JPH0545799A - Photographic film product and image forming method - Google Patents

Abstract

PURPOSE:To provide a photographic film product and an image forming method, for remarkably improving the sharpness of a color print from a small format color negative film. CONSTITUTION:The photographic film product and image forming method have a characteristic as follows; when the photographic film is loaded on a camera, the film is rolled up on a spool inside a cartridge having a posture control means so that the outlet of the film is kept in a plain including an exposing stage inside the camera, and a direction where the film is taken in/out is in parallel with a photographic film taking up direction inside the camera, the width of the film is 15--35mm, the area of one frame of an image exposing part is formed 3cm<2>-7cm<2>, and simultaneously, the supporting body of the film is a polycarbonate base.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photographic film product and an image forming method. More specifically, the present invention relates to a high-quality photographic film product which is suitable for a small camera that is convenient to carry and is also excellent in protecting the environment of the earth, and a high-quality image forming method.

[0002]

2. Description of the Related Art In recent years, graininess, sharpness and color reproducibility of silver halide color light-sensitive materials for photography (including color negatives and color reversal light-sensitive materials; hereinafter simply referred to as color negatives) have been improved and zoom lenses or The widespread use of cameras equipped with bifocal lenses has made it possible to obtain even more variety of high-quality photos.

However, in a camera equipped with a boom lens or a bifocal lens, if the focal length on the telephoto side is extended, the camera becomes large and the portability deteriorates. It had the drawback of being a camera without. As means for solving the above-mentioned problems, U.S. Pat.Nos. 3,490,844, 4583831 and 465030.
No. 4 and others have proposed a so-called pseudo-zoom method, focusing on the recent progress in the performance of color negative films. The pseudo-zoom method detects the focal length information of the lens that was input to the film at some stage during the shooting stage, and then stretches out a portion of the negative film screen, resulting in a telescopic effect. Is to

This pseudo-zoom technique is currently the mainstream method.
This is based on a silver halide color negative roll film stored in a 5-format cartridge.
If the pseudo-zoom method is adopted, it is expected that the lens will be downsized by shortening the focal length of the lens, but it requires a lens having an image circle compatible with the 135 format, and the use of a cartridge compatible with the 135 format. It was difficult to realize an epoch-making small camera as compared with a 135 format camera.

In the pseudo zoom system, 1
The pseudo-zoom shooting and the normal shooting are mixed in the film of the book. A monitor test revealed that many general users are concerned about the difference in image quality between pseudo-zoom print and normal print. Further, in the pseudo zoom method, the ratio of the effective screen area of the negative used for printing the print to the total area of the negative film is low, so that the material of the negative film and the processing liquid are wasted. Therefore, it can be said that the pseudo zoom system is not preferable from the viewpoint of resource saving and global environment protection.

In order to solve the above problems, it is most effective to reduce the image area of the lens by reducing the screen area of the color negative film. However, a monitor test on the image quality of prints revealed that it is not acceptable to general users unless the image quality (graininess, sharpness) of the prints that deteriorates due to the reduction of the screen area of the film is improved. In particular, there was a strong demand for improvement in sharpness.

[0007]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a small format color negative film product which provides prints with excellent sharpness.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to have a spool shaft 14 for winding a photographic film in a roll shape and a film outlet 13 for loading and unloading the photographic film, and to store the spool rotatably around its axis. Cartridge 1
In the photographic film product having the above, the cartridge keeps the film outlet in the plane (A) including the exposure stage 12 in the camera when loaded in the camera, and the photographic film loading / unloading direction (B). Has a posture restraining means so as to be parallel to the photographic film winding direction (C) in the camera, and the area of one screen of the photographic film is 3 cm ^{2 to} 7 cm ² , and further the support of the photographic film is provided. Achieved by making the body a polycarbonate. Furthermore, after the photographic film product is loaded into a camera and photographed, the photographic film is developed to form a negative image, which is printed on a photographic paper having a resolution of 5 / mm or more to form a positive image. Good results have been obtained.

The graininess of the print is strongly dependent on the color negative film. Therefore, it is important to improve the graininess of the color negative film. Specific means for this will be described later. However, various analysis experiments have revealed that the sharpness of the print depends on many factors such as the color negative film, the camera lens, the flatness of the film in the camera, the printer lens, the color paper, and the flatness of the paper in the printer. Became. Therefore, it has been clarified as a result of various studies that the sharpness of the print can be efficiently improved by improving each factor in a balanced manner as a system. Specific means for this will be described later.

First, the screen size will be described in more detail. The area of one screen of a photographic film product is 3 cm ^{2 to} 7 cm
^By setting it to ² , the object of the present invention can be achieved. Effect of the present invention becomes more pronounced and more preferably a 4cm ² ~6cm ^2. If the screen size is large, the print quality is good, but the camera cannot be made small enough. If the size of the screen is small, it is easy to downsize the camera, but the image quality of the print is insufficient. Further, if the camera is made extremely small, it becomes more convenient to carry, but since the operability at the time of shooting deteriorates, there is a camera size region that is preferable for the user. Considering these facts comprehensively, it was concluded that the above screen area is preferable.

The aspect ratio of the screen is 1: 1 to
The ratio is more preferably 1: 2 and more preferably 1: 1 to 1: 1.6. It is also possible to cut the top and bottom of the screen or use two screens to make a so-called panorama print with an aspect ratio of 1: 2 to 1: 4. The film width is preferably 15 to 35 mm,
It is 20 to 30 mm. The height of the camera can be reduced by narrowing the film width. The narrow film is particularly advantageous for miniaturization of a camera incorporating a penta prism of a zoom finder or a single-lens reflex finder.

The film length is determined by the number of photographic frames and the screen size. It is preferable that 24 to 36 frames can be photographed. Next, the attitude control means of the film cartridge and the cartridge will be described in detail. In the 110 format, which can be exemplified as a typical small format film of the related art, there is no pressure plate for ensuring the flatness of the film in the camera, and the shading paper that impairs the flatness of the film exists on the back surface of the film. Therefore, the sharpness of the obtained print was not fully satisfactory. Therefore, the 110 format does not give an answer to the problem of the present invention.

The 135 format cartridge (patrone) has been used for several decades, but as a result of a species study, if it is applied to a format having a smaller screen area than the 135 format, the sharpness of print is lowered. It turned out to be one of the causes. That is, since the body portion of the 135 format cartridge has a cylindrical shape as shown in FIG. 1, when the cartridge is loaded in the camera, the attitude of the cartridge in the camera cannot be uniquely controlled. For this,
In the combination of the 135 cartridge and a general 135 camera, the film exit of the cartridge and the plane including the exposure stage of the camera cannot always be kept substantially flush with each other when the camera is loaded, and once loaded, the cartridge exits. A photo is taken in the flat state.

When the film exit of the cartridge greatly deviates from the surface of the exposure stage of the camera, the film near the film exit is loaded in the camera in a bent state.
When the bent film is sent to the exposure stage of the camera, the flatness of the exposed film is impaired, leading to poor focus. In particular, in a small format system, the enlargement ratio becomes high, and thus the above-mentioned poor planarity of the film becomes a serious defect. That is, it was found that the poor flatness of the film on the exposure stage of the camera greatly hinders the sharpness of the film.

The cartridge in the photographic film product of the present invention, when loaded in a camera as shown in FIGS.
A means for controlling the posture of the photographic film so that it is kept in a plane (A) including 2 and the photographic film take-in / out direction (B) is parallel to the photographic film take-up direction (C) in the camera.
By providing the attitude control means, when the cartridge is loaded in the camera and the photographic film 2 is loaded from the film outlet of the cartridge to the film winding means in the camera on the other side by pushing the exposure stage out. The flatness of the photographic film, especially the flatness of the film near the film outlet of the cartridge can be maintained. "Film exit 3 is the exposure stage 12 of the camera
"Keeping in a plane (A) including" does not mean that the photographic film 2 is bent near the film outlet of the cartridge. Further, the film exit 3 and the exposure stage 12 of the camera do not have to be in contact with each other.

In order to uniquely control the attitude of the cartridge so as to maintain the above-mentioned flatness when the camera is loaded, basically, the cartridge rotationally moves around the spool shaft 4 in the cartridge loading chamber 13 in the camera. You can set it so that it cannot be done. Specifically, it is preferable to provide means for engaging the camera so that the cartridge maintains the above-mentioned flatness. Further, in order to obtain a better engagement relationship, it is preferable to improve the accuracy of the outer dimensions of the cartridge.

The specific means for setting the above-mentioned attitude control of the cartridge, in other words, the engagement means of the cartridge and the camera, include, for example, the following. First, the shape of the surface of the cartridge perpendicular to the spool axis (excluding the film outlet portion) can be made non-circular to engage with the cartridge loading chamber of the camera. The surface perpendicular to the spool axis to be non-circular may be either the body portion (cross section) or the side edge portion (end surface) of the cartridge, but only the side edge portion or both the body portion and the side edge portion. Is preferred.

As an example where the side edge portion is non-circular, the cross-sectional area (S ₂ ) of the side edge portion is more than the cross-sectional area (S ₁ ) of the body portion of the cartridge.
It is also possible to control the attitude of the cartridge in the camera by increasing. However, if the cross-sectional area (S ₂ ) of the side edge is too large, it is not preferable for downsizing the camera. Therefore, the S ₂ / S ₁ ratio is generally 1.2 or less, preferably
It is 1.1 or less, particularly preferably 1.05 or less.

