Note: Descriptions are shown in the official language in which they were submitted.
WO93/012~ PCT/USg2/05393
21122~1)
Aqueous coatina Composition
This invention relates to aqueous compositions
useful as primers useful for enhancing the adhesion of
coatings to polyolefin substrates.
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 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. The
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 adhestion 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.
Numerous polymeric materials have been investigated
as possible components for such ashesion promoters.
Chlorinated polyolefins have been found to be very
satisfactory as the polymeric component for primer
compositions due to their cost and performance. For
example, U.S. 3,5~9,485, 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.
.
,, , , ., . ,, ,, ,, , ~ .. .. ...... , , ., . .. .. , .. .. , ,.,
Wo~3/012~ PCT/US92/05393
. . ~
- 2 --
Even though chlorinated polyolefins have been used
to prepare adhesion promoting compositions which are
entirely satisfactory, the chlorinated polyolefins had
to be formulated with an organic solvent, such as xylene
or toluene. Use of an organic solvent is undesirable
because unless elaborate solvent recovery methods are
employed 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.
One approach to overcoming the problems associated
with the use of organic solvents in primer coating
compositions has been to replace the vast majority of ^
the organic solvent. For example, a chlorinated
polyolefin containing primer coating composition which
is substantially free of organic solvents is disclosed
in W090~12656. This composition is a five component -~
composition containing a chlorina~ed polyolefin, a
surfactant, an amine, a polyol and water.
The use of the polyol in the composition disclosed
in WO~12656 can create a significant toxicity problem,
particularly if the polyol is ethylens glycol~ In
addition to the concers about polyol toxacology,
volatilization of the polyols during heat curinq of the
coating can cause polution problems similar to those
encountered when organic solvents are used.
We have now discovered an entirely satisfactory
water based chlorinated polyolefin composition which
does not contain a polyol. Thus, the elimination of the
polyol results in a composition which exhibits
significantly improved toxicity properties and is more
environDentally friendly that the polyol containing
composition.
WO93/012~ 2 1 1 2 2 3 ~ PCT/US92/05393
Broadly, the composition of this invention can be
thought of as a four component composition containing
A) a chlorinated polyolefin having a particular
range of molecuIar weight, softening point and
amount of chlorine,
(B) a nonionic surfactant,
(C) a primary, secondary or tertiary amine, and
(D) water.
The chlorinated polyolefins useful in this
invention are can be broadly described as~a chlorinated
polyolefin having a molecular weight in the range of
s,ooo to 45,000, a softening point in the range of 75 to
105C and an amount of chlorine in the range of 15 to 35
weight percent, based on the weight of the polyolefin.
These polymers are known in the art and are disclosed in
U.5. 3,579,485. In a preferred embodiment, the
chlorinated polyolefin has a molecular weig~t 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 ran~e of -~
l8 to 22 percent, based on the weight of the polyolefin.
In this invention the molecular weight of~the
chlorinated polyolefin is average number molecular
weight.
The total amount of polyolefin in the composition
is not significant as long as the relative amounts of
components (B~ and (C) are within the ranges for these
materials.
The surfactant useful in this invention can be
broadly described as a non-ionic surfactant~ By the
term "non-ionic surfactant" we mean a surfactant which
contains no positively or negatively charqe~ functional
groups.
In this invention the surfactants can have a
molecular weight of up to 500 or even higher and can
include polymeric materials. The surfactants include
W093/012~ PCT/US92/053g3
. .
~ 4 _
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 alkly phenols. Particularly preferred
classes of surfactants include alkyl phenoxy
poly(ethyleneoxy) alcohols, primary ethoxylated alcohols
and secondary ethoxylated alcohols. Preferably the
surfactant is a primary ethoxylated alcohol having 12 to
15 carbon atoms or a secondary ethoxylated alcohol -
having 11 to 15 carbon atoms.
