CA2191130C - Percarboxylic acid rinse method - Google Patents

Abstract

The invention includes compositions and methods for sanitizing ware without staining or spotting. In its most preferred mode, the method comprises the steps of washing the ware in an automated ware washing machine and rinsing the ware at either high or low temperatures with a sanitizing rinse composition. The destaining, sanitizing concentrate composition preferably comprises peroxyacetic acid, acetic acid, and hydrogen peroxide. The sanitizing rinse composition may preferably be used at a concentration ranging from about 600 ppm to 4,000 ppm.

Description

_ 2191 130 PERCARBOXYLIC ACID RTNSE METF~41~
Field oz the Invention ~r.e inve;~t:.o : is a method and cornposit'_o:_ rcr sanitizing ar~d rinsing ware articles used for t~.e preparation, servi:3.g and consu:rptior_ cf rood. 'the invention provides spot-free, film-tree ware prod::cts upon = irs:.nc wi th an added sanitiz i ng ef f ect . The invention :nay be used in either manual or automated washing and rinsing processes to provide a high 1=vel of sanicizi_~g efficacy without t= a harmful. drawbacks of certain': other sanitizing agents suc h as ha":oge ns .
Generally, t:~e sanitizing agent of the inver_tion comprises ene or ;pore carboxylic acids anal peroxide to result :. n a cflmpcsiticn which preferably cempr~.ses, at equiiibriu~,t, hydroaer. peroxide, car:ooxy'yic acid, and peroxycarbcxylic acid.
Baokc~zound of the Invention In high volume ins;.'_tutional rood pxeparat'cn and service ir_stallat=o ns, che:rieal sar_=tizir~g compositions are often used :.n manual and automated ware washing processes o destroy bacteria during :inaing operations to meet minimum sanitation standards. lrs ;rany znstallat:.ons sanitation standards are me:t through the use of very higr. temperature rinse water 82-9?°C (180°-19S°F). Where such temperatures are not achievable, a che:niCal sanitizing agent is often added to one cr more aaueous material that contacts kitchenware or tableware to produce a bacteria ki_ling e=feet at t:he lew temperature conditions of approximately ~t8-6G°C (120-=40~F) . The use o~ the terms "higi: te~,pe=ratuxe" and °law temperature" herein relate approxyrn~~.te'.:y to the above temperature ranges.
Low temperature methods and equipment are illustrated in the following, Fox et al., United States Patent Nog. 2,592,884, 2,592,885, and 2,;92,886, 3,044,092 and 3,146,718, as well as Fcx, United States A~AENDED SHEET

~.VI' . _. w,m c.. ~_. .~ .~ ._ .v_..v ~V~

2~~1 l30 Patent =do. 3,370.59'7. Ir larger park these machines follow a cleaning wegimen wherein t:~e soiled kitchenware or =ableware can be prescraped either ma::.ua7.ly or with a:: automatic machine scraping stage involving a water spray to remove large bulk sail. The ware can then be directed to a none wherein the ware is co:.tacted with a:
aqueous alkaline cleaning cornpositior: that arts to remeve soil by attacking protein, fat or ca=i,~ohycrate soils chemically. '."he cleaned ware can then be directed 20 to a sanitizing stage wherein the ware is contacted with sanitizes material. Alternatively, t:~e ware may be directed to a cornbi:~ed rinsing-sanitizing stage w~:ere the ware is contacted with a combination of rinse agent and sanitizes. Lastly, the ware can be ~liracted ~c a stage were the. artic=es are dried either actively by heating cr pass:.ve7.y by ambie:a evaporati.or_.
The need far sani tization ::as lead t:o th a consideration of various agents. One cf the most ~ommon sanitizers for ware washing is aqueous s<rdium , ypoczlcrite (waOCl) . However, while sodium ypochlorite is effective, low cost and generally avai?ab~.e, sodium hypachlorite has sever_~' disadvantages. First, hypochlorite can react with ardness ions :.n service water including calcium, magnesium, iron, and manganese. Such chemical interaction car. cause liming ar_d miners' depos.ts on machi:~e parts. Suc: deposits can tend tc~ form in and on the water passages of a ware wash;ng machine which can substantial=y change the ~low rates of various aqueous materials t::rough the machir_e. Any such change can seriously reduce the efrectiver_ess of machine operatic~.
Chyorine, as a constituent of sodium hyg,ochlorzte, may also present compatibility problems when used with other chemicals which have desirable sheeting and rinse aid characteristics, such as nonionic surfactants. =urther, the interaction between sodium hypochlorite and various ' aM~~~~~~~ ~~~~

r.v~in . _. _.... _ - , ~ ~ , ., ~. . , _ m. .._ n . vv r mir~erals in service water can result in the spotting and filming of ware prccucts.
Sodium hypochlori=a use ter_ds to substantially increase the total Gisso~.ved solids p=went in aqueous S sanitizing compositicns. High ccn,cantrations of sclids can tend to increase the tendency of agents to =eave unwanted spotting and streaking upon drying. In fact, while chlorine has a noted sanitizing effect, t~:e increased solids resulting Trom this constituent can film, spot and otherwise ,~eave a residue or ware products subjected to the rinse. Chlcrvne :ray also react and degrade or corrode tableware comprising rr.etals as well as metals =ound in the environment o' use.
Sod.um hypochlcrite is aisa a strong- cxidizir:g chemical and can substantially corrode a var,_ety of materials used ir~ machine man ufacture anct in tab 1 eware and kitchenware commonly used in today's =r.stitutional env=ronment . Jas~.Iy, spi-is c. sody~,::n hypoch 1 on to are unp=easant, can cause damage Go b.eachabs.e s-~ryaces, and are difficult to clean.
I-n the meantime, various =inse aid ::omoositions have been developed for use in both low temperature and high temperature was: systems_ For eaample, _;aula et al., United States latent. No. 4,147,559 and Jn=t<ed States neissue Patent No. 30,53% taach an apparatus and a method for rinsing and a hernically sar_it~izing foodwar a items. The disclosure is primarily directed ~o machine related components for ensuring adequate cleaning ar_d sanitizing.
further, a number of rin,ss aid compositions, based largely on nonic~n::c surfactants without ~sanitv_zers are also known. Altenschopfsr, United States Patent No.

3,592,774, teaches saccharide-based nonionic rinsing agents. Rue et al., United States Patent Ne. 3,525,90'_, 3S teach surfactar~ts used as rinse aids ~.aving lcw foaming properties. Dawson et al., United States Patent I3o.
3,941,'713, teach machine ware washing rinse agents ~iv~EF!~En aHE' hav::ng an ants-resoiling or non-stick add.itwve for treating aluminum or other s~.:ch metal kitchenware.

~odri~CUez et al. , Inited States Patent No. :~, C05, C24, teach a rinse aid corzposition contain~_ng organosilane and Inonofunctional organic acids ti:a;. act. as rise agents- Herold et al., United States Pat.et No.

4, 187, 121, Peach a ri nse agent conce:arat:e based c__ saccharide glycol et__er technology.

Further, Mcrganscn et al. , united States Fater:t iJo.

4,624,7?3, teach a solidifies rinse agent: composit=_on contai~'::.ng a nonionic rinsing agent, urea, water and . otter components . Surreys cf non=_onic surfacta :ts and rinse adcitives contain-g no:'zion:~c surf:~Cta nts ==a found in Schick, 'rVcr_ior~ic Surfactants" , p~:b~oiahea by 18 Marvel Dekker, and John L, Wilson, Soau and C2em_cai Specialties, February 1958, pp. 48-52 an<i 17Q-:.7_.

i~
Oakes et a? . , WO 93 i'4=?1~ , describes an n ar_tirnicrobial concentrate co:rposition comprising a synergistic co~nbinat'_on of a low moiec:~l:ar weig~:t 2C peroxyacid from 3.-~ carbon atone with a lzi.g: molecular i -weight peroxfcarboxylic ac_d having 6-~8 carbon atoms.

