JPH09281651A - Polyester supporting body and photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester base body which can be easily curled, has good dimensional stability, excellent adhesion property between the base body and a photosensitive layer, and does not influence photosensitive performance with time when the base body is used for a photosensitive material. SOLUTION: This base body is composed of a polyester film and a base coating layer on at least one surface of the polyester film. The base coating layer contains a hydrophilic resin containing at least a solvent or swelling solvent for the polyester, or it contains a vinylidene chloride copolymer. After the whole base coating layer is applied and dried, the film is cooled from the temp. 25 deg.C higher than the glass transition temp. of the polyester film to the temp. 5 deg.C higher than the glass transition temp. for >=20sec. The solvent or swelling solvent for the polyester is included by 1 to 20wt.% of the base coating liquid containing the solvent or swelling solvent for the polyester. The solvent or swelling solvent is preferably an aromatic compd. containing hydroxyl groups or an aromatic compd. containing carboxyl groups or acid anhydrides of these.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester support, and more specifically, it has less curl, has good dimensional stability, and has excellent adhesiveness. It relates to an unaffected polyester support.

[0002]

2. Description of the Related Art A biaxially stretched polyethylene terephthalate film (hereinafter referred to as a PET film) has excellent transparency, mechanical strength and dimensional stability, and for printing where dimensional stability is strictly required. It is used in light-sensitive materials, X-ray films that require transparency and elasticity.

In recent years, however, as seen in facsimile light-sensitive materials, the core diameter in which the light-sensitive material is wound becomes smaller due to the downsizing of the equipment, and the PET film has no curl recovery property after the development processing. The sample placed in the time roll state has a large curl curl, and there is a problem that automatic conveyance during facsimile photographing or jamming during conveyance to an automatic developing machine occurs.

Therefore, it has been desired to reduce the curl curl of a polyester film typified by a PET film.

From such a point of view, as a method for reducing the curl curl of a polyester film, JP-A-51-16 has been proposed.
No. 358, a thermoplastic resin film has a glass transition temperature (hereinafter, referred to as Tg) of −5 ° C. to Tg−30 ° C.
A method of heat treatment for 1500 hours has been proposed. Further, in JP-A-6-35118, Tg is 90 to 200.
A method has been proposed in which a polyester film at 0 ° C. is subjected to undercoating and then heat treated at 50 ° C. to Tg for 0.1 to 1500 hours.

Further, the use environment of photographic light-sensitive materials has been diversified, and the adhesiveness between the polyester film and the silver halide photographic light-sensitive material has been further required.

The above thermoplastic resin film is treated with Tg-5 ° C.
The method of heat treatment at ˜Tg−30 ° C. for 0.1 to 1500 hours includes a PET film or a polyethylene naphthalate film (hereinafter referred to as PEN film), a crystalline or semicrystalline thermoplastic resin curl. Although it seems to be effective because it has an effect of reducing curl, there is a problem that such long-term heat treatment at a relatively low temperature significantly impairs the quality of the film.

Further, after the polyester film is subbed, 5
The method of heat treatment at 0 ° C. to Tg for 0.1 to 1500 hours is, in principle, exactly the same as the method described in JP-A-51-16358. Therefore, curl curl is sufficiently reduced. In order to do so, heat treatment near the Tg of the film is necessary.

That is, in general, a photographic light-sensitive material 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 light-sensitive 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. After that, it is cut into a final product form and is packaged.

It is advantageous that the intermediate product is as wide and long as possible in terms of shortening the switching time and improving productivity, and the weight of the intermediate product is increasing more and more. As a result, a considerable load is actually applied to the winding core.

By the way, it is well known that when a thermoplastic resin film is heated near its Tg, its elastic modulus sharply decreases. Therefore, if a heat treatment is carried out for a long time near the Tg of the thermoplastic resin film under a heavy load, the film cannot withstand the load, and various photographic supports such as wrinkles, folds, and presses are formed. As a result, a surface failure that cannot be used will occur.

Since the undercoat layer is a layer for firmly adhering the support and the photosensitive layer, it is necessary to bring the front and back adhesive layers into close contact with each other and to apply heat to bond the front and back adhesive layers together. It will be attached, and problems such as blocking may occur when unwinding again.

Further, the dimensional stability is also affected by the thickness of the undercoat layer. In other words, the design of the undercoat layer is designed with the idea of applying a thick soft layer against peeling to absorb stress and increase the adhesive force, but in this case, since the undercoat layer is soft, When a photographic photosensitive layer is adhered to a support having a different behavior, there is a problem that the dimensional stability is deteriorated due to the extension of the undercoat layer. Therefore, it is necessary to make the undercoat layer thin, but for this purpose, it is necessary to apply an undercoat layer having good compatibility with the polyester as the support.

