JP3467667B2 - Method for producing support for silver halide photographic material and silver halide photographic material - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a support for a silver halide photographic light-sensitive material which is wound into a roll and used, and a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art Conventionally, a silver halide photographic light-sensitive material (hereinafter also simply referred to as a photographic light-sensitive material) is a cellulose fiber-based polymer represented by triacetyl cellulose (hereinafter abbreviated as "TAC"). Alternatively, it is produced by coating at least one silver halide photographic photosensitive layer on a plastic support made of a polyester polymer represented by polyethylene terephthalate (hereinafter abbreviated as “PET”). .

In general, many photographic light-sensitive materials are used in the form of a roll film, and typically, they are stored in a cartridge with a width of 35 mm or less, and are generally loaded into a camera for photographing. Examples thereof include color or black-and-white negative films used for, and black-and-white light-sensitive material films for bright rooms, scanners, facsimiles and the like. TAC is mainly used as a support for a roll film, and the greatest feature of this is that it has no optical anisotropy and high transparency. Further, another advantage is that it has a very excellent property of decurling after development processing.

That is, the TAC support is characterized by its molecular structure and has a high water absorption as a plastic support, and a curl curl developed by being rolled and stored as a roll film absorbs water during development processing. It is considered that the polymer has excellent properties in decurling because the molecular chains move and the immobilized molecular chains rearrange. As a result, it has an excellent property that the curling curl once formed is eliminated.

On the other hand, in a photographic light-sensitive material using a support having no curling curl eliminating property, when it is used in a roll state, for example, scratches are generated in the printing step, defocusing,
Jamming or the like occurs during transportation, and a jamming phenomenon similarly occurs during transportation of a black-and-white photosensitive material film for a bright room, a scanner, a facsimile, or the like.

By the way, since the PET support has excellent mechanical properties, dimensional stability and high productivity, the TAC
However, in the roll form widely used as a photographic light-sensitive material, the curling curl strongly remains, so that the handleability after development processing is poor,
Further, the black-and-white light-sensitive material film used in a rolled state has a poor handling property, and although it has the above-mentioned excellent properties, its range of use has been limited.

Further, when used as a support for a photographic light-sensitive material, it is used at room temperature after being developed and dried. At this time, in the use of the printing material for which the dimensional stability is particularly required, the coefficient of temperature expansion and the coefficient of humidity expansion are required to be small. The dimensional change of the support for photographic light-sensitive material is
It is greatly affected by temperature and humidity. Of these, the effect of temperature is that it is used while carefully avoiding large deformation (heat shrinkage) that occurs at temperatures above the glass transition temperature of the support after development and baking of the photosensitive material. That is, it depends on the temperature change of the use atmosphere. Therefore, the coefficient of thermal expansion is required to be low and controlled so as not to be affected by the temperature change of the atmosphere used. On the other hand, as for the influence of humidity, since the light-sensitive material undergoes the processes of development, fixing and drying, the moisture absorption changes greatly, so the humidity expansion coefficient should be as low as possible in order to eliminate the influence of humidity. Is preferred. The humidity expansion coefficient of the oriented PET support can be controlled to some extent by the film forming conditions, but the polymer species is dominant, and there is a limit to lowering the humidity expansion coefficient. Therefore, it is preferable that the support is at least equal to or less than the current PET support.

From the above viewpoint, since the PET support has a strong curling curl in the form of a roll, the photographic light-sensitive material used in a roll state retains at least the dimensional stability of the PET support and also has a PET support. There has been a strong demand for improvement of the curl curl, which is the biggest drawback of the body.

[0009]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is not to impair the excellent thermal, mechanical, physical, chemical and optical properties of the PET support, and to have excellent dimensional stability. Moreover, it is an object of the present invention to provide a method for producing a support for a silver halide photographic light-sensitive material having less curling curl and excellent in workability and handleability, and a silver halide photographic light-sensitive material using the support.

[0010]

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

(1) A laminated support comprising polyethylene terephthalate as a main constituent and at least two layers of polyethylene terephthalate having different proportions of copolymerization components, wherein the outermost layer is the outermost layer of the support. A layered support having a difference in the proportion of copolymerization components of the constituent layers of 2 mol% or more and 15 mol% or less, a coefficient of thermal expansion of 25 × 10 ⁻⁶ cm / cm / ° C. or less, and a coefficient of humidity expansion of 15 × Of the two layers constituting the outermost layer of the support for a silver halide photographic light-sensitive material having a concentration of 10 ⁻⁶ cm / cm /% RH or less, at least one layer of a light-sensitive halogenated layer is provided on the layer side having a small proportion of copolymerization components A silver halide photographic light-sensitive material having a silver emulsion layer, which is used by being rolled up.

(2) The silver halide photographic light-sensitive material according to (1), wherein the difference in the proportion of the copolymerization components of the layers constituting the outermost layer of the laminated support is 4 mol% or more.

(3) The silver halide photographic light-sensitive material according to (1) or (2), wherein the copolymerization component is at least one selected from adipic acid, cyclohexanedicarboxylic acid, diethylene glycol and neopentyl glycol. material.

(4) The silver halide photographic light-sensitive material described in (1), (2) or (3), which has a curl degree of 80 m ^-1 or less.

(5) The silver halide photographic light-sensitive material as described in (1), (2) or (3), which has a curl degree of 60 m ^-1 or less.

(6) The above (1), (2) or (3)
(Tg ₁ -25) ° C. to (Tg ₂ +60) at the time of forming a film from the laminated support of the support for silver halide photographic light-sensitive materials described above.
At least 3. both vertically and horizontally in the temperature range of ° C.
A method for producing a support for a silver halide photographic light-sensitive material, which comprises stretching at 0 times or more and heat-treating at 200 to 240 ° C. (wherein Tg ₁ and Tg ₂ are each in the polymer constituting the laminated support). Represents the highest and lowest glass transition temperatures).

The present invention will be described in detail below.

The above object of the present invention is a laminated support comprising polyethylene terephthalate as a main constituent and at least two or more layers of polyethylene terephthalate having different ratios of copolymerization components are laminated. Of a laminated support having a difference in the proportion of copolymerization components of the layers constituting the outermost layer of 2 mol% or more and 15 mol% or less, and a temperature expansion coefficient of 25 × 10 ⁻⁶ cm / cm / ° C. or less,
A support for a photographic light-sensitive material having a humidity expansion coefficient of 15 × 10 ⁻⁶ cm / cm /% RH or less, and of the two layers constituting the outermost layer of the support, the layer side to be curled outward.
That is, it is generally achieved by a photographic light-sensitive material which has at least one silver halide emulsion layer on the side having a small proportion of copolymerization components and is wound in a roll shape with the emulsion-coated surface inside. It was

That is, two or more different PET-based polymer layers are laminated, and the two or more different PET-based polymer layers have different ratios of the copolymerization component to the reaction product. . As the copolymerization component, preferably 15 mol% or less of adipic acid, cyclohexanedicarboxylic acid, diethylene glycol or neopentyl glycol monomer may be contained, and 10 mol% or less is preferable. When the content of the copolymerization component is more than 15 mol%, the mechanical properties originally possessed by the PET support are impaired, which is not preferable. Adipic acid as a copolymerization component is added as dimethyl adipic acid. In addition, a support made of a copolymerized PET-based polymer single layer containing up to 15 mol% of these copolymerization components has a higher draw ratio, heat setting temperature, etc. than a support made of a PET homopolymer single layer. If the film conditions are almost the same, the refractive index will be slightly different depending on the kind and proportion of the copolymerization component, but the refractive index will be almost the same.

By the way, the temperature expansion coefficient has a linear relationship with the refractive index, and can be uniquely explained by the refractive index. Therefore,
The coefficient of thermal expansion differs greatly depending on the degree of orientation. The higher the refractive index, the smaller the coefficient of thermal expansion. If the refractive index is the same, the coefficient of thermal expansion is almost the same within the measurement error range. On the other hand, the humidity expansion coefficient is not so remarkable that it depends on the film forming conditions such as the draw ratio and the heat setting temperature as much as the temperature expansion coefficient, but it also has the film forming condition dependency. That is, it has a linear relationship with the refractive index, and can be uniquely explained by the refractive index. Similarly, the coefficient of humidity expansion differs depending on the degree of orientation, and the coefficient of humidity expansion decreases as the refractive index increases. If the refractive index is the same, the humidity expansion coefficient is almost the same within the measurement error range. Particularly, in the case of a support composed of a copolymerized PET-based polymer single layer containing the above-described adipic acid, cyclohexanedicarboxylic acid, diethylene glycol, neopentyl glycol monomer as a copolymerization component, the copolymerization amount up to 15 mol% is sufficient for the copolymerization. If the film forming conditions are almost the same, the humidity expansion coefficient is almost the same as that of a support composed of a PET homopolymer single layer.

On the other hand, it contains polyethylene glycol, polyoxyethylene dicarboxylic acid, sulfoisophthalic acid metal salt, etc., which are the water-absorbing copolymerization components described in JP-A-6-11795 and JP-A-6-240020. Since the support made of a single layer of the copolymerized PET polymer absorbs moisture, it has a much larger coefficient of hygroscopic expansion than the support made of a single layer of PET homopolymer, and is inferior in dimensional stability.

