JPH0196648A - Silver complex diffusion transfer method - Google Patents

Abstract

PURPOSE:To make possible negative type silver complex salt diffusion transfer using a direct positive silver halide photographic sensitive material which has the high sensitivity and is useful for a flashing exposure by comprising at least one layer of a specified direct positive silver halide emulsion layer in a photosensitive material. CONSTITUTION:At least one layer of the direct positive silver halide emulsion layer contg. in the photosensitive material usable for the silver complex salt diffusion transfer comprises a silver halide emulsion which is composed of a silver halide particle contg. about >=80mol.% a chloride, and adsorbs a sensitizing dye having a spectral sensitizing peak of 600-700nm, and the surface of said particle is substituted with a bromide. Thus, the negative type silver complex salt diffusion transfer using the direct positive silver halide photographic sensitive material which has the high sensitivity and is useful for the flashing exposure, is permitted.

Description

Detailed Description of the Invention (A) Industrial Application Field The present invention relates to a negative type silver complex diffusion transfer method using a direct positive silver halide light-sensitive material. This invention relates to a negative type silver complex salt diffusion transfer method using a sensitive direct positive silver halide photographic light-sensitive material.

(B) Prior art and its problems The direct positive silver halide photographic light-sensitive material referred to in the present invention is a material containing a silver halide photographic emulsion consisting of silver halide grains with a fogged surface and an electron acceptor. Yes, for example British Patent No. 723,019 and U.S. Patent No. 3,
This is described in the specification of No. 501,307 and the like.

In the field of graphic arts, it is well known that a wide variety of photographic materials are used in the process of making printing plates from manuscripts. They are required to have various properties depending on their use, and those skilled in the art are actively continuing to improve them by making full use of the latest photographic technology. Particularly in recent years, in order to improve quality stability, speed up work, and streamline operations, the introduction of devices that utilize electronics and laser technology, such as computer typesetting machines and scanners, has become increasingly popular, and the exposure time of photosensitive materials has been rapidly shortened. Therefore, the importance of photographic materials with excellent so-called flash exposure characteristics is increasing.

Thus, in recent years, with the increase in speed of image processing, scanning type output devices have been introduced, and in the wavelength range of 600 to 700 nm,
A flash light source having an emission wavelength is utilized. for example,
Helium-neon laser (He-Ne laser)
, red light emitting diode (red LED), etc., and in recent years,
Red semiconductor lasers (red LDs) are also being developed.

The principle of silver complex diffusion transfer method (hereinafter referred to as DTR method) is as follows.
It is described in US Pat. No. 2,352,014 and is well known.

In the DTR method, an imagewise exposed silver halide emulsion layer is brought into contact with an image-receiving layer in the presence of a developing agent and a silver halide complexing agent. In the silver halide emulsion layer, the silver halide grains with development nuclei are developed into silver (chemical development) and therefore cannot be dissolved or diffused any further. Silver halide grains without development nuclei are converted to soluble silver complex salts, which are transferred to the image-receiving layer where they form a silver border, usually in the presence of physical development nuclei.

Negative photography using direct positive silver halide photographic materials
In this type of silver complex diffusion transfer process, a transferred silver image is produced in the exposed areas, resulting in a negative transferred image with respect to the original.

Negative photography using direct positive silver halide photographic materials
As an application field of the type silver complex diffusion transfer method, there is a negative type direct offset printing plate, for example, Japanese Patent Application Laid-Open Nos. 52-106902, 52-112402, 53-21601, and 54-49203. It is stated in the specification of etc. However, there is no description of a negative type silver complex salt diffusion transfer method using a high-sensitivity direct positive silver halide photographic material for flash exposure.

Another field of application is the DTR method for reproducing documents or preparing printing materials; for example, U.S. Pat.
, 531,290, JP-A-58-18628, etc.

However, there is no description of a negative type silver complex salt diffusion transfer method using a high-sensitivity direct positive silver halide photographic material for flash exposure.

There are many aspects of the high-intensity reciprocity law failure characteristics of direct positive silver halide photographic light-sensitive materials that have not been elucidated, and there are many differences in the photographic properties at low-intensity exposure. In the silver complex diffusion transfer method using direct positive silver halide photographic materials,
Further complicating factors are involved.

