JPH0473640A - Silver halide photographic sensitive material which allows discrimination of front and rear - Google Patents

Abstract

PURPOSE:To allow the easy discrimination of the front and rear of the photosensitive material by setting the matte degree on the side of this material where photosensitive silver halide emulsion layers are provided at the value lower than the matte degree on the side opposite therefrom and specifying the difference therebetween. CONSTITUTION:The matte degree of the photosensitive material on the side A where the photosensitive silver halide emulsion layers are provided is the value lower than the matte degree on the side B opposite therefrom and the difference therebetween is specified to >=50mmHg. Namely, the matte degree of the surface A is lower than the matte degree of the surface B and the difference therebetween may be >=50mmHg and more preferably there is >=60mmHg. The matte degree of the surface A is more particularly preferably 20 to 60mmHg and the matte degree of the surface B is more particularly preferably 150 to 230mmHg. The discrimination of the front and rear is facilitated in this way and the erroneous loading to a cassette is eliminated.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a silver halide photographic material.

More specifically, the present invention relates to a silver halide photographic material having a light-sensitive silver halide emulsion layer on one side of a support and non-light-sensitive on the other side.

[Background of the invention]

In order to obtain high sensitivity and high density, photographic materials are known in which light-sensitive emulsion layers are formed on both sides of a support, but such materials have a problem of poor image sharpness. One reason for this is that even if an attempt is made to expose only the emulsion layer on one side of the support, the light (crossover light) that passes through the support also exposes the emulsion layer on the opposite side. This has long been known as the crossover effect. Crossover effects significantly reduce sharpness.

Examples of photographic materials having light-sensitive emulsion layers on both sides of the support include radiation-sensitive materials, particularly direct X-ray-sensitive materials.

In recent years, the pursuit of improved sharpness has been intense, and in particular, for direct imaging of breasts, ear bones, etc. that require high sharpness, or for tomography, it is necessary to form a photosensitive emulsion layer only on one side of the support. Photosensitive materials (hereinafter also referred to as "single-sided photosensitive materials") have come to be used.

In single-sided light-sensitive materials, the silver halide emulsion layer is coated only on one side of the support, so for X-ray light-sensitive materials, the fluorescent intensifying screen (the emulsion layer is exposed to light by the light emitted from the fluorescent intensifying screen) is also coated on one side. It is used only on the side of Therefore, only one intensifying screen is required.

By the way, when using a single-sided photosensitive material using a fluorescent intensifying screen like this, the film is generally loaded into a cassette in a darkroom, but in this case, the light-emitting surface of the film of the photosensitive material and the intensifying screen are It must be in proper contact with the surface. That is, there is a need to distinguish between front and back sides.

For this reason, in conventional devices of this type, a notch is generally provided at a specific location in the photosensitive material to distinguish between front and back sides. However, the shape and position of the notch vary depending on the type of photosensitive material (film) and the manufacturer, and it is not always easy to distinguish them in a dark room.

Therefore, this may lead to incorrect loading during darkroom loading, which may lead to serious mistakes.

[Object of the Invention] The present invention solves the above-mentioned problems and provides a silver halide light-sensitive material that is a single-sided photosensitive material with good image sharpness, that allows easy discrimination between front and back sides, and eliminates incorrect loading into a cassette. The purpose is to provide photographic materials.

[Structure of the invention]

The above object of the present invention is to provide a photographic material having at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive layer on one side of a support, and having a fluorescent intensifying screen. A silver halide photographic light-sensitive material that is loaded into a cassette and photographed, in which the matte grain on the side having the light-sensitive silver halide emulsion layer of the light-sensitive material has a lower value than the matte grain on the opposite side. This was achieved using a silver halide photographic material characterized in that the difference is 50 anHg or more.

The present inventor has conducted intensive research to solve the above-mentioned problems, and has developed a method for determining the front and back sides of a photosensitive material having a photosensitive emulsion layer on one side of the support by varying the matteness of both sides of the photosensitive material. The present invention has been completed based on the discovery that a photosensitive material that meets the purpose of the present invention can be obtained by setting the difference in matte ratio between the two sides as described above. This is what I did.

The present invention will be explained in more detail below.

