TECHNICAL FIELD
[0001] This invention relates to a protective-film coated stainless steel sheet whose protective
film exhibits a superior resistance to dragging (or scoring) when worked by pressing,
and moreover can be removed with an alkali solution after the pressing.
BACKGROUND ART
[0002] Stainless steel sheets have so good corrosion resistance and appearance that they
are used for many purposes with their surface texture as they are, as seen in kitchen
implements, construction materials and so forth. Such stainless steel sheets, however,
have a disadvantage that any change having once occurred in the surface state tends
to be very conspicuous even when it is partial. Accordingly, when, e.g., members that
utilize the surface texture of a stainless steel sheet as it is are produced by pressing,
a protective film formed of vinyl chloride resin is stuck on the surface in order
to prevent dragging, a phenomenon in which the steel sheet surface abrades because
of its friction with a mold. Also, since the protective film formed of vinyl chloride
resin has insufficient lubricity and workability, the stainless steel sheet is worked
while applying a press oil on the protective film, and, after protective films are
manually peeled, the surfaces of products obtained by working are washed with a chlorine
type solvent such as trichloroethane or an aqueous alkali solution
[0003] However, because of the insufficient lubricity of the protective film formed of vinyl
chloride resin, film cuts may partly occur when the stainless steel sheet is worked
by pressing, tending to cause the dragging on the steel sheet surface. Also, it takes
much labor, time and cost to manually peel protective films. In addition, since the
part having been drawn by working comes in firm adhesion to the stainless steel sheet,
the films may break when peeled or can not be peeled to remain at some portions. Accordingly,
in order to prevent as far as possible the films from cutting when peeled, the protective
film is formed in a large thickness, where the protective film must be formed in a
large thickness even when members not so severely worked by pressing are produced,
resulting in a high material cost. Also, application of the press oil and removal
thereof cause a bad operating environment.
[0004] Accordingly, in order to solve such problems, a method is proposed in which, in place
of the protective film formed of vinyl chloride resin, an aqueous solution or aqueous
dispersion comprised of an alkali-soluble resin composition chiefly composed of acrylic
resin is coated on the stainless steel sheet to provide a protective film formed of
acrylic resin. The stainless steel sheet on which the protective film has been formed
by this method is worked into members and thereafter the members obtained are treated
with an alkali solution to dissolve protective films to thereby remove them, and hence
it is unnecessary to peel the protective films. Thus, the protective film can be formed
on the stainless steel sheet in the state the former firmly adheres to the latter
so as not to cause peeling when worked by pressing, and not to cause the dragging.
Also, since protective films are entirely dissolved by the alkali solution, the protective
films may by no means remain unremoved.
[0005] This alkali-soluble composition is a composition made soluble in alkali by adjusting
the acid value of an acrylic resin. Its adhesion to articles to be protected is known
to be controlled by a method of controlling it in accordance with glass transition
temperature of the acrylic resin or by a method of controlling it by modifying the
acrylic resin with an oligomer or prepolymer of a different resin. As an example in
which a composition whose adhesion is improved by controlling the glass transition
temperature is used to form the protective film of a stainless steel sheet, there
is known a stainless steel sheet on the surface of which a lower-layer coating film
of from 1 µm to 60 µm thick, formed of an acrylic resin having an acid value of from
40 to 400 and a glass transition temperature of from -10°C to 30°C, and an upper-layer
coating film of from 3 µm to 60 µm thick, formed of an acrylic resin having an acid
value of from 40 to 400 and a glass transition temperature of from 40°C to 80°C are
successively formed, and the upper- and lower-layer coating films have a total thickness
of from 5 µm to 100 µm (Japanese Patent Application Laid-open No. 8-156177).
