Note: Descriptions are shown in the official language in which they were submitted.
" 12, 635
BACKGROUND OF THE IN~NTION
This invention pertains to ~he preparation of
s~able, aqueous colloidal dispersions o:f carboxylic acid
or sul~onic acid-con~a~ning vinyl resins and moxe parti-
cularly ~o their prepara~ion of vinyl resin.colloidal dis-
persions by mlx;ng said resins with water~ base~ an organic
solvent, an organic co-solYent and a macromolecular compound.
Solution polymeriæed vinyl halide res ms have
be~n widely used as an in~erior coating resin for the
10 beex and beverage cans. Th~y are FDA approved v hicles,
provide good protection or the metallic subs~rates from
corrosive efects of the contentsg and excellent blush-
resistance during pasteurization whlle contribut;ng no
undesirable taste properties. For these reasons, they
are pre~erred over most of the other coating resins for
thls demanding application.
Because these vinyl halide resins are normally
applied as a lacquer, a large amoun~ of organic solvents
is evolved during ~he applicatio~. Being ecologically
undesirable and expensive~ this technology has been re-
placed rapidly by other technologies where the solvent
requirement can be reduced to a much lower level. The
most prominent one is the wa~erborne coatings technology.
A waterborne coating may be formed rom a water
soluble resins3 a latex, or an emulsion. A water~soluble
rPsin formulation is oftell too water ~ensiti~e to pass th
required blush resistance test. On ~he ot~er hand~ lat~ces
and emulsions produced by the conventional methods almos~
always contain one or a combination of surfactan~s to
~'
~ ~ ~ 6 ~ ~ ~ 12,635
effect the dispersion as well as fragments from ~he
initiator system used. Thes~ addi~ives often become a
source of either poor blush resis~ance or possibly bad
taste propeEties, or both.
It is therefore an object of this invention
~o prepare water-borne colloidal dispersions of vinyl
resins suited for variou~ coating applications.
SUMMARY OF THE INVENTION
A method of preparing water colloidal dispersiGns
Qf vinyl resins suitable for various coating applications
has been found which comprises:
(A) ble~ing ~inyl resins selected from the
class con~isting of ~inyl chloride~ vinylidene chloride
or vinyl chloride/vinylidene chloride copolymers having
carboxylic or sulfonic acid groups contained therein
wîth:
(a) water;
(b) a water-miscible base;
(c) an organic water-miscible macro-
molecular compound;
~ (d) at least one water-miscible, organir
solve~t which has an affinity for said reslns
~nd boils b~low about 160C.; and
(e) an organic and waker-miscible cu-
solvent which is a poor solven~ or said resins
but is miscible with ~he organic solvent (d); and
12~635
(f) optionally a water-immiscible
organic diluent until a stable colloidal dis-
persion forms; and
(B) stripping the colloidaL disperslon thus
ormed un~il the ~otal organic sol~ent content and diluent~
(d~ ~e) and ~f~, of the final colloidal dispersion is
about 0.2 to about 20% by volume.
I~ is preerred to prepare these colloidal dis-
persions ~y b lPnd ing:
~A) a normally solid vinyl resin contain-
ing carhoxylic or sulfonlc acid group5 and having ~he
following moieties copolymerized here~n
(1) tCH2-C~m
Cl
Cl
(2) ~C~ C
Cl
W
(3) ~ C
X
Y Z
~4) ~CH - CH~
.
L2~; 12,635
(5~ (>
. ~ ~
COOH
wherein m and n ar~ percerlt~ge~ ~ach havlng a value or'
Q-99%,
e ~8 a pe~centage ha~sring ~ ~alue of 0~59Z;
p 1~ ~ per entage having a value of 1-30%;
whea~ ~ ~ O
q 18 a percen~age having a ~ralue of 1~307O;
wherl p ~ O w~th the pro~o ~hat r~ 7Q and
1 99%, ~hat s~tn+ttp~ - 1007," that when m ~ 0, n i~ ~e
lea~l: 1 Rnd tha~ when ~ ~ 0~ ~ ls ~t least 1;
wherein X ~8 a monovalent radle~l ~elected from the
group eonsi3ting of -~ a~d lower alkyl~ havlng 1-4
carbon~;
W ~ ~ monovalent s~adlc~l ~elected froa
the group con~l~t:;n~ of -H, lowe~ ~lkyl~, aryl ha~ g
6 I:o abou~ 9 carbon~,
S~
~ ~s .~
~OR, ~ ~ 2 ~1
~ wh~r@in ~ n ~nteger haY~ng ~al~e~ o 1-3~ .
,635
.. .
C-O-C112-C~CH2 " -OR (wherein R is a Cl Cl~
~lkyl) ~ OH~ ~C-N~Rl)2 (wherein Rl is a monovalent radical
selected from the group consistin~ of -H, methyl or
ethyl~ and -CN;
Y is a monovalent radical selected from the
group consisting of -~, methyl,
O O
,- ..
~CH2 ~ C-OR, or ~CH2 ~ C-OH, wherein b is an in~eger
having values of 0-4, and
Z is a monovalent radical selected from the
group consisting of
O
~CH2~C OH" -S03H and -56H4 S03H, with the proviso ~hat
Y and 2 are never -COOH and -S03H at the same t~me~
(B) sufficient water-miscil~le base to
neu~ralize about 10% to 1007~ of said carboxylic or
sul~onic acid groups 7
(C) 1 to about SOO parts~ per 100 parts by
weight of vinyl resin, of a water-miscible normally
liquid ~olvent iEor said vinyl resin hav;ng a boiling
point below 1~0C. " selected from the group consisting
of lower aliphatic ke~ones ~ esters or ethers having 3 co
about 6 carbon ~toms and cycloaliphatic ketones or ethers
havi~g 4 to about 6 carbon atoms y
(D) 1 to about 500 p3rts~ per 10~ parts by
wel~ght of vinyl resirl" o a normally liquid co~olvent
whlch i8 ~ poor solvell~ for ~che vinyl resin but is miseible
with water and solvent ~C3, selected from ~he g~eoup
6~
1~ ,635
consisting of: . _
(1) glycol monoalkyl etherj ha~ing
~he f or~nula:
HC~CHR CHR O~R
where each o~ D ~ H oa~ CH39 g 1 an
inteBer h~rin~ valu~ of 1 to 3 and R"'~ 1~ an al~yl
gro~p hav~ng 1 ~o abou~ 6 carbon atoms, or phenylD
~ 2) aliph~ ac~die ether~ having
the formula:
~ ~CO~
whereln R""' ia an ~lkyl group ha~Ylng 1 ~o
4 carbon atoms
(3~ amino e~eers havin~ the ormul~;
o
^O~C~2-)~2;
~,4) am~no ketoneQ ha~rlg, the Pormul~-
.~
(5~ allph2tic ~loohols havlng the
~0 formul~:
Rj!,OHo where ~2 i$ a3.kyl lhavin~ 1 ~ocarborl~ s
7.
12,635
(6~ ~liphatic car~oxyllc ~ld~ having
the fo~ula:
R3~H, where R3 18 H or alkyl h~vin~ 1 ~o
4 c~rbons,
t7) aliphatlc amine~ having the fo~ula:
B. -N-R
4 5
. ~6
where R4 and R5 are H or alkyl ha~ing 1 ~o 6 carbon~
lO and R6 i~ alkyl having 1 to 6 carbon~ w~ the proviso
~ha~ ~he total number of ca~bGn in the ~ o R ~ R t
4 ~ `
R6 ~ 6~
~8) aliphatic amino ethers having ttle
ormula:
~ 7 t~2~3~r
whe~e R~ methyl os ethyl, ~nd ~a3 value3 of 1-4
~9~ al~phatlc dialkyl amides hav~g
the fonnula:
8 ~ON (R7) 2
where R~ or alkyl having 1 ~o 5 carbon~
Hydroxymethyl~a~rylamlde a~a~
N~ ydsoxymethyl~eeh~cryl~mide having ~he ~orsnula~
CH2~C~eON}lC}120
wh re R~ o~ 3"
cyclo~lip~atic ~her ~lcot~ol~
havis~g ~h~ ~ormula:
8.