For example, there were many unknown points, such as the re-inversion characteristic (characteristic in which the density decreases as the exposure amount increases) on the high exposure side. The present inventor has repeatedly studied various aspects of the silver complex diffusion transfer method using a direct positive silver halide photographic light-sensitive material.

(C) Object of the Invention One object of the present invention is to provide a negative type silver complex salt diffusion transfer method using a high-sensitivity direct positive silver halide photographic light-sensitive material for flash exposure.

Another object of the present invention is to provide a negative flash exposure
Our goal is to provide a type of direct offset printing plate.

Another object of the present invention is to provide a DTR method for producing negative type printing material for flash exposure.

Another object of the present invention is to develop a negative type silver complex diffusion transfer method using a high-sensitivity direct positive silver halide photographic light-sensitive material compatible with a flash light source having an emission wavelength in the wavelength range of 600 to 700 nm. It is about providing.

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 inventor conducted various studies and discovered that the following structure is preferable. Namely, for a light-sensitive material for silver complex diffusion transfer, 10- In a silver complex diffusion transfer method in which an image is formed by high-intensity exposure for 3 seconds or less, the light-sensitive material for silver complex diffusion transfer contains at least one direct positive silver halide emulsion layer, a. The silver halide emulsion consists of silver halide grains containing about 80 mol % or more of chloride, b. The silver halide emulsion grains have a spectral sensitization peak of 600 to 700
This is a silver complex salt diffusion transfer method characterized in that a sensitizing dye having a wavelength of nm is adsorbed, and c. the surface of the silver halide emulsion grains is substituted with bromide.

The sensitizing dye used in the present invention has a spectral sensitization peak of 600 to 7 when adsorbed to silver halide grains.
00 nm.

The sensitizing dye used in the present invention is
The optically sensitized electron acceptor described in No. 307 is preferred.

The sensitizing dye used in the present invention has the following general formula [I
] is preferable.

(Space below) Rz R4 (Xe)q General formula (I) Here, R1, R2, R3, and R4 are alkyl groups (e.g., methyl, ethyl, propyl, etc.) substituted alkyl groups (e.g., γ-sulfopropyl, β -sulfobutyl, etc.), alkenyl groups (e.g., allyl, propenyl, butyryl, etc.), or aryl groups (e.g., phenyl, p-tolyl, p-methoxyphenyl, p-ethoxyphenyl, p-
chlorophenyl, etc.). R5, Re, R? and R
8 is a hydrogen atom or a halogen atom (for example, a chlorine atom,
bromine atom, etc.). X represents an anion, preferably an acid anion such as chloride, bromide, iodide, p-toluenesulfonate, thiocyanate. q is O or 1; when q is 0, an inner salt is formed.

The sensitizing dye used in the present invention is as follows - Bottom (II
) is preferable.

R2(Xe)q General formula (II) Here, Q represents an atomic group necessary to complete the nucleus to make the trimethine cyanine dye, and is a benzothiazole nucleus (e.g. benzothiazole, 6-nitropenzothiazole). Pyrrolo[2,3-b]pylidene nucleus, for example (where R11 and Rlz represent an alkyl group, R1
3 represents an alkyl group or a substituted alkyl group. ) etc. are preferred.

R1, R2, R5, R6 and X are synonymous with -bottom (I).

The sensitizing dye used in the present invention is as follows - Bottom (II
A compound represented by I) is preferred.

Re Rlo (Xe)q-bottom (III) Here, A and A1 represent an aryl group, R9 and R
lo represents an alkyl group or a substituted alkyl group, and Y represents a hydrogen atom or an aryl group.

Specific examples of the sensitizing dyes used in the present invention are listed below.

(The following are blank spaces) (a-'1) (b-1> (b-2) (c-1> (c-2) The amount of the sensitizing dye used in the present invention is per mole of silver halide, '+omy~2g, preferably 1o
It ranges from omy to 1 g. The sensitizing dye is preferably added before the surfaces of the silver halide emulsion grains are replaced with bromide.

The silver halide emulsion used in the present invention is composed of silver halide grains containing about 90 mol% or more of chloride, which adsorbs a sensitizing dye, and coats the surface of the silver halide grains with bromide. It has been replaced.

