Silver halide light-sensitive film material subjected to antistatic treatment

The present invention provides a silver halide light-sensitive film material having a backcoat layer which is sufficiently subjected to antistatic treatment. This material has an electrically conductive polymer layer comprising a copolymer of N-methylol(meth)acrylamide and styrenesulfonic acid as an antistatic layer between a film base and the backcoat layer.

BACKGROUND OF THE INVENTION 
The present invention relates to a silver halide photographic 
light-sensitive material and more particularly, to a backcoat layer 
prevented from accumulation of static charges. 
Films, papers and the like are used as a base for silver halide 
photographic materials and various problems have been brought about due to 
their low electrical conductivity. 
One of the problems is that when a coating composition containing silver 
halide is coated on a film, a paper or the like, the composition is coated 
by a coater at a high speed and the base is electrically charged during 
being rubbed by roller, and upon being discharged, silver halide undergoes 
fogging (antistatic fogging). If electrical conductivity of backcoat layer 
is enhanced and thus, antistatic treatment is made, since usually the 
backcoat layer is coated before coating of silver halide emulsion, this 
backcoat layer also improves the antistatic properties of the opposite 
surface of the base on which the emulsion is coated, through the base, 
whereby antistatic fogging can be inhibited. 
Another problem is that when users use light-sensitive materials, if the 
materials are electrically charged, dusts adhere to the light-sensitive 
materials and they often form undesired images such as pin holes during 
exposing and photographic treatments and besides, the light-sensitive 
materials stick to each other, resulting in deterioration of operability. 
Moreover, there is the problem that discharging occurs through hands of 
workers. 
It is important that the materials must have good antistatic 
characteristics both before and after the treatments such as development, 
fixation and rinsing. 
Japanese Patent Kokai Nos.56-92535 and 61 174542 disclose to provide an 
antistatic layer between a backcoat layer and a base to increase 
antistatic properties and besides, to use an aziridine hardener for 
improving adhesion between the antistatic layer and the backcoat layer. 
However, the aziridine hardener causes eruption of skin and is not desired 
for sanitary reasons. In addition, since the antistatic layer is provided 
between the base and the backcoat layer, adhesion of the backcoat layer is 
not sufficient and drying characteristics are inferior. 
SUMMARY OF THE INVENTION 
The object of the present invention is to provide a backcoat layer which 
has superior antistatic properties, inhibits blocking, has no influence on 
filter dyes contained therein, and is superior in adhesion and 
coatability. 
That is, the present invention is a silver halide light-sensitive film 
material which has an electrically conductive polymer layer between a 
backcoat layer containing gelatin and a film base, wherein the 
electrically conductive polymer is a copolymer of 
N-methylol(meth)acrylamide and styrenesulfonic acid. 
This silver halide light-sensitive film material of the present invention 
has further industrial merits in the following embodiments. 
The first embodiment is that the electrically conductive polymer has a 
copolymerization ratio of N-methylol(meth)acrylamide of 10-60% by weight. 
The second embodiment is that pH of the coating composition for the polymer 
layer is 1.5-3.0. 
The third embodiment is that drying temperature for coating of the polymer 
layer is 40.degree. C. or higher and the film is taken up in an atmosphere 
of 40-60% in relative humidity after completion of drying. 
The fourth embodiment is that the electrically conductive polymer layer 
contains a specific surface active agent. 
The fifth embodiment is that the electrically conductive polymer layer 
contains a matting agent. 
DESCRIPTION OF THE INVENTION 
The present invention will be explained in detail below. 
The electrically conductive polymer used in the present invention is a 
copolymer of N-methylol(meth)acrylamide and styrenesulfonic acid, which is 
crosslinked upon heating. Proportion of N-methylol(meth)acrylamide in the 
copolymer is generally 5-70% by weight, more preferably 10-60% by weight. 
The copolymer can be prepared by carrying out polymerization of a mixture 
of preferably p-styrenesulfonic acid or an alkali metal salt thereof and 
N-methylol(meth)acrylamide which are preferably dissolved in an 
alcohol/water mixed solvent, namely, in such a system that they are 
soluble in the solvent in the form of monomers, but polymer produced with 
progress of polymerization is insoluble in the solvent and precipitated. A 
water/alcohol mixed solvent system containing at least 40% by weight of 
alcohol is especially preferred. The precipitated polymer can be obtained 
in the form of fine particles if a resin which is soluble in the solvent 
is previously allowed to be present in carrying out such polymerization. 
That is, polymerization is carried out under such conditions that the 
monomers are soluble in the solvent, but the resulting polymer is 
insoluble in the solvent in the presence of a polymer which acts as a 
dispersion stabilizer. 
Moreover, in the present invention, various monomers can be used as a third 
component in addition to the styrenesulfonic acid or alkali metal salt 
thereof and N-methylol(meth)acrylamide. Among them, especially 
copolymerization of a monomer having an acid group can further improve 
heat curability of the coat. As such monomers, preferred are acidic 
monomers such as (meth)acrylic acid, 2-acrylamide-2-methylpropanesulfonic 
acid and maleic acid. Copolymerization ratio of such acidic monomer is 
preferably about 0.5-10% by weight. 
The polymer for imparting antistatic properties which has heat curability 
is synthesized in the above manner and a water resistant antistatic film 
having sufficient performance is formed, but if necessary, monomers such 
as styrene and derivatives thereof and (meth)acrylate esters may be 
further copolymerized as other monomers than those mentioned above. 
Alkali metal ions such as sodium ion and potassium ion are preferred as a 
counter ion of styrenesulfonic acid. 
