Note: Descriptions are shown in the official language in which they were submitted.
`
W093/03~04 2 1 ~ 7 3 2 8 PCT/~92/062~6 Z
i. . 1
- Anueous Coatinq ComPosition
This invention relates to compositions which are
useful as primers for ~nhancing the adhesion of coatings
to polyolefin substrates. The compositions of this
invention do not contain large quantities of organic
solvent. This invention also relates to a process for
prepaxation of these compositions.
The application of paints and other coatings to
substrates of polyolefin, such as polypropylene,
thermoplastic olefin and polyethylene, is typically
difficult because polyolefins are substantially
chemically inert.
This problem has previously been overcome by the
use of two different approaches which employ adhesion
promoting compositions. One approach is to use an
adhesion promoting composition as a separate primer
coating between the polyolefin substrate and the paint.
~he primer coating adheres adequately to both the
polyolefin and the paint and thereby creates a unitary
three component structure with the paint as the outer
portion of the structure. Another approach to coating
polyolefins has been to use an adhesion promoting
composition as an additive along with the paint. This
technique is sometimes known in the art as use of a
"stir in" adhesion promoter.
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W093/03104 PCT/US92/06286
~1 3~
Numerous polymeric materials have been investigated
as possible components for such adhesion promoters.
Chlorinated polyolefins have been found to be very
satisfactory as the polymeric component for primer
5 compositions due to their cost and performance. For
example, U.S. 3,579,485, U.S. 4,070,421, U.S. 4,966,947,
U.S. 4,962,149 and U.S. 4,954,573 disclose chlorinated
polyolefins which are,entirely satisfactory for the
polymeric component of adhesion promoting compositions
useful for coating polyolefin substrates.
Even though chlorinated polyolefins have bePn used
to prepare adhesion promoting compositions which are
entirely satisfactory, the chlorinated polyolefins had
to be formulated with large quantities of an organic
solvent, such as xylene or toluene. Use of large
quantities of an organic solvent is undesirable because
unless elaborate solvent recovery methods are empioyed
application of the primer coating composition results in
release of the organic solvent into the atmosphere which
can result in both pollution problems and health
problems for workers applying the primer coating
composition.
We have now discovered an entirely satisfactory
water based primer coating composition which preferably
does not contain a large quantity of organic solvent.
WO93/~3104 ~ Q PCT/US92/06286
Y~ ~h
A composition which is comprised of a chlorinated
polyolefin, water and other materials and is reported to
be useful as a primer coating for polyolefins is
disclosed in WO 9012056.
A composition which is comprised of two types of
polymers, water and other materials and is reported to
be useful as a primer coating for polyolefins is
disclosed in GB 2 272 418.
~roadly, the composition of this invention can be
thought of as a three component composition comprising
A) a chlorinated polyolefin having a particular
: range of molecular weight, softening point and
amount of chlorine,
(B) a carboxylic acid functional resin, and
(C) water.
Optionally, an amine, a surfactant and an organic
solvent may be present in the composition.
The chlorinated polyolefins useful in this
invention can be broadly described as a chlorinated
polyolefin having a molecular weight in the range of
9,000 to 150,000, a softening point in the range of 75
to 115~C and an amount of chlorine in the range of 15 to
35 weight percent, based on the weight of the
~,
polyolefin. One embodiment of the chlorinated
polyolefin useful in this invention is disclosed in U.S.
3,579,485. A chlorinated polyolefin useful in another
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~: , :. - . . ...
W093/03104 ~CT/US92/0628fi
~;
~ ~f~
embodiment of this invention is the chlorinated
polyolefin disclosed in U.S. 3,579,485 reacted with a
hydroxyl group containing primary amine to form a
chlorinated, imidized polyolefin. These polyolefins are
Xnown in the art and are described in U.S. 4,g54,573.
Thus, since it is within the scope of the invention to
use either the chlorinated, non-imidized polyolefin
described in U.S. 3,579,485 or the chlorinated, imidized
polyolefin described in U.S. 4,954,573 the term
10 "chlorinated polyolefin' is meant to include both of
these polymers. In one embodiment of the invention the
chlorinated polyolefin can comprise a chlorinated
polyolefin having a molecular weight in the range of
lO0,000 to 150,000, a ~oftening point in the range of 80
15 to 115C and an amount of chlorine in the range of 20 to
35 percent, based on the weight of the chlorinated
polyolefin. In another embodiment of the invention the
chlorinated polyolefin can comprise a chlorinated
polyolefin having a molecular eight in the range of
20 110,000 to 130,000, a softening point in the range of 95
to 105C and an amount of chlorine in the range of 25 to
30 percent, based on the weight of the chlorinated
polyolefin. In a preferred embodiment, the chlorinated
polyolefin has a molecular weight in the range of 9,000
25 to 16,000, a softening point in the range of 80 to 95C
and an amount of chlorine in the range of 18 to 22
:
W~93/03104 PC~/VS92/~6286
2~7328
percent, based on the weight of the polyolefin. In this
invention the molecular weight of the chlorinated
polyolefin is average number molecular weight.
In this invention the amount of chlorinated
polyolefin in the composition is in the range of 70 to
30 weight percent, prefera~ly in the range of 70 to 40
weight percent, and more preferably in the range of 70
to 4S weight percent, based on th~ combined weight of
the chlorinated polyolefin and the carboxylic acid
lo function21 resin.
The carboxylic acid functional resins useful in
this invention can comprise any polymer which has a
sufficiently high molecular weight to form an admixture
with the chlorinated polyolefin and also has sufficient
carboxylic acid functionality to be compatible with the
chlorinated polyolefin in the sense i~ will combine with
the chlorinated polyolefin and form the primer coating
composition of this invention.
