CA1060136A

CA1060136A - Cured epoxy polymer having improved adhesive properties

Info

Publication number: CA1060136A
Application number: CA201,055A
Authority: CA
Inventors: Charles A. Mcpherson
Original assignee: Western Electric Co Inc
Current assignee: AT&T Corp
Priority date: 1973-06-11
Filing date: 1974-05-28
Publication date: 1979-08-07
Also published as: DE2427030C3; IL44997A; CH603725A5; JPS5034094A; DE2427030B2; BR7404745A; SE7407533L; DE2427030A1; NL7407729A; NL162118B; IL44997A0; JPS544398B2; FR2232614A1; IE39796B1; FR2232614B1; GB1448415A; IT1011946B; ES427131A1; NL162118C; MY7700290A

Abstract

Abstract of the Disclosure A cured epoxy polymer having improved adhesive properties is disclosed. The epoxy polymer is the reaction product of a mixture comprising a resin component comprising (a) a diglycidyl ether based upon linoleic dimer acid, (b) an elastomerically modified epoxy resin blend and (c) a diglycidyl ether of bisphenol A and/or bisphenol F and a suitable curing agent. The reaction mixture is heated at a suitable temperature for a period of time sufficient to attain a full cure of the epoxy. The resulting cured epoxy shows good adhesion to electro-less metal deposited thereon without the need for pretreatment such as etching, solvation, abrasion etc. This is extremely useful in the production of metal-plated polymer parts.

Description

6~:)136 C ,~ McPhersorl 3 ,~ :
:l. Backgro~ cl o~ the Irlvention __ _ _~

2 l. l~ield of the Invention :~

3 This lnventlon relates to a cured epoxy ;

4 polymer h-lvi.ng improved adhesive properties to a ~ : 1-metal dep,~sit,~d on a surfaoe thereof, and more 6 particularly, to a cured cpoxy polymer resulting 7 ~rom cur-J.ng a mixture comprising (a) a diglycidyl 8 ether based upon llnoleic dimer acid~ ~b) an 9 elastomerically modlfied epoxy resin blend, ~c3 a diglycidyl ether of bi3phenol A (4,~'-isopropylidene 11 diphenol) and/or bisphenol ~ (methylenediphenol) an 12 (d) a sultable curlng agent. :
13 2. Descriptlon of the Prior Art During the past ~ew years, a market ~or metal~plated polymer par~s has grown rapidl~J~as 16 manufacturers have begun to appreoiate the functional~
17 appearance o~ such~parts when plated wlth brlgh~
18 metallic ~inlshes, and to take advantage o~ economies~
l9 ln cost and~weight a~forded:b~ substltuting molde~d polymeric parts ~or metal. Furthermore, such plated -~
21 ~lnishes are not as susceptible to pittirlg and ~
22 corrosion because there is not a ~alvanic reaction 23 between a polymeric sub3trate and a plated metal.
24 Beeause polymexic materials normally~do no~t~
conduct electrlclt~, it ~9 oommon~gractlce ~o p~7vi~e~a~

:
~; :: .

~ ~ 31 ; ~'.~, : :

1~6¢~1L3 conductive layer or coatiny, such as copper, by electroless deposition so that an additional thickness of metals, par-ticularly copper, nickel and chromium, can be electrolytically ;~ ~E
plated onto the electroless copper layer. Electroless de-position refers to an electrochemical deposition of a metal coating on a conductive, non-con~uctive, or semiconductive substrate in the absence of an external electrical source.
While there are several methods of applying this metallic coatiny by a combined use of electroless and electrolytic procedures, it was not until quite recently that processes were developed which can provide even minimal adhesion of the conductive coating to the polymer. This is because overall adhesion is governed by the bond strength between the polymer substrate and the electroless copper layer. Even ~:ith these `
ir.lproved processes, reasonable adhesion can be obtained with only a very few polymers, and then only when great care is -;
taken in all of the ste~s for the preparation and plating of ~ :~
the polyr.ler substrate.
Polymers extensively employed and upon which electro-: . . .
less deposition is conducted, especially in the printed circuit industry are epoxy polymers resulting from curing uncured di~
glycidyl ethers of bisphenol A resins produced by a condensation -~
reaction between bisphenôl A and epichlorohydrin. The conden-sation reaction products or epoxy resins have a general structure 0\ CEI OH CH
2 2 E O ~-c~_OcH2 cE~_ cH2 _ l _ o ~_ c~
3 3 J `;
f O
~ 0 C~ CH/\ ~
~, ~:;

.

where n is the number of repeated units in the resin chain.
The varying types of these epoxy resins are described in terms of their viscosity or softening point, epoxide equivalent weight and hydroxyl content. The epoxide equivalent weigh-t is defined as the number of grams of resin containing one gram equivalent of epoxide. The epoxide equivalent weight is determinative of the number of repeated units in the epoxy resin chain. The hydroxyl content is defined as the number of equivalents of hydroxyl groups contained in 100 grams of resin.
One of the valuable properties of epoxy ~;
resins, i.e., diglycidyl ethers of bisphenol A and variants or modifications thereof, is their ability to transform readily from a liquid or viscous state to tough, hard thermoset solids, i.e., transform from a linear structure to a network crosslinked in three dimensions. This hardening is accomplished by the addition of a chemically active reagent known as a curing agent. Some curing agents promote - `
curing by catalytic action, others participate directly in ` 20 the curing reaction and are absorbed into the resin chain.
The surface of a cured or crosslinked epoxy article is hydrophobic and is therefore not wet by liquids havin~ a high surface tension. Since electroless de~ositions usually employ aqueous sensitizing and "
activating solutions having metal ions therein, the surface will not be wet thereby. Since the sensitizing and `
activating solutions will not wet the surface, the -catalytic species are not absorbed onto the surface and subsequent deposition of the metal ions cannot proceed.
In the present state of the art, various methods are available for rendering the surface of a polymer :~
-3- ~

- - :.~ , ,. ~ , , 6~3~36 ; ~

or a plastic material hydrophilic. One method in common practice in plating plastic materials entails mechanical -roughening of the surface of the plastic. Initially, this ;
surface roughening is accomplished by some form of mechanical -deglazing, such as scrubbing with an abrasive slurry, wet , .
tumbling, dry rolling or abrasive (sand) blasting. However, this prior art method gives an adhesion of up to 3 lbs./
in. at 25C for a copper pattern on a cured polymer based , .
upon the diglycidyl ether of bisphenol A. This adhesion is unsatisfactory for printed circuit boards having a copper :~
pattern thereon. It has been empirically established ;~
that a minimum peel strength of about 5 lbs./in., at a 90 ; ~ :" . ~ , peel and a peel rate of 2 in./min. at 25C is required ,, ~ , .
to prevent a metal coating from blistering or peeling `~
from a plastic surface during variations in temperature and to allow for various processing steps usually employed in generating the copper pattern. The adhesion requirements for printed circuit boards is therefore at least 5 lbs./in.
at a 90 peel and a peel rate of 2 in./min. at 25C
(for a copper thickness of 1.4 mil).
In addition, this mechanical deglazing process ,: .
is costly in that many parts have to be finished by hand and, in the case of relatively small parts, or parts with complex contours, it is very difficult to abrade the surface uniformly by conventional means. Of greatest disadvantage, however, is in forming printed circuits, utilizing a photoimaging process, such as the photoselective metal deposition process revealed in U.S. Patent No.

3,562,005, assigned to the assignee hereon. The `
photoimaging process inherently requires a high pattern ,~ "~, resolution. This resolution is limited by the topography of ::

,'"; :: ' ,.
'.:

'." " " .' , ' ' ' ' ', ' . . ' . ' ' ", ,' ' ' ' ' ` ;;., ' ' ' ' ,, , "' ~ , ~.~1, . . .

- `` 16)6~)~36 ~: the surface on which the pattern is generated. When mechanical deglazing ls employed, e.g., by sand blasting, the resolution of the pattern suffers because of the mechanically roughened surface.
; In more recent years, chemical cleglazing or etchir.g techniques were developed for various plastics using strong acidic solutions. U.S. Patent No. 3,437,507 reveals a chromic acid treatmen-t of plastics, such as an acrylonitrile~
batadiene-styrene (A-B-S) and an amine cured diglycidyl ether of bisphenol A epoxy, to improve the adherence of an electroless deposit to the surface thereof. Again, as indicated above, a minimum adhesion value of 5 lbs./in. `
; has to be met for printed circuit boards. A cured diglycidyl ether of bisphenol A epoxy polymer treated with -;
chromic acid gives adhesion values of about 3 lbs./in. for metallic patterns deposited thereon.
Another method, generally employed for plastics, such as A-B-S, comprises treating the plastic with an ~' organic solvent thereof. U.S. Patent No. 3,425,946 reveals-such a method with A-B-S plastic. However, what ~
solvents are effective depend on the plastic employed and is therefore empirical in nature. Organic s~lvent pretreatment ~, .
alone is ineffective in raising the adherence of metallic patterns to cured epoxies such as the epoxy polymers resulting from curing the diglycidyl ether of bisphenol A.
A cured diglycidyl ether of bisphenol A epoxy treated in ; ~ -this fashion exhibits an adhesion of about 3 lbs./in., whereas as stated above, 5 lbs./in. is the minimum amount desired for printed circuit boards (at 25C~
There has not heretofore been electroless metallization of a virgin epoxy, i.e., an as-cured epoxy ~
' ~:

60~3~i ;
without pretreat~ent of any surface thereof with solvents, etchants, abrasives, etc., to render such surface hydrophilic.
A cured epoxy surface which gives improved adherence with respect to an electroless metal deposited thereon, without pretreatment thereof (etching, solvation, abrading, etc.), is ~ ;~
, ~
therefore needed and is an object of this invention.
Sum~lary of the Invention ~;
Broadly stated, this invention relates to a cured epoxy polymer having improved adhesive properties to a metal deposited on a surface thereof and more particularly, to a cured epoxy polymer resulting from curing a mixture comprising (a) a diglycidyl ether based upon linoleic dimer acid, (b) an elastomerically modified epoxy resin ~lend, (c) a diglycidyl ~;
ether of bisphenol A (4,4'-isopropylidenediphenol) and/or bisphenol F (methylenediphenol) and (d) a suitable curiny agent.
ore specifically, according to the invention there is provided a cured epoxy polyrner having improved adhesive ;~
properties comprising the reaction product of a mixture com~
.
prising: (1) a resin component comprising, (a) about 25 to -20 about 95 parts by weight per 100 parts by weight of said resin component of a diglycidyl ether based upon linoleic dimer acid selected from the group consisting of (al) an adduct of two moles of the diglycidyl ether of bisphenol A and one mole of linoleic ~imer acid having a structural formula of H2C-CH-CH -0 ~ CH3 -0-CH2-CH-CE~2-o 0 0 OH CH~ 0 C C_o-cH2-cH-c~2-o~ c-~-ocH2-cH-cH2 ~ .... . .
( ~ 7 (/~2)7 3 _cH=cH_~cH2~_cH3 (C~2)5 C~3 ; t ~ - 6 ~

: .. ~ . : - . .. . ~ . - ~ .