Synthesis examples are shown below. 
SYNTHESIS EXAMPLE 1 
7 g of polyvinylpyrrolidone, 70 g of sodium p-styrenesulfonate and 30 g of 
N-methylolacrylamide were charged in a 500 ml four-necked flask provided 
with a stirrer, a thermometer, a nitrogen introduction pipe and a reflux 
condenser, followed by adding 200 g of ethanol and 100 g of distilled 
water and dissolving the above compounds in the mixed solvent at 
70.degree. C. Then, 1 g of AIBN was added at 75.degree. C. in a nitrogen 
atmosphere and polymerization was initiated to yield a stable white 
emulsion. 
After elapsing of 3 hours from initiation of the polymerization, ethanol 
was distilled off under reduced pressure to obtain a homogeneous aqueous 
polymer solution of low viscosity. 
SYNTHESIS EXAMPLE 2 
In the same manner as in Synthesis Example 1, 7 g of polyvinylpyrrolidone, 
70 g of sodium p-styrenesulfonate, 30 g of N-methylolacrylamide and 5 g of 
2 acrylamide-2-methylpropanesulfonic acid were dissolved in a mixed 
solvent comprising 150 g of ethanol and 150 g of distilled water at 
70.degree. C. and polymerization was initiated by adding thereto 1.0 g of 
AIBN at 75.degree. C. in a nitrogen atmosphere. Immediately after 
initiation of the polymerization, white polymer fine particles were 
precipitated to form a milk-white emulsion. After about 1 hour from 
initiation of the polymerization, 50 g of ethanol was added to the 
emulsion, followed by further stirring for about 2 hours under heating. 
Then, ethanol was distilled off under reduced pressure to obtain a 
homogeneous aqueous solution. 
SYNTHESIS EXAMPLE 3 
In the same manner as in Synthesis Example 1, 7 g of polyvinylpyrrolidone, 
70 g of sodium p-styrenesulfonate, 25 g of N-methylolacrylamide and 5 g of 
methacrylic acid were dissolved in 200 g of ethanol and 100 g of distilled 
water and polymerization was initiated by adding thereto 1.0 g of AIBN at 
75.degree. C. 
The product was a stable emulsion having a particle size of 1 micron or 
less. 
SYNTHESIS EXAMPLE 4 
In the same manner as in Synthesis Example 1, 10 g of polyvinyl alcohol 
(PVA203 manufactured by Kuraray Co. Ltd.; a partial saponification product 
of polyvinyl acetate), 70 g of sodium p-styrenesulfonate, 30 g of 
N-methylolacrylamide and 5 g of 2 acrylamide-2-methylpropanesulfonic acid 
were dissolved in a mixed solvent comprising 150 g of ethanol and 150 g of 
distilled water. 
Polymerization was initiated by adding thereto 1.0 g of AIBN at 75.degree. 
C. in a nitrogen atmosphere and furthermore, 50 g of ethanol was added 
dropwise thereto over a period of 3 hours for stabilization of the 
resulting emulsion. 
Then, ethanol was distilled off under reduced pressure to obtain a 
homogeneous aqueous solution. 
The heat-curable antistatic agent obtained in the present invention alone 
forms a film on a support such as a film and completely crosslinks in a 
few hours under a heating condition such as about 50.degree. C. 
Coating amount of the electrically conductive polymer of the present 
invention is usually 0.1-5 g/m.sup.2, preferably 0.5-2.0 g/m.sup.2 in 
solid content. If it is less than 0.1 g/m.sup.2, antistatic properties are 
inferior and not practical and if it is more than 5 g/m.sup.2, adhesion to 
the backcoat layer deteriorates. 
The electrically conductive polymer layer may contain other binders, if 
necessary. 
The electrically conductive polymer layer must be provided between the 
backcoat layer containing gelatin and the film base and should not be 
provided in other positions. 
For example, if the antistatic polymer layer is provided not on the film 
base, but on the backcoat layer provided on the film base, film of the 
antistatic polymer layer is not sufficiently formed and resistance is high 
and besides, since the backcoat layer generally contains filter dyes, 
elimination of the dyes becomes insufficient and this is not preferred. If 
the antistatic polymer layer is provided between emulsion layer and the 
film base, this is not preferred since organic solvent is used for 
application of stripping film for emulsion layer and thus, the emulsion 
layer side requires higher adhesion than the back side. 
Moreover, if the antistatic polymer layer is provided between emulsion 
layer and protective layer or outside the protective layer, film of the 
polymer layer is not sufficiently formed and resistance is high. This is 
also not preferred from the points of progress of development and fixation 
speed. 
Therefore, the antistatic polymer layer should be provided between the film 
base and the backcoat layer containing gelatin. 
There may be considered such construction that the backcoat layer contains 
no gelatin and thus only a polymer layer is provided or only the 
electrically conductive polymer layer is provided, but in this case, since 
the emulsion layer and the protective layer are mainly composed of 
gelatin, curling of the light-sensitive material occurs much and damages 
practical value. As aforementioned, in the electrically conductive polymer 
used in the present invention, proportion of N-methylol(meth)acrylamide is 
preferably 10-60% by weight. If it is less than 10% by weight, the polymer 
is not sufficiently crosslinked upon heating and cannot stand alkaline or 
acidic photographic treatments. If it is more than 60% by weight, 
proportion of styrenesulfonic acid or alkali metal salt thereof which 
concerns with antistatic properties correlatively decreases and sufficient 
antistatic properties cannot be obtained. 
