JPH01298350A - Photographic sensitive material - Google Patents

Abstract

PURPOSE:To facilitate to solve the curl of the title material due to winding habit after development processing, and to prevent the deterioration of the shelf-life of a latent image by specifying the haze of a polyester film to <=3% and the moisture content of the polyester film to >=0.5wt.% respectively, and by incorporating a polyoxy ethylene compd. in an emulsion layer or a nonphotosensitive layer existing in the same side to the emulsion layer contd. in the photosensitive material. CONSTITUTION:The photosensitive material comprises a supporting body which contains the polyester film having the haze of <=3% and the moisture content of >=0.5wt.%, and a silver halide emulsion layer mounted on the supporting body. The polyoxy ethylene compd. is incorporated in the layer existing in the same side to the emulsion layer. And, the moisture content of the polyester film is preferably 0.6-5.0wt.%. Thus, the recovery ratio of the curl is improved, and the deterioration of the shelf-life of the latent image is prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a photographic window light material, and in particular, it uses a polyester material as a support and has excellent curl removal properties after development processing and good latent image preservation. This invention relates to photographic materials with good properties.

BACKGROUND OF THE INVENTION Photographic materials are generally produced by coating at least one photographically sensitive layer on a plastic film support. As this plastic film, generally used are fiber-based polymers typified by triacetyl cellulose (hereinafter referred to as rTAcJ) and polyester-based polymers typified by polyethylene terephthalate (hereinafter referred to as (PET)).

Conventionally, PET film has excellent productivity, mechanical strength,
It has also been considered to be a substitute for TAC due to its dimensional stability, but in the roll form widely used as photographic light-sensitive materials, strong curls remain, making it difficult to handle after development processing. Although it has the above-mentioned excellent properties, its range of use has been limited.

In general, photographic materials are in sheet form such as X-ray film, plate-making film, and cut film, and typical roll films are 35m/m/m
It is housed in a patrone with a width or smaller width,
It is a color or black and white negative film that is loaded into a general camera and used for taking pictures.

On the other hand, TAC, which is mainly used for roll films,
The most important feature of film as a photographic support is that it has no optical anisotropy and has high transparency. Even more-
One of its outstanding features is that it also has excellent properties in terms of decurling properties after development. That is, T
Due to its molecular structure, AC film has a relatively high water absorption property for a plastic film, so the curling that occurs when it is rolled as a roll film over time is caused by the molecular chains flowing due to water absorption during the development process. , the immobilized molecular chains undergo rearrangement over time.

As a result, it has an excellent property of eliminating curls that have already formed. In photographic light-sensitive materials such as TAC, which uses a film that does not have curl recovery properties, when used in roll form, for example, printing to form an image on photographic paper after development is a process. , problems such as scratches, out of focus, and jamming during transportation may occur.

By the way, the uses of photographic materials have diversified in recent years, such as faster film transport during photography, higher photographic magnification,
In addition, the miniaturization of imaging devices has progressed significantly. In this case, the support for the photographic light-sensitive material is required to have properties such as strength, dimensional stability, and thin film formation.

However, due to the rigid molecular structure of TAC, the resulting film is fragile and cannot be used for these applications. Although PET film has excellent mechanical properties, there is a problem in that it cannot be used, and there has been a desire to improve it.

On the other hand, when there is a considerable amount of time between exposure (photography) and development processing, such as with silver halide negative photosensitive materials for photography, the latent image formed by exposure tends to disappear; This is called "latent image regression."

Preservability of latent images is one of the important properties of photographic materials.

(Object of the Invention) Therefore, the object of the present invention is to provide a photographic light-sensitive material which is composed of a support having excellent transparency and mechanical properties, which can easily eliminate curling after development processing, and which does not have poor latent image storage stability. It is about providing.

(Disclosure of the Invention) These objects of the present invention are to provide a polyester film having a haze of 30% or less and a water content of 0.5% by weight or more, and a support having a small amount (in both cases, one layer) on the support. This was achieved by a silver halide photographic material having a silver halide emulsion layer, which contains a polyoxyethylene compound on the same side as the emulsion layer.

The moisture content of the polyester film of the present invention is measured by conditioning the film at 23°C and 30% RH for 13 hours, then immersing it in distilled water at 23°C for 15 i, and then using a trace moisture meter. For example, the drying process is carried out using a Mitsubishi Kasei 073iCA-02 type) at a drying temperature of 150'C.

The polyester film of the present invention is characterized in that the water content measured by this method is Q,5Pr amount % or more, preferably 0.6 to 5.0 m:%.

Moisture content is 0. If it is less than 5% by weight, the ability to eliminate loose curls after the phenomenon treatment will not be improved, and on the other hand, if the water content is too high, the dimensional stability will deteriorate due to moisture absorption.

In the present invention, polyester is a polyester whose main components are aromatic dibasic acids and glycols. Typical dibasic acids include terephthalic acid and isofucleic acid, and examples of glycols include ethylene glycol. ,
Examples include propylene glycol, butanediol, neopentyl glycol, 1°4-cyclohexanediol, diethyl glycol, and the like. Among the polyesters made of these components, polyethylene terephthalate (PET) is the most convenient in terms of availability.
This will be explained below using PET.

