Photographic light-sensitive silver halide material containing an antistatic block copolymer

A static-inhibited photographic light-sensitive material is provided by incorporating a fluorine-containing block polymer derived from a polymerizable hydrophobic monomer containing at least one fluorine atom and a polymerizable hydrophilic monomer, as an antistatic agent in at least one layer thereof. Unlike known antistatic agents and methods, the use of the above antistatic agent does not adversely affect the photographic characteristics, antitack property, marring resistance, etc., of the photographic light-sensitive material.

FIELD OF THE INVENTION 
This invention relates to a photographic light-sensitive material and more 
particularly to a photographic light-sensitive material having an improved 
antistatic property. 
BACKGROUND OF THE INVENTION 
Photographic light-sensitive materials generally comprise an electrically 
insulating support coated with photographic layers, and it often happens 
during their production that static charges are built up as they are 
rubbed against each other or other surfaces. The static charges so 
accumulated can cause many problems, the most serious of which is that the 
static charge so built up discharges to sensitize the light-sensitive 
emulsion layer before development so that when the film is developed, 
there occur punctate defects or dentritic or feathery streaks. These are 
generally called static marks, and detract considerably from the market 
value of a photographic film, or, at worst, destroy the value completely. 
It is easy to understand that if static marks are formed on medical or 
industrial X-ray film, for instance, they may lead to a dangerous 
misdiagnosis or judgement. Since this blemish becomes apparent for the 
first time only upon development of the film, it presents a very serious 
problem. Moreover, the accumulated static charge may induce secondary 
problems, such as deposition of dust on the film surface and/or failures 
to obtain uniform coating results. 
While the aforesaid static charge is often built up in the course of 
production, handling and use of a photographic light-sensitive material, 
such static charge build-up in the course of production takes place, for 
example, due to friction between the photographic film and the roller 
assembly or the exfoliation of the emulsion layer from the support during 
the take-up or rewinding of the film. It also develops due to contact or 
peeling stress between the X-ray film and the mechanical parts of 
fluorescent sensitizing paper in the automatic camera. Another cause is 
contact with packaging materials. The static marks on the photographic 
light-sensitive material as caused by such accumulation of static charge 
become more conspicuous as the sensitivity of the light-sensitive material 
and/or the photographic processing speed are increased. Particularly, 
recent years have witnessed an increasing opportunity of photographic 
light-sensitive materials being exposed to very tortuous conditions such 
as an increased sensitivity of the light-sensitive materials themselves, 
high speed coating processes, high speed photographing, high speed 
automatic processing, etc., and these factors have been contributing to an 
increasing incidence of static marks. 
To overcome these problems due to static electricity, it is desirable to 
incorporate an antistatic agent in photographic light-sensitive materials. 
However, all the antistatic agents commonly used in other fields of art 
cannot be used as such in photographic light-sensitive materials, but 
antistatic agents that can be used must meet several requirements peculiar 
to this field of art. Thus, in addition to a high static inhibiting 
action, the antistatic agent useful for photographic light-sensitive 
materials must have the following and other characteristics. Thus, it 
should not exert untoward effects on the photographic characteristics of 
light-sensitive materials, such as sensitivity, fog, grain properties, 
sharpness, etc. Secondly, there should not be an adverse influence on the 
film strength of the photographic light-sensitive material (i.e., the 
light-sensitive material should be resistant to abrasion and scratching). 
Thirdly, the antitack property of the light-sensitive material should not 
be adversely affected (i.e., the light-sensitive materials should not be 
made liable to stick to each other or to other surfaces). Moreover, the 
antistatic agent should not accelerate the fatigue of the processing 
solutions used for the photographic light-sensitive material. In addition, 
the antistatic agent should not be one that may reduce the bond strength 
between constituent layers of the photographic light-sensitive material. 
Thus, the application of an antistatic agent to photographic 
light-sensitive materials is subject to these and other restrictions. 
An approach toward eliminating these troubles due to static electricity is 
that of increasing the electrical conductivity of the surfaces of 
photographic light-sensitive materials, to thereby dissipate the 
accumulated static charge in a short time before a discharge of the static 
charge takes place. Accordingly, various methods have been proposed for 
improving the electrical conductivity of the support and various coating 
layers superimposed thereon of the photographic light-sensitive material. 
Thus, the use of various hygroscopic agents and water-soluble inorganic 
salts, certain types of surfactants, polymers, etc., has been recommended. 
For example, 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., mention such polymers; 
U.S. Pat. Nos. 2,982,651, 3,428,456, 3,457,076, 3,454,625, 3,552,972, 
3,655,387, etc., refer to surfactants; and U.S. Pat. Nos. 3,062,700, 
3,245,833, 3,525,621, etc., mention metal oxides, colloidal silica, etc. 
However, many of these substances display properties specific only to some 
types of film supports and photographic compositions, and while these 
substances may produce satisfactory results with certain kinds of support 
films, photographic emulsions, and other photographic elements, they are 
quite useless or even exert adverse effects on photographic 
characteristics with other kinds of supports and photographic elements. 
On the other hand, there also are many antistatic substances that cannot be 
used because they have adverse effects on photographic characteristics 
such as the sensitivity, fog, graininess, sharpness, etc., of the 
emulsion, notwithstanding the fact that they have excellent antistatic 
action. By way of illustration, polyethylene oxide compounds are generally 
known to have an antistatic effect, but tend to cause ill effects on 
photographic characteristics, such as increased fog, desensitization, 
graininess degradation, etc. 
Particularly in regard to a direct X-ray-sensitive material for medical 
use, the support of which carries a radiographic emulsion layer on either 
side, it has been difficult to establish a technique for imparting an 
antistatic property thereto without sacrificing its photographic 
characteristics. Thus, it is very difficult to apply an antistatic agent 
to photographic light-sensitive materials, and the range of application 
has been limited. 
