JPH07219143A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material having good adhesion, excellent dynamic characteristic and good antistatic performance and which is hardly curled by incorporating a polyamide-epichlorohydrin resin into the undercoat on a substrate with the surface treated with a glow discharge or irradiated with UV. CONSTITUTION:A polyamide-epichlorohydrin resin is incorporated into the undercoat on a substrate with the surface treated with a glow discharge or irradiated with UV and having 90 to 250 deg.C glass transition temp. (Tg). The polyester substrate is previously heat-treated above the Tg and then below the Tg. This photosensitive material is rolled in a spool having 5 to 11mm outer diameter. Pressure fogging is caused in the photographic emulsion at <5mm diameter, and a camera is not miniaturized if 11mm. Accordingly, the spool diameter should be controlled to be 5 to 11mm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material having a roll-shaped film which is less prone to curling and excellent in adhesiveness.

[0002]

2. Description of the Related Art Although PET film is excellent in productivity, mechanical strength and dimensional stability, it has a great curl and is difficult to handle after development. The range has been limited.

In recent years, the use of photographic light-sensitive materials has been diversified, and there is a demand for downsizing of cameras, speeding up of film transportation during photographing, and higher magnification of printing. Along with this, the support is required to have strength, dimensional stability, thinning, and the like. Further, with the miniaturization of cameras, there is an increasing demand for miniaturization of patrones. In order to miniaturize the Patrone, it is necessary to solve two problems. The first issue is
This is to prevent the mechanical strength from lowering as the film becomes thinner. The second problem is to reduce the strong curl that occurs during storage over time as the spool becomes smaller.

As a method of reducing the curl of a polyester film, for example, JP-A-51-16358, JP-A-1-131550, and US Pat. Nos. 4,141,735.
The method as described in the issue is known. But,
The environment in which the silver halide photographic light-sensitive material is used varies, and it may be left in a car in the summer and may be exposed to a temperature of nearly 90 ° C for a while. But it has become necessary not to deteriorate.

In order to adhere the silver halide emulsion layer to the polyester support, it is necessary to provide an undercoat layer. As an undercoat layer for a polyethylene terephthalate support, JP-A-48-24723 and JP-B-49-2658 can be used.
No. 0, JP-A-51-114120, JP-A 1-210.
947, JP-A-3-109545 and the like. However, the polyester support of the present invention is less likely to be bonded than a polyethylene terephthalate support, and cannot be bonded by conventional techniques. Furthermore, as the environment in which silver halide photographic light-sensitive materials are used is wide-ranging, the adhesion performance of the emulsion layer on the polyester support is deteriorated in the prior art, and it has become even more required. When a polyester support is used, the polyester support is easily charged during photography or during transportation in an automatic processor.
As a result, electric discharge may occur. In addition, the current technology for preventing electrification causes the problem that the material used elutes in the processing liquid, so the antistatic performance is erased after development processing, and the dust adhering due to electrification appears at the time of printing. Is not sufficient.

[0006]

SUMMARY OF THE INVENTION The first object of the present invention is to provide a photographic light-sensitive material having good adhesion and excellent mechanical properties. A second object of the present invention is to provide a photographic light-sensitive material having less curl and good antistatic performance.

[0007]

The present invention relates to a silver halide photographic light-sensitive material having at least one light-sensitive layer on a polyester support, the surface of which is subjected to glow discharge treatment or ultraviolet irradiation to give a glass transition temperature ( It was achieved by a silver halide photographic light-sensitive material characterized in that an undercoat layer on the support having a Tg of 90 ° C. or higher and 200 ° C. or lower contains a polyamide-epichlorohydrin resin.

First, the aromatic polyester support which is the support of the present invention will be described. The aromatic polyester of the present invention is formed by using a diol and an aromatic dicarboxylic acid as essential components. The essential aromatic dicarboxylic acid is one having at least one benzene nucleus in the dicarboxylic acid. Moreover, you may mix with an aliphatic dicarboxylic acid as needed. Such usable aromatic and aliphatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, and naphthalenedicarboxylic acid (2,6
-, 1,5-, 1,4-, 2,7-), diphenylene p, p'-dicarboxylic acid, tetrachlorophthalic anhydride,
Succinic acid, glutaric acid, adipic acid, sebacic acid, succinic anhydride, maleic acid, fumaric acid, maleic anhydride, itaconic acid, citraconic anhydride, tetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid, halogenated terephthalic acid, bis (p-carboxyphenol) ether, 1,1-dicarboxy-2-phenylethylene, 1,4-dicarboxymethylphenol, 1,3-
Examples thereof include dicarboxy-5 phenylphenol, sodium 3-sulfoisophthalate, and the like.

Next, as the diol, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7 -Heptanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanediol, 1,1 Examples thereof include cyclohexanedimethanol, catechol, resorcin, hydroquinone, 1,4-benzenedimethanol, dimethylolnaphthalene, p-hydroxyethyloxybenzene and bisphenol A. Also,
If necessary, a monofunctional or trifunctional or more polyfunctional hydroxyl group-containing compound or acid-containing compound may be copolymerized. Further, the polyester of the present invention may be copolymerized with a hydroxycarboxylic acid having at the same time a hydroxyl group and a carboxyl group (or its ester) in the molecule.

Among these dicarboxylic acid monomers,
Preferred aromatic dicarboxylic acids are 2,6-naphthalenedicarboxylic acid (NDCA), terephthalic acid (TPA),
Isophthalic acid (IPA), orthophthalic acid (OPA),
Paraphenylenedicarboxylic acid (PPDC) is preferred,
Particularly, 2,6-naphthalenedicarboxylic acid is preferable. The diols are ethylene glycol (EG), polyethylene glycol (PEG), cyclohexanedimethanol (C
HDM), neopentyl glycol (NPG), bisphenol A (BPA) and biphenol (BP) are preferable, and ethylene glycol is particularly preferable. Also, as the hydroxycarboxylic acid, para-hydroxybenzoic acid (PHB
A), 6-hydroxy-2-naphthalenecarboxylic acid (H
NCA) may be used.

These monomers are polymerized to form polyesters. Preferred examples include homopolymers such as polyethylene naphthalate and polycyclohexanedimethanol terephthalate (PCT), and terephthalic acid.
Copolymer of naphthalenedicarboxylic acid and ethylene glycol (mixing molar ratio of terephthalic acid and naphthalenedicarboxylic acid is preferably between 0.9: 0.1 and 0.1: 0.9, 0.8: 0.2-0. 2: 0.8 is more preferable), a copolymer of terephthalic acid, ethylene glycol and bisphenol A (mixing molar ratio of ethylene glycol and bisphenol A is preferably between 0.6: 0.4 and 0: 1.0, Further, 0.5: 0.5 to 0: 0.9 is preferable.), Isophthalic acid, para-phenylenedicarboxylic acid, a copolymer of terephthalic acid and ethylene glycol (isophthalic acid; para-phenylenedicarboxylic acid is used in a molar ratio of terephthalic acid). 1 is 0.1 to 0.
5, 0.1 to 0.5, and more preferably 0.2
.About.0.3, 0.2 to 0.3 are preferable), terephthalic acid, a copolymer of neopentyl glycol and ethylene glycol (the molar ratio of neopentyl glycol and ethylene glycol is 1: 0 to 0.7: 0.3). Preferably, 0.9: 0.1 to 0.6: 0.4) terephthalic acid, a copolymer of ethylene glycol and biphenol (the molar ratio of ethylene glycol and biphenol is 0:
1.0 to 0.8: 0.2 is preferable, and 0.1: 0.9 to 0.7: 0.3 is more preferable. ), Parahydroxybenzoic acid, a copolymer of ethylene glycol and terephthalic acid (the molar ratio of parahydroxybenzoic acid and ethylene glycol is preferably 1: 0 to 0.1: 0.9, more preferably 0.9: 0.1). .About.0.2: 0.8) and the like are preferable. Among these, polyesters containing 2,6-naphthalenedicarboxylic acid are particularly preferable. Specifically, it is a polyester containing 0.1-1.0 of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene 2,6-naphthalate is particularly preferable.

