JPH09111019A - Antistatic plastic film material and silver halide photographic photosensitive material using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a transparent plastic film material or silver halide photographic photosensitive material, dealt with such problems as transparency, coating liquid stability and workability, and having high antistatic performance even in a low-humidity atmosphere. SOLUTION: This film material has at least one electroconductive layer which is obtained by coating a substrate film with a coating liquid containing at least two ingredients, i.e., electroconductive particles or semiconductive particles and a water-soluble binder. The particles accounts for 1-50vol% of the electroconductive layer. The film material is >=4×10<5> Ω in the absolute value of impedance at a frequency of 20Hz.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic film having an antistatic property improved so as to reduce the influence of humidity change, such as a magnetic tape, a floppy disk, a flexible substrate, a membrane switch substrate, and a printer recording paper. Since it can be used as a film, and a film that does not particularly impair transparency can be provided, it can be used for applications such as OHP films, liquid crystal display devices, touch panels, and stained glass. Further, since its excellent transparency is good without adversely affecting photographic characteristics, it can be used for photographic light-sensitive materials. In particular, in the case of a photographic light-sensitive material, due to its excellent characteristics, it is possible to use not only the silver salt that has been used conventionally but also a field using a light-sensitive material other than a silver salt.

[0002]

2. Description of the Related Art Generally, a plastic film has a strong charging property, and is often restricted in use except for the purpose of utilizing this physical property. For example, in a photographic light-sensitive material, a plastic film having an electrically insulating property is generally used as a support, and it is a so-called composite material composed of this support and a photographic light-sensitive layer. Alternatively, it tends to be charged during contact friction or peeling with the surface of a different substance. The electrostatic charge accumulated by charging causes many obstacles. The most serious obstacle is that the photosensitive emulsion layer is exposed to light by discharging the electrostatic charge accumulated before the development process, and when the photographic film is processed for development, it is a dot-shaped spot or so-called static mark. It is the formation of dendritic and feather-like spots. For example, if this phenomenon appears in a medical or industrial X-ray film or the like, it will lead to a very dangerous judgment. This phenomenon becomes apparent only after development, and is one of the very troublesome problems. Further, these accumulated electrostatic charges may cause a failure such as dust adhering to the film surface or failure in uniform coating on the film surface.

A large number of static failures due to such charging occur in various processes. For example, in the manufacturing process, it is caused by contact friction between the photographic film and the roller, or winding of the photographic film, separation of the support surface and the emulsion surface during the rewinding process, and the like. In the case of finished products, the photographic film is wound and the base surface and emulsion surface are separated when switching is performed, or the mechanical part during X-ray film automatic photography or contact with the fluorescent intensifying screen. It is caused by separation etc. It also occurs when it comes into contact with other packaging materials. The static marks of the photographic light-sensitive material, which are induced by the accumulation of such electrostatic charges, become more noticeable as the sensitivity of the photographic light-sensitive material increases and the processing speed increases.
Particularly in recent years, the development of photographic light-sensitive materials and the increased chances of severe handling due to high-speed coating, high-speed photography, high-speed automatic processing, etc. have made it easier to generate static marks.

Further, the adhesion of dusts after the development process has become a big problem in recent years, and improvement for keeping the antistatic property after the development process is required.

The best way to eliminate these static disturbances is to increase the electrical conductivity of the material so that the stored charge can be dissipated in a short time before it discharges.

Therefore, conventionally, a method for improving the conductivity of a support of a photographic light-sensitive material or various coated surface layers has been considered, and various hygroscopic substances, water-soluble inorganic salts, certain surfactants
Attempts have been made to use polymers and the like. For example, JP
Nos. 9-91165 and 49-121523 disclose examples of applying an ionic polymer having a dissociative group in the polymer main chain. Other Japanese Patent Application Laid-Open No. 2-9689,
Conductive polymers as described in JP-A-2-182491, JP-A-63-55541 and JP-A-63-
Inventions relating to surfactants such as those described in JP-A-148254, JP-A-63-148256 and JP-A-1-314191 are known.

However, many of these materials show specificity depending on the type of film support and photographic composition, and give good results for certain film supports and photographic emulsions and other photographic components. , Other different film supports and photographic components not only have no antistatic effect, but can also adversely affect photographic properties. As a more important drawback, many of these substances lose their function as conductive layers under low humidity.

For the purpose of improving the performance deterioration under low humidity, Japanese Patent Publication No. 35-6616 and Japanese Examined Patent Publication No. 1-20735 describe a technique of using a metal oxide as an antistatic treatment agent. The former technique discloses a method using a colloidal sol dispersion, and the latter technique uses a highly crystalline metal oxide powder treated at high temperature for the purpose of improving the conductivity problem of the former. The method of use has been disclosed. However, since the latter technique uses powder having high crystallinity, it is described that it is necessary to consider the particle diameter and the particle / binder ratio, etc., for light scattering. Further, in JP-A-4-29134, in order to improve not only the performance under low humidity but also other defects, a conductive material used in a photographic light-sensitive material contains a particulate metal oxide and a fibrous metal. Although a method using an oxide is disclosed, the problem of the amount added remains.

