CA1119450A - Silver halide film with a subbing layer comprising corona treated acrylic or methacrylic copolymer - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Photographic film bases and sensitised photographic films are produced by coating a supporting film with a subbing copolymer comprising one or more comonomers selected from acrylic acid and/or methacrylic acid and/or derivatives thereof which is then subjected to a surface modifying corona discharge treatment.
Light-sensitive photographic emulsions adhere directly to the treated subbing layer without the need for and intermediate gelatin subbing layer.

Description

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 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~

.Px 2 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 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 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.

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~.

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~,

Claims (10)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for the production of a light-sensitive photo-graphic film, which comprises coating the surface of a self-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 methacrylate and dimethyl-aminoethyl methacrylate, and 0 to 43 mole % of one or more monomers selected from styrene, butadiene, vinyl chloroacetate, vinyl benzoate, vinyl pyridine, vinyl chloride, vinylidene chloride, maleic acid and anhydride and itaconic acid and anhydride, and then subjecting the surface of the applied subbing 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.

2. A process for the production of a light-sensitive photo-graphic film according to claim 1, in which the copolymer of the subbing composition is derived from ethyl acrylate and methyl methacrylate.

3. A process for the production of a light-sensitive photographic film according to claim 1, in which the copolymer of the subbing composition is a copolymer of 7 mole % of glycidyl methacrylate, 1 mole % of hydroxyethyl methacrylate, 35 mole % of ethyl acrylate, 21 mole % of methyl methacrylate and 36 mole % of acrylonitrile.

4. A process for the production of a light-sensitive photographic film according to claim 1, in which the subbing com-position is applied to the plastics film during the process by which the film is produced.

5. A process for the production of a light-sensitive photographic film according to claim 4, in which the plastics film is biaxially oriented by stretching in two mutually perpendi-cular directions and the subbing composition is applied between the stretching operations in the two directions.

6. A process for the production of a light-sensitive photographic film according to claim 1, in which the plastics film comprises a biaxially oriented and heat-set polyethylene terephthalate film.

7. 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 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 methacrylate and dimethylaminoethyl methacrylate, and 0 to 43 mole % of one or more 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.

8. A photographic film according to claim 7, in which the copolymer of the subbing layer is derived from ethyl acrylate and methyl methacrylate.

9. A photographic film according to claim 7, in which the copolymer of the subbing layer is a copolymer of 7 mole % of glycidyl methacrylate, 1 mole % of hydroxyethyl methacrylate, 35 mole % of ethyl acrylate, 21 mole % of methyl methacrylate and 36 mole % of acrylonitrile.

10. A photographic film according to claim 7, in which the plastics film comprises a biaxially oriented and heat-set polyethylene terephthalate film.