6~13~

and an epoxide equivalent weight of 650 to 750, Ib1) a digly~
cidyl ether of linoleic dimer acid having a structural formula of /0 o o /o\ ,, H2c_cEl_c~2_o_c C-0-C~2-CH-CH2 ,-, .. . .
(CI12)7 ~CH2)7 H2-CH=CH-(CH2)~ CH3 (,CH2)5 3' : `
and an epoxide equivalent weight of 400 to 420, and ~cl) a .
mixture thereof; (b) about 5 to about 50 parts by ~7eight per 100 parts by wei~ht of the resin component of an elastomerically :
modified epoxy resin blend comprising the reacti.on product of , ~ ., .
about ~0 weight percent of a carboxyl terminated acrylonitrile/

butadiene random copolymer having a structural formula of CH3 C~1 HOOC-CH2CH2C ~ (CH2CH=CHCH2)5C~12CH ~ C-C~12CH2C~OH, CN CN CN
containing 2.37 percent carboxyl groups, 18 to 19 percent bound acrylonitrile and having a number average molecular weight of :.
3200, cor.lbined with about 60 weight percent of a diglycidyl ether selecte~ from the group consisting of a diglycidyl ether of bisphenol A having an epoxide equivalent weight of 180 to 195 and a diglycidyl ether of bisphenol F having an epoxide equivalent weight of 152 to 167; and (c) a remainder of a di-glycidyl ether selected from the group consisting of a diglycLdyl ether of bisphenol A, a diglycidyl ether of bisphenol F or a mixture thereof; and ~2) a curing agent selected from ~a) acid anhy~ride present in an amount ranging from about 16 to :;~
about 60 parts ky weight per 100 parts by weight of the resin ~.
component, (b) a polyamine present in an e~ual role-to-mole _ 7 _ i, h ';' ' ~ '. ~' , : ` ` ' ;; , ' " : , .', ,, ' ` ' .: ' ' ' ` ' 6~ 3~i ratio ~ith the resin component, (c) a mixture comprising said ~olya~line in (b) above co~ined with at leas-t 5 parts by weight per 100 parts by weight of the resin component of an acid :: :
Ir~J ~f J~ On~ : .:
anhydride, (d) a n:ixture comprising said~acid anhydride in (a) above combined with up to about 30 parts by weigllt per 100 parts by weight of the resin component of a carbo~ylic acid selected from the group consisting of dicarboxylic acid having a structural formula of O ' .. . . .
(HO--C) 2R'', where R'' is an organic radical selected 'rom 10 CH2 (C~I2) 5cH2 ~ CH2 (C 2) 6 (Cl 2) 6 2 ~ ~ :
H 2 CH= CE~ ( C~12 ) ~ C~13 ( CH2 ) 5CH3 ,CH 3 ,C~I 3 2 2 , ~ 2CH CHCH2) 5-CH2-CH--3~-CH CH a d CN CN CN . ~ :

CH2CH2C~ (C~2CH=CHCH2 ) 5CH2CH~ CH CH2 ) ,C CH2 CH2;
CN CN COOH CN
a trimmer acid having a stocchiometry of C54H9606, and a mixture thereof, and (e) a mixture of the foregoing.
Description of the Drawing : :
The present invention will be more readily understood by reference to the drawing taken in conjunction t~,ith the .
detailed description, wherein the Figure is a -' - ~,~ .- ~ . - .

136 ; ~ ~
cross-sectional view of a laminar body of the invention ~;
comprising a cured epoxy-coated subs-trate plated with an electroless metal deposit.
Detailed_Description The present invention is described primarily ` ~ ;
in terms of an adherent copper deposit, deposited from an electroless plating bath, upon a cured epo~y having improved adhesive properties. However, it will be understood that ;~-such description is exemplary only and is for purposes of exposition and not for purposes of limitation. It will be readily appreciated that the inventive concept described is equally applicable to applying to the cured epoxy other conventional species which may be utilized in cementing, printing and metallizing the epoxy. Again, it is, of course, to be understood that by a "cured epoxy" is meant the product resulting from curing a curable mixture comprising a resin component of (a) a diglycidyl ether based upon ;~
linoleic dimer acid, (b) an elastomerically modified epoxy resin blend and (c) a diglycidyl ether of bisphenol A
and/or bisphenol F, cured with a suitable curing agent component selected from an acid anhydride, a polyamine, a ~ ;
mixture of an acid anhydride and a polyamine, and a mixture of an acid anhydride and a suitable carboxylic acid.
A suitable diglycidyl ether based upon linoleic dimer acid is the adduct of two moles of the diglycidyl ether of bisphenol A and one mole of linoleic dimer acid (ratio of 2:1) having the structural formula ;
~", _g_ ' :
' ~

'':

(1) ~12C-CH-C~12-0~C~ 0-cEl2-c~I-`cH2-o~) .j "~--C C-o-cH2-cE~-c~l2- 0~--C~ G CH2 2 (CH2)7 (CH2)7 C 3 j~
~C~2-Cll=CEl- (C:M2) ~--C~13 `;

These uncured modified diglycidyl ethers are described in terms of their epoxide equivalent weight. The epoxide equivalent ,. ~ . ~ .
weight is defined as the number of grams of resin containins one gram equivalent of epoxide. The above-described linoleic aimer ester modified diglycidyl ether of bisphenol A employed has an epoxi~e equivalent weight of 650 to 750.
A second suitable diglycidyl ether of linoleic dimer acid is one haviny a general structural formula O O O O .".' ' \ " " / \ , ~ ~
(2) H2C-CIl-CH2-0-C C-0-CH2-CH-cH2 2)7 (OEi2)7 \ ~ CH2-CH=CH-(CH2)~ C~13 (~H2)5-CH3 and an epo~ide equivalent weight of 400 to 420. ;~
The concentration of the above~described suitable diglycidyl ether based upon linoleic dimer acid resins in the resin component ranges from a minimum of about 0 parts by weight per 100 parts by weight of the total resin component (to be cured) to a ma~:imum representing the entire resin component, i.e., lO0 parts by weight per lO0 parts by weight of the resin. A preferred concentration ranges from about 25 to about 95 parts by weight per lO0 parts by weight of the total resin cor.~ponent.

- 1 0 - ' ' '.~` ' .

1~60~36 Combined with the diglycidyl ether based upon linoleic ~ ;~
dimer acid, when of course the resin component to be cured cor~lprises less than 100 parts by weight of the diglycidyl ether based upon linoleic dimer acid, is a suitable elasto~
merically modified epoxy resin blend. ~ suitable elastomerically modified epoxy resin blend comprises the react.ion product of about 40 weight percent of a carboxyl terminated acrylonitrile/
butadiene random copolymer having a structural formula of ,CH3 , 3 ;~

2 2, ~ CH2C~I=CHCH-2~5~H2 CII~o c- c~l C~l COOH;
CN CN CN .
containing 2.37 percent carboxyl groups' 18 to 19 percent bound acrylonitrile, having a number average molecular weight of 3200 and a viscosity of 110,000 cps at 27C combined ~;ith about 60 weight percent of a dlglycidyl ether selected from (1) bisphenol A, having a structural formula ~ .
0 ~ CH OH
H2C-CH-C~lz ~ o ~ C ~ -OCH2CH CH2 ~n ~--O~C~OCH2CH-CH2, tJhere n is the number of repeated units in the resin chain, and having an epo~ide equivalent weight of 180 to 195 and (2) bisphenol F, having a structural formula of H2C_cH_oH2~o_~--C~2~_oC~12cH_cH2~o_~~CH2~) ~ ~

/0\
O-CH2CH-CH2 .
where n is the number of repeated units in the resin chain, and ,: ,~, .

.. . . .

l.

havlng an e~oxide equivalent ~eiyht o~ 152 to 167.
The ~lglycidyl ether (60 ~elght percen-t~ of bisphenol A or blsphenol F is typically reacted with the carboxyl ter-minated acrylonitrlle/butadiene random copolymer (40 weight percent) at 300F for 30 m.inutes to yield a desired reaction product or elastomerically Mo~ified epoxy resin blend. lhe desired reaction product or elastomerically modified epoxy resin blend comprises a mixture of the diglycidyl ether of ~ ~ :
bisphenol ~ or bisphenyl F and the adduct of -t~o moles of the diglycidyl ether of hisphenol A or bisphenol F and one mole of the carboxyl terminated acrylonitrile/butadiene copolyrner which is believed to have the following structural formula .
0 ~ OH 0 CH :
H2/C-C~I-C~I2-0 ~ -C ~ -OCH2CH C~I2-OC-CH2CH2C ~ CH2CH=CHCH
R CN
. .;
tCH3 0 OH R 0 2 ,H ~ oC ~H2CH2-c-ocH2cH-cH2-o ~ -C ~ 2 2' CN CN R
where R is a radical selected from H and CH3.
~hen the diglycidyl ether of bisphenol ~ is employed .. . .
as the reactant, the resultant desired reaction blend or mixture has an epoxide equivalent weight of 335 to 355, a viscosity of Y-Z (Gardner-Holdt, 80% N.V. in methyl cellosolve [methoxy :
ethanol~), and an acid value of less than 0.2 (number of milli-20 grams of KOH neutralized per one gram of the reaction resin :~
blend). ~-~hen the diglycidyl ether of bisphenol F is ernployed ~ ~
as the reactant, the resultant desired reaction blen~ or ~:.
mixture has an epoxide equivalent weight of 285 to 305, a .;~ :
viscosity of X-Y `~

..,; :,:`
'`.' ' ~:
', '. "

: ,: ' : ~ 12 -. . . -106~36 :

(Gardner-Holdt, 80% N.V. in methyl cellosolve), and an acid value of less than 0.2 (milligrams of KOH neutralized per ~;~
one gram of the reaction resin blend). , The concentration of the above-described elastomerically modified epoxy resin blend ranges from a maximum of about 50 parts by weight per 100 parts by weight of the resin component down to zero (where for example the resin component comprises essentially all of the diglycidyl ether based upon linoleic dimer acid). A preferred concentration range however ranges from about 5 parts to -~
about 50 parts by weight per 100 parts by weight of the resin component.
The resin component may also comprise a remainder -o~ a suitable diglycidyl ether selected from a diglycidyl ether of bisphenol A, a diglycidyl ether of bisphenal F or a mixture of the two. Again, it is, of course, understood that such a remainder is dependent upon the amounts of `
the other epoxy-group containing materials of the resin component. The diglycidyl ethers of bisphenol A are described in terms of their viscosity or softening point, ;~
epoxide equivalent weight and hydroxyl content. Again, the epoxide equivalent weight is defined as the number of grams of resin containing one gram equivalent of ~ `
epoxide. The hydroxyl content is defined as the number of equivalents of hydroxyl groups contained in 100 grams of `~
resin.
Some typical suitable diglycidyl ethers of bisphenol A resins are those having an epoxide equivalent weight of 170 to about 4000. Some typical examples of these epoxy resins are (1) DER ~31 which is a trademark product `
of Dow Chemical Company and which is an epoxy resin having ~ ' ~ -13-, .

~L~)60~3~;

an epoxide equivalent ~eiyht of 182 to 190 and a viscosity of 10,000 to 16,000 cps; (2) Epon ~ 836 which is a trademark product of Shell Chemical Company and which is an epo~y resin having an epoxide equivalent weight of 280 to 350, a softening point of 40 to 45C and a hydroxyl content of 0.21; (3~ Epon ~ ~
1001 which is a trademar~ product of Shell Chemical Company ;~ -and ~hich is an epoxy resin having an epoxide equivalent weight of 450 to 550, a softening point of 65 to 74C and an hydro~yl content of 0.28; (4) Araldite ~ 6097 which is a trademark :
product of Cioa-Geigy Corporation and which is an epoxy resin having an epoxide equivalent weight of 2,000 to 2,500 and a `~
softening point of 125 to 135C; t5) Epon C) 1009 which is a : traaemark product of Shell Chemical Company and which is an epoxy resin having an epoxide equivalent ~7eiyht of 2,500 to 4,000 and a softening point of 1~5 to 155C.
Some typical suitable epoxy resins incorporating :
tetra~roll;obisphenol A (3,3',5,5'-tetrabromo-4,4'~isopropylidene-diphenol) to impart fire retardancy to the cured composite are the diglycidyl ethers of tetrabromobisphenol A having a 20 structural formula ~ :
0 Br CH3 Br 0\ :

(3) CH2-CH-CH2-0 ~ C ~ 0 C~2 2' ;~
Br CH3 r and epoxy resins containing both bisphenol A and tetrakron~.o- ;
bisphenol A having a structural formula ... - .

f 2 C CH2 tO~--C~--O--CH2- CH- C112~- ~

~ CH3 /0\ ~ .

o ~ -C ~ 2 2' '!..