The amount of surfactant is broadly in the range of
18 to 50 weight % and is preferably in the ranqe of 20
to 25 weight %, based on the weight of t~e chlorinated
polyolefin.
The amine component which is used in the
composition of this invention can be a primary, `
secondary or tertiary amine. Although the amine can be ;~
aromatic or aliphatic, aliphatic amines are preferred. -
In a preferred embodiment the aliphatic amine has an
amine functionality of between 1 and 3, and optionally
contains other oxygen containing functional groups. The
amines useful in this invention generally have a
molecular weight of less than 100.
2S A highly preferred group of amines are primary,
secondary and tertiary aliphatic amines having a
functionality of 1 to 3 and can be generally represented
by the general formulae:
... :
R2
Rl - ~ R3 ; or
- 35
R2 R4
Rl ~ R3 5 ; or
W093/012~ 2 1 1 2 2 ~ o PCT~US92~0s393
-- 5 --
R2 R~ R6
Rl ~ R3 _ ~ R5 ~ - R
wherein Rl = R7 are independently selected from H or
straight or branched chain alkyl, hydroxyalkyl, or
alkoxylalkyl groups of 1 to 20 carbon atoms; Rl - R7 can
additionally include a substituted alkyl group, i.e.,
where one or more of the carbons in the radical is
replaced with or has substituted thereon another
functionality, e.g., 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 the above Formulae in which Rl - R
is specifically substituted with or contains one or more
hydroxyl (-OH) functionalities.
Another group of preferred amines can be
represented by the formulae:
2S Rg Rg
R8 - (NH2)n or Rg - (~H)n or R8 - (Rlo ~ Rll)
wherein n is 1 or 2 and R8, Rg, Rlo and Rll are
independently selected from straight or branched chain
, 3S alkyl, hydroxyalkyl or alkoxyalkyl 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(oxyalkylene)diamines. Et~oxylated
or propoxylated materials are particularly preferred.
W093/012~ PCT/US92/05393
Exemplary amines preferred for use in the present
invention include:
2-amino-1-butanol;
4-amino-1-butanol; :
2-aminoethanethiol;
2-aminoheptane; -~
2-amino-1-hexanol;
6-amino-1-hexanol; ` ~-
allylamine;
2-amino-3-methyl-1-butanol; ~;
2-amino-2-methyl-1,3-propanediol; ~
2-amino-2-methyl-1-propanol; :;
2-amino-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; -
1 - [N, N-bis(2-hydroxyethyl)aminol-2-propanol;
N,N'-bis(2-hydroxyethyl)ethylenediamine;
decylamine;
1,4-diaminobutane;
l,10-diaminodecane;
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;
WOg3/012~ PCT/US92/05393
21~22~
1,3-diaminopropane;
dibutylamine;
3-(dibutylamino)propylamine;
diethanolamine;
S diethylamine;
5-diethylamino-2-pentanol;
3-(diethylamino)-1,2-propanediol;
l-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;
l-dimethylamino-2-propanol;
2-dimethylaminoethanol
3-dimethylamino-1-propanol;
3-dimethylaminopropylamine;
1,3-dimethylbutylamine;
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;
WO93/012~ PCT/US92/05393
(+)-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;
N'-isopropyl-2-methyl-1,2-propanediamine; ;~
N,N,N',N'-tetramethyl-1,4-butanediamine;
N,N,N',N'-tetramethyldiaminomethane;
N,N,N',N'-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;
triethylamine;
triisooctylamine;
triisopropyanolamine;
trimethylamine;
methylamine;
2-(methylamino)ethanol;
N-Methylbutylamine;
l-methylbutylamine;
WO93/012~ PCT/US92/0539~
2112230
2-methylbutylamine;
N-methyldiethanolamine;
N-methylethylenediamine; `~
N-methyl-1,3-propanediamine;
morpholine
nonylamine;
octylamine;
teri-octylamine;
propylamine;
2-(propylamino)ethanol;
1-tetradecylamine; and
tris~3-aminopropyl)amine. Mixtures of such materials
may a}so be employed.