That is, the present invention has a temperature expansion coefficient of 25 ×
10 ^-6 cm / cm / ° C or less, humidity expansion coefficient of 15 × 10
^-6 cm / cm /% RH or less support for photographic light-sensitive material,
Preferably, the coefficient of thermal expansion is 20 × 10 ⁻⁶ cm / cm /
Humidity expansion coefficient of 12 × 10 ^-6 cm / cm /% or less
It is a support for a photographic light-sensitive material of RH or less.

By the way, the temperature and the humidity expansion coefficient of the commercially available homopolyethylene terephthalate (PET) support are measured, and they are various as follows (MD in the longitudinal direction,
The width direction is represented as TD).

1) Temperature expansion coefficient (unit: cm / cm / ° C.) unstretched support / MD / TD: 70 × 10 ⁻⁶ MD uniaxially stretched support / MD: (−6 to −20) × 10 ^{− 6} (Shrinks as temperature rises) TD: (90 to 120) × 10 ⁻⁶ Biaxially oriented balance support / MD / TD: (5 to 50) × 10 ⁻⁶ Vertical tensioned support / MD: (2 Up to 5) × 10 ⁻⁶ · TD: (20 to 40) × 10 ⁻⁶ 2) coefficient of humidity expansion (unit: cm / cm /% RH) unstretched support / MD / TD: 22 × 10 ⁻⁶ MD Uniaxially stretched support: MD: (7-18) × 10 ⁻⁶ · TD: (25-30) × 10 ⁻⁶ Biaxially oriented balance support · MD / TD :: (9-15) × 10 ⁻⁶ vertical Tenshiraizu support · MD: (7~9) × 10 -6 · TD: (11~13) × 10 -6 temperature commercial PET support, Degree expansion coefficient is a different temperature expansion coefficient of the present invention is 25 × 10 ^-6 cm / cm
/ ° C or less, humidity expansion coefficient is 15 × 10 ^-6 cm / cm /%
To satisfy the following RH is, when forming a film of the laminated base material was stretched at _{(Tg 1 -25) ℃ ~ (} Tg 2 +60) Temperature range ° C., the longitudinal and transverse directions both at least 3.0 times It is necessary to perform heat treatment at 200 to 240 ° C.
Although the draw ratio is particularly important, as described above, the temperature and humidity expansion coefficients have a linear relationship with the refractive index, and the higher the refractive index, the smaller the temperature and humidity expansion coefficient. The refractive index and the stretch ratio have a good correlation, but even with the same stretch ratio, the lower the temperature is, the higher the refractive index is, resulting in a smaller temperature and humidity expansion coefficient. Therefore, it is more important to control the refractive index than the draw ratio. Both the longitudinal and lateral refractive indices of the PET support are 1.61 or more, preferably 1.63.
If it is above, the temperature and the humidity expansion coefficient of the PET support of the present invention can be satisfied. If the upper limit of the longitudinal and lateral refractive index of the PET support is a balance type,
The length and width are both about 1.685.

In order to satisfy the above temperature and humidity expansion coefficient ranges, a general stretching temperature, that is, (Tg ₁ -25) ° C.
In the temperature range of (Tg ₂ +60) ° C., both the longitudinal and transverse directions are stretched at least 3.0 times or more, preferably 3.1 times or more and 4.7 times or less, and heat treated at 200 to 240 ° C. , Coefficient of thermal expansion is 25 × 10 ^-6 cm / cm / ° C
Hereinafter, 5 × 10 ⁻⁶ cm / cm / ° C. or higher, a coefficient of humidity expansion of 15 × 10 ⁻⁶ cm / cm /% RH or lower, 9 × 10 ⁻⁶ cm
/ Cm /% RH or more, preferably a coefficient of thermal expansion of 20 ×
10 ^-6 cm / cm / ° C or less, 5 × 10 ^-6 cm / cm / ° C
Above, humidity expansion coefficient is 12 × 10 ^-6 cm / cm /% RH
Hereinafter, a laminated support satisfying 9 × 10 ⁻⁶ cm / cm /% RH or more can be obtained.

By the way, as the copolymerization component of the PET polymer increases, if the film forming conditions (stretching ratio, heat setting temperature) are the same, the orientation is generally suppressed and the temperature and the humidity expansion coefficient tend to increase. PET is a copolymerized PET containing a maximum of 15 mol% of a copolymerization component of adipic acid, cyclohexanedicarboxylic acid, diethylene glycol and neopentyl glycol with respect to the reaction product.
It is possible to obtain the same temperature and humidity expansion coefficient of the present invention as those of the homopolymer simple substance support.

In particular, when adipic acid, cyclohexanedicarboxylic acid, diethylene glycol or neopentyl glycol copolymerized PET is used, the low temperature heat shrinkage is extremely large, and these problems can be easily solved, and it is equivalent to a PET homopolymer simple support. The inventors have found that the temperature and humidity expansion coefficients of the present invention can be obtained and reached the present invention. Of course, it goes without saying that PET containing these copolymerization components may be used in combination.

That is, the degree of curling of the laminated PET-based polymer support varies depending on the type of the copolymerization component, the ratio of the copolymerization component to the reaction product, the thickness of the composition, and the number of layers, but the curl is on one side of the support. Has the following characteristics:
This property is used to eliminate curling curl.

The support of the present invention in which two or more different PET polymer layers are laminated may be laminated in any number, but two or three layers are preferable in view of ease of production. The laminated PET-based polymer support may have different types and ratios of the copolymerization components of the PET-based polymer constituting each layer, and the layers may have different thicknesses.

For the sake of simplicity, the description will be given with examples of two layers and three layers.

In the case of a two-layer laminated PET polymer support,
If the lamination thickness is the same, in the case of the same copolymerization component, the layer having a large ratio of the copolymerization component to the reaction product is placed inside and curled. In this case, the curl shows the maximum when the laminated thickness on the curling side occupies 1/2 of the total thickness. Further, in the case of a combination having the same laminated thickness and the same ratio of the copolymerization component to the reaction product, but in the case of a combination in which the type of the copolymerization component is different, the curling direction differs depending on the combination and cannot be specified. Curls in the direction of, or rarely balances to flatten.

In the two-layer laminated PET-based polymer support, the thickness (m ₂ ) of the inner side of the copolymerized PET-based polymer layer to be curled and the thickness of the outer side of the curled copolymerized PET-based polymer layer ( m ₁ ), that is, a combination of the thickness composition ratios of m ₂ / m ₁ (generally, when the same copolymerization component and the proportion of the copolymerization component of m ₂ are larger than m ₁ , the curl phenomenon described above causes m ₂ to be inside. Occurs in (0 to 0)
100%) / (although there can be a combination of 100% to 0%), from the cost point of view of the laminated PET based polymer support, since the cost copolymerized component is great, m ₂
Is preferable, and the thickness composition ratio of m ₂ / m ₁ is preferably (20 to 50)% / (80 to 5).
0)%, more preferably (30-50)% / (70-
50)% combination is preferable.

In the case of a two-layer laminated PET-based polymer support composed of the same copolymerization component, the copolymerized PET forming both layers
The difference in the proportion of the copolymerization component of the base polymer support is 2 to 15
It is good to be mol%, preferably 4 mol% or more and 15 mol% or less. This extreme combination is
It is a combination of a base polymer and a PET homopolymer. If this range is satisfied, the curling force of the two-layer laminated PET-based polymer support will be the emulsion (gelatin).
Anti-curl force that counters the contraction stress of the tape works as an anti-curl force against curling curl.

In the case of a combination of different types of copolymerization components, the direction and degree of curl differ depending on the combination.
Although it cannot be specified, the emulsion may be coated on the copolymerized PET polymer layer on the outside of the curl with a difference of about 2 to 15 mol%, and the emulsion coated surface may be wound inside and rolled up. .

In the case of a three-layer laminated PET-based support, a copolymerized PET-based polymer layer is laminated on both sides of the central PET-based support. The PET-based support layer of the central layer may be the same as or different from the copolymerized PET layers on both sides, but PET homopolymer is preferable from the viewpoint of cost reduction. When the two layers constituting the copolymerized PET-based polymer layer on both sides have the same laminated thickness and the same kind of the copolymerization component, the side having a large ratio of the copolymerization component to the reaction product is placed inside. Curl. In this case, the curling behavior is maximized if the laminated thickness on the inside curl side is the same as the laminated thickness on the opposite side. Also, in the case of a combination of different types of copolymerization components, the curling direction differs depending on the combination and cannot be specified.

In the case of a three-layer laminated PET-based polymer support, when the outermost layer is composed of the same copolymerization component, the P of the center layer is
Irrespective of the ET polymer support, the difference in the copolymerization components of both layers is 2 to 15 mol%, preferably 4 mol% or more. In the case of a combination of different kinds of copolymerization components, the direction and degree of curl vary depending on the combination and cannot be specified, but similarly 2 to 15 mol%, preferably 4 to 15 mol%, As in the case of the two-layer laminated PET-based polymer support, the emulsion layer may be coated on the copolymerized PET-based polymer layer on the outside of the curl, and the emulsion-coated surface may be wound inside and rolled up.

