Note: Descriptions are shown in the official language in which they were submitted.
20~4131.
PATENT
A HIGH PERFORMANCE EPOXY BASED COVERLAY AND BOND
PLY ADHESIVE WITH HEAT ACTIVATED CURE MECHANISM
by
Thomas F. Gardeski
BACKGROUND
During the past quarter century, the growth of the
electronic circuits industry at an unrivaled pace has resul-
ted in the development of higher performance materials of
construction. However, the development of higher perfor-
mance materials of construction has not resulted in the
development of corresponding high performance adhesive
materials and systems to bond the materials of construction
together, especially in severe environmental conditions
found in under-the-hood automotive and military applica-
tions. Adhesive materials and systems that are currently
available meet some of the requirements for such properties
as peel strength, chemical resistance, moisture resistance,
high temperature stability, dimensional stability especially
in the Z-axis direction adequate flow, room temperature
storage stability prior to processing and ease of proces-
sing, but typically fail to meet one or more of the require-
ments for one or more of the properties.
2004131
PATENT
A need has therefore been felt for an adhesive
material that meets all the requisite property requirements
for severe environmental conditions while retaining the ease
of application.
SUMMARY
It is an object of the present invention to pro-
vide an improved adhesive material.
It is a feature of the present invention to pro-
vide an improved material for use in bonding electronic
circuit construction materials.
It is another feature of the present invention to
provide an adhesive material using a two stage reaction
sequence.
It is yet another feature of the present invention
to provide an adhesive material using a two stage reaction
sequence wherein the intermediate adhesive material result-
ing from the first reaction stage can be stored for long
periods of time without deterioration of the properties of
the adhesive material.
It is a still further feature of the present in-
vention to provide an improved adhesive material by provid-
ing a first reaction between an aziridine component and a
polyester component and by providing a second reaction
2004131.
PATENT
between the aziridine/polyester component and at least one
epoxy component, the at least one epoxy component being an
electronic grade resin.
The foregoing and other features are accomplished,
according to the present invention, by reacting a hydroxyl
terminated polyester component with an aziridine cure
component, the reaction proceeding at room temperature. The
resulting polyester/aziridine component reacts with at least
one and preferably two epoxy components, one of the epoxy
components being an electronic grade resin such as tris
methane novolac epoxy. The second reaction requires a
temperature of 250°F to 400°F. The high reaction
temperature permits the unreacted intermediate mixture of
the polyester/azirdine component and the epoxy components)
to have a long shelf life during which the implementation of
the second reaction phase will result in high performance
bonding. The intermediate mixture can be stored on a
substrate protected by a release substrate or can be stored
between two release substrates until needed.
These and other features of the present invention
will be understood from the following description.
DESCRIPTION
The composition of materials of the present
invention comprises at least one and preferably two epoxy
components, one epoxy component of which must be selected
. 2004131
4 PATENT
from a family of electronic grade resins such as tris
methane epoxy novolac sold by Dow under the designation
Quatrex 5010. The optional components are epoxies such as
the flexible "bis-epi" and hard "novolac" types such as
Celanese Epi-Rez*5132 and Dow D.E.N* 438, respectively. The
composition of materials includes a high molecular weight
hydroxyl terminated polyester component with minimal
carboxylic acid functionality, such as DuPont's 49002 and
an aziridine curative component such as Xama 2 or 7 supplied
by Cordova Chemical Co.
The two stage cure (reaction) sequence consists of
first reacting the aziridine with the carboxcylic acid
groups on the polyester as follows:
O H2C CH2
II ~-X-
2RCOH + H2C CHZ
R.T.
O O
2 5 II II
RCO-CHZCHZ-N-X-N-CHZCHZ-OCR
H H
where R designates the high molecular weight polyester
components and X designates the repeating unit of the
aziridine component. This reaction takes place at room
temperature.
