USOO8691018B2

( 12) Unlted States Patent ( 10) Patent N 0. : US 8, 691, 018 B2

Olson et al. ( 4 5 ) Date of Patent: * A p r . 8, 2014
( 5 4 ) HIGH MOLECULA RWEIGHT 2003 / 017 63 05 A 1 9/ 2003 Hoy tetal.
2008/ 023 3 3 90 A 1 9/ 2008 6011111011 etal.
POLYA CRYLA TES FOR A LUMIN UM 2008/ 0287 3 3 5 A 1* 11/ 2008 Smith . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 10/ 220
PROTECTION IN WA REWA SH 2009/ 002915 5 A 1 1/ 2009 Gothlic h etal.
A PPLICA TION S 2009/ 017 6685 A 1 7 / 2009 War d
2010/ 0298193 A 1* 11/ 2010 Tjeltaetal. . . . . . . . . . . . . . . . . . . . 5 10/ 224
( 7 5 ) Inv entor s: Er ik Chr istian Olson, Sav ag e, MN 2010/ 03 004 93 A 1 12/ 2010 SHOdg r ass et al'
( 7 3 )
( * )
( 21)
( 22)
( 65 )
( 5 1)
( 5 2)
( 5 8)
( US) ; Dev on Beau Hammel,
Minneap olis, MN ( U S)
A ssig nee: Ec olab USA Inc . , Saint Paul, MN ( U S)
N otic e: Sub jec t to any disc laimer , the ter m of this
p atent is ex tended or adjusted under 3 5
U. S. C. 15 4 ( b ) b y 12 day s.
This p atent is sub jec t to a ter minal dis
c laimer .
A p p l. N 0. : 12/ 869, 815
Filed: A ug . 27 , 2010
Pr ior Pub lic ation Data
US 2012/ 005 3 104 A 1 Mar . 1, 2012
Int. Cl.
3 083 3 / 04 ( 2006. 01)
C11D 1/ 00 ( 2006. 01)
CIID 3 / 08 ( 2006. 01)
C11D 3 / 3 7 ( 2006. 01)
U. S. Cl.
USPC . . . . . . . . . . . . . . . . . . . 13 4 / 2; 13 4 / 4 1; 13 4 / 4 2; 5 10/ 24 5 ;
5 10/ 267 ; 5 10/ 4 3 4 ; 5 10/ 4 66; 5 10/ 4 7 6; 5 10/ 4 7 7
Field of Classi? c ation Sear c h
USPC . . . . . . . . . . . . . . . . . 5 10/ 24 5 , 267 , 4 3 4 , 4 66, 4 7 6, 4 7 7 ;
13 4 / 2, 4 1, 4 2
See ap p lic ation ? le f or c omp lete sear c h histor y .
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ECOLA B USA Inc . et al. , PCT/ IB2011/ 05 3 7 4 1 ? led A ug . 25 , 201 1,
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Wr itten Op inion of the Inter national Sear c hing A uthor ity mailed
May 3 0, 2012.
* c ited b y ex aminer
Pr imar y Ex aminer * Br ian P Mr uk
( 7 4 ) A ttor ney , A g ent, or Fir m * Mc Kee, Voor hees & Sease,
P. L. C.
( 5 7 ) A BSTRA CT
A w ar ew ashing deter g ent c omp osition is p r ov ided f or use f or
in c leaning of alkaline sensitiv e metals suc h as aluminum or
aluminum c ontaining alloy s. The c omp ositions inc lude alter
nativ es to sodium tr ip oly p hosp hate and/ or other p hosp hor ous
c ontaining r aw mater ials, w hile r etaining c leaning p er f or
manc e and c or r osion p r ev ention. A c c or ding to the inv ention,
hig h molec ular w eig ht p oly ac r y lates ( p oly ac r y lic ac id
homop oly mer s) w ith a molec ular w eig ht of at least ab out
5 000 ar e used as c or r osion inhib itor s and c an b e inc luded f or
aluminum p r otec tion in a numb er of dif f er ent deter g ent c om
p ositions.
10 Claims, N o Dr aw ing s
US 8, 691, 018 B2
1
HIGH MOLECULA R WEIGHT
POLYA CRYLA TES FOR A LUMIN UM
PROTECTION IN WA REWA SH
A PPLICA TION S
FIELD OF THE IN VEN TION
The inv ention r elates to c or r osion inhib iting c omp ositions
and deter g ent and c leaning c omp ositions inc or p or ating the
same, p ar tic ular ly w ar ew ashing c omp ositions c omp r ising
p oly ac r y lates ( or p oly ac r y lic ac id) , and their use f or c leaning
of alkaline sensitiv e metals suc h as aluminum or aluminum
c ontaining alloy s.
BA CKGROUN D OF THE IN VEN TION
In r ec ent y ear s ther e has b een an ev er inc r easing tr end
tow ar ds saf er and sustainab le deter g ent c omp ositions. This
has led to the dev elop ment of alter nativ e c omp lex ing ag ents,
b uilder s, thr eshold ag ents, c or r osion inhib itor s, and the like,
w hic h ar e used instead of p r edominantly p hosp hor ous c on
taining c omp ounds. Phosp hates c an b ind c alc ium and mag
nesium ions, p r ov ide alkalinity , ac t as thr eshold ag ents, and
p r otec t alkaline sensitiv e metals suc h as aluminum and alu
minum c ontaining alloy s.
Other c or r osion inhib itor s inc lude silic ates, suc h as,
sodium silic ate. Sodium silic ate has a tendenc y to b eg in p r e
c ip itating f r om aq ueous solution at a p H b elow 1 1, thus r educ
ing its ef f ec tiv eness to p r ev ent c or r osion of the c ontac ted
sur f ac es w hen used in c leaning solutions hav ing a low er p H.
A dditionally , w hen allow ed to dr y on a sur f ac e silic ates f or m
? lms and/ or sp ots w hic h ar e v isib le and themselv es ar e v er y
dif ? c ult to r emov e. The p r esenc e of these silic on c ontaining
dep osits c an af f ec t the tex tur e, ap p ear anc e and on c ooking or
stor ag e sur f ac es the taste of the mater ials that c ome into
c ontac t w ith the c leaned sur f ac es.
It is an ob jec t of the inv ention to addr ess at least one of the
ab ov e p r ob lems and/ or to of f er deter g ent c omp ositions w ith
usag e and/ or env ir onmental b ene? ts.
SUMMA RY OF THE IN VEN TION
The disc ov er y that using hig h molec ular w eig ht p oly ac r y
lates, namely those w ith molec ular w eig hts of 5 000 or ab ov e
and ideally those w ith molec ular w eig hts of 10, 000 or ab ov e,
c an ac hiev e c or r osion p r otec tion f or A luminum and alumi
num c ontaining alloy s.
In one emb odiment, the p r esent inv ention r elates to a c or
r osion inhib iting c omp osition that may b e used in f or mula
tion of deter g ents, c leaning c omp ositions, and in p r otec ting
aluminum and aluminum c ontaining alloy s f r om c or r osion.
The c or r osion inhib iting c omp osition c omp r ises the use of
hig h molec ular w eig ht p oly ac r y lates, ( or p oly ac r y lic ac id
homop oly mer s) . The p oly ac r y lates ( or p oly ac r y lic ac id
homop oly mer ) or c omb ination of the same p r ef er ab ly
inc ludes those w ith a molec ular w eig ht of 5 000 or ab ov e,
mor e p r ef er ab ly , 10, 000 or ab ov e. A c c or ding to the inv ention,
these hig h molec ular w eig ht p oly mer s ac hiev e c or r osion inhi
b ition and c leaning in deter g ent c omp ositions w ithout the
need f or p hosp hor ous c ontaining c omp onents.
In one emb odiment a deter g ent c omp osition is p r ov ided
ac c or ding to the inv ention. A deter g ent c omp osition inc lud
ing an alkalinity sour c e, and at least one hig h molec ular
w eig ht p oly ac r y late ( or p oly ac r y lic ac id homop oly er ) f or
c or r osion inhib ition. The c leaning ag ent also p r ef er ab ly
inc ludes a deter siv e amount of a sur f ac tant. The alkaline
sour c e c an b e p r ov ided in an amount ef f ec tiv e to p r ov ide a use
20
25
3 0
3 5
4 0
4 5
5 0
5 5
60
65
2
c omp osition hav ing a p H of at least ab out 8. The hig h molec u
lar w eig ht p oly ac r y late ( or p oly ac r y lic ac id homop oly mer ) is
p r ov ided in an amount suf ? c ient to r educ e c or r osion of alu
minum and/ or aluminum c ontaining alloy s at a p H of ab out 8
or g r eater .
A r tic les w hic h r eq uir e suc h c leaning ac c or ding to the
inv ention inc ludes any ar tic le w ith a sur f ac e that c ontains an
alkaline sensitiv e metal, suc h as, aluminum or aluminum
c ontaining alloy s. Suc h ar tic les c an b e f ound in industr ial
p lants, maintenanc e and r ep air ser v ic es, manuf ac tur ing
f ac ilities, kitc hens, and r estaur ants. Ex emp lar y eq uip ment
hav ing a sur f ac e c ontaining an alkaline sensitiv e metals
inc lude sinks, c ookw ar e, utensils, mac hine p ar ts, v ehic les,
tanker tr uc ks, v ehic le w heels, w or k sur f ac es, tanks, immer
sion v essels, sp r ay w asher s, and ultr asonic b aths. In addition,
a deter g ent c omp osition is p r ov ided ac c or ding to the inv en
tion that c an b e used in env ir onments other than inside a
dishw ashing mac hine. A lkaline sensitiv e metals in need of
c leaning ar e f ound in sev er al loc ations. Ex emp lar y loc ations
also inc lude tr uc ks, v ehic le w heels, w ar e, and f ac ilities. One
ex emp lar y ap p lic ation of the alkaline sensitiv e metal c leaning
deter g ent c omp osition f or c leaning alkaline sensitiv e metals
c an b e f ound in c leaning v ehic le w heels in a v ehic le w ashing
f ac ility . Comp ositions inc luding the nov el c or r osion inhib itor
of the inv ention may b e used in any of these ap p lic ations and
the like.
The inv ention also inc ludes methods f or c leaning alumi
num and/ or aluminum c ontaining alloy s b y c ontac ting the
sur f ac e of the same w ith the deter g ent/ c leaning c omp ositions
of the inv ention. The deter g ent/ c leaning c omp ositions
inc lude a c or r osion inhib iting amount of one or mor e molec ular w eig ht p oly ac r y lates ( or p oly ac r y lic ac id
homop oly mer s) hav ing a molec ular w eig ht of at least ab out
5 000.
The inv ention also inc ludes methods f or p r otec ting alumi
num and/ or aluminum c ontaining alloy s f r om c or r osion b y
use of the nov el c or r osion inhib iting c omp osition of the
inv ention. The method inv olv es the step of c ontac ting the
sur f ac e of aluminum, or an aluminum c ontaining alloy w ith
the c or r osion inhib iting c omp osition of the inv ention. The
nov el c or r osion inhib iting c omp osition inc ludes one or mor e
hig h molec ular w eig ht p oly ac r y lates ( or p oly ac r y lic ac id
homop oly mer s) hav ing a molec ular w eig ht of at least ab out
5 000.
A lso inc luded is a method f or manuf ac tur ing a deter g ent
c omp osition. The method c an inc lude a step of adding a
c or r osion inhib itor c omp r ising one or mor e hig h molec ular is
w eig ht p oly ac r y lates ( or p oly ac r y lic ac id homop oly mer s)
hav ing a molec ular w eig ht of at least ab out 5 000 to a deter
g ent c omp osition. The c or r osion inhib itor c an b e added to the
deter g ent c omp osition w hen the deter g ent c omp osition is a
c onc entr ate and/ or w hen the deter g ent c omp osition is a use
solution.
