JPH1039448A - Photographic support - Google Patents

Abstract

PROBLEM TO BE SOLVED: To lower the tendency to curl and to enhance operation efficiency by heat treating the support while conveying it in a temperature range higher than a glass transition point Tg with a specified tension. SOLUTION: The photographic support of a biaxially stretched polyester film is subjected to heat treatment while conveying it from after drying an undercoat layer to coating it with an emulsion layer in a tension of 5-60kg/m in the temperature range of Tg-Tg+35 deg.C. The heat treatment method is not especially limited, and for example, the support is continuously conveyed by holding both ends of the film with pins or clips or by using a group of plural rolls or blowing air upon the film to float it in the air, and heat treated by blowing heated air upon one side or both sides of the film through plural slits, or using radiation heat, or bringing it with plural heated rolls in the single method of them or a combination of them 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 support used for a silver halide photographic light-sensitive material manufactured or used by being wound into a roll, and more particularly to a silver halide excellent in workability which is hard to be wound. The present invention relates to a support for a photographic light-sensitive material.

[0002]

2. Description of the Related Art When photographic light-sensitive materials are used in various sizes, they are often used by taking out a necessary amount from a rolled form from the viewpoint of easy handling and space saving. Particularly in the printing and plate making industry, they are used in large amounts in the form of roll films.

When using such a roll-shaped film, a problem in operation is curling due to winding of the film. For example, when performing continuous cutting with an automatic roll cutter, the cut film does not overlap well if the winding of the film is strong, or there is a problem such as poor adhesion when performing close exposure with a document. I was

[0004] In recent years, with the miniaturization of the apparatus, the roll film has also tended to be compact, and the core wound in a roll has also been miniaturized, and there has been a strong demand for a roll film with little curl.

As a method for improving the curl, for example, a method for reducing the curl of a polyester film is disclosed in JP-A-51-16358.
A method has been proposed in which a thermoplastic resin film is heat-treated at Tg-5 ° C to Tg-30 ° C for 0.1 to 1500 hours. Further, in Japanese Patent Application Laid-Open No. 6-35118, Tg is 9
After undercoating a polyester film at 0 ° C to 200 ° C, 5
A method of performing heat treatment at 0 ° C. to Tg for 0.1 to 1500 hours has been proposed.

However, these methods require a long-time heat treatment at a relatively low temperature, which is inefficient in manufacturing.
In addition, when a product is manufactured in a long length, it must be heat-treated for a long time once in a roll state wound as an intermediate product, and a problem arises in that the winding in the diameter wound in that state is attached in advance. There is. Then, when the silver halide photographic light-sensitive material is subsequently processed into rolls, there is a problem in that a sufficient effect cannot be obtained due to the influence of the winding previously applied by this heat treatment.

This problem is small in the case of a roll-shaped silver halide photographic light-sensitive material wound around a relatively small core diameter such as a color negative film or the like, but is relatively small for a relatively large core such as a printing photosensitive material. In the case of a roll-shaped silver halide photographic light-sensitive material wound in a diameter, the influence is large, which is a problem.

Further, when heat treatment is performed in a roll state, there is a problem of deterioration of flatness and sticking between contacting surfaces, and there is a limitation in a heat treatment process.

[0009]

In view of the above problems, an object of the present invention is to provide a roll-shaped silver halide photographic light-sensitive material having a relatively large diameter such as a printing light-sensitive material. It is an object of the present invention to provide a photographic support which can be used as a silver halide photographic light-sensitive material which is hardly curled and excellent in workability.

[0010]

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

(1) In a photographic support comprising a biaxially stretched polyester film, the support is coated at 5 kg / m from the time when the undercoat layer is coated and dried until the emulsion layer is coated. While transporting with a tension of ~ 60 kg / m,
A photographic support, wherein the polyester film is heat-treated at a temperature of Tg to Tg + 35C.

(2) The photographic support is 10 kg / m or more.
The photographic support according to (1), wherein the photographic support is heat-treated while being conveyed at a tension of 30 kg / m.

(3) The photographic support according to (1) or (2), wherein the photographic support is heat-treated at a temperature of Tg + 5 ° C. to Tg + 25 ° C. of the polyester film.

(4) The polyester film is stretched and formed while giving a temperature difference of 10 ° C. to 40 ° C. on the front and back surfaces during the film forming process. 2. The photographic support according to claim 1.

