Photographic silver halide element having polyester support and exhibiting improved dry adhesion

The invention provides a photographic element comprising a polyester support bearing a light-sensitive silver halide photographic emulsion layer, the support having adjacent thereto a polymer-containing subbing layer, the subbing layer having adjacent thereto a layer comprising a hydrophilic binder containing dispersed droplets of a high boiling hydrophobic organic liquid, said liquid having a logarithm of its octanol/water partition coefficient (log P) value greater than 7.7. The invention also includes a process for preparing a photographic element of the invention and a process for forming an image in an element of the invention. The invention further includes a photographic element comprising a polyester support bearing a hydrophilic layer containing an antihalation agent, such as elemental silver, with or without an intervening subbing layer.

FIELD OF THE INVENTION 
This invention relates to silver halide photographic materials, and more 
specifically to multilayer photographic materials comprising a polyester 
support having coated thereon a hydrophilic layer containing droplets of a 
hydrophobic, high-boiling organic liquid. 
BACKGROUND OF THE INVENTION 
It is well-known to coat silver halide photographic materials on cellulose 
acetate supports. In certain instances, it has been found advantageous to 
coat these materials on polyester supports when increased dimensional 
stability or mechanical strength of the photographic element is desired, 
as described in U.S. Pat. No. 3,649,336. In particular, it has been found 
that a polyethylene naphthalate ("PEN") support has excellent mechanical 
strength and curl relaxation characteristics compared to other supports. 
However, it is more difficult to obtain the required adhesion 
characteristics when coating aqueous-based photographic compositions on 
these polyester films, in contrast to the conventionally employed 
cellulose acetate based support, as noted in U.S. Pat. Nos. 5,292,628 and 
4,116,696 and European Patent Publication EP 035,614. 
It is well-known to apply to a support one or more subbing layers followed 
by the direct coating of a photographic layer in order to improve the 
adhesion of a subsequent layer. 
It is also well-known to improve the adhesive strength between a layer 
adjacent to a support and the surface of the support by way of a surface 
treatment. Examples of these surface activation treatments include, but 
are not limited to: a chemical treatment, a mechanical treatment, a corona 
discharge, a flame treatment, a UV irradiation, a radio-frequency 
treatment, a glow discharge, an active plasma treatment, a laser 
treatment, a mixed acid treatment or ozone-oxidation. Such treatment may 
be employed with or without the application of a subbing layer. With a 
polyester based support, even the additional application of a polymer 
subbing layer has failed to provide the desired degree of adhesion. 
If the adhesion between the photographic layers and the support is 
insufficient, several practical problems arise. If the photographic 
material is brought into contact with a sticky material, such as splicing 
tape, the photographic layers may be peeled from the support resulting in 
a loss of image-forming capability. In the manufacturing process, the 
photographic material is subjected to slitting or cutting operations and 
in many cases perforated holes are punched into the material for film 
advancement in cameras and processors. Poor adhesion can result in a 
delamination of the photographic layers from the support at the cut edges 
of the photographic material which can generate many small fragments of 
chipped-off emulsion layers which then cause spot defects in the imaging 
areas of the photographic material. 
The foregoing property may be referred to as "dry adhesion". This property 
may be distinguished from "wet adhesion" which refers to the tendency of a 
photographic element to delaminate during wet processing of exposed film. 
The element may undergo spot delamination or blistering due to processing 
at elevated temperatures or may be damaged by transport rollers during 
processing or subsequent thereto. 
In U.S. Pat. No. 4,116,696, improved dry adhesive strength between a 
polyethylene terephthalate support and a photographic layer was obtained 
using a subbing layer containing a hydrophilic resin and droplets of a 
nonvolatile or low volatile hydrophobic liquid, which is not completely 
miscible with the subbing layer composition, having a boiling point above 
about 120.degree. C. and a solubility in water of about 10 g/100 g water 
or less at 25.degree. C. Thus, this improvement was obtained by altering 
the composition of the subbing layer which is coated directly on the 
polyester support, as opposed to the present invention, which involves the 
composition of the bottom-most photographic layer, coated above the 
subbing layer. We have found incorporation of liquids in a 
polymer-containing subbing layer to be ineffective at aiding dry adhesion 
due to incompatibility and level constraints in the very thin subbing 
layers employed. 
Furthermore, U.S. Pat. No. 4,116,696 specifies hydrophobic liquids having a 
solubility in water of about 10 g/100 g water or less. As later discussed, 
this corresponds to liquids with a logarithm of their octanol/water 
partition coefficient (log P) value of approximately 2.0 or more. There is 
no differentiation among liquids over a very wide range of log P values in 
this patent. 
U.S. Pat. No. 5,292,628 teaches that improved wet adhesion of photographic 
layers to a polyester film base is provided with a substrate layer 
containing an oil-in-water emulsion consisting of oil-formers, colloidal 
silicon dioxide, and gelatin. Again, the solution to the adhesion problem 
involves improved subbing layer technology, as opposed to formulation of 
the bottom-most photographic layer as described in the present invention. 
The patentee notes that "both the high oil-former content and the presence 
of colloidal silicic acid is a condition for adhesion improvement." In 
addition, the high-boiling organic liquids employed cover a very wide 
range of log P values (2.57 or greater). 
U.S. Pat. No. 4,495,273 describes a color photographic element coated on 
cellulose triacetate support with improved mechanical properties. Dry 
adhesion between the photographic layers and the support is increased 
using a combination of droplets of a water-immiscible high boiling organic 
liquid and an adhesion promoting quantity of a vinyl addition polymer 
latex to the antihalation layer of the photographic element. The support 
is a wholly different class. Again, the liquids are taught without regard 
to the log P values and all of the liquids exemplified in the examples are 
not within the necessary range in accordance with the invention herein. 
Further, the patentee also requires the presence of a vinyl addition 
polymer latex which is not essential in the present invention. 
Methods of improving adhesion to polyester supports which depend on 
altering the subbing layer, which is usually a very thin layer containing 
very low levels of gelatin, make it difficult to incorporate effective 
quantities of an adhesion promoting liquid. Also, substantial additions to 
this layer cause its thickness to be increased, which can result in the 
subbing layer being less effective at promoting adhesion of subsequently 
applied photographic emulsion layers. Increased thickness is also not 
desirable due to other system constraints such as providing a maximum 
number of exposures in a cartridge. 
The problem to be solved is to provide a photographic element having a 
polyester support which has improved dry adhesion of the applied layers to 
the polyester support. 
SUMMARY OF THE INVENTION 
The invention provides a photographic element comprising a polyester 
support bearing a light-sensitive silver halide photographic emulsion 
layer, the support having adjacent thereto a polymer-containing subbing 
layer, the subbing layer having adjacent thereto a layer comprising a 
hydrophilic binder containing dispersed droplets of a high boiling 
hydrophobic organic liquid, said liquid having a logarithm of its 
octanol/water partition coefficient (log P) value greater than 7.7. The 
invention also includes a process for preparing a photographic element of 
the invention and a process for forming an image in an element of the 
invention. The invention further includes a photographic element 
comprising a polyester support bearing a hydrophilic layer containing an 
antihalation agent, such as elemental silver, with or without an 
intervening subbing layer. 
The invention provides a photographic element having a polyester support 
which has improved dry adhesion of the applied layers to the polyester 
support and which exhibits reduced fogging upon storage at elevated 
temperatures.

DETAILED DESCRIPTION OF THE INVENTION 
Supports which can be used in this invention include any supports of 
hydrophobic, high molecular weight polyesters. Suitable supports typically 
have a glass transition temperature (T.sub.g) greater than 90.degree. C. 
The support may be produced from any suitable synthetic linear polyester 
which may be obtained by condensing one or more dicarboxylic acids or 
their lower alkyl esters, e.g., terephthalic acid, isophthalic, phthalic, 
2,5-, 2,6-, and 2,7-naphthalene dicarboxylic acid, succinic acid, sebacic 
acid, adipic acid, azelaic acid, diphenyl dicarboxylic acid, and 
hexahydroterephthalic acid or bis-p-carboxyl phenoxy ethane, optionally 
with a monocarboxylic acid, such as povalic acid, with one or more 
glycols, e.g., ethylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl 
glycol and 1,4-cyclohexanedimethanol. Suitable supports include, for 
example, polyesters such as polyethylene terephthalate, polyhexamethylene 
terephthalate, polyethylene-2,6-naphthalate, polyethylene-2,5-naphthalate, 
and polyethylene-2,7-naphthalate. Within the contemplation of the 
invention are supports based on copolymers and/or mixtures of polyesters 
based on different monomers. 
