Note: Descriptions are shown in the official language in which they were submitted.
CA 02383323 2002-03-13
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Description
PRE-PAINT TREATMENT OF METAL AND PRODUCT THEREOF
FIELD AND BACKGROUND OF THE INVENTION
The present invention relates to a pre-paint aqueous treatment agent which is
used to make functionally surface treated steel sheets that are variously
known as
"colored", "painted", or "PCM" steel sheets, a process for manufacturing such
a
s functionally surface treated metal material with superior adhesion using
this pre-paint
aqueous treatment agent, and a metal material so made.
Functionally surface treated steel sheets are used in household electrical
appli-
ances, construction materials, automobiles, etc. Such steel sheets are covered
with an
organic coating film after the metal substrate has been subjected to a
chromate conver-
,o sion coating treatment; accordingly, such plates have superior design
properties in addi-
tion to superior workability and corrosion resistance. However, as concern for
the protec-
tion of the global environment has increased in recent years, the movement to
avoid the
use of substances harmful to the human body (in the case of colored steel
sheets, hexa-
valent chromium contained in the undersurface and organic coating film) has
become
,s stronger. Recently, therefore, there has been an increased demand for
chromium-free
(non-chromate type) undersurface treatment agents and chromium-free (non-
chromate
type) organic coating film agents.
Conventional techniques relating to such agents are disclosed in Japanese
Patent Application Kokai No. 59-116381 and Japanese Patent Application Kokai
No. 4-
20 66173, etc. The technique disclosed in Japanese Patent Application Kokai
No. 59-
116381 is a process in which zinc and zinc alloy surfaces are treated with an
aqueous
solution that contains tannic acid and a silane coupling agent, and a coating
film is
formed on these surfaces. However, since tannic acid is soluble in water, the
adhesion
that is the goal of this invention cannot be obtained in the case of coating
films produced
25 by this process. The technique disclosed in Japanese Patent Application
Kokai No. 4-
66173 relates to metal sheets in which the surfaces of aluminum-plated metal
sheets or
aluminum plates are coated with a treatment solution whose essential
components are
one or more compounds selected from a set consisting of fluorine compounds of
titanium
or zirconium, and one or more agents selected from a group consisting of
silane coupling
so agents that have amino groups, epoxy groups or mercapto groups, after which
this
coating is dried and a heat-resistant resin containing sulfur atoms is formed
on top of this
coating. The metal sheets obtained by this process have a superior heat
resistance;
however, the adhesion that is the goal of this invention cannot be obtained.
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Thus, under current conditions, conversion coating films with superior
corrosion
resistance and adhesion which can be used as pre-paint undersurfaces instead
of chro-
mate conversion coating films cannot be obtained using any process known to
the appli-
cants.
s Major objects of the present invention are to provide a pre-paint aqueous
treatment agent which can form a coating film that has superior corrosion
resistance and
paint adhesion properties on the surface of a metal material, a process for
manufacturing
a metal substrate coated using this pre-paint aqueous treatment agent, and an
article of
manufacture including such a coated metal material substrate.
BRIEF SUMMARY OF THE INVENTION
It has been discovered that a coating film possessing not only corrosion
resist-
ance but also superior adhesion can be formed by treating the surface of a
metal
material with an aqueous treatment agent that contains a specified resin, a
silane
coupling agent and fine particles with a particle size of 1.0 millimeter
(hereinafter usually
,s abbreviated as "mm") or smaller. This discovery led to the present
invention.
DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS
Specifically, the pre-paint aqueous liquid treatment agent of the present
invention,
which has superior adhesion, is characterized by the fact that said agent
comprises,
preferably consists essentially of, or more preferably consists of, water and
the following
2o components:
(a) from 20 to 70 percent by weight of a component selected from a group
consisting
of urethane resins, epoxy resins, and acrylic resins;
(b) from 10 to 60 percent by weight of a component of silane coupling agent;
and
(c) from 10 to 40 percent by weight of a component of dispersed solid
particles with
2s a mean particle size of 1.0 Nm or less,
all of the percentage values specified above for components (a), (b), and (c)
being
percentage of the non-volatiles content of the treatment agent only.
In a process of the present invention, at least one surface of a metal
substrate,
which may optionally have been previously subjected to a chemical plating
treatment or
so a phosphate conversion coating treatment is coated with a liquid layer of
the aforemen-
tioned pre-paint aqueous treatment agent, and later, usually preferably more
or less
immediately after the liquid coating layer has been formed, the liquid coating
is dried,
without any of the non-volatile content of the liquid layer having been
removed by any
method other than volatilization, e.g., by rinsing with another liquid. A dry
coating film
ss thus formed preferably has a mass per unit area coated, a value often
referred to as
"coating weight", that is from 0.05 to 1.0 grams of dry coating per square
meter of
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surface coated, this unit of coating weight being applicable to any kind of
coating and
being hereinafter usually abbreviated as "g/m2".
Moreover, an article of manufacture according to the invention is
characterized
by the fact that said article of manufacture includes a surface made by the
aforemen-
s tinned manufacturing process.
Any urethane resins that constitute all or part of component (a) as described
above preferably contain hydrophilic moieties such as carboxyl moieties,
hydroxy
moieties or amino moieties, etc., as functional moieties. There are no
particular
restrictions on the process of manufacture used for the resins. Suitable
processes
~o include auto-emulsification processes in which an aqueous system is formed
using the
aforementioned hydrophilic functional moieties and emulsion polymerization
processes
using surfactants. Examples of such urethane resins that are commercially
available
include SUPERFLEX 90, 107M, 110, 130, 150, 300, 410, 700, and 820 resins
manufactured by Daiichi Kogyo Seiyaku K.K.; ADEKABONTIGHTER HUX-550, HUX-
~s 232, HUX-670, and HUX-293 resins manufactured by Asahi Denka Kogyo K.K.;
and
PERMALIN UA-200 and UA-300 resins manufactured by San'yo Kasei Kogyo K.K.