According to one theory the carboxylic acid
functional resin performs two functions. First, the
resin serves as the medium in which the chlorinated
polyolefin can be formed into an admixture having a
fluid homogenous character. Second, the car~oxylic acid
~ functionality of the resin, through neutralization,
; 25 provides a mechanism for the creating the admixture of
the two polymers and the water. Thus, important
W093/03104 PCT/US92/06286
2~
characteristics of the resin are that the resin be
compatible enough with the chlorinated polyolefin to
make a fluid homogenous mixture and that the resin have
acid functionality to allow dispersion through amine
neutralization of the acid group.
Preferably, the carboxylic acid functional resin is
an alkyd resin, a polyester resin or an acrylic resin.
More preferably the carboxylic acid functional resin is
either an alkyd resin or an acrylic resin.
The alkyd resins useful in this invention are well
known in the art and are polyesterification products of
polyhydric alcohols and poly-functional acids where part
of the acid component may be a long chain fatty acid
from vegetable oil. Examples of poly-functional acids
include phthalic anhydride, adipic acid, maleic
anhydride, isophthalic acid, sebacic acid, azelaic acid,
terephthalic acid, trimellitic anhydride, linoleic acid,
linolenic acid, benzoic acid, hexahydrophthalic
anhydride, tetrahydrophthalic anhydride, 1,4-
cyclohexanedicarboxylic acid or fumaric acid. Examplesof polyhydric alcohols include glycerol,
trimethylolethane, trimethylolpropane, diethylene
glycol, neopentyl glycol, 1,4-cyclohexanedimethanol,
2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,2-
propylene glycol, 1,2-propanediol, ethylene glycol,
butylene glycol, dipropylene glycol, and
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~ W093/03~04 PCT/US92/062~6
~`` 21~7328
pentaerythritol. The oil which is used to modify the
alkyd resin may come from the group of oils which
includes tung, linseed, soya, safflower, castor, corn,
cotton seed, pPralla, sesame, soybean, cocoanut,
dehydrated castor and tall oils. The amount of oil
modification in resins useful in the invention can be in
the range of c45% (short oil alkyds) or in the xange of
45 to 65% (medium oil alkyds).
The al~yd resins which are useful in the invention
can have a number averaye molecular weight in the range
of 300 to 30,000 grams per mole and an acid number
greater than 20. More preferably the acid number of the
alkyd resin should be in the range 25 to 150.
Most preferably, the alkyd resin is a medium oil
alkyd having 70 percent non-volatile content, a Gardner
viscosity in the range of Z to Z2 and an acid value in
the range of 50 to S9.
The acrylic resins useful in this invention are
well known in the art and are addition polymers which
are the reaction products of acrylic monomers which come
from a large number of acrylic and methacrylic acids and
esters. Examples of acids and esters which can be used
include acrylic acid, methacrylic acid, styrene, methyl
methacrylate, ethyl acrylate, butyl acrylate, m~thyl
acrylate, ethyl methacrylate, butyl methacrylate, 2-
hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
.:
.
,
, - .,
~093/03104 PCT/VS~2/0~2~'
butyl acrylate, propyl methacrylate, lauryl
methacrylate, 2-hydroypropyl methacrylate, 2-ethyl hexyl
methacrylate, hexyl methacrylate, cyclohexyl
methacrylate, ethoxyethyl acrylate, ethylhexyl acrylate,
cyclohexyl acrylate, hexyl acrylate, butadiene~ vinyl
toluene, vinyl pyrrolidine and 2-hydroxypropyl acrylate.
The acrylic resins useful in this invention have a
number average molecular weight in the range of 400 to
40,000 grams per mole and an acid nu~ber greater than
20. More preferably the acrylic resin has an acid
number in the range of 25 to 150.
In a preferred embodiment, the acrylic resin is a
solid acrylic oligomer having an acid value in the range
of 220 to 250, a ring and ball softening point in the
range of lO0 to 120C and an average number molecular
weight in the range of 2000 to 3000.
The polyester resins useful in this invention are
well known in the art and are condensation polymers
which are the polyesterification product of
polyfunctional carboxylic acid and polyfunctional
alcohols. Examples of polyfunc~ional carboxylic acids
include phthalic anhydride, isophthalic acid,
cyclohexanedicarboxylic acid, àdipic acid, azelaic acid,
maleic anhydride, sebacic acid, terephthalic acid,
trimellitic anhydride, linoleic acid, linolenic acid,
benzoic acid, hexahydrophthalic anhydride,
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W093/03104 2 1 0 7 3 ~ ~ PCT/US92/06~86
.~
~. . .
tetrahydrophthalic anhydride, fumaric acid, 1,4-
cyclohexanedicarboxylic acid and succinic acid.
Examples of polyfunctional alcohols include ethylene
glycol, neop-entyl glycol, diethylene glycol, 1,6-
hexanediol, cyclohexanedimPthanol, glycerol,
trimethylolethane, trimethylolpropane, butylene glycol,
1,4-cyclohexanedimethanol, 1,2-propylene glycol, 1,2
propanediol, dipropylene glycol, pentaerythritol and
2,2,4-trimethyl-1,3-pentanediol.
Polyesters which are useful in the present
invention have a number average molecular weight in the
range of 100 to 10,000 grams per mole. Useful polyester
resins are those which have a acid number greater than
20. More preferable polyester resins are those which
have an acid number in the range 25-150.
The amount of the carboxylic acid functional resin
is in the range of 30 to 70 weight percent, preferably
in the range of 30 to 60, and more preferably in the
range of 30 to 55 weight percent, based on the combined
weight of the chlorinated polyolefin and the carboxylic
acid functional resin.
