[0001] This invention relates to coated stainless steel strips and a process for preparing
the same.
BACKGROUND OF THE INVENTION
[0002] Stainless steel characterized by high corrosion resistance has been widely used in
a variety of fields including chemical industry. In the recent years, there is an
increasing demand for etched, polished, colored or otherwise surface treated stainless
steel as interior materials of large buildings. Especially, etched or polished and
colored stainless steel having decorative features now finds widespread use as entrance
materials in hotels and apartments.
[0003] Most colored stainless steel strips rely on chemical color development which utilizes
surface oxide layers formed by concentrated chromic acid solution or the like. The
chemically colored stainless steel is versatile in that a color tone is available
in accordance with the finish of the underlying steel because color development is
based on optical interference within a very thin oxide layer. On the other hand, coated
stainless steel often used as roof covers are few in this field because the stainless
steel surface is completely covered with color coatings based on color pigments which
do not reflect the polished or etched finish of the underlying steel.
[0004] Nevertheless, the coating technique has several advantages over the chemical coloring
method in that the coating method is easy to carry out and the coated stainless steel
is resistant against fingerprint and easy in storage and maintenance when used as
interior material. Therefore, attempts have been made in the coating technique in
order to develop transparent color coatings capable of reflecting the surface of the
underlying substrate, but none of them have succeeded in producing transparent color
coated stainless steel meeting all the requirements of coating's durability, workability,
and weather resistance.
[0005] Often, coated stainless steel is subject to a number of complex working steps. Since
the paint coating can be stripped where substantial work is done, the use of coated
stainless steel is limited in such applications requiring noticeable working.
[0006] Stainless steel is well resistant against corrosion due to a passive film on its
surface, but unsusceptible to surface treatment such as coating because of the same
surface inertness. The passive film must be removed electrochemically before electroplating
can be carried out. In the case of paint coating, it is impossible in practice to
carry out such complete pretreatment. Particularly for worked articles of stainless
steel, a pretreatment for coating should be as easy as possible.
[0007] Most stainless steel strips are bent as by rolling and pressing when used as building
materials. As the radius of curvature at the bend is reduced, the degree of working
is drastically increased. Therefore, for coated stainless steel, the adhesion of the
coating against working and the durable adhesion of the coating at worked sites are
critical.
[0008] One known pretreatment for coating is chromate treatment as disclosed in Japanese
Patent Application Kokai No. 161069/1982. Transparent color coated stainless steel
is generally required to have a faintly colored coating (having a reduced amount of
coloring pigment) so that the finish of the underlying steel may be seen through the
coating. In this respect, it is undesirable that the pretreatment for improving coating
receptivity leaves the steel surface colored or spotted. Most chromate treatment results
in a more or less colored steel surface. There is a need for chromate treatment capable
of minimizing surface coloring.
SUMMARY OF THE INVENTION
[0009] Therefore, an object of the present invention is to provide a coated stainless steel
strip based on a steel substrate having improved coating receptivity and provided
with a transparent resin coating through which the finish of the steel substrate is
seen. Another object of the present invention is to provide a process for producing
such a coated stainless steel strip.
[0010] According to the present invention, there is provided a coated stainless steel strip
comprising a stainless steel strip having a chromate layer on a surface thereof with
a total chromium content of 0.5 to 50 mg/m². Trivalent chromium occupies at least
60% by weight of the total chromium content and amounts up to 40 mg/m². A transparent
resin coating is on the chromate layer.
[0011] Such a coated stainless steel strip is produced by a process comprising the steps
of chromating a stainless steel strip on a surface thereof to form a chromate layer
as defined above and applying a transparent resin composition to the chromated strip.
[0012] The term "transparent" used with the resin coating means that the texture of the
underlying steel strip can be substantially seen through the coating.
DETAILED DESCRIPTION OF THE INVENTION
[0013] The subject stainless steel strip which is to be processed and coated according to
the present invention is a group of cold rolled stainless steel plates, sheets, coils
and similar products. Such starting strips are obtained by cold rolling hot rolled
stainless steel slabs to a desired thickness, followed by annealing and pickling or
bright annealing for relieving internal stresses introduced by the cold rolling and
imparting appropriate mechanical properties, and optional shot blasting, dull skin
pass, polishing or similar post-treatment for regulating the surface finish.
[0014] The type of stainless steel is not critical. Any desired type of stainless steel
may be used although high corrosion resistant stainless steel of a grade equal to
or higher than SUS 304 is recommended for service as exterior materials.
[0015] According to the present invention, stainless steel strips are subject to chromate
treatment prior to coating.
[0016] Chromate treatment prior to coating as such is common to ordinary steels and has
also been recently practiced on stainless steel in accordance with the widespread
use of coated stainless steel. However, most of conventional coated steel strips including
stainless steel strips used coating compositions containing pigments in high contents
for coloring purpose so that the resulting coats were opaque. As a result, no difference
was observable in outer appearance to know whether the underlying strips were of ordinary
steel, stainless steel or aluminum. Then any type of pretreatment was acceptable prior
to coating as long as it can impart coating receptivity.
[0017] With the recent advance of transparent color coatings through which attractive lustrous
or versatile surface finishes of stainless steel can be seen, the conventional pretreatments
for coating were found ineffective for transparent color coating because they resulted
in undesirable color development or luster change.
[0018] The present invention employs chromate treatment for the purposes of imparting enhanced
adhesion to subsequent overlying coatings and forming a light transmitting chromate
film. A chromate layer capable of meeting both the requirements of coating adhesion
and transparency can be formed by controlling such that the layer may have a total
chromium content of 0.5 to 50 mg/m², preferably 5 to 50 mg/m², more preferably 5 to
30 mg/m² and trivalent chromium occupy at least 60% by weight of the total chromium
content and amount up to 40 mg/m², preferably 5 to 30 mg/m².
[0019] A total chromium content of less than 0.5 mg/m² fails to achieve any improvement
in coating adhesion whereas chromate layers containing more than 50 mg/m² of chromium
become white or green and opaque even when the trivalent chromium content is at least
60% thereof. If the content of trivalent chromium is less than 60% by weight of the
total chromium content, differently stated, if the proportion of hexavalent chromium
increases, the chromate layer would lose transparency and exhibit brown colored spots.
A trivalent chromium content in excess of 40 mg/m² undesirably causes the entire chromate
layer to turn green.
[0020] The chromate layer may contain colloidal silica or a particulate organic resin such
as acrylic resin.
[0021] The chromate layer may be formed on a surface of a stainless steel strip by thoroughly
degreasing and cleaning the strip surface, and applying a chromate treating solution
thereto, followed by drying. The chromate solution used herein is an aqueous solution
containing anhydrous chromic acid, phosphoric acid, silica, and optionally, acrylic
resin, epoxy resin, silane coupling agent or the like. In the case of transparent
coatings through which ultraviolet light can reach the chromate layer, it is desirable,
particularly in building exterior applications, to avoid the addition of resinous
components to the chromate solution for the purpose of retaining weather resistance.
[0022] Also contained in the chromate solution is a reducing agent for reducing hexavalent
chromium of chromic acid into trivalent chromium, the reducing agent including glycols
(e.g., glycerin and ethylene glycol), hydrogen peroxide, saccharides (e.g., sucrose
and starch), alcohols (e.g., methanol), and hydrazine. Phosphoric acid or phosphorous
acid is added to the chromate solution for the purpose of adjusting pH and inhibiting
precipitation of chromium ions. Silica is added for the purpose of retaining coating
adhesion on bending and useful examples are colloidal silica and silica synthesized
by gas phase method.
[0023] The chromate solution may be applied to the strip surface to a predetermined build-up
by means of a roll coater for transfer coating or by spray or shower coating followed
by squeezing by means of a Ringer roll. Subsequent heating at a temperature of about
70 to 120°C yields a chromate layer.
[0024] A specific total chromium content and specific trivalent chromium content and proportion
of the chromate layer within the above-defined ranges may be achieved by regulating
the coverage of the chromate solution and the proportion of trivalent chromium relative
to the total chromium in the chromate solution which in turn, is regulated by controlling
the degree of reduction.
[0025] The thus pretreated stainless steel strip is adapted to receive a transparent resin
coating thereon. The resin coating composition which can be coated herein include
a resin component which may be selected from fluoro resins, acrylic resins, acrylic-silicone
resins, epoxy resins, polyester resins, vinyl chloride resins, and urethane resins.
[0026] Since the coating is transparent enough to allow ultraviolet light to pass through
the coating interior to the stainless steel surface where light reflects and reenters
the coating, the coating undergoes severer deterioration than conventional opaque
coatings. In this regard, the use of fluoro resins characterized by weather resistance
is recommended particularly for use as building exteriors.
[0027] Pigments or dyes are added to the resin coating composition for coloring purpose
insofar as the composition is maintained transparent. UV absorbers such as oxalic
anilide are desirably blended for preventing pigments from being degraded by ultraviolet
light. Examples of the pigment or dye include inorganic pigments such as red iron
oxide, carbon black, and titanium oxide; and organic pigments or dyes such as Phthalocyanine
Blue, Phthalocyanine Green, Quinacridone Red, and Indanthrene Orange. These coloring
agents such as pigments and dyes are added in such amounts that their content in the
dry coating is up to 3% by weight whereby a transparent color coating is obtained.
[0028] In applying a transparent resin coating to the chromate treated stainless steel strip,
any desired well-known coating techniques, for example, brush coating, roll coating,
flow coating, and spray coating may be used. Flow coating is desirable for coating
a number of large flat plates. Roll coating is often used for steel coils. After the
resin coating composition is applied, it is cured into a transparent coating through
an appropriate measure for a particular type of resin, for example, heating and UV
exposure or simply by allowing to stand at room temperature. The resin coating is
usually 5 to 30 µm thick.
[0029] As opposed to the conventional coated stainless steel strips, the coated stainless
steel strips according to the present invention have the feature that the steel surface
can be directly seen from the outside through the coating, thus offering products
capable of taking advantage of the inherent surface texture of stainless steel. By
applying the present process to the stainless steel surface which has undergone a
certain surface finish, for example, by hair line polishing, ordinary polishing, dull
finishing, and various types of etching, there are obtained good looking coated steel
strips which are particularly useful as building exteriors. The coated steel strips
are worked by panel forming and roll forming into a variety of configured members
which will find a variety of applications including interior and exterior wall members,
roof covers, floor members, and ceiling members.
EXAMPLE
[0030] Examples of the present invention are given below by way of illustration and not
by way of limitation.
Examples 1-5 & Comparative Examples 1-8
[0031] Hair line polished 1.5-mm thick strips of stainless steel SUS 304 were cleaned by
alkali degreasing. Three chromate solutions having a percentage reduction of hexavalent
chromium to trivalent chromium of 30%, 60% and 90% were applied to the strips by means
of a roll coater and dried at 70°C, obtaining chromated strips having a total chromium
content as reported in Table 1. A highly transparent fluoro resin coating composition
commercially available under the trade name of New Gamet #9300 Clear from Toa Paint
Co., Ltd. was applied to the chromated strips by means of a roll coater and dried
at 190°C for 5 minutes, yielding a coating of 20 µm thick.
[0032] The coated strips were visually observed for a change of the steel surface through
the clear coating. Additionally, the coated strips were examined for coating adhesion
by a cross cut tape test using a pressure sensitive adhesive Cellophane tape (Scribed
peeling test) and a cross cut tape test using a pressure sensitive adhesive Cellophane
tape following scribed Erichsen working (6 mm cupping) (Scribed Erichsen test) according
to the standard coating adhesion test prescribed under JIS K5400, item 8.5.2.
[0033] The results are shown in Table 1.
[0034] As seen from Table 1, the chromated strips all showed improved coating adhesion over
the only degreased sample. With respect to the surface appearance under the coating,
however, Comparative Examples 1, 2, 3 and 5 having a lower trivalent chromium proportion
developed a brown spot pattern associated with hexavalent chromium and Comparative
Examples 4, 6 and 7 having a higher trivalent chromium proportion developed greenish
white color. In contrast, Examples 1 to 5 having a total chromium content, trivalent
chromium proportion and trivalent chromium content within the scope of the present
invention not only offered a surface appearance under the coating comparable to the
only degreased sample, but also retained the coating tightly.
Examples 6-7 & Comparative Examples 9-10
[0035] Using a continuous coating apparatus, transparent color coated stainless steel coils
were manufactured from 2B-finished 0.7-mm thick coils of stainless steel SUS 304.
After the coils were cleaned by alkali degreasing, a chromate solution having a percentage
reduction of hexavalent chromium to trivalent chromium of 90% was applied to the coils
by means of a roll coater and dried at 110°C, obtaining chromated coils having a total
chromium content of 20 mg/m². Then fluoro resin coating compositions were applied
to the chromated coils by means of a roll coater and baked at 200°C, yielding a coating
of 20 µm thick. The coating compositions used were commercially available under the
trade name of New Gamet #9300 Bronze (Example 6) and Gold (Example 7) from Toa Paint
Co., Ltd.
[0036] For comparison purposes, a sample was manufactured by the same procedure as above
except that chromate treatment was omitted over a portion of the coil. The non-chromated
and coated sample and the chromated and coated sample were compared by a visual observation.
Both the samples had a bronze or gold colored coating which was enough transparent
to see the underlying stainless steel therethrough. The chromated and coated sample
exhibited no spots or color, with no recognizable difference from the non-chromated
and coated sample.
[0037] The samples were subject to a scribed Cellophane tape peeling test and a scribed
Erichsen peeling test as in Examples 1-5. The chromated and coated sample retained
the coating tightly as seen from Table 2.
[0038] Although some preferred embodiments have been described, many modifications and variations
may be made thereto in the light of the above teachings. It is therefore to be understood
that within the scope of the appended claims, the invention may be practiced otherwise
than as specifically described.
1. A coated stainless steel strip comprising
a stainless steel strip having a chromate layer on a surface thereof with a total
chromium content of 0.5 to 50 mg/m², trivalent chromium occupying at least 60% by
weight of the total chromium content and amounting up to 40 mg/m², and
a transparent resin coating on the chromate layer.
2. The coated stainless steel strip of claim 1 wherein said chromate layer has a total
chromium content of 5 to 50 mg/m².
3. The coated stainless steel strip of claim 1 wherein trivalent chromium is present
in said chromate layer in an amount of 5 to 30 mg/m².
4. The coated stainless steel strip of claim 1 wherein said chromate layer has a total
chromium content of 5 to 50 mg/m², trivalent chromium occupying at least 60% by weight
of the total chromium content and amounting from 5 to 30 mg/m².
5. The coated stainless steel strip of claim 1 wherein said transparent resin coating
is 5 to 30 µm thick.
6. A process for producing a coated stainless steel strip, comprising the steps of:
chromating a stainless steel strip on a surface thereof to form a chromate layer
with a total chromium content of 0.5 to 50 mg/m², trivalent chromium occupying at
least 60% by weight of the total chromium content and amounting up to 40 mg/m², and
applying a transparent resin composition to the chromated strip.
7. The process of claim 6 wherein the chromating step includes applying a chromate solution
to the strip surface followed by drying.