JPH06202279A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material not giving curling tendency, superior in aptitude to perforation and dynamic characteristics and capable of compacting a cartridge. CONSTITUTION:The silver halide photographic sensitive material is provided with a support made by using a biaxially stretched polyester resin heat treated until an endothermic peak occurring striding a temperature of a glass transition point Tg becomes 100-1000mcal/g and having its lost elastic modulus (tan 6) of 0.01-0.1, a crystallization degree of 0.3-0.5, a Tg of 90-200 deg.C), a Young's modulus of 670-530kg/mm<2>, a breaking elongation percentage of 60-200%, and a refractive index ratio of film face direction to film thickness of 1.10-1.22.

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, and in particular, a heat-treated polyester having a specific mechanical property value is used as a support and a spool having an outer diameter of 5 to 11 mm is used. The present invention relates to a rolled silver halide photographic light-sensitive material which is wound, is hard to curl, and has excellent perforation processability.

[0002]

Photographic light-sensitive materials are generally prepared by coating at least one photographic light-sensitive layer on a plastic film support. As the plastic film, generally, a fiber type polymer represented by triacetyl cellulose (hereinafter referred to as “TAC”) and a polyester type polymer represented by polyethylene terephthalate (hereinafter referred to as “PET”) are used. Generally, as a photographic light-sensitive material, a film for X-ray,
A sheet-shaped product such as a plate-making film and a cut film, and a typical roll film have a length of 35 m.
It is a color or black and white negative film which is stored in a cartridge with a width of / m or less and is used for photographing by loading it in a general camera. TAC is mainly used as a support for roll films, but the greatest feature is that it has no optical anisotropy and high transparency. Another feature is that it has an excellent characteristic in decurling after development processing. That is, the characteristic of the TAC film due to its molecular structure is that it has relatively high water absorption as a plastic film,
The curling curl that occurs over time in the state of being wound as a roll film causes the molecular chains to flow due to water absorption in the development process, and the fixed molecular chains undergo rearrangement over time. As a result, it has an excellent property of eliminating curling curl once formed. TA like this
In a photographic light-sensitive material using a film having no curl curl recovery property such as C, when used in a roll state, scratches are generated in a printing process for forming an image on photographic printing paper after development, for example. However, problems such as defocusing and jamming at the time of transportation will occur. On the other hand, PET film has been considered as an alternative to TAC because of its excellent productivity, mechanical strength, and dimensional stability. However, in the roll form widely used as a photographic light-sensitive material, curling curl Remains strong and the handling property after development is poor, and the range of use has been limited despite the excellent properties described above.

By the way, the use of photographic light-sensitive materials has been diversified in recent years, and the speed of film transport at the time of photographing, the increase of photographing magnification, and the downsizing of photographing apparatus have been remarkably advanced. In that case, as the support for the photographic light-sensitive material,
Properties such as strength, dimensional stability, and thinning are required. Further, with the downsizing of the photographing device, there is an increasing demand for downsizing of the cartridge. In the conventional 135 system, a cartridge with a diameter of 25 mm has been used, but this spool (core) is set to 10 mm or less, and at the same time, the current 135
If the thickness of the TAC support used in the system is reduced from 122 μm to 90 μm, the thickness of the cartridge will be 20 mm.
The size can be reduced as follows. On the other hand, when the diameter of the spool is 3 mm or less, pressure fog is generated on the sensitive material, and it is impossible to further reduce the size. There are three problems in miniaturizing such a cartridge. The first problem is a reduction in mechanical strength as the film becomes thinner. In particular, bending elasticity decreases in proportion to the cube of the thickness. A silver halide photographic light-sensitive material is generally coated with a photosensitive layer dispersed in gelatin, and this layer causes shrinkage at low humidity to generate a toy-like curl. The support is required to have bending elasticity sufficient to withstand this contraction stress.

The second problem is the strong curl that occurs during storage over time as the spool becomes smaller. In the conventional 135 system, the winding diameter is the smallest in the cartridge 3
Even with a 6-shot film, the roll diameter is 14 mm. This one
When the size is reduced to 0 mm or less, a remarkable curl is generated, which causes various troubles. For example,
When developing with a minilab automatic developing machine, one end is fixed to the reader and the other end is not fixed, so the film winds up and the supply of the processing liquid is delayed, causing "processing unevenness". . Also, the roll-up of this film is crushed by the rollers in the minilab, causing "folding". A third problem is a reduction in processability such as perforation property due to an increase in the mechanical strength of the film. When it is attempted to improve the mechanical strength, particularly the elastic modulus in order to achieve further thinning, in the case of a biaxially stretched film, it is common practice to increase the draw ratio or the crystallinity. The film produced in this manner was a film that was brittle and easily opened, and problems such as easy occurrence of perforated scraps particularly at the time of perforation occurred.

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a silver halide photographic light-sensitive material having excellent mechanical properties, less curling, and excellent perforation properties. .

[0006]

These problems are addressed in a silver halide photographic light-sensitive material rolled in a roll in which at least one silver halide emulsion layer is provided on a support, and the glass transition of the support. The endothermic peak that appears across the temperature (Tg) is 100 mcal / g or more, 1000 m
heat treating the support until cal / g or less, and
Loss elastic modulus (tan δ) is 0.01 or more and 0.1 or less,
Crystallinity is 0.3 or more and 0.5 or less, Tg is 90 ° C or more 2
Young's modulus of 670 kg / mm ² or less 530 at 00 ° C or less
kg / mm ² or more, elongation at break 60% or more and 200% or less, ratio of refractive index in the film surface direction to the thickness direction is 1.22
This is achieved by a silver halide photographic light-sensitive material characterized by using a biaxially oriented polyester having physical properties of 1.10 or more as a support.

First, a description will be given of the measuring methods used hereinafter and terms relating to them. (1) Core set To wrap the film around the spool and add a curl.
Unless otherwise specified, after being wound on a winding core having a diameter of 8 mm, a heat treatment is performed at 80 ° C. for 2 hours so that the winding is performed. (2) Core set curl A curl in the length direction attached by the core set. The degree of winding is T of ANSI / ASC PH1.29-1985.
1 / R [m] measured according to est Method A
(R is the curl radius). (3) Glass transition temperature (Tg) and endothermic peak appearing across Tg. Using a differential thermal analyzer (DSC), sample film 10
The arithmetic mean temperature of the temperature at which deviation from the baseline begins and the temperature at which the temperature returns to the new baseline when Tg is increased in the helium-nitrogen stream at 20 ° C / min, or Tg
When an endothermic peak appears in, the temperature showing the maximum value of this endothermic peak is defined as Tg. When the DSC measurement of the sample film heat-treated at Tg or less is performed by the above method,
An endothermic peak appears near Tg. The two points where this endothermic peak returns to the baseline are connected by a straight line, and the area enclosed by this straight line and the endothermic peak is taken as the endothermic amount of the endothermic peak that appears across Tg. The "endothermic peak appearing across Tg" in the present invention means that the endothermic peak is such that Tg falls between the above two points.