3 `

, c -- 1 ~
'' ' :. , . . . : . . -~ ~ :
60~3~
where n is the number of repeated units in the resin chain and X is either bromine or hydrogen depending upon the method of manufacture of the epoxy resin. Some typical - suitable diglycidyl ethers of tetrabromobisphenol A resins are (1) DER ~ 542 which is a trademark product of Dow Chemical Company and which is an epoxy resin havlng an epoxide equivalent weight of 325 to 375, a softening point of 45 to 55C and a bromine content of 44-48% by weight and -~
l2) Epi-Rez 3 163 which is a trademark product of Celanese Corporation and which is an epoxy resin having an epoxide 10equivalent weight of 350 to 450 and a bromine content of 50~ -~
by weight. Typical examples of suitable epoxy resins containing both bisphenol A and tetrabomobisphenol A are ,`
(1) Epon~ 1045 which is a trademark product of Shell Chemical Company and which is an epoxy resin having an epoxide equivalent weight of 450 to 500 and a bromine content of 19% by weight and (2) Araldite~ 8011 which is a trademark `
product of Ciba-Geigy Corporation and which is an epoxy , ::
resin having an epoxide equivalent weight of 455 to 500 and a bromine content of 19-23% by weight.
The diglycidyl ethers of bisphenol F are described in terms of their epoxide equivalent weight. Some typical -suitable diglycidyl ethers of bisphenol F resins are those having an epoxide equivalent weight of 165 to 180. ;
The resin component is then combined with a curing agent component to form the curable mixture (reaction --~
mixture). A curing agent is one selected from (a) a -suitable acid anhydride, (b) a suitable polyaminer (c) a ~;
mixture of the acid anhydride and the polyamine, (d) a :~
mixture of the acid anhydride and a suitable carboxylic acid and (e) mixtures of the foregoing.

; ~ '.' ':, -15- -~

1~)60136 Typical suitable anhydrides are chlorendic anhydride, the maleic anhydride adduct of methylcyclopentadiene [a light yellow semiviscous liquid with a viscosity of 138.4 cps. at 25C (available commercially as "Nadic Methyl Anhydride")] havin~ a ; ;~
structural formula H3~>

phthalic anhydride, citraconic anhydride, glutaric ;~
anhydride, maleic anhydride, and mixtures thereof. Other .
typical anhydrides which may be employed are described in .
U.S. Patent No. 3,329,652.
The total concentration of the uncombined acid anhydride curing agent ranges from a minimum of about .. :
16 parts by weight to about 60 parts by weight per 100 parts : ;~
by weight of the resin component. An anhydride to epoxide `~
molar ratio of 0.6 to 0.9 yields the optimum adhesive properties of the cured polymer. ~ .
Typical suitable polyamines include dicyandiamide, metaphenylenediamine, hexamethylenediamine, triethylenetetra amine, polyoxypropylenediamine having a structural formula of (6) CIH3 ,3 (H2NCH-cH2-[ocH2cH ~nNH2, .~ ;
where n is about 2), and -polyoxypropylenetriamine havln~ a structural formula of -.
~, '~ :

, :. :; :.: , . . . . -. : ~ : . , ~ : ;:

L36 `~
(7) C~l3 ~ ~
c~2-LCll2cH 3X NH2 ~ C~13 ~ ~

(~12C-CH2 C-CH2- LC~I2CH 1yNH2 ¦ 3 CH2-~OCH2CH-~z NH2 where x ~ y + z = 5.3).
The polyamine curing agent i5 typically combined to give equimolar concentrations of amine hydrogen and epoxide. It has been found that a mixture of the ~;~
polyamine and a suitable acid anhydride such as glutaric anhydride, maleic anhydride, citraconic anhydride, etc., can also be employed where the acid anhydride is present ~ ~
in the mixture in an amount ranging up to about 10 parts -by weight per 100 parts by weight of the resin component.
Typical suitable carboxylic acids which may be combined with the acid anhydride curing agent are linoleic dimer acid having a structural formula of ~ .
(8) 0 (HO~C) C-OH), CH2 ~ 2)7 H2CH=CH(CH2)4CH3 ~ _ ~ (CH2)5C~3 linoleic trimer acid having a stoichiometry of C54H9606, an acid value of 145 to 185 and an average molecular weight of about 810, aza~eic acid having a structural formula of g ) O O ,, (HOC-(CH2)7-C-OH), and a carboxyl terminated acrylonitrile/butadiene random ~

copolymer selected from one having a structural formula of ~ -, `'~

6~)~36 (10) '~

CH3 CH3 ;~ ~;
Hooc_cH2CH2C --CH2CH=CHcH2--5CH2CH 10 , 2 2 CN CN CN
containing 2.37 percent carboxyl groups, 18 to 19 percent `
bound acrylonitrile, having a number average molecular weight of about 3200 and a viscosity of 110,000 cps at 27C;
and one having a structural formula o~
(11 ) ,CH3 CH3 2 2, {~ 2CH CHC~2-5CH2CH~lo (cHcH2)c-cH2cH2cooH ~ ~;
CN CN COOH CN ;;~
containing 2.93 percent carboxyl groups, 18 to 19 percent bound acrylonitrile, having a number average molecular `~
weight of about 3400 and a viscosity of 125,000 cps at 27C. !~1 The carboxylic acid concentration present in an acid anhydride-carboxylic acid curing agent mixture ranges up to about 20 parts by weight per 100 parts by weight of the resin component combined with about 20 to about 60 parts by -;
weight per 100 parts by weight of the resin component of the `
acid anhydride. ~ -It is, of course, to be understood that the selecte.d curing agent can be combined with other type curing agents or accelerators therefor, e.g., an amine such as benzyldimethylamine. It is also to be understood that conventional filler materials, such as aluminum oxide, silicon dioxide, titanium dioxide and flame retardant `
additives such as antimony trioxide may also be added to the resultant resin-curing agent reaction mixture.
The mixture of epoxy resin and curing agent may then be heated to attain homogenization, complete liquification and initiate a partial cure, e.g., typically at ~" .. - .. , ., . . . .. . , . , . . ., :
~-,.,;: - : . , . '.
::: . . ..

6~3~ ~

50-lQ0C for 5 to 60 minutes. It is to be noted that, when ~;
physically expedient to do so, the mixture may be used without a pre-cure heat treatment. Also, alternatively, the reaction mixture may be dissolved in a suitable solvent, ~;
e.g., acetone.
Referring to the Figure, a sui-table substrate or base 21 is selected. A suitable substrate or base 21 may comprise any material which is compatible with the ;
epoxy resin with which it is destined to be coated and ~-which resin is destined to be cured. For printed circuit ~-manufacture, the substrate 21 may be of a rigid material, e.g., glass, metal, etc., or of a flexible material, e.g., a polymer or plastic, e.g., a polyester. Applied to a surface 22 of the substrate 21 is the curable mix-ture comprising the resin component, the curing agent component and any solvents, ;
fillers or additives. The mixture may be applied to the surface 22 by any conventional means, e.g., spraying, ;~-dipping, spinning, etc., whereby a coat or layer 23 thereof forms. The layer 23 may be of any desired thickness, typically it may range from 0.5 to 20 mils thick.
The coated substrate 21 is then heated under conditions of time and temperature, e.g., typically ranging ~;
from 5 to 60 minutes at 140-170C, whereby a fully cured epoxy polymer results. By a full cure one means that the epoxy groups originally present have been consumed during the curing reaction and the degree of cross-linking provides optimum physical properties for the desired application.
For the desired time and temperature relations ascribed to above infrared spectroscopy shows that the anhydride and epoxy groups have been consumed. In addition, the epoxy polymer no longer flows when submi-tted to a heat and pressure cycle.

-19- `;

., . ' ' !
':
.'' ' ~" ' ' , ' ' ~ ' ~O~ L3~

It is, of course, to be understood that the ~.
time and temperature curing parameters are interdependent -~
and that variations in the temperature will require variations in the time whereby optimum results will be attained. In this regard, the various cur:ing parameters and i ~;~
~ -,, , their independency are well known in the a;rt, and their i ;
interaction between one another is also we:ll known or can be . .
easily ascertained experimentally by one skilled in the art in the light of the subject invention disclosed herein. ;`~:
A suitable species is then deposited on a .
surface 24 of the cured epoxy layer or coat 23. A suitable species may be any of a multitude of materials well known in the art which can be deposited upon a cured epoxy surface and comprises in part conventional aqueous or organic based paints, lacquers, inks and adhesives, aqueous or non-aqueous ;
solutions of inorganic salts, aqueous or non-aqueous ~ .
electroless metal deposition solutions and the metal deposits resulting therefrom, metals, etc. The suitable species may be deposited or applied to the cured epoxy surface 24 by any standard means known in the art including dipping, brushing, spray coating, spin coating, vapor i.
depositing, electroless depositing with or without electrodepositing, sputtering, etc~
It is to be noted and stressed at this point that unlike prior epoxy formulations and methods of ;~
metallization thereof, the virgin epoxy disclosed in this invention, i.e~, the cured epoxy which results (which~
i.ncludes aged material and/or reconstituted from scrap material), does not have to be pretreated (etched, solvated, ; ;
sand blasted, etc~) -to be rendered hydrophilic to ach:ieve adherent electroless metallization (as well as adherent ~.

---`` 10~;0~36 ~:

electrodeposited metallization) to a surface thereof. This is a surprising and unexpected property of the epoxy disclosed herein and the method employed in its metallization.
The selected species-deposited, cured epoxy surface 24 is then thermally aged or post baked for a period of time sufficient to insure adequate adhesion of the `~
selected species to the cured epoxy surface, e.gO, an -adequate adhesion typically being represented by a metal deposit (electroless and electro) evidencing a peel strength of at least 5 lbs./linear in. at 25C. The thermal aging typically may be as low as a temperature of 120C for 10 minutes or as high as 180C for one hour. ~gain, it is to ~ ~
be understood and stressed that the above temperature and ;
time parameters are all interdependent and that variations `~
in temperature will produce variations in the other parameters whereby optimum results will be attained. In this regard, the time-temperature adhesion parameters can `~
be easily ascertained experimentally by one skilled in the art in view of the subject invention disclosed herein.
Where the selected species is an electrolessly deposited metal, a standard electroless -technique may be employed. Again, it is to be pointed out that the cured epoxy surface 24 is a virgin surface in that it has not been etched, roughened, solvated, swell-etched, etc., to render the surface more receptive to electroless `
plating sensitizing, activating and plating solutions, such ;~
an expedient being unnecessary. A typical electroless ~ `
.;. , .
technique which is illustrative only and not restrictive is as follows. The cured epoxy surface 24 is thoroughly rinsed , :
-21- ~

` ~'' ', '` '' ~

'; ' ., ', ' ,,'~ ~ . .~.' ' '.','; ' ' ' . . ' ' ' ' , ' ~6~L36 :~
with water or any other suitable cleaning agent. Proper ;~
rinsing is essential in order to remove essentially all contamination, such as contaminating particles, etc., so as - not to contaminate a sensitizing, an activating and an electroless plating solution to ~hich the epoxy surface 24 is destined to be subjected. Contamination, particularly of the plating bath, is undesirable because the stability of ;;
such plating baths is frequently adversely affected by such ~
a condition. ~ ~ `
After rinsing, the cured epoxy surface 24 is `~
then sensitized. Sensitization consists of depositing or absorbing on the epoxy surface 24 a sensitizing species, e.g., Sn 2 ions, which is readily oxidized. Conventionally, ;
the cleaned surface 24 is dipped into a standard sensitizing solution, e.g., aqueous stannous chloride with a supporting medium such as HCl, ethanol, ethanol and caustic, or ethanol and hydroquinone. It is to be understood that the ~ensitizing solutions and the conditions and procedures of ~ "
sensitizing are well known in the art and will not be 20 elaborated herein. Such sensitizers and procedures may be found, in part, in Metallic Coating of Plastics, William ~: .
; Goldie, Electrochemical Publications, 1968.
After sensitizing, the sensitized epoxy ; surface 24 is rinsed, then activated. It is to be noted that it is important that the sensitized surface 2~ be ~
rinsed thoroughly in a cleaning medium, e.g., deionized ~ `
- water, after sensitizing. If such is not done, there is a possibility that excess sensitizer on the surface will cause reduction of an activating species, e.g., Pd+2, to which the sensitized surface is destined to be exposed, in non-adherent form on the surface 24. Activation relates to providing -22~

