Note: Descriptions are shown in the official language in which they were submitted.
ffl9~
The present invention relates to a process for the pro-
duction of a coated photographic ~ilm base and to the production of
a light-sensitive photograpl~ic film by the application of a light-
sensitive photographic emulsion to the film base and to the products.
It has been widely accepted in the photographic art that
a light-sensitive photographic emulsjon applied directly to the
surface of a plastics support film does not exhibit sufficient
adhesion to the support film for use in most of the usual photo-
graphic end uses. ~s a result, it has become common practice to
interpose two or more subbing layers between the support film and
the photographic emulsion. For example, when the photographic
emulsion comprises a gelatinous sil~er halide composition, a
polymeric subbing layer and then a gelatinous subbing may be applied
to the sur~ace of the support film prior to the application of the
photographic emulsion to the gelatinous subbin~ layer.
According to the present invention, there is provided a
process for the production of a light-sensitive photographic film,
which comprises coating the surface of a seIf-supporting plastics
film with a subbing composition comprising a copolymer comprising
57 to 100 mole ~ of one or more monomers selected from glycidyl
acrylate and glycidyl methacrylate; methyl, ethyl, propyl, isopropyl,
butyl, hexyl, heptyl, n-octyl, and 2-ethylhexyl acrylates, halo-
substituted acrylates, and methacrylates; acrylamide, methacrylamide,
N-methylol acrylamide, N-ethanol acrylamide, N-propanol acrylamide,
N-methylol methacrylamide, N-ethanol methacrylamide, N-methyl
acrylamide, and N-tertiary-butyl acrylamide; acrylonitrile, halo-
substituted acrylonitrile, and methacrylonitrile; hydroxyethyl meth-
acrylate and dimethylaminoethyl methacrylate, and 0 to ~3 mole % of
n -2-
:
one or more monomers selected ~rom styrene, butadiene, vinyl chloro-
acetate, vlnyl benzoate, vinyl pyridine, vinyl chloride, vinylidene
chloride, maleic acid and anhydride and itaconic acid and anhydr.ide,
and then subjecting the surface of the applied subbiny layer to a
modifying treatment by corona discharge, and applying a light-
sensitive silver halide emulsion layer directly to the surface of
the treated polymeric subbing layer.
The present invention also provides a photographic film
base, which comprises a self-supporting plastics film and a subbing
layer comprising a copolymer comprising at least 57 to 100 mole ~ of
one or more monomers selected from glycidyl acrylate and glycidyl
methacrylate; methyl, ethyl, propyl, isopropyl, butyl, hexyl, heptyl,
n-octyl, and 2-ethylhexyl acrylates, halo-substituted acrylates,
and methacrylates; acrylamide, methacrylamide, N-methylol acrylamida,
N-ethanol acrylamide, N-propanol acrylamide, N-methylol methacryl-
amide, N-ethanol methacrylamide, N-methyl acrylamide, and N-
tertiary-butyl acrylamide, acrylonitrile, halo-substituted acrylo-
nitrile, and methacrylonitrile; hydro~yethyl methacrylate; and
dimethylaminoethyl methacrylate, and O to 43 mole ~ of one or more
20 monomers selected from styrene, butadiene, vinyl chloroacetate,
vinyl benzoate, vinyl pyridine, vinyl chloride, vinylidene chloride,
maleic acid and anhydride and itaconic acid and anhydride, the
subbing layer being adherent to the plastics film and having been
subjected to a surface-modifying treatment by corona discharge, and
a light-sensitive silver halide emulsion layer adhered directly to
the surface of the treated polymeric layer.
According to this invention, light-sensitive photographic
emulsions, such as gelatinous silver hal:ide emulsions, adhere
4~
directly to -the corona discharge treated copolymeric subbing layer
of the base without further treatment or coating, e.g. with a
gelatinous subbing layer. On the other hand, it has been found
that gelatinous subbing layers also adhere strongly to the treated
copolymeric subbing layer and that light-sensitive photographic
emulsion layers adhere strongly via the gelatinous subbing layer.
Therefore, according to this invention, a gelatinous subbing layer
may be interposed between the treated copolymeric subbing layer and
the light-sensitive emulsion layer of a light-sensitive photographic
emulsion, although it is preferred to apply the light-sensitive
photographic emulsion directly to the surface of the treated
copolymeric subbing layer for simplicity and economy of production
and also to avoid certain technical disadvantages which may be
associated with gelatinous layers, for example tackiness in damp
or humid conditions, high surface friction which can create winding
problems, optical interference patterns on the film, static charge
generation and an effect termed l'ageing in contact'l which:.results
from components, such as hardening agents, included in coatings on
the other side of the film migrating into the gelatinous subbing
: 20 layer when the coated film is wound into a reel and causing
premature cross-linking of the gelatin subbing layer which impairs
the adhesion of the l.ight-sensit.ive emulsion to the gelatin subbing
layer.