Another approach toward obviating problems due to static charges in 
photographic light-sensitive materials is that of controlling the surface 
static potential of the light-sensitive material so as to minimize the 
generation of static electricity due to friction and contact. For example, 
attempts have been made to use fluorine-containing surfactants as 
described in British Pat. Nos. 1,330,356 and 1,524,621, U.S. Pat. Nos. 
3,666,478 and 3,589,906, Japanese Patent Publication No. 26687/77, 
Japanese patent application (OPI) Ser. Nos. 46733/74 and 32322/76 (the 
term "OPI" as used herein refers to a "published unexamined Japanese 
patent application open to public inspection"), and so on in photographic 
light-sensitive materials for the above-mentioned purposes. However, since 
the static charge characteristics of photographic light-sensitive 
materials containing such fluorine-containing surfactants are dependent on 
the characteristics of the surfactant used, such as formation of a 
unimolecular film, they vary markedly with different processing conditions 
to which such photographic light-sensitive materials are subjected in the 
course of their production. The result is that uniform products having 
uniform static charge characteristics cannot be produced on a consistent 
basis. For example, the static charge characteristics of products vary 
widely in response to the temperature and humidity conditions used in the 
stages where the respective layers of the photographic light-sensitive 
materials are formed or the temperature, humidity, or/and drying time used 
in the drying stage subsequent to the coating processes. Therefore, while 
satisfactory products are obtained at times, products with quite poor 
static charge characteristics are produced at other times, thus presenting 
a serious obstacle to effective quality control. Thus, said 
fluorine-containing surfactants that have been used have the foregoing and 
other disadvantages. 
To overcome the above-mentioned disadvantages of fluorine-containing 
surfactants, attempts have also been made to utilize fluorine-containing 
polymers in photographic light-sensitive materials. For example, U.S. Pat. 
No. 4,266,015 teaches the use of an emulsion (latex) of a homopolymer of a 
fluorine-containing alcohol acrylic or methacrylic acid ester or of a 
copolymer of such ester monomer with some other monomer and U.S. Pat. No. 
4,299,524 discloses the use of a copolymer of said fluorine-containing 
monomer with a polyethylene oxide chain-containing monomer. Japanese 
Patent Publication No. 15376/82 teaches the use of a copolymer of a 
fluorine-containing monomer such as said fluorine-containing monomer, a 
fluorine-containing carboxylic acid vinyl ester, a fluorine-containing 
vinyl ether, or a fluorine-substituted olefin with a quaternary 
nitrogen-containing monomer, while U.S. Pat. No. 3,753,716 teaches the use 
of a terpolymer of a fluorine-containing alcohol maleic acid ester, maleic 
acid, and another monomer in the photographic light-sensitive material 
(particularly in its surface layer). When such a fluorine-containing 
polymer is applied to a photographic light-sensitive material, the surface 
static potential of the light-sensitive material can be modulated to a 
certain extent so that the generation of static charges due to friction or 
contact can be somewhat decreased. Moreover, this technique overcomes, in 
some measure, the above-mentioned disadvantages of fluorine-containing 
surfactants, namely, the disadvantage that the static charge 
characteristics of light-sensitive materials vary a great deal with 
production conditions and the disadvantage that said characteristics age 
or deteriorate with time. However, photographic light-sensitive materials 
incorporating such fluorine-containing polymers have various drawbacks, 
for example, in respect of said static charge characteristics or in regard 
to photographic characteristics and film physical properties which are 
important factors in photographic light-sensitive materials, and these 
drawbacks detract considerably from their market value so that virtually 
these polymers cannot be used in photographic light-sensitive materials. 
The layer of a photographic light-sensitive material which contains the 
fluorine-containing polymer emulsion as described in U.S. Pat. No. 
4,266,015 is so tacky that there tends to occur an adhesion between the 
emulsion layers or between the emulsion layer and the backing layer of the 
material, and once adhered to each other, they cannot be separated, or if 
they can be separated, a conspicuous adhesion scar remains. Moreover, the 
polymer-containing layer of the photographic light-sensitive material 
tends to be marred by frictional contact with other surfaces or by 
scratching and such mars detract from the market value of photographic 
light-sensitive materials in a remarkable degree. On the other hand, the 
fluorine-containing polymers described in U.S. Pat. No. 4,299,524, 
Japanese Patent Publication No. 15376/82, and U.S. Pat. No. 3,753,716 must 
be added in substantial amounts to photographic light-sensitive materials, 
for they are quite deficient in their ability to control the static 
potential. This means not only an increased production cost, but also 
produces adverse effects on photographic characteristics such as decreased 
sensitivity, reduced density, and fog as well as on film properties such 
as liability to stick, or to be marred. Therefore, these polymers cannot 
be utilized in photographic light-sensitive materials. 
To obviate the above-mentioned disadvantages of fluorine-containing 
polymers, British Pat. No. 2,080,559 and U.S. Pat. No. 4,362,812 teach a 
fluorine-containing polymer obtainable by copolymerizing a hydrophobic 
fluorine-containing monomer, which is a styrene derivative, with a 
water-soluble monomer. This fluorine-containing polymer enables one to 
adjust the static charge potential with a reduced amount as compared with 
the first-mentioned fluorine-containing polymer so that the production 
cost can be reduced. Moreover, the above-mentioned adverse effects on 
photographic characteristics such as decreased sensitivity, reduced 
density, and fogging, and on film properties such as liability to stick or 
be easily marred can be alleviated. 
However, the sensitivity of photographic light-sensitive materials has been 
on a steady increase in recent years, as epitomized by the development of 
color reversal film and color negative film with an ISO sensitivity of 
1600. 
