JPH07219133A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material with a polyester base inhibiting coloring due to thin film interference, maintaining superior dynamic characteristics even in the case of a reduced thickness and less liable to curl. CONSTITUTION:This silver halide photographic sensitive material has a base made of polyester having 50 to 200 deg.C glass transition temp. (Tg) and heat-treated at a temp. between (Tg-50 deg.C) and Tg for 0.1 to 1,500hr. The thickness of the base is 50 to 300mum and the surface of the base has 1 to 500nm surface roughness (expressed in terms of average height) or the base has an adjacent layer having 1 to 500nm surface roughness (expressed in terms of average height). The base has an antistatic layer on the surface and a polymer layer having 0.1 to 5mum thickness on the antistatic layer. When light with 400 to 750nm wavelength is made incident on the base from the polymer layer side at 6 deg. incident angle, the amplitude of reflected light is <=5% of the intensity of the incident light.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic light-sensitive material, and in particular, a silver halide photographic light-sensitive material having a polyester support which is suppressed from coloring due to thin film interference, has excellent mechanical properties, and is hard to have curl. It is about.

[0002]

Photographic light-sensitive materials are generally prepared by coating at least one photographic light-sensitive layer on a plastic film support. This plastic film is generally triacetyl cellulose (hereinafter referred to as "T
Fiber-based polymers represented by "AC") and polyester-based polymers represented by polyethylene terephthalate (hereinafter referred to as "PET") are used. A TAC film is mainly used as a film support for rolls, and a PET film has been considered as a substitute for TAC because of its excellent mechanical strength and dimensional stability. In the roll form used, the curl is strongly retained and the handleability after development is poor, and the range of use has been limited to a sheet film while having the above-mentioned excellent properties.

By the way, in recent years, the downsizing of photographing apparatuses has been remarkably advanced from the viewpoint of handleability. With the downsizing of the photographing device, there is an increasing demand for downsizing the cartridge. Conventionally, in the 135 system, a cartridge having a diameter of 25 mm has been used. However, if the diameter of the spool (winding core) is reduced, and at the same time, the thickness of the support used in the existing 135 system is reduced, the cartridge is further improved. It can be miniaturized. However, there are two problems to be solved in order to reduce the size of the cartridge by the above method. The first problem is a decrease in mechanical strength as the support becomes thinner. The second problem is a strong curl during storage over time, which occurs with the miniaturization of Patrone.

On the other hand, a support used for a photographic light-sensitive material is generally electrically insulating, and is subjected to contact friction or peeling with the surface of the same kind or different kinds of materials during the manufacturing process of the photographic light-sensitive material and at the time of use, whereby electrostatic charge is generated. Is easily accumulated. The accumulated electrostatic charges cause various obstacles to the light-sensitive material. Among them, the electrostatic charges accumulated before the development process are discharged, so that the photosensitive layer is exposed to light, and as a result, spotted spots are formed after the development process. There is a big problem that a resin-like streak is generated, and the accumulated electrostatic charge attracts dust at the time of printing and it is reflected on the screen. In order to prevent these obstacles, it is most effective to apply an antistatic layer, which retains antistatic properties before and after development, onto the photosensitive material.
For example, JP-A-63-63035, JP-B-60-4989
4, it is known to apply an antistatic layer containing a conductive metal oxide as described in JP-B-1-20734. However, coating an antistatic layer containing a metal oxide on the side of the photosensitive layer (particularly between the photosensitive layer and the support) deteriorates the adhesion between the photosensitive layer and the support, and causes fog in the photosensitive layer. It is not preferable because

Therefore, it is preferable to coat an antistatic layer containing a conductive metal oxide on the back side of the photosensitive material. However, such an antistatic layer generally has very poor strength as a film, and if this antistatic layer is applied as the outermost layer, the metal oxide is removed. Therefore, it is necessary to coat a transparent polymer layer on the antistatic layer in order to protect it. However, since the conductive metal oxide has a much higher refractive index than the polymer, strong reflection of light occurs at the interface between the polymer layer and the antistatic layer, and as a result, strong thin film interference occurs inside the polymer layer, which may cause a problem from the back surface. When you look at the material, it looks strongly colored. This phenomenon is especially due to whether the support surface has a surface roughness of 1 nm to 500 nm in average height or an adjacent layer having a surface roughness of 1 nm to 500 nm in average height, and At least one polymer layer on the antistatic layer is 0.1 μm
It occurs remarkably when the thickness is 5 μm or less. Coloring of sensitive materials due to thin-film interference changes greatly with the subtle changes in the film thickness of the polymer layer.For example, when a reversal film is placed in a mount for slide projection or when printing on photographic paper, It may appear as a deviation in the color tone of, or it may appear as a stain. Furthermore, when the film is viewed directly, the color tone also changes depending on the viewing angle (this is because the optical path length changes depending on the viewing angle).
Therefore, it becomes difficult to determine the color tone actually captured.

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a silver halide photographic light-sensitive material having a polyester support which is suppressed from coloring due to thin film interference, has excellent mechanical properties, and is hard to have a curl. Especially.

[0007]

These problems are solved in a silver halide photographic light-sensitive material having a silver halide emulsion layer on one side of a support, the support having a glass transition temperature (Tg) of 50 ° C. It is mainly composed of polyester having a temperature of ~ 200 ° C and has a temperature of Tg ~ (Tg-50 ° C) of 0.1 to 0.1%.
Heat-treated for 1500 hr, its thickness is 50-300 μm
Or the surface of the polyester support has an average height of 1 nm to 500 nm, or the surface of the support has an average height of 1 nm.
Having an adjacent layer having a surface roughness of ˜500 nm, and at least one layer on the surface having the surface roughness is an antistatic layer containing a conductive metal oxide, and At least one layer on the antistatic layer has a thickness of 0.
It has a polymer layer of 1 to 5 μm, and light of 400 to 750 nm is made incident from the side having the polymer layer at an incident angle of 6 degrees, and the amplitude of reflected light is 5% or less of the intensity of incident light. Was achieved in a silver halide photographic light-sensitive material.

First, a method of suppressing coloring due to thin film interference of the present invention will be described. Either the polyester support surface has a surface roughness of 1 nm to 500 nm in average height, or an adjacent layer having a surface roughness of 1 nm to 500 nm in average height, and At least one layer on any of the above-mentioned surfaces having a surface roughness is an antistatic layer containing a conductive metal oxide, and a polymer layer of 0.1 to 5 μm is further provided on at least one layer on the antistatic layer. In that case, remarkable coloring of the photosensitive material may occur due to thin film interference of light reflected at the interface between the antistatic layer and the polymer layer. Such coloring causes a failure such as when the reversal film is placed in a mount for slide projection and when it is printed on photographic paper, as a color tone shift on the screen or as a stain. In order to prevent such a failure due to coloring of the light-sensitive material, it is sufficient to reduce the coloring, and specifically, 400 to 750 nm at an incident angle of 6 degrees from the side having the polymer layer.
Light is incident, and the amplitude of the reflected light is 5% of the incident light intensity.
It was to do the following. Therefore, in the present invention, the amplitude of the reflected light under that condition must be set to 5% or less of the incident light intensity. The above-mentioned "amplitude of reflected light" means the line connecting the peaks of the curve obtained by taking the wavelength of the reflected light on the horizontal axis and the intensity of the reflected light on the vertical axis, and connecting the valleys and valleys. It is the width (difference) at the point where the width of the dash is the largest. Generally, when light is incident on a thin film, the incident light is repeatedly reflected at both interfaces sandwiching the thin film to cause so-called thin film interference, and as a result, the light that appears outside the thin film has a color tone and appears to be colored. (For example, soap bubbles, oil on the surface of the water, etc.)
It has an amplitude in the wavelength region of 0 to 750 nm, and it is because the superposition of the light of the wavelength of the peak portion of the amplitude appears as a color tone. Further, the coloring caused by the light caused by the thin film interference becomes more visible as the amplitude of the interference light increases. In the present invention, reflected light (including interference light)
It is considered that there is little or very little coloring, because the amplitude of is small as described above.

In the light-sensitive material handled here, since the difference in the refractive index between the conductive metal oxide and the polymer is large, the reflection of light occurs particularly strongly at the interface between the antistatic layer and the polymer layer, and this reflected light The amplitude of light generated by thin film interference in the polymer layer is increased. And the polymer layer is 0.1 μm
When a light having a thickness of ˜5 μm and a wavelength of 400 to 750 nm is made incident at an incident angle of 6 degrees, the coloring causes a failure when the amplitude of the reflected light exceeds 5%. Polymer layer thickness is 0.1
If the thickness is less than μm, the thin film interference of light having a wavelength of 400 nm or more does not occur in consideration of the refractive index of the polymer layer, so that no failure occurs. Further, if the thickness of the polymer layer is thicker than 5 μm, even if the amplitude of the reflected light is large, the light of the interfering wavelengths increases and the color tone when superposed becomes nearly colorless, and no failure occurs. When the surface roughness of the surface of the support or the layer adjacent to the support is 1 nm or less in average height, light is strongly reflected at the support or the interface immediately above the support and the layer immediately above the support, and this is charged. Since the light reflected by the interface between the prevention layer and the polymer layer interferes well and is canceled, the amplitude of the reflected light does not exceed 5% of the incident light intensity, and the failure due to the coloring of the light-sensitive material due to thin film interference does not occur. Absent. Generally, the surface roughness of the surface of the support or the adjacent layer of the support is formed by etching treatment or coating of an undercoat layer, and it is a method usually used for improving the adhesion between the support and the layer above it. Then, the surface roughness state is, for example, the type and amount of the etching agent, the drying condition, and the type and amount of the binder
Depending on the solvent type and other additives (fine particles, etc.),
The average height varies from 1 nm to 500 nm.

In the present invention, the polymer layer has a thickness of 0.1 μm to 5 μm.
When the thickness is m, it is preferable that the amplitude of reflected light when light of 400 to 750 nm is incident at an incident angle of 6 degrees is smaller.
However, it is extremely difficult in principle to completely eliminate it, and it is preferably 4% or less, more preferably 3% or less, further preferably 2% or less, and particularly preferably 1% or less. When the amplitude of reflected light is 1 to 5%, the film thickness of the polymer layer on the antistatic layer can be controlled in order to further suppress coloring due to thin film interference. At this time, the thickness of the polymer layer is preferably 0.7 to 5 μm. Film thickness 0.7 ~
By setting the thickness to 5 μm, the number of lights having wavelengths that cause thin film interference increases, and the purity of the color tone when they are superposed decreases, so that coloring is further suppressed. In this way, by controlling the film thickness, it is possible to determine the color tone when the film is directly viewed. Among the film thicknesses of 0.7 to 5 μm, it is preferable to design the film thickness so that the coloring due to thin film interference has a color tone of green blue to blue to violet. The color tone of the coloring is determined by three parameters of the refractive index of the polymer forming the polymer layer, the film thickness and the viewing angle. More preferably, the color tone is The film thickness is designed so that there are many angular components that look like greenish blue to blue to blue purple as a color tone when viewed at an angle of 3 to 70 degrees with respect to the line. The closer to greenish blue to blue to bluish purple the color tone is, the less visible the color of the light-sensitive material becomes. More preferably, the film thickness is designed so that the angle components that appear as greenish blue to blue to blue purple as the color tone are increased when viewed while tilted at an angle of 5 to 60 degrees. It is particularly preferable to design the film thickness so that the angle components that appear as greenish blue to blue to blue purple as the color tone are increased when viewed while tilted at an angle of 5 to 50 degrees.

Next, the antistatic layer of the present invention will be described. The antistatic layer of the present invention contains a conductive metal oxide as an antistatic agent and is coated on the back side of the photosensitive material. Then, this antistatic layer affects the degree of thin film interference occurring at the interface sandwiching the polymer layer, and determines the strength of coloring. Examples of conductive metal oxides include Zn
O, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , S
Fine particles of at least one crystalline metal oxide selected from among iO ₂ , MgO, BaO, MoO ₃ , and V ₂ O ₅ or a composite oxide thereof (fibrous, needle-like, spherical, plate-like, indefinite Shape). For fine particles of metal oxides or composite oxides thereof, see JP-A-56-143.
No. 430 and No. 60-258541. These conductive metal oxide fine particles can be prepared by first burning the metal oxide fine particles and then heat-treating them in the presence of different atoms to improve conductivity. Second, burning the metal oxides. There are used a method of coexisting different kinds of atoms during the production of fine particles of particles, a third method of introducing oxygen defects by reducing the oxygen concentration during firing. Heteroatoms include Al and In for ZnO, Nb and Ta for TiO ₂ , and Sb, Nb for SnO ₂ .
Examples thereof include P, B, In, V and halogen. The addition amount of the heteroatom is preferably in the range of 0.01 mol to 30 mol%, particularly preferably 0.1 to 10 mol%. Furthermore, in order to improve the dispersibility of fine particles and the transparency, a silicon compound may be added during the formation of fine particles.

Further, as described in JP-B-59-6235, a conductive material obtained by adhering the above-mentioned metal oxide to other crystalline metal oxide particles or fibrous material (for example, titanium oxide) is used. Good. In order to suppress coloring of the light-sensitive material, which is an object of the present invention, it is necessary to make it difficult for thin film interference to occur at the interface sandwiching the polymer layer. As a method of making thin film interference less likely to occur, reducing the coating amount of the conductive metal oxide per unit area and reducing the weight ratio of metal oxide / binder in the antistatic layer can be mentioned. The effect is to reduce the coating amount of the conductive metal oxide per unit area. By reducing the coating amount of the metal oxide per unit area, the interface between the metal oxide and the binder is reduced, and the intensity of the reflected light from the surface of the antistatic layer is reduced. The shape, size, volume resistivity and the like of the conductive metal oxide used in the present invention differ depending on the type, but in terms of reducing the coating amount per unit area, the shape is most preferably a fibrous shape with a large aspect ratio. Next, the order is needle-like, plate-like, irregular shape, spherical. The volume resistivity is preferably as low as possible, preferably 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less, and further preferably 10 ² Ω · cm or less. The amount of application per unit area including the shape and volume resistivity of the conductive metal oxide can be most reduced by using SnO ₂ as the main component and antimony oxide of about 5
Metal oxide is contained 20% and it still other components (e.g. silicon oxide, boron, phosphorus, etc.) metal oxide is _{contained, ZnO, TiO 2, In 2} O 3 ( or irregular shape), V ₂ O ₅ (fibrous), which are preferably used in the present invention. Among them, particularly preferable is a metal oxide containing SnO ₂ as a main component and containing about 5 to 20% of antimony oxide, and a metal oxide containing another component (for example, silicon oxide, boron, phosphorus, etc.), V ₂ O ₅ .

If the conductive metal oxide of the present invention has an irregular shape or a spherical shape, the primary particle size is preferably 0.0001 to 1 μm, and 0.001 to 0.5 μm provides good stability after dispersion. preferable. In addition, it is particularly preferable to use conductive particles having a size of 0.001 to 0.3 μm in order to improve the light transmittance because a transparent photosensitive material can be formed. These particles are secondary aggregates in which the particles in the dispersion liquid and the coating film are usually several primary particles or more, and the average particle diameter thereof is preferably 0.5 to 0.005 μm,
From the viewpoint of reducing the coating amount per unit area of the present invention, it is preferably 0.3 to 0.005 μm, more preferably 0.2 to 0.01 μm, particularly preferably 0.18 to
It is 0.01 μm. The smaller the coating amount per unit area, the better, and the target for suppressing coloring of the light-sensitive material of the present invention, that is, 400 to 75 at an incident angle of 6 degrees from the side having the polymer layer.
In order to make 0 nm light incident and the amplitude of the reflected light be 5% or less of the incident light intensity, 700 mg / m ² or less is sufficient. However, if the coating amount is too small, the antistatic property is lost. Therefore, the coating amount per unit area may be 1 to 800 mg / m ² , and preferably 2
To 400 mg / m ² , more preferably 5 to 250 mg /
m ² , particularly preferably 10 to 150 mg / m ² . When the conductive metal oxide is fibrous or acicular, the coating amount per unit area can be reduced as the aspect ratio (ratio of major axis / minor axis length) increases. The fibrous or acicular conductive metal oxide preferably used in the present invention has a length of 20 μm or less and a diameter of 1 μm or less, more preferably 10 μm or less and a diameter of 0.3 μm or less, particularly preferably The length is 10 μm or less and the diameter is 0.1 μm or less. Also,
The aspect ratio is 5 or more, preferably 10 or more, more preferably 20 or more. The coating amount per unit area may be a 0.1 to 500 mg / m ^2, preferably 0.5~300mg / m ^2, more preferably 0.5 to 1
50 mg / m ² , particularly preferably 1 to 100 mg / m ² .

