Photographic materials

Static property in a photographic material is effectively prevented by incorporating a specific copolymer formed from, as the copolymerizable components, a betaine-containing polymerizable monomer and a fluorine-containing polymerizable monomer, in the protective layer, backing layer, or an overcoat of the photographic material without exhibiting adverse influences on the photographic properties of the photographic material.

BACKGROUND OF THE INVENTION 
This invention relates to photographic materials having an improved 
antistatic property, and more particularly, it relates to silver halide 
photographic materials having an improved antistatic property and 
resistance to adhesion without exhibiting adverse influences on the 
photographic properties. 
Since a photographic material is generally composed of a support having an 
electric insulating property and photographic layers, electrostatic 
charges are frequently accumulated by contact friction between or 
separation from the surfaces of the same or dissimilar materials during 
the production or use of the photographic material. The electrostatic 
charges thus accumulated cause various problems, but the most serious 
trouble is that accumulated static charge may discharge before development 
of the photographic material to cause lightening-like exposure of 
photosensitive emulsion layers, whereby in the development of the 
photographic film, spot-like, twig-like, or feather-like marks form. These 
marks are so-called static marks, and occurrence of the static marks 
greatly reduces the commercial value of the photographic film, or in some 
cases may result in complete loss of commercial value. For example, it 
will be easily understood that if such a static mark appears in medical or 
industrial X-ray films, etc., it may induce a very dangerous misdiagnosis. 
This phenomenon is a very troublesome problem since the occurrence of the 
phenomenon is first found only at the time of developing the photographic 
film. The static charges accumulated also cause secondary problems, such 
as dust attaching to the surface of the photographic film and preventing 
coating of coating compositions from being uniformly performed. 
Static charges frequently accumulate during the production and use of 
photographic materials as noted above. For example, such charges may be 
produced by contact friction of a photographic film against rollers during 
the production of the photographic film, or by separation of the surface 
of the emulsion layer from the surface of the support during winding or 
rewinding of the photographic film. Static charges are also produced in a 
finished photographic film by separation of the emulsion layer surface 
from the base surface in the case of performing winding or rewinding of a 
photographic film or in X-ray films by contact, separation, etc., between 
the X-ray films and mechanical parts or fluorescent intensifying screens 
in an automatic camera for X-ray films. The occurrence of static marks of 
photographic materials induced by the accumulation of such static charges 
becomes more severe as the sensitivity of photographic materials increases 
and as the processing speed for photographic materials increases. In 
particular, since the sensitivity of photographic materials has become 
higher, and there is an increased likelihood that the photographic 
materials will be treated under severe conditions, such as high-speed 
coating, high-speed photographing, high-speed automatic processing, etc., 
static marks have become increasingly likely to form. 
Also, if a static charge is accumulated on the surface of a subbing layer 
in the case of forming the subbing layer on a film support and coating 
thereon a hydrophilic colloid layer such as a photosensitive silver halide 
emulsion layer, uneven distribution of the static charge appears and 
results in uneven coating of the hydrophilic colloid layer, which is a 
serious defect. 
In one of the methods of overcoming the problems caused by these static 
charges, the electric conductivity of the surface of a photographic 
material is increased to dissipate the static charge in a short period of 
time before the accumulated charge discharges in a film-damaging manner. 
Therefore, various methods have hitherto been considered to improve the 
conductivity of the supports and various surface coating layers of 
photographic materials, and it has been attempted to utilize various 
hygroscopic materials and water-soluble inorganic salts as well as certain 
kinds of surface active agents, polymers, etc. For example, there are the 
polymers as described in U.S. Pat. Nos. 2,882,157, 2,972,535, 3,062,785, 
3,262,807, 3,514,291, 3,615,531, 3,753,716, 3,938,999, etc.; surface 
active agents as described in U.S. Pat. Nos. 2,982,651, 3,428,456, 
3,457,076, 3,454,625, 3,552,972, 3,655,387, etc.; and zinc oxide, 
semiconductors, colloid silica, etc., as described in U.S. Pat. Nos. 
3,062,700, 3,245,833, 3,525,621, etc. 
However, these many materials as noted above show specificities depending 
upon the kinds of film supports and photographic compositions. That is, 
they may give good results for a specific film support and specific 
photographic emulsions as well as specific photographic elements, but they 
are not only useless for the static prevention of other different film 
supports and photographic elements, but also exhibit adverse influences on 
the photographic properties thereof. 
Particularly, static prevention for hydrophilic colloid layers is very 
difficult, and it frequently happens that the reduction in surface 
resistance is insufficient in low humidity conditions, and adhesion 
troubles occur in a photographic material itself or between a photographic 
material and other dissimilar matters at high temperature and high 
humidity conditions. 
On the other hand, some materials have very excellent antistatic effects, 
but cannot be used for photographic materials since they exhibit adverse 
influences on the photographic properties of silver halide photographic 
emulsions, such as sensitivity, fog, granularity, sharpness, etc., or they 
form scum in a fix solution. For example, it is generally known that 
polyethylene oxide series compounds have a static prevention effect, but 
they frequently exhibit adverse influences on the photographic properties 
of silver halide emulsions, such as increasing fog, desensitization, 
reduction in granularity, etc. 
In another method of overcoming the problems of photographic materials 
caused by static charges, the static potential of the photographic 
materials is controlled to reduce the generation of static electricity by 
friction and separation. 
For such purpose, it has hitherto been attempted to use the 
fluorine-containing surface active agents described, for example, in 
British Pat. Nos. 1,330,356 and 1,524,631, U.S. Pat. Nos. 3,666,478 and 
3,589,906, Japanese Patent Publication No. 26687/77 and Japanese Patent 
Application (OPI) Nos. 46733/74 and 32322/76 (the term "OPI" as used 
herein refers to a "published unexamined Japanese patent application"), 
but it sometimes happens that the static preventing ability of the surface 
active agents decreases with the passage of time since they transfer or 
diffuse during the preservation of the photographic materials. 
Furthermore, when these fluorine-containing surface active agents are used 
with above-mentioned conductive materials, they sometimes reduce greatly 
the conductivity of the conductive materials. 
Also for controlling the static potential of photographic materials, it has 
been attempted to overcome the aforesaid faults of the surface active 
agents by using fluorine-containing polymers as described, for example, in 
British Pat. No. 1,497,256, Japanese Patent Application (OPI) Nos. 
15822/79 and 129520/77, Japanese Patent Publication No. 23828/74, British 
Patent Application No. 2,024,440 A, etc. However, when, for example, a 
copolymer of a polyethylene oxide-containing monomer and a 
fluorine-containing acrylic acid ester monomer is applied to photographic 
materials, it is attended by an increase in fog, desensitization, and 
reduction in granularity by the polyethylene oxide group, as described 
above. Also, when a copolymer of a quaternary nitrogen-containing monomer 
and a fluorine-containing acrylic acid ester is applied to photographic 
materials, it may be effective in the points of static prevention ability 
and the prevention of adhesion problems, but it exhibits serious adverse 
influences on the photographic properties of silver halide photographic 
emulsions, such as sensitivity, fog, etc. Thus, it is not very 
satisfactory to use these compounds for photographic materials. 
SUMMARY OF THE INVENTION 
A first object of this invention is to provide photographic materials 
having an improved antistatic property. 
