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DESCRIPTION
TITLE OF THE INVENTION
Chromate-Free Coated Metal Sheet
5
TECHNICAL FIELD
[0001]
The present invention relates to an inexpensive
decorative chromate-free coated metal sheet in which a
10 coating film (a) not containing a highly environmentalloading
hexavalent chromium is formed on at least one
surface of the metal sheet, and which is particularly
excellent in the workability (or stampability), corrosion
resistance, scratch resistance and the like.
15
BACKGROUND ART
[0002]
For home electric appliances, building materials,
automobiles and the like, instead of the conventional
20 post-coated product, which is coated after the forming
(or stamping) thereof, for example, a pre-coated steel
sheet coated with a colored organic film or a clear precoated
metal sheet directly taking advantage of metallic
texture of a metal surface has come into use. Such a
25 decorative steel sheet can be obtained by applying a
colored organic film to an antirust-treated steel sheet
or a plated steel sheet, or applying a clear coating film
to a metal sheet taking on a metallic luster, and is
characterized by having workability (or stampability) as
30 well as beautiful appearance and exhibiting good
corrosion resistance.
[0003]
For example, Patent Document 1 discloses a technique
where a pre-coated steel sheet excellent in the
35 workability, stain resistance and hardness is obtained by
specifying the film structure. On the other hand, Patent
Document 2 discloses a pre-coated steel sheet in which
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the end corrosion resistance is improved by using a
specific chromate treatment solution. These pre-coated
steel sheets are aiming at achieving workability and
paint adherence as well as good corrosion resistance by a
combined effect of a plating film, a chromate treatment
film and a primer (undercoating) film containing a
chromium-based anti-rust pigment added thereto, and also
aiming at improving the productivity and quality by
omitting the coating after forming (or stamping).
[0004]
However, in consideration of the environmental load
of the hexavalent chromium which may be eluted from the
chromate treatment film, and the organic film containing
a chromium-based anti-rust pigment, demands for a
chromate-free antirust treatment and a chromate-free
organic film are recently increasing. To meet such
demands, a chromate-free pre-coated steel sheet excellent
in the corrosion resistance is disclosed, for example, in
Patent Documents 3 and 4 and has already been used in
practice.
[0005]
In the coating to be used for these pre-coated steel
sheets, the thickness of the coated film thereof is as
large as 10 ~ or more. Moreover, because of the use of
a solvent-based coating material in a large amount, a
special coating system such as incinerator and odor
control unit is required, and the pre-coated steel sheet
is generally produced in on a line specialized in the
coating only. That is, the production process includes
an extra coating step, in addition to the production
steps for a steel sheet to provide the original sheet for
coating, and therefore high costs are entailed, in
addition to the costs of materials which are necessary
for the coating. Accordingly, the thus obtained precoated
steel sheet becomes expensive.
[0006]
However, due to diversified user needs, the
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decorative steel sheet finds its demand also in the field
where the purpose is sufficiently attained when the steel
sheet has a durability under daily use conditions, such
as horne electric appliance and interior building
material, and a lower-cost product is being required.
That is, diversified demands cannot be adequately
satisfied only by the conventional expensive pre-coated
steel sheet.
[0007]
,I
10 To meet such a need, as for the decorative steel
sheet which can be produced at a low cost, for example,
Patent Document 5 discloses a colored steel sheet in
which a colored resin layer having a thickness of 5 ~m or
less is provided, and Patent Document 6 discloses a
15 colored steel sheet having a color film on the surface of
a steel sheet with a specific roughness. However, these
colored steel sheets are designed to secure the corrosion
resistance by providing a chromate treatment film, and
therefore they cannot serve the recent need for chromate-
20 free coating. In addition, the design thereof is not
prepared in consideration of the resistance to scratches
to be caused during handling or pressing thereof or of
the masking of a region where the colored layer is
stretched, and accordingly, there is caused a problem
25 that the outer appearance of the scratched part or
pressed part is extremely impaired.
[0008]
On the other hand, Patent Document 7 discloses a
heat-resistant clear pre-coated metal sheet excellent in
30 the decorative property. The clear coating film used
here has a relatively small thickness of 10 ~ or less
and is chromate-free. However, a solvent-based paint is
used therein as the coating material for forming the
clear coating film, and therefore a special coating
35 system is necessary. In addition, there is a problem
that the scratch resistance is not sufficiently high,
although the decorative property or workability is
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excellent.
PRIOR ART DOCUMENTS
PATENT DOCUMENTS
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[0009]
[Patent Document 1] JP-A (Japanese Unexamined Patent
Publication; KOKAI) No. 8-168723
[Patent Document 2] JP-A No. 3-100180
[Patent Document 3] JP-A No. 2000-199075
[Patent Document 4 ] JP-A No. 2000-262967
[Patent Document 5] JP-A No. 5-16292
[Patent Document 6] JP-A No. 2-93093
[Patent Document 7] JP-A No. 2008-149608
15 SUMMARY OF THE INVENTION
PROBLEMS TO BE SOLVED BY THE INVENTION
[0010]
Under these circumstances, an object of the present
invention is to provide an inexpensive decorative
20 chromate-free coated metal sheet, which does not contain
highly environmental-loading hexavalent chromium and is
particularly excellent in the workability, corrosion
resistance, scratch resistance and the like.
25 MEANS TO SOLVE THE PROBLEM
[0011]
In general, the workability is a performance
technically contradicting the corrosion resistance and
scratch resistance. In order to secure the workability,
30 it is important that the coating film covering the
surface of a metal sheet follows the deformation such as
elongation occurring during the forming of the metal
sheet without causing cracking or delamination. This is
because, when the cracking or delamination is produced in
35 the coating film, this may seriously impair the
decorative appearance thereof. For the purpose of
enhancing the followability of the coating film to
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deformation of a metal sheet, an organic resin which is
relatively soft and excellent in elongation may
preferably be used as the film-forming component of the
coating film. However, it is difficult to secure the
5 corrosion resistance or scratch resistance only by using
a soft organic resin.
As one of the techniques for enhancing the corrosion
resistance or scratch resistance, there is known a
technique of adding inorganic oxide particles to a
10 coating film containing an organic resin as the filmforming
component. However, the addition of inorganic
oxide particles gives rise to a reduction in the
elongation property of the coating film, and therefore it
has heretofore been a very difficult problem to satisfy
15 all of workability, corrosion resistance and scratch
resistance.
Further, as one of the techniques for enhancing the
scratch resistance, there is also known a technique of
adding a lubricant such as polyolefin resin particles,
20 fluororesin particles and molybdenum disulfide particles
to the coating film. However, it has been newly revealed
that in a chromate-free coating film of 10 ~m or less,
which is a relatively thin film as a coated metal sheet,
the corrosion resistance may sometimes be greatly reduced
25 depending on the addition conditions for such a
lubricant.
As a result of earnest study by the present
inventors for solving the above problems, the present
inventors have found that, when two kinds of silica
30 particles each having a specific particle shape and
differing in the particle diameter ranges thereof are
added to and dispersed in a coating film using an organic
resin as the film-forming component, the corrosion
resistance and scratch resistance can greatly be improved
35 without reducing the workability thereof.
In addition, the present inventors have also found
that polyolefin resin particles are preferable as the
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lubricant to be added to the coating film, and when the
average particle size of the polyolefin resin particles
is limited and further, the ratio of the coating film
thickness to the average particle size of the polyolefin
5 resin particles is controlled to a specific range, the
scratch resistance can greatly be improved without
reducing the corrosion resistance.
By combining these discoveries, in a chromate-free
thin-film coated metal sheet of 10 ~ or less, all of
10 workability, corrosion resistance and scratch resistance,
which have been contradictory performances in the prior
art, can successfully be satisfied at a high level.
[0012]
That is, the gist of the present invention resides
15 in the followings.
[0013]
[1] A chromate-free coated metal sheet, comprising
a metal sheet having on at least one surface thereof (a)
a coating film containing (A) an organic resin as film-
20 forming component, (C) silica particles and (D)
polyolefin resin particles, wherein
when the average particle size of the polyolefin
resin particles (D) is "a" ~ and the thickness of the
coating film (a) is "b" ~, these satisfy 0.5~a~3, 2~b~10
25 and 0.1~a/b~0.8, and
the silica particles (C) contain both (C1) spherical
silica particles having an average particle size of 5 to
50 nm and (C2) spherical silica particles having an
average particle size of 0.3 to 5 ~m.
30 [0014]
[2] The chromate-free coated metal sheet according
to claim 1, wherein the organic resin (A) contains (Ae) a
polyester resin having a sulfonic acid group in the
structure.
35 [0015]
[3] The chromate-free coated metal sheet according
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to claim 2, wherein the organic resin (A) further
contains (Au) a polyurethane resin having a urea group in
the structure.
[0016]
5 [4] The chromate-free coated metal sheet according
to claim 1 or 2, wherein the coating film (a) further
contains (E) a color pigment.
[0017]
[5] The chromate-free coated metal sheet according
10 to claim 1 or 2, wherein the softening point of the
polyolefin resin particles (D) is 125°C or more.
[0018]
[6] The chromate-free coated metal sheet according
to claim 1 or 2, wherein the polyolefin resin particles
15 (D) is (D1) a high-density polyethylene resin particles
having a density of 950 kg/m3 or more and a penetration
hardness of 2 or less.
[0019]
[7] The chromate-free coated metal sheet according
20 to claim 1 or 2, wherein the average molecular weight of
the polyolefin resin particles (D) is from 3,000 to
6,000.
[0020]
[8] The chromate-free coated metal sheet according
25 to claim 1 or 2, wherein the content of the polyolefin
resin particles (D) in the coating film (a) is from 0.5
to 10 mass%.
[0021]
[9] The chromate-free coated metal sheet according
30 to claim 1 or 2, wherein when the average particle size
of the spherical silica particle (C2) is "c" ~ and the
thickness of the coating film (a) is "b" /lm, these
satisfy 0.1~c/b~0.7.
[0022]
35 [10] The chromate-free coated metal sheet according
to claim 1 or 2, wherein the organic resin (A) is a resin
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cured by (B) a curing agent.
[0023]
[11] The chromate-free coated metal sheet according
to claim 10, wherein the curing agent (B) contains (B1) a
melamine resin.
10
[0024]
[12] The chromate-free coated metal sheet according
to claim 1 or 2, wherein the coating film (a) is formed
by applying (X) an aqueous coating material composition
containing components of the coating film (a) on at least
one surface of the metal sheet and heat-drying the coated
composition.
[0025]
[13] The chromate-free coated metal sheet according
15 to claim 12, wherein the temperature at the time of heatdrying
the aqueous coating material composition (X) is
from 150 to 250°C in terms of the ultimate sheet
temperature of the metal sheet and the heat-drying time
is from 2.5 to 20 seconds.
20 [0026]
[14] The chromate-free coated metal sheet according
to claim 12, wherein a water cooling step is further
provided after heat-drying of the aqueous coating
material composition (X) and when the softening point of
25 the polyolefin resin particles (0) is TsoC, the sheet
temperature of the metal sheet at water cooling is TMoC
and the water temperature of the cooling water is TwoC,
these satisfy TM>Ts and Tw~(TM-150)/4.
[0027]
30 [15] An aqueous coating material composition (X)
containing (A) an organic resin, (C) silica particles and
(0) a polyolefin resin, wherein
the average particle size of the polyolefin resin
particles (0) is from 0.5 to 3 ~m, and
35 the silica particles (C) contain both (C1) spherical
silica particles having an average particle size of 5 to
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50 nm and (C2) spherical silica particles having an
average particle size of 0.3 to 5 ~m.
EFFECT OF THE INVENTION
5 [0028]
The decorative chromate-free coated metal sheet
according to the present invention does not contain a
highly environmental loading hexavalent chromium, is
inexpensive, and is particularly excellent in the
10 workability, corrosion resistance, scratch resistance and
the like. Accordingly, the coated metal sheet according
to the present invention may be very promising as an
inexpensive, highly decorative, high value-added and
environmentally friendly material and may make a very
15 significant contribution to each of the industrial
fields.
BRIEF DESCRIPTION OF THE DRAWINGS
[0029]
20 [Fig. 1] Fig. 1 is a schematic cross-sectional view
showing one example of the cross-section structure of the
chromate-free coated metal sheet according to the present
invention.
25 MODE FOR CARRYING OUT THE INVENTION
[0030]
The chromate-free coated metal sheet according to
the present invention is a chromate-free coated metal
sheet characterized in that it comprises a metal sheet
30 having on at least one surface thereof (a) a coating film
containing (A) an organic resin as film-forming
component, (C) silica particles and (D) polyolefin resin
particles, wherein
when the average particle size of the
35 polyolefin resin particles (D) is "a" ~ and the
thickness of the coating film (a) is "b" ~m, these
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satisfy 0.5~a~3, 2~b~10 and 0.1~a/b~0.8, and
the silica particles (C) contain both (C1)
spherical silica particles having an average particle
size of 5 to 50 nm and (C2) spherical silica particles
5 having an average particle size of 0.3 to 5 ~.
[0031]
More specifically, in the chromate-free coated metal
sheet according to the present invention, (a) a coating
film containing (A) an organic resin as film-forming
10 component, which contributes to securing the workability
or corrosion resistance (effect of shielding a corrosion
factor) of the coating film, (C) silica particles
contributing to improving the corrosion resistance or
scratch resistance of the coating film, and (0)
15 polyolefin resin particles acting as a lubricant and
contributing to enhancing the lubricity of the coating
film and improving the scratch resistance thereof, is
formed on at least one surface of a metal sheet, which is
a base material. When the average particle size of the
20 polyolefin resin particles (0) is denoted by "a" ~ and
the thickness of the coating film (a) is denoted by "b"
~m, these values satisfy the relationships of 0.5~a~3,
2~b~10 and 0.1~a/b~0.8, whereby the scratch resistance may
greatly be enhanced without reducing the corrosion
25 resistance; and the silica particles (C) contain both
(C1) spherical silica particles having an average
particle size of 5 to 50 nm and (C2) spherical silica
particles having an average particle size of 0.3 to 5 ~m,
whereby the corrosion resistance and scratch resistance
30 may greatly be enhanced without reducing the workability.
That is, all of the workability, corrosion resistance and
scratch resistance may be achieved at a high level.
[0032]
The coating (a) may preferably be formed by applying
35 (X) an aqueous coating material composition containing
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components of the coating film (a) in an aqueous solvent,
on at least one surface of the metal sheet, and heatdrying
the coated composition. The aqueous solvent as
used herein means a solvent where water is the main
5 component of the solvent. The amount of water
constituting the aqueous solvent of the subject
application may preferably be 50 mass% or more. The
solvent other than water to be contained in the aqueous
solvent of the subject application may be an organic
10 solvent. However, the solvent other than water may
preferably be a solvent not coming under the organic
solvent-containing compositions defined in the Ordinance
on the Prevention of Organic Solvent Poisoning of the
Japanese Industrial Safety and Health Act (i.e., the
15 solvent containing an organic solvent in excess of 5% by
weight, which is designated in appended Table 6-2 of the
Order for Enforcement of the Industrial Safety and Health
Act). The use of such an aqueous solvent may make it
unnecessary to additionally pass the metal sheet through
20 a coating-only line for using an organic solvent-based
coating material, and accordingly, such a use may enable
a great reduction in the production cost. Moreover, this
use may also be environmentally advantageous, for
example, because the discharge of a volatile organic
25 compound (VOC) may greatly be suppressed.
[0033]
The coating film thickness of the coating film (a)
may be from 2 to 10 ~, preferably from 3 to 7 ~m. If
the coating film thickness is less than 2 ~m, adequate
30 decorative property (masking) or corrosion resistance may
not be obtained. On the other hand, if the film
thickness exceeds 10 ~' not only this thickness may be
economically disadvantageous but also, for example, when
the coating film (a) is formed of an aqueous coating
35 material composition, a coating film defect such as
bubble or pinhole may be generated, whereby an outer
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appearance required for an industrial product cannot be
obtained stably in some cases.
[0034]
The thickness of the coating film (a) can be
5 measured by observing the cross-section of the coating
film, or utilizing an electromagnetic thickness meter or
the like. In addition, the thickness may also be
calculated by dividing the mass of the coating film
attached per unit area by the specific gravity of the
10 coating film or the specific gravity of the coating
solution after drying. The method of measuring the mass
of the coating film attached may appropriately be
selected from known techniques, for example, for
measuring the difference in mass between before and after
15 the coating, measuring the difference in mass between
before and after the separation of the coating film
coated, or measuring the abundance of an element whose
content in the film is previously known, by using
fluorescent X-ray analysis of the coating. The method of
20 measuring the specific gravity of the coating film or the
specific gravity of the coating solution after drying may
appropriately be selected from known techniques, for
example, for measuring the volume and mass of the
isolated coating film, measuring the volume and mass
25 after taking an appropriate amount of a coating solution
in a vessel and drying the solution, or calculating the
specific gravity from the blending amounts of components
of the coating film and the known specific gravity of
each component.
30 [0035]
Among these measuring methods, those for observing
the cross-section of the coating film may be preferred,
because even a coating film differing in the specific
gravity or the like can be measured simply with good
35 accuracy.
[0036]
The method of observing the cross-section of the
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coating film (a) may not be particularly limited.
However, it is possible to use suitably, for example, a
method of embedding the coated metal sheet in an ordinary
temperature drying-type epoxy resin perpendicularly to
5 the thickness direction of the coating film, and after
the mechanically polishing of the embedding surface,
observing the cross-section by SEM (scanning electron
microscope); or a method of cutting out an observation
sample of 50 to 100 nm in thickness from the coated metal
10 sheet by using an FIB (focused ion beam) system so as to
show the vertical cross-section of the coating film, and
observing the coating film cross-section by TEM
(transmission electron microscope), etc.
[0037]
15 The organic resin (A) is the film-forming component
of the coating film (a). The organic resin (A) may not
be particularly limited in its kind. Specific examples
thereof may include: a polyester resin, a polyurethane
resin, an epoxy resin, an acrylic resin, a polyolefin
20 resin, and a modification product thereof. The
modification product as used herein may refer to a resin
which has been obtained by reacting a reactive functional
group contained in the structure of those resins with
"another compound" (such as monomer or crosslinking
25 agent) containing, in the structure thereof, a functional
group capable of reacting with the functional group
above. As for the organic resin (A), one kind or a
mixture of two or more kinds of organic resins may be
used, or one kind of or a mixture of two or more kinds of
30 organic resins which has been obtained by modifying at
least one kind of an organic resin in the presence of at
least one kind of another organic resin may be used.
[0038]
The content of the film-forming component (in a case
35 where the organic resin (A) is not cured with the laterdescribed
curing agent (B), the content of only the
organic resin (A), and in a case where the organic resin
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(A) is cured with the later-described curing agent (B),
the total amount of the organic resin (A) and the curing
agent (B)) may preferably be from 55 to 80 mass% based on
the coating film. If the content is less than 55 mass%,
the workability may be reduced, and if the content
exceeds 80 mass%, the scratch resistance may be reduced.
[0039]
From the standpoint of satisfying all of
workability, corrosion resistance and scratch resistance
at a high level, the organic resin (A) may preferably
contain (Ae) a polyester resin having a sulfonic acid
group in the structure. The ester group contained in the
structure of the polyester resin may have an appropriate
cohesive energy, so that the film properties (balance
between elongation and strength) of the coating film can
be elevated to a high level. That is, it may be very
effective in satisfying both of workability and scratch
resistance at a high level to apply a polyester resin as
the film-forming component of the coating film.
[0040]
Further, the coating film containing, as the filmforming
component, a polyester resin having a sulfonic
acid group In the structure may have a high free surface
energy due to high polarity of the sulfonic acid group.
On the other hand, the polyolefin resin particles as an
essential component of the coating film may have a
relatively low polarity and accordingly, may have a low
surface free energy. Therefore, by incorporating, as the
film-forming component, a polyester resin having a
sulfonic acid group, the polyolefin resin particles may
tend to be concentrated in the coating film surface side
at the stage of forming the coating film due to the
difference in the surface free energy between the filmforming
component and the polyolefin resin particles of
the coating film. The polyolefin resin particles may act
as a lubricant, and therefore its orientation on the
coating film surface may be effective in reducing the
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friction resistance with another object to be contacted
therewith, and may make it possible to further enhance
the scratch resistance.
