CA1196125A - Vinyl resin metal coating compositions - Google Patents

Abstract

IMPROVED VINYL RESIN METAL COATING COMPOSITIONS

ABSTRACT OF THE DISCLOSURE
Vinyl and vinylidene halide resins containing carboxyl or sulfonic acid functionalities can be formulated as stable, aqueous, colloidal dispersions by converting them to ionomers in a mixture of water-miscible base, water, organic water-miscible macromolecular compound, water-miscible organic solvent having an affinity for the resin and water-miscible organic co-solvent which is a poor solvent for the resins and optionally a water-immiscible organic diluent and then stripping the mixture to a total organic solvent content of about 0.2 to about 20% by volume.

S P E C I F I C A T I O N

1.

Description

" 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

. ~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 ~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~ .

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 .

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 .

(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.

~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 .

~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 .

~ 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, 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`

() 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~

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 % 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.

,~

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.

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.

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 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, 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 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.

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 .

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~

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 .~

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 .

Claims (31)

WHAT IS CLAIMED IS:

1. Method of preparing water-borne colloidal dispersions of vinyl resins selected from the group con-sisting of vinyl chloride, vinylidene chloride or vinyl chloride/vinylidene chloride copolymers having carboxylic or sulfonic acid groups contained therein which comprises:
A. blending said resins with (a) a water-miscible base;
(b) water;
(c) an organic water-miscible macro-molecular compound;
(d) at least one water-miscible organic solvent which has an affinity for said resins and boils below about 160°C.; and (e) an organic and water-miscible co-solvent which is a poor solvent for said resins but is miscible with the organic solvent (d); and (f) 0 to about 49 parts by weight of a water-immiscible organic diluent per hundred parts by weight of organic solvent (d) until a colloidal dispersion forms; and B. stripping of the colloidal dispersion until the total content of organic soluents (d) and (e) and diluent (f) of the final colloidal dispersion is about 0.2 to about 20% by volume.
44.

2. Method of preparing water-borne colloidal dispersions of vinyl resins which comprises blending:

(A) a normally solid vinyl resin containing carboxylic or sulfonic acid groups and having the following moieties copolymerized herein (1) (2) (3) (4) (5) wherein m and n are percentages each having a value of 0-99%;
t is a percentage having a value of 0-59%;
p is a percentage having a value of 1-30%;
when q = 0;

45.

q is a percentage having a value of 1-30%;
when p = 0 with the proviso that m+n+t is ? 70 and ? 99%, that m+n+t+p+q = 100%, that when m = 0, n is at least 1 and that when n = 0, m is at least 1, wherein X is a monovalent radical selected from the group consisting of -H and lower alkyls having 1-4 carbons;

W is a monovalent radical selected from the group consisting of -H, lower alkyls, aryl having 6 to about 9 carbons, wherein a is an integer having values of 1-3, -OR(wherein R is a C1-C18 alky), (wherein R1 is a monovalent radical selected from the group consisting of -H, methyl or ethyl), and -CN;
Y is a monovalent radical selected from the group consisting of -H, methyl;

, wherein b is an integer having values of 0-4; and Z is a monovalent radical selected from the group consisting of 46.

, -SO3H and -C6H4- SO3H, with the proviso that Y and Z are never COOH and -SO3H at the same time, (B) sufficient water-miscible base to neutralize about 10% to 100% of said carboxylic or sulfonic acid groups, (C) 1 to about 500 parts, per 100 parts by weight of vinyl resin of a water-miscible normally liquid solvent for said vinyl resin having a boiling point of up to 160°C., selected from the group con-sisting of lower aliphatic ketones, esters or ethers having 3 to about 6 carbon atoms and cycloaliphatic ketones or ethers having 4 to about 6 carbon atoms;

(D) 1 to about 500 parts, per 100 parts by weight of vinyl resin, of a normally liquid co-solvent which is a poor solvent for the vinyl resin but is miscible with water and solvent (C), selected from the group consisting of:

(1) glycol monoalkyl ethers having the formula:
where each of R", R"' is H or CH3, r is an integer having values of 1 to 3 and R"" is an alkyl group having 1 to about 4 carbon atoms, 47.

(2) aliphatic acidic ethers having the formula:
wherein R"" ' is an alkyl group having 1 to 4 carbon atoms (3) amino esters having the formula:

;

(4) amino ketones having the formula:
;

(5) aliphatic alcohols having the formula:
R2OH, where R2 is alkyl having 1 to 5 carbons, (6) aliphatic carboxylic acids having the formula:
, where R3 is H or alkyl having 1 to 4 carbons, (7) aliphatic amines having the formula:

48.

where R4 and R5 are H or alkyl having 1 to 6 carbons and R6 is alkyl having 1 to 6 carbons with the proviso that the total number of carbons in the sum of R4 + R5 +
R6 ? 6, (8) aliphatic amino ethers having the formula:
where R7 is methyl or ethyl, and g has values of 1-4;

(9) aliphatic dialkyl amides having the formula:
R8 CON(R7)2 where R8 is H or alkyl having 1 to 5 carbons, (10) N (Hydroxymethyl)acrylamide and N-(hydroxymethyl)methacrylamide having the formula:
CH2=CR9CONHCH2OH

where R9 is H or -CH3, (11) cycloaliphatic ether alcohols having the formula:

where R10 is alkylene having 1 to 3 carbons and v is an integer having values of 1 to 5, (12) hydroxy esters having the formula:

49.

