U.S. patent application number 10/769416 was filed with the patent office on 2004-09-23 for very ultra thin conductor layers for printed wiring boards.
Invention is credited to Smith, Gordon C..
Application Number | 20040185275 10/769416 |
Document ID | / |
Family ID | 32228798 |
Filed Date | 2004-09-23 |
United States Patent
Application |
20040185275 |
Kind Code |
A1 |
Smith, Gordon C. |
September 23, 2004 |
Very ultra thin conductor layers for printed wiring boards
Abstract
Disclosed is a metal-clad laminate product having a carrier
film, a aqueous soluble release or parting layer deposited onto the
carrier film and which can be mechanically separated from the
carrier film, and an ultra thin metal layer deposited onto the
parting layer. Also disclosed is a method for making the metal-clad
laminate product.
Inventors: |
Smith, Gordon C.; (Arlington
Heights, IL) |
Correspondence
Address: |
Bingham McCutchen LLP
Three Embarcadero Center
San Francisco
CA
94111-4067
US
|
Family ID: |
32228798 |
Appl. No.: |
10/769416 |
Filed: |
January 30, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10769416 |
Jan 30, 2004 |
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10283413 |
Oct 29, 2002 |
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6702916 |
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Current U.S.
Class: |
428/457 ;
156/233; 428/96 |
Current CPC
Class: |
Y10T 428/28 20150115;
B32B 15/08 20130101; B32B 38/18 20130101; Y10T 428/23986 20150401;
B32B 2038/0092 20130101; H05K 2201/0317 20130101; H05K 2203/0769
20130101; Y10T 428/12569 20150115; H05K 2201/0355 20130101; B32B
7/06 20130101; B32B 37/025 20130101; H05K 3/025 20130101; H05K
2203/0786 20130101; Y10T 428/12438 20150115; Y10T 428/2839
20150115; B32B 2457/08 20130101; Y10T 428/31678 20150401 |
Class at
Publication: |
428/457 ;
156/233; 428/096 |
International
Class: |
B44C 001/00 |
Claims
It is claimed:
1. A metal-clad laminate product for the manufacture of printed
circuit boards, the product comprising: (a) a carrier film; (b) a
release agent layer covering a surface of the carrier film, the
release agent layer comprising an aqueous soluble polymer, the
release agent layer being capable of being mechanically peeled from
the carrier layer; and (c) a conductive metal layer deposited onto
the release agent layer, the metal layer having a thickness of at
most 10,000 Angstroms.
2. The laminate product of claim 1 wherein the release agent layer
comprises polyvinyl pyrrolidone.
3. The laminate product of claim 2 wherein the polyvinyl
pyrrolidone in the release layer has a molecular weight of between
10,000 and 5,000,000.
4. The laminate product of claim 1 wherein the carrier layer is a
polymeric film.
5. The laminate product of claim 1 wherein the carrier layer is a
metal foil.
6. The laminate product of claim 1 further comprising an adhesive
layer on the metal layer on its side opposite from the release
agent layer.
7. The laminate product of claim 1, further comprising at least one
semi-cured resin laminate layer adhered to the conductive metal
layer.
8. A metal-clad laminate intermediate product for use in the
manufacture of printed circuit boards, the product comprising: (a)
a carrier film; (b) a release agent lay covering one surface of the
carrier film, the release agent layer comprising an organic polymer
which facilitates the release layer being mechanically peeled from
the carrier film; (c) a primary conductive metal layer deposited
onto the release layer, the metal conductive layer being no thicker
that about 10,000 Angstroms; and (d) a secondary metal layer
deposited on the primary metal layer, the secondary layer having a
thickness of at most 300 Angstroms.
9. The laminate product of claim 8 wherein the release agent layer
comprises polyvinyl pyrrolidone.
10. The laminate product of claim 9 wherein the polyvinyl
pyrrolidone in the release layer has a molecular weight of between
10,000 and 5,000,000.
11. The laminate product of claim 8 wherein the carrier layer is a
polymeric film.
12. The laminate product of claim 8 wherein the carrier layer is a
metal foil.
13. The laminate product of claim 8 further comprising an adhesive
layer on the metal layers on the side opposite from the release
agent layer.
14. The laminate product of claim 8 further comprising at least one
semi-cured resin layer adhered to the conductive layer.
15. A method for making a metal-clad laminate product comprising
the steps of: (a) providing a carrier film of dimensionally stable
material; (b) depositing onto the carrier layer a release agent
layer, the release agent layer comprising an aqueous soluble
polymer, the release agent layer being capable of being
mechanically peeled from the carrier layer; (c) forming a
conductive metal layer on the release agent layer, the metal layer
comprising a metal selected from the group consisting of copper,
gold, chrome, tin, nickel, aluminum, titanium, zinc, and mixtures
thereof, the metal layer having a thickness of at most about 10,000
Angstroms; (d) bonding the metal layer to a resin circuit board
laminate layer; and (e) peeling the carrier film from the metal
layer without damaging the metal layer attached to the circuit
board laminate layer.