[0006] If a single-layer coating film is made to have a higher adhesion and a higher solubility
in alkali, the film may become highly sticky to cause blocking when stainless steel
sheets are piled up, and also the stainless steel sheet may show an insufficient resistance
to dragging when worked by pressing. Hence, in the above protective film, the lower-layer
and upper-layer coating films are made alkali-soluble, and in that state the lower-layer
coating film is made to have a glass transition temperature lower than the upper-layer
coating film so that the adhesion to the stainless steel sheet can be improved. However,
because of still insufficient adhesion and strength of the film, the stainless steel
sheet may cause the dragging when severely worked by pressing. Also, since the protective
film is removed after the pressing and is thrown away, it is economically preferable
to make the film thickness smaller, but because of a low film strength it has been
difficult to make the thickness smaller than 5 µm.
[0007] Meanwhile, as an example of a composition in which the acrylic resin is modified
with an oligomer or prepolymer of a different resin to improve adhesion, an acryl-urethane
resin is known which is obtained by allowing an acrylic resin to react with a prepolymer
having at least one active isocyanate group and a blocked isocyanate group in the
molecule to produce an acrylic resin containing a blocked isocyanate, followed by
addition of water and thereafter addition of an amino group-containing compound to
react with the acrylic resin containing a blocked isocyanate (Japanese Patent Application
Laid-open No. 4-328173). However, when this composition is applied to form the protective
film of stainless steel sheet, no uniform coating film can be formed in the case of
coating films with a thickness smaller than 3 µm, and hence it has been necessary
to form coating films in a larger thickness. For this reason, the composition must
be used in a large quantity per unit area, resulting in an increase in the cost for
the protective film.
[0008] An object of the present invention is to provide an alkali-soluble protective-film
coated stainless steel sheet improved in adhesion of the protective film so as to
cause no dragging even when worked by severe pressing.
[0009] Another object of the present invention is to provide an alkali-soluble protective-film
coated stainless steel sheet that may cause no dragging in the stainless steel sheet
even when the film is formed in a small thickness.
[0010] Still another object of the present invention is to provide an alkali-soluble protective-film
coated stainless steel sheet having a uniform coating film even when it is formed
in a thin film of 3 µm or less.
DISCLOSURE OF THE INVENTION
[0011] The protective-film coated stainless steel sheet of the present invention comprises
a stainless steel sheet and successively formed on its surface i) a lower-layer coating
film formed of an epoxy-modified acrylic resin obtained by modifying an acrylic resin
having an acid value of from 40 to 300 and a glass transition temperature of from
0°C to 20°C with an epoxy oligomer having a molecular weight of from 500 to 2,000,
to a degree of from 3% by mass to 20% by mass, and ii) an upper-layer coating film
formed of an acrylic resin having an acid value of from 40 to 300 and a glass transition
temperature of from 40°C to 80°C; the upper- and lower-layer coating films having
a total thickness of from 1 µm to 20 µm.
[0012] In order to impart the coating film adhesion and alkali-solubility to the protective
film, it is advantageous to make the protective film have a double-layer structure
as disclosed in Japanese Patent Application Laid-open No. 8-156177. Accordingly, the
present inventors made various studies in order to improve the resistance to dragging
when worked by pressing. As a result, they have discovered that the resistance to
dragging is improved when the acrylic resin is epoxy-modified. Table 1 shows results
obtained when epoxy-modified acrylic resins obtained by allowing an acrylic resin
having an acid value of 100 and a glass transition temperature of 10°C, synthesized
by copolymerisation of methyl methacrylate, butyl acrylate and methacrylic acid, changing
the proportion of the respective components, to react with epoxy oligomers having
different molecular weights were coated on the surface of stainless steel sheets,
followed by drying, and the coating films formed were tested to examine their dissolution
by an aqueous alkali solution, the coating film adhesion, the resistance to dragging
and the resistance to blocking. As is seen therefrom, the resistance to dragging is
improved when epoxy-modified acrylic resins modified with epoxy oligomers having molecular
weights of from 500 to 2,000 are used. The coating film properties shown in Table
1 are tested and evaluated by the methods described later in Example 1.