Furthermore, pH of coating composition for forming the electrically 
conductive polymer layer is preferably 1.5-3.0, especially preferably 2.5 
or less. If pH is more than 3.0, an electrically conductive layer which 
can stand photographic treatments cannot be formed and if it is too much 
acidic, filter dyes in the backcoat layer are adversely affected and 
absorbance is generally reduced and thus, pH is generally at least 1.5, 
more preferably at least 2.0. 
Any acids may be used for adjusting pH to the above range. Inorganic acids 
such as phosphoric acid, hydrochloric acid, sulfuric acid and nitric acid 
are especially preferred, but organic acids such as those having 
carboxylic acid group or sulfonic acid group may also be used. 
Drying temperature at coating of the copolymer comprising N 
methylol(meth)acrylamide and styrenesulfonic acid is generally 40.degree. 
C. or higher, preferably 50.degree. C. or higher. If the drying 
temperature is lower, not only the film which can stand photographic 
treatments cannot be formed, but also resistance becomes higher after the 
treatments and this is not preferred. A method in which the 
light-sensitive material is not sufficiently dried, but taken up in the 
form of mill roll and heated at high temperatures (at least 40.degree. C.) 
for many weeks can also be considered. In this case, however, blocking is 
apt to occur and besides, many weeks are required for heating in the form 
of mill roll and this is not economical. 
In coating of the copolymer comprising N-methylol(meth)acrylamide and 
styrenesulfonic acid of the present invention, the light-sensitive 
material is taken up in the form of mill roll and relative humidity in 
this case is especially important. This relative humidity is preferably 
40-60%, especially preferably 45-55%. If this is less than 40%, resistance 
is high probably because of too high density of the resulting film and 
besides, adhesion to the backcoat layer is inferior. If it is more than 
60%, blocking readily occurs and besides, adhesion to the backcoat layer 
is inferior. 
In the present invention, the electrically conductive polymer layer 
preferably contains a surface active agent represented by the following 
formula [I] or [II]. 
##STR1## 
(wherein n is a natural number of 1-20, M is H or an alkali metal, and R 
is an alkyl group of 5-15 carbon atoms or 
##STR2## 
in which R.sub.1 is an alkyl group of 5-15 carbon atoms and R.sub.2 is an 
alkyl group of 1-3 carbon atoms, H or a halogen atom). 
The surface active agent of the formula [I] is disclosed in U.S Pat. No. 
3,026,201, but this patent makes no mention of matching between the 
copolymer comprising styrenesulfonic acid and N-methylol(meth)acrylamide 
and the surface active agent. 
In the formula [I], n is preferably 20 or less. If it is 21 or more, 
coatability becomes inferior. It is especially preferably 3-15. The alkyl 
group of R has 5-15 carbon atoms. If the carbon number is 4 or less, the 
compound does not acts as a surface active agent to cause deterioration of 
coatability, resulting in practical problem. If it is 16 or more, 
oleophilicity is too strong and uneven coating is brought about. The 
carbon number is especially preferably 8-12. The same as for the alkyl 
group of R can be applied to R.sub.1. M is H or an alkali metal. 
Especially preferred is sodium ion or potassium ion. R.sub.2 is an alkyl 
group of 1-3 carbon atoms, H or a halogen atom. 
Examples of the surface active agents of the formula [I] are shown below. 
##STR3## 
(wherein n is a natural number of 1-20, R.sub.1 is an alkyl or aryl group 
of 5-15 carbon atoms which may be substituted and R.sub.2 is an alkyl 
group of 1-5 carbon atoms which may he substituted.) 
The surface active agent of the formula [II] is known, but no mention is 
made of matching between the copolymer comprising styrenesulfonic acid and 
N-methylol(meth)acrylamide and the surface active agent. 
In the formula [II], n is preferably 20 or less. If it is 21 or more, 
coatability becomes inferior. It is especially preferably 3-15. The alkyl 
group of R.sub.1 has 5-15 carbon atoms. If the carbon number is 4 or less, 
the compound does not acts as a surface active agent to cause 
deterioration of coatability, resulting in practical problem. If it is 16 
or more, oleophilicity is too strong and uneven coating is brought about. 
The carbon number is especially preferably 8-12. R.sub.2 is an alkyl group 
of 1-5 carbon atoms which may be substituted with halogen atom or the 
like. 
Examples of the surface active agents of the formula [II] are shown below. 
##STR4## 
Addition amount of these surface active agents is preferably 0.05-10 g, 
especially preferably 0.5-5.0 per 1 liter of coating solution. They may be 
added at any time. 
Furthermore, the electrically conductive layer preferably contains a 
matting agent. The matting agent is organic or inorganic powder which has 
an average particle size of preferably 0.2-10.mu., especially preferably 
0.3-5.mu.. Examples of the matting agent as organic compounds are water 
dispersible vinyl polymers such as polymethyl(meth)acrylate, cellulose 
acetate propionate and starch. 
Examples of the matting agent as inorganic compounds are strontium barium 
sulfate, calcium carbonate, silicon dioxide, magnesium oxide and titanium 
oxide. 
Amount of the matting agent is usually 10 mg-1.0 g, preferably 30 mg-300 mg 
per 1 liter of coating solution of the electrically conductive polymer. 
Amount of gelatin in the backcoat layer is 0.5-8 g/m.sup.2, preferably 1-5 
g/m.sup.2. If necessary, the backcoat layer may further contain the 
above-mentioned electrically conductive polymers, other electrically 
conductive polymers, water soluble polymers, hardeners, matting agents, 
antihalation dyes, surface active agents and the like. 
