U.S. patent number 3,775,157 [Application Number 05/183,482] was granted by the patent office on 1973-11-27 for metal coated structure.
Invention is credited to Howard A. Fromson.
United States Patent |
3,775,157 |
Fromson |
November 27, 1973 |
**Please see images for:
( Certificate of Correction ) ** |
METAL COATED STRUCTURE
Abstract
A metal coated structure is disclosed and includes a substrate,
an actinic-sensitive coating thereon which becomes adherent upon
exposure to actinic radiation and a thin metal coating over the
actinic-sensitive coating which will transmit actinic radiation for
rendering the actinic-sensitive coating adherent to the substrate
and the metal coating. After exposure to actinic radiation, the
adhered metal coating is useful per se or provides a basis for
further metal coatings such as electroless and electrolytic
deposited metal coatings.
Inventors: |
Fromson; Howard A. (Weston,
CT) |
Family
ID: |
22672976 |
Appl.
No.: |
05/183,482 |
Filed: |
September 24, 1971 |
Current U.S.
Class: |
428/674; 428/926;
205/187; 427/404; 427/553; 428/457; 428/626; 428/656; 427/250;
427/443.1; 428/336; 428/621; 428/652; 428/686 |
Current CPC
Class: |
H05K
3/048 (20130101); H05K 3/185 (20130101); H05K
3/24 (20130101); G03F 7/016 (20130101); Y10T
428/1275 (20150115); H05K 2203/0525 (20130101); Y10T
428/265 (20150115); H05K 3/388 (20130101); H05K
2201/0347 (20130101); H05K 3/146 (20130101); H05K
2203/072 (20130101); Y10T 428/12778 (20150115); H05K
3/0023 (20130101); Y10T 428/12569 (20150115); Y10T
428/12903 (20150115); Y10S 428/926 (20130101); Y10T
428/12535 (20150115); Y10T 428/31678 (20150401); Y10T
428/12986 (20150115); H05K 2203/0723 (20130101) |
Current International
Class: |
H05K
3/24 (20060101); H05K 3/04 (20060101); H05K
3/02 (20060101); H05K 3/18 (20060101); G03F
7/016 (20060101); H05K 3/00 (20060101); H05K
3/38 (20060101); H05K 3/14 (20060101); C23c
013/02 () |
Field of
Search: |
;117/71M,71R,93
;204/38R,38E,38B |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Kendall; Ralph S.
Claims
What is claimed is:
1. Metal coated structure comprising
a. a substrate;
b. an actinic-sensitive photochemical coating on said substrate
which becomes adherent upon exposure to actinic radiation; and
c. a metal layer over said actinic-sensitive coating which will
transmit actinic radiation to initiate a photochemical reaction in
the actinic-sensitive coating thereby rendering same adherent to
the substrate and the metal layer.
2. Structure of claim 1 wherein said metal layer is vacuum
deposited.
3. Structure of claim 1 wherein said metal layer is selected from
the group of copper, gold, alloys of copper and gold, silver,
aluminum, zinc, nickel and chromium.
4. Structure of claim 1 wherein said metal layer has a thickness of
from about 4,000 to about 10,000 Angstroms.
5. Structure of claim 1 wherein said metal layer has a thickness of
up to about 1.5 microns.
6. Structure of claim 1 wherein said actinic-sensitive material is
a diazo resin.
7. Structure of claim 1 wherein a layer of electroless deposited
metal is applied to said metal layer after exposure of the
actinic-sensitive layer to actinic radiation.
8. Structure of claim 7 wherein said electroless deposited metal is
copper.
9. Structure of claim 7 wherein an electroplated metal layer is
applied to said electroless deposited metal layer.
10. Structure of claim 1 exposed to actinic radiation.
11. Structure of claim 1 exposed to actinic heat radiation.
12. Process for making a metal coated structure which comprises
coating a substrate having an actinic-sensitive photochemical layer
thereon with a metal layer which will transmit actinic radiation to
initiate a photochemical reaction in the actinic-sensitive layer
thereby rendering same adherent to the substrate and the metal
coating.
13. Process of claim 12 wherein said metal layer is vacuum
deposited.
14. Process of claim 13 wherein the vacuum deposited metal layer
has applied thereto a layer of electroless deposited metal after
exposure of the actinic sensitive layer to actinic radiation.
15. Process of claim 14 which includes the step of electroplating a
metal layer to the electroless deposited metal layer.
Description
BACKGROUND
This invention relates to vacuum deposited metal coatings
characterized by excellent adhesion to the substrate coated.
Moreover, this invention relates to post-adhering vacuum deposited
metal coatings using actinic radiation by a technique herein termed
"photogluing."
