JP3016170B2 - Film integrated camera - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention particularly relates to a thin support, which is hardly curled at high temperatures, facilitates the work of extracting the tongue end of the film, and does not cause unevenness in the development process and breakage of the rear end. The present invention relates to a film-integrated camera having excellent adhesiveness.

[0002]

BACKGROUND OF THE INVENTION Photographic materials are generally prepared by coating at least one photographic 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. I have.

In general, photographic light-sensitive materials are in the form of sheets such as X-ray films, plate making films and cut films, and typical roll films are 35 m / m or less in width. This is a color or black-and-white negative film that is housed in a patrone and is loaded into a general camera and used for photographing.

[0004] As a roll film support, mainly T
AC is used, but its greatest feature is that it has no optical anisotropy and high transparency. There is one more excellent feature, which is that it has excellent properties in terms of curl removal after development. That is, TA
The characteristic of C film is its relatively high water absorbency as a plastic film due to its molecular structure. Therefore, curled curl caused by aging in the state of being wound as a roll film causes molecular chains to flow due to water absorption during development processing. In turn, the immobilized molecular chains undergo rearrangement with the elapse of time.

[0005] As a result, it has an excellent property that the curl once formed is eliminated. TA like this
In the case of a photographic photosensitive material using a film having no curl recovery property such as C, when used in a roll state, for example, a baking process or the like in which an image is formed on a photographic printing paper after development causes scratches. In addition, problems such as defocusing and jamming at the time of conveyance occur.

[0006] On the other hand, PET film has been considered to be an alternative to TAC because of its excellent productivity, mechanical strength, and dimensional stability. Due to the strong curl remaining, the handleability after the development processing is poor, and the range of use has been limited despite the excellent properties described above.

In recent years, the use of photographic light-sensitive materials has been diversified, and the speed of film transport during photographing, the increase in photographing magnification, and the miniaturization of photographing apparatuses have been remarkably progressing. In that case, as a support for the photographic photosensitive material,
Properties such as strength, dimensional stability, and thinning are required. Further, with the downsizing of the photographing apparatus, the demand for downsizing the patrone has increased. Conventionally, in the 135 system, a patrone having a diameter of 25 mm has been used. For example, the spool (core) is reduced to 10 mm or less, and at the same time, the current 1
122μ of TAC support thickness used in 35 system
If the thickness of the patrone is reduced to 90 μm from
mm or less.

There are two problems in reducing the size of such a patrone. The first problem is a decrease in mechanical strength due to thinning of the film. In particular, the bending elasticity decreases in proportion to the cube of the thickness. A silver halide photographic light-sensitive material is generally provided with a photosensitive layer dispersed in gelatin, and this layer causes shrinkage due to low humidity, and curls in the width direction (U-shape). The support must have sufficient bending elasticity to withstand this contraction stress.

[0009] The second problem is a strong curl generated during storage over time due to the miniaturization of the spool. In the conventional 135 system, the winding diameter becomes the smallest inside the patrone.
The winding diameter is 14 mm even for a six-image film. If it is attempted to reduce the size to 10 mm or less, a remarkable curl is attached, which causes various troubles. For example,
When development processing is performed on the minilab automatic 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, which causes "process unevenness". In addition, the winding of the film is crushed by a roller in the mini lab, and "breaking" occurs.

In general, this type of film-integrated camera finishes photographing all the frames of the unexposed film loaded in the supply chamber, winds up the entire film in the empty cartridge loaded in the hoisting chamber, and then moves the camera itself. The cartridge is broken, the patrone is taken out and developed, and the camera body is broken each 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 frames or 24 frames.
There are no 36 frames. The reason is,

If the shooting conditions are limited to a sunny day or a bright room, and the number of frames is large, all the frames cannot be used up and the film may be wasted. Since the price of the film is directly reflected in the price of the camera, the smaller the number of frames, the cheaper the camera. This is to satisfy the user's desire to develop as soon as possible.

However, in recent years, disposable cameras have
With its spread, functions and shooting conditions have been improved, and beautiful pictures can be easily taken anytime, anywhere.
It is no longer necessary to use all the pieces at a limited time, and because of the recent tendency to emphasize quality over price,
The reason was no longer a problem. In addition, there are voices saying that "the number of frames is so small that they cannot be taken" when shooting 12 frames or 24 frames, and when two similar cameras are purchased, the cost of photography is increased by the amount of the camera itself. Therefore, taking the above various points into consideration, it can be said that the appearance of a film-integrated camera loaded with a 36-frame film is expected.

On the other hand, in the case of the same twenty-four frames, there is a need to increase the portability by putting the camera in a pocket such as clothes or trousers without making the camera smaller and more easily bulky.

[0014]

However, since the 36-frame film is about 60% longer than the 24-frame film, the unexposed film drawn from the patrone is rolled up and loaded into the supply chamber. The longer the number of turns, the greater the number of turns and the sealed state (the more difficult to loosen). In addition, in this case, the diameter of the innermost layer of the film in the supply chamber is naturally smaller than the diameter of a 24-frame film, so that the winding start end (film tongue end) is tightly curled. Therefore,
After the photographing of all the frames, the tongue end with the tight curl of the film accommodated in the patrone came into close contact with the inner wall of the patrone, which made it extremely difficult to extract the tongue end with a jig during development.

That is, the film-integrated camera does not have the back cover as in a normal camera, and the patrone containing the photographed film is opened along with the patrone insertion / removal lid provided at the lower end of the winding chamber. If the film tongue end is not completely housed in the patrone, it will become a hindrance and cannot be taken out. Therefore, when developing the patrone taken out from the film-integrated camera, the tongue end extraction work using a jig always accompanies, and the loading of the 36-frame shooting film, which makes the work difficult, is from the development standpoint. Was shunned.

Further, in taking 24 frames, it is necessary to reduce the winding diameter in order to further reduce the thickness of the camera, but this causes a problem that curling is likely to occur and the tongue end extraction operation becomes extremely difficult. In particular, when exposed to a high-temperature and high-humidity atmosphere in the summer, the curl becomes stronger and the tongue tip extraction work becomes more difficult. In addition, unevenness and rear end breakage occur in the rear-end-free developing processor such as the minilab described above. Causes catastrophic failure and further failure due to adhesion between the emulsion surface and the back surface.

In view of the above, it is an object of the present invention to provide a minilab in which the adhesion between the emulsion surface and the back surface hardly occurs even if the core is set at a high temperature without making it difficult to extract the tongue end of the film. It is another object of the present invention to provide a camera integrated with 24 to 36 frames taking film which does not cause uneven development and break of the rear end.

[0018]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for manufacturing a photographic material , comprising:
An unexposed film containing a matting agent is rolled into at least one of the surfaces of the solution and loaded into the supply chamber, and an empty patrone is loaded into the take-up chamber. in the film integral camera comprising configured to wind the, and naphthalene dicarboxylic acid support gaga glass transition temperature is below 200 ° C. 90 ° C. or more of the film Echirengo
It is made of polyester whose main material is recall (however,
Copolymerization of aromatic dicarboxylic acid having metal sulfonate group
Excludes polyester made as a combined component)
After forming the support by stretching and heat setting, and with an undercoat layer
After it is given before or subbing layer applied before emulsion coating, in which heat-treated at a temperature below the glass transition temperature or higher 50 ° C.
When the exposure film having the support is empty at the center or
This is achieved by a film-integrated camera, which is loaded while being wound on a spool having a core diameter of 9 mm or less .

First, a description will be given of the curl measurement method used hereinafter and terms relating thereto, etc., in order to facilitate understanding.

(1) Winding a core set film around a spool to give a curl. (2) Core set curl The core set curl is applied in the length direction. The degree of curling is determined by T of ANSI / ASC pH 1.29-1985.
est Method A, 1 / R
[M] (R is the radius of the curl).

