JPH06308664A - Cartridge for 35mm camera - Google Patents

Abstract

PURPOSE:To provide a cartridge for a 35mm camera housing >=42 frames by improving the operation to remove the tongue end of a film after setting a high-temp. core, thereby improving the cartridge in such a manner that the uneven development processing does not arise and the break at the rear end of the film at the time of development processing does not occur. CONSTITUTION:The base of the rolled film of the cartridge for the 35mm camera in which the 35mm rolled film is housed is the arom. dicarboxylate system polyester base of polyethylene which has 105 to 50mum thickness, 50 to 200 deg.C glass transition point and is subjected to a heat treatment for 0.5 to 1500 hours at a temp. lower by >=40 deg.C than the glass transition point before application of an under coating layer or after the application of the under coating layer. The number of the housed frames of the rolled film is 42 to <=100 frames.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cartridge for a 35 mm camera, and more particularly to a cartridge for a 35 mm camera in which a film having a large number of frames which is hard to curl at a high temperature is stored.

[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, a fiber-based polymer represented by triacetyl cellulose (hereinafter referred to as "TAC") and a polyester-based polymer represented by polyethylene terephthalate (hereinafter referred to as "PET") are generally used. There is.

In general, a roll film as a photographic light-sensitive material is typically contained in a cartridge with a width of 35 m / m or less, and is a color or black-and-white film which is loaded into a general camera and used for photographing. Is. TAC is mainly used as the support for the roll film, but the greatest feature is that it has no optical anisotropy and high transparency. A further outstanding feature is that it has curl elimination after development processing. That is, since the TAC film has a high water-absorbing property as a plastic film, which is a characteristic of its molecular structure, the curling curl that occurs when the film is rolled as a roll film ages and the molecular chain flows due to water absorption in the developing process. Then
That is, the fixed molecular chains undergo rearrangement over time. As a result, it has an excellent property of eliminating curling curl once formed.

However, a drawback of TAC film is that its film strength is insufficient, and the current international table 10 standard (IS
The cartridge defined by O1007) requires a TAC thickness of 115 μm or more. When winding a typical ASA400 negative color film of roll film sensitive material around this TAC, the spool diameter is 11.5 mm.
The maximum number of full-size frames is 39 in a cartridge inner diameter of 23 mm, and a maximum number of frames cannot be stored.

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 and the miniaturization of photographing cameras have been remarkably advanced. Even in such a situation, the 35 mm film made of the conventional TAC support cannot store a large number of frames in the current cartridge, and must be replaced frequently. Especially in sports photography, many high-speed shots are required, and the conventional 36-shot film sometimes misses a photo opportunity. Alternatively, on overseas travel where ease of use is required,
It was necessary to carry around a lot of refillable 35mm film, and improvement of the bulkiness was required.

In order to store a large amount of 35 mm film in such a cartridge, there are two problems. 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 light-sensitive layer dispersed in gelatin, and this layer causes shrinkage at low humidity to generate curl in the width direction (U-shape).
The support is required to have bending elasticity sufficient to withstand this contraction stress.

The second problem is a strong curl in the winding core portion which occurs during storage over time due to a large amount of winding.
In the conventional 135 system, the spool diameter is 11.5m.
However, in the case of a 39-sheet film having a minimum winding diameter, the winding diameter of the film is substantially 13.5 mm even if it is stored up to 39 sheets. If this is wound around the spool diameter of 11.5 mm, it will be markedly wound and various troubles will occur. For example, when developing with a mini-lab automatic developing machine, one end is fixed to the reader and the other end is not fixed, so the film rolls up and the supply of the processing liquid is delayed, causing "processing unevenness". . In addition, the roll-up of this film is crushed by a drying roller etc. in the minilab and the film "folds".
Occurs.

[0008]

In order to achieve the above two problems, that is, high mechanical strength and small curl, a polyester support represented by polyethylene terephthalate (PET) of the present invention, which is excellent in mechanical strength, is used. On the body,
This is a method to improve the curling tendency. In order to achieve these objects, polyethylene terephthalate, which is inexpensive and has excellent productivity, mechanical strength and dimensional stability, has been considered as a substitute for TAC. However, in a roll form widely used as a photographic light-sensitive material, curling curls strongly remain,
Although it has difficulty in extracting the tongue end to pull out the film that has been caught in the cartridge after shooting and that it is difficult to handle after development processing, it has the above-mentioned excellent properties, but its range of use for roll film Has been limited. In view of the above points, the present invention allows the tongue end to be easily extracted even when the core is set at a high temperature, does not cause uneven development of the film and rear end folds, and accommodates a 35 mm film of 42 frames or more. The purpose is to provide a cartridge. In order to achieve the above object, the present invention has found that it is effective to use a polyethylene aromatic dicarboxylate-based polyester as a support in a thin film and heat-treated before coating an emulsion. It has been found that when it is incorporated into a film cartridge, it is extremely effective in increasing the number of frames and making it thinner.

