Photographic polyester support

A photographic polyester support is disclosed which hardly curls when heat-treated at a temperature of from 50.degree. C. to the glass transition temperature thereof in the form of a bulk roll, its thickness pattern satisfying the conditions of (1) Max-Min in the whole widthwise direction (TD R value): 8 .mu.m or less, (2) Max-Min of 5 m length in the lengthwise direction (MD R value): 10 .mu.m or less, (3) the difference in thickness between the adjacent hill and hollow (MD fluctuation): 8 .mu.m or less, and (4) the maximum value of hills above a base line of the average thickness of both ends (TD base line value): 5 .mu.m or less. The surface flatness of the heat-treated support is good. When the support is coated with photographic emulsions, the surface of the coated photographic material is even.

FIELD OF THE INVENTION 
The present invention relates to a photographic polyester support which 
hardly curls and the smoothness of the surface of which is hardly worsened 
when subjected to heat treatment. An emulsion may be coated thereover with 
no unevenness. 
BACKGROUND OF THE INVENTION 
In general, a photographic material is produced by coating at least one 
photographic layer on a plastic film support. As the plastic film for a 
photographic support, a cellulosic polymer such as typically triacetyl 
cellulose (hereinafter referred to as "TAC") and a polyester polymer such 
as typically polyethylene terephthalate (hereinafter referred to as "PET") 
are generally employed. Recently, the use of polyethylene naphthalate 
having higher heat resistance than PET as a photographic support has been 
investigated. 
A photographic material is generally grouped into one of two groups: one 
being in the form of a sheet film such as an X-ray film, a film for 
photomechanical processes and a cut film, and the other being in the form 
of a roll film such as typically a color or black-and-white negative film 
having a width of 35 m/m or less. The latter is generally housed in a 
patrone (cartridge) and is charged in a camera for picture-taking. 
As a support for a roll film, heretofore, TAC has been used essentially. 
The characteristics of TAC film as a photographic support are that TAC has 
no optical anisotropy and has a high transparency and that TAC has an 
excellent property of easily smoothing the curl of a developed 
photographic material having it as a support. The excellent property of 
TAC of easily smoothing the curl of a developed photographic material 
having it as a support results from the molecular structure of the TAC 
film itself. Specifically, since a TAC film has a relatively high 
water-absorbing property, though being a plastic film, because of its 
characteristic molecular structure, the molecular chain of the film comes 
to be fluid after the support film of TAC has absorbed water during 
development of a curled roll film so that the curl of a long-time stored 
roll film may be smoothed by rearrangement of the molecular chain as fixed 
in the long-time stored and curled roll film. 
If a photographic material having a film support not having an uncurling 
property is used as a roll film, it would involve problems of having 
scratches and out-of-focusing during the printing step of forming an image 
on a photographic paper from the developed roll film and also a problem of 
jamming during feeding of the roll film. 
The use of photographic materials has been diversified widely in these 
days, and the technology for rapid feeding of a photographic film in a 
camera or the like during picture-taking with it, elevation of the image 
magnification and reduction of the size of picture-taking devices has 
advanced noticeably. Under the advanced technology, the support of 
photographic materials is needed to have high strength and high dimension 
stability and to be thin as much as possible. 
Since a TAC film has a rigid molecular structure, the film quality of it is 
brittle. Therefore, at present, use of the film involves various difficult 
problems. 
As opposed to a TAC film, a polyester film has excellent producibility, 
mechanical strength and dimension stability. Therefore, it has heretofore 
been considered that such a polyester film would be substitutable for a 
TAC film. 
Since a polyester film strongly curls and the curl of the film remains much 
when it is rolled, handling of a developed photographic material having a 
support of the film is troublesome. Therefore, despite the above-mentioned 
excellent properties, use of the film as a support for a roll film was 
unfavorable. As a means of overcoming the curling property of the film, 
U.S. Pat. No. 4,141,735 has proposed heat treatment of the film for 
reducing the curl of the film. However, if a bulk roll of the film is 
simply heated on an industrial scale, it would be shrunk, spotted or 
wrinkled to cause unevenness of an emulsion layer to be coated thereover. 
Because of this reason, such a heat-treated bulk roll of the film could 
not be put to practical use. 
SUMMARY OF THE INVENTION 
An object of the present invention is to provide a photographic polyester 
support which hardly curls and still has a smooth surface when 
heat-treated. 
This and other objects have been attained by a photographic polyester 
support which has a thickness pattern satisfying the following conditions: 
______________________________________ 
(1) Max-Min in the whole widthwise 
8 .mu.m or less 
direction (TD R value): 
(2) Max-Min of 5 m length in the 
10 .mu.m or less 
lengthwise direction (MD R value): 
(3) Difference in thickness between 
8 .mu.m or less 
the adjacent hill and hollow 
(MD fluctuation): 
(4) Maximum value of hills above 
5 .mu.m or less. 
a base line of being the average 
thickness of the both ends 
(TD base line value): 
______________________________________ 
That is, the present invention is directed to a photographic polyester 
support which has a thickness pattern having a TD R value, an MD R value, 
an MD fluctuation and a TD base line value as follows: 
______________________________________ 
(1) TD R value: 8 .mu.m or less 
(2) MD R value: 10 .mu.m or less 
(3) MD fluctuation: 8 .mu.m or less 
(4) TD base line value: 
5 .mu.m or less. 
______________________________________ 
By satisfying the above conditions, the polyester support hardly curls when 
heat-treated at a temperature of from 50.degree. C. to the glass 
transition temperature thereof in the form of a bulk roll.

DETAILED DESCRIPTION OF THE INVENTION 
A thickness pattern is a set of the following conditions: 
(1) TD R value, (2) MD R value, (3) MD fluctuation, (4) TD base line value, 
in which TD means a transverse direction, MD means a machine direction, 
and R means a range, all of which are defined below for present invention. 
The technical meanings of the conditions (1) to (4) are analyzed in the 
figure. The condition (1) is directed to a so-called TD R value of 8 .mu.m 
or less, preferably 4 .mu.m or less, which is obtained by subtracting the 
minimum height Min from the maximum height Max in the whole widthwise 
direction on the surface of a photographic polyester film support. The 
condition (2) is directed to a so-called MD R value of 10 .mu.m or less, 
preferably 5 .mu.m or less, which is obtained by subtracting the minimum 
height Min from the maximum height Max in the range of a length of 5 m in 
the lengthwise direction on the surface of the same. The condition (3) is 
directed to a so-called MD fluctuation of 8 .mu.m or less, preferably 4 
.mu.m or less, which corresponds to the difference in the thickness 
between the adjacent hill and hollow of the same support irrespective of 
the widthwise direction and the lengthwise direction. The condition (4) is 
directed to a so-called TD base line value of 5 .mu.m or less, preferably 
3 .mu.m or less, which corresponds to the maximum value of hills above a 
base line of the average thickness of both ends of the same support. 
From the conditions (1) to (4), the surface of the photographic support is 
extremely smooth and the thickness thereof is extremely uniform. When 
heat-treated, the support does not curl and the surface thereof is 
extremely smooth. When the heat-treated support is coated with an 
emulsion, it is free from coating unevenness. Thus, the support satisfying 
the conditions (1) to (4) has extremely excellent properties. 
The thickness of a base of the photographic support is varied, depending on 
the ejecting pressure of its melt, the viscosity of its melt, etc. Then, 
the thickness is measured to adjust a lip clearance. The controlling of 
the thickness is conducted by feeding back the obtained data to an 
extruding portion. 
The photographic polyester support of the present invention is made of a 
polymer obtained by polycondensation of a dibasic carboxylic acid or its 
ester derivative and a glycol consisting essentially ethylene glycol. Any 
other polymers and additives may be added thereto, or two or more dibasic 
acids and two or more glycols may be copolymerized, or two or more 
polyesters may be blended, provided that such does not detract from the 
transparency, dimension stability and mechanical strength of the film. 
Polyesters for use in the present invention are composed of a diol and a 
dicarboxylic acid. For instance, such polyesters may be obtained by 
polymerizing a dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid 
(NDCA), terephthalic acid (TPA), isophthalic acid (IPA), orthophthalic 
acid (OPA), cyclohexanedicarboxylic acid (CHDC) or 
paraphenylenedicarboxylic acid (PPDC) and a diol such as ethylene glycol 
(EG), cyclohexane dimethanol (CHDM), neopentyl glycol (NPG), bisphenol A 
(BPA) or biphenol (BP) and optionally also a hydroxycarboxylic acid such 
as parahydroxybenzoic acid (PHBA) or 6-hydroxy-2-naphthalene-carboxylic 
acid (HNCA). 
Of them, preferred are homopolymers or copolymers of 
naphthalene-dicarboxylic acid, terephthalic acid and ethylene glycol (in 
which the molar ratio of naphthalene-dicarboxylic acid to terephthalic 
acid is preferably from 0.3/0.7 to 1.0/0, more preferably from 0.5/0.5 to 
0.8/0.2); homopolymers or copolymers of terephthalic acid, ethylene glycol 
and bisphenol A (in which the molar ratio of ethylene glycol to bisphenol 
A is preferably from 0.6/0.4 to 0/1.0, more preferably 0.5/0.5 to 
0.1/0.9); homopolymers or copolymers of isophthalic acid, 
paraphenylene-dicarboxylic acid, terephthalic acid and ethylene glycol (in 
which the molar ratio of isophthalic acid to terephthalic acid and that of 
paraphenylene-dicarboxylic acid to the same are preferably from 0.1/1 to 
10.0/1 and from 0.1/1 to 20/1, respectively, more preferably from 0.2/1 to 
5.0/1 and from 0.2/1 to 10.0/1, respectively); homopolymers or copolymers 
of naphthalene-dicarboxylic acid, neopentyl glycol and ethylene glycol (in 
which the molar ratio of neopentyl glycol to ethylene glycol is preferably 
from 1/0 to 0.7/0.3, more preferably from 0.9/0.1 to 0.6/0.4); 
homopolymers or copolymers of terephthalic acid, ethylene glycol and 
biphenol (in which the molar ratio of ethylene glycol to biphenol is 
preferably from 0/1.0 to 0.8/0.2, more preferably from 0.1/0.9 to 
0.7/0.3); and homopolymers or copolymers of parahydroxybenzoic acid, 
ethylene glycol and terephthalic acid (in which the molar ratio of 
parahydroxybenzoic acid to ethylene glycol is preferably from 1/0 to 
0.1/0.9, more preferably from 0.9/0.1 to 0.2/0.8). Also suitable are 
polymer blends of, for example, PEN and PET (in which the ratio of the two 
is preferably from 0.3/0.7 to 1.0/0, more preferably from 0.5/0.5 to 
0.8/0.2); and PET and PAr (in which the ratio of the two is preferably 
from 0.6/0.4 to 0/1.0, more preferably from 0.5/0.5 to 0.1/0.9). 