.~ , , - ~ . . , ~6~)~3~
" , . ~;
a deposit of a catalytic metal, e.g., Pd, over the surface of the cured epoxy polymer, ln sufficient quan-tities to successfully catalyze a plating reaction once the surface ~-24 is introduced into an electroless plating bath. The sensitized surface 24 is exposed to a solution containing -the activating species, e.g., a noble metal ion, wherein the ; ~ -sensitizing species is readily oxidized and the noble metal ion, e.g., Pd+2, is reduced to the metal, e.g., Pd, which ;
in turn is deposited on the cured epoxy surface 24. The deposited activating metal, e.g., Pd, acts as a catalyst for localized fur-ther plating. Again, it is to be understood that the various activating metal ions and their solutions,~
the conditions and procedures of activation are well known in the art and will not be elaborated herein. Such ~ ;
activators and procedures may be found, in part, in Metallic Coatinq of Plastics, previously referred to. ~;
. . .
After the activating step, the activated `
epoxy surface 24 is rinsed with deionized water and then immersed in a standard electroless plating bath containing a metal ion, e.g., Cu+2, destined to be reduced by the ;~
catalytic metal species, e.g., Pd. The metal ion, e.g., Cu 2, ;
is reduced by the catalytic metal, e.g., Pd, and is electrolessly deposited on the polymeric surface 24 to form a metallic, e.g., Cu, layer or deposit 26 (referring to the Figure). Again, it is to be pointed out that the electroless -baths, the electroless plating conditions and procedures are well known in the art and will not be elaborated herein. ~`
Reference is again made to Metallic Coating of Plastics, previously referred to, for some typical examples of electroless baths and plating parameters. It is to be noted that in some cases, it is possible to combine the :~ .

-~ 136 . ~ .
sensitizing and activatlng steps ~.
into one step. The electroless metal-deposited, cured epoxy composite is then thermally aged, e.g., at 110 to 180C for -~
10 to 60 minutes whereby an adherent electroless metal deposit is attained. It is to be noted that the electroless metal deposit may be subjected to a conventional electroplating treatment whereby it is built up. In such a situation, it is, of course, understood that there may be an additional thermal aging or post bake or just one thermal aging, after the final electroplating treatment.
A preferred method of electrolessly depositing a metal on the resultant cured epoxy surface is the method revealed in U.S. Patent No. 3,562,005, assigned to the assignee hereof. The preferred method entails applying a photopromoter solution to the surEace 2~ utilizin~
procedures revealed in U.S. Patent No. 3,562,005. A
photopromoter is defined as a substance which, upon being exposed to appropriate radiation, either ta) dissipates chemical energy already possessed thereby or (b~ stores chemical energy not previously possessed thereby. When ;-the substance possesses or has stored chemical energy it is capable of promoting, other than as a catalyst, a chemical reaction whereby it, the photopromoter, undergoes a chemical change in performing its function (unlike a catalyst). The resultant photopromoter-covered, cured epoxy surface 2g may then be rinsed with deionized water (depending on the type of photopromoter employed) and is ~-then dried. The photopromoter-coated surface 24 is then selectively exposed to a source of ultraviolet radiation, -through a suitable mask, to form at least one region which is capable of reducing a precious metal from a precious . . - . . . .
,. ~ .

6~)136 metal salt, e.g., PdC12. The region so capable is exposed to -the precious metal salt, e.g., `~
PdC12, whereby the precious metal salt is reduced to the - precious me-tal, e.g., Pd, which in turn is deposited thereon.
The precious metal-deposited region is then ~`
exposed to a suitable electroless mekal plating bath, e.g., copper, wherein the metal, e.g, copper, is pla-ted on the region forming an adherent metal deposit or layer 26 on the cured epoxy surface 24. The electroless metal-deposited i;
cured epoxy surface 24 is then thermally aged or post baked, ~` `
e.g., typically at 110 to 180C for 10 to 60 minutes, whereby an adherent electroless metal deposit 26 is ~-attained. It is to be noted that the electroless metal deposit may be subjected to a conventional electroplating treatment whereby the electroless metal deposit is built up.
In such a situation, it is again to be understood that there ~ `
may be an additional thermal aging or just one thermal aging, after the electroplating treatment.
A suitable photopromoter soluiion may be either a positive type or a negative type as discussed in .
U.S. Patent No. 3,562,0~5. A suitable mask, either positive or negative, depending on whether the photopromoter is positive or negative, is one as discussed in U.S. Patent No. 3,562,005, and typically comprises a quartz body having a radiation opaque pattern thereon. The ultraviolet radiation source is a source of short wavelength radiation (less than 3,000A, and typically about 1,800A to about "~
O ~ : -2,900A).

EXAMPLE I

An epoxy resin-curing agent mixture (liquid) was prepared in the following manner. One hundred fifty : ~ `,:, : . .... . . . .. . .

~L~6[)~36 yrams (75 parts by weisht per 100 parts by welght of the resin component of the mixture) of a commercially,obtained epoxy resin, the adduct of two moles of the dislycidyl etIIer of bisphenol A (epoxide equivalent weight of 180 to 195) and one ;~
mole of linoleic dimer acid having the structural formula O\C~I3 OII ~"
, H2C-(~CH2-o~ ~-0CH2CH-CH2-0--~ , H -C ~ -0~I:2CH-CH2~ , ~

C~2)7 (CH2)7 3 , ,.~ ;
;'' ':;, ~\ ~ (C~I2) -CH

and an epoxide equivalent weight of 650 to 750 was combined ' ~.:
with 50 g.rams (25 parts by weight per 100 parts by weight of :~
the resin component) of a cormercially obtained, custom-10 synthesized elastomerically modified epoxy resin blend comprisins ,.~
the reaction product of a mixture comprising (1) 40 we~ight ~ :
percent of a carboxyl terminated acrylonitrile/butadiene random copolymer having a structural formula of : ; :
CH3 , 3 Hooc-cH2CI~2-C ~ CH2C~I=c~lc~l2)5cH2c~l ~ oC-c'~I2cH2 C~ CN CN
containing 2.37 percent carboxyl groups, 18 to 19 percent bound acrylonitrile, having a number average molecular weight of 3200 and a viscosity of 110,000 cps at 27C and (2) 60 weight percent of a diglycidyl ether coMprising bisphenol ~ having an ' epoxide equivalent weight of 180 to 195. The mixture had been ~ :
20 heated at 300~ for 30 minutes to yield a reaction product or blend having an epoxide ?~ :

':

.36 ., :
equivalent weight o~ 335 to 355, an acid value or number of less than 0.2 ~illigram of KOH/gram of reaction product, and `
a viscosi-ty of Y-Z (Gardner-Holdt 80~ N.V. in methyl `~
cellosolve [methoxy ethanol]). ~ ~ -To the resin component was added 40 grams of ; ~
, ~. , .
chlorendlc anhydride (20 parts by weight per 100 parts by weight of the resin component) and 5 grams of phthalic anhydride (two and one-half parts by weight per 100 parts by weight of the resin component) to form the epoxY resin-curlng agent mlxture. The resultant mixture was then heated to liquifaction at 60C for 30 minutes. i -~
Referring to the Figure, a commercially obtained ;~
epoxy-glass laminate was employed as a substrate 21.
The liquified epoxy resin-curing agent mixture was applied ` ;
to a surface 22 thereof, using a conventional means, to form an epoxy (partially cured) layer 23 thereon ~0.5 to 2 mils thick). The coated substrate 21 was then heated at 150C for 30 minutes to obtain a fully cured epoxy layer or coat 23 as evidenced by infrared spectroscopy which revealed a disappearance of anhydride and epoxide functional groups.

The fully cured epoxy-coated substrate 21 (virgin epoxy coated) was then sensitized by immersion in a `
conventional aqueous hydrous oxide tin sensitizer ~a 3.5 weight percent SnC12.2H20 and 1 weight percent SnC14.5H2O
aqueous solution) for one minute at 25C, activated in a .05 weight percent aqueous PdC12 solution by immersion therein for 30 seconds, water rinsed for two minutes and then ~ ~
:',' ,:
immersed in a commercially obtained electroless copper ~-plating bath to deposit an electroless copper layer 26 on the epoxy layer 23. The electroless copper layer 26 was then subjected to a conventional electroplating to obtain a :~ , . , .- . . ,. , , ; . . . : :
.:~: . . . - ; : - : , . ,,. : - - .

36~1136 ~-1.5 mil thick copper layer 26 and thereby form a laminar ;~
article comprising a metal (Cu) layer 26 deposited on an ~ ;
epoxy layer 23. The electroplated deposited substrate 21 was the~ heated or baked at 120C for 10 minutes. -A peel strength measurement of the deposited metal was undertaken at a 90 peel at a rate of two inches per minute employing a conventional peel testing apparatus. ; ;~
The peel strength was 14.3 lbs./linear inch at 25C. At 90C the peel c.trength value was 1.1 lb~/linear inch. For ;~
printed circuit manufacture a peel strength of 5 lbs./linear inch at 25C is adequate.
EXAMPLE II
The procedure of Example I was repeated except that the resin component of the mixture comprised the following:
(a) 30 grams ~30 parts by weight/100 parts ~
by weight of the resin component) of the adduct of two moles ~ ; ;
of the diglycidyl ether of bisphenol A having an epoxide equivalent weight of 180 to 195 and one mole of linoleic ;
dimer acid (of Example I);
(b) 30 grams (30 parts by weight/100 parts by weight of the resin component) of the reaction product or ;~
elastomerically modified epoxy resin blend resulting from ;
combining 40~ by weight carboxyl terminated butadiene/
acrylonitrile random copolymer and 60% by weight of the . . ~ ,.:
diglycidyl ether of bisphenol A having an epoxide equivalent weight of 180 to 195 [of Example I]; and (c) 40 grams (40 parts by weight/100 parts by weight of the resin component) of a brominated diglycidyl ether of bisphenol A, commercially obtained, having an epoxide equivalent weight of 450 and 500 and containing ...

0136 `~

18-20~ by ~eight of bromine and having the s-tructural formula previously described and designated as structural formula (4), ~ -above, ~ ;

C~2 - Ci~- C112--EO ~ - C ~-0 C~12 CH_ci l 2 ~ ~--C~
x CH3 _ n 3 O :: :
OCH2-CH-C'~I2' ' where n = number of repeated units and x = H or Br.
l'he resin component was combined with a curing agent component comprising 30 grams (30 parts by weisht/100 parts by weight of the resin component) of chlorendic anhydride and 16 grams (16 parts ~y weight/100 parts by weight of the resin component) of an auxiliary anhydride comprising the adduct of ~: , .
methylcyclopentadiene and rlaleic anhydride having a structural ~ ;
formula designated as structural formula (5), above.

/ IH C ~ ;~
_~O ;` :

,~
The combined components of resin and curing agent .
were not heated prior to applyins the mixture to the substrate 21. Again the epo~y resin-curing agent coated substrate was heated at 120C for 30 minutes to attain a fully cured epoxy as evidenced by an infrared spectrur.l which revealed the disappearance of the anhydride and epoxide functional groups.
A post-bake of 170C for 30 minutes of the metaI-deposited substrate 21 was undertaken.

