Note: Descriptions are shown in the official language in which they were submitted.
CA 02324628 2000-11-22
DESCRIPTION
Water Based Adhesion Promoter for Polypropylene and Method for
Coating to Polypropylene Materials Using the Promoter
This application is divided out of Canadian Patent Application
No. 2,320,276.
TECHNICAL FIELD
The present invention relates to: a water based adhesion promoter for
improving the paint adhesion to polypropylene materials; and a method for
coating to polypropylene materials using the promoter.
BACKGROUND ART
Polyolefins such as polypropylene are comparatively cheap and has
excellent properties such as formability and chemical resistance, so they are
widely used in the industrial fields including the automobile industry. The
amount thereof as used tends to increase, because their recycling is possible
and
because their prices are low. Polypropylene materials are, for example, used
for exterior decoration parts of automobiles, such as bumpers and molds, and
their surfaces are usually coated to both improve their weather resistance and
give the design property thereto.
The polypropylene material is inferior in wettability. Therefore,
when being coated with a paint, the polypropylene material undergoes the
following treatments: first, a degreasing treatment with a water base cleaning
agent and a pretreatment to enhance the wettability using a surface-active
agent, and then coating and baking treatments of a primer, and then a coating
treatment of a paint. Incidentally, the coating treatment of the primer is
carried out to enhance the adhesion of paints,
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but, in fact, as much as about 70 % of the amount of the primer as used is
lost during application and therefore is not effectively used, thus
resulting in high coating cost. Furthermore, there are problems in that:
the primer needs to be baked after being coated, so a large baking furnace
is needed and the equipment cost is therefore high.
From the above circumstances, it is desired to develop a method for
coating to polypropylene materials without primer coating.
DISCLOSURE OF THE INVENTION
OB1ECT OF THE INVENTION
An object of the present invention is to provide: a water base
adhesion promotor to enhance the paint adhesion to polypropylene
materials instead of the primer coating; and a method of coating to
polypropylene materials using the promotor.
SUMMARY OF THE INVENTION
The present inventors made various examinations and experiments
to solve the above problems. As a result, they attained the present
invention by finding that: a composition, comprising a grafted
polypropylene chloride of high adhesion to polypropylene materials, an
amine-neutralized water-soluble resin of high water resistance, and a
wettability-improving agent, could enhance the paint adhesion to
polypropylene materials, so that the primer coating could be omitted.
That is to say, a water base adhesion promotor for polypropylene,
according to the present invention, comprises:
a grafted polypropylene chloride, which includes a polypropylene
chloride moiety and a malefic anhydride moiety as bonded thereto, and
which has a chlorine content of 1525 weight % and a malefic anhydride
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moiety content of 1 ~5 weight %;
an amine-neutralized water-soluble resin;
a wettability-improving agent; and
water;
and is characterized by having:
a combination ratio of 2590 weight % as of the grafted
polypropylene chloride to the total of the grafted polypropylene chloride
and the amine-neutralized water-soluble resin;
a combination ratio of 2.56.0 weight % as of the wettability-
improving agent to the entirety of the promotor; and
a solid content of 210 weight % of the entirety of the promotor.
A method for coating to polypropylene materials, according to the
present invention, comprises:
a pretreatment step in which a polypropylene material is beforehand
cleaned, and then the above water base adhesion promotor is applied,
then dried; and
a coating step in which a paint is coated to the material after the
pretreatment step.
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, each component, constituting the present invention
water base adhesion promotor for polypropylene, is explained in detail,
and then the water base adhesion promotor for polypropylene and the
method for coating to polypropylene materials are explained.
(Grafted polypropylene chloride):
The grafted polypropylene chloride, as used in the present
invention, is a component to enhance the adhesion to polypropylene
materials. The grafted polypropylene chloride is a polypropylene
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derivative which includes a polypropylene chloride moiety and a malefic
anhydride moiety as bonded thereto, and is usually used in the form of
an emulsion having the high handling property.
The polypropylene chloride moiety is a moiety comprising a
polypropylene having at least one chlorine atom as a substituent. In
addition, the malefic anhydride moiety is a moiety as obtained by grafting
malefic anhydride, and has a cyclic acid anhydride group (deriving from
malefic anhydride) and/or two free carboxyl groups.