[0009]

These objects of the present invention are, in a cartridge for a 35 mm camera in which a 35 mm roll film is housed, a support for the roll film having a thickness of 105 μm to 50 μm and a glass transition point. Is 50 to 200 ° C., and a polyethylene aromatic dicarboxylate polyester support heat-treated at a temperature of 40 ° C. or higher and a glass transition temperature or lower for 0.5 to 1500 hours before application of an undercoat layer or after application of an undercoat layer to before emulsion coating. It is a body and the number of frames of the rolled film stored is 42 to 10
Achieved by a camera cartridge characterized by 0 frames. First, a description will be given of the winding curl measurement method used thereafter and terms related thereto. (1) Core set To wrap a film around a spool and add a curl. (2) Glass transition temperature (Tg) Using a differential thermal analyzer (DSC), sample film 10
When an endothermic peak appears in the arithmetic mean temperature or Tg of the temperature at which deviation from the baseline begins and the temperature at which the baseline returns to a new baseline when mg is heated at 20 ° C / min in a helium-nitrogen stream, this The temperature shown at the maximum value of the endothermic peak is defined as Tg.

First, the polyester which is the support of the present invention will be described. Although there are various polyesters of the present invention, the polyester having benzenedicarboxylic acid and ethylene glycol as the main components has high performance by balancing the difficulty of rolling and the mechanical strength, and the cost, and especially , Polyethylene-terephthalate (PE
Preferred are T) and polyethylene naphthalate-based polyesters. The polyester of the present invention is formed with a diol and an aromatic dicarboxylic acid as essential components,
Dibasic acids that can be used include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, naphthalenedicarboxylic acid, succinic acid, glutaric acid, 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 Acid, 1,4-cyclohexanedicarboxylic acid,

[0011]

[Chemical 1]

[0012]

[Chemical 2]

And the like. The essential aromatic dicarboxylic acid is one having at least one benzene nucleus among the above-mentioned dicarboxylic acids. Next, as the diol, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol are used. 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-benzenedimethanol,

[0014]

[Chemical 3]

[0015]

[Chemical 4]

And the like. Further, if necessary, a monofunctional or trifunctional or higher polyfunctional hydroxyl group-containing compound or acid-containing compound may be copolymerized. The polyester of the present invention may be copolymerized with a compound having a hydroxyl group and a carboxyl group (or an ester thereof) at the same time in the molecule, and examples thereof include the following.

[0017]

[Chemical 5]

Among the polyesters containing these diols and dicarboxylic acids, more preferred are homopolymers such as polyethylene terephthalate, polyethylene naphthalate and polycyclohexanedimethanol terephthalate (PCT), and particularly preferred essential aromatic compounds. 2,6-naphthalenedicarboxylic acid (NDCA), terephthalic acid (TPA), isophthalic acid (IPA), orthophthalic acid (OPA), paraphenylenedicarboxylic acid (PPDC) as dicarboxylic acid, and (poly) ethylene glycol (PEG) as diol Or E
G)), cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), bisphenol A
Examples thereof include (BPA), biphenol (BP), and a copolymerized component of hydroxycarboxylic acid such as parahydroxybenzoic acid (PHBA) and 6-hydroxy-2-naphthalenecarboxylic acid (HNCA).

Among these, more preferable are:
Copolymer of terephthalic acid, naphthalenedicarboxylic acid and ethylene glycol (mixing molar ratio of terephthalic acid and naphthalenedicarboxylic acid is 0.9: 0.1 to 0.1: 0.9
Is preferable, and 0.8: 0.2 to 0.2: 0.8 is more preferable. ), Terephthalic acid and ethylene glycol,
Copolymer of bisphenol A (mixing molar ratio of ethylene glycol and bisphenol A is 0.6: 0.4 to 0:
It is preferably between 1.0 and more preferably 0.5: 0.5 to 0 :.
0.9 is preferred. ), Isophthalic acid, paraphenylenedicarboxylic acid, and a copolymer of terephthalic acid and ethylene glycol (isophthalic acid; the molar ratio of paraphenylenedicarboxylic acid is 0 when terephthalic acid is 1).
1-0.5, 0.1-0.5, more preferably 0.2-0.3, 0.2-0.3, respectively), terephthalic acid, copolymer of neopentyl glycol and ethylene glycol ( The molar ratio of neopentyl glycol and ethylene glycol is preferably 1: 0 to 0.7: 0.3, more preferably 0.9: 0.1 to 0.6: 0.4).
Copolymer of terephthalic acid, ethylene glycol and biphenol (The molar ratio of ethylene glycol and biphenol is preferably 0: 1.0 to 0.8: 0.2, more preferably 0.1: 0.9 to 0.7: 0.3),
Para-hydroxybenzoic acid, a copolymer of ethylene glycol and terephthalic acid (the molar ratio of para-hydroxybenzoic acid and ethylene glycol is preferably 1: 0 to 0.1: 0.9, more preferably 0.9: 0.1-0). 2: 0.
Copolymers such as 8) are preferred.

