Note: Descriptions are shown in the official language in which they were submitted.
2 ~
Attorney's Docket
IN-1165
oA~oDIc ~3CTRO~Oa~ PRI~E~ CONT~NI~ ~aTBR IN80 ~BL~
S oRoANo-LeAD COMPOUND8 ~ CORR08ION IN~IB$TOR8
Technical Field
The field of art to which this invention pertains is
electrodepositable resin compo~itions and, more
specifically, electrodepositable resin compositions
containing cross-linking agent~ for use in cathodic
electrodeposition coating processes.
~kgroun~ o~ t~ v-nt~o~ -
The electrodeposition of aqueou3 cationic resin
compositions onto conductive substrates i~ well known in
the coating arts. It is standard operating practice among
auto~obile manufactures to coat auto~obile frames and sheet
metal with anti-corrosive, electrodeposited, cathodic,
aqueous film-forming resin compositions which are cured to
a hard, durable, protective coatings. ~he use of
electrocoat primer coating~ has enabled automobile
manufacturer~ to providQ extended warran~ies covering body
corrosion. These electrocoat coatings are also used by
manufactur~rs of various products includ~ng trucks,
construction equipment, appliances, auto~obil¢ part~, etc.
In a typical cathodic electrodeposition process, an
aqueous bath is prepared from a principal resin ~olution or
emulsion and a pig~ent paste. The principal resin solution
or ~ulsion typically compri3es an epoxy-a~ine resin adduct
or ~n acrylic polymsr containing amine functional mono~ers
which can bo ~alted wi~h an acid to solubili2e the
prlncipal resin in water, and a cxossDlinking agent.
Typical cross-linking agents include the blocked
polyisocyanates and am~noplast crosslinkers . The pigment
paste typically compri~es a mixture of a ~pecifically
d~signed and formulated epoxy-amin~ resin adduct (known as
a grind resin), which has been ~alted with an acid, and a
pigment. The grind resin and pig~ent are ground together
2 ~
to form a pigment paste. The pigment paste is mixed with
the principal emulsion and distilled water at the coating
site to form an aqueous coatirlg bath having the desired
solids concentration. The aqueous coating bath is
typically contained within ~n in~ulated tank having
sufficient capacity to completely immerse all articles that
will be coated therein. Additiv2s conventional in the art
such as organic coalescent solvents may be added to the
bath to improve coating characteristics.
10An article which is to be coated typically comprises
an electrically conductive material. The ar~icle is
connected to a direct current circuit to act as a cathode.
The tank contains an anode or serves, itsalf, as the anode
of the DC circuit. When the ob~ct i~ immersed in the
15coating bath (contained within the coating tank), a flow of
electricity acro~s the ob~ect causes the principal emul~ion
and pigment pa~te to be depo~ited on the sur~aces of the
article along with any additives. The article i3 typically
remov~d from the bath when the desired thickness of film
20haa been depo~ited, after which the article i8 optionally
washed with distilled water. ~he article having ~he
deposited film i9 then typically placed in an oven where
; t~e film is cured to a smooth, hard, durable, cross-linked
coating.
25Cathodic electrodepositable amine-epoxy resin adduct
compositions, method~ of manufacturing these cathodic
el~ctrodepo~itable resin compositions, aqueous cationic
ol-ctrod~po-ition b~ths processes for the deposition of
th-~- resin~ from a coating bath onto a conductive ob;ect
30ar dl~cloc0d in U.S. PaSent Nos. 3,984,299, 3,468,770,
~,116,900, 4,093,S94, 4,137,140, 4,104,147, 4,22S,478,
4,419,467, and 4~l432,850, 4,575,523, and 4,57S,524, which
ars incorporat~d by re~er~nce. Cathodic, electrodeposition
acrylic resin composition~, methods o~ manufacture, aqueous
3Scationic coating bath~, and nethods o~ el~ctrcdeposition of
these compositions are disclosed in U. S. Patent Nos.
3,883,483 and 3,853,803 which are incorpor~ted by
2 ~ 2 0
reference.
Cathodic electrodepositable resin coatings, also known
as "Electrocoats" or "E-Coats, n provide a metal substrate
with ~ superior corrosion-re~istant primer coating. It is
S known that cationic E-Coats provide superior protection to
a steel substrate in comparison to anodic resin
compositions. In th~ automotive industry, these coatings
are typically overcoated with a decorative and protective
multi-layer top coating such as the industry'~ standard
inner base coat and 8 clear outer top coat coating sy~tem.
It i~ th~ practice in the art to include lead pigments
in electrocoat coating bath~, typically lead silicate and
lead ~ilico-chromate and/or lead chromate. The lead is
believed to serve as an anticorrosive agent. It is
deposited with the cathodic E-Coat and enhances the
corr~ion inhibiting characteristic~ of the E-Coat.
However, there are disadvantag~ presently a~sociat~d with
the use of lead compound~ in cathodic electroco~t
processe~. ~ir~t of all, lead compounds are typically
introduc~d into E-Coat coatings baths through the inclusion
of lead pigments in the coating baths. The lead pigments
tend to settle out and foul bath tanks, piping, pumps,
filters and associated equipment.
S~tting o~ lead pigment results in dirt in
electrodepos~tabl~ films and also results in sludge
accumulations in tank~ and proce~s equipment. This sludge
mu~t be disposed o~ as a wast~ material. Ther~ hav~ been
att-~pts to rQmove lead pigments from coating baths.
Cat~odic coating baths containing soluble lead salts are
di-closed in U.S. Patent No. 4,115,226. The level of
~oluble lead ~alts such as lead acetate and lead lactate
is difficult to control in a coating bath containing
soluble lead. Typically exce~sive levels of water-borne
lead are pr~sQnt producing higher ~han acceptable
conductivity, resulting in inad~quate coating bath throw
power and unacceptablQ coatings. In addit$on~ lead
pigments c~nnot be introduced into a coating bath as a dry
2~ 3 ~20
pigment. They must be ground with specially de~igned and
formulated E-Coat grind resins to for~ lead additiYe pastes
or lead-containing pigment pastes. The lead-additive
pa~te~ are ~hen added to the cathodic E-Coat coating baths.
The gxinding process is typically a dusty operation and
extensive environmental controls are necessary to prevent
workers from exposure to airborne lead particulates.
A tin catalyst 6uch as dibutyl tin oxide is typically
added to an agueous cathodic electrodeposition coating bath
to catalyze the cro~-linking reaction. The catalyst is a
dry powder which mu~t be added to the E-Coat coating bath
a~ p~rt of a pigment paste. The catalyst i extre~ely
difficult to grind and dispers2 in a pigment paste. In
addition, the cataly t is dif~icult to maintain in
suspension in ths aqueous C08ting bath and tends to ~ettle
out. 'Tin catalysts of the liquid type such as dibutyl tin
dilaurata are 5U pected a8 crater causing agents.
What i~ needed in thi~ are cathodic electrocoat
coating cOmpOBitiOn~ coating baths and methods of coating
which do not require solid lead pigments, water soluble
lead compounds, or tin catalyst~.
