U.S. patent number 3,855,047 [Application Number 05/321,444] was granted by the patent office on 1974-12-17 for sheet-like nonwoven web and flexible article of polyester and aromatic polyamide staple fibers.
This patent grant is currently assigned to Minnesota Mining and Manufacturing Company. Invention is credited to Gaylord L. Groff.
United States Patent |
3,855,047 |
Groff |
December 17, 1974 |
SHEET-LIKE NONWOVEN WEB AND FLEXIBLE ARTICLE OF POLYESTER AND
AROMATIC POLYAMIDE STAPLE FIBERS
Abstract
The disclosed laminate is suitable for use in the art of printed
circuitry and comprises an electrically conductive layer and a
nonwoven backing layer. The nonwoven backing has unusual
dimensional stability under a wide variety of conditions and
preferably comprises a blend of at least 15 wt. % polyester staple
and at least 10 wt. % aromatic polyamide staple. This blend is
impregnated with a thermosettable resin.
Inventors: |
Groff; Gaylord L. (North Saint
Paul, MN) |
Assignee: |
Minnesota Mining and Manufacturing
Company (St. Paul, MN)
|
Family
ID: |
27368349 |
Appl.
No.: |
05/321,444 |
Filed: |
January 5, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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152591 |
Jun 14, 1971 |
|
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53120 |
Jul 8, 1970 |
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Current U.S.
Class: |
428/220; 57/255;
174/258; 428/359; 442/117; 174/254; 442/79 |
Current CPC
Class: |
D04H
1/4342 (20130101); H05K 1/0366 (20130101); D04H
1/435 (20130101); D04H 1/43835 (20200501); H05K
2201/0284 (20130101); H05K 2201/0145 (20130101); Y10T
428/2904 (20150115); H05K 2201/0278 (20130101); Y10T
442/2164 (20150401); H05K 2201/0293 (20130101); Y10T
442/2475 (20150401) |
Current International
Class: |
D04H
1/42 (20060101); H05K 1/03 (20060101); D04h
001/04 (); B32b 007/04 () |
Field of
Search: |
;161/150,170,151,169,152,227,214,231,156,165 ;174/68.5 ;57/14BY
;117/138.8F,138.8N |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Abstract 717,034, Baker et al. pub. 6/27/50, 161-214..
|
Primary Examiner: Lesmes; George F.
Assistant Examiner: Ives; Patricia C.
Attorney, Agent or Firm: Alexander, Sell, Steldt &
DeLaHunt
Parent Case Text
This application is a division of copending application Ser. No.
152,591, filed June 14, 1971, now abandoned, which is a
continuation-in-part of Ser. No. 53,120 filed July 8, 1970, now
abandoned.
Claims
What is claimed is:
1. A sheet-like nonwoven web impregnated with an electrically
insulative, moisture-insensitive thermoset resin, said sheet-like
nonwoven web being formed from a fiber blend comprising between 15
and 60 weight % undrawn polyester staple fibers at least partially
heat softenable at temperatures below 200.degree. C. 0 up to 60
weight percent drawn polyester staple fiber, and, in intimate
admixture with said undrawn polyester staple fibers, at least 10
but no more than about 75 weight % discontinuous aromatic polyamide
staple fibers.
2. A sheet-like nonwoven web according to claim 1 wherein said
fiber blend contains 25-65 weight percent of said aromatic
polyamide staple fibers.
3. A sheet-like nonwoven web according to claim 1 wherein said web
is formed from a fiber blend comprising drawn and undrawn polyester
staple fiber and heat resistant aromatic polyamide staple fiber,
the amount of said drawn polyester staple fiber being no more than
twice the amount of said undrawn polyester staple fiber.
4. A flexible, sheet-like article, said article being less than 20
mils in thickness and being at least as flexible as a 10-mil thick
biaxially oriented poly (ethylene terephthalate) film said article
comprising a sheet-like nonwoven web impregnated with an
electrically insulative, moisture-insensitive thermoset resin, said
sheet-like nonwoven web, prior to impregnation, having a Gurley
value, ASTM Test D 726, Method A, of less than 100 seconds per 100
cc of air per 5 mils of thickness, said sheet-like nonwoven web
comprising:
0 - 60 weight per cent drawn polyester staple fiber;
15 - 60 weight per cent undrawn polyester staple fiber, and
10 - 75 weight per cent aromatic polyamide staple fiber,
said sheet-like nonwoven web being autogenously bonded.
5. An article according to claim 4 wherein the amount of said drawn
polyester staple fiber is no greater than twice the amount of said
undrawn polyester staple fiber.
Description
This invention relates to impregnated, fibrous, paperlike sheets
used as flexible printed circuit backings. An aspect of this
invention relates to a critical blend of chemically diverse fibers
which provide a synergistic dimensional stability effect. A still
further aspect of this invention relates to a laminate of metal
foil and a nonwoven backing, the backing comprising a critical
blend of polyester and aromatic polyamide fibers.
Aromatic polyamides having recurring units of the formula
--NR.sub.1 --Ar.sub.1 CO--
or the formula
--NR.sub.1 Ar.sub.1 --NR.sub.1 CO--Ar.sub.2 --CO--
(wherein Ar.sub.1 and Ar.sub.2 are the same or different and are
divalent aromatic nuclei which are linked meta or para into the
recurring units, and wherein R.sub.1 is hydrogen or lower alkyl)
can be made into fibers, films, and "fibrids" and are known for
their resistance to the degradative effects of high temperature.