The bromides used in the present invention include sodium bromide,
Water-soluble bromides such as potassium bromide.

The amount of bromide used in the present invention is preferably set so that when added, the EAg of the silver halide emulsion is 60rIIV or less, and is 0.03 mol to 0.03 mol per mol of silver halide. A range of 2 moles is preferred.

For other halides, such as chloride, fluoride, E
It is virtually difficult to cause Ag601'1 vomiting, and iodide does not increase sensitivity at high illuminance.

EAg represents the silver potential when a silver chloride electrode is used as a comparison electrode. When EAg exceeds 60IIIV, sensitivity decreases at high illuminance.

Hydrophilic binders advantageously used for preparing light-sensitive emulsions include lime-treated gelatin, acid-treated gelatin, gelatin derivatives (e.g., Japanese Patent Publication Nos. 38-4854, 1983-
No. 5514, No. 12237 of 1972, No. 26 of 1972
No. 345, U.S. Patent No. 2,525.753, U.S. Patent No. 2,
No. 594,293, No. 2,614,928, No. 2
, 763.639, 3,118,766, 3,132,945, 3,186,846, 3,312,553, British Patent No. 861.414, 1,033,189), proteins such as albumin and casein, cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose, agar, natural polymers such as sodium alginate, polyvinyl alcohol, poly-N-vinyl Synthetic hydrophilic binders such as pyrrolidone, polyacrylic acid copolymers, polyacrylamide or derivatives thereof, and partially hydrolyzed products include synthetic hydrophilic binders, and these hydrophilic binders can be used alone or in combination. These hydrophilic binders are also advantageously used to create non-photosensitive layers such as antihalation layers, interlayers, protective layers (or release layers), backing layers or image-receiving layers.

The binder in the silver halide emulsion layer is used in a weight ratio of 0.3 to 5, preferably 0.5 to 3, based on silver halide converted to silver nitrate.

The silver halide emulsion used in the present invention has a suitable fog on the surface of the silver halide grains, but this is achieved by using a reducing agent alone or a reducing agent and a gold compound in combination. fog is applied.

In the present invention, reducing agents used to impart fog to silver halide include aldehyde compounds such as formalin, organic amine compounds such as hydrazine, triethylenetetramine, thiourea dioxide, and imino-amino-methanesulfinic acid. Inorganic reducing agents such as stannous chloride, or reducing agents such as amine borane are preferably used.

In the present invention, examples of the gold compound used to impart fog to silver halide include potassium chloroaurate,
Chloroauric acid, thiocyanate plating, etc. are preferably used.

The direct positive silver halide emulsion of the present invention can be produced using the above method and a sulfur-containing compound (e.g., sodium thiosulfate, potassium thiosulfate, allylthiourea, etc.) or a thiocyanate compound (e.g., potassium thiocyanate, thiocyanate). It can also be suppressed by combining with ammonium (ammonium, etc.).

In the present invention, an electron acceptor is characterized by its polarographic half-wave potential, ie its redox potential determined polarographically. Electron acceptors useful in the present invention are those for which the sum of polarographic anodic potential and polarographic cathodic potential is positive. Regarding the method of measuring the redox potential, see, for example, U.S. Patent No. 3,50
No. 1,307.

A particularly effective electron acceptor for use in the present invention is the imidazo(4,5-b)quinoxaline cyanine dye described in Belgian Patent No. 660,253. Another particularly effective electron acceptor is U.S. Pat.
．． This is an indole cyanine dye having an aromatic substitution at the 2-position and is described in specifications such as No. 314,796 and No. 3,505,070.

In the present invention, the electron acceptor is preferably used at a concentration ranging from 0.19 to 2.09 per mole of silver halide. More preferably, the concentration is in the range of 0.2g to 0.6g. Specific examples of electron acceptors used in the present invention include 1.1"-dimethyl-2,2'-
Diphenyl-3,3-introcarpocyanine bromide, 2,2-di-p-methoxyphenyl-1,1
--Dimethyl-3,3'-introcarbocyanine bromide, 1,1'-dimethyl-2,2',8-triphenyl-3,3=-indolocarbocyanine verchlorate, 1,3-diallyl -2-(2-(9-methyl-
3-carbazolyl)vinyl]imidazo(4,5-b)quinoxalium p-toluenesulfonate, 1,3-diethyl-1--2-phenyl imidazo(4,5-b)
Quinoxalino 3--introcarbocyanine iodide, 1.1-, 3,3-tetraethylimidazo (4,5-b) quinoxalinocarbocyanine chloride, 1,1'', 3,3-tetramethyl -2-phenyl-3-indropyrrolo(2,3-b)pyridocarbocyanine iodide, 1. lower.