Examples of preferable epoxy resins for component (a) include resins obtained
by reaction of epichlorohydrin with at least one of bisphenol-A, bisphenol-F,
hydrogenated bisphenol-A, and novolak type phenol-formaldehyde resins. There
are no
2o particular restrictions on the process of manufacture used for these
resins, and the same
techniques as noted above for urethane resins are also applicable for epoxy
resins.
Examples of commercially available suitable resins include EPI REZ 3519W50,
3522W60, 3540WY55, 3551 WY43, 5003W55, and 6006W70 resins manufactured by
Yuka Shell Epoxy K.K. and ADEKARESIN EPE-0410 and EPE-0425W resins
2s manufactured by Asahi Denka.
Any acrylic resins used in component (a) as described above preferably contain
(meth)acrylic acid or a derivative of (meth)acrylic acid as their chief
component. There
are no narrow restrictions on the process of manufacture used; however, it is
preferable
that the process used be an emulsion polymerization process using a surfactant
so emulsifying agent, more preferably a copolymerizable emulsifying agent such
as sulfo-
ethyl acrylate. Examples of commercially available resins of this type include
PRIMALL
K-3, TR-934, HA-8, NW-1402, NW-1715, E-693, and E-1242E resins manufactured by
Rohm and Haas Co.; MOVINYL 860, 940, 700, 709, 745, and 931 resins
manufactured
by Hoechst Gosei K.K.; and BONCOAT 3625, 3660K, EC-863, EC-898, EC-818, EC-
35 840, EC-846, and EC-856 resins manufactured by Dai-Nippon Inki Kagaku Kogyo
K.K.
The non-volatile content of component (a) preferably is from 25 to 65 percent
by
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weight, or more preferably 30 to 60 percent by weight, relative to 100 percent
by weight
of the total non-volatiles content of the liquid treatment agent. If the non-
volatiles content
of component (a) is less than 20 percent by weight relative to 100 percent by
weight of
the total non-volatiles content, the retention power of component (c) in the
coating film
s drops so that the corrosion resistance drops, which is undesirable. On the
other hand,
if the non-volatiles content of component (a) exceeds 70 percent by weight,
the relative
proportions of component (b) and component (c) drop so that there is a drop in
the corro-
sion resistance and adhesion, which is also undesirable.
It is desirable that the silane coupling agent of component (b) used in the
present
,o invention be a compound which has functional moieties that possess
reactivity with the
resin. Examples of such silane coupling agents include vinyltrichlorosilane,
vinyltrimeth-
oxysilane, vinyltriethoxysilane, vinyltris(~3-methoxyethoxy)silane, ~i-(3,4-
epoxycyclohexyl)-
ethyltrimethoxysilane,y-glycidoxypropyltrimethoxysilane,y-
glycidoxypropyltriethoxysilane,
y-methacryloxypropylmethyldimethoxysilane, y-
methacryloxypropyltrimethoxysilane, y-
is methacryloxypropylmethyldiethoxysilane, y-
methacryloxypropyltriethoxysilane, N-(3-
(aminoethyl)-y-aminopropylmethyldimethoxysilane,N-~i-(aminoethyl)-y-
aminopropyltrime-
thoxysilane, N-(3-(aminoethyl)-y-aminopropyltriethoxysilane, y-
aminopropyltrimethoxysi-
lane, y-aminopropyltriethoxysilane, N-phenyl-y-aminopropyltrimethoxysilane, y-
chloro-
propyltrimethoxysilane and y-mercaptopropyltrimethoxysilane. Furthermore, the
silane
2o coupling agent component used in the present invention may also consist of
two or more
coupling agents used in combination.
The non-volatiles content of component (b) preferably is at least, with
increasing
preference in the order given, 15, 18, 20, 22, or 24 percent by weight and
independently
preferably is at least, with increasing preference in the order given, 50, 40,
38, or 36
25 percent by weight of the total non-volatiles content. If the non-volatiles
content of
component (b) is less than 20 percent by weight relative to 100 percent by
weight of the
total non-volatiles content, the adhesion of the coating film drops, as is
undesirable. On
the other hand, if the non-volatiles content of component (b) exceeds 60
percent by
weight, the relative proportion of component (a) in the coating film drops, so
that the cor-
so rosion resistance drops, as is also undesirable. Good practical results are
facilitated by
a concentration within the more preferred ranges.
Component (c) preferably is selected from the group consisting of plastic pig-
ments, phosphorus-containing anti-rust pigments, and colloidal-sized silica
(including
fumed silica), alumina, zirconia, and titania. It is more preferable if any
silica, alumina,
ss zirconia, or titania used for component (c) has in fact been prepared as a
stable colloid
dispersed in a fluid continuous phase. If the mean particle size of component
(c) ex-
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ceeds 1.0 mm, some of the particles are likely to protrude from the surface of
the coating
film; as a result, moisture may easily invade the surface of the material from
the particle
interfaces, thus causing a drop in corrosion resistance and adhesion.