The self-supporting plastics film may consist of any
suitable plastics film, such as films of polysulphones
,r~
;~J 3a-
o Px 29011
and linear p~ ter~ ~hich Yaay be obtain~d by conden~ing
on~ oxq rnor~ di.car~ c acids nr -th~lr lower alkyl
di~t~r~ 9 a~Og~ t~!r~l'i;hiEll:lC ac:id~ l~o~phLtha~ ph~h lic/
29~, 25~ and ~7~t~lal~n0 dicarbo~cylio acld~ 8uccin:Lc
5 acid5, ~ebaclc a~id9 adlpl¢ acid, az~laiG ac,ld, d:Lphenyl
dicarboxylic acid, and h~x~hydr~r~phthalio a~ld or
bi~ carbo~l p~eno~y ~th~e~ opl;ionally with ~ monocar~oxylio
acld, $uch a~ pi~ali~ aoi~l~ with on~ or ~ore glycol~g
eOgO *thylene g~:ysol" 1 ~3~p:L~opa~d:1019 1 ~4-b~tanedlol"
10 neopentyl glycol a~d 1 ~4~cycloh~xane~diDn~Lanol~ Biaxially
oriented an~ h~at-~t fi1m~ o~ po~thylen~ terepl~thalat~
ar~ p~rticularly u~ful ~or th~ produ~tion o~ the
photogr~phiG ~ ac~ording to thl~ rentionO Such
8~ 9,uppalrting pla~t;icEs :~i~s may be tran~parent ~d
15 li~ht-tran~mitt:Lng~ optlo~ally l~ludin~ photographi.cal~y
in~rt dye~t~ , e~g~ blu~ dY~tUI~ or X ray fllms, or
may be r~3nder~d op q~e by the ~ddition o~ addlti~s, ~uch
as plep~ents ~d :~iller~" ~d ~ay in partlcular have a whlte
and paper~lik~ t~xture ~h:lch m~r be achie~cl by the addltl~sn
20 of su~table flller~ and~or by voLdill~o The white and pap~r-
~l,k~ a~ be u~ed a~ ba~ or photographic print~
'rhe acrylic acid and/or metha~lrylic aoid ~d~/or
d~rivative of aorylic acid and/or 1~ethacrylic acid
comonom~r(~) ar~ pre~rably the ~sa~r ~ingle or, wh~n ~wo
25 or more ~uch eomo~om~rs are u~, in comblna~lon with the
m~:o~ ~ingl~ monomeric constil;uen~ o~ th~ ~ubbing Gopolymer3
iaeO th~ ~olar proportlon o~ ~uch co~ono~r(~) pre~rably
~xc~ed~ the ~olar pr~ortlo~ of ally oth~r comonom~r~
Ga~erally, th~ molar praportion of ~uch comono~r(~)
30 ~hould pre~erablg ~x~eed 25 mole % o~ the copolymerq
MoYlo~erlc d~rivatlve~ o:f acryllc acid and ~etha~rylic
acid whlch ~re ~uitable ~or th~ ~oFmation o~ the su~bi~g
copolymer~ lnclude ~l~cidyl ~crsrlate and glyci~yl ~eth-
acry~ate, alk~rï esters in ~hich the al~l group Go~pri~es
35 ~p to 10 car~on atom~, e"g. methyl~ ~thyl, propyl, isopropylv
~ Px 29011
_. ~
butyl, hexyl~ h~ptyl" n~Qctyl~ and 2~ethylhexyl acrylat~
halo ~ub~tit~at~d a~ylat~ ~d methacry:Late~ ~mide~
inc:Luding N~a~ylol and N~alky~ ub~tituted arn~d~9
~.g. acrylamid~, m~t;haorylam~de9 lN ~thylol a~rylam~de9
5 N.-ethanol acrylamid~ " N~propanolacrylamide ~ N-m~ thylol
m~tha~rylamidc ~ N~th&~ol meth~crylamid~ 9 ~-~ethyl
acryl~mid~ t~r~tlary~but~l~csr~r1Lamid~ ni~rile~
eOgl acr~rlonitrile~ halo~ubstituted acr~rlonitrlle
and ~ethacrylonitrilel, acryl~o and m~thacrylic co~pourld
10 co~ainlng f~ t~onal h3rdrophilio ~roup~, and ~in~
inclu~ing dlmet~ylamir~oethylmethacx~lat~.
E:thyl acrylate and ;a~thgl methacr~vlate ar~ lparticularly
use~ul alkyl e3t~r como~ r~ ~nd provlde u~0~ul ~ubbing;
properti~ lfrhen copol~ri~ed together and when copolym~ri~d
1~ wlth other comonomer~ .
