U.S. patent number 3,743,777 [Application Number 05/053,976] was granted by the patent office on 1973-07-03 for process for hardening coatings with lasers emitting infra-red radiation.
This patent grant is currently assigned to Vianova-Kunstharz, A.G.. Invention is credited to Franz Aussenegg, Hans-Dieter Hanus.
United States Patent |
3,743,777 |
Hanus , et al. |
July 3, 1973 |
**Please see images for:
( Certificate of Correction ) ** |
PROCESS FOR HARDENING COATINGS WITH LASERS EMITTING INFRA-RED
RADIATION
Abstract
This invention is directed to a process for hardening or curing
conventional protective coatings applied to a suitable substrate
utilizing lasers emitting infra-red radiation with a wave length of
from 1-100.mu. and preferably 3-25.mu.. The coatings are hardened
within a few minutes of treatment without discoloration normally
associated with short curing durations.
Inventors: |
Hanus; Hans-Dieter (Graz,
OE), Aussenegg; Franz (Graz, OE) |
Assignee: |
Vianova-Kunstharz, A.G.
(Vienna, OE)
|
Family
ID: |
25599968 |
Appl.
No.: |
05/053,976 |
Filed: |
July 10, 1970 |
Foreign Application Priority Data
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|
|
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Jul 17, 1969 [OE] |
|
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A 6914/69 |
Apr 14, 1970 [OE] |
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A 3387/70 |
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Current U.S.
Class: |
219/121.66;
219/121.8; 427/554; 522/81; 522/111; 522/166; 427/508; 522/2;
522/105; 522/142 |
Current CPC
Class: |
B05D
3/02 (20130101); C08L 67/00 (20130101); C08L
67/00 (20130101); C08L 61/20 (20130101) |
Current International
Class: |
B05D
3/02 (20060101); C08L 67/00 (20060101); B23k
009/00 () |
Field of
Search: |
;219/121L
;117/93.3,119.6 ;118/642,643 ;250/49 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
AGA Laboratories Research Bulletin 92, November 1962, pp. 32-47
.
"Practical Uses of Lasers" Science Journal, June 1966, pp. 32-43
.
"Laser Application," IEEE Spectrum, May 1968, pp. 82-92.
|
Primary Examiner: Goldberg; E. A.
Assistant Examiner: Montanye; George A.
Claims
It is claimed:
1. The method of forming a protective coating on a substrate
comprising the steps of
1. providing a substrate coated with a coating composition in the
unhardened state but which is capable of hardening to a thermoset
state when exposed to infra-red radiation;
2. periodically and controllably scanning the entire surface of
said coated substrate with an infra-red laser beam in a dosage
effective to harden said unhardened coating composition by thermic
action, the wavelengths of the radiation being in the range of from
about 1 to 100 .mu.; and
3. discontinuing said scanning when said coating on said substrate
is hardened to the thermoset state.
2. The method according to claim 1 wherein said scanning is with a
diverged infra-red laser beam, said diverging being performed by
directing said beam through an optical element.
3. The method according to claim 1 wherein said scanning is with an
undiverged laser beam.
4. The method according to claim 3 wherein said scanning is
accomplished by moving the laser.
5. The method of claim 3 wherein said scanning is accomplished by
moving optical elements to deflect the laser beam.
6. The method according to claim 1 wherein the scanning is
accomplished by periodically moving the protective coating being
irradiated relative to the laser beam.
7. The method according to claim 1 wherein said scanning is
accomplished by moving both said beam and protective coating being
irradiated.
8. The method according to claim 1 wherein said laser beam is
provided from a CO.sub.2 laser.
Description
FIELD OF THE INVENTION
The present invention is concerned with the curing of protective
coatings. More particularly, it is concerned with a process for
hardening coatings with lasers emitting infra-red radiation.
Hardening or curing as used herein embraces the physical and/or
chemical formation of films of protective coatings on substrates
from a solution or dispersion of a paint, varnish or the like.
Laser (light amplification by stimulated emission of radiation) is
a source of light or radiation emitting monofrequency radiation
(monocolored light) in optimally parallel form.
The heat sources utilized in hardening coatings can be convection
ovens or thermical infra-red radiators. The heat transport by
convection is effected in most cases by the air which is heated
with heating rods or the like, and which will transfer the heat to
the object by natural or artificial flow. Infra-red radiators are
advantageous over convection ovens in that a part of the heat
energy is directly absorbed by the coating and not by the air. From
the start of the curing,the coating will harden not only on the
surface -- as is the case in convection ovens -- but throughout the
coating. Solvents and/or eventual decomposition products are
released completely, i.e. evaporate or volatilize. Deficiencies of
the surface of the cured film are,therefore,minimized.