By utilizing the curling characteristic of the above-mentioned support, curling curl generated by storing the photosensitive material in a direction opposite to the curling direction can be canceled and a flat photographic photosensitive material can be obtained. The material is to be obtained.

The present invention will be described in more detail below. First, the polyethylene terephthalate-based polymer support of the present invention will be described.

In the present invention, a support containing polyethylene terephthalate (PET) as a main constituent mainly means a polyester using terephthalic acid as an acid component and ethylene glycol as a glycol component.
The acid component of the copolymer may be one of bifunctional acids such as adipic acid and cyclohexyl adipic acid, or a copolymer or polymer mixture using 15 mol% or less of two or more of them, and as the glycol component, It may be a copolymer or polymer mixture using 15 mol% or less of one or more diol compounds of diethylene glycol and neopentyl glycol.

The polyethylene terephthalate polymer support may contain stabilizers such as phosphoric acid, phosphorous acid and their esters.

The difference in the ratio of the copolymerization component between the two layers constituting the outermost layer of the laminated PET-type polymer support to the reaction product varies depending on the type of the copolymerization component, the constitutional thickness and the number of layers, but is 2 mol% or more. Then, if the curl degree is 80 m ^-1 or less and 4 mol% or more, 60 m ^-1 or less can be achieved.

The polyethylene terephthalate (PET) polymer used in the present invention is melt-polymerized by a conventionally known method.

The support may contain inorganic fine particles, antioxidants, UV absorbers, antistatic agents, dyes, pigments, dyes, etc., in order to impart functionality, within a range not impairing the object of the present invention. Is possible.

The polymer used for forming the PET polymer film has an intrinsic viscosity of 0.45 to 0.75 (measured at 35 ° C. of o-chlorophenol. The unit is 100 cc / g), preferably 0.1. Those of 50 to 0.70 are used. When the intrinsic viscosity is less than 0.45, it is impossible to obtain a support having excellent film-forming properties and strength characteristics. The upper limit of the intrinsic viscosity is 0. from the viewpoint of film formability (breakage due to increase in stretching tension, etc.) and melt viscosity (filter pressure) increase.
The limit is about 75.

Further, the PET type polymer support of the present invention comprises
PET-based polymer pellets at 120-180 ° C for 1-2
Crystallize and dry for 4 hours under vacuum or atmospheric pressure under an inert gas atmosphere such as air or nitrogen. The moisture content of the target pellets is not particularly limited, but from the viewpoint of preventing the mechanical strength and the like of the support from decreasing due to hydrolysis, it is 0.
It is good to dry it to 05% or less, preferably 0.01% or less. However, these methods are not particularly limited as long as the purpose is achieved.

The laminated PET-type polymer support comprises PET-type polymer pellets having different copolymerization components from 260 to 350.
After being laminated in a laminar flow in a state of being melted at ℃, it is pressed by a T-die and cooled and solidified while electrostatically applied on a casting roll to prepare an unstretched support, or a PET-based unstretched support that is cooled and solidified. Alternatively, a PET-based uniaxially stretched support is extrusion-laminated with a PET-based molten polymer having a different copolymerization component, or the same copolymerization component but a different copolymerization ratio, and then, in both longitudinal and transverse directions or in a uniaxial stretching direction. It is obtained by stretching in a direction perpendicular to and heat setting.

The stretching method is a known method, for example,
In addition to the sequential biaxial stretching method in which longitudinal stretching and transverse stretching are performed in order, lateral bidirectional / longitudinal stretching sequential biaxial stretching method, transverse / longitudinal / vertical stretching method, longitudinal / transverse / longitudinal stretching method, longitudinal / longitudinal / transverse stretching method law, or it is possible to adopt a simultaneous biaxial stretching method, etc., it can be appropriately selected depending on the mechanical and thermal properties which are required, (Tg ₁
In the temperature range of −25) ° C. to (Tg ₂ +60) ° C., stretching is performed at least 3.0 times in both the longitudinal and transverse directions, and then 200
For a photographic light-sensitive material having a desired temperature expansion coefficient of 25 × 10 ⁻⁶ cm / cm / ° C. or less and a humidity expansion coefficient of 15 × 10 ⁻⁶ cm / cm /% RH or less in a manufacturing method of heat treatment at ˜240 ° C. This is the preferred method of making the support.

Here, Tg ₁ and Tg ₂ represent the highest and lowest glass transition temperatures of the polymers constituting the laminated support, respectively.

Generally, a sequential biaxial stretching method in which stretching is carried out first in the longitudinal direction and then in the width direction is preferred. Laminated PET
In the case of a system support, the glass transition temperature (Tg) of each laminated layer
Varies depending on the copolymerization ratio and the stretching temperature is not uniquely determined, but stretching at 70 to 140 ° C. is preferred. The stretching temperature in the width direction is preferably slightly higher than that in the longitudinal direction.

Next, this stretched support is heat-treated. As the heat treatment temperature, a temperature of 200 ° C. to 240 ° C. is adopted for photography, printing, and medical applications that require dimensional stability. The heat treatment time is not particularly limited, but is usually 3 seconds to 100 seconds. Longitudinal heat relaxation, if necessary
It goes without saying that lateral heat relaxation treatment may be applied.

In addition to the above, surface treatment (giving a gas barrier property by coating with vinylidene chloride, providing slipperiness by applying in-line coating, providing easy adhesion, etc.) may be performed by the same method. The above-mentioned film forming method can be appropriately changed according to its use and purpose, and the present invention is not limited to these methods for any reason.

The thickness of the polyethylene terephthalate-based polymer stretched support thus obtained varies depending on the use of the photographic light-sensitive material, but is 60 to 122 for a color light-sensitive material.
μm, 100 μm for medical and printing materials, 17 for X ray
There are various thicknesses of 5 μm, but those having a thickness of 50 to 250 μm are usefully used.

Next, the subbing treatment of the support before coating the hydrophilic colloid layer for silver halide photographic light-sensitive materials will be described.
When applying the undercoat layer, it is preferable to perform chemical treatment, mechanical surface roughening treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, etc. . The surface tension of the surface is preferably 50 dyne / cm or more by these treatments. As the subbing layer, any of those used in the art may be used. The subbing layer may be a single layer, but it is preferably a multi-layer in order to obtain more functionality and enhance the adhesive strength.

The subbing layer method will be described below. In the multi-layer method, the first subbing layer preferably adheres well to the support, and the raw materials include unsaturated carboxylic acids such as methacrylic acid and acrylic acid or esters thereof, styrene, vinylidene chloride, vinyl chloride and the like. Examples thereof include polymers or copolymers obtained from monomers, water-dispersed polyesters, polyurethanes, polyethyleneimines, and epoxy resins. Of these, preferred are copolymers having a water-dispersible polyester and a styrene polymer as constituent elements. The copolymer or composition containing the water-dispersible polyester and the styrene polymer as constituent elements will be described.

The water-dispersible polyester is a substantially linear polymer obtained by a polycondensation reaction of a polybasic acid or its ester-forming derivative with a polyol or its ester-forming derivative. The polybasic acid component of this polymer includes terephthalic acid, isophthalic acid, phthalic acid,
Phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,
Examples thereof include 4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid and dimer acid. Unsaturated polybasic acids such as maleic acid, fumaric acid, itaconic acid and p
A small proportion of hydroxycarboxylic acids such as -hydroxybenzoic acid and p- (β-hydroxyethoxy) benzoic acid can be used.

As the polyol component, ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, triglyceride. Methylolpropane, poly (ethylene oxide) glycol,
Examples thereof include poly (tetramethylene oxide) glycol.

In order to impart water dispersibility and water solubility to the water-dispersible polyester, introduction of a sulfonate, diethylene glycol, polyalkylene ether glycol or the like is an effective means. In particular, a dicarboxylic acid component having a sulfonate (a dicarboxylic acid having a sulfonate and / or
Or its ester-forming derivative) is preferably contained in an amount of 5 to 15 mol% with respect to the total dicarboxylic acid component in the water-dispersible polyester.

As the dicarboxylic acid having a sulfonic acid salt and / or its ester-forming derivative used in the undercoat layer of the present invention, one having an alkali metal sulfonate group is particularly preferable, for example, 4-sulfoisophthalic acid, 5
-Alkali metal salts such as sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5- (4-sulfophenoxy) isophthalic acid or ester-forming derivatives thereof are used. However, 5-sulfoisophthalic acid sodium salt or its ester-forming derivative is particularly preferable. From the viewpoint of water solubility and water resistance, it is particularly preferable that the dicarboxylic acid having these sulfonates and / or the ester-forming derivative thereof is used in an amount of 6 to 10 mol% based on the total dicarboxylic acid component.

