Silver halide photographic light-sensitive material

Disclosed is a silver halide photographic light-sensitive material comprising a support provided thereon, a layer selected from the group consisting of a first layer and a second layer, and a silver halide emulsion layer in this order, wherein said support comprises a syndiotactic styrene polymer or a copolymer thereof, and a first layer comprises a polymer composition composed of a polyester component with a styrene polymer component, and a second layer comprises a diene type polymer.

FIELD OF THE INVENTION 
The present invention relates to a silver halide light-sensitive 
photographic material obtained by the use of a support, having excellent 
sizing stability, and having a subbing layer thereon, by which excellent 
coating and adhesion properties to the photographic constituent layers 
provided thereon, is obtainable. 
BACKGROUND OF THE INVENTION 
Various properties are required for a photographic support, including, for 
example, not only optical transparency, but also accessibility to 
treatment for improving adhesion to a hydrophilic photographic emulsion 
layer to be provided thereon, sizing stability and anti-curling property. 
For these reasons, use of a variety of synthetic resin sheets and films 
have heretofore been proposed and attempted. 
Generally, for a photographic support used by being wound on a small core, 
cellulose triacetate(TAC) is often employed and as for the photographic 
support used in the form of a roll wound around a larger core or sheets, 
polyethyleneterephthalate(PET) is popularly used. 
Recently, with the increased demand of enhancing information density per 
unit area, stricter size stability of the light-sensitive photographic 
material has also been demanded. For the photographic light-sensitive 
material used as a intermediate recording medium for a variety of purposes 
and, an image is obtained by using several kinds of recording media in 
sequence, and an adverse consequence is that once a wrong measurement is 
used, it becomes impossible to obtain a clear photographic image. 
These sort of dimensional discrepancies are caused partly because 
hydrophilic binder consisting mainly of gelatin used in the constituent 
layers of the light-sensitive photographic material is easily affected by 
the environmental humidity, and partly because PET and TAC comprise 
hydrophilic portions in their molecules as structure and, therefore, they 
are also effected by the environmental humidity. 
As a countermeasure, for example, a technique of providing a water-proof 
layer consisting of polyvinylidene chloride on the support is known, 
however, there are problems that, (a) when the support is stored for a 
long time, dechlorination progresses gradually, yellow stain occurs on the 
film, that (b) when the cut-off edge portions are collected and re-used in 
a film coating step, the above-mentioned yellow stain takes place due to 
dechlorination, and that (c) re-use of the support resin becomes 
impossible because of vinylidene chloride is present as impurities, and 
once upon incineration, chlorine gas is generated, which has an adverse 
effect on the environment. 
Generally, polystyrene does not have dimensional stability due to heat as 
it is not crystalline, however, so-called syndiotactic polystyrene 
disclosed in Japanese Patent Publication O.P.I. Publication No. 
131843/1991, is a highly crystalline and has an advantage in that it shows 
an excellent dimensional stability. 
On the contrary, however, because of its excellent crystalline property, 
the syndiotactic polystyrene can not be easily treated with surface 
treatment to obtain good adhesion property. Further, there is a problem 
that the syndiotactic polystyrene has a high hydrophobicity on its 
surface, so that coating property is bad and uneven coating tends to occur 
when a subbing layer is provided on the surface thereof. 
The present invention has been accomplished in view of the above mentioned 
background state of the art, and, accordingly the object of the present 
invention is to improve coating performance and adhesion property of the 
photographic constituent layers on a photographic support made of 
syndiotactic polystyrene, which has excellent dimensional stability. 
SUMMARY OF THE INVENTION 
The above-mentioned object of the present invention can be achieved by the 
following constitutions. 
Item 1: A silver halide photographic light-sensitive material comprising a 
support providing thereon, a hydrophobic polymer layer, and a silver 
halide light-sensitive layer, wherein said support comprises a styrene 
polymer having a racemo chain as a main chain or a composition containing 
said styrene polymer. 
Item 2: The silver halide photographic light-sensitive material of item 1, 
wherein said hydrophobic layer comprises a styrene-diene copolymer. 
Item 3: A method for preparing the silver halide photographic 
light-sensitive material of item 1, wherein said method comprising the 
steps of: 
(a) subjecting said support to a corona discharge treatment, a grow 
discharge treatment, a flame treatment or a ultraviolet radiation 
treatment, and 
(b) coating said hydrophobic polymer layer and a silver halide photographic 
light-sensitive layer. 
Item 4: The method of item 3, wherein a de-electrification treatment is 
carried out before or after subjecting said support to a corona discharge 
treatment, a grow discharge treatment, a flame treatment or a ultraviolet 
radiation treatment. 
Item 5: A method for preparing the silver halide photographic 
light-sensitive material of item 1, wherein said method comprising casting 
steps of: 
(a) coating said hydrophobic polymer on said support, 
(b) extending the polymer coated support in at least one direction, 
(c) applying a heat treatment to the extending support, and 
(d) coating said silver halide photographic light-sensitive layer on the 
heat-treatment support. 
Item 6: The method for preparing the silver halide photographic 
light-sensitive material of item 5, wherein said hydrophobic polymer layer 
comprises a styrene-diene copolymer. 
Item 7: A method for a silver halide photographic light-sensitive material 
comprising a support and provided thereon, a hydrophobic layer, a 
hydrophilic layer, and a silver halide photographic light-sensitive layer, 
comprising the steps of: 
(a) coating said polymer layer and said hydrophilic colloid layer on said 
support, wherein said support comprises a styrene polymer having a racemo 
chain as a main chain or a composition containing said styrene polymer, 
(b) applying a heat-treatment to the coated support at a temperature range 
of not less than 40.degree. C. and not more than of a glass transition 
temperature of said support, and 
(c) coating a silver halide emulsion layer on the heat treatment material. 
Item 8: The method of item 7, wherein said hydrophobic polymer layer 
comprises a styrene-diene copolymer. 
Item 9: The method of item 5, wherein said method comprises a step of 
applying a heat-treatment to the coated support at a temperature range of 
not less than 40.degree. C. and not more than of a glass transition 
temperature of said support after coating step of said hydrophobic layer 
and before coating step of said silver halide photographic light-sensitive 
layer. 
Item 10: The method of item 9, wherein said hydrophobic polymer layer 
comprises a styrene-diene copolymer. 
Item 11: A silver halide photographic light-sensitive material comprising a 
support containing a syndiotactic styrene based polymer having a racemo 
chain, and thereon, a hydrophilic photographic layer through a layer, 
wherein said layer comprises a polymeric composition containing a 
water-dispersible or a water-soluble polyester and a styrene based 
polymer, and a compound represented by formula I. 
Item 12: The silver halide photographic light-sensitive material of item 
11, wherein the polymeric composition is selected from the group 
consisting of a first dispersion polymerization of a styrene in the 
presence of a water-dispersive or a water-soluble polyester and a second 
dispersion polymerization of a styrene and a monomer being capable of 
reacting the styrene in the presence of a water-dispersive or a 
water-soluble polyester. 
Item 13; The silver halide photographic light-sensitive material of item 
11, wherein said polymeric composition comprises a polymer prepared by 
polymerizing styrene and a monomer being capable of copolymerizing with 
styrene in the presence of a water dispersible or water-soluble polyester 
as a main chain. 
Item 14: The silver halide photographic light-sensitive material of item 
11, 12 or 13, wherein said layer comprises a water-soluble 
electron-conductive compound and a polyglycerin compound. 
Item 15: The silver halide photographic light-sensitive material of item 
11, 12 or 13, wherein said silver halide photographic light-sensitive 
material is prepared by a method comprising the steps of: 
(a) coating said layer comprising said polymeric composition on said 
support, 
(b) extending the coating material to at least one direction, 
(c) applying a heat treatment to the extended coating material so as to 
orientate to crystal of said syndiotactic polystyrene of said support, and 
(d) coating a hydrophilic photographic layer on the heat treatment 
material. 
That is to say, the present inventors have reached the present invention by 
finding a fact that a composition which is most suitable for a subbing 
layer, in the case where a syndiotactic polystyrene based support having 
excellent dimensional stability is used as a the support. 
Below, the present invention is further explained in detail. 
In the present invention, the term "a film having a syndiotactic styrene 
polymer as its main component" shows a styrene polymer or a composition 
containing it, of which tacticity (stereoregularity structure) consists 
mainly of a syndiotactic structure, and when the syndiotactic styrene 
polymer is composed of a homopolymer of styrene, it can be obtained 
according to the method disclosed in Japanese Patent O.P.I. Publication 
No. 62-117708(1987) and according to the method disclosed in Japanese 
patent O.P.I. Publication Nos. 1-46912(1990) and 1-178505(1990), etc. in 
the case of other polymers. 
Its tacticity can be analyzed quantitatively by using nuclear magnetic 
resonance method (13C-NMR) using an isotope of carbon. The quantitative 
analysis by using the nuclear magnetic resonance is carried out by the 
similar method disclosed in Macromol. Chem, 176, 3051 (1975). 
The tacticity measured by the 13C-NMR can be calculated as the existence 
ratio of the structural unit having a plural of the continuous number. For 
example, a tacticity as diad in the case of two continuous number, a 
tacticity as triad in the case of three continuous number and a tacticity 
as pentad in the case of five continuous number, are respectively 
calculated. 
In the present invention, the syndiotactic styrene polymer or the copolymer 
thereof has a racemo-diad of not less than 75 mole %, preferably of not 
less than 85 mole % and more preferably of not less than 95 mole %. 
As the racemo diad of the present invention, each of monomer units forming 
the racemo diad may be same or different. 
Furthermore, the above-mentioned racemo diad is preferably represented by 
Formula 3. 
##STR1## 
wherein R.sub.1 and R.sub.2 each represents a hydrogen, a chloro atom, a 
bromine atom, a fluorine atom, an iodine atom, an alkyl group, an aryl 
group, an alkoxy group, an carboxyl group, a sulfo group, a hydroxy group, 
an amino group, a sulfamoyl group, a carbamoyl group, a halogenated alkyl 
group, a cyano group, an alkoxycarbonyl group. 
As for specific monomers being capable of forming the syndiotactic styrene 
polymer composition, for example, a styrene, an alkyl styrene such as a 
methyl styrene; a halogenated alkyl styrene such as chloromethylstyrene 
and chlorostyrene, an alkoxystyrene, an ester of vinylbenzoate and a 
mixture of thereof. Particularly, a copolymer of an alkylstyrene and 
styrene is one of preferable combinations in order to obtain a film having 
thickness of not less than 50 .mu.m. 
When preparing the polystyrene based resin having the syndiotactic 
structure of the present invention, a transition metal compound and a 
compound having aluminoxane as a main component or a transition metal 
compound and a compound being capable of forming an ionic complex by the 
reaction with the transition metal compound disclosed in Japanese Patent 
O.P.I. Publication No. 320448/1993, can be employed as a polymerization 
catalyst. 
In order to prepare the styrene polymer used for the film of the present 
invention, first the above-mentioned styrene monomer is polymerized, after 
sufficient refining, in the presence of any one of the above-mentioned 
polymerization catalysts. The polymerization is carried out usually at the 
temperature of -50.degree. and 200.degree. C. and, more preferably, 
30.degree. to 100.degree. C. for the period of one second to 10 hours and, 
more preferably, for the period of one minute to six hours. For the manner 
of polymerization, any one of slurry polymerization method, solution 
polymerization method, bulk polymerization method and gas-phase 
polymerization can be employed. Further it may be either a continuous or a 
non-continuous polymerization. Here, in the solution polymerization, as 
the solvent, for example, one or more kinds of solvents selected from, for 
example, aromatic hydrocarbon solvent such as benzene, toluene, xylene and 
ethylbenzene; an aliphatic hydrocarbon solvent such as cyclopentane, 
hexane, heptane, octane can be employed either singly or two or more kinds 
in combination. 
In this case, a volume ratio of the monomer to the solvent may optionally 
be selected. Further, regulation of molecular weight and the composition 
may be controlled according to the ordinary method which is commonly 
employed in the art. 
Adjustment of molecular weight of the polymer can be made by, for example, 
hydrogen, temperature and monomer concentration. 
It may be possible to copolymerize other monomers being capable of 
copolymerization together with the above-mentioned styrene monomer within 
the extent which does not jeopardize the advantage of the present 
invention. 
Polymers used for film manufacturing of the SPS (syndiotactic styrene 
polymer) has a weight average molecular weight of not less than 10,000 
and, more preferably, of not less than 30,000. Polymers having weight 
average molecular weight of less than 10,000 do not usually become films 
having excellent strength and anti-heat resistant properties. 
Although there is no specific limit as to the upper limit of the weight 
average molecular weight, however, in the case it exceeds 1,500,000, there 
is a possibility that tearing off of the film due to stretching tension 
takes place. 
Although there is no specific limitation as to the molecular weight of the 
SPS as far as a film can be manufactured, it is preferable that the weight 
average molecular weight is 10,000 to 3,000,000 and, more preferably, 
30,000 to 1,500,000. Further as to the molecular weight distribution given 
in terms of a number average molecular weight/a weight average molecular 
weight is preferably 1.5 to 8. This molecular weight distribution can be 
adjusted by mixing polymers having different molecular weight. 
Further, the syndiotactic styrene polymer of the present invention is dried 
by drying syndiotactic styrene polymer pellets at a temperature of 
120.degree. to 180.degree. C. for 1 to 24 hours under reduced pressure or 
the atomospheric pressure and inactive gas surroundings such as air or 
nitrogen gas. There is no specific limitation as to the moisture content, 
however, in the view of preventing deterioration of the mechanical 
strength by hydrolysis, the moisture content is not more than 0.05%, 
preferably not more than 0.01% and, more preferably, not more than 0.005%. 
However, of course, so far as the advantages of the present invention are 
attainable, the method is not limited to the above-mentioned. 
The SPS film of the present invention preferably consists solely of an SPS 
film prepared from styrene, however, it is possible to control 
crystallization speed and make the film stronger by mixing a styrene 
polymer having an isotactic structure (IPS). 