There are two groups of thermal radiators, light infra-red
radiators and dark infra-red radiators. The light infra-red
radiators emit radiation of a wave length of from 0.5- 4.0.mu. with
a maximum emission at a wave length of 1-2.mu.. Such radiators have
disadvantages in that the solvents and decomposition products
released during the hardening are highly absorptive of the short
infra-red wave lengths of the spectrum, and thus the major portion
of the energy is lost in the heating of the ambient, and the
advantages of hardening by infra-red radiation -- uniform hardening
of the entire coat without deficiencies of the surface, etc., --
are realized only to a minor extent. Furthermore, the absorption of
the coating in the near infra-red region is dependent upon the
binding agent and the pigments, so that different color shades will
not harden uniformly. The dark infra-red radiators emit infra-red
radiation of longer wave length with maximum wave lengths between
3-5.mu.. Solvents and decomposition products absorb these longer
waves to a minor extent. The absorption of the longer waves by the
coating is substantially independent from the type of the binding
agent and the pigments. However, the power per surface unit of the
dark radiator is much lower on account of the lower temperature and
thus radiators with greater surfaces are required. Since the
radiation power emitted by a plane radiator cannot be concentrated
at random, the radiation flux density obtainable with dark
infra-red radiators is relatively small. The hardening times are
therefore considerably longer than with light infra-red
radiators.
It has now been found that with a laser radiator emitting infra-red
radiation, the hardening time required with dark infra-red
radiators can be shortened considerably. The essence of the
invention is the fact that coatings are hardened with laser
emitting infra-red monofrequency and parallel radiation with a
small beam diameter. Thus irradiation with great density and high
local temperatures in the irradiated coating and the substrate,
respectively, are possible, which results in very short hardening
times. The hardened films have no deficiencies. Despite the high
temperatures the films are not discolored due to the short
hardening times. Thus, the invention is characterized in that
coatings based on condensation resins or polymerization resins are
hardened with lasers emitting infra-red radiation with a wave
length of from 1-100.mu., preferably 3-25.mu..
The radiation emitted by lasers within the range selected according
to this invention will be absorbed by the coating, independent from
the type of binding agent, or pigments, etc. Thus, laser hardening
combines the advantage of high density (higher than that of light
infra-red radiators) with the advantage of an infra-red emission
frequency which is, in comparison to dark infra-red radiators,
still more distant from the visible range. The hardening times
required with this source of infra-red radiation lie between 30
seconds and a few minutes. All chemical and/or physical
film-forming coating materials can be hardened with lasers, e.g.
polycondensation resins, polymerization resins, sinterable
synthetic resin powders, polymers, etc., which are optionally
present as solutions and can form films by releasing the solvents.
The coatings can be hardened on metals, stone materials, glass,
wood, rubber, synthetic materials, etc. However, the hardening
process of the invention is particularly suitable for painting or
coating small parts, e.g. parts of precision instruments, and also
for the refinishing of coatings, since the heating by radiation can
be localized very exactly.
The laser beam can be diverged by optical elements such as mirrors,
lenses, etc. With relatively simple means, e.g. a motile mirror, it
is possible to periodically pass the undiverged beam with a
determined speed over the surface to be irradiated ("scanning"). In
this way, coatings on large objects can be hardened. The high power
CO.sub.2 lasers available up to now, however, have a far field
pattern with multimode structure, i.e. the distribution of the
radiation intensity is not uniform within the beam diameter.
Furthermore, the distribution varies during the action. With the
above-mentioned optical measures alone, such as beam diversion,
beam division, combination, etc., it is not possible to obtain an
optimal uniformity of the irradiation of an area. An optimally
uniform hardening of coatings is obtained, if the laser beam is
diverged by optical elements and the diverged beam is passed over
the area to be scanned, directly or indirectly over an element in
the beam path. Instead of the periodic movement of the beam, the
object or objects and beam may be moved. The higher the frequency
of the movement periods, the more similar is the effect to that of
a constant irradiation. It is important that in the average of time
each point of the areas receives the same amount of
irradiation.