As such an undercoat layer, a solvent which dissolves or swells the polyester is contained, or a resin such as a vinylidene chloride copolymer having a good compatibility with the polyester is used. However, the solvent that dissolves or swells the polyester affects the photographic photosensitive layer if it remains in the undercoat layer, while the vinylidene chloride-based copolymer decomposes over time and affects the photographic photosensitive layer. was there.

[0015]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to prevent curling habit, to have good dimensional stability, and to have excellent adhesiveness between a photosensitive layer and a support, and also to make the photosensitive material sensitized over time. It is to provide a light-sensitive material that does not affect the performance.

[0016]

The above object of the present invention is to provide an undercoat layer having a hydrophilic resin containing a polyester solvent or a swelling solvent on at least one side of a polyester film, or an undercoat layer having a vinylidene chloride copolymer. After coating and drying all undercoat layers, the glass transition temperature of polyester film + 25 ° C to glass transition temperature + 5 ° C
Until now, this has been achieved with a polyester support that is cooled for over 20 seconds.

The polyester solvent or swelling solvent is contained in an amount of 1 to 20% by weight of an undercoating processing liquid containing the polyester solvent or swelling solvent, a hydroxyl group-containing aromatic compound, or a carboxyl group. A preferred embodiment is the acid anhydride-containing aromatic compound.

The present invention will be described in more detail below.

The polyester which constitutes the support of the present invention is not particularly limited, but a polyester having a film-forming property, which comprises a dicarboxylic acid component and a diol component as main constituent components, is preferable.

The constituent dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethane dicarboxylic acid, Examples thereof include cyclohexanedicarboxylic acid, diphenyldicarboxylic acid, diphenylthioetherdicarboxylic acid, diphenylketone dicarboxylic acid, phenylindanedicarboxylic acid and the like. As the diol component, ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4
-Hydroxyphenyl) propane, 2,2-bis (4-
Hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, diethylene glycol,
Examples include neopentyl glycol, hydroquinone, cyclohexanediol and the like.

Among the polyesters containing these as the main constituents, terephthalic acid is used as the dicarboxylic acid component, ethylene glycol is used as the diol component, and / or 1,4 from the viewpoints of transparency, mechanical strength and dimensional stability. −
Polyesters containing cyclohexanedimethanol as the main constituent are preferred. Among them, polyesters containing PET as a main constituent, copolymerized polyesters containing terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and polyesters containing a mixture of two or more of these polyesters as main constituents are preferable.

When the content of ethylene terephthalate unit in the polyester is 70% by weight or more, a film having excellent transparency, mechanical strength and dimensional stability can be obtained.

The polyester constituting the biaxially stretched polyester film may be copolymerized with other copolymerization components, or may be mixed with other polyesters, as long as the effects of the present invention are not impaired. . Specifically, the above-mentioned dicarboxylic acid component and diol component, or polyesters composed of them can be mentioned.

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. There is no particular limitation on the kind of the antioxidant to be contained, and various kinds of antioxidants can be used, and examples thereof include antioxidants such as hindered phenol compounds, phosphite compounds, and thioether compounds. Of these, hindered phenol-based antioxidants are preferable in terms of transparency.

The content of the antioxidant is usually 0.01 to 2% by weight, preferably 0.1 to 2% by weight with respect to the polyester.
0.5% by weight. Within this range, the so-called fog phenomenon in which the density of the unexposed portion of the photographic light-sensitive material becomes high can be prevented, and the haze of the film can be suppressed to a low level, so that a photographic support having excellent transparency can be 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 slipperiness, if necessary. The slipperiness imparting means is not particularly limited, but external particle addition method of adding inert inorganic particles to polyester, internal particle precipitation method of precipitating a catalyst added at the time of polyester synthesis, or a surfactant or the like on the film surface. The application method is generally used. Among these, the internal particle deposition method in which the deposited particles can be controlled to be relatively small is preferable because slipperiness can be imparted without impairing the transparency of the film. As the catalyst, various known catalysts can be used,
In particular, calcium and manganese are preferable because high transparency can be obtained. These catalysts may be one kind,
Two or more kinds may be used in combination.

The method for synthesizing the polyester as the raw material for the biaxially stretched polyester film is not particularly limited, and the polyester can be produced by a conventionally known method for producing polyester.
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, and an ester exchange reaction is performed between this and the diol component, and this is heated under reduced pressure. A transesterification method in which the excess diol component is removed to perform polymerization 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. Further, in each step during the synthesis, anti-coloring agent, antioxidant, crystal nucleating agent, slip agent, stabilizer, anti-blocking agent, ultraviolet absorber, viscosity modifier, defoaming agent, clarifying agent, antistatic agent, pH adjuster,
Various additives such as dyes and pigments may be added.

