JPH0675333A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photographic polyester support superior in adhesiveness to an emulsion layer by allowing a specified naphthalene dicarboxylic acid or its ester to react with a specified glycol. CONSTITUTION:The polyester film of the support is obtained by allowing the aromatic dicarboxylic acid having the naphthalene dicarboxylic acid represented by the formula and typified by 2,6- and 2,7-naphthalene-dicarboxylic acids and the like, and an aromatic dicarboxylic acid having a hydrophilic metal sulfonate with the glycols composed essentially of ethylene glycol. The aromatic dicarboxylic acid having the hydrophilic metal sulofonate can be embodied by 5-Na, -K, or -Li sulfoisophthlate, and 2-Na, -K, or -Li sulfoterephthalete and the glycol can be embodied by di- and tri-ethylene glycols and the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic light-sensitive material excellent in adhesiveness with an emulsion layer.

[0002]

Photographic light-sensitive materials are generally prepared by coating at least one photographic light-sensitive layer on a plastic film support. This plastic film is generally triacetyl cellulose (hereinafter referred to as "T
Fiber-based polymers represented by "AC") and polyester-based polymers represented by polyethylene terephthalate (hereinafter referred to as "PET") are used. By the way, in recent years, the applications of photographic light-sensitive materials have been diversified, and the speed of film transportation during photographing, the increase in photographing magnification, and the downsizing of photographing apparatuses have been significantly advanced. In that case, the support for the photographic light-sensitive material is required to have properties such as strength, dimensional stability and thinning. Polyethylene naphthalate (hereinafter referred to as "PEN") has superior mechanical strength and thermal stability compared to PET, and has already been used for magnetic tapes, packaging, capacitors, etc., and the stability of the support to thin film dimension stability. In recent years, it has been considered for photography from the viewpoint of the above. However, when PEN is used as the photographic film, there is a problem in that the adhesion to the emulsion layer is inferior to that of PET. Poor adhesion between the emulsion and the support causes a fatal problem that the image recorded and recorded is lost.

[0003]

SUMMARY OF THE INVENTION The present invention is to provide a photographic polyester support having excellent adhesion to an emulsion layer.

[0004]

The present invention relates to a photographic light-sensitive material having a polyester film support and at least one light-sensitive layer, wherein the polyester film is a naphthalene dicarboxylic acid represented by the following general formula (I). And a photographic material obtained by reacting an aromatic dicarboxylic acid having a hydrophilic metal sulfonate with a glycol mainly containing ethylene glycol. General formula (I)

[0005]

[Chemical 2]

In the present invention, the polyester film is a polyester mainly composed of naphthalenedicarboxylic acid, an aromatic dicarboxylic acid having a hydrophilic metal sulfonate and ethylene glycol, and a typical naphthalenedicarboxylic acid is 2,6- There are naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid and 2,5-naphthalenedicarboxylic acid, and 5-sodium sulfoisophthalic acid, 2-sodium as an aromatic dicarboxylic acid having a hydrophilic metal sulfonate. Sulfoterephthalic acid, 4-sodium sulfophthalic acid, 4-sodium sulfo-2,6 naphthalene dicarboxylic acid, 4-sodium sulfo-2,7 naphthalene dicarboxylic acid, 4-sodium sulfo 2,5 naphthalene dicarboxylic acid and this Sodium other metals, can be cited for example potassium, compounds substituted with lithium. Examples of glycols include diethylene glycol, triethylene glycol, butanediol, cyclohexamethanediol, neopentyl glycol, xylylenediol and the like. The polyalkylene glycol preferably has a molecular weight of 600 to 10,000. The content of the aromatic dicarboxylic acid having a metal sulfonate is 1 to 30%, preferably 2 to 20%, more preferably 3 to 10% in the dicarboxylic acid including naphthalenedicarboxylic acid. When the amount is too small, the adhesion is insufficient, and when the amount is too large, the film becomes brittle and the folding endurance rapidly deteriorates.

The polyester (A) of the present invention can be synthesized by a conventionally known polyester production method. For example, the acid component can be directly esterified with the glycol component, or when the acid component is used as a dialkyl ester, a transesterification reaction with the glycol component can be used. Alternatively, the acid component may be an acid halide and reacted with glycol. At this time, if necessary, a transesterification reaction, a catalyst or a polymerization reaction catalyst may be used, or a heat resistance stabilizer may be added. Regarding the polyester components and the synthetic method described above, for example, Polymer Experimental Science Vol.
It can be carried out with reference to the descriptions of pages 0 to 103, pages 103 to 136, “Synthetic Polymer V” (Asakura Shoten, 1971), pages 187 to 286. The preferred average molecular weight range of the polyester (A) used in the present invention is from about 3,000 to about 100,000.