Suitable supports are described in Research Disclosure, September 1994, 
Item 36544 available from Kenneth Mason Publications Ltd, Dudley House, 12 
North Street, Emsworth Hampshire PO10 7DQ, England (hereinafter "Research 
Disclosure") and in Hatsumei Kyoukai Koukai Gihou No. 94-6023, Japan 
Invention Association, Mar. 15, 1994, available from the Japanese Patent 
Office. Supports with magnetic layers are described in Research 
Disclosure, November 1992, Item 34390. 
The supports and associated layers may contain any known additive 
materials. They may be transparent or can contain a dye or a pigment such 
as titanium dioxide or carbon black. 
If desired, the support may be subjected to a surface treatment to activate 
the surface. Such treatments include, for example, a chemical treatment, a 
mechanical treatment, a corona discharge, a glow discharge, a flame 
treatment, a UV irradiation, a radio frequency treatment, a glow 
discharge, an active plasma treatment, electrodeless discharge, a laser 
treatment, a mixed acid treatment, or ozone-oxidation treatment. Specifics 
on such treatments may be found, for example, in U.S. Pat. Nos. 3,462,335; 
3,761,299; and 4,072,769; U.K. Patent 891,469; and in Hatsumei Kyoukai 
Koukai Gihou No. 94-6023, Japan Invention Association, Mar. 15, 1994. 
In a suitable embodiment, the support may be initially treated with an 
adhesion promoting agent such as, for example, one containing at least one 
of resorcinol, orcinol, catechol, pyrogallol, 1-naphthol, 
2,4-dinitrophenol, 2,4,6-trinitrophenol, 4-chlororesorcinol, 2,4-dihydroxy 
toluene, 1,3-naphalenediol, 1,6-naphthalenediol, acrylic acid, sodium salt 
of 1-naphthol-4-sulfonic acid, benzyl alcohol, trichloroacetic acid, 
dichloroacetic acid, o-hydroxybenzotrifluoride, m-hydroxybenzotrifluoride, 
o-fluorophenol, m-fluorophenol, p-fluorophenol, chloral hydrate, and 
p-chloro-m-cresol. 
The photographic element of the invention includes a polymer-containing 
subbing layer on the treated support in a particular embodiment. By the 
term polymer-containing subbing layer it is not meant to exclude the 
presence of layer components useful for purposes other than adhesion. It 
is intended to mean that one or more of the binder components is a 
polymer. Examples of suitable polymers for this purpose are shown in U.S. 
Pat. Nos. 2,627,088; 2,968,241; 2,764,520; 2,864,755; 2,864,756; 
2,972,534; 3,057,792; 3,071,466; 3,072,483; 3,143,421; 3,145,105; 
3,145,242; 3,360,448; 3,376,208; 3,462,335; 3,475,193; 3,501,301; 
3,944,699; 4,087,574; 4,098,952; 4,363,872; 4,394,442; 4,689,359; 
4,857,396; British Patent Nos. 788,365; 804,005; 891,469; and European 
Patent No. 035,614. Often these include polymers of monomers having polar 
groups in the molecule such as carboxyl, carbonyl, hydroxy, sulfo, amino, 
amido, epoxy or acid anhydride groups, for example, acrylic acid, sodium 
acrylate, methacrylic acid, itaconic acid, crotonic acid, sorbic acid 
itaconic anhydride, maleic anhydride, cinnamic acid, methyl vinyl ketone, 
hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxychloropropyl 
methacrylate, hydroxybutyl acrylate, vinylsulfonic acid, potassium 
vinylbenezensulfonate, acrylamide, N-methylamide, N-methylacrylamide, 
acryloylmorpholine, dimethylmethacrylamide, N-t-butylacrylamide, 
diacetonacrylamide, vinylpyrrolidone, glycidyl acrylate, or glycidyl 
methacrylate, or copolymers of the above monomers with other 
copolymerizable monomers. 
Additional examples are polymers of ethylenically unsaturated esters or 
ethylenically unsaturated acids represented by, for example, acrylic acid 
esters such as ethyl acrylate or butyl acrylate, methacrylic acid esters 
such as methyl methacrylate or ethyl methacrylate, acrylic acid or 
methacrylic acid, or the acid derivatives thereof, or copolymers of these 
monomers with other vinylic monomers; or copolymers of polycarboxylic 
acids such as itaconic acid, itaconic anhydride, maleic acid or maleic 
anhydride with vinylic monomers such as styrene, vinyl chloride, 
vinylidene chloride or butadiene, or trimers of these monomers with other 
ethylenically unsaturated monomers. These polymers can be used as an 
aqueous solution, a solution in an organic liquid or a dispersion as a 
latex in water. 
The layer applied over the subbing layer contains a hydrophilic binder and 
dispersed high-boiling organic liquid droplets. Examples of suitable 
hydrophilic binders for the photographic layer (hydrophilic organic 
protective colloid), which can be used in this invention, include 
synthetic or natural hydrophilic high molecular weight gelatin-based 
compounds, for example, gelatin, acylated gelatin (phthalated gelatin or 
maleated gelatin), cellulose derivatives such as carboxymethyl cellulose 
or hydroxyethyl cellulose, grafted gelatin prepared by grafting acrylic 
acid, methacrylic acid or the amides thereof to gelatin the copolymers 
thereof or the partially hydrolyzed products thereof. Often these include 
polymers of monomers having polar groups in the molecule such as carboxyl, 
carbonyl, hydroxy, sulfo, amino, amido, epoxy or acid anhydride groups, 
for example, acrylic acid, sodium acrylate, methacrylic acid, itaconic 
acid, crotonic acid, sorbic acid' itaconic anhydride, maleic anhydride, 
cinnamic acid, methyl vinyl ketone, hydroxyethyl acrylate, hydroxyethyl 
methacrylate, hydroxychloropropyl methacrylate, hydroxybutyl acrylate, 
vinylsulfonic acid, potassium vinylbenezensulfonate, acrylamide, 
N-methylamide, N-methylacrylamide, acryloylmorpholine, 
dimethylmethacrylamide, N-t-butylacrylamide, diacetonacrylamide, 
vinylpyrrolidone, glycidyl acrylate, or glycidyl methacrylate, or 
copolymers of the above monomers with other copolymerizable monomers These 
binders can be used individually or in admixture. 
Additional examples are polymers of ethylenically unsaturated esters or 
ethylenically unsaturated acids represented by, for example, acrylic acid 
esters such as ethyl acrylate or butyl acrylate, methacrylic acid esters 
such as methyl methacrylate or ethyl methacrylate, acrylic acid or 
methacrylic acid, or the acid derivatives thereof, or copolymers of these 
monomers with other vinylic monomers; or copolymers of polycarboxylic 
acids such as itaconic acid, itaconic anhydride, maleic acid or maleic 
anhydride with vinylic monomers such as styrene, vinyl chloride, 
vinylidene chloride or butadiene, or trimers of these monomers with other 
ethylenically unsaturated monomers. 
Of the above-described binders, gelatin including a gelatin derivative is 
most generally used, but gelatin can be partially replaced with a 
synthetic high molecular weight substance. 
Suitable organic liquids usable in the present invention include 
high-boiling hydrophobic organic liquids with a log P value greater than 
7.7. Suitable boiling points of the liquids are above about 120.degree. 
C., preferably above about 160.degree. C. They generally have a very low 
solubility in water, preferably 1.0 mg/L of water or less. Suitably, the 
organic liquid has a solubility of 0.2 mg/L of water or less. 
As indicated, the Log P of a liquid is the logarithm of the liquid's 
octanol/water partition coefficient. It may be determined experimentally 
in accordance with standardized procedure or may be calculated in 
accordance with Medchem version 3.54 software available from the Medicinal 
Chemistry Project, Pomona College, Claremont, Calif. or from C. Hansch and 
A. J. Leo, Substituent Constants for Correlation Analysis in Chemistry and 
Biology, Wiley, New York, 1979. 
Specific examples of suitable liquids include, but are not limited to, 
tri-(2-ethylhexyl)phosphate, tri-octylphosphineoxide, 
1,4-cyclohexylenedimethylene bis-(2-ethylhexanoate), p-dodecylphenol, 
hexadecane, isopropylpalmitate, di-n-octyl phthalate, 
bis-(2-ethylhexyl)phthalate, dinonyl phthalate, didecylphthalate, 
didodecylphthalate, bis-(2-ethylhexyl) azelate, trioctylamine, 
dodecylbenzene, dioctylsebacate, diisooctylsebacate, dioctyl adipate, 
bis-(2-ethylhexyl)adipate and tri-(2-ethylhexyl) citrate, 
di-(2,4-di-t-butylphenyl)isophthalate, 
di-(isodecyl)4,5-epoxytetrahydrophthalate, di-amyl naphthalene, and 
tri-amylnaphthalene. 