A second object of this invention is to prevent the occurrence of static 
charges on photographic materials without exhibiting adverse influences on 
the photographic properties (sensitivity, fog, granularity, sharpness, 
etc.). 
A third object of this invention is to provide photographic materials 
having an improved antistatic property without causing adhesion problems. 
A fourth object of this invention is to provide photographic materials 
having improved antistatic property without forming scum in a fix 
solution. 
A fifth object of this invention is to provide photographic materials which 
show less reduction in antistatic properties with the passage of time. 
These objects of this invention have been attained by incorporating a 
copolymer including, as copolymerizable components, a betaine-containing 
polymerizable monomer (i.e., containing a betaine group) represented by 
formula (I) or (II) and a fluorine atom-containing polymerizable monomer 
represented by formula (III) in at least one layer of a photographic 
material: 
##STR1## 
wherein R.sub.1 represents hydrogen, a halogen atom, an alkyl group, or a 
substituted alkyl group; R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, and 
R.sub.7 each represents hydrogen, an alkyl group, or a substituted alkyl 
group; R.sub.8 represents a monovalent substituent or when m&gt;1 said 
R.sub.8 s may combine with each other to form a ring; A and X each 
represents a divalent group; Z represents an atomic group forming a 
heterocyclic ring; a and b each represents 0 or a positive integer, except 
that a and b are not simultaneously 0; m represents 0 or an integer of 1 
to 4; n represents an integer of 1 to 5; B represents --COO or --SO.sub.3 
; and R.sub.f represents an alkyl group, an aralkyl group, a substituted 
aralkyl group, an aryl group, or a substituted aryl group, wherein at 
least one hydrogen has been substituted by a fluorine atom. 
DETAILED DESCRIPTION OF THE INVENTION 
In preferred embodiments, 
R.sub.1 represents hydrogen, a halogen atom, or an alkyl group having from 
1 to 4 carbon atoms, and more preferably 1 or 2 carbon atoms, and said 
alkyl group may have a substituent (preferably, a hydroxy group, a halogen 
atom, etc.); 
R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, and R.sub.7 each represents 
hydrogen or an alkyl group having from 1 to 6 carbon atoms, more 
preferably from 1 to 4 carbon atoms, said alkyl group may have a 
substituent (preferably, a hydroxy group, a halogen atom, etc.); at least 
one of R.sub.6 and R.sub.7 being, however, a group different from R.sub.4 
and R.sub.5 when b.noteq.0; 
R.sub.8 represents a monovalent substituent such as, preferably, a hydroxy 
group, a nitro group, a halogen atom, an alkyl group having from 1 to 6 
carbon atoms, more preferably from 1 to 4 carbon atoms, said alkyl group 
may have a substituent (preferably, a halogen atom, a hydroxy group, 
etc.), --O--R.sub.9 (wherein R.sub.9 represents an alkyl group having from 
1 to 6 carbon atoms, more preferably from 1 to 4 carbon atoms, or a 
substituted alkyl group) or 
##STR2## 
or when m&gt;1 said R.sub.8 s may combine with each other to form a ring; 
A represents a chemical bond or a divalent bonding group, such as an 
alkylene group having from 1 to 8 carbon atoms, said alkylene group may 
have a substituent (preferably, a halogen atom, a hydroxy group, etc.), an 
aralkylene group having from 6 to 11 carbon atoms, said aralkylene group 
may have a substituent (preferably, a hydroxy group, a nitro group, a 
lower alkyl group, a halogen, atom, etc.), --COO--R.sub.10 -- (wherein 
R.sub.10 represents a chemical bond or a divalent group such as an 
alkylene group having from 1 to 8 carbon atoms, and preferably from 1 to 6 
carbon atoms, an aralkylene group having from 6 to 11 carbon atoms, an 
arylene group, etc.), --O--CO--R.sub.10 --, or 
##STR3## 
(wherein R.sub.11 represents hydrogen an alkyl group having from 1 to 8 
carbon atoms, more preferably from 1 to 6 carbon atoms, said alkyl group 
may have a substituent (preferably, a hydroxy group, a halogen atom, 
etc.), or an atomic group necessary for forming together with R.sub.2, 
R.sub.3 or R.sub.6 a heterocyclic ring such as a piperazine ring; 
X represents a chemical bond or a divalent bond, such as --R.sub.12).sub.x 
Y--R.sub.13).sub.y W-- (wherein Y and W represent a chemical bond or a 
divalent bond, such as, for example, --O--, --COO--, --OCO--, 
##STR4## 
--S--, --SCO--, 
##STR5## 
R.sub.12 and R.sub.13 represent a chemical bond or a divalent bond, such 
as an alkylene group having from 1 to 8 carbon atoms, more preferably from 
1 to 6 carbon atoms, an aralkylene group having from 6 to 11 carbon atoms, 
or an arylene group; and x and y are 0 or 1); said X being, preferably 
--R.sub.12 --O--R.sub.13 --, 
##STR6## 
--R.sub.12 --COO--R.sub.13 --, --R.sub.12 --OCO--R.sub.13 --, 
##STR7## 
Z represents an atomic group forming a heterocyclic ring which is 
preferably a 5-membered or 6-membered ring including a quaternary nitrogen 
atom, and said ring may contain an oxygen atom or a nitrogen atom 
(non-quaternary), and said ring may have a substituent such as an alkyl 
group, a substituted alkyl group, a nitro group, a hydroxy group, etc.; 
examples of the heterocyclic ring being a pyridine ring, an imidazole 
ring, a benzimidazole ring, etc.; 
a and b represent 0 or a positive integer (preferably 1 to 6, and more 
preferably 1 to 4), except that both a and b are not simultaneously 0; 
m represents 0 or an integer of 1 to 4; 
n represents an integer of 1 to 5; 
B represents --COO or --SO.sub.3 ; and 
R.sub.f represents an alkyl group having from 1 to 24 carbon atoms, more 
preferably from 1 to 18 carbon atoms, and most preferably from 1 to 12 
carbon atoms, an aralkyl group, or an aryl group, said groups may have a 
substituent (e.g., a hydroxy group, a halogen atom other than fluorine, 
and, as a substituent for the benzene ring, a nitro group, an amino group, 
--O--R.sub.9, 
##STR8## 
etc.), said R.sub.f s may combine with each other or with R.sub.8 to form 
a ring (such as a benzene ring, a heterocyclic ring, etc.), wherein at 
least one hydrogen has been substituted by a fluorine atom. 
Typical examples of the betaine monomers of formula (I) or (II) 
particularly preferably used in this invention are illustrated below, 
although the betaine monomers used in this invention are not limited 
thereto. 
##STR9## 
Typical examples of the fluorine-containing monomers of formula (III) 
particularly preferably used in this invention are illustrated below, 
although the invention is not limited thereto: 
##STR10## 
Also, the copolymer used in this invention may further contain other 
copolymerizing component but from the viewpoints of solubility and the 
objects of this invention, it is preferred that the mol% of the total 
content of the betaine monomer and the fluorine-containing monomer are 
above 50%, and it is more preferred that the content of the betaine 
monomer is from 95 to 50 mol%, the content of the fluorine-containing 
monomer is from 50 to 5 mol%, and the content of other monomer components, 
be from 45 to 0 mol%. 