The silver halide photographic material of the present invention has at least one light-sensitive silver halide emulsion layer on one side of the support,
It has at least one non-photosensitive layer. The other side of the support may for example have a backing layer. here"
The term "backing layer" refers to a non-photosensitive hydrophilic colloid layer formed on the side opposite to the side having the photosensitive silver halide emulsion layer. The backing layer may be one layer, or two layers (top and bottom).
It may consist of layers, or even more layers. (In this specification, "lower" means the side closer to the support, "upper"
means the side farthest from the support).

The side having the photosensitive silver halide emulsion layer preferably has at least one surface protective layer as a non-photosensitive layer.

In the silver halide photographic light-sensitive material of the present invention, the matte surface on the side on which the light-sensitive silver halide emulsion layer is coated (hereinafter this side may be referred to as "Side A") is the opposite. This value is lower than that of the matte side (hereinafter this side may be referred to as "Side B" as appropriate). Like this A
By making the matte texture of the surface and B side different, the physical properties of the seeds on each side, such as the surface roughness of each side and the reflectance of light, become different, making it easy to distinguish between the two sides. become.

In the present invention, matteness refers to the roughness of the film surface, and can be measured as follows.

That is, in this specification, mat farming means a temperature of 23°C.
The suction pressure of an unexposed photosensitive material (so-called raw film) that has been conditioned for 4 hours at a humidity of 48% RH is measured under the same conditions, and is expressed in mmHg. The larger this value is, the higher the matte degree is. In the Examples described later, a Smoostar (manufactured by Toei Electronics Co., Ltd.) was used to measure the suction pressure.

Usually, a matting agent is used to impart a matte degree to a photosensitive material. Matting agents are generally fine particles of water-insoluble organic or inorganic compounds. Any matting agent can be used, such as those well known in the art. For example, as an organic matting agent, U.S. Patent No. L 939213, U.S. Pat. Those described in various specifications such as No. 448 can be used.

As inorganic matting agents, No. 1260.772, No. 2
No. 192, 241, No. 3,257,206, No. 3, 3
No. 70.951, No. 3,523,022, No. 3.76
Those described in various specifications such as No. 9.020 can be used.

For example, specifically, examples of organic compounds that can be used as matting agents include polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, acrylonitrile-α-
Examples of cellulose derivatives include methylcellulose, polystyrene, styrene-divinylhenzene copolymer, polyvinyl acetate, polyethylene carbonate, polytetrafluoroethylene, etc.
Ethyl cellulose, cellulose acetate, cellulose acetate propionate, and other starch derivatives such as carboxy starch, carboxy nitrophenyl starch, urea-formaldehyde-starch reactants, etc. Gelatin and coacervate hardened with known hardening agents to form hollow microcapsules. Hardened gelatin in the form of granules can be preferably used. Examples of inorganic compounds include silicon dioxide, titanium dioxide, mag7sium dioxide, aluminum oxide,
Barium sulfate, calcium carbonate, silver chloride desensitized by a known method, silver bromide, glass, diatomaceous earth, and the like can be preferably used.

The above-mentioned matting agents can be used by mixing different types of substances as necessary.

There are no particular limitations on the size or shape of the matting agent, and matting agents of any particle size can be used. When carrying out the present invention, it is preferable to use particles with a particle size of 0.1 μm to 15 μm.

The particle size distribution of the matting agent used may be narrow or broad, and may be monodisperse or polydisperse. Here, the monodisperse matting agent refers to one in which the number of particles having a particle diameter within ±20% of the average particle diameter is 90% or more of the total number of particles.

In the present invention, the matte degree of the A side is lower than the matte degree of the B side, and the difference between them is preferably 50 Hg or more, but the difference is 55 mm.
It is preferable that there is a difference of Hg or more, and it is more preferable that there is a difference of 60 mmHg or more. Specifically, each surface can have the following matte degree.

That is, the matte ratio of side A is preferably 10 to 90 plate lag, more preferably 15 to 7 Q wn Hg, and particularly preferably 20 to 5 Q mm Hg.

Further, the matte resistance of side B is preferably 100 to 300 mmHg, more preferably 120 to 250 mmHg, and particularly preferably 150 to 230 mmHg.

However, the values of the degree of matting of the above-mentioned sides A and B may be adjusted as appropriate depending on the particle size (type) and amount of the matting agent used.

In the present invention, the matting agent is preferably contained in the outermost surface layer of the photosensitive material, a layer that functions as the outermost surface layer, or a layer close to the outer surface, and is also contained in a layer that functions as a so-called protective layer. Preferably. That is, on the A side, it is preferably contained in the protective layer, which is a non-photosensitive layer, and on the B side, it is preferably contained in the banking layer, and when there are two or more banking layers, the surface side ( It is preferably contained in the layer on the upper layer side).

