JPS63226647A - Silver complex salt diffusion transfer process for regenerating continuous gradation - Google Patents

Abstract

PURPOSE:To form an image having a fine color tone and fine continuous gradation by using a developing soln. for diffusion transfer having a specified compsn. CONSTITUTION:When a photographic sensitive material for silver complex salt diffusion transfer (DTR) is superposed on an image receiving material and passed through a developing soln. for DTR to reproduce the continuous gradation, >=0.4mol/l amino-alcohol compd. >=0.05mol/l p-dihydroxybenzene compd. and about 5X10<-5>-5X10<-4>mol/l compd. represented by the formula (where R1 is H or <=3C alkyl and each of R2 and R3 is H, <=3C alkyl or acyl) are incorporated into the developing soln. The compd. represented by the formula may be separated from the developing soln. and used as a component of a replenishing compsn. added by a replenishing system. The developing soln. can be adapted to the development of various sensitive materials. When the developing soln. is used for a DTR process, continuous gradation can be reproduced with a fine color tone, high Dmax and high contrast.

Description

DETAILED DESCRIPTION OF THE INVENTION (A) Industrial Application Field The present invention relates to a silver complex diffusion transfer method for reproducing continuous gradations.

CB) Prior art and its problems Principle of silver complex diffusion transfer method (hereinafter referred to as DTR method)
U.S. Patent No. 2,352,014 F! It is described in Book Aa, and many other documents and patents are publicly known.

In the DTR method, the silver complex salt solubilized in the silver halide emulsion layer is diffused into the image-receiving layer and transferred according to the image.
In the presence of physical development nuclei, it is converted into a silver image. For this purpose, an imagewise exposed silver halide emulsion layer is
It is placed or brought into contact with the image receiving layer in the presence of a developing agent and a silver halide solvent to convert the unexposed silver halide to a soluble silver complex salt. In the exposed portions of the silver halide emulsion layer, the silver halide is developed into silver, so that it cannot be further 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.

The DTR method has a wide range of applications, such as document reproduction, lithographic printing plate production, printing plate material production, and continuous tone reproduction.

Regarding the silver complex diffusion transfer method for reproducing continuous gradations, for example, Japanese Patent Publication No. 57-33775 and Japanese Patent Application Laid-Open No. 54-9
It is publicly known as described in specifications such as No. 9436. The methods disclosed in these specifications include determining the weight ratio of silver halide and hydrophilic colloid, and
- Dihydroxybenzene compound and 3-pyrazolidone compound are all used in combination, but the drawback of such a method is poor running properties.

In order to solve the above problems,
The methods described in Specification No. 911 and Japanese Patent Application No. 62-2694 were effective. However, it could not be said that the gradation properties for reproducing continuous gradations were necessarily sufficient.

Now, when the DTR method is used for reproduction of Class 9, draft preparation in the plate making field, design work, etc., images reproduced in continuous tone are often used for layout (positioning), and at the same time ultra-high contrast images are used. A reversal photosensitive material is often used. The diffusion transfer processing liquid used for such photosensitive materials for ultra-high contrast images and photosensitive materials for reversal is preferably a general-purpose developer type with high running properties, such as:
JP-A-60-212760, JP-A-60-21276
It is characterized by the use of a large amount of aminoalcohol compounds, as described in Mei No. 1 and other documents. The disadvantages of general-purpose developers containing such amino alcohol compounds and p-dihydroxybenzene compounds in excess of a certain amount are that they are inferior in tonality for reproducing continuous gradation and in the color tone of continuous gradation images. This resulted in a high-contrast, sepia-toned color tone.

The present inventors have improved the above-mentioned general-purpose developer and have studied a developer suitable for reproducing continuous gradations.

(C) Object of the present invention An object of the present invention is to provide a developer suitable for reproducing continuous gradations.

Another object of the present invention is to provide a silver complex diffusion transfer method for reproducing continuous gradations.

Other objects of the invention will become apparent from the following description.

(D) Structure of the Invention In order to achieve the above object, the present inventors conducted various studies and discovered the following method.

That is, in the silver complex diffusion transfer method for reproducing continuous gradation by overlaying a photographic light-sensitive material for silver complex diffusion transfer with an image-receiving material and passing it through a developer for diffusion transfer, the diffusion transfer The developing solution contains an amino alcohol compound of 0.4 mol/l or more, a p-dihydroxybenzene compound of 0.05 mol/l or more, and about 5 x 10-5 to about 5 x 1
"A silver complex diffusion transfer method for reproducing continuous gradation, characterized by containing 0-' mol/l of a compound of the following general formula (1)."

■ N-R.

General formula (1) (where R1 is a hydrogen atom, an alkyl group having 3 or less carbon atoms, R2 and R5 are hydrogen atoms, an alkyl group having 3 or less carbon atoms,
It is an acyl group. ) General formula (The following is a specific example of NH-C
H.