The film base used in the present invention is mainly polyethylene 
terephthalate film, but other polyester bases may also be used. 
On another side of the film base there are provided emulsion layer, 
protective layer and the like.

EXAMPLE 1 
The following solutions were prepared. 
______________________________________ 
Coating solution for antistatic layer 
(I-a) 
Distilled water 500 ml 
10 wt % solution of polystyrenesulfonic 
500 ml 
acid containing 30% by weight of 
N-methylolacrylamide 
SNP-4N of Nikko Chemical Co. 
1.0 g 
Coating solution for backcoat layer 
(I-b) 
Distilled water 950 ml 
Inert gelatin 50 g 
Dye (B-1) 1.0 g 
Dye (B-2) 1.0 g 
Dye (B-3) 1.0 g 
10 wt % solution of AEROL OP of 
20 ml 
Toho Chemical Co. 
10 wt % 2,4 Dichloro-6-hydroxy-S-triazine 
25 ml 
Dye (B-1) 
##STR5## 
Dye (B-2) 
##STR6## 
Dye (B-3) 
##STR7## 
Coating solution for emulsion 
(1-c) 
Distilled water 740 ml 
Inert gelatin 30 g 
AgCl emulsion* 200 g 
(monodispersion of 0.15.mu. ) 
10 wt % AEROL OP 20 ml 
10 wt % 2,4-Dichloro-6-hydroxy-S-triazine 
10 ml 
Coating solution for protective layer 
(1-d) 
Distilled water 945 ml 
Inert gelatin 50 g 
10 wt % AEROL OP 40 ml 
10 wt % 2,4-Dichloro-6-hydroxy-S-triazine 
15 ml 
______________________________________ 
*Monodispersed AgCl emulsion of 0.15.mu. which was prepared by double je 
process. 200 g of this emulsion contained 100 g of silver and 20 g of 
gelatin. 
These coating solutions were coated in an amount of 20 ml/m.sup.2 for 
antistatic layer and 60 ml/m.sup.2 for backcoat layer on one side of a 
polyethylene terephthalate film and 60 ml/m.sup.2 for emulsion layer and 
20 ml/m.sup.2 for protective layer on another side. Each layer was 
separately coated and was heated at 50.degree. C. for one day for every 
coating. 
The position of the antistatic polymer layer was as follows: (a) between 
backcoat layer and base; (b) on backcoat layer which was provided on base, 
namely, as the outermost layer; (c) between emulsion layer and base; (d) 
between emulsion layer and protective layer; (e) on protective layer, 
namely, as the outermost layer on another side of base. Furthermore, a 
sample (f) which did not have the antistatic layer was prepared. 
These samples which had been heated were processed by automatic processing 
machine GR-14 manufactured by Konishiroku Photo Industry Co., Ltd. 
Development was carried out with MRA CD-101 manufactured by Mitsubishi 
Paper Mills Ltd. at 35.degree. C. for 20 seconds and fixation was carried 
out with CF-901 manufactured by Mitsubishi Paper Mills Ltd. at 35.degree. 
C. for 20 seconds. 
Antistatic property was evaluated by measuring surface resistance of 
samples before and after processing which were left to stand in an 
atmosphere of 25.degree. C. and 50% RH (relative humidity) for 2 hours by 
surface resistometer model HT-210 manufactured by Mitsubishi Petrochemical 
Co., Ltd. When the surface resistance is higher than 10.sup.12 .OMEGA., 
the antistatic property is bad and when it is 10.sup.11 .OMEGA. or lower, 
the antistatic property is good. 
Two kinds of adhesion test were conducted. One is adhesion test on back 
side of the sample and this was carried out by making scratches at an 
interval of 5 mm on the surface of the coat by cutter knife, applying 
water thereto, then strongly rubbing the surface by a tissue paper ten 
times and observing the rubbed surface. Adhesion of layers on the back 
side of all samples was good according to this test method. 
Another adhesion test was carried out using base cut solution used for 
application of stripping film. 
The base cut solution is to be used only for surface of emulsion layer and 
so, this test was not carried out for the backcoat side. The base cut 
solution was one prepared by Dainippon Ink & Chemicals Inc. The surface of 
emulsion layer was wetted with this solution and was lightly rubbed by 
tissue paper 3 times. Evaluation was conducted by the following criteria. 
x: Peeling occurred over the whole surface. 
.DELTA.: Peeling occurred on about half portion. 
.largecircle.: Peeling occurred a little. 
With reference to elimination of dye, unexposed portions of ten processed 
samples were stacked and visually evaluated by the following criteria. 
x: Practically inferior. 
.DELTA.: Somewhat bad though practically usable. 
.largecircle.: Good 
The results are shown in Table 1. 
TABLE 1 
__________________________________________________________________________ 
Surface resistance 
Adhesion 
Position of (.OMEGA./cm.sup.2) 
Adhesion 
tested by 
Dye 
Sample 
antistatic 
Before 
After (back 
base cut 
elimina- 
No. polymer layer 
processing 
processing 
side) 
solution 
tion Note 
__________________________________________________________________________ 
(a) Between 5 .times. 10.sup.9 
6 .times. 10.sup.10 
.smallcircle. 
.smallcircle. 
.smallcircle. 
The present invention 
backcoat layer 
and base 
(b) On backcoat 
7 .times. 10.sup.11 
7 .times. 10.sup.12 
.smallcircle. 
.smallcircle. 
.DELTA. 
Comparative 
layer, namely, 
as outermost 
layer 
(c) Between 5 .times. 10.sup.9 
7 .times. 10.sup.10 
.smallcircle. 
x .smallcircle. 