Specifically, as shown in FIGS. 5 and 6,
The cartridge 1 may be a side edge portion having a non-circular portion 21 and a body portion 22 having a circular cross section. The non-circular portion 21 and preferably the body portion 22 are provided with a spring 32 provided in the cartridge loading chamber 13 of the camera,
Preferably, by 33, the camera is engaged for attitude control.

An example of the non-circular shape of the body portion is that at least one side surface of the body of the cartridge is made flat as shown in FIG. The planar shape means that the side surface of the cartridge has a flatness sufficient for carrying out the posture control according to the present invention, and may have a curved surface to some extent. Further, it is preferable that the flat surface of the cartridge is aligned with a specific surface of the cartridge loading chamber in the camera so as to be substantially in contact therewith. Here, “substantially contact” means contact that is sufficient to perform the posture control according to the present invention, and does not necessarily mean perfect contact.

As means for engaging the cartridge and the camera,
Secondly, at least one joint portion that can hold the cartridge in the cartridge loading chamber in the camera so as to control the attitude according to the present invention is provided in the cartridge and the camera. The installation place, the number of installations, and the shape of the joint portion may be any as long as the attitude control of the cartridge according to the present invention is achieved.

For example, as the joining means, there may be mentioned a method in which a so-called protrusion and a recess to be fitted therein are provided in the camera and the cartridge, respectively. For example, in FIG.
As shown in FIG. 4, a convex protrusion 8 can be provided on the side edge portion 6 of the body of the cartridge so as to engage the recess provided in the cartridge loading chamber of the camera. Such engaging means is
It is preferably provided on both end faces of the cartridge.

Alternatively, as shown in FIG. 4, a linear protrusion 9 is provided on the side surface 5 of the body of the cartridge so as to be engaged with a linear recess for fitting with the protrusion provided in the cartridge loading chamber of the camera. be able to. Further, as shown in FIG. 5, a protrusion 27 is provided at the film outlet of the cartridge,
It can be engaged with a recess 26 provided in the exposure stage of the camera. Such a protrusion may be provided at any of the film exits 3, and may be provided, for example, in a straight line along the film exit, or may be provided at one location at the center of the film exit.

In the above description, the protrusion may be provided on the camera side, and the recess that fits the protrusion may be provided on the cartridge. Further, the protrusion and the depression may have a fitting relationship sufficient to achieve the attitude control according to the present invention. As a further joining means, there is a method in which at least one pair of protrusions is provided on both the camera and the cartridge and the protrusions are joined to hold the cartridge in the cartridge loading chamber in the camera.

For example, as shown in FIGS. 5 and 6, the projection 23 of the cartridge and the projection 34 in the camera, and the projection 24 of the cartridge and the projection 35 in the camera can respectively hold the cartridge in the cartridge loading chamber in the camera. it can. Depending on the case, either one of the holding means is sufficient. Further, the holding means by the projection 24 of the cartridge and the projection 35 in the camera may be provided on both end surfaces of the cartridge.

The engaging means for controlling the attitude of the cartridge according to the present invention as described above is any one of the above.
If there is one, it is sufficient, but two or more may be used in combination (see FIGS. 3, 4 and 5). Further, in order to better set the above attitude control, the dimensional accuracy of the outer shape of the cartridge is preferably ± 0.5 mm or less, and more preferably ± 0.3 mm or less.

In order to ensure this accuracy, it is preferable to mold the cartridge using resin. The plastic material used in the present invention is an addition polymerization of an olefin having a carbon-carbon double bond, a ring-opening polymerization of a small ring compound,
It can be produced by a method such as polycondensation (condensation polymerization) between two or more polyfunctional compounds, polyaddition, and addition condensation between a phenol derivative, a urea derivative, a melamine derivative and a compound having an aldehyde.

The raw material of the plastics material is an olefin having a carbon-carbon double bond, for example, styrene,
Typical examples include α-methylstyrene, butadiene, methyl methacrylate, butyl acrylate, acrylonitrile, vinyl chloride, vinylidene chloride, vinylpyridine, N-vinylcarbazole, N-vinylpyrrolidone, vinylidene cyanide, ethylene and propylene. Can be mentioned. Examples of small ring compounds include ethylene oxide, propylene oxide, glycidol, 3,3
-Bischloromethyloxetane, 1,4-dioxane,
Typical examples include tetrahydrofuran, trioxane, ε-caprolactam, β-propiolactone, ethyleneimine, and tetramethylsiloxane.

Examples of polyfunctional compounds include carboxylic acids such as terephthalic acid, adipic acid and glutaric acid, isocyanates such as toluene diisocyanate, tetramethylene diisocyanate and hexamethylene diisocyanate, alcohols such as ethylene glycol, propylene glycol and glycerin. Typical examples include amines such as hexamethylenediamine, tetramethylenediamine, and paraphenylenediamine, epoxies, and the like. Also, phenol derivatives, urea derivatives,
Typical examples of the melamine derivative include phenol, cresol, methoxyphenol, chlorophenol, urea and melamine. Further, as a compound having an aldehyde, formaldehyde, acetaldehyde, octanal, dodecanal, benzaldehyde, etc. are representative. These raw materials may be used alone or in combination of two or more, depending on the target performance.

When a plastic material is produced using these raw materials, a catalyst or a solvent may be used.
As the catalyst, (1-phenylethyl) azodiphenylmethane, dimethyl-2,2'-azobisisobutyrate, 2,2'-azobis (2-methylpropane), benzoyl peroxide, cyclohexanone peroxide, potassium persulfate Radical polymerization catalyst such as, sulfuric acid, toluenesulfonic acid, trifluorosulfuric acid, perchloric acid, trifluoroboron, cationic polymerization catalyst such as tin tetrachloride, n
-Butyllithium, sodium / naphthalene, 9-fluorenyllithium, anionic polymerization catalysts such as phenylmagnesium bromide, triethylaluminum / tetrachlorotitanium type Ziegler-Natta
A system catalyst, sodium hydroxide, potassium hydroxide, potassium metal or the like is used.

The solvent is not particularly limited as long as it does not inhibit the polymerization, and examples thereof include hexane, decalin, benzene, toluene, cyclohexane, chloroform, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, tetrahydrofuran and the like. In molding the plastics of the present invention, a plasticizer is mixed with the plastics as necessary. As the plasticizer, for example, trioctyl phosphate, tributyl phosphate, dibutyl phthalate, diethyl sebacate, methyl amyl ketone, nitrobenzene, γ-valerolactone, di-n-octyl succinate, bromonaphthalene, butyl palmitate, etc. are typical. It is something.

Specific examples of the plastic material used in the present invention are shown below, but the invention is not limited thereto. P-1 Polystyrene P-2 Polyethylene P-3 Polypropylene P-4 Polymonochlorotrifluoroethylene P-5 Vinylidene chloride resin P-6 Vinyl chloride resin P-7 Vinyl chloride-vinyl acetate copolymer resin P-8 Acrylonitrile-butadiene- Styrene copolymer resin P-9 methyl methacrylic resin P-10 vinyl formal resin P-11 vinyl butyral resin P-12 polyethylene phthalate P-13 Teflon P-14 nylon P-15 phenol resin P-16 melamine resin Especially for the present invention. A preferred plastic material is made of polystyrene, polyethylene, polypropylene or the like in which carbon black, a pigment or the like is kneaded.

The outer diameter of the cartridge is 23 to 15 m / m, more preferably 21 to 17 m / m. The height of the cartridge is preferably 40 to 20 m / m, more preferably 30 to 25 m / m.
Is. By using the cartridge of the above size, it becomes easier to make the body of the camera smaller and thinner. In order to further reduce the size of the cartridge, it is necessary to further reduce the screen size or the film base thickness, which is not preferable in terms of image quality and film handling.

Cellulose triacetate is mainly used for the support of the current mainstream roll film for photographing. However, as a result of various analysis experiments, it was found that a roll film for photographing using cellulose triacetate as a support may cause a problem that the photosensitive layer is out of focus due to delicate movement in the camera. .. In the case of the polyester base currently used as a support for some roll films, the stability of focus in the camera is superior to that of cellulose triacetate, and unless exposed to a temperature above its glass transition point, A roll film having a polyester base as a support is preferable because it is difficult to wind and has excellent focusing accuracy in a printing process, but when exposed to a temperature around a glass transition point of 70 to 80 ° C., the film is greatly wound. It turned out that there was a problem that was attached. Since the temperature inside the automobile left in the sun can be about 80 ° C., the above phenomenon cannot be ignored as a special case.

To solve this problem, polycarbonate
Proved to be effective. That is, polycar
Roll film camera with Bonate base as support
In-focus stability is based on cellulose triacetate
It is superior to the case of, and even at a high temperature of 70-80 ℃
When exposed, the curl is based on polyester
Better. More particularly the posture in the camera mentioned above
When combined with a cartridge having control means, its improved effect
The fruit becomes more prominent. The area of one screen is 3 cm ²More than 7
cm²In the roll film below, this means
Useful.

The polycarbonate base used in the present invention will be described in detail below. The polycarbonate base in the present invention is a general term for polymer compounds containing a carbonic acid ester type structure obtained by transesterification of a disubstituted carbonic acid ester and a diol or a reaction of phosgene and a diol as a structural unit in the main chain. In general,
Polycarbonates obtained from 4,4'-dihydroxyphenylalkanes and their analogues are used as diols.

