Note: Descriptions are shown in the official language in which they were submitted.
WO 96105260 PCTlEP95103145
Water-dispersible acrylic graft copolymer, method for
making it and water-based paint
[Industrial field of application]
The present invention relates to novel water
dispersible graft copolymers which have a main chain
l0 which forms a stabilizing layer and side chains which
constitute a dispersed layer and are useful as paint-
film-forming components, to a method for making them,
and to water-based paint which includes an afore-
mentioned water-dispersible acrylic graft copolymer.
[Prior art]
Water-based paints have come to be widely adopted
instead of solvent-based paints on account of their
superiority from the point of view of environmental
protection and worker safety. For example, in the field
of metallic paint painted onto the outside panels of
cars, etc., solvent-based paints using large quantities
of organic solvents are being progressively replaced by
water-based paints in which water is used as the
solvent.
The hydrophillic resins generally employed in
water-based paints or water-based paint composit~.ons
are random copolymers having a quantity of carboxyl
groups necessary to render them hydrophillic; and
dispersions formed by neutralizing such a polymer with
a basic substance and dispersing it in an aqueous
medium are used in water-based paint.
However, although water-based paints from such
aqueous dispersions, such as water-based paint from an
aqueous dispersion of an acrylic type random copolymer
for example, are suitable for improving appearance
because pigment dispersion and the rheological
properties of the paint liquid are good and they form
paint films of outstanding gloss and smoothness, the
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WO 96105260 PGTlEP95103145
durability of the paint film is low because of the high
acid number of the acrylic type polymers. When the
viscosity of water-based paints obtained from these is
adjusted to make it suitable for painting, the solids
concentration thereof decreases dramatically, and
painting faults such as drip and uneven application,
etc., are prone to be produced.
In order to improve such points, water-based paint
compositions have been offered which include an acrylic
graft copolymer from a hydrophillic component and a
hydrophobic component. For example, in Japanese
Unexamined Patent 56-49760 water-based paint
compositions are described which contain as the resin
component an acrylic graft copolymer obtained by
copolymerizing an acrylic polymer of acid number 40-200
containing unsaturated groups, obtained by reacting an
unsaturated monomer containing a glycidyl group with a
carboxy-functional acrylic polymer, and a monomer
combination combining an a,(i-ethylenic unsaturated
carboxylic acid and another copolymerizable unsaturated
monomer to give an acid number of 530, such that the
difference in acid number in the reaction product
composition is 25-200, and by this means making a graft
copolymer which has an acid number of 15-40 and a glass
transition temperature of -10°C to 70°C.
However, in making an acrylic graft copolymer such
as described above it is necessary first to react a
carboxy-functional acrylic polymer with an unsaturated
monomer containing a glycidyl group, and then to graft
copolymerize a monomer combination; therefore the
manufacturing process is complicated by~ a 2-stage
reaction process. Moreover, in the preliminary reaction
of an acrylic polymer with an unsaturated monomer
containing a glycidyl group, it is necessarily to
employ a polymerization stopper so that the grafted
chains are not extended by free radical polymerization
of the unsaturated monomer, and in the subsequent
reaction it is necessary to add a large quantity of
CA 02196181 2005-08-30
29018-83
3
polymerization initiator so that free radical polymerization
will proceed to form a grafted chain even though the
polymerization stopper may be present; and polymerization
side reactions become prone to occur. When an acrylic graft
copolymer made by the method described above is used as the
main resin in a water-based paint the paint film formed may
yellow due to contamination of the paint with the
polymerization stopper. Improvement in ease of painting
would also be desirable.
The present invention provides novel and useful
water-dispersible acrylic graft copolymers which can be
employed as the paint-film-forming resin (main resin) of
water-based paint, which when so used enable the formation
of paint films which have excellent paint performance traits
such as resistance to water (water resistance) and
resistance to chemicals (chemical resistance), etc., and
excellent finished appearance, and have outstanding ease of
application and storage stability.
The present invention also provides a method
whereby the acrylic graft copolymers can be made efficiently
and simply by a single-stage reaction starting from an
acrylic copolymer.
The present invention also provides water-based
paints containing an acrylic graft polymer described above,
which can form paint films which have excellent paint
performance traits such as water-resistance and chemical
resistance, etc., and excellent finished appearance, and
have outstanding ease of application and storage stability.
The present invention is the following acrylic
graft copolymers, a method for making them and water-based
paint.
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WO 96/05260 PCT/EP95I03145
(1) Water-dispersible acrylic graft copolymers
characterized in that they are graft copolymers made by
reacting
an acrylic copolymer of acid number 35-120 mg
ROH/g, hydroxyl group number 50-150 mg ROH/g, glass
transition temperature -20 to +50°C and number average
molecular mass 4500-9000 comprising a copolymer of a,(3
ethylenic unsaturated monomers (a), and
a monomer combination combining an a,[3-ethylenic
unsaturated monomer containing a glycidyl group (b1)
and an a,[3-ethylenic unsaturated monomer containing a
hydroxyl group (b2) to give an acid number of S15 mg
ROH/g and a hydroxyl group number of 50-150 mg KOH/g
(b),
in the proportions (a) / (b) (weight ratio) = 10/90
to 60/40 with (b1)/(a) (mol ratio) 0.4-1.5,
and have an acid number of 10-30 mg ROH/g, a
hydroxyl group number of 50-150 mg ROH/g, a glass
transition temperature of -20 to +50°C and a number
average molecular mass of 10,000-100,000.
(2) A method for making a water-dispersible
acrylic graft polymer, characterized in that
an acrylic copolymer of acid number 35-120 mg
ROH/g, hydroxyl group number 50-150 mg ROH/g, glass
transition temperature -20 to +50°C and number average
molecular mass 4500-9000 comprising a copolymer of a,(3-
ethylenic unsaturated monomers (a), and
a monomer combination combining an a,[3-ethylenic
unsaturated monomer containing a glycidyl group (b1)
3o and an a,(3-ethylenic unsaturated monomer containing a
hydroxyl group (b2) to give an acid number of 515 mg
ROH/g and a hydroxyl group number of 50-150 mg KOH/g
(b) ,
are reacted in the proportions (a)/(b) (weight
ratio) = 10/90 to 60/40 with (bl)/(a) (mol ratio)
0.4-1.5,
to make a water-dispersible graft copolymer having
an acid number of 10-30 mg KOH/g, a hydroxyl group
number of 50-150 mg KOH/g, a glass transition
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WO 96105260 PCT/EP95103145
temperature of -20 to +50°C and a number average
molecular mass of 10,000 to 100,000.
(3) Water-based paint characterized in that it
contains an acrylic graft copolymer according to (1)
above.
Water-dispersible- acrylic graft copolymers of the
present invention (also called simply acrylic graft
copolymers hereafter) are graft polymers in which the
to main chain is a hydrophillic acrylic copolymer (a)
which hydrates when dispersed in water and forms a
stabilizing layer, and hydrophobic side chains which
form a dispersed layer when dispersed, and a monomer
combination (b) is polymerized to this main chain to
give hydrophobic side chains which form a dispersed
layer when dispersed, grafted on via ether linkages.
In the present invention the expressions "(meth)
acrylic acid" and "(meth)acrylate" respectively signify
"acrylic acid and/or methacrylic acid" and "acrylate
and/or methacrylate".