These homopolymers and copolymers can be synthesized according to conventionally known methods for producing polyesters. 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 so, it can be synthesized. Alternatively, the acid component may be an acid halide and reacted with glycol. At this time, if necessary, a transesterification reaction catalyst, a polymerization reaction catalyst, 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), pp. 103-136.
Page, "Synthetic Polymer V" (Asakura Shoten, 1971), 18th
It can be performed with reference to the descriptions on pages 7 to 286. The preferred average molecular weight range for these polyesters is about 1
It is 50,000 to 500,000. 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-49-548.
2, ibid. 64-4325, JP-A-3-192718, research disclosure 283, 739-41, ibid.
84, 779-82 and 294, 807-14, it can be easily formed.

The polyester of the present invention has a Tg of 50 ° C.
As described above, the conditions of use are not generally handled with sufficient caution, and the temperature is often exposed to 40 ° C. especially in the midsummer outdoors. From this viewpoint, the Tg of the present invention is safe. The temperature is preferably 55 ° C or higher. More preferably, Tg is 60 ° C. or higher, and particularly preferably 70 ° C. or higher. This is because the effect of improving the curling habit by this heat treatment disappears when exposed to a temperature exceeding the glass transition temperature, so that the temperature is a severe condition when used in a general user, that is, the temperature in summer exceeds 40 ° C. Polyesters having a glass transition temperature above the temperature are preferred. On the other hand, there is no general-purpose polyester film which is transparent and has a temperature higher than 200 ° C. Therefore, the Tg temperature of the polyester used in the present invention needs to be 50 ° C. or higher and 200 ° C. or lower.

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 compound example P-0: [Terephthalic acid (TPA) / ethylene glycol (EG)) (100/100)] (PET)
Tg = 80 ° C. P-1: [2,6-naphthalenedicarboxylic acid (NDC
A) / Ethylene glycol (EG) (100/10
0)] (PEN) Tg = 119 ° C. P-2: [terephthalic acid (TPA) / cyclohexanedimethanol (CHDM) (100/100)]
Tg = 93 ° C. P-3: [TPA / bisphenol A (BPA) (1
00/100)] Tg = 192 ° C. P-4: 2,6-NDCA / TPA / EG (50/5
0/100) Tg = 92 ° C. P-5: 2,6-NDCA / TPA / EG (75/2
5/100) Tg = 102 ° C. P-6: 2,6-NDCA / TPA / EG / BPA
(50/50/75/25)
Tg = 112 ° C. P-7: TPA / EG / BPA (100/50/5
0) Tg = 105 ° C. P-8: TPA / EG / BPA (100/25/7
5) Tg = 135 ° C. P-9: TPA / EG / CHDM / BPA (100 /
25/25/50) Tg = 115 ° C

P-10: IPA / PPDC / TPA / E
G (20/50/30/100) Tg = 95 ° C. P-11: NDCA / NPG / EG (100/70/3)
0) 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. 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 (50/25/2
5) Tg = 108 ° C. P-20: TPA / 5-sulfoisophthalic acid (SI
P) / EG (95/5/100)
Tg = 65 ° C

These supports have a thickness of 50 μm or more and 105 μm or more.
The thickness is m or less. If it is less than 50 μm, it cannot withstand the shrinkage stress of the photosensitive layer generated during drying.
If it exceeds μm, it is inconsistent with the purpose of reducing the thickness for compactness. 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, PET had strong bending elasticity,
PEN is used, and it is possible to reduce the film thickness required for TAC of 122 μm to 100 μm or less. Next, the polyester support of the present invention is characterized by being subjected to a heat treatment, and in that case, it is necessary to perform the treatment at a temperature of 40 ° C. or higher and a glass transition temperature or lower for 0.1 to 1500 hours. This effect progresses faster as the heat treatment temperature increases. However, when the heat treatment temperature exceeds the glass transition temperature, the molecules in the film move rather disorderly and conversely the free volume increases, so that the molecules easily flow, that is, the film is easily curled.
Therefore, this heat treatment needs to be performed at a temperature not higher than the glass transition temperature.

Therefore, this heat treatment is preferably carried out at a temperature slightly below the glass transition temperature for the purpose of shortening the processing time, and is preferably 40 ° C. or higher and the glass transition temperature or lower, more preferably
The temperature is not less than 30 ° C. below the glass transition temperature and not more than the glass transition temperature. On the other hand, when performing heat treatment under these temperature conditions,
The effect is recognized after 0.1 hour. Further, at 1500 hours or more, the effect is almost saturated. Therefore, 0.
It is preferable to perform heat treatment for 1 hour or more and 1500 hours or less. Furthermore, in the method for heat-treating the polyester of the present invention, it is preferable to preliminarily heat to Tg or more for a short time (preferably, to perform Tg treatment at 20 ° C. or higher and 100 ° C. or lower for 5 minutes to 3 hours) in order to shorten the time. . Further, in the heating method, the film roll may be left as it is in a heating warehouse for heat treatment, but it may be further transferred to a heating zone for heat treatment, and the latter is preferred in view of the suitability for production. Further, the roll core used in the heat treatment preferably has a structure in which an electric heater is built in or a high-temperature liquid can be poured so that the film can be hollow or heated in order to efficiently propagate the temperature to the film. The material of the roll winding core is not particularly limited, but it is preferably one that does not undergo strength reduction or deformation due to heat, and examples thereof include stainless steel and glass fiber-containing resin.