(3) Glass transition temperature (Tg) Using a differential thermal analyzer (DSC), the sample film 10
mg in a helium nitrogen stream at a rate of 20 ° C./min. When the absorption peak appears at the arithmetic mean temperature or Tg of the temperature that begins to deviate from the baseline and the temperature that returns to a new baseline. The temperature indicated by the maximum endothermic peak is defined as Tg.

First, the support of the present invention will be described. The Tg of the support of the present invention is a polyester of 90 ° C. to 200 ° C., and is heat-treated at a temperature of 50 ° C. or more and Tg or less, which will be described below. There are two ways to achieve high mechanical strength and low curl. The first method is to use a TAC having rolled recovery properties.
This is a method that denatures and improves mechanical strength. The second method is a method of improving the mechanical strength so that the polyester support represented by PET is hardly curled.

To accomplish this task in the former way,
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 this is reduced to 90 .mu.m, the flexural modulus is proportional to the cube of the thickness, and therefore decreases to 40% of the 122 .mu.m support. That is, it is necessary to achieve a support having a 2.5 times higher elastic modulus. If the spool diameter is 10
When the diameter is reduced to not more than mm, even TAC having curl recovery property cannot be sufficiently recovered during the development processing, and the above-mentioned "processing unevenness" and "folding" occur. in this way,
"2.5 times improvement in elastic modulus" and "improved curl recovery"
It is considered very difficult to solve these two problems at the same time.

On the other hand, when the latter method is to be achieved, for example, a bending elasticity equivalent to TAC of 122 μm can be achieved at 90 μm due to the inherently high elastic modulus when PET is used. Furthermore, polyethylene naphthalate (PE
When N) is used, the modulus of elasticity is higher than that of PET and 80 μm.
m can be reduced. So in the latter case,
It is only necessary to improve the curling of these supports, and as a result of investigation, the present invention has been reached.

Several attempts have conventionally been made to reduce the curl of a polyester film. For example, a method described in JP-A-51-16358, that is, a method of performing heat treatment at a temperature lower by 30 ° C. to 5 ° C. than the glass transition temperature is known. According to this method, the enthalpy is relaxed in the film during the heat treatment to reduce the free volume, thereby suppressing the flow of molecules and making the film hard to be curled.

Although this method has the effect of making it difficult to curl, ordinary polyester is exposed to the highest temperature when used by general users, that is, the temperature in a car in summer of 80 ° C. If it reaches, it will have a strong curl again.

Some attempts have been made to reduce the curl of the polyester film.
For example, a method described in JP-A-51-16358, that is, a method of performing heat treatment at a temperature lower than the glass transition temperature by 30 ° C. to 5 ° C. is known.

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 the product is curled in a direction opposite to the winding direction, and
There is a method of offsetting the curl with the lapse of time during product storage.
In this method, in a successive biaxial stretching step, permanent curl is imparted by giving a difference in crystallinity and orientation by giving a temperature gradient to the front and back surfaces of the film between longitudinal stretching and transverse stretching. When using this method, when wound around a thin spool as the subject of the present invention,
A sufficient curling improvement effect could not be obtained.

This is because the effect of this heat treatment disappears when exposed to a temperature exceeding the glass transition temperature. Therefore, it is desirable to use a polyester having a high glass transition temperature as much as possible. That is, it is necessary to have a glass transition temperature of 90 ° C. or more as a temperature exceeding 80 ° C. in a car in summer.

[0030]

There are various types of such polyesters. Among them, polyesters having naphthalenedicarboxylic acid and ethylene glycol as main raw materials have high performance by balancing both difficulty in winding and mechanical strength. Among them, particularly, polyethylene-2,6-naphthalenedicarboxylate (PEN) was used. These supports need to 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 during drying, while if it is more than 90 μm, it is inconsistent with the purpose of reducing the thickness for compactness.

This heat treatment must be performed at a temperature of 50 ° C. or more and a glass transition temperature or less, preferably for 0.1 to 1500 hours. This effect proceeds faster as the heat treatment temperature is higher. However, when the heat treatment temperature exceeds the glass transition temperature, the molecules in the film move in a random manner, and conversely, the free volume increases, and the film easily flows, that is, the film is easily rolled. Therefore, this heat treatment must be performed at a temperature lower than the glass transition temperature. On the other hand, at a temperature of 50 ° C. or less, this effect only proceeds at an extremely slow speed, so that it takes a lot of time and is impractical.

Therefore, this heat treatment is desirably performed at a temperature slightly lower than the glass transition temperature in order to shorten the processing time, and is preferably 50 ° C. or higher and lower than the glass transition temperature, more preferably
It is not less than 30 ° C. below the glass transition temperature and not more than the glass transition temperature. On the other hand, when heat treatment is performed under this temperature condition,
The effect is observed after 0.1 hour. On the other hand, after 1500 hours or more, the effect is almost saturated. Therefore 0.1
It is necessary to perform the heat treatment for not less than 1500 hours.

Hereinafter, the present invention will be described in more detail. However, the present invention is not limited by these. First, the glass transition temperature used in the present invention is 90.
A polyester having a temperature of 200 ° C. or higher and 200 ° C. or lower is described. The polyester having a glass transition temperature of 90 ° C. or higher of the present invention is formed from a diol and a dicarboxylic acid, and usable dibasic acids include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, succinic acid, and 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,

[0035]

Embedded image

[0036]

And the like. Usable diols include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptane Diol, 1,8-octanediol, 1,10-decanediol, 1,12-
Dodecanediol, 1,4-cyclohexanediol,
1,4-cyclohexanedimethanol, 1,3-cyclohexanediol, 1,1-cyclohexanedimethanol, catechol, resorcinol, hydroquinone, 1,4
-Benzene dimethanol,

[0038]

[0039]

(However, not only diols but also compounds having both a hydroxyl group and a carboxy group in the molecule at the same time are included).

[0041]

Among these polyesters comprising diols and dicarboxylic acids, more preferred are homopolymers such as polyethylene-2,6-dinaphthalate (PEN ) and 2,6-naphthalenedicarboxylic acid as a dicarboxylic acid. (NDCA ) and the diol include those obtained by copolymerizing ethylene glycol (EG ) and 6-hydroxy-2-naphthalenecarboxylic acid (HNCA). Among them, naphthalenedicarboxylic acid, a copolymer of terephthalic acid and ethylene glycol (a mixture molar ratio of naphthalenedicarboxylic acid and terephthalic acid is preferably between 0.3: 0.7 to 1.0: 0, 0.5: 0.5 to 0.8: 0.2 ), naphthalenedicarboxylic acid, a copolymer of neopentyl glycol and ethylene glycol (the molar ratio of neopentyl glycol to ethylene glycol is 1:
0 to 0.7: 0.3 is preferable, and more preferably 0.
9: 0.1-0.6: 0.4 ) and PE
N and PET (composition ratio is preferably 0.3: 0.7 to 1.0: 0, more preferably 0.5: 0.5 to 0.8: 0.2 ) are preferable, and a polymer blend such as .

PEN is the most balanced of these polyesters, has mechanical strength, especially high elastic modulus, and has a sufficiently high glass transition temperature of around 120 ° C.
However, it has the disadvantage of emitting fluorescence. On the other hand, P
CT has a high mechanical strength and a high glass transition temperature of around 110 ° C., but has an extremely high crystallization rate, and has a drawback that it is difficult to obtain a transparent film. PAr has a high glass transition temperature (192 ° C.) among these polymers, but has the disadvantage that the mechanical strength is weaker than that of PET. Therefore, in order to make up for these drawbacks, it is possible to use a blend of these polymers or a copolymer of monomers forming them.

These homopolymers and copolymers can be synthesized according to a conventionally known polyester production method. For example, when an acid component is directly esterified with a glycol component, or when a dialkyl ester is used as an acid component, first, a transesterification reaction is performed with the glycol component, and this is heated under reduced pressure to remove excess glycol components. By doing so, it can be synthesized. Alternatively, an acid component may be used as an acid halide and reacted with glycol. At this time, if necessary, a transesterification reaction, a catalyst or a polymerization reaction catalyst may be used, or a heat resistance stabilizer may be added. These polyester synthesis methods are described, for example, in Polymer Science, Vol. 5, “Polycondensation and Polyaddition” (Kyoritsu Shuppan, 1980), pp. 103-136.
Page, "Synthetic Polymer V" (Asakura Shoten, 1971), No. 18,
It can be carried out with reference to the description on pages 7 to 286.

The preferred average molecular weight range for these polyesters is from about 10,000 to 500,000.

The polymer blend of the polymer thus obtained is described in JP-A-49-5482 and JP-A-49-5482.
4325, JP-A-3-192718, Research Disclosure 283, 739-41, 284, 779
-82, 294, 807-14. Further, these polyesters can be partially blended with other polyesters, copolymerized with other monomers, or copolymerized with a monomer having an unsaturated bond to undergo radical crosslinking.

Next, preferred specific examples of the polyester used in the present invention will be shown, but the present invention is not limited thereto. Examples of polyester compounds ・ Homopolymer PEN: [2,6-naphthalenedicarboxylic acid (NDCA) / ethylene glycol (EG) (100/100)] Tg = 119 ° C. Copolymer (() indicates a molar ratio. ) PBC-1 2,6-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-8 NDCA / NPG / EG (100/70/30) Tg = 105 ° C・ Polymer blend (in parentheses) represents a weight ratio.) PBB-1 PEN / PET (60/40) Tg = 95 ℃ PBB-2 PEN / PET (80/20) Tg = 104 ℃ PBB 6 PEN / PET / PAr (50/25/25) Tg = 108 polyester as described above ℃ all have strong song modulus than TAC, it is possible to realize a thinning of the film is the original purpose. However, among these, PEN had the strongest bending elasticity, and when it was used, TAC was 1%.
It is possible to reduce the film thickness from 22 μm to 80 μm.

Further, an ultraviolet absorber may be kneaded into these polymer films for the purpose of preventing fluorescence and imparting stability over time. It is desirable that the ultraviolet absorber has no absorption in the visible region, and the amount thereof is usually 0.5% by weight to 20% by weight based on the weight of the polymer film.
% By weight, preferably about 1 to 10% by weight. If it is less than 0.5% by weight, the effect of suppressing the deterioration of ultraviolet rays cannot be expected. As the ultraviolet absorber, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,2 ′, 4,4 Benzophenones such as 4'-tetrahydroxybenzophenone and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone;
(2'-hydroxy-5-methylphenyl) benzotriazole, 2 (2'-hydroxy3 ', 5'-di-t-
Benzotriazoles such as butylphenyl) benzotriazole and 2 (2'-hydroxy-3'-di-t-butyl-5'-methylphenyl) benzotriazole; and salicylic acid-based ultraviolet absorbers such as phenyl salicylate and methyl salicylate. Can be

One of the problems that arises when a polyester film is used as a support for photographic light-sensitive materials is the problem of fogging that occurs because the support has a high refractive index. The refractive index of polyester, particularly aromatic polyester, is as high as 1.6 to 1.7, while the refractive index of gelatin, which is the main component of the photosensitive layer coated thereon, is 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-based film causes a so-called light piping phenomenon (edge fogging).

As a method of avoiding such a light piping phenomenon, a method of incorporating inert inorganic particles or the like into a film and a method of adding a dye are known. A preferred method of preventing light piping in the present invention is a method by adding a dye which does not significantly increase the film haze. The dye used for film dyeing is not particularly limited, but the color tone is preferably gray dyeing due to the general properties of the photosensitive material, and the dye has excellent heat resistance in the film forming temperature range of the polyester film, and polyester. Those having excellent compatibility with are preferred.

As the dye, Mitsubishi Kasei Chemical Co., Ltd.
The purpose can be achieved by mixing dyes commercially available for polyesters such as Diaresin and Kayaset manufactured by Nippon Kayaku. Regarding the dyeing density, it is necessary that the color density in the visible light range is measured with a color densitometer manufactured by Macbeth Co., and that it is at least 0.01. More preferably, it is 0.03 or more.

The polyester film according to the present invention can be provided with lubricity according to the application, and the means for imparting lubricity is not particularly limited.
The kneading of an inert inorganic compound or the application of a surfactant is used as a general method. Such inert inorganic particles include SiO ₂ , TiO ₂ , BaSO ₄ , CaC
O ₃ , talc, kaolin and the like are exemplified. In addition to the lubricity imparted by the external particle system in which inert particles are added to the polyester synthesis reaction system described above, a lubricity imparting method using an internal particle system in which a catalyst or the like to be added during the polymerization reaction of the polyester is precipitated can also be adopted. It is.

The means for imparting lubricity are not particularly limited, but transparency is an important requirement for the support for a photographic light-sensitive material. It is desirable to select SiO ₂ having a refractive index relatively close to that of the polyester film, or an internal particle system capable of relatively reducing the particle diameter of the precipitated film.

Further, in the case of imparting lubricity by kneading, a method of laminating layers provided with functions 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.

Next, the matting agent used in the present invention will be described. Generally, the light-sensitive material has an outermost layer (surface layer) containing a hydrophilic organic colloid represented by gelatin as a binder. Therefore, the surface of the photosensitive material has an increased adhesiveness or tackiness in a high-temperature, high-humidity atmosphere, and easily adheres to another object by coming into contact therewith.

This adhesion phenomenon occurs when the photosensitive material is manufactured, stored,
During photographing, processing, projection, or storage after processing, it occurs between the photographic materials or between the photographic materials and an object in contact with the photographic materials, and often causes serious inconvenience. In order to improve the occurrence of adhesion under such high temperature and high humidity conditions, it is known that the surface of the photosensitive material is provided with irregularities. Methods are known in the art for increasing the so-called matting and reducing the adhesion.

However, as the surface is roughened, the sharpness of the photographic light-sensitive material is reduced and the haze is increased, so that the average particle size and content thereof are limited. The matting agent used in the present invention has an average particle size of 10 ^-3 to 102 μm, preferably 10 ^-1 to 10 μm, more preferably 0.5 to ⁵ μm. The content is, for example, 0.1 to 10 ³ mg / m ² , preferably 5 to 300 mg / m ² , more preferably ²⁰ to ² irrespective of the spherical or irregular matting agent.
50 mg / m ² .

The layer containing the matting agent is not particularly limited as to which layer is on the emulsion side or on the back side, and may be included in a plurality of layers. Preferably, it is the outermost layer on the emulsion side or on the back side. The thickness of the outermost layer is not particularly limited, but is preferably 0.05 to 10 μm, and more preferably 0.15 to 6 μm. The composition of the matting agent used is not particularly limited, but it is an inorganic compound or a polymer compound having a glass transition temperature Tg of 50 ° C. or higher. The Tg of the matting agent in the polymer compound is preferably 60 ° C. or higher, more preferably 65 ° C. or higher. These matting agents can be used in combination of two or more.

The inorganic compound of the matting agent of the present invention includes, for example, barium sulfate, manganese colloid, titanium dioxide,
There are fine powders of inorganic substances such as strontium barium sulfate and silicon dioxide. Further, for example, silicon dioxide such as synthetic silica obtained by a wet method or gelation of silicic acid, or titanium dioxide (rutile type or Anatase type). Further, it can also be obtained by pulverizing an inorganic substance having a relatively large particle size, for example, 20 μm or more, and then performing classification (vibration filtration, air classification, etc.).

As the high molecular compound, polytetrafluoroethylene, cellulose acetate, polystyrene, polymethyl methacrylate, polypropyl methacrylate,
Polymethyl acrylate, polyethylene carbonate,
There are starches and the like, and pulverized and classified products thereof.
Alternatively, a polymer compound synthesized by a suspension polymerization method, a spherical polymer compound by a spray drying method, a dispersion method, or the like, or an inorganic compound can be used.

Further, one of the monomer compounds described below
A polymer compound of a kind or two or more kinds of polymers may be formed into particles by various means. Specific examples of the monomer compound of the high molecular compound include acrylic acid ester, methacrylic acid ester, itaconic acid diester, crotonic acid ester, maleic acid diester, and phthalic acid diesters. Ethyl, propyl, isopropyl, butyl, hexyl, 2-ethylhexyl, 2-chloroethyl, cyanoethyl, 2-acetoxyethyl, dimethylaminoethyl, benzyl, cyclohexyl, furfuryl, phenyl, 2-hydroxyethyl, 2-ethoxyethyl, glycidyl, ω -Methoxy polyethylene glycol (number of added moles: 9);

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate,
Examples thereof include vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate, and vinyl salicylate. Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, and 2,3-dimethylbutadiene.

As styrenes, for example, styrene,
Examples include methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, trifluoromethylstyrene, and methyl vinyl benzoate.

Examples of acrylamides include acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tertbutylacrylamide, phenylacrylamide, dimethylacrylamide and the like; methacrylamides such as
Methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, tert
Allyl compounds such as allyl acetate, allyl caproate, allyl laurate, allyl benzoate and the like; vinyl ethers such as
Methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether and the like; vinyl ketones such as methyl vinyl ketone, phenyl vinyl ketone and methoxyethyl vinyl ketone; vinyl heterocyclic compounds such as vinyl pyridine and N -Vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, N-vinylpyrrolidone, etc .; unsaturated nitriles, such as acrylonitrile, methacrylonitrile, etc .; polyfunctional monomers, such as divinylbenzene, methylenebisacrylamide, ethylene glycol Dimethacrylate and the like.

Further, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate (for example,
Monoalkyl maleate (e.g., monomethyl maleate, etc.); styrenesulfonic acid, vinylbenzylsulfonic acid, vinylsulfonic acid, acryloyloxyalkylsulfonic acid (e.g.,
Methacryloyloxyalkylsulfonic acid (eg, methacryloyloxyethylsulfonic acid); acrylamidoalkylsulfonic acid (eg, 2-acrylamide-2-)
Methacrylamidoalkylsulfonic acid (eg, 2-methacrylamido-2-)
Acryloyloxyalkyl phosphate (eg, acryloyloxyethyl phosphate). These acids may be salts of alkali metals (eg, Na, K, etc.) or ammonium ions. Still other monomer compounds include U.S. Pat. Nos. 3,459,790, 3,438,708 and 3,554,987,
Nos. 4,215,195 and 4,247,673
And the crosslinking monomers described in JP-A-57-205735 and the like can be preferably used.
As an example of such a crosslinkable monomer, specifically, N
-(2-acetoacetoxyethyl) acrylamide, N
-(2- (2-acetoacetoxyethoxy) ethyl) acrylamide and the like can be mentioned.

These monomer compounds may be used in the form of polymer particles which are polymerized singly, or may be used in the form of copolymer particles obtained by combining and polymerizing a plurality of monomers.
Among these monomer compounds, acrylic esters, methacrylic esters, vinyl esters, styrenes, and olefins are preferably used. Also, the present invention relates to JP-A Nos. 62-14647 and 62-1774.
Particles having a fluorine atom or a silicon atom as described in JP-A Nos. 4 and 62-17743 may be used.

Among these, the particle compositions preferably used are polystyrene, polymethyl (meth) acrylate, polyethyl acrylate, poly (methyl methacrylate / methacrylic acid = 95/5 (molar ratio), poly (styrene / styrene sulfonic acid = 95). / 5 (molar ratio), polyacrylonitrile, poly (methyl methacrylate / ethyl acrylate / methacrylic acid = 50/40/10),
Silica and the like can be mentioned.

Further, the particles of the present invention are disclosed in JP-A-64-770.
No. 52, EP 307855, particles having a reactive (especially gelatin) group can also be used. Further, a large amount of a group which is soluble in an alkaline or acidic state can be contained. Hereinafter, specific examples of the matting agent of the present invention will be described, but the present invention is not limited thereto.

[0069]

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The binder of the layer containing the matting agent of the present invention is not particularly limited, and may be a lipophilic binder or a hydrophilic binder. As the lipophilic binder, known thermoplastic resins, thermosetting resins, radiation-curable resins, reactive resins, and mixtures thereof can be used. The resin has a Tg of -40C to 200C and a weight average molecular weight of 10,000 to 300,000, preferably 10,000 to 100,000.

As the thermoplastic resin, vinyl chloride.
Vinyl acetate copolymer, vinyl chloride, copolymer of vinyl acetate and vinyl alcohol, maleic acid and / or acrylic acid, vinyl chloride / vinylidene chloride copolymer, vinyl chloride / acrylonitrile copolymer, ethylene / vinyl acetate copolymer Vinyl copolymers such as polymers, nitrocellulose, cellulose derivatives such as cellulose acetate propionate, cellulose acetate butyrate resin, acrylic resin, polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane, polycarbonate polyurethane Resin, polyester resin, polyether resin, polyamide resin, amino resin, rubber resin such as styrene butadiene resin, butadiene acrylonitrile resin, silicone resin, fluorine resin And the like can be given.

Among them, vinyl chloride resin poly (meth) acrylic ester resin, cellulose derivative, acrylic resin, urethane resin and styrene resin are preferable. As the radiation-curable resin, a resin obtained by bonding a group having a carbon-carbon unsaturated bond as a radiation-curable functional group to the above-mentioned thermoplastic resin is used. Preferred functional groups include an acryloyl group and a methacryloyl group.

In the binder molecules listed above, a polar group (epoxy group, CO ₂ M, OH, NR ₂ , NR ₃ X, SO
₃ M, OSO ₃ M, PO ₃ M ₂ , OPO ₃ M ₂ , wherein M is hydrogen, an alkali metal or ammonium, and when a plurality of M are present in one group, they may be different from each other; Is a hydrogen or an alkyl group).

The polymer binders listed above are used alone or in a mixture of several kinds, and can be cured by adding a known isocyanate-based crosslinking agent and / or a radiation-curable vinyl monomer. As the hydrophilic binder to be used, Research Disclosure No.
No. 17643, page 26, and No. 18716, 65
It is described on page 1 and exemplifies water-soluble polymers, cellulose esters, latex polymers, water-soluble polyesters and the like. Examples of the water-soluble polymer include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, maleic anhydride copolymer, and the like.Cellulose esters include carboxymethyl cellulose,
And hydroxyethyl cellulose. Latex polymers include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylate-containing copolymers, vinyl acetate-containing copolymers, butadiene-containing copolymers, and the like. Among these, gelatin is most preferred.

In the production process, before extraction of gelatin, so-called alkali-treated (lime-treated) gelatin immersed in an alkaline bath, acid-treated gelatin immersed in an acid bath, and double-immersed gelatin that has been subjected to both treatments. And enzyme-treated gelatin. If necessary, a portion of colloidal albumin, casein, carboxymethyl cellulose, cellulose derivatives such as hydroxyethyl cellulose, agar, sodium alginate, starch derivatives,
A saccharide derivative such as dextran, a synthetic hydrophilic colloid such as polyvinyl alcohol, poly N-vinylpyrrolidone, a polyacrylic acid copolymer, polyacrylamide or a derivative thereof, a partial hydrolyzate or a gelatin derivative may be used in combination with gelatin. Good.

The matting agent layer containing gelatin is preferably hardened. Examples of the hardening agent include aldehyde compounds such as formaldehyde and glutaraldehyde.
Ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethylurea), 2-hydroxy-
4,6-dichloro-1,3,5-triazine, and other U.S. Patent Nos. 3,288,775 and 2,732,30
No. 3, UK Patent Nos. 974,723 and 1,167,2
No. 07, etc., compounds having a reactive halogen, divinyl sulfone, 5-acetyl-1,3-
Diacryloylhexahydro-1,3,5-triazine, and other U.S. Pat.
Compounds having a reactive olefin, such as those described in U.S. Pat. No. 232,763 and British Patent No. 994,869;
-Hydroxymethylphthalimide, other N-methylol compounds described in U.S. Pat. Nos. 2,732,316 and 2,586,168, U.S. Pat.
Isocyanates described in US Pat. Nos. 103,437 and 3,017,280 and 2,983, US Pat.
611 and the like, the acid derivatives described in U.S. Pat. Nos. 2,725,294 and 2,725,295, and the like, U.S. Pat.
Epoxy compounds described in 1,537 and the like, and halogen carboxaldehydes such as mucochloric acid can be mentioned. Alternatively, as a hardener of an inorganic compound, chromium ban, zirconium sulfate, and JP-B-56-12
No. 853, No. 58-32699, Belgian patent 82
5,726, JP-A-60-225148, JP-A-5
Examples thereof include carboxyl group-active hardeners described in JP-A No. 1-126125, JP-B-58-50699, JP-A-52-54427 and U.S. Pat. No. 3,321,313.

The hardener is used in an amount of usually 0.01 to 30% by weight, preferably 0.05 to 20% by weight, based on dry gelatin.
% By weight. In addition, the matting agent-containing layer described above may contain various additives such as a smoothing agent, a surfactant, an antistatic agent, a thickener, an ultraviolet absorber, a silver halide, and a formalin trapping agent, if necessary. I can do it.

Next, when a polyester polymer film is used for the support, since all of these polymer films have a hydrophobic surface, a photographic layer comprising a protective colloid mainly composed of gelatin (for example, a photosensitive halogen) is provided on the support. It is very difficult to firmly bond the silver halide emulsion layer, the intermediate layer, the filter layer, etc.). Techniques for overcoming such difficulties include (1) chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, (2) a method of obtaining an adhesive force by directly applying a photographic emulsion after performing a surface activation treatment such as an ozone oxidation treatment;
There are two methods: a method in which an undercoat layer is provided after or once without such surface treatment, and a photographic emulsion layer is coated thereon. (See, for example, US Pat. No. 2,698,241)
Nos. 2,764,520 and 2,864,755
Nos. 3,462,335 and 3,475,193
Nos. 3,143,421 and 3,501,301
No. 3,460,944, No. 3,674,531
Nos. 788,365 and 804,005.
No. 891,469, JP-B-48-43122,
No. 51-446, etc.).

All of these surface treatments are thought to be due to the formation of polar groups on the originally hydrophobic support surface and an increase in the crosslink density of the surface. It is considered that the affinity of the components contained in the undercoat solution with the polar group increases, or the fastness of the adhesive surface increases. Various modifications have been made to the structure of the undercoat layer, and a layer (hereinafter, abbreviated as the first undercoat layer) that adheres well to the support is provided as a first layer, and a second layer is formed thereon as a second layer. A so-called multi-layer method of applying a hydrophilic resin layer (hereinafter abbreviated as a second undercoat layer) that adheres well to a layer, and a single layer of applying only one resin layer containing both a hydrophobic group and a hydrophilic group. There is a law.

Among the surface treatments (1), the corona discharge treatment is the most well-known method, and any of the conventionally known methods, for example, JP-B-48-5043 and JP-B-47-5.
1905, JP-A-47-28067 and JP-A-49-83
No. 767, No. 51-41770, No. 51-13157
No. 6, etc. can be achieved.
The discharge frequency is 50 Hz to 5000 KHz, preferably 5 Hz.
KHz to several hundred KHz are appropriate. If the discharge frequency is too low, stable discharge cannot be obtained, and pinholes occur in the object to be processed, which is not preferable. If the frequency is too high,
A special device for impedance matching is required, which increases the price of the device, which is not preferable. Regarding the processing strength of the object to be treated, in order to improve the wettability of a plastic film such as a normal polyester or polyolefin, it is 0.001 KV · A · min / m ^{2 to} 5 KV · A · min / m ^2.
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, glow discharge treatment, which is the most effective surface treatment, can be performed by any conventionally known method, for example, JP-B-35-7578 and JP-B-36-1033.
No. 6, No. 45-22004, No. 45-22005,
Nos. 45-24040, 46-43480, U.S. Pat. Nos. 3,057,792, 3,057,795, 3,179,482, 3,288,638, 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-53-129262, etc. Can be used.

The glow discharge processing conditions are generally such that the pressure is set at 0.
005 to 20 Torr, preferably 0.02 to 2 Torr
r is appropriate. 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, sparks are likely to occur, it is dangerous, and there is a risk of destroying the workpiece. The discharge is generated by applying a high voltage between metal plates or metal rods arranged at one or more spaces in a vacuum tank. This voltage depends on the composition of the atmosphere gas,
Although various values can be taken depending on the pressure, a stable steady-state glow discharge usually occurs in the range of 500 to 5000 V within the above pressure range. A particularly suitable voltage range for improving the adhesion is from 2000 to 4000V.

Further, as seen in the prior art, the discharge frequency is from a direct current to several thousands MHz, preferably 50H.
z to 20 MHz is appropriate. Regarding the discharge treatment strength, 0.01 KV ·
A · min / m ² ５5 KV · A · min / m ² , preferably 0.
15 KV · A · min / m ² to ¹ KV · A · min / m ² is appropriate.

As a preferable ultraviolet treatment as a pretreatment for the organic solvent-based undercoating, any conventionally known method is used, for example, Japanese Patent Application Nos. 39-14534 and 39-16094 and Japanese Patent Publication No. 45-3828. be able to.

In the undercoating liquid used herein, in addition to the organic solvent, additives for the purpose of reinforcing the undercoating layer, improving the adhesion to the support or the emulsion layer, preventing static charge, or coloring the support. An agent, that is, a hardening agent, an antistatic agent, a dye, or the like may be added. In some cases, by adding a hardening agent such as an ethyleneimine derivative or an epoxy derivative to the undercoat liquid, the desired adhesiveness may be obtained even with ultraviolet irradiation shorter than in the case where no hardener is added.

[0086] Particularly effective ultraviolet rays in the present invention are ultraviolet rays having a wavelength of 3200 to 2200 °.

Next, the undercoating method of (2) will be described. All of these methods have been well studied. In the first layer of the undercoating method in the multilayer method, for example, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid Numerous polymers such as copolymers starting from monomers selected from the group consisting of, for example, itaconic acid and maleic anhydride, as well as polyethyleneimine, epoxy resin, grafted gelatin, and nitrocellulose In the layer, its properties have mainly been studied for gelatin.

In the single layer method, in many cases, good adhesion is achieved by swelling the support and mixing it with the hydrophilic undercoat polymer at the interface. Examples of the hydrophilic undercoat polymer used in the present invention include a water-soluble polymer, a cellulose ester, a latex polymer, and a water-soluble polyester. Examples of the water-soluble polymer include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, maleic anhydride copolymer, and the like.Cellulose esters include carboxymethyl cellulose,
And hydroxyethyl cellulose. Latex polymers include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylate-containing copolymers, vinyl acetate-containing copolymers, butadiene-containing copolymers, and the like. Among these, gelatin is most preferred.

Compounds which swell the support used in the present invention include resorcin, chlorresorcin, methylresorcin, o-cresol, m-cresol, p-cresol, phenol, o-chlorophenol, p-chlorophenol, Chlorphenol, trichlorophenol, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid, chloral hydrate and the like can be mentioned. Preferred among these are resorcin and p-chlorophenol.

Various gelatin hardeners can be used in the underlayer of the present invention. Gelatin hardeners include chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine, etc.), epichlorohydrin resin And the like.

The subbing layer according to the present invention comprises SiO ₂ , Ti
O ₂ , inorganic fine particles such as a matting agent, or polymethyl methacrylate copolymer fine particles (1 to 10 μm) can be contained. In addition, various additives can be contained in the undercoat liquid as needed. Examples include 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 layer of the undercoat is used, it is not necessary to include an etching agent such as resorcin, chloral hydrate, chlorophenol in the undercoat liquid at all. However, if desired, the above-mentioned etching agent may be contained in the undercoat.

The undercoating liquid according to the present invention can be prepared by applying a well-known coating method such as a tip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, or US Pat. It can be applied by an extrusion coating method using a hopper described in Japanese Patent No. 2,681,294. Optionally, U.S. Pat. No. 2,761,791
Nos. 3,508,947 and 2,941,898
No. 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).

As an example, an example of an undercoat layer using an organic solvent will be described. In the multi-layer undercoat, the hydrophobic binder as the first layer preferably has an affinity for polyester,
Examples include amorphous polyester, vinyl chloride-vinyl acetate copolymer, polyvinyl acetal, and nitrocellulose. The second layer often has gelatin dispersed in an organic solvent.

In the case of a single-layer undercoat, a hydrophilic binder is directly applied to polyester and adhered thereto. The binder may be one in which gelatin is dispersed in an organic solvent, or one in which gelatin and nitrocellulose are dispersed. However, in this system, it is necessary to apply a polyester swelling agent at the same time, anchor the binder into the polyester, and physically adhere strongly to the polyester.

As the hydrophilic binder, -O is added to the side chain.
H, -COOH, = O (CO ) =, - SO 3 M (M is H
Or an alkali metal), - NH _2, cyclic amide, -CON
R ₁ R ₂ (R ₁ and R ₂ are H or an alkyl group of C = 4 or less), or a heterocyclic group containing nitrogen alone or two or more equivalents, is soluble in organic solvents and swells in water Soluble synthetic polymer compound: for example, cellulose acetate phthalate, cellulose acetate malate, vinyl copolymer containing maleic anhydride, for example, vinyl acetate and maleic anhydride (1: 1) copolymer (if necessary, German patent No. 1040898), S of polyvinyl alcohol
O ₃ mixture acetal compound containing M group (see British Patent No. 894,509), polyvinyl alcohol -CO
Many hydrophilic resins, such as a mixed acetal containing an OM group, a partially esterified product of a divalent acid, and a mixture of polyvinylpyrrolidone and polyacrylic acid, may be used. Also, an undercoating solution comprising a dispersion of gelatin is used in place of the above hydrophilic binder solution.

Examples of the polyester solvent or swelling agent used in the present invention include ketones or aldehydes containing aromatic or partially saturated aromatic groups and aldehydes containing nitrogen-containing heterocyclic groups (GB Patent 772600). General formula R-COOH or R
A carboxylic acid represented by -X-COOH or an anhydride, ester, amide or nitrile obtained from the acid, wherein R is aromatic or an aromatic heterocyclic compound containing nitrogen in the ring, and X is- CH ₂ or —OCH ₂
(See British Patent No. 776157), aliphatic monohydric alcohols or amines containing aromatic groups (see British Patent No. 785789), alcohols, ketones, carboxylic acids and those having a substituent thereof or their esters (United Kingdom). Patent No. 797425), -NO ₂ to the aromatic nucleus, benzyl alcohol replacing -Cl (US Patent No. 2,830,030), chloral hydrate (German Patent No. 1020457), pyrrole (German Patent No. 1,092,652) and the like There are specific examples of the solvent described above, benzoic acid, salicylic acid, salicylic acid ester, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, 2-nitropropanol, benzyl alcohol, benzaldehyde, acetonylacetone , Acetophenone, ben Amide, benzonitrile, benzylamine, methyl nicotinate and the like. In addition,
Known polyester solvents or swelling agents include phenol, orthochlorophenol, cresol and other phenol derivatives.

The organic solvent used in the present invention must contain 1 to 25% (weight percentage) of the polyester solvent or swelling agent as exemplified above in the undercoat liquid component. When the content is 25% or more, the flatness of the completed film is significantly impaired in many cases, and when it is 1% or less, the desired effect is hardly obtained. The amount of the polyester solvent or swelling agent to be added can be changed depending on the type of the polyester solvent or swelling agent and the type of other coexisting organic solvent, in addition to the polyester film support to be used and the irradiation conditions. As a matter of course, two or more kinds of polyester solvents or swelling agents may be mixed and used at the same time. In this case, the amount added
The total amount of the mixed polyester solvent or swelling agent is 1 to 25% of the total organic solvent.

The binder of the back layer may be a hydrophobic polymer or a hydrophilic polymer as used in the underlayer. The back layer of the light-sensitive material of the present invention may contain an antistatic agent, a lubricant, 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, for example, a carboxylic acid and a carboxylate as an anionic polymer electrolyte,
A polymer containing a sulfonic acid salt, for example, as disclosed in JP-A-48-220
No. 17, JP-B-46-24159, JP-A-51-30
No. 725, JP-A-51-129216 and JP-A-55-129216.
No. 95942. Examples of the cationic polymer include, for example, JP-A-49-12152.
No. 3, JP-A-48-91165, and JP-B-49-245.
No. 82, for example. Also, ionic surfactants are anionic and cationic, and are described in, for example, JP-A-49-85826 and JP-A-49-33630.
No., US 2,992,108, US 3,206,31
2, JP-A-48-87826, JP-B-49-1156
7, JP-B-49-11568, JP-A-55-708
No. 37 and the like.

The most preferred antistatic agent for the back layer of the present invention is ZnO, TiO ₃ , SnO ₂ , Al ₂
O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO
_3. Fine particles of at least one kind of crystalline metal oxide or a composite oxide thereof selected from among the _three . 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 0.1.
It is desirable to set it to 01-0.7μ, especially 0.02-0.5μ.

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 material will be described. The light-sensitive material of the present invention only needs to have at least one layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support. There is no particular limitation on the number of layers and the order of the non-photosensitive layers. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The light-sensitive layer is a unit light-sensitive 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, generally, the unit light-sensitive layer is The arrangement is such that a red-sensitive layer, a green-sensitive layer, and a 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 layers of the same color sensitivity.

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

(Types of Additives) (RD17643) (RD18716) 1 Chemical sensitizer page 23, page 648, right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, supersensitizer 23 to 24, page 648 right column to Page 649 Right column 4 Brightener page 24 5 Antifoggants and stabilizers 24-25 Page 649 Right column 6 Light absorbers, filter dyes, UV absorbers 25-26 Page 649 Right column 650 pages Left column 7 Stain inhibitor page 25 right column page 650 left to right column 8 Dye image stabilizer page 25 9 hardener 26 page 651 left column 10 Binder 26 same as above 11 Plasticizer and lubricant 27 page 650 right column 12 Coating Auxiliaries and surfactants, pages 26 to 27, right column, page 650 In order to prevent the deterioration of photographic performance due to formaldehyde gas, it is described in U.S. Pat. Nos. 4,411,987 and 4,435,503. It is preferable to add a compound that can react with formaldehyde and be fixed to the light-sensitive material.

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. (Example 1) PET chip, PEN chip, PAr chip and poly (oxyisophthaloyloxy-2,6-)
Dimethyl-1,4-phenyleneisopropylidene-3,
5-dimethyl-1,4-phenylene) chip (POD
P) was melt extruded, and then 3.4 times in the longitudinal direction.
The film was stretched four times in the transverse direction to produce a biaxially stretched polyester film having a thickness of 80 μm.

PEN has an extrusion temperature of 300 ° C., a longitudinal stretching temperature (CD side) of 140 ° C., a transverse stretching temperature of 130 ° C., and a heat setting of 2
A film was formed at 50 ° C. for 6 seconds. PAr, PODP, PET were also prepared by a similar method, and samples A-1 to A-1 shown in Table 1 were prepared.
A-4 and B-1 to B-2 were obtained.

[0124]

[Table 1]

2) Coating of Undercoat Layer Each of the above support samples was subjected to a corona discharge treatment on both surfaces thereof, and then an undercoat layer having the following composition was provided on the high temperature side during stretching. For corona discharge treatment, a solid state corona treatment machine 6KVA model manufactured by Pillar Co., Ltd. was used.
Process at 0 m / min. At this time, the object was processed at 0.375 KV · A · min / m ^{2 based on} the current / voltage readings. The discharge frequency during processing is 9.6 KHz,
The gap clearance between the electrode and the dielectric roll is 1.6
mm.

Gelatin 3 g Distilled water 250 cc Sodium α-sulfodi-2-ethylhexyl succinate 0.05 g Formaldehyde 0.02 g

3) Coating of Back Layer A back layer having the following composition was coated on the surface of the support after the undercoat opposite to the side on which the undercoat layer was provided. 3-1) Preparation of conductive fine particle dispersion (tin oxide-antimony oxide composite dispersion): 230 parts by weight of stannic chloride hydrate and 23 parts by weight of antimony trichloride were added to ethanol 300
It was dissolved in 0 parts by weight to obtain a homogeneous solution. To this solution was added dropwise a 1N aqueous solution of sodium hydroxide 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 red-brown colloidal precipitate.

The reddish brown colloidal precipitate was separated by centrifugation. Water was added to the precipitate to remove excess ions, and the precipitate was washed with water by centrifugation. This operation was repeated three times to remove excess ions. Colloidal precipitate from which excess ions have been removed 2
00 parts by weight were re-dispersed in 1500 parts by weight of water and sprayed into a baking furnace heated to 600 ° C. to give a bluish average particle size of 0.2.
A fine particle powder of a tin oxide-antimony oxide composite of μm was obtained. The specific resistance of this fine particle powder was 25 Ω · cm.

A mixture of 40 parts by weight of the fine particle powder and 60 parts by weight of water was adjusted to pH 7.0, and after roughly dispersing with a stirrer,
Horizontal Sand Mill (trade name: Dino Mill; WILLYA B)
(Manufactured by ACHOFENAG) until the residence time became 30 minutes.

3-2) Coating of Back Layer: Following Formula [A]
And dried at 130 ° C.
For 30 seconds. On this, the following coating liquid for coating layer (B) was further applied so as to have a dry film thickness of 0.1 μm.
Dry at 130 ° C. for 2 minutes. [Formulation A] The conductive fine particle dispersion 10 parts by weight Gelatin 1 part by weight Water 27 parts by weight Methanol 60 parts by weight Resorcinol 2 parts by weight Polyoxyethylene nonylphenyl ether 0.01 parts by weight [Coating layer coating solution (B)] Cellulose triacetate 1 part by weight Acetone 70 parts by weight Methanol 15 parts by weight Dichloromethylene 10 parts by weight p-chlorophenol 4 parts by weight

4) Heat treatment of the support After coating the undercoat layer and the back layer by the above method,
The heat treatment was performed under the following conditions. All the heat treatments were carried out with a 30 cm diameter stainless steel core and the undercoating surface wound outside. Further, as a comparative example, one not subjected to heat treatment was also prepared.

Among the mechanical strengths of these supports, the most important bending elasticity was measured as the support became thinner. The measurement of the curvature modulus was performed using a method called a ring method. That is, a sample having a width of 35 mm and a slit slit parallel to the length direction was used to form a ring having a circumference of 10 cm, placed horizontally, and measured the load when deformed by 12 mm to obtain a measure of the bending elastic modulus. . In this measurement, the measurement was performed so that the undercoat layer was the inner circumference of the ring, and the measurement was performed at 25 ° C. and 60% RH.

Table 1 shows the measurement results. P
EN indicates a curvature modulus of 80 μm, which is almost equivalent to TAC of 122 μm. This value did not change even when the heat treatment of the present invention was performed.

5) Coating of Photosensitive Layer On the undercoating side of the support obtained by the above method, each layer having the following composition was applied in a multi-layered manner to prepare a multilayer color photosensitive material. However, the fifteenth layer contained the matting agent of the present invention as shown in Table 3 below. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

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

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

Third layer (low-sensitivity red-sensitive emulsion layer) Emulsion A silver 0.25 Emulsion B silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-33 0.1 × 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 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 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion E silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.12 ExC-3 0.045 ExC-6 0.020 ExC-8 0.025 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20

Sixth layer (intermediate layer) Cpd-1 0.10 HBS-1 0.50 Gelatin 1.10.

Seventh layer (low-sensitivity green-sensitive emulsion layer) Emulsion C Silver 0.35 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-1 0.010 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Speed 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

Tenth 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 Speed 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

Fourteenth 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

15th layer (second protective layer) H-1 0.40 Matting agent (SBR or M-2) 0.10 (Table 3)
B-1 0.1 S-1 0.20 Gelatin 1.20 Here, SBR indicates a styrene / butadiene copolymer.

In order to improve the storability, processability, pressure resistance, fungicidal / antibacterial properties, antistatic properties and coatability of each layer, W-1 to W-3, B-1 to B- 4, F-1 to F
-17 and iron salts, lead salts, gold salts, platinum salts, iridium salts, and rhodium salts. The properties of emulsions A to F used in each layer are as shown in Table 2.

[0151]

[Table 2]

In Table 2, (1) Emulsions A to F were subjected to reduction sensitization during the preparation of grains 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. Have been. (3) For preparing 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 using a high-pressure electron microscope.

The chemical formulas of the additives used for each layer are shown below.

[0154]

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[0155]

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[0158]

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[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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[0166]

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[0167]

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[0168]

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6) Processing The photographic film sample thus prepared was slit and pierced to a length of 35 mm and a length of 1.8 m.
It was humidified with RH for 3 hours and incorporated into the unit shown in FIG. 1 or FIG. Then, samples A1-1-1 to B2-10
I got 6-1) Extraction of tongue tip, development processing, and curl measurement After the film-integrated camera wound at 80 ° C. for 2 hours was allowed to cool overnight in a room at 25 ° C. and 60% RH,
The tongue tip is extracted with a jig, and developed with an automatic developing machine (Minilab FP-550B: manufactured by Fuji Photo Film Co., Ltd.). Immediately at 25 ° C. and 60% RH under ANSI.
The curl was measured. 6-2) Evaluation of Adhesion Resistance After leaving the film-integrated camera at 80 ° C. for 2 hours, the adhesion between the emulsion side and the back side was evaluated.

The adhesion level was evaluated in three grades of ○, Δ, and ×. Adhesion level: （(no adhesion): △ (0-49% adhesion): × (50% or more 〃) Except for ○, it is not acceptable

The developing conditions are as follows.

Processing Step Temperature Time Color Development 38 ° C. 3 minutes Stop 38 ° C. 1 minute Rinse 38 ° C. 1 minute Bleach 38 ° C. 2 minutes Rinse 38 ° C. 1 minute Fix 38 ° C. 2 minutes Rinse 38 ° C. 1 minute Stabilizing bath 38 ° C. for 1 minute The treatment liquid used has the following composition. Color developing solution Caustic soda 2 g Sodium sulfite 2 g Potassium bromide 0.4 g Sodium chloride 1 g Eagle sand 4 g Hydroxylamine sulfate 2 g Ethylenediaminetetraacetic acid disodium dihydrate 2 g 4-Amino-3-methyl-N-ethyl-N- (β -Hydroxyethyl) aniline / monosulfate) 4 g Add water to total 1 liter Stop solution Sodium thiosulfate 10 g Ammonium thiosulfate (70% aqueous solution) 30 mL Acetic acid 30 mL Acetic acid 5 g Potash alum 15 g Add water to total 1 liter Bleaching Liquid Sodium ethylenediaminetetraacetate (III) sodium dihydrate 100 g Potassium bromide 50 g Ammonium nitrate 50 g Folic acid 5 g Ammonia water Adjust the pH to 5.0 Add water and add 1 liter fixer Sodium thiosulfate 150 g Sodium sulfite 15 g Houda sand 12 g Glacial acetic acid 15 ml Potassium alum 20 g Add water 1 liter in total Stabilization bath Boric acid 5 g Sodium citrate 5 g Sodium metaborate (tetrahydrate) 3 g Potash alum 15 g Add water 1 liter in total (Results) The measurement results are shown in Tables 3 to 7.

[0173]

[Table 3]

[0174]

[Table 4]

[0175]

[Table 5]

[0176]

[Table 6]

[0177]

[Table 7]

Poly (oxyisofuroyloxy-2,6-dimethyl-1,4-phenyleneisopropylidene-3,5-dimethyl-1,4-phenylene having a Tg of 225 ° C. was inferior in transparency of the film. PEN having a glass transition temperature (Tg) of more than 90 ° C.
In PAr, after forming a film with a stretching temperature difference, 110 ° C.,
It can be seen that the heat treatment for 24 hours shows a clear curl reduction. As a result, there was no trouble in the work of extracting the tongue tip, and no development unevenness and rear end break occurred.

On the other hand, in the evaluation of the adhesion resistance, a film-integrated camera having extremely excellent adhesion resistance even at high temperatures can be produced by combining a matting agent having a high Tg (> 90 ° C.) with the above-mentioned PEN and PAr. I understand. From the above results, it can be seen that the present invention provides a film having a thinner support, less curl at high temperatures, less curling of the film, improved work of extracting the tongue end of the film, and excellent development processing unevenness, rear end breakage and adhesion resistance. It can be seen that an expression camera can be created.

Example 2 1) Preparation of photosensitive material The polyester used for the support was PEN, PET, PA
r, PCT pellets were dried in vacuum at 150 ° C. for 4 hours in advance, then kneaded and extruded at 280 ° C. using a twin-screw kneading extruder at a mixing ratio as shown in Table 4, and pelletized. This polyester was formed into a film under the same stretching conditions as PEN of Example 1. This was further heat-treated according to the formulation of Example 1, and then an undercoat layer and a back layer were applied with the following compositions. (Undercoat layer composition) Gelatin 0.2 g Salicylic acid 0.1 g Methanol 15 cc Acetone 85 cc Formaldehyde 0.01 g

(Applying Back Layer) The formulation [A] of Example 1 was applied to a dry film thickness of 0.3 μm and dried at 130 ° C. for 30 seconds. A coating solution for coating containing a matting agent having the following composition was applied thereon, and dried at 130 ° C. for 2 minutes.・ Diacetyl cellulose 0.2 g / m ²・ Colloidal silica (aerosil) 0.02 〃 ・ C ₁₅ H ₃₁ COOC ₄₀ H ₈₁ 0.02 _２・ C ₂₁ H ₄₃ COO (CH ₂ CH ₂ O) ₃ —COC ₉ H ₁₉ 0.01 〃 · C ₂₁ H ₄₃ OOC (CH ₂ ) ₁₈ —COOC ₁₈ H ₃₇ 0.01 〃 · Poly (vinylidene difluoride / vinylidene tetrafluoride) (molar ratio 9: 1) 0.01 〃 Poly (methyl methacrylate / divinylbenzene) (molar ratio 9: 1, average particle size 1.0 μm) 0.03０．０ · Silica (average particle size 1.0 μm) 0.005〃 The flexural modulus was evaluated using the ring method in the same manner as in the examples.

Table 8 shows the results.

[0183]

[Table 8]

(Coating of photosensitive layer) The undercoating side of the support obtained by the above method was coated in exactly the same formulation as the photosensitive material described in Example 1 of JP-A-2-93641. That is, the first layer has an antihalation layer, the second layer has an intermediate layer, and the third to third layers.
The thirteenth layer is a photosensitive layer, and the fourteenth to fifteenth layers are protective layers.

However, the second protective layer of the fifteenth layer had the following composition. Thus, the photosensitive material C-1
-1 to C-3-2, D-1-1 to D-3-2, E-1-
1 to E-3-2 and F-1-1 to F-3-2 were produced.
(Tables 9, 10, 11, 12)

[0186]

[Table 9]

[0187]

[Table 10]

[0188]

[Table 11]

[0189]

[Table 12]

Fifteenth layer (second protective layer) H-1 0.40 Matting agent (SBR, M-3 or M-1) 0.10 B-1 0.10 S-1 0.20 Gelatin 1.20 The details of the matting agent are shown in Tables 9 to 12. Here, SBR is a styrene-butadiene copolymer. (Evaluation of Samples) The samples prepared in this way and the evaluation results are shown in Tables 9 to 12.

(Results) In the PEN / PET blend polymer, a film was formed on a support having a Tg of 90 ° C. or higher, and then subjected to a heat treatment at a temperature lower by 10 ° C. than the Tg, thereby showing a clear curl reduction. Also, the heat treatment time was as short as 6 hours, which was effective. Further, the curvature modulus by the ring method also showed a value close to 36 g at a TAC of 122 μm.

The above results show that PEN is not contained.
The PAr / PCT blend polymer was also recognized when Tg was 90 ° C. or higher. On the other hand, in the case of the blend polymer having a Tg of less than 90 ° C., the curl reduction as described above was not observed. On the other hand, the evaluation of the adhesion resistance shows that a film-integrated camera having very excellent adhesion resistance even at high temperatures could be produced by combining a matting agent having a high Tg (100 ° C.) with the above-mentioned polyester blend polymer.

The above results support that the present invention can be applied if the Tg is 90 ° C. or more regardless of the composition of the multi-polyester blend polymer.

[0194]

According to the present invention, the film is hardly curled, the work of extracting the tongue end is improved, and the unevenness in the development processing is reduced.
A film-integrated camera that does not break at the rear end and has excellent adhesion resistance can be obtained.

[Brief description of the 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 integrated film camera of the present invention.

[Explanation of symbols]

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

────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-1-291248 (JP, A) JP-A-5-307235 (JP, A) JP-A-2-62535 (JP, A) JP-A-4- 124644 (JP, A) JP-A-2-24645 (JP, A) JP-A-2-300256 (JP, A) JP-A-63-69864 (JP, A) JP-A-50-40655 (JP, A) JP-A-5-105786 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03C 3/00 575 G03C 3/00 540 G03C 1/795 G03C 1/91

Claims (4)

(57) [Claims] 1. A bag of photosensitive material drawn from a patrone.
Matting agent on at least one of the
The unexposed film was rolled into the supply chamber by rolling in the unexposed film, and an empty patrone was loaded into the winding chamber.The unexposed film was pulled out of the supply chamber for each photographing.
In the film integral camera comprising configured to wind within the cartridge, the support Gaga glass transition temperature is below 200 ° C. 90 ° C. or more naphthalene dicarboxylate of the film
Polyester made mainly of boric acid and ethylene glycol
(Excluding aromatic compounds having a metal sulfonate group)
Consists of a polyester containing dicarboxylic acid as a copolymer component
The support is formed by biaxial stretching and heat setting.
After, and before or after the application of the undercoat layer, before the application of the emulsion, before the coating of the emulsion , an exposure film having the support that has been heat-treated at a temperature of 50 ° C. or more and a glass transition temperature or less,
A film-integrated camera, wherein the camera is loaded with its center portion empty or wound around a spool having a core diameter of 9 mm or less . Wherein said matting agent is an inorganic compound or a glass transition temperature of 50 ° C. or more polymeric compounds, average particle size is ^{10 -3 ~10 2 μm, 0.1~10 3} mg
^2. The film-integrated camera according to claim 1, wherein the content of the film-integrated camera is equal to or less than 1 m / m ² . 3. Before Kipo Riesuteru polyethylene -2,
The film-integrated camera according to claim 1 or 2, wherein the camera is 6-naphthalenedicarboxylate. 4. The polyester-based support having a thickness of 50
The film-integrated camera according to any one of claims 1 to 3 , wherein the thickness is from 90 to 90 m.