The copolymerized polyethylene terephthalate film preferably used in the present invention is composed of a copolymerized polyethylene terephthalate film containing an aromatic dicarboxylic acid component having a metal sulfonate as a copolymerization component.

Specifically, the aromatic dicarboxylic acid having a metal sulfonate includes 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 4-sodium sulfophthalic acid, and 4-sodium sulfo-2,6-naphthalene dicarboxylic acid. And these sodiums are substituted with metals such as potassium and lithium. On the other hand, it is preferably 2 to 15 mol%, particularly preferably 4 to 10 mol%.

The copolymerized polyethylene terephthalate film used in the present invention is further copolymerized with an aliphatic dicarboxylic acid component having 4 to 20 carbon atoms, which improves transparency, particularly suppresses whitening on the surface of the copolymerized polyethylene terephthalate film and improves foldability. Preferable from the viewpoint of sex.

Specific examples of the aliphatic dicarboxylic acid component having 4 to 20 carbon atoms include succinic acid, adipic acid, and sebacic acid, among which adipic acid is preferred.

The copolymerization ratio of the aliphatic dicarboxylic acid component having 4 to 20 carbon atoms is preferably 3 to 25 with respect to the terephthalic acid component.
Mol%, particularly preferably 5-? It is 20%.

In addition, in the polyester film of the present invention, it is also possible to further copolymerize other acid components or glycol components as long as the proportion is small within a range that does not impair transparency and mechanical properties. For example, polyalkylene glycol, especially polyethylene glycol, can be copolymerized with 0 to IO weight percent. The molecular weight of the polyalkylene glycol used for this purpose is 600 to t.
o, ooo are preferable.

Furthermore, various additives can be contained in the polyethylene terephthalate film of the present invention. For example, one of the problematic properties when using polyester film as a support for photographic photosensitive material (F4) is the problem of fringing caused by the high refractive index of the support. Photographic supports include triacetyl cellulose (TAC) and polyethylene terephthalate (P).
Polyester-based polymers such as TAC (ET) are commonly used, but one of the major differences in optical properties between TAC and PET is the refractive index. This refractive index is P
While ET is about 1.6, TAC is as small as 1.5.On the other hand, the refractive index of gelatin, which is mostly used in subbing layers and photographic emulsion layers, is 1°50 to 1.55; Taking the ratio of 1. for PET. 5/1. 6
And smaller than 1, the light is from the film edge! When heated, polyester films tend to reflect at the interface between the base and emulsion layers, and therefore polyester films cause so-called light piping phenomenon (edge fog).

As a method for avoiding such a light piping phenomenon, there are known methods such as making the film contain inert particles, cryo, etc., and adding a dye. In the present invention, a preferred method for preventing light piping is film haze. This method involves adding dye that does not significantly increase the

There are no restrictions on the dye used for film dyeing, but due to the general properties of five-light materials, gray dyeing is preferable, and dyeing ↑4 is based on heat resistance in the film forming temperature range of polyester film. It is preferable that the amount of carbon dioxide is small and that the compatibility with polyester is excellent.

As a dye, Diares manufactured by Mitsubishi Kasei is used from the above points.
The purpose can be achieved by mixing commercially available dyes for polyester, such as Kayase L manufactured by Nippon Kayaku.

Regarding the dyeing density, the color temperature in the visible light range is measured using a color densitometer manufactured by Macbeth and must be at least 0°01 or higher. More preferably, it is 0.03 or more.

The polyester film of the present invention can be imparted with lubricity depending on the application, and there are no particular limitations on the means for imparting lubricity. Application of an activator and the like are commonly used.

Such inert y51 particles include 5iOz, Ti0*
, Ba5Oa, CaC0*, talc, kaolin, etc. In addition to the above-mentioned method of imparting slipperiness using an external particle system in which inert particles are added to the polyester synthesis reaction system, it is also possible to adopt a method of imparting slipperiness using an internal particle system that precipitates catalysts added during the polyester polymerization reaction. It is.

There are no particular limitations on these means for imparting slipperiness, but since transparency is an important requirement for a support for photographic light-sensitive materials, in the method for imparting slipperiness mentioned above, polyester is used as the external particle system. It is desirable to select SiO□, which has a refractive index relatively close to that of the film, or an internal particle system that allows the precipitated particle size to be relatively small.

Furthermore, when imparting slipperiness by kneading, it is also preferable to laminate functionalized layers in order to obtain greater transparency of the film. Alternatively, a coextrusion method using a multi-manifold die is exemplified.

In the present invention, depending on the copolymerization ratio, precipitation of low polymers may become a problem during the heat treatment when forming the subbing layer. It is possible to do so, and even in that case, the coextrusion method is used as a blind means.

The raw material polymer for the copolymerized polyethylene terephthalate film of the present invention can be synthesized according to conventionally known polyester production methods.For example, when an acid component is directly esterified with a glycol component, or when a dialkyl ester is used as an acid component, Copolymerized polyethylene terephthalate can be obtained by carrying out a transesterification reaction with a glycol component and heating this under reduced pressure to remove excess glycol components. At this time, a transesterification reaction catalyst or a polymerization reaction catalyst may be used, or a heat-resistant stabilizer may be added, if necessary.