" 
emulision layer 
and base 
(d) Between 3 .times. 10.sup.12 
6 .times. 10.sup.12 
.smallcircle. 
.smallcircle. 
.smallcircle. 
" 
emulsion layer 
and protective 
layer 
(e) On protective 
3 .times. 10.sup.11 
4 .times. 10.sup.12 
.smallcircle. 
.smallcircle. 
.smallcircle. 
" 
layer, namely, 
outermost layer 
(f) -- 3 .times. 10.sup.13 
5 .times. 10.sup.13 
.smallcircle. 
.smallcircle. 
.smallcircle. 
" 
__________________________________________________________________________ 
As can be seen from Table 1, when copolymer of N-methylol(meth)acrylamide 
and styrenesulfonic acid is used as antistatic layer, it is most preferred 
to provide this polymer between backcoat layer and base. 
EXAMPLE 2 
To 500 ml of distilled water was added 500 ml of a 10 wt % solution of 
sodium polystyrenesulfonate containing 30% by weight of 
N-methylolacrylamide and thereto was further added 10 ml of 10 wt % 
polyethylene oxide anionic surface active agent. Then, pH was varied from 
1.3 to 4.0 by adding various acids. 
Then, each solution was coated on a subbed polyethylene terephthalate film 
of 100.mu. thick at a coating amount of 20 ml/m.sup.2. The coat was heated 
at 50.degree. C. for 24 hours and thereon was coated a gelatin layer 
containing a filter dye as a backcoat layer. 
Backcoating solution contained each of the following dyes B-1, B-2 and B-3 
in an amount of 50 mg/m.sup.2. 
##STR8## 
Inert gelatin was used as gelatin and was coated on electrically conductive 
antistatic polymer layer at a coating amount of 3.0 g/m.sup.2. As a 
surface active agent, a 10 wt % solution of AEROL OP of Toho Chemical Co. 
was added in an amount of 2% based on volume of backcoating solution and 
as a hardener, 10 wt % 2,4-dichloro-6-hydroxy-S-triazine was added in an 
amount of 0.5 ml based on 1 g of gelatin. 
These samples were subjected to development and fixation in the same manner 
as in Example 1. 
Antistatic property was measured and evaluated in the same manner as in 
Example 1. 
Adhesion property was evaluated as follows. Surface of the sample was cut 
crosswise by a knife to form squares having a side of 5 mm, and the sample 
was dipped in water of 30.degree. C. for 30 seconds and then the surface 
was rubbed by a tissue paper. The results were evaluated by the following 
criteria. 
.largecircle.: No peeling occurred. 
.DELTA.: Peeling slightly occurred. 
x: Peeling somewhat occurred. 
Discoloration of the filter dye was evaluated by comparing with a sample in 
which the backcoat layer was coated on the base without the polymer layer 
as standard. 
x: Discoloration somewhat occurred. 
.DELTA.: Discoloration slightly occurred. 
.largecircle.: No discoloration occurred. 
The results are shown in Table 2. 
TABLE 2 
______________________________________ 
Surface resistance 
(.OMEGA./cm.sup.2) 
Before After 
Acid pH processing 
processing 
Adhesion 
Discloration 
______________________________________ 
Sulfuric 
1.3 9 .times. 10.sup.8 
8 .times. 10.sup.9 
.smallcircle. 
x 
acid 1.5 3 .times. 10.sup.9 
1 .times. 10.sup.10 
.smallcircle. 
.DELTA. 
2.0 3 .times. 10.sup.9 
2 .times. 10.sup.10 
.smallcircle. 
.DELTA. 
2.5 5 .times. 10.sup.9 
2 .times. 10.sup.10 
.smallcircle. 
.smallcircle. 
3.0 7 .times. 10.sup.9 
1 .times. 10.sup.10 
.DELTA. 
.smallcircle. 
3.2 4 .times. 10.sup.10 
8 .times. 10.sup.10 
x .smallcircle. 
3.5 4 .times. 10.sup.10 
1 .times. 10.sup.12 
x .smallcircle. 
4.0 8 .times. 10.sup.10 
3 .times. 10.sup.12 
x .smallcircle. 
Phos- 1.3 2 .times. 10.sup.9 
1 .times. 10.sup.10 
x x 
phoric 1.5 2 .times. 10.sup.9 
2 .times. 10.sup.10 
.smallcircle. 
.DELTA. 
acid 2.0 5 .times. 10.sup. 9 
1 .times. 10.sup.10 
.smallcircle. 
.DELTA. 
2.5 6 .times. 10.sup.9 
3 .times. 10.sup.10 
.smallcircle. 
.smallcircle. 
3.0 6 .times. 10.sup.9 
3 .times. 10.sup.10 
.smallcircle. 
.smallcircle. 
3.2 7 .times. 10.sup.10 
3 .times. 10.sup.12 
x .smallcircle. 
3.5 8 .times. 10.sup.10 
1 .times. 10.sup.12 
x .smallcircle. 
4.0 6 .times. 10.sup.10 
5 .times. 10.sup.12 
x .smallcircle. 
Hydro- 1.3 1 .times. 10.sup.9 
1 .times. 10.sup.10 
.smallcircle. 
x 
chloric 
1.5 3 .times. 10.sup.9 
2 .times. 10.sup.10 
.smallcircle. 
.DELTA. 
acid 2.0 2 .times. 10.sup.9 
2 .times. 10.sup.10 
.smallcircle. 
.DELTA. 