As the monomer of the styrene polymer used in the undercoat layer of the present invention, when styrene is used alone or when it is copolymerized, for example, alkyl acrylate or alkyl methacrylate (wherein the alkyl group is a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, phenyl group, benzyl group, phenylethyl group, etc.); 2-hydroxyethyl acrylate, 2-hydroxy Hydroxy-containing monomers such as ethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate; acrylamide, methacrylamide, N-methylmethacrylamide, N-methylacrylamide, N-methylolmethacrylamide, N-methylo. Le acrylamide, N, N-
Amido group-containing monomers such as dimethylolacrylamide and N-methoxymethylacrylamide; amino group-containing monomers such as N, N-diethylaminoethyl acrylate and N, N-diethylaminomethacrylate; epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate; acrylic acid Monomers containing carboxyl groups or salts thereof such as methacrylic acid and salts thereof (sodium salt, potassium salt, ammonium salt); styrenesulfonic acid, vinylsulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt) Monomers containing sulfonic acid groups or salts thereof such as; itaconic acid, maleic acid, fumaric acid and salts thereof (sodium salt,
Monomers containing carboxyl groups such as potassium salts and ammonium salts) or salts thereof; monomers containing acid anhydrides such as maleic anhydride and itaconic anhydride; vinyl isocyanate, allyl isocyanate, vinyl methyl ether, vinyl ethyl ether, acrylonitrile , Vinyl chloride, vinyl acetate, vinylidene chloride and the like.
The above-mentioned monomers can be copolymerized by using one kind or two or more kinds.

In order to modify the water-dispersible polyester into a vinyl polymer, an addition-polymerizable group is introduced at the terminal of the water-dispersible polyester and copolymerized with a monomer of the vinyl copolymer for grafting. There are methods such as a method of polymerizing a vinyl-based copolymer and introducing a reactive group at the time of condensation polymerization of a water-dispersible polyester such as a carboxylic acid, a glycidyl group or an amino group as a monomer, and grafting.

The polymerization initiator includes ammonium persulfate, potassium persulfate, sodium persulfate, etc., and ammonium persulfate is preferably used.

Further, regarding the polymerization, a soap is not particularly required and the reaction can be carried out soap-free. But,
For the purpose of improving the polymerization stability, a surfactant can be used as an emulsifier in the system, and any general nonionic and anionic surfactant can be used.

The ratio of modification of the above water-dispersible polyester and styrene copolymer is 99/1 to 5/95, preferably 97/3 to 50/50, and more preferably 95/5.
~ 80/20 is good.

In order to improve the coatability, it is preferable to add an activator or a cellulose compound such as methylcellulose to the first subbing layer.

The subbing treatment may be carried out after the film formation on the support, but if the subbing composition can be stretched, before the longitudinal stretching which is in the course of the film formation and between the longitudinal stretching and the lateral stretching. It can be performed at any place such as after transverse stretching and before heat treatment. When stretching is not possible For example, when a polymer having a hydrophilic group is used, it may not be possible to stretch due to strong interaction between hydrophilic polymers, but stretching under steam, polyglycerin as a stretching aid, etc. It becomes possible to stretch by adding.

Preferred among the monomers having a hydrophilic group are unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic anhydride. From the viewpoint of water resistance, the content is preferably 1 to 10% by weight, more preferably 1 to 8% by weight, and further preferably 1
-6% by weight, most preferably 1-4% by weight. Further, as the fourth component of this copolymer, other copolymerizable monomers may be copolymerized in the range of 0 to 15% by weight, preferably 0 to 10% by weight, if necessary. Examples thereof include alkyl-substituted styrenes such as methylstyrene, halogenated styrenes such as chlorostyrene and chloromethylstyrene, unsaturated nitrile compounds such as acrylonitrile, aliphatic acrylates such as methyl acrylate, methyl methacrylate and t-butyl acrylate. , Alicyclic such as cyclohexyl methacrylate, aromatic (meth) such as benzyl acrylate
Examples thereof include acrylic acid ester compounds, and rubber-modified compounds such as butadiene and isoprene.

The method for producing these copolymers is not particularly limited, and can be usually obtained by radical polymerization using a generally known radical initiator.

The copolymer of these monomers, GP
The standard polystyrene equivalent weight average molecular weight measured by the C method is preferably 1500 to 700,000, and more preferably 2000 to 500,000.

The second subbing layer is preferably a hydrophilic resin layer which adheres well to the photographic emulsion layer. As a binder that constitutes the hydrophilic resin layer, gelatin, a gelatin derivative,
Casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, carboxymethyl cellulose, water-soluble polymers such as hydroxyethyl cellulose, a combination of polystyrene sulfonate sodium copolymer and a hydrophobic latex, and the like, Gelatin is preferred.

A hardener is preferably used in the two undercoat layers to enhance the film strength. Examples of such hardener include aldehyde compounds such as formaldehyde and glutaraldehyde, US Pat. 732, 303
No. 3,288,775, British Patent 974,723.
No. 1,167,207, etc., compounds having a reactive halogen, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethyl)
Urea, 2-hydroxy-4,6-dichloro-1,3,5
-Triazine, divinyl sulfone, 5-acetyl-1,
3-Diacryloylhexahydro-1,3,5-triazine, U.S. Pat. Nos. 3,232,763 and 3,635.
718, compounds having reactive olefins described in British Patent 994,809, etc., US Pat. No. 3,539,64
No. 4, No. 3,642, 486, Japanese Patent Publication No. 49-1356
No. 8, No. 53-47271, No. 56-48860,
JP-A-53-57257, JP-A-61-128240,
No. 62-4275, No. 63-53541, No. 63-
Vinylsulfone compounds described in No. 264572, N-
Hydroxymethylphthalimide, US Patent 2,732
No. 316, 2,586,168, etc., N-methylol compounds, US Pat. No. 3,103,437, etc., isocyanate compounds, US Pat. No. 2,983,611.
And the aziridine compounds described in U.S. Pat. Nos. 2,725,294 and 2,725,2.
Acid derivatives described in US Pat. No. 3,100,7
No. 04, etc., carbodiimide compounds, U.S. Pat. No. 3,091,537, etc. epoxy compounds, U.S. Pat. Nos. 3,321,313, 3,543,292, etc. isoxazole compounds. , Organic hardeners such as halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, and inorganic hardeners such as chromium alum, zirconium sulfate and chromium trichloride. Further, as a hardener having a relatively fast hardening effect on gelatin, compounds having a dihydroquinoline skeleton described in JP-A-50-38540, JP-A-51-59625 and JP-A-62-26 are known.
No. 2854, No. 62-264044, No. 63-184.
No. 741 N-carbamoylpyridinium salts,
It has two or more acyl imidazoles described in JP-B-55-38655, N-acyloxyimidazoles described in JP-B-53-22089, and two or more N-acyloxyimino groups described in JP-B-53-22089. Compounds, compounds having an N-sulfonyloxyimide group described in JP-A-52-93470, JP-A-58-113
A compound having a phosphorus-halogen bond described in No. 929,
JP-A-60-225148 and 61-240236.
Nos. 63-41580 and chloroformamidinium compounds are known.

The second subbing layer preferably contains, as a slip agent, inorganic fine particles such as silicon dioxide and titanium oxide, and an organic matting material (1 to 10 μm) such as polymethylmethacrylate. In addition to these, various additives such as an antistatic agent, an antihalation agent, a coloring dye, a pigment, and a coating aid may be contained, if necessary.

Among these, it is preferable to include an antistatic agent. Preferred antistatic agents include non-photosensitive conductors and / or semiconductor fine particles.

The non-photosensitive conductor and / or semiconductor fine particles used in the undercoat layer of the present invention are electrically conductive due to charge carriers existing in the particles, such as cations, anions, electrons and holes. As shown, it may be an organic material, an inorganic material, or a composite material of both. Preferably, it is a compound showing electron conductivity, and if it is an organic material, polyaniline,
Examples thereof include polymer fine particles such as polypyrrole and polyacetylene. Oxygen-deficient oxide if inorganic material,
Examples thereof include metal oxide fine particles that easily form a non-stoichiometric compound such as a metal excess oxide, a metal deficient oxide, and an oxygen excess oxide. If it is a charge transfer complex or an organic-inorganic composite material, a phosphazene metal complex or the like can be mentioned.
Among these, the most preferable compound for the undercoat layer of the present invention is metal oxide fine particles which can be manufactured by various methods. The conductor in the undercoat layer of the present invention has a volume resistivity of 10 ³ Ω · cm or less, and the semiconductor has a volume resistivity of 10 ¹² Ω · cm or less as a conductor and a semiconductor, respectively.

A preferred method for producing conductive fine particles will be described below.

<Preparation of Semiconductor Fine Particle Solution> 65 g of stannic chloride hydrate was dissolved in 2000 cc of water / ethanol mixed solution to obtain a uniform solution. Then, this was boiled to obtain a coprecipitate. The formed precipitate is taken out by decantation, and the precipitate is washed with distilled water many times. Silver nitrate was dropped into distilled water after washing the precipitate, and after confirming that there was no reaction of chlorine ions, 1000 cc of distilled water was added to bring the total amount to 20.
00cc. 40cc of 30% ammonia water
In addition, the mixture was heated in a water bath to obtain a colloidal gel dispersion liquid.

<Preparation of Semiconductor Fine Particle Powder> Stannous chloride hydrate (65 g) and antimony trichloride (1.5 g) were dissolved in ethanol (1000 g) to obtain a uniform solution. 1N- in this solution
A sodium hydroxide aqueous solution was added dropwise until the pH of the solution became 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate. The reddish brown colloidal precipitate was separated by centrifugation. To remove excess ions, water was added to the precipitate and washed by centrifugation. This operation was repeated 3 times to remove excess ions.
100 g of colloidal precipitate from which excess ions were removed was added with 50 g of barium sulfate having an average particle size of 0.3 μm and 1000 g of water.
It was mixed with g and sprayed in a firing furnace heated to 900 ° C. to obtain a bluish powder mixture of stannic oxide and barium sulfate having an average particle size of 0.1 μm.