This ant:.rnicro;vial concentrate carnpositi~~ is uses specifically in the food processing industry on har3 surfaces and equipment involved in food ;processing 25 operations.

French Fatent Pz:blicatior: 2, 32., 3C1 G~.eSCr:.~ea an antimicrobial composition comprising e~.th.er =eracetic or perpropionic acid, _ydrogen peroxide ar~d water as a d=sinfectant for preventing the growt:~ of germs or.

30 equipment ~~n the health and food industries.

Patent publication WO 91/15122 describes a microbiocide and anticorrosive two-part system where the first part contains acetic acid, hydrogen peroxide a~.d peracetic acid and the second part canta.ins a specific 35 wettir_g agent namely a reactio:'~ product cf 9odiurr~

hydroxide, an a7.iphatic alcohol and phosphorous pentoxide or a potassium salt perLluaroa;lkylsulfonate.

AMEfdDED SHEET

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~ . . . ~ o a ~ ~ ~ n _ . _ v - . a n a c .
- 2~ 91 ~~~
Tris system r;.ay be prem_xed and is used for cleaning and preve_~_tin3 Corroslori or dental and medical equipr,~ent .
:xOWeVer, nor_e of these rinse aid6 h«ve been able to combine ezfective sheetir_g and ri.~.sing action with 5 sa:~.itizing a=ficacy. F~ccording~.y, a strer_g need exists _n the art to provide a rinszng sa:wtizing ages-t the=
can promote sheet_ng and removal of spctt,lng, provide substantial sanitizing action, work safel~~ within the er~v_ronment, and result in operations without Gny substantial deposit formation an ware cr dish machines or corrosion of machine components or :citchenware, and tableware.
Brief Description of the Invention rn accordance with a first aspect c.. the i::vention there is provided, a method of saniwiz~rc; and destaining ware comprising the step of applying a sanitizir_g, destaining concentrate composit:.cn comprising a peroxycarboxylic acid, a Gl_a carbaxy lit acid, hydrogen peroxide, and a ba-ai:ce of carrier.
In accordance with a mere preferred aspect of the invention, there is provice3 a method of sanitizing ware without cxeatin,g a film residue comprising the steps of washir.,g the ware i : az~. automated ware waaahina machine, and rinsing the ware at a temperature ranging froth 48-60°C (x.20°F tc '_40°c) with a san_tizing descaining r_oncentraLe composition comprising perox;~acetic acid, acetic acid, and hydrogen peroxids in an aqueous carrier. optionally, the r~.nsing step m:ay also compr,'_se 3o the introduction of a sheeting agent into the automated ware washing rnach_ne dLring the ri.~.s-ng sten or a combined product may be used where the sheetz.ng agent is combined with the sanitizer.
The invention is a method for destairing and san_tizing tableware. ;he invention generally comprises a peroxyacid material which opt:.or~ally may be used :.n combination with effective sheeting agenas that provide ,w,~~,ncn cucFT

~.~, _~~-911-~~- -_ -.-_ __ improved destaining an3 sanitizatioz~:, taut does not cavase significa~-a corrcs'_or_ of machzne paxta ax waxe. we have found that the ef=ec~iJa concer_tration cf the rnateriais result in low total solids fcrmulations wPich S substantially resist spotting. More specifically, as she sanitizing desraining concentrate conpos~tian of t~~e inventior_ comprises a peroxyaCid, the compo6ition ce:erally evaporates from, rather than f_lrning an, t::e wage subjected to the rinse.

1Q Lastly, the carboxy::ic acids to which the peroxy acies degrade are non-toxic and non-con=osive and are compatible with commonly available materials used in the nvanufacture of dish machines, Kitchenware:, tableware and glassware.

i5 For the purpose of this i~-vention, t:he term "sheeting cr rinse agent" refs=s to the <:hemical species t_:at causes the aqueous r_nse to sheet. :he term "ri:se aid" reflects the concentrated material. which is diluted with an aqueous diiuent to form aqueous r:.nse. The 20 terms "wa=e, tGbleware, k~.tcheniaare or dishware" refers - to various types of articles used in the preparation, serving and consumption of foodstuffs inr'~.uding pots, pans, baking dishes, processin g equipcrien':., trays, pitchers, bawls,. p~.ates, saucers, cups, ~~lass, fcrks, 25 knives, spoors, spatulas, grills, grddl~es, burners including chose materials made from polymeric thermoplastics and thexmtosets, Ceramics including 'iced and blown g~.asses, and elemental and alloyed metals such as silver, gold, bronze, copper, pewter, and steel among 3o othex materials. The term "rinsing" or "sheetinc"

relates to the capacity of the aqueous rinse who: in ccntact with table ware to form a substan~ially continuous thin sheet of aqueous rinse which dra=ns even?y from the ware leaving little or no spotting upon ' 35 evaporation of the water.

The invention is concerned primarily with lpw temperature ea_uipment in cleaning and sa:nit_zing i ' AMENDED SHEET

2191w130 attic=es, but can be Gpplicable to high t~?:~:perature machines to p=cv:.de an increased degree of ce~fidence that ware are adequately destained and sa:Zitized.
. Detailed Deacri,~tion of the Invention The iven:=on is a method of sanitizi=g azd destaining ware, includi g those ute.~.si7.s used . the preparation, serv:~g, and ccnsump;.-ion o~ ~_ood and codstu~~s. The method o. the inventio: includes the J application oz a sanitizir_g concentrate comprising a peroxycarboxyl:.C acid reacticn product of one or more carboxylic acids and an oxidiser. Optional=y the composition c' the inventicY nay also comprise oxidizer stab? a seqtzest:ants and sclubi Iiz°rs as ~reli as ether .5 adjuvants suc~: as carriers and sheeting agents. whic'.~.
axe also stable in the pr=sence of an ox'_.dizer. These adjuvants may be premixed w:.th the composition of the :.nventior, as well as separately irtroduc:ed irate tie envirortttent GF uSe SirttultaneouSly Or alter the ~ins2 aid 2 ~ ~ a f t!.e invert ian .
The concEntrate of the invention is Lypically formulated in a liquid diluent compatible with the peroxyacid sanitize; and any rinse aids present :.n the composition. The uniqueness of the invert-or~ relates to 25 the fact that to active components (1) are stable at substantial concentrations '_n the undiluted concentrate, (2) era signiz~.cant improvements over the use o~ sodiun hypachlorite in an aqueous rinse, and (3) provide effective sheeting as well as improved ware appearance.
3~~ Lastly, the compositions o= the invention are non-corrosive is contact with materials common in the automatic dish machines and in Ware.
A. The Sanitizincr. Desta;rin~ncentrate 33 The compositions used in tze invention contain a peroxycarboxylic acid sanitizing composit:.on. The j peroxycarboxylic acid sanitizer material. can comprise at r AMENDED SHEET

