CA2105657A1 - Photodefinable interlevel dielectrics - Google Patents

Abstract

A predetermined pattern of a dielectric polymer is formed on a substrate from either a first prepolymer which is the ether of the oligomeric condensation product of dihydric phenol and formaldehyde or a mixture of said oligomer with a second prepolymer which is the ether of the oligomeric condensation product of a dialdehyde and 3 to 4 moles of a phenol.

Description

wo92/l7N2n PCT/~'S92/02352 f~

PHOTO~EFINABLE INTERLEVEL DIELECTRICS

PRIOR ART
This invention relates to materials used to provide isolation of conductive layers in microelectronic circuitry. In particular, it relates to polymeric materials which can be photopolymerized so that dielectric layers can be formed where desired in ~ultilayer structures. Such layers must be excellent insulators, have good chemical resistance and, of course, must adhere to the substrate on which they are placed.
Polyimides have been used for such dielectrics since they have superior temperature and chemical resistance compared to many other polymers. Literature and patents disclosing of the use of polyimides are extensively discussed by the present inventor in U. S.
Patent 4,908,096, which is incorporated herein by reference. The disadvantages of the polyimides are discussed, namely, that they release large amounts of volatiles during curing, absorb moisture, have poor adhesion, and have a relatively high coefficient of expansion. The patent discloses and claims the use of other polymers as interlevel dielectrics having improved properties, namely, vinylbenzyl or alkyl ethers of the condensation products of dialdehydes and phenols.
The present invention relates to other 2S polymers which have been found to provide useful interlevel dielectrics.
In U. S. 4,8S5,375 the present inventor has disclosed oligomers which are ethers of bisphenols and formaldehyde which have application to making laminated boards for electronic applications. In U.S. Pat. No.
4,816,498 another family of oligomeric condensation products was disclosed which differ from those just ' ~09~/17X2~ PCT/~S92/0235 ~ vG`~ 2 discussed in being the condensation products of dialdehydes with 3 to 4 moles of phenols. These oligomers also are etherified to provide a mixture of vinylbenzyl and alkyl ethers. They may be used to make laminated boards for electronic applications. ~oth of such oligomers now have been found to be u~eful as interlevel dielectrics, as will be seen in the discussion below. Related polymers are disclosed in PCT/US9l/09391 and PCT/US9l/09392.

~UMMARY OF THE INVENTIO~
This invention comprises a method of forming a predetermined pattern from a polymer on a substrate and the thus-created dielectric layers.
Such patterns are created by coating onto the substrate a prepolymer and then irradiating the exposed portions of a masking pattern to render the prepolymer insoluble, then selectively dissolving the non-irradiated masked portions of the coating leaving the insoluble irradiated prepolymer, and curing the irradiated prepolymer to form an infusible glassy solid in the predetermined pattern.
The prepolymer is either an ether of the oligomeric condensation product of a dihydric phenol and formaldehyde or a mixture of said oligomer with a second prepolymer which is the ether of the oligomeric condensation product of a dialdehyde and 3 to 4 moles of a phenol.
The first oligomer has the formula ': ~

WO92/17X20 PCT/~'S92/023~' ~ J;7 _~CH,--(Q) ~}

(X)~ (X), (Z)b~}R2 (Z)b~R2 E~ O~E
1s where the recurr~n~ unit Q has the ~tructure, 2c E
_~CH,-- ~CH2--2s (X)~ OR (X)s - (~}R2 (~)b$_R2 E~ E~

.. . . .

WO 92/17820 PCI`/US92/02352 r ~

a~d n is an integer from 1 to lO;
s is O or 1:
each X is independently selected from the group consisting of CH2, C(CH3)2, o, S, SO2, CO, and OC~O:
each R~ and R2 is independently selected from the group consisting of hydrogen, alkyl and alkoxy moieties containing 1 to 10 carbon atoms, phenyl and phenoxy;
lo a and b are independently O or integers from 1 to 4;
Z is Cl or Br;
E is selected from the group consisting of the vinyl-benzyl moiety, alkyl moieties containing 1 to 10 carbon atoms, or benzyl, sub~ect to the constraint that at least 50% of all E's are the vinylbenzyl moiety.
In a preferred embodiment, E is at laast 70%
vinyl benzyl and the remaining E's are propyl and X is C(CH3)2 or both C(CH3)2 and CO.
The seGond oligomer is an ether of the oligomeric condensation product of (a) l molar proportion of a dialdehyde and (b) from about 3 to about 4 molar proportions of a phenol; where the dialdehyde is selected from the group consisting of OHC(CH2)~CHO, where m - O or an integer from 1 to 6, cyclopentanedialdehyde, phthalaldehyde, isophthalaldehyde, terephthalaldehyde, hexahydrophthalaldehyde, cycloheptanedialdehyde, hexahydroisophthalaldehyde, hexahydroterephthalaldehyde, and cyclooctanedialdehyde; where the phenol has the structure R3C~OH and where R3 is hydrogen or an alkyl group containing from l to about lO carbon atoms; and where the phenol residue of said oligomeric condensation product is etherified with one or more substituents to afford ether moieties randomly selected from the group . . , . ~ .
- .. .. . , . : .
~- , ?
. ..

.: .
., . : .

2~ PCT/~S92/02352 i j f consisting of vinylbe~zyl, alkyl moieties containing from 1 to 10 carbon atoms, cycloalkyl moieties from 5 to carbon atoms, and benzyl, with the ratio of vinylbenzyl to other moieties being from 1:1 to about 6:1.

DESCRIP~ION OF THE PREFERRED EMBODIME~TS
Polvmeric Resins In U.S. Patent No. 4,855,375, the present inventor disclosed the preparation and use of the ethers of the oligomeric condensation products of a dihydric phenol and formaldehyde and their use in composites, especially laminated boards for electronic uses. It has now been found that these compositions Gan be used as interlevel dielectrics in combination with the oligomers of U.S. Pat. No. 4,816,498, where they have the advantages of low water absorption, low dielectric constant, low coefficients of thermal expan ion, high glass transition temperature, high thermal stability, high solids coating concentrations, and are photochemically curable, thermally curable, and generate little or no volatiles during the cure process.
The prepolymers used in forming a pattern are of two types. The first has the formula:

,- - . - . .. .

w092/17x20 PCT/~S92/02352 3 ~ 3 ~7 (Z)a{~CH~ (C)n~}
(X), (X), Z)b{~}R~ (Z)b~}R2 0 ~ C~E
E

They result from the etherification of oligomers which are the condensation product of a 15 dihydric phenol and formaldehyde. The product will be a mixture of oligomers with varying molecular weight.
The number, n, of recurring units Q generally will vary from 1 to 10. Preferably, n is 1 or an integer from 1 to 6 and the number average of n is about 3.
The recurring unit Q itself has the structure, _~CH,-- ~CH,--~) OR _~

30 (~R2 (Z)b{~}

E~ E~

... .. .
- . .- .

-. .

Not~ con~ lon m~y occu: ~th-r cn ~ ~as~lo rln." a~ ~ h- rlght hand ~truc~ , or in dl~rer~nt rlng~, a~ in t~ t ~nd tzuctur~. Th~ aromatic r~:~g~ ir. the r-~:urrlng Un~ Q ar- e~th~ ~oinsd, ~r~ctly 5 or ar~ e~pas~t-d ~y ~n int~ r.in~ ~ol~y (X)s~ '~at ~, S 1~ O or i. ISach o~ o ~oi-ti-- X ~ r ~e'chyl-n-~CE~ opropyli~ne tc(c~)i], an oxyg~n, ~ulrur, ul~onyl ~52]~ carbonyl ~COJ~ or~d~o~h-nyl~n~group t OC~,O ~ wh-~- th- oX~g-n~ o~ tt-r ç~ rally ~r-10 para or mota to oach oth~r. ~-~-r~ly X i~ C~CX3~)2 o:
~ot~ C~ 2 and CO.
EaC~ c~ roDu~tlo r~ nq~ ~ay b~s ~ub-t~tu nt~ or may b- co~ t~ly un-~b-t~tut-d Thu~, and R2 are ~nd~p-nd-ntly ~-l-ct~d ~ro~ ~ole~ uch hydrog~n, alXy~ ~o~ o ~ont~ining ~ro~ 1 to lo oarbon ~tom , th ph-nyL ~o~y, ~lkoxy mo~tio~
cont~in~n~ Jro~ 1 to 10 c~rbon ~o~-, A~n~ ~henox~, C~O Ex~lo~ o~ ~uit~ble alkyl mo~-t~ nclu~-~ thyl, thyl, ~ropyl, ~utyl, p~ntyl, h xyl, ~optl, octyl, ~o~yl, and d-oy~l ~o~-t~ ho ~othyl an~ t-rt-~utyl group- Ar- pr rr~ alkyl ~o~-t~ lthough th-v~ t wh r~ R~ - X ~ gu~t- d-~lr~b}-1~- ba~lc ~o-ln- c~n b- 20dl~-d to b r~t~r~nt by ln¢orpor~t~ng h~log-n ato~ lnto th-aro~at~c rln~- ~huo, Z ~y ~- a halog-n ~om, ~ ¢~ally bro~n-, ~n~ wh r- t~ ~som~tlo rin~
halog n~t d ~ And b ~so i~t-g~r~ ~ro~ 1 to 4 ~olyh~o~-n~t-d ~at-r~al- ~r~ pr~S-rs~ m~
ratar~ant~, ~n~ thu- ~ ~nd ~ ar r-co~ n~-d to b~ 2, 3, 30 or 4.
~ h ol~go~r~c ~ond n~t~on ~rod~et~ ~av- a ~ult~pllc~y o~ ph no~c hyd~oxyl g~oup- ub-t~n~l~lly all o~ whlch a~- end-c~pp-d ~ th~r grou~ ~n our SU~ST~TU~E SHEE t ' n r,~ 93 .
. . ~ .