Examples of comonomers which may be used together with the above-described 
monomers used in this invention are acrylic acid, methacrylic acid, the 
alkyl esters of these acids (e.g., methyl methacrylate, ethyl acrylate, 
hydroxyethyl acrylate, propyl acrylate, cyclohexyl acrylate, 2-ethylhexyl 
acrylate, decyl acrylate, .beta.-cyanoethyl acrylate, .beta.-chloroethyl 
acrylate, 2-ethoxyethyl acrylate, sulfopropyl methacrylate, etc.), vinyl 
esters (e.g., vinyl acetate, vinyl propionate, vinyl butyrate, etc.), 
vinyl ethers (e.g., methyl vinyl ether, butyl vinyl ether, oleyl vinyl 
ether, etc.), vinyl ketones (e.g., methyl vinyl ketone, ethyl vinyl 
ketone, etc.), styrenes (e.g., styrene, methylstyrene, dimethylstyrene, 
2,4,6-trimethylstyrene, ethylstyrene, laurylstyrene, chlorostyrene, 
methoxystyrene, cyanostyrene, chloromethylstyrene, vinylbenzoic acid, 
styrenesulfonic acid, .alpha.-methylstyrene, etc.), vinylheterocyclic 
compounds (e.g., vinylpyridine, vinylpyrrolidone, vinylimidazole, etc.), 
acrylonitrile, vinyl chloride, vinylidene chloride, ethylene, propylene, 
butadiene, diisobutylene, isoprene, chloroprene, etc. 
The invention is not limited to the above-described additional 
copolymerizable monomers, and any copolymers having structural units 
derived from monomers of formulae (I) or (II) and (III) may be used in 
this invention. 
Practical examples of the typical copolymers used in this invention are 
illustrated below, wherein the copolymerization ratios x, y, and z 
(representing mol% content values) shown in the following examples are 
particular examples, and the copolymers used in this invention are not 
limited to these ratios. 
##STR11## 
Methods for preparing the betaine monomers used in this invention are 
described, for example, in U.S. Pat. Nos. 2,777,872, 2,846,417, 3,411,912, 
3,832,185 and 4,012,437, and Japanese Patent Publication Nos. 3832/70, 
19951/70, 30293/71 and 1040/74 and Polymer, Vol. 18, 1058 (1977). Typical 
methods for producing the betaine monomer include a method wherein an 
.alpha.-halogenated organic acid such as monochloric acid is added to a 
tertiary amino group-having monomer such as N,N-dimethylaminopropyl 
acrylate, and a method wherein a lactone such as .beta.-propiolactone is 
ring-opened and added to a tertiary amino group-having monomer. 
Methods for producing the fluorine-containing monomers used in this 
invention are described, for example, in U.S. Pat. Nos. 2,436,144, 
2,592,069, 2,628,958, 2,642,416, 2,803,615, 3,102,103, 3,491,169 and 
3,714,245, Japanese Patent Publication Nos. 12883/67, 9205/68, 20466/68, 
851/69, 1994/69, 26286/69, 29724/71, 42371/71, 43894/71 and 20609/72, 
Japanese Patent Application (OPI) Nos. 52019/75, 121184/75, 134040/75 and 
134046/75, Journal of Polymer Science, Vol. 15, 515 (1955), and ibid., 
Vol. 15, 520 (1955). 
Typical methods for producing the fluorine-containing monomers used in this 
invention include a method wherein aminostyrene or aminomethylstyrene is 
reacted with R.sub.f COCl, a method wherein hydroxymethylstyrene is 
reacted with R.sub.f COCl, and a method wherein vinylbenzoic acid chloride 
is reacted with R.sub.f CH.sub.2 NH.sub.2 (wherein R.sub.f has the same 
meaning as described above). 
These raw materials for preparing the aforesaid monomers may be prepared by 
referring to, for example, Kobunshi Ronbun Shu (Polymer Reports), Vol. 32, 
308 (1975), Journal of the Chemical Society, 1515 (1962), Journal of 
Applied Polymer Science, Vol. 5, 452 (1961), Journal of Polymer Science, 
A-1, Vol. 7, 725 (1969), Lovelace et al., Aliphatic Fluorine Compounds, 
published by Reinhold Co. (1958), Journal of American Chemical Society, 
Vol. 78, 4999 (1956), ibid., 5621 (1953), British Pat. No. 717,232 and 
U.S. Pat. No. 2,559,630. 
The copolymers used in this invention may be prepared by a solution 
polymerization method, an emulsion polymerization method, etc., and the 
reaction solvent, reaction temperature, etc., may be properly selected 
according to the polymerization method employed. Furthermore, after 
copolymerizing the monomer containing a tertiary amine for forming the 
betaine and the fluorine-containing monomer, the betaine-forming reaction 
may be performed. 
Typical examples of preparing the monomers and the copolymers used in this 
invention are shown below. 
SYNTHESIS EXAMPLE 1 
Synthesis of Compound (I-1) 
In a reaction vessel were placed 94.5 g (1 mol) of monochloroacetic acid 
and 350 ml of methanol, and the mixture was stirred at 0.degree. to 
5.degree. C. To the mixture was added dropwise slowly 193 g of a 28% 
methanol solution of sodium methylate so that the temperature of the 
system was not over 30.degree. C. Thereafter, a mixture of 156.2 g (1 mol) 
of 3-acrylamidopropyldimethylamine and 300 ml of methanol was added to the 
mixture. (Furthermore, 0.5 g of phenothiazine was added as a 
polymerization inhibitor.) Then, after heating the system to 60.degree. 
C., the mixture was further stirred for 10 hours. Thereafter, sodium 
chloride formed was removed by filtration, and the remaining reaction 
mixture was crystallized in a large amount of acetone. The identification 
of the compound formed was performed by the nuclear magnetic resonance 
(NMR) spectral analysis, elementary analysis, infrared spectral analysis, 
etc. The amount of the product was 145 g (yield of 68%). 
SYNTHESIS EXAMPLE 2 
Synthesis of Compound (I-3) 
In a reaction vessel were placed 72.06 g (1 mol) of .beta.-propiolactone 
and 250 ml of acetonitrile and after cooling the system to -20.degree. C., 
the mixture was stirred at the temperature. To the mixture was added 
dropwise a mixture of 170 g (1 mol) of 3-methacrylamidopropyldimethylamine 
and 700 ml of acetonitrile while controlling the temperature of the system 
not exceeding -10.degree. C. The reaction mixture was allowed to stand 
overnight at 0.degree.-5.degree. C., whereby white hygroscopic crystals 
formed. By recovering the crystals of filtration, 202 g of the desired 
compound was obtained with a yield of 84%. The structure of the compound 
was confirmed by NMR spectral analysis, elementary analysis, and infrared 
spectral analysis. The melting point thereof was 109.degree.-111.degree. 
C. 
SYNTHESIS EXAMPLE 3 
Synthesis of Compound (II-3) 
In a reaction vessel were placed 70 g (0.58 mol) of 1,3-propanesultone and 
800 ml of ethyl acetate and after cooling the mixture to 10.degree. C., 
the mixture was stirred at the temperature. To the mixture was added 
dropwise 50 g (0.46 mol) of 1-vinyl-2-methylimidazole and the mixture was 
stirred for 1 hour at 10.degree.-15.degree. C. Then, the temperature of 
the system was gradually increased to 50.degree. C. and the mixture was 
stirred for 5 days. Crystals formed were recovered by filtration and dried 
to provide 104 g of the desired compound with a yield of 87%. 
