JPH07219145A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photographic sensitive material having satisfactory adhesion and superior dynamic strength and less liable to curl. CONSTITUTION:When a silver halide emulsion layer is formed on at least one side of a polyester base to produce a silver halide photographic sensitive material, at least one side of the polyester made of polyester having 90 to 200 deg.C glass transition temp. is treated with a flame and the objective silver halide photographic sensitive material is obtd.

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 flame-treated polyester having a glass transition temperature (Tg) of 90 ° C. or more and 200 ° C. or less as a support.

[0002]

2. Description of the Related Art On a support of a photographic light-sensitive material, a fibrin-based polymer generally represented by triacetyl cellulose (hereinafter referred to as "TAC") and a polyethylene-based polymer such as polyethylene terephthalate (hereinafter referred to as "PET"). ]) Is used. Generally, photographic light-sensitive materials include sheet-like forms such as X-ray films, plate-making films and cut films, and color or black-and-white negative roll films used in a cartridge with a width of 35 mm or less. is there. TAC used as a support for roll film has high transparency and further has excellent properties in decurling after development processing. On the other hand, PET film is excellent in productivity, mechanical strength and dimensional stability, but it has poor curl after handling due to the strong curl remaining, so that it has the above-mentioned excellent properties and is in a usable range. Has been limited.

In recent years, the applications of photographic light-sensitive materials have become diversified, and there is a demand for downsizing of cameras, speeding up of film transportation during shooting, and higher shooting magnification. 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 for reducing the curl of the polyester film, for example, Japanese Patent Application Laid-Open No. 51-16
No. 358, JP-A-1-131550, US Pat. No. 4,
Methods such as those described in U.S. Pat. No. 141,735 are known. The environment in which the silver halide photographic light-sensitive material is used is various, and in recent years, the silver halide photographic light-sensitive material may be primarily left at a temperature close to 90 ° C., and the curl does not deteriorate even if it is left at such a temperature. Has become necessary. Therefore, the glass transition temperature of the polyester film used must be 90 ° C. or higher.

As a major problem in using a polyester film as a support for a silver halide photographic light-sensitive material, the adhesiveness between the support and the silver halide emulsion layer is strongly required. A surface treatment technique for adhering a silver halide emulsion layer to a polyester support is described in JP-A-48-
Plasma surface treatment represented by corona discharge treatment as described in JP-A No. 28067, JP-A No. 51-30274, etc.
A method incorporating the ultraviolet irradiation treatment described in No. 1-101077 or the like is known. Further, regarding the surface treatment by flame treatment as in the present invention, Japanese Patent Application Laid-Open No. 50-11357.
No. 8, JP-A-47-15625, JP-A-51-417.
No. 70, etc. However, the support examined in these patent examples is a polyester having a glass transition temperature of less than 90 ° C., such as polyethylene terephthalate, and even if the polyester having a glass transition temperature of 90 ° C. or more is treated in the same manner, it is halogenated. The silver emulsion layer cannot be adhered and the problem of the present invention cannot be solved. 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. Further, the current technology for preventing electrification has a problem that the material used is eluted into the processing liquid, so that the antistatic property is erased after the development processing and the dust adhered due to electrification is reflected at the time of printing.

[0005]

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.

[0006]

The above-mentioned object of the present invention can be achieved by the following silver halide photographic light-sensitive material of the present invention. That is, (1) a silver halide photographic light-sensitive material having a silver halide emulsion layer on at least one side of a polyester support has a glass transition temperature of 90 ° C. or higher and 20 ° C. or higher.
A silver halide photographic light-sensitive material characterized by subjecting at least one side of the polyester support made of polyester having a temperature of 0 ° C. or lower to a flame treatment, preferably (2) a glass transition temperature of 90 ° C. or higher. At least one side of the polyester support made of polyester having a temperature of 200 ° C. or lower is subjected to flame treatment, and at any point before or after the flame treatment, at a temperature of 50 ° C. or higher and lower than the glass transition temperature of the polyester support. The silver halide photographic light-sensitive material as described in (1) above, which is heat-treated.

First, the polyethylene aromatic dicarboxylate type polyester support which is the support of the present invention will be described. The glass transition temperature (Tg) of the polyester used in the present invention is preferably 90 ° C. or higher and 200 ° C. or lower. The Tg in the present invention is defined as follows using a scanning differential thermal analyzer (DSC). First, 10 mg of a 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.
Here, in the present invention, the sample is preferably a powdery amorphous polyester, but its value hardly changes even if a support is used. In the following description of the present specification, the glass transition temperature of the polyester support may be used for convenience of description, but the present invention is not limited thereto.

The aromatic polyester of the present invention comprises 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, 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 Acid, itaconic acid, citraconic anhydride, tetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid, halogenated terephthalic acid, bis (p-carboxyphenol) ether, 1 , 1-
Examples thereof include dicarboxy-2-phenylethylene, 1,4-dicarboxymethylphenol, 1,3-dicarboxy-5phenylphenol and sodium 3-sulfoisophthalate.

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.