Accordingly, such
a large mean particle size is undesirable.
s Examples of commercially available fine particles with a mean particle size
of 1.0
Nm or less that are suitable for component (c) include the following: SNOWTEX
20, 30,
40, 50, C, N, O, S, 20L, L, UP, OUP, XL, YL, ZL, P-1040, MP-3040, MP-4540, AK,
and
BK and QAS 40 and 25 colloidal dispersions of silica in water, all
manufactured by
Nissan Kagaku Kogyo K.K.; AEROSIL 130, 200, 300, 380, TT600, MOX80, and MOX170
,o fumed silicas manufactured by Nippon Aerosil K.K.; ALUMINA-SOL 100, 200,
520
dispersions of alumina in water manufactured by Nissan Kagaku Kogyo K.K.; NZS -
20A,
-30A, and -30B dispersions of zirconia in water manufactured by Nissan Kagaku
Kogyo
K.K.; pulverized zinc phosphate, aluminum phosphate, and calcium phosphate as
examples of phosphorus-containing rust-inhibiting pigments; and MUTICLE 100P
and
,s 240D plastic pigments manufactured by Mitsui Kagaku K.K., ROPAQUE OP-62 and
HP-
91 plastic pigments manufactured by Rohm and Haas Co., and MP-1000, -1100, -
1201,
-1450, -1451, -1600, -2701, -3100, and -4009 plastic pigments manufactured by
Soken
Kagaku K.K. Furthermore, component (c) may also consist of a mixture of two or
more
types of particles.
The solids content of component (c) preferably is from 10 to 35 percent by
weight, or more preferably 10 to 30 percent by weight, relative to 100 percent
by weight
of the total non-volatiles content of the aqueous liquid treatment. (Because
component
(c) is defined to be dispersed solids, its solids content is the same as its
non-volatiles
content.) If the solids content of component (c) is less than 10 percent by
weight relative
2s to 100 percent by weight of the total non-volatiles content, the adhesion
drops.
Accordingly, such a small solids content is undesirable. On the other hand, if
the solids
content of component (c) exceeds 40 percent by weight, the coating film
becomes hard
and brittle so that the corrosion resistance and adhesion drop. Accordingly,
such a large
solids content is also undesirable.
so The pH of the pre-paint aqueous treatment agent of the present invention is
pref-
erably in the range of 2 to 10, and is even more preferably in the range of
2.5 to 9.5. If
the pH of the treatment agent is less than 2, there is a danger that the metal
substrate
will be etched and that the corrosion resistance will drop. Accordingly, such
a low pH is
undesirable. On the other hand, if the pH exceeds 10, the alkali component
remaining
ss in the coating film usually causes a drop in the water resistance.
Accordingly, such a
high pH is also undesirable. Furthermore, there are no narrow restrictions on
the
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material used to adjust the pH of the treatment agent. However, if the pH is
to be
adjusted to the acidic side, it is desirable to use at least one substance
selected from the
group consisting of: organic acids, such as formic acid, acetic acid, butyric
acid, oxalic
acid, succinic acid, lactic acid, L-ascorbic acid, tartaric acid, citric acid,
DL-malic acid,
s malonic acid, malefic acid, and phthalic acid; phosphoric acids, such as
meta-phosphoric
acid, pyrophosphoric acid, ortho-phosphoric acid, triphosphoric acid or
tetraphosphoric
acid; and fluorine-containing acids, such as hexafluorozirconic acid,
hexafluorotitanic
acid, hexafluorosilicic acid, and hydrofluoric acid. If the pH is instead to
be adjusted to
the alkaline side, it is preferable to use ammonia or amine compounds such as
,o methylamine, ethylamine, propylamine, isopropylamine, butylamine,
amylamine,
dimethylamine, diethylamine, dipropylamine, diisopropylamine, trimethylamine,
triethylamine, tripropylamine and/or triisopropylamine.
The concentration of the non-volatiles content in the pre-paint aqueous
treatment
agent of the present invention preferably is in a range of from 0.1 to 50 %.
If the concen-
tration of the non-volatiles content is less than 0.1 %, it is difficult to
obtain the desired
amount of coating film; on the other hand, if the concentration of the non-
volatiles
content exceeds 50 %, it becomes difficult to adjust the treatment agent
because of its
high viscosity, so that such a large non-volatiles content is undesirable.
More preferably,
to facilitate practical achievement of a desired coating weight, the
concentration of the
2o non-volatiles content is at least, with increasing preference in the order
given, 0.5, 1.0,
2.0, 3.0, 3.5, or 3.9 % and independently preferably is not more than, with
increasing
preference in the order given, 40, 30, 20, 15, 12, 10, 8, or 6 %.
Metal materials on which the pre-paint aqueous treatment agent of the present
invention can be used include steel, e. g., cold-rolled steel sheets and hot-
rolled acid-
2s washed plates; galvanized steel sheets, e. g., zinc-electroplated steel
sheets, melt-gal-
vanized steel sheets, alloyed galvanized steel sheets, aluminum-containing
galvanized
steel sheets, zinc-nickel-plated steel sheets, zinc-cobalt-plated steel sheets
and vacuum-
deposition type galvanized steel sheets; and aluminum and predominantly
aluminum
alloys.
so Leveling agents, viscosity enhancing agents and film-forming assistants,
etc.,
commonly used in aqueous treatment agents may also optionally be added to the
pre-
paint aqueous treatment agent of the present invention.
When directly applied to the surface of a metal and then dried, the pre-paint
aqueous treatment agent of the present invention can endow the metal material
with a
35 superior corrosion resistance and adhesion; however, such a metal material
can be
endowed with an even more superior corrosion resistance and adhesion by
subjecting
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the material to a chemical plating treatment or a phosphate formation
treatment and then
applying a treatment agent according to this invention over this precoating.
There are
no narrow restrictions on chemical plating processes that can be used, but it
is preferred
to plate iron, cobalt, and/or nickel and independently to have a plating
coating weight of
1 to 50 milligrams per square meter of surface treated (hereinafter usually
abbreviated
as "mg/m2"), calculated as elemental metal. Similarly, there are no narrow
restrictions
on the type of phosphate conversion coating processes that can be used, but it
is
preferable to use a zinc phosphate conversion coating with a coating weight in
the range
from 0.5 to 3 g/m2.
