Note: Descriptions are shown in the official language in which they were submitted.
wo 94/01~17 2 i 3 .~ 9 2 o Pcr/US93/063~9
Descrinlion
AQUEOUS LUBRICATION AND SIJRFACE CONDITIONING FOR
FORMED METAL SURFACES
BACKGROUND OF THE INVENTION ~
Field of the Invention
This invention relates to processes and compositions which accomplish at least
one, and most preferably all, of the following related objectives when applied to
5 formed meial surfaces. more particularly to the surfaces of cleaned aluminum and/or
tin plated cans: (i) reducing the coefficient of static friction of the treated surfaces
after drying of such surfaces, without adversely affecting the adhesion of paints or lac-
quers applied thereto; (ii) promoting the drainage of water from treated surfaces,
withou~ causing "water-breaks", i.e., promoting drainage that results in a thin?10 continuous film of water on the cans, instead of distinct water droplets separated by
the relatively dry areas called "water-b~eaks" be~ween the water droplet~; and (iii)
lowering the dryoff oven temperature required for drying said surfaces after they have
been rinsed with water.
Discussion of Related Art
The following discussion and the description of the invention will be set forth
primarily for aluminum cans, as these represent the largest volume area of application
of the invention. However, it is to be understood that, with the obviously necessary
modifications, both the discussion and the description of the invention apply also to
tin plated steel cans and to other types of formed metal surfaces for which any of the
20 above stated intended purposes of the invention is practically in~eresting.
Aluminum cans are commonly used as containers for a wide variety of prod-
ucts. After their manufacture, the aluminum cans are typically washed with acidic
cleaners to remove aluminum fines and other contaminants therefrom. Environrnental
i considerations and the possibility that residues remaining on the cans following acidic
25 cleaning could influence the flavor of beverages packaged in the cans has led to an
interest in alkaline or acid clearling to remove such fines and contaminants. However,
such cleaning of aluminum cans generally results in differential rates of metal surface
etch on the outside versus on the inside of the cans. For example, optimum conditions
wo 94/01517 2 i Pcr/uss3/o635
required to attain an aluminum fine-free surface on the inside of the cans usùally leads
to can mobility problems on conveyors because of the increased roughness on ~he
outside can surface.
Aluminum cans ~hat lack a low coefficient of sta~ic friction (hereinafter often
s abbreviated as "COF") on the outside surface usually do not move past each other and
through ~he trackwork ol a can plant smoothly. ClAe~g the jams resulting from
failures of smooth flow is inconvenient to the persons operating the plant and costly
-
because of lost produc~ion. The COF of the int~rnal surface is also important when
the cans are processed ~hrough most conven~ional can decorators. The opera~ion of
these machines requires cans tC slide onto a rotating mandrel which is then used to --
transfer the can past rotating cylinders which transfer decorative inks to the exterior ;
surface of the cans. A can that does not slide easily on or off the mandrel can not be
decorated properly and results in a produc~on fault called a "printer trip". In addition
to the misloaded can that directly causes such a printer trip, three to four cans before ~ `-
and after the misloaded one are generally lost as a consequence of the mechanics of
the pnnter and conveyor systems. Jams and printer trips have become increasinglytroublesome problems as line speed have increased during recen~ years to levels of
- about 1200 to 1500 cans per minute tha~ are now common. Thus, a need has arisen i~
in the can manufacturing industry, particularly with aluminum cans, to modify the
COF on the outside and inside surfaces of the cans to irnprove their mobility. i '; `
An important consideration in modifying ~he surface properties of cans is the
concern that such modification may interfere with or adversely affect ~he ability of the
can to be printed when passed to a printing or labeling station. For example, after
cleaning the cans, labels may be printed on their outside surface, and lacquers may be . `
sprayed on their inside surface. ln such a case, the adhesion of the paints and `~
lacquers is of major concern. lt is therefore an object of this invention to improve
mobility without adversely affecting adhesion of paints, decorating inks, lacquers, or
the like. ~-
In addition, the current trend in the can manufacturing industry is directed ~. I
toward using thinner gauges of aluminum metal stock. The down-gaugin~ of alumi-
num can metal stock has caused a production problem in that? after washing. the cans
require a lower drying oven temperature in order to pass the column strength pressure
2 `.
.~
wO 94/01517 2 1 3 ~ Pcr/US93/06359
qualily conlrol test. However. Iowering Lhe drying oven temperature resulted in ~hc
cans not being dry enough when they reached the printino sta~ion1 and caused label
ink smears and a higher rate of can rejecls.
One means of lowering the drying oven temperature would be to reduce the
5 amount of water remaining on the surface of the cans after water rinsing. Thus, it is
advantageous to promote the drainage of rinse water from the treated can surfaces.
However, in doing so, it is generally important to prevent the formation of surfaces
with water-breaks as noted above. Such water-breaks give rise to at least a per-ception. and increase the possibility in realityl of non-uniforrnity in practically
.o important properties among various areas of the surfaces treated.
Thusl it iS? desirable to provide a means of improving the mobility of aluminum
cans through single filers and printers to increase production1 reduce line jammings
minimi~e down time, reduce can spoila~e, improve or at least not adversely affect ink
laydownl and enable lowering the drying oven temperature of washed cans.
In the most widely used current commercial practice, at least for large scale
operations, alurninum cans are typically subjected to a succession of six cleaning and
rinsing operations as described in Table 1 below. (Contact with arnbient temperature
tap water before any of the stages in Table 1 is sometimes used also; when used, this
stage is often called a "vestibule" to the numbered stages.)
I ~
Table 1
~ =
STAGE ACTION ON SURFACE DURING STAGE
NUMBER
_ = _ __ = - _ , .
1 Aqueous Acid Precleaning ¦
I _ . .
. 2 Aqueous Acid and Surfactant Cleaning l
I _ _ . . I
2s 3 Tap Water Rinse l
I _ ; -- _ . I
4 Mild Acid Postcleaning, Conversion
Coating? or Tap Water Rinse l
I , _ . I
Tap Water Rinse
I . _ _ .
6 Deionized ("DI") Water Rinse
, ~ . .
It is currently possible to produce a can which is satisfactorily mobile and to
which subsequently applied inks and/or lacquers have adequate adhesion by usin~ suit-
WO 94/01517 2 1 3 5 9 2 0 Pcr/VS93/063~9 ~
~.~`'' ~',
able surfactants eithcr in ~tag~ 4 or S~age 6 as noted above. Preferred treatments for
use in Stage 6 are described in U. S. Patents 4.944.889 and 4,859.351, and some of
them are commercially available from the Parker+Amchem Division of Henkel Cor-
poration (hereinafter often abbreviated as "P+A") under the name ME-40(~
s However, many manufacturers have been found t~ be reluctant to use chemi-
cals such as ME-40(i~ in Staoe 6. In some cases, this rell~nce is due to the presence
of a carbon filter for the DI water (normal Stage 6~ s~ stem, a filter that can become
inadequately effective as a result of adsorption o~`lubricant and surface conditioner
formin~ additives such as those in ME-40(~; in other cases, it is due to a reluctance
to make the engineering changes necessary to run ME-40.
For those manufacturers that prefer not to add any lubricant and surface condi-
tioner rnaterial to the final staoe of rinsing but still wish to achieve the advantages tha~
can be obtained by such additions, alternative treatments for use in Stage 4 as
described above have been developed and are described in U. S. Patents 5,030,323 and
5,064,500. Some of these materials are commercially available from P+A under tbe name FIXODINE~) 500.
However7 the reduction in coefficient of friction provided by prior art trea~
ments in either Stage 4 or Stage 6 can be substantially reduced, often to an unaccept^
able level, ii the treated cans are subjected to extraordinary heating after completion
of the six process stages described above. Such extraordinary heating of the cans in
the drying oven occurs whenever a hi~h speed production line is stalled for even a few
minutes, an event that is by no means rare in practice. ln practical terms, the higher
.