~ ~ ~ r ~ r ^~

ir~te_~ ev~ c~ric r-oin~ b-~t c~-- r~s~
wh-r- tho th~r po~lon, E, i~ nylb~nzyl molety, th~t i~, o~ tructur~

CH,'CH~C~r whloh m~y b~ r ~ ~-t~- or p~ra~ r, ~d wh~eh u-u~lly 1- ~ ~lxt~:o of th- m ta- and p~ra-i60~er~.
10 Alt~ough lt la 0.~ o hJ~Y~ ~.11 th~ ph~nolic r.yd-oxyl- nd-c~pp-d with vinylb-nzyl ~oi-ti~ r- i-a co~t ~dv~ntag~ wher, ~w~r th~n all o~ t~r group~
~0 ~,r~ nylb-nzyl, bu' uzu~l ly ~t t~- xp-n-- o~
wh~t low - dl~ trlc c2n~t~nt. At l-~-t S0~ o~ th-15 E mo~ -t~ hou~ inyl~nzyl ~ol-ty, but b~tt~:
perr~r~nce c~aractn:i~tics re~ult wh-n ~ 70 to 100 o~ ther group~ ~r~ vlnylbonzy~, ~d th- b--_ pr~polym~r product r~cu~:c ~m~n 95 ~o 100~ oS zuch group- ~r- v~nyl~nzyl. Xo~r-v r, ~or ~ny ~pplic~tlon-20 lo~ th~n compl-t- nd-c~yping wtth ~rlnyl b-nzyl group-, i6 accep~ , bUt all o~ hyc~roxyl group~ c~ou~d ~-cappad,.
o th~ s groupz ~ nclui oth r th~
Y~nylb~nsyl, thl ~ ~c an ~11~1 slroup cos~ ning ~rom 1 25 to 1~ c~r~on~ or ~ ~-nzyl ~-oup. ~nes- E ~ c ~n ~lkyl grou~, t~ prl~ry ~lkyl group- ar~ pr ~!-rroCI, ~-~acially th- ~rl~ary lowar ~Xyl grou~- contalnlng ~ro~ 1 to 4 o~rbon ato~ ~hU~ mo-t ~ -lr~bl-~kyl group- con~l~t o2 Dl t~yl, ~tbyl, 1-p~o~yl, 1-3 0 butyl, ~nd ~ yl- -p~pyl . O~ ~ cyl group- ar-~ ~r~ d by ~ yl, 1-h~yl, 1-~-ptyl, 1-octyl, 1-.r~onyl, 1-d ~yl, 2-~yl-1-~utyl, 3q~ ~chy~ yl~ 2,3-d$~t~yl~ tyl, 3,3-d$D~-~,hyl-~-bu~cyl, and 2-~athyl-1-~-ntyl.
~iT'~ HC-~

. . - . - .
. .. . . . .
- ~. - ., :~ ` ..... .
.. . ..

wo 92/17X2n PC~/US92/02352 ~ _ 3 -i ~ v ~

In a preferred embodiment E is at least 70%
vinyl benzyl and the remaining E ' s are propyl .
The second type of oligomers are ethers of oligomeric condensation products of 1 molar proportion 5 of certain dialdehydes with from about 3 to about 4 molar proportions of a phenol. More particularly, the ~^
ether moiety is randomly selected from among the vinylbenzyl moiety, alkyl moieties containing from 1 to 10 carbon atoms, cycloalkyl moieties having from 5 to 10 about 10 carbon atoms, and the benzyl moiety, where the ratio of the vinylbenzyl to other ether ~noieties is at least 1:1 and may be as great as 6 :1.
The phenol ic ol igomers are the condensation products of 1 molar proportions of selected dialdehydes 15 with 3 to 4 ~olar proportions of a phenol. Although ~ore than 4 molar proportions of a phenol can be used in the practice of this invention, no more than 4 molar proportions will react with the dialdehydes.
One class of dialdehydes which may be used in 20 this invention aré the linear, terminal alkylene dialdehydes of formula OHC(CH2)~,CHO where m is 0 or an integer from 1 to 6. Such dialdehydes include glyoxal, malondialdehyde, succinidialdehyde, glutaraldehyde, adiphaldehyde, pimelaldehyde, and sebacaldehyde. Those 25 aldehydes where m is 0-4 are particularly preferred, and glyoxal (m~0) is especially favored in the practice of this invention.
Other aldehydes which may be employed in - preparation of the oligomeric condensation products 3 0 include cyclopentanedialdehyde, phthalaldehyde, - i s ophth a 1 d ehy d e , t e r ephth a 1 a 1 d ehy d e , th e hexahydrophthalaldehydes (i.e., the reduced counterpart of the phthalaldehydes where the aromatic ring has been .
~ , , .

- . .. -. , wo92/1782n PCTtUS92/02352 t' v ~ 1 0 reduced to a cyclohexane ring), cycloheptanedialdehyde, and cyclooctanedialdehyde.
The oligomers are the condensation pr~duct of 1 molar proportion of the aforementioned dialdehydes s with from 3 to about 4 molar proportions of a phenol.
The phenol has the general structure R3C~OH where R3 is hydrogen or an alkyl group containing from 1 through about 8 carbon atoms. The most desirable phenol is phenol itself, that is, the case where R3 is hydrogen.
Where R3 is an alkyl group it is most desirable that the alkyl group contain from 1 to about ~ carbon atoms, and cresol, the case where R3 is a methyl group is another preferred species of phenol.
The condensation product is analogous to phenol-formaldehyde resins. That is, the products result from the condensation of 2 molar proportions of a phenol with each aldehyde group. In the simplest case, which can be looked as the "monomeric" product, using phenol and glyoxal to exemplify the reaction, the product has the structure ~CH C~

HO~ ~OH

where the hydroxyls are almost exclusively ortho and para, and largely para, to the point of condensation of the phenol and glyoxal. Howevex, the product above has 4 phenolic groups per molecule, and any one of these may react with another molecule of glyoxal which then further condenses with three other molecules of phenol to give the structure .
:' ~

wo 92/1782n PCI/lJS92/0235' HO~ ,~--OH

CH--CH
HO~ ~CH--C~

The oligomeric product above results from a molar proportion of 7 phenols to 2 glyoxals. This oligomer in turn can react with another molecule of glyoxal and the latter can react further with 3 additional phenols to gi~e the next higher oligomer of the structure ~ ~ ~ H-C

~ CH ~ H

HO ~ ~

f1., , " ,~

: : ~ :

.

'lOa6S7 12 whlch ~ th~ mol~ ~ati~ o~ lo ph~ c group- to 3 ~lyoxals. ;n a ~m~lnr ~achion, th- n~xt h~h~r ~ligo~er ~ ola- ~atlo o~ p~eno~ to glyoxhl Or ~3:4, tho n~xt hlg~-r o~ 16: 5 wit~ ~ li~$tin~ mola~ rat$o 5 ~-ing 3 ~ n~-dJ to ~o ~-nt~ o:~d t,h~t ~ r~tlo 1~8-~than ~ 111 n~v~r bo A cb,i-v-d wit~hout int-rn-.l cycllzAt$on, ~.-., on- ~o~,ac~l- o~ ~lyox~ r-~ulro~
to r-a~t ~rich ~t loast 2 ph-nol~c ~oi~t$~ o~ tho ol ~om~r . ~n ~ ilar a~hion, t~o con~n~tion O pro~uct wh~ ch i~ "~ono~r" h~ m~ ting ratlo o~
phenol-gly3xal o~ 4 :1.
~ con~ tion produc_s ~r~ th-~-ol~-c ph-ncl~ m-nt' ona~ abo~r~, and ~r~ a ~ xturo o~
ollgomorr. ~hl~ m~xturo can ~ charact-riz-d by th~
~5 nu2bor o~ p~nol~c moi-ti-~ p~r ~olocul-. W- ~r~
oonc-rn-d ~it~ tho~ cond-n-~tion p~o~uct~ whlc~ h~v~
~ro~ 4 to a5out 60 phano~lc ~oi~ti~ p~r molocul~, and mor u~ually ~-tw~on ~ou~ an~ a~out 22 pb-nolic ~tle~
p-r ~ol-cul~. ~h- pro~uct b~lng ~ ~ixt~ oS ollgo~or~, ZO ~h pr~S-rr-d ~lxt~r~ i~ dh~r~oterl~ed by haviny ~r ~n a~rag~ b~tw~-n ~bou_ 5 an~ ~bou~ 8 ph nol~c ~o~-ti-~
p-r ~ol~cul-~
Mor- ~p~c'~¢illy, wh-r~ th- d~ald-hy~
glyox~l an~ t~ p~-ncl i~ phenol lt~ ch oll~o~eric ~roduct ~a~ a ~ol-cul-~ w~l~ht b~tw~ bout 400 ~d 6000, ~nd mor~ d~lra~ly ~-t~? -n ~bout 400 ~nd ~out 220~ . T~ or ol~ gom~r~ ~ p~oducto s~y b-charao~r~-d ~y ~n ~ r~g- ~ol-cul~r w~lg~t o~ b~two-n ~out 500 ~nd ~bout 8C0.
~h t~ o~-tt~ ro~ o~ th~o lnY~t~c~n ~r-r- o~ or~--cr~ ol~go~ic cond-n-~tlon prcduct-. In Gn- ~arlan~ o~ our i~v n~lon t~ ph nollc con~-n~tlon p:o~uct- ~ h~log-n~t~d pr~o~ to ~th~r ~or~ o~ ~ ord r to ~8~- th- ~n~ r-oln- ~or- ~ o SU~iTITU~E SH~

- ~.
:.

W092/1~82~ PcTlus92/o23s~

2 ~ .. 7 retardant. Increased flame retardancy occurs especially when the halogen is chlorine or bromine, and the use of a brominated product is preferred. The halogen is introduced into positions ortho and para to the phenolic hydroxyl group. If all of the ortho and para positions Are available a maximum of three halogen atoms per phenolic moiety may be introduced. Often it is desirable to prepare the maximally halogenated oligomeric condensation product, although at times a halogen content less than the maximum is advantageous.
However, in the latter variant it should be clear that there is at least one chlorine or bromine atom per phenolic moiety. The phenolic condensation products are capped so as to convert substantially all (greater than about 99.5%) of the hydroxyls to ether moieties. Each of the ether moieties is randomly selected from the group consisting of vinylbenzyl, alkyl containing 1 to ~0 carbon atoms, cycloalkyl of from 5 to 10 carbon atoms, and benzyl moieties as described above with respect to the first type of oligomer where the ratio of the vinylbenzyl to all other ether moieties is at least 1:1 and may be as high as 6:1.
The prepolymers may be prepared by acid catalyzed condensation of dihydric phenols with formaldehyde followed by end-capping substantially all the phenolic hydroxyls by converting them to ethers.
Acid catalyzed condensation is preferred to avoid the formation of terminal hydroxyl methylene groups, -CH20H.
End-capping by ether formation can be effected by any suitable means, such as by reacting the phenolic condensation product with an alkyl or benzyl halide in a basic medium.
The resulting thermosetting oligomers may be poly~erized with attendant crosslinking by a variety of . ~ , . .
' ' ' :' , : ,' , .
.~ - .

