JP2786515B2 - Silver complex diffusion transfer reversal method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (A) Field of Industrial Application Silver salt diffusion reversibility (hereinafter abbreviated as DTR method) is widely used in photography and plate making printing. The present invention relates to a DTR method for a non-printing plate, and more particularly to improvement in density and color tone of a positive image formed in an image receiving layer. In the present specification, the non-printing plate DTR method means that a material obtained by DTR is used for a purpose other than a lithographic printing plate, for example, an underlay material.

B. Prior art and its problems The principle of the DTR method is described, for example, in U.S. Pat.
See Lottery, E. Wade, "Photographic Silver Halide, The Diffusion Process," Focal Press (1972). In the development processing after exposure, the silver halide in the exposed area undergoes chemical development with a developing agent, whereas in the unexposed area, the silver halide is solubilized by the formation of complex ions in the presence of a silver ion solvent, It diffuses into an image receiving layer containing physical development nuclei, where it is reduced to a silver image by a developer.

In this way, a DTR image is formed, but unfortunately,
Often, the image formed on the image receiving layer is not satisfactory in density, color tone and the like. Therefore, many attempts have been made to improve the image density and color tone.

For example, U.S. Pat. No. 3,042,514 describes the use of 5-phenyl-2-mercaptotetrasol in the passive layer. U.S. Pat. No. 4,310,613 also states that quaternary ammonium salts improve the permeation concentration. However, the reflection density appears to be impaired.

The terms "transmission density" and "reflection density" used here mean the diffuse transmission density and the diffuse reflection density, respectively, and are American Standard PH2.19 (1959) and PH2.
Measured according to the requirements of 17 (1958). The reflection density is affected by the speed of image formation, that is, the adhesion speed of image silver, the size and shape of silver particles forming an image, the depth of adhesion of silver particles in an image receiving layer, and the like.

Increasing the density of the image in the image receiving layer is necessary to prevent the bronzing effect. If the internal scattering is not promoted from the surface scattering column of the incident light, a neutral color image cannot be obtained and, for example, a brown image is obtained. To avoid this, the aforementioned U.S. Pat.
No. 042,514 and JP-A-62-98350 and JP-A-62-98349 are used.

However, these compounds cause sludge in the processing solution and have many disadvantages such as being impractical or effective although the color tone improving effect is recognized. Have been.

C. Object of the Invention It is an object of the present invention to provide a color tone improver which does not show a decrease in reflection density.

D. Constitution of the Invention The object of the present invention has been achieved by performing DTR treatment in the presence of the compound of the general formula (I). By using this compound, the reflection density could be enhanced without significantly lowering the transmission density of the transferred image, and at the same time, the color tone of the transferred image was improved and the transfer time was not delayed.

In the formula, R ¹ is a mercapto group, an amino group, a dialkylamino group, an alkoxy group, and R ² is a hydrogen atom, a chloro atom,
Represents a carboxyl group.

Compound (I) is an image receiving material, a silver halide photosensitive material,
Although the addition to any of the processing solutions is effective, the addition to the image receiving material is most effective.

 Next, examples of the color tone improving agent of the present invention are shown.

These compounds can be easily synthesized according to JOC 26 .729 (1961).

When the compound of the formula (I) of the present invention is added to a light-sensitive material or an image-receiving material, it is 1.0 × 10 ^{−3 to} 5.0 × 10 ⁻¹ mg / m ² , preferably 5.0 × 10 ^{−3 to} 5.0 × 10 ^−2. it is preferable to use mg / m ^2.
Also, when added to the processing solution, 0.1 to 10 g /, preferably,
It is good to use 0.5-3g /.

It is preferable to add it as a solution when adding it, and it is better to dissolve it in a 2NHaOH aqueous solution to form a salt, and as it is, DMF, MeO
It may be added by dissolving in an organic solvent such as H. It is also possible to isolate once in the form of a salt and add it as it is.