The coating liquid concentration of the undercoat layer composition is usually 20% by weight or less, preferably 15% by weight or less. The coating amount is preferably 1 to 30 g, and more preferably 5 to 20 g in terms of coating liquid weight per 1 m ² of the support.

As a coating method, various known methods can be applied. For example, a roll coating method, a gravure roll coating method, a spray coating method, an air knife coating method, a bar coating method, an impregnation method, a curtain coating method, or the like can be applied alone or in combination.

Next, the photographic layer of the photographic light-sensitive material of the present invention will be described. The silver halide photographic light-sensitive material according to the present invention is preferably subjected to photographic processing after exposure by an automatic processor having at least four processes of development, fixing, washing (or stabilizing bath) and drying.

As the developing solution used in the present invention, known developing agents can be used. Specifically, dihydroxybenzenes (eg, hydroquinone, hydroquinone monosulfonate, etc.), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone, 1-phenyl-4-).
Methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-
Pyrazolidone), aminophenols (eg o-aminophenol, p-aminophenol, N-methyl-)
o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.), ascorbic acids (ascorbic acid, sodium ascorbate, erythorbic acid, etc.) and metal complex salts (EDTA iron salt, DTPA)
(Iron salt, DTPA nickel salt, etc.) can be used alone or in combination. Among them, it is preferable to use a developing solution containing ascorbic acid and its derivative. Ascorbic acid and its derivatives are known as developing agents and are disclosed in, for example, US Pat. No. 2,688,548.
No. 2, No. 2,688,549, No. 3,022,168
Nos. 3,512,981, 4,975,354 and 5,326,816 can be used.

Further, the developing agents for ascorbic acid and its derivatives and 3-pyrazolidones (for example, 1-phenyl-
3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl- 3-pyrazolidone) and aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4)
-Diaminophenol, etc.) or dihydroxybenzenes substituted with a hydrophilic group (for example, hydroquinone monosulfonate, hydroquinone monosulfonic acid sodium salt,
It is preferable to use a developing agent such as 2,5-hydroquinone disulfonic acid potassium salt) in combination. When used in combination, the developing agent for 3-pyrazolidones, aminophenols and dihydroxybenzenes substituted with a hydrophilic group is usually 0.0
It is preferably used in an amount of 1 or more and less than 0.2 mol.
In particular, a combination of ascorbic acid and its derivative with 3-pyrazolidones, and a combination of ascorbic acid and its derivative with 3-pyrazolidones and dihydroxybenzenes substituted with a hydrophilic group are preferably used.

An alkaline agent (sodium hydroxide, potassium hydroxide, etc.) and a pH buffering agent (eg carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, alkanolamine, etc.) are added to the developer. Preferably. As the pH buffering agent, carbonate is preferable, and the addition amount thereof is preferably 0.5 mol or more and 2.5 mol or less per 1 liter, and 0.1.
The range of 75 mol or more and 1.5 mol or less is more preferable. If necessary, a solubilizing agent (for example, polyethylene glycols, their esters, alkanolamines, etc.), a sensitizer (for example, nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants, Antifoaming agents, antifoggants (eg, potassium bromide, halides such as sodium bromide, nitrobenzindazole,
Nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (eg ethylenediaminetetraacetic acid or its alkali metal salts, nitrilotriacetic acid salts, polyphosphate salts, etc.), development accelerators (eg US Pat. 2, 304, 025, compounds described in JP-B-47-45541, etc.), a film hardening agent (eg glutaraldehyde or its bisulfite adduct), or a defoaming agent can be added. The pH of the developer is preferably adjusted to 7.5 or more and less than 10.5. More preferably, the pH is 8.5 or more and 10.4.
It is the following.

As the fixing solution, those having a generally used composition can be used. The fixing solution generally has a pH of 3-8. As a fixing agent, sodium thiosulfate,
Thiosulfates such as potassium thiosulfate and ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate,
In addition to thiocyanates such as ammonium thiocyanate, it is possible to use an organic sulfur compound capable of forming a soluble stable silver complex salt, which is known as a fixing agent.

The fixing solution contains a water-soluble aluminum salt which acts as a hardening agent, such as aluminum chloride, aluminum sulfate, potassium alum, and aldehyde compounds (eg, glutaraldehyde and a sulfite adduct of glutaraldehyde).
Etc. can be added.

If desired, the fixer may contain preservatives (eg, sulfite, bisulfite), pH buffers (eg, acetic acid, citric acid), pH adjusters (eg, sulfuric acid), and chelates having a water softening ability. Compounds such as agents may be included.

After the fixing treatment, it is washed with water and / or treated in a stabilizing bath. As the stabilizing bath, for the purpose of stabilizing an image, inorganic and organic acids and salts thereof, or alkaline agents and salts thereof (for adjusting the pH of the film surface after treatment to 3 to 8) for the purpose of stabilizing the image ( For example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid,
Used in combination with polycarboxylic acid, citric acid, oxalic acid, malic acid, acetic acid, etc.), aldehydes (eg formalin, glyoxal, glutaraldehyde etc.), chelating agents (eg ethylenediaminetetraacetic acid or its alkali metal salts, nitrilotriacetic acid salts) , Polyphosphate, etc., antifungal agent (eg phenol, 4-chlorophenol, cresol, O-phenylphenol, chlorophene, dichlorophene, formaldehyde, P-hydroxybenzoic acid ester, 2- (4-thiazoline) -benzo. Imidazole, benzisothiazolin-3-one, dodecyl-benzyl-methylammonium chloride, N- (fluorodichloromethylthio) phthalimide, 2,4,4'-
Trichloro-2'-hydroxydiphenyl ether, etc., a color tone adjusting agent and / or a residual color improving agent (for example, a nitrogen-containing heterocyclic compound having a mercapto group as a substituent);
Specifically, sodium 2-mercapto-5-sulfonate-benzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole, 2-
Mercapto-5-propyl-1,3,4-triazole, 2-mercaptohypoxanthine and the like).
Among them, it is preferable that the stabilizing bath contains an antifungal agent. These may be replenished in liquid or solid form.

The temperature of the developing, fixing, washing and / or stabilizing bath is preferably between 10 and 45 ° C., and the temperature of each may be adjusted separately.

In order to shorten the developing time, the total processing time (Dry) from when the leading edge of the film is inserted into the automatic developing machine to when it comes out of the drying zone when processing using the automatic developing machine
to Dry) is preferably 60 seconds or less and 10 seconds or more.

The halogen composition of silver halide in the silver halide emulsion is not particularly limited, but in the case of processing with a small replenishment amount or rapid processing, silver chloride, 60 mol%
It is preferable to use a silver halide emulsion having the above composition of silver chlorobromide containing silver chloride and silver chloroiodobromide containing 60 mol% or more of silver chloride.

The average grain size of silver halide is 1.2 μm.
m or less, and particularly 0.8 to 0.1 μm
Is preferred. The average particle size is a term that is commonly used and easily understood by experts in the field of photographic science. The particle size means a particle diameter when the particles are spherical or particles which can be approximated to a sphere. When the particle is a cube, it is converted into a sphere, and the diameter of the sphere is taken as the particle size. For details of the method for determining the average particle size, see Mies, James: The Theory of the Photographic Process (CE.
Mees & T. H. James: The theor
y of the photographic pro
ccs), 3rd edition, pp. 36-43 (1966 (published by Macmillan "Mcmilllan")).

The shape of silver halide grains is not limited,
Any shape such as a flat plate shape, a spherical shape, a cubic shape, a tetradecahedral shape, a regular octahedron shape or the like may be used. Further, the grain size distribution is preferably narrow, and a so-called monodisperse emulsion in which 90%, preferably 95% of the total grain number falls within the grain size range of ± 40% of the average grain size is particularly preferable.

For details of the silver halide emulsion and its preparation method, see Research Disclosure (Res).
search Disclosure) 176 No. 1764
3, pages 22 to 23 (December 1978) or cited.

The silver halide emulsion may or may not be chemically sensitized. As chemical sensitization methods, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization are known, and any of these may be used alone or in combination.

The light-sensitive material used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. . That is, many compounds known as antifoggants or stabilizers such as azoles, mercaptopyrimidines, mercaptotriazines, azaindenes, benzenethiosulfonic acid, benzenesulfinic acid, and benzenesulfonic acid amide can be added. .

As the binder or protective colloid of the photographic emulsion, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

As gelatin, in addition to lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Gelatin enzymatic degradation products can also be used.

Inorganic or organic hardeners are added to the photographic emulsion and the non-photosensitive hydrophilic colloid layer as a crosslinking agent for hydrophilic colloids such as gelatin. These hardeners are available from Research Disclosure (Research D
(Isclosure) 176, 17643 (published December 1978), page 26, A to C.

Various other additives are used in the light-sensitive material. Examples thereof include desensitizers, plasticizers, slip agents, development accelerators, oils and the like.