(5) The heat treatment is performed at a relative humidity of 20% RH.
(1) characterized by being carried out in an atmosphere of 100% RH, in superheated steam, or in a water bath.
The photographic support according to any one of the above (4).

Hereinafter, the present invention will be described in detail.

The heat treatment of the present invention is different from the annealing treatment performed in a roll state in a temperature range equal to or lower than the Tg of the support, and a specific heat treatment in a temperature range higher than Tg. This is a method of performing heat treatment while transporting under tension, thereby making it difficult to curl.

The heat treatment of the support in the present invention is characterized in that the heat treatment is carried out continuously while being transported. That is, while transporting at a tension of 5 kg / m to 60 kg / m,
Heat treatment is performed at a temperature of Tg to Tg + 35 ° C. More preferably, the heat treatment is performed at a temperature of Tg + 5 ° C. to Tg + 25 ° C., and the transport tension is 10 kg / m to
More preferably, it is 30 kg / m.

The transport tension can be adjusted by controlling the torques of the feed shaft and the take-up shaft. If the transport tension is 5 kg / m or less, wrinkling may occur or the surface of the support may be reduced. It is not preferable because the property deteriorates. If it is 60 kg / m or more, the flatness is deteriorated, the effect of improving the curling is not so much improved, and there is a risk of the support being torn.

In the heat treatment of the present invention, the method of performing the heat treatment while transporting is not particularly limited.
The film is transported continuously by gripping both ends of the film with pins or clips, or by roll transport by multiple roll groups or air transport that blows air to the film and floats it, etc., from multiple slits A method in which heated air is blown onto one or both surfaces of the film, a method using radiant heat from an infrared heater or the like, a method in which the heated air is brought into contact with a plurality of heated rolls, or a combination of a plurality of methods is used for heat treatment.

In the heat treatment of the present invention, it is preferable to convey the film while holding it in a flat state. There is no particular limitation, but for example, the above-mentioned conveying method using pins and clips, air conveying method, and roll conveying method. And the like. The roll transport method is not completely flat because the roll is transported with a wrap angle with the film, but the film is in contact with the roll alternately and the winding direction of the film does not become one direction. In general, the film can be considered flat.

The time required for the heat treatment of the present invention is 0.05
Minutes to 60 minutes, preferably 0.5 minutes to 30 minutes, more preferably 1 minute to 15 minutes. The heat treatment time can be controlled by changing the transport speed of the film or changing the length of the heat treatment zone.

The heat treatment of the present invention is more effective when performed in the presence of more water. Specifically, the relative humidity of the atmosphere in the heat treatment zone is set to 20% RH to 100% R.
H is preferable. More preferably, 50% RH
１００100% RH. In the case of heat treatment exceeding 100 ° C., the heating steam can be blown into the zone. Alternatively, when the heat treatment temperature is lower than 100 ° C., the same heat treatment as described above may be performed in a water bath set at the heat treatment temperature.

It should be noted that the heat-treated film of the present invention loses its effect when heated at a temperature of 100 ° C. or more for 0.5 minutes or more. Therefore, the heat treatment of the present invention is preferably performed after the undercoat layer is applied to the film and dried, and before the photographic photosensitive layer is applied. Specifically, after applying and drying the undercoat layer, it may be performed while being kept flat continuously, or, after winding once, installing necessary transport equipment and heating equipment. The re-transport processing may be performed.

Further, after applying and drying various functional layers such as a backing layer, a conductive layer, a slippery layer, and a magnetic recording layer, the same treatment as described above may be performed.

The film heat-treated as described above is cooled from Tg + 5 ° C. to normal temperature and wound up. In order to maintain the flatness of the film, the cooling at this time is preferably as fast as possible to lower the temperature to room temperature over Tg, and it is preferable to cool at a temperature of at least -10 ° C / sec or more.

The support thus heat-treated and cooled to room temperature and wound up is preferably spread over a core as large as possible when it is stored until it is sent to the next step. Has an outer diameter of 200 mm or more,
More preferably 300 mm or more, further preferably 40 mm or more.
0 mm or more.

When the film is stored, the moisture content of the film is adjusted to 0.1.
By adjusting the content to 1% or less, curling during storage can be prevented, which is preferable. The moisture content of the film is a value determined by measuring the film at a drying temperature of 150 ° C. using a trace moisture meter (for example, CA-05 manufactured by Mitsubishi Kasei Corporation).