In order to enable the rapid formation of a silver complex salt with the aid of a silver halide solvent, the silver halide of the photographic silver halide emulsion of the light-sensitive material used according to the present invention contains silver chloride containing 70 mol% or more of chloride, It is preferable to use silver chlorobromide, silver chloroiodide, or silver chloroiodobromide.

Silver halide emulsions can also be sensitized blue, green and red. It can be a merocyanine, cyanine dye or other sensitizing dye.

Further, the silver halide emulsion can be chemically sensitized with various sensitizers. For example, sulfur sensitizers (eg, hypo, thiourea, gelatin containing unstable sulfur, etc.), noble metal sensitizers (eg, gold chloride, rhodium gold, ammonium chloroplatinate, silver nitrate, silver chloride, palladium salt, rhodium salt,
Iridium salts, rutinium salts, etc.), U.S. Pat.
No. 698 polyalkylene polyamine compounds,
Imino-amine-methanesulfonic acid described in German Patent 1,020,864, reduction sensitizer (for example, stannous chloride, etc.)
Are advantageously used.

Suitable coverage of silver halide expressed about 1 m ² in silver nitrate g is in the range of 1 to 5 g / m ^2.

Gelatin is preferred as the binder in the photographic silver halide emulsion layer. However, instead of or together with 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 (eg carboxymethylcellulose, modified gelatin), etc. Can be used. The weight ratio of the hydrophilic colloid to silver halide in terms of silver nitrate in the silver halide emulsion layer of the light-sensitive material is in the range of 0.3 to 5, preferably 0.5 to 3.

In addition to the binder and the silver halide, the light-sensitive material contains any commonly used compound in the photographic silver halide emulsion layer and / or in one or more layers in water-permeable relationship therewith. it can.

For example, mercapto compounds, antifoggants or stabilizers such as tetraazaindene, saponins as surfactants, sodium alkylbenzene sulfonates, sulfosuccinates, and anionic salts such as alkylaryl sulfonates described in U.S. Patent No. 2,600,831 Compounds and amphoteric compounds as described in U.S. Pat. No. 3,133,816, as well as waxes, polyol compounds, wetting agents such as glycerides or higher alcohol esters of higher fatty acids, N-guanylhydrazone-based compounds, quaternary onium compounds, tertiary Antistatic agents such as mordantes such as amine compounds, diacetylcellulose, styrene-perfluoroalkylene sodium maleate copolymers, and alkali salts of reaction products of styrene-maleic anhydride copolymers and P-aminobenzenesulfonic acid Polymethacrylic acid esters, polystyrene, colloidal such matting agent of silicon oxide, acrylic acid esters, such as film properties modifiers of various latexes, styrene - maleic acid copolymer, JP-B-36-
Thickeners, antioxidants, developing agents, pH adjusters and the like as described in No. 21574 can be used.

The photographic hydrophilic colloidal silver halide emulsion layer can be hardened with an appropriate hardening agent. Specific examples of the hardening agent include aldehyde compounds such as formaldehyde and glital aldehyde, and diacetyl and cyclopentanedione. Ketone compounds, bis (2-chloroethylurea) -2-hydroxy-4,6-dichloro-1,3,5-triazine, compounds having a reactive halogen as described in U.S. Pat. No. 3,288,775, vinyl sulfone, U.S. Pat. No. 3,635,718, compounds having a reactive olefin as described in U.S. Pat.
N-methylol compounds as described in 732,316, isocyanates as described in U.S. Pat.No.3,103,437, aziridine compounds as described in U.S. Pat. Epoxy compounds as described in U.S. Pat. One or two
It can be used in combination of more than one species.

As a support of the photosensitive material used in the present invention, a polystyrene, a polycarbonate film, a plastic film such as cellulose triacetate and polyethylene terephthalate, a polyethylene laminated paper coated with polyethylene, a baryta paper and the like are used.

The back layer desirably provided on the back surface of the support contains a hydrophilic colloid in an amount necessary to maintain a curl balance with the photosensitive layer side. The amount depends on the total amount of the hydrophilic colloid on the photosensitive layer side, the amount of the white inorganic pigment, and the like.