The essential components of the acrylic copolymer
which forms a stabilizing layer (a) are an a,(3-
ethylenic unsaturated monomer containing a carboxyl
group and an a,[3-ethylenic monomer containing a
hydroxyl group; and it can be made from these a,(i-
ethylenic unsaturated monomers, with the addition if
necessary of other copolymeri2able unsaturated
monomers, by a known method of solution polymerization
in the presence of a suitable polymerization catalyst.
Examples of a,(i-ethylenic unsaturated monomers
containing a carboxyl group include acrylic acid,
methacrylic acid, crotonic acid and malefic acid, etc.
These can be employed singly or in combinations of 2 or
more.
Examples of a,(3-ethylenic unsaturated monomers
containing a hydroxyl group include hydroxyalkyl esters
of (meth)acrylic acid such as 2-hydroxyethyl (meth)-
acrylate, 2-hydroxypropyl (meth)acrylate and 3-hydroxy-
2i9bi$~
WO 9G/05260 PCTIEP95I03145
propyl(meth)acrylate, etc., polyether polyols such as
polyethylene glycol and polypropylene glycol, etc.,
monoethers with a.,[3-ethylenic unsaturated monomers
containing a hydroxyl group such as 2-hydroxyethyl
(meth)acrylate, etc., and lactone-modified a,(3-
ethylenic unsaturated monomers in which 1-10 mol of a
lactone such as e-caprolactone or y-butyrolactone, etc.,
has been added to a hydroxyalkyl ester of (meth)acrylic
acid, etc. These can be used singly or in combinations
l0 of 2 or more.
Other copolymerizable monomers which can be used
if necessary include esters - for example C1-C1a alkyl
esters of (meth)acrylic acid such as methyl (meth)-
acrylate, ethyl (meth)acrylate, propyl (meth)acrylate,
isopropyl (meth)acrylate, butyl (meth)acrylate, hexyl
(meth)acrylate, octyl (meth)acrylate and lauryl (meth)-
acrylate, etc., and alkoxyalkyl esters of (meth)acrylic
acid such as methoxybutyl (meth)acrylate, methoxyethyl
(meth)acrylate and ethoxybutyl (meth)acrylate, etc.;
amides of acrylic acid or methacrylic acid - amides of
(meth)acrylic acid such as g1-methylol(meth)acrylamide
and Z1-isobutoxymethylol(meth)acrylamide, etc.; and
aromatic vinyl compounds such, as styrene, a
methyl'styrene and vinytoluene, etc.
An acrylic copolymer (a) can be obtained by
performing solution polymerization according to an
ordinary method using these monomers in the presence of
3o a known polymerization initiator such as azobis(iso-
butyronitrile), benzyl peroxide, ~-butyl peroxy-
benzoate, ~-butyl peroxide or t-butylperoxy-2-
ethylhexanoate, etc. This reaction is performed in such
a way that the acrylic co-polymer (a) that is produced
has an acid number of 35-120 mg KOH/g, and preferably
50-110 KOH/g, a hydroxyl group number of 50-150 mg
KOH/g, and preferably 60-150 mg KOH/g, a glass
transition temperature of -20 to +50°C, and preferably
-20 to +30°C, and a number average molecular mass of
4500-9000, and preferably 4800-7000.
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WO 96/05260 PCT/P,P95f03145
When the acid number of the acrylic copolymer (a)
is less than 35 mg KOH/g its action as a stabilizing
layer is inadequate, and therefore the acrylic graft
copolymer is prone to agglutinate in aqueous media and
storage properties are inferior; and when it exceeds
120 mg KOH/g it becomes highly hydrophillic, so that
the water-resistance of paint films formed from water
based paint containing a resulting acrylic graft
1o copolymer are inferior.
When the hydroxyl group number of the acrylic
copolymer (a) is less than 50 mg KOH/g the chemical
resistance of the resulting paint films is inferior
because resulting acrylic acid graft copolymers do not
have enough crosslinking points with amino resins used
as hardening agents; and when it exceeds 150 mg KOH/g
hydrophillic properties are conferred on the resulting
acrylic graft copolymers, and therefore the water
resistance of paint films formed from paint including
them is inferior.
When the glass transition temperature of the
acrylic copolymer (a) is less than -20°C the resulting
acrylic graft copolymers that are obtained are prone to
conglutinate in aqueous media and the storage stability
of the aqueous dispersion is inferior, and when the
glass transition temperature exceeds +5D°C the
softening temperature of the resulting acrylic graft
copolymers becomes high and therefore the smoothness of
films of water-based paints containing them is
inferior.
When the number average molecular mass of the .
acrylic copolymer (a) is less than 4500 it cannot form
an adequate stabilizing layer, and the storage
stability of aqueous dispersions of the resulting
acrylic graft copolymers is inferior; and when it
exceeds 9000 the viscosity of aqueous dispersions of
the resulting acrylic graft copolymers becomes high,
the paint solids content of water-based paints prepared
from them is lowered and they are inferior when it
comes to dripping.
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WO 96105260 PCT/EP95103145
The essential components of the monomer
combination (b) reacted with an acrylic copolymer (a)
described above are an a,(3-ethylenic unsaturated
monomer containing a glycidyl group (b1) and an a,[3-
ethylenic unsaturated ethylenic monomer containing a
hydroxyl group (b2), combined if necessary with other
copolymerizable monomers which can copolymerize with
these (b3), to give an acid number of 515 mg KOH/g, and
preferably 510 mg ROH/g, a hydroxyl group 50-150 mg
ICOH/g, and preferably 50-120 mg KOH/g.
Examples of a,~3-ethylenic unsaturated monomers
containing a glycidyl group (b1) include glycidyl
(meth)acrylate and allyl glycidyl ether, etc. a,[3-
ethylenic unsaturated monomers containing a hydroxyl
group (b2) and other copolymerizable molecules (b3)
include those given as examples in the discussion of
the aforementioned acrylic copolymer (a).
When the acid number of the monomer combination
(b) exceeds 15 mg KOH/g the resulting acrylic graft
copolymers become water-soluble, their viscosity
becomes high, and the ease of application of water-
based containing them becomes poor. Water-resistance is
also inferior.
When the hydroxyl group number of the monomer
combination (b) is less than 50 mg KOH/g the number of
crosslinking points between the resulting acrylic graft
copolymers and the amino resins that are used as
hardening agents is inadequate, and therefore the
chemical resistance of the resulting paint is inferior,
and when it exceeds 150 mg KOH/g the polymer becomes
highly hydrophillic, and the water-resistance of the
resulting paint films is inferior.
Acrylic graft copolymers of the present invention
are obtained by reacting an aforementioned acrylic
copolymer (a) with the monomer combination (b). This
reaction is performed under the conditions that the
ratio of the acrylic copolymer (a) and the monomer
combination (b) (a)/(b) (weight ratio) is 10/90 to
60/40, and preferably 20/80 to 40/60, and (b1)/(a) (mol
ratio) is 0.4-1.5, and preferably 0.8-1.2.
219~1~1
R'O 96105260 PCTJEP95103145
The number of mols of the acrylic copolymer (a)
can be decided by calculation from the polyethylene-
equivalent number average molecular weight determined
by ordinary gel permeation chromatography.