~ ' - 29 - ~

Peel strengths of 2.6 to 3.7 lbs./linear inch at 0C, 9 to 10 lbs./linear inch at 25C and 5 to 7 lbs./linear inch at 90C were obtained.
EXAMPLE III
The procedure of Example I was repeated except that the resin mixture comprised:
(a) 40 grams (40 parts by weight/100 parts by weight of the resin component) of the adduct of two moles of the diglycidyl ether of bisphenol A having an ~poxide equivalent weight of 180 to 195 and one mole of linoleic dimer acid (of Example I); ~ ;
(b) 30 grams (30 parts by weight/100 parts hy weight of the resin component) of an elastomerically ~-modified epoxy resin blend comprising the reaction product resulting from the reaction at 300F for 30 minutes of (1) , .
40 weight percent of the carboxyl terminated acrylonitrile/butadiene copolymer of Example I and (2) 60 weight percent of the diglycidyl ether comprising bisphenol F having an epoxide equivalent weight of 152 to 167 (the reaction product or elastomerically modified epoxy resin ,~
blend having an epoxide equivalent weight of 285 to 305, an acid value of less than 0.2 milligrams of K~H per one gram of the resultant reaction blend and a viscosity of X-Y
[Gardner-Holdt, 80% N.V. in methyl cellosolve]); and ~`
. .
(c) 30 grams (30 parts by weight/100 parts by weight of the resin component) of the brominated diglycidyl ether of bisphenol A (of Example II).
The resin mixture was combined with a mixture ~
comprising: -; 30 (a) 20 grams (20 parts by weight/100 parts by weight of the resin component) of chlorendic anhyclride curing agent;

, ~; , ~.

. . :,: : : ~ : ::

L0~0~.3~ ~ ~

(b) 10 grams (10 parts by weight/100 parts by weight of the resin component) of the adduct of methylcyclopentadiene and maleic anhydride lof Example II, above] curing agent; ,;
(c) 10 grams (10 parts by weight/100 parts ;
by weight of the resin component) of citraconic anhydride -curing agent;
(d) 1 gram of benzyldimethylamine curing agent accelerator; and . ::, (e) 2 grams of antimony trioxide.
,-, : ,, ,~, .. .
The combined components were then directly applied to the substrate 21 and fully cured at 150C for one hour. The peel strength obtained (af-ter the post bake of ~;
the metal-deposited substrate 21 (laminate) was 8 lbs./
linear inch a-t 25C.
EXAMPLE IV ~-The procedure of Example I was repeated except ~ ;
that the resin mixture comprised~
(a) 30 grams (28.8 parts by weight/100 parts by weight of the resin component) of the diglycidyl ether of linoleic dimer acid, commercially obtained, and having the structural formula previously described and designated as structural formula (2), above, i.e., /0\ 0 0 /0\ `.~ ~ -H2C-CHCH2-0-C ,C OCH2CH CH2 ~ ~ ?~

(CH2)7 2)7 2CH CH(CH2)4CH

(CH ) CEI
2 5 3 `~
and an epoxide equivalent weight of 400 to 420; ~;~

(b) 34 grams (32.7 parts by weight/100 parts by weight of the resin component) of the reaction product (300 F, 30 minutes) of 40~ by weight of the carboxyl . . ,, ,., . , . , , , ~, ~L~6~)~L36 ~

terminated butadiene/acrylonitrile copolymer and 60~ by weight of the diglycidyl ether of blsphenol A having an epoxide equivalent weight of 180 to 1~5 [o:E Example I]; and (c) 40 grams (38.5 parts by weight/lOQ parts by weight of the resin component) of the brominated :
., ~ ", diglycidyl ether of bisphenol A (o~ Example II).
The resin mixture component was combined with a mixture comprising~
(a) 25 grams (24 parts by weigh~/100 parts by weight of the resin component) of chlorendic anhydricle .`
curing agent;
(b) 25 grams (24 parts by weight/100 parts ~
by weight of the resin component) of the adduct of ..
methylcyclopentadiene and maleic anhydride [of Example II, above] curing agent; and (c) one gram of a curing agent accelerator, commercially obtained, having the structural formula OH

(CH3)2NCH2 ~ 2 ( 3)2 ~H

2 ( 3~2 The combined components were then directly applied to the substrate 21 and fully cured at 150C for 30 minutes. The peel strength obtained (after the post bake of the metal-deposited laminate) was 8 lbs./linear inch at 25C. ~:
EXAMPLE V
The procedure of Example I was repeated except ; ~;~
that the resin component of the mixture comprised the following: :

~0~i()13~
... . .
(a) 750 grams (17 parts b~ weight per 100 parts by weight of the resin component) of the diglycidyl ~:
ether of linoleic dimer acid having the structural forrnula :
-to\ O O /o ,: -,,H2C-CH-CH2-0-C C-O-CH2CE~-CH2l (CH2)7 ( 2)7 :
< ~ H2cH=cH-(cH2)4 CH3 ~ (CH2)5-CH3 ~
and an epoxide equivalent weight of 400 to 420; ~ :
(b) 1250 grams (28.5 parts by weight per ~
,~ , , 100 parts by weight of the resin component) of the adduct of two moles of the diglycidyl ether of bisphenol A having an ,:
epoxide equivalent weight of 180 to 195 and one mole of linoleic dimer acid (of Example I); and (c) 2400 grams (54.5 parts by weight per ~i 100 parts by weight of the resin component) of the :
brominated diglycidyl ether of bisphenol A (of Example II).
. .
The resin mixture was combined with a mixture comprising~
(a) 1000 grams (22.7 parts by weight per 100.
parts by weight of the resin componentj of chlorendic anhydride curing agent; ; ~.
(b) 1000 grams (22.7 parts by weight per .` :~
100 parts by weight of the resin component) of the adduct of methylcyclopentadiene and maleic anhydride curing agent (of Example II);
(c) 400 grams (9.1 parts by weight per 100 parts b~ w~ight of the resin component) of a carboxyl terminated butadiene/acrylonitrile random copolymer having a structural formula of `: :
~33-': , , `,,. ' , .
., ' '~

1~6~)~L36 , , ......................................................... , - .

l ~ _ , 3 HOOC-CH2CH2-C~ _ 2 CHCH2 5CH2CH , 10l CH2CH2C
: , containing 2.37 percent carboxyl groups, 18.8 percent bound acrylonitrile, having a number average molecular weight of 3200 and a viscosity of 110,000 cps at 27C;
(d) 200 grams ~4.5 part~ by weight per 100 ~ .
parts by weight of the resin component) of a carboxyl terminated butadiene/acrylonitrile random copolymer having a structural ~ormula of ,CH3 3 HooC-CH CH2C {cH2cH=cHcH2-scH2cH ~ 10(CH CH2~, 2 2 CN CN COOH CN
containing 2.93 percent carboxyl groups, 18 to 19 percent bound acrylonitrile, having a number average molecular weight of 3400 and a viscosity of 125,000 cps at 27C;
(e) 200 grams (4.5 parts by weight per 100 :: . :
parts by weight of the resin component) of a ground mixture comprising 70 parts by weight of antimony oxide and 30 parts by weight of a butadiene/acrylonitrile copolymer containing 33 percent acrylonitrile and having a specific gravity of 0.98 and an average Mooney viscosity of 80; and (f) 50 grams (1.1 parts by weight per 100 parts by weight of the resin component) of benzyldimethyl- ;~
amine. ;
The combined components were then applied to and impregnated a glass cloth having a thickness of about 4 mils and cured at 160C for six minutes and 150C for 15 minutes to obtain a full cure. The peel strength obtalned of the metallized composite, after a 170C bake for 30 `
minutes, was 7 to 9 lbs./linear in. a~ room temperature.
' -34- ~ ~
`

. . , , : : ., , :

1~6~)136 ::

Example VI
:' :
The procedure of Example I was repeated except that the resin component mixture comprised the following~
(a) 1000 grams (50 parts by weight per 100 parts by weight of the resin component) of the adduct of two moles of the diglycidyl ether of bisphenol A having an epoxide equivalent weight of 180 to 198 and one mole of ::
linoleic dimer acid (of Example I); and :
(b) 1000 grams (50 parts by weight per 100 parts by weight of the resin component) of the brominated diglycidyl ether of bisphenol A (of Example II).
The resin componen-t mixture was combined with ;;
a mixture comprising:
(a) 500 grams (25 parts by weight per 100 parts by weight of -the resin component) of the adduct of ~ :
methylcyclopentadiene and maleic anhydride (of Example II);
(b) 300 grams (15 parts by weight per 100 parts by weight of the resin component) of chlorendic anhydride; ~ :
(c) 240 grams (12 parts by weight per 100 ~
parts by weight of the resin component) of a carboxyl `~ ;
terminated butadiene/acrylonitrile random copolymer having a number average molecular weight of 3200, containing 2.37 percent carboxyl groups and 18 to 19 percent acrylonitrile, :
having the structural formula ~`
,CH3 1 3 Hooc-cH2-cH2-c~H2cH=cH-cH2-5cH2cH~loc-cH2cH2cooH;
CN CN CN ~; , (d) 200 grams (10 parts by weight per 100 parts by weight of the resin component) of the tri-carboxylic ~ :

~.

6~)13~i ~

acid obtained from the trime~ization of linoleic acid having - a molecular weight of approximately 810 and an acid value of 145 to 185 and a stoichiometry of C54H9606;
(e) 66 grams (3.3 parts by weight per lQ0 parts by weight of the resin component) of a paste made by grinding mixture of 60 parts by weight of antimony oxide and 40 parts by weight of the diglycldyl ether of bisphenol A having an epoxide equivalent weight of 180 to 195; and (f) 20 grams (1.0 part by weight per 100 parts by weight of the resin component) of benzyldimethylamine. ~; ;
The combined components were applied to and impregnated a glass cloth having a thickness of about 4 mils ;
and cured at 150C for 20 minutes to give a fully cured composite. The peel strength, obtained after a bake at 170C
for 30 minutes of the resultant copper-epoxy composite was 16 to 20 lbs./linear in. at room temperature. ;
EXAMPLE VII ~
~ ~
An epoxy resin-amine curing agent solution was prepared in the following manner. One hundred and fifty grams of the adduct of two moles of the diglycidyl ether of bisphenol A having an epoxide equivalent weight of 180 to 195 and one mole of linoleic dimer acid (of Example I) was combined with 6.2 grams of hexanediamine, 50 ml. of xylene and 100 ml. of acetone. A 4 mil thick glass cloth (commercially obtained) was immersed into the solution and allowed to drain. The impregnated or coated cloth was then fully cured at 140C for one hour. The fully cured epoxy-glass was then metallized as described in Example I ~`
and baked at 120C for 10 minutes. A peel strength measurement of the deposited copper metal (90C peel at two ~ ;~

:
' . : `,' :~;

inches per minute) gave a value of 8 lbs./llnear in. at room temperature.
E XAMP LE V I I I ~ , A commercially obtained epoxy-glass hardboard ;~

was coated, to form a layer 0.5 mil thick, with an epoxy j ~ :
resin-curing agent solution comprising (a) 550 grams ``
of the epoxy resin comprising the adduct of two moles of the diglycidyl ether of bisphenol A having an epoxide equivalent weight of 180 to 195 and one mole of linoleic dimer acid (of ~ ~ -Example I), Ib) 16.2 grams diethylenetriamine, (c) 150 ml.
of xylene and (d) 300 ml. of toluene. The coated epoxy~
glass hardboard was allowed to cure under ambient conditions for one day. The cured board was then metallized as described in Example I and then baked at 140C for one hour. A peel value of 8 lbs./linear in. was obtained.
EXAMPLE IX
_ One hundred and fifty grams of the adduct of two moles of the diglycidyl ether of bisphenol A having an epoxide equivalent weight of 180 -to 195 and one mole of linoleic dimer acid (of Example I) was combined with (a) 3 ;;
grams of diethylenetriamine, (b) 25 grams of a polyoxy- ~;
propylenediamine having an approximate molecular weight of 1,000 and a structural formula of `

,CH3 ,CH3 H2NCH-[CH2-OCH2CH-]nNH
where n = 15.9, (c) 50 ml. of xylene, (d) 75 ml. of isophorene and (e) 100 ml. of acetone. A commercially `
obtained epoxy-glass hardboard was coated with the resultant ~ ;
epoxy resin-curing agent solution to form a layer 2 mil ~ ;

thick. The coated board was allowed to cure at ambient conditions for one day and then metallized as described in ., -37- ~
, .