The copolymerized polyethylene terephthalate obtained above is molded into granules at once, dried, and then melt extruded to form an unstretched sheet, which is then biaxially stretched and heat treated to form the desired film.

Biaxial stretching is! 11. Either horizontal sequential stretching or time stretching between two axes may be used, and the stretching ratio is not particularly specified, but usually 2.0 to s or @ is appropriate. After the horizontal stretching, the film may be re-stretched in either the vertical or horizontal directions.

The drying force before melt extrusion in the present invention is preferably a vacuum drying method or a dehumidification/drying lambda method.

In the present invention, the temperature at the time of Nobeoki is 7
0~100" C1 Yokonobu offshore is preferably 80~160°C.

Heat fixation temperature change is 150~210°C1, especially 160~
Preferably it is 200°C.

The thickness of the copolymerized polyethylene terephthalate film used in the present invention can be set appropriately depending on the field of use of the photographic film, but it is preferably 25 to 250 μm, more preferably 4 μm.
A thickness of 0 to 150μ is employed.

The copolymer composition according to the present invention has the excellent transparency and breaking strength that PET originally has.
”, the initial elastic modulus is 200 to 500 kg/mm2, and the tear strength at a film thickness of 50 μm is 30 g or more at a thickness of 120 μm. If the strength is less than this, the excellent practical properties that PET originally has This results in a loss of compassion towards TAC.

In the present invention, transparency, breaking strength, initial elastic modulus, and tear strength are determined as follows.

[Transparent 1st raw] Film haze AS'1.1-D 1003-52
Measured according to

[Fracture IJfr strength and initial elastic modulus]

According to JIS-21702-1976, width 10mm,
A strip piece with a length of 100 mm, the tensile speed is 300 n++n/min when measuring the breaking strength, and the initial elastic modulus is 20 au.
/min [Measurement of tear strength] Using a light load type tear strength tester (manufactured by Toyo Seiden O-Riki), a 13 mm incision was made in a sample size of 51 x 64 + p, m, and the remaining 51 mm was torn, and the indicated value was I read it.

The polyester film and support of the present invention are characterized by excellent curl resolving properties (hereinafter referred to as curl recovery rate) after image processing. It is preferable that the curl recovery rate is 50% or more, particularly 80% or more.

[Measurement of curl recovery rate]

Wrap a sample size 12cm x 35nun film around a 10mm diameter core and heat at 60°C x 30%RHX 72
hr treatment, then released from the winding core, immersed in steaming water at 40°C for 15 minutes, and then heated at 55°C with a load of 50g applied.
The sample was dried for 3 minutes in a constant air bath, hung vertically, and the sample length was measured to evaluate how much the sample length had recovered to its original 12 cm.

The copolymerized polyethylene terephthalate film used in the present invention is characterized by superior adhesion to various coating layers such as emulsion layers, compared to conventional polyethylene terephthalate films.

The polyester film of the present invention can be previously subjected to various surface treatments such as corona discharge treatment, chemical treatment, fire treatment, etc., as necessary, in order to improve adhesiveness and wetting characteristics of coating liquid.

Among these surface treatments, the most preferably used in the present invention is corona discharge treatment, which causes less 1 degree polymer to be detected on the film surface.

The polyester support of the present invention preferably has a subbing layer in order to increase the adhesive strength with a photographic layer such as a photosensitive layer coated thereon.

Examples of the subbing layer include a subbing layer using a polymer latex made of a styrene-butadiene copolymer or a vinylidene chloride copolymer, and a subbing layer using a hydrophilic binder such as gelatin.

The subbing layer preferably used in the present invention is a subbing layer using a hydrophilic binder.

As the hydrophilic binder used in the present invention, water i9 i
Examples include raw polymers, cellulose ester polymers, and water-soluble polyesters.

At 7? S polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, maleic anhydride copolymers, and cellulose esters include carboxymethyl cellulose and hydroxyethyl cellulose. etc. Latex polymers include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers,
These include acrylic acid ester-containing copolymers, vinyl acetate-containing copolymers, butadiene-containing copolymers, etc. Among these, gelatin is most preferred.

Examples of compounds that swell the support used in the present invention include resorcinol, chlorresorcinol, methylresorcinol, 0-cresol, m-cresol, p-cresol,
Examples include phenol, 0-chlorophenol, p-chlorophenol, dichlorophenol, trichlorophenol, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid, and chloral hydrate. Among these, the preferred one is
They are resorcin and p-chlorophenol.

Various gelatin hardeners can be used in the subbing layer of the present invention.

Chromium salt (chromium alum) as a gelatin hardening agent
, aldehydes (formaldehyde, geltaraldehyde, etc.), isocyanates, active halogen compounds (
(2,4-dichloro-6-hydroxy-3-) riazine, etc.), epichlorohydrin resin, and the like.