See U.S. Pat. No. 3,094,511 (Hill, et al.) issued June 18, 1963;
U.S. Pat. No. 3,300,450 (Clay) issued Jan. 24, 1967; and U.S. Pat.
No. 3,354,127 (Hill, et al.) issued Nov. 21, 1967; see also U.S.
Pat. No. 3,203,933 (Hoffman, et al.) issued Aug. 31, 1965 or U.S.
Pat. No. 3,225,011 (Preston, et al.), issued Dec. 21, 1965. The
aromatic polyamide art contains suggestions relating to the use of
such fibers, films, or "fibrids" in electrical insulation, e.g., in
printed circuits, see, for example, the aforementioned Hill, et al.
patents. Among the fibrous materials described in the prior art are
waterleaf-type sheets of "fibrids" and staple fibers (see the
aforementioned Clay patent) which ordinarily are calendered to
reduce porosity. See British Pat. No. 1,129,097. Further details
regarding fibrid structures can be found in U.S. Pat. No. 2,999,788
(Morgan), issued Sept. 12, 1961 and U.S. Pat. No. 2,988,782
(Parrish, et al.), issued June 20, 1961.
It is known to use porous, nonwoven webs of polyester (e.g.
polyethylene terephthalate) staple in making electrical insulation
and the like. Such nonwoven webs can be impregnated with the
heat-curable resins used as electrical insulating varnishes. See
U.S. Pat. No. 3,309,260 (Boese) issued May 14, 1967. Electrical
insulation of the type disclosed in the aforementioned Boese patent
has excellent properties (e.g. high tear strength), but may lack
dimensional stability when exposed to high temperatures, e.g.,
above 230.degree. F. (110.degree. C.). In the printed circuit art,
the paper-like backing for the circuit is subjected to processing
temperatures of about 250.degree. F. (about 121.degree. C.) or
higher, and generally is submerged or floated on a solder bath
which is at temperature of, for example, about
400.degree.-500.degree. F. (205.degree.-260.degree. C.). This
complex heat history, coupled with other processing steps such as
metal-cladding, etching, etc., warps or distorts a polyester or
varnish-impregnated polyester backing to the point where it is
highly unsatisfactory or even unusable. Attempts to carefully
control the heat history and cladding, etching, or similar
processing steps have not been successful in preserving dimensional
stability.
The prior art teachings relating to paper-like sheets made from
fibers and fibrids of aromatic polyamide and aromatic polyamide
films appear to suggest an answer to the dimensional stability
problems encountered in the manufacture of paper-like printed
circuits. The use of aromatic polyamide films in the manufacture of
printed circuits is not practical for thin, sheetlike backings,
because such films lack sufficient tear strength and are
characterized by high moisture sensitivity. A calendered paper-like
sheet made from fibers and/or fibrids of aromatic polyamide (see
the discussion of calendering in British Pat. No. 1,129,097),
whether treated or untreated with resinous electrical insulating
varnishes, has good tear strength but surprisingly suffers about as
much distortion due to printed circuit processing and heat history
as the polyester insulation. Uncalendered paper-like sheets made
from fibers and fibrids of aromatic polyamide, after coating with a
resin, make unacceptable printed circuit backings due to their poor
tear strength. Apparently the selection of a suitable dimensionally
heat stable fiber is only one factor involved in the fabrication of
nonwoven webs suitable for use as printed circuit backings.
It is known in the art of making nonwoven webs to blend various
fibers; see, for example, column 8 of U.S. Pat. No. 2,723,935
(Rodman), issued Nov. 15, 1955. This knowledge has been extended to
the field of fibrid/staple fiber papers; see the aforementioned
Morgan and Parrish, et al., patents. However, the blending of
fibers would not appear to be a likely prospect for improving the
dimensional stability of a nonwoven web subjected to a complex heat
history and a variety of processing steps. The dimensional
stability and heat resistance of the aromatic polyamides would be
hard to improve upon, particularly as compared to relatively
heat-sensitive fibers such as polyethylene terephthalate. In any
event, the prior art contains no guidelines as to what sort of
fiber blends would be suitable in this particular context of
printed circuit technology.
Accordingly, this invention contemplates the fabrication of
flexible printed circuit backings which will not be adversely
affected by the processing (including steps involving elevated
temperatures) involved in manufacturing printed circuits.
This invention further contemplates a printed circuit or a similar
type of laminate having a nonwoven, paper-like printed circuit
backing comprising a blend of fibers which is resistant to
distortion, warping, degradation, and other ill effects caused by
the heat history of the printed circuit and/or the various chemical
and physical steps involved in cladding with an electrically
conductive foil, etching the conductive foil, soldering, etc.
Briefly, this invention involves
blending discontinuous aromatic polyamide fibers, e.g. of the type
disclosed in the aforementioned Hill, et al. and Clay patents, with
at least 25% by weight (or at least 15% by wt. undrawn)
discontinuous polyester fiber, e.g., a mixture of drawn and undrawn
staple fibers derived from a polymer of an alkylene glycol and an
aromatic dicarboxylic acid;
forming a thin (less than about 20 mils or about 0.5 mm), porous
(i.e. having a Gurley value, as determined by ASTM test D 726,
method A, of less than about 100 seconds per 100 cc. of air for a 5
mil [0.125 mm] layer of material), nonwoven web from the blend of
discontinuous fibers;
impregnating this thin, porous, nonwoven web with a suitable
electrically insulating, heat curable or thermosettable organic
polymeric synthetic resin; and
processing the impregnated thin, porous, nonwoven web according to
the usual practices of printed circuits technology, e.g.,
laminating or plating with a conductive film, etching, soldering,
etc.
