JPH1039447A - Photographic support and its manufacture and silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance mechanical strength and dimensional stability and to eliminate defective conveyability in the case of reducing a reel diameter by specifying the curling degree of the support and a heat emission amount at a heat absorption peak occurring near to the glass transition point (Tg) of the support. SOLUTION: The curling degree of the support is set to <=80m<-1> and the heat emission amount at a heat absorption peak occurring near to the glass transition point (Tg) of the support is set to <=100mcal/g. This photographic support is preferably a polyester film, and it is preferred that the polyester is composed essentially of a dicarboxylic acid component and a diaol component and this film has a film forming ability and it is biaxially stretched, and among main polyester, it is composed essentially of terephthalic acid as a dicarboxylic acid component and ethylene glycol and/or 1,4-cyclohexane-dimethanol as a diol component from the view points of transparency and mechanical strength and dimensional stability and the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic light-sensitive material which is hard to be curled even when stored in a roll and has excellent flatness and dimensional stability. The present invention relates to a production method and a silver halide photographic material using the same.

[0002]

2. Description of the Related Art In recent years, applications of photographic light-sensitive materials have been diversified, and the speed of unwinding a film at the time of photographing, the increase in photographing magnification, and the miniaturization of photographing apparatuses have been remarkably progressing. Therefore, a support for a photographic light-sensitive material is required to have properties such as excellent mechanical strength and dimensional stability. Further, roll-shaped photographic light-sensitive materials are being used in office feeling, that is, output is like a computer printer,
Since the imaging device is compact, the diameter of the core must be reduced.

A biaxially stretched polyethylene terephthalate film (hereinafter referred to as a PET film) has excellent transparency, mechanical strength, and dimensional stability. It is used in printing materials requiring strict requirements, and films for X-rays requiring transparency and stiffness. However, PET
The film has no curl recovery property after development processing.When used for a photographic photosensitive material in the form of a roll film, the sample placed in a roll state for a long time will have a large curl curl, and automatic transport during photographing and There has been a problem that jamming or the like occurs at the time of conveyance to the automatic processing machine.

[0004] Therefore, it has been strongly desired to reduce curl of a polyester film typified by a PET film as a method capable of solving the above-mentioned problems.

[0005] From such a viewpoint, Japanese Patent Application Laid-Open No. Sho 51-1 discloses a method for reducing curl of a polyester film.
No. 6358 describes that a thermoplastic resin film has a Tg of -5 ° C or higher.
A method of performing heat treatment at Tg-30 ° C. for 0.1 to 1500 hours has been proposed. Further, Japanese Patent Application Laid-Open No. 6-35118 proposes a method in which a polyester film having a Tg of 90 ° C. to 200 ° C. is undercoated and then heat-treated at 50 ° C. to Tg for 0.1 to 1500 hours.

[0006]

The thermoplastic resin film is heated at Tg-5 ° C to Tg-30 ° C for 0.1 to 1500 hours.
The heat treatment method has an effect of reducing curling of crystalline or semi-crystalline thermoplastic resin, such as a PET film or a polyethylene naphthalate film (hereinafter referred to as a PEN film). However, such a long-time heat treatment at a relatively high temperature has a problem that the quality of the film is significantly impaired.

That is, a photographic material generally has a plastic film or the like as a base material, and various functional layers such as an adhesive layer and an antistatic layer and a photographic photosensitive layer are laminated on the surface thereof. As a manufacturing procedure, usually, a wide and long plastic film is coated with the above-mentioned functional layer, and wound around a core having a relatively large diameter as an intermediate product. Then, it is cut into the final product form and packaged.

It is advantageous for the intermediate product to be as wide and long as possible from the viewpoint of shortening the switching time and improving the productivity, and the weight of the intermediate product is increasing more and more. As a result, there is a problem in that the winding diameter becomes large and the heat transfer becomes poor. That is, heat is not uniformly applied outside and inside the winding. Also, plastic films are known to expand thermally.However, when heated in a rolled state, they tend to expand as heat is transmitted, but in the rolled up state, the stretched portions cannot be stretched well, resulting in wrinkles. In addition, various surface failures such as breaking, pressing, etc., which cannot be used as a photographic support, may occur.

A method of subjecting a polyester film having a Tg of 90 ° C. to 200 ° C. to an undercoating and then performing a heat treatment at a temperature of 50 ° C. to Tg for 0.1 to 1500 hours is described in principle in JP-A-51-16.
358 is exactly the same as that described in US Pat.
In order to sufficiently reduce curl, the film T
Heat treatment near g is necessary. For example, if Tg is 90
In the case of a polyester film at a temperature of 60 ° C., sufficient effects cannot be obtained unless heat treatment is performed at 60 ° C. or higher, and in a polyester film having a Tg of 120 ° C., sufficient effects cannot be obtained unless heat treatment is performed at 90 ° C. or higher. is there. Therefore,
Since the film has a high Tg and must be heat-treated at a very high temperature, the following new problems occur in addition to the above-mentioned problem that the film quality is significantly impaired.

That is, in general, the maximum temperature of a photographic light-sensitive material that can be normally used is at most 50 ° C., and the use at a higher temperature is limited to a short time. The heat resistance of the undercoat layer composed of various functional layers is usually designed in consideration of the ordinary temperature condition. Therefore, these undercoat layers cannot withstand the heat treatment for sufficiently reducing the curl of winding of the film, and the transfer of the additives to the surface of the coating, bleeding out, deterioration and decomposition of the material, It causes various problems such as cracks on the surface.

As described above, there have been provided excellent mechanical strength and dimensional stability which enable high speed film unwinding at the time of photographing, high magnification of photographing, and downsizing of photographing apparatus. However, even if the diameter of the core is reduced, an excellent photographic support having no transport failure has not been obtained.

[0012]

The object of the present invention has been attained by the following constitutions of the present invention.

(1) The curl degree of the support is 80 m ^-1 or less, and the calorific value of the endothermic peak developed near the glass transition temperature (Tg) of the support is 100 mcal / g or less. Photographic support.

(2) The photographic support described in the above item 1,
A photographic support comprising a polyester having an ethylene-terephthalate unit or an ethylene-naphthalenedicarboxylate unit as a main component.

(3) In the method for producing a photographic support according to the above item 1 or 2, the average cooling rate in the step of cooling from Tg to room temperature is from 1000 ° C./min to 1 ° C./mi.
n, a method for producing a photographic support.

(4) A silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer on the photographic support according to item 1 or 2.

Hereinafter, the present invention will be described in detail.

The photographic support of the present invention is preferably a polyester film. The polyester constituting the photographic support is not particularly limited, but has a film-forming property comprising a dicarboxylic acid component and a diol component as main components. And a biaxially stretched polyester film.

The main dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2,6-
Naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfonedicarboxylic acid, diphenyletherdicarboxylic acid, diphenylethanedicarboxylic acid,
Examples thereof include cyclohexanedicarboxylic acid, diphenyldicarboxylic acid, diphenylthioetherdicarboxylic acid, diphenylketonedicarboxylic acid, and phenylindanedicarboxylic acid. As the diol component, ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexane dimethanol,
2,2-bis (4-hydroxyphenyl) propane,
Examples thereof include 2,2-bis (4-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, bisphenol full orange hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, and cyclohexanediol.