Although the mixing weight ratio of the SPS and the IPS (a styrene based 
polmer having an isotactic structure in which a main chain is a 
meso-continuous chain) may be varied depending on the degree of 
stereoregularity of the respective polymers, however, it is 30:70 and 99:1 
in terms of a weight ratio and, more preferably 50:50 to 98:2 in terms of 
a weight ratio. 
In the support of the present invention, in order to have a function, a 
variety of additives including, for example, inorganic fine particles, an 
anti-oxidation agent, a ultraviolet-ray absorbent, an anti-static agent, a 
coloring agent, a pigment, a dye, etc can be incorporated within the 
extent which jeopardize the object of the present invention. 
For the extruding method at the time of manufacturing the film, any 
conventional method may be applied. For example, a extrusion method by the 
use of a T-die is preferable. An unstretched film is manufactured by 
melting a syndiotactic polystyrene pellet at a temperature of 280.degree. 
to 350.degree. C., extruding, cooling and solidified on a casting roll 
while applying electrostatic potential. 
Next this unstretched is biaxially stretched for the polymer crystal to set 
to be oriented biaxially. For the method of stretching, any appropriate 
method from a variety of known methods, for example, including one after 
another biaxial stretching method in which a longitudinal stretching and a 
lateral stretching are carried out in this order, another one after 
another biaxial stretching method in which a lateral stretching and a 
longitudinal stretching are carried out in this order, a 
lateral-longitudinal-lateral stretching method, a 
longitudinal-lateral-longitudinal stretching method, a 
longitudinal-longitudinal-lateral stretching method or simaltaneous 
biaxial stretching method may optionally be selected depending on the 
required properties such as mechanical strength and dimensional stability, 
etc. 
Generally in the continuous manufacturing, longitudinal stretching means 
stretching in the above-mentioned longitudinal direction, and lateral 
stretching means stretching in the width direction. That is to say, in the 
continuous manufacturing, one after another biaxial stretching, in which a 
film is first stretched in the above-mentioned longitudinal direction and, 
subsequently in the lateral direction, is preferable. In this case, 
stretching magnification is 2.5 to 6 times with respect to the 
longitudinal direction, and, the longitudinal stretching temperature 
depends upon Tg (the glass transition temperature) of the polymer, so that 
the longitudinal stretching temperature is usually set to be Tg plus 
10.degree. C. to Tg plus 50.degree. C. 
In the case of a syndiotactic polystyrene based film, it may be preferably 
carried out at the temperature of 110.degree. to 150.degree. C. The 
lateral stretching temperature is preferably carried out at the 
temperature of 115.degree. to 160.degree. C. being a slightly higher than 
longitudinal stretching temperature. 
Next, this stretched film is subjected to heat treatment. In this case, the 
treatment temperature may be varied depending upon utility. For the 
shrinkage packing use, usually not more than 150.degree. C., For 
photographic, printing or medical use, in which excellent dimensional 
stability is required, a temperature of 150.degree. to 270.degree. C. may 
optionally be selected. 
Although there is no specific limitation as to the time for the heat 
treatment, one second to two minutes is usually applied. As a matter of 
course, if necessary, a heat relaxation treatment either in the 
longitudinal direction or in the lateral direction can be employed. 
Hereafter, the film may be cooled rapidly and wound up. However, after 
cooling down the temperature gradually at the temperature between Tg and 
the heat treatment temperature while spending 0.1 minute to 1500 hours, 
the film is wound around a core having a larger diameter, and further, 
cooling down is carried out at the cooling rate of -0.01.degree. to 
-20.degree. C./min at the temperature range of 40.degree. C. and Tg. It is 
preferable from a viewpoint that curling habit may not easily be conferred 
on the film. Of course, the heat treatment at a temperature of 40.degree. 
C. and Tg is preferably carried out for a time of 0.1 minute to 1500 hours 
in a thermostatic chamber during a period in which a support film is wound 
up, a silver halide emulsion is coated on the support film, and the silver 
halide emulsion coated film is cut. 
In addition to the film-manufacturing process as mentioned above, for the 
purposes of conferring enhanced lubrication, adhesion or anti-static 
properties on the film, a SPS-laminated SPS film, in which a SPS support 
is laminated on at least one surface of the SPS support, may also be 
manufactured. SPS laminating on the SPS support may be performed by, for 
example, after laminating with layer flow state under which the resin is 
melted, extruding from a die, or by laminating by extrusion with melting 
SPS resin on a cooled and solidified SPS unstretched support or on a SPS 
mono-axially stretched support and, thereafter, stretching thus 
SPS-laminated SPS film support in both longitudinal and lateral directions 
or in the direction perpendicular to the direction in the mono-axial 
stretching and thermally fixing this. Extruding conditions of the SPS 
resin, stretching temperature, magnification rate of stretching, 
thermal-fixing temperature, etc. may be varied depending on the 
combination of the SPS to be laminated, however, a fine tuning of the film 
manufacturing condition is carried out, so that it is possible to select 
the optimum condition, and therefore, a drastic revision of the film 
manufacturing condition is not necessary. 
Needless to say, lamination may consist of two or more layers, and they are 
combinations of either the similar kinds of polymers, including 
combinations of copolymers, or different kinds of polymers. 
The above film-manufacturing method can optionally be changed depending 
upon its use and object and, accordingly, the manner of manufacturing is 
by no means limited to those mentioned above. 
Thickness of the thus obtained syndiotactic polystyrene based stretched 
film can vary depending upon its use, including, for example, 0.3 .mu.m 
for extremely thin condensers, 6 .mu.m or 12 .mu.m for ordinary 
condensers, 100 .mu.m for light-sensitive materials for medical and 
printing uses and 250 .mu.m-thick for electric insulating materials 
(Slotriner), however, the above-mentioned film manufacturing method is 
effectively applied to a film having a thickness of 0.3 to 500 .mu.m. 
In the present invention, the thickness of the support is 50 to 500 .mu.m, 
and more preferably, 70 to 250 .mu.m and the haze of the support is 
preferable not more than 5%. 
Next, respective ingredients used in the subbing layer of the present 
invention are explained. 
The polyester used in the present invention is a substantially linear 
polymer obtained by through condensation polymerization of a polybasic 
acid, a polybasic acid having a sulfo group or ester-forming derivative 
thereof and a polyol or an ester-forming derivative thereof. As for the 
polybasic acid ingredient of the polymer, for example, terephthalic acid, 
isophthalic acid, phthalic acid, phthalic acid anhydride, 
2,6-naphtharenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic 
acid, sebacic acid, trimellitic acid, pyromellitic acid and dimeric acid 
can be mentioned. Together with those mentioned above, a small proportion 
of an unsaturated polybasic acid such as maleic acid, fumaric acid and 
itaconic acid or a hydroxylcarbonic acid such as p-hydroxylbenzoic acid 
and p-(.beta.-hydroxyethoxy)benzoic acid. The polyester is preferably a 
water-dispersible polyester, and in the present invention, a term "a 
water-dispersible polyester" is defined as a polyester having polyester 
particle size of several tens nm to several hundreds nm in water. 
As for the polyol ingredients, for example, ethylene glycol, diethylene 
glycol, 1,4-butane diol, neopentyl glycol, dipropyrene glycol, 1,6-hexane 
diol, 1,4-cyclohexane dimethanol, xylirene glycol, trimethylol propane, 
poly(ethyleneoxide)glycol, and poly(tetramethyleneoxide)glycol can be 
mentioned. 
As for the dicarboxylic acid or ester derivative thereof having a 
sulfonate, used in the present invention, one having an alkali sulfonate 
group is particularly preferable, including, for example, an alkali metal 
salt or an ester derivative thereof of 4-sulfo-isophthalic acid, 
5-sulfo-isophthalic acid, sulfoterephthalic acid, 4-sulfo-phthalic acid, 
4-sulfonaphthalene-2,7-dicarboxylic acid and 5-(4-sulfophenoxy) 
isophthalic acid can be mentioned, and a sodium isophthalate or an esteric 
derivative thereof is particularly preferable. 
These are preferably contained in an amount of 5 to 15 mol %, particulayr 
preferably in an amount of 6 to 10 mole % of the total dicalboxylic 
ingredient in the polyester in view of water-dispersibility and water 
solubility in a subbing layer coating solution and in view of water 
resisting qualities of a coating film. 
Futher, in order to improve water-resisting qualities and adhesive 
properties, it is preferable to modify a styrene polymer. 
Further, the styrene polymer may either be a homopolymer or a copolymer 
produced from the monomers given below. 
A styrene such as styrene, methyl styrene, dimethyl styrene, trimethyl 
styrene, ethyl styrene, iso-propyl styrene, butyl styrene, hexyl styrene, 
cyclohexyl styrene, chloromethyl styrene, acetoxymethyl styrene, methoxy 
styrene, chloro styrene, dichloro styrene, 2-bromo-4-trifluoromethyl 
styrene, vinyl benzoic acid and vinyl benzoic acid methyl ester. 
In the present invention, styrene content of the copolymer is not less than 
50 mole %, and more preferably, not less than 60mole %. 
Further, it may be a copolymer produced from the above-mentioned monomers 
and one or more monomers given below: 
For example, acrylic acid esters, acrylamides, methacrylic acid esters, 
methacrylamides, allyl compounds, vinyl ethers, vinyl esters, vinyl 
heterocyclic compounds, N-vinyl compounds, chrotonic acid compounds, 
itaconic acid compounds, olefins and maleic acid anhydrides can be 
mentioned. 
As more specific examples, acrylic acids such as acrylic acid; acrylates 
such as ethyl acrylate, butyl acrylate, amyl acrylate, octyl acrylate, 
2-butoxyethyl acrylate, chloroethyl acrylate, cyanoethyl acrylate, 
dimethylaminoethyl acrylate, diethyleneglycol-mono acrylate, 
trimethylolpropane-mono-acrylate, glycidyl acrylate, benzyl acrylate, and 
methoxybenzyl acrylate, methacrylic acids such as methacrylic acid, 
methacrylates such as methyl methacrylate, ethyl methacrylate, isopropyl 
methacrylate, benzyl methacrylate, cyanoacetoxyethyl methacrylate, 
chlorobenzyl methacrylate, ethyleneglycolmono methacrylate, 
3-hydroxypropyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, 
diethylene glycol monomethacrylate, glycidyl methacrylate, 
dimethylaminophenoxyethyl methacrylate and phenyl methacrylate, 
acrylamides such as acrylamide, N-substituted acrylamides such as methyl 
acrylamide, ethyl acrylamide, butyl acrylamide, t-octyl acrylamide, benzyl 
acrylamide, dimethylaminoethyl acrylamide, phenyl acrylamide, 
hydroxyphenyl acrylamide, dimethyl acrylamide, dibutyl acrylamide, 
methacrylamides such as methacrylamide, N-substituted methacrylamide such 
as methyl methacrylamide, t-butyl methacrylamide, t-octyl methacrylamide, 
benzyl methacrylamide and cyclohexyl methacrylamide, allyl compounds, for 
example, allyl esters such as allyl acetate, allylcaprate and allyl 
laurate; allyloxy ethanol, allylbutyl ether, allylglycidyl ether and 
allylphenyl ether; vinyl ethers such as methylvinyl ether, butylvinyl 
ether, hexylvinyl ether, octylvinyl ether, ethylhexylvinyl ether, 
methoxyethylvinyl ether, chloroethylvinyl ether, 2-ethylbutyl ether and 
hydroxyethylvinyl ether; vinyl esters such as vinyl acetate, vinyl 
propionate, vinyl butylate, vinyl isobutylate, vinyldimethyl propionate, 
vinylethyl butylate, vinyl valerate, vinyl caproate and 
vinylchloroacetate, vinylheterocyclic compounds such as N-vinyl 
oxazolidone, vinyl pyridine, N-vinyl imidazole, N-vinyl pyrrolidone, 
N-vinyl carbazole, and n-vinylethyl acetamide, crotonic acid compounds 
such as crotonic acid, croton amide, crotonic acid ester such as butyl 
crotonate, vinyl ketones such as methylvinyl ketone and phenylvinyl 
ketone; olefins such as dicyclopentadiene diene, ethylene, propylene, 
1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene, itaconic acids such 
as itaconic acid, itaconic acid anhydride and methyl itaconate, crotonic 
acids such as crotonamide and methyl crotonate, sorbic acid, cinnamic 
acid, methyl sorbate, glycidyl sorbate, citraconic acid, chloro acrylate, 
mesaconic acid, maleic acid and fumaric acid, unsaturated nitriles such as 
acrylonitrile and methacrylonitrile can be mentioned. 
In the copolymer of the present invention, a styrene as a monomer unit is 
preferably contained in an amount of not less than 50 mole % and more 
preferably, of not less than 60 mole %. 
Method of conducting dispersion polymerization of the above-mentioned 
styrene and other monomers capable of copolymerization with styrene in the 
presence of a polyester is as follows. More specifically, the 
above-mentioned monomer is dispersed in the solution containing polyester, 
and then, the above-mentioned monomer is polymerized at a temperature of 
30.degree. to 100.degree. C. and, more preferably, of 50.degree. to 
80.degree. C., using as a polymerization initiator such as ammonium 
persulfate, potassium persulfate, ammonium cerium nitrite, ammonium cesium 
sulfate, hydrogen peroxide, azobisisobutyronitrine or a benzoyl peroxide. 
In this case, a surface active agent is not always necessary and the 
above-mentioned monomer is capable of polymerization under the soap free 
condition, however, for the purpose of improving polymerization stability, 
a general nonionic or anionic surface active agent may be used as an 
emulsifying agent. 
Further, a graft polymer composed of the water dispersible polyester and 
styrene or styrene and a monomer being capable of copolymerization with 
styrene, may be obtained according to copolymerization of the 
above-mentioned monnomer and the polyester denatured by introducing a 
reactive group being capable of addition polymerization in the end group 
of the polyester, or a method, in which first, polymerizing the 
above-mentioned styrene, and then, during a end group of the 
above-mentioned styrene, is active, introducing a reactive group such as a 
hydroxyl group, an amino group, a carboxyl group, a glycidyl group or an 
amino group and introducing this copolymer when the condensation reaction 
takes place. 