,o The amount of coating film from a treatment according to the invention
preferably
is from 0.05 to 0.5 g/m2. If the amount of coating film that is formed is less
than 0.05
g/m2, the corrosion resistance and adhesion are usually insufficient.
Accordingly, such
a small amount of coating film is undesirable. On the other hand, if the
amount of
coating film exceeds 1.0 g/m2, cohesive failure of the coating film itself
tends to occur
,s more frequently, so that there is a danger that the adhesion will drop.
Accordingly, such
a large amount of coating film is undesirable.
There are no narrow restrictions on the process used to apply the pre-paint
aque-
ous treatment agent of the present invention directly to the surface of the
metal material
or the process used to dry said pre-paint aqueous treatment agent. Examples of
suitable
2o coating processes include roll coating, immersion, and electrostatic
coating. Examples
of suitable drying processes include forced hot air and induction heating.
Independently,
it is desirable that the highest temperature reached by the metal substrate
during drying
be in the range from 50 to 250 °C, and a temperature in the range from
60 to 220 °C is
even more preferable.
2s There are no narrow restrictions on the paint that is applied to the
surface of the
metal material that has been subjected to a pre-paint treatment using the pre-
paint
aqueous treatment agent of the present invention. Examples of suitable paints
include
those containing conventional chromic acid type anti-rust pigments, phosphate
type anti-
rust pigments, molybdate type anti-rust pigments, finely powdered silica, and
other metal
so oxide pigments such as TiOz, and the paints may also contain other coloring
pigments.
Furthermore, one or more further coatings, the last of which is usually called
a "top coat",
may be applied over the ordinary primer or other first coat applied directly
to the surface
formed by a process according to the invention. There are no narrow
restrictions on the
types of paints used in such top coats. Suitable examples include all of epoxy
resin type,
35 polyester resin type, acrylic resin type, urethane resin type, alkyd resin
type, and fluoro-
resin type paints.
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The present invention may be further appreciated by consideration of the
working
examples of the present invention and comparative examples presented below.
Howev-
er, the scope of the present invention is not limited by these working
examples.
The test samples, pretreatments and pre-paint aqueous treatment agent coating
s processes used in the following working examples and comparative examples
are de-
scribed below.
1. Preparation of Test Samples
(1-1) Tested Metal Substrates
The commercially marketed materials indicated below, with short codes used to
,o identify the substrates in a table below following each type in
parentheses, were used
as test materials:
Melt-galvanized steel sheets ("GI") - Sheet thickness = 0.5 millimeter
(hereinafter
usually abbreviated as "mm"), coating weight = 90/90 g/m2;
Melt-galvanized steel sheets containing 5 % aluminum in the galvanizing
coating ("GF")
- Sheet thickness = 0. 5 mm, coating weight = 90/90 g/m2;
Melt-55 %-zinc-45 % aluminum galvanized steel sheets ("GL") - Sheet thickness
= 0.
8 mm, coating weight = 90/90 g/m2;
A-1100 type aluminum plates ("AL") - Sheet thickness = 0.8 mm.
(1-2) Degreasing Treatment
zo The test substrates were subjected to a spray treatment for 2.0 minutes at
a
temperature of 60 °C, using as degreaser a solution in water of
FINECLEANER~ 4336
alkaline degreasing agent concentrate (commercially available from Nihon
Parkerizing
Co., Ltd., Tokyo) at a concentration of 20 grams of the concentrate per liter
of degreasing
agent, this unit of concentration being freely used hereinafter for any
constituent of any
Zs liquid and being usually abbreviated as "g/1". The test substrates were
then washed for
30 seconds with pure water and dried.
(1-3) Pretreatments
(1-3-1) Chemical Plating Treatment
The test substrates which had been subjected to the abovementioned degreasing
so treatment were subjected to a spray treatment at a concentration of 100 g/1
and a
temperature of 50 °C, using PREPALENE~ 4015 chemical nickel plating
liquid
(commercially available from Nihon Parkerizing Co., Ltd.). The test substrates
were then
washed for 30 seconds with deionized water and dried. The amount of adhering
nickel
was found to be 20 mg/m2.
ss (1-3-2) Phosphate Formation Treatment
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Test substrates which had been subjected to the abovementioned degreasing
treatment were dipped for 10 seconds at a temperature of 30 °C in a
solution containing
1.0 g/1 in water of PREPALENE~ Z surface conditioning agent concentrate
(manufac-
tured by Nihon Parkerizing Co., Ltd.). Afterward, the test substrates were
subjected to
s a dipping treatment at a temperature of 60 °C in a solution in water
of 60 g/1 of PAL-
BOND~ L3300 phosphate conversion coating agent (manufactured by Nihon
Parkerizing
Co., Ltd.). The test substrates were then washed for 30 seconds with deionized
water
and dried. The amount of phosphate conversion coating was 2 g/m2.
(1-4) Application of Surface Treatment Agents According to the Invention
,o The pre-paint aqueous treatment agents described below were applied by
means
of a bar coater, and were dried at a temperature of 300 °C.
2. Preparation and Constitution of the Aqueous Pre-Paint Treatment Agents
(Note: All "parts" and percentages stated below are by weight.)
