JPS6095431A - Photosensitive material for diffusion transfer - Google Patents

Abstract

PURPOSE:To prevent a shift of an image and the piercing of pinholes by incorporating fine particles having a smaller average particle size than the thickness of a silver halide emulsion layer into the emulsion layer formed on a support. CONSTITUTION:A silver halide emulsion layer is formed on a support of synthetic paper, cellulose acetate or the like, and fine particles of silica, polystyrene or the like having a smaller average particle size than the thickness of the emulsion layer are incorporated into the emulsion layer to obtain a photosensitive material for diffusion transfer. The photosensitive material is imagewise exposed, the emulsion surface of the photosensitive material is brought into contact with the image receiving surface of an image receiving material, and the materials are introduced into a developing device contg. a developer to carry out development. At this time, the slipping of the materials from each other can be prevented, so a shift of an image is prevented, and no pinholes are pierced.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a diffusion transfer method, and particularly to a silver halide photographic material used therein.

The principle of the silver complex diffusion transfer method (DTR method) is described in US Pat. No. 2,352,014 and is well known.

In the DTR process, silver complex salts are imagewise transferred by diffusion from the silver halide emulsion layer to the receiver, where they are converted into a silver image, often in the presence of physical development nuclei.

For this purpose, an imagewise exposed silver halide emulsion layer is placed or brought into contact with an image-receiving layer in the presence of a developing agent and a silver halide complexing agent;
The unexposed silver halide is exchanged for a soluble silver complex.

In the exposed portions of the silver halide emulsion layer, the silver halide is developed into silver (chemical development) so that it can no longer be dissolved and therefore cannot be diffused.

In the unexposed portions of the silver halide emulsion layer, the silver halide is converted to soluble silver complex salts, which are transferred to the image-receiving layer where they form a silver image, usually in the presence of development nuclei.

In a direct positive silver halide emulsion, the effects of silver halide in exposed and unexposed areas are reversed.

In such a silver complex diffusion transfer method, the quality of the image-receiving material finally obtained, such as image density, image tone, image contrast, and storage stability of the obtained copy, are important. Depending on the application, continuous-tone original images may be reproduced on image-receiving materials, but higher contrast, sharpness, and resolution are required for reproduction of documents, printed matter, etc., or for use as base material for plate making. do.

However, no matter how well-designed the photosensitive material, image-receiving material, and processing solution are used to obtain excellent images, the film surfaces of the photosensitive material and image-receiving material overlap and come into close contact with each other, and during development, they are If slippage occurs between the materials, it is no longer possible to obtain high-quality images.

It is easy to think that this slippage 9 between materials is caused by the adhesiveness of the film surface, and when the developer contains a thickening agent such as carboxymethyl cellulose or hydroxyethyl cellulose, this slippage occurs. engineering becomes noticeable.

In order to prevent adhesion and adhesion of such photosensitive materials, and further to prevent static electricity, it is widely practiced to roughen the surface layer of photosensitive materials by using a matting agent. Therefore, by using a matting agent on the surface, it is possible to prevent the above-mentioned slipping between the two materials that are in close contact with each other. By the way, the present inventors discovered that silver missing areas (called pinholes) as large as the holes of a needle exist in the silver image area formed on the image-receiving material. However, it was confirmed that when used as a transmitted image, such as with an image-receiving material using a transparent film support, a very noticeable number of pinholes were formed.

The pinholes are considered to be due to the fact that the diffusion of the silver complex from the photosensitive material is locally blocked and does not reach the image-receiving layer. Although the causes of pinholes cannot be fully elucidated, the inventors have discovered one of them.
It has been found that one of the major causes is the use of a matting agent in the surface layer of the photosensitive material as described above.

Therefore, there is no slippage when the photosensitive material and image-receiving material are in close contact with each other.
It has been desired to develop a light-sensitive material for diffusion transfer that does not generate pinhole sounds.9 It is an object of the present invention to provide all such light-sensitive materials.

The above-mentioned object of the present invention is to provide a light-sensitive material for diffusion transfer having at least a silver halide emulsion layer on a support, in which an average grain size not exceeding the layer thickness is formed in the emulsion layer. This was achieved by the photosensitive material described above, which is characterized in that it contains fine particles having the following properties.

The present invention will be explained in more detail below.

A general light-sensitive material for silver complex diffusion transfer is composed of at least one silver halide emulsion layer provided on a support, and the silver halide in terms of silver nitrate is generally 0.5y-
5f/n? It is applied within the range of It is also known that, in addition to this silver halide emulsion layer, auxiliary layers such as an undercoat layer, an intermediate layer, a protective layer, and a release layer, as well as a backing layer, may be provided as necessary.

Further, the photosensitive material of the present invention can be used, for example, in Japanese Patent Publication No. 38-181
34, No. 38-18135, etc., such as methyl cellulose, sodium salt of carboxymethyl cellulose, sodium alginate, etc., can be used as a coating layer for the silver halide emulsion layer to ensure uniform transfer. The layer can be thin so that it does not substantially prevent or inhibit diffusion.

