JPH06308663A - Photographic substrate - Google Patents

Abstract

PURPOSE:To provide a photographic substrate especially maintaining its mechanical strength, capable of reducing film thickness, excellent in handleability and straightening property in short-time processing and suitable for use in a miniature camera. CONSTITUTION:This photographic substrate is a polyester film having 0.3-1wt.% initial water content and increasing the water content by 0.3-1.5% after immersion in warm water at 38 deg.C for 7min. The polyester film is made of copolymerized polyester contg. arom. dicarboxylic acid having a metallic sulfonate group. The initial water content is the water content of the film after adjustment at 23 deg.C and 55% relative humidity for >=1 day.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film used in the form of a roll, and more specifically, it has excellent curl resolving ability while maintaining strength, particularly curl resolving ability in processing equipment, and The present invention relates to a photographic support having excellent strength and suitable for a silver halide photographic light-sensitive material.

[0002]

BACKGROUND OF THE INVENTION A small camera which can be easily photographed and is convenient to handle and carry has been put into practical use. However, considering the convenience and convenience of carrying, further miniaturization is desired, but in pursuit of miniaturization, it is indispensable to make the storage space of the built-in photographic film compact. Usually, a roll of film wound on a spool is built in as a photographic film, so in order to make the space compact and to secure a certain number of shots (for example, 36 shots), It is necessary to reduce the thickness of the film itself. In particular, the thickness of the triacetyl cellulose (TAC) film, which is the support of the photographic film, is about 120 to 125 μm even at present, and is considerably thicker than the thickness of the photosensitive layer (about 25 to 30 μm) thereon, Reducing the thickness of this support is considered to be the most effective means for reducing the thickness of the entire photographic film. By the way, since the TAC film originally has low mechanical strength, it is difficult to make it thinner than the current one.
In addition, TAC uses methylene chloride in the production of a film, which is not preferable because of high cost.

[0003]

On the other hand, a polyester of polyethylene terephthalate has been conventionally known as a support and has been used for an X-ray film and a plate-making film. 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 that the curl resolving ability is inferior, that is, the curl attached when the film is wound and stored for a long period of time is hardly removed even after the development processing.

As a means for eliminating the curl of the polyester support, a method of imparting hydrophilicity to the polyester support,
For example, Japanese Patent Application Laid-Open No. 1-244446 discloses an improvement technique by hydrophilization. However, an amount of a copolymerization component for improving the curl eliminating property after development processing to the same extent as TAC is added, and it is simply added. The hydrophilicity of the copolyester support will greatly increase the curl before the development process.
When it is processed by a short-time processing type minilab type automatic developing machine in which a series of drying processes takes about 7 minutes, the curl does not disappear and the handleability is poor and it cannot be put to practical use.

Further, the strength is lowered by adding the amount of the copolymerization component, and when the film thickness is 100 μm or less, perforation is usually applied to both ends of the film because the film is usually incorporated in a camera for a photographic film. However, there was a defect in the mechanical strength of the film that it was deformed or torn in the perforations at the both ends of the film when it was developed, and it could not be put to practical use. Further, JP-A-4-235036 discloses a technique for improving curl habit elimination by a film obtained by laminating a copolyester having hydrophilicity and a polyester. In this technique, a short treatment time of 7 minutes is also disclosed. In the mold development process, the curl did not disappear and the handleability was poor and it could not be put to practical use. Furthermore, since the support itself does not have anti-curl in the width direction, the emulsion layer of the photographic material after processing contracts and the width of the width of the photographic material is large, and the emulsion surface side of the photographic material floats in the subsequent printing process. Since it could not be conveyed in the print processing process, improvement was necessary. As described above, in the current photographic industry, in order to obtain a photographic material that can be used for photography, a thin support that has excellent strength, curl resolving property in a short time processing, and good curl Development of the body is necessary.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above technical problems, and its object is to maintain the mechanical strength, enable thin film formation, curl habit elimination in a short-time treatment, and handleability. Another object of the present invention is to provide a photographic support suitable for a small camera which is excellent.

[0007]

In order to achieve the above object, the photographic support according to the invention has a film initial water content of 0.3 to 1% and is immersed in warm water of 38 ° C. for 7 minutes. A polyester film having an increased water content of 0.3 to 1.5%, wherein the film is a copolyester containing an aromatic dicarboxylic acid having a metal sulfonate group.

Further, the photographic support according to the present invention has a water content increase amount after the film initial water content is 0.3 to 1% on at least one side of the polyester layer and the film is immersed in warm water at 38 ° C. for 7 minutes. Is 0.3 to 1.5%, and the film is formed by laminating a copolyester layer containing an aromatic dicarboxylic acid having a metal sulfonate group.

Further, as a copolymerization component of the above-mentioned copolymerized polyester, an aromatic dicarboxylic acid having a metal sulfonate group is contained in an amount of 3 to 10 mol% with respect to all ester bonds, and has a repeating structure of at least alkyleneoxy units. It is characterized by containing one or more of a compound represented by the following chemical formula B and / or a derivative thereof, a saturated aliphatic dicarboxylic acid, and a compound represented by the following chemical formula A and / or a derivative thereof. Initial moisture content: moisture content of the film after humidity conditioning at 23 ° C. and 55% RH for 1 day or more.

The water content here is% by weight.

[0011]

[Chemical 2] _{X: -, O, C (} CH 3) 2, SO 2, S Y: COO, O, OOC R 1: (CH 2) l l: 1~4 R 2, R 3: H or a carbon number from 1 to 4 Alkyl group R ⁴ : (CH ₂ ) _n n: 2-4 m: 10 or more integer Next, the detail of the evaluation method of the physical-property value of the film in this invention is described.

Evaluation Method [Initial Moisture Content] After moisture conditioning of the film at 23 ° C. and 55% RH for 3 days, a trace moisture meter (for example, manufactured by Mitsubishi Kasei Co., Ltd.)
CA-05 type) at a drying temperature of 150 ° C. The water content is expressed in% by weight. After the preparation of the light-sensitive material, the silver halide emulsion layers on both sides and / or coated on the support of the light-sensitive material
Alternatively, the gelatin back layer or the like can be peeled by using pancreatin or an aqueous solution of sodium hypochlorite, and the measurement is almost the same.

[Increase in water content] Film at 23 ° C., 5
After humidity conditioning at 5% RH for 3 days, it is immersed in warm water at 38 ° C for 7 minutes, and then excess water is wiped off with a gauze, and a trace moisture meter (for example, CA-05 type manufactured by Mitsubishi Kasei Co., Ltd.) is used for drying temperature. It was carried out at 150 ° C. Then, the initial water content was subtracted from the water content for calculation. Moisture content is expressed in weight percent. After the preparation of the light-sensitive material, the silver halide emulsion layer and / or the gelatin back layer on both sides coated on the support of the light-sensitive material are peeled off using pancreatin or an aqueous solution of sodium hypochlorite. However, since they are almost the same, the measurement may be performed after peeling in this way.