The base material of the present invention may contain precipitate-free fine particles such as 5iOz, TiO□, or polymethyl methacrylate copolymer fine particles (1 to 10 μm) as a matting agent.

The undercoating layer according to the present invention can be applied by a generally well-known coating method, such as a dip coating method, an air knife coating method, a curtain coating method, a wire barcoding method, a clavier coating method, an extrusion coating method, etc. It is possible.

In addition to the photosensitive layer, the photosensitive material of the present invention can have non-photosensitive layers such as an antihalation layer, an intermediate layer, a back layer, and a surface protection layer.

The binder for the back layer may be a hydrophobic polymer or a hydrophilic polymer such as that used for the subbing layer.

The back layer of the photosensitive material of the present invention may contain an antistatic agent, a lubricant, a pine L agent, a surfactant, a dye, etc. As the antistatic agent used in the back layer of the present invention, in particular, There is no limitation, and examples of anionic polymer electrolytes include polymers containing carboxylic acids and -J)Lt carbonates and sulfonates, such as those described in JP-A No. 48-22017;
JP 46-24159, JP 51-30725, JP 51-129216, JP 55-9594
It is a polymer as described in No. 2. Examples of cationic polymers include those described in JP-A-49-121523, JP-A-48-91165, and JP-B-49-24582.

There are also anionic and cationic ionic surfactants, such as JP-A-49-85826 and JP-A-49-85826.
No. 33630, US 2,992,108, US 3,20
6,312, JP-A-48-87826, JP-A-49-
No. 11567, Special Publication No. A9-ilssa, Japanese Patent Application Publication No. 1983
Compounds such as those described in No.-70837 and the like can be mentioned.

The most preferable antistatic agent for the back layer of the present invention is Z'n'0STi(h, Snow SAj!xO
1,1nzos, S i OH, MgOlBaOl
At least 1f selected from M o Oz! These are fine particles of a crystalline metal oxide or a composite oxide thereof.

The conductive crystalline oxide or composite oxide fine particles used in the present invention have a volume resistivity of 10 7 Ωcm or less, more preferably 10% ΩC 1 fl or less.

In addition, the particle size is 0.01 to 0.7 μ, especially 0.0
It is desirable that the thickness be 2 to 0.5μ.

Regarding the method for producing fine particles of conductive crystalline metal oxide or composite oxide used in the present invention,
143430 and 60-258541, ``Firstly, a method in which metal oxide fine particles are produced by firing and then heat-treated in the presence of a different type of atom to improve conductivity,'' secondly. The second method is to coexist different atoms to improve conductivity when manufacturing metal oxide fine particles by firing, and the third method is to lower the oxygen concentration in the atmosphere when manufacturing gold layer fine particles by firing to eliminate oxygen defects. It is easy to find out how to do this. Examples containing different atoms include A2, In, etc. for ZnO, Nb, Ta, etc. for Ti1t, and Sb, Nb, halogen elements, etc. for SnO. The amount of foreign atoms added is 0.01 to 30 mo1%
A range of O, l = lomo 1% is preferred for poetry.

Next, the photographic layer of the photographic light-sensitive material of the present invention will be described.

The most preferred photographic materials of the present invention include, for example, color negative films, color positive films, color reversal films, and black and white negative films. Particularly preferred is black and white negative film.

As the photosensitive silver halide used in the present invention, silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chlorobromoiodide can be used. Preferably silver iodobromide,
It is silver chloriobromoiodide.

The average particle size is preferably 0.5 mμ or more. The particle size distribution may be narrow (or wide).

The silver halide grains in the emulsion may have a regular crystal shape such as a cube or an octahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape.
It may have a crystalline form (ilar) or a composite form of these crystalline forms. It may also consist of a mixture of particles of various crystalline forms. Furthermore, tabular grains having a particle diameter of 5 times or more the particle thickness are preferably used in the present invention.

Such tabular grains are described in US Pat.

≠3g, 2.2 No. Otsu, same No. ≠, 4134t, 2.2
It is described in detail in the specifications of JP-A No. 7, JP-A-Shoj, l'-/ko-7ri, No. 2/, etc.

The light-sensitive silver halide emulsion used in the present invention is described in "Chimney Photography" by P. Glafkides.
ie et Physique Photo-gra
phique) J (Paul Montek Pau1Mo
``Photograph Emulsion Chemist''' by G.F. Duffin
ic Emulsion Chemistry)
J (The Focal Press)
Published by rQSS, /ri, <&), Gui El Zelikman et al.
``Making and Coating Photographic Emulsions'' by Ma Young and C.
oating Photographic Emuls
ion ) J (Focal Press The Fo
It can be prepared using the method described in, for example, published by Cal Press, 2003).

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any one-sided heating method, simultaneous mixing method, or a combination thereof. .

A method in which particles and silver ions are formed in excess (so-called back mixing method) can also be used.

As one type of simultaneous mixing method, a method in which p A g in a liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used.

This method yields silver halide emulsions with regular crystal shapes and nearly uniform grain sizes.

