JPH07114139A - Silver halide photographic sensitive material and its intermediate product - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material or its intermediate product less liable to curl and free from ununiformity in winding and scratch by controlling a method for winding a silver halide photographic sensitive material or its intermediate product. CONSTITUTION:(1) A silver halide photographic sensitive material with at least one silver halide emulsion layer on the protruding side of the photographic polyester base having a curl in the transverse direction is wound around a spool with the protruding side of the base inward. (2) When the silver halide photosensitive material is product, its intermediate product is wound around a spool with the protruding side of the base inward.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material or an intermediate product thereof, and more specifically, winding deviation caused by curling of a support,
And a silver halide photographic light-sensitive material or an intermediate product thereof in which the occurrence of scratches is prevented.

[0002]

2. Description of the Related Art At present, a compact camera which can be easily photographed and is convenient to handle and carry has been put into practical use.
However, in view of convenience and convenience of carrying, further miniaturization is desired. In order to pursue miniaturization, it is essential to make the storage space of the built-in photographic film compact.

Usually, a photographic film is incorporated in a state that a roll-shaped film is wound on a spool. Therefore, in order to make the space compact and to secure a fixed number of images (for example, 36 images), It is necessary to reduce the thickness of the photographic film itself. In particular, the thickness of the support of photographic film is 120 to 125 μm even at present, and it is considerably thicker than the thickness of the photosensitive layer (25 to 35 μm) above it, so reduce the thickness of this support. This is considered to be the most effective means for reducing the thickness of the entire photographic film.

Incidentally, a triacetate film such as triacetyl cellulose (hereinafter sometimes abbreviated as TAC) is typical as a plastic film support used conventionally, but the TAC film is originally mechanical. Due to its low strength, it is not suitable as a photographic support when it is made thinner than the current one. Also, TA
C uses a large amount of methylene chloride in the production of the film, and from the viewpoint of environmental protection, many auxiliary equipment such as a recovery device is required, which is unfavorable because of high cost.

On the other hand, polyethylene terephthalate has hitherto been known as a support and has been used for X-ray films and plate-making films. Due to its excellent strength, application to color negative films is also possible. However, although the polyethylene terephthalate support is excellent in strength, it has a drawback in that the winding curl once attached is hardly removed even after the development processing, and the removability of the curling curl is poor.

As a means for eliminating the curling of the polyester support, a method of imparting hydrophilicity to the polyester support, for example, JP-A-2-120857 and JP-A1-244446, shows an improved technique by hydrophilization. However, in order to improve the curl-eliminating property after development processing to the same extent as TAC, simply adding a copolymerization component to make it hydrophilic makes curling of the copolyester support before development processing. On the contrary, there is a problem that the handling property before the development processing is deteriorated.

In order to solve this problem, for example, Japanese Patent Application No. 4-344017 discloses a technique in which a polyester support having a curl in the width direction is used to prevent curling. ing. However, when a polyester support having a curl in the width direction is used in advance, when producing a silver halide photographic light-sensitive material, or when producing an intermediate product thereof,
It has been found that when the photosensitive material or the intermediate product is wound up, the curl of the width may cause misalignment, or scratches and the like caused by the misalignment.

[0008]

The object of the present invention is to solve the above problems by controlling the winding method of a silver halide photographic light-sensitive material or an intermediate product thereof.
Another object of the present invention is to provide a silver halide photographic light-sensitive material or an intermediate product thereof which is hard to curl up and is free from winding misalignment and scratches.

[0009]

The above object of the present invention can be achieved by any one of the following constitutions.

A polyester photographic support having curl in the width direction has at least one silver halide emulsion layer on the convex side, and the convex side of the photographic support is wound into a spool and wound up on a spool. A characteristic silver halide photographic light-sensitive material.

When producing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on the convex surface side of a polyester photographic support having curl in the width direction, the convex surface is wound inside the roll. An intermediate product of silver halide photographic light-sensitive material, characterized by being taken.

The polyester film photographic support is
The silver halide photographic light-sensitive material and the intermediate product thereof, which is a polyester laminated film, and in which the laminated structures on both sides of the film are asymmetric with respect to the position where the thickness is divided into two parts.

The silver halide photographic light-sensitive material and the intermediate product thereof, wherein the polyester film photographic support has a curl degree in the width direction of -5 to -35 (1 / m).

The present invention will be specifically described below.

The silver halide photographic light-sensitive material of the present invention comprises a polyester support, an undercoat layer coated on the support, a photosensitive silver halide emulsion layer, and a back layer.

The intermediate product of a silver halide photographic light-sensitive material is a product in the intermediate stage from the polyester support to the silver halide photographic light-sensitive material, which is a polyester support or the support. A product in which an undercoat layer is applied, or a product in which an undercoat layer and a back layer are applied to the support is referred to.

-Polyester film support-As the polyester film used in the present invention,
There is no particular limitation as long as it has sufficient strength as a photographic support. For example, terephthalic acid, isophthalic acid, phthalic acid,
Polyethylene terephthalate, which is a polymer of a condensate of aromatic dicarboxylic acid such as and naphthalenedicarboxylic acid, and glycols such as ethylene glycol, 1,3-propanediol, and 1,4-butanediol, polyethylene-2,6- Copolymerized polyesters such as dinaphthalate, polypropylene terephthalate and polybutylene terephthalate can be mentioned.