Further, various additives can be contained in the polyester resin film of the present invention. One of the properties that poses a problem when a polyester film is used as a support for a photographic light-sensitive material is the problem of fogging caused by the high refractive index of the support. The polyester support of the present invention has a refractive index of about 1.6 to 1.7, and the gelatin used exclusively for the subbing layer and the photographic emulsion layer has a refractive index of 1.50 to 1.55. The ratio of the refractive index of gelatin to that of the polyester support of the present invention is 1.5 / 1.6 to 1.7, which is smaller than 1, and when light enters from the film edge, it is reflected at the interface between the base and the emulsion layer. Cheap. Therefore, the polyester film is apt to cause a so-called light piping phenomenon (fogging). In the present invention, in order to avoid such a light piping phenomenon, a dye that does not increase the film haze can be added. As the dye used,
Although not particularly limited, a dye having a gray color tone is preferable in view of general properties of the light-sensitive material, and a dye having excellent heat resistance in the film forming temperature range of the polyester film and excellent compatibility with polyester is preferable. From the above viewpoints, specific dyes include Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku. The dyeing density is required to be at least 0.01 or more, preferably 0.03 or more as measured by a Macbeth color densitometer.

It is possible to impart slipperiness to the polyester film depending on the application. The slipperiness imparting means is not particularly limited, but kneading with an inert inorganic compound, coating a surfactant, or the like is generally used. Also, a method using an internal particle system in which a catalyst or the like added during the polyester polymerization reaction is precipitated can be used. As the above-mentioned inert inorganic compound, SiO ₂ , T
Examples thereof include iO ₂ , BaSO ₄ , CaCO ₃ , talc, kaolin and the like. Since transparency is an important requirement for a support for a photographic light-sensitive material, SiO ₂ having a refractive index relatively close to that of a polyester film or an internal particle system capable of relatively reducing the precipitated particle size is used. It is desirable to select. When imparting slipperiness by kneading,
A method of laminating functionalized layers to obtain more transparency of the film is also preferably used. Specific examples include a co-extrusion method using a plurality of extruders and feed blocks, or a multi-manifold die.

To laminate polyester, coextrusion method,
The in-line laminating method and the off-line laminating method are used. The co-extrusion method is a method of introducing different resins from two or more extruders into one die and stacking them in the die to perform extrusion molding of a multi-layer structure. The co-extrusion method has a manifold according to the number of layers and joins at the die land part. There are two types, one is a manifold die and the other is a foot block in which a conduit unit of a single layer die is provided with a merging mechanism in layers. Usually 2
Nine layers can be stacked. The in-line laminating method is a method in which biaxially stretched orientation is completed after laminating on an unoriented film before completion of biaxial orientation and / or longitudinal or lateral uniaxial orientation film in the polyester film forming step, and dry lamination or hot melt for lamination. Lamination,
Extrusion lamination is used. Lamination using an adhesive containing a solvent is not preferable because the solvent remains. The off-line laminating method is a method of laminating on a film after completion of biaxial stretching, and the lamination method is used. When the polyester is film-formed, the polymerized polyester may be subjected to the film-forming step in a molten state, or may be once formed into pellets and then subjected to the film-forming step. When pelletized, it is preferably dried before extrusion.

Melt extrusion and biaxial stretching are preferred for film formation. That is, melt-extruded at a melting point or higher and 350 ° C or lower into a rotary cooling body to form an amorphous amorphous sheet,
Then 120-150 ° C, preferably 125-130 ° C
2.0 to 5.0 times in the vertical direction, preferably 2.2 to 4.
Roll stretch 0 times, then 110-150 in transverse direction
2.0 to 5.0 times at ℃, preferably 120 to 135 ℃,
Tenter stretching is preferably carried out at a draw ratio of 2.2 to 4.0, and then transverse drawing temperature or higher and 280 ° C. or lower, preferably 180 to 25.
It is heat-fixed at 0 ° C. or lower, then heat-relaxed by 0.1 to 10%, preferably 0.5 to 5%, then cooled to room temperature and wound. For the stretching, simultaneous biaxial stretching of the tenter clip system is also preferably used. It is also possible to carry out longitudinal stretching again after transverse stretching. In this film forming step, the polyester containing a metal sulfonyl group is laminated by the coextrusion method or the in-line laminating method as described above. Inline lamination may be further performed on the multilayer film formed by the coextrusion method, or inline lamination may be performed to form a multilayer.