0~L3~

Example I. The copper-deposited sample was then baked at 140C for one hour. A peel strength of 12 lbs./linear in.
was obtained at room temperature.
EXAMPLE X
The procedure of Example IX was repeated except that there was a bake at 140C for 30 minutes prior;~
to metallization and a bake after metallization of 140C for one hour. The peel value obtaind was 8 lbs./linear ln. ~ ~
EXAMPLE XI ~.,~;.
The procedure of Example I was repeated except ~ ;
that 125 grams of the adduct of two moles of the diglycidyl ether of bisphenol A having an epoxide equivalent weight of 180 to 195 and one mole of linoleic dimer acid (of Example I) was col~ined with (a) 12.2 grams of a polyoxypropylenetriamine having an approximate molecular wei~ht of 403, having a structural formula CH 2 ~ CH2 CH~XNH2 ~: :
CH3CH2 ( ' CH2~0CH2 CH~yNH2 I , 3 CH2-~OCH2CH-]zNH2, where x + y + z = 5.3, and (b) 125 grams of toluene. An epoxy-glass hardboard, commercially obtained, was coated with the resultant solution and cured at 120C for one hour.
The fully cured board was then metallized as described in Example I and baked at 120C for 10 minutes. The resultant peel value was 7.5 lbs./linear in. at 25C.
,~~ EXAMPLE XII -~
The procedure of Example I was repeated except that 75 grams of the adduct of two moles of the . ~,. :

: ~; . , . . : : , . -. , . ' ' .,;: . ,- .:. ;, . , ,~ .
... . . . . . . . .

1~)6~36 diglycidyl ether of bisphenol A having an epoxide equivalent weight of 180 to 195 and one mole of linoleic dimer acid (of Example I) was combined with (a) 25 grams of a reaction mixture (300F for 30 minutes) comprising (1) 40 parts by weight of a carboxyl terminated butadiene/acrylonitrile -copolymer (of Example VI) having a number average molecular weight of 3200, and (2) 60 parts by weight of a diglycidyl ether of bisphenol A having an epoxide equivalent weight of 180 to lq5, (b) 12 grams of a polyoxypropylenetriamine (of ~;
Example XI), and (c) 25 grams of xylene. An epoxy-glass hardboard was coated with the resultant solution and cured at 120C for one hour. The fully cured board was then metallized as described in Example I and baked at 170C for 30 minutes. A peel value of 6 lbs./linear in. at 25C was obtained.
EXAMPLE XIII ;
The procedure of Example I was repeated except :.
that the resin component comprised:
(a) 24 grams of the reaction product (at 300F for 30 minutes) of (1) 60 weight percent of the ~`
diglycidyl ether of bisphenol A having an epoxide equivalent `~
weight of 180 to l9S and (2) 40 weight percent of a carboxyl terminated butadiene/acrylonitrile copolymer (of Example VI) having a number average molecular weight of 3200, and (b) 80 grams of the diglycidyl ether of-~; ;`
bisphenol A having an epoxide equivalent weight of 180 to -195. "~
The resin component was combined with 32 grams of polyoxypropylene triamine (of Example XI).
The combined components were then coated on an epoxy-glass hardboard, commercially obtained, and cured ' ' , . ., : . . ~ - ' .
.: , : . . , . , . :

- 1~6~)136 at 100C for one hour. The cured board was metallized and then baked at 170C for 30 minutes. Peel values of 8.8 to 12.5 lbs./linear in. at 25C, 7 lbs./linear in. at 0C and 3.5 lbs./linear in. at 90C were obtained.
EXAMPLE XIV
The procedure of Example XI was repeated except tha-t the resin component comprised~
(a) 50 grams of the reac-tion product (at ~ ~ ;
300F for 30 minutes) of (1) 60 weight percent of the diglycidyl ether of bisphenol A having an epoxide equivalent weight of 180 to 195 and (2) 40 weight percent of the carboxyl terminated butadiene/acrylonitrile copolymer (of Example VI) having a number average molecular weight of 3200; and ; (b) 50 grams of the diglycidyl ether of tetrabromo bisphenol A having an epoxide equivalent weight of ~50 to 500 (of Example II).
The resin component was combined with 13 grams of polyoxypropylenetrlamine (of Example XI). The `
combined components were then coated on the epoxy-~lass hardboard and cured at 120C for 30 minutes. The cured board was metalli2ed and then baked at 170C for 30 minutes.
A peel value of 10 lbs./linear in. at 25C was obtained.
It is to be understood that the above-described embodiments are simply illustrative of the principles of the invention. Various other modifications and changes may be made by those skilled in the art which will embody the principles of the invention and fall within the spirit `~
and scope thereof.

,~ ~
.~
'" "

` .

Claims

1. A cured epoxy polymer having improved adhesive properties comprising the reaction product of a mixture com-prising:
(1) a resin component comprising, (a) about 25 to about 95 parts by weight per 100 parts by weight of said resin component of a diglycidyl ether based upon linoleic dimer acid selected from the group consisting of (a1) an adduct of two moles of the diglycidyl ether of bisphenol A and one mole of linoleic dimer acid having a structural formula of and an epoxide equivalent weight of 650 to 750, (b1) a diglycidyl ether of linoleic dimer acid having a structural formula of and an epoxide equivalent weight of 400 to 420, and (c1) a mixture thereof;
(b) about 5 to about 50 parts by weight per 100 parts by weight of the resin component of an elasto-merically modified epoxy resin blend comprising the reaction product of about 40 weight percent of a carboxyl terminated acrylonitrile/butadiene random copolymer having a structural formula of containing 2.37 percent carboxyl groups, 18 to 19 percent bound acrylonitrile and having a number average molecular weight of 3200, combined with about 60 weight percent of a diglycidyl ether selected from the group consisting of a diglycidyl ether of bisphenol A having an epoxide equivalent weight of 180 to 195 and a diglycidyl ether of bisphenol F
having an epoxide equivalent weight of 152 to 167; and (c) a remainder of a diglycidyl ether selected from the group consisting of a diglycidyl ether of bisphenol A, a diglycidyl ether of bisphenol F or a mixture thereof;
and (2) a curing agent selected from (a) at least one acid anhydride present in an amount ranging from about 16 to about 60 parts by weight per 100 parts by weight of the resin com-ponent, (b) a polyamine present in an equal mole-to-mole ratio with the resin component, (c) a mixture comprising said polyamine in (b) above combined with at least 5 parts by weight per 100 parts by weight of the resin component of ? acid anhydride, (d) a mixture comprising said at least one acid anhydride in (a) above combined with up to about 30 parts by weight per 100 parts by weight of the resin component of a carboxylic acid selected from the group consisting of dicarboxylic acid having a structural formula of (HO-?)2R'' , where R'' is an organic radical selected from CH2(CH2)5CH2, , , and ;

a trimer acid having a stocihiometry of C54H96O6, and a mixture thereof, and (e) a mixture of the foregoing.

2. The cured epoxy polymer as defined in claim 1 wherein said curing agent comprises at least one acid anhydride present in an amount which yields an anhydride-to-epoxide molar ratio of 0.6 to 0.9.

3. The cured epoxy polymer as defined in claim 1 wherein said reaction mixture comprises:
said diglycidyl ether in (a1) above, present in an amount of about 75 parts by weight per 100 parts by weight of said resin component;

said elastomerically modified epoxy resin blend in (b) above, where said combined diglycidyl ether comprises bisphenol A, present in an amount of about 25 parts by weight per 100 parts by weight of said resin component;
and said at least one acid anhydride, in (2) (a) above, comprising an anhydride mixture which comprises about 20 parts by weight per 100 parts by weight of said resin component of chlorendic anhydride and about 2.5 parts by weight per 100 parts by weight of said resin component of phthalic anhydride.

4. The cured epoxy polymer as defined in claim 1 wherein said reaction mixture comprises:
said diglycidyl ether in (a1) above, present in an amount of about 30 parts by weight per 100 parts by weight of said resin component;
said elastomerically modified epoxy resin blend in (b) above, where said combined diglycidyl ether of bisphenol A, present in an amount of about 30 parts by weight per 100 parts by weight of said resin component;
said remainder in (c) above, comprising said diglycidyl ether of bisphenol A which comprises about 40 parts by weight per 100 parts by weight of said resin component of a brominated diglycidyl ether of bisphenol A, containing 18 to 20 weight percent of bromine and having an epoxide equivalent weight of 450 to 500; and said at least one acid anhydride, in (2) (a) above, comprising an anhydride mixture which comprises about 30 parts by weight per 100 parts by weight of said resin component of chlorendic anhydride and about 16 parts by weight per 100 parts by weight of said resin component of the adduct of methylcyclopentadiene and maleic anhydride.

5. The cured epoxy as defined in claim 1 wherein said reaction mixture comprises:
said diglycidyl ether in (a1) above, present in an amount of about 40 parts by weight per 100 parts by weight of said resin component;
said elastomerically modified epoxy resin blend in (b) above, where said combined diglycidyl ether of bisphenol F, present in an amount of about 30 parts by weight per 100 parts by weight of said resin component;
said diglycidyl ether, in (c) above, comprising a brominated diglycidyl ether of bisphenol A, containing 18 to 20 weight percent of bromine and having an epoxide equivalent weight of 450 to 500, present in an amount of about 30 parts by weight per 100 parts by weight of said resin component; and said at least one acid anhydride, in (2) (a) above, comprising an anhydride mixture which comprises about 20 parts by weight per 100 parts by weight of said resin component of chlorendic anhydride, about 10 parts by weight per 100 parts by weight of said resin component of the adduct of methylcyclopentadiene and maleic anhydride, and about 10 parts by weight per 100 parts by weight of said resin component of citraconic anhydride.

6. The cured epoxy as defined in claim 1 wherein said reaction mixture comprises:
said diglycidyl ether in (b1) above, present in an amount of about 28.8 parts by weight per 100 parts by weight of said resin component;
said elastomerically modified epoxy resin blend in (b) above, where said combined diglycidyl ether of bisphenol A, present in an amount of about 32.7 parts by weight per 100 parts by weight of said resin component;
said diglycidyl ether of bisphenol A, in (c) above, comprising about 38.5 parts per 100 parts by weight of said resin component of a brominated diglycidyl ether of bisphenol A, containing 18 to 20 weight percent of bromine and having an epoxide equivalent weight of 450 to 500; and said at least one acid anhydride, in (2) (a) above, comprising an anhydride mixture which comprises about 24 parts by weight per 100 parts by weight of said resin component of chlorendic anhydride and about 24 parts by weight per 100 parts by weight of said resin component of the adduct of methylcyclopentadiene and maleic anhydride.