The above-described porosity is essential for ease of impregnation.
In order to provide the above-described nonwoven web with the
required porosity, it is preferred to avoid blending the fibrids
disclosed by Morgan and Parrish, et al., with the discontinuous
(i.e. staple) fiber blend, because such fibrids have a tendency to
reduce porosity, thereby making impregnation difficult. For optimum
porosity (the range of Gurley values defined previously) a staple
fiber blend is preferred wherein the fibers are about 0.5 - 10
denier by at least 3 mm. in length. Preferably, the fibers,
particularly the fine denier fibers, are monofilaments.
There appears to be no simple or direct theoretical explanation for
the improved performance of the nonwoven webs of this invention,
and this invention is not, in any event, bound by any theory. It
would appear to be contrary to the teachings and experience of the
art to strive for greater dimensional stability by diluting heat
resistant aromatic polyamide fibers with heat sensitive polyester
fibers. The reason for the improved performance of the blend
probably involves such factors as compensating for the moisture
sensitivity of the aromatic polyamide and/or balancing expansion
coefficients of the fibers (and/or the resinous impregnant and/or
the conductive film cladding).
For example, it has been found that an impregnated nonwoven web can
be made according to this invention such that it has a fairly
constant linear thermal expansion coefficient throughout a
significantly large temperature range (e.g. room-temperature up to
160.degree. C.). Furthermore, this coefficient can be very close to
the linear expansion coefficient for conductive metals such as
copper, silver, gold, and aluminum, even though the nonwoven web
contains at least 15 wt. % of temperature-sensitive (or heat
softenable) fiber.
Reported values for the linear thermal expansion coefficient of
various epoxy resins used in impregnating printed circuit backings
are generally at least 65 .times. 10.sup..sup.-6 per .degree.C.
(All coefficients of linear thermal expansion referred to in this
application are expressed as a ratio of inch/inch or cm/cm per
degree centigrade.) The reported thermal coefficient values for
polyester films are lower than these epoxy resin values and are
roughly comparable to some of the higher reported values for
commonly used electrical conductors and semi-conductors, the
thermal coefficients of most of these conductive substances
reportedly being in the range of about 5 to about 30 .times.
10.sup..sup.-6 per .degree.C., in rare instances as low as 4 or as
high as 33 .times. 10.sup..sup.-6 per .degree.C. The thermal
expansion coefficients of most metals, as solids, tend to be
independent of temperature, in most cases remaining below 30
.times. 10.sup..sup.-6 /.degree.C. throughout the entire range of
temperature relevant to the principles and practice of this
invention.
It has now been found that epoxy resin-impregnated nonwoven webs of
poly(ethylene terephthalate) fiber can have more than one linear
expansion coefficient, depending on the temperature at which the
coefficient is determined. For temperatures below 100.degree. C.
these values are close to the aforementioned reported values for
polyester films, but for the higher temperatures frequently
encountered in making laminates of this invention, these values are
significantly larger and may be doubled or even tripled, as is
shown subsequently in Example 5(C) of this application.
According to reported values, aromatic polyamide fibers and yarns
have a linear expansion coefficient value which is in the 5 to 30
.times. 10.sup..sup.-6 per .degree.C. range discussed previously.
However, the linear expansion coefficient of paper-like webs made
from fibrous poly(m-phenyleneisophthalamide) is, apparently,
temperature dependent, though less so than that of the polyester
webs discussed previously.
Accordingly, the low and relatively constant values of thermal
expansion coefficients for impregnated nonwoven webs used in this
invention are not predictable from previously published thermal
expansion data on the component parts of the web and appear to be a
factor contributing to the surprising dimensional stability effects
observed in practicing this invention, e.g., substantial flatness
and low shrinkage. In short, thermal expansion data indicate that
the combination of the component parts of this invention possesses
properties not inherent in these parts individually.
As will be apparent from this description, a high level of
dimensional stability is obtained according to this invention by
blending a raw nonwoven web from (1) at least 15 weight %
discontinuous synthetic fibers which are at least partially heat
softenable at temperatures below 200.degree. C., which fibers may
have a temperature-dependent linear thermal expansion coefficient,
with (2) 10-75% by weight of fibers resistant to temperatures of at
least 250.degree. C. which also may have a linear thermal expansion
coefficient with some degree of temperature dependency. The raw web
thus obtained is then impregnated with a curable resin impregnant
which cures to a moisture insensitive, electrically insulative
material. This combination of materials can provide a backing with
a substantially constant linear expansion coefficient, preferably
below 30 .times. 10.sup..sup.-6 per .degree.C., at least throughout
a temperature range from normal ambient (20.degree.-25.degree. C.)
up to 120.degree. C. and preferably up to 160.degree. C. The
impregnated web is clad with an electrically conductive substance
(i.e., conductor, or semi-conductor), which will ordinarily have a
linear thermal expansion coefficient of less than 30 .times.