Among the polyesters containing these as main components, from the viewpoints of transparency, mechanical strength, dimensional stability, etc., terephthalic acid as a dicarboxylic acid component, ethylene glycol and / or 1,4- Polyesters containing cyclohexanedimethanol as the main constituent are preferred. Above all, a polyester mainly composed of polyethylene terephthalate (PET), a polyester (PEN) composed of 2,6-naphthalenedicarboxylic acid and ethylene glycol, and a mixture of two or more of these polyesters are used as the major components. Is preferred.

When the content of the ethylene terephthalate unit or the ethylene naphthalenedicarboxylic acid unit is 70% by weight or more with respect to the polyester, the transparency,
A film with excellent mechanical strength and dimensional stability can be obtained.

The polyester constituting the biaxially stretched polyester film may be further copolymerized with other copolymer components as long as the effects of the present invention are not impaired.
Other polyesters may be mixed. Examples of these include the above-mentioned dicarboxylic acid components and diol components, and polyesters composed thereof.

The polyester constituting the biaxially stretched polyester film is preferably made of an aromatic dicarboxylic acid having a sulfonate group or an ester-forming derivative thereof, a dicarboxylic acid having a polyoxyalkylene group or a dicarboxylic acid having a polyoxyalkylene group, in order to prevent delamination of the film. An ester-forming derivative, a diol having a polyoxyalkylene group, or the like may be copolymerized.

Among them, 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 4-sodium sulfophthalic acid, and 4-sodium sulfo-2,6-naphthalenedicarboxylic acid are preferred in view of polymerization reactivity of polyester and transparency of film. Compounds obtained by substituting acids and their sodium with other metals (eg, potassium, lithium, etc.), ammonium salts, phosphonium salts and the like, or ester-forming derivatives thereof, polyethylene glycol, polytetramethylene glycol, polyethylene glycol-polypropylene glycol copolymers A compound or a compound which is obtained by oxidizing a hydroxy group at both ends thereof to form a carboxyl group is preferred. The proportion copolymerized for this purpose is preferably from 0.1 to 10 mol% based on the bifunctional dicarboxylic acid constituting the polyester.

For the purpose of improving the heat resistance of the film, a bisphenol compound and a compound having a naphthalene ring or a cyclohexane ring can be copolymerized.
The copolymerization ratio is preferably from 1 to 20 mol% based on the bifunctional dicarboxylic acid constituting the polyester.

The polyester used in the present invention may contain an antioxidant. In particular, the effect is remarkable when the polyester contains a compound having a polyoxyalkylene group. The type of the antioxidant to be contained is not particularly limited, and various antioxidants can be used. For example, hindered phenol compounds,
Antioxidants such as phosphite compounds and thioether compounds can be mentioned. Above all, an antioxidant of a hindered phenol compound is preferable in terms of transparency.

The content of the antioxidant is usually from 0.01 to 2% by weight, preferably from 0.1 to 2% by weight, based on the polyester.
0.5%. By setting the content of the antioxidant in this range, it is possible to prevent the so-called fogging phenomenon in which the density of the unexposed portion of the photographic light-sensitive material is increased, and the haze of the film can be suppressed to be low, so that a photograph having excellent transparency can be obtained. Support is obtained. In addition, these antioxidants may be used alone or in combination of two or more.

The biaxially stretched polyester film may be provided with lubricity as required. The means for imparting lubricity is not particularly limited, but a method of adding external particles to the polyester to add inert inorganic particles, a method of depositing internal particles to precipitate a catalyst to be added during the synthesis of the polyester,
Alternatively, a method of applying a surfactant or the like to the film surface is generally used. Among these, an internal particle precipitation method that can control the particles to be deposited relatively small is preferable because lubricity can be imparted without impairing the transparency of the film. As the catalyst, various known catalysts can be used, but it is particularly preferable to use Ca and Mn because high transparency can be obtained. One of these catalysts may be used, or two or more of them may be used in combination.

The biaxially stretched polyester film may have a multilayer structure composed of different types of polyester. For example,
Ethylene terephthalate unit or ethylene-2,6
A layer composed of a polyester having a naphthalate unit as a main component, a layer A, and a layer composed of another polyester a layer B.
In the case of a layer or a C layer, a two-layer structure composed of an A layer and a B layer may be used, or an A layer / B layer / A layer, an A layer / B layer / C layer,
A three-layer structure such as B layer / A layer / B layer or B layer / A layer / C layer may be used. Further, a configuration having four or more layers is of course possible, but it is not practically preferable because the manufacturing equipment becomes complicated. The thickness of the layer A is preferably 30% or more, more preferably 50% or more, of the total thickness of the polyester film.

By using polyethylene terephthalate, polyethylene naphthalate, other homopolyesters, or other copolymerized polyesters having excellent transparency, mechanical strength, dimensional stability, etc. as the polyester constituting the layer B or layer C, In addition, the transparency, mechanical strength, dimensional stability and the like of the entire film can be improved.

Further, when the biaxially stretched polyester film has a multilayer structure, the above-mentioned functions such as antioxidation and lubricity, or the addition of various additives other than those described above may be performed only on the surface layer. The film can maintain high transparency.

The method for synthesizing the polyester as a raw material for the biaxially stretched polyester film is not particularly limited, and the polyester can be produced according to a conventionally known polyester production method. For example, a direct esterification method in which a dicarboxylic acid component is directly esterified with a diol component, first, a dialkyl ester is used as a dicarboxylic acid component, a transesterification reaction between the dialkyl ester and the diol component is performed, and this is heated under reduced pressure. A transesterification method in which polymerization is carried out by removing an excess diol component can be used. At this time, if necessary, a transesterification catalyst or a polymerization reaction catalyst may be used, or a heat stabilizer may be added.
In addition, in each process during the synthesis, a coloring inhibitor, an antioxidant, a crystal nucleating agent, a slipping agent, a stabilizer, an antiblocking agent, an ultraviolet absorber, a viscosity modifier, an antifoaming agent, a clarifying agent, an antistatic agent,
A pH adjuster, a dye, a pigment, and the like may be added.

Next, the curl curl specified in the present invention will be described.

<Curl curl> The curl curl indicates a curl in the winding direction when wound around a core. Specifically, a silver halide photographic material is 120 mm × 35 mm
And cut in an atmosphere of 23 ° C. and 55% RH.
Condition for 4 hours. This sample was wound around a patrone core (diameter 10.8 mm) of a commercially available color film, which was barrier-wrapped, heat-treated at 55 ° C. for 4 hours, and then allowed to cool in an atmosphere of 23 ° C. and 55% RH. 24
After a time, the film was released from the core and the curl of the film was measured.

The curl value is expressed by 1 / R (m ^-1 ).
This R represents the radius of curvature of the curled film.

From the viewpoint of handleability and the like, the curl value of the photographic support of the present invention measured above is 80 m ^-1.
Or less, more preferably 70 m ^-1 or less, and most preferably 60 m ^-1 or less.

The thickness of the biaxially stretched polyester film preferably used in the present invention is not particularly limited.
What is necessary is just to set so that it may have required intensity | strength according to the use purpose. In particular, when the film is used for a color negative photographic light-sensitive material, it is 20 to 125 μm, particularly 40 to 90 μm.
m is preferable. When used for medical or printing photographic materials, the thickness is 50 to 300 μm, particularly 80 μm.
It is preferably from 200 to 200 μm. If the thickness is less than this range, the required strength may not be obtained, and if the thickness is too large, the curl will be larger.