7. A curable epoxy composition comprising a mixture which comprises:
(1) a resin component comprising:
(a) about 25 to about 95 parts by weight per 100 parts by weight of said resin component of a diglycidyl ether based upon linoleic dimer acid selected from the group consisting of (a1) an adduct of two moles of the diglycidyl ether of bisphenol A and one mole of linoleic dimer acid having a structural formula of and an epoxide equivalent weight of 650 to 750, (b1) a diglycidyl ether of linoleic dimer acid having a structural formula of and an epoxide equivalent weight of 400 to 420, and (c1) a mixture thereof;
(b) about 5 to about 50 parts by weight per 100 parts by weight of the resin component of an elastomerically modified epoxy resin blend comprising the reaction product of about 40 weight percent of a carboxyl terminated acrylonitrile/butadiene random copolymer having a structural formula of containing 2.37 percent carboxyl groups, 18 to 19 percent bound acrylonitrile and having a number average molecular weight of 3200, combined with about 60 weight percent of a diglycidyl ether selected from the group consisting of a diglycidyl ether of bisphenol A having an epoxide equivalent weight of 180 to 195 and a diglycidyl ether of bisphenol F
having an epoxide equivalent weight of 152 to 167; and (c) a remainder of a diglycidyl ether selected from the group consisting of a diglycidyl ether of bisphenol A, a diglycidyl ether of bisphenol F or a mixture thereof;
and (2) a curing agent selected from (a) at least one anhydride present in an amount ranging from about 16 to about 60 parts by weight per 100 parts by weight of the resin component, (b) a polyamine present in an equal mole-to-mole ratio with the resin component, (c) a mixture comprising said polyamine in (b) above combined with at least 5 parts by weight per 100 parts by weight of the resin component of an acid anhydride, (d) a mixture comprising said at least one acid anhydride in (a) above combined with up to about 30 parts by weight per 100 parts by weight of the resin component of a carboxylic acid selected from one group consisting of a dicarboxylic acid having a structural formula of (HO-?)2R'', where R'' is an organic radical selected from CH2(CH2)5CH2, , , and ;

a trimer acid having a stoichiometry of C54H96O6, and a mixture thereof, and (e) a mixture of the foregoing.

8. The composition as defined in claim 7 wherein said curing agent comprises at least one acid anhydride present in an amount which yields an anhydride-to-epoxide molar ratio of 0.6 to 0.9.

9. The composition as defined in claim 7 wherein the mixture comprises:
said diglycidyl ether in (1) (a1) above, present in an amount of about 75 parts by weight per 100 parts by weight of said resin component;
said elastomerically modified epoxy resin blend in (1) (b) above, where said combined diglycidyl ether of bisphenol A, present in an amount of about 25 parts by weight per 100 parts by weight of said resin component; and said at least one acid anhydride, in (2) (a) above, comprising an anhydride mixture which comprises about 20 parts by weight per 100 parts by weight of said resin component of chlorendic anhydride and about 2.5 parts by weight per 100 parts by weight of said resin component of phthalic anhydride.

10. The composition as defined in claim 7 wherein the mixture comprises:
said diglycidyl ether in (1) (a1) above, present in an amount of about 30 parts by weight per 100 parts by weight of said resin component;
said elastomerically modified epoxy resin blend in (1) (b) above, where said combined diglycidyl ether of bisphenol A, present in an amount of about 30 parts by weight per 100 parts by weight of said resin component;
said remainder in (1) (c) above, comprising said diglycidyl ether of bisphenol A which comprises about 40 parts by weight per 100 parts by weight of said resin component of a brominated diglycidyl ether of bisphenol A, containing 18 to 20 weight percent of bromine and having an epoxide equivalent weight of 450 to 500; and said at least one acid anhydride, in (2) (a) above, comprising an anhydride mixture which comprises about 30 parts by weight per 100 parts by weight of said resin component of chlorendic anhydride and about 16 parts by weight per 100 parts by weight of said resin component of the adduct of methylcyclopentadiene and maleic anhydride.

11. The composition as defined in claim 7 wherein the mixture comprises:
said diglycidyl ether in (1) (a1) above, present in an amount of about 40 parts by weight per 100 parts by weight of said resin component;
said elastomerically modified epoxy resin blend in (1) (b) above, where said combined diglycidyl ether of bisphenol F, present in an amount of about 30 parts by weight per 100 parts by weight of said resin component;
said diglycidyl ether, in (1) (c) above, comprising a brominated diglycidyl ether of bisphenol A, containing 18 to 20 weight percent of bromine and having an epoxide equivalent weight of 450 to 500, present in an amount of about 30 parts by weight per 100 parts by weight of said resin component; and said at least one acid anhydride, in (2) (a) above, comprising an anhydride mixture which comprises about 20 parts by weight per 100 parts by weight of said resin component of chlorendic anhydride, about 10 parts by weight per 100 parts by weight of said resin component of the adduct of methylcyclopentadiene and maleic anhydride, and about 10 parts by weight per 100 parts by weight of said resin component of citraconic anhydride.

12. The composition as defined in claim 7 wherein the mixture comprises:
said diglycidyl ether in (1) (b1) above, present in an amount of about 28.8 parts by weight per 100 parts by weight of said resin component;
said elastomerically modified epoxy resin blend in (1) (b) above, where said combined diglycidyl ether of bisphenol A, present in an amount of about 32.7 parts by weight per 100 parts by weight of said resin component;
said diglycidyl ether of bisphenol A, in (1) (c) above, comprising about 38.5 parts per 100 parts by weight of said resin component of a brominated diglycidyl ether of bisphenol A, containing 18 to 20 weight percent of bromine and having an epoxide equivalent weight of 450 to 500; and said at least one acid anhydride, in (2) (a) above, comprising an anhydride mixture which comprises about 24 parts by weight per 100 parts by weight of said resin component of chlorendic anhydride and about 24 parts by weight per 100 parts by weight of said resin component of the adduct of methylcyclopentadiene and maleic anhydride.

13. An article which comprises:
a first layer comprising a fully cured virgin epoxy polymer resulting from fully curing a mixture of (1) a resin component comprising, (a) about 25 to about 95 parts by weight per 100 parts by weight of said resin component of a diglycidyl ether based upon linoleic dimer acid selected from the group consisting of (a1) an adduct of two moles of the diglycidyl ether of bisphenol A and one mole of linoleic dimer acid having a structural formula of and an epoxide equivalent weight of 650 to 750, (b1) a diglycidyl ether of linoleic dimer acid having a structural formula of and an epoxide equivalent weight of 400 to 420, and (c1) a mixture thereof; (b) about 5 to about 50 parts by weight per 100 parts by weight of the resin component of an elasto-merically modified epoxy resin blend comprising the reaction product of about 40 weight percent of a carboxyl terminated acrylinitrile/butadiene random copolymer having a structural formula of containing 2.37 percent carboxyl groups, 18 to 19 percent bound acrylinitrile and having a number average molecular weight of 3200, combined with about 60 weight percent of a diglycidyl ether selected from the group consisting of a diglycidyl ether of bisphenol A having a general structural formula of where n is the number of repeated units in the resin chain, having an epoxide equivalent weight of 180 to 195 and a diglycidyl ether of bisphenol F having a general structural formula of where n is the number of repeated units in the resin chain having an epoxide equivalent weight of 152 to 167, and (c) a remainder of the resin component of a diglycidyl ether selected from the group consisting of a diglycidyl ether of bisphenol A, having a general structural formula of where n is the number of repeated units in the resin chain, a diglycidyl ether of bisphenol F having a general structural formula of where n is the number of repeated units in the resin chain and a mixture thereof; and (2) a curing agent selected from the group consisting of (a) at least one acid anhydride present in an amount ranging from about 16 to about 60 parts by weight per 100 parts by weight of the resin component, (b) a polyamine present in an equal mole-to-mole ratio with the resin component, (c) a mixture comprising said polyamine in (b) above combined with at least 5 parts by weight per 100 parts by weight of the resin component of an acid anhydride, (d) a mixture comprising said at least one acid anhydride in (a) above combined with up to about 30 parts by weight per 100 parts by weight of the resin component of a carboxylic acid selected from the group consisting of a dicarboxylic acid having a structural formula of (HO-?)2R", where R" is an organic radical selected from the group consisting of - , , and ;

and a trimer acid having a stoichiometry of C54H96O6, and a mixture thereof, and (e) a mixture of the foregoing; and an adherent metal layer deposited on at least a portion of said first fully cured virgin epoxy layer.

14. The article as defined in claim 13 wherein said curing agent comprises at least one acid anhydride present in an amount which yields an anhydride-to epoxide molar ratio of 0.6 to 0.9.

15. The article as defined in claim 13 wherein said mixture comprises:
said diglycidyl ether in (a1) above, present in an amount of about 75 parts by weight per 100 parts by weight of said resin component;
said elastomerically modified epoxy resin blend in (b) above, where said combined diglycidyl ether of bisphenol A, present in an amount of about 25 parts by weight per 100 parts by weight of said resin component;
and said at least one acid anhydride, in (2) (a) above, comprising an anhydride mixture which comprises about 20 parts by weight per 100 parts by weight of said resin component of chlorendic anhydride and about 2.5 parts by weight per 100 parts by weight of said resin component of phthalic anhydride.

16. The article as defined in claim 13 wherein said mixture comprises:
said diglycidyl ether in (a1) above, present in an amount of about 30 parts by weight per 100 parts by weight of said resin component;
said elastomerically modified epoxy resin blend in (b) above, where said combined diglycidyl ether of bisphenol A, present in an amount of about 30 parts by weight per 100 parts by weight of said resin component;
a remainder of (c) above, comprising said diglycidyl ether of disphenol A, which comprises about 40 parts by weight per 100 parts by weight of said resin component of a brominated diglycidyl ether of bisphenol A, containing 18 to 20 weight percent of bromine and having an epoxide equivalent weight of 450 to 500; and said at least one acid anhydride, in (2) (a) above, comprising an acid anhydride mixture which comprises about 30 parts by weight per 100 parts by weight of said resin component of chlorendic anhydride and about 16 parts by weight per 100 parts by weight of said resin component of the adduct of methylcyclopentadiene and maleic anhydride.

17. The article as defined in claim 13 wherein said mixture comprises:
said diglycidyl ether in (a1) above, present in an amount of about 40 parts by weight per 100 parts by weight of said resin component;
said elastomerically modified epoxy resin blend in (b) above, where said combined diglycidyl ether of bisphenol F, present in an amount of about 30 parts by weight per 100 parts by weight of said resin component;
said diglycidyl ether, in (c) above, comprising a brominated diglycidyl ether of bisphenol A, containing 18 to 20 weight percent of bromine and having an epoxide equivalent weight of about 450 to 500, present in an amount of about 30 parts by weight per 100 parts by weight of said resin component; and said at least one acid anhydride, in (2) (a) above, comprising an acid anhydride mixture which comprises about 20 parts by weight per 100 parts by weight of said resin component of chlorendic anhydride, about 10 parts by weight per 100 parts by weight of said resin component of the adduct of methylcyclopentadiene and maleic anhydride, and about 10 parts by weight per 100 parts by weight of said resin component of citraconic anhydride.

18. The article as defined in claim 13 wherein said mixture comprises:
said diglycidyl ether in (b1) above, present in an amount of about 28.8 parts by weight per 100 parts by weight of said resin component;

said elastomerically modified epoxy resin blend in (b) above, where said combined diglycidyl ether of bisphenol A, present in an amount of about 32.7 parts by weight per 100 parts by weight of said resin component;
said diglycidyl ether of bisphenol A, in (c) above, comprising about 38.5 parts per 100 parts by weight of said resin component of a brominated diglycidyl ether of bisphenol A, containing 18 to 20 weight percent of bromine and having an epoxide equivalent weight of 450 to 500; and said at least one acid anhydride, in (2) (a) above, comprising an acid anhydride mixture which comprises about 24 parts by weight per 100 parts by weight of said resin component of chlorendic anhydride and about 24 parts by weight per 100 parts by weight of said resin component of the adduct of methylcyclopentadiene and maleic anhydride.