2~ ~~ ~ ~o east ore monocarbGxylic acid havi g from ~. to 5 carbon starts. Commonly, the peroxycarboxyiic acid material can be made by oxidizir_g a.morocarbox-~=is acid directly to the peracid material which is then solubilized in the aqueo;zs ccncertrate compositions of the invention.
Further, the materials can be made by combining the L310X_C:32eC~. aci3 with hydrogen peroxide to geners.te the ac_d in situ eithex prior to bl=nding the fatty peroxyacid w~.th the cor_certrate or after the concentrate '?o is formulated.
Generally when the percxycarboxylic acid is ror-iul=~.ed ir_ accordance with zhe invention, a monrcarboxylic ac=d, s~ach as acetic acid, is combin~e3 with an cxidizer such as :=ydroge: peroxide. .he result z5 of this combination is a reaction produc=.~g a peroxycarboxylic acid, such as peroxyacet:ic aci3, and water. The reactor. folyows an equilibri::m .n accorcance with ~he following eguati.an:
20 ' HaOa + CFi3:0UH =-_-_- CH3COOOH +
wherein the K~ is 2Ø
The importance of the eguil ibrium sterns froz~ the prose~ce of hydrogen peroxide, the caxbo:xyi::c acid and 25 t:~e peroxyCarboxylic acid in the same composition at the same time. This combination pro~rides enhanced sarti.tizing with none of the deleterious cc~rosive o;
tarnishing effects of other rinse agents, additives, car compositions.
30 The first constituent of the equi.ibrium nixture comer=ses one or more carboxy~.~.c acids. Generally, carboxylic acids have the formula. R-COO( where'_n tie R
'nay represent any number of different gr oups includi ng aliphatic groups, alicyclic groups; aror.~atic groups, 3~ heteracyclic groups, all of wrich may b~: saturated ox unsaturated as well as substituted ar unsubstituted.
,_ Aii~~fvG~v ~~t=

.. 2~ 91 ~ 3~
a Carboxylic acids a l so occur t~.aving ore, two, three, or :pore - carboxyl. groups .
Carboxy?ic acids provi3e a precursor reactant to the peraxycarboxylic acid and aci3izy aq~:eous compositibns in which they art present aC the hydrogen ato;r, of the caxbexyl group is ac=,_v=. Moreover, ti-:e carboxyl.c acid ccnstituenc used _n the ir_ven4_o maintains the campositior. at an acidic phi which stabilizes and maintains tr~e equi libr ium conce:~~.ration of peroxycarbcxylic acid.
Specific examples of suitable C.-C~ carboxylic acids which can be used to make the peroxycarbcxylic ac=d mat2riais or to combine wits ryuroger. pe::oxide to forty peroxyacid ;raterials include such sa_srated fatty acids 5 as rnbthanoic, acatic aci3, prop~.onic acid, ~~utyric acid, pentanoic, hexano_c acid, and mixtures thereof.
Further, the carboxylic a..~.d peroxycarboxylic acids useful. in t:~is invention include C;,.6 carboxylic and peroxycarboxyli c acids and derivat=ves t:~ereof .incltiding :.0 aGid~esters, acid aa'_ts, ar_d shorter ar_d "_onger chair acids present as contaLn~.::antS .
These acids can be drawn from both natura:. or synthetic sources . ~laturai sources :.r.c? tide animal and vegetable fats or oils whic_ should be fuyly 25 hydrogenated. Syr~theti~c acids Gap be produce3 by the oxidation o~ petrole~.:m 'vax. one cariavxyl_c acid preferrea for use in the cc-mposition of the: invention comprises acetic acid or acetic acid as blended with other C;_6 carboxylic acids. The preferred carboxylic 3o acid is acetic acid which produces perox:ycarbcxylic acid to increase the sanitizing effectiveness of the t materials.
The composition used it tre invention also comprises an oxidizer. Any number of ox;dzzers may be ~5 used as a precursor to t~~e formation of a peroxyearboxylic acid. Generally, the antimicrobial composition of the invention comprises hydrogen .
~il~~~isri~..~ 1~:~..~.

peroxide. ydrcgen pecx'_de in ccmbiraticn w=t . the carboxylic acid arid peroxycarboxylic acrd proviaes a surprising level of a:~timicrob_al actin agair_st.
microcxgan~.sms, even iw the presence of high loadings c.
S organic sediment.
.A,n additional advantage of hydrogen perox=de is the acceptabi_icy of these c:ernpositior_s en food cortac~
surfaces, upon ase and decomposition. rcr example, combinations of peroxyacetic acid and hya.rogen peroxide result in acetic acid, water, and oxygen, upor_ decomposition. All cf these ccnst,:~tuente> are food prod~.:c t comp atib_e .
hydrogen percxi de iuzOz) , has a mole<:ular weichc of 34. 04 and it zs a weakly acidic, clear, colorless 13 lia_uid. The four atoms are covalently bor_ded, i:~ a .?-C-O-H structure. Generally, hydrogen. pero~cide has a melting paint of -0.4i~C, a boiling point of 150.2°C, a density at 25°C or ? .4425 grams per c~:3, a::d a viscosity of 0.0:.245 amiCm-se. ;1.245 centipoisa) at 2C°; ..
Generally, t.~e concentration of hydrogen peroxide writ~in she composition used in the process of the in~rer~tiarl ra:~ges f=om 1 wt-% to 50 wt-%, preferably from 3 wt-% to 40 a_-%, and meat preferably from 10 wt-% to 3G wt-% in the concentrate, prier to use. T?~is cancearat=on of hydrogen perc:cide is most preferred as providing optimal antirnicrabiai effect.
In ail, altering the ccncencration of the oxidizi:~g ages will e~fect the eqwil=brium mix of the peroxycarboxylic acid used .n the inrer_tion.
3a The other pr..~.ciple component of the artim:~,crobial composition. used in the inventio=1 is an oxidized carboxylic acid. This oxidized or peroxycarboxylic acid provides heightened antimicrobial efficacy when combined With hydrogen peroxide and tT~e monocarbaxylic acid in an equilibrium reaction mixture. Percarbgxyiic acids - generally have the formula R~c03x)~" where R is an alkyl, ~=~t~~- _ .. CA 02191130 2004-10-05 ZZ
s.
arylalkyl, cycloalkyl, aromatic or heterocyclic group, i and h is one or more.
While peroxy carboxylic acids are not very stable, their stability generally increases with increasing molecular we~.ght. Thermal decomposition of these acids may generally proceed by free radical and ronradical paths, by photodecomposition or xadi.cal-induced decomposition, or by the act~.on of metal ions or complexes. Percarboxylic acids may be made by the direct, acid catalyzed equilibrium action of 30-98 wt-o hydrogen peroxides with the carboxylic acid, by autoxidation of aldehydes, or from acid chlorides, or carboxylic anhydrides with hydrogen. or sodium peroxide.
Peroxyearboxylic acids ,useful. i.n th~.s ~.nvention inc?ude Cl_6 pexoxycarboxylic, acids such as._permethanoic peracetic acid, perpropanoic acid, perbutarcic acid, perpentanoic acid, pexhexanoic acid and m~.:~tures thereof. These percarboxylic acids have been found to provide~good antimicrobial action with good stability in.
aqueous streams.
In a more preferred mode, the process of the ' invention uses peracetic acid, Peracetic acid is a peroxy carboxylic acid hav~.ng the~formula:
'CH3COOOH .
Generally, peracetic acid is a liquid having an acrid odor and is freely soluble in water, alcohol, ether, and sulfuric acid. Peracetic acid may be prepared through any number of means known to those of s'~cill in the art including preparation from acetaldehyde and oxygen in the presence of cobalt acetate. A 50°-.
solution of peracetic acid may be obtazned by combining acetic anhydride, hydrogen peroxide and sulfuric acid.
Other methods of formulation of peracetic acid include those diaclo8ed in U.S. Patent No.2,833,813.
The preferred peroxyacetic acid materials uaed,in the invention can be used Go increase the sanitizing >, , ;
f , a - . ~", ..__ -2.~.~ y ~ ~~ - _... .._ __ effectiveness of tree materials. Wher_ a ble:ded ac~.d is used-, the peroxyacetic acid is blended i n p~°oporti ons that range from 1 to SO parts cf percxyGc~=_~--c acid per Aac:: part of of~er peroxycarboxylic acid. Prafexably, the peroxyacetic acid is use3 at a ratio of 8 par4s per part of other peroxycarboxyl_c acid.
_e above saitizer material can provide an=ibacterial activity to the rinse aid sanitizers of the ir=Jention against a wide variety o~ microorganisms 1~ such as gram positive (for example, Staphylococcus aureusi and gram negative tfor example, ~schericis coli? microorganisms, yeast, r:5olds, bact4:ria1 spore , viruses, etc.
The co~,pcsition used in the irrva:~ticn also 1S comprises a carrier . 'fhe carrier f:~nctic.ns ;.o pxovide a reaction medium for the so'ubilization e~ constituents and the production cf percaxboxy~.ic acid as well as a medium ::or t he development of an equilibri um mixture o=
oxidizer, percarboxylic acid, and carboxylic GL_d. ~e 20 carrier aisc functions to deliver ar_3 wet the antimierobial composition of the invea~on to the intended substrate.
'r-c this and, the carrier may compri~ae a::y aqueous or organic component or components whit: will fac_litate 2~ these functions. Generally, the carrier comprises water which is an excellent solubilizer and medi~arn for reactipn and eCUilibriurn. Water is also readily accepted in ware washing environments. The carrier may also comprise any nucriber of other constituents such as 3a var:.ous crga :ic compounds which facilitate the turctions provided above.
Crganics which oan be uset~al include s_mple alkyl a7.cohols such as ethanol, isopropanol, a.rd n-propanol.
Polyols are also useful carriers in accordar_ce w:.th the 3S invention, inc'_uding propylene glycol, polyethylenegly~ol, glycerol, and sorbitol. Any of these compounds may be used siZgly or iri combination.
1~~. ryrr...