The ~poxy ~oup o~ the glycidyl m~thacrylat~
~d glyc~lyl aG~rlat~ monomer~ if cti~ în cro~
li~i~ the ~ubbl~g copolym~r thereby pr~ding a
barri~r again~t the p~netrat~on of organlc ~ol~ents
20 whi~h might f~ction to wea~en or ~troy the bo~d
b~tw~en th~ subbing la~er and the support ~ilm.
Cro~ nlci,g may b~ I~urther enhanced by the
pre~ence o~ a hy~r~philic acrylic or me~hacrylic como~o~er
in con~unction wlth gl~rcidyl a~rylata and/or glycidyl
25 methacr~rlate ~lnce th~ hydrophlli~ group can cros~
llnk with th~ epoxy group o~ ~h~ glycidyl m~thacrylate
or glycidyl acrylate thus con~ributing to the barrier
propertie~ o~ the layer~ Suitable monomers ar~ hydroxyalkyl
methaorylate~ such a.s hydroxyethyl metha~rylate, and
~0 ~llane~ which hydrolyse in aqueous media to introduae
functlonal hydro~yl groups, SUGh a~ ~-m~thacryloxypropyl
trim~thoxysilane.
~ crylonitrile is another useful comonomer ~or
a ~ubbing copolymer which has barrier propertie~ against
~olv~nt penetration.
Px 2901 1
-- 6
Anti~tatlc prop~rtie~ may b¢ lr3corporated into
the copoly~er by the us~ o~ acrylic and meth~cryl:lc
comon~mer~ ha~rlng an ionie character9 e.g~ dim~thyl-
aminoethyl m~thac~late acetat~ ~alt~
The subbln~ ~opol~rmer may al~o b~ deri~e~l from
oth~r copolymerlsable ~t~lenicalïy unsaturated eomonomer~
in addition to the acrylic acid and/or methacryll~
acid andlor d~ri~ati~ thereoI which are d~cribed
a~otre" ior exa~p1e ~tyr~rle~ d~rivativ~el oî s~yren~9
butad~Le~e, ~rinyl chloroao~tate, ~rin~l benzoate9 ~inyl
pyridine, vinyl ch1pride ? vinylid~ns chlor1de, mal~ic
acid ~d anhydrid~ and itacs~ I c acid and anhy~ride,
The subbing ~opol~aer pr~erably co~pris~ from
25 to 100 mole ~6 o~ ~he ~mo~om~r(~ co~rising acr5rl1o
acid and~or me~a¢rylic acid and/or d~ri~rative3 thereoî
and mo~ pre~erab1y 51 to 100 mole %" pro~id~d that
wh~n ~uch como~omers ~oD~pri3e 100 mole %~ the copo}ymer
i3 d~ri~ted ~rom tw~ or more monoDl~rs con~pr~sing ~cryl~-c
acid and/or methaGryllc acid and/or deri~ati~re~ th~r¢o~
ZO and th~ total of th~ ~o~omaric proportlo~s amount
to ~ mole %,,
Particularly suitable su~bing copolym~rs Ior
u~ aocording to thls im~ntloltl Go~prise 3 to 25 ~oIe
% of glycidyl ~ne~hacrylate or gly~idyl a~rylate, ~
1 to 60 mol~ % o~ a~r~rlo~Litrile and 35 ~o 95 mole %
o~ on~ or more other comoT~omers ~omprlsi~g aorylio
acid ~nd/or methac~rlic acid an~or derivatlve~ thereo~
su¢h as ~n acrylic a~d/or m~thacryll~ ~aid e~ter~3)
andlor an acryl~o or alle3thaor~rlic monom~r ha~ing a
~ ctional group, e~pe~ial~y a hydroxyalkyl ~hacrylate.
Prs~erably" 3u¢h copol~ r~ co~pri~e 5 to 10 ~nolq~ %
o:e glycidyl methacryl~te or gly¢~dyl acrylat~, 1
to 5 mole % o~ a hydroxyalkyl methacrylate, 1 to 40
~ele % o~ acrylorlitrile and 50 to 8~) mole % o:f ac~llc
andlor meth~or~ aoid ~ter(~)0 ~ e~pecially 3ultable
.~ .
9~ 9017
-- 7 ~
~uhbin~ o~pol~rmer OI thls cla3~ con~i~t~ of 7 mole %
o~ glycidyl m~thacrylat~ 1 mole 96 o~ hydroxy~thyl
ma~hac~rlatet ~5 mole % of et~rl acrylate, 21 mole 96
of me~yl meth~c~rlate and ~6 mo:L~ % of acrylo~itrile.