3.3.3',3'-hexamethylpyrrolo(2,3-
b) Pyridocarbocyanine verchlorate, 1,1”
3゜3-tetramethyl-5-nitro-2'-phenylindo-3'-indocarbocyanine iodide, 1
．． 1''3,3.3',3'-hexamethyl-5
, 5-dinitroindocarbocyanine P. toluenesulfonate, 3'-ethyl-1-methyl-2-phenyl-6-m: Tolo 3-indrothiacarbocyanine P
-Toluenesulfonate, pinacryptol yellow, 5-m-nitrobenzylidene-rhodanine, 5-m-nitrobenzylidene-3-7enylrhodanine, 1,3-
Examples include iodide of diethyl-6-nitrothia 2'-cyanine iodide.

The direct positive silver halide emulsion of the present invention may contain stabilizers, development accelerators, brighteners, color couplers, surfactants, hardeners, post-dye improvers, thickeners, etc., as necessary. can be included.

The direct positive silver halide emulsions of the present invention can be applied to a suitable support such as glass, cellulose acetate film, polyethylene terephthalate film, paper, baryta coated paper, polyolefin (e.g. polyethylene, polypropylene, etc.) coated paper. applied on top. These supports are
It may be corona treated by a known method, and if necessary, it may be undercoated by a known method.

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

Furthermore, when the direct positive 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-mentioned black pigment and white pigment.

Various additives may be contained in the constituent elements of the diffusion transfer material according to the present invention.

For example, mercapto compounds, antifoggants 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, mordants such as tertiary amine compounds, diacetyl cellulose, styrene-fluoroalkylene sodium maleate copolymers, styrene-
Antistatic agents such as alkali salts of the reaction product of anhydrous mylene public polymer and P-aminebenzenesulfonic acid, matting agents such as polymethacrylic esters, polystyrene, colloidal silicon oxide, acrylic esters, and various latexes. Film property improvers, styrene-maleic acid copolymers, thickeners such as those disclosed in Japanese Patent Publication No. 36-21574, antioxidants, developing agents, pH adjusters, etc. can be used.

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.

By providing a layer consisting of a direct positive silver halide emulsion on a suitable support and further providing a surface layer containing physical development nuclei consisting of fine particles of heavy metals or their sulfides, negative and A type of direct offset printing plate is obtained. When this direct offset printing plate is imagewise exposed and developed, the silver halide in the unexposed areas is reduced to silver, but the silver halide in the exposed areas becomes a silver complex salt and dissolves, forming an upper layer. It diffuses and is reduced and precipitated using physical development nuclei as catalyst nuclei, forming a silver image. The areas where the silver image is not exposed are made of protective colloids such as gelatin, polyvinyl alcohol, etc. and are hydrophilic, but the exposed areas of the silver image are lipophilic due to the precipitated silver. It has ink affinity.

As physical development nuclei, known ones such as metals such as antimony, bismuth, cadmium, cobalt, palladium, nickel, silver, lead, and zinc, and their sulfides can be used. The image-receiving layer contains one or two hydrophilic colloids such as gelatin, carboxymethyl cellulose, gum arabic, sodium alginate, hydroxyethyl starch, dextrin, hydroxyethyl cellulose, polystyrene sulfonic acid, a copolymer of vinylimidazole and acrylamide, and polyvinyl alcohol. It may contain more than one species. The hydrophilic colloid contained in the image-receiving layer is preferably 0.5 g/TIi or less.

Hygroscopic substances such as humectants such as sorbitol, glycerol, etc. may be present in the image-receiving layer. In addition, the image-receiving layer may contain pigments for preventing scumming such as barium sulfate, titanium dioxide, china clay, and silver, developing agents such as hydroquinone, and hardening agents such as formaldehyde and dichloro-8-triazine. .