The present invention will be described in detail below. The film of the present invention has an initial water content of 0.3 to 1%,
After soaking in warm water at 8 ℃ for 7 minutes, the increase in water content is 0.3
% To 1.5%, characterized in that the film is a copolyester containing an aromatic dicarboxylic acid having a metal sulfonate group, preferably further at least represented by Formula B: A photographic support containing one or more of a compound and / or a derivative thereof, a saturated aliphatic dicarboxylic acid, a compound represented by the chemical formula A and / or a derivative thereof.

The initial water content is preferably 0.5 to 0.8%
Therefore, the increment of water content is preferably 0.7 to 1.3%. If the initial water content exceeds 1%, the curl becomes noticeable during long-term storage, and the curl does not disappear in a short-time development process. Even if the initial water content is 1% or less, the water content is less than 1%. If the increase is less than 0.3%, the curl does not disappear in the short-time or rapid processing type development processing. Further, when the increase in the water content exceeds 1.5%, the curl is eliminated, but there is a problem that the perforated portion is deformed or torn off while being conveyed by the developing processor.

The film of the present invention may be composed of a single layer of copolyester, and when laminated, it may be composed of two or three layers.
The polyester layer or the copolyester layer of the present invention has a thickness of 2 μm or more, and the undercoat layer and the like are not included therein. In the case of stacking, two or three layers are generally preferable from the viewpoint of complicating the manufacturing equipment.
In the case of three or more layers, within the range that does not impair the effects of the present invention,
The inner layer is a polyester layer and the outer layer is a copolyester layer,
Alternatively, the outer layer may be a polyester layer and the inner layer may be a copolyester layer.

The polyester used in the laminated polyester film of the present invention is a polyester having a dicarboxylic acid and a diol as main constituents, preferably an aromatic dibasic acid and a glycol as main constituents. There are terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and the like. As glycols, ethylene glycol, propylene glycol, butanediol,
Examples include neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol and p-xylene glycol. Among them, polyethylene terephthalate containing terephthalic acid and ethylene glycol as main constituents and polyethylene-2,6-naphthalate containing 2,6-naphthalenedicarboxylic acid and ethylene glycol as main constituents are preferable. In addition, within the range that the original excellent properties of polyester are not impaired, the main repeating unit of these is 8
It may be a copolymer of 5 mol% or more, or may be blended with another polymer. The intrinsic viscosity of the polyester is preferably 0.45 to 0.80, and particularly preferably 0.55 to 0.70. If it exceeds this range, the stretchability during the production of a laminated film may be deteriorated, which is not preferable.

The copolyester used in the single-layer or laminated polyester film of the present invention comprises an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component, a dicarboxylic acid and a diol as main constituents, and preferably an aromatic dicarboxylic acid. It is a copolyester mainly composed of a dibasic acid and glycol, and the dibasic acid includes terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, etc., and the glycol is ethylene glycol,
Examples include propylene glycol, butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol and p-xylene glycol. Among them, copolymerized polyethylene terephthalate containing terephthalic acid and ethylene glycol as main constituents
Copolymerized polyethylene-2,6-naphthalate containing 6-naphthalenedicarboxylic acid and ethylene glycol as main constituents is preferred. The intrinsic viscosity of the copolyester is preferably 0.35 to 0.75, and particularly preferably 0.45 to 0.65. If it exceeds this range, the stretchability during the production of a laminated film may be deteriorated, which is not preferable.

The aromatic dicarboxylic acid containing a metal sulfonate group of the present invention includes 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 4-sodium sulfoterephthalic acid and 4-sodium sulfo-2,6.
-Naphthalenedicarboxylic acid and the like, and ester-forming derivatives thereof and compounds obtained by substituting these sodiums with other metals (potassium, lithium, etc.) may be used.

[Structure of Laminated Polyester Film] In the present invention, the initial water content and the increase in water content are set within the specified ranges to improve the curl resolving property in a short time treatment and prevent the mechanical strength from deteriorating and causing film deformation. To avoid
In the case of a laminated film, the thickness of each layer can be appropriately determined depending on the polyester and the copolyester used, but preferably the ratio of the total thickness d ₂ of the copolyester layer to the thickness d ₁ of the polyester layer is 0.7. ≤ d ₂
/ D ₁ ≦ 3, more preferably 1 ≦ d ₂ / d ₁ ≦ 2, and the thickness of one polyester layer is preferably 50 μm or less, more preferably 40 μm or less. The total thickness of the support is not particularly limited, but is preferably 40 to 100 μm, particularly preferably 50 to 90 μm. As the tank configuration, from the viewpoint of eliminating the curl in a short time treatment, two layers, three layers are preferable, and particularly preferably, in the case of laminating a polyester layer as an inner layer and a copolyester layer as an outer layer in a three-layer configuration. preferable.

In the case of laminating, in the case of including two layers, three layers, and in the case of a constitution of four or more layers, the film of the present invention is curled in the width from the viewpoint of protection of the emulsion layer and handling after processing. Is preferred, and it is preferred that the layer structure is asymmetric above and below the plane that divides the total thickness of the film of the present invention in half. Furthermore, in the case of a three-layer structure,
In consideration of handling property after treatment and elimination of curl, it is preferable that both outer layers have different thicknesses. When the thickness of each outer layer is d _A and d _B , the ratio d _A / d _B is not particularly limited, but preferably 1.1
≦ d _A / d _B ≦ 5, particularly preferably 1.5 ≦ d _A / d _B
≦ 3. In order to improve the handleability after the treatment, in addition to the difference in the thickness of both outer layers, the main constituents or the amount of main constituents of the polyester species of the upper and lower layers constituting the outer layers of the laminated film are different, or the copolymerization component is different. Alternatively, it is preferable that the amount of the copolymerization component is different, and further that the intrinsic viscosity is different.

The asymmetry of these laminated films can be measured using various analytical instruments, and the layer structure can be confirmed by observing the cross section of the film with a microscope and taking a micrograph. Further, the film is subjected to microscopic observation to shave off each layer, or shave from the top and bottom of the film up to the surface at which the film is divided into halves to obtain the analytes of the upper and lower layers, respectively, and perform liquid chromatography, NM
The asymmetry can be measured by measuring R, GPC (gel permeation chromatography), intrinsic viscosity, IR (infrared spectroscopic instrument) and the like. When the film of the present invention has a width curl, it is necessary to use the film of the present invention in the form of a roll with the concave surface thereof unwound when the film is used in the form of a roll.