Treatment Agent A
,s Amounts of 100 parts of SUPERFLEX 700 (concentration of non-volatiles
content
35 %) urethane resin manufactured by Daiichi Kogyo Seiyaku K.K. to supply
component
(a), 35 parts of y-glycidoxypropyltriethoxysilane (concentration of non-
volatiles content
100 %) manufactured by Toshiba Silicone K.K. to supply component (b), and 150
parts
of SNOWTEX 20 (concentration of solids 20 %) colloidal silica dispersion
manufactured
2o by Nissan Kagaku Kogyo K.K. to supply component (c) were measured and mixed
with
1710 parts of deionized water by means of propeller agitation. The pH of this
treatment
solution was adjusted to 8 by the dropwise addition of an appropriate amount
of a 5
aqueous solution of ammonia. The part of the total non-volatiles content of
the treatment
solution that was component (a) was 35 percent, the part of total non-
volatiles content
2s of the treatment solution that was component (b) was 35 percent, and the
part of total
non-volatiles content of the treatment solution that was solids content of
component (c)
was 30 percent. The concentration of the total non-volatiles content of the
treatment
solution was 5.0 %.
Treatment Agent B
so Amounts of 100 parts of EPI REZ 5003W55 (concentration of non-volatiles
content 55 %) epoxy resin manufactured by Yuka Shell Epoxy K.K. to supply
component
(a), 25 parts of N-~i-(aminoethyl)-y-aminopropylmethyldimethoxysilane
(concentration of
non-volatiles content 100%) manufactured by Toshiba Silicone K.K. to supply
component
(b), and 100 parts of ZIRCONIA-SOL NZS-20A (concentration of solids content
20%) zir-
35 conia sol manufactured by Nissan Kagaku K.K. to supply component (c) were
measured
out and dispersed in 2275 parts of deionized water by means of propeller
agitation. The
CA 02383323 2002-03-13
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pH of this treatment solution was adjusted to 4 by the dropwise addition of an
appropriate
amount of a 5 % aqueous solution of acetic acid. The weight of the non-
volatiles content
of component (a) was 55 percent by weight, the weight of the non-volatiles
content of
component (b) was 25 percent by weight, and the weight of the solids content
of corn-
s ponent (c) was 20 percent by weight, all relative to 100 percent by weight
of the total non-
volatiles content of the treatment solution, and the total concentration of
the non-volatiles
content of the treatment solution was 4 %.
Treatment Agent C
Amounts of 100 parts of PRIMALL K-3 (concentration of non-volatiles content 46
,o %) acrylic resin manufactured by Rohm and Haas Co. to supply component (a),
20 parts
of y-mercaptopropyltrimethoxysilane (concentration of non-volatiles content
100 %)
manufactured by Toshiba Silicone K.K. as component (b), and 94 parts of
SNOWTEX
OUP (concentration of non-volatiles content 15 %) colloidal silica
manufactured by
Nissan Kagaku Kogyo K.K. to supply component (c) were measured out and
dispersed
,s in 2286 parts of deionized water by means of propeller agitation. The pH of
this
treatment solution was adjusted to 9 by the dropwise addition of an
appropriate amount
of a 5 % aqueous solution of triethylamine. The weight of the non-volatiles
content of
component (a) was 58 percent by weight, the weight of the non-volatiles
content of
component (b) was 25 percent by weight and the weight of the solids content of
2o component (c) was 17 percent by weight, relative to 100 percent by weight
of the total
non-volatiles content of the treatment solution. The concentration of the
total non-
volatiles content of the treatment solution was 4 %.
Treatment Agent D
Amounts of 80 parts of EPI REZ 5003W55 (concentration of non-volatiles content
2s 55 %) epoxy resin manufactured by Yuka Shell Epoxy K.K. and 60 parts of
FINETEX ES-
2200 (concentration of non-volatiles content 25 %) epoxy resin manufactured by
Dai-
Nippon Inki Kagaku Kogyo K.K. to jointly supply component (a), 31 parts of y-
glycidoxypropyltriethoxysilane (concentration of non-volatiles content 100 %)
manufac-
tured by Toshiba Silicone K.K. to supply component (b), and 100 parts of
ALUMINA-SOL
so 100 (concentration of solids content 10 %) alumina sol manufactured by
Nissan Kagaku
Kogyo K.K. to supply component (c) were measured out and dispersed in 729
parts of
deionized water by means of propeller agitation. The pH of this treatment
solution was
adjusted to 3 by the dropwise addition of an appropriate amount of a 5 %
aqueous
solution of phosphoric acid. The weight of the non-volatiles content of
component (a)
ss was 59 percent by weight, the weight of the non-volatiles content of
component (b) was
31 percent by weight, and the weight of the solids content of component (c)
was 10
CA 02383323 2002-03-13
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percent by weight, all relative to the total non-volatiles content of the
treatment solution.
The concentration of the non-volatiles content of the treatment solution was
10 %.
Treatment Agent E
Amounts of 100 parts of PRIMAL K-3 (concentration of non-volatiles content 46
s %) acrylic resin manufactured by Rohm and Haas Co. to supply component (a),
10 parts
of y-glycidoxypropyltriethoxysilane (concentration of non-volatiles content
100 %) and 10
parts of y-chloropropyltrimethoxysilane (concentration of non-volatiles
content 100 %)
both manufactured by Toshiba Silicone K.K. were measured out to supply
component
(b), and 32 parts of MUTICLE 240D (concentration of non-volatiles content 44
%) plastic
,o pigment manufactured by Mitsui Kagaku K.K. to supply component (c) were
measured
out and dispersed in 1098 parts of deionized water by means of propeller
agitation. The
pH of this treatment solution was adjusted to 8 by the dropwise addition of an
appropriate
amount of 5 % aqueous ammonia. The weight of the non-volatiles content of
component
(a) was 58 percent by weight, the weight of the non-volatiles content of
component (b)
,e was 25 percent by weight and the weight of the non-volatiles content of
component (c)
was 17 percent by weight, relative to 100 percent by weight of the total non-
volatiles con-
tent of the treatment solution. The concentration of the total non-volatiles
content of the
treatment solution was 8 %.