[0041]
5 On the other hand, a corrosion factor may readily
intrude into the grain boundary between the film-forming
component and the polyolefin resin particles. Therefore,
when the polyolefin resin particles are present in a
manner of penetrating the entire thickness of the coating
10 film, the grain boundary (intrusion route for the
corrosion factor) may reach even the underlying metal
sheet, and this may give rise to great reduction in the
corrosion resistance. In the present invention, as
described above, a polyester resin having a sulfonic acid
15 group may be contained as the film-forming component and
due to an interaction between the film-forming component
and the polyolefin resin particles of the coating film,
the polyolefin resin particles may be allowed to orient
on the coating film surface. Due to such orientation,
20 there is provided a structure where the grain boundary
stays only in the upper part of the coating film may be
designed to prevent the intrusion route for a corrosion
factor from reaching the underlying metal, whereby the
reduction in the corrosion resistance can be suppressed.
25 That is, both of the scratch resistance and corrosion
resistance can be satisfied at a high level.
[0042]
In addition, in this embodiment, the sulfonic acid
group contained in the polyester resin may contribute
30 also to enhancing the adherence to a metal sheet (in a
case where a primer treatment is to be conducted, to the
primer treatment layer) as the base material, and
therefore may be suitable for enhancing the workability
and scratch resistance. Further, in a case where the
35 coating material composition for forming the coating film
is an aqueous composition, the sulfonic acid group may
have high hydrophilicity, and therefore may be suitable
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also for enhancing the stability of the polyester resin
in the aqueous coating material composition (preventing,
for example, caking of the coating material composition
or generation of an aggregate thereof). Particularly, in
5 the case of using the later-described curing agent in
combination, the coating material composition may
sometimes undergo large pH fluctuation to reduce the
stability of the coating material. However, when a
polyester resin having a sulfonic acid group is used, the
10 resin may be less affected by the pH fluctuation of the
coating material composition, and reduction in the
stability of the coating material can be suppressed.
Incidentally, the polyester resin having a sulfonic acid
group may have a property of being less liable to be
15 dissolved in an organic solvent (it can be dissolved only
in some polar solvents) and for this reason, this resin
cannot be substantially used in an organic solvent-based
coating material composition using an organic solvent as
the solvent. Further, in the case of using a curing
20 agent, a curing catalyst such as sulfonic acid groupcontaining
compound may generally be used in combination,
but such a curing catalyst may reduce the corrosion
resistance of the coating film. On the other hand, the
polyester resin having a sulfonic acid group can be cured
25 by low temperature drying/curing, even without using a
curing catalyst, and therefore there is no need to add a
curing catalyst and no fear of reduction in the corrosion
resistance due to the addition of a curing catalyst. The
polyester resin having a sulfonic acid group cannot be
30 applied to a coating material using an organic solvent as
the solvent, and in a case where a coating film is formed
by using such a coating material, the above-described
effect of the sulfonic acid, particularly, the effect of
satisfying both corrosion resistance and scratch
35 resistance, cannot be expected.
[0043]
The content of the polyester resin (Ae) may
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preferably be from 60 to 100 mass%, more preferably from
80 to 100 mass%, based on the organic resin (A). If the
content is less than 60 mass%, the effect of improving
the workability, scratch resistance and corrosion
resistance may not be obtained.
[0044]
The polyester resin (Ae) may preferably further
contain a bisphenol structure in the structure thereof.
The bisphenol structure may not only have a high cohesive
energy but also be excellent in the water resistance, and
therefore in view of enhancing the scratch resistance and
corrosion resistance, it may be preferred to contain the
bisphenol structure.
[0045]
The polyester resin (Ae) may not be particularly
limited, as long as it contains a sulfonic acid group in
the structure, but the resin may be obtained, for
example, by condensation-polymerizing a polyester raw
material composed of a polycarboxylic acid component and
a polyol component. Further, the thus obtained polyester
resin may be dissolved in water, or may be dissolved to
make an aqueous system.
[0046]
Specific examples of the polycarboxylic acid
component may include: for example, one kind of a
component or a plurality of kinds of components, such as
phthalic acid, phthalic anhydride, tetrahydrophthalic
acid, tetrahydrophthalic anhydride, hexahydrophthalic
anhydride, methyl tetraphthalic acid, methyl
tetrahydrophthalic anhydride, himic anhydride,
trimellitic acid, trimellitic anhydride, pyromellitic
acid, pyromellitic anhydride, isophthalic acid,
terephthalic acid, maleic acid, maleic anhydride, fumaric
acid, itaconic acid, adipic acid, azelaic acid, sebacic
acid, succinic acid, succinic anhydride, lactic acid,
dodecenylsuccinic acid, dodecenylsuccinic anhydride,
cyclohexane-1,4-dicarboxylic acid and endo-anhydride.
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5
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[0047]
Specific examples of the polyol component may
include: for example, one kind of a component or a
plurality of kinds of components, such as ethylene
glycol, diethylene glycol, 1,3-propanediol, 1,2propanediol,
triethylene glycol, 2-methyl-1,3propanediol,
2,2-dimethyl-1,3-propanediol, 2-butyl-2ethyl
1,3-propanediol, 1,4-butanediol, 2-methyl-1,4butanediol,
2-methyl-3-methyl-1,4-butanediol, 1,5-
pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol,
1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol,
1,2-cyclohexanedimethanol, hydrogenated bisphenol-A,
dimer diol, trimethylolethane, trimethylolpropane,
glycerin and pentaerythritol.
[0048]
The method of introducing the above-mentioned
sulfonic acid group into a polyester resin may not be
particularly limited, but may include, for example, a
method of using, as a polyester raw material,
dicarboxylic acids such as 5-sulfoisophthalic acid, 4sulfonaphthalene-
2,7-dicarboxylic acid and 5(4sulfophenoxy)
isophthalic acid; or glycols such as 2sulfo-
1,4-butanediol and 2,5-dimethyl-3-sulfo-2,5hexyldiol.
[0049]
The sulfonic acid group may refer to a functional
group represented by -S03H and may be a group obtained by
neutralizing the sulfonic acid group with alkali metals,
amines inclusive of ammonia, or the like. In a case
30 where the sulfonic acid group is neutralized, an already
neutralized sulfonic acid group may be incorporated into
the resin, or a sulfonic acid may be incorporated into
the resin and then neutralized. Among these, a sulfonic
acid metal salt group obtained by neutralization with
35 alkali metals such as Li, Na and K may be particularly
preferred, in view of enhancing the adherence to the base
material or enhancing the dispersibility of a color
25
• - 19 -
pigment having a hydrophobic surface, and a sulfonic acid
Na salt group may be most preferred.
[0050]
The amount the sulfonic acid group-containing
5 dicarboxylic acid or glycol to be used may preferably be
from 0.1 to 10 mol% based on all polycarboxylic acid
components or all polyol components. If the content is
less than 0.1 mol%, the effect of enhancing the adherence
may not be obtained. Also, in the case of using an
10 aqueous solvent, the solubility or dispersibility for
water may be reduced. Further, in the case of using a
color pigment, the dispersibility of the color pigment
may be reduced so as to deteriorate the decorative
property. If the content exceeds 10 mol%, the corrosion
15 resistance may be reduced. In consideration of the
balance of performances, the content may be more
preferably from 0.5 to 7 mol%.
[0051]
The method of introducing the bisphenol structure
20 may not be particularly limited, but may include, for
example, a method of using, as a polyester raw material,
glycols such as ethylene oxide adduct of bisphenol A,
propylene oxide adduct of bisphenol A, ethylene oxide
adduct of bisphenol F and propylene oxide adduct of
25 bisphenol F.
[0052]
The amount the bisphenol structure-containing glycol
to be used may preferably be from 1 to 40 mol% based on
all polyol components. If the content is less than 1
30 mol%, the effect of enhancing the scratch resistance and
corrosion resistance may not be obtained. On the other
hand, if the content exceeds 40 mol%, the workability may
be deteriorated. In consideration of the balance of
performances, the content may be more preferably from 5
35 to 30 mol%.
[0053]
In an embodiment of the present invention where the
•
5
10
15
- 20 -
organic resin (A) contains the polyester resin (Ae), in
view of enhancing the corrosion resistance and scratch
resistance, it may be particularly preferred to further
contain (Au) a polyurethane resin having an urea group in
the structure. In order to satisfy all of the
workability, scratch resistance and corrosion resistance,
it may be important to provide a coating film excellent
in both elongation and strength, and to increase the
adherence to a metal sheet (in the case of including a
primer treatment, the primer treatment layer) as the base
material. When the urea group-containing polyurethane
resin (Au) having a very high cohesive energy is mixed
with the polyester resin (Ae) and used, a coating film
which is excellent in both elongation and strength and is
excellent also in the adherence to the base material can
be designed.
[0054]
20
30
25
In a case where the coating film (a) contains the
polyurethane resin (Au) together with the polyester resin
(Ae), the total content of the polyester resin (Ae) and
the polyurethane resin (Au) may preferably be from 60 to
100 mass%, more preferably from 80 to 100 mass%, based on
the organic resin (A). If the content is less than 60
mass%, the effect of improving the workability, scratch
resistance and corrosion resistance may not be obtained.
[0055]
The solid content mass ratio (Ae)/(Au) between the
polyester resin (Ae) and the polyurethane resin (Au) may
preferably be from 50/50 to 90/10. If the ratio is less
than 50/50, the workability may be reduced. On the other
hand, if the ratio exceeds 90/10, the effect of improving
the corrosion resistance and scratch resistance may not
be obtained.
[0056]
35 The polyurethane resin (Au) may not be particularly
limited, as long as it contains a urea group in the
structure. Specific examples thereof may include: a
5
10
• - 21 -
resin obtained by reacting a polyol compound and a
polyisocyanate compound and thereafter, further
elongating the chain with an amino group-containing chain
extender agent.
[0057]
The polyol compound may not be particularly limited,
as long as it is a compound containing two or more
hydroxy groups per molecule. Specific examples thereof
may include: a polycarbonate polyol, a polyester polyol,
a polyether polyol, a polyesteramide polyol, an acryl
polyol, a polyurethane polyol, and a mixture thereof.
[0058]
The polyisocyanate compound may not be particularly
limited, as long as it is a compound containing two or
15 more isocyanate groups per molecule. Specific examples
thereof may include: an aliphatic isocyanate, an
alicyclic diisocyanate, an aromatic diisocyanate, an
aromatic-aliphatic diisocyanate, and a mixture thereof.
[0059]
20 The chain extender agent may not be particularly
limited, as long as it is a compound containing one or
more amino groups in the molecule. Specific examples
thereof may include: an aliphatic polyamine such as
ethylenediamine, propylenediamine, hexamethylenediamine,
25 diethylenetriamine, dipropylenetriamine,
triethylenetetramine and tetraethylenepentamine, an
aromatic polyamine such as tolylenediamine,
xylylenediamine and diaminodiphenylmethane, an alicyclic
polyamine such as diaminocyclohexylmethane, piperazine,
30 2,5-dimethylpiperazine and isophoronediamine, hydrazines
such as hydrazine, succinic acid dihydrazide, adipic acid
dihydrazide and phthalic acid dihydrazide, and an
alkanolamine such as hydroxyethyldiethylenetriamine, 2[(
2-aminoethyl)amino]ethanol and 3-aminopropanediol. One
35 of these compounds may be used alone, or two or more
kinds thereof may be used as a mixture.
[0060]
•
5
10
15
20
25
30
35
- 22 -
The organic resin (A) may preferably further contain
an acrylic resin. When it contains an acrylic resin, the
adherence thereof to a metal sheet (in the case of
including a primer treatment, the primer treatment layer)
as the base material may be enhanced, and the scratch
resistance may be improved. In addition, in a case where
the coating material composition for forming the coating
film (a) is denoted by an aqueous composition and further
contains the later-described color pigment (E) and the
color pigment is a pigment having a hydrophobic surface,
such as carbon black (El) described later, the effect of
uniformly dispersing the pigment in the aqueous coating
material composition can be obtained by incorporating an
acrylic resin. Accordingly, it may be preferred to
contain an acrylic resin also in view of uniformly
dispersing the color pigment in the thus formed coating
film (a) and of imparting an excellent decorative
property.
[0061]
The acrylic resin may not be particularly limited.
Specific examples thereof may include: for example, a
homopolymer of or a copolymer of two or more monomers of
an ethylene-based unsaturated carboxylic acid alkyl ester
monomer, such as methyl (meth) acrylate, ethyl
(meth) acrylate, n-butyl (meth)acrylate and 2-ethylhexyl
(meth) acrylate; or a polymer obtained by copolymerizing
such a homopolymer or copolymer with a single monomer or
two or more monomers of an ethylene-based unsaturated
carboxylic acid monomer such as acrylic acid, methacrylic
acid, maleic acid and itaconic acid; a monoester monomer
of an ethylene-based unsaturated dicarboxylic acid, such
as ethyl maleate, butyl maleate, ethyl itaconate and
butyl itaconate; a hydroxyl group-containing ethylenebased
unsaturated carboxylic acid alkyl ester monomer
such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl
(meth) acrylate, 4-hydroxybutyl (meth)acrylate and a
reaction product of 2-hydroxyethyl (meth)acrylate with an
- 23 -
5
10
25
15
8-caprolactone; an ethylene-based unsaturated carboxylic
acid aminoalkyl ester monomer such as aminoethyl
(meth) acrylate, dimethylaminoethyl (meth) acrylate, and
butylaminoethyl (meth) acrylate; an ethylene-based
unsaturated carboxylic acid aminoalkylamide monomer such
as aminoethyl(meth)acrylamide,
dimethylaminomethyl(meth)acrylamide and
methylaminopropyl(meth)acrylamide; other amide groupcontaining
ethylene-based unsaturated carboxylic acid
monomers such as acrylamide, methacrylamide, Nmethylolacrylamide,
methoxybutylacrylamide and
diacetoneacrylamide; an unsaturated fatty acid glycidyl
ester monomer such as glycidyl acrylate and glycidyl
methacrylate; a vinyl cyanide-based monomer such as
(meth)acrylonitrile and u-chloroacrylonitrile; a
saturated aliphatic carboxylic acid vinyl ester monomer
such as vinyl acetate and vinyl propionate; and a
styrene-based monomer such as styrene, u-methylstyrene
and vinyltoluene. The method of polymerizing such a
monomer may not be particularly limited and may include,
for example, a method of radical-polymerizing such a
monomer in an aqueous solution by using a polymerization
initiator. The polymerization initiator may not be
particularly limited and, for example, a persulfate such
as potassium persulfate and ammonium persulfate, or an
azo compound such as azobiscyanovaleric acid and
azobisisobutyronitrile, can be used.
[0062]
The content of the acrylic resin may preferably be
30 from 0.5 to 20 mass% based on the organic resin (A). If
the content is less than 0.5 mass%, the decorative
property and scratch resistance may be reduced. On the
other hand, if the content exceeds 20 mass%, the
corrosion resistance or workability may be deteriorated.
20
35 [0063]
In view of improving the scratch resistance or
10
- 24 -
corrosion resistance, the organic resin (A) may
preferably be a resin which has been cured with (B) a
curing agent. The curing agent (B) may not be
particularly limited, as long as it cures the organic
5 resin (A). Specific examples thereof may include: (Bl) a
melamine resin, and a polyisocyanate compound.
The melamine resin (Bl) is a resin where the
methylol group of a product obtained by condensing
melamine and formaldehyde is partially or entirely
etherified with a lower alcohol such as methanol, ethanol
and butanol.
[0064]
15
20
The polyisocyanate compound may not be particularly
limited. Specific examples thereof may include:
hexamethylene diisocyanate, isophorone diisocyanate,
xylylene diisocyanate, and tolylene diisocyanate.
Examples of the blocked product thereof may include: a
blocked product of hexamethylene diisocyanate, a blocked
product of isophorone diisocyanate, a blocked product of
xylylene diisocyanate, a blocked product of tolylene
diisocyanate, which are a blocked product of the abovementioned
polyisocyanate compound. One of these curing
agents may be used, or two or more thereof may be used in
combination.
~i Ii
III
25 [0065]
The content of the curing agent (B) may preferably
be from 5 to 35 mass% per 100 mass% of the organic resin
(A) • If the content is less than 5 mass%, the curing by
baking may insufficiently proceed and the corrosion
30 resistance and scratch resistance may be reduced. On the
other hand, if the content exceeds 35 mass%, curing by
baking may excessively proceed and the corrosion
resistance and workability may be deteriorated.
[0066]
35 From the standpoint of scratch resistance, the
curing agent (B) may preferably contain (Bl) a melamine
resin. The content of the melamine resin (Bl) may
i!
115
10
20
35
- 25 -
preferably be from 30 to 100 mass% based on the curing
agent (B). If the content is less than 30 mass%, the
effect of improving the scratch resistance may not be
obtained.
5 [0067]
In the case of using the curing agent (B)
(particularly, when the curing agent (B) contains the
melamine resin (B1)), for the purpose of causing a curing
reaction thereof, the coating film should be formed by
heating and drying the coating film at a relatively high
baking temperature of 150°C or more, with respect to the
conventional aqueous coating material. In the case of
heating and drying the coating film at a baking
temperature of 150°C or more, the polyolefin resin
particles may readily flow out from the coating film, and
the portion after flowing out of the particles may become
a pinhole and incur reduction in the corrosion
resistance. In such a case, for suppressing the
reduction in the corrosion resistance, it is particularly
effective to control the average particle size of the
polyolefin resin particles (D), the thickness of the
coating film and the ratio therebetween to the abovementioned
specific ranges.
[0068]
25 As essential requirements of the present invention,
the coating film (a) using the organic resin (A) as the
film-forming component contains (C) silica particles and
(D) polyolefin resin particles; when the average particle
size of the polyolefin resin particles (D) is denoted by
30 "a" /lIn and the thickness of the coating film (a) is
denoted by "b" /-lm, these satisfy 0.5~a~3, 2~b~10 and
0.1~a/b~0.8; and the silica particles (C) contain both
(C1) spherical silica particles having an average
particle size of 5 to 50 nm and (C2) spherical silica
particles having an average particle size of 0.3 to 5 /lIn.
The "spherical" as used in the present invention refers
5
10
15
- 26 -
to not only a true sphere, but also a shape close to a
sphere and may encompass an ellipsoid. However, in the
case of an ellipsoid, the ratio of the minor axis to the
major axis may preferably be 0.7 or more, in view of
workability, corrosion resistance and scratch resistance,
and more preferably 0.8 or more.
[0069]
The spherical silica particle (C1) which is a fine
particle having an average particle size of 5 to 50 nm
may have a considerable effect of enhancing the corrosion
resistance, and the spherical silica particle (C2) which
is a relatively large particle having an average particle
size of 0.3 to 5 ~m may have a considerable effect of
enhancing the scratch resistance. These particles having
different properties and differing in the particle size
are simultaneously contained in the coating film (a) and
may synergistically enhance the corrosion resistance and
scratch resistance of the coated metal sheet.
II
[0070]
20 The relatively large spherical silica particle (C2)
having an average particle size of 0.3 to 5 ~m may also
have an effect of decreasing the luster of the coated
metal plate, and this may be advantageous in that, even
when a little scratch is put on the coating film (a), the
25 scratch is less recognizable. In the case of a colored
coating film where the coating film (a) further contains
the later-described color pigment (E), the above effect
is particularly great.
[0071]
30 If the average particle size of the spherical silica
particle (C1) is less than 5 nm, this may be technically
difficult in view of stability of the particle in the
coating material composition (lack of stability may cause
a problem such as aggregation of particles or gelling of
35 the coating material composition). On the other hand, if
the average particle size exceeds 50 nm, the effect of
5
10
15
20
25
30
35
- 27 -
enhancing the corrosion resistance is small. The average
particle size of the spherical silica particle (C1) may
preferably be from 8 to 30 nm. If the average particle
size of the spherical silica particle (C2) is less than
0.3 ~, the effect of enhancing the scratch resistance of
the coated metal sheet may be small. On the other hand,
if the average particle size exceeds 5 ~, the
workability or corrosion resistance may be reduced.