The biaxially stretched polyester film preferably has a small rising curl obtained by the following method. If the curl curl of the film is too large, the transportability and the workability in an automatic developing machine are deteriorated. Therefore, the smaller the better. The problem begins to occur when it exceeds 30 mm.

The thickness of the biaxially stretched polyester film of the present invention is not particularly limited and may be set so as to have a necessary strength depending on the purpose of use. 50 to 300μ when used in medical and printing photographic light-sensitive materials
m, particularly preferably 80 to 200 μm.

The haze of the biaxially stretched polyester film is preferably 3% or less, more preferably 1
% Or less. The haze is ASTM-D1003-
52 was measured in accordance with No. 52.

The Tg of the biaxially stretched polyester film is 6
0 ° 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. T
When g is not less than this value, the film is not deformed in the drying step of the development processor, and a photosensitive material having a small curl curl after the development processing can be obtained.

The measuring method of Tg is as follows.

10 mg of the film is melted at 300 ° C. in a nitrogen stream of 300 cc / min and immediately quenched in liquid nitrogen. This quenched sample was set in a differential scanning calorimeter (manufactured by Rigaku Denki Co., Ltd .: DSC8230 type), and 100 c / min.
In the nitrogen gas stream of c, the temperature is raised at a temperature rising rate of 20 ° C./min to obtain Tg
Is detected. 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. The measurement start temperature is 50 from the measured Tg.
The temperature shall be lower than ℃. Incidentally, the Tg of PET used in this example measured by this method was 75 ° C.

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

The method for obtaining an unstretched sheet and the method for uniaxially stretching in the machine direction can be carried out by conventionally known methods.
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 and solidified, and unstretched. Get the sheet.
Then, the obtained unstretched sheet is treated with a plurality of roll groups and / or
Alternatively, it is a method in which the polyester is heated within a range of Tg to Tg + 100 ° C. through a heating device such as an infrared heater and longitudinally stretched in one stage or in multiple stages. The draw ratio is usually 2.5 times
It is necessary to set it in a range of 6 times so that the subsequent transverse stretching is possible. When the sheet has a multi-layered structure, the stretching temperature is preferably set on the basis of the Tg of the polyester of the thickest layer among the Tg of the polyester of each constituent layer.

At this time, a conventionally known method may be used for laminating polyester. For example, a co-extrusion method using a plurality of extruders and a feed block type die or a multi-manifold type die, a single-layer film constituting a laminate or a laminate on a laminate film, other resins are melt-extruded from an extruder. Examples thereof include an extrusion laminating method of cooling and solidifying on a cooling drum, and a dry laminating method of laminating a monolayer film or a laminated film constituting a laminated body with an anchor agent or an adhesive as necessary. Among them, the coextrusion method is preferable because the number of manufacturing steps is small and the adhesion between the layers is good.

Next, 1 in the vertical direction obtained as described above.
The axially stretched polyester film is treated with Tg to Tm-2.
The film is transversely stretched within a temperature range of 0 ° C. and then heat set. The transverse stretching ratio is usually 3 to 6 times, and the ratio of the longitudinal stretching ratio to the transverse stretching ratio is appropriately adjusted so that the obtained biaxially stretched film has physical properties measured and has desirable 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 depending on the purpose of use. At this time, it is preferable to laterally stretch while sequentially raising the temperature difference in the range of 1 to 50 ° C. in the stretching region divided into two or more because the distribution of the physical properties in the width direction can be reduced. After further transverse stretching, the film is made to have a Tg of -40 ° C or higher at a temperature of not more than Tg-40 ° C at the final transverse stretching temperature or less.
Holding for 01 to 5 minutes is preferable because the distribution of physical properties in the width direction can be further reduced.

Heat setting is carried out at a temperature higher than the final transverse stretching temperature,
Within the temperature range of Tm-20 ° C or lower, usually 0.5 to 300.
Heat set for 2 seconds. At this time, it is preferable to heat-set while sequentially raising the temperature difference in the range of 1 to 100 ° C. in the region divided into two or more.

The heat-fixed film is usually cooled to Tg or less, cut at the clip holding portions at both ends of the film, and wound up. At this time, below the final heat setting temperature, Tg
Within the above temperature range, 0.
It is preferable to perform a relaxation treatment of 1 to 10%. Also, cooling is
It is preferable to gradually cool 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 carried out by conventionally known means, but it is particularly 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 obtained by (T1-Tg) / t, where T1 is the final heat setting temperature and t is the time required for the film to reach Tg.