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,
Further, 2,6-naphthalenedicarboxylic acid is preferable. The diol is preferably ethylene glycol (EG), polyethylene glycol (PEG), cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), bisphenol A (BPA) or biphenol (BP), and more preferably ethylene glycol. Also,
As the hydroxycarboxylic acid, parahydroxybenzoic acid (PHBA) or 6-hydroxy-2-naphthalenecarboxylic acid (HNCA) may be used.

These monomers are polymerized to form polyesters, and 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, in the present invention, a support produced using a polyester having a Tg of 90 ° C. or higher is preferable. On the other hand, there is no film which is transparent and is made of a general-purpose polyester having a Tg of more than 200 ° C. Therefore, the Tg temperature of the polyester used in the present invention is 90 ° C. or higher and 2
It is necessary to be not higher than 00 ° C.

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 (50/50/75/25) Tg = 112 ° C. P-7: TPA / EG / BPA (100/50/50) Tg = 10 ℃ 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)]

These supports of the present invention have a thickness of 50 μm or more and 300 μm or less. If it is less than 50 μm, it cannot withstand the shrinkage stress of the photosensitive layer generated during drying, whereas if it exceeds 300 μm, it is inconsistent with the purpose of reducing the thickness for compactness. More preferably from the strength of the waist, the thicker one is preferably 50 to 200 μm,
Furthermore, 80 to 115 μm is preferable, and 8 is particularly preferable.
It is 5 to 105 μm. All of the polyesters of the present invention as described above have a flexural modulus higher than that of TAC, and it was possible to realize the original thinning of the film. However, among these, PEN has strong bending elasticity.
By using this, it is possible to reduce the film thickness, which was required to be 122 μm for TAC, to 105 μm or less.

The heat treatment is carried out at a temperature of 50 ° C. or higher and lower than Tg, more preferably Tg −20 ° C. or higher and lower than Tg. 5
If the temperature is lower than 0 ° C., it takes a long time to obtain a sufficient curling effect, resulting in poor industrial productivity. The heat treatment may be performed at a constant temperature within this temperature range, or the heat treatment may be performed while cooling. The average cooling rate of cooling is −0.01 to −20 ° C./hour, more preferably −0.1 to −5 ° C./hour. This 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 less than 0.1 hours, a sufficient effect cannot be obtained, and 1
When the time is 500 hours or more, the effect is saturated, but the support is likely to be colored or brittle.

In order to further increase the effect of eliminating the curling habit, after the heat treatment is performed at a temperature not lower than Tg and lower than the melting point (melting temperature determined by DSC) before this heat treatment, the heat history of the support is erased. The heat treatment may be performed at a temperature of 50 ° C. or higher and lower than Tg. In the present invention, this heat treatment is referred to as "preheat treatment".
The heat treatment at 50 ° C. or higher and lower than Tg described in the previous section is called a “post heat treatment” to distinguish them. The preheat treatment temperature is Tg or higher and lower than the melting point, and more preferably Tg + 20 ° C. or higher and crystallization temperature (crystallization temperature determined by DSC) or lower.
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). Pre-heat treatment time is 0.1 minutes or more 1500
The time is less than or equal to the hour, more preferably 1 minute or more and less than 1 hour. If it is less than 0.1 minutes, a sufficient effect cannot be obtained,
After 1500 hours or more, the effect is saturated, while the support is likely to be colored or embrittled. After this pre-heat treatment, a post-heat treatment is performed. However, by rapidly cooling from the pre-heat treatment end temperature to the post-heat treatment start temperature. Alternatively, it may be gradually cooled to the post-heat treatment starting temperature across Tg. Alternatively, the temperature may be once cooled to room temperature and then raised to the post-heat treatment temperature. 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, the cooling rate from Tg to Tg−20 ° C. is -0.1- 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 in the form of a web while being conveyed. 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, unevenness is imparted by a treatment such as coating with conductive inorganic fine particles such as SnO ₂ or Sb ₂ O ₅ ) to reduce squeaking between the supports, which may cause winding tightening. It is desirable to take measures such as preventing wrinkles or preventing the cut edge of the winding core from appearing by giving a knurl to the end of the support and slightly raising the end only. 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.
This is because if the pre-heat treatment is carried out in the form of a web, a surface failure is less likely to occur than in the case of performing it in the form of a roll, and it is preferable to carry out the post-heat treatment in the form of a roll because it takes a relatively long time. Is.

These heat treatments may be carried out at any stage after the film formation on the support, after the flame treatment, after coating the back layer (antistatic agent, slipping agent, etc.), and after coating 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. Furthermore, in the method for heat-treating the polyester of the present invention, in order to shorten the time, heating is performed in advance to Tg or more for a short time (preferably 5 to 20 ° C. and 100 ° C. or less of Tg).
It is preferable that the treatment is performed for 3 minutes to 3 hours. Further, the roll core used in the heat treatment is preferably one having a built-in electric heater or a structure capable of flowing a high-temperature liquid so that it can be hollow or heated for efficient temperature propagation to the film. The material of the roll winding core is not particularly limited, but it is preferable that the material does not undergo strength reduction or deformation due to heat, such as stainless steel, aluminum,
A resin containing glass fiber can be mentioned. Further, rubber or resin may be lined on these winding cores, if necessary.