16. A method as claimed in claim 15 wherein the release agent layer
is formed of polyvinyl pyrrolidone.
17. A method for making a metal-clad laminate product comprising
the steps of: (a) providing a carrier film of dimensionally stable
suitable material; (b) depositing onto the carrier film a release
agent layer, the release agent layer comprising an aqueous soluble
polymer, the release agent layer being capable of being
mechanically peeled from the carrier layer; (c) forming a
conductive metal layer on the release agent layer, the metal layer
comprising a metal selected from the group consisting of copper,
gold, chrome, tin, nickel, aluminum, titanium, zinc, and mixtures
thereof, the metal layer having a thickness of at most about one
.mu.m; (d) applying a first one resin circuit board laminate layer
to the metal layer and semi-curing the resin; (e) applying a second
resin circuit board laminate layer to the first resin circuit board
laminate layer and semi-curing the second layer while additionally
curing the first layer; and (f) removing the carrier film without
damaging the conductive metal layer.
18. A method as claimed in claim 17 wherein the release agent layer
is polyvinyl pyrrolidone.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority from provisional
application Serial No. 60/047,019, filed May 13, 1997.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] Not applicable.
BACKGROUND OF THE INVENTION
[0003] The electronics industry continues to seek enhanced
performance from products such as printed wiring boards used with
integrated circuits in order to meet consumer demand for higher
performance, lower cost computers and electronics equipment.
Driving forces within the electronics industry include a desire for
increased speed and functionality which requires reduced size of
both components and interconnectors. Among the means by which
interconnection circuitry can be reduced in size include the design
of circuit boards that have smaller, finer lines and spaces to
increase the line density on boards. Increasing line density leads
to fewer circuit layers and smaller, lighter, electronic
devices.
[0004] Printed wiring board circuitry can reside on a rigid
fiberglass reinforced plastic or on flexible films to which are
adhered metal foils used to form conductive circuit connections.
The boards can contain interconnecting circuitry on one layer, two
layers, or multiple layers. Boards with three or more layers can be
manufactured using multiple two layer boards laminated together
forming a multi-layer construction, or can be built up from a two
layer board by sequentially adding dielectric layers and
circuits.
[0005] Multilayer boards are most typically manufactured by
laminating circuitized double sided boards in a stack using sheets
of thermosetting polymers impregnated in fiberglas's, known as
pre-preg. Typically the outer most circuitized layers are added by
using a sheet of pre-preg and a sheet of metal foil. The circuit
connections on the double sided core circuits are usually
manufactured by using subtractive techniques, while the outer metal
conductor layer is shaped in a semi-additive method. The multiple
circuit layers are electrically connected by mechanical drilling of
holes through the board and plating with a conductive metal.
[0006] Sequential built-up boards are manufactured by laminating
foils coated with thermosetting resins to a circuitized double
sided board. The coated resin layer serves as a controlled
dielectric layer separating the built-up circuit layer from the
double sided circuit board. Electrical connections between circuit
layers are made by plasma or laserdrilling, followed by plating the
resulting connecting hole. Circuitizing the built-up circuit is
accomplished using semi-additive methods. Build-up layers can be
stacked forming a circuit with many layers.
[0007] Circuit board designers require substrate materials on which
extremely fine lines and spaces can be formed with a high degree of
precision. Thin metal foils are generally a preferred substrate for
the formation of circuit lines on circuit boards. The use of
thicker foils results in greater waste of metal and reduces the
line density that can be achieved. The metal films are most
commonly formed by electrodeposition. Electrodeposited copper films
typically must be of a defined minimum thickness, >1 .mu.m, to
avoid holes or discontinuities.
[0008] Metal foils that are currently in use in the industry are
typically at least 5 .mu.ms in thickness. The use of thinner metal
foil in printed circuit board would allow the formation of more
densely packed lines and would reduce production costs. There is a
significant interest in developing methods for obtaining thin
copper foils. Existing methods for obtaining and placing a very
thin metal foil on a laminate are limited.
[0009] U.S. Pat. No. 4,357,395 discloses a copper-clad laminate
that is made by first forming a layer of silica on an aluminum
carrier and then sputtering a copper film onto the silica layer.
The copper layer is then laminated to a substrate, and the carrier
and silica layer are mechanically stripped away, leaving the copper
layer exposed. The examples disclosed that copper films 5-10 .mu.ms
in thickness were obtained by this method.
