5.0 detergent builder (soda ash) 49.015.0 sodium bicarbonate 5.0 lO.O
Detergent composition A had a pH of 11.3 while B had a pH of 11.7. Lexan polycarbonate plates soiled with corldensed milk incubated for 2 weeks at room temperature were immersed in the solutions of 3A and 3B, respectively~ and held at 150F. for 7 minutes. After removal from the detergent solutions the plates were drained, rinsed with tap water and alr dried. The Lexan plates from both solutions were clean and free of water spots.
Example ~
Forty parts by weight of the granular detergent of Example 1 were dissolved in 60 parts by weight o~ clean water. The aqueous C-21 dicarboxylic detergent concentrate was a non-viscous amber colored liquid. Detergent use solutions were prepared from this liquid concentrate by mixing 100 parts by weight of the forty percent solution with 1273 parts of water.
This gave a 3 percent by weight use solution.
E~sample 5 The ~ollowing C-21 dicarboxylic detergents were dry blended and then tested for cleaning capability in dilute aqueous solutions.

(D) Modified oxyethylated straight chain alcohol sold under the trademark PLURAF~C RA-43 ' ',:

~qi96g COMPOSITIO~
INGREDIENT ~ B C
C-21 dicarboxylic acid 6.0 - 6.0 C-21 dicarboxylic sulfate - 6.0 3.0 Soda ash (light) 33.0 33.0 30.0 Trisodium phosphate (anhydrous) 7.0 7.0 7.0 Tetrasodium pyro-phosphate 7.0 7,0 7.0 Sodium metasilicate ~5H20) 30.0 30.0 30.0 Sodlum methyl naphthalene sulfonate7.0 7.0 7.0 Defoaming Agent 4.0(B) 4.0(B) 4,0(B) Surface Active Agent l.O~C) l,O(C) 1 O(C) Sodium bicarbonate 5.0 5.0 5.0 The above granular C-21 dicarboxylic detergents (A through C) were separately dissolved in water at 3 percent by welght concentrations.
After bringing the temperature to about 150F. Lexan polycarbonate plates were immersed in the aqueous solutions for 7 mlnutes. The Lexan poly-carbonate plate~s were soiled with condensed milk whlch was a:Llowed to ln-cubate for about 2 months. After removal from the detergent solutions, the polycarboaate plates were rinsed with clean water for about one-half minute and then allowed to air dry. The plates which were cleaned by the res-pective detergent solutions A through C were all clear and free of soil.
Example 6 Following the procedure of Example 5, one percent by weight oE the following defoaming agents were separately substituted for the Ethoxy-lated stralght chain alcohol ~PI.URAFAC RA-43) used in the compositlon of Example 5-A:

(B) and (C) see Example 1 , ~, ' .' , - . - . : . . , .: . :. .
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1(;)~:1969 sodium salt of dicarboxylic caprylic acid ~MIRANOL* J2M), disodium-N-tallow betamino diproplonate (DERIPHAT* 154), nonylphenoxy polyethyleneoxy e~hanol (IGEPAL* CO 850), sodium sulfate of 2 ethyl-l-hexanol (TERGITOL* 08).
Three percent by weight aqueous solutions of the above granular detergents were evaluated against condensed milk soil following the pro-cedure of Example 4. In all cases the polycarbonate plates were clean and clear.
Example 7 A granular concentrate was prepared by dry blending the following materials expressed as percent by weight: C-21 dicarboxylic acid-3, sodium metasilicate pentahydrate-5, sodium tripolyphosphate-15, sodium bicarbonate-20, sodium methyl naphthalene sulfonate-5, sodium sesquisilicate (builder) -30, sodium sulfate (builder)-15, ethylene oxide-ethylene glycol conden-sate antlstatic agent (PLURONIC F68LF) -2, and N tallow betaamino dipro-plonate surfactant (DERIPHAI 154)-5.
The granular concentrate was dissolved in water at 2% by weight concentration. The pH was 10.5. After ad~usting the temperature to 190F. polycarbonate plates which were soiled by incubated condensed milk, were immersed in the solution. Soil from the plates started to lift off almost immediately. Within 5 to 7 minutes, the plates were completely cleaned, but immersion was continued for 15 minutes. After removal from the detergent solution, the plates were water rinsed and alr drled. The polycarborlate plates were clear and clean.