The more optimal heat setting conditions, cooling conditions and relaxation treatment conditions differ depending on the polyester constituting the film. Therefore, the physical properties of the obtained biaxially stretched film are measured and appropriately adjusted so as to have preferable properties. It may be determined by

In the production of the above film, functional layers such as an antistatic layer, a slipping layer, an adhesive layer and a barrier layer may be coated before and / or after stretching. At this time, various surface treatments such as corona discharge treatment and chemical treatment can be applied as necessary. Further, for the purpose of improving the strength, it is also possible to carry out stretching which is used for known stretched films such as multi-stage longitudinal stretching, re-longitudinal stretching, re-longitudinal transverse stretching and transverse / longitudinal stretching. Of course, the clip grips at both ends of the cut film are
After being pulverized, or after being subjected to granulation treatment, depolymerization / repolymerization, etc., if necessary, it can be reused as a raw material for films of the same type or as a raw material for films of different types. Good.

As the solvent for swelling or dissolving the polyester used in the present invention, as the hydroxyl group-containing aromatic compound, resorcin, methylresorcin, phenol, chlorophenol, cresol and the like can be mentioned.
Examples of the aromatic compound containing a carboxyl group or an acid anhydride thereof include carboxylic acids such as salicylic acid and benzoic acid, and acid anhydrides thereof.

The content of these solvents is 1 to 1 of the undercoat processing liquid in order to satisfy both the flatness and the adhesiveness of the film.
It is preferably 20 parts by weight.

As the hydrophilic resin for the undercoat layer which is used together with the solvent for swelling or dissolving the polyester, a hydrophilic group on the side chain, that is, a hydroxyl group, a carboxyl group or an acid anhydride, or an amino group or a cyclic amide group is used. It is a natural or synthetic polymer containing one or a plurality of polymers.

Another undercoat layer of the present invention is a vinylidene chloride copolymer. Here, the vinylidene chloride-based copolymer means 99.9 to 50 mol% of vinylidene chloride and 8 to
Vinyl monomer having 0.1 mol% of carboxyl group,
Further, if necessary, it means a copolymer composed of a monomer of a third component or more and a vinylidene chloride main component. Second
With a vinyl monomer having a carboxyl group that is a component,
Examples thereof include acrylic acid, methacrylic acid, maleic acid (copolymerized in the form of maleic anhydride, and ring-opening during or at the end of the polymerization), itaconic acid, and salts thereof.

The vinylidene chloride copolymer is preferably in the form of latex in the state of the undercoat processing liquid.
In this case, the composition of the center and the outside of so-called latex particles having a uniform or core-shell shape may be different.

A surface treatment is required to apply this latex to a polyester film. As the surface treatment for such purpose, corona discharge treatment, ultraviolet treatment,
Examples thereof include a method of surface activation treatment such as glow discharge treatment, plasma treatment, and flame treatment, and a method of etching treatment such as resorcin treatment, phenol treatment, alkali treatment, amine treatment, and trichloroacetic acid treatment. These methods may be used alone or in combination.

When coating the undercoat layer, various conventionally known methods can be used. For example, a coating method using an air knife coater, a dip coater, a curtain coater, a wire bar coater, a gravure coater, an extrusion coater, or the like may be used before or after the completion of biaxial orientation of the polyester film.

The photosensitive layer may be directly coated on the layer made of these hydrophilic resins or latex, but after the hydrophilic colloid layer (second subbing layer) is further coated thereon, the photosensitive layer is formed. It is also good to apply a layer for enhancing the adhesiveness. In this case, the time for cooling to Tg + 25 ° C. to Tg + 5 ° C. for 20 seconds or more is after coating and drying the hydrophilic colloid layer.

Examples of the binder that constitutes the hydrophilic colloid include gelatin, gelatin derivatives, casein, agar, and the like. Further, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer,
Although water-soluble polymers such as carboxymethyl cellulose and hydroxyethyl cellulose, a sodium polystyrene sulfonate copolymer and a hydrophobic latex may be combined, gelatin is preferably used as a main component.

The second subbing layer preferably contains inorganic fine particles such as silicon dioxide and titanium dioxide, and an organic matting agent (1 to 10 μm) such as polymethylmethacrylate. In addition to these, various additives such as antistatic agents, antihalation agents, coloring dyes, pigments, coating aids, and the like can be contained as required.

A hardener is preferably mixed in the undercoat layer or the photosensitive layer. In this case, known hardeners can be used, and specific examples thereof include aldehyde compounds such as formaldehyde and glutaraldehyde, compounds having a reactive halogen, ketone compounds such as diacetyl and cyclopentanedione, and bis (2-chloroethyl). Urea, 2,4-
Dichloro-6-hydroxy-1,3,5-triazine,
5-acetyl-1,3-diacryloylhexahydro-
Vinyl sulfone compounds such as 1,3,5-triazine and divinyl sulfone, N-hydroxymethylphthalimide, isocyanate compounds, aziridine compounds, carbodiimide compounds, isoxazole compounds, halogenocarboxaldehydes such as mucochloric acid, dihydroxydioxane, Examples thereof include organic hardeners such as dioxane derivatives such as dichlorodioxane, and inorganic hardeners such as chromium alum, zirconium sulfate and chromium trichloride. or,
Examples of hardeners having a relatively fast hardening effect on gelatin include compounds having a dihydroquinoline skeleton, N-carbamoylpyridinium salts, acylimidazoles, N-acyloxyimidazoles, and N-acyloxyimidazoles described in JP-B-55-38655. -A compound having two or more acyloxyimino groups in the molecule, a compound having an N-sulfonyloxyimide group, a compound having a phosphorus-halogen bond, a chloroformamidinium compound, a water-soluble polyfunctional epoxy compound and the like can be mentioned. .