;2t ~ ~ &'~l 14 c~rlng m~an~. Wh~n cur~ng i~ ct-d by th~:~al ~-~n~, $t g-n~:~lly 1~ auto~nit~ted ~y hc~t~ng th- ollgo~-r r~ln 'n ~1~ or ~n lner~ at~o~p~re at a t-mpo~at~re b~tween ~bout lOo ~nd 300'C, and 30~- partl~ul~rly 5 b-tw--n ~bout 120 and ~OO-C. Curing al~o ~y b~ brought ~bout by c~mlc~ anc u-~ng a ~r~ ra~lcal in~t~ atcr uch ~c azo-b~ cbutyron~tr~l-, bon~oyl p-roxld-, ~nd dl-t-~utyl p~r~xl~ th- pra--nt $nv-nt~on cu~ng 1~
b gun by lrrad~t~on, e~poclal~y by v~ and 10 ultravlolet llg~t $n th~ pr-s-nc- or ~nc- o~ a ~n~ltt z-r o~ photols~itl~tor, ~ollowed by th~ l curing to prod~c~ an ln~bl~, ln~ol~l- gl~-~y ol~d Photed~ilna~l~ A~ cation~
The ollgom-r~ D~y b- u~ed a- a p~ nt, ~e ~n ln~-rl-vel ~l~loc:r~c, ~- a ~c oS pro~la$ng d~
d~p d~-l-c~rlc isolst~on ~nsulator ~lating ~ronohe~ high ~onp-r~tur- ~ol~r ~a~, or photoro~i~ Although ~uoh o~ ~h~t ~ollow~ c~b-~
2~ ~t- u~ r~ly ~- ~n lntorl-~-l d~ ot~c, t~o klllod worX-r wlll ~ooqn~z- ~o~ th~o d~er~ptlon how to ~ ~ th~ ~t~ o~ th- lnYontlon ln oth~r ~ppl~c~tion~
T~- ollgo~er~ ar~ i-d ~ ~ ¢o~tlng ~o a 25 - u~ta~ ub-tr~t-. Pr-~rably~ th- ao~ng will ha~
a thleXn~-o o~ 2 to 15 ~m, ~o~t pro~erably 5 to 10 ~
For th- ~o-~ p~rt t~o ~ub~tr~t-J u--~ will ~ a ~llleon wa~-r, ~ eon d~ip o~ ~n ~ntogratod cireu~t, a pr~ nt-~ ¢lreult board or ~ e~r~ie ~ub~tsat~ o 30 photoBen~lt~V~ 011~4~r~ may b- aFpli-d by ~pln eoat~ng, ~pr~y eoatlng, b~ u-- o~ ~ doetor ~nl~-, or ~ny ~t~ r eonv-n~lonaL t~chniquQ~ ~nown ~n tho ~rt ~D obta~n a u~i~orffl ~oatn~. ~h-r~ th~ vl-co~ty l~ too high, a ~olut~Dn o~ th~ r-~ln ln a ~ul~abl- olv-nt ~y ~ u~

T~U~ U~

.... . - . .

, . .. ... , , :....... -. . -`~ 3 ~ ,7 lS
5ho ollgc~er~ a~ lubl~ in a bro~d claa~ o~ o~v~nt~
'nc'u~ing pol~r ~pro_ic solYenta, crom~t~c hydrocar~on-, h~lo~-n~t-d hy~oc~rbon~, X-tono~ t~r. Ex~pl~- o~
~olven~ whic~ m~y ~- e~p~oy-d in ~he pr~ctic~ o~ ou:
lnv~ntion lnclud- ~i~et~yl~or~am~a- ~DMF), hexa~ethylpho-phor~lde (H~P~)~ N-m~thy~ac-t~mid-tX~AC), N,~-dic~hylac-t~id- ~D~Ac), d~ thyloulroxld~
(~MSO), ~-D-thylpyrrolidone ~NMR), b-n~an-, tolu~ne, xyl-n-, ethylbonz-n-, o~no, d~chlo~ han~, chloro~or~, ca~on tetr~chlsrldo, chlo~obens-n-, t~t-~chlo~o~han~,:otr~chloroethylQn~,tr~chtoroe~han~, g~m~-butyrol~cton~ thy~ thyl k-ton-, O.l-thyl ~ .on~ x~non~, h-ptanono, oct~none, ~ethyl ~otat-, thyl aoet~' e, ~utyl ~cetate, 2-~-~oxyet~lyl ~c~t~t-, ~thoxy ethanol, e~hoxy _h~nol, dlslym-, ant t~i~lym~.
~h~ oo~-nt ~hould b~ unr-~ctiv- ~th bo~h th~ ~ub~trate an~ the photoo~n~itl~e oligo~r~ and ablB to dl--olv~
th~ re~in~ to prov~d- ~t l~-t obout a ~O wolght~rolum-p rc-nt ~olut~on. s~nc- ~h~ ~ol~-nt 1- typ~c~lly ao ~c~o~ pr~or to ~ur~h-r proc~o~lng, ~t ~ o pr-~or~b~- th~t ~- low boll~n~ ~ ~olv~nt ~ po~-$bl~ bo u~ con~-t-nt w~th th~ ~or-go$ng con~ ration~.
Although t~ ol~om r- ~y ~o photo7O1y~ rlz~
d~r-ctly, a photo--n~it~zer or p~oto~n~tl~tor ~y b~
2S u~ nd ~ay b~ u~ul to ~-cro~-~ irr~atlon ~
Wher- ~ photo--n~it~zor or photo~nit~tor ~ u--d lt wllS b- ad~-d wi~h th- ol~go~ r~ ~t th~ ooat~ng tag ~n~ will b- p~ n: ~n an a~ount rrsm ~bo~t 0~001 to ~bout 5. 0 w~ght p-ro~nt r~ v- to th~ ollgo~ r~.
~xa~pl-s o~ ~hoto~on~it~zar- or photo~ni~la~or~ w~leh ~ay b- succ~-~lv~ly u~d ~n th- pr~ct~c o~ thl~
inv~n~lon ~nclud~ u~h m~t-r~al~ a~ ~-nzo~h-~on-, 4,4'-b ~ t ~yla~ 1~ o) b ~ s op~ no ~- , 4 , 4 ' -d~ t~oxy~n~oph ~on-, x~nt~on~, ac-~oph-non-, 4-lTUTF S~-~ ' .

S 5 ~ 7 t~t~luorom-thy!-ac-top~onono, ts$~h~nyl-n-, th~oY~nthon-, ~nt~aqulnon-, 4-p~nylb-n~ophenon-, naphth~l-n-, 2-~c-tonaphth~l-n~ c-tonap~thal-ne, ch~y~eno, an~hrac~n~, 9,10-~lc~loro~rthrac-n-, pyr 0-, S tr~phonyl~n~ luoronaphtha~en~ chloron~p~thalcnc, l-~ro~onaphth~l~n~ odon~phthalan-, 1,3-dlcyanob~ nQ, ~ hyl icophth~lat-, dl-thyl l~ophthala~ t~.yl 3-ey~no-b-n~o~t-, thyl 3-cyano-b-nzo~t-, ph~nyl 3-cy~no-b-nz~t-, 2,2-diD~tbo~ c-toph-non-, 2,2-~ oxy~c-toph-non-, 2,2'-dl~ethoxy-2-phonylace~ophsno~, 2,2'-dl-thoxy-2-ph~nylacotoph-non~, ~onzol~ ~thy~ oth~r, ~nd l-ph-nyl-1,2-p~opsn-dion--2-0-b-nzoyloxi~- ~r~ sod ~n~itizcr~ Lncludo b-n~oph-non-, 4,4'-lS ~ m-thyl~Lno)b~nzophenone, ',3-d~cyanob~n~n~, dl~ t~yl t~o~hthala~-, diot~yl i~ophthal-te, ~thy7 3-cyano-~nzoat~, a~d phonyl 3-cya~0-~0~80~t~
Wh-r- th- pho7~0~-n~lt~v- oli~ r~ ~a~o ~
appli~ a~ ~ ~olut~on to th- ~u~ra~- tho olv-nt u--d 20 ~N~t ~o r~o~ r~or :o ~rr~dlat~on Con~gu-nt~y, it conv-nttonal to h-~t th- CD~t-d u~-trate ~or a t~
U~ cl-nt tD r-~ov- eo~t~ally ~ll of th~ co~nt pr - ~ t, ~r any, prior to ~rr~i3~t~on, ~ ~t~g~ own th~ l~oo~tb~X- " It io for th~s re~oon that tho UJ~ o~
2~ o3l1ng ol-~-nt i~ ~r-~-rrod. It i- ~co~ bl- to u-~ ~nough hoat to ~roYid~ a ~ ~ icur-d c~tln~, ~pecially ~lnce the ollgomer~ ~ay b~gin ~o cure at t-mp-r~turo- ~- low a- ~bout l~O-C ~h- o~t~k- o~n b-carri-d ou~ ~n vaGuu~, und-r ~n in-st at~o-Fh-r~
nltrogon, h~llu~ ~n~ ~rgon) or ln ~lr A ~X oon~alnin~ th! ~ -ir-d p~tt-rn or '~g-~ pla~d ln cont~ot ox ~n prox~m~ty ~ th- co~t-d ~ub~rat- and ~h- ollgo~rc eoatlng ~ thQn l_ra~t~t-~
thxou~h th~ by x-r~y, l~ctron b-~, on b-a~r ;TITUT~. C~

.. .. . . . .
... . . . . .