[Single-Layer Polyester Film] When the film of the present invention comprises a single-layer polyester layer,
In order to prevent the deformation of the film by improving the initial water content and increasing the water content within the specified range to improve the curl resolving property in a short-time treatment, the polyester layer is preferably a copolyester layer or a polyester containing a copolyester. It is preferably a blended monolayer. The film thickness of the single-layer film is preferably 40 to 100 μm, more preferably 60 to 90 μm in order to eliminate curl and prevent film deformation.

The copolyester used in the present invention will be described in more detail. Regarding the copolymerization component,
In order to eliminate the curl habit and prevent the film from deforming, the copolymerized polyester used should contain 3 to 10 mol% of an aromatic dicarboxylic acid having a metal sulfonate group based on all ester bonds. Is preferred, and further preferably at least a compound represented by the chemical formula B and / or a derivative thereof, a saturated aliphatic dicarboxylic acid,
It contains one or more of the compound represented by the chemical formula A and / or its derivative, and the amount of the copolymerization component is the compound represented by the chemical formula B and / or its derivative, and the saturated aliphatic dicarboxylic acid is based on the whole polymer. 5 to 10% by weight, for compound A 3 to all ester bonds
It is particularly preferable to contain 10 mol%.

In particular, when the film of the present invention is a single layer, it is preferable that the aromatic dicarboxylic acid having a metal sulfonate group is contained in an amount of 3 to 6 mol% based on all ester bonds in order to prevent deformation of the film. From the viewpoint of eliminating curl habit of short-time treatment, one or more of a compound represented by the chemical formula B and / or a derivative thereof, a saturated aliphatic dicarboxylic acid, a compound represented by the chemical formula A and / or a derivative thereof. And a compound represented by the chemical formula B and / or a derivative thereof as the amount of the copolymerization component, and a saturated aliphatic dicarboxylic acid of 5 to 7 with respect to the total polymer.
% By weight, for compound A 3 for all ester bonds
It is particularly preferable that the content is up to 6%.

The compound represented by the chemical formula B of the copolymerization component in the present invention includes polyalkylene glycol or polyalkyleneoxydicarboxylic acid.

As the copolymerization component, polyalkylene glycol is particularly preferable from the viewpoint of curl resolving ability, and polyethylene glycol, polytetramethylene glycol or the like is used, and the molecular weight is not particularly limited, but it is 300 to 20.
000, preferably 600 to 10000, particularly preferably 1000 to 5000. Polyethylene glycol is particularly preferable as the polyalkylene glycol.

As the polyalkyleneoxydicarboxylic acid, polyethyleneoxydicarboxylic acid, polytetramethyleneoxydicarboxylic acid or a derivative thereof may be used, and the molecular weight is not particularly limited, but it is 600 to 2000.
0, preferably 1000 to 10000, particularly preferably 2000 to 5000. In particular, as the polyalkyleneoxydicarboxylic acid, polyethyleneoxydicarboxylic acid or its derivative is preferable from the viewpoint of curl resolving property.

As the saturated aliphatic dicarboxylic acid, for example, an ester-forming derivative is actually used, and for example, dimethyl adipate, dimethyl sebacate, which is an ester of adipic acid or sebacic acid, is used. Dimethyl adipate is preferred.

The copolymerized polyester used in the present invention may be further copolymerized with other components or may be blended with other polymers as long as the effects of the invention are not impaired.

Both the polyester and the copolyester used in the present invention are phosphoric acid, phosphorous acid and their esters and inorganic particles (silica,
Kaolin, calcium carbonate, calcium phosphate, titanium dioxide, etc.) may be contained, or the polymer may be blended with inorganic particles after the polymerization. Further, a pigment, an ultraviolet absorber, an antioxidant, etc. may be added appropriately at any stage of the polymerization and after the polymerization.

To obtain the copolyester resin constituting the support of the present invention, melt polymerization may be carried out after the above-mentioned copolymerization component is added after transesterification, or the copolymerization component may be added before transesterification. Melt polymerization may be carried out after transesterification using the above mixture, or it may be carried out by a known synthesis method such as solid phase polymerization of the polymer obtained by melt polymerization.

The polyester film used in the present invention may contain various additives. For example, light piping phenomenon (flickering) that occurs when light enters the film coated with a photosensitive emulsion layer from the edge.
A dye may be added to the polyester film for the purpose of preventing the above phenomenon. The type of film dye is not particularly limited, but in the polyester film forming process,
Those having excellent heat resistance are preferable, and examples thereof include anthraquinone chemical dyes. Further, as a film color tone, gray dyeing is preferable as seen in general light-sensitive materials, and one kind or two or more kinds of dyes may be mixed and used.

The method for producing a polyester film having a single layer according to the present invention will be described. The method for obtaining the unstretched sheet is not limited and may be a conventionally known method. For example, after sufficiently drying the obtained resin, it is melt-extruded into a sheet through a filter and a die, and cast on a rotating cooling drum to be cooled and solidified. There is a method of doing. As a method of biaxially stretching the finished sheet, biaxial stretching is performed in the temperature range of glass transition temperature (Tg) to Tg + 100 ° C.
For example, the following processes (A) to (D) can be adopted.

(A) A method in which an unstretched sheet is first stretched in the machine direction and then stretched in the transverse direction. (B) A method in which an unstretched sheet is first stretched in the transverse direction and then in the longitudinal direction. (C) A method in which an unstretched sheet is stretched in the longitudinal direction in one or multiple stages, then stretched in the longitudinal direction again, and then stretched in the transverse direction. (D) A method in which an unstretched sheet is stretched in the longitudinal direction in one stage or in multiple stages, then stretched in the transverse direction, and then stretched in the longitudinal direction again.

The above stretching is performed in an area ratio of 4 to 1 in order to satisfy the mechanical strength and dimensional stability of the film support.
It is preferable to carry out in a range of 6 times. Also, heat setting is 1
It can be performed in a temperature range of 50 to 240 ° C. Also,
The method for producing a film comprising the laminate of the present invention includes, for example, melt-extruding polyester and copolyester from separate extruders, and then extruding the melted polymer in a conduit or in an extrusion die by joining them in a laminar fashion in multiple layers. , A method of cooling and solidifying on a cooling drum to obtain an unstretched film, then biaxially stretching and heat setting, or a polyester or copolymerized polyester simple substance and a laminated film are melt-extruded from an extruder and cooled and solidified on a cooling drum. The surface of the unstretched film or the uniaxially oriented film obtained by uniaxially stretching the unstretched film is coated with an anchor agent, an adhesive, etc., if necessary, and then a polyester or copolymerized polyester simple substance and a laminated film are extrusion laminated. And then heat set after completing biaxial stretching And the like emission lamination methods, co-extrusion method from simplicity of process is preferred.