5 l~}is i~ an exan~p~e o~ a copolymer in which th~ total
molar proportions of acrylic and methacryllc a~id
d~rlvati~es a~ount to 100 laole ~0
~ on~rentiona:L addltives may be i~clud~d in the
copolymsr.ic ~;ubbing layer, e~g. adh~sion promoters9
10 ~uch as a partially hydrolysed ~inyl acetate/~in~l
chlorid~ copol3rmer optionally ad~lx~d with a chlorinated
phenolp slip and anti;3tatlc agentsO
Iî d~ired, ~he ooating disper~ion or solutlon
may con~ain a oro~linking agent whlch ~nction~
~5 to cro~3~ k th~ subbi~g copolymer thereby in~provlllg
adhe~ion to the pla3tiLc8 ~ilmO ~dditionally9 the
cro~-linking agen~t ~hould pre:eerably b8 capabl0 of
irlternal cro3~-linking in order to pr~vld~ prarte~Gti.on
again~t solv~nt penatratlonO Sulta~le Gros~ klng
20 co~pon~nts may co~pri ~ epoxy resins~ alkyd re~ins~
amln~ derivati~es such as hexametho~m21th~l m~lamirle,
and/or cond~nsation products of an ~mln~, e"g. melamine,
diazine, urea, cy~lic ethylene urea, cyclic propyl~ne
urea, thiourea, cyclic ethrlens3 thlourea, alkyl ~lamines,
25 aryl melamlnes, benzo guanamin~ guanamir~es, all~rl
guana~nes and argl guanamln~s with an aldehyde, e~,g.
~ormaldeh~rde,, A useful conden~at~on product l~ that
of melamine with ~ormald~hyd~,, The conden~ation product
may optionally be alkox9lat~d. The aros~-llnking
30 agent rnay be u~ed in amount~ o:E up to 25% b~ wei~ht
based on the wei~t o~ th~ polymer ln the subbir~
oo~po~ition.
A ~at~ïyst ls also pre~erably emplo~d to ~acilitate
cros~-linki~g~ Pre~erred catalysts ~or cros~-linki~
35 melami~ ~or~aldehyd~ :In~lud~ ammonlum chloride, ammonlu~
L9
.Px 2
-- 8 --
nitrat~9 ~olliwn thioc~a~ate, ~o~lum d~hydrogen
phosphate9 amm~ ulphate9 dlam~oni~ h~drog~n
p~o~phate, para tolu~ne ~ul~honi~ aold ~ ~al~ic aci.d
~tabili~d by reaotlon wlth a baseg an~ ~Loirph~:31iniu~
5 para toluen~ ~3UlphQ~late~9
A~cordlng to th~ in~ention~ the copo~ rlc ~ubblng
layer may be applled to the pla~tios ~i.lm dLuring or
a~t~r the co~ tio~ of the proc~s~ by whlGh the pla~ti¢~
s produ~ed~,
Wh~n the layer i~ appll~ a~t~r the prodllction
of the plastic~ the ~ asr b~ pr~trea~ed or
ooat~d i~ h a way to ~pr~ th~ adhe~ion of ~
r to ~ f~lm urIaceO Ch~ml~al or ~ysic~l pr~-
tr~at~nt~ y b~ ~ploy~ to mod~y th~ ac~.
Su~h pr~tre~tn~t~ may ;Inv~l~re coatiLxlg th~ ~:Llm ~ace
wlt~ a ~olution havi~ ~ ol~ent or oxidi~
aotlo~ on l;~e rilm. AlterYlati~ro~y or addltional:ly,
thæ ~ilm may b~ ~ub~eotsd to ~oro~a di~eh~rge trea~nt~
tr~atment, or ultra-~riolot li~ht9 When the .
?O pla~tic fi~ a li~ar poly~ter, ~uGh a~ polye~hyl~ne
t~ hthalat~, the pr~treatm~nt ~ay imrol~e th~ appli~a~on
to.l;h~ a~e o~ a material havlrlg a swelling
or ~olvont aetlon upon ~h~ 93~ a solu~io~
a coDlmon organi~ ~o~n~ such as ac~to~ or m~anol
o~ hloro-~cr~ol" 2~4~dichloro~eno~ 2,4,6~ or
2"4g5 ~trlohloroph~nol or 4~hloror~orGi~l or a ~i~uro
o~ ~ueh mat~rial~ in a com~non organlc 30~ lt. I~
d~lrod, th~ pr~treatlx~g ~olu~ion rllay contailn a polr~rlo
con~ponent, ~.g. a copolym~r o~ vinyl Ghlorid~ and
vl~yl acetate. A:~ter such a solution ha~ bee~ appli~d
to tho ~llm ~ a~ it may be dr~ed al; a~ eïevat~d
tamperatur~ Ior a îew mlnute~ be~or~ applyiTlg the
sub~ing coDqpo~ition. Al~rnati~rely9 the pla~t$c3
~ilm may carry a~ adhe~lon-pro~oting polymeric ~ayer
to wh~h the layer contaln:l~g ~e polymeric co~poxlent
Lg~5~3
Px 2901 1
may be applled~ Suitable layers ~lud~ polymer3
~d c~poly~r~ o~ acrylic and m~thacrylic aci d~ and
th~ir e~ter~ ~ a:nd cs~olymers of ~riny~lid~ne chloride .