The structure of the compound was confirmed by NMR spectral analysis, 
elementary analysis, and infrared spectral analysis. 
SYNTHESIS EXAMPLE 4 
Synthesis of Compound (III-2) 
In a reaction vessel were placed 300 ml of acetonitrile, 33.9 g (0.3 mol) 
of vinylbenzylamine (mixture of meta/para isomers at about 6/4), 30.3 g 
(0.3 mol) of triethylamine, and 0.5 g of 2,6-di-t-butylphenol and the 
mixture was stirred under ice-cooling. To the mixture was added dropwise 
109.5 g (0.3 mol) of 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-n-heptanoic acid 
chloride (b.p. of 131.degree.-133.degree. C.). Thereafter, the mixture was 
stirred for 1 hour at room temperature and triethylamine hydrochloride 
thus formed was removed by filtration. Then, acetonitrile was distilled 
off under reduced pressure from the reaction mixture, and after adding 
thereto 200 ml of ethyl acetate, insoluble materials formed were removed 
by filtration. After distilling off ethyl acetate, 300 ml of n-hexane was 
added to the reaction mixture and the white crystals precipitated were 
recovered by filtration and dried in vacuo at room temperature to provide 
90.1 g (yield of 65%) of the desired compound. The compound was confirmed 
by NMR spectral analysis, elementary analysis, and infrared absorption 
spectral analysis. The melting point thereof was 53.degree.-57.degree. C. 
SYNTHESIS EXAMPLE 5 
Synthesis of Copolymer (P-1) 
In a reaction vessel were placed 34.2 g (0.16 mol) of 
##STR12## 
9.3 g (0.02 mol) of 
##STR13## 
and 150 ml of methanol and the mixture was stirred while heating to 
60.degree. C. in nitrogen atmosphere. To the mixture was added dropwise a 
solution containing 0.2 g of .alpha.,.alpha.'-azobisisobutyronitrile 
(AIBN), having the formula 
##STR14## 
in 20 ml of methanol and the reaction was performed for 8 hours. After 
allowing cooling of the reaction mixture, methanol was removed to form an 
aqueous solution. By removing the unreacted monomers by dialysis and 
lyophilizing the product, a white powder was obtained. The amount of the 
product was 36.2 g. The product was confirmed to have the composition of 
Copolymer (P-1) by elementary analysis, etc. 
SYNTHESIS EXAMPLE 6 
Synthesis of Copolymer (P-3) 
In a reaction vessel were placed 85 g (0.5 mol) of 
##STR15## 
23.06 g (0.05 mol) of 
##STR16## 
and 350 ml of methanol and the mixture was stirred while heating to 
60.degree. C. in nitrogen atmosphere. As in Synthesis Example 5, a 
solution of 0.5 g of AIBN in 50 ml of methanol was added dropwise to the 
mixture and the polymerization was performed for 8 hours. To the polymer 
solution formed were added 52 g (0.55 mol) of monochloroacetic acid and 
106 g (0.55 mol) of a 28% methanol solution of sodium methylate, and then 
the mixture was heated to 60.degree. C. for 6 hours. After cooling the 
reaction mixture, a part of the solution was collected, diluted with pure 
water, and then the Cl.sup.- content was determined with 0.1 N silver 
nitrate. Thus, the reactivity calculated was 100%. 
Thereafter, by performing the same procedure as in Synthesis Example 5, 122 
g of a white polymer was obtained. The polymer had the composition of 
Copolymer (P-3). 
The copolymer of this invention is incorporated in at least one layer of a 
photographic material and the photographic layers are, for example, a 
surface protective layer, a backing layer, interlayers, a subbing layer, 
etc., in addition to silver halide photographic emulsion layers. When a 
backing layer is composed of two layers, the compound may be incorporated 
in one or both of the two layers. Furthermore, when an overcoat is formed 
on a surface protective layer, the compound may be incorporated in the 
overcoat. 
In order to obtain the effect of this invention most remarkably, it is 
preferred to incorporate the compound of the invention in a surface 
protective layer, a backing layer, or an overcoat of a photographic 
material. 
For applying the copolymer of this invention to a photographic material, 
the copolymer of this invention is dissolved in water or an organic 
solvent such as methanol, isopropanol, acetone, etc., or a mixture 
thereof, the resulting solution is added to a coating composition for the 
surface protective layer, a backing layer, an overcoat, etc., and the 
coating composition is coated by a dip coating method, air knife coating 
method, or an extrusion coating method using the hopper described in U.S. 
Pat. No. 2,681,294, or two or more such coating compositions are 
simultaneously coated by a method as described in U.S. Pat. Nos. 
3,508,947, 2,941,898, 3,526,528, etc. Alternatively, the photographic 
material may be immersed in a solution containing the antistatic agent (or 
the copolymer) of this invention. Still further, a solution containing the 
antistatic agent (or the copolymer) of this invention may be coated on the 
surface of a protective layer. 
It is preferred that the amount of the copolymer of this invention be from 
0.01 to 20 g, and more preferably from 0.02 to 5.0 g per square meter of a 
photographic material. The optimum amount of the copolymer will differ 
according to the kind of the photographic film base employed, the 
photographic compositions, the form of the photographic films, and the 
coating system for making the photographic films. 
As the supports used for the photographic materials of this invention, 
there are, for example, cellulose nitrate films, cellulose acetate films, 
cellulose acetate butyrate films, polystyrene films, polyethylene 
terephthalate films, polycarbonate films, laminates of these films, etc. 
Furthermore, there are baryta-coated papers and papers coated or laminated 
with a polymer of an .alpha.-olefin having, in particular, from 2 to 10 
carbon atoms, such as polyethylene, polypropylene, ethylene-butene 
copolymer. 
In the photographic materials of this invention, each photographic layer 
may contain various binders, for example, hydrophilic colloids including: 
proteins such as gelatin, colloidal albumin, casein, etc.; cellulose 
compounds such as carboxymethyl cellulose, hydroxyethyl cellulose, etc.; 
sugar derivatives such as agar agar, sodium alginate, starch derivatives, 
etc.; synthetic hydrophilic polymers such as polyvinyl alcohol, 
poly-N-vinylpyrrolidone; polyacrylic acid copolymers, polyacrylamide, and 
the derivatives or partially decomposed products of them. If desired, 
these colloids may be used as a mixture of two or more. 
Among the above-described hydrophilic colloids, gelatin is most generally 
used, and the term "gelatin" used in this specification includes so-called 
lime-treated gelatin, acid-treated gelatin, and enzyme-treated gelatin. 
Gelatin may be partially or wholly replaced with a synthetic polymer or 
may be replaced with a gelatin derivative obtained by modifying gelatin 
with a reagent having one radical capable of reacting with the amino 
group, imino group, hydroxy group or carboxy group contained in the 
gelatin molecule as a functional group or with a graft polymer obtained by 
bonding the molecular chain of a polymer to gelatin. 
A silver halide emulsion used for the photographic material of this 
invention is usually prepared by mixing an aqueous solution of a 
water-soluble silver salt (e.g., silver nitrate) and an aqueous solution 
of a water-soluble halide (e.g., potassium bromide) in the presence of an 
aqueous solution of a water-soluble polymer such as gelatin. Examples of 
the silver halide used in this invention are silver chloride and silver 
bromide as well as mixed silver halides such as silver chlorobromide, 
silver iodobromide, silver chloroiodobromide, etc. 