Preferred dihydroxy compounds are 4,4'-dihydroxyphenylmethane, 4,4'-dihydroxyphenyl-1,1-ethane and 4,4'-dihydroxyphenyl-1,1-butane. 4,4'-dihydroxyphenyl-1,1-isobutane, 4,4'-dihydroxyphenyl-2,2-propane, 4,4'-dihydroxyphenyl-2,2-butane, 4,4'-dihydroxyphenyl -2,2-hexane, 4,4'-dihydroxyphenyl-1,1-cyclohexane, 4,4'-dihydroxyphenyl sulfone,
4,4'-dihydroxyphenyl sulfoxide, 4,
Examples thereof include 4'-dihydroxyphenyl sulfide and 4,4'-dihydroxyphenyl ether.

These may be used singly as a polycarbonate or as a copolymer polycarbonate by using two or more kinds. Further, a diol component other than the above dihydroxyphenyl derivative may be contained by copolymerization, and examples of such a component include ethylene glycol,
1,3-propanediol, 1,4-butanediol,
1,6-hexanediol, 1,4-cyclohexanediol, 4,4'-dihydroxyethoxyphenylmethane, hydroquinone, resorcin, catechol, 2,6-
Examples thereof include dihydroxynaphthalene.

As the acid component, an aromatic or aliphatic dibasic acid such as terephthalic acid, isophthalic acid, adipic acid or an ester thereof can be used as a copolymerization component. In this case, a carbonate ester type is contained in the main chain. In addition to the structure, a carboxylic acid ester structure will be partially introduced. Among these polycarbonates, 4,4'-dihydroxyphenyl-2,2 'is particularly preferable in the present invention.
-Polycarbonate using propane (commonly called bisphenol A) as a diol component alone or as a main component of a copolymer.

The structure of the polycarbonate described above,
For the manufacturing method, etc., Shunsuke Murahashi, Minoru Imoto, Hisaya Tani, “Synthetic Polymer V, pages 287 to 294, Asakura Shoten 1971”
Are described in detail in. The solution casting method according to the present invention refers to the following method. Polycarbonate is dissolved in an organic solvent to obtain a solution called uniform dope. The dope is cast on a moving metal plate, dried for a certain period of time, stripped off from the metal plate, conveyed while being held by a metal roll, dried by sending hot air, and dried after a certain amount of drying.

Typical solvents for dissolving polycarbonate include methylene chloride, dioxinsa, m-cresol, chlorobenzene and the like, but methylene chloride is particularly preferable. Further, two or more kinds of solvents may be mixed for the purpose of adjusting the viscosity and drying property of the dope or adjusting the solubility of polycarbonates having different structures. Examples of the solvent that can be mixed include ethyl acetate, methanol, ethanol, 2-propanol, ascent, and methyl ethyl ketone.

In such a film-forming method, when a resin having a relatively low molecular weight is used, the strength of the buffy coat base is weak in the film-forming step, making it difficult to stretch the film. Can't get The average molecular weight of the polycarbonate of the present invention is preferably 10,000 to 200,000, and more preferably 20,000 to 80,000.

In the present invention, by using a resin having a higher molecular weight average molecular weight, the stretching ratio can be freely controlled in the film forming process, and the strength of the completed film itself becomes stronger. Preferably 1 in machine direction
Stretching is 0% or more. By changing the drying temperature condition in the film forming process, the amount of solvent remaining in the wound film can be controlled. Preferably, the residual solvent is 1% by weight or less.

The thickness of the base of the present invention can be freely selected according to the application. In the present invention, 90μ-150μ,
Preferably 100μ-140μ, more preferably 110
Use a polycarbonate base of μ-130μ. It is preferable that the thickness of the base is thin because the diameter of the cartridge can be made small, but on the other hand, the thinning of the base lowers the bending strength of the base, which causes a problem in handling the film in the camera or in the laboratory. Further, if the base is made thick, the diameter of the cartridge becomes large, and if the base becomes too thick and the bending strength of the base becomes too large, the problem of handling the film in the camera or in the laboratory also becomes a problem. Considering the diameter of the cartridge and the bending strength of the base, a polycarbonate base having the above thickness is preferably used in the present invention.

Particularly, the residual solvent in the polycarbonate base having an average molecular weight of 20,000 to 80,000 is set to 1.0% by weight or less, and the thickness 110 μ to 13 μm which is stretched by 10% or more in the machine direction during film formation.
It is preferable to use it as a base of 0 μ because the handling property of the photographic film in a camera, a film developing machine, a printer and the like is greatly improved. The polycarbonate base of the present invention may contain various additives. For example, a dye can be added for the purpose of reducing light piping or adjusting the tint of the base.

The dye used for dyeing the film is not particularly limited, but the color tone is preferably gray dyeing due to the general properties of the light-sensitive material, and the dye is excellent in heat resistance in the film forming temperature range of the polycarbonate film. Further, those having excellent compatibility with polycarbonate are preferable. Regarding the dyeing density, it is necessary that the color density in the visible light region is measured with a color densitometer manufactured by Macbeth Co. and is at least 0.01 or more. More preferably, it is 0.03 or more.

The polycarbonate support of the present invention preferably has a subbing layer in order to increase the adhesive force with a photographic layer such as a photosensitive layer coated thereon. Examples of the subbing layer include a subbing layer using a polymer latex made of a styrene-butadiene copolymer or a vinylidene chloride copolymer, and a subbing layer using a hydrophilic binder such as gelatin.

The subbing layer preferably used in the present invention is a subbing layer using a hydrophilic binder. Examples of the hydrophilic binder used in the present invention include water-soluble polymers, cellulose esters, latex polymers and water-soluble polyesters. 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, and carboxymethyl cellulose as a cellulose ester,
Hydroxyethyl cellulose and the like. Examples of the latex polymer include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylic ester-containing copolymers, vinyl acetate-containing copolymers and butadiene-containing copolymers. Of these, gelatin is the most preferable.

Various gelatin hardeners can be used in the subbing layer of the present invention. As gelatin hardening agents, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine, etc.), epichlorohydrin resin And so on.

The subbing layer of the present invention comprises SiO ₂ , Ti.
Inorganic fine particles such as O ₂ or polymethylmethacrylate copolymer fine particles (1 to 10 μm) can be contained as a matting agent. The undercoat layer according to the present invention can be applied by a generally well-known coating method, for example, a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, or the like. Is.

The light-sensitive material of the present invention may have a non-light-sensitive layer such as an anti-halation layer, an intermediate layer, a back layer and a surface protective layer in addition to the light-sensitive layer. When the back layer is provided, a hydrophobic binder may be used, but it is preferable to use a hydrophilic polymer such as that used for the undercoat layer because the humidity dependence of curl of the light-sensitive material is reduced. The thickness of the back layer is preferably 2 μ to 10 μ, more preferably 3 μ to 8 μ.

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, and examples of the anionic polymer electrolyte include polymers containing a carboxylic acid, a carboxylic acid salt and a sulfonic acid salt, for example, JP-A-48-22017.
No. 4, JP-B-46-24159, JP-A-51-3072
5, JP-A-51-129216, JP-A-55-95.
It is a polymer as described in No. 942. Examples of the cationic polymer include, for example, JP-A-49-121523.
No. 4, JP-A-48-91165, JP-B-49-2458.
There are some as described in No. 2. 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.
No., US2,992,108, US3,206,31
2. JP-A-48-87826 and JP-B-49-1156.
7, JP-B-49-11568, JP-A-55-708.
The compound as described in No. 37 etc. can be mentioned.

The most preferable antistatic agent for the back layer of the present invention is ZnO, TiO ₃ , 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 0.0
It is desirable that the thickness is 1 to 0.7 μ, and particularly 0.02 to 0.5 μ.

Regarding the method for producing the fine particles of the conductive crystalline metal oxide or composite oxide used in the present invention, JP-A-56-143430 and JP-A-60-258541.
Are described in detail in the specification. First, a method in which metal oxide fine particles are produced by firing, and heat treatment is performed in the presence of a heteroatom to improve conductivity, and secondly, a method for improving conductivity when producing metal oxide fine particles by firing. A method of coexisting atoms, a third method of introducing oxygen defects by lowering the oxygen concentration in the atmosphere when producing the metal fine particles by firing are easy. As an example including a heteroatom, ZnO is Al, In, etc., and TiO ₂ is N.
b, Ta, etc., and SnO ₂ includes Sb, Nb, halogen elements and the like. Addition amount of hetero atoms is 0.01-30
The range of mol% is preferable, but 0.1 to 10 mol% is particularly preferable.

The color negative film preferably applied to the present invention will be described in detail below, but the light-sensitive material of the present invention is not limited to this. Total thickness of photosensitive layer is 3
It is 0 μm or less, preferably 25 μm or less, more preferably 21 μm or less, 12 μm or more. The total film thickness of the photosensitive layer includes the antihalation layer in contact with the base, the uppermost protective layer, and other intermediate layers. If the total thickness of the photosensitive layer is too large, the light incident on the photosensitive layer is strongly scattered, so the sharpness of the image is reduced, and the flatness of the photosensitive material in the exposure station of the camera is highly dependent on humidity.
This causes problems such as an increased possibility of causing poor focus.