In this case, the stretching conditions of the film are not particularly limited, but generally, the Tg of the polyester layer or the copolyester layer having the higher glass transition temperature (Tg) is used.
It is possible to adopt the methods A to D and the like in the biaxial direction in the temperature range of 1 to Tg + 100 ° C. in the biaxial direction. The stretching ratio is preferably in the range of 4 to 16 times in area ratio. Also, heat setting is 150-24
It can be carried out in the temperature range of 0 ° C. The film of the present invention is applicable to various photographic supports currently known, but is particularly useful as a photographic support used in a roll-shaped film.

The film of the present invention constitutes a silver halide photographic light-sensitive material by having at least one silver halide emulsion layer on at least one side thereof. At least one emulsion layer may be provided on one side of the support, or at least one layer or two or more layers may be provided on both sides of the support. In the case of a support having curl within the present invention, 23 ° C., 55% R
At least one silver halide emulsion layer is provided on the convex side of the support in an H 2 atmosphere. This silver halide emulsion layer can be coated directly on the support, or can be coated via another layer such as a hydrophilic colloid layer containing no light-sensitive silver halide emulsion. A hydrophilic colloid layer as a protective layer may be coated on the silver halide emulsion layer. The silver halide emulsion layer may be coated separately in two or more layers having different color sensitivities, and further different sensitivity, for example, high sensitivity and low sensitivity (and intermediate sensitivity) of each halogenation. The silver emulsion layers may be separately coated. 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, or on the back surface side, an intermediate layer, a protective layer,
A non-photosensitive hydrophilic colloid layer such as an antihalation layer or a backing layer may be provided.

The silver halide used in the silver halide photographic light-sensitive material utilizing the photographic support of the present invention may be of any composition. For example, silver chloride, silver chlorobromide,
There are silver chloroiodobromide, silver bromide or silver iodobromide or mixtures thereof.

A sensitizing dye, a plasticizer, an antistatic agent, a surfactant, a hardener and the like can be added to the silver halide emulsion and / or other hydrophilic colloid used in the present invention. To develop the silver halide photographic light-sensitive material of the present invention, for example, T.W. H. James The Theory Of The Photographic Process 4th Edition (The
Theory of the Photographi
c Process, Fourth Edition)
Pages 291-334 and the Journal of the American Chemical Society (Journal o
f theAmerican Chemical So
Citiy, Vol. 73, page 3100 (1951).

[0041]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these. Example 1 To 100 parts by weight of dimethyl terephthalate and 64 parts by weight of ethylene glycol, 0.1 part by weight of a hydrate of calcium acetate as an ester exchange catalyst was added, and a transesterification reaction was carried out by a conventional method. 5-sodium sulfo-di (β-hydroxyethyl) isophthalic acid (abbreviation:
SIP) ethylene glycol solution (concentration 35% by weight)
28 parts by weight, polyethylene glycol (abbreviation: PEG)
(Number average molecular weight: 3000) 8 parts by weight, antimony trioxide 0.05 parts by weight, phosphoric acid trimethyl ester 0.13
In parts by weight, Irganox 1010 (C
IBA-GEIGY) 0.2 parts by weight and sodium hydroxide 0.02 parts by weight were added. Then, the temperature was gradually raised and the pressure was reduced to carry out polymerization at 280 ° C. and 0.5 mmHg to obtain a copolyester having an intrinsic viscosity of 0.55.

1 each of this copolyester and commercially available polyethylene terephthalate (intrinsic viscosity 0.65)
After vacuum drying at 50 ° C, 285 ° C using three extruders
Was melt-extruded, and the three layers were joined in layers in a T-die so that each layer was made of the materials shown in Table 1, and rapidly solidified on a cooling drum to obtain a laminated unstretched film. At this time, the extrusion amount of each material was adjusted and the thickness of each layer was changed as shown in Table 1. Then, after longitudinal stretching (3.4 times) at 85 ° C, the temperature is 95 ° C.
After transverse stretching (3.4 times), the film was heat set at 210 ° C. to obtain a biaxially stretched film having a thickness of 80 μm. The physical properties of the film are shown in Table 1.

(Preparation of Photosensitive Material) (Undercoating) Unless otherwise specified, the following g to mg indications indicate amounts per m ² . Both sides of the film of the support are subjected to a corona discharge treatment of 8 W / m ² · min,
On one surface, apply the following subbing coating solution B-3 to a dry film thickness of 0.8 μm.
As a subbing layer B-3, and a subbing layer B-4 below on the side opposite to the subbing layer B-3 with a support interposed therebetween so as to have a dry film thickness of 0.8 μm. It was applied as B-4.

However, if the support film is at 23 ° C. and 55
In the case of having a curl in the width of% RH, the undercoat layer B-3 was coated on the convex surface of the support film, and the undercoat layer B-4 was coated on the opposite side.

Coating liquid B-3 Copolymer latex liquid (30% solid content) of 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of butylene and 25% by weight of 2-hydroxyethyl acrylate (270 g) Compound (UL-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Make up to 1000 ml with water.

Coating liquid B-4 Copolymer latex liquid of butyl acrylate 40% by weight, styrene 20% by weight and glycidyl acrylate 40% by weight (solid content 30%) 270 g Compound (UL-1) 0.6 g Hexa Methylene-1,6-bis (ethylene urea) 0.8 g Make up to 1000 ml with water.

Further, a corona discharge treatment of 8 W / m ² · min was performed on the undercoat layer B-3 and the undercoat layer B-4, and the following coating solution B- was formed on the undercoat layer B-3. 5 for dry film thickness 0.1μ
As the undercoat layer B-5 having a thickness of m, the following coating solution B-6 is provided on the undercoat layer B-4 so as to have a dry film thickness of 0.8 μm and having an antistatic function. It was applied as B-6.

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 having an average particle size of 3 μm 0.1 g Water 1000 ml To finish.

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 Water to make 1000 ml.

The structures of the compounds used are summarized below. 25 W / m ² · min corona discharge treatment was applied on the undercoat layer B-5, and 8 W / m ² · mi was applied on the undercoat layer B-6.
n corona discharge treatment was performed. Further, the following emulsion layers and the like were formed on the subbing layer B-5, and the following backing layer was formed on B-6 from the side of the support to prepare a multilayer color photographic light-sensitive material.