Also, the dispersion stability in the coating material
composition may be poor (precipitation or the like may
occur). The average particle size of the spherical
silica particle (C2) may preferably be 0.5 to 3 ~.
[0072]
The spherical silica particle (C1) may not be
particularly limited in its kind, and examples thereof
may include: silica particles such as colloidal silica
and fumed silica. Examples of the commercially available
product may include: Snowtex 0, Snowtex N, Snowtex C and
Snowtex IPA-ST (Nissan Chemical Industries, Ltd.);
Adelite AT-20N and AT-20A (Asahi Denka Co., Ltd.); and
Aerosi1200 (Nippon Aerosil Co., Ltd.)
[0073]
The spherical silica particle (C2) may not be
particularly limited in its kind, and examples thereof
may include: functional spherical silica HPS Series
(Toagosei Co., Ltd.) and Nipsil Series (Tosoh Silica
Corporation). By virtue of the particle shape being
spherical, both the scratch resistance and the
workability can be satisfied at a high level.
[0074]
The content of the spherical silica particle (C1)
may preferably be from 3 to 30 mass%, more preferably
from 5 to 20 mass%, based on the coating film (a). If
the content is less than 5 mass%, the effect of enhancing
the corrosion resistance and scratch resistance may not
be obtained. On the other hand, if the content exceeds
- 28 -
30 mass%, the corrosion resistance and workability may be
reduced.
[0075]
The content of the spherical silica particle (C2)
5 may preferably be from 3 to 20 mass%, more preferably
from 5 to 15 mass%, based on the coating film (a). If
the content is less than 3 mass%, the effect of enhancing
the scratch resistance may not be obtained. On the other
hand, if the content exceeds 20 mass%, the corrosion
10 resistance and workability may be reduced.
[0076]
The total content of the spherical silica particle
(C1) and the spherical silica particle (C2) may
preferably be from 10 to 40 mass%, more preferably from
15 10 to 30 mass%, based on the coating film (a). If the
content is less than 10 mass%, the effect of enhancing
the corrosion resistance and scratch resistance may not
be obtained. On the other hand, if the content exceeds
40 mass%, the corrosion resistance and workability may be
20 reduced. The ratio between the spherical silica particle
(C1) and the spherical silica particle (C2) contained in
the coating film may preferably be from 30/70 to 80/20 in
terms of mass ratio. Also, the ratio between the average
particle sizes of the spherical silica particle (C1) and
25 the spherical silica particle (C2) contained in the
coating film (a) may preferably be from 1/350 to 1/16.
[0077]
When the average particle size of the spherical
silica particle (C2) contained in the coating film (a) is
30 denoted by "c" J.tm and the thickness of the coating film
(a) is denoted by "b" J.tffi, these may preferably satisfy
0.1~c/b~0.7. If c/b is less than 0.1, the effect of
enhancing the scratch resistance may not be obtained. On
the other hand, if c/b exceeds 0.7, the corrosion
35 resistance and workability may be reduced.
[0078]
- 29 -
The average particle size of the polyolefin resin
particles (0) may be from 0.5 to 3~. If the average
particle size is less than 0.5 ~, the effect of
enhancing the scratch resistance may not be obtained. On
5 the other hand, if the average particle size exceeds 3
~m, the corrosion resistance may be reduced.
[0079]
When the average particle size of the polyolefin
resin particles (0) dispersed in the coating film (a) is
10 denoted by "a" ~m and the thickness of the coating film
(a) is denoted by "b" ~m, these should satisfy
0.1~a/b~0.8. If alb is less than 0.1, the effect of
enhancing the scratch resistance may not be obtained. On
the other hand, if alb exceeds 0.8, the corrosion
15 resistance may be reduced.
[0080]
The content of the polyolefin resin particles (0)
may preferably be from 0.5 to 15 mass%, more preferably
from 1 to 10 mass%, based on the coating film (a). If
20 the content is less than 0.5 mass%, the effect of
enhancing the scratch resistance may not be obtained. On
the other hand, if the content exceeds 10 mass%, the
corrosion resistance and workability may be reduced.
[0081]
25 In the present invention, the polyolefin resin
particles (0) may preferably have a softening point of
125°C or more. When (0) polyolefin resin particles having
a softening point of 125°C or more are incorporated, at
the time of heating and drying to form the coating film
30 (a), the polyolefin resin particles may less flow out
from the coating film, and therefore the generation of a
pinhole or outflow of the polyolefin resin particles may
be suppressed, and as a result, the corrosion resistance
or scratch resistance may be enhanced.
35 [0082]
- 30 -
15
10
25
20
f[
The "softening point" of the polyolefin resin
particles as used in the description of the present
invention means a temperature at which the polyolefin
resin particles heated is softened and starts deforming,
5 and refers to a temperature to be measured by the method
described in JIS K2207.
[0083]
Examples of the polyolefin resin particles (0)
having a softening point of 125°C or more may include
polyethylene resin particles such as Chemipearl W900,
W700, W300, W308, W800, W3I0 (all having a softening
point of 132°C) and Chemipearl WI00 (softening point:
128°C) mfd. by Mitsui Chemicals, Inc.; A-113 (softening
point: 126°C), A-375, A-575 and AB-50 (all having a
softening point of 125°C) mfd. by Gifu Shellac
Manufacturing Co., Ltd.; and Hitech E-4A, E-4B, E-I000
and E-63I4 (softening point: 138°C) mfd. by Toho Chemical
Industrial Co., Ltd.; and polypropylene resin particles
such as Chemipearl WPI00 (softening point: 148°C) mfd. by
Mitsui Chemicals, Inc., AC-35 (softening point: 143°C)
mfd. by Gifu Shellac Manufacturing Co., Ltd., and Hitech
P5043 (softening point: 157°C) and P-5300 (softening
point: 145°C) mfd. by Toho Chemical Industrial Co., Ltd.,
but the resin may not be limited to these resin
particles.
[0084]
It may also be preferred that the polyolefin resin
particles (0) is (01) a high-density polyethylene resin
particles having a density of 950 kg/m3 or more and a
30 penetration hardness of 2 or less. If the density of the
polyolefin resin particles (0) is less than 950 kg/m3
, the
corrosion resistance or scratch resistance may be
disadvantageously reduced. Also, if the hardness of the
polyolefin resin particles (0) exceeds 2, the corrosion
35 resistance or scratch resistance may be disadvantageously
- 31 -
reduced. The "density" of the polyolefin resin particles
as used in the disclosure of the present invention can be
measured by the method described in JIS K6760, and the
"penetration hardness" can be measured by the method
5 described in JIS K2207.
[0085]
f
10
15
20
25
The number-average molecular weight of the
polyolefin resin particles (0) may preferably be from
3,000 to 6,000. If the number-average molecular weight
of the polyolefin resin particles (0) is less than 3,000,
the scratch resistance may be disadvantageously reduced.
On the other hand, if the number-average molecular weight
of the polyolefin resin particles (0) exceeds 6,000, the
scratch resistance may be disadvantageously reduced. The
"number-average molecular weight (Mn)" of the polyolefin
resin particles as used in the description of the present
invention can be measured by GPC (gel permeation
chromatography). Alliance 2000 (mfd. by Waters) was used
as the GPC measuring apparatus, TSKgel GMH6-HTx2+TSKgel
GMH6-HTLx2 (each 7.5 rom I.0.x30 cm, mfd. by Tosoh
Corporation) were used as the column, and 0dichlorobenzene
(Wako Pure Chemical Industries, Ltd.,
guaranteed reagent) was used as the mobile phase. The
measurement was performed under the conditions of a
column temperature of 140°C and a mobile-phase flow
velocity of 1.0 mL/min, and a differential refractometer
was used for detection. A monodisperse polystyrene was
used for the molecular weight calibration.
[0086]
30 The coating film (a) may preferably further contain
at least one kind of (F) resin particles selected from
those of an acrylic rein and a silicone resin. The resin
particles (F) may have an effect of enhancing the scratch
resistance similarly to the spherical silica particle
35 (C2) and have an effect of decreasing the luster of the
coated metal sheet and have an effect of making the
- 32 -
scratch less recognizable even when somewhat scratched.
[0087]
The acrylic resin particles may not be particularly
limited in its kind, and examples thereof may include: a
5 crosslinked methyl polymethacrylate, a crosslinked butyl
polymethacrylate, a non-crosslinked methyl
polymethacrylate, a non-crosslinked butyl
polymethacrylate, a polystyrene, and an alkyl
polyacrylate. From the standpoint of satisfying both the
10 scratch resistance and the workability at a high level, a
crosslinked methyl polymethacrylate may be particularly
preferred.
[0088]
The silicone resin particles may not be particularly
15 limited in its kind, and examples thereof may include:
dimethylpolysiloxane and polyorganosilsesquioxane. From
the standpoint of satisfying both the scratch resistance
and the workability at a high level,
polyorganosilsesquioxane may be particularly preferred.
20 [0089]
The average particle size of the resin particles (F)
may not be particularly limited, but a spherical particle
having an average particle size of 1 to 5 ~m. If the
average particle size is less than 1 ~m, the effect of
25 enhancing the scratch resistance of the coated metal
sheet may not be obtained. On the other hand, if the
average particle size exceeds 5 ~m, it may be difficult
to secure the dispersion stability in the coating
material composition, and there may arise a problem such
30 as precipitation of particle and solidification. In
addition, the workability may be reduced.
[0090]
When the average particle size of the resin
particles (F) contained in the coating film (a) is
35 denoted by "d" ~m and the thickness of the coating film
(a) is denoted by "b" ~m, these may preferably satisfy
5
- 33 -
0.3~d/b~1.2. If d/b is less than 0.3, the effect of
enhancing the scratch resistance of the coated metal
sheet may not be obtained. On the other hand, if d/b
exceeds 1.2, the corrosion resistance and workability may
be reduced.
[0091]
The content of the resin particles (F) may
preferably be from 0.5 to 15 mass% based on the coating
film (a). If the content is less than 0.5 mass%, the
10 effect of enhancing the scratch resistance of the coated
metal sheet may not be obtained. On the other hand, if
the content exceeds 15 mass%, the corrosion resistance
and workability may be reduced. The content of the resin
particles (F) may be more preferably from 1 to 10 mass%.
15 [0092]
The coating film (a) may further contain (E) a color
pigment. The color pigment (E) may not be particularly
limited in its kind. Specific examples thereof may
include: an inorganic color pigment such as titanium
20 dioxide, carbon black, graphite, iron oxide, lead oxide,
coal dust, talc, cadmium yellow, cadmium red and chromium
yellow; an organic color pigment such as phthalocyanine
blue, phthalocyanine green, quinacridone, perylene,
anthrapyrimidine, carbazole violet, anthrapyridine, azo
25 orange, flavanthrone yellow, isoindoline yellow, azo
yellow, indanthrone blue, dibromanzusrone red, perylene
red, azo red and anthraquinone red; and a luster material
such as aluminum powder, alumina powder, bronze powder,
copper powder, tin powder, zinc powder, iron phosphide
30 powder, metal-coated mica powder, titanium dioxide-coated
mica powder, titanium dioxide-coated glass powder and
titanium dioxide-coated alumina powder.
[0093]
In a case where the coating film (a) is colored a
35 dark color, or an excellent decorative property is
imparted by using a thin film having a thickness of 10 ~
- 34 -
or less, the color pigment (E) may preferably contain a
carbon black.
[0094]
The carbon black may not be particularly limited.
5 Specific example thereof may include: a known carbon
black such as furnace black, Ketjen black, acetylene
black and channel black. Also, a carbon black which has
been subjected to a known ozone treatment, plasma
treatment or liquid phase oxidation treatment may be
10 used. The particle size of the carbon black to be used
may not be particularly limited, as long as the range
thereof does not pose a problem in the dispersibility in
the coating material composition, the quality of the
coating film and the coating property. More
15 specifically, a carbon black having a primary particle
size of 10 to 120 nm can be used. In consideration of
the decorative property or corrosion resistance of a thin
film, a fine particulate carbon black having a primary
particle size of 10 to 50 nm may preferably be used. In
20 the case of dispersing such a carbon black in an aqueous
solvent, aggregation may occur in the dispersion process,
and therefore it may generally be difficult to disperse a
carbon black still having a primary particle size. That
is, in practice, the carbon black may be present in the
25 form of a secondary particle having a particle size
larger than the primary particle size in the coating
material composition, and may be present in the same form
also in the coating film (a) which has been formed from
the coating material composition. In order to secure the
30 decorative property and corrosion resistance of a thin
film, the particle size of the carbon black to be
dispersed in the coating film (a) may be important, and
the average particle size may preferably be from 20 to
300 nm.
35 [0095]
When the content of the carbon black in the coating
film (a)
- 35 -
is denoted by "e" mass% and the thickness of the
coating film (a) is denoted by "b" fJlTl, these may
preferably satisfy e~15, b~10 and exb~20. In order to
secure the decorative property (masking), it may also be
5 important to keep the absolute amount of the carbon black
to be contained in the coating film (a) at a given amount
or more. The absolute amount of the carbon black can be
expressed by the product of the content of carbon black
to be contained in the coating film (e mass%) and the
10 thickness of the coating film (b ~m). That is, if (exb)
is less than 20, the decorative property (masking) may be
reduced. Also, if e exceeds 15, the film-forming
property of the coating film may be deteriorated and the
corrosion resistance or workability may be reduced.
15 [0096]
In the case of coloring the coating film (a) a light
color, the color pigment (E) may preferably contain
titanium dioxide. The content of the titanium dioxide in
the coating film (a) may preferably be from 10 to 70
20 mass%. If the content is less than 10 mass%, the
decorative property (masking) may be reduced. On the
other hand, if the content exceeds 70 mass%, the
workability or corrosion resistance may be reduced. In
general, in a case where the coating film (a) contains
25 the carbon black and is colored a dark color, the coating
film may be characterized in that, when scratched, the
scratch is easily recognizable, as compared with that in
the case of being not colored or of being colored a light
color. The titanium dioxide may have an effect of
30 improving the scratch resistance and moreover, have an
effect of giving the appearance to be close to a light
color and making the scratch less recognizable.
Accordingly, in order to enhance the scratch resistance
while securing the decorative property (masking) when
35 colored, the workability and corrosion resistance of a
thin film having a film thickness of 10 ~m or less, both
- 36 -
the carbon black and the titanium dioxide may preferably
be incorporated into the coating film (a). In this case,
the carbon black and the titanium dioxide may preferably
be contained in a ratio of 0.5/9.5 to 3/7 in terms of
5 mass ratio.
[0097]
In general, it may be sometimes difficult to specify
the shape or size of particles contained in a thin
coating film. Even so, unless the particulate component
10 contained in a coating material composition to be used
for the formation of a coating film is subject to some
physical or chemical change (for example, connection or
aggregation of particles to each other, significant
dissolution in the coating material solvent, or reaction
15 with another component) in the course of forming the
coating film, the component may be regarded as keeping
the shape or size of the particle present in the coating
material, even after the coating film formation. The
spherical silica particle (C1), the spherical silica
20 particle (C2), the polyolefin resin particles (0), the
color pigment (E), and the at least one resin particles
(F) selected from an acrylic resin and a silicone resin,
which are a particulate component usable in the present
invention, may be selected not to significantly dissolve
25 in the solvent of the coating material composition used
for the formation of a coating film (~), and not to react
with the solvent or other components constituting the
coating film. Also, for the purpose of causing the
particulate component to more highly keep the shape with
30 which the component is present in the coating material,
as desired, a particulate component previously dispersed
in a solvent by using a known dispersant such as
surfactant or dispersive resin may be used as a raw
material of the coating material composition.
35 Accordingly, the particle size of the particulate
component contained in the coating film, which is
specified in the present invention, can be expressed by
- 37 -
the particle size of the particulate component in the
coating material composition to be used for the formation
of the coating film (a).
[0098]
5 More specifically, the particle sizes of the
spherical silica particle (C1), the spherical silica
particle (C2), the polyolefin resin particles (D), the
color pigment (E), and the at least one resin particles
(F) selected from an acrylic resin and a silicone resin,
10 which are a particulate component usable in the present
invention, can be measured by a dynamic light scattering
method (Nano-track method). According to the dynamic
scattering method, the diameter of a fine particle in a
dispersion medium whose temperature, viscosity and
15 refractive index are known, can easily be determined.
The particulate component for use in the present
invention may be selected so that it is not significantly
dissolved in the solvent of the coating material, and it
does not react with the solvent or other components
20 constituting the coating film. Therefore, after the
measurement of the particle size in a predetermined
dispersion medium, the thus measured particle size can be
employed as the particle size of the particulate
component in the coating material composition. In the
25 dynamic light scattering method, a fine particle being
dispersed in a dispersion medium and undergoing Brownian
motion may be irradiated with laser light, the light
scattered from the particle may be observed, the
autocorrelation function may be determined by the photon
30 correlation method, and the particle size may be measured
by using the cumulant method. As the apparatus for
measuring the particle size by the dynamic light
scattering method, for example, FPAR-1000 mfd. by Otsuka
Electronics Co., Ltd. can be used. In the present
35 invention, a dispersion sample containing particles to be
measured may be measured at 25°C so as to determine the
cumulant average particle size, and the average value of
- 38 -
5 measurements in total may be taken as the average
particle size of the particle. The measurement of the
average particle size by the dynamic light scattering
method is described in detail, for example, in Journal of
5 Chemical Physics, Vol. 57, No. 11, page 4814 (December,
1972).
[0099]
Also, in a case where at least one of the spherical
silica particle (C1), the spherical silica particle (C2),
10 the polyolefin resin particles (D), the color pigment
(E), and the at least one resin particles (F) selected
from an acrylic resin and a silicone resin is present as
a particulate component in the coating film (a), it may
also be possible to directly determine the shape or
15 particle size of the component by observing the crosssection
of the coating film (a). In a case where the
particle is not truly spherical, the major axis and the
minor axis of the particle may be measured, and the
average value thereof may be employed as the particle
20 size. The method of observing the cross-section of the
coating film (a) may not be particularly limited, but
there can be suitably used, for example, a method of
embedding the coated metal sheet in an ordinary
temperature drying-type epoxy resin perpendicularly to
25 the thickness direction of the coating film, and after
the mechanical polishing of the embedding surface,
observing the cross-section by SEM (scanning electron
microscope); or a method of cutting out an observation
sample of 50 to 100 nm in thickness from the coated metal
30 sheet by using an FIB (focused ion beam) system so as to
show the vertical cross-section of the coating film, and
observing the coating film cross-section by TEM
(transmission electron microscope) .
[0100]
35 The coating film (a) of the present invention may
preferably be formed by applying the composition as an
- 39 -
aqueous coating material composition by using an aqueous
solvent, and then heat-drying the thus coated
composition. The method of applying the aqueous coating
material composition may be not particularly limited, but
5 a known method such as roll coating, spray coating, bar
coating, dipping and electrostatic coating may
appropriately be used.
[0101]
The process for producing the aqueous coating
10 material composition may not be particularly limited, but
may include: for example, a method of adding respective
coating film (a)-forming components in water and
dissolving or dispersing the components by stirring with
a disper. In order to enhance the solubility or
15 dispersibility of respective coating film (a)-forming
components, a known hydrophilic solvent or the like, for
example, alcohols such as ethanol, isopropyl alcohol,
tert-butyl alcohol and propylene glycol; cellosolves such
as ethylene glycol monobutyl ether and ethylene glycol
20 monoethyl ether; esters such as ethyl acetate and butyl
acetate; and ketones such as acetone, methyl ethyl ketone
and methyl isobutyl ketone, may be added, as desired.
[0102]
As described above, the present invention is
25 characterized in that the coating film (a) contains (A)
an organic resin as film-forming component, two kinds of
specific spherical silica particles (Cl and C2), and (0)
polyolefin resin particles having a specific average
particle size.