A dicarboxylic acid having a metal sulfonate group may be used as the copolymerization component, and polyethylene glycols may be used. Examples of these resins include, for example, U.S. Pat.No. 3,052,543, JP-B-57-28336, JP-A-59-33894, and JP
The polyesters disclosed in 1-244446, U.S. Pat. No. 5,138,024 and the like are preferable.

As the polyalkylene glycols, polyethylene glycol, polytetramethylene glycol and derivatives thereof are used. Among them, the polyethylene glycol represented by the formula (a) is preferable, and the molecular weight is not particularly limited, but 300 It is preferably from 20,000 to 20,000, more preferably from 600 to 10,000, and particularly preferably from 1,000 to 5,000.

H (O—CH ₂ CH ₂ ) _n —OH (a) As the polyalkylene glycols, the terminal —H of polyethylene glycol is represented by ═CH ₂ COOR (R: H or alkyl having 1 to 10 carbon atoms). Group, n: a positive integer) and substituted with a polyethyleneoxydicarboxylic acid represented by the formula (b) or a polyether dicarboxylic acid represented by the formula (c) (R ': alkylene having 2 to 10 carbon atoms). Group, n: positive integer) and the like, the same effect can be obtained.

[0021] _{ROOCCH 2 - (OCH 2 CH 2} ) n -OCH 2 COOR (b) ROOCCH 2 - (O-R ') n-OCH 2 COOR (c) (b), represented by the formula (c) The molecular weight of the compound is also not particularly limited, but it is preferably 300 to 20000, more preferably 600 to 10000, and particularly preferably 1000 to 5000.

The polyester used for the photographic support in the present invention has an intrinsic viscosity of 0.4 in a mixed solution of phenol / 1,1,2,2-tetrachloroethane (60/40 weight ratio) of 0.4. It is preferably -1.0, more preferably 0.5-0.8.

The polyester film support comprises phosphoric acid, phosphorous acid and their esters, and inorganic particles such as silica, kaolin, calcium carbonate, calcium phosphate and titanium dioxide, matting agents, antistatic agents, lubricants and surface active agents. It may contain various additives such as an agent, a stabilizer, a dispersant, a plasticizer, a UV absorber, a conductive substance, a tackifier, a softening agent, a fluidity enhancer, a thickener and an antioxidant. it can.

The polyester film support of the present invention can be produced by a known synthesis method such as melt polymerization or solid phase polymerization of a polymer obtained by melt polymerization.

The polyester film support of the present invention is obtained by, for example, sufficiently drying the copolyester and then melt-extruding it into a sheet form through an extruder, a filter, a die and the like controlled in a temperature range of 260 to 320 ° C. The polymer is cooled and solidified on a rotating cooling drum to obtain an unstretched film. After that, the unstretched film can be produced by biaxially stretching in the machine direction and the transverse direction and heat-setting.

Examples of the method for biaxially stretching the film include the following methods (A) to (C).

(A) A method in which an unstretched film is first stretched in the longitudinal direction and then stretched in the transverse direction (B) A method in which an unstretched film is stretched in the transverse direction first and then in the longitudinal direction (C) Unstretched A method in which the film is stretched in the longitudinal direction in one stage or multiple stages, then stretched in the longitudinal direction again, and then stretched in the transverse direction. The stretching is performed in order to satisfy the mechanical strength, dimensional stability, etc. of the polyester film support. , Area ratio 4-16
It is preferable to carry out in a double range.

The polyester film support of the present invention may be a single-layer film or sheet formed by the above-mentioned method, and has a multi-layer structure laminated by a coextrusion method or a laminating method. Good.
The obtained polyester film support is particularly suitable as a support for a photographic film used in a roll form.

The curl of the polyester film support of the present invention will be described below. The curl of the support means the curl (curvature) of the support itself, the degree of which can be measured according to the international standard ISO4330, and is expressed in 1 / R (unit: 1 / m) described in the international standard.
It is expressed by. Further, the curl on the emulsion side is indicated by + (plus), and the curl on the back layer side is indicated by- (minus). In the present invention, the curl of the support is preferably curled concavely in the width direction on the back layer side, and more preferably -5 to -35 (1 /
The range is m).

As a method of preliminarily providing a widthwise curl on the polyester film support of the present invention, in the case of a single layer film, one of the methods described in, for example, JP-A-64-70748 is used when the polyester film is stretched. A method in which one side surface and the other side surface are heated so as to have different surface temperatures, and a film is provided by stretching while making a temperature gradient exist from the surface of the film to the other surface, or during undercoating of the support. There is a method of applying a subbing composition made by adding an organic solvent such as phenol or cresol which is a solvent for a polyester film or a swelling agent to provide a curl.