Further, the conductive metal oxide of the present invention can be applied as a mixture of two or more kinds. In particular, if a mixture of irregular shape, spherical shape, fibrous shape and needle shape is used, the light-sensitive material is further colored. In some cases, it can be expected to suppress the effect. For example, SnO ₂
The effect of suppressing coloring of the photosensitive material is enhanced by mixing 1/50 by weight of V ₂ O ₅ with a metal oxide containing 5 to 20% of antimony oxide as a main component. The conductive metal oxide of the present invention may be applied from a coating solution without a binder, but in consideration of adhesion with the polymer layer on the antistatic layer and peeling off of the metal oxide in the manufacturing process, a binder is used. It is preferably applied together with. As the binder, any polymer capable of forming a film can be used. For example, it may be a water-soluble binder such as gelatin, dextran, polyacrylamide, starch, polyvinyl alcohol, or poly (meth) acrylic acid ester, polyvinyl acetate, polyurethane, polyvinyl chloride, polyvinylidene chloride, styrene / butadiene copolymer. Synthetic polymer binders such as polystyrene, polyester, polyethylene, polyethylene oxide, polypropylene and polycarbonate may be used in the organic solvent, and further these polymer binders may be used in the form of an aqueous dispersion. At this time, the conductive metal oxide / binder weight ratio is 99 / if the conductive metal oxide has an irregular shape or a spherical shape.
It is 1 to 10/90, and it is better that the weight ratio of the conductive metal oxide / binder is smaller and the antistatic property is higher. In order to reduce the weight ratio of conductive metal oxide / binder and increase the antistatic property, two or more kinds of binders are mixed to cause phase separation, or an additive such as a metal oxide flocculant is added. In addition, it is preferable to design the metal oxides so that they are well connected in a small amount in the antistatic layer. The conductive metal oxide / binder weight ratio is preferably 95/5 to 30/70, more preferably 90.
/ 10 to 50/50, particularly preferably 85/15 to 60
/ 40. If the conductive metal oxide is fibrous or acicular, it is 80/20 to 0.1 / 99.9, preferably 70/30 to 1/90, more preferably 50/50.
˜1 / 90, particularly preferably 30/70 to 1/90.

The electric resistance of the antistatic layer containing the conductive metal oxide of the present invention is preferably as low as possible.
It is 10 ¹² Ω or less, preferably 10 ¹¹ Ω or less, more preferably 10 ¹⁰ Ω or less, still more preferably 10 ⁹ Ω or less at 0 ° C. and 60% relative humidity. When the electrical resistance is 10 ¹² Ω or less at 25 ° C. and 60% relative humidity, the photosensitive layer is exposed by discharging the electrostatic charge accumulated in the photosensitive material before the development processing, and as a result, the dots are formed after the development processing. It is possible to prevent a failure that causes spots or resin-like lines, and a failure that accumulated electrostatic charges attract dust during printing and that is reflected on the screen. In the present invention, in addition to the antistatic layer containing a conductive metal oxide, an antistatic layer containing an ionic conductive polymer or latex or an ionic surfactant may be newly coated. . This antistatic layer can be coated on either the emulsion side or the back side. For example, protective layer, intermediate layer, emulsion layer, UV layer, antihalation layer,
Examples thereof include an undercoat layer, a back layer and a back protective layer. Of these, a protective layer, an intermediate layer, an antihalation layer, an undercoat layer, a back layer and a back protective layer are preferable, and an undercoat layer, a back layer, an intermediate layer and an antihalation layer are particularly preferable. The effect of preventing the photosensitive material after the development processing from attracting dust is that the electric resistance of the antistatic layer containing the conductive metal oxide of the present invention is 1
If less 0 ¹³ Omega well, partial ionic conductive polymer to be insufficient to prevent exposure of the photosensitive material due to the discharge of the development processing prior to electrostatic charge -, or supplemented with an antistatic layer containing latex be able to. The ionic conductive polymer or latex preferably used is not particularly limited, and any of anionic, cationic, betaine and nonionic may be used, but among them, preferred is anionic.
It is cationic. More preferred are anionic sulfonic acid-based, carboxylic acid-based, and phosphoric acid-based polymers or latexes, and tertiary amine-based, quaternary ammonium-based, and phosphonium-based polymers. These conductive polymers are disclosed, for example, in JP-A-48-22017 and JP-B-46-
24159, JP-A-51-30725, JP-A-51
-129216, JP-A-55-95942, JP-B-52-25251, JP-A-51-29923, JP-B-60-48024, and anionic polymers or latexes described in JP-A-48-91165 and JP-A-48-91165. Kai 49-1
No. 21523, Japanese Patent Publication No. 49-24582, Japanese Patent Publication No. 57
-18176, 57-56059, 58-56
856, US Pat. No. 4,118,231 and the like cationic polymers or latexes can be mentioned.

The conductive polymer or latex of the present invention may be coated from a coating solution without a binder, but it is more preferable to coat with a binder. The conductive polymer or latex of the present technology may be co-coated with a binder. The coating amount of the conductive polymer or terax of the present invention is 0.005
A 5 g / m ^2, preferably from 0.01 to 3 g / m ^2, more preferably 0.02 to 1 g / m ^2. Further, the binder is 0.005 to 5 g / m ² , and preferably,
0.01 to 3 g / m ² , particularly preferably 0.01 to ² g
/ M ² . The conductive polymer or latex / binder ratio is 100/1 to 10/100 by weight ratio, preferably 95/5 to 15/85, and particularly preferably 90/10 to 20/80. . Specific examples of these conductive polymers or latices will be described below, but the present invention is not limited thereto.

[0017]

[Chemical 1]

[0018]

[Chemical 2]

[0019]

[Chemical 3]

Specific examples of the ionic surfactant include JP-A-49-85826 and JP-A-49-33630.
No. 4, JP-A-48-87826, JP-B-49-1156.
7, JP-B-49-11568, JP-A-55-708.
No. 37, US2,992,108, US3,206,3
12, etc. The electric resistance of the antistatic layer produced as described above is preferably as low as possible.
It is 10 ¹³ Ω or less, preferably 10 ¹² Ω or less, more preferably 10 ¹¹ Ω or less, still more preferably 10 ¹⁰ Ω or less at 0 ° C. and 60% relative humidity. The antistatic layer containing the conductive metal oxide of the present invention, and the ionic conductive polymer or latex, the antistatic layer containing the ionic surfactant, heat resistance within the range that does not impair the antistatic property. Agent,
A weathering agent, inorganic particles, a water-soluble resin, an emulsion and the like may be added for matting and improving the film quality. For example, inorganic fine particles may be added to the antistatic layer containing the metal oxide of the present invention. Examples of inorganic fine particles to be added include
Silica, colloidal silica, alumina, alumina sol,
Kaolin, talc, mica, calcium carbonate and the like can be mentioned. The fine particles have an average particle diameter of 0.01 to 10 μm.
Is more preferable, 0.01 to 5 μm is more preferable, and 0.05 to 10 parts by weight ratio to the solid content in the coating agent is preferable, and 0.1 to 5 parts is particularly preferable.

Further, various organic or inorganic curing agents may be added to the coating agent of these conductive agents. These curing agents may be low molecular weight compounds or high molecular weight compounds, and these may be used alone or in combination. Examples of low molecular weight curing agents include, for example, "The Theory of the Photog Process" by TH James.
Raphic Process) ", 4th edition, pp. 77-88, low molecular weight curing agents are used, among which those having vinyl sulfonic acid, aziridine group, epoxy group, triazine ring are preferred, and especially JP-A Sho 53-41221
And low molecular weight compounds described in JP-A-60-225143 are preferred.

The polymer hardening agent is preferably a compound having a molecular weight of 2000 or more and having at least two groups which react with a hydrophilic colloid such as gelatin in the same molecule, and reacts with the hydrophilic colloid such as gelatin. Examples of the group include an aldehyde group, an epoxy group, an active halide (dichlorotriazine, chloromethylstyryl group, chloroethylsulfonyl group, etc.), an active vinyl group, an active ester group and the like. Examples of the polymer curing agent used in the present invention include polymers having an aldehyde group such as dialdecit starch, polyacrolein and acrolein copolymers described in US Pat. No. 3,396,029, and US Pat. No. 3,623. No. 878, a polymer having an epoxy group, Research Disclosure No. 1
Polymers having a dichlorotriazine group described in 7333 (1978), polymers having an active ester group described in JP-A-56-66841, JP-A-56-142524, and US Pat. No. 4,161. , 4
07, JP-A-54-65033, Research Disclosure No. A polymer having an active vinyl group described in 16725 (1978) or a group serving as a precursor thereof is preferable, and particularly, JP-A-56-142.
It is preferable that the active vinyl group or a group serving as a precursor thereof is bonded to the polymer main chain by a long spacer as described in No. 524.

Next, the polymer layer on the antistatic layer of the present invention will be described. At least one layer of this polymer layer is coated on the antistatic layer, and the film thickness is 0.1 to 5
μm. When the number of polymer layers is two or more, it is preferable that the adjacent polymer layers have the same refractive index as much as possible. The difference in refractive index between adjacent polymer layers is preferably ± 0.1 or less, more preferably ± 0.05 or less, and particularly preferably ± 0.03 or less. If the difference in refractive index is ± 0.1 or more, strong light reflection occurs at the interface between the polymer layers, which causes coloring of a new photosensitive material due to thin film interference, which is not preferable. Further, in order to suppress coloring of the light-sensitive material due to thin film interference of light reflected at the interface between the antistatic layer containing the conductive metal oxide of the present invention and the polymer layer, the incident angle of 6 from the side having the polymer layer. The thickness of the polymer layer is preferably 0.7 to 5 [mu] m when the light of 400 to 750 nm is incident and the amplitude of the reflected light is 1 to 5% of the incident light intensity. By setting the film thickness to 0.7 to 5 μm, the number of lights having wavelengths that cause thin film interference increases, and the purity of the color tone when they are superposed decreases, so that coloring is suppressed. When the amplitude of reflected light is 1 to 5% of the intensity of incident light, the more preferable film thickness is 1 to 5 μm.
m, and a more preferable film thickness is 1.3 to 5 μm.
As the binder used in the polymer layer of the present invention,
Various hydrophobic binders or hydrophilic binders having a film forming property can be used. Examples of the hydrophobic binder include thermoplastic resins, thermosetting resins, and radiation curable resins. Examples of the thermoplastic resin include vinyl chloride / vinyl acetate copolymer, vinyl chloride, vinyl acetate / vinyl alcohol, maleic acid and / or acrylic acid copolymer, vinyl chloride / vinylidene chloride copolymer, vinyl chloride / vinyl chloride Acrylonitrol copolymer, vinyl-based copolymers such as ethylene / vinyl acetate copolymer / nitrocellulose, cellulose diacetate, cellulose triacetate, cellulose acetate propionate,
Cellulose derivatives such as cellulose acetate butyrate resin, acrylic resin, polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane, polycarbonate polyurethane resin, polyester resin, polyether resin,
Rubber resins such as polyamide resin, amino resin, styrene butadiene resin, butadiene acrylonitrile resin,
Silicone-based resins, fluorine-based resins and the like can be mentioned.

The thermosetting resin whose molecular weight becomes extremely large when heated is, for example, phenol resin, phenoxy resin, epoxy resin, curable polyurethane resin,
Urea resin, melamine resin, alkyd resin, silicone resin, acrylic reaction resin, epoxy-polyamide resin,
Included are nitrocellulose melamine resins, high molecular weight polyester resins, urea formaldehyde resins, low molecular weight glycol / high molecular weight diol mixtures, polyamine resins, and mixtures thereof. As the radiation curable resin, the above-mentioned thermoplastic resin to which a group having a carbon-carbon unsaturated bond is bonded as a radiation curable functional group is used. Preferred functional groups include an acryloyl group and a methacryloyl group. The binders listed above may be used alone or as a mixture of several kinds, and a known crosslinking agent of epoxy type, aziridine type, isocyanate type, and / or a radiation curable vinyl type monomer may be added for curing treatment. The isocyanate cross-linking agent is a polyisocyanate compound having two or more isocyanate groups,
For example, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, naphthylene-
Isocyanates such as 1,5-diisocyanate, o-toluidine diisocyanate, isophorone diisocyanate, and triphenylmethane diisocyanate, and reaction products of these isocyanates and polyalcohols (for example, 3 mol of toluene isocyanate and 1 mol of trimethylol lopan). Products), and polyisocyanates produced by condensation of these isocyanates.

The radiation-curable vinyl-based monomer is a compound that can be polymerized by irradiation with radiation, and has at least one carbon-carbon unsaturated bond in the molecule.
(Meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl esters, vinyl esters, vinyl heterocyclic compounds, N-vinyl compounds, styrene, (meth) acrylic acid, crotonic acid, itaconic acid, Examples thereof include olefinic acid. Of these, preferred are (meth) acrylates of polyethylene glycol such as diethylene glycol di (meth) acrylate and triethylene glycol di (meth) acrylate having two or more (meth) acryloyl groups, trimethylolpropane tri (meth) acrylate, and the like. ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, a reaction product of a polyisocyanate and a hydroxy (meth) acrylate compound, and the like. These cross-linking agents are preferably 5 to 45 wt% with respect to the total binder containing the cross-linking agents. Examples of hydrophilic binders include Research Disclosure No. 17643, page 26, and No. 187.
16, pages 651, and water-soluble polymers, cellulose esters, latex polymers, water-soluble polyesters, aqueous polyurethanes, etc. are exemplified. Water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, maleic anhydride copolymers, etc., and carboxymethyl cellulose, hydroxyethyl cellulose as cellulose ester. And so on. Examples of the latex polymer include acrylic acid ester-based, polyolefin-based, vinyl chloride-based, vinyl acetate-based, styrene-based, silicon-based, acrylonitrile-based, vinylidene chloride-based, epoxy-based and butadiene-based copolymers.

When the polymer layer is a hydrophilic binder, particularly when it is a polymer containing gelatin as a main component, it is desirable to harden the film. Examples of hardeners that can be used in the polymer layer include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethylurea), and 2-hydroxy-4,6. -Dichloro-1,3,5
-Triazine and others U.S. Pat. No. 3,288,775
No. 2,732,303, British Patent 974,72
No. 3, 1,167,207 and the like, compounds having a reactive halogen, divinyl sulfone,
5-acetyl-1,3-diacryloylhexahydro-
1,3,5-triazine and others US Pat. No. 3,63
5,718, 3,232,763, British Patent No. 9
94,869 and the like, compounds having a reactive olefin, N-hydroxymethylphthalimide, and other U.S. Pat. Nos. 2,732,316 and 2,5.
N-methylol compounds described in US Pat. No. 86,168, isocyanates described in US Pat. No. 3,103,437, US Pat. No. 3,017,280.
No. 2,983,611 and the like, aziridine compounds described in US Pat. Nos. 2,725,294 and 2,725,295, and the like.
Examples thereof include epoxy compounds described in US Pat. No. 3,091,537 and halogen carboxaldehydes such as mucochloric acid. Alternatively, as an inorganic compound hardening agent, chrome alum, zirconium sulfate, JP-B-56-12853, JP-A-58-32699.
No., Belgian Patent No. 825,726, JP-A-60-22
5148, JP-A-51-126125, JP-B-58
Examples include carboxyl group-activating type hardeners described in JP-A-50699, JP-A-52-54427, US Pat. No. 3,321,313 and the like.

When a hardener is used, its amount is not particularly limited, but is preferably 1 to 5 relative to the weight of the binder.
It is 0% by weight, more preferably 1 to 25% by weight. You may mix several types of binders used for the polymer layer described above. Also, the glass transition temperature (Tg) of the polymer layer
Is -40 ° C to 300 ° C, preferably 0 ° C to 300 ° C,
More preferably 30 ° C to 300 ° C, particularly preferably 50.
C to 300C. The polymer layer of the present invention is generally well-known coating method, for example, dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, or US Pat. It can be constructed by an extrusion coating method using a hopper described in Japanese Patent No. 294. Also, if necessary, US Pat. Nos. 2,761,791, 3,508,947, 2,9
No. 41,898 and No. 3,526,528, Yuji Harazaki, "Coating Engineering", page 253 (published by Asakura Shoten in 1973), and the like can be used to simultaneously coat two or more layers. .

