JPH06295043A - Image receiving material for silver complex salt diffusion transfer - Google Patents

Abstract

PURPOSE:To provide an image receiving material for silver complex salt diffusion transfer having strong image intensity in the image receiving layer and high max. reflection density in a picture image part. CONSTITUTION:The image receiving material for silver complex salt diffusion transfer has at least one image receiving layer containing physical developing nuclei. The image receiving layer containing physical developing nuclei and/or a water-permeable hydrophilic colloid layer contain a compd. expressed by formula I and/or formula II and an org. solvent of high boiling point. In formulae, R is an alkyl group or aryl group and R1 is an alkyl group or aralkyl group. X<-> is an anion and when R1 contains a sulfo group or carboxyl group, X<-> is not present. R2-R5 are hydrogen atoms, alkyl groups, alkenyl groups or alkoxy groups and R2-R5 may be same or different. Or, R2 and R3, or R3 and R4 may be connected to form carbon rings. R6 is a n-valent residue bonded to a carbonyl carbon which forms carboxylic acid ester with carbon atoms or nitrogen atoms.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver complex salt diffusion transfer image receiving material in which a light-sensitive material and an image receiving material are combined.

[0002]

The silver complex salt diffusion transfer method generally comprises a light-sensitive material having a silver