These homopolymers and copolymers can be synthesized according to conventionally known methods for producing polyesters. For example, an acid component may be directly esterified with a glycol component (direct weighting method), or a dialkyl ester may be used as an acid component to undergo a transesterification reaction with a glycol component, which is then heated under reduced pressure to remove excess surplus. The glycol component may be removed (transesterification method), or it can be synthesized. Alternatively, the acid component is set as an acid halide,
It may be reacted with glycol. At this time, if necessary, a transesterification reaction catalyst, a polymerization reaction catalyst, or a heat resistance stabilizer may be added. These polyester synthesis methods are described, for example, in Polymer Experimental Science No. 5
Volume "Polycondensation and Polyaddition" (Kyoritsu Shuppan, 1980) No. 10
Pages 3 to 136, "Synthetic Polymer V" (Asakura Shoten, 19
71) pp. 187-286 can be referred to.

The preferred average molecular weight range for these polyesters is about 5,000 to 200,000. Furthermore, in order to improve the adhesiveness with other polyesters, these polyesters may be partially blended with another polyester, or the monomers constituting the other polyester may be copolymerized, or these polyesters may be copolymerized. A monomer having an unsaturated bond can be copolymerized therein to radically crosslink. A polymer blend obtained by mixing two or more kinds of the obtained polymers is disclosed in JP-A-49-
5482, 64-4325 and JP-A-3-19271.
8. Research Disclosure 283,739-4
1, the same 284, 779-82, the same 294, 807-14
It can be easily formed according to the method described in 1.

The Tg of the polyester of the present invention is 90 ° C. or higher. The photographic light-sensitive material of the present invention is actually exposed to various environmental conditions. It is expected that the vehicle will be left in a car parked outdoors in the middle of summer, in which case the room temperature is known to reach 80 ° C or higher. Considering this, the Tg of the support of the present invention is preferably 90 ° C. or higher. On the other hand, it has transparency and 2
Until now, there is no general-purpose polyester film having a temperature higher than 00 ° C. Therefore, the T of the polyester used in the present invention
The g temperature needs to be 90 ° C. or higher and 200 ° C. or lower. The Tg referred to here is the scanning differential thermal analyzer (DS
It is defined as follows using C). First, 10 mg of sample
Is heated to 300 ° C. at a heating rate of 20 ° C./min in a nitrogen stream and then rapidly cooled to room temperature. After that, when the temperature is raised again at 20 ° C./min, the arithmetic mean value of the temperature at which the temperature starts to deviate from the baseline and the temperature at which the temperature returns to the new baseline is defined as Tg.

Next, examples of preferable specific compounds of the polyester used in the present invention are shown, but the present invention is not limited thereto. Polyester homopolymer-Example P-1: [2,6-naphthalenedicarboxylic acid (NDCA) / ethylene glycol (EG) (100/100)] (PEN) Tg = 119 ° C P-2: [terephthalic acid (TPA) / Cyclohexanedimethanol (CHDM) (100/100)] Tg = 93 ° C. P-3: [TPA / bisphenol A (BPA) (100/100)] Tg = 192 ° C. Polyester Copolymer-Example P-4: 2,6- NDCA / TPA / EG (50/50/100) Tg = 92 ° C. P-5: 2,6-NDCA / TPA / EG (75/25/100) Tg = 102 ° C. P-6: 2,6-NDCA / TPA / EG / BPA (50/50/75 / Tg = 112 ° C. P-7: TPA / EG / BPA (100/50/50) Tg = 105 ° C. P 8: TPA / EG / BPA (100/25/75) Tg = 135 ℃ P-9: TPA / EG / CHDM / BPA (100/25/25/50) Tg = 115 ℃

P-10: IPA / PPDC / TPA / EG (20/50/30/100) Tg = 95 ° C. P-11: NDCA / NPG / EG (100/70/30) Tg = 105 ° C. P-12 : TPA / EG / BP (100/20/80) Tg = 115 ° C. P-13: PHBA / EG / TPA (200/100/100) Tg = 125 ° C. Polyester Polymer Blend Example P-14: PEN / PET ( 60/40) Tg = 95 ° C. P-15: PEN / PET (80/20) Tg = 104 ° C. P-16: PAr / PEN (50/50) Tg = 142 ° C. P-17: PAr / PCT (50 / 50) Tg = 118 ° C. P-18: PAr / PET (60/40) Tg = 101 ° C. P-19: PEN / PET / PAr (50/25/25) Tg = 108 ° C. P-20: PEN / SIP / EG (99/1/100) Tg = 115 ° C. However, the above abbreviations include: NDCA: 2,6-naphthalenedicarboxylic acid TPA: terephthalic acid IPA: isophthalic acid OPA: orthophthalic acid PPDC : Paraphenylenedicarboxylic acid EG: ethylene glycol PEG: polyethylene glycol CHDM: cyclohexanedimethanol NPG: neopentyl glycol BPA: bisphenol A BP: biphenol PHBA: parahydroxybenzoic acid HNCA: 6-hydroxy-2-naphthalenecarboxylic acid SIP: sulfo Isophthalic acid PCT: Polycyclohexanedimethanol terephthalate PET: Polyethylene terephthalate PAr: Polyarylate [TPA / BPA (10
0/100)]

The thickness of these supports of the present invention is 60 to.
122 μm is desirable. In a photographic film, a gelatin layer having water absorbency is generally coated on a support in an amount of 3 to 30 μm, so that this layer shrinks in a dry state to generate a large shrinkage stress, and as a result, the film deforms like a gutter. . Such a gutter-like curl lowers the flatness at the time of shooting and printing, and lowers the passability. Therefore, a support having a sufficient elastic modulus to withstand this contraction stress is required. At present, there is no polymer having versatility and capable of forming a film on a transparent film and having an elastic modulus sufficient to reduce the thickness to 60 μm or less. On the other hand, if 122 μm or more, T
It is a thickness that can be achieved with AC, and it is not possible to achieve thinning, which is one of the objects of the present invention. Therefore, the thickness of the support is preferably 60 to 122 μm.

The core diameter of the present invention is 5 to 11 mm.
The minimum core diameter of the conventional 135 system is 14 mm. To make the camera smaller, it is possible to make the spool smaller, but if the diameter is less than 5 mm, the photographic emulsion will suffer pressure overhang, so the core diameter must be at least 5 mm. If it exceeds 11 mm, the size of the camera, which is the main purpose of the light-sensitive material, cannot be reduced. Therefore, the diameter of the winding core needs to be 5 to 11 mm.

The heat treatment method for improving the curl of the present invention will be described. When the minimum winding core diameter of the conventional 135 system, 14 mm, is reduced to 5 to 11 mm, the curl tends to be formed even when the polyester support of the present invention is used. In order to solve this problem of curl, we have investigated the glass transition temperature (T
It has been found that a heat treatment at a temperature below g) results in a support with significantly less curl.

This heat treatment is a method for reducing the free volume in the support and making it less likely to have a curl. Usually, the polyester support is rapidly cooled from Tg or higher to Tg or lower after film formation, stretching and heat setting. The rapidly cooled support has a Tg
Since it is fixed while maintaining the large free volume described above, it is in a state in which it is easy to have a curl. When this is heat-treated at a temperature of Tg or lower, it is transformed into an equilibrium state in which the free volume is small, and it is possible to make it hard to have a curl. In order to further increase the effect of eliminating the curl, heat treatment is performed at a temperature of Tg or higher and lower than the melting point (melting temperature determined by DSC) to erase the heat history of the support, and then at a temperature of 50 ° C. or higher and lower than Tg. Reheat treatment may be performed. In the present invention, the heat treatment at a temperature of Tg or higher and lower than the melting point is referred to as "preheat treatment", and the heat treatment at 50 ° C or higher and lower than Tg is referred to as "post heat treatment". Pre-heat treatment temperature is Tg or higher and lower than melting point, more preferably Tg + 20 ° C.
5 below the crystallization temperature (the crystallization temperature determined by DSC)
It is recommended to do this for 3 to 3 minutes. When the pre-heat treatment is performed at a temperature equal to or higher than the melting point, the elasticity of the support is remarkably reduced, which causes problems in surface condition and transportability. The pre-heat treatment may be carried out within this temperature range at a constant temperature (constant temperature pre-heat treatment), may be carried out while lowering the temperature (pre-heat treatment before cooling), or may be carried out while raising the temperature (rise of temperature). Pre-heat treatment). The pre-heat treatment time is 0.1 minutes or more and 1500 hours or less, more preferably 1 minute or more and 1 hour or less. If the time is 0.1 minutes or less, a sufficient effect cannot be obtained, and if the time is 1500 hours or more, the effect is saturated, while the support is likely to be colored or brittle.