The most suitable method of moving the beam relative to the object
or vice versa, is dependent upon the requirements of a particular
application. However, the following methods are representative:
a. The laser beam is diverged in two dimensions with a concave
mirror or with a focusing lens. The direction of the beam is
deflected by suitable movement of the optical elements. The
movement can be an eccentric rotation or a periodic swinging. In
the latter case, in order to cause a uniform irradiation, the
periodic swinging must be carried out with constant velocity (with
the exception of the turning points) and the deflection angle
should be a linear function of time. The deflection of the beam can
also be effected by a moving plane mirror.
b. The laser beam is diverged in one dimension by a cylindrical
concave mirror or by a cylindrical focusing or cylindrical
diverging lens (diversion to a strip). Through a swinging movement
(linear function of time as above) of the diverging elements, the
beam is periodically deflected vertically. Also in this case the
deflection may be effected with an additional plane mirror.
c. The laser beam is not diverged but is periodically deflected in
two dimensions by means of one or two plane mirrors. The duration
of the periods may be equal or different. In an extreme case, the
movement in one of the two dimensions can be without return, i.e.
the area is scanned periodically only in one direction, and only
once in the other direction (linear scanning).
With method (a) the inhomogeneous intensity of the laser beam is
compensated in restricted areas only. The decreasing intensity
towards the edges of the beam cannot be compensated and will result
in a relatively broad marginal area getting reduced irradiation
intensity. Methods (b) and (c) have an advantage over (a) in that
the "exposure" of the area is dependent with method (b) partly and
with method (c) exclusively upon the relative movement between
laser beam and object and can thus be controlled better. It is
evident that in all cases the movements of beam and/or object can
be combined. For hardening coatings on objects of complicated shape
and/or with other than plane surfaces, the elements and movements
are varied in known manner so that a uniform irradiation is
obtained. The following Examples are being set forth to illustrate
the invention. However, they are not to be construed as limiting
its scope.
EXAMPLE 1
a. A paint is applied to a steel panel 0.9 mm thick with a film
applying blade to give a wet film thickness of 0.150 mm. The film
is allowed to dry for 5 minutes at room temperature and is then
hardened with a CO.sub.2 laser at a wave length of 10.6.mu., a
maximum power of 100 watt, and a beam diameter of 1,5 cm.
The Paint Composition is as follows:
binding agent:
80 parts by weight (p.b.w.) of commonly available stoving alkyd
resin based on dehydrated castor oil fatty acid, about 34 percent
fatty acid content, 60 percent in xylol/butanol
20 p.b.w. available melamine-formaldehyde resin, non-plasticized,
partially etherified with butanol, 60 percent in butanol
pigmentation: total binding agent (solid resin) :
Ti O.sub.2 (Rutile type) = 1 : 1
The same paint was applied and hardened in an analogous manner,
to:
wood, 1 cm thickness,
glass, 0.5 cm
asbestos cement, 0.7 cm
polypropylene, 0.3 cm
Irradiation time and obtained film hardness is shown in Table
I.
EXAMPLES 2-6
Analogous to Example 1 five different paints were applied to a
steel panel and hardened. The results are shown in Table II and are
compared with the stoving schedules required in convection ovens to
obtain equal film hardness.
Paint (a) comprises:
binding agent:
80 p.b.w. available saturated polyester resin based on dicarboxylic
acids and polyhydric alcohols (so-called oil-free alkyd resin), 60
percent in xylol/butanol
20 p.b.w. available non-plasticized melamine-formaldehyde resin,
partially etherified with butanol, 60 percent in butanol
pigmentation: total binding agent (solid resin): Ti O.sub.2 (Rutile
type) = 1 : 1
Paint (b) comprises:
binding agent:
80 p.b.w. available heat-hardenable acrylic resin,
50 percent in xylol/butanol
20 p.b.w. available melamine-formaldehyde resin, partially
etherified with butanol, 50 percent butanol
pigmentation: total binding agent (solid resin): Ti O.sub.2 (Rutile
type) = 1 : 1
Paint (c) comprises:
binding agent: available heat cross-linking acrylic resin, 50
percent xylol/butanol
pigmentation: total binding agent (solid resin): Ti O.sub.2 (Rutile
type) = 1 : 1
Paint (d) comprises:
clear varnish
70 p.b.w. available, relatively low molecular epoxide resin, 50
percent isobutylketone
30 p.b.w. available non-plasticized etherified phenolic resin, 50
percent xylol/butanol/isobutylketone
Paint (e) comprises:
dipping primer, dark-grey, 67 percent in water and alcohols
binding agent: available water soluble, plasticized phenolic type
stoving resin
pigmentation: binding agent (solid resin): pigments and fillers, 1
: 1.8.
