JPH03260644A - Image receiving material for silver complex salt diffusion transfer method - Google Patents

Abstract

PURPOSE:To improve the color tones of transferred silver images, the max. density and contrast by incorporating a specific compd. into the image receiving material. CONSTITUTION:The compd. of formula I and/or II is incorporated into the physical development nucleus-contg. image receiving layer of the image receiving material and/or the nonphotosensitive hydrophilic colloidal layer having a water permeation relation therewith. The photosensitive material having the silver halide emulsion layers is subjected to exposing according to the images and is superposed on the image receiving material. The materials are then developed to form the transferred silver images on the image receiving material. In the formulas, R denotes alkyl or aryl; R1 denotes alkyl or aralkyl; X<-> denotes anion (where, there is no X<-> when R1 contains a sulfo group, etc.); R2 to R5 denotes H, alkyl, etc.; R6 denotes a residual group; (n) denotes 2 to 4; (m) denotes 0 or 1. The more specific examples of these formulas include the compd. of formula III, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (M) Industrial Application Field The present invention relates to an image-receiving material for use in a silver complex diffusion transfer method.

(B) Prior art and its problems The silver complex salt diffusion transfer 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. copies of documents;
For example, it is widely used in copies of printed matter, handwritten documents, blueprints, and as a material for plate making, and requires faithful image reproduction of the original manuscript.

Furthermore, in the above DTR method, it is important to obtain a pure black to blue-black silver image in the image-receiving layer. It is known that in order to obtain such a transferred silver image, a so-called color toning agent may be included in the image-receiving layer or the diffusion transfer processing liquid.

Various color toning agents are known.

For example, US Pat. No. 3,042,514 describes the use of organic sulfur compounds such as phenylmercaptotetrazole in the image receiving layer. However, such compounds have the disadvantage of significantly inhibiting the rate of transfer.

Therefore, the amount of such toning agents used is limited, resulting in insufficient toning effects and rapid transfer to obtain silver images with high maximum density, high contrast and high sharpness. It inhibits development and usually makes such properties unsatisfactory.

(C) OBJECTS OF THE INVENTION It is an object of the present invention to provide an image-receiving material for use in a silver complex diffusion transfer method for obtaining transferred silver images with improved color tone, maximum density, contrast and sharpness.

(D) Structure of the Invention It is an object of the present invention to imagewise expose a light-sensitive material containing a photographic silver halide emulsion layer and to develop the exposed emulsion layer with the aid of an alkaline processing solution containing a silver halide solvent. Then, a silver complex salt is diffused into an image-receiving material including an image-receiving layer containing physical development nuclei.

As a result, in the image-receiving material in which a silver transfer image is formed, the compound represented by the following general formula (I) and/or (n) is added to the physical development nucleus-containing image-receiving layer and/or
Alternatively, this can be achieved by an image-receiving material for a silver complex diffusion transfer method, which is characterized in that it is contained in a non-photosensitive hydrophilic hazy coid layer that has a water-permeable relationship therewith.

General formula (I) General formula (IO) (wherein R represents an alkyl group or an aryl group, R1 represents an alkyl group or an aralkyl group, and when R1 is a group containing a sulfo group or a carboxyl group, Xo is Does not exist.X
e represents an anion. fL2. Ba5-R4 and BS
each represents a hydrogen atom, an alkyl group, an alkenyl group, or an alkoxy group. R1, R ink.

R4 and R5 may be the same or different, or R2 and R5 or R3 and R4 may be linked to each other to form a carbocyclic ring.

R4 represents an n-valent residue bonded to a carbonyl carbon forming a carboxylic acid ester using a carbon atom or a nitrogen atom, n represents 2.3 or 4, and m represents 0 or 1. ) The alkyl group represented by R in the general formula may be chain-like or branched, and may be further substituted with a suitable group (eg, halogen, alkoxy group, etc.).

Preferably it has 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, and n-hexyl.

Trichloromethyl etc., phenyl group as aryl group,
Aromatic groups such as naphthyl groups are preferred, and these aromatic groups may be substituted with appropriate groups (eg, halogen, alkyl groups, nitro groups, etc.).

The alkyl group represented by B1 may be linear or branched, and may also be substituted with a suitable group (eg, sulfo group, carboxyl group).