After this pre-heat treatment, the post-heat treatment is carried out, but it may be rapidly cooled from the pre-heat treatment end temperature to the post-heat treatment start temperature, or may be gradually cooled to the post-heat treatment start temperature across Tg. Good. After cooling to room temperature once,
The post-heat treatment temperature may be raised. Post heat treatment temperature is 50
℃ or more and less than Tg, more preferably Tg -20 ℃ or more Tg
Heat treatment is performed at less than. If the temperature is lower than 50 ° C., it takes a long time to obtain a sufficient curling effect, resulting in poor industrial productivity. The post heat treatment may be carried out at a constant temperature within this temperature range,
You may heat-process, cooling. The average cooling rate of cooling is −0.01 to −20 ° C./hour, more preferably −0.1.
~ -5 ° C / hour. The post heat treatment time is 0.1 hours or more and 1500 hours or less, and more preferably 0.5 hours or more and 200 hours or less. If the time is 0.1 hours or less, a sufficient effect cannot be obtained, and if the time is 1500 hours or more, the effect is saturated, while the support is likely to be colored or brittle. Although there are several combinations of these pre-heat treatment and post-heat treatment methods, after the constant temperature pre-heat treatment at Tg + 20 ° C. or higher and the crystallization temperature or lower, a cooling rate of −0.1 to Tg−20 ° C. A post-heat treatment is preferably performed while cooling at -5 ° C / hour.

The heat treatment of such a support may be carried out in the form of a roll or may be carried out while being conveyed in the form of a web. In the case of heat treatment in the form of a roll, it may be carried out by any of a method of heat-treating the roll from room temperature in a constant temperature bath, and a method of winding and heat-treating the roll in a constant temperature during web conveyance. Good. The former method requires time for raising and lowering the temperature, but has an advantage of requiring less equipment investment. The latter method requires a winding facility at high temperature, but has an advantage that the heating time can be omitted. In the roll-shaped heat treatment, due to the heat shrinkage stress generated during the heat treatment, wrinkles due to winding tightness and surface defects such as cut-outs of the core portion are likely to occur. For this reason, unevenness is imparted to the surface (for example, conductive inorganic fine particles such as SnO ₂ and Sb ₂ O ₅ are applied) to reduce creaking between the supports, thereby preventing wrinkles due to winding tightening, and It is desirable to make a contrivance such that a knurl is provided on the end of the core and the end of the core is slightly raised to prevent the cut end of the winding core from appearing. On the other hand, when the heat treatment is carried out in the form of a web, a long post-heat treatment step is required, but a better surface condition of the support can be obtained as compared with the heat treatment in the form of a roll. Among these heat treatment methods, it is preferable that the pre-heat treatment is performed in a web shape and the post-heat treatment is performed in a roll shape. When the pre-heat treatment is performed in web form,
This is because a planar failure is less likely to occur as compared with the case of performing in a roll shape, and the post heat treatment requires a relatively long time.

These heat treatments may be carried out at any stage after the film formation on the support, after the surface treatment, after the coating of the back layer (antistatic agent, lubricant, etc.) and after the coating of the undercoat. Preferred is after the antistatic agent is applied. As a result, it is possible to prevent the attachment of dust due to electrification, which causes a surface failure of the support during heat treatment. The roll core used for the heat treatment preferably has a hollow structure capable of flowing a high-temperature liquid or one having an electric heater built therein so that it can be heated in order to efficiently propagate the temperature to the film. The material of the roll winding core is not particularly limited, but it is preferable that the material is not deteriorated in strength or deformed by heat, and examples thereof include stainless steel, aluminum, and resin containing glass fiber. If necessary, rubber or resin may be lined on these cores.

Further, an ultraviolet absorber may be kneaded into these polymer films for the purpose of imparting stability with time. It is desirable that the UV absorber has no absorption in the visible region, and the amount thereof is usually 0.5% to 20% by weight, preferably about 1% to 10% by weight, based on the weight of the polymer film. Is. If it is less than 0.5% by weight, the effect of suppressing the deterioration of ultraviolet rays cannot be expected.
As the ultraviolet absorber, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,
2-hydroxy-4-n-octoxybenzophenone,
4-dodecyloxy-2-hydroxybenzophenone,
Benzophenone-based compounds such as 2,2 ', 4,4'-tetrahydroxybenzophenone and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2 (2'-hydroxy-5-methylphenyl) benzotriazole, 2
(2'-hydroxy 3 ', 5'-di-t-butylphenyl) benzotriazole, 2 (2'-hydroxy-3'
Examples thereof include benzotriazole-based UV absorbers such as -di-t-butyl-5'-methylphenyl) benzotriazole and salicylic acid-based ultraviolet absorbers such as phenyl salicylate and methyl salicylate.

Polyesters, especially aromatic polyesters, have a high refractive index of 1.6 to 1.7, while gelatin, which is the main component of the photosensitive layer coated thereon, has a refractive index of 1.5.
Since this value is 0 to 1.55, which is smaller than this value, when light is incident from the film edge, it is reflected at the interface between the base and the emulsion layer to cause a so-called light piping phenomenon (edge covering). In order to avoid such a light piping phenomenon, a method of incorporating inert inorganic particles and the like into the film, a method of adding a dye, and the like are known. The method of adding a dye is preferable because it does not significantly increase the film haze. Regarding the dye used for film dyeing, it is preferable that the color tone is gray dyeing due to general properties of the light-sensitive material, excellent heat resistance in the film forming temperature range of the polyester film, and excellent in compatibility with polyester. . As a dye,
From the above viewpoint, it is possible to achieve the object by mixing commercially available dyes for polyester such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku.

The polyester film according to the present invention can be imparted with slipperiness according to the intended use, and kneading with an inert inorganic compound or coating with a surfactant is generally used. Such inert inorganic particles include SiO ₂ , TiO ₂ , BaSO ₄ , CaCO ₃ ,
Examples are talc and kaolin. Further, in addition to the slipperiness imparted by an external particle system in which inert particles are added to the polyester synthesis reaction system described above, a slipperiness imparting method by an internal particle system in which a catalyst or the like added during the polyester polymerization reaction is precipitated can also be adopted. Is. As the external particle system, it is desirable to select SiO ₂ having a refractive index relatively close to that of the polyester film, or an internal particle system capable of relatively reducing the precipitated particle size. Further, in the case of kneading, a method of laminating a layer imparted with a function in order to obtain more transparency of the film is also preferable. As this means, specifically, a plurality of extruders and feed blocks,
Alternatively, a coextrusion method using a multi-manifold die is exemplified.

In order to firmly adhere a photographic layer (a photosensitive silver halide emulsion layer, an intermediate layer, a filter layer, a protective layer, a conductive layer and a back layer) to the support of the present invention, a glow discharge treatment or an ultraviolet ray treatment is carried out. After the treatment, an undercoat layer is provided and a photographic photosensitive layer is provided thereon.

The gas composition of the discharge atmosphere during the glow discharge treatment may be only the gas species generated in the container when the support itself is subjected to the discharge treatment as described in JP-A-59-556430. However, Japanese Patent Application No. 5-199
It is preferable to carry out the glow discharge treatment in the presence of water vapor described in No. 704. Water vapor partial pressure is 10% or more and 100%
The following is preferable, and 40% or more and 90% or less is more preferable. The gas other than water vapor is air composed of oxygen, nitrogen and the like. The method of quantitatively introducing water vapor into the glow discharge treatment atmosphere is as follows. Can be achieved by quantifying.