The polyester constituting the biaxially oriented polyester film of the present invention is not particularly limited, but is preferably a film-forming polyester having a dicarboxylic acid component and a diol component as main components. .

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.

Examples of the diol component include ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4-hydroxyethoxyphenyl) propane. , Bis (4-hydroxyphenyl) sulfone, bisphenol full orange hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone,
Cyclohexanediol and the like can be mentioned.

Among the polyesters containing these as main constituents, terephthalic acid and / or 2,6-naphthalenedicarboxylic acid and diol components as dicarboxylic acid components from the viewpoint of transparency, mechanical strength and dimensional stability. And polyesters containing ethylene glycol and / or 1,4-cyclohexanedimethanol as main constituents. Among them, polyesters having polyethylene terephthalate or polyethylene 2,6-naphthalate as a main component, copolymerized polyesters composed of terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and mixtures of two or more of these polyesters Is preferred as a main component. When the polyethylene terephthalate unit or the polyethylene-2,6-naphthalate unit is contained in an amount of 70% by weight or more with respect to the polyester, a film having excellent transparency, mechanical strength, dimensional stability, and the like can be obtained. It is well known that a film containing polyethylene-2,6-naphthalate as a main component has better mechanical strength and heat resistance than a film containing polyethylene terephthalate as a main component. On the other hand, a film containing polyethylene-2,6-naphthalate as a main component also has disadvantages such as a property of emitting fluorescent light and an expensive resin. Therefore, depending on the purpose of use, a film containing polyethylene terephthalate as a main component is usually used, and polyethylene-2,6 is used especially when a highly thin film is required or when it is used abundantly at a high temperature. −
A film containing naphthalate as a main component may be used. Further, by mixing both, the disadvantages of each other can be compensated.

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

The photographic support of the present invention may contain an antioxidant. The type of the antioxidant to be contained is not particularly limited, and various antioxidants can be used. Examples thereof include antioxidants such as hindered phenol compounds, phosphite compounds, and thioether compounds. Can be. 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
It is 2% by weight, preferably 0.1-0.5%. By setting the content of the antioxidant in this range, the density of the unexposed portion of the photographic light-sensitive material is increased, that is, the so-called fogging phenomenon can be prevented, and the haze of the film can be suppressed to be low, so that the transparency is excellent. A photographic support is obtained. In addition, these antioxidants may be used alone or in combination of two or more.

The photographic support of the present invention may be provided with lubricity as required. The means for imparting lubricity is not particularly limited, but a method of adding external particles to add inert inorganic particles, a method of depositing internal particles to precipitate a catalyst to be added at the time of polymer polymerization, or a method of applying a surfactant to the film surface are used. The method 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.

The thickness of the photographic support pair of 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 used for medical or printing photographic light-sensitive materials, 50 to 250 μm, particularly 70 to 250 μm
It is preferably 200 μm.

The haze of the biaxially oriented polyester film of the present invention 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 photosensitive material,
The image becomes blurred. The haze is ASTM-D10
It is measured according to 03-52.

The Tg of the biaxially oriented polyester film of the present invention is preferably at least 60 ° C., more preferably at least 70 ° C. 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.

Next, a method for producing the polyester film of the present invention will be described.

A method for obtaining an unstretched sheet and a 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. Next, the obtained unstretched sheet is subjected to Tg + 100 from the glass transition temperature (Tg) of the polyester through a plurality of roll groups and / or a heating device such as an infrared heater.
This is a method in which the film is heated in the range of ° C. and longitudinally stretched. The stretching ratio is usually in the range of 2.5 to 6 times.

At this time, by making the stretching temperature have a temperature difference between the front and back sides of the support, it is possible to make the winding hard. More specifically, the temperature can be controlled by providing a heating means such as an infrared heater on one side during the longitudinal stretching. The temperature difference during stretching is preferably 10 ° C.
To 40 ° C, more preferably 15 ° C to 30 ° C. If the temperature difference is larger than 40 ° C., the film cannot be stretched uniformly, and the flatness of the film tends to deteriorate.

As described above, the effect of the film which has been formed by longitudinal stretching at a temperature difference and formed into a photographic material so that the surface stretched at a higher temperature becomes a roll is more effective. .

