JPH04304448A - Photosensitive material for diffusion transfer - Google Patents

Abstract

PURPOSE:To provide the rolled photosensitive material which is improved in adhesiveness, does not generate pinholes and have the good transporting property to allow the use in a DTR bright room camera processor. CONSTITUTION:A matting agent is incorporated at 0.005 to 0.1g/m<2> into the replenishing liquid emulsion side of the photosensitive material for diffusion transfer having at least one layer of silver halide emulsion layers and the matting agent is incorporated at 1 to 5g/m<2> into the back layer side thereof. The rolled photosensitive material for DTR bright room camera processor which minimizes the generation of the pinholes and does not generate troubles in transportation is obtd. in this way.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material used in a diffusion transfer method, and more particularly to a roll-shaped photographic material used in a DTR bright room camera processor.

0002

[Prior Art] The silver complex diffusion transfer method (DTR method) generally consists of a photosensitive material in which a silver halide emulsion layer is formed on a support as a photosensitive layer, and an image receiving layer containing physical development nuclei is formed on the support. It consists of a processing liquid containing an image-receiving material and a silver halide solvent. The principle of the silver complex diffusion transfer method is that the silver halide in the exposed areas of the exposed photosensitive layer is developed by a processing solution or a developing agent in the photosensitive material, and at the same time, the silver halide in the unexposed areas is developed by the halogen in the processing solution. It reacts with a silver oxide solvent to form a soluble silver complex salt, which diffuses into the image-receiving material and deposits on physical development nuclei in the image-receiving layer to form a silver image. The DTR method has a wide range of possible applications. It is widely used for copying documents, such as copies of printed matter, handwritten documents, and blueprints, as well as as printing material for plate-making work, and requires image reproduction that is faithful to the original manuscript.

Incidentally, silver halide photographic materials generally use a highly hydrophilic substance such as gelatin as a binder for layer formation, and the surface thereof is extremely smooth and hygroscopic. Therefore, under high temperature and high humidity conditions, the adhesion of the layer surface increases. This increase in adhesiveness makes it easy to damage the outer surface of the photosensitive materials due to contact with each other when the photosensitive materials are wound into a roll. , electrostatic failure is likely to occur due to discharge generated during friction or peeling between the above-mentioned photosensitive materials, and it also causes various inconveniences such as difficulty in obtaining satisfactory vacuum adhesion during contact exposure.

[0004] The DTR bright room camera processor conveys the photosensitive material in close contact with a conveyor belt by drawing a vacuum from the back side of the photosensitive material. Depending on the model, the vacuum from the back is temporarily stopped on the photographic glass, the air between the photographic glass and the photosensitive material is removed, and the two are placed in close contact with each other to take the photograph. After shooting, the camera is vacuumed from the back again, brought into close contact with the conveyor belt, and sent to the processor section. As mentioned above, if the surface of the photosensitive material is smooth, it will not be able to respond smoothly to vacuum switching, and not only will it not be possible to obtain satisfactory vacuum adhesion, but it will also become clogged mid-way, resulting in poor conveyance. It will bring.

[0005] In order to improve adhesion, it is widely practiced to roughen the surface layer of a photosensitive material by using a matting agent. Therefore, by using a matting agent in the surface layer, the adhesiveness of the contact surface of the photosensitive material is reduced, and the antistatic effect and vacuum adhesion are improved. However, in a photosensitive material that uses a matting agent, if the matting agent used in the photographic emulsion layer is used in an amount sufficient to eliminate the failure caused by increased adhesion, this photosensitive material will naturally have poor sharpness. Even if the image quality is high, the sharpness will deteriorate considerably due to the matting agent used. Further, silver missing portions (referred to as pinholes) as large as the holes of a needle occur in the silver image area of the image-receiving material after diffusion transfer.

[0006] Even if this pinhole does not impair practical quality, especially in a reflective image, it becomes very noticeable when used as a transmitted image, such as with an image receiving material using a transparent film support. It becomes a number of pinholes. Japanese Patent Publication No. 63-36653 discloses that by containing a matting agent having an average particle diameter larger than the thickness of the undercoat layer, there is no slippage when the photosensitive material and image-receiving material are in close contact with each other, and pinholes can be prevented. A light-sensitive material for diffusion transfer that does not cause this phenomenon has been described. However, if a sufficient amount of matting agent is used in such an embodiment to eliminate the increased adhesion failure described above, loading the photosensitive material into a DTR light room camera processor will result in the vacuum switching described above. It turned out that it was not possible to respond smoothly. Further, the number of pinholes depends on the amount of the matting agent contained in the emulsion layer side, particularly in the emulsion layer, and it is preferable to use the smallest possible amount of the matting agent.