Backing layer 1st layer Gelatin 4.5 g Sodium-di-(-2-ethylhexyl) -sulfosuccinate 1.0 g Sodium tripolyphosphate 76 mg Citric acid 16 mg Carboxyalkyl dextran sulfate 49 mg Vinyl sulfone type hardener 23 mg

Second layer Gelatin 1.5 g Polymer beads (average particle size 3 μm polymethylmethacrylate) 24 mg Sodium-di-(-2-ethylhexyl) -sulfosuccinate 15 mg Carboxyalkyl dextran sulfate 12 mg Vinyl sulfone type hard film 30 mg Fluorine-based surfactant ((a) + (b)) total (molar ratio 1: 1) 20 mg

[0053]

[Chemical 3]

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 Particle 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 DIR compound (D-2) 0.01 g High boiling point solvent (Oil-1) 0.55 g Gelatin 1 0.0 g

Fourth layer: High-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (average grain size 0.7 μm, average iodine content 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 point solvent (Oil-1) 0. 25g gelatin 1.0g

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, average iodine content 8.0 mol%) 0.6 g Silver iodobromide emulsion (average Particle 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) g Sensitizing dye (S-7) 2.0 × 10 ⁻⁴ (mol / silver 1 mol) g Sensitizing dye (S-8) 0.3 × 10 ^-4 (mol / silver 1 mol) g Magenta coupler (M-1) 0.30 g Magenta coupler (M-2) 0.13 g Colored cyan coupler (CC-1) 0.04 g DIR compound (D-2) 0.004g High boiling point solvent (Oil-1) 0.35g Gelatin 1.0g

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

Ninth layer: 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 Particle size 0.4 μm, average iodine content 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

Layer 10: High-sensitivity red-sensitive emulsion layer (BH) Silver iodobromide emulsion (average grain size 0.8 μm, average iodine content 8.5 mol%) 0.5 g Sensitizing dye (S-10 ) 3.0 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-11) 1.2 × 10 ⁻⁴ (mol / silver 1 mol) Yellow coupler (Y-1) 0.18 g Yellow coupler ( Y-2) 0.10 g High boiling point solvent (Oil-2) 0.05 g Gelatin 2.0 g

Eleventh layer: First protective layer (PRO-1) Silver iodobromide emulsion (average particle size 0.08 μm) 0.3 g Ultraviolet absorber (UV-1) 0.07 g Ultraviolet 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-2) 0.07 g Gelatin 0.8 g

Twelfth layer: Second protective layer (PRO-2) Compound (WAX-1) 0.04 g Compound (SU-3) 0.004 g Polymethyl methacrylate (average particle size 3 μm) 0.02 g Methyl methacrylate: ethyl Methacrylate: methacrylic acid = 3: 3: 4 (weight ratio) copolymer (average particle size 3 μm) 0.13 g Gelatin 0.7 g

The silver iodobromide used in the 10th layer was prepared by the following method. A silver iodobromide emulsion was prepared by a double jet method using monodisperse silver iodobromide grains (silver iodide content 2 mol%) having an average grain size of 0.33 μm as seed crystals. Solution (G-
1) is maintained at a temperature of 70 ° C., pAg 7.8 and pH 7.0,
A seed emulsion corresponding to 0.34 mol was added with thorough stirring.

(Formation of Internal High Iodity Phase-Core Phase) After that, while maintaining a flow ratio of (H-1) and (S-1) of 1: 1, the accelerated flow rate (the flow rate at the end is Initial flow rate 3.
6 times) and was added over 86 minutes.

(Formation of External Low Iodity Phase-Shell Phase) Subsequently, while maintaining pAg 10.1 and pH 6.0, (H-
2) and (S-2) were added at a flow rate accelerated by the flow rate ratio (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 were formed, they were washed with water by a conventional flocculation method, and then gelatin was added to redisperse them, and the pH and pAg were adjusted to 5.8 and 8.06 at 40 ° C., respectively. The obtained emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 μm, a distribution width of 12.4% and a silver iodide content of 8.5 mol%.

(G-1) Ocein gelatin 100.0 g Compound-1 25.0 ml 28% aqueous ammonia solution 440.0 ml 56% acetic acid aqueous solution 660.0 ml Water 5000.0 ml Compound-1: polypropyleneoxy polyethyleneoxy di 10% ethanol solution of disodium succinate

(H-1) Ocein gelatin 82.4 g Potassium bromide 151.6 g Potassium iodide 90.6 g 1030.5 ml with water

(S-1) Silver Nitrate 309.2 g 28% Aqueous Aqueous Solution Equivalent Water 1030.5 ml

(H-2) Ocein gelatin 302.1 g Potassium bromide 770.0 g Potassium iodide 33.2 g Water 3776.8 ml

(S-2) Silver Nitrate 1133.0 g 28% Aqueous Aqueous Solution Equivalent Water 3776.8 ml

In the same manner, the average grain size of the seed crystal, the humidity,
The emulsions having different average grain sizes and silver iodide contents were adjusted by changing pAg, pH, 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 to obtain a sensitizing dye, a stabilizer ST-1,
Antifoggant AF-1 was added. The above-mentioned photosensitive materials further include compounds Su-1, Su-2, viscosity modifiers, hardening agents H-1, H-2, stabilizers ST-1, antifoggants 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 ).

The structures of the compounds used for forming the photographic constituent layers are shown below. UL-3: 1,3,5-triacryloyl-hexahydro-1,3,5-triazine Oil-1: dioctyl phthalate Oil-2: tricresyl phosphate Oil-3: dibutyl phthalate HS-1: hydantoin HS-2 : 4-ureidohydantoin H-1: 2,4-dichloro-4-hydroxy-s-triazine sodium salt H-2: bis (vinylsulfonylmethyl) ether SU-1: sodium tri (i-propyl) naphthalenesulfonate SU-2: sulfosuccinic acid dioctyl ester / sodium salt SU-3: sulfosuccinic acid di (2,2,3,3,4,4,4)
5,5,6,6,7,7-dodecylfluoroheptyl)
Ester sodium salt ST-1: 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene AF-1: 1-phenyl-5-mercaptotetrazole AF-2: Poly-N-vinylpyrrolidone

[0077]

[Chemical 4]

[0078]

[Chemical 5]

[0079]

[Chemical 6]

[0080]

[Chemical 7]

[0081]

[Chemical 8]

[0082]

[Chemical 9]

[0083]

[Chemical 10]

[0084]

[Chemical 11]

Evaluation Method The prepared silver halide photographic light-sensitive material was evaluated as follows and is shown in Table 1. (Sample No. 1) Twenty photosensitive materials having a width of 35 mm and a length of 120 cm were used. After perforating the light-sensitive material, winding it on a winding core having a diameter of 10.8 mm,
Heat treatment was performed at 20% RH for 4 hours. After that, the core was released, and ordinary development processing was performed with a minilab type film development processor (drying temperature 60 ° C.) used in the market.