Next, the support used in the present invention will be described. The support used in the present invention is a polyester derivative (polyethylene aromatic dicarboxylate polyester) having a glass transition temperature (Tg) of 50 ° C to 200 ° C.
Is. The term "Tg" used herein means a scanning differential thermal analyzer (DSC) in the form of a film for a light-sensitive material obtained by biaxial stretching.
Is defined as follows. First, 10 mg of a sample is heated to 300 ° C. at a heating rate of 20 ° C./min in a nitrogen stream, and then rapidly cooled to room temperature. Then, the arithmetic average value of the temperature at which the temperature starts to deviate from the baseline when the temperature is raised again at 20 ° C./minute and the temperature at which the temperature returns to the new baseline is Tg. The support made of a polyester derivative (polyethylene aromatic dicarboxylate polyester) having a Tg of 50 ° C. to 200 ° C. according to the present invention is preferably formed by using a diol and an aromatic dicarboxylic acid as components, but other dicarboxylic acids Mixing with is also good. Examples of usable dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, and naphthalenedicarboxylic acid (2,6-, 1,5
-, 1,4-, 2,7-), diphenylene p, p'-dicarboxylic acid, tetrachlorophthalic anhydride, succinic acid, glutaric acid, adipic acid, sebacic acid, succinic anhydride, maleic acid, fumaric acid, Maleic anhydride, itaconic acid, citraconic anhydride, tetrahydrophthalic anhydride, 3,6
-Endomethylene tetrahydrophthalic anhydride, 1,4-
Cyclohexanedicarboxylic acid, halogenated terephthalic acid, bis (p-carboxyphenol) ether,
1,1-dicarboxy-2-phenyl ethylene, 1,
Examples thereof include 4-dicarboxymethylphenol, 1,3-dicarboxy-5phenylphenol, and sodium 3-sulfoisophthalate. Among the above-mentioned dicarboxylic acids, preferred aromatic dicarboxylic acids are those having at least one benzene nucleus.

Examples of the diol include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 7-heptanediol, 1,8-octanediol, 1,10
-Decanediol, 1,12-dodecanediol, 1,
4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanediol, 1,
Examples thereof include 1-cyclohexanedimethanol, catechol, resorcin, hydroquinone, 1,4-benzenedimethanol, dimethylolnaphthalene, P-hydroxyethyloxybenzene and bisphenol A. In addition, a monofunctional or trifunctional or higher polyfunctional hydroxyl group-containing compound or acid-containing compound may be copolymerized, if necessary. The polyester derivative of the present invention may be copolymerized with a compound having a hydroxyl group and a carboxyl group (or its ester) at the same time in the molecule, and examples thereof include salicylic acid.

Among these dicarboxylic acid and diol monomers, particularly preferable aromatic dicarboxylic acid is 2,
6-naphthalenedicarboxylic acid (NDCA), terephthalic acid (TPA), isophthalic acid (IPA), orthophthalic acid (OPA), paraphenylenedicarboxylic acid (PPD)
C), as particularly preferred diols, (poly) ethylene glycol (PEG or EG)), cyclohexanedimethanol (CHDM), neopentyl glycol (N
PG), bisphenol A (BPA), biphenol (BP), and a copolymerized component of hydroxycarboxylic acid such as parahydroxybenzoic acid (PHBA) and 6-hydroxy-2-naphthalenecarboxylic acid (HNCA). Can be mentioned. Among the above polyester derivatives composed of dicarboxylic acid and diol, more preferred are polyethylene terephthalate (PET), polyethylene-2,6-dinaphthalate (PEN), polyarylate (PAr), polycyclohexanedimethanol terephthalate ( Homopolymers such as PCT) and 2,6-naphthalenedicarboxylic acid (N
DCA), terephthalic acid (TPA), isophthalic acid (I
PA), orthophthalic acid (OPA), cyclohexanedicarboxylic acid (CHDC), paraphenylenedicarboxylic acid (PPDC), as diol, ethylene glycol (EG), cyclohexanedimethanol (CHDM),
Neopentyl glycol (NPG), Bisphenol A
(BPA), biphenol (BP), parahydroxybenzoic acid (PHBA) as hydroxycarboxylic acid, 6-
Examples thereof include copolymers obtained by copolymerizing hydroxy-2-naphthalenecarboxylic acid (HNCA).

Specifically, a copolymer of naphthalene dicarboxylic acid, terephthalic acid and ethylene glycol (mixing molar ratio of naphthalene dicarboxylic acid and terephthalic acid is preferably between 0.3: 0.7 and 1.0: 0, 0 .5:
0.5-0.8: 0.2 is more preferable. ), A copolymer of terephthalic acid, ethylene glycol, and bisphenol A (the mixing molar ratio of ethylene glycol and bisphenol A is preferably between 0.6: 0.4 and 0: 1.0, more preferably 0.5: 0.5). 0.1 to 0.9 is more preferable), isophthalic acid, para-phenylenedicarboxylic acid, a copolymer of terephthalic acid and ethylene glycol (isophthalic acid; the molar ratio of para-phenylenedicarboxylic acid is 0 when terephthalic acid is 1). 1-10.
0, 0.1 to 20.0, more preferably 0.2 each
It is -5.0 and 0.2-10.0. ), Naphthalenedicarboxylic acid, a copolymer of neopentyl glycol and ethylene glycol (the molar ratio of neopentyl glycol and ethylene glycol is preferably from 1: 0 to 0.7:
0.3, and more preferably 0.9: 0.1-0.
It is 6: 0.4. ) Terephthalic acid, copolymer of ethylene glycol and biphenol (The molar ratio of ethylene glycol and biphenol is preferably 0: 1.0 to 0.
8: 0.2, more preferably 0.1: 0.9-
It is 0.7: 0.3. ), Isophthalic acid, paraphenylenedicarboxylic acid, a copolymer of terephthalic acid and ethylene glycol (isophthalic acid; the molar ratio of paraphenylenedicarboxylic acid is 0.1-0.5, 0.1-0 when terephthalic acid is 1, respectively). .5, and more preferably 0.2 to 0.3 and 0.2 to 0.3 respectively),
Copolymer of terephthalic acid, neopentyl glycol and ethylene glycol (the molar ratio of neopentyl glycol and ethylene glycol is preferably 1: 0 to 0.7: 0.3, more preferably 0.9: 0.1 to 0.6). : 0.
4) Copolymer of terephthalic acid, ethylene glycol and biphenol (The molar ratio of ethylene glycol and biphenol is preferably 0: 1.0 to 0.8: 0.2, more preferably 0.1: 0.9 to 0. 7: 0.3), para-hydroxybenzoic acid, a copolymer of ethylene glycol and terephthalic acid (the molar ratio of para-hydroxybenzoic acid, ethylene glycol is preferably 1.0:
0 to 0.1: 0.9, more preferably 0.9:
It is 0.1-0.2: 0.8. ) And the like. Among these, particularly preferred are PET and polyethylene 2,6-naphthalate (PEN).

The preferred average molecular weight range of the polyester derivative of the present invention is about 5,000 to 500,000, particularly 5,000 to 200,000. These homopolymers and copolymers can be synthesized according to conventionally known polyester production methods. For example, when the acid component is directly esterified with the glycol component or when a dialkyl ester is used as the acid component, first, an ester exchange reaction with the glycol component is performed, and this is heated under reduced pressure to remove the excess glycol component. By doing so, they can be synthesized. Also, the acid component is set as an acid halide,
It may be reacted with glycol. At this time, if necessary, a transesterification reaction catalyst, a polymerization reaction catalyst, or a heat resistance stabilizer may be added. These polyester synthesis methods are described, for example, in Polymer Experimental Science No. 5
Volume "Polycondensation and Polyaddition" (Kyoritsu Shuppan, 1980) No. 10
Pages 3 to 136, "Synthetic Polymer V" (Asakura Shoten, 19
71) pp. 187-286 can be referred to.

Further, these polyesters may be partially blended with another polyester in order to improve the adhesion with another type of polyester, or the monomers constituting the other polyester may be copolymerized, or A monomer having an unsaturated bond can be copolymerized with these polyesters to be radically crosslinked. Polymer blends obtained by mixing two or more kinds of the obtained polymers are disclosed in JP-A-49-5482, 64-64325, JP-A-3-192718 and Research Disclosure 28.
3,739-41, 284, 779-82, 29.
It can be easily formed according to the method described in 4,807-14. For example, PEN and PET (composition ratio is preferably 0.3: 0.7 to 1.0: 0, more preferably 0.5: 0.5 to 0.8: 0.2), PET.
And PAr (preferably composition ratio 0.6: 0.4 to 0: 1.
0, more preferably 0.5: 0.5 to 0.1:
It is 0.9. ) And other polymer blends may be used.

Preferred specific examples of the polyester derivative used in the present invention are shown below, but the present invention is not limited thereto. Example of polyester compound (()
The inside represents the molar ratio. ) Homopolymer PET: [terephthalic acid (TPA) / ethylene glycol (EG) (100/100)] Tg = 80 ° C. PEN: [2,6-naphthalenedicarboxylic acid (NDCA) / ethylene glycol (EG) (100) / 100)] Tg = 119 ° C. PCT: [terephthalic acid (TPA) / cyclohexanedimethanol (CHDM) (100/100)] Tg = 93 ° C. PAr: [TPA / bisphenol A (BPA) (100/100)] Tg = 192 ° C

Copolymer (() represents a molar ratio.) PBC-12,6-NDCA / TPA / EG (50/50/100) Tg = 92 ° C. PBC-2-2,6-NDCA / TPA / EG (75/25/100) Tg = 102 ° C. PBC-3 2,6-NDCA / TPA / EG / BPA (50/50/75/25) Tg = 112 ° C. PBC-4 TPA / EG / BPA (100 / 50/50) Tg = 105 ° C. PBC-5 TPA / EG / BPA (100/25/75) Tg = 135 ° C. PBC-6 TPA / EG / CHDM / BPA (100/25/25/50) Tg = 115 ° C. PBC-7 IPA / PPDC / TPA / EG (20/50/30/100) Tg = 95 ° C. PBC-8 NDCA / NPG / EG (100/70/30) Tg = 105 ℃ PBC-9 TPA / EG / BP (100/20/80) Tg = 115 ℃ PBC-10 PHBA / EG / TPA (200/100/100) Tg = 125 ℃ ・ Polymer blend (weight ratio in () PBB-1 PEN / PET (60/40) Tg = 95 ° C. PBB-2 PEN / PET (80/20) Tg = 104 ° C. PBB-3 PAr / PEN (50/50) Tg = 142 ° C. PBB- 4 PAr / PCT (50/50) Tg = 118 ° C. PBB-5 PAr / PET (60/40) Tg = 101 ° C. PBB-6 PEN / PET / PAr (50/25/25) Tg = 108 ° C. PBB-7 TPA / 5-sulfoisophthalic acid (SIP) / EG (95/5/100) Tg = 65 ° C. PBB-8 PEN / SIP / EG (99/1/100) Tg = 115 ℃

These supports of the present invention have a thickness of 50 μm to 3 μm.
It has a thickness of 00 μm. If it is less than 50 μm, it cannot withstand the shrinkage stress of the photosensitive layer generated during drying.
If it exceeds 0 μm, it is inconsistent with the purpose of reducing the thickness for compactness. The thickness is more preferably 50 to 200 μm, further preferably 80 to 115 μm, and particularly preferably 85 to
It is 105 μm. All of the polyesters of the present invention as described above have a flexural modulus higher than that of TAC, and it was possible to realize the original thinning of the film. However, among these, PET has particularly strong flexural elasticity.
PEN is used, and it is possible to reduce the film thickness of 122 μm required for TAC to 105 μm or less.

An ultraviolet absorber may be kneaded into the support used in the present invention for the purpose of preventing fluorescence and imparting stability with time. It is desirable that the ultraviolet absorber does not have absorption in the visible region, and the addition amount thereof is usually 0.5% by weight to 20% by weight, preferably about 1% by weight to 10% by weight based on the weight of the polymer film. Is. 0.5% by weight
If it is less than the above, the effect of suppressing the deterioration of ultraviolet rays cannot be expected. 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2 as an ultraviolet absorber
-Hydroxy-4-n-octoxybenzophenone, 4
-Dodecyloxy-2-hydroxybenzophenone,
Benzophenone-based compounds such as 2,2 ', 4,4'-tetrahydroxybenzophenone and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2 (2'-hydroxy-5-methylphenyl) benzotriazole, 2
(2'-hydroxy 3 ', 5'-di-t-butylphenyl) benzotriazole, 2 (2'-hydroxy-3'
Examples thereof include benzotriazole-based UV absorbers such as -di-t-butyl-5'-methylphenyl) benzotriazole and salicylic acid-based UV absorbers such as phenyl salicylate and methyl salicylate.

Polyester derivatives, particularly aromatic polyesters, have a high refractive index of 1.6 to 1.7, while gelatin, which is the main component of the photosensitive layer coated thereon, has a refractive index of 1.50 to 1.50. Since the value is 1.55, which is smaller than this value, when light is incident from the edge of the support, it is reflected at the interface between the base and the emulsion layer to cause a so-called light piping phenomenon (edge covering). In order to avoid such a light piping phenomenon, a method of adding inert inorganic particles and the like to the support and a method of adding a dye are known. The method of adding a dye is preferable because it does not significantly increase the haze of the support. Regarding the dye used for dyeing the support, the color tone is preferably gray dyeing due to the general properties of the light-sensitive material, excellent in heat resistance in the film-forming temperature range of the polyester support, and excellent in compatibility with polyester. Those are preferable. As a dye,
From the above viewpoint, it is possible to achieve the object by mixing commercially available dyes for polyester such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku.

The polyester support according to the present invention can be imparted with slipperiness depending on the intended use, and kneading with an inert inorganic compound or coating with a surfactant is generally used. S as an inert inorganic particle
iO ₂ , TiO ₂ , BaSO ₄ , CaCO ₃ , talc,
Kaolin and the like are exemplified. Further, as described above, in addition to the slipperiness imparted by the external particle system in which the inert particles are added to the polyester synthesis reaction system, the slipperiness imparting method by the internal particle system in which the catalyst or the like added during the polymerization reaction of the polyester is precipitated is also used. Applicable. As the method for imparting slipperiness, it is desirable to select SiO ₂ having a refractive index relatively close to that of the polyester support, or an internal particle system capable of making the precipitated particle diameter relatively small. Further, in the case of kneading, a method of laminating a layer imparted with a function in order to obtain more transparency of the film is also preferable. Specific examples of this means include a co-extrusion method using a plurality of extruders and feed blocks, or a multi-manifold die.

Next, the surface treatment of the support used in the present invention will be described. A photographic layer (eg, a light-sensitive silver halide emulsion layer,
In order to firmly adhere the intermediate layer, filter layer, conductive layer, etc.), chemical treatment, mechanical treatment, corona treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow treatment, active plasma treatment, laser treatment, mixed acid It is effective to apply the photographic layer directly after the surface activation treatment such as treatment or ozone oxidation treatment, or to apply the photographic emulsion layer on the undercoat layer after the surface treatment is performed once. (For example, US Pat. Nos. 2,698,241, 2,764,520, 2,864,755, 3,462,335, 3,475,193, and 3,143). , 421, 3,501,301, 3,460,944, 3,674,531, British Patents 788,365, 804,005, 89.
No. 1,469, Japanese Patent Publication No. 48-43122, No. 51-4
No. 46). As the surface treatment of the support, corona treatment, ultraviolet treatment, glow treatment, and flame treatment are particularly effective among the above treatments, and the most effective treatment is glow treatment.

Examples of corona treatment, ultraviolet treatment, glow treatment, and flame treatment will be shown below, but the present invention is not limited thereto. The corona treatment is the most well-known method, and any conventionally known method, for example, JP-B-48-5.
043, 47-51905, JP-A-47-280.
No. 67, No. 49-83767, No. 51-41770.
No. 51-131576 and the like. Discharge frequency is 50Hz-5000
A suitable frequency is kHz, preferably 5 kHz to several hundreds of kHz.
If the discharge frequency is too low, stable discharge cannot be obtained and pinholes are generated in the object to be treated, which is not preferable. On the other hand, if the frequency is too high, a special device for impedance matching is required, which increases the cost of the device, which is not preferable. Regarding the treatment strength of the object to be treated, in order to improve the wettability of ordinary polyester derivatives, 0.001 KV ・ A ・
Min / m ^{2 to 5} KV ・ A ・ min / m ² , preferably 0.01 KV ・ A
・ Minute / m ^{2 to 1} KV · A ・ Minute / m ² is suitable. Gap clearance between electrode and dielectric roll is 0.5-2.5m
m, preferably 1.0 to 2.0 mm is suitable. For example, a solid state corona processor 6 manufactured by Pillar
When using the KVA model, the discharge frequency during processing is
It is 5 to 40 KHz, and more preferably 10 to 30 KHz. The waveform is preferably an AC sine wave. The gap clearance between the electrode and the dielectric roll is 1 to 2 mm, more preferably 1.4 to 1.6 mm. The processing amount is 0.3-
0.4 KV · A · min / m ² , more preferably 0.34 to
It is 0.38 KV · A · min / m ² .

Next, the ultraviolet treatment will be described. UV treatment is performed in Japanese Examined Patent Publication No. 43-2603 and Japanese Examined Publication No. 43-2604.
It is preferable to carry out the treatment method described in JP-B-45-3828. Mercury lamps are high-pressure mercury lamps and low-pressure mercury lamps that consist of quartz tubes, and the wavelength of ultraviolet rays is 180 to 320 nm.
Those in the range are preferred. The ultraviolet treatment is preferably performed during the film forming step (stretching step, heat setting, after heat setting), and specifically, it is preferably performed in the latter half of the stretching step or at the time of heat setting. 15 if heat fixing
Since the irradiation treatment is carried out at a high temperature of 0 ° C. to 250 ° C., the purpose can be achieved with an irradiation time of 1/2 to 2/3 as compared with the irradiation after heat setting, which is advantageous. For the method of UV irradiation, see 365
If the nm high-pressure mercury lamp whose main wavelength, the irradiation light quantity 20~10000 (mJ / cm ²⁾ C., more preferably 50~2000 (mJ / cm ^2). 254n
In the case of low-pressure mercury lamp to the m and dominant wavelength, the irradiation light quantity 100~10000 (mJ / cm ²⁾ C., more preferably 300~1500 (mJ / cm ^2).