S When (a)/(b) (weight ratio) is less than 10/90 an
adequate stabilizing layer cannot be formed, and the
storage stability of aqueous suspensions of the
resulting acrylic graft copolymers is inferior, and
when it exceeds 60/40 the viscosity of aqueous
dispersions of the graft copolymers obtained becomes
exceedingly high, the painted solids content of water-
based paints containing such an acrylic graft copolymer
is lowered and drip properties are inferior.
Similarly, when the quantity of a,~i-ethylenic
unsaturated monomer containing a glycidyl group (b1)
included relative to the acrylic copolymer (a) as a mol
ratio is less than 0.4, grafting with component (b)
becomes inadequate and the resulting acrylic graft
polymers will not disperse readily in aqueous
2o dispersion, or the storage properties of the aqueous
dispersion obtained will be poor; and when it exceeds
1.5 gelling is produced and it is impossible to make an
acrylic graft copolymer.
The reaction of an acrylic copolymer (a) with a
monomer combination (b) can be performed by solution
polymerization of a separately made acrylic copolymer
(a) with a monomer combination (b) in an organic
solvent by a known method, or performed by solution
polymerization in an organic solvent by a known method
as a continuation of making the acrylic copolymer (a),
by adding the monomer combination (b) to the reaction
liquor from making the acrylic copolymer (a). The
latter is preferred because in this case the
manufacture of the acrylic copolymer (a) can be made
continuous with the manufacture of the acrylic graft
copolymer.
As the organic solvent above, toluene, methyl
isobutyl ketone, methyl ethyl ketone, ethylene glycol
monoethyl ether (ethyl Cellosolve), ethylene glycol
monobutyl ether (butyl Cellosolve), propylene glycol
2196181
WO 96105260 PCTIEP95103145
monopropyl ether or propylene glycol monoethyl ether,
etc., or a mixture thereof can be used. When performed
as a continuation of making the acrylic copolymer (a),
the organic solvent used in making the acrylic polymer
(a) can be employed as it stands, or new solvent can be
added.
As the polymerization initiator the same polymer-
ization initiators given as examples in the case of
making the acrylic copolymer (a) can be used. When
performed as a continuation of making the acrylic
copolymer (a) only the quantity lacking needs to be
added.
It is desirable that the total concentration of
the acrylic copolymer (a) and the monomer combination
(b) in the reaction liquid is 30-90 wt%, and preferably
50-80 wt%, and that the concentration of polymerization
initiator relative to the total quantity of monomers is
0.1-l0 wt%, and preferably 0.5-5 wt%. It is also
desirable that the reaction temperature is 20-180°C,
2o and preferably 40-160°C, and that the reaction time is
1-l0 hours.
The acid number, hydroxyl group number, glass
transition temperature and number average molecular
weight of the acrylic graft copolymer that is obtained
can be adjusted by selection of the type and quantity
of acrylic copolymer (a) and monomer combination (b),
and the reaction conditions such as reaction
temperature, reaction time and the type and quantity of
the initiator employed.
In the reaction above, free radical polymerization
of the monomer (bl)-(b3) proceeds simultaneously with
ring-scission addition of the carboxy groups of the
acrylic copolymer (a) and the glycidyl groups of the
component containing a glycidyl group (b1), to perform
graft polymerization and make an acrylic graft
copolymer in a single reaction stage.
In a method such as in the aforementioned Japanese
Unexamined Patent 56-49760 in which an acrylic
copolymer is first reacted with a monomer containing a
glycidyl group it becomes necessary to use a
2i961~1
WO 96105260 PCT/EP95/03145
polymerization stopper in order to stop the radical
polymerization of the monomer containing a glycidyl
group, but in the present invention a polymerization
stopper is not necessary because the addition reaction
and free radical reaction occur simultaneously;
therefore the yellowing of paint films caused by the
polymerization.stopper is prevented.
Acrylic graft copolymers of the present invention
are graft copolymers made as described above, and are
water-dispersible acrylic graft copolymers having an
acid number of 10-30 mg KOH/g, and preferably 15-30 mg
KOH/g, a hydroxyl group number of 50-150 mg KOH/g, and
preferably 50-120 mg KOH/g, a glass transition
temperature of -20 to +50°C, and preferably -10 to
+30°C, and a number average molecular weight of 10,000-
100,000, and preferably 10,0D0-50,000.
When the acid number of the acrylic graft
copolymer is less than 10 mg KoH/g it becomes difficult
to disperse in aqueous media and storage properties are
inferior; and when it exceeds 30 mg KOH/g the viscosity
of the resulting aqueous dispersions becomes
exceedingly high, and this lowers the painted solids
content of paint containing it and gives inferior drip
properties.
When the hydroxyl group number of the acrylic
graft copolymer is less than 5o mg KoH/g the number of
crosslinking points between the acrylic graft copolymer
and amino resins used as curing agents is inadequate,
and therefore the water-resistance of the resulting
paint films is inferior; and when it exceeds 150 mg
KOH/g the water resistance of the resulting paint film
is inferior because the acrylic graft copolymer becomes
very hydrophillic.
When the glass transition temperature of the
acrylic graft copolymer is less than -20°C the acrylic
graft copolymers become prone to conglutinate in
aqueous media, and the storage properties of the
aqueous dispersions obtained are inferior; and when it
exceeds +50°C the smoothness of the paint films formed
219~1~1
R'O 96105260 PCTIEP95I03145
from water-based paints containing the acrylic graft
copolymers is inferior.
When the number average molecular weight of the
acrylic graft copolymer is less than 10,000 the
chemical resistance and water resistance of paint films
formed from Water-based paints containing these acrylic
graft copolymers are inferior; and over 100,000 is
undesirable because of the possibility of gel formation
when making water-based paint.
After making an acrylic graft copolymer of the
present invention as described above, it can be made
into an aqueous dispersion by removing the solvent,
neutralizing it with a basic substance, and dispersing
in an aqueous medium. Dispersion in an aqueous medium
IS can be performed by an ordinary method: for example, it
can be performed by neutralizing at least 40% of the
carbDxyl groups present in the acrylic graft copolymer
by using methylethanolamine, etc. The aqueous medium is
preferably one in which water accounts for 40-80 wt%.
Aqueous dispersions so obtained can be employed as
they stand as water-based paint, but they can also be
made into water-based paint by concentration or
dilution, or by being powdered and then resuspended. An
acrylic graft copolymer can be used on its own as the
paint-film-forming component of the water-based paint;
but further combination with a hardening agent to
prepare a water-based paint (Water-based paint
composition) in which it is the main resin component is
preferred because paint-forming performance is further
improved.
As the hardening agent it is desirable that an
amino resin, and particularly an amino resin of a
number average molecular mass of <_1000, is employed.
Examples of such amino resins available -as commercial
33 products include Cymel 301, Cymel 303, Cymel 325 and
Cymel 327 (trade names Mitsui Scitech), Nikalac MW-30
and Nikalac MX43 (trade names Sanwa Chemicals) and
Yuban 120 (Mitsui Toatsu Chemicals). The number average
molecular weight of the amino resin is the
4o polyethylene-equivalent number average molecular weight
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WO 96/05260 1 ~ PCT/EP95103145
determined in the ordinary way by gel permeation
chromatography.
If necessary, hydrophillic- organic solvents can be
added to water-based paint of the present invention.