The addition amount of these is preferably 0.001 to 10 g per liter of the processing liquid for the undercoat layer or the photosensitive layer.

The photosensitive layer provided on the polyester support of the present invention, particularly the photosensitive layer of a silver halide photographic light-sensitive material, will be described below.

The silver halide photographic light-sensitive material (hereinafter also referred to as silver salt light-sensitive material) applicable to the present invention is a black-and-white film for photography, a light-sensitive material for printing, a black-and-white silver halide photographic light-sensitive material such as an X-ray film. , Negative color roll film,
There are silver halide color photographic light-sensitive materials such as negative color cut film, positive color roll film, positive color cut film, etc., and they can be applied to any of them.
Here, the photosensitive material for printing will be mainly described.

The silver halide used in the silver salt sensitive material is as follows.
Usual silver halide emulsions of silver bromide, silver chloride, silver iodobromide, silver chlorobromide and silver chloroiodobromide can be optionally used, and any of acidic method, neutral method and ammonia method can be used. What was obtained by the method can also be used. Preferred silver halides for printing emulsions are silver chloride, particularly silver chlorobromide containing 60 mol% or more of silver chloride or silver chloroiodobromide containing 60 mol% or more of silver chloride.

The silver halide grain may be a grain having a uniform silver halide composition distribution within the grain or a core / shell grain having a different silver halide composition between the inside of the grain and the surface layer. It may be an internal latent image type particle which is mainly formed inside the particle or a surface latent image type particle.

As the silver halide grains, grains having a single shape may be used, or grains having various shapes may be mixed. Further, those having any grain size distribution may be used, and a polydisperse emulsion or a monodisperse emulsion may be mixed and used.

The silver halide emulsion grains of the photosensitive material for printing are preferably monodisperse. Specifically, they are contained within a grain size range (coefficient of variation) of ± 20% around the average grain size r. The silver halide content is preferably 60% or more, more preferably 70% or more, still more preferably 80% or more of the total silver halide. The term "particle size" as used herein means the diameter of spherical silver halide grains, or the diameter of a projected image of a non-spherical grain converted into a circular image of the peripheral area. A highly uniform monodispersion is preferred as a photographic image. Monodisperse emulsions are disclosed in JP-A Nos. 55-48521 and 5
It can be obtained by referring to the methods described in 8-49938 and 60-122935.

The shape of the silver halide grains is not limited,
Any shape such as a flat plate shape, a spherical shape, a cubic shape, a 14-sided shape, a regular octahedron shape, or the like may be used. For example, Japanese Patent Laid-Open No. 5-204
Tabular grains can be obtained by the method described in No. 070.

As the method of reacting the soluble silver salt and the soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof and the like can be used.

It is also possible to use a so-called reverse mixing method in which grains are formed in the presence of excess silver ions. As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is formed, a so-called controlled double jet method can be used. According to this method, the crystal form is regular. It is possible to obtain a silver halide emulsion having a substantially uniform grain size.

The silver halide grains used in the silver halide emulsion have a cadmium salt, a zinc salt, a lead salt, at least one of a grain forming process and a growing process.
It is preferable to add thallium salt, iridium salt (including complex salt), and rhodium salt (including complex salt).

For details of the silver halide emulsion and its preparation method, Research Disclosure (RD) 1
76, 17643, 22-23 (December 1978)
Reference can be made to the documents described or cited in (Month).

The light-sensitive silver halide emulsion can be used as it is as a so-called unripened (Primitive) emulsion without chemical sensitization, but it is usually preferable to carry out chemical sensitization.

In the silver halide emulsion, various photographic additives can be used in the steps before and after physical ripening or chemical ripening. Examples of the compound used in such a step include RD17643, pages 23 to 29, RD1871 described above.
6,648-651 (November 1979) and RD3
08119, 996-p. 1009 (December 1989)
The various compounds described in (Month) can be used.

In addition to this, Product Licensing Magazine (P
product Leicensing) 92, 107
The description on page 110 (December 1978) can also be referred to.