Of these compounds, tri-(2-ethylhexyl)phosphate, 
1,4-cyclohexylenedimethylene bis-(2-ethylhexanoate), 
bis-(2-ethylhexyl)phthalate, didecylphthalate, and didodecylphthalate are 
particularly suitable. 
In the present invention, other photographically useful materials may also 
be present in the layer adjacent to the treated and/or subbed support. 
These include, antihalation components such as black colloidal silver as 
well as preformed dyes, ultraviolet absorbing compounds, oxidized 
developer scavengers, sequestering agents, etc. These materials may or may 
not be dispersed in a high-boiling organic liquid. 
In the case in which other high-boiling organic liquids with log P values 
less than 7.7 are also employed in the layer adjacent to the subbed 
support, it is preferred that the high log P liquid (greater than 7.7) 
comprise 33 wt %., suitably at least 67% of the total organic liquid in 
the layer. 
In a preferred embodiment of the invention, it is also desirable that the 
ratio of hydrophilic binder (preferably gelatin) to total liquid be 
greater than 3.0 in the layer adjacent to the subbed support. 
Unless otherwise specifically stated, substituent groups usable on 
molecules herein include any groups, whether substituted or unsubstituted, 
which do not destroy properties necessary for photographic utility. When 
the term "group" is applied to the identification of a substituent 
containing a substitutable hydrogen, it is intended to encompass not only 
the substituent's unsubstituted form, but also its form further 
substituted with any group or groups as herein mentioned. Suitably, the 
group may be halogen or may be bonded to the remainder of the molecule by 
an atom of carbon, silicon, oxygen, nitrogen, phosphorous, or sulfur. The 
substituent may be, for example, halogen, such as chlorine, bromine or 
fluorine; nitro; hydroxyl; cyano; carboxyl; or groups which may be further 
substituted, such as alkyl, including straight or branched chain alkyl, 
such as methyl, trifluoromethyl, ethyl, t-butyl, 
3-(2,4-di-t-pentylphenoxy) propyl, and tetradecyl; alkenyl, such as 
ethylene, 2-butene; alkoxy, such as methoxy, ethoxy, propoxy, butoxy, 
2-methoxyethoxy, sec-butoxy, hexyloxy, 2-ethylhexyloxy, tetradecyloxy, 
2-(2,4-di-t-pentylphenoxy) ethoxy, and 2-dodecyloxyethoxy; aryl such as 
phenyl, 4-t-butylphenyl, 2,4,6-trimethylphenyl, naphthyl; aryloxy, such as 
phenoxy, 2-methylphenoxy, alpha- or beta-naphthyloxy, and 4-tolyloxy; 
carbonamido, such as acetamido, benzamido, butyramido, tetradecanamido, 
alpha-(2,4-di-t-pentyl-phenoxy)acetamido, 
alpha-(2,4-di-t-pentylphenoxy)butyramido, 
alpha-(3-pentadecylphenoxy)-hexanamido, 
alpha-(4-hydroxy-3-t-butylphenoxy)-tetradecanamido, 2-oxo-pyrrolidin-1-yl, 
2-oxo-5-tetradecylpyrrolin-1-yl, N-methyltetradecanamido, N-succinimido, 
N-phthalimido, 2,5-dioxo-1-oxazolidinyl, 3-dodecyl-2,5-dioxo-1-imidazolyl, 
and N-acetyl-N-dodecylamino, ethoxycarbonylamino, phenoxycarbonylamino, 
benzyloxycarbonylamino, hexadecyloxycarbonylamino, 
2,4-di-t-butylphenoxycarbonylamino, phenylcarbonylamino, 
2,5-(di-t-pentylphenyl)carbonylamino, p-dodecyl-phenylcarbonylamino, 
p-toluylcarbonylamino, N-methylureido, N,N-dimethylureido, 
N-methyl-N-dodecylureido, N-hexadecylureido, N,N-dioctadecylureido, 
N,N-dioctyl-N'-ethylureido, N-phenylureido, N,N-diphenylureido, 
N-phenyl-N-p-toluylureido, N-(m-hexadecylphenyl)ureido, 
N,N-(2,5-di-t-pentylphenyl)-N'-ethylureido, and t-butylcarbonamido; 
sulfonamido, such as methylsulfonamido, benzenesulfonamido, 
p-toluylsulfonamido, p-dodecylbenzenesulfonamido, 
N-methyltetradecylsulfonamido, N,N-dipropyl-sulfamoylamino, and 
hexadecylsulfonamido; sulfamoyl, such as N-methylsulfamoyl, 
N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-hexadecylsulfamoyl, 
N,N-dimethylsulfamoyl; N-3-(dodecyloxy)propyl!sulfamoyl, 
N-4-(2,4-di-t-pentylphenoxy)butyl!sulfamoyl, 
N-methyl-N-tetradecylsulfamoyl, and N-dodecylsulfamoyl; carbamoyl, such as 
N-methylcarbamoyl, N,N-dibutylcarbamoyl, N-octadecylcarbamoyl, 
N-4-(2,4-di-t-pentylphenoxy)butyl!carbamoyl, 
N-methyl-N-tetradecylcarbamoyl, and N,N-dioctylcarbamoyl; acyl, such as 
acetyl, (2,4-di-t-amylphenoxy)acetyl, phenoxycarbonyl, 
p-dodecyloxyphenoxycarbonyl methoxycarbonyl, butoxycarbonyl, 
tetradecyloxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, 
3-pentadecyloxycarbonyl, and dodecyloxycarbonyl; sulfonyl, such as 
methoxysulfonyl, octyloxysulfonyl, tetradecyloxysulfonyl, 
2-ethylhexyloxysulfonyl, phenoxysulfonyl, 2,4-di-t-pentylphenoxysulfonyl, 
methylsulfonyl, octylsulfonyl, 2-ethylhexylsulfonyl, dodecylsulfonyl, 
hexadecylsulfonyl, phenylsulfonyl, 4-nonylphenylsulfonyl, and 
p-toluylsulfonyl; sulfonyloxy, such as dodecylsulfonyloxy, and 
hexadecylsulfonyloxy; sulfinyl, such as methylsulfinyl, octylsulfinyl, 
2-ethylhexylsulfinyl, dodecylsulfinyl, hexadecylsulfinyl, phenylsulfinyl, 
4-nonylphenylsulfinyl, and p-toluylsulfinyl; thio, such as ethylthio, 
octylthio, benzylthio, tetradecylthio, 
2-(2,4-di-t-pentylphenoxy)ethylthio, phenylthio, 
2-butoxy-5-t-octylphenylthio, and p-tolylthio; acyloxy, such as acetyloxy, 
benzoyloxy, octadecanoyloxy, p-dodecylamidobenzoyloxy, 
N-phenylcarbamoyloxy, N-ethylcarbamoyloxy, and cyclohexylcarbonyloxy; 
amine, such as phenylanilino, 2-chloroanilino, diethylamine, dodecylamine; 
imino, such as 1 (N-phenylimido)ethyl, N-succinimido or 
3-benzylhydantoinyl; phosphate, such as dimethylphosphate and 
ethylbutylphosphate; phosphite, such as diethyl and dihexylphosphite; a 
heterocyclic group, a heterocyclic oxy group or a heterocyclic thio group, 
each of which may be substituted and which contain a 3 to 7 membered 
heterocyclic ring composed of carbon atoms and at least one hetero atom 
selected from the group consisting of oxygen, nitrogen and sulfur, such as 
2-furyl, 2-thienyl, 2-benzimidazolyloxy or 2-benzothiazolyl; quaternary 
ammonium, such as triethylammonium; and silyloxy, such as 
trimethylsilyloxy. 
If desired, the substituents may themselves be further substituted one or 
more times with the described substituent groups. The particular 
substituents used may be selected by those skilled in the art to attain 
the desired photographic properties for a specific application and can 
include, for example, hydrophobic groups, solubilizing groups, blocking 
groups, releasing or releasable groups, etc. Generally, the above groups 
and substituents thereof may include those having up to 48 carbon atoms, 
typically 1 to 36 carbon atoms and usually less than 24 carbon atoms, but 
greater numbers are possible depending on the particular substituents 
selected. 
To control the migration of various components, it may be desirable to 
include a high molecular weight hydrophobe or "ballast" group in the 
component molecule. Representative ballast groups include substituted or 
unsubstituted alkyl or aryl groups containing 8 to 42 carbon atoms. 
Representative substituents on such groups include alkyl, aryl, alkoxy, 
aryloxy, alkylthio, hydroxy, halogen, alkoxycarbonyl, aryloxcarbonyl, 
carboxy, acyl, acyloxy, amino, anilino, carbonamido, carbamoyl, 
alkylsulfonyl, arysulfonyl, sulfonamido, and sulfamoyl groups wherein the 
substituents typically contain 1 to 42 carbon atoms. Such substituents can 
also be further substituted. 