On the other hand, if almost no matting agent is used, poor vacuum adhesion will occur. Additionally, if a sufficient amount of matting agent is used on the back layer side of the photosensitive material to eliminate failures due to increased adhesion, it may not adhere well to the conveyor belt of the DTR bright room camera processor, causing conveyance defects. Put it away. If little matting agent is used, not only will the outer surface of the photosensitive material be damaged due to its adhesive properties on the contact surface, but as mentioned above, it will not be possible to respond smoothly to vacuum switching, and the amount of matting agent used will be limited. There were limitations and it was not possible to satisfy everything.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a roll-shaped photosensitive material with improved adhesion, no pinholes, and improved transportability for use in a DTR bright room camera processor. be.

[0009]

[Means for Solving the Problems] The above objects of the present invention are as follows:
In a light-sensitive material for diffusion transfer having at least one silver halide emulsion layer on a support, 0.005 to 0.1 g/m2 of a matting agent is contained on the photographic emulsion layer side of the light-sensitive material,
Moreover, this was achieved by a light-sensitive material for diffusion transfer, which is characterized in that the back layer side contains a matting agent of 1 to 5 g/m2. The present invention will be explained in more detail below.

In order to enable rapid formation of a silver complex salt with the aid of a silver halide solvent, the silver halide in the silver halide emulsion of the light-sensitive material of the present invention is a silver chloride salt containing 90 mol % or more of chloride. It is preferable to use silver bromide, silver chloroiodide, and silver chloroiodobromide. Silver halide emulsions can also be spectrally sensitized in blue, green, and red. It can be a merocyanine, cyanine dye or other sensitizing dye. Furthermore, the silver halide emulsion can be chemically sensitized with various sensitizers. For example, sulfur sensitizers (e.g. hypo, thiourea, gelatin containing labile sulfur, etc.), noble metal sensitizers (e.g. gold chloride, gold rhodan, ammonium chloroplatinate, silver nitrate, silver chloride, palladium salts, rhodium salts,
iridium salt, ruthenium salt, etc.), U.S. Patent Nos. 2 and 5
Polyalkylene polyamine compounds described in German Patent No. 18,698, iminoaminomethanesulfonic acid described in German Patent No. 1,020,864, reduction sensitizers (for example, stannous chloride, etc.), and the like are advantageously used.

The preferred coverage of silver halide in grams of silver nitrate per square meter ranges from 1 to 5 grams. The binder for the silver halide emulsion layer is preferably gelatin. However, instead of or in addition to gelatin, one or more other natural and/or synthetic hydrophilic colloids, such as albumin, casein, zein, polyvinyl alcohol, alginic acid or its salts, cellulose derivatives (
For example, carboxymethylcellulose, modified gelatin), etc. can also be used. The weight ratio of hydrophilic colloid to silver halide in terms of silver nitrate in the silver halide emulsion layer of the light-sensitive material is used in the range of 0.3 to 5, preferably 0.5 to 3.

In addition to the binder and silver halide,
The light-sensitive material can contain any type of commonly used compounds in the silver halide emulsion layer and/or in one or more layers in water-permeable relationship therewith. For example, mercapto compounds, antifoggants such as tetraazaindene,
or stabilizers, surfactants such as saponins, sodium alkylbenzene sulfonates, sulfosuccinic ester salts, anionic compounds such as the alkylaryl sulfonates described in U.S. Pat. No. 2,600,831 and U.S. Pat. No. 3,133, In addition to amphoteric compounds such as those described in No. 816, wetting agents such as waxes, polyol compounds, glycerides of higher fatty acids or higher alcohol esters, mordants such as N-guanyl hydrazone compounds, quaternary onium compounds, and tertiary amine compounds. , diacetyl cellulose, styrene-perfluoroalkylene sodium maleate copolymer, antistatic agents such as alkali salts of reaction products of styrene-maleic anhydride copolymer and p-aminobenzenesulfonic acid, acrylic esters, various Film property improvers such as latex, styrene-maleic acid copolymers, thickeners such as those disclosed in Japanese Patent Publication No. 36-21574, antioxidants, and developing agents can be used.