[0009]

As described above, although efforts have been made for many years to overcome the obstacles of plastic films due to static electricity, the relationship between their generation mechanism and materials is still unknown. Especially in the field of photography, where obstacles have a fatal effect on merchandise, application of highly conductive materials, such as conductive metal oxide particles, has been chosen as the best means. However, with regard to a photographic light-sensitive material provided with a layer containing conductive metal oxide particles, since the publication of Japanese Examined Patent Publication No. 35-6616, as a means for improving the performance deterioration under low humidity, it has been used for a long time of 30 years or more. Despite being studied for many years, it still has many unsolved problems.

For example, when a layer containing such conductive metal oxide particles is provided in contact with silver halide, pressure fog or scratches are likely to occur on an image due to friction during handling, or , When mixed with a binder, the fine particles existing on the surface will fall off due to friction during the manufacturing process or handling, so in the manufacturing process there will be a problem of scratching the product that adheres to the rollers and is conveyed. Is. Further, materials containing these metal elements as main components generally have a high specific gravity, and when applied to a photographic light-sensitive material, there is a problem such as settling of fine particles, which causes problems in the uniformity of the coating solution, storage stability, and the like. Was there.

Most of these problems can be solved by atomizing the particles, but atomization causes the following new problems. That is, there are problems such as a thickening phenomenon of the coating liquid due to atomization, a problem of workability caused by the phenomenon, and a problem of sedimentation of agglomerated particles due to an increase in cohesive force. One means for solving the problem of thickening the coating solution can be solved by reducing the amount of particles added. The problem of agglomerated particle settling also lowers the concentration,
That is, it becomes possible to improve by reducing the addition amount of the conductive particles.

Therefore, an object of the present invention is to exhibit high antistatic performance even at a low concentration, and solve problems such as transparency, stability of coating liquid, workability, etc., which are caused by a large amount of addition, Further, it is to provide a transparent plastic film material or a silver halide photographic light-sensitive material having a high antistatic property even under low humidity. The present invention is particularly effective for improving transparency, but the effects of the present invention can be applied to other than transparent films.

[0013]

The above object of the present invention is a film material having at least one conductive layer, the conductive layer comprising at least two components of conductive particles or semiconductor particles and a water-soluble binder. Is formed by a process of applying a mixture containing the conductive particles and the semiconductor particles are 1 vol% or more and 50 vol% or less of the conductive layer, and the absolute value of impedance of the film material at a frequency of 20 Hz is 4 × 10. Achieved with an antistatic plastic film material characterized by greater than ⁵ Ω.

The present invention can be applied to magnetic tapes, floppy disks, flexible substrates, base materials for membrane switches, printer recording papers, etc., in addition to photographic light-sensitive materials, and can provide a film that does not particularly impair transparency. Film, liquid crystal display, touch panel,
It can be used for antistatic of various films including applications such as stained glass.

As is known, the conductivity of a material depends on the cation,
It is expressed by anions or charge carriers existing in the particles such as electrons and holes.

When the main charge carrier is an ion, it becomes a solid electrolyte, and when the charge carrier is an electron, it becomes a semiconductor. An ordinary conductive material is a conductor in which both are mixed, and a nonstoichiometric compound such as an oxygen-deficient oxide, a metal-excess oxide, a metal-deficient oxide, or an oxygen-excess oxide becomes a semiconductor. The conductivity of many conductive materials is exerted in this way, and a method of dispersing fine particles composed of a conductor or a semiconductor material in an insulating polymer and imparting conductivity to the polymer to prevent electrification is Well studied. The inventors investigated various combinations of polymers and conductive particles or semiconductor particles, and found conditions satisfying both transparency and conductivity.

Further, a detailed study of the conductivity shows that generally, as shown in the following known formula, if the conductivity of the material increases, the absolute value of the impedance Z including the term of resistance decreases. Is well known.

[0018]

(Equation 1)

However, R: resistance, C: capacitance, ω: 2π
f, f: represents frequency.

However, under special conditions where the amount of the conductive particles added to the organic substance as the binder component is reduced, when the absolute value of the impedance at a frequency of 20 Hz is 4 × 10 ⁵ Ω or more, the film formation such as dust adhesion is prevented. It has been found that the problems caused by charging are solved. For example, in order to prevent electrification, when the conductive film is coated with excessive conductive particles to the extent that the transparency of the film is impaired, the conductivity of the film surface is improved, and the magnitude of the surface resistivity measured using direct current is increased. Is sufficiently low, and at the same time, the absolute value of the impedance measured by AC is also low. Such a film material does not cause electrostatic damage, but defeats the purpose of the present invention because it significantly impairs transparency. When priority is given to transparency and the amount of conductive particles added is reduced, the surface resistivity increases and the absolute value of impedance also increases. However, problems such as adhesion of dust and the like occur due to static electricity, and transparency is improved but antistatic performance is deteriorated.

As is apparent, if the surface resistivity is reduced,
That is, if the absolute value of impedance is lowered, antistatic performance is improved. Although the antistatic technology up to now has been continuously developed based on such a concept, the present invention does not sacrifice transparency, but uses a special combination of an absolute value of impedance and a composition to generate static electricity. Overcoming obstacles.