If the total thickness of the photosensitive layer is too thin, the scratch resistance of the photosensitive layer deteriorates, which is not preferable. The total film thickness of the photosensitive layer can be easily measured using a micrograph of a cross section of the photosensitive material or a film thickness meter. The photographic film of the present invention may be provided with at least one layer of a silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer on a support,
There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. 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, the arrangement of the unit photosensitive layers is generally , But a red color-sensitive layer, a green color-sensitive layer and a blue color-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer. In the intermediate layer, JP-A Nos. 61-43748, 59-113438, 59-113440 and 6-
The couplers and DIR compounds as described in the specifications of 1-20037 and 61-20038 may be contained, and a color mixing inhibitor may be contained as is commonly used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are a high sensitivity emulsion layer and a low sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure of emulsion layers can be preferably used. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
JP-A-57-112751, JP-A-62-200350
No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer, (BL) / high sensitivity blue photosensitive layer (B
H) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH
/ RL, or BH / BL / GH / GL / RL / R
It can be installed in the order of H or the like.

Further, as described in JP-B-55-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in No. 6, it is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

Further, as described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest photosensitivity, the middle layer is the silver halide emulsion layer having a lower photosensitivity, and the lower layer is the middle layer. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. It may be arranged in the order of layer / high-speed emulsion layer / low-speed emulsion layer.

As described above, various layer structures and arrangements can be selected according to the purpose of each photosensitive material.
The preferred silver halide contained in the photographic emulsion layer of the photographic film used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 25 mol% silver iodide.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, and irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane 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 about 0 micron, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No.
17643 (December 1978), pp. 22-23,
"I. Emulsion preparation and type
s) ”and ibid. No. 18716 (11 November 1979)
Mon), pp. 648, "The Physics and Chemistry of Photography" by Graphide,
Published by Paul Montel (P.Glafkides, Chemicet Phisique
Photographique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffi)
n, Photographic Emulsion Chemistry (Focal Press, 1
966)): "Production and coating of photographic emulsions" by Zelikman et al., Published by Focal Press (VLZelikman et al., Ma.
king and Coating Photographic Emulsion, Focal Pres
s, 1964) and the like.

US Pat. Nos. 3,574,628 and 3,
655,394 and British Patent No. 1,413,748.
The monodisperse emulsions described in JP-A No. 1994-1999 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 (Gutoff, P
hotographic Science and Engineering), Vol. 14, 2
48-257 (1970); U.S. Pat. No. 4,43.
4,226, 4,414,310, 4,43
It can be easily prepared by the method described in 3,048, 4,439,520 and British Patent 2,112,157.

The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and silver halides having different compositions may be bonded by epitaxial bonding. May be
Further, it may be bonded 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. Additives used in such a process are described in Research Disclosure No. 17643 and No. 18716, and the corresponding portions 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 described below.

Additive type RD7643 RD18716 1 Chemical sensitizer, page 23, page 648, right column 2 Sensitivity enhancer, same as above 3 Spectral sensitizer, pages 23 to 24, page 648, right column Supersensitizer, page 649, right column 4, sensitized White agent 24 pages 5 Antifoggants 24 to 25 pages 649 right column and stabilizer 6 Light absorbers, 25 to 26 pages 649 right column to filter dyes, 650 left column UV absorbers 7 Stain inhibitors 25 pages right Column page 650 left to right column 8 dye image stabilizer page 25 9 hardener 26 page 651 page left column 10 binder page 26 same as above 11 plasticizer, lubricant page 27 page 650 right column 12 coating aid, 26-27 Page 650 page right column surface active agent 13 static page 27 same as above In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. Nos. 4,411,987 and 4,435,5 It is preferable to add a compound capable of being immobilized by reacting with formaldehyde gas described in No. 03 to the light-sensitive material.

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG. .. Examples of yellow couplers include U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024, 4,401,752, and 4,248,961. issue,
Japanese Patent Publication No. 58-10739, British Patent No. 1,425,0
20, No. 1,476,760, and U.S. Pat. No. 3,9.
73,968, 4,314,023, 4,
511,649 and EP 249,473A, especially those mentioned are preferred.

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. 3,725,064, Research
Disclosure No. 24220 (June 1984)
, JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238, 60-.
No. 35730, No. 55-118034, No. 60-18.
5951, 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-based and naphthol-based couplers, and US Pat.
52,212, 4,146,396, and 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. 4,327,173
, West German Patent Publication No. 3,329,729, European Patents 121,365A, 249,453A, U.S. Patents 3,446,622, 4,333,999.
No. 4,753,871, No. 4,451,55
9, No. 4,427,767, No. 4,690,8
89, 4,254,212 and 4,296,4
Those described in JP-A No. 199, JP-A-61-42658 and the like are preferable.

Colored couplers for correcting unnecessary absorption of color forming dyes are Research Disclosure No.
17643, Section VII-G, U.S. Pat. No. 4,163,67
No. 0, Japanese Patent Publication No. 57-39413, US Pat.
Those described in 4,929, 4,138,258 and British Patent 1,146,368 are preferable. Examples of couplers in which the color forming dye has an appropriate diffusibility include U.S. Pat. No. 4,366,237 and British Patent 2,125,57.
Those described in No. 0, European Patent No. 96,570 and West German Patent (Publication) No. 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are 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 and British Patent 2,102,173. Examples of couplers that release an engraving agent or a current color accelerator during development include British Patent Nos. 2,097,140 and 2,097,140.
131,188, JP-A-59-157638, JP-A-5-157638.
Those described in 9-170840 are preferable.

Other couplers which can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,42.
Competitive couplers described in US Pat.
No. 472, No. 4,338, 393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DI described in JP-A-62-24252, etc.
R redox compound-releasing couplers, DIR coupler-releasing couplers, DIR coupler-releasing redox compounds or DIR redox-releasing redox compounds, couplers releasing a dye that recolors after release according to EP 173,302A, D. 11449, 24241, bleach accelerator releasing couplers described in JP-A-61-201247, ligand releasing couplers described in U.S. Pat. No. 4,553,477, and leuco described in JP-A-63-75747. Examples thereof include couplers that release dyes.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,222.
No. 027 and the like. The color photographic light-sensitive material according to the present invention has the RD. No. 17643, 28-
The development processing can be carried out by a usual method described on page 29, and 615, left column to right column of No. 18716.

Japanese Patent Application No. 1-218 for the cartridge of the present invention
62, Japanese Patent Application No. 1-172594, US Pat. No. 483.
4306, No. 4846418, No. 4832275, and the like may be provided with a film supply mechanism. The light-sensitive material for photographing of the present invention is described in US Pat.
No. 82947, No. 4279945, No. 4302523
It may have a magnetic recording layer described in No.

Next, a print material suitable for the present invention will be described with an emphasis on a color print photosensitive material, but the present invention is not limited to this. By printing on a printing material having a resolution of 5 lines / mm or more, preferably 7 lines / mm or more, the effect of the photographic film product of the present invention becomes more remarkable. Here, the spatial frequency that gives an MTF value of 0.5 is defined as the resolution.

When the exposure for MTF measurement is given, the exposure is balanced so that the image becomes gray. Visual density is measured to determine MTF. (Definition of MTF: The Th
eoryof the Photographic Process 4th ed THJames.
(1977) Macmillan Publishing Co., Ltd p596
(See Reference) In order to obtain a printing material having a high resolution as described above, it is important to prevent the light when exposed from bleeding over a wide area of the printed surface and causing blurring.

For this purpose, there are a method of using a water-soluble dye, a method of providing a coloring layer for preventing halation, and a method of increasing the reflectance near the surface of the reflective support. The use of water-soluble dyes for preventing irradiation is described in, for example, JP-A Nos. 50-145125 and 52-208.
30, No. 50-147712, No. 59-111
No. 641, No. 61-148448, No. 61-15
No. 1538, No. 61-151649, No. 61-1
No. 51650, No. 61-151651, No. 61-
170742, 61-175638, 61
-235837, 61-248044, 6
2-164043, 62-253145, 62-253146, 62-253142, 62-275262, 62-283336 and Research Disclosure RD-17643.
No. (December 22, 1978 page) and RD-18716 (November 1979, page 647). A method for providing an antihalation layer (AH) on a color light-sensitive material is disclosed in, for example, US Pat.
No. 82156, No. 2839401, No. 37065.
63, JP-A-55-33172, and JP-A-59-193.
No. 447 and No. 62-32448, and the like.

It is also described in JP-A-63-286849 that the optical reflection density when these diffusible dyes and colorants such as AH are used is set to a certain level or more. Originally, baryta paper was used as a support for a color print light-sensitive material, but recently, a water-resistant support in which polyethylene is laminated on both sides of a base paper is used for speeding up development processing. Titanium oxide or zinc oxide is dispersed in the polyethylene layer to improve the sharpness of the printed image, and improvement of the polyethylene layer containing titanium oxide is being studied to further improve the sharpness. Examples of these are described in JP-B-58-43734, JP-A-58-17433, JP-A-58-14830, and JP-A-61-259246.

In order to increase the filling rate of titanium oxide and further improve the sharpness, the water-resistant resin layer on the base paper is made of an unsaturated organic compound having one or more double bonds in one molecule which can be polymerized by an electron beam. A method in which a coating solution containing a white pigment and a base paper is applied and then cured by electron beam irradiation while heating is provided, for example, in JP-A-57-27257, 57-49946 and 61-61. Nos. 262738 and 62-61049.

As a method of increasing reflection near the surface and improving sharpness, a silver halide light-sensitive material using a specular or type II diffuse reflection support is also known. For example, JP-A-63-24251 to 24253
No. etc. In the color print light-sensitive material according to the present invention, a hydrophilic colloid layer is added in order to improve image sharpness and the like, and European Patent EP 0,337,4.
90A2, pages 27 to 76, it is preferable to add a dye capable of being decolorized by a developing treatment so that the optical reflection density at 680 nm of the light-sensitive material becomes 0.30 or more. A pyrazolone oxonol dye is particularly preferable as the dye. Further, it is preferable to contain 12% by weight or more of titanium oxide in the water resistant resin layer of the support, and particularly 14
It is preferable that the content is at least wt%.

Further, a wavelength of 5 is used as an antihalation layer.
It is also preferable to provide a colored layer having an optical reflection density of 0.2 or more at 50 nm light between the support and the emulsion layer. It is also preferable to use a specularly reflective or second type diffusely reflective support as the support. As the silver halide used in the color print material of the present invention, silver chloride, silver bromide, silver (iodo) chlorobromide, silver iodobromide and the like can be used. The content of silver chloride substantially free of silver halide is 90 mol% or more, and further 95
It is preferable to use silver chlorobromide or silver chloride emulsion in an amount of not less than%, particularly not less than 98%.

Further, in the light-sensitive material for color printing according to the present invention, a coupler is used together with European Patent EP 0,277,
It is preferable to use a color image keeping improving compound as described in 589A2. In particular, it is preferably used in combination with a pyrazoloazole coupler. That is, the compound (F) that chemically bonds to the aromatic amine-based developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or the aroma remaining after the color development processing. The simultaneous use of the compound (G), which forms a chemically inactive and substantially colorless compound by chemically bonding with an oxidant of a group amine color developing agent, for example, in storage after processing. It is preferable in order to prevent the occurrence of stains and other side effects due to the formation of a coloring dye due to the reaction of the coupler with the residual color developing agent in the film or its oxidation product.

Further, in the light-sensitive material for color print according to the present invention, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, JP-A-63-27 is used.
It is preferable to add an antifungal agent as described in No. 1247. As the support used in the light-sensitive material for color print according to the present invention, a support in which a white polyester support or a layer containing a white pigment is provided on a support having a silver halide emulsion layer for display. May be used. In particular, it is also preferable to set the transmission density of the support in the range of 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light. Further, upon exposure, it is preferable to use the band stop filter described in U.S. Pat. No. 4,880,726. As a result, the light color mixture is removed, and the color reproducibility is significantly improved.

The exposed light-sensitive material for color printing can be subjected to a developing treatment, but for the purpose of rapid processing, it is preferable to carry out a bleach-fixing treatment after the color development. Particularly when the above high silver chloride emulsion is used, the pH of the bleach-fixing solution is preferably about 6.5 or less, more preferably about 6 or less for the purpose of promoting desilvering. Silver halide emulsions and other materials (additives and the like) and photographic constituent layers (layer arrangement and the like) applied to the light-sensitive material for color print according to the present invention, and a processing method applied to process the light-sensitive material. The following patent publications, particularly European Patent EP 0,355,
Those described in 660A2 (Japanese Patent Application No. 1-107011) are preferably used. ──────────────────────────────────── Photographic elements, etc. JP 62-215272 JP 2 -No. 33144 EP0,355,660A2 No. ──────────────────────────────────── Silver halide page 10 Upper right Column Line 6 to page 28 Upper right column Line 16 Page 45 Line 53 to page 47 Emulsion page 12 Lower left column Line 5 and page 29 Right lower column 11 Line 3 and page 47 Line 20 Lower right column 4th from the bottom and page 30 2nd line to 22nd line 2nd to page 13 Upper left column 17 5th line 5th silver halide Page 12 lower left column 6th line to ───── ──── Solvent 14 Lines and 13 Upper left column 3rd line from bottom to page 18 Lower left column Last line Chemical sensitizer page 12 Lower left column from bottom 3 Page 29 Lower right column 12th line 47 Page 4th line to 9th line Eye to bottom right column Bottom to bottom line 5th line and page 18 Bottom right column 1st line to page 22 Top right column Bottom to line 9 Spectral sensitizer page 22 Top right column bottom to page 30 Top left column 1 line Eye 47 Lines 10 to 15 (Spectral sensitization method) Lines to page 38 Last line to line 13 Emulsion stabilizer Page 39 Upper left line 1 to page 30 Upper left column Line 14 Page 47 Lines 16 to 19 Page 72 Top right column Last line ~ Top right column 1st line

Development Accelerator, page 72, lower left column, line 1 to ────────── page 91, upper right column, line 3 color coupler page 91, upper right column, line 4 to page 3, upper right column, line 14, page 4, line 15 Lines 27 to 27 (Cyan, page 121, upper left column, line 6 to page 18, upper left column, end line, page 5 lines 30 to 28, magenta, eye and page 30, upper right column, line 6 last line, page 45, line 29 Eye Yellow Coupler Line ~ Page 35 Lower right column ~ Line 31, Line 47, Page 23 Line 23) Line 11 ~ Page 63 Line 50 Line Enhancer 121 Page Upper left column Line 7 ──── ───── Page 125 Top right column 1st line UV absorber Page 125 Top right column 2nd line Page 37 Bottom right column 14th line 65 Page 22 Lines 31 to 31 Page 127 Bottom left column Last line ~ Page 38 Top left column 11th line

Anti-fading agent Page 127, lower right column, line 1 Page 36, lower right column, line 12 Page 4 line 30 to page 5 to 23 (image stabilizer ~ page 137, lower left column, line 8 to page 37, upper left column, line 19) Page, page 29, 1st line ~) page 45, page 25, 45, page 33, line 33-40, page 65, line 2-21, high boiling point and / page 137, lower left column, line 9, page 35, right Bottom line, line 14 Page 64, lines 1 to 51 or low boiling point-Page 144 Top right column, end line to page 36 Top left column, bottom or machine solvent to line 4 Page 144, left bottom column, line 1 for photographic additives Page 27 Lower right column 10th line Page 63 51st line to 64th page 56 Dispersion method ~ Page 146 Upper right column 7th line to 28th page Upper left column Last line Last line and 35th lower right column 12th line to 36th page Top right column 7th line Hardener 146 pages Top right column 8th line ──── ──── 〜 155 Left bottom column 4th line

Development agent Precursor 155, lower left column, line 5 ──── ───── 〜 page 155, lower right column, second line Development inhibitor release, page 155, lower right column, third line ──────── -Compound ~ Line 9 Support 155 Page lower right column 19 line 38 Page upper right column 18 line 66 Page 29 line 29 ~ 67 page 13 ~ 156 upper left column line 14 ~ 39 upper left column line 3 line 3 Photosensitive layer composition Page 156 Upper left column 15th line Page 28 Upper right column 1st line 45th page 41st line to 52nd line ~ 156 Lower right column 14th line to 15th line

Dye 156 Page lower right column 15 line 38 Page upper left column 12 line 66 Page 18 lines 22 to 22 page 184 Lower right column last line to upper right column 7th line Color mixture inhibitor 185 upper left column Line 1 Page 36 Upper right column Line 8 Page 64 Line 57 to 65 Page 1 to 188 Lower right column Line 3 to 11 Line Line Tone control agent Page 188 Lower right column Line 4 ──── ──── ~ Line 8 Stain prevention Page 188 Lower right column 9th line 37 Page upper left column Last line 65th line 32nd line to 66th page 17 Agents ~ Page 193 Lower right column 10th line to lower right column 13th line Line 201 Surfactant Page 201 Lower left column 1st line Page 18 Upper right column 1st line ──── 〜 210 Page upper right column Last line 〜 24 Right lower column Last line Eye and page 27 Lower left column Lower line 10 Eye-lower right column, line 9

Fluorine-containing compound 210, lower left column, first line, page 25, upper left column, first line ──── (Antistatic agent, page 222, lower left column, line 5 to page 27, lower right column, line 9 Coating aid, moisture Binder 222 Page, lower left column, line 6 Page 38, upper right column, line 8 Page 66, lines 23 to 28 (hydrophilic roller, page 225, upper left column, end line to line 18) Id) Thickener page 225, upper right column, first line ──── ───── ~ page 227, upper right column, second line Antistatic agent, page 227, upper right column, third line ───────── ~ 230 Upper left column first line

Polymer 230, page 2, upper left column, second line ──── ──── tex ~ page 239, last line Mat agent 240 page, upper left column, first line ──── ──── ~ page 240, upper right column, last line Photographic processing method Page 3, upper right column, line 7 to page 39, upper left column, line 4 Page 67, line 14, line 69 to page 28 (Processing and page 10, upper right column, line 5 to page 42, upper left column, end line Line Additives Etc.) ──────────────────────────────────── Note) Citation of JP-A-62-215272 The section also includes the content amended by the procedure amendment dated March 16, 1987 published at the end of this publication.

Among the above color couplers, yellow couplers are disclosed in JP-A-63-231451 and JP-A-62-12.
3047, 63-241547 and JP-A-1-173499, 1-
It is also preferable to use the so-called short-wave type yellow couplers described in JP-A Nos. 213648 and 1-250944. Further, as a cyan coupler, in addition to the diphenylimidazole type cyan coupler described in JP-A-2-33144, European Patent E
3-Hydroxypyridine cyan couplers described in P0,333,185A2 (among others, couplers (42) listed as specific examples, which are 4-equivalent couplers with a chlorine-releasing group to make them 2-equivalent, and couplers (6 ) And (9)
Is particularly preferable) and cyclic active methylene cyan couplers described in JP-A-64-32260 (specifically, coupler examples 3, 8, and 34 listed as specific examples) are also preferably used.

[0094]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Example 1 (1) Preparation of Color Negative Film for Photographing (1-1) Preparation and Application of Coating Liquid On the undercoated cellulose triacetate film support (thickness 115 μm), each layer having the following composition was laminated. Application was performed to prepare Sample 101 (sensitivity ISO-400) which is a multilayer color negative photosensitive material. (Photosensitive layer composition) The numbers corresponding to the respective components indicate the coating amount in g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer. (Sample 101) First layer (antihalation layer) Black colloidal silver 0.18 gelatin 1.40 Second layer (intermediate layer) 2,5-di-t-pentadecylhydroquinone 0.18 EX-1 0.18 EX-3 0.020 EX-12 2.0 × 10 ^-3 U-1 0.060 U-2 0.080 U-3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 1.04

Third Layer (First Red Sensitive Emulsion Layer) Emulsion A Silver 0.25 Emulsion B Silver 0.25 Sensitizing Dye I 6.9 × 10 ^-5 Sensitizing Dye II 1.8 × 10 ^-5 Sensitizing Dye III 3.1 × 10 ^-4 EX -0.17 EX-10 0.020 EX-14 0.17 U-1 0.070 U-2 0.050 U-3 0.070 HBS-1 0.060 Gelatin 0.87 4th layer (2nd red-sensitive emulsion layer) Emulsion G Silver 1.00 Sensitizing dye I 5.1 x 10 ^-5 sensitizing dye II 1.4 × 10 ^-5 sensitizing dye III 2.3 × 10 ^-4 EX-2 0.20 EX-3 0.050 EX-10 0.015 EX-14 0.20 EX-15 0.050 U-1 0.070 U-2 0.050 U -3 0.070 Gelatin 1.30

Fifth Layer (Third Red Sensitive Emulsion Layer) Emulsion D Silver 1.60 Sensitizing Dye I 5.4 × 10 ^-5 Sensitizing Dye II 1.4 × 10 ^-5 Sensitizing Dye III 2.4 × 10 ^-4 EX-2 0.097 EX -3 0.010 EX-4 0.080 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63 6th layer (intermediate layer) EX-5 0.040 HBS-1 0.020 Gelatin 0.80

Seventh layer (first green-sensitive emulsion layer) Emulsion A Silver 0.15 Emulsion B Silver 0.15 Sensitizing dye IV 3.0 × 10 ^-5 Sensitizing dye V 1.0 × 10 ^-4 Sensitizing dye VI 3.8 × 10 ^-4 EX -1 0.021 EX-6 0.26 EX-7 0.030 EX-8 0.025 HBS-1 0.10 HBS-3 0.010 Gelatin 0.63 Eighth layer (second green emulsion layer) Emulsion C Silver 0.45 Sensitizing dye IV 2.1 × 10 ^-5 Sensitizing dye V 7.0 × 10 ^-5 Sensitizing dye VI 2.6 × 10 ^-4 EX-6 0.094 EX-7 0.026 EX-8 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.50

Ninth Layer (Third Green Sensitive Emulsion Layer) Emulsion E Silver 1.20 Sensitizing Dye IV 3.5 × 10 ^-5 Sensitizing Dye V 8.0 × 10 ^-5 Sensitizing Dye VI 3.0 × 10 ^-4 EX-1 0.013 EX -11 0.065 EX-13 0.019 HBS-1 0.25 HBS-2 0.10 Gelatin 1.54 10th layer (yellow filter layer) Yellow colloidal silver 0.050 EX-5 0.080 HBS-1 0.030 Gelatin 0.95 11th layer (1st blue emulsion layer) ) Emulsion A Silver 0.080 Emulsion B Silver 0.070 Emulsion F Silver 0.070 Sensitizing dye VII 3.5 × 10 ⁻⁴ EX-8 0.042 EX-9 0.72 HBS-1 0.28 Gelatin 1.10

Twelfth Layer (Second Blue Sensitive Emulsion Layer) Emulsion G Silver 0.45 Sensitizing Dye VII 2.1 × 10 ⁻⁴ EX-9 0.15 EX-10 7.0 × 10 ⁻³ HBS-1 0.050 Gelatin 0.78 13th Layer (third layer) 3 Blue-sensitive emulsion layer) Emulsion H Silver 0.77 Sensitizing dye VII 2.2 × 10 ^-4 EX-9 0.20 HBS-1 0.070 Gelatin 0.69

Fourteenth Layer (First Protective Layer) Emulsion I Silver 0.20 U-4 0.11 U-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 Furthermore, all layers have preservability, processability, pressure resistance, mildew / bacterial resistance, To improve the antistatic property and coating property W-1,
W-2, W-3, B-4, B-5, F-1, F-2, F
-3, F-4, F-5, F-6, F-7, F-8, F-
9, F-10, F-11, F-12, F-13, and iron salt, lead salt, gold salt, platinum salt, iridium salt, and rhodium salt are contained.

Table-1 ──────────────────────────────────── Average AgI Average grain size to diameter Silver Volume ratio Particle size variation / thickness Content (%) (μm) Coefficient (%) Ratio (AgI content%) ─────────────────────── ────────────── Emulsion A 4.0 0.45 27 1 core / shell = 1/3 (13/1), double structure grains 〃 B 8.9 0.70 14 1 core / shell = 3/7 (25/2), double structure particles 〃 C 10 0.75 30 2 core / shell = 1/2 (24/3), double structure particles 〃 D 16 1.05 35 2 core / shell = 4/6 (40/0 ), Double structure particles 〃 E 10 1.05 35 3 core / shell = 1/2 (24/3), double structure particles 〃 F 4.0 0.25 28 1 core / shell = 1/3 (13/1), double Structural particles 〃 G 14.0 0.75 25 2 core / shell = 1/2 (42/0), double structure particles 〃 H 14.5 1.30 25 3 core / shell = 37/63 (34/3), double structure particles 〃 I 1 0.07 15 1 Uniform particles ─────── ────────────────────────────

[0102]

[Chemical 1]

[0103]

[Chemical 2]

[0104]

[Chemical 3]

[0105]

[Chemical 4]

[0106]

[Chemical 5]

[0107]

[Chemical 6]

[0108]

[Chemical 7]

[0109]

[Chemical 8]

[0110]

[Chemical 9]

[0111]

[Chemical 10]

[0112]

[Chemical 11]

[0113]

[Chemical formula 12]

[0114]

[Chemical 13]

Next, instead of the cellulose triacetate film, a polycarbonate film having an average molecular weight of 30,000 copolymerized with phosgene and bisphenol A (thickness: 115 μ)
Sample 1 exactly the same as Sample 101 except that
02 was produced. (1-2) Processing of Color Negative Film Samples 101 and 102 were processed into a 135 format roll film and wound into a 135 format cartridge. 101 (135), 1 for each film
02 (135).

Further, a 135-format roll film was wound into a cartridge formed of polystyrene having 5% carbon black kneaded in the shape shown in FIG.
101 (NC), 102 (N
C).

(2) Preparation of color paper for printing (2-1) Preparation of support LBKP (hardwood bleached, sulfate pulp) for photographic printing paper 1
00% (weighing 175 g / m ² , thickness about 180 μ); A white pigment-containing resin layer made of water resistant titanium oxide having the following composition was provided on the surface of a white base paper to prepare a support A. (I) Water-resistant resin layer on the surface of white base paper (thickness 30 μ) Polyethylene composition 90 parts by weight (density 0.92 g / cc, melt index (MI) 5.0 g / 10 minutes) Anatase titanium oxide white pigment 10 parts by weight (oxidation Surface treatment with silicon and aluminum oxide) (II) Water resistant resin layer on back side of white base paper (thickness 20μ) Polyethylene composition (density 0.95 g / cc, MI 8.0 g / 10 minutes) Next, the polyethylene composition of (I) To 85 parts by weight,
Further, a support B was prepared in exactly the same manner as the preparation of the support A, except that the surface treatment agent for the titanium oxide white pigment was changed to trimethylolethane and the amount was changed to 15 parts by weight.

The dispersibility of the white pigment particles on the surface portion of the water resistant resin layer of the support according to the present invention was measured by observing the white pigment particles with an electron microscope by etching the resin of about 0.05 μm from the surface by the ion sputtering method. The projected area ratio Ri of each particle is obtained for 6 consecutive 6 μm × 6 μm unit areas, and the standard deviation thereof is obtained.

[0119]

[Equation 1]

The average particle occupation area ratio (%) R was determined. As a result, the coefficient of variation (S / R) of the particle occupation area is
It is 0.25 for support A and 0.10 for support B.
The white pigment has excellent dispersibility. (2-2) Preparation and Application of Coating Liquid On the undercoated support A, each layer having the composition as shown below is multilayer-coated to form a multilayer color paper photosensitive material 201.
Was produced.