[0010] The method disclosed in U.S. Pat. No. 4,357,395 is not
suitable for the manufacture of copper-clad laminates having an
very ultra thin (0.1-0.3 .mu.m) copper foil, because very ultra
thin foils are susceptible to picking when the carrier and silica
layers are mechanically removed.
[0011] U.S. Pat. No. 4,431,710 reveals an aluminum carried copper
foil where the copper was deposited onto the aluminum foil using
vapor deposition at temperatures between about 100.degree. C. and
250.degree. C. Copper film of 5 .mu.ms in thickness was
demonstrated. After lamination to a substrate, the aluminum carrier
is removed with a peel force of 0.5 lbs./in. to 2.0 lbs./in. The
disclosure discusses the variability in the peel strength
experiences by this method. The high peel strengths and variability
would be detrimental to very ultra thin foils of less than 1 .mu.m
in thickness. In addition, the exemplified foil is shown to have a
significant impact on peel strength, dependent on contaminants.
[0012] U.S. Pat. No. 5,262,247 describes a foil consisting of a
copper carrier layer, a chromate parting layer, a copper-nickel
alloy layer, and finally a thin copper foil layer. Upon lamination
the copper carrier plus chromate layer is removed. The resulting
metallized substrate requires etching of the copper-nickel layer to
reveal the copper layer. It is emphasized and claimed that the thin
copper foil layer must be 1 .mu.m to 10 .mu.ms in thickness. Below
1 .mu.m copper thickness is not used due to the etching step
required to remove the copper-nickel layer. Etching the
copper-nickel layer will also etch the underlying copper layer.
[0013] What is needed in the art is a method for obtaining very
ultra thin metal foil laminates for the manufacture of printed
circuit boards.
BRIEF SUMMARY OF THE INVENTION
[0014] It is the object of the present invention to provide a
metal-clad laminate for use in the manufacture of printed circuit
boards, the laminate-having a very ultra thin metal foil that will
support the formation of very fine lines and spaces thereon.
[0015] Another object of the present invention is to provide a
method for large scale production of a metal-clad laminate for the
manufacture of printed circuit boards, the laminate having a very
ultra thin metal foil that will support the formation of very fine
lines and spaces.
[0016] It is a further objective of the invention to supply a foil
for use in multi-layer and built-up circuit boards, the foil being
very ultra thin to enable fine line circuit formation.
[0017] The present invention is a metal-clad laminate for the
manufacture of printed circuit boards, the laminate having a very
ultra thin metal foil that is at most about one .mu.m in
thickness.
[0018] The present invention is also a method of manufacturing a
metal-clad laminate for the manufacture of printed circuit boards,
the laminate having a very ultra thin metal foil that is at most
about one .mu.m in thickness.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0019] FIG. 1 is a cross-sectional illustration of a metal-clad
laminate intermediate constructed in accordance with the present
invention.
[0020] FIG. 2 is a cross-sectional illustration of an alternative
metal-clad laminate constructed in accordance with the present
invention.
[0021] FIGS. 3-6 illustrate cross-sectional views of alternative
embodiments of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0022] The present invention is directed toward very ultra thin
metal conductive layers which are formed by vapor deposition or
sputtering of the conductive metal on a polymeric or metal carrier
film which has been coated with an organic polymeric release agent.
The metal conductive layer can then be bonded to a printed wiring
board substrate, such as an epoxy based laminate. Then the carrier
film can be separated from the polymeric release agent, leaving the
metal conductive layer bonded to the substrate. Using this
approach, conductive metal layers in the range of 0.005 .mu.m to
1.0 .mu.m (50 to 10,000 Angstroms) become practical.
[0023] In accordance with the present invention, a metal-clad
laminate product for use in the manufacture of printed circuit
boards can be made including a polymer or metal foil carrier layer,
a polymeric parting layer formed on the carrier film, a very ultra
thin metal layer formed on the release agent layer. Shown in FIG. 1
is a metal-clad intermediate 10 made in accordance with the present
invention. The intermediate 10 is made up of a carrier film 11 to
which is applied a polymeric release agent layer 12, onto which is
applied a very ultra thin conductive metal layer 13.
[0024] Shown in FIG. 2 is an alternative embodiment of such a metal
clad laminate product here designated 20. In the embodiment of FIG.
2, a carrier film 21 has applied to it a polymeric release agent
layer or parting layer, 22. Onto the release agent layer 22 is
deposited a primary very ultra thin conductive metal layer 2.3. On
top of the primary metal layer 23 is a secondary metal layer 24,
also preferably formed by sputtering or vapor deposition.
[0025] Shown in FIG. 3 is an alternative embodiment metal clad
intermediate 30 is illustrated which includes a carrier film 31, a
release agent or parting layer 32, and a primary very ultra thin
conductive metal layer 33. Also deposited on the metal layer 33 is
an adhesion layer 35.