That is, in order to satisfy the transparency, it is necessary to reduce the addition amount of the fine particles, but if the addition amount of the fine particles is reduced, it becomes difficult to improve the surface resistivity as described above. However, the inventors diligently studied the relationship between the antistatic performance and the impedance, and within a range in which the transparency is not affected, the absolute value of the impedance is less than 4 × 10 ⁵ Ω in a region where a small amount of conductive particles is added. It has been discovered that increasing the size makes it possible to prevent electrification. Increasing the absolute value of impedance does not need to increase the amount of conductive particles added, and it becomes possible to control it with a polymer binder that does not have conductivity but can improve various physical properties of the film. It has been discovered that it is a new means of achieving antistatic protection while being limited.

As described above, the absolute value of the impedance at the frequency of 20 Hz is controlled by selecting the water-soluble binder in the addition region where the amount of the conductive particles is small to the extent that the transparency is not affected, and the transparency and the antistatic property are prevented. It is thought that a film satisfying both of the above conditions can be completed, and the condition of the absolute value of the impedance to be satisfied by the film material, the clarification of the addition amount of the conductive particles that does not affect the transparency, and the water-swellable binder in that range. The present invention has been completed by making an effort to clarify the above. Hereinafter, the present invention will be described in detail.

Regarding the impedance measurement of the film material in the present invention, a general impedance measuring device used for measuring the dielectric constant of electronic parts can be used.
Preferably, the impedance measuring device capable of measuring a frequency of 1 Hz or higher is combined with a film measuring electrode. For example, Yokogawa Hewlett-Packard (hereinafter YHP) Precision LCR meter HP
This is a combination of 4284A and HP16451B. When using another device, it is necessary to correct the electrode portion. In order to achieve the present invention, it is necessary to measure the impedance of the film material correctly, so that a preferable result cannot be obtained when an uncorrectable device is used. An example of obtaining the absolute value of the impedance at 20 Hz by this combination of devices will be described in detail, but the present invention does not limit the measuring method as long as the absolute value of the impedance at the accurate frequency of 20 Hz of the film material can be measured.

Using a precision LCR meter HP4284A connected to HP16451B having two electrodes composed of parallel planes and a guard electrode, 23 ° C., 20% R
The absolute value of the impedance of the film material is measured by the void method in an H atmosphere. Regarding the measurement of the void method, H
Follow the electrode non-contact method described in the instruction manual of P16451B. The size of the sample is not particularly limited as long as it is larger than the electrode plane, but the diameter of the main electrode is 3.
In the case of 8 cm, the size is 6 cm x 6 cm to 5 cm x
A 5 cm square sample is preferred. If the magnitude of the surface resistivity measured using the direct current of the sample is equal on the front and back sides, either side may be placed on the upper side, but if they are not the same on the front and back sides, the side with the lower surface resistivity is placed on the upper side. Towards
A sample is placed between two electrodes composed of parallel planes, and measurement is performed by the void method while applying an AC voltage.

The preferable range of the measured impedance is 4 × 10 ⁵ Ω or more, preferably 8 × 10 ⁵ Ω or more, more preferably the absolute value of impedance at a frequency of 20 Hz measured using an electrode having an area of 11 to 12 cm ^2. 1 x 10 ⁶ Ω
Above 10 ²⁰ Ω or less, a film material having both antistatic performance and transparency can be produced within the following composition range.

Regarding the amount of conductive particles added, the preferable range of the amount added varies depending on the type of particles such as the color, morphology and composition of the conductive particles, but considering transparency, per unit volume in the antistatic layer. The content is 50 vol% or less, preferably 40 vol% or less, more preferably 37 vol% or less. If the transparency condition is strictly selected, it is preferably 28 vol% or less, more preferably 20 vol% or less. The minimum required amount of conductive particles is selected from the conditions that the absolute value of impedance falls within the preferable range described above. If this condition is emphasized, the conductive particles must be 1 vol% or more, preferably 5 vol% or more, more preferably 10 v.
ol% or more is required.

The antistatic layer of the present invention is composed of the conductive particles and the water-soluble binder as basic components, and the absolute value of impedance is controlled. If necessary, a crosslinking agent and a surface active agent may be added within the scope of the present invention. Other components such as agents and mat materials may be added. However, addition of these other components to the extent that the absolute value of impedance is lowered, that is, addition beyond the range of the present invention, is not preferable because the purpose of the present invention cannot be achieved.

The main component of the conductive particles is 10 in volume resistivity.
The material is ⁹ Ωcm or less and 10 ⁻⁵ Ωcm or more, and may be composed of the same material or may be a combination of different materials. White or colorless metal oxide-based particles are preferable, and since conductivity of such particles tends to be low, a material of 10 ⁹ Ωcm or less and 10 ^-1 Ωcm or more is selected. Amorphous metal oxide sols are preferred for use in photographic light-sensitive materials where transparency is desired, and 10 ⁸ Ω
cm or less, a material of 10 ¹ Ωcm or more is selected.