Comparative Treatment Agent F
2o Amounts of 35 parts of y-glycidoxypropyltriethoxysilane (concentration of
non-
volatiles content 100 %) manufactured by Toshiba Silicone K.K. and 150 parts
of SNOW-
TEX 20 (concentration of non-volatiles content 20 %) colloidal silica
manufactured by
Nissan Kagaku Kogyo K.K. were measured out and dispersed in 1115 parts of
water by
means of propeller agitation. The pH of this treatment solution was adjusted
to 8 by the
25 dropwise addition of an appropriate amount of 5 % aqueous ammonia. The
concentra-
tion of the non-volatiles content of this treatment solution was 5 %. This
treatment
solution did not contain any material corresponding to component (a) of a
treatment
composition according to this invention.
Comparative Treatment Agent G
so Amounts of 100 parts of SUPERFLEX 700 (concentration of non-volatiles
content
35 %) urethane resin manufactured by Daiichi Kogyo Seiyaku K.K. and 150 parts
of
SNOWTEX 20 (concentration of non-volatiles content 20 %) colloidal silica
manufactured
by Nissan Kagaku Kogyo K.K. were measured out and dispersed in 1050 parts of
de-
ionized water by means of propeller agitation. The pH of this treatment
solution was ad-
ss justed to 8 by the dropwise addition of an appropriate amount of 5 %
aqueous ammonia.
The concentration of the non-volatiles content of this treatment solution was
5 %. This
1i
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treatment solution did not contain any material corresponding to component (b)
of a
treatment solution according to this invention.
Comparative Treatment Agent H
Amounts of 100 parts of SUPERFLEX 700 (concentration of non-volatiles content
35 %) urethane resin manufactured by Daiichi Kogyo Seiyaku K.K. and 35 parts
of y-
glycidoxypropyltriethoxysilane (concentration of non-volatiles content 100 %)
manufac-
tured by Toshiba Silicone K.K. were measured out and dispersed in 1265 parts
of deion-
ized water by means of propeller agitation. The pH of this treatment solution
was adjust-
ed to 8 by the dropwise addition of an appropriate amount of 5 % aqueous
ammonia.
The concentration of the non-volatiles content of this treatment solution was
5 %. This
treatment solution did not contain any material corresponding to component (c)
of a treat-
ment solution according to this invention.
Comparative Treatment Agent I
Amounts of 220 parts of SUPERFLEX 700 (concentration of non-volatiles content
35 %) urethane resin manufactured by Daiichi Kogyo Seiyaku K.K., 13 parts of y-
glyci-
doxypropyltriethoxysilane (concentration of non-volatiles content 100 %)
manufactured
by Toshiba Silicone K.K., and 50 parts of SNOWTEX 20 (concentration of non-
volatiles
content 20 %) colloidal silica manufactured by Nissan Kagaku Kogyo K.K., were
mea-
sured out and dispersed in 1717 parts of deionized water by means of propeller
agitation.
2o The pH of this treatment solution was adjusted to 8 by the dropwise
addition of an appro-
priate amount of 5 % aqueous ammonia. The concentration of the non-volatiles
content
of this treatment solution was 5 %. The weight of the non-volatiles content of
the mater-
ial corresponding to component (a) in a composition according to this
invention was 77
percent by weight, the weight of the non-volatiles content of the material
corresponding
25 to component (b) in a composition according to this invention was 13
percent by weight,
and the weight of the non-volatiles content of the material corresponding to
component
(c) was 10 percent by weight, relative to 100 percent by weight of the total
non-volatiles
content of the treatment solution. Thus, the weight of the non-volatiles
content of the
material corresponding to component (a) exceeded the upper limit specified for
a compo-
ao sition according to this invention.
Comparative Treatment Agent J
Amounts of 40 parts of SUPERFLEX 700 (concentration of non-volatiles content
35 %) urethane resin manufactured by Daiichi Kogyo Seiyaku K.K., 46 parts of y-
gly-
cidoxypropyltriethoxysilane (concentration of non-volatiles content 100 %)
manufactured
35 by Toshiba Silicone K.K., and 200 parts of SNOWTEX 20 (concentration of non-
volatiles
content 20 %) colloidal silica dispersion manufactured by Nissan Kagaku Kogyo
K.K.
12
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were measured out and dispersed in 1714 parts of deionized water by means of
propeller agitation. The pH of this treatment solution was adjusted to 8 by
the dropwise
addition of an appropriate amount of 5 % aqueous ammonia. The concentration of
the
non-volatiles content of this treatment solution was 5 %. The weight of the
non-volatiles
s content of the material corresponding to component (a) in a composition
according to
this invention was 14 percent by weight, the weight of the non-volatiles
content of the
material corresponding to component (b) in a composition according to this
invention was
46 percent by weight, and the weight of the non-volatiles content of the
material
corresponding to component (c) in a composition according to this invention
was 40 per-
,o cent by weight, relative to 100 percent by weight of the total non-
volatiles content of the
treatment solution. Thus, the weight of the non-volatiles content of component
(a) was
below the lower limit specified for a composition according to this invention.