Further, in the case of a film obtained by laminating two or more layers of polyester, in order to impart curl in the width direction to the polyester film, in the case of a two-layer structure, preferably the two layers forming the film are It is preferably composed of a polyester layer, and the thickness may be the same or different, and more preferably, the polyester species of the upper and lower layers of the laminated film have different main constituents or different main constituents, or a copolymerization constituent. Alternatively, it is preferable that the amounts of the copolymerization components are different. For example, it is not particularly limited, but may be composed of a polyester layer and a copolyester layer, or a copolyester layer and a copolyester layer. The copolymerization component preferably contains an aromatic dicarboxylic acid having a metal sulfonate group, and further preferably contains a polyalkylene glycol and / or a saturated aliphatic dicarboxylic acid. In this case, as a copolymerization component in the copolymerized polyester used, an aromatic dicarboxylic acid having a metal sulfonate group is contained in an amount of 2 to 7 mol% based on all ester bonds, and polyalkylene glycols are further used as a copolymerization component. It is particularly preferable to contain 3 to 10% by weight of the saturated aliphatic dicarboxylic acid with respect to the total weight of the copolymerization component. When it is composed of two layers, a curl in the width direction can be imparted to the laminated film by appropriately adjusting the above items.

In the case of a three-layer structure, it is preferable that the two outer layers are composed of polyester layers. However, if the effect of the present invention is not impaired, even if the central layer is a polyester layer, other materials, such as polycarbonate, are not particularly limited. , Polyether, polyamide, polyimide, polyphthalamide, polyphthalimide and the like. It is preferable that all three layers are polyester layers. As the layer constitution, it is preferable that the outer layers have different thicknesses, and when the thicknesses of the outer layers are d _A and d _B from the thickest one, the ratio d _A / d _B is not particularly limited. Is 1.1 ≦ d _A / d _B ≦ 5, preferably 1.3 ≦ d _A /
d _B ≦ 3. Further, in the case of a three-layer structure, the thickness of the outer layer may be the same or different, but the polyester species of the upper and lower layers which are the outer layers of the laminated film are the main constituent components or the amount of the main constituent components is different, It is preferable that the copolymerization component or the amount of the copolymerization component be different, and further that the intrinsic viscosity be different. In this case, as a copolymerization component in the copolymerized polyester used, an aromatic dicarboxylic acid having a metal sulfonate group is contained in an amount of 2 to 7 mol% based on all ester bonds, and polyalkylene glycols are further used as a copolymerization component. It is particularly preferable to contain 3 to 10% by weight of the saturated aliphatic dicarboxylic acid with respect to the total weight of the copolymerization component. When it is composed of three layers, the widthwise curl can be imparted to the laminated film by appropriately adjusting the above items. Intrinsic viscosity difference ΔIV is 0.02
~ 0.5, preferably 0.05 ~ 0.4, particularly preferably 0.1 ~
It is 0.3.

In addition, in the case of the above-mentioned two-layer, three-layer, and the constitution of four or more layers, what is necessary for imparting a width curl to the film of the present invention is the total thickness of the film. A width curl can be imparted to a surface divided in half if the layer structure is asymmetrical above and below the surface.

The asymmetry referred to here is not particularly limited, but, for example, the order in which the polyester layer or the layer made of another material is constituted, the thickness of the polyester layer or the layer made of another material, and the upper and lower sides of the surface divided in half. It also includes that the amount of the main constituent component of the polyester species is different, that the amount of the copolymerization component or the amount of the copolymerization component is different, and that the intrinsic viscosity is different.

As a method for measuring the asymmetry of these laminated films, various analytical instruments can be used,
Although not particularly limited, the cross-section of the film can be observed under a microscope and a micrograph can be taken regarding the layer structure. In addition, while observing the film under a microscope, each layer is scraped off, or the film is divided into halves, and each of the upper and lower layers is scraped from the upper and lower sides to obtain an analyte.
Hydrolysis and liquid chromatography or NMR
It may be measured by various measuring devices such as the like, or the inherent viscosity may be measured by NMR, GPC (gel permeation chromatography) or the like after the analyte is dissolved in a solvent, or the analyte may be powdered as it is. It is possible to measure IR (infrared spectroscopic instrument) etc. by mixing with X-ray spectroscopic instrument or KBr etc., and as a result, absolute amount or asymmetry in the difference in peak position, intensity etc. of the measurement result corresponding to it. Can be measured.

When the film of the present invention has a laminated structure of two layers, in the case of a polyester layer and a copolyester layer, the copolyester layer side usually has a concave curl in the width direction, and the copolyester layer. In the case of the two, the curl in the width direction can be adjusted by appropriately adjusting the film thickness and the composition amount. In the case of a three-layer structure, in the case of a copolyester layer as the outer layer, the above-mentioned curl in the width direction of the concave surface on the d _A side can usually be imparted, and the copolyester layer as the inner layer and the polyester layer as the outer layer. in the case of can normally d _B side to impart a concave Habate curl. Further, the film of the present invention is not limited to these, even if it has two layers, three layers, four layers or more, and the above-mentioned layer constitution, film thickness, amount of copolymerization components, etc. of the present invention described above are appropriately used. A curl can be imparted by appropriately adjusting the items.

== Undercoat Layer == In the present invention, the polyester support has a silver halide emulsion layer coated thereon, and an undercoat layer for increasing the adhesion with the back layer. Is preferred.