Examples of such hydrophillic organic solvents include
ethylene glycol monoethyl ether, ethylene glycol mono-
butyl ether, diethylene glycol monobutyl ether,
ethylene glycol monohexyl ether, propylene glycol
monomethyl ether, propylene glycol monoethyl ether and
propylene glycol monobutyl ether, etc.
If necessary metallic pigments, inorganic pigments
and/or organic pigments, etc., can also be added. There
is no specific restriction as to the method used for
adding pigments, and this can be performed by a prior
known method. Moreover, if necessary additives such as
acid catalysts and surface preparation agents, etc.,
conventionally added to water-based paints can also be
included.
Water-based paints of the present invention have
outstanding storage stability and are also
outstandingly easy to apply; and the paint films
obtained from them have excellent paint film
performance traits such as water-resistance, chemical
resistance, durability and smoothness, etc.
Water-based paints of the present invention can be
employed as a base coat; in this case, the same methods
can be implemented as with ordinary water-based base
coating, and they are particularly suitable for the
prior known 2 coats 1 bake method in which the base
coat and top coat are applied wet on wet and the two
are baked simultaneously.
They can be applied by any method of painting such
as roller coating, brush, or spray application, etc.
They can be baked at 60-180°C for 10-60 minutes, and
preferably at 110-150°C for 15-30 minutes.
[0034]
Benefits such as those described can be obtained
when the ranges of values hitherto explained in the
present invention, for example the properties of the
WO 96105260 PCT/EP95I03145
~a
acrylic copolymer (a) and the monomer combination (b),
the proportions of these in the reaction, the reaction
conditions, and the physical properties of the acrylic
graft copolymer, etc., are within the recorded ranges
of values; and particularly outstanding benefits are
obtained when the ranges of the various values are
within the ranges of values described as preferred
ranges of values.
[8enefita of the invention]
1o Water-dispersible acrylic graft copolymers of the
present invention are novel and are useful as paint-
forming resins for water-based paints. Since acrylic
graft copolymers of the present invention are
constituted from a main chain which forms a stabilizing
layer, and side chains which form a dispersed layer,
they are outstandingly water-dispersible, and
consequently when such an acrylic graft copolymer is
used as a paint-film-forming resin in a water-based
paint the resulting water-based point does not
agglutinate and has excellent storage properties. Since
acrylic graft copolymers of the present invention are
also made by reacting in specified proportions
specified acrylic copolymers (a) and monomer copolymers
(b) having specified properties, and also have
specified properties, when such acrylic graft
copolymers are used as paint-film-forming resins in
water-based paints the ease of application of the
resulting water-based paints is excellent, and paint
films formed from them have outstanding paint film
performance traits such as water resistance and
chemical resistance, etc " and also an excellent
finished appearance.
Since the method for making water-dispersible
acrylic graft copolymers of the present invention
reacts in specified proportions specified acrylic
copolymers (a) and monomer combinations (b) having
specified properties, it enables acrylic graft
copolymers above to be made simply and efficiently from
acrylic copolymers (a) by a single-stage reaction.
WO 96105260 a ~ PCT/EP95/03145
Since water-based paints of the present invention
contain an acrylic graft copolymer above as a paint-
film-forming resin they have outstanding ease of
application and storage properties, and moreover paint
films formed Prom them have outstanding paint film
performance traits such as water resistance and
chemical resistance, etc., and also an excellent
finished appearance.
[Embodiments]
The present invention will next be explained in
more detail by means of practical embodiments; however,
the present invention is not limited in any way by
these examples. In the examples "parts" signifies
"parts by weight" unless it is indicated otherwise. The
method of painting and the methods for evaluating paint
film appearance, paint film performance traits and
storage stability are as follows.
[Method of painting
As the test sheets for painting the following was
used. Thus, zinc-phosphate-treated sheet steel electro
coated with electrocoat paint (Aqua No. 4200; trade
name Nippon Oils & Fats) to give a dry film thickness
of 20 ;Cm and baked at 185°C for 2o minutes, and then
air sprayed with a mid-coat paint ("Haiepiko°' No. 100CP
sealer; trade name Nippon Oils & Fats) to give a dry
film thickness of 40~m and baked at 140°C for
2o minutes, was used.
Water-based paint compositions prepared in the
different embodiments were applied to these test sheets
by the known 2 coats 1 bake method. Thus, the water
based paint Was spray coated on in a painting
environment of temperature 25°C and relative humidity
75% to give a dry film thickness of 15 Vim, and then
dried by heating at a temperature of 80°C for 10
minutes, after which it was cooled to room temperature
and then a commercial clear topcoat paint (Belcoat No.
6000; trade name Nippon Oils & Fats) was spray coated
on to give a dry film thickness of 40 ~,m, followed by
setting for 10 minutes and then baking at 140°C for 30
21~~181
VVO 96105260 PCTIEP95/03145
I6
minutes. The object being painted was held vertical in
the same position throughout.
(Paint film appearance]
1) 60° gloss
By the JIS 85400 (1990) 7.6 mirror surface gloss.
2) Smoothness
The paint film was evaluated with the naked eye as
follows:
o : favourable
Lo x : inferior
3) Drip
Assessed from the length of drip under a 10-mm
diameter hole opened in the painted sheet, when painted
to give a dry film thickness of 30 Vim, according to the
following criteria.
o : < 2 mm
x : Z2 mm
(Paint film performance traits]
1) water resistance
Assessed by observation of the state of the
surface with the naked eye after immersion for 4 hours
in hot water of 290°C, according to the following
criteria.
o : no abnormality
x : blistering
2) Chemical resistance
Assessed by observation of the state of the
surface with the naked eye after immersion for 1 hour
in regular gasoline at 40°C, according to the following
criteria.
o : no abnormality
x : shrinkage
(Storage stability]
The change (%) in the viscosity of the water-based
composition after storage at 40°C for 20 days relative
to the initial viscosity (ps/6 rpm (B viscosimeter))
Was assessed according to following criteria.
o : <~15%
x : 2~15%
2~~b~:81
R'O 96105260 PCT/EF95103145
17
Embodiments 1-8
1) Making an acrylic graft copolymer
Methyl isobutyl ketone 56.4 parts was put into a
reaction vessel provided with a stirrer, a temperature
regulator, a cooling tube and a dropping device,
stirred as the temperature was raised, and refluxed.
Next, a mixture of 2-hydroxyethyl methacrylate
41.8 parts, acrylic acid 11:6 parts, g-butyl acrylate
l0 93.6 parts, 2-ethylhexyl methacrylate 33.0 parts and
azobis(isobutyronitrile) 3.6 parts was added dropwise,
requiring 2 hours. Stirring under reflux Was continued
for a further 2 hours to complete polymerization
(hereafter this reaction process is referred to as
"Process 1").
The resin obtained was an acrylic copolymer having
an acid number of 5o mg KOH/g, a hydroxyl group number
of 100 mg KOH/g, a glass transition temperature of
-20°C and a number average molecular mass of 5000.
2o Next, methyl isobutyl ketone 328.6 g was put into
this resin solution, and it was refluxed under
stirring. Then a mixture of glycidyl methacrylate 5.1
parts, 2-hydroxyethyl methacrylate 97.5 parts, methyl
methacrylate 200.2 parts, H-butyl acrylate 122.3 parts
and azobis(isobutyronitrile) 6.3 parts were added
dropwise, requiring 2 hours. The addition and
polymerization reaction was completed by continuing
stirring for a further 5 hours (hereafter this reaction
process is called "Process 2").
3o The resulting acrylic graft copolymer A-1 was a
resin solution having an acid number of 12 mg KOH/g, a '
hydroxyl group number of 100 mg ROH/g, a glass
transition temperature of +13°C and a number average
molecular mass of 42,000.
Acrylic graft copolymers A-2 to A-8 were also made
by the same method according to the formulations of
Table 1 and Table 2. Their properties are shown in
Table 1 and Table 2.
~I9~181
VUO 96f05260 PCT/EP95/03145
18
[Table 1j
Table 1
crylic graft copolymer No. A-1 A-2 A-3 A-4
rocess 1 (parts by weight)
Solvent composition
Methyl isobutyl ketone' 56.4 155.2 - 76.4
Toluene - - 770
Monomer composition
2-Hydroxyethyl methacrylate 41.8 55.7 27.9 41.8
Acrylic acid 11.6 15.4 15.4 15.4
n-Butyl acrylate 93.6 124.9 28.7 3.2
2-Ethylhexyl methacrylate 33.0 44.0 48.0 47.6
Styrene - - - 12.0
Initiator
Azobis(isobutyronitrile) 3.6 4.8 -
t-Butylperoxy-2-ethyl-
hexanoate - - 3.0
t-Butyl peroxybenzoate - - - 3.6
Reaction temperature reflux reflux reflux reflux
rocess 2
Solvent composition
Methyl isobutyl ketone 328.6 227.6 - 303.0
Toluene - - 156.9
Ethylene glycol monoethyl
ether - - 150.0
Monomer composition
2-Hydroxyethyl methacrylate 97.5 83.6 111.4 110.9
Acrylic acid - - - -
Methyl methacrylate 200.2 171.6 228.8 134.9
n-Butyl acrylate 122.3 104.8 139.8 138.2
Styrene - - - 96.0
Glycidyl methacrylate 5.1 7.0 3.5 3.5
Initiator
Asobis(isobutyronitrile) 6.3 5.4 -
t-Butylperoxy-2-ethylhexanoate - 96 -
-
t-butyl peroxybenzoate - - - 12.0
Reaction temperature reflux reflux 120C reflux
roperties of component (a)
btained by Process 1
Acid number (mg KOH/g) 50 50 100 100
Hydroxyl number (mg KOH/g) 100 100 100 150
Glass transition temp. (C) -20 -20 0 +30
Number av. molecular mass 5000 4900 4900 4800
Properties of monomer
ombination (b) polymerized
in Process 2
Acid number (mg KOH/g) 0 0 0 0
Hydroxyl number (mg KOH/g) 100 I00 100 100
Glass transition temp. (C ) +30 +30 +30 +30
SUBSTITUTE SHEET (RULE 26y
W O 96!05260 PCTIEP95103145
erties of the acrylic
t copolymer
Acid number (mg KOH/g) 12 15 18 20
Hydroxyl number (mg KOH/q) 100 100 100 107
Glass transition temp. (C) +13 +8 +23 +30
Number av. molecular mass 42000 32000 34000 31000
Components (a)/(b) (w/w) 30/70 40/60 20/80 20/80
Components (bl)/(a) (mol/mol)I.0 1.0 1.0 1.0
2196181
W O 96105260 PCT/EP95103145
[Table 2] 20
Table 2
crylic graft copolymer No. A-5 A-6 A-7 A-8
rocess 1 (parts by weight)
Solvent composition
Methyl isobutyl ketone 95.5 - - -
Toluene - 77.0 77.0 115.5
Monomer composition
2-Hydroxyethyl methacrylate 34.8 27.9 27.9 41.8
Acrylic acid 9.6 15.4 15.4 23.1
n-Butyl acrylate 78.1 76.7 76.7 43.2
2-Ethylhexyl methacrylate 27.5 - - 719
Styrene - - -
Initiator
Azobis(isobutyronitrile) - -
t-Butylperoxy-2-ethyl-
hexanoate - 3.0 3.0 4.5
t-Butyl peroxybenzoate 4.5 -
Reaction temperature reflex reflex reflex reflex
rocess 2
Solvent composition
Methyl isobutyl ketone 285.5 - - -
Toluene - 154.5 310.5 264.3
Ethylene glycol monoethyl
ether - 150.0 -
Monomer composition
2-Hydroxyethyl methacrylate 52.2 111.4 111.4 97.5
Acrylic acid 5.8 - - -
Methyl methacrylate 209.4 228.8 228.8 200.2
n-Butyl acrylate 92.6 139.8 139.8 122.3
Styrene 90.0 - - -
Glycidyl methacrylate 3.5 3.5 3.5 5.2
Initiator
Asobis(isobutyronitrile) - -
t-Butylperoxy-2-ethyl-
hexanoate -
t-Butyl peroxybenzoate 11.3 12.0 6.0 10.5
Reaction temperature reflex reflex reflex reflex
Properties of component
(a) obtained by Process 1
Acid number (mg KOH/g) 50 100 100 100
Hydroxyl number (mg KOH/gy 100 120 120 100
Glass transition temp. (C) -20 -16 -16 0
Number av. molecular mass 4800 4900 4900 4900
Properties of monomer
combination (b) polymerized
in Process 2
Acid number (mg KOH/g) 10 0 D 0
Hydroxyl number (mg KOH/g) 50 100 100 100
Glass transition temp. (C) +50 +30 +30 +3D
P'TtFf~ SNP? (fl~.E 28~
X196181
W O 96105260 PCTIEF95103145
erties of the acrylic
t copolymer
Acid number (mg KOH/q) 20 18 18 27
Hydroxyl number (mg KOH/g)59 104 104 100
Glass transition temp. +29 +20 +20 +20
(C)
Number av. molecular mass 31000 21000 43000 27000
Components (a)/(b) (w/w) 25/75 20/80 20/80 30/70'
Components (bl)/(a) (mol/mol)0.8 1.0 1.0 1.0
21~ g~~~ ~
WO 96105260 °2 ~ PCT/EP95103145
2) Making an aqueous disøers9.on
Ethylene glycol monobutyl ether 80.0 parts was
added to 533.0 parts of acrylic graft copolymer A-1
obtained in 1) above, and then 205.0 parts of methyl
isobutyl ketone were evaporated off under decreased
pressure. Dimethylethanolamine 3.o parts (carboxyl
group equivalent 0.5) was added to this polymer
solution, and after stirring, 588.9 parts of deionized
water were added and stirred until it became
homogeneous, to obtain a milky white low-viscosity
aqueous dispersion B-1 of acrylic graft copolymer A-1.
Aqueous dispersions B-2 to B-8 of acrylic graft
copolymers A-2 to A-8 were made by the same method
using the combinations shown in Table 3. The nature of
the aqueous dispersions obtained is shown in Table 3.
WO 96105260 PCTIEP95I03145
[Table 3j 23
>'
o
3y
,
a0 m O O O a0N O
M
x ,
y
N N
, v0 m
G1 Q V1 0~ O a7 M
m m
'
N V1 ~,
M N
M
3 >
'
O
3
tv 1~ O O O ~DvY O
x ,.
.y N
N
~T vYv0 r1 O
H
N N ~ M
N N
M
3>
9
o
3 ~
,o vo o O ,oa N M
%
x
, , n , , H
a a .o .-i
o
~
a7 6 ,n ~ ~ " a
a.