Comparative Treatment Agent K
Amounts of 200 parts of SUPERFLEX 700 (concentration of non-volatiles content
,s 35 %) urethane resin manufactured by Daiichi Kogyo Seiyaku K.K., 5 parts of
y-glycid-
oxypropyltriethoxysilane (concentration of non-volatiles content 100 %)
manufactured by
Toshiba Silicone K.K., and 125 parts of SNOWTEX 20 (concentration of non-
volatiles
content 20 %) colloidal silica dispersion manufactured by Nissan Kagaku Kogyo
K.K.,
were measured out and dispersed in 1670 parts of deionized water by means of
2o propeller agitation. The pH of this treatment solution was adjusted to 8 by
the dropwise
addition of an appropriate amount of 5 % aqueous ammonia. The concentration of
the
non-volatiles content of this treatment solution was 5 %. The weight of the
non-volatiles
content of the material corresponding to component (a) in a composition
according to
this invention was 70 percent by weight, the weight of the non-volatiles
content of the
2s material corresponding to component (b) in a composition according to this
invention was
percent by weight, and the weight of the non-volatiles content of the material
corresponding to component (c) in a composition according to this invention
was 25 per-
cent by weight, relative to 100 percent by weight of the total non-volatiles
content of the
treatment solution. Thus, the weight of the non-volatiles content of the
material
so corresponding to component (b) in a composition according to this invention
was below
the lower limit specified for a composition according to this invention.
Comparative Treatment Agent L
Amounts of 60 parts of SUPERFLEX 700 (concentration of non-volatiles content
35 %) urethane resin manufactured by Daiichi Kogyo Seiyaku K.K., 64 parts of y-
ss glycidoxypropyltriethoxysilane (concentration of non-volatiles content 100
%) manufac-
tured by Toshiba Silicone K.K., and 75 parts of SNOWTEX 20 (concentration of
non-
13
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WO 01/20058 PCT/US00/24930
volatiles content 20 %) colloidal silica dispersion manufactured by Nissan
Kagaku Kogyo
K.K., were measured out and dispersed in 1801 parts of deionized water by
means of
propeller agitation. The pH of this treatment solution was adjusted to 8 by
the dropwise
addition of an appropriate amount of 5 % aqueous ammonia. The concentration of
the
s non-volatiles content of this treatment solution was 5 %. The weight of the
non-volatiles
content of the material corresponding to component (a) in a composition
according to
this invention was 21 percent by weight, the weight of the non-volatiles
content of the
material corresponding to component (b) in a composition according to this
invention was
64 percent by weight, and the weight of the non-volatiles content of the
material
,o corresponding to component (c) in a composition according to this invention
was 15
percent by weight, relative to 100 percent by weight of the total non-
volatiles content of
the treatment solution. Thus, the weight of the non-volatiles content of the
material
corresponding to component (b) in a composition according to this invention
exceeded
the upper limit specified for a composition according to this invention.
,s Comparative Treatment Agent M
Amounts of 220 parts of SUPERFLEX 700 (concentration of non-volatiles content
35 %) urethane resin manufactured by Daiichi Kogyo Seiyaku K.K., 18 parts of y-
gly-
cidoxypropyltriethoxysilane (concentration of non-volatiles content 100 %)
manufactured
by Toshiba Silicone K.K., and 25 parts of SNOWTEX 20 (concentration of non-
volatiles
2o content 20 %) colloidal silica dispersion manufactured by Nissan Kagaku
Kogyo K.K.,
were measured out and dispersed in 1737 parts of deionized water by means of
pro-
peller agitation. The pH of this treatment solution was adjusted to 8 by the
dropwise
addition of an appropriate amount of 5 % aqueous ammonia. The concentration of
the
non-volatiles content of this treatment solution was 5 %. The weight of the
non-volatiles
25 content of the material corresponding to component (a) in a composition
according to
this invention was 77 percent by weight, the weight of the non-volatiles
content of the
material corresponding to component (b) in a composition according to this
invention was
18 percent by weight and the weight of the non-volatiles content of the
material corre-
sponding to component (c) in a composition according to this invention was 5
percent
so by weight, relative to 100 percent by weight of the total non-volatiles
content of the
treatment solution. Thus, the weight of the non-volatiles content of the
material
corresponding to component (c) in a composition according to this invention
was below
the lower limit specified for a composition according to this invention.
Comparative Treatment Agent N
35 Amounts of 100 parts of SUPERFLEX 700 (concentration of non-volatiles
content
35 %) urethane resin manufactured by Daiichi Kogyo Seiyaku K.K., 15 parts of y-
gly-
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cidoxypropyltriethoxysilane (concentration of non-volatiles content 100 %)
manufactured
by Toshiba Silicone K.K., and 250 parts of SNOWTEX 20 (concentration of non-
volatiles
content 20 %) colloidal silica dispersion manufactured by Nissan Kagaku Kogyo
K.K.,
were measured out and dispersed in 1635 parts of deionized water by means of
pro-
s peller agitation. The pH of this treatment solution was adjusted to 8 by the
dropwise
addition of an appropriate amount of 5 % aqueous ammonia. The concentration of
the
non-volatiles content of this treatment solution was 5 %. The weight of the
non-volatiles
content of the material corresponding to component (a) in a composition
according to
this invention was 35 percent by weight, the weight of the non-volatiles
content of the
,o material corresponding to component (b) in a composition according to this
invention was
15 percent by weight, and the weight of the non-volatiles content of the
material corre-
sponding to component (c) was 50 percent by weight, all relative to 100
percent by
weight of the total non-volatiles content of the treatment solution. Thus, the
weight of the
non-volatiles content the material corresponding to component (c) exceeded the
upper
is limit specified for a composition according to this invention.
3. Processes Used to Further Coat Test Substrates after Treating Them with a
Treatment Solution According to the Invention.
The respective treated substrates prepared in the working examples and compar-
ative examples were coated with a commercially marketed undercoat paint (V
NITTO
20 #200 manufactured by Dai-Nippon Toryo K.K.) (film thickness: 5.5 Nm) and
were baked
at 200 °C. Then, a top coat paint (V NITTO # 500 manufactured by Dai-
Nippon Toryo
K.K.) was applied (film thickness: 17 Nm), and this was baked at 220
°C, thus producing
the coated substrates subjected to the tests noted below.