The biaxially stretched polyester film is
The haze is preferably 3% or less. More preferably, it is 1% or less. When the haze is more than 3%, when the film is used as a support for a photographic light-sensitive material, an image is blurred and becomes unclear. The haze is ASTM-D1
003-52.

The Tg of the biaxially stretched polyester film is
60 ° C. or higher is preferred. Tg is determined as an average value of a temperature measured by a differential scanning calorimeter at which a baseline starts to be shifted and a temperature at which the baseline returns to a new baseline.
When the Tg is at least this value, a photosensitive material having no deformation of the film in the drying step of the developing machine and having a small curl after development can be obtained.

Next, a method for producing a polyester film preferably used in the present invention will be described.

The method for obtaining an unstretched sheet and the method for uniaxially stretching in the longitudinal direction can be performed by a conventionally known method.
For example, the raw material polyester is molded into pellets, dried with hot air or vacuum dried, melt-extruded, extruded into a sheet from a T-die, adhered to a cooling drum by an electrostatic application method, cooled, solidified, and unstretched Get a sheet. Then, the obtained unstretched sheet is heated in a range from the glass transition temperature (Tg) of the polyester to Tg + 100 ° C. through a plurality of roll groups and / or a heating device such as an infrared heater, and subjected to single-stage or multi-stage longitudinal stretching. It is. The stretching ratio is usually in the range of 2.5 to 6 times, and it is necessary to make the subsequent transverse stretching possible. When the sheet has a multilayer structure, the setting of the stretching temperature is preferably based on the highest Tg of the Tg of the polyester of each constituent layer.

At this time, when the polyester is laminated,
A conventionally known method may be used. For example, a plurality of extruders and a co-extrusion method using a feed block type die or a multi-manifold type die, melt extrusion of a single layer film constituting a laminated body or other resin constituting a laminated body on a laminated film from an extruder, and cooling. Examples thereof include an extrusion lamination method of cooling and solidifying on a drum, and a dry lamination method of laminating a single-layer film or a laminated film constituting a laminate via an anchor agent or an adhesive as necessary. Among them, a co-extrusion method that requires a small number of production steps and has good adhesion between the layers is preferable.

Next, the polyester film uniaxially stretched in the machine direction obtained as described above is transversely stretched within a temperature range of Tg to Tm-20 ° C., where Tm is a melting point, and then hot stretched. Fix it. The transverse stretching ratio is usually 3 to 6 times, and the ratio between the longitudinal and transverse stretching ratios is determined by measuring the physical properties of the obtained biaxially stretched film and appropriately adjusting the film to have preferable characteristics. In the case of the present invention, the elastic modulus in the width direction is made larger than the elastic modulus in the longitudinal direction. It may be changed according to the purpose of use. At this time, it is preferable to perform transverse stretching while sequentially increasing the temperature in the range of 1 to 50 ° C. in the stretching region divided into two or more portions because the distribution of physical properties in the width direction can be reduced, which is preferable. After further transverse stretching, the film is subjected to T
It is preferable to maintain the temperature in the range of g-40 ° C. or higher for 0.01 to 5 minutes because the distribution of physical properties in the width direction can be further reduced.

The heat setting is carried out at a temperature higher than the final transverse stretching temperature and within a temperature range of Tm-20 ° C. or lower, usually from 0.5 to 30 ° C.
Heat set for 0 seconds. At this time, it is preferable to heat-set while sequentially increasing the temperature in a range of 1 to 100 ° C. in the two or more divided regions.

The heat-fixed film is usually cooled to Tg or less, cut off the clip holding portions at both ends of the film, and wound up. At this time, within the temperature range of not more than the final heat-setting temperature and not less than Tg, 0.1 to 0.1 in the width direction and / or the longitudinal direction.
It is preferable to perform a 10% relaxation treatment. Further, it is preferable that the cooling is gradually performed from the final heat setting temperature to Tg at a cooling rate of 100 ° C. or less per second. The means for cooling and relaxing treatment is not particularly limited, and can be performed by a conventionally known means. In particular, it is preferable to perform these treatments while sequentially cooling in a plurality of temperature regions from the viewpoint of improving the dimensional stability of the film.
The cooling rate is a value determined by (T1−Tg) / t, where T1 is the final heat setting temperature and t is the time required for the film to reach Tg from the final heat setting temperature.

Since the most optimal conditions for the heat setting, cooling and relaxation treatments differ depending on the polyester constituting the film, the physical properties of the obtained biaxially stretched film are measured and adjusted appropriately so as to have preferable characteristics. It may be determined by doing so.

In the production of the film, a functional layer such as an antistatic layer, a lubricating layer, an adhesive layer and a barrier layer may be applied before and / or after stretching. At this time, various surface treatments such as corona discharge treatment and chemical treatment can be performed as necessary. Further, for the purpose of improving the strength, stretching used for known stretched films such as multi-stage longitudinal stretching, re-longitudinal stretching, re-longitudinal-horizontal stretching, and horizontal / longitudinal stretching can be performed.
Of course, the clip gripping portions at both ends of the cut film are crushed, or after granulation, depolymerization, repolymerization, etc., if necessary, as raw materials for the same type of film or different types May be reused as a film raw material.

The biaxially stretched polyester film obtained as described above still has a property of being easily rolled. Therefore, in the present invention, the film is formed by the T method obtained by the following method.
Heat treatment is performed so that the endothermic peak appearing in the vicinity of g is 100 mcal / g or less.

<Glass Transition Temperature Tg> 10 mg of the produced film is melted at 300 ° C. in a nitrogen stream of 300 cc / min and immediately quenched in liquid nitrogen. This quenched sample is subjected to a differential scanning calorimeter (DS8230 manufactured by Rigaku Denki Co., Ltd.).
Type), and in a nitrogen flow of 100 cc / min, 2 min / min.
The temperature is raised at a temperature rising rate of 0 ° C., and Tg is measured. Tg is a temperature of an average value of a temperature at which the baseline starts to be biased and a temperature at which the baseline returns to a new one. Note that the measurement start temperature is a temperature lower than the measured Tg by 50 ° C. or more.

<Endothermic Peak> The emulsion layer and the backing layer of the photographic light-sensitive material thus prepared were peeled off using Higher (Kao Corporation bleaching agent), the remaining subbing layers on both sides were dissolved and removed with acetone, and only the support was removed. obtain. First, the obtained sample was subjected to the aforementioned Tg.
After measuring Tg by the measurement method, the obtained sample 10
mg of differential scanning calorimeter (manufactured by Rigaku Denki Co., Ltd., DSC823).
0) and heated at a rate of 20 ° C./min in a nitrogen stream at 100 cc / min.
g + 20 ° C.). Note that the measurement start temperature is a temperature lower than the measured Tg by 50 ° C. or more.

A more preferable range of the heat treatment is Tg ° C. or higher,
The treatment is performed in a temperature range in which an endothermic peak of Tg + 25 ° C. or less appears. When the film has a multilayer structure, the highest Tg among the polyesters constituting the layer substantially responsible for the rigidity of the film is used as a reference.