12~635
~ 11) cycloallphaeie ether ~lcohola
havlng ~hc formula.
R~
whe~e R~o ~ alkylene ~aving 1 ~o 3 carbons and ~ ~s
an ~nteger havlng v~lue~ of 1 to 5,
(12~ hydroxy e~ter~ having th¢ onmul~:
o
..
R~ 2)~, 0~, a~d
~133 hydroxy ketones having ~he formulaO
O .
~8~C (C~23 ~ OH;
(E) 0 to about 49 parts by weig~t of ~
water~immiscible organic diluent per hundred par~s by
weight cf organic solvent ~D) selected from the group
consisting of alkane~ having abou~ 5 to a~ou~ 20
carbon atoms and halogenated alkanes having abou~ 2
to about 20 carbon atoms, cycloalkanes and halo-
genated cycloalkanes having about 5 to about 12 carbon
atoms, aromatic hydrocarbons having 6 to about 12 carbon
~ atoms, aliphatic or cycloalipha~ic ketones having about
7 to about 12 carbon atoms~ alkaryl ketones having about
7 to about 12 carbon atoms~ aliphatic and aromatic esters
having about 7 to abo~t 12 carbon atoms and olefins ha~ing
abou~ 6 to abou~ 20 carbon a~oms;
(F) a wa~er-miscible, normally solid
macromolecular organic compound selected from the
group consiting o-f cellulose ethers, poly(alkylen~
o~ides), homopolymers o~ vinyl alcohol~ acrylic
~r 12 1163~
. ~ .. .
~:r
acid9 methacrylic acid3 N vinyl pyrrolldoIle or acryl-
amide and copolymers o virlyl alcoholi, acrylic acid"
.. .
methacrylic acid, N-vinyl pyrrolidoneg maleie acid or
acrylamide cont~n~ at least one of ~he follow:Lng
.~ lipophilic moie~ies c3polymerized ~hexe~
! ~s
H2~ C~
. OGOR
:,,
.: Y
(2) ~H - C~
C02R,
;. (3~ ~CH2~ G~
OR
- wherein Y and R are as indicated above; ~nd
" .
sufficierlt water to provide an aqueous
,'~ colloidal dlspersion having ~r total sollds content of
up to about 60% by weight; and then s~ripping the
,~ colloidal dispersion UTIti~ the total content of organic
~' 20 solvents ~C) and (D) and diluent (E) ls about 002 to
about 20% by volume.
The vinyl reslns useful in this lnvention in
he:ir broadest ~ense s.re ropolymers of v~yl chloxide3
. . .
v~ylidene ~loride or both copolymerized with a
vinyl comonom~r containing a~ ~ east one carboxylie acid
group, COOH or sulorlic acid group . ~S03H . E~ceD~lary
resins include copolymers of vinyl c~loride and acrylic
or methacrylic acid, vinyl chlorlde and maleic acld3
viny~ chloride and styrene sulXorlie acid and the like;
copolymers s~f ~7inyliderle chloride and a- rylic or
lOo
1~ ~, &35
methacrylic acid, ~nylidene chloride a~d maleic acid,
vinylidene chloride and s tyrene sulfonic acid, and ~he
like .
The~e ~lnyl ~Psin~ al~o enco~pa~8 thre~ com-
ponerlt copotymers cont~inlng fo~ exa~sple the followlng
~ono~ers copoly~erized ~hereln:
~inyl c}iloride/~lny3 ~ce~ate~acryllc ~c~t
~lnyl ch~.oride/ vinyl ace~atetmaleie ~ci~
~nyl chloride/vinyl acetate/croconlc acid
vinyl chlor~de~nyl acei:ate/5-nofboFrlene-2, 3-
di~carb~xylic acid, monobu~yl ~qt~r
~nyl chloridervlnyl ace~s~e/fumar~c aeid
Y~nyl chloride/methyl methaery7~tet~Lale~c acld
~lnyl chlorid~/~crylonltrile/mal~lc acld
vinyl chloridel~tyre~e/ma~c ~cid
~inyl chloridelvi~yl stearate1malelc acld
~inyl chloride~2~propenyl aceeaee~maleic acld
~inyl chlorideJhyd~oxypropylacrylate/m~le~c acld
vin~l chlor~delgly~idyl methacrylaee~malelc acid
vinyl chlor~de/acryla~ide/maleic ~cld
vinyl chloride/vlnyl ~lcoholJm~leic acld
vinyl chloride/vlnyl butyl etherJmalelc se~d
Yinyl chloride/ethyl acrylace/male~c acid
Y~nyl chloride/ethylene/~aleic acid
vinyl chlor~de/ethylene/aerylic aeid
yi chlorlde/propylene/~aleic acld
Y~yl chlorlde/styrene/acryliG acid
~lnyl chlorld Ivinyl acee~te/~yrena ~ulfon~c
~cld
v~yl chlorlde/Yinyl acetat~/vl~yl ~ulfonl~
ac d, and the ll~e ~ well a~ oeh*r t~rpolymer~ in wh~ch
ll o
12 9 635
~nylideno ehlorlde ~ 3u'b~t~euted ~or virlyl chlor~te
i~ th~
~ n ~ddi~ on os~r componerat quadripolymer~
cu~ o ~e used w~eseln bo~h vinyl chloride ~nd ~inyl~dene
shloride are copolysnerized with the other comonomer~
~ho~ ~ n ~e eerpolymers ~n ~he pr~cedlng p~ragr~ph .
~ he amotmt of each morlom~r copolymeri2Pd in
the vinyl ~esins 1~ no~c nar~owly crit~ ca~ .
The ~thylenlcally ~sa~u~a~ed ea~boxyl~c acid3
10 en~nesated a~boYe ~ ~ell a~ the other con~nomers are
commerc~ ally sYa~lable . ~e ~ore comnon 3ulfonic acld
concalTIing ~nomers ara al o cons~erclall~ available or
can ~e ~ynthe~i~ed by 8ulfon8tlon of ethylenicall~ ~-
saturated D~nomer~ ranging from al~phat~c monomer3, ueh
88, ethylene to aro~natlc ~onomer~, ~uch 8, ls~Qne~
~l~h known ~ulfona~ion agents, ~uch a~ e~ in l'Uni~
ProceYqes in Organlc Synthesi~" ~y P.~. ~roggin~, ~tcGraw-
Hill Co., ~nc. ~ p~ge 262 NYC ~1947~.
T~e in~rention 1~ not li~lted to ~lngle co-
20 polymer~ a~d ~o varlous combLnatiorl~ o~ two or more o
~he3e vinyl resln~ can b0 emul~lfi~Ad as well.
Preferred vinyl chlorlde se~ln~ includ~ ~lnylchlor~te ~erpolymers ~avirlg abou~ 60 ~o BbOUl: 91 W~ tlg
2 Y~n~rl ehloridel abo~t 10 ~o ~bout 25 welght ~ vinyl
alc2eae~ And ~bouc 1 eo ~bou~ lS weigh~ Z o ~slei~ ~ci~
u~rl6 ae~d or crotorlic ~c~d cQpoly~erized ~herein.
Such ~erpolymers may be obt~ ed comm~rclally o~ may ~
~ynthe~lz~d ~y ~ free radical in~tiaeed poly~Der~zation
~2635
hlo~d~r ~Y~nyl ~c~t~ n~ ~le~
~alele ~nhydrld~ ~ fumarle ac~d or crotorl~ c ~c~ .