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

17 :
ultr~iol~t, c- vl~ lc ~ndia'~on. For ~ on~ o~
~-onomy ~nd ~ac~ o~ rication lt ~ ~ p.-~errod to us~
r~d~lon in ~- rz~ng~ ~-om a~out 200 to a~out aoo n~no~ot-r~. Stnc~ low~r wavo long'~h ra~1ation 'c-nd~ to S a~o:~ b~ r r--olut~on, lrra~l-t~on in t~- 200-300 n~
r~ng~ r-~-rr~. W~t~ th~ tro~ent ~ irs~ t-d po:t~ on o~ t~c co~t~ns ~-co~o~ croc~linkod o t~at th-p~otoeroc~' lnXed oligom-r t 1~ rat~r ~n~olu~le ln th-e col~rent ~ n whic~ thc ori~ l photo--n~itiv~
lo ol lgom so r-~ln ~au t t~ oolu~
Irr~d.iat~on m~y ~e don~ lss ett~er t~e p-e--nco or a~c-nc~ o~ oxyg~n. Expo~uro tim- nee~cary ~or ad~qu~t- photoero~llnXing to a~ord ~h- difrerential ~olubility ch~ract~rlctl¢ ~ought ~p~n~ ~pon tho w~v~l~n~th o~ t~ ht u~e~, it~ int~nci~y, the pr~onco or ab-~no- o~ ~ p~otoc-n~ltlz~s or photoiniti~tor w~th a ~ar~t~on ~ro~ w ~econ~e up tA~ough ~ r~ nut ~. For pro~uction purpo--~ th-hort-r ~xpo~ura tl~-- ar- h~ghly ~r~-rr-d. On-~0 d-~lrabl- charactori~tlc o~ th- ~hoto~-n~tlv~ ollgom r-o~ thi~ inv~t~on ~ that t~y photoch~loally croc~link throughout t~ ~hi~Xn~-~ Or th4 f~l~. The~-~or-, th~
patt~rn how~ no or ~lnl~al und-rcut~ing upon d~v-lopuent.
Th~ CtiY- p~t ~ ~p~-~r~ upon ~ lopn~n~
~ith ~h- ~olv~nt. A~ m~ntion-d Abovo, u~on lrradl~tlon th p~oto--n-lt~- ol~go~r~c r~ln b-co~ x~-n-~Y-ly cro~ k d w~th ~ ~u~o~u-nt ~s~- d~ r-n~t ~olubllity ~t~on tho cro~ n~od~ or irradl~ , ~nd non-cro-~link-~, o~ non-~rrad~tod, por.tion~ o~ tha ol~gQmer-. Th- ~olY-n~ U~ n t~ ~ev-lop~ nt ~r- in g~n~- 1 th- ~um on-- u~-d ~n pr~p~r~ng ~ ~olut~on o~
t~- ~llgo~ar- ~o: co ting ~urpo~ hu~ cla~ of ~ol~ nt- J nclud- aprot~c olv~nt~, ar ~tio .

.

~ J 7 ~y~o~~bon-, halog-nat~d hyd:oc~bonc, ~ton-~, estar~, t~- g~ Carb~tol~, and ~ d ~olvont ~y-tom~
Upon ~-vclop~-nt ~el-ctl~ p~ttor~ pp-ar wh~r- th~ v~t-d por~ ~ orl- corro~pond to th-5 photoc~u~lc~lly c~ d o~qo~r~ r~llo~
~t~ctur-~ ~so th~ y cur-d to ~ord ~ hl~hly c~o~ n~ , ln~u~ible, gl~--y olld ~ghly ro~l~tant to ~lov~t-d t~p~r~tur-~ ¢~l degra~at~on, lon t:~por~, an~ wh~c~ ~cr~ a~ an Qfr~ot~y- protcc~lv~
10 l~y r and d~-locts~o ~n~ul~to~. Cur~ng ~ t~n~ y cros~ ng~ c~ rlnyl grou~ and `m~y b~ ct-d r th-rso~lly, eS~L~c~l~y, or pSotoch~ y, wlt~
thern~ 1 ~u~lng ~r-~-rr-d . Th~l cu~lng i~ r~l~y don~ in t S- t~p-r~tur r~slgo bc~w~on ~bout 100 ' C u~d 15 ~out 30C>C, ~nd o~ton ~ ~ done ln ~t~go-. So, 'or x~pl~, cur~ng m~y ~r~t ~ ect~d ~t a t-mp-ra~u~~
betw--n ~bout 150'C ~nd about 200 C ~or 0.5-~ hour- w~th po~tcuring ~t about 180 C-300 C ror about 0.5-24 hour~
Cur~ ng ~ ~o m~y ~ ~rDught a~out u~ ~ng a ~ro- radic~l in~tiato~, ~u~h ao ~zo~ obutyronlt~ zoyl p~rox~d-, ~nd d~-t-butylp~roxid .
~ h- ol~go~-r- o~ tha ~nv-ntlon hav~ n found p~rtlcul~rly u~-~ul Ln photo~-rln~bl- applicat~on- ~nc-th~y ~ b~ co~t d a~ olut~on~ w~h ~lgh col~- l-v-l-2S ~od thu~ ol~nt ~u~t bo evapor~t-d. Aloo, ~nc-no ~ol~tl~- by-~ro~uct~ ar~ g~n ~t-d au~ing curing th-hr~nka~- o~ th~ ~c 1~ m~ni~lz~.

~ S,~ PROC~SSNt~
~h- ~ub-tr~t~ tl - . c ra~c, alu~lna, ~ con, ~n~ print-d w~rlng bo~rd) ~y ~o oloan-~ wit~
oorv~ntion~l ol-~ning ~olY-nt~ (-.g., m-t~yl-n-SlJ8~iT!TUTE SU~

. ~ , . " ...... . . . .. . . . . . . .
-. -,: : - , . - .
~: :- . ' .. -. - . :. , . , , . . . . , .: . , - :

c~lorlde, c~.lor~o:2, Genel~o~ v , trlchloroethylon~, o-~sanol, m~.anol, o~u~ bl~ulfit, odiusl~ ~ul~lt-, and pota~ploying no~al cl-~n~ng proc-o~o~
a~ Xnown ln ~ ar~. In ~ltlon, t~ ra~ y 5 contain clrc~ ,r ~lr~y d~poa~ t-d upon ~ t. ~h-~u~ctr~ta ~y b- u~ d a~ r thc c~-~n~g proc--- or may b~ ~ur~c- t~ od ~o p~o~ot~ o~ on between tho tr~ nd ~ ~t~ or polym-~ d~ c~cr~ c lay r.
~ u-~d, an ad~ on pro~ot-r b-t~lrc--n ~ho sub~tratQ and~ d~ ctr~c l~yor may ~o cho~ rom a -~ng~ o~ ~r~o~ s~ lyl~t~ng ag-nta cor~t~ln~ng r~ac~iv-group~ c~p~lQ or r~actln~ wl~ tho poly~rs o th-ln~rentlon. Exa~ploo o~ ~us~aoe ~l~ylat$ng ~g~ wl~ich 15 can ~ p~ oy~d ar~ nyl ~thyldlmo~hoxy~ n-, v~nyltr~m--~oxy~lla~-, v~nyl~t~yldl-t~oxy~ no, v ~ n y 1 ~ r 1 o t h o x y o i 1 ~ n c, ~ ~t~oxynothylvlnylph-n-thyl~ n-, d~-thoxy~-thylvlnylphon-thyl~llan-, 20 tr~th~Yy~lnylp~enethyl-llan-, and tri~t~oxy-.rinylphen-~hyl~ll~-. ~r-~-rr~l 6~ lyl~tlng ~g~nt- ar~ vlnyl ~thyl~i~ot~oxy-llan-, 1 n y 1 ~ ~ h y 1 d ~ ~ t ~ o x y o i 1 a n , dlethoxy~t~ylvlnylph~n-thyl~ , and 2t ~ ~o~-~yl~nylph~-thy~ no ~- ~ur~aco ~llylat~ g-nt woul8 b- ~ -d to th ub-tsat~ v~a dipp~ng, pln co~tl ng, or o~-r t-o~nlguo- ~ro~ ~n alcohol-w~t r olutl o~. For x~pl~, a to ~.0 wt. ~
~o3.ut~ on o~ ~h~ .ylat~ng ~g~t 1~ olv-d ~n 8 5 to 30 9~ wt.% o~ ~l¢oho~ ~-.g., ~t~anol, ~t~anol, ~nd l~oprop~nol) ~ 1 to 13 w~.% o~ w~t~ tr~c d ~n t~ olutlon ~or 1~ con~ to 5 m~nut~-, Bi~ for 1 ~inute to 5 ~our-, ~ Sh-n ,T~ t-C~

-: ` . : ' , ' .

- ` ' ' '' o't :t:a~c-q for 1 ~nute to S hou-- at 60 to lOO-C ~lth-r Ln ~ con~Qct~on o~en, vacuu~ o~-n or ho~ plat~.
Th~ c~-an-d ~n~/or ~u~S~ce tro~tod u~-tr~t-wi l b- cover-d w~th ~ ~-tal p~ttern ~-~or~ ng cov-r~d w~h th~ d~'ol-c~ric l~y~ o~ tho ~n~ntlon. For xu~pl~ 500 to looo ~ l~y~r o~ o~ro~lu~, 8000 to 20000 A lay~r o~ copp~r and ~ 500 ~o looO ~ lay-r o~
¢hro~um may b cputt-rod onto tb< ~urfac-. Th n, th-~-tal l~y~r 1~ coated with a co~or¢ial photor-ci~t and proo--J~d accord~n~ to tho r-co3mondod proc~ ch-n-ut~ ing ~ sp~n co~t, co~t ba~c, i~ag~ng, d~-lop~n~
and h~rd b~- cycl~. Thl- exp~-o- pc~t~on~ o~ th- ~tal l~ycr to ~e romovo~ ~y tchlng to ~r~at- th~ pat~-~n.
Th~ ~ tal~ ar- ~tch-d utlllz~ng ~andas~ w~ t-chnlqu--, ~or ~xa~pl-: Th- top chro~ium lay~ QtC~d with ~ 1 t~ 30 % ~y~ro dlo~ c~ ~olutlon ~c~ t~d w~t~
~lu~lnu~ ~Dr ~0 ~cond~ to 5 ~lnut--~ th~ o~pp r l~y-:
i~ t~h~ wlth a ~o~lu~ p-~-ul~a~- ~olutlon ~or lo -cond~ to 10 ~Lnut~ h botto~ ohro~lu~ l~y~r ~
~tch-d wlt~ ~ 1 to 30 % hydrochlorlc ac~ ~olutlon -~ctl~t-~ w~th alu~lnu~ ~or lo -con~o to S ~l~ut~o: and ~lnally tho ~tch~d ~ub~trat- ~ wa~d w~th d~lon~zo~
w~te~ ~or 10 tD 60 ~-con~-. T~-n th- r~in~ng ~o~or~ t i~ ~tr~p-~ ~ro~ th- ~-t~l p~t~n - p-~
~S th- proc~ n~ t-c~nlqu -~¢o~-nd d ~or th~
photor~ t. Fin~lly th- cl-~n-d ub~tr~t- ~ dr~d p~$or to th- n~xt proc---ln~ ot-p.
Th ~l-l-otrlc l~y-r ~ co~t-d onto tr~t- ~nt 1~- ~ t~l p~tt~n d ~roc---o~
~ollow~ pr-poly~2~ ~- g, 10 to 80 wt ~ n ~n p~op~ ol~nt t~.~., toluene, NNP, D~F) $~ ~pln eo~-d ont~ Jtr~t-, at ~ ~p~d o~ 500 to 2~00 r~
~o~ 30 t~ ~o ~-c~ , ~e pr-poly~ co~to~ ctr~t-o~t b~ t a ~ p-r~ o~ ~S to ~O C ~r ~S ~nut-~