Dl-olo-ur- of th- Inv-~tio~
Novel agu~ou~ cathodlc~ electrodQpo~itable resinous
coating compo~ition~ are di~clo3ed. The coating
compo~ition~ co~pris~ an electrodepo~itAbl~ principal re in
co~position, ~ cros~-linking agent, and an organolead
co~pound co~pri~ing ~ water in~oluble lead salt of an
aliph~tic acid having at least six carbon ato~ or a water
in-olublo lead salt of an aro~tic carboxyl~c acid. As
used throughout thi~ disclosure and the appended clai~s,
the t-rm n insolublQ le~d ~alt~ denote~ lead salt~ that
pos8e~8 solubilities of 0.05 p~rt~ or le88 per 100 parts of
water at 2S-C. The coating compo~itions, when deposited as
a ~ilm on a conductive substrate in an aqueous, cathodic
electrodepo~ition process, and cured to a hard, durable
coating, have excellent corrosion re~istance without the
need for lead pigments or tin catalysts~
Another aspect of the present invention i~ an article
coated with an aqueous, cathodic electrodepositable
principal resinous coating composition. The coating
composition comprises an electrodepositable principal resin
composition, a cross-linking agent, and an organo-lead
compound compri3ing a water insoluble lead ~alt of an
aliphatic acid having at lea~t 6 carbon atoms or a water
insoluble lead salt o~ an aromatic carboxylic acid. The
coating composition when deposited as ~ film onto the
article in a cathodic electrodeposition process has
excellent corrosion re~istance without the need for lead
pigment~ or tin catalysts.
Yet another aspect of the present invention is an
aqueous, cathodic electrodeposition coa~ing bath. The
coating bath comprises an acid-salted cathodic,
electrodepo~itable principal resin composition, a cros~-
linking agent, and an organo-lead compound comprising a
water insoluble salt of an aliphatic acid having at least
2 0 5iX carbon atoms or a water in~oluble alt of an aromatic
carboxylic ac$d. A coating electrodepo~ited from the bath
onto a substrate and cured to a hard, durable, film has
excellent corrosion resistance without the need for lead
pigments or tin catalysts.
Yet another aspect of the present invention i~ an
improved 2ethod of cathodic electrodeposition of agueous
coating co~po~itions. The method compri~es forming an
agu-ou~, cathodic electrodepositio~ coating bath wherein
th~ ooating bath compri~es an agueous, cationic
~l-ctrodepo6itable princip~l resin composition and a cross-
linking ~gent. The bath i8 contained in an ~lectrically
in~ulated vess~l containing an anode. Then an~electrically
conductive article, connected to an electric circuit to act
a3 a cathode, is immersed in the bath and ~ufficient
electrical power i8 caused to flow across the article so
that a film of coating co~position i~ deposited on the
surfaces of the article. Then the article is removed from
2 ~
the coating bath and the film is cured to a hard, durable
coating. The improvement comprises including at least one
organo-lead compound in the coating bath. The organo-lead
compound comprises a water insoluble lead salt of an
aliphatic acid containing at least six carbon atoms or a
water insoluble lead salt of an ~romatic, carboxylic acid.
The resulting coatings containing the organo-lead compounds
have excellent corrosion resistance and cure to hard,
durable coatings without the need for lead pigments or tin
catalysts.
The foregoing, and other features and advant~ges of
the present invention will become more apparent from the
following description.
~B8T ~OD8 FOR CARRYlN~ O~T T~ NTION
'The organo-lead compound~ of the present invention
includa the water in~oluble lead salts of aliphatic acids
having at least six carbon atoms and water insoluble lead
salts of arom~tic carboxylic acids. The lead compounds may
be liquid~ or they may be solids which are ~oluble in
organic medium or solids which form liguid like pastes when
mixed with a suitable organic medium, such ~8 a solvent or
oil. Particularly preferred le~d ~alts include lead 2-
ethyl hexanoate, lead naphthenate, lead octanaote, lead
stearate, lead dodeconoate, and lead ol~ate.
Uæ~ul blocked polyisocyanates for use in the coating
compo~ition~ of the present invention a~ cross-linking
ag~nt~ lncludQ those which are stabl~ ln the dispersion
~yst~u~ at ordinary room te~perature and which react with
tho resinous product of this invention at elevated
temperatures~
In the preparation of the bloc~ed organic
polyisocyanates, any ~uitable organic polyisocyanate can be
u~ed. R~pre~ent~tive example~ are the aliphatic compounds
such as trimethylene, tetra~ethyl~n~, pentamethylene,
hexamethylene, 1,2-propylene, 1,2-butylene, and 1,3-
butylene diisocyanates; 3-isocyanatomethyl-3,5,5-
trimethylcyclohexylisocyanat~; the aromatic compounds such
as ~ phenylene, p-phenylene, 4,4'-diphenyl, and 1,4-
xylylene diisocyanates; the triisocyanates ~uch as
tr$phenyl methane-4,4'4'-triisocyanate, 1,3,5-benzene
triisocyanate and 2,4,6-toluene triisocyanate: and the
tetraisocyanates such as 4,4~-diphenyldimethyl methane-
2,2',5,5'-tetraisocyanate: the polymerized polyisocyanates
such as toluene diisocyanate dimers and trimers,
polymethylenepolyphenylene polyisocyanates having -N=C=o
functionalitie6 o~ 2 to 3, and the lik~.
In addition, the orgznic polyi~ocyanate can be a
prepolymer derived ~rom a polyol such as glycol~, e.g.
ethylene glycol and propylene glycsl, a~ well as other
polyol~ ~uch as glycerol, trimethylolpropan~, hexanetriol,
pentaerythritol, and the like, as w~ll as monoethers, such
2S d~ethylene glycol, tripropylene glycol and the like and
polyothers, i.e., alkylene oxide condensates o~ the above.
A~ong the alkyl~ne oxides that ~ay be condensed with these
polyolY to form polyethers are ethylene oxide, propylene
oxide, butyl~n~ oxide, ~tyrene oxide and the like. These
are generally called hydroxy-terminated polyether~ and can
~e lin~ar or branched. ~specially preferr~d are polyols
such a~ ethylen~ glycol, diethylene glycol, triethylene
glycol, 1,4-butylene glycol, 1,3-butylene glycol, 1,6-
hexan~diol, and the mixture~; glyc~rol, trimethylolethane,tri~ethylolpropane, 1,2,6-hexanetriol, pentaerythritol.
d~penta~rythritol,tripentaerythritol,polypentaerythritol,
sorbltol, ~thyl gluco~ide~, sucro~ and the lik~ with
alkylon~ oxide3 ~uch a3 ethyl~ne oxide, propylen~ oxide,
th~lr ~lYtur~, and the like.
Particularly pre~erred polyisoGyanate~ include the
re ction product of toluene diisocyanatQ and trimethylol
propan¢ and, the i~ocyanurate of h~xam~hyle~e diisocyana~
~trimer of 1,6-hexamethylene diisocyanate).
Th~ blocking ag~nts wh~ch c~n be u6Qd to block the
polyisocyanat~s and polyether polyol polyisocyanat~ adducts
are thosQ known ~n the art. Any suitable aliphatic,
~ ~ 9 ~
cycloaliphatic, aromatic, alX:yl monoalcohol and phenolic
compounds and secondary amine compounds can be used as a
blocking agent in the practice of the pre~ent invention,
including lower aliphatic alcohol~, such as methyl, ethyl,
chloroethyl, propyl, butyl, amyl, hexyl, heptyl, octyl,
nonyl, 3,3,5-trimethylhexyl, decyl and lauryl alcohols, and
the like; the aromatic-alkyl alcohols such as
phenylcarbinol, the monoethyl, monobutyl and monopropyl
ethers of ethylene glycol and the like; the phenolic
compounds such a~ phenol itself, substituted phenol~ in
which the substitusnt~ do not adversaly affect the coating
operations. Example~ of the latter includa cresol,
nitrophenol, chlorophenol tertiary butyl phenol, secondary
amines such as dibutyl amine, and hydroxy containing
ester~.