2.5 5 .times. 10.sup.9 
1 .times. 10.sup.10 
.smallcircle. 
.smallcircle. 
3.0 4 .times. 10.sup.9 
2 .times. 10.sup.10 
.DELTA. 
.smallcircle. 
3.2 6 .times. 10.sup.10 
9 .times. 10.sup.10 
x .smallcircle. 
3.5 9 .times. 10.sup.10 
3 .times. 10.sup.12 
x .smallcircle. 
4.0 8 .times. 4 .times. 10.sup.12 
x .smallcircle. 
______________________________________ 
As can be seen from Table 2, if pH of coating solution for polymer layer is 
less than 1.5, the dyes discolor and this is not preferred and if it is 
more than 3.0, resistance after processing increases and besides, adhesion 
deteriorates. Therefore, when a polymer of N-methylol(meth)acrylamide and 
styrenesulfonic acid is used as an antistatic layer and a gelatin layer is 
coated on the antistatic polymer layer, pH of the polymer layer is 
preferably 1.5-3.0. 
EXAMPLE 3 
To 500 ml of distilled water was added 500 ml of a 10 wt % solution of 
sodium polystyrenesulfonate containing 30% by weight of 
N-methylolacrylamide and thereto was further added 10 ml of 10 wt % 
solution of the surface active agent I-a exemplified above. 
The above coating solution was coated on a subbed polyethylene 
terephthalate film of 100.mu. thick with changing the maximum temperature 
of drying zone of coater at every 10.degree. C. from 20.degree. C. to 
70.degree. C. Coating amount was 20 ml/m.sup.2 and coating speed was 20 
m/min. Atmosphere of the portion from completion of drying until winder 
was of 25.degree. C. and 50% in relative humidity. 
The sample wound by winder was put in a moistureproof bag as it was and 
left to stand for 3 days at room temperature. 
Thereafter, a gelatin solution was coated as a backcoat on the above coated 
electrically conductive polymer layer. The gelatin solution was a solution 
of 50 g of inert gelatin in 950 ml of distilled water, to which was added 
20 ml of 10 wt % solution of compound 1-a as surface active agent. As a 
hardener, 25 ml of 10 wt % 2,4-dichloro-6-hydroxy-S-triazine was further 
added and this gelatin solution was coated at a coating amount of 50 
ml/m.sup.2. Drying temperature in this case was 45.degree. C. 
The resulting samples were heated at 50.degree. C. for 1 day and were 
processed in the same manner as in Example 1. 
The samples were subjected to evaluation of antistatic property and 
adhesion property in the same manner as in Example 2. The results are 
shown in Table 3. 
TABLE 3 
______________________________________ 
Maximum Surface resistance 
drying (.OMEGA./cm.sup.2) 
tempera- Before After 
No. ture processing 
processing 
Adhesion 
Others 
______________________________________ 
1 20.degree. C. 
8 .times. 10.sup.9 
4 .times. 10.sup.12 
x Partial 
blocking 
occurred 
2 30.degree. C. 
7 .times. 10.sup.9 
5 .times. 10.sup.12 
x 
3 40.degree. C. 
5 .times. 10.sup.9 
2 .times. 10.sup.11 
.DELTA. 
4 50.degree. C. 
6 .times. 10.sup.9 
3 .times. 10.sup.10 
.smallcircle. 
5 60.degree. C. 
5 .times. 10.sup.9 
2 .times. 10.sup.10 
.smallcircle. 
6 70.degree. C. 
5 .times. 10.sup.9 
4 .times. 10.sup.10 
.smallcircle. 
7 75.degree. C. 
6 .times. 10.sup.9 
3 .times. 10.sup.10 
.smallcircle. 
______________________________________ 
As can be seen from Table 3, when the drying temperature is lower than 
30.degree. C., adhesion and resistance after processing are not 
satisfactory. It seems that even if a drying temperature of 
20.degree.-30.degree. C. is employed, satisfactory result will be obtained 
if drying is carried out for a long time, but the data shows substantially 
no change even if coating speed is 10 m/min. Thus, it appears that water 
retention characteristics of the polymer are concerned therewith. 
EXAMPLE 4 
Example 3 was repeated except that the maximum temperature of the drying 
zone of coater was 50.degree. C., temperature of atmosphere from 
completion of drying until winder part was 25.degree. C. and relative 
humidity thereof was changed from 30-70% at every 10%. 
The results are shown in Table 4. 
TABLE 4 
______________________________________ 
Relative Surface resistance 
humidity of 
(.OMEGA./cm.sup.2) 
winding- Before After 
No. up part processing 
processing 
Adhesion 
Others 
______________________________________ 
1 30% 5 .times. 10.sup.11 
2 .times. 10.sup.12 
x 
2 40% 7 .times. 10.sup.9 
1 .times. 10.sup.11 
.smallcircle. 
3 50% 6 .times. 10.sup.9 
3 .times. 10.sup.10 
.smallcircle. 
4 60% 5 .times. 10.sup.9 
3 .times. 10.sup.10 
.DELTA. 
5 70% 4 .times. 10.sup.9 
4 .times. 10.sup.10 
x Partial 
blocking 
occurred 
______________________________________ 
As can be seen from Table 4, when relative humidity of the above atmosphere 
is 30%, the sample is inferior in adhesion and low in resistance. In the 
case of 70%, the sample is inferior in adhesion and shows partial 
blocking. Therefore, when a polymer of N-methylol(meth)acrylamide and 
styrenesulfonic acid is used as antistatic layer, it is important that 
drying temperature is 40.degree. C. or higher and humidity at winding is 
40-60%. 