<< Perforated Shape >> The following three grades were evaluated.
There is no problem if the grade is practically △, but ○ is preferable.
Grade is required. ◯: Percentage of deformed perforations less than 2% Δ: Percentage of deformed perforations 2-5
% X: The proportion of the number of deformed perforations exceeds 5%, or the perforations are torn off.

<< Removal of curl tendency >> 20 after the above development processing
Five books were randomly selected and evaluated. After development 2
Under the atmosphere of 3 ° C. and 55% RH, the outside of the film was grabbed and hung to adjust the humidity for 1 day. The length of the portion 12 cm from the tip corresponding to the core when naturally hanging was measured, the ratio to the original length was obtained, and the average of 5 was evaluated in the following 3 stages. A grade of ○ is required for the performance of photographic film. ◎: Over 70% ○: 50-70% ×: Less than 50% << Curl width >>

The sample after the above development treatment was cut out in the lengthwise direction at 2 mm and evaluated. After the humidity was controlled for 1 day under an atmosphere of 23 ° C. and 55% RH, the width of the curl was measured. The photographic film needs to have an appropriate curl so that the emulsion surface is not damaged, and the evaluation is performed according to the following three grades. The curl here is the radius of curvature measured as plus when the emulsion surface side is concave. On the performance of photographic film, △ is no problem,
A grade of ◯, particularly ◎ is preferable. ^{◎: 10~25m -1 ○: 5~10,25~35m -1} △: 0~5,35~40m -1 ×: over the emulsion surface is convex, the 40 m ^-1

Example 2 The copolyester obtained in Example 1 and a commercially available polyethylene terephthalate (intrinsic viscosity 0.65) were each vacuum dried at 150 ° C., and then each of the three layers was made of the materials shown in Table 1. A biaxially stretched film having a film thickness of 80 μm and a film thickness of 100 μm was obtained in the same manner as in the method of Example 1 except that the above operation was performed. The emulsion layer and the backing layer were applied in the same manner as in Example 1 to prepare a light-sensitive material, and the same evaluation results are shown in Table 1. (Sample Nos. 2 to 4)

Comparative Example 1 The copolyester obtained in Example 1 and a commercially available polyethylene terephthalate (intrinsic viscosity 0.65) were respectively vacuum-dried at 150 ° C., and the polyester layer was formed on both sides of the copolyester layer. A biaxially stretched film having a film thickness of 100 μm was obtained in the same manner as in Example 1 except that the three layers were formed from the materials shown in Table 1.
The emulsion layer and the backing layer were applied in the same manner as in Example 1 to prepare a light-sensitive material, and the same evaluation results are shown in Table 1. (Sample No. 5)

Comparative Example 2 The copolyester obtained in Example 1 and a commercially available polyethylene terephthalate (intrinsic viscosity 0.65) were each vacuum dried at 150 ° C., and then a copolyester layer 3 was formed on both sides of the polyester layer. Layers were prepared in the same manner as in Example 1 except that each layer was made of the material shown in Table 1.
A biaxially stretched film having a film thickness of 80 μm and 100 μm was obtained.
The emulsion layer and the backing layer were applied in the same manner as in Example 1 to prepare a light-sensitive material, and the same evaluation results are shown in Table 1. (Sample Nos. 6 to 8)

Example 3 A copolyester having the same composition as in Example 1 and a commercially available polyethylene terephthalate (intrinsic viscosity 0.65) were each vacuum dried at 150 ° C., and then two extruders were used to
A biaxially stretched film having a thickness of 80 μm and a thickness of 65 μm was obtained in the same manner as in Example 1 except that each layer was made of the materials shown in Table 1. The emulsion layer and the backing layer were the same as in Example 1. Table 1 shows the results of coating and producing a light-sensitive material and similarly evaluated. (Sample Nos. 9 and 10)

Comparative Example 3 The copolyester obtained in Example 1 was vacuum dried at 150 ° C., and then 28 from the T-die using one extruder.
The film was melt extruded at 0 ° C. and rapidly cooled on a cooling drum to obtain an unstretched film. This unstretched film is preheated to 80 ° C., longitudinally stretched at 80 ° C. (3.4 times), laterally stretched at a temperature of 80 ° C. (3.4 times), and further heat set at 210 ° C. to obtain a film thickness. An 80 μm biaxially stretched film was obtained.
The emulsion layer and the backing layer were applied in the same manner as in Example 1 to prepare a light-sensitive material, and the results of the same evaluation are shown in Table 1. (Sample No. 11)

Comparative Example 4 Commercially available polyethylene terephthalate (intrinsic viscosity 0.6
After vacuum-drying 5) at 150 ° C., a single extruder was used to perform melt extrusion into a film form at 285 ° C. from a T-die, followed by rapid cooling on a cooling drum to obtain an unstretched film.
This unstretched film was preheated to 95 ° C. and longitudinally stretched (3.3
After that, the film was transversely stretched (3.3 times) at a temperature of 95 ° C. and further heat-set at 220 ° C. to obtain a biaxially stretched film having a thickness of 80 μm. The emulsion layer and the backing layer were applied in the same manner as in Example 1 to prepare a light-sensitive material, and the results of the same evaluation are shown in Table 1. (Sample No. 12)

[0095]

[Table 1]

When the initial water content and the increase in water content of the present invention are within the stipulations of the present invention, not only the perforation shape but also the minilab which is developed in a short time of 7 minutes is excellent in eliminating curl habit. It can be seen that if the water content or the increase in water content is outside the scope of the present invention, either the shape of the perforation or the curl resolving property after development is poor, and it is not practical for photography. Further, the film of the present invention is excellent in curl of the width and is particularly useful for photography. On the other hand, those other than the present invention are inferior to the film of the present invention in eliminating curl habit.

Example 4 and Comparative Example 5 Sample No. 1 of Example 1 A biaxially stretched film having the film thickness shown in Table 2 was obtained in the same manner as in Example 1 except that the take-up speed of the cooling drum was changed and the total film thickness of the laminated unstretched film was changed. The emulsion layer and the backing layer were coated in the same manner as in Example 1 to prepare a light-sensitive material, and the results of the same evaluation are shown in Table 2. (Sample Nos. 13 to 17)

[0098]

[Table 2]

Those having an initial water content and an increased water content of the present invention within the specifications of the present invention are excellent in the perforation shape, curl resolving property, and curl of the width, but the increased initial water content and the increased water content. However, those not satisfying the requirements of the present invention are inferior in either the shape of the perforation or the curl resolving property after development processing.