When the glow discharge treatment is carried out while the support to be surface-treated is preheated, the adhesion can be improved in a short time and the yellowing of the support can be greatly reduced. The preheating temperature is preferably 50 ° C. or higher and Tg or lower, and 70
C. or higher and Tg or lower are more preferable, and 90.degree. C. or higher and Tg or lower are even more preferable. Specific methods for raising the polymer surface temperature in vacuum include heating with an infrared heater and heating with contact with a hot roll. The glow discharge treatment is preferably performed using the discharge electrode and the discharge treatment device described in Japanese Patent Application No. 147864/1993. The degree of vacuum during glow discharge treatment is preferably 0.005 to 20 Torr, more preferably 0.02 to 2 Torr. The voltage is 500-
It is preferably between 5,000 V and more preferably 500-3.
It is 000V. The discharge frequency used is DC to several 1
000 MHz, more preferably 50 Hz to 20 MHz,
More preferably, it is 1 KHz to 1 MHz. Discharge intensity is 0.01 KV · A · min / m ^{2 to 5} KV · A · min /
m ² is preferable, more preferably 0.15 KV · A · min /
m ^{2 to 1} KV · A · min / m ² . It is preferable that the temperature of the support subjected to the glow discharge treatment is immediately lowered by using a cooling roll by the method described in JP-A-3-39106.
This can prevent deterioration of flatness due to plastic deformation due to external force at high temperature and deterioration of transparency and blocking resistance due to deposition of low molecular weight substances (monomers, oligomers, etc.) on the surface of the support. .

The ultraviolet irradiation treatment is conducted in Japanese Examined Patent Publication No. 43-2603.
It is preferable to use the processing methods described in JP-B No. 43-2604 and JP-B No. 45-3828. The mercury lamp is a high pressure mercury lamp consisting of a quartz tube and has an ultraviolet wavelength of 220.
Those between ˜380 nm are preferred. The UV irradiation may be performed in the stretching step of the support, at the time of heat setting, or after the heat setting.
Regarding the method of ultraviolet irradiation, a high-pressure mercury lamp having a main wavelength of 365 nm can be used as the light source if there is no problem in the performance of the support that the surface temperature of the support rises to around 150 ° C. When low temperature treatment is required, a low pressure mercury lamp having a dominant wavelength of 254 nm is preferable. It is also possible to use an ozone-less type high pressure mercury lamp and a low pressure mercury lamp. Regarding the amount of light to be treated, the larger the amount of treatment is, the more the adhesive force between the support and the layer to be adhered is improved. For the polyester support of the present invention, a high-pressure mercury lamp having a main wavelength of 365 nm, and the irradiation light amount is preferably ^{20 to} 10000 (mJ / cm ² ), more preferably 50 to 2000 (mJ / cm ² ). . In the case of a low-pressure mercury lamp whose main wavelength is 254 nm, the irradiation light intensity is 100
~ 10,000 (mJ / cm ² ) is good, more preferably 300
˜1500 (mJ / cm ² ).

Examples of the binder for the undercoat layer of the polyester support of the present invention include gelatin, vinyl chloride, vinylidene chloride, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, diolefin monomers, vinyl monomers and the like. Examples thereof include monomers and copolymers thereof, and nitrocellulose.

Gelatin which is a preferred subbing layer of the present invention includes acid-processed gelatin, alkali-processed gelatin, enzyme-processed gelatin which is enzyme-processed in the production process of gelatin, and gelatin derivatives, that is, a functional group in a molecule. It may be modified by treating with a reagent having an amino group, an imino group, a hydroxyl group and a carboxyl group and having a group capable of reacting with them. Regarding the gelatin production method, for example, T.W. H. James: The Theory of
the Photographic Process
4th. ed. 1977 (Macmillan) 55
Pages, pages 72 to 75 (Maruzen) of the Science Handbook (top), and 119-124 (Corona Publishing Co., Ltd.), the basics of photographic engineering-silver salt photography edition.

Calcium ion in gelatin (Ca ⁺⁺ ).
The content is preferably 2500 ppm or less, more preferably 1000 ppm or less, and further preferably 500 ppm or less with respect to dry gelatin in order to impart stability to the coating solution. To reduce the calcium ion content in gelatin to 2500 ppm or less, dissolve gelatin in water and remove fat impurities.
Subsequently, the aqueous gelatin solution can be obtained by passing it through a column of cation exchange resin or by contacting with the cation exchange resin by batch treatment. Gelatin used in the present invention is an acid-processed gelatin produced from collagen or ossein, which is the main component of animal bones or skins, with a treatment such as hydrochloric acid in the production process, and a lime produced with a treatment such as lime. They are processed gelatin, functional group-substituted gelatin derivatives and modified gelatin, and enzyme-processed gelatin. For details of the manufacturing method and properties of these gelatins, see Arthur Weis, The Macromolecular Chemistry of Gelatin (The).
Macromolecular Chemistry
of Gelatine, (Academic Press, 1964) 1
Pp. 87-217. Further, it is preferable to contain a nonionic surfactant in order to prevent aggregation of the gelatin undercoat solution and to improve the coatability of the undercoat. Preferred nonionic surfactants include compound I-5, compound I-6, compound I-12 described in JP-B-3-27099.
Examples thereof include compound I-13, compound I-23, compound I-31 and the like.

One of the subbing solutions of the present invention comprises 70 to 9
It is a liquid containing a vinylidene chloride copolymer comprising 9.9% by weight of a vinylidene chloride monomer and 0.1 to 5% by weight of a vinyl monomer having one or more carboxyl groups. Examples of vinyl monomers having one or more carboxyl groups of the present invention include acrylic acid, methacrylic acid, itaconic acid, citraconic acid and the like. The vinylidene chloride copolymer of the present invention is preferably an aqueous dispersion of latex. In this case, in addition to a normal latex having a uniform structure, a so-called core-shell type latex having different structures of the core part and the shell part of latex particles may be used.

Further, one of the undercoating liquids of the present invention is a liquid containing a copolymer of 10 to 90% by weight of a diolefin monomer and 90 to 10% by weight of one or more vinyl monomers. The diolefin monomer is an aliphatic unsaturated hydrocarbon CnH2n-2
(N is an integer of 4 to about 20), the cyclic structure CnH2n-4
(N is an integer) may be used. Specific examples include butadiene, isoprene, chloroprene, etc., but butadiene is particularly preferable from the viewpoint of adhesion to the support. Content is 10-9
0% by weight is preferred. The second component vinyl monomer is a monomer that forms a hard segment in the copolymer. Among them, vinyl aromatic, αβ-unsaturated nitrile, methacrylic acid ester, vinyl halide, vinyl ester such as styrene, acrylonitrile, methyl methacrylate, vinyl chloride, vinyl acetate and the like are preferable.

The polyamide-epichlorohydrin resin used in the subbing layer of the present invention forms a polyamide by heating a saturated or unsaturated dibasic carboxylic acid and a polyalkylene polyamine together at the reaction temperature, and then forming the polyamide. A conventional method for reacting polyamide with epichlorohydrin (for example, Japanese Patent Publication No. 35-35).
47, US Patent 292616, US Patent 31255.
No. 52, etc.). Examples of the above dibasic carboxylic acid include saturated dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sevalic acid. In addition, examples of the above polyalkylene polyamine include polyethylene polyamines such as diethylene triamine, triethylene tetramine, and tetraethylene pentamine, or polypropylene polyamines such as dipropylene triamine. Preferred combinations of dibasic carboxylic acid and polyalkylene polyamine include adipic acid and diethylene triamine, adipic acid and tetraethylene pentamine, and particularly preferred are adipic acid and diethylene triamine. The amount of the polyamide-epichlorohydrin resin added is 1 to 20% by weight, preferably 3 to 15% by weight, more preferably 5 to 10% by weight, based on the weight of the binder of the undercoat.

The most preferable antistatic agents of the present invention are ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ and In _2.
O ₃ , SiO ₃ , MgO, BaO, M _O O ₃ , V ₂ O ₅
It is a fine particle of at least one crystalline metal oxide or a composite oxide thereof selected from the above. Among these, a particularly preferable material is a conductive material containing SnO ₂ as a main component and containing about 5 to 20% of antimony oxide and / or further containing other components (for example, silicon oxide, boron, phosphorus, etc.). The fine particles of these conductive crystalline oxides or their composite oxides have a volume resistivity of 10 ⁷ Ωcm or less,
It is more preferably 10 ⁵ Ωcm or less. The particle size is 0.002-0.7 μm, particularly 0.005-0.
It is preferably 3 μm. This conductive layer may be on the silver halide emulsion layer side of the support or on the back layer opposite to the silver halide emulsion layer. The binder used in that case is not particularly limited, and may be a water-soluble or organic solvent-based binder,
Alternatively, it may be crosslinked like a latex. The volume resistance of the obtained antistatic layer is 10 ¹² Ω to 10 ³ Ω, more preferably 10 ¹⁰ Ω to ^{10 3} Ω, and further 10
⁹ Ω to 10 ³ Ω is preferable.