Two or more types of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

For details of the multilayer structure halogenated grain emulsion preferably used in the present invention, many known documents can be referred to.
Examples include No. 3o, No. 6O-1lttJt, No. A, and No. 2-/2g Hiro 3.

As a binder for the photographic layer, white matter such as gelatin and casein; cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose; sugar derivatives such as sodium chloride, sodium alginate, and starch derivatives; synthetic hydrophilic colloids such as borivinyl alcohol and poly-17N. −
Vinyl pyrrolidone, polyacrylic acid copolymer, or their pure or partial hydrolyzates can also be used in combination.

Gelatin referred to herein refers to so-called lime-treated gelatin, acid-treated gelatin, and Cy-treated gelatin. As the gelatin, gelatin containing the polymer component (1) described in JP-A-02-87952 is preferred.

The photographic window optical material of the present invention can be used in a photographic process (1.l layering).
No. 2, written in Special Publication No. 45-5331, etc. '63 (7)
'f' Lucyl acrylate latex may be included.

Although the silver halide emulsion can be used as a so-called "primilive" emulsion without chemical sensitization, it is usually chemically sensitized. For chemical sensitization, the above-mentioned book by Glafkldes or Zeikman et al. or Il, Fr1eser, ed.
gender I'hoto6rapl+1schen
Prozesse 5lit 5ilbarl+al
oHeniden (Yakademischa Ver.
lagsBa5ellscl+aft, 1968) can be used.

In other words, a sulfur sensitization method using a sulfur-containing compound that can react with silver ions or activated gelatin, or an elemental substance? A reduction sensitization method using t, a noble metal enhancement method using a noble metal compound such as gold or oil, etc. can be used alone or in combination. As the sulfur sensitizer, other compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. can be used, and specific examples thereof are described in U.S. Pat. No. 1,574.944.
No. 2.410,611, 2. ．． 278.947, 2.728.668, and 3,656.955. Examples of reduction sensitizers that can be used include stannous salts, amines, hydrazine salts, formamidine sulfinic acid, and silane compounds. For noble metal sensitization, in addition to gold complex salts, I? Complex salts of metals of Group 1 of the i+ 1111 table can be used.

The light-sensitive material of the present invention may contain 1+n compounds as antifoggants or stabilizers.

i.e. azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles 1i, benzimidazoles (particularly nitro- or halogen substituted); for heterocyclic mercapto compounds such as mercaptothiazole, mercaptobenzothiazole in, mercapto; Benzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly l-phenyl''5-mercaptotetrazole), mercaptopyridines - the above heterocyclic mercapto compounds having water-soluble groups such as carboxyl groups and sulfone convex necks: Thioketo compounds such as oxazolinthione; azaindenes such as tetraaza-indenes; (especially 4
-Hydroxy position IIA (1,3,3a.

Many compounds known as antifoggants or stabilizers can be added, such as (7) tetraazaindenes); benzenethiosulfonic acid, benzenesulfine, etc.

For more detailed examples of these and how to use them, see, for example, U.S. Patent No. 3. 954. 474, No. 3.982.947, No. 4.021.248, and Japanese Patent Publication No. 52-28゜660 fu.

Hardening agents include mucochloric acid, formaldehyde, dimethylol urea, glyoxal, succinaldehyde,
Aldehyde compounds such as glutaraldehyde; divinyl sulfone, methylene bismaleimide, 5-acetyl-
1,3-diacryloyl-hexahydro-)riazine, 1,3゜5-triacryloyl-hexahydro-
3-triazine, l, 3.5-)rivinylsulfonyl-hexahydro-5-)lyazine bis(vinylsulfonylmethyl) ether, 1,3-bis(vinylsulfonylmethyl)propanol-2, bis(α-vinyls) 2. Active vinyl-based compounds such as rubonyl-7-amide)ethane;2.
Active halogen compounds such as 4-dichloro-6-hydroxy-5-1-riazine sodium salt: N-carbamoylpyridinium salt tl (1-morpholinocarbonyl-
(3-pyridinio)methanesulfonate, etc.), haloamidinium salts tff (1-(1-chloro-1-pyridinomethylene)pyrrolidinium, 2-naphucrenesulfonate, etc.), and inorganic compounds such as chromium aerobane. can.

The photographic emulsion layer or other 114 layers of the photosensitive material T81 of the present invention contains coating aids, antistatic properties, smoothness improvement, and emulsifying content 11.
In addition, surfactants other than those of the present invention may be included for various purposes such as preventing tB adhesion and improving photographic properties (for example, promoting development, increasing contrast, and increasing sensitization).

For example, saponin (steroid type), alkylene oxide Lj R form (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol alkyl ethers, Non-ionic compounds such as alkylene glycol alkylamines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Surfactant; alkyl carboxylate, al; torsulfonate, alkylbenzene sulfonate, alkylnafucrene sulfonate, alkyl (, A acid esters, alkyl phosphate esters, N-acyl-N-alkyl taurine Carboxy groups, sulfo groups, phosphoconvex, sulfate ester groups, such as acids, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc.
Anionic surfactants containing acidic groups such as phosphate groups;
Amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphate esters, alkyl carboxylic acids,
Amphoteric surfactants such as amine oxides: alkylamine salts, aliphatic or aromatic quaternary ammonium salts, IM monocyclic quaternary ammonium salts such as pyridinium and imidazolium, and aliphatic or heterocyclic phosphonium or Cationic surfactants such as sulfonium salts can be used.