[0026] Shown in FIG. 4 is another embodiment which includes in a
metal clad intermediate 40, a carrier film 41, a release agent
layer 42, a very ultra thin primary metal layer 43, a secondary
metal layer 44 and an adhesive layer 45.
[0027] In FIG. 5 an alternative metal clad intermediate 50 is shown
which includes a carrier film 51, a release agent layer 52, a very
ultra thin primary metal layer 52, and an adhesion layer 54. This
embodiment also includes two layers of circuit board resin laminate
material or pre-preg, designated here 56 and 57.
[0028] Shown in FIG. 6 is another alternative metal clad
intermediate 60 including a carrier film 61, a release agent layer
62, a primary metal layer 63, a secondary metal layer 64, an
adhesion layer 65, and two layers of resin laminate materials 66
and 67.
[0029] These alternative embodiments are illustrated and discussed
to exemplify the wide variation in selection and number of layers
that can be used to assemble such intermediates.
[0030] Preferably, the carrier film comprises a flexible,
dimensionally stable material with good tear and chemical
resistances. The carrier film should be able to tolerate
above-ambient temperatures. Preferably, the carrier film is made of
a material having low absorbed moisture and residual solvent,
because water and solvents can interfere with the metallization
step. Suitable materials include polymeric film or metal foils. A
metal foil is preferred because metal foils tend to have high
tensile strength at elevated temperatures, low absorbed moisture,
and low residual solvent.
[0031] The carrier film employed in the examples below was an
electroplated copper foil or a polyimide film. Other metal foils
that would make suitable carrier films include rolled or
electrodeposited metal and metal alloys including steel, aluminum
(Alcoa, AllFoils), and copper (Gould Inc., Oak Mitsui Inc.). It is
expected that certain polymeric films would be suitable for the
practice of the present invention. Examples of suitable polymeric
films include polyesters such as polyethylene terephthalate,
poly-butylene terephthalate and polyethylene naphthalate
(Kaladex.RTM., ICI America), polypropylene, polyvinyl fluoride
(Tedlar.RTM., DuPont), polyimide (Kapton.RTM., DuPont; Upilex.RTM.,
UBE Industries), and nylon (Capran.RTM., AlliedSignal).
[0032] The release agent layer (11 in FIG. 1, 21 in FIG. 2, 31 in
FIG. 3, etc.) is used to facilitate removal of the carrier film
from the very ultra thin metal layer. In order to avoid the problem
of picking, which results in incomplete transfer of the very ultra
thin metal foil to the substrate under lamination, the release
agent layer is designed to peel at the interface between the
parting layer and film carrier. The parting layer is subsequently
removed with the aid of a plasma, an oxidating environment, intense
light, or an appropriate solvent. Preferably, the layer is removed
by washing with a sol vent, most preferably an aqueous solution. In
methods that lack a release agent layer, and in methods that employ
a release agent layer that peels at the interface between the
parting layer and the very ultra thin metal layer, incomplete
transfer of the metal of the very ultra thin metal foil to the
substrate commonly occurs.
[0033] The parting layer (12 in FIG. 1, 22 in FIG. 2, etc.) is made
of a polymeric material. Preferably, the parting layer is an
aqueous-soluble material to facilitate its convenience removal from
the very ultra thin metal layer. Because photo resists are
developed in an alkaline environment, it would be most preferable
to use a parting layer that is soluble in an alkaline aqueous
solution. A useful polymer is one that is of a good film-forming
material. The polymer can be coated from water with the aid of a
volatile base such as ammonium hydroxide to aid solubility.
Optionally, the parting layer comprises a water-soluble surfactant
to improve solution wetting properties, and to control drying
defects.
[0034] As detailed in the examples below, one useful release agent,
or parting layer, is applied as a formulation comprising a
polyvinylpyrrolidone (PVP) polymer, a surfactant, and water. The
wet weight composition of the parting layer formulation described
in the examples is 10% PVP and 0.5% surfactant. It is expected that
formulations containing PVP in the range of from about 1% PVP to
about 50% PVP, and surfactant in the range of from about 0%
surfactant to about 5% surfactant would also be suitable for the
practice of the present invention. Preferred PVPs for use in the
present invention have a molecular weight in the range of about
10,000 to about 5,000,000. It is reasonable to expect that a
release agent layer comprising a polymer such as acid modified
acrylic polymers, acrylic copolymers, urethanes, and polyesters.,
carboxylic acid functional styrene acrylic resins (S.C.Johnson Wax,
Joncryl.RTM.), polyvinyl alcohols (Air Products & Chemicals,
Airvol.RTM.), and cellulose based polymers could be successfully
employed in the practice of the present invention. Other suitable
water soluble surfactants that could be used to in the parting
layer of the present invention include alkylarylpolyether alcohols
(Rohm & Haas, Triton.RTM. X100), glycerin, ethoxylated castor
oil (CasChem Inc., Surfactol.RTM. 365), and fluoroaliphatic
polymeric esters (3M Corporation, Fluorad.RTM. 430). The release
agent layer formulation is applied in an amount sufficient to
achieve a dry weight of from about 10 mg/ft.sup.2 to about 1000
mg/ft.sup.2, about 0.1 .mu.m to 10 .mu.m in thickness. Preferably,
the release agent layer formulation is applied in an amount
sufficient to achieve a dry weight of from about 100 mg/ft.sup.2 to
about 400 mg/ft.sup.2, about 1 .mu.m to 4 km in thickness.