Table 1
| No. |
Epoxy oligomer |
Coating film |
Dragging resistance |
Blocking resistance |
| |
Molecular weight |
Degree of modification |
solubility |
adhesion |
|
|
| 1 |
400 |
20 |
A |
A |
B |
B |
| 2 |
500 |
20 |
A |
AA |
A |
B |
| 3 |
800 |
3 |
AA |
AA |
A |
B |
| 4 |
800 |
20 |
A |
AA |
A |
B |
| 5 |
1,000 |
1 |
AA |
A |
B |
B |
| 6 |
1,000 |
3 |
AA |
AA |
A |
B |
| 7 |
1,000 |
5 |
AA |
AA |
A |
B |
| 8 |
1,000 |
10 |
AA |
AA |
A |
B |
| 9 |
1,000 |
15 |
A |
AA |
A |
B |
| 10 |
1,000 |
20 |
A |
AA |
A |
B |
| 11 |
1,000 |
25 |
C |
AA |
A |
B |
| 12 |
1,200 |
3 |
AA |
AA |
A |
B |
| 13 |
1,200 |
10 |
AA |
AA |
A |
B |
| 14 |
1,600 |
3 |
A |
AA |
A |
B |
| 15 |
2,000 |
3 |
A |
AA |
A |
B |
| 16 |
2,400 |
3 |
C |
AA |
A |
B |
Remarks:
(1) The degree of modification with epoxy oligomer is indicated as % by mass.
(2) Coating films are in a thickness of 10 µm each. |
[0013] In the present invention, based on the foregoing findings, the upper- and lower-layer
coating films are both formed using materials having large acid values as in the conventional
cases, the lower-layer coating film is formed of an epoxy-modified acrylic resin having
a lower glass transition temperature, having been modified to a degree of from 3 to
20% by mass, and the upper-layer coating film is formed of an acrylic resin having
a higher glass transition temperature, to thereby harmonize the solubility in aqueous
alkali solution of coating films, the resistance to dragging and the resistance to
blocking.
[0014] In the present invention, the lower-layer coating film is a film formed of an epoxy-modified
acrylic resin obtained by modifying an acrylic resin having an acid value of from
40 to 300 and a glass transition temperature of from 0°C to 20°C with an epoxy oligomer
to a degree of from 3 to 20% by mass. The acid value is defined to be from 40 to 300
because, if it is less than 40, it becomes difficult to remove the coating film by
dissolution with an aqueous alkali solution and, if it is more than 300, the coating
film strength may lower to cause a possibility that the coating films are scraped
off when worked. In order to harmonize the alkali-solubility and the coating film
strength, the acid value may preferably be set within the range of from 100 to 300.
Here, the acid value refers to the milligram number of potassium hydroxide that is
necessary to neutralize a free fatty acid contained in 1 g of the acrylic resin solution.
The glass transition temperature is defined to be from 0 to 20°C because, if it is
lower than 0°C, the coating film may have an insufficient strength at room temperature
to cause a lowering of resistance to dragging, and, if it is higher than 20°C, no
high adhesion can be obtained. Also, the resistance to blocking can be more improved
when the acrylic resin has a glass transition temperature of from 10 to 20°C.
[0015] The molecular weight of the epoxy oligomer used for modifying the acrylic resin is
defined to be from 500 to 2,000 because, if it is less than 500, the resistance to
dragging may be unsatisfactory, and, if it is more than 2,000, the alkali-solubility
may be damaged. The degree of epoxy-modification is defined to be from 3 to 20% by
mass because, if it is less than 3% by mass, no sufficient resistance to dragging
can be obtained, and, if it is more than 20% by mass, the alkali-solubility may be
damaged. In order to harmonize the resistance to dragging and the alkali-solubility,
the epoxy oligomer may preferably have a molecular weight of from 800 to 1,200 and
be modified to a degree of from 3 to 10% by mass.