DETA ILED DESCRIPTION OF THE IN VEN TION
In this sp ec i? c ation and the c laims that f ollow , r ef er enc e
w ill b e made to a numb er of ter ms that shall b e de? ned to hav e
the f ollow ing meaning s:
The p hr ase alkaline sensitiv e metal identi? es those met
als that ex hib it c or r osion and/ or disc olor ation w hen ex p osed
to an alkaline deter g ent in solution. A n alkaline solution is an
aq ueous solution hav ing a p H that is g r eater than 8. Ex em
p lar y alkaline sensitiv e metals inc lude sof t metals suc h as
aluminum, nic kel, tin, Z inc , c op p er , b r ass, b r onz e, and mix
tur es ther eof . A luminum and aluminum alloy s ar e c ommon
US 8, 691, 018 B2
3
alkaline sensitiv e metals that c an b e c leaned b y the w ar ew ash
deter g ent c omp ositions of the inv ention.
A s used her ein, w eig ht p er c ent ( w t-%) , p er c ent b y w eig ht,
% b y w eig ht, and the like ar e sy nony ms that r ef er to the
c onc entr ation of a sub stanc e as the w eig ht of that sub stanc e
div ided b y the total w eig ht of the c omp osition and multip lied
b y 100.
A s used her ein, the ter m ab out modif y ing the q uantity of
a c omp onent or ing r edient in the c omp ositions of the inv en
tion or emp loy ed in the methods of the inv ention r ef er s to
v ar iation in the numer ic al q uantity that c an oc c ur , f or
ex amp le, thr oug h ty p ic al measur ing and liq uid handling p r o
c edur es used f or making c onc entr ates or use solutions in the
r eal w or ld; thr oug h inadv er tent er r or in these p r oc edur es;
thr oug h dif f er enc es in the manuf ac tur e, sour c e, or p ur ity of
the ing r edients emp loy ed to make the c omp ositions or c ar r y
out the methods; and the like. The ter m ab out also enc om
p asses amounts that dif f er due to dif f er ent eq uilib r ium c on
ditions f or a c omp osition r esulting f r om a p ar tic ular initial
mix tur e. Whether or not modi? ed b y the ter m ab out, the
c laims inc lude eq uiv alents to the q uantities.
The ter m sur f ac tant or sur f ac e ac tiv e ag ent r ef er s to an
or g anic c hemic al that w hen added to a liq uid c hang es the
p r op er ties of that liq uid at a sur f ac e.
Cleaning means to p er f or m or aid in soil r emov al,
b leac hing , de-sc aling , de-staining , mic r ob ial p op ulation
r educ tion, r insing , or c omb ination ther eof .
A s used her ein, the ter m sub stantially f r ee r ef er s to c om
p ositions c omp letely lac king the c omp onent or hav ing suc h a
small amount of the c omp onent that the c omp onent does not
af f ec t the p er f or manc e of the c omp osition. The c omp onent
may b e p r esent as an imp ur ity or as a c ontaminant and shall b e
less than 0. 5 w t. %. In another emb odiment, the amount of the
c omp onent is less then 0. 1 w t. % and in y et another emb odi
ment, the amount of c omp onent is less than 0. 01 w t. %.
A s used her ein, the ter m w ar e inc ludes items suc h as
eating and c ooking utensils. A s used her ein, the ter m w ar e
w ashing r ef er s to w ashing , c leaning , or r insing w ar e.
A s used her ein, a solid c leaning c omp osition r ef er s to a
c leaning c omp osition in the f or m of a solid suc h as a p ow der ,
a p ar tic le, an ag g lomer ate, a ? ake, a g r anule, a p ellet, a tab let,
a loz eng e, a p uc k, a b r iq uette, a b r ic k, a solid b loc k, a unit
dose, or another solid f or m know n to those of skill in the ar t.
The ter m solid r ef er s to the state of the deter g ent c omp osi
tion under the ex p ec ted c onditions of stor ag e and use of the
solid deter g ent c omp osition. In g ener al, it is ex p ec ted that the
deter g ent c omp osition w ill r emain in solid f or m w hen
ex p osed to elev ated temp er atur es of 100 F. and p r ef er ab ly
1200 F. A c ast, p r essed, or ex tr uded solid may take any f or m
inc luding a b loc k. When r ef er r ing to a c ast, p r essed, or
ex tr uded solid it is meant that the har dened c omp osition w ill
not ? ow p er c ep tib ly and w ill sub stantially r etain its shap e
under moder ate str ess, p r essur e, or mer e g r av ity . For
ex amp le, the shap e of a mold w hen r emov ed f r om the mold,
the shap e of an ar tic le as f or med up on ex tr usion f r om an
ex tr uder , and the like. The deg r ee of har dness of the solid c ast
c omp osition c an r ang e f r om that of a f used solid b loc k, w hic h
is r elativ ely dense and har d similar to c onc r ete, to a c onsis
tenc y c har ac ter iz ed as b eing malleab le and sp ong e-like, simi
lar to c aulking mater ial.
It should b e noted that, as used in this sp ec i? c ation and the
ap p ended c laims, the sing ular f or ms a, an, and the
inc lude p lur al r ef er ents unless the c ontent c lear ly dic tates
other w ise. Thus, f or ex amp le, r ef er enc e to a c omp osition
c ontaining a c omp oun inc ludes a mix tur e of tw o or mor e
c omp ounds. It should also b e noted that the ter m or is
20
25
3 0
3 5
4 0
4 5
5 0
5 5
60
65
4
g ener ally emp loy ed in its sense inc luding and/ or unless the
c ontent c lear ly dic tates other w ise.
The ter m ac tiv es or p er c ent ac tiv es or p er c ent b y
w eig ht ac tiv es or ac tiv es c onc entr ation ar e used inter
c hang eab ly her ein and r ef er s to the c onc entr ation of those
ing r edients inv olv ed in c leaning ex p r essed as a p er c entag e
minus iner t ing r edients suc h as w ater or salts.
A s used her ein, the ter ms sodium tr ip oly p hosp hate-f r ee
or STPP-f r ee r ef er s to a c omp osition, mix tur e, or ing r edi
ents that do not c ontain tr ip oly p hosp hates or to w hic h the
same has not b een added. Should sodium tr ip oly p hosp hate
or iother p hosp hate c ontaining c omp ounds b e p r esent
thr oug h c ontamination of a c omp osition, mix tur e, or ing r e
dients, the amount of the same shall b e less than 0. 5 w t. %. In
a p r ef er r ed emb odiment, the amount of the same is less than
0. 1 w t. % and in a mor e p r ef er r ed emb odiment, the amount is
less than 0. 01 w t. %.
The ter m sub stantially similar c leaning p er f or manc e
r ef er s g ener ally to ac hiev ement b y a sub stitute c leaning p r od
uc t or sub stitute c leaning sy stem of g ener ally the same deg r ee
( or at least not a sig ni? c antly lesser deg r ee) of c leanliness or
w ith g ener ally the same ex p enditur e ( or at least not a sig ni?
c antly lesser ex p enditur e) of ef f or t, or b oth.
Many ar tic les hav ing a sur f ac e that r eq uir es c leaning c on
tain an alkaline sensitiv e metal, suc h as, aluminum or alumi
num c ontaining alloy s. Suc h ar tic les c an b e f ound in indus
tr ial p lants, maintenanc e and r ep air ser v ic es, manuf ac tur ing
f ac ilities, kitc hens, and r estaur ants. Ex emp lar y eq uip ment
hav ing a sur f ac e c ontaining an alkaline sensitiv e metals
inc lude sinks, c ookw ar e, utensils, mac hine p ar ts, v ehic les,
tanker tr uc ks, v ehic le w heels, w or k sur f ac es, tanks, immer
sion v essels, sp r ay w asher s, and ultr asonic b aths. In addition,
a w ar ew ash deter g ent c omp osition is p r ov ided ac c or ding to
the inv ention that c an b e used in env ir onments other than
inside a dishw ashing mac hine. A lkaline sensitiv e metals in
need of c leaning ar e f ound in sev er al loc ations. Ex emp lar y
loc ations also inc lude tr uc ks, v ehic le w heels, w ar e, and f ac ili
ties. One ex emp lar y ap p lic ation of the alkaline sensitiv e
metal c leaning / w ar ew ash deter g ent c omp osition f or c leaning
alkaline sensitiv e metals c an b e f ound in c leaning v ehic le
w heels in a v ehic le w ashing f ac ility . Comp ositions of the
inv ention may b e used in any of these ap p lic ations.
A c c or ding to one emb odiment of the inv ention a deter g ent
c omp osition is p r ov ided c omp r ising an alkaline sour c e and a
nov el c or r osion inhib itor c omp r ising one or mor e hig h
molec ular w eig ht p oly ac r y lates ( or p oly ac r y lic ac id
homop oly mer s) hav ing a molec ular w eig ht of at least ab out
5 000.
The c omp osition may also p r ef er ab ly inc lude a deter siv e
amount of a sur f ac tant. The alkaline sour c e c anb e p r ov ided in
an amount ef f ec tiv e to p r ov ide a use c omp osition hav ing a p H
of at least ab out 8. The c or r osion inhib itor is p r ov ided in an
amount suf ? c ient to r educ e c or r osion of aluminum w hen the
deter g ent c omp osition is p r ov ided as a use c omp osition f or
w ashing aluminum and aluminum c ontaining alloy s.
The deter g ent c omp osition c an b e made av ailab le as mul
tip le c onc entr ates that ar e diluted and c omb ined at the situs of
use to p r ov ide a use solution f or ap p lic ation to alkaline sen
sitiv e metals. A n adv antag e of p r ov iding c onc entr ates that ar e
later c omb ined is that ship p ing and stor ag e c osts c an b e
r educ ed b ec ause it c an b e less ex p ensiv e to ship and stor e a
c onc entr ate r ather than a use solution and is also mor e sus
tainab le b ec ause less p ac kag ing is used. A lthoug h the deter
g ent c omp osition ac c or ding to the inv ention c an b e p r ov ided
as multip le c onc entr ates, it should b e under stood that the
c omp osition c an b e p r ov ided as a r eady to use solution. In
addition, the multip le c onc entr ates c an inc lude tw o or mor e
US 8, 691, 018 B2
5
c onc entr ates that ar e added tog ether . In addition, the c onc en
tr ates c an b e p r ov ided in the f or m of a liq uid solid, p aste, g el,
g r anulate, or p ow der .
The c leaning c omp osition c an b e c har ac ter iz ed as inc lud
ing an alkaline c omp onent and a c or r osion inhib itor c omp o
nent. The alkaline c omp onent inc ludes a sour c e of alkalinity .
The sour c e of alkalinity is p r ov ided so that the use solution
has a p H of at least 8. 0. The c or r osion inhib itor c omp onent
inc ludes a c or r osion inhib itor of p oly ac r y lic ac id and p oly
maleic ac id homop oly mer s ( or salts ther eof ) . The c or r osion
inhib itor c omp onent is p r ov ided f or r educ ing c or r osion of
alkaline sensitiv e metals b y the use solution hav ing a p H of at
least 8. 0.
A sur f ac tant c omp onent may also b e p r esent. The sur f ac
tant c omp onent p r ov ides c leaning p r op er ties w hen used as
p ar t of the use solution at a p H of at least 8. 0. A thr eshold
inhib itor / c r y stal modi? er c an also b e p r ov ided to p r ev ent
c alc ium c ar b onate p r ec ip itation in a use solution p r ov ided at
a p H in the r ang e of 8. 0 to 14 . 0. Fur ther additional c omp o
nents inc lude the use of c helants as disc ussed her einaf ter .
Sour c e of A lkalinity
The sour c e of alkalinity c an b e any sour c e of alkalinity that
is c omp atib le w ith the other c omp onents of the deter g ent
c omp osition and that w ill p r ov ide a use solution w ith the
desir ed p H. Ex emp lar y sour c es of alkalinity inc lude alkali
metal hy dr ox ides, alkali metal salts, silic ates, p hosp hates,
amines, and mix tur es ther eof . Ex emp lar y alkali metal
hy dr ox ides inc lude sodium hy dr ox ide, p otassium hy dr ox ide,
and lithium hy dr ox ide. The alkali metal hy dr ox ide may b e
added to the c omp osition in a v ar iety of f or ms, inc luding f or
ex amp le in the f or m of solid b eads, dissolv ed in an aq ueous
solution, or a c omb ination ther eof . A lkali metal-hy dr ox ides
ar e c ommer c ially av ailab le as a solid in the f or m of p r illed
solids or b eads hav ing a mix of p ar tic le siz es r ang ing f r om
ab out 12-100 U. S. mesh, or as an aq ueous solution, as f or
ex amp le, as a 4 5 w t. %, 5 0 w t. % and a 7 3 w t. % solution.