(13) hydroxy ketones having the formula:

(E) a water-miscible, nonmally solid macro molecular organic compound selected from the group consisting of cellulGse ethers, poly(alkylene oxides), homopolymers of vinyl alcohol, acrylic acid, meth-acrylic acid, vinyl pyrrolidone or acrylamide and copolymers of vinyl alcohol, acrylic acid, methacrylic acid, vinyl pyrrolidone, maleic acid or acrylamide containing at least one of the following lipophilic moieties copolymerized therein:

(1) (2) (3) wherein Y and R are as indicated above; and 50.

(F) 0 to about 49 parts by weight of water immiscible organic diluent per 100 parts of organic solvent (D) selected from the group consisting of:

(1) alkanes having about 5 to about 20 carbon atoms and halogenated alkanes having about 2 to about 20 carbon atoms;
(2) cycloalkanes and halogenated cycloalkanes having about 5 to about 12 carbon atoms;
(3) aromatic hydrocarbons having 6 to about 12 carbon atoms;
(4) aliphatic or cycloaliphatic ketones having about 7 to about 12 carbon atoms;
(5) alkaryl ketones having about 7 to about 12 carbon atoms;
(6) aliphatic or aromatic esters having about 7 to about 12 carbon atoms,and (7) olefins having about 6 to about 20 carbon atoms;
(G) sufficient water to provide an aqueous colloidal dispersion having a total solids content of up to about 60% by weight; and then stripping the colloidal dispersion until the total content of organic solvents (C) and (D) and diluent (F) is about 0.2 to about 20% by volume.

3, Method claimed in claim 2 wherein the vinyl resin contains about 60 to about 91 weight %
vinyl chloride, about 10 to about 25 weight % vinyl acetate and about 1 to about 15% carboxyl-containing ethylenically unsaturated hydrocarbon.

51.

4. Method claimed in claim 3 wherein the carboxyl-containing ethylenically unsaturated hydro-carbon is maleic acid or fumaric acid.

5. Method claimed in claim 3 wherein the vinyl resin contains about 75 to about 99 weight %
vinyl chloride about 1 to about 25% acrylic or meth-acrylic acid copolymerized therein.

6. Method claimed in claim 2 wherein a mixture of a vinyl chloride/vinyl acetate/maleic acid terpolymer and a vinyl chloride/vinyl acetate/glycidyl acrylate or methacrylate terpolymer is used.

7. Method claimed in claim 2 wherein a mixture of a vinyl chloride/vinyl acetate/maleic acid terpolymer and a vinyl chloride/vinyl acetate/hydroxy-alkyl acrylate or methacrylate having 2 to 3 carbons in the alkyl group is used.

8. Method claimed in claim 2 wherein a mixture of a vinyl chloride/vinyl acetate/maleic acid terpolymer and a vinyl chloride/vinyl acetate/vinyl alcohol terpolymer is used.

9. Method claimed in claim 2 wherein the vinyl resin is a terpolymer of vinyl chloride, vinylidene chloride and an ethylenically unsaturated carboxylic acid.

52.

10. Method claimed in claim 9 wherein the ethylenically unsaturated carboxylic acid is maleic acid or fumaric acid.

11. Method claimed in claim 9 wherein the ethylenically unsaturated carboxylic acid is acrylic or methacrylic acid.

12. Method claimed in claim 2 wherein the vinyl resin is a copolymer of vinyl chloride and an ethylenically unsaturated carboxylic acid.

13. Method claimed in claim 2 wherein the ethylenically unsaturated carboxylic acid is acrylic or methacrylic acid.

14. Method claimed in claim 2 wherein the vinyl resin is a copolymer of vinylidene chloride and an ethylenically unsaturated carboxylic acid.

15. Method claimed in claim 2 wherein a crosslinking amount of a thermosetting resin is blended into the colloidal dispersion,

16. Method claimed in claim 2 wherein the thermosetting resin is an epoxy resin.

17. Method claimed is claim 2 wherein the thermosetting resin is a hexamethoxymethylmelamine.

53.

18. Method claimed in claim 17 wherein the thermosetting resin is a methylated urea-formaldehyde resin.

19. Water-borne colloidal dispersion obtained by the method claimed in claim 1.

20. Method claimed in claim 2 wherein either a part or all of the macromolecular organic com-pound (E) is added after stripping the colloidal dis-persion.

21. Article comprising a substrate and adhering thereto a film deposited from the water borne colloidal dispersion claimed In claim 19.

22. Method claimed in claim 1 wherein organic solvent (D) is acetone or methyl ethyl ketone, the organic co-solvent (E) is butyl Cellosolve or a butanol, and the water immiscible organic diluent (F) is toluene or a hexane.

23. Method claimed in claim 1 wherein the organic water-miscible macromolecular compound is a homopolymer or copolymer of vinyl alcohol.

24. Method claimed in claim 23 wherein the copolymer contains the moiety:

wherein R is as defined above.

54.

25. Method claimed in claim 1 wherein the organic water-miscible macromolecular compound is a homopolymer or copolymer of N-vinyl pyrrolidone.

26. Method claimed in claim 25 wherein the copolymer contains the moiety:
wherein R is as defined above.

27. Method claimed in claim 1 wherein the resin is blended with about 1 to about 25 parts by weight of a water-immiscible organic diluent per 100 parts by weight of organic solvent (d).

28. Method claimed in claim 27 wherein the water-immiscible organic diluent is n-hexane.

29. Method claimed in claim 27 wherein the water immiscible organic diluent is toluene.

30. Method claimed in claim 27 wherein the water-immiscible organic diluent is dibutyl ketone.

31. Method claimed in claim 1 wherein up to about 25 parts by weight of a coalescing aid, selected from the class consisting of glycols having 2 to about 6 carbon atoms and glycerine, per 100 parts by weight of water are added to the stripped colloidal dispersion.
55.