The photosensitive silver halide emulsion layer, the intermediate layer, the filter layer, the protective layer, the conductive layer and the back layer constituting the light-sensitive material of the present invention are mainly composed of a hydrophilic colloid layer.
Examples of the binder for the hydrophilic colloid layer include 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 such as polyvinyl alcohol. , Poly-N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide, or their derivatives and partial hydrolysates, dextran, polyvinyl acetate, polyacrylic acid ester, rosin and the like. Mixtures of two or more of these colloids may be used if desired.

Next, the photographic layer of the photographic light-sensitive material of the present invention will be described. The silver halide emulsion layer may be either black or white for color. Here, a color silver halide photographic light-sensitive material will be described. The light-sensitive material of the present invention may have at least one silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer provided on a support. There is no particular limitation on the number of layers and the order of layers of 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 a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, it is generally a unit photosensitive layer. The arrangement is such that the red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer are arranged in this order from the support side. 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-61-4
No. 3748, No. 59-113438, No. 59-113
No. 440, No. 61-20037, No. 61-20038
The couplers as described in the specification, DIR compounds and the like may be contained, and a color mixing inhibitor may be contained as is commonly used. 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 Nos. 57-112751, 62-200350, and 6
2-206541, 62-206543, 56
-25738, 62-63936, 59-20.
No. 2464, Japanese Patent Publication No. 55-34932, No. 49-15
495. The silver halide grains have regular crystal shapes such as cubes, octahedra and tetradecahedrons, irregular crystal shapes such as spheres and plates, and crystal defects such as twin planes. It may have one or a combination 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 (December 1978), pp. 22-23, "I. Emulsion preparation and types", and ibid.
18716 (November 1979), p.648, Graphide, "Physics and Chemistry of Photography", published by Paul Montell (P. G.
lafkides, Chemie et Phisique Photographique, Paul
Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin Photographic Emul).
sion Chemistry (Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikman et al., VL Zelikman et al., Making and Coating Photog
It can be prepared using the method described in raphic Emulsion, Focal Press, 1964) and the like. Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 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 Gutoff, Photographic Science and En
gineering), Vol. 14, pp. 248-257 (1970)
); U.S. Pat. Nos. 4,434,226 and 4,41
4,310, 4,433,048, 4,43
It can be easily prepared by the method described in 9,520 and British Patent No. 2,112,157. The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with 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.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. 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 N
No. 17643 and No. 18716, 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.

(Types of Additives) (RD17643) (RD18716) 1 Chemical sensitizer, page 23, page 648, right column 2 Sensitivity enhancer, same as above 3 Spectral sensitizer, supersensitizer, page 23 to page 648, right column ~ Page 649 Right column 4 Whitening agent Page 24 5 Antifoggants and stabilizers 24 to 25 pages 649 Right column to 6 Light absorbers, filter dyes, UV absorbers 25 to 26 pages 649 Right column to 650 left columns 7 Anti-staining agent Page 25 Right column Page 650 Left-right column 8 Dye image stabilizer Page 25 9 Hardener 26 Page 651 Left column 10 Binder 26 Same as above 11 Plasticizers and lubricants Page 27 650 Right column 12 Coating Auxiliary agents, surface active agents, pages 26 to 27, page 650, right column Also, in order to prevent deterioration of photographic performance due to formaldehyde gas, they are described in US Pat. Nos. 4,411,987 and 4,435,503. It is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with formaldehyde.

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG. . Examples of yellow couplers include U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024, 4,401,752, and 4,248,961. issue,
Japanese Patent Publication No. 58-10739, British Patent No. 1,425,0
20, No. 1,476,760, and U.S. Pat. No. 3,9.
73,968, 4,314,023, 4,
Those described in 511, 649, European Patent No. 249,473A, etc. are preferable. 5 for magenta coupler
-Pyrazolone-based and pyrazoloazole-based compounds are preferable, and U.S. Pat. Nos. 4,310,619 and 4,35.
1,897, European Patent 73,636, US Patents 3,061,432, 3,725,067, Research Disclosure No. 24220 (1984).
June 60), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238, 6).
0-35730, 55-118034, 60-
185951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630,
Those described in WO (PCT) 88/04795 and the like are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, No. 249,453A, U.S. Patent Nos. 3,446,622 and 4,333,999.
No. 4,753,871, No. 4,451,55
No. 9, No. 4,427, 767, No. 4, 690, 8
No. 89, No. 4,254,212, No. 4,296,
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable. Research Disclosure No. 1 is a colored coupler for correcting unwanted absorption of color forming dyes.
7643, Section VII-G, U.S. Pat. No. 4,163,670.
No. 57/39413, U.S. Pat. No. 4,000
Those described in 4,929, 4,138,258 and British Patent 1,146,368 are preferable. Examples of couplers in which the color forming dye has excessive diffusibility include U.S. Pat. No. 4,366,237 and British Patent 2,125,57.
No. 0, European Patent No. 96,570, and West German Patent (Publication) No. 3,234,533 are preferable. Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820, 4,080,211, 4,367,282, and 4,409,320.
U.S. Pat. No. 4,576,910, British Patent 2,102,13.
No. 7, etc.

A coupler which releases a photographically useful residue upon coupling is also preferably used in the present invention. The DIR coupler which releases the development inhibitor is the above-mentioned R
Patents described in D17643, VII to F, JP-A-5
7-151944, 57-154234, 60
Those described in U.S. Pat. No. 4,184,248, No. 63-37346, and U.S. Pat. No. 4,248,962 are preferable. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patents 2,097,140 and 2,131,188, JP-A-59-157638.
Nos. 59-170840 and No. 59-170840 are preferable.
Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. Nos. 4,283,472, and 4,338,393. No. 4,310,618 and the like, multiequivalent couplers, JP-A-60-185950.
No. 6, JP-A-62-24252 and the like, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DI.
R redox-releasing redox compounds, EP 17
No. 3,302A, a coupler that releases a dye that recovers color after separation, R.I. D. No. 11449 and No. 24241, couplers releasing bleaching accelerators described in JP-A No. 61-201247, couplers releasing ligands described in US Pat. No. 4,553,477, JP-A-63-75747. Examples thereof include couplers that release the leuco dye described.
The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents 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, and aniline derivatives. , Hydrocarbons and the like. 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 the latex dispersion method, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230. 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, and the film swelling speed T 1/2 is preferably 30 seconds or less. The film thickness is 25
℃ means a film thickness measured at a relative humidity of 55% (2 days), the film swelling rate T _1/2 can be measured in accordance with a known method in the art. For example, A. Green et al. Photographic Science and Engineering (Photogr. Sci. En
g.), Vol. 19, No. 2, pp. 124-129, and can be measured by using a swellometer (swelling meter) of the type, T _1/2 is 30 ° C. for 3 minutes 15 seconds with a color developer. 90% of the maximum swollen film thickness reached upon treatment is defined as the saturated film thickness, and is defined as the time required to reach this T1 / 2 film thickness. The film swelling rate T1 / 2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is 150
~ 400% is preferred. The swelling rate is calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness)
/ Can be calculated according to the film thickness.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29 and No. 1
The development can be carried out by the usual method described in the left column to the right column of 615 of 8716. 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, the Schiff base type compounds described in U.S. Pat. No.

[0050]

【Example】

Example 1 1) Preparation of support Pellets of the compounds PEN, PET, PAr, and PCT used were previously dried at 150 ° C. for 4 hours. The support mixed in the proportions shown in Table 1 was prepared by first mixing individual pellets in the indicated proportions, then extruding at 280 ° C. using a twin-screw kneading extruder, and then pelletizing. To these polyester solids, 54 ppm each of the dyes described in Japanese Patent Application No. 5-316676, compound I-6 and compound I-24 were added,
It was dried by a conventional method. These pellets were melted at 300 ° C, extruded from a T-die, stretched 3.1 times in the longitudinal direction at Tg + 30 ° C and 3.5 times in the transverse direction at Tg + 20 ° C, and heat set at 250 ° C for 6 seconds. 90μ
A biaxially oriented polyester support of m was prepared.