Preferred amines are morpholine, triethanolamine,
ethanolamine, 2-dimethylaminoethanol, triethylamine and
ammonium hydroxide. Particularly preferred amines are
morpholine and ammonium hydroxide.
The amount of amine can be in the range of 2 to 10
weight % and preferably is in the range of 4 to 6 weight
%, based on the weight of the chlorinated polyolefin.
The compositions of this invention further 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 typically be reguired 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
W093/0l2~ PCT/US92/053g3
q~ 10~
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. Although the precise amount of water
necessary to form the required admixture can vary,
generally there must be at Ieast 40 weight % water in
the composition, based on the weight of the total
composition, in order to form an admixture with p~urable
viscosity characteristics. ~-
The compositions of this invention are
characterized as "containing" of the four components. -~
By the term "containing" we mean that the compositions
can contain other materials in major amounts. For
example, the compositions of this invention can contain
materials typically used in the paint industry to
prepare paint formu}ations, such as thickeners, wetting
agents and flow aids, pigments, resins and solvents.
The term "containing" also means that the
compositions can contain organic solvents but preferably
the compositions are substantially free of organic
solvents. Thus, the compositions of this invention
preferably contain less that 10%, more preferably less
than 5% and most preferably less than 1% organic -
solvent. The preferably small quantity of organic
WO93/012~ PCT/US92/05393
`i 2112231) ``
solvent can be present as an impurity or can be present
as in intended component of the composition.
The term "containing" also means that the
- compositions of this invention do not contain
S significant quantities of polyol. Examples of polyols
that are not present in significant quantities in the
compositions of this invention include the polyols
disclosed in WO~12656.
- The compositions of this invention can be used as
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
adaitives and then applying the diluted composition to
a polyolefin substrate to form a coating using
conventional means, such as spraying, brushing or
dipping. ~fter 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
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 resultinq admixture is applied to the
polyolefin substrate to form a single coatinq which
adheres to the polyolefin substrate. ,
WO93/012~ PCT/US92/05393
The compositions of this invention can be prepared
according to techniques well known in the art for
preparing polyolefin wax emulsions. For example, the
compositions can be prepared by introducing the four
components into an agitated pressure vessel and
agitating the components at a suitable temperature and
pressure for a suitable time. Although the particular
conditions must be selected based on the particular
equipment available, the particular components of the
composition and other factors, typically the temperature
will be in the range of 100C to 150C, the pressure in
the range of 14 psi to 70 psi, and the time will be in -
the range of 10 minutes to 45 minutes. Other
temperatures, pressures and times can be used and are
within the understanding of those skilled in the art.
In a preferred embodiment the compositions can be
prepared using a temperature of 120C, a pressure of 30
psi and a time of 20 minutes. -~
The compositions of this invention are admixtures
which have a particle size suitably small to make the
admixtures useful in coating enbodiments. Therefore,
the compositions of this invention include not only what
some authorizes call "emulsions" and "dispersions" but
include as well as all other physical forms in which the
various components can be become admixed. For example,
æome authorities characterize water containing
admixtures wherein the particle size in the range of 0.1
to lO microns as an "emulsionsn. 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
WO93/012~ PCT/US92/05393
i 21~22311
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.
In the foll~wing examples compositions of the
invention were prepared from a chlorinated polyolefin, a
nonionic surfactant, an amine and~sufficient water to
produce emulsions having 24 percent, based on the weight
of the total composition, of the chlorinated polyolefin.
The compositions were prepared by introducing the four
components into a sealed vessel equipped with a means
for agitation. Agitation was started and the contents
of the vessel heated to 120C and the resulting pressure
wàs 30 psi. This temperature and pressure was i~
maintained and the vessel was agitated for 20 minutes. ~
: "
' ExamDle 1 ;~:
This example illustrates preparation~of a
composition of the invention using a particular
chlorinated poIyolefin, one type of nonionic surfactant
and a ~econdary amine.