The grafted polypropylene chloride is a product by reacting a
polypropylene upon malefic anhydride and chlorine to internally graft the
polypropylene, and is, for example, produced by reacting chlorine and
malefic anhydride upon a polypropylene. Incidentally, whichever of
chlorine and malefic anhydride may be reacted earlier than the other. The
reaction with chlorine is, for example, carried out by introducing a
chlorine gas into a solution including a polypropylene. In addition, the
reaction with malefic anhydride is, for example, carried out by reacting
malefic anhydride upon a polypropylene (or its chloride) in the presence
of a peroxide.
The chlorine content in the grafted polypropylene chloride is in the
range of 15-25 weight %o, preferably 1822 weight %. In the case where
the chlorine content is less than 15 weight %o, the melting point of the
grafted polypropylene chloride is so high that the crystallization easily
occurs and that the emulsification is difficult, thus resulting in
depression of the storage stability of the resultant water base adhesion
promotor. On the other hand, in the case where the chlorine content
exceeds 25 weight %, the grafted polypropylene chloride is noncrystalline,
thus resulting in depression of the adhesion and the water resistance.
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The malefic anhydride moiety content in the grafted polypropylene
chloride is in the range of 1 ~5 weight %, preferably 34.5 weight %. In the
case where the malefic anhydride moiety content is less than 1 weight %,
the emulsification is difficult, thus resulting in depression of the storage
stability of the resultant water base adhesion promotor. On the other
hand, in the case where the malefic anhydride moiety content exceeds 5
weight %, the acid anhydride group content is too much, thus resulting
in depression of the adhesion and the water resistance.
The weight-average molecular weight of the grafted polypropylene
chloride is not especially limited, but is preferably in the range of
20,000100,000, more preferably 30,00080,000. In the case where the
weight-average molecular weight is less than 20,000, the promotor might
swell with a solvent for a top paint, so that the adhesion might be
deteriorated. On the other hand, the weight-average molecular weight
exceeds 100,000, the viscosity of the resultant water base adhesion
promotor might be so high that the emulsification might be difficult and
that the storage stability might be low.
(Amine-neutralized water-soluble resin):
The amine-neutralized water-soluble resin, as used in the present
invention, is a resin as water-solubilized by neutralization with an
amine, and is a film-formable component having high water resistance.
Incidentally, for example, water-soluble resins, which are not obtained by
the amine neutralization, such as polyethylene glycol and
polyvinylpyrrolidone, merely have low water resistance, because, even
after film formation by drying, such water-soluble resins remain and
retain its water solubility. In comparison, the amine-neutralized water-
soluble resin, as used in the present invention, displays high water
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resistance, because it volatilizes the amine in the drying step, and thus
loses the water solubility.
The amine-neutralized water-soluble resin, as used in the present
invention, is not especially limited if it is a resin as neutralized with an
amine, and examples thereof include products by neutralization of resins
such as urethane resins, alkyd resins, and acrylic resins. These may be
used either alone respectively or in combinations with each other.
Examples of the amine, as used for the above neutralization, include
ammonia, triethylamine, and monoethanolamine. These may be used
either alone respectively or in combinations with each other.
(Wettability-improving agent):
The wettability-improving agent, as used in the present invention,
is a component to enhance the wettability of the water base adhesion
promotor upon polypropylene materials (having much water-
repellency). The use of this wettability-improving agent enables a coating
film, resultant from the grafted polypropylene chloride and the amine-
neutralized water-soluble resin as above, to adhere well to polypropylene
materials.
The wettability-improving agent is not especially limited, but
examples thereof include ethylene glycol hexyl ether,
dimethylpolysiloxane-polyethylene glycol block polymer (Polyflow KL-
245). These may be used either alone respectively or in combinations
with each other. Particularly, ethylene glycol hexyl ether improves the
wettability, and further does not lower the water resistance because it
volatilizes in the drying step and therefore does not remain in the
resultant coating film. In comparison, materials as conventionally used
to enhance the wettability, such as alkylphenylpolyethylene glycol, do not
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volatilize in the drying step, but remain in the coating film, thus
depressing the water resistance.
(Other components):
The water base adhesion promotor of the present invention may
further comprise the following other components: resin emulsions such
as acrylic emulsions, urethane emulsions, and polyvinyl chloride
emulsions; inorganic pigments such as titanium white and carbon black,
extenders such as talc and precipitated barium; and various organic color
pigments.