Preferably, the aralkyl group has 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, n-hexyl, carboxymethyl, sulfopropyl, etc.
It may be linear or branched, and may be further substituted with a suitable group (eg, sulfo group, carboxyl group).

Preferably, it has 7 to 15 carbon atoms, examples of which include hensyl, 7-enethyl, phenylpropyl, 2-carboxybenzyl, etc. However, if 111 is a group containing a sulfo group or a carboxyl group, Xe is not exist.

Xe represents an anion, preferably -rogen ion, alkylsulfonate or arylsulfonate.

The alkyl groups represented by Rz, Ri%84 and B5 may be linear or branched,
Preferably, the alkenyl group has 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, 1so-7'robyl, n-butyl, tert-butyl, n-hexyl, etc. The alkenyl group is linear or branched. It may be in the form of
Preferably, it has 1 to 8 carbon atoms, such as allyl, butenyl, or octenyl.

Examples of al;oxy groups include methoxy, ethoxy, n
-propoxy, n-butoxy% n-octoxy, benzyloxy, etc. Also, when R1 and R1 or 31 and R4 are linked to each other to form a carbocycle, examples of this carbocycle include, for example, a benzene ring. Or 8
A condensed ring having from 1 to 14 members, preferably a naphthalene ring and the like.

Substituents may be bonded to these carbon rings.

Among the compounds represented by the general formula, one particularly preferred in the present invention is IB! , R1, R4 and Ri are all hydrogen atoms, or Bz and Rs or Rs and B4 are linked to each other to form a benzene ring.

Examples of R6 include alkylene (ethylene, propylene, 1,2-dimethylethylene, tetramethylene, octamethylene, etc.), alkenylene (vinylene, ethynylene,
flobenylene, etc.), cycloalkylene (I,3-cyclopentylene, 1,4-cyclohexylene group), arylene (m-phenylene, p-phenylene, 1,3-s7tylene, etc.), alkylene diimino (tetramethylene diimino, hexamethylene diimino, etc.), 1,4-cyclohexylene diimino, 1,3-phenylene diimino, etc.

Specific examples of the compounds represented by the general formula (I) or (II) of the present invention are listed below, but the compounds of the present invention are not limited thereto.

The compound represented by general formula (I) or general formula (If) used in the present invention can be synthesized very easily by referring to JP-A-56-36645 and JP-A-59-20369. can. The amount of the above compound used is 1 q/m
The amount added is preferably about 1 to 1 f/d.

The silver halide of the photographic silver halide emulsion of the light-sensitive material used according to the invention contains more than 90 mol chloride, in order to enable the rapid formation of a silver complex salt with the aid of a silver halide solvent. , silver chlorobromide, silver chloroiodide, and silver chloroiodobromide are preferably used.

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 sensitizers6, such as sulfur sensitizers (e.g., hypo, thiourea, unstable 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 clay, etc.), polyalkyleneboriaelectron compounds described in U.S. Patent No. 2,518.698, imino-amino-methanesulfone compounds described in German Patent No. 1,020,864, reduction sensitizers (e.g. (stannic chloride, etc.) are advantageously used.

The preferred coverage of silver halide expressed in t of nitrate 1 silver for 1i is 1 to 5 f/w? is within the range of

The binder for the photographic silver halide emulsion layer is preferably gelatin. However, instead of or in addition to gelatin, there are over 111 other natural and/or synthetic compounds! Hydrophilic colloids such as albumin, casein, zein, polyvinyl alcohol, alginic acid or its salts, cellulose derivatives (eg carboxymethyl cellulose, modified gelatin), etc. can also be used. Hydrophilicity to silver halide in terms of silver nitrate in the silver halide emulsion layer of the JI photosensitive material; the weight ratio of roid is 0.3 to 5, preferably 0.5 to
Used in a range of 3.

In addition to the binder and silver halide, the photosensitive material may contain any type of compounds commonly used in the photographic silver halide emulsion layer and/or in one or more layers in water permeable relationship thereto. Can be included.