The ~oYe~de~crlbed ~iny~ ~hlor~de reslr.s Gan
al30 ~i3 blended wileh ~inyl çhlos~de/~rinyl acePa~e
t~rpoly~er~ conealning ~lycidyï s~e hydroxyalkyl acrylaee~
or ~thacrylat@~ ha~ng 2 ~r 3 carborl~ ln the ~lky:l
group ~o afford e~osslinked co~ngs. On2 c~n ~l~a ~dd
thermose~lng re~n3, BtlCh a8~ epoxy rc~ln~ ur~a re9in~
and ~ela~ne rPs~n~ ~o ob ~in a hlgher degree o~ cro~
10 linking. Pref rr~d epoxy re~in~.~nclude liquid arad
solid tiglycidyl ~her~ o~ blsphenol A which ~re
e~mmerc~all~ ava~lable ~d te3cribed ~n "Epoxy Resin3"
S~ ~1. Le~ ~nd, ~. Ne~ J MoGsaw-~ill and Co. " Inc.
NYC 1957, inc~rpo~ated hereirl 'by reer~nce.
~ r~fesred ~elamlrle r~ins a~e th~ hexametho~
methylmel~ e resin~A Prefer~ed urea re~n~ ~re ~he
~e~hylated urea-formaldehyde re~insO The~e are
co~mercially ~va~lable,
Blu~h or whi~enlng o Sh~ coatings i8 dete~-
20 ~ined ~ub3ectively~ a ee~e well ~nown to tho~e ~killedin the art.
Wet adhesion is measured by cross-hatch adhesive
failure determ~nations. These are made by i~mersing
coated specimens in water at 75C for 45 minutes,
scratching a cross on the coated substrates with a
sharp pointed lnstrument, pressing sections of Scotch
tape across the scratched portions and then ripping the
Scotsh tape away from the cuated surface. Failures are
indicated by the amount of coating which pulls away from
the substrate.
1~ 635
Exemplary co~solvents ~re pr~sen~ed belo~.7.
~epresene~tiye ~lyco~ ~noal3cyl ~phenyl) ethers are
~nonome~hyl, eehyl, pr;: pyl, butyl ether~ of ethylene
~lycol, d~e~hylen glycol, tr~et:hylerle glycol ~ propylene
~lyeol, dlpr~pylene glycol, phenyl glycol e ther 7 ~nd the
l~ke .
Repre~en~t~ve alipha~c a~âd~c e~herj ~nclude
ethoxyac~ c acld, ~-methoxy~propion~e acid, dime~aoxy
~eet~c acid, ~oxy propion~c ac~d, a2ld the lilce.
R~pre~entat~ve afnir~o e~erg ~ncltlde ~e~hyl
minoprop~ ona~e, ethyl aminoacetate, ethyl
a2rLinopropiorlate, and the l~k~.
Represent~tiYe amlno k~eones ~nclude ~ino-
acetone, ~am~nobueanone, and the l~ke,
Represe2lea~c~ve aliphaoc~c alcoho~ include 3
~etl~anol~ ethanol, prop~nol~3 but~nols, pent~noï~, ~nd
th~ like.
~epr~en~ative ~ lphaeic ~srb4xyllc ~c~t~ ~n-
clude ~rmlc, aceti~, propiorlic, ~butyr~c, and like ~cid~
iRepreYentati~re alipha~lc amine~ include me~hyl~
amine, dime~hyla~ine, me thyl~e~hylamine, dlmethylami~ 3
~r~ hyl~ ne, n-~utylamine, hexyasni~e, and ~he lik2.
~pre~entative al~pha~e ~m~na ether~ include
e~hoxy-~-pxop~lamlne~ ~oe~hoN:y-n-propylamlrle,
1~ .
12635
ethoxy~1~obutylamin@, 6B-ethoxy-n-bueyl~M~Tle, ~n~
the ~e.
~ epresen~cat~v~ allph~tlc d~lk~l ~mldes
elude N,N-d~e~hylformamld~, N,Ns d~thylformazoide, N,~
d~imethyl~cet2mide/ and th~ e~
Repre~eneative sycloallp~a~ie ~her alcohol~
tnclude ~lycidol 9 ee~rahydrofusfuryl ~lcohol, and ~he
like .
Repre~entativ~ hydroxy es~ers ~nclude meehyl
10 lactate ~ ~ethyl- ~ ~hydroxy$: ropionate, ~thyl~
hydroxypropionate, and the l~ke.
~ epre$erltati~Je hydroxy ketones include 1-
hydroxy-~-propanone, l-hydsoxy~3~'butanone, 3~eeh~14
hydroxy~-butaIIone ~ l-hydrvx~-2-pentanone, 4~hydroxy~2
pentanone, and ~he lilce,
The or~er of Rddltion ~f ~he eo~ponen~s used
to prepare these colloidal disp~rsions is not critical. T~us
for example one may firfit mflke a varni8h of the vinyl resin
with the solvent and co-solvent, and optionally fl diluent
followed by.conversion to an ionomer with base and then
emulsi~ication with water. The water can be added to ~he
varnish or vice versa. One may also make these colloidal
dispersions from dry vinyl resin ~ather than a varnish
thereof, ~y adding pulverized xesin pellets to a mixture of
solvent, co-solvent, base~ water and optionally a diluent.
Alternatively9 the resin may be ed in the
mol~en state from a vent extruder or a thin film evapo-
rator into a mixturP o~ solvent 9 cosolvent, water miscible
organic macromolecular compounda base3 and water with
15 .
12635
6~1L2~
vigorous s t lrrîng .
The degree of neutralization of the acid
moieties in the vinyl resin components can as pointed
out above vary over a wide range, i. e ., from about 10%
~:o ~bou~ lûOZ. The op~lm~n degr~e of nelltr~llzation
depend~ upon ~he aDt~unt of acid mo~ety ~n the ~inyl
ro5irl~ ThuS f~r ~sample al v~nyl r2sin contsinlng ~
low ~oune of ac~d ~noiety9 ~Og~ 2 02' 3 welg11t ~ ~hould
~e neu~r~ ed w~h base eo ~ s~uch grea~er exten~ ~han
10 $ v~nyl re~n cos~taln~ng a lar2e ~mourlt of ac~d moie~cies.
Thi~ ~s bel~eved ~o be du~ to the higher pol~r~ty of
ehe h~gher ~cid moie~Sr coslt~in~ng ~inyl re~;1TIS.
No ~peclal equipmeTIt ~s needed to effect
~mulsificatlon o~cher than ~gitac~on or mixl~g equipment
known Co ehose ~lcilled in ~he ar~.
not wi~hing to be bound by any
theoret~c~l explarlat:Lon, ~t ~ ~el~ eve~ ~h~t ~e ornrulation
of the colloidal dlspersions of this in~ention is
~ch~eved wl~chout ~he nQcesslty o~ employing surfac~cants
2 0 by ~he us e of a cost~ lon of:
(A) an org~nic ~olvens w~ch
(~) 18 ~ater-misc~ble, i.~., a~ leas~
1% ~nd prefer~bly lO~ or more wacer is soluble in saLd
solvent; on a weight basis;
has ~n ~ffin~sy ~or th~ ~nyl
resln used, 1.~.~ the ~ol~ ne/resirl ~nter~c~Lt~n $~
gr2~te~ ~han ~che re~ln/re~in interaet~on;
~ 1) hs8 ~ ~oil~ng poln~ lbe~ow
~bou~ . D
16 .
12635
(B) an organic co-solvent ~lich:
(i3 is as water-miscible as ~he
solvent in (A); and
(ii) is a poor solvent for ~he vinyl
resin used, i.eO~ the co solvent/resin interaction is
the resi~/resin interaction,
(C) an optional water-~mmiscible organic diluent;~.