Physical development nuclei, such as heavy metals such as nickel, cobalt, palladium, gold, silver, or their sulfides, are present in one or more layers of the image-receiving material used in the DTR method for document reproduction or for the preparation of printing materials. It can include things. In one or more layers of the image-receiving material, substances which play a significant role in the formation of the diffusion transfer image, such as black toners such as those described in British Patent No. 561,875 and Belgian Patent No. 502,525, e.g. -Phenyl-5-mercaptotetrazole may be included.

The image-receiving material may also contain a fixing agent such as sodium thiosulfate in an amount of about α1 to about 49/d.

The processing liquid used in the diffusion transfer method contains alkaline substances,
For example, sodium hydroxide, potassium hydroxide, lithium hydroxide 1. silver halide solvents such as sodium triphosphate, sodium thiosulfate, ammonium thiothianate,
Cyclic imide compounds, thiosalicylic acid, etc., preservatives, such as sodium sulfite, IJ agents, such as hydroxyethylcellulose, carboxycellulose, anti-capri agents,
For example, potassium bromide, 1-phenyl-5-mercaptotetrazole, etc., development modifiers, such as polyoxyalkylene compounds, onium compounds, developing agents, such as hydroquinone, 1-phenyl-3-pyrazolidone, etc., alkanolamines, etc. can be included. .

The present invention will be explained below with reference to examples, but the present invention is not limited thereto.

Example 1 While keeping an aqueous solution of inert gelatin at 60°C and stirring vigorously, 4 ml of an aqueous sodium chloride solution and an aqueous silver nitrate solution were added at the same time.
A silver chloride emulsion was prepared by adding at an addition rate of d/min. These emulsion grains have an average size of 0.3
μ, the crystal habit was cubic, and more than 90% of all particles were within ±30% of the average particle size.

The emulsion thus obtained was precipitated and washed with water in a conventional manner, then redissolved, and a gelatin solution was added to adjust the weight ratio of gelatin to eye to 1:1.

Next, add 7 m of potassium iodide solution to a ratio of 0.01 mole/mole Aa, pH 6.5, EA.
(II wo 230 IIlvk: After adjustment, thiourea dioxide and potassium chloroaurate were added, and the mixture was aged at 60° C. for 90 minutes to turn it over.

After this, II was set to 5.5 and the following dye (a-1>300
ff15F/mole Ag and Hina Cliftol I Low 200! Add IIg/mole Ag, add a potassium bromide aqueous solution equivalent to 8.5 mol%/mole Ag, and turn off the EAO to 5 mV. E.A.
G、Measure at 40℃.

Next, a hardener and a surfactant were added and the pH was adjusted to 6.5.

A gelatin layer necessary for curl control is provided on one side of the 100 μm polyethylene terephthalate film (PET) shown below, and 0.3 g/Trt of carbon black for antihalation is contained in this layer. (@
surface).

Next, an undercoat layer containing 10 g/T/i of titanium oxide and 3.0 g/m of gelatin is provided on the other side, and the above made-up emulsion is coated on the undercoat layer with an amount of silver of 1.3 g/Trt and gelatin coated. An emulsion layer was formed by coating at an amount of 1.49/m.

A palladium sulfide sol prepared by the method described below was applied onto this emulsion layer.

Preparation of palladium sulfide sol Palladium chloride 59 Liquid A Hydrochloric acid 40d Water 11 Sodium sulfide 8.6g Liquid B Water 11! Liquids A and B were mixed with stirring, and after 80 minutes, they were purified by passing through a column containing an ion exchange resin made for pure water production, and liquid C was added to prepare a coating liquid. (Adjusted to pH 4) Polyvinyl alcohol 10g (10% liquid) C liquid Polymer No.3 3y10% saponin aqueous solution described in JP-A-53-21602 20ml water
181 The sample obtained in this way is used as a sample (
1).

As a comparison sample, an emulsion containing mainly silver bromide was prepared as follows.