The polyester film of the present invention is previously treated with a corona discharge treatment, a flame treatment, an ultraviolet treatment, a high frequency treatment, a glow discharge treatment, an active plasma treatment, a laser treatment and a mixed acid treatment in order to improve the adhesiveness and the wettability of the coating liquid. Surface treatment such as ozone oxidation treatment can be performed as necessary. The corona discharge treatment is carried out by any conventionally known method, for example, Japanese Patent Publication Nos. 48-5043 and 47-5190.
5, JP-A-47-28067 and JP-A-49-83767.
No. 51-41770, No. 51-131576, and the like. Discharge frequency 50 Hz to 5000 kHz, preferably 5 kHz to several tens
0kHz is suitable. If the discharge frequency is too low, stable discharge cannot be obtained and pinholes are generated in the object to be treated, which is not preferable. If the frequency is too high, a special device for impedance matching is required, which increases the cost of the device, which is not preferable. Regarding the treatment strength of the object to be treated, 0.001 KV is required for improving the wettability of ordinary plastic films such as polyester and polyolefin.
· A · min / m ² ~5KV · A · min / m ^2, preferably 0.01
KV · A · min / m ² ~1KV · A · min / m ^2, are suitable. The gap clearance between the electrode and the dielectric roll is 0.5-
2.5 mm, preferably 1.0 to 2.0 mm is suitable.

In many cases, the glow discharge treatment, which is the most effective surface treatment, is carried out by any conventionally known method, for example, Japanese Patent Publication Nos. 35-7578 and 36-1033.
No. 6, No. 45-22004, No. 45-22005,
45-2440, 46-43480, U.S. Pat. Nos. 3,057,792, 3,057,795, 3,179,482, 3,288,638 and 3,309. No. 299, No. 3,424,735, No. 3,462,335, No. 3,475,307, No. 3,761,299, British Patent 997,093, JP-A No. 53-129262, etc. Can be used.

The glow discharge treatment conditions are generally pressure of 0.
005 to 20 Torr, preferably 0.02 to 2 Torr is suitable. If the pressure is too low, the surface treatment effect will be reduced, and if the pressure is too high, an excessive current will flow and sparks will easily occur, which is dangerous and may damage the object to be treated. The electric discharge is generated by applying a high voltage between metal plates or metal rods arranged in a vacuum tank with one or more pairs of spaces. This voltage can take various values depending on the composition of the atmospheric gas and the pressure, but normally within the above pressure range, stable steady glow discharge occurs between 500 and 5000V. A particularly suitable voltage range for improving the adhesion is 2000 to 4000V.

The discharge frequency is from direct current to several thousand MHz, preferably 50 Hz, as seen in the prior art.
20MHz is suitable. Regarding the discharge treatment strength, 0.01KV · A · min /
m ² ~5KV · A · min / m ^2, preferably 0.15KV · A · min
/ m ^{2 to 1} KV · A · min / m ² is suitable.

The polyester support of the present invention preferably has a subbing layer in order to increase the adhesive force with a photographic layer such as a photosensitive layer coated thereon. As the subbing layer, a subbing layer using a polymer latex made of a styrene-butadiene-based copolymer or a vinylidene chloride-based copolymer,
There is a subbing layer that uses a hydrophilic binder such as gelatin. The subbing layer preferably used in the present invention is a subbing layer using a hydrophilic binder. Examples of the hydrophilic binder used in the present invention include water-soluble polymers, cellulose esters, latex polymers and water-soluble polyesters. Water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, maleic anhydride copolymers, etc., and carboxymethyl cellulose, hydroxyethyl cellulose as cellulose ester. And so on. Examples of the latex polymer include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylic acid ester-containing copolymers, vinyl acetate-containing copolymers and butadiene-containing copolymers. Of these, gelatin is the most preferable.

As the compound for swelling the support used in the present invention, resorcin, chlorresorcin, methylresorcin, o-cresol, m-cresol, p-cresol, phenol, o-chlorophenol, p-chlorophenol, di-resin. Examples include chlorophenol, trichlorophenol, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid, and chloral hydrate. Of these, resorcin and p-chlorophenol are preferred.

Various gelatin hardeners can be used in the subbing layer of the present invention. As a gelatin hardening agent, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine, etc.), epichlorohydrin resin And so on. The subbing layer of the present invention is S
Inorganic fine particles such as iO ₂ and TiO ₂ or fine particles of polymethylmethacrylate copolymer (1 to 10 μm) can be contained as a matting agent. The undercoat layer according to the present invention can be applied by a generally well-known coating method, for example, a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method or the like. Is. The light-sensitive material of the present invention may have a non-light-sensitive layer such as an anti-halation layer, an intermediate layer, a back layer and a surface protective layer in addition to the light-sensitive layer. As the binder of the back layer,
It may be a hydrophobic polymer or a hydrophilic polymer used in the underlayer.