Other dibasic acids of polyester components include phthalic anhydride, 
succinic acid, glutaric acid, adipic acid, sebacic acid, succinic 
anhydride, maleic acid, fumaric acid, maleic anhydride, itaconic acid, 
citraconic anhydride, tetrahydrophthalic anhydride, 
diphenylene-p,p'-dicarboxylic acid, tetrachlorophthalic anhydride, 
3,6-endomethylene-tetrahydrophthalic anhydride, 
1,4-cyclohexanedicarboxylic acid, and the following dibasic acids: 
##STR1## 
Other diols include 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 
1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 
1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 
1,3-cyclohexanediol, 1,1-cyclohexane-dimethanol, catechol, resorcinol, 
hydroquinone, 1,4-benzene-dimethanol and the following diols: 
##STR2## 
If desired, copolyesters containing additional comonomers of 
mono-functional or tri- or more polyfunctional hydroxyl group-containing 
compounds or acid-containing compounds may also be used in the present 
invention. 
Also suitable in the present invention are copolyesters containing 
additional comonomers of compounds having both hydroxyl group(s) and 
carboxyl (or its ester) group(s) in the molecule. 
Examples of such comonomers include the following compounds: 
##STR3## 
Preferred examples of polyesters for use in the present invention are 
mentioned below: 
______________________________________ 
Homopolymers: 
PEN: [2,6-naphthalene-dicarboxylic acid 
Tg = 119.degree. C. 
(NDCA)/ethylene glycol (EG) 
(100/100)] 
PCT: [terephthalic acid (TPA)/cyclohexane 
Tg = 93.degree. C. 
dimethanol (CHDM) (100/100)] 
PAr: [TPA/bisphenol A (BPA) (100/100)] 
Tg = 192.degree. C. 
Copolymers (the parenthesized ratio is by mol): 
PBC-1: 2,6-NDCA/TPA/EG (50/50/100) 
Tg = 92.degree. C. 
PBC-2: 2,6-NDCA/TPA/EG (75/25/100) 
Tg = 102.degree. C. 
PBC-3: 2,6-NDCA/TPA/EG/BPA Tg = 112.degree. C. 
(50/50/75/25) 
PBC-4: TPA/EG/BPA (100/50/50) Tg = 105.degree. C. 
PBC-5: TPA/EG/BPA (100/25/75) Tg = 135.degree. C. 
PBC-6: TPA/EG/CHDM/BPA (100/25/25/50) 
Tg = 115.degree. C. 
PBC-7: IPA/PPDC/TPA/EG (20/50/30/100) 
Tg = 95.degree. C. 
PBC-8: NDCA/NPG/EG (100/70/30) 
Tg = 105.degree. C. 
PBC-9: TPA/EG/BP (100/20/80) Tg = 115.degree. C. 
PBC-10: 
PHBA/EG/TPA (200/100/100) 
Tg = 125.degree. C. 
Polymer Blends (the parenthesized ratio is by weight): 
PBB-1: PEN/PET (60/40) Tg = 95.degree. C. 
PBB-2: PEN/PET (80/20) Tg = 104.degree. C. 
PBB-3: PAr/PEN (50/50) Tg = 142.degree. C. 
PBB-4: PAr/PCT (50/50) Tg = 118.degree. C. 
PBB-5: PAr/PET (60/40) Tg = 101.degree. C. 
PBB-6: PEN/PET/PAr (50/25/25) Tg = 108.degree. C. 
______________________________________ 
Of the above-mentioned polyesters, PEN (polyethylene 2,6-dinaphthalate) has 
the most-balanced properties. Specifically, it has a high mechanical 
strength, especially a high modulus of elasticity, and has a sufficiently 
high glass transition temperature of about 120.degree. C. However, this 
polyester has a drawback of being fluorescent. On the other hand, PCT has 
a high mechanical strength and a high glass transition temperature of 
about 110.degree. C. However, this polyester has a drawback of being 
hardly transparent since its crystallization speed is extremely high. PAr 
has the highest glass transition temperature (190.degree. C.) among them, 
but it has a drawback of having a lower mechanical strength than PET. 
Therefore, in order to compensate for the drawbacks, blends of these 
polymers or copolymers of them may be employed. 
These homopolymers and copolymers may be produced by conventional known 
methods of producing ordinary polyesters. For instance, an acid component 
and a glycol component are directly esterified; or if a dialkyl ester is 
used as an acid component, it is first interesterified with a glycol 
component, and the resulting product is then heated under reduced pressure 
to remove the excess glycol component. Alternatively, an acid halide is 
used as an acid component and may be reacted with a glycol component. In 
the case of inter-esterification, the addition of a catalyst or 
polymerization catalyst or the addition of a heat-resistant stabilizer may 
be employed, if desired. Regarding the polyester producing methods, for 
example, one can refer to the descriptions of Studies of Polymer 
Experiments, Vol. 5, "Polycondensation and Addition Polymerization" 
(published by Kyoritsu Publishing Co., 1980), pp. 103-136; and Synthetic 
Polymers V (published by Asakura Shoten KK, 1971), pp. 187-286. 
In addition, one can also refer to the descriptions of JP-B-48-40414, and 
JP-A-50-81325, JP-A-50-109715, JP-A-1-287129, JP-A-1-266130, 
JP-A-1-266133, JP-A-55-115425, JP-A-1-244446 and JP-A-4-93937 (the term 
"JP-B" as used herein means an "examined Japanese patent publication", and 
the term "JP-A" as used herein means an "unexamined published Japanese 
patent application"). 
The polyesters for use in the present invention preferably have a mean 
molecular weight of approximately from 10,000 to 500,000. 
Polymer blends of such polymers may easily be formed in accordance with the 
methods described in JP-A-49-5482, JP-A-64-4325, and JP-A-3-192718, and 
Research Disclosure 283739-41, 284779-82 and 294807-14. 
The polyesters may be blended with a part of other polyesters or may be 
copolymerized with comonomers constituting other polyesters or may be 
copolymerized with unsaturated bond-containing monomers for their radical 
crosslinking, in order to improve the adhesiveness of them to other 
polyesters. 
The photographic polyester support of the present invention is preferably 
PET, polyethylene naphthalate, polycyclohexane-dimethanol terephthalate, 
polyacrylate, and their blends. Of them, especially preferred is 
polyethylene naphthalate (or polyethylene 2,6-dinaphthalate). The 
polyester film of the present invention may contain various additives. 
Furthermore, it is preferred to use a polyester support which is made of a 
polyester obtained by reacting 2,6-naphthalene-dicarboxylic acid or 
dimethyl 2,6-naphthalene-dicarboxylate and a glycol consisting essentially 
of ethylene glycol. 
Use of the polyester film as a support of a photographic material involves 
one problem about its properties, which is that the support causes 
light-piping due to its high refractive index. 
Polyesters have a high refractive index of from 1.6 to 1.7, while gelatin, 
which is the essential component of a subbing layer and a photographic 
emulsion layer to be coated over the polyester base film, has a refractive 
index of from 1.50 to 1.55. Thus, the ratio of the refractive index of 
gelatin to that of polyesters is lower than 1, and therefore, where light 
has been introduced into the film from its edge, it easily reflects on the 
interface between the base and the emulsion layer. Because of this reason, 
a polyester film causes a so-called light-piping phenomenon. 
For avoiding such a light-piping phenomenon in the present invention, dyes 
which do not increase the film haze may be added to the film. The dyes to 
be used for coloring the film for this purpose are not specifically 
defined. Preferred are gray coloring dyes in view of the general 
properties of photographic materials. Also preferred are dyes having high 
heat resistance in the temperature range for forming the polyester film 
and having excellent compatibility with polyesters. In view of the 
above-mentioned points, specifically mentioned are commercial dyes such as 
Mitsubishi Kasei's Diaresin or Nippon Chemical's Kayaset. The coloring 
density due to the addition of such dyes is needed to be at least 0.01 or 
more, more preferably 0.03 or more, as a visible color density measured 
with a Macbeth's color densitometer. 
The polymer film of the present invention may contain an ultraviolet 
absorbent for the purpose of antifluorescence and stabilization in 
storage, by kneading the absorbent into the film. As the ultraviolet 
absorbent, preferred are those not absorbing visible rays. The amount of 
the absorbent to be in the polymer film is generally approximately from 
0.01% by weight to 20% by weight, preferably approximately from 0.05% by 
weight to 1.0% by weight. Preferred examples of the ultraviolet absorbent 
are benzophenone compounds such as 2,4-dihydroxybenzophenone, 
2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 
4-dodecyloxy-2-hydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 
and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone; benzotriazole compounds 
such as 2-(2'-hydroxy-5-methylphenyl)benzotriazole, 
2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, and 
2-(2'-hydroxy-3'-di-t-butyl-5'-methylphenyl)benzotriazole; and salicylic 
acid compounds such as phenyl salicylate and methyl salicylate. 
The ultraviolet absorbent may also be added to the subbing layer, backing 
layer, emulsion layer or antihalation layer constituting the photographic 
material having the polyester support of the present invention. 
The polyester film of the present invention may be treated to be 
lubricative. The means for making the film lubricative is not specifically 
defined. For instance, generally employable is a method of kneading an 
inactive inorganic compound into the film or a method of coating a 
surfactant over the film. Also employable is a method of precipitating 
internal grains where grains of catalysts or the like as added during 
polymerization of polyesters are precipitated out. 
Inactive inorganic grains usable for this purpose are, for example, 
SiO.sub.2, TiO.sub.2, BaSO.sub.4, CaCO.sub.3, talc, kaolin and the like. 
No specific means of making the polyester film lubricative is required. 
However, since it is important that the support of a photographic material 
be transparent, the grains to be added to the polyester by the former 
method are desired to be selectively SiO.sub.2 grains which have a 
refractive index relatively near to that of the polyester film, and the 
internal grains to be precipitated in the polyester film by the latter 
method are desired to be selectively those having a relatively small grain 
size. 
Where the polyester film is made lubricative by the grains-kneading means, 
a method of laminating a functional layer over the film is also preferably 
employable so as to elevate the transparency of the film significantly. 
Examples of the method are co-extrusion with plural extruders and feed 
blocks and also co-extrusion with multi-manifold dies. 