Preferred blocking agents include the monopropyl ether
of ethylene glycol and dibutyl amine. Additional blocking
agents include tertiary hydroxyl amines, such as
diethylethanolamine and oxim~, such a~ methylethyl
ketoxime, acetone oxime and cycloh~xanone oxime, and
caprolactam. ~nother preferred oxime is me~hyl-n-amyl
ketoxime.
The ca~hodic electrodepositable principal resin
compositions of this invention comprise epoxy re~ins which
are reacted with amines to form adducts, and amine
functional acrylic copolymers. The epoxy resins may be
optionally chain extended resulting in an increa~e in the
mol~cular wolght o~ the epoxy molecule~ by reacting with
w~tor ~i~c$bl2 or water 801ubl~ polyol~.
The epoxid¢s use~ul in the practice of thi~ invention
are ~he polyepoxides typically u~ed in this art and
compris~ a resinous material containing at least one epoxy
group per molecule.
The aminoplast crosslinking agents useful in the
practice of th~ present invention include: alkylated
melamine-formaldehyde resins, including ~uch melamine-
formaldehyde resin~ which are characterized a~ being one o~
2 ~
the following types highly methylated, partially
methylated and containing methylol functionality,
methylated and containing imino functionality, highly
butylated, partially butylated and containing methylol
functionality, butylated and contalning imino
functionality, mix~d methylated/butylated, mixed
methylated/butylated contain~ng methylol functionality,
mixed methylated/butylated and containing imino
functionality, cr such other melamines as could be
envisioned by exhaustiv~ or partial etherif~cation with an
alcohol o~ the reaction product of 106 moles of
formaldehyde for every mole of melamine ~xamples of
suitable melamine-for~aldehyde resins which are
commercially available include Cymel- 300, Cymel~ 301,
Cymel- 303, Cymel- 350, Cy~el 323, Cymel 325, Cymel- 327,
Cymel~ 370, Cymel~ 373, Cymel- 380, Cymel- 385, ~ymel-
1116, Cym~l- 1130, Cymel~ 1133, Cymel 1168, Cymel~ 1156,
Cymel- 1158, from tha American Cyanamid Company (Plastics
Division, WallingPord, CT 06492), ~nd Resi~ene- 891,
Resimene- 882, Re~im~ne~ 881, ~esimene- 879, ~esimena- 876,
Resimene- 875, Resimene- 872, Resimen~ 747, Resi~ene 746,
Re~imene- 745, Re~imene- 741, Resimsne- 740, Resimene~ 735,
Re~imene- 731, Re~im~ne- 730, Resimene 717, RQsimene- 714,
Resimene- 712, Resimene- 764, Resimene- 755, Re~imene~ 753,
ResimenQ- 750, fro~ the Monsanto Company (St ~oui~, M0
63166) The aminoplast ~rosslinking agent~ that are useful
in the practice o~ the present invention al~o include
~on~oguanamlne-~ormaldehyde re~lns which have been
parti~lly or rully eth~rified with a suitable alcohol,
typic~lly mQth~nol or butanol or a mixture ~hereof, and
which may also contain m2thylol function~lity and/or imino
functionality An example of this type of-cro~slinking
agent would include the commercial product Cym81- 1123 from
the A~erican Cyanamid Co~pany
The ~minopla~t cro~slinking agent~ that are use~ul in
the practice of this invention also include glycoluril-
formaldehyde resins ~hlch have been partially or fully
etherified with a suitable alcohol, typically methan31 or
butanol or a mixture thereof, and which msy also contain
methylol functionality and/or imino functionality.
Examples of commercially available croæslinking agents of
this type include Cymel- 1170, Cy~el- 1171, and Cymel~ 1172
from the American Cyanamid Company.
The aminoplast crocslinking agents that are useful in
the practice of this invention also include urea-
for~aldehyde resins which have been partially or fully
etheri~ied with a suitabl~ alcohol, typically methanol or
butanol, and which may also contain methylol functionality
and/or imino functionality. Ex~mples of commercially
available cro~slinking agent of thi~ type include Beetle
5S, Beetle- 60, Beetle- 65, and Beetlee 80 from the
American Cyanamid Comp~ny and Resimene- 960, Re imene~ 975,
Resi~ene- 970, Resimene- 955, Re~imene~ 933, Resimene~ 920,
Resimene- 918, Resimene~ 915, Re~imene 907, Reaimene- 901,
Resimene- 980, fro~ the Monsanto Company.
The aminoplast crosslinking agent~ that are useful in
the practice of thi3 inv~ntion al~o include carboxyl
modified aminopla~t r~sin. These crosslinking ag~nt~ would
include~elamine~formaldehyde,benzoguanamine-formaldehyde,
glycolurilfor~aldehyde, and ure~-formaldehyde type
crosslinking agents that include carboxylic acid
functionality a~ well ~5 ~lkoxymethyl f~nctionality,
typically ~ethoxym~thyl, ethoxymethyl, and butoxymethyl, or
a mixture therQof, and which may ~180 contain methylol
functionality and/or imino ~unctionality. Examples of
co~ercially zvailable cro~linking agents of thi~ type
in~lud~ Cymel- 1141 and Cy~el- 1125 from the A~rican
Cyana~id Company.
A particularly useful cla~s of polyepox~de are the
glycidyl polyethers of polyhydric phenols. Such
polyepoxide resin~ are derived ~rom an epihalohydrin and a
dihydric phenol ~nd have an spoxide equivalent weiqht (EEW)
of about 400 to about 4,000. Examples of epihalohydrins
are epichlorohydrin, epibromohydrin and epiiodohydrin with
3 2 ~
epichlorohydrin, epibromohydrin and epiiodohydrin with
epichlorohydrin being preferred. Dihydric phenols are
exemplified by resorcinol, hydroquinone, p,p'-dihydroxy-
diphenylpropane (or bisphenol A as it is commonly called),
p,p'-dihydroxybenzophenone, p,p'dihydroxydiphenylethane,
bis- ( 2 -hydroxynaphthyl)methane, 1,5-dihydroxynaphthylene
and the like, with bi phenol A being preferred. These
polyepoxide resin~ are well known in the art and are made
in desired molecular weight by reacting the epihalohydrin
and the dihydric phenol in various ratioc or by reacting a
dlhydric phenol in various ratios or by reacting a dihydric
phenol with a lower molecular weight polyepoxids resin.
Particularly preferred polyepoxide resins are glycidyl
polyethers of bi~phenol A having epoxida equivalent weights
of about 450 to about 2,000, ~ore typically about 800 to
abou~ 1,600, and preferable about 800 to about 1,500.
The polyepoxides used in the practice of this
invention will have a relatively high ~olscular weight,
that i~, typically about 1,600 to about 3,200, and
preferably ~bout 1,600 to about 2,80Q.
Another quite useful clas~ of polyepoxides are
produced si~ilarly from novolak re~ins or similar
polyphenol resin~.