EXAMPLE 5 
To 500 ml of distilled water was added 500 ml of a 10 wt % solution of 
sodium polystyrenesulfonate containing 30% by weight of 
N-methylolacrylamide and thereto was further added 10 ml of 10 wt % 
solution of the surface active agent shown in the following Table 5. 
TABLE 5 
______________________________________ 
No. Name Maker Type 
______________________________________ 
A-a AEROL OP Toho Chemical Co. 
Anionic 
A-b ACTINOL K Matsumoto Yushi Co. 
Nonionic 
A-c ZONTES TL Matsumoto Yushi Co. 
Cationic 
A-d SUNSTAT 1007 Sanyo Kasei Co. Amphoteric 
A-e I-a -- Polyethylene 
Oxide.anion 
A-f II-a -- Polyethylene 
Oxide.anion 
______________________________________ 
Then, each solution was coated on a subbed polyethylene terephthalate film 
of 100.mu. thick at a coating amount of 20 ml/m.sup.2 and thereafter, 
heated at 50.degree. C. for 24 hours and a gelatin solution was coated 
thereon as a backcoat layer. 
The gelatin solution was a solution of 50 g of inert gelatin in 950 ml of 
distilled water, to which was added 20 ml of 10 wt % solution of AEROL OP 
as a surface active agent. As a hardener, 20 ml of 10 wt % 
2,4-dichloro-6-hydroxy-S triazine was further added and this gelatin 
solution was coated on the above coated polymer layer at a coating amount 
of 50 ml/m.sup.2. 
These samples were heated at 50.degree. C. for 1 day and processed in the 
same manner as in Example 1. 
Evaluation of antistatic property and adhesion property were conducted in 
the same manner as in Example 2. 
The results are shown in Table 6. 
TABLE 6 
______________________________________ 
Surface resistance 
(.OMEGA./cm.sup.2) 
Sample 
Before After Ad- 
No. processing 
processing hesion 
Others 
______________________________________ 
A-a 3 .times. 10.sup.9 
2 .times. 10.sup.10 
.smallcircle. 
Uneven 
coating. 
Polymer 
layer 
was hazed. 
A-b 3 .times. 10.sup.11 
Over range* .DELTA. 
Good coating 
A-c 4 .times. 10.sup.10 
Over range* .DELTA. 
Some uneven 
coating 
occured. 
A-d 4 .times. 10.sup.9 
6 .times. 10.sup.11 
.DELTA. 
Good coating. 
Polymer 
layer 
was hazed. 
A-e 6 .times. 10.sup.9 
3 .times. 10.sup.10 
.smallcircle. 
Good coating 
A-f 7 .times. 10.sup.9 
5 .times. 10.sup.10 
.smallcircle. 
Good coating 
______________________________________ 
*"Over range" means the surface resistance of more than 10.sup.13 
.OMEGA./cm.sup.2. 
As can be seen from Table 6, when AEROL OP was used, coatability was 
inferior and the polymer layer was hazed. This material was not accepted, 
when ACTINOL K was used, coatability was good, but adhesion was somewhat 
inferior and resistance after processing was high. When ZONTES TL was 
used, some uneven coating occurred and resistance after processing was 
high. When SUNSTAT 1007 was used, coatability was good, but adhesion was 
somewhat bad and the polymer layer was hazed and resistance after 
processing was high. From these results, it can be seen that the compounds 
I-a and II-a of the present invention are superior in coatability, 
resistance and adhesion. 
EXAMPLE 6 
Example 5 was repeated except that content of N-methylolacrylamide was 
variously changed and compound I-c exemplified above was used. 
The results are shown in Table 7. 
TABLE 7 
______________________________________ 
Content of 
N-methy- Surface resistance 
lol-acryla- 
(.OMEGA./cm.sup.2) 
mide (% Before After Ad- 
No. by weight) 
processing 
processing 
hesion 
Others 
______________________________________ 
1 5 7 .times. 10.sup.8 
-- x Film 
peeled 
after 
pro- 
cessing. 
2 10 3 .times. 10.sup.9 
1 .times. 10.sup.11 
.DELTA. 
3 20 4 .times. 10.sup.9 
5 .times. 10.sup.10 
.smallcircle. 
4 30 6 .times. 10.sup.9 
3 .times. 10.sup.10 
.smallcircle. 
5 40 8 .times. 10.sup.9 
4 .times. 10.sup.10 
.smallcircle. 
6 50 1 .times. 10.sup.10 
5 .times. 10.sup.10 
.smallcircle. 
7 60 5 .times. 10.sup.10 
6 .times. 10.sup.11 
.smallcircle. 
8 70 5 .times. 10.sup.11 
8 .times. 10.sup.12 
.smallcircle. 
9 80 7 .times. 10.sup.11 
Over range 
.smallcircle. 
10 90 -- -- -- Polymer 
could not 
be syn- 
thesized. 
11 95 -- -- -- Polymer 
could not 
be syn- 
thesized. 
______________________________________ 
As can be seen from Table 7, when content of N-methylolacrylamide was less 
than 5% by weight, crosslinking of the polymer was insufficient and the 
coat somewhat peeled off in the automatic processing machine. When content 
of N-methylolacrylmide was more than 90% by weight, synthesis of the 
polymer was difficult. When it was 70-80% by weight, resistance after 
processing was high and this was not preferred. Therefore, content of 
N-methylol(meth)acrylamide is preferably 10-60% by weight. 
EXAMPLE 7 
Example 6 was repeated except that compound II-e was used in place of 
compound I-c as a surface active agent. 