(D) a vinyl resin containing an ionomer
functionality cQpolymerized therein; and
(E) a water~miscible organic m~cromolecular
compound for providing greater stability an~ better Vi9-
cosity control of the dispersion
T~ ~bo~e-de~cribed co~bln~on ~f ~olven~
and ~o-~ol~ent surprisingly l~wer~ the interfacial
ten~ion between the v~nyl resin ~nd the aqueou~ phase
while ~voiding co~ula~lonO Th~8 affords th~ form~tion
of a colloidal dispersion where the droplets qre stabilized
by the ionîc repulsion of the ionomer moiety and the
surfactant-like property of the co-solvent. When this
stage i.s reached it is no longer necessary to maintain the
original levels o~ solvent, co~solvent and/or diluent and
concentration of the colloidal dlspersion can be effected
to afford a higher solids content. In the application
o these colloidal disper~ions to a subs~rate to
o~m ~ co~ting ~he co~l~ent al~o can ~e removed from
the sy~eem with th~ waSer le~ing ~ly the ~nyl ~e~in
~o cons~ltu~ ~h~ coatln~, In eh~ ca~e o~ ~in~l res~n~
3~ neu~s~llzed wlth ~ ~ol~lle b~e~ the lonomer ~n ~he
vinyl r~8~n reYert~ h~ or~g~n~l free aeid mole~y~
1~535
The presence of a water-miscible macromolecular
compound ensures a greater storage stability as well as
a correct VlSCoSity - total solids relationship during
spraying operations. ._
It is a unique feature of the dispersions
described herein that all necessary ingredients for a
satisfactory interior can coating may be introduced at the
t~me of emulsification. The finished colloidal dispersion
may be u~ed as is 9 or s~ripped to higher to~al solids by
vacuum distillation~ or thinned down to lower total
solids by adding back water. Coa~ing formulations pre-
pared in this manner will exhib~t sa~is~actory flow,
atomiæatlon, and we~ting characteristics which are essen-
tial requirements in airless spray ~pplications.
Additionally~ due to the extremely fine parti-
cle sizes present in these dispersions 7 very thin con~inu-
ous protective films can be laîd on both metallic and
non metallic substratesO The resultant films are pin-
hole free, blush resistant and adhere tenaciously to the
substrates,
If so desired~ the water soluble macro~molecules can be partially or completely withheld during
the emulsification and introduced after the solven~
stripping. For the purpose of viscosity control~ addl-
tional thickening agents can also be employed preferably
after the emNlsification~ Suitable thickening agen~s
include such water soluble r~sins as, hydrQlyzed poly-
vinyl acetates or pol~vinyl alcohol 9 water-soluble
18.
12635
~llulo~e ~erilrat~ve~ ., hydroxy@~hyl cel~ulo~e,
polye~hylen~ glycolQ; ~cryllc or ~ethacrylic ~cld po~
mers,poly~-caprolaceon@)7 po~ yl pyrrolldone,
poly~me~hylvinyl eth~r), and the llke.
Other additlve~ known to ~ho3e ~Icilled ~ ~h~
~rt can al~o ~e lncorpora~ed lrleo lthe colloidal disperslons
lf desired. ~he~e lnclude dye~, plgmen~ " flllcr~ ~
ox~d~nt~, ultra~iole~ ~tab~l~zer~ he~ ~tabillzeræ,
and the lil~
Fs~r ~:he purpo e~ of thl~ lnverl~lo~ ~he ~
"water~ clble ~fl.9e3~ i0 u3ed ~n the bro~d sen~e of any
proton ~ceep~or wh~ch will neul~rsli2e thg ~eLt
unctlonal~t~e~ he ~rln~l ~e~ o 9 ~COOH or SC)3H
group~ ~nd whose ~olu~bLlity ~ at leas~ ~bout ~L g. per
1000 SC o~ w~te~. Exemplary ba~es ~hich may lbe ~rg nlc
os inorg~n~c, lnclude ~lkall metal or ~lkalin~ esrth
hydro~Eide~, ~uch sa, ~odium hydroscide, po~a~slu~D hydroxide9
l~thlum hydroxlde, magnesiu~ 'hydr~xideO c~lclu~ hydroxlde5
~trontiu~ hydrox~de, bari~ hydro7cide, ~sld the l~ke;
~nd ammonium hydroxide; or~anic amine.q $ncludin~ moro~
~lkylamine3, alkenediam~n2s 9 alkanolamines, ~romatiLc
~mine~, cycl1 c amines, alkaryl araines, and the like . Fo~
~conom~c reasons and ready ava1l~billey alkal~ metal,
alksline earth and ammon~um hydroxite~ a:re pre~erred in-
organ~c ba~e~. In coatlng appl~oati.on lt i~ preferred
~o ~x volatile bases which are fug:le~e ~nt corl~equently
reYer~ble iorlomer~ ase formed. For exa~le, ~mmonium
hydroxlde or lower molecular weight ~lkylamine~ fo~
.
19 .
635
~orlomers which afford coa~ing~ where~n th~ ionomer
~let~e~ re~rer~c to acid and from which Sh~ base, being
~1gitlvo, ~ removed. Thi~ en~iances bïu~h re~gtan~e
and ~D$nimlz@ color forma~iQn upon ~xpssuse o ehe ~n~1
60ating eo the ~lemen~. P~rticularly preferred ~lkylD
~mlne~ lnclude ~onome~hyl am~ne, dil3185:hyl amln~, tr~
~chyl ~min*, trie~hyl amlne, and ehe lik~.
- In general, preferred alkyl amines ~a~e ~h~
~ormuls:
R ~ N - R
where~n each ~ R ~ ~baT~ ~e ~ ~ ~ 6 ~i~cy~ ~lt~
g~e ~o~ ~h~ R ~ 6 ~ o
e ~
~referred alkylene diamine~ ha~e ~e formul~o
~ N ~D~
wher~ x ~ 1 ~ 8 and D i~ alkylenP r~dicsl.
Prer~rred alXanola~ine3 :~nclude monv~, di-,
an~ tri~ ethanola~ne, N~ e thyl e thanolamirle, N ~ ~
dime t~y~e thanola~ine, N, N- die t~Lyl e ~Lanol~mine, N-
asa~noethylet~anolamine, N-methyl diethanolamine, and
the like.
P~eferred cycllc ~nine~ include marpholine,
~m~thyl morpholine, plperidlne, pyrrolldlne, plper~
~æine, N-me~hyl plperazine, N- ~2-hydroxyethyl3piper-
azine, ~aminoethyl piperazille, 2,5~dime~hyl plperazine,
hexamethylene ~e~ram~n~, and t~e llke.
20 .
12635
~ referred lower allphatic ~etone ~olven~
lnclude ~cetone, methyl et~yl lcetone ~:~C), diethyl
ketone, me~hyl n-propyl ketone, me~hyl l~opropyl
ketorle, ace~yl aceeorle, l~me~hoxy~2~propflnone, and ~he ll~ce.
Preferred lower ~l~phatic e3ter s~lven~
lnelude methyl formate, ethyl formaee, methyl ~cetat@,
e~hyl acet~e, i~opropyl aee~a~e, ~nd th~ like.
Preferred low~r al~pha~:lc eth~er ~ol~en~:~
~ncll~de die~ yl ee~er, e~hyl propyl etl~er, di-n~propyl
1.0 ~the~r, and ehe lllce,
~ refe~red cycloal~p~tic ketones ~olvenes
~nclude cyclobu~anon~, cyclopen~anone, cyclohexanone,
and the like~
Pra~erred cyclo~liphatic et~er ~olYent~
clude, dloxane, tetrahydro~urano,- a~t the ~ike.
~- Depending on the particular vinyl halide
resin used, it may be preferable to use mixtures of
these solvents rather than a single solvent. For ex-
ample, with a vinyl chloride/vinylacetate/maleic acid
terpolymer the combination of acetone with another
ketone, such as methyl ethyl ketone9 will give dispersions
superior to those formulated with acetone alone. It is
also permissable to use a mixture of cosolvent instead
of a single cosolvent.