Ex emp lar y alkali metal salts inc lude sodium c ar b onate,
tr isodium p hosp hate, p otassium c ar b onate, and mix tur es
ther eof . Ex emp lar y silic ates inc lude sodium metasilic ates,
sesq uisilic ates, or thosilic ates, p otassium silic ates, and mix
tur es ther eof . Ex emp lar y p hosp hates inc lude sodium p y r o
p hosp hate, p otassium p y r op hosp hate, and mix tur es ther eof .
Ex emp lar y amines inc lude alkanolamine. Ex emp lar y alkano
lamines inc lude tr iethanolamine, monoethanolamine, dietha
nolamine, and mix tur es ther eof .
The sour c e of alkalinity is p r ov ided in an amount suf ? c ient
to p r ov ide the use solution w ith a p H of at least 8. 0. The use
solution p H r ang e is p r ef er ab ly b etw een ab out 8. 0 and ab out
13 . 0, and mor e p r ef er ab ly b etw een 10. 0 to 12. 5 . In g ener al,
the amount of alkalinity p r ov ided in the c onc entr ate c an b e in
an amount of at least ab out 0. 05 w t. % b ased on the w eig ht of
the alkaline c onc entr ate. The sour c e of alkalinity in the c on
c entr ate is p r ef er ab ly b etw een ab out 0. 05 w t. % and ab out 99
w t. %, mor e p r ef er ab ly is b etw een ab out 0. 1 w t. % and ab out
95 w t. %, and most p r ef er ab ly is b etw een 0. 5 w t. % and 90 w t.
%.
Cor r osion Inhib itor Comp onent
The inv ention c omp r ises a nov el c or r osion inhib itor c om
p onent of one or mor e hig h molec ular w eig ht p oly ac r y lates
( or p oly ac r y lic ac id homop oly mer s) hav ing a molec ular
w eig ht of at least ab out 5 000 The c or r osion inhib itor c omp o
nent ef f ec tiv ely r educ es c or r osion to alkaline sensitiv e metals
suc h as aluminum or aluminum c ontaining alloy s at a p H of
ab out 8 or g r eater .
A c c or ding to one emb odiment of the p r esent inv ention, one
or mor e hig h molec ular w eig ht p oly ac r y lates ar e used as a
c or r osion inhib itor . The p oly ac r y late c ontains a p oly mer iz a
20
25
3 0
3 5
4 0
4 5
5 0
5 5
60
65
6
tion unit der iv ed f r om the monomer selec ted f r om the g r oup
c onsisting of ac r y lic ac id, methac r y lic ac id, methy l ac r y late,
methy l methac r y late, ethy l ac r y late, ethy l methac r y late, b uty l
ac r y late, b uty l methac r y late, iso-b uty l ac r y late, iso-b uty l
methac r y late, iso-oc ty l ac r y late, iso-oc ty l methac r y late,
c y c lohex y l ac r y late, c y c lohex y l methac r y late, g ly c idy l ac r y
late, g ly c idy l methac r y late, hy dr ox y ethy l ac r y late, hy dr ox
y p r op y l ac r y late, 2-hy dr ox y ethy l ac r y late, 2-hy dr ox y ethy l
methac r y late, 2-hy dr ox y p r op y l ac r y late, 2-hy dr ox y p r op y l
methac r y late and hy dr ox y p r op y l methac r y late and a mix tur e
ther eof , among w hic h ac r y lic ac id. methac r y lic ac id, methy l
ac r y late, methy l methac r y late, b uty l ac r y late, b uty l meth
ac r y late, iso-b uty l ac r y late, iso-b uty l methac r y late, hy dr ox y
ethy l ac r y late, 2-hy dr ox y ethy l ac r y late, 2-hy dr ox y ethy l
methac r y late, 2-hy dr ox y p r op y l ac r y late, and 2-hy dr ox y p r o
p y l methac r y late, and a mix tur e ther eof ar e p r ef er r ed.
The ab ov e-mentioned ac r y late monomer s c an b e selec ted
f r om the g r oup c onsisting of methy l ac r y late, methy l meth
ac r y late, b uty l ac r y late, 2-p henox y ethy l ac r y late, ethox y
lated 2-p henox y ethy l ac r y late, 2-( 2-ethox y ethox y ) ethy l
ac r y late, c y c lic tr imethy lolp r op ane f or mal ac r y late, . b eta.
c ar b ox y ethy l ac r y late, laur y l( meth) ac r y late, isooc ty l ac r y
late, stear y l( meth) ac r y late, isodec y l ac r y late, isob or ny ( meth)
ac r y late, b enz y l ac r y late, hy dr ox y p iv aly l hy dr ox y p iv alate
diac r y late, ethox y lated 1, 6-hex anediol diac r y late, dip r op y
lene g ly c ol diac r y late, ethox y lated dip r op y lene g ly c ol dia
c r y late, neop enty l g ly c ol diac r y late, p r op ox y lated neop enty l
g ly c ol diac r y late, ethox y lated b isp henol-A di( meth) ac r y late,
2-methy l-1, 3 -p r op anediol diac r y late, ethox y lated 2-methy l
1, 3 -p r op anediol diac r y late, 2-b uty l-2-ethy l-1, 3 -p r op anediol
diac r y late, ethy lene g ly c ol dimethac r y late, diethy lene g ly c ol
dimethac r y late, 2-hy dr ox y ethy l methac r y late p hosp hate, tr is
( 2-hy dr ox y ethy l) isoc y anur ate tr iac r y late, p entaer y thr itol
tr iac r y late, ethox y lated tr imethy lolp r op ane tr iac r y late, p r o
p ox y lated tr imethy lolp r op ane tr iac r y late, tr imethy lolp r o
p ane tr imethac r y late, p entaer y thr itol tetr aac r y late, ethox y
lated p entaer y thr itol tetr aac r y late, ditr imethy lolp r op ane
tetr aac r y late, p r op ox y lated p entaer y thr itol tetr aac r y late, p en
taer y thr itol tetr aac r y late, dip entaer y thr itol hex aac r y late,
( meth) ac r y late, hy dr ox y ethy l ac r y late ( HEA ) , 2-hy dr ox y
ethy l methac r y late ( HEMA ) , tr ip r op y lene g ly c ol di( meth)
ac r y late-1, 4 -b utanediol di( meth) ac r y late, 1, 6-hex anediol
di( meth) ac r y late, ally lated c y c lohex y l di( meth) ac r y late, iso
c y anur ate di( meth) ac r y late, ethox y lated tr imethy lol p r op ane
tr i( meth) ac r y late, p r op ox y lated g ly c er ol tr i( meth) ac r y late,
tr imethy lol p r op ane tr i( meth) ac r y late, and tr is( ac r y lox y eth
y l) isoc y anur ate, and a mix tur e ther eof .
Poly ac r y lic ac ids, ( C3 H4 O2) n or 2-Pr op enoic ac id
homop oly mer ; A c r y lic ac id p oly mer ; Poly ( ac r y lic ac id) ; Pr o
p enoic ac id p oly mer ; PA A hav e the f ollow ing str uc tur al f or
mula:
w her e n is any integ er .
Ex amp les of p oly ac r y lates ( p oly ac r y lic homop oly mer s)
w hic h may b e used f or the inv ention and that ar e those w ith a
molec ular w eig ht of at least ab out 5 000. One sour c e of c om
US 8, 691, 018 B2
7
mer c ially av ailab le p oly ac r y lates ( p oly ac r y lic homop oly
mer s) usef ul f or the inv ention inc ludes the A c usol 4 4 5 ser ies
f r om The Dow Chemic al Comp any , Wilming ton Del. , USA .
The p oly ac r y lates ( p oly ac r y lic homop oly mer s) c ommer
c ially av ailab le ar e A c usol 929 ( 10, 000 MW) and A c umer
15 10 ( 60, 000 MW) b oth also av ailab le f r om Dow Chemic al.
Yet another c ommer c ially av ailab le p oly ac r y lic ac id is
A QUA TREA T A R-6 ( 100, 000 MW) f r om A kz oN ob el Str aw
insky laan 25 5 5 107 7 Z Z A mster dam Postb us 7 5 7 3 0 107 0A S
A mster dam. Other suitab le p oly ac r y lates ( p oly ac r y lic
homop oly mer s) f or use in the inv ention inc lude, c an b e
ob tained f r om sup p lier s suc h as A ldr ic h Chemic als, Milw aul
kee, Wis. , and A CROS Or g anic s and Fine Chemic als, Pitts
b ur g , Pa.
The c or r osion inhib itor c omp onent c an b e p r ov ided in the
c or r osion inhib itor c onc entr ate in an amount suf ? c ient to
p r ov ide a desir ed lev el of c or r osion inhib ition w hen used in
the use solution. Ther e should b e su? ic ient amount of c or r o
sion inhib itor to p r ov ide the desir ed c or r osion inhib iting
af f ec t. It is ex p ec ted that the up p er limit on the c or r osion
inhib itor c omp onent w ill b e c ontr olled b y solub ility . The
c or r osion inhib itor c omp onent c an b e p r ov ided in the c or r o
sion inhib itor c onc entr ate in an amount of at least ab out 0. 005
w t. %. It is p r ef er r ed that the c or r osion inhib itor c omp onent
b e p r ov ided in the c onc entr ate in an amount of b etw een ab out
0. 5 w t. % and ab out 5 0 w t. %, mor e p r ef er ab ly b etw een ab out
1 w t. % and ab out 3 0 w t. %, and most p r ef er ab ly b etw een 5 %
and 15 % ac tiv e p oly mer .
A s f ur ther p r ov ided her ein, additional c or r osion inhib itor s
may also b e added to the deter g ent/ c leaning c omp ositions of
the inv ention.
Cleaning A g ent/ Sur f ac tant
The deter g ent c omp osition c an inc lude at least one c lean
ing ag ent c omp r ising a sur f ac tant or sur f ac tant sy stem. A
v ar iety of sur f ac tants c an b e used in a w ar ew ashing c omp o
sition, suc h as anionic , nonionic , c ationic , and Z Witter ionic
sur f ac tants. It should b e under stood that sur f ac tants ar e an
op tional c omp onent of the deter g ent c omp osition and c an b e
ex c luded. The deter g ent c omp osition, w hen p r ov ided as a
c onc entr ate, c an inc lude the c leaning ag ent in a r ang e of
b etw een ab out 0. 5 w t. % and ab out 20 w t. %, mor e p r ef er ab ly
in a r ang e b etw een ab out 1 w t. % and 10 w t. %, and most
p r ef er ab ly in a r ang e b etw een ab out 1. 5 w t. % and 5 w t. %.
A dditional ex emp lar y r ang es of sur f ac tant in a c onc entr ate
inc lude ab out 0. 05 w t. % to 7 . 5 w t. %, mor e p r ef er ab ly ab out
0. 5 w t. % to 5 w t. %, and most p r ef er ab ly ab out 1 w t. % to 3
w t. %.
Ex emp lar y sur f ac tants that c an b e used ar e c ommer c ially
av ailab le f r om a numb er of sour c es. For a disc ussion of sur
f ac tants, see Kir k-Othmer , Enc y c lop edia of Chemic al Tec h
nolog y , Thir d Edition, v olume 8, p ag es 900-912. When the
c omp osition inc ludes a c leaning ag ent, the c leaning ag ent c an
b e p r ov ided in an amount ef f ec tiv e to p r ov ide a desir ed lev el
of c leaning .
A nionic sur f ac tants usef ul deter g ent c omp ositions inc lude,
f or ex amp le, c ar b ox y lates suc h as alky lc ar b ox y lates ( c ar
b ox y lic ac id salts) and p oly alkox y c ar b ox y lates, alc ohol
ethox y late c ar b ox y lates, nony lp henol ethox y late c ar b ox y
lates, and the like; sulf onates suc h as alky lsulf onates, alky l
b enz enesulf onates, alky lar y lsulf onates, sulf onated f atty ac id
ester s, and the like; sulf ates suc h as sulf ated alc ohols, sulf ated
alc ohol ethox y lates, sulf ated alky lp henols, alky lsulf ates, sul
f osuc c inates, alky lether sulf ates, and the like; and p hosp hate
ester s suc h as alky lp hosp hate ester s, and the like. Ex emp lar y
anionic sur f ac tants inc lude sodium alky lar y lsulf onate, alp ha
ole? nsulf onate, and f atty alc ohol sulf ates.