In addition, a polymerization of styrene by using a polymerization catalyst 
is finished, and during an end group of the styrene polymer is still 
active, a compound having a hydroxyl group, an amino group, a carboxyl 
group, a halogen atom, a halogenated alcohol compound such as 
4-bromophenetyl alcohol, 4-chlorophenol, 3-bromo-1-propanol or a 
halogenated carboxylic acid such as .alpha.-bromo-toluilic acid, 
p-bromo-benzoic acid or 2-bromo-propionic acid are added in a reaction 
vessel, and reacted for about one hour at a temperature of 30.degree. to 
80.degree. C. in a reaction vessel. Thus, the above-mentioned graft 
polymer can be also obtained. 
The component ratio of polyester to styrene in the copolymer is 99:1 to 
5:95, preferably, 97:3 to 50:50 and more preferably, 95:5 to 80:20 by 
weight. 
Next, the polymer subbing layer used in the present invention is explained. 
The polymer layer is used as a first subbing layer, and for the polymer 
diene-type rubber-like material is preferably used as the polymer. This 
rubber-like material is usually composed of a copolymer consisting of a 
vinyl monomer and a diolefin monomer. For the vinyl monomer, for example, 
styrene, acrylonitrile, methacrylonitrile, methyl methacrylate, methyl 
acrylate, vinyl acetate and as for diolefin, butadiene, isoprene and 
chloroprene are used preferably. In addition to these ingredients, as for 
unsaturated carboxylic acid, such as acrylic acid, methacrylic acid, 
itaconic acid, maleic acid anhydride or a derivative in which a part of 
these ingredients are alkylesterified; acrolein, methacrolein, glycidyl 
acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl 
methacrylate, allyl acrylate, allyl methacrylate, an ingredient being 
capable of crosslinking such as N-methylol acrylamide, N-methylol 
methacrylamide, vinyl isocyanate and allyl isocyanate may preferably be 
added. The content of diolefin is preferably 10 to 60% by weight with 
respect to the total polymer. 
For the copolymers, which are preferable in view of easy availability on 
the market, for example, styrene-butadiene, styrene-isoprene, 
styrene-chloroprene, methylmethacrylate-butadiene and 
acrylonitrile-butadiene can be mentioned. Among these, styrene-butadiene 
is preferably employed. 
For the method of polymerization, for example, emulsion polymerization, 
solution polymerization, bulk polymerization suspension polymerization and 
radioactive polymerization, etc. can be mentioned. 
In the present invention, the diene monomer which is a monomer constituent 
forming the copolymer, denotes a monomer containing two ethylenic linkages 
in a molecule, and the diene monomer may be either an aliphatic 
unsaturated hydrocarbon or one having a cyclic structure. Specifically, it 
includes, for example, conjugated dienes such as butadiene, isoprene and 
chloroprene; non-conjugated dienes such as 1,4-pentadiene, 1,4-hexadiene, 
3-vinyl-1,5-hexadiene, 1,5-hexadiene, 3-methyl-1,5-hexadiene, 
3,4-dimethyl-1,5-hexadiene, 1,2-divinylcyclobutane, 1,6-heptadiene, 
3,5-diethyl-1,5-heptadiene, 4-cyclohexyl-1,6-heptadiene, 
3-(4-pentenyl)-1-cyclopentene, 1,7-octadiene, 1,8-nonadiene, 
1,9-decadiene, 1,9-octadecadiene, 1-cis-9-cis-1,2-octadecatriene, 
1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene,1,13-tetradecadiene, 
1,14-pentadecadiene, 1,15-hexadecadiene, 1,17-octadecadiene and 
1,21-docosadiene can be mentioned. Among these olefin monomers, conjugated 
dienes such as butadiene, isoprene and chloroprene may preferably be used 
and, particularly, butadiene is employed advantageously. 
In the present invention, for the styrene derivative, which is another 
monomer being capable of forming the copolymer, for example, 
methylstyrene, dimethyl styrene, ethyl styrene, diethylstyrene, isopropyl 
styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, 
benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, 
ethoxymethyl styrene, acetoxymethyl styrene, methoxy styrene, 
4-methoxy-3-methyl styrene, dimethoxy styrene, chloro styrene, dichloro 
styrene, trichloro styrene, tetrachloro styrene, pentachloro styrene, 
bromo styrene, dibromo styrene, iodo styrene, fluoro styrene, trifluoro 
styrene, 2-bromo-4-trifluoro styrene, 4-fluoro-3-trifluoromethyl styrene, 
vinyl benzoic acid, and vinyl methyl benzoate can be mentioned. styrene, 
The content of the diolefin monomer in the copolymer according to the 
present invention is preferably 10 to 60% by weight and, particularly, 15 
to 40% by weight of the total copolymer. 
Particularly, it is preferable that the content of styrene is 70 to 40% by 
weight of the total copolymer. 
Further, for the monomer containing two or more vinyl group, acryloyl 
group, methacryloyl group or allyl group in the molecule, for example, 
divinyl benzene, 1,5-hexadiene-3-in, hexatriene, divinyl ether, 
divinylsulfone, diallyl phthalate, diallyl carbinol, diethylene glycol 
dimethacrylate, trimethylolpropane trimethacrylate and trimethylolpropane 
dimethacrylate, which are known as a linking agent added on the 
polymerization of a vinyl monomer, can be mentioned. 
The copolymer used in the present invention is a latex, the gel fraction of 
which is 50 to 95% by weight. 
Herein the term "gel" denotes a copolymer in which copolymer constituents 
are polymerized in three dimensions. When a copolymer ingredients are 
copolymerize three-dimensionally as the copolymer according to the present 
invention, solubility of the copolymer to a solvent varies depending on 
the degree of three dimensional polymerization. That is to say, the higher 
the degree of three dimensional polymerization is, the lower becomes the 
solubility of the copolymer in the solvent. Accordingly, the degree of 
three-dimensional polymerization ma be assumed from its solubility. 
Of course, since the solubility varies depending on the solvent to be used, 
and, therefore, the definition of the three-dimensional polymerization 
varies depending on the solvent, however, in the present invention, the 
term "gel" denotes the state of polymerization in tree dimensions and the 
degree of the three-dimensional polymerization is to an extent, under 
which the polymer is not soluble in tetrahydrofurane when it is dipped in 
it at 20.degree. C. for 48 hours. 
The polymerization method of diene-type polymers are disclosed in detail, 
for example, in U.S. Pat. Nos. 2,852,386, 2,853,4547, 3,411,911, 
3,411,912, and 4,197,127; Belgian Patent Nos.688,882, 691,360 and 712,823; 
Japanese Patent Examined Publication No. 5331(1970); Japanese Patent 
O.P.I. Publication Nos. 18540(1985), 130217(1976), 137831(1983) and 
50240(1980). 
The average particle size of the diene-type polymers is preferably 0.005 to 
2.0 .mu.m and, particularly preferably 0.01 to 0.8 .mu.m. 
In the case of the diene-type polymers polymerized in the organic solvent, 
It can be employed by dispersing the polymer in water and replacing the 
organic solvent with water under the condition of reducing pressure. 
The polymer used in the first subbing layer is prepared as an aqueous 
dispersion (latex), and, if necessary, it is preferable to this aqueous 
dispersion a necessary additive including, for example, a crosslingking 
agent, a surface active agent, a swelling agent, a matting agent, and an 
antistatic agent. For the crosslingking agent, for example, triazine 
compounds disclosed in U.S. Pat. Nos, 3,325,28, 3,288,775 and 3,549,377 
and Belgian Patent Nos. 6,602,226; dialdehyde type compounds disclosed in 
U.S. Pat. Nos. 3,291,624 and 3,232,764; French Patent No. 1,543,694 and 
British Patent No. 1,270,578; epoxy compounds disclosed in U.S. Pat. No. 
3,091,537 and Japanese Patent Examined Publication No. 49-26580(1974); 
vinyl-type compounds disclosed in U.S. Pat. No. 3,642,486; aziridine-type 
compounds disclosed in U.S. Pat. No. 3,392,024; ethyleneimine-type 
compounds disclosed in U.S. Pat. No. 3,549,378 and methylol-type compounds 
can be mentioned. Among these compounds, dichlorotriazine derivatives are 
preferable. 
In the first subbing layer according to the present invention, it is 
preferable that a water-soluble polymer is incorporated for the purpose of 
improving coating performance. 
As for the water-soluble polymer, for example, hydroxyethyl cellulose(HEC), 
carboxymethyl cellulose(CMC), methyl cellulose(MC), hydroxypropylmethyl 
cellulose(HPMC), ethylhydroxyethyl cellulose(EHEC), modified hydroxyethyl 
cellulose(HMHEC),poly(vinyl pyrrolidone)(PVP), polyethylene oxide(PEO), 
xanthane, cationic hydroxyethyl cellulose(CATHEC), polyvinyl alcohol(PVA), 
poly(acrylamide), sodium alginate and carbopol(registered trademark) 
acrylamide viscosity-increasing composition can be mentioned. The 
water-soluble polymer of the present invention have a water-solubility of 
not less than 0.1 % by weight at a temperature of 25.degree. C., and it is 
preferable that the water-soluble polymer is contained in an amount of 0.5 
to 5% by weight of the subbing layer. 
Sodium carboxymethyl cellulose(CMC) which is useful to practice the present 
invention can be obtained from various materials. One example is CMC-7LX(a 
product of Aqualon Ltd., Wilminton, Del.). This product usually shows 
aqueous viscosity of 200 to 1000 mPa.s under an aqueous 5% concentration 
by weight and carboxymethyl substitution degree of 0.65 to 0.80. Needless 
to say that these other kinds of CMC, which are applicable to the present 
invention, has wide molecular weight range and various carboxymethyl 
substitution degrees. 
Methyl cellulose(MC) and hydroxyethyl cellulose(HEC) are sold by Aqualon 
Company, ethylhydroxy cellulose is sold by Berol Nobel, and 
hydroxypropylmethyl cellulose is sold by Aqualon Company and Dow Chemical 
Company. 
Next, the compound by represented by Formula I is explained in detail. 
##STR2## 
wherein R.sub.1 and R.sub.2 each represents a straight or an branched 
alkyl group having a carbon number of 1 to 18, M represents a cation, and 
n represents an integer of 1 to 50. 
The compound represented by Formula I of present invention is an 
alkylarylpolyethersulfate compound and, when a specific balance between 
the number of carbon atoms in the alkyl group introduced into the aryl 
group and the polymerization degree of the polyether structure, is 
attained, preferable surface activity and preferable emulsion stability 
can be obtained, so that the smooth and uniform film-forming property of 
the subbing layer are achieved. 
As for the alkyl group represented by R.sub.1 and R.sub.2 in Formula 1, a 
branched alkyl group is preferably employed, and two branched alkyl groups 
is particularly preferably employed. 
The cation represented by M may be optional so far as it does not 
jeopardise the surface activity and the water-solubility of the compound, 
however, potassium, sodium and ammonium ions are usually employed. 
Further, n is preferbly an integer of 1 to 30, and more preferably, of 1 to 
13. 
Below, specific representative compounds represented by Formula I! are 
given, however, the scope of the invention is not limited by these. 
##STR3## 
As for the electrically conductive compounds which can be incorporated in 
the subbing layer according to the present invention, for example, 
polymers or copolymers having a structural unit represented by Formula 2, 
can be mentioned as given below. 
##STR4## 
In the formula, m and n each represents an integer; M represents a hydrogen 
atom, an alkaline metal or an alkaline earth metal and X represents other 
monomer being capable of copolymerization. 
As for the other monomer capable of copolymerization, for example, a 
styrene compound such as styrene, .alpha.-methytlstyrene, vinyltoluene and 
p-methylstyrene; acrylic esters such as methyl acrylate, ethyl acrylate, 
butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, 2-hydroxyethyl 
acrylate and 2-hydroxyethyl methacrylate; a mono- or di-carboxylic acid 
anhydride such as acrylic acid, methacrylic acid, crotonic acid, maleic 
acid, fumaric acid and itaconic acid; an aliphatic conjugated diene such 
as butadiene, isoprene, 2-chloro-1,3-butadiene and 1-chloro-1,3-butadiene; 
a vinyl cyano compound such as acrylonitrile and methacrylonitrile; vinyl 
chloride, vinylidene chloride, vinylethylketone, vinylmethylether, vinyl 
acetate, vinyl formate, allyl acetate, methaallyl acetate, acrylamide, 
N-methylol acrylamide, glycidyl acrylate, glycidyl methacrylate, acrolein 
and allyl alcohol can be mentioned. 
In the present invention, it is preferable in the view of anti-static 
property, transparency and adhesion property of the support that the 
electrically conductive compound preferably contains the other monomer 
capable of copolymerization in an amount of 10 to 50 mole %. Although 
there is no specific limitation as to the number average molecular weight 
of the polymeric compound measured by GPC (Gel Permeation Chromatography), 
however, in the view of transparency after biaxial stretching, it is 
preferably 500 to 1,000,000 and, more preferably, 1,000 to 10,000. In the 
present invention, the electrically conductive compound is added at the 
time of preparing a coating solution. 
As for the counter ion for the sulfonic acid in the structural unit, for 
example, H.sup.+, Na.sup.+, K.sup.+, NH.sub.4.sup.+, Li.sup.+ and 1/2 
Ca.sup.+ may be mentioned and, among these, H.sup.+ and NH.sub.4.sup.+ are 
preferable in view of anti-static property and transparency. 
Polyglycerin incorporated in the subbing layer composition according to the 
present invention, a compound represented by the formula is preferable. 