Th~ prac~dure ~or applying the subblng ¢ompo~ition
5 may be any of the l~wn coating te~iqus~, ~uch a~
dlp ~oati~g~ bead ~oa~ing" re~erse roller ~oa~ln~
or ~lot coat~ l th~ ~on~po~ition may b~ appli~d
a~ an aqueou~ la~ex or ~olukio~ or a~ a ~olutio~ ln
an orlsanic solv~n~t~
I~ the ~ilm i~ produced by a proc~ss o~ molecular
orier.,tatlon ~hich i3 normall~ achi~v~d by stretch~ng;
in one or Door~ direction~ it ~3 con~enlent to apply
th~ copolyæ~ric ~ubbl~g lay~r during the ~:~1~ productio~.
U~uall~, orl~nt~d ~ are biaxlally orient~d by
~tretehi~g in two m~tually perper~dlclllar dlreet;ions,
~or ~xaEple a9 $~ t~ ca~ w~h poly~th~flen~ tor~phth~lat~
qlhe ~ubbing lay~r may be a~plied be~or~ th~
stret~hirlg op~ratio~ i~ commenced, or ellor~ pr~ferabIy
b~ n the ~tretchi~g operations appll~d in th~ l;w~
perpendicular direction~. Such a sequenGe o~ coa~ing
beltwe~n ~h~ ~tr~tchlng op~ratlc)ns i~ pref~rred for
the ci~a~ing of ~rient~d polyethyle~e tere~hthalate
filla3. 1~ subbi~g layer i~ pre~e~ably ap~lied a~
an aqu~ou~ dispersio~ in ~uoh an operatlon.
Alt8xnatlvely, th~ pla~tics ~iL~ and *he ~ubblng
layer may be ~ormed by ~oextrusion or they ~nay b0
~orm2d by ind~p*nde~t o~perationa and then lamiLnated.
Corona discharge treatmQnt ~ay be 0~fect~d l~
air at ~tmospheric pre~ure wlth comrent~on~ uipment
u~ing ~ re~uency, high ~vltage generator, prererably
ha~ing a power output o~ ~rom 1 to 20 }c~ at a pot~ntial
of 1 to 100 k~r~ Dl~char~ l~ conveni~ntly ac~onqpllshed
by passing the ~ilm ov~r a dlelectrlc support roller
at th~ dl~charge ~tation at a linear sp~3d pr~:Eerably
of 100 to 500 m per D~i~ute,, The di3~,harg~ el~ctrode~
Px 2907 1
.- 10 ~;
ma~ be positlo~d Ool to 10.0 ~ from th~ ~o~lng ~llm
sur~a~e. Th~ ~pll~d ~ubblrlg lay~r ~hould pr~erably
e~lbit a wettin~ t~st valu~ a~t~r coro~a dl30har~
tr~at~ edin~ 56 dy~s/cm when mea~ d by th~
Union Carbld~ Standard W~ttlng Te3t (SYC 81-3/1964)
with a ~Eorm~mid~J1Cello~ol~' ~ure, wher~a~ the
value o~lbit~d by arl u~treated layer ls gs~rall~
in th~ rang~ 35 to 45 dynes/emO ~ thi~ te~t, ~ uid
.~ m~xture~ having a rang~ O:e ~urîac~ t~n~ion~ nade
^~0 up u~ ari~us coneentrat~ of formamld~ C~llo~olv~
(2~thoxy ~thanol~ a~d bru~d ori~o th~ ac~ to
be ~c~in~d. The ~etti~g t~t val~ 1~ ~he ~tar~ac~
t~n~n of th~ liquld mlxtur~ ha~ring the lhi~he~t ~ ace
t~n~io~ whio~ doe3 not oon~raot ~n~o ~opl~ts b~i~hln.
two second~ aft0r ap~loal;io~ on~o th~ a~0
C'opol~ ri~ ~ubbl~g lay~rs h~Ying a ooat ~ig~Lt
in t~le ran~ 0.1 to 10 D~ æ prGvid~ sa~ a6tQry
ad~lon. Coat ~ ht3 in ~ r~e 1.0 to 3.0 ~/d~
ar~ pr~ rr~d,
- ~0 ~he oo~olym~riG ubbing l~y~r~ appli~d a~¢ord$n~
to t~i3 inv~n~io~ to polyeth~l~no t~repht~alate ~
are ~uch t~at ~a ~ ba~ is ~uitable ~or r~oycliIlg
throu~ or~sing ~xtrud~r and ~tr~tching aquip~e~tO
~he i~ntion al~o r~lates t;o a proce~ îor th~
prodll~tio~ of a photographlc fllm whlch ~o~pri~s
a~pIyi~s a ligihg-s~n~iti~ photo~ hie ~ lorl o~r~r
the ~ acé modi~led c~polym~ri~ ~ubbing l~y~r o~
a photogral?hic ~ilm ba~e pr~du~:ed a~ d~crlb~d abo~re
and to the photoe;ra~hic Pilm.