Combinations of parti~ular chlorinated polyolefins
and particular carboxylic acid functional resins
represent a particularly preferred embodiment of this
invention. For example, when the preferred chlorinated
polyolefin is the non-imidized material, use of the
:,
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WO93/03104 PCT/US92~062~h
3?~
above described medium oil alkyl having 70 percent non-
volatile content, a Gardner viscosity in the range of Z
to Z2 and an acid value in the range of 50 to 59 is a
particularly preferred embodiment of the invention.
S Additionally, when the preferred chlorinated polyolefin
in the imidized material, use of the above described
solid acrylic oligomer having an acid value in the range
of 220 to 250, a ring,and ball softening point in the
range of 100 to 120C and an average number molecular
weight in the range of 2000 to 3000 represents a
particularly preferred embodiment of this invention.
The compositions of this invention contain water.
The amount of water can vary widely depending on
numerous factors, such as the needs of the manufacturer,
transportation efficiencies and the needs of the
particular customer. An important property of the
compositions of this invention is that these
compositions can be manufactured using less water than
would ~e typically be required to apply the compositions
as a coating and water can be subsequently added by the
customer at a later time to prepare a coating
composition. This can be done by simply pouring
additional water into the composition prepared by the
manufacturer without having to consider in detail any
particular temperature, pressure or time used to prepare
the diluted composition. Thus the manufacturer can
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WO93/03104 ~ 1 0 ~ 3 ~ 8 PCT/VS92/0~28~
, . ~
- 11
prepare a "concentrated" product which is low in water
and ship the concentrated product to the customer
without the necessity of incurring the additional cost
. of also shipping additional amount to customer. A
"concentrated~ product is also often desired if the
adhesion promoter composition is to be used as an
additive to the paint in order to prevent excessive
dilution of the paint.
Even though the amount of water can vary widely and
there is no upper limit on the amount of water there is
a lower limit on the amount of water because there must
at least be sufficient water in the composition to
result in the formation of an admixture of the four
components. ~lthough the precise amount of water
necessary to form the required admixture can vary,
generally there must be at least 40 weight % water in
the composition, based on the weight of the total
composition, in order to form an admixture with pourable
viscosity characteristics.
The compositions of this invention can optionally
contain an amine. Although the amine can be aromatic or
aliphatic, aliphatic amines are preferred. In a
preferred embodiment the aliphatic amine can be either a
primary, secondary or tertiary amine and optionally
contains other oxygen containing functional groups. The
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WO93/03104 PCT/USg2/06286
3? ~ ~
- 12
amines useful in this invention generally have a
molecular weight in the range of 20 to 200.
A highly preferred group of amines are primary,
secondary and tertiary aliphatic amines having a
functionality of 1 to 3 which can be generally
represented by the general formulae:
R2
R1 ~ R3 i or
R2 R4
Rl ~ R3 - ~ - R5 i or
2 4 6
Rl ~ R3 ~ _ R5 ~ R
wherein R1 = R7 are independently selected from H or
straight or branched chain alkyl, hydroxyalkyl, or
alkoxylalkyl groups of 1 to 20 carbon atoms; R1 - R7 can
additionally include a substituted al~yl group, i.e.,
where one or more of the carbons in the radical is
replaced with or has substituted thereon another
functionality, e.~., an amine, ether, hydroxy or -
mercapto moiety, e.g., tris-(3-aminopropyl) amine.
Another group of highly preferred amines within the
above classes are those primary, secondary or tertiary
aliphatic amines of ~he above Formulae in which R1 - R7
is specifically substituted with or contains one or more
hydroxyl (-OH) functionalities.
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WO93/03104 PCT/US92/~286
, 210~3~8
13
Another group of preferred amines can be
represented by the formulae:
Rg Rg
R~ - (NH2)n or Rg - (~H)n or R8 - (Rlo ~ R11)
wherein n is 1 or 2 and R8, ~9, R1o and R11 are
independently selected from straight or branched chain
alXyl, hydroxyalkyl or alkoxyalXyl groups of 1 to 20
carbon atoms. These chains may also be substituted with
another functionality as described above.
Yet another group which comprise amines preferred
in the practice of the present invention are primary,
secondary and tertiary aliphatic amines with an amine
functionality of 1-3 which also contain one or more
ether or alkoxy linkages. Such materials are sometimes
referred to as poly(oxyalXylene)diamines. Ethoxylated
or propoxylated materials are particularly preferred.
Exemplary amines preferred for use in the present
invention include:
2-amino-1-butanol;
4-amino-1-butanol;
2-aminoethanethiol;
2S 2-aminoheptane;
2-amino-1-hexanol;
6-amino-1-hexanol;
allylamine;
., , . : ~--.: . . :
W093/03104 PCT/US92/~6286
14
2-amino-3-methyl-1-butanol;
2-amino-2-methyl-1,3-propanediol;
2-amino-2-methyl-1-propanol;
2-amin~-1-pentanol;
5-amino-1-pentanol;
3-amino-1-propanol;
ammonium hydroxide
amylamine;
butylamine;
N,N'-bis(2-aminoethyl)-1,3 propanediamine;
N,N'-bis(3-aminopropyl)-1,3-propanediamine;
1,3-bis(dimethylamino)-2-propanol;
l-[N,N-bis(2-hydroxyethyl)amino]-2-propanol;
N,NI-bis(2-hydroxyethyl)ethylenediamine;
decylamine;
1,4-diaminobutane;
1,10-diaminPdecane;
1,12-diaminododecane;
1,7-diaminoheptane;
1,3-diamino-2-hydroxypropane;
3,3'-diamino-N-methyldipropylamine;
1,2-diamino-2-methylpropane;
1,9-diaminononane;
1,8-diaminooctane;
1,5-diaminopentane;
1,2~diaminopropane;
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~WO93/03104 21 0 7 3 2 ~ PCT/US~2/06286
`. ~ !