Occaslonally, it may be desirable to modify
the solvent s~stem w~th a minor amount o~ a water~immiscible
- organic diluent for rPasons of matching the
solubility parameters between the solvent system and ~he
resin(s) to be disp~rsed. This may be done wîthout
adversely a~fecting the quality of the finished dispers
ions as long as the solvent system as a whole retains an
21,
12635
adequate degrPe o~ water miscibility. I~ is preferred,
however, that the water~Lmmiscible organic diluent or it~
~zeotrope with water boils at a lower ~emperature than
water to facilitate its removal during the vacuum distil-
lation.
Exemplary water-immiscible organic diluents
which are miscible with both ~he solvents and cosolvents
include:
alkanes having about 5 to about 20 carbon atoms
and hal.ogenated alkanes having about 2 to about 20 carbon
atoms~ such as~ pentane, hexane~ heptane, l-chloropen-ane~
1~2-dichloroethane, trichloroethylene~ tetrachloroethylene~
1,2-dibromohexane~ and the like;
cycloalkanes and halogenated cycloalkanes having
about S to about 12 carbon atoms, such as, cyclopentane,
cyclohexane, cycloheptaneJ chlo~ocyclohexane~ and the
like;
aromatic hydrocarbsns having 6 to about 1~ car-
bon atoms~ including both unsubs~ituted and alkyl or
~0 halogen substitu~ed hydrocarbons, such as~ benzene, toluene,
xylenes~ chlorobenzene~ o-chlorotoluene,and the like;
aliphatic ketones having about 7 to about 12
carbon atoms 7 such as 3 propylbutyl ketona~ dibutyl ke-
tone, butylhe~yl ketone, and the like;
cycloaliphatic ketones having about 7 ~o abou~
12 carbon atoms, such as, cyclohexyl ketone9 cycloheptyl
ketsne, and the likej
alkaryl ketones having about 7 to abou~ 12
carbon atoms, such as; ace~ophenone, propiophenone, and
the like;
~ 635
aliphatic and aroma~ic esters having about 7
to about 12 carbon atoms, such as, me~hyl benzoa~e,
hexyl benz~a~e, methyl hexsnoate9 propyl octanoate,
hexyl acetate, and the like;
olefins having ~bout 6 ~o about 20 carbon atoms9
such as, hexene-l, oc~ene 2, oc~ene-19 eicosene 19 and
the like~
While these wa~er-immiscible dlluents can be
used at a level of up to about 49 par~s per hundred parts
by weight of organic solvent~ it is preferred however t9
use a level of about 1 to about 25 parts per hundred par~s
b~ weight of organic solvent.
A particularly preferre~ method of preparing
colloidal dispersions of ~he vinyl resins described above
comprises:
A. blending said resins with:
(a) water;
(b) a wa~er-miscible base;
(c) an organic water-miscible macromole-
cular compound;
(d~ about 1 to abou~ 500 par~s per hundred
parts by weigh~ of resins of at least one watermiscible
organic solvent which hss an affinity for said resin and
boils below abou~ 160C.;
(e) about 1 ~o abou. 500 parts per
hundred parts by weight of resin of an organic water~
miscible co~solvent whi~h is a poor ~olvent for said
resins but ls miscible with the organic solvent (d3
23.
.f`
1263
() 0 to about 49 parts of water
~mmiscible organic diluent per h~mdred parts by w~ight of
organic solvent (d3;
until a stable colloidal dispersion forms; and
(B) stripping the colloidal dispers~on until
the total content of organic solven~s (d) and (e~ and
diluen~ (f) of ~he final colloidal dispersion is about
0.2 to ~bout 20~/o by volume.
If the total oxganic solvent concent falls
below about 0.2% by volume the coatings produced
from such formulation may contain pin holes and other
voids. If the total content of organic solvents and
diluen~ goes above about 20% by volume general ecology
standards are violatPd.
While it is not absolutely essential ~ if
desired, an organic coalescing aid may b~ added ~o the
stripped colloidal dispersion.
Exemplary coalescing aids include:
(1) glycols ha~ing 2 ~o about 6 carbon atoms 9
such as, ethylene glycol, 1,2-propylene glycolg diethylene
glycol, triethylene glycol, and the like;
(2) glycerine~
When used the coalescing aids should be present
in an amount up to about 25 parts by weig~t per 100 parts
by weight of water in the colloidal dispersionO
The colloidal dispersions of this.in~ntlon
are particularly adapted to co~ting cans although other
substrates both metallic and non metallic can also be
coated with these dispersions for their ~mproved utility
24.
~ 5 12635
in packaging and myriad o~her applications which will be-
come apparent to those skilled in the art upon a :reading
of the specification.
Cupric sulfate test is a test commonly used
for detecting the presence of pin holes in an interior
can coating. Sa-tisfactory coatings should reveal no
visible defects in this test.
Interior can coatings are usually applied by
airless spray, a technique well known to those skilled
in the art. While most examples described in this in-
vention are based on 2-piece aluminum cans, this invention
is equally useful to 2-piece cans constructed of other
metals as well as to 3-piece cans. Those metallic cans
are used widely for the packaging of beer, beverage, and
food.
The invention is further described in the
examples which follow. All parts and percentages are
by weight unless otherwise specified. A la~oratory
airless can spray unit consisting of an emulsion reservoir,
a pumping unit, a press~lrate gauge, a timer, a heating
device, a nozzle assembly, and a ro-tary can mount was
employed.
Example 1
Preparation of Ammonium Hydroxide Ionomer Dispersion
To a varnish composed of 211.9g. of BAKELIT
VMCC vinyl resin (a terpolymer containing 81% vinyl
chloride, 17% vinyl acetate and 1% maleic acid copolymerized
therein), 105g. of BAKELITE~ VERR vinyl resin (a terpolymer
containing 80% vinyl chloride, 11% vinyl acetate, and
9% glycidyl methacrylate copolymerized therein), l~08.8g.
25.
.~
~a6~
12635
of methyl ethyl ketone, and 68.1g. of butyl CELLOSOLVE
(a trade-mark of Union Carbide Corporation for the
monobutyl ether of ethylene glycol), was added with
vigorous stirring 1,423g. of an aqueous solution contain-
ing 10.5g. o a 58% ammonium hydroxide solution, 21g. of
Gelvatol~-2050 poly(vinyl alcohol) resin (a partially
hydrolyzed poly(vinyl acetate) resin produced by Monsanto),
10.5g of Beetle~-60 (a methylated urea-formaldehyde resin
produced by American Cyanamid). An aqueous dispersion
characterized by an intense Tyndall scattering effect was
obtained. The latter is usually associated with the
formation of microemulsions or colloidal dispersions as
defined in "Microemulsions - Theory and Practice", Academic
Press, p. 7 (1977), edited by L. M. Prince. After vacuum
stripping, the finished dispersion possessed the following
composition and physical properties:
% by Weight
Total Solids 32
Butyl CELLOSOLVE 3.5
Ammonium Hydroxide1 (approx.)
Water 63.5
Brookfield Viscosity1200 centipoise
pH 7.5
Surface Tensionl~2 dynes/cm
Example 2
Example 1 was repeated with the exception that
BAKELITE T~MCC vinyl resin was replaced with BAKELITE VMCA
vinyl resin (a terpolymer contai.ning 78% vinyl chloride 9
20% vinyl acetate and 2% maleic acid copolymerized therein)
26.
,~
s
12,635
and Gelvatol~-2060 poly(vinyl alcohol) resin was replaced
with Gelvato1~-2030 (a partially hydrolyzed poly(vinyl
acet~te)resin of lower molecular weight). After vacuum
strippingS the finished dispersion exhibited the following
composition and physical properties:
% by Weight
Total Solids 40
Butyl CELLOSOLVE 3
~mmonium Hydroxide1 (approx.)