Next, the glow processing will be described. The glow treatment is a conventionally known method, for example, Japanese Patent Publication No. 35-75.
No. 78, No. 36-10336, No. 45-22004.
No. 45-22005, No. 45-24040, No. 46-43480, JP-A No. 53-129262, US Pat. No. 3,057,792, and No. 3,057,795.
Issue 3, Issue 3,179,482, Issue 3,288,638
No. 3,309,299, No. 3,424,735
No. 3, 3,462,335, 3,475,307
No. 3, No. 3,761,299, No. 4,072,769,
British patents 891,469 and 997,093, etc. can be used. In the glow treatment of the present invention, the most excellent adhesion effect can be obtained especially when water vapor is introduced into the atmosphere. Further, this method is also very effective for suppressing yellowing of the support and preventing blocking.

The partial pressure of water vapor when the glow treatment is carried out in the presence of water vapor is preferably 10% or more and 100% or less,
More preferably, it is 40% or more and 90% or less. If it is less than 10%, it becomes difficult to obtain sufficient adhesiveness. The gas other than water vapor is air composed of oxygen, nitrogen and the like. A method for quantitatively introducing water vapor into the glow discharge treatment atmosphere is to use a quadrupole mass spectrometer (Nippon Vacuum M
SQ-150) and conduct it while quantifying the composition. Furthermore, if the substrate to be surface-treated is subjected to vacuum glow treatment in a pre-heated state, the adhesiveness is improved in a shorter time than that at room temperature, and the yellowing of the substrate is significantly reduced. You can The preheating described here is different from the heat treatment for improving the winding tendency described later. The preheating temperature is preferably 50 ° C. or higher and Tg or lower, more preferably 70 ° C. or higher and Tg or lower, and further preferably 90 ° C. or higher and Tg or lower. Preheating at a temperature of Tg or higher deteriorates adhesion. Specific methods for raising the surface temperature of the support in vacuum include heating with an infrared heater and heating with contact with a hot roll. A widely known heating method can be used as the heating method. In the glow treatment, it is preferable that a plurality of electrodes each having a hollow portion that serves as a refrigerant flow path are disposed so as to face each other in the width direction of the film, and the treatment is performed while the support is being transported.

The degree of vacuum during glow processing is 0.005 to 20.
Torr is preferred. More preferably 0.02 to 2
It's Torr. If the pressure is too low, the surface of the support cannot be sufficiently modified and sufficient adhesiveness cannot be obtained. On the other hand, if the pressure is too high, stable discharge does not occur.
Further, the voltage is preferably between 500 and 5000V. More preferably, it is 500-3000V. If the voltage is too low, the surface of the support cannot be sufficiently modified and sufficient adhesiveness cannot be obtained. On the other hand, if the voltage is too high, the surface will be deteriorated, and conversely the adhesiveness will decrease. Also,
The discharge frequency used is from direct current to several 1000 MHz, preferably 50 Hz to 20 M, as found in the prior art.
Hz, and more preferably 1 KHz to 1 MHz. Discharge treatment intensity is 0.01 KV · A · min / m ^{2 to 5} KV ·
A · min / m ² is preferable, more preferably 0.15 KV
A desired adhesive performance is obtained at A · min / m ^{2 to 1} KV · A · min / m ² .

It is preferable that the temperature of the support thus subjected to the glow treatment is immediately lowered by using a cooling roll. The support is likely to be plastically deformed by an external force as the temperature rises, and the flatness of the support is impaired. Furthermore, low-molecular weight substances (monomers, oligomers, etc.) may be deposited on the surface of the support, which may deteriorate transparency and blocking properties. The flame treatment method may be natural gas or liquefied propane gas, but the mixing ratio with air is important. In the case of propane gas, the preferable mixing ratio of propane gas / air is 1/14 to 1/22, preferably 1/16 to 1/19 by volume. In the case of natural gas, it is 1/6 to 1/10, preferably 1/7 to 1/9. The flame treatment may be performed in the range of 1 to 50 Kcal / m ² , more preferably 3 to 20 Kcal / m ² . It is more effective if the distance between the tip of the internal flame of the burner and the support is less than 4 cm. A frame processing device manufactured by Kasuga Electric Co., Ltd. can be used as the processing device. Further, the backup roll that supports the support during the flame treatment is a hollow roll, and it is preferable that the backup roll is water-cooled by cooling water and always treated at a constant temperature.

The undercoat layer provided between the surface-treated support of the present invention and the photographic layer will be described below. As the undercoat layer, a layer that adheres well to the support as the first layer (hereinafter abbreviated as the undercoat first layer) is provided, and a layer that adheres the undercoat first layer and the photographic layer as the second layer thereon There is a so-called multi-layer method in which an undercoating second layer is abbreviated), and a single layer method in which only one layer which adheres a support and a photographic layer well is applied.
In the first undercoat layer in the multi-layer method, for example, a single layer selected from vinyl chloride, vinylidene chloride, butadiene, vinyl acetate, styrene, acrylonitrile, methacrylic acid ester, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc. A copolymer having a monomer as a starting material, an epoxy resin, gelatin, nitrocellulose, polyvinyl acetate and the like are used. (For these, EHImmerg
ut “Polymer Handbook” P 187-231, Interscien
See Se Pub. New York 1966 etc.). Gelatin is mainly used in the second undercoat layer.

In the single layer method, a method is often used in which the support is swollen and interfacially mixed with the undercoat polymer to obtain good adhesiveness. This undercoat polymer, gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, water-soluble polymers such as maleic anhydride copolymers, carboxymethyl cellulose,
Cellulose ester such as hydroxyethyl cellulose,
A latex polymer such as a vinyl chloride-containing copolymer, a vinylidene chloride-containing copolymer, an acrylic acid ester-containing copolymer, a vinyl acetate-containing copolymer, a vinyl acetate-containing copolymer and the like are used. Of these, gelatin is preferred. As gelatin, so-called lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, gelatin derivatives, modified gelatin, and the like commonly used in the art can be used. Among these gelatins, lime-processed gelatin and acid-processed gelatin are most preferably used. These gelatins contain various impurities such as 0.01 to 20 in the production process.
000ppm of metals (Na, K, Li, Rb, Ca,
Mg, Ba, Ce, Fe, Sn, Pb, Al, Si, T
metals such as i, Au, Ag, Zn, Ni, and their ions), ions (F, Cl, Br, I, sulfate ions,
Nitrate ion, acetate ion, ammonium ion, etc.) may be contained. In particular, it is common knowledge in the art to contain Ca and Mg ions in lime-processed gelatin, and the content thereof is very wide, from 10 to 3000 ppm, but 1000 ppm or less is preferable in view of undercoat coating performance, and more preferably 500 ppm or less. is there.

In the case of the synthetic hydrophilic compound, other components may be copolymerized, but if the amount of the hydrophobic copolymerization component is too large, the moisture absorption amount and the moisture absorption rate of the non-photosensitive hydrophilic layer become small, and the curl is taken into consideration. Out of place. These hydrophilic compounds may be used alone or in combination of two or more. The primer polymer described above can be cured. Examples of the hardener include chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), epoxy compounds, isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-s-).
Triazine, etc.), epichlorohydrin resin, polyamide-epichlorohydrin resin (Japanese Patent Publication No. Sho 49-2658).
0, JP-A-51-3619) and cyanuric chloride compounds (for example, JP-A-47-6151 and JP-A-47-33).
380, 54-25411, JP-A-56-130.
No. 740), vinyl sulfone or sulfonyl compounds (for example, JP-B-47-24259).
No. 50-35807, JP-A-49-24435.
Nos. 53-41221 and 59-18944), and carbamoyl ammonium salt compounds (for example, Japanese Examined Patent Publication Nos. 56-12853 and 58-32).
699, JP-A-49-51945, 51-596.
25, 61-9641, and amidinium salt compounds (for example, JP-A-60-22514).
8) and carbodiimide compounds (for example, JP-A-51-126125 and JP-A-52-48311).
Compounds described in JP-A-58-50699, JP-A-52-5442.
7, JP-A-57-44140 and 57-46538.
No. 825,7)
26, U.S. Pat. No. 3,321,313, JP-A-50.
-38540, 52-93470, 56-43.
Examples thereof include compounds described in Nos. 353 and 58-113929.

The undercoat layer of the present invention may contain various additives, if desired. For example, surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids, antifoggants and the like. Further, the undercoat layer of the present invention may contain inorganic or organic fine particles as a matting agent to such an extent that the transparency and graininess of an image are not substantially impaired. As a matting agent for inorganic fine particles, silica (SiO ₂ ), titanium dioxide (TiO ₂ ), calcium carbonate, magnesium carbonate, etc. can be used. As the organic fine particle matting agent, polymethylmethacrylate, cellulose acetate propionate, polystyrene, a treatment solution soluble one described in U.S. Pat. No. 4,142,894, U.S. Pat. 396,
Polymers described in No. 706 can be used. The average particle size of these fine particle matting agents is 0.01
It is preferably 10 μm. More preferably 0.0
It is 5 to 5 μm. The content is 0.5 to 600.
mg / m ² is preferable, and more preferably 1 to 400 m
It is g / m ² . As the compound for swelling the support used in the present invention, resorcin, chlorresorcin, o-
Cresol, m-cresol, p-cresol, phenol, o-chlorophenol, p-chlorophenol,
Dichlorophenol, trichlorophenol, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid, chloral hydrate and the like are used. Of these, preferred are resorcin and p-chlorophenol.

Next, the heat treatment method for improving the curl of the support of the present invention will be described. In general, a polyester support is rapidly cooled from Tg or higher to Tg or lower after film formation, stretching and heat setting, and is fixed while maintaining a large free volume at Tg or higher, so that a curling tendency is likely to occur. However, by carrying out the heat treatment described here, the free volume in the support can be reduced and the curl can be made less likely to occur. The heat treatment temperature is Tg to (Tg-50 ° C), more preferably Tg to (Tg-30 ° C), and further preferably Tg to (Tg-30 ° C).
(Tg-20 ° C). When the heat treatment temperature exceeds the glass transition temperature, the support becomes easy to curl. (Tg-
If it is performed at a temperature lower than 50 ° C., it takes a long time to obtain a sufficient curling habit improving effect, resulting in poor industrial productivity. The heat treatment may be carried out at a constant temperature within this temperature range, or the heat treatment may be performed while lowering the temperature. The average cooling rate is -0.01 to -20 ° C /
Time, more preferably −0.1 to −5 ° C./hour.
The heat treatment time is 0.1 to 1500 hours, more preferably 0.5 to 500 hours, and further preferably 1 to 200 hours.
It's time. If 0.1 hours or less, no sufficient effect can be obtained, and if 1500 hours or more, the effect is saturated, while
The support is likely to be colored or brittle. When the support thus heat-treated is measured by a differential thermal analyzer, T
An endothermic peak appears in the vicinity of g, and the larger the endothermic peak is, the less the tendency of curling occurs.

In order to further increase the effect of eliminating the curling habit, after the heat history is erased by performing a heat treatment at a temperature of Tg or higher and lower than the melting point (melting temperature determined by DSC) before this heat treatment. The heat treatment may be performed at the temperature of Tg to (Tg-50 ° C). In the present invention, this heat treatment is called "pre-heat treatment", and the heat treatment of Tg to (Tg-50 ° C) described in the preceding paragraph is called "post-heat treatment" to distinguish them. Pre-heat treatment temperature is T
g or more and less than melting point is preferable, more preferably Tg + 10
℃ or higher and crystallization temperature (crystallization temperature determined by DSC) or lower,
More preferably, it is performed at Tg + 20 ° C. or higher and the crystallization temperature or lower. If the pre-heat treatment is performed at a temperature equal to or higher than the melting point, the elasticity of the support is remarkably reduced, causing surface failure and transport failure. The pre-heat treatment may be carried out within this temperature range at a constant temperature (constant temperature pre-heat treatment), may be carried out while lowering the temperature (pre-heat treatment before cooling), or may be carried out while raising the temperature (rise of temperature). Pre-heat treatment). The pre-heat treatment time is preferably 0.1 minutes or more and 1500 hours or less, more preferably 1 minute or more and 10 hours or less, and further preferably 1 minute or more and 1 hour or less. If it is 0.1 minutes or less, a sufficient effect cannot be obtained, and if it is 1500 hours or more, the effect is saturated, while the support is likely to be colored or brittle. After this pre-heat treatment, a post-heat treatment is carried out, but it may be rapidly cooled from the pre-heat treatment end temperature to the post-heat treatment start temperature, or may be gradually cooled to the post-heat treatment start temperature across Tg. Alternatively, the temperature may be once cooled to room temperature and then raised to the post-heat treatment temperature. Although there are several combinations of these pre-heat treatment and post-heat treatment methods, after the constant temperature pre-heat treatment at Tg + 20 ° C. or higher and the crystallization temperature or lower, the cooling rate from Tg to Tg−20 ° C. is -0.1- A post-heat treatment is preferably performed while cooling at 5 ° C / hour.

The heat treatment of such a support may be carried out in the form of a roll (A) or while being conveyed in the form of a web (B). When heat-treated in the form of a roll (A), a method of heat-treating the roll from room temperature in a constant temperature bath,
Any method may be used, in which the web is heated to a predetermined temperature during the web conveyance and then wound into a roll and subjected to heat treatment. Although the method of (1) requires a long time for raising and lowering the temperature, it has an advantage of requiring less equipment investment. The method of (1) requires winding equipment at high temperature, but has an advantage that the heating time can be omitted. In the roll-shaped heat treatment, due to the heat shrinkage stress generated during the heat treatment, wrinkles due to winding tightness and surface defects such as cut-outs of the core portion are likely to occur. Therefore, unevenness is imparted to the surface (for example, conductive inorganic fine particles such as SnO ₂ doped with Sb ₂ O ₅ are applied) to reduce creaking between the supports to prevent wrinkles due to winding tightening. It is desirable to take measures such as giving a knurl to the end of the support and slightly raising only the end to prevent the cut end of the winding core from appearing. On the other hand, when the heat treatment is performed in the web form (B), a long post-heat treatment step is required, but a better surface condition of the support can be obtained as compared with the heat treatment in the roll form. Among these heat treatment methods,
It is preferable that the pre-heat treatment is performed in a web shape and the post-heat treatment is performed in a roll shape. That is, when pre-heat treatment is carried out in web form,
This is because the planar failure is less likely to occur as compared with the case of performing the roll-like process, and the post heat treatment requires a relatively long time. In addition, the roll core used in the heat treatment has a built-in electric heater or has a structure capable of flowing a high-temperature liquid with a hollow inside so that the temperature can be efficiently propagated to the film and heated. Those having are preferred. The material of the roll winding core is not particularly limited, but it is preferably one that does not undergo strength reduction or deformation due to heat, and examples thereof include stainless steel and glass fiber-containing resin. These heat treatments may be carried out at any stage after the film formation of the support, the surface treatment of the support, the application of the back layer (antistatic agent, slip agent, etc.), and the application of the undercoat. Preferred is after the antistatic agent is applied. As a result, it is possible to prevent the attachment of dust due to electrification, which causes a surface failure of the support during heat treatment.