Next, the flame treatment of the present invention will be described. The flame treatment used in the present invention may be any conventional method. The flame treatment method may be natural gas or propane gas, but the mixing ratio with air is important, and the preferred gas / air mixing ratio is from 1/13 by volume.
The range is 1/21, particularly preferably 1/14 to 1/20. The flame treatment may be appropriately adjusted within the range of 1 to 50 kcal / m ² . Further, it is more effectively achieved by setting the distance between the tip of the internal flame of the burner and the polyester support to be treated to 0 to 4 cm. The position of the tip of the internal flame of the burner is defined as 0, the inside of the internal flame is defined as a negative number, and the outside of the internal flame is defined as a positive number.

The undercoat layer of the polyester support of the present invention may be any material conventionally used,
Specific examples thereof include monomers such as vinyl chloride, vinylidene chloride, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride and copolymers thereof, gelatin, nitrocellulose and the like. Of these, gelatin is particularly preferable. It is preferable to include a curing agent in these undercoat materials. As the curing agent, a polyamide-epichlorohydrin resin is preferable.

The polyamide-epichlorohydrin resin used in 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 reacting the polyamide with epichlorohydrin. The usual method of squeezing (for example, Japanese Examined Patent Publication No. 35-3547,
U.S. Pat. No. 292616, U.S. Pat. No. 3,125,552, 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 heat treatment method for improving the curl of the present invention will be described. The minimum core diameter of the conventional 135 system is 14 mm. If it is attempted to reduce the size to 5 to 11 mm, even if the polyester support of the present invention is used, a curl will be formed and a conveyance problem will occur during the development processing. If the outer diameter is less than 5 mm, the photographic emulsion suffers pressure overload, and the spool cannot be further reduced. To solve this problem of curl, we have found that when the film-formed polyester support of the present invention is heat-treated at a temperature of 50 ° C. or higher and lower than the glass transition temperature (Tg), a support having a marked curl is obtained. I found it.

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.

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 a commercially available dye such as Diaresin manufactured by Mitsubishi Kasei or Kayaset manufactured by Nippon Kayaku for polyester.

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 SiO2, TiO2, BaSO4, CaCO3,
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 SiO2 having a refractive index relatively close to that of the polyester film, or an internal particle system capable of making the precipitated particle diameter relatively small. 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.

Next, the antistatic agent of the present invention will be described. The most preferable antistatic agent of the present invention is Zn
O, TiO2, SnO2, Al2 O3, In2 O3, S
It is fine particles of at least one crystalline metal oxide selected from iO2, MgO, BaO, M0 O3 and V2 O5 or a composite oxide thereof. Among these, particularly preferable ones are those containing SnO2 as a main component and antimony oxide of about 5 to 20.
% And / or further other components (eg silicon oxide,
It is a conductive material containing boron, phosphorus, etc.). The fine particles of these conductive oxides or composite oxides thereof have a volume resistivity of 10 ⁷ Ωcm or less, more preferably 10 ⁵ Ωcm or less. The primary particle size is 0.002-0.7 μm, especially 0.005-0.3 μm.
Is desirable. 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,
It may be water-soluble or an organic solvent-based binder, or may be crosslinked like a latex. The resulting resistance of the antistatic layer 10 ¹² Ω~10 ³ Ω, and more preferably ¹⁰ 10 Ω~10 ³ Ω, more 10 ⁹ Ω~10 ³
Ω is preferred.

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 the 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 Engineering.
and Engineering), Volume 14, 248-257 (19
70 years); U.S. Pat. Nos. 4,434,226 and 4,4
14,310, 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.

As the silver halide emulsion, those which have been 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. The additives used in such a process are Research Disclosure N.
O. 17643 and N 0.18716, and the relevant parts are summarized in the table below. Known photographic additives that can be used in the present invention are also the above-mentioned two research products.
It is described in the disclosure, and the relevant parts are shown in the table below.

(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 may be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) N0.17643, 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. N0. 11449 and 2424
1, bleaching accelerator releasing couplers described in JP-A-61-2201247, ligand-releasing couplers described in U.S. Pat. No. 4,553,477, and JP-A-63-7574.
Examples thereof include couplers that release the leuco dye described in No. 7. 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 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, and the film swelling speed T1 /
2 is preferably 30 seconds or less. The film thickness is 25 ° C and relative humidity is 5
Means the film thickness measured under 5% humidity control (2 days), and the film swelling rate T1 / 2 can be measured according to a method known in the art. For example, A Green (A. Gree
n) Photographic Science and
Engineering (Photogr. Sci. Eng.), Volume 19, 2
No., pages 124-129, and can be measured by using a swellometer (swelling meter) of the type described above, and T1 / 2 is the maximum swelling film thickness reached when processed with a color developer at 30 ° C. for 3 minutes and 15 seconds. 90% of the saturated film thickness is defined as the time required to reach the film thickness of T1 / 2. 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 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 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.