The method of performing the heat treatment of the present invention is not particularly limited. However, the present invention is characterized in that the heat treatment can be performed in a much shorter time than the conventional curl reduction method, whereby the curl reduction effect can be obtained. is there. Therefore, a method that can uniformly heat the film in a short time is preferable. As such a method, for example, the film is continuously transported by gripping the both ends of the film with pins or clips, or transporting the roll by a plurality of rolls or air transport that blows air onto the film and floats the film. Heat treatment by spraying heated air from one or more slits on one or both sides of the film surface, using radiant heat from an infrared heater, or contacting with a plurality of heated rolls. Method.

Further, since the heat treatment temperature is equal to or higher than the Tg of the film, if the film is heat-treated while being wound in one direction, a habit of the wound state will be formed. Therefore, it is preferable to perform the heat treatment while maintaining the film in a flat state. However, if necessary, the film is brought into contact with the film so that the curl balance with the photographic emulsion layer can be obtained when the photographic material is finally formed. It is also possible to adjust the diameter of the heat roll or the like, or to make it pass through an appropriate curved surface by air conveyance, thereby giving a proper winding state.

The method of keeping the film flat is as follows:
Although there is no particular limitation, for example, the above-described pin and clip transfer method, air transfer method, roll transfer method, and the like can be used. The roll transport method is not perfectly flat because the roll is transported with a wrap angle with the film, but
Since the film is alternately contacted with the roll on the front and back, and the winding direction of the film does not become one direction, the film can be regarded as substantially flat.

The step of applying the above heat treatment may be any step from the production of the film to the cutting and packaging of the final product.

The heat treatment may be performed in one stage, or may be performed in two or more zones with a temperature difference. Slow cooling may be performed. Also, an adhesive layer, a conductive layer,
After applying and drying various functional layers (so-called undercoat layers) such as a slippery layer and a magnetic recording layer, it is preferable to subsequently perform heat treatment.

Also in this case, the heat treatment can be performed by adjusting the drying temperature or by adding necessary heating equipment, and it is not necessary to newly install a transfer equipment. The heat treatment may be performed in one stage, or may be performed in two or more zones with a temperature difference.

The heat-treated base thus obtained is
Since it is higher than Tg, it needs to be cooled to room temperature. If the film is cooled slowly with Tg in between, the flatness of the film will be degraded. Therefore, the faster the cooling, the faster it is better to obtain the flatness, and it is preferably 1000 ° C. to 1 ° C./min.

The film heat-treated as described above and cooled to room temperature is wound up and stored until it is sent to the next step.

Next, a method for forming a photographic light-sensitive material will be described.

In general, when a hydrophobic polymer film is used as a photographic support, a necessary adhesive strength cannot be obtained even if a hydrophilic photographic emulsion layer is directly applied to the polymer film. Therefore, polymer films usually require surface treatment. Examples of such surface treatments include corona discharge treatment, ultraviolet treatment, glow discharge treatment, plasma treatment, flame treatment, and other surface activation treatments, resorcinol treatment, phenols treatment, alkali treatment, amine treatment, and trichloroacetic acid treatment. And a method of laminating one or more adhesive layers. These methods may be used alone or in combination.

The material that can be used in the method of laminating the adhesive layer is not particularly limited, but for example, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, and maleic anhydride are used as starting materials. Including coalescence, polyethylene imine, polyester, polystyrene, polyurethane, epoxy resin,
Examples include grafted gelatin, nitrocellulose and the like, and mixtures thereof. In these adhesive layers, surfactants, antistatic agents, antihalation agents, crossover cutting agents, coloring dyes, pigments, thickeners, coating aids, antifoggants, antioxidants, ultraviolet absorbers, ultraviolet light stabilizers One or two or more of various additives such as an agent, an etching agent, a magnetic powder, and a matting agent may be contained.

Further, an antistatic layer, a slippery layer, a barrier layer, an antihalation layer, a crossover cut layer,
An ultraviolet absorbing layer, a magnetic recording layer and the like may be laminated.

The method for laminating these adhesive layers and the like is not particularly limited, and various conventionally known methods can be used. For example, before the biaxial orientation of the polyester film is completed or after the completion of the biaxial orientation, the coating method such as air knife coater, dip coater, curtain coater, wire bar coater, gravure coater, extrusion coater, etc. Extrusion and lamination methods can be used.

When the undercoat layer is applied, the surface of the support is
Chemical treatment (Japanese Patent Publication No. 311031, Japanese Patent Publication No. 38-2)
No. 2148, Japanese Patent Publication No. 40-2276, Japanese Patent Publication No. 41-1
No. 6423, Japanese Patent Publication No. 44-5116), chemical mechanical surface roughening treatment (Japanese Patent Publication No. 47-19068, Japanese Patent Publication No. 5)
No. 5-5104), corona discharge treatment (Japanese Patent Publication No. 39-39)
No. 12838, JP-A-47-19824, JP-A-48-48
-28067), flame treatment (Japanese Patent Publication No. 40-123)
No. 84, JP-A-48-85126), UV treatment (JP-B-36-18915, JP-B-37-14493)
No., JP-B-43-2603, JP-B-43-2604
No., JP-B-52-25726), high-frequency processing (described in JP-B-49-10687), glow discharge (JP-B-37)
No. -17682), active plasma treatment, laser treatment and the like. As described in JP-B-57-487, it is preferable that the contact angle between the surface of the support and water is 58 ° or less.

The undercoating process may be performed for a single layer.
In order to obtain more functionality and increase the adhesive strength, it is desirable to use the multilayer method.

In the multilayer method, the undercoating first layer is preferably a layer that adheres well to the support, and the material may be an unsaturated carboxylic acid such as methacrylic acid or acrylic acid or an ester thereof, or a synthetic styrene or the like. Polymers or copolymers obtained from resin monomers, water-dispersed polyesters, polyurethanes, polyethyleneimines, epoxy resins, and the like are included.

The monomers of the synthetic resin used in the undercoat layer of the present invention include styrene and derivatives thereof, unsaturated carboxylic acids such as methacrylic acid, acrylic acid and itaconic acid, and esters thereof such as alkyl acrylate and alkyl methacrylate (as an 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, and 2-hydroxypropyl methacrylate; acrylamide, methacrylamide, N-methyl methacrylamide, N-methyl acrylamide, N-methylol methacrylamide;
Amide group-containing monomers such as N-methylol acrylamide, N, N-dimethylol acrylamide, N-methoxymethyl acrylamide; N, N-diethylaminoethyl acrylate, amino group-containing monomers of N, N-diethylamino methacrylate; glycidyl acrylate;
Epoxy group-containing monomers such as glycidyl methacrylate; carboxyl groups or salts thereof such as acrylic acid and methacrylic acid salts (sodium salt, potassium salt, ammonium salt); styrene sulfonic acid, vinyl sulfonic acid and salts thereof ( Monomers containing a sulfonic acid group or a salt thereof such as a sodium salt, a potassium salt or an ammonium salt; a carboxyl group or a salt thereof such as a salt of an itaconic acid, a maleic acid or a fumaric acid (a sodium salt, a potassium salt or an ammonium salt) Monomers containing acid anhydrides such as maleic anhydride and itaconic anhydride; and vinyl isocyanate, allyl isocyanate, vinyl methyl ether, vinyl ethyl ether, acrylonitrile, and vinyl acetate. The above-mentioned monomers can be copolymerized using one kind or two or more kinds.