30 [0103]
Incidentally, in the case of scaly silica (nonspherical
silica particles), it may tend to be difficult
for the coating film (a) to satisfy both the scratch
resistance and the workability.
35 [0104]
In connection with the scratch resistance, the term
• - 40 -
5
25
10
15
"abrasion resistance" may be known. As for "abrasion
resistance" and "scratch resistance", a distinct
definition may not be necessarily provided for the
difference therebetween. However, the "abrasion
resistance" may generally refer to a resistance to an
abrasion flaw (a scratch produced by repeated abrasion
under a relatively low surface pressure), which is caused
by rubbing between a finished article and a corrugated
box due to vibration, when the finished article in the
corrugated box is transported. On the other hand, the
"scratch resistance" may generally cover all of scratches
which are generated during handling, press forming,
transportation and the like of a steel sheet.
Accordingly, from this standpoint, the "abrasion
resistance" may be encompassed by the "scratch
resistance".
That is, even a coated steel sheet having "abrasion
resistance" may not always satisfy the "scratch
resistance". For example, in the case of using the
above-mentioned scaly silica, as described later, unlike
spherical silica, operation and effect such that the
silica particle avoids contact thereof with a material to
be contacted therewith while rolling cannot be obtained,
and the friction resistance may become large.
Accordingly, the scaly silica may be useful to secure the
abrasion resistance but cannot be expected to provide an
effect on the scratch resistance.
[0105]
According to the knowledge of the present inventors,
30 actual scratches covered by the scratch resistance, which
cause a problem from the user side in practice, may not
be an abrasion flaw, even when they are generated during
transportation. However, they may be scratches caused by
rubbing with a hard material such as metal, but not with
35 a relatively soft material such as corrugated box. For
example, they may be scratches caused by rubbing with a
metal powder such as burr debris generated from a steel
20
• - 41 -
sheet, or scratches caused by rubbing due to roughening
of the metal mold surface during press forming.
Accordingly, an evaluation method of simulating the
"scratch resistance" in a harsher condition than for
5 abrasion, which is widely referred to, may be necessary,
and as such an evaluation method, for example, evaluation
of scratch resistance to steel wool, which is employed in
the evaluation of the subject application, can be used.
[0106]
10 In order to enhance the above-mentioned scratch
resistance, it may be important to avoid the contact with
a material to be contacted (such as burr debris and metal
mold) with the underlying metal, and even if contacted,
it may be important to reduce the friction resistance.
15 In particular, when the material to be contacted is a
hard material, the contact can be prevented by the
presence of hard particles in the coating film. However,
the hard particle itself may serve as an abrasive and
scratch the underlying metal, and for preventing this,
20 the shape should be designed. A spherical (silica
particle) shape may be very effective, because it can
avoid contact while rolling, and accordingly, can reduce
the friction resistance with the underlying metal. In
contrast, a scaly (silica particle) shape may be
25 improper, because the particle may be trapped in the
coating film due to a large contact area with the coating
film of the particle in the coating film, and may be
hardly movable and highly probably act as an abrasive.
[0107]
30 In the present invention, it may also be important
to enhance the scratch resistance and not to reduce the
workability, which is a performance contradicting it.
When a hard particle is added to the coating film so as
to enhance the scratch resistance, the coating film may
35 become hard and reduced in the workability. In
particular, when the particle has a scaly shape, the
particle may be present in layers in the coating film,
- 42 -
and therefore the workability may tend to be greatly
reduced (cracks may readily be generated in the coating
film upon elongation of the underlying metal). On the
other hand, when the shape is spherical (silica
5 particle), reduction in the workability can be minimized.
[0108]
In the present invention, the contact with the
underlying metal may be prohibited by a hard and
relatively large spherical particle, and the friction
10 resistance may be reduced by a soft and low-polarity
polyolefin resin particles, so that very high scratch
resistance can be obtained. In particular, when the
material to be contacted is hard, a soft and low-polarity
polyolefin resin may be effective.
15 [0109]
In the present invention, the mixing of the abovementioned
spherical silica and polyolefin resin particles
may produce a remarkable effect on enhancement of the
scratch resistance. According to the knowledge of the
20 present inventors, it may be presumed that the
combination use of the spherical silica and the
polyolefin resin particles makes it possible, for
example, for the head of the spherical silica in the
coating film surface side to prevent a steel wool from
25 scratching the coating film and for the polyolefin resin
particles to facilitate slippage of a steel wool.
Further, it may also be considered that the combination
use of the polyolefin resin particles and the spherical
silica makes it possible for the polyolefin resin
30 attached in a small amount to a steel wool to facilitate
the rolling of the spherical silica. In addition, the
sulfonic acid group contained in the polyester resin may
also be considered to facilitate the rolling of the
spherical silica.
35 [0110]
In the present invention, in an embodiment where, as
described above, the polyester resin as the film-forming
- 43 -
component (matrix component) of the coating film has a
relatively high polarity (for example, an embodiment
where the polyester resin contains a sulfonic acid
group), polyolefin resin particles having a relatively
5 low polarity may tend to be oriented on the coating film
surface at the stage of forming the coating film due to
difference in the surface free energy therebetween. The
orientation of the polyolefin resin on the coating film
surface may be effective in reducing the friction
10 resistance with a material to be contacted, and may make
it possible to further enhance the scratch resistance.
[0111]
In this way, in order to secure the corrosion
resistance of a chromate-free coated metal sheet, the
15 polyolefin particle should avoid the contact with the
surface of the underlying metal sheet, which is the base
material. In addition, in order to prevent scratching,
the polyolefin resin particles should appear from the
surface of the coating film formed from a mixture of the
20 film-forming component (matrix component) of the coating
film and the polyethylene resin particles. For such a
purpose, the present inventors have found it preferred to
"separate" the polyolefin resin particles from the
underlying metal sheet as the base material at the stage
25 before the drying of the coating film. As one of means
to "separate" the polyolefin resin particles from the
underlying metal sheet as the base material, the abovementioned
difference in the surface free energy may be
suitably utilized.
30 [0112]
The method of baking or drying the coating material
composition for forming the coating film (a) according to
the present invention may not be particularly limited,
and the metal sheet may be previously heated, the metal
35 sheet may be heated after coating, or the drying may be
performed by a combination thereof. The heating method
may not be particularly limited, and hot air, induction
- 44 -
heating, near infrared ray, direct flame and the like may
be used individually or in combination. The
baking/drying temperature may preferably be from 150 to
250°C, more preferably from 170 to 240°C, and most
5 preferably from 180 to 230°C, in terms of the ultimate
sheet temperature of the metal sheet. If the ultimate
temperature is less than 150°C, curing by baking may be
insufficient, and the workability, corrosion resistance
and scratch resistance may be reduced. On the other
10 hand, if the temperature exceeds 250°C, the amount of the
polyolefin resin particles (D) flowed out from the
coating film (a) may be increased, and the corrosion
resistance and scratch resistance may be reduced, or
curing by baking of the coating film (a) may excessively
15 proceed so as to impair the corrosion resistance and
workability. The baking/drying time may preferably be
from 2.5 to 20 seconds, more preferably from 3 to 15
seconds. If the baking/drying time is less than 2.5
seconds, curing by baking may be insufficient, and the
20 corrosion resistance and scratch resistance may be
reduced. On the other hand, if the time exceeds 20
seconds, the productivity may be reduced. Also, in the
case of short-time heating for 20 seconds or less, if
polyolefin resin particles having a low softening point
25 are used, the polyolefin resin particles may readily flow
out from the coating film during heat-drying of the
coating film, and reduction in the corrosion resistance
or scratch resistance may be increased. However, when
the polyolefin resin particles (D) having a softening
30 point of 125°C or more, which is one embodiment of the
present invention, is applied, reduction in the corrosion
resistance and scratch resistance may be suppressed even
in the short-time heating.
[0113]
35 The baking/drying step may be further followed by a
cooling step, as desired. The cooling method may not be
• - 45 -
particularly limited, but a water cooling method may be
preferred. In a case where the baking/drying step is
followed by a cooling step, particularly a rapid cooling
step such as water cooling, if polyolefin resin particles
5 having a low softening point are used, the polyolefin
resin particles may readily flow out from the coating
film during cooling, and reduction in the corrosion
resistance or scratch resistance may be increased.
However, when the polyolefin resin particles (0) having a
10 softening point of 125°C or more, which is one embodiment
of the present invention, is applied, reduction in the
corrosion resistance and scratch resistance may be
suppressed even when a cooling step is provided.
[0114]
15 When the softening point of the polyolefin resin (0)
is TsoC, the sheet temperature of the metal sheet at water
cooling is TMoC and the water temperature of the cooling
water is TwoC, the temperature of the heat-dried metal
sheet and the temperature of the cooling water in the
20 cooling step may preferably satisfy TM>Ts and Tw~(TM-150)/4
in consideration of the softening point of the polyolefin
resin particles (0) for use in the present invention. If
the sheet temperature of the metal sheet at water cooling
is higher than the softening point of the polyolefin
25 resin particles (0), the polyolefin resin particles (0)
may be softened and enter a state of readily flowing out
from the coating film (a), and as the sheet temperature
of the metal sheet is higher and the temperature of the
cooling water is lower (as the cooling is rapider), the
30 outflow of the polyolefin resin particles (0) from the
coating film (a) may more readily occur and the corrosion
resistance and scratch resistance may be more likely to
be reduced. That is, in a case where the sheet
temperature of the metal sheet is high, the temperature
35 of the cooling water may be set high accordingly, whereby
the outflow of the polyolefin resin particles (0) from
- 46 -
i'.·.~ ~ Ij
j
the coating film (a) can be inhibited and reduction in
the corrosion resistance or scratch resistance can be
minimized. More specifically, the temperature of cooling
water may preferably be controlled to satisfy Tw~(TM150)/
4.
[0115]
5
10
In the present invention, the coating film (a) may
preferably have (p) a primer treatment layer in the lower
side. The primer treatment layer (p) may not be
particularly limited, but by providing (p) a primer
treatment layer containing at least one member selected
from a silane coupling agent, an organic resin and a
polyphenol compound, the adherence to the underlying
metal sheet can be more enhanced, and the corrosion
15 resistance can be more improved. Also, by providing (p)
a primer treatment layer containing all of a silane
coupling agent, an organic resin and a polyphenol
compound, the adherence to the underlying metal sheet can
be still more enhanced, and the corrosion resistance can
20 be still more improved.
[0116]
The silane coupling agent to be contained in the
underlying coating layer (p) may not be particularly
limited. Specific examples thereof may include:
25 vinyltrimethoxysilane, vinyltriethoxysilane, yaminopropyltrimethoxysilane,
y-aminopropyltriethoxysilane,
N-[2-(vinylbenzylamino)ethyl]-3-
30
35
aminopropyltrimethoxysilane, ymethacryloxypropylmethyldimethoxysilane,
ymethacryloxypropyltrimethoxysilane,
ymethacryloxypropylmethyldiethoxysilane,
ymethacryloxypropyltriethoxysilane,
yglycidoxypropyltriethoxysilane,
yglycidoxypropylmethyldiethoxysilane,
yglycidoxypropyltrimethoxysilane,
2-(3,4-
- 47 -
epoxycyclohexyl)ethyltrimethoxysilane, N-~(aminoethyl)yaminopropyltrimethoxysilane,
N-~-(aminoethyl)-yaminopropyltriethoxysilane,
N-~-(aminoethyl)-yaminopropylmethyldimethoxysilane,
N-phenyl-y-
5 aminopropyltrimethoxysilane, ymercaptopropyltrimethoxysilane,
which may be sold from
Shin-Etsu Chemical Co., Ltd., Dow Corning Toray Co.,
Ltd., Chisso Corporation, Momentive Performance Materials
Japan Inc., and the like. One of these silane coupling
10 agents may be used alone, or two or more thereof may be
used in combination.
[0117]
The organic resin to be contained in the primer
treatment layer (~) may not be particularly limited, and
15 for example, a known organic resin such as polyester
resin, polyurethane resin, epoxy resin, phenol resin,
acrylic resin and polyolefin resin may be used. In order
to more enhance the adherence to the underlying metal
sheet, at least one of a polyester resin, a polyurethane
20 resin, an epoxy resin and a phenol resin may preferably
be used, and from the standpoint of increasing the
compatibility with the polyester resin (Al ) contained in
the black coating film (a) and enhancing the adherence,
it may be more preferred to contain a polyester resin in
25 the primer treatment layer (~).
[0118]
The polyphenol compound to be contained in the
primer treatment layer (~) refers to a compound having
two or more phenolic hydroxyl groups bonded to a benzene
30 ring, or a condensation product thereof. Examples of the
compound having two or more phenolic hydroxyl groups
bonded to a benzene ring may include: gallic acid,
pyrogallol, and catechol. The condensation product of a
compound having two or more phenolic hydroxyl groups
35 bonded to a benzene ring may not be particularly limited
and may include, for example, a polyphenol compound which
- 49 -
layer (p) may not be obtained. On the other hand, if the
amount exceeds 1,000 mg/m2
, the primer treatment layer (p)
may readily cause a cohesive failure and the adherence
may be reduced. In view of stable effect and
5 profitability, the amount attached may be more preferable
from 50 to 500 mg/m2
•
[0123]
The method of forming the primer treatment layer (p)
may not be particularly limited, but the layer may be
10 formed by applying the coating agent for forming the
primer treatment layer (p) to at least one surface of the
metal sheet and heat-drying it. The method of applying
the coating agent may not be particularly limited, but a
known method such as roll coating, spray coating, bar
15 coating, dipping and electrostatic coating may
appropriately be used. The baking/drying method may not
be particularly limited, and the metal sheet may be
previously heated, the metal sheet may be heated after
coating, or the drying may be performed by a combination
20 thereof. The heating method may not be particularly
limited, and hot air, induction heating, near infrared
ray, direct flame and the like may be used individually
or in combination. The baking/drying temperature may
preferably be from 60 to 150°C, more preferably from 70 to
25 130°C, in terms of the ultimate temperature. If the
ultimate temperature is less than 60°C, drying may be
insufficient, and the adherence to the base material or
the corrosion resistance may be reduced. On the other
hand, if the temperature exceeds 150°C, the adherence to
30 the base material may be deteriorated.
[0124]
35
The metal sheet which can be applied in the present
invention may not be particularly limited and examples
thereof may include: iron, an iron-based alloy, aluminum,
an aluminum-based alloy, copper, and a copper-based
alloy. A plated metal sheet obtained by applying an I.I1
• - 50 -
5
10
15
20
arbitrary plating to a metal sheet surface may also be
used. Among these, a zinc-based plated steel sheet and
an aluminum-based plated steel sheet are most preferably
applied in the present invention.
[0125]
The zinc-based plated steel sheet may include a
zinc-based plated steel sheet such as galvanized steel
sheet, zinc-nickel plated steel sheet, zinc-iron plated
steel sheet, zinc-chromium plated steel sheet, zincaluminum
plated steel sheet, zinc-titanium plated steel
sheet, zinc-magnesium plated steel sheet, zinc-manganese
plated steel sheet, zinc-aluminum-magnesium plated steel
sheet and zinc-aluminum-magnesium-silicon plated steel
sheet, and a plated steel sheet where cobalt, molybdenum,
tungsten, nickel, titanium, chromium, aluminum,
manganese, iron, magnesium, lead, bismuth, antimony, tin,
copper, cadmium, arsenic or the like is incorporated into
the plating layer above as a small amount of a dissimilar
metal element or impurity or where an inorganic material
such as silica, alumina and titania is dispersed in the
plating layer.
[0126]
The aluminum-based plated steel sheet may include
aluminum or an alloy of aluminum and at least one of
silicon, zinc and magnesium, for example, an aluminumsilicon
plated steel sheet, an aluminum-zinc plated steel
sheet, and an aluminum-silicon-magnesium plated steel
sheet.
[0127]
30 Further, the present invention can also be applied
to a multilayer plating where the above-mentioned plating
is combined with other kinds of plating such as iron
plating, iron-phosphorus plating, nickel plating and
cobalt plating. The plating method may not be
35 particularly limited and may be any known method such as
electroplating, hot-dip plating, deposition plating,
diffusion coating and vacuum plating.
25
, - 51 -
EXAMPLES
[0128]
The present invention is described below by
5 referring to Examples. However, the present invention is
not be limited to these Examples.
[0129]
(1) Metal Sheet
The types of metal sheets used are shown in Table 1.
10 For the base material of the plated metal sheet, a soft
steel sheet having a thickness of 0.5 mm was used. As
the SUS sheet, a ferritic stainless steel sheet (steel
components: C: 0.008 mass%, Si: 0.07 mass%, Mn: 0.15
mass%, P: 0.011 mass%, S: 0.009 mass%, AI: 0.067 mass%,
15 Cr: 17.3 mass%, Mo: 1.51 mass%, N: 0.0051 mass%, Ti: 0.22
mass%, balance: Fe and unavoidable impurities) was used.
The metal sheet was used after subjecting its surface to
an alkali degreasing treatment, water washing and drying.
[0130]
20 Table 1
No. Metal Sheet (thickness: 0.5 ffiffi, two-sided plating)
M1 electrogalvanized steel sheet (plating deposition: 20 g/m2
)
M2 hot-dip galvanized steel sheet (plating deposition: 60
g/m2
)
M3 hot-dip galvannealed steel sheet
(Fe: 10%, plating deposition: 45 g/m2
)
M4 electro Zn-10% Ni alloy plated steel sheet
(plating deposition: 20 g/m2
)
M5 hot-dip Zn-ll% Al-3% Mg-0.2% Si plated steel sheet
(plating deposition: 60 g/m2
)
M6 hot-dip Zn-55% Al-1.6% Si plated steel sheet
(plating deposition: 75 g/m2
)
M7
hot-dip Al-9% Si plated steel sheet
(plating deposition: 40 g/m2
)
M8 SUS plate (ferritic stainless steel sheet)
[0131]
(2) Primer Treatment Layer
The coating agent for forming the primer
25 treatment layer was prepared by blending an organic resin
(Table 2), a silane coupling agent (Table 3) and a
- 52 -
polyphenol compound (Table 4) in the blending amounts
(mass% as solid content) shown in Table 5 and stirring
the blend with use of a disperser for coating materials.
The surface of the metal sheet prepared in the step (1)
5 above was coated with the coating agent by a roll coater
to give an attached amount of 100 mg/m2 and dried under
the condition of an ultimate sheet temperature of 70°C to
form a primer treatment layer (P1 to P9) as needed.
[0132]
10 Table 2
No. Organic Resin
a1
aqueous polyester resin
(Vylonal MD-1200, mfd. by Toyobo)
a2
aqueous epoxy resin
(Adeka Resin EM0436FS-12, mfd. by asahi Denka)
a3
aqueous phenol resin
(PR-NPK-261, mfd. by Sumitomo Bakelite)
a4
aqueous acrylic resin
(Kanevinol KD-5, mfd. by NSC Japan)
[0133]
Table 3
No. Silane Coupling Agent
b1 3-g1ycidoxypropyltrimethoxysilane
b2 3-aminopropyltriethoxysilane
15 [0134]
Table 4
No. Polyphenol Compound
cl
tannic acid (Tannic Acid AL, mfd. by Fuji Chemical
Industry)
[0135]
, - 53 -
Table 5
Organic Resin Silane Polyphenol Other Components
No.
Coupling Agent Compound
Kind Amount Kind Amount
Kind
Amount Kind Amount
(%) (% ) (% ) (% )
/31 B1 100
/32 C1 100
/33 01 100
/34 B1 40 C1 30 01 30
/35 B2 40 C1 30 01 30
/36 B3 40 C1 30 01 30
/37 B4 40 C1 30 01 30
/38 B1 40 C2 30 01 30
/39 B1 30 C1 25 01 25 *silica 20
*silica: Snowtex N (mfd. by Nissan Chemlcal Industrles,
Ltd. )
5 [0136]
(3) Coating Film
The coating material composition for forming the
coating film was prepared by blending (A) an organic
resin (Production Examples 1 to 5 and Table 6), (B) a
10 curing agent (Table 7), (C) silica particles (Table 8),
(D) polyolefin resin particles (Table 9), (E) a color
pigment (Table 10), and (F) at least one resin particles
selected from an acrylic resin and a silicone resin
(Table 11) in the blending amounts (mass% as solid
15 content) shown in Tables 12 to 22 and stirring the blend
with use of a disperser for coating materials. The thus
obtained coating material composition was applied on the
primer treatment layer formed in (2) above (when the
primer treatment layer was not formed, on the metal sheet
20 prepared in step (1) above) by a roll coater to give a
predetermined film thickness and heat-dried at a
predetermined ultimate sheet baking temperature to form a
coating film.