10.sup..sup.-6 per .degree.C., preferably less than 25 .times.
10.sup..sup.-6 per .degree.C., e.g. nickel, copper, aluminum, and
precious metals such as silver and gold. Insofar as the practice of
this invention is concerned, these metals have substantially
constant, i.e., temperature-independent, thermal expansion
coefficients.
For purposes of this application, the term "moisture insensitive"
denotes a moisture absorption which is less than the raw fiber
blends used in this invention, i.e., less than 6% and preferably
less than 5% (by weight) after 3 days at 95% relative humidity.
The term "resistant to temperatures of at least 250.degree. C.," as
used in relatin to fibers, means, in its broadest aspect, a fiber
which can be exposed to temperatures up to 250.degree. C. (e.g.,
from floating on a hot solder bath) for 10 seconds or more and
exhibit little or no shrinkage due to melting, relief of strains,
disorientation of molecular structure, or similar physical or
chemical changes. Fibers which satisfy this criterion include the
aromatic polyamides described previously and high-melting and/or
degradation-resistant cellulosic fibers, preferably regenerated
cellulose fibers such as rayon. Using known spinning techniques,
fibers can be made from heat resistant, dimensionally stable
polyimides, e.g. polymers formed from aromatic diamines such as
4,4'-diaminodiphenylether and aromatic di-anhydrides such as
pyromellitic anhydride. The resulting fibers are resistant to
temperatures up to 250.degree. C. and are low in thermal expansion.
The heat resistant fibers most preferred for use in this invention,
when tested at room temperature after 24 hours exposure to dry air
at 260.degree. C., have at least 60% of the pre-exposure breaking
strength. These fibers also preferably have a linear expansion
coefficient less than about 30 .times. 10.sup..sup.-6 /.degree.C.
at temperatures below 120.degree. C.
The raw (i.e. unimpregnated) nonwoven webs used in this invention
can be prepared by a series of known steps. First, the desired
blend of discontinuous fibers of aromatic polyamide and polyester
is made into a nonwoven web, preferably by a conventional
air-laying process, e.g., Rando-webbing or garnetting. Second, the
fluffy, air-laid nonwoven web is needle-loomed or otherwise
processed by increase density and/or provide strength and
uniformity. Third, the nonwoven, needle-loomed web is preferably
hot pressed and/or calendered to further increase strength by
autogenously bonding the web and increasing both density and
strength. The length of the staple fibers should be consistent with
the objectives of good tear strength and ease of web formation.
Rando-webbing, garnetting or equivalent air-laying processes are
convenient to use with staple fibers longer than about 0.3 cm and
preferably longer than about 1.5 cm. Fibers longer than about 8 or
10 cm are not convenient to use even on a garnett.
Whatever the web-forming technique, it is preferred that the
discontinuous aromatic polyamide and polyester fibers of this
invention be monofilament staple having filament diameters greater
than 5 but less than 35 microns, or roughly 0.5 - 10 denier. The
aromatic polyamide staple comprises a polyamide which is preferably
of the type disclosed in the aforementioned Hill, et al., and Clay
patents, i.e.,
--NR.sub.1 --Ar.sub.1 --NR.sub.1 --CO--Ar.sub.2 --CO --.sub.n.
Among these preferred polymers are those wherein R.sub.1 is
hydrogen and Ar is a meta- or para-phenylene radical, e.g.
poly(m-phenylene-[diamine]isophthalamide). These preferred polymers
substantially maintain their physical properties at temperatures
above 300.degree. C. They do not melt, but degrade rapidly above
370.degree. C. The index of polymerization ("n") should be high
enough to provide the high molecular weights used in spun
filaments. Other aromatic polyamides, e.g. those of the formula
--NR.sub.1 --Ar.sub.1 --CO--.sub.n also are well known in the art
for their desirable thermal properties; see the aforementioned
Hoffman, et al., and Preston, et al., patents.
The preferred polyester fibers comprise polyesters of the
formula
--O--A--O--CO--Ar--CO--.sub.n
wherein A is a divalent straight chain or cyclic aliphatic radical,
Ar is a divalent aromatic radical, e.g. meta- and/or para-phenylene
and n is the index of polymerization. These polyesters are prepared
in a known manner from difunctional alcohols, e.g. ethylene glycol,
propylene glycol, and 1,4-cyclohexanedimethanol, and difunctional
carboxylic acids (or esters thereof), e.g., terephthalic acid,
isophthalic acid, and mixtures thereof. Fibers and filaments made
from these polyesters are readily available, e.g. "Dacron" (a
trademark of duPont Co.), which is drawn
poly(ethyleneterephthalate). The polyester fiber need not be drawn
(i.e., stretched or oriented and crystalline in structure) and can
be undrawn (non-oriented and substantially amorphous); in fact, at
least some of the polyester staple should be undrawn.
The raw nonwoven webs of this invention can comprise the following
fiber blend: Staple Fiber Wt. %
______________________________________ Drawn polyester (as
described previously) 0 - 60 Undrawn polyester (as described
previously) 15 - 60 Aromatic polyamide (as described previously) 10
- 75 ______________________________________
An important feature of this fiber blend is that it contains at
least 15 wt. % undrawn fibers, which begin to soften at
temperatures below 100.degree. C., e.g. 75.degree. C. The balance
of the fibers (both the drawn polyester and the aromatic polyamide)
do not even begin to soften at such low temperatures. The drawn
polyester starts to soften at higher than 200.degree. C., e.g.,
250.degree. C., and the aromatic polyamide resists temperatures
above 250.degree. C. and even above 300.degree. or 350.degree.