20
25
3 0
3 5
4 0
4 5
5 0
5 5
60
65
8
N onionic sur f ac tants usef ul in the deter g ent c omp osition
inc lude, f or ex amp le, those hav ing a p oly alky lene ox ide p oly
mer as a p or tion of the sur f ac tant molec ule. Suc h nonionic
sur f ac tants inc lude, f or ex amp le, c hlor ine-, b enz y l-, methy l-,
ethy l-, p r op y l-, b uty l- and other like alky l-c ap p ed p oly ethy l
ene g ly c ol ether s of f atty alc ohols; p oly alky lene ox ide f r ee
nonionic s suc h as alky l p oly g ly c osides; sor b itan and suc r ose
ester s and their ethox y lates; alkox y lated ethy lene diamine;
alc ohol alkox y lates suc h as alc ohol ethox y late p r op ox y lates,
alc ohol p r op ox y lates, alc ohol p r op ox y late ethox y late p r o
p ox y lates, alc ohol ethox y late b utox y lates, and the like; non
y lp henol ethox y late, p oly ox y ethy lene g ly c ol ether s and the
like; c ar b ox y lic ac id ester s suc h as g ly c er ol ester s, p oly ox y
ethy lene ester s, ethox y lated and g ly c ol ester s of f atty ac ids,
and the like; c ar b ox y lic amides suc h as diethanolamine c on
densates, monoalkanolamine c ondensates, p oly ox y ethy lene
f atty ac id amides, and the like; and p oly alky lene ox ide b loc k
c op oly mer s inc luding an ethy lene ox ide/ p r op y lene ox ide
b loc k c op oly mer suc h as those c ommer c ially av ailab le under
the tr ademar k PLURON IC ( BA SE-Wy andotte) , and the
like; and other like nonionic c omp ounds. Silic one sur f ac tants
suc h as the A BIL B885 2 c an also b e used.
Cationic sur f ac tants that c an b e used in the deter g ent c om
p osition inc lude amines suc h as p r imar y , sec ondar y and ter
tiar y monoamines w ith C1_ 8 alky l or alkeny l c hains, ethox y
lated alky lamines, alkox y lates of ethy lenediamine,
imidaz oles suc h as a 1-( 2-hy dr ox y ethy l) -2-imidaz oline, a
2-alky l-1-( 2-hy dr ox y ethy l) -2-imidaz oline, and the like; and
q uater nar y ammonium salts, as f or ex amp le, alkq uuater nar y
ammonium c hlor ide sur f ac tants suc h as n-alky l( C12-C18)
dimethy lb enz y l ammonium c hlor ide, n-tetr adec y ldimethy l
b enz y lammonium c hlor ide monohy dr ate, a nap hthy lene-sub
stituted q uater nar y ammonium c hlor ide suc h as dimethy l-1
nap hthy lmethy lammonium c hlor ide, and the like. The
c ationic sur f ac tant c an b e used to p r ov ide sanitiz ing p r op er
ties.
Z w itter ionic sur f ac tants that c an b e used in the deter g ent
c omp osition inc lude b etaines, imidaz olines, and p r op inates.
If the deter g ent c omp osition is intended to b e used in an
automatic dishw ashing or w ar ew ashing mac hine, the sur f ac
tants selec ted, if any sur f ac tant is used, c an b e those that
p r ov ide an ac c ep tab le lev el of f oaming . It should b e under
stood that w ar ew ashing c omp ositions f or use in automatic
dishw ashing or w ar ew ashing mac hines ar e g ener ally c onsid
er ed to b e low -f oaming c omp ositions.
The sur f ac tant c an b e selec ted to p r ov ide low f oaming
p r op er ties. One w ould under stand that low f oaming sur f ac
tants that p r ov ide the desir ed lev el of deter siv e ac tiv ity ar e
adv antag eous in an env ir onment suc h as a dishw ashing
mac hine w her e the p r esenc e of lar g e amounts of f oaming c an
b e p r ob lematic . In addition to selec ting low f oaming sur f ac
tants, one w ould under stand that def oaming ag ents c an b e
utiliz ed to r educ e the g ener ation of f oam. A c c or ding ly , sur
f ac tants that ar e c onsider ed low f oaming sur f ac tants as w ell
as other sur f ac tants c an b e used in the deter g ent c omp osition
and the lev el of f oaming c an b e c ontr olled b y the addition of
a def oaming ag ent.
Thr eshold A g ent/ Cr y stal Modi? er Comp onent
The deter g ent c omp osition may also inc lude a thr eshold
ag ent or c r y stal modi? er . f or r educ ing p r ec ip itation of c al
c ium c ar b onate in the use solution. In g ener al, it is ex p ec ted
that the thr eshold ag ent/ c r y stal modi? er c omp onent w ill
loosely hold c alc ium to r educ e p r ec ip itation of c alc ium c ar
b onate onc e it is sub jec ted to a p H of at least 8. 0.
Ex emp lar y thr eshold ag ents/ c r y stal modi? er s inc lude
p hosp honoc ar b ox y lic ac ids, p hosp honates, p hosp hates,
c helants, p oly mer s, and mix tur es ther eof . Ex emp lar y
US 8, 691, 018 B2
p hosp honoc ar b ox y lic ac ids inc lude those av ailab le under the
name Bay hib itTM A M f r om Bay er , and inc lude 2-p hosp ho
nob utane-1, 2, 4 , tr ic ar b ox y lic ac id ( PBTC) . Ex emp lar y p hos
p honates inc lude amino tr i( methy lene p hosp honic ac id) ,
1-hy dr ox y ethy lidene 1-1-dip hosp honic ac id, ethy lene
diamine tetr a( methy lene p hosp honic ac id) , hex amethy lene
diamine tetr a( methy lene p hosp honic ac id) , diethy lene tr i
amine p enta( methy lene p hosp honic ac id) , and mix tur es
ther eof . Ex emp lar y p hosp honates ar e av ailab le under the
name Deq uestTM f r om Monsanto. Ex emp lar y p oly mer s
inc lude p oly ac r y lates, p oly methac r y lates, p oly ac r y lic ac id,
p oly itac onic ac id, p oly maleic ac id, sulf onated p oly mer s,
c op oly mer s and mix tur es ther eof . It should b e under stood
that the mix tur es c an inc lude mix tur es of dif f er ent ac id sub
stitutedp oly mer s w ithin the same g ener al c lass. In addition, it
should b e under stood that salts of ac id sub stituted p oly mer s
c an b e used. The usef ul c ar b ox y lated p oly mer s may b e
g ener ic ally c ateg or iz ed as w ater -solub le c ar b ox y lic ac id
p oly mer s suc h as p oly ac r y lic and p oly methac r y lic ac ids or
v iny l addition p oly mer s. Of the v iny l addition p oly mer s c on
temp lated, maleic anhy dr ide c op oly mer s as w ith v iny l
ac etate, sty r ene, ethy lene, isob uty lene, ac r y lic ac id and v iny l
ether s ar e ex amp les. The p oly mer s tend to b e w ater -solub le or
at least c olloidally disp er sib le in w ater . The molec ular w eig ht
of these p oly mer s may v ar y ov er a b r oad r ang e althoug h it is
p r ef er r ed to use p oly mer s hav ing av er ag e molec ular w eig hts
r ang ing b etw een 1, 000 up to 1, 000, 000, mor e p r ef er ab ly a
molec ular w eig ht of 100, 000 or less, and most p r ef er ab ly a
molec ular w eig ht b etw een 1, 000 and 10, 000.
The p oly mer s or c op oly mer s ( either the ac id-sub stituted
p oly mer s or other added p oly mer s) may b e p r ep ar ed b y either
addition or hy dr oly tic tec hniq ues. Thus, maleic anhy dr ide
c op oly mer s ar e p r ep ar ed b y the addition p oly mer iz ation of
maleic anhy dr ide and another c omonomer suc h as sty r ene.
The low molec ular w eig ht ac r y lic ac id p oly mer s may b e
p r ep ar ed b y addition p oly mer iz ation of ac r y lic ac id or its salts
either w ith itself or other v iny l c omonomer s. A lter nativ ely ,
suc h p oly mer s may b e p r ep ar ed b y the alkaline hy dr oly sis of
low molec ular w eig ht ac r y lonitr ile homop oly mer s or c op oly
mer s. For suc h a p r ep ar ativ e tec hniq ue see N ew man U. S. Pat.
N o. 3 , 4 19, 5 02.
The thr eshold ag ent/ c r y stal modi? er c omp onent should b e
p r ov ided in an amount suf ? c ient so that w hen it is in the use
solution, it suf ? c iently disr up ts c r y stal g r ow th or p r ev ents the
p r ec ip itation of c alc ium c ar b onate and other insolub le salts
suc h as mag nesium silic ate, mag nesium hy dr ox ide, and the
like. In a p r ef er r ed emb odiment, the thr eshold ag ent/ c r y stal
modi? er c omp onent c an b e p r ov ided in a r ang e of ab out
0. 0001 w t. % to ab out 25 w t. %, and mor e p r ef er ab ly in a
r ang e b etw een ab out 0. 001 w t. % and ab out 10 w t. %, and
most p r ef er ab ly b etw een ab out 0. 01% and 8% b ased on the
w eig ht of the c onc entr ate. It should b e under stood that the
p oly mer s, p hosp honoc ar b ox y lates, and p hosp honates c an b e
used alone or in c omb ination.
Hy dr otr op e Comp onent
A hy dr otr op e c omp onent c an b e used to help stab iliz e the
sur f ac tant c omp onent. It should b e under stood that the hy dr o
tr op e c omp onent is op tional and c an b e omitted if it is not
needed f or stab iliz ing the sur f ac tant c omp onent. In many
c ases, it is ex p ec ted that the hy dr otr op e c omp onent w ill b e
p r esent to help stab iliz e the sur f ac tant c omp onent. Ex amp les
of the hy dr otr op es inc lude the sodium, p otassium, ammo
nium and alkanol ammonium salts of x y lene, toluene, ethy l
b enz oate, isop r op y lb enz ene, nap hthalene, alky l nap hthalene
sulf onates, p hosp hate ester s of alkox y lated alky l p henols,
p hosp hate ester s of alkox y lated alc ohols, shor t c hain ( C8 or
less) alky l p oly g ly c oside, sodium, p otassium and ammonium
20
25
3 0
3 5
4 0
4 5
5 0
5 5
60
65
10
salts of the alky l sar c osinates, salts of c umene sulf onates,
amino p r op ionates, dip heny l ox ides, and disulf onates. The
hy dr otr op es ar e usef ul in maintaining the or g anic mater ials,
inc luding the sur f ac tant, r eadily disp er sed in the c leaning
c omp osition and/ or aq ueous c leaning solution.
A dditional Cor r osion Inhib itor s
A dditional c or r osion inhib itor s w hic h may b e op tionally
added to the deter g ent c omp ositions of this inv ention inc lude
mag nesium and/ or z inc . Pr ef er ab ly , the metal ions ar e p r o
v ided in w ater solub le f or m. Ex amp les of usef ul w ater solub le
f or ms of mag nesium and z inc ions ar e the w ater solub le salts
ther eof inc luding the c hlor ides, nitr ates and sulf ates of the
r esp ec tiv e metals. If any of the alkalinity p r ov iding ag ents ar e
the alkali metal c ar b onates, b ic ar b onates or mix tur es of suc h
ag ents, mag nesium ox ide c an b e used to p r ov ide the Mg ion.
The mag nesium ox ide is w ater solub le in suc h solutions and
is a p r ef er r ed sour c e of Mg ions. In or der to maintain the
disp er sib ility of the mag nesium and/ or z inc c or r osion inhib i
tor s in aq ueous solution, and in the p r esenc e of ag ents w hic h
w ould other w ise c ause p r ec ip itation of the z inc or mag ne
sium ions, e. g . , c ar b onates, p hosp hates, etc . , it mig ht b e
adv antag eous to inc lude a c ar b ox y lated p oly mer to the solu
tion.