Hydrophilic binders that are advantageously used to prepare a light-sensitive emulsion in the silver halide photographic light-sensitive material of the present invention include lime-treated gelatin, acid-treated gelatin, and gelatin derivatives (for example, Japanese Patent Publication No. 38-4854, Japanese Patent Publication No. 38-4854, 5514
No. 40-12237, No. 26345-1973, U.S. Patent No. 2,525,753, U.S. Patent No. 2,594,
No. 293, No. 2.614,928, No. 2,763
, No. 639, No. 3.118,766, No. 3,13.
No. 2,945, No. 3.186,846, No. 3.3
12,553, British Patent No. 861,414, British Patent No. 1
, gelatin derivatives described in , 033, 189, etc.), proteins such as albumin and casein, cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose, agar, natural polymers such as sodium alginate, yt'lJ hinyl alcohol, poly-N- Synthetic hydrophilic binders such as vinyl pyrrolidone, polyacrylic acid copolymers, polyacrylamide, derivatives thereof, and partially hydrolyzed products can be used, and these hydrophilic binders can be used alone or in combination.

These hydrophilic binders are also advantageously used to form non-photosensitive layers such as subbing layers or image-receiving layers.

The amount of binder in the silver halide emulsion layer is desirably at most 2.5 parts by weight, preferably up to 1.5 parts by weight, based on silver halide calculated as silver nitrate.

The silver halide may be any one of silver chloride, silver bromide, silver chlorobromide, or a combination thereof with silver iodide.

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, such as sulfur sensitizers (e.g. hypo, thiourea, labile sulfur-containing gelatin, etc.), noble metal sensitizers (e.g. gold chloride, gold rhodan, ammonium chloroplatinate, silver nitrate, silver chloride, palladium salts, rhodium salts, iridium salts, rutinium salts, etc.), U.S. Patent No. 2,51
8,698, imino-amino-methanesulfinic acid described in German Patent No. 1,020,864, reduction sensitizers (for example, stannous chloride, etc.), etc. are advantageously used. used.

Underneath the silver halide emulsion j-, it is preferable to provide an undercoat containing a pigment or dye such as carbon black, which also serves as a nolation prevention layer.

The hydrophilic binder in the subbing layer can be in any amount, but generally from about 1 to about 8 f/rr? is within the range of

The light-sensitive material for diffusion transfer of the present invention comprises a norogen recording emulsion j
- Contains fine particles whose average particle diameter does not exceed the binder thickness of the emulsion layer. Such fine particles can be selected from materials conventionally known to those skilled in the art as matting agents.

According to the usual method of use as a matting agent, it is common to include all fine particles in the surface layer with an average particle diameter larger than the layer thickness (for example, Japanese Patent Application Laid-Open No. 53-11614
No. 3, Publication No. 57-104133, etc.). However, it has been found that such a method of use, although matting the surface layer, causes pinholes when diffusion transfer development is performed in close contact with an image-receiving material.

The fine particles used in the present invention have an average particle diameter that does not exceed the thickness of the binder in the emulsion layer, and generally has a diameter of 0.
．． 1 μm to 6 μm, preferably about 0.5 μm to 4 μm, and 0.2 to 1 μm of the emulsion layer binder thickness.
．． It is desirable to use particles with an average particle diameter of about 0 times, preferably about 0.4 to 0.9 times.

The amount of fine particles contained in the emulsion layer is about 0.1 to 30% by weight, preferably 0.2 to 10% by weight based on the hydrophilic binder.
It is about the weight level.

The fine particles can be arbitrarily selected from known particles as described in the above patents, as long as they have a particle size that corresponds to the thickness of the emulsion layer, such as silica, titanium dioxide, magnesium oxide, barium sulfate, etc. , calcium carbonate,
Inorganic or organic powder substances such as polystyrene, alkyl-substituted polystyrene, and (meth)acrylic acid esters are known as typical examples.

When an undercoat layer is provided, the undercoat layer may further contain all of the fine particles.

Preferable fine particles have an average particle diameter larger than the binder thickness of the undercoat layer.

The constituent elements of the silver halide photographic material of the present invention may further contain various additives.

For example, hardeners such as formalin, mucochloric acid, chromium alum, vinyl sulfone compounds, epoxy compounds, and ethyleneimine compounds; anti-capri agents or stabilizers such as mercapto compounds and tetraazaindene; saponins as surfactants; Sodium alkylbenzene sulfonate, sulfosuccinate salt, U.S. Patent No. 2,600,
831 and amphoteric compounds such as those described in U.S. Pat. No. 3,133,816.
Fluorescent brighteners such as No. 7127, waxes, wetting agents such as glycerides of higher fatty acids or higher alcohol esters, mordants such as N-guanylhydrazone compounds, quaternary onium compounds, tertiary amine compounds, diacetyl cellulose, styrene, etc. Antistatic agents such as perfluoroalkylene sodium maleate copolymers, alkali salts of reaction products of styrene-maleic anhydride copolymers and P-aminobenzenesulfonic acid, film property improvers such as various latexes, glycerin , gelatin plasticizers such as those disclosed in Japanese Patent Publication No. 43-4939, styrene-maleic acid copolymers, thickeners such as those disclosed in Japanese Patent Publication No. 36-21574, antioxidants, P
H regulators etc. can be used.