The photographic characteristics of these high sensitivity photographic 
light-sensitive materials are very delicate and the addition of even a 
minor impurity may alter the photographic characteristics in a remarkable 
measure. Therefore, when an antistatic agent is to be added to such a high 
sensitivity photographic material, the antistatic agent must not only be 
inert to the photographic emulsion but must also be capable of producing a 
potent antistatic effect even when used in a small amount. 
The above-mentioned fluorine-containing polymer realizes a sufficient 
antistatic effect without affecting the photographic characteristics as 
long as it is used in a low sensitivity photographic light-sensitive 
material, but it cannot be used with respect to the above-noted recent 
high sensitivity photographic materials. Thus, the untoward effects on 
photographic characteristics such as decreased sensitivity, reduced 
density, and fogging are inevitable and unavoidable with the polymer just 
mentioned insofar as it is applied to high sensitivity photographic 
materials. 
Moreover, the development process has also become more rapid than ever 
before, and today photographic light-sensitive materials are developed 
under remarkably tortuous conditions. 
As mentioned in regard to the recent trend toward an ever increasing 
sensitivity of photographic materials, photographic characteristics are 
becoming more and more delicate so that, in this regard too, the 
antistatic agent must not only be inert to the photographic emulsion but 
be capable of affording a sufficient antistatic effect while being used in 
as small an amount as possible. When a static-inhibited photographic 
light-sensitive material incorporating the above fluorine-containing 
polymer is subjected to rapid development, its photographic 
characteristics are adversely affected. Therefore, the above-mentioned 
fluorine-containing polymer cannot be utilized in conjunction with rapid 
development materials. 
In addition, high speed coating technology has recently been applied to the 
production of photographic light-sensitive materials as well, and, mainly 
during take-up of the photographic light-sensitive material, the surface 
of the light-sensitive material is subjected to high pressure. Under the 
circumstances, it has become necessary that the surface of the 
photographic light-sensitive material will not stick, but rather will be 
low in tackiness. 
In earlier low speed production processes, the surface of the photographic 
light-sensitive material was only subject to moderate pressure and, 
therefore, even the above-mentioned fluorine-containing polymer was 
sufficient to ensure the necessary antitack property. However, with the 
recent development of high speed coating technology, the surface of the 
photographic light-sensitive material has come to be subjected to very 
substantial pressure, so that the fluorine-containing polymer just 
mentioned is unable to ensure a sufficient antitack property. 
In this connection, it is important to understand that the 
fluorine-containing polymers mentioned hereinbefore belong to the category 
of "random copolymers". Generally, a random copolymer is a copolymer in 
which two or more kinds of monomer units are randomly arranged. In the 
production of a random copolymer, the mixing of the constituent units 
takes place on a monomer scale so that a homogeneous polymer compound 
tends to be obtained. However, because of the interactions between the 
constituent monomers, for instance, it is in many cases impossible to 
obtain the characteristics typical of the respective homopolymers. On the 
other hand, a "blending" of dissimilar polymers does not give a uniform 
composition in many cases but the respective polymers form distinct phases 
so that the phenomenon called phase separation takes place. In contrast to 
the above polymers, the so-called block polymer in which a polymer chain 
consisting of monomer units of a given kind is connected to a polymer 
chain consisting of monomer units of another kind in a linear fashion is 
characterized in that because the two dissimilar polymer segments are 
joined together by chemical bonding, it does not undergo as serious a 
phase separation as does a polymer blend, but does undergo the so-called 
microphase separation, assuming a multiphase structure. This is an 
outstanding feature which is not found in random copolymers and polymer 
blends. 
Various characteristics of block polymers are generally described, for 
example, in the Society of High Polymer Chemistry: Polymer Alloys (Tokyo 
Kagaku Dojin, 1981); R. J. Ceresa, Block and Graft Polymerization, Vol. 1 
(John Wiley & Sons, 1973); and Yamashita et al., Oil Chemistry, Vol. 29, 
pp. 219-225 (1980). 
Paying attention to these various characteristics of block polymers, the 
present inventors conducted an intensive research to develop an antistatic 
agent free of the above disadvantages of fluorine-containing random 
copolymers. As a result, it was found surprisingly that the use of a block 
polymer derived from a hydrophobic fluorine-containing monomer and a 
hydrophilic monomer as an antistatic agent in the photographic 
light-sensitive material results in complete elimination of all the 
aforesaid disadvantages of said fluorine-containing random copolymers. 
SUMMARY OF THE INVENTION 
A first object of this invention is to provide a static-inhibited 
photographic light-sensitive material which is substantially free from 
build-ups of static charge. 
A second object of this invention is to provide a static-inhibited 
photographic light-sensitive material which is free from the adverse 
influence of increased sensitivity upon photographic characteristics such 
as density, fog, etc. 
A third object of this invention is to provide a static-inhibited 
photographic light-sensitive material which is free from adverse effects 
on photographic characteristics even under extreme developing and 
processing conditions, such as rapid processing, etc. 
A fourth object of this invention is to provide a static-inhibited 
photographic light-sensitive material which does not stick even if its 
surface is subjected to high pressure due to high speed production, etc. 
These objects have now been accomplished by the present invention, which 
comprises incorporating a fluorine-containing block polymer, derived from 
a polymerizable hydrophobic fluorine-containing monomer having at least 
one fluorine atom and a polymerizable hydrophilic monomer, as an 
antistatic agent, in at least one layer of a photographic light-sensitive 
material. 
Also, said fluorine-containing block polymer may contain a third 
polymerizable monomer unit. 