40 grams of a 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 95C and an amount
of chlorine in the range of 18 to 22 percent, based on -~
the weight of the polyolefin, 10 grams of a nonyl
phenoxy poly(ethyleneoxy) alcohol, 2 grams of
morpholine, and 114 grams of water were ch~rged to the ~;
vessel and the above described procedure undertaken.
The resultant composition was diluted with ~ufficient
WO93/012~ PCT/US92/05393
14 -
additional water to result in a primer coating
composition composed of 8 percent chlorinated
polyolefin, based on the weight of total composition.
This composition was applied to polypropylene. The
composition was also applied to a polyol~fin which has
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 by
baking for 10 minutes at 160DF.
Storage stability tests were conducted by visual
inspection in glass jars. The results of these tests
are as follows:
Stability at 75F for 8 weeks: Slight settling
Stability at 125F for 4 weeks: Slight settling
Freeze~thaw stability tests were conducted in
accordance with ASTM D2243 with visual inspection.
Results of this test were no change after 5 cycles.
Paint adhesion tests were conducted in accordance -~
with ASTM D 3359-83, Method A. Results of this test
were as follows:
Paint adhesion on polypropylene: 30%
Paint adhesion on TPO: lOQ%
~xam~le 2
This e~ample illustrates preparation of a
composition of the invention using the same chlorinated
polyolefin used in Example 1, the same nonionic
surfactant used in Example 1 and a tertiary amine.
40 grams of polyolefin, 10 grams of surfactant, 2
grams of 2-dimethyl-aminoethanol, and 114 grams of water
are introduced into the vessel and the above described
procedure undertaken. The resultant composition was
diluted with sufficient additional water to result in a
primer coating composition composed of 8 percent
WO93/012~ 2 1 1 2 2 3 0 PCT/USg2/05393
- 15 -
chlorinated polyolefin, based on the weight of the total
composition. This composition was applied to
polypropylene and TP0 by spraying and then dried by
baking for 10 minutes at 160F.
Storage stability tests were conducted by visual
inspection in glass jars. The results of these tests
are as follows:
Stability at 75F for 8 weeks: Slight settling
Stability at 125F for 4 weeks: Slight settling
Freeze~thaw stability tests were conducted in
accordance witASTM D2243 with visual inspection.
Results of this test were no change after 5 cycles.
Paint adhesion tests were conducted in accordance
with ASTM D 3359-83, Method A. Results of this test
were as follows:
Paint adhesion on polypropylene: 45%
- Paint adhesion on TP0: 100% ~;
.
Exa D le 3
This example illustrates preparation of a
composition of the invention using the same chlorinated
polyolefin use* in Example l, the same nonionic
1'.' ~
surfactant used in Example 1 and a tertiary amine.
40 grams of polyolefin, 10 grams of surfactant, 2 -;
2S grams of triethanol amine and 114 grams of water are
- introduced into the vesæel and the above described
procedure undertaken. The resultant composition was
diluted with sufficient additional water to result in a
primer coating composition composed of 8 percent
chlorinated polyolefin, based on the weight of total
- composition. This composition was applied to
polypropylene and TP0 by spraying and then dried by
baking for 10 minutes at 160F.
WO93/012~ PCT/US92/05393
16 -
Storage stability tests were conducted by visual
inspection in glass jars. The results of these tests
are as follows:
Stability at 75F for 8 weeks: Slight settling
Stability at 125F for 4 weeks: Slight settling
Freeze~thaw stability tests were conducted in
accordance with ASTM D2243 with visual inspection.
Results of this test were no change after 5 cycles.