The photographic elements can be single color elements or multicolor 
elements. Multicolor elements contain image dye-forming units sensitive to 
each of the three primary regions of the spectrum. Each unit can comprise 
a single emulsion layer or multiple emulsion layers sensitive to a given 
region of the spectrum. The layers of the element, including the layers of 
the image-forming units, can be arranged in various orders as known in the 
art. In an alternative format, the emulsions sensitive to each of the 
three primary regions of the spectrum can be disposed as a single 
segmented layer. 
A typical multicolor photographic element comprises a support bearing a 
cyan dye image-forming unit comprised of at least one red-sensitive silver 
halide emulsion layer having associated therewith at least one cyan 
dye-forming coupler, a magenta dye image-forming unit comprising at least 
one green-sensitive silver halide emulsion layer having associated 
therewith at least one magenta dye-forming coupler, and a yellow dye 
image-forming unit comprising at least one blue-sensitive silver halide 
emulsion layer having associated therewith at least one yellow dye-forming 
coupler. The element can contain additional layers, such as filter layers, 
interlayers, overcoat layers, subbing layers, and the like. 
If desired, the photographic element can be used in conjunction with an 
applied magnetic layer as described in Research Disclosure, November 1992, 
Item 34390 published by Kenneth Mason Publications, Ltd., Dudley Annex, 
12a North Street, Emsworth, Hampshire P010 7DQ, ENGLAND, the contents of 
which are incorporated herein by reference. 
Research Disclosure, June 1994, Item 36230 provides information on suitable 
film adaptions for small format film. 
In the following discussion of suitable materials for use in the emulsions 
and elements of this invention, reference will be made to Research 
Disclosure, September 1994, Item 36544, available as described above, 
which will be identified hereafter by the term "Research Disclosure". The 
contents of the Research Disclosure, including the patents and 
publications referenced therein, are incorporated herein by reference, and 
the Sections hereafter referred to are Sections of the Research 
Disclosure. 
The silver halide emulsions employed in the elements of this invention can 
be either negative-working or positive-working. Suitable emulsions and 
their preparation as well as methods of chemical and spectral 
sensitization are described in Sections I through V. Various additives 
such as UV dyes, brighteners, antifoggants, stabilizers, light absorbing 
and scattering materials, and physical property modifying addenda such as 
hardeners, coating aids, plasticizers, lubricants and matting agents are 
described, for example, in Sections II and Vi through VIII. Color 
materials are described in Sections X through XIII. Scan facilitating is 
described in Section XIV. Supports, exposure, development systems, and 
processing methods and agents are described in Sections XV to XX. 
Coupling-off groups are well known in the art. Such groups can determine 
the chemical equivalency of a coupler, i.e., whether it is a 2-equivalent 
or a 4-equivalent coupler, or modify the reactivity of the coupler. Such 
groups can advantageously affect the layer in which the coupler is coated, 
or other layers in the photographic recording material, by performing, 
after release from the coupler, functions such as dye formation, dye hue 
adjustment, development acceleration or inhibition, bleach acceleration or 
inhibition, electron transfer facilitation, color correction and the like. 
The presence of hydrogen at the coupling site provides a 4-equivalent 
coupler, and the presence of another coupling-off group usually provides a 
2-equivalent coupler. Representative classes of such coupling-off groups 
include, for example, chloro, alkoxy, aryloxy, hetero-oxy, sulfonyloxy, 
acyloxy, acyl, heterocyclyl, sulfonamido, mercaptotetrazole, 
benzothiazole, mercaptopropionic acid, phosphonyloxy, arylthio, and 
arylazo. These coupling-off groups are described in the art, for example, 
in U.S. Pat. Nos. 2,455,169, 3,227,551, 3,432,521, 3,476,563, 3,617,291, 
3,880,661, 4,052,212 and 4,134,766; and in U.K. Patents and published 
application Nos. 1,466,728, 1,531,927, 1,533,039, 2,006,755A and 
2,017,704A, the disclosures of which are incorporated herein by reference. 
Image dye-forming couplers may be included in the element such as couplers 
that form cyan dyes upon reaction with oxidized color developing agents 
which are described in such representative patents and publications as: 
U.S. Pat. Nos. 2,367,531, 2,423,730, 2,474,293, 2,772,162, 2,895,826, 
3,002,836, 3,034,892, 3,041,236, 4,333,999, 4,883,746 and 
"Farbkuppler-eine LiteratureUbersicht," published in Agfa Mitteilungen, 
Band III, pp. 156-175 (1961). Preferably such couplers are phenols and 
naphthols that form cyan dyes on reaction with oxidized color developing 
agent. 
Couplers that form magenta dyes upon reaction with oxidized color 
developing agent are described in such representative patents and 
publications as: U.S. Pat. Nos. 2,311,082, 2,343,703, 2,369,489, 
2,600,788, 2,908,573, 3,062,653, 3,152,896, 3,519,429, and 
"Farbkuppler-eine LiteratureUbersicht," published in Agfa Mitteilungen, 
Band III, pp. 126-156 (1961). Preferably such couplers are pyrazolones, 
pyrazolotriazoles, or pyrazolobenzimidazoles that form magenta dyes upon 
reaction with oxidized color developing agents. 
Couplers that form yellow dyes upon reaction with oxidized and color 
developing agent are described in such representative patents and 
publications as: U.S. Pat. Nos. 2,298,443, 2,407,210, 2,875,057, 
3,048,194, 3,265,506, 3,447,928, 4,022,620, 4,443,536, and 
"Farbkuppler-eine LiteratureUbersicht," published in Agfa Mitteilungen, 
Band III, pp. 112-126 (1961). Such couplers are typically open chain 
ketomethylene compounds. 
Couplers that form colorless products upon reaction with oxidized color 
developing agent are described in such representative patents as: U.K. 
Patent No. 861,138; U.S. Pat. Nos. 3,632,345, 3,928,041, 3,958,993 and 
3,961,959. Typically such couplers are cyclic carbonyl containing 
compounds that form colorless products on reaction with an oxidized color 
developing agent. 
Couplers that form black dyes upon reaction with oxidized color developing 
agent are described in such representative patents as U.S. Pat. Nos. 
1,939,231; 2,181,944; 2,333,106; and 4,126,461; German OLS No. 2,644,194 
and German OLS No. 2,650,764. Typically, such couplers are resorcinols or 
m-aminophenols that form black or neutral products on reaction with 
oxidized color developing agent. 
In addition to the foregoing, so-called "universal" or "washout" couplers 
may be employed. These couplers do not contribute to image dye-formation. 
Thus, for example, a naphthol having an unsubstituted carbamoyl or one 
substituted with a low molecular weight substituent at the 2- or 3- 
position may be employed. Couplers of this type are described, for 
example, in U.S. Pat. Nos. 5,026,628, 5,151,343, and 5,234,800. 
It may be useful to use a combination of couplers any of which may contain 
known ballasts or coupling-off groups such as those described in U.S. Pat. 
No. 4,301,235; U.S. Pat. No. 4,853,319 and U.S. Pat. No. 4,351,897. The 
coupler may contain solubilizing groups such as described in U.S. Pat. No. 
4,482,629. The coupler may also be used in association with "wrong" 
colored couplers (e.g. to adjust levels of interlayer correction) and, in 
color negative applications, with masking couplers such as those described 
in EP 213.490; Japanese Published Application 58-172,647; U.S. Pat. Nos. 
2,983,608; 4,070,191; and 4,273,861; German Applications DE 2,706,117 and 
DE 2,643,965; U.K. Patent 1,530,272; and Japanese Application A-113935. 
The masking couplers may be shifted or blocked, if desired. 