[0051]

[Table 1]

[0052]

[Table 2]

2) Heat Treatment and Surface Treatment of Support The support formed by the above method was subjected to pre-heat treatment and post-heat treatment under the conditions shown in Table 1. All the heat treatments were carried out with the core having a diameter of 30 cm and the undercoat surface facing outside. After that, both sides of the support were subjected to glow discharge treatment (denoted as G) or ultraviolet irradiation treatment (denoted as UV) by the following method. In the glow discharge treatment, first, a cylindrical electrode having a cross section of 2 cm in diameter and having a length of 40 cm was fixed on four insulating plates at intervals of 10 cm. This electrode plate is fixed in the vacuum tank, 15 cm away from this electrode surface,
A biaxially stretched film having a thickness of 90 μm and a width of 30 cm was run such that the surface treatment was performed for 2 seconds so as to face the electrode surface. Immediately before the film passes through the electrodes, the film is 3/4 on a heating roll with a temperature controller of 50 cm in diameter.
The heating roll was arranged so as to make circumferential contact, and the film surface temperature was controlled at 115 ° C. by bringing a thermocouple thermometer into contact with the film surface between the heating roll and the electrode zone. The pressure inside the vacuum chamber was 0.15 Torr, and the partial pressure of H ₂ O in the atmospheric gas was 80%. Discharge frequency is 30K
Hz, output 2500 W, treatment intensity 0.5 KV · A · min / m ² . The vacuum glow discharge electrode is Japanese Patent Application No. 5-147.
The method described in 864 was followed. After the discharge treatment, the diameter of the support should be 50 so that the surface temperature becomes 30 ° C before the support is wound up.
It was wound by contacting a cooling roll with a temperature controller of cm. Ultraviolet irradiation is provided on both sides of the support parallel to the film surface at a distance of 10 cm, width 50 cm, arc length 3
Irradiation was carried out at 115 ° C. in air for 2 minutes using a cylindrical 1 KW quartz high-pressure mercury lamp having a main wavelength of 365 nm of 0 cm. The irradiation light amount was 500 mJ / cm ² .

3-1) Coating of undercoat layer (emulsion layer side) A methanol-based undercoat solution having the following composition was coated on a support at 10 ml / m ² with a wire bar, dried at 115 ° C. for 2 minutes, and then rolled. I took it.・ Gelatin (Ca ⁺⁺ content 100 ppm) 10.0 parts by weight ・ Water 24.0 parts by weight ・ Methanol 962.0 parts by weight ・ Salicylic acid 3.0 parts by weight ・ Polyamide-epichlorohydrin resin-1 (solid content) X parts by weight Nonionic surfactant described in JP-B-3-27099 1.0 part by weight Compound I-13 A photosensitive layer described below was coated on this undercoat surface.

Polyamide-Epichlorohydrin Resin-
Preparation method 1 Dissolve 500 g of diethylenetriamine in 222 ml of water,
Next, while introducing nitrogen gas, 632 g of adipic acid is added and dissolved. The mixture at 130-170 ° C. for 2.5 hours,
Heat at 170-225 ° C for 1.5 hours, and in the meantime, add water 41
Distill off 0 ml. Remove the heating bath and slowly cool to 90-110
When the temperature reached ℃, water was added to dissolve the mixture, and the total amount was 7480 ml. While stirring the obtained polyamide aqueous solution at 50 to 55 ° C., 441 g of epichlorohydrin is added over 1 hour. After the addition, stir at 70 ° C. for 1 hour. The reaction product obtained is cooled to room temperature and adjusted to pH 5.5 with 6N hydrochloric acid. Further, water was added to dilute the total amount to 8480 ml. Thus, an aqueous solution of polyamide-epichlorohydrin containing 15% of solid content was obtained. The addition amount X represents the solid content.

3-2) Coating of first layer of back layer After undercoating, on the surface opposite to the side on which the undercoat layer of the support was provided, a methanol-based back formulation having the following composition was used at 5 ml / m using a wire bar. ^Two coats were applied, dried at 115 ° C. for 2 minutes, and then scraped off. -Gelatin (Ca ⁺⁺ content 100 ppm) 10.0 parts by weight-Water 51.0 parts by weight-Methanol 937.0 parts by weight-Acetic acid 1.0 part by weight-Polyamide-epichlorohydrin resin-1 (solid content) X parts by weight -Nonionic surfactant described in JP-B-3-27099 1.0 part by weight Compound I-13

3-3) Second back layer 230 parts by weight of stannic chloride hydrate and antimony trichloride 2
3 parts by weight was dissolved in 3000 parts by weight of ethanol to obtain a uniform solution. A 1N aqueous sodium hydroxide solution was added dropwise to this solution until the solution had a pH of 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 500 ° C., and the bluish average particle size was 0.005 μm.
Fine particles of stannic oxide antimony monoxide composite were obtained. The resistivity of this fine particle powder was 25 Ω · cm. A mixed solution of 40 parts by weight of the fine powder and 60 parts by weight of water was added to pH 7.0.
Was roughly dispersed in a stirrer and then dispersed in a horizontal sand mill (Dynomill, manufactured by Willy A. Backfen AG) until the residence time reached 30 minutes, and some of the primary particles were aggregated to form a secondary aggregate. A dispersion having a particle size of 0.05 μm was prepared.

A liquid having the following formulation was applied so that the dry film thickness was 0.3 μm, and dried at 110 ° C. for 30 seconds.・ The above conductive fine particle dispersion liquid (SnO ₂ / Sb ₂ O ₃ , 0.15 μm) Y parts by weight ・ Gelatin (Ca ⁺⁺ content 100 ppm) 10 parts by weight ・ Water 270 parts by weight ・ Methanol 600 parts by weight ・ Resorcin 20 parts by weight Part Nonionic surfactant described in JP-B-3-27099 0.1 part by weight Compound I-13 Compound containing no conductive fine particle dispersion (Y parts by weight), 25 or 100 parts by weight of additive Three levels were prepared. The volume resistance of the antistatic layer is 10 ₁₄ Ω and 10 ₁₁ respectively.
Ω was 10 ₈ Ω.

3-4) Back Third Layer A liquid having the following formulation was applied to give a dry film thickness of 1.2 μm. Drying was performed at 110 ° C. Diacetyl cellulose 100 parts by weight Trimethylolpropane-3-toluene diisocyanate 25 parts by weight Methyl ethyl ketone 1050 parts by weight Cyclohexanone 1050 parts by weight

3-5) Back Fourth Layer Preparation of Sliding Layer The following 1 solution was heated and dissolved at 90 ° C., added to 2 solutions, and then dispersed by a high pressure homogenizer to prepare a slip dispersion stock solution. 1 liquid-compound _{C 6 H 13 CH (OH)} (CH 2) 10 COOC 40 H 61 0.7 g · Compound _{n-C 50 H 101 O (} CH 2 CH 2 O) 16 H 1.1 g · Xylene 2 0.5 g 2 liquid-propylene glycol monomethyl ether 34.0 g The following binder and solvent were added to the above slip dispersion stock solution to prepare a coating solution. Diacetyl cellulose 3.0 g Acetone 600.0 g Cyclohexanone 350.0 g The slip coating solution was wire bar coated at a coating amount of 10 cc / m ² .

4) Preparation of Light-Sensitive Material On a base coated with an undercoat, JP-A-5-323540 is used.
No., Example 1. Each layer described in Sample 103 was applied in multiple layers to prepare a sample which is a multilayer color light-sensitive material.