[0035] As described in detail in the examples, a thin primary
conductive metal layer (13 in FIG. 1, 23 in FIG. 2, etc.) can be
deposited onto the parting layer by sputtering using a Desk III
sputtering unit. It is expected that any sputtering or vapor
deposition method known in the art may be successfully used in this
invention. The primary metal layer is used as a plating seed layer
for subsequent circuit formation. In the examples below, the metal
layer was made from gold, chrome, or copper. Other suitable metals
include, but not limited to, tin, nickel, aluminum, titanium, zinc,
chromium-zinc alloy, brass, bronze, and alloys of the same. The
metal layer may be made from a mixture of suitable metals. The
primary layer is from about 0.005 .mu.m (50 Angstroms) to about 1.0
.mu.m (10,000 Angstroms) in thickness. Most preferably the primary
layer has thickness of from about 0.1 .mu.m to about 0.3 .mu.m
(1000 to about 3000 Angstroms).
[0036] Optionally, a secondary metal layer (such as layer 24 in
FIG. 2, 44 in FIG. 4, or 64 in FIG. 6) may be employed to protect
the primary layer from oxidation, to increase adhesion during
lamination, or to act-as a barrier to metal migration. The
secondary layer may be from about 0.001 .mu.m (10 Angstroms) to
about 0.1 .mu.m (1000 Angstroms) in thickness. Most preferably the
secondary layer has thickness of from about 0.01 .mu.m (100
Angstroms) to about 0.03 .mu.m (300 Angstroms). To form the
secondary metal layer, a layer of zinc, indium, tin, cobalt,
aluminum, chrome, nickel, nickel-chrome, brass, or bronze is
deposited on the first metal layer. Other suitable metals include
magnesium, titanium, manganese, bismuth, molybdenum, silver, gold,
tungsten, zirconium, antimony, and chromium-zinc alloys. The
secondary metal layer prevents the metal in the first metal layer
from oxidizing after removal from the metallizing chamber, and
increases adhesion to thermosetting resin systems.
[0037] Optionally, an adhesion layer (e.g. 35 in FIG. 3, 45 in FIG.
4, etc.) can be applied to the metal layer. The adhesion layer may
be employed in order to increase the bond between the metal layers
and the substrate layers following lamination. The adhesion layer
may be organic, organometallic, or inorganic compounds, and applied
to a thickness of 0.0005 .mu.m (5 Angstroms) to 10 .mu.m (100,000
Angstroms). Multiple layers may be used such as an organometallic
layer followed by an organic layer. Typically when an
organometallic layer is used, such as a silane, the coating will be
from 0.0005 .mu.m (5 Angstroms) to 0.005 .mu.m (500 Angstroms) in
thickness. When using organic adhesion layers, such as
thermoplastics, thermosetting polymers, or mixtures, the coating
would be 0.1 .mu.m (1000 Angstroms) to 10 .mu.m (100,000 Angstroms)
in thickness.
[0038] Useful organometallic compounds include materials based on
zirconium, titanium, and silicon. Silicon based organometallics,
known as silanes or coupling agents., are widely used and
available. The coupling agent may be applied neat or applied after
dissolving it in an appropriate solvent. Suitable coupling agents
typically have a silane-hydrolyzable end group with alkoxy,
acyloxy, or amine functionality, and an organofunctional end group.
The hydrolyzable end group reacts with the metal surface while the
organofunctional group bonds to the substrate layer to which the
metal is laminated. Coupling agents can be subjected to a
hydrolysis reaction prior to coating if dissolved in an acidic
medium. Useful coupling agents include compounds such as
N-(2-aminoethyl)-3-aminopropyltrimethoxy silane (Dow Corning, Huls
America Inc.) and 3-Glycidoxypropyltrimethoxy silane (Dow Corning,
Huls America Inc.). Organic adhesion layers consisting of
thermoplastics, thermosetting polymers, or mixtures are appropriate
adhesion layers. These adhesives can be based on polyimide resins,
epoxy resins, polyester resins, acrylic resins, butadiene rubbers,
and the like. One useful adhesive consisting of a polyester epoxy
system is available (Cortaulds, Z-Flex.TM.).