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Exam?ie 8 Returnable contalners are frequently solled wlth aromatlc and allphatlc organlc materlals Includlng gasollne whlch have a tendency to remaln In the pores of the contalner, survlve the contalner cleanlng operatlon and then contamlnate the food. I evaluated my detergent composltlon for cleanlng various conta~ners In whlch I had stored Isooctane, toluene, and mlxtures of ~sooctane and toluesne for a perlod of 14 days at room temperature. Followlng thls storage perlod, the organlc llqulds were expelied from the contalners rlnsed wlth water and then washed wlth the followlng detergent composltlon - C-21 dlcarboxyllc detergent - 6, sodlum ¦ ~ - metaslllcate - 15, tetrasodlum pyrophosphate ~ 14, sodlum methyl de l'oc~ q 7 naphthalene sulfonate - 7, -~ffle~~ agent - 4, sodlum blcarbonate -1-~
S, sodlum carbonate~48 and antlstatlc agent - 1, all percentages belng ~y welght. I used the cleaner at a concentratLcn of 3% by welght In water by soaklng the contalners at 145 150F~ for two mlnutes and then followed 5, by three water rlnses. Followlng the above clean~ng, the contalners were fllled w1th mllk and held at 37F. for 10 days. The mllk was then analyzed for resldual hydrocarbon by gas chromatography uslng a Perkln-Elmer Model 900 equlpped wlth flame lonlzatlon detector.
The mllk analyzed at less than 0,5 ppm hydrocarbon for both glass and polycarbonate contalners and after exposure to the Isooctane, toluene and mlxtures of both. Th~ only polyethylene container tested showed an Isooctane level in mllk at 50 parts per mllllon. The 0, 5 parts per milllon hydrocarbon Is the same analytlcal result (control) obtaLned when mLlk was analyzed In the same manner but wlth no exposure to a contalner prevlously fllled wlth hydrcarbon. No hydrocarbon oder was detectable In the mllk.

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iO7~9~9 Example 9 The following detergent compositions were used at 3% by weight concentration in water to clean polycarbonate panels soiled with two month old residue of ice cream mix and condensed milk mold.

A B C
Percent by Weight C-21 dicarboxylic acid 9 3 sodium trlpolyphosphate (alkali metal phosphate) 27 5 3 alkall metal methyl naphthalene sulfonate~ 15 15 3 sodium bicarbonate 15 7 5 sodium metasillcate (alkali builder) 28 5 5 sodium sesquisillcate (detergent bullder) 0 63 83 (defoaming agent) 6 0 0 (detergent) O 1 0 (antlstatlc agent) 0 1 0 The soak cycle for cleaners A and B were 7 mlnutes at 150F.
followed by a two mlnute cold water spray rinse. The panels were clean, attra~tlve looklng and free of water spots. The C cleaner required a 20 mlnute soak tlme at 150F. to remove the same soil as the A and B cleaners at 7 mlnutes soak.

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Example io 1~719~9 The ~ollowlng granular ~ormulatlon was dlssolved In water and used to clean and sanltlze both glass and polycarbonate returnable mllk contalners: soda ash tdense) - 39. 5, C-21 dlcarboxyllc acld - 1. 5, ~e~o~-n4 a~
~5 PI.URAFAC RA-43 ~ - S. 0, antlstatlc agent - 1. 0, sodlum trlpolyphosphate - 10, sodlum hexametaphosphate - 5, sodium metasllicate -, 15, sodlum blcarbonate - 89 sodlum methyl naphthalene sulphonate - 3 and chlorlnated trlsodlum phosphate - 12, all flgures belng percent by welght, The granular concentrate was used In a spray washer at a concentratlon of

2, 3 to 2. 7 percent by welght In water. The washlng temperature was held constant wlthln the range oE 130 to 140F. Gallon contalners whlch had been solled wlth Ice cream mlxes from 2 seasons ago were placed Inverted Into a case and Introduced to the washer at the rate of one per mlnute.
~ The machlne provlded a 4 mlnute vertlcal spray-wash cycle, a flve mlnute vertlcal spray water rlnse cycle and a 1 mlnute vertlcal spray , ., water rlnse cycle. The water rlnses were held at a temperature of about 120F. The cleanlng was very good on both the glass and LEXAN poly-carbonate contalners wlth only two passes through the washer. There was no Increase In foam level after 30 mlnutes of operatlon.
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Claims (13)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY OR
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. The granular concentrate for dissolving in water to clean soiled surfaces made from polycarbonate, polypropylene, polyethylene or glass, said concentrate consisting essentially of the following ingredients expressed as percent by weight:
Alkali metal silicate selected from the group consisting of orthosilicates and metasilicates - 5 to 28, Alkali metal phosphate - 5 to 27, Alkali metal methyl naphthalene sulfonate - 1 to 15, Sodium bicarbonate - 5 to 15, Defoaming agent - 0 to 6, Detergent builder selected from the group consisting of sodium sulfate, sodium chloride, sodium sesquicarbonate, sodium sesqui-silicate, sodium carbonate, sodium bicarbonate, and mixtures thereof - 83 to 0 and C-21 dicarboxylic detergent represented by the formula in which one X is hydrogen while the second X is carboxylic, "in which R can be COOH and CH2OSO3H and their alkali metal salts" 1 to 9.