19. The article as defined in claim 13 wherein said mixture comprises:
said diglycidyl ether in (a1) above, present in an amount of about 50 parts by weight per 100 parts by weight of said resin component;
said diglycidyl ether of bisphenol A in (c) above which comprises a brominated diglycidyl ether of bisphenol A, containing 18 to 20 weight percent of bromine and having an epoxide equivalent weight of 450 to 500, present in an amount of about 50 parts by weight per 100 parts by weight of said resin component; and said curing agent, in (2) (d) above, comprising about 15 parts by weight per 100 parts by weight of said resin component of chlorendic anhydride, about 25 parts by weight per 100 parts by weight of the resin component of the adduct of methylcyclopentadiene and maleic anhydride, about 12 parts by weight per 100 parts by weight of the resin component of said dicarboxylic acid, where R" is and 10 parts by weight per 100 parts by weight of the resin component of said trimer acid.

20. The article as defined in claim 19 wherein said curing agent comprises said mixture comprising said acid anhydride and said carboxylic acid.

21. The article as defined in claim 19 wherein said fully cured virgin epoxy layer results from fully curing said mixture in situ.

22. The article as defined in claim 19 wherein said adherent metal layer has a peel strength of at least 5 pounds per inch at a 90° peel and a peel rate of 2 inches per minute at 25°C.

23. An article which comprises:
a first layer comprising a fully cured virgin epoxy polymer resulting from reacting a mixture of (1) a resin component comprising a first resin comprising up to about 70 parts by weight per 100 parts by weight of said resin component of a diglycidyl ether selected from the group consisting of a diglycidyl ether of bisphenol A, having a general structural formula of where n is the number of repeated units in the resin chain a diglycidyl ether of bisphenol F having a general structural formula of where n is the number of repeated units in the resin chain and a mixture thereof, combined with a second resin selected from the group consisting of (a) about 25 to about 95 parts by weight per 100 parts by weight of said resin component of a diglycidyl ether based upon linoleic dimer acid selected from the group consisting of (a1) an adduct of two moles of the diglycidyl ether of bisphenol A and one mole of linoleic dimer acid having a structural formula of and an epoxide equivalent weight of 650 to 750, (b1) a diglycidyl ether of linoleic dimer acid having a structural formula of and an epoxide equivalent weight of 400 to 420, and (c1) a mixture thereof; (b) about 5 to about 50 parts by weight per 100 parts by weight of the resin component of an elastomerically modified epoxy resin blend comprising the reaction product of about 40 weight percent of a carboxyl terminated acrylonitrile/butadiene random copolymer having a structural formula of , containing 2.37 percent carboxyl groups, 18 to 19 percent bound acrylinitrile and having a number average molecular weight of 3200, combined with about 60 weight percent of a diglycidyl ether selected from the group consisting of a diglycidyl ether of bisphenol A having general structural formula of where n is the number of repeated units in the resin chain, having an epoxide equivalent weight of 180 to 995 and a diglycidyl ether of bisphenol F having a general structural formula of where n is the number of repeated units in the resin chain, having an epoxide equivalent weight of 152 to 167, and (c) a mixture of (a) and (b); and (2) a curing agent selected from the group consisting of (a) at least one acid anhydride present in an amount ranging from about 16 to about 60 parts by weight per 100 parts by weight of the resin component, (b) a polyamine present in an equal mole-to-mole ratio with the resin component, (c) a mixture comprising said polyamine in (b) above combined with at least 5 parts by weight per 100 parts by weight of the resin component of an acid anhydride, (d) a mixture comprising said at least one acid anhydride in (a) above combined with up to about 30 parts by weight per 100 parts by weight of the resin component of a carboxylic acid selected from the group consisting of a dicarboxylic acid having a structural formula of (HO-?)2R", where R" is an organic radical selected from the group consisting of , , and ;

and a trimer acid having a stoichiometry of C54H96O6, and a mixture thereof, and (e) a mixture of the foregoing; and an adherent metal layer directly deposited on at least a portion of said first fully cured virgin epoxy layer.

24. The article as defined in claim 23, wherein said second resin comprises (b).

25. The article as defined in claim 23 wherein said fully cured virgin epoxy layer results from fully curing said mixture in situ.

26. The article as defined in claim 23 wherein said adherent metal layer has a peel strength of at least 5 pounds per inch at a 90° peel and a peel rate of 2 inches per minute at 25°C.

27. In an improved method of depositing an adherent metal deposit on a surface comprising a cured epoxy existing in a virgin state comprising the steps of:

(A) rendering the surface capable of having an electroless metal deposited thereon from an electroless plating solution;
(B) treating the rendered surface with an electro-less plating solution to deposit an electroless metal thereon, wherein the improvement comprises:
prior to step (A) above, coating the surface of a suitable substrate with a reaction mixture comprising (1) a resin component which comprises (a) x parts by weight per 100 parts by weight of the resin component of a diglycidyl ether based upon linoleic dimer acid selected from the group consisting of (a1) an adduct of two moles of the diglycidyl ether of bisphenol A and one mole of linoleic dimer acid having a structural formula of and an epoxide equivalent weight of 650 to 750, (b1) a diglycidyl ether of linoleic dimer acid having a structural formula of and an epoxide equivalent weight of 400 to 420, and (c1) a mixture thereof; (b) y parts by weight per 100 parts by weight of the resin component of an elastomerically modified epoxy resin blend comprising the reaction product of about 40 weight percent of a carboxyl terminated acrylonitrile/
butadiene random copolymer having a structural formula of , containing 2.37 percent carboxyl groups, 18 to 19 percent bound acrylonitrile and having a number average molecular weight of 3200, combined with about 60 weight percent of a diglycidyl ether selected from the group consisting of a diglycidyl ether of bisphenol A having an epoxide equivalent weight of 180 to 195 and a diglycidyl ether of bisphenol F
having an epoxide equivalent weight of 152 to 167; and (c) z parts of a suitable diglycidyl ether selected from the group consisting of a diglycidyl ether of bisphenol A, a diglycidyl ether of bisphenol F and a mixture thereof where x + y + z = 100 parts and z is a concentration less than 100 parts by weight; and (2) a curing agent selected from (a) at least one acid anhydride present in an amount ranging from about 16 to about 60 parts by weight per 100 parts by weight of the resin component, (b) a polyamine present in an equal mole-to-mole ratio with the resin component, (c) a mixture comprising said polyamine in (b) above combined with at least 5 parts by weight per 100 parts by weight of the resin component of an acid anhydride, (d) a mixture comprising said at least one acid anhydride in (a) above combined with up to about 30 parts by weight per 100 parts by weight of the resin component of a carboxylic acid selected from the group consisting of a dicarboxylic acid having a structural formula of:

(HO-?)2R'', where R'' is an organic radical selected from CH2(CH2)5CH2, , , and ;

and a trimer acid having a stochiometry of C54H96O6, and a mixture thereof, and (e) a mixture of the foregoing; and curing the mixture to obtain a cured epoxy coated surface.

28. The method as defined in claim 27 wherein x ranges from about 25 to about 95, y ranges from about 5 to about 50 and z ranges from 100-(x + y), in said resin component.

29. The method as defined in claim 27 wherein said curing agent comprises at least one acid anhydride present in an amount which yields an anhydride to epoxide molar ratio of 0.6 to 0.9.

30. The method as defined in claim 27 wherein said mixture comprises:
said diglycidyl ether in (a1) above, present in an amount of about 75 parts by weight per 100 parts by weight of said resin component;
said elastomerically modified epoxy resin blend in (b) above, where said combined diglycidyl ether of bisphenol A, present in an amount of about 25 parts by weight per 100 parts by weight of said resin component; and said curing agent, in (2) (a) above, comprising an anhydride mixture which comprises about 20 parts by weight per 100 parts by weight of said resin component of chlorendic anhydride and about 2.5 parts by weight per 100 parts by weight of said resin component of phthalic anhydride.

31. The method as defined in claim 27 wherein said mixture comprises:
said diglycidyl ether in (a1) above, present in an amount of about 30 parts by weight per 100 parts by weight of said resin component;
said elastomerically modified epoxy resin blend in (b) above, where said combined diglycidyl ether of bisphenol A, present in an amount of about 30 parts by weight per 100 parts by weight of said resin component;
a remainder of (c) above, comprising said diglycidyl ether of bisphenol A which comprises about 40 parts by weight per 100 parts by weight of said resin component of a brominated diglycidyl ether of bisphenol A, containing 18 to 20 weight percent of bromine and having an epoxide equivalent weight of 450 to 500; and said curing agent, in (2) (a) above, comprising an anhydride mixture which comprises about 30 parts by weight per 100 parts by weight of said resin component of chlorendic anhydride and about 16 parts by weight per 100 parts by weight of said resin component of the adduct of methylyclopentadiene and maleic anhydride.

32, The method as defined in claim 27 wherein said reaction mixture comprises:

said diglycidyl ether in (a1) above, present in an amount of about 40 parts by weight per 100 parts by weight of said resin component;
said elastomerically modified epoxy resin blend in (b) above, where said combined diglycidyl ether of bisphenol F, present in an amount of about 30 parts by weight per 100 parts by weight of said resin component;
said diglycidyl ether, in (c) above, comprising a brominated diglycidyl ether of bisphenol A, containing 18 to 20 weight percent of bromine and having an epoxide equivalent weight of 450 to 500, present in an amount of about 30 parts by weight per 100 parts by weight of said resin component; and said curing agent, in (2) (a) above, comprising an anhydride mixture which comprises about 20 parts by weight per 100 parts by weight of said resin component of chlorendic anhydride, about 10 parts by weight per 100 parts by weight of said resin component of the adduct of methylcyclopentadiene and maleic anhydride, and about 10 parts by weight per 100 parts by weight of said resin component of citraconic anhydride.

33. The method as defined in claim 27 wherein said reaction mixture comprises:
said diglycidyl ether in (b1) above, present in an amount of about 28.8 parts by weight per 100 parts by weight of said resin component;
said elastomerically modified epoxy resin blend in (b) above, where said combined diglycidyl ether bisphenol A, present in an amount of about 32.7 parts by weight per 100 parts by weight of said resin component;

said diglycidyl ether of bisphenol A, in (c) above, comprising about 38.5 parts per 100 parts by weight of said resin component of a brominated diglycidyl ether of bisphenol A, containing 18 to 20 weight percent of bromine and having an epoxide equivalent weight of 450 to 500; and said curing agent, in (2) (a) above, comprising an anhydride mixture which comprises about 24 parts by weight per 100 parts by weight of said resin component of chlorendic anhydride and about 24 parts by weight per 100 parts by weight of said resin component of the adduct of methylcyclopentadiene and maleic anhydride.

34. The method as defined in claim 27 wherein said reaction mixture comprises:
said diglycidyl ether in (a1) above, present in an amount of about 50 parts by weight per 100 parts by weight of said resin component;
said diglycidyl ether of bisphenol A in (c) above, present in an amount of about 50 parts by weight per 100 parts by weight of said resin component, which comprises a brominated diglycidyl ether of bisphenol A, containing 18 to 20 weight percent of bromine and having an epoxide equivalent weight of 450 to 500; and said curing agent, in (2) (d) above, comprising about 15 parts by weight per 100 parts by weight of said resin component of chlorendic anhydride, about 25 parts by weight per 100 parts by weight of the resin component of the adduct of methylcyclopentadiene and maleic anhydride, about 12 parts by weight per 100 parts by weight of the resin com-ponent of said dicarboxylic acid where R " is and 10 parts by weight per 100 parts by weight of the resin component of said trimer acid.

35. The method as defined in claim 27 which further comprises heating the electroless metal-deposited surface.

36. The method as defined in claim 27 wherein said reaction mixture comprises y parts of said elastomerically modified epoxy resin blend and z parts of said diglycidyl ether, where y + z = 100 parts.