Also ~uitable are the polyepoxide~ comprising similar
polygly~idyl ether~ of polyhydric alcohol-q which may be
deriv~d from ~uch polyhydric alcohols as ethylene glycol,
diethylenQ glycol, triethylene glycol, 1,2-propylene
glycol, 1,4-propylene glycol, 1,5-pentanediol, 1,2,6-
hexanatriol, glycerol, bis-(4-hydroxycyclohexyl)-2,2-
prop~ne and tho like. There can ~l~o be u~ed polyglycidyl
e~ter~ of polycarboxylic acid~, w~ich are produced by the
re~ction of epichlorohydrin or similar epoxy compound~ with
an aliphatic or aromatic polycarboxylic acid terephthalic
acid, 2,~,-naphthalenedicarbocylic acid, dimerized
linolenic ~cid and the like. Examples re glyeidyl adipate
and glycidyl phthalate. Also useful are polyepoxides
derived fro~ the epoxidation of an olefinically unsaturated
11
~a ~ ~2~
- alicyclic co~pound. Included are diepoxides comprising in
part one or more monoepoxides. These polyepoxides are
nonph~nolic and are obtained by the epoxidation of
alicyclic olefins. For exa~ple, by oxygen and selected
method catalysts, by perbenzoic acids, by acetaldehyde
monoperacetate, or by peracetic acid. A~ong such
polyepoxides are the epoxy alicyclic ethers and esters
which are well known in th~ art.
Other ~poxy-containing compounds and resin~ include
nitrogenous diepoxides such a3 disclosed in U.S. Patent No.
- 3,365,471; epoxy resin~ from l,l-methylene bis-(5-
cubstituted hydantoin), U.S. Patent No. 3,391,0S7; bis-
imide containing diepoxidesl U.S. Patent No. 3,45,711;
epoxyl~ted aminomethyldiphenyl oxides, U.S. Patent No.
3,312,664; heterocyclic ~,M'-d~glycidyl compound~, U.S.
Pate~t No. 3,503,979: amino epoxy phosphonate~, Briti~h
Patent No. 1,172,916; 1,3,5-triglycidyl i~ocyanurates, as
well a~ other epoxy-containing materials known in the art.
Any cationic, epoxy-a~ine resin adducts, a~ well as
cationic epoxy amin~ re~in adducts conventionally known and
used in the cathodic electrodeposition art~, can b~ u~ed in
the practice of the present invention including modified
epoxy resins adduct~. For ex~mple, the modified epoxy
resins u~ed in ~he practic~ of this invention ~ay comprise
one of the aforementioned epoxy resin co~pos~tions chain
extended with wat~r mi~cible or w~er 801uble polyol,
reacted with oxce~s amine, and finally react~d with a fatty
acid or aliphatic monoepoxide. The~e epoxy amine resin
adduot compo~itions are disclosed in U.S. Pa~ent Nos.
4,575,523 and 4,575,524, the di~clo~ur~ o~ which are
incorporat~d by refarence. However, any epoxy-a~ine resin
adducts produc~d by method known in the art, such AS by the
diketimine Method a~ disclosed in U.S. Patent No. 3947339,
- and other m~thods ~ay be used in th~ practice of the
present ~nvention.
The polyamines used in the practice of this invention
to form epoxy-amine resin adducts when an "~xce3~-a~ine"
12
prOCe~B i8 used are typical of those known in the art such
as the polyamines disclosed in U.S. Patent No. 4,139,510,
whic~ is inrorporated by reference.
The amine-~unctional acrylic copolymer~ useful in the
5practice o~ the present invention include copolymers of two
or ~ore of the monomers such a~ hydroxy ethyl acrylate,
dimethyl ethyl amino methacrylate, dimethylethylamino
~ethacrylate, styren~, butyl acrylate, ethyl acrylate and
other monomers typically used to form acrylic copolymer
10resins. The copolymer resins will compris~ copoly~ers of
esters of methacrylic acid, ~ unsaturated monomer~ such
as styr~ne, hydroxyl functional e~ters of acrylic acid or
methacrylic acid and an amine-functional ~ unsaturated
monomer, or copolymer~ of glycidyl methacrylate or acrylate
15reacted with an a~ine. Cathodir, ~lectrod~positable amine-
~unc~ional acrylic compositions ar~ disclos~d in U.S.
Patent No. 3,~83,483 which is incorporated by reference.
Suficient guant~ti~s of block~d polyisocyanate or
aminopla~t cross-linking agents are incorporated into the
20electrodepo~itable coating compositions of this invention
such that the deposited coating will be compl~tely cured
upon baking. Also, th~ coating compo~ition~ will be
designQd ~o that there will be no free isocyanate groups
remaining aftar curing when using polyisocyanate cro s-
25linking agent~.
Typically, about 10 wt.% to about 60 wt.t o~ blocked
polyi~ocyan~tQ i~ incorporated based upon the total weight
oS the princip~l r~in composition and ¢ros~-linking agent,
~or typically ~bout 20 wt.% ~o about 50 w~.~, preferably
30abcut 25 wt.% to about 35 wt.%. Typically about 10 wt~% to
about 60 wt.% o~ the aminopla~t cros~-linXing agent i8 u~ed
ba3ed upon the total weigh~ o~ the cro~s~ king agent and
the principal re~in co~positions, pre~erably about 20 wt.%
to ~bout 40 wt.%.
35The blocked polyisocyanate~ o~ thi8 invention are
mixed with the principal re~in co~po~itions, ~or exa~ple
the epoxy-amine adduct or the amine-functional ~crylic
~ 3 ~
copolymer, by adding the blocked polyisocyanates to a
ves~el containing the epoxy-a~in~ rQ~in adduct composition
or the amine-functional acrylic copoly~er and mixing the
charge for about one-half hour. Aminoplast cross-linking
agents are typically added in a similar manner.
In oxder to solubilize or disperse into an emulsion
cathodic electrodepositable resin conposition, it is
necessary to salt the amine containin~ resin with a water
soluble acid. The acid~ whlch can be used include tAose
known in the art such a~ ~ormic ~cid, ~cetic acid,
phosphoric acid, lactic acid, hydrochloric acid, etc.
Suf~icient quantities of the acid are ~ixed with the
electrodepositable resin compo~ition~ to solubilize or
disperse the resin composition in w~ter. One method, which
is preferred, in whlch the salting process i~ accomplished
i3 by, chaxging the resin composition, an acid, cosolvent~,
water ~nd surfact~nts conventional in the art, into
vessel, and ~ixing the ch~rge with a ~low spe~d mixer,
. Typically, about 0.1 Meg to about 0.8 Meq of acid i~
used per gra~ of olid resin, mor~ typically about 0.2 Meq
to about 0.7 ~Rq, and preferably about 0.2 Meq to about 0.5
Meq.
The principal resin ~olution or emulsion 18 typically
incorporated directly into the coati~g b~h ~t the coating
~ite. Typically, a principal xesin solution or e~ulsion of
the presQnt invention comprises about 10 wt.% about 90 wt.%
of amine-epoxy re~in adduct or amins func~ional acrylic
re~in, ~or~ typ~cally about 20 wt.% to about 30.0 wt.~ and
pr~-rably ~bout 22 ~t.%, although principal re~ins
30 solution or emulsions having higher or low~r concentrations
ca~ b~ u~d.
Th~ concentration of cathodic, electrodepositable
principal resin c~mpositions in an aqueou~, cat~odic
electrodspo~ition coating bath i~ typi~ally ~bout 5 wt.%
to about 50 % wt.%, more typically a~out 10 wt.% to about
25 wt.%, ~nd preferably a~out 15 wt.%.
It should be noted that thc cathcdic, electro-
14
2 ~
depositable resin coating compositions are typically
shipped by the manufacturer to the user as a salted aqueous
dispersion having a concentration of about 20 wt.% to about
36 wt.% of solids.