For forming a polyester into a polyester film, either a finished polyester 
may be formed into a film while it is a melt or it may be pelletized and 
the resulting polyester pellets may be formed into a film. In the latter 
case, the pellets are desired to be dried prior to being extruded to a 
film. 
For forming the film, melt extrusion or biaxial stretching is preferred. 
For instance, a polyester is melt-extruded onto a rotary cooling device at 
a temperature of from the melting point of the polymer to 350.degree. C. 
to form an amorphous non-crystalline sheet, the sheet is roll-stretched 
from 3.0 to 3.5 times in the lengthwise direction at 70.degree. to 
160.degree. C., preferably at 80.degree. to 130.degree. C. and then 
tenter-stretched from 2.8 to 4.2 times in the crosswise direction at a 
temperature higher than the temperature for the lengthwise stretching and 
at 70.degree. to 150.degree. C., preferably from 80.degree. to 130.degree. 
C., then it is heat-fixed at a temperature higher than the temperature for 
the crosswise stretching and lower than 260.degree. C., preferably from 
150.degree. to 250.degree. C., then it is subjected to heat-relaxation of 
from 0.1 to 10%, preferably from 0.5 to 5%, and then it is cooled and 
reeled up. For the stretching, simultaneous biaxial stretching using 
tenter clips is also preferred. If desired, the crosswise stretched film 
may be again lengthwise stretched. 
The thickness of the polyester film of the present invention is desired to 
be from 60 to 90 .mu.m. Measurement of the glass transition temperature 
and the thickness pattern of the film of the present invention is effected 
by the methods mentioned below. 
Measurement of Glass Transition Temperature Tg 
Using a differential scanning colorimeter (DSC), 10 mg of a sample film is 
heated in a nitrogen stream at a rate of 20.degree. C./min, and a 
mathematical average temperature of the temperature at which the heated 
film begins to be shifted from its base line and the temperature at which 
it comes back to a new base line is obtained. 
Measurement of Thickness Pattern 
Using an electronic micrometer manufactured by Anritsu Electric Co., the 
thickness of a sample film is measured at a line speed of 600 mm/min, and 
the measured data is recorded on a chart sheet with a scale of 1/20 at a 
chart speed of 30 mm/min. The recorded data are measured with a ruler and 
rounded off to integers. 
The photographic polyester film of the present invention may be knurled. 
The knurling may be effected by a known method such as that described in 
JP-B-57-36129. It is preferred that the knurled thickness is thicker than 
the mean thickness of the bulk roll by 5 to 50 .mu.m. 
The polyester film of the present invention may previously be subjected to 
various surface treatments such as corona-discharging treatment, chemical 
treatment or flame treatment so as to improve the adhesiveness and the 
wettable characteristic with coating liquids. Of such surface treatments, 
most preferred for the film of the present invention is corona-discharging 
treatment by which precipitation of lower polymers onto the surface of the 
treated film is little. 
The polyester support of the present invention preferably has a subbing 
layer in order to increase its adhesiveness with the photographic layers 
such as light-sensitive layers to be coated thereover. 
For instance, a subbing layer of a polymer latex such as a 
styrene-butadienne copolymer or vinylidene chloride copolymer and a 
subbing layer of a hydrophilic binder such as gelatin can be used. 
Of the two, a subbing layer of a hydrophilic binder is preferred for the 
present invention. 
Hydrophilic binders suitable for the present invention include 
water-soluble polymers, cellulose esters, latex polymers and water-soluble 
polyesters. The water-soluble polymers include gelatin, gelatin 
derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, 
polyacrylic acid copolymers and maleic anhydride copolymers, and the 
cellulose esters include carboxymethyl cellulose and hydroxyethyl 
cellulose. The latex polymers include vinyl chloride-containing 
copolymers, vinylidene chloride-containing copolymers, acrylate-containing 
copolymers, vinyl acetate-containing copolymers and butadiene-containing 
copolymers. Of them, most preferred is gelatin. 
Compounds for swelling the support of the present invention include 
resorcinol, chlororesorcinol, methyl resorcinol, o-cresol, m-cresol, 
p-cresol, phenol, o-chlorophenol, p-chlorophenol, dichlorophenol, 
trichlorophenol, monochloroacetic acid, dichloroacetic acid, 
trifluoroacetic acid and chloral hydrate. Of them, preferred are 
resorcinol and p-chlorophenol. 
The subbing layer of the present invention may contain various gelatin 
hardening agents. Suitable gelatin hardening agents are, for example, 
chromium salts (chromium alum, etc.), aldehydes (formaldehyde, 
glutaraldehyde, etc.), isocyanates, active halogen compounds 
(2,4-dichloro-6-hydroxy-s-triazine, etc.), epichlorohydrin resins and 
others. 
The subbing layer of the present invention may contain fine inorganic 
grains such as SiO.sub.2, TiO.sub.2 or mat agents or fine grains(having a 
grain size of from 1 to 10 .mu.m) of polymethyl methacrylate copolymers. 
The subbing layer may be coated on the support by any well-known method, 
for example, by a dip-coating, air knife-coating, curtain-coating, wire 
bar-coating, gravure-coating or an extrusion coating method. 
The photographic material of the present invention may have various 
non-light-sensitive layers such as an anti-halation layer, interlayer, 
backing layer and surface protective layer, in addition to light-sensitive 
layers. 
The binder of the backing layer may be made of a hydrophobic polymer or may 
also be made of a hydrophilic polymer such as that in the subbing layer. 
The backing layer of the photographic material of the present invention may 
contain an antistatic agent, a lubricant, a mat agent, a surfactant, a dye 
and other additives. The antistatic agent in the backing layer is not 
specifically defined. For instance, it includes anionic polyelectrolytes 
of polymers containing carboxylic acids, carboxylic acid salts or sulfonic 
acid salts, such as those described in JP-A-48-22017, JP-B-46-24159, 
JP-A-51-30725, JP-A-51-129216 and JP-A-55-95942; and cationic polymers 
such as those described in JP-A-49-121523, JP-A-48-91165 and 
JP-B-49-24582. The ionic surfactant in the layer may be either an anionic 
one or cationic one. For instance, usable compounds as described in 
JP-A-49-85826, JP-A-49-33630, U.S. Pat. Nos. 2,992,108, 3,206,312, 
JP-A-48-87826, JP-B-49-11567, JP-B-49-11568 and JP-A-55-70837. 
The most preferred antistatic agent to be in the backing layer of the 
present invention is fine grains of at least one crystalline metal oxide 
selected from ZnO, TiO.sub.2, SnO.sub.2, Al.sub.2 O.sub.3, In.sub.2 
O.sub.3, SiO.sub.2, MgO, BaO and MoO.sub.2 or a metal composite of them. 
The fine grains of the conductive crystalline oxide or composite oxide 
usable in the present invention have a volume resistivity of 10.sup.7 
.OMEGA.cm or less, more preferably 10.sup.5 .OMEGA.cm or less. The grain 
size of them is desirably from 0.01 to 0.7 .mu.m, especially preferably 
from 0.02 to 0.5 .mu.m. 
Methods of preparing fine particles of conductive crystalline metal oxides 
or composite oxides to be used in the present invention are described in 
JP-A-56-143430 and JP-A-60-258541. The first method is such that fine 
particles of metal oxides are formed by firing and then heat-treated in 
the presence of hetero atoms so as to improve their conductivity. The 
second method is such that fine particles of metal oxides are formed by 
firing in the presence of hetero atoms for improving their conductivity. 
The third method is such that fine particles of metal oxides are formed by 
firing in an atmosphere having a lowered oxygen concentration so as to 
introduce oxygen defects into them. For the introduction of hetero atoms, 
Al, In or the like to ZnO; Nb, Ta or the like to TiO.sub.2 ; and Sb, Nb, a 
halogen element or the like to SnO.sub.2 can be used. The amount of the 
hetero atoms to be added is preferably from 0.01 to 30 mol %, more 
preferably from 0.1 to 10 mol %. 
The photographic layers constituting the photographic material of the 
present invention will now be mentioned. The photographic material of the 
present invention is most preferably a silver halide photographic material 
such as silver halide color negative film, color positive film, color 
reversal film and black-and-white negative film. 
The photographic emulsions to be used in the present invention may be 
prepared by known methods such as those described in P. Glafkides, Chemie 
et Physique Photographique (published by Paul Montel, 1967); G. F. Duffin, 
Photographic Emulsion Chemistry (published by The Focal Press, 1966); and 
V. L. Zelikmann et al., Making and Coating Photographic Emulsion 
(published by The Focal Press, 1964). For instance, they may be prepared 
by any of an acid method, a neutral method and an ammonia method. As a 
system of reacting a soluble silver salt and soluble halide(s) for forming 
the emulsions, any of a single jet method, a double jet method and a 
combination of them may be employed. 
Also employable is a so-called reversed mixing method where silver halide 
grains are formed in the presence of excess silver ions. As one system of 
a double jet method, a so-called controlled double jet method can be used 
where the pAg value in the liquid phase of forming silver halide grains is 
kept constant. 
According to this method, an emulsion of silver halide grains having a 
regular crystalline morphology and having an almost uniform grain size 
distribution may be obtained. 
Two or more silver halide emulsions separately prepared may be blended to 
form a blend emulsion for use in the present invention. 
In the step of forming silver halide grains or of ripening the grains, a 
cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt 
or its complex, a rhodium salt or its complex, and/or an iron salt or its 
complex may be added to the reaction system. 
As a binder or protective colloid for the photographic emulsions for use in 
the present invention, gelatin is advantageously used, but any other 
hydrophilic colloids may also be used. 
For instance, various synthetic hydrophilic polymer substances are usable, 
including proteins such as gelatin derivatives, graft polymers of gelatin 
and other high polymers, albumin and casein; cellulose derivatives such as 
hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates; 
saccharide derivatives such as sodium alginate and starch derivatives; and 
homopolymers or copolymers such as polyvinyl alcohol, polyvinyl alcohol 
partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic 
acid, polyacrylamide, polyvinylimidazole and polyvinyl pyrazole. 
As gelatin, a lime-processed gelatin and an acid-processed gelatin and also 
an enyzme-processed gelatin such as that described in Bull. Soc. Sci. 
Phot. Japan, No. 16, page 30 (1966) can be used. In addition, hydrolysates 
of gelatin and enzyme-decomposed products thereof are also usable. Gelatin 
derivatives include reaction products obtained by reacting gelatin and 
various compounds such as acid halides, acid anhydrides, isocyanates, 
bromoacetic acid, alkanesultones, vinylsulfonamides, maleinimide 
compounds, polyalkylene oxides and epoxy compounds. Examples of the 
derivatives are described in, for example, U.S. Pat. Nos. 2,614,928, 
3,132,945, 3,186,846, 3,312,553, British Patents 861,414, 1,033,189, 
1,005,784, and JP-B-42-26845. 