The particle size of these particles is not particularly limited, but in the image taken by an electron microscope, the smaller size is preferably 10 μm or less, more preferably 1 μm or less. When transparency is required,
The thickness is preferably 0.5 μm or less, and most preferably 0.001 μm or more and 0.5 μm or less in the form of an amorphous metal oxide sol.

Regarding the value of the volume resistivity, a value obtained by dividing the volume resistivity of the molded body obtained by applying a constant pressure to the powder by 10 ² is adopted. The constant pressure is not particularly limited, but a pressure of 10 kg / cm ² or more is preferable, and more preferably 100 kg / cm ² or more and 10 t /
A value obtained by dividing the volume resistivity of the material molded by applying a pressure of less than cm ² by 10 ² is adopted. In general, regarding the pressure applied to the powder and the volume resistivity of the compact, the higher the pressure, the lower the volume resistivity tends to be. However, even when an isostatic pressure of 3 t / cm ² is applied by a hydrostatic pressure device, a value lower than the volume specific resistance value obtained with a single crystal cannot be obtained, and the value is about 100 times higher. Therefore, a value obtained by dividing the volume specific resistance of a molded body obtained by applying a constant pressure in a powder state by 10 ² is adopted.

In general, a semiconductor is a material having a volume resistivity of 10 Ωcm or more and less than 10 ¹² Ωcm, and a conductor is
A material of less than 10 Ωcm. In the present invention, both semiconductor and conductor are referred to as conductive particles.

The structure of the particles may be crystalline or amorphous, and the higher-order structure may have a graded composition, a regular composition distribution, or a non-uniform distribution. Any structure may be used as long as the structure and purpose of the present invention are achieved.

Examples of the particles include particles of metal, chalcogenite glass having conductivity, and particles of a metal oxide. From the viewpoint of chemical stability, a metal oxide is preferable, but the object of the present invention is achieved. If possible, any inorganic material having conductivity may be used. When a metal oxide is used, the synthesis method may be any known method that can achieve the object of the present invention. For example, a coprecipitation method using a metal or a compound containing a metal as a raw material, a multistage wet method,
Examples thereof include sol-gel method, atomizing method, plasma pyrolysis method, and other methods for producing fine particles and ultrafine particles.
Here, the metal or the compound containing the metal means Li, Na, K, Rb, Cs, Be, Mg, depending on the powder synthesis method.
Ca, Sr, Ba, Sc, Y, La, Ce, Ti, Z
r, V, Nb, Cr, Mo, W, Mn, Fe, Co, N
i, Ru, Rh, Pd, Os, Ir, Pt, Cu, A
g, Au, Zn, Cd, Hg, Al, Ga, In, T
l, Si, Ge, Sn, Pb, As, Sb, Bi, S
a compound containing e, Te and Po elements, preferably N
i, Ir, Rh, Nb, Ce, Zr, Th, Hf, Z
n, Ti, Sn, Al, In, Si, Mg, Ba, M
It is a compound containing o, W, and V as main components. Preferably a water-soluble or organic solvent-soluble compound such as Fe
SO ₄ · 7H ₂ O, water-soluble metal salts such as CuSO _4, N
Metal compounds soluble in organic solvents such as iCl ₂ and PdCl ₂ , metal alkoxides such as Ti (OC ₃ H ₇ ) ₄ and organometallic compounds such as ferrocene are selected. Alternatively, a material containing a compound containing a metal as a main component and solid at room temperature can be used in combination. Anything is fine.

The composition and crystal form of the metal oxide particles obtained by these production methods are not limited, and any composition and crystal form can be used as long as the object of the present invention can be achieved, whether amorphous or crystalline.

For example, simple cubic lattice, body centered cubic lattice, face centered cubic lattice, simple square lattice, body centered square lattice, simple orthorhombic lattice, bottom centered orthorhombic lattice, body centered orthorhombic lattice, face centered orthorhombic lattice. , Simple monoclinic lattice, bottom center monoclinic lattice, triclinic lattice, rhombohedral lattice,
A compound having a specific structure such as a hexagonal lattice is included.

In the present invention, the crystalline porous material is also
It can be used.

In addition to these specific crystalline compounds, powders which do not give a sharp diffraction peak when evaluated by powder X-ray diffractometry may be used. If the composition originally takes a specific crystal form, or most of the diffraction peak values can be identified in a specific crystal, but it is unclear because it is partially widened, or Amorphous powders that are all broadened can also be used if the object of the present invention can be achieved. Examples of such metal oxides include colloidal SnO ₂ sols. This compound does not cause problems such as sedimentation,
It is a compound suitable for achieving the object of the present invention. S
Regarding the method for producing nO ₂ ultrafine particles, temperature conditions are particularly important, and a method involving heat treatment at a high temperature is not preferable because it causes the growth of primary particles and the phenomenon that crystallinity increases.
When it is necessary to perform heat treatment, 400 ℃
It should be kept below 300 ° C, preferably below 200 ° C, more preferably below 150 ° C. Sn of the manufacturing method described in JP-B-35-6616
O ₂ sol is a suitable example for the present invention. Further, in accordance with the method described in JP-B-35-6616, fluorine,
A material doped with a different element such as Sb is also suitable.