The cathodic electrodepositable coating baths of this
invention are typically formed by mixing the solubilized
(i.e., salted) cathodic electrodepositable resin
compositions oP this invention in concentrate form with
water, although un alted resin could be used in baths
already containing the solubilizing acid. The
electrodeposition bath may contain additional ingredients
such as pigments, cosolvents, antioxidants, surfactants,
etc., which are typically used in electrodeposition
processes known in the art. Pigment compositions may be of
any conventional type and are one or more of such piqments
as tne iron oxides, dye, carbon black, titanium dioxide,
talc, barium sulfate, barium yellow, cadmium red, chromic
green, etc. Additionally, hydrophobic dyes as described
in copending Patent Application Sarial No. (Attorney's
Docket IN-1128) can be u~ed. Sufficient quantities of
pigment are used to achieve the appearance charac~eristics
desired such as gloss, reflectance, hue, tint and other
desired characteristics. Typically, when using a pigment
the amount of pig~ent in the coating bath is expressed in
a ratio of total pigment to total binder. Typically a
pigment to b$nder ratio of about 0.01 to about 0.95 is used
in the electrodepositablo re~in compositions of the present
invention, ~ore typically about 0.01 to about 0.4. Pigment
is typically added to the electrodepo~ition bath in paste
Por~, i.e., predisper~ed in a paste composition comprising
pigment, cathodic, electrodepositable grind co~position and
surfactants and additives conventional
Sufficient quantitie~ of the water insoluble organo-
lead compound~ of th~ present invention will be
incorporated into the coating compositions of the present
invention to provid~ sufficient corrosion resi~tance of the
coated substrate. The organo-lead compounds may be
2 ~
incorporated into the principal resin solution or emulsion
or into the pigment pa~te. When incorporated into the
principal resin solution or emulsion or coating bath the
weight percentage of water insoluble organo~lead to
principal resin will typically be about 0.1 wt.% to about
10 wt.~, preferably about 0.5 wt.% to about 5.0 wt.% water
insoluble organo-lead compounds are incorporated into a
principal resin ox emulsion by mixing with the principal
resin or princip~l r~sin/cros~linker ~ixture prior to
salting and dispersing in water, ~imilarly, the water
insoluble organo-lead co~pound3 are incorporated into the
pigment paste by ~ixing with the grind resin prier to
disper~ing into water.
The electrodeposition baths may contain coupling
solvents which are water soluble or partially water soluble
orga~ic solvent~ for the resinou~ vehicles used in the
practice o~ thi~ invention. The coupling solvents or
cosolvents used in the practice of thi~ invention are those
typically used and known in the art.
The ~moothne88 of the cured coating i8 a function of
the "flow~ of the depo~ited coating composition. Flow is
defined a~ the tendency o~ the electrodepo~ited coating
composition to liqui~y during the curing operation and form
a smooth coh~Eive film over ths surfacQ o~ a coated article
prior to the onsct cros~-linklng. T~i8 ~S accompli~hed in
part by co-solvent3.
Exa~ple~ o~ such coupling ~olvents include ethylene
glycol mono~ethyl ether, 2thyle~e glycol monoe~hyl ether,
ethylen~ glycol ~onobutyl e~her, diethylene glycol
monobutyl ether, ethanol, isopropanol, n-butanol, etc.
Suf~icient amounts of coupling ~olvent are optionally used
so that a good ~u18~ on resulting in a ~EOO~h, deposited
film i8 produced.
The alectrodeposition proce~ typicAlly take3 place in
an Qlectrically insulated tAnk containing an electrically
conductive anode whic~ iB attached to a direc~ current
source. The ~ize of the tank will depend on the size of
2~ 5>2~
the article to be coated. Typically, the tank is
con~tructed of stainlesc stee.l or mild teel and lined with
a dielectric coating such as epoxy impregnated fiberglass
or polypropylene. ~he electrocoat coating co~positions of
thi~ invention are typically used to coa~ article~ such as
automobile or truck bodie~, car parts, applications, etc.
The typical size of an electrodeposition bath tank used for
this purpose c~n range from about several hundr~d to about
120,000 gallons. However, any electrically conductive
article of any ~ize ranging from ~aRteners such a~ nuts and
bolts to construction equipment to structural members may
be coated with the E-Coat compositions of the present
invention.
Typically, the article to be coated is connected to
the direct current circuit so that the electrically
conductive article act~ as the cathode. When the article
is immersed in the coating bath, a flow of electricity
across the articla result^~ in ~ film of the cationic
elQctrodepositable coating co~position b~ing deposited on
the surfaces of the article. The E-Coat composition ha a
net positive charge and i8 therefore attracted to the
negative cathodic ~ur~ace o~ the conductive article being
coated. The thickness of the coating deposited upon the
article during its re~idence in the cathodic E-Coat coating
bath i~ a function of the cathod~c, electrodepositable E-
Coat coating compo~ition, the voltage across the arti~le,l
the curr~nt ~lux, the pH o~ the coating bath, the
conductivity, thQ residence ti~e, etc. Sufficien~ voltage
will ba appli~d to the articl~ for a ~ufficient time to
obt~in a co~ting of su~ficient thickness and uniform
cov-~ago. Typlcally, the voltage appli~d across tha coated
art~cle i8 about 50 volt8 to about 500 volts, ~ore
typically about 200 to ~bout 350 volt~, and preferably
about 225 volts to about 3Q0. The current den~ity is
typically about 0.5 ~mpere per ~q. ft. to about 30 a~per~s
per 8q. ft., more typically about on~ ampere per sq. ~t. to
about 25 ampere~ per sq. ft., and prefer~bly about one
17
ampere per sq. ft. The article typically remains in the
coating bath for a sufficient period of time to produ~e a
co~ting or film of sllfficient thickne6s, having sufficient
re~istance to corrosion. The residence time or holding
ti~e i5 typically from about E~ few seconds to about a few
seconds to about 3 minute, more typically about 1 minute to
about 2-1/2 minutes, and preferably about 2 minutes;
however, this will vary and depend upon the previously
mentioned parameters.
The pH of the coating bath is cufficient to produce a
coating which will not rupture under the applied voltage.
That is, sufficient pH to maintain the stability of the
coating bath ~o that the resin does not kick-out of the
dispersed st~te and to control the conductivity of the
bath. Typically, the pH iB about 4 to about 7 more
typic'ally about 5 to about 6.8, and preferably about 5.5 to
about 6.~.
The conductivity of the coating bath will be
sufflcient to produ~e a coated film of ~ufficient
thickness. Typically the conductivity will be about 800
micromhos to about 3,000 micro~ho~, more typically about
800 micromhos to 800 micromhos to ~bout 2,200 micromhos,
and pr~ferably about 900 micromhos to about 1,800
micromhos.
The desirable coating thicknes~e~ are ~ufficient to
provide r~istance to corro~ion while hav~ng adequate
flexibility. Typlcally, the film th~cknes~e~ of the coated
ob~ect~ of thi~ invention will be about 0.4 mil to about
1 8 ~il8 . Thinner or thicker fil~s ~ay be deposited as
requir~d.
When the desired thicknes~ of the coating has ~een
achi~v~d ths co~ted article i5 removed ~ro~ the
electrodepo~ition bath and cured. Typically, the
electrodepo~ited coating~ are cured in a conventional
convection oven at a suf~cient temperature for a
sufficient length of time to unblock the blocked
polyisocyanate~ (when blocked polyisocyanates are used) and
18
2 0
allow for cross-linking of the electrodepositable resin
co~positions. Typically, the coated articles will be baked
at a metal temperature of about 200'F (93rC) to about 600-F
(315~ ore typically ~bout 250-F ~121-C) to about 390-F
(l99-C), and preferably about 300-F (149-C) to about 375-F
(l91-C). The coated articles will be baked for a time
period of about 10 minutes to about 40 minutes~ more
typically about ten minutes to about 35 minutes, and
preferably about 15 minutes to about 30 minutes. Once
lo again, it will be appreciated by thos~ skilled in the art
that times and temperatures will vary.