C.
The concentration of drawn polyester fiber can and should fall
below 10 wt. % (even to zero) as the heat resistant aromatic
polyamide fiber concentration approaches 75 wt. %, e.g. 65 wt. % or
more. However, as this heat resistant polyamide component
approaches the lower limit of 10 wt. %; at least some drawn
polyester fiber should then be present to provide more fibers which
resist softening in the 150.degree. - 250.degree. C. range. For
example, if the concentration of aromatic polyamide fiber is less
than 25 wt. %, the drawn polyester fiber concentration should be at
least 25 Wt. %. The optimum fiber blend is therefore;
Staple Fiber Wt. % ______________________________________ Total of
drawn + undrawn polyester (for total polyester component,
drawn:undrawn .congruent. 30/70 at 35 wt. %; drawn;undrawn .gtoreq.
30/70, but < 2:1, at 75 wt. %) 35 - 75 Aromatic polyamide 65 -
25 ______________________________________
It should be noted that either excessive aromatic polyamide (more
than 75 wt. %) or excessive polyester (drawn + undrawn more than
90%) fiber concentrations will result in a non-woven backing having
poor dimensional stability and significant distortion of a
metal-clad backing can be expected during printed circuit
fabrication procedures.
The moisture sensitivity and flexibility of the raw webs is also a
significant factor in this invention. The water absorption of a raw
web containing less than 75 wt. % aromatic polyamide fiber
(determined on a bone-dry specimen conditioned for 3 days at 95%
relative humidity) is less than about 6% and can easily be brought
below 5% by increasing the polyester fiber component. The moisture
absorption can be further reduced by selecting a
moisture-insensitive thermosettable resin, e.g., the resins
described in U.S. Pat. No. 3,027,279 (Kurka, et al.), issued Mar.
27, 1962. However, problems caused by the moisture sensitivity of
webs containing more than 75% aromatic polyamide fibers are not
eliminated by resin coating or impregnating. When such
high-polyamide, resin-coated or -impregnated webs are metal-clad
and subjected to the conditions of soldering, serious blistering of
the metal cladding occurs. This blistering is substantially
eliminated by the fiber blends of this invention, particularly with
the lower aromatic fiber concentrations. It is not necessary to
resort to minimum aromatic polyamide fiber content to eliminate
solder blistering, however. For example, no visible blistering
occurs with a web containing 50% poly(m-phenylene isophthalamide)
and 50% poly(ethyleneterephthalate) staple fiber and impregnated
with the Kurka, et al., polymer, even though this impregnated web
has a moisture absorption of about 2% (3% for the raw web).
The raw (unimpregnated) web must be porous to permit impregnation.
The Gurley value (ASTM test D 726, method A) for the raw webs
preferably is less than 100 seconds per 100 cc of air when
determined on a single 0.125 mm layer of nonwoven material. The raw
web is preferably not so open or so loosely laid as to have no
Gurley value whatever, however. If 10 thicknesses of nonwoven
material of this invention are super-imposed, and 300 cc instead of
100 cc of air are forced through the resulting 1.25 mm thickness of
material, a Gurley value of at least 0.5 second and generally at
least 1 or 2 seconds will be observed. In industrial practice, the
raw web has a thickness of less than about 0.5 mm and preferably
less than about 0.4 mm. The weight of a 2880 or 3000 square foot
ream of the raw web can range from about 45 to about 75 pounds,
i.e. about 75 - 135 g/m.sup.2, preferably 50-65 lbs. per 2,880
ft..sup.2 ream (23-30 kg per 260 m.sup.2). Greater thicknesses
could result in an undue loss of flexibility after metal-cladding
of the backing. It is essential for rapid, efficient, and
continuous printed circuit manufacture that the metal-clad backing
(the metal-clad, impregnated web) be flexible enough to be passed
around rolls and the like. A backing web or film that was stiffer
than 10 mil (.25 mm) biaxially oriented poly(ethyleneterephthalate)
film (e.g. 10 mil "Mylar" film, trademark of E. I. duPont and
Company) would be insufficiently flexible for continuous industrial
printed circuit manufacture; in fact, the flexibility of 5 mil (.13
mm) "Mylar" (which measures 700 mg on the "Gurley Stiffness Tester"
available from W. and L. E. Gurley Co. of Troy, N.Y.) is considered
about standard for flexible backings now used in industry. The
printed circuit backings of this invention are at least as flexible
as 10 mil (0.25 mm) Mylar film and can be more or less flexible
than 5 mil (.13 mm) Mylar, depending on the flexibility of the
resin impregnant, etc. In some printed circuit applications, the
backing can be as flexible as desired; in others, a minimum
stiffness, e.g. a Gurley Stiffness value of more than 100 mg. is
required. A typical circuit backing of this invention has a Gurley
Stiffness value of about 500 mg.