Gelatin graft polymers include reaction products obtained by grafting 
gelatin with various homopolymers or copolymers of vinyl monomers such as 
acrylic acid, methacrylic acid, their derivatives such as their esters and 
amides, acrylonitrile and styrene. Of them, especially preferred are graft 
polymers of gelatin with polymers which are miscible with gelatin in some 
degree, such as copolymers of acrylic acid, methacrylic acid, acrylamide, 
methacrylamide and/or hydroxyalkyl methacrylates. Examples of them are 
described in, for example, U.S. Pat. Nos. 2,763,625, 2,831,767 and 
2,956,884. 
Typical synthetic hydrophilic polymer substances usable in the present 
invention are described in German Patent OLS 2,312,798, U.S. Pat. Nos. 
3,620,751 and 3,879,205 and JP-B-43-7561. 
The photographic emulsions for use in the present invention may contain 
various compounds for the purpose of preventing them from fogging and for 
the purpose of stabilizing their photographic properties during the steps 
of preparing, storing and processing photographic materials. For instance, 
they may contain various compounds known as an anti-foggant or stabilizer, 
for example, azoles such as benzothiazolium salts, nitroindazoles, 
nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, 
mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, 
mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles 
and mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); 
mercaptopyrimidines; mercaptotriazines; thioketo compounds such as 
oxazolinethione; azaindenes such as triazaindenes, tetrazaindenes 
(especially 4-hydroxy-substituted (1,3,3a,7)-tetrazaindenes) and 
pentazaindenes; and benzenethiosulfonic acids, benzenesulfinic acids, and 
benzenesulfonic acid amides. For instance, those compounds disclosed in 
U.S. Pat. No. 3,954,474, U.S. Pat. No. 3,982,947 and JP-B-52-28660 may be 
used. 
The photographic emulsions for use in the present invention may contain, 
for example, polyalkylene oxides or their derivatives such as ethers, 
esters, amines, thioether compounds, thiomorpholines, quaternary ammonium 
salt compounds, urethane derivatives, imidazole derivatives, 
3-pyrazolidones, etc. Specifically, the compounds described in U.S. Pat. 
Nos. 2,400,532, 2,423,549, 2,716,062, 3,617,280, 3,772,021 and 3,808,003 
and British Patent 1,488,991 may be used for this purpose. 
The photographic emulsion of the present invention may be color-sensitized 
with methine dyes and others. Usable for the color sensitization are 
cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine 
dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and 
hemioxonole dyes. Of them, especially usable are cyanine dyes, merocyanine 
dyes and complex merocyanine dyes. These dyes may have any nuclei which 
are generally in cyanine dyes as basic heterocyclic nuclei. 
Such nuclei include, for example, pyrroline nuclei, oxazoline nuclei, 
thiazoline nuclei, pyrrole nuclei, oxazole nuclei, thiazole nuclei, 
selenazole nuclei, imidazole nuclei, tetrazole nuclei and pyridine nuclei; 
nuclei with alicyclic hydrocarbon rings fused to these nuclei; and nuclei 
with aromatic hydrocarbon nuclei fused to these nuclei, such as indolenine 
nuclei, benzindolenine nuclei, indole nuclei, benzoxazole nuclei, 
naphthoxazole nuclei, benzothiazole nuclei, naphthothiazole nuclei, 
benzoselenazole nuclei, benzimidazole nuclei and quinoline nuclei. These 
nuclei may have substituents on the carbon atoms. 
Merocyanine dyes or complex merocyanine dyes for use in the present 
invention may have 5-membered or 6-membered heterocyclic nuclei such as 
pyrazolin-5-one nuclei, thiohydantoin nuclei, 2-thioxazolidine-2,4-dione 
nuclei, thiazolidine-2,4-dione nuclei, rhodanine nuclei and thiobarbituric 
acid nuclei, as ketomethylene nuclei. 
Examples of sensitizing dyes usable in the present invention are described 
in, for example, German Patent 929,080, U.S. Pat. Nos. 2,231,658, 
2,493,748, 2,503,776, 2,519,001, 2,912,329, 3,656,959, 3,672,897, 
3,694,217, 4,025,349, 4,046,572, British Patent 1,242,588, and 
JP-B-44-14030 and JP-B-52-24844. 
These sensitizing dyes may be used either singly or in combination thereof. 
A combination of sensitizing dyes is often employed for the purpose of 
super-color sensitization. Specific examples of such combinations are 
described in U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 
3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 
3,703,377, 3,769,301, 3,814,609, 3,837,862, 4,026,707, British Patents 
1,344,281, 1,507,803, JP-B-43-4936, JP-B-53-12375, JP-A-52-110618 and 
JP-A-52-109925. 
The photographic emulsions of the present invention may contain dyes which 
themselves have no color-sensitizing activity or substances which do not 
substantially absorb visible rays but have supercolor-sensitizing activity 
in combination with sensitizing dyes. For instance, they may contain 
aminostilbene compounds substituted by nitrogen-containing heterocyclic 
group(s) (such as those described in U.S. Pat. No. 3,635,721), aromatic 
organic acid-formaldehyde condensate compounds (such as those described in 
U.S. Pat. No. 3,743,510), cadmium salts and azaindene compounds. In 
particular, combinations described in U.S. Pat. Nos. 3,615,613, 3,615,641, 
3,617,295 and 3,635,721 are especially useful. 
The photographic material of the present invention may contain 
water-soluble dyes in the hydrophilic colloid layers as filter dyes or for 
anti-irradiation or for other various purposes. Such dyes include, for 
example, oxonole dyes, hemioxonole dyes, styryl dyes, merocyanine dyes, 
cyanine dyes and azo dyes. Of them, oxonole dyes, hemioxonole dyes and 
merocyanine dyes are useful. Specific examples of usable dyes are 
described in U.S. Pat. No. 1,177,429, JP-A-48-85130, JP-A-49-99620, 
JP-A-49-114420, JP-A-52-108115, U.S. Pat. Nos. 2,274,782, 2,533,472, 
2,956,879, 3,148,187, 3,177,078, 3,247,127, 3,540,887, 3,575,704, 
3,653,905, 3,718,472, 4,071,312 and 4,070,362. 
The photographic material of the present invention may contain a 
brightening agent of stilbene compounds, triazine compounds, oxazole 
compounds or coumarin compounds in the photographic emulsion layers or in 
any other hydrophilic colloid layers. The brightening agent may be either 
soluble or insoluble in water. In the latter case, the agent is in the 
layers as a dispersion thereof. Specific examples of usable brightening 
agents are described in, for example, U.S. Pat. Nos. 2,632,701, 3,269,840, 
3,359,102, and British Patents 852,075 and 1,319,763. 
The photographic material of the present invention may contain known 
anti-fading agents or color stabilizers, such as those mentioned below, 
singly or as a mixture of two or more thereof. Known anti-fading agents 
include hydroquinone derivatives described in U.S. Pat. Nos. 2,360,290, 
2,418,613, 2,675,314, 2,701,197, 2,704,713, 2,728,659, 2,732,300, 
2,735,765, 2,710,801, 2,816,028, and British Patent 1,363,921; gallic acid 
derivatives described in U.S. Pat. Nos. 3,457,079 and 3,069,262; 
p-alkoxyphenols described in U.S. Pat. Nos. 2,735,766, 3,698,909, 
JP-B-49-20977, and JP-B-52-6623; p-hydroxyphenol derivatives described in 
U.S. Pat. Nos. 3,432,300, 3,573,050, 3,574,629, 3,764,337, JP-A-52-35633, 
JP-A-52-147434, and JP-A-52-152225; and bisphenols described in U.S. Pat. 
No. 3,700,455. 
The photographic material of the present invention may contain hydroquinone 
derivatives, aminophenol derivatives, gallic acid derivatives and ascorbic 
acid derivatives as a color-fogging inhibitor. Specific examples of them 
are described in U.S. Pat. Nos. 2,360,290, 2,336,327, 2,403,721, 
2,418,613, 2,675,314, 2,701,197, 2,704,713, 2,728,659, 2,732,300, 
2,735,766, JP-A-50-92988, JP-A-50-92989, JP-A-50-93928, JP-A-50-110337, 
JP-A-52-145235 and JP-B-50-23813. 
The present invention may be applied to a multi-layer multi-color 
photographic material having at least two layers each having a different 
color sensitivity on the support. A multi-layer natural-color photographic 
material generally has at least one red-sensitive emulsion layer, at least 
one green-sensitive emulsion layer and at least one blue-sensitive 
emulsion layer on the support. The order of these layers may be selected 
freely in accordance with necessity. In general, the red-sensitive 
emulsion layer contains cyan-forming couplers, the green-sensitive 
emulsion layer contains magenta-forming couplers, and the blue-sensitive 
emulsion layer contains yellow-forming couplers. As the case may be, any 
other different combination may be employed. 
The most preferred photographic material of the present invention is a 
picture-taking color negative film roll. 
The color negative film of the present invention may contain any known 
color couplers. 
For instance, it may contain compounds (hereinafter referred to as 
couplers) capable of reacting with an oxidation product of an aromatic 
amine (generally, primary amine) developing agent to form a dye. The 
couplers are desired to be non-diffusive ones containing hydrophobic 
group(s) in the molecule. The hydrophobic group is called a ballast group. 
The couplers may be either 4-equivalent ones or 2-equivalent ones to 
silver ions. It may also contain colored couplers having an effect for 
color compensation or couplers of releasing a development inhibitor during 
development (so-called DIR couplers). The couplers may also be those 
capable of forming a colorless product by a coupling reaction. 
Suitable yellow-coloring couplers include known ketomethylene couplers. In 
particular, benzoylacetanilide compounds and pivaloylacetanilide compounds 
are advantageous. Specific examples of usable yellow-coloring couplers are 
described in, for example, U.S. Pat. Nos. 2,875,057, 3,265,506, 3,408,194, 
3,551,155, 3,582,322, 3,725,072, 3,891,445, German Patent 1,547,868, 
German Patent OLS Nos. 2,219,917, 2,261,361, 2,414,006, British Patent 
1,425,020, JP-B-51-10783, JP-A-47-26133, JP-A-48-73147, JP-A-51-102636, 
JP-A-50-6341, JP-A-50-123342, JP-A- 50-130442, JP-A-51-21827, 
JP-A-50-87650, JP-A-52-82424 and JP-A-52-115219. 