It is contemplated that the coated articles of the
present invention may al~o be cured by using radiation,
vapor curing, contact with heat transfer fluids, and
equivalent methods.
~t will be appreciated by those skilled in the art
that each of the coating parameters may vary according to
the coating composition, bath characteristics, and the size
and ~hape of the articles, coating perfor~ance requirements
and the like.
Typic~lly the coated article~ of this invention will
comprise conductive substrates such as metal, including
st~Ql, aluminum, bras~, gold, silver, pl~tinum, nickel,
chrome, zinc, coated ~teels, copper, and the like, however,
any conductive sub~trate having ~ conductivity similar to
the afore~entioned metal may be used. The articles to be
coated ~ay comprise any sh pe ~o long a~ all surfaces can
be wetted by the electrodeposit~on bath. T~e charact-
~rt~tica o~ th~ arti~ls which have an effect on the coa~ing
d~po~ition include the shape o~ th~ article, the capacity
of the surface~ to be wetted by the coating, and the degree
of shielding from the anode. Shielding is defined as the
degree of interference with tha electromotive field
produced between the cathode and the anode, thereby
preventing the coating compo~ition from being deposited in
~hose shielded areas. A measure of the ability of the
co~ting bath to coat remote areas of tha ob;ect is
19
- 2 ~ 2 ~
throwpower. Throwpower is a function of the electrical
configuration of the anode and cathode as well a~ the
conductivity of the electrodepo~ition bath. High
conductivity cause by ~oluble lead i~ known to decrease
throw-power.
~ oluble lead compounds a8 described in US Patent
4,115,226 such lead aoetate or lead lactate tend to cause
an increase in both t~ bath conductivity and the depo~ited
film conductivity. Thi~ reduce~ the voltage at whioh the
nrticle can ba coated without experiencing rupturing.
Rupturing i8 a coatlng defect which can re~emble film
boiling or blowing, resulting in an unacceptable appearance
and performance. The reduced rupture voltage i~ in part
responsi~l4 for the reduced throwpower. The reduced
voltaqe al80 may reduce the maximum film bu$1d obtained,
whlc~ may re ult in poor coating performance.
The coating of the coated articl4s of thi~ invention
exhibit ~uperior smoothness, glo~s, 1exibility, durabillty
and resi~tance to corro~ion. Smoothness and glos~ are
related to the flow Or the electrodeposited cathodic resin.
Durability, flexibility and resistance to corrosion are
related to the chemical nature o~ the electrodeposited
cathodic E-Coat co~positions a~ well a~ the smoothne~ of
the depositRd coatings. Thes~ coating composition~ readily
accept an auto~otive prlmer or an overcoat ~uch as the
industry stand~rd inner pigmented ba~e coat 2nd outer clear
top coat.
The aquoou~ E-Coat coating bath~ o~ the present
invsntion do not contAin water ~oluble lead compound~, lead
pignent~ or tin catalysts. Coating~ without w ter 801uble
lead co~pounds, lead pigment~, or tin catalyst~ contain
cro~slinkers o~ the blocked isocyanat~ typ~ d~ not cure to
hard, solvent resi3tant, durable films having acceptable
corrosion per~ormanc~. Surpri~ingly, water insoluble
~5 organo-lead compounds ~an be used in aqueous E-Cozt baths
in place of water soluble lead co~pound~ ad pig~ents, or
tin catalyst~, and pro~uc~ d~posit~d, cured coating which
3 2 ~
have hard, durable, soluble resistant films with ~xcellentcorro~ion resistance. ~lso surpri~ingly, water insoluble
organo-lead compounds do not reduce the rupture voltage,
decrea~e the throwpower, or lower the maximum film build
obtain~ble.
It should be noted that t:he articles coated by the E-
coat coating composition~ of this invention are typically
automobile bodle~ which have been pretreated to remove
impurities and contaminants in a phosphatizing bath,
however, the coating compositions may be used to coat
virtually any ob;ect comprising a conductive ~ubstrate
whether pretreated, precoated or not.
The following examples are illu~trative of the
principles and practice o~ this invention, although not
limited thereto. Parts and percentages where used are
part~ and percentages by weight.
R~P~ NTA~I~E ~SA~ O~ ~YPICAL ~O~YX$RIC NaT~RIAI8
~8~L ~N ~ ~9~T~ON
~D~ 1
Ethyl cellosolve (290.0 parts by weight3 and 106,0
partY o~ butyl cellosolve are charged into a reactor
equipped wi~h conden~er, ~tirrer, thermometer, and dropping
~unn~l. The mixturs is heated to 120--130-C a~d held at
this tamperature. To this mixture i~ then added, over a
period oP 3 hours, mixture oP 580.0 part~ butyl acrylate,
350.0 part~ atyr~ne, 140.0 parts N,~-dimethylaminoethyl
~etha~rylnte, 58.0 parts 2-hydroxyethyl methacrylate, and
17.0 part~ -azobisisobutyronitrile. A mixture of 2.0
part- t-butyl-pRroxyisopropyl carbonate and 1.5 parts ethyl
celiosolv~ i~ then added. The reaction i8 h~ld at 120-C
for 1 hour, a~ter which a sacond ~ddition of said
component~ i~ added and, likewise, the reaction is
permitted to continue for 1 hour~, after which a third and
final addition of said ~omponent~ i8 added and tho reaction
iq permitted to continue for 2 hours.
2 ~ 2 ~
P~ ~
A reaction vessel is charged with 727.6 part~ Epon
829, 268.1 parts PCP-0200, and 36.1 part~ xylene and heated
with a nitrogen sparge to 210-C. The reaction is held at
re1ux for about 1/2 hour to remove water. The reaction
mixture is cooled to 150-C and 197.8 parts bisphenol A and
1.6 parts benzyldimethylamine catalyst are added and the
reaction mixture heated to 150--190 C and held at this
temp¢rature for about 1 1/2 hours and then cooled to 130-C.
Then 2.2 parts of the benzyldimethylamine cataly~t are
added and the reaction ~ixture held at 130-C for 2 1/2
hours until a reduced Gardner-Holt viscosity (50 percent-
resin solids solution in 2-ethoxyethanol) of P is obtained.
Then 73.1 parts of a diketimine derivative derived from
diethylenetriamine and methyl isobutyl ketone (73 percent
solld~ in methyl isobutyl ketone), and 39.1 parts N-
methylethanola~ine are added ~nd the temperature of the
reaction mixture is brought to 110~C and held at this
temperature for 1 hour. To this ~ixture, 76.5 parts 2
hexoxyethanol are added.
B~A~Ph~ 3
To a clean dry reactor, 115 parts ~ylene are added.
The mix$n~ liquid i8 blanketed with pure nitroqen and
heated to ~2 C. An addition of 568.1 parts of Epon~ lOOlF
- (EEW ~ 520 - 540) is ~ads at such a rat~ that the batch
temperatura n~ver drops below 60'C, usually ov~r a period
of two hours. Heating i~ continued until 100-C. At this
point, 75.9 parts dodecyl phenol are added and heated to
118-C. Yacuum drying by di~tillation Or xylen~ i~ started
at ~hi~ tQ~p~ratur~ and continued while h~ating to 125-C.