SU8~1YUTE ~

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~ 24 hour- in a vacu~ o~-n wit~. or wi~ou~ ~ nltrogon bla-d ~ o2t-bak-d coating ~ 8 th-n ~a$-d wl~ ~ W
llght sourc- (220-320 nD rang-) ~or 1~ ~con~ to 30 ninut~ mploylng ~ f d--~r-d d~o. v~ nd t~- lik~ pho~ocur~ polysl~er i~n d~-lop-d with an epprop~at- ~ol~ont yc~. g., tol~no, tolu~ne~h-Y~n~, tolu~no~-thanol,cycloh-xan-, t~yl~c-t~to, ~utyloc~tat~, d~71y~) ~t 2~ to 35'C wit~
o~ w~thout ultrasonlc~ or ~a praytn~ for S to 120 .o ~aonds~ th- d-Y~op-d 6u~-t~t- can t~en ba xpo~d to a ~'op os~ rt n~ b~t~ cr ol ~r~r.t ~pr~y ~a~-~' upon ~olv~nt ~y~t~ ~i-ci~lo with the d~Y~lopln~ eol~a~t but . poor solv-nt ~or ch- ~o~ ymer ~y~t ~ fo~ ~x~mpl~
h~x~n~, p~ntan-, and ~t~anol~ ~opt~on~l ~top); t~
15 ~r~, then cl~o~ w~: a pla~ or w ~ tch; and. ~inally ~ho dri-d ~ t~at~ i~ h~r~ ba~d ~n ~r~cuu~ ~r und~r ~n in~rt at~o-ph~r- (Q.Sl. ~ n~tro~n an~ ~rgon) wit~ ~
pr~r~red cu~- cycl~ includ~ng a r~p ~ro~ 2~- to 300-C
~or 38 m~nut-- to lo hour~, a hold at 3~0-C ~os~ 5 hou~
20 ~Ld th n a cool ~own ~ro~ 300' to 2~'C wt~ ~ 30 ~nut~
to 10 hour s Ullp .
~ h- pr~e--~ lo r-po~t~d a- r~qulr-~ in ordcr to ~orm ~n l-ct~on~c ~nt~rconnect ~truct~r~ o~ de~ir d l-ct:l~sl 3~ diolcctrc l~v~

Syn~h~ o~ ~tvren~ r~l~at-d Bl-ohe~ol-A-FQx~ald~hvd~
.t~A~F ~lOO_V~
50.0 g of ~-ph-no~-A ~orm-la~hyd~ ~B~A-F) ~n - 3g4r ~ - 680, ~-p~r~ity o~ 1-7) ~AO di-~olvod ~n 220 o~ ac-ton~ ~n a 1000 ~L 3-n-o~ round ~otto~ fl~-~~qu~pod wi~h ~-ch~n~c~ ~t~r~r~, th~r~ t-r, Therm-0-Wat~h, ~ond~n~ d~itlon ~unn~l nd-n~t~o~n purg-.
66 ~ ~0.46~ ~ol-~) o~ ~ln~l~en~ylch~osld- (60/40 ;, SUBSTITUTE SH~E~

, . ~ .. .. . . . ~. -- ~ , WO92/17X2~ PCT/US92/02352 ~, I ~;~''1 para/meta isomer ratio) was added to the reaction mixture and stirred for 30 minutes. The reaction mixture was ~eated to 65 C and then 41.80 g (0.745 moles) of potassium hydroxide in 143 mL of methanol was added to the reaction mixture over a 1 Hr period. The reaction was refluxed for 1 Hr. with stirring, the reaction mixture was cooled to a~bient temperature and allowed to stir for an additional 18 Hrs. The reaction mixture was recovered, dried over magnesium sulfate, filtered and concentrated under vacuum yielding a red resinous product of Mn = 501, Mw = 778, dispersity of 1.6 ~xam~le 2 SYnthesis of Stvrene Terminated Bis~henol-A-Formaldehvde rSTBPA-F (70VBz/30Pr~
Bisphenol-A formaldehyde ~BPA-F) was prepared as follows: 4S6.58 g (2.00 moles) of bisphenol-A, 90.00 g (3.00 mole of formaldehyde functionality) of paraformaldehyde, and 500 mL of ethanol were charged into a 2000 mL 3-necX flask equipped with a mechanical stirrer, thermometer, Therm-0-Watch, condenser, addition funnel and nitrogen purge. The reaction mixture was heated to 80-C, 2.00 mL of concentrated sulfuric acid was added dropwise over a 30 minute interval. The reaction was maintained at 80-C for 1 day. The solvent was distilled from the reaction mixture with the reactor equipped with a Dean-Stark trap and then the resin was poured into an aluminum pan, yielding 508.7 g of resin, Mn = 740, Mw - 8800, dispersity of 12Ø
228.31 grams of the above 8PA-F was dissolved in 700 mL of N-methylpyrrolidinone (NMP) in a 2000 mL 3-neck round bottom flask equipped with mechanical stirrer, addition funnel, condenser, thermometer, nitrogen purge and Therm-O-Watch. To this reaction .

. ~
..
' WO 92/1, 82~ PCl`~l lS92/0235~

~ ~ &, 7 mixture was added 213.67 g (1.400 moles) of vinylbenzylchloride (60/40 para/meta isomer ratio) and 0.10 g of 2,6-di-tert-butyl-p-cresol (BHT). The reaction mixture was heated to 60 C and 98.2 g (1.750 moles) of potassium hydroxide in 325 mL of methanol was added dropwise over a 1.5 hr interval. The reaction was maintained at 60 C for 19 hrs with stirring under a nitrogen purge. 99.63 g (0.810 moles) of n-propylbromide was added to the reaction mixture, to this reaction mixture was then added 45.45 g (0.810 moles) of potassium hydroxide in 150 mL of methanol over a 2 hr.
interval, the reaction was maintained at 60-C for 18 hrs. After cooling to room temperature the reaction mixture was transferred to a separatory funnel, 2 Liters of toluene was added and then washed four times with 2 Liters of water, dried over magnesium sùlfate, filtered and stripped under vacuum, yielding 636.6 g of resin: Nn = 1100, Mw ~ 18000, dispersity of 17.0: IR indicates presence of no residual hydroxyl moieties.
~x~Ple ~
Svnthesis of Stvrene Terminated Bis~henol-A-Formaldehvde (S~BPA-F (7OVBz/3OPr)) Bisphenol-A formaldehyde (BPA-F) was prepared as follows: 456.6 g (2.00 moles) of bisphenol-A, 45.04 g (1.50 mole of formaldehyde functionality) of paraformaldehyde, and 350 mL of ethanol were charged into a 2000 mL 3-neck flask equipped with a mechanical stirrer, thermometer, Therm-O-Watch, condenser, addition - funnel and nitrogen purge. The reaction mixture was heated to 80-C, 4.00 mL of concentrated sulfuric acid was added dropwise over a 5 minute interval. The reaction was ~aintained at 80-C for 1 day. The solvent was distilled from the re~ction mixture with the reactor equipped with a Dean-Stark trap and then the resin was ....
: ~ .. ;- . , , - ' , :. . .: ~ :

.`

~os~/l7~2~ PCT/US92/0235 5r~

poured into an aluminum pan, yielding 447.6 g of resin, = 230, Mw = 1400, dispersity of 5.8.
228.29 grams of the above BPA-F was dissolved in 700 mL of N-methylpyrrolidinone (NMP) in a 2000 mL 3-neck round bottom flask equipped with mechanicalstirrer, addition funnel, condenser, thermometer, nitrogen purge and Therm-O-Watch. To this reaction mixture was added 213.67 g (1.400 moles) of vinyl~enzylchloride (60/40 para/meta isomer ratio) and 0.10 g of 2,6-di-tert-~utyl-p-cresol (BHT). The reaction mixture was heated to 60-C and 98.19 g (1.750 moles) of potassium hydroxide in 430 mL of methanol was added dropwise over a 2.0 hr interval. The reaction was maintained at 60'C for 19 hrs with stirring under a nitrogen purge. 99.63 g (0.810 moles) of n-propylbromide was added to the reaction mixture, to this reaction mixture was then added 4S.45 g (0.810 moles) of potassium hydroxide in 230 mL of methanol over a 1.25 hr. interval, the reaction was maintained at 60-C for 18 hrs. Analysis of a small aliquot of the reaction mixture after work-up indicates residual hydroxyl groups. 9.96 g (0.081 moles) of n-propyl~romide was added to the reaction mixture and then 4.54 g (0.081 moles) of potassium hydroxide in 30 mL of methanol was added to the reaction mixture and reacted 6 hrs. at 60-C. After cooling to room temperature the reaction mixture was transferred to a separatory funnel, 1.5 Liters of toluene was added and then washed four times with 1 Liter of water, dried over magnesium sulfate, filtered and stripped under vacuum, yielding 334.73 g of resin; Mn - 730, Mw = 1800, dispersity of 2.5: IR
indicates presence of no residual hydroxyl moieties.

~O92/1782~ PCT/US92/0235 ExamPle 4 nthesis o Stvrene Terminated ~is~henol-A-Formaldeh~de-~ihYdrox~benzohenone rST~PA-F-BP (70VBz/30Pr)) S8isphenol-A-formaldehyde-dihydroxybenzcphenone (BPA-F-BP) was prepared as follows: 433.75 g (1.90 moles) of bisphenol-A, 21.42 g (0.10 moles) of 4,4'-dihydroxybenzophenone, 69.07 g (2.30 moles of formaldehyde functionality) of paraformaldehyde, and 500 mL of ethanol were charged into a 2000 mL 3-neck flask equipped with a mechanical stirrer, thermometer, Therm-O-Watch, condenser, addition funnel and nitrogen purge.
~he reaction mixture was heated to 80-C, 4.00 mL of concentrated sulfuric acid was added dropwise over a 3 minute interval. ~he reaction was maintained at 80-C
for 1 day. The solvent was distilled from-the reaction mixture with the reactor equipped with a Dean-Stark trap and then the resin was poured into an aluminum pan, yielding 415.5 g of resin, Mn z 300, Mw = 2300, dispersity of 7.9.
228.29 grams of the above BPA-F-BP was dissolved in 700 mL of N-methylpyrrolidinone (NMP) in a 2000 mL 3-neck round bottom f}ask equipped with mechanical stirrer, addition funnel, condenser, thermometer, nitrogen purge and Therm-O-Watch. To this reaction mixture was added 213.67 g (1.400 moles) of vinylbenzylchloride (60/40 para/meta isomer ratio). The reaction mixture was heated to 60-C and 98.19 g (1.750 moles) of potassium hydroxide in 375 mL of methanol was added dropwise over a 2.0 hr interval. The reaction was maintained at 60 C for 19 hrs with stirring under a nitrogen purge. 99.63 g (0.810 moles) of n-propylbromide was added to the reaction mixture, to this reaction mixture was then added 45.45 g (0.810 moles) of - , :
.