For example, in a color negative element, the materials of the invention 
may replace or supplement the materials of an element comprising a support 
bearing the following layers from top to bottom: 
(1) one or more overcoat layers containing ultraviolet absorber(s); 
(2) a two-coat yellow pack with a fast yellow layer containing "Coupler 1": 
Benzoic acid, 
4-chloro-3-((2-(4-ethoxy-2,5-dioxo-3-(phenylmethyl)-1-imidazolidinyl)-3-(4 
-methoxyphenyl)-1,3-dioxopropyl)amino)-, dodecyl ester and a slow yellow 
layer containing the same compound together with "Coupler 2": Propanoic 
acid, 
2-5-4-2-2,4-bis(1,1-dimethylpropyl)phenoxy!acetyl!amino!-5-(2,2,3 
,3,4,4,4-heptafluoro-1-oxobutyl)amino!-4-hydroxyphenoxy!-2,3-dihydroxy-6-( 
propylamino)carbonyl!phenyl!thio!-1,3,4-thiadiazol-2-yl!thio!-, methyl 
ester and "Coupler 3":1-((dodecyloxy)carbonyl) 
ethyl(3-chloro-4-((3-(2-chloro-4-((1-tridecanoylethoxy) 
carbonyl)anilino)-3-oxo-2-((4)(5)(6)-(phenoxycarbonyl)-1H-benzotriazol-1-y 
l)propanoyl)amino))benzoate; 
(3) an interlayer containing fine metallic silver; 
(4) a triple-coat magenta pack with a fast magenta layer containing 
"Coupler 4": Benzamide, 
3-((2-(2,4-bis(1,1-dimethylpropyl)phenoxy)-1-oxobutyl)amino)-N-(4,5-dihydr 
o-5-oxo-1-(2,4,6-trichlorophenyl)-1H-pyrazol-3-yl)-,"Coupler 5": Benzamide, 
3-((2-(2,4-bis(1,1-dimethylpropyl)phenoxy)-1-oxobutyl)amino)-N-(4',5'-dihy 
dro-5'-oxo-1'-(2,4,6-trichlorophenyl) (1,4'-bi-1H-pyrazol)-3'-yl)-, 
"Coupler 6": Carbamic acid, (6-(((3-(dodecyloxy)propyl) 
amino)carbonyl)-5-hydroxy-1-naphthalenyl)-, 2-methylpropyl ester , 
"Coupler 7": Acetic acid, ((2-((3-(((3-(dodecyloxy)propyl)amino) 
carbonyl)-4-hydroxy-8-(((2-methylpropoxy)carbonyl) 
amino)-1-naphthalenyl)oxy )ethyl)thio)-, and "Coupler 8" Benzamide, 
3-((2-(2,4-bis(1,1-dimethylpropyl) 
phenoxy)-1-oxobutyl)amino)-N-(4,5-dihydro-4-((4-methoxyphenyl) 
azo)-5-oxo-1-(2,4,6-trichlorophenyl)-1H-pyrazol-3-yl)-; a mid-magenta 
layer and a slow magenta layer each containing "Coupler 9": a ternary 
copolymer containing by weight in the ratio 1:1:2 2-Propenoic acid butyl 
ester, styrene, and 
N-1-(2,4,6-trichlorophenyl)-4,5-dihydro-5-oxo-1H-pyrazol-3-yl!-2-methyl-2 
-propenamide; and "Coupler 10": Tetradecanamide, 
N-(4-chloro-3-((4-((4-((2,2-dimethyl-1-oxopropyl) 
amino)phenyl)azo)-4,5-dihydro-5-oxo-1-(2,4,6-trichlorophenyl)-1H-pyrazol-3 
-yl)amino)phenyl)-, in addition to Couplers 3 and 8; 
(5) an interlayer; 
(6) a triple-coat cyan pack with a fast cyan layer containing Couplers 6 
and 7; a mid-cyan containing Coupler 6 and "Coupler 11": 
2,7-Naphthalenedisulfonic acid, 
5-(acetylamino)-3-((4-(2-((3-(((3-(2,4-bis(1,1-dimethylpropyl)phenoxy) 
propyl)amino)carbonyl)-4-hydroxy-1-naphthalenyl) 
oxy)ethoxy)phenyl)azo)-4-hydroxy-, disodium salt; and a slow cyan layer 
containing Couplers 2 and 6; 
(7) an undercoat layer containing Coupler 8; and 
(8) an antihalation layer. 
In a reversal format, the materials of the invention may replace or 
supplement the materials of an element comprising a support bearing the 
following layers from top to bottom: 
(1) one or more overcoat layers; 
(2) a nonsensitized silver halide containing layer; 
(3) a triple-coat yellow layer pack with a fast yellow layer containing 
"Coupler 1": Benzoic acid, 
4-(1-(((2-chloro-5-((dodecylsulfonyl)amino)phenyl) 
amino)carbonyl)-3,3-dimethyl-2-oxobutoxy)-, 1-methylethyl ester; a mid 
yellow layer containing Coupler 1 and "Coupler 2": Benzoic acid, 
4-chloro-3-2-4-ethoxy-2,5-dioxo-3-(phenylmethyl)-1-imidazolidinyl!-4,4- 
dimethyl-1,3-dioxopentyl!amino!-, dodecylester; and a slow yellow layer 
also containing Coupler 2; 
(4) an interlayer; 
(5) a layer of fine-grained silver; 
(6) an interlayer; 
(7) a triple-coated magenta pack with a fast and mid magenta layer 
containing "Coupler 3": 2-Propenoic acid, butyl ester, polymer with 
N-1-(2,5-dichlorophenyl)-4,5-dihydro-5-oxo-1H-pyrazol-3-yl!-2-methyl-2-pr 
openamide; "Coupler 4": Benzamide, 
3-((2-(2,4-bis(1,1-dimethylpropyl)phenoxy)-1-oxobutyl)amino)-N-(4,5-dihydr 
o-5-oxo-1-(2,4,6-trichlorophenyl)-1H-pyrazol-3-yl)-; and "Coupler 5": 
Benzamide, 
3-(((2,4-bis(1,1-dimethylpropyl)phenoxy)acetyl)amino)-N-(4,5-dihydro-5-oxo 
-1-(2,4,6-trichlorophenyl)-1H-pyrazol-3-y1)-; and containing the stabilizer 
1,1'-Spirobi(1H-indene), 
2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-5,5',6,6'-tetrapropoxy-; and in 
the slow magenta layer Couplers 4 and 5 with the same stabilizer; 
(8) one or more interlayers possibly including fine-grained nonsensitized 
silver halide; 
(9) a triple-coated cyan pack with a fast cyan layer containing "Coupler 
6": Tetradecanamide, 
2-(2-cyanophenoxy)-N-(4-((2,2,3,3,4,4,4-heptafluoro-1-oxobutyl)amino)-3-hy 
droxyphenyl)-; a mid cyan containing "Coupler 7": Butanamide, 
N-(4-((2-(2,4-bis(1,1-dimethylpropyl)phenoxy)-1-oxobutyl)amino)-2-hydroxyp 
henyl)-2,2,3,3,4,4,4-heptafluoro- and "Coupler 8": Hexanamide, 
2-(2,4-bis(1,1-dimethylpropyl)phenoxy)-N-(4-((2,2,3,3,4,4,4-heptafluoro-1- 
oxobutyl)amino)-3-hydroxyphenyl)-; and a slow cyan layer containing 
Couplers 6, 7, and 8; 
(10) one or more interlayers possibly including fine-grained nonsensitized 
silver halide; and 
(11) an antihalation layer. 
The invention materials may be used in association with materials that 
accelerate or otherwise modify the processing steps e.g. of bleaching or 
fixing to improve the quality of the image. Bleach accelerator releasing 
couplers such as those described in EP 193,389; EP 301,477; U.S. Pat. No. 
4,163,669; U.S. Pat. No. 4,865,956; and U.S. Pat. No. 4,923,784, may be 
useful. Also contemplated is use of the compositions in association with 
nucleating agents, development accelerators or their precursors (UK Patent 
2,097,140; U.K. Patent 2,131,188); electron transfer agents (U.S. Pat. No. 
4,859,578; U.S. Pat No. 4,912,025); antifogging and anti color-mixing 
agents such as derivatives of hydroquinones, aminophenols, amines, gallic 
acid; catechol; ascorbic acid; hydrazides; sulfonamidophenols; and non 
color-forming couplers. 
The invention materials may also be used in combination with filter dye 
layers comprising colloidal silver sol or yellow, cyan, and/or magenta 
filter dyes, either as oil-in-water dispersions, latex dispersions or as 
solid particle dispersions. Additionally, they may be used with "smearing" 
couplers (e.g. as described in U.S. Pat. No. 4,366,237; EP 96,570; U.S. 
Pat. No. 4,420,556; and U.S. Pat. No. 4,543,323.) Also, the compositions 
may be blocked or coated in protected form as described, for example, in 
Japanese Application 61/258,249 or U.S. Pat. No. 5,019,492. 
The invention materials may further be used in combination with 
image-modifying compounds such as "Developer Inhibitor-Releasing" 
compounds (DIR's). DIR's useful in conjunction with the compositions of 
the invention are known in the art and examples are described in U.S. Pat. 