(4) Loss Elastic Modulus (tan δ) The loss elastic modulus tan δ in the present invention is calculated by dividing the loss elastic modulus E ″ by the storage elastic modulus E ′ as tan δ = E ″ / E ′. E ″ and E ′ were measured using RHEO Vibro DDV-II-EA manufactured by Toyo Boardwin Co., Ltd., and the sample had a thickness of 75 μm, a length of 20 mm and a width of 2 m.
m, and the measurement conditions were a vibration frequency of 11 Hz and a dynamic displacement of ± 16 μm, and tan δ was calculated from E ″ and E ′ at 50 ° C. (5) Elongation at break / Young's modulus JIS-Z1702 According to -1976, width 10mm,
A strip having a length of 100 mm was measured at a pulling speed of 300 mm / min when measuring the breaking elongation and 20 mm / min when measuring the Young's modulus. (6) Refractive Index Using an Appe refractometer (1T type manufactured by Atago Co., Ltd.), measurement was performed at 25 ° C. using a D line of a sodium lamp. The refractive index is obtained in the film forming direction (MD), the transverse direction (TD) and the thickness direction (TH), and {(MD direction refractive index + TD direction refractive index) / 2} / (TH direction refractive index) is defined as the film surface direction. The ratio of the refractive indices in the thickness direction was used. (7) Crystallinity The density at 25 ° C. is measured using a density gradient tube in which carbon tetrachloride and n-hexane are mixed in an appropriate amount. The crystallinity is determined according to 100 × (density of sample film−amorphous density) / (density of crystal−amorphous density) (%). Amorphous samples were made by melting in a nitrogen stream at a temperature above the melting point for 5 minutes and then rapidly cooling in liquid nitrogen.
An amorphous sample prepared by the above method was crystallized isothermally at a crystallization temperature until no exotherm was observed in DSC.

In the present invention, by using the following biaxially stretched polyester for a photographic support, a photographic light-sensitive material satisfying three problems, namely mechanical strength, curling, and processability can be produced. The endothermic peak appearing across Tg. A method of making it difficult to cause curling by heat treatment at a temperature of Tg or lower is described in JP-A-51-16358 and is interpreted as follows. During film formation, the film is usually rapidly cooled from a temperature of Tg or higher in a rubber state to a temperature of Tg or lower in a glass state, so that the inside of the film after film formation is fixed in a rubber state having a large free volume. Therefore, the molecules inside are easily creeped, and as a result, the film is easily rolled. When such a film is heat-treated at a temperature of Tg or lower, the free volume is reduced, and the structure inside the film is changed so as to be in a stable glass state. A similar reduction in free volume can also be achieved by raising the temperature to Tg or higher and then performing cooling at a rate that catches up with the relaxation of the free volume of the film in the base. Therefore, such heat treatment makes the film less likely to creep and thus less likely to curl. The stable structure thus formed can be detected using a differential thermal analyzer (DSC). When the temperature is raised from Tg or lower, an endothermic peak is detected across Tg. This is because when the film forming a structure having a small free volume by heat treatment at Tg or less is heated to Tg, the frozen Micro Brownian motion is released and the rubber state rapidly becomes large in free volume. At this time, the energy of the difference from the stable structure to the rubber state is absorbed. This is observed by DSC. Therefore, this amount of heat absorption is a parameter of the size of the free volume and less likely to creep, and is less likely to be wound, and the larger the amount of heat absorption, the more difficult it is to wind.

When the endothermic peak is 100 mcal / g or less, a sufficient reduction in free volume cannot be obtained, and the curling tends to occur. On the other hand, the larger the heat absorption amount, the smaller the free volume and the more difficult it is to curl, but at the same time, it becomes a brittle film with low extensibility and the processability is deteriorated. Therefore, in order to obtain a film having a manufacturing suitability for a photographic support, there is an upper limit to this heat absorption amount as well, and the heat absorption amount is 1000 mcal / g.
The following are suitable supports. In addition, as the amount of heat absorption increases, the elongation of the effect on the curl becomes saturated, and 1000 mcal
Even if it goes over / g or more, the winding curl becomes almost the same value. Therefore,
When it is used as a photographic support, it has been clarified that the heat treatment should be performed so as to be 100 mcal / g or more and 1000 mcal / g or less.

Elongation at Break If the elongation at break is made too large, "beard" remains around the hole during drilling, resulting in a decrease in processing accuracy. On the other hand, if it is made too small, chips tend to be generated, and if it adheres to the film surface, it causes a failure. Therefore, it became clear that the breaking elongation is preferably 60% or more and 200% or less. Young's modulus When used as a photographic support, a layer of a hydrophilic binder is always coated as a photosensitive layer. Since this layer has water absorbency, it exhibits a large expansion / contraction behavior due to relative temperature. Therefore, the support must have a Young's modulus sufficient to counter this expansion / contraction. If you want to thin the film,
This becomes an even bigger problem. In the case of TAC support,
Since the Young's modulus is low, it cannot be made thinner than 100 μm. With PET, this can be made as thin as 90 μm. 530 kg / m to make it thinner than this
A Young's modulus of m ² or more is required. On the other hand, 670 kg /
If the height is increased to mm ² or more, the blade will be worn out significantly during drilling. Therefore, the Young's modulus is 530 kg / mm
It is necessary to use a support of ² or more and 670 kg / mm ² or less.

Refractive index ratio in the film surface direction and the thickness direction In order to make the film thinner, it is necessary to increase the Young's modulus as described above. In the case of biaxially oriented polyester, increasing the draw ratio is generally performed. Accordingly, the polymer molecules are oriented along the film surface, so that the refractive index in the film surface direction is high, while the refractive index in the film thickness direction is small. Therefore, the larger the ratio of the refractive index in the plane direction to the thickness direction (plane direction / thickness direction), the larger the Young's modulus. Therefore, in order to obtain a sufficient Young's modulus, this ratio needs to be 1.10 or more. On the other hand, if this ratio is too large, cracks are likely to be formed in the film surface direction in the cross-section that is punched during punching. This is because if the stretching is too strong and the molecular orientation is adjusted too much, the molecules will be arranged in layers in the film, and the layers will be easily peeled off, resulting in cracks due to the impact during perforation. In order to prevent this, the ratio of the refractive indexes needs to be 1.22 or less. Thus, the refractive index ratio between the film surface direction and the thickness direction must be 1.10 or more and 1.22 or less.

Crystallinity To increase the Young's modulus for thinning the film, increasing the crystallinity is also effective. In order to obtain a sufficient Young's modulus as described above, a crystallinity of 0.3 or more is indispensable. On the other hand, when this value is 0.5 or more, the life of the cutting edge is remarkably shortened during perforation, and the brittleness of the film is increased, which easily causes generation of scraps during perforation. Therefore, the crystallinity must be 0.3 or more and 0.5 or less. Loss elastic modulus (tan δ) tan δ represents the ratio of the viscous term and the elastic term.
The larger this value, the easier the loose flow. That is, it is shown that the curl is easy to be attached and is easily removed. The above-mentioned heat treatment makes it more difficult for the curl to stick, but it is more preferable that the curl once applied recovers during the development processing. As a measure for this, tan δ at 50 ° C. can be used.
If this value is 0.01 or less, the curl is hardly recovered during the development processing. On the other hand, if it is 0.1 or more, the curl is sufficiently restored, but on the other hand, the curl tends to be attached. Therefore, tan δ is 0.1 or less and 0.01 or less because it is difficult to curl and has good recoverability in development.
The above value is desirable.