[0016] Various methods are available as methods by which the acrylic resin having an acid
value of from 40 to 300 and a glass transition temperature of from 0 to 20°C is modified
with the epoxy oligomer having a molecular weight of from 500 to 2,000, to a degree
of from 3 to 20% by mass. The methods can be typified by a method in which first the
acrylic resin having an acid value of from 40 to 300 and a glass transition temperature
of from 0 to 20°C is synthesized and then the epoxy oligomer having a molecular weight
of from 500 to 2,000 is added, where an amine is added and thereafter the mixture
obtained is heated to about 100°C to allow carboxyl groups of the acrylic resin to
react with epoxy groups of the epoxy oligomer, and a method in which epoxy groups
of the epoxy oligomer is allowed to react with a carboxyl compound having an unsaturated
bond, e.g., acrylic acid, methacrylic acid, maleic anhydride or an unsaturated fatty
acid, followed by polymerization while dropwise adding an acrylic monomer.
[0017] The upper-layer coating film is formed using an acrylic resin having an acid value
of from 40 to 300 and a glass transition temperature of from 40°C to 80°C. The acid
value is defined to be from 40 to 300 for the same reason as in the case of the lower-layer
coating film. Meanwhile, the glass transition temperature is defined to be from 40°C
to 80°C because, if it is lower than 40°C, the coating film may also become sticky
when temperature rises in the summer season where the temperature in factories may
rise to about 40°C, and, if it is higher than 80°C, the coating film may become brittle
and may crack or peel when films are formed.
[0018] If the lower-layer coating film and upper-layer coating film have a total thickness
smaller than 1 µm, the steel sheet surface can not be prevented from dragging when
worked by pressing. If they have a total thickness larger than 20 µm, the coating
films may be scraped off by a mold in a very large quantity, so that the mold may
have to be frequently repaired, resulting in a lowering of productivity. Hence, they
may preferably have a total thickness of from 1 to 20 µm, and more preferably from
1 to 5 µm. When the lower-layer coating film has a lower glass transition temperature,
the upper-layer coating film may be made to have a thickness larger by at least 1/2
of that of the lower-layer coating film, whereby the resistance to dragging can be
improved.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Fig. 1 is a cross-sectional view of a draw-bead testing mold used in a coating film
dragging resistance test made in Example 1.
BEST MODES FOR WORKING THE INVENTION
[0020] The acrylic resins used in the lower-layer and upper-layer coating films may be polymers
or copolymers of acrylic acid and/or methacrylic acid or copolymers of any of these
monomers with an acrylate, a methacrylate or the like optionally added, the acid value
and glass transition temperature of which have been controlled by the degree of polymerization
and the components of copolymerization. Here, the acrylate or methacrylate may include
methyl acrylate or methacrylate, ethyl acrylate or methacrylate, butyl acrylate or
methacrylate, and 2-ethylhexyl acrylate. The copolymerization monomers may be further
copolymerized with monomers copolymerizable with acrylate or methacrylate, as exemplified
by styrene, acrylonitrile, acrylamide, butadiene and vinyl acetate.
[0021] To the upper-layer coating film, a high-polymer resin powder may be added as a lubricant.
This brings about an improvement in lubricity to enable working without application
of oil, so that an oiling step and a degreasing step can be omitted and also the resistance
to dragging can be improved. If, however, the resin powder is added in an amount less
than 1% by mass, the lubricity may be poorer than the case when press oil is applied,
and if added in an amount more than 25% by mass, the powder may be dispersed in a
treating solution with difficulty to form a gel. Hence, the resin powder may be added
in an amount of from 1 to 25% by mass, and preferably from 1 to 10% by weight taking
account of long-term stability of the treating emulsion. If the resin powder has an
average particle diameter smaller than 0.1 µm, the coating film can have a smaller
coefficient of friction, but can not have so much lubricity. If it has an average
particle diameter larger than 10 µm, the resin powder may come off when worked and
can exhibit no lubricity. Hence, the powder resin may have an average particle diameter
of from 0.1 to 10 µm.