(Water base adhesion promotor for polypropylene and method for
coating):
The water base adhesion promotor for polypropylene, according to
the present invention, needs to comprise the grafted polypropylene
chloride, the amine-neutralized water-soluble resin, the wettability-
improving agent, and water (these components are explained in detail
above), and may further comprise the above other components if
necessary. Conditions, such as order, for mixing these components are
not especially limited.
The combination ratio of the grafted polypropylene chloride, as
contained in the present invention water base adhesion promotor for
polypropylene, is in the range of 2590 weight %, preferably 3050 weight
%, of the total (the total solid content) of the grafted polypropylene
chloride and the amine-neutralized water-soluble resin. In the case
where the combination ratio of the grafted polypropylene chloride is less
than 25 weight %, the adhesion and the water resistance are both low. On
the other hand, in the case where the combination ratio of the grafted
polypropylene chloride exceeds 90 weight %, the adhesion and the water
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resistance as well as the film formability are low.
The combination ratio of the wettability-improving agent is in the
range of 2.56.0 weight %o, preferably 3.04.0 weight %, of the entirety of
the water base adhesion promotor. In the case where the combination
ratio of the wettability-improving agent is less than 2.5 weight %, the
polypropylene material crawls with the water base adhesion promotor, so
uniform coating is impossible. On the other hand, in the case where the
combination ratio of the wettability-improving agent exceeds 6.0 weight
%, the storage stability of the water base adhesion promotor is low, and
the grafted polypropylene chloride aggregates to precipitate.
The solid content of the present invention water base adhesion
promotor for polypropylene is the nonvolatile matter and is in the range
of 210 weight %, preferably 4--6 weight %, of the entirety of the water
base adhesion promotor. In the case where the solid content is less than 2
weight %, the film thickness of the coating film resultant from the water
base adhesion promotor is too thin, so the adhesion and the water
resistance are both low. On the other hand, in the case where the solid
content exceeds 10 weight %, marks of sagging are left after coating the
water base adhesion promotor, so the resultant coating film has
unevenness, and the appearance is therefore unfavorable.
The method of coating to polypropylene materials, according to the
present invention, comprises the pretreatment step and the top coating
step.
The pretreatment step includes the steps of cleaning the
polypropylene material and applying the above water base adhesion
promotor and then drying the material.
The cleaned polypropylene material is, for example, prepared by the
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following steps (1)~(3) in the pretreatment step.
(1) A step of spray-washing a polypropylene material with warm
water of 6080 °C.
(2) A step of degreasing the polypropylene material with an alkaline
cleaning agent after the above step (1).
(3) A step of washing the alkaline cleaning agent off the
polypropylene material by spray-washing the polypropylene material
with deionized water after the above step (2).
The coating film of the water base adhesion promotor is formed on
the surface of the polypropylene material by applying the water base
adhesion promotor onto the cleaned polypropylene material and then
drying the material. This applying step may be accomplished by, for
example, pouring, atomized spraying, dipping and/or showering. The
choice of a given applying step for any specific part may be based on
economic, process, and quality considerations. For some parts it is
preferable to hold the polypropylene material upright after applying step
and to then dry the material. For other parts, notably those in which the
coating material may pool and/or sag after application, it is preferable to
hold the polypropylene material at a slight angle, preferably about
1020°
and most preferably about 15° from the vertical during drying.
During the holding step, it is preferred to maintain an atomosphere
within the environment to promote even coating after drying, For
example, the holding environment may be preferably maintained at a
temperature of between about 1530 °C and about 4070% relative
humidity and most preferably between 2025 °C and about 4070%
relative humidity. This holding step is commonly referred to as flash
condition.
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The method for drying after the flash condition is not especially
limited, and the drying is usually carried out with ovens such as hot-air
drying ovens, long-wave infrared ovens, and short- wave infrared ovens
at about 60120 °C for about 515 minutes. The thickness of the dried
film, as obtained from the water base adhesion promotor in the above
way, is preferably in the range of 0.11 Vim.
The coating step includes the step of coating a top paint to the above
material after the pretreatment step and is carried out by coating the top
paint and then drying it.
The type of the top paint is not especially limited, but examples
thereof include one-component melamine baking paints, two-
component urethane paints, and one-component lacquer paints.