Suitable magenta couplers include pyrazolone compounds, indazole compounds 
and cyanoacetyl compounds. In particular, pyrazolone compounds are 
advantageous. Specific examples of magenta-coloring couplers are described 
in, for example, U.S. Pat. Nos. 2,600,788, 2,983,608, 3,062,653, 
3,127,269, 3,311,476, 3,419,391, 3,519,429, 3,558,319, 3,582,322, 
3,615,506, 3,834,908, 3,891,445, German Patent 1,810,464, German Patent 
OLS Nos. 2,408,665, 2,417,945, 2,418,959, 2,424,467, JP-B-40-6031, 
JP-A-51-20826, JP-A-52-58922, JP-A-49-129538, JP-A-49-74027, 
JP-A-50-159336, JP-A-52-42121, JP-A-49-74028, JP-A-50-60233, JP-A-51-26541 
and JP-A-53-55122. 
Suitable cyan-coloring couplers include phenol compounds and naphthol 
compounds. Specific examples of them are described in, for example, U.S. 
Pat. Nos. 2,369,929, 2,434,272, 2,474,293, 2,521,908, 2,895,826, 
3,034,892, 3,311,476, 3,458,315, 3,476,663, 3,583,971, 3,591,383, 
3,767,411, 4,004,929, German Patent OLS Nos. 2,414,830, 2,454,329, 
JP-A-48-59838, JP-A-51-26034, JP-A-48-5055, JP-A-51-146828, JP-A-52-69624 
and JP-A-52-90932. 
Suitable colored couplers include those described in, for example, U.S. 
Pat. Nos. 3,476,560, 2,521,908, 3,034,892, JP-B-44-2016, JP-B-38-22335, 
JP-B-42-11304, JP-B- 44-32461, JP-A-51-26034, JP-A-52-42121, and German 
Patent OLS No. 2,418,959. 
Suitable DIR couplers include those described in, for example, U.S. Pat. 
Nos. 3,227,554, 3,617,291, 3,701,783, 3,790,384, 3,632,345, German Patent 
OLS Nos. 2,414,006, 2,454,301, 2,454,329, British Patent 953,454, 
JP-A-52-69624, JP-A-49-122335, and JP-B-51-16141. 
The photographic material of the present invention may contain compounds 
capable of releasing a development inhibitor by development, in addition 
to DIR compounds. For instance, those described in U.S. Pat. Nos. 
3,297,445, 3,379,529, German Patent OLS No. 241,794, JP-A-52-15271 and 
JP-A-53-9116 can be used. 
Two or more different couplers may be in the same layer of the photographic 
material of the present invention. If desired, the same compound may be in 
two or more layers of the material. 
In general, the couplers may be added to the emulsion layer in an amount of 
from 2.times.10.sup.-3 to 5.times.10.sup.-1 mol, preferably from 
1.times.10.sup.-2 to 5.times.10.sup.-1 mol, per mol of silver in the 
layer. 
For introducing the above-mentioned couplers into the silver halide 
emulsion layers constituting the photographic material of the present 
invention, known methods such as the method described in U.S. Pat. No. 
2,322,027 may be employed. For instance, they are dissolved in alkyl 
phthalates (e.g., dibutyl phthalates dioctyl phthalate), phosphates 
(diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, 
dioctylbutyl phosphate), citrates (e.g., tributyl acetylcitrate), 
benzoates (e.g., octyl benzoate), alkylamides (e.g., diethyllaurylamide) 
or fatty acid esters (e.g., dibutoxyethyl succinate, dioctyl azelate), or 
in an organic solvent having a boiling point of approximately from 
30.degree. C. to 150.degree. C., for example, lower alkyl acetates such as 
ethyl nitrate or butyl acetate, or ethyl propionate, secondary butyl 
alcohol, methyl isobutyl ketone, .beta.-ethoxyethyl acetate or methyl 
cellosolve acetate; and then the resulting solutions are dispersed in 
hydrophilic colloids. The above-mentioned high boiling point organic 
solvents and low boiling point organic solvents may be mixed to form mixed 
solvents for dissolving the couplers. 
In addition, the dispersing method of JP-B-51-39852 and JP-A-51-59953 using 
polymers may also be employed. 
Where the couplers have acid groups such as a carboxylic acid group or 
sulfonic acid group, they may be introduced into hydrophilic colloids as 
their aqueous alkaline solutions. 
The photographic material of the present invention may contain ultraviolet 
absorbents in the hydrophilic colloid layers. For instance, usable are 
aryl group-substituted benzotriazole compounds (such as those described in 
U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (such as those 
described in U.S. Pat. Nos. 3,314,794 and 3,352,681), benzophenone 
compounds (such as those described in JP-A-46-2784), cinnamate compounds 
(such as those described in U.S. Pat. Nos. 3,705,805 and 3,707,375), 
butadiene compounds (such as those described in U.S. Pat. No. 4,045,229) 
and benzoxazole compounds (such as those described in U.S. Pat. No. 
3,700,455). In addition, ultraviolet absorbents described in U.S. Pat. No. 
3,499,762 and JP-A-54-48535 may also be used. Ultraviolet absorbing 
couplers (e.g., .alpha.-naphthol cyan dye-forming couplers) and 
ultraviolet absorbing polymers may also be used. These ultraviolet 
absorbents may be mordanted in particular layers. 
For processing the photographic material of the present invention, any 
known methods may be employed. Any known processing solutions may be 
employed for the processing. The processing temperature may be selected 
from the range of from 18.degree. C. to 50.degree. C. However, it may be a 
temperature lower than 18.degree. C. or higher than 50.degree. C., if 
desired. Any of black-and-white photographic processing for forming silver 
images and color photographic processing for forming color images may be 
applied to the photographic material, in accordance with the object. 
The color developer to be used for processing the photographic material 
generally comprises an aqueous alkaline solution containing a color 
developing agent. The color developing agent may be any known general 
aromatic amine developing agent of, for example, phenylenediamines (e.g., 
4-amino-N,N-diethylaniline, 3-methyl-4-amino-N,N-diethylaniline, 
4-amino-N-ethyl-N-.beta.-hydroxyethylaniline, 
3-methyl-4-amino-N-ethyl-N-.beta.-hydroxyethylaniline, 
3-methyl-4-amino-N-ethyl-N-.beta.-methanesulfonamidoethylaniline, 
4-amino-3-methyl-N-ethyl-N-.beta.-methoxyethylaniline). 
In addition, the compounds described in L. F. A. Mason, Photographic 
Processing Chemistry (published by Focal Press, 1966), pages 226 to 229, 
and U.S. Pat. Nos. 2,193,015 and 2,592,364 and JP-A-48-64933 may also be 
used. 
The color developer may additionally contain a pH buffer such as alkali 
metal sulfites, carbonates, borates and phosphates; and a development 
inhibitor or antifoggant such as bromides, iodides and organic 
antifoggants. If desired, it may further contain a water softener; a 
preservative such as hydroxylamine; an organic solvent such as benzyl 
alcohol and diethylene glycol; a development accelerator such as 
polyethylene glycol, quaternary ammonium salts and amines; a dye forming 
coupler; a competing coupler; a foggant such as sodium borohydride; an 
auxiliary developing agent such as 1-phenyl-3-pyrazolidone; a tackifier; a 
polycarboxylic acid chelating agent such as those described in U.S. Pat. 
No. 4,083,723; and an antioxidant such as those described in German Patent 
OLS 2,622,950. 
After being color-developed, the photographic emulsion layers are generally 
bleached. Bleaching of the layers may be effected simultaneously with or 
separately from fixation thereof. Bleaching agents for this step include 
compounds of polyvalent metals such as iron(III), cobalt(III), 
chromium(IV) and copper(II), peracids, quinones and nitroso compounds. For 
instance, usable are ferricyanides; bichromates; organic complexes with 
iron(III) or cobalt(III), for example, complexes of aminopolycarboxylic 
acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid and 
1,3-diamino-2-propanoltetraacetic acid, or complexes of organic acids such 
as citric acid, tartaric acid and phosphoric acid; persulfates; 
permanganates; and nitrosophenol. Above all, a bleaching solution or 
bleach-fixing solution having a weak oxidizing power and containing sodium 
ethylenediaminetetraacetato/iron(III) or ammonium 
ethylenediaminetetraacetato/iron(III) is advantageous, since the couplers 
of the present invention may form dyes having a high color density. 
Ethylenediaminetetraacetato/iron(III) complexes are advantageous either in 
an independent bleaching solution or in a mono-bath bleach-fixing 
solution. 
The bleaching solution or bleach-fixing solution may contain various 
bleaching accelerators such as those described in U.S. Pat. Nos. 3,042,520 
and 3,241,966, JP-B-45-8506 and JP-B-45-8836, thiol compounds such as 
those described in JP-A-53-65732, and also other various additives. 
The photographic polyester film support of the present invention has an 
extremely good surface flatness, being different from any other 
conventional film supports. Therefore, even after being heat-treated, it 
still maintains the good flatness. It is therefore considered that a 
photographic material having the support is not curled. The reasons have 
not been clarified theoretically as yet but are merely within the range of 
presumption. Since the surface flatness of the heat-treated film is good, 
the photographic layers to be formed by coating emulsions thereon are even 
and the photographic material having such a flat support and such even 
emulsion layers may therefore form high-quality images. 
Next, the present invention will be explained in more detail by way of the 
following examples, which, however, are not intended to restrict the scope 
of the present invention. All parts, percents, ratios and the like are by 
weight unless otherwise indicated. 
EXAMPLE 1 
(1) Kinds and Heat-Treatment of Supports (Polyester Films) 
Preparation of Bulk Rolls 
PEN 
To 100 parts by weight of PEN pellet having an intrinsic viscosity of 0.60, 
was added Diaresin as a dye (a product of Mitsubishi Kasei Corp., 
hereinafter the same) so as to make an absorbance of the mixture 0.05 at 
400 nm, followed by drying at 170.degree. C. for 4 hours. After melting at 
300.degree. C., the mixture was stretched 3.1 times in the longthwise 
direction at 140.degree. C. and stretched 3.5 times in the crosswise 
direction at 140.degree. C., followed by heat-fixation at 250.degree. C. 
for 6 seconds. 