[0041]

EXAMPLES First, a method for measuring a curl and a term relating to the method will be described. (1) Core set To wrap the film around the spool and add a curl. (2) Core set curl A curl in the length direction attached by the core set. The degree of curling is ANSI / ASC pH 1.29-1
Measured according to Test Method A of 985, 1 / R [m]
(R is the curl radius). (3) Absolute core set curl This is the core set curl of the photographic film before the curl is improved. (4) Controlled core set curl The core set curl of the photographic film after the curl has been improved. (5) True core set curl (Absolute core set curl)-(Controlled core set curl) (6) Curl reduction rate (True core set curl / Absolute core set curl) × 1
00

The present invention is further described below with reference to examples, but the present invention is not limited thereto. Example 1 1) Preparation of support After PET and PEN chips were melt extruded, they were stretched 3.4 times in the machine direction and 4 times in the transverse direction to prepare a biaxially stretched polyester support having a thickness of 80 μm. did.
PEN has an extrusion temperature of 300 ° C and a longitudinal stretching temperature of 140
C., the transverse stretching temperature of 130.degree. C., and the heat setting of 250.degree. On the other hand, PET has an extrusion temperature of 270 ° C., a longitudinal stretching temperature of 100 ° C., a transverse stretching temperature of 110 ° C.,
Supports T-1 to 3 were formed into a film by heat setting at 220 ° C for 6 seconds.

2) Heat Treatment and Surface Treatment of Support The support formed by the above method was subjected to post heat treatment under the conditions shown in Table 1. The post heat treatments were all carried out with the winding core having a diameter of 30 cm and the undercoat surface facing outside. In addition, those not subjected to the post heat treatment were designated as N-1 and T-1. After this, the supports N-1 to N-5,
The following flame treatment was performed on both surfaces of No. 7, T-1 to T-3.

[0044]

[Table 1]

A flame processing device manufactured by Kasuga Electric Co., Ltd. was used as the flame processing device. Both sides of the support, propane gas / air ratio = 1/17, flame treatment amount 20 kca
Flame treatment was performed at 1 / m ² and the distance between the inner flame and the support was 1 cm. For comparison, PEN film-formed under the same conditions on both sides without flame treatment is designated as N-6.

3) Coating of Undercoat Layer (Emulsion Layer Side) The supports N and T were coated with 10 ml / m ^{2 of} an undercoat solution having the following composition, dried at 115 ° C. for 2 minutes and then scraped off. Gelatin 1.0 parts by weight Water 1.0 parts by weight Acetic acid 1.0 parts by weight Methanol 50.0 parts by weight Ethylene dichloride 50.0 parts by weight P-chlorophenol 4.0 parts by weight A photosensitive layer described below is formed on this undercoat surface. It was painted.

4) Coating of Back Layer A back formulation having the following composition was coated on the surface opposite to the side where the undercoat layers of the supports N and T after undercoating were provided. (4-1) Preparation of conductive fine particle dispersion (tin oxide-antimony oxide composite dispersion) 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.
After roughly dispersing with a stirrer, the residence time is 30 with a horizontal sand mill (Dynomill, manufactured by Willy A. Backfen AG).
Dispersion was carried out until a minute, and primary particles were partially aggregated to prepare a dispersion liquid having a secondary aggregation of 0.05 μm.

(4-2) Coating of antistatic layer The following formulation was applied so that the dry film thickness would be 0.2 μm,
It was dried at 115 ° C for 30 seconds (At this time, the temperature inside the casing of the conveying system and the substantial temperature of the conveying roller were 115 ° C.
Was confirmed).・ Conductive fine particle dispersion (SnO ₂ / Sb ₂ O ₃ , 0.05 μm) 10 parts by weight ・ Gelatin 1 part by weight ・ Water 27 parts by weight ・ Methanol 60 parts by weight ・ Resorcin 2 parts by weight ・ Poly (degree of polymerization 10) oxy 0.01 parts by weight of ethylenenonylphenyl ether Further, a level N-7 containing no conductive fine particle dispersion was prepared.

(4-3) Coating of Back Layer A liquid having the following formulation was applied so that the dry film thickness was 1.5 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

(4-4) Coating 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 part compound (3-4) 0.7 g compound (5-3) 1.1 g xylene 2.5 g 2 parts propylene glycol model 34.0 g nomethyl ether The following binder and solvent were added to the above slip dispersion stock solution. An additional coating liquid was used. 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 .

5) Preparation of Light-Sensitive Material On the undercoated support (on the side opposite to the back layer), each layer having the following composition was multi-layered to prepare a sample as a multi-layer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows. ExC: Cyan coupler ExM: Magenta coupler ExY: Yellow coupler ExS: Sensitizing dye UV: Ultraviolet absorber HBS: High boiling organic solvent H: Gelatin hardener The numbers corresponding to each component are coatings expressed in g / m ² units For silver halide, the coating amount in terms of silver is shown. However, regarding the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10-3 Solid Disperse Dye ExF-2 0.030 Solid Disperse Dye ExF-3 0.040 HBS-1 0.15 HBS- 2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion M Silver 0.065 ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A Silver 0.25 Silver iodobromide 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-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium-Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C 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 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.40 ExS-1 2.4 × 10-4 ExS-2 1.0 × 10-4 ExS-3 3.4 × 10-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion E Silver 0.15 Silver iodobromide emulsion F Silver 0.10 Silver iodobromide emulsion G Silver 0.10 ExS-4 3.0 × 10-5 ExS-5 2.1 X10-4 ExS-6 8.0 x10-4 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) Silver Iodobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10-5 ExS-5 2.2 × 10-4 ExS-6 8.4 × 10-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10-3 Gelatin 0.80