Examples of the undercoat layer include undercoat using polymer latex and undercoat using hydrophilic binder such as gelatin.

In the present invention, the undercoat layer may have conductivity. To impart conductivity, the undercoat layer can be formed by incorporating a hygroscopic substance or a conductive substance. Examples of the substance that imparts conductivity include a surfactant, an anionic conductive polymer, a cationic conductive polymer, and an inorganic metal oxide.

The undercoat layer according to the present invention can be applied by a generally well-known coating method, for example, a dip coating method, an air knife coating method, a wire bar coating method or the like.

The undercoat layer may be formed by biaxially stretching the polyester support and then applying the film, or by first stretching the polyester support in the machine or transverse direction and then applying the undercoat layer. Then, it may be stretched in the transverse or longitudinal direction, or may be a method in which a polyester unstretched film is coated with an undercoat layer and then biaxially stretched to form a film.

-Silver Halide Emulsion Layer- The silver halide emulsion layer comprises a silver halide emulsion containing silver halide and other components, directly or indirectly on the surface of one or both sides of the polyester film support. It can be formed by coating by various methods.

The silver halide emulsion may be coated directly on the polyester film support, or may be coated via another layer such as a hydrophilic colloid layer containing no silver halide emulsion. Further, a hydrophilic colloid layer as a protective layer may be coated on the silver halide emulsion layer. Further, the silver halide emulsion layers may be separately coated on each of the silver halide emulsion layers having different sensitivities, for example, high sensitivity and low sensitivity. In this case, an intermediate layer may be provided between each silver halide emulsion layer. That is, you may provide the intermediate layer which consists of hydrophilic colloids as needed.
Further, between the silver halide emulsion layer and the protective layer, an intermediate layer,
A non-photosensitive hydrophilic colloid layer such as a protective layer, an antihalation layer and a back layer may be provided.

The silver halide used in the silver halide emulsion may have any composition.
Examples thereof include silver chloride, silver chlorobromide, silver chloroiodobromide, pure silver bromide and silver iodobromide.

Further, this silver halide emulsion may contain other components such as a binder, a sensitizing dye, a plasticizer, an antistatic agent, a surfactant and a hardener.

As the method for coating the silver halide emulsion layer, various methods such as dip coating, air knife coating, curtain coating, and extrusion coating can be used to coat one layer at a time or multiple layers at the same time.

The content of the hydrophilic colloid in the emulsion layer is 0.5 to 30 g / m ² .

-Back layer (3) -The back layer comprises a back layer coating containing gelatin and other components on the side opposite to the side of the polyester film support on which the silver halide emulsion layer is formed. It can be formed by applying a single layer or a plurality of layers on the surface.

In the present invention, the outermost layer of the back layer may contain a fluorinated anionic surfactant and a fluorinated cationic surfactant.

As the gelatin, lime-processed gelatin, acid-processed gelatin, alkali-processed gelatin, and hydrolyzed or enzymatically decomposed products of gelatin and other gelatin derived from gelatin can be used.

The back layer in the present invention further comprises, as other components, compounds known per se such as hydrophilic colloids, matting agents, slip agents, surfactants, hardeners, dyes, thickeners and polymer latices. Can be included.

Examples of the hydrophilic colloid include compounds having the same properties as gelatin, for example, natural or synthetic hydrophilic polymers. The content of the hydrophilic colloid in the back layer is not particularly limited, but is preferably 0.1 to 15 g / m ² .

The matting agent, the slip agent, the surfactant, and the hardener are described in Research Disclosure, 17643 (1978), for example.
The compounds described in Section XVI, Section XII, Section XI and Section X, respectively, can be used.

A magnetic recording layer may be provided on the back layer of the present invention.

As the magnetic fine powder used in the magnetic recording layer, metal magnetic powder, iron oxide magnetic powder, Co-doped iron oxide magnetic powder, chromium dioxide magnetic powder, barium ferrite magnetic powder and the like can be used. .

[0056]

EXAMPLES Examples of the present invention will be described in detail below.
It goes without saying that the present invention is not limited to this.

Example 1 (Production of Polyester Laminated Film Supports 1 to 5) Polyester supports 1 to 5 as intermediate products of silver halide photographic light-sensitive materials were produced by the following method.

100 parts by weight of dimethyl terephthalate, 64 parts by weight of ethylene glycol, and 0.1 part by weight of calcium acetate hydrate as a transesterification catalyst were added to carry out a transesterification reaction by a conventional method.

The product obtained is treated with 5-sodium sulfo-
Di (β-hydroxyethyl) isophthalic acid (abbreviation; SI
P) 28 parts by weight of ethylene glycol solution (concentration 35% by weight), and polyethylene glycol (abbreviation: PEG)
(Number average molecular weight: 3000) Add 8.1 parts by weight, then
Antimony trioxide 0.05 part by weight, phosphoric acid trimethyl ester 0.13 part by weight, Irganox 1010 as an antioxidant
(CIBA-GEIGY) 0.2 parts by weight and sodium hydroxide
0.02 part by weight was added. Then gradually raise the temperature and reduce the pressure,
Polymerization was carried out under the conditions of 280 ° C. and 0.5 mmHg to obtain a copolyester having an intrinsic viscosity of 0.55.