The class of thermosettable resins used to impregnate the raw webs
of this invention are any of those prior art resins which can be
cured, without undue shrinkage, to form coatings or layers with
good electrical insulative properties, low moisture sensitivity,
and good thermal and mechanical properties, including good
flexibility. Prior to cure, the resin composition should be fluid
enough to impregnate a porous web. Resins which cure by a
condensation mechanism that liberates water (e.g. urea-aldehyde,
melaminealdehyde, and phenol-aldehyde resins) are less preferred,
since moisture absorbed in the web can cause blistering during a
soldering operation. Thermosettable polyurethanes and silicones can
be used, as can thermosettable (unsaturated) polyesters, acrylic
resins, and the like. A problem with curable polyesters is that
shrinkage can occur during curing and must be taken into account.
Curable epoxy systems, e.g., conventional polyhydric
phenol-polyglycidyl ether compositions, are suitable insulating
impregnants. A particularly suitable insulative epoxy composition
comprises a blend of (1) a branched-chain, acid-terminated
polyester of dicarboxylic acid, dihydroxy alcohol and a
polyfunctional compound selected from the class consisting of
polyhydric alcohols having at least three non-tertiary hydroxyl
groups and polybasic acids having at least three carboxyl groups,
not more than one-half of the total of said acids and alcohols
containing aromatic rings, which polyester contains an average of
2.1 to 3.0 carboxyl groups per molecule, has an acid number of
15-125, a hydroxyl number of less than 10, and is free from
ethylenic unsaturation in its skeletal chain, and (2) an epoxy
compound containing on the average at least 1.3 groups readily
reactive with the carboxyl group, at least one of which groups is
the oxirane group, said groups being separated by a chain of at
least two carbon atoms, the chain being free from ethylenic
unsaturation. See U.S. Pat. No. 3,027,279 (Kurka, et al.), issued
Mar. 27, 1962. For example, an epoxy-polyester composition of this
type can comprise a blend of (1) a polyester derived from adipic
acid, isophthalic acid, propylene glycol, and trimethylol propane,
and (2) a liquid epoxy resin such as the polyglycidyl ether of
bisphenol A or resorcinol, the condensation product of
1,1,2,2-tetrakis (4-hydroxylphenyl)ethane and epichlorohydrin,
limonene dioxide, cyclopentadiene dioxide, vinyl cyclohexene
dioxide and/or
3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexane
carboxylate.
The weight ratio of web to impregnant in the backings of this
invention ranges from 1:1 to 1:4 and is preferably about 2:3.
The resulting impregnated backings of this invention can be
provided with a conductive layer on one or both surfaces in a
conventional manner, e.g., with suitable adhesives or by an
electroless plating process which provides enough of a metal
deposit to permit electroplating. Suitable conductive layers
include foils of copper, aluminum, nickel, silver, gold, or
suitable transition metals. The thickness of the metal foil is
commonly on the order of about 0.02 - 0.05 mm. The resulting
impregnated, nonwoven web/metal foil laminate is, as has been
pointed out, particularly useful for forming a printed circuit,
though it can itself serve as a capacitor or as a structural
material, e.g., a protective or heat reflective lining. After metal
cladding, a conductor pattern can be provided on the nonwoven
backing by selectively etching off portions of the metal foil in a
conventional manner. The etched laminates can then be floated upon
or immersed in a solder bath for several seconds in the
conventional manner, the temperature of the solder bath being at
least 230.degree. C. and even as high as 340.degree. C. This solder
bath treatment is conventionally used to solder on previously
attached electrical or electronic circuit connections and/or
components such as resistors, transistors, semiconductor diodes,
capacitors, etc. The resulting printed circuit is illustrated in
the Drawing, which will be described subsequently.
For both single-clad (foil/web) and double-clad (foil/web/foil)
laminates, it is highly desirable that the nonwoven backing be at
least semi-transparent to facilitate inspection by the manufacturer
for proper adherence of cladding and/or register of top and bottom
cladding. It is a feature of this invention that the nonwoven webs
are inherently transparent or semitransparent.
As the skilled technician will readily appreciate, printed circuit
manufacturing technology places severe demands upon the dimensional
stability of the backing and the adherence of the metal cladding
thereto. For purposes of this description, the following
measurement has been devised to compare the distortion of various
backings of this invention and the prior art:
1. an impregnated, double-clad laminate is prepared in a
standardized manner, the cladding being 1.4 mils (.035 mm) of
copper;
2. the laminate of step (1) is cut to a 3 inch .times. 3 inch (7.62
cm .times. 7.62 cm) test sample size;
3. one side of the laminate is protected with masking tape and all
of the copper cladding is etched (with ammonium persulfate etchant
solution) from the other side to maximize distortion. The etched
laminate is dried for 30 minutes at room temperature. The first
measurement of distortion is them made;
4. the laminate of step (3) is heated to 250.degree. F.
(121.degree. C.) for 30 minutes to simulate typical printed circuit
processing steps. The second measurement of distortion is then
made;
5. the laminate of step (4) is immersed for 10 seconds in a
tin-lead solder bath maintained at 450.degree. F. (232.degree. C.).
A third measurement of distortion is made after this step.
The distortion measurements are made by placing the etched and/or
heated 3 inch .times. 3 inch (7.62 cm .times. 7.62 cm) sample which
would be more or less warped or curved, on a flat surface so that
the concave curved surface of the sample will form an arch over the
flat surface. The distance from the flat surface to the top of the
arch is the "distortion." A distortion of less than about 0.125
inch (about 3.2 mm) is considered very good.