[0022] The resin powder may include, but not particularly limited to, powders of fluorine
resins, polyethylene resins or polyester resins. Any of these resin powders may be
used alone or in combination, or may be melt-blended. In order to improve the lubricity
of coating films, a fluorine resin powder having a good lubricity and a polyethylene
resin powder that may deform with difficulty under a high surface pressure may preferably
be used in the form of a mixture.
[0023] To form the lower-layer and upper-layer coating films on the surface of the stainless
steel sheet, an emulsion of the epoxy-modified acrylic resin may be coated by a coating
process that can form a uniform coating film, e.g., roll coating, followed by drying,
and thereafter an emulsion of the acrylic resin having an acid value of from 40 to
300 and a glass transition temperature of from 40°C to 80°C may be similarly coated
thereon, followed by drying.
EXAMPLES
Example 1
[0024] A plurality of treating emulsions of acrylic resins having different acid values
and glass transition temperatures were prepared by copolymerizing methyl methacrylate,
butyl acrylate and methacrylic acid, changing the proportion of the respective components.
Thereafter, among these, those having lower glass transition temperatures were allowed
to react with bisphenol-A epoxy oligomers so as to be epoxy-modified. Next, emulsions
of the epoxy-modified acrylic resins thus obtained were each coated on the surface
of a stainless steel sheet (steel type: SUS304; finished: BA; sheet thickness: 0.6
mm) by means of a bar coater, followed by drying in an oven to form a lower-layer
coating film. Thereafter, acrylic resins having glass transition temperatures higher
than the acrylic resins having not been epoxy-modified were each similarly coated
on the lower-layer coating film, followed by drying to form an upper-layer coating
film. The coated stainless steel sheets thus obtained, having acrylic resin coating
films, were as shown in Tables 2 and 3.
[0025] Then, these steel sheets were examined on the following properties. Results obtained
are shown in Table 4.
(1) Solubility of coating films:
[0026] Test pieces were immersed in an aqueous NaOH solution (pH: 12; liquid temperature:
40°C), and those which took less than 2 minutes until their coating films completely
dissolved were evaluated as "A"; from 2 minutes to less than 5 minutes, as "B"; and
5 minutes or more, as "C".
(2) Coating film adhesion:
[0027] Test pieces were subjected to a Du Pont impact test (drop height of a weight: 500
mm; weight of the weight: 500 g), and to a taping test in which a cellophane tape
was once stuck to convex portions and then peeled. Those having a coating film retention
of 80% or more were evaluated as "AA"; from 60% to less than 80%, as "A"; from 40%
to less than 60%, as "B"; from 20% to less than 40%, as "C"; and less than 20%, as
"CC".
(3) Resistance to dragging:
[0028] Test pieces (30 mm x 250 mm) were subjected to a draw-bead test as shown in Fig.
1 (pressure applied: 1,500 N; draw rate: 8.3 x 10
-2 m/sec). Those having a coating film retention of 80% or more at the tested portions
were evaluated as "AA"; from 60% to less than 80%, as "A"; from 40% to less than 60%,
as "B"; from 20% to less than 40%, as "C"; and less than 20%, as "CC".
(4) Resistance to blocking:
[0029] Test pieces were superposed in the manner that their protective film sides were put
together, and were left to stand for 24 hours at a temperature of 40°C under application
of a pressure of 1,200 N/cm
2. Test pieces naturally separated thereafter were evaluated as "AA"; those which were
forcedly separated and in which coating films did not peel, as "A"; those in which
coating films partly peeled, as "B"; those in which coating films wholly peeled because
of blocking, as "C".