Using this copolymerized polyester and photographic polyethylene terephthalate (intrinsic viscosity: 0.65) used as the polyester layer, a photographic support was obtained as follows.

The copolymerized polyester and polyethylene terephthalate were respectively vacuum dried at 150 ° C.,
Using three extruders, melt extrusion at 285 ° C., so that the ratio of the thickness of copolyester / polyethylene terephthalate / copolyester from the emulsion layer coated side of the support becomes the layer constitution shown in Table 1. Was laminated in a T-die in a layered manner, and rapidly cooled and solidified on a cooling drum to prepare a polyester laminated unstretched film. This laminated unstretched film,
The film was stretched 3.5 times in the vertical direction at 85 ° C., further stretched 3.5 times in the horizontal direction at 95 ° C., and then heat-set at 210 ° C. to obtain polyester film supports 1 to 5 having a thickness of 90 μm.

(Production of Support 6) Polyethylene terephthalate (PET) (intrinsic viscosity 0.65) melt-extruded in a film form at 280 ° C. from a T-die is rapidly cooled and solidified on a cooling drum to prepare an unstretched film. During stretching, the surface temperature on the emulsion side of the support was 85 ° C, and the surface temperature on the backing layer side of the support was 75 ° C.
After being stretched 3 times in the transverse direction at 100 ° C., it was heat set at 220 ° C. to obtain a polyester film support 6 having a thickness of 90 μm.

(Evaluation Method) << Method for Evaluating Curling Degree of Support >> Polyester Supports 1 to 6
About 35 mm in the width direction of the film, 2 in the longitudinal direction
The sample was cut with a width of 3 mm. The curl degree in the width direction was measured under the environment of 23 ° C. and 55 RH% (after humidity conditioning for 24 hours) and expressed as the reciprocal of the radius of curvature (unit: 1 / m). Further, the symbols are indicated by + (plus) when curled on the emulsion layer coating side, and by- (minus) when curled on the back layer coating side.

<< Evaluation of winding characteristics >> Polyester support 1
About 6 to 6, after the polyester support having a width of 1000 mm is formed into a film, the core having a diameter of 25 cm is rolled up by 1000 m into a roll so that the curled convex surface of the support is wound in or out. Distance of end face width direction deviation (mm)
Was measured and evaluated.

At the same time, the appearance of the roll surface is
It was judged in stages.

⊚: No wrinkles were found on the roll surface. ◯: Slight wrinkles were found on the end of the roll. Δ: Partially wrinkles were found. ×: Wrinkles were found on the entire surface of the roll. Occurrence is observed. In practical use, if it is ◯ or above, it is at a level with no problem.

[0067]

[Table 1]

As is clear from Table 1, during the production of a polyester photographic support, which is an intermediate product of a silver halide photographic light-sensitive material, it should be wound up so that the curled convex surface of the support is in the roll after film formation. Thus, it can be seen that winding deviation is prevented and winding characteristics are excellent. It is particularly effective when the polyester photographic support is an asymmetric laminated polyester film.

(Example 2) 8 W / (m ² · min) was applied to both surfaces of the polyester supports 1 to 6 prepared in Example 1.
Corona discharge treatment of
-3 is applied to give a dry film thickness of 0.8 μm to form an undercoat layer B-3, and the undercoating coating solution B-4 shown below is applied to the other surface of the support at a dry film thickness of 0.8 μm. To form an undercoat layer B-4.

<Undercoating Coating Liquid B-3> A copolymer latex liquid containing 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene, and 25% by weight of 2-hydroxyethyl acrylate (solid content: 30%). %) 270 g Compound (UL-1) 0.6 g Hexamethylene-1,6-bis (ethyleneurea) 0.8 g Finish with water 1000 ml <Undercoating liquid B-4> 40 wt% butyl acrylate, 20 wt% styrene and Copolymer latex liquid containing 40% by weight of glycidyl acrylate (solid content 30%) 270 g Compound (UL-1) 0.6 g Hexamethylene-1,6-bis (ethyleneurea) 0.8 g Finish with water 1000 ml Further undercoat layer 8 W / on top of B-3 and subbing layer B-4
A corona discharge of (m ² · min) is applied, and the following coating solution B-5 is applied on the undercoat layer B-3 so that the dry film thickness is 0.1 μm to form the undercoat layer B-5. On the undercoat layer B-4, the following coating solution B-6 was applied so as to have a dry film thickness of 0.8 μm to form an undercoat layer B-6 having an antistatic function.

<Coating Liquid B-5> Gelatin 10 g Compound (UL-1) 0.2 g Compound (UL-2) 0.2 g Compound (UL-3) 0.1 g Silica particles (average particle size: 3 μm) 0.1 g Water Finish 1000 ml <Coating liquid B-6> Water-soluble conductive polymer (UL-4) 60 g Latex liquid containing compound (UL-5) as a component (solid content 20%) 80 g Ammonium sulfate 0.5 g Curing agent (UL-6 ) 12 g Polyethylene glycol (weight average molecular weight 600) 6 g Finished with water 1000 ml The structures of the compounds (UL-1 to 6) used are collectively shown below.