The silver halide photographic emulsions used in this invention can be 
subjected to a spectral sensitization or supersensitization using 
polymethine sensitizing dyes such as cyanine, merocyanine, carbocyanine, 
etc., solely or a combination thereof or as a combination with styryl 
dyes. 
Also, the silver halide photographic emulsions for the photographic 
materials of this invention may further contain various additives for 
preventing the reduction in sensitivity and the formation of fog during 
the production, preservation, or processing of photographic materials. As 
such additives, there are not only 
4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene, 3-methylbenzothiazole, 
1-phenyl-5-mercaptotetrazole, etc., but also many known compounds such as 
heterocyclic compounds, mercury-containing compounds, mercapto compounds, 
metal salts, etc. 
In the case of using silver halide photographic emulsions for color 
photographic materials, couplers may be incorporated in the silver halide 
emulsion layers. Examples of the couplers useful in this invention include 
known couplers such as 4-equivalent type diketomethylene yellow couplers, 
2-equivalent type diketomethylene yellow couplers, 4-equivalent type 
pyrazolone magenta couplers, 2-equivalent type pyrazolone magenta 
couplers, indazolone magenta couplers, .alpha.-naphthol cyan couplers, and 
phenolic cyan couplers. 
The silver halide emulsion layers and other photographic layers of the 
photographic materials of this invention can be hardened by various kinds 
of organic or inorganic hardening agents (solely or as combinations of 
them). Typical examples of the hardening agents are aldehyde series 
compounds such as mucochloric acid, formaldehyde, trimethylolmelamine, 
glyoxal, 2,3-dihydroxy-1,4-dioxane, 2,3-dihydroxy-1,4-dioxane, 
2,3-dihydroxy-5-methyl-1,4-dioxane, succinaldehyde, glutaraldehyde, etc.; 
active vinyl compounds such as divinylsulfone, methylenebismaleimide, 
1,3,5-triacryloylhexahydro-s-triazine, 
1,3,5-trivinylsulfonylhexahydro-s-triazine bis(vinylsulfonylmethyl) ether, 
1,3-bis(vinylsulfonylmethyl)propanol-2, 
bis(.alpha.-vinylsulfonylacetamido)ethane, etc.; active halides such as 
2,4-dichloro-6-hydroxy-s-triazine.sodium salt, 
2,4-dichloro-6-methoxy-s-triazine, etc.; and ethyleneimine compounds such 
as 2,4,6-triethyleneimino-s-triazine, etc. 
In the photographic layers of the photographic materials of this invention, 
surface active agents may be incorporated solely or as a combination 
thereof. They are used as a coating aid but they are sometimes used for 
other purposes, e.g., for emulsification, for the improvement of 
photographic properties such as sensitivity, etc., and for controlling 
static property, etc. 
As such surface active agents, there are natural surface active agents such 
as saponin, etc.; nonionic surface active agents such as alkylene oxide 
series, glycerol series, and glycidol series surface active agents; 
cationic surface active agents such as higher alkylamines, quaternary 
ammonium salts, heterocyclic compounds (e.g., pyridine, etc.), phosphonium 
compounds, sulfonium compounds, etc.; anionic surface active agents 
containing acid groups such as carboxylic acid, sulfonic acid, phosphoric 
acid, sulfuric acid ester, phosphoric acid, ester, etc.; and amphoteric 
surface active agents such as aminoacids, aminosulfonic acids, amino 
alcohol sulfuric acid or phosphoric acid esters, etc. 
Some surface active agents useful in this invention are described in U.S. 
Pat. Nos. 2,271,623, 2,240,472, 2,288,226, 2,739,891, 3,068,101, 
3,158,484, 3,201,253, 3,210,191, 3,294,540, 3,415,649, 3,441,413, 
3,442,654, 3,475,174, 3,545,974, 3,666,478, and 3,507,660, British Pat. 
No. 1,198,450 as well as Ryohei Oda, et al., Synthesis and Application of 
Surface Active Agents, published by Maki Shoten, 1964, A. W. Perry, 
Surface Active Agents, published by Interscience Publication Incorporated, 
1958, J. P. Sisley, Encyclopedia of Surface Active Agents, Vol. 2, 
published by the Chemical Publishing Company, 1964. 
In this invention, fluorine series surface active agents can be used, and 
examples of such fluorine surface active agents are described, for 
example, in British Pat. Nos. 1,330,356 and 1,524,631, U.S. Pat. Nos. 
3,666,478 and 3,589,906, Japanese Patent Publication No. 36687/77 and 
Japanese Patent Application (OPI) Nos. 46733/74 and 32322/76. 
Also, in this invention the photographic layers may further contain 
lubricating compositions such as the modified silicones described, for 
example, in U.S. Pat. Nos. 3,079,837, 3,080,317, 3,545,970 and 3,294,537 
and Japanese Patent Application (OPI) No. 129520/77. 
The photographic layers of the photographic materials of this invention can 
further contain polymer latexes as described in U.S. Pat. Nos. 3,411,911 
and 3,411,912 and Japanese Patent Publication No. 5331/70 and also silica, 
strontium sulfate, barium sulfate, polymethyl methacrylate, etc., as a 
matting agent. 
By the practice of this invention, the problems due to static charges 
occurring during the production and/or use of the photographic materials 
can be prevented. 
For example, the occurrence of static marks caused by: (1) contact between 
the surface of the emulsion layers and the surface of backing layer of 
photographic materials, (2) contact between the surface of the emulsion 
layer and the surface of the emulsion layer of photographic materials, and 
(3) contact of photographic materials with other materials which are 
frequently brought into contact with the photographic materials, e.g., 
rubber, metals, plastics, and fluorescent intensifying screens, can also 
be prevented.

The invention is practically explained by the following examples. It should 
be understood that the invention is not limited to embodiments shown in 
these examples. 
EXAMPLE 1 
Samples 1 to 8 were each prepared by coating one surface of a polyethylene 
terephthalate film (about 175 .mu.m thick (dry)) with a silver halide 
emulsion layer and then a protective layer as described below, and then 
drying. 
Silver halide emulsion layer (about 5 .mu.m thick (dry)) 
Binder: 2.5 g/m.sup.2 of gelatin 
Silver coverage: 5 g/m.sup.2 
Silver halide composition: 1.5 mol% AgI and 98.5 mol% AgBr 
Antifoggant: 1-phenyl-5-mercaptotetrazole in an amount of 0.5 g/100 g of Ag 
Protective layer (about 1 .mu.m thick (dry)) 
Binder: 1.7 g/m.sup.2 of gelatin 
Coating agent: 7 mg/m.sup.2 of N-oleyl-N-methyltaurine sodium salt 
Hardening agent: 2,4-dichloro-6-hydroxy-1,3,5-triazine.sodium salt at 0.4 
g/100 g of gelatin 
Sample 1 was composed of the aforesaid composition only, and Samples 2 to 6 
further contained 500 mg/m.sup.2 of Copolymers (P-1), (P-3), (P-5), (P-7), 
and (P-9) of this invention, respectively, in the protective layers. 
Also, for comparison, Samples 7 and 8, each having the above-mentioned 
compositions and further containing 500 mg/m.sup.2 of following Comparison 
Polymer A disclosed in Japanese Patent Application (OPI) No. 125726/75 and 
Comparison Polymer B disclosed in Japanese Patent Application (OPI) No. 