In the light-sensitive material for printing, a high-contrast agent is contained in the silver halide emulsion layer or the non-light-sensitive layer in order to improve halftone quality, or a high-contrast processing is carried out in the developing process. The preferred contrast enhancer is a hydrazine compound or a tetrazonium compound. As the hydrazine compound,
JP-A-7-114126, pp. 23-32 (paragraph 011)
Examples of the compounds and tetrazolium compounds described in 1 to 0157) include compounds described in JP-A-6-208188, pages 8 to 10 (paragraphs 0059 to 0067).

The silver salt light-sensitive material has at least one silver halide emulsion layer and at least one emulsion protective layer on the photosensitive layer side on a photographic support, and on the other side, a layer having a certain function and its protection. There is a back layer in which at least one layer is provided. There is no particular limitation on the number of silver halide emulsion layers or back layers.

Gelatin is mainly used as the binder used in the emulsion layer or protective layer, intermediate layer, back layer and the like. This gelatin includes lime-processed, acid-processed and enzyme-processed gelatin, and those subjected to decalcification process, inertization process, inactivation process and the like can also be used. Derivative gelatin such as phthalated gelatin can also be used. Other water-soluble substances can also be mixed in the gelatin binder. For example, a polymer of sodium styrenesulfonate or a copolymer with other monomers, poly-
N-vinylpyrrolidone, maleic anhydride copolymer, polyacrylamide and its derivatives, polyacrylic acid and its derivatives and copolymers, casein, albumin, carboxymethylcellulose, hydroxyethylcellulose, sodium alginate, etc., synthetic or processed natural Things are used. Further, the polymer latex described in U.S. Pat. No. 3,411,911 can be incorporated in the photographic constituent layers.

A function can be imparted to each layer of the back layer. Examples of functionalized layers include an antistatic layer, an antihalation layer, an irradiation prevention layer, and a magnetic recording layer. These layers may be adjacent to the undercoat layer, on the surface, or at any position depending on the purpose.

It is important that the printing photosensitive material has a curl balance between the photosensitive layer side and the back layer side. for that reason,
Ratio of binder such as gelatin in back layer and hydrophilic polymer such as gelatin in photosensitive layer side (back layer / photosensitive layer side)
Is preferably 0.1 or more in terms of weight ratio, and practically 0.32 to 1.50 is particularly preferably used. This ratio depends on the material and thickness of the support of the photosensitive material, the total amount of hydrophilic polymers such as gelatin, the amount of silver or the amount of other additives (for example, polymer latex). It is determined by the design such as the developing rate or the drying rate after processing.

The back layer has various functions as described above. For example, for the image sharpness of the light-sensitive material, the antihalation function and the antiirradiation function, the RD
Appropriate antihalation dyes and antiirradiation dyes described in the section of Dyes can be used.

For the function of preventing sticking between the light-sensitive layer and the back layer of the light-sensitive material, the matting agent and slipping agent described in the above RD can be appropriately used. The shape and particle size of the matting agent are not limited, but a spherical matting agent having an average particle size of 10 to 50 μm can also be used.

As the slip agent, in addition to the above-mentioned RD, a typical one is a silicone-based slip agent; a higher fatty acid-based slip agent,
Alcohol-based and acid amide-based lubricants; metal soaps; ester-based and ether-based lubricants and taurine-based lubricants can be used.

Regarding the development processing of the photographic light-sensitive material, known development described in Journal of the American Chemical Society (J. Am. Chem. Soc.) Volume 73, page 3100 (1951). Agents can be used. The photosensitive material for printing can be developed, for example, by the processing described in JP-A Nos. 5-123292 and 53-17719.

[0077]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

(Preparation of undercoating liquid) An undercoating liquid having the following composition was prepared.

Subbing processing liquid 1 Gelatin 1 g Water 1 g Acetic acid 1 g Methanol 47 g Methylene dichloride 46 g p-Chlorophenol 4 g Subbing processing liquid 2 Vinylidene chloride latex (LX-1) 7 g Silica particles (average particle size 3 μm; 10% water dispersion) Liquid) 1 g Hardener (H-1) 2 g Water 90 g LX-1: Vinylidene chloride / methyl methacrylate / acrylonitrile / glycidyl acrylate (90/3/2 /)
5 mol ratio; solid content 50%) H-1: 2,4-dichloro-6-hydroxy-1,3
5-triazine / sodium undercoating liquid 3 Styrene-butadiene latex (LX-2) 16 g Hardener (H-1) 2 g Water 82 g LX-2: Styrene / butadiene / acrylic acid / itaconic acid (38/54 / 5/3 molar ratio; solid content 50%) PET obtained by subjecting these undercoating working liquids 1 to 3 to corona discharge
Simultaneous coating on both sides of the film to give a coating weight of 10 g / m ² , then at 65 ° C for 6 seconds, then at 160 ° C for 1 second.
After drying for 2 seconds and further at 80 ° C. for 5 seconds, it was rapidly cooled to room temperature.