On the undercoat layer B-5, 25 W / (m ² · mi
n) Corona discharge was applied, and 8W on the undercoat layer B-6.
/ (M ² · min) corona discharge was applied. Further, the following emulsion layers and the like were sequentially formed on the surface of the undercoat layer B-5, and the following back layer was formed on the surface of the undercoat layer B-6 to prepare a silver halide photographic light-sensitive material.

The following back layers were sequentially formed on the surface of the subbing layer B-6 to obtain intermediate products of the silver halide photographic light-sensitive material, Samples 001 to 006, in which only the silver halide emulsion layer was not applied.

The formulation of the back layer is shown below.

<Back Layer> First Layer The following components were mixed together with a dissolver and then dispersed with a sand mill to obtain a dispersion liquid. It was applied so as to have a dry film thickness of 2 μm.

Nitrocellulose 35 parts by weight Polyurethane resin 35 parts by weight Lauric acid 1 part by weight Oleic acid 1 part by weight Butyl stearate 1 part by weight Cyclohexanone 75 parts by weight Methyl ethyl ketone 150 parts by weight Toluene 150 parts by weight Co Coated γ-Fe ₂ O ₃ (Long width 0.2 μm, short axis 0.05 μm, Hc = 650 oersted) 5 parts by weight Second layer The following coating liquid was applied onto the first layer so that the concentration was 10 ml / m ² .

Carnauba wax 1 g Toluene 700 g Methyl ethyl ketone 300 m
l

[0078]

[Chemical 1]

[0079]

[Chemical 2]

(Evaluation Method) << Method of Evaluating Curling Degree of Support >> Photosensitive Material Intermediate Product Sample 00
With respect to Nos. 1 to 006, the back layer and the undercoat layer were peeled off using acetone, and then the sample was cut into a width of 35 mm in the width direction and a width of 2 to 3 mm in the longitudinal direction. Curling degree in the width direction is measured under the environment of 23 ° C and 55RH% (after conditioning for 24 hours),
It was expressed by the reciprocal of the radius of curvature (unit: 1 / m). Further, the symbols are indicated by + (plus) when curled on the emulsion layer side, and by- (minus) when curled on the back layer side.

The degree of curl of the support did not change before and after coating the back layer and the undercoat layer.

<< Evaluation of winding characteristics >> As for intermediate products 001 to 006 of intermediate products of silver halide photographic light-sensitive materials, an intermediate product having a width of 1000 mm was wound on a core having a diameter of 25 cm with a curled convex surface of a support inside or outside. 1000m in a roll so that
Distance of roll end face widthwise deviation when wound (m
m) was measured and evaluated.

At the same time, the appearance of the roll surface is
It was judged in stages.

⊚: No wrinkles were observed on the roll surface ◯: Slight wrinkles were observed on the end of the roll Δ: Wrinkles were observed partially ×: Wrinkles were observed on the entire roll surface Occurrence of is seen.

In practical use, if it is ◯ or above, there is no problem.

[0086]

[Table 2]

As is clear from Table 2, the intermediate product of the silver halide photographic light-sensitive material in which the polyester photographic support was coated with an undercoat layer and a back layer was used. It can be seen that the winding property is excellent and the winding property is prevented by winding the film in such a manner that the winding is performed. In particular,
It is effective when the polyester photographic support is an asymmetric laminated polyester film.

Example 3 A silver halide photograph was prepared by coating the following emulsion layer on the surface of the undercoat layer B-5 of the intermediate product samples 001 to 006 of the silver halide photographic light-sensitive material prepared in Example 2. Photosensitive material samples 7 to 12 were prepared.