COF measùrements correlate with the loss of mobility, thereby defeatino the purpose
of introducing mobility enhancing surfactants into can washing formulations. Accord- ~
ingly, it is an object of this invention to provide means of improvin~ the mobility of ,`
aluminum cans and/or one of the other objects stated above that are superior to means
taught in the prior art7 particularly with respect to stàbility of the beneficial effects to ~ .
heating well beyond the minimum extent necessary .for drying the treated surfaces.
I:)ESCRI~llON OF THE INVENTIQN
~o Other than in the operating examples, or where otherwise indicated, all num~
bers expressing quantities of in~gredients or reaction conditions used herein are to be .
understood as modified in all instances by the terrn "about" in describing the broadest '. .;
4 ~:
wo 9~/01517 2 1 ~ 5 9 2 0 PC~/US93/06359
, . . ..
scope of lhe invention. Practice within the numerical limits given~ howeven is gener-
ally preferred.
Also, unless there is an explicit statement to the contrary, the description below
of ~roups of chemical materials as suitable or preferred for a particular ingredient ac-
5 cording to the invention implies that mixtures of two or more of the individual groupmembers are equally as suitable or preferred as the individual members of the group
used alone. Furthermore, the specification of chemical materials in ionic form should
be understood as implying the presence of some counterions as necessary for electrical
neutrality of the total composi~ion. In general, such counterions should first be select-
10 ed to the extent possible from the ionic materials specified as part of the invention;any remaining counterions needed may generally be selected freely, except for
avoiding any counterions that are detrimental to the objects of the invention.
Summary of the Invention
In accordance with ~his invention, it has been found that the coefficient of fric-
15 tion of a surface treated with a lubricant and surface conditioner is less easily darn-
aged by heating when the lubricant and surface conditioner composition includes at
least one of the following organic materials: alkoxylated or non-alkoxylated castor oil
triglycerides and hydrogenated castor oil derivatives; aL~oxylated and non-aL~oxylated
amine salts of a fatty àcid including mono-, di-, tri-, and poly-acids; alkoxylated and
20 non-alkoxylated amino fatty acids; alkoxylated and non-alkoxylated fatty amine N-ox-
ides, alkoxylated and non-alkoxylated quaternary ammonium salts~ alkyl esters of 2-
substituted alkoxylated fatty alkyloxy acetic acids (briefly denoted hereinafter as "oxa-
acid esters") as described more fully in PCT Application US93/014Il filed February
23, 1993, and water-soluble alkoxylated and non-aLkoxylated polymers. Furthermore,
25 if the lubricant and surface conditioner is not applied to the surface from the last
aqueous composition with which the surface is contacted before the last drying of the
surface before automatic conveying, the composition including the organic materials
should also include a metallic element selected from the group consisting of zirconi-
um, titanium, cerium. aluminum. iron, tin, vanadium, tantalum, niobium, molybdenum,
30 tungsten, and hafnium in metallic or ionic form, and the film formed on the surface
as part of the lubricant and surface conditioner in dried form should include some of
this metallic element along with o~anic material.
WO94/01517 213S9~ PCr/US93/06359~,~
Description of Preferred Emhodiments '
Preferred alkoxyla~ed. especially e~hoxylatcd, castor oil triolycerides tha~ arccommercially available include Trylox(i~) 5900, Trylox~ 5902. Trylox(~ 5904, Trylox(~
5906, Trylox(~ 5907, Trylox(~ 5909, Trylox(~) 5918. and p,referred hydrogena~ed castor
oil deriva~ives include commercial ma~erials such as TE~ X(~ 5921 and Trylox6~ 5922,
all available from Henkel Corporation. These ,ma~tèrials are particularly useful as
additives to final stage rinses, because they pr~v;de a dried lubricant and surface
conditioner film on the trea~ed surl`ace tha~ resists rise of the COF wi~h heating beyond
~he minimum necessary ~o dry the surface.
Another preferred group of organic materials cornprise water-soluble alkoxyl-
ated, preferably ethoxylated, propoxylated, or mixed ethoxylated and propoxylated
materials, most preferably ethoxylated, and non-ethoxylated or~anic materials selected
from asnine salts of fatty acids includin~ mono-, di-, tri-, and poly-acids, amino fatty
acids, fatty arnine N-oxides. and quaternary salts, and water soluble polymers.
Preferred amine salts of fatty acids include arnmonium, quaternary ammonium,
phosphonium, and aLkali metal salts of fatty acids and derivatives thereof containing
up to 50 moles of alkylene oxide in either or both the cationic or anionic species
Specific examples include Amphoteric N and Amphoteric 400 iminodipropionate sod-ium salts, available from Exxon Chemical Co.; Deriphat(~) 154 disodium N-tallow-beta
iminodipropionate and Deriphat(~) 160, disodium N-lauryl-beta iminodipropionate,available from Henkel Corp.
Preferred amino acids include alpha and beta amino acids and diacids and salts
thereof, including alkyl and alkoxyiminodipropionic acids and their salts and sarcosine
derivatives and their salts. Speci~lc examples include Armeen(~) Z, N-coco-beta-aminobutyric acid, available from Akzo Chemicals Inc.; Amphoteric N, Amphoteric
400, Exxon Chemical Co.; sarcosine (N-methyl glycine); hydroxyethyl glycine;
Harnposyl~ TL-40 triethanolamine lauroyl sarcosinate, Hamposyl~9 O oleyl sarcosin-
ate, Hamposyl~) AL-30 ammoniumlauroyl sarcosinate, Hamposyl~ L lauroyl sarcosin-ate, and Harnposyl~9 C cocoyl sarcosinate, all available from W.R. Grace & Co.
Preferred amine N-oxides include amine oxides where at least one alkyl sub-
stituent contains at least three carbons and up to 20 carbons. Specific examplesinclude Aromox~) C/12 bis-(2-hydroxyethyl)cocoalkylamine oxide. Aromox(~) Ttl2
wo 94/01517 213 S 9 2 0 Pcr/us93/o63s9
A ~ ' ;", .
bis-(2-hydroxyethyl~tallowalkylamineoxide, Aromox(~) DMC dimethylcocoalkylamine
oxide, Aromox(~) DMHT hydro,~enated dimethyltallowaLkylamine oxide, Aromox(~ ,i
DM-16 dimethylheaxdecylalkylamine oxide, all available from Akzo Chemicals lnc.;and Tomah(~ AO-14-2 and Tomah@; AO-72~ available from Exxon Chemical Co.
Preferred quaterna~ly salts include quaternary arnmonium derivatives of fatty
amines containing at least one substituent containin~ from 12 to 20 carbon atoms and
zero to 50 moles of ethylene oxide and/or zero to 15 moles of propylene oxide where
the counter ion consists of halide, sulfate, nitrate, carboxy~ate, aLIcyl or aryl sulfate,
allcyl or aryl sulfonate or derivatives thereof. Specific examples include Arquad~ 12-
37W dodecylt imethylammoniumchloride, Arquad(~ 18-50 octadecyltrimethylammoni-
um chloride, Arquad(~ 210-50 didecyldimethylammonium chloride, Arquad~ 218-100
dioctadecyldimethylammoniumchloride,Arquad(~316(W)trihexadecylmethylammoni-
um chloride, Arquad~) B-100 benzyldimethyl(C,2.18)alkylammonium chloride, Etho-
quad~) C/12 cocomethyl[POE(2)3amrnonium chloride, Ethoquad(9 C/25 cocomethyl-
[POE(15)]ammonium chloride, Ethoquad~9 C/12 ni~rate salt, Ethoquad(9 T/i3 Acetate
tris(2-hydroxyetnyl)tallowalkyl ammonium acetate, Duoqaud~) T-50 N,N,N',N',N'-
pentamethyl-N-tallow-1,3-diammoniumdichloride,Propoquad~2HT/11di(hydrogenat-
ed tallowalkyl)(2-hydroxy-2-methylethyl)methylarnmoniumchloride, Propoquad(~T/ 12
tallowalkylmethyl-bis-(2-hydroxy-2-methylethyl)ammonium methyl sulfate, all avail-
able from Akzo Chemicals inc.; Monaquat(~) P-TS stearamidopropyl PG-diammonium
-chloride phospha~e, available from Mona Industries Inc.; Chemquat(~ 12-33 lauryltri-
methylammonium chloride, Chemquat~) 16-50 Cetyltrimethylammonium chloride
available from Chemax Inc.; and tetraethylammonium pelargonate~ laurate? myristate,
oleate, stearate or isostearate.