EQU HO(CH.sub.2 CH(OH)CH.sub.2 O).sub.n H (2.ltoreq.n.ltoreq.20) 
In the present invention, polyglycerin is contained in an amount of 0.01 to 
50% by weight, and more preferably, of 5 to 40% by weight of the total 
solid ingredients of the subbing layer composition prepared in the weight 
ratio of the electrically conductive compound to the polymeric composition 
containing polyester and a styrene polymer as the structural constituents, 
being 70 to 15:30 to 85. 
By incorporating poly glycerin in the subbing layer composition, it becomes 
possible to prevent coagulation or gelation of said composition, and the 
preferable transparency may be achieved. 
In addition, in the subbing layer composition according to the present 
invention may comprise an anionic surface active agent, a nonionic surface 
active agent, an aliphatic polyhydroxyl compound, a sulfonated compound of 
a natural water-soluble polymer, a carboxylation compound of a natural 
water-soluble polymer, a phosphoration compound of a natural water-soluble 
polymer, a sulfoalkylation compound of a natural water-soluble polymer, a 
alkylphosphoration compound of a natural water-soluble polymer or a salt 
thereof, an anti-blocking agent an organic or inorganic filler, a pigment, 
or an ultraviolet-ray absorbent within the range which does not fail to 
the advantage of the present invention. 
Coating of the subbing layer may be carried out after film-manufacturing 
process, however, if stretching of the subbing layer composition is 
possible, it may be carried out at an optional step such as a period prior 
to stretching in the longitudinal direction during the film-making 
process, at a period between stretching in the longitudinal direction and 
stretching in the lateral direction, or a period prior to heat treatment 
after stretching in the lateral direction. 
It is preferable that the film strength of the subbing layer composition is 
enhanced by using a hardening agent, including, for example, 
aldehyde-type, aziridine-type, isooxazole-type, epoxy-type, 
vinylsulfon-type, acryloyl-type, carbodiimide-type, triazine-type, 
polymer-type, maleimide-type, acetyrene-type, or methanesulfonate-type h 
hardening agent. 
The first subbing layer according to the present invention can be 
manufactured by coating a coating solution, in which coating composition 
according to the present invention is mixed, on the SPS film and drying 
it. 
The coated amount of the polymer used in the first subbing layer is 
preferably 100 to 1000 mg per square meter and the drying temperature of 
the subbing layer is set at 80.degree. to 200.degree. C. and, more 
preferably, 80.degree. to 140.degree. C. 
Further, it is preferable that this first subbing layer is provided within 
film-making step of the SPS film, or it is provided by coating on a film 
before completion of crystal orientation, and, subsequently, by carrying 
out stretching, heat-fixation and completing crystal orientation. 
In the present invention, the term "a film before completion of crystal 
orientation" means an unstretched film prepared by steps of a heat-melting 
step of a polymer and a film manufacturing step or an incompletely 
stretched film not having not a final stretching magnification such as a 
mono-axially stretched film which has been stretched only in longitudinal 
or lateral direction or an incompletely biaxially stretched film, wherein 
a further stretching in both longitudinal and lateral directions is 
carried out, so that the crystallization by orientation is completely 
finished. 
The concentration of this coating solution is usually not more than 20% by 
weight and, more preferably, not more than 15% by weight. Moreover, the 
coated amount is preferably 1 to 20 g and more preferably, 5 to 15 g per 1 
square meter of the film by the weight of the coating solution. 
As for coating method, various conventional coating methods can be 
employed. For example, a roll-coating method, a gravure-roll coating 
method, a spray coating method, an air-knife coating method, a bar coating 
method, a dip coating method and a curtain coating method can be used 
either individually or in combination. 
Incidentally, SPS film has a specific feature that dielectric loss is 
small. For this reason, it has a characteristic feature that once it is 
charged, it is hardly discharged naturally. 
Accordingly, a subbing layer coating condition is changed depending on the 
electric charge distribution, so that it is tend to occur uneven coating. 
Therefore, it is preferable to discharge by force before and after coating 
the subbing layer coating solution, 
The discharging method which is preferably applied to the present 
invention, includes, for example, a method of grounding rolls being 
contact with the transporting support, a method of spraying water 
vaporized by applying ultra-sonic waves, a method of neutralizing electric 
charge by generating ionized air with radioactive irradiation; a method of 
using a discharging brush; an applying high voltage method and a 
bomabarding ionized wind method. 
Further, when providing the first subbing layer, immediately before 
coating, the following surface treatments are preferably employed. 
This is because the SPS film has highly hydrophobic surface. In order to 
overcome this sort of problems, after surface activation treatment such as 
chemical treatment, mechanical treatment, corona discharge, flame 
treatment, ultra-violet-rays treatment, high frequency electromagnetic 
waves treatment, glow discharge treatment, active plasma treatment, laser 
treatment, mixed acis treatment or ozone oxidation treatment is carried 
out, the first subbing layer is provided, and, thereafter, a silver halide 
photographic sensitie emulsion layer is coated thereon. Among these 
treatments, corona discharge treatment, flame treatment and glow discharge 
treatment are particularly preferable. 
Further, the surface tension of the support is preferably 50 to 70 dyn/cm. 
Among these preferable surface treatments, the corona discharge treatment 
can be carried out with reference to the methods disclosed in, for 
example, Japanese Patent Examined Publication No. 48-5043(1973) and 
47-51905(1972); Japanese Patent O.P.I. Publication Nos. 47-28067(1972), 
49-83767(1974) 51-41770(1976), and 51-131576(1976). Discharge frequency is 
preferably 50 to 5000 KHz and, more preferably, 5 to several hundred KHz. 
If the discharging frequency is too low, stable discharge property may 
hardly be obtainable. It is also unpreferable that pinholes tend to be 
occurred on the subject. When, on the other hand, the frequency is to 
high, a special equipment for adjusting impedance may be required and this 
is unpreferable because it raises the price of the equipment. As regards 
treatment strength of the subject, it is 0.001 to 5 kV.A.min./m.sup.2 and, 
more preferably 0.01 to 1 kV.A.min./m.sup.2. Further, gap-clearance 
between the electrode and the electro-inductive roll is generally 0.5 to 
2.5 mm and, more preferably, 1.0 to 2.0 mm. 
Grow discharge treatment, which is another preferable surface treatment may 
be carried out with reference to the method disclosed in, for example, 
Japanese Patent Examined Publication Nos. 35-7578(1960), 36-10336(1961), 
45-22004(1970), 45-22005(1970), 45-24040(1970) and 46-43480(1971); U.S. 
Pat. Nos. 3,057,792, 3,057,795, 3,179,482, 3,288,638, 3,309,299, 
3,424,735, 3,462,335, 3,475,307 and 3,761,299; British Patent No. 997,093 
and Japanese Patent O.P.I. Publication No. 53-129262(1978). 
As discharging frequency, as known in the art, it is the direct current to 
several thousand MHz and, preferably, 50 to 20 MHz. As regards strength of 
the discharging treatment, it is 0.01 to 5 kV.A.min./m.sup.2 and, 
preferably 0.15 to 1 kV.A.min./m.sup.2 in the view to obtaining enhanced 
adhesion. Further, ultra-violet ray irradiation treatment, which is 
especially advantageous for the pre-treatment of the organic solvent-type 
subbing treatment, any one of the methods which are known in the art can 
be used. For example, those methods disclosed in the Japanese Patent 
Examinee Publication Nos. 39-14534(1964), 39-16094(1964) and 45-3828(1970) 
can be used. 
The surrounding gas composition at the time of glow discharge treatment has 
partial water vapor pressure of not less than 10 and not more than 100% 
and, more preferably, of not less than 40 and not less than 90%. Other gas 
than the water vapor consists of an air comprising oxygen, nitrogen, etc. 
The manner of quantitatively introducing the water vapor into the 
atmosphere can be attained by introducing the gas from a sampling tube 
attached to the glow discharging device to quadropole mass 
spetrometer(type MSQ-6150, a product of Nihon Shinkuu Co., Ltd.), and by 
analyzing the composition of the gas. 
When the glow discharge treatment is carried out while heating the support 
to be subject to surface treatment, the adhesion property can be improved 
in a short period of time and yellow stain occurence of the support can be 
reduced to a considerable degree. The pre-heating temperature, in this 
case, is set to be not less than 50.degree. C. and not more than the glass 
transition temperature(Tg) of the support, more preferably, not less than 
70.degree. C. and not more than Tg, and more preferably, not less than 
90.degree. C. and not more than Tg. For the specific method of raising the 
polymer surface temperature in the vacuum, for example, heating by the use 
of a infra-red ray heater and heating by getting the support into contact 
with a heat roller, can be mentioned. 
It is preferable that the glow discharge treatment is carried out by 
providing electrodes having a intermediate area as a cooling flow path in 
the lateral direction of the film while transporting the support. 
Discharging frequency is the direct current to several thousands MHz, 
preferably, 50 Hz to 20 MHz, more preferably, 1 KHz to 1 MHz. 
The discharging treatment strength is preferably 0.01 to 5 kV.A.min/m.sup.2 
and, more preferably, 0.15 to 1 kV.A.min./m.sup.2. 
It is preferable that the support to which glow discharge treatment has 
been completed is immediately cooled down its temperature by the use of a 
cooling roll, as disclosed in Japanese Patent O.P.I. Publication No. 
3-39106(1991). 
It is preferable that the treatment with ultra-violet ray-irradiation is 
carried out in accordance with the methods disclosed in Japanese Patent 
Examined Publication Nos. 43-2603(1968), 43-2604(1968) and 45-3828(1970). 
As a mercury lamp, a high pressure mercury lamp, which is made of quartz 
tube and wave length range of ultraviolet rays is preferably 180 to 380 
nm. Irradiation of the ultraviolet rays may be performed either during the 
stretching step of the support, at the time of thermal fixing or after 
thereof. 
Concerning the manner of ultraviolet rays irradiation, if no problems are 
caused when the surface temperature of the support is risen up to about to 
150.degree. C., then a high pressure mercury lamp having the main 
wavelength of 365 nm can be employed. In the case where treatment at low 
temperatures is required, then, a low pressure mercury lamp having the 
main wavelength of 254 nm may preferably be used. it is also possible to 
use an ozoneless-type high pressure mercury lamp or a low pressure mercury 
lamp. 
For the preferable manner of practicing irradiation, the irradiation amount 
of 20 to 10000 mJ/cm.sup.2 with a high pressure mercury lamp habing the 
main wavelength of 365 nm is preferable and, more preferably, 50 to 2000 
mJ/cm.sup.2. In the case that a low pressure mercury lamp having the main 
irradiation wavelength of 254 nm is used, the irradiation amount is 
preferably 100 to 10000 mJ/cm.sup.2 and, more preferably, 300 to 1500 
mJ/cm.sup.2. Treatment can be performed with reference to the methods 
disclosed, for example, in Japanese Patent Examined Publication Nos. 
39-12838(1964), Japanese Patent O.P.I. Publication Nos. 47-19824(1972), 
48-28067(1973) and 52-42114(1977). 
Gas to used for flame treatment can be any one of natural gas, liquid 
propane gas and city gas, however, mixing ratio with the air is important. 
This is because the effects of the fire-flame treatment is considered to 
be brought by plasma containing active oxygen and there are two important 
features, that is to say, activity(temperature) of the plasma and the 
oxygen content The decisive factor of the two features is the gas/oxygen 
ratio and when the gas reacts with oxygen neither too much nor too little, 
energy concentration becomes maximum and the activity of the plasma the 
highest. To be more specific, preferable mixing ratio of the natural 
gas/air in terms of volume is between 1/6 and 1/10 and, more preferably, 
between 1/7 and 1/9; In the case of liquid propane gas/air it is between 
1/14 and 1/22 and, more preferably, 1/16 and 1/19 and between 1/2 and 1/8 
and, more preferably between 1/3 and 1/7 in the case of town gas/air. 
Amount of flame treatment is generally 1 to 50 kcal/m.sup.2 and, more 
preferably 3 to 20kcal/m.sup.2. Distance between the front edge of the 
inner flame of the burner and the support is generally 3 to 7 cm and, more 
preferably, 40 to 6 cm. As the shape of the nozzle(s) of the burner, 
ribbon-type (by Flynn Burner, the U.S.), multi-hole type(by the Wise Ltd., 
the U.S.), ribbon-type(by Aerogen Ltd,, the U.K.), multi-hole in zigzag 
arrangement(by Kasuga Electric Co. Ltd., Japan) or zigzag multi-hole 
type(by Koike Oxygen Co.,Ltd., Japan) is preferable. Back-up roll which 
sustains the support is preferably made of a hollow cylinder roll, 
water-cooled so that the treatment can be performed at a predetermined 
temperature. 
In the present invention, it is preferable to provide a hydrophilic 
colloidal layer on the subbing layer. As for the hydrophilic polymer used 
in the present invention, for example, a polymer, a cellulose ester, a 
latex polymer and a polyester can be mentioned. The polymer includes, for 
example, gelatin, a gelatin derivative, casein, agar, sodium arginate, 
starch, polyvinyl alcohol, polyacrylicacid copolymer and maleic acid 
anhydride copolymer can be mentioned. As for cellulose ester, 
carboxymethyl cellulose, hydroxyethyl cellulose, etc. can be mentioned, As 
for the latex polymer, for example, a copolymer containing vinyl chloride, 
a copolymer containing vinylidene chloride, a copolymer containing 
acrylate, a copolymer containing vinyl acetate, and a copolymer containing 
butadiene can be mentioned. Among these the most preferable hydrophilic 
polymer is gelatin. As for gelatin, any one which is usually used in the 
art can be used, including, for example a lime-treated gelatin, an 
acid-treated gelatin, an oxygen-treated gelatin, gelatin derivative and 
modified gelatin. Among these, the most popularly used are a lime-treated 
gelatin and an acid-treated gelatin. These gelatin may comprise various 
kinds of impurities which are incorporated in the manufacturing steps 
thereof, including, for example 0.01 to 20,000 ppm of metals or an ion 
thereof,(such as Na, K, Li, Rb, Ca, Mg, Ba, Ce, Fe, Sn, Pb, Al, Si, Ti, 
Au, Ag, Zu and Ni); an ion (such as F, Cl, Br, I, a sulfate ion, a nitrate 
ion, an acetate ion, and an ammonium ion. Particularly, it is well known 
in the art that the lime-treated gelatin contains calcium and magnesium 
ions. The content of these ions is usually to 10 to 3,000 ppm, preferably 
not more than 1000 ppm and, still more preferably, not more than 500 ppm 
in the view of properties of the subbing layer 
The subbing solution can contain, if necessary, a variety of additives 
including, for example, a surface active agent, an anti-static agent, an 
anti-halation agent, a coloring dye, a pigment, a coating aid and an 
anti-foggant in addition to the above-mentioned. 