(Preparation of Photographic Support) After subjecting the obtained undercoated supports (3 types) to corona discharge, one side of the undercoating upper layer processing solution having the following composition and the other side of the antistatic layer processing are processed. Liquid
Simultaneous coating on both sides to a dry film thickness of 0.1 μm and 0.2 μm respectively, then at 75 ° C. for 6 seconds, then 160
After drying at ℃ for 16 seconds and 140 ℃ for 5 seconds, 100 ℃
Between −80 ° C., it was cooled (gradual cooling) at the temperature shown in Table 1, and finally it was rapidly cooled to room temperature at 10 ° C./sec to obtain support samples 1-16.

Undercoat Upper layer processing liquid gelatin (10% aqueous solution) 80 g Methylcellulose 15 g Sodium dodecylbenzenesulfonate 3 g Hardener (H-1) 2 g Pure water 100 g Antistatic layer processing liquid gelatin 20 g Methylcellulose 5 g Crystalline tin oxide fine particles ( Antimony dope) 70 g Sodium dodecylbenzene sulfonate 3 g Hardener (H-1) 2 g Pure water 100 g (Preparation of photosensitive material) A silver halide emulsion of the following prescription 1 was added to the undercoat upper layer of each support in an amount of 2 g of silver. 9.9 g / m ² , and a gelatin amount of 1.2 g / m ^2, and a coating solution of the following formulation 2 as a protective layer on the gelatin solution of 0.6 g / m 2
Simultaneous multi-layer coating of the emulsion layer and the protective layer was performed so as to obtain ² . On the antistatic layer on the opposite side, the back layer of the following formulation 3 had a gelatin content of 0.6 g / m ^2, and the back layer protective layer of the following formulation 4 had a gelatin content of 0. Four
Simultaneous multi-layer coating was applied so as to obtain g / m ² , to obtain photosensitive material samples for printing (Nos. 1 to 16).

Formulation 1: Emulsion layer composition (per 1 m ^{2 of} coated sample) Sensitizing dye (SD-1) 0.6 mg Hydrazine compound (additive-1) 30 mg Additive-2 50 mg Surfactant (SU-1) 100 mg Latex polymer (LX-3) 1.0 g Hardener (H-1) 30 mg Surfactant (SU-2) 0.7 mg 2-Mercapto-6-hydroxypurine 10 mg Sodium ethylenediaminetetraacetate 50 mg Prescription 2: Emulsion protective layer Composition (per 1 m ^{2 of} coated sample) Gelatin 0.6 g Surfactant (SU-2) 12 mg Matting agent (monodisperse silica having an average particle size of 3.5 μm) 25 mg Hardener (H-2) 30 mg Surfactant (SU -3) 1 mg of colloidal silica (average particle size 0.05 .mu.m) 20 mg formulation 3: back layer composition (coating samples 1 m ² per) gelatin 0.6 g Surfactant (SU-2) 5 mg Latex polymer (LX-3) 0.3 g Colloidal silica (average particle size 0.05 μm) 70 mg Sodium polystyrene sulfonate 20 mg Hardener (H-3) 100 mg Formulation 4: Bag Layer protective layer composition (per 1 m ^{2 of} coated sample) Gelatin 0.4 g Matting agent (monodisperse PMMA having an average particle size of 5 μm) 50 mg Surfactant (SU-4) 10 mg Surfactant (SU-3) 1 mg Dye (F- 1) 20 mg H (OCH ₂ CH ₂ ) ₆₈ OH 50 mg Hardener (H-2) 15 mg Polysiloxane 0.7 g SU-1: ethylene oxide 3 of p-nonylphenol
5 mol adduct SU-2: Sodium sulfosuccinate (i-amyl decyl) sodium salt SU-3: Sodium p-nonyloxybenzenesulfonate H-3: 1,3-Diglycidyl glycerol

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(Evaluation of Photosensitive Material) Photosensitive Material Samples 1 to 16
The adhesive properties, dimensional stability, curl habit, and actual copying performance were evaluated as follows.

<< Adhesiveness >> With a film provided with a silver halide emulsion layer, a film in a dry state before development (hereinafter referred to as a raw film) and a film in a dry state after development (hereinafter referred to as a dry film) Was evaluated by the following evaluation method.

Before the development treatment and after the development treatment, the surface of the emulsion layer of the sample which had been dried was scratched with a razor at a 45 ° angle to reach the PET film of the support, and a cellophane tape was adhered to it, which was then rapidly peeled off. And measure the peeled area of the emulsion layer.
It was rated on a scale.