Nos. 3,137,578; 3,148,022; 3,148 062; 3,227,554; 3,384,657; 3,379,529; 
3,615,506; 3,617 291; 3,620,746; 3,701,783; 3,733,201; 4,049,455; 4,095 
984; 4,126,459; 4,149,886; 4,150,228; 4,211,562; 4,248 962; 4,259,437; 
4,362,878; 4,409,323; 4,477,563; 4,782 012; 4,962,018; 4,500,634; 
4,579,816; 4,607,004; 4,618 571; 4,678,739; 4,746,600; 4,746,601; 
4,791,049; 4,857 447; 4,865,959; 4,880,342; 4,886,736; 4,937,179; 
4,946,767; 4,948,716; 4,952,485; 4,956,269; 4,959,299; 4,966,835; 
4,985,336 as well as in patent publications GB 1,560,240; GB 2,007,662; GB 
2,032,914; GB 2,099,167; DE 2,842,063, DE 2,937,127; DE 3,636,824; DE 
3,644,416 as well as the following European Patent Publications: 272,573; 
335,319; 336,411; 346, 899; 362, 870; 365,252; 365,346; 373,382; 376,212; 
377,463; 378,236; 384,670; 396,486; 401,612; 401,613. 
Such compounds are also disclosed in "Developer-inhibitor-Releasing (DIR) 
Couplers for Color Photography," C. R. Barr, J. R. Thirtle and P. W. 
Vittum in Photographic Science and Engineering, Vol. 13, p. 174 (1969), 
incorporated herein by reference. Generally, the developer 
inhibitor-releasing (DIR) couplers include a coupler moiety and an 
inhibitor coupling-off moiety (IN). The inhibitor-releasing couplers may 
be of the time-delayed type (DIAR couplers) which also include a timing 
moiety or chemical switch which produces a delayed release of inhibitor. 
Examples of typical inhibitor moieties are: oxazoles, thiazoles, diazoles, 
triazoles, oxadiazoles, thiadiazoles, oxathiazoles, thiatriazoles, 
benzotriazoles, tetrazoles, benzimidazoles, indazoles, isoindazoles, 
mercaptotetrazoles, selenotetrazoles, mercaptobenzothiazoles, 
selenobenzothiazoles, mercaptobenzoxazoles, selenobenzoxazoles, 
mercaptobenzimidazoles, selenobenzimidazoles, benzodiazoles, 
mercaptooxazoles, mercaptothiadiazoles, mercaptothiazoles, 
mercaptotriazoles, mercaptooxadiazoles, mercaptodiazoles, 
mercaptooxathiazoles, telleurotetrazoles or benzisodiazoles. In a 
preferred embodiment, the inhibitor moiety or group is selected from the 
following formulas: 
##STR1## 
wherein R.sub.I is selected from the group consisting of straight and 
branched alkyls of from 1 to about 8 carbon atoms, benzyl, phenyl, and 
alkoxy groups and such groups containing none, one or more than one such 
substituent; R.sub.II is selected from R.sub.I and -SR.sub.I ; R.sub.III 
is a straight or branched alkyl group of from 1 to about 5 carbon atoms 
and m is from 1 to 3; and R.sub.IV is selected from the group consisting 
of hydrogen, halogens and alkoxy, phenyl and carbonamido groups, 
--COOR.sub.V and --NHCOOR.sub.V wherein R.sub.V is selected from 
substituted and unsubstituted alkyl and aryl groups. 
Although it is typical that the coupler moiety included in the developer 
inhibitor-releasing coupler forms an image dye corresponding to the layer 
in which it is located, it may also form a different color as one 
associated with a different film layer. It may also be useful that the 
coupler moiety included in the developer inhibitor-releasing coupler forms 
colorless products and/or products that wash out of the photographic 
material during processing (so-called "universal" couplers). 
As mentioned, the developer inhibitor-releasing coupler may include a 
timing group which produces the time-delayed release of the inhibitor 
group such as groups utilizing the cleavage reaction of a hemiacetal (U.S. 
Pat. No. 4,146,396, Japanese Applications 60-249148; 60-249149); groups 
using an intramolecular nucleophilic substitution reaction (U.S. Pat. No. 
4,248,962); groups utilizing an electron transfer reaction along a 
conjugated system (U.S. Pat. Nos. 4,409,323; 4,421,845; Japanese 
Applications 57-188035; 58-98728; 58-209736; 58-209738) groups utilizing 
ester hydrolysis (German Patent Application (OLS) No. 2,626,315; groups 
utilizing the cleavage of imino ketals (U.S. Pat. No. 4,546,073); groups 
that function as a coupler or reducing agent after the coupler reaction 
(U.S. Pat. No. 4,438,193; U.S. Pat. No. 4,618,571) and groups that combine 
the features describe above. It is typical that the timing group or moiety 
is of one of the formulas: 
##STR2## 
wherein IN is the inhibitor moiety, Z is selected from the group 
consisting of nitro, cyano, alkylsulfonyl; sulfamoyl (--SO.sub.2 
NR.sub.2); and sulfonamido (--NRSO.sub.2 R) groups; n is 0 or 1; and 
R.sub.VI is selected from the group consisting of substituted and 
unsubstituted alkyl and phenyl groups. The oxygen atom of each timing 
group is bonded to the coupling-off position of the respective coupler 
moiety of the DIAR. 
Suitable developer inhibitor-releasing couplers for use in the present 
invention include, but are not limited to, the following: 
##STR3## 
Especially useful in this invention are tabular grain silver halide 
emulsions. Specifically contemplated tabular grain emulsions are those in 
which greater than 50 percent of the total projected area of the emulsion 
grains are accounted for by tabular grains having a thickness of less than 
0.3 micron (0.5 micron for blue sensitive emulsion) and an average 
tabularity (T) of greater than 25 (preferably greater than 100), where the 
term "tabularity" is employed in its art recognized usage as 
EQU T=ECD/t.sup.2 
where 
ECD is the average equivalent circular diameter of the tabular grains in 
micrometers and 
t is the average thickness in micrometers of the tabular grains. 
The average useful ECD of photographic emulsions can range up to about 10 
micrometers, although in practice emulsion ECD's seldom exceed about 4 
micrometers. Since both photographic speed and granularity increase with 
increasing ECD's, it is generally preferred to employ the smallest tabular 
grain ECD's compatible with achieving aim speed requirements. 
Emulsion tabularity increases markedly with reductions in tabular grain 
thickness. It is generally preferred that aim tabular grain projected 
areas be satisfied by thin (t&lt;0.2 micrometer) tabular grains. To achieve 
the lowest levels of granularity it is preferred that aim tabular grain 
projected areas be satisfied with ultrathin (t&lt;0.06 micrometer) tabular 
grains. Tabular grain thicknesses typically range down to about 0.02 
micrometer. However, still lower tabular grain thicknesses are 
contemplated. For example, Daubendiek et al U.S. Pat. No. 4,672,027 
reports a 3 mole percent iodide tabular grain silver bromoiodide emulsion 
having a grain thickness of 0.017 micrometer. Ultrathin tabular grain high 
chloride emulsions are disclosed by Maskasky U.S. Pat. No. 5,217,858. 
As noted above tabular grains of less than the specified thickness account 
for at least 50 percent of the total grain projected area of the emulsion. 
To maximize the advantages of high tabularity it is generally preferred 
that tabular grains satisfying the stated thickness criterion account for 
the highest conveniently attainable percentage of the total grain 
projected area of the emulsion. For example, in preferred emulsions, 
tabular grains satisfying the stated thickness criteria above account for 
at least 70 percent of the total grain projected area. In the highest 
performance tabular grain emulsions, tabular grains satisfying the 
thickness criteria above account for at least 90 percent of total grain 
projected area. 
Suitable tabular grain emulsions can be selected from among a variety of 
conventional teachings, such as those of the following: Research 
Disclosure, Item 22534, January 1983, published by Kenneth Mason 
Publications, Ltd., Emsworth, Hampshire P010 7DD, England; U.S. Pat. Nos. 
4,439,520; 4,414,310; 4,433,048; 4,643,966; 4,647,528; 4,665,012; 
4,672,027; 4,678,745; 4,693,964; 4,713,320; 4,722,886; 4,755,456; 
4,775,617; 4,797,354; 4,801,522; 4,806,461; 4,835,095; 4,853,322; 
4,914,014; 4,962,015; 4,985,350; 5,061,069 and 5,061,616. 
The emulsions can be surface-sensitive emulsions, i.e., emulsions that form 
latent images primarily on the surfaces of the silver halide grains, or 
the emulsions can form internal latent images predominantly in the 
interior of the silver halide grains. The emulsions can be 
negative-working emulsions, such as surface-sensitive emulsions or 
unfogged internal latent image-forming emulsions, or direct-positive 
emulsions of the unfogged, internal latent image-forming type, which are 
positive-working when development is conducted with uniform light exposure 
or in the presence of a nucleating agent. 