~y suitable lie~ht-~en~iti~re photo~r~phic emulslon~
3uch a~ a co~v~ntio~al ga:latl~ou~ ~l~er halide em~ ion;
may be applie~ by ~on~r~ntlo~l techx~iqu~ to the stlr~a~e
modt~.ad ~ubbi~lg layer, Such an emulsio:ll may conta~n
any o~ the conventio~al addlti~e~. It h~ b~en i~ou~d
3~ that light-~en~ititr~ emul~ion~ bon~ with good adh~ion,
~ -r~ ~ P~
~ 11
as stated above; a~ter dlrect appllcat~on -~o the surfac~
modified lagerD Th~r~ore~ according to thi~ rention,
it is pr~f ~rred to apply t;h~ ht ~ensitive emulsi~n
direetly to the sur~ace modl~ied subbing layer in
5 the productlon o~ ht-s~næitlve photographic ~iilms!.
!~ev~rthel~s 9 conv~ntional gelati~u~ subbing
lay~rs may, ~f deaired, b~ interposed bet~.Yeerl the
sur~ac~e modi~ied ~opolymeric subbing layer and the
light-~nsil;lYe photograph~c em~lsion lLayer. SUçh
10 gelatin subbing layer~ ~nay c:ontain any of the usual
additives such a~ pol~vin~l aeetate, particulate materials~
eOg, ~llicaD anti;~locking agen-ts ald cross~lir~ing
agents, e.g~, formalin, and ma~r be ap~lled by a~y known
t~ohni.que 1~
me inventlon i~ ~urth~r ~llustrated by the i~ollowing
examples, in which drr a~d wet adhe~on have the ~ollowing
meaniIlgs and were as~es~ed by ~he ~ollobring t~sts.
~ refer~ to the adhesion o~ a gel~inous
sil~rer halide 2mul~ion via an underl~ing gelatin ~ubblng
20 layer, if p~esent, to the pla~t~cs film in the ~ina~
photo~raphi¢ ~ilm9 a~ses~d, both b~fore and aiter
proce~sing in standard photographic chem~al~, by
sticki~g a self-adhe~ive tape along the torn sdge.
o~ the film and rapidly ~eparating th~ tape ~rom th~
25 ~ilm~
W~t adhesion refers to ~h~ adheslon o~ ~ gelatinou~
__
silvar halide emul~lon vla an urlderlying ~:Lati~ ~ubbing
layer, if present, to the plastic~ iilm in the final
photographic ~ilm~ a~es5ed~ after prooe8slng in th~
30 standa~d photographic chemicals an~l washlng in water
for l~i minutes by rubbirlg wlth a ~ponge over a 3eries
of lines ~cor*d in the st:Lll wet emul~ion~
Px 2901 1
- 12
A ~ubbin~ CoD~o~itio~ waæ prepared from ~ mo~o~2r
x~ctu~
eth~l acrylat~ ~6 mol~ %
~thyl m0~aacryl~t~ :29 ~ole
dyl ~e~h~cryïate 8 ~ole %
hydroxye~l ~ethacrylate2 mol~ %
acrylonitrlle 25 ;~o~e %
600 ~ B O:e water, ~0 g o~ $~1si~ier whi~
1~3~10` 1~ c~ rcl~lly a~rallable a~R13610j 2 ~1~
OI ~i~ethylaminoethanol ~ 0 . 6 D~L o~ lauryl merca~n
to control mol~cu~ar weight9 ~0% by weight o~
total moxlomer contell~ and 2596 by wsighlt o~ ~e total
cataly2~1; cont~n~ w~re ¢harged 1t~ a ~la~k5, dega~d7
15 ~tirred and h~al;ed at a polymeri~atlon tea~peratulre
o~ 60~C u:nder a~ ert atDIo~pher~, The total Yolu~
oi th~ ~oIlo~r~ wa~ ~bout 600 D~ ;t aYld 0~ ~e ~at81y3t
300 ~18 o~ ~ 0"196 aqu~ou~ 801ution 0~ pota~s1um per~ulpha~eO
A~ter ~e r~acl;ion had progre~ed ~or 30 D~lnut~,
20 ~ rs~a1nl~g ~o~o~r~ a~d a ~urther 55% by ~e1~ht
of l~he cataly~st wer~ ~ed irl ov~r a p~riod o~ about
3 hour~, ~e re~ult1~g la~ex wa~ ~t~rred ~o~ a ~~ her
15 ~Lutes, ~ re~ixl~g 20% by weie~ o~ c~alr~t
add~d9 ~nd t~he ba~h wa~ ~tlr:r~d Xor ~url~er 15
ml~ut~ before dl~charge. ~ ex wa~ æ~rlp~d
o~ r~3~dllal mo~om~r~ und~r pa~t~Lal ~acuula. ,
Thi8 COD~pO8it;iOXI wa~ dilut~d to 31~5% by wei~ht
sol~d~ a~d 0.5% by ~rolume o~f, a~o~ioIllo ~Ur:lEaCtallt
s~Ailable com~eroially a~ p~N ~a~ add0d.