129520/77, respectively, in each protective layer were prepared. 
##STR17## 
The antistatic property of these samples was determined by the following 
method. 
After humidifying the unexposed samples for 2 hours at 25.degree. C. and 
25% RH, each of the samples was rubbed by a Neoprene rubber roller on the 
emulsion layer side of the sample, developed in a developer having a 
composition as shown below, fixed, and washed, and then the extent of 
formation of static marks was determined. 
______________________________________ 
Developer Composition 
______________________________________ 
Warm Water 800 ml 
Sodium Tetrapolyphosphate 
2.0 g 
Anhydrous Sodium Sulfite 
50 g 
Hydroquinone 10 g 
Sodium Carbonate (monohydrate) 
40 g 
1-Phenyl-3-pyrazolidone 0.3 g 
Potassium Bromide 2.0 g 
Water to make 1,000 ml 
(pH 10.2) 
______________________________________ 
Then, after exposing the unexposed samples on a tungsten lamp through 
Filter SP-14 made by Fuji Photo Film Co., Ltd. at an exposure amount of 
1.6 CMS (candela meter second), each sample was developed in the developer 
having the above composition for 30 sec at 35.degree. C., fixed, washed, 
and then the sensitivity and fog were measured. Furthermore, after 
preserving corresponding unexposed samples for 3 days at 50.degree. C., 
each of the preserved samples was exposed and processed under the same 
conditions as above, and then the sensitivity and fog were measured. Thus, 
the influence of the additives on the photographic properties was 
determined. 
The resulting antistatic and photographic properties of each sample are 
shown in Table 1. 
TABLE 1 
__________________________________________________________________________ 
Photographic Properties 
Directly after 
Sample Antistatic* 
Coating After Preservation 
No. Antistatic Agent 
Property 
Fog 
Sensitivity 
Fog 
Sensitivity 
__________________________________________________________________________ 
1 None (control) 
D 0.16 
0 0.17 
-0.01 
2 Copolymer (P-1) 
A 0.16 
0 0.16 
0 
3 Copolymer (P-3) 
A 0.16 
0 0.16 
0 
4 Copolymer (P-5) 
A 0.16 
0 0.16 
0 
5 Copolymer (P-7) 
A 0.16 
0 0.17 
0 
6 Copolymer (P-9) 
A 0.16 
0 0.16 
0 
7 Comparison Polymer A 
B 0.18 
+0.01 0.40 
+0.02 
8 Comparison Polymer B 
A-B 0.17 
0 0.37 
+0.01 
__________________________________________________________________________ 
Indicates the degree of the formation of static marks. 
In Table 1 the extent of the formation of static marks was evaluated 
visually using the following four grades: 
A: No static marks formed. 
B: Static marks formed a little. 
C: Static marks formed considerably. 
D: Static marks formed over most of surface. 
The sensitivity in Table 1 was determined by taking the sensitivity of the 
control sample (Sample No. 1) directly after coating as a standard 
sensitivity with an arbitrary value 0, and the sensitivity of other 
samples was a deviation from the standard sensitivity shown by the 
absolute value of log E. No deviation from the standard sensitivity 
indicates that here was no influence on the photographic property. 
From the results shown in Table 1, it is understood that the antistatic 
compounds of this invention had excellent antistatic effect, forming 
almost no static marks, and did not exhibit any adverse influences on the 
photographic properties such as fog, sensitivity, etc. On the other hand, 
it is clear that in the case of using the comparison polymers, the 
formation of fog after preserving the photographic films increased 
greatly, and hence the comparison polymers did exhibit influences on the 
photographic properties of the photographic materials. 
EXAMPLE 2 
Sample 9 was prepared in the same manner as Example 1 except that 500 
mg/m.sup.2 of the Comparison Polymer C disclosed in German Patent 
Application (OLS) No. 3,038,818 was incorporated in the protective layer 
in place of the Comparison Polymers A and B. 
Then, for Samples 1 to 6 of Example 1 and Sample 9 in this example, the 
surface specific resistance and the static potential charge were measured 
by the following manners. 
##STR18## 
(a) Measurement of surface specific resistance: 
After humidifying the sample for 2 hours at 25.degree. C. and 25% RH 
(relative humidity), the sample was placed between brass electrodes (the 
portion of each electrode which was brought into contact with the sample 
was made by stainless steel) of 10 cm length at a distance between 
electrodes of 0.14 cm under the same conditions as above and the surface 
specific resistance of 1 minute value was measured by means of an 
electrometer, TR-8651, made by Takeda Riken K. K. 
(b) Measurement of static charge generated: 
Two samples (2 cm.times.11 cm) were laminated with each other using a 
two-sided adhesive tape in such manner that the protective layers were on 
the outside surfaces, and after humidifying the samples for 2 hours at 
25.degree. C. and 25% RH, the sample laminate was passed through two 
rotary white rubber rollers. Thereafter, the samples were placed in a 
Faraday cage and the static charge generated was measured by means of an 
electrometer (units in volts). 
The results are shown in Table 2. 
TABLE 2 
______________________________________ 
Surface 
Specific Static 
Sample Resistance Potential 
No. Antistatic Agent (.OMEGA.) (volt) 
______________________________________ 
1 None 3.0 .times. 10.sup.14 
+150 
2 Copolymer (P-1) 6.2 .times. 10.sup.12 
-10 
3 Copolymer (P-3) 5.5 .times. 10.sup.12 
0 
4 Copolymer (P-5) 7.9 .times. 10.sup.12 
-5 
5 Copolymer (P-7) 7.0 .times. 10.sup.12 
+10 
6 Copolymer (P-9) 6.8 .times. 10.sup.12 
-10 
9 Comparison Polymer C 
8.7 .times. 10.sup.12 
+155 
______________________________________ 
From the results shown in Table 2, it is understood that the antistatic 
compounds of this invention were also effective for the reduction in 
surface specific resistance and static potential in addition to static 
prevention. On the other hand, the comparison polymer used in Sample No. 9 
reduced the surface specific resistance but did not reduce the static 
potential. 
EXAMPLE 3 
After humidifying Samples 1 to 8 as in Example 1 and Sample 9 as in Example 
2 for 2 days at 40.degree. C. and 70% RH, two sheets (4 cm.times.4 cm) of 
each sample were rubbed with each other at the surfaces of the protective 
layers, preserved for 1 day under the conditions of 40.degree. C., 70% RH, 
while applying thereon a load of 800 g, then the sample sheets were 
separated from each other, and the area of the stuck portion was measured, 
evaluated as described below. 
______________________________________ 
Rank A: Area of stuck portion 
0-40% 
Rank B: " 41-60% 
Rank C: " 61-80% 
Rank D: " .gtoreq.81% 
______________________________________ 
The results are shown in Table 3. 
TABLE 3 
______________________________________ 
Sample Adhesion 
No. Antistatic Agent 
Resistance 
______________________________________ 
1 None C 
2 Copolymer (P-1) A 
3 Copolymer (P-3) A 
4 Copolymer (P-5) A 
5 Copolymer (P-7) A 
6 Copolymer (P-9) A 
7 Comparison Polymer A 
D 
8 Comparison Polymer B 
C 
9 Comparison Polymer C 
C 
______________________________________ 
From the results shown in Table 3, it is clear that the samples using the 
compounds of this invention show less adhesion of protective layers with 
each other and showed good adhesion resistance as compared with the 
samples using the comparison compounds. 