Solder blistering is tested for by conditioning the laminate of
step (3) with controlled humidity conditions and subjecting the
preconditioned laminate to step (5). Any blistering which occurs is
caused by escaping moisture which blows or puffs up or otherwise
delaminates the copper.
In addition to the lack of solder blistering and distortion,
another desirable feature of the metal-clad laminates of this
invention is their low shrinkage. This low shrinkage is further
evidence of good dimensional stability. Still another desirable
property of the backings of this invention is good tear
strength.
The invention is illustrated by the following non-limiting
Examples.
EXAMPLE 1
A. Formation of Raw Nonwoven Web
The following fiber mixture was weighed, then opened and blended
together on a fiber blender:
Parts by Weight ______________________________________
poly(m-phenyleneisophthalamide) Staple (under the trademark "Nomex"
aromatic polyamide), 2 denier .times. 1.5 inches (3.81 cm) 50
undrawn poly(ethyleneterephthalate), 3 denier .times. 1.5 inches
(3.81 cm), available as "Celanese type 450" (trademark) 50
______________________________________
The well blended mixture was then formed into a web on a Rando
Webber machine at a speed of about 5 feet per minute (1.52 m/sec.).
After the web was formed, it was then passed through a needle loom
machine where the light fluffy web was needled for greater strength
and uniformity. After this, and in the same operation, the web
passed through steel nip rolls which were heated to 375.degree. F.
(190.degree. C.). This densified the web, and at this point the web
thickness was about 12 mils (0.31 mm). The web was then densified
more by running through oil heated calender rolls at 475.degree. F.
(246.degree. C.) and 5,000 pounds (2275 kg) nip pressure, two
passes. After this operation, the web caliper was 8 mils (.20 mm)
and the web weight was 3.0 ounce/sq. yard = 60 pounds per ream (102
g/m.sup.2). The web was porous, dense and tough.
B. Formation of Circuit Backing from Raw Web
The raw web produced in Part A of this Example was dip coated with
the epoxy-polyester resin of Example 2 of U.S. Pat. No. 3,027,279;
i.e., the reaction product of adipic acid/isophthalic
acid/propylene glycol trimethylolpropane polyester, an
epichlorohydrin-bisphenol A epoxy resin, and tris
(2,4,6-dimethylaminomethyl) phenol. This resin coating was cured
for 30 minutes at 400.degree. F. (205.degree. C.). The resulting
impregnated web had a caliper of 10 mils (.25 mm), good tear
strength, and an 80:20 ratio (by weight) of resin-to-fiber (i.e.,
resin:raw web).
C. Copper Cladding Procedure
An adhesive coat (same resin composition used in Example 1-B) of
about 1 mil (0.025 mm) dry thickness (both sides) was applied over
the first cured coat. This was dried and B-staged for 20 minutes at
300.degree. F. (149.degree. C.). One ounce per square foot (0.03
g/cm.sup.2) Treatment A copper (Circuit Foil Corporation) was then
laminated to both sides by passing through the nip of pressure
rolls heated to 280.degree. F. (138.degree. C.). One roll was
steel; the other was rubber. After laminating, the adhesive was
cured 15 minutes at 400.degree. F. (205.degree. C.). The resulting
flat, double-clad laminate was flexible and had an overall
thickness of 14.8 mils (.392 mm). The copper was found to be
securely bonded to the backing.
D. Coefficient of Thermal Expansion
A second copper-clad sample was made according to Parts A through C
of this Example. The copper cladding was completely etched off to
provide a nonwoven, impregnated web, the overall caliper of the
dielectric being 12 mils (0.30 mm). The linear thermal expansion
coefficient was measured throughout the temperature range of
30.degree. - 160.degree. C. and found to be 17 .times.
10.sup..sup.-6 per .degree.C. A one ounce per square foot (0.03
g/cm.sup.2) Treatment A copper foil (Circuit Foil Corp.), 1.4 mils
(0.035 mm) in thickness, was found to have a linear expansion
coefficient of 18 .times. 10.sup..sup.-6 per .degree. C. in this
temperature range, a value which agrees well with the literature
value of 17 .times. 10.sup..sup.-6 /.degree.C.
EXAMPLES 2 - 4
The method of Example 1(A) was used to make webs of varying fiber
content, with the following exceptions: a garnett machine was used
to both blend the fibers and prepare the light, fluffy webs. The
densification procedure was with a platen press instead of nip
rolls and was as follows:
Examples Platen Press Conditions
______________________________________ 2 and 3 325.degree. F.
(163.degree. C.), 500 psi (35 kg/cm.sup.2), 15 min. 4 450.degree.
F. (232.degree. C.), 500 psi (35 kg/cm.sup.2), 15 min.
______________________________________
The fiber blends were:
Example Staple Fiber Wt. % ______________________________________ 2
"Nomex" (see Example 1(A) ) 10 Undrawn polyester (see Example 1(A)
) 40 Drawn poly(ethyleneterephthalate) 3 denier .times. 1.5 in.
(3.81 cm.) ("Celanese Type 410") 50 3 "Nomex" (see Example 1(A) )
25 Undrawn polyester (see Example 1(A) ) 50 Drawn polyester (see
Example 2) 25 4 "Nomex" (see Example 1(A) ) 75 Undrawn polyester
(see Example 1(A) ) 25 ______________________________________
The resulting raw webs of Examples 2, 3 and 4 measured 4.5, 5.8,
and 6 mils (0.114, 0.147, and 0.152 mm) in thickness,
respectively.