Preferred water-soluble polymers include homopolymers and heteropolymers
of ethylene oxide, propylene oxide, butyIene oxide, ac~l~lic acid and its derivatives, ~ -
maleic acid and its derivatives, vinyl phenol and its derivatives, and vinyl alcohol.
Specific examples include Carbowax(9 200, Carbowax~ 600, Carbowax~9 900, Carbo~
- ~ wax~) 1450, Carbowax~ 3350, Carbowax(9 8000, and Compound 20M, all available
from Union Carbide Corp.; Pluronic~ L61, Pluronic69 L81, Pluronic g) 31Rl, Pluron-
ic~) 25R2, Tetronictfi) 304, Tetronic~ 701, Tetronic~9 908, Tetronic~) 90R4? andTetronic~g) 150R1, all available from BASF Wyandotte Corp.; Acusol~) 410N sodium ' ~
:'
WO 94/01~17 2 1 ~ 5 9 2 0 Pcr/~sg3/0635~
salt of polyacrylic acid, Acusol(~ 445 polyacrylic acid, Acusol~ 460ND sodium salt
of maleic acid/olefin copolymer, and Acusol(~ 479N sodium salt of acrylic acid/maleic
acid copolymer, all available from Rohm & Haas Company; and N-methylglucamine
adducts of polyvinylphenol and N-me~hylethanolamine adducts of polyvinylphenol.
sAdditional improvements can often be achi~ Jparticularly for lu~brican~ and
surface condition treatments applied before the f~ontact of the treated surface with
an aqueous composition, by using an inorganic~a~erial selected from metallic or ionic
zirconiurn, titanium, cerium, aluminum, iron, vanadium, tantalum, niobium, molybden~
um. tungsten, hafnium or tin to produce a film combining one or more of these metals
10with one or more of the above-described organic materials. A thin film is produced
having a coef~icient of static friction that is not rnore than 1.5, preferably not more
th~n 1.2, more preferably not more than l.0, or still more preferably not more than
0.80, ~nd is less than the coefficient without such film, thereby improving can
mobility in high speed conveying without interfering with subsequent lacquering. other
15painting, printing, or other similar decorating of the containers.
The technique of incorporating such inorganic materials is described, in partic-ular detail with reference to zirconium containing materials, in U.S. Patents 5,030,323
of July 9, l99l and 5,064,500of November 12, 1991, the entire disclosures of which,
to the extent not inconsistent with any explicit statement herein, are hereby in-
20corporated herein by reference. The substitution of other metallic materials for those
taught explicitly in one of these patents is within the scope of those skilled in the art.
In a further preferred embodiment of the process of the present invention, in
order to provide improved water solubility, especially for the non-ethoxylated organic
materials described herein, and to produce a suitable film on the can surface having
2sa coef~lcient of static friction not more than l.5 after drying, one employs a mixture
of one or more surfactants, preferably alkoxylated and most preferably ethoxylated,
along with such non-ethoxylated organic material to contact the cleaned can surface
prior to ~mal drying and conveyin~. Preferred surfactants include ethoxylated and
non-ethoxylated sulfated or sulfonated fatty alcohols, such as lauryl and coco alcohols.
30Suitable are a wide class of anionic, non-ionic, cationic, or amphoteric surfactants.
Alkyl polyglycosides such as C~ - C18 alkyl polyglycosides having average degrees of
polymerization between 1.2 and 2.0 are also suitable. Other classes of surfactants suit-
WO94/01517 ~a~u
- Pcr/US93/06359
able in combination are ethoxylated nonyl and octyl phenols containing from 1.5 to
100 moles of ethylene oxide, preferably a nonylphenol condensed with from 6 to 50 ~-
moles of e~hylene oxide such as Igepal~ C0-887 available from Rhone-Poulenc; al- -
kyl/aryl polyethers, for example, Triton(~ DF-16; and phosphate esters of which Tri-
ton(~ H-66 and Triton(~ QS-44 are examples, all of the Triton~ products being avail-
able from Union Carbidé Co., and Ethox(~) 2684 and Ethfac(~) 136, both available from
Ethox Chemicals Inc., are representative examples; polyethoxylated and/or polypropox-
ylated derivatives of linear and branched alcohols and derivatives thereof, as for ex-
ample Trycol~ 6720 ~Henkel Corp.), Surfonic(~) LF-17 (Texaco) and Antarox~ LF-
330 (Rhone-Poulenc); sulfonated derivatives of linear or branched aliphatic alcohols,
for example, Neodol~ 25-3S (Shell Chemical Co.); sulfonated aryl derivatives, for ex-
arnple, Dyasulf~) 9268-A, Dyasulf~ C-70, Lomar(~) D (all available from Henkel
Corp.) and Dowfax~ 2Al (available from Dow Chemical Co.); and ethylene oxide
and propylene oxide copolymers, for example, Pluronic~) L-61, Pluronic~ 81, Pluron-
iC~) 31R1, Tetronict~ 701, Tetronic(5~ 90R4 and Tetronic(3 150R1, all available from
BASF Corp
Further, the lubricant and surface conditioner n accordance with this invention
may comprise a phosphate acid ester or preferably an ethoxylated aLkyl alcohol .phosphate ester. Such phosphate esters are commercially available under the trade
name Gafac~) PE 510 from GAF Corporation, Wayne, NJ, and as Ethfac(~) 136 and
Ethfac~ 161 from Ethox Chemicals, Inc., Greenville, SC. In general, the organic
phosphate esters may comprise alkyl and aryl phosphate esters with and without
ethoxylation.
The lubricant and surface conditioner for aluminum cans may be applied to the
cans during their wash cycle, during one of their treatment cycles such as cleaning or
conversion coating, during one of their water rinse cycles, or during their final water
rinse cycle. In addition, the lubricant and surface conditioner may be applied to the
cans after their final water rinse cycle, i.e., prior to oven drying, or after oven drying,
by fine mist application from water or another volatile non-infl~nmable solvent
solution. It has been found that the lubricant and surface conditioner is capable of de-
positing on the surface to provide it with the desired characteristics. The lubricant and
surface condidoner may be applied by spraying and interacts with the surface through ~
. :
.
W O 94/01517 2 1 ~ 5 9 ~ ~ PC~r/US93/06359,`~ ~
chemisorption or physiosorption to provide it with the desired dried lubrlcant and
surface conditioner film.
The arnount of lubricant and surface conditioner to be applied to the cans
should be sufficient to reduce the coefficient of static friction on the outside surface
of the cans to a value of about 1.5 or lower, and preferably to a value of about 1 or
lower. Generally speaking, such amount should b&~ ~he order of from about 3
mg/m2 to about 60 mg/m2 of lubricant and surface~ditioner on the outside surfaceof the cans. m '
For a fuller appreciation of the invention, reference should be made to the fol-t:) lowing examples, which are intended to be merely descriptive, illustrative, and not
limiting as to the scope of the invention.