As for gelatin hardener, for example a chromium salt such as chromium 
alunite; an aldehyde compound such as formaldehyde and glutaraldehyde; an 
isocyanate, an epichlorohydrin resin, polyamide-epichlorohydrin resin (as 
disclosed in Japanese Patent Examined Publication No. 49-26580(1974) and 
Japanese Patent O.P.I. Publication No. 51-3619(1976); a cyanuric chloride 
compound such as those disclosed in Japanese Patent O.P.I. Publication 
Nos. 47-6151(1972), 47-33380(1972), 54-25411(1983) and 56-130740(1981); a 
vinylsulfone or a sulfonyl compound such as those disclosed in Japanese 
Patent Examined Publication Nos. 47-24259,(1972) and 50-35807(1975), 
Japanese Patent O.P.I. Publication Nos. 49-24435(1974), 53-41221(1978) and 
59-18944(1984); a carbamoyl ammonium salt compound such as those disclosed 
in Japanese Patent publication Nos. 56-12853(1981) and 58-32699(1983), 
Japanese Patent O.P.I. Publication Nos. 49-51945(1974), 51-59625(1976) and 
61-9641(1986); an amidinium-type compound such as those disclosed in 
Japanese Patent O.P.I. Publication Nos. 61-225148(1986); a 
carbodiimide-type compound such as those disclosed in Japanese Patent 
O.P.I. Publication Nos. 65-126125(1990) and 52-48311(1977); a pyridiniuym 
salt-type compound such as those disclosed in Japanese Patent Publication 
No. 58-50699(1983), Japanese Patent O.P.I. Publication Nos. 
52-544427(1977), 57-44140(1982) and 57-46538(1982) and other compounds 
such as those disclosed in Belgian Patent No. 825,726, U.S. Pat. No. 
3,321,313, Japanese Patent O.P.I. Publication Nos. 50-38540(1975), 
52-93470(1977), 56-43353(1981) and 58-113929(1983) can be mentioned. 
In the subbing layer according to the present invention, organic or 
inorganic fine particles can be incorporated as matting agent within the 
extent which does not jeopardise transparency or graininess of the image 
to be produced. 
As inorganic matting agent, for example, silica dioxide, titanium dioxide, 
calcium carbonate, and magnesium carbonate can be used. 
As organic fine particle matting agent, for example, polymethyl 
methacrylate, cellulose acetate propionate, polystyrene, a processing 
solution-soluble compounds disclosed in U.S., Pat. No. 4,142,894 and 
polymers disclosed in U.S. Pat. No. 4,396,706 can be used. 
Average particle size of the above-mentioned fine particle matting agent is 
preferably 0.01 to 10 .mu.m and, more preferably 0.05 to 5 .mu.m, and the 
fine particle matting agent is preferably contained in an amount of 0.5 to 
600 mg/m.sup.2 and, more preferably, 1 to 400 mg/m.sup.2 of the subbing 
layer. 
The subbed film thus obtained is subsequently provided with the layers in 
order according to the manner mentioned above, adhesive property may 
further be improved by passing through a heat treatment mentioned below. 
As the first heat treatment process, it is carried out at a temperature of 
40.degree. C. to the glass transition temperature(Tg) of the support for 
the period for 0.1 minute to 1500 hours after the sublayer has been coated 
or before the silver halide emulsion layer has been coated. The adhesive 
property is improved by this treatment. 
The second heat treatment method can be carried out by treating the subbed 
support, which was once subjected to heat treatment at a temperature of 
not less than the transition point(Tg) of the support and less than the 
melting temperature (melting temperature measured by DSC) thereof, is 
again subjected to heat treatment at the temperature of not less than 
above-mentioned 40.degree. C. and less than the glasstransition 
temperature(Tg). 
The above-mentioned heat treatment is preferably carried out at the 
temperature of not less than the transition temperature(Tg) and less than 
the melting temperature, and more preferably, not less than Tg plus 
20.degree. C. and less than the crystallizing temperature of the 
support(measured by DSC). The heat treatment may also be performed at a 
pre-determined temperature within the above-mentioned temperature 
range(pre-heat treatment). Or this may be carried out while either 
decreasing(temperature-decreasing pre-heat treatment) or increasing the 
temperature(temperature-increasing pre-heat treatment). 
Period of the heat treatment is 0.1 minute to 1500 hours and, more 
preferably, not less than 1 minute and less than 100 hours. 
After this heat treatment, a post heat treatment is performed. From the 
temperature at the time of completion of this heat treatment to the 
initial temperature of the post heat treatment, rapid cooling may be done 
or gradually cooling may be done through the glasstransition temperature 
of the support to the initial temperature of the post heat treatment. 
Further, after once cooling down to the room temperature, it may be raised 
to the temperature of the post heat treatment. 
The post hear treatment may be carried out at the temperature of not less 
than 40.degree. C. and less than the glasstransition temperature of the 
support and, more preferably, not less than 20.degree. C. and less than 
the glasstransition temperature(Tg). 
The post heat treatment may be carried out at a fixed temperature of the 
above-mentioned temperature range, or it may also be carried out while 
cooling down or increasing the temperature. Among these the preferable 
embodiment is the heat treatment at the fixed temperature or the treatment 
while cooling down the temperature. In this case the average cooling rate 
is -0.01.degree. to -20.degree. C./hour and, more preferably, -0.1.degree. 
to -5.degree. C./hour. The period of this heat treatment is not less than 
0.1 minute and not more than 1500 hours and, more preferably, not less 
than 0.5 minute and not more than 200 hours. 
Although there are some preferable combinations of the pre-heat treatment 
and the post-heat treatment, it is preferable that, after the pre- heat 
treatment is conducted at the temperature of not less than the 
glasstransition temperature plus +20.degree. C. and not more than the 
crystallizing temperature, post-heat treatment is carried out at the 
temperature of the glasstransition temperature of the support to the 
glasstransition temperature -20.degree. C., while cooling down is carried 
out at a cooling rate of -0.1.degree. to -5.degree. C./hour. 
The light-sensitive photographic material according to the present 
invention comprises at least one silver halide emulsion layer provided at 
least one surface of the support. For the silver halide emulsion to be 
used for the silver halide emulsion layer may optionally be selected from 
various types of silver halide emulsions which are commonly known and used 
in the art. Further the silver halide emulsion can undergo chemical 
sensitization using a conventional method and it may be sensitized 
optically to a desired wavelength range by the use of a sensitizing dye. 
In this silver halide emulsion a variety of photographic additives 
including, for example, an anti-foggant, a hardener and a anti-oxidizing 
agent. For the binder for the silver halide emulsion, it is usually 
advantageous to use gelatin. 
The silver halide emulsion layer can be enhanced its film strength by the 
use of a hardening agent and as for such hardening agent, for example, an 
aldehyde-type compound, an aziridine-type compound, an iso-oxazole-type 
compound, an epoxy-type compound, a vinylsulfonyl-type compound, an 
acryloyl-type compound, a carbodiimide-type compound, a triazine-type 
compound, a polymeric compound, a maleimide-type compound, an 
acetyrene-type compound, a methanesulfonic acid ester-type compound, can 
be used either individually or two or more kinds in combination. Further 
other photographic additives including, for example, a plasticizer, 
synthetic polymer latex which is not or sparsely soluble in water, a 
coupler, a coating aid, an anti-static agent, a formalin scavenger, a 
fluorescent whitening agent, a matting agent, a lubricant, an image 
stabilizer, a surface active agent, anti-color foggant, a development 
accelerator, a development retarder and a bleach accelerating agent can 
also be incorporated. 
In the silver halide light-sensitive photographic material according to the 
present invention, a variety of hydrophilic colloidal layer can be 
provided in addition to the above-mentioned silver halide emulsion layer. 
Such hydrophilic colloidal layer includes, for example, a protective 
layer, a filtering layer, a back-coating layer, an anti-halation layer, an 
anti-irradiation layer and an intermediate layer, etc. can be mentioned.

EXAMPLE 1 
1! Synthesis Example of SPS 
Polymerization Example 1 
A SPS pellet was manufactured according to the method disclosed in Japanese 
Patent O.P.I. Publication No. 3-131843. 
Polymerization example is described below, All the operations were carried 
out in the argon atmosphere in the germ-free chamber. 
17.8 g (71 mmol) of cupric sulfate pentahydrate (CuSO.sub.4.5H.sub.2 O), 
200 ml of refined benzene and 24 ml of trimethyl aluminium were put in a 
glass vessel, of which inner volume is 500 ml, and agitated at 40.degree. 
C. for eight hours. 
After this was filtered with glass filter of No. 3A in the argon 
atmosphere, and the filtered solution was freeze-dried while it may not 
contact with the air. 
Then, after the pressure was returned to the normal pressure under argon 
atmosphere, the produced material was taken out. 
The produced material, tri-isobutyl aluminium pentamethylcyclopentadienyl 
titan trimethoxyd and pentadiethyl titan trimethoxyd were mixed, put into 
a stainless reaction vessel having the inner volume of 2 liters, and 
heated to 90.degree. C. in an oil bath. 
Then, 1 liter of sufficiently dehydrated and refined styrene and 70 ml of 
paramethyl styrene were added to this and the mixture was subjected to 
polymerization reaction at this temperature for 87 hours. Thereafter, one 
liter of methylene chloride was added, and adding a methanol solution of 
sodium methylate under agitation, the mixture was taken out of from the 
aseptic chamber (or germ-free chamber). 
After this was added dropwise gradually into 20 liters of methanol, 
filtered with a glass filter of No. 3 and washed with 1 liter of methanol 
for three times, and this was dried under reduced pressure for 12 hours. 
The weight average molecular weight measured by GPC and the glass 
transition temperature of the product were 430,000 and 98.degree. C., 
respectively. 
Polymerization Example-2 
Polymerization was carried out in the similar manner as in polymerization 
Example-1, except that in stead of styrene, 930 ml of sufficiently 
hydrated and refined styrene and 70 ml of .alpha.-methylstyrene were used. 
The glass transition temperature in this case was 97.degree. C. 
After respective products were made into a pellet by extruding machine, 
these pellets were crystallized at a temperature of 130.degree. C. 
2! Manufacture of the coating solution of the light-sensitive material 
Preparation of a coating solution for silver halide 
emulsion Em-1! 
The following &lt;Solution A&gt;and &lt;Solution B&gt;were mixed by the control 
double-jet mixing for eleven minutes. 
&lt;Solution 
______________________________________ 
Gelatin 5.6 g 
10% ethanol solution of 0.56 ml 
HO(CH.sub.2 CH.sub.2 O)n(CH.sub.2 CH.sub.2 CH.sub.2 O).sub.17 (CH.sub.2 
CH.sub.2 O)mH 
(m + n = 6) 
Sodium chloride 0.12 ml 
Conc. nitric acid 0.43 ml 
Distilled Water 445 ml 
______________________________________ 
&lt;Solution 
______________________________________ 
Silver nitrate 60 g 
Conc. nitric acid 0.208 ml 
Distilled water 85.2 ml 
______________________________________ 
&lt;Solution 
______________________________________ 
Gelatin 3 g 
10% ethanol solution of 0.3 ml 
HO(CH.sub.2 CH.sub.2 O)n(CH.sub.2 CH.sub.2 CH.sub.2 O).sub.17 (CH.sub.2 
CH.sub.2 O)mH 
(m + n = 6) 
Sodium chloride 20.2 g 
Sodium hexachlorodium (1% aqueous solution) 
20 ml 
Distilled water 85.61 ml 
______________________________________ 
&lt;Solution 
______________________________________ 
Gelatin 3 g 
10% ethanol solution of 
HO(CH.sub.2 CH.sub.2 O)m(CH.sub.2 CH.sub.2 CH.sub.2 O).sub.17 (CH.sub.2 
CH.sub.2 O)mH 0.14 ml 
(m + n = 6) 
Distilled water 48.8 ml 
______________________________________ 
Average grain size of the thus obtained silver halide grains was 0.12 .mu.m 
and the degree of mono-dispersity thereof was 8-15%. To the thus prepared 
emulsion, &lt;Solution D&gt;was added, and pH was adjusted at 6.0 with sodium 
carbonate and, subsequently, 200 mg of 
4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added, Thereafter, 
respective silver halide emulsions were washed and desalinated according 
to a conventional method and, then, &lt;Solution E&gt;was added as a 
preservative. 
&lt;Solution 
______________________________________ 
2-methyl-5-chloroisothiazole-3-one 
15 mg 
Pure water 0.3 ml 
______________________________________ 
To the above emulsion, 200 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene 
as a stabilizer and 3.6 g of gelatin were added. 
Further, the following additives were added to the coating solution, and 
added water to make the total volume of the coating solution to be 303 ml, 
to prepare the coating solution for silver halide emulsion Em-1. 