For the above-mentioned additives and other known additives, see Research Disclosure N.
o. 17643 (December 1978), the same No. 187
16 (November 1979) and No. 16 of the same. 308119
(December 1989).

The light-sensitive material of the present invention is used for radiography.
It can be used for various purposes such as printing plate making, general photography such as color or black and white negative film, and direct viewing.

[0101]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

The curling curl measuring method, workability evaluating method, and temperature expansion coefficient (αt), humidity expansion coefficient (αh), and glass transition temperature of the laminated PET-type polymer support of the silver halide photographic light-sensitive material are as follows. The measuring method will be described.

(1) Curling curl Curling curl indicates curling in the lengthwise direction wound on the core. The sample size of the silver halide photographic light-sensitive material film was 12 cm (longitudinal direction during production) × 35 mm (horizontal direction during production) at 23 ° C.
After conditioning the humidity for 1 day under the condition of 55% RH, wind this on a winding core having a diameter of 10.8 mm, and heat it at 55 ° C. for 20%.
The heat treatment was performed for 4 hours in the RH atmosphere. Then, after allowing to cool in an atmosphere of 23 ° C. and 55% RH for 30 minutes, the core is released, and after 1 minute, the curl degree of curling of the film is measured.

The above curl curl test conditions are as follows:
This is almost the same as the state after storage for 2 years when a photosensitive material for printing is wound around a core having a diameter of 2-3 inches which is commonly used.

The curling curl degree is represented by 1 / R (m ^-1 ). This R represents the radius of curvature of the curled film,
The unit is m (meter).

(2) Workability evaluation method Heat treatment (55 ° C., 20% R) by the method described in (1) above.
(H, 4 hours) A sample was continuously cut out from a product roll wound on a core having an inner diameter of 3 inches and used for a printing plate making scanner, and the workability was evaluated as follows.
Note that this condition was adopted as being equivalent to the accelerated test when left at room temperature for 2 years.

A) No jamming occurs, the cut sheet cut out is flat, and there is no problem in workability: ◎ b) No jamming occurs, and the cut out sheet is curled weakly No problem in workability: ○ c) A lot of jamming occurs, the curl of the cut sheet is severe and the workability is very problematic: × (3) Laminated PET polymer support Coefficient of thermal expansion (α
t), and humidity expansion coefficient (αh) measurement method (3-1) Laminated PET polymer support Using the laminated PET polymer support formed into a film, the temperature expansion coefficient (αt) and the humidity expansion coefficient (αh) Was measured. The measured values were not different from those obtained by measuring the laminated PET-based polymer support obtained by peeling the emulsion layer and the back coat layer from the photographic light-sensitive material using a Kao Co., Ltd.

(3-2) Measurement of temperature expansion coefficient (αt) and humidity expansion coefficient (αh) (a) Temperature expansion coefficient (αt) With a thermal mechanical analyzer (TMA), the humidity was kept constant at 55%, The dimensions at 23 ° C and 65 ° C were measured, and the coefficient of thermal expansion (α
t) was calculated.

(B) Humidity expansion coefficient (αh) With a thermal mechanical analyzer (TMA), the temperature was kept constant at 23 ° C. and the relative humidity was 20% and the relative humidity was 80%.
The dimension in% was measured, and the coefficient of humidity expansion (αh) was calculated as linearly changing during this period.

(4) Method for measuring glass transition temperature (Tg) of laminated PET-based polymer support The PET-based polymer constituting each layer of the laminated PET-based polymer support was extruded independently from an extruder,
When the support was sampled and a differential scanning calorimeter (DSC) was used to heat 10 mg of the sample support in a nitrogen stream at a temperature of 20 ° C./min, the temperature at which deviation from the baseline started and a new baseline It is defined as the arithmetic mean temperature (℃) with the temperature returning to. However, when an endothermic peak appears, the temperature showing the maximum value of this endothermic peak is defined as Tg (° C.).

Next, an example of producing a laminated PET polymer support will be described.

The laminated support was manufactured as follows.

(1) PET homopolymer and copolymer P
Polymerization of ET Upon polymerization of a normal PET homopolymer, copolymer monomers were added to the PET basic skeleton as shown in Tables 1 to 4 to obtain a PET copolymer.

(2) Preparation of laminated PET-based polymer support The obtained PET homopolymer and copolymerized PET polymer pellets were dried at 150 ° C. for 3 hours in a nitrogen atmosphere and crystallized, and at 280-320 ° C. Polymers are extruded by separate extruders, the polymers are laminated in a laminated die in a molten state, melt-extruded into a support, and then rapidly cooled and solidified on a cooling drum at 30 ° C by an electrostatic application method, and unlaminated. A support was prepared. An unstretched support was obtained in which the thickness composition ratio of each layer of the laminated unstretched support was as described in Tables 1 to 4.

(A). Examples 1 to 14 and Comparative Examples 1 to 4 have a thickness of 930 μm. In Examples 15 to 23 and Comparative Examples 5 to 11, unstretched supports having a thickness of 990 μm were obtained.

This unstretched support was treated with (a). Examples 1 to 14 and Comparative Examples 1 to 4 are 75 to 90 ° C.
Then, after stretching 3.0 times in the longitudinal direction, stretching 3.1 times in the transverse direction at 85 to 105 ° C., and heat setting at 215 ° C. for 15 seconds to support a biaxially oriented laminated PET-based polymer having a thickness of 100 μm. The body was wound to obtain a roll-shaped support.

(B). Examples 15-23, Comparative Examples 5-1
No. 1 has a draw ratio of 3.1 times in the machine direction and 3.2 in the cross direction.
The biaxially oriented laminated PET-based polymer support was wound in exactly the same manner except that the number of times was changed to obtain a roll-shaped support.

(3) Preparation of Photosensitive Light-Sensitive Material Both surfaces of the surface-treated laminated PET-based polymer support were treated with 7 Watt.
A support subjected to corona discharge treatment at a rate of min / m ² was obtained.

Undercoat of Laminated PET Polymer Support An antistatic undercoat layer containing styrene-glycidyl acrylate and tin oxide particles was formed.

Undercoating of Laminated PET Polymer Support and Coating of Silver Halide Photosensitive Layer On one of the above-mentioned undercoating layers, a gelatin subbing layer of the following Formulation 1 was added in an amount of 0.5 g of gelatin. / M ² so that the silver halide emulsion layer 1 of the formula 2 is silver amount 1.
5 g / m ² , the amount of gelatin is 0.5 g / m ² , and a coating solution of the following formulation 3 as an intermediate protective layer is further formed on the upper layer so that the amount of gelatin is 0.3 g / m ² and the upper layer. The silver halide emulsion layer 2 of Formula 4 was added in an amount of 1.4 g / g
Simultaneous multilayer coating was performed so that the amount of m ² and the amount of gelatin were 0.4 g / m ^{2 and} that the coating solution of the following formulation 5 was 0.6 g / m ² . On the other side of the undercoat layer, a backing layer of the following formulation 6 was formed so that the amount of gelatin was 0.6 g / m ^2, and a hydrophobic polymer layer of the following formulation 7 was further formed on the backing layer, and the following formulation was also formed on the hydrophobic polymer layer. A sample was obtained by simultaneously coating the backing protective layer of No. 8 with the emulsion layer side so that the amount of gelatin was 0.4 g / m ² .

Formulation 1 (Composition of gelatin subbing layer) Gelatin 0.5 g / m ² Solid dispersion fine particles of dye AD-1 (average particle size 0.1 μm) 25 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² S-1 (Sodium-iso-amyl-n-decylsulfosuccinate) 0.4 mg / m ² Formulation 2 (composition of silver halide emulsion layer 1) Silver halide emulsion A described later A silver amount of 1.5 g / m ² Solid dispersion fine particles of dye AD-8 (average particle size 0.1 μm) 20 mg / m ² cyclodextrin (hydrophilic polymer) 0.5 g / m ² sensitizing dye d-1 5 mg / m ² sensitizing dye d-2 5 mg / M ² Hydrazine derivative H-7 20 mg / m ² Redox compound: RE-1 20 mg / m ² Compound e 100 mg / m ² Latex polymer f 0.5 g / m ² Hardener g 5 mg / m ² S- 1 0.7 mg / m ² 2-mercapto-6-hydroxypurine 5 mg / m ² EDTA 30 mg / m ² colloidal silica (average particle size 0.05 μm) 10 mg / m ² formulation 3 (interlayer composition) gelatin 0.3 g / m ² S-1 2 mg / m ² Formulation 4 (composition of silver halide emulsion layer 2) Silver halide emulsion B described later so that the amount of silver was 1.4 g / m ² Sensitizing dye d-1 was increased by 3 mg / m ^2. Sensitizing dye d-2 3 mg / m ² hydrazine derivative H-20 20 mg / m ² Nucleation accelerator: Exemplified compound Nb-12 40 mg / m ² Redox compound: RE-2 20 mg / m ² 2-mercapto-6-hydroxypurine ^{5mg / m 2 EDTA 20mg / m} 2 latex polymer ^{f 0.5g / m 2 S-1} 1.7mg / m 2 formulation 5 (emulsion protective layer composition) gelatin 0.6 g / ^{m 2} dye AD-5 solid Chikarada (average particle size ^{0.1μm) 40mg / m 2 S-} 1 12mg / m 2 Matting agent: average particle size 3.5μm monodisperse silica 25 mg / m ² nucleation accelerator: Example Compound Na-3 40 mg / m ² 1,3-vinylsulfonyl-2-propanol 40 mg / m ² surfactant h 1 mg / m ² colloidal silica (average particle size 0.05 μm) 10 mg / m ² hardener: K-1 30 mg / m ² formulation 6 (Backing layer composition) Gelatin 0.6 g / m ² S-1 5 mg / m ² Latex polymer f 0.3 g / m ² Colloidal silica (average particle size 0.05 μm) 70 mg / m ² Sodium polystyrene sulfonate 20 mg / m ² compound i 100 mg / m ² formulation 7 (hydrophobic polymer layer composition) latex (methyl methacrylate: acrylic acid = 97: 3) 1.0g / m 2 hardener g 6 mg / ² Formulation 8 (backing protective layer) Gelatin 0.4 g / m ² Matting agent: monodispersed polymethylmethacrylate 50 mg / m ² Sodium an average particle diameter of 5 [mu] m - di - (2-ethylhexyl) - sulfosuccinate 10 mg / m ² surface Activator h 1 mg / m ² Dye k 20 mg / m ² H (OCH ₂ CH ₂ ) ₆₈ OH 50 mg / m ² Hardener: K-1 20 mg / m ²