Example 1, Parts B and C, were followed in making printed circuit
backings, except that a platen press was used in the copper
cladding procedure, the conditions being 400.degree. F.
(205.degree. C.) and 125 psi (8.75 kg/cm.sup.2) for 30 minutes. The
thickness and resin/raw web ratio of the impregnated webs were
measured, as follows:
Example Thickness, mils Resin: Raw Web Ratio (by wt.)
______________________________________ 2 6.8 (.173 mm) 54:46 3 7.6
(.193 mm) 57:43 4 8.9 (.226 mm) 70:30
______________________________________
EXAMPLE 5
A. Distortion Tests
The distortion test outlined in the portion of the specification
preceding these Examples was followed by 3 in. .times. 3 in. (7.62
.times. 7.62 cm) samples cut from the laminates of Examples 1-4. To
provide a standard of performance for the insulative materials of
this invention, the procedure of Example 1 was followed to provide
double-clad laminates from the following backings:
Backing (I): An all-polyester web, i.e. 50/50 drawn/undrawn
poly(ethylene-terephthalate), as "Kendall M-1482"; thickness, raw
web 5 mils (.127 mm) thickness, impregnated web 7.5 mils (.191 mm)
resin: raw web ratio (by wt.) of impregnated web 57:43 Backing
(II): An all "Nomex" (see Example 1(A) ) web, i.e. Porous nonwoven
web comprising 100% "Nomex" fiber bonded with 10 wt. %
thermosetting acrylic binder, as "Kendall ST-477.1"; thickness, raw
web 3 mils (.076 mm) thickness, impregnated web 7 mils (.178 mm)
resin: raw web ratio of impregnated web 78:22
The double-clad laminates obtained from Webs (I) and (II) had 1.4
mil (.035 mm) copper foils laminated to each side.
The results of the distortion tests are given in the following
table:
TABLE I
__________________________________________________________________________
DISTORTION OF DOUBLE-CLAD BACKINGS
__________________________________________________________________________
Distortion, flat surface to top of arch, inches (mm)
__________________________________________________________________________
Wt. % After 250.degree.F. 450.degree. F. "Nomex" in Etch
(121.degree.C.) (232.degree. C.) Laminate fiber blend 30 min.
solder
__________________________________________________________________________
Double-clad Backing (I)* 0 0.63 (16) 0.88 (22) 1.00 (25.4) Ex. 2*
10 0.44 (11) 0.82 (21) 0.69 (18) Ex. 3* 25 0.13 (3.3) 0.13 (3.3)
0.13 (3.3) Ex. 1* 50 0.09 (2.3) Flat (0.0) 0.03 (0.8) Ex. 4** 75
0.33 (8.4) 0.32 (8.1) 0.19 (4.8) Double-clad Backing (II)** 100
0.38 (9.7) 0.32 (8.1) 0.75 (19)
__________________________________________________________________________
* Distortion characterized by bowing toward the backing. **
Distortion characterized by bowing toward the unetched copper
cladding
B. Solder Blistering Tests
The soldering blistering test (450.degree. F. [232.degree. C.]
solder), also outlined previously, was carried out for an identical
set of samples. The samples were etched and dried as described
previously and conditioned for 24 hours at 50% relative humidity.
Solder blistering was not detectible with 0 - 50 wt. % Nomex fiber
content. Some slight solder blistering can occur at 75 wt. % Nomex
fiber content. The 100% Nomex sample (Backing (II)) ) was quite
obviously blistered.
The 3 day/95% R.H. moisture absorption of the resin impregnant of
Example 5(B) is only about 1%, and this is typical of resinous
electrically insulating coating and impregnating compositions.
C. Coefficients of Thermal Expansion
The linear expansion coefficient of Backing (I) was obtained by
etching off all the cladding and determining the coefficient in
both the machine direction and cross direction of the web at
30.degree. -100.degree. C. and 100.degree. -160.degree. C. The
results were as follows:
TABLE II ______________________________________ THERMAL EXPANSION
OF ALL-POLYESTER WEB ______________________________________ Linear
Expansion Coefficient, in./in. or cm/cm per .degree.C.
______________________________________ Temperature Machine Cross
Range Direction* Direction* ______________________________________
30 - 100.degree. C. 30 .times. 10.sup..sup.-6 46 .times.
10.sup..sup.-6 100 - 160.degree. C. 66 .times. 10.sup..sup.-6 100
.times. 10.sup..sup.-6 ______________________________________ * The
terms "machine direction" and "cross direction" refer to the manner
of laying of fibers into a web structure, and are determined by the
type and operation of the web-making machine.
The reported linear expansion coefficient for Nomex (see Example 1)
fiber of yarn is 20 .times. 10.sup.-.sup.6 per .degree.C. However,
a commercially available 5 mil (0.127 mm) Nomex fibrid paper had,
in the machine direction, a linear expansion coefficient of 11
.times. 10.sup.-.sup.6 /.degree.C. at 70.degree. -120.degree. C.
and 35 .times. 10.sup.-.sup.6 /.degree.C. at 120.degree.
-155.degree. C. Thus, the expansion coefficient data of webs made
according to this invention (see Example 1(D) ) further reflects
significant advantages in dimensional stability over all-polyester
webs (see Table II) and commercially available
poly(m-phenyleneisophthalamide) papers.
* * * * *