Glass transition temperature (Tg) The curling reduction effect of the heat treatment of Tg or lower performed in the present invention disappears when exposed to a temperature of Tg or higher. This is because, when the glass having a small free volume due to the heat treatment is exposed to a temperature of Tg or higher, it is returned to the rubber having a large free volume, so that it is easy to be wound again. On the other hand, the highest temperature encountered in everyday photographic film is the temperature in a car in summer.
Here, it reaches about 80 ° C. Therefore, the Tg of the support needs to exceed this temperature, and the Tg of 90 ° C. or higher is required. Higher Tg is desirable, but it is versatile and there is no polymer film having a Tg of more than 200 ° C. Therefore, Tg is 9
The temperature is preferably 0 ° C or higher and 200 ° C or lower.

The support having such characteristics is 60 μm.
It is desirable to use it in the range of m to 122 μm. If it is 122 μm or more, it can be realized by TAC, and it is meaningless to use the polyester of the present invention. On the other hand, if it is attempted to reduce the thickness to 60 μm or less, an elastic modulus of 1500 kg / cm ² or more is required, which is versatile, and it is not currently possible to obtain this value with a transparent polymer film. Further, it is desirable that the spool around which this film is wound has a diameter of 5 mm to 11 mm. If the thickness is less than 5 mm, the emulsion layer is fogged by pressure and cannot be used. On the other hand, if the diameter is 11 mm or more, 3
The outer diameter of the film when wound for 6 shots is 18 to 20
It will be over mm, which is not much different from the current 135 system. Therefore, the spool should have a diameter of 5 mm to 11 mm.

As such a polymer film, biaxially stretched 2,6-polyethylene naphthalate (PEN)
And derivatives thereof. For example, the following can be mentioned. Homopolymer 2,6-Polyethylene naphthalate (PEN) Polymer composite At least one of polycyclohexanedimethanol (PCT), polycarbonate (PC), polyarylate (PAr), polyethylene terephthalate (PET), and polybutylene terephthalate (PBT) Polymer blend of type and PEN. PCT, PC, and PAr are preferably added from the viewpoint of increasing Tg and making it difficult to curl, but any of these is an amorphous polymer, and addition thereof reduces Young's modulus. Therefore, the blending ratio is preferably 30 parts by weight or less with respect to 100 parts by weight of PEN, in the total direction. On the other hand, P
Although ET and PBT have low Tg, they are less expensive than PEN. PE may be blended to reduce cost, but PE
It is desirable to add 30 parts by weight or less to 100 parts by weight of N. This is because if these are added too much, the Tg will be lowered and the material will be easily wound. In addition to such bunred, it may be used as a laminate of PEN and these polymers.

Copolymer 2,6-naphthalenedicarboxylic acid, ethylene glycol and ester thereof are used as main raw materials, and terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, succinic acid and glutaric acid are also used as dicarboxylic acids. , Adipic acid, sebacic acid, succinic anhydride, maleic acid, fumaric acid, maleic anhydride, itaconic acid, citraconic anhydride,
Tetrahydrophthalic anhydride, diphenylene p, p'-dicarboxylic acid, tetrachlorophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid,

[0018]

[Chemical 1]

[0019]

[Chemical 2]

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- Cyclohexanedimethanol, catechol, resorcin, hydroquinone, 1,4-pentendimethanol,

[0021]

[Chemical 3]

[0022]

[Chemical 4]

Etc. may be copolymerized. Other than this, a compound having a hydroxyl group and a carboxyl group (or its ester) at the same time in the molecule may be copolymerized. Examples of such compounds include:

[0024]

[Chemical 5]

Among these copolymers, the dicarboxylic acid component containing 2,6-naphthalenedicarboxylic acid and its ester in an amount of 70 mol% or more and the diol component containing ethylene glycol and its derivative in an amount of 70 mol% or more are preferable. desirable. When copolymerization is performed at a ratio higher than this,
This is because the regularity in the molecule is reduced and the crystallinity is significantly reduced, making it difficult to obtain the required Young's modulus. These PEN and 2,6-naphthalenedicarboxylic acid and derivatives, and the copolymers of these ester bodies and ethylene glycol and derivatives as the main raw materials can be synthesized according to conventionally known polyester production methods. For example, when the acid component is directly esterified with the glycol component, or when a dialkyl ester is used as the acid component, first, the transesterification reaction with the glycol component is performed, and this is heated under reduced pressure to remove the excess glycol component. By doing
Can be synthesized. Alternatively, the acid component may be an acid halide and reacted with glycol. On this occasion,
If necessary, a transesterification reaction, a catalyst or a polymerization reaction catalyst may be used, or a heat resistance stabilizer may be added. Regarding these polyester synthesis methods, for example, Polymer Experimental Science Vol. 5, "Polycondensation and Polyaddition" (Kyoritsu Shuppan, 1980)
Years) 103-136, "Synthetic Polymer V" (Asakura Shoten, 1971), pages 187-286.

The preferred average molecular weight range for these polyesters is about 10,000 to 500,000. The polymer blends of the polymers thus obtained are described in JP-A-49-5482 and 64-432.
5, JP-A-3-192718, Research Disclosure 283, 739-41, 284, 779-8.
2, according to the method described in 294, 807-14,
It can be easily formed.

An ultraviolet absorber may be kneaded into the polymer thus synthesized for the purpose of preventing fluorescence and 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 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, 2,2 ', 4. 4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,
Benzophenone-based compounds such as 4'-dimethoxybenzophenone, 2 (2'-hydroxy-5-methylphenyl) benzotriazole, 2 (2'-hydroxy 3 ', 5'-di-t-butylphenyl) benzotriazole, 2 (2 ′
Examples thereof include benzotriazole-based UV absorbers such as -hydroxy-3'-di-t-butyl-5'-methylphenyl) benzotriazole and salicylic acid-based UV absorbers such as phenyl salicylate and methyl salicylate.

Further, one of the properties which poses a problem when the polyester film is used as a support for a photographic light-sensitive material is a problem of fogging due to the high refractive index of the support. Polyester, particularly aromatic polyester, has a high refractive index of 1.6 to 1.7, while gelatin, which is the main component of the photosensitive layer coated on the polyester, has a refractive index of 1.50 to 1.55. Less than this value. Therefore, when light enters from the film edge, it is easily reflected at the interface between the base and the emulsion layer. Therefore, the polyester film causes a so-called light piping phenomenon (fogging). As a method of avoiding such a light piping phenomenon, a method of adding inert inorganic particles and the like to the film, a method of adding a dye, and the like are known. The preferred method for preventing light piping in the present invention is a method by adding a dye that does not significantly increase the film haze. The dye used for film dyeing is not particularly limited, but the color tone is preferably gray dyeing due to the general property of the light-sensitive material, and the dye is excellent in heat resistance in the film forming temperature range of the polyester film, and polyester Those having excellent compatibility with are preferable. From the above viewpoints, as the dye, it is possible to achieve the object by mixing a commercially available dye for polyester such as Diaresin manufactured by Mitsubishi Kasei or Kayaset manufactured by Nippon Kayaku with these polymers. Regarding the dyeing density, it is necessary to measure the color density in the visible light region with a color densitometer manufactured by Macbeth Co. and be at least 0.01 or more. More preferably, it is 0.03 or more.