The content of the matting agent is determined so that the difference in matte degree between sides A and B is within the range of the present invention, and it is preferably contained so that each side has the above-mentioned preferred matte degree.

Further, two or more layers may contain the same type of matting agent or different types of matting agents, in which case the layer to which the matting agent is added may be an emulsion layer, a protective layer, or an undercoat layer provided as necessary, or an intermediate layer. Any layer may be used.

The light-sensitive material of the present invention has a side (A) having a light-sensitive emulsion layer.
A mordant layer may be provided on the surface side).

Thereby, sharpness can be further improved.

Further, the photosensitive material of the present invention preferably contains a dye on the B side. Any dye may be used as appropriate depending on the photosensitivity of the photosensitive material, and there are no particular restrictions on the type of dye.

The silver halide grains used in the light-sensitive silver halide emulsion layer to constitute the light-sensitive material of the present invention are not particularly limited.
Optional. Tabular grains are also preferably used.

That is, any silver halide used in ordinary silver halide emulsions, such as silver bromide, silver iodobromide, silver chlorobromide, and silver chloride, can be used as appropriate. Preferably, silver iodobromide is used.

The crystal habit and grain size of the silver halide grains are also not limited and are arbitrary.

The silver halide emulsion used may be spectrally sensitized.

For example, ortho sensitization, panchromatic sensitization, and even infrared spectral sensitization can be performed.

Any silver halide photographic emulsion can be used, such as a polydisperse emulsion with a wide grain size distribution or a monodisperse emulsion with a narrow grain size distribution. There may be. Monodispersed emulsions can be preferably used.

Examples of the binder (binding agent, protective colloid) used in the photosensitive silver halide emulsion layer, non-photosensitive layer such as a protective layer, and other hydrophilic colloid layers of the photographic material of the present invention include coal-treated gelatin, acid It is preferable to use gelatin such as treated gelatin, derivative gelatin, or gelatin graft polymer.

Other hydrophilic colloids such as hydroxyethyl cellulose, polyvinyl alcohol, and polyvinylimidazole can also be used.

In the light-sensitive material of the present invention, the support on which the emulsion layer and other layers are coated is preferably a flexible support commonly used for light-sensitive materials (polyethylene terephthalate, cellulose triacetate, paper, etc.). . Useful as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta paper or alpha-olefin polymers. (For example, paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer), etc.

The support may be colored using dyes or pigments.

It may be made black for the purpose of blocking light. The surface of these supports may be subjected to a subbing treatment to improve adhesion with emulsion layers and the like. The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

The photosensitive material of the present invention may contain other optional additives (these are listed in Research Disclosure 1).
Volume 76, Nα17643 (December 1978) and 1
It is described in Volume 87, Nα18716 (November 1976), and the relevant parts are summarized in the table below.

Known photographic additives that can be used in preparing the emulsion of the light-sensitive material of the present invention are also described in the above two Research Disclosures, and the descriptions are shown in the following table.

The photosensitive material of the present invention can be used, for example, for printing, for X-ray, -t
It can be embodied as various photosensitive materials such as C negative, general standard, general positive, and direct positive.

The light-sensitive material of the present invention can be suitably applied to an X-ray photographic light-sensitive material. In that case, viewed from the direction of X-ray irradiation,
It can be suitably embodied as a silver halide photographic light-sensitive material for X-ray photography, which is exposed by a cassette having a sheet of fluorescence-enhancing paper on its front surface.

That is, what is illustrated in FIG.
In such a case, as shown in FIG. 2, the intensifying screen 2 is set so that its light-emitting surface 20 faces the back cover side. . Thereby, the above-mentioned preferable configuration can be achieved. In addition, in Figure 2,
21 is a support for the fluorescent intensifying screen, 22 is a phosphor layer, and 23 is a surface protective layer.

The photosensitive material of the present invention is preferably developed under the conditions represented by the following formula (I).

2 (I) 1°'7s
, and T is the time required to pass through 2 (unit: 2 seconds)
represents.

Further, it is preferable to perform the processing using a roller conveyance type automatic developing machine under conditions corresponding to the following.

Formula (I) %Formula % However, l is the 10th point of the insertion opening of the roller conveyance type automatic developing machine.
It is the length (unit: m) from the core of the roller to the core of the final roller at the drying outlet, and T is the time (unit: 2 seconds) used to pass through the above p.