<Emulsion layer> First layer; Antihalation layer (HC) Black colloidal silver 0.15 g UV absorber (UV-1) 0.20 g Compound (CC-1) 0.02 g High boiling point solvent (Oil-1) 0.20 g High boiling point solvent (Oil-2) 0.20 g Gelatin 1.6 g Second layer; Intermediate layer (IL-1) Gelatin 1.3 g Third layer; Low sensitivity red sensitive emulsion layer (RL) Silver iodobromide emulsion (average grain size 0.3 μm, average iodine content 2.0 mol%) 0.4 g Silver iodobromide emulsion (average grain size 0.4 μm, average iodine content 8.0 mol%) 0.3 g Sensitizing dye (S-1) 3.2 × 10 ⁻⁴ (mol / Silver 1 mol) Sensitizing dye (S-2) 3.2 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-3) 0.2 × 10 ⁻⁴ (mol / silver 1 mol) Cyan coupler (C-1) ) 0.50 g Cyan coupler (C-2) 0.13 g Colored cyan coupler (CC-1) 0.07 g DIR compound (D-1) 0.006 g IR compound (D-2) 0.01 g High boiling point solvent (Oil-1) 0.55 g Gelatin 1.0 g Fourth layer; high-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (average grain size 0.7 μm, average iodine content) Amount 7.5 mol%) 0.9 g Sensitizing dye (S-1) 1.7 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-2) 1.6 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.1 × 10 ⁻⁴ (mol / silver 1 mol) Cyan coupler (C-2) 0.23 g Colored cyan coupler (CC-1) 0.03 g DIR compound (D-2) 0.02 g High boiling solvent (Oil -1) 0.25 g Gelatin 1.0 g Fifth layer; Intermediate layer (IL-2) Gelatin 0.8 g Sixth layer; Low sensitivity green sensitive emulsion layer (GL) Silver iodobromide emulsion (average grain size 0.4 μm, containing average iodine) Amount 8.0 mol%) 0.6 g silver iodobromide emulsion (average grain size 0.3 μm, average iodine content 2.0 mol%) 0.2 g sensitizing dye (S-4) 6.7 × 10 ^{− 4} (mol / silver 1 mol) Sensitizing dye (S-5) 0.8 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M-1) 0.17 g Magenta coupler (M-2) 0.43 g Colored magenta coupler ( CM-1) 0.10 g DIR compound (D-3) 0.02 g High boiling point solvent (Oil-2) 0.7 g Gelatin 1.0 g Seventh layer; high sensitivity green sensitive emulsion layer (GH) Silver iodobromide emulsion (average grain size 0.7 μm, average iodine content 7.5 mol%) 0.9 g Sensitizing dye (S-6) 1.1 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-7) 2.0 × 10 ⁻⁴ (mol / silver) Sensitizing dye (S-8) 0.3 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M-1) 0.30 g Magenta coupler (M-2) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-3) 0.004 g High boiling point solvent (Oil-2) 0.35 g Gelatin 1.0 g Eighth layer; Yellow Filter layer (YC) Yellow colloidal silver 0.1 g Additive (HS-1) 0.07 g Additive (HS-2) 0.07 g Additive (SC-1) 0.12 g High boiling point solvent (Oil-2) 0.15 g Gelatin 1.0 g Layer 9: Low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (average grain size 0.3 μm, average iodine content 2.0 mol%) 0.25 g Silver iodobromide emulsion (average grain size 0.4 μm, average iodine content) Amount 8.0 mol%) 0.25 g Sensitizing dye (S-9) 5.8 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.6 g Yellow coupler (Y-2) 0.32 g DIR compound (D- 1) 0.003 g DIR compound (D-2) 0.006 g High boiling point solvent (Oil-2) 0.18 g Gelatin 1.3 g 10th layer; high-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (average grain size 0.8 μm , average iodine content of 8.5 mol%) 0.5 g sensitizing dye (S-10) 3 × 10 -4 ( mol / mole of silver) Sensitive dye (S-11) 1.2 × 10 -4 ( mol / mole of silver) Yellow coupler (Y-1) 0.18 g Yellow coupler (Y-2) 0.10 g High boiling solvent (Oil-2) 0.05 g Gelatin 2.0 g 11th layer; 1st protective layer (PRO-1) Silver iodobromide emulsion (average particle size 0.08 μm) 0.3 g UV absorber (UV-1) 0.07 g UV absorber (UV-2) 0.10 g Additive ( HS-1) 0.2 g Additive (HS-2) 0.1 g High boiling point solvent (Oil-1) 0.07 g High boiling point solvent (Oil-3) 0.07 g Gelatin 0.8 g 12th layer; 2nd protective layer (PRO-2) ) Compound (Compound A) 0.04 g Compound (Compound B) 0.004 g Polymethylmethacrylate (average particle size: 3 μm) 0.02 g Methylmethacrylate: ethylmethacrylate: methacrylic acid = 3: 3: 4 (weight ratio) Copolymer (average particle size: 3 μm) 0.13 g Gelatin 0.7 g-iodine Preparation of silver halide emulsion - silver iodobromide emulsion used in the 10th layer was prepared by the following method.

A silver iodobromide emulsion was prepared by the double jet method using monodisperse silver iodobromide grains having an average grain size of 0.33 μm (silver iodide content 2 mol%) as seed crystals.

A solution <G-1> having the following composition was added at a temperature of 70 ° C. and p
While maintaining Ag 7.8 and pH 7.0, a seed emulsion corresponding to 0.34 mol was added while stirring well.

(Formation of Internal High Iodity Phase-Core Phase) Then, a solution <H-1> having the following composition and a solution <S- having the following composition:
1> and 1> were added at an accelerated flow rate (the flow rate at the end was 3.6 times the initial flow rate) over 86 minutes while maintaining the flow rate ratio of 1: 1.

(Formation of External Low Iodity Phase-Shell Phase) Next, <H-2> and <H2> while maintaining the pH at 10.1 and the pH at 6.0.
S-2> and S-2> were added at a flow rate accelerated by 1: 1 (the flow rate at the end was 5.2 times the initial flow rate) over 65 minutes.

The pAg and pH during grain formation were controlled using an aqueous potassium bromide solution and a 56% aqueous acetic acid solution. After the particles are formed, they are washed with water by a conventional flocculation method, and then gelatin is added to redisperse them.
H and pAg were adjusted to 5.8 and 8.06, respectively.