* Trademarks
204131
PATENT
The second reaction, which is unique to the
present invention, is comprised of reacting the -~- groups
5 -~~ groups of the epoxy components as follows:
O O
- - CHz-OCR+ CHz-CH- X -CH-CHz
RCO-CH2CHz-N-X
N CH2
H H
Q (300-400F)
2 0 RCO-CH
CH
2 N X N CHZCHz-OCR
z
H -C-H H- C-H
H -C--- OH H-C--OH
X
I I
H -C-OH H- C-OH
H i H H i H
O
RCO-CH
CH
2 N X N CH2CHz-OCR
z
where Y designates the tris methane epoxy either alone or in
conjunction with a bis-epi and/or novolac epoxy having
structures shown below:
~Hs OH H3 O
z z~
4 5 CH -CH-CH L O-~- j -~-.-OCHz-CH-CHz ~O-s~--~-~-...OCH2--CH-CHZ
CH3 ~ CH3
200411
PATENT
"BIS-EPI" EPOXY
CH2 CHCHz -O /O
OCHZCH - CH2 O--CH2 C~HZ
Sb .--..~ CH2 ~ CH2
"NOVOLAC" EPOXY
E_xamole of the Process
A mixture is prepared with the following
components: a polyester resin component having a solids
content of 17-20%, composed of DuPont 49002 base resin in a
solvent mixture of 90% methylene chloride and 10% cyclohexa-
none by weight; an epoxy novolac is dissolved in methylethyl
ketone, with an 85% solids content by weight, known commer-
cially as Dow DEN 438 an electronic grade epoxy resin at 75%
solids in methylethyl ketone known commercially as Dow
Quatrex 5010; and a polyfunctional aziridine known commer-
cially as Xama 7. The components mixture is prepared by
combining 80% by solids content (by weight) of the polyester
component to 10% by solids content (by weight) of the epoxy
novolac to 10% by solids content (by weight) of the elec-
tronic grade epoxy and 0.25 parts (by weight) of the aziri-
dine to 100 parts by weight of the above mixture including
solvents. The component mixture can be prepared in two
ways:
7 ~ ~ PATENT
Procedure 1) The polyester and aziridine are combined,
thoroughly mixed, then allowed to stand at room temperature
for a minimum of 30 minutes prior to the epoxy additions to
allow onset of the aziridine/ carboxylic acid reaction; or
Procedure 2) The polyester, epoxies, and aziridine are
added separately without any mixing until all the components
are in the vessel then thoroughly blended and allowed to
stand for a minimum of 30 minutes prior to use to allow for
onset of the aziridine/ carboxylic acid reaction.
The homogeneous solution is then applied by
reverse roll coating technique to a 2 mil polyimide (e. g.,
Kapton) film to yield a 1 mil dry coating on the polyimide
film. The polyimide film is dried in a 75 foot oven at 25
fpm (feet per minute) and 212°F, combined to a 1 mil release
substrate at the coater/laminator combining station, rolled
up and stored at room temperature for future use. (Accord-
ing to another application, the homogeneous solution is
stored between two release substrates, the adhesive material
thereby being available for use with any surfaces to be
bonded:)
Sections are cut from the roll, the release
substrate is removed, then the coated film was placed over a
sheet of 1 oz. copper. The composite structure is then
placed between two caul plates with a high temperature
release material on both sides and pressed in a hydraulic
press for 1 hour at 375°F and 250 psi pressure. The
resulting composite laminate structure exhibits the
properties exhibited in Table I when tested in accordance
with the ANSIIPC-FC-232B and 241B procedures.
* Trademark
C
PATENT
Initial Peel 20 PLI
Peel After Solder 21 PLI
Chemical Resistance
MEK 21 PLI
TOL 20 PLI
IPA 21 PLI
T111/MC 21 PLI
Solder Float Pass
Aging (96 hrs @ 275F No Bond Strength
in air circulating oven) Change
where;
PLI - Pounds per lineal inch
MEK - Methylethyl ketone
TOL - Toluene
IPA - Isopropylalcohol
T111 = Trichloroethylene
MC - Methylene Chloride
TABLE I
____________________________________________________
OTHER EXAMPLES
1. The adhesive mixture is coated on polyimide
(and laminate) film to foil in line at 300°F and 90-100 psi
pressure. The resulting structure is post cured for 2 hours
at 150°F, 2 hours @ 275°F and 2 jpirs at 35-°F.
2. Coat release substrate and combine to another
release substrate to yield an unsupported film.
2004131.
PATENT
The adhesive composition of the present invention
provides a coverlay and bond ply adhesive coating material
consisting of 50-90% by weight polyester and 90-50~ by
weight epoxy with unique latent heat reactive cure mechanism
comprised of one and preferably two epoxy components, one of
which must be selected from a family of electronic grade
resins such as tris methane epoxy novolac and the other
epoxy or epoxies from the novolac or bis-epi epoxy families
and a high molecular weight hydroxyl terminated polyester
with a carboxcylic acid functionality as determined by an
acid number ranging from 0.2 to 4Ø The adhesive material
is cured in a two stage reaction sequence to provide a fully
crosslinked network without the evolution of volatile by-
products to provide an advanced laminating, coverlay, and
bond ply adhesive for film to film, foil to film, foil to
foil and hardboard to hardboard applications. The adhesive
material has with excellent flexibility, superior bond
strength, solder resistance, moisture and chemical resis-
tance and superior Z-axis stability along with continuous
and/or deferred processing capability. The high temperature
of the second stage curing process provides that the coating
material can be stored for long periods of time prior to the
implementation of the curing process. The epoxy based
adhesive materials can be coated on an insulating film or
release substrate by a continuous process and stored at room
temperature indefinitely prior to further processing, or
laminated in-line to various foils or films, and which can
be cured without the evolution of volatile by-products to
provide a flexible bond-ply with superior overall properties
to any currently available system with the added advantage
of excellent Z-axis stability.
200413..
PATENT
The foregoing description is included to illus-
trate the operation of the preferred embodiment and is not
meant to limit the scope of the invention. The scope of the
invention is to be limited only by the following claims.
5 From the foregoing description, many variations will be
apparent to those skilled in the art that would yet be
encompassed by the spirit and scope of the invention.