The binder used in the present invention is not particularly limited as long as it is a film-forming substance and water-soluble, and examples thereof include proteins such as gelatin and casein, hydroxyethyl cellulose, acetyl cellulose, diacetyl cellulose, and triacetyl cellulose. Examples thereof include cellulose compounds such as acetyl cellulose, dextran, agar, sodium alginate, sugars such as starch derivatives, polyvinyl alcohol, polyvinyl acetate and other synthetic polymers. In particular, gelatin (lime-processed gelatin, acid-processed gelatin, enzyme-decomposed gelatin, phthalated gelatin, acetylated gelatin, etc.), acetyl cellulose, diacetyl cellulose, triacetyl cellulose, polyvinyl acetate, polyvinyl alcohol and the like are preferable.

A method of dispersing the binder and the conductive particles or the semiconductor particles, which is a method of utilizing free rotation motion,
How to use the obstacle motion in a container with a baffle, how to use the falling motion to rotate a closed container around a horizontal axis, how to use the shaking motion to shake the container up and down, on the roll There are various methods such as utilizing the shearing force, but any method may be selected as long as the object of the present invention is not impaired.

Regarding the conditions for mixing, the binder and the conductive or semiconductor particles are mixed at a concentration of less than 5%. Preferably, the concentration is less than 2%, more preferably less than 1%. However, mixing in a state of being diluted to a concentration of less than 0.01% consumes a large amount of energy in the subsequent concentration process, which is not preferable. After mixing under such a dilute condition, when applying, it is concentrated to a concentration of 5% or more and used. More preferably, it is concentrated to a concentration of 8% or more,
It is preferable to use it after re-diluting it to a concentration necessary for coating. In the concentration process, high concentration of 40% or more
It is not preferable because a precipitate is formed. Although the cause is not clear, the characteristic value of the present invention can be obtained by lowering the concentration at the time of dissolution preparation to a certain extent, concentrating once before coating, and then coating, to obtain a layer with a high antistatic effect. be able to.

The plastic film material used in the present invention includes, for example, cellulose nitrate film, cellulose acetate film, cellulose acetate butyrate film, cellulose acetate propionate film, polystyrene film, polyethylene terephthalate film, polycarbonate film and others. There is a laminated product, etc.

These plastic film materials can be used as a support for a photographic light-sensitive material. Further, the transparent support is not limited to a colorless and transparent one, but it can be colored and transparent by adding a dye or a pigment.

Of these film materials, it is also possible to select polymer polymerization conditions and use a highly stereoregular polymer. For example, a plastic film containing syndiotactic polystyrene (SPS) as a main component may be used. The effect of the present invention is more effective in a film that is particularly easily charged, such as an SPS film.

In the present invention, the film containing syndiotactic polystyrene as a main component means that the stereoregular structure (tacticity) is mainly a syndiotactic structure,
That is, a phenyl group or a substituted phenyl group, which is a side chain with respect to the main chain formed from carbon-carbon bonds, has a three-dimensional structure alternately positioned in the opposite direction, and the main chain of the main chain is a racemo chain. A styrene-based polymer or a composition containing the styrene-based polymer, and a styrene homopolymer can be polymerized by the method described in JP-A-62-117708. It can be obtained by polymerization according to the method described in JP-A-1-46912, JP-A-1-178505 and the like.

The tacticity is quantified by a nuclear magnetic resonance method ( ¹³ C-NMR method) using isotope carbon. ¹³ C-
The tacticity measured by the NMR method can be indicated by the abundance ratio of a plurality of continuous constitutional units, for example, diad in the case of 2, triad in the case of 3, and pentad in the case of 5. The styrene-based polymer having a predominantly syndiotactic structure as used in the present invention is usually 75% or more in terms of racemic dyad, preferably 8%.
5% or more, or 60% or more of racemic triad, preferably 75% or more, or 30% or more of racemic pentad, preferably 50% or more.

Specific monomers of the polymer constituting the syndiotactic polystyrene composition include alkylstyrene such as styrene and methylstyrene, halogenated (alkyl) styrene such as chloromethylstyrene and chlorostyrene, alkoxystyrene, and the like. It is a single or a mixture containing vinyl benzoate as a main component. In particular, a copolymer of alkyl styrene and styrene has a
This is a preferable combination for obtaining a film having a thickness of at least m.

The polystyrene resin having a syndiotactic structure of the present invention is a transition metal (a) (a) described on page 4-10 of JP-A-5-320448 as a catalyst for polymerization using the above raw material monomers. A compound and (b) an aluminoxane-based compound, or (b) a (a) transition metal compound and (c) a compound capable of reacting with a transition metal compound to form an ionic complex as a main component are used. It can be polymerized and produced.

As the light-sensitive material according to the present invention, an ordinary black-and-white silver halide light-sensitive material (for example, a black-and-white light-sensitive material for photographing,
Ordinary multilayer color light-sensitive materials (eg, black-and-white light-sensitive material for X-ray, black-and-white light-sensitive material for printing) (for example, color reversal film, color negative film, color positive film, etc.),
Various photosensitive materials such as transfer image forming materials (for example, color proof used for proof printing of printing) can be mentioned.