Supports used in the practice of the present invention include plastic films and laminated films thereof such as cellulose acetate, cellulose acetate butyrate, polyethylene terephthalate, polystyrene, and polypropylene, synthetic paper,
Examples include baryta paper, paper laminated with a plastic film such as a-olefin polymer such as polyethylene, etc., and may contain a coloring agent to prevent halation.

The processing liquid used in the diffusion transfer method contains an alkaline substance such as sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium phosphate, etc., a silver halide solvent such as sodium thiosulfate, ammonium thiothianate, a cyclic imide compound, Preservatives such as thiosalicylic acid, such as sodium sulfite, thickening agents such as hydroxyethyl cellulose, carboxymethyl cellulose, anti-fogging]E
development agents such as potassium bromide, 1-phenyl-5-mercaptotetrazole, etc.; developer modifiers such as polyoxyalkylene compounds, onium compounds; developing agents such as hydroquinone, 1-phenyl-3-pyrazolidone, etc.; May contain metal.

However, in a highly alkaline processing solution containing this developing agent, the developing agent has the disadvantage of being subject to air oxidation and becoming ineffective.
Therefore, it is known that this drawback can be largely avoided by incorporating a developing agent into the DTR material, ie into the silver halide emulsion layer and/or into the hydrophilic colloid layer which has a water-permeable relationship therewith.

In diffusion transfer materials containing such a developing agent, an alkaline active liquid containing no or substantially no developing agent is usually used.

The DTR method using an alkaline activating solution was published in Japanese Patent Publication No. 39-2
7568, 1977-30856, 1977-4377
8 etc. can be referred to in their entirety.

Next, in order to explain the present invention more specifically, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto, and various applications can be made within the scope of the claims.

Example 1 An image-receiving layer consisting of gelatin containing nickel sulfide cores and carboxymethyl cellulose (4:1) was provided on one side of a subbed-treated polyethylene terephthalate film support so that the total dry weight of hydrophilic colloid was 3 tons or more. An image receiving material was prepared.

On the other hand, on a polyethylene-coated paper support, there was a gold undercoat layer containing carbon black and gold for antihalation, and silver chlorobromide (5 molt of silver bromide) with an average particle size of 0.3μ was coated on top of this. Ortho-sensitized containing 3.0 f/- in terms of silver nitrate, and 0.21/d of 1-phenyl-4-methyl-
A photosensitive material (blank sample)' was prepared by providing a gelatin silver halide emulsion layer containing pyrazolidone and 0.7 v/- of hydroquinone. This blank sample contains 4 f/d gelatin in the undercoat layer and 3.0 f/m" gelatin in the emulsion layer. After exposing the photosensitive material gold image, the emulsion side of this photosensitive material and the image receiving surface of the image receiving material were brought into contact with each other, passed through a conventional developing machine containing a developer for silver complex diffusion transfer having the composition shown below, and both materials were peeled off within 15 seconds after exiting the squeezing roller.

A silver image with a high transmission density was obtained with respect to the image receiving layer pressure, but among the 30 sheets that were continuously processed, the images on 6 sheets were distorted due to slippage between the two materials.

On the other hand, a similar test was conducted using a comparative sample prepared in exactly the same manner as the blank sample, except that the silver halide emulsion layer contained 111-5% by weight (75q/rr?) of silica particles with an average grain size of 7 μm. Although none of the materials had image misalignment, many pinholes were found in the image areas of all the image receiving materials.

(Approximately 500 pinholes were present in the sample width of 10 crn x 10 crn.) Furthermore, 75 μm of silica particles with an average particle size of 2 μm were added to the emulsion layer.
~ (invention sample A), 15011Vz rent (invention sample B)
) When two types of samples A and B were prepared in the same manner as the blank sample except that the content was contained in a ratio of There was none.

Also, there are 3 pinholes in a 10 cm x 10 cm sample.
It was within 0.

Example 2 The silica particles used in Emulsion 1- of the inventive sample of Example 1 were coated with 20 my/- 100 q/m'', and each undercoat layer was coated with silica particles with an average particle diameter of 7 μm at 100 my/min.
n? When two types of samples were tested, Example 1
Similar to the sample of the present invention, there was no image shift and there were very few pinholes.

Example 3 In place of the silica particles in the emulsion layer of Example 1, an average particle size of 2
．． 5 μm silica particles, polystyrene or methyl methacrylate microparticles were used.

Similar results were obtained.

Claims (1)

[Claims] (1) In a light-sensitive material for diffusion transfer having at least a silver halide emulsion layer on a support, the emulsion layer contains fine particles having an average grain size not exceeding the layer thickness. A photosensitive material for diffusion transfer characterized by: