JPH0682980A - Camera incorporated with film - Google Patents

Abstract

PURPOSE:To obtain the camera improved to eliminate the folding of the tailing edge of the film in a development processing without causing irregular development by improving tongue edge pulling out work after a high temperature core setting. CONSTITUTION:In this camera 1 constituted in such a manner that an unexposed film 8 pulled out from a cartridge 6 is wound and loaded in a supply room 4, an empty cartridge is loaded in a winding room 5, and the unexposed film is pulled out from the supply room whenever photographing is executed and wound in the cartridge, the film incorporated type camera has a polyester supporting body as a supporting body, 90 deg.C-200 deg.C glass-transition temperature and the loading of the unexposed film thermally processed at the temperature of >=50 deg.C glass-transition temperature or below before or after an under coat is imparted and before coating with an emulsion is attained, in a state where the center of the unexposed film is empty or it is wound on the spool.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film-integrated camera, which is a so-called disposable camera, and more particularly, it improves the work of extracting a tongue end of a film with a curl at a high temperature, uneven development processing, and development processing. The present invention relates to a film-integrated camera with improved film breakage.

[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, as a photographic light-sensitive material, a sheet-shaped material such as an X-ray film, a plate-making film and a cut film, and a typical roll film have a width of 35 m / m or less. It is a color or black-and-white negative film that is stored in a cartridge and is loaded into a general camera and used for shooting. 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. Another feature is that it has excellent properties in decurling after development. That is, since the TAC film is characterized by its molecular structure, it has a relatively high water absorption property as a plastic film, and therefore curling curl that occurs over time in a situation where it is wound as a roll film is absorbed by water in the development process to cause a molecular chain. The molecular chains that flow and are fixed with time of winding undergo rearrangement.

As a result, it has an excellent property that the curling curl once formed is eliminated. 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 step for forming an image on photographic printing paper after development. However, problems such as defocusing and jamming at the time of transportation will occur.

On the other hand, PET film has been considered as a substitute for TAC because of its excellent productivity, mechanical strength and dimensional stability, but in the roll form widely used as a photographic light-sensitive material. Since the curling curl strongly remains, the handleability after development processing 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 transportation at the time of photographing, the high magnification of photographing, and the miniaturization 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. Conventionally, in the 135 system, a cartridge with a diameter of 25 mm has been used, but for example, this spool (core) is set to 10 mm or less, and at the same time, the current 1
The thickness of the TAC support used in the 35 system is 122μ.
If the thickness is reduced from 90 m to 90 μm, the cartridge will have a diameter of 20
The size can be reduced to mm or less.

In order to miniaturize 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 the strong curl that occurs during storage over time as the spool becomes smaller. Conventional 135
In the system, the roll diameter is 14 mm even for the 36-sheet film having the smallest roll diameter inside the cartridge. Attempts to reduce the size to 10 mm or less cause a marked curl, which causes various troubles. For example,
When developing with a minilab automatic developing machine, one end is fixed to the reader, the other end is not fixed,
The film rolls up, and the supply of the processing liquid is delayed there, causing "processing unevenness". Also, the roll-up of this film is crushed by the rollers in the minilab, causing "folding".

In general, a film-integrated camera of this type finishes photographing all frames of an unexposed film loaded in a supply room, and after winding up all of them in an empty cartridge loaded in a winding room, the camera itself is taken up. The cartridge is broken and the cartridge is taken out and developed, and the camera body is broken every time one film is used and is thrown away. Therefore, this film-integrated camera needs to be as simple and inexpensive as possible. Currently, the film loaded in this type of camera is limited to 12 or 24 frames,
There is no 36 shots. The reason is that shooting conditions are limited to sunny days or in a bright room. If the number of frames is large, all the frames may not be used up and the film may be wasted.

Since the price of the film is reflected as it is in the price of the camera, the camera can be provided at a lower price if the number of frames is small. This is to satisfy the wishes of users who want to develop as soon as possible after taking a picture. However, in recent years, with the spread of disposable cameras, the functions and shooting conditions have improved, and it has become possible to easily take beautiful pictures anytime and anywhere, so it is no longer necessary to use all the frames in a limited time. , Due to the recent tendency to attach importance to quality rather than price, the above reasons ~ have become less of an issue. In addition, there are some people who say that the number of frames is 12 or 24, and the number of frames is too small to respond, so if two similar cameras were purchased, the cost of photography would increase by the amount of the camera itself. Therefore, when the above-mentioned various points are put together, it can be said that the advent of a film-integrated camera in which a 36-frame shooting film is loaded.

On the other hand, with the same number of 24 sheets, there is a need to make the camera smaller and put it in a pocket such as chest or pants without increasing the bulkiness and increasing portability.

[0012]

However, since the 36-frame shooting film is about 60% longer than the 24-frame shooting film, when the unexposed film drawn from the cartridge is rolled into a roll and loaded into the supply chamber, The longer the number of turns, the greater the number of turns, resulting in a tightly wound state (hard to loosen). Moreover, in this case, since the diameter of the innermost layer of the film in the supply chamber is naturally smaller than the diameter of the 24-frame shooting film, the winding start end (the tongue end of the film) becomes a tight curl. Therefore,
After the filming of all frames was completed, the tongue end of the film housed in the cartridge was tightly curled and stuck to the inner wall of the cartridge, making it extremely difficult to pull out the tongue end with a jig during development.

That is, the film-integrated type camera does not have a back cover like a normal camera, and the cartridge in which the photographed film is housed is opened along the axial direction by opening the cartridge insertion / removal lid provided at the lower end of the winding chamber. Since the tongue of the film must be completely housed in the cartridge, it cannot be taken out. Therefore, when developing a cartridge taken out from the film-integrated camera, the tongue end extraction work using a jig is always involved, so loading the 36-frame shooting film, which makes the work difficult, is difficult from the standpoint of the developing side. I was shunned.

Further, even when shooting 24 frames, it is necessary to reduce the winding diameter in order to make the camera thinner.
If so, curling is likely to occur, and the work of the tongue end becomes extremely difficult, which is a problem. In particular, when exposed to a high-temperature atmosphere in the summer, the curls become stronger and the work at the tip of the tongue becomes more difficult, as well as non-uniformity and the fatal failure of trailing edge breakage in the trailing edge free development processing such as the minilab mentioned above. .

In view of the above points, the present invention integrates a 24- or 36-frame taking film which does not cause uneven development and trailing end breakage in a minilab without making the tongue end work of the film difficult even when core-set at a high temperature. The purpose is to provide a camera.

[0016]

In order to achieve the above object, the present invention provides a thin film of a polyester film having a glass transition temperature Tg of 90 ° C. or higher and 200 ° C. or lower as a support, and a temperature of 50 ° C. or higher and a Tg temperature of 50 ° C. or higher before emulsion coating. We have found that it is effective to use a film that has been heat-treated at the following temperatures, and found that incorporating this film into a film-integrated camera is extremely effective in increasing the number of frames and making it thinner. It was

That is, the present invention has achieved the above object by the following means. (1) The unexposed film drawn from the patrone is rolled up and loaded into the supply chamber, the empty patrone is loaded into the winding chamber, and the unexposed film is pulled out from the supply chamber and rolled up into the patrone for each shooting. In the film-integrated camera configured as described above, the support is a polyester support and the glass transition temperature is 90 ° C.
An unexposed film which is heat-treated at a temperature of 50 ° C. or higher and a glass transition temperature or lower at a temperature of not lower than 200 ° C. and not higher than 200 ° C. and before applying an undercoat layer or before applying an undercoat layer,
A film-integrated camera characterized in that the central part is empty or is wound in a spool.

(2) The film-integrated camera according to item (1), wherein the polyester-based support is a polyester containing naphthalenedicarboxylic acid and ethylene glycol as main materials. (3) The film-integrated camera according to item (1) or (2), wherein the polyester of the polyester support is polyethylene-2,6-naphthalenedicarboxylate.

(4) The film-integrated camera according to item (1), wherein the spool has a core diameter of 9 mm or less. (5) The thickness of the polyester support is 50 to 90 μm.
The film-integrated camera according to any one of items (1) to (3), wherein m is m. 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) Core set curl A curl in the length direction attached by the core set. The degree of curling is ANSI / ASC pH 1.29-1985.
1 / R, measured according to Test Method A of
[M] (R is the radius of the curl). (3) 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.

In order to achieve the above-mentioned two problems, that is, high mechanical strength and low curl, there are two methods. The first method is a method in which TAC having a curl-up recovery property is modified so as to improve the mechanical strength. The second method is a method of improving the mechanical strength of a polyester support typified by PET so that it is less likely to be curled.

To achieve this task by the former method,
Expected to be very difficult. That is, the thickness of the TAC support used in the current color negative photographic material is 122
.mu.m, and when it is reduced to 90 .mu.m, the flexural modulus is proportional to the cube of the thickness, and therefore it is reduced to 40% of the 122 .mu.m support. That is, it is necessary to achieve a support having a modulus 2.5 times stronger. In addition, the spool diameter is 10
If it is reduced to less than mm, even TAC having curl recovery property cannot be fully recovered during the development process, and the above-mentioned "processing unevenness" and "folding" occur, and the tongue tip work becomes difficult. As described above, it is considered difficult to simultaneously solve the three problems of “improvement of elastic modulus by 2.5 times”, “improvement of curling and curling recovery”, and “improvement of tongue end work”.

On the other hand, when the latter method is used, for example, the bending elasticity equivalent to TAC of 122 μm can be achieved at 90 μm because of the strong elastic modulus inherent in the case of using PET. In addition, polyethylene naphthalate (PE
N) has a higher elastic modulus than PET and is 80μ.
It can be thinned to near m. So in the latter case,
It is only necessary to improve the curling of these supports, and as a result of the study, the present invention was achieved.

Several attempts have hitherto been made as methods for reducing the curl of a polyester film.
For example, the method described in JP-A-51-16358,
That is, a method of heat treatment at a temperature lower than the glass transition temperature by 30 ° C. to 5 ° C. is known. In this method, enthalpy relaxation is performed in the film during the heat treatment to reduce the free volume, so that the flow of molecules is suppressed and the curling is less likely to occur.

When this method is used, the effect of making it harder to curl is recognized, but when it is exposed to the highest temperature when used by general users, that is, when the temperature in the car in summer reaches 80 ° C. The strong curl curls again. On the other hand, a method as disclosed in Japanese Patent Application Laid-Open No. 1-131550, that is, a structure is provided in the base so that a curl is formed in a direction opposite to the winding direction as a product, and the curl with time is offset when the product is stored. There is a way to do it. In this method, in a sequential biaxial stretching step, a permanent curl is provided by imparting a difference in crystallinity and orientation by providing a temperature gradient on the front and back surfaces of the film between longitudinal stretching and transverse stretching. When this method is used, it is not possible to obtain a sufficient winding curl improvement when it is wound on a thin spool as the subject of the present invention.

This is because the effect of this heat treatment disappears when exposed to a temperature exceeding the glass transition temperature. Therefore, a polyester having a glass transition temperature as high as possible is desirable, and the temperature exposed to the highest temperature when used in a general user. ,
That is, the temperature in the car in the summer is over 80 ℃
It is necessary to have the above glass transition temperature. On the other hand, there is no general-purpose polyester film which is transparent and has a temperature higher than 200 ° C. Therefore, the temperature of the polyester used in the present invention needs to be 90 ° C. or higher and 200 ° C. or lower.

There are various kinds of polyesters as described above, but those having a high performance by balancing both the difficulty of rolling and the mechanical strength and the high performance are polyesters containing naphthalene dicarboxylic acid and ethylene glycol as main components. Among them, polyethylene-2,6-naphthalene dicarboxylate (PEN) is particularly preferable. These supports preferably have a thickness of 50 μm or more and 90 μm or less. If it is less than 50 μm, it cannot withstand the shrinkage stress of the photosensitive layer generated at the time of drying, while if it exceeds 90 μm, it contradicts the purpose of reducing the thickness for compactness.

This heat treatment must be carried out at a temperature of 50 ° 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. On the other hand, at a temperature of 50 ° C., this effect is unrealistic because it takes a lot of time because it proceeds only at a remarkably slow speed.

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 50 ° 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.

The present invention will be further described in detail below. However, the present invention is not limited to these. First, the glass transition temperature used in the present invention is 9
The polyester of 0 ° C. or higher and 200 ° C. or lower will be described.
The polyester of the present invention having a glass transition temperature of 90 ° C. or higher is formed from a diol and a dicarboxylic acid, and usable dibasic acids include terephthalic acid, isophthalic acid,
Phthalic acid, phthalic anhydride, 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, 1,4-cyclohexanedicarboxylic acid,

[0030]

[Chemical 1]

[0031]

[Chemical 2] Etc. can be mentioned. Usable diols include 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-benzenedimethanol,

[0032]

[Chemical 3]

[0033]

[Chemical 4] Etc. can be mentioned. In addition, if necessary, a monofunctional or trifunctional or higher polyfunctional hydroxyl group-containing compound, or
The acid-containing compound may be copolymerized. In addition, 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.

Examples of such compounds include the following.

[0035]

[Chemical 5] Among the polyesters composed of these diols and dicarboxylic acids, more preferred are homopolymers such as polyethylene terephthalate, 2,6-dinaphthalate (PEN), polyacrylate (PAr) and polycyclohexanedimethanol terephthalate (PCT). , And 2,6-naphthalenedicarboxylic acid (NDCA), terephthalic acid (TPA), isophthalic acid (IPA), orthophthalic acid (OPA), cyclohexanedicarboxylic acid (CHDC), paraphenylenedicarboxylic acid (PPDC), as dicarboxylic acid, As diol, ethylene glycol (EG), cyclohexanedimethanol (CHD
M), neopentyl glycol (NPG), bisphenol A (BPA), biphenol (BP), and parahydroxybenzoic acid (PHB) as a hydroxycarboxylic acid.
A), 6-hydroxy-2-naphthalenecarboxylic acid (H
NCA) is copolymerized. More preferred among these are naphthalene dicarboxylic acid, terephthalic acid and ethylene glycol copolymers (mixing molar ratio of naphthalene dicarboxylic acid and terephthalic acid is preferably between 0.3: 0.7 and 1.00, 0.
It is more preferably 5: 0.5 to 0.8: 0.2. ), A copolymer of terephthalic acid, ethylene glycol, and bisphenol A (the mixing molar ratio of ethylene glycol and bisphenol A is preferably between 0.6: 0.4 and 0: 1.0, more preferably 0.5: 0.5). .About.0: 0.9), isophthalic acid, paraphenylenedicarboxylic acid, and a copolymer of terephthalic acid and ethylene glycol (isophthalic acid; the molar ratio of paraphenylenedicarboxylic acid is 0.1 when terephthalic acid is 1). 10.
0, 0.1 to 20.0, and more preferably 0.
2 to 5.0, preferably 0.2 to 10.0), naphthalene dicarboxylic acid, a copolymer of neopentyl glycol and ethylene glycol (the molar ratio of neopentyl glycol and ethylene glycol is 1: 0 to 0.7: 0. 3 is preferable, and 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), a copolymer of para-hydroxybenzoic acid, ethylene glycol and terephthalic acid (molar ratio of para-hydroxybenzoic acid, ethylene glycol is 1: 0 to 0.1 :).
0.9 is preferable, and 0.9: 0.1 is more preferable.
0.2: 0.8) and other copolymers and PEN and PET
(A composition ratio of 0.3: 0.7 to 1.0: 0 is preferable, and 0.
5: 0.5 to 0.8: 0.2 is more preferable), PET
And PAr (composition ratio of 0.6: 0.4 to 0: 1.0 is preferable, and 0.5: 0.5 to 0: 0.9 is more preferable).

PEN is the most balanced of these polyesters, has a mechanical strength, especially a high elastic modulus, and has a sufficiently high glass transition temperature of about 120 ° C.
However, it has the drawback of emitting fluorescence. On the other hand, P
Although CT has a high mechanical strength and a glass transition temperature as high as around 110 ° C., it has a defect that it is difficult to obtain a transparent film because the crystallization rate is extremely high. PAr has the highest glass transition temperature (190 ° C.) of these polymers, but has a drawback that mechanical strength is weaker than that of PET. Therefore, in order to make up for these drawbacks, blends of these polymers or copolymers of the monomers forming them can be used.

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 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.

Further, in order to improve the adhesiveness with other polyesters, these polyesters may be partially blended with another polyester within a range where the glass transition temperature is not lower than 90 ° C. It is possible to copolymerize the monomers constituting the polyester, or to copolymerize a monomer having an unsaturated bond in these polyesters and radically crosslink the monomers.

Next, examples of preferable specific compounds of the polyester used in the present invention are shown, but the present invention is not limited thereto. Example of polyester compound Homopolymer PEN: [2,6-naphthalenedicarboxylic acid (NDCA) / ethylene glycol (EG) (100/100)] Tg = 119 ° C. PCT: [terephthalic acid (TPA) / cyclohexanedimethanol (CHDM) ) (100/100)] Tg = 93 ° C. PAr: [TPA / bisphenol A (BPA) (100/100)] Tg = 192 ° C. Copolymer (() represents a molar ratio.) PBC-12 , 6-NDCA / TPA / EG (50/50/100) Tg = 92 ° C. PBC-2 2,6-NDCA / TPA / EG (75/25/100) Tg = 102 ° C. PBC-3 2,6-NDCA / TPA / EG / BPA (50/50/75/25) Tg = 112 ° C. PBC-4 TPA / EG / BPA (100/50 50) Tg = 105 ° C. PBC-5 TPA / EG / BPA (100/25/75) Tg = 135 ° C. PBC-6 TPA / EG / CHDM / BPA (100/25/25/50) Tg = 115 ° C. PBC- 7 IPA / PPDC / TPA / EG (20/50/30/100) Tg = 95 ° C. PBC-8 NDCA / NPG / EG (100/70/30) Tg = 105 ° C. PBC-9 TPA / EG / BP (100 / 20/20) Tg = 115 ° C. PBC-10 PHBA / EG / TPA (200/100/100) Tg = 125 ° C. Polymer blend (() represents weight ratio.) PBB-1 PEN / PET (60 / 40) Tg = 95 ° C. PBB-2 PEN / PET (80/20) Tg = 104 ° C. PBB-3 PAr / PEN (50/50) Tg = 1 2 ° C. PBB-4 PAr / PCT (50/50) Tg = 118 ° C. PBB-5 PAr / PET (60/40) Tg = 101 ° C. PBB-6 PEN / PET / PAr (50/25/25) Tg = 108 All of the polyesters above ℃ have a higher flexural modulus than TAC, and it is possible to realize the thinning of the film, which is the original purpose. However, PEN had the strongest bending elasticity among these, and when it was used, TAC was 1
It is possible to reduce the required film thickness of 22 μm to 80 μm.

An ultraviolet absorber may be kneaded into these polymer films for the purpose of preventing fluorescence and imparting stability with time. It is desirable that the ultraviolet absorber does not have absorption in the visible region, and the addition amount thereof is usually 0.01% by weight to 2% based on the weight of the polymer film.
0% by weight, preferably 0.05 to 10% by weight
It is a degree. If it is less than 0.01% by weight, the effect of suppressing deterioration of ultraviolet rays cannot be expected. 2,4-as an ultraviolet absorber
Dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2, 2'-dihydroxy-
Benzophenone series such as 4,4'-dimethoxybenzophenone, 2 (2'-hydroxy-5-methylphenyl)
Benzotriazole, 2 (2'-hydroxy 3 ', 5'
-Di-t-butylphenyl) benzotriazole, 2
Examples thereof include benzotriazole-based UV absorbers such as (2′-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. Polyesters, especially aromatic polyesters, have a high refractive index of 1.6 to 1.7, while gelatin, which is the main component of the photosensitive layer coated thereon, has a refractive index of 1.50 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 for avoiding such a light piping phenomenon, a method of adding inert inorganic particles and the like to the film and a method of adding a dye 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. 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 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 commercially available dyes for polyester such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku. 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.

The polyester film according to the present invention can be imparted with slipperiness depending on 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, an external particle system is used. It is desirable to select SiO ₂ having a refractive index relatively close to that of the polyester film, or an internal particle system capable of relatively reducing the precipitated particle size.

Further, 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 the formation of polar groups on the surface of the support, which was originally hydrophobic, to some extent, and the increase of the crosslink density of the surface. 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. 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 most 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.

The discharge frequency is from direct current to several thousand MHz, preferably 50, as seen in the prior art.
Hz to 20 MHz is suitable. 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 to ¹ KV · A · min / m ² is suitable.

Next, regarding the undercoating method (2), 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 multilayer 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 substrates 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. As the water-soluble polymer, gelatin, gelatin derivative, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, maleic anhydride copolymer, etc.,
Examples of the 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, 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 comprises SiO ₂ , Ti
O ₂ and 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 such as 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.

The most preferable antistatic agent for the back layer of the present invention is ZnO, TiO ₂ , SnO ₂ or Al _2.
O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO
It is fine particles of at least one crystalline metal oxide selected from the group ₃ or a composite oxide thereof. The fine particles of the conductive crystalline oxide or the composite oxide thereof used in the present invention have a volume resistivity of 10 ⁷ Ωcm or less, more preferably 10 ⁵ Ωcm or less. The particle size is 0.002-0.7 μm, especially 0.005-0.3 μm.
Is desirable.

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 light-sensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045, and JP-A No. 57-1127.
No. 51, No. 62-200350, No. 62-20654.
No. 1, No. 62-206543, No. 56-25738.
No. 62-63936, 59-202464,
It is described in Japanese Examined Patent Publication Nos. 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, twin planes and the like. It may have a crystal defect or a composite form thereof.

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) N.
17643 (December 1978), pp. 22-23,
"I. Emulsion preparation
ion and types) "and the same No. 18
716 (November 1979), p.648, Graphide, "Physics and Chemistry of Photography," published by Paul Montel (P.Gl.
afkides, Chemie et Phisiqu
e Photographique, PaulMont
el, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photo.
graphic Evolution Chemistr
y (Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (VL Zelikman et al., Maki).
ng and Coating Photograph
ic Emulsion, Focal Press, 1
964) and the like.

US Pat. Nos. 3,574,628 and 3,
655,394 and British Patent 1,413,748.
The monodisperse emulsions described in JP-A No. 1989-2000 are also preferable. Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described 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.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The efficiency of the present invention is particularly remarkable when an emulsion sensitized with a gold compound and a sulfur-containing compound is used. The additives used in such a process 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) (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 page 649 right column to 6 light absorbers, filter dyes, ultraviolet absorbers 25 to 26 page 649 right column to 650 left column 7 Anti-staining agent, page 25, right column, page 650, left to right column, 8 Dye image stabilizer, page 25, hardener, page 26, page 651, left column 10 Binder, page 26, ibid. 11 Plasticizer, lubricant, page 27, page 650, right column 12 Application Auxiliaries and surfactants, pages 26 to 27, page 650, right column Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is described in US Pat. Nos. 4,411,987 and 4,435,503. Taho It is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with lumaldehyde.

Various color couplers can be used in the present invention, and specific examples thereof 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 shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137 and the like.

A coupler that 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.

As a coupler which releases a nucleating agent or a development accelerator in an image form at the time of development, British Patent No. 2,092
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. 2,322,027. The boiling point at atmospheric pressure used in oil-in-water dispersion method is 17
Specific examples of the high boiling point organic solvent having a temperature of 5 ° C. or higher include phthalic acid esters, phosphoric acid or phosphonic acid esters, benzoic acid esters, amides, alcohols or phenols, aliphatic carboxylic acid esters, and aniline derivatives. , Hydrocarbons and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C or higher and about 16 ° C.
An organic solvent at 0 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

The steps of the latex dispersion method, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230. 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 treated min 15 seconds and the saturated film thickness, which time defined to reach the thickness of the T ^_1/2.

[0081] The film swelling speed 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.

[0082]

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. PEN: 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., extruded from a T-die and longitudinally stretched 3.3 times at 140 ° C., and then 130 times.
The film was transversely stretched 3.3 times at 0 ° C., and further heat set at 250 ° C. for 6 seconds. PET: 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.・ TAC: Methylene chloride / methanol = 82 / 8w by a normal solution casting method of triacetyl cellulose
t ratio, TAC concentration 13%, plasticizer TPP / BDP = 2 /
1 (where TPP; triphenyl phosphate, BD
P; biphenyl diphenyl phosphate) 15 wt
% Band method.・ PEN / PET = 4/1 (weight ratio); PE in advance
The N and PET pellets were vacuum dried at 150 ° C. for 4 hours, kneaded and extruded at 280 ° C. using a biaxial kneading extruder, and then pelletized.

A film of this polyester was formed under the same conditions as for PEN.

2) Coating of undercoat layer Each of the above supports was subjected to corona discharge treatment on both sides thereof, and then the undercoat liquid having the following composition was applied to provide the undercoat layer on the high temperature surface side during stretching. . For the corona discharge treatment, a solid state corona treatment machine 6KVA model manufactured by Pillar Co. is used, and a 30 cm wide support is treated at 20 m / min. 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 the treatment was 9.
At 6 KHz, the gap clearance between the electrode and the dielectric roll was 1.6 mm.

Gelatin 3 g Distilled water 250 cc Sodium α-sulfodi-2-ethylhexyl succinate 0.05 g Formaldehyde 0.02 g For Support C, an undercoat layer having the following composition was provided.

Gelatin 0.2 g Salicylic acid 0.1 g Methanol 15 cc Acetone 85 cc Formaldehyde 0.01 g

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
00 parts by weight was redispersed in 1500 parts by weight of water, and sprayed in a baking furnace heated to 600 ° C. to obtain a bluish average particle size of 0.2
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.BA).
CHOFENAG) and dispersed 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 would be 0.1 μm,
It was dried at 115 ° C. for 3 minutes. [Formulation A] 10 parts by weight of the conductive fine particle dispersion described above 1 part by weight of gelatin 27 parts by weight of water 60 parts by weight of methanol 2 parts by weight of resorcin 0.01 part by weight of polyoxyethylene nonylphenyl ether [coating liquid for coating layer (B)] Cellulose triacetate 1 part by weight Acetone 70 parts by weight Methanol 15 parts by weight Dichloromethylene 10 parts by weight p-Chlorophenol 4 parts by weight

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 method, each layer having the composition shown below was coated in multiple layers to prepare a multilayer color photosensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in 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 0.18 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

4th layer (medium-speed 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

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

Twelfth layer (medium-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.

[0109]

[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 for each layer are shown.

[0112]

[Chemical 6]

[0113]

[Chemical 7]

[0114]

[Chemical 8]

[0115]

[Chemical 9]

[0116]

[Chemical 10]

[0117]

[Chemical 11]

[0118]

[Chemical 12]

[0119]

[Chemical 13]

[0120]

[Chemical 14]

[0121]

[Chemical 15]

[0122]

[Chemical 16]

[0123]

[Chemical 17]

[0124]

[Chemical 18]

[0125]

[Chemical 19]

[0126]

[Chemical 20]

6) Processing of photographic film sample The photographic film sample prepared in this way is 35 m long.
A film-integrated camera was produced by slitting the film to a width of 1.8 m and punching it into a unit as shown in FIG. 1 or 2. FIG. 1 is a top view showing the internal structure of a film-integrated camera which is one form of the present invention.
In this camera 1, a unit 3 is housed inside a camera outer case 2. In this unit 3, the unexposed film 8 pulled out from the cartridge 6 is rolled up and the supply chamber 4
Is loaded into. Then, the film is pulled out from the supply chamber 4 and wound up in the cartridge 6 each time the image is taken. Reference numeral 7 is a taking lens, and 9 is a film supporting surface.

FIG. 2 shows only the unit 13 portion of another type of film-integrated type camera according to the present invention, which is the spool 21 in the cartridge 16 (the spool is described in FIG. 1). The spool 22 is provided in the sub-lay chamber 14 as well. The film 18 uses 36 frames. 7) Core set The above-mentioned film-integrated camera was heated at 80 ° C. for 2 hours to have a curl. This temperature condition is a condition assuming a vehicle in the summer. 8) Extraction of tongue end, development process, curl measurement After the film-integrated camera with a curled curl under the above conditions was left to cool overnight in a room at 25 ° C, the tongue end was extracted with a jig and Automatic processor (Mini Lab FP-55
0B: made by Fuji Photo Film Co., Ltd.) and immediately processed to 25
Curl measurement was performed at 60 ° C. and 60% RH.

The development processing conditions are as follows.

Treatment Step 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 Settlement 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 a total volume of 1 liter Stop solution Sodium thiosulfate 10g Ammonium thiosulfate (70% aqueous solution) 30 ml Acetic acid 30 ml Sodium acetate 5 g Potassium alum 15 g Ethylenediaminetetrairon (trivalent) sodium dihydrate 100g Potassium bromide 50g Ammonium nitrate 50g Horic acid 5g Ammonia water Adjust pH to 5.0 Total volume with water 1 liter Fixer Sodium thiosulfate 150g Sulfurous acid Over da 15g Ho sand 12g glacial acetic acid 15 ml Potassium alum 20g Water to make the total amount 1 liter stabilizing bath Ho acid 5g sodium citrate 5g Metaho sodium (tetrahydrate) were added to 3g potassium alum 15g water total amount 1 liter

9) Measurement results The above results are shown in Tables 2 and 3. With the film-integrated camera using the film made of the support of the present invention, the tongue end can be easily pulled out, and the trouble of uneven development of the film and folding of the rear end does not occur. Further, although not shown in Tables 2 to 3, even if the type of the support is PEN, if the thickness of the support is less than 50 μm, the support cannot have bending elasticity to withstand the contraction stress of the photosensitive layer. A gutter-like curl was generated, and scratches were generated in the development processing step. The same was true for other polyesters. If the support has a thickness of 90 μm or more, the camera and the cartridge cannot be downsized.

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-1,4) having a Tg of 225 ° C. is used. -Phenylene) could not be applied to a light-sensitive material because a transparent support was not obtained.

[0133]

[Table 2]

[0134]

[Table 3]

[0135]

In the film-integrated camera of the present invention, the glass transition temperature is 90 ° C. with the polyester support.
It is loaded with an unexposed film produced from a support heat-treated at a temperature of not lower than 200 ° C. and not higher than 200 ° C. and before applying an undercoat layer or after applying an undercoat layer and at a temperature of not lower than 50 ° C. and not higher than the glass transition temperature. The edges can be easily pulled out, curling is hard to occur, 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.

[Brief description of drawings]

FIG. 1 is a top view showing the internal structure of one type of film-integrated camera of the present invention.

FIG. 2 shows a partial cross-sectional top view of a unit of another type of film-integrated camera of the present invention.

[Explanation of symbols]

 1 ... Film integrated camera 2 ... Camera outer box 3,13 Units 4,14 Supply room 5,15 Winding room 6,16 Patron 7 Photo lens 8 ...・ ・ Film 9 ・ ・ ・ ・ Film support surface 17 ・ ・ ・ Lens unit 18 ・ ・ ・ Film (36 frames taken) 20 ・ ・ ・ Exposed frame 21, 22 ・ Spool

Claims (5)

[Claims] 1. An unexposed film drawn from a cartridge is loaded into a supply chamber, and an empty cartridge is loaded into a winding chamber. In a film-integrated camera configured to be rolled up,
The support is a polyester-based support and has a glass transition temperature of 90 ° C. or higher and 200 ° C. or lower, and is heat-treated at a temperature of 50 ° C. or higher and a glass transition temperature or lower before applying the undercoat layer or after applying the undercoat layer and before applying the emulsion. A film-integrated camera, characterized in that an unexposed film, which is the same as the original film, is loaded in a state where the center part is empty or wound on a spool. 2. The film-integrated camera according to claim 1, wherein the polyester support is a polyester containing naphthalenedicarboxylic acid and ethylene glycol as main materials. 3. The film-integrated camera according to claim 1, wherein the polyester of the polyester-based support is polyethylene-2,6-naphthalenedicarboxylate. 4. The film-integrated camera according to claim 1, wherein the spool has a core diameter of 9 mm or less. 5. The polyester support has a thickness of 50.
The film-integrated camera according to claim 1, wherein the film-integrated camera has a thickness of about 90 μm.