2. The detergent concentrate of claim 1 in which the alkali metal phosphate is selected from the group consisting of sodium tripolyphosphate tetrasodium pyrophosphate, tetrapotassium pyrophosphate, trisodium phosphate, sodium hexametaphosphate and mixtures thereof.

3. The granular detergent concentrate of claim 1 to which there is added from about 0.5 to 2 parts by weight of an antistatic agent to about 99.5 to 98 parts by weight of the concentrate of claim 1.

4. The granular detergent concentrate of claim 1 to which there is added about 0.5 to 5 parts by weight of a surface active agent to about 99.5 to 95 parts by weight of the concentrate of claim 1.

5. The granular detergent concentrate of claim 1 to which there is added about 1 to 3 parts by weight of a dichloroisocyanurate to about 99 to 97 parts by weight of the concentrate of claim 1.

6. The granular detergent concentrate of claim 1 to which there is added about 5 to 12 parts by weight of chlorinated trisodium phosphate to about 95 to 88 parts by weight of the concentrate of claim 1.

7. The aqueous detergent solution consisting essentially of water and from about 0.25 to 40 percent by weight of the concentrate of claim 1.

8. The granular concentrate for dissolving in water to clean soiled surfaces made from polycarbonate, polypropylene, polyethylene or glass, said concentrate consisting essentially of the following ingredients expressed as percent by weight:
Alkali metal silicate selected from the group consisting of orthosilicates and metasilicates - 10 to 20, Alkali metal phosphate - 10 to 20, Alkali metal methyl naphthalene sulfonate - 5 to 10, Sodium bicarbonate - 5 to 10, Defoaming agent - 3 to 5, Detergent builder selected from the group consisting of sodium sulfate, sodium chloride, sodium sesquicarbonate, sodium sesquisilicate, sodium carbonate, sodium bicarbonate and mixtures thereof - 62 to 28, and C-21 dicarboxylic detergent represented by the formula in which one X is hydrogen while the second X is carboxylic, "in which R can be COOH and CH2OSO3H and their alkali metal salts" ~ 5 to 7.

9. The detergent concentrate of claim 8 in which the alkali metal phosphate is selected from the group consisting of sodium tripolyphosphate tetrasodium pyrophosphate, tetrapotassium pyrophosphate, trisodium phosphate, sodium hexametaphosphate and mixtures thereof.

10. The aqueous detergent solution consisting essentially of water and from about 0.25 to 40 percent by weight of the concentrate of claim 8.

11. The granular concentrate for dissolving in water to clean soiled surfaces made from polycarbonate, polypropylene, polyethylene or glass, said concentrate consisting essentially of the following ingredients expressed as percent by weight:
Alkali metal silicate selected from the group consisting of orthosilicates and metasilicates - 10 to 20, Alkali metal phosphate - 15 to 27, Alkali metal methyl naphthalene sulfonate - 2 to 5, Sodium bicarbonate, 5 to 10, Defoaming agent - 4 to 6, Detergent builder selected from the group consisting of sodium sulfate, sodium chloride, sodium sesquicarbonate, sodium sesqui-silicate, sodium carbonate, sodium bicarbonate, and mixtures thereof - 63 to 30, and C-21 dicarboxylic detergent represented by the formula in which one X is hydrogen while the second X is carboxylic, "in which R can be COOH and CH2OSO3H and their alkali metal salts" - 1 to 2.

12. The detergent concentrate of claim 11 in which the alkali metal phosphate is selected from the group consisting of sodium tripolyphosphate, tetrasodium pyrophosphate, tetrapotassium pyrophosphate, trisodium phosphate, sodium hexametaphosphate and mixtures thereof.

13. The aqueous detergent solution comprising essentially of water and from about 0.25 to 40 percent by weight of the concentrate of claim 7.