Next, in order to further enhance the function of the polyester of the present invention as a photographic support, it is preferable to coexist various additives. An ultraviolet absorber may be kneaded into these polyester films for the purpose of preventing fluorescence and imparting stability with time. It is desirable that the ultraviolet absorber has no absorption in the visible region, and the addition amount thereof is usually 0.01% by weight to 20% by weight, preferably 0.05% by weight based on the weight of the polyester film.
It is about 10% by weight to 10% by weight. If it is less than 0.01% by weight, the effect of suppressing deterioration of ultraviolet rays cannot be expected. 2,4-dihydroxybenzophenone as an ultraviolet absorber,
2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,
2 ', 4,4'-tetrahydroxybenzophenone,
Benzophenone-based compounds such as 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 UV absorbers such as phenyl salicylate and methyl salicylate.

Further, one of the properties which becomes a problem when the polyester film of the present invention 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. Furthermore, the refractive index of the polyester of the present invention, particularly the aromatic polyester, is 1.6 to 1.
7 is high, the refractive index of gelatin which is the main component of the photosensitive layer coated thereon is 1.50 to 1.55, which is smaller 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 incorporating inert inorganic particles and the like into a 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 film haze. At this time, 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. Further, those having excellent compatibility with polyester are preferable. As the dye, from the above viewpoint, Dia manufactured by Mitsubishi Kasei
The purpose can be achieved by mixing a commercially available dye for polyester such as resin and Kayase manufactured by Nippon Kayaku. Regarding the staining density,
It is necessary that the color density in the visible light range is measured with a color densitometer manufactured by Macbeth Co., Ltd. and is at least 0.01 or more. More preferably, it is 0.03 or more.

The polyester film according to the present invention can be imparted with slipperiness according to the use, and the slipperiness imparting means is not particularly limited.
The kneading of an inert inorganic compound or the coating of a surfactant is used as a general method. Such inert inorganic particles include SiO ₂ , TiO ₂ , BaSO ₄ , CaC.
Examples are O 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 a support for a photographic light-sensitive material. Therefore, in the slipperiness imparting method means, a polyester film is used as an external particle system. 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.

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 support, since each of these polymer films has a hydrophobic surface, a photographic layer (for example, a photosensitive silver halide emulsion layer containing a protective colloid mainly containing gelatin) is provided on the support. , The intermediate layer, the filter layer, etc.) are very difficult to adhere firmly. As conventional techniques attempted to overcome such difficulties, (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 adhesive strength, 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 polar groups on the surface of the support, which was originally hydrophobic, to some extent, 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. Furthermore, an adhesion mechanism due to generation of radicals is also considered. Also, various arrangements have been made for the composition of the undercoat layer, and a layer that adheres well to the support (hereinafter referred to as the first undercoat layer) is provided as the first layer, and the second layer is photographed as the second layer. 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, Japanese Patent Publication Nos. 48-5043 and 47-5.
1905, JP-A-47-28067 and JP-A-49-83.
No. 767, No. 51-41770, No. 51-13157.
This can be achieved by the method disclosed in No. 6 or the like.
Discharge frequency is 50 Hz to 5000 KHz, preferably 5
KHz to several hundred KHz is suitable. If the discharge frequency is too low, stable discharge cannot be obtained and pinholes are generated in the object to be treated, which is not preferable. If the frequency is too high,
A special device for impedance matching is required, which increases the cost of the device, which is not preferable. Regarding the treatment strength of the object to be treated, 0.001 KV · A · min / m ^{2 to} 5 KV · A · min / m ² for improving the wettability of ordinary polyester, polyolefin and other plastic films.
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.

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

The glow discharge treatment conditions are generally pressure of 0.
005-20 Torr, preferably 0.02-2 Torr
r 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 is the composition of the atmosphere gas,
Although various values can be obtained depending on the pressure, in the pressure range described above, a stable steady glow discharge usually occurs between 500 and 5000V. A particularly suitable voltage range for improving the adhesion is 2000 to 4000V. Further, as seen in the prior art, a suitable discharge frequency is from direct current to several 1000 MHz, preferably 50 Hz to 20 MHz. Regarding the discharge treatment strength, 0.01KV · A · min / m ² to 5KV is obtained because the desired adhesion performance can be obtained.
・ A · min / m ² , preferably 0.15 KV · A · min / m
^{2 to 1} KV · A · min / m ² is suitable.

Next, the undercoating method (2) will be described. All of these methods have been well researched. For example, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid are used for the first undercoating layer in the multi-layer method. , Itaconic acid, maleic anhydride, and other copolymers starting from selected monomers, such as polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and many other polymers. The properties of the two layers have been investigated mainly for gelatin.
In the single layer method, good adhesion is often achieved by swelling many supports and interfacially mixing with the hydrophilic undercoat polymer. Examples of the hydrophilic undercoating polymer used in the present invention include water-soluble polymers, cellulose esters, latex polymers and water-soluble polyesters. Water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, maleic anhydride copolymers, etc., and carboxymethyl cellulose, hydroxyethyl cellulose as cellulose ester. And so on. Examples of the latex polymer include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylic acid ester-containing copolymers, vinyl acetate-containing copolymers and butadiene-containing copolymers. Of these, gelatin is the most preferable.

As the compound for swelling the support used in the present invention, resorcin, chlorresorcin, methylresorcin, o-cresol, m-cresol, p-cresol, phenol, o-chlorophenol, p-chlorophenol, di-resin. Examples include chlorophenol, trichlorophenol, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid, and chloral hydrate. Of these, resorcin and p-chlorophenol are preferred. Various gelatin hardeners can be used in the subbing layer of the present invention. As a gelatin hardening agent, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine, etc.), epichlorohydrin resin And so on. The subbing layer of the present invention includes SiO ₂ , TiO
_2. Inorganic fine particles such as a matting agent or polymethylmethacrylate copolymer fine particles (1 to 10 μm) can be contained as a matting agent. 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, dip 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 for the back layer may be either 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, and is disclosed in, for example, JP-A-49-85826 and JP-A-49-33630.
U.S. Pat. No. 2,992,108, U.S. Pat. No. 3,2
06, 312, JP-A-48-87826, JP-B-49
-11567, JP-B-49-11568, JP-A-5
The compound as described in 5-70837 etc. can be mentioned.

Most preferred as an antistatic agent for the back layer of the present invention
Preferred are ZnO and TiO₂, SnO₂, Al₂
O₃, In₂O₃, SiO₂, MgO, BaO, MoO
₃V ₂O_FiveAt least one crystalline gold selected from
It is a fine particle of a group oxide or a complex oxide of these.
Conductive crystalline oxide used in the present invention or composite thereof
Oxide particles have a volume resistivity of 10⁷Ωcm or less,
More preferably 10^FiveΩcm or less. Also its particles
The size is 0.002-0.7 μm, especially 0.005-
It is desirable to set it to 0.3 μm.

The 35 mm film cartridge of the present invention is the above-mentioned international standard 35 mm cartridge. That is, the metal cartridge has a tongue end with a light-shielding cloth called a telempu. In the present invention, the number of frames of the 35 mm film stored in the 35 mm cartridge is 42 to 100 frames, more preferably 45 to 100 frames, and further preferably 50 to 80 frames. The emulsion thickness of the roll film used in the present invention is 5 to 30 μm, preferably 10 to 25 μm. Therefore, in the present invention, it is important to define the total thickness in order to accommodate a large number of film frames, and preferable examples will be described below. In the present invention, a preferable film is a roll-shaped color film, and the emulsion thickness thereof is generally 15
˜30 μm. The thickness of the emulsion which is particularly preferably used is 25 μm. In that case, when the thickness of the support is 50 μm, 100 frames can be stored and the thickness of the support is 10 μm.
With 5 μm, 48 frames can be stored. 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 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. The number of layers and the non-photosensitive layer and the order of the layers are not particularly limited. 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-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. For the intermediate layer, JP-A Nos. 61-43748, 59-113438, 59-113440 and 6-61 are used.
The couplers and DIR compounds as described in 1-20037 and 61-20038 may be contained, and a color mixing inhibitor may be contained as is usually 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-57-112751.
No. 62-200350, No. 62-206541.
No. 62-206543, No. 56-25738,
62-63936, 59-202464, JP-B-55-34932, and 49-15495.

The silver halide grains include those having regular crystals such as cubes, octahedra and tetradecahedrons, those having irregular crystal shapes such as spheres and plates, and twin planes. It may have a crystal defect or a composite form thereof. The grain size of silver halide may be fine grains of about 0.2 μm or less, or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No. 176.
43 (Dec. 1978), pp. 22-23, "I. Emulsion preparation a.
nd types) ", and No. 18716 (1).
(November, 1997), p.648, "The Physics and Chemistry of Photography" by Grafkid, published by Paul Montel (P. Glafkid).
es, Chemie et Phisique Pho
tographie, PaulMontel, 19
67), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photograph.
ic Emulsion Chemistry (Foc
al Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., published by Focal Press, Inc. (V.L.
Zelikman et al. , Making an
d Coating Photographic Em
ulsion, Focal Press, 1964) and the like.

US Pat. Nos. 3,574,628 and 3,
655,394 and British Patent 1,413,748.
The monodisperse emulsions described in JP-A No. 1989-2000 are also preferable. Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering (Gut
off, Photographic Science
and Engineering), Volume 14, 248
~ 257 (1970); U.S. Pat. No. 4,434,2.
No. 26, No. 4,414, 310, No. 4,433, 04
No. 8, 4,439,520 and British Patent No. 2,1.
It can be easily prepared by the method described in No. 12,157. 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. Silver halide emulsion,
Usually, those which have been physically aged, chemically aged and spectrally sensitized are 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 No. 17643 and No. 18
716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table. (Additive type) (RD176439) (RD187169) 1 Chemical sensitizer, page 23, page 648, right column 2 Sensitivity enhancer, same as above 3 Spectral sensitizer, supersensitizer, page 23 to 24, 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 column 7 Stain prevention Agent page 25 right column page 650 left to right column 8 dye image stabilizer page 25 9 film hardening agent page 26 651 page left column 10 binder page 26 same as above 11 plasticizer, lubricant page 27 650 right column 12 coating aid, Surfactants, pages 26 to 27, page 650, right column Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, formaldehyde described in U.S. Pat. Nos. 4,411,987 and 4,435,503. React with, it is preferable to add a compound capable of immobilizing the photosensitive material.

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.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984)
, JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238, and 60.
-35730, 55-118034, 60-1
85951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, W.
Those described in O (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.

Colored couplers for correcting unwanted absorption of color forming dyes are Research Disclosure N.
VII-G, 17643, U.S. Pat.
670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,
Those described in 004,929, 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,
570, EP 96,570, and West German Patent (Publication) 3,234,533 are preferable.
Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820 and 4,080,211.
No. 4,367,282, No. 4,409,32
No. 0, 4,756,910, British Patent 2,10
2, 137, etc. Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are disclosed in the above-mentioned RD17643, VII to F patents, JP-A-57-151944, and JP-A-57-15.
No. 4234, No. 60-184248, No. 63-373.
Those described in US Pat. No. 46 and US Pat. No. 4,248,962 are preferable.

As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,093
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Other couplers that can be used in the light-sensitive material of the present invention include U.S. Pat. No. 4,130,4.
Competitive couplers described in U.S. Pat. No. 27, US Pat.
No. 3,472, No. 4,338,393, No. 4,3
Multiequivalent couplers described in JP-A No. 10,618, etc., JP-A-60
-185950, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound described in JP-A-62-24252 and the like, and after separation as described in EP 173,302A Couplers that release dyes that recolor, R.I. D. No. 11449 and 2
4241, couplers for releasing bleaching accelerators described in JP-A No. 61-201247, couplers for releasing ligands described in US Pat. No. 4,553,477, JP-A-63-7.
Examples thereof include couplers releasing the leuco dye described in No. 5747.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,222.
No. 027 and the like. Specific examples of the high boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters, phosphoric acid or phosphonic acid esters, benzoic acid esters, amides, Examples thereof include alcohols or phenols, aliphatic carboxylic acid esters, aniline derivatives and hydrocarbons. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230. Light-sensitive material of the present invention the total film thickness of all the hydrophilic colloid layers on the side having emulsion layers is not more than 28 .mu.m, and the film swelling speed T _^1/2 is preferably not more than 30 seconds. The film thickness is 25
℃ means a film thickness measured at a relative humidity of 55% (2 days), the film swelling rate T _^1/2 can be measured in accordance with a known method in the art. For example, by A. Green et al.
Science and Engineering (Photog
r. Sci. Eng. ), Volume 19, Issue 2, 124-12
Can be measured by using a type of Swellometer described (swelling meter) pages 9, T _^1/2 is 30 ° C. in a color developing solution, 3
90% of the maximum swollen film thickness reached when processed for 15 minutes
Was saturated film thickness is defined as time until it reaches the thickness of the T _^1/2. Film swelling rate T _^1/2 can be adjusted to gelatin as a binder by adding a hardening agent, or by changing the aging conditions after coating.
The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness.

[0051]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. Example 1 1) Material of Support, etc. Each support used in this example was prepared by the following method. a) PEN: 100 parts by weight of commercially available polyethylene-2,6-naphthalate polymer and Tinu as an ultraviolet absorber
vinP. 2 parts by weight of 326 (manufactured by Geigy) was dried by a conventional method, melted at 300 ° C., extruded from a T-die and longitudinally stretched 3.3 times at 140 ° C., and then 13
The film was transversely stretched 3.3 times at 0 ° C., and heat-set at 250 ° C. for 6 seconds to obtain a PEN film. b) PET: A commercially available polyethylene terephthalate polymer was biaxially stretched and heat-set according to a conventional method to obtain a PET film. c) TAC: Methylene chloride / methanol = 82/8 by a normal solution casting method using triacetyl cellulose
wt ratio, TAC concentration 13%, plasticizer TPP / BDP = 2
/ 1 (where TPP; triphenyl phosphate, B
DP; Biphenyldiphenylphosphate) 15w
It was created by the t% band method. d) PEN / PET = 4/1 (weight ratio); P in advance
The EN and PET pellets were vacuum dried at 150 ° C. for 4 hours, kneaded and extruded at 280 ° C. using a twin-screw kneading extruder, and then pelletized. This polyester is
A film was formed under the same conditions as EN.