Water 56
Brookfield Viscosity1,400 centipoise
pH 7.0
Surface Tension42 dynes/cm
Example 3
To a varnish composed of 45g. of BAKELITE~ VMCH
vinyl resin ~a terpolymer containing 86.5% vinyl chloride,
12.5% vinyl acetate, and 1% maleic acid), 11~.3~. of methyl
ethyl ketone, and 22.7g. of butyl CELLOSOLVE, was added
with vigorous stirring 364g. of an aqueous solution
containing 3g. of 58% ammonium hydroxide solution9
6g. of Gelvatol~-2090 poly(vinyl alcohol) resin (a partially
hydrolyzed p~ly~vinyl acetate) resin produced by Monsanto),
3g. of Cymel-301 melamine-forma]dehyde resin
(hexamethoxymethylmelamine sold by American Cyanamid).
A uniform dispersion was obtained, which was strlpped
under vacuum to yield the following product:
% by Weight
Total Solids 18
Butyl CELLOSOLVE 5.7
Ammonium Hydroxide1 (approx.)
Water 75.3
Brookfield Vlscosity1,040 centipoise
pH 7.5
Surface Tension39 dynes/cm
. `L ~i'J
~ 5 12635
Example
To a varnish composed of gOg. of B~KELITE VMCH
vinyl resin, 102g. of ME~, and 34g. of t-butyl alcohol was
added with vigorous stirring an aqueous solution con~aining
3g. of ammonium hydroxlde~ 5g. of Gelvatol-2090
poly(vinyl alcohol) resin~ 3g. of Cymel-301 melamine-
formaldehyde rPsin and 357g. of wa~er. The resulting
e~ulsion was concentrated under vacuum at 50C to yield
a product of the following composition and charact~ristics:
% by weisht
Total Solids 20
A~monium Hydroxide1 (approx.)
water 79
srookfield viscosity 2,500 centipoise
pH 7.0
Surface Te~sion62 dynes/cm
Example 5
Example 4 was repeated with the exception that
BAKELITE VMCH vinyl resîn was replaced with an equal
amount of B~KELITE VMCC vinyl resin. The finished dispersion
had the following composition and properties:
% b~ Welght
Total Solids 20
Ammonium Hydroxide1 (approx.)
Water 79
Brookfield Viscosity 2,000 centipoise
pH ` 7.0
Surface Tension63 dynes/cm
Example 6
Example 4 was repeated with the excep~ion that
BAKELITE ~MCH vinyl resin was replaced with an equal amount
of BAKELITE VMCA vlnyl resin. The finished dispersion had
the following composition and properties:
28.
s
12635
% by Weight
Total Solids 19
Ammonium Hydroxide1 (approx.)
Water 80
Brookfield Viscosity2,000 centipolse
pH 6,5
Surface Tension63 dynes/cm
Example 7
Example 1 was repeated with the excep-tion that
Beetle-60 urea-formal~ehyde resin was replaced with an
equal amount of Cymel-301 melamine-formaldehyde resin.
The finished dispersion had the following composition
and properties:
% by Weight
Total Solids 34
Butyl CELLOSOLVE 3.6
Ammonium Hydro~ide1 (approx.)
Water 61.4
Brookfield Viscosity1,600 centipoise
pH 7.5
Surface Tension41 dynes/cm
Example 8
~ Example 1 was repeated with the exception that
Beetle-6~ urea-formaldehyde resin was replaced with 14.3g.
of Beetle-$5 urea-formaldehyde resin (a partially
methylated urea-formaldeh~de resin produced by American
Cyanamid C~.) and Gelvatol-2060 was replaced with 28.59
of Elvanol-51-05-G (a partially hydrolyzed poly(vinyl
acetate) resin produced by DuPont). The finished dispersion
had the following composition and properties:
% by Weight
To~al Solicls 38
Butyl CELLOSOLVE 3
Ammonium Hydroxide1 (approx.)
Water 58
Brookfield Viscositu610 centipoise
pH 7.0
Surface Tension43 dynes/cm
29.
,~
12635
Example 9
Example 1 was repeated with the exception that
Gelvatol~-206 poly(vinyl alcohol) resin was replaced with
Vinol~-540 (a partially hydrolyzed poly(vinyl acetate)
produced by Air Products and Chemicals Inc.). The finished
dispersion had the following composition and properties:
% by Weight
Total Solids 30
Butyl CELLOSOLVE 4
Ammonium Hydroxide1 (approx.)
Water 65
Brookfield Viscosity3,700 Centipoise
pH 7.6
Surface Tension39 dynes/cm
Example 10
To a varnish composed of 60g. of VMCC and 30g~ of
VERR vinyl resins, 81g. of acetone, 27g. of isopropyl aceta~e,
and 27g. of butyl CELLOSOLVE was added with vigorous stirring
404g. of an aqueous solution containg 6g. of Beetle-60
urea-formaldehyde resin, and 3g. of ammonium hydroxide.
A uniformly dispersed emulsion was ob-tained.
Example 11
Example 10 was repeated with the excep-tion -that
isopropyl acetate was replaced with an equal amount of
hexane. A unlformly dispersed emulsion was obtained.
Example 12
Example 10 was repeated with the exception that
isopropyl acetate was replaced with an equal amount of
tetrahydrofurane. A uniformly dispersed emulslon wa~
obtained.
30.
12635
Example 13
One-half the amount of isopropyl acetate
employed in Example 10 was replaced with toluene. A
uniformly dispersed emulsion was obtained.
Example 14
To a varnish composed of 90g. of R~.LITE VMCC
vinyl resin, 108.8g. of MEK and 27~2go Of butyl CELLOSOLVE
was added with vigorous stirring 393g. of an aqueous solution
cont~;ning 5gO of Gelvatol-2060 poly(vinyl alcohol) resin,
3g. o Beetle-55 urea formaldehyde resin, 3g. of
ammonium hydroxide and 381g. of water. The dilute dispersion
was vacuum stripped a~ 55C to yield ~he following product:
% by Weight
Total Solids 35
Butyl CELLOSOLVE 4
Ammonium Hydroxide 1 (approx.)
Water 60
srookfield Viscosity 1,100 centipoise
pH 7
Surface Tension 39 dynes/cm
Example lS
Example 14 was repeated with the exception that
an equal amount of Cymel-301 was used to subs~itute for
the Beetle-55. After vacuum strippin~ ~he finished
dispersion possessed the following composition and
characteristics: .
~ by Weight
Total Solids 32
Butyl CELLOSOLVE
Ammonium Hydroxide 1 (approx.)
water 63
Brookfield Viscosity 980 centipoise
pH 7.5
Surface Tension 39 dynes/cm.
635
Example 16
To a varnish consisting of 90g. of a (vinyl
chloride-vinyl acetate-maleic acid) terpolymer, having
th~ follow.ing composition and characteristics:
~ by Wei~ht -
Vinyl Chloride64, 5
Vinyl Acetate 23
Maliec Acid 12.5
Reduced Viscosity0.18
(measured i~ cyclohexanone at 25C)
108.8g. o methyl acetate and 27.2g. of butyl CELLOSOLVE
was added with vîgorous stirring 393g. of an aqueous
solution identical to the one employed in Example 14.
The dilute dispersion was concentrated under vacuum to
yield the following produc~:
. ~ by Weight
Total Solids 35
Butyl CELLOSOLVE3.S
Ammonium Hydroxide 1 (approx.3
~ Water 61.5
Brookfield Viscoslty 1,400 cent.ipoise
6.5
Surface Tension41 dynes/cm
Example 17
Example 16 was repeated with the excep~ion ~hat
the 3g. of ammonium hydroxide was replaced with 6g. of
N~N-dimethyl ethanol amlne. After solvent stripping,
the inished emulsion possessed the following composition
and charac teris t ic s:
~ by Weight
Total Solids 35
Butyl CELLOSt)LVE 3 . 5
N, N Dimethyl Ethanolamine 2
Water 59, 5
Brookfield Visc05ity 1, 600 cen~ipoise
pH 7. 5
Surface Tension39 dyne~/cm
3~ .