'
~M N
N
M
3 >
O
'
T C
V1 V1 O O O ,-1Ov ,~~
~
N N
, , m o .o . vin ,-,
a0 - o H
M
Ci a ,~ N uo~tL V
o,
~M~
N
3 >'
O
G
of O O O O ~ ~ x ,.O~
N %
v ' H
, t u1 , V1vD r1 O
1 O
Cp 6 a ~ N ,tiV V
11
~H~
N
'
' b
3 '
x'0
3
e "n o o voa ,
~,'m~
w ~
x
H
m m
07 6 ,mn n-1~ v~1~ o
H
~ W
.,
a
M
3 >
'O
N
_ ~
_ o b
3 ~
N N o 0 o m N >,
~
x m y
'
, N
, ,~., m o ' "'o H ' d,
w
cp < ,n N u1 u ri M
~ M
% H
> V'
'CS
9
0
G >,
r1 v-1 O O O C N T
~
x F. 19
,..,
N
~ M H
Ci G' u1 N v~1y' ~ >~
W A' 3~ b
'
M M
3 >
'
O m
O N
W
~
m a C 7 ~ C~ > f0
~ , M
.
N O M n-1 H r1 N Tl r1H N
H a o 'O 3 I
v
m . a % m m o m H O G
a m a, G a m m
p 8 a ut ~ m m >
%
a . ow >,u o>H o% m m ,ca. a a
we
m m a L ~ ~
m
M H H 00 O~ M
mH
V e0H W ~0H N N m'i7 H m 'O W b
V
m O m m >> M H m m r-1m O 'U
C1 N V OgCL m T N Nm ~~
~ Nm'OH
C M uM>> m0 ,~mm G G t M m'G r1 N
QJ O rl'iG M M .~ '~ G m m 1tC H O
,O H N M
m T O T O T t O H O m O O m
O O N N %
7 Hp. OY,G. tG LLV rIT7m E M VOL
az C ~ ~ a m x C a x m
o 8 69 H ~ P o
a
SUBS'f111FCE SHEET (RtJIE 2B)
R'O 96/05260 ~ ~ ~ PCT/EP95/03145
24.
3) Preparation and performance testing of water-based
paint compositions
Water-based paint compositions were prepared based
on the combinations shown in Table 4. Thus, water-based
paint compositions of 65 wt% solids were prepared by
adding an aqueous dispersion B-1 to B-8 obtained in 2)
above, an amino resin (Cymel 327 (Mitsui SciTech) trade
name), titanium dioxide (Teika Rutile Titanium Dioxide
JR602 (trade name Teika RR), dimethylethanolamine and
deionized water. For evaluation using the method of
application described previously, these water-based
paints were prepared to a viscosity of 3 t 1 ps using a
B viscosimeter at 6 rpm, by adding deionized water.
The results for the appearance of the resulting
paint films and of performance tests, and also results
for storage stability are shown in Table 5.
WO 96105260
PCT/EP95/03145
(Table 4]
N O O O t~ I~ f~ n
H
, , , , i , N O O O O~ t0 ~O CV
, ~ u1 O ,(1 ~D M M v0
N ~ O
M r1
,"~ ,n O O O vY ~Y ~ N
""~,oo, N O 0 0 0 ~T v1'O
N u1 O u1 i~ I~ IW O
M 'f1 O
'i
u1 O O O vY O O u1
, , , , , W , ' H h O O N
N ~ O ~
M N O
"W t1 O O O ~ n
'
V1 ,,,,N,,, ,-IO O O
u1 O N ~ 1~ h v0
M 'n O
-I ~t1O O O ~ M tW D
n ' . m , , , , .-~O O O O a0 07 N
N u1 O V1 1~ M M VD
t1 'f1 O
,l1O O O ~ I~ [v i~
M ' ' ~ ' ' ' n W O O O O v0 tD N
1
N u1 O n!1 1~ M M tD
M 'n O
'i
,f1O O O ~ M M M
N ' ~ ' ' ' ' ' m -t O O O O M M N
N u'1O u1 Iy Y d' ~O
M u1 O
ri
M O O O vo ao ao V1
.-1N , , , , , , , ,-tO O O O 1~ n d
u1 O u1 1~ O ~O
M O
n n n n n n n
a a a a a a a
m x x x m x
oD eD eD m o0
M M M .,a .,..~.,a M
N '~ ~ '~ ~ ~ 3 3 3
3 3 3 3
, , ,
, , , , ' p o o a p
. . a p
ca o7 as a7 w w w ap
M N N N N N N
t1 la H H H H H
N vE N N N N ~f
w w w w w w w
.. .. .. .. .. ..
>,
C
M
S-, W
O
M
N c1 U
N
ro a ~
o ., o m d
ar ..
~
>
~ ~ ~ N
N
.C M r~ 8 3 ro
i'1 an
a ,~ a ro m ~
d ro ~ ,~ y ro ~
ro..
d' e ro
N v
~ m N N
O
, O U ...M
b I ~
O r1
d N N '~,O O Oro N
-0 .O X13. R ~ 1! .~ H ..i 11 M
Ij t3
,
H W d d ~ U H W A D E W
SI.BSTITtFrE SHEET (RtRE 26~
W 0 96!05260 PCT/EP95103145
[Table 5]
Table 5
Embodiment 1 2 3 4 5 6 7 8
No.
Dry film Hase coat (pm) 15 15 14 15 15 16 15 15
thickness Clear coat (um) 41 41 40 41 40 40 40 39
Painted 60 gloss 94 93 96 95 94 95 94 96
appearance Smoothness O 0 O O O O 0 O
Drip properties 0 0 0 0 0 0 0 0
Paint film Water resistanceO 0 0 0 O O 0 O
performance Chemical
resistance O 0 0 0 O O O O
Storage stability 0 0 0 0 O 0 O 0
Comparison Examples 1-10
1) Making an acrylic graft copolymer
Acrylic- graft copolymers a-1 to a-10 were made by
the same method as in Embodiments 1-8 1) according to
the formulations shown in Table 6 to Table 8. Their
properties are shown in Table 6 to Table 8.