[0137]
25
A reaction vessel equipped with a stirrer, a
condenser and a thermometer was charged with 199 parts of
•
5
10
15
20
- 54 -
terephthalic acid, 232 parts of isophthalic acid, 199
parts of adipic acid, 33 parts of 5-sodium
sulfoisophthalic acid, 312 parts of ethylene glycol, 125
parts of 2,2-dimethyl-1,3-propanediol, 187 parts of 1,5pentanediol
and 0.41 parts of tetrabutyl titanate, and an
esterification reaction was performed from 160°C to 230°C
over 4 hours. Subsequently, the pressure in the system
was gradually decreased and after reducing the pressure
to 5 mmHg over 20 minutes, a polycondensation reaction
was further performed under vacuum of 0.3 mmHg or less at
260°C for 40 minutes. Thereafter, 20 parts of
butylcellosolve and 42 parts of methyl ethyl ketone were
charged into 100 parts of the copolymerized polyester
resin obtained and dissolved with stirring at 80°C for 2
hours, and 213 g of ion-exchanged water was further
charged to perform water dispersion. The solvent was
then removed by distillation under heating, the residue
was filtered through a nylon mesh of 200 meshes to obtain
Polyester Resin Water Dispersion (A1) having a solid
content concentration of 30%.
[0138]

A reaction vessel equipped with a stirrer, a
condenser and a thermometer was charged with 199 parts of
25 terephthalic acid, 266 parts of isophthalic acid, 199
parts of adipic acid, 312 parts of ethylene glycol, 125
parts of 2,2-dimethyl-1,3-propanediol, 187 parts of 1,5pentanediol
and 0.41 parts of tetrabutyl titanate, and an
esterification reaction was performed from 160°C to 230°C
30 over 4 hours. Subsequently, the pressure in the system
was gradually decreased and after reducing the pressure
to 5 mmHg over 20 minutes, a polycondensation reaction
was further performed under vacuum of 0.3 mmHg or less at
260°C for 40 minutes. In a nitrogen stream, after cooling
35 to 220°C, 23 parts of trimellitic anhydride and 16 parts
of ethylene glycol bisanhydrotrimellitate were charged
•
5
10
- 55 -
and a reaction was performed for 30 minutes. Thereafter,
20 parts of butylcellosolve and 42 parts of methyl ketone
were charged into 100 parts of the copolymerized
polyester resin obtained and dissolved with stirring at
80°C for 2 hours, and 23 parts of isopropyl alcohol and
3.5 parts of triethylamine were charged. Water
dispersion was performed with 213 parts of ion-exchanged
water, and the solvent was then removed by distillation
under heating. The residue was filtered through a nylon
mesh of 200 meshes to obtain Polyester Resin Water
Dispersion (A2) having a solid content concentration of
30%.
[0139]

15 A reaction vessel equipped with a stirrer, a
condenser and a thermometer was charged with 199 parts of
terephthalic acid, 232 parts of isophthalic acid, 199
parts of adipic acid, 33 parts of 5-sodium
sulfoisophthalic acid, 250 parts of ethylene glycol, 125
20 parts of 2,2-dimethyl-1,3-propanediol, 187 parts of 1,5pentanediol,
62 parts of bisphenol A ethylene oxide
adduct and 0.41 parts of tetrabutyl titanate, and an
esterification reaction was performed from 160°C to 230°C
over 4 hours. Subsequently, the pressure in the system
25 was gradually decreased and after reducing the pressure
to 5 mmHg over 20 minutes, a polycondensation reaction
was further performed under vacuum of 0.3 mmHg or less at
260°C for 40 minutes. Thereafter, 20 parts of
butylcellosolve and 42 parts of methyl ketone were
30 charged into 100 parts of the copolymerized polyester
resin obtained and dissolved with stirring at 80°C for 2
hours, and 213 g of ion-exchanged water was further
charged to perform water dispersion. The solvent was
then removed by distillation under heating, the residue
35 was filtered through a nylon mesh of 200 meshes to obtain
Polyester Resin Water Dispersion (A3) having a solid
- 56 -
content concentration of 30%.
[0140]

230 Parts of polyester polyol having an average
5 molecular weight of 900, which was synthesized from an
adipic acid having a hydroxyl group at the terminal and
1,4-butylene glycol, and 15 parts of 2,2bis(
hydroxymethyl)propionic acid were added to 100 parts
of N-methyl 2-pyrrolidone and dissolved under heating at
10 SO°C. Thereafter, 100 parts of hexamethylene diisocyanate
was added, and the mixture was reacted for 2 hours under
heating at 110°C. The reaction product was neutralized by
adding 11 parts of triethylamine, and the obtained
solution was added dropwise under vigorous stirring to an
15 aqueous solution prepared by mixing 5 parts of
ethylenediamine and 570 parts of ion-exchanged water to
obtain Polyurethane Resin Water Dispersion (A4) having a
solid content concentration of 30%.
[0141]
20
SO Parts of polyester polyol having an average
molecular weight of 900, which was synthesized from an
adipic acid having a hydroxyl group at the terminal and
1,4-butylene glycol, 120 parts of bisphenol A propylene
25 oxide 3-mol adduct having an average molecular weight of
700, and 12 parts of 2,2-bis(hydroxymethyl)propionic acid
were added to 100 parts of N-methyl 2-pyrrolidone and
dissolved under heating at SO°C. Thereafter, 100 parts of
hexamethylene diisocyanate was added, and the mixture was
30 reacted for 2 hours under heating at 110°C. The reaction
product was neutralized by adding 11 parts of
triethylamine, and the obtained solution was added
dropwise under vigorous stirring to an aqueous solution
prepared by mixing 5 parts of ethylenediamine and 570
35 parts of ion-exchanged water to obtain Polyurethane Resin
(A5) having a solid content concentration of 30%.
[0142]
Table 6
- 57 -
No. Organic Resin (A)
Al aqueous polyester resin (Production Example 1, containing an
ester group and an Na sulfonate group)
A2
aqueous polyester resin (Production Example 2, containing an
ester group and a carboxyl group)
A3 aqueous polyester resin (Production Example 3, containing an
ester group, a bisphenol skeleton and an Na sulfonate group)
A4
aqueous polyurethane resin (Production Example 4, containing
a urethane group, a urea group and a carboxyl group)
aqueous polyurethane resin (Production Example 5, containing
A5 a urethane group, a urea group, a bisphenol skeleton and a
carboxyl group)
A6 aqueous epoxy resin (Adeka Resin EM0436FS-12, mfd. by
Asahi Denka)
A7
aqueous acrylic resin (Joncryl J-61, mfd. by Johnson
Polymer)
A8
aqueous polyolefin resin (HYTEC S-3121, mfd. by Toho
Chemical)
[0143]
5 Table 7
No. Curing Agent (8)
81
melamine resin (Cymel 303, mfd. by Nihon Cytec
Industries)
82 melamine resin (Cymel 325, mfd. by Nihon Cytec
Industries)
83 isocyanate compound (Takenate WD-725, mfd. by
Mitsui Chemical Polyurethane)
[0144]
Table 8
No. Silica particles (C)
C1 spherical silica particle (Snowtex N, mfd. by Nissan Chemical, particle size: 15 nm)
C2 spherical silica particle (Snowtex NXS, mfd. by Nissan Chemical, particle size: 5 nm)
C3 spherical silica particle (Snowtex XL, mfd. by Nissan Chemical, particle size: 50 nm)
C4 spherical silica particle (Snowtex YL, mfd. by Nissan Chemical, particle size: 65 nm)
C5 spherical silica particle (MP-1040, mfd. by Nissan Chemical, particle size: o. 1 J.lTIl)
C6 spherical silica particle (MP-2040, mfd. by Nissan Chemical, particle size: o. 2 J.lTIl)
C7 spherical silica particle (MP-4540, mfd. by Nissan Chemical, particle size: 0.45 J.lTIl)
C8 spherical silica particle (HPS-0500, mfd. by Toagosei, particle size: o. 5 J.lTIl)
C9 spherical silica particle (HPS-1000, mfd. by Toagosei, particle size: 1 J.lTIl)
C10 spherical silica particle (HPS-2000, mfd. by Toagosei, particle size: 2 J.lTIl)
C11 spherical silica particle (HPS-3500, mfd. by Toagosei, particle size: 3 . 5 J.lTIl)
C12 spherical silica particle (SHARKSIL 100-type, mfd. by Tokai Chemical Industry, particle size: 5 J.lTIl)
C13 spherical silica particle (HS-302, mfd. by, Nippon Steel Materials Micron, particle size: 6.8 J.lTIl)
C14 amorphous silica particle (Nipsil, mfd. by Tosoh Silica, particle size: 2 . 5 J.lTIl)
C15
scaly silica particle (SUNLOVELY LFS HB-020SN, mfd. by Dohkai Chemical Industries, particle size:
o. 2 J.lTIl)
•
U1
CD
* ".R. 014i £ *,§\!t,VAC¥iMlIi&iW1b..JS ....t#,;M;;;Uii tkJi.k?L $f1!C:;;;;::;:..;z;as,.yi:Z;ll.-;"B,;.; ),H)/%.-%il j,M H'4.,,' $ 1,.." $, ~,Qv< .wJM¥,-," t f,·,,,, ,~,,.jU£ LX4;"itL" ~.®W!£1_,. .Hj ;z ",,;4$~ ,";,J4.£.13 , gzaL· ,J, ~ZlM&&.• &Z AL liM ~
[0145]
Table 9 •
Polyolefin Resin particles (D)
No. Softening Particle Density
Penetro- Average
Classification Brand
(0 C) (kg/m3
)
meter Molecular
Point size (f.1m) Hardness Weight
Dl high-density polyethylene Chemipearl XWF3002 (mfd. by Mitsui
132 0.2 970 less than 1 4000
Chemical)
D2 high-density polyethylene Chemipearl W900 (mfd. by Mitsui
132 0.6 970 less than 1 4000
Chemical)
D3 high-density polyethylene Chemipearl W700 (mfd. by Mitsui
132 1 970 less than 1 4000
Chemical)
D4 high-density polyethylene Chemipearl W300 (mfd. by Mitsui
132 3 970 less than 1 4000
Chemical)
D5 high-density polyethylene Chemipearl W308 (mfd. by Mitsui
132 6 970 less than 1 4000
Chemical)
D6 high-density polyethylene Chemipearl WlOO (mfd. by Mitsui
128 3 970 1 2000
Chemical)
D7 high-density polyethylene Chemipearl XWH201 (mfd. by Mitsui
140 1 970 less than 1 7000
Chemical)
D8 polypropylene Chemipearl WPIOO (mfd. by Mitsui
148 1 900 less than 1 10000
Chemical)
D9 high-density polyethylene A-110 (mfd. by Gifu Shellac) 126 5 980 less than 1 4000
DIO high-density polyethylene A-375 (mfd. by Gifu Shellac) 125 2 980 1 to 2 4000
Dll high-density polyethylene AB-50 (mfd. by Gifu Shellac) 125 1 980 1 to 2 4000
D12 polypropylene AC-35 (mfd. by Gifu Shellac) 143 0.8 890 less than 1 10000
D13 low-density polyethylene
Chemipearl W4005 (mfd. by Mitsui
110 0.5 920 3 5000
Chemical)
D14 low-density polyethylene
Chemipearl W40l (mfd. by Mitsui
110 1 920 3 5000
Chemical)
D15 low-density polyethylene
Chemipearl W400 (mfd. by Mitsui
110 4 920 3 5000
Chemical)
D16 low-density polyethylene Chemipearl W950 (mfd. by Mitsui
113 0.6 920 10 2000
Chemical)
D17 low-density polyethylene
Chemipearl WF640 (mfd. by Mitsui
113 1 920 10 2000
Chemical)
D18 low-density polyethylene Chemipearl W500 (mfd. by Mitsui
113 2.5 920 10 2000
Chemical)
D19 low-density polyethylene A-348 (mfd. by Gifu Shellac) 115 3 940 4 2500
D20 low-density polyethylene AE-04 (mfd. by Gifu Shellac) 117 2.5 930 4 2000
D2l low-density polyethylene AG-23 (mfd. by Gifu Shellac) 100 1 920 2 to 3 3000
U1
\.0
; - ¥ "\L. X. ¢. L,· ·'~ii"JMX.CL& ¥I""" $ 3+ A%
[0146]
Table 10
- 60 -
No. Color Pigment (E)
E1
carbon black (MCF#980, mfd. by Mitsubishi Chemical,
particle size: 16 nm)
E2
carbon black (MA100, mfd. by Mitsubishi Chemical,
particle size: 24 nm)
E3
titanium oxide (R-780, mfd. by Ishihara Sangyo,
particle size: 240 nm)
5 [0147]
Table 11
No. Resin particles (F)
F1
spherical acrylic resin particles (SSX-101, mfd. by
Sekisui Plastics, particle size: 1 flIIl)
F2
spherical acrylic resin particles (SSX-102, mfd. by
Sekisui Plastics, particle size: 2 flIIl)
F3
spherical acrylic resin particles (SSX-103, mfd. by
Sekisui Plastics, particle size: 3 flIIl)
spherical acrylic resin particles (SSX-104, mfd. by
F4
Sekisui Plastics, particle size: 4 flIIl)
spherical acrylic resin particles (SSX-105, mfd. by
F5
Sekisui Plastics, particle size: 5 flIIl)
spherical acrylic resin particles (SSX-108, mfd. by
F6
Sekisui Plastics, particle size: 8 flIIl)
spherical acrylic resin particles (SSX-llO, mfd. by
F7
Sekisui Plastics, particle size: 10 flIIl)
spherical silicon resin particles (Tospearl 120, mfd. by
F8
Momentive Performance Materials, particle size: 2 flIIl)
spherical silicon resin particles (Tospearl 130, mfd. by
F9
Momentive Performance Materials, particle Slze: 3 flIIl)
FlO
spherical silicon resin particles (Tospearl 145, mfd. by
Momentive Performance Materials, particle size: 4.5 flIIl)
amorphous silicon resin particles (Tospearl 240, mfd. by
Fll
Momentive Performance Materials, particle size: 4 flIIl)
spherical silicon resin particles (X-52-854, mfd. by
F12
Shin-Etsu Chemical, particle size: 0.8 flIIl)
spherical silicon resin particles (KMP-590, mfd. by
F13
Shin-Etsu Chemical, particle size: 2 flIIl)
[0148]
Table 12 • Coating Film (a)
Curing Color
Silica particles (C)
Resin
Organic Resin (A) Agent Pigment Silica Silica particles
Polyolefin Resin
Particle particles (D)
PTL CF (B) (A)+ (B) (E) Particle (C2) (F) FT UT: H/D CWT: STF STF of
No. MS (Cl)
([3) (a) / (a) *4 *4 (~) TM Time CM Tw of Tw;:o, (TM-
*1 *1 *1 *2 (%) *3 *3 *4 *3 *4 PS *3 PS
SP: *3 PS : b (OC) (sec) (OC) TM>Ts 150)/4
KD AMT KD AMT KD AMT KD AMT KD AMT KD AMT PS KD AMT (~): KD AMT KD Ts AMT
(%) (%) (% ) (% ) (%) ( %) (nm) ( %) c (%) (~) (OC) (% ) (~)
: d : a
Example 1 Ml P4 al Al 100 Bl 20 77 Cl 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 2 Ml P4 a2 A2 100 Bl 20 77 Cl 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 3 Ml P4 a3 A3 100 Bl 20 77 Cl 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 4 Ml P4 a4 A6 100 Bl 20 77 Cl 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 5 Ml P4 a5 A7 100 Bl 20 77 Cl 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 6 Ml P4 a6 A8 100 Bl 20 77 Cl 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 7 Ml P4 a7 Al 50 A4 50 Bl 20 77 Cl 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 8 Ml P4 a8 A2 50 A4 50 Bl 20 77 Cl 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 9 Ml P4 a9 A3 50 A4 50 Bl 20 77 Cl 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 10 Ml P4 alO Al 50 A5 50 Bl 20 77 Cl 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 11 Ml P4 all A2 50 A5 50 Bl 20 77 Cl 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 12 Ml P4 a12 A3 50 A5 50 Bl 20 77 Cl 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 13 Ml P4 a13 Al 90 A8 10 Bl 20 77 Cl 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 14 Ml P4 a14 Al 45 A4 45 A8 10 Bl 20 77 Cl 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 15 Ml P4 a15 Al 45 A5 45 A8 10 Bl 20 77 Cl 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 16 Ml P4 a16 Al 100 77 Cl 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 17 Ml P4 a17 Al 50 A4 50 77 Cl 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 18 Ml P4 a18 Al 50 A5 50 77 Cl 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 19 Ml P4 a19 Al 50 A4 50 B2 20 77 Cl 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 20 Ml P4 a20 Al 50 A4 50 B3 20 77 Cl 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 21 Ml P4 a21 Al 50 A4 50 Bl 3 77 Cl 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 22 Ml P4 a22 Al 50 A4 50 Bl 5 77 Cl 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 23 Ml P4 a23 Al 50 A4 50 Bl 35 77 Cl 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 24 Ml P4 a24 Al 50 A4 50 Bl 40 77 Cl 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 25 Ml P4 a25 Al 50 A4 50 Bl 20 77 J2 15 5 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 26 Ml P4 026 Al 50 A4 50 Bl 20 77 J3 15 50 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 27 Ml P4 a27 Al 50 A4 50 Bl 20 77 Cl 15 15 C7 5 0.45 D3 132 3 1 5 200 10 WC 20 A A
Example 28 Ml P4 a28 Al 50 A4 50 Bl 20 77 Cl 15 15 C8 5 0.5 D3 132 3 1 5 200 10 WC 20 A A
Example 29 Ml P4 a29 Al 50 A4 50 Bl 20 77 Cl 15 15 C10 5 2 D3 132 3 1 5 200 10 WC 20 A A
Example 30 Ml P4 a30 Al 50 A4 50 Bl 20 77 Cl 15 15 Cll 5 3.5 D3 132 3 1 5 200 10 WC 20 A A
MS: Metal Sheet, PTL: Primer Treatment Layer, CF: Coating Film, KD: Kind, AMT: Amount, PS: Particle size, SP: Softening Point, FT: Film Thickness, UT:
Ultimate Temperature, H/D: Heating/Drying, CM: Cooling Method, CWT: Cooling Water Temperature, STF: Satisfaction, WC: water cooling
Ol
I-'