The composition of each layer is shown below. Numbers represent coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

First layer gelatin 0.8 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (blue sensitive emulsion layer) The above emulsion Em-3 0.09 The above emulsion Em-6 0.21 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.18 Solvent (Solv-7) 0.18 Color image stabilizer (Cpd-7) 0.06

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.99 Color mixing inhibitor (Cpd-5) 0.08 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08 Fifth layer (Green-sensitive emulsion layer) The above emulsion Em- 2 0.04 Emulsion described above Em-5 0.07 Gelatin 1.24 Magenta coupler (ExM) 0.23 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.16 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer Agent (Cpd-9) 0.02 Solvent (Solv-2) 0.40

Sixth layer (UV absorbing layer) Gelatin 1.58 UV absorbing agent (UV-1) 0.47 Color mixing inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Seventh layer (red sensitive emulsion layer) The above emulsion Em-1 0.07 Emulsion described above Em-4 0.16 Gelatin 1.34 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-6) 0.18 colors Image stabilizer (Cpd-7) 0.40 Color image stabilizer (Cpd-8) 0.05 Solvent (Solv-6) 0.14

Eighth Layer (UV Absorbing Layer) Gelatin 0.53 UV Absorbing Agent (UV-1) 0.16 Anti-Color Mixing Agent (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Ninth Layer (Protecting Layer) Gelatin 1.33 Polyvinyl alcohol Acrylic modified copolymer (Modification degree: 17%) 0.17 Liquid paraffin 0.03 Further, the following dyes (in parentheses represent coating amount) were added to the emulsion layer to prevent irradiation.

[0126]

[Chemical 14]

[0127]

[Chemical 15]

[0128]

[Chemical 16]

[0129]

[Chemical 17]

[0130]

[Chemical 18]

[0131]

[Chemical 19]

[0132]

[Chemical 20]

[0133]

[Chemical 21]

[0134]

[Chemical formula 22]

[0135]

[Chemical formula 23]

Table-2 List of silver chloride emulsion size (μ) Coefficient of variation Sensitizing dye (mol / mol Ag) Em1 0.46μ 0.09 V-6 1 × 10 ⁻⁴ 2 0.44μ 0.08 V−41 5 × 10 ⁻⁴ 3 0.82μ 0.11 V−34 2 × 10 ⁻⁴ V−36 2 × 10 ⁻⁴ 4 0.38μ 0.07 V− 6 1.2 × 10 ⁻⁴ 5 0.37μ 0.07 V−41 6 × 10 ⁻⁴ 6 0.70μ 0.10 V− 34 2.5 × 10 ^-4 V-36 2.5 × 10 ^{-4 The} above emulsion contains nucleic acid, sensitizing dye, 0.05 μm silver bromide emulsion (
0.3-0.6 mol%) (2 potassium diiridium hexachloride)
10 ^-5 mol / mol Ag content) was added, and triethylthiourea and chloroauric acid were added for optimum chemical sensitization,
Furthermore, 1- (5-methylureidophenyl) -5-mercaptotetrazole is added. Further, the following compounds were added to Em1 and 4 at 2.6 × 10 ⁻³ mol / mol Ag.

[0137]

[Chemical formula 24]

Next, the support B was used in place of the support A, and black colloidal silver 0.2 g / m ² , Cpd (1
A sample 202 was prepared in exactly the same manner as the sample 201 except that 0.002 g / m ^{2 of} 2) was added. (2-3) Processing of color paper Samples 201 and 202 were slit to prepare a roll having a width of 127 m / m. (2-4) Measurement of MTF The samples 201 and 202 were subjected to balanced exposure so as to give a gray image, through a MTF chart, and subjected to development processing described later to measure MTF.

Resolution measured by visual density (MTF value
The spatial frequency giving 0.5) was 4 lines / mm for sample 201 and 8 lines / mm for sample 202. First, the sample 201 is subjected to gray exposure so that the developed silver amount becomes 30% of the applied silver amount, and a solution having the following processing step and processing solution composition is used to replenish twice the tank capacity for color development. The continuous treatment (running test) was carried out.

Treatment process Temperature Time Replenisher ^* Tank capacity Color development 35 ℃ 45 seconds 161 ml 17 liter Bleach fixing 30-35 ℃ 45 seconds 215 ml 17 liter Rinse (1) 30-35 ℃ 20 seconds -10 liter rinse ( 2) 30 to 35 ° C 20 seconds −10 liters Rinse (3) 30 to 35 ° C 20 seconds 350 ml 10 liters Dry 70 to 80 ° C 60 seconds * Replenishment amount per 1 m ² of light-sensitive material (rinse (3) → (1 (3) Countercurrent system to 3) The composition of each processing solution is as follows.

Color developer tank replenisher replenisher water 800 ml 800 ml ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1.5 g 2.0 g potassium bromide 0.015 g-triethanolamine 8.0 g 12.0 g sodium chloride 1.4 g-potassium carbonate 25 g 25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 7.0 g N, N-bis (carboxymethyl) hydrazine 4.0 g 5.0 g N, N-di (sulfoethyl) hydroxylamine 1Na 4.0 g 5.0 g Optical brightener (WHITEX 4B, Sumitomo Chemical Co., Ltd.) 1.0 g 2.0 g ───────────────── ───────────────── Add water 1000 ml 1000 ml pH (25 ℃) 10.05 10.45

Bleach-fixing solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetic acid disodium 5 g Ammonium bromide 40 g ───────────────────────────────── 1000 ml pH (25 ℃) 6.0 Rinse solution ( The tank liquid and the replenisher are the same.) Ion-exchanged water (calcium and magnesium are below 3 ppm each)

(3) Modification of camera The Olympus OM-1 and Olympus Pen F were used as they were for the usual 135 format cartridge. An Olympus pen F with a modified film loading chamber was used as the photographic material wound in the attitude-controllable cartridge according to the present invention. (4) Photographing After the photographic material was loaded into the camera, one frame was photographed, the film was wound up, and after 24 hours had elapsed, two consecutive frames were photographed, and the photograph of the second frame was used for evaluation.

Photographing was performed under a constant artificial light source set to dark cloudy brightness. The exposure conditions measured by an exposure meter were 1/125 seconds and the diaphragm 4. Focal length 40
mm was set, and a person was photographed at a distance of 3 m without issuing a strobe.

(5) Development of color negative film Processing was carried out by the following method using an automatic processor. Processing method Process processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38 ° C 45 ml 10 liters Bleaching 1 minute 00 seconds 38 ° C 20 ml 4 liters Bleach fixing 3 minutes 15 seconds 38 ° C 30 ml 8 liters Water Washing (1) 40 seconds 35 ℃ From (2) to (1) 4 liters countercurrent piping system Water washing (2) 1 minute 00 seconds 35 ℃ 30 ml 4 liters Stability 40 seconds 38 ℃ 20 ml 4 liters Dry 1 minute 15 seconds 55 ℃ Replenishment amount is 35mm width 1m length

Next, the composition of the processing liquid will be described. (Color developer) Mother liquor (g ) Replenisher (g ) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg -Hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.5 5.5 Add water 1.0 liter 1.0 liter pH 10.05 10.10

(Bleach) Mother liquor and replenisher common (unit: g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol

[0148]

[Chemical 25]

Ammonia water (27%) 15.0 ml Water was added to 1.0 liter pH 6.3 (bleach-fixing solution) common for mother liquor and replenisher (unit g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 240.0 ml Ammonia water (27%) 6.0 ml Water is added to 1.0 liter pH 7.2

(Washing liquid) common to mother liquor and replenishing liquid Tap water was mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH type anion exchange resin (Amberlite IR-400). Water was passed through a packed mixed-bed column to adjust the concentration of calcium and magnesium ions to 3 mg / l or less, and then 20 mg / l of sodium diisocyanurate dichloride and 0.15 g / l of sodium sulfate were added. The pH of this solution was in the range 6.5-7.5.

(Stabilizer) Mother liquor, replenisher common (unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Water was added. 1.0 liter pH 0.5-8.0

(6) Printing and Evaluation An L size print was prepared using the color printing papers 201 and 202, and the sharpness of the image was evaluated by sensory evaluation by 10 panelists. "Satisfied (4 points)""Almost satisfied (3 points)""Slightly dissatisfied (2 points)""Dissatisfied (1 point)"
The average score was obtained by classifying into four stages.

The results are shown in Table 3. Table-3 Color Negative Camera Color Paper Evaluation Results ────────────────────────────────── 101 (135) Olympus 201 3.2 (Comparison) OM-1 ────────────────────────────────── 101 (135) Olympus 201 2.3 (Comparison) Pen F ────────────────────────────────── 101 (NC) Olympus 201 2.8 (Comparison) Pen F (modification) ) ────────────────────────────────── 102 (NC) Olympus 2013.4 (Invention) Pen F (Modification) ────────────────────────────────── 102 (NC) Olympus 202 3.8 (invention) pen F (Modification) ────────────────────────────────── As is clear from the results in Table 3, the present invention The print quality related to the above is extremely sharp even though it is a small format.