Photographic elements can be exposed to actinic radiation, typically in the 
visible region of the spectrum, to form a latent image and can then be 
processed to form a visible dye image. Processing to form a visible dye 
image includes the step of contacting the element with a color developing 
agent to reduce developable silver halide and oxidize the color developing 
agent. Oxidized color developing agent in turn reacts with the coupler to 
yield a dye. 
With negative-working silver halide, the processing step described above 
provides a negative image. The described elements can be processed in the 
known C-41 color process as described in The British Journal of 
Photography Annual of 1988, pages 191-198. To provide a positive (or 
reversal) image, the color development step can be preceded by development 
with a non-chromogenic developing agent to develop exposed silver halide, 
but not form dye, and followed by uniformly fogging the element to render 
unexposed silver halide developable. Alternatively, a direct positive 
emulsion can be employed to obtain a positive image. 
Preferred color developing agents are p-phenylenediamines such as: 
4-amino-N,N-diethylaniline hydrochloride, 
4-amino-3-methyl-N,N-diethylaniline hydrochloride, 
4-amino-3-methyl-N-ethyl-N-(.beta.-(methanesulfonamido) ethyl)aniline 
sesquisulfate hydrate, 
4-amino-3-methyl-N-ethyl-N-(.beta.-hydroxyethyl)aniline sulfate, 
4-amino-3-.beta.-(methanesulfonamido)ethyl-N,N-diethylaniline hydrochloride 
and 
4-amino-N-ethyl-N-(2-methoxyethyl)-m-toluidine di-p-toluene sulfonic acid. 
Development is usually followed by the conventional steps of bleaching, 
fixing, or bleach-fixing, to remove silver or silver halide, washing, and 
drying. 
The entire contents of the various patents and other publications cited in 
this specification are incorporated herein by reference. 
EXAMPLE 1 
Preparation of Dispersion A 
4.0 g of a n-octadecyl-3-(3'-5'-di-t-butyl-4'-hydroxyphenyl) propionate as 
Irganox-1706.RTM. (Ciba-Geigy Co.) was dissolved in 400.0 g of 
diethylphthalate at 50.degree. C., then combined with an aqueous solution 
consisting of 400.0 g gelatin. 300.0 g of a 10% solution of a mixture of 
the isomers of the sodium salt isopropylnaphthalene sulfonic acid as 
Alkanol-XC.RTM. (DuPont de Nemours & Co.), 7.2 g of a 0.7% solution of a 
biocide blend of 5-chloro-2-methyl-4-isothiazolin-3-one and 
2-methyl-4-isothiazolin-3-one as Kathon LX.RTM. (Rohm and Haas Co.), and 
3488.8 g of distilled water, also at 50.degree. C. 
This mixture was then premixed using a Silverson mixer for 5 minutes at 
5000 rpm and then passed through a Crepaco homogenizer one time at 5000 
psi to form a dispersion consisting of 8.0% liquid, 8.0% gel. 
Preparation of Dispersions B through O 
Dispersions B through O were prepared like Dispersion A except that 400.0 g 
diethylphthalate was replaced with 400.0 g of another high-boiling organic 
liquid as outlined in Table I below. 
TABLE I 
______________________________________ 
Dispersion 
Type Organic Liquid Log P 
______________________________________ 
A Comp Diethylphthalate 2.57 
B Comp Dicyclohexylphthalate 
6.80 
C Inv Bis(2-ethylhexyl)phthalate 
8.92 
D Inv Didecylphthalate 11.04 
E Inv Didodecylphthalate 13.16 
F Comp Trihexyl phosphate 6.70 
G comp Oleyl alcohol 7.69 
H Comp Acetyl-tri-butyl citrate 
4.78 
I Comp Phenyl ethyl benzoate 
4.21 
J Comp Dibutyl sebacate 5.98 
K Comp N-n-Butylacetanilide 
2.29 
L lnv 1,4-Cyclohexylenedimethylene bis(2- 
8.14 
ethylhexanoate) 
M Inv Tri(2-ethylhexyl)phosphate 
9.49 
N Comp Dibutylphthalate 4.69 
O Comp Tricresylphosphate 6.58 
______________________________________ 
These dispersions were added to the coating solution used for the 
antihalation layer to provide a dry coating weight of 0.484 g/m.sup.2. 
To a corona-discharge-treated polyethylene-2,6-naphthalene support, which 
was coated with a continuous subbing layer consisting of a terpolymer of 
n-butyl acrylate, 2-aminoethyl methacrylate hydrochloride, and 
2-hydroxyethyl methacrylate (50:05:45) at 0.317 g/m.sup.2 ; deionized 
gelatin at 0.056 g/m.sup.2 ; matte beads at 0.001 g/m.sup.2 ; and 
surfactant 10G.RTM. (Dixie) at 0.012 g/m.sup.2 ; the following layers were 
applied in the indicated sequence to produce Coating 1-1. The quantities 
quoted each relate to g/m.sup.2. Emulsion sizes as determined by the disc 
centrifuge method are reported in Diameter.times.Thickness in microns. 
Layer 1: black colloidal silver at 0.151; gelatin at 1.614; sulfuric acid 
at 0.0014; Triton X-200.RTM. (Rohm and Haas) at 0.040; hexasodium salt of 
metaphosphoric acid at 0.011; disodium salt of 3,5-disulfocatechol at 
0.270; Dye 1 at 0.118; Dye 2 at 0.024; Dye 3 at 0.005; AF-1 at 0.0009; 
AF-2 at 0.0012. 
Layer 2 (Slow cyan layer): a blend of two silver iodobromide emulsions 
sensitized with Dye Set 1: (i) a small tabular emulsion (1.1.times.0.09, 
4.1 mole % I) at 0.414 and (ii) a very small tabular grain emulsion 
(0.5.times.0.08, 1.3 mole % I) at 0.506; gelatin at 1.69; cyan dye-forming 
coupler C-1 at 0.513; bleach accelerator releasing coupler B-1 at 0.037; 
masking coupler MC-1 at 0.026. 
Layer 3 (Mid cyan layer): a red-sensitized (same as above) silver 
iodobromide emulsion (1.3.times.0.12, 4.1 mole % I) at 0.699; gelatin at 
1.79; C-1 at 0.180; DIR-1 at 0.010; MC-1 at 0.022. 
Layer 4 (Fast cyan layer): a red-sensitized (same as above) tabular silver 
iodobromide emulsion (2.9.times.0.13, 4.1 mole % I) at 1.076; C-1 at 
0.104; DIR-1 at 0.019; DIR-2 at 0.048; MC-1 at 0.032; gelatin at 1.42. 
Layer 5 (Interlayer): gelatin at 1.29. 
Layer 6 (Slow magenta layer): a blend of two silver iodobromide emulsions 
sensitized with Dye Set 2: (i) 1.0.times.0.09, 4.1 mole % iodide at 0.280 
and (ii) 0.5.times.0.08, 1.3% I at 0.542; magenta dye-forming coupler M-1 
at 0.255; masking coupler MC-2 at 0.059; gelatin at 1.58. 
Layer 7 (Mid magenta layer): a green sensitized (as above) silver 
iodobromide emulsion: 1.3.times.0.12, 4.1 mole % iodide at 0.968, M-1 at 
0.054; MC-2 at 0.064; DIR-3 at 0.024; gelatin at 1.26. 
Layer 8 (Fast magenta layer): a green sensitized (as above) tabular silver 
iodobromide (2.3.times.0.13, 4.1 mole % I) emulsion at 0.968; gelatin at 
1.116; Coupler M-1 at 0.043; MC-2 at 0.054; DIR-4 at 0.011 and DIR-5 at 
0.011. 
Layer 9 (Yellow filter layer): AD-1 at 0.108 and gelatin at 1.29. 
Layer 10 (Slow yellow layer): a blend of three tabular silver iodobromide 
emulsions sensitized with sensitizing dye YD-A: (i) 0.5.times.0.08, 1.3 
mole I at 0.193, (ii) 1.0.times.0.25, 6 mole % I at 0.32 and (iii) 
0.81.times.0.087, 4.5 mole % I at 0.193; gelatin at 2.51; yellow 
dye-forming couplers Y-1 at 0.750 and Y-2 at 0.289; DIR-6 at 0.064; C-1 at 
0.027 and B-1 at 0.003. 
Layer 11 (Fast yellow layer): a blend of two blue sensitized (as above) 
silver iodobromide emulsions: (i) a large tabular emulsion, 
3.3.times.0.14, 4.1 mole % at 0.227 and (ii) a 3-D emulsion, 
1.1.times.0.4, 9 mole % I at 0.656; Y-1 at 0.206; Y-2 at 0.080; DIR-6 at 
0.047; C-1 at 0.029; B-1 at 0.005 and gelatin at 1.57. 