2) Coating of undercoat layer Each of the above-mentioned supports has corona discharge treatment, U
After V discharge treatment and further glow discharge treatment, an undercoat liquid having the following composition was applied to provide an undercoat layer on the high temperature surface side during stretching.
For the corona discharge treatment, a solid state corona processor 6KVA model manufactured by Pillar Co. was used, and a 30 cm wide support was 20 m.
/ Min. At this time, the object to be treated was treated at 0.375 KV · A · min / m ^{2 based on} the current / voltage readings. The discharge frequency during treatment is 9.6 KHz, and the gap clearance between the electrode and the dielectric roll is 1.6 mm.
Met.

Gelatin 3 g Distilled water 25 cc Sodium α-sulfodi-2-ethylhexyl succinate 0.05 g Formaldehyde 0.02 g Salicylic acid 0.1 g Diacetyl cellulose 0.5 g P-chlorophenol 0.5 g Resorcin 0.5 g Cresol 0.5 g ( CH2 = CHSO2CH2CH2NHCO) 2CH2 0.2g trimethylolpropane triazine 0.2g trimethylolpropane tritoluene diisocyanate 0.2g methanol 15cc acetone 85cc formaldehyde 0.01g

3) Coating of back layer A back layer having the following composition was coated on the surface opposite to the side where the undercoat layer of the above support was provided after undercoating. 3-1) Preparation of conductive fine particle dispersion liquid (tin oxide-antimony oxide composite dispersion liquid): 230 parts by weight of stannic chloride hydrate and 23 parts by weight of antimony trichloride were 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. Colloidal precipitate from which excess ions have been removed 2
100 parts by weight of water was redispersed in 1500 parts by weight of water and sprayed in a baking furnace heated to 600 ° C.
A fine powder of tin oxide-antimony oxide composite having a size of μm was obtained. 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; WILLYA.BACHOF).
It was prepared by dispersing with ENAG) until the residence time reached 30 minutes.

3-2) Preparation of back layer: the following formulation [A]
To a dry film thickness of 0.3 μm,
And dried for 60 seconds. The following coating solution (B) for coating layer was further applied onto this so that the dry film thickness was 1 μm.
It was dried at 5 ° C for 3 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 diacetate 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 Silica particles (average particle size 0.2 μm) 0.01 parts by weight Polysiloxane 0.005 parts by weight C ₁₅ H ₃₁ COOC ₄₀ H ₈₁ / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H = (8/2 weight ratio) 0.01 parts by weight Dispersion (average particle size 20 nm) 0.02 parts by weight Toluene Diisocyanate

4) Heat Treatment of Support After the undercoat layer and the back layer were applied by the above method, heat treatment was carried out under the conditions shown in Tables 2 and 3 below. All the heat treatments were carried out with the core having a diameter of 30 cm and the outer surface of the undercoat surface wound.

5) Coating of Photosensitive Layer On the support obtained by the above-mentioned method, each layer having the following composition was multilayer coated to prepare a multilayer color photosensitive material. The thickness of the emulsion layer was 25 μm. (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.

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 0.1
8 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 0.010 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

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

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

11th layer (low-sensitivity blue-sensitive emulsion layer) Emulsion C Silver 0.18 ExS-7 8.6 × 10 ^-4 ExY-1 0.020 ExY-2 0.22 ExY-3 0.50 ExY- 4 0.020 HBS-1 0.28 Gelatin 1.10

12th layer (medium-sensitivity blue-sensitive emulsion layer) Emulsion D Silver 0.40 ExS-7 7.4 × 10 ^-4 ExC-7 7.0 × 10 ^-3 ExY-2 0.050 ExY-30 .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 compounds and iron salts, lead salts, gold salts,
It contains platinum salt, iridium salt and rhodium salt.
The composition of the emulsion used in each layer is shown in Table 1.

[0074]

[Table 1]

In Table 1, (1) Emulsions A to F were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to F were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Has been done. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in tabular grains and normal crystal grains having a grain structure by using a high voltage electron microscope.

Next, the chemical formulas of the compounds used in each layer are shown.

[0077]

[Chemical 6]

[0078]

[Chemical 7]

[0079]

[Chemical 8]

[0080]

[Chemical 9]

[0081]

[Chemical 10]

[0082]

[Chemical 11]

[0083]

[Chemical 12]

[0084]

[Chemical 13]

[0085]

[Chemical 14]

[0086]

[Chemical 15]

[0087]

[Chemical 16]

[0088]

[Chemical 17]

[0089]

[Chemical 18]

[0090]

[Chemical 19]

[0091]

[Chemical 20]

6) Processing of photographic film sample The photographic film sample prepared in this way is 35 m long.
It was slit with a width of m, perforated, assembled in a 135 standard cartridge, and stored in a 35 mm film cartridge. 7) Core set The above cartridge was heated at 40 ° C. for 24 hours to be wound. This temperature condition is a condition assuming outdoor in summer. 8) Pull out the tongue, develop, and measure curl.
After being left to cool in a room at 5 ° C, the tongue tip was extracted with a jig, and this was developed with an automatic processor (Minilab FP-550B: made by Fuji Photo Film) and immediately at 25 ° C, 60%.
The curl measurement was performed under RH.