[0039] Resin layers can be applied to the metal layer or to the
adhesive layer (if present) in uses where a controlled dielectric
thickness is required. Such uses include built up technologies.
Typically the resins are thermosetting systems that are coated from
an appropriate solvent. After drying, the resins can be cured to a
semi-cured state if additional cure is required before lamination
to a circuit board. A single semi-cured resin layer can be used.
Preferably, two resin layers are used where the first resin layer
down (primary layer) is cured to a greater extent than the second
resin layer. The first resin layer serves as a controlled
dielectric spacing layer and has a thickness of from about 5 to
about 500 .mu.ms, preferably from about 20 to about 50 .mu.ms.
Appropriate resin systems include (but not limited to): epoxy
resins cured by phenolic or dicyandiamide hardeners, cyanate
esters, bismaleimides, and polyimide systems. The second layer can
have a different composition than the primary layer; however, to
attain good interlayer adhesion, it is preferable that the
composition of the second layer is similar to that of the first
resin layer. The second resin layer serves as an adhesion layer and
as a void filling layer during lamination and has a thickness
between 5 and 500 .mu.ms, preferably between 20 and 50 .mu.ms.
[0040] By "laminating under suitable lamination conditions" it is
meant laminating under-appropriate conditions of temperature and
pressure for a suitable period of time to adhere the layers
together for practical use in making a circuit board laminate.
[0041] The following nonlimiting examples are intended to be purely
illustrative.
EXAMPLE 1
[0042] Upilex.RTM. 50 .mu.m polyimide film was obtained from the
Ube Industries for use as the carrier film. 0.15 .mu.m (1500
Angstroms) of copper was sputtered coated, followed by 0.01 .mu.m
(100 Angstroms) of a nickel-chrome alloy. The sample was pressed to
make a circuit board laminate. Four layer's of an FR-4 pre-preg
known as FR406 (AlliedSignal) was placed on a glass reinforced
Teflon.RTM. sheet. Under the sheet was a stainless steel press
plate. The above construction was placed metal side down on the
Fr406 pre-preg. A second layer of glass reinforced Teflon.RTM.
sheet was placed on the top and covered with a second stainless
steel press plate. The stack was placed in a pre-heated press at
350.degree. F. and pressed for 1.2 hours at 50 psi. The film was
attempted to be peeled, but was difficult. Peel strength measured
at an angle of 180.degree. and found to vary between 1-5 lbs./in.
Sections of the metal coating approximately 100 .mu.m in size did
not transfer and were left on the film. The metal coating "picked".
The above was attempted a second time, and was found the metal
coating would not peel from the film carrier. Metal adhesion to the
film was high enough to cause the film to tear during a peel
attempt.
EXAMPLE 2
[0043] A sample of 1 oz. electroplated copper foil was obtained
from Gould Inc. for use as a carrier film. AK release agent layer
was formed by coating parting layer formulation P1 (Table 1) onto
the copper carrier layer using a No. 18 wire-wound rod. Following
application to the carrier film, the release agent layer was dried
at 160.degree. C. for about 2 minutes. The coating was clear. A
gold metal conductive layer was sputtered onto the clear parting
layer using a Desk III sputtering unit with air as the processing
gas. Gold was deposited for 3 minutes. Examination an edge of the
gold coating by microscopy revealed that a gold layer of
approximately 0.3 .mu.m (3000 Angstroms) in thickness was
deposited.
[0044] The sample was pressed to make a circuit board laminate.
Four layers of an FR-4 epoxy based pre-preg known as FR406
(AlliedSignal) was placed on a glass reinforced Teflon.RTM. sheet.
Under the sheet was a stainless steel press plate. The above
construction was placed metal side down on the FR406 pre-preg. A
second layer of glass reinforced Teflon.RTM. sheet was placed on
the top and covered with a second stainless steel press plate. The
stack was placed in a preheated press at about 350.degree. F. and
pressed for about 1.2 hours at 50 psi. After cooling to room
temperature, the copper carrier film peeled easily revealing the
parting layer transferred completely with the metal coating.
Washing the surface in warm water removed the release agent layer
and revealed a shiny metal surface.