DETAILED DESCRIPTION OF THE INVENTION 
The preferred examples of the fluorine-containing block polymer according 
to this invention are as follows. The fluorine-containing block polymer 
according to this invention is preferably a fluorine-containing block 
polymer comprising one of repeating units represented by formulae (I), 
(II) and (III): 
EQU --(A).sub.r (B).sub.s (I) 
EQU --(A).sub.t (B).sub.u (A).sub.v (II) 
EQU --(B).sub.w (A).sub.x (B).sub.y (III) 
Referring to formulae (I), (II), and (III), A represents the monomer unit 
of a polymer obtainable by polymerizing a polymerizable 
fluorine-containing monomer having at least one fluorine atom; B 
represents the monomer unit of the polymer obtainable by polymerizing a 
polymerizable hydrophilic monomer; r, t, v, and x each represents the 
average degree of polymerization of monomer A and is a number between 2 
and about 1,000; and s, u, w, and y each represents the average degree of 
polymerization of monomer B and is a number between 2 and about 5,000. 
The block polymer of formula (I) is a block polymer consisting of two 
homopolymer segments, while the block polymer of formulae (II) and (III) 
each is a block polymer consisting of 3 homopolymer segments. A so-called 
multiblock polymer consisting of four or more homopolymer segments is also 
within the scope of this invention. Furthermore, these fluorine-containing 
block polymers may further contain a polymerizable third monomer. 
The polymerizable hydrophobic fluorine-containing monomer having at least 
one fluorine atom as represented by A in formula (I), (II) or (III) is 
selected according to the contemplated mode of polymerization, but is 
preferably an addition-polymerizable monomer containing an ethylenically 
unsaturated group or a ring-opening polymerizable monomer. 
The addition-polymerizable fluorine-containing monomer having an 
ethylenically unsaturated group is preferably a monomer of formula (IV) or 
a monomer of formula (V). 
The monomer of formula (IV) is represented by 
##STR1## 
wherein R.sup.1 is a hydrogen atom, a chlorine atom, or an alkyl group 
containing from 1 to 3 carbon atoms; R.sup.2 is a monovalent substituent 
group or two R.sup.2 's can jointly form a ring; R.sup.f is an alkyl, 
aralkyl, aryl, or alkylaryl group containing from 1 to 30 carbon atoms and 
having one or more of its hydrogen atoms replaced by fluorine atoms; X is 
a divalent linking group represented by the formula --(R).sub.o L-- or 
--L--(R).sub.o, where R is an alkylene, arylene, or aralkylene group 
containing 1 to 10 carbon atoms, --L-- is an --O--, --S--, --NR.sup.3 -- 
(R.sup.3 is an alkyl group containing from 1 to 4 carbon atoms), --CO--, 
--OCO--, --SCO--, --CONR.sup.3 --, --SO.sub.2 --, --NR.sup.3 SO.sub.2 --, 
--SO.sub.2 NR.sup.3 -- or --SO-- group, and o is 0 or 1; l is an integer 
of 0 to 4, and preferably an integer of 0 to 2, m is an integer of 0 to 4, 
and preferably an integer of 0 or 1; and n is an integer of 1 to 5, and 
preferably an integer of 1 or 2. 
The monomer of formula (V) is represented by 
##STR2## 
wherein R.sup.1, X, R.sup.f, and m are the same as defined for formula 
(IV). 
Referring to formulae (IV) and (V), R.sup.1 is more preferably a hydrogen 
atom or a methyl group; R.sup.2 may, for example, be halogen, nitro, 
amino, alkylamino, carboxy, sulfo, carboxylic acid ester, sulfonic acid 
ester, carbamoyl, sulfamoyl, alkylsulfonyl, alkoxy, thioalkoxy, alkyl, or 
aryl. These and other examples are well-described in the literature, such 
as The Chemical Society of Japan: Kagaku Binran (Chemical Handbook) 
Fundamentals II, Revised 2nd Edition (Maruzen Co.), pp. 1012-1013; and 
Zeng Guangzhi, Acta Chim. Sinica, Vol. 32, p. 107 (1966). R.sup.2 is 
preferably a halogen, nitro, alkyl, or the like. The R.sup.2 's can 
jointly form a ring, which may, for example, be a benzene ring. R.sup.f 
represents an alkyl, aralkyl, aryl or alkylaryl group containing from 1 to 
30 carbon atoms (preferably from 1 to 20), and has one or more of its 
hydrogen atoms replaced by fluorine atoms, preferred examples of which 
include perfluoromethyl, perfluoroethyl, perfluoropropyl, perfluorohexyl, 
perfluorooctyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,4,4,5,5-octafluoroamyl, 
2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl, 2,2,2-trifluoroethyl, 
2,2,3,3,4,4,4-heptafluorobutyl, 1,1,1,3,3,3-hexafluoro-2-propyl, 
1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propyl, 
1,1,2,2-tetrafluoro-2-hydroxyethyl, p-fluorophenyl, 
p-trifluoromethylphenyl, 2,3,4,5,6-pentatrifluoromethylphenyl, etc. 
Exemplary monomers of formulae (IV) and (V) are as follows. 
##STR3## 
Referring to said polymerizable hydrophobic fluorine-containing monomer 
having at least one fluorine atom as represented by A in formula (I), 
(II), or (III), the monomers which undergo ring-opening polymerization are 
preferably 2-oxazoline monomers represented by formula (VI) 
##STR4## 
wherein X, R.sup.f and m are the same as defined in formula (V). 
The following is an exemplary list of monomers of formula (VI). 
##STR5## 
Like the hydrophobic fluorine-containing monomer A, the polymerizable 
hydrophilic monomer represented by B in formula (I), (II), or (III) is 
also selected according to the intended mode of polymerization, and is 
preferably an addition-polymerizable monomer containing an ethylenically 
unsaturated group or a ring-opening polymerizable monomer. 