PEN/PET=1/1 
To 50 parts by weight of PEN pellet and 50 parts by weight of PET pellet 
each having an intrinsic viscosity of 0.60, was added Diaresin as a dye to 
make an absorbance of the mixture 0.05 at 400 nm, followed by drying at 
170.degree. C. for 4 hours. After melting at 300.degree. C., the mixture 
was stretched 3.1 times in the lengthwise direction at 120.degree. C. and 
stretched 3.5 times at 120.degree. C. in the crosswise direction, followed 
by heat-fixation at 250.degree. C. for 6 seconds. 
PET 
To 100 parts by weight of PET pellet having an intrinsic viscosity of 0.60, 
was added Diaresin as a dye to make an absorbance of the mixture 0.05 at 
400 nm, followed by drying at 170.degree. C. for 4 hours. After melting at 
280.degree. C., the mixture was stretched 3.1 times in the lengthwise 
direction at 100.degree. C. and stretched 3.5 times in the crosswise 
direction at 100.degree. C., followed by heat-fixation at 240.degree. C. 
for 6 seconds. 
Using these, bulk rolls of various polyester films as shown in Tables 1 to 
6 below were prepared, the films each having the thickness pattern as 
indicated in the tables. The films of Tables 1 to 3 were heat-treated 
under the conditions as shown in the tables and the surface flatness of 
the thus heat-treated films was checked as to whether or not the films 
were wrinkled or ridged. Then, the films were processed in accordance with 
the following processes (2) and others. The films of Tables 4 to 6 were 
directly coated with a subbing layer and a backing layer in accordance 
with the following processes (2) and (3), without being heat-treated, and 
thereafter heat-treated in accordance with the following process (4). 
After the polyester supports were biaxially stretched, the strength of them 
was insufficient for use as a photographic support when the lengthwise 
stretching was less than 3 times or more than 3.5 times and when the 
crosswise stretching was less than 2.8 times or more than 4.2 times. In 
addition, if the thickness of the support was less than 60 .mu.m the 
strength of the support was also insufficient. 
TABLE 1-1 
__________________________________________________________________________ 
(without subbing and backing layers) 
Support 
Glass Transition Bulk Roll Condition for Heat 
Treatment 
No. Kind Point (.degree.C.) 
Thickness (.mu.m) 
Length (m) 
Width (m) 
Temp. (.degree.C.) 
Time 
__________________________________________________________________________ 
(hr) 
1 (sample of the 
PEN 120 75 3500 1.5 110 48 
invention 
2 (sample of the 
PEN 120 75 3500 1.5 110 24 
invention) 
3 (sample of the 
PEN 120 75 3500 1.5 110 120 
invention) 
4 (sample of the 
PEN 120 75 3500 1.5 100 240 
invention) 
5 (sample of the 
PEN 120 75 3500 1 110 48 
invention) 
6 (sample of the 
PEN 120 75 5000 1.5 10 48 
invention) 
7 (sample of the 
PEN 120 85 3500 1.5 110 48 
invention) 
8 (sample of the 
PEN/PET = 
100 75 3500 1.5 90 48 
invention) 
1/1 
9 (sample of the 
PET 80 75 3500 1.5 65 48 
invention) 
__________________________________________________________________________ 
TABLE 1-2 
__________________________________________________________________________ 
(without subbing and backing layers) 
Thickness Pattern 
TD Base Surface 
TD R 
MD R 
MD Line Knurling Flatness 
Unevenness 
Value 
Value 
Fluctuation 
Value 
Thickness 
Width 
after Heat 
of Emulsion 
No. (.mu.m) 
(.mu.m) 
Value (.mu.m) 
(.mu.m) 
(.mu.m) 
(mm) 
Treatment 
Layer Coated 
__________________________________________________________________________ 
1 (sample of the 
5 4 5 3 40 15 Good No 
invention 
2 (sample of the 
4 4 3 4 40 12 Good No 
invention) 
3 (sample of the 
4 3 3 2 40 15 Good No 
invention) 
4 (sample of the 
4 3 3 4 40 15 Good No 
invention) 
5 (sample of the 
5 4 5 3 40 15 Good No 
invention) 
6 (sample of the 
4 4 4 3 50 15 Good No 
invention) 
7 (sample of the 
4 5 3 3 40 15 Good No 
invention) 
8 (sample of the 
5 9 7 4 40 15 Good No 
invention) 
9 (sample of the 
5 4 5 3 40 15 Good No 
invention) 
__________________________________________________________________________ 
TABLE 2-1 
__________________________________________________________________________ 
(without subbing and backing layers) 
Support 
Glass Transition Bulk Roll Condition for Heat 
Treatment 
No. Kind Point (.degree.C.) 
Thickness (.mu.m) 
Length (m) 
Width (m) 
Temp. (.degree.C.) 
Time 
__________________________________________________________________________ 
(hr) 
1 (comparative 
PEN 120 75 3500 1.5 110 48 
sample) 
2 (comparative 
PEN 120 75 3500 1.5 110 48 
sample) 
3 (comparative 
PEN 120 75 3500 1.5 110 48 
sample) 
4 (comparative 
PEN 120 75 3500 1.5 110 48 
sample) 
5 (comparative 
PEN 120 75 5000 1.5 110 48 
sample) 
6 (comparative 
PEN 120 85 3500 1.5 110 48 
sample) 
7 (comparative 
PEN/PET = 
100 75 3500 1.5 90 48 
sample) 1/1 
8 (comparative 
PEN/PET = 
100 75 3500 1.5 90 48 
sample) 1/1 
__________________________________________________________________________ 
TABLE 2-2 
__________________________________________________________________________ 
(without subbing and backing layers) 
Thickness Pattern Surface 
TD R 
MD R 
MD TD Base 
Knurling Flatness 
Unevenness 
Value 
Value 
Fluctuation 
Line Value 
Thickness 
Width 
after Heat 
of Emulsion 
No. (.mu.m) 
(.mu.m) 
Value (.mu.m) 
(.mu.m) 
(.mu.m) 
(mm) 
Treatment 
Layer Coated 
__________________________________________________________________________ 
1 (comparative 
10 4 5 3 40 15 Bad Yes 
sample) 
2 (comparative 
5 12 5 3 40 15 Bad Yes 
sample) 
3 (comparative 
5 4 10 3 40 15 Bad Yes 
sample) 
4 (comparative 
5 4 5 7 40 15 Bad Yes 
sample) 
5 (comparative 
9 4 5 3 40 15 Bad Yes 
sample) 
6 (comparative 
5 12 5 3 40 15 Bad Yes 
sample) 
7 (comparative 
10 4 7 3 40 15 Bad Yes 
sample) 
8 (comparative 
5 13 5 4 40 15 Bad Yes 
sample) 
__________________________________________________________________________ 
TABLE 3-1 
__________________________________________________________________________ 
(without subbing and backing layers) 
Support 
Glass Transition Bulk Roll Condition for Heat 
Treatment 
No. Kind Point (.degree.C.) 
Thickness (.mu.m) 
Length (m) 
Width (m) 
Temp. (.degree.C.) 
Time 
__________________________________________________________________________ 
(hr) 
9 (comparative 
PEN/PET = 
100 75 3500 1.5 90 48 
sample) 1/1 
10 (comparative 
PEN/PET = 
100 75 3500 1.5 90 48 
sample) 1/1 
11 (comparative 
PEN 80 75 3500 1.5 65 48 
sample) 
12 (comparative 
PEN 80 75 3500 1.5 65 48 
sample) 
13 (comparative 
PEN 80 75 3500 1.5 65 48 
sample) 
14 (comparative 
PEN 80 75 3500 1.5 65 48 
sample) 
__________________________________________________________________________ 
TABLE 3-2 
__________________________________________________________________________ 
(without subbing and backing layers) 
Thickness Pattern Surface 
TD R 
MD R 
MD TD Base 
Knurling Flatness 
Unevenness 
Value 
Value 
Fluctuation 
Line Value 
Thickness 
Width 
after Heat 
of Emulsion 
No. (.mu.m) 
(.mu.m) 
Value (.mu.m) 
(.mu.m) 
(.mu.m) 
(mm) 
Treatment 
Layer Coated 
__________________________________________________________________________ 
9 (comparative 
4 5 10 4 40 15 Bad Yes 
sample) 
10 (comparative 
4 5 4 7 40 15 Bad Yes 
sample) 
11 (comparative 
11 4 5 2 40 15 Bad Yes 
sample) 
12 (comparative 
3 13 4 3 40 15 Bad Yes 
sample) 
13 (comparative 
4 4 10 3 40 15 Bad Yes 
sample) 
14 (comparative 
4 5 6 8 40 15 Bad Yes 
sample) 
__________________________________________________________________________ 
TABLE 4-1 
__________________________________________________________________________ 
(with subbing and backing layers) 
Support 
Glass Transition Bulk Roll Condition for Heat 
Treatment 
No. Kind Point (.degree.C.) 
Thickness (.mu.m) 
Length (m) 
Width (m) 
Temp. (.degree.C.) 
Time 
__________________________________________________________________________ 
(hr) 
10 (sample of the 
PEN 120 75 3500 1.5 110 48 
invention 
11 (sample of the 
PEN 120 75 3500 1.5 110 24 
invention) 
12 (sample of the 
PEN 120 75 3500 1.5 110 120 
invention) 
13 (sample of the 
PEN 120 75 3500 1.5 110 240 
invention) 
14 (sample of the 
PEN 120 75 3500 1 110 48 
invention) 
15 (sample of the 
PEN 120 75 5000 1.5 10 48 
invention) 
16 (sample of the 
PEN 120 85 3500 1.5 110 48 
invention) 
17 (sample of the 
PET/PEN = 
100 75 3500 1.5 90 48 
invention) 
1/1 
18 (sample of the 
PET 80 75 3500 1.5 65 48 
invention) 
__________________________________________________________________________ 
TABLE 4-2 
__________________________________________________________________________ 
(with subbing and backing layers) 
Thickness Pattern Surface 
TD R 
MD R 
MD TD Base 
Knurling Flatness 
Unevenness 
Value 
Value 
Fluctuation 
Line Value 
Thickness 
Width 
after Heat 
of Emulsion 
No. (.mu.m) 
(.mu.m) 
Value (.mu.m) 
(.mu.m) 
(.mu.m) 
(mm) 
Treatment 
Layer Coated 
__________________________________________________________________________ 
10 (sample of the 
6 5 5 4 30 15 Good No 
invention 
11 (sample of the 
6 4 5 5 30 12 Good No 
invention) 
12 (sample of the 
4 3 2 5 30 15 Good No 
invention) 
13 (sample of the 
5 5 3 4 30 15 Good No 
invention) 
14 (sample of the 
4 4 5 4 30 15 Good No 
invention) 
15 (sample of the 
3 3 4 3 10 15 Good No 
invention) 
16 (sample of the 
5 5 3 2 30 15 Good No 
invention) 
17 (sample of the 
6 9 7 4 30 15 Good No 
invention) 
18 (sample of the 
5 4 8 5 30 15 Good No 
invention) 
__________________________________________________________________________ 
TABLE 5-1 
__________________________________________________________________________ 
(with subbing and backing layers) 
Support 
Glass Transition Bulk Roll Condition for Heat 
Treatment 
No. Kind Point (.degree.C.) 