Example 2 Instead of the samples 101 and 102 of Example 1, samples 301 and 302 (each having ISO-1) were prepared by using a photosensitive layer having the following composition.
00) was prepared and the same test as in Example 1 was carried out to obtain the same result as in Example 1. First layer (antihalation layer) Black colloidal silver 0.15 Gelatin 1.90 ExM-1 5.0 × 10 ^-3 Second layer (intermediate layer) Gelatin 2.10 UV-1 3.0 × 10 ^-2 UV-2 6.0 × 10 ^-2 UV-3 7.0 x10 ^-2 ExF-1 4.0 x10 ^-3 Solv-2 7.0 x10 ^-2

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, spherical equivalent diameter 0.3 μm, variation coefficient of spherical equivalent diameter 29%, normal crystal, twin crystal Mixed particles, diameter / thickness ratio 2.5) Silver coating amount 0.50 Gelatin 1.50 ExS-1 1.0 × 10 ^-4 ExS-2 3.0 × 10 ^-4 ExS-3 1.0 × 10 ^-5 ExC-1 0.11 ExC-3 0.11 ExC-4 3.0 × 10 ^-2 ExC-7 1.0 × 10 ^-2 Solv-1 7.0 × 10 ^-3 4th layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, sphere equivalent) Diameter 0.55 μm, variation coefficient of sphere equivalent diameter 20%, normal crystal, twin mixed particles, diameter / thickness ratio 1.0) Silver coating amount 0.85 Gelatin 2.00 ExS-1 1.0 × 10 ^-4 ExS-2 3.0 × 10 ^-4 ExS -3 1.0 × 10 ^-5 ExC-1 0.16 ExC-2 8.0 × 10 ^-2 ExC-3 0.17 ExC-7 1.5 × 10 ^-2 ExY-1 2.0 × 10 ^-2 ExY-2 1.0 × 10 ^-2 Cpd-1 0 1.0 × 10 ^-4 Solv-1 0.10

Fifth Layer (High Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, sphere equivalent diameter 0.7 μm, sphere equivalent diameter variation coefficient 30%, twin mixed particles, diameter / thickness ratio 2.0) silver coverage 0.70 gelatin ^{1.60 ExS-1 1.0 × 10 -4} ExS-2 3.0 × 10 -4 ExS-3 1.0 × 10 -5 ExC-5 7.0 × 10 -2 ExC-6 8.0 × 10 - ² ExC-7 1.5 × 10 ^-2 Solv-1 0.15 Solv-2 8.0 × 10 ^-2 6th layer (intermediate layer) Gelatin 1.10 P-2 0.17 Cpd-1 0.10 Cpd-4 0.17 Solv-1 5.0 × 10 ^-2

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, sphere equivalent diameter 0.3 μm, variation coefficient of sphere equivalent diameter 28%, normal crystal, twin crystal Mixed particles, diameter / thickness ratio 2.5) Silver coating amount 0.30 Gelatin 0.50 ExS-4 5.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS-6 0.3 × 10 ^-4 ExM-1 3.0 × 10 ^-2 ExM-2 0.20 ExY-1 3.0 × 10 ^-2 Cpd-11 7.0 × 10 ^-3 Solv-1 0.20 Eighth layer (medium sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, sphere equivalent) Diameter 0.55 μm, variation coefficient of spherical equivalent diameter 20%, normal crystal, twin crystal mixed particles, diameter / thickness ratio 4.0) Silver coating amount 0.70 Gelatin 1.00 ExS-4 5.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS ^{-6 3.0 × 10 -5 ExM-1} 3.0 × 10 -2 ExM-2 0.25 ExM-3 1.5 × 10 -2 ExY-1 4.0 × 10 -2 Cpd-11 9.0 × 10 -3 Solv-1 0.20

9th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, sphere equivalent diameter 0.7 μm, variation coefficient of sphere equivalent diameter 30%, normal crystal, twin crystal Mixed particles, diameter / thickness ratio 2.0) Silver coating amount 0.50 Gelatin 0.90 ExS-4 2.0 × 10 ^-4 ExS-5 2.0 × 10 ^-4 ExS-6 2.0 × 10 ^-5 ExS-7 3.0 × 10 ^-4 ExM-1 ^{1.0 × 10 -2 ExM-4 3.9} × 10 -2 ExM-5 2.6 × 10 -2 Cpd-2 1.0 × 10 -2 Cpd-9 2.0 × 10 -4 Cpd-10 2.0 × 10 -4 Solv-1 0.20 Solv -2 5.0 x 10 ^-2

10th Layer (Yellow Filter Layer) Gelatin 0.90 Yellow Colloid 5.0 × 10 ⁻² Cpd-1 0.20 Solv-1 0.15 11th Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 4 mol%, Internal high AgI type, sphere equivalent diameter 0.5 μm, variation coefficient of sphere equivalent diameter 15%, octahedral grain) Silver coating amount 0.40 Gelatin 1.00 ExS-8 2.0 × 10 ^-4 ExY-1 9.0 × 10 ^-2 ExY-3 0.90 Cpd-2 1.0 x10 ^-2 Solv-1 0.30

Twelfth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, sphere equivalent diameter 1.3 μm, variation coefficient of sphere equivalent diameter 25%, normal crystal, twin crystal Mixed particle, diameter / thickness ratio 4.5) Silver coating amount 0.50 Gelatin 0.60 ExS-8 1.0 × 10 ^-4 ExY-3 0.12 Cpd-2 1.0 × 10 ^-3 Solv-1 4.0 × 10 ^-2 13th layer (1st protection) Layer) Fine grain silver iodobromide (average particle size 0.07 μm, AgI 1 mol%) 0.20 Gelatin 0.80 UV-2 0.10 UV-3 0.10 UV-4 0.20 Solv-3 4.0 × 10 ^-2 P-2 9.0 × 10 ^-2

14th layer (second protective layer) Gelatin 0.90 B-1 (diameter 1.5 μm) 0.10 B-2 (diameter 1.5 μm) 0.10 B-3 2.0 × 10 ^-2 H-1 0.40 Furthermore, storage stability and treatment In order to improve the property, pressure resistance, antifungal / antibacterial property, antistatic property, and coating property, the following Cpd-
3, Cpd-5, Cpd-6, Cpd-7, Cpd-
8, P-1, W-1, W-2, W-3 were added.

In addition to the above, n-butyl-p-hydroxybenzoate was added. B-4, F-1, F
-4, F-5, F-6, F-7, F-8, F-9, F-
10, F-11, and iron salt, lead salt, gold salt, platinum salt,
It contains iridium salt and rhodium salt. Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

[0163]

[Chemical formula 26]

[0164]

[Chemical 27]

[0165]

[Chemical 28]

[0166]

[Chemical 29]

[0167]

[Chemical 30]

[0168]

[Chemical 31]

[0169]

[Chemical 32]

[0170]

[Chemical 33]

[0171]

[Chemical 34]

[0172]

[Chemical 35]

[0173]

[Chemical 36]

[0174]

[Chemical 37]

[0175]

[Chemical 38]

Example 3 Photographic film 101 (N) of Example 1 except that a polyethylene terephthalate film having an average molecular weight of 30,000 (thickness 115 μ) was used in place of the cellulose triacetate film.
Film 103 (NC) for photography was prepared in exactly the same manner as in C). 101 (NC), 102 (NC), 1 to simulate the situation inside a car under direct sunlight.
03 (NC) was left in a box heated to 80 ° C. for 3 hours. These films were developed with a minilab film processor (10VE Fuji Photo Film Co., Ltd.). 101 (NC) with strong curl due to heating at 80 ° C
And 103 (NC) passed the roller of the processor without being unraveled, causing the film to break. On the other hand, 102 (NC) passed through the film processor without any problem despite heating to 80 ° C. Next, the films 101 (NC), 102 (NC), 103 (N) which have not been subjected to the heat treatment at 80 ° C.
The passage property of the processor C) was examined, but there was no problem at all.

As a result, the photographic film 102 of the present invention is obtained.
It became clear that (NC) can be used safely even under severe conditions.

[Brief description of drawings]

FIG. 1 is a perspective view showing a photographic film product and a camera having a current 135 format cartridge for explaining the present invention.

FIG. 2 is a perspective view showing a photographic film product and a camera according to the present invention.

FIG. 3 is a perspective view showing a photographic film product and a camera according to the present invention.

FIG. 4 is a perspective view showing a photographic film product and a camera according to the present invention.

FIG. 5 is a diagram showing an engagement relationship between a photographic film product and a camera according to the present invention.

FIG. 6 is a diagram showing an engagement relationship between a photographic film product and a camera according to the present invention.

FIG. 7 is a perspective view of a cartridge used in the photographic film product of the present invention.

Claims (2)

[Claims] 1. A photographic film product having a spool shaft for winding a photographic film in a roll shape, a film outlet for loading and unloading the photographic film, and a cartridge for rotatably storing the spool around an axis. one screen area of the film is 3cm ² ~7cm ^2,
And when the cartridge is loaded in the camera, the film outlet is kept in a plane including the exposure stage in the camera, and the direction of taking in and taking out the photographic film is parallel to the winding direction of the photographic film in the camera. A photographic film product having means for controlling the attitude so that the support of the photographic film is a polycarbonate base. 2. An image forming method in which the photographic film product of claim 1 is loaded into a camera, and after taking a photograph, the photographic film is developed to form a negative image, which is printed on photographic paper to obtain a positive image. An image forming method characterized in that the resolution of photographic paper is 5 lines / mm or more.