Such addition-polymerizable hydrophilic monomer containing an ethylenically 
unsaturated group includes, but is not limited to, nonionic monomers such 
as acrolein, acrylamide, methacrylamide, N-methylolacrylamide, 
N,N-dimethylaminoethylacrylamide, N,N-dimethylaminopropylacrylamide, 
hydroxyethyl methacrylate, N,N-dimethylaminoethyl acrylate, 
N,N-dimethylaminoethyl methacrylate, poly(ethyloxy)acrylate, 
poly(ethyloxy)methacrylate, 2-vinylpyridine, 4-vinylpyridine, 
1-vinyl-2-pyrrolidone, 1-vinylimidazole, 1-vinyl-2-methylimidazole, etc.; 
cationic monomers such as vinylbenzyltrimethylammonium, 
vinylbenzyltriethylammonium, vinylbenzyltripropylammonium, 
vinylbenzyldimethylamine hydrochloride, 
methacryloxyethyltrimethylammonium, methacryloxyethyldimethylethylammonium 
, N,N-dimethylaminoethyl methacrylate hydrochloride, etc., and anionic 
monomers such as acrylic acid, methacrylic acid, maleic acid, 
styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, etc., and 
salts thereof. 
Examples of said ring-opening polymerizable monomer include substituted or 
unsubstituted cyclic ethers such as ethylene oxide, glycidol, propylene 
oxide, tetrahydrofuran, trioxane, etc.; 2-oxazoline and 
substituted-2-oxazolines such as those represented by the formula 
##STR6## 
wherein p is a number of 1 to 50; R.sup.4 is a hydrogen atom or an alkyl 
group containing 1 to 3 carbon atoms; and lactones such as 
.beta.-propiolactone, etc. 
For additional examples, see Saekusa, Ring-Opening Polymerization (I), 
(Kagaku Dojin, 1971). 
The third monomer copolymerizable with the fluorine-containing block 
polymer according to this invention is exemplified by olefins such as 
ethylene, propylene, 1-butene, etc.; styrene and its derivatives such as 
.alpha.-methylstyrene, vinyltoluene, chloromethylstyrene, divinylbenzene, 
etc.; ethylenically unsaturated esters of organic acids such as vinyl 
acetate, acrylic acetate, etc.; ethylenically unsaturated carboxylic acid 
esters such as methyl acrylate, methyl methacrylate, n-butyl acrylate, 
n-butyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl 
acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, etc.; 
ethylenically unsaturated carboxylic acid amides such as 
N-butylacrylamide, N-amylacrylamide, etc.; dienes such as butadiene, 
isoprene, etc.; acrylonitrile; vinyl chloride; maleic anhydride; etc. In 
addition, the ring-opening polymerizable monomers described in Saekusa, 
Ring-Opening Polymerization (I) and (II), (Kagaku Dojin, 1971) may also be 
used. It is to be understood that said third monomer is not limited to 
those mentioned above. 
The fluorine-containing block polymer of this invention can be synthesized 
by various methods such as radical polymerization, anionic polymerization, 
cationic polymerization, coordination polymerization, sequential growth 
reaction, etc.; the preferred method of synthesis depends on the 
structures and reactivities of the starting material hydrophobic 
fluorine-containing monomer and hydrophilic monomer. 
Methods of synthesis of block polymers are described in various literature, 
such as in Polymer Alloy, pp. 10-22 (Tokyo Kagaku Dojin, 1981); R. J. 
Ceresa, Ed., Block and Graft Polymerization, Vol. 1 (John Wiley & Sons, 
1973), etc., and these methods can be applied to the synthesis of the 
fluorine-containing block polymer of this invention. 
Examples of the fluorine-containing block polymer according to this 
invention are as follows. 
##STR7## 
Examples of synthesis of fluorine-containing block polymer according to 
this invention are as follows. 
SYNTHESIS EXAMPLE 1 
Synthesis of Fluorine-Containing Graft Polymer BP-1 
A glass reaction vessel in which a high vacuum was established with an oil 
rotary pump and mercury diffusion pump was charged with 80 ml of a 
solution of the initiator cumylpotassium in tetrahydrofuran (0.183 mol/l; 
prepared in accordance with Shin Jikken Kagaku Koza (Lectures on New 
Experimental Chemistry), Vol. 19, published by The Chemical Society of 
Japan; Polymer Chemistry (I), pp. 64-65 (Maruzen, 1978). Then, at room 
temperature, 500 ml of a solution of fluorine-containing Monomer IV-12 in 
tetrahydrofuran (0.29 mol/l) was added and the anionic polymerization of 
fluorine-containing Monomer IV-12 was conducted. A small sample was taken 
from the resulting polymer of Monomer IV-12 and the number average degree 
of polymerization was measured by the vapor pressure depression method. 
The average degree of polymerization was 7.2. 
To the same reaction vessel was added 88 g of cooled ethylene oxide and the 
polymerization reaction was conducted for 30 hours. The reaction product 
was purified by repeated precipitation and dried to give 71 g of 
fluorine-containing Block Polymer BP-1. Based on elemental analysis, the 
average degree of polymerization of the ethylene oxide was 89. 
SYNTHESIS EXAMPLE 2 
Synthesis of Fluorine-Containing Block Copolymer BP-2 
A 500 ml three-necked flask fitted with a stirrer, calcium chloride 
desiccator and reflux condenser was charged with 100 g of polyethylene 
glycol (average degree of polymerization 35; available commercially from 
Nippon Oils and Fats Co., Ltd., under the trade name of PEG-1540). After 
the polyethylene glycol was dissolved in 200 ml of pyridine, 37 g of 
p-toluenesulfonyl chloride was added at room temperature. The reaction was 
conducted at 50.degree. C. for 4 hours, whereby 60 g of polyethylene 
glycol di(p-toluenesulfonate) was obtained. Then, 12 g of this polymer, 40 
g of fluorine-containing Monomer VI-4, and 200 ml of solvent 
tetrahydrofuran were placed in a tube and after purging with nitrogen gas, 
the tube was sealed. The tube was heated at 60.degree. C. to conduct a 
cationic polymerization. The reaction product was purified by repeated 
precipitation, and dried to give 38 g of fluorine-containing Block 
Copolymer BP-2. 