Other A dditiv es
The deter g ent c omp osition c an inc lude other additiv es
suc h as c helating / seq uester ing ag ents, b leac hing ag ents,
deter g ent b uilder s or ? ller s, har dening ag ents or solub ility
modi? er s, def oamer s, anti-r edep osition ag ents, thr eshold
ag ents, stab iliz er s, disp er sants, enz y mes, aesthetic enhanc ing
ag ents ( i. e. , dy e, p er f ume) , and the like. A djuv ants and other
additiv e ing r edients w ill v ar y ac c or ding to the ty p e of c om
p osition b eing manuf ac tur ed. It should b e under stood that
these additiv es ar e op tional and need not b e inc luded in the
c leaning c omp osition. When they ar e inc luded, they c an b e
inc luded in an amount that p r ov ides f or the ef f ec tiv eness of
the p ar tic ular ty p e of c omp onent.
Water c onditioning p oly mer s c an also b e used as a f or m of
b uilder . Ex emp lar y w ater c onditioning p oly mer s inc lude
p oly c ar b ox y lates. Ex emp lar y p oly c ar b ox y lates that c an b e
used as b uilder s and/ or w ater c onditioning p oly mer s inc lude
those hav ing p endant c ar b ox y late ( iCOZ T) g r oup s and
inc lude, f or ex amp le, p oly ac r y lic ac id, maleic / ole? n c op oly
mer , ac r y lic / maleic c op oly mer , p oly methac r y lic ac id, ac r y lic
ac id-methac r y lic ac id c op oly mer s, hy dr oly z ed p oly ac r y la
mide, hy dr oly z ed p oly methac r y lamide, hy dr oly z ed p oly a
mide-methac r y lamide c op oly mer s, hy dr oly z ed p oly ac r y
lonitr ile, hy dr oly z ed p oly methac r y lonitr ile, hy dr oly z ed
ac r y lonitr ile-methac r y lonitr ile c op oly mer s, and the like. For
a f ur ther disc ussion of c helating ag ents/ seq uestr ants, see
Kir k-Othmer , Enc y c lop edia of Chemic al Tec hnolog y , Thir d
Edition, v olume 5 , p ag es 3 3 9-3 66 and v olume 23 , p ag es
3 19-3 20, the disc losur e of w hic h is inc or p or ated b y r ef er enc e
her ein.
Bleac hing ag ents f or use in a c leaning c omp ositions f or
lig htening or w hitening a sub str ate, inc lude b leac hing c om
p ounds c ap ab le of lib er ating an ac tiv e halog en sp ec ies, suc h
as C12, Br 2, 4 OCL and/ or 4 OBr _ , under c onditions ty p ic ally
enc ounter ed dur ing the c leansing p r oc ess. Suitab le b leac hing
ag ents f or use in the p r esent c leaning c omp ositions inc lude,
f or ex amp le, c hlor ine-c ontaining c omp ounds suc h as c hlo
r ine, hy p oc hlor ite, and/ or c hlor amine. Ex emp lar y halog en
r eleasing c omp ounds inc lude the alkali metal dic hlor oisoc y a
nur ates, c hlor inated tr isodium p hosp hate, the alkali metal
hy p oc hlor ites, monoc hlor amine and dic hlor amine, and the
like. Enc ap sulated c hlor ine sour c es may also b e used to
enhanc e the stab ility of the c hlor ine sour c e in the c omp osition
( see, f or ex amp le, U. S. Pat. N os. 4 , 618, 914 and 4 , 83 0, 7 7 3 ,
US 8, 691, 018 B2
11
the disc losur e of w hic h is inc or p or ated b y r ef er enc e her ein) .
A b leac hing ag ent may also b e a p er ox y g en or ac tiv e ox y g en
sour c e suc h as hy dr og en p er ox ide, p er b or ates, sodium c ar
b onate p er ox y hy dr ate, p hosp hate p er ox y hy dr ates, p otassium
p er monosulf ate, and sodium p er b or ate mono and tetr ahy
dr ate, w ith and w ithout ac tiv ator s suc h as tetr aac ety lethy lene
diamine, and the like. The c omp osition c an inc lude an ef f ec
tiv e amount of a b leac hing ag ent. In a p r ef er r ed emb odiment
w hen the c onc entr ate inc ludes a b leac hing ag ent, it c an b e
inc luded in an amount of ab out 0. 1 w t. % to ab out 60 w t. %,
mor e p r ef er ab ly b etw een ab out 1 w t. % and ab out 20 w t. %,
and most p r ef er ab ly b etw een ab out 3 w t. % and ab out 8 w t. %.
The c omp osition c an inc lude an ef f ec tiv e amount of deter
g ent ? ller s, w hic h does not p er f or m as a c leaning ag ent p er se,
b ut c oop er ates w ith the c leaning ag ent to enhanc e the ov er all
c leaning c ap ac ity of the c omp osition. Ex amp les of deter g ent
? ller s suitab le f or use in the p r esent c leaning c omp ositions
inc lude sodium sulf ate, sodium c hlor ide, star c h, sug ar s,
Cl-Clo alky lene g ly c ols suc h as p r op y lene g ly c ol, and the
like. When the c onc entr ate inc ludes a deter g ent ? ller , it c an b e
inc luded an amount of ab out 1 w t. % to ab out 20 w t. % and
b etw een ab out 3 w t. % to ab out 15 w t. %.
A def oaming ag ent f or r educ ing the stab ility of f oam may
also b e inc luded in the c omp osition to r educ e f oaming . When
the c onc entr ate inc ludes a def oaming ag ent, the def oaming
ag ent c an b e p r ov ided in an amount of b etw een ab out 0. 01 w t.
% and ab out 3 w t. %.
Ex amp les of def oaming ag ents that c an b e used in the
c omp osition inc ludes ethy lene ox ide/ p r op y lene b loc k
c op oly mer s silic one c omp ounds suc h as silic a disp er sed in
p oly dimethy lsilox ane, p oly dimethy lsilox ane, and f unc tion
aliz ed p oly dimethy lsilox ane suc h as those av ailab le under the
name A b il B995 2, f atty amides, hy dr oc ar b on w ax es, f atty
ac ids, f atty ester s, f atty alc ohols, f atty ac id soap s, ethox y
lates, miner al oils, p oly ethy lene g ly c ol ester s, alky l p hos
p hate ester s suc h as monostear y l p hosp hate, and the like. A
disc ussion of def oaming ag ents may b e f ound, f or ex amp le, in
Us. Pat. N o. 3 , 04 8, 5 4 8 to Mar tin et al. , U. S. Pat. N o. 3 , 3 3 4 ,
14 7 to Br unelle et al. , and Us. Pat. N o. 3 , 4 4 2, 24 2 to Rue et
al. , the disc losur es of w hic h ar e inc or p or ated b y r ef er enc e
her ein.
The c omp osition c an inc lude an anti-r edep osition ag ent f or
f ac ilitating sustained susp ension of soils in a c leaning solu
tion and p r ev enting the r emov ed soils f r om b eing r edep osited
onto the sub str ate b eing c leaned. Ex amp les of suitab le anti
r edep osition ag ents inc lude f atty ac id amides, ? uor oc ar b on
sur f ac tants, c omp lex p hosp hate ester s, sty r ene maleic anhy
dr ide c op oly mer s, and c ellulosic der iv ativ es suc h as hy dr ox y
ethy l c ellulose, hy dr ox y p r op y l c ellulose, and the like. In a
p r ef er r ed emb odiment, the anti-r edep osition ag ent, w hen
inc luded in the c onc entr ate, is added in an amount b etw een
ab out 0. 5 w t. % and ab out 10 w t. %, and mor e p r ef er ab ly
b etw een ab out 1 w t. % and ab out 5 w t. %.
Stab iliz ing ag ents that c an b e used inc lude p r imar y ali
p hatic amines, b etaines, b or ate, c alc ium ions, sodium c itr ate,
c itr ic ac id, sodium f or mate, g ly c er ine, maleonic ac id, or g anic
diac ids, p oly ols, p r op y lene g ly c ol, and mix tur es ther eof . The
c onc entr ate need not inc lude a stab iliz ing ag ent, b ut w hen the
c onc entr ate inc ludes a stab iliz ing ag ent, it c an b e inc luded in
an amount that p r ov ides the desir ed lev el of stab ility of the
c onc entr ate. In a p r ef er r ed emb odiment the amount of stab i
liz ing ag ent is ab out 0 to ab out 20 w t. %, mor e p r ef er ab ly
ab out 0. 5 w t. % to ab out 15 w t. %, and most p r ef er ab ly ab out
2 w t. % to ab out 10 w t. %.
Disp er sants that c an b e used in the c omp osition inc lude
maleic ac id/ ole? n c op oly mer s, p oly ac r y lic ac id, and mix
tur es ther eof . The c onc entr ate need not inc lude a disp er sant,
20
25
3 0
3 5
4 0
4 5
5 0
5 5
60
65
12
b ut w hen a disp er sant is inc luded it c an b e inc luded in an
amount that p r ov ides the desir ed disp er sant p r op er ties.
Ex emp lar y r ang es of the disp er sant in the c onc entr ate c an b e
b etw een ab out 0 and ab out 20 w t. %, mor e p r ef er ab ly
b etw een ab out 0. 5 w t. % and ab out 15 w t. %, and most
p r ef er ab ly b etw een ab out 2 w t. % and ab out 9 w t. %.
Enz y mes c an b e inc luded in the c omp osition to aid in soil
r emov al of r ob ust soils suc h as star c h, p r otein, and the like.
Ex emp lar y ty p es of enz y mes inc lude p r oteases, alp ha-amy
lases, and mix tur es ther eof . Ex emp lar y p r oteases that c an b e
used inc lude those der iv ed f r om Bac illus lic henif ar mix ,
Bac illus lenus, Bac illus alc alop hilus, and Bac illus amy
l0liq uef ac ins. Ex emp lar y alp ha-amy lases inc lude Bac illus
sub lilis, Bac illus amy loliq uef ac eins and Bac illus lic henif or
mis. The c onc entr ate need not inc lude an enz y me. When the
c onc entr ate inc ludes an enz y me, it c an b e inc luded in an
amount that p r ov ides the desir ed enz y matic ac tiv ity w hen the
w ar ew ashing c omp osition is p r ov ided as a use c omp osition.
Ex emp lar y r ang es of the enz y me in the c onc entr ate inc lude
b etw een ab out 0 and ab out 15 w t. %, mor e p r ef er ab ly
b etw een ab out 0. 5 w t. % and ab out 10 w t. %, and most
p r ef er ab ly b etw een ab out 1 w t. % and ab out 5 w t. %.
In addition to p r ov iding alkalinity and hav ing anti-r edep o
sition p r op er ties silic ates c an also p r ov ide f ur ther metal p r o
tec tion. Ex emp lar y silic ates inc lude sodium silic ate and
p otassium silic ate. The deter g ent c omp osition c an b e p r o
v ided w ithout silic ates, b ut w hen silic ates ar e inc luded, they
c an b e inc luded in amounts that p r ov ide f or desir ed metal
p r otec tion. The c onc entr ate c an inc lude silic ates in a r ang e
b etw een ab out 10 w t. % and ab out 80 w t. %, mor e p r ef er ab ly
b etw een ab out 3 0 w t. % and ab out 7 0 w t. %, and most p r ef
er ab ly b etw een ab out 4 0 w t. % and 60 w t. %.