Next, the slip agent preferably used in the present invention will be described. In the present invention, the slip agent is used to prevent scratches when the film is conveyed. And, the sliding performance required by the slip agent is 25 ° C. and 60% RH.
The coefficient of dynamic friction measured using a stainless steel ball having a diameter of 5 mm is 0.25 or less, preferably 0.16 or less, and more preferably 0.13 or less. Dynamic friction coefficient is 0.2
If it exceeds 5, it is not preferable because scratches appear on the print when the film is conveyed. Examples of the slip agent used in the present invention include polyorganosiloxanes as disclosed in JP-B-53-292 and higher fatty acids as disclosed in US Pat. No. 4,275,146. Amide, Japanese Patent Publication No. 58-33541, British Patent No. 927, 446, or JP-A No. 55-12.
Higher fatty acid esters (esters of fatty acids having 10 to 24 carbon atoms and alcohols having 10 to 24 carbon atoms) as disclosed in 6238 and 58-90633, and US Pat. No. 3,933,516. Higher fatty acid metal salts as disclosed in the specification and also JP-A-58-
Esters of linear higher fatty acids and higher alcohols, as disclosed in 50534, WO 901081.
Higher fatty acid-higher alcohol esters containing a branched alkyl group as disclosed in 15.8 are known. Among these, as polyorganosiloxanes, there are generally known polyalkylsiloxanes such as polydimethylsiloxane polydiethylsiloxane, polyarylsiloxanes such as polydiphenylsiloxane and polymethylphenylsiloxane, and Japanese Patent Publication No. 53-292. , JP-B-55-49294, JP-A-60-140341, etc., organopolysiloxanes having an alkyl group of C5 or more, alkylpolysiloxanes having a polyoxyalkylene group in the side chain, alkoxy, hydroxy in the side chain. A modified polysiloxane such as an organopolysiloxane having a hydrogen, carboxyl, amino, or mercapto group may be used, a block copolymer having a siloxane unit, or JP-A-60-191240.
It is also possible to use a graft copolymer having a siloxane unit in the side chain as shown in. Examples of higher fatty acids and their derivatives and higher alcohols and their derivatives include higher fatty acids, metal salts of higher fatty acids, higher fatty acid esters, higher fatty acid amides, polyhydric alcohol esters of higher fatty acids, and higher aliphatic alcohols and higher fatty acids. Use of aliphatic alcohol monoalkyl phosphite, dialkyl phosphite, trialkyl phosphite, monoalkyl phosphate, dialkyl phosphate, trialkyl phosphate, higher aliphatic alkyl sulfonic acid, amide compound or salt thereof, etc. You can

As represented by the general formulas (1) and (2),
The long-chain alkyl compound is preferable in that sufficient slip properties and scratch resistance can be obtained before and after the development treatment. General formula (1) R ¹ X ¹ R ² General formula (2) R ³ X ² R ⁴ X ³ R ^{5 In} this general formula (1), R ¹ and R ² are aliphatic hydrocarbon groups. The total carbon number of this compound must be 25 or more and 120 or less. The total number of carbons needs to be 25 or more in order to obtain sufficient slipperiness. If the total number of carbon atoms is more than 120, the solubility in an organic solvent is poor and it becomes difficult to apply it by dispersion or coating. The total carbon number is more preferably 30 or more and 100 or less, further preferably 40 or more and 8
It is 0 or less. Further, R ¹ and R ² are each preferably an aliphatic hydrocarbon group having 10 or more and 70 or less carbon atoms in order to obtain sufficient scratch resistance and suppress deterioration of slipperiness under various use conditions. When the carbon number is 10 or less, the scratch resistance is deteriorated, and the sliding property is deteriorated by the transfer of the lubricant under various use conditions. Further, one-terminal functionalized aliphatic compounds having 70 or more carbon atoms are not generally known. This aliphatic hydrocarbon group may have a linear structure, may contain an unsaturated bond, may partially have a substituent, or may have a branched structure. Of these, the linear structure is particularly preferable from the viewpoint of scratch resistance. The carbon number of R ¹ and R ² is more preferably 15 or more and 50 or less.

In the general formula (2), R ³ , R ⁴ and R ⁵ are aliphatic hydrocarbon groups. The total carbon number of this compound is 30
The above is required and 150 or less. The total carbon number needs to be 30 or more in order to obtain sufficient slipperiness. If the total number of carbon atoms is more than 150, the solubility in organic solvents is poor and it becomes difficult to disperse or apply by coating. The total carbon number is more preferably 40 or more and 130 or less, still more preferably 50 or more and 120 or less. In addition, in order to prevent deterioration of slipperiness under various usage conditions with sufficient scratch resistance,
It is preferable that R ³ and R ⁵ are each an aliphatic hydrocarbon group having 10 to 70 carbon atoms, and R ⁴ is an aliphatic hydrocarbon group having 10 to 50 carbon atoms. Regarding R ³ and R ⁵ ,
When the carbon number is 10 or less, the scratch resistance is deteriorated, and the sliding property is deteriorated by the transfer of the lubricant under various use conditions. Further, an aliphatic compound having a carbon number of 70 or more and having one end functionalized is not generally known. This aliphatic hydrocarbon group may have a linear structure, may contain an unsaturated bond, may partially have a substituent, or may have a branched structure. Of these, the linear structure is particularly preferable from the viewpoint of scratch resistance. The number of carbon atoms of R ³ and R ⁵ is particularly preferably 15 or more and 50 or less. Further, as for R ⁴ , when the carbon number is 10 or less, the scratch resistance deteriorates,
Under various conditions of use, the slippery transfer causes deterioration of slipperiness. Further, an aliphatic compound having a carbon number of 50 or more and having both ends functionalized is not generally known. The aliphatic hydrocarbon group may have a linear structure, may contain an unsaturated bond, may have a partial substituent, or may have a branched structure. Of these, the linear structure is particularly preferable from the viewpoint of scratch resistance. The carbon number of R ⁴ is preferably 10 or more and 30 or less. Particularly preferred is 12 or more and 25 or less.

In the general formulas (1) and (2), X
¹ , X ² and X ³ are divalent linking groups. Specifically, -C (O)
O-,-C (O) NR-, -SO _3- , -OSO _3- , -SO ₂ NR-, -O-, -S-, -NR
-, -OC (O) NR- and the like are shown (R represents H or an alkyl group having 8 or less carbon atoms). Specific examples of the compounds represented by the general formulas (1) and (2) are shown below.

(1-1) n-C ₁₅ H ₃₁ COOC ₃₀ H ₆₁ -n (1-2) n-C ₁₇ H ₃₅ COOC ₄₀ H ₈₁ -n (1-3) n-C ₁₅ H ₃₁ COOC ₅₀ H ₁₀₁ -n (1-4) n-C ₂₇ H ₅₃ COOC ₂₈ H ₅₇ -n (1-5) n-C ₂₁ H ₄₃ COOCH ₂ CH (CH ₃ ) -C
₉ H ₁₉ (1-6) n-C ₂₁ H ₄₃ COOC ₂₄ H ₄₉ -iso

(2-1) n-C ₂₉ H ₄₉ OCO (CH ₂ )
₂ COOC ₂₄ H ₄₉ -n (2-2) n-C ₁₈ H ₃₇ OCO (CH ₂ ) ₄ COOC ₄₀
H ₈₁ -n (2-3) n-C ₁₈ H ₃₇ OCO (CH ₂ ) ₁₈ COOC ₁₈
H ₃₇ -n (2-4) iso-C ₂₄ H ₄₉ OCO (CH ₂ ) ₄ COOC
₂₄ H ₄₉ -n (2-5) n-C ₄₀ H ₈₁ OCO (CH ₂ ) ₂ COOC ₅₀
H ₁₀₁ -n (2-6) n-C ₁₇ H ₃₅ COO (CH ₂ ) ₆ OCOC ₁₇
H ₃₅ -n (2-7) n-C ₂₁ H ₄₃ COO (CH ₂ ) ₁₈ OCOC ₂₁
H ₄₃ -n (2-8) iso-C ₂₃ H ₄₇ COO (CH ₂ ) ₂ OCOC
₂₃ H ₄₇ -n (2-9) iso-C ₁₅ H ₃₁ COO (CH ₂ ) ₆ OCOC
₂₁ H ₄₃ -n

The polyether-containing compound used in the present invention as described above is obtained, for example, by sequentially adding ethylene oxide to a corresponding higher alcohol by a conventional method, or by adding the higher alcohol polyether to a corresponding dicarboxylic acid. It can be easily synthesized by dehydration condensation of the product or condensation of a higher carboxylic acid with the higher alcohol polyether adduct. A more preferable slip agent is a compound having a polar substituent in at least one of R ¹ and R 2 in the general formulas (1) and (2) or in at least one of R ³ , R ⁴ and R ^5. is there. The polar substituent here means a group capable of forming a hydrogen bond or an ionic dissociative group. The polar substituent is not particularly limited, -OH, -COOH, -COOM, -NH 3, -
NR ₄ ⁺ A ⁻ , —CONH _{2 and the} like are preferable. Here, M is a cation such as an alkali metal, an alkaline earth metal or a quaternary ammonium salt, R is H or a hydrocarbon group having 8 or less carbon atoms,
A ⁻ is an anion such as a halogen atom. Moreover, among these groups, —OH is particularly preferable. There may be any number of the polar substituents in one molecule. The amount of the slip agent represented by the general formulas (1) and (2) of the present invention is not particularly limited, but its content is 0.001 to 0.1 g in order to exhibit sufficient slip and scratch resistance. / M ² is preferable, and more preferably 0.005 to 0.05 g / m ² . Specific examples will be given below, but the present invention is not limited thereto.

(3-1) HOCO (CH ₂ ) ₁₀ COOC ₂₁ H ₄₃ (3-2) C ₁₇ H ₃₅ COOCH ₂ CH (OH) C ₁₂ H
₂₅ (3-3) C ₉ H ₁₉ C (OH) (C ₉ H ₁₉ ) CH ₂ CO
OC ₂₅ H ₅₁ (3-4) C ₆ H ₁₃ CH (OH) (CH ₂ ) ₁₀ COOC
₄₀ H ₈₁ (3-5) C ₁₄ H ₂₉ CH (NH ₂ ) COO (CH ₂ ) _{n
CH (CH 3) (CH 2} ) m -CH 3 (n +
m = 15) (3-6) CH ₃ (CH ₂ ) ₂ CH (COONa) (C
_{H 2) 6 COO - C 40} H 81 (3-7) HOCH 2 (CH 2) 6 CH (OH) CH
_{(OH) (CH 2) 4} COO-C 50 H 101 (3-8) C 17 H 33 COO (CH 2) 16 OH (3-9) CH 3 (CH 2) 2 CH (OH) (CH 2) ₆
CONHC ₂₁ H ₄₂ (3-10) C ₇ H ₁₅ -φ-COOCH (CONH ₂ ) C
₁₆ H ₃₃ (3-11) C ₂₇ H ₅₅ COOCH ₂ CH (OH) CH ₂ O
_{H (3-12) HOCO (CH 2} ) 5 COOC 40 H 81 (3-13) CH 3 (CH 2) 15 CH (SO 3 Na) CO
_{OCH 2 CH (C 13 H 27} ) -C 10 H 21

(4-1) C ₁₄ H ₂₉ CH (OH) COO
_{(CH 2) 5 OCOCH (OH} ) -C 14 H 29 (4-2) C 10 H 21 COOCH (C 2 H 5) (CH 2) 7
_{CH (C 2 H 4 COOH)} -OCOC 10 H 21 (4-3) NaOCO (CH 2) 11 COO (CH 2) 10
_{OCO (CH 2) 11 -COOH (} 4-4) C 9 H 19 C (OH) (C 9 H 19) CH 2 CO
_{O (CH 2) 15 CO-} NH-C 10 H 21 (4-5) H 2 NCO (CH 2) 10 COOCH (C 6 H
_{13) (CH 2) 10 COO} -C 30 H 61 (4-6) C 14 H 29 CH (N + (CH 3) 4 Cl -) C
_{OO (CH 2) 10 -OCO-} C 17 H 33 (4-7) C 6 H 13 CH (OH) (CH 2) 10 COO
_{(CH 2) 8 OCO- (CH} 2) 10 CH (OH) C 6 H 13 (4-8) C 15 H 31 COOCH 2 CH (OH) CH 2 O
COC ₁₅ H ₃₁ (4-9) C ₈ H ₁₇ NHCO (CH ₂ ) ₁₀ COO (CH
₂ ) ₁₅ OH (4-10) C ₄₀ H ₈₁ OCO (CH ₂ ) ₅ COO (C
_{H 2) 5 COOH (4-11)} CH 3 (CH 2) 15 CH (SO 3 Na) CO
_{O (CH 2) 2 CH- (} CH 3) - (CH 2) 2 OCOC 17
_{H 35 (4-12) HOCH 2 CH} (OH) CH 2 OCO (CH
_{2) 3 CH- (C 2 H} 5) - CH 2) 9 COOC 50 H 101 φ: -C 6 H 4 -

Many of the compounds of the above general formula have poor solubility in solvents. Therefore, it is preferable to disperse and use it in a nonpolar organic solvent such as toluene or xylene.
At this time, any dispersant may be used as long as it does not deteriorate slipperiness and scratch resistance, but preferable dispersants include those described in the following general formula (3). General formula (3) R ⁶ YBD In the general formula (3), R ⁶ is an aliphatic hydrocarbon group having 25 or more and 70 or less carbon atoms. This hydrocarbon group may contain an unsaturated bond, may be substituted with various substituents, and may contain a branched structure. A straight-chain aliphatic hydrocarbon group is particularly preferable in terms of slipperiness and scratch resistance. The carbon number of this hydrocarbon group is in the range of 25 or more and 70 or less. A hydrocarbon group having 25 or less carbon atoms causes problems such as sufficient slippage, scratch resistance not being exhibited, and deterioration of slipperiness after treatment. As a hydrocarbon compound having a carbon number of 70 or less and having one end functionalized, a long-chain linear or branched aliphatic alcohol or the like is known.
Compounds having 0 or more hydrocarbon groups are generally unknown. Particularly preferred as carbon number is 3
It is 0 or more and 60 or less.

Y is a divalent linking group. Specifically, -C (O) O-, -OCO-, -C (O) NR'-, -NR'CO-, -SO ₂ NR'-, -N
R'SO _2- , -O-, -S-, -NR-, -OCOR "COO-, -OCOR" O-, etc. can be mentioned (R 'is H or carbonized with 8 or less carbon atoms. Represents a hydrogen group, and R ″ represents a hydrocarbon group having 0 to 8 carbon atoms). B is-(CH ₂ CH ₂ O) _a- , or-
(CH ₂ CH (OH) CH ₂ O) _b -or-((CH ₂ ) _c CH (R) CH ₂ O) _d -or-(CH ₂ CH ₂ O) _e- (CH ₂ CH (OH ) CH ₂ O) _f -((CH ₂ ) _c CH (R) CH ₂ O)
_It consists of one unit of _g- , a is 3-40, b,
d is 3 to 30, c is 1 to 3, e is 0 to 40, and f and g are 0.
~ 30, e + f + g is 3-40, R is H, C
H ₃ and a phenyl group. If the length of these nonionic groups is too short, sufficient solubility of the slip agent cannot be obtained,
Alternatively, sufficient dispersion stability cannot be obtained when dispersed.
On the other hand, if it is too long, sufficient problems such as slippage and scratch resistance may not be exhibited, and after treatment, slippage may deteriorate over time. Particularly preferred among the above nonionic groups are-(CH
₂ CH ₂ O) _a −, and a is preferably 5 to 30. The use ratio of this general formula (3) to the slip agent (1) or (2) is
Preferably from 1: 9 to 9: 1, more preferably from 6: 4.
2: 8. The method of dispersing the slip agent will be described later. Specific examples of the compound represented by the general formula (3) are shown below.

(5-1) n-C ₃₀ H ₆₁ O (CH ₂ CH ₂ O) ₁₀ H (5-2) n-C ₄₀ H ₈₁ O (CH ₂ CH ₂ O) ₁₅ H (5-3) n-C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (5-4) n-C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₃₀ H (5-5) n-C ₄₀ H ₈₁ O ( _{CH 2 CH 2 O) 10 H} (5-6) n-C 50 H 101 (CH 2 CH 2 O) 16 H (5-7) n-C 50 H 101 - (CH (CH 3) CH 2 O)
_{3 - (CH 2 CH 2 O} ) 16 H (5-8) n-C 50 H 101 - (CH 2 CH (OH) CH 2
_{O) 3 - (CH (OH} ) CH 2 O) 3 - (CH 2 CH
₂ O) ₁₅ H (5-9) n-C ₄₀ H ₈₁ OCOCH ₂ CH ₂ COO (CH
_{2 CH 2 O) 16 H (} 5-10) n-C 50 H 101 OCOCH = CHCOO (C
_{H 2 CH 2 O) 16 H} (5-11) n-C 50 H 101 OCOCH 2 CH 2 COO-
_{(CH 2 CH (OH) CH} 2 O) 3 - (CH 2 CH 2 O) 15
H

The use of a binder capable of forming a film in the layer containing the compounds of the general formulas (1), (2) and (3) improves the surface condition of the lubricant applied and improves the film strength of the lubricant layer. Is particularly preferable in terms of. Examples of such a polymer include known thermoplastic resins, thermosetting resins, radiation curable resins,
Reactive resins, and mixtures thereof, hydrophilic binders such as gelatin can be used. Examples include those described in the section of polymer layer.

Some additives may be added to the above-mentioned lubricant layer in order to impart other functions. For example, a surfactant having a sulfonic acid or sulfuric acid ester as a hydrophilic part may be added as an additive in order to improve repellency caused by a hydrophobic slip agent, and examples thereof include compounds represented by the following general formula (4). General formula (4) R ⁷ ZEM ^{1 In} general formula (4), R ⁷ is an aromatic or aliphatic hydrocarbon group. The hydrocarbon group is not particularly limited, but specifically, straight chain alkyl, branched alkyl, substituted or unsubstituted phenyl group, naphthalene group, succinic acid ester of alkyl group, ester of phosphoric acid, etc. can give. Z is a divalent linking group. This linking group may be omitted. The linking group is not particularly limited, but specifically includes -R-, -OR-, -COOR-, -OCOR-, etc., and R is an alkyl group having 0 to 10 carbon atoms, a polyoxyethylene group, A polyoxypropylene group and the like. Also, E is -OSO
₃ − and −SO ₃ −. M ¹ is H or an alkali metal,
It is a cation such as an alkaline earth metal or a quaternary ammonium salt. Specific examples of the compound represented by the general formula (4) are shown below.