It is also possible to impart slipperiness according to the application, and the slipperiness imparting means is not particularly limited, but kneading with an inert inorganic compound or adding a surfactant Coating or the like is used as a general method. Such inert inorganic particles include SiO ₂ , Ti
Examples thereof include O ₂ , BaSO ₄ , CaCO ₃ , talc, kaolin and the like. 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. These slipperiness imparting means are not particularly limited, but transparency is an important requirement for the support for a photographic light-sensitive material. It is desirable to select SiO ₂ having a refractive index relatively close to that, or an internal particle system capable of relatively reducing the precipitated particle size.

The above-mentioned homopolymer is a polymer composite,
If necessary, after kneading these dyes, UV absorbers and mobilizers into the polymer blend, dry them 3
After melting at 00 ° C., it is extruded from a die with a thickness of 900 μm (a laminate is co-extruded from a multi-manifold die), cast on a casting drum, and longitudinally stretched 3.5 times at 153 ° C., and then 130 ° C. Was transversely stretched to 3.8 times and further heat-set at 250 ° C. for 6 seconds. Further, this was annealed at 110 ° C. for 24 hours to obtain 90% of the present invention.
A photographic support having a thickness of μm was obtained. Although these examples are shown in Table 1, the present invention is not limited thereto.

[0031]

[Table 1]

Further, when imparting slipperiness by kneading, a method of laminating a layer imparted with a function in order to obtain more transparency of the film is also preferable. Specific examples of this means include a co-extrusion method using a plurality of extruders and feed blocks, or a multi-manifold die. When these polymer films are used for a photographic support, since each of these polymer films has a hydrophobic surface, a photographic layer comprising a protective colloid mainly containing gelatin on the support (for example, a photosensitive silver halide). It is very difficult to firmly adhere the emulsion layer, intermediate layer, filter layer, etc.). The conventional techniques attempted to overcome such difficulties are (1) chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment. , A method of surface activation such as mixed acid treatment, ozone oxidation treatment, etc., and then directly applying a photographic emulsion to obtain the adhesive force, and (2) after these surface treatments once or without surface treatment, There are two methods: a method of providing an undercoat layer and a method of coating a photographic emulsion layer on the undercoat layer. (For example, US Pat. No. 2,69
8,241, 2,764,520, 2,86
4,755, 3,462,335, 3,47
5,193, 3,143,421, 3,50
1,301, 3,460,944, 3,67
4,531, British Patents 788,365, 80
No. 4,005, No. 891,469, Japanese Patent Publication No. 48-43
122, 51-446, etc.).

All of these surface treatments are considered to be caused by forming a polar group on the surface of the support which was originally hydrophobic, and increasing the crosslink density of the surface. As a result, It is considered that the affinity of the component contained in the undercoat liquid with the polar group is increased, or the fastness of the adhesive surface is increased. In addition, various arrangements have been made for the composition of the undercoat layer. A layer that adheres well to the support (hereinafter referred to as the first undercoat layer) is provided as the first layer, and a second layer is used as a photograph. A so-called multi-layer method of applying a hydrophilic resin layer (hereinafter, abbreviated as the second undercoat layer) that adheres well to a layer, and a single layer of applying a single resin layer containing both a hydrophobic group and a hydrophilic group There is a law. Among the surface treatments of (1), corona discharge treatment is the most well-known method, and any conventionally known method, for example, JP-B-48-5.
043, 47-51905, JP-A-47-280.
No. 67, No. 49-83767, No. 51-41770.
No. 51-131576 and the like. Discharge frequency is 50Hz-5000
A suitable frequency is kHz, preferably 5 kHz to several hundreds of kHz.
If the discharge frequency is too low, stable discharge cannot be obtained and pinholes are generated in the object to be treated, which is not preferable. On the other hand, if the frequency is too high, a special device for impedance matching is required, which increases the cost of the device, which is not preferable. Regarding the treatment strength of the object to be treated, 0.001 KV · A · min / m ^{2 to 5} KV · A is required to improve the wettability of ordinary plastic films such as polyester and polyolefin.
・ Min / m ² , preferably 0.01 KV ・ A ・ Min / m ^{2 to 1} KV ・
A · min / m ² is appropriate. The gap clearance between the electrode and the dielectric roll is 0.5 to 2.5 mm, preferably 1.
0 to 2.0 mm is suitable.

In many cases, the glow discharge treatment, which is the most effective surface treatment, is carried out by any conventionally known method, for example, Japanese Patent Publication Nos. 35-7578 and 36-1033.
No. 6, No. 45-22004, No. 45-22005,
45-2440, 46-43480, U.S. Pat. Nos. 3,057,792, 3,057,795, 3,179,482, 3,288,638 and 3,309. No. 299, No. 3,424,735, No. 3,462,335, No. 3,475,307, No. 3,761,299, British Patent 997,093, JP-A No. 53-129262, etc. Can be used. The glow discharge treatment condition is generally a pressure of 0.005 to 20 To
rr, preferably 0.02 to 2 Torr is suitable. If the pressure is too low, the surface treatment effect will be reduced, and if the pressure is too high, an excessive current will flow and sparks will easily occur, which is dangerous and may damage the object to be treated. The electric discharge is generated by applying a high voltage between metal plates or metal rods arranged in a vacuum tank with one or more pairs of spaces. This voltage can take various values depending on the composition of the atmospheric gas and the pressure, but it is usually 500 within the above pressure range.
A stable steady-state glow discharge occurs between ~ 5000V. A particularly suitable voltage range for improving adhesion is 2000
~ 4000V. The discharge frequency is, as seen in the prior art, from DC to several thousand MHz, preferably 50 Hz to 20 MHz. Regarding the discharge treatment strength, 0.01KV ・
A · min / m ^{2 to 5} KV · A · min / m ² , preferably 0.15 KV
・ A ・ min / m ² 〜 1KV ・ A ・ min / m ² is appropriate.