Examples Group I
Uncleaned alurninum cans from an industrial can manufacturer are washed
clean in examples Type A with alkaline cleaner available from Parker+Amchem Divi-
sion, Henkel Corporation, Madison Heights, Michi~an, employing the Ridoline~ 3060/
306 process and in Examples Type B with an acidic cleaner, Ridoline(g) 125 CO from
the same company. Following initial rinsing and before final drying, the cleaned cans
are treated with a lubricant and surface conditioner composition comprising one of the
following (i) about a 1 % by weight aqueous solution in deionized water of active
organic material (I) as specified in Table 2 below; (ii) about 1 % of the active organic
(I) in deionized water plus about 2 gm/l (0.2 %) of the inorganic constituent (II) as
specified in Table 2; (iii) about 1% active organic (I) in deionized water plus about
0.5 % of surfactant (III~ as specified in Table 2; (iv~ about 1 % active organic (l)?
about 0.2% inorganic (Il), and about 0.5% surfactant ~III) as specified in Table 2.
2s Among the compositions of the aqueous lubrication and surface conditioning
treatment in this group, the ones containing inorganic constituent (lI) from Table 2 are
applied in Stage 4 as de~med above, while those not containing this ingredient are ap-
plied immediately before final drying.
In addition, the cans after drying are evaluated for their coefficient of static
fricdon using a custom built slip dme tester. This apparatus consisted of three timing
stadons attached to a motor driven inclinable rarnp. Two cans are placed horizontally
in each stadon and a third placed on top of them in the opposite direction. This
WO 94/01517 ~ ~L 3 5 9 ~ O PCI`/US93/06359
TABLE 2
_ . . _ :.
Ex- Active Organic (I) Inorganic Surfactant (III) pH
am (II)
ple Trade Chemical
Type Name Descriptior~
. .
A Emery 657 Caprylic acid Al2(S04)3 IGEPAL C0-887 2.2
B Emery 659 Capric acid H~ZrF6 TRITON X-lOl 2.2. .
A Emery 651 Lauric acid FeF3 NEODOL 25-5-3 2.3
B Emery 655 Myristic acid SnC14 TERGITOL 2.3
TMN-6
I
A Emersol Palmitic acid Ce(NO3)4 TRITON DF-16 2.6143 91% l
I . .. -
B Emersol Stearic acid H.TiF6 TRYCOL 6720 2.6 ¦
153 NF 92% ~ I
l I .A Emersol Isostearic acid H2HfF6 ANTAROX LF- 2.6 ¦
871 330 I
I _ i , ,,
B Emersol Oleic acid 75% (NH4)2ZrF6 TRITON H-55 2.6 ¦
6313 NF l ~;
I .. ,
A Empol Dimer acid Fe2(SO4)3 TRITON H-66 2.6 ~ ~:
: - 1014 95%
I ~ I -:
B Emery Azelaic acid Al(NO3)3 TRITON QS-44 2.6 ``
I , .
B Ethox MI5 Ethoxylated iso- TiCl4 TRYCOL 6720 3.0 stearic acid
,
- ~ A Emulphor Polyoxyethylat- CeI3 SURFONlC LF- 3.0 ` ;~
~1~ VN 430 ed oleic acid 17
. ~ 1 ~ ~ ~ : ~ ~ I .. .
B ~ Ethox Polyoxyethylat- FeP3 LOMAR D 3.0
M05 ; ed obic acid I ~;
~A Monamide ~ Lauric alkanol- FeCl3 DOWFAX 2A1 2.0
150 LW amide ~; `
_ .
'B Monamide Myris~c àlka- FeBr3 ~ DYASULF 9268- ! 30 i -
l 150 MW nolamide A
- ~ A Monamide Isostearic alka- H2ZrF6 DYASULF C-70 4.0
~ - 150 IS nolamide - -
' : _ .....
-~
' ~...
... Table 2 continued on next page ...
~ .
:' : ` ',',:-'~
. .
;:
WO 94J01517 ~ ~ 3 5 9 2 0 PCr/lJS93/0635~;, ;,`,.. ,. . :
- ,
. _ . .. , ,. .
Ex- Active Organic (l) lnorganic Surfactant (III) pH
am- ~ (II)
ple Trade Chemical : ~:
Type Name Description
~ , . _- .
B Monamide Stearic aL~canol- H~TiF6 IGEPAL co-ssr s.o ¦
718 amide
~ . _ . - I
A Gafac BH Aliphatic phos- Fe(NO313''~; POLYTER&ENT 2.0 j
650 phate ester, acid ~; ~' SLF-18 l ~: -. for~n ~ _ _
¦ B Ethox Aromatic phos- (NH32ZrF~ PLURONIC L-61 3.0 ¦
l PP16 pha~e ester
~ , l
¦ A Gafac BL Aliphatic phos- TaF5 TETRONIC 701 6.0 ¦ ~.
l 750 phate ester, acid
I . _ . .
¦ B Gafac Aromatic phos- NbF5 PLURONIC 31 R 1 5.0 ¦PE510 phate ester, acid ¦
I form
, .
¦ A Ethfac Aliphatic phos- H2ZrF6 PLURONIC 4.0 I -.-
142W phate ester 150R1
I _ _ _ ~ .
B Gafac RA Aliphatic phos- (NH4)2Mo APG 300 6.0 ¦
600 phate ester, acid 4
~Oll 1
. _ I
A Armeen Z N-Coco-B- H~TiF6 TRITON CF-2] 6.0 l
aminobutyric ¦ ;: ::
acid
B Hamposyl Lauroyl sarcos- VF4 TRITON DF-18 5.0
L ine
I . . _ . _ _ ..
A Harnposyl Cocoyl sarcos- FeF3 TRITON GR-7M 4.0
C ine
I . _ , _ _ _
B Hamposyl Oleoyl sarcos- SnC14 TRITON H-55 3.0
O ine
_
A Hamposyl Stearyl sarcos- Al2(SO4)3 TRITON X-100 2.0
S ine ::
i _
B Acusol Polyacrylic H2ZrF6 TRITON X-120 4.0~ 410N salt, _
... Table 2 continued on next page ...
12
WO 94tO1517 2 i 3~ 9 2 0 Pcr/us93/o63~9
, =
Ex- Active Organic (I) lnorganic Surfactant (III) pH
am- (II)
ple Trade Chen~ical
Type Name Description
_ I
B Triton GR- Dioctylsulfo- Al(NO3)3 TRYCOL 5882 ~ 6.0 ¦
SM succinate I
. . _
A Avanel S Sodium aLkyl- VOSO4 TRYCOL 5887 5.0
ether sulfonate I -~
I ~-.. '.
B lgepon Sod~um N-co- VF5 TRYCOL 5964 4.0 ¦
TC-42 conut and N-
methyl taurate ~
I _ ~:.
A Igepon Sodium N- VF3 IGEPAL C0-887 3.0
: TK-32 methyl-N-tall
~ oil acid :taurate
- I : : _
B Neodol 25- Sulfonated line- (NH4)2W04 IGEPAL C0-630 3.0
3A ar alcohol, am-
monium salt l
l _ . ,~ ~.
: ~ : I A ~ Aromox Bis(2-hydroxy- (NH4)2ZrF6 NEODOL 25-3 3.0
: : CJ12 ~ ethyl) cocamine ~ I
oxide :: I :
I ~ ~ . ~:,'.,.
~: Bl~ ~ ~ I Aromox ~ ; ~ Dimed~ylcoc- FeF3 NEODOL 25-35 3.0
~ ~ : ~ DMC arnine oxide ~
: ~: I: : . : :: -- I ,.";,,.
: ~ A~: Ethoquad Oleyl Fe2(SO4)3 NEODOL 25-9 2.0
: ~ : ~ 0/25~ ~ [POE(15)]
~ ~ ~ammonium
1: ~ : :~ ~ ~ : : I
~:B ~ E~hoquad~ ~Cocomethyl :: Al2(SO4)3 NEODOL 91-25 3.0
~ C~/12~ : lPOE(2)3
: ~ : ~ : ~ ammonium : :
:: : ~: ~ : chlo~ide : I -
1 ~ : : ~ : ~ I
; A ~ ~ ~E oquad~ ; Octadecyl Sn(S04) TRITON Q5-15 3.0
ammonium ~ .