The c onc entr ate c an inc lude w ater . In g ener al, it is
ex p ec ted that w ater may b e p r esent as a p r oc essing aid and
may b e r emov ed or b ec ome w ater of hy dr ation. It is ex p ec ted
that w ater may b e p r esent in b oth the liq uid c onc entr ate and in
the solid c onc entr ate. In the c ase of the liq uid c onc entr ate, it
is ex p ec ted that w ater w ill b e p r esent in a r ang e of b etw een
ab out 5 w t. % and ab out 95 w t. %, mor e p r ef er ab ly b etw een
ab out 20 w t. % and ab out 7 5 w t. %, and most p r ef er ab ly
b etw een ab out 3 0 w t. % and ab out 5 0 w t. %. In the c ase of a
solid c onc entr ate, it is ex p ec ted that the w ater w ill b e p r esent
in r ang es b etw een ab out 5 w t. % and ab out 60 w t. %, mor e
p r ef er ab ly b etw een ab out 15 w t. % and ab out 4 5 w t. %, and
most p r ef er ab ly b etw een ab out 25 w t. % and ab out 4 0 w t. %.
It should b e additionally ap p r ec iated that the w ater may b e
p r ov ided as deioniz ed w ater or as sof tened w ater .
Var ious dy es, odor ants inc luding p er f umes, and other aes
thetic enhanc ing ag ents c an b e inc luded in the c omp osition.
Dy es may b e inc luded to alter the ap p ear anc e of the c omp o
sition, as f or ex amp le, Dir ec t Blue 86 ( Miles) , Fastusol Blue
( Mob ay Chemic al Cor p . ) , A c id Or ang e 7 ( A mer ic an Cy ana
mid) , Basic Violet 10 ( Sandoz ) , A c idYellow 23 ( GA F) , A c id
Yellow 17 ( Sig ma Chemic al) , Sap Gr een ( Key stone A naline
and Chemic al) , Metanil Yellow ( Key stone A naline and
Chemic al) , A c id Blue 9 ( Hilton Dav is) , Sandolan Blue/ A c id
Blue 182 ( Sandoz ) , Hisol Fast Red ( Cap itol Color and
Chemic al) , Fluor esc ein ( Cap itol Color and Chemic al) , A c id
Gr een 25 ( Cib a-Geig y ) , and the like.
Fr ag r anc es or p er f umes that may b e inc luded in the c om
p ositions inc lude, f or ex amp le, ter p enoids suc h as c itr onellol,
aldehy des suc h as amy l c innamaldehy de, a jasmine suc h as
C1 S-jasmine or jasmal, v anillin, and the like.
When the c omp onents that ar e p r oc essed to f or m the deter
g ent ar e p r oc essed into a b loc k, it is ex p ec ted that the c om
p onents c an b e p r oc essed b y ex tr usion, c asting , or p r essed
solid tec hniq ues. In g ener al, w hen the c omp onents ar e p r o
US 8, 691, 018 B2
13
c essed b y ex tr usion tec hniq ues, it is b eliev ed that the c omp o
sition c an inc lude a r elativ ely smaller amount of w ater as an
aid f or p r oc essing c omp ar ed w ith the c asting tec hniq ues. In
g ener al, w hen p r ep ar ing the solid b y ex tr usion, it is ex p ec ted
that the c omp osition c an c ontain b etw een ab out 2 w t. % and
ab out 10 w t. % w ater . When p r ep ar ing the solid b y c asting , it
is ex p ec ted that the amount of w ater c an b e p r ov ided in an
amount b etw een ab out 20 w t. % and ab out 5 0 w t. %.
The deter g ents of the inv ention may ex ist in a use solution
or c onc entr ated solution that is in any f or m inc luding liq uid,
f r ee ? ow ing g r anular f or m, p ow der , g el, p aste, solids, slur r y ,
and f oam. The c leaning solutions ar e suitab le to tr eat any
metal sur f ac e c ontaminated w ith a w ide v ar iety of c ontami
nants. Ex emp lar y c ontaminants inc lude g r ease, c lay , dir t, and
ox ide b y -p r oduc ts. The p r esent solutions may b e used b y
c ontac ting the c ontaminated metal p ar ts w ith an ef f ec tiv e
amount of the aq ueous solution. Pr ef er r ed c ontac t methods
inc lude immer sion or some ty p e of imp ing ement in w hic h the
c leaning solution is c ir c ulated or c ontinuously ag itated
ag ainst the metal p ar t or is sp r ay ed ther eon. A lter nativ ely ,
ag itation c an b e p r ov ided as ultr asonic w av es. The p r esent
inv ention is also suitab le f or c lean-in-p lac e op er ations that do
not r eq uir e disassemb ly of eq uip ment.
The w ar ew ash deter g ents of this inv ention may b e used at
any temp er atur e, inc luding an elev ated temp er atur e of ab out
90-1800 F.
The v ar ious f or ms of the w ar ew ashing c omp osition c on
c entr ate c an b e p r ov ided in a w ater solub le p ac kag ing ? lm.
That is, solids and liq uids c an b e p ac kag ed in the w ater
solub le ? lms. Ex emp lar y solids that c an b e p ac kag ed in a
w ater solub le ? lm inc lude p ow der s, p ellets, tab lets, and
b loc ks. Ex emp lar y liq uids that c an b e p ac kag ed in the w ater
solub le ? lm inc lude g els and p astes.
The w ar ew ashing c omp osition c an b e p r ov ided in the f or m
of a solid. Ex emp lar y solid dishw ashing c omp ositions ar e
disc losed in Us. Pat. N o. 6, 4 10, 4 95 to Lentsc h et al. , U. S.
Pat. N o. 6, 3 69, 021 to Man et al. , U. S. Pat. N o. 6, 25 8, 7 65 to
Wei et al, U. S. Pat. N o. 6, 17 7 , 3 92 to Lentsc h et al. , U. S. Pat.
N o. 6, 164 , 296 to Lentsc h et al. , U. S. Pat. N o. 6, 15 6, 7 15 to
Lentsc h et al. , and Us. Pat. N o. 6, 15 0, 624 to Lentsc h et al.
The c omp ositions of eac h of these p atents ar e inc or p or ated
her ein b y r ef er enc e.
Har d w ater is of ten c har ac ter iz ed as w ater c ontaining a
total dissolv ed solids ( TDS) c ontent in ex c ess of 200 p p m.
This ty p e of w ater is of ten r ef er r ed to as hig h solids c ontain
ing w ater . In c er tain loc alities, the w ater c ontains a total
dissolv ed solids c ontent in ex c ess of 4 00 p p m, and ev en in
ex c ess of 800 p p m. The dissolv ed solids r ef er s to the p r esenc e
of c alc ium and mag nesium. These c omp onents of har d w ater
c an b e addr essed b y sof tening and/ or tr eating the w ater , using
b uilder s, thr eshold ag ents, c r y stal modi? er s and/ or seq ues
tr ants in the deter g ent c omp osition. In the c ase of w ater sof t
ening , sodium is of ten used to disp lac e the c alc ium and mag
nesium. The w ar ew ashing c omp osition c an inc lude b uilder
and/ or seq uestr ant to handle the c alc ium and ther eb y r educ e
its tendenc y to p r ec ip itate w ith the c alc ium c ar b onate.
The deter g ent c omp osition c an inc lude an ef f ec tiv e amount
of anti-etc hing ag ent to p r ev ent c or r osion to g lassw ar e. The
c alc ium that is av ailab le in a use c omp osition f or p r ec ip itating
w ith the aluminum ion c anb e r ef er r ed to as f r ee c alc ium ion
and is g ener ally c onsider ed to b e the unc helated c alc ium ion
in the use c omp osition. When the lev el of f r ee c alc ium ion is
r elativ ely small, it is b eliev ed that the w eig ht r atio of the Z inc
ion to the aluminum ion c an b e p r ov ided at lev els that p r o
v ides the desir ed c or r osion r esistanc es ex hib ited b y a lac k of
etc hing . Bec ause the p r esenc e of f r ee c alc ium ion is not a
p ar tic ular c onc er n, it is b eliev ed that ? lming c aused b y p r e
20
25
3 0
3 5
4 0
4 5
5 0
5 5
60
65
14
c ip itation of c alc ium ion and aluminum ion w ill not b e v er y
sig ni? c ant. A s a r esult, the r atio of the Z inc ion to the alumi
num ion c an b e selec ted as desc r ib ed in Us. ap p lic ation Ser .
N o. 10/ 612, 4 7 4 that w as ? led w ith the United States Patent
and Tr ademar k Of ? c e on J ul. 2, 2003 , and w hic h is inc or p o
r ated her ein b y r ef er enc e in its entir ety . By w ay of ex amp le,
the w eig ht r atio of the Z inc ion to the aluminum ion c an b e
p r ov ided in a r ang e of b etw een ab out 20: 1 to ab out 1: 6, mor e
p r ef er ab ly w ith a w eig ht r atio of the Z inc ion to the aluminum
ion in a r ang e of b etw een ab out 15 : 1 and ab out 1: 2. In situa
tions w her e the f r ee c alc ium ion is av ailab le in the use c om
p osition at a lev el suf ? c ient to c ause p r ec ip itation of the
c alc ium ion and the aluminum ion to p r ov ide v isib le ? lming ,
the r atio of the Z inc ion to the aluminum ion c an b e c ontr olled
to p r ov ide r esistanc e to etc hing and also r esistanc e to v isib le
? lming f r om p r ec ip itation of the c alc ium ion and the alumi
num ion. For ex amp le, w hen the use c omp osition c ontains in
ex c ess of 200 p p m f r ee c alc ium ion, the w eig ht r atio of the
Z inc ion to the aluminum ion c an b e p r ov ided at g r eater than
2: 1. By w ay of an ex emp lar y r ang e, it is b eliev ed that the
w eig ht r atio of the Z inc ion to the aluminum ion c an b e
p r ov ided in a r ang e b etw een ab out 20: 1 and ab out 2: 1, mor e
p r ef er ab ly the w eig ht r atio of Z inc ion to aluminum ion c an b e
g r eater than ab out 3 : 1, and mo st p r ef er ab ly c an b e p r ov ided in
a r ang e b etw een ab out 15 : 1 and ab out 3 : 1. In addition, the
w eig ht r atio of Z inc ion to aluminum ion c an b e p r ov ided at
g r eater than ab out 4 : 1 and c an b e p r ov ided at g r eater than
ab out 6: 1 . It should b e under stood that the r atio of Z inc ion to
aluminum ion may ex c eed 15 : 1 and 20: 1 w hen c or r osion
r esistanc e c an still b e p r ov ided. Fur ther mor e, it should b e
under stood that the r ef er enc e to the w eig ht r atio of the Z inc
ion and the aluminum ion r ef er s to a w eig ht r atio b ased up on
the Z inc c omp onent of the Z inc ion and the aluminum c om
p onent of the aluminum ion. That is, it is the w eig ht of the
metal that is deter mined f or p ur p oses of the w eig ht r atio
r ather than the w eig ht of the entir e molec ule that may c ontain
the metal. For ex amp le, in the c ase of sodium aluminate, the
w eig ht of the aluminum ion r ef er s to the aluminum c omp o
nent of the molec ule r ather than the entir e aluminate ion.
For mulating the Deter g ent Comp osition
The deter g ent c omp osition c an b e f or mulated to handle the
ex p ec ted c or r osion in a g iv en env ir onment. That is, the c on
c entr ation of the c or r osion inhib itor c an b e adjusted dep end
ing up on sev er al f ac tor s at the situs of use inc luding , f or
ex amp le, w ater har dness, f ood soil c onc entr ation, alkalinity
and the like. In mac hine w ar ew ashing ap p lic ations, a soil
c onc entr ation of ab out 25 g r ams p er g allon or mor e is c on
sider ed hig h, a c onc entr ation of ab out 15 to ab out 24 g r ams
p er g allon is c onsider ed medium, and a c onc entr ation of
ab out 14 g r ams p er g allon or less is c onsider ed low . A lso,
w ater har dness ex hib iting 15 g r ains p er g allon or mor e is
c onsider ed hig h, ab out 6 to ab out 14 g r ains p er g allon is
c onsider ed medium, and ab out 5 g r ains p er g allon or less is
c onsider ed low . In a use c omp osition, an alkalinity of ab out
3 00 p p m or hig her is c onsider ed hig h, an alkalinity of ab out
200 p p m to ab out 3 00 p p m is c onsider ed medium, and an
alkalinity of ab out 200 p p m or less is c onsider ed low . In a use
c omp osition, a b uilder c onc entr ation of ab out 3 00 p p m or
mor e is c onsider ed hig h, a b uilder c onc entr ation of ab out 15 0
p p m to ab out 3 00 p p m is c onsider ed medium, and a b uilder
c onc entr ation of 15 0 p p m or less is c onsider ed low .