[0050]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the present invention.

(Dispersion of conductive particles P1) 65 g of stannic chloride hydrate was dissolved in 2000 cc of an aqueous solution to obtain a uniform solution. Then, this was boiled to obtain a coprecipitate. The resulting precipitate is removed by decantation, and the precipitate is washed with distilled water many times. Silver nitrate is dropped into distilled water from which the precipitate has been washed to confirm that there is no reaction of chloride ions. This precipitate is added and dispersed in 1000 cc of distilled water, and the total amount is made 2000 cc. Further, add 30% ammonia water to 40
When cc is added and heated in a water bath, 1.5 wt% SnO
_{2 A} sol solution is produced.

Regarding the volume resistivity of particles contained in this sol solution, a value measured by a four-terminal method after forming a thin film on silica glass using the sol solution was taken as the volume resistivity value of the particles. Measured volume resistivity is 3.4 × 10 ⁴ Ω
cm.

(Conductive Particle P2 Dispersion) An aqueous solution of 65 g of stannic chloride hydrate and 1.0 g of antimony trichloride in 200 aqueous solution.
It was dissolved in 0 cc to obtain a uniform solution. Then, this was boiled to obtain a coprecipitate. The resulting precipitate is removed by decantation, and the precipitate is washed with distilled water many times. Silver nitrate is dropped into distilled water from which the precipitate has been washed to confirm that there is no reaction of chloride ions. 1000cc of distilled water
After adding and dispersing in it, the total amount is 2000 cc. Further, when 40 cc of 30% aqueous ammonia is added and heated in a water bath, a SnO ₂ sol solution is generated.

This sol solution was sprayed into an electric furnace heated to 400 ° C. to synthesize a conductive powder. After molding the obtained powder with a tablet molding machine, the volume resistivity measured by the four-terminal method was 1.5 × 10 ¹ Ωcm.

This conductive powder was dispersed in ammonia water having a pH of 10 so as to have a concentration of 1 wt%.

(Example 1) (Preparation of support for silver halide photographic light-sensitive material) A biaxially stretched and heat-fixed polyethylene terephthalate film having a thickness of 100 μm was subjected to a corona discharge treatment of 8 W min / m ² on both sides. As described in JP-A-59-19941, an undercoating coating solution B-1 described below was applied as an undercoating layer B-1 to a dry film thickness of 0.8 μm and dried at 100 ° C. for 1 minute. did. On the surface opposite to the undercoat layer B-1 of the polyethylene terephthalate film, there is disclosed in JP-A-59-7743.
As described in No. 9, the following subbing coating solution B-2 was applied as a subbing layer B-2 to a dry film thickness of 0.8 μm,
It was dried at 100 ° C. for 1 minute.

* Undercoating first layer <Undercoating coating liquid B-1> Copolymer of 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene and 25% by weight of 2-hydroxyethyl acrylate Latex liquid (solid content 30%) 270 g Compound A 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Water is made up to 1 liter.

<Undercoating Coating Liquid B-2> Copolymer latex liquid of butyl acrylate 40% by weight, styrene 20% by weight and glycidyl acrylate 40% by weight (solid content 30%) 270 g Compound A 0.6 g Hexa Methylene-1,6-bis (ethylene urea) 0.8 g Make up to 1 liter with water.

* Undercoating second layer (A) Further, a corona discharge of 8 W min / m ² was applied on the above-mentioned undercoating layer B-1 so that the following coating solution B-3 had a dry film thickness of 0.1 μm. As an undercoat layer B-3, and dried at 100 ° C. for 1 minute.

<Undercoating Coating Liquid B-3> Gelatin 10 g Compound A 0.4 g Compound B 0.1 g Silica particles having an average particle size of 3 μm 0.1 g Water is made up to 1 liter.

* Second layer for undercoating (B) 10 g of gelatin is dissolved in 500 g of water to prepare an aqueous gelatin solution. 4000 g of the dispersion liquid of the conductive particles P1
A gelatin aqueous solution is dropped into the mixture while stirring with a homomixer. After mixing with a homomixer for 30 minutes, water is removed using an evaporator and the mixture is concentrated until it reaches 500 g. 500 g of water, 0.4 g of compound A and 0.1 g of compound B were added to this concentrated solution to prepare a subbing coating solution B-3-1.

On the above-mentioned undercoat layer B-2, corona discharge of 8 W min / m ² was applied, and the undercoat coating solution B-3-1 was applied to the undercoat layer B-3 so as to have a dry film thickness of 0.1 μm. -1, and dried at 100 ° C. for 1 minute.

An appropriate amount of the undercoat coating solution B-3-1 was sampled and heated in air at 800 ° C. When the ratio of SnO ₂ particles (specific gravity 7) to gelatin was determined from the ash obtained from this treatment, it was 46 vol%.

[0064]

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(Emulsion preparation) Grains containing rhodium in an amount of 10 ^-5 mol per mol of silver were prepared by a control double jet method in an acidic atmosphere of pH 3.0. The particles were grown in a system containing 30 mg of benzyladenine per liter of a 1% aqueous gelatin solution. After mixing silver and halide 6-methyl-4-hydroxy-1,3,3a, 7-
Tetrazaindene 600m per mol of silver halide
g, then washed with water and desalted.