The back layer of the light-sensitive material of the present invention may contain an antistatic agent, a slip agent, a matting agent, a surfactant, a dye and the like. The antistatic agent used in the back layer of the present invention is not particularly limited, and examples of the anionic polymer electrolyte include polymers containing a carboxylic acid, a carboxylic acid salt and a sulfonic acid salt, for example, JP-A-48-22017.
No. 4, JP-B-46-24159, JP-A-51-3072
5, JP-A-51-129216, JP-A-55-95.
It is a polymer as described in No. 942. Examples of the cationic polymer include, for example, JP-A-49-121523.
No. 4, JP-A-48-91165, JP-B-49-2458.
There are some as described in No. 2. Further, the ionic surfactant has anionic property and cationic property, and is disclosed in, for example, JP-A-49-85826 and JP-A-49-33630.
No., US2,992,108, US3,206,31
2, JP-A-48-87826, JP-B-49-1156
7, JP-B-49-11568, JP-A-55-708.
Compounds such as those described in No. 37 can be mentioned.

The most preferable antistatic agent for the back layer of the present invention is ZnO, TiO ₃ , SnO ₂ or Al _2.
O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO
It is fine particles of at least one crystalline metal oxide selected from the group ₃ or a composite oxide thereof. The fine particles of the conductive crystalline oxide or the composite oxide thereof used in the present invention have a volume resistivity of 10 ⁷ Ωcm or less, more preferably 10 ⁵ Ωcm or less. The particle size is 0.
It is desirable that the thickness is 01 to 0.7 μ, and particularly 0.02 to 0.5 μ. The method for producing fine particles of a conductive crystalline metal oxide or composite oxide used in the present invention is described in detail in JP-A-56-143430 and JP-A-60-258541. First, a method in which metal oxide fine particles are produced by firing, and heat treatment is performed in the presence of a heteroatom to improve conductivity, and secondly, different method for improving conductivity when producing metal oxide fine particles by firing. A method of making atoms coexist, a third method of introducing oxygen defects by lowering the oxygen concentration in the atmosphere when producing metal fine particles by firing, and the like are easy. As an example including a heteroatom, ZnO is Al, In, etc., and TiO ₂ is N.
b, Ta, etc., and SnO ₂ includes Sb, Nb, halogen elements and the like. The addition amount of heteroatoms is 0.01 to 3
The range of 0 mol% is preferable, but 0.1-10 mol% is particularly preferable.

Next, the photographic light-sensitive material of the present invention will be described in detail. The light-sensitive material of the present invention is composed of a silver halide emulsion layer, a back layer, a protective layer, an intermediate layer, an antihalation layer and the like, and these are mainly used in the hydrophilic colloid layer. In that case, the binder of the hydrophilic colloid layer includes, for example, proteins such as gelatin, colloidal albumin and casein; cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose; sugar derivatives such as agar, sodium alginate and starch derivatives; synthetic hydrophilic colloids. For example, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide or derivatives thereof and partial hydrolysates,
Examples thereof include dextran, polyvinyl acetate, polyacrylic acid ester, rosin and the like. Mixtures of two or more of these colloids may be used if desired. The most used of these is gelatin or its derivatives, and the gelatin referred to here is so-called lime-processed gelatin, acid-processed gelatin and enzyme-processed gelatin.

In the present invention, the anion, nonion,
A cation and a betaine fluorine-containing surfactant can be used in combination. These fluorine-containing surfactants are disclosed in JP-A-49-
No. 10722, British Patent No. 1,330,356, JP-A Nos. 53-84712, 54-14224, and 50.
-113221, U.S. Pat. No. 4,335,201,
U.S. Pat. No. 4,347,308, British Patent No. 1,417,91.
No. 5, Japanese Examined Patent Publication No. 52-26687, No. 57-26719
No. 59-38573, JP-A-55-149938.
No. 54, No. 54-48520, No. 54-14224, No. 58-200235, No. 57-146248, No. 5
8-196544, British Patent No. 1,439,402
No., etc. Preferred examples of these are described below.