As the synthetic resin referred to in the present invention, a rubber-like substance may be used. The rubbery substance generally comprises a vinyl monomer-diolefin. As the vinyl monomer, styrene, acrylonitrile, methacrylonitrile, methyl methacrylate, methyl acrylate, vinyl acetate, etc. are preferably used. As the olefin, butadiene, isoprene and chloroprene are preferably used. In addition to these components, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, or alkyl esters thereof, acrolein, methacrolein, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, N-methylol acrylamide, N-
Methylol methacrylamide, vinyl isocyanate,
It is preferable to add a crosslinkable component such as allyl isocyanate. The content of diolefin is 10 to 60% by weight.
Is preferred.

Preferred polymers which are commercially available and easily available include styrene-butadiene, styrene-isoprene, styrene-chloroprene, methyl methacrylate-butadiene, acrylonitrile-butadiene and the like.

Examples of these polymerization methods include an emulsion polymerization method, a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and a radiation polymerization method.

In solution polymerization, a mixture of monomers at a suitable concentration in a solvent (usually a mixture of not more than 40% by weight, preferably 10 to 25% by weight based on the solvent) is added to a mixture of about 10% by weight in the presence of an initiator. It is obtained by conducting the polymerization at a temperature of from 200 to 200 ° C, preferably from 30 to 120 ° C, for about 0.5 to 48 hours, preferably for 2 to 20 hours.

The initiator may be any as long as it is soluble in the polymerization solvent. Examples thereof include organic solvent-based initiators such as benzoyl peroxide, azobisisobutyronitrile (AIBN) and di-tert-butyl peroxide. Water-soluble initiators such as ammonium sulfate (APS), potassium persulfate, and 2,2'-azobis- (2-amidinopropane) -hydrochloride, and combinations thereof with reducing agents such as Fe2 ⁺ salts and sodium bisulfite. Redox-based polymerization initiators and the like can be mentioned.

The solvent may be any as long as it can dissolve a mixture of monomers, and includes, for example, water, methanol, ethanol, dimethylsulfoxide, dimethylformamide, dioxane, or a mixed solvent of two or more of these. be able to.

After completion of the polymerization, the reaction mixture is poured into a medium in which the formed copolymer is not dissolved, and the product is allowed to settle.
Then, the unreacted mixture can be separated and removed by drying.

In the emulsion polymerization method, water is used as a dispersion medium, and 10 to 50% by weight of a monomer based on water and 0.05 to 5% by weight of a polymerization initiator, 0.1 to 20% by weight based on the monomer.
About 30 to 100 ° C., preferably 60 to 100 ° C.
It is obtained by polymerizing under stirring at 90 ° C. for 3 to 8 hours. The monomer concentration, initiator amount, reaction temperature, time, etc. can be varied widely and easily.

Examples of the initiator include a water-soluble peroxide (eg, potassium persulfate, ammonium persulfate, etc.), a water-soluble azo compound (eg, 2,2′-azobis- (2-amidinopropane) -hydrochloride, etc.) And Fe ²⁺
Redox polymerization initiators combined with a reducing agent such as a salt or sodium hydrogen sulfite can be used.

Examples of the dispersant include anionic surfactants, nonionic surfactants, and water-soluble polymers.
The molecular weight of the polymer obtained in this way cannot be unambiguously determined depending on the intended use, but is usually
About 5 in terms of polystyrene or polyethylene oxide
00 to 5,000,000, preferably 1,000 to 5
00,000.

Regarding the method for synthesizing a hydrophobic polymer, US Pat. Nos. 2,852,386 and 2,853,457,
No. 3,411,911, No. 3,411,912, No. 4,197,127, Belgian Patent 688,882
Nos. 691,360, 712,823, JP-B-45-5331, JP-A-60-18540, and 51
No. 130217, No. 58-137831, No. 55-
No. 50240 and the like.

The average particle size of the hydrophobic polymer is from 0.01 to
0.8 μm is particularly preferred, and any one of 0.005 to 2.0 μm can be preferably used.

When the hydrophobic polymer is polymerized in an organic solvent, it can be used by further dispersing in water and reducing the pressure to replace the solvent with water.

Examples of the water-dispersible polyester which can be used in the present invention include polybasic acids or ester-forming derivatives thereof, dicarboxylic acids having sulfonic acid groups and / or ester-forming derivatives thereof, and polyols or ester-forming derivatives thereof. Is a substantially linear polymer obtained by a condensation polymerization reaction with Examples of the polybasic acid component of this polymer include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid,
Examples include trimellitic acid, pyromellitic acid, dimer acid, and the like. Along with these components, unsaturated polybasic acids such as maleic acid, fumaric acid and itaconic acid and hydroxycarboxylic acids such as p-hydroxybenzoic acid and p- (β-hydroxyethoxy) benzoic acid can be used in a small proportion.

Examples of the polyol component include ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, triglycol, and the like. 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, it is effective to introduce a sulfonate, diethylene glycol, polyalkylene ether glycol or the like. In particular, a dicarboxylic acid component having a sulfonic acid salt (a dicarboxylic acid having a sulfonic acid salt and / or
Or an ester-forming derivative thereof) in an amount of from 5 to 15 mol% based on all dicarboxylic acid components in the water-dispersible polyester.

As the dicarboxylic acid having a sulfonic acid salt and / or the ester-forming derivative thereof used in the undercoat layer of the present invention, those having a group of an alkali metal salt of a sulfonic acid are 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, and ester-forming derivatives thereof are used. However, sodium 5-sulfoisophthalate or an ester-forming derivative thereof is particularly preferred. The dicarboxylic acid having a sulfonic acid salt and / or an ester-forming derivative thereof is particularly preferably used in an amount of from 6 to 10 mol% based on all dicarboxylic acid components from the viewpoint of water solubility and water resistance.

Further, a copolymer containing water-dispersible polyester and a styrene-based polymer as constituents is also preferable. this is,
A copolymer or a composition comprising the above-mentioned water-dispersible polyester and a styrene-based polymer as constituent elements.

The water-dispersible polyester is a linear polymer obtained by a polycondensation reaction between the above polybasic acid or its ester-forming derivative and a polyol or its ester-forming derivative.

When the peroxide that can be used in the present invention is not water-soluble, it can be used by dispersing it in water, but it is preferably water-soluble. Examples of the water-soluble peroxide include an initiator used in the synthesis of the vinyl polymer, for example, a water-soluble peroxide (for example, potassium persulfate, ammonium persulfate, etc.) and hydrogen peroxide. Preferably it is hydrogen. The amount of peroxide used is 0.1 to 0.1% of the solid content of the undercoat layer in terms of effective amount.
Preferably it is 30% by weight. More preferably, 1
-10% by weight.

It is preferable that a hardener is mixed in the undercoat layer of the present invention.

It is preferable that the undercoating solution further contains an activator or a cellulose compound such as methylcellulose in order to improve coating properties.

The undercoating second layer is preferably a hydrophilic resin layer which adheres well to the photographic emulsion layer. A hydrophilic resin layer,
As the constituent binder, gelatin, gelatin derivative, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, carboxymethylcellulose, hydroxyethylcellulose,
And the like, and a combination of a sodium polysulylenesulfonate copolymer and a hydrophobic latex. Gelatin is preferred.

It is preferable to add a hardening agent among them.

The second subbing layer preferably contains inorganic fine particles such as silicon dioxide and titanium oxide and an organic mat material (1 to 10 μm) such as polymethyl methacrylate.