wo s2/17X2n PCr/US92/0235 potassium hydroxide in 250 mL of methanol over a 2 hr.
interval, the reaction was maintained at 60-C for 18 hrs. A small aliquot was removed from the reaction mixture, worked-up and IR analysis indicates residual hydroxyl moieties. 9.96 g (0.081 moles) of n-propylbromide was added to the reaction mixture, and then 4.54 g (0.081 moles) of potassium hydroxide in 20 mL of methanol was added and the reaction mixture was reacted for 18 hrs. After cooling to room temperature the reaction mixture was transferred to a separatory funnel, 1.5 Liters of toluene was added and then washed thrice with 1 Liter of water, dried over magnesium sulfate, filtered and stripped under vacuum, yielding 222.8 g of resin; Mn = 700, Mw = 2400, dispersity of 3.4; IR indicates presence of no residual hydroxyl moieties .
Fxample 5 , SYnthesis of Stvrene-Terminated Tetra~henol Ethane (70% Vinvlbenzvl/30% Pro~vl~
, 20 (STTPE(70 VBz~30 Pr~) To a 3000 mL round bottom, 3-neck flask eguipped with a mechanical stirrer, addition funnel, condenser, thermometer, Therm-O-Watch, drying tube and nitrogen purge was added 353.0 g of tetraphenol ethane (Mn= 274, Mw- 711) (0.500 moles), 3.30 g of BHT (0.0150 moles) and 1670 mL of N-methyl pyrrolidinone (NMP).
- Upon dissolution of the TPE, 373.89 g (2.4S moles) of vinylbenzyl chloride (YBC1 were added. The reaction mixture was heated to 60-C and 160.25 g (2.500 moles) of potassium hydroxide in 360 mL of methanol were added dropwise over a 30 minute interval. The mixture was kept at 60-C for an additional 3.5 hours, then 127.0 mL
of l-bromopropane (1.400 moles) was added. 68.68 g (1.070 moles) of potassium hydroxide in 150 mL of ' ~

.

.
. ~

.

~09~1782~ PCT/~'S92/023 methanol was then added dropwise over a 30 minute interval anA the temperature maintained at 60 C and additional 1.5 hours.
~ he ~ixture was cooled and 2 L of toluene were added. The mixture was washed once with 5 L of water and thrice with 5 L of 1 M sodium chloride solution.
The organic phase was dried over sodium sulfate, filtered through Celite, filtered and concentrated under vacuum yielding 84 % of resinous product, Mn=576, Mw=915, dispersity of 1.59.
ExamDle 6 Svnthesis of Stvrene-Terminated TetraDhenol Et~ane rlO0~ VinvlbenzYlL_(STTpE( 100 VBz)) 0l To a 2000 mL round bottom, 3-neck flask equipped with a mechanical stirrer, addition funnel, condenser, thermometer, Therm-0-Watch, drying tube and , nitrogen purge was added 200.0 g of tetraphenol ethane (Mn= 274, Mw= 711) (0.284 moles), 1.88 g of BHT (0.00853 moles) and 950 mL of N-methyl pyrrolidinone (NMP). Upon dissolution of the TPE, 242.65 g (1.50 moles) of -~ vinylbenzyl chloride (~BC) were added. The reaction mixture was heated to 60-C and 101.95 g (1.590 moles) of potassium hydroxide in 230 mL of methanol were added dropwise over a 30 minute interval. The mixture was kept at 60-C for an additional 4.75 hours. 15.17 g (0.0994 moles) of vinylbenzyl chloride was added. 6.37 g (O.0994 moles) of potassium hydroxide in 15 mL of ` methanol was then added dropwise over a 30 minute ;x interval and the temperature maintained at 60-C and - 30 additional 1.7 hours. 15.17 g (0.0994 moles) of vinylbenzyl chloride was added. 6.37 g (0.0994 moles) of potassium hydroxide in 15 mL of methanol was then added dropwise over a 30 minute interval and the te~perature maintained at 60-C and additional 1.0 hour ~:' .
, .~

.
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92~ 1, 8~(, PCrll 'S92/0235 The mixture was cooled and 1.2 L of toluene were added. The mixture was washed once with 3 L of water and twice with 3 L of 1 M sodium chloride ; solution. The organic phase was dried over sodium sulfate, filtered through Celite, filtered and concentrated under vacuum yielding 95 % of resinous product, Mns778, Mw=1079, dispersity of 1.39.
Exam~le 7 A series of styrene terminated bisphenol-A
formaldehyde (STBPA-F) resins, Samples A, B, C, and D of - ~xample 1, 2, 3, and 4 respectively, were cured via the following cure cycle 2 hrs. at 80-C, 16 hrs. at lOO-C, 4 hrs. at 120-C, 16 hrs. at 160-C, 2 hrs. at 200 C and 1 hr at 225-C and their properties measured. The results are summarized in the following table.

~abl- 1 ; 8~BPA-F Prop-rties ` Sample No. A B C D
20 Tg (-C)~-) 206 >300 >300 >300 Tsp (-C) tb)193+6 118+5 205+3 153+3 ~,p (ppm/-C)~') 55+1 52+4 49+3 80+8 ~ t~2~ (ppm/ C)77+1 66+4 7s+4 125+6 '' ~- ~"') 3.29 2.86 2.86 2.91 tan ~f~ 0.004 0.001 0.006 0.006 ~- 30 ~'t~) ND 2.90 2.91 2.94 tan ~ ~h) ND 0.0005 0.006 0.017 % Water Absorption~i~ ND 0.~54 0.300 0.264 . .

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ND: Not Determined r (a) Glass transition temperature by differential scanning calorimeter.
(b) Softening point by Thermo Mechanical Analysis -minor thermal transition.
` (c) Coefficient of thermal expansion between 25 C and softening point.
(d) Coefficient of thermal expansion between 25 C and - 10 260 C.
(e) Dielectric constant at 1 MHz and 0% Relative Humidity at 25-C.
(f) Loss tangent at 1 MHz and 0% Relative Humidity at 25 C.
(g) Dielectric constant at 1 MHz and 50% Relative Humidity at 25-C.
(h) Loss tangent at 1 MHz and 50% Relative Humidity at 25-C.
(i) At 50% Relative Humidity, 25-C for 168 hours.
` 20 E~am~le 8 3~ Samples A through D were prepared from Solution 1: 0.4936 g of STBPA-F of Example 1 was dissolved in 4.4493 g of DMF. Samples E through H were . 25 prepared from Solution 2: 0.5049 g of STBPA-F of Example x ~ and 0.0063 g of 4,4'-bis(dimethylamino)benzophenone was dissolved in 4.6008 g of DMF. Sample I through L
~ were prepared from Solution 3: 0.475 g of STBPA-F of - Example 1 and 0.0250 g of 4,4'-`30 bis(dismethylamino)benzophenone was dissolved in S.3100 g of DMF.
iThese solutions were spin coated onto silicon ;;wafers at 1150 rpm for 10 seconds. The wafers were . . . .
~ .

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WO92/17~2~ PCT/~S92/0235' `L) ~

; exposed to 200 watt Mercury Vapor Lamp fsr varying time intervals and then checked for solubility in DMF.

Table 2 Sam~le W EXDOSUre Time Solubility Testina (sec~ Results A 30 Dissolves readily; slight ` r e s i s t a n c e t o dissolution.
8 60 Resistant to dissolution;
dissolves with long ~ exposure (>0.5 Hrs) to ; solvent.
"` 15 C 120 Resistant to dissolution;
dissolves with long exposure (>0.5 Hrs.) to solvent.
. . .- "
- D 300 Very resistant to ~ dissolution.
. . .
:.:' E 30 Some resistance to dissolution; dissolves with long exposure (>0.5 Hrs.) to solvent.
. ~ .
F 60 Resistant to dissolution;
dissolves with long exposure (>0.5 Hrs.) to solvent.

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~-Wos2/~7s2n PCT/US92/0235' 3 ~ r~ rl G 120 Resistant to dissolution;
dissolves with long exposure (>0.5 Hrs.) to solvent.

H 300 Very resistant to dissolution.
.

I 30 Resistant to dissolution;
dissolves with long exposure (>1.0 Hr.) to solvent.

` J 60 Resistant to dissolution;
'j 15 dissolves with long exposure (>l.0 Hrs.) to solvent.
', K 120 Very resistant to dissolution.

L 300 Very resistant to dissolution.
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wo 92/17820 PC'r/l,'S92/023S' , S, ,; ,~ 1 , ~xam~le 9 - A 40.60 wt. % STBPA-F (Example 2) solution in toluene was spin coated onto a silicon surface at 1000 rpm for 60 seconds. The coated discs were soft baked at 25-C for 18 hours under vacuum. Then, they were exposed for 3 minutes to W irradiation with a 200 watt mercury vapor lamp with a quartz/water filter. The irradiated coatings and uncured coatings were then exposed to various solvents and the amount of resin dissolved was measured. The results are shown in the following tables.
Table 3 'i ~issolution Studv of STBPA-F~
~ % STBPA-F Removed .~t 15 Time (sec)Solvent tToluene:Ethanol)b ~ 100:0 80:20 60:40 40:60 20:80 0:100 '~ O O O O O O O
;:~ 30 95.88 96.93 54.71 25.95 6.51 -1.20 98.82 99.39 61.18 31.01 8.28 -2.41 120 98.24 99.39 65.29 36.08 11.24 -3.01 180 97.65 100.00 66.47 38.61 13.02 -1.81 300 98.24 100.00 68.82 42.41 15.98 -1.20 a) STBPA-F coated on silicon wafer and soft baked at 2525-C for 18 Hrs.
~- b) Weight % solutions.

Table 4 ~; ~issolution Studv of STBPA-~
~ 30% STBPA-F Removed :,'J, Time tsec~ Solvent ~Toluene:n-Hexane)b b~ 1 0 0 0 80:20 60:40 40:60 20:80 0:100 O O O O O O O
. i~
~ 30 95.88 94.27 90.S9 56.82 14.04 0.00 .,;

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w092/17x20 PCT/~S92/0235~

u 7 98.82 98.44 95~88 64.39 1~.13 -1.21 120 98.24 96.88 95.29 70.45 22.22 0.00 - 180 97.65 97.92 96.47 74.24 26.32 0.00 300 98.24 98.44 97.06 78.03 30.41 1.21 a) STBPA-F coated on silicon wafer and soft baked at 25-C for 18 Hrs.
b) Weight % solutions.