[0023]

[Chemical 3]

[0024]

[Chemical 4]

[0025]

[Chemical 5]

[0026]

[Chemical 6]

[0027]

[Chemical 7]

[0028]

[Chemical 8]

[0029]

[Chemical 9]

[0030]

[Chemical 10]

[0031]

[Chemical 11]

[0032]

[Chemical 12]

[0033]

[Chemical 13]

In the present invention, a nonionic surfactant may be used. Specific examples of the nonionic surfactant preferably used in the present invention are shown below.

[0035]

[Chemical 14]

[0036]

[Chemical 15]

[0037]

[Chemical 16]

[0038]

[Chemical 17]

[0039]

[Chemical 18]

The layer to which the fluorine-containing surfactant and the nonionic surfactant used in the present invention are added is not particularly limited as long as it is at least one layer of the photographic light-sensitive material. For example, a surface protective layer, an emulsion layer, an intermediate layer, Examples thereof include an undercoat layer and a back layer. The amount of the fluorine-containing surfactant and nonionic surfactant used in the present invention may be 0.0001 g to 1 g per 1 square meter of the photographic light-sensitive material, more preferably 0.0005 to 0.5 g, Particularly preferred is 0.0005 g to 0.2 g. Further, two or more kinds of these surfactants of the present invention may be mixed.

Further, a polyomal compound such as ethylene glycol, propylene glycol, 1,1,1-trimethylolpropane, etc., as shown in JP-A-54-89626, may be added to the protective layer or another layer of the present invention. You can Other known surfactants may be added to the photographic constituent layers of the present invention alone or in combination. Although they are used as coating aids, they are sometimes applied for other purposes such as emulsion dispersion, sensitization and other improvement of photographic characteristics. Further, in the present invention, a lubricating composition, for example, US Pat. Nos. 3,079,837 and 3,
Nos. 3,080,317, 3,545,970, 3,294,537, and modified silicones disclosed in JP-A No. 52-129520 can be incorporated in the photographic constituent layers.

The photographic light-sensitive material of the present invention contains US Pat. Nos. 3,411,911 and 3,411,912 in the photographic constituent layers.
And polymer latexes described in JP-B-45-5331 and the like. The silver halide emulsion layer and the other hydrophilic colloid layers in the photographic light-sensitive material of the present invention can be hardened by various organic or inorganic hardeners (alone or in combination). In particular, a color reversal film and a color negative film can be mentioned as typical examples of the silver halide color photographic light-sensitive material preferred in the present invention. Particularly, a color negative film for general use is a preferable color photographic light-sensitive material. Description will be made below using a general-purpose color negative film.

The light-sensitive material of the present invention may have at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red color-sensitive layer and the green color. The color sensitive layer and the blue color sensitive layer are installed in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. A non-photosensitive layer such as an intermediate layer of each layer may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer. In the intermediate layer, JP-A-61-43748,
No. 59-113438, No. 59-113440, No. 61-20037, No. 61-20038 may contain a coupler, a DIR compound and the like, and are usually used. A color mixing inhibitor may be included. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045, JP-A-57-112.
No. 751, No. 62-200350, No. 62-2065.
No. 41, No. 62-206543, No. 56-25738.
No. 62-63936, 59-202464,
It is described in JP-B-55-34932 and JP-B-49-15495.

The silver halide grains include those having regular crystals such as cubes, octahedra and tetradecahedrons, those having irregular crystal forms such as spheres and plates, and twin planes. It may have a crystal defect or a composite form thereof. The grain size of silver halide may be fine grains of about 0.2 μm or less, or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No. 1764
3 (Dec. 1978), pp. 22-23, "I. Emulsion preparation and types", and N.
o. 18716 (November, 1979), p.648, "The Physics and Chemistry of Photography" by Graphide, published by Paul Montel (P. Glafkides, Chemie et Phisique Photographique,
Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photogra
phic Emulsion Chemistry (Focal Press, 196
6)), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et al., Making
and Coating Photographic Emulsion, Focal Press, 1
964) and the like.

US Pat. Nos. 3,574,628 and 3,
655,394 and British Patent 1,413,748.
The monodisperse emulsions described in JP-A No. 1989-2000 are also preferable. Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described in Gutof, Photographic Science and Engineering (Gutof
f, Photographic Science and Engineering), 14th
Volume 248-257 (1970); U.S. Pat. No. 4,
No. 434, 226, No. 4,414, 310, No. 4, 4
It can be easily prepared by the method described in 33,048, 4,439,520 and British Patent 2,112,157.