~ j ~ chloride
. .
;. . ;
. ::
~: ~ ... Table 2 continued on next page
13 "
"
Wo94~01517 21~$~
PCr/USs3/06359
1 ' . . _ _
_ _ _, _
Ex- Acti~e Organic (I) lnorganic Surfactant (III) pH
am- Trade ~ Chemical (Il) ;;
Type Name Description ~
_ , . . ~ _
B Propo~uad TallowaL~cyl- Ce2(SO,,~ TRITON DF- 1~ 2 .0 ¦ T/12 methyl-bis-(2-
hydroxy-2- c~
methylethyl) ~,
ammonium
methyl sulfate
l . _ .- . ~ :.'
¦ A Ethfac 136 Phosphate esterH~ZrF6 IGEPAL C0-887 2.3
h8o4x Phosphate esterH ZrF6 IGEPAL C0-887 2.7
A Trylox Ethoxylated H~ZrF6 IGEPAL C0-887 2.3 I -
5922 hydrogenated
castor oil
_ . .
B 5T9Y2l1X " H2TiF6 IGEPAL C0-887 2.7 ¦ ~
. . _ I ,, .
~ 5T9Y215X _ H~ZrF6 TRITON H-66 2.7
procedure insures that the burr on the cut edge of the cans does not interfere with the
motion of the cans. The test begins as the ramp is raised toward the vertical. The
elapsed time from the start of the ramps movement to the time when the third canslides is recorded as the "Slip Time." This time is then converted into a (Static)
Coefficient of Friction ("COF") according to the equation: ;
COF = Tangent of [4.84 ~ (2.79-t)] ;
where t is the time Slip Time in seconds. Fifteen slip times were collected, converted
to COF's and then averaged to give the C(:)F result discussed here. In some cases the
tested cans were subjected to an additional bake out at 210 C for 5 minutes and the
ICOF redetermined; this result is denoted hereinafter as "COF-2".
In all cases in this group of examples, the COF produced on the surface is less
than 1.5.
Examples and Comparison Examples Group II
In this group, various candidate materials for forming a lubricant and surface
14
wo 94/01517
Pcr/~lS93/06359
.~.. ;................................................................................ .
conditioner were tested at lower concentrations than in Group I.
II. 1 General Proced ures. Mobility enhancer/rinse aid process solutions were prepared
using deionized water with a conductivity less than 5 ,usiemens; unless otherwise
noted, all other solutions were prepared in tap water. Drawn and wall ironed alumi~
5 num cans were obtained from cornmercial factory production.
Most cans were tested on a pilot scale beltwasher, a single track seven stage
conveyor belt type washer (hereinafter denoted "BW") at its highest speed of 6.2 feet
per minute ("fpm"). Alternatively, a carousel type can washer (hereinafter "CCW")
that processes 14 cans in a sequence of batch steps under microprocessor control was
10 employed. Both types of washer were capable of simulating the sequences, dwell and
blow off characteristics of full scale production washers.
Free Acidity and Fluoride Acdvides of the cleaner baths were determined as
~-~ described in the P+A Technical Process Bulletin (No. 968) for Ridoline 124C. The
cleaned and treated cans were dried in an electric forced air oven as described below.
15 Can mobility was tested as in Group I.
Foam helghts were determined by placing 50 milliliters (hereinafter "mL") of
the process solution in a 100 mL stoppered graduated cylinder and shaking vigorously
for l0 seconds. The total volume of fluid, liquid plus foam, was de~ermined immedi-
ately and after 5 minutes of standing. These "foam heights" will be referred to herein-
- 20 :after as "IFH" (initial foam height) and "PFH" (persistent foam height) respectively
The water break characteristics of cans treated with candidate final rinse mobil-
ity enhancers ("FRME's) were evaluated by visually rating the amount of waterbreak
on each of the four myor surfaces of the can: interior dorne and sidewall and exterior
dome and sidewall. In this rating scheme a value of 2 is assigned to a completely wa-
2s terbreak free surface, uro to a completely waterbroken surface and intermediate val-
ues to waterbreaks in between. Four cans are evaluated in this way and the scores tot-
aled to give a number between 32 and 0, the waterbreak free (VVBF) result.
, ~ ~ - I . ; , . .
II.2 Effect of Cleaner Bath Fluoride Activity On COF and Reflectivity. The CCW `
and subsequent drying oven were used as follo~vs~
Stage 1 tap water, 54.4 C, 30 sec. ` `
Stage 2 RIDOLINE~9 124C, 15 mL Free ~icid, 3.4 g total of
surfactant, Fluoride Activity 10 to -20 mV in l0 mV in- ~;
crements, 60 C, 60 sec.
,x~
} .
W0 94/01517 2 ~ 3 S ~
Pcr/US93/06359 ~.
Stage 3 tap water, 30 sec.
Stage 4 deionized water, 90 sec.
Stage 5 optional application of 0.4~0 M.E.40, 20 sec. ~;
Stage 6 not used
Oven 5 minutes at 210 C
The "fluoride activity" noted for Stage 2 abo~ defined and can conveniently
be measured by means of a fluoride sensi~ive e~le;;~rode as described in U. S. Patent
3,431rl82 and commercially available from Ori`~n Instruments. "Fluoride activity" as
10 this term is used herein was measured relative to a 120E Activity Standard Solution
commercially available from the Parker+Amchem ("P+A") Division of Henkel Corpor-ation by a procedure described in detail in P+A Technical Process Bulletin No. 968.
The Orion Fluoride Ion Electrode and the reference electrode provided with the Orion ;
instrument are both immersed in the noted Standard Solution and the millivolt meter
15 reading is adjusted to O with a Standard Knob on the instrument, after waidng if nec-
essary for any drift in readmgs. The electrodes are then rinsed with deionized or dis-
tilled water, dried, and immersed in the sarnple to be measured, which should be
, .
-brought to the same temperature as the noted Standard Soludon had when it was used -
. ~ - to set the meter reading to 0. The reading of the electrodes immersed in the sample
20 iS taken directly from the millivolt (hereinafter often abbreviated "mv" or "mV") meter
on the instrument. With this instrument, lower positive mv readings indicate higher
iluoride acdvity, and negatdve mv readings indicate still higher fluoride acdvity than
any positive readings, with negative readings of high absolute value indicating high
fluoride activity. ~-
- 25 ~ ~ Effectiveness of soil removal was measured by use of the "brightness tester."
This device consisted of a power stabiliud hi~gh intensity lamp and a fiber opdc bun-
dle co~lveying the light to the can surface. The light reflected from the can impinged
on a photocell whose current output was amplified and converted to a digital readout
by an International Microtronics Inc. Model 350 amplifier; the number displayed was
~o recorded as the brightness of the surface. The instrument is calibrated with a back
silvered plane- mirror to a measured reflecdvity of 440. Once calibrated, the reflecdvi-
ties of fourteen cans were measured and avera~ed. With this device it was possible
to measure the overall interior reflectivity and exterior dome reflecdvity. Results are
shown in Figures l(a) - l(d).