The photographic emulsion of the present invention may be spectrally enhanced by methine dyes and others. Dyes used include cyanine dyes,
Merocyanine pigment? Included are M merocyanine dyes, IM merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and omyoxonol dyes. Particularly useful r! ! , is a pigment belonging to cyanine pigments, merocyanine pigments, and merocyanine pigments. Any of the nuclei commonly used for cyanine dyes can be used as the Onkyo 11'A node r2 nucleus for these dyes. Zunawara, one pyrroline, one sasoline nucleus, thiazoline nucleus, virole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.Alicyclic hydrocarbon ring in these nuclei are fused (Pig; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus,
A naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a henzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thiotoxazolidine-2 nucleus as a nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, and the like can be applied.

The polyoxycartylene compound used in the present invention preferably has at least one oxyethylene group, more preferably 2 to 100 oxyethylene groups.

As the polyoxyethylene compound, compounds represented by the following general formulas (1-/), [I-2] and (II) are particularly preferred.

General formula (1-/) R□-A so0820820 几-T 几2 General formula [1-2] General formula Cl-3] In the formula, 1 is a hydrogen atom or a substituted or unsubstituted carbon number 1 to 3 o an alkyl group, an alkenyl group or an aryl group, A
is 10- group, -8- group, -COO--8O2N-R,1
5 groups (herein, "14" represents a hydrogen atom or a substituted or unsubstituted alkyl group).

R2 has the same meaning as R1 or 几□-he1 described above.

R3, IL4, R8, 几. , 几1□ and R14 are hydrogen atoms, substituted or unsubstituted alkyl groups, aryl groups,
It represents an alkoxy group, a halogen atom, an acyl group, an amide group, a sulfonamide group, a carbamoyl group or a sulfamoyl group. In addition, in the formula, R7, IL9, "11 and 几13 are substituted or unsubstituted alkyl groups, aryl groups, alkoxy groups, halogen groups, acyl groups, amide groups,
Represents a sulfonamide group, carbamoyl group or sulfamoyl group.

R5 and IL6 represent a hydrogen atom, a substituted or substituted alkyl group, an aryl group, or a heteroaromatic group.

Rin, 1t7 and R8, Ro and Rin. , l(+1, and FL1□ and IL13 and R□4 may be connected to each other to form a substituted or unsubstituted ring. n s , n 2, R
3 and R4 is the average degree of polymerization of ethylene oxide, and is 2 to 1.
It is a number of 00.

Moreover, m is an average degree of polymerization, and is a number from 1 to 10.

In the general formulas (1-/), (1--2) and (1--?), R1 is preferably a hydrogen atom or carbon fi4<
-yJ is an alkyl group, alkenyl group, or alkylaryl group of #, particularly preferably a hydrogen atom, a butyl group, a hexyl group, a dodecyl group, an isostearyl group, an oleyl group, or t-butylphenyl i, -x.

II-sheet t-7' tylphenyl group, 2. 2. These include Hiro-dinonylphenyl group, octylna-phthyl group, and the like.

I'L R'RR,R 几、■
Mo31 4＼ 7% 8X 9%
10 11'几, lt and RJ1
4 is preferably methyl, l 2 13 ethyl, i-propyl, t-butyl, t-amyl, t
-Number of carbon atoms such as hexype t-octyl, nonyl, tecyl, dodecyl, trichloromethyl, tribromomethyl, phenylethyl, cophenyl-2-propyl, etc.
~20 substituted or unsubstituted alkyl groups, phenyl groups, p
-Chlorophenyl group, etc. (7) R-substituted or unsubstituted aryl group, -CH16 (herein, 16 represents a substituted or unsubstituted alkyl group or aryl group having carbon number/~1θ; the same applies hereinafter) A substituted or unsubstituted alkoxy group, a halogen atom such as a chlorine atom or a bromine atom, an a/l group represented by -COl□6, -I'JR,,7Co(
Here, R1□ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. amide group represented by (the same applies hereinafter), -NR
, SO 216 is a sulfamoyl group coated with YL3, IL4.
1(it, 几 and ■'L14 may have 8% 10 12 hydrogen atoms. Among these, R7, R9, R1□ and "13 are preferably an alkyl group or) rogen atom, particularly preferably It is a bulky tertiary alkyl group such as a t-butyl group, a t-amyl group, or a t-octyl group.R,8
, Rlo, R1□ and )R14 are particularly preferably hydrogen atoms.

R5 and R6 are preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl n-heptyl group, l-ethylamyl group, n-undefur group, trichloromethyl group, tribromomethyl group Substituted or unsubstituted alkyl groups such as α-furyl group, phenyl group, naphthyl group, p-ria phenyl group, p-methquinophenyl group,
It is a substituted or unsubstituted aryl group such as m-nitrophenyl group.