The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and silver halide having different compositions may be bonded by epitaxial bonding. May be
Further, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. The efficiency of the present invention is particularly remarkable when an emulsion sensitized with a gold compound and a sulfur-containing compound is used. Additives used in such processes are Research Disclosure No. 17643 and No. 1871.
It is described in No. 6, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table. Additive type RD17643 RD18716 1 Chemical sensitizer, page 23, page 648, right column 2 Sensitivity enhancer, same as above 3, Spectral sensitizer, pages 23 to 24, page 648, right column ~ Supersensitizer, page 649, right column 4, whitening agent Page 24 5 Antifoggant 24 to 25 page 649 right column ~ and stabilizer 6 Light absorber, page 25 to 26 page 649 right column ~ Filter dye, page 650 left column UV absorber 7 Stain inhibitor 25 page right Column page 650 left to right column 8 dye image stabilizer page 25 9 hardening agent page 26 651 page left column 10 binder page 26 same as above 11 plasticizer, lubricant page 27 650 page right column 12 coating aid, 26-27 Page Same as above Surfactant

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,98
It is preferable to add a compound which can be immobilized by reacting with formaldehyde described in No. 7 and No. 4,435,503 to the light-sensitive material. Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure (RD) No. 17643, VII mentioned above.
-C-G.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. The boiling point at atmospheric pressure used in oil-in-water dispersion method is 17
Specific examples of the high boiling point organic solvent having a temperature of 5 ° C. or higher include phthalic acid esters, phosphoric acid or phosphonic acid esters, benzoic acid esters, amides, alcohols or phenols, aliphatic carboxylic acid esters, aniline. Examples thereof include derivatives and hydrocarbons. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C or higher and about 16 ° C.
An organic solvent at 0 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like. The steps of latex dispersion method, effects, and specific examples of latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230. It is described in.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is 28 μm or less,
Moreover, the film swelling speed T _1/2 is preferably 30 seconds or less. The film thickness means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example,
Photographic Science and Engineering (Photogr.
Sci. Eng.), Vol. 19, No. 2, pp. 124-129, and can be measured by using a swellometer (swelling meter) of the type, and T _1/2 is a color developing solution at 30 ° C. for 3 minutes. 90% of the maximum swollen film thickness reached after the treatment for 15 seconds is defined as the saturated film thickness, and is defined as the time until the film thickness of T _1/2 is reached. The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing aging conditions after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness-film thickness) / film thickness.

The photographic light-sensitive material prepared in this manner was cut into a predetermined width (for example, if it was 135, it was 35 mm.
Width, if 110, 10 mm width), perforation processing is performed, and the product is stored in a predetermined cartridge or the like and used for camera photography.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, and N.
The development can be performed by a usual method described in the left column to the right column of 615 of O.18716. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds of US Pat. Nos. 3,342,597, 3,342,599, Research Disclosures 14,850 and 15,1.
Schiff base type compounds described in No. 59, and No. 13,924 described therein.

[0053]

The present invention will be described below with reference to specific examples.
The present invention is not limited to this. Preparation of support (1) Synthesis of polymer containing water-absorbing metal sulfonate Polymer having the composition shown in Table 2 (polymers A to N) according to a conventional method
Was synthesized.

(2) Preparation of Support Containing Water-Absorbing Metal Sulfonate As a UV absorber, 100 parts by weight of the above polymers A to N are used.
Tinuvin P. 2 parts by weight of 326 (manufactured by Geigy) were dried by a conventional method, melted at 300 ° C., extruded from a T-die and longitudinally stretched 3.3 times at 140 ° C., and then at 130 ° C. for 3. The film was transversely stretched 3 times and further heat set at 250 ° C. for 6 seconds to obtain 90 μm supports A to N.

(3) Preparation of PEN film Commercially available polyethylene-2,6-naphthalate polymer 1
00 parts by weight and Tinuvin P. 326
2 parts by weight of (manufactured by Geigy) was dried by a conventional method, melted at 300 ° C., and then extruded from a T-die 14
Longitudinal stretching of 3.3 times is performed at 0 ° C., and then at 130 ° C. for 3.
The film is transversely stretched 3 times and further heat-set at 250 ° C for 6 seconds to 90
A support of μm was obtained.

(4) Fabrication of PET film PET pellets were melted and biaxially stretched by a conventional method 9
A 0 μm film was obtained.