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 treating solution 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 a total volume of 1 liter Stop solution Sodium thiosulfate 10g Ammonium thiosulfate (70% aqueous solution) 30ml Acetic acid 30ml Sodium acetate 5g Potassium alum 15g Total volume 1l Bleach solution Ethylenediamine tetra-iron acetate (trivalent) sodium dihydrate 100g Potassium bromide 50g Ammonium nitrate 50g Folic acid 5g Ammonia water Adjust pH to 5.0 Total volume of water added 1 liter

Fixing solution Sodium thiosulfate 150 g Sodium sulfite 15 g Hoh sand 12 g Glacial acetic acid 15 ml Potassium alum 20 g Water was added to make the total amount 1 liter Stabilization bath 5 g Sodium citrate 5 g Sodium metaphorate (4 hydrate) 3 g Potassium salt Ban 15g Water is added and the total amount is 1 liter

9) Results The above results are shown in Tables 2-3. Comparative Samples 1 to 3 not using the polyester support of the present invention were conventional TAC as a support, and when the film thickness was thin, the tongue tip work was difficult regardless of the presence or absence of heat treatment. Further, even with the polyester support of the present invention, Comparative Samples 4 to 6 and 10 to 13 which are not subjected to the heat treatment not only cause rear end folds, but sometimes it is difficult to extend the tongue end. However, uneven development occurs. Further, in Comparative Samples 18 to 19 which were outside the heat treatment temperature of the present invention, the tongue end work was difficult and the rear end was broken.
On the other hand, Samples 7 to 9 and 14 to 17 of the present invention comprising the polyester support having the heat treatment and thickness of the present invention can accommodate a large number of 35 mm film frames in the cartridge and develop the tongue end workability well and develop There was no unevenness or rear end breakage. Although not shown in Tables 2-3 here,
Even if the type of the support is PET or PEN, if the thickness of the support is less than 50 μm, the support cannot have flexural elasticity to withstand the contraction stress of the photosensitive layer, and a gutter-like curl occurs, resulting in a development process. Back edge breakage and scratches occurred in the process.

As a polymer having a glass transition temperature Tg of more than 200 ° C., poly (oxyisophthalooxy-2,6-dimethyl-1,4-phenyleneisopropylidene-3,5-dimethyl-1,2 having a Tg of 225 ° C. is used. 4-phenylene) could not be applied to a light-sensitive material because a transparent support was not obtained. Further, all of the photosensitive materials prepared by using water instead of the conductive fine particle dispersion in the [formulation A] of the back layer showed the generation of static marks, and in the present invention, the conductive layer was not provided. , It is essential to enhance the marketability of the sensitive material.

[0098]

[Table 2]

[0099]

[Table 3]

[0100]

According to the present invention, in a 35 mm camera cartridge containing a 35 mm roll film,
The thickness of the roll-shaped film support is 105 μm to 50 μm.
μm, its glass transition point is 50 ° C. to 200 ° C., and 40 ° C. before applying the undercoat layer or after applying the undercoat layer and before applying the emulsion.
A polyethylene aromatic dicarboxylate-based polyester support that has been heat-treated at a temperature not higher than the glass transition temperature for 0.5 to 1500 hours, characterized in that the roll film can accommodate 42 or more and 100 or less frames. Since it is a cartridge for a 35 mm camera, a large number of film frames can be stored, it is easy to pull out the tongue end, it is hard to curl, and there is little curl after development processing. Also, there are few rear end breaks. Further, a film produced from the above-mentioned support has no emulsion unevenness and a good image can be obtained.

Claims (4)

[Claims] 1. A 35 mm camera cartridge containing a 35 mm roll film, wherein the roll film support has a thickness of 105 μm to 50 μm, a glass transition point of 50 ° C. to 200 ° C., and before an undercoat layer is applied. Or a polyethylene aromatic dicarboxylate polyester support which is heat-treated at a temperature of 40 ° C. or higher and a glass transition temperature or lower for 0.5 to 1500 hours after the undercoat layer is applied and before the emulsion is applied, and the roll-shaped film frame is stored. Number four
A camera cartridge characterized by 2 to 100 frames. 2. The 35 mm according to claim 1, wherein the polyethylene aromatic dicarboxylate-based support is a polyester containing benzenedicarboxylic acid, naphthalenedicarboxylic acid and ethylene glycol as main raw materials.
Cartridge for camera. 3. The 35 mm according to claim 2, wherein the polyester of the polyester support is polyethylene terephthalate or polyethylene naphthalate.
Cartridge for camera. 4. The cartridge for a 35 mm camera according to claim 1, which is a film having a conductive layer and / or a slip agent layer and / or a matting agent layer in at least one layer.