The image receiving layer of the image receiving material used according to the present invention can be coated on an opaque or transparent support which can be one of the supports described above for the photosensitive material.

Physical development nuclei include silver, gold, platinum, palladium,
Metals such as copper, cadmium, lead, cobalt and nickel or sulfides and selenides thereof can be used. These are preferably colloidal.

One or more layers of the non-photosensitive material containing the image receiving layer may include a surfactant, a matting agent, a fluorescent dye, a discoloration inhibitor, a toning agent,
Developing agents (for example, hydroquinone and its derivatives,
-Phenyl-3-pyrazolidone and its derivatives), and a solvent for silver halide (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 may consist of or contain any of the binders described above for silver halide. Gelatin is the preferred binder for the image receiving layer.

The image-receiving layer can be hardened with a suitable hardener described in the photographic hydrophilic colloidal silver halide emulsion layer.

The plurality of hydrophilic colloid layers can be applied separately in several parts, or can be applied simultaneously. The coating method may be any known method and is not limited.

The processing liquid used for the diffusion transfer method is an alkaline substance,
For example, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium tertiary phosphate and the like, silver halide solvents such as sodium thiosulfate, ammonium thiocyanate, cyclic imide compounds, thiosalicylic acid and the like, preservatives such as sodium sulfite and the like, Thickeners such as hydroxyethylcellulose and carboxymethylcellulose; antifoggants such as potassium bromide and 1-phenyl-5-mercaptotetrazole; development modifiers such as polyoxyalkylene compounds, onium compounds and developing agents such as hydroquinone; It can include 1-phenyl-3-pyrazolidone, hydroxylamine, and the like.

However, in a highly alkaline processing solution containing this developing agent, the developing agent has a drawback that it undergoes oxidative deactivation due to air oxidation, and therefore, the developing agent is contained in the DTR material, that is, the silver halide emulsion layer or / and the water permeation thereof. The disadvantage can be largely avoided by a method of incorporating the compound into a hydrophilic colloid layer having a sexual relationship.

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

The DTR method using an alkaline activating solution is disclosed in JP-B-39-27568,
Reference can be made to the specifications of JP-A-47-30856 and JP-A-51-43778.

(E) Examples Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto.

Gelatin silver chloride emulsion usually hardened with formaldehyde (gelatin AgNO ₃ = 1.67, coating amount 0.6g / m ^{2 in} terms of AgNO ₃
C paper was applied at 45 ° C. After drying the emulsion layer, a topcoat solution having the following composition was applied at 45 ° C. at a ratio of 1/20 m ² and dried.

The light-sensitive material prepared according to the above method was exposed imagewise, and then only the emulsion side was wetted with the following processing solution.

After 3 to 5 seconds, the wet photosensitive material was brought into close contact with the image receiving layer prepared by the following method for 8 seconds. The image receiving layer was formed by applying the following dispersion at a ratio of 1/15 m ² after corona discharge using RC paper as a support.

After adhesion, peeling, transmission density of the transferred image (D _TR), it was measured saturation concentration (Dmax) and the reflection density (D _RT). Saturated concentration is the highest concentration in the wedge spectrum. The value of D _TR in the table below is a value obtained by subtracting the density 0.66 of RC paper.

The color of the blank transfer silver is brownish black,
Otherwise blank for the above table is black neutral without bronzing, Dmax, both D _RT is superior blank.

(F) Effect of the Invention The color tone adjusting agent of the present invention improves color tone, reflection density ( _DRT ) and maximum density (Dmax) by preventing the bronzing effect in DTR images.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-49-11333 (JP, A) JP-B-46-11630 (JP, B1) JP-B-43-4137 (JP, B1) (58) Field (Int.Cl. ⁶ , DB name) G03C 8/36

Claims (1)

(57) [Claims] 1. A silver complex salt diffusion transfer reversal method, which comprises developing in the presence of a compound represented by the following general formula (I). General formula (I) (In the formula, R ¹ represents a mercapto group, an amino group, a dialkylamino group, or an alkoxy group, and R ² represents a hydrogen atom, a chloro atom, or a carboxyl group.)