5) Evaluation of Photographic Film The curl of the photographic film sample was evaluated according to the following procedure. 5-1) Core set The produced film was slit into a width of 35 mm and a length of 1.2 m. After conditioning this at 25 ° C. and 60% RH overnight,
Inner winding of photosensitive layer, spool diameter 4mm as shown in Table 1.
/ Cartridge inner diameter 14.5 mm, spool diameter 5 mm / cartridge inner diameter 15.0 mm, spool diameter 7 mm / cartridge inner diameter 15.5 mm This was placed in a sealed container and heated at 80 ° C. for 2 hours to give a curl. This temperature condition is a condition assuming a film placed in a car in the summer. 5-2) Evaluation of folding of the trailing edge of the film after development and unevenness of development processing After the film having a curl under the above conditions is allowed to cool at 25 ° C, the sample film is taken out from the sealed container and automatically developed. Machine (Made by Fuji Photo Film: Minilab FP-56
0B, CN-16FA processing solution).
The film used was treated with a processing solution prepared by separately running the previously imagewise exposed film until the color development replenishment amount was 3 times the tank volume. After processing, visually inspect the film, ◎ if there is no fold at the trailing edge of the film, ∘ if there is a slight fold but the print image is normal and the printed image is normal, ∘ Those that also hinder the transportation of time are marked with x. The unevenness in the processing of the development is ∘ when the film after processing is visually observed and uniformly processed, and the unevenness is not observed in the printed image although there is some unevenness in the film after the processing and there is no problem in practical use. ◯, when the film after processing had unevenness and the printed image also had unevenness, it was evaluated as x.

6) Adhesion Evaluation 6-1) Adhesion Evaluation Method During Drying A razor was used to make 6 cuts at intervals of 5 mm in length and width to make 25 squares, and adhesive tape (Nitto Denki) Adhere a knit tape manufactured by Kogyo Co., Ltd. and quickly peel it off in the 180 ° direction. In this method, 95% or more of the unpeeled portion is class A, 90% or more is class B, 60% or more is class C, and less than 60% is class D. Adhesive strength that can withstand practical use as a photographic material is one classified into Class A in the above four-stage evaluation. 6-2) Adhesion Evaluation Method When Wet In each of the following processing steps of color development, fixing and stabilizing bath, a scratch mark is marked on the emulsion surface of the film in a liquid with a pencil to mark it. Adhesion is evaluated by the maximum peeling width, which is peeled along the line of ×, by rubbing the fingertip with a rubber sack 5 times. Class A when the emulsion layer does not peel more than scratches,
When the maximum peeling width is 2 mm or more, it is class B, when the maximum peeling width is 5 mm or less, it is class C, and the others are class D. Adhesive strength that can withstand practical use as a photographic material is one classified into Class A in the above four-stage evaluation.

7) Static mark evaluation 7-1) Static mark test After unconditioning the unexposed sample at 25 ° C. and 10% RH for 6 hours, the sample was tested for various materials in a dark room under the same air conditioning conditions. After rubbing with a rubber roller and a urethane roller in order to investigate what the static mark looks like, it was processed by the above-mentioned automatic developing machine to examine the generation degree of the static mark. The degree of occurrence of static marks was evaluated in the following three stages. A: Static mark is not observed at all B: 〃 Slightly recognized C: 〃 Equally recognized

7-2) Dust test A sample (20 cm × 20 cm) before and after the development treatment was thoroughly rubbed with nylon under conditions of temperature and humidity of 25 ° C. and 10% RH to examine the adhesion of tobacco ash. The evaluation was performed in the following three stages. A: No dust is seen B: 〃 Slightly recognized C: 〃 Equivalent

8) Results The results are shown in Table 1. The Tg of the present invention is 90 ° C. or higher and 200 ° C.
The following polyester supports, Levels 1 to 12, and 15 are less prone to curling and less likely to cause uneven processing and trailing edge folding of the film during development processing. On the other hand, when the Tg is less than 90 ° C., the levels 13 and 14 are likely to cause a winding habit, resulting in uneven processing and trailing edge folding of the film during development processing. Further, the levels 3 and 6 which were subjected only to the surface treatment and to which the polyamide-epichlorohydrin resin was not added and the levels 1 and 2 which were not subjected to the surface treatment and used only the polyamide-epichlorohydrin resin of the present invention had poor adhesiveness. Those which have been surface-treated and to which a polyamide-epichlorohydrin resin has been added to the undercoat layer have good adhesiveness. 0.5w for undercoat binder
The adhesion was slightly inferior in Level 4 containing t%. Level 5 with 5 wt% addition shows a sufficient adhesion level. The level 9 in which the electroconductive fine particle dispersion liquid was removed had a poor AS property and had static marks and dust. It can be seen that when conductive fine particles are added and the volume resistance becomes 10 ₁₁ Ω, the AS property is considerably improved, and when it becomes 10 ₈ Ω, no static mark or dust is generated at all.

Example 2 1) Preparation of support The polyester pellets shown in Table 2 were preliminarily dried at 150 ° C. for 4 hours.
Dried for hours. For these polyester solids,
The dyes described in Japanese Patent Application No. 5-316676, Compound I-6 and Compound I-1 were added at 65 ppm and 216 ppm, respectively,
It was dried by a conventional method. These pellets were melted at 300 ° C, extruded from a T-die, stretched 3.1 times in the longitudinal direction at Tg + 30 ° C and 3.5 times in the transverse direction at Tg + 20 ° C, and heat set at 250 ° C for 6 seconds. 90μ
A biaxially oriented polyester support of m was prepared.

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[Table 3]

[0069]

[Table 4]

2) Surface Treatment and Heat Treatment of Support The support formed by the above method was subjected to pre-heat treatment and post-heat treatment under the conditions shown in Table 1. All the heat treatments were carried out with the core having a diameter of 30 cm and the undercoat surface facing outside. After that, both sides of the support were subjected to glow discharge treatment (denoted as G) or ultraviolet irradiation treatment (denoted as UV) by the following method. The glow discharge treatment device is the same as that in the first embodiment. The pressure in the vacuum tank is 0.2
0 Torr, H ₂ O partial pressure in atmospheric gas is 75%, discharge frequency is 30 KHz, output is 3000 W, and treatment intensity is 0.65.
It was conducted at KV · A · min / m ² . The ultraviolet irradiation is the same as in Example 1 except that a cylindrical high pressure mercury lamp of 1.5 KW having a main wavelength of 365 nm is used. 3) Coating of undercoat layer (emulsion layer side) An aqueous undercoat solution having the following composition was applied on a support at 10 ml / m ² using a wire bar, dried at 115 ° C. for 2 minutes, and then stripped off. -Gelatin (Ca ⁺⁺ content 200ppm) 10.0 parts by weight-Water 985.5 parts by weight-Salicylic acid 2.5 parts by weight-Polyamide-epichlorohydrin resin-2 (solid content) X parts by weight-Japanese Patent Publication No. 3-27099 2.0 parts by weight of the described nonionic surfactant Compound I-13 A photosensitive layer described below was coated on this undercoat surface.

Polyamide-Epichlorohydrin Resin-
Method of 2 Polyamide-epichlorohydrin resin-1 In the case of polyamide-epichlorohydrin resin-1 except that 915 g of tetraethylenepentamine is used instead of diethylenetriamine and 1455 g of epichlorohydrin is used instead of 441 g of epichlorohydrin. Under the same conditions and the same operation as above, an aqueous solution of polyamide-epichlorohydrin containing 15% of solid content was obtained. Addition amount X
Represents the solid content.

4) Coating of backing layer After undercoating, on the surface opposite to the side on which the undercoating layer of the support was provided, an aqueous backing layer first layer formulation of the following composition was applied using a wire bar at 5 ml / m ² It was applied, dried at 115 ° C. for 2 minutes, and then scraped off. -Gelatin (Ca ⁺⁺ content 200ppm) 10.0 parts by weight-Water 987.0 parts by weight-Acetic acid 1.0 part by weight-Polyamide-epichlorohydrin resin-2 (solid content) X parts by weight-JP-B-3-27099 Nonionic surfactant described above 2.0 parts by weight Compound I-13 Coating of antistatic layer as back second layer on back first layer, coating of third back layer, slippage as fourth back layer The coating of layers was the same as in Example 1.

5) Preparation of light-sensitive material On a support provided with an undercoat layer, JP-A-2-854, Example 1. The layers described in Sample 101 were coated in multiple layers to prepare a sample which is a multilayer color light-sensitive material.