The application amount of the fluorine-containing block polymer of this 
invention varies according to types and forms of photographic 
light-sensitive material, coating method, etc. Generally, however, it is 
used in a proportion of from 0.001 to 0.1 g/m.sup.2 of photographic 
light-sensitive material and preferably 0.001 to 0.02 g/m.sup.2. 
As regards the method of incorporating the block polymer of this invention 
in a layer or layers of the photographic light-sensitive material, one may 
employ the steps of dissolving it in an organic solvent (e.g., methanol, 
ethanol, acetone, methyl ethyl ketone, ethyl acetate, acetonitrile, 
dioxane, dimethylformamide, formamide, dimethyl sulfoxide, methyl 
cellosolve, ethyl cellosolve, etc.) or a mixture of such organic solvents 
and having the solution contained in the light-sensitive emulsion layer or 
a non-light-sensitive auxiliary layer (for example, a backing layer, 
antihalation layer, interlayer or protective layer) or applying it to the 
surface of the photographic light-sensitive material by spraying, coating 
or dipping, followed by drying. 
It is also possible to use the block polymer of this invention in 
combination with a binder such as gelatin, polyvinyl alcohol, cellulose 
acetate, cellulose acetate phthalate, polyvinyl formal, polyvinyl butyral 
or the like to form an antistatic layer. 
It is also possible to use other antistatic agents in the layer containing 
the fluorine-containing block polymer of this invention or in other layer 
or layers, whereby still more satisfactory antistatic effects may 
sometimes be obtained. Examples of such other antistatic agents include 
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, 4,070,189 and 
4,147,550, German Pat. No. 2,800,466, and Japanese patent application 
(OPI) Ser. Nos. 91165/73, 94433/73, 46733/74, 54672/75, 94053/75, and 
129520/77; surfactants as described in U.S. Pat. Nos. 2,982,651, 
3,428,456, 3,457,076, 3,454,625, 3,552,971, and 3,655,387, for instance; 
the metal oxides described in U.S. Pat. Nos. 3,062,700, 3,245,833, and 
3,525,621, for instance; and the so-called matting agent comprising 
colloidal silica or composed of strontium barium sulfate, polymethyl 
methacrylate, methyl methacrylate-methacrylic acid copolymer and colloidal 
silica or silica powder, for instance. 
The layer containing the fluorine-containing block polymer of this 
invention may, for example, be the emulsion layer or the subbing layer, 
interlayer, surface protective layer or overcoat layer on the same side of 
the emulsion layer or the backing layer on the opposite side of the 
emulsion layer. Of these layers, an outermost layer, such as the surface 
protective layer, overcoat layer, or backing layer is preferred. 
The support of the photographic light-sensitive material to which the 
fluorine-containing block polymer of this invention can be applied 
includes films of polyolefins such as polyethylene, etc., polystyrene, 
cellulose derivatives such as cellulose triacetate, etc., and polyesters 
such as polyethylene terephthalate, etc., and baryta paper, synthetic 
paper, paper, etc., both sides of which have been covered with such 
polymer films, as well as other support materials analogous thereto. 
The support layer used in accordance with this invention may be provided 
with an antihalation layer. For this purpose, carbon black or various dyes 
such as oxonol dyes, azo dyes, arylidene dyes, styryl dyes, anthraquinone 
dyes, merocyanine dyes and tri(or di)arylmethane dyes, etc., can be 
utilized. As binders for carbon black and dyes, cellulose (di- or 
mono-)acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl acetal, 
polyvinyl formal, polymethacrylates, polyacrylates, polystyrene, 
styrene-maleic anhydride copolymer, polyvinyl acetate, vinyl 
acetate-maleic anhydride copolymer, methyl vinyl ether-maleic anhydride 
copolymer, polyvinylidene chloride, and their derivatives may be employed. 
The photographic light-sensitive materials according to this invention may 
be made available in various forms, for example, ordinary black-and-white 
silver halide light-sensitive materials (e.g., black-and-white 
light-sensitive materials for photography, X-ray use, printing, etc.), 
ordinary multilayer color light-sensitive materials (e.g., color reversal 
film, color negative film, color positive film, etc.) and so on. The 
effects of this invention are realized particularly well in silver halide 
light-sensitive materials for high temperature rapid processing and high 
sensitivity silver halide light-sensitive materials. A photographic layer 
for a silver halide light-sensitive material according to this invention 
is described below. 
As the binder for the photographic layer, proteins such as gelatin, casein, 
etc., cellulose compounds such as carboxymethyl cellulose, hydroxyethyl 
cellulose, etc., carbohydrates such as agar, sodium alginate, starch 
derivatives, etc., synthetic hydrophilic colloids such as polyvinyl 
alcohol, poly-N-vinyl-pyrrolidone, acrylic copolymers, polyacrylamide, and 
derivatives, partial hydrolysates, etc., thereof may be used in 
conjunction. 
The term "gelatin" as used herein means any of lime-treated gelatin, 
acid-treated gelatin, and enzyme-treated gelatin. 
The gelatin may be replaced, either in part or as a whole, with a synthetic 
high polymer or a gelatin derivative obtainable by modifying gelatin with 
a chemical reagent having a group reactive to the functional groups (such 
as amino, imino, hydroxy, or carboxyl) present in the molecule. It is also 
possible to use gelatin grafted to some other macromolecular chain. 
There is substantially no limitation on the type and method of production 
of silver halide that may be used for the silver halide emulsion layer of 
the photographic light-sensitive material according to this invention, nor 
are there limitations on the method of chemical sensitization, antifogging 
agent, stabilizer, film hardener, antistatic agent, plasticizer, 
lubricant, coating assistant, matting agent, whitener, spectral 
sensitizing pigment, dye, color coupler, etc. Further detailed information 
regarding silver halide emulsions and components and additives therefor, 
references are described in literature such as Product Licensing, No. 92, 
pp. 107-110 (Dec., 1971) and Research Disclosure, No. 176, pp. 22-31 
(Dec., 1978). 