For example, mercapto compounds, antifoggants or stabilizers such as tetraazaindene, saponin as a surfactant, sodium alkylbenzene sulfonate, sulfosuccinic acid ester salt, US patent rate 2.6 o o, s a
Anionic compounds such as alkylaryl sulfonates described in No. Infiltrating agents, N-guanyl hydrazone compounds, quaternary onium compounds, tertiary adenoid compounds such as mordants, diacetylcellulose, sterene-perfluora-alkylene sodicum maleate copolymer, styrene-anhydrous! an antistatic agent such as an alkali salt of a reaction product of Reishun copolymer and P-7 minobenzenesulfonic acid;
Matting agents such as polymethacrylate ester, polystyrene, colloidal silicon oxide, acrylic acid esters, film property improvers such as various latexes, styrene-maleic acid copolymers, thickeners such as Japanese Patent Publication No. 36-21574, Antioxidants, active agents, pHw4 adjusters, etc. can be used.

The photographic hydrophilic colloidal silver halide emulsion layer can be hardened with a suitable hardener. Specific examples of hardeners include aldehyde compounds such as formaldehyde and geltaraldehyde, diacetyl, and cyclobentanedione. Chthonic compounds such as his(2-ria*2-hydroxy-2-hydroxy-4,6-dichloro-1,3,5) riazine, reactive compounds such as those described in U.S. Patent No. 3,288,775 Halogen-containing compound, divinyl sulfone, US patent rate 3
, 635゜718, N-methylol compounds as described in U.S. Patent No. 2.732,316, U.S. Patent No. 3,103,437
Isocyanates as described in No. 1, US patent rate 3.017
．． 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. Patent No. 3,09
These include epoxy compounds as described in No. 1,537, logenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane, and inorganic hardeners such as chromium alum, potassium alum, and zirconium sulfate. It is possible to combine about 1 or 2211 or more combinations.

As the support for the photosensitive material used in the present invention, plastic films such as polystyrene, polycarbonate film, cellulose triacetate, and polyethylene Tele 7 Talley F, or polyethylene-coated polyethylene laminated F paper, baryta paper, etc. are used. be done.

The pack layer desirably provided on the back side of the support contains a hydrophilic colloid in an amount necessary to maintain overall balance with the photosensitive layer side. The amount is the total amount of hydrophilic colloid on the photosensitive layer side,
It depends on 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 photosensitive materials.

Physical development nuclei include silver, gold, platinum, palladium, copper,
Metals such as 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-tarnishing agents, toning agents, active agents such as hydroquinone and its derivatives, 1-
phenyl-3-pyrazolidone and its derivatives, etc.), No.1
A solvent for silver 0genide (eg, sodium thiosulfate, ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate, etc.) can be included. Even more g! A neutralizing layer and a subbing layer for improving adhesion to the support may be provided below the layer.

The image-receiving layer can be comprised of any of the binders described above for silver halide. 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, tertiary phosphorus, silver halide solvent such as sodium thiosulfate, ammonium thiocyanate, and a cyclic imide compound. , thiosalicyl alcohol, etc., preservatives 1, such as sodium sulfite, etc.

Thickeners such as hydroxyethyl cellulose, carboxymethyl cellulose, etc., anti-capri agents such as potassium bromide, 1-phenyl-5-mercaptotetrazole, etc., developer modifiers such as polyoxyalkylene compounds, onium compounds, developing agents.

Examples include hydroquinone, 1-phenyl-3-pyrazolidone, hydroxylamine, and the like.

However, in a highly alkaline processing solution containing this developing agent, the developing agent is subject to air oxidation and loses its effectiveness.
Therefore, this drawback can be largely avoided by incorporating the developing agent into the DTR material, that is, into the silver halide emulsion Mi and/or 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 activated liquid was developed by the Japanese Patent Publication Publication No. 39-27
568% Dosho 47-30856, Dosan 51-43778
You can refer to the specifications of .

(E) Examples The present invention will be explained below using Examples, but the present invention is not limited in any way.

Example 1 The photosensitive material is a polyethylene laminate paper with an undercoat layer containing carbon black to prevent scratches, and on top of that an undercoat layer containing orn-sensitized silver chlorobromide (with an average particle size of 0.3μ). Convert silver bromide (5 molt) to silver nitrate: 1.5
It was produced by coating a gelatin silver halide emulsion layer containing 0.2 fβ of 1-phenyl-3-pyrazolidone, 0.7 f/wl of hydroquinone, and 4 of gelatin.

The silver halide emulsion layer is impregnated with a hardening agent and hardened so as not to interfere with the diffusion transfer process.

For the image-receiving material, a solution was prepared as described in 1 below, and the solution was coated on polyethylene laminate paper of 90 f/d, which had been previously treated with corona discharge, to a gelatin density of 2 f/d, and dried.