6) Evaluation of photographic film 6-1) Core setting method The prepared film was slit into a width of 35 mm and a length of 1.2 m. After conditioning this at 25 ° C. and 60% RH overnight,
Inner winding of photosensitive layer, spool diameter 4mm as shown in Table 1.
/ Cartridge inner diameter 14.5 mm, spool diameter 5 mm / cartridge inner diameter 15.0 mm, spool diameter 7 mm / cartridge inner diameter 15.5 mm This was placed in a sealed container and heated at 80 ° C. for 2 hours to give a curl. This temperature condition is a condition assuming a film placed in a car in the summer. The film with the curl is allowed to cool at 25 ° C., and then the sample film is taken out from the sealed container, which is then processed with an automatic processor (H6R-360 manufactured by Noritsu Co., Ltd.),
Development processing was performed using a processing solution (CR-56 standard processing solution manufactured by Fuji Photo Film Co., Ltd.). 6-2) Curling habit measurement method The degree of curling in the lengthwise direction attached by the core set is determined according to ANSI / ASC pH 1.29-1985.
It was measured according to Test Method A and displayed in 1 / R [m] (R is the radius of the curl). If the curl value of the film before the development process is 65 or more, the film operability during the automatic development process and the film handling property in the automatic development processor are impaired. 6-3) Evaluation of scratches when passing through the printer's film carrier The developed film is passed through an automatic printer (8C6910-2 manufactured by Fuji Photo Film Co., Ltd.), and scratches do not occur on the surface of the film, causing problems with printing. Those that did not exist were marked with ◯, and scratches on the film surface when passing through the film carrier, and those that were visible in the print were marked with x. 6-4) Pressure exposure After the exposure is adjusted so that the density after development is minimized,
After being wound in the same manner as the core set, heat-treated, and developed. The pressure fog (color density unevenness) of the film was visually evaluated, and the product without the fog was represented by O, and the product with the fog was represented by X.

7) Results The results are shown in Table 2. The Tg of the present invention is 90 ° C. or higher and 200 ° C.
The following polyester supports, Levels 1 to 11, were less prone to curling, and had good film operability during automatic development and film handling in the automatic development processor. On the other hand, when the Tg is less than 90 ° C., level 12 is likely to cause a crease habit, and the film surface is scratched when passing through the film carrier of the printer, resulting in print failure. Further, the levels 3 and 6 which were subjected only to the surface treatment and to which the polyamide-epichlorohydrin resin was not added and the levels 1 and 2 which were not subjected to the surface treatment and used only the polyamide-epichlorohydrin resin of the present invention had poor adhesiveness. Surface treatment,
The one in which the polyamide-epichlorohydrin resin is added to the undercoat layer has good adhesiveness. The level of addition of 0.1 wt% or more to the undercoat binder shows a sufficient adhesion level. The level 7 with a diameter of 4 mm of the cartridge has pressure overburden, but the level 6 with a diameter of 5 mm is good without pressure overburden.

Example 3 The compound P-1 (PEN) support 90 μm on both sides was subjected to the glow discharge treatment described in Example 1. After that, the following two types of emulsion undercoat first layer and second layer shown below were coated, and the back layer was coated with the same back layers 1 to 4 as in Example 2, dried and wound up. Pre-heat treatment and post-heat treatment were performed under the same conditions as in 1. On the undercoated support, JP-A-2
-854, Example 1. Each layer described in Sample 101 was applied in multiple layers to prepare a sample of a multilayer color light-sensitive material. The rolling habit and the adhesion when rolled into a 7 mm spool were evaluated. The result is that the habit of rolling is good and the glow discharge treatment is performed.
In addition, the undercoat layer containing the polyamide-epichlorohydrin resin had good adhesion.

(A-1) Emulsion Undercoat A-First Layer Formulation Vinylidene chloride latex 15 parts by weight Polystyrene fine particles (average particle size 3 μm) Added to a coating amount of 80 mg / m ² Polyamide-epichlorohydrin resin-1 (solid) Min) 1.2 parts by weight Distilled water is added 100 parts by weight Coating liquid temperature 10 ° C. Dry film thickness 0.9 μm Drying condition 170 ° C. for 2 minutes (A-2) Undercoat A-second layer formulation Gelatin 1 part by weight Methylcellulose 0 0.05 parts by weight Acetic acid 0.2 parts by weight Nonionic surfactant described in JP-B-3-27099 0.01 parts by weight Compound I-13 100 parts by weight with addition of distilled water Coating solution temperature 25 ° C Dry film thickness 0. 1μm drying condition 170 ℃ 2 minutes

(B-1) Emulsion Undercoat B-First Layer Formulation An emulsion polymer obtained by emulsion polymerization of the following monomers according to Synthesis Example 1 was applied as an undercoat B-first layer. (Monomer) Butadiene 38 Monomer Styrene 54 〃 Acrylic acid 5 〃 Itaconic acid 3 〃 4 g of this undercoat liquid (resin content 50%), Polyamide-epichlorohydrin resin-1 (solid content) 0.1 g, Japanese Patent Publication No. 3- Nonionic surfactant compound I described in 27099
0.01 g of -13 was dissolved in 100 ml of distilled water, and coating and drying were performed under the following conditions. Coating amount 20 ml / m ² Drying condition 170 ° C. for 2 minutes (Synthesis example 1) Butadiene 38 Monomer Styrene 54 〃 Acrylic acid 5 〃 Itaconic acid 3 〃 Sodium dodecylbenzene sulfonate: Surfactant 3 Third dodecyl mercaptan: Molecular weight adjustment Agent 0.2 Tripotassium phosphate: Dispersant 0.3 Ammonium persulfate: Polymerization catalyst 0.3 Water 100 The synthesis method was as follows. The above substances were placed in a stirring autoclave in which the atmosphere was replaced with nitrogen gas, and the polymerization temperature was 50 ° C. Pressure 5 atm
Emulsion polymerization was carried out for 20 hours (pressure with butadiene), and the residual monomer (about 5% of the monomer) was distilled off to obtain a latex having a dry solid content of 49% by weight. (B-2) Undercoat B-second layer formulation (A-2) Undercoat The same formulation as the second layer formulation was applied and dried. A photosensitive layer was coated on the surface coated with the above two types of undercoat.

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As described above, the polyester support having a glass transition temperature (Tg) of 90 ° C. or more and 200 ° C. or less according to the present invention is less likely to have a curl and has a film handling property during or after development processing. It can be seen that a good silver halide photographic light-sensitive material can be produced. The effect of being hard to curl up is remarkable when the thickness of the support is small, and therefore it is particularly effective when wound on a small spool diameter, and a great effect that the cartridge can be miniaturized was obtained. The surface of the support of the present invention is subjected to glow discharge treatment or ultraviolet irradiation, and the undercoat layer is made of polyamide-
When the epichlorohydrin resin is contained, the adhesion to the photographic photosensitive layer is good.

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Claims (6)

[Claims] 1. A silver halide photographic light-sensitive material comprising a polyester support and at least one light-sensitive layer having a glass transition temperature (Tg) of 90 ° C. or more and 200 ° C. when the surface is subjected to glow discharge treatment or ultraviolet irradiation. A silver halide photographic light-sensitive material characterized in that the following undercoat layer on the support contains a polyamide-epichlorohydrin resin. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the polyester support is preheated at a temperature of Tg or higher and then postheated at a temperature lower than the glass transition temperature. 3. The photographic light-sensitive material has at least one conductive layer on at least one side, and the electrically conductive material of the conductive layer is Zn, Ti, Sn, Al, In, S.
i, Mg, Ba, Mo, W, V as a main component and at least one selected from metal oxides having a volume resistivity of 10 ⁷ Ωcm or less.
2. The silver halide photographic light-sensitive material described in 2. 4. The photographic light-sensitive material has an outer diameter of 5 mm to 11 mm.
4. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide photographic light-sensitive material is in the form of a roll wound around the spool. 5. The silver halide photographic light-sensitive material according to claim 1, wherein the polyester support is composed of a polyester containing naphthalenedicarboxylic acid and ethylene glycol as main components. 6. The silver halide photographic light-sensitive material according to claim 1, wherein the polyester support is polyethylene-2,6-naphthalenedicarboxylate.