According to the present invention, the layer to which the matting agent is added may be in any layer when the photographic emulsion layer side consists of two or more layers, or may be added in divided layers. Under the silver halide emulsion layer, it is preferable to provide an undercoat layer containing a pigment such as carbon black or a dye, which also serves as an antihalation layer. In order to reduce pinholes, it is preferable to add a matting agent to the undercoat layer, but the effect of improving adhesion is weaker than when it is added to the emulsion layer. For this reason, a large amount of matting agent is used, and some of the matting agent is also found in the emulsion layer after coating and drying, so in reality, the effect of the matting agent is
It is more appropriate to consider the amount added per 2. The amount of matting agent added to the emulsion layer side is 0.005 to 0.1 g/m2. The hydrophilic binder in the subbing layer may be present in any amount, but generally ranges from about 1 to 8 g/m2. A protective layer may be provided above the silver halide emulsion layer. The amount of hydrophilic binder in the protective layer may be any amount, but generally ranges from about 0.2 to 1 g/m2.

[0014] The matting agent in the present invention is a powder of an organic or inorganic compound, and the particle size range of the powder is as follows:
Average particle diameter of about 1 to 20 μm, preferably 2 to 10 μm
That's about it. As specific examples of the matting agent, preferred organic compounds include water-dispersible vinyl polymers such as polymethyl methacrylate, cellulose acetate propionate, and starch. Preferably used inorganic compounds include silver halide, barium strontium sulfate, calcium carbonate, silicon dioxide, magnesium oxide, and titanium dioxide. In particular, matting agents of water-dispersible vinyl polymers such as homopolymers of acrylic esters, such as methyl methacrylate, glycidyl acrylate, and glycidyl methacrylate, or copolymers of these acrylic esters with other vinyl monomers are used. preferable. Particularly preferred are polymethyl methacrylate or silicon dioxide.

The silver halide emulsion layer can be hardened with a suitable hardening agent, and specific examples of the hardening agent include aldehyde compounds such as formaldehyde and glutaraldehyde, diacetyl, and cyclopentanedione. Ketone compounds, bis(2-chloroethylurea)-2-hydroxy-4,6-dichloro-1,3,5-triazine, compounds with reactive halogens such as those described in U.S. Pat. No. 3,288,775, divinyl Sulfone, U.S. Patent No. 3,
Compounds with reactive olefins as described in US Pat. No. 635,718, N as described in U.S. Pat.
- methylol compounds, isocyanates such as those described in U.S. Pat. No. 3,103,437, U.S. Pat.
No. 280, aziridine compounds as described in No. 2,983,611, carbodiimide compounds as described in U.S. Pat. No. 3,100,704, U.S. Pat. No. 3,091
, 537, halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane, inorganic hardeners such as chromium alum, potassium alum, and zirconium sulfate. Two or more types can be used in combination.

As the support for the photosensitive material used in the present invention, plastic films such as polystyrene, polycarbonate film, cellulose triacetate and polyethylene terephthalate, polyethylene laminated paper coated with polyethylene, baryta paper, etc. are used. The back layer desirably provided on the back side of the support contains a hydrophilic colloid in an amount necessary to maintain curl balance with the photosensitive layer side. The amount depends on the total amount of hydrophilic colloid on the photosensitive layer side, the amount of white inorganic pigment, etc.

The image-receiving layer of the image-receiving material used according to the invention can be coated on an opaque or transparent support, which can be one of the supports mentioned above for light-sensitive materials. As physical development nuclei, metals such as silver, gold, platinum, palladium, copper, cadmium, lead, cobalt, nickel, or their sulfides, selenides, etc. can be used. These are preferably colloidal.

The one or more layers of non-photosensitive material containing the image-receiving layer may include surfactants, matting agents, fluorescent dyes, anti-tarnish agents, toning agents, developing agents such as hydroquinone and its derivatives, 1-phenyl -3-pyrazolidone and its derivatives, etc.), silver halide solvents (eg, sodium thiosulfate, ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate, etc.). Further, a neutralizing layer and a subbing layer for improving adhesion to the support may be provided below the image-receiving layer.