2~91~~~ __ ._ with other organ_c or vnorganic constitueats or, in combination wit'. water or in m=xtures t~:ereof .
Generally, the caxrier comprises a large portion o~
the composition of the invention and.:nay essentially be S the balance of the corn~positior_ apart ~rom the a;tive antimicrobial composition, and acjuvants. Here again, _ t .e carrier cor_;.s:~trai..lOi~ and type wi .1 cepend upon the nature of the composition as a whole, t'_~_ewnzironment cf storage and meti~od of application inclucirg concentratioof the an=imicrobia,- acent, among ot:ner zactors. Notably the carrier bhould be chosen and used at a concen:ratio:~ whic:~ does not inhibit t::e anLimicrobial efficacy oz tr~e active in the composition C, the inventior_.
H . Ad-iuvar.ts The comnositior_ used in the invention may also opt_onally cor,~przse any number of adjuvais which are stable in an oxidizing ?wirormenr:, and add beneficial properties of stability, sequestration, sheet.na anc rinsing, etc. These adjuvants may be pry=formulated with the rinse aid of the invention cr adaed t:o the system simultar_eo~.a~.y, or even of ;.er, t he addition o~ the rinse aid o~ the i.vention.
2~
ST~3ILeZER
The composition used in the invention may also contain a polyvalent metal complexing or chelating agent that aids in reducing the harrnfu= effects of ardness components and sexvice water. The typically ha=rnful effects of calcium, magnesium, frog, and manganese ions present in service water can ~.nterfere with Lhe action of either the washing Gompcsitions or rinsing compositions or can tend to decompose th.e active peroxygen sanitizes :materials. The cheiating agent or sequestering agent can effectively complex and remove I~L ~ . WJ~ ~~Y'y VIL L~C.Ht.~ U~~ ' :.1' 1 ' LV ~ ~e5 ~ l :l V G m . v a . a T'i':J of ~JJ.rt-rp;J ~ ;F 1 v nc .o~c nv.av rnuG a~
:rt~.. 2 ~ 9 ~ ~ ~ ~

such ions 'ro~~, inappropriate interaction with active i__~_gredients thus increasing rinse aid pexforr,~ar_ce.
moth ogan':c and inorganic chelating~ agents m«y be used. Inorganic chelating agarts ir_clude such compounds as sodi u~t t=ipclyp hosg~-ate and ocher higher ? inear and cyclic polyphcsphate species. Organic cheiating agents include both polvmEric and small mo'_ecul~; chelat:~nc agents. Sriall molecu=a organ_c che=Gc'_ng~ agents i.~.clude sal;.s o= ethylene diamine tetraacetic acid, a=ethylerle io triamir~e penta acetic acid, nitrilocriacetic acid, ethyle:~e d~.amire propionates, triethyl=__~_e_ tat=aaTnine hexacetates and tre respective alcali ;petal, ammoniu;n and substituted arnrr~onium Salts thereof . po_y;reric chelating agents commonly comprise polyamianic I5 compositions such as polyacrylic acid compo~;rcs. ~~nino phosphates and phosphonates are also solvable for use as celating agents in the wompositions of the ir_vent'cn a ad include ethylene diarnia ;tetramethy~.ene p~_csprcnates), itrilot=ismethylene phosphates,.
20 diethylenetr:.amine tpent3met~:yiere phosp:hona=es' . T::ese ~ «mino phesphonates commonly contain alkyl cr alkalir_e i groups with less than 8 ca=bon atoms.
preferred chelati:~g age: is for use in t~:is inversion include improved food additive chelat;ng 25 agents such as disodium salts of ethylene diamine tet:aacetic acid or the well known phosphonates sold in the form of DE~";1EST materials, fcr example, 1-hydroxyethylidEne-~,, ~.-diphcsphonic acid, etc. 'the phosphonic acid may also compzise a law molecular weight 3D phospcsonopolycarboxylic acid such as one: having 2-4 carboxylic acid mo:.eties and 1-3 phosphonic acid groups.
Such acids include 1-phosphono-I-methyl~cucc_r_=c ac=d, _ phosphonosuccinic acid and 2-phosphonobutane-=.2,4 triCarboxylio acid. Other organic phosF>honic acids 35 include those available from Mcnsanto Industrial Chem_cals Ca., St. Louia, MO, such as DFQL'EST 2010, which is a 58-62% aqueous so~.ut~.on; amizio ., 1 .~'W T.-~ (1) !~~T

i~Jnn ~ . i J.v ~ V .. v. , n J .,. -_ W ,. _ _ ( -V.- .
2191'130_ [tri !nethy.enep'r~csphor~ic acid) ~ (~~ [C-ZPC;u~; 3) , ava~,lab_!
' irom Monsanto as REQUEST 2000, as a 50"s a.quaaus so"_utian; ethyle::ediamine (tetra(Tethyle :e:p::csphon'_c acid)J avai_Gble ~rom Mcr:santo as BEQUEST 2041, as a S 9C% solid aciG produce.; an3 2-prosphaacbu~:a. e-1, 2, 4-tricarboxylic ac=d ava~.labie from Mobay C=:ern:.cal ~orporaticn, Inorganic Chemicals ~iv;sion, Pittsburgh, PA, as 3ayhib=t AM, as a 45-50% aqueous qo~.ution.
uhz above-mer_tioned phosphonic acids can also a~
10 used in the form of water soluble acid sa_~s, particular) y t'.~.a alkali metal salts, suc as sodiu,;~ or potass;um; the a~rmonium salts or t a alkylol amix:e salts where the aikylol has 2 ~a 3 carbo: atoms, su4h as mono-di-, or tri-e=hanolami_~e salts. I~ desWed, mixtures 15 of the individual phosphonic acids or their acid salts can also be used.
~i:~ae A, A comp orent which may bz added to or useu with t_~s composition aced in tha invent:.on is a ri:ae agent ssch as G sur~ac~ant system used to promote s:~eeting.
Generally, any r_umb~r of surfactan=s may be cased co~sistent with the purpose of this constit-~ent. Far example tY~:e surfactant ri:~se agent may comprise a nonidniC, anionic, cat_onic, er artphoteric s~a;factant.
2These surfactant rinse aids may a prasent in she sanitizing, destaining conce~trate used in the =r.~vention as formulated, Alternatively, these r~.ns~e agents m.ay be introduced du-ing application: to the warE:. In such an instance, regardless of w:~ether autoc~ated or manual, the rinse agent may be ccmbi~:ed with the concentrate cf the invention prier to applicaz=on cr codisper:sed separa=ely during applicati4n.
Anianic surfactants useful with the ir.~re: tiori comprise alkyl carboxylates, linear alkylber~zene ~ su~.fonates, paraffin su'? forates and secondary n-al ka :e sulfor~ates, su~.fosuccinate esters and salfated linear alcohols.
AfvZEF,J~~~ r~.=;