EXAMPLE 4 
In 10 ml of water was dissolved 8 g of each of the Copolymers (P-3), (P-6), 
(P-10) and (P-12) of this invention and the Comparison Polymers A, B, and 
C and the solution was diluted with a mixture of 650 ml of methanol and 
350 ml of acetone. The solution obtained was coated on a cellulose 
triacetate film at a coverage of 50 mg/m.sup.2 and dried. Furthermore, a 
diacetyl cellulose solution using a mixture of 850 ml of acetone and 150 
ml of methanol was coated on the layer. 
Then, the opposite surface of the film base having the coated layers was 
coated with a direct X-ray silver halide photographic emulsion containing 
9% by weight gelatin and 9% by weight silver halide. 
Thus, Sample 10 containing no antistatic agent, and Samples 11 to 17 
containing the Copolymers (P-3), (P-6), (P-10) and (P-12) of the invention 
and the Comparison Polymers A, B and C, respectively, were prepared. The 
antistatic property of these samples was determined in the same manner as 
in Example 1, except that the back surface of the film opposite to the 
emulsion layer side was rubbed by a Neoprene rubber roller. Furthermore, 
the adhesion resistance was determined in the same manner as in Example 3, 
except that the back surface was tested in place of the protective layer. 
The results are shown in Table 4. 
TABLE 4 
______________________________________ 
Formation 
Sample Adhesion of 
No. Antistatic Agent Resistance 
Static Mark 
______________________________________ 
10 None (control) C D 
11 Copolymer (P-3) A A 
12 Copolymer (P-6) A A 
13 Copolymer (P-10) A A 
14 Copolymer (P-12) A A 
15 Comparison Polymer A 
D B 
16 Comparison Polymer B 
B A-B 
17 Comparison Polymer C 
C B 
______________________________________ 
From the results shown in Table 4, it is understood that the samples using 
the compounds of this invention scarcely formed static marks and showed 
very good adhesion resistance. On the other hand, it is clear that in the 
samples using the compairson compounds, static marks formed to a greater 
extent, and in the control sample containing no antistatic agent, static 
marks formed over the whole surface, and these samples showed poor 
adhesion resistance. 
EXAMPLE 5 
Samples 18 to 21 were prepared, each having, on a triacetyl cellulose 
support, in sequence, an antihalation layer, a red-sensitive silver halide 
emulsion layer, an interlayer, a green-sensitive silver halide emulsion 
layer, a yellow filter layer, a blue-sensitive silver halide emulsion 
layer, and a protective layer. The compositions of the layers are shown 
below. 
Antihalation layer 
Binder: 4.4 g/m.sup.2 of gelatin 
Hardening agent: 1,3-bis(vinylsulfonyl)propanol-2 at 1.2 g/100 g of binder 
Coating aid: 4 mg/m.sup.2 of sodium dodecylbenzenesulfonate 
Antihalation component: 0.4 g/m.sup.2 of black colloid silver 
Red-sensitive silver halide emulsion layer 
Binder: 7 g/m.sup.2 of gelatin 
Hardening agent: 1,3-bis(vinylsulfonyl)propanol-2 at 1.2 g/100 g of binder 
Coating aid: 10 mg/m.sup.2 of sodium dodecylbenzenesulfonate 
Silver coverage: 3.1 g/m.sup.2 
Silver halide composition: 2 mol% AgI and 98 mol% AgBr 
Antifoggant: 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene at 0.9 g/100 g of 
Ag 
Coupler: 
1-hydroxy-4-(2-acetylphenyl)azo-N-[4-(2,4-di-tert-amylphenoxy)butyl]-2-nap 
hthamide at 38 g/100 g of Ag 
Sensitizing dye: 
anhydro-5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)thiacarbocyaninehydrox 
ide.pyridinium salt at 0.3 g/100 g of Ag 
Interlayer 
Binder: 2.6 g/m.sup.2 of gelatin 
Hardening agent: 1,3-bis(vinylsulfonyl)propanol-2 at 1.2 g/100 g of binder 
Coating aid: 12 mg/m.sup.2 of sodium dodecylbenzenesulfonate 
Green-sensitive silver halide emulsion layer 
Binder: 6.4 g/m.sup.2 of gelatin 
Hardening agent: 1,3-bis(vinylsulfonyl)propanol-2 at 1.2 g/100 g of binder 
Coating aid: 9 mg/m.sup.2 of sodium dodecylbenzenesulfonate 
Silver coverage: 2.2 g/m.sup.2 
Silver halide composition: 3.3 mol% AgI and 96.7 mol% AgBr 
Stabilizer: 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene at 0.6 g/100 g of Ag 
Coupler: 
1-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-tert-amylphenoxy)acetamido]-4-(4-me 
thoxyphenyl)azo-5-pyrazolone at 37 g/100 g of Ag 
Sensitizing dye: 
anhydro-5,5'-diphenyl-9-ethyl-3,3'-di(2-sulfoethyl)oxacarbocyanine-hydroxi 
de.pyridinium salt at 3 g/100 g of Ag 
Yellow filter layer 
Binder: 2.3 g/m.sup.2 of gelatin 
Filter component: 0.7 g/m.sup.2 of yellow colloid silver 
Hardening agent: 1,3-bis(vinylsulfonyl)propanol-2 at 1.2 g/100 g of binder 
Surface active agent: 7 mg/m.sup.2 of 2-sulfonatosuccinic acid 
bis(2-ethylhexyl) ester sodium salt 
Blue-sensitive silver halide emulsion layer 
Binder: 7 g/m.sup.2 of gelatin 
Hardening agent: 1,3-bis(vinylsulfonyl)propanol-2 at 1.2 g/100 g of binder 
Coating aid: 8 mg/m.sup.2 of sodium dodecylbenzenesulfonate 
Silver coverage: 2.2 g/m.sup.2 
Silver halide composition: 3.3 mol% AgI and 96.7 mol% AgBr 
Stabilizer: 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene at 0.4 g/100 g of Ag 
Coupler: 
2'-chloro-5'-[2-(2,4-di-tert-amylphenoxy)butyramido]-.alpha.-(5,5'-dimethy 
l-2,4-dioxo-3-oxazolidinyl)-.alpha.-(4-methoxybenzoyl)acetanilide at 45 
g/100 g of Ag 
Protective layer 
Binder: 2 g/m.sup.2 of binder and 0.3 g/m.sup.2 of a (1:1) copolymer of 
styrene-maleic anhydride having a mean molecular weight of about 100,000 
Hardening agent: 1,3-bis(vinylsulfonyl)propanol-2 at 1.2 g/100 g of binder 
Coating aid: 5 mg/m.sup.2 of sodium dioctylsulfosuccinate 
Sample 18 had the layers of the above-described compositions only, whereas 
Samples 19 to 21 further contained 500 mg/m.sup.2 of Copolymers (P-2) and 
(P-3) of this invention, and Comparison Polymer B, respectively, in each 
protective layer. 
The antistatic property was determined in the same manner as in Example 1, 
except that an ordinary color development was performed instead of 
performing the black-and-white development in Example 1. The results are 
shown in Table 5. 