Table 5 pissolution Studv of Photocured STBPA-Fa % STBPA-F Removed Time (sec) Solvent rToluene:Ethanol~b 100:0 80:20 60:40 40:60 20:80 0:100 1.74 4.71 1.16 -0.61 -0.60 -0.58 1.16 3.53 1.74 -1.22 -1.80 -1.73 120 1.74 4.12 0.58 -1.22 -2.40 -2.31 180 1.74 4.71 0.00 -5.49 -1.80 -2.31 300 2.91 -3.53 2.91 1.22 -1.80 -1.73 a) STBPA-F coated on silicon wafer and soft baked at 25-C for 18 Hrs, 3 minute cure 200 Watt Mercury Vapor Lamp with quartz/water filter.
b) Weight S solutions.

Table 6 Dissolution Studv of Photocured STBPA-P
% STBPA-F Removed ~.ime (sec~ Solvent (Toluene:n-Hexane~b 100:0 80:20 60:40 40:60 20:80 0:100 30 1.74 0.60-0.61 0.00 0.00 -0.51 60 1.16 0.600.00 -1.17 -1.20 -2.02 ~: '., ' :,'; " ' ' ; , ' ' . .
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120 1.74 0.00 0.61 -1.75 -1.8~-2.53 180 1.74 1.19 0.61 0.60 -0.60-3.03 300 2.91 1.79 1.83 1.75 -1.20-3.03 a) STBPA-F coated on silicon wafer and soft baked at 25-C for 18 Hrs, 3 minute cure 200 Watt Mercury Vapor Lamp with quartz/water filter.
b) Weight % solutions.

Table 7 Dissolution StUdy of STBPA-Fa % STBPA-F Removed Time (sec~ Solvent (Cyclohexane:Hexane)b 100:0 80:20 60:40 0:100 1.07-1.05 -2.20 0.00 2.671.05 0.00 -1.21 120 4.282.62 1.65 0.00 180 6.424.19 3.30 0.00 300 9.637.33 6.59 1.21 a) STBPA-F coated on silicon wafer and soft baked at 2S-C for 18 Hrs.
b) Weight % solutions.
Table 8 Dissolution Studv of Photocured STBPA-Fa % ST8PA-F Removed Time (sec) Solvent !Cyclohexane:Hexane)b 100:080:2060:40 0:100 O O O O O
-2.67-l.S5 -2.58 -0.51 -2.14-1.55 -2.06 -2.~2 120 -2.67-2.07 -2.58 -2.53 ... ..... . . . . .

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180 -4.28 -4.15 -5.15 -3.03 300 -3.21 -1.04 -2.06 -3.03 a) STBPA-F coated on silicon wafer and soft baked at 25 C for 18 Hrs, 3 minute cure 200 Watt Mercury Vapor Lamp with quartz/water filter.
b) Weight ~ solutions.

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and 59.40 % toluene. This solution was spin coated onto a silicon surface utilizing spin coating rates from 500 to 2000 rpm for 60 seconds; soft baked for 18 hours at 25-C under vacuum. The samples were then exposed for 60 to 180 seconds to W irradiation with a 200 watt mercury lamp employing an USAF Test Resolution Pattern and a quartz/water filter. The photocured polymer was then developed for 45 seconds to 120 seconds at 25-C with: a) toluene with a hexane rinse, or b) diglyme with an ethanol rinse. The air dried substrate was hard baked employing a cure cycle under vacuum of 25-C to 230 C
ramp in 2 hours, held at 230-C for 1 hour and then cooled to room temperature over a 2 hour period.
The film thickness of the photocured polymer was analyzed employing a Taylor-Hobson Talysurf 10 profilometer.

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w092tl7~2~ PCT/US92/0235 Example 11 STBPA-F of Example 2 was dissolved in xylene to yield a solution of composition 42.16 wt. % STBPA-F
and 57.84 ~ xylene. This solution was spin coated onto a silicon surface utilizing spin coating rates from 500 to 2000 rp~ for 60 seconds; soft baked for 18 hours at 25'C under vacuum. The samples were then exposed for 120 to 180 seconds to W irradiation with a 200 watt mercury lamp employing an USAF Test Resolution Pattern and a quartz/water filter. The photocured polymer was then developed for 45 seconds to 120 seconds at 25-C
with ethyl acetate ~EtAc) or diglyme with an ethanol rinse. The air dried substrate was hard baked employing a cure cycle under vacuum of 25-C to 230-C ramp in 2 hours, held at 230-C for 1 hour and then cooled to room temperature over a 2 hour period, The film thickness of the photocured polymer was analyzed employing a Taylor-Hobson Talysurf lO
profilometer.

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Exam~le 12 A 60.87 wt. % STBPA-F-BP (Example 4) solution in toluene was spin coated onto a silicon surface at 1000 rpm for 40 seconds. The coated discs were soft baked at 25 C for 18 hours under vacuum. Then, they were exposed for 3 minutes to W irradiation with a 200 watt mercury vapor lamp with a quartz/water filter. The irradiated coatings and uncured coatings were then exposed to various solvents and the amount of resin dissolved was measured. The results are shown in the following tables.

Table 15 Dissolution StudY of STBPA-F-~P
15 % STBPA-F-BP Removed Solvent Time Cyclo- Chloro-(sec) Toluene ~exane hexane Xylene Cumene benzene 96.62 2.06 6.34 99.00 96.23 96.15 100.00 2.75 9.86 101.00 99.69 99.04 120 --- 5.50 14.44 --- --- ---180 --- 5.15 19.72 --- --- ---25 300 --- 4.47 19.37 --- --- ---a) STBPA-F-BP coated on silicon wafer and soft baked at 25'C for 18 Hrs~

~'' ,'' ~- , ' ~ , ~ 0 9'/ 1 7820 PCr/US92/0235~

;~ L ~ r~ r~~ rj1 Table 16 Dissolution Studv o Photocured STBPA-F-BP~
% STBPA-F-BP Removed Solvent 5 TimeCyclo- Chloro-(secl Toluene Hexane hexane Xvlene Cumene benzene O O O O O O O
7.43 1.01 1.03 6.29 6.18 6.64 7.77 2.02 3.09 7.34 8.73 9.59 10 120 9.80 1.68 3.09 7.34 11.64 9.23 180 9.80 2.02 4.47 7.69 12.36 9.59 300 9.46 2.69 3.09 8.39 15.64 8.86 a) S~BPA-F-BP coated on silicon wafer and soft baked at 25-C for 18 Hrs, 3 minute cure 200 Watt Mercury Vapor Lamp with quartz/water filter.

Table 17 ~issolution Studv of STBPA-F-BP-~b % ST~PA-F-BP Removed Time Solvent ~sec~ DMF Ethanol EtAc ~uAc DMAc O O O O O O O
95.86 98.65 4.53 97.63 98.95 100.00 100.69 100.34 7.32 100.00 98.95 100.72 120 --- --- 8.01 --- --- ---180 --- --- 9.06 - - --- ---300 --- --- 8.36 --- --- ---a) STBPA-F-BP coated on silicon wafer and soft baked at 25-C for 18 Hrs.
b) Ethanol rinse utilized after each exposure to developing solvent.

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WO92/17820 PCT/US92/0235' . ~ ` ) Table 18 Dissolution StudY of Photocured STBPA-F-8~b % STBPA-F-BP Removed Time Solvent s ~sec) NMP ~MF ~hanol EtAc BuAc pMAc O O O O o O O
15.32 16.61 2.10 13.71 4.75 6.78 13.25 17.29 2.80 19.40 8.14 7.12 120 12.91 16.27 2.10 22.07 13.56 7.46 180 11.92 17.29 1.40 22.74 16.61 7.46 300 14.24 15.93 2.10 23.41 20.00 6.44 ., .
a) STBPA-F-BP coated on silicon wafer and soft baked at 25-C for 18 Hrs, 3 minute cure 200 Watt Mercury Vapor Lamp with quartz/water filter.
b) Ethanol rinse utilized after each exposure to dev~loping solvent.
:,', .
~, Table 19 ., 20 Di~solution Study of ST8PA-F-BP^~b % STBPA-F-BP Removed Solvent Time l-methoxy- Nitro-~ (sec)Dialyme 2-~ro~anol methane ., 25 0 0 0 0 97.93 81.91 21.05 99.66 90.78 25.96 3 120100.00 93.52 29.12 180 ---- 93.S2 30.88 30 300 ---- 93.86 31.93 ., ~, a) ST8PA-F-BP coated on silicon wafer and soft baked at 25-C for 18 Hrs.
-., , : . . . . .

wo92/1782n PCT/US92/0235 ~ 3:, ~

b) Ethanol rinse utilized after each.exposure to developing solvent.

~able 20 Dissolution Stud~ of Photocured STBPA-F-BP~b % STBPA-F-~P Removed ~,olve~t Time l-methoxy- Nitro-~sec) Di~lvme ,2-~ro~anolmethane 1030 13.98 6.64 8.25 13.26 6.99 3.30 120 12.90 8.39 2.97 180 1~.19 8.39 2.31 300 12.19 8.04 2.31 a) STBPA-F-BP coated on silicon wafer and soft baXed at 25-C for 18 Hrs, 3 minute cure 200 Watt Mercury Vapor Lamp with guartz/water filter.
b) Ethanol rinse utilized after each exposure to developing solvent.

Exam~le 13 STBPA-F-BP of Example 4 was dissolved in toluene to yield a solution of composition 46.17 wt. %
STBPA-F-BP and 53.83 % toluene. This solution was spin coated onto a silicon surface utilizing spin coating ,rates from 500 to 2000 rpm for 40 seconds; soft baked for 18 hours at 25-C under vacuum. The samples were then exposed for 30 to 90 seconds to W irradiation with ` 30 a 200 watt mercury lamp employing an USAF ~est Resolution Pattern and a quartz/water filter. The photocured polymer was then developed for 15 seconds at 25-C with butyl acetate (BuAc) or diglyme with an ~' ethanol rinse. The air dried substrate was hard baked ,~

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- . .

w092/1~82~ PCT/~'S92/0235' employing a cure cycle under vacuum of 25'C to 230-C
ramp in 2 hours, held at 230 C for 1 hour and then cooled to room temperature over a 2 hour period.
The film thickness of the photocured polymer was analyzed employing a Taylor-Hobson Talysurf 10 profilometer.