Next, the polyester film uniaxially stretched in the machine direction obtained as described above was subjected to Tg to Tg + 1.
In the temperature range of 20 ° C., the film is stretched laterally and then heat-set.
The transverse stretching ratio is usually 3 to 6 times, and the ratio between the longitudinal and transverse stretching ratios is to measure the physical properties of the obtained biaxially stretched film.
It is adjusted appropriately so as to have preferable characteristics.

Next, heat fixing is performed at a temperature higher than the final transverse stretching temperature and within a temperature range of Tg + 180 ° C. or lower, usually 0.5 ° C.
Heat set for ~ 300 seconds.

Next, the undercoat layer used for the support of the present invention will be described.

In general, when a hydrophobic polymer film is used as a photographic support, the 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 the like. These surface treatments may or may not be performed. However, in the support of the present invention, one or more undercoat layers are coated and dried, and then subjected to a specific heat treatment while the emulsion layer is coated. Is what you do.

The material which can be used in the method of coating the undercoat layer is not particularly limited, but for example, starting materials are vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, and maleic anhydride. Including copolymers, polyethylene imine, polyester, polystyrene, polyurethane, epoxy resin,
Examples include grafted gelatin, nitrocellulose and the like, and mixtures thereof. Surfactants, antistatic agents, antihalation agents, crossover cut agents, coloring dyes, pigments, thickeners, coating aids, antifoggants, antioxidants, ultraviolet absorbers, ultraviolet light One or more of various additives such as a stabilizer, 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 of applying these undercoat layers is not particularly limited, and various conventionally known methods can be used. Examples of the method include a coating method using an air knife coater, a dip coater, a curtain coater, a wire bar coater, a gravure coater, an extrusion coater, and the like, and a method of co-extrusion or lamination during melt film formation of a polyester film.

It is preferable to impart conductivity to the undercoat layer of the present invention.

In the present invention, the surface resistivity (23 ° C., 20% RH) on the side having the conductive layer is preferably 1 × 10 ¹² Ω or less, more preferably 5 × 10 ¹¹ Ω or less, and still more preferably. It is 1 × 10 ¹¹ Ω or less. In addition, the surface resistivity after development processing on the side having the conductive layer (23 ° C., 20% R
H) is preferably 1 × 10 ¹² Ω or less. More preferably 5 × 10 ¹¹ Ω or less, further preferably 1 × 10 ¹¹ Ω.
Ω or less.

In the support of the present invention, the electroconductive layer may be any layer as long as it is present on at least one side of the photographic light-sensitive material, but it may be in the silver halide emulsion layer or the backing layer. The protective layer and the intermediate layer may be conductive layers. Alternatively, at least one layer in the silver halide emulsion layer or the undercoat layer between the backing layer and the support may be a layer having conductivity.

Next, a photographic material using the support of the present invention will be described.

-Photosensitive layer- The halogen composition of the silver halide in the silver halide emulsion used in the present invention is not particularly limited. Silver chloride, 6
It is preferable to use a silver halide emulsion having a composition of silver chlorobromide containing 0 mol% or more of 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 light-sensitive material used in the present invention comprises a silver halide emulsion of at least one silver halide emulsion layer,
Tabular grains containing tabular grains, and preferably 50% or more of the total projected area of all grains in the emulsion layer in which the tabular grains are used, are tabular grains having an aspect ratio of 2 or more, particularly the proportion of tabular grains. It is more preferable that the value be increased from 60% to 70% and further to 80%. The aspect ratio represents the ratio of the diameter of a circle having the same area as the projected area of a tabular grain to the distance between two parallel planes.

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. As the sulfur sensitizer, known sulfur sensitizers can be used. Preferred sulfur sensitizers include, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, Rhodanins, polysulfide compounds and the like can be used. As the selenium sensitizer, a known selenium sensitizer can be used. For example, U.S. Pat. No. 1,623,499, JP-A-50-7132
No. 5, JP-A-60-150046 and the like can be preferably used.

The photographic material used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1
-Phenyl-5-mercaptotetrazole) and the like; mercaptopyrimidines and mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes and tetrazaindenes (especially 4-hydroxy-substituted-1,3 , 3a, 7-tetrazaindenes), pentazaindenes and the like; adding many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide and the like. Can be.

Gelatin is advantageously used as a binder or protective colloid of the photographic emulsion used in 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 such as polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole 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 used in the present invention may contain a dispersion of a water-insoluble or sparingly 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, or acrylic acid, methacrylic acid,
A polymer having a combination of α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid and the like as a monomer component can be used.

In the photographic emulsion and the non-photosensitive hydrophilic colloid layer used in the present invention, an inorganic or organic hardener is added as a crosslinking agent for a hydrophilic colloid such as gelatin. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis [β- (vinylsulfonyl) propionamide], etc.), active halogen compounds ( 2,4-dichloro-6-hydroxy-s-triazine and the like), mucohalic acids (mucochloric acid, phenoxymucochloric acid and the like) isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, Carboxy The group activated hardeners, etc., may be used alone or in combination. These hardeners are available from Research Disclosure.
loss) 176, 17643 (issued in December 1978), page 26, paragraphs A to C.

The photographic 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, it is preferable that the following compounds are contained in the constituent layers of the photographic material.

(1) Solid Dispersed Fine Particles of 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
(22) Compound described on page (11) SPS support Support described in JP-A-3-54551 The above-mentioned additives and other known additives are described below.
For example, Research Disclosure No. 17643
No. (December 1978). 18716 (1979
No.) and the same No. 308119 (December 1989
Month). The types of compounds and the locations described in these three research disclosures are listed below.

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 IV Desensitizing dye 23 IV 998 B Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right Fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Brightener 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surface activity 26 to 7 XI 650 right 1005 to 6 XI Antistatic agent 27 XII 650 right 1006 to 7 XIII Plasticizer 27 XII 650 right 1006 XII sliding agent 27 XII matting agent 28 XVI 650 right 1008 to 9 XVI binder 26 XXII 1003 to 4 IX support 28 XVII 1009 XVII

[0070]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1-Preparation of Supports 1 to 16-(Preparation of Film 1) 0.05 parts by weight of magnesium acetate hydrate as a transesterification catalyst was added to 100 parts by weight of dimethyl terephthalate and 65 parts by weight of ethylene glycol. Then, transesterification was carried out 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 raised and the pressure was reduced, and polymerization was carried out at 280 ° C. and 0.5 mmHg to obtain polyethylene terephthalate having an intrinsic viscosity of 0.65.

Further, the polyethylene terephthalate was vacuum-dried at 150 ° C. for 8 hours, and then dried using an extruder.
It was melt-extruded at 85 ° C., adhered to a 30 ° C. cooling drum while applying static electricity, cooled and solidified to obtain an unstretched sheet.
The unstretched sheet was heated at 85 ° C. using a roll-type longitudinal stretching machine.
And stretched 3.3 times in the machine direction. The temperature difference between the front and back surfaces was within 5 ° C.

The obtained uniaxially stretched film is stretched by a tenter type transverse stretching machine in a first stretching zone at 90 ° C. by 50% of the total transverse stretching ratio, and further in a second stretching zone at 100 ° C. by a total transverse stretching ratio of 3. The film was stretched three times. Then 70
Heat treatment at 2 ° C for 2 seconds, and first heat fixation zone at 150 ° C
For 5 seconds and a second heat set zone at 220 ° C. for 15 seconds. Next, a biaxially stretched polyethylene terephthalate film 1 having a thickness of 100 μm was obtained.

The Tg of the polyethylene terephthalate film 1 was 75 ° C.

On one surface of the film 1, 8 W / (m
² min) of corona discharge treatment, and the following undercoating coating solutions A-1 and A-2 were respectively applied thereon, and the undercoating layers A-1 and A-2 each had a dry film thickness of 0.1 mm. 8 μm,
It was applied so as to have a thickness of 0.1 μm. Further, the other surface is subjected to a corona discharge treatment of 8 W / (m ² · min), and the undercoating coating solutions B-1 and B-2 described below are used thereon. B-2 each had a dry film thickness of 0.
After coating to 8 μm and 1.0 μm, a film transport device consisting of a plurality of roll groups (zone length 100 m)
The heat treatment was carried out while being transported in a heat treatment type oven having At this time, the set temperature in the oven was changed as shown in Table 1. The heat treatment time is 10 minutes (line speed 10 minutes).
m / min).

<Undercoat Coating Solution A-1> A copolymer latex solution (solids: 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene, and 25% by weight of 2-hydroxyethyl acrylate) 270 g Compound (UL-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finished with water 1000 ml <Undercoating coating solution B-1> Butyl acrylate 40% by weight, styrene 20 270 g Compound (UL-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finished with water 1000 ml <Undercoating solution 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) 0.1 g Finished with water 1000 ml <Undercoat coating solution B-2> Water-soluble conductive polymer (UL-4) 60 g Compound (UL-) Latex liquid containing 5) as a component (solid content: 20%) 80 g Ammonium sulfate 0.5 g Hardener (UL-6) 12 g Polyethylene glycol (weight average molecular weight 600) 6 g Finish with water 1000 ml

[0077]

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[0078]

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<Coating of Emulsion Layer / Backing Layer> The following (emulsion layer) and (backing layer) were coated on A-2 and B-2, respectively, on Samples Nos. 1 to 16 to prepare Sample No. 1 which is a silver halide photographic material. 1 to 16 were prepared. Incidentally, gelatin coating amount at this time, the emulsion layer side is 2.7 g / m ^2, including gelatin in the emulsion, as gelatin total amount to be 5.0 g / m ² Backing layer side in 2.7 g / m ² Was applied.

(Preparation of Emulsion) A rhodium hexachloride complex was added to a silver sulfate solution and an aqueous solution of sodium chloride and potassium bromide at 8 ×.
The solution added so as to be 10 ⁻⁵ mol / Agmol was
A cubic crystal containing 0.13 μm in particle size and 1 mol% of silver bromide was added simultaneously to the gelatin solution while controlling the flow rate and desalting.
A monodispersed silver chlorobromide emulsion was obtained. This emulsion was sulfur sensitized by a conventional method, and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added as a stabilizer.
The following additives were added to prepare an emulsion coating solution.

(Preparation of Emulsion Coating Solution) Gelatin 1.0 g / m ² Compound (a) 1 mg / m ² NaOH (0.5 N) Adjusted to pH 5.6 Compound (b) 40 mg / m ² Compound (c) 30 mg / m ² saponin (20% aqueous solution) 0.5 ml / m ² sodium dodecylbenzenesulfonate 20 mg / m ² 5-methylbenzotriazole 10 mg / m ² compound (d) 2 mg / m ² compound (e) 10 mg / m ² compound ( f) 6 mg / m ² latex (m) 1.0 g / m ² Styrene-malenic acid copolymerized aqueous polymer (thickener) 90 mg / m ² (emulsion protective layer coating solution) Gelatin 0.5 g / m ² compound (g) ) (1% aqueous solution) 25 cc / m ² compound (h) 120 mg / m ² spherical monodisperse silica (8 μm) 20 mg / m ² spherical monodisperse silica (3 μm) 10 mg / m ² compound (i) 100 mg / m ² latex (m) 0.5 g / m ² Citric acid Adjusted to pH 6.0.

(Backing Layer Coating Solution) Gelatin 0.8 g / m ² Compound (j) 100 mg / m ² Compound (k)
18 mg / m ² compound (l) 100 mg / m ² saponin (20% aqueous solution) 0.6 cc / m ² latex (m) 300 mg / m ² 5-nitroindazole 20 mg / m ² Styrene-maleic acid copolymer aqueous polymer (increase Nebazai) 45 mg / m ² glyoxal 4 mg / m ² (backing protective layer coating solution) gelatin 0.5 g / m ² compound (g) (1% aqueous solution) 2 cc / m ² spherical polymethylmethacrylate (4μ) 25mg / m ² Sodium chloride 70 mg / m ² Glyoxal 22 mg / m ² Compound (n) 10 mg / m ² Latex (m) 0.5 g / m ²

[0083]

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[0084]

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-Coating of Emulsion Layer and Backing Layer-On the obtained supports 1 to 16, the following (emulsion layer) and (backing layer) were coated on A-2 and B-2, respectively. Photographic material samples 1 to 16 were prepared.

Samples 1 to 16 of photosensitive material prepared as described above
Was evaluated as described below, and the results are shown in Table 1.

(Evaluation method)-Glass transition temperature Tg-10 mg of film or pellet was added at 300 cc / min.
Melted at 300 ° C. in a nitrogen stream, and immediately quenched in liquid nitrogen. The quenched sample was set on a differential scanning calorimeter (DSC8230, manufactured by Rigaku Denki Co., Ltd.) and the quenched sample was set at 100 / min.
cc in a nitrogen stream at a rate of 10 ° C./min.
g is detected. Tg was defined as the average value of the temperature at which the baseline began to be skewed and the temperature at which it returned to the new baseline.
Note that the measurement start temperature is a temperature lower than the measured Tg by 50 ° C. or more.