Next, 60 m per mol of silver halide
g of 6-methyl-4-hydroxy-1,3,3a, 7-
After the addition of tetrazaindene, sulfur sensitization was performed. 6-methyl-4-hydroxy- as a stabilizer after sulfur sensitization
1,3,3a, 7-Tetrazaindene was added.

(Silver Halide Emulsion Layer) Additives were prepared and added to the above emulsions in the amounts shown below, and coated on the undercoat layer B-3-1 of the support.

Latex polymer: styrene-butyl acrylate-acrylic acid terpolymer 1.0 g / m ² tetraphenylphosphonium chloride 30 mg / m ² saponin 200 mg / m ² polyethylene glycol 100 mg / m ² sodium dodecylbenzene sulfonate 100 mg / m ² hydroquinone 200 mg / m ² phenidone 100 mg / m ² sodium styrenesulfonate-maleic acid copolymer (Mw = 250,000) 200 mg / m ² gallic acid butyl ester 500 mg / m ² tetrazolium compound 30 mg / m ² 5-methylbenzo triazole 30 mg / m ² 2-mercaptobenzimidazole-5-sulfonic acid 30 mg / m ² Inner toe Thane gelatin (isoelectric point ^{4.9) 1.5g / m 2 1- (} p- acetyl amide Fe Le) -5-mercaptotetrazole 30 mg / m ² silver amount 2.8 g / m ²

[0069]

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(Emulsion Layer Protective Film) An emulsion layer protective film was prepared and coated in the following amounts.

Fluorinated dioctyl sulfosuccinate 300 mg / m ² matting agent: polymethylmethacrylate (average particle size 3.5 μm) 100 mg / m ² lithium nitrate 30 mg / m ² acid-treated gelatin (isoelectric point 7.0) 1.2 g / m ² colloidal silica 50 mg / m ² sodium styrenesulfonate-maleic acid copolymer 100 mg / m ² mordant 30 mg / m ² dye 30 mg / m ²

[0072]

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(Backing Layer) A backing dye having the following composition was coated on the support on the side opposite to the emulsion layer. The gelatin layer was hardened with glyoxal and 1-oxy-3,5-dichloro-S-triazine sodium salt and a hydroxy-containing epoxy compound (d).

Hydroquinone 100
mg / m ² phenidone 30 mg / m ² latex polymer: butyl acrylate-styrene copolymer 0.5 g / m ² styrene-maleic acid copolymer 100 m
g / m ² citric acid 40 mg / m ² benzotriazole 100 mg / m ² styrene sulfonic acid-maleic acid copolymer 100 mg / m ² lithium nitrate 30 mg / m ² backing dyes (a) (b) (c) 40,30 , 30 mg / m ² ossein gelatin 2.0 g / m ²

[0075]

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The sample obtained as described above was exposed on the whole surface and developed using the developing solution and fixing solution shown below, and then the surface resistivity test and the ash adhesion test method were performed. The results are shown in Table 1.

<Developer formulation> Hydroquinone 25 g 1-phenyl-4,4-dimethyl-3-pyrazolidone 0.4 g Sodium bromide 3 g 5-methylbenzotriazole 0.3 g 5-nitroindazole 0.05 g diethylaminopropane-1, 2-diol 10 g potassium sulfite 90 g sodium 5-sulfosalicylate 75 g sodium ethylenediamine tetraacetate 2 g Water was made up to 1 liter.

The pH was adjusted to 11.5 with caustic soda.

<Fixer Formulation> (Composition A) Ammonium thiosulfate (72.5 w% aqueous solution) 240 m
l Sodium sulfite 17g Sodium acetate ・ trihydrate 6.5g Boric acid 6g Sodium citrate ・ dihydrate 2g Acetic acid (90 wt% aqueous solution) 13.6 ml (Composition B) Pure water (ion exchanged water) 17 ml Sulfuric acid (50 wt% aqueous solution) ) 3.0 g Aluminum sulfate (aqueous solution having an Al ₂ O ₃ conversion content of 8.1 wt%) 20 g When the fixing solution was used, the above composition A and composition B were dissolved in this order in 500 ml of water to make 1 liter. The pH of this fixer was about 5.6.

(Development processing conditions) (Process) (Temperature) (Time) Development 40 ° C. 8 seconds Fixing 35 ° C. 8 seconds Rinsing at room temperature 10 seconds (Evaluation of antistatic performance: Ash adhesion test method) 23 ° C., 20
Under the condition of% RH, the emulsion side of the developed sample was rubbed with a rubber roller several times, and tobacco ash was brought close to it, and it was examined whether or not it sticked to the film according to the following evaluation.

◯: No adhesion even when approached to 1 cm ○ Δ: Adhesion when approached to 1 cm to 4 cm Δ: Adhesion when approached to 4 cm to 10 cm ×: Adhesion even at 10 cm or more ○ Δ If practically impaired Absent.