The above i can be determined, for example, based on a photosensitive material having a photographic constituent layer on a polyethylene terephthalate support having a thickness of 175 μm.

When using an automatic processor, insert the leading edge of the film into the core of the 10th roller in the insertion slot, then proceed to the developing tank, transfer section, fixing tank, transfer section, washing tank, transfer section, etc. The total time it takes for the film to pass through the drying section and the drying section until the leading edge of the film emerges from the final roller at the drying outlet [In other words, the total length of the processing line (m) is expressed as the line conveyance speed (m/s
It can be said to be the quotient (sec, ) divided by ec, ).

The reason why the time for the transition part should be included here is that it is well known in the industry that even in the transition part, the liquid from the previous process swells in the film of gelatin, etc. This is because it can be considered that the treatment process is progressing.

The total number of transport rollers in the automatic processor used in the processing method of the present invention is such that the value obtained by dividing i, which is the processing section of the automatic processor, by the number of rollers is in the range of 0.01 to 0.04. is preferred. Further, it is preferable that the time for each treatment site is as follows.

Further, the time for each treatment site is preferably within the following range.

Inserter development 10-cross fixing + cross-water washing + cross-squeeze drying 25-40% 1゛2-25% 10-25% 25-45% The rollers used have a conveyor diameter of 12 mm to 60 mm.
The length is preferably between 30CI11 and 110CI11, and various materials can be used. For example, Bakelite-based (which may contain glass powder, metal powder, and plastic powder) is used in the developing, fixing, washing, and drying parts. Rubber-based materials (neobrene, isoprene, silicone rubber, etc.) can be used. The transition part and squeeze part are made of water-repellent and elastic silicone rubber, etc., and highly water-absorbing synthetic leather called "Talalino" (manufactured by Kuraray ■).
It is preferable to use

Preferably in the present invention, l exceeds 0.7 and 4
．． The range is less than 0, which gives preferable results. ! When is smaller than 0.7, each processing step becomes smaller and the number of rollers used becomes smaller, resulting in decreased sensitivity and poor conveyance. On the other hand, if l is larger than 4.0, the transport speed becomes too high, the film is likely to be scratched, and the durability of the automatic developing machine is deteriorated.

If the product of 2°·75 and T is less than 50, the sensitivity of the processed film will decrease, and in films where 100 mg/rrr or more of sensitizing dye is used per side of the support, color retention may occur. It becomes a problem. This problem was discovered through study by the present inventor. Preferably I! 0.7S
The product of T and T is 76 or more.

EMBODIMENT OF THE INVENTION Hereinafter, examples of the present invention will be described in detail. It should be noted that, as a matter of course, the present invention is not limited to the examples described below.

Example-1 On one side (the side that becomes side A) of a 175 μm thick polyethylene terephthalate film support that has been undercoated,
A high-sensitivity silver iodobromide emulsion for direct X-rays containing 2.3 mol% of silver iodide and a protective layer coating liquid are coated on the upper layer, and a banking upper layer liquid is further applied on the opposite side (the side that becomes side B). and a backing lower layer liquid were applied to produce a silver halide photographic window optical material according to the present invention having a photogenic silver halide emulsion layer and its upper protective layer on the A side, and a backing lower layer and an upper layer on the B side. . However, silicon dioxide fine particles with an average particle size of 1.5 μm were added to the protective layer as a matte layer, and polymethyl methacrylate fine particles with an average particle size of 4.3 μm were added to the banking upper layer.

The amount of each added was adjusted so that the matte agricultural value would be the value shown in Table-1.

The obtained photosensitive material was 1iff 125.4 cm, width 30.
It was processed into a size of 5 cm to obtain a film sample for single-sided direct X-ray photography according to the present invention.

The additives used in the emulsion layer, the protective layer, the upper and lower backing layers, and the coating liquid compositions for forming each layer were as shown below.

(Emulsion Additive) The following compound was used as an additive to the photosensitive silver halide emulsion layer. That is, 40011 g of t-butyl-catechol and 3 g of 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene per mole of silver halide.

Polyvinylpyrrolidone (molecular weight 10.000) 1.0
g, styrene/maleic anhydride copolymer 2.5 g, trimethylolpropane 10 g, diethylene glycol 5 g, nitrophenyl-triphenylphosphonium chloride 50 mg, ammonium 1,3-dihydroxybenzene-4-sulfonate 4 g.