Paint adhesion tests were conducted in accordance
with ASTM D 3359-83, Method A. Results of this test
were as follows:
Paint adhesion on polypropylene: 95%
Paint adhesion on TP0: 100%
Example 4
This example illustrates preparation of a
composition of the invention using the same chlorinated
polyolefin used in Example 1, the same nonionic -~
surfactant used in Example 1 and a tertiary amine.
40 grams of polyolefin, 10 grams of surfactant, 2
grams of triethyl amîne and 114 grams of water are ~
introduced into the vessel and the above described ~`
procèdure undertaken. The resultant composition was
diluted with sufficient additional water to result in a
primer coating composition composed of 8 percent
chIorinated polyolefin, based on the weight of the total ~-~
composition. This composition was applied to
polypropylene and TP0 by spraying and then dried by
baking for 10 minutes at 160F. `~
Storage stability tests were conducted by visual
inspection in glass jars. The results of these tests
are as follows:
Stability at 75F for 8 weeks: Slight settling `~
Stability at 125F for 4 weeks: Slight settling
WO93/012~ PCT/US92/05393
2112230
Freeze~thaw stability tests were conducted in
accordance with ASTM D2243 with visual inspection.
Results of this test were no change after 5 cycles.
Paint adhesion tests were conducted in accordance
with ASTM D 3359 - 83, Method A. Results of this test
were as follows:
Paint adhesion on polypropylene: 45%
Paint adhesion on TP0: 100%
Example 5
This example illustrates preparation of a
composition of the invention using the same chlorinated
polyolefin used in Example 1, another nonionic
surfactant and a secondary amine.
40 grams of polyolefin, 10 grams of a nonyl phenoxy
poly(ethyleneoxy) alcohol, 2 grams of morpholine and 114
grams of water are introduced into the vessel and the -
above described procedure undertaken. The resultant ;
composition was diluted with sufficient additional water
to result in a primer coating composition composed of 8
percent chlorinated polyolefin, based on the weight of
the total composition. This composition was applied to
polypropylene and TP0 by spraying and then dried by
ba~ing for 10 minutes at 160F.
Storage stability tests were conducted by visual
inspection in glass jars. The results of these tests -
are as follows:
Stability at 75~ for 8 weeks: Slight settling
&tability at 125F for 4 weeks: Slight settling
Freeze~thaw stability tests were conducted in
accordance with ASTM D 2243 with visual inspection.
- Results of this test were no change after 5 cycles.
Paint adhesion tests were conducted in accordance
with ASTM D 3359-83, Method A. Results of this test
were as fol~ows:
W~93/012~ PCT/US92/05393
G
- 18 -
Paint adhesion on polypropylene: 50%
Paint adhesion on TP0: 100%
Example 6
This example illustrates preparation of a
composition of the invention using the same chlorinated
polyolefin used in Example 1, another nonionic ;~
surfactant and a primary amine.
40 grams of polyolefin, 10 grams of a C11-C15
secondary ethoxylated alcohol, 2 grams of ethanolamine
and 114 grams of water are introduced into the vessel
and the above described procedure undertaken. The
resultant composition was diluted with sufficient
additional water to result in a primer coating
composition composed of 8 percent chlorinated
polyolefin, based on the weight of the total
composition. This composition was applied to --
polypropylene and TP0 by spraying and then dried by
baking for 10 minutes at 160F.
Storage stability tests were conducted by visual
inspection in glass jars. The results of these tests
are as follows: -~
Stability at 75F for 8 weeks: Slight settling
Stability at 125F for 4 weeks: Slight settling
Freeze~thaw stability tests were conducted in
accordance with ASTM D 2243 with visual inspection.
Results of this test were no change after 5 cycles.
Paint adhesion tests were conducted in accordance
with~STN D 3359-83, Method A. Results of this test
were as follows:
Paint adhesion on polypropylene: 35%
Paint adhesion on TP0: 100%
W093/0l2~ PCT/US92/053g3
21~22~0
-- 19 --
Exam~le 7
This example illustrates preparation of a
composition of the invention using the same chlorinated
polyolefin used in Example 1, the same nonion~c
surfactant used in Example 6 and a secondary amine.