In addition to the above, various additives such as an antistatic agent, an antihalation agent, a coloring dye, a pigment, and a coating aid can be contained as necessary.

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

In the present invention, an automatic developing machine having the following method and mechanism can be preferably used.

(1) Deodorizing device: JP-A-64-37560
No. 544 (2), upper left column to page 545 (3), upper left column.

(2) Washing water regeneration purifying agent and apparatus: JP-A-6-250352, page (3), “0011” to page (8), “0058”.

(3) Waste liquid treatment method: JP-A-2-6463
No. 8, 388 (2) lower left column to 391 (5) lower left column.

(4) Rinse bath between developing bath and fixing bath: JP-A-4-313949, page (18), "0054" to (2)
1) Page "0065".

(5) Water replenishment method: JP-A-1-28144
No. 6, page 250 (2), lower left column to lower right column.

(6) Method of controlling the drying air of an automatic developing machine by detecting the outside air temperature and humidity: JP-A-1-315745
6 (2) lower right column to 501 (7) lower right column and
No. 108051 No. 588 (2), lower left column to 589 (3)
The lower left column of the page.

(7) Method for recovering silver from fixing waste liquid:
No. 27623, page (4) “0012” to page (7) “00”
71 ".

The halogen composition of the silver halide in the silver halide photographic light-sensitive material of the present invention is not particularly limited. However, when processing is carried out with a small replenishing amount or when rapid processing is carried out, 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 the silver halide is 1.2 μm.
m or less, particularly 0.8 to 0.1 μm
Is preferred. The average particle size is a term that is commonly used by experts in the field of photographic science and is easily understood. The particle size means a particle diameter when the particles are spherical or spherical particles. If the particles are cubic, they are converted into spheres, and the diameter of the sphere is defined 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. By James: The theor
y of the photographic pro
ses), Third Edition, pp. 36-43 (1966 (published by Macmillan "Mcmillan")).

The shape of the silver halide grains is not limited.
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Further, it is preferable that the particle size distribution is narrower, and in particular, a so-called monodisperse emulsion in which 90%, preferably 95% of the total number of particles falls within a particle size range of ± 40% of the average particle size is preferable.

The silver halide emulsion and its preparation method are described in detail in Research Disclosure (Res).
(Earth Disclosure) 176 No. 1764
3, pages 22 to 23 (December 1978).

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

In the silver halide photographic light-sensitive material of the present invention,
Various compounds can be contained for the purpose of preventing fogging during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance.

It is advantageous to use gelatin as a binder or protective colloid of the photographic emulsion of the silver halide photographic light-sensitive material of the present invention, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol Use of various kinds of synthetic hydrophilic high-molecular substances such as mono- or copolymers of polyvinyl alcohol, partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be.

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

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of improving dimensional stability and the like. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide,
Vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene or the like alone or in combination;
Alternatively, it is possible to use a polymer having a monomer component of a combination of these with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid, or the like. it can.

In the photographic emulsion and the non-photosensitive hydrophilic colloid layer of the present invention, an inorganic or organic hardener is added as a crosslinking agent for a hydrophilic colloid such as gelatin.

These hardeners are available from Research Disclosure 1
76, 17643 (published December 1978), page 26, paragraphs A to C.

The photosensitive material used in the present invention contains various other additives. For example, a desensitizer, a plasticizer, a slipping agent, a development accelerator, an oil and the like can be mentioned.

In the present invention, the following compounds are preferably contained in the constituent layers of the silver halide photographic material.

(1) Solid-dispersed fine particles of a dye JP-A-7-5629, page (3) [0017] to (1)
6) Compound described on page [0042] (2) Compound having an acid group Compound described in JP-A-62-237445, page 292 (8), lower left column, line 11 to page 309 (25), lower right column, line 3 (3) Acidic polymer JP-A-6-186659, page (10) [0036]
(4) Sensitizing dye JP-A-5-224330, page (3) [0017] to (17)
(13) Compound described on page [0040] JP-A-6-194777 (page 11) [0042]
Compound described in [0094] to page (22) [0015] to page (2) in JP-A-6-242533
(8) Compound described on page [0034] JP-A-6-337492 (3) page [0012]-
(34) Compound described on page [0056] JP-A-6-337494 (4) page [0013]-
(14) Compound described on page [0039] (5) Supersensitizer JP-A-6-347938 (3) page [0011] to
(16) Compound described on page [0066] (6) Hydrazine derivative JP-A-7-114126, page (23) [0111]
(7) Nucleation accelerator: JP-A-7-114126, page (32) [0158]
(8) Tetrazolium compound JP-A-6-208188, page (8), [0059] to
(10) Compound described on page [0067] (9) Pyridinium compound JP-A-7-110556 (5) page [0028] to
(29) Compound described in [0068] (10) Redox compound JP-A-4-245243, pages 235 (7) to 250
Compounds described on page (22) The above-mentioned additives and other known additives are described, for example, in Research Disclosure No. 17643
No. (December 1978). 18716 (1979
No.) and the same No. 308119 (December 1989
Month). The following table shows the types and locations of the compounds shown in these three research disclosures.

Additive RD-17643 RD-18716 RD-308119 page Classification page Classification page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IVA Desensitizing dye 23 IV 998 IVB Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right antifoggant / stabilizer 24 IV 649 Upper right 1006-7 VI Brightener 24 V 998 V Hardener 26 X 651 Left 1004-5 X

[0119]

The present invention will be described in more detail with reference to the following examples.

The intrinsic viscosity of the polyester used in the examples was measured as follows.

(1) Intrinsic viscosity The film or pellet was prepared by mixing phenol with 1,1,2,2
Mixed solvent of 2-tetrachloroethane (weight ratio 60/4)
0), and dissolved at a concentration of 0.2 g / dl, 0.6 g / dl,
A 1.0 g / dl solution is prepared, and the specific viscosity (η _sp ) at each concentration (C) is determined at 20 ° C. using an Ubbelohde viscometer. Next, η _sp / C is plotted against C, and the obtained straight line is extrapolated to zero concentration.

[0122]

(Equation 1)

Is obtained. The unit is indicated by dl / g.

Next, the method for producing the film used here will be described collectively.

(Preparation of polyester) 100 parts by weight of dimethyl terephthalate and 65 parts by weight of ethylene glycol were mixed with 0.05 g of magnesium acetate hydrate as a transesterification catalyst.
A part by weight was added, and a transesterification reaction was performed according to a conventional method. 0.05 parts by weight of antimony trioxide and 0.03 parts by weight of trimethyl phosphate were added to the obtained product. Then, the temperature was gradually increased and the pressure was reduced.
Polymerization was performed at mmHg to obtain a polyester having an intrinsic viscosity of 0.65. The Tg of this polyester was 76 ° C.

Using this polyester, 150 ° C.
, And then extruded at 285 ° C using an extruder, extruded in layers from a T-die, brought into close contact with a cooling drum at 30 ° C while applying static electricity, cooled and solidified to form a two-layer laminate. A stretched sheet was obtained.

This unstretched sheet was stretched 3.3 times in the machine direction at 95 ° C. using a roll-type longitudinal stretching machine.