Example 5 and Comparative Example 6 100 parts by weight of dimethyl terephthalate, 64 parts by weight of ethylene glycol, SE-2 (manufactured by Meisei Chemical Industry Co., Ltd.) (see Table 3 for added parts by weight) were used as acetic acid as an ester exchange catalyst. 0.1 parts by weight of calcium hydrate was added, and transesterification reaction was carried out by a conventional method. The obtained product was added to a solution of 5-sodium sulfo-di (β-hydroxyethyl) isophthalic acid (abbreviation: SIP) in ethylene glycol (concentration: 35
28% by weight, polyethylene glycol (abbreviation:
PEG) (number average molecular weight: 3000) (see Table 3 for the addition weight part), 0.05 part by weight of antimony trioxide, 0.13 part by weight of trimethyl ester of phosphoric acid, Irganox 1010 (CIBA-GEIGY company) as an antioxidant. Made)
0.2 parts by weight and 0.02 parts by weight of sodium hydroxide were added. Then gradually raise the temperature and reduce the pressure to 280 ° C.,
Polymerization was performed at 0.5 mmHg to obtain a copolyester having an intrinsic viscosity of 0.55.

Using the obtained copolyester and commercially available polyethylene terephthalate (intrinsic viscosity 0.65),
Using three extruders, a support was prepared in the same manner as in Example 1 (Sample No. 1) by using the same material.
Then, an emulsion layer and a backing layer are applied to prepare a light-sensitive material, and the same evaluation results are shown in Table 3. (Sample No. 1
8-21) The initial water content and the water content increase of the present invention within the stipulations of the present invention are excellent in perforation shape and curl eliminating property,
If the initial water content and the increase in water content are outside the scope of the present invention,
Either the shape of the perforation or the tendency to eliminate the curl after development is poor.

Example 6 To 100 parts by weight of dimethyl terephthalate, 70 parts by weight of ethylene glycol, and 10 parts by weight of dimethyl adipic acid (DMA), 0.1 part by weight of a hydrate of calcium acetate as an ester exchange catalyst was added. Transesterification reaction was carried out. 5-sodium sulfo-di (β
-Hydroxyethyl) isophthalic acid (SIP) in ethylene glycol solution (concentration 35% by weight) 22 parts by weight, antimony trioxide 0.05 parts by weight, trimethyl ester phosphoric acid 0.15 parts by weight, Irganox 1 as an antioxidant
010 (manufactured by CIBA-GEIGY) and 0.04 part by weight of sodium hydroxide were added. Then, the temperature was gradually raised and the pressure was reduced to carry out polymerization at 280 ° C. and 0.5 mmHg to obtain a copolyester having an intrinsic viscosity of 0.55.

In the same manner as in Example 1, except that this copolymerized polyester and commercially available polyethylene terephthalate (intrinsic viscosity 0.65) were used and three extruders were used, the same procedure as in Example 1 was carried out. A biaxially stretched film having a film thickness of 80 μm made of the same material was obtained. Then the emulsion layer,
Table 3 shows the measurement results obtained by coating a backing layer to prepare a light-sensitive material and similarly evaluating it. (Sample No. 22)

Example 7 100 parts by weight of dimethyl terephthalate, 64 parts by weight of ethylene glycol, 28 parts by weight of a solution of 5-sodium sulfo-di (β-hydroxyethyl) isophthalic acid (abbreviation: SIP) in ethylene glycol (concentration 35% by weight) Part, polyethylene glycol (abbreviation: PEG) (number average molecular weight: 1
000) 8 parts by weight, 0.1 part by weight of calcium acetate hydrate as a transesterification catalyst, and 0.05 part by weight of antimony trioxide, 0.13 part by weight of trimethyl ester of phosphoric acid, an example as an antioxidant. Similarly to 1, Irganox 1010 (manufactured by CIBA-GEIGY) was added so as to be 1% by weight with respect to the product polymer to prepare a mixed solution of unreacted materials. Then gradually raise the temperature and reduce the pressure to 1
After transesterification at 70 ° C., polymerization was carried out at 280 ° C. and 0.5 mmHg to obtain a copolyester. Using the obtained copolyester and commercially available polyethylene terephthalate (intrinsic viscosity 0.65), a support was prepared in the same manner as in Example 1 by using three extruders, and a support was prepared in the same manner. A support having a thickness of 80 μm was obtained. Next, the emulsion layer and the backing layer are applied to prepare a light-sensitive material, and the same evaluation results are shown in Table 3. (Sample No. 23)

[0105]

[Table 3]

It can be seen that those having an initial water content and an increased water content of the present invention within the stipulations of the present invention do not impair the perforation shape, and are excellent in curl resolving property and curl of the width.
Further, when combined with the above-mentioned Example 1, in the method for polymerizing the copolyester of the present invention, the copolymerization component may be added after transesterification, or all the polymerization components may be mixed before transesterification and then after transesterification. Polymerization may be performed,
It is understood that the effects of the present invention can be obtained regardless of the polymerization method. However, as a polymerization method, it is preferable to add the copolymerization component after transesterification and perform melt polymerization from the viewpoint of slightly curling habit.

Example 8 and Comparative Example 7 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate,
To 56 parts by weight of ethylene glycol and 15 parts by weight of SE-2 (manufactured by Meisei Chemical Industry Co., Ltd.), 0.1 part by weight of calcium acetate hydrate was added as a transesterification catalyst, and transesterification was carried out by a conventional method. . 5 to the obtained product
A solution of sodium sulfo-di (β-hydroxyethyl) isophthalic acid (SIP) in ethylene glycol (concentration 35
22% by weight, polyethylene glycol (PE
G) (Number average molecular weight: 3000) 10 parts by weight, antimony trioxide 0.04 parts by weight, phosphoric acid trimethyl ester 0.1 part by weight, Irganox 101 as an antioxidant
0 (manufactured by CIBA-GEIGY) and 0.04 part by weight of sodium hydroxide were added. Then, the temperature was gradually raised and the pressure was reduced to carry out polymerization at 285 ° C. and 0.5 mmHg to obtain a copolyester having an intrinsic viscosity of 0.50.