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I 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 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

Layer 10 (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.60

11th layer (low-sensitivity blue emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.09 ExS-7 8.6 × 10-4 ExC-8 7.0 × 10-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 -3 HBS-1 0.28 Gelatin 1.20

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Silver 1.00 ExS-7 4.0 × 10-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10-3 HBS-1 0.070 Gelatin 0.70

13th layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 ExF-8 0.045 ExF-9 0.050 HBS-1 5.0 × 10-2 HBS-4 5.0 × 10-2 Gelatin 1.8

14th layer (second protective layer) Silver iodobromide emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70

Further, W-1 to W-3, B-4 to B- are added to each layer in order to improve storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0067]

[Table 2]

In Table 2, (1) Emulsions J to L 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 I 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 the tabular grains by using a high voltage electron microscope. (5) Emulsion L is a double structure grain containing an internal high iodine core described in JP-A-60-143331.

Preparation of Dispersion of Organic Solid Disperse Dye Dye ExF-2 shown below was dispersed by the following method. That is, water
21.7 ml and 3 ml of 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethane sulfonate and 0.5 g of 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (polymerization degree 10) and 0.5 g were put in a 700 ml pot mill, Add 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) to make the contents 2
Time dispersed. A BO type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After dispersion, take out the contents and take 12.5%
Add to 8 g of gelatin aqueous solution, filter out beads,
A gelatin dispersion of the dye was obtained. The average particle size of fine dye particles is
It was 0.44 μm.

Similarly, the dyes ExF-3 and ExF-4 are used.
And a solid dispersion of ExF-6 was obtained. The average particle diameters of the dye fine particles were 0.24 μm, 0.45 μm and 0.52 μm, respectively. The dye ExF-5 is a European Patent Application Publication (EP) No. 549,48.
The microprecipitation described in Example 1 of the 9A specification (Microprecipi
tation) dispersed by the dispersion method. Average particle size is 0.06μm
Met.

[0071]

[Chemical 1]

[0072]

[Chemical 2]

[0073]

[Chemical 3]

[0074]

[Chemical 4]

[0075]

[Chemical 5]

[0076]

[Chemical 6]

[0077]

[Chemical 7]

[0078]

[Chemical 8]

[0079]

[Chemical 9]

[0080]

[Chemical 10]

[0081]

[Chemical 11]

[0082]

[Chemical 12]

[0083]

[Chemical 13]

[0084]

[Chemical 14]

[0085]

[Chemical 15]

[0086]

[Chemical 16]

6) Evaluation of Photographic Film The photographic film samples N and T thus prepared were evaluated for curl according to the following procedure. 6-1) Core set The sample film was slit into a width of 35 mm and a length of 1.2 m. After humidity-adjusting this at 25 ° C. and 60% RH overnight, the photosensitive layer was wound inside and wound on a spool of 4 to 12 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. 6-2) Measurement of curl after development processing and evaluation of development processing unevenness and film breakage (film rear end breakage) The film having a curl under the above conditions was allowed to cool at 25 ° C, and then the sample film was removed from the sealed container. The film was taken out, developed with an automatic processor (Minilab FP-560B: manufactured by Fuji Photo Film Co., Ltd.), and subjected to curl measurement using a curl plate under the conditions of 25 ° C. and 60% RH. Curl measurement is A
NSI / ASC PH1.29-1985 Test
Measured using a curl plate according to Method A, 1 /
It is indicated by R [m] (R is the radius of the curl). Uneven development processing is processed by an automatic processor (Minilab FP-560B),
Visually observe the post-treatment film, and if it is uniformly treated, ○, after the treatment there is a little unevenness, but the printed image can not observe the unevenness, there is no practical problem △, the unevenness in the processed film When there was unevenness in the printed image, it was evaluated as x. The trailing edge folds of the film are processed by an automatic processor (Minilab FP-560B), and after processing, the film is visually observed. If there is no fold, it is ○, there is a slight fold, but there is no problem in conveyance during printing, and the printed image Also, the normal ones are Δ, and the ones that cause the film to be broken and hinder the conveyance during printing are marked with X.