~f 1s Zwitterionic or amphoteric surfactants useful withi the ~.nvention comprise (3-N-alkylaminopropionic acids, ri alkyl-a-iminodipropionic acids, imidazoline carboxylates, n-alkylbetaines, amine oxides, sulfobetaines and sultaines.
Generally, these surfactants find preferred use in manual applications.. The choice of surfactants depends on the foaming properties that the individual, or combination, of surfactants bring to the composition of the invention.
Nonionic surfactants useful in the context of this invention are generally polyether (also known as polyalkylene oxide, polyoxyalkylene or polyalkylene .
glycol) compounds. More particularly, the polyether 1S .compounds are generally polyoxypropylene or polyoxyethylene glycol compounds. Typically, the surfactants useful in the context of this invent:.on are synthetic organic polyoxypropylene (PO)-polyoxyethylene (EO) block copolymers. These surfactants comprise a diblock polymer comprising an EO block and a PO block, a center block of polyoxypropylene units (PO), and having blocks of polyoxyethylene grafted onto the polyoxypropylene unit or a center~block of EO with attached PO blocks. Further, this surfactant can have further blocks of either polyoxyethylene or polyoxypropylene in the molecule. The average molecular weight of useful suxfactants ranges ~rom looo to 40,000 and the weight percent content of ethylene oxide ranges from 10-80a by weight.
3o Also useful in the context of this invention are surfactants comprising alcohol alkoxylates having EO, PO
and BO blocks. Straight chain primary aliphatic alcohol alkoxylates can be particularly useful as sheeting agents.. Such alkoxylates'are also available from several sources including BASF Wyandotte where they are known as ~~Plurafac" surfactants. A paxt~.cular group of alcohol alkoxylates found to be useful are those having i, g.
* Trademark .vJw .. ~~ '_ ' ' . ._. _ the general for;r~u? a R- (Ed) ,~- (?Oi n wherein :~ is an integer of 2-10 and n is an irtager from 2-2C . R can be ary suitable xadical s~~ch Gs a straight _air. al'_~cyl groin haring from 6-20 carbon atoms.
Other. useful nonionic sur~Gctants ef th2 invention cornpyise capped aliphatic alcohol a=koxylatas. These end caps i=clLde bet are not yimited to ma,thy'_, ethyl, propyl, butyl, berzyl ar_d chlorine _ pref~;~abiy, such surfactants have a molecular weig;.~t :;f 400 to ? 0, ~~0~ .
'!0 Capping imprevAs the compat,ibili_y between the non'_onic and the oxidizers hydrogen peroxide and ps:rcaroxy=is acid, w hen formulated into a single composition:. An especially preferred nonionic is ?lurafac i~Fi3i ~rom - BASr with a structure Cl;_; (EO) ~ (30) 1..R ~~herein R is a C~.s ~5 alkyl moiety and preferably with 60% of the structures being me thy 1 capped, R comer lees C:33 . Other use L1 nonionic surfactants are alkylpolyglycosi~es, ,other useful nonionic surfactant o~ the izwenr.ion comprises a fatty acid alkoxy:.ate wherein the sur=acta t 20 comprises a fatty acid moiety with an ester gro,.:p comprising a block of EO, a block of PO or a rn~xed bloc:c or heteric croup, The molecular weights or such surfactants range fro«< 4C0 ;.0 1,0, 000, a preferred surfactant comprises an E'0 content cf 3v-SO wt-% and 25 wherein the fatty acid moiety contair_s from 8 to LE
carbon atoms.
Similarly, alkyl phenol alkcxylates have also been found useful ~.n vh a manufacture cf t'_:a =rose agents oz the intention. Such s~wrfactants can be made fron an 30 alkyl phenol moiety havi..g an alkyl group with 4 to 18 carbon atoms, car_ cvnta_r, an ethylene cx:ide b_ock, a propylene oxide block or a mixed ethylene oxide, propylene oxide block or heteric polyc~er :aoiety.
Preferably such su_faCtants have a molecular weight o;
35 400 to l0,OO0 and have from 5 to 20 ~inits o~ ethylene oxide, propylene oxide or mixtures thereof.
AME!~1DEQ SHEET

1$
SOLL'$ I' L I ZER
uhe compcsitions used in the i.nve~ticn rnay also include a hydrotrope coup'er or solub=liter. Such materials car. be used to e:~sure that the compositior_ remains p~iase stable and in a single high~.y act_ve aquaous form. Such hydrotrope sclubiliasrs or coup=?rs can be used in composi4icns which Taintain phase stability bu~ do not resu'_t in ur_warted compositicn~l interaction.
Representative classes of hydrotrope solubilizers or ccuplina ages is include are anion:.c surfactant such as an alkyl su~~ate, an alley:. or alkane sulfonatQ, a linear al!tyl benzena or napl2thalene sulfonate, a secondary al:~are su' fr~nate, alkyl other su_fate or ~sulfo: ata, an alkyl phosphate cr phasphonate, dialkyl sulfaswccin-c acid ester, sugar esters ;e.g., sorbitan esters? snd a alkyl glucoside.
Preferred coupling agents for use .r. the rinse agents oz the inve:aion include n-octa:a sul'onate and 2G axomatic sulrcnates such as an alkyl ben2ene sulfor~ate to . g. , sodium xylere suifenate or naphtr~.lene sulfonate) . :zany hydrotr~ope sol,sbilizers; independent=y exhibit some degree of ancim:.crobial act.~.vity at low pH.
Such acticn adds. LC C~1° efficacy of t::e '_.nventior_ but is not a pximary criterion used in selecting a:: apprcpriate solubilizing agent. Since the presence cf the perac'_d material in the protonaGed ne~.aral state prc~rides beneficial biocidal or sariti2ing activity, the coupling agent should be s2-acted not for its indepencea anti microbial activity but for its abiJ.ivy to provide effective si:~gle phase composition stability in the presence of substantia3.'_y insoluble peracid materials and the more soluble compositions of the invention.
C. Formulation The compositior_s used in the invention car. be formulated by comb_ning the rinse agent m«terials A ~is~l . ~ s-~ W ~