The method of coating the top paint is not especially limited, but the
spray coating is preferable. The method for drying the coated top paint is
not especially limited, and the drying is usually carried out with ovens
such as hot-air drying ovens, long-wave infrared ovens, and short-wave
infrared ovens at 70120 °C for 20-60 minutes. The thickness of the
dried
film, as obtained from the top paint in the above way, is not especially
limited, but is preferably in the range of 1560 ~.m.
In the method for coating to polypropylene materials, the use of the
above water base adhesion promotor in the pretreatment step enables the
omission of the primer coating. Therefore, the productivity in the
coating step is largely improved.
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention is more specifically illustrated by
the following examples of some preferred embodiments in comparison
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with comparative examples not according to the invention. However,
the invention is not limited to the below-mentioned examples.
Hereinafter, the unit "part(s)" is "weight part(s)."
(EXAMPLE 1 )
First, 6 parts (nonvolatile matter: 1.8 parts) of a grafted
polypropylene chloride emulsion (chlorine content = 16 weight %, malefic
anhydride moiety content = 1.5 weight %, nonvolatile matter = 30 weight
%), 12 parts (nonvolatile matter: 4.2 parts) of a water-soluble urethane
(made by Sanyo Kasei Co., Ltd., U-Coat UWS-145, nonvolatile matter = 35
weight %) (as the amine-neutralized water-soluble resin), 3 parts of
ethylene glycol hexyl ether (as the wettability-improving agent), and 79
parts of water were mixed in this order under stirring, thus preparing
water base adhesion promotor (1) of 100 parts in entirety. Incidentally,
the ratio of (grafted polypropylene chloride)/(amine-neutralized water-
soluble resin) (ratio in terms of solid content) was 30/70, and the
combination ratio of ethylene glycol hexyl ether was 3 weight % of the
entirety of water base adhesion promotor (1), and the solid content of
water base adhesion promotor (1) was 6 weight % as determined from its
nonvolatile matter.
A polypropylene material was spray-washed with warm water of
6080 °C, and then degreased by spray-washing with an alkaline cleaning
agent (Surf Cleaner PL-1000, made by Nippon Paint Co., Ltd.), and then
spray-washed with deionized water of room temperature to wash the
alkaline cleaning agent off, thus preparing a washed polypropylene
material. This polypropylene material was immersed into water base
adhesion promotor (1), and then left standing upright at room
temperature for 1 minute, and then dried at 80 °C for 10 minutes. Next,
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an isocyanate curing type polyester resin paint (R-763, made by Morton
Nippon Coatings Co., Ltd.) (as the top paint) was spray-coated to the above
polypropylene material, and the coated paint was then dried at 80 °C
for
40 minutes, thus obtaining coated product (1). Incidentally, the dried-film
thickness was in the range of 1525 Vim.
The properties of water base adhesion promotor (1) were evaluated
by the following methods. The results thereof are shown in Table 1.
(Evaluation method):
1. Adhesion:
A cross-cut test was carried out for the coated product in accordance
with JIS K5400. First, 100 cross-cuts of 2 mm x 2 mm were prepared to
carry out the cellophane tape peeling test, and the evaluation was made
on the following evaluation standard:
O: no peeling-off was seen;
x: one or more cross-cuts peeled off.
2. Water resistance:
The coated product was immersed into warm water of 80 °C for 3
hours, and water on the surface was then wiped off. Thereafter, the
coated product was left for 1 hour, and the above adhesion evaluation
was then carried out. The evaluation standard was the same as that for
the adhesion.
3. Appearance:
A polypropylene material of 7.5 cm x 10 cm was prepared, and then
treated with the water base adhesion promotor, and then stood upright,
and then dried at 80 °C for 30 minutes, thus evaluating whether a
sagging
mark was seen or not with the eye on the following evaluation standard:
O: no sagging mark;
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x: a sagging mark was seen.
4. Storage stability:
A polypropylene material was immersed into the water base
adhesion promotor as had been stored at room temperature for 1 month,
thus evaluating whether an aggregate was seen or not with the eye on the
following evaluation standard:
~: no aggregate;
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x: an aggregate was seen.
(EXAMPLES 2~4 AND COMPARATIVE EXAMPLES 1 ~7)
Water base adhesion promoters (2)~(4) and comparative water base
adhesion promoters (1)~(7) were prepared to evaluate their properties in
the same way as of Example 1 except that the type and the combination
amount of the grafted polypropylene chloride emulsion and the
combination amounts of the water-soluble urethane and the ethylene
glycol hexyl ether were changed to those as shown in Tables 1 and 2.