The obtained image-receiving material is impregnated with a hardening agent and hardened so as not to interfere with the diffusion transfer process.

A diffusion transfer treatment solution having the following composition was used.

The photosensitive material produced as described above is imagewise exposed, the emulsion surface of the photosensitive material and the receiving surface of the image receiving material are overlapped, and the material is passed through a processor having an aperture roller containing the above-mentioned diffusion transfer processing solution. Both materials were peeled off after 30 seconds.

The image-receiving material is washed with water for about 30 seconds and then dried, and the reflection density of the black area is
It was determined using a fr-f Kubes RD519 reflection densitometer.

The same method was repeated several times, except that the above-mentioned materials and the preparation of the transfer image using the processing solution according to the DTR method were changed as shown in Table 1 above and below for the compounds according to the present invention. Blank means that no compound according to the invention is present in the image-receiving layer.

Table 1 Blank 1.45 Brown compound 2 1.51 Neutral black compound 5
1.52 Neutral black compound 7 1.60
Neutral black compound 8 14S Neutral black compound 15 1.49 Neutral black compound 21
1.58 Neutral Black The results shown in Table 1 show that the reflection density measured for the transferred images obtained with compounds 2.5.7.8, 15 and 21 according to the invention is greater than that of the blank. It shows.

The color tone of the transferred image obtained as a blank was brown. On the other hand, the color tone of the transferred images obtained with Compounds 2.5.7, 8.15 and 21 was a good neutral black.

Example 2 An image receiving material was produced as follows. Adjust the coating liquid below,
The gelatin gelatin solution described in Example 1 was coated on Neato paper at a concentration of 2 f/d.

The layer formed while still wet was coated with the coating solution described below to a gelatin content of 1.5 f/l/l.

The obtained image-receiving material is hardened with a hardening agent so as not to interfere with the diffusion transfer process.

A diffusion transfer treatment solution having the following composition was used.

The photosensitive material was prepared as described in Example 1.

Photosensitive material manufactured as above, for diffusion transfer 161
Using the same liquid and image receiving material, the same treatment as in Example 1 was carried out.
The same procedure was repeated several times, except that the compounds according to the invention were changed as shown in Table 2 below.

Blank means that no compound according to the invention is present in the non-photosensitive hydrophilic colloid layer covering the recipient layer.

Table 2 Compound 7 1.65 Neutral black compound 10
1.63 Neutral black compound 18 1.58
Neutral black compound 22 1.57 Neutral black compound 23 1.61 Neutral black compound 24
1.60 Neutral Black The results shown in Table 2 show that compounds according to the invention 7.10.18.22.23 and 24
It is shown that the reflection density measured for the transferred image obtained in the above is higher than that of the blank.

The color tone of the transferred image obtained as a blank was brown. In contrast, compounds 7.10.18.22.23 and 24
The color tone of the transferred image obtained was a good neutral black.

Blank 1. SO brown color

Claims (1)

Claims: 1. imagewise exposing a light-sensitive material containing a photographic silver halide emulsion layer and developing the exposed emulsion layer with the aid of an alkaline processing solution containing a silver halide solvent; Diffusing a silver complex salt into an image receiving material including an image receiving layer containing physical development nuclei,
As a result, in the image-receiving material in which a silver transfer image is formed in the layer, the following general formula (I) and/or (II) is used.
An image-receiving material for a silver complex diffusion transfer method, characterized in that the compound represented by the above is contained in the physical development nucleus-containing image-receiving layer and/or a non-photosensitive hydrophilic colloid layer having a water-permeable relationship therewith. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R represents an alkyl group or an aryl group, and R_1 represents an alkyl group or an aralkyl group. and when R_1 is a group containing a sulfo group or a carboxyl group, X^■ does not exist. X^■ represents an anion. R_2, R_3, R_4 and R_5 are each a hydrogen atom,
Indicates an alkyl group, alkenyl group or alkoxy group. R_2, R_3, R_4 and R_5 may be the same or different from each other, or R_2 and R_3 or R_3
and R_4 may be connected to each other to form a carbon ring. R_6 represents an n-valent residue bonded to a carbonyl carbon forming a carboxylic acid ester using a carbon atom or a nitrogen atom. n represents 2, 3 or 4; m represents 0 or 1; )