1,3-diaminopropane;
dibutylamine;
3-(dibutylamino)propylamine;
diethanolamine;
diethylamine;
5-diethylamino-2-pentanol;
3-(diethylamino)-1,2-propanediol;
1-diethylamino-2-propanol;
3-diethylamino-1-propanol;
3-diethylaminopropylamine;
diethylenetriamine;
N,N-diethylethanolamine;
N,N-diethylethylenediamine;
N,N-diethylmethylamine;
N,N'-diethyl-1,3-propanediamine;
diisobutylamine;
diisopropanolamine;
diisopropylamine;
2-(diisopropylamino)ethanol;
3-diisopropylamino-1,2-propanediol;
N,N-diisopropylethylamine;
1-dimethylamino-2-propanol;
2-dimethylaminoethanol
3-dimethylamino-1-propanol;
3-dimethylaminopropylamine;
1,3-dimethylbutylamine;
.
. . .
WO93/03104 PC~/US92/0~2~i
3~
3,3-dimethylbutylamine;
N,N-dimethylethanolamine;
N,N-dimethylethylamine;
N,N-dimethylethylenediamine;
N,N-dimethyl-N'-ethylethylenediamine; -
N,N'-dimethyl-1-,6-hexanediamine;
2,5-dimethyl~2,5-hexanediamine;
1,5-dimethylhexylamine;
2,2-dimethyl~1,3-propanediamine;
(~) 1,2-dimethylpropylamine;
dipropylamine;
dodecylamine;
ethanolamine;
3-ethoxypropylamine;
ethylamine;
2-(ethylamino)ethanol;
N-ethylbutylamine;
2-ethylbutylamine;
N-ethyldiethanolamine;
ethylenediamine;
hexamethylenediamine;
1,6-hexanediamine;
hexylamine;
isoamylamine;
isopropylamine;
N-isopropylethylenediamine;
WO93/03104 PCT/US92/06286
,-: 21~732~
N'-isopropyl-2-methyl-1,2-propanediamine;
N,N,N',N'-tetramethyl-1,4-butanediamine
N,N,N',N'-tetramethyldiaminomethane;
- N~N~Nl~Nl-tetramethylethylenediamine;
N,N,N',N'-tetramethyl-1,6-hexanediamine;
N,N,N',N'-tetramethyl-1,3-propane-diamine;
N,N,2,2-tetramethyl-1,3-propanediamine;
tributylamine;
tridecyamine;
triethanolamine;
t~iethylamine;
triisooctylamine;
triisopropyanolamine;
trimethylamine;
methylamine;
2-(methylamino)ethanol;
N-Methylbutylamine;
1-methylbutylamine;
2-methylbutylamine;
N-methyldiethanolamine;
N~methylethylenediamine;
N-methyl-1,3-propanediamine;
morpholine
nonylamine;
octylamine;
: teri-octylamine;
.. ....
~- .
... ~ :. ~ ~ ..
WO9~/03104 P~T/US92/062~
3~
lg
propylamine;
2-(propylamino)ethanol;
1-tetradecylamine; and
tris(3-aminopropyl)amine. Mixtures of such materials
may also be employed.
Preferred amines are ammonium hydroxide,
dimethylethanolamine, triethylamine, diethanolamine,
ethanolamine, dimethylamine, diethylamine, piperazine,
morpholine and 2-amino-2-methyl-1-propanol. When the
car~oxylic acid functional resin is an alkyd resin a
particularly preferred amine is ammonium hydroxide.
When the carboxylic acid functional resin is an acrylic
a preferred amine is dimethylethanolamine.
The amount of amine can be in the range of O to 20
weight percent, preferably in the range of lO to 20
weight percent, based on the combined weights of the
chlorinated polyolefin and carboxylic acid functional
resin.
The surfactants useful in this invention include
~oth non-ionic and cationic surfactants. By the term
"non-ionic surfactant" we mean a surfactant which
contains no positively or negatively charged functional
groups. By the term "cationic surfactant" we mean a
surfactant which ionizes in water to produce a large
positively charged ion and a small negatively charged
ion.
WQ93/03~04 PCT/US92/0628~ i
ff 2107328
..
19
In this invention the non-ionic surfactants can
have a molecular weight of up to 500 or even higher and
can include polymeric materials. The non-ionic
surfactants include materials which contain groups of
varying polarity whereby one part of the molecule is
hydrophilic and the other part of the molecule is
hydrophobic. Examples of such materials include
polyethyleneoxy polyols and ethoxylated alkyl phenols.
Particularly preferred classes of non-ionic surfactants
include alkyl phenoxy poly(ethyleneoxy) alcohols,
primary ethoxylated alcohols and secondary ethoxylated
alcohols. Preferably the non-ionic surfactant is an
alkyl phenoxy poly(ethyleneoxy) alcohol having 22 to 215
carbon atoms.
The cationic surfactants useful in this invention
have a molecular weight in the range of lOO to lOOO and
can be broadly be described as alkoxylated amines.
Preferably the cationic surfactant is an alkoxylated
fatty amine or an akloxylated tallow amine.
The amount of surfactant is broadly in the range of
1 to 30 weight percent, based on the combined weight of
the chlorinated polyolefins and carboxylic acid
functional resin.
The compositions can contain other materials in
major amounts. For example, the compositions of this
invention can contain materials typically used in the
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WO93/~3104 PC~/~S92/06286
3~ ~
paint industry to prepare paint f ormulations, such as
thickeners, wetting agents and flow aids, pigments,
resins and solvents.
The compositions can contain organic solvents as
long as the amount of organic solvent is not large.