Tables 1 and 2 further show the ratio of (grafted polypropylene
chloride)/(amine-neutralized water-soluble resin) (ratio in terms of solid
content) and the combination ratio and the solid content of the ethylene
glycol hexyl ether.
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Table 1
Example
1 2 3 4
Grafted 1.8 1.5 4.0 4.0
I polypropylene
Water chloride
base (CPO)
adhesion Water-soluble4 1 6 1
2 5 0 0
promotor urethane . . . .
(AU)
(parts)*
1
Ethylene 3.0 5.0 3.0 4.0
glycol
hexylether
(EGHE)
Chlorine 16 21 25 21
content
of CPO
(weight
%)
Malefic 1.5 4.5 1.0 4.5
anhydride
content
of
CPO (weight
%)
CPO/AU 30/70 50/50 40/60 80/20
(ratio
in terms
of
solid
content)
Combination 3 5 3 4
ratio
of EGHE
(weight
%)
Solid 6 3 10 5
content
(weight
%)
Adhesion 0 0 0
EvaluationWater resistance
results Appearance ~ 0
Storage stability
* 1 Amount of each component in 100 weight parts of water base adhesion
promotor; the balance is
water.
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Table 2
Comparative
Example
1 2 3 4 5 6 7
Grafted 1.0 9.5 1.8 1.8 1.8 0.5 6.0
polypropylene
Water chloride
base (CPO)
adhesion Water-soluble4.0 0.5 4.2 4.2 4 0 1
2 5 0
promotor urethane . . .
(AU)
(parts)*
1
Ethylene 3.0 3.0 3.0 3.0 7.0 3.0 3.0
glycol
hexyl ether
(EGHE)
Chlorine 21 16 27 21 21 21 21
content
of CPO
(weight
%)
Malefic 4. 1. 1.5 7 .0 4. 4. 4.
anhydride 5 5 5 S 5
content
of
CPO (weight
%)
CPO/AU 20/80 95/5 30/70 30/70 30/70 50/50 50/50
(ratio
in terms
of
solid
content)
Combination 3 3 3 3 7 3 3
ratio
of EGHE
(weight
%)
Solid 5 10 6 6 6 1 12
content
(weight
%)
Adhesion x x x x 0 x
EvaluationWater resistancex x x x 0 x
results Appearance ~ ~ ~ ~ 0 ~ x
Storage stability--- --- --- --- x --- ---
* 1 Amount of each component in 100 weight parts of water base adhesion
promotor; the balance is
water.
<Evaluation results>:
Examples 1 ~4 all provide excellent results with regard to the
adhesion, the water resistance, the appearance, and the storage stability,
and enable the omission of the conventional primer coating step.
Comparative Examples 1 and 2 provide inferior results with regard to the
adhesion and the water resistance, because the combination ratio of the
grafted polypropylene chloride is out of the claimed range. Comparative
Example 3 provides inferior results with regard to the adhesion and the
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water resistance, because the chlorine content of the grafted
polypropylene chloride is too large. Comparative Example 4 provides
inferior results with regard to the adhesion and the water resistance,
because the malefic acid moiety content is too large. Comparative
Example 5 provides inferior results with regard to the storage stability,
because the combination ratio of the ethylene glycol hexyl ether is too
large. Comparative Example 6 provides inferior results with regard to the
adhesion and the water resistance, because the coating film resultant
from the water base adhesion promotor is thin due to too small solid
content. Comparative Example 7 provides inferior results with regard to
the appearance, because the coating film resultant from the water base
adhesion promotor is thick due to too large solid content.
INDUSTRIAL APPLICATION
The use of the present invention water base adhesion promotor for
polypropylene in the pretreatment step prior to coating of polypropylene
materials enables the omission of the primer coating, and further,
provides excellent results with regard to the adhesion of the paint and the
water resistance and appearance of the coating film.
The present invention method for coating to polypropylene
materials involves the use of the above water base adhesion promotor in
the pretreatment step and therefore enables the omission of the primer
coating and the great improvement of the productivity of the coating
step. In addition, in this method, the water base adhesion promotor that
does not remain on the polypropylene material can be recovered and
recycled through the process, providing economical advantages to the
process.
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