1TABLE 1 Composition of parting layer formulation P1. Component
Source Amount Polyvinylpyrrolidone, ISP Technologies 5.00 g PVP-K90
Surfactol 365 CasChem 0.025 g Water 44.975 g
EXAMPLE 3
[0045] A sample of 1 oz. electroplated copper foil was obtained
from Gould Inc for use as the carrier film. A release agent layer
was formed by coating formulation P1 (Table 1) onto the copper
carrier film using a No. 18 wire-wound rod. Following application
to the carrier film, the parting layer was dried at 160.degree. C.
for about 2 minutes. The coating was clear. A gold metal layer was
sputtered onto the clear parting layer using a Desk III sputtering
unit with air as the processing gas. Gold was deposited for 3
minutes. Examination an edge of the gold coating by visible
microscopy revealed that a gold layer of approximately 0.3 .mu.m
(3000 Angstroms) in thickness was deposited. A first resin layer
was made by coating formulation R1 (Table 2) onto the gold layer
using a No. 18 wire-wound rod. The first resin later was dried at
about 50.degree. C. for about 1 hour, then held at about 65.degree.
C. for about 1 hour, and finally cured at about 170.degree. C. for
about 6 minutes. A second resin layer was made by coating
formulation R1 onto the first layer using a No. 18 wire-wound rod.
The second resin was dried using the same drying conditions that
were employed in for the first resin layer.
[0046] Four layers of an FR-4 pre-preg known as FR406
(AlliedSignal) were placed on a glass-reinforced Teflon.RTM. sheet.
Under the sheet was a stainless steel press plate. A second layer
of glass-reinforced Teflon.RTM. sheet was placed on the top and
covered with a second stainless steel press plate. The stack was
placed in a pre-heated press at 350.degree. F. and pressed for 1.2
hours at 50 psi. After cooling to room temperature, the stack was
broken down and the glass reinforced Teflon.RTM. sheet removed
revealing and unclad laminate. The above construction was placed on
top of the unclad laminate with resin side contacting the laminate.
A glass reinforced Teflon sheet covered the construction followed
by a stainless steel press plate. A second stainless steel press
plate was placed under the laminate. The stack was placed in a
pre-heated press at 350.degree. F. and pressed for 1.2 hours at 50
psi. After cooling to room temperature, the copper carrier film was
peeled easily revealing the parting layer transferred completely
with the metal coating and resin layers. Washing the surface in
warm water removed the parting layer and revealed a shiny metal
surface.
2TABLE 2 Composition of resin formulation R1. Component Source
Amount Epon 1031A70 Shell Chemical 1.98 g DER732 Dow Chemical 5.67
g PKHS-40 Phenoxy 18.16 Associates Ciba 1138A85 Ciba Geigy 15.91 g
Quatrex 6410 Dow Chemical 22.69 BT2110 Mitsubishi Gas & 34.97 g
Chemical DMF 7.37 g Methyl Ethyl Ketone 46.13 g
[0047]
3TABLE 3 Composition of parting layer formulation P2. Component
Source Amount Polyvinylpyrrolidone, PVP-K120 ISP Technologies 5.00
g Surfactol 365 CasChem 0.025 g Water 44.975 g
[0048] This formulation P2 differs from P1 in the choice of PVP
K120, which has a weight average molecular weight of 2,900,000. The
PVP used in the Formulation P1 was PVP K90, which has a weight
average molecular weight of 1,270,000. Higher molecular weight is
desirable for coating and film formation while lower molecular
weight is desirable for increased layer solubility.
EXAMPLES 4-7
[0049] A sample of 1/2 oz. electroplated high temperature
elongation copper foil was obtained from Oak-Mitsui for use as a
carrier film. Release agent formulation P2 was coated on the
carrier film using a No. 18 wire-wound rod and dried at 160.degree.
C. for 2 minutes. The coating was clear and measured to be 250
mg/ft.sup.2. Different metal layer combinations are sputter
deposited onto the P2 coating using argon as the processing
gas:
4 Metal Layer (s) Comments Example 4 Gold, 3000 Angstroms Example 5
Chrome, 100-200 Angstroms Example 6 Copper, 3000 Angstroms, The
thin chrome layer followed by, Chrome, 100 is used as a Angstroms
passivation layer between the copper and the laminate. Example 7
Copper, 1500 Angstroms, The thin zinc layer is followed by, Zinc,
50-100 used as a passivation Angstroms layer between the copper and
the laminate. When the construction is heated in the press, the
zinc alloys with a thin layer of the copper forming brass
[0050] The constructions are of the form illustrated in FIG. 1.
[0051] An adhesion layer consisting of a silane was coated on the
metal layer in example 6 and 7. A solution of
Gamma--glycidoxypropyl trimethoxy silane was made to 0.5% in a
mixture of methanol and water, where the methanol was 90% and the
water was 10%. The solution was coated on the metal surface and
dried at 90.degree. C. for 1 minute.
[0052] Each sample was pressed to make a circuit board laminate.