The obtained uniaxially stretched film was stretched in a first stretching zone at 100 ° C. by 50% of the total transverse stretching ratio using a tenter type transverse stretching machine, and further at a second stretching zone at 115 ° C. at a total transverse stretching ratio of 3. The film was stretched three times. Then 70
C. for 2 seconds, further heat-set at 150 ° C. in the first heat-setting zone for 5 seconds, and heat-set in the second heat-setting zone at 230 ° C. for 15 seconds in the width direction by about 3%. This was cooled to room temperature.

<Coating of Undercoat Layer> The above film was subjected to undercoat treatment as follows.

23 W / (m ² · min) on both sides of the support
The undercoating liquid A-1 is applied to the surface A of the support so as to have a dry film thickness of 0.8 μm to form an undercoat layer A-1, and the other side of the support The undercoat layer B-1 was formed on the B surface, which is the surface of the above, so that the undercoating processing liquid B-1 had a dry film thickness of 0.8 μm.

<Undercoat Coating Solution A-1> Latex of butyl acrylate / t-butyl acrylate / styrene / hydroxyethyl acrylate = 30/20/25/25 (each part by weight) (solid content: 30%) 270 g Compound (UL -1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finished with water 1000 ml <Subbing coating solution B-1> Latex liquid of butyl acrylate / styrene / glycidyl acrylate = 40/20/40 (Solid content 30%) 270 g Compound (UL-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finished with water 1000 ml Further, subbing layer A-1 and subbing layer B-1 8W / (m
² · min), and a coating liquid A-2 shown below was applied on the undercoat layer A-1 to a dry film thickness of 0.1 μm to form an undercoat layer A-2. On the undercoat layer B-1, the following coating solution B-2 was applied to a dry film thickness of 4.0 μm to form a layer B-2 having an antistatic function.

<Coating Liquid A-2> Gelatin 10 g Compound (UL-1) 0.2 g Compound (UL-2) 0.2 g Compound (UL-3) 0.1 g Silica particles (average particle size: 3 μm) 1 g Finished with water 1000 ml <Coating solution B-2> Antimony-doped tin oxide powder SN-100P manufactured by Ishihara Sangyo Co., Ltd. 200 g Polyester Toyobo Co., Ltd. Byron 28SS (moisture swelling coefficient 5 × 10 ⁻⁵ ) 100 g Cyclohexanone 140 g Methyl ethyl ketone 280 g 280 g of toluene

[0133]

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Further, the following coating solution OC-1 was applied on the coating layer of B-2 at a concentration of 10 ml / m ² .

<OC-1> Carnauba wax 1 g Toluene 700 ml Methyl ethyl ketone 300 ml <Heat treatment after undercoating> The obtained undercoated base was heat-treated as shown in Table 1, and then the emulsion was coated to obtain a photographic light-sensitive material. Obtained.

<Coating of Photosensitive Layer> The film obtained by the heat treatment was subjected to a corona discharge treatment of 25 W / (m ² / min), and the following printing was performed on the A side of 1-1 to 1-23. A photographic constituent layer for a light-sensitive material and a backing layer for a printed light-sensitive material described below were sequentially formed on side B.

[Preparation of silver halide emulsion coating solution Em-1] In a nitric acid acidic atmosphere at a temperature of 40 ° C. and a pH of 3.0, a solution B was added to the following solution A while maintaining a silver potential EAg at 170 mV with 1N NaCl. Solution C was mixed in a controlled double jet method for 11 minutes.

Solution A Gelatin 5.6 g HO (CH ₂ CH ₂ O) _n (CH (CH ₃ ) CH ₂ O) ₁₇ (CH ₂ CH ₂ O) _m H (n + m = 6) 10% ethanol solution 0 .56 ml sodium chloride 0.12 g concentrated nitric acid 0.43 ml distilled water 445 ml solution B silver nitrate 60 g concentrated nitric acid 0.208 ml distilled water 85.2 ml solution C gelatin 3 g HO (CH ₂ CH ₂ O) _n (CH (CH ₃ ) CH ₂ O) ₁₇ (CH ₂ CH ₂ O) _m H (n + m = 6) 10% ethanol solution 0.3 ml sodium chloride 20.2 g distilled water 85.61 ml solution D gelatin 1.4 g HO (CH ₂ CH ₂ O) _{n (CH (CH 3) CH} 2 O) 17 (CH 2 CH 2 O) m H ( where n + m = 6) 10% ethanol solution 0.14ml of distilled water 48.8ml resulting halogeno The average particle size of grains is 0.12μm
The monodispersity was 8 to 15%.

Solution D was added to the emulsion thus prepared, the pH was adjusted to 6.0 with sodium carbonate, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added. 200 mg was added. Thereafter, each silver halide emulsion was washed with water and desalted according to a conventional method, and solution E was added as a preservative.

Solution E 2-Methyl-5-chloroisothiazol-3-one 15 mg Pure water 0.3 ml As a stabilizer, 4-hydroxy-6-methyl-
200 mg of 1,3,3a, 7-tetrazaindene and 8.6 g of gelatin were added.

Further, the following coating additives were added, and the mixture was adjusted with pure water so that the total amount of the coating solution was 303 ml, thereby preparing a silver halide emulsion coating solution Em-1.

Saponin 33% (W / V) aqueous solution 2.2 ml Sodium dodecylbenzenesulfonate 20% (W / V) aqueous solution 2.2 ml 1-decyl-2- (3-isopentyl) succinate-2-sodium sulfonate 4 % (W / V) aqueous solution 0.3 ml Polymer latex 20% (W / V) emulsion 31.8 ml (copolymer of cyclohexyl-methacrylate, isononyl acrylate, glycidyl acrylate, styrene-isoprene sulfonic acid having an average particle size of 0.25 μm) The following hydrazine derivative (Hd) 2% (W / V) methanol solution 7.5 ml The following amine compound (Am) 5% (W / V) aqueous solution 4 ml Citric acid 7% (W / V) aqueous solution 0.4 ml p-C 2% _{9 H 19 PhO (CH 2 CH} 2 O) 35 H (W / V) aqueous solution of 26 5 ml 2-mercaptohypoxanthine 0.5% (W / V) alkaline aqueous solution 4 ml ethylenediaminetetraacetate 5% (W / V) aqueous solution 10 ml 5% of spirobis (3,3-dimethyl-5,6-dihydroxyindane) (W / V) Methanol solution 1.5 ml Hydroquinone 20% (W / V) aqueous solution 2.5 ml 4% (W / V) aqueous solution of a water-soluble copolymer of styrenesulfonic acid and maleic acid 4 ml 2-methyl-5-chloroisothiazole -3-one 5% (W / V) methanol solution 0.1ml

[0143]

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[Preparation of Coating Solution M-1 for Intermediate Layer] The following additives were added and mixed, and adjusted with pure water so that the total amount became 14,14 ml, thereby preparing coating solution M-1 for intermediate layer.

Gelatin 12% (W / V) aqueous solution 250ml Saponin 33% (W / V) aqueous solution 12.3ml Sodium dodecylbenzenesulfonate 20% (W / V) aqueous solution 12.3ml Citric acid 7% (W / V) Aqueous solution 3 ml Dimazon S 2% (W / V) methanol solution 20 ml Resorcin 20% (W / V) aqueous solution 40 ml Garlic acid propyl ester 10% methanol solution 60 ml Dye 2% (W / V) aqueous solution of the following E 700 ml with styrene sulfonic acid 4% (W / V) aqueous solution of a water-soluble copolymer of maleic acid 22.7 ml 2-Bromo-2-nitro-1,3-propanediol 0.1% (W / V) aqueous solution 6 ml The following fine particle dispersion Bu 250 ml [ Preparation of Coating Solution P-1 for Protective Layer] The following additives are added and mixed to make a total amount of 1414 ml. Was prepared by the protective layer coating solution P-1 adjusted so that pure water.