4. Evaluation Tests
25 4.1 Corrosion Resistance Test
Scratches that reached the metal material were formed in the coating films by
means of a cutter, and the salt water spray test stipulated in Japanese
Industrial Stand-
ard (hereinafter usually abbreviated as "JIS") 22371 was performed for 480
hours. The
width (in mm) of the rust extending from the cut parts was measured as an
evaluation
so criterion and is reported in tables below on the following scale:
o: less than 3 mm
O: 3 mm or greater, but less than 5 mm
O: 5 mm or greater, but less than 10 mm
X: 10 mm or greater.
35 4.2 Folding Adhesion Tests
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4.2.1 Primary Folding Adhesion Test
In accordance with the test process described in JIS-63312, the respective
test
coated substrates were subjected to a 2T folding test with two spacing sheets
inside the
fold at 20 °C. An evaluation of the extent of stripping of the coatings
from the test coated
s substrates was performed; following the stripping of the tape over the part
of the coated
substrate evaluated, and is reported using the following scale:
o: no stripping
o - O: stripped area of less than 10
O: stripped area of 10 % or greater, but less than 50
,o D: stripped area of 50 % or greater, but less than 80
X: stripped area of 80 % or greater.
4.2.2 Secondary Folding Adhesion Test
The test sheets were immersed in boiling water for 2 hours, and were then al-
lowed to stand for one day. Afterward, a test was performed in the same manner
as the
,5 primary folding adhesion test. The reporting scale was the same as for the
primary
folding adhesion test.
4.3 Coin Scratching Test
A copper coin approximately the size of a U.S. quarter dollar (a Japanese 10-
yen
coin) was positioned at an angle of 45 degrees relative to each test sheet,
and this coin
2o was rubbed across the coating film at a constant speed under a load of 3
kilograms. The
susceptibility of the coating film to scratching was then evaluated and is
reported using
the following scale:
o: 0 % exposure of any part of the substrate under the primer
o - O: less than 10 % exposure of any part of the substrate under the primer
25 O: exposure of 10 % or greater, but less than 50 %, of any part of the
substrate
under the primer
D: exposure of 50 % or greater, but less than 80 %, of any part of the
substrate
under the primer
X: exposure of 80 % or greater of any part of the substrate under the primer.
so A summary of the test conditions used for the pre-paint aqueous treatment
agents is shown in Table 1, and a summary of the coated sheet performance test
results
obtained with these pre-paint aqueous treatment agents is shown in Table 2.
Working Examples No. 1 through 13 in Table 1 show the coated sheet perform-
ance values for metal materials on which coating films were formed by applying
and dry-
ss ing pre-paint aqueous treatment agents of the present invention. It may be
seen that the
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corrosion resistance, primary folding adhesion, secondary folding adhesion and
coin
scratching properties were all good. In Comparative Examples No. 1 through 11
in Table
1, the corrosion resistance, primary folding adhesion, secondary folding
adhesion and
coin scratching properties were all inferior. Accordingly, the contribution of
the present
invention to industry is extremely significant.
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Table 1
Identifier Sub-Pretreatment Treat-Peak MetalCoating
strate ment TemperatureWeight,
Ma- SolutionDuring g/m2
terial Used Drying,
C
Example 1 GI None A 70 0.4
Example 2 GI None B 70 0.4
Example 3 GI None C 70 0.4
Example 4 GI None D 70 0.4
Example 5 GI None E 70 0.4
Example 6 GF None A 70 0.4
Example 7 GL None B 70 0.4
Example 8 AL None C 70 0.4
Example 9 GI None D 120 0.4
Example 10 GI None E 180 0.4
Example 11 GI None A 70 1.0
Example 12 GI Chemical Plating A 70 0.1
Example 13 GI Phosphate ConversionB 70 0.1
Coating
Comparative ExampleGI None F 70 0.4
1
Comparative ExampleGI None G 70 0.4
2
Comparative ExampleGI None H 70 0.4
3
Comparative ExampleGI None I 70 0.4
4
Comparative ExampleGI None J 70 0.4
Comparative ExampleGI None K 70 0.4
6
Comparative ExampleGI None L 70 0.4
7
Comparative ExampleGI None M 70 0.4
8
Comparative ExampleGI None N 70 0.4
9
Comparative ExampleGI Chemical Plating I 70 0.4
Comparative ExampleGI Phosphate ConversionJ 70 0.4
11 Coating
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Table 2
Identifier Coated
Substrate
Performance
Ratings
CorrosionFolding Adhesion Coin Scratching
Resistanceprimary Secondary
Example 1 0 0 0 0 - O
Example 2 0 - O o 0 0 - O
Example 3 0 - O o 0 0 - O
Example 4 0 - O o 0 0 - O
Example 5 0 - O o 0 0 - O
Example 6 0 0 0 0 - O
Example 7 0 - O o 0 0 - O
Example 8 0 - O o 0 0 - O
Example 9 0 0 0 0 - O
Example 10 0 0 0 0 - O
Example 11 0 0 0 - O o - O
Example 12 0 - O o 0 0
Example 13 0 0 0 - O o
Comparative ExampleX X X X
1
Comparative ExampleX X X X
2
Comparative ExampleX X X X
3
Comparative ExampleD 0 X D
4
Comparative ExampleX X X X
Comparative ExampleX X X X
6
Comparative Example0 X X X
7
Comparative ExampleX X X X
8
Comparative ExampleX X X X
9
Comparative ExampleO D D 0
Comparative Example0 0 D D
11
19