Layer 12 (UV filter layer): gelatin at 0.699; silver bromide Lippman 
emulsion at 0.215; UV-1 at 0.108 and UV-2 at 0.108. 
Layer 13 (Protective overcoat): gelatin at 0.882; colloidal silica at 
0.108. 
Hardner (bis(vinylsulfonyl)methane hardener at 1.75% of total gelatin 
weight), antifoggants (including 
4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene), surfactants, coating aids, 
emulsion addenda, sequestrants, lubricants, matte and tinting dyes were 
added to the appropriate layers as is common in the art. 
##STR4## 
Coatings 1-2 through 1-16 were prepared as Coating 1-1 except that the 
high-boiling organic liquids shown in Table I were incorporated as 
dispersions into the Layer 1 at a coated level of 0.484 g/m.sup.2 in each 
coating as summarized in Table II. Coating 1-17 was a repeat of Coating 
1-1, containing no high-boiling liquid. 
Film Adhesive Peel Force Test 
A coated photographic film to be tested was scribed with a sharp blade in a 
straight line approximately 2 cm in length. An adhesive tape (3M 4171 
vinyl tape) was adhered over the scribed line, and the edges of the strip 
were cut off to a width of 1.9 cm. Peeling of the tape was initiated by 
hand and then the tape was peeled off at an angle of 180.degree. at a peel 
rate of 5.1 cm/min. The adhesive strength was determined by measuring the 
minimum force (in grams) needed to peel the emulsion layers off the 
support. 
Film Cutting Test 
A coated photographic film to be tested was placed between two parallel 
blades, one stationary and another traveling at a fixed speed, with a 
constant narrow clearance set between the blades. The film is cut when the 
moving blade passes the stationary blade. The cutting performance was 
evaluated by microscopic examination of the cut edges. 
TABLE II 
______________________________________ 
Appearance of 
Coating # 
Type Dispersion 
Min Peel Force - g 
Cut Edge 
______________________________________ 
1-1 Comp no liquid 
371 no delamination 
1-2 Comp A 336 no delamination 
1-3 Comp B 297 no delamination 
1-4 Inv C 529 no delamination 
1-5 Inv D 594 no delamination 
1-6 Inv E 574 no delamination 
1-7 Comp F 205 delamination 
1-8 Comp G 186 delamination 
1-9 Comp H 161 delamination 
1-10 Comp I 250 delamination 
1-11 Comp J 233 delamination 
1-12 Comp K 396 delamination 
1-13 Inv L 477 no delamination 
1-14 Inv M 463 no delamination 
1-15 Comp N 178 no delamination 
1-16 Comp O 235 not tested 
1-17 Comp no liquid 
324 not tested 
Avg-1 Comp no liquid 
348 -- 
Avg-2 Comp check 248 -- 
liquid 
Avg-3 Inv inv liquid 
527 -- 
______________________________________ 
The results show, on average, an improvement of 50% in peel force by the 
layer containing the inventive organic liquids over the same layer with no 
organic liquid and an improvement of over 100% in peel force versus the 
layer containing the comparative organic liquid. 
The minimum peel force data shown in Table II is plotted in FIG. 1 to 
illustrate the effect of organic liquid log P, coated in the layer 
adjacent to the treated and subbed support, on film dry adhesion. The 
results clearly indicate that liquids with a log P value greater than 7.7 
provide improved dry adhesion compared to lower log P liquids or no 
organic liquid at all. The more hydrophilic liquids (log P values between 
3.0 and 7.7) were found to be detrimental to dry adhesion compared to the 
no organic liquid coatings. The most hydrophilic liquids (log P values 
less than 3.0) produced results similar to those obtained with no added 
organic liquid. This is attributed to diffusion of these liquids out of 
the layer in which they were coated to other layers of the multilayer 
film. 
It is clear from these data that only the films containing the high log P 
(greater than 7.7) liquids in the bottom photographic layer provided good 
dry adhesion and exhibited no peeling or delamination at the cut edges. 
EXAMPLE 2 
Coating 2-1 was prepared like Coating 1-1 of Example 1. Coatings 2-2 
through 2-20 were also prepared similarly, except for the liquid 
dispersion types and levels coated in the layer, as outlined below in 
Table III. 
TABLE III 
______________________________________ 
Coating # 
Type Organic Liquid (Coated Levels in g/m.sup.2) 
______________________________________ 
2-1 Comp no liquid 
2-2 Comp dispersion O (0.484) 
2-3 Inv dispersion M (0.161) + dispersion O (0.323) 
2-4 Inv dispersion M (0.242) + dispersion O (0.242) 
2-5 Inv dispersion M (0.323) + dispersion O (0.161) 
2-6 Inv dispersion M (0.484) 
2-7 Inv dispersion M (0.242) 
2-8 Inv dispersion M (0.430) 
2-9 Inv dispersion M (0.538) 
2-11 Comp dispersion O (0.484) 
2-12 Comp dispersion O (0.323) + dispersion N (0.161) 
2-13 Comp dispersion O (0.242) + dispersion N (0.242) 
2-14 Comp dispersion O (0.161) + dispersion N (0.323) 
2-15 Comp dispersion N (0.484) 
2-16 Comp dispersion N (0.242) 
2-17 Comp dispersion N (0.430) 
2-18 Comp dispersion N (0.538) 
2-19 Comp dispersion N (0.726) 
2-20 Comp no liquid 
______________________________________ 
These coatings were then subjected to the adhesive peel force and edge 
cutting tests described the previous example and the following results 
were obtained. 
TABLE IV 
______________________________________ 
Wt. % High 
Log P 
Liquid Minimum 
Appearance 
Coating # 
Type Gel/Liquid 
Dispersed 
Peel Force 
of Cut Edge 
______________________________________ 
2-1 Comp infinity 0 405 no 
delamination 
2-2 Comp 3.33 0 261 no 
delamination 
2-3 Inv 3.33 33 343 no 
delamination 
2-4 Inv 3.33 50 362 no 
delamination 
2-5 Inv 3.33 67 427 no 
delamination 
2-6 Inv 3.33 100 618 no 
delamination 
2-7 Inv 6.66 100 526 no 
delamination 
2-8 Inv 3.75 100 544 no 
delamination 
2-9 Inv 3.00 100 534 no 
delamination 
2-11 Comp 3.33 0 213 no 
delamination 
2-12 Comp 3.33 0 241 no 
delamination 
2-13 Comp 3.33 0 238 delamination 
2-14 Comp 3.33 0 213 delamination 
2-15 Comp 3.33 0 184 delamination 
2-16 Comp 6.66 0 271 delamination 
2-17 Comp 3.75 0 216 delamination 
2-18 Comp 3.00 0 186 delamination 
2-19 Comp 2.24 0 184 delamination 
2-20 Comp infinity 0 365 no 
delamination 
Avg-1 Comp Var. No Liquid 
385 -- 
Avg-2 Comp Var. Check 221 -- 
Liquid 
Avg-3 Inv Var. Inv Liquid 
479 -- 
______________________________________ 
The results show that, on the average, the adhesion for the layer 
containing the high boiling organic liquid of the invention had a 25% 
improvement over that with no organic liquid and 120% over that with the 
comparison hydrophilic liquid. The results clearly show that dry adhesion 
is improved as the proportion of high log P liquid in the bottom 
photographic layer is increased. Hence, this invention is also useful even 
when other more hydrophilic liquids are present in the same layer. This is 
important since it may be desirable to incorporate other photographically 
useful compounds in this layer which are dispersed in more hydrophilic 
liquids which degrade dry adhesion (e.g., coating 2-2 and coatings 2-11 
through 2-19). A review of the data confirms that it is desirable to 
provide sufficient high Log P liquid to constitute at least 33% of the 
total high boiling liquid in the layer, and more desirable to provide 
sufficient high Log P liquid to constitute 67% of the total high boiling 
liquid in the layer. Inventive coatings 2-3 and 2-4 demonstrate improved 
adhesion over coatings with the check organic liquid (2-2 and 2-11 through 
2-19). These inventive coatings contain 33% high Log P liquid. Inventive 
coatings 2-5 through 2-9 demonstrate improved adhesion over coatings with 
the check organic liquid (2-2 and 2-11 through 2-19) and over a coating 
with no organic liquid (2-1 and 2-20). These inventive coatings contain 67 
wt % of the total liquid. 
Improvements in dry adhesion were also observed with lower levels of high 
log P organic liquid. (coating 2-2 through 2-8 vs. 2-9). Since 
delamination at the cut edge was observed with a high level of total 
organic liquid, it is preferred to practice this invention with a 
gel/organic liquid ratio greater than 3.0.