1 9~
~L ~ 12635
Example 18
The waterborne co~tirlg formulation~ prepared
in the above examples may be modified by a variety of
add;tiYes commonly used in the coatings industry. For
instance, the dispersion prepared in Example 1 may be
modified with additional organic solvent(s) for achieving
better wetting, rheological, and 1 lmin~ proper~ies.
Some examples are ~isted in Table I~ All formulations in
Table I contained 20% by weight of total solids. Dilu~ion
w~s carried out by mi~ing the original dispersion with an
aqueous solution containing the appropriate solvent or
sol~entsO
~ABLE I
CHARACTERISTICS i:)F SOLVENT-MODIFIED
VINYL IONO~RIC COLLOIDAL DISPERSIONS
. 8ROORFIELD NO. 4 PORD CUP
RESIDUAL SOLVENT TYPE( ) SUR~ACE TENSION VISCOSITY FLOW TIME
(~ BY WEIGHT IN VOLATILE PHASE)DYNES/CM CPS SEC.
~C~3.4~ 44 67 13.8
BC(3.4); POH58.~) 34 51 14.0
BCt4.4); nBOH(3.7) 30 35 ~1.6
BC(3.4); PSB(0.9) 41 74 14.2
BC(3.4); nHC(0.8); EO~(7.5) 31 26 12.2
BC(3.4); PSB~.l); POHt6.3~ 31 26 12.4
BC(3.4); PSP(~.l)~ POH~6.3) 34 4~ 13.6
BC(4.4); PG (1.6)~3) 43 275, 42
(1) WHE~E ~C = B~TYL CELLOSOLVE; EOH - ErHANOL; POH ~ PROPYL ALCOHO~;
nBOH = n-BUTYL ALCOHOL; PS~ = PROPASOL SOLVENT-B, A UNION CAR3IDE T~ADE N~ME
FOR ~HE MONOBUTYL ETHER OP PROPYLENE GLYCOL; nHC = n-HEXYL CELLOSOLVE;
PSP - PROPASO~ SOL~ENT-P, A MONOPROPYL ETHER OF PROPYLENE GLYCOL;
PG ~ PROPYLENE GLYCOL
(2) A VISCOMETER, THE LONGER THE ~LOW TIM2 THE GREATER THE VISCOSITY.
~3) Contain~d 24% total solids
33
12635
Example 19
Emulsions prepared in the above examples were
evaluated as interior can coa~ings for some typical
2-piece aluminum cans= Coa~ings were applied with an
airless spray uni~ consisting of a paint reservoir) a
pump unit, a pre-heater~ a spray-timP controller, a
noæzle assembly, and a rotary can mount. The sprayed can
was baked in an air-drift oven to cure the coating.
A dispercion prepared according to E~ample 1
was diluted with water and butyl CEL WSOLVE to yield the
following form~lation:
~ by Weight
Vinyl Resins 25
Gelvatol-2060 1.67
Beetle-60 0.83
Ammonium Hydroxlde 1 (approxO)
Butyl CELLOSOLVE 3.6
Wa~er 67.9
~00~
Brookfield Viscosity 216 centipoise
No. 4 Ford Cup Flow Time 25 sec.
pH 8.5
The above dispersion was sprayed at room temperature under
a pres~ure of 90 psi for 150 micro sec. to produce a dry
coating weight of 187 mg./can. Baking was carried out
at 175C for 2 min. The finished intPrior coating
exhibited the following properties:
Type of Cans - Cl~aned - only
aluminum cans
Appearance - Clear and Glossy
Mottling - None
CuSO4 Test - Passed
- Enamel RatPr Test - Below 20 MA
Blush Resistance - Satisfactory
Wet Adhesion - SatisEactory
Taste Test - Satisfactory
34,
2 5
12635
Example 20
A disper~ion prepared according to E~ample 3
was thinned down with water and Propasol Solven~-B to
gi~e the following formula~ion:
% by Weight
~inyl Resin 13.5
Gelvatol-2090 1.0
Cymel-301 0.5
Ammonium Hydroxide 1 (approx.)
1~ Butyl CELLaSOLVE 3.9
Propasol Solvent-~ 1.3
~ater. 88.~
srookfield Viscosity 280 centipoise
No. ~ Ford Cup Flow Time 30 sec.
p~ . 8.5
The abo~e dispersion was sprayed at room te~perature under
a pressur~ of 85 psi for 180 micro-sec, to produce a dry
coating weight of 170 mg./can. Baking was carried out at
1755 for 2 min. The finished lnterior coating exhibited
the following properties:
Type of Cans - Alodine 404 (non~chrome)
with Reynolds "A" bottom
can configuration.
Appearance - Clear and Glossy
Mottling - None
CuSO4 Test - Passed
Enamel Ratex Test - Below 20 MA
Blush Resistance - Satisfactory
Wet Adhesion - Satisfactory
Taste Test - Satisfactory
12635
Example 2 1
A dispersion prepared according to Exarllple 14
wa~ diluted with an aqueous solution contairling
isopropyl alcohol and Propasol Solvent~P to yield the
following formulatiorl:
~ by Weight
Vinyl Resin 25
Gelvat~l ~060 1. 4
Beetle-55 o . 7
~mmonium Hydroxide
Isopropyl Alcohol 2
Propa sol Solvent~P 2
Butyl CELL050LVE
Wa ter 6 5 . 9
Brookfield viscosity215 centipoise
No. 4 Ford Cup Flow Time 31 ~ec.
The above dispersion was sprayed a~ 40C under a pressure
of 95 psi for 100 micro-sec. to produce a dry coatin~
weighe of 183 mg./can, ~akin~ was carried ou~ at 175(~ for
20 2 min. The finished interio~ coating showed the following
propert ies:
5~ype of Cans - Same as used in Example 20.
P.ppearance - Clear and Glossy
Mottling - None
CuS04 Te~t - Passed
Enamel ~ater ~est - Below 20 MP~
~lush Resistance - Satisfactory
Wet Adhesion ~ Sati~factory
T~ste Test - 5ati~sactory
Example 22
A dispersion prepared ~ccordin~ tD Example 1
but withou~ the ~eetle-60 ure~ for~ldehyde resirl w~s used
for 1q~5~klng the follow~ng heae-~e~l~ble laminated films:
lJ2 m~l el ~ck dry coating wa~ ~pplïed on ~ 1 mil
almealed s~ n~m foil by u51~g ~ wi~e~wound rod and
ollow~d by b~?king B~; 175G for 8 Tn~Utes, The coa~ced
aluminum foil was smoo~h and glos~yO Hea~ ~esls were
36 .
~ 5 12635
prepared using a Sentinel heat sealer with the hot bar
set at 235C~ a clamping pressure of 50 psi, and a duration
of 2 seconds. The seals were ~ound to have a satis~actory
peel s~rength of 2 lbs~/in. (ASTM-D-1376~61T~ A control
applied from MEK/toluene solution yielded a peel strength
o~ 2.1 lbsO/in.
Example 23
To a varnish composed o 90g~ of BAKELITE VMCC
vinyl resin, 108g oE MEK~ and 27, 2g of t butyl alcohol,
was added with vigorous stirring 416.5g of an aqueous
solution containing 3g of ammonium hydroxide9 3g of
Beetle-55~ 12g o GAF'5 PVP/~A I-335 resin (a copolymer of
N-vinyl pyrrolidone (30%) and vinyl acetate (70%)~ and
386,5g of wa~er. An aqueous dispersion characterized by
an intense Tyndall scattering effect was obtained. After
vacuum stripping, the finished dispersion possessed the
following romposition and physical properties:
~/O by Weight
To~al Solids 26
Total organic solvents 0.2 (approx.)
Ammonium Hydroxide 1 (approx.)