Regarding the antifogging agent and stabilizer, in particular, 
4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene-3-methylbenzothiazole, 
1-phenyl-5-mercaptotetrazole and many other heterocyclic compounds, 
mercury-containing compounds, mercapto compounds, metal salts and numerous 
other compounds can be utilized. As examples of said film hardener, there 
may be mentioned aldehyde compounds such as mucochloric acid, muchbromic 
acid, mucophenoxychloric acid, mucophenoxybromic acid, formaldehyde, 
dimethylolurea, trimethylolmelamine, glyoxal, monomethylglyoxal, 
2,3-dihydroxy-1,4-dioxane, 2,3-dihydroxy-5-methyl-1,4-dioxane, 
succinaldehyde, 2,5-dimethoxytetrahydrofuran, glutaraldehyde, etc.; active 
vinyl compounds such as divinylsulfone, methylenebismaleimide, 
5-acetyl-1,3-diacryloyl-hexahydro-s-triazine, 
1,3,5-triacryloylhexahydro-s-triazine, 
1,3,5-trivinylsulfonyl-hexahydro-s-triazine bis(vinylsulfonylmethyl)ether, 
1,3-bis(vinylsulfonylmethyl)propanol-2, 
bis(.alpha.-vinylsulfonylacetamido)ethane, etc.; active halogen compounds 
such as 2,4-dichloro-6-hydroxy-s-triazine sodium, 
2,4-dichloro-6-methoxy-s-triazine, 
2,4-dichloro-6-(4-sulfonailino)-s-triazine sodium, 
2,4-dichloro-6-(2-sulfoethylamino)-s-triazine, 
N,N'-bis(2-chloroethylcarbamyl)piperazine, etc.; epoxy compounds such as 
bis(2,3-epoxypropyl)methylpropylammonium p-toluenesulfonate, 
1,4-bis(2',3'-epoxypropoxy)butane, 1,3,5-triglycidylisocyanurate, 
1,3-diglycidyl-5-(.gamma.-acetoxy-.beta.-oxypropyl)isocyanurate, etc.; 
ethyleneimine compounds such as 2,4,6-triethyleneimino-s-triazine, 
1,6-hexamethylene-N,N'-bisethyleneurea, 
bis-.beta.-ethyleneiminoethylthioether, etc.; methanesulfonic acid ester 
compounds such as 1,2-di(methanesulfonyloxy)ethane, 
1,4-di(methanesulfonyloxy)butane, 1,5-di(methanesulfonyloxy)pentane; 
carbodiimide compounds, isoxazole compounds; and inorganic compounds such 
as chrome alum, etc. 
In the photographic layer of this invention, there may be incorporated one 
or more of the hitherto known surfactants. The surfactants that can be 
used include natural surfactants such as saponin, etc.; nonionic 
surfactants such as alkylene oxides, glycerin, glycidol and other 
surfactants; cationic surfactants such as higher alkylamines, quaternary 
ammonium salts, pyridine and other heterocyclic compounds, phosphonium or 
sulfonium compounds, etc.; anionic surfactants containing acidic groups 
such as carboxylic acids, sulfonic acids, phosphoric acids, sulfuric acid 
esters, phosphoric acid esters, etc.; and amphoteric surfactants such as 
amino acids, aminosulfonic acids, sulfuric or phosphoric acid esters of 
aminoalcohols, and so on. 
The photographic light-sensitive material according to this invention may 
contain the alkyl acrylate latices described in U.S. Pat. Nos. 3,411,911 
and 3,411,912, Japanese Patent Publication No. 5331/70, etc. 
The following examples are intended to illustrate this invention in further 
detail and should be no means construed as limiting the scope of the 
invention.

EXAMPLE 1 
(1) Preparation of Samples 
The emulsion layer dope and surface protective layer dope mentioned below 
were prepared and used to coat a subbed polyethylene terephthalate support 
film as thick as 180 .mu. in the order of the emulsion layer and 
protective layer by the concurrent extrusion coating method, followed by 
drying. 
The other side of the support was also coated with the same dopes in the 
same manner as above to give a photographic light-sensitive material. The 
coating amount or coverage of silver on either side of the support was 4.0 
g/cm.sup.2. The gelatin coverage for the surface protective layer was 1.1 
g/m.sup.2. 
The fluorine-containing block polymer of this invention or the control 
fluorine-containing polymer was added to the protective layer dope. 
Preparation of the Silver Halide Emulsion 
Silver iodide grains (silver iodide 1.5 mol %) (average particle size 1.35 
.mu.) were prepared in the presence of ammonia by the double jet method 
and chemically sensitized with chloroaurate and sodium thiosulfate. After 
this chemical sensitization, an antifogging agent 
(1-phenyl-5-mercaptotetrazole), a stabilizer 
(4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene) and coating assistants were 
added so as to give an emulsion dope. The specific gravity of the coating 
dope was 1.12 and the weight ratio of silver to gelatin was 1.55. 
Preparation of the Surface Protective Layer Dope 
A 10% aqueous gelatin solution was prepared using gelatin, sodium 
polystyrenesulfonate, dispersed polymethyl methacrylate (average particle 
size 3.0 .mu.), sodium t-octylphenoxyethoxyethoxyethanesulfonate and 
N,N'-ethylenebis(vinylsulfonylacetamide) for use as a coating dope for 
formation of a surface protective layer. 
(2) Test Methods 
Method of Measuring the Static Potential 
The above sample was cut into a rectangular specimen measuring 30 cm by 40 
cm and conditioned for moisture at 25.degree. C. and 25% R.H. for 5 hours. 