The image-receiving layer can be comprised of any of the binders described above for the silver halide emulsion layer. Gelatin is the preferred binder for the image receiving layer. The image-receiving layer can also be hardened with suitable hardeners as described for photographic hydrophilic colloidal silver halide emulsion layers. A plurality of hydrophilic colloid layers can be applied in several parts, or can be applied in multiple layers simultaneously. The coating method may be any known method and is not limited.

The processing liquid used in the diffusion transfer method contains an alkaline substance such as sodium hydroxide, potassium hydroxide,
Lithium hydroxide, trisodium phosphate, etc., silver halide solvents, such as sodium thiosulfate, ammonium thiocyanate, cyclic imide compounds, thiosalicylic acid, etc., preservatives, such as sodium sulfite, thickening agents, such as hydroxyethylcellulose, carboxylic acid, etc. methylcellulose etc.
Antifoggants such as potassium bromide, 1-phenyl-5
- mercaptotetrazole, etc., developer modifiers, such as polyoxyalkylene compounds, onium compounds, developing agents,
For example, hydroquinone, 1-phenyl-3-pyrazolidone, hydroxylamine, etc. can be included.

However, in a highly alkaline processing solution containing this developing agent, the developing agent has the disadvantage that it is subject to air oxidation and becomes deactivated. This drawback can be largely avoided by incorporating it into a hydrophilic colloid layer that has a water-permeable relationship with the colloid. In diffusion transfer materials containing such a developing agent, an alkaline active liquid containing no or substantially no developing agent is usually used. Regarding the DTR method using an alkaline activated liquid, reference can be made to specifications such as Japanese Patent Publication No. 39-27568, Japanese Patent Publication No. 47-30856, and Japanese Patent Publication No. 51-43778.

[0022]

[Examples] The present invention will be explained below with reference to Examples, but the present invention is not limited in any way.

Example 1 (1) Preparation of photosensitive material An undercoat layer containing carbon black for antihalation is provided on one side of a subbed-treated polyethylene terephthalate film support. Ortho-sensitized silver chlorobromide (silver bromide 5 mol%)
is converted into silver nitrate, 1.5g/m2, and further 0.2g/m2.
m2 of 1-phenyl-3-pyrazolidone and 0.7 g/m
A gelatin silver halide emulsion layer containing 2 g/m2 of hydroquinone and 4 g/m2 gelatin was coated. The back layer was coated with the same gelatin used in the emulsion layer at a density of 5 g/m2. And as a matting agent, the average particle size is 7 μm.
of silica particles were added to each layer as shown in Table 1. The obtained photosensitive material was impregnated with a hardening agent so as not to interfere with the diffusion transfer process, wound into a roll, and heated at 40°C and 80%
It was left under RH conditions for 6 days.

(2) Formation of an image The photosensitive material produced as described above is loaded into a Mitsubishi Paper Mills Meisho DTR camera OS-7 equipped with a Mitsubishi Paper Mills one-step activator OS-ACII (processing liquid), Mitsubishi Paper Mills One Step OS-PC100 (
Diffusion transfer processing was performed using a receiver film). Pinholes were evaluated by the number of pinholes in a 10 cm x 10 cm area, and conveyance performance was evaluated by the number of troubles when passing through 10 sets of 10 x 12 inches.

[0025]

[Table 1]

Example 2 In place of the silica particles of Example 1, a matting agent of polymethyl methacrylate having an average particle diameter of 4 μm was added to each layer as shown in Table 2.

[0027]

[Table 2]

[0028]

Effects of the Invention As is clear from the examples, sample No. 1 of the present invention. 3, 4, 9, 13, 15, 16, 19, 2
Sample No. 2 had fewer pinholes and no transportation problems, but sample No. 2 of the comparative example had few pinholes and no transportation troubles. 6, 10, 11, 12, 17, 2
Samples No. 0, 21, and 23 have many pinholes (more than 50), and sample Nos. Items 1, 2, 5, 7, 8, 14, and 18 had particularly many transportation problems. Furthermore, in the sample according to the present invention, good results were obtained regarding adhesiveness and vacuum adhesion.

Claims (1)

[Claims] Claim 1: In a light-sensitive material for diffusion transfer having at least one silver halide emulsion layer on a support, a matting agent of 0.005 to 0.1 is applied to the photographic emulsion layer side of the light-sensitive material.
g/m2 and a matting agent on the back layer side.
The above-mentioned photosensitive material, characterized in that it contains 5 g/m2.