The development processing conditions are shown below. The sample used for the measurement was processed using a processing solution prepared by separately subjecting a sample which had been previously subjected to imagewise exposure to a running process until the color development replenishing amount was replenished by 3 times the tank volume. Treatment process Temperature Time Color development 38 ° C 3 minutes Bleaching 38 ° C 2 minutes Fixing 38 ° C 3 minutes Washing 38 ° C 3 minutes Stabilizing bath 38 ° C 0.5 minutes

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 Add water to a total volume of 1 liter Bleach solution Ethylenediaminetetrairon (III) acetate dihydrate 100g Potassium bromide 50g Ammonium nitrate 50g Horic acid 5g Ammonia water Adjust pH to 5.0. Add water to make the total amount 1 liter Fixer Sodium thiosulfate 150 g Sodium sulfite 15 g Hoh sand 12 g Glacial acetic acid 15 ml Potassium alum 20 g Add water to a total amount 1 liter Stabilized bath 5 g Sodium citrate 5 g Sodium metaphorate (4 water salt) ) 3g RiAkiraban 15g Water to make total volume of 1 liter

6-3) Adhesion evaluation method at the time of drying The surface of the emulsion surface and the back surface were separated by a razor 6 at intervals of 5 mm in length and width.
Cut each book to make 25 squares, and then sticky tape (Nitto tape manufactured by Nitto Denki Kogyo Co., Ltd.) on top of this
Paste and peel off in 180 degree direction. In this method, those that do not peel are Class A, and the unpeeled portion is 95
% Or more is B grade, 90% or more is C grade, 60%
The above case is classified as D class, and the case of less than 60% is classified as E class. Adhesive strength that can withstand practical use as a photographic material is classified into A and B grades in the above-mentioned 5 grade evaluation.

6-4) Evaluation Method of Adhesion in Wetness At each of the above-mentioned processing steps of color development, fixing and stabilizing bath, scratch marks are marked on the emulsion surface and back surface of the film with a writing brush with a pencil. It was rubbed 5 times strongly with a fingertip with a rubber sack, and the adhesive strength was evaluated by the maximum peeling width peeled along the line x. Class A when the emulsion and back layer do not peel off more than scratches, and B when the maximum peeling width is 2 mm or more.
Class, when the maximum peeling width is within 5 mm, it is classified as C class, and the others are classified as D class. Adhesive strength that can withstand practical use as a photographic material is one that is classified into Class A in the above four-stage evaluation.

6-5) Static Mark Test The unexposed sample was conditioned at 25 ° C. and 10% RH for 6 hours, rubbed with a rubber roller and a urethane roller in a dark room under the same air conditioning conditions, and then automatically developed. Machine (Minilab FP-560B), and the generation degree of static marks was examined. The degree of occurrence of static marks is evaluated by the following 4
It was divided into stages. A: Static mark is not observed at all B: 〃 Somewhat recognized C: 〃 Significantly recognized D: 〃 Almost entirely recognized Photographic materials that can withstand practical use are grade A among the above four grades It is a thing classified into.

6-6) Dust Test A sample (20 cm × 20 cm) before and after the development treatment was rubbed well 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 four stages. A: No dust was seen at all B: 〃 Somewhat recognized C: 〃 Somewhat recognized D: 〃 was markedly recognized. A material that can withstand practical use as a photographic material is grade A among the above four grades. It is a thing classified into.

7) Results The results are shown in Table 3. The curls of N-1 and T-1 in which the support is not heat-treated in either PEN or PET are very large and rear end folds occur. When heat treatment is applied to PEN, the heat treatment temperature is higher than 50 ° C and lower than the Tg of PEN N-
2, while the curl of N-4 is very small and good, N-heat-treated at a temperature of Tg or higher or 50 ° C. or lower
Nos. 3 and N-5 had large curls and rear end folds were generated, and the effect of heat treatment was not observed. On the other hand, although the T-2 obtained by heat-treating PET at 60 ° C shows a slight heat treatment effect based on the result of curling, the curl of T-3 heat-treated at the expected summer vehicle temperature of 80 ° C does not show any improvement in curl. I can't. Further, it can be seen that when the support is subjected to flame treatment, good adhesion is achieved in both the emulsion layer and the back layer. Further, the one provided with a layer having electric conductivity has a good AS property after the developing treatment, whereas N-7 which does not contain a conductive layer has a poor AS property.

[0095]

[Table 3]

Example 2 1) Preparation of support PEN, PET, PAr, PCT to be used, and pellets of polyester copolymer shown in levels 17 to 23 of Table 4 were previously dried at 150 ° C. for 4 hours, and then used alone and The mixture was extruded at 280 ° C. using a twin-screw kneading extruder at a mixing ratio shown in Levels 3 to 11 in Table 4 and then pelletized. 100 parts by weight of this polyester and dye Dia so that the absorbance (400 nm) is 0.05 at a polyester thickness of 85 μm.
Resin (manufactured by Mitsubishi Kasei) was added, dried by a conventional method, melted at 300 ° C., and then extruded from a T-type die Tg +
Stretching was performed 3.3 times at 30 ° C., then transverse stretching was performed 3.3 times at Tg + 20 ° C., and further heat-set at 250 ° C. for 6 seconds to obtain film levels 1 to 23 having thicknesses shown in Table 4. It was

2) Post-heat treatment of the support When the support formed by the above method is wound up, the support is heated at the surface temperature of Tg + 10 ° C. shown in Table 4 and the support temperature of the winding core is Tg. Up to -5 ° C -0.05
The temperature was lowered at ° C / min, and post heat treatment was performed. All post heat treatments have a diameter of 3
A 0 cm winding core was used with the undercoat surface facing outside.