TABLE 5 
______________________________________ 
Sample Formation of 
No. Antistatic Agent 
Static Mark 
______________________________________ 
18 None D 
19 Copolymer (P-2) A 
20 Copolymer (P-3) A 
21 Comparison Polymer B 
B 
______________________________________ 
From the results shown in Table 5, it is clear that the samples using the 
copolymers of this invention formed almost no static marks. 
Each of the samples was also exposed based on the JIS K7613/1976 method and 
color developed in a conventional manner. The results were that Sample 21 
using the comparison polymer formed severe fog in the green-, blue-, and 
red-sensitive silver halide emulsion layers, but in the case of the 
samples of this invention, the copolymers of this invention used had 
scarcely any adverse influences on the photographic properties. 
EXAMPLE 6 
One surface of a cellulose triacetate film support was coated with a 
backing layer and a protective layer for the backing layer, and the 
opposite surface thereof was coated with the multilayer color photographic 
layers as in the control sample (Sample No. 18) in Example 5. The 
compositions of the backing layer and the protective layer for the backing 
layer were as follows: 
Backing layer 
Binder: 6.2 g/m.sup.2 of binder 
Salt: 0.1 g/m.sup.2 of potassium nitrate 
Hardening agent: 1,3-bis(vinylsulfonyl)propanol-2 at 1.2 g/100 g of binder 
Protective layer for backing layer 
Binder: 2.2 g/m.sup.2 of gelatin 
Matting agent: 20 mg/m.sup.2 of polymethyl methacrylate (mean grain size of 
2.5 .mu.m) 
Hardening agent: 1,3-bis(vinylsulfonyl)propanol-2 at 1.2 g/100 g of binder 
Coating aid: 40 mg/m.sup.2 of sodium dioctylsulfosuccinate 
In this example, Sample 22 had layers formed from the above compositions 
only, but Samples 23 to 25 further included 0.8 g/m.sup.2 of the 
Copolymers (P-3), (P-6) and (P-8), respectively, of this invention in each 
backing layer. The surface specific resistance of each of the backing 
layers of these samples was determined in the same manner as in Example 2. 
The results are shown in Table 6. 
TABLE 6 
______________________________________ 
Surface Specific 
Sample Resistance 
No. Antistatic Agent 
(.OMEGA.) 
______________________________________ 
22 None 4.0 .times. 10.sup.13 
23 Copolymer (P-3) 
1.3 .times. 10.sup.11 
24 Copolymer (P-6) 
3.5 .times. 10.sup.11 
25 Copolymer (P-8) 
2.6 .times. 10.sup.11 
______________________________________ 
From the results shown in Table 6, it is understood that the use of the 
copolymers of this invention greatly reduced the surface specific 
resistance and was effective for static prevention. 
EXAMPLE 7 
A photographic material having the same composition as Sample 1 in Example 
1 was immersed in an aqueous solution of 2% by weight of the compound 
shown in Table 7 for 5 seconds and then spontaneously dried under the 
conditions of 25.degree. C. and 65% RH. Then, after humidifying each of 
the samples for 2 hours at 25.degree. C. and 25% RH, the formation of 
static mark was determined in the same manner as in Example 1. The results 
are shown in Table 7. 
TABLE 7 
______________________________________ 
Sample Formation of 
No. Antistatic Agent 
Static Mark 
______________________________________ 
26 None D 
27 Copolymer (P-4) 
A 
28 Copolymer (P-10) 
A 
29 Copolymer (P-12) 
A 
______________________________________ 
From the results shown in Table 7, it is clear that when the compounds of 
this invention were applied to photographic material as an aqueous 
solution thereof, they showed good antistatic effect. 
EXAMPLE 8 
A cellulose acetate film (130 .mu.m thick (dry)) having a gelatin subbing 
layer thereon was coated with a solution having the following composition 
to form an antistatic layer. 
______________________________________ 
Antistatic Agent 8 g 
Water 10 ml 
Methanol 600 ml 
Acetone 400 ml 
______________________________________ 
On the antistatic layer were formed, in sequence, an antihalation layer and 
a red-sensitive silver halide emulsion layer having the same compositions 
described in Example 5 by means of a co-extrusion method. The uneven 
coating of the silver halide emulsion layer caused by the static 
phenomenon during coating was observed visually using transmitted light, 
and the results are shown in Table 8. 
TABLE 8 
______________________________________ 
Sample 
No. Antistatic Agent 
Uneven Coating 
30 None Significant 
31 Copolymer (P-3) 
Scarcely observed 
32 Copolymer (P-6) 
" 
______________________________________ 
From the results shown in Table 8, it becomes clear that the sample 
containing the antistatic agent of this invention between the subbing 
layer and the silver halide emulsion layer gave substantially no uneven 
coating when coating of the silver halide emulsion layer. 
EXAMPLE 9 
A polyethylene terephthalate film support (175 .mu.m thick (dry)) was 
coated with an aqueous solution of 2.5% by weight copolymer composed of 48 
mol% butadiene, 47 mol% styrene, and 5 mol% itaconic acid and 0.15% by 
weight 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt at a coverage of 
20 ml/m.sup.2 and dried for 10 minutes at 120.degree. C. In this case 
Sample 33 contained no antistatic agent and Samples 34 and 35 contained 
1.0% by weight of Copolymers (P-2) and (P-7), respectively, of the 
invention. The surface specific resistance of these samples was measured 
by the same method as in Example 1, and the results obtained are shown in 
Table 9. 
TABLE 9 
______________________________________ 
Surface Specific 
Sample Resistance 
No. Antistatic Agent 
(.OMEGA.) 
______________________________________ 
33 None Above 10.sup.15 
34 Copolymer (P-2) 
2.1 .times. 10.sup.12 
35 Copolymer (P-7) 
5.4 .times. 10.sup.12 
______________________________________ 
From the results shown in Table 9, it is understood that the copolymers of 
this invention were effective for greatly reducing the surface specific 
resistance and static prevention in the case of subbing layer. 
EXAMPLE 10 
For confirming the formation of scum in the cases of processing with a 
developer and fix solution, about 3 m.sup.2 of each of Samples 1 to 8 as 
described in Example 1 was processed by a simple automatic processer, Fuji 
X-ray Processor RN (trademark of Fuji Photo Film Co., Ltd.) using a 
developer Fuji RD-III (trademark of Fuji Photo Film Co., Ltd.) and a fix 
solution Fuji F (trademark of Fuji Photo Film Co., Ltd.) of 12 liters 
each, and then the formation of scum in the developer and the fix solution 
was observed visually. 
The developer and the fix solution used were the developer and the fix 
solution for processing medical X-ray film made by Fuji Photo Film Co., 
Ltd. The results of the scum test are shown in Table 10. 
TABLE 10 
______________________________________ 
Sample Formation of Scum 
Formation of Scum 
No. in Fix Solution 
in Developer 
______________________________________ 
1 None None 
2 " " 
3 " " 
4 " " 
5 " " 
6 " " 
7 Small amount Large amount 
8 " " 
______________________________________ 
From the results shown in Table 10, it is clear that the samples using the 
compounds of this invention formed less scum as compared with the samples 
using the comparison cation polymers. 
While the invention has been described in detail and with reference to 
specific embodiments thereof, it will be apparent to one skilled in the 
art that various changes and modifications can be made therein without 
departing from the spirit and scope thereof.