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WO92/17820 PCT/US92/023S' ) ¦ ~3 ~ i ~ l so ExamDle 14 A series (Samples A, B , and C, below) of mixtures styrene terminated bisphenol-A formaldehyde (STBPA-F) of Example 2 and styrene terminated tetraphenolethane (STTPE) of Example 5 were cured prepared and cured via the following cure cycle: 2 hrs.
at 80-C, 16 hrs. at lOO-C, 4 hrs. at 120-C, 16 hrs. at 160-C, 2 hrs. at 200-C, and 1 hour at 225 C and their properties were measured.

Table 22 STBPA-F:STTPE Pro~erties Sample No. A_ B C
STBPA-F:STTPE 90:10 75:25 50:50 Tg (-C)~') >300 >300 >300 Tsp (-C) ~b) 130+5 134+6 218+7 ~sp (ppm/-c)~C) 51+3 66+2 39+2 t~2~ (ppm/-c)~) 62+2 85+2 44+1 ~"" 2.85 2.85 2.90 tan ~ 0.0003 0.002 0.003 ~ ~t9) 2.89 2.88 2.94 tan ~th) 0.002 0.002 0.003 % Water Absorption~i~ 0.169 0.152 0.163 (a) Glass transition temperature by differential scanning calorimeter.

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wos~/17x2n PCT/~S92/023~2 (b) Softening point by Thermo Mechanical Analysis - minor thermal transition.
(c) Coefficient of thermal expansion between 25-C and softening point.
5 (d) Coefficient of thermal expansion between 25-C and 260 C.
(e) Dielectric constant at 1 MHz and 0%
Relative Humidity at 25-C
(f) Loss tangent at 1 MHz and 0% Relative Humidity at 25-C.
(g) Dielectric constant at 1 MHz and 50%
Relative Humidity at 25 C.
(h) Loss tangent at 1 MHz and 50% Relative Humidity at 25-C.
(i) At 50~ Relative Humidity, 25-C for 168 hours.
~; Exam~le 15 `~ A 39.89% resins solids coating solution of ~' 50:50 STBPA-F ~Example 2):STTPE (Example 5) was prepared ~, 20 in toluene solution. The solution was applied to a ~ silicon surface via spin coating at 1000 rpm for 60 '7~ seconds. The coated discs were soft baked at 25-C for 18 hours under vacuum. Then, they were exposed for 3 minutes to W irradiation with a 200 watt mercury vapor lamp with a guartz/water filter. The irradiated coatings and uncured coatings were then exposed to various solvents and the amount of resin dissolved was ;~5 measured. The results are shown in the following tables.

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W092/17X20 PCT/~lS92/0235' Table 25 Dissolution Study of 50:50 STBPA-F:STTPE~b % STBPA-F/STTPE Removed Time Solvent rsec) E~ BuAc QMAc DMF Di~lvme '. O o O o O O
83.s3 85.15 86.8186.7887.36 94.12 94.06 93.4196.6795.40 120 94.12 93.07 94.5195.5694.25 18092.94 94.06 93.4195.56 95.40 x 30092.94 95.05 94.5195.56 95.40 a) 50:50 STBPA-F:STTPE coated on silicon wafer and soft baked at 25-C for 18 Hrs.
b) Ethanol rinse of sample after developing solvent exposure.
~able 26 Dissolution Studv of Photocured 50:50 STBPA-F: ST~PE-~b % STBPA-F/STTPE Removed Time ~Qlvent ~, 20 ~sec) E5~,c BuAc E~a~ ~F Dialvme ~x" O O O o O O
; 30 11.11 8.70 21.6518.18 19.78 ~ 60 23.33 21.74 24.7421.59 20.88 ,~ 12016.67 16.30 18.5613.64 16.48 18020.00 20.65 23.7118.18 18.68 30020.00 19.57 22.6819.32 16.48 ~ a) 50:50 STBPA-F:STTPE coated on silicon wafer and `~ soft baked at 25 C for 18 Hrs, 3 minute cure 200 '"A Watt Mercury Vapor Lamp with guartz/water ~,~ 30 filter.
b) Ethanol rinse of sample after developing solvent exposure.
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32.95 46.59 -3.33 ~` 60 47.73 63.64 4.44 10 120 50.00 68.18 3.33 180 51.14 69.32 3.33 300 54.55 70.45 3.33 a) 50:50 STBPA-F:STTPE coated on silicon wafer and , soft baked at 25-C for 18 Hrs.
15 b) Ethanol rinse of sample after developing solvent exposure.
' Table 28 ~, Dissolution Studv of Photocured 50:50 STBPA-F:STTPE'~b , % STBPA-F/S~TPE Removed ~, 20Solvent , Timel-methoxy-~-;, (sec)Nitromethane 2-pro~anol E~Q~
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307.61 10.64 7.37 ~s 25 60 10.87 12.77 8.42 `~ 1207.61 12.77 8.42 1807.61 12.77 8.42 007.61 12.77 6.32 ~) 50:50 ST~PA-F:STTPE coated on silicon wafer and soft baked at 25-C for 18 Hrs, 3 minute cure 200 Watt Mercury Vapor Lamp with quartz/water .~j filter.
b) Ethanol rinse of sample after developing solvent exposure.
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toluene. This solution was spin coated onto a silicon surface utilizing spin coating rates from 500 to 2000 rpm for 60 seconds; soft baked for 18 hours at 25-C
under vacuum. The samples were then exposed for 60 to 180 seconds to W irradiation with a 200 watt mercury lamp employing an USAF Test Resolution Pattern and a quartz/water filter. The photocured polymer was then developed for 15 seconds to 45 seconds with butyl ; acetate (BuAc) or diglyme with an ethanol rinse at 25 C.
The air dried substrate was hard baked employing a cure ~;i 15 cycle under vacuum of 25-C to 230-C ramp in 2 hours, held at 230-C for 1 hour and then cooled to room ~ temperature over a 2 hour period.
'i The film thickness of the photocured polymer was analyzed employing a Taylor-Hobson Talysurf 10 profilometer.

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Claims (12)

CLAIMS:

1. A method of forming a polymer on a substrate in a predetermined pattern comprising:
(a) coating a substrate with a prepolymer which is an ether of the oligomeric condensation product of a dihydric phenol and formaldehyde having the formula where the recurring unit Q has the structure, OR and n is an integer from 1 to 10;
s is 0 or 1;
each X is independently selected from the group consisting of CH2, C(CH3)2, O, S, SO2, CO, and OC6H4O;
each R1 and R2 is independently selected from the group consisting of hydrogen, alkyl and alkoxy moieties containing 1 to 10 carbon atoms, phenyl and phenoxy;
a and b are independently 0 or integers from 1 to 4;
Z is Cl or Br;
E is selected from the group consisting of the vinylbenzyl moiety, alkyl moieties containing 1 to 10 carbon atoms, or benzyl, subject to the constraint that at least 50% of all E's are the vinylbenzyl moiety;

(b) irradiating the coated prepolymer of (a) through a masking pattern to selectively crosslink the portion of said coating being irradiated;
(c) selectively dissolving the non-irradiated part of the prepolymer coating of (a); and (d) curing the crosslinked portion of the prepolymer coating by heating at a temperature in the range of 100°C to 300°C for a time sufficient to further crosslink said crosslinked coating and to transform the prepolymer to an infusible glassy solid.

2. A method of forming a polymer on a substrate in a predetermined pattern comprising:
a. coating a substrate with a mixture of prepolymers which comprises (1) an ether of the oligomeric condensation product of a dihydric phenol and formaldehyde having the formula where the recurring unit Q has the structure, OR and n is an integer from 1 to 10;
s is 0 or 1:
each X is independently selected from the group consisting of CH2, C(CH3)2, O, S, SO2, CO, and OC6H4O;
each R1 and R2 is independently selected from the group consisting of hydrogen, alkyl and alkoxy moieties containing 1 to 10 carbon atoms, phenyl and phenoxy;
a and b are independently 0 or integers from 1 to 4;
Z is Cl or Br;
E is selected from the group consisting of the vinylbenzyl moiety, alkyl moieties containing 1 to 10 carbon atoms, or benzyl, subject to the constraint that at least 50% of all E's are the vinylbenzyl moiety; and (2) an ether of the oligomeric condensation product of (a) 1 molar proportion of a dialdehyde and (b) from about 3 to about 4 molar proportions of a phenol: when the dialdehyde is selected from the group consisting of OHC(CH2)mCHO, where m = 0 or an integer from 1 to 6, cyclopentanedialdehyde, phthalaldehyde, isophthalaldehyde, terephthalaldehyde, hexahydrophthalaldehyde, cycloheptanedi-aldehyde, hexahydroisophthalaldehyde, hexahydroterephthalaldehyde, and cyclooctanedialdehyde;
where the phenol has the structure R3C6H4 and R3 is hydrogen or an alkyl group containing from 1 to about 10 carbon atoms; and where the phenol residue of said oligomeric condensation product is etherified with one or more substituents to afford ether moieties randomly selected from the group consisting of vinylbenzyl, alkyl moieties containing from 1 to 10 carbon atoms, cycloalkyl moieties from 5 to 10 carbon atoms, and benzyl, with the ratio of vinylbenzyl to other moieties being from 1:1 to about 6:1;
b. irradiating the coated prepolymer of (a) through a masking pattern to selectively crosslink the portion of said coating being irradiated;
c. selectively dissolving the non-irradiated part of the prepolymer coating of (a); and d. curing the crosslinked portion of the prepolymer coating by heating at a temperature in the range of 100°C to 300°C for a time sufficient to further crosslink said crosslinked coating and to transform the prepolymer to an infusible glassy solid.

3. The method of Claim 1 or 2 wherein R1 and R2 are hydrogen or alkyl with 1-10 carbon atoms.

4. The method of Claim 1 or 2 wherein R1 and R2 are methyl or t-butyl moieties.

5. The method of Claim 1 or 2 wherein Z is Br and a and b are 1-4.

6. The method of Claim 1 or 2 wherein E is at least 70-100% vinyl benzyl moieties and the remaining E's are alkyl with 1-10 carbon atoms.

7. The method of Claim 2 wherein the dialdehyde is OHC(CH2)mCHO and m is 0 or an integer from 1 to 6.

8. The method of Claim 2 where R3 is hydrogen or methyl.

9. The method of Claim 2 wherein the ether moieties of condensation product (2) are about 70% vinyl benzyl and 30% propyl.

10. The method of Claim 2 wherein the molecular weight of condensation product (2) is 400 to 6000.

11. An electronic interconnect structure comprising the cured polymer produced by the method of Claim 1 or 2.

12. An electronic interconnect structure of Claim 11 wherein said cured polymer is adhered to a chromium metal layer.