Thus, the compositions of this invention preferably
contain less than 50%, more preferably less than 25~
organic solvent based on the weight of the composition.
The compositions of this invention can be used as
lo aa adhesion promoting composition according to two
different approaches. Selection of the preferred
approach depends on numerous factors, such as the
specific characteristics of the paint, the particular
substrate to be painted, the nature and extent of the
other materials to be used in the paint formulation and
other factors. In accordance with one approach, the
coating compositions of this invention can be used as a
separate primer coat by preferably diluting the
manufactured composition with water, adding any desired
additives and then applying the diluted composition to
a polyolefin substrate to form a coating using
conventional means, such as spraying, brushinq or
dipping. After the composition has been applied as a
coating and the coating has dried a paint is applied
over the primer coating. The primer coating adheres to
both the polyolefin and the paint and thereby creates a
WO93/03104 P~TIUS92/06286
2 ~
. ;
-21
unitary three component structure with the paint as the
outer portion of the structure. In accordance with the
other approach, the compositions of this invention can
be used as a so-called "stir-in" paint additive. In
this approach the composition is added admixed with the
paint and the resulting admixture is applied to the
polyolefin substrate to form a single coating which
adheres to the polyolefin substrate.
The compositions of this invention are admixtures
which have a particle size suitably small to make the
admixtures useful in coating embodiments. Therefore,
the compositions of this invention include not only what
some authorities call "emulsions" and "dispersions" but
include as well as all other physical forms in which the
various components can be become admixed. For example,
some authorities characterize water containing
admixtures wherein the particle size in the range of 0.1
to 10 microns as a "emulsions". Other authorities
regard water containing admixtures wherein the particle
size is greater than 10 microns as a "dispersion".
While both of these types of admixtures are within the
scope of this invention, the invention is not limited to
these or any other kind of particular admixture and
includes all possible types of admixtures regardless of
physical form as long as the particle size is small
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W093/03104 PCT/US~2/06286
~9 22
enough for the admixtures to have utility in coating
applications.
While the compositions of this invention are
particularly useful as adhesion promoters to enhance the
adhesion of paints to polyolefin substrates it is within
the scope of the invention for the compositions to be
used by themselves as a paint to form a final protective
coating which not only protects the substrate but also
is decorative as a result of the addition of pigments.
The compositions of this invention are prepared by
a novel process comprised of two steps. First an
admixture of the chlorinated polyolefin and carboxylic
acid functional resin is prepared and then an admixture
is prepared composed of the admixture of the polyolefin
and resin and water.
The chlorinated polyolefin and carboxylic acid
functional resin can be prepared into an admixture by
methods well known in the art by preparing admixtures of
polymeric materials. If the chlorinated polyolefin and
carboxylic acid functional resins are both solids they
can be admixed in a double screw extruder or can be
powdered and the mixed powders extruded in a single
screw extruder. Additionally the admixture can be
prepared by combining the resin and chlorinated
polyolefin on a hot roll mill such as a hot three roll
mill. The admixture can be cooled and then pulverized
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W093/03104 2 ~ ~ ~ 3 2 ~ PCT/US92/0~286
23
to a powder prior to addition of the other materials.
When the chlorinated polyolefin is a solid and the
carboxylic acid functional resin is a liquid or
solution, the admixture can be prepared by heating the
mixture above the softening poin~ of the chlorinated
polyolefin and stirring the chlorinated polyolefin and
the resin together. The chlorinated polyolefin can be
mixed with the resin by applying high-shear mixing.
The admixture of water, and optionally an amine and
surfactant, and the admixture of the chlorinated
polyolefin and carboxylic acid functional resin can be
prepared by methods well known in the art for preparing
admixtures of polymers and water. According to one
method the admixture is prepared by subjecting the
materials to high shear in a vessel equipped with a
means to create high shear, such as a stirrer.
According to another method, a heated admixture of the
chlorinated polyolefin a~d the carboxylic acid
functional resin is combined with a heated admixture of
water and amine using agitation techniques well known in
the art.
In the following examples compositions of the
invention were prepared from a chlorinated polyolefin, a
carboxylic acid functional resin, water and optionally
an amine, a surfactant and an organic solvent. In some
examples, the chlorinated polyolefin and the carboxylic
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WO93/03104 pCT/-]S92/~6286
24
acid functional resin were introduced into a vessel
equipped with means to agitate the materials.
Agitation was started and the contents of the vessel
were heated at a specific temperature for a specific
period of time. In other examples the chlorinated
polyolefin and the carb~xylic acid functional resin were
combined into the admixture using a standard three roll
mill. Water and optionally an amine, a surfactant and
an organic solvent were then added and an admixture
formed by agitation with high shear. Storage stability
tests of selected compositions were conducted by visual
inspection in glass jars after 2 to 8 weeks at 25C.
Paint adhesion tests of selected compositions were
conducted in accordance with ASTM D 3359-83, Method A.
Paint adhesion tests were conducted by applying the
composition to polypropylene and to a polyolefin which
had been modified with an elastomeric polymer. These
materials are generally designated in the trade as
"thermoplastic olefins" and are abbreviated "TPO". The
composition was applied by spraying and then dried at
room temperature. A commercially available automotive
paint system, was applied and baked 30 minutes at 250F.
Example l
This example illustrates preparation of a
composition of the invention using a particular
,,, . . . , .:
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WO93/03104 2 1 0 ~ 3 2 ~ PCT/US92/06286
.; .
,:.
- 25
chlorinated polyolefin, a particular carboxylic acid
functional resin, water and an amine.