NH2 CN(CH3)2! NH-n-C5H7 NH-COCH5 NCCHs)2! N(C2H5)2 Compounds of general formula (I) are about 5X10-5 to about 5X10
- It is effective when contained at mol/1, about 5×
If it is less than 10-5 mol/l, it will not be effective and about 5 x 10"
If it exceeds mol/l, negative effects such as a decrease in the maximum concentration occur.

The compound of general formula (1) used in the present invention can also be separated from the developer solution and used as an element of a replenishment composition that is added in a replenishment manner.

That is, adding the compound of the general formula (1) in a replenishing manner means adding the compound of the general formula ( Since continuous tone light-sensitive materials can be processed by adding the compound 1), it has the advantage that a single developing solution can be used for various light-sensitive materials. Moreover, in this case, the gradation can be changed depending on the amount of the compound of general formula CI) to be replenished.

The developer for silver complex diffusion transfer used in the present invention is:
It contains at least 0.4 mol μ of an amino alcohol compound and 0.05 mol/l of a p-dihydroxybenzene compound.

The amino alcohol compound used in the present invention is
For example, JP-A-60-212760, JP-A-61-739
No. 50 and JP-A-61-73951.

The amino alcohol contained in the developer for silver complex diffusion transfer used in the present invention is a 1.2 and 3a amine compound having at least one hydroxyalkyl a. Preferably, secondary and tertiary amino alcohols are used. Amino alcohol includes a compound represented by the following general formula (A).

General formula (A) (X and X' represent a hydrogen atom, a hydroxyl group, or an amino group. L and m are 0 or an integer of 1 or more, and n is 1
) Specifically, ethanolamine, jetanolamine, triethanolamine, cynobrobanolamine, N-methylethanolamine,
N-aminoethylethanolamine, N,N-diethylethanolamine, N,N-dimethylethanolamine, N-methylgetanolamine, N-ethergetanolamine, 3-aminopropanol, 1-amino-propane-2 -ol, 4-aminobutanol, 5-amino-pentan-1-ol.

3.31-Iminodiglobanol, N-ether-2,2
'-Iminodiethanol and the like can be mentioned.

In addition, the above-mentioned 2-amino-2-(hydroxymethyl)
Propane-1,3-diol, 2-amino-2-methylpropane-1,3-diol, and the like can also be used.

The amino alcohol contains at least 1 amino alcohol with a pKa value of less than 9 and an amino alcohol with a pKa value of 9 or more in an aqueous solution containing 50% by weight ethanol (25°C).
It is particularly preferred to contain seeds.

The pKa value of amino alcohol is, for example, l'-8TAB
-IIJTY C0N5TANTS OF METAL
-1ONCO-MPLEXBSJ (5special
Publication A17 (1964) and Ni 25 (1971), 'rHE C former MIC Nakaku 5OC
Published by IETY LONDON), [Chemistry Handbook Basic Edition nJ
(Revised 3rd edition, June 25, 1980, published by Maruzen Co., Ltd.), etc., and can be easily measured.

The amount of the amino alcohol compound used in the present invention is required to be at least 0.4 mol per developer 1 for silver complex salt diffusion transfer, and if it is less than this value, the running properties will deteriorate significantly.

The p-dihydroxybenzene compound contained in the developer for silver complex diffusion transfer used in the present invention is a compound represented by the general formula CB).

Specific examples of the p-dihydroxybenzene compound include hydroquinone, methylhydroquinone, and chlorohydroquinone.

The -ih of the p-dihydroxybenzene compound contained in the developer for silver complex diffusion transfer used in the present invention is required to be at least 0.05 mol per developer. unsuitable for treatment.

Hydrophilic colloids which are advantageously used for preparing photosensitive emulsions include lime-treated gelatin, acid-treated gelatin, gelatin derivatives (e.g. Japanese Patent Publications No. 38-4854, No. 39-5).
No. 514, No. 12237 of 1972, No. 263 of 1973
No. 45, U.S. Patent No. 2,525,753, U.S. Pat.
No. 94,293, No. 2.614,928, No. 2,
No. 763,639, No. a, +18,766, No. 3,13°2,945, No. 3,186,846,
No. 3,312,553, British Patent No. 861,414
No. 1,033,189), proteins such as aldimine and casein, cellulose compounds such as carboxyl methyl cellulose and hydroxyethyl cellulose, agar, natural polymers such as sodium alginate, polyvinyl alcohol, and polyvinyl alcohol. Synthetic hydrophilic binders such as -N-vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamide, or partial hydrolysates of these derivatives are available, and these hydrophilic colloids can be used alone or in combination. Can be used.