______________________________________ 
33%(W/V) aqueous solution of saponin 
2.2 ml 
20%(W/V) aqueous solution of sodium dodecylbenzene 
2.2 ml 
sulfonate 
4%(W/V) aqueous solution of sodium 1-decyl-2- 
0.3 ml 
(3-isopentyl)succinate-2-sulfonate 
20%(W/V) emulsion solution of polymer latex 
31.8 ml 
(cyclohexylmethacrylate/isononylacrylate/ 
glycidylacrylate/styrene-isoprene sulfonic acid) 
having an average particle size of 0.25 .mu.m 
2%(W/V) methanol solution containing a hydrazine 
7.5 ml 
derivative (A-1) 
5%(W/V) aqueous solution containing an amine 
4 ml 
compound (A-2) 
7%(W/V) aqueous solution containing citric acid 
0.4 ml 
2%(W/V) aqueous solution containing 
26.5 ml 
a nonionic surface active agent(A-3) 
0.5%(W/V) alkaline aqueous solution containing 
4 ml 
2-mercaptohypoxanthin 
5%(W/V) aqueous solution containing sodium 
10 ml 
ethylenediaminetetraacetic acid 
5%(W/V) methanol solution containing spirobis 
1.5 ml 
(3,3-dimethyl-5,6-dihydroxy indane) 
20%(W/V0 aqueous solution containing hydroquinone 
2.5 ml 
4%(W/V) aqueous solution containing a copolymer 
4 ml 
of styrene sulfonic acid and maleic acid 
5%(W/V) methanol solution containing 2-methyl-5- 
0.1 ml 
chloroisothiazole-3-one 
______________________________________ 
##STR5## 
Preparation of a coating solution for the protective layer P-1! 
A coating solution for the protective layer P-1 was prepared by adding and 
mixing the following additives, and added pure water to make the total 
volume to be 1414 ml, 
______________________________________ 
12%(W/V) aqueous solution containing gelatin 
250 ml 
4%(W/V) aqueous solution containing sodium 1-decyl-2- 
50 ml 
(3-isopentyl)succinate 2-sulfonic acid 
4%(W/V) solution of sodium 50 ml 
10%(W/V) aqueous solution containing sodium chloride 
22 ml 
Amorphous silica(average diameter: 3.5 .mu.m) 
2 g 
Amorphous silica(average diameter: 6 .mu.m) 
4 g 
0.08%(wt) methanol solution containing an anionic 
70 ml 
surface active agent (A-4) 
7%(W/V) aqueous solution containing citric acid 
5.1 ml 
2%(W/V) methanol solution containing (dimezon S) 
20 ml 
2%(W/V) aqueous solution containing the dye 
700 ml 
(A-5) given below 
4%(W/V) aqueous solution containing a copolymer 
22.7 ml 
of styrene sulfonic acid and maleic acid 
0.1%(W/V) aqueous solution containing 
6 ml 
2-bromo-2-nitro-1,3-propane diol 
Dye dispersion Bu 250 ml 
______________________________________ 
##STR6## 
Preparation of dye dispersion Bu! 
After dispersing a dye(A-6) given below at a quantity equivalent to 100 
mg/m.sup.2 as coated, which was dissolved in 200 ml of ethyl acetate 
together with 30 g of gelatin, 147 mg of citric acid, 400 mg of 
isopropylnaphthalene sulfonic acid and 3 g of phenol dissolved in pure 
water and made 250 ml in total, in a PD dispersing machine, removed 
ethylacetate while heating the mixture under reduced pressure, added pure 
water to make the total volume to be 250 ml and cooled to set the mixture, 
to prepare a dye dispersion containing dye having average grain diameter 
of 0.2 .mu.m. 
##STR7## 
Preparation of a coating solution for the backing layer 
BC-1! 
A coating solution for the backing layer BC-1 was prepared by adding and 
mixing the additives given below, and adjusting with pure water so that 
the total volume became 895 ml. 
______________________________________ 
Gelatin 32.4 g 
Pure water 696 ml 
6%(W/V) aqueous solution of dye (A-7) 
64 ml 
5%(W/V) aqueous solution of dye(A-8) 
24 ml 
33%(W/V) aqueous solution of saponin 
6.6 ml 
20%(W/V) polymer latex emulsion 
33.6 ml 
(Copolymer of cyclohexyl methacrylate, isononyl acrylate, 
glycidyl acrylate and styrene-isoprene sulfonic acid; 
average diameter: 0.11 .mu.m) 
10% solid fine powder dispersion of zinc oxide 
10 ml 
(average diameter: 0.15 .mu.m) 
Solid fine powder dispersion of 
10 ml 
(A-9; average diameter: 0.1 .mu.m) 
7%(W/V) aqueous solution of citric acid 
3.8 ml 
4%(W/V) aqueous solution of sodium styrene sulfonate 
23 ml 
______________________________________ 
##STR8## 
Preparation of a coating solution for the backing layer BP-1! 
A coating solution for the backing layer BP-1 was prepared by adding and 
mixing the additives given below, and adjusting with pure water so that 
the total volume became 711 ml. 
______________________________________ 
Gelatin 24.9 g 
Pure water 605 ml 
2%(W/V) dispersion of methyl methacrylate 
72 ml 
(average diameter: 7 .mu.) 
4%(W/V) aqueous solution containing sodium salt of 
11 ml 
1-decyl-2-(3-isopentyl) succinate-2-sulfonic acid 
4%(W/V) aqueous solution containing glyoxal 
4 ml 
Preparation of a solution containing a hardening agent 
BH-1 for adding to the backing layer inline! 
Pure water 27.22 ml 
Methanol 1.5 ml 
Hardening agent (A-10) shown below 
1.28 ml 
NaCl 0.005 g 
______________________________________ 
##STR9## 
Preparation of a coating solution for the silver halide emulsion layer! 
A coating solution for the silver halide emulsion containing AgBrI 
emulsion, which comprises mono-disperse twin-crystal core/shell-type 
silver halide grains, of which silver iodide content of 2.0 mol %, average 
grain diameter of 0.4 .mu.m, a grain diameter distribution width of 12%, 
average aspect ratio of 1.0 to 1.5 and ratio of {100} plane and 
{111}-plane is 64:36, and the following additives was prepared. 
______________________________________ 
1,1-dimethylol-1-bromo-1-nitromethane 
70 mg 
t-butyl catecol 400 mg 
Polyvinyl pyrrolidone (molecular weight: 10,000) 
1.0 mg 
Styrene-maleic acid anhydride copolymer 
2.5 g 
Nitrophenyl-treiphenyl phosphonium chloride 
50 mg 
2-anilino-4,6-dimercapto-s-triazine 
40 mg 
Ammonium 1,3-dihydroxy benzene-4-sulfonate 
4 g 
Sodium salt of 2-mercaptobenzimidazole-5-sulfonic acid 
1.5 mg 
C.sub.4 H.sub.9 OCH.sub.2 CH(OH)CH.sub.2 N(CH.sub.2 COOH).sub.2 
1 g 
1-Phenyl-5-mercaptotetrazole 
15 mg 
______________________________________ 
Preparation of a solution for the protective layer! 
Amount of additives used in the solution for the protective layer is given 
in terms of the amount per one liter of the solution. 
______________________________________ 
Lime-treated inert gelatin 68 g 
Acid treated gelatin 2 g 
Sodium-1-amyl-decylsulfo succinate 
0.3 g 
Poly(methyl methacrylate (matting agent having area an 
1.1 g 
average surface grain diameter of 3.5 .mu.m) 
Silica dioxide (matting agent having an average surface 
0.5in g 
diameter of 1.2 .mu.m) 
CH.sub.2 .dbd.CHSO.sub.2 CH.sub.2 OCH.sub.2 SO.sub.2 CH.dbd.CH.sub.2 
500 mg 
C.sub.4 F.sub.9 SO.sub.3 K 20 mg 
C.sub.12 H.sub.25 CONH(CH.sub.2 CH.sub.2 O).sub.5 H 
2.0 g 
C.sub.3 F.sub.17 SO.sub.2 N(C.sub.3 H.sub.7)(CH.sub.2 CH.sub.2 O).sub.15 
H 100 mg 
______________________________________ 
3! Preparation of a solution for the subbing treatment layer 
Solution for the first subbing layer A 
______________________________________ 
Styrene-butadiene latex (Nippol LX432A; product 
25 parts by weight 
of Nippon Zeon Co., Ltd.) 
Methyl cellulose (10%) 10.0 Parts by weight 
Silica-type matting agent (average diameter: 
0.5 part by weight 
3.0 .mu.) 
Sodium 2,4-dichloro-6-hydroxy-s-triazine 
0.5 part by weight 
Pure water 66 parts by weight 
______________________________________ 
Solution for the first subbing layer B 
______________________________________ 
Styrene-butadiene latex (Nippol LX432A; product 
25 parts by weight 
of Nippon Zeon Co., Ltd.) 
Silica-type matting agent (average diameter: 
0.5 part by weight 
3.0 .mu.) 
Sodium 2,4-dichloro-6-hydroxy-s-triazine 
0.5 part by weight 
Pure water 24 parts by weight 
______________________________________ 
Dye Dispersion 
To an aqueous solution, in which 5 parts by weight of a surface active 
agent(Triton X200, a product of Union Carbide co., ltd.)is dissolved in 
285 parts by weight of water, 1 part by weight of citric acid, and 12 
parts by weight of dye(A-11) were added and pre-dispersed with an 
ultrasonic mixer. Then this solution was put in a sand-mil (Igarashi 
machine manufacturing), added 1200 parts by weight of zirconium oxide 
beads and dispersed at 2000 rpm for 24 hours Diameter of the thus obtained 
solid dispersion dye was 0.1 .mu.m. 
Solution for the second subbing layer C 
______________________________________ 
Aqueous gelatin solution (10%) 
80 parts by weight 
Methyl cellulose (10%) 
20 parts by weight 
C.sub.12 H.sub.25 O(CH.sub.2 CH.sub.2 O).sub.10 SO.sub.3 Na 
4 parts by weight 
(Proxel) 0.3 part by weight 
Hardening agent (A-12) 
0.5 part by weight 
Add pure water to make the total volume of 1 liter. 
______________________________________ 
Solution for the second subbing layer D 
______________________________________ 
Aqueous gelatin solution (10%) 
140 parts by weight 
Matting agent (3 .mu.m silica) 
5 parts by weight 
Anion-nonion surface active agent (A-13) 
21 parts by weight 
Dye dispersion 75 parts by weight 
Add pure water to make the total volume to be 1 liter 
______________________________________ 
##STR10## 
4! Manufacture of a subbed support 
Manufacture of a subbed support 1 (for example) 
A SPS pellet, which was obtained in Synthesis Example 1 was melted at 
330.degree. C., extruded through a pipe on a cooled casting drum from a 
die-slit while applying electrostatic potential and cooled, to obtain a 
sheet, of which thickness is 1 mm. Said sheet was, after being pre-heated 
at 110.degree. C., stretched in the longitudinal direction with stretching 
magnification degree at 3.3 times while heating by infrared heater, and 
was further stretched in the lateral direction with the stretching 
magnification degree at 3.3 times. Then, after thermally fixed at 
230.degree. C., to obtain a film of 100 .mu.m thickness. After subjecting 
the both surfaces of the thus obtained film to corona discharge treatment, 
the both surfaces were discharged with an ion wind using an ion blower 
and, then, the coating solution for the subbing treatment A was coated on 
both surfaces one by one in order so that the dry thickness of the layer 
is set to be 1.0 .mu.m, and, subsequently dried at 160.degree. C. 
Then the solution C for the second subbing treatment was coated on both 
surfaces one by one in order so that the dry thickness becomes to be 0.2 
.mu.m, and, then dried at 140.degree. C. 
This subbed base was then subjected to heat treatment for two minutes and 
was wound up after transported at 75.degree. C. for ten minutes. This 
subbed substratum was cooled down to the room temperature spending three 
days. 
Manufacture of a subbed support 2(for comparison) 
In accordance with the disclosure of Japanese Patent O.P.I. Publication No. 
3-131343(1991), a hydrophilic subbing coating was carried out in place of 
providing the above-mentioned layers. 
______________________________________ 
Aqueous gelatin solution (5% by weight) 
9 parts by weight 
Pure water 90 parts by weight 
Aqueous formalin solution (4% by weight) 
1 part by weight 
______________________________________ 
The coating solution with the above-mentioned composition was coated on the 
film obtained in the above-mentioned Support 1 and dried at 100.degree. C. 
Manufacture of a subbed support 3 
After coating the solution for the first subbing treatment in the same 
manner as in the case of support 1, solution for the second subbing 
treatment D was coated and dried at 140.degree. C. Heat treatment was 
carried out in the same manner as support 1. 
Manufacture of subbed support 4 
The obtained sheet was pre-heated at 110.degree. C. and subsequently 
stretched in the longitudinal direction at a stretching magnification of 
3.3 times. Then the both surfaces were subjected to corona discharging 
treatment. Next, after the both surfaces were discharged with an ion bower 
(Type RH-20), the above-mentioned solution for the first subbing treatment 
A was coated with a wire bar coater so that the coating thickness after 
biaxial stretching becomes to be 0.2 .mu.m, stretched in the lateral 
direction with a stretching magnification at 3,3 times and thermally fixes 
at 230.degree. C. 
The solution for the second subbing treatment C was coated on both surfaces 
in the same manner as in the case of subbed support 1 and, thereafter, the 
support was dried and thermally treated. 
Manufacture of subbed support 5 
Coating was carried out in the same manner as in the case of support 1, 
however in this example glow discharging treatment was carried out in 
stead of corona discharging treatment under the partial moisture pressure 
at 75% and 0.15 Torr. 
5! Coating of emulsion layers 
Both surfaces of these subbed Supports 1,2,3 and 5 were simultaneously 
coated with Em-1 using a slide hopper. 
With respect to support 4, both surfaces were simultaneously, provided that 
one surface was coated with Em-1 and the other surface was provided width 
a backing layer while in-line adding the hardening solution BH. 
In both cases the protective layer was coated simultaneously with the 
emulsion layer. 
6! Evaluation of Properties 
(Evaluation of uneven coating) 
Subbed supports 1,2.3 and 5 were subjected to the normal processing for a 
silver halide light-sensitive materials for X-ray use, and with respect to 
support 4, a normal processing for the light-sensitive materials for 
photo-lithography were conducted and evaluated visually. 
1. remarkable uneven coating was observed and the emulsion layer is 
partially peeled off. 