An admixture was prepared composed of 50 grams of a
- chlorinated, non-imidized polyolefin which has a
molecular weight in the range of 9,000 to 16,000, a
softening point in the range of 80 to 95C and an amount
of chlorine in the range of 18 to 22 percent, based on
the weight of the polyolefin, and 50 grams of a
carboxylic acid functional resin which is a medium oil
alkyd resin (70% solids) having an acid number in the
range of 50 to 59. The admixture was heated for 2 hours
at 105C. 10 grams of ammonium hydroxide (2B%) and 200
grams of water were then added and an admixture formed
by high shear agitation for 10 minutes. The resultant
composition was diluted with sufficient additional water
to result in a primer coating composition typical of
that used in the trade and paint adhesion tests were
conducted with the following results.
Polypropylene 100% adhesion
TPO 100% adhesion
Example_2
This example illustrates preparation of a
composition of the invention using different amounts of
the same materials used in Example 1.
.
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WO93/03104 P~T/~S92/062X6
3~ f~
26
An admixture was prepared composed of 30 grams
polyolefin and 70 grams of alkyd resin. The admixture
was heated for 1 hour at 121C. 8 grams of ammonium
hydroxide (28%) and 150 grams of water were then added
and an admixture formed by high shear agitation for 10
minutes. The result of a stability test at 25C for 8
weeks was slight settling. The composition was diluted
with sufficient additional water to result in a primer
coating composition typical of that used in the trade
and paint adhesion tests were conducted with the
following results.
Polypropylene 100% adhesion
TP0 100% adhesion
Example 3
This example illustrates preparation of a
composition of the invention using a different amine
than used in Example 1.
An admixture was prepared composed of 50 grams
polyolefin and 50 grams of alkyd resin. The admixture
was heated for 2 hours at 121C. 4 grams of
dimethylethanolamine and 200 grams of water were then
added and an admixture formed by high shear agitation
for 10 minutes. The result of a stability test at 25C
for 8 weeks was no change. The composition was diluted
with sufficient additional water to result in a primer
.. . ., . . . - , . . -:
.: - : . .: :
. ' :~ ' , : . . . .
W093/03104 PCT/U~92/06286
~` 2~7~2~
27
coating composition ~ypical of that used in the trade
and paint adhesion tests were conducted with the
following results.
Polypropylene 100% adhesion
TPO 100% adhesion
Example 4
This example illustrates preparation of a
composition of the invention using a different amount of
the same materials used in Example 3.
An admixture was prepared composed of 70 grams
polyolefin and 30 grams of alkyd resin. The admixture
was heated for 12 hours at 121C. 2 grams of
dimethylethanolamine and 200 grams of water were then
added and an admixture formed by high shear agitation
for 10 minutes. ~he xesult of a stability test at 25C
for 8 weeks was slight settling. The composition was
diluted with sufficient additional water to result in a
primer coating composition typical of that used in the
trade and paint adhesion tests were conducted with the
following results.
Polypropylene 100% adhesion
TP0 100% adhesion
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W093/03104 PCT/~S92/0~2~6
3~
28
ExamPle 5
This example illustrates preparation of a
composition of the invention using differen~ amounts of
the same materials used in Example 1.
An admixture was prepared composed of 25 grams
polyolefin and 25 grams of alkyd resin. The admixture
was heated for 2 hours at 121C. The lOg ammonium
hydroxide (28~) and lO~g water were then added and an
admixture formed by high shear agitation for 10 minutes.
The result of a stability ~est at 25C for 6 weeks was
slight settling. The composition was diluted with
sufficient additional water to result in a primer
coating composition typical of that used in the trade
and paint adhesion tests were conducted with the
following results.
Polypropylene 100% adhesion
TP0 100% adhesion
Example 6
This example illustrates preparation of a
composition of the invention using different amounts of
the same materials used in Example 5.
An admixture was prepared composed of 3S grams
polyolefin and 15 grams of alkyd resin. The admixture
was heated for 2 hours at 121C. 5 grams of ammonium
hydroxide (28%~ and 100 grams of water were then added
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W093/03104 , PCT/US92/06286
~1~7~
2g
and an admixture formed by high shear agitation for lo
minutes. The result of a stability test at 25c for 6
weeks was heavy settling. The composition was diluted
with sufficient additional water to result in a primer
coating composition typical of that used in the trade
and paint adhesion tests were conducted with the
following results.
Polypropylene 20% adhesion
TPO 100~ adhesion
Exam~le 7
This example illustrates preparation of a
composition of the invention using different amounts of
the same materials used in Example 5.
An admixture was prepared composed of 25 grams
polyolefin and 25 grams of alkyd resin. The admixture
was~heated for 2 hours at 121C. 1 gram of ammonium
hydroxide (28) and 100 grams of water were then added
and an admixture formed by high shear agitation for 10
minutes. The result of a stability test at 25C for 6
weeks was heavy settling. The composition was diluted
with sufficient additional water to result in a primer
coating composition typical of that used in the trade
and paint adhesion tests were ~onducted with the
following results.
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W093/03104 PC~/US92/06286
3~
Polypropylene o% adhesion
TPO .4 0% adhesion
Example 8
This example illustrates preparation of a
composition of the invention using a different
carboxylic acid functional resin than used in Example 7.
An admixture was prepared composed of 50 grams
polyolefin and 50 grams of a chain stopped alkyd resin
(70% solids) with 35 acid number. The admixture was
heated for 10 minutes at 121C. 8 grams of ammonium
hydroxide (28%) and 100 grams of water were then added
and an admixture formed by high shear agitation for 10
minutes. The result of a stability test at 25c for 8
weeks was heavy settling. The composition was diluted
with sufficient additional water to result in a primer
coating composition typical of that used in the trade
and paint adhesion tests were conducted with the
following results.