While keeping an aqueous solution of inert gelatin at 60°C and stirring strongly, add 4 m of a potassium bromide aqueous solution and a silver nitrate aqueous solution at the same time.
A silver bromide emulsion was prepared by adding at an addition rate of ff/min. These emulsion grains have an average size of 0.
3μ, crystal habit is cubic, 90% by weight of all particles
The above particles were within ±30% of the average particle size.

The emulsion thus obtained was precipitated and washed in a conventional manner, then redissolved, and a gelatin solution was added to adjust the weight ratio of gelatin to eye to 1:1.

Next, the potassium iodide aqueous solution was processed to have a ratio of 0.01 mole/mole Ag, the pH was adjusted to 6.5, and EAg was 2
The temperature was adjusted to 30 II lv, thiourea dioxide and potassium chloroaurate were added, and the mixture was aged at 60'C for 90 minutes to turn over.

After this, the pH was adjusted to 5.5, and 300ff of the following dye (a) was added.
ig/mo 10Ag and Pinacryptol Yellow 20Qmy/mole A! IJ was added, and an aqueous potassium bromide solution was added to adjust the EA() to 5 mV. Next, a hardening agent and a surfactant were added to adjust the pH to 6.5.

Samples were prepared in the same manner and used as comparison (a).

(Margins below) Thus, the obtained sample (1) and comparison (a) were cut into appropriate sizes, and exposed through a wedge with a density difference of 0.15 for low-light exposure (1 second) and high-light exposure. Exposure (104 seconds)
After that, development was performed at 30'C for 1 minute using a silver complex diffusion transfer developer having the following composition.

Silver complex diffusion transfer developer water 750r
r11 Sodium hydroxide 15g Anhydrous sodium sulfite 509 Hydroquinone 10g 1-phenyl-3-pyrazolidone 1g Sodium thiosulfate
15g potassium bromide Make 11 with 1g water.

After development, the film was treated with a neutralizing solution having the following composition at 25° C. for 20 seconds, excess solution was removed using a squeezing roller, and the film was dried at room temperature.

Neutralized liquid water 600
d Citric acid 10g Sodium citrate 35g Colloidal silica (20% liquid) 5rr11 Niletine glycol
Add 5d water to bring the total volume to 11.

The results of sensimetry of the sample thus obtained are shown in Table 1.

The relative sensitivity referred to here is the relative value of the reciprocal of the exposure value at the boundary point where no precipitated silver is present.

As is clear from Table 1, Sample (1), which is an embodiment of the present invention, has less high-intensity failure than Comparative (A), and even with high-intensity exposure of 10-3 seconds or less, It had favorable properties.

Sample (1) and comparison (a) were subjected to scanning exposure using a helium laser light source, and developed with the above silver complex salt diffusion transfer developer at 30'C for 1 minute to neutralize the sample (a). The sample was treated with liquid for 20 seconds at 25°C, excess liquid was removed using a squeezing roller, and the sample was dried at room temperature.

Next, when printing was carried out in the same manner as described in Example 1 of the specification of Japanese Patent Publication No. 61-23546, the comparison (A) was 500.
Samples (1.5 or less) cause deterioration of the printed image;
), no deterioration of the printed image occurred after 2000 copies.

The spectral sensitization peak of sample (1) is about 69 onm
Met.

From this example, it was found that sample (1), which is an embodiment of the present invention, is preferable as a negative type direct offset printing plate for flash exposure.

Example 2 Sample (2) and comparison (b) were prepared in the same manner as in Example 1, except that dye (b-1> was used instead of dye (a)), and the same treatment was carried out thereafter. The results shown in Table 2 were obtained.

C113C1”+3 cgo.

Dye (b-1> As is clear from Table 2, sample (2), which is the actual tM embodiment of the present invention, has less high-intensity failure than the comparison (b), and has a high-intensity failure of 10-3 seconds or less. It also had favorable characteristics with respect to illuminance exposure.

Hereinafter, a printing test was conducted in the same manner as in Example 1, and it was found that in comparison (B), the printed image deteriorated after 500 copies or less, whereas in sample (2), the printed image did not deteriorate after 2000 copies. It did not occur.

The spectral sensitization peak of sample (1) was about 650 nm.

From this example, sample (2) which is the actual tM embodiment of the present invention
has been found to be preferred as a negative type direct offset printing plate for flash exposure.