L iUS, M ( WI ;",,30':1,-:"':,\ ~,$Aij£i"I§&)4iLSJbYf;,A # "jJ;S:4i".JW£k",,,,.q;\>'I!L,,,." w. 6 ",./dH_,,4:!Si.iii\%¥ ::2£.&&,,' p,-AU;;'; "" ;.bAt. iAi!iJ!&iJ&i#iI,J4C42a::ZX;~"'~,,, ¥t'f'<;;-,}:;J·"t'!L~#:P:;;;Zljii!t, w;,.A",·_>· iJi #1·,·3;#.4 j ,,",',_ .'i,"\"" ""'q" Q&b,,.)!iLj,,,jiit,!ii, ,}J!A'I$ll!&i@'
[0149]
Table 13 • Coating Film (a)
Curing Color
Silica particles (C)
Resin
Silica Polyolefin Resin
Organic Resin (A) Agent Pigment
Particle Silica particles particles (0)
No. MS PTL CF (B) (A)+(B) (E) (C1) Particle (C2 ) (F) E'T UT: H/O CWT: STF STF of
(P) (a) Ita) *4 *4 (lID\) TM Time CM Tw of Tw~ (TM-
*1 *1 *1 *2 (%) *3 *3 *4 *3 *4 PS *3 PS
SP: *3 PS : b (OC) (sec) (OC) TM>Ts 150)/4
KO AMT KO AMT KO AMT KO AMT KO AMT KO AMT PS KO AMT (lID\) : KO AMT KO Ts AMT
(% ) (%) ( %) (% ) (%) (% ) (nm) (%) c (% ) (lID\) (OC) (%) (lID\)
: d : a
Example 31 M1 P4 a31 A1 50 A4 50 B1 20 77 C1 15 15 C12 5 5 03 132 3 1 5 200 10 WC 20 A A
Example 32 M1 P4 a7 A1 50 A4 50 B1 20 77 C1 15 15 C9 2 1 03 132 3 1 5 200 10 WC 20 A A
Example 33 M1 P4 a7 A1 50 A4 50 B1 20 77 C1 15 15 C9 3 1 03 132 3 1 5 200 10 WC 20 A A
Example 34 M1 P4 a7 A1 50 A4 50 B1 20 77 C1 15 15 C9 10 1 03 132 3 1 5 200 10 WC 20 A A
Example 35 M1 P4 a7 A1 50 A4 50 B1 20 77 C1 15 15 C9 15 1 03 132 3 1 5 200 10 WC 20 A A
Example 36 M1 P4 a7 A1 50 A4 50 B1 20 77 C1 15 15 C9 25 1 03 132 3 1 5 200 10 WC 20 A A
Example 37 M1 P4 a32 A1 50 A4 50 B1 20 74 C1 15 15 C9 5 1 F1 3 1 03 132 3 1 5 200 10 WC 20 A A
Example 38 M1 P4 a33 A1 50 A4 50 B1 20 74 C1 15 15 C9 5 1 F2 3 2 03 132 3 1 5 200 10 WC 20 A A
Example 39 M1 P4 a34 A1 50 A4 50 B1 20 74 C1 15 15 C9 5 1 F3 3 3 03 132 3 1 5 200 10 WC 20 A A
Example 40 M1 P4 a35 A1 50 A4 50 B1 20 74 C1 15 15 C9 5 1 F4 3 4 03 132 3 1 5 200 10 WC 20 A A
Example 41 M1 P4 a36 A1 50 A4 50 B1 20 74 C1 15 15 C9 5 1 F5 3 5 03 132 3 1 5 200 10 WC 20 A A
Example 42 M1 P4 a37 A1 50 A4 50 B1 20 74 C1 15 15 C9 5 1 F6 3 8 03 132 3 1 5 200 10 WC 20 A A
Example 43 M1 P4 a38 A1 50 A4 50 B1 20 74 C1 15 15 C9 5 1 F9 3 3 03 132 3 1 5 200 10 WC 20 A A
Example 44 M1 P4 a39 A1 50 A4 50 B1 20 77 C1 15 15 C9 5 1 02 132 3 0.6 4 200 10 WC 20 A A
Example 45 M1 P4 a7 A1 50 A4 50 B1 20 77 C1 15 15 C9 5 1 03 132 3 1 4 200 10 WC 20 A A
Example 46 M1 P4 a40 A1 50 A4 50 B1 20 77 C1 15 15 C9 5 1 04 132 3 3 4 200 10 WC 20 A A
Example 47 M1 P4 a41 A1 50 A4 50 B1 20 77 C1 15 15 C9 5 1 06 128 3 3 4 200 10 WC 20 A A
Example 48 M1 P4 a42 A1 50 A4 50 B1 20 77 C1 15 15 C9 5 1 07 140 3 1 4 200 10 WC 20 A A
Example 49 M1 P4 a43 A1 50 A4 50 B1 20 77 C1 15 15 C9 5 1 08 148 3 1 4 200 10 WC 20 A A
Example 50 M1 P4 a44 A1 50 A4 50 B1 20 77 C1 15 15 C9 5 1 010 125 3 2 4 200 10 WC 20 A A
Example 51 M1 P4 a45 A1 50 A4 50 B1 20 77 C1 15 15 C9 5 1 Oll 125 3 1 4 200 10 WC 20 A A
Example 52 M1 P4 a46 A1 50 A4 50 B1 20 77 C1 15 15 C9 5 1 012 143 3 0.8 4 200 10 WC 20 A A
Example 53 M1 P4 a47 A1 50 A4 50 B1 20 77 C1 15 15 C9 5 1 013 110 3 0.5 4 200 10 WC 20 A A
Example 54 M1 P4 a48 A1 50 A4 50 B1 20 77 Cl 15 15 C9 5 1 014 110 3 1 4 200 10 WC 20 A A
Example 55 M1 P4 a49 A1 50 A4 50 B1 20 77 C1 15 15 C9 5 1 016 113 3 0.6 4 200 10 WC 20 A A
Example 56 M1 P4 a50 A1 50 A4 50 B1 20 77 C1 15 15 C9 5 1 017 113 3 1 4 200 10 WC 20 A A
Example 57 M1 P4 a51 A1 50 A4 50 B1 20 77 C1 15 15 C9 5 1 018 113 3 2.5 4 200 10 WC 20 A A
Example 58 M1 P4 a52 A1 50 A4 50 B1 20 77 C1 15 15 C9 5 1 019 115 3 3 4 200 10 WC 20 A A
Example 59 M1 P4 a53 A1 50 A4 50 B1 20 77 C1 15 15 C9 5 1 020 117 3 2.5 4 200 10 WC 20 A A
Example 60 M1 P4 a54 A1 50 A4 50 B1 20 77 C1 15 15 C9 5 1 021 100 3 1 4 200 10 WC 20 A A
MS: Metal Sheet, PTL: Primer treatment Layer, CF: Coating Film, KO: Kind, AMT: Amount, PS: Particle size, SP: Softening Point, FT: Film Thickness, UT:
Ultimate Temperature, H/O: Heating/Orying, CM: Cooling Method, CWT: Cooling Water Temperature, STF: Satisfaction, WC: water cooling
0'>
N
"* ,j, .$ v;:; qw .Q $. ,J iii iP ~,AJEg;IW@!',31$"L,." ¥l; gO.l"'.QkM&.4J14l);S¥,iifMW&Q!h( ; ,} ,JiWJ4k;q;;;ge;SZ:;g;z;;;JR:,,:,..,;,. ."AM!)!; m&:&tkth,{".. 4 ;T";:&\'.; __ ~". Jit:. ~ C . giRL $i4£ "J,,@ ,.J"t. &US}'"'. »£,"!'!"x "" «~.~ i$JiMUiJ ,M#dI@,$~
[0150]
Table 14 • Coating Film (a)
Curing Color
Silica particles (C)
Resin
Silica polyolefin Resin
Organic Resin (A) Agent Pigment
No. MS PTL CF (B) (A)+ (B) (E) Pa(rCt1ic) le PartSiicllieca(C2) part(Fic) les particles (D) FT UT: H/D CW'l': STF STF of
(~) (a) / (a) *4 *4 ().lIn) TM Time CM Tw of Tw~(TM-
*1 *1 *1 *2 (% ) *3 *3 *4 *3 *4 PS *3 PS
SP: *3 PS : b (OC) (sec) (OC) TM>Ts 150)/4
KD AMT KD AMT KD AMT KD AMT KD AMT KD AMT PS KD AMT ().lIn) : KD AMT KD Ts AMT
( %) (%) (% ) (% ) ( %) (% ) (nm) (%) c (% ) ().lIn) (OC) (% ) ().lIn)
: d : a
Example 61 M1 ~4 a55 Al 50 A4 50 B1 20 80 C1 15 15 C9 5 1 D3 132 0.3 1 4 200 10 WC 20 A A
Example 62 M1 ~4 a56 Al 50 A4 50 B1 20 80 C1 15 15 C9 5 1 D3 132 0.5 1 4 200 10 WC 20 A A
Example 63 M1 ~4 a57 Al 50 A4 50 B1 20 79 C1 15 15 C9 5 1 D3 132 1 1 4 200 10 WC 20 A A
Example 64 M1 ~4 a58 Al 50 A4 50 B1 20 73 C1 15 15 C9 5 1 D3 132 7 1 4 200 10 WC 20 A A
Example 65 M1 ~4 a59 Al 50 A4 50 B1 20 70 C1 15 15 C9 5 1 D3 132 10 1 4 200 10 WC 20 A A
Example 66 M1 ~4 a60 Al 50 A4 50 B1 20 68 C1 15 15 C9 5 1 D3 132 12 1 4 200 10 WC 20 A A
Example 67 M1 P4 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 2 200 10 WC 20 A A
Example 68 M1 ~4 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 3 200 10 WC 20 A A
Example 69 M1 P4 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 7 200 10 WC 20 A A
Example 70 M1 ~4 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 10 200 10 WC 20 A A
Example 71 M1 P4 a40 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D4 132 3 3 5 200 10 WC 20 A A
Example 72 M1 P4 a39 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D2 132 3 0.6 5 200 10 WC 20 A A
Example 73 M1 P4 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 4 140 10 WC 20 A A
Example 74 M1 P4 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 4 150 10 WC 20 A A
Example 75 M1 ~4 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 4 170 10 WC 20 A A
Example 76 M1 P4 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 4 180 10 wc 20 A A
Example 77 M1 P4 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 4 230 10 wc 20 A A
Example 78 M1 ~4 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 4 240 10 WC 20 A C
Example 79 M1 ~4 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 4 250 10 WC 20 A C
Example 80 M1 ~4 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 4 260 10 WC 20 A C
Example 81 M1 ~4 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 4 200 2 WC 20 A A
Example 82 M1 ~4 a7 Al 50 A4 50 Bl 20 77 C1 15 15 C9 5 1 D3 132 3 1 4 200 2.5 WC 20 A A
Example 83 M1 ~4 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 4 200 3 wc 20 A A
Example 84 M1 P4 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 4 200 15 WC 20 A A
Example 85 M1 P4 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 4 200 20 WC 20 A A
Example 86 M1 P4 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 4 200 30 WC 20 A A
Example 87 M1 ~4 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 4 200 10 SC - A A
Example 88 M1 P4 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 4 200 10 WC 0 A C
Example 89 M1 P4 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 4 200 10 WC 10 A C
Example 90 M1 P4 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 4 200 10 WC 25 A A
MS: Metal Sheet, PTL: Primer treatment Layer, CF: Coating Film, KD: Kind, AMT: Amount, PS: Particle size, SP: Softening Point, FT: Film Thickness, UT:
Ultimate Temperature, H/D: Heating/Drying, CM: Cooling Method, CWT: Cooling Water Temperature, STF: Satisfaction, WC: water cooling, SW: standing to cool
Ol
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[0151]
Table 15 • Coating Film (a)
Curing Color
Silica particles (C)
Resin
Silica polyolefin Resin
Organic Resin (A) Agent Pigment
Particle
No. MS PTL CF (B) (A)+(B) (E) (C1) PartSiicllieca(C2) part(Fic) les particles (D) FT UT: H/D CWT: STF STF of
(13) (a) / (a) *4 *4 (~) TM Time CM Tw of Tw2: (TM-
*1 *1 *1 *2 (% ) *3 *3 *4 *3 *4 PS *3 PS
SP: *3 PS : b (OC) (sec) (OC) TM>Ts 150)/4
KD AMT KD AMT KD AMT KD AMT KD AMT KD AMT PS KD AMT (~): KD AMT KD Ts AMT
(% ) (%) (% ) (% ) (% ) (%) (nm) ( %) c (% ) (~) (OC) (% ) (~)
: d : a
Example 91 M1 (34 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 4 240 10 wc 25 A A
Example 92 M1 (34 a61 Al 100 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 wc 20 A A
Example 93 M1 (34 a62 A2 100 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 94 M1 (34 a63 A3 100 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 wc 20 A A
Example 95 M1 (34 a64 A6 100 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 96 M1 (34 a65 A7 100 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 97 M1 (34 a66 AS 100 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 9S M1 (34 a67 Al 50 A4 50 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 wc 20 A A
Example 99 M1 (34 a6S A2 50 A4 50 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 100 M1 (34 a69 A3 50 A4 50 B1 20 7l E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 101 M1 (34 a70 Al 50 A5 50 B1 20 7l E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 102 M1 (34 a7l A2 50 A5 50 B1 20 7l E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 103 M1 (34 an A3 50 A5 50 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 104 M1 (34 a73 Al 90 AS 10 B1 20 7l E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 105 M1 (34 a74 Al 45 A4 45 AS 10 B1 20 7l E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 106 M1 (34 a75 Al 45 A5 45 AS 10 B1 20 7l E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 wc 20 A A
Example 107 M1 (34 a76 Al 100 7l E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example lOS M1 (34 a77 Al 50 A4 50 7l E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 109 M1 (34 a7S Al 50 A5 50 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 110 M1 (34 a79 Al 45 A4 45 AS 10 B2 20 7l E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 111 M1 (34 aSO Al 45 A4 45 AS 10 B3 20 7l E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 112 M1 (34 aS1 Al 45 A4 45 AS 10 B1 3 7l E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 113 M1 (34 aS2 Al 45 A4 45 AS 10 B1 5 7l E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 114 M1 (34 aS3 Al 45 A4 45 AS 10 B1 35 7l E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 115 M1 (34 aS4 Al 45 A4 45 AS 10 B1 40 7l E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 wc 20 A A
Example 116 M1 (34 aS5 Al 45 A4 45 AS 10 B1 20 7l E1 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 wc 20 A A
Example 117 M1 (34 aS6 Al 45 A4 45 AS 10 B1 20 65
E23+E 6+6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 wc 20 A A
Example 11S M1 (34 aS7 Al 45 A4 45 AS 10 B1 20 73 E2 4 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 119 M1 (34 aSS Al 45 A4 45 AS 10 B1 20 67 E2 10 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 wc 20 A A
Example 120 M1 (34 aS9 Al 45 A4 45 AS 10 B1 20 62 E2 15 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 wc 20 A A
MS: Metal Sheet, PTL: Primer treatment Layer, CF: Coating Film, KD: Kind, AMT: Amount, PS: Particle size, SP: Softening Point, FT: Film Thickness, UT:
Ultimate Temperature, H/D: Heating/Drying, CM: Cooling Method, CWT: Cooling Water Temperature, STF: Satisfaction, WC: water cooling
m
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[0152]
Table 16 • Coating Film (a)
Curing Color
Silica particles (C)
Resin
Silica Polyolefin Resin
Organic Resin (A) Agent Pigment
PTL CF (B) (A)+ (8) (E) Particle Silica particles particles (D)
No. MS (Cl) Particle (C2) (F) FT UT: H/D CWT: STF STF of
(J3) (a) / (a) *4 *4 (lIDl) TM Time CM Tw of Tw:2:(TM-
*1 *1 *1 *2 ( %) *3 *3 *4 *3 *4 PS *3 PS
SP: *3 PS : b (OC) (sec) (OC) TM>Ts 150)/4
KD AMT KD AMT KD AMT KD AMT KD AMT KD AMT PS KD AMT (lIDl) : KD AMT KD Ts AMT
(%) (% ) (%) ( %) (%) (% ) (nm) (% ) c (% ) (lIDl) (OC) (%) (lIDl)
: d : a
Example 121 Ml J34 a90 Al 45 A4 45 A8 10 Bl 20 60 E2 17 Cl 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 122 Ml J34 a91 Al 45 A4 45 A8 10 Bl 20 71 E2 6 C2 15 5 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 123 Ml J34 a92 Al 45 A4 45 A8 10 Bl 20 71 E2 6 c3 15 50 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 124 Ml J34 a93 Al 45 A4 45 A8 10 Bl 20 84 E2 6 Cl 2 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 125 Ml J34 a94 Al 45 A4 45 A8 10 Bl 20 83 E2 6 Cl 3 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 126 Ml J34 a95 Al 45 A4 45 A8 10 Bl 20 56 E2 6 Cl 30 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 127 Ml J34 a96 Al 45 A4 45 A8 10 Bl 20 51 E2 6 cl 35 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 128 Ml J34 a97 Al 45 A4 45 A8 10 Bl 20 71 E2 6 Cl 15 15 C7 5 0.45 D3 132 3 1 5 200 10 WC 20 A A
Example 129 Ml J34 a98 Al 45 A4 45 A8 10 Bl 20 71 E2 6 Cl 15 15 C8 5 0.5 D3 132 3 1 5 200 10 WC 20 A A
Example 130 Ml J34 a99 Al 45 A4 45 A8 10 Bl 20 71 E2 6 Cl 15 15 Cl0 5 2 D3 132 3 1 5 200 10 WC 20 A A
Example 131 Ml J34 alOO Al 45 A4 45 A8 10 Bl 20 71 E2 6 Cl 15 15 Cll 5 3.5 D3 132 3 1 5 200 10 WC 20 A A
Example 132 Ml J34 alOl Al 45 A4 45 A8 10 Bl 20 71 E2 6 Cl 15 15 C12 5 5 D3 132 3 1 5 200 10 WC 20 A A
Example 133 Ml J34 al02 Al 45 A4 45 A8 10 Bl 20 71 E2 6 Cl 15 15 C14 5 2.5 D3 132 3 1 5 200 10 WC 20 A A
Example 134 Ml J34 al03 Al 45 A4 45 A8 10 Bl 20 74 E2 6 Cl 15 15 C9 2 1 D3 132 3 1 5 200 10 WC 20 A A
Example 135 Ml J34 alOO Al 45 A4 45 A8 10 Bl 20 73 E2 6 Cl 15 15 C9 3 1 D3 132 3 1 5 200 10 WC 20 A A
Example 136 Ml J34 alas Al 45 A4 45 A8 10 Bl 20 66 E2 6 cl 15 15 C9 10 1 D3 132 3 1 5 200 10 WC 20 A A
Example 137 Ml J34 al06 Al 45 A4 45 A8 10 Bl 20 61 E2 6 Cl 15 15 C9 15 1 D3 132 3 1 5 200 10 WC 20 A A
Example 138 Ml J34 alO7 Al 45 A4 45 A8 10 Bl 20 51 E2 6 cl 15 15 C9 25 1 D3 132 3 1 5 200 10 WC 20 A A
Example 139 Ml J34 alOB Al 45 A4 45 A8 10 Bl 20 68 E2 6 cl 15 15 C9 5 1 Fl 3 1 D3 132 3 1 5 200 10 WC 20 A A
Example 140 Ml J34 alOO Al 45 A4 45 A8 10 Bl 20 68 E2 6 Cl 15 15 C9 5 1 F2 3 2 D3 132 3 1 5 200 10 WC 20 A A
Example 141 Ml J34 allO Al 45 A4 45 A8 10 Bl 20 68 E2 6 Cl 15 15 C9 5 1 F3 3 3 D3 132 3 1 5 200 10 WC 20 A A
Example 142 Ml J34 alll Al 45 A4 45 A8 10 Bl 20 68 E2 6 cl 15 15 C9 5 1 F4 3 4 D3 132 3 1 5 200 10 WC 20 A A
Example 143 Ml J34 all2 Al 45 A4 45 A8 10 Bl 20 68 E2 6 cl 15 15 C9 5 1 F5 3 5 D3 132 3 1 5 200 10 WC 20 A A
Example 144 Ml J34 all3 Al 45 A4 45 A8 10 Bl 20 68 E2 6 Cl 15 15 C9 5 1 F6 3 8 D3 132 3 1 5 200 10 WC 20 A A
Example 145 Ml J34 all4 Al 45 A4 45 A8 10 Bl 20 68 E2 6 Cl 15 15 C9 5 1 F7 3 10 D3 132 3 1 5 200 10 WC 20 A A
Example 146 Ml J34 all5 Al 45 A4 45 A8 10 Bl 20 68 E2 6 Cl 15 15 C9 5 1 F8 3 2 D3 132 3 1 5 200 10 WC 20 A A
Example 147 Ml J34 all6 Al 45 A4 45 A8 10 Bl 20 68 E2 6 Cl 15 15 C9 5 1 F9 3 3 D3 132 3 1 5 200 10 WC 20 A A
Example 148 Ml J34 all7 Al 45 A4 45 A8 10 Bl 20 68 E2 6 cl 15 15 C9 5 1 FlO 3 4.5 D3 132 3 1 5 200 10 WC 20 A A
Example 149 Ml J34 all8 Al 45 A4 45 A8 10 Bl 20 68 E2 6 Cl 15 15 C9 5 1 Fll 3 4 D3 132 3 1 5 200 10 WC 20 A A
Example 150 Ml J34 all9 Al 45 A4 45 A8 10 Bl 20 68 E2 6 Cl 15 15 C9 5 1 F12 3 0.8 D3 132 3 1 5 200 10 WC 20 A A
MS: Metal Sheet, PTL: Primer treatment Layer, CF: Coating Film, KD: Kind, AMT: Amount, PS: Particle size, SP: Softening Point, FT: Film Thickness, UT:
Ultimate Temperature, H/D: Heating/Drying, CM: Cooling Method, CWT: Cooling Water Temperature, STF: Satisfaction, WC: water cooling
0'U1
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[0153]
Table 17 • Coating Film (a)
Curing Color
Silica particles (C)
Silica Silica Resin Polyolefin Resin
PTL CF Organic Resin (A) Agent
(A)+(B)/
Pigment
No. MS (B) (E) Particle Particle Particle (F) Particle (D) FT UT: H/D CWT: STF STF of (P) (a) (a) (Cl) (C2) (J.U1l) : TM Time CM Tw of Tw~ (TM-
*1 *1 *1 *2 (%) *3 *3 *4 *3 *4 PS *3 *4 PS SP: *3 *4 PS b (OC) (sec) (OC) TM>Ts 150)/4
KD AMT KD AMT KD AMT KD AMT KD AMT KD AMT PS KD AMT (J.U1l) : KD AMT (J.U1l) : KD Ts AMT (J.U1l) :
(% ) (%) (%) (%) (%) (% ) (run) (%) c (%) d (OC) (% ) a
Example 151 Ml /34 al20 Al 45 A4 45 AS 10 Bl 20 6S E2 6 Cl 15 15 C9 5 1 Fl3 3 2 D3 132 3 1 5 200 10 WC 20 A A
Example 152 M1 /34 a121 Al 45 A4 45 AS 10 B1 20 71 E2 6 C1 15 15 C9 5 1 F3 0.3 3 D3 132 3 1 5 200 10 WC 20 A A
Example 153 M1 /34 a122 Al 45 A4 45 AS 10 B1 20 71 E2 6 C1 15 15 C9 5 1 F3 0.5 3 D3 132 3 1 5 200 10 WC 20 A A
Example 154 M1 /34 a123 Al 45 A4 45 AS 10 B1 20 66 E2 6 C1 15 15 C9 5 1 F3 5 3 D3 132 3 1 5 200 10 WC 20 A A
Example 155 M1 /34 0024 Al 45 A4 45 AS 10 B1 20 61 E2 6 C1 15 15 C9 5 1 F3 10 3 D3 132 3 1 5 200 10 WC 20 A A
Example 156 M1 /34 a125 Al 45 A4 45 AS 10 B1 20 56 E2 6 C1 15 15 C9 5 1 F3 15 3 D3 132 3 1 5 200 10 WC 20 A A
Example 157 M1 /34 0026 Al 45 A4 45 AS 10 B1 20 51 E2 6 C1 15 15 C9 5 1 F3 20 3 D3 132 3 1 5 200 10 WC 20 A A
Example ISS M1 /34 a127 Al 45 A4 45 AS 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D2 132 3 0.6 4 200 10 WC 20 A A
Example 159 M1 /34 a74 Al 45 A4 45 AS 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 4 200 10 WC 20 A A
Example 160 M1 /34 a128 Al 45 A4 45 AS 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D4 132 3 3 4 200 10 WC 20 A A
Example 161 M1 /34 a129 Al 45 A4 45 AS 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D6 12S 3 3 4 200 10 WC 20 A A
Example 162 M1 /34 a130 Al 45 A4 45 AS 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D7 140 3 1 4 200 10 WC 20 A A
Example 163 M1 /34 al3l Al 45 A4 45 AS 10 B1 20 71 E2 6 C1 15 15 C9 5 1 DS 14S 3 1 4 200 10 WC 20 A A
Example 164 M1 /34 al32 Al 45 A4 45 AS 10 B1 20 71 E2 6 C1 15 15 C9 5 1 010 125 3 2 4 200 10 WC 20 A A
Example 165 M1 /34 a133 Al 45 A4 45 AS 10 B1 20 71 E2 6 C1 15 15 C9 5 1 Dll 125 3 1 4 200 10 WC 20 A A
Example 166 M1 /34 al34 Al 45 A4 45 AS 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D12 143 3 O.S 4 200 10 WC 20 A A
Example 167 M1 /34 al35 Al 45 A4 45 AS 10 B1 20 71 E2 6 C1 15 15 C9 5 1 DB 110 3 0.5 4 200 10 WC 20 A A
Example 16S M1 /34 al36 Al 45 A4 45 AS 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D14 110 3 1 4 200 10 WC 20 A A
Example 169 M1 /34 a137 Al 45 A4 45 AS 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D16 113 3 0.6 4 200 10 WC 20 A A
Example 170 M1 /34 al38 Al 45 A4 45 AS 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D17 113 3 1 4 200 10 WC 20 A A
Example 171 M1 /34 al39 Al 45 A4 45 AS 10 B1 20 71 E2 6 C1 15 15 C9 5 1 DIS 113 3 2.5 4 200 10 WC 20 A A
Example 172 M1 /34 0140 Al 45 A4 45 AS 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D19 115 3 3 4 200 10 WC 20 A A
Example 173 M1 /34 0141 Al 45 A4 45 AS 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D20 117 3 2.5 4 200 10 WC 20 A A
Example 174 M1 /34 0142 Al 45 A4 45 AS 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D21 100 3 1 4 200 10 WC 20 A A
Example 175 M1 /34 0143 Al 45 A4 45 AS 10 B1 20 74 E2 6 C1 15 15 C9 5 1 D3 132 0.3 1 4 200 10 WC 20 A A
Example 176 M1 /34 0144 Al 45 A4 45 AS 10 B1 20 74 E2 6 C1 15 15 C9 5 1 D3 132 0.5 1 4 200 10 WC 20 A A
Example 177 M1 /34 0145 Al 45 A4 45 AS 10 B1 20 73 E2 6 C1 15 15 C9 5 1 D3 132 1 1 4 200 10 WC 20 A A
Example 17S M1 /34 0146 Al 45 A4 45 AS 10 B1 20 67 E2 6 C1 15 15 C9 5 1 D3 132 7 1 4 200 10 WC 20 A A
Example 179 M1 /34 0147 Al 45 A4 45 AS 10 B1 20 64 E2 6 C1 15 15 C9 5 1 D3 132 10 1 4 200 10 WC 20 A A
Example ISO M1 /34 0148 Al 45 A4 45 AS 10 B1 20 62 E2 6 C1 15 15 C9 5 1 D3 132 12 1 4 200 10 WC 20 A A
MS: Metal Sheet, PTL: Primer treatment Layer, CF: Coating Film, KD: Kind, AMT: Amount, PS: Particle size, SP: Softening Point, FT: Film Thickness, UT:
Ultimate Temperature, H/D: Heating/Drying, CM: Cooling Method, CWT: Cooling Water Temperature, STF: Satisfaction, WC: water cooling
0'0'.I d.*h~ q ?::,,;,A£_##iJA%~)l,;,,;; £..$. ,; !I! ".".li!i&i£ili1i4£;&JI,;;;;£jlJJJUL" 92,.,~"· A 4. -,M¥. #, t42ii!U!!$!!i.,",:"h :;; JJMlAi!)it4i£MA ",m:g:\j%:i',""""- -*-6. ¢ w<1l :;;;J&9if,J!4 4,,,.1., bj£M", "'''''"",,",,* • -,-it.. ,~", __ tJLQtj@,t,K.._ 'f4A'-~. r,"'-:-':'--~':-1)j.M• .,kd ·';..AJ 4£i ,,],l¥A
[0154]
Table 18 • Coating Film (a)
Curing Color
Silica particles (C)
Silica Silica Resin Polyolefin Resin
PTL CF Organic Resin (A) Agent
(A)+(B)/
Pigment
No. MS (B) (E) Particle Particle Particle (F) Particle (D) FT UT: H/D CWT: STF STF of
(B) (a) (a) (Cl) (C2) (Ilffi) : TM Time CM Tw of Tw<>:(TM-
*1 *1 *1 *2 (%) *3 *3 *4 *3 *4 PS *3 *4 PS SP: *3 *4 PS b (OC) (sec) (OC) TM>Ts 150)/4
KD AMT KD AMT KD AMT KD AMT KD AMT KD AMT PS KD AMT (Ilffi) : KD AMT (Ilffi) : KD Ts AMT (Ilffi) :
(%) (%) (%) (%) (% ) (%) (nm) (% ) c (% ) d (OC) (% ) a
Example 181 Ml B4 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 Cl 15 15 C9 5 1 D3 132 3 1 2 200 10 WC 20 A A
Example 182 Ml B4 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 3 200 10 WC 20 A A
Example 183 M1 B4 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 7 200 10 WC 20 A A
Example 184 M1 B4 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 10 200 10 WC 20 A A
Example 185 M1 B4 al28 Al 45 A4 45 A8 10 Bl 20 71 E2 6 C1 15 15 C9 5 1 D4 132 3 3 5 200 10 WC 20 A A
Example 186 M1 B4 alZ7 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D2 132 3 0.6 5 200 10 WC 20 A A
Example 187 M1 B4 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 Cl 15 15 C9 5 1 D3 132 3 1 4 140 10 WC 20 A A
Example 188 M1 B4 a74 Al 45 A4 45 A8 10 Bl 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 4 150 10 WC 20 A A
Example 189 M1 B4 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 4 170 10 WC 20 A A
Example 190 Ml B4 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 4 180 10 WC 20 A A
Example 191 M1 B4 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 Cl 15 15 C9 5 1 D3 132 3 1 4 230 10 WC 20 A A
Example 192 M1 [34 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 4 240 10 WC 20 A C
Example 193 M1 B4 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 4 250 10 WC 20 A C
Example 194 M1 B4 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 4 260 10 WC 20 A C
Example 195 Ml B4 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 Cl 15 15 C9 5 1 D3 132 3 1 4 200 2 WC 20 A A
Example 196 M1 B4 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 Cl 15 15 C9 5 1 D3 132 3 1 4 200 2.5 WC 20 A A
Example 197 M1 B4 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 4 200 3 WC 20 A A
Example 198 M1 B4 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 4 200 15 WC 20 A A
Example 199 M1 B4 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 Cl 15 15 C9 5 1 D3 132 3 1 4 200 20 WC 20 A A
Example 200 M1 B4 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 4 200 30 WC 20 A A
Example 201 M1 B4 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 Cl 15 15 C9 5 1 D3 132 3 1 4 200 10 SC - A A
Example 202 M1 B4 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 4 200 10 WC 0 A C
Example 203 M1 B4 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 4 200 10 WC 10 A C
Example 204 M1 B4 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 4 200 10 WC 25 A A
Example 205 M1 B4 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 4 240 10 WC 25 A A
Example 206 M1 B4 a97 Al 45 A4 45 A8 10 B1 20 71 E2 6 Cl 15 15 C7 5 0.45 D3 132 3 1 3 200 10 WC 20 A A
Example 207 M1 B4 a98 Al 45 A4 45 A8 10 B1 20 71 E2 6 Cl 15 15 C8 5 0.5 D3 132 3 1 3 200 10 WC 20 A A
Example 208 M1 B4 a99 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C10 5 2 D3 132 3 1 3 200 10 WC 20 A A
Example 209 M1 B4 alOO Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 Cll 5 3.5 D3 132 3 1 3 200 10 WC 20 A A
Example 210 M1 B4 a97 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C7 5 0.45 D3 132 3 1 10 200 10 WC 20 A A
MS: Metal Sheet, PTL: Primer treatment Layer, CF: Coating Film, KD: Kind, AMT: Amount, PS: Particle size, SP: Softening Point, FT: Film Thickness, UT:
Ultimate Temperature, H/D: Heating/Drying, CM: Cooling Method, CWT: Cooling Water Temperature, STF: Satisfaction, WC: water cooling, ST: standing to cool
01
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[0155]
Table 19 • Coating Film (a)
Curing Color
Silica particles (C)
Silica Silica Resin Polyolefin Resin
PTL CF Organic Resin (A) Agent (A)+ (B) / Pigment
No. MS (B) (E) Particle Particle Particle (F) Particle (D) FT UT: H/D CWT: STF STF of
(13) (a) (a) (Cl) (C2) (~): TM Time CM Tw of Tw;:>,(TM-
*1 *1 *1 *2 (%) *3 *3 *4 *3 *4 PS *3 *4 PS SP: *3 *4 PS b (OC) (sec) (OC) TM>Ts 150)/4
KD AMT KD AMT KD AMT KD AMT KD AMT KD AMT PS KD AMT (~): KD AMT (~): KD Ts AMT (~):
(%) (%) (%) (% ) (%) (%) (nm) (%) c (% ) d (OC) (% ) a
Example 211 Ml 134 a98 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C8 5 0.5 D3 132 3 1 10 200 10 WC 20 A A
Example 212 M1 134 a99 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C10 5 2 D3 132 3 1 10 200 10 WC 20 A A
Example 213 M1 134 a100 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 Cll 5 3.5 D3 132 3 1 10 200 10 WC 20 A A
Example 214 M1 134 a10B Al 45 A4 45 A8 10 B1 20 68 E2 6 C1 15 15 C9 5 1 F1 3 1 D3 132 3 1 3 200 10 WC 20 A A
Example 215 M1 134 a109 Al 45 A4 45 A8 10 B1 20 68 E2 6 C1 15 15 C9 5 1 F2 3 2 D3 132 3 1 3 200 10 WC 20 A A
Example 216 M1 134 a110 Al 45 A4 45 A8 10 B1 20 68 E2 6 c1 15 15 C9 5 1 F3 3 3 D3 132 3 1 3 200 10 WC 20 A A
Example 217 M1 134 a111 Al 45 A4 45 A8 10 B1 20 68 E2 6 C1 15 15 C9 5 1 F4 3 4 D3 132 3 1 3 200 10 WC 20 A A
Example 218 M1 134 a112 Al 45 A4 45 A8 10 B1 20 68 E2 6 C1 15 15 C9 5 1 F5 3 5 D3 132 3 1 3 200 10 WC 20 A A
Example 219 M1 134 a10B Al 45 A4 45 A8 10 B1 20 68 E2 6 C1 15 15 C9 5 1 F1 3 1 D3 132 3 1 10 200 10 WC 20 A A
Example 220 M1 134 a109 Al 45 A4 45 A8 10 B1 20 68 E2 6 C1 15 15 C9 5 1 F2 3 2 D3 132 3 1 10 200 10 WC 20 A A
Example 221 M1 134 a110 Al 45 A4 45 A8 10 B1 20 68 E2 6 C1 15 15 C9 5 1 F3 3 3 D3 132 3 1 10 200 10 WC 20 A A
Example 222 M1 134 a111 Al 45 A4 45 A8 10 B1 20 68 E2 6 C1 15 15 C9 5 1 F4 3 4 D3 132 3 1 10 200 10 WC 20 A A
Example 223 M1 134 a112 Al 45 A4 45 A8 10 B1 20 68 E2 6 C1 15 15 C9 5 1 F5 3 5 D3 132 3 1 10 200 10 WC 20 A A
Example 224 M1 134 a113 Al 45 A4 45 A8 10 B1 20 68 E2 6 c1 15 15 C9 5 1 F6 3 8 D3 132 3 1 10 200 10 WC 20 A A
Example 225 M1 134 a114 Al 45 A4 45 A8 10 B1 20 68 E2 6 c1 15 15 C9 5 1 F7 3 10 D3 132 3 1 10 200 10 WC 20 A A
Example 226 M1 134 a149 Al 45 A4 45 A8 10 B1 20 65 E2+E:: 4+20 C1 15 15 C9 5 1 D3 132 3 1 10 200 10 WC 20 A A
Example 227 M1 134 a150 Al 45 A4 45 A8 10 B1 20 65 E3 50 C1 15 15 C9 5 1 D3 132 3 1 10 200 10 WC 20 A A
Example 228 M1 134 a151 Al 45 A4 45 A8 10 B1 20 65 E2+E:: 4+20 C1 15 15 C9 5 1 F4 3 4 D3 132 3 1 10 200 10 WC 20 A A
Example 229 M1 134 a152 Al 45 A4 45 A8 10 B1 20 65 E3 50 C1 15 15 C9 5 1 F4 3 4 D3 132 3 1 10 200 10 WC 20 A A
Example 230 M1 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 231 M1 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 232 M1 a110 Al 45 A4 45 A8 10 B1 20 68 E2 6 C1 15 15 C9 5 1 F3 3 3 D3 132 3 1 5 200 10 WC 20 A A
Example 233 M1 131 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 234 M1 132 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 235 M1 133 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 236 M1 135 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 237 M1 136 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 238 M1 137 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 239 M1 138 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 240 M1 139 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
MS: Metal Sheet, PTL: Primer treatment Layer, CF: Coating Film, KD: Kind, AMT: Amount, PS: Particle size, SP: Softening Point, FT: Film Thickness, UT:
Ultimate Temperature, H/D: Heating/Drying, CM: Cooling Method, CWT: Cooling Water Temperature, STF: Satisfaction, WC: water cooling
(j)
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[0156]
Table 20 '. Coating Film (a)
Curing Color
Silica particles (C)
Silica Silica Resin Polyolefin Resin
PTL CF Organic Resin (A) Agent
(A)+ (B) /
Pigment
No. MS (B) (E) Particle Particle Particle (F) Particle (D) FT UT: H/D CWT: STF STF of
(3) (a) (a) (Cl) (C2) (J.UU) : TM Time CM Tw of Tw<:(TM-
*1 *1 *1 *2 (%) *3 *3 *4 *3 *4 PS *3 *4 PS SP: *3 *4 PS b (OC) (sec) (OC) TM>Ts 150)/4
KD AMT KD AMT KD AMT KD AMT KD AMT KD AMT PS KD AMT (J.UU) : KD AMT (J.UU) : KD Ts AMT (J.UU) :
(%) (% ) (% ) (% ) (% ) (%) (nm) (%) c (%) d (OC) (%) a
Example 241 M2 a7 A1 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 242 M2 a74 A1 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 243 M2 aliO A1 45 A4 45 A8 10 B1 20 68 E2 6 C1 15 15 C9 5 1 F3 3 3 D3 132 3 1 5 200 10 WC 20 A A
Example 244 M2 ~4 a7 A1 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 245 M2 ~4 a74 A1 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 246 M2 ~4 aliO A1 45 A4 45 A8 10 B1 20 68 E2 6 C1 15 15 C9 5 1 F3 3 3 D3 132 3 1 5 200 10 WC 20 A A
Example 247 M3 a7 A1 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 248 M3 a74 A1 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 249 M3 Ts 150)/4
K AMT K AMT K AMT K AMT (%) KD AMT K AMT PS K AMT (/-Ull) : K AMT (/-Ull) : K T AMT (/-Ull) :
D (%) D (%) D (%) D D (%) D (%) D D s
(%) (% ) (nm) c (%) d (OC) (% ) a
Example 271 M7 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 272 M7 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 273 M7 aliO Al 45 A4 45 A8 10 B1 20 68 E2 6 C1 15 15 C9 5 1 F3 3 3 D3 132 3 1 5 200 10 WC 20 A A
Example 274 M7 134 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 275 M7 134 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 276 M7 134 aliO Al 45 A4 45 A8 10 B1 20 68 E2 6 C1 15 15 C9 5 1 F3 3 3 D3 132 3 1 5 200 10 WC 20 A A
Example 277 M8 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 278 M8 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 279 M8 al10 Al 45 A4 45 A8 10 B1 20 68 E2 6 C1 15 15 C9 5 1 F3 3 3 D3 132 3 1 5 200 10 WC 20 A A
Example 280 M8 134 a7 Al 50 A4 50 B1 20 77 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 281 M8 134 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Example 282 M8 134 aliO Al 45 A4 45 A8 10 B1 20 68 E2 6 C1 15 15 C9 5 1 F3 3 3 D3 132 3 1 5 200 10 WC 20 A A
MS: Metal Sheet, PTL: Primer treatment Layer, CF: Coating Film, KD: Kind, AMT: Amount, PS: Particle size, SP: Softening Point, FT: Film Thickness, UT:
Ultimate Temperature, H/D: Heating/Drying, CM: Cooling Method, CWT: Cooling Water Temperature, STF: Satisfaction, WC: water cooling
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[0158]
Table 22 • Coating Film (a)
Curing Color
Silica particles (C)
Silica Silica Resin Polyolefin Resin
PTL CF Organic Resin (A) Agent
(A)+(B)/
Pigment
No. MS (B) (E) Particle Particle Particle (F) Particle (D) FT UT: H/D CWT: STF STF of
((3) (a) (a) (Cl) (C2) (1JIll) : TM Time CM Tw of Tw~ (TM-
*1 *1 *1 *2 (%) *3 *3 *4 *3 *4 PS *3 *4 PS SP: *3 *4 PS b (OC) (sec) (OC) TM>Ts 150)/4
KD AMT KD AMT KD AMT KD AMT KD AMT KD AMT PS KD AMT (1JIll) : KD AMT (1JIll) : KD Ts AMT (1JIll) :
(%) (% ) (% ) (%) (% ) (% ) (run) (%) c (%) d (OC) (% ) a
CEoxmapmaprlaetiv1e Ml (34 a153 Al 50 A4 50 Bl 20 92 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Comparative
Example 2 Ml (34 al54 Al 50 A4 50 Bl 20 77 C9 20 1 D3 132 3 1 5 200 10 WC 20 A A
CEoxmampaprlaetiv3e Ml (34 al55 Al 50 A4 50 Bl 20 77 C4 15 65 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