-Curse- A photographic material having a width of 35 mm and a length of 210 mm is prepared by
After conditioning for one day under the conditions of 23 ° C. and 55% RH, the photographic photosensitive layer side is fixed inside so that the photographic photosensitive layer side is not wound around a core having a diameter of 2 inches (50 mm). Next, in this state, it is put in an aluminum barrier bag, heat-treated under the condition of 55 ° C. and 20% RH for 4 hours, and further allowed to cool at 23 ° C. and 55% RH for 1 hour. Thereafter, the film was released from the winding core, and the heights of the four corners rising with the convex portions of the film facing down were measured, and the average value was obtained. The unit is mm.

The value obtained by the above method is called the rising curl of the film. The stronger the curling, the larger the amount. If the rising curl is too large, it may cause poor transportability and workability on an automatic machine.
The following is preferred.

-Evaluation of Support Flatness- Support samples 1 to 16 were cut out to a size of 60 cm x 100 cm (width x length), placed on a table having excellent flatness, and visually evaluated for unevenness of the base.

：: Good flatness and tightly adhered to the table △: Distorted base in some places ×: Distorted overall due to distorted base.

[0093]

[Table 1]

As is clear from Table 1, when the support subjected to the heat treatment of the present invention is used, the curl curl is greatly improved and the flatness of the support is improved. I understand.

Example 2 At the time of preparing the film 1 of Example 1, the film was stretched with a temperature difference between the front and back sides by applying an electric heater to one surface at the stretching temperature for longitudinal stretching. At this time, the cooling drum surface side was set to the high temperature side, and the supports 17 to 22 were prepared as changed as shown in Table 2.

Next, silver halide photographic light-sensitive material samples 17 to 22 were prepared by coating an emulsion layer on the casting drum surface side and a backing layer on the opposite side, and evaluated in the same manner as in Example 1. Table 2 shows the results.

[0097]

[Table 2]

As is apparent from Table 2, when the support stretched by applying a temperature difference between the front and back sides during the longitudinal stretching is heat-treated,
It can be seen that the curl is improved.

Example 3 Films 1 prepared in the same manner as in Example 1 were subjected to heat treatment of the support by changing the relative humidity in the heat treatment zone as shown in Table 3 to prepare supports 23 to 27. 28,29
During heat treatment, superheated steam was blown into the zone.

Further, the supports 30 to 32 were subjected to a heat treatment by setting a transport roller in a warm water layer.

The support 23 heat-treated as described above
In the same manner as in Example 1, an emulsion layer and a backing layer were coated on Samples Nos. 1 to 32 to prepare silver halide photosensitive material samples 23 to 32 and evaluated. Table 3 shows the results.

[0102]

[Table 3]

As is evident from Table 3, when the heat treatment of the present invention is performed in an atmosphere in which a large amount of water is present, the curl is further improved.

[0104]

According to the present invention, there is provided a support for a silver halide photographic light-sensitive material which is hardly curled and has excellent workability, which is manufactured or used by being wound into a roll. can do.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location B29K 67:00 B29L 7:00

Claims (5)

[Claims] 1. A photographic support comprising a biaxially stretched polyester film, wherein the support has a weight of 5 kg / m.sup.3 from the time when the undercoat layer is coated and dried until the emulsion layer is coated. A photographic support, wherein the polyester film is heat-treated at a temperature of Tg to Tg + 35 ° C. while being conveyed at a tension of 60 kg / m. 2. The method according to claim 1, wherein the photographic support is 10 kg / m to 30 kg / m.
2. The photographic support according to claim 1, wherein the photographic support is heat-treated while being transported at a tension of kg / m. 3. The photographic support according to claim 1, wherein the photographic support is heat-treated at a temperature of Tg + 5 ° C. to Tg + 25 ° C. of the polyester film. 4. The film according to claim 1, wherein the polyester film is stretched and stretched while giving a temperature difference between the front and back surfaces of 10 ° C. to 40 ° C. during stretch film formation. The photographic support as described. 5. The heat treatment is performed at a relative humidity of 20% RH to 1%.
The photographic support according to any one of claims 1 to 4, wherein the photographic support is performed in an atmosphere of 00% RH, in superheated steam, or in a water bath.