[0122]

[Chemical 1]

[0123]

[Chemical 2]

[0124]

[Chemical 3]

[0125]

[Chemical 4]

(Preparation of Silver Halide Emulsion A) A silver chlorobromide core grain having an average thickness of 0.05 μm and an average diameter of 0.15 μm, which is composed of 70 mol% of silver chloride and the rest is silver bromide, is prepared by a double-mixing method. Prepared. When the core particles were mixed, K ₃ RuCl ₆ was added in an amount of 8 × 10 ^-8 mol per mol of silver. The core particles were shelled using the double jet method. At that time, K ₂ I
3 × 10 ⁻⁷ mol of rCl ₆ was added per mol of silver. The obtained emulsion has an average thickness of 0.10 μm and an average diameter of 0.25.
μm core / shell monodisperse (variation coefficient 10%) (1
Chloroiodobromide (silver chloride 90
Mol%, silver iodobromide 0.2 mol% and the rest silver bromide). Then, JP-A-2-280
Modified gelatin described in JP-A-139 (a gelatin in which an amino group in gelatin is substituted with phenylcarbamyl, for example, Japanese Patent Laid-Open No. 2-53967).
-280139, Exemplified Compound G-8 on page 287 (3))
Was used to desalt. EAg after desalting is 190 mV at 50 ° C
Met.

4-Hydroxy-6-methyl-1,3,3a7-tetrazaindene was added to the resulting emulsion at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added to adjust the pH to 5. .6, adjust to EAg123mV,
After adding 2 × 10 ^-5 mol of chloroauric acid, add 3 × of inorganic sulfur
10 ⁻⁶ mol was added and chemical ripening was performed at a temperature of 60 ° C. until maximum sensitivity was obtained. After completion of the ripening, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was added in an amount of 2 × 10 ^-3 mol, 1-phenyl-5-mercaptotetrazole in an amount of 3 × 10 ^-4 mol and gelatin in 1 mol of silver. Was added.

(Preparation of Silver Halide Emulsion B) 60 mol% of silver chloride, 2.5 mol% of silver iodide, the rest of which is silver bromide with an average thickness of 0.05 μm and an average diameter of 0.
15 μm silver chloroiodobromide core grains were prepared. When mixing core particles, K ₃ Rh (H ₂ O) Br ₅ was added in an amount of 2 × 1 per mol of silver.
^0-8 mol was added. The core particles were shelled using the double jet method. At that time, K ₂ IrCl ₆ was added in an amount of 3 × 10 ^-7 mol per mol of silver. The resulting emulsion had a core / shell type monodisperse (variation coefficient of 10%) of 0.10 μm in average thickness and 0.42 μm in average diameter and had a silver chloroiodobromide content (90 mol% silver chloride, 0.5 mol silver iodobromide). %, The rest consists of silver bromide)
It was a tabular grain emulsion. Next, JP-A-2-28013
The modified gelatin described in JP-A No. 9- (A gelatin group in which the amino group is substituted with phenylcarbamyl, for example, JP-A-2-2
Desalination was carried out by using Exemplified Compound G-8) of No. 80139, page 287 (3). The EAg after desalting was 180 mV at 50 ° C.

4-Hydroxy-6-methyl-1,3,3a7-tetrazaindene was added to the resulting emulsion at 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were further added to adjust the pH to 5. .6, adjust to EAg123mV,
After adding 2 × 10 ^-5 mol of chloroauric acid, N, N, N'-
Trimethyl-N'-heptafluoroselenourea 3x1
0 ^-5 mol was added and chemical ripening was performed at a temperature of 60 ° C until the maximum sensitivity was obtained. After completion of the ripening, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was added in an amount of 2 × 10 ^-3 mol, 1-phenyl-5-mercaptotetrazole in an amount of 3 × 10 ^-4 mol and gelatin in 1 mol of silver. Was added.

Examples 1 to 14 and Comparative Examples 1 to 4 (Tables 1 and 2) A roll-shaped support of a biaxially oriented laminated PET polymer support was surface-treated and coated with an undercoat layer as described above. , Undercoat layer coating, and silver halide emulsion coating were carried out, and in sequence, Example 1
14 and the photographic light-sensitive material product roll films of Comparative Examples 1 to 4 were obtained.

In the case of a two-layer laminated support, the laminated support is
It is composed of a first layer and a second layer, and there is no third layer. Three
In the case of a layer laminated support, it is composed of the first to third layers,
The third layer constitutes the central layer. Both the two-layer and three-layer laminated supports have the property of curling with the second layer inside.

A silver halide photographic light-sensitive material was prepared by coating an emulsion layer on the first layer of the laminated support and a back coat layer on the second layer and winding the emulsion layer side, that is, the first layer side inside, around the core. When stored as, the anti-curl force that tends to curl with the second layer side, that is, with the backcoat layer inside, is generated against the curl curl force generated with the emulsion layer inside, and these forces cancel each other out. A flat film is obtained when it is fitted and released from the core.

On the contrary, surface treatment, undercoat layer coating, undercoat layer coating, silver halide emulsion layer was formed on the opposite side (layer containing a large amount of copolymerization components) of the biaxially oriented laminated PET polymer support of Example 1. When a coated light-sensitive material was prepared and wound with the emulsion layer on the inside, curling curls were strong and could not be used.

The glass transition temperature of each support is shown below.

* PET homopolymer support (Tg); 76.0 (° C) * Copolymerization PET polymer support (Tg) -Adipic acid (15 mol%); 57.1 (° C) -〃 (8 mol% ); 61.1 (° C) -〃 (5 mol%); 67.0 (° C) -Cyclohexanedicarboxylic acid (15 mol%); 68.9 (° C) -〃 (8 mol%); 70.9 ( ℃) ・ 〃 (5 mol%) ； 71.5 (℃) ・ Diethylene glycol (15 mol%) ； 69.7 (℃) ・ 〃 (8 mol%) ； 70.8 (℃) ・ 〃 (5 mol%) ); 71.9 (° C) -Neopentyl glycol (15 mol%); 73.4 (° C) -〃 (8 mol%); 74.8 (° C) -〃 (5 mol%); 75.1 ( ℃) In addition, the glass transfer of the copolymerized PET polymer support with different copolymerization ratio Temperature, PET homopolymer support Tg
And each copolymerized PET polymer support (15 mol%) Tg
Varies between.

[0136]

[Table 1]

* 1: adipic acid (added in the form of dimethyl adipic acid)

[0138]

[Table 2]

Examples 1 to 11 and Comparative Examples 1 to 1 shown in Table 1
2 and the results of Examples 12 to 14 and Comparative Examples 3 to 4 shown in Table 2, the curl degree of the silver halide photographic light sensitive material is 80.
It is understood that workability is excellent when it is m ^-1 or less, preferably 60 m ^-1 or less. Further, at this time, if the thickness composition ratio of the layers forming both outermost layers of the laminated support is 1: 1 and the difference in the copolymerization components is 2 mol% or more, the curl degree is 80 m ^-1 or less, If it is 4 mol% or more, the curl degree is 60 m.
^-It is understood that ^-1 or less can be achieved.

The coefficient of thermal expansion of the laminated PET supports of Examples 1 to 14 and Comparative Examples 1 to 4 was (22 to 25) × 10 ^-6.
cm / cm / ° C., humidity expansion coefficient is (12 to 15) × 10
^-6 cm / cm /% RH, the temperature expansion coefficient of the homo-PET monolayer support formed under the same manufacturing conditions {(22-25)
× 10 ^-6 cm / cm / ° C}, humidity expansion coefficient {(13 to 1
5) × 10 ⁻⁶ cm / cm /% RH}, which is a good numerical value almost equal to or higher than that. For comparison, TAC of 100 μm and a film formed under the same production conditions as in Examples and Comparative Examples (containing 0.5 mol% of polyethylene glycol + 4.5 mol% of sodium sulfoisophthalate) copolymer PET / PET homopolymer = The humidity expansion coefficient of the laminated PET support having a thickness of 1/1 and 100 μm is 50 × 10 ⁻⁶ cm / cm /
% RH and 40 × 10 ⁻⁶ cm / cm /% RH were very inferior.