Vacuum deposited metal coatings have been widely used to provide
shaped articles made from plastic for example with metal finishes.
The technique of so-called "vacuum metallizing" has thus been used
extensively to make interior automobile parts molded from plastic
appear to be made from more expensive metal. Bright chrome and
aluminum finishes have been extensively used in this and other
applications.
A major problem associated with vacuum metallizing which has
seriously limited its usefulness in other than decorative
applications has been the generally poor adhesion of the metal
coating to the substrate coated. Thus, coated articles readily
scratch and mar exposing the substrate. Base and top coats have
been used but increase the time and cost of vacuum metallizing.
Moreover, top coats render the metal coating passive to further
metallizing such as by electroless plating.
Etching pretreatments have also been used to improve adhesion but
these often involve as much as five or six separate treatment steps
which unduly adds to the cost of vacuum metallizing.
The present invention provides a post-coating technique for
obtaining excellent adhesion of vacuum metallized coatings. Not
only is adhesion greatly improved but also the avenue opened for
fabricating further structures using widely practiced metal
deposition techniques.
SUMMARY
The metal coated structure of the invention broadly comprises (a) a
substrate; (b) an actinic-sensitive coating on said substrate which
becomes adherent upon exposure to actinic radiation and (c) a metal
layer over said actinic-sensitive material which will transmit
actinic radiation for rendering the actinic-sensitive coating
adherent to the substrate and the metal coating.
Additionally, the metal layer can have applied thereto a layer of
electroless deposited metal after exposure of the actinic-sensitive
layer through the metal coating. Following this, the structure may
be electroplated over the electroless metal layer.
The process of this invention comprises coating a substrate having
an actinic-sensitive layer thereon with a preferably vacuum
deposited metal layer which will transmit actinic radiation for
rendering the actinic-sensitive layer adherent to the substrate and
the metal coating.
The process of the invention also embodies the additional steps of
depositing an electroless metal layer on the metal layer and
electroplating over the electroless deposited metal.
DESCRIPTION OF THE DRAWING
In the accompanying drawing schematic edge-on views are shown and
the thickness of the various layers have been greatly exaggerated
for ease of understanding, it being understood that in practice
these layers are relatively thin. Also the terms light-sensitive
and actinic-sensitive are used interchangeably.
In FIG. 1, substrate 10 is shown having an unexposed
light-sensitive layer 12 thereon over which is applied a preferred
vacuum deposited metal layer 14.
In FIG. 2, the structure of FIG. 1 is shown positioned below a
source 20 of actinic radiation which passes through layer 14 to
layer 12 thereby rendering same adherent to substrate 10 and layer
14.
In FIG. 3, a layer of electroless deposited metal 40 is shown
applied to the layer 14.
In FIG. 4, the structure of FIG. 3 is shown with an electroplated
layer 50 over the electroless layer 40.
DESCRIPTION
In general, the substrate may be virtually any shaped or flat
article such as a sheet or a laminate which may be rigid or
flexible with varying thicknesses. The substrate may be a synthetic
resin, plastic film or sheet, metallic sheets or foils or papers
and textiles formed from natural or synthetic fibers or
filaments.
The light-sensitive layer or coating used in the structure of this
invention must become strongly adherent to both the substrate and
the metal layer upon exposure and may be formed from a host of
photochemical materials known in the art. Such light-sensitive
materials include dichromated colloids, such as those based on
organic colloids, gelatin, process glue, albumens, caseins, natural
gums, starch and its derivatives, synthetic resins, such as
polyvinyl alcohol and the like; unsaturated compounds such as those
based on cinnamic acid and its derivatives, chalcone type
compounds, stilbene compounds and the like; and photopolymerizable
compositions, a wide variety of polymers including vinyl polymers
and copolymers such as polyvinyl alcohol, polyvinyl acetals,
polyvinyl acetate vinyl sorbate, polyvinyl ester acetal, polyvinyl
pyrrolidone, polyvinyl butyrol, halogenated polyvinyl alcohol;
cellulose based polymers such as cellulose-acetate
hydrogenphthalate, cellulose alkyl ethers; urea-formaldehyde
resins; polyamide condensation polymers; polyethylene oxides;
polyalkylene ethers; polyhexamethylene adipamide; polychlorophene;
polyethylene glycols, and the like. Such compositions utilize as
initiators carbonyl compounds, organic sulphur compounds,
peroxides, redox systems, azo and diazo compounds, halogen
compounds and the like. These and other photochemical materials
including their chemistry and uses are discussed in detail in a
text entitled Light-Sensitive Systems, Jaromir Kosar, John Wiley
and Sons, Inc., New York, 1965. Diazo resins are particularly
preferred.