Four layers of an FR-4 pre-preg known as FR406 (AlliedSignal) was
placed on a glass reinforced Teflon.RTM. sheet. Under the sheet was
a stainless steel press plate. The above construction was placed
metal side down on the FR406 pre-preg. A second layer of glass
reinforced Teflon.RTM. sheet was placed on the top and covered with
a second stainless steel press plate. The stack was placed in a
pre-heated press at 350.degree. F. and pressed for 1.2 hours at 50
psi. After cooling to room temperature, the copper carrier film
peeled easily revealing the parting layer transferred completely
with the metal coating. Washing the surface in warm water removed
the parting layer and revealed the shiny metal surface of the
conductive layer.
[0053] The peel force required to remove the carrier layer was
measured at an angle of 180.degree. on Example 6 and Example 7. The
peel force was determined to be very low and was highly repeatable.
Example 6 was measured at 0.025 lbs./in. while Example 7 was
measured at 0.015 lbs./in.
EXAMPLE 8
[0054] Upilex.RTM. 50 .mu.m polyimide film was obtained from the
Ube Industries. Formulation P2 was coated on the carrier film using
a No. 18 wire-wound rod and dried at 160.degree. C. for 2 minutes.
The coating was clear and measured to be 250 mg/ft.sup.2. A gold
metal layer was sputtered on the clear coating using a Desk III
sputtering unit with air as the processing gas. Gold was deposited
for 3 minutes. Examining an edge of the gold coating using a
visible microscope revealed 0.3 .mu.m (3000 Angstroms) of gold was
deposited.
[0055] The sample was pressed to make a circuit board laminate.
Four layers of an FR-4 pre-preg known as FR406 (AlliedSignal) was
placed on a glass reinforced Teflon.RTM. sheet. Under the sheet was
a stainless steel press plate. The above construction was placed
metal side down on the FR406 pre-preg. A second layer of glass
reinforced Teflon was placed on the top and covered with a second
stainless steel press plate. The stack was placed in a pre-heated
press at 350.degree. F. and pressed for 1.2 hours at 50 psi. After
cooling to room temperature, the polyimide film peeled easily
revealing the parting layer, transferred completely with the metal
coating. Washing the surface in warm water removed the parting
layer and revealed a shiny metal surface.
EXAMPLE 9
[0056] Upilex.RTM. 50 .mu.m polyimide film was obtained from the
Ube Industries for use as the carrier film. Release formulation P2
is coated on the carrier film using a No. 18 wire-wound rod and
dried at 160.degree. C. for 2 minutes. The coating was clear and
measured to be 250 mg/ft.sup.2. A copper metal layer was vapor
deposited on the clear coating using a CVE vacuum Chamber
manufactured by CVC Products, Inc. Copper was deposited for
approximately 4 minutes.
[0057] An adhesion layer consisting of a silane was coated on the
metal layer. A solution of Gamma--glycidoxypropyl trimethoxy silane
was made to 0.5% in a mixture of methanol and water, where the
methanol was 90% and the water was 10%. The solution was coated on
the metal surface and dried at 90.degree. C. for 1 minute.
[0058] The sample was pressed to make a circuit board laminate. Six
layers of an FR-4 pre-preg known as FR408 (AlliedSignal) was placed
on a glass reinforced Teflon.RTM. sheet. Under the sheet was a
stainless steel press plate. The above construction was placed
metal side down on the FR408 pre-preg. A second layer of glass
reinforced Teflon.RTM. sheet was placed on the top and covered with
a second stainless steel press plate. The stack was placed in a
pre-heated press at 350.degree. F. and pressed for 1.2 hours at 50
psi. After cooling to room temperature the polyimide film peeled
easily revealing the parting layer transferred completely with the
metal coating. Washing the surface in warm water removed the
parting layer and revealed a shiny metal surface.
[0059] The peel force required to remove the carrier layer was
measured at an angle of 180.degree. and found to be very low at
0.010 lbs./in. and to be highly repeatable.
EXAMPLE 10
[0060] A sample of the 1/2 oz. electroplated high temperature
elongation copper foil was obtained from Oak-Mitsui for use as a
carrier film. Release formulation P2 was coated using a No. 18
wire-wound rod and dried at 160.degree. C. for 2 minutes. The
coating was clear and measured to be 250 mg/ft.sup.2; A copper
metal layer was vapor deposited on the clear coating using a CVE
vacuum Chamber manufactured by CVC Products, Inc. Copper was
deposited for approximately 4 minutes.
[0061] The sample was pressed to make a circuit board laminate.
Four layers of an FR-4 pre-preg known as FR406 (AlliedSignal) was
placed on a glass reinforced Teflon.RTM. sheet was placed on the
top and covered with a second stainless steel press plate. The
stack was placed in a pre-heated press at 350.degree. F. and
pressed for 1.2 hours at 50 psi. After cooling to room temperature,
the copper carrier film peeled easily revealing the parting layer
transferred completely with the metal coating. Washing the surface
in warm water removed the parting layer and revealed a shiny metal
surface.
* * * * *