16
WO 94/01517 ~13 5 !3 2 0 PCr/US93/06359
II.3 Screening of Diverse Ma~erials For ~RME Aclivin~. The CCW was operated ac-
cording to ~he following scheme, in which the extended Stage 3 rinse time simulated
a production sequence wherein the normal Stage 3, 4, and 5 applications were used
as rinses~
s Stage l sulfuric acid, pH 2.0, 30 sec., 54.4 C
Stage 2 RIl:~Ol,INE~ 124C, lS mL Free Acid, 3.4 g/L total of ~ ~ -
surfactart, Fluoride Activity -lO mV, 90 sec.. 54.4 C
Stage 3 deionized water, 150 sec. (ca. 17.7 L)
Stage 4 as noted in Table 3, 30 sec., 29.4 C temperature
Stage 5 not used : -~
Stage 6 not used
For this work MacaminelM SO was predissolved by adding 15 ~ isopropanol. For thecompositions containing IgepalTM 430 or polyvinyl alcohol, 1.6 g/L of IgepalTM CO~
887 was added to obtain a homogeneous solution. Nitroguanidine was insoluble andwas not investigated further. Results are shown in Table 3. Amine oxides with ---
hydroxyethyl groups bonded to the amine oxide nitrogen, such as AromoxTM C/12 and
T/12, and oxa-acid esters such as those identified in the table as OAE 1 - 4, are pre-
. .~, .
ferred lubricants and surface conditioners, as are the ethoxylated castor oil derivatives
considered in more detail below.
., ~.
~II.4 Eth~xylated Cas~or Oil F~ME's. The CCW was charged and operated as de- ~`
scribed in II.3 with the exceptions that the Stage 3 deioni~ed water rinse was applied
for 130 sec and the ~lrst oven treatrnent was performed at 200 C rather than 150 C. ~
The Stage 4 compositions were as sbown in Table 4. The exper~ment using TryloxTM i ` -
5921 included 0.2 g/L of IgepalTM C0-887 in an unsuccessful attempt to clarify the ^ -
..~ .
solution; a slight cloudiness persisted even in the presence of the cosurfactant. ; :~
II.5 The E~ct of Ethylene Onde Content On The Properties of Isostearyl FRME's .`~
And Binar~ Mixtures With Other Surfac~ants. The CCW was charged and operated ~,
as described in II.3 with the Stage 4 variations shown in Table 5. The results indi~
cate that only very slight defoaming at best was achievable with these defoamers. ~"
However, lower amounts of ethoxylation of the primary ethoxylated isostearic acid ;i
lubricant and surface conditioner forming composition result in less foam, with COF ~ -
values that are fully adequate for most applications. Mixtures of the "defoamers"
PluroniclM 31E~1 and TrycollM LF-l with E~hoxlM MI-9 produce somewhat more foam
17 ~ `
WO 94/01517 2 1 3 ~ 9 2 0 PCr/US93/063~9 `
5: o _ ~ o ~ -- o -- ~` ~ o ~ _ ~ ~ o ~ ~ o --
~ I . , ~ ~ ~ ~ r~ ~ ~ ~. . r~.v. ~ ~ r~ ~o ~ ~ ~, ~ ~o 1-- ~.
~1 ,~
!r o~ ~ O ~ ~ ~ '~ O ~
9~ X
~ V~l -- ~---- -- ~ ~ ~ -- .
c ~ o ~ -
c '' ~
O~ . -- O ~ ~ O cr~ O ~ 00 ~ ~ C~ ~ O 00 ~ _ _
_ ~o ~ u~ o r~ ~ ~ O ~ ~ -- r-- ~ ~ ~, oo O ~
~S ~ C~ _ _ _ ~ _ _ ~ ~ ~ r_ O _ ~ _ _ O ~ ~ ~ _ ~_ O _ ~ _ ~ ~ ~
C o ~ 00 00 ~ t ~ _ ~ ~. ~ ~ ~1 ~ O O~
~ ~ C~ ~ ~ 00 ~ ~ ~ ~ 00 ~ C~ O ~ _ _
8 ~ ~ ~ ~! ~! ~ X ~ ~
-
~; ~ . . . . , , j ,
~ 3
Z
~ _ o o Z :
_ C ~ ~r~ o ~ o
O ~ O O O 11 ~1 1l 1l 1l '` `~ '`
,,, ,,, Ll ~ ~,,, ,, ~ z;, Z Z Z . . .. ~ ~ ~ ~
Z ~ :
¦ ' ~ a a _ _ A ~ O
. I OO~0
c~ C~ 'C 'e c O O O O O O ~ ;~
I ~ 5 .' 5 C 5 .e .5 .' .9 = ~ ~ 5 ~ o ~C, C~
_ C ~ ~ E E ~ ~ o
: !
g
~ I O ~ O O ` '
~ o E ~ C~ .5 ~ ~ ~ 8 v~
¦ Y ~ -o o ~o ~ c ~ Y Y Y ~ ~ ~ o ~ 8
18
~'O 94/1)1517 C ~ ~ a Y;~ U PCI/US93/06359
':-~'`:''
~ ~t o o o ~ o o ~ o _ o ~ _ _ _ ~ ~ ~ ~ o :
.~' v- . . . . ~n ~n v, ~ v. v, ~n v, ~n ~ ~n v, n ~ o . , , v,, . , ~.
_ oo ~ o ~ C~ o ~ o ~ o 00 ~ ~
_ v, , , . , u~ ~n v, v~ n V~ v, ~n
~ gl'Y~~'''''',,,,,~~~~~ ~~~~ '~
c ~oox~
~1 ~ oo ~ ~, , ,,, ,,,,, , _ ~ 1~ ~ ~n ~ ~ ~,,
-- o o a~ ~-- ~ v, o ~o ~ _ ~ ~ ~ ~ ~ ~n ~ oo ~ ~O ~ o ~ ~-- o -- x o ~
C~ ~. ~ ~ -- o ~ o ~ ~ ?~ ~ O O 52 ~ ~ ~ O -- ~ :
~ _ ~ ?--.--~--~"'~~ ? ? " ? ? '~V--V~---- -~
O ~ ~ _ ~ ~ _ _ ~ o
Vi Vi ~ ~ O ~ ~. V ~ V. Cr~ O ~ ~ O O ~ ~ ?~ 00 0 ~ V.
_ l , , , , , , , , , , , , , , , , , _ , ._ _ _ _ _ _ _ , , , X . . " " .
. ,_, _ ~ ~ ,-, ~ -
_ -- o -- ~ o~ X o `~.-.. :
c V~ ~ o ~ ,~
~ ^ ~ . . .
~I v, ~ v. ~o o o
g ~ I I v ~ ~ ~ ~ ~ O C ~ ~ c
v ^ .
C r3 ~; ~ -- _ _ _ _ _ _ _ _ _ r~
I r _ _ V` ~ r ) I I I I ~ r ' ~ V r r~l r t~ _ ` ' `~'`,
r~ ~ r.~ "~ _ _ _ _ _ .
i'A ~ ~ et~ ~ ~ ~ ~ ~ ~ ¢ ~ ~ rv . O O Q Q --
~3 ~ ~ ~ X X X X X X ~ X X X '_ O O C ~ e~ 6 ~ `
., ~ ~ , '~ 3 ,, .~ ~ ~ ~ ~ D ~ ~ r~ r--V r--V C- r--V C~ ~V ~ ~ ~ ~ ; -`
~v ~ v v ~ 'v ~ v~''va a ~ ~ v~ va ~ a .
C~
rv ',
r~ ~ . `
~ _ S ~ y < , y ~ . B
19 "`: :,'
WC~ 94/0151 7 ~ 1 3 5 9 2 0 PCl /US93/06359 .-' :
k~l ,.