Polypropylene 100% adhesion
TP0 100% adhesion
Example 9
This example illustrates preparation of a
composition of the in~ention using a different
carboxylic acid functional resin than used in Example 8.
WO93/03104 PCT/US9~/06286
3;~
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31
An admixture was prepared composed of 30 grams
polyolefin and 70 grams of an acrylic resin (65% solids)
with 90 acid number. The admixture was heated for 2
hours at 12i~C. 6 grams of ammonium hydroxide (28~) and
100 grams of water were then added and an admixture
formed by high shear agitation for 10 minutes. The
composition was diluted with sufficient additional water
to result in a primer coating composition typical of
that used in the trade and paint adhesion tests were
conducted with the following results.
Polypropylene 100% adhesion
TP0 100% adhesion
Example 10
This example illustrates preparation of a
composition of the invention using a chlorinated
polyolefin, a carboxylic acid functional resin, an
amine, a surfactant and water.
An admixture was prepared composed of 50 grams
polyolefin and 50 grams of an alkyd resin with 85 acid
number. The admixture was heated for 2 hours at 121C.
4 grams of dimethylethanolamine, 1 gram of a nonyl
phenoxy poly(ethyleneoxy) alcohol having an HBL value in
the range of 13 to 14 and 200 grams of water were then
added and an admixture formed by high shear agitation
for 10 minutes. The result of a stability test for 2
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~093/03104 PCT/US92/06286
~ ~ '`` 32 ~ ?
weeks and 25C was heavy settling. The composition was
diluted with sufficient additional water to result in a
primer coating composition ~ypical of that used in the
trade and paint adhesion tests were csnducted with the
following results.
Polypropylene 100% adhesion
TPo 100% adhesion
Example 11
This example illustrates preparation of a
composition of the invention similar to that prepared in
Example 10 except a different carboxylic acid functional
resin was used.
An admixture was prepared composed of 50 grams
polyoiefin and 50 grams of a acrylic resin (60% solids)
with 90 acid number. The admixture was heated for 2
hours at 121C. 4 grams of dimethylethanolamine, 2
grams of an alkyl phenoxy poly(ethyleneoxy) alcohol and
200 grams of water were then added and an admixture
formed by high shear agitation for lO minutes. The
result of a stability test for 2 weeks and 25C was no
change. The composition was diluted with sufficient
additional water to result in a primer coating
composition typical of that used in the trade and paint
adhesion tests were conducted with the following
results.
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W093/03104 2 1 0 7 3 2 ~ P~r/Us92/o62B6
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Polypropylene 100% adhesion
TP0 100% adhesion
ExamPle 12
This example illustrates preparation of a
composition of the invention similar to that prepared in
Example lO except a different carboxylic acid functional
resin was used.
- An admixture was prepared by subjecting to high
shear 50 grams polyolefin and 50 grams of an acrylic
resin (70~ solids) with acid number 45. 4 grams of
dimethylethanolamine, 2 grams of an alkyl phenoxy
poly(ethyleneoxy) alcohol and 200 grams of water were
then added and an admixture formed by high shear
agitation for 10 minutes. The result of a stability
test for 2 weeks and 25C was heavy settling. The
composition was diluted with sufficient additional wa~er
to result in a primer coating composition typical of
that used in the trade and paint adhesion tests were
conducted with the following r~sults.
Polypropylene 20% adhesion
TP0 100% adh~sion
Exam~le 13
This example illustrates preparation of a
composition of the invention composed of a chlorinated
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W093/03104 PCT/US92/0628~
~QI~ t'~
34
polyolefin, a carboxylic acid functional resin, an amine
and water.
An admixture was prepared by subjecting to high
shear 50 grams polyolefin and 50 grams of an acrylic
resin (80% solids) with acid number 35. 4 grams of
dimethylethanolamine and 200 grams of water were then
added and an admixture formed by high shear agitation
for 10 minutes. The r~sult of a stability test for 2
weeks and 25C was heavy settling. The composition was
diluted with sufficient additional water to result in a
primer coating composition typical of that used in the
trade and paint adhesion tests were conducted with the
following results.
Polypropylene 20% adhesion
TP0 100~ adhesion
Exam~le 14
This example illustrates preparation of a
composition of the invention similar to Example 12
except that a different carboxylic acid functional resin
was used.
An admixture was prepared by subjecting to high
shear 50 grams polyolefin and 50 grams of an alkyd resin
(80~ solids) with acid number 34. 4 gra~.s of
dimethylethanolamine, 4 grams of an alkyl phenoxy
poly(ethylenoxy~ alcohol and 250 grams of water were
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- ; ~
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WO 93tO3104 ~ 3 2 8 PCT/US92/OS286
; ,: .;' . .
then added and an admixture formed by high shear
agitation for 10 minutes. The result of a stability
test for 2 weeks and 25C was heavy settling. The
composition was diluted with sufficient additional water
to result in a primer coating composition typical of
that used in the trade and paint adhesion tests were
conducted with the following results.
Polypropylene o% adhesion
TPo 100% adhesion
Exam~le 15
Thîs example illustrates preparation of a
composition of the invention similar to Example 14
except that a different carboxylic acid functional resin
was used.
An admixture was prepared by subjecting to high
shear 50 grams polyolefin and 50 grams of a saturated
polyester resin (75% solids) with acid number 68. 4
grams of dimethylethanolamlne, 2 grams of an alkyl
phenoxy poly(ethyleneoxy) alcohol and 200 grams of water
were then added and an admixture formed by high shear
agitation for 10 minutes. The result of a stability
test for 2 weeks and 25C was reversible phase
separation.
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W0~3/03104 PCT/US92/06286
3 36
Example 16
This example illustrates preparation of a
composition of the invention similar to Example 15
except that a different carboxylic acid functional resin
was used.