The obtained emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 μm, a broad distribution of 12.4% and a silver iodide content of 8.5 mol%.

<G-1> Solution Ocein gelatin 100.0 g 10% by weight solution of the following compound-I in methanol 25.0 ml 28% aqueous ammonia solution 440.0 ml 56% acetic acid aqueous solution 660.0 ml Finish with water 5000.0 ml * Compound-I: polypropyleneoxy・ Polyethyleneoxy disuccinate / Natrium <H-1> solution Ocein gelatin 82.4 g Potassium bromide 151.6 g Potassium iodide 90.6 g Finish with water 1030.5 ml <S-1> solution Silver nitrate 309.2 g 28% ammonia solution equivalent Finish with water 1030.5 ml <H-2> solution Ocein gelatin 302.1 g Potassium bromide 770.0 g Potassium iodide 33.2 g Finish with water 3776.8 ml <S-2> solution Silver nitrate 1133.0 g 28% ammonia solution equivalent Finish with water 3776.8 ml For silver iodobromide emulsions used in emulsion layers other than the 10th layer, the average grain size of seed crystals, temperature, pAg, p
The above emulsions having different average grain sizes and silver iodide contents were prepared by changing H, flow rate, addition time, and halide composition.

All were core / shell type monodisperse emulsions having a distribution of 20% or less. Each emulsion was subjected to optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate, and a sensitizing dye, 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene, 1-phenyl-5-mercaptotetrazole was added.

The above-mentioned light-sensitive material further comprises compounds Su-1, Su-2, a viscosity adjusting agent, a film hardener H-1, and H-.
2, stabilizer ST-1, antifoggant AF-1, AF-2
(Weight-average molecular weight of 10,000 and 1,100,000), dyes AI-1, AI-2 and compound DI-1
(9.4 mg / m ² ).

[0099]

[Chemical 3]

[0100]

[Chemical 4]

[0101]

[Chemical 5]

[0102]

[Chemical 6]

[0103]

[Chemical 7]

[0104]

[Chemical 8]

[0105]

[Chemical 9]

[0106]

[Chemical 10]

[0107]

[Chemical 11]

[0108]

[Chemical 12]

(Evaluation Method) The silver halide photographic light-sensitive material samples 007 to 012 prepared as described above were evaluated as described below, and the results are shown in Table 3.

<< Method for Evaluating Curling Degree of Support >> Photosensitive Material Sample
Regarding 007 to 012, the emulsion layer was peeled off using pancreatin, and the back layer and the subbing layer were peeled off using acetone, and then the width direction of the film was 35 mm and the longitudinal direction was 2 to 2.
The sample was cut with a width of 3 mm. The curl degree in the width direction was measured under the environment of 23 ° C. and 55 RH% (after humidity conditioning for 24 hours) and expressed as the reciprocal of the radius of curvature (unit: 1 / m). Further, the symbols are indicated by + (plus) when curled on the emulsion layer side, and by- (minus) when curled on the back layer side.

The degree of curl of the support is such that the emulsion layer, back layer,
It did not change before and after the application of the undercoat layer.

<Scratch> Photosensitive material samples 007 to 012 were slit to a width of 35 mm with a width and cut to a length of 118 cm. At 23 ℃, 22RH% environment (after humidity control for 1 day), the curled convex surface of the support should be inside or outside the cartridge for photographic photosensitive material with cartridge inner diameter 22mm and spool outer diameter 11mm. I got involved.

A print obtained by printing the wound sample through a printer so that the resolution chart was at a magnification of 0.061 times was visually evaluated for the degree of occurrence of scratches according to the following criteria.

◯: No scratches were generated. Δ: Scratches were slightly generated. X: Scratches were considerably generated.

If the rank is not less than Δ, there is no problem in practical use.

[0116]

[Table 3]

As is clear from Table 3, the occurrence of scratches is prevented by winding the silver halide photographic light-sensitive material on a spool so that the curled convex surface of the support is within the roll. . It is particularly effective when the polyester photographic support is an asymmetric laminated polyester film.

[0118]

According to the present invention, in a silver halide photographic light-sensitive material or an intermediate product thereof, a halogen which prevents winding deviation and scratches caused by curling of the support in the width direction is used. Silver halide photographic material,
Or the intermediate product can be provided.

Claims (4)

[Claims] 1. A polyester photographic support having curl in the width direction has at least one silver halide emulsion layer on the convex side, and the photographic support is wound into a spool and wound up on a spool. A silver halide photographic light-sensitive material characterized by the above. 2. When producing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on the convex surface side of a polyester photographic support having curl in the width direction, the convex surface is formed in the roll. Intermediate product of silver halide photographic light-sensitive material, characterized by being rolled up. 3. A polyester film photographic support,
The silver halide photographic light-sensitive material and the intermediate product thereof according to claim 1 or 2, which is a polyester laminated film, and the laminated structure on both sides of the film is asymmetrical with respect to a position where the thickness is divided into two parts. 4. The silver halide photographic light-sensitive material and its intermediate product according to claim 1, wherein the polyester film photographic support has a curl degree in the width direction of -5 to -35 (1 / m).