2. remarkable uneven coating was observed and partial repulsion was 
observed. 
3. Uneven coating having rainbow color was observed. 
4. A slight uneven coating was observed when looked obliquely. 
5. No uneven coating observed. 
(Evaluation of adhesion) 
Adhesion before processing 
Emulsion adhesion 
After coating the emulsion layer, the surface of the silver halide emulsion 
layer of the samples were cut with a razor blade in cross stripes so that 
the scratches reaches the SPS film, put an adhesive Sellotape the surface 
of the scratched film and the thus scratched film surface was rapidly 
peeled off and the adhesion of the silver halide emulsion layer was 
evaluated according to the following five standards. 
Standards for evaluation 
1. Adhesive force is very weak, and a silver halide emulsion layer is 
completely peeled off. 
2. The peeled off area is not less than 50%, and not less than 100%. 
3. The peeled off area is not less than 20%, and not less than 50%. 
4. The adhesive force is strong, and the peeled off area is not less than 
5%, and not less than 20% 
5. The adhesive force is very strong and the peeled off area is less than 
5%. 
When the standard for evaluation is not less than 4, it can be considered 
that the silver halide light-sensitive material has safficiently strong 
adhesive force for practical use. 
Wet-emulsion-adhesion 
The samples were dipped in distilled water, and after 30 seconds, a silver 
halide emulsion layer is scratched with a pointed needle in order that 
scratch becomes the lattice of damages and the emulsion layer of the 
respective samples were rubbed strongly for the period of ten seconds with 
hands with rubber gloves thereon. Strength of adhesion was evaluated in 
five grades by measuring the area of the silver halide emulsion layer 
according to the similar standards as in the case of the pre processing 
adhesion. Results are shown in Table 1 
TABLE 1 
______________________________________ 
Subbed Support 
Uneven Emulsion Wet-emulsion 
No. Coating adhesion adhesion 
______________________________________ 
1 (Invention) 
4 4 5 
2 (Comparative) 
2 2 1 
3 (Invention) 
4 5 5 
4 (Invention) 
5 5 5 
5 (Invention) 
5 5 5 
______________________________________ 
It is obviously understood that the supports of the present invention show 
excellent properties. 
On the contrary, comparative samples show insufficient properties. 
EXAMPLE 2 
Supports Nos. 5 to 8 having silver halide emulsion layer respectively, were 
prepared in the same manner as 2 ! through 6! above, except that the 
following mentioned, and the same evaluations as in Example 1 were carried 
out. 
Solution for the first subbing treatment E 
______________________________________ 
Styrene-butadiene latex No. 0545 (a product of 
20 parts by weight 
Nippon Synthetic Rubber) 
Sodium dodecylbenzene sulfonate 
2 parts by weight 
Silica-type matting agent (average diameter: 3.0 .mu.m) 
1 part by weight 
Sodium 2,4-dichloro-6-hydroxy-s-triazine 
1 part by weight 
Pure water 76 parts by weight 
______________________________________ 
Solution for the first subbing treatment F 
______________________________________ 
Acrylonitrile-butadiene latex No. 0910 (product of 
25 parts by weight 
Nippon Synthetic Rubbers co., Ltd.) 
Sodium dodecylbenzene sulfonate 
2 parts by weight 
Silica-type matting agent (average diameter: 3.0 .mu.m) 
2 parts by weight 
2,6-diethyleneiminehexane 
1 part by weight 
Pure water 70 parts by weight 
______________________________________ 
Solution for the second subbing treatment G 
______________________________________ 
Aqueous gelatin solution (10%) 
80 parts by weight 
Methyl cellulose (10%) 
20 parts by weight 
Compound 7 4 parts by weight 
Proxel 0.3 part by weight 
Crystaline tin oxide 80 parts by weight 
Silica-type matting agent 
5 parts by weight 
(average diameter: 3.0 .mu.m) 
______________________________________ 
##STR11## 
Manufacture of support 6 with silver halide emulsion (for example) 
A SPS pellet, which was obtained in polymerization Example 2 was melted and 
extruded at 320.degree. C. and casted on a casting drum, while applying 
electrostatic potential and cooled, to obtain a SPS sheet having thickness 
of approximately 1 mm. Obtained sheet was, after being pre-heated at 
110.degree. C., stretched in the longitudinal direction with stretching 
magnification degree at 3.3 times, and was further stretched in the tenter 
in the lateral direction with the stretching magnification degree at 3.3 
times. Then, after fixing thermally at 230.degree. C., the film was 
thermally reluxed at 110.degree. C. by approximately 3% by reducing width 
of the clip. After undergoing corona discharge on one surface of the thus 
obtained 100-.mu.m-thick film, the surface of the film was discharged by 
moisting water-vapor. Then, solution for the first subbing treatment E was 
coated thereon so that dry thickness of the layer became to be 0.4 .mu.m 
and dried at 130.degree. C. Then after conducting corona discharge on this 
layer coating, the solution for the second subbing treatment was coated so 
that dry thickness of the layer may be 0.1 .mu.m and was dried at 
150.degree. C. Next, the other surface of the film was treated with flame, 
coated with the solution for the first subbing treatment F so that the dry 
thickness of the layer became 0.15 .mu.m and was dried at 125.degree. C. 
Further thereon after conducting flame treatment, the solution for the 
second subbing treatment B was coated so that the dry thickness of this 
layer may be 0.1 .mu.m and was dried at 170.degree. C. The obtained film 
was wound up while gradually cooling down the temperature to 80.degree. C. 
and then, maintained at 50.degree. C. for three days. 
By the use of the thus obtained subbed support, a backing layer while 
inline adding a hardening agent BH-1 on the first coated surface, and a 
silver halide emulsion Em-1 on the second coated surface, were coated 
simultaneously on both surfaces of the support by the use of a slide 
hopper-type coater. In all cases, the protective layer was provided 
simultaneously with the emulsion layer. 
Support 7 with an silver halide emulsion 7 (for comparison) 
On the both surfaces of a SPS film support prepared in the same manner as 
Support 6, after undergoing corona discharge treatment, the following 
coating composition was coated according to the method disclosed in 
Japanese Patent O.P.I. Publication No. 3-131843(1991) so that the dry 
thickness of the layer may be 0.7 .mu.m and dried at 100.degree. C., to 
prepare a subbed support 7 for comparison. 
______________________________________ 
Aqueous gelatin solution (5% by weight) 
9 parts by weight 
Pure water 90 parts by weight 
Formalin (4% by weight) 
1 part by weight 
______________________________________ 
On both surfaces of this layer, a silver halide emulsion Em-1 and the 
backing layer were provided in the same manner as in the case of subbed 
support 6, simultaneously with the protective layer using a slide hopper 
coater. 
Support-8 with emulsion 
A SPS pellet, which was obtained in polymerization Example 2 was melted and 
extruded at 320.degree. C. and casted on a casting drum while applying 
electrostatic potential. Then the both surfaces of the thus obtained 
approximately 1 mm thick sheet underwent corona discharge treatment. This 
sheet was, after being pre-heated at 110.degree. C., stretched in the 
longitudinal direction using an infra-red heater with stretching 
magnification degree of 3.3 times. Then, the both surfaces of this sheet 
underwent flame treatment and were coated with the solution for the first 
subbing treatment F so that the dry thickness of the layer became to be 
0.2 .mu.m and after this was dried in the tenter at 100.degree. C., was 
further stretched in the lateral direction with the stretching 
magnification degree of 3.3 times, and fixed thermally at 230.degree. C. 
Thus obtained film was thermally relaxed at 160.degree. C. by 
approximately 3% by reducing width of the clip. The obtained film was 
wound up at 110.degree. C. around a core with the outer diameter of 40 cm. 
This stainless core was cooled down at a cooling rate at 1.degree. C./min. 
to 70.degree. C. and then, maintained at this temperature for three days. 
After the temperature of the core was cooled down to the room temperature, 
the solution for the second subbing treatment G and the solution for the 
second subbing treatment D were coated, after corona discharging 
treatment, on the inner surface and on the outer surface of the roll film, 
respectively so that dry thickness of the respective layers became to be 
0.1 .mu.m, and dried at 65.degree. C. On the outer surface thereof Em-1 as 
an emulsion layer and on the inner surface thereof a backing layer while 
inline-adding a hardening agent BH-1, were provided, respectively together 
with a protective layer by simultaneous coating. 
With respect to the thus obtained supports 6 through 8 with silver halide 
emulsion, after they are left in the atomospheric condition at 23.degree. 
C., 55% R.H., adhesion strength of the both sides of the support was 
evaluated according to the same standards described in 6! above. 
TABLE 2 
__________________________________________________________________________ 
Emulsion Emulsion Emulsion 
adhesion before 
adhesion during 
adhesion after 
processing 
processing 
processing 
Support with 
Uneven 
Emulsion 
BC Emulsion 
BC Emulsion 
BC 
Emulsion No. 
Coating 
Side side 
Side Side 
Side Side 
__________________________________________________________________________ 
6 5 4.5 4.5 5 5 5 4.5 
(According to 
the Invention) 
7 (Comparison) 
2.5 2 1.5 1.5 1 1 1 
8 5 5 5 5 5 5 5 
(According to 
the Invention) 
__________________________________________________________________________ 
It is obvious from Table 2 that Support with an emulsion Nos 6 and 8 
according to the present invention have excellent adhesion property, while 
Support with an emulsion No. 7, which is for comparison has only inferior 
properties. 
EXAMPLE 3 
The present invention is further explained with reference to working 
examples, however, the embodiments of the present invention are not 
limited to these, 
&lt;Preparation of modified polyester A-1&gt; 
800 g of a polyester (product of Eastman Kodak Co.: WD-size)was put into 
5600 g of heated water and stirred for five hours to dissolve. Then 200 g 
of styrene and 1.0 g of ammonium persulfate were added to this solution 
and reaction was performed at 80.degree. C. for eight hours, to produce a 
polymer. In the present invention, the polyester obtained by the 
above-mentioned is defined as modified polyester. 
&lt;Preparation of modified polyester A-2&gt; 
Modified polyester A-2 was prepared in the same manner as in the 
preparation of A-1, except that styrene/methyl methacrylate/acrylic 
acid=6/2/2 was replaced with styrene. 
&lt;Preparation of modified polyester A-3&gt; 
Modified polyester A-3 was prepared in the same manner as in the 
preparation of A-1, except that styrene/glycidyl methacrylate=8/2 was 
replaced with styrene. 
&lt;Preparation of modified polyester A-4&gt; 
Modified polyester A-4 was prepared in the same manner as in the 
preparation of A-1, except that 
styrene/acrylamide/glycidylmethacrylate=7/2/1 was replaced with styrene. 
&lt;Preparation of Support-1&gt; 
SPS pellet, which was obtained in Synthesis Example 1 was melted at 
330.degree. C., extruded through a pipe on a cooled casting drum from a 
die-slit while applying electrostatic potential and cooled, to obtain a 
SPS unstretched sheet. Said unstretched sheet was, after being pre-heated 
at 115.degree. C., stretched in the longitudinal direction with stretching 
magnification degree of 3.3 times, and was further stretched in the 
lateral direction with the stretching magnification degree of 3.3 times. 
Then, after fixing thermally at 225.degree. C., while relaxing it slightly 
in the lateral direction, the sheet was subjected to heat relaxation at 
170.degree. C. for five minutes and cooled down to 100.degree. C., and 
further thermally treated at 80.degree. C. for about ten minutes, to 
obtain a support. 
Then, the both surfaces of the thus obtained support were subjected to 
corona discharging treatment and, after coating the composition mentioned 
below was coated, it was dried at 140.degree. C. for three minutes, to 
obtain Support-1. 
______________________________________ 
Modified polyester A-1 66 g 
Compound I-7 (1.0% aqueous solution) 
3 g 
Sodium 2,4-dichloro-6-hydroxy-s-triazine 
2 g 
(1.5% aqueous solution) 
Add pure water to make the total volume to be 
100 g. 
______________________________________ 
&lt;Preparation of Support 2&gt; 
Support 2 was prepared in the same manner as in Support 1, except that the 
modified polyester is replaced with a polyester of A-2. 
&lt;Preparation of Support 3&gt; 
66 g of modified Polyester 3 and Compound I-3(1.0% aqueous solution) 
according to the present invention were mixed and added pure water to make 
the total volume to be 100 g. 
A SPS pellet, which was obtained in Synthesis Example 1 was melted at 
330.degree. C., extruded through a pipe on a cooled casting drum from a 
die-slit while applying electrostatic potential and cooled, to obtain a 
SPS unstretched sheet of 1000 .mu.m. Said unstretched sheet was, after 
being pre-heated at 115.degree. C., stretched in the longitudinal 
direction with stretching magnification degree of 3.3 times, and was 
further stretched in the lateral direction with the stretching 
magnification degree of 3.3 times. Then, after fixing thermally at 
225.degree. C., while relaxing it slightly in the lateral direction, the 
sheet was subjected to heat relaxation at 170.degree. C. for five minutes 
and cooled down to 100.degree. C., and further thermally treated at 
80.degree. C. for about ten minutes, to obtain Support 3. 
&lt;Preparation of Support 4&gt; 
Modified polyester A-4 and electroconductive Compound C were mixed at a 
weight ratio of A-4 to C being 55:35 by and then adjusted so that solid 
ingredient is 10% by weight. To 100 parts by weight of the thus prepared 
solution, 0.1 part by weight of Compound I-5 and 2 parts by weight of poly 
glycerin D were added, to prepare a solution for subbing treatment. 
##STR12## 
Support 4 was prepared in the same manner as in the preparation of Support 
3. 
&lt;Preparation of Support 5&gt; 
According to the method disclosed in Japanese Patent O.P.I., Publication 
No. 3-131843(1991), an aqueous gelatin solution (5% by weight) and an 
aqueous formalin solution (4% by weight) were mixed at a proportion by 
weight of 7:1 and added pure water to make the total to be 100 parts. Then 
this solution was coated on the SPS sheet so that dry thickness became 0.7 
.mu.m and dried. 