Based on the desir ed minimum c onc entr ation of the c or r o
sion inhib itor in the use c omp osition, the amount of the c or
r osion inhib itor in the c onc entr ate c an b e c alc ulated know ing
the solids c ontent of the use c omp osition and the c onc entr ate
c an b e f or mulated to p r ov ide at least the desir ed lev el of
c or r osion p r otec tion.
US 8, 691, 018 B2
15
For ming the Conc entr ate
The c omp onents c an b e mix ed/ b lended, ex tr uded, or c ast to
f or m a solid suc h as p ellets, p ow der s or b loc ks. Heat c an b e
ap p lied f r om an ex ter nal sour c e to f ac ilitate p r oc essing of the
mix tur e.
A mix ing sy stem p r ov ides f or c ontinuous mix ing of the
ing r edients at hig h shear to f or m a sub stantially homog e
neous liq uid or semi-solid mix tur e in w hic h the ing r edients
ar e distr ib uted thr oug hout its mass. The mix ing sy stem
inc ludes means f or mix ing the ing r edients to p r ov ide shear
ef f ec tiv e f or maintaining the mix tur e at a ? ow ab le c onsis
tenc y , w ith a v isc osity dur ing p r oc essing of ab out 1, 000-1,
000, 000 c P, p r ef er ab ly ab out 5 0, 000-200, 000 c P. The mix ing
sy stem c an b e a c ontinuous ? ow mix er or a sing le or tw in
sc r ew ex tr uder ap p ar atus.
The mix tur e c an b e p r oc essed at a temp er atur e to maintain
the p hy sic al and c hemic al stab ility of the ing r edients, suc h as
at amb ient temp er atur es of ab out 20-800 C. , and ab out 25 -5 5
C. A lthoug h limited ex ter nal heat may b e ap p lied to the mix
tur e, the temp er atur e ac hiev ed b y the mix tur e may b ec ome
elev ated dur ing p r oc essing due to f r ic tion, v ar ianc es in amb i
ent c onditions, and/ or b y an ex other mic r eac tion b etw een
ing r edients. Op tionally , the temp er atur e of the mix tur e may
b e inc r eased, f or ex amp le, at the inlets or outlets of the mix ing
sy stem.
A n ing r edient may b e in the f or m of a liq uid or a solid suc h
as a dr y p ar tic ulate, and may b e added to the mix tur e sep a
r ately or as p ar t of a p r emix w ith another ing r edient, as f or
ex amp le, the c or r osion inhib itor c omp onent may b e sep ar ate
f r om the r emainder of the deter g ent. One or mor e p r emix es
may b e added to the mix tur e.
The ing r edients ar e mix ed to f or m a sub stantially homo
g eneous c onsistenc y w her ein the ing r edients ar e distr ib uted
sub stantially ev enly thr oug hout the mass. The mix tur e c an b e
disc har g ed f r om the mix ing sy stem thr oug h a die or other
shap ing means. The p r o? led ex tr udate c an b e div ided into
usef ul siz es w ith a c ontr olled mass. The ex tr uded solid c an b e
p ac kag ed in ? lm. The temp er atur e of the mix tur e w hen dis
c har g ed f r om the mix ing sy stem c an b e suf ? c iently low to
enab le the mix tur e to b e c ast or ex tr uded dir ec tly into a
p ac kag ing sy stem w ithout ? r st c ooling the mix tur e. The time
b etw een ex tr usion disc har g e and p ac kag ing c an b e adjusted
to allow the har dening of the deter g ent b loc k f or b etter han
dling dur ing f ur ther p r oc essing and p ac kag ing . The mix tur e
at the p oint of disc har g e c an b e ab out 20-900 C. , and ab out
25 -5 5 C. The c omp osition c an b e allow ed to har den to a solid
f or m that may r ang e f r om a low density , sp ong e-like, mal
leab le, c aulky c onsistenc y to a hig h density , f used solid, c on
c r ete-like b loc k.
Op tionally , heating and c ooling dev ic es may b e mounted
adjac ent to mix ing ap p ar atus to ap p ly or r emov e heat in or der
to ob tain a desir ed temp er atur e p r o? le in the mix er . For
ex amp le, an ex ter nal sour c e of heat may b e ap p lied to one or
mor e b ar r el sec tions of the mix er , suc h as the ing r edient inlet
sec tion, the ? nal outlet sec tion, and the like, to inc r ease ? u
idity of the mix tur e dur ing p r oc essing . Pr ef er ab ly , the tem
p er atur e of the mix tur e dur ing p r oc essing , inc luding at the
disc har g e p or t, is maintained at ab out 20-900 C.
When p r oc essing of the ing r edients is c omp leted, the mix
tur e may b e disc har g ed f r om the mix er thr oug h a disc har g e
die. The solidi? c ation p r oc ess may last any w her e f r om a f ew
minutes to ab out six hour s, dep ending , f or ex amp le, on the
siz e of the c ast or ex tr uded c omp osition, the ing r edients of the
c omp osition, the temp er atur e of the c omp osition, and other
like f ac tor s. Pr ef er ab ly , the c ast or ex tr uded c omp osition sets
up or b eg ins to har den to a solid f or m w ithin ab out 1 minute
20
25
3 0
3 5
4 0
4 5
5 0
5 5
60
65
16
to ab out 6 hour s, mor e p r ef er ab ly w ithin ab out 1 minute to
ab out 3 hour s, and most p r ef er ab ly w ithin ab out 1 minute to
ab out 1. 0 hour s.
The c onc entr ate c an b e p r ov ided in the f or m of a liq uid.
Var ious liq uid f or ms inc lude g els and p astes. Of c our se, w hen
the c onc entr ate is p r ov ided in the f or m of a liq uid, it is not
nec essar y to har den the c omp osition to f or m a solid. In f ac t, it
is ex p ec ted that the amount of w ater in the c omp osition w ill
b e suf ? c ient to p r ec lude solidi? c ation. In addition, disp er s
ants and other c omp onents c an b e inc or p or ated into the c on
c entr ate in or der to maintain a desir ed distr ib ution of c omp o
nents.
The p ac kag ing r ec ep tac le or c ontainer may b e r ig id or
? ex ib le, and c omp osed of any mater ial suitab le f or c ontaining
the c omp ositions p r oduc ed ac c or ding to the inv ention, as f or
ex amp le g lass, metal, p lastic ? lm or sheet, c ar db oar d, c ar d
b oar d c omp osites, p ap er , and the like. The c omp osition is
p r oc essed at ar ound 15 0-17 00 F. and ar e g ener ally c ooled to
100-15 00 b ef or e p ac kag ing allow ing the mix tur e to b e
dir ec tly added to the c ontainer or other p ac kag ing sy stem
w ithout str uc tur ally damag ing the r ec ep tac le. A s a r esult, a
w ider v ar iety of mater ials may b e used as p ac kag ing sy stems.
The p ac kag ing mater ial c an b e p r ov ided as a w ater solub le
p ac kag ing mater ial suc h as a w ater solub le p ac kag ing ? lm.
Ex emp lar y w ater solub le p ac kag ing ? lms ar e disc losed in
Us. Pat. N os. 6, 5 03 , 87 9; 6, 228, 825 ; 6, 3 03 , 5 5 3 ; 6, 4 7 5 , 97 7 ;
and 6, 63 2, 7 85 , the disc losur es of w hic h ar e inc or p or ated
her ein b y r ef er enc e. A n ex emp lar y w ater solub le p oly mer that
c an p r ov ide a p ac kag ing mater ial that c an b e used to p ac kag e
the c onc entr ate inc ludes p oly v iny l alc ohol. The p ac kag ed
c onc entr ate c an b e p r ov ided as unit dose p ac kag es or multip le
dose p ac kag es. In the c ase of unit dose p ac kag es, it is
ex p ec ted that a sing le p ac kag ed unit w ill b e p lac ed in the
c leaning ap p ar atus, suc h as the deter g ent c omp ar tment of the
dishw ashing mac hine, and w ill b e used up dur ing a sing le
w ash c y c le. In the c ase of a multip le dose p ac kag e, it is
ex p ec ted that the unit w ill b e p lac ed in a hop p er and a str eam
of w ater w ill er ode a sur f ac e of the c onc entr ate to p r ov ide a
liq uid c onc entr ate that w ill b e intr oduc ed into the dishw ash
ing mac hine.
While the inv ention is desc r ib ed in the c ontex t of a w ar e
w ashing c omp osition f or w ashing ar tic les in an automatic
dishw ashing mac hine, it should b e under stood that the c om
p osition c an b e used f or w ashing non-w ar e items. That is, the
c omp osition c an b e r ef er r ed to as a c leaning c omp osition and
c an b e used to c lean v ar ious items and, inp ar tic ular , items that
may suf f er f r om c or r osion and/ or etc hing . It should b e under
stood that b ec ause the deter g ent is intended to b e used in an
automatic dishw ashing mac hine c er tain c omp onents c an b e
ex c luded f r om the deter g ent c omp ositions not intended f or
use in w ar ew ash mac hines, and v ic e v er sa. For ex amp le,
sur f ac tants that g ener ate a lot of f oam may b e used in a
c leaning c omp osition not intended f or use in an automatic
dishw ashing mac hine.
Ex emp lar y r ang es of the deter g ent c omp osition in its sim
p lest f or m inc lude a sour c e of alkalinity and a c or r osion
inhib itor . It is p r ef er r ed that the sour c e of alkalinity c omp r ises
a r ang e of 3 0-99 w t. %, mor e p r ef er ab ly a r ang e of 3 5 -80 w t.
% and most p r ef er ab ly a r ang e of 4 0-7 0%. The c or r osion
inhib itor of the inv ention is p r esent in a p r ef er r ed r ang e of
l-3 0 w t. %, a mor e p r ef er r ed r ang e of 5 -25 w t. % and a most
p r ef er r ed r ang e of 10 to 20 w t. % of ac tiv e p oly mer .
A c c or ding to the inv ention, the c or r osion inhib itor c om
p r ises one or mor e hig h molec ular w eig ht p oly ac r y lates
( p oly ac r y lic homop oly mer s) hav ing a molec ular w eig ht of at
least ab out 5 000.
US 8, 691, 018 B2
17
Ex emp lar y r ang es f or ty p ic al c omp onents of deter g ent
c omp ositions inc luding the c or r osion inhib itor of the inv en
tion ar e show n in tab les 1 and 2. Ex emp lar y r ang es w hen
p r ov ided as a g el or a p aste ar e show n in Tab le 1. Ex emp lar y
r ang es f or c omp onents of the deter g ent c omp osition w hen
p r ov ided as a solid ar e show n in Tab le 2.
1 8
A c usol 929-10, 000 MW p oly ac r y late, 4 5 % ac tiv e
A c umer 15 10-7 0, 000 MW p oly ac r y late, 25 % ac tiv e
A c usol 4 4 5 N D-4 , 5 00 MW p oly ac r y late, 95 -100% ac tiv e
The c omp onents of the test deter g ents ar e listed in Tab les A
and B b elow .