Gelatin 12% (W / V) aqueous solution 250 ml 1-decyl-2- (3-isopentyl) succinate-2-sodium sulfonate 4% (W / V) aqueous solution 50 ml NaCl 10% aqueous solution 22 ml Amorphous silica (average particle size) Diameter 3.5 μm) 2 g Amorphous silica (average particle size 6 μm) 4 g 0.08% methanol solution of p-C ₉ F ₁₇ OPhSO ₃ Na 70 ml Citric acid 7% (W / V) aqueous solution 5.1 ml Dimezone S2% ( (W / V) methanol solution 20 ml dye 2% (W / V) aqueous solution of the following E 700 ml 4% (W / V) aqueous solution of a water-soluble copolymer of styrenesulfonic acid and maleic acid 22.7 ml 2-bromo-2-nitro- 1,3-propanediol 0.1% (W / V) aqueous solution 6 ml The following fine particle dispersion Bu 250 ml

[0147]

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[Preparation of Dye Dispersion Bu] An amount of 100 mg / m ² of the following dye Se was applied so that ethyl acetate 2
Solution dissolved in 00 ml, gelatin 30 g, citric acid 14
7 mg, isopropyl naphthalene sulfonic acid 400 m
g and 3 g of phenol dissolved in 250 ml of pure water are dispersed by a PD disperser, and then ethyl acetate is removed while heating under reduced pressure. After finishing to 250 ml with pure water, it was cooled and set to prepare a dye dispersion having an average dye particle diameter of 0.20 μm.

[0149]

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[Preparation of Backing Layer Coating Solution BC1] The following additives were added and mixed, and then adjusted with pure water so that the total amount became 895 ml, thereby preparing a backing layer coating solution BC1.

Gelatin 32.4 g Pure water 696 ml 6% (W / V) aqueous solution of the following dye C 64 ml 5% (W / V) aqueous solution of the following dye D 24 ml Saponin 33% (W / V) aqueous solution 6.6 ml Polymer latex 33.6 ml of 20% (W / V) emulsion (cyclohexyl methacrylate, isononyl acrylate, average particle size 0.10 μm, copolymer of glycidyl acrylate and styrene-isoprenesulfonic acid) 10% (W / V) solid of zinc oxide Fine particle dispersion (average particle size 0.15 μm) 10 ml Co ³⁺ (H ₂ NC (NH) NHC (NH) NH ₂ ) ₃ (BPh ^4- ) ₃ solid fine particle dispersion (average particle size 0.1 μm) 10 ml Citric acid 7% (W / V) aqueous solution 3.8ml Sodium styrene sulfonate 4% (W / V) aqueous solution 23ml

[0152]

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[Preparation of Coating Solution BP1 for Backing Protective Layer] After the following additives were added and mixed, the mixture was adjusted with pure water to a total amount of 711 ml to prepare a coating solution BP1 for the backing protective layer.

Gelatin 24.9 g Pure water 605 ml 2% (W / V) dispersion of methyl methacrylate (average particle size 7 μ) 72 ml 1-decyl-2- (3-isopentyl) succinate-2-sodium sulfonate 4% (W / V) aqueous solution 11 ml Glyoxal 4% (W / V) aqueous solution 4 ml [Preparation of hardening agent solution BH1 for in-line addition of backing layer] Pure water 27.22 ml Methanol 1.5 ml Hardening agent H1 1.28 ml below NaCl 0 0.005 g The above additives were mixed to prepare 30 ml of a hardening agent liquid BH1 to be mixed and added in-line immediately before application to the protective layer coating liquid.

[0155]

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[Preparation of Samples No. 1 to No. 13] The above-mentioned silver halide emulsion coating solution E-1 was dried with gelatin at 1.0 g.
/ M ^2, so that the grain-weight 3.5 g / m ^2, an intermediate layer coating solution M-1 so that the gelatin dry weight 0.3 g / m ^2, the coating solution P-1 for protective layer With a gelatin dry weight of 0.
Simultaneous multi-layer coating was performed so as to be 3 g / m ² . At that time, the hardener H-1 was added in-line.

At the same time, the backing layer coating solution BC1 was coated on the opposite side of the support with the hardening agent solution B for backing layer in-line addition.
H1 and the coating liquid BP1 for backing protective layer having a dry gelatin weight of 0.8 g / m ² while being mixed with H1 just before the coating at the finish ratio described above so that the dry weight of gelatin is 1.8 g / m ² .
Multi-layer coating was performed so as to be 5 g / m ² . After applying all the coating solutions at a coating solution temperature of 35 ° C., set them by treating them with cold air of 5 ° C. for 6 seconds, and sequentially controlling the conditions for keeping the dry-bulb temperature 35 ° C. or less and the film surface temperature 20 ° C. or less. The coated layer was dried for 2 minutes, and treated at a dry bulb temperature of 50 ° C and a dew point of -5 ° C for 50 seconds within 20 seconds after the completion of the drying.

<Transportability of Automatic Developing Machine> The obtained photographic light-sensitive material was wound around a 2.8-inch paper core with the emulsion surface wound therein, and heat-treated at 40 ° C. for 72 hours (corresponding to a self-release time of 2 years). )
After the application, the film was set in an automatic developing machine, and the transportability was evaluated as follows.

：: No jamming occurs even when 100 sheets are passed. Δ: 10 out of 100 sheets are jammed.

<Workability> The obtained photographic light-sensitive material was used in the following manner.
Wrap the emulsion surface in and out of an 8 inch paper core.
A heat treatment at 0 ° C. × 72 hours (corresponding to a self-release time of 2 years) was performed. The material wound inside the roll and the material wound outside the roll were aligned so that the emulsion surfaces were in contact with each other, and a hole was drilled.

：: Accurate pin-hole drilling operation △: Accurate pin-hole operation by holding down the sample: Some problem in workability ×: Pin hole shifts when pin-hole operation is performed by holding down the sample.

[0162]

[Table 1]

In the present invention, it can be seen that a silver halide photographic light-sensitive material having no problem in coatability of the emulsion layer in a short time and having no problem in workability even when stored in a roll state can be obtained.

[0164]

According to the constitution of the present invention, a silver halide photograph which is a support excellent in coatability of an emulsion and transportability of a self-developing machine, has little curl even when stored in a roll and has excellent workability. A photosensitive material was obtained.

Claims (4)

[Claims] 1. A photograph wherein the degree of curl of the support is 80 m ^-1 or less, and the calorific value of an endothermic peak developed near the glass transition temperature (Tg) of the support is 100 mcal / g or less. Support. 2. The photographic support according to claim 1, wherein the photographic support is a polyester having an ethylene-terephthalate unit or an ethylene-naphthalenedicarboxylate unit as a main component. 3. The method for producing a photographic support according to claim 1, wherein the average cooling rate in the step of cooling from Tg to room temperature is 1000 ° C./min to 1 ° C./min. A method for producing a photographic support. 4. A silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer on the photographic support according to claim 1.