. _ . . ; " v' ' . . ._ '- . r ~ v . . c . . . r . r - . ~. _ . . _ , ~ _ _ -includi:lg ot':er ad~uvant eCr'tponents with the materials that :orm the san:.tizar c~ompositior., =re carboxy=is acid or avid b-end, h~!~crocen.percxide any: optiona7.ly, hydrotrobe solubiliz~r.
The cornpositi~~_s can a'_so be f~ar:nulateu with preformed peroxy aci3s. The preferr_d cc:npesitians the i: vent..on can be made by :n_xing the carboxylic acid or mixture thereof with an oLtioral hyGrotrone solubi_izer o: coup-er, reacting tie mixture w:.th hyd~'cg°~ peroxide an ~, then adding to ba_ance of xequiYed i::gredients to prcv.-'.de rins_ng an,d san'tiz_ng GC.IOIi.
stable equilibri:~m mixture is pro3uce3 cc =tai.r.inG
the carboxyi.ic acrd or blend with '.:;Jd=agen perox'da and 1~ allowing the :rixcure to star_d for 1-7 days at 1~~C ar more. Wit: th~.s p reparator~r method, an s:_r~:ilibr_urn mixture ~a_I1 be 'a=~.,e3 containing ar_ amount of hyaroce~a psrcxide, uroxidiaFd acid; oxid:.zed cr peracid and typical'_y ~~nmodiziad ~~ouplers, soZuail::z~r , cr stabilizers.
D. Cor_cenr;ated Jse Gomposwtiors The 7.nvertion contemplates a co.~.centrate composition which is diluted to a use solution prior to its utilization as a sa nitizer. Pr_~narily for reasons of economics, the ccr_centrate would norma?ly be marketer and an end user urould preferably dilute the concentrate _ with water or an aqueous d~.lue.nt to a use: solut-ar_.
The general cc:atituen= concentrations of the sa:~=tw2er concentrate fox~mul.ated .n aecerdance with tire inventio:~ may be round i n the Tab:.e belovu.
f~;~ia'v =~_ ~= _~.

191130.

TAB~E

CONCENTRATE (wt-%) -at~Equiiibrium-More Moss Constituent preferred Preterxed preferred -'.oOZ 1-50 3--"~0 ~.C-3l~

i0 =eroxy acid G.5-25 1-20J 3--~

Carboxylic aci3 2-7~0 5-5C S-40 Stabil.zer 0-5 0.7-4 v.~-1.5 Solubilzzer 0-20 0-15 -10 Rzr~se Agent C-40 5-35 10-30 Carrier Balance ~alance Sala:~ce Tha level cf active ccmpone:~ts .-:n .the cor<centrate composition is depenc.ent or. the intended dilution factor and :he desired act_vity of the surfactant and peroxy f~ty acid compot:.nd and the desired acidity in she ~ase so?ution. Generally, di_utian of 30 ml. (1 fluid o;~nce) o. ~9ncentx'ate t4 4 .4-60 ? ite~s i:.-I5 C~y'allonS;
~f Wa=~r , i . a . a dilution o; fro:r. 1 part cf ~encetrate to ~

parts by volume of water up to i part of ~c~once ntrate to 2000 ~a;ts by volume of water can be obtained w_th 2 to 20 wt- total peracid in t::e concentrate. At this rate, the composition sho-~rn in tre preferred co?um,~ ~of Tabe shown above tray be used at a ra~e of 600 pDm ~d 4~OC
ppm in the rinsing environment. F:ighew ~~se dilutiens can be employed if elevated use temperature (greater than zOdC) or extended expoSUre time {greaCer than 30 5ecc7ridS) Can be employed. In the typical use loc~s, the c~ncentrte is dilated with a major proportion cf water and used or fiesta-ning and sanitiz,_ng us.ng commonly avai.'lab'e tap or service water~m:.xzng the materials at a dilution ratio of i5-300 ml (0.5 to 10 ounces) ef concentrate psr each 35.2 liters {3 gal:~ons) of water.
s At equilibrium, aqueous anwirnicrobial sanitizing use sol;aions can comprise at least i part'per -niilion, preferably :c0 to 400 pprr~, a nd mcre pre=erably 1o tc 200 parts per million of the peroxyfatty acid r~:aterial, 20 ppm to 650 ,ppm, and preferably 20 ppm to 4170 pp:r: of carboxylic acid; at least 20 parts psr mil: ion, typically up to 300 parts per million and ;,preferably 15 to 2C0 parts per mili3on, and most prefQrabJIy 4G to x.0'0 parts per million o= the sh set: ~:g cr rinsi::~g agent; and ZO 100 to 1206 pasts par mill~.on and preferably 20 tc NCO
paxts per million oz hydrogen peroxide. The «cueous us°
solution can =urther Comprise at -east 1 pp=n, preferabl~.~
2 to 20 ppm of the hydrotrc~pe s:~lucil izer, and rave a pH
in the use solation =r_ the range cf 2 tc 9, pref6rably 3 to 8.
In use, 'he campcsitien cf t::e invert i on may be Combznec with a surfactant ri nse aiG. The: surfactan t rinse aid may be uses in the dssired enviror_mert at the ollowing cor_ceatr«~iors (wt-°s) : , ~ More Mast ~re=err2C. ~~e~erreC~ ~L"°farro~
Suryactant 0.0002 0.0003 O.,OC04 Rinse Aid, 0.005 0.002 0.002 ., i5 = Methods of Use As noted above, ccmpositions of the .invention are useful in rins~,ng steps of manual was:~ir~g procedures as well as commonly ova=Table ware wash=rg machines, The san_tiairg destai :ing concea_ate of the invent_on may be used in any manual procedure known to those of skill in art. One example of~such a procedure is a three tub washing procedure for was':~.irg, rinsing, and sanitizing ware. Generally suc h pxoc~edurAs za~te place at temperatures ranging frflm 2o°C to 35°C, While the configuration and corstr~~c:tion of wa=a wasr~irig machines do vaxy from high temperature tc .ow temperature machines and from manufacturer to AMENDED SHEET

2191:130 -rnanu'acturer, all machi~.es share Cosmos operating parameters in that the aa_ueaus rinse cctz;poaitions are sprayed on dishes in a rinse step at a gen~ral:~y f_xed temperature for a generally fixed period otime. Tr, such machines, the aqueous rinse ccmpositio= is r.~xepared by diluting rinse agant with an appropriate proportion of water, placing the aqueous rise in a sump or othex contain.ex and drawi::g and sprayi :g the aa~:eous rinse from the su;np. Such aaueaue rinses eftan sprayed '_t7 through nozzles attached to rotating bars or f_xed sprayer nozzles attached or :.nstalled in the ware washing crachine in a location that optimizes contact between the aqueous rinse and war..
The no2Zl~es are often manufactured with a geometry that enhances a spray pattern fcr complete ccverage.
The spray arms car. be fixed cr car_ recipra~cate or rctate within the maci~.ine pxaviding complete coverage. Tia agueous di?a.:ted concentrate of the invention in a low temperature mac_~ine can be pu:.:ped at a rate of 88-440 liters (20 to 1v0), preferably 1?'6-352 liters (~0 tc 8v ga21ons1 per minute and is commonly contacted with d=shes at temperatures between 48 and 60°C (120 and 140°F). In a high temperature machine, the aqueous rime Zs sprayed.at a rGte oz 4.4-21 liters (z.0-2.5 ~S gallons) per~rack cd,_shes at a temperat.~~re of 65-88°C
1150 to 190°Fl. The rinse cycle can extend in time for from 7 to 30 seconds, preferab:.y ~,a to 2b secor?ds to ensure thaC the dishes are both fully rinsed and sanitized in the rinsing stage. The terns "sanitizing~~
is used :.n the descriation ar-d methods of ~he i vention indicates a reduct~.or. in the population of m~.mbers of undesirable microorganisms by 5 orders o:f magr_itude ar greater t99.999~ reduction) after a 30 second exposure j time. In other words, 99.999% of the-microbial 35. population present in a :eat site axe eliminated by using the composition of the invention, as me«suxed by GersniCidaJ. and Detergent Sanitizing Action of AMEi~DtD SHEEN

191r130 -disinfectants, Official Methods of Ana?ysis of tre Association o= Ofzicial Analytical Chemists, paragraph 96D.09, and applicable subparagraphs, lSth Ed'zion.
g ~ WORKING EX.n.MPLES
The yol':cw:.ng exampla is intended to illustrate tha invetion and should rot be construed to narrow its scope. One Skilled =:~ the art will readi7_y r?cogr_' ze that these examples suggest many other ways in whic~_ the 10 invention can be practiced.