An emulsion layer coating solution was prepared by adding 15 mg of sodium 2-mercabutohentzimidazole-5-sulfonate, 10 mg of H 1,1-dimethylol-1-from-1-nitromethane, and the like.

(Protective layer additive) The following compound was added as a protective layer additive to prepare a protective layer coating solution. That is, 3 mg of C, F, SO, and K per 1 g of gelatin.

CJ+, 0(CHzCHzO+]CHzC)IzOH5
11g, sodium chloride 3mg, formalin 20mg.

Glyoxal 30mg, silicon dioxide fine particles with an average particle size of 1.5μm (matting agent)
The amount to give the matte degree shown in Table 1 was added.

Margin below co2COO(CHz)9CH) C) ICOO(CH2)zCH(CH,)z7mg, OJa (backing layer) In addition, the coating liquid that requires backing is was used.

(Backing lower layer coating solution) The following (Banking upper layer coating solution) Backing dye A o3Na Backing dye B Below margins Also, as a cassette for the film, a fluorescent intensifying screen was placed only on the front side (X-ray irradiation side). (See Figures 1 and 2).

Each of the film samples was loaded into the cassette thus obtained in a dark room, and then the tube voltage was 90 kvp and the tube current was 120 kvp.
After photographing a chest fan dome (manufactured by Kyoto Kagaku) under mA conditions, XD-3
Development processing was performed using R and XF-SR processing solutions (both manufactured by Konica ■). The shooting was repeated 30 times for each film.

For each of the 30 samples thus obtained, the number of correctly photographed images was counted and shown in Table 1. (There was a problem when a sample was loaded into a cassette with the front and back sides mixed up and no image was produced.) As is clear from the margin table-1 below, the sample according to the present invention has a matte texture on sides A and B. By making them different within the scope of the present invention, it is easy to distinguish between the front and back sides without making any mistakes.

It can be seen that the photosensitive material film can be loaded into the cassette by ensuring that the light-sensitive surface of the film and the light-emitting surface of the intensifying screen are aligned.

Further, when the sample according to the present invention was processed as follows after the above exposure, a good image was obtained.

Developer: XD-3R (development temperature = 35°C)
Fixer: XF-3R (Fixer temperature: 35°C) Processing time: 45 seconds Automatic developer used: 5RX-501 (Developer, fixer, and automatic developer are all manufactured by Konica ■) The above conditions were as follows. T in formula (I) = 45 (seconds), l-2
, 72(m).

〔Effect of the invention〕

As mentioned above, the silver halide photographic light-sensitive material of the present invention maintains effects such as good sharpness as a single-sided light-sensitive material, and also makes it easy to distinguish between front and back sides, and eliminates the risk of incorrect loading into a cassette. It is.

[Brief Description of the Drawings] Figure 1 is a configuration diagram showing an example of a cassette.
1(a) is a top view, and FIG. 1(b) is a side view. FIG. 2 is an explanatory diagram showing the setting of a fluorescent screen in a cassette. 1... Back cover of the case, 2... Fluorescent intensifying screen.

Claims (1)

[Claims] 1. A photographic device having at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive layer on one side of a support, and having a fluorescent intensifying screen. A silver halide photographic light-sensitive material which is loaded into a commercial cassette and photographed, wherein the matte degree on the side having a light-sensitive silver halide emulsion layer of the light-sensitive material is lower than the matte degree on the opposite side. A silver halide photographic material characterized in that the difference between the two is 50 mmHg or more. 2. The light-sensitive material is an X-ray photographic light-sensitive material, and is exposed by a cassette having one fluorescent intensifying screen on the front surface when viewed from the direction of X-ray irradiation. silver halide photographic material. 3. The silver halide photographic material according to claim 1 or 2, which is developed under the conditions represented by the following formula (I). Formula (I) l^0^. ^7^5×T=50~150 (0.7<l<
4.0) However, l is the processing length when processing the photosensitive material (unit: m)
, and T is the time required to pass l (unit: seconds)
It is. 4. The silver halide photographic material according to claim 1 or 2, which is processed in a roller conveyance type automatic processor under the conditions represented by the following formula (I). Formula (I) l^0^. ^7^5×T=50~150 (0.7<l<
4.0) However, l is the length (unit: m) from the first roller at the insertion opening of the roller type automatic processor to the exit roller, and T is the time required to pass through l (unit: seconds). be.