The polymer was vacuum dried at 150 ° C., melt-extruded into a film form at 290 ° C. from a T-die using one extruder, and rapidly cooled on a cooling drum to give an unstretched film. Obtained. At this time, the take-up speed of the cooling drama was changed to change the film thickness of the unstretched film. This unstretched film is preheated to 120 ° C., longitudinally stretched at 120 ° C. (3.2 times), and then transversely stretched at a temperature of 125 ° C. (3.2 times).
Then, heat setting was further performed at 220 ° C. to obtain a single-layer biaxially stretched film having a film thickness as shown in Table 4. Next, the emulsion layer and the backing layer are applied to prepare a light-sensitive material, and the same evaluation results are shown in Table 4. (Sample No. 24-2
9)

[0109]

[Table 4]

Example 9 and Comparative Example 8 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate,
To 56 parts by weight of ethylene glycol and 15 parts by weight of SE-2 (manufactured by Meisei Chemical Industry Co., Ltd.), 0.1 part by weight of calcium acetate hydrate was added as a transesterification catalyst, and transesterification was carried out by a conventional method. . 5 to the obtained product
A solution of sodium sulfo-di (β-hydroxyethyl) isophthalic acid (SIP) in ethylene glycol (concentration 35
22% by weight, polyethylene glycol (PE
G) (Number average molecular weight: 3000) 20 parts by weight, antimony trioxide 0.04 parts by weight, phosphoric acid trimethyl ester 0.1 part by weight, Irganox 101 as an antioxidant
0 (manufactured by CIBA-GEIGY) and 0.04 part by weight of sodium hydroxide were added. Then, the temperature was gradually raised and the pressure was reduced to carry out polymerization at 280 ° C. and 0.5 mmHg to obtain a copolyester having an intrinsic viscosity of 0.55.

This copolymerized polyester and commercially available polyethylene-2,6-naphthalate were mixed in the proportions shown in Table 5, dried in vacuum at 150 ° C., and mixed with T using one extruder.
The film was melt extruded from a die at 280 ° C. and rapidly cooled on a cooling drum to obtain an unstretched film. This unstretched film is preheated to 110 ° C., longitudinally stretched at 110 ° C. (3.2 times), and then transversely stretched at a temperature of 115 ° C. (3.2 times).
Then, heat setting was further performed at 220 ° C. to obtain a single-layer biaxially stretched film having a film thickness as shown in Table 5. Next, the emulsion layer and the backing layer are coated to prepare a light-sensitive material, and the same evaluation results are shown in the table. (Sample No. 30 to 3
4)

[0112]

[Table 5]

From Table 1, Table 4 and Table 5, whether the film is a laminated film or a single layer film, the initial water content and the water content increase of the present invention are within the definition of the present invention. , Which is excellent in curl resolving ability, but whose initial water content and increase in water content are outside the scope of the present invention are perforated,
Either of the curl eliminating properties after development processing is poor. Within the scope of the present invention, the curl of the width is excellent and it is useful for photography. Further, combining Tables 1, 2, and 3 shows that the laminated film of the present invention is more preferable for photographic use than the single-layer film of the present invention in terms of the width curl after development processing. Further, when combined with the above-mentioned examples, an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component in the polyester film of the present invention,
Further, it is found that it is preferable to contain the compound B, the saturated aliphatic dicarboxylic acid, and the compound A.

Example 10 100 parts by weight of dimethyl terephthalate, 64 parts by weight of ethylene glycol, 9 parts by weight of polyethyleneoxydicarboxylic acid (abbreviation: PEO) (number average molecular weight: 3000) and hydrate of calcium acetate as an ester exchange catalyst. 0.1
A part by weight was added, and transesterification was carried out by a conventional method.
35 parts by weight of an ethylene glycol solution of 5-sodium sulfo-di (β-hydroxyethyl) isophthalic acid (abbreviation: SIP) (concentration: 35% by weight), antimony trioxide 0.05 parts by weight, phosphoric acid 0.13 parts by weight of trimethyl ester, Irganox 1 as antioxidant
010 (manufactured by CIBA-GEIGY), 0.2 parts by weight, and sodium hydroxide, 0.02 parts by weight, were added. Then gradually raise the temperature and reduce the pressure to 280 ° C. and 0.5 mmHg.
Polymerization was carried out to obtain a copolyester having an intrinsic viscosity of 0.55. Using the obtained copolyester and commercially available polyethylene terephthalate (intrinsic viscosity 0.65), using three extruders, the same material as in Example 1 and Example 2 was used, and a support was similarly prepared. Was prepared to obtain a support having a film thickness of 80 μm. Next, the emulsion layer and the backing layer are applied to prepare a light-sensitive material, and the same evaluation results are shown in Table 6.
(Sample No. 35 to 37)

[0115]

[Table 6]

It can be seen that those having an initial water content and an increased water content according to the present invention within the stipulations of the present invention do not impair the perforation shape, and are excellent in curl resolving ability and curl of the width.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 23, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Chemical 1]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

[0011]

[Chemical 2] Next, the details of the method for evaluating the physical properties of the film in the present invention will be described.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kenji Nakanishi 1st Sakura-cho, Hino-shi, Tokyo Konica Co., Ltd. (72) Inventor Yoshioki Okubo 2-33-5 Soja-sha, Hofu-shi, Yamaguchi (72) Inventor Hashimura Tetsutaro 1751-15 Nitta, Hofu City, Yamaguchi Prefecture (72) Inventor Hiroshi Naito 2265-5 Yoshikashi, Yamaguchi City, Yamaguchi Prefecture

Claims (3)

[Claims] 1. A polyester having an initial water content of 0.3 to 1% as defined below and an increase in water content of 0.3 to 1.5% after being immersed in warm water at 38 ° C. for 7 minutes. A photographic support, wherein the film is a copolyester containing an aromatic dicarboxylic acid having a metal sulfonate group. Initial moisture content: moisture content of the film after humidity conditioning at 23 ° C. and 55% RH for 1 day or more. The water content here is% by weight. 2. The photographic support according to claim 1, wherein the film is formed by laminating a copolyester layer containing an aromatic dicarboxylic acid having a metal sulfonate group on at least one side of the polyester layer. . 3. An aromatic dicarboxylic acid having a metal sulfonate group is contained as a copolymerization component of the copolymerized polyester in an amount of 3 to 10 mol% with respect to all ester bonds, and
A compound having at least a repeating structure of an alkyleneoxy unit represented by the following chemical formula B and / or a derivative thereof, a saturated aliphatic dicarboxylic acid, and one or more of a compound represented by the following chemical formula A and / or a derivative thereof. The photographic support according to claim 1 or 2. [Chemical 1] _{X: -, O, C (} CH 3) 2, SO 2, S Y: COO, O, OOC R 1: (CH 2) l l: 1~4 R 2, R 3: H or a carbon number from 1 to 4 alkyl group ^{_{R 4: (CH 2) n}} n: 2~4 m: 10 or more integer