Thickness (.mu.m) 
Length (m) 
Width (m) 
Temp. (.degree.C.) 
Time 
__________________________________________________________________________ 
(hr) 
15 (comparative 
PEN 120 75 3500 1.5 110 48 
sample) 
16 (comparative 
PEN 120 75 3500 1.5 110 48 
sample) 
17 (comparative 
PEN 120 75 3500 1.5 110 48 
sample) 
18 (comparative 
PEN 120 75 3500 1.5 110 48 
sample) 
19 (comparative 
PEN 120 75 5000 1.5 110 48 
sample) 
20 (comparative 
PEN 120 85 3500 1.5 110 48 
sample) 
21 (comparative 
PEN/PET = 
100 75 3500 1.5 90 48 
sample) 1/1 
22 (comparative 
PEN/PET = 
100 75 3500 1.5 90 48 
sample) 1/1 
__________________________________________________________________________ 
TABLE 5-2 
__________________________________________________________________________ 
(with subbing and backing layers) 
Thickness Pattern Surface 
TD R 
MD R 
MD TD Base 
Knurling Flatness 
Unevenness 
Value 
Value 
Fluctuation 
Line Value 
Thickness 
Width 
after Heat 
of Emulsion 
No. (.mu.m) 
(.mu.m) 
Value (.mu.m) 
(.mu.m) 
(.mu.m) 
(mm) 
Treatment 
Layer Coated 
__________________________________________________________________________ 
15 (comparative 
10 5 5 4 30 15 Bad Yes 
sample) 
16 (comparative 
6 12 5 5 30 15 Bad Yes 
sample) 
17 (comparative 
4 3 10 3 30 15 Bad Yes 
sample) 
18 (comparative 
4 4 3 7 30 15 Bad Yes 
sample) 
19 (comparative 
9 5 5 3 30 15 Bad Yes 
sample) 
20 (comparative 
6 12 5 4 30 15 Bad Yes 
sample) 
21 (comparative 
10 4 6 4 30 15 Bad Yes 
sample) 
22 (comparative 
4 13 3 4 30 15 Bad Yes 
sample) 
__________________________________________________________________________ 
TABLE 6-1 
__________________________________________________________________________ 
(with subbing and backing layers) 
Support 
Glass Transition Bulk Roll Condition for Heat 
Treatment 
No. Kind Point (.degree.C.) 
Thickness (.mu.m) 
Length (m) 
Width (m) 
Temp. (.degree.C.) 
Time 
__________________________________________________________________________ 
(hr) 
23 (comparative 
PEN/PET = 
100 75 3500 1.5 90 48 
sample) 1/1 
24 (comparative 
PEN/PET = 
100 75 3500 1.5 90 48 
sample) 1/1 
25 (comparative 
PEN 80 75 3500 1.5 65 48 
sample) 
26 (comparative 
PEN 80 75 3500 1.5 65 48 
sample) 
27 (comparative 
PEN 80 75 3500 1.5 65 48 
sample) 
28 (comparative 
PEN 80 75 3500 1.5 65 48 
sample) 
__________________________________________________________________________ 
TABLE 6-2 
__________________________________________________________________________ 
(with subbing and backing layers) 
Thickness Pattern Surface 
TD R 
MD R 
MD TD Base 
Knurling Flatness 
Unevenness 
Value 
Value 
Fluctuation 
Line Value 
Thickness 
Width 
after Heat 
of Emulsion 
No. (.mu.m) 
(.mu.m) 
Value (.mu.m) 
(.mu.m) 
(.mu.m) 
(mm) 
Treatment 
Layer Coated 
__________________________________________________________________________ 
23 (comparative 
4 5 10 4 30 15 Bad Yes 
sample) 
24 (comparative 
5 5 4 7 30 15 Bad Yes 
sample) 
25 (comparative 
11 3 4 3 30 15 Bad Yes 
sample) 
26 (comparative 
4 13 5 4 30 15 Bad Yes 
sample) 
27 (comparative 
2 5 10 3 30 15 Bad Yes 
sample) 
28 (comparative 
5 5 5 8 30 15 Bad Yes 
sample) 
__________________________________________________________________________ 
(2) Coating of Subbing Layer 
Each support sample was subjected to corona discharging on both surfaces, 
and the coating liquid described below was coated over one surface to form 
a subbing layer thereon. For the corona discharging, a solid state 
corona-discharging machine 6KVA Model (manufactured by Pillar) was used, 
and the 30 cm-wide support was treated at a speed of 20 m/min. From the 
current and voltage values as read out, the strength treating the support 
was 0.375 KV.A.min/m.sup.2. The discharging frequency for the treatment 
was 9.6 KHz, and the gap clearance between the electrode and the 
dielectric roll was 1.6 mm. 
______________________________________ 
Composition of Subbing Layer: 
______________________________________ 
Gelatin 3 g 
Distilled Water 250 cc 
Sodium .alpha.-sulfo-di-2-ethylhexyl 
0.05 g 
Succinate 
Formaldehyde 0.02 g 
______________________________________ 
(3) Coating of Backing Layer 
After the subbing layer was coated on one surface of each support sample, a 
backing layer having the composition described below was coated on the 
other surface thereof. 
(3-1) Preparation of Dispersion of Fine Conductive Grains (Dispersion of 
Tin Oxide-Antimony Oxide Composite) 
230 parts by weight of stannic chloride hydrate and 23 parts by weight of 
antimony trichloride were dissolved in 3000 parts by weight of ethanol to 
obtain a uniform solution. 1 N aqueous sodium hydroxide solution was 
dropwise added to the uniform solution until the latter had pH of 3, 
whereby co-precipitates of colloidal stannic oxide and antimony oxide were 
formed. The co-precipitates thus formed were allowed to stand at 
50.degree. C. for 24 hours to obtain reddish brown colloidal precipitates. 
The reddish brown colloidal precipitates were separated by centrifugation. 
In order to remove the excess ions, water was added to the co-precipitates 
for washing them by centrifugation. The operation was repeated three times 
whereby the excess ions were removed from the co-precipitates. 
200 parts by weight of the colloidal precipitates from which the excess 
ions had been removed were again dispersed in 1500 parts by weight of 
water, and the resulting dispersion was sprayed into a firing furnace of 
600.degree. C. to obtain a bluish powder of fine grains of a tin 
oxide-antimony oxide composite having a mean grain size of 0.2 .mu.m. The 
specific resistivity of the fine powdery grains was 25 .OMEGA..cm. 
A mixed liquid comprising 40 parts by weight of the fine powdery grains and 
60 parts by weight of water was adjusted to have a pH of 7.0 and roughly 
dispersed with a stirrer. This was then further dispersed in a horizontal 
sand mill (Dyno Mill, trade name by Willya Ibachofenag) until the 
residence time became 30 minutes. 
(3-2) Formation of Backing Layer 
The following composition (A) was coated on the support sample and dried at 
115.degree. C. for 60 seconds to have a dry thickness of 0.3 .mu.m. In 
addition, the following coating liquid (B) was coated over the layer and 
dried at 115.degree. C. for 3 minutes to have a dry thickness of 0.1 
.mu.m. 
______________________________________ 
Composition (A): 
Dispersion of Conductive Fine Grains 
10 wt. pts. 
(prepared above) 
Gelatin 1 wt. pt. 
Water 27 wt. pts. 
Methanol 60 wt. pts. 
Resorcinol 2 wt. pts. 
Polyoxyethylene Nonylphenyl Ether 
0.01 wt. pt. 
Coating Liquid (B): 
Cellulose Triacetate 1 wt. pt. 
Acetone 70 wt. pts. 
Methanol 15 wt. pts. 
Dichloromethylene 10 wt. pts. 
P-chlorophenol 4 wt. pts. 
______________________________________ 
(4) Heat Treatment of Support Sample 
The films of Tables 4 to 6 were, after having been coated with the 
above-mentioned subbing layer and backing layer, heat-treated under the 
condition as shown in the tables. The heat treatment was effected in such 
a way that each sample film was wound around a reel core having a diameter 
of 30 cm with the coated surface facing outward. After the heat treatment, 
the surface flatness of the sample was checked as to whether or not the 
sample was wrinkled or ridged. The results are shown in Tables 4 to 6. 
(5) Each support sample as treated in the manner described above was coated 
with plural photographic layers each having the composition described 
below to form a multi-layer color photographic material sample. 
Compositions of Photographic Layers 
Essential components constituting the photographic layers are grouped as 
follows: 
ExC: Cyan Coupler 
UV: Ultraviolet Absorbent 
ExM: Magenta Coupler 
HBS: High Boiling Point Organic Solvent 
ExY: Yellow Coupler 
H: Gelatin Hardening Agent 
ExS: Sensitizing Dye 
The number for each component indicates the amount coated in g/m.sup.2. The 
amount of silver halide coated is represented as the amount of silver 
therein coated. The amount of sensitizing dye coated is represented as a 
molar unit to mol of silver halide in the same layer. 