3) Surface treatment of support: Support levels 1, 3 to 6, 8 to 13, 15, 17 to 18,
The same flame treatment as in Example 1 was performed on both sides of Nos. 20-23. The flame-treated support was wound in contact with a cooling roll with a temperature controller of 50 cm in diameter so that the surface temperature was 30 ° C. before being wound up. For comparison, the following corona discharge treatment was performed on both sides of 2, 7, 14, 16, and 19. For corona discharge treatment, use Solid State Corona Disposer 6KVA model manufactured by Pillar Co., 30c
The m-width support was processed at 20 m / min. At this time, the object to be processed is 0.375 KV.A.
Min / m ² was processed. The discharge frequency during processing is
The gap clearance between the electrode and the dielectric roll was 9.6 KHZ and 1.6 mm.

4) Evaluation of Base Blocking Property After Surface Treatment After performing flame treatment or corona discharge treatment, base width 1
It was wound into a roll while applying a tension of 70 g per cm, and the blocking property after standing for 1 day was evaluated. Good ones that did not cause blocking were evaluated as ◯, and those that caused blocking were evaluated as x. 5) Coating of undercoat layer (emulsion layer side) Apply 10 ml / m ² of the undercoat solution of the following composition at 115 ° C.
And dried for 6 minutes. Gelatin 1.0 parts by weight Salicylic acid 0.3 parts by weight Resorcin 1.0 parts by weight Curing agent ^* 0.05 parts by weight Poly (polymerization degree 10) oxyethylene nonyl phenyl ether 0.1 parts by weight Water 2.2 parts by weight Methanol 95 0.35 parts by weight * Polyamide-epichlorohydrin resin shown below.

[0100]

[Chemical 17]

The emulsion layer, the antistatic layer, the back layer and the sliding layer were all coated in the same manner as in Example 1. 6) Evaluation of photographic film Evaluation of wrapping curl of the photographic film thus produced (folding of the trailing edge of the film during development processing) and adhesion during dry and wet was performed in the same manner as in Example 1.

7) Results The results are shown in Table 4.

[0103]

[Table 4]

Levels-1, 6, 13, 15, and 18 in which the glass transition temperature of the flame-treated polyester support of the present invention is 90 ° C. or higher and 200 ° C. or lower, the adhesion is good, whereas the flame-treated polyester support is flame-treated. Levels not performed-2, 7, 14, 16,
No. 19 has poor adhesion. Further, at a level -8 where the glass transition temperature of the polyester support is 90 ° C. or less, good adhesion is obtained, but the blocking property of the base after the surface treatment and the trailing edge fold of the film during the development process are poor, and the level -12 is also the surface treatment. It can be seen that the subsequent blocking property and the trailing edge fold of the film during development processing are inferior.

Example 3 1) Preparation of Supports Supports A-1 to 17 and B to G were prepared by the method described below.
It was created. Support A: 100 parts by weight of commercially available polyethylene-2,6-naphthalate polymer and Diaresin as a dye
(Manufactured by Mitsubishi Kasei) was added to have a thickness of 80 μm and an absorbance at 400 nm of 0.05, dried by a conventional method, melted at 300 ° C., and extruded from a T-die 140.
The film was longitudinally stretched 3.3 times at ℃, then transversely stretched 3.3 times at 130 ° C., and heat-set at 250 ° C. for 6 seconds to give a thickness of 5
Films of 5 μm, 60 μm and 80 μm were obtained. Support B: Commercially available polyethylene terephthalate polymer is biaxially stretched according to a suitable method and further heat-set to have a thickness of
A 0 μm film was obtained. Supports C, D, E, F, G: Dye concentration is added so as to be the same as that of Support A, after drying, melted at 300 ° C., extruded from T type die, and longitudinally stretched 3.3 times at Tg + 30 ° C. Then, the film was transversely stretched 3.3 times at Tg + 20 ° C., and heat-set at 250 ° C. for 6 seconds to obtain a film having a thickness shown in Table 5.

2) 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 5, and subsequently to the following surface treatment. 3) Surface treatment on support The propane gas / air mixing ratio and the amount of flame treatment for flame treatment were controlled under the conditions shown in Table 5. The distance between the internal flame and the surface of the support was the same as in Example 1.

5) Undercoat layer (emulsion layer side), antistatic layer,
The back layer, sliding layer and emulsion layer were formed in the same manner as in Example 2. Only A-14 was coated with a liquid containing no conductive fine particle dispersion instead of the antistatic layer.

6) Evaluation of Photographic Film Photographic Films A-1 to 17 and B thus prepared
About G: Gutter-like curl, pressure covering, film rear edge folding, adhesion during dry and wet, static mark test,
The evaluation of the test with dust was performed. 6-1) Gutter-like curl A sample coated with a photosensitive layer was slit into a width of 35 mm and a length of 1.2 m, and the humidity was adjusted overnight at 25 ° C. and 10% RH, which was then placed on a flat table. The photosensitive layer was placed so as to face down, and the height at that time was measured using a caliper. 7.0 m
Those having a value larger than m were represented by x, and the followings were similarly represented by o. 6-2) Pressure Covering A sample with a photosensitive layer was slit to a width of 1.2 mm with a width of 35 mm, wound on a spool shown in Table 6 and allowed to stand for 30 minutes. After development, the fog was visually evaluated. The product in which the fog was generated was represented by x, and the product in which it was not coated was represented by o.