40 grams of polyolefin, 10 grams of surfactant, 2
grams of morpholine and 114 grams of water are -
introduced into the vessel and the above described
procedure undertaken. The resultant composition was
diluted with sufficient additional water to result in a `i
primer coating composition composed of 8 percent `
chlorinated polyolefin, based on the weight ofthe total `~
composition. This composition was applied to `~
polypropylene and TP0 by spraying and then dried by
baking for 10 minutes at 160F. ~;
Storaqe stability tests were conducted by visual
inspection in glass jars. The results of these tests
are as follows~
Stability at 75F for 8 weeks: Slight settling
Stability at 125F for 4 weeks: Slight settling
Freeze~thaw stability tests were`conducted in
accordance with ASTM D 2243 with visual inspection.
Results of this test were no change after 5 cycles.
Paint adhesion tests were conducted in accordance
with ASTM D 3359-83, Method A. Results of this test
were as follows:
Paint adhesion on polypropylene: 50%
Paint adhesion on TP0: 100%
.
ExamDle 8
This example illustrates preparation of a
composition of the invention using the same chlorinated
polyolefin used in Example 1, the same nonionic
surfactant used in Example 7 and ammonium hydroxide.
-
WO93/012~ PCT/US92/05393
s~
- 20 -
40 grams of polyolefin, 10 grams of surfactant, 2
grams of ammonium hydroxide and 114 grams of water are
introduced into the vessel and the above described
procedure undertaken. The resultant composition was
diluted with sufficient additional water to result in a
primer coating composition composed of 8 percent
chlorinated polyolefin, based on the weight of the total
composition. This composition was applied to -~
polypropylene and TP0 by spraying and then dried by
baking for 10 minutes at 160F. ;
Storage stability tests were conducted by visual
inspection in glass jars. The results of these tests
are as follows:
Stability at 75F for 8 weeks: Slight settlinq
Stability at 125F for 4 weeks: Slight settling
Freeze~thaw stability tests were conducted in ~-~
accordance with ASTM D 2243 with visual inspection.
Result~ of this test were no change after 5 cycles. `~
Paint adhesion tests were conducted in accordance
with ASTM D 3359-83, Method A. Results of this test
were as follows:
Paint adhesion on polypropylene: 95%
Paint adhesion on TP0: 100% ~-
The use of CP 343-1, a nonionic surfactant and a
primary amine in this Example represents a more
preferred embodiment of the invention.
Example 9
This example illustrates preparation of a
composition of the invention using the same chlorinated
polyolefin used in Example 1, the same nonionic
surfactant used in Example 8 and a tertiary amine.
40 grams of polyolefin, lO grams of surfactant, 2
grams of triethanolamine and 114 grams of water are
introduced into the vessel and the above described
W093/012~ PCT/US92/05393
2112~0 ~
- 21 -
' "
procedure undertaken. The resultant composition was
diluted with sufficient additional water to result in a
primer coating composition composed of 8 percent
chlorinated polyolefin, based on the weight of the total
composition. This composition was applied to
polypropylene and TPO by spraying and then dried by
baking for 10 minutes at 160F.
Storage stability tests were conducted by visual
inspection in glass jars. The results of these tests
are as follows:
Stability at 75F for 8 weeks: Slight settling
Stability at 125F for 4 weeks: Slight settling
Freeze~thaw stability tests were conducted in
accordance with ASTM D 2243 with visual inspection.
Results of this test were no change after 5 cycles.