The specimen was then passed through a revolving pair of white neoprene 
rubber rollers (roller diameter 12 cm, roller width 1 cm, pressure between 
rollers 6 kg/cm.sup.2, linear velocity 320 m/min.) and, in a Faraday cage, 
the static potential was measured with an electrometer. Photographic 
Characteristic Test: 
The above film was sandwiched between a couple of Fuji Photographic Film 
Hi-Standard Screens (calcium tungstate) and exposed to X-rays through an 
aluminum wedge for 1/20 second. Using a roller-transport automatic 
developing machine (Fuji RU, built by Fuji Photo Film Co., Ltd.) and the 
developer solution of the following composition, development was carried 
out at 35.degree. C. for 25 seconds. The developed specimen was fixed at 
34.degree. C. for 25 seconds, rinsed at 33.degree. C. for 25 seconds and 
dried at 45.degree. C. Then, sensitometry was carried out. 
______________________________________ 
Formulation of the Developer Solution 
______________________________________ 
Potassium Hydroxide 29.14 g 
Glacial Acetic Acid 10.96 g 
Potassium Sulfite 44.20 g 
Sodium Bicarbonate 7.50 g 
Boric Acid 1.00 g 
Diethylene Glycol 28.96 g 
Ethylenediaminetetraacetate 
1.67 g 
5-Methylbenzotriazole 0.06 g 
5-Nitroindazole 0.25 g 
Hydroquinone 30.00 g 
1-Phenyl-3-pyrazolidone 
1.50 g 
Glutaraldehyde 4.93 g 
Sodium Metabisulfite 12.60 g 
Potassium Bromide 6.00 g 
Water to make 1 liter 
pH adjusted to 10.25 
______________________________________ 
Antitack Test 
The above sample was cut into square sheets each measuring 4 cm by 4 cm and 
conditioned for moisture at 25.degree. C. and 70% R.H. for 2 days. Two of 
the sheets were superimposed and, under a 1,500 g load, allowed to stand 
at 50.degree. C. and 70% R.H. for 1 day. The two sheets were then pulled 
apart and the area of the stuck portion was measured and evaluated 
according to the following scheme. 
______________________________________ 
Rank A Bonded area 0-40% 
B Bonded area 41-60% 
C Bonded area 61-80% 
D Bonded area 81-100% 
______________________________________ 
(3) Results 
The results are shown in Table 1. 
TABLE 1 
__________________________________________________________________________ 
Static 
Photographic Characteristics 
Antistatic Agent 
Potential 
Sensitivity 
Maximum Antitack 
Sample No. 
(coating on either side, mg/m.sup.2) 
(volts) 
Fog 
(relative value) 
Density Property 
__________________________________________________________________________ 
1 (Blank) 
-- +410 0.15 
100 2.8 C 
2 (Invention) 
Block Polymer BP-1 (0.5) 
+190 " " " B 
3 (Invention) 
Block Polymer BP-1 (1) 
+90 " " " B 
4 (Invention) 
Block Polymer BP-1 (1.5) 
0 " " " A 
5 (Invention) 
Block Polymer BP-4 (0.5) 
+220 " " " B 
6 (Invention) 
Block Polymer BP-4 (1) 
+80 " " " B 
7 (Invention) 
Block Polymer BP-4 (2) 
-20 " " " A 
8 (Invention) 
Block Polymer BP-5 (1.5) 
0 " " " A 
9 (Invention) 
Block Polymer BP-2 (2) 
+10 " " " B 
10 (Invention) 
Block Polymer BP-7 (3) 
-10 " " " B 
11 (Control) 
Control Polymer 1 (2) 
+ 110 
0.16 
97 2.8 C 
12 (Control) 
Control Polymer 1 (4) 
+80 0.17 
95 2.6 C 
13 (Control) 
Control Polymer 1 (8) 
-10 0.18 
93 2.5 B 
14 (Control) 
Control Polymer 2 (4) 
+130 0.17 
98 2.8 C 
15 (Control) 
Control Polymer 2 (8) 
+60 0.19 
97 " C 
16 (Control) 
Control Polymer 2 (12) 
+10 0.20 
95 " B 
__________________________________________________________________________ 
CONTROL POLYMER 1 
Polymer P-1 (random copolymer), British Pat. No. 2,080,559 
##STR8## 
CONTROL POLYMER 2 
Polymer P-1 (random copolymer), U.S. Pat. No. 4,362,812 
##STR9## 
It is clear from the test results set forth in Table 1 that whereas the 
static charge on the blank sample free of an antistatic agent (Sample No. 
1) was large, the samples containing appropriate amounts (1.5 to 3 
mg/m.sup.2) of the block polymer of this invention (i.e., Sample No. 4: 
1.5 mg/m.sup.2, No. 7: 2 mg/m.sup.2, No. 8: 1.5 mg/m.sup.2, No. 9: 2 
mg/m.sup.2, No. 10: 3 mg/m.sup.2) were substantially not charged. On the 
other hand, the addition of Control Polymer 1 or 2 also resulted in a 
suppression of static charge, but it is clear that they had to be used in 
larger amounts for achieving the desired result (Sample No. 13: 8 
mg/m.sup.2, No. 16: 12 mg/m.sup.2). Moreover, whereas the addition of the 
block polymer of this invention did not cause any significant influence on 
photographic characteristics, the addition of the control polymers caused 
increases in fog, decreases in sensitivity and reductions in maximum 
density. Particularly, at high levels of addition sufficient to reduce the 
static charge to zero, the control polymers exerted pronounced adverse 
effects on photographic characteristics. In regard to antitack property, 
while the addition of the graft polymer according to this invention 
resulted in remarkable improvements as compared with the blank sample 
(Sample No. 1), the addition of control polymers resulted in an improving 
tendency, but the degree of improvement was extremely small. 
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.