(6-1) C ₁₂ H ₂₅ OSO ₃ Na (6-2) C ₁₆ H ₃₃ OSO ₃ Na (6-3) C ₁₈ H ₃₇ φSO ₃ Na (6-4) C ₈ H ₁₇ φSO ₃ Na (6-5) C ₁₂ H ₂₅ φSO ₃ Na (6-6) C ₆ H ₁₃ OCOCH ₂ CH (C ₆ H ₁₃ OC
_{O) SO 3 Na φ: -C} 6 H 4 -

The amount of the additive represented by the general formula (4) of the present invention is preferably 0.001 g / m ² or more and up to the solid content of the slip agent, and from 0.005 g / m ² An amount up to 1/2 of the solid content of the agent is more preferable. The above-mentioned slipping agent can be formed as a slipping agent layer by applying a coating solution prepared by dissolving or dispersing this in a suitable water or organic solvent to the surface of the support, the surface of the back layer and the surface of the emulsion layer and drying. In the present invention, it is particularly preferable to coat the outermost layer on the back side. As a method of dispersing the slip agent, a generally known emulsification / dispersion method can be used.
Specifically, there are a method of dissolving in an organic solvent and emulsifying in water, a method of melting a lubricant at a high temperature and emulsifying in water, a solid dispersion method using a ball mill, a sand grinder, and the like. Such emulsification / dispersion methods are described in textbooks such as "Karimai, Pebble, Hidaka" and "Handbook for Emulsification / Dispersion Technology Application" (Science Forum Edition).

The slip agent used in the present invention may be dispersed in an organic solvent by various methods. As a method for dispersing in an organic solvent, a generally known method can be used. As a preferred method, specifically, a method in which a lubricant is solid-dispersed by a ball mill, a sand grinder or the like in an organic solvent, a lubricant is heated and dissolved in an organic solvent, and cooling precipitation is performed with stirring. Dispersion method, or a method in which a lubricant is dissolved in an organic solvent by heating and then added to an organic solvent at room temperature or in a cooled state to disperse by cooling and precipitation, and mutually compatible. Not emulsifying with organic solvents. Among these, a preferred method is a method in which the slipping agent is dissolved in an organic solvent by heating, and this is added to an organic solvent at room temperature or in a cooled state, cooled, precipitated and dispersed. The organic solvent used for this dispersion is not particularly limited, but a solvent having a high polarity is preferable as the cooling medium to which the lubricant solution is added. A particularly preferable method is a method in which the lubricant is heated and dissolved at 60 ° C. to 150 ° C. and is dispersed as a cooling medium in a solvent having a solubility of 1% or less at room temperature. Among the solvents in which the solubility of the lubricant at room temperature is 1% or less, ketones and alcohols are particularly preferable because of good dispersibility. Further, as the disperser used in this dispersion, an ordinary stirrer can be used, but an ultrasonic disperser and a homogenizer are particularly preferable.

The diluting solvent used for coating may be any one that does not deteriorate the dispersion stability or solubility of the slip agent, for example, water, water containing various surfactants, alcohols (methanol, ethanol). , Isopropanol, butanol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), esters (acetic acid, formic acid, oxalic acid, maleic acid, succinic acid, and other methyl, ethyl, propyl, butyl esters, etc.), hydrocarbons ( Hexane, cyclohexane, etc.) Halogenated hydrocarbons (methylene chloride, chloroform, carbon tetrachloride, etc.), aromatic hydrocarbons (benzene, toluene, xylene, benzyl alcohol, benzoic acid, anisole, etc.), amides (dimethylformamide, Dimethylacetamide, n-meth Pyrrolidone, etc.), ethers (diethyl ether, dioxane, tetrahydrofuran, etc.), ether alcohols such as propylene glycol monomethyl ether, glycerol, diethylene glycol, dimethyl sulfoxide and the like. Among them, water for handling, water containing various surfactants, alcohols,
Ketones and esters are preferred.

Next, the matting agent preferably used for improving the blocking properties of the emulsion side and the back side of the light-sensitive material will be described. The matting agent has a number average particle size of 1
It is possible to use a developing treatment solution-soluble matting agent and a developing treatment solution-insoluble matting agent having a thickness of μm to 10 μm. The number average particle diameter of the matting agent is preferably 1.5 μm to 8 μm, more preferably 1.5 μm to 6 μm, and further preferably 2
μm to 6 μm. The number average particle diameter in the present invention can be investigated by taking an electron micrograph of the matting agent and randomly measuring the particle diameters of 500 or more matting agents from the photograph. The content of the matting agent is 0.1 to 10
00 mg / m ² , preferably 1 to 500 mg /
m ^2, more preferably 5 to 300 mg / m ^2, more preferably from 10 to 200 mg / m ^2. The matting agent preferably contains a matting agent soluble in the developing treatment solution and a matting agent insoluble in the developing treatment solution together. The ratio of insoluble matting agent / soluble matting agent is not particularly limited, but is 10 /
1 to 1/10 is preferable, and more preferably 5/1 to 1 /
10 and more preferably 4/1 to 1/6.

The layer containing the matting agent is not particularly limited, and may be contained in any of the layers on the emulsion side and the back side, and may be contained in a plurality of layers. The emulsion side is particularly preferable, and the outermost layer on the emulsion side is most preferable. The thickness of the layer containing the matting agent of the present invention is not particularly limited, but is preferably 0.05 to 10 μm, more preferably 0.15 to 6 μm, and further preferably 0.15 to 3 μm. The average height of the surface protrusions formed by the matting agent is 0.02 to 8 μm, preferably 0.1 to 8 μm.
m, more preferably 0.1 to 6 μm, and particularly preferably 0.5 to 5 μm. The matting agent used is not particularly limited, but an inorganic compound or a polymer compound having a glass transition temperature (Tg) of 40 ° C. or higher is preferable. Among them, the preferred Tg of the high molecular compound matting agent is 5
It is 0 ° C or higher, and more preferably 60 ° C or higher. Two or more kinds of matting agents preferably used in the present invention can be mixed and used. Examples of matting agents of inorganic compounds include barium sulfate, manganese colloid, titanium dioxide,
There are fine powders of strontium barium sulphate, silicon dioxide, etc., but further, for example, silicon dioxide such as synthetic silica obtained by a wet method or gelation of silicic acid, or titanium dioxide (rutile type or anatase type) produced by titanium slag and sulfuric acid. ) And the like. It can also be obtained by crushing from an inorganic material having a relatively large particle size, for example, 20 μm or more, and then classifying (vibrating filtration, air classification, etc.). As the matting agent of a polymer compound, there are polytetrafluoroethylene, cellulose acetate, polystyrene, polymethyl methacrylate, polypropyl methacrylate, polymethyl acrylate, polyethylene carbonate, starch and the like, and pulverized and classified products thereof. Alternatively, a polymer compound synthesized by a soap-free polymerization method or a suspension polymerization method, a polymer compound spherically formed by a spray drying method or a dispersion method, or an inorganic compound can be used.

The polymer compound matting agent of the present invention is made of one or more monomer compounds as described below. Specific examples of the monomer compound, acrylic acid ester, methacrylic acid ester, itaconic acid diester, crotonic acid ester, maleic acid diester, phthalic acid diesters, and the like, as ester residues, methyl, ethyl, propyl, Isopropyl, butyl, hexyl, 2-ethylhexyl, 2-chloroethyl, cyanoethyl, 2-acetoxyethyl, dimethylaminoethyl, benzyl, cyclohexyl, furfuryl, phenyl, 2-hydroxyethyl, 2-ethoxyethyl, glycidyl, ω-methoxy polyethylene glycol. (Additional mol number 9) and the like. In addition, vinyl esters, olefins, styrenes, acrylamides,
Methacrylamides, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, unsaturated nitriles and the like are also preferably used.

Further, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate (for example,
Monoethyl itaconate, etc .; monoalkyl maleate (eg, monomethyl maleate, etc .; styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkyl sulfonic acid (eg,
Acryloyloxymethyl sulfonic acid etc.); methacryloyloxyalkyl sulfonic acid (eg methacryloyloxyethyl sulfonic acid etc.); acrylamidoalkyl sulfonic acid (eg 2-acrylamido-2-
Methyl ethane sulfonic acid etc.); Methacrylamide amidoalkyl sulfonic acid (eg 2-methacrylamido-2-
Methyl ethane sulfonic acid, etc.); acryloyloxyalkyl phosphate (eg, acryloyloxyethyl phosphate, etc.); These acids may be salts of alkali metals (eg Na, K, etc.) or ammonium ions. Still other monomer compounds include U.S. Pat. Nos. 3,459,790, 3,438,708, 3,554,987,
No. 4,215,195, No. 4,247,673
And the crosslinkable monomers described in JP-A No. 57-205735 and the like can be used. Specific examples of such a crosslinkable monomer include N- (2
-Acetoacetoxyethyl) acrylamide, N- (2
Examples include-(2-acetoacetoxyethoxy) ethyl) acrylamide and the like. Among these monomer compounds, acrylic acid and its esters, methacrylic acid and its esters, vinyl esters, styrenes and olefins are preferably used, and among them, acrylic acid and its esters are particularly preferred. , Methacrylic acid and its esters, and styrene. Also,
The present invention includes JP-A Nos. 62-14647 and 62-177.
Particles having a fluorine atom or a silicon atom as described in No. 44 and No. 62-17743 may be used. Among the matting agents preferably used in the present invention, particularly preferred is a matting agent containing acrylic acid, its esters, methacrylic acid, its esters, and styrene in a total composition of 80 wt% or more.
Above all, it is most preferable that the total content is 90 wt% or more.

For example, a preferred polymer compound matting agent will be described. Methyl methacrylate / acrylic acid copolymer (97/2 to 40/60 (molar ratio)), methyl methacrylate / methacrylic acid copolymer ( 97/2 to 4
0/60 (molar ratio)), a styrene / acrylic acid copolymer (97/2 to 40/60 (molar ratio)), and more preferred is a methyl methacrylate / acrylic acid copolymer (95 / 5-45 / 55 (molar ratio)), methyl methacrylate / methacrylic acid copolymer (95 / 5-45 /
55 (molar ratio)), styrene / acrylic acid (95/5
45/55 (molar ratio)), more preferably a methyl methacrylate / acrylic acid copolymer (93/7 to 50/5).
0 (molar ratio)), a copolymer of methyl methacrylate / methacrylic acid (93/7 to 50/50 (molar ratio)), styrene / acrylic acid (93/7 to 50/50 (molar ratio)), etc. is there. As for the matting agent insoluble in the developing solution, the total content of acrylic acid and methacrylic acid in the composition of the matting agent is preferably 0 to 35 wt%, more preferably 3 to 2
It is 5 wt%, and more preferably 5 to 20 wt%. Further, regarding the developing agent-soluble matting agent, the total content of acrylic acid and methacrylic acid in the matting agent composition is 6
0 to 35 wt% is preferable, and 55 to 40 is more preferable.
wt%, and more preferably 53 to 43 wt%.

Acrylic acid preferably used in the present invention,
And its esters, methacrylic acid, its esters, and a polymer compound matting agent containing styrene as a main component have a weight average molecular weight of 5,000 to 500,000, preferably 5,000 to 100,000, and more preferably Is 7,
000 to 70,000, particularly preferably 10,000 to
It is 50,000. Examples of preferred inorganic compounds and polymer compounds of the present invention are silica, polystyrene, polymethyl (meth) acrylate, polyethyl acrylate, poly (methyl methacrylate / acrylic acid = 90/1.
0, or 55/45 (molar ratio)), poly (styrene / acrylic acid = 95/5, or 60/40 (molar ratio)), poly (methyl methacrylate / methacrylic acid = 90/10,
Or 54/46 (molar ratio)), poly (styrene / styrene sulfonic acid = 95/5, or 60/40 (molar ratio)), polyacrylonitrile, poly (methyl methacrylate / ethyl acrylate / methacrylic acid = 50 / 40 /
10 (molar ratio)) and the like. Further, as the particles of the present invention, particles having a reactive (particularly gelatin) group described in JP-A No. 64-77052 and European Patent No. 307855 can be used. Specific examples of the matting agent of the present invention are shown below, but the invention is not limited thereto.

[0078]

[Chemical 4]

[0079]

[Chemical 5]

The number average particle diameter of the layer within 5 layers from the layer containing the matting agent preferably used in the present invention to the support side is 1 μm.
It is more preferable to contain fine particles of m or less of an inorganic compound or an organic compound. The number average particle diameter is preferably 0.001 to 0.8 μm, more preferably 0.01.
˜0.5 μm, more preferably 0.02 to 0.3 μm. Further, it is particularly preferable that the fine particles are insoluble in the developing solution. The fine particles may be contained in any layer as long as they are within 5 layers on the support side, and may be contained in a plurality of layers. The fine particles have the effect of preventing the matting agent from sinking into the film forming the photosensitive layer under conditions of high temperature and high humidity, and further improving the blocking property. The content of the fine particles is 0.1 to 2000 mg / m ² per layer,
Preferably 1 to 1500 mg / m ² , more preferably 1
0 to 1000 mg / m ² , more preferably 50 to 500
It is mg / m ² . The layer containing the fine particles is preferably close to the layer containing the matting agent of the present invention, and particularly preferably the layer containing the present invention or a layer immediately below it. The closer to the layer containing the matting agent of the present invention, the greater the effect of preventing sinking of the matting agent, which is preferable. It is preferable that the light-sensitive material does not have surface irregularities by containing the fine particles. If unevenness is given, it becomes a factor that deteriorates transparency (haze). The increase in haze due to the inclusion of the fine particles may be 7 or less, preferably 5 or less, more preferably 3 or less, still more preferably 1 or less as compared with the case where no fine particles are contained. The thickness of the layer containing fine particles is not particularly limited, but is preferably 0.05 to 10 μm.
And more preferably 0.15 to 6 μm, and further preferably 0.15 to 3 μm. The fine particles may be an inorganic compound or an organic compound, and two or more kinds may be mixed and used. If the binder of the layer containing fine particles is mainly composed of gelatin, silicon dioxide (such as silica) and a polymer compound are preferable. Among them, polymer compounds obtained from silica and monomer compounds such as acrylic acid esters, methacrylic acid esters, vinyl esters, styrenes, and olefins are particularly preferable.

Particles preferably used in the polymer compound include, for example, polystyrene, polymethyl (meth) acrylate, polyethyl acrylate, poly (methyl methacrylate / acrylic acid = 90/10 (molar ratio)), poly ( Styrene / acrylic acid = 95/5 (molar ratio)), poly (methyl methacrylate / methacrylic acid = 9
0/10 (molar ratio)), poly (styrene / styrenesulfonic acid = 95/5 (molar ratio)), polyacrylonitrile, poly (methyl methacrylate / ethyl acrylate / methacrylic acid = 50/40/10 (molar ratio) )) And the like. The binder of the layer containing the matting agent of the present invention is not particularly limited and may be a lipophilic binder or a hydrophilic binder. The same applies to the binder of the layer containing the above-mentioned fine particles. Specific binders are described in the above undercoat layer.

In the present invention, an anion, nonion, cation or betaine fluorine-containing surfactant can be used in combination. These fluorine-containing surfactants are disclosed in JP-A-49-1
0722, British Patent No. 1,330,356, JP-A Nos. 53-84712, 54-14224, and 50-.
113221, U.S. Pat. Nos. 4,335,201, 4,347,308, British Patent 1,417,915.
No. 52/26687 / 57-26719
No. 59-38573, JP-A-55-149938.
No. 54, No. 54-48520, No. 54-14224, No. 58-200235, No. 57-146248, No. 5
8-196544, British Patent No. 1,439,402
No., etc. Preferred examples of these are described below.