Example 3 An emulsion was prepared in the same manner as in Example 1 except that dye (C-1) was used instead of dye (a>).

A gelatin layer necessary for curl control was provided on one side of the polyethylene-laminated paper.

(Back side).

Next, an undercoat layer was provided on the other side by adding 10 g of titanium oxide/TIt, 39/TIt of gelatin, and carbon black so that the reflection density of the undercoat layer was 0.2. Silver FF11.
An emulsion layer was formed by coating the gelatin at a coating amount of 0 g/TIt and a coating amount of 2.5 y/m. In this way, sample (3), which is a light-sensitive material for diffusion transfer, was produced.

Next, a comparison (c) was produced in the same manner as in Example 1.

r dye (c-1>) The thus obtained sample (3) and comparison (c) were cut into appropriate sizes, passed through a wedge with a density difference of 0.15, and exposed to low light (1 second) and high light. Illuminance exposure (10 seconds) was carried out. Mitsubishi Paper Mills One Step Developer AD was put into Mitsubishi Paper Mills One Step Processor S■, and
The exposed sample (3) and comparison (c) were kept at .degree. C. and passed through one-step IP (image receiving material li+) manufactured by Mitsubishi Paper Mills Co., Ltd., and peeled off after 30 seconds.

Table 3 shows the results of sensitometry of the sample thus obtained.
It was shown to.

(The following is a blank space) Table 3 The spectral sensitization peak of sample (3) was approximately 660 nm.

As is clear from Table 3, sample (3), which is an embodiment of the present invention, has fewer high-intensity failures than the comparison (c), and has 1
It also had favorable characteristics for high-intensity exposure of 0-3 seconds or less.

From this example, sample (3), which is an embodiment of the present invention, is a negative type D for preparing a plate for flash exposure.
It was found that this method is preferable as the TR method.

Example 4 This example shows the effect of bromide.

Comparison (d) was prepared in the same manner as in Example 3, except that an aqueous potassium chloride solution was added instead of an aqueous potassium bromide solution. The EAg of the above emulsion was 125IlIv.

The sample thus obtained was treated in the same manner as in Example 3 to obtain the results shown in Table 4.

As is clear from Table 4, the sensitivity of Comparison (d) is low even when exposed to low illuminance, but when exposed to high illuminance, the illuminance becomes even lower, compared to sample (3) which is an embodiment of the present invention. is a big difference.

From this example, it was found that sample (3), which is an embodiment of the present invention, is preferable as a negative tear DTR method for preparing a plate for flash exposure.

Claims (5)

[Claims] (1) For photosensitive materials for silver complex diffusion transfer, 10^-^3
In the silver complex diffusion transfer method in which an image is formed by performing high-intensity exposure for less than a second, the light-sensitive material contains at least one direct positive silver halide emulsion layer, and a. consisting of silver halide grains containing 80 mol% or more of chloride; b. A sensitizing dye having a spectral sensitization peak of 600 to 700 nm is adsorbed onto the silver halide emulsion grains; c. The halogenated A silver complex salt diffusion transfer method characterized in that the surface of silver emulsion grains is substituted with bromide. (2) The silver complex salt diffusion transfer method according to claim 1, wherein the sensitizing dye is a compound represented by the following general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [I] (Here, R_1, R_2, R_3, R_4 represent an alkyl group, substituted alkyl group, alkenyl group, or aryl group, R_5, R_6, R_7, R_8 represents a hydrogen atom or a halogen atom, X represents an anion, and q
represents 0 or 1. ) (3) The silver complex salt diffusion transfer method according to claim 1, wherein the sensitizing dye has the following general formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] (Here, Q represents the atomic group necessary to complete the aromatic ring nucleus to make the trimethine cyanine dye. R_1,
R_2, R_5, R_6 and X have the same meanings as in general formula [I]. ) (4) The silver complex diffusion transfer method according to claim 1, wherein the sensitizing dye has the following general formula [III]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [III] (Here, A, A_1 represent an aryl group, R_9, R
_1_0 represents an alkyl group or a substituted alkyl group,
Y represents a hydrogen atom or an aryl group. ) (5) EAg of the silver halide emulsion at 40°C is 60^m
^V or less, the silver complex salt diffusion transfer method according to claim 1.