TABLE I
Substrate Laser Radiation Pencil Stoving Schedule Power/watt Time
Hardness Convection Oven* Paint according to Example 1 on: steel 30
45 sec 2 H C wood 10 180 sec H glass 30 40 sec 2 H C asbestos
cement 30 60 sec 2 H polypropylene 10 150 sec H *to provide
equivalent hardness
TABLE II
Substrate Laser Radiation Pencil Stoving Schedule Power/watt Time
Hardness Convection Oven* Example 2, paint a) on steel 30 90 sec 4
H C Example 3, paint b) on steel 30 75 sec 4 H C Example 4, paint
c) on steel 30 180 sec 3 H C Example 5, paint d) on steel 30 150
sec 3 H C Example 6, paint e) on steel 30 240 sec 2 H C *to provide
equivalent hardness
EXAMPLE 7
A pigmented paint is applied to a steel panel of 0.9 mm with a
rotospinner, type 334/II of Messrs. Erichsen, to give a wet film
thickness of 0.09 mm, and is allowed to dry at room temperature for
15 minutes and is then hardened with a laser beam. The laser beam
is diverged by means of a convex mirror of 11.8 cm radius. The
diverged beam is deflected to the predried film over a periodically
swinging plane mirror. If the plane mirror is not moved, the beam
will reach the panel such that an elliptic area with only the
semi-axis of 2 cm and 4 cm being hardened. By swinging the plane
mirror an area of 8 .times. 10 cm is hardened. In this arrangement
this means a deflection of the axis of the diverged beam by about
6.degree.. (The deflection angle should be a linear function of
time.) The swinging has a frequency of about 1 Hertz. The pigmented
paint consists of 80 parts by weight of a commonly available
stoving alkyd resin based on dehydrated castor oil fatty acid,
about 34 percent fatty acid content, 60 percent in xylol/butanol,
and 20 p.b.w. of an available non-plasticized
melamine-formaldehyde-resin, partially etherified with butanol, as
binding agent. Pigmentation: total binding agent (solid resin) : Ti
O.sub.2 (Rutile type) 1 : 1. Laser: CO.sub.2 laser, type LG 106,
Siemens A.G., Munich, power 100 watt, beam diameter 1.5 cm.
Laser Powermeter: Model 201 Broad Band CW Laser Powermeter of
Coherent Radiation Laboratories, Palo Alto, Calif., USA.
A comparison of Radiation Time and Stoving Conditions in Convection
Ovens to obtain Equal Film Hardness is as follows:
sec Watt/cm.sup.2 Radiation Pendulum Convection oven *) Time sec
hardness 100.degree.C Minutes Persoz**) 120.degree.C 135.degree.C
2.2 - 2.4 120 210 50 20 18 2.1 - 2.7 150 230 60 25 23 2.1 - 2.3 180
236 60 25 23 2.0 - 2.3 195 241 70 30 25 2.2 - 2.7 210 242 70 30 25
2.1 - 2.4 240 255 90 35 30 *) measured power density W/cm.sup.2 of
the diverged laser beam under the conditions of hardening **) 0.4
.mu. dry film thickness
All films cured in the oven were yellowed to a relatively great
extent, whereas the films cured with lasers were free of
yellowing.
EXAMPLE 8
A paint coating according to Example 1 is hardened with the
following laser arrangement: The laser beam is diverged by means of
a cylindrical mirror with a radius of 14.7 cm. The beam is directed
to the paint film. The cylindrical mirror is swung periodically. If
the mirror is not moved, the beam will harden an area of 5 .times.
1 cm. This area is increased to 5 .times. 9.5 cm by swinging the
mirror. The axis of the beam in this arrangement is deflected by
about 12.degree.. The swinging has a frequency of about 0.25 Hertz.
The deflection angle should be a linear function of time. The
results are as follows:
measured power density of the diverged laser beam irradiation time
pendulum hardness Watt/cm.sup.2 sec Persoz, sec 10 - 11 60 111 10 -
11 70 155 10 - 11 80 194 10 - 11 90 211
EXAMPLE 9
The pigmented paint of Example 1 is hardened with the following
laser arrangement. The coherent laser beam is directed to the dried
film over a periodically swinging plane mirror. The coated object
is moved forward vertically to the plane of the scanning laser
beam. The scanning breadth is 9 cm, which corresponds to a
deflection of the axis of the laser beam of about 16.degree.. The
deflection angle should be a linear function of time. The swinging
mirror has a frequency of about 0.25 Hertz. The feed to the
scanning beam is 0.3 - 0.5 mm/sec. The results are as follows:
measured power irradiation pendulum density of the time hardness
feed laser beam Persoz Watt/cm.sup.2 sec sec 39 -- 43 30 115 0.5
mm/sec 38 -- 43 40 187 0.37 mm/sec 38 -- 43 50 201 0.3 mm/sec
The power of the laser was measured with the laser powermeter
during the hardening of the coatings.
It should be appreciated that the present invention is not to be
construed as being limited by the illustrative embodiments. It is
possible to produce still other embodiments without departing from
the inventive concept herein disclosed. Such embodiments are within
the ability of one skilled in the art.
* * * * *