WO 96/05260 PCTIEP95103145
[Table 6]
Table 6
crylic graft copolymer No. a-1 a-2 a-3 a-4
Process 1 (parts by weight)
Solvent composition
Methyl isobutyl ketone
Toluene 95.5 95.5 95.5 95.5
Monomer composition
2-Hydroxyethyl
methacrylate 27.9 34.8 3.5 69.6
Acrylic acid 15.5 19.4 19.4 19.4
n-Butyl acrylate 106.6- 50.3 50.4
n-Butyl methacrylate - 34.5 - 10.6
Methyl methacrylate - 61.3 76.8
2-Ethylhexyl methacrylate - - -
Initiator
t-Butyl peroxybenzoate 4.5 4.5 4.5 4.5
Reaction temperature reflux reflux reflux reflux
rocess 2
Solvent composition
Methyl isobutyl ketone - - -
Toluene 286.7286.6 286.6 286.6
Monomer composition
2-Hydroxyethyl
methacrylate 104.4104.4 104.4 104.4
n-Butyl methacrylate - - -
Acrylic acid - - -
Methyl methacrylate 214.5214.5 214.5 214.5
n-Butyl acrylate 131.1131.1 131.1 131.1
Glycidyl methacrylate 4.3 4.4 4.4 4.4
Initiator
t-Butylperoxy-2-ethyl-
hexanoate 9.0 9.0 9.0 9.0
Reaction temperature reflux reflux reflux reflux
Properties of component
(a) obtained by Process 1
Acid number (mg ROH/g) 80 100 100 100
Hydroxyl number (mg ROH/g) 80 100 10 200
Glass transition temp. (C) -28 +70 +30 +10
Number av. molecular mass 4900 4800 4800 4700
Properties of monomer
combination (b) polymerized
in Process 2
Acid number (mg ROH/g) 0 0 0 0
Hydroxyl number (mg ROH/g) 100 100 100 100
Glass transition temp. (C) +30 +30 +30 +30
WO 96105260 ~ PCTIEP95I03145
2~
erties of the acrylic
t copolymer
Acid number (mg ROH/g) 22 22 22 22
Hydroxyl number (mg ROH/g) 95 100 78 125
Glass transition temp. (C ) +13 +39 +30 +25
Number av. molecular mass 31000 33000 31000 31000
Components (a)/(b) (w/w) 25/75 25/75 25/75 25/75
Components (bl)/(a)
(mol/mol) 1.0 1.0 1.0 1.0
~~~1~8~1i
WO 96105260 PCT/EP95103145
[Table 7]
Table 7
Acrylic graft copolymer No. a-5 a-6 a-7
Process 1 (parts by weight)
Solvent composition
Methyl isobutyl ketone - 95.5 19.1
Toluene 95.5 - -
Monomer composition
2-Hydroxyethyl methacrylate 34.8 34.8 7.0
Acrylic acid 19.4 19.4 3.9
n-Butyl acrylate 35.8 35.8 7.1
n-Butyl methacrylate - - -
Methyl methacrylate - - -
2-Ethylhexyl methacrylate 60.0 60.0 12.0
Initiator
t-Butyl peroxybenzoate 9.0 4.5 0.9
Reaction temperature reflux reflux reflux
Process 2
Solvent composition
Methyl isobutyl ketone - 286.7 370.1
Toluene 273.2 - -
Monomer composition
2-Hydroxyethyl methacrylate 104.4 104.4 132.2
n-Butyl methacrylate - - -
Acrylic acid - 17.3 -
Methyl methacrylate 214.5 170.7 271.7
n-Butyl acrylate 131.1 157.5 166.1
Glycidyl methacrylate 8.8 4.4 0.9
Initiator
t-Butylperoxy-2-ethyl-
hexanoate 13.5 9.0 9.0
Reaction temperature reflux reflux reflux
Properties of component (a)
obtained by Process 1
Acid number (mg ROH/g) 100 100 100
Hydroxyl number (mg ROH/g) 100 100 100
Glass transition temp. (C) 0 0 0
Number av. molecular mass 2400 4700 4700
roperties of monomer
ombination (b) polymerized
'n Process 2
Acid number (mg ROH/g) 0 30 0
Hydroxyl number (mg ROH/g} 100 100 100
Glass transition temp. (C) +30 +20 +30
W'O 96105260 ~ ~ ~ ~ ~ ~' ~ PCTIEP95103145
perties of the acrylic
ft copolymer
Acid number (mg ROH/g) 22 44 4
Hydroxyl number (mg ROH/g) 100 100 100
Glass transition temp. (C) +22 +15 +28
Number av. molecular mass 9300 31000 24000
Components (a)/(b) (w/w) 25/75 25/75 5/95
Components (bl)/(a) (mol/mol) 1.0 1.0 1.0
2196181
R'O 96105260 PCT/EP95/03145
[Table 8j
Table 8
crylic graft copolymer No. a-8 a-9 a-10
rocess 1 (parts by weight)
Solvent composition
Methyl isobutyl ketone 95.5 95.5 95.5
Toluene - - -
Monomer composition
2-Hydroxyethyl methacrylate 34.8 34.8 34.8
Acrylic acid 28.9 19.4 19.4
n-Butyl acrylate 50.6 35.8 35.8
n-Butyl methacrylate - - -
Methyl methacrylate
2-Ethylhexyl methacrylate 35.7 60.0 60.0
Initiator
t-Butyl peroxybenzoate 4.5 4'.5 4.5
Reaction temperature reflux reflux reflux
rocess 2
Solvent composition
Methyl isobutyl ketone 286.6 286.6 286.6
Toluene - - -
Monomer composition
2-Hydroxyethyl methacrylate 104.4 41.8 208.8
n-Butyl methacrylate - - -
Acrylic acid - - -
Methyl methacrylate 214.5 264.0 132.0
n-Butyl acrylate 131.1 144.2 109.2
Glycidyl methacrylate 4.4 4.4 4.4
Initiator
t-Butylperoxy-2-ethyl-
hexanoate 9.0 9.0 9.0
Reaction temperature reflux reflux reflux
roperties of component (a)
btained by Process 1
Acid number (mg ROH/g) 150 100 100
Hydroxyl number (mg ROHIg) 100 100 100
Glass transition temp. (C) 0 0 0
Number av. molecular mass 4700 4700 4700
iProperties of monomer
;combination (b) polymerized
in Process 2
Acid number (mg ROH/g) 0 0 0
Hydroxyl number (mg ROH/g) 100 40 200
Glass transition temp. (C) +30 +30 +30
PCTlEP9s103145
wo 9s~osxso ~ ~ ~ b 181
erties of the acrylic
t copolymer
Acid number (mg ROH/g) 34 22 22
Hydroxyl number {mg ROH/g) 100 55 175
Glass transition temp. (C) +22 +22 +22
Number av. molecular mass 31000 31000 31000
Components (a)/(b) {w/w) 25/75 25/75 25/75
Components (bl)/(a)
(mol/mol) 1.0 1.0 1.0
2) Making aqueous dispersions
Aqueous dispersions b-1 to b-10 of acrylic graft
copolymers a-1 to a-10 were prepared from the acrylic graft
copolymers a-1 to a-10 obtained in 1) above by the same
method as in Embodiments 1-8 2) using the combinations
shown in Table 9. However, when acrylic graft copolymer a-7
was used and the final 589.0 parts of deionized water were
added and stirred a precipitate was produced, and a stable
dispersion could not be obtained (Comparison Example 7)
2396181
W O 96J05260 PC1'IEP95103145
33
[Table 9j
o O o ,o a L
N Nn ~ ' i, m
m O m N d .a p
YL, mn.l
m N m
u1 u wt O
t U C'
t 0 Z i,-.
m.,.
.a .w
r 'a
O O O vo a >, o C
.,L.,
~
, m o m . .n a ~.ya ~.i
.La
i o
7
O
um1 m N N L l
V P
~'
m~ 3.
si
> o
m ro o 0 0 ,o a ,~ 3
"9,
n m O m , eD .am V Q, i~
I~ m u1 ~
N in~ ; ~ G
b
O O O O O
N
f7 n0 ,~ ~ O a0 fl
N V1
C
O
0 0 0 .a m ~ 7
',
..; o ..; , ,-im , a
"
' o ~
f7 61 1f1 N ~ "'~ m
m
N N ~.i
m
.1
O O O v0 d A m ..i
~
m O . .n a' m
n i p 7
'Y
d n . a ,
m N m .