Paint adhesion tests were conducted in accordance
with ASTM ~ 3359-83, Method A. Results of this test ;
were as follows:
Paint adhesion on polypropylene: 80%
Paint adhesion on TPO: 100% ~
Example 10 -
This example illustrates preparation of a
composition of the invention using the same chlorinated
polyolefin used in Example 1, another nonionic -~
surfactant and a secondary amine. -
40 grams of polyolefin, 10 grams of a Cll-C15
; 30 secondary ethyloxylated alcohol, 2 grams of morpholine
and 114 grams of water are introduced into the vessel --
and the above deQcribed procedure undertaken. The `
resultant composition was diluted with sufficient
additional water to result in a primer coating
composition co~posed of 8 percent chlorinated
WO93/012~ P~T/US92/05393
22 -
polyolefin, based on the weight of the total
composition. This composition was applied to
p~lypropylene and TP0 by spraying and then dried by
baking for 10 minutes at 160F.
Storage stability tests were conducted by visual
inspection in glass jars. The results of these tests
are as follows:
Stability at 75F for 8 weeks: Slight settling
Stability at 125F for 4 weeks: Slight settling
Freeze~thaw stability tests were conducted in
accordance with ASTM D 2243 with ~isual inspection.
Results of this test were no change after 5 cycles.
Paint adhesion tests were conducted in accordance
with ASTM D 3359-83, Method A. Results of this test
were as follows:
Paint adhesion on polypropylene: 45%
Paint adhesion on TP0: 100%
Example 11
This example illustrates preparation of a
composition of the inv,ention using the same chlorinated ~
polyolefin used in Example 1, a different nonionic '
surfactant and a secondary anine.
40 grams of polyolefin, 10 grams of a C12-C15
primary ethlyoxylated alcohol, 2 grams of morpholine and
114 grams of water are introduced into the vessel and
the above described procedure undertaken. The resultant
composition was diluted with sufficient additional water ~;~
to result in a primer coating composition composed of 8
percent chlorinated polyolefin, based on the weight of
the total composition. This composition was applied to
polypropylene and TP0 by spraying and then dried by
baking for 10 minutes at 160F.
W O 93/01244 PC~r/US92/05393
21122~0
- 23 -
Storage stability tests were conducted by visual
inspection in glass jars. The results of these tests
are as follows:
Stability at 75F for 8 weeks: Slight settling ~`
Stability at 125F for 4 weekc: Slight settling
Freeze~thaw stability tests were conducted in
accordance with ASTM D 2243 with visual inspection.
Results of this test were no change after 5 cycles.
Paint adhesion tests were conducted in accordance
with ASTM D 3359-83, Method A. Results of this test
were as follows:
Paint adhesion on polypropylene: 40%
Paint adhesion on TP0: 100%
The use of CP 343-1, a nonionic surfactant and a
secondary amine in this Example represents a more
preferred embodiment of the invention.
Example 12
This example illustrates preparation of a
composition of the invention using the same chlorinated
polyolefin used in Example 1, another nonionic
surfactant and a secondary amine.
40 grams of polyolefin, 10 grams of a C12-C15
primary ethyloxylated alcohol, 2 grams of morpholine and
114 grams of water are introduced into the vessel and
the above described procedure undertaken. The resultant
composition was diluted with sufficient additional water --
to result in a primer coating composition composed of 8
percent chlorinated polyolefin, based on the weight of '
the total composition. This composition was applied to
polypropylene and TP0 by spraying and then dried by
baking for 10 minutes at 160F.
Storage stability tests were conducted by visual
inspection in glass jars. The results of these tests
are as follows:
WO93/01244 PCT/US92/05393
- 24 -
Stability at 75F for 8 weeks: Slight settling
Stability at 125F for 4 weeks: Slight settling
Freeze~thaw stability tests were conducted in
accordance with ASTM D 2243 with visual inspection.
Re~sults of this test were no change after 5 cycles.
Paint adhesion tests were conducted in accordance
with ASTM D 3359-83, Method A. Results of this test
were as follows:
Paint adhesion on polypropylene: 50%
Paint adhesion on TP0: 100%