Coating of Undercoat Layer The above-mentioned support was provided with an undercoat layer having the following composition after corona discharge treatment on both sides thereof. For the corona discharge treatment, a solid state corona treatment machine 6KVA model manufactured by Pillar Co. is used, and a 30 cm wide support is treated at 20 m / min. From the current and voltage readings at this time, the object to be processed is 0.375.
KV / A / min / m ² was processed. The discharge frequency during the treatment was 9.6 KHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm. Gelatin 3 g Distilled water 250 cc Sodium α-sulfodi-2-ethylhexyl succinate 0.05 g Formaldehyde 0.02 g

Coating of Back Layer A back layer having the following composition was coated on the surface opposite to the side provided with the undercoat layer of each support after undercoating. 1) Preparation of conductive fine particle dispersion liquid (tin oxide-antimony oxide composite dispersion liquid): 230 parts by weight of stannic chloride hydrate and 23 parts by weight of antimony trichloride were dissolved in 3000 parts by weight of ethanol to obtain a uniform solution. It was A 1N aqueous sodium hydroxide solution was added dropwise to this solution until the pH of the solution reached 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate. The reddish brown colloidal precipitate was separated by centrifugation. To remove excess ions, water was added to the precipitate and washed by centrifugation. This operation was repeated 3 times to remove excess ions. 200 parts by weight of the colloidal precipitate from which excess ions were removed was redispersed in 1500 parts by weight of water and sprayed in a baking furnace heated to 600 ° C. to obtain a bluish tin oxide-antimony oxide composite having an average particle size of 0.2 μm. Fine particle powder of The specific resistance of this fine powder is 25
It was Ω · cm. A mixed solution of 40 parts by weight of the above fine particle powder and 60 parts by weight of water was adjusted to pH 7.0 and roughly dispersed by a stirrer, and then a horizontal sand mill (trade name: Dynomill; WILLYA.1BACH).
OFENAG) was dispersed and prepared until the residence time reached 30 minutes.

2) Preparation of back layer: The following formulation [A] was applied so that the dry film thickness would be 0.3 μm, and the coating was carried out at 130 ° C. for 3 hours.
It was dried for 0 seconds. The following coating solution (B) for coating layer was further applied onto this so that the dry film thickness would be 0.1 μm, and 1
It was dried at 30 ° C. for 2 minutes. [Formulation A] 10 parts by weight of the conductive fine particle dispersion described above 1 part by weight of gelatin 27 parts by weight of water 60 parts by weight of methanol 2 parts by weight of resorcin 0.01 part by weight of polyoxyethylene nonylphenyl ether [coating liquid for coating layer (B)] Cellulose triacetate 1 part by weight Acetone 70 parts by weight Methanol 15 parts by weight Dichloromethylene 10 parts by weight p-Chlorophenol 4 parts by weight

Coating of Photosensitive Layer On the support obtained by the above-mentioned method, each layer having the composition shown below was multilayer-coated to prepare a multilayer color photosensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ^-3 HBS-1 0.20

[0062]

Third layer (low-sensitivity red-sensitive emulsion layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Emulsion D Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.025 ExC-7 0.0010 ExC-8 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high sensitivity red-sensitive emulsion layer) Emulsion E Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.12 ExC-3 0.045 ExC-6 0.020 ExC-8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20

6th layer (intermediate layer) Cpd-1 0.10 HBS-1 0.50 gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Emulsion C Silver 0.35 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Emulsion D Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExM-2 0.13 ExM-3 0.030 ExY-1 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.90

9th layer (high-sensitivity green-sensitive emulsion layer) Emulsion E Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.030 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.040 HBS-1 0.25 HBS-2 0.10 Gelatin 1.44

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.030 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60

Eleventh Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Emulsion C Silver 0.18 ExS-7 8.6 × 10 ^-4 ExY-1 0.020 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 HBS-1 0.28 Gelatin 1.10

Twelfth layer (medium speed blue emulsion layer) Emulsion D Silver 0.40 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.050 ExY-3 0.10 HBS-1 0.050 Gelatin 0.78

13th layer (high-sensitivity blue emulsion layer) Emulsion F Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0.86

14th layer (first protective layer) Emulsion G Silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00

Fifteenth layer (second protective layer) H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.20

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt and rhodium salt.

[0077]

[Table 1]

In Table 1, (1) Emulsions A to F were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to F were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in tabular grains and normal crystal grains having a grain structure by using a high voltage electron microscope.

[0079]

[Chemical 19]

[0080]

[Chemical 20]

[0081]

[Chemical 21]

[0082]

[Chemical formula 22]

[0083]

[Chemical formula 23]

[0084]

[Chemical formula 24]

[0085]

[Chemical 25]

[0086]

[Chemical formula 26]

[0087]

[Chemical 27]

[0088]

[Chemical 28]

[0089]

[Chemical 29]

[0090]

[Chemical 30]

[0091]

[Chemical 31]

[0092]

[Chemical 32]

[0093]

[Chemical 33]

Development Processing The development processing conditions are as follows.