A rinse agent composition was arepared ay b3ending C . 79 gram of a rise open ~ composition cotnpri sing an 15 aqueous rinse aid comprising 10 wt-% L. 4;z8 (benzyl capped linear alcohol ethoxylate), 1G wt-% ~ C97 is EOfPO block Copolymer termir_ated with Pd), I wt-% oz a nonyl phenol ethoxylace having 9.5 moles of ethylene oxide, Q.1 wt-% of ethyle::e diamine tetraacetic acid 24 sodium salt, 0.08 wt-% of a 37 wt-% active a~.~eaus formaldehyde solution, 14 wt-% cf a sodium xylene sulEcnate (44 wt-% actwe aqueous solar=cn) ~r_d 0.01 wt-% of a green dye blended with a material selected from the group consisting of &.23 grams c~f aodi-.~m 28 hypochlorite (9.8 wt-°s active aqueous NaG'1) ;Examz~le lA), 13.4 grams of peracetic acid prepara'ion (~xample 1B) or 6.~ grams of a peracetic acid preparation (Example 1C). The peracetic ac=d preparation cor,~.prises 28 .3 wt-% of !:~~rd=open peroxide, a wt-% of acer_i c acid, 30 5 . 8% peracetic acid, C~ . 9 wt-°s of a phosrhorate stabilizer comprising hydroxyethylidene dinhcsphonic acid and the balance being water.
These three materials were used i.z~ :a machine ware washa.ng experiment wherein drinking glas,~es were washed 35 and rinsed. A wash cycle was used in wh.ch x.37 grams o~ a commercial dishwashing deterger_t was introduced into the wash cycle. In Conducting the ~axperiment, city ?,i,~E~i~.j ~ a~~ -water having ~ 25 ppm total dissolved salids and softe;~.ed wel? waver containirg 255 pprn total dissolved soJ.ids were used. In each expex:.ment a 20 cycle machine evaluation with 10 miz~.v~tes dry time between cycles was 5 use~?. G?asses wexe evaluated at the end of 2a cycles for fi-m ad spots, a'~thcugh filming was taken to be a mere ~el.ab~e ind~ca=or ef glass appearance in the test.
Heavily filmed glasses do not show spots u~el1 because a ':ea:ry fi.;~ prevents appearance of shots. In th ese tests 10 the dish T'lac~7.l.::e nas a 7 . 5 li ter s ( 1 . 7 gal.lor:) sump .
Into each batch of wash ware= was added 2:14 ararns of pureed bee= stew sci= a;:d 1.07 grams of "::ot point'' sc=1. ~ set of test glasses (c.uriz:g the '<;o cycle :est?
was di~~ed into whole milk and dr_ed at 3'?°C t~.00°~) fox 1 S ? 0 minutes be;.ween each cycl e. The of:~_er set cf glasses was r_ct d:.pned into :r.ilk, but allowed t~~ air dry between cycles. The milk soiled glass dupl=sates the soil_ng and drying of soil experie~?ced in restaur<~nt Cor_ditions .
Water te:~.pexature was maintained between ~~4-o'G°C.tl3G-2v 140°F) . sac g_~ass was graded ay three s~epaxace graders. Filming was g=aged in a dark room blac:~ box and the results are the consensus value cf t he t hree film. grade criteria are as follows: no f,_1:~ = 1.0;
trace of T i'_rn = 2 . 0 ; l i ght _ i lm vis ibis ur:der r_orm,al 25 lightir_g conditions = 3.0: moderate fi_m = 4.0; and heavy f i l;n = S . 0 .

W .. .. . l~ . r ~ ~ v ... .. ~ n~.L GV
219 lw~ 3 0 TABLE I
Film results far the 20 cyc~.e tests are as foiiows:
FIj M G;ADES
S
. Sof toned Ci t~~
SA_'vTI'~T_2ER Grade - Grade 1 L _.-Example 1(a) with with milk 4.0 with :r.ilk 3.7 sodiun hyaochlorite w/o milk 3.5 w/c mi.k 2.5 Examp3e 1(b) with with milk 1.G with :silk peracetic acid w/o milk i.5 w/o mi.k 1.4 (:agh dose) Examp_a 1 (c) with with miJ.k 1.7 with m_lk beracet=c acid w; o milk . .7 w/o mi_k ~. , 9 20 slow dose) Ar. examination of the data shown in 'fab:.a I
dE::~onstrates that the use ci cclorine bleach i_~. a rinse 25 agent results in substantial filming on co~'~en glassware. The use cf a peracetic ae:.d hy~drogen~
peroxide sanitizer in combiation with a low foa~ring rir_se agent produces substartially irnprov~:d filT,ing when compared with the hypochlorite based rinse sanitizes 30 system.
WCRK~NG J?:XAMP7~
A fury.~.er analysis of the antimicrob~.a- nature of the invention was undertak?n using the 3e:-micidal and 35 Detergent Sanitizes Test, (Official Final Action, A.O.A.G. Methods of Ar~alysis l5ch Edition,. 1990, 9611.09 A-J) . T:~e test system was prepared by asept~:ca3.ly adding 5 ml of phosphate buf f er to ~ a 24 h:r . agar sl ant of each test system. ~he growth was washed off and =insed back into phosphate buffer. The suspension was than mixed wsll and 2 m1 of this suspensi«n was placed onto each French slant. Tre~slants were tiltmd hack and forth to completely cover the surface. T:he excess AMENDED SHEET