~:1 ~ ~ ~ ~ r. ~ ~.r^.r~ ~.~.~ r~ ~ r~.r.~.~ ~ ~.r.~r.. r.~r~ r~ ~ ~ ~ ,r~,
: 1 0 0 ~ O O o --
C~
~: ~ ~ ~t o V~ ",.;
~ ~ ,,,,, ~ Vi
9 ~ u~ O O ~
~C~ ___________ _______~___~
_ V~ o
O ~ I~ o ~ ~o ~ `C -- ~ ~ ~ ~ ~ ~t o~ ~ ~ ~t V~ _ o ~,
, ~ ~ r~ o ~ ~ oo r~ ~ O -- O x o ~ -- ~ ~ o ~ ~ ~
_ ~ ~ D oc , , , , , , 05 _ X _ X C~ ~ 00 _ ~ 00 ~ , ,
~ 91 ~-- ~o r- 1--0 ~ ~ oo g ~ ~ ~ ~ 1_ ~ ~ ~ O ~~ ~ ~ ~ ~ ~t ~ ~ O ~ ~0 ~
O G V~ O ~ ~ O '~J ~`1 ~) 1--
X I _ _ _ _ _ r.~; I I I . I . I -- -- -- t~o -- I I I I I I I I -
~ -- r- O x!t C~ ; O O O O O ~, o '~ ~ z r. r~ r~ -
t~ ~ ~ r~ ~ ~. ~ r~ ~r o ~ o rJ~ c
~ ,,~,, .... ~ t,~r~ ~~~~tarJ~
~o 3
' _ C :
r~ , Z ~ ~ r ~ C '~
_ o o ~ o ~ ~ ~ o ~ o ~ C ~ C C C ^ ^ C ~ ` C O ' ~ Z
_ ,~ ,, C~ ~ ~C-- ~--~ Z Z
~, .
O o C -` C _~
C--,--~ CoC>~
v " ,~ ~v ,~
o ,~ ~ , J ~ - ? ~
c t~c -- -- -- ~ r,o r,o oc ~ ~ ~ _ -- ~
~ _ O O g o ~
_ ,,~ ....,.r~ ,,zzzzzC^C_
8 ~ C o ~ ~ R ~ vi o ô o o O ~ c
E~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ r~ ~; _ C; C~; C 7 r~ 7 ~; ) r~ O C
) ~ C; ;~ ,
c ~ O
C ~ C ~ S ~ S ~ 8 8
2n
WO 94/û1517 - PCI/~S93/063~9
~ ~ ~ ~ ~ ~ ~ ~ 1 ~ . ~ 00 0 ~ ~
_ O O O C O O ~ ~ ~ O ~ , 00 0 ,~ O
1~ O ~ ~. V~ . ~ 00 ~O ~ ~ ~,,,
_ ~ O ~ _ ~ O ~ ~ O _ ~ O C
~ O ~ r, C E ~
~ ~. ~ oo o V ~
~ ~ , ., ~ C- ",,'
o ~a cr~
~) ~ _
O~ ~ O oo ~ ~ O ~ oo r~ ~_~ o
L~ 91 ~ ~ ~ 8 g ~' ~ O O O O ~ ~ O ~
O ~ ~ _ ~ :
~ I ~ O _ ~ ~ ~ 00 0 ~ O ~ er~ c
~c
o. ~ -3 ':
3 Z _ Z c ~ o ~ ;
1l 2. Cii) _ ~ o
_ c~ , . 8
3: O ~ ~ Q O o c~ O o ~~) v E ~ '
O ~ a ~- x ~:
O V~ ,c
O ~ 5 ~ oo :~
~ ~ ~ ~ o ~o ~ c ^ ~ ; ':
_ . ' ' ~ O .;`~.
O v~ c~) ,: .'`,
E ~ C-5--~ ~ ~ ~ ~ ~ ~ ~ '~ C ~ o o g e ¦ ~
a ~ o~ 3~ ~ ~ Y ~ ~ 5 = ~ 8 ¦ ,
wo 94/01~17 PC~/U~93/0~359 ~-
2135920
,
. . = = . _
Table 4 ~
ETHO~YLATED HYDROGENATED CASTOR OIL DERIVATIVES AND
COMPARISONS AS FINAL RINSE M$?1tILITY ENHANCERS
Product Gran~/ _COF ~ ~ ~0~-2 IFH PFH
Name 8 Liters ~
Me~n StD Mean SlD
None 0 1.2~1 .149
TryloxTM 5922 1.6 .479 .072 .503 .08569 65
Trylox 5g22 0.4 .974 .161 1.055 .15160 56
10Trylox~M 5922 0.8 1.~07 .1~7 1.131 .13270 60
Trylox 5921 1.6 .511 .108 .548 .09374 68
Trylox 5921 0.4 1.072 .144 1.034 .20163 59
TryloXTM 5921 0.8 .883 .154 .95~ .15262 54
Trylox 5925 3.2 .914 .140 1.139 .15767 62
15Trylox M 5925 6.4 1.020 .149 1.231 .12274 67
Trylox 592~ 9.6 .965 .180 1.007 .12273 63
~thoxTM Ml-~14 1.6 .621 .118 1.059 .14475 70
,
than compositions with an equal total amount of EthoxTM MI-9 alone, but also give
further reductions in the COF. The interactions are evidently complex and difficult
to predict.
II.6 Final Rinse Mobilit~ Enhancers and Rinse Aids. The BW was operated as
25follows:
Stage 1 sulfuric acid, pH 2.0, 54.4 C
Stage 2 RIDOLlNE 124C, 15 mL Free Acid, 3.4 g/L of total surfactant, Fluoride Activity -10 mV, 60 C
Stage 3 tap water
30Stàge 4 not used
Stage 5 deionized water
Stage 6 as noted in Table 6, 0.2 g/L total acdve additive
~he line speed of this washer was controlled by a rheostat with the following approxi- -
mate relationship between percentage of output and line speed in feet per minute:
22
WO 94/01~17 ~ ~L 3 5 9 2 0 PCI/US93/063~9 `~::
'~. ;~ -' , . :
, .
Table 5
EFFECT OF VARIATION OF DEGREE OF ETHO~CYLATION IN PRIMARY LUBRICANT : -~
AND SURFACE CONDITIONER (ETHOXYLATED ISOSTEARIC ACID) AND OF
5VARIATION OF COSURFACTANT ADDED AS ATI'EMPIED DEFOAMER ~ `
COF _ Ethoxylated Defoamer _ IFH PFH
lsostear~c Acid
Mean S~D ~ # of EO ~/8L Narne
~ per
Molecule ~-
1.139 .170 0 - 0
1.159 .181 0 - 0 - - -
1.069 .165 0 - 0
1.190 .158 0 - 0
1.154 .198 0 - 0 - - -
1.142 .174 (Average of re~ult with above five can lots)
.587 .170 0 - 1.60 Pluronic~ 31R1 77 50
.817 155 0 - 1.60 Triton~ DF-16 79 55
.659 175 0 - 1.60 Trycol~ LF-1 50 50
499 099 1.60 9 0 - 55 55 ~-
2s478 072 1.20 9 .40 Pluronic~ 31R1 61 58
.479 .Qg3 1.20 9 .40 Triton~ DF-16 63 62
423 .027 1.20 9 .40 Trycol~ LF-l 69 67
408 .038 .80 9 .80 Pluronic~ 31R1 65 63
.576 .172 .80 9 .80 Triton~ DF-16 72 69
.467 .103 .80 9 .80 Trycol~ LF-1 65 63
.496 .122 .40 9 1.20 Pluronic~ 31R1 67 64
628 .176 .40 9 1.20 Triton~ DF-16 78 76
656 .194 .40 9 1.20 Trycol~ LF-l 73 66 -
~s457 .074 1.60 10.5 0 - 60 60 `,
465 .121 1.20 lO.S .40 Pluronic~ 31R1 60 59
.531 .108 1.20 10.5 .40 Triton~ DF-16 67 66 -~
566 .186 1.20 10.5 .40 Trycol~ LF-1 65 65
583 .114 . ao lo . s . 80 Pluronic~ 31R1 58 57
40564 .142 .80 10.5 .80 Triton~ DF-16 72 72
550 .114 .80 10.5 .80 Trycol~ LF-1 69 65 ` -
.539 .111 .40 10.5 1.20 Pluronio~ 31R1 55 53
.685 .205 .40 10.5 1.20 Triton~ DF-16 75 70
.644 .133 .40 10.5 1.20 Trycol~ LF=l 77 62
444 .104 1.60 14 0 - 76 75
477 .098 1.60 14 0 - 77 75
.534 .093 1.20 14 .40 Pluronic~ 31R1 74 71
456 .121 1.20 14 .40 Triton~ DF-16 80 75 -
516 .148 1.20 14 .40 Trycol~ LF-l 81 80
505 .106 .80 14 .8~0 Pluronic~ 31Rl 82 79
532 .128 .80 14 .80 Triton~ DF-16 85 84
.456 .078 .80 14 .80 Trycol~ LF-1 86 83
681 .178 .40 14 1.20 Pluroni~ 31R1 82 79
55615 .149 .40 14 1.20 Triton~ DF-16 81 78
.538 .106 .40 14 1.20 Trycol~ LF-1 80 76
23
wO 94/01517 2 1 3 5 9 2 0 PCI/US93~1)6359 . ..