A polyet~len~ t~r~phthal~te ~ilm wa~ elt extruded
and que~ch~d to t~ morph~u~ ~t~i;e on a cooled rotaitln~
druD~. Th~ resulti~g ~ wa~ ~tretched 1:~ ~e directio~
o~ ~xtru~ion to about 3.5 timei~ it~ origi~al l~gth.
~.
Px 2901 1
~ 13 -
It wa~ then coat~d on both ~ld~s with the ~queou~
disp~r~ion d~cribed above by ~ roller coating ~chniqu~
~nd ~a~ed lnto a ~te~e~ oven wh~re ~he coating
was dried. Th~ drie~l coated ~ was th~ ~tr~tched
5 ~idewa~ about 3.5 t:Lm~ it~ original ~ldth and ïinalïy
h~at ~t at a t~per~tllre of aboult 210~. q~e flnal
~hiclme~ o~ the ~ubbl~g layer on ~a~ ~:Lde of the
bi~ally dr~ about 003 micro~, and ~he
total ~ickrle~ o~ th~ was ~bout 100 micro~.
T~e oopolym~ric ~ubbi~g l~rer wa~ coro~a dl~charge
treat~d at at~o~ph~ric p~ ur~ ln a co~er¢lally
~allable V~taph~s 3 k~ tr~ater to produc~ a coati~
havi~g IJn~on Carbide We~ting Te~t ~alue ~reater tha~
56 d~/cm~ m~ trea~l1aent cond~tion~ w~r0 film
15 ~p~ed 20 ~ 9 pow~r Z kw, el~strod~ to ~il~ di5tÇ~lCe
1, 5 -mm,
A converltio~al X~r~y ~i:Lver halide photographic
emulsio~ w~ a~plied direotly to the corona discharge
treat,ed ~ur~ce o:E the ~ubbi~ layers, wlthout in~erpoRing
20 a g~latl~ subbin~ la~er. The wet a~d dry ~ ion
adheslon~ were ~ati~iactoryO
A Gonve~tio~ biaxially ori~nted 100 micro~
t~hic~ clear pol~thylene t~rephthalat~ ~Eilm wa~ pretreat~d
wit~ 1~e ~ol~owin~ ~olution:
p-chloro~m-cresol 5 e
A vinyl ac~tate/~inyl chloride
copolymer which is com~ercially
availalble a~ L~ 1 g
tt ~
.Acetone 100 ~1
The ~olu-tlon was applied to giV13 a ~et coat
weight o~ 100 mg~dm2 and drled ~or ~ minute~ at 80C,
:3L~'.lL~4~0 Px 29011
ollowlng ~ubbi~g ~o~po~i~io2~ W&18 appli~d
to th~ prstrea~ed ~ur:~aoe~
A carboxy ~odi~l~d ~crylic poly~er
ch 1~ comm~rcia~Lly ~ail~ble ~
~ Z671 5 æ
~yGC~r~
Di~tlll~d water ~5 g
The ooat~d f~ WilB dried at 80~C for 3 ~l~ute~
lto gi~e a dry poly~ric ~u~b~s co~ w~iLg~ OI 2 l~lg/~12.
The ~ wa~ di~ided i~to two ps~rt~ A a~d B.
1û Par~ A
A co~re~tion~l gelati~ou~ r h~lid~ X-ray
e~l3ion wa3 applied dlr~c~:ly to the copolys~r layer
wlt~out coro~a di~charg~ tr~at~t~ chilled to g~l.
~ coa~in~9 a~d d$~i~d ~or 20 D~u$e~ at 35C.
~ er hali~ e~ lo~L ws~ th~ t~t~d ~r
adh~a~on,, ~ dry adh~io~ b~i~g go~ but the w~lt
io~ was ~ry poor ar~d ~ e~ ion could b~
s~parat~d ~ro~ y rubbl~.
Th~ copol~ri~ ~u~bi~g lay~r wa~ coro~a dl~ohar
tr~a~d u~ g th~ ~q~ipD~ aDLd condit~o~ ~p~c~fied
Exa~ 10
Final:Ly ~tae tr~ated fll~ wa~ co~ted wli;h a g~latinou~
~ilv@r halid~ X r~y e~ lo~L a~ for Par~ A abov~3.
Th~ photo~raphlc ~at~r~al wa~ tested ~or
a~he~ion. ~ adh~ion ~s exc~lle~t be3~0r~ a~d
a:~t~r pro~essi~g and th~ wet ad~e~lo~ durlll~ proc~
wa~ o excell~ t.