1: Adhesive strength is very weak, 100% or more of the area is completely peeled off 2: 50% to less than 100% of the area is peeled off 3: 20% to less than 50% of the area is peeled off 4: Adhesive strength is strong, and an area of 5% to less than 20% peels off. 5: Adhesive strength is very strong, peeling area is less than 5% and no peeling occurs. If the evaluation is 4 or more, it can be considered that the film is sufficiently strong in practical use. .

<< Rising curl curl >> A photosensitive material sample after emulsion coating was conditioned under conditions of 23 ° C. and 55% RH for 24 hours, cut into 50 mm × 210 mm, and wound into a core having a diameter of 3 inches. . This was barrier-wrapped and then heated at 40 ° C. (thermo treatment; time shown in Table 1), and thereafter, the rising heights of the four open corners were averaged.

«Dimensional stability» A photosensitive material sample after emulsion coating was conditioned under conditions of 23 ° C. and 20% RH for 24 hours, cut into 50 mm × 610 mm, and cut on a glass dry plate, which is a negative original, at 560 mm intervals. The drawn line is exposed again by the sample, and this is Konica automatic processor GR
The development temperature was set to 42 ° C. with −48 (manufactured by Konica) and development was performed.

After that, the humidity was controlled again for 24 hours under the conditions of 23 ° C. and 20% RH, and the deviation from the line of the glass plate which is a positive document obtained by returning the glass plate of the document was returned.

Further, this sample was conditioned in a room at 23 ° C. and 55% RH for 24 hours, and then the deviation from the positive original was measured in this room, and the difference between the deviations was taken as the elongation of the photosensitive material.

<Photographic performance-actual image quality> A photosensitive material sample after emulsion coating was conditioned in a room at 23 ° C. and 55% RH for 24 hours, and then thermoprocessed at 40 ° C. for the time shown in Table 1 using a sample. The line drawing original was photographed with a camera, and developed, fixed, washed with water and dried using an automatic processor. Development temperature is 28 ℃ ・ 6
Seconds, fixing temperature 28 ° C. for 6 seconds, water washing 25 ° C. for 6 seconds, and drying temperature 60 ° C. for 6 seconds.

The processed sample thus obtained was evaluated by visual observation in five grades.

1. Not practical 2. It is within the practical range, but not preferable. Practical 4. Good 5. Very good However, for the live-action evaluation, a comprehensive evaluation including sensitivity, line drawing reproducibility, and graininess is performed.

The developing process was performed as follows.

(Processing conditions) Process Temperature Time Image 38 ° C 12 seconds Fixing 35 ° C 10 seconds Washing 40 ° C 10 seconds Drying 50 ° C 12 seconds Total 44 seconds Street.

Developer composition (per liter) Diethylenetriaminepentaacetic acid pentasodium salt 3 g Sodium sulfite 50 g Potassium carbonate 40 g Hydroquinone 21 g 4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone (dimesone S) 0.9 g Potassium bromide 5 g Benzotriazole 0.2 g 5-Methyl-benzotriazole 0.13 g Boric acid 8 g Diethylene glycol 40 g 2-Mercapto-6-hydroxypurine 0.06 g Water was added to 1 liter and pH was adjusted to 1 liter with potassium hydroxide. Adjust to.

Fixer composition (per liter) Ammonium thiosulfate (70% aqueous solution) 200 ml Sodium sulfite 22 g Boric acid 9.8 g Sodium acetate trihydrate 34 g Acetic acid (90% aqueous solution) 14.5 g Tartaric acid 3.0 g Aluminum sulfate ( 27% aqueous solution) 25 ml When using, add water to make 1 liter. The pH of the used solution was 4.9.

The results are summarized in Table 1.

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[Table 1]

It is clear that the samples according to the invention are excellent.

[0102]

According to the present invention, a polyester support having good adhesiveness to the photosensitive layer, excellent dimensional stability and being hard to curl can be obtained, and a silver halide emulsion is further provided on the support. The photographic light-sensitive material coated with the layer showed very little change in photographic performance over time.

Claims (4)

[Claims] 1. A subbing layer having a hydrophilic resin containing a polyester solvent or a swelling solvent, or a subbing layer having a vinylidene chloride-based copolymer, and at least one subbing layer on at least one of the polyester films. A polyester support characterized in that after coating and drying, the polyester film is cooled from the glass transition temperature + 25 ° C to the glass transition temperature + 5 ° C over 20 seconds or more. 2. The polyester support according to claim 1, wherein the polyester solvent or the swelling solvent is contained in an amount of 1 to 20% by weight of an undercoating processing liquid containing the polyester solvent or the swelling solvent. 3. The polyester according to claim 1, wherein the polyester solvent or the swelling solvent is a hydroxyl group-containing aromatic compound, or a carboxyl group or an acid anhydride-containing aromatic compound thereof. Support. 4. A photosensitive material having a photosensitive layer on at least one of the polyester supports according to claim 1.