Next, regarding the undercoating method (2), all of these methods have been well studied, and for example, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid can be used for the first layer of the undercoating in the multi-layer method. A large number of polymers such as polyethyleneimine, epoxy resin, grafted gelatin, and nitrocellulose, including copolymers starting from monomers selected from the group consisting of itaconic acid, maleic anhydride, etc. Layers have been investigated for their properties primarily with respect to gelatin. In the single layer method, in many cases, good adhesion is achieved by swelling the support and interfacial mixing with the hydrophilic undercoat polymer. As the hydrophilic undercoat polymer used in the present invention, a water-soluble polymer, a cellulose ester,
Examples include latex polymers and water-soluble polyesters. Water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch,
Examples thereof include polyvinyl alcohol, polyacrylic acid copolymer, and maleic anhydride copolymer, and examples of cellulose ester include carboxymethyl cellulose and hydroxyethyl cellulose. Examples of the latex polymer include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylic acid ester-containing copolymers, vinyl acetate-containing copolymers and butadiene-containing copolymers. Of these, gelatin is the most preferable. As the compound for swelling the support used in the present invention, resorcin, chlorresorcin, methylresorcin, o-cresol,
Examples thereof include m-cresol, p-cresol, phenol, o-chlorophenol, p-chlorophenol, dichlorophenol, trichlorophenol, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid and chloral hydrate. Of these, resorcin and p-chlorophenol are preferred.

Various gelatin hardeners can be used in the subbing layer of the present invention. As gelatin hardening agents, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine, etc.), epichlorohydrin resin And so on. The subbing layer of the present invention is S
Inorganic particles such as iO ₂ , TiO ₂ and matting agent or polymethylmethacrylate copolymer particles (1 to 10 μm)
m) can be included. In addition to this, the undercoat liquid may contain various additives as required. For example, surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids, antifoggants and the like. In the present invention, when the undercoat liquid for the first undercoat layer is used, it is not necessary to include an etching agent such as resorcin, chloral hydrate, chlorophenol, etc. in the undercoat liquid. However, if desired, an etching agent as described above may be contained in the base coat.

The undercoating liquid according to the present invention is a well-known coating method, for example, tip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, or US Pat. It can be applied by the extrusion coating method using the hopper described in the specification of 2,681,294. If desired, US Pat. No. 2,761,791
Issue No. 3,508,947 Issue 2,941,898
, And 3,526,528, Yuji Harasaki,
Two or more layers can be simultaneously coated by the method described in “Coating Engineering”, page 253 (1973, published by Asakura Shoten).

The binder of the back layer may be a hydrophobic polymer or a hydrophilic polymer used in the subbing layer. The back layer of the light-sensitive material of the present invention may contain an antistatic agent, a slip agent, a matting agent, a surfactant, a dye and the like. The antistatic agent used in the back layer of the present invention is not particularly limited, and for example, as the anionic polymer electrolyte, carboxylic acid and carboxylic acid salt,
A polymer containing a sulfonate is disclosed in, for example, JP-A-48-220.
17, JP-B-46-24159, JP-A-51-30
725, JP-A-51-129216, JP-A-55-
It is a polymer as described in No. 95942. Examples of the cationic polymer include, for example, JP-A-49-12152.
3, JP-A-48-91165, JP-B-49-245.
No. 82 is available. Further, the ionic surfactant has anionic property and cationic property. For example, JP-A-49-85826 and JP-A-49-33630 are available.
No., US2,992,108, US3,206,31
2, JP-A-48-87826, JP-B-49-1156
7, JP-B-49-11568, JP-A-55-708.
Compounds such as those described in No. 37 can be mentioned. The most preferable antistatic agent for the back layer of the present invention is ZnO, TiO ₃ , SnO ₂ , Al ₂ O.
₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃
It is fine particles of at least one crystalline metal oxide or a composite oxide thereof selected from the above. The fine particles of the conductive crystalline oxide or the composite oxide thereof used in the present invention have a volume resistivity of 10 ⁷ Ωcm or less, more preferably 10 ⁵ Ωcm or less. The particle size is 0.0
It is desirable that the thickness be 1 to 0.7 μ, particularly 0.02 to 0.5 μ.

Regarding the method for producing fine particles of a conductive crystalline metal oxide or composite oxide used in the present invention, JP-A-56-143430 and JP-A-60-258541 are used.
In the specification of the issue. First, a method of producing metal oxide fine particles by firing and performing heat treatment in the presence of a heteroatom that improves conductivity, and second, a method of improving conductivity when producing metal oxide fine particles by firing. A method of making atoms coexist, a third method of introducing oxygen defects by lowering the oxygen concentration in the atmosphere when producing metal fine particles by firing, and the like are easy. Examples of containing different kinds of atoms include Al, In, etc. for ZnO, Nb, Ta, etc. for TiO ₂ , Sb, Nb, halogen elements, etc. for SnO ₂ . The addition amount of the heteroatom is 0.01 to
The range of 30 mol% is preferable, but 0.1 to 10 mol%
If so, it is particularly preferable.

Next, the photographic layer of the photographic light-sensitive material of the present invention will be described. The silver halide emulsion layer may be any of black and white colors. 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 layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer provided on a support, and a silver halide emulsion. 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 consisting 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 a color sensitivity to any of blue light, green light, and red light. The arrangement is such that the red-sensitive layer, the green-sensitive layer and the blue-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-61-43
748, 59-113438, 59-1134
No. 40, No. 61-20037, No. 61-20038 may contain a coupler, a DIR compound, etc. as described in the specification, and may contain a color mixing inhibitor as is commonly used. . A plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,4.
70 or British Patent No. 923,045, JP-A-5
7-112751, 62-200350, 62
-206541, 62-206543, 56-
25738, 62-63936, 59-202.
No. 464, Japanese Patent Publication Nos. 55-34932, 49-154
No. 95. The silver halide grains are
Those with regular crystals such as cubes, octahedra and tetradecahedrons, those with irregular crystal shapes such as spheres and plates, those with crystal defects such as twin planes, or those It may be a composite type.

The grain size of the silver halide may be fine grains of about 0.2 micron or less or large grains having a projected area diameter of up to about 10 microns, 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.
17643 (December 1978), pp. 22-23,
"I. Emulsion preparation and types",
And No. 18716 (November 1979), 648.
P. Glafkides, Chemie et Phisique Photograp, "Physics and Chemistry of Photography," by Graphide.
hique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin Photo
graphic Emulsion Chemistry (Focal Press, 196
6), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et al., Making an
d Coating Photographic Emulsion, Focal Press, 19
64) and the like. U.S. Pat. Nos. 3,574,628 and 3,65
The monodisperse emulsions described in, for example, 5,394 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, Pho
tographic Science and Engineering), Volume 14, 24
8-257 (1970); U.S. Pat. No. 4,434,434.
No. 226, No. 4,414, 310, No. 4,433, 0
48, 4,439,520 and British Patent No. 2,
It can be easily prepared by the method described in No. 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 compounds other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. The efficiency of the present invention is particularly remarkable when an emulsion sensitized with a gold compound and a sulfur-containing compound is used. Additives used in such processes are Research Disclosure 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
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, 249,453A, U.S. Patents 3,446,622, 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 the polymerized dye-forming couplers are U.S. Pat.
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 US Pat. No. 4,130,427, US Pat. Nos. 4,283,472, and 4,338,393. No. 4,310,618 and the like, multiequivalent couplers, JP-A-60-185950.
No. 2, 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, 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 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 means a film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T1 / 2 can be measured according to a method known in the art. For example, A Green (A.
Green) et al., Photographic Science and Engineering (Photogr. Sci. Eng.), 19
It can be measured by using a swellometer (swelling meter) of the type described in Vol. 2, No. 2, p.
Is 90% of the maximum swollen film thickness reached when the film is processed with a color developing solution at 30 ° C. for 3 minutes and 15 seconds.
It is defined as the time to reach the film thickness of. Membrane swelling speed T
1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is 150-40.
0% is preferable. 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, pp. 28-29, and N.
Development can be carried out by a usual method described in the left column to the right column of 615 of o. 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, US Pat. Nos. 3,342,597, indoaniline compounds, 3,342,599, Research Disclosures 14,850 and 15,
Schiff base type compound described in No. 159, No. 13,924
No.