TA BLE A
TA BLE 1
Cor r osion Inhib itor Comp onent
Gel or Paste Deter g ent Comp osition ( w t. %) 10
Cor r osion
Fir st Sec ond Thir d Inhib itor CON TROL EXPl EXP2 EXP3
Comp onent Ex emp lar y Ex emp lar y Ex emp lar y
STPP 25 w t. % 0 0 0
Water 5 95 20 7 5 3 0 5 0 Poly A c r y late A c usol 929 A c umer A c usol
Silic ate/ 0-65 25 -60 3 5 -5 5 ( 4 5 %) 15 10 ( 25 %) 4 4 5 N D
alkaline sour c e 15 22 w t. % 4 0 w t. % 10 w t. %
Bnilder 0-3 0 3 -20 6-15
Stab iliz er 0-20 0. 5 -15 2-10
Disp er sant 0 20 05 15 2 9
Enz y me 0 15 05 10 1 5
Poly ac r y late 0. 5 5 0 1 3 0 5 20 TA BLE B
Cor r osion 20
Inhib itor War ew ash deter g ent c omp onents
Sur f ac tant 0. 5 15 1 10 2 5
Fr ag r anc ? o_ 1o 0. 015 0. 1_ 2 CON TROL EXPl EXP2 EXP3
Dy 6 0-1 0-001-0-5 0-01-0-25 Sof tened 3 0. 87 7 w t. % 24 w t. % 6 w t. % 3 6 w t. %
w ater
25 Sour c e of 25 . 85 w t. % 5 3 w t. % 5 3 w t. % 5 3 w t. %
alkalinity
TA BLE 2 Sur f ac tant . 86 w t. % 1 w t. % 1 w t. % 1 w t. %
Solid Deter g ent Comp o ition ( w t. %) ~ ~ ~
The ex p er r mental deter g ent c omp ositions and the c ontr ol
Fir s: 5 6 01? Thir ii 3 0 w er e tested ac c or ding to standar d p r otoc ol in a multi-c y c le
c omp omnt Ex emp My Emmp My Ex emp my aluminum c or r osion inhib ition ev aluation f or w ar ew ash
Water 5 -60 15 -4 5 25 -4 0 deter g ents as desc r ib ed her einaf ter .
Blinder 0' 60 25 ' 5 0 3 5 ' 4 5 A 13 " > < 9" aluminum sheet p an w as ob tained b y c utting a
Slhc ate/ ( > 65 25 60 3 5 5 5 13 " > < 18" an in half The an w as entl c leaned w ith w ar m
alkaline sour c e 3 5 p ' p ' g y '
Disp er sant 0-10 0. 001-5 0. 01-1 soap y w ater and a non-ab r asiv e sp ong e to ensur e any f or eig n
Enz y me 0' 15 1' 10 2' 5 mater ials or r esidues f r om c utting and stor ag e w er e r emov ed.
Poly ac r y late 0. 5 5 0 1 3 0 5 20 . .
Cor r osion N ex t a d1shw asher w as ? lled w r th w ater and heater s w er e
Inhib itor tur ned on. For hig h temp er atur e mac hines, the w ash temp er a
Sur f ac tant 0-5 ' 15 1' 10 2' 5 4 o tur e w as set to 160 F. and the ? nal r inse temp er atur e w as
Fr ag r anc e 0 10 0. 01 5 0. 1 2 - o - ~ -
Dy ? 0_ 1 0_ 001_ 0_ 5 0_ 01_ 0_ 25 adjusted to 180 The Mac hine w as then p r 1med w r th the
des1r ed c onc entr atr on of deter g ent and the p an w as p lac ed 1n
the sec ond slot f r om f r ont w ith the r im f ac ing dow n and c ut
The ab ov e sp ec i? c ation p r ov ides a b asis f or under standing edg e f ac ing up
the b r oad meets and b ounds Of the inv ention. The f OllOWlhg 4 5 The p an r ac k w as then p ushed into the mac hine, the door
ex amp les and F65 1 data Pr ov lde an_ under 5 1and1ng Of c enaln w as c losed, and the c y c le w as star ted. A t the b eg inning of
Sp em? c emdelmems Of the lllv emlc f n- The ex amp les ar e 1101 eac h c y c le, the ap p r op r iate amount of deter g ent w as added to
meant to limit the sc op e of the 1nv entr onthat has b een set f or th the w ash tank to make up f or the r inse dilution This w as
In the f or eg omg desc np non' Vananon Wltmn the Conc ep ts Of r ep eated until the desir ed numb er of c y c les w er e c omp leted.
the 1nv entr on ar e ap p ar ent to those skilled 1n the ar t. 5 0
RESULTS
EXA MPLES
Pans w er e r ated v isually and p hotog r ap hed ag ainst a b lac k
E 1 1 b ac kg r ound. The r ating sc ale used w as as f ollow s and w as the
x am e
p 5 5 same f or the f r ont and b ac k of eac h p an:
A c c or ding to the inv ention, sev er al deter g ent c omp ositions
w er e p r ep ar ed w ith hig h molec ular w eig ht p oly ac r y lates
( p oly ac r y lic ac id homop oly mer ) hav ing a molec ular w eig ht Ratng Film
of at least ab out 5 000 as the c or r osion inhib itor and c omp ar ed 60 1 N o c or r osion or disc olor ation
to a c ommer c ially av ailab le c ontr ol f or mulation c ontaining 2 A p p r ox imately 25 % Of the p an is disc olor ed author c or r oded
sodium tr ip oly p hosp hate as a c or r osion inhib itor . The deter - 3 A p p r ox imately 5 0% of the p an is disc olor ed and/ or c or r oded
g ent c omp onents w er e kep t c onstant ex c ep t f or the c or r osion 4 A p p r ox unmly 7 5 % OM16 Pan ls { moo-lor d and c omm
. . . . . . 5 A ll or near ly all of the p an 1s heav r ly dlsc olor ed and/ or c or r oded
1nh1b 1tor c omp onent. Commer c r ally av ar lab le h1g h molec ular
w eig ht p oly ac r y lates ( p oly ac r y lic ac id homop oly mer ) hav ing 65
a molec ular w eig ht of at least ab out 5 000 used in the 3
samp les ar e listed b elow .
The r esults show n in the f ollow ing tab le c or r elate to the
c omp ositions show n ab ov e. Results ar e g r aded v isually f r om
US 8, 691, 018 B2
19
1 ( b est) to 5 ( w or st) dep ending up on the amount of b lac ken
ing / c or r osion of an aluminum p an.
Pr oduc t Cy c les Conc ( p p m) Fr ont Sc or e Bac k Sc or e
SMP In-Line 5 0 2000 1 1
SMP 1 5 0 97 5 1 1. 5
SMP 2 5 0 97 5 1. 5
SMP 3 5 0 97 5 5 5
A s c an b e seen, the hig h molec ular w eig ht p oly ac r y lates
( ac r y lic ac id homop oly mer ) c leaned almost as w ell as the
c ontr ol, and ar e muc h mor e env ir onmentally f r iendly as the
f or mulations c ontained to p hosp hor ous.
A s also c anb e seen the at molec ular w eig hts of under 5 000,
the c or r osion inhib ition w as unsatisf ac tor y , thus the p oly ac r y
late ( p oly ac r y lic ac id homop oly mer ) shouldhav e a molec ular
w eig ht of at least ab out 5 000 and p r ef er ab ly 10, 000 or mor e.
What is c laimed is:
1. A deter g ent c omp osition c omp r ising :
( a) a metal silic ate in an amount ef f ec tiv e to p r ov ide a use
c omp osition hav ing a p H of at least ab out 8 and ob tained
b y diluting the deter g ent c omp osition w ith w ater ,
w her ein said ef f ec tiv e amount of metal silic ate is
b etw een 3 0 w t. % and 5 5 w t. %; and
( b ) a c or r osion inhib itor c omp onent in an amount suf ? c ient
f or r educ ing c or r osion of aluminum or aluminum c on
taining alloy s, the c or r osion inhib itor c omp onent c on
sisting of one or mor e p oly ac r y lic ac id homop oly mer s
hav ing a molec ular w eig ht of at least ab out 5 , 000 dal
tons, w her ein said suf ? c ient amount of c or r osion inhib i
tor is b etw een 5 w t. % and 3 0 w t. %;
w her ein said c omp osition c ontains less than ab out 0. 1% b y
w eig ht of p hosp hor ous;
w her ein said c omp osition does not inc lude 1-hy dr ox y eth
y lidene l-l-dip hosp honic ac id; and
w her ein said c omp osition does not inc lude sodium c ar b on
ate.
2. The deter g ent c omp osition ac c or ding to c laim 1 f ur ther
c omp r ising :
( c ) a c leaning ag ent c omp r ising a deter siv e amount of a
sur f ac tant.
3 . The deter g ent c omp osition ac c or ding to c laim 2,
w her ein the deter g ent c omp osition c omp r ises b etw een ab out
0. 5 w t. % and ab out 20 w t. % of the c leaning ag ent.
4 . The deter g ent c omp osition ac c or ding to c laim 1,
w her ein said ac r y lic ac id homop oly mer has a molec ular
w eig ht of g r eater than 10, 000 daltons.
20
25
3 0
3 5
4 0
20
5 . The deter g ent c omp osition ac c or ding to c laim 2,
w her ein the c leaning ag ent c omp r ises at least one of an
anionic sur f ac tant, a nonionic sur f ac tant, a c ationic sur f ac
tant, or a z w itter ionic sur f ac tant.
6. The deter g ent c omp osition ac c or ding to c laim 1 w her ein
the deter g ent c omp r ise less than ab out 0. 05 % b y w eig ht of
p hosp hor ous.
7 . The deter g ent c omp osition ac c or ding to c laim 1 w her ein
the deter g ent is sub stantially p hosp hor ous f r ee.
8. A method f or manuf ac tur ing a deter g ent c omp osition,
the method c omp r ising :
( a) p r ov iding an amount of c or r osion inhib itor in a deter
g ent c omp osition c onc entr ate su? ic ient to p r ov ide a
lev el of c or r osion inhib itor in a use c omp osition as a
r esult of diluting the deter g ent c onc entr ate w ith w ater at
a r atio of w ater to the deter g ent c onc entr ate of at least
ab out 20: 1 w her ein said c or r osion inhib itor is b etw een 5
w t. % and 3 0 w t. % in the c onc entr ate and c omp r ises one
or mor e ac r y lic ac id homop oly mer s hav ing a molec ular
w eig ht of at least ab out 5 , 000 daltons and c omp r ises less
than ab out 0. 1% b y w eig ht of p hosp hor ous, and w her ein
said deter g ent c omp osition c onc entr ate c omp r ises an
alkaline sour c e b etw een 3 0 w t. % and 90 w t. %, and
f ur ther w her ein said alkaline sour c e inc ludes a metal
silic ate and does not inc lude 1-hy dr ox y ethy lidene 1-1
dip hosp honic ac id or sodium c ar b onate.
9. A method f or p r otec ting aluminum or aluminum c on
taining alloy s f r om c or r osion c omp r ising :
c ontac ting the sur f ac e of the same w ith a c or r osion inhib itor
c omp r ising :
( a) one or mor e ac r y lic ac id homop oly mer s hav ing a
molec ular w eig ht of at least ab out 5 , 000 daltons, and
w her ein said c or r osion inhib itor is b etw een 5 w t, % and
3 0 w t. % of a deter g ent c omp osition, said deter g ent
c omp osition inc luding less than ab out 0. 1% b y w eig ht of
p hosp hor ous and f ur ther inc luding
( b ) an alkaline sour c e in an amount ef f ec tiv e to p r ov ide a
use c omp osition hav ing a p H of at least ab out 8, w her ein
said ef f ec tiv e amount of alkaline sour c e is b etw een 3 0
w t. % and 5 5 w t. %, and f ur ther w her ein said alkaline
sour c e inc ludes a silic ate;
( c ) w her ein said c or r osion inhib itor does not inc lude
sodium c ar b onate; and
( d) w her ein said c or r osion inhib itor does not inc lude l-hy
dr ox y ethy lidene l-l-dip hosp honic ac id.
10. The method of c laim 9, w her ein the c or r osion inhib itor
c omp r ises one or mor e ac r y lic ac id homop oly mer s hav ing a
molec ular w eig ht of g r eater than 10, 000 daltons.
* * * * *
UN ITED STA TES PA TEN T A N D TRA DEMA RK OFFICE
CERTIFICA TE OF CORRECTION
PA TEN T N O. 2 8, 691, 018 B2 Pag e 1 of l
A PPLICA TION N O. : 12/ 869815
DA TED : A p r il 8, 2014
IN VEN TOR( S) : Er ik Chr istian Olson et a1.
It is c er tif ied that er r or ap p ear s in the ab ov e-identif ied p atent and that said Letter s Patent is her eb y c or r ec ted as show n b elow :
In the Claims
Col. 20, Claim 9, Line 3 3 :
DELETE af ter b etw een 5 w t, %
A DD af ter b etw een --5 w t. %-
Sig ned and Sealed this
Sev enteenth Day of J une, 2014
WMZ 4 4 L_
Mic helle K. Lee
Dep uty Dir ec tor 0f the United States Patent and Tr ademar k O? ic e