A oo~e~ltionally biaxially orie~lted 100 ~aicron
. thlck cl~ar polyet~ylen~ ~er~ph~hala~ ~lu whi~
ha~ he~ precoal;~d wi~ a ~o~- 11nk0d copol~r
~or~ed ~rom~ by ~ , 4$% eth~rl acr~rl~e, 50g6 m~thyl
~t~ha~rylat~ ~nd 5% ~thaorylaD~id~ wa~ coat3d o~rer
4~ Px 2901 1
- 15 -
the precoating wi~ a ~ubbing ~olution o~ ollowlng
i~gradient~:
Ethyl ~-chlvro~cryl~thyl
acrylate~ltaconic acid
c~po~y~ 60~35~ L0 %
resp~cti~ly) 3 g
A~to~e lOû ml
The copolym~ric ~ubbing l~y0r wa~ coroxla discharg~
~re~ted u~i~g the ~quipm~nt and coxldi.tio;n~ ~pecl~ied
10 in Exa~ple 1 and a co~entional gelatino~ rer
halid~ photographic e~ ion wa~ appll~d oYr~r the
tr~ated ~rf ac~,
q~e wet a~d dry adhasio~ oi the applied e~l~;:Lon
wa~ 3atisfactory.
EXA~
The proce~re OI Exa~le 1 w~s repeated to stretch
a polyethylene t~reph~halate ~ nd coat it wit~
a ~ubbing co~po~itio~ co~pri~lngO
A carboxy modified a~crylio polymer
which :L~ ¢o~mercially a~allable as
~ Hycar ~ 260X84 10 g
Di~tilled water 90 g
q~he polymeric ~ubbing layer was corona disc~arge
l;reated in accordar~ce with Exa~ple 1 and coat~d with
25 a convention~l ~elatinou~ sil~rer halide photog~aphic
emulsion. The e3ml1sion wa~ ~ubjec-ted to accelerated
ageing at 50C and 6796 relati~re h~idlty for 16 hour~
be~ore testing for adhe~ion. The wet and dry a~e~ion
o~ the emulsion wa~ satisI~tory.
''
Px 2901 1
- 16 ~
~AMPLE 5
The prooe~Lure of Exa~ple 1 w~s repeat~d to ~tretch
a polye~ylelle tareph~h~late ~ilm and ~oat ilt wit~
a ~ubblng coD~po~ition oo~prl~lng:
An aorylic/vinrl chlorld~
oopolym~r which i~
con~rclally availabl~ as
~",~ 450~Z0 10 g
Dlstillsd w~ter 90 g
The copoly~eric ~ubbi~g lay~r w~s coro~a di~charee
treated in accordance with Ex~le 'I and coated with
a collventio~al gelatl~o~ rer h~:Llde photogr~phic
emul~lon. The e~ ioIl e~hlbited e~ccell~nt we~ and
ary adll~ion.
EXAMPLE 6
E:xaD~ple 5 wa~ repea~ed exceplt ~hat the ~ubbi~g
co~posltlon on~a~n~d th~ ~ollow:lng is~3redient~:
An acrylic~acry~onitrLle/~tyrexl~,
~opolymer w~lch iæ co~mercl~
a~railable ~rom Mo~on Willi~s
Limited a~d d~lgnat~d AA42110 ~
- Di~till~d w~t~r 90 g
Ths applied emuls~on ~xhlblted excellent wet
and dry adhe~ion upo~ ~anual ~roce~ing and al~o
i~ con~ntio~al ~olution~ ~or u~ in a~om~t~c ~rooe~sin~
appar~tu~.
EXAMPLE 7
Exampls 3 wa~ repeat~d exse~t ~h~t ~he ~ubbi~g
co~po~itlo~ compri~d:
A chloroacrylonitril~ethyl
acrylatetit~conic aoid
copolym~r ~60/35/5 ~ole %
rea~ectivel~) ~ g
Ac~tone 100 ml
4~ Px 29011
'I 7
The emul~ion appl~d to th~ corona dlscharge
tre~t~d copoly~rlc ~u~bl~ Lay~r wa~ a corl~e~:ion~l
g~latinous ~ilv~r h~ïide X ray ~ io~ l~e wet
and dry adhe~ioa~ o:~ the ~ lo~ wa~ good.,
EXAMPL~3 8
Exa~ple 5 wa~ rep~ated ~xcept that th~ ~ubbl~g
con~pv~it~on con~aln~d the :~ollowiY~ gredient~c
A~ ~ t;hyl acryl~te/~ethyl la~thacr,ylate/
t;aconic ~cid~tyrene ccpoly~r
(28~5/28,5/5/3~S mol~ % r~peGtiv,~ly~
1 atls: c 10 g
Di~tilled wa~r 90 g
~ he ~ reIS halide e~ll~ioIl ~ppli~d to ~e cor~a
dis~harge treated colpo1ymeric subbing lay~r wa~
~o~e:~tional X-r~Ly photograph1c e~ io~,