Table 2
| Sample No. |
Lower-layer coating film |
| |
Acrylic resin |
Molecular weight of epoxy oligomer |
Epoxy modification (mass %) |
Thickness (µm) |
| Acid value |
Glass transition temp. (°C) |
|
|
|
| Example |
|
|
|
|
|
| 1 |
100 |
0 |
1,000 |
10 |
5 |
| 2 |
100 |
10 |
1,000 |
3 |
0.5 |
| 3 |
100 |
20 |
2,000 |
15 |
2 |
| 4 |
200 |
20 |
800 |
10 |
4 |
| 5 |
300 |
10 |
1,000 |
20 |
4 |
| 6 |
300 |
20 |
1,200 |
5 |
10 |
| 7 |
40 |
0 |
500 |
20 |
6 |
| 8 |
40 |
10 |
800 |
10 |
10 |
| Comparative Example |
|
|
|
|
|
| 1 |
100 |
10 |
- |
- |
10 |
| 2 |
100 |
0 |
2,000 |
25 |
0.2 |
| 3 |
100 |
10 |
2,400 |
1 |
10 |
| 4 |
35 |
10 |
400 |
20 |
5 |
| 5 |
100 |
30 |
2,000 |
20 |
6 |
| 6 |
400 |
10 |
1,000 |
10 |
5 |
| 7 |
100 |
20 |
2,000 |
10 |
5 |
| 8 |
100 |
-10 |
1,000 |
10 |
15 |
| 9 |
100 |
10 |
1,000 |
10 |
20 |
Table 3
| Sample No. |
Upper-layer coating film |
Total thickness of upper- and lower-layer coating films (µm) |
| |
Acrylic resin |
Thickness (µm) |
|
| |
Acid value |
Glass transition temperature (°C) |
|
|
| Example |
|
|
|
|
| 1 |
100 |
40 |
3 |
8 |
| 2 |
100 |
40 |
0.5 |
1 |
| 3 |
100 |
80 |
3 |
5 |
| 4 |
200 |
45 |
1 |
5 |
| 5 |
300 |
60 |
2 |
10 |
| 6 |
300 |
50 |
5 |
15 |
| 7 |
40 |
40 |
2 |
8 |
| 8 |
40 |
40 |
10 |
20 |
| Comparative Example |
|
|
|
|
| 1 |
100 |
40 |
10 |
20 |
| 2 |
100 |
30 |
0.2 |
0.4 |
| 3 |
100 |
40 |
5 |
15 |
| 4 |
35 |
30 |
10 |
15 |
| 5 |
100 |
80 |
4 |
10 |
| 6 |
400 |
40 |
2 |
7 |
| 7 |
100 |
85 |
10 |
15 |
| 8 |
100 |
40 |
5 |
20 |
| 9 |
100 |
40 |
5 |
25 |
Table 4
| Sample No. |
Coating film solubility |
Coating film adhesion |
Dragging resistance |
Blocking resistance |
| Example |
|
|
|
|
| 1 |
AA |
AA |
A |
AA |
| 2 |
AA |
AA |
AA |
AA |
| 3 |
A |
AA |
AA |
AA |
| 4 |
AA |
AA |
AA |
AA |
| 5 |
A |
AA |
A |
AA |
| 6 |
AA |
AA |
A |
AA |
| 7 |
A |
AA |
A |
A |
| 8 |
A |
AA |
A |
AA |
| Comparative Example |
|
|
|
|
| 1 |
AA |
A |
B |
AA |
| 2 |
C |
AA |
B |
C |
| 3 |
C |
A |
B |
AA |
| 4 |
C |
A |
B |
B |
| 5 |
A |
A |
B |
AA |
| 6 |
AA |
AA |
B |
AA |
| 7 |
Evaluation was impossible because of cracks produced in coating films. |
| 8 |
AA |
AA |
B |
A |
| 9 |
AA |
AA |
B |
AA |
Example 2
[0030] Methyl methacrylate, butyl acrylate and methacrylic acid were copolymerized to synthesize
an acrylic resin having an acid value of 100 and a glass transition temperature of
10°C. This acrylic resin was allowed to react with an epoxy oligomer having a molecular
weight of 1,000 to obtain an epoxy-modified acrylic resin modified to a degree of
10% by mass. Then, a treating emulsion of this resin was coated on the surfaces of
the same stainless steel sheets as used in Example 1 by means of a bar coater, followed
by drying in an oven to form on each steel sheet a lower-layer coating film with a
layer thickness of 5 µm. Thereafter, methyl methacrylate, butyl acrylate and methacrylic
acid were copolymerized to synthesize an acrylic resin having an acid value of 100
and a glass transition temperature of 40°C. To the treating emulsions obtained, polyethylene
resin powder and/or fluorine resin powder was/were added, and the mixtures obtained
were left to stand in an atmosphere of 40°C for 10 days or 20 days. After leaving,
the treating emulsions obtained were each coated on the lower-layer coating film in
the same manner as the above, followed by drying to form each upper-layer coating
film. Table 5 shows the treating emulsions used for the upper-layer coating film and
also shows the results of the following tests made on the acrylic-resin coating-film
coated stainless steel sheets thus obtained.