Setting: 100% Speed: 6.2 fpm
3.4 "
1.8 "
Three sets of 14 cans each were treated and collected at ~e end of the washer using
5 tongs. The cans were stacked on a light ga~g~ aluminum baking pan arl~ weighedwith ~he tongs taking care to lose as little watèr as possible duling :he manipulations.
The cans. tongs and tray we~e then dried at 210 C for ten minutes and reweighed.
The average of three replicate runs was taken as an estimation of the water retention
of the finished cans. A fourth set of cans was collected, dried at 210 C for 3 minutes ~
and tested to determine their COF. For those cases where the COF was less than l.00 ~:
the COF-2 was deLermined. Results are shown in Table 6. ~.
~ _ . . . . .
Table 6
VARIATION OF WATER DRAINAGE WITH LINE SPEED AND ADDITIVE
~5 TO FINAL RINSE
Lubricant andlor Water Line Water Reten~ion COF COF-2
Draina e Promo~in . Additive Speed Mean S~D Mean SlD ~) ~`~
None 100 31.72 - - - -
None 100 30.44 - - - -
None 70 28.40
None 70 28.29 .81 1.446.071
None 70 27.02 1.00
None 40 23.34 - - - -
Ethox~ MI-14 40 19.11
Neodol~ 91-2.5 70 15.65 37 1 356.211
Pluronic~ L-81 70 17.44 14 1 124
Pluronic~ L-61 70 17.71 .09 1.206
Neodol~ 91-6 70 20.83 .27 1.201.175
Pluronic~ l-81 (1:1) 21.02 .53 .728 - .970
Ethox~ MI-14/ 70 21.63 .32 .725 _ .832
Pluronic L-61 (1:1)
Ethal~ OA-23 70 21.64 .72 .919 - 1.141
Ethox~ MI-14 70 21.68 .18
Ethox~ ~I-14 70 21.69 - - - -
Ethox~ MI-10.5 70 21.93 .38 .550 - .727
Neodol~ 91-8 70 22.55 .30 1.0Q9.204
Ethox~ MI-14/ 70 24.07 1.00 .581 - .707
Trylox 5922 (1:1)
Trylox~ 5925 70 24.62 .92 1.090 - -
Trylox~ 5922 70 25.21 .97 .581 - .680 ~-
Trylox~ 5921 70 25.88 .26 .546 - .645
Ethox~ MI-14 100 26.60
.. ..... . . .. ... .... ........ _ .
24 ~ ~
wo 94/0lsl7 . Pcr/uss3/o6359
---............................................................................. -
Some surfactants were found that are better at prornoting water drainage than
the ethoxylated isostearic acids that are very effective in providing lubricant and sur- ~ -
face conditioner films. However, the surfactants that are exceptionally good at pro-
moting water drainage are much poorer than ethoxylated isostear~c acids ~n reducing
COF. Mixing the two types permits improvement in water drainage, while retaining ~ ~;
the ability to achieve COF values that are adequate in many applications.
Examples and Comparison Examples Group III
The combination of ethoxylated castor oil derivatives and fluozirconic acid ~-
shown in Table 3 above has been found to have an unexpected additional adv~ntage,
which is illustrated further in this group.
Some beverages packaged in aluminum cans are pasteurized, and unless the
temperature and the composition(s) of the aqueous solution(s) with which cans are
contacted during pasteurization are very carefully controlled, staining of the dome of
the can often occurs during pasteurization. An FRME combining fluozirconic acid
~5 and hydrogenated castor oil derivatives in proper concentrations has been found to ~;
provide both protection against dome staining during pasteurization and adequatelowering of the COF for most purposes.
The can washing setup for this group of examples was:
Stage 1 sulfuric acid, pH 2.0, 30 sec., 54.4 C
Stage 2 RIDOLINE~}) 124C, 15 mL Free Acid, 3.4 g/L total of
surfactant, Fluoride Activity -10 mV, 90 sec., 54.4 C
Stage 3 deionized water, 150 sec. (ca. 17.7 L)
Stage 4 as noted in Table 7 and below, 20 sec. spray ~ 20 sec.
dwell, 29.4 C temperature
Stage 5 not used
Stage 6 not used
ln addition to the ingredients listed in Table 7, the solutions were all adjusted
to pH 4.5 by addidon of aqueous ammonia or nitric acid as required.
Dome staining was evaluated by first removing the domes from ~he treated -
~o cans with a can opener. The domes were then placed in a water bath cont~ining 0.2
g/L of borax at 65.6 C for 30 minutes, then rinsed in deionized water and dried in
an oven. Staining resistance was evaluated visually by comparison with known satis-
wo 94/01~ ~75 9 ~ O Pcr/US93/06359
factory and unsatisfactory standards. Results are shown in Table 7. The last two con-
di~ions shown in the Table are highly sa~isfactory with respect to both COF and dome
staining resistance duling pasteuri~ation.
_ . ~ . .. . .
s Table 7r.
E~CT OF CONCENTRAllONS OF,E~HOXYLATED CASTOR OIL
DERIVATIVE AND OF F~UOZIRCO~IC ACID ON DOME STAINING
RESISTANCE AND COEFPICIENT OF FRICTION
10Grarns ofGrams of COFPasteurization
_?ZrF6/LiterTryloxlM Protection Ratin
5921/Liter
O O 1.16Fail
0 0.2 0.57Fail
0.14 0.2 0.52Fail
~5 0.29 0.2 0.61Marginal
0.58 0.2 0.63Pass
1.16 0.2 0.70Pass
.
Examples and Comparison Examples Group IV
This group illustrates use with tin cans. Three types of materials were tried
as lubricant and surface conditioner forming and water drainage promoting agents for
tin cans: (i) EthoxTM ~ 14; (ii~ a combination of 1 part by weight of PluronicTM31R1 and 4 parts by weight of Plurafac~ D25; and (iii) TergitolTM Min-FoamTM lX.Of these, the EthoxTM, TergitolTM, and PlurafacTM products are ethoxylated fatty acids
2s or alcohols, with a poly{propylene oxide} block cap on the end of the poly{ethylene
oxide } block in some cases, while the Pluronic~M is a block copolymer of ethylene and
propylene oxides, with poly~propylene oxide 3 block caps on the ends of the polymers.
' All were used at a concentration of 0.2 g/L of active material with deionizèd water in
a fLnal rinse before drying, after an otherwise conventional tin can washing sequence
30 Water retention and COF values were measured as generally described above. Results
are shown in Table 8.
`' ~;,
- 26
'
''` ;`.'
WO 9~/01517 ~ 1 3 ~ 9 2 o PCr/US93/06359 ~ .
. ,, ~ .
, ., ;,
Table 8: RESULTS WITH TIN-PLATED STEEL D&I CANS
Additive to Final Rinse Mean COF ValuePercent Water Retention ~::
None 1.04 100 ~O (Defined) :.
EthoxTM 0.70 83.6
PluronicTM/PlurafaclM 0.81 77.3
TergitolTM 0.82 78.6 ~-
.:
,
27 ~:
