U.S. patent number 3,775,266 [Application Number 05/267,045] was granted by the patent office on 1973-11-27 for process for forming resinous films on anodized aluminum substrates.
This patent grant is currently assigned to Kuboko Paint Company, Limited, Riken Lightmetal Industry Company, Limited. Invention is credited to Isao Hayashi, Katsushige Ikeda, Takashi Kato, Toshihiro Nagano, Toshiro Takahashi, Kenji Wada.
United States Patent |
3,775,266 |
Ikeda , et al. |
November 27, 1973 |
PROCESS FOR FORMING RESINOUS FILMS ON ANODIZED ALUMINUM
SUBSTRATES
Abstract
A process is disclosed for producing a smooth, level and firmly
adhered resinous film on an aluminum or aluminum alloy surface. The
process is carried out at certain temperatures to reduce the
viscosity of water-soluble resin coatings.
Inventors: |
Ikeda; Katsushige (Osaka,
JA), Hayashi; Isao (Osaka, JA), Kato;
Takashi (Osaka, JA), Takahashi; Toshiro
(Shizuoka, JA), Nagano; Toshihiro (Shizuoka,
JA), Wada; Kenji (Shizuoka, JA) |
Assignee: |
Kuboko Paint Company, Limited
(Osaka-shi, JA)
Riken Lightmetal Industry Company, Limited (Shizuoka-shi,
JA)
|
Family
ID: |
12774164 |
Appl.
No.: |
05/267,045 |
Filed: |
June 28, 1972 |
Foreign Application Priority Data
|
|
|
|
|
Jun 29, 1971 [JA] |
|
|
46/47404 |
|
Current U.S.
Class: |
205/201; 205/224;
205/213; 205/229 |
Current CPC
Class: |
C25D
11/18 (20130101) |
Current International
Class: |
C25D
11/18 (20060101); C23f 017/00 (); C23b
009/02 () |
Field of
Search: |
;204/38E,38A,35N,58
;117/75,62,49 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Mack; John H.
Assistant Examiner: Andrews; Richard L.
Claims
What is claimed is:
1. A process for coating an aluminum or aluminum alloy surface
which comprises: degreasing, cleaning and water-rinsing the
surface; etching the water-rinsed surface with an alkaline
solution; neutralizing and water-washing the etched surface;
anodizing the surface; water-rinsing the anodized surface;
immersing the surface in a resin coating composition comprising 20
- 35 percents of one or mone water-soluble thermosetting resins
selected from the group consisting of high temperature reaction
type acrylic resins, alkyd resins, melamine resins, phenolic
resins, urea resins and aminoalkyd resins and 0.1-10 per cent of a
high boiling organic amine, said composition being heated at
40.degree. - 70.degree.C; allowing the resins to set; and drying
and hardening the coated surface at a temperature of 150.degree. -
200.degree.C for 15 - 30 minutes.
Description
This invention relates to a process for producing on an aluminum
surface a protective, ornamental film and more specifically to an
improved process which permits the formation on an aluminum or
aluminum alloy surface of a smooth, level and strong resinous film
by immersion-deposit of a coating at certain elevated
temperatures.
This invention is directed to improvements in the process disclosed
in our copending U.S. Pat. application Ser. No. 27,424 filed on
Apr. 10, 1970, wherein anodized porous aluminum or aluminum alloy
surface is treated and covered with a resinous protective film
while the surface is wet and moist subsequent to rinsing with
water.
A number of processes have hitherto been proposed for treating and
finishing aluminum-bearing substrates so that product aluminum
articles are resistant to environmental attack, i.e., corrosion by
acidic or alkaline atmosphere and present a continuous, smooth,
level surface appearance.
One of the prior-art processes is an immersion-deposit process
wherein pretreated aluminum-bearing substrates may be immersed in
an immersion bath containing a thermosetting resin coating, pulled
out, disposed to set and heated to harden. However, highly viscous
resin coatings are difficult by such conventional processes to form
a smooth, level and thick resinous film on an aluminum surface
because the coatings tend to gather locally at the lower part of
the surface and because of relatively high surface tension of the
coating tending to retard the wetting of the aluminum surface. It
is known that the viscosity and surface tension of thermosetting
resin coatings decrease with increasing temperature.
Various coating processes employing heated coating compositions are
known, including, a hot spray coating, a hot airless spray coating
and a hot electrostatic coating. Since the coating according to
these processes is heated immediately before applying, there are
encountered no critical problems associated with preservation of
the coating and evaporation of solvents.
However, in the immersion-deposit process conducted at elevated
temperature a resin coating tends to polymerize resulting in
increased viscosity and less stability for preservation.
Furthermore, organic solvents incorporated in the coating tend
themselves to quick vaporization with the result that the film
obtained is not smooth or level. It has therefore been difficult to
carry out the immersion-deposit process with success at an elevated
temperature.
Whereas, it is an object of the present invention to provide a new,
useful process which will eliminate or alleviate the foregoing
disadvantages encountered with the prior-art processes for the
production of coated films on aluminum or aluminum alloy
substrates.
It is a further object of this invention to provide an economical
process for forming on an aluminum or aluminum alloy surface a
smooth, level, thick and firmly adhered film.
It is still another object of this invention to provide an improved
process for forming a level and thick film on an elongate workpiece
of aluminum or aluminum alloy whereby the coating is prevented from
being locally collected on the workpiece.
These objects and other features of this invention will be apparent
from the following description taken in connection with certain
embodiments of the invention.
As a result of extensive reserch of the relationship between the
aluminum surface characteristics and the coating compositions to be
applied thereon, said relationship having a bearing upon the
quality of the film, it has been found that the above-mentioned
objects of the invention may be achieved by the use of certain
water-soluble, thermosetting resin coating compositions and of
certain process steps that appear hereinafter.
Briefly stated, the inventive concept of this invention resides in
a process wherein a pretreated aluminum or aluminum alloy surface,
which may be electrically anodized, is immersed without prior
filling of cavities formed in the surface by said anodization in a
coating composition comprising 20 - 35 percent of one or more of
water-soluble thermosetting resins selected from the group
consisting of high temperature reaction type acrylic resins, alkyd
resins, acrylalkyd resins, melamine resins, phenolic resins, urea
resins and aminoalkyd resins and 0.1 - 10 percent of high boiling,
organic amine (stabilizer) such as dimethylethanolamine,
monoethanolamine, mono normal propylamine, triethanolamine,
tetraethylenepentamine and ethylene diamine, heated at 40.degree. -
70.degree.C, and allowed to set, dry and harden at 150.degree. -
200.degree.C over a period of 15 - 30 minutes.
Acrylic resins employed herein may be prepared by the process in
which one or more of acrylic acid, methacrylic acid and esters
thereof having a hydroxy group or other derivatives of acrylic acid
are polymerized at 80.degree. - 120.degree.C in a high boiling
water-soluble solvent such as ethylcellosolve, isopropylcellosolve,
butylecellosolve, butylcarbinol in the presence of an initiator
such as benzoylperoxide, and to the resulting polymers are added
alcohol amines of high boiling point thereby obtaining water
soluble amine salts.
It has been found that the water-soluble thermosetting resins when
added in amounts of less than 20 percent of the coating composition
will fail to form a desirably thick film on an aluminum surface,
but when added in amounts exceeding 35 percent will produce
irregularities in the surface finish.
Importantly, therefore the immersion-deposit process according to
the present invention should be carried out at temperatures ranging
between 40.degree. - 70.degree.C. Repeated experiments have
indicated that temperatures lower than 40.degree.C tend to increase
objectionably the viscosity of the coating, while temperatures
higher than 70.degree.C provide inadequate viscosity.
The immersion operations need not be repeated any definite number
of times, but it is sufficient to dip the aluminum substrate in the
immersion bath only until its temperature grows substantially equal
to the temperature of the coating.
The speed of pulling the substrate out of the immersion bath is
also not imperative, but a preferred range of this speed is between
20 and 100 mm/sec. Satisfactory results have been obtained by
setting the substrate for 10 - 15 minutes in the air heated at
30.degree. - 50.degree.C. The substrate should preferably be dried
by means of an infrared drying apparatus or a hot air drying
apparatus. It has been also found that a firmly adhered film as
desired may be obtained by applying to anodized porous aluminum
surface a coating which has been heated at a predetermined
temperature in accordance with the invention. The coating when
heated will readily penetrate into the pores or pits in anodized
aluminum surface believably due to increased momenta of the coating
particles.
The following examples are provided to further illustrate the
process of the present invention, but these are not to be regarded
as limiting.
EXAMPLES I - VIII
An aluminum test piece 50 .times. 50 .times. 1,000 mm in size was
dipped in a 10% caustic soda at 70.degree.C to dissolve oxides and
other foreign particles thereon, washed with water and subsequently
with 10% nitric acid solution at room temperature and again with
water. The pretreated test piece was subjected to anodization using
a 15% H.sub.2 SO.sub.4 electrolyte operated with a DC 16 volts at a
current density of 1 A/dm.sup.2 at a bath temperature of
20.degree.C. It was thereafter washed with water and immersed in a
manner that the test piece was hung down longitudinally by a hoist
cable and thus dipped for 2 minutes in an immersion bath containing
the coating compositions (shown in Table 1) which have been diluted
with water of 100 parts or 130 parts and heated at 40.degree.C or
60.degree.C. The test piece was taken out of the bath of a speed of
50 mm/sec. and disposed to set over a period of 10 minutes at
50.degree.C. The coated aluminum surface was then heated in an
electrical furnace at a temperature of 180.degree.C for 20 minutes,
until it was dried and hardened. A smooth and level resinous film
was formed on the aluminum test pieces as shown in Table 2. The
finished aluminum test piece was subjected to X-ray microanalyzer
to reveal the presence of carbon about 2 microns deep in pores of
the aluminum surface, indicating a firm deposit of the resin
coating on the aluminum surface.
TABLE 1
Coat A B Water-soluble acrylic resins 40 40 High temperature
reaction type melamine resins 10 10 Diethylene glycol
monobutylether -- 38.5 Ethylene glycol monobutylether 38.5 --
Dimethylethanolamine 5.6 5.6 Water 11.5 11.5 Total 105.6 105.6
Note: The figures appearing in the foregoing Table are parts by
weight.
TABLE 2
Level- Thickness of the film (.mu.) ing of Temp. upper lower dif.
the Ex. Coat (.degree.C) end end film 9.7 12.0 2.3 9.4 12.5 3.1
well I B 40 10.5 12.5 2.0 (100) 9.9 12.3 2.4 8.3 11.0 2.7 9.1 12.1
3.0 Do. II B 40 8.4 11.4 3.0 (130) 8.6 11.5 2.9 10.3 14.2 3.9 11.6
14.9 3.3 Do. III A 40 11.3 14.8 3.5 (100) 11.1 14.6 3.5 10.5 12.3
1.8 10.6 11.4 0.8 Do. IV A 40 10.0 12.2 2.2 (130) 10.3 12.0 1.7
10.6 12.8 2.2 9.4 12.5 3.1 Do. V B 60 10.7 13.7 3.0 (100) 10.2 13.0
2.8 10.2 13.4 3.2 9.0 12.3 3.3 Do. VI B 60 10.1 11.9 1.8 (130) 9.8
12.5 2.7 10.2 14.0 3.8 11.0 14.9 3.9 Do. VII A 60 11.3 14.7 3.4
(100) 10.8 14.5 3.7 10.9 12.1 1.2 10.9 13.5 2.6 Do. VIII A 60 9.9
12.6 2.7 (130) 10.6 12.7 2.1 Note: Bracketed figures in the above
Table indicate parts of added water to the coating.
The aluminum test piece coated in accordance with Example I was
subjected to various performance tests as shown in Table 3.
TABLE 3
Test Results of Test Conditions of Test Gloss above 120 Reflection
ratio of 60.degree. mirror surface Pencil hardness above 3H
Mitsubishi UNI pencil Cross cut test 100/100 Erichsen test above
4.5 mm Erichsen tester Bending test below 3mm Bending tester Impact
test .phi.1/2inch.times.500g.times. Dupont impact tester 50 cm
Peeling test 23 kg/cm.sup.2 Riken Peeling tester Wear resistance
15.4 mg/1000 r.p.m. Taper wear tester (CS17500g) Yellowing
resistance no change Sterilizing lamp(15W 20 cm) 500 hours
Weathering test: by weather-ometer no change 500 hours by dew-cycle
do. 100 hours in the open air do. 1 year Alkali resistance no
change 5% NaOH 10 hours Acid resistance do. 5% H.sub.2 SO.sub.4 10
hours Humidity resistance do. 40.degree.C, 100% RH 400 hours Mortar
resistance no change Portland cement 100 parts Sand 300 parts Water
100 parts 5 days Solvent resistance: xylol no change Immersion for
30 minutes at 20.degree.C methanol do. Immersion for 30 minutes at
20.degree.C Stain resistance rouge no change Wipe off after three
days dry ink do. Wipe off with thinner after three days ink do.
Water-wash after three days tobacco do. Wipe off with thinner after
three days sauce do. Water-wash after three days Cass test rating
No. 10 JIS method 80 hours Salt spraying test rating No. 10 JIS
method 200 hours
Although the present invention has been illustrated by reference to
specific examples, it will be understood that such various changes
and modifications thereof will be apparent to those skilled in the
art as fall within the scope of the appended claims.
* * * * *