(1) Treating emulsion stability:
[0031] The acrylic resin treating emulsions for the upper-layer coating film were hermetically
enclosed in glass containers, and those which neither thickened nor gelled even when
left to stand in an atmosphere of 40°C for 20 days were evaluated as "AA"; those which
neither thickened nor gelled during the first 10 days, as "A"; those which thickened
or gelled before the lapse of 10 days, as "C".
(2) Workability:
[0032] Using disk test pieces, cylinder drawing was tested (punch diameter: 40 mm; draw
ratio: 2.35; blank holding force: 2.5 x 10
4 N). Regarding test piece diameter before working as L
1 and test piece average diameter after working as L
2, those in which L
2/L
1 was less than 0.88 were evaluated as "AA"; from 0.88 to less than 0.90, as "A"; from
0.90 to less than 0.94, as "B"; and 0.94 or more, as "C".
(3) Resistance to dragging:
[0033] Evaluated in the same manner as in Example 1.
Table 5
| Sample No. |
Upper-layer coating film |
Upper/ lower layers total thickness (µm) |
Emulsion stability |
Workability |
Dragging resistance |
| |
Resin powder |
|
|
|
|
| |
Type |
Amount (mass%) |
Average particle diam. (µm) |
Thickness (µm) |
|
|
|
|
| 11 |
I |
5 |
0.1 |
2 |
7 |
AA |
A |
AA |
| 12 |
II |
10 |
0.5 |
3 |
8 |
AA |
A |
AA |
| 13 |
III |
1 |
2 |
7 |
12 |
AA |
AA |
AA |
| 14 |
III |
2 |
4 |
10 |
15 |
AA |
AA |
AA |
| 15 |
III |
5 |
1 |
3 |
8 |
AA |
AA |
AA |
| 16 |
III |
10 |
1.5 |
5 |
10 |
AA |
AA |
AA |
| 17 |
III |
25 |
10 |
15 |
20 |
A |
AA |
AA |
| 11 |
I |
30 |
1 |
(*2) |
- |
C |
- |
- |
| 12 |
II |
10 |
0.01 |
2 |
7 |
AA |
B |
A |
| 13 |
III |
10 |
0.05 |
3 |
8 |
AA |
B |
A |
| 14 |
III |
25 |
13 |
3 |
8 |
A |
B |
A |
| 15 |
III |
0.5 |
1 |
5 |
10 |
AA |
B |
A |
| 16 |
III |
30 |
4 |
(*2) |
- |
C |
- |
- |
| 17 |
- |
0 |
- |
5 |
10 |
AA |
B |
A |
Remarks:
(1) In the item of "Resin powder", I: polyethylene resin powder; II: fluorine resin
powder; and III: a 9/1 (weight ratio) mixture of polyethylene resin powder and fluorine
resin powder.
(2) *2: Treating emulsions of Comparative Samples 11 and 16 gelled and were difficult
to coat. |