Also, 几 and R6, R7 and IL 8, 几 and 1t1o,
R1□ and R1□ and 几13 and R may be connected to each other to form a substituted or unsubstituted ring, for example, a cyclohexyl ring. Among these, FL5 and R6 are particularly preferably a hydrogen atom, an alkyl group having carbon number/~r, a phenyl group, or a furyl group. n n n and R4 are particularly preferably numbers from 1 \ 21 3 j to 30. R3 and 04 may be the same or different. -Among the polyoxyethylene compounds represented by formulas (1), (II) and (III), compounds of formula [■] are particularly preferred.

Next, specific examples of the polyoxyethylene compound of the present invention will be shown.

Compound example 1-/ C1□■4□3COOfCH2CH20 cod H-r C5H3□COO+CH2CH20) T-, H01□
FI33COO(CH2CH20+V5CF■3■-HiroshiCl8H350(CH2CH20mo, H-r C1□H250(CH2CH20+voHC16H33
SOCH2CH2O Beat ■] ■-Rice CIO SOCH2CH20 H ■-ta! -70 1-i i ■-72 1-/3 1-iμ -i r 1-/4 1-/7 1-/J' 1-/ri, C1□H25S-fCI4□CH2O+v6H1-r
θ CH2CH20fCH2CH20+T-2H ■--22 ■-23 ■--Hiroshi CH-t C4H0-t -2s CH-1C4H9-1 The polyoxyethylene compound of the present invention can be used depending on the type, form, or coating method of the photographic material used. The amount used varies depending on the factors, but in general, the amount used is A
It is preferably 6.0 mg or more per mole of g (especially preferably 60 mg or more).

The polyoxyethylene compound of the present invention is preferably added to the light-sensitive emulsion layer of the photographic light-sensitive material, but it may be added to other non-light-sensitive layers.

The method of using these polyoxyethylene compounds in the layers of photographic materials is to add them to the coating solution for forming the layers.
These compounds are added as they are, or after being dissolved in water, an organic solvent such as methanol, ethanol, acetone, or a mixed solvent of water and the organic solvent, and the coating solution is applied and dried, or the coating solution is applied to the surface of the support. The solution may be sprayed, applied, or immersed in the solution and dried.

When added to the emulsion layer, it may be added to the emulsion during the emulsion manufacturing process (such as a chemical ripening process) or after the process is completed.

(Example) The present invention will be further explained below with reference to Examples.

Example-1 ■) Creation of polyethylene terephthalate film 100 parts by weight of dimethyl terephthalate, 70 parts by weight of ethylene glycol
Part by weight, 1 dimethyl 5-sodium sulfoisophthalate
0 parts by weight and 10 parts by weight of dimethyl adipate, 0.1 parts by weight of calcium acetate and 0.0 parts by weight of antimony dioxide.
3 parts by weight was added and transesterification was carried out by a conventional method. Add 0.0 phosphoric acid trimethyl ester to the obtained product.
Add 5 parts by weight, gradually raise the temperature and reduce the pressure, and finally 2 parts by weight.
Polymerization was carried out at 80° C. and below 1 mHg to obtain copolymerized polyethylene terephthalate.

After drying the copolymerized polyethylene terephthalate in a conventional manner, it was melt-extruded at 280°C to create an unstretched sheet.
Next, the film was sequentially stretched 3.5 times in the longitudinal direction at 90°C and 3.7 times in the transverse direction at 95°C, and then heat-set at 200°C for 5 seconds to obtain a biaxially stretched film with a thickness of lOOμ. Ta. Film properties include haze of 1°2%, breaking strength of 12kg/m,
The initial elastic modulus was 340 kg/kg, and the transparency and mechanical properties were good.

Note that transparency, breaking strength, and initial elastic modulus were measured under the following conditions.

Transparency: Film haze was measured according to ASTN-D100152.

Breaking strength and initial elastic modulus: Width 10aw according to J l5-21702-1976
, a strip piece with a length of 100 a+m, the tensile speed was 300 m/min when measuring the breaking strength, and the initial elastic modulus was measured at 20 m/min.

2) Measurement of Curl Recovery Rate The moisture content of the PET film (thickness 50 mμ) according to the present invention prepared as described above and a commercially available PET film (same thickness) was measured by the method of the present invention.

Furthermore, the curl recovery power was measured by the following method, and the results shown in Table 1 were obtained.

[How to evaluate curl]

A film with a sample size of 12C11
After processing for 72 hours, it was released from the core and rolled for 40 hours.
After immersing in distilled water at °C for 15 minutes, a load of 50 g was applied.
The sample was dried for 3 minutes in an air thermostat at 5°C, hung vertically, and the sample length was measured to evaluate how much the sample length had recovered to its original 12 cm.

Table 1 As is clear from Table 1, the moisture content is 0. 7% by weight PE
It can be seen that the T film has an extremely excellent curl recovery rate.