The pr2ssur~ should be between 65 cm and 69 c~ Hg (88 kP -
92 kP) ~t full vacuum. The drying stag~ should take
between 1.0 and 1.5 hours. Break vacuum with pure nitrogen
only. The batch i8 cooled (the 8ampl8 at thi~ point should
be 94.3-95.3 ~ non-volatiles) and at 115-C, 1.1 parts
benzyldimethyla~ine are added. The peak exotherm
22
2 ~ 2
temperature should reach 129--132-C. The temperature is
maintained at 128--132-C and t:he polymerization i5 followed
by EEW titration. Every 30 minutes the reaction is sampled
and i~ stopped at an end point of 1090-1110 EEW. The
typical reaction time is three hours. Ad~ustments to the
catalyst level may be neceassary if extension period
deviates more than ~0 minutes from three hours. At the
target EEW, 12.1 parts butyl cello~olve and 74~7 parts
xylene are added ~ollswed by 42.6 parts DEOA (diethanol
amine). The temperature of this reaction Rhsuld not exceed
132-C. Cooling may be neces~ary at thi~ point with jacket
or coils. A vacuum suction is ~tarted im~ediately after
the DEOA addition and pressure is reduced to 18 inches of
Hg and held for 5 minutes. The pres~ure i8 further reduced
in 2 inch Hg increments followed by short holding period
until~ 26-2~ inch2s of Hg is achieved. The batch i3 then
cooled to 90-C in one hour following addi~ion of DEOA. To
achieve thi~, a good reflux rat~ should be attained in 20-
25 minutes a~ter the DEOA addition. All ~olvents are
returned to the raactor. A~ter one hour of vacuu~ cooling
(T ~ 90-C), 40.6 part~ ethylene glycol monohexyl ether and
107.7 parts isobutanol ar~ added without breaking vacuum.
Th~ batch is cooled for 35 mlnutes to 57--61- C under full
vacuum to achieve the target temperature during the
specified time t~bles. After the 35 m$nute cooling period,
13.3 parts Or di~ethylamino propyl~mine (D~PA) are charged
aa fn~t aY pos~ible. The batch i~ k~pt be~ween 54--60- C
for t~o hour~ ~fter the exotherm. Then it i~ heated to
90-C over one hour and thi~ temperature i~ held for one
hour. The batch is then cooled to 80-C~
~A~ 4
To a suitablQ reactor, 1881.7 parts o~ triethylene
tetramine are added. ~eat and agitation i8 applied and, at
104-C, lg44.8 parts o~ an epoxide resin ~olution at 59.4%
solids in ethylene glycol monomethyl ether (the epoxide
resin being glycidyl polyether of bisphenol A having an
2 ~ 2
epoxide equivalent weight of 895) are slowly added. The
epoxide resin addition is co~pleted in 65 minutes and the
te~perature drops to 99-C. The temperature is slowly
raised to 121-C over 45 minutes and i8 held between 121~
127-C for 1 hour to complete the adducting reaction. The
excess unreacted amine and the ~olvent is removed by
heating the adduct solution to 232 C under vacuum (25 mm
Hg pres~ure). When the distillation is completed, vacuum
i8 released and the temperature is reduced to 182-C. This
0 i5 followed by the addition of 700 parts of ethylene glycol
monome~hyl ether, which reduce~ the temperature to about
118'C. When the solution i~ homogeneou~, 458.3 parts of
the glycidyl ether of mixed fatty alcohols containing
predominantly n-octyl and n-decyl groups, the glycidyl
ether having an epoxide equivalent weight of 229 are added
at a,temperature of 107--116-C. Heating i~ stopped after
an additional bour at 116-C. The resulting product should
have a solids content of 71.3 %, and a Gardner-Holt
viscosity of Z6 -Z7.
~XA~PL~ 5
A blocked isocyanate (polyurethane cros~-linking
agent, reverse ordor) i8 prepared according to the
following procedure. Slowly and with stirring in a
nitrogan atmosphera, 291 parts of an 80/20 isomeric ~ixture
of 2,4-/2,6-tolu~n~ d~isocyanate, 0.08 part~ of dibutyltin
dilaurate and ~80 parts of methyl i~obutyl ke~one are
ch~rgod to a ~uit~ble reactor, the temperature being
malntained below 38-C. The mixture is m~intained at 38'C
for a ~urth~r half hour after which 75 parts of
tri~cthylolpropana are added. Aft~r Allowing the reaction
to proc~ed for about 10 hours, 175 parts of ethylene glycol
monopropyl Qther are added ~nd the ~ixture reaction kept
1.5 hours at 121-C until essentially all the isocyanate
groups are reacted. This depletion i8 recognized from the
in~rared spectrum.
The normal order blocked isocyana~e can be prepared by
24
2 ~
the altering of the foregoing order of addition pursuant to
Example 1 of Ger~an Offenlegungsschrift 2,701,002.
~A~P~ 6
A blocked i8 isocyanate crosslinker tpolyurea) is
prepared according to the following procedure. To a dry
reactor., 4B3 parts of triisocyanurated hexamethylene-
diisocyanate and 193 parts of 2-hexanone are charged.
Dibutylamine (307 part~) i5 added slowly and with stirring
under nitrogen atmospher~ so that the temperature does not
exceed ~0-C. After all amine has reacted, 14 parts of n-
butanol and 0.2 parts of dibutyl tin dilaurate are added.
~A~PL~ 7
A qua~ernizing agent for use in preparing a pigment
grin~ resin is prepared by adding 320 parts 2-ethylhexanol
half-capped toluene diisocyanate (95% solids in methyl
isobutyl ketone) to 87.2 parts dimethylethanolamine in a
suitable reactor at room temperature. The mixture is
allowed to exotherm and i~ stirred for 1 hour at 80-C.
Lactic acid ~117.6 parts o~ 88% aqueou~ lactic acid
solution) i8 then charged followed by the ~ddition of 39.2
parts 2-butoxyethanol. The reaction mixture is stirred for
about 1 hour at 65-C. to form the desired quaternizing
agent.
The gr$nd resin i8 prepared by ~harging 713 parts o~
Epon- 839 and 289.6 part8 of bi~phenol A to a suitable
reaction ve8841 and heated to 150--160-C to initiate an
exoth~rm. The re~ction mixture is per~itted to exotherm
for 1 hour at 150--160-C. The reaction ~ixture is then
cool~d to 85--90~C, homogenized and then charged with 71.2
parts deionized water followed by the addition of 496.3
parts of the above described quaternizing agents. The
temperatur~ of the reaction mixture i8 held a~ 80--85-C
until an acid value of about 1 is obtained.
- 2 ~ 2 ~
Æ~AMPL~ 8
Into a reaction vessel, 27.81 parts of the diglycidyl
ether o~ bisphenol A and 1.44 parts xylene are changed.
The charge i8 heated to 82-C under a dry nitrogen
atmosphere. The heating i8 discontinued, and a charge of
5.81 parts bisphenol A is added, tcqether with 0.002 parts
triphenyl phosphine catalyst. ~he heating of the reaction
ves~el is then continued to a temperature o~ 127-C, where
the reaction begin to exotherm on its own, with a peak of
about 150~-160-C. The extension i8 held above 1~0-C until
an EEW of 340 360 is achieved (about 345). Onc~ the target
EEW is reached, 21.08 parts butyl cellosolve i8 added to
the reaction vess~l and the reaction mixture i8 then cooled
to 49-C. After a temperature of 49-C is achieved, a
mixtur~ of 7.77 parts of 9-amino-3,6-dioxanonan-1-ol and
4.07 'part dimethylaminopropylamine are added to the
reaction vessel over a period o~ 6 minutes, followed by a
pump flush of 0.53 parts ethylene glycol monobutyl ether.