The homo-PET (A) constituting the first layer of Examples 6 to 11 and the second layer of Examples 3 to 6 were constituted.
A single layer of adipic acid component 15 mol% copolymerized PET (B) and adipic acid component 20 mol% copolymerized PET (C) were formed under the same film forming conditions as described in Examples 1 to 11 and Comparative Examples 1 and 2. The support was prepared and the mechanical strength was measured according to the method of ASTM D882-61T.

Longitudinal (kg / mm ² ) Horizontal (kg / mm ² ) A 21.1 19.9 B 20.0 19.7 C 12.4 12.7 From the above results, it is confirmed that the copolymer PET support is If the proportion of the copolymerization component exceeds 15 mol%, the mechanical properties inherent to the PET support are lost, so the proportion of the copolymerization component is preferably 15 mol% or less.

Examples 15 to 23, Comparative Examples 5 to 7 (Table 3) Examples 1 to 14 and Comparative Examples except that the stretching ratios in the longitudinal and transverse directions were 3.1 and 3.2, respectively. 1-4
In the same manner as above, a roll-shaped support of a biaxially oriented laminated PET support was obtained. This roll-shaped support was subjected to surface treatment, undercoat layer coating, undercoat layer coating, and silver halide emulsion coating in the same manner as in Examples 1 to 14 and Comparative Examples 1 to 4, and Examples 15 to 15 in that order.
23, roll films of photographic light-sensitive material products of Comparative Examples 5 to 7 were obtained.

[0144]

[Table 3]

* 2: Cyclohexanedicarboxylic acid * 3: Diethylene glycol * 4: Neopentyl glycol From the results of Examples 15 to 23 and Comparative Examples 5 to 7 shown in Table 3, the curl degree of the silver halide photographic light sensitive material is 80 m. It is understood that workability is excellent when it is ^-1 or less, preferably 60 m ^-1 or less. At this time, the copolymerization component is * 2
(Cyclohexanedicarboxylic acid), * 3 (diethylene glycol), * 4 (neopentyl glycol), a two-layer laminated support of a copolymer PET and a PET homopolymer. If the difference is ¹ , the curl degree is 80 m ⁻¹ or less if the difference in the copolymerization components is 7 mol% or more, and the curl degree is 60 if the difference is 11 mol% or more.
It is understood that m ⁻¹ or less can be achieved.

Further, the coefficient of thermal expansion of the laminated PET supports of Examples 15 to 23 and Comparative Examples 5 to 7 was (15 to 20) × 10.
^-6 cm / cm / ° C, the coefficient of humidity expansion is (9-12) × 10
^-6 cm / cm /% RH, the temperature expansion coefficient of the homo-PET monolayer support formed under the same manufacturing conditions {(15 to 20)
× 10 ^-6 cm / cm / ° C}, humidity expansion coefficient {(10 to 1
2) × 10 ⁻⁶ cm / cm /% RH} which is almost equal to or better than the above. This value is for comparison TAC1
A film was formed under the same manufacturing conditions as in Example 1 to 23 and Comparative Examples 1 to 7 (00 μm, (polyethylene glycol 0.5
Mol% + containing 4.5 mol% of sodium sulfoisophthalate) Copolymerization PET / PET homopolymer = 1/1 Laminated PET It was smaller than the humidity expansion coefficient of 100 μm (described above) and it was very excellent.

If the proportion of the copolymerization component of the PET-based support exceeds 15 mol%, the original mechanical properties (strength, etc.) of the PET support are lost, so the proportion of the copolymerization component should be 15 mol% or less. Good to have.

Examples 24 to 25, Comparative Examples 8 to 11 (Tables 4 and 5) In order to evaluate dimensional stability, multicolor printing was carried out to evaluate color misregistration.

Example 24 is the support of Example 6, Example 25 is the support of Example 17, and Comparative Example 8 is the same copolymerized PET / PET homopolymer laminate support of Example 24. The thickness of the unstretched support having a thickness of 100 μm is the same as in Example 2 and Example 17, except that the stretching ratios in the longitudinal and transverse directions of the unstretched support having a thickness of 760 μm are 2.7 times and 2.8 times, respectively. A biaxially oriented laminated PET support was obtained. Comparative Example 9 has a thickness of 9 consisting of a PET homopolymer monolayer support.
An unstretched support having a thickness of 30 μm was produced under the same film forming conditions as in Example 24 (Example 6). Comparative Example 10
Is a TAC 100 μm support, and Comparative Example 11 is a copolymer PET / PET (containing 0.5 mol% polyethylene glycol + 4.5 mol% sodium sulfisoisophthalate).
Homopolymer = 1/1 laminated PET support of 100 µm (film forming conditions are the same as in Example 24).

PE of Examples 24 to 25 and Comparative Examples 8 to 9
Table 4 shows the values of the refractive index, temperature and humidity expansion coefficient of the T homopolymer support and the PET-based laminated support.

[0151]

[Table 4]

Dimensional stability evaluation (multicolor printing): Ortho, panchromatic photographic films, and UV-sensitive silver halide films were prepared using the supports described in Examples and Comparative Examples.

The manuscript was screened using a plate-making photographic camera, and at the same time using red, green and blue-violet filters, from ortho and panchromatic photographic films using a support corresponding to the respective Examples and Comparative Examples. , Red, green, blue-violet black and white color separation negatives, and black color separation negatives were made in no time. From this color separation negative, halftone shooting (high pressure mercury lamp, 36) was carried out by using an ultraviolet-sensitive silver halide film using a support corresponding to each Example and Comparative Example.
After baking for 5 seconds at 5 nm), a positive mesh was produced without waiting time. The halftone positive was printed on the printing plate without any time, and each plate was printed with cyan ink, magenta ink, yellow ink, and black ink.

For color printing, four-color printing was performed for 1000 sheets, and the dimensional difference (color misregistration value) per 60 cm of the sample in which the four colors did not overlap precisely and the color misregistration occurred was measured. It is expressed by a value (μm).

The accuracy of the set temperature is ± 1 ° C.
Since the evaluation was carried out with care so that it falls within the range of, it is estimated that the dimensional difference due to the dimensional change is due to the actual humidity change, but in order to suppress the dimensional change due to the humidity change as much as possible,
The drying was also carried out for a sufficient time, and the temperature change was suppressed within ± 2 ° C and the humidity change was suppressed within 10% RH.

[0156]

[Table 5]

As described above, Examples 24 to 25 and Comparative Examples 8 to 11
From the results, it is understood that the laminated polyethylene terephthalate-based polymer support of the present invention has a dimensional stability equal to or higher than that of the PET homopolymer support.

By using the laminated polyethylene terephthalate polymer support of the present invention in a photographic light-sensitive material, it is possible to more efficiently obtain a photographic light-sensitive material which is hard to curl and has excellent dimensional stability.

[0159]

Industrial Applicability According to the present invention, the excellent thermal, mechanical, physical, chemical and optical properties of the PET support are not impaired, the dimensional stability is excellent, and the curling curl is small. It was possible to provide a support for a silver halide photographic light-sensitive material having excellent properties and handleability, a method for producing the same, and a silver halide photographic light-sensitive material using the support.

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Claims (6)

(57) [Claims] 1. A laminated support comprising polyethylene terephthalate as a main constituent component, and at least two or more layers made of polyethylene terephthalate having different proportions of copolymerization components, which are the outermost layers of the support. The layer made of a laminated support having a difference in the proportion of the copolymerization components of 2 to 15 mol% from each other has a temperature expansion coefficient of 2
5 × 10 ^-6 cm / cm / ° C or less, humidity expansion coefficient of 15 ×
Of the two layers constituting the outermost layer of the support for a silver halide photographic light-sensitive material having a concentration of 10 ⁻⁶ cm / cm /% RH or less, at least one layer of a light-sensitive halogenated layer is provided on the layer side having a small proportion of copolymerization components A silver halide photographic light-sensitive material having a silver emulsion layer, which is used by being rolled up. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the difference in the ratio of the copolymerization components of the layers constituting the outermost layer of the laminated support is 4 mol% or more. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the copolymerization component is at least one selected from adipic acid, cyclohexanedicarboxylic acid, diethylene glycol and neopentyl glycol. 4. The silver halide photographic light-sensitive material according to claim 1, 2 or 3, which has a curl degree of 80 m ^-1 or less. 5. The silver halide photographic light-sensitive material according to claim 1, 2 or 3, wherein the curl degree is 60 m ^-1 or less. 6. When forming a film from a laminated support of the support for silver halide photographic light-sensitive material according to claim 1, 2 or 3,
In the temperature range of (Tg ₁ -25) ° C to (Tg ₂ +60) ° C,
Stretching at least 3.0 times both in the machine and transverse directions,
A method for producing a support for a silver halide photographic light-sensitive material, characterized by performing heat treatment at 200 to 240 ° C. (here, T
g ₁ and Tg ₂ respectively represent the highest and lowest glass transition temperatures in the polymers constituting the laminated support).