In addition, these hydrophilic colloids can be used in antihalation layers,
O/(++41) is also advantageously used to create non-photosensitive layers such as hack layers or image-receiving layers.

The hydrophilic colloid in the silver halide emulsion layer is used in a weight ratio of 1 to 6 based on silver halide converted to silver nitrate.

The light-sensitive material for silver complex diffusion transfer according to the present invention has a silver halide emulsion layer coated on a support, and, if necessary, an overlayer and/or an undercoat layer. Good too.

Specific examples of the support include paper supports such as baryta paper and polyethylene laminated paper, and film supports such as polyethylene terephthalate.

In the present invention, the amount of silver in the silver halide emulsion is preferably at most 1.3 r/m' in terms of silver nitrate.

If the amount is 1.32 or more in terms of silver nitrate, the contrast will be too high and it will not be suitable for reproduction of continuous tone images.

In the present invention, silver halide contains 8
It is preferable that the emulsion is a silver halide emulsion containing silver bromide in an amount greater than 10% and containing silver chloride as a main component. The emulsion containing silver chloride as a main component as used in the present invention is an emulsion containing at least 60 moles of chloride based on the total molar amount of silver halide. If the chloride content is less than 60 molt, the color tone becomes sepia tone, which is not preferable.

On the other hand, if the bromide layer has an 8-mole groove, the contrast will be too high and it will not be suitable for reproduction of continuous-tone images.

The present invention is not limited to ``specifying that the chloride content in the halogen composition of the silver halide emulsion is 90 mole or more'' as described in JP-A-57-33775.

Rather, it contains more than 10 moles of bromide and 90 moles of chloride.
It is possible to obtain softer photographic characteristics when it is less than 100%.

Silver halide emulsions can also be spectrally sensitized in the back, green, and red. It may 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 salts, etc.), polyalkylene polyamine compounds described in U.S. Pat. 1, tin, etc.) are advantageously used.

In the present invention, in the photosensitive material for silver complex diffusion transfer, 0
It is preferable to contain a -dihydroxybenzene compound and a 3-pyrazolidone compound.

Specific examples of the O-dihydroxy-7benzene compound used in the present invention include catechol and 3-methylcatechol. In the present invention, the silver halide emulsion layer contains 0.
It is preferable to use above 2S'/m''μ, .0.
2t/pr? If it is too small, it will not be suitable for continuous tone image reproduction.

Specific examples of the 3-pyrazolidone compound used in the present invention include 1-phenyl-3-pyrazolidone (phenidone), 1-phenyl-4-'fk-3-pyrafM)Yn (
phenidone Z), 1-phenyl-4,4-dimethyl-3
-pyrazolidone (dimezone), 1-phenyl-4-methylol-3-pyrazolidone (dimezone S), and the like. Although it is also possible to use these 3-pyrazolidone compounds in combination,
These 3-pyrazolidone compounds are preferably used in an amount equal to or less than the 0-dihydroxybenzene compound.

In the present invention, it is preferable to use a p-dihydroxybenzene compound in addition to the above two. Specific examples of the p-dihydroxybenzene compound include hydroquinone and methylhydroquinone.

Chlorhydroquinone, etc. In the present invention, p
- The amount of the dihydroxybenzene compound added is at most 10 molar ratio to the 0-dihydroxybenzene compound.
% is preferable.

In the present invention, it is preferable to use a water-soluble 10-genide. Specific examples of water-soluble/S chlorides include:
These include chlorides such as sodium chloride and potassium chloride, and bromides such as sodium bromide and potassium bromide.

The image-receiving material used in the present invention has one or more types of physical development nuclei selected from nickel sulfide, cobalt sulfide, and silver sulfide, or two or more types of physical development nuclei forming a mixed crystal on the support. It is preferable to apply a dispersion of a hydrophilic colloid in a hydrophilic colloid. Methods for producing physical development nuclei are known in the art; for example, Nie Lott and E.
It is described in "Photographic Silver Halide Dehydration Processes" by Robert Waite, pages 54-57.

The constituent elements of the diffusion transfer material according to the present invention may further contain various additives.

For example, mercapto compounds, anti-capri agents or stabilizers such as tetraazaindene, saponins as surfactants, sodium alkylbenzene sulfonates, sulfosuccinic acid ester salts, and alkylaryl sulfonates as described in U.S. Pat. No. 2,600,831. In addition, waxes, polyol compounds, wetting agents such as glycerides of higher fatty acids or higher alcohol esters, N-guanyl hydrazone compounds, etc. , quaternary onium compounds, tertiary amine compounds such as mordants, diacetyl cellulose, sterene-fluoroalkylene sodium maleate copolymers, reaction products of sterene maleic anhydride copolymers and p-aminobenzenesulfonic acid. Antistatic agents such as alkali salts, polymethacrylic esters, polystyrene, matting agents such as colloidal silicon oxide, acrylic esters, film property improvers such as various latexes, styrene-maleic acid copolymers, Japanese Patent Publication No. 1983- Thickeners such as No. 21574, antioxidants, developing agents, pH adjusters, etc. can be 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 is the total amount of hydrophilic colloid on the photosensitive layer side,
It depends on the amount of white inorganic pigment, etc.