3) Preparation of photographic material 3-1) Coating of subbing layer After each of the PET films described above was subjected to corona discharge treatment, a subbing layer having the following composition was provided. The degree of corona discharge treatment is
It was 0.02KVA・minute/portion.

gelatin 3g distilled water
250cc Sodium α-
Sulfodi 2-ethylhexyl succinate 0.05 g Formaldehyde 0.02 g 3-2) Preparation of photosensitive silver halide emulsion Potassium bromide and potassium iodide and silver nitrate were added to the gelatin aqueous solution with vigorous stirring,
Thick plate-shaped iodobromide 11 with an average particle size of 1μ! (average iodine content 8 mol%) was prepared. Thereafter, it was washed with water using a conventional precipitation method, sensitizing dye 1 was added, and chemical sensitization was performed using a gold/sulfuric acid sensitization method using chloroauric acid and sodium thiosulfate to obtain a photosensitive silver iodobromide emulsion A. . In the same manner, however, by changing the amount of potassium iodide and the preparation temperature, a photosensitive silver iodobromide emulsion B of plate-like silver iodobromide (average iodine content 6 mol%) with an average grain size of 0.6 μm was obtained. Ta.

Sensitizing Dye-1 Samples 1 to 11 were prepared by sequentially applying the following layers on a support at the same time from the support side.

(Bottom layer) Binder; Gelatin - 11 g/Po coating coating aid; Poly-p-styrene potassium hydroxide salt, 2.47. '-1) '0°0'''''' Binder: Gelatin - 11g/g / Po: 1O-4 mol/Po 1O-4 mol/rrl Fixing accelerator 3X10-3 units/M (Intermediate layer) Binder; Gelatin - 10.4 g/m Coating aid; Poly P-styrene sulfonic acid potassium salt 3.3 μg/■ (Emulsion layer-1) Coating silver amount; Emulsion 8 1.5 g/anti-binder; Gelatin-2 2 g/Bo additive; Listed in Table 2 Coating aid: Poly p-styrene sulfonic acid potassium salt 50 μ/rd Hardener: 1,2-bis(vinylsulfonylacetamide) Ethane 45 μ/po (emulsion layer-2) Coating amount of silver: Emulsion A 4g/g/Polymer; Binder; Gelatin - 26.8g/Polymer; Listed in Table 2 Trimethylolpropane 420g/Polymer Coating aid: Poly p-styrene sulfonic acid potassium rum salt 170mg/Poly( Surface protective layer) Gelatin - 30.8 g/po 1llt Polybotacium ρ-vinylbenzenesulfonate 6/rrr Polymethyl methacrylate fine particles (average particle size 3 mμ) 0.13+ag/po 4-
Hydroxy-6-methyl-1,3,3a,7-chitrazaindene 140■/MCs II
IJ (CHx C1l zoh-HCll t C
tlCIl z 0) TIH 50■/Bo (3) Sensitometry After applying these samples at a temperature and humidity of 30°C and 65%RH 7
Stored for days. Each sample was tested in the following manner.

<Evaluation of latent image storage stability> (i) Fresh performance Each sample was exposed to 400 lux tungsten light for 1/10 seconds through an optical wedge, and then immediately developed with the following developer at 20°C for 7 minutes.

The photographic sensitivity at a constant density (optical density of 0°2) higher than the fog density was measured using the same method for each fixed, washed, and dried sample.

Developer Metol 2g Sodium sulfite 100g Hydroquinone
5g Pollux・10H,02
g Add water 11 Fixer:
Fuji Fix (Fuji Photo Film Co., Ltd. % formula % i) Same as Fresh performance except that after exposure, it was left in a dark room at 30° C. and 70% for 7 days, and then developed.

The latent image storage stability was evaluated based on the amount of change in i) and ii).

These results are shown in Table 1.

The gelatin used in this example is as follows.

Gelatin Proportion of high-volume ingredients (% by weight) 1
15.9% 2 4.1% 3 13.2% *Results of measurement using the method described in JP-A No. 62-87952 As can be seen from Table 2, on PET with a moisture content of 0.7%. It can be seen that the latent image storage property of the photosensitive material coated on the photosensitive material is poor, but the latent image storage property of the sample containing the polyoxyethylene compound of the present invention is not poor. Therefore, it can be seen that only the sample having the structure of the present invention has a good curl recovery rate and no deterioration in latent image storage property.

Claims (1)

[Scope of Claims] 1) A photographic light-sensitive material having at least one silver halide emulsion layer on a polyester film support, wherein the polyester film has a haze of 3% or less and a water content of 0.5% by weight or more. A photographic light-sensitive material characterized in that the emulsion layer or the non-photosensitive layer on the same side as the emulsion layer contains a polyoxyethylene compound. 2) The polyester film is a copolymerized polyester film containing an aromatic dicarboxylic acid having a metal sulfonate as a copolymerization component, and its breaking strength is 8 to 25 kg/m.
The photographic material according to claim 1, having an initial elastic modulus of 200 to 500 kg/mm^2. 3) The photographic light-sensitive material according to claim 2, wherein the support is a copolymerized polyester film obtained by copolymerizing an aliphatic dicarboxylic acid component having 4 to 20 carbon atoms as a copolymerization component other than the aromatic dicarboxylic acid component having a metal sulfonate. .