suspension was decanted off and the slants were i incubated at 37~C fox 18-24 hours. ' After incubation, the test system was removed from the French slant agar surface by adding 3 ml phosphate buffer and sterile glass beads. The beads were then rotated back and forth to remove the growth. The suspens~.on was filtered through euchnex Funnel with Whatmari~tvo, 2 filter paper and collected in a sterile test tube. Standardization.of both test systems was performed on spectrophotometer at 580 nm.
Standardization was as follows:
S. aureus Initial 4T = 0.3. , 24 ml of'phosphate buffer was then added.
Finai %T = 1.2.
A test substance was prepared for testing in this race. The test substance had the following composition:
ronst,~~u,e~t w -peroxyacetic acid 5.25 _ , hydrogen peroxide 24.15 inert ingredients ~ 70.60 (includ~,ng carrier?
In operation, 100 ml of prepared test substance was dispensed into a 100 m1 volumetric and 1 ml eras removed.
This 99 ml was dispensed into a sterile 250 ml erlenmeyer flask, placed into a 120°F (48.89°C) water bath and allowed to equilibrate fox 10 minutes. Then, 1 ml of test system was added to~flask while swirling.
After a 30 second exposure, 1 ml was transferred into 9, ml neutralizer. Samples were enumerated using serial dilutions. Incubation was at 37°C for 48 hours.
The neutralizer ~nras prepared with 1% sodium thiosulfate, (J.T. Esker Chemical Co., Phi?lipsburg, New Jersey),.1% Peptone, tDifco Laboratories, Detroit, 3S Michigan); and 1 g Sodium Thiosulfate + I, g.Peptone/90 ml distilled water. This was dispensed and autoclaved as concentrated Thiopeptone:, Also added was 0.02So Cata~.ase,. (Sigma Chemical Co, S,t. Louis, Missouri) .
. , *Tr'ademark _ . __ ~ . _ - . ._ ' I J i~ . . . G'/i T yj.J r . -y . i . v . . _ t\ J~~ 1 .F.~'.!~' jj ~ ,i/ ~~
L~
flri the test date, O.o25°s Catalas2 was prepared by adding 0.125 g Catalase is ;,0 5o m? water. T is solut~.an was filter steri~.ized through a o.4S u:n fzlter. .hen, m1 0~ 0.025% Ca:.alase was added to 90 ml Thi,opeptone an d mixed. ~ 9 ml o~ th' s solution was dispensed ~.rto 25 mm x 150 r~ test tubes Lo be used ds the :~.euLralizer.
:==...
lij~.,, ~; ~r 2~ 9~ i 3~
~~~

~A8~ LE rI
RESULTS
Test Temperaware: 120°-F (48.89°C) ~ 0.2°C./Test Expo3ure Time: 30 seconds Plating Medium: Trypticasa Glucose Ex~ract- Agaz Disco Laboratories, Detroit, Michigan Percent ReductiQr.(%R)_ I:;itial Inocu 1 urn-Survivor ~iu:rbers X
initial. Inocuium Staphylococcus aT.~re~a ATCC 6538 ~~.tial Sup fivors Test Inoculum Numbers Percea Exarzple Water (cfu/ml) (cfu/mi) Reduction 2A 500 ppm 7.97x10~' <10 X9.999 28 S00 ppn 7.9?x10' <1G 99.999 Esc~ieri~h~'_a coil ATCC .? 229 rni t i al Survivoz-s Test In,oculum Numbers Percent Exa;r.ple Water . (cfu/ml) (cfu/ml) Reduction 2A 500 ppm '1.01x108 <10 99.99 2H 500 ppm ?.01x108 <l0 99.999 CONGIrUS TON
The test substar_ce at a concentration of 30 rL;35.2 liters (1 oz/8 gallons) ~~arich is 0.098% (1.96 ml produce in 1998.04 ml d=luent) diluted'in 500 ppn aynthetic hard water (as CaC03), has been shown to be a~ effactive sanitixer an inanimate food contact sur~acE~s against Staphylococcus aureus and Esc:~eric:~ia co:.i by y~_elding a 99.999% reductio.~. within a 30 second exposure time at 220°F (48.89°C) .
AMENDED SHEET

' ~g ' r WORtC?NG EXAMPLE 3 Corro .oxt Exueriments , A sexies of experiments were carried out to measure the relative corrcsive action of hypochlorite solutions vexsus the concentrate composition of the invention on stainless steel. In one series of tests, these solutions were dripped onto hot stainless steel to simulate what one sees in the filed when a feed line breaks, causing th,e ur_.dilutad solution Go drip onto the outside of the hot warewashing machine. Two sx8 incr panels, one maae of 304 stainless steal and the othex from 316 stainless steel, were each divided into four sections and placed in an oven at 37°C (i0fl°F). Each section of each plate was treated with s,0 drops of one of the following solutions daily, g~gr,E COMPOS I T ION
COMP_ARATiVE EXAMPLE 3A HypoChlorite solution of 6.0%
Available Chlorin°
COMPART~TIVE EXnMPLE 3H Hypochlorite solution of ~.8%
Available Chlorine COMPARATIVE EX~h:PLE 3C Hypochlorite solution of 2.I%
Available Chlorine WORKING EXAM1?LE 3A Peracetic Acid solution of 5%
Peracetic Acid ., The panels were treated in this manner ovtr a period of two months. The panels were rinsed with water at the end of each week during this period and observed..
At the end of two weeks, the section of both panels traated with_t~.e hypochlorite solutions (Comparative Examples 3A - 3C) began to corrode, but the sections treated with the peracstic acid solutions (working Example 3A), did not, ' Over the two month period, the hypochlorite treated surfaces gxew progressively worse and exhibited brown diecolorations and pitting whereas the peracetic acid a r ", " CA 02191130 2004-10-05 . ~ ~. .
treated surfaces showed no change except for a slight a lightening.

An exanple of she destaining capability of the S sanitizes was demonstrated using a Hobart* ET-40 double rack dish machine and softened water at a temperature between 48-60°C (120°-140°F1. The peracid sanitizes was the same as that specified ir~ Example 1H. This concentration works out to be 23 ml per rinse cycle.
10 At the beginning of the test, the coffee and tea cups were badly stained. The test was conducted fox one week. Durinr,~, this time, the coffee and tea cups were used and washed in the normal manner. At the end of the one week test; the coffee and tea cups were examir_ed and 15 found to have been deetained.
The above Specification, examples and data provide a complete description of the manufacture and use..af the composition of the invention. .
* Trad~mar~~

Claims (14)

WHAT IS CLAIMED IS:

1. A method of sanitizing and destaining dishware, kitchenware and tableware products, said method comprising steps of:
washing said ware in an automated ware washing machine; and rinsing said washed ware in an automated ware washing machine with a sanitizing destaining concentrate composition comprising:
0.5 to 25 wt-% of a peroxycarboxylic acid selected from the group consisting of permethanoic, peracetic, perpropanoic, perbutanoic, perpentanoic and perhexanoic acid;
2 to 70 wt-% of a carboxylic acid selected from the group consisting of methanoic, acetic, propanoic, butanoic, pentacnoic and hexanoic acid;
1 to 50 wt-% of hydrogen peroxide; and a balance of carrier;
wherein prior to the rinsing step the concentrate composition is diluted to a concentration of 600 ppm to 4000 ppm.

2. The method of claim 1, wherein the rinse step the concentrate composition is applied at a temperature of 49°C to 60°C.

3. The method of claim 1, wherein the concentrate composition is applied to the ware in combination with a surfactant rinse aid.

4. The method of claim 3, wherein the concentrate composition and the surfactant rinse aid are intermixed prior to application.

5. The method of claim 3, wherein said sanitizing, destaining concentrate and said rinse aid are separately applied at the same time during application.

6. The method of claim 3, wherein said surfactant is selected from the group consisting of a nonionic surfactant, and anionic surfactant, a zwitterionic surfactant and mixtures thereof.

7. The method of claim 1, wherein said carrier is water.

8. A method of sanitizing and destaining dishware, kitchenware and tableware products, said method comprising steps of:
washing said ware in an automated ware washing machine; and rinsing said washed ware in an automated ware washing machine with a sanitizing destaining concentrate composition comprising:
0.5 to 25 wt-% of peroxyacetic acid;
2 to 70 wt-% of acetic acid;
1 to 50 wt-% of hydrogen peroxide; and a balance of carrier;
wherein prior to the rinsing step the concentrate composition is diluted to a concentration of 600 ppm to 4000 ppm.

9. The method of claim 8, wherein in the rinse step the concentrate composition is applied at a temperature of 49°C to 60°C.

10. The method of claim 8, wherein the concentrate composition is applied to the ware in combination with a surfactant rinse aid.

11. The method of claim 10, wherein the concentrate composition and the surfactant rinse aid are intermixed prior to application.

12. The method of claim 10, wherein said sanitizing, destaining concentrate and said rinse aid are separately applied at the same time during application.

13. The method of claim 10, wherein said surfactant is selected from the group consisting of a nonionic surfactant, an anionic surfactant, a zwitterionic surfactant and mixtures thereof.

14. The method of claim 10, wherein said carrier is water.