..,
7
~
~
b f1 ~ v S
1 '
~
" m
".
> D
b
d d O O O V d Ty ~
~ A
. . m O . m m a .r.1i03 ,-1
m V ~
m
7 N N ~i b
~N
> U si
a m
>> C) ~1
O O O V 3 rm .,way~ N m
. . . ~ N
~ O ' m "~".C b C
O U
~'
p d .n N m S i'~ i~ m
m ~
w b m
> d 'Q
m i1 m
N N O O
O ,D d >o m
a
m o . n u, ~
w
y
o
a . VI m O
m O
~ ,
o.
t m . w ~ z s ~' G 3 O
n ~
"'
" m
, .
> a m >,
m
t m
~' ~
'o ~
3
0 0 0 .o d r, m m
..
.
m o . m ~; a ", i ~ a
y.
>
.. >,
m . m
o ~
.O m ~ w N t 3.r i
~ ~ U d 4
> ~.
l
m m as
1
O ~
i m .
s. m .
.
O > W O.
m m W a ' .-~I
m m
m ~ m- ,
t .N N
.r .-n ~ o w 3 0~ ~.~
s. 9 O.
a o V
a
a m m m
m L g , C m w ~I C
G A ~ V L m m > L m m
r m
a w ow >,u > > H m m m s a ~ ~ D R
a
m $a ~~ a i m
m m ' "
mm
. . o ..
v . i m m v s. m .on
eo w ao w o w o
s. ..
m o O m i~ ..i 4 m ..1m O E
V V C N m m >~ N m r1
n ~ m 9 S.
O ,. u,.~ .a m o t .,m a ~ ..~ N e~
, m ~ g ~ s
o -~..c.a.. a,c m m L a r. o~
.aa ~ m
o >,O 7>~O >v ,C041 700 O 300
3 6. s. a t a a ~
. a ~
t $ V ,-mo a a ~ a
~ m
<z a m~ ~~ o o-i~a o o aeo
u s
.
PCTIEP95I03145
WO 96105260
34
3) Preparation and performance testing of water-based
paint compositions
Water-based paint compositions were prepared by
the same method as in Embodiment 1-8 3 ) , based on the
combinations in Table 10 and evaluated in the same way
as for Embodiments 1-8. The results are shown in Table
11.
2i~~~~9
W O 96f05260 PCTIEP95103145
[Table 10]
,~ m o 0 0 ,-a o o m
o , , , . , , . , o; ,~ 0 0 0 o r~ ~ o;
N V1 O u'7 n m m u1
m ,t~ O
H
.-~ m O O O .-I O O u1
00 , i , , , , , N , ,-I ~ N O O N
O ~ d ~Y vo
O
v-1 m O O O r1 K1 V1 vD
m , n , , n , m n n N O O O m m m n
N V1 O u1 v0 N N ,f1
,-a n O O O N o7 m N
D , n " n m , v m '7 0 0 0 m ~t ~t 0
u1 O V7 O Ov Om l1
V1 N N
H
N m O O O .-1 O O O
n ' m ' ' n n ,~ O O O O O O V1
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~JBS?1TUTE SHEET (RULE 2b~
WO 96105260 2 i 9 b 181 PCTIEP95103145
TablB ~~
ComparisonNo. 1 2 3 5 8 10
4 6 9
Dry film Base coat (um) 1516 15 151615 1615
15
thicknessClear coat (Nm)4040 41 414140 4041
40
Painted 60 gloss 9390 95 949395 9495
93
appearanceSmoothness O X O O 0 O
O O 0
Drip
properties O O O O x O
O X 0
Paint Water
film
performanceresistance O O O X X x
x x 0
Chemical
resistance O O X X O O
O O X
Storage X O O O O O
stability O O O
-
It is evident from Table 11 that in Comparison
Example 1 the storage stability of the water-based
paint composition was inferior because the glass
transition temperature of component (a) of the acrylic
graft copolymer was too low.
In Comparison Example 2 the smoothness .of the
paint film obtained was inferior because the glass
transition temperature of component (a) of the acrylic
graft copolymer was too high.
In Comparison Example 3 the chemical resistance of
the paint film obtained was inferior because the
hydroxyl group number of component (a) of the acrylic
graft copolymer was too low.
In Comparison Example 4 the water resistance of
3o the paint film obtained was inferior because the
hydroxyl group number of component (a) of the acrylic
graft copolymer was too high.
In Comparison Example 5 the water resistance and
chemical resistance of the paint film obtained were
inferior because the number average molecular Weight of
the acrylic graft copolymer was too low.
In Comparison Example 6 the acid value of
component (b) of the acrylic graft copolymer was too
high and the acid value of the acrylic graft copolymer
was too high so that the painted solids of the
resulting water-based paint was lowered, drip was
produced and the appearance of the paint film was
inferior. The water resistance of the paint film
obtained was also inferior.
R'O 96105260 J7 ~~ ~ ~ ~ ~ ~ PCT/EP95/03145
In Comparison Example 8 the acid value of
component (a) of the acrylic graft copolymer was too
high and the acid value of the acrylic graft copolymer
was too high so that the painted solids of the
resulting water-based paint was lowered, drip was
produced and the appearance of the paint film was
inferior. The water resistance of the paint film
obtained was also inferior.
In Comparison Example 9 the chemical resistance of
the resulting paint film was inferior because the
hydroxyl group number of component (b) was too low.
In Comparison Example 10 the water resistance of
the resulting paint film was inferior because the
hydroxyl group number of component (b) of the acrylic
graft copolymer was too high, and consequently the
hydroxyl group number of the acrylic graft copolymer
was too high.
By contrast, it is evident from Table 5 that the
water-based paint compositions of Embodiments 1-8 had
outstanding finished appearance, ease of application,
paint film performance and storage properties.
Comparison ExamSle
Methyl isobutyl ketone 95.5 parts was put into a
reaction vessel provided with a stirrer, a temperature
regulator, a cooling tube and a dropping device,
stirred as the temperature was raised, and refluxed. A
mixture of 2-hydroxyethyl methacrylate 34.8 parts,
acrylic acid 19.4 parts, ~-butyl acrylate 35.8 parts,
2-ethylhexyl methacrylate 60.0 parts and t-butyl
peroxybenzoate 4.5 parts was then added dropwise over 2
hours. Stirring under reflux was continued for a
further 2 hours to complete polymerization. The resin
obtained was an acrylic copolymer of acid number 100 mg
KOH/g, hydroxyl group number 100 mg KOH/g, glass
transition temperature 0°C and number average molecular
mass 4700.
Methyl isobutyl ketone 293.6 parts was then put
into this resin solution, and refluxed under stirring.
Then a mixture of glycidyl methacrylate 4.4 parts, 2-
PC'T/EP95/03145
WO 96105260 2 ~ 9 6181
hydroxyethyl methacrylate 104.4 parts, methyl
methacrylate 214.5 parts, ~-butyl acrylate 1311 parts
and ~-butylperoxy 2-ethylhexanoate 2.0 parts was added
dropwise, requiring 2 hours. This mixture had an acid
number of 0 mg KOH/g, a hydroxyl group number of 100 mg
KOH/g; the weight ratio of component (a)/component (b)
was 25/75 and the mol ratio of component (bl)/component
(a) was 1Ø When stirring was continued after dropwise
addition gelling was produced and it was impossible to
make a graft copolymer.