[0049]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Example 1 1) Preparation of Supports The following Supports A to C were prepared by the method described below. Support A (polyethylene naphthalate (PEN): thickness 55 μm, 65 μm, 90 μm) Support B (polyethylene terephthalate (PET): thickness 90 μm) Support C (triacetyl cellulose (TAC): thickness 1
10, 122 μm) Support A: 100 parts by weight of commercially available polyethylene-2,6-naphthalate polymer and Tinuv as an ultraviolet absorber
inP. 2 parts by weight of 326 (manufactured by Geigy Co.) were dried by a conventional method, melted at 300 ° C., and then longitudinally stretched, laterally stretched and heat set under the conditions shown in Table 2-1 to obtain thicknesses 55, 65, 9
A 0 μm film was obtained. Support B: A commercially available polyethylene terephthalate polymer was biaxially stretched and heat-set according to a conventional method to obtain a film having a thickness of 90 μm. Support C: methylene chloride / methanol = 82/8 wt of triacetyl cellulose by a normal solution casting method
Ratio, TAC concentration 13% Plasticizer TPP / BDP = 2/1
(Here TPP; triphenyl phosphate, BD
P: Biphenyldiphenylphosphate) 15 wt
% Band method.

[0050]

[Table 2]

[0051]

[Table 3]

2) Surface Treatment of Supports Supports A and B were each subjected to UV light treatment on both sides.
In the UV light treatment, the support was heated to 200 ° C. and irradiated with a 1 kW high pressure mercury lamp from a distance of 20 cm for 30 seconds. 3) Heat Treatment of Supports Supports A and B were subjected to heat treatment after surface treatment in order to reduce curling. All the supports of A except A-2 have a diameter of 30c.
Wrap the emulsion coating surface on the m core by wrapping 110
It heat-processed at 24 degreeC for 24 hours. Only the A-2 support was heat-treated at a temperature of Tg or higher, that is, by slowly cooling from 130 ° C. to 110 ° C. over 2 hours. The support B was also wound on a core having a diameter of 30 cm with the emulsion-coated surface outside and heat-treated at Tg or less, that is, 60 ° C. for 72 hours.

3) Coating of undercoat layer For the supports A and B, an undercoat liquid having the following composition was used in an amount of 10 ml / m ^2.
It was applied and dried at 110 ° C. for 2 minutes. Gelatin 1 part by weight Distilled water 1 part by weight Acetic acid 1 part by weight Methanol 50 parts by weight Ethylene chloride 50 parts by weight p-Chlorophenol 4 parts by weight Support C is applied with an undercoating liquid of the following composition at 20 ml / m ² and at 90 ° C. It was dried for 3 minutes. Gelatin 275 parts Formaldehyde 12.1 parts Salicylic acid 82.4 parts Methanol 4372 parts Methylene chloride 22200 parts Acetone 31000 parts Distilled water 626 parts

4) Coating of Back Layer A back layer having the following composition was coated on the surface opposite to the side on which the undercoat layer of the supports A to C after undercoating was provided. 4-1) Preparation of conductive fine particle dispersion (tin oxide-antimony oxide composite dispersion): 230 parts by weight of stannic chloride hydrate and 23 parts by weight of antimony trichloride were added to 300 parts of ethanol.
It was dissolved in 0 part by weight to obtain a uniform solution. A 1N aqueous sodium hydroxide solution was added dropwise to this solution until the pH of the solution reached 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate. The reddish brown colloidal precipitate was separated by centrifugation. To remove excess ions, water was added to the precipitate and washed by centrifugation. This operation was repeated 3 times to remove excess ions. 200 parts by weight of the colloidal precipitate from which excess ions were removed was redispersed in 1500 parts by weight of water and sprayed in a baking furnace heated to 600 ° C. to obtain a bluish tin oxide-antimony oxide composite having an average particle size of 0.2 μm. Fine particle powder of The specific resistance of this fine particle powder was 25 Ω · cm. A mixed solution of 40 parts by weight of the fine particle powder and 60 parts by weight of water was adjusted to pH 7.0, and roughly dispersed by a stirrer, and then a horizontal sand mill (trade name: Dynomill; WI).
LLYA. BACHOFENAG) with a residence time of 30
It was prepared by dispersing until it reached the end.

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

5) Evaluation of Support Regarding the support which has been subjected to undercoating and coating of the back layer,
The following evaluation was performed according to the method described above. (A) Tg and heat absorption at Tg DSC after scraping off the undercoat and back surfaces with a razor
Measured using. (B) Crystallinity The undercoat surface and the back surface were scraped off with a razor, and then measured using a density gradient tube. (C) tan δ REO VIBRON with undercoat and back layer
(Made by Toyo Baldwin). (D) Young's modulus, elongation at break Measured using a tensile tester with the undercoat and the back layer attached. (E) Refractive index ratio Measured with an Abbe ′ refractometer before coating the back layer and the undercoat layer, after UV light treatment, and after heat treatment.

5) Coating of Photosensitive Layer On the support obtained by the above-mentioned method, each layer having the composition shown below is multilayer-coated to form multilayer color photosensitive materials A-1 to 21 and B-.
1, C-1 and C-2 were created. (Photosensitive layer composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ⁻³ HBS-1 0.20

Second Layer (Intermediate Layer) Emulsion G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-7 0.0050 ExC-8 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

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

Fifth Layer (High Sensitivity Red Sensitive Emulsion Layer) Emulsion E Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.12 ExC-3 0.045 ExC-6 0.020 ExC-8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20

Sixth Layer (Intermediate Layer) Cpd-1 0.10 HBS-1 0.50 Gelatin 1.10

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

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

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

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

Eleventh layer (low-sensitivity blue emulsion layer) Emulsion C Silver 0.18 ExS-7 8.6 × 10 ^-4 ExY-1 0.020 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 HBS-1 0.28 Gelatin 1.10

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

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

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

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

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

[0074]

[Table 4]

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

[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]

[0087]

[Chemical 17]

[0088]

[Chemical 18]

[0089]

[Chemical 19]

[0090]

[Chemical 20]