CEoxmampaprlaetiv4e Ml (34 al56 Al 50 A4 50 Bl 20 82 Cl 15 15 D3 132 3 1 5 200 10 WC 20 A A
Comparative
Example 5 Ml (34 0057 Al 50 A4 50 Bl 20 77 Cl 20 15 D3 132 3 1 5 200 10 WC 20 A A
Comparative
Example 6 Ml (34 aJ58 Al 50 A4 50 Bl 20 77 Cl 15 15 C5 5 0.1 D3 132 3 1 5 200 10 WC 20 A A
CEoxmampaprlaetiv7e Ml (34 0059 Al 50 A4 50 Bl 20 77 Cl 15 15 C6 5 0.2 D3 132 3 1 5 200 10 wc 20 A A
CEoxmapmaprlaetiv8e Ml (34 alED Al 50 A4 50 Bl 20 77 Cl 15 15 CD 5 6.8 D3 132 3 1 5 200 10 wc 20 A A
CEoxmampaprlaetiv9e Ml (34 al61 Al 50 A4 50 Bl 20 77 Cl 15 15 C14 5 2.5 D3 132 3 1 5 200 10 wc 20 A A
Comparative
Example 10 Ml (34 al62 Al 50 A4 50 Bl 20 77 Cl 15 15 CIS 5 0.2 D3 132 3 1 5 200 10 wc 20 A A
Comparative
Example 11 Ml (34 al63 Al 50 A4 50 Bl 20 74 Cl 20 15 F3 3 3 D3 132 3 1 5 200 10 WC 20 A A
Comparative
Example 12 Ml (34 al64 Al 50 A4 50 Bl 20 74 Cl 15 15 C6 5 0.2 F3 3 3 D3 132 3 1 5 200 10 WC 20 A A
CEoxmamppalreati1v3e Ml (34 al65 Al 50 A4 50 Bl 20 80 Cl 15 15 C9 5 1 5 200 10 WC 20 A A
CEoxmamppalreati1v4e Ml (34 ala; Al 50 A4 50 Bl 20 77 Cl 15 15 C9 5 1 Dl 132 3 0.2 4 200 10 wc 20 A A
Comparative
Example 15 Ml (34 al67 Al 50 A4 50 Bl 20 77 Cl 15 15 C9 5 1 D5 132 3 6 4 200 10 WC 20 A A
CEoxmamppalreati1v6e Ml (34 alEE Al 50 A4 50 Bl 20 77 Cl 15 15 C9 5 1 D9 126 3 5 4 200 10 wc 20 A A
CEoxmamppalreati1v7e Ml (34 al69 Al 50 A4 50 Bl 20 77 Cl 15 15 C9 5 1 DIS 110 3 4 4 200 10 WC 20 A A
CEoxmamppalreati1v8e Ml (34 a7 Al 50 A4 50 Bl 20 77 Cl 15 15 C9 5 1 D3 132 3 1 1 200 10 WC 20 A A
Comparative
Example 19 Ml (34 a40 Al 50 A4 50 Bl 20 77 Cl 15 15 C9 5 1 D4 132 3 3 2 200 10 wc 20 A A
Comparative
Example 20 Ml (34 a40 Al 50 A4 50 Bl 20 77 Cl 15 15 C9 5 1 D4 132 3 3 3 200 10 wc 20 A A
CEoxmamppalreati2v1e Ml (34 a39 Al 50 A4 50 Bl 20 77 Cl 15 15 C9 5 1 D2 132 3 0.6 7 200 10 WC 20 A A
Comparative
Example 22 Ml (34 al70 Al 50 A4 50 Bl 20 86 E2 6 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
MS: Metal Sheet, PTL: Primer treatment Layer, CF: Coating Film, KD: Kind, AMT: Amount, PS: Particle size, SP: Softening Point, FT: Film Thickness, UT:
Ultimate Temperature, H/D: Heating/Drying, CM: Cooling Method, CWT: Cooling Water Temperature, STF: Satisfaction, WC: water cooling
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• (continued)
Coating Film (a)
Curing Color
Silica particles (C)
Silica Silica Resin Po1yo1efin Resin
PTL CF Organic Resin (A) Agent (A)+(B) Pigment
No. MS (/3) (a) (B) (a/ ) (E) Pa(rCt1i)cle Pa(rCt2i)cle Particle (F) Particle (D) (1JFffTi) : UTTM: THim/De MC CWTwT: SoTfF TSwT<=F(ToM-f
*1 *1 *1 *2 *3 *3 *4 *3 *3 *4 PS SP: *3 *4 PS b (OC) (sec) (OC) TM>Ts 150)/4
K AMT K AMT K AMT K AMT (%) KD AMT KD AMT PS KD AMT *4 PS K AMT (1Jffi) : KD Ts AMT (1Jffi) :
D (%) D (%) D (%) D (%) (%) ( %) (nm) (%) (1Jffi): c D (%) d (OC) (% ) a
Comparative
Example 23 M1 /34 0171 Al 50 A4 50 B1 20 71 E2 6 C9 20 1 D3 132 3 1 5 200 10 WC 20 A A
CEoxmampparleati2v4e M1 /34 0172 Al 50 A4 50 B1 20 71 E2 6 C4 15 65 C9 5 1 D3 132 3 1 5 200 10 WC 20 A A
Comparative
Example 25 M1 /34 0173 Al 50 A4 50 B1 20 76 E2 6 Cl 15 15 D3 132 3 1 5 200 10 WC 20 A A
CEoxmamppalreati2v6e M1 /34 0174 Al 50 A4 50 B1 20 71 E2 6 C1 20 15 D3 132 3 1 5 200 10 WC 20 A A
CEoxmamppalreati2v7e M1 /34 0175 Al 50 A4 50 B1 20 71 E2 6 C1 15 15 C5 5 0.1 D3 132 3 1 5 200 10 WC 20 A A
Comparative
Example 28 M1 /34 0176 Al 50 A4 50 B1 20 71 E2 6 C1 15 15 C6 5 0.2 D3 132 3 1 5 200 10 WC 20 A A
Comparative
M1 /34 0177 Al 50 A4 50 B1 20 71 E2 6 C1 15 15
C1
Example 29 3 5 6.8 D3 132 3 1 5 200 10 WC 20 A A
Comparative
M1 /34 0178 Al 50 A4 50 B1 20 71 E2 6 C1 15 15
C1
Example 30 4 5 2.5 D3 132 3 1 5 200 10 WC 20 A A
Comparative M1 /34 0179 Al 50 A4 50 B1 20 71 E2 6 C1 15 15
C1
Example 31 5 5 0.2 D3 132 3 1 5 200 10 WC 20 A A
Comparative
Example 32 M1 /34 alSO Al 50 A4 50 B1 20 68 E2 6 C1 20 15 F3 3 3 D3 132 3 1 5 200 10 WC 20 A A
Comparative
Example 33 M1 /34 a181 Al 50 A4 50 B1 20 68 E2 6 C1 15 15 C6 5 0.2 F3 3 3 D3 132 3 1 5 200 10 WC 20 A A
Comparative
Example 34 M1 /34 a182 Al 45 A4 45 A8 10 B1 20 74 E2 6 C1 15 15 C9 5 1 5 200 10 WC 20 A A
Comparative
Example 35 M1 /34 a183 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D1 132 3 0.2 4 200 10 WC 20 A A
Comparative
Example 36 M1 /34 a184 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D5 132 3 6 4 200 10 WC 20 A A
Comparative
Example 37 M1 /34 a185 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D9 126 3 5 4 200 10 WC 20 A A
Comparative M1 /34 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1
Example 38 a186 D51 no 3 4 4 200 10 WC 20 A
A
CEoxmamppalreati3v9e M1 /34 a74 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D3 132 3 1 1 200 10 WC 20 A A
CEoxmamppalreati4v0e M1 /34 a128 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D4 132 3 3 2 200 10 WC 20 A A
Comparative
Example 41 M1 /34 a128 Al 45 A4 45 A8 10 B1 20 71 E2 6 Cl 15 15 C9 5 1 D4 132 3 3 3 200 10 WC 20 A A
Comparative
Example 42 M1 /34 a127 Al 45 A4 45 A8 10 B1 20 71 E2 6 C1 15 15 C9 5 1 D2 132 3 0.6 7 200 10 WC 20 A A
MS: Metal Sheet, PTL: Primer treatment Layer, CF: Coating Film, KD: Kind, AMT: Amount, PS: Particle size, SP: Softening Point, FT: Film Thickness, UT:
Ultimate Temperature, H/D: Heating/Drying, CM: Cooling Method, CWT: Cooling Water Temperature, STF: Satisfaction, WC: water cooling
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5
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• - 73 -
[0159]
(4) Coated Metal Sheet
The coating film configuration and coating film
thickness of the coated metal sheet prepared in (1) to
(3) above, the heat-drying time, the cooling method (when
rapidly cooled by submersion in water immediately after
heat-drying, the method is denoted by water cooling, and
when left standing to naturally cool after heat-drying,
the method is denoted by standing to cool), and the
temperature of cooling water at the water cooling are
shown in Tables 12 to 22. In addition, when the
softening point of the polyolefin resin particles (0) is
TsoC, the sheet temperature of the metal sheet at water
cooling is TMoC and the water temperature of the cooling
water is TwoC, whether the relationship of TM>Ts or Tw~(TM150)/
4 is satisfied or not (denoted by satisfaction) is
also shown in Tables 12 to 22 (denoted by "A" when
satisfied, and denoted by "c" when not satisfied).
[0160]
20 The average particle sizes of the silica particles
(C), the polyolefin resin particles (0), the color
pigment (E), and the at least one resin particles (F)
selected from an acrylic resin and silicone resin, which
may be contained in the coating film, are shown in Tables
25 12 to 22. An observation sample of 50 to 100 nm in
thickness was cut out from the coated metal sheet
prepared in (1) to (3) above, by using an FIB (focused
ion beam) system to show the vertical cross-section of
the coating film, the coating film cross-section was
30 observed by TEM (transmission electron microscope) at
arbitrary 10 portions, the particle size was measured at
arbitrary 20 portions in each cross-section, and each of
the average particle sizes above was determined from the
average value thereof. The particle size of a particle
35 falling in a range of 20 ~m was determined when observing
a particle of 1 ~m or more; the particle size of a
• - 74 -
5
particle falling in a range of 5 ~m was determined when
observing a particle of 100 nm to less than 1 ~, and the
particle size of a particle falling in a range of 1 ~m
was measured when observing a particle of less than 100
nm. In a case where the particle was not spherical, the
minor axis and major axis of the particle were measured,
and the average value thereof was taken as the particle
size.
15
25
10
20
[0161]
In addition, the values of alb, clb and dlb, which
were determined from the average particle size (a ~m) of
the polyolefin resin particles (0), the thickness (b ~m)
of the coating film, the average particle size (c ~) of
the silica particle coming under the (C2) spherical
silica particle having an average particle size of 0.3 to
5 ~ out of the silica particles (C), and the average
particle size (d ~) of the at least one resin particles
(F) selected from an acrylic resin and a silicone resin,
are shown together in Tables 12 to 22.
[0162]
(5) Evaluation Test
The coated metal sheet (test sheet) obtained in (4)
was evaluated for the workability, corrosion resistance
and scratch resistance by the following evaluation
methods and evaluation standards. The evaluation results
obtained are shown in Tables 23 to 29.
[0163]
(Workability)
The test sheet was subjected to 180° bending, and the
30 appearance on the outer side of the bent part was
evaluated according to the following evaluation
standards. The bending was performed in an atmosphere of
20°C by sandwiching a 0.5 mm spacer between the sheets
(generally called "IT bending") .
35 5: A problem such as cracking was not observed in
•
5
10
15
20
25
30
35
- 75 -
the coating film and the outer appearance was uniform; in
a case where the coating film was colored, the colored
outer appearance was uniform and no color fading were
observed.
4: Although very slight cracking was observed in the
coating film, the outer appearance was substantially
uniform; in a case where the coating film was colored,
although slight color fading was observed, the colored
outer appearance was substantially uniform (of a level
where the difference could be somehow recognized when a
test sheet before test was arranged alongside) .
3: Slight cracking was observed in the coating film,
and therefore the outer appearance was slightly nonuniform;
in a case where the coating film was colored,
alight color fading was observed, but the colored outer
appearance was substantially uniform (of a level where
the difference could be easily recognized when a test
sheet before test was arranged alongside) .
2: Cracking was observed in the coating film and the
outer appearance was non-uniform; in a case where the
coating film was colored, color fading was recognized (of
a level where the color fading could be somehow
recognized by viewing only the test sheet).
1: Cracking was observed in the coating film and the
outer appearance was non-uniform; in a case where the
coating film was colored, extreme color fading was
recognized (of a level where the color fading could be
easily recognized by viewing only the test sheet).
[0164]
(Corrosion Resistance)
A test sheet was tape-sealed at end faces and then a
salt water spray test (SST) was performed in accordance
with JIS 22371 for 120 hours. The state of rusting was
observed and evaluated according to the following
evaluation standards.
5: No rusting
4: Rusted area of less than 1%
• - 76 -
3 : Rusted area of 1% or more and less than 2.5%
2: Rusted area of 2.5% or more and less than 5%
1 : Rusted area of 5% or more
[0165]
5 (Scratch Resistance)
A test sheet was placed in a rubbing tester and
after rubbing by moving back and force a steel wool
(#0000) on the sheet 10 times under a load of 49.03 kPa
(0.5 kgf/cm2
) or 196.12 kPa (2.0 kgf/cm2
), the film state
10 was evaluated according to the following evaluation
standards.
5: The rubbed face was not scratched at all.
4: The rubbed face was slightly scratched (of a
level where the rubbed mark could be somehow recognized
15 when looked carefully) .
3: The rubbed face was slightly scratched (of a
level where the rubbed mark could be easily recognized
when looked carefully) .
2: The rubbed face was clearly scratched (of a level
20 where the rubbed mark could be recognized at once).
1: The underlying metal sheet of the rubbed surface
was exposed.

• - 86 -
CLAIMS
[Claim 1]
A chromate-free coated metal sheet, comprising a
metal sheet having on at least one surface thereof (a) a
5 coating film containing (A) an organic resin as filmforming
component, (C) silica particles and (0)
polyolefin resin particles, wherein
when the average particle size of the
polyolefin resin particles (0) is "a" JlITl and the
10 thickness of the coating film (a) is by "b" !-tm, these
satisfy 0.5~a~3, 2~b~10 and 0.1~a/b~0.8, and
the silica particles (C) contain both (Cl)
spherical silica particles having an average particle
size of 5 to 50 nm and (C2) spherical silica particles
15 having an average particle size of 0.3 to 5 !-tm.
[Claim 2]
The chromate-free coated metal sheet according to
claim 1, wherein the organic resin (A) contains (Ae) a
polyester resin having a sulfonic acid group in the
20 structure.
[Claim 3]
The chromate-free coated metal sheet according to
claim 2, wherein the organic resin (A) further contains
(Au) a polyurethane resin having a urea group in the
25 structure.
[Claim 4]
The chromate-free coated metal sheet according to
claim 1 or 2, wherein the coating film (a) further
contains (E) a color pigment.
30 [Claim 5]
The chromate-free coated metal sheet according to
claim 1 or 2, wherein the softening point of the
polyolefin resin particles (0) is 125°C or more.
[Claim 6]
35 The chromate-free coated metal sheet according to
claim 1 or 2, wherein the polyolefin resin particles (0)
• - 87 -
is (01) a high-density polyethylene resin particles
having a density of 950 kg/m3 or more and a penetration
hardness of 2 or less.
[Claim 7J
5 The chromate-free coated metal sheet according to
claim 1 or 2, wherein the average molecular weight of the
polyolefin resin particles (0) is from 3,000 to 6,000.
[Claim 8J
The chromate-free coated metal sheet according to
10 claim 1 or 2, wherein the content of the polyolefin resin
particles (0) in the coating film (a) is from 0.5 to 10
mass%.
[Claim 9 J
The chromate-free coated metal sheet according to
15 claim 1 or 2, wherein when the average particle size of
the spherical silica particle (C2) is "c" /-lm and the
thickness of the coating film (a) is "b" /-lm, these
satisfy 0.1~c/b~0.7.
[Claim 10J
20 The chromate-free coated metal sheet according to
claim 1 or 2, wherein the organic resin (A) is a resin
cured by (B) a curing agent.
[Claim 11]
The chromate-free coated metal sheet according to
25 claim 10, wherein the curing agent (B) contains (B1) a
melamine resin.
[Claim 12J
The chromate-free coated metal sheet according to
claim 1 or 2, wherein the coating film (a) is formed by
30 applying (X) an aqueous coating material composition
containing components of the coating film (a) on at least
one surface of the metal sheet and heat-drying the coated
composition.
[Claim 13J
35 The chromate-free coated metal sheet according to
claim 12, wherein the temperature at the time of heat.'
- 88 - Idrying
~he aqueous coating material composition (X) is
from 150 to 250°C in terms of the ultimate sheet
temperature of the metal sheet and the heat-drying time
is from 2.5 to 20 seconds.
5 [Claim 14]
The chromate-free coated metal sheet according to
claim 12, wherein a water cooling step is further
provided after heat-drying of the aqueous coating
material composition (X) and when the softening point of
'"
10 the polyolefin resin particles (0) is TsoC, the sheet
tempera~ure of the metal sheet at water cooling is TMoC
and the water temperature of the cooling water is TwoC,
these satisfy TM>Ts and Tw~(TM-150)/4.
[Claim 15]
15 An aqueous coating material composition (X)
containing (A) an organic resin, (C) silica particles and
(0) a polyolefin resin, wherein
the average particle size of the polyolefin
resin particles (0) is from 0.5 to 3 ~, and
20 the silica particles (C) contain both (C1)
spherical silica particles having an average particle
size of 5 to 50 nm and (C2) spherical silica particles
having an average particle size of 0.3 to 5 ~.
C)~\~;
DEEP KUMAR
OF REMFRY & SAGAR
ATTORNEY FOR THE APPLICANT[S]
•
J