7) Results The results are shown in Tables 5 and 6.

[0110]

[Table 5]

[0111]

[Table 6]

Effect of Support Flame Treatment on Adhesion While level A-1 without flame treatment on a PEN support having a glass transition temperature of 119 ° C. has poor adhesion,
The flame-treated levels A-2 to A-5 show practically no problem adhesion. It can be seen that although the propane gas / air mixing ratio is 1/13, it is in a practically good range, but a range of 1/14 to 1/20 is even better. Further, it can be seen from Levels A-7 to 10 that the flame treatment amount of 1 to 50 kcal / m ² shows very good adhesion, whereas the treatment amount of less than 1 kcal / m ² results in poor adhesion. Effect of the glass transition temperature of the support on the curl When the PEN support having a glass transition temperature of 119 ° C. is used, the trailing edge of the film during development processing does not occur. On the other hand, PET having a glass transition temperature of 69 ° C. causes the trailing edge of the film to be bent during development processing. It can be seen that the flame-treated polymers C to G having a Tg of 90 ° C. or more and 200 ° C. or less have good adhesion and no rear end breakage. Effects of pre-heat treatment above the glass transition temperature of the support and post-heat treatment below the glass transition temperature on the rear edge folds The levels A-6 and 11 without pre-heat treatment are the levels A-5 and 9 after pre-heat treatment. It can be seen that the rear end is badly broken in comparison. Also, the level of A-15 after post heat treatment at Tg of PEN or more
Indicates that the rear end breakage is worse than the levels A-5 and 9 after the post heat treatment at the Tg of PEN or less. Effect of Support Thickness and Spool Diameter Level A-12 with a PEN thickness of less than 50 μm produces a gutter-like curl, and a thickness greater than 50 μm does not occur. Further, at the level A-17 where the spool diameter is less than 5 mm, pressure is applied and both winding and winding deteriorate. Support thickness is 50 μm
From the above, it can be seen that when the outer diameter of the spool is 5 mm or more, it is effective for curling and pressure overload. Static mark of antistatic layer using metal oxide,
Effect with dust The resistance of level A-14 without metal oxide is 1 × 10 ^15.
Ω or more, the antistatic ability at low humidity (25 ° C., 10% RH) is poor, and the levels A-1 to 13 and 15 to 17 according to the invention.
Compared with (resistance is 1 × 10 ⁹ Ω), it is inferior in touch marks and dust. It can be seen that the use of a metal oxide having a volume resistivity of 1 × 10 ⁷ Ωcm or less has excellent antistatic ability.

[0113]

By carrying out the flame treatment of the present invention, a silver halide photographic light-sensitive material which is excellent in adhesion between the support and the emulsion layer and the back layer, is hard to curl, and has no rear end fold during development. I was able to create it. 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.

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Claims (9)

[Claims] 1. A silver halide photographic light-sensitive material having a silver halide emulsion layer on at least one side of a polyester support, the polyester support being made of polyester having a glass transition temperature of 90 ° C. or higher and 200 ° C. or lower. A silver halide photographic light-sensitive material, characterized in that at least one side thereof is subjected to flame treatment. 2. A flame treatment is applied to at least one side of the polyester support made of a polyester having a glass transition temperature of 90 ° C. or higher and 200 ° C. or lower, and 50 ° C. or higher at any point before or after the flame treatment. The silver halide photographic light-sensitive material according to claim 1, which is heat-treated at a temperature lower than the glass transition temperature of the polyester support. 3. The gas / air mixing ratio of the flame treatment is 1 /
The silver halide photographic light-sensitive material according to claim 1 or 2, which is flame-treated in the range of 13 to 1/21. 4. A silver halide photographic light-sensitive material according to any one of claims 1 to 3, wherein a polyamide-epichlorohydrin resin is contained in the undercoat of the polyester support. . 5. The silver halide photographic light-sensitive material according to claim 4, which has been preheated at a temperature of Tg or higher before the heat treatment. 6. The silver halide according to claim 1, wherein the polyester support is composed of a polyester containing naphthalenedicarboxylic acid and ethylene glycol as main components. Photographic material. 7. The photographic light-sensitive material has at least one conductive layer on at least one side, and the conductive conductive material of the conductive layer is Zn, Ti, Sn, Al, In, S.
The at least one selected from the group consisting of metal oxides containing i, Mg, Ba, Mo, W and V as main components and having a volume resistivity of 10 ⁷ Ωcm or less. The silver halide photographic light-sensitive material according to claim 6. 8. The silver halide photographic light-sensitive material is in the form of a roll wound around a spool having an outer diameter of 5 mm to 11 mm, according to any one of claims 1 to 7. Silver halide photographic light-sensitive material. 9. The silver halide photographic light-sensitive material according to claim 1, wherein the polyester support is polyethylene-2,6-naphthalenedicarboxylate. material.