Water 72.8
Brookfield Viscosity - 26 cen~ipoise
pH
~xample 24
Example 23 was repeated with the exception that
GAF's PVP¦VA I-335 xesin wa~ replaced with &AFas PVP/VA
I-535 (a copolymer of N-vinyl pyrrolidone (50~/0) and vinyl
acetate (50%). After vacwm strippir.g, the inished dis-
31.
12635
persion posses~ed the following composi~ion and physicalproperties:
% by Weight
Total solids ~8
Total organic solvents 0,2 (approx.~ -
Ammonium Hydroxide 1 (approx.)
Water 70.8 -
Brookfield Viscosity 24 centipoise
P~ 7.5
10~ Example 25
Ex~mple 23 was repea~ed with the exception that GAF's
PVP/VA I-335 resin was replaced wi~h GAF's PVP/VA I 735 ~a
copolymer of N-vinyl pyrrolidone (70%) and vinyl acetate
(30%), After vacu13m stripping, the f~nished dispersion
possessed ~he following compositlon and physical propert-Tes:
% by Weight
Total solids 26
Total organic solvents 0,2(approx.)-
Ammonium Hydroxide 1 ~appro~O)
Water 72.8
Brookfield viscosity 32 cen~ipoise
pH 7.5
Example 26
To a varnish cornposed of 92 . 8 lg o~ BAI{ELITE
VMCC vinyl resin" ~07.5 g of acetone,, 46.6g of toluene~
and 69.3g of n-butyl alcohol, was added with vigorous
stirring an aqueous solution containing 4~64g of Gelvatol-
4010 (a partially hydrolyzed PVOH resin produced by
Monsan~o) 4~2g of ammonium hydroxide, and 404 g of wa~er.
A fine dispersion was obtained. After stripping ~mder
vacuum9 ~he fiIlished dispersion possessed the followirLg
composition and physical properties:
38 .
1~635
% by Weight
Total solids 25
Total organic solven~s 0 .2 (apyrox. )
arnmonium ~ydroxide74-~ (approx.)
Brookfield ~7iscosity 46 centipoise
pH 7
Example 2 7
To a varnlsh composed of 60g o BAKELITE VMCC
vinyl res~, 30g of VEE~ vinyl resin, la2g o ~EK, and 34g
o~ t-but~l alcohol, was added Wittl vigorous stirring
316g of aqueous solutlon cont~n~ng 4g of Gelva~ol-40109
3g of Beetle~60 and 3g of ammoniurn hydroxide. A fine
disper~ion was obtained. Aft~r stripping under ~acu~n,
che finished dispersion posses~ed the following composi-
tion and physical proper~ies:
~/O by Weight
Total solids 30
To~al organic solverlts 0 .2 tapprox. )
ammonium hydro~ide0.8 (approx,)
water 69
Brookfield ViscositySS centipoise
pH 7.S
Sur~ace ~ension 68 dynes/cm
E}:ample 2 8
Example 27 was repeated with th~ exception that
only 90g of VMCC vinyl resin was used, and Beetle 60 in
the aqueous phase was replaced wit~ the same amount of
Cymel-301D A tran~lucent dispersion was obtainedO
After stripping under vacuum, the finishe~ dispersion
had a tota:L solids conten~ of 38~4~/o by weigh~c.
39 .
12635
Example 29
A 200 gm quantity of the stripped dispersion
prepared in Example 28 was mixed in a Waring blender
with 5.lg of Gelvato ~-2090 PVOH resin, ].2.3g of n-butyl
alcohol, 12.3g of Propasol Solvent-B, and 109g of water.
The diluted dispersion possessed the following composition
and physical properties:
% by Weight
Total solids 24
Total organic solvents 7.2
ammonium hydroxide 0.8 (approx.)
water 68
Brookfield viscosity248 centipoise
pH 7
Surface tension 32.7 dynes/cm
No. 4 Ford Cup Flow Time 48.8 sec.
Example 30
To a varnish composed of 87.lg of VMCA vinyl
resin, 98g MEK and 32.7g of Ethyl Cellosolve was added
with vigorous stirring 269.7g of an aqueous solution
containing lg o CELLOSIZ ~-QP-40 (a h-ydroxyethyl cellulose
resin produced by Union Carbide), 2g of Cymel~-301 and
8.7 g of trimethylamine (~5% aqueous solution~. A
uniform dispersion was obtained. After vacuum stripping
at 50C a dispersion containing 36.7% of total solids was
obtained . It possessed a pH of 6.75 and a Brookfield
viscosity of 656 centipoise.
Example 31
Example 30 was repeated with the excep~ion
that VMCA vinyl resin was replaced wi-th 60g of VMCC and
30g VERR vinyl resins, and CELLOSIZE-QP-40 was replaced
with 1 g of CEL~OSIZE-QP~15,000. A ~miform dispersion
40.
~.t
z~
12635
was obtalned. After vacuum stripping at 50C a dispersion
containing 32.4% total solids was obtained. It possessed
a pH a 7.8 and a Brookfield viscosity of 756 centipoise.
Example 32
Example 30 was repeated with the exception that
the aqueous solution was replaced with another aqueous
solution containing 24g of Carbowa ~ 200 (a poly(ethylene-
glycol) resin produced by Union Carbid~) 5g of Beetle 60,
2.7g of ammonium hydroxide and 258g of water. A uniform
dispersion was obtained. After solvent stripping, the
finished product possessed a total solids content oE 38%,
a pH of 6.95, and a Brookfield viscosity o-f 38 centipoise.
Example 33
Example 32 was repeated with the exception that
Carbowax~ 200 was replaced with Carbowax~ 6,000. A fine
dispersion was achieved. After vacuum stripping, the
-~ finished product possessed a total solids o~ 33.6%, a
pH of 7.2 and a Brookfield viscosity of 176 cen~ipoise.
Example 34
Example 26 was repeated with the exception that
no Gelvato ~ 4010 was used in the aqueous during the
emulsification. A fine dispersion was obtained, which
was vacuum distilled to a total solids of 35%.
One hundred grams of the above concentrated
dispersion was mixed in a Waring blender with 2.45g of
.~,
36~Z~ 12~jJ5
.
Gelvatol-4010~ 37.6g o water, and two drops of ammonium
hydroxide ~o yield ~ uniform formulaeion. The latter
had a total ~olids of 25%~ a pH of 7.8, and a ~rookfield
viscosity of 75 ce~tipoise.
Example 35
A dispersion prepared according to Example 14
was modified with an aqueous solu~ion containing Gelva~ol-
2090, Beetlc-55, Butyl CEL~OSOLV~, and Propylene glycol to
yield the followlng formulation:
~/O by weight
Vinyl Resin 20
Gelvatol-2060 and -2090 1.8
Beetle-55 o.g
Butyl CELLOSOLVE 4.8
Propylene ~lycol 1.6
Ammonium Hydroxide 0.8 (approx.)
Water 70.1
Brookfield Viscosity 285 cen~ipoise
No. 4 Ford Cup Flow Time 32 ~ec.
The above dispersion was sprayed at 40C under
a pressure of 95 as~ for 120 mlcro-seconds to produce a
dry coating weight of 165 mg./can. Baking was carried out
atl75C for 2 minu~es, The finished interior coating
showed the follswing proper~ies:
Type of can~ - S~me as used ~n Example 20
App~arance - Cl~r and gl~sy
Mo~llng - None
42O
.~
6:~2~ 1~, 635
C4S04 Tes~ - Passed
Enamel Rater Test - Below 20 ~A
Blush Resistance ~; Satisfactory
Wet Adhesion Satisfactory
Taste Test: Satisfactory
Although the invention has been described in
its pref2rred for{ns wi~h a certain degree of partloulari~y,
it is understood that the present disclosure has bPen
made only by way of example ~ and that numerous changes
10 can be made without departing from the spirit and scope
of the invention.
~ 3 .