The foregoing photochemicals are often used in the printing plate
art where negative working, light-sensitive materials are applied
or coated onto a suitable support or substrate and are of such a
nature that before exposure to actinic radiation they are soluble
in a particular solvent (usually water). When exposed to actinic
radiation, however, the material becomes insoluble in the solvent.
Other positive working light-sensitive materials function just the
opposite, that is, they are insoluble and become soluble upon
exposure to actinic radiation.
The criteria for the present invention, however, is not based on
relative solubility but on the ability of the photochemical
material to become adherent to both the substrate be it
hydrophilic, oleophilic or ampholic and the vacuum deposited metal
layer upon exposure to actinic radiation.
The thickness of the layer 14 may range from a layer which is
atomic in dimension, that is 1 molecule thick up to a thickness of
about 1.5 microns. The layer 14 preferably has a thickness of from
about 2,000 to about 15,000 Angstroms and more preferably from
about 4,000 to about 10,000 Angstroms.
The thickness of the layer 14 can also be expressed as a function
of the wave length of the actinic radiation utilized to expose the
light-sensitive layer 12. It has been found that generally the
thickness of the layer 14 should not be greater than about 10 times
the wave length of the actinic radiation and preferably not greater
than 5 times the wave length. By definition, actinic radiation is
that which will initiate a photochemical reaction and includes
x-rays, infrared, visible light and ultraviolet light. Generally,
speaking an intense source of visible and/or ultraviolet light is
used.
The thickness of the layer 14 must be such that it is capable of
transmitting actinic radiation to the light-sensitive coating.
Generally the layer 14 is deposited in thicknesses within the
ranges specified above such that there is at least 5 percent and
preferably at least 30 percent transparency so as to transmit
actinic radiation to the underlying light-sensitive layer.
The layer 14 according to this invention may be vacuum depositable
metal elected from the group of the metals of Groups I B, II B, III
A, IV A, VI B, VII, of the Periodic Chart. Two or more metals may
be used in combination to form the protective coating. Examples of
preferred metals include chromium, copper, aluminum, gold, gold
alloys, silver, zinc, platinum, iron, cobalt and nickel.
The metal layer 14 has been referred herein as vacuum coated which
is the preferred deposition technique. However, metal layer 14 can
be applied or deposited using coating techniques which result in
uniform deposition of the metal on the light-sensitive layer and
which will not adversely affect the light sensitive layer such as
by premature exposure. Suitable coating techniques include vacuum
coating, sputtering, ion plating, gas plating, and metallized
coatings produced by spray metal techniques.
The preferred coating technique is vacuum coating. In vacuum
coating, metal particles are deposited by vacuum distillation over
the light-sensitive layer to form the metal layer. The substrate
with the light-sensitive layer thereon is placed in a coating
chamber which is evacuated to eliminate molecular interference
between the source of the coating material and the surface to be
coated. Readily high vacuum pumps or diffusion pumps may be used to
evacuate the coating chamber. The metal is heated intensely, for
example, by resistance, induction or electron beam methods, so that
it vaporizes and travels from the course to the substrate with the
light-sensitive coating thereon. The high vacuum facilitates
evaporation of the metal and the absence of air in the coating
chamber permits the vaporized metal to travel directly to the
relatively cool coated substrate where it condenses to form a layer
having a thickness in the range mentioned above. Processes for
vacuum coating are well known as disclosed for example in U.S. Pat.
Nos. 2,206,020; 2,562,182; 2,622,041; 2,635,579; 2,643,201;
2,664,852; 2,664,853; 2,665,233-9; 2,665,320; 2,963,521; 2,903,544;
and 3,562,141.
Metals readily deposited by vacuum coating normally have a
deposition constant of at least 5 .times. 10.sup.-.sup.6 grams per
square centimeter per second at 1 micron pressure (absolute).
Metals especially suited for vacuum coating include aluminum,
silver, gold, lead, zinc, chromium, nickel, copper, tin, iron,
platinum and the like.
The above-mentioned coating techniques are well known and widely
practiced in the art. Details regarding these techniques including
vacuum coating in addition to the above mentioned patents may be
found in Kirk-Othmer Encyclopedia of Chemical Technology, 2nd
Edition, Interscience Publishers, New York, 1967, Vol. 13, pages
249 through 284.