The silver halide emulsion layer of the present invention can improve image reproducibility when combined with an antihalation layer containing a black pigment.

Further, when the silver halide emulsion layer of the present invention is combined with an antihalation layer containing a white pigment, image reproducibility can be improved.

Furthermore, image reproducibility can also be improved when combined with an antihalation layer containing the above point color pigment and white pigment.

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.
□ Below, an example will be explained based on BIJI'.

(E) Examples Example 1 A breast milk preparation was prepared based on the following prescription.

A1: Maintain the temperature at 1150°C, add solution B over 2 minutes while stirring, age for 20 minutes, and adjust the pH to 3.4 with sulfuric acid.
Then, 2804 t" of Na was added, precipitated, and washed with water. (
Breast milk (b)).

Next, gelatin was added and redissolved in this breast milk, and sulfur sensitization and gold sensitization were performed using sodium thiosulfate and potassium chloroaurate. The emulsion thus prepared was orthosensitized by adding a sensitizing dye, adjusted to pH=4.5, and divided into 7. Add gelatin to the desired amount of gelatin coverage, add 0.6% catechol, 1-phenyl-4,4-
Dimethyl-3-pyrazolidone was added in an amount of 0.22β, a hardening agent and a surfactant were added to make up.

The emulsion prepared in this way was converted to silver nitrate and was 1.2
The amount of silver coated on the back was 7.0, and the amount of gelatin coated on the back was 7.0.

Two of the following compositions were applied onto a polyethylene-coated paper support.
It was coated in a coating amount of 01- to prepare an image-receiving material.

Next, sample (A) is exposed through a step wedge having a density difference of t'0.15, and combined with the above image-receiving material (receiver), the following silver complex salt diffusion transfer developer (DTR developer) is added. ), overlapped, and peeled off by 1 minute diameter.

DTR developer [■] Next, the compound of general formula (I) was added to the DTR developer according to Table 1, and the same treatment was performed.

The treatment temperature was 23°C. The material obtained in this way was subjected to sensitometry, and the results are shown below.

In the table, S represents the relative sensitivity, and L represents the logarithm of the relative exposure amount of the minimum density Dmin plus 0.05 and 90% of the maximum 0 degrees.
Dmax represents the maximum density.

As is clear from Table 1, Samples 2 to 6, which are embodiments of the present invention, have improved color tone and softer tone than Ratio Example 1 (Sample 1). It has favorable properties for tonal reproduction.

In addition, Comparative Example 1 is 1-
Continuous story despite containing phenyl-5-mercaptotetrazole! ! 11f, it can be seen that the color tone and gradation are not good enough for reproduction.

From this example, it has become clear that the silver complex diffusion transfer method for reproducing continuous gradation according to the present invention is a preferred embodiment for achieving the object of the present invention.

Example 2 A light-sensitive material for diffusion transfer and an image-receiving material were prepared in the same manner as in Example 1, and processed in the same manner as in Example 1 except that a general-purpose developer (n) Th having the following formulation was used as a general-purpose developer. .

Next, the compound (dl'k) was added according to Table 2, and the same treatment was performed to obtain the results shown in Table 2.

General-purpose developer [■] Table 2 As is clear from Table 2, sample 9.10, which is an embodiment of the present invention, has a lower color tone,
On the other hand, in sample 8,
There was no color tone or tone effect, and Sample 11 was found to be inferior in Dmax. From this example, it has become clear that the silver complex diffusion transfer method for reproducing continuous gradation according to the present invention is a preferable embodiment for achieving the object of the present invention.

Claims (1)

[Claims] (1) In the silver complex diffusion transfer method for reproducing continuous gradation by overlaying a photographic light-sensitive material for silver complex diffusion transfer with an image-receiving material and passing it through a developer for diffusion transfer, the developer for diffusion transfer The liquid contains an amino alcohol compound of 0.4 mol/l or more, a p-dihydroxybenzene compound of 0.05 mol/l or more, and about 5 x 10^-^5 to about 5
A silver complex salt diffusion transfer method for reproducing continuous gradation, characterized by containing a compound of the following general formula (I) in an amount of ×10^-^4 mol/l. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (I) (Here, R_1 is a hydrogen atom, an alkyl group with 3 or less carbon atoms, R_2, R_3 are a hydrogen atom, an alkyl group with 3 or less carbon atoms, an acyl group. be.)