(Measurement Method of Absolute Value of Impedance) For impedance measurement, a combination of Precision LCR meter HP4284A and HP16451B manufactured by Yokogawa-Hewlett-Packard (hereinafter YHP) was used.

The absolute value of the impedance of the film material was measured by the void method in an atmosphere of 23 ° C. and 20% RH.
For measurement of the void method, refer to the HP 16451B instruction manual (part number 16451-97000, print 198).
Electrode non-contact method described in December 1997). Using Electrode-A having a main electrode diameter of 3.8 cm, the sample size was cut into a square of 5.5 cm x 5.5 cm. The dispersed layer of conductive particles was measured upward.

(Haze test) A sample subjected to the undercoating treatment up to the second layer was used as a turbidimeter Model T-2 manufactured by Tokyo Denshoku Co., Ltd.
The haze was measured by using 600 DA and expressed in%.

Example 2 10 g of gelatin is dissolved in 500 g of water to prepare an aqueous gelatin solution. Conductive particles P
An aqueous gelatin solution is added dropwise to 4000 g of the dispersion liquid of 2 while stirring with a homomixer. After mixing with a homomixer for 30 minutes, water is removed using an evaporator and the mixture is concentrated until it reaches 500 g. 500 g of water, 0.4 g of compound A and 0.1 g of compound B were added to this concentrated solution to prepare a subbing coating solution B-3-2.

A corona discharge of 8 W / m ² was applied on the undercoat layer B-2, and the undercoat coating solution B-3-2 was applied to the undercoat layer B-3 so that the dry film thickness was 0.1 μm. -2, and dried at 100 ° C. for 1 minute.

An appropriate amount of the undercoat coating solution B-3-2 was sampled and heated in air at 800 ° C. The ratio of the conductive particles (specific gravity 7) to gelatin was calculated from the ash obtained from this treatment, and it was 36 vol%.

The sample preparation conditions were as follows: instead of the undercoating coating solution B-3-1 as the second undercoating layer, the undercoating coating solution B-3-2 was used.
Was prepared in the same manner as in Example 1 except that was used, and the same evaluation as in Example 1 was performed.

(Comparative Example 1) Sample preparation conditions are:
Subbing coating solution B instead of subbing coating solution B-3 as a layer
It was prepared in the same manner as in Example 1 except that −0 was used, and the same evaluation as in Example 1 was performed.

<Undercoating Coating Liquid B-0> Gelatin 10 g Compound A 0.4 g Compound B 0.1 g Silica particles having an average particle size of 3 μm 0.1 g Water is made up to 1 liter.

(Comparative Example 2) The sample preparation conditions are the second subbing
Subbing coating solution B instead of subbing coating solution B-3 as a layer
Example 1 was prepared in the same manner as in Example 1 except that -02 was used.
The same evaluation was performed. However, the tin oxide powder contained in the undercoat coating liquid B-02 is a powder obtained by firing tin oxide containing 3% of antimony oxide at a temperature of 900 ° C. and crushing it with a ball mill. This powder had an average particle size of 0.5 μm and a specific gravity of 6.8.

The subbing coating solution was prepared in the same manner as in Example 1, but a tin oxide powder precipitate was observed in the coating solution container after coating the film.

<Undercoating Coating Liquid B-02> Gelatin 5 g Compound A 0.4 g Compound B 0.1 g Tin oxide powder 9.6 g Water 200 g

[0094]

[Table 1]

As is clear from Table 1, the photographic light-sensitive material of the present invention has a good ash adhesion test and good transparency. Further, in the photographic light-sensitive material of the present invention, generation of pressure fog and scratches was not recognized.

[0096]

EFFECT OF THE INVENTION A plastic film material and a silver halide photographic light-sensitive material having excellent transparency without generation of pressure fog and scratches and having high antistatic performance even under low humidity can be provided.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location C09D 5/24 PQW C09D 5/24 PQW 7/12 PSR 7/12 PSR

Claims (6)

[Claims] 1. A film material having at least one conductive layer, the process comprising applying a mixture coating solution in which the conductive layer contains conductive particles or semiconductor particles and at least two components of a water-soluble binder. The conductive particles and the semiconductor particles are formed in an amount of 1 vol% or more and 50 vol% or less of the conductive layer, and the absolute value of impedance of the film material at a frequency of 20 Hz is 4 × 10 ^5.
An antistatic plastic film material having a resistance of Ω or more. 2. 50% or more of the solvent constituting the coating liquid is water, contains a water-soluble binder and conductive particles or semiconductor particles, and is prepared at a solid content concentration of less than 5 wt%,
The plastic film material according to claim 1, further comprising an antistatic layer formed by applying a coating solution having a solid content concentration of 8 wt% or more after mixing. 3. The conductive particles or semiconductor particles are oxide sols containing a metal element.
Or the plastic film material according to 2. 4. The conductive particles or the semiconductor particles are 40
The plastic film material according to any one of claims 1 to 3, which is an oxide containing a metal element produced at a temperature of 0 ° C or lower. 5. The plastic film material according to claim 1, wherein the plastic film material is a film containing syndiotactic polystyrene as a main component. 6. A silver halide photographic light-sensitive material comprising the film material according to any one of claims 1 to 5 as a support.