The results are shown in Table 8. 
TABLE 8 
______________________________________ 
Content of 
N-methy- Surface resistance 
lol-acryla- 
(.OMEGA./cm.sup.2) 
mide (% Before After 
No. by weight) 
processing 
processing 
Adhesion 
Others 
______________________________________ 
1 5 8 .times. 10.sup.8 
-- x Film 
peeled 
after 
pro- 
cessing. 
2 10 5 .times. 10.sup.9 
2 .times. 10.sup.11 
.DELTA. 
3 20 4 .times. 10.sup.9 
6 .times. 10.sup.10 
.smallcircle. 
4 30 7 .times. 10.sup.9 
5 .times. 10.sup.10 
.smallcircle. 
5 40 6 .times. 10.sup.9 
4 .times. 10.sup.10 
.smallcircle. 
6 50 2 .times. 10.sup.10 
6 .times. 10.sup.10 
.smallcircle. 
7 60 4 .times. 10.sup.10 
6 .times. 10.sup.11 
.smallcircle. 
8 70 6 .times. 10.sup.11 
8 .times. 10.sup.12 
.smallcircle. 
9 80 8 .times. 10.sup.11 
Over range 
.smallcircle. 
10 90 -- -- -- Polymer 
could not 
be syn- 
thesized. 
11 95 -- -- -- Polymer 
could not 
be syn- 
thesized. 
______________________________________ 
As can be seen from Table 8, when content of N-methylolacrylmide was less 
than 5% by weight, crosslinking of the polymer was insufficient and the 
coat somewhat peeled off in the automatic processing machine. When content 
of N-methylolacrylmide was more than 90% by weight, synthesis of the 
polymer was difficult. When it was 70-80% by weight, resistance after 
processing was high and this was not preferred. Therefore, content of 
N-methylol(meth)acrylamide is preferably 10-60% by weight. 
EXAMPLE 8 
To 500 ml of distilled water was added 500 ml of a 10 wt % solution of 
sodium polystyrenesulfonate containing 30% by weight of 
N-methylolacrylamide and thereto was added 10 wt % solution of compound 
I-a as a surface active agent and thereto was further added a matting 
agent (SY-244 manufactured by Fuji Davidson Co.) with changing the 
addition amount thereof. 
Each solution obtained above was coated on a subbed polyethylene 
terephthalate film of 100.mu. thick at a coating amount of 20 ml/m.sup.2 
and then dried. The sample after dried was cut to A4 size and ten of these 
samples of A4 size were stacked and sandwiched between two plates and left 
to stand at 50.degree. C. for 24 hours under application of strong 
pressure. 
Thereafter the stacked samples were peeled off from each other and state of 
blocking was observed and evaluated by the following criteria. 
x: Blocking occurred over the whole surface. 
.DELTA.: Blocking partially occurred. 
.largecircle.: No blocking occurred. 
The results are shown in Table 9. 
TABLE 9 
______________________________________ 
Amount of SY-244 per 1 l 
No. of coating solution 
Blocking State of coat 
______________________________________ 
1 0 x Transparent 
2 10 mg .DELTA. 
" 
3 30 mg .smallcircle. 
" 
4 100 mg .smallcircle. 
" 
5 300 mg .smallcircle. 
Somewhat hazed 
6 1.0 g .smallcircle. 
Hazed 
7 3.0 g .smallcircle. 
" 
______________________________________ 
As can be seen from Table 9, blocking occurred in the samples containing no 
matting agent. 
Next, a gelatin solution was coated as a backcoat layer on the polymer 
layer of the above samples 2-7. 
The gelatin solution was a solution of 50 g of inert gelatin in 950 ml of 
distilled water, to which was added 20 ml of 10 wt % solution of AEROL OP 
as a surface active agent. As a hardener, 20 ml of 10 wt % 
2,4-dichloro-6-hydroxy-S-triazine was further added and this gelatin 
solution was coated on the above coated polymer layer at a coating amount 
of 50 ml/m.sup.2. 
These samples were heated at 50.degree. C. for 1 day and processed in the 
same manner as in Example 1. 
Evaluation of antistatic property and adhesion property were conducted in 
the same manner as in Example 2. 
TABLE 10 
______________________________________ 
Amount 
of SY244 per 
Surface resistance 
1 l of (.OMEGA./cm.sup.2) 
coating Before After State 
solution processing 
processing 
Adhesion 
of coat 
______________________________________ 
10 mg 5 .times. 10.sup.9 
3 .times. 10.sup.10 
.smallcircle. 
Transparent 
30 mg 4 .times. 10.sup.9 
2 .times. 10.sup.10 
.smallcircle. 
" 
100 mg 5 .times. 10.sup.9 
3 .times. 10.sup.10 
.smallcircle. 
" 
300 mg 6 .times. 10.sup.9 
2 .times. 10.sup.10 
.smallcircle. 
" 
1.0 g 2 .times. 10.sup.10 
3 .times. 10.sup.11 
.DELTA. 
Somewhat 
hazed 
3.0 g 3 .times. 10.sup.11 
3 .times. 10.sup.12 
x Hazed 
______________________________________ 
As can be seen from Table 10, when too much amount of matting agent was 
contained, resistance increased and adhesion became inferior and besides, 
the coat was hazed. Therefore, amount of the matting agent is preferably 
10 mg/m.sup.2 to 1.0 g/m.sup.2. This amount is similar for any matting 
agents. 
In the above Examples 2, 3, 5 and 8, a protective layer and an emulsion 
layer were coated on another side of the film base in the same manner as 
in Example 1.