While vacuum coated articles are useful per se especially where
scratch and abrasion resistance is improved as in the present
invention, in many instances it is desirable to further reinforce
the vacuum coated structure. This can be done by using conventional
electrodeposition techniques to deposit further metal coatings over
the vacuum metal layer after exposure of the light-sensitive layer
therethrough. An especially suitable electrodeposition technique as
referred to is electroless plating and is desirable since the
initial vacuum metal layer need only be thick enough for the
electroless deposited metal to bridge molecules in the layer. Such
electroless plating techniques are well-known and widely practiced
in the art. For example, vacuum metal layers according to the
invention formed from copper, aluminum, nickel, gold, molybdenum,
iron, tin, and platinum will catalyze the electroless chemical
reduction deposition of copper, nickel, cobalt, lead, platinum,
iron, silver, aluminum, gold, palladium, and magnesium among
others. Protective layers formed from cobalt, nickel and iron will
also catalyze the deposition of chromium. A preferred metal for
electroless deposition is copper which can be accomplished by
immersing the structure shown in FIG. 2, for example, in an
electroless copper bath containing copper salt, complexing agents
to keep the copper in solution and a reducing agent. The
electroless clad structure of the present invention is shown in
FIG. 3, for example.
The structure shown in FIG. 3 may also be utilized to fabricate
further structures. This can be accomplished by electroplating the
electroless metal layer 40 with layer 50. Electroplating can be
carried out using conventional techniques such as set forth in
Kirk-Othmer Encyclopedia of Chemical Technology, 2nd Edition,
Interscience Publishers, New York, 1965, Vol. 8, pages 36-74.
The present invention finds particular application in the making of
shaped and flat articles from metal, glass, plastic, composites and
the like having a metal finish for use as automotive trim, both
interior and exterior, machine parts, decorative trim and plaques
and the like. Also and very importantly, the present invention
makes it possible to replace relatively heavy and expensive "core"
materials with cheaper (e.g. plastic for metal), lighter and in
many cases stronger or more resilient materials which can be
readily metal clad to retain the desirable properties of the metal
exterior. Examples are precious metal figures, jewelery and machine
parts and more common articles such as automotive bumpers, rails
and the like.
The following examples are intended to further illustrate the
present invention without limiting the same in any manner.
GENERAL COATING PROCEDURE
Metal layers according to the present invention are vacuum
deposited using a bell jar coater in which a single sample is
exposed to a resistance heated vapor source while under vacuum. The
sample to be coated is held against a plate at distances ranging
between about 10 and 20 inches depending on the metal being vacuum
coated. A resistance heated tungsten wire or a molybdenum strip
formed into a boat shape so as to contain the material to be
evaporated is utilized. Between the vacuum source and the work, a
moveable baffle is interposed to allow the material being deposited
to attain the proper vaporizing temperature prior to exposure and
to time the length of the vacuum coating. The baffle prevents the
deposition of powdery or non-adherent coatings which can occur
before full vaporizing temperature is reached. The bell jar coater
is also provided with sight ports to permit measurements of the
vapor source temperature and observation of the melt source itself
during the coating operation.
In actual operation, an extruded polyethylene sheet is sensitized
with a diazo resin and taped to the plate in a darkened room. A
small glass slide strip alongside permits ready measurement of the
vacuum deposited coating. Care must be taken to keep the sheet
shielded from light while placing it in the bell jar coater. Once
the coater is closed, the vacuum pump is started and after a vacuum
of about 0.1.mu. is achieved the heat is turned on to melt the
metal to be vacuum deposited. When the melt reaches the proper
vaporizing temperature, the shutter is opened for a period of time
sufficient to deposit a coating of the thickness desired.
PHOTOGLUING PROCEDURE
Vacuum coated, presensitized polyethylene diazo resin sheets are
exposed to a source of UV light to render the diazo resin adherent
to both the polyethylene sheet and the vacuum metal layer. Scratch
and abrasion resistance is then tested by dragging a weighted point
across the vacuum metal layer. If no metal is removed the specimen
is marked as passing the test and, if metal is removed, the
specimen is marked as failing the test. Adhesion is tested by
applying a pressure sensitive adhesive tape to the vacuum metal
layer and then rapidly stripping it off at a right angle by hand. A
pass or fail is noted as in the scratch and abrasion resistance
test.
EXAMPLES 1-8
Employing the general coating procedure the following materials are
vacuum deposited using the conditions indicated: ##SPC1##
The vacuum metal coatings in Examples 1-8 were approximately 45 to
55 percent transparent.
EXAMPLES 9-11
The specimens prepared in Examples 1 and 5 and 6 are each
electroless plated with copper after being exposed to UV using a
plating bath containing copper sulfate and a reducing agent for the
copper. Excellent coatings are obtained.
EXAMPLE 12
An electroless plated sheets prepared according to Examples 9-11 is
electroplated with copper using conventional techniques. Excellent
quality coatings are obtained.
* * * * *