An admixture was prepared by subjecting to high
shear 50 grams polyolefin and 50 grams of an saturated
polyester resin (85% solids in xylene) with an acid
number in the range of 24 to 34. 4 grams of
dimethylethanolamine, 2 grams of an alkyl phenoxy
poly(ethyleneoxy) alcohol and 200 grams of water were
then added and an admixture formed by high shear
agitation for 10 minutes. The result of a stability
test for 2 weeks and 25C was reversible phase
separation.
Example 17
This example illustrates preparation of a
composition of the invention composed of a chlorinated
polyolefin, a carboxylic acid functional resin, an
20 n amine, a surfactant, an organic solvent and water~
An admixture was prepared by subjecting to high
shear 50 grams polyolefin and 50 grams of an acrylic
modified polyester resin (50% solids) with acid value in
the range of 58 to 66. 4 grams of dimethylethanolamine,
4 grams of an alkyl phenoxy poly(ethyleneoxy) alcohol, 4
WO~3/03104 PCT/US92/~6286
`: 21~3~
37
grams of xylene and 200 grams of water were then added
and an admixture formed by high shear agitation for 10
minutes. The result of a stability test for 2 weeks and
- 25C was slight settling. The composition was diluted
with sufficient additional water to result in a primer
coating composition typical of that used in the trade
and paint adhesion tests were conducted with the
followiny results.
Polypropylene 100% adhesion
lo TPO 100% adhesion
Example 18
This example illustrates preparation of a
composition of the invention similar to ~xample 16
except that a different carboxylic acid functional resin
was used.
An admixture was prepared by subjecting to high
shear So grams polyolefin and 50 grams of an acrylic
resin (70% solids) with acid number. 4 grams of
dimethyl~thanolamine, 2 grams of an alkyl phenoxy
poly(ethyleneoxy) alcohol and 200 grams of water were
then added and an admixture formed by high shear
agitatio~ for 10 minutes. The result of a stability
test for 2 weeks and 25~C was heavy settling. The
composition was diluted with sufficient additional water
to result in a primer coating composition typical of
~ . :
WO93/03104 PCT/US92/06286
~9~13~ 38
that used in the trade and paint adhesion tests were
conducted with the following results.
Polypropylene 90% adhesion
TP0 100~ adhesion
E amPle 19
This example illustrates preparation of a
composition of the invention composed of a chlorinated
polyolefin, a carboxylic acid functional resin, an
amine, a surfactant, an organic solvent and water.
An admixture was prepared by combining on a 3 roll
mill 13 grams of an imidized chlorinated polyolefin
which has a molecular weight in the range of 9,000 to
16,000, a softening point in the range of 80 to 95OC and
an amount of chlorine in the range of 18 to 22 percent,
based on the weight of the polyolefin, 13 grams of a
solid acrylic resin with acid number 230. The admixture
was cooled and pulverized into granules and the granules
heated at 121C for 1 hour. 15 grams of ammonium
hydroxide, 1 gram of a non-ionic nonyl phenoxy(ethylene
oxy) alcohol with HLB of 18.6, 10 grams of xylene and
150 grams of water were then added and an admixture
formed by high shear agitation for 20 minutes. The
composition was diluted with sufficient additional water
to result in a primer coating composition typical of
WO g3/03104 2 1 ~ ~ 3 ~i~ PCT/U~92/~628~
39
that used i~ the trade and paint adhesion tests were
conducted with the following results.
Polypropylene 100% adhesion
TP0 100% adhesion
Example 20
This example illustrates preparation of a
composition of the invention composed of a chlorinated
polyolefin, a carboxylic acid functional resin, an
amine, an organic solvent and water.
An admixture was prepared by combining at 66C 50
grams of a chlorinated polyolefin having a molecular
weight in the range of 100,000 to 150,000, a softening
point in the range of 80 to 115C and an amount of
chlorine in the range of 20 to 35 percent, based on the
weight of the polyolefin, S0 grams of a carboxylic acid
functional resin which is an alkyd resin (70% solids)
having an acid number in the range of 50 to 59, and S0
grams of xylene. 10 grams of dimethylethanolamine and
250 grams of water were then added and an admixture
formed by high shear agitation for 10 minutes. The
result of a stability test for 3 weeks and 25C was
slight settling. The composition was diluted with
sufficient additional water to result in a primer
coating composition typical of that used in the trade
: .
WO93/03104 PCT/US92/06286
3~
~o
and paint adhesion tests were conducted with the
following results.
Polypropylene 0% adhesion
TPO 70~ adhesion -
Example 21
This example illustrates preparation of a
composition of the inventi~n composed of a chlorinated
polyolefin, a carboxylic acid functional resin, an
amine, an organic solvent and water.
An admixture was prepared by combining at 66C 50
grams of a chlorinated polyolefin having a molecular
weight in the range of 110,000 to 130,000, a ssftening
point in the range of 95 to 105C and an amount of
chlorine in the range of 25 to 30 percent, based on the
weight of the polyolefin, 50 grams of a carboxylic acid
functional resin which is an alkyd resin (70% solids)
having an acid number in the range of 50 to 59, and 50
grams of xylene. 10 grams of dimethylethanolamine and
250 grams of water were then added and an admixture
formed by high shear agitation for 10 minutes. The
result of a stability test for 3 weeks and 25C was no
change. The composition was diluted with sufficient
additional water to result in a primer coating
composition typical of that used in the trade and paint
:: : ; ................................ :
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.~ WO93/03104 PCT/~S92/06286
- 21~732~
.~ .s
. . 41
adhesion tests were conducted with the following
results.
Polypropylene 0% adhesion
~; - TP0 100% adhesi~nf
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