After an anti-electrostatic layer and a anti-halation layer were provided 
on the respective supports thus prepared, the following photographic 
constituent layers and a backing layer were formed by the use of a curtain 
coater. Herein, as the silver halide emulsion, a silver chlorobromide 
emulsion comprising tabular-shaped silver chlorobromide grains, silver 
chloride content of which is 60 mol % and inside of which has been doped 
with iridium at a quantity of 10.sup.-6 mol per mol of silver was used. 
The emulsion was sensitized with 8.2 mg of sodium thiosulfate, 163 mg of 
potassium thiocyanate, 5.4 mg of auric chloride and 2.0 mg of 
diphenylpentachlorophenyl chloride per 1 mol of silver, respectively. 
Average grain size and the average aspect ratio of the silver halide 
grains contained in the higher-sensitive emulsion layer are 0.13 .mu.m and 
1.5, respectively, those in the lower-sensitive layer are 0.14 .mu.m and 
2, respectively. and sensitivity difference between the higher-sensitive 
emulsion layer and the lower-sensitive emulsion layer was 32%. 
&lt;Photographic constituent layers&gt; 
First Layer(Reflection light-absorbing layer) 
______________________________________ 
Gelatin 0.3 mg/m.sup.2 
Matting agent (Average grain size: 2 .mu.m) 
0.02 g/m.sup.2 
solid dispersion dye (average grain size: 0.06 .mu.m) 
0.03 g/m.sup.2 
Solid particle dispersed dye B 
##STR13## 
Viscosity-increasing agent: Polystyrene 
Sulfonic acid (M.W. = 500,000) 
0.1 g/m.sup.2 
Styrene-maleic acid copolymer 
0.1 g/m.sup.2 
Polyvinyl pyrrolidone 0.1 g/m.sup.2 
______________________________________ 
Second layer(Higher-sensitive emulsion layer 
______________________________________ 
Silver halide (converted into silver) 
1.5 g/m.sup.2 
Gelatin 1.0 g/m.sup.2 
Poly(ethyl methacrylate-butylacrylate 
0.5 g/m.sup.2 
Copolymer latex 
Solid dispersion hardening agent 
0.02 g/mol Ag 
(average grain size: 0.12 .mu.m) 
1-formyl-2-{4-(2,4-di-tert-pentylphenoxy) 
butylamide!phenyl}hydrazine 
Sensitizing dye: Potassium salt of 
1 .times. 10.sup.-3 
mol/mol Ag 
5-3-(4-sulfobutyl)-5-thiohydantion 
Viscosity-increasing agent: 
0.1 g/m.sup.2 
polystyrene sulfonic acid 
(M.W. = 500,000) 
Styrene-maleic acid copolymer 
0.1 g/m.sup.2 
Poly(vinyl pyrrolidone) 
0.1 g/m.sup.2 
______________________________________ 
Third layer(Intermediate layer) 
______________________________________ 
Gelatin 0.3 g/m.sup.2 
Viscosity-increasing agent: polystyrene 
0.1 g/m.sup.2 
sulfonic acid (M.W. = 500,000) 
______________________________________ 
Fourth Layer(Lower-sensitive emulsion layer) 
______________________________________ 
Silver halide (converted into silver) 
1.5 g/m.sup.2 
Gelatin 1.0 g/m.sup.2 
Poly (ehtyl methacrylate-butyl acrylate) 
0.5 g/m.sup.2 
copolymer latex 
Solid dispersion contrast increasing agent 
0.02 g/mol Ag 
average particle size: 0.12 .mu.m: 
1-formyl-2-(4-{4-2-(2,4-di-tert- 
pentylphenoxy)butylamide!phenyl)hydrazine 
Solid dispersion redox compount (average 
0.02 g/mol Ag 
particle size: 0.12 .mu.m: 1-(5-nitroindazole-- 
1-il)-2-}4-2,4-di-tert- 
pentylphenoxy)butylamide!phenyl)hydrazine 
Solid dispersion contrast increasing aid: bis 
0.2 g/mol Ag 
(1-piperidino triethylene oxide) thio ether 
Sodium Nonylphenoxyethyleneoxide 
0.2 g/mol Ag 
sulfonate 
Anti-foggant: 
Hydroquinon mon sulfonate 
12 mg/mol Ag 
Hydroquinone aldoxym 12 mg/mol Ag 
1-(p-carboxyphenyl)-5-mercapto tetrazole 
12 mg/mol Ag 
Benzotriazole 12 mg/mol silver 
1-butane sulfonic acid-2,3-dithiacyclohexane 
12 mg/mol Ag 
adenin 
Butyl gallate 12 mg/mol Ag 
Sensitizing dye: Potassium salt of 5-3- 
1 .times. 10.sup.-3 
mol/mol Ag 
(4-sulfobutyl)-5-chloro-2-oxazolizidene!- 
1-hydroxyethyl-3-(2-pyridyl)- 
2-thiohydantion 
Viscocity-increasing agent: polystyrene 
0.1 g/m.sup.2 
sulfonic acid (M.W.: 500,000) 
Styrene - maleic acid copolymer 
0.1 g/m.sup.2 
Poly(vinylpyrrolidone 
0.1 g/m.sup.2 
______________________________________ 
Fifth layer(Lower protective layer) 
______________________________________ 
Gelatin 0.5 g/m.sup.2 
Viscosity-increasing agent; 
0.1 g/m.sup.2 
polystyrene sulfonic acid 
(M.W. = 500,000) 
Styrene - maleic acid copolymer 
0.1 g/m.sup.2 
Polyvinyl pyrrolidone 0.1 g/m.sup.2 
Ethyl methacrylate-butyl acrylate 
0.2 g/m.sup.2 
copolymer latex 
Matting agent; silica dioxide 
0.03 g/m.sup.2 
(Average diameter; 4 .mu.m) 
Solid dispersion safe-light dye (average 
60 mg/m.sup.2 
diameter: 0.06 .mu.m): 4,4'-bis 
1-(4-carboxyphenyl)-3-carboxyethylpyrazole- 
5-one!heptamethine 
Alkali-soluble solid dispersion of development 
60 mg/m.sup.2 
inhibitor (average grain diameter: 0.07 .mu.m): 
4-Nitro indazole 
______________________________________ 
Sixth layer(upper protective layer) 
______________________________________ 
Gelatin 0.5 g/m.sup.2 
Viscosity-increasing agent; 
0.1 g/m.sup.2 
polystyrene sulfonic acid 
(M.W. = 500,000) 
Styrene - maleic acid copolymer 
0.1 g/m.sup.2 
Polyvinyl pyrrolidone 0.1 g/m.sup.2 
Ethyl methacrylate-butyl acrylate 
0.2 g/m.sup.2 
copolymer latex 
Matting agent; silica dioxide 
0.03 g/m.sup.2 
(Average diameter; 4 .mu.m) 
Solid dispersion safe-light dye (average 
60 mg/m.sup.2 
diameter: 0.06 .mu.m): 4,4'-bis 
1-(4-carboxyphenyl)-3-carboxyethylpyrazole- 
5-one!heptamethine 
Alkali-soluble solid dispersion of development 
60 mg/m.sup.2 
inhibitor (average grain diameter: 0.07 .mu.m): 
4-Nitro indazole 
______________________________________ 
These layers were coated after pyrrolidinocarbamoyl pyridine ethane 
sulfonate was added as a hardener to the anti-halation layer in order that 
the amount of addition is 0.3 mmol/g with respect to gelatin contained in 
the whole layers. 
&lt;Preparation of a coating solution for the backing layer&gt; 
After mixing the composition given below, pure water was added to make the 
total volume to be 895 ml, to prepare a coating solution for the backing 
layer. 
______________________________________ 
Gelatin 32.4 g 
Pure water 696 ml 
6% (W/V) aqueous solution of Dye C 
64 ml 
5% (W/V) aqueous solution of Dye D 
24 ml 
33% (W/V) aqueous solution of saponin 
6.6 ml 
20% (W/V) aqueous solution of polymer latex 
33.6 ml 
Copolymer of cyclohexyl methacrylate/iso-nonyl 
acrylate/glycidyl acrylate/styrene-isoprene 
sulfonate having average diameter of 0.10 .mu.m 
10% (W/V) Solid dispersion of fine zinc oxide 
10 ml 
(average diameter; 0.15 .mu.m 
6% (W/V) solid dispersion of Compound N 
10 ml 
(average diameter: 0.1 .mu.m) 
7% (W/V) aqueous solution of citric acid 
3.8 ml 
4% (W/V) aqueous solution of sodium styrene 
23 ml 
sulfonate 
______________________________________ 
&lt;Preparation of a coating solution for backing protective layer&gt; 
After mixing the composition given below, pure water was added to make the 
total volume to be 711 ml, to prepare a coating solution for the backing 
protective layer. 
______________________________________ 
Gelatin 24.9 g 
Pure water 605 ml 
2% (W/V) aqueous solution of methyl methacrylate 
72 ml 
(average diameter: 7 .mu.m) 
4% (W/V) aqueous solution of sodium 1-decyl-2- 
11 ml 
(3-isopentyl) succinate-2-sulfonate 
4% (W/V) aqueous solution of glyoxal 
4 ml 
______________________________________ 
To the above-mentioned coating solution for the backing protective layer, 
an aqueous solution containing a hardener, of which composition is given 
below, was added immediately before coating and both coating solutions 
were coated simultaneously so that coating amount of gelatin for the 
backing layer is 2.5 g/m.sup.2 and that for the backing protective layer 
is 0.5 g/m.sup.2, respectively. 
______________________________________ 
Pure water 27.22 ml 
Methanol 1.5 ml 
Hardener H1 1.28 ml 
Sodium chloride 0.005 g 
______________________________________ 
##STR14## 
Perspective properties were measured as follows: 
&lt;Adhesive property of the coated layer&gt; 
The coated film(primer layer)obtained by coating on the surface of a 
polyester film was cut with a razor blade at an angle of 45.degree. put an 
adhesive Sellotape, peeled off rapidly the coating and the area of the 
primer layer which was peeled off was evaluated with five grades. 
Standards for evaluation 
1. Adhesive force is very weak, and the area of not less than 100% is 
peeled off. 
2. The peeled off area is not less than 50%, and not less than 100%. 
3. The peeled off area is not less than 10%, and not less than 50%. 
4. The adhesive force is strong, and the peeled off area is not less than 
5%, and not less than 10% 
5. The adhesive force is very strong and the peeled off area is less than 
5% or no substantial peeled off is obserbed. 
&lt;Cracking occurence in the primer layer&gt; 
After the primer layer has been coated, dyeing the primer layer with 
methylene blue, and the surface of the primer layer was observed with a 
microscope and evaluated according to the following evaluation standards. 
1: Large cracks of not less than 50 .mu.m are observed. 
2: Small cracks of less than 50 .mu.m are observed. 
3: No substantial cracks are observed. 
&lt;Adhesion property of light-sensitive material&gt; 
In the samples in which a silver halide emulsion layer was provided on the 
SPS film having the primer layer, an adhesion property (hereafter referred 
to emulsion adhesion) before developing process, an adhesion property 
(hereafter referred to wet-emulsion adhesion) during developing process 
and an adhesion property (hereafter referred to dry-emulsion adhesion) 
after developing process are respectively evaluated by the following 
method. 
&lt;Emulsion adhesion&gt; 
After coating the emulsion layer, the surface of the silver halide emulsion 
layer of the samples were cut to have a lattice-like damage with a razor 
blade in order that the damage reaches to the SPS film, and an adhesive 
Sellotape is contacted to the surface of the damaged film and thus the 
surface of the damaged film was rapidly peeled off and the adhesive 
property of the silver halide emulsion layer was evaluated according to 
the following five standards. 
Standards for evaluation 
1. Adhesive force is very weak, and a silver halide emulsion layer is 
completely peeled off. 
2. The peeled off area is not less than 50%, and less than 100%. 
3. The peeled off area is not less than 20%, and less than 50%. 
4. The adhesive force is strong, and the peeled off area is not less than 
5%, and less than 20% 
5. The adhesive force is very strong and the peeled off area is less than 
5%. 
When the standard for evaluation is not less than 4, it can be considered 
that the material has sufficiently strong adhesive force for practical 
use. 
&lt;Wet emulsion adhesion&gt; 
The samples were dipped in the developing solution, fixing solution and 
washing solution, respectively in this order and the emulsion layer of the 
respective samples were rubbed strongly for ten seconds with hands put on 
rubber gloves. Adhesive force was evaluated in five grades by measuring 
the area of the silver halide emulsion layer according to the similar 
standards as in the case of emulsion adhesion. 
&lt;Photographic properties--adaptability to practical photo-taking&gt; 
When using samples, in which a silver halide emulsion layer was provided on 
the SPS film support having a primer layer, a line image was photographed 
on a film by using a camera, and the film was developed at 28.degree. C. 
for 6 seconds, fixed at 28.degree. C. for 6 seconds, rinsed at 25.degree. 
C. for 6 seconds and dried at 60.degree. C. for 6 seconds by using an 
automatic processor, and the thus obtained line image was evaluated by 
visual observation having five grade steps. 
1. not employed for commercial use. 
2. employed, however, not preferable for commercial use. 
3. employed for commercial use. 
4. good for commercial use. 
5. Excellent for commercial use. 
Evaluation of photographic properties were made comprehensively in view of 
sensitivity, line image reproduction ability and graininess, etc. Results 
are given below. 
______________________________________ 
Adhesiveness of 
light-sensitive 
Adhesion 
Existence 
material Photo- 
of of coated Wet- graphic 
Sample 
Sup- coated layer of 
Emulsion 
emulsion 
perfor- 
No. port layer cracks adhesion 
adhesion 
mance 
______________________________________ 
1 1 5 3 5 4 4 
2 2 5 3 5 4 4 
3 3 5 3 4 5 5 
4 4 5 3 5 5 5 
5 5 3 2 2 1 2 
______________________________________