6) Evaluation of Film with Emulsion 6-1) Evaluation of Rolled Film Photographic film sample A-2 thus prepared
Winding evaluation was performed on Nos. 1, B-1, and C-1 and C-2. The evaluation was performed according to the following procedure. The core set sample film was slit into a width of 35 mm and a length of 1.2 m. This was conditioned at 25 ° C. and 60% RH overnight, then the inner side of the photosensitive layer was adjusted to 4 to 12 as shown in Tables 2-1 to 2-2.
Wrapped around a mm spool. This was placed in a sealed container, heated at 80 ° C. for 2 hours and wound. This temperature condition is a condition on the assumption that the film was placed in a car during the daytime in summer. Development processing, curl measurement After the film wound under the above conditions was allowed to cool in a room at 25 ° C overnight, the sample film was taken out from the sealed container, and immediately after curl measurement using a curl plate,
This was developed with an automatic processor (Minilab FP-550B: manufactured by Fuji Photo Film Co., Ltd.) and immediately subjected to curl measurement using a curl plate at 25 ° C. and 60% RH. Also, at this time, check whether the back end of the film is broken,
The ones in which no breakage occurred are indicated by ◯, and the ones in which breakage occurs are indicated by x, and are shown in Table 2-2. The development processing conditions are as follows.

Treatment process Temperature Time Color development 38 ° C. 3 minutes Stop 38 ° C. 1 minute Water wash 38 ° C. 1 minute Bleach 38 ° C. 2 minutes Water wash 38 ° C. 1 minute Fixation 38 ° C. 2 minutes Water wash 38 ° C. 1 minute Stabilizing bath: 38 ° C. for 1 minute The treatment liquid used has the following composition. Color developer Caustic soda 2g Sodium sulfite 2g Potassium bromide 0.4g Sodium chloride 1g Hoh sand 4g Hydroxylamine sulfate 2g Ethylenediaminetetraacetic acid disodium dihydrate 2g 4-Amino-3-methyl-N-ethyl-N- (β -Hydroxyethyl) aniline monosulfate) 4g Water added to make a total of 1 liter

Stop solution Sodium thiosulfate 10 g Ammonium thiosulfate (70% aqueous solution) 30 ml Acetic acid 30 ml Sodium acetate 5 g Potassium alum 15 g Water-added total 1 liter Bleach solution Ethylenediaminetetrairon (III) acetate dihydrate 100 g Bromide Potassium 50g Ammonium nitrate 50g Horic acid 5g Ammonia water Adjust the pH to 5.0 and add water to a total volume of 1 liter Fixer Sodium thiosulfate 150g Sodium sulfite 15g Hog sand 12g Glacial acetic acid 15ml Potassium alum 20g Add water to a total volume of 1 liter Stable Bath Folic acid 5 g Sodium citrate 5 g Sodium metaphoric acid (tetrahydrate) 3 g Potassium alum 15 g Total volume with water 1 liter

6-2) Perforability These films were perforated by using the perforation apparatus shown in the examples of JP-A 1-210299. 13 perforations
Both ends of the film were performed according to the method of the 5 system. 1
After perforation was carried out for 00 m, it was judged based on the state of generation of chips and the state of generation of "whiskers" on the perforated portion. Based on the PET film sample (B-1), those with more chips or more "whiskers" generated are x, those equivalent to or less than PET are ○, slightly inferior to PET, but acceptable The range is represented by Δ. 6-3) Toy curl After slitting the sample to 25 mm, the humidity is adjusted overnight in a room at 25 ° C and 10%. After placing this with the emulsion side facing down, measure the highest part of the toy-like part. The TAC 100 μm film sample (C-1) was used as a type, and those higher than this were represented by x, and those equivalent or lower than this were represented by ◯.

7) Results Examples of the present invention are shown in A-1 and A-2. When A-1 is heat-treated at a constant temperature, A-2 shows Tg from a temperature of Tg or higher.
This is an example in which heat treatment is carried out while being cooled by straddling. In each case, curling, piercing, and toy curl are all good.
In A-3 to A-6, the heat treatment time was changed and the heat absorption amount at Tg was changed. A-3 has an endothermic amount of 100 mcal /
It is less than g and the curl does not decrease sufficiently,
The back end is broken. On the other hand, the endothermic amount is 100 m c
With A-4 that exceeds al / g, the curl is sufficiently reduced and no trouble has occurred in the minilab. In A-5, the endothermic amount exceeds 1000 mcal / g. Here, the curl is sufficiently reduced, but the breaking elongation is reduced to 60% or less along with it, so that chips are generated during perforation. On the other hand, A-6
Is 1000 mcal / g or less, and the breaking elongation is 6
It is 0% or more, and there is no problem of perforation lines. Thus, the heat absorption is 100 mcal / g or more, 1000 mcal
/ G or less is desirable.

A-7 to 11 are films formed by changing the stretching ratio. A-7 is the one in which the draw ratio is increased, whereby the Young's modulus is 670 kg / mm ² or more and the refractive index ratio is 1.22 or more. This makes the membrane brittle and less perforative. On the other hand, A-8 has a Young's modulus of 670 kg or less, a breaking elongation of 60% or more, and a refractive index ratio of 1.22 or less, and there is no problem in piercing property. On the other hand, A-9
Indicates that the draw ratio has been reduced, and the Young's modulus is 530
kg / mm ² or less, elongation rate was 210% or more, refractive index ratio was 1.10 or less, and the occurrence of "beard" at the perforated portion was considerably larger than that of the type PET film, and the perforability was outside the allowable range. . Also, due to the decrease in mechanical strength, toy curls were also NG. On the other hand, Young's modulus of A-10 is 53
It was 0 kg / mm ² or more, the extension rate was 210% or less, and the refractive index ratio was 1.10 or more, and there was no problem in providing perforability and toy curl. Thus Young's modulus 530 kg / mm ² or more, 670 kg / mm ² or less, elongation at break 60% 20
It is desirable that the refractive index ratio is 0% or less and the refractive index ratio is 1.10 or more and 1.22 or less.

A-11 to A-14 are different heat setting conditions. A-11 is a product in which heat fixing is performed for a long time to increase the crystallinity, which exceeds 0.51. Along with this, the film becomes brittle, and there is a problem that piercing chips are easily generated. In contrast,
With A-12 having a crystallinity of 0.5 or less, there was no problem in piercing property. On the other hand, in A-13 in which the heat setting was shortened and the crystallinity was 0.3 or less, the Young's modulus was 520 kg or less and the toy-like curl was large. On the other hand, with A-14 having a crystallinity of 0.3 or more, there was no problem in the toy curl. Thus, the crystallinity must be 0.3 or more and 0.5 or less. A-15 to 19 are those in which the diameter of the spool around which the film is wound is changed. For A-15, a spool having a diameter of 5 mm or less was used. Although not shown in Table 2-2, pressure fogging occurred in the emulsion layer on this spool. On the other hand, pressure fog did not occur in A-16 using a spool having a diameter of 5 mm. Further, when a spool having a diameter of 12 mm is used, as shown in A-17, even if heat treatment is not performed, that is, even if the endothermic amount across Tg is 0, the winding is large enough to cause problems such as rear end breakage. Did not occur. On the other hand, A-18 using a spool with a diameter of 11 mm,
In No. 19, in A-19 which was subjected to the heat treatment of the present invention, rear end fold did not occur, but in which A-18 was not subjected to heat treatment.
Then this is happening. As described above, in the present invention, it is preferable to wind the spool around the spool having a diameter of 5 to 11 mm.