Treatment process Temperature Time Color development 38 ° C. 3 minutes Stop 38 ° C. 1 minute Water wash 38 ° C. 1 minute Bleach 38 ° C. 2 minutes Water wash 38 ° C. 1 minute Fixing 38 ° C. 2 minutes Water wash 38 ° C. 1 minute Stabilizing bath: 38 ° C. for 1 minute The treatment liquid used has the following composition. Color developer Caustic soda 2g Sodium sulfite 2g Potassium bromide 0.4g Sodium chloride 1g Hoh sand 4g Hydroxylamine sulfate 2g Ethylenediaminetetraacetic acid disodium dihydrate 2g 4-Amino-3-methyl-N-ethyl-N- (β -Hydroxyethyl) aniline monosulfate) 4g Water is added and the total amount is 1 liter Stop solution Sodium thiosulfate 10g Ammonium thiosulfate (70% aqueous solution) 30 ml Acetic acid 30 ml Sodium acetate 5 g Potassium alum 15 g Total amount 1 liter Bleach Liquid Ethylenediaminetetrairon (III) acetate sodium dihydrate 100 g Potassium bromide 50 g Ammonium nitrate 50 g Folic acid 5 g Ammonia water Adjusting pH to 5.0 Total volume with water 1 liter Fixing solution Sodium thiosulfate 150 g Sodium sulfite -Soda 15g Ho sand 12g Glacial acetic acid 15ml Potassium alum 20g Water added to a total amount of 1 liter Stabilization bath Folic acid 5g Sodium citrate 5g Sodium metaphorate (tetrahydrate) 3g Potassium alum 15g Water added to a total amount 1 liter

Evaluation of Adhesiveness The adhesiveness of the sample prepared as described above was evaluated as follows. Adhesiveness evaluation at the time of drying Make 7 nicks on the surface of the material with a razor at intervals of 5 mm in length and width to make 36 squares, and stick adhesive tape (Nitto tape manufactured by Nitto Electric Industry Co., Ltd.) on this 18
Peel off quickly in the 0 degree direction. In this method, if the unpeeled portion is 95% or more, it is A grade, and if 90% or more, it is B grade.
Class, 60% or more is C class, and less than 60% is D class. Hereinafter, the sample before the development treatment is referred to as a raw sample, and the sample after the development treatment is referred to as a dried sample. Evaluation of adhesiveness when wet Wet scratches on the emulsion surface of the film in the processing liquid with a writing brush at the X mark in each stage of development, fixing, and washing with water. Adhesive strength is evaluated by the maximum peeling width peeled off. Class A is used when the emulsion layer does not peel off more than scratches, Class B is used when the maximum peeling width is 2 mm or less, Class C is used when the maximum peeling width is 5 mm or less, and Class D is used otherwise.

Measurement of Folding Strength Using a MIT Fatigue Resistance Tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.), the number of reciprocations until bending and breaking was measured according to the ISO 8776-1988 standard. Results As shown in Table 2, it can be seen that in the present invention, the adhesiveness is improved without impairing the strength (folding strength) of the film as compared with the case of using polyethylene terephthalate or polyethylene naphthalate.

[0098]

[Table 2]

[0099]

By using polyethylene naphthalate having a hydrophilic sulfonic acid group as a support, it is possible to obtain a silver halide photographic light-sensitive material having good adhesion between the support and the emulsion layer.

Claims (3)

[Claims] 1. A photographic light-sensitive material comprising a polyester film support and at least one light-sensitive layer, wherein the polyester film is mainly a naphthalene dicarboxylic acid represented by the following general formula (I): A silver halide photographic light-sensitive material obtained by reacting an ester thereof with an aromatic dicarboxylic acid having a hydrophilic metal sulfonate or an ester thereof with a glycol mainly comprising ethylene glycol. General formula (I) 2. The silver halide photographic light-sensitive material according to claim 1, wherein the naphthalenedicarboxylic acid is 2,6-naphthalenedicarboxylic acid. 3. The aromatic carboxylic acid having a hydrophilic metal sulfonate is 5 sodium sulfoisophthalic acid, 2 sodium sulfoterephthalic acid, 4-sodium sulfophthalic acid, 4-sodium sulfo 2,6 naphthalene dicarboxylic acid, 4 sodium sulfo- 2. The photographic light-sensitive material according to claim 1, which is 2,7 naphthalene dicarboxylic acid, 4-sodium sulfo 2,5 naphthalene dicarboxylic acid, and 4 sodium sulfo-1,5 naphthalene dicarboxylic acid.