F-1 C ₈ F ₁₇ SO ₃ K F-2 C ₇ F ₁₅ COONa F-3 C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) -CH ₂ COO
_{K F-4 C 8 F 17} SO 2 N (C 3 H 7) - (CH 2 CH
_{(OH) CH 2 O) 3} - (CH 2) 4 SO 3 Na F-5 C 8 F 17 SO 2 N (C 3 H 7) (CH 2 CH 2
_{O) 4 (CH 2) 4} -SO 3 Na F-6 C 8 F 17 SO 2 N (C 3 H 7) CH 2 CH 2 -
O-P (= O) ( ONa) 2 F-7 C 8 F 17 CH 2 CH 2 OOC-CH 2 -CH
_{(SO 3 Na) -OCOC 8 H} 17 F-8 C 8 F 17 SO 2 NHCH 2 CH 2 CH 2 (OCH
^{_{2 CH 2) 3 -N (+}} ) (CH 3) 2 -CH 2 COO (-) F-9 C 8 F 17 SO 2 NHCH 2 CH 2 N-N
⁽⁺⁾ (CH ₃ ) ₃・ I ^(-) F-10 C ₈ F ₁₇ SO ₂ NHCH ₂ CH ₂ CH ₂ (OCH ₂ CH ₂ ) ₃ N ⁽⁺⁾ (CH ₃ ) ₃・
_{CH 3 -C 6 H 4 -SO 3} (-) F-11 C 8 F 17 SO 2 N (C 10 H 21) - (CH 2 CH
₂ O) ₁₆ H

Further, in the present invention, a nonionic surfactant may be used. Specific examples of the nonionic surfactant preferably used in the present invention are shown below. _{N-1 C 11 H 23 COO} (CH 2 CH 2 O) 8 H N-2 C 17 H 33 COO (CH 2 CH 2) 5 (CH 2 -CH (OH) -CH 2) 3
_{(CH 2 CH 2 O) 5} H N-3 C 16 H 33 O (CH 2 CH 2 O) 12 H N-5 C 9 H 19 -C 6 H 4 -O (CH 2 CH 2 O) 10
H The layer to which the fluorine-containing surfactant and the nonionic surfactant used in the present invention are added is not particularly limited as long as it is at least one layer of the photographic light-sensitive material, and examples thereof include a surface protective layer, an emulsion layer, an intermediate layer and an undercoat layer. , A sliding layer, an antistatic layer and the like. Fluorine-containing surfactants used in the present invention,
The amount of the nonionic surfactant used is preferably 0.0001 to 1 g / m ² per layer, more preferably 0.001 to 1 g / m ² .
05-0.5 g / m ² , particularly preferably 0.0005-
It is 0.2 g / m ² . Further, two or more kinds of these surfactants of the present invention may be mixed. Further, a polyol compound such as ethylene glycol, propylene glycol, 1,1,1-trimethylolpropane, etc., as shown in JP-A-54-89626, may be added to each layer of the present invention. Other known surfactants may be added to the photographic layer of the present invention alone or as a mixture. Although they are used as coating aids, they are sometimes applied for other purposes such as emulsion dispersion, sensitization and other improvement of photographic characteristics.

Next, the photographic layer of the photographic light-sensitive material of the present invention will be described. The silver halide emulsion layer may be color or black and white. Here, a color silver halide photographic light-sensitive material will be described. The light-sensitive material of the present invention may have at least one silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer provided on a support. There is no particular limitation on the number of layers and the order of layers of the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, it is generally a unit photosensitive layer. The arrangement is such that the red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. The boiling point at atmospheric pressure used in oil-in-water dispersion method is 17
Specific examples of the high boiling point organic solvent having a temperature of 5 ° C. or higher include phthalic acid esters, phosphoric acid or phosphonic acid esters, benzoic acid esters, amides, alcohols or phenols, aliphatic carboxylic acid esters, and aniline derivatives. , Hydrocarbons and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C or higher and about 16 ° C.
An organic solvent at 0 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like. The steps of latex dispersion method, effects, and specific examples of latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230. It is described in. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is 28 μm or less, and the film swelling speed T
_1/2 is preferably 30 seconds or less. The film thickness means a film thickness measured at 25 ° C. 55% relative humidity (2 days), the film swelling rate T _1/2 can be measured in accordance with a known method in the art. For example, A Green (A. Gr
een) et al., Photographic Science and Engineering (Photogr. Sci. Eng.), Volume 19,
No. 2, pages 124 to 129, can be measured by using a swellometer (swelling meter) of the type described, and T _1/2 is the maximum swell reached when processed at 30 ° C. for 3 minutes and 15 seconds with a color developer. 90% of the film thickness is defined as the saturated film thickness, which is defined as the time required to reach the film thickness of T _1/2 . Membrane swelling speed T
_1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is 150 to 400.
% Is preferred. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness-film thickness) / film thickness.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, and the same No.
Development can be carried out by a usual method described in the left column to the right column of 615 of 18716. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents.
For example, the Schiff base type compounds described in U.S. Pat. No.

First, the method of measuring the curl and the terms related thereto will be described. (1) Core set To wrap the film around the spool and add a curl. (2) Core set curl A curl in the length direction attached by the core set. The degree of curling is ANSI / ASC pH 1.29-1
Measured according to Test Method A of 985, 1 / R [m]
(R is the curl radius). (3) Absolute core set curl This is the core set curl of the photographic film before the curl is improved. (4) Controlled core set curl The core set curl of the photographic film after the curl has been improved. (5) True core set curl (Absolute core set curl)-(Controlled core set curl) (6) Curl reduction rate (True core set curl / Absolute core set curl) × 1
00

[0089]

EXAMPLES The present invention will be described in more detail with reference to specific examples, but the invention is not limited to the examples as long as the gist of the invention is not exceeded. Example 1 A sample was prepared as follows. (1) Preparation of Support After melt-extruding a PEN chip, it was made to be 3.4 in the longitudinal direction.
Double stretching was performed 4 times in the transverse direction to prepare a biaxially stretched support having a thickness of 90 μm. The PEN support has an extrusion temperature of 3
A film was formed at 00 ° C, a longitudinal stretching temperature of 140 ° C, a lateral stretching temperature of 130 ° C, and a heat setting of 250 ° C for 6 seconds. In addition, necessary amounts of yellow, cyan, and magenta dyes were added to each support for the purpose of preventing light piping.

(2) Surface Treatment of Support The surface of the support PEN was subjected to any one of ultraviolet treatment, corona treatment, glow treatment and flame treatment. For the UV treatment, the method shown in the example of JP-B-45-3828 was used. For the corona treatment, a solid state corona treatment machine 6KVA model manufactured by Pillar Co. was used and treated at 20 m / min. At this time, the processing intensity is calculated from the current and voltage readings.
The treatment was 0.375 kV · A · min / m ² . The discharge frequency during the treatment was 9.6 kHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm. Glow treatment was performed as follows. Four rod-shaped electrodes having a diameter of 2 cm and a length of 40 cm were fixed on the insulating plate in the vacuum tank at intervals of 10 cm. At this time, the film was set to run 15 cm away from the electrodes. Also, the diameter is 50
A heating roll with a cm temperature controller was placed immediately in front of the electrode, and the film was set so as to come into contact with this heating roll for 3/4 round. A biaxially stretched film having a thickness of 90 μm and a width of 30 cm was run and heated with a heating roll so that the temperature of the film surface between the heating roll and the electrode zone was 115 ° C. The film surface temperature was controlled by contacting it with a thermocouple thermometer. Then, this film was conveyed at a speed of 15 cm / sec and subjected to glow treatment. The pressure in the vacuum chamber is 0.
The partial pressure was ₂ Torr, and the H ₂ O partial pressure in the atmospheric gas was 75%. The discharge frequency was 30 KHz, the output was 2500 W, and the treatment intensity was 0.5 KV · A · min / m ² . The vacuum glow discharge electrode was in accordance with the method described in Japanese Patent Application No. 5-147864.
Flame treatment was carried out using a frame processing device manufactured by Kasuga Electric Co., Ltd. The distance between the tip of the internal flame of the burner and the support is 1c
m. The volume ratio of propane gas / air is 1/17,
The treatment strength was 15 Kcal / m ² .

(3) Heat Treatment of Support The PEN support was wound on a roll having a diameter of 30 cm. PE
After heating N to 160 ° C., it was cooled to 115 ° C., kept at that temperature for 24 hours, and then returned to room temperature. (4) Coating of emulsion-side undercoat layer An undercoat layer having the following formulation was provided on one surface of the surface-treated PEN support. The dry film thickness was designed to be 0.02 μm. The drying temperature was 110 ° C. Gelatin 1 part by weight Distilled water 1 part by weight Acetic acid 1 part by weight Methanol 50 parts by weight Ethylene dichloride 50 parts by weight p-Chlorophenol 4 parts by weight

(5) Coating of Back First Layer (Undercoat Layer) On the other surface of the surface-treated PEN support, a back-side undercoat layer was provided according to the following formulation. Further, in order to change the surface roughness of the adjacent layer of the support, the amount of P-chlorophenol added was changed to 0, 1, 4, 20 parts by weight and applied. The coating was applied so that the dry film thickness was 0.01 μm. Drying temperature is 110
℃ was made. Gelatin 1 part by weight Distilled water 1 part by weight Acetic acid 1 part by weight Methanol 50 parts by weight Ethylene dichloride 50 parts by weight P-chlorophenol See above (6) Application of back second layer (antistatic layer) Stannous chloride hydrate 230 parts by weight and antimony trichloride 23
A part by weight was dissolved in 3000 parts by weight of ethanol to obtain a uniform solution. A 1N aqueous sodium hydroxide solution was added dropwise to this solution until the pH of the solution reached 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained precipitate was left at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate. The reddish brown colloidal precipitate was centrifuged, water was added to the precipitate to remove excess ions, and the precipitate was washed with water by centrifugation.
200 parts by weight of the colloidal precipitate from which excess ions were removed was redispersed in 1500 parts by weight of water and sprayed in an incinerator heated to 600 ° C. to prepare a tin oxide-antimony oxide composite having an average primary particle size of 0.005 μm. A fine particle powder was obtained. The specific resistance of this fine particle powder was 1 Ω · cm. A 1N sodium hydroxide aqueous solution was added to a mixed solution of 40 parts by weight of the fine particle powder and 60 parts by weight of water to roughly disperse with a stirrer, and then dispersed with a horizontal sand mill to obtain secondary particles having an average particle diameter of 0.06 μm.
To obtain a conductive fine particle dispersion (pH = 7.0).

A liquid having the following formulation was applied while changing the amount of conductive fine particles applied. The drying temperature was 110 ° C. The conductive fine particle dispersion liquid 10 parts by weight Gelatin 1 part by weight Water 27 parts by weight Methanol 60 parts by weight Resorcin 2 parts by weight Polyoxyethylene nonylphenyl ether 0.01 parts by weight

(7) Coating of back third layer (polymer layer) A coating solution was prepared according to the following formulation using diacetyl cellulose as a binder.・ Silicon dioxide (average particle size 0.3 μm) 0.01 parts by weight ・ Aluminum oxide 0.03 parts by weight ・ Diacetyl cellulose 1.0 parts by weight ・ Methyl ethyl ketone 9.4 parts by weight ・ Cyclohexanone 9.4 parts by weight ・ Poly (polymerization 10) Oxyethylene paranonylphenol ether 0.06 part by weight-Trimethylolpropane 3 toluene diisocyanate adduct 0.03 part by weight-Colloidal silica (aerosil average particle size 0.02 μm) 0.02 part by weight-C ₈ F ₁₇ SO ₂ N (CH ₃ ) (CH ₂ CH ₂ O) ₆ H 0.01 parts by weight Poly (vinylidene difluoride / vinylidene tetrafluoride) 0.01 parts by weight (molar ratio 9: 1) Poly (methyl methacrylate) / Divinylbenzene) 0.01 parts by weight (molar ratio 9: 1, average particle size 1.0 μm) Coating on the back second layer while changing the dry film thickness. Drying was performed at 115 ° C. for 3 minutes.

(8) Coating of back fourth layer (sliding agent layer) The following two kinds of lubricating agents were mixed in a ratio of 4: 1, an equal weight of xylene was added and the mixture was heated and dissolved at 100 ° C. Stir while stirring. Further, 10 times the weight of the slip agent solution at room temperature isopropanol was added all at once to this solution to prepare a slip agent dispersion. This dispersion liquid was diluted with xylene / cyclohexanone / isopropanol (70/25/5 weight ratio), and a high pressure homogenizer (25 ° C., 300 kg / cm) was used.
Finely dispersed in ² ) to obtain a lubricant coating solution having a lubricant concentration of 0.1% by weight. The coating was performed by a slide coating method so that the coating amount was 15 mg / m ² , and the coating was dried at 115 ° C. for 5 minutes. _{n-C 17 H 35 COOC 30} H 61 -n 4 parts by weight _{n-C 30 H 61 O (} CH 2 CH 2 O) 10 H 1 part by weight (9) on a support subjected to Coating undercoat photosensitive layer Then, each layer having the composition shown below was applied in multiple layers to prepare a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid Disperse Dye ExF-2 0.030 Solid Disperse Dye ExF-3 0.040 HBS-1 0.15 HBS- 2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion M Silver 0.065 ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion A Silver 0.25 Silver iodobromide emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion C Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion E Silver 0.15 Silver iodobromide emulsion F Silver 0.10 Silver iodobromide emulsion G Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.80

9th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.60

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

Twelfth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

13th layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 gelatin 1.8

14th layer (second protective layer) Silver iodobromide emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 2.5 μm) 5.0 × 10 ^-2 B-2 (diameter 2.5 μm) 0.15 B- 3 0.05 S-1 0.20 Gelatin 0.70 Furthermore, storability, processability, pressure resistance, anti-mold,
To improve antibacterial property, antistatic property and coating property W-
1 to W-3, B-4 to B-6, F-1 to F
-17, and iron salt, lead salt, gold salt, platinum salt, palladium salt, iridium salt, and rhodium salt.

[0110]

[Table 1]

In Table 1, (1) Emulsions J to L were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to I were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains by using a high voltage electron microscope. (5) Emulsion L is a double structure grain containing an internal high iodine core described in JP-A-60-143331.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
ml and 5% aqueous solution of p-octylphenoxyethoxyethoxyethaneethanesulfonate (3 ml) and 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (polymerization degree 10: 0.5 g) were put in a 700 ml pot mill, and dye ExF- 5.0 g of 2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added to disperse the contents for 2 hours. A BO type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After the dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye fine particles was 0.44 μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the dye fine particles were 0.24 μm, 0.45 μm and 0.52 μm, respectively.
ExF-5 is a microprecipitation described in Example 1 of European Patent Application Publication (EP) 549,489A.
It was dispersed by the dispersion method. The average particle size was 0.06 μm.

[0114]

[Chemical 6]

[0115]

[Chemical 7]

[0116]

[Chemical 8]

[0117]

[Chemical 9]

[0118]

[Chemical 10]

[0119]

[Chemical 11]

[0120]

[Chemical 12]

[0121]

[Chemical 13]

[0122]

[Chemical 14]

[0123]

[Chemical 15]

[0124]

[Chemical 16]

[0125]

[Chemical 17]

[0126]

[Chemical 18]

[0127]

[Chemical 19]

[0128]

[Chemical 20]

[0129]

[Chemical 21]

(10) Processing of Sample The sample was cut into a film having a width of 35 mm and 24 sheets taken. (11) Development processing of photographic film The development processing of the obtained photographic film was carried out by the following method. The developing machine used was a cine type automatic developing machine FNCP-900 manufactured by Fuji Photo Film Co., Ltd. Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing with water 2 minutes 10 seconds Fixing 4 minutes 20 seconds Washing with water 3 minutes 15 seconds Stability 1 minute 05 seconds The composition of the treatment liquid used in each step was as follows.