The batch exothar~s to 104--110-C, ~nd the reaction mixture
i8 then held at or below 115-C for ona hour. Next, 4.92
parts butyl cello~olv2 are charged into the reaction vessel
and the batch i8 cooled to 77-C. Next, 14.9 parts
nonylphenolglycidyl ether are charged into the reaction
vessel followed by a pump flush of 1.53 parts of ethylene
glycol monobutyl ether. The batch exotherms to 88-~93-C,
and th~ batch i~ then held at this temperature ~or one
hour. Fin~lly, 10.03 parts butyl c~llosolve is charged
into th~ reaction vefi3~1 and the batch cooled to 66-C. The
r~sult~nt product is then filtered through 25 micron bags
and dru~med.
~A~PL~8 OY T~J INCORPORA~IO~ O~ ~AT~R I~80~LR ORGANO-
L~aD CO~O~o W IN ~NCIPAL R~8I~ ~OL~T~ON8
~AK~LE 9 - ~5
This general procedure ~pplies to ~he examples 9 - 15.
Specific formulations for these examples are ~hown in Ta~le
1. All a~ounts shown in Table 1 represent the weight of
26
2 ~
the non-volatile portion.
Charge a suitable mixing ve~sel with the crosslinker.
Optionally, if a hydrophobic dye is included, the dye is
add~d to the crosslinker with slow stirring, and i5 mixed
for about 30 minutes. Plasticizer and organic solvents are
then added to the mixture, c:ontinuing the slow agitation.
Principal resin, at 21--4!3-~, i3 then added to the
continuously ~ixing batc~. ~fter 30 minutes of continuous
stirring, the water insoluble organo-lead compound(s) is
added. The ~ixing is continued uninterrupted for 30
minute~, then all remaining additive~, flow agents,
solvent, antifoam agent~, and curfactants are added.
TABLE
~5
INGREDIENTS EXAMPLES
, 9 10 11 12 13 14 15
. ~
Crosslinker30.531.0 15.0 31.0 14.0 31.0
(Exa~ple 5)
Crosslinker 15.0 14.0
(Example 6)
Cymel- 1141 31.0
Paraplex~ 7.6 7.6 7.6 7.6 7.6 7.6
WP-1
(Rohm & Haas)
Orasol- RL 1.2 1.2
black dye
Prin. resin 67.0
(Exampl~ 1)
Prin. Rosin 57.3
(Exa~ple 2)
Pr~n. re~in56.657.3 57.3 57.3
(ExaJple 3)
Prin. resin 57~3
(Example 5)
Lead (III) 1.8 1.8 1.8 1.8
2-ethyl
hexanoate
(42% Pb)
Lead (III) 3.2
octanoate
(24% Pb)
2 ~ 0
(Table 1 continued~
Lead
naphth~nate 3.2
s(24% Pb)
F1QW
additive 2.3 2.3 2.3 2.3 2.3 2.3
~A~PL~ OF I~CO~PORA~O~ 0~ R IN80~U~LÆ OR~ANO-~AD
CO~PO~N W ~TO ~RINCI~AL ~J~I~ ~W ~8IO~
~XAMF~B~ 1~ - 23
This g~neral procedure applies to examples 16 - 23.
The specific for~ulations ~or these examples are shown in
Table 2.
First, principal resin solutions containing the
crossl~nker, pla~ticizer, the organo-lead ~o~po~nd(s), and
other applicable ingredient~ are ~ixed together as
de~cribed for the pr~vious sQt o~ ~xa~ple3 (9 - 14). A
solubilizing acid is then added to the principal resin
~olution, and then th~ resultant solubilized principal
resin ~olu~ion i8 then Dix~d with deionized wat~r, or
op~ionally, a deionized water/surfactant ~ixtur~.
2 5 TAB~ 2
INGREDIENTS EXAMPLES
16 17 18 19 20 21 22 23
Exampl~ 9 269.7
(74% NV)
Exampl~ 10 269.7 269.7
t74% NV)
~Ya-P1~ 1~ 269 . 7
(7~
EXA~P1~ 12 269.7
(74%-NV)
Exa~pl~ 13 269.7
(74% NV)
Example 14 269.7
(74% NV)
Exa~ple 15 269.7
~74% NV)
2 ~ 2 ~3
(Table 2 continued)
~cetic 2.53 2.53 2.53 3.19 2.92 3.31 2.53
Acid
(Glacial)
Lactic aoid 4.46
(85S)
Deionized 298.0 298.0 296.1 298.0 ~97.3 297.6 297.2 298.0
water
1 0 - --
~ AMPL~8 o~ PIOE~NT PA~B~, ~ITE AND ~IT~O~T T~E
INCoRPo~ATIO~ OF ~T~R I~80~WaL~ OR~N~L~AD COM~OUN~8
- ~AKPLE 2~
To a suitable mixing vessel, 198.3 parts of grind
resin from Example 8 are mixed with 11.1 parts acetic acid,
~.O parts of Tristar~ 27 defoamer (Tristar Che~ical Co.,
Dall~s, TX), and 342.6 parta deionized water. Once
homogeneous, 12.6 parts carbon black, 63.0 parts clay
extender, and 329.7 parts titanium dioxide are dispersed
into the mixture. Using a high speed Cowles disperser,
sandmill, ballmill, or other pigment dispersinq eguipment,
a finenese of gr~nd (F.O.G.) o~ 5-7 is obtained.
~AMPL$ 25
To a suitable mixing vessel, 226.36 of grind resin
from Exa~ple 7 are mixed with 388.9 parts of deionized
water, 16.54 parts carbon black, and 564.31 parts titanium
dioxid~. Th~ mixture is ground until a Hegman fineness of
grind o~ 5 - 7 i8 obtained.
~XU~L~ 26
. To a ~uitable mixins vessel, 198.3 parts of grind
resin from Example 8 are mixed wi~h 27.2 parts of Lead-2-
Ethylhexanoate, and stirred for about 30 minute~. Then,
11.1 parts acetic acid, 700 parts of Tristar 27- defoamer,
and 342.6 parts deionized water are added, continuing the
mixing. Once homogeneous, 12.6 parts carbon black, 63.0
parts clay extender, and 329.7 parts titanium dioxide are
added and dispersed to a Hegman finene~s of grind of 5 - 7.
29
2 ~ 2 0
~SA~LE OF C~T~ODIC' PAIN~8 CO~T~I~IN~
W~T~R IN80~L~ L~AD CO~PO~N W
~A~P~R8 27 - 3~
Example are prepared according to the formulations
outlined in Table 3.
ING~EDIENTS EXAMPLE
27 28 29 30 31 32 33 34
Emul~ion
(Example 16) 571.4
` Emul~ion 400.7
(Example 1~)
Emulsion 413.2
(Example 18)
Emulsion 400~7
(Exa~ple 19)
Emulsion 413.2
(Example 20)
Emul ion 400 7
(Example 21)
Emulsion
(Example 22)
Emulsion 571.4 400.2
(Example 23)
Pzste 109.8 109.8 109.8
(Example 24)
Paste 95.0 95.0
(Example 25)
Paste 112.0
(Exa~ple 2~)
Deionized 428.6 489.5 491.8 489.5 491.8 489.5 428.5 487.8
wator
Total 1000 1003 1000 1000 1000 1000 1000 1000
Although this invention has beQn shown and described
with respect to the detalled e~bodi~ents thereof, it will
be under~tood by those skilled in the art ~hat various
changes in form and detail ~hereo~ may be made without
departing from the spirit and scope of this invention.