A-20 and 21 are films having different film thicknesses. A-20 has a thickness of 60 μm or less, which is a problem that a toy-like curl occurs due to insufficient mechanical strength. On the other hand, with A-21, the thickness is 60 μm or more, and the toy-like curl is at a level without any problem. On the other hand, the current color negative film uses a TAC support, and the thickness of the TAC support is 122 μm. If this is set to 110 μm, the toy-like curl becomes large and the passability of a printer or the like deteriorates. Therefore, when the support of the present invention is used at a thickness of 122 μm or less, a sufficient merit for TAC can be obtained, and in this case, the miniaturization of the cartridge can be achieved well. Therefore, the support of the present invention is preferably used in the range of 60 μm to 122 μm. PET on B-1
An example of the support is shown. Since the Tg of this support is 90 ° C. or less, the core set at 80 ° C. for 2 hours causes a significant curling, which causes a processing trouble. On the other hand, T of PEN
Since g exceeds 90 ° C., there is no problem with winding as shown in A-1 and A-2. Thus, it is preferable to use a support having a Tg of 90 ° C. or higher. As described above, by using the support of the present invention, it is possible to provide a photographic light-sensitive material having a small curl, excellent mechanical properties and excellent perforation property.

Example 2 1) Preparation of Sensitive Material Polyester used for the support is PEN, PET, PA.
Pellets of r, PCT, and polycarbonate (PC) were vacuum-dried in advance at 130 ° C. for 4 hours, and then kneaded and extruded at 300 ° C. using a biaxial kneading extruder at a mixing ratio shown in Table 4-1, and then pelletized. All of the polyesters were film-formed and heat-treated in the same manner as Level A-1 in Table 2-1. Further, an undercoat layer and a back layer were formed by coating in the same manner as in the method of the support A of Example 1. A photosensitive layer was applied to this in the same manner as in the examples to prepare samples D1 to D11. 2) Evaluation of sample The refractive index ratio of the support after film formation and heat treatment was
Tg, heat absorption amount at Tg, tan δ, crystallinity, Young's modulus, elongation at break of those coated up to the back layer, and curling, toy-like curl and perforation of those coated up to the emulsion layer, respectively. Evaluation was carried out in the same manner as in Example 1.

3) Results The results are shown in Table 4-2.

[0101]

[Table 5]

[0102]

[Table 6]

A blend of PEN and PET was used as D-
It showed in 1-6. D with PEN content of 60 wt% or more
In -1 to 5, tan δ at 50 ° C is 0.1 or more. By comparing the winding curls before and after development, 3
The curl value is smaller than 0. On the other hand, D-6 is 5
The tan δ at 0 ° C. is 0.1 or less, and the curling due to the development is reduced by only 15 and as a result, the trailing edge of the film is bent. This reflects that tan δ at 50 ° C. is small, that is, plastic flow is difficult to occur, plastic flow in the drying zone (50 ° C.) after development processing is small, and curl recovery during development is small. . On the other hand, in D-11,
tan δ exceeds 0.1. With such a large size, the plastic flow at a normal temperature becomes large, so that it becomes easy to curl. That is, there is a curl that cannot be completely recovered by the development process, and troubles such as rear end breakage occur. On the other hand, t
With D-10 having an δ of 0.1 or less, such trouble did not occur. Thus, tan δ is preferably 0.1 or less and 0.01 or more. In addition to these, as shown in D-7-9, in the case where tan δ is in this range, the uneasiness of curling and the recoverability of curling are well balanced, and problems during development processing occur. Does not occur.

Example 3 1) Preparation of Sensitive Material For a polyester having a glass transition temperature of 90 ° C. or higher, a stainless steel autoclave was used, and dimethanol terephthalate (TPDM) and 2,6-naphthalene dicarboxylic acid dimethanol ( NDCDM), ethylene glycol (EG) as diol, bisphenol A
(BPA), cyclohexanedimethanol (CHDM)
Were mixed in the composition shown in Table 5-1 and polycondensed by the transesterification method using 0.025 mol of antimony trioxide (based on the acid component) as a catalyst. The polyester thus synthesized was formed into a film by the same method as in Level A-1 of Example 1. This was further surface-treated, heat-treated, coated with an undercoat layer, and coated with a back layer according to Level A-1 of Example 1. A photosensitive layer was coated on this in accordance with Example 1 to obtain photographic film samples E-1 to E-4.

2) Evaluation of sample Regarding the support after film formation and heat treatment, Tg, heat absorption amount at Tg, tan δ, crystallinity, Young's modulus of the refractive index ratio of the support coated with the undercoat and the back layer The film having the elongation at break applied up to the emulsion layer was wound, and the toy-like curl and piercing property were evaluated in the same manner as in Example 1. 3) Results The results are shown in Table 5-2.

[0106]

[Table 7]

[0107]

[Table 8]

Among the copolymers other than PEN, E-1 to 4 satisfying the requirements of the invention showed good winding, mechanical properties and perforation.

[0109]

EFFECTS OF THE INVENTION Heat treatment is carried out until the endothermic peak appearing across the Tg of the support becomes 100 mcal / g or more and 1000 mcal / g or less, and tan δ is 0.01 or more and 0.1 or less and crystallinity is 0.3 or more. 0.5 or less, Tg of 90 to 200 ° C., Young's modulus of 670 kg / mm
² or less 530 kg / mm ² or more, breaking elongation 60% or more and 200% or less, and refractive index ratio 1.22 or less 1.10 or more biaxially stretched polyester film is used as a support to prevent curling It is possible to provide a silver halide photographic light-sensitive material having excellent perforation suitability and mechanical properties. Therefore, when using this photosensitive material, the cartridge can be downsized.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material wound in a roll, in which at least one silver halide emulsion layer is provided on a support, and the glass transition temperature (T
Endothermic peak appearing across g) is 100 mcal / g
As described above, the support is heat-treated until it becomes 1000 mcal / g or less, and the loss elastic modulus (tan δ) of the support is 0.01 or more and 0.1 or less, and the crystallinity is 0.3 or more.
0.5 or less, Tg is 90 ° C. or higher 200 ° C. or less, a Young's modulus of 670 kg / mm ² or less 530 kg / mm ² or more, 200% elongation at break 60% or less, the ratio of the refractive index of the film surface direction and thickness direction Is 1.22 or less 1.10
A silver halide photographic light-sensitive material, which is the above biaxially stretched polyester. 2. A silver halide photographic light-sensitive material having a roll-shaped photographic film support wound around a spool having an outer diameter of 5 mm to 11 mm and a silver halide emulsion layer, the support having a film thickness of 2. The silver halide photographic light-sensitive material according to claim 1, wherein the thickness is 60 μm to 122 μm, and the support is biaxially stretched polyethylene naphthalate.