______________________________________ 
First Layer: Anti-halation Layer 
Black Colloidal Silver 0.18 as Ag 
Gelatin 1.40 
ExM-1 0.18 
ExF-1 2.0 .times. 10.sup.-3 
HBS-1 0.20 
Second Layer: Interlayer 
Emulsion G 0.065 as Ag 
2,5-Di-t-pentadecylhydroquinone 
0.18 
ExC-2 0.020 
UV-1 0.060 
UV-2 0.080 
UV-3 0.10 
HBS-1 0.10 
HBS-2 0.020 
Gelatin 1.04 
Third Layer: Low-sensitivity Red-sensitive 
Emulsion Layer 
Emulsion A 0.25 as Ag 
Emulsion B 0.25 as Ag 
ExS-1 6.9 .times. 10.sup.-5 
ExS-2 1.8 .times. 10.sup.-5 
ExS-3 3.1 .times. 10.sup.-4 
ExC-1 0.17 
ExC-3 0.030 
ExC-4 0.010 
ExC-5 0.020 
ExC-7 0.0050 
ExC-8 0.010 
Cpd-2 0.025 
HBS-1 0.10 
Gelatin 0.87 
Fourth Layer: Middle-sensitivity 
Red-sensitive Emulsion Layer 
Emulsion D 0.70 as Ag 
ExS-1 3.5 .times. 10.sup.-4 
ExS-2 1.6 .times. 10.sup.-5 
ExS-3 5.1 .times. 10.sup.-4 
ExC-1 0.13 
ExC-2 0.060 
ExC-3 0.0070 
ExC-4 0.090 
ExC-5 0.025 
ExC-7 0.0010 
ExC-8 0.0070 
Cpd-2 0.023 
HBS-1 0.10 
Gelatin 0.75 
Fifth Layer: High-sensitivity 
Red-sensitive Emulsion Layer 
Emulsion E 1.40 as Ag 
ExS-1 2.4 .times. 10.sup.-4 
ExS-2 1.0 .times. 10.sup.-4 
ExS-3 3.4 .times. 10.sup.-4 
ExC-1 0.12 
ExC-3 0.045 
ExC-6 0.020 
ExC-8 0.025 
Cpd-2 0.050 
HBS-1 0.22 
HBS-2 0.10 
Gelatin 1.20 
Sixth Layer: Interlayer 
Cpd-1 0.10 
HBS-1 0.50 
Gelatin 1.10 
Seventh Layer: Low-sensitivity 
Green-sensitive Emulsion Layer 
Emulsion C 0.35 as Ag 
ExS-4 3.0 .times. 10.sup.-5 
ExS-5 2.1 .times. 10.sup.-4 
ExS-6 8.0 .times. 10.sup.-5 
ExM-1 0.010 
ExM-2 0.33 
ExM-3 0.086 
Exy-1 0.015 
HBS-1 0.30 
HBS-3 0.010 
Gelatin 0.73 
Eight Layer: Middle-sensitivity 
Green-sensitivie Emulsion Layer 
Emulsion D 0.80 as Ag 
ExS-4 3.2 .times. 10.sup.-5 
ExS-5 2.2 .times. 10.sup.-4 
ExS-6 8.4 .times. 10.sup.-4 
ExM-2 0.13 
ExM-3 0.030 
ExY-1 0.018 
HBS-1 0.16 
HBS-3 8.0 .times. 10.sup.-3 
Gelatin 0.90 
Ninth Layer: High-sensitivity 
Green-sensitive Emulsion Layer 
Emulsion E 1.25 as Ag 
ExS-4 3.7 .times. 10.sup.-5 
ExS-5 8.1 .times. 10.sup.-5 
ExS-6 3.2 .times. 10.sup.-4 
ExC-1 0.010 
ExM-1 0.030 
ExM-4 0.040 
ExM-5 0.019 
Cpd-3 0.040 
HBS-1 0.25 
HBS-2 0.10 
Gelatin 1.44 
Tenth Layer: Yellow Filter Layer 
Yellow Colloidal Silver 0.030 as Ag 
Cpd-1 0.16 
HBS-1 0.60 
Gelatin 0.60 
Eleventh Layer: Low-sensitivity 
Blue-sensitive Emulsion Layer 
Emulsion C 0.18 as Ag 
ExS-7 8.6 .times. 10.sup.-4 
ExY-1 0.020 
ExY-2 0.22 
EXY-3 0.50 
ExY-4 0.020 
HBS-1 0.28 
Gelatin 1.10 
Twelfth Layer: Middle-sensitivity 
Blue-sensitive Emulsion Layer 
Emulsion D 0.40 as Ag 
ExS-7 7.4 .times. 10.sup.-4 
ExC-7 7.0 .times. 10.sup.-3 
ExY-2 0.050 
ExY-3 0.10 
HBS-1 0.050 
Gelatin 0.78 
Thirteenth Layer: High-sensitivity 
Blue-sensitive Emulsion Layer 
Emulsion F 1.00 as Ag 
ExS-7 4.0 .times. 10.sup.-4 
ExY-2 0.10 
ExY-3 0.10 
HBS-1 0.070 
Gelatin 0.86 
Fourteenth Layer: First Protective Layer 
Emulsion G 0.20 as Ag 
UV-4 0.11 
UV-5 0.17 
HBS-1 5.0 .times. 10.sup.-2 
Gelatin 1.00 
Fifteenth Layer: Second Protective Layer 
H-1 0.40 
B-1 (diameter 1.7 .mu.m) 5.0 .times. 10.sup.-2 
B-2 (diameter 1.7 .mu.m) 0.10 
B-3 0.10 
S-1 0.20 
Gelatin 1.20 
______________________________________ 
In addition, the respective layers contained any of W-1 through W-3, B-4 
through B-6, F-1 through F-17, and iron salt, lead salt, gold salt, 
platinum salt, iridium salt and rhodium salt, so as to have improved 
storability, processability, pressure resistance, fungicidal and 
bactericidal property, antistatic property and coatability. 
Structural formulae of the compounds used as well as the emulsions used are 
shown below. 
TABLE 7 
__________________________________________________________________________ 
Mean 
Fluctuation Ratio of Silver 
Mean AgI 
Grain 
Coefficient 
Ratio of 
Contents [core/inter- 
Content 
Size 
to Grain 
Diameter/ 
layer/shell] 
Structure and Shape of 
(%) (.mu.m) 
Size (%) 
Thickness 
(as AgI content %) 
Grains 
__________________________________________________________________________ 
Emulsion A 
4.0 0.45 
27 1 [1/3] (13/1) 
two-layer structural 
octahedral grains 
Emulsion B 
8.9 0.70 
14 1 [3/7] (25/2) 
two-layer structural 
octahedral grains 
Emulsion C 
2.0 0.55 
25 7 -- uniform structural 
tabular grains 
Emulsion D 
9.0 0.65 
25 6 [12/59/29] (0/11/8) 
three-layer structural 
tabular grains 
Emulsion E 
9.0 0.85 
23 5 [8/59/33] (0/11/8) 
three-layer structural 
tabular grains 
Emulsion F 
14.5 1.25 
25 3 [37/63] (34/3) 
two-layer structural 
tabular grains 
Emulsion G 
1.0 0.07 
15 1 -- uniform structural 
fine grains 
__________________________________________________________________________ 
In Table 7 above: 
(1) Emulsions A to F had been subjected to reduction sensitization with 
thiourea dioxide and thiophosphonic acid during formation of the grains, 
in accordance with the example of JP-A-2-191938; 
(2) Emulsions A to F had been subjected to gold sensitization, sulfur 
sensitization and selenium sensitization in the presence of the color 
sensitizing dyes to be in the respective light-sensitive layers and sodium 
thiocyanate, in accordance with the example of JP-A-3-237450; 
(3) for preparation of tabular grains, a low molecular gelatin was used in 
accordance with the example of JP-A-1-158426; and 
(4) tabular grains and normal crystalline grains having a granular 
structure were observed to have dislocation lines as described in 
JP-A-3-237450, with a high-pressure electronic microscope. 
Chemical formulae of the compounds used above are mentioned below. 
##STR4## 
(6) Development 
The photographic material samples were developed in accordance with the 
process described below. 
______________________________________ 
Color Development Process: 
Step Temperature 
Time 
______________________________________ 
Color Development 
38.degree. C. 
3 min 
Stopping 38.degree. C. 
1 min 
Rinsing 38.degree. C. 
1 min 
Bleaching 38.degree. C. 
2 min 
Rinsing 38.degree. C. 
1 min 
Fixation 38.degree. C. 
2 min 
Rinsing 38.degree. C. 
1 min 
Stabilization 38.degree. C. 
1 min 
______________________________________ 
Compositions of the processing solutions used above are described below. 
______________________________________ 
Color Developer: 
Sodium Hydroxide 2 g 
Sodium Sulfite 2 g 
Potassium Bromide 0.4 g 
Sodium Chloride 1 g 
Borax 4 g 
Hydroxylamine Sulfate 2 g 
Disodium Ethylenediaminetetraacetate 
2 g 
Dihydrate 
4-Amino-3-methyl-N-ethyl-N-(.beta.-hydroxy- 
4 g 
ethyl)aniline Monosulfate 
Water to make 1 liter 
Stopping Solution: 
Sodium Thiosulfate 10 g 
Ammonium Thiosulfate 30 ml 
(70% aqueous solution) 
Acetic Acid 30 ml 
Sodium Acetate 5 g 
Potassium Alum 15 g 
Water to make 1 liter 
Bleaching Solution: 
Sodium Ethylenediaminetetraacetate/ 
100 g 
Iron(III) Dihydrate 
Potassium Bromide 50 g 
Ammonium Nitrate 50 g 
Boric Acid 5 g 
Aqueous Ammonia to make pH of 5.0 
Water to make 1 liter 
Fixer: 
Sodium Thiosulfate 150 g 
Sodium Sulfite 15 g 
Borax 12 g 
Glacial Acetic Acid 15 ml 
Potassium Alum 20 g 
Water to make 1 liter 
Stabilizer: 
Boric Acid 5 g 
Sodium Citrate 5 g 
Sodium Metaborate Tetrahydrate 
3 g 
Potassium Alum 15 g 
Water to make 1 liter 
______________________________________ 
The multi-layer color photographic material samples as prepared in the 
manner described above were examined with respect to the condition of the 
surface of the photographic layers coated thereon. The results are shown 
in Tables 1 to 6 above. 
From Tables 1 to 6 above, it is understood that the surface flatness of the 
heat-treated supports of the present invention was good and therefore the 
photographic material samples having them were free from unevenness of 
their surfaces coated with the emulsion layers. As opposed to them, the 
surface flatness of the comparative support samples Nos. 1 to 14 and 15 to 
28 in which at least one of the four values defining the thickness pattern 
was not within the scope of the present invention was bad and therefore 
the surfaces of the emulsion layers coated on them were uneven. 
As explained in detail above, the photographic polyester support of the 
present invention is heat-treated at a temperature of from 50.degree. C. 
to the glass transition temperature while it is in the form of a bulk 
roll. The thus heat-treated support is hardly curled and the surface 
flatness of the support is not worsened even when rolled up into a roll. 
In addition, when the support is coated with photographic emulsions, the 
coated surface is even. 
The photographic polyester support of the present invention has higher 
mechanical strength than TAC. Therefore, the thickness of the support can 
be reduced significantly. Using the support with such advantages, 
down-sizing of cameras and film cartridges is possible. 
While the invention has been described in detail and with reference to 
specific embodiments thereof, it will be apparent to one skilled in the 
art that various changes and modifications can be made therein without 
departing from the spirit and scope thereof.