Color developer Diethylenetriaminepentaacetic acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 g Hydroxylamine Sulfate 2.4 g 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulphate 4.5 g Water was added to 1.0 l pH 10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium Salt 100.0 g Ethylenediaminetetraacetic acid disodium salt 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Water was added to 1.0 l pH 6.0

Fixing solution Ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate aqueous solution (70%) 175.0 g Sodium bisulfite 4.6 g Water was added to 1.0 l pH 6.6 Stabilizing solution Formalin ( 40%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g Water was added to 1.0 l

The samples prepared as described above were evaluated for the following items. (1) Evaluation of Surface Roughness of Adjacent Layer on Support The average height of surface irregularities of the PEN support coated with the first back layer was measured using an atomic force microscope (AFM). (2) Evaluation of Amplitude of Reflected Light The light of 400 to 750 nm was made incident from the side having the polymer layer of the photosensitive material (back surface) at an incident angle of 6 degrees with respect to the normal direction of the film, and the reflected light was observed. . Since the reflected light draws a fringe in that wavelength range, Yamato and Tani of the fringe are connected by a smooth curve. And 400-7
The maximum width of the distance between the curve connecting the mountains and the curve connecting the valleys in the wavelength range of 50 nm is the amplitude of the reflected light,
The magnitude of the reflected light amplitude with respect to the incident light intensity was determined. A Hitachi spectrophotometer U-3500 was used as a measuring device. (3) Printed image of coloring of sensitive material The film after photography and development processing was magnified 16 times, and visually evaluated for stains and color tone shift due to coloring of the sensitive material on the screen. If there was no stain or color tone deviation, it was evaluated as ○, and if there was, it was evaluated as ×. (4) Evaluation of curling habit The sensitive material prepared as described above was slit into a width of 35 mm and a length of 1.2 m. After humidity-controlling this at 25 ° C. and 60% RH overnight, the photosensitive layer was wound inside and wound on a 5 mm spool. This was placed in a closed container and heated at 80 ° C. for 2 hours to give a rolling habit. The light-sensitive material having a crease habit was allowed to cool in a room at 25 ° C. for 12 hours, then taken out from the closed container and developed, and immediately subjected to curl measurement using a curl plate under the conditions of 25 ° C. and 60% RH. The development processing conditions are as described above. The degree of rolling habit is ANSI / ANC pH 1.
29-1985 Test Method A, 1 /
It is indicated by R [m] (R is the curl radius). The smaller the value is, the less the curl is. (5) Evaluation of Folding of Film After Development Processing The film after development processing was visually observed, and those with no crease marks were marked with ◯, and those with crease marks were marked with x. (6) Evaluation of development processing unevenness The developed photosensitive material was magnified and printed 16 times, and it was visually evaluated whether there was processing unevenness due to the development processing on the screen.
○ If there is no processing unevenness, × if there is processing unevenness
And

(7) Evaluation of Adhesion between Support and Photosensitive Layer, and Support and Back Layer After development, the emulsion layer and back layer of the film were cut in a grid pattern with a single-edged razor at intervals of 5 mm, with 7 lines in each length and width. Then, an adhesive tape (Nitto tape manufactured by Nitto Denki Kogyo Co., Ltd.) was stuck on this, and after 5 hours, it was quickly peeled off in the direction of 180 ° to perform a peeling test. When both the emulsion layer and the back layer were not peeled at all, it was evaluated as O, and when either one was peeled off at all, it was evaluated as X. (8) Evaluation of the dynamic friction coefficient of the back surface of the photosensitive material The dynamic friction coefficient was measured with the HEIDON-14 dynamic friction measuring device to be 25.
The measurement was performed under the conditions of ° C and 60% RH. (Stainless steel ball with a diameter of 5 mm, load 100 g, running speed 60 cm / min) (9) Printed image of scratches on the photosensitive material After being photographed by the camera, it was transported in the development processing device and printing device and printed at 16 times. It was visually evaluated whether scratches were reflected on the screen. If there were no scratches, it was rated as O, and if there were scratches, it was rated as X. (10) Evaluation of Antistatic Property (Conductivity) A silver paste was applied to the facing edges of the film having a width of 1 cm after development, and the resistance was measured by connecting it to a resistance measuring machine. The atmosphere was 25 ° C. and 60% RH. In addition,
Resistance is logarithmic. The smaller the value, the better the conductivity (antistatic property). (11) Printed image of dust on the photosensitive material After rubbing the developed photosensitive material three times with a nylon cloth and leaving it in the air for 1 hour to adhere the dust, print it 16 times and dust it on the screen. Was visually evaluated. If there is no dust in the image, it is O. If dust is in the image, it is X.

The evaluation results are shown in Tables 2 and 3. The average height is 1 nm on a PEN support having a glass transition temperature of 119 ° C., which is heat-treated at 115 ° C. for 24 hours and has a thickness of 90 μm.
It has an undercoat layer having a surface roughness of ˜500 nm, an antistatic layer containing a conductive metal oxide (tin oxide) is applied on the undercoat layer, and an antistatic layer of 0. 1
In a photographic light-sensitive material having a DAC layer of ˜5 μm, 400-750 n at an incident angle of 6 degrees from the side having a polymer layer.
m of light is incident, and the amplitude of the reflected light is 5 of the incident light intensity.
% Or less in the silver halide photographic light-sensitive material of Levels 1 to 6 of the present invention, coloring due to thin film interference can be suppressed,
Further, a silver halide photographic light-sensitive material having excellent mechanical properties and being hard to have a curling tendency could be produced. Furthermore, 10 ¹²
By applying an antistatic layer having an electrical resistance of Ω or less and applying a sliding layer with a dynamic friction coefficient of 0.15 or less on the back layer surface, it is possible to suppress dust adhesion and scratches when the film is transported to equipment. It was possible to prepare a silver halide photographic light-sensitive material capable of producing It has been found that when the curl of the silver halide photographic light-sensitive material has a value of 1 / R [m] of 70 or less, the film does not fold or the development processing unevenness does not occur. Further, it was found that when the coefficient of dynamic friction of the surface of the back layer is 0.25 or less, it is possible to suppress scratches during transport of the film equipment (camera, development processing apparatus, printing apparatus). In the comparative example of level 7, the amplitude of the reflected light exceeded 5% of the incident light intensity, so that the color of the light-sensitive material appeared on the screen when printed on photographic paper. In the comparative example of level 8, as compared with level 7, since the surface of the undercoat layer of the support had no irregularities, the amplitude of the reflected light did not exceed 5% of the incident light intensity. The same was true even if the coating amount of the metal oxide was increased. Level 9
In the comparative example, the thickness of the DAC layer on the antistatic layer is thicker than 5 μm even when the amplitude of the reflected light exceeds 5% of the incident light intensity. Therefore, the coloring of the sensitive material is not visible on the screen when printed on photographic paper. There wasn't. In the comparative example of level 10, since the support was not subjected to heat treatment, the curl was markedly formed, and the film was broken or the development process was uneven. In level 11, since the surface treatment of the support was not performed, the emulsion layer and the back layer were slightly peeled off, which is somewhat undesirable. In the comparative example of level 12, since there was no antistatic property, dust adhered to the light-sensitive material, and when printed on photographic paper, the dust appeared on the screen. In the comparative example of level 13, the coefficient of kinetic friction was 0.45, which was very large and had no slipperiness, and therefore scratches were generated when the film was transported to the equipment, and the scratches appeared on the screen when printed on photographic paper.

[0136]

[Table 2]

[0137]

[Table 3]

The thickness of the PEN support is 50, 75,
The investigation was conducted at 100, 200 and 300 μm, but the same results as above were obtained. Furthermore, Tg shown in Table 4
When a support having a temperature of 50 ° C. or higher was examined in the same manner as above, the same result as that of PEN was obtained.
However, the pre-heat treatment before the heat treatment of the present invention was performed at Tg + 40 ° C. Therefore, the glass transition temperature (Tg) is 50 ℃ ~
Mainly composed of polyester at 200 ° C., Tg
(Tg-50 ° C) is heat-treated for 0.1 to 1500 hours,
A polyester support having a thickness of 50 to 300 μm, and the surface of the polyester support has an average height of 1 nm to 500 nm, or the surface has an average height. At least one of which has an adjacent layer having a surface roughness of 1 nm to 500 nm, and at least one layer on the surface having the surface roughness is an antistatic layer containing a conductive metal oxide, Further, in a photographic light-sensitive material having a polymer layer of 0.1 to 5 μm on at least one layer on the antistatic layer, light of 400 to 750 nm is incident from the side having the polymer layer at an incident angle of 6 degrees, and the amplitude of the reflected light is Is less than 5% of the incident light intensity, coloring due to thin film interference is suppressed, and a silver halide photographic light-sensitive material having a polyester support which has excellent mechanical properties and is hard to have a curl It has been shown that the material can be made. Furthermore, an antistatic layer having an electric resistance of 10 ¹² Ω or less is coated, and the dynamic friction coefficient of 0.
By coating a sliding layer of 25 or less, a silver halide photographic light-sensitive material capable of suppressing the adhesion of dust and the scratching of the film during transportation of the equipment could be produced.

[0139]

[Table 4]

Example 2 Preparation of a support, heat treatment of a support,
Surface treatment of support, coating of undercoat layer on emulsion side, back 1st
The coating of the layer, the coating of the back second layer (antistatic layer), the coating of the back third layer (polymer layer), the coating of the back fourth layer (sliding agent layer), and the processing of the sample were performed in Example 1. I did exactly the same as. The light-sensitive layer is a reversal color emulsion layer.
The same thing as the sample 101 of Example 1 was coated.
Further, the development processing of the light-sensitive material was carried out according to the development processing method for color reversal light-sensitive material shown in JP-A-2-854 Example 1. Evaluation of surface roughness of adjacent layer on support, evaluation of amplitude of reflected light, evaluation of curl, evaluation of breakage of film after development processing, evaluation of adhesion between support and photosensitive layer, and support and back layer The evaluation of the dynamic friction coefficient of the photosensitive material back surface and the evaluation of the antistatic property (conductivity) were the same as in Example 1. (1) Slide projection image of coloring of sensitive material When the film after shooting and development is slide-projected at 100 times, it is visually evaluated whether there is a stain or color shift due to coloring of the sensitive material on the screen. did. If there was no stain or color tone deviation, it was evaluated as ○, and if there was, it was evaluated as ×. (2) Slide projection image of uneven development process When the film after photography and development process was slide-projected at 100 times, it was visually evaluated whether the uneven development process appeared on the screen. When there was no development unevenness, it was rated as O, and when there was development unevenness, it was rated as X. (3) Sliding projection image of scratch on photosensitive material When the film after photographing and developing was slide-projected at 100 times, it was visually evaluated whether the scratch on the photosensitive material appeared on the screen. If there were no scratches, it was rated as O, and if there were scratches, it was rated as X. (4) Sliding projection image of dust on the photosensitive material After rubbing the developed photosensitive material three times with a nylon cloth and leaving it in the air for 1 hour to attach dust, slide projection at 100 times , And visually evaluated whether dust was reflected on the screen. If there is no dust in the image, it is O. If dust is in the image, it is X.

The evaluation results are shown in Tables 5 and 6. The average height is 1 nm on a PEN support having a glass transition temperature of 119 ° C., which is heat-treated at 115 ° C. for 24 hours and has a thickness of 90 μm.
It has an undercoat layer having a surface roughness of ˜500 nm, an antistatic layer containing a conductive metal oxide (tin oxide) is applied on the undercoat layer, and an antistatic layer of 0. 1
In a photographic light-sensitive material having a DAC layer of ˜5 μm, 400-750 n at an incident angle of 6 degrees from the side having a polymer layer.
m of light is incident, and the amplitude of the reflected light is 5 of the incident light intensity.
% Or less, the silver halide photographic light-sensitive material of the present invention having a level of 14 to 19 of the invention is capable of suppressing coloring due to thin film interference, has excellent mechanical properties, and is hard to have a curl. I was able to. Furthermore, 1
By coating an antistatic layer having an electrical resistance of 0 ¹² Ω or less and setting a dynamic friction coefficient of 0.15 or less on the surface of the back layer, it is possible to prevent dust from adhering and scratches when the film is transported to equipment. A silver halide photographic light-sensitive material could be produced. The curl of the silver halide photographic light-sensitive material is 1
It was found that when the value of / R [m] was 70 or less, the film did not fold or the development processing unevenness did not occur. Further, it was found that when the coefficient of dynamic friction of the surface of the back layer is 0.25 or less, it is possible to suppress scratches during transport of the film equipment (camera, development processing apparatus, printing apparatus). Level 2
In the comparative example of 0, the coloring of the sensitive material was reflected on the screen when projected on a slide. In the comparative example of level 21, the surface of the undercoat layer of the support had no unevenness as compared with level 20, and therefore the amplitude of reflected light did not exceed 5% of the incident light intensity. The same was true even if the coating amount of the metal oxide was increased. Level 2
In Comparative Example 2, the thickness of the DAC layer on the antistatic layer is thicker than 5 μm even when the amplitude of the reflected light exceeds 5% of the incident light intensity. Therefore, when projected with a slide, the coloring of the sensitive material is not reflected on the screen. There wasn't. In the comparative example of level 23, since the support was not subjected to heat treatment, the curling tendency was remarkable, and the film was broken and the development process was uneven. In level 24, the support was not surface-treated, and therefore the emulsion layer and the back layer were peeled off, which is somewhat undesirable. In the comparative example of level 25, since there was no antistatic property, dust adhered to the photosensitive material, and when projected on a slide, the dust appeared on the screen. In the comparative example of level 26, the coefficient of kinetic friction was 0.47, which was very large and had no slipperiness, so scratches were generated when the film was conveyed to the equipment, and when the film was projected on a slide, the scratches appeared on the screen.

[0142]

[Table 5]

[0143]

[Table 6]

Also, the thickness of the PEN support is 50, 75,
The investigation was conducted at 100, 200 and 300 μm, but the same results as above were obtained. Furthermore, Tg shown in Table 4
When a support having a temperature of 50 ° C. or higher was examined in the same manner as above, the same result as that of PEN was obtained.
However, the pre-heat treatment before the heat treatment of the present invention was performed at Tg + 40 ° C. Therefore, the glass transition temperature (Tg) is 50 ℃ ~
Mainly composed of polyester at 200 ° C, Tg
Is a polyester support having a thickness of 50 to 300 μm, which is heat-treated at a temperature of (Tg−50 ° C.) for 0.1 to 1500 hr, and the surface of the polyester support has an average height of 1 nm to 500 nm. Or has an adjacent layer on the surface of the support having an average height of 1 nm to 500 nm of surface roughness.
At least one layer on the surface having the surface roughness is an antistatic layer containing a conductive metal oxide, and at least one layer on the antistatic layer has a polymer layer of 0.1 to 5 μm. The incident angle 6 from the side having the polymer layer.
By making light having a wavelength of 400 to 750 nm incident thereon and having a property that the reflected light has an amplitude of 5% or less of the incident light intensity, coloration due to thin film interference is suppressed, and excellent mechanical characteristics are obtained. It was shown that a silver halide photographic light-sensitive material having a polyester support which is hard to have a curl can be prepared. Furthermore, by coating an antistatic layer having an electric resistance of 10 ¹² Ω or less and a sliding layer having a dynamic friction coefficient of 0.25 or less on the surface of the back layer, dust is adhered and scratches when the film is transported to a device. It was possible to produce a silver halide photographic light-sensitive material capable of suppressing sticking.

[0145]

EFFECT OF THE INVENTION Glass transition temperature (Tg) 50 ° C. to 20
0.1g to 1500h at Tg- (Tg-50 ° C) at 0 ° C
r heat treated, having a polyester support characterized in that its thickness is 50 to 300 μm, and the surface of the polyester support has an average height of 1 nm to 500 nm, or an average height of In addition, it has either an adjacent layer having a surface roughness of 1 nm to 500 nm, and at least one layer on the surface roughness is an antistatic layer containing a conductive metal oxide, In a photographic light-sensitive material having a polymer layer of 0.1 to 5 μm on at least one layer on the prevention layer, 400 to 750 nm of light is incident from the side having the polymer layer at an incident angle of 6 degrees, and the amplitude of the reflected light is incident. By setting it to 5% or less of the light intensity,
Coloring due to thin film interference is suppressed, and it has excellent mechanical properties.
Moreover, a silver halide photographic light-sensitive material having a polyester support which is hard to have a curl can be prepared.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location G03C 1/81 1/825 1/85 1/91

Claims (9)

[Claims] 1. A silver halide photographic light-sensitive material having a silver halide emulsion layer on one side of a support, wherein the support is mainly composed of polyester having a glass transition temperature (Tg) of 50 ° C. to 200 ° C. , Tg- (Tg-50
C.) at a temperature of 0.1 to 1500 hr and a thickness of 50 to 300 μm, and the surface of the polyester support has an average height of 1 nm to
Either having a surface roughness of 500 nm or having on the surface of the support an adjacent layer having an average height of 1 nm to 500 nm surface roughness and having that surface roughness At least one layer on the surface is an antistatic layer containing a conductive metal oxide, and at least one layer on the antistatic layer has a polymer layer of 0.1 to 5 μm, and the side having the polymer layer. From 400 at an incident angle of 6 degrees
A silver halide photographic light-sensitive material, characterized in that light having a wavelength of 750 nm is made incident and the amplitude of the reflected light is 5% or less of the intensity of the incident light. 2. The support has a glass transition temperature (Tg) of 9.
The silver halide photographic light-sensitive material according to claim 1, which is a polyester derivative at 0 ° C to 200 ° C. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the support is preheat-treated at a temperature of Tg or higher and lower than the melting point before the heat-treatment. 4. The surface of the support is surface-treated by at least one of corona treatment, ultraviolet treatment, glow treatment and flame treatment.
The silver halide photographic light-sensitive material as described in any one of 3 above. 5. The halogenated product according to claim 1, wherein the polyester mainly constituting the support comprises a polyester derivative containing naphthalenedicarboxylic acid and ethylene glycol as main components. Silver photographic light-sensitive material. 6. The silver halide photographic light-sensitive material according to claim 1, wherein the polyester mainly constituting the support is polyethylene-2,6-naphthalenedicarboxylate. material. 7. The electric resistance of the antistatic layer is 10 ¹² Ω (2
5. The silver halide photographic light-sensitive material according to claim 1, wherein the temperature is 5 ° C. and 60% RH) or less. 8. The amplitude of the reflected light is 1 to 5% of the incident light intensity.
2. The silver halide photographic light-sensitive material according to claim 1, wherein the polymer layer has a thickness of 0.7 to 5 μm. 9. At least one or more lubricants composed of higher fatty acid and its derivative, higher alcohol and its derivative are contained in at least one layer on the side having the polymer layer,
2. The silver halide photographic light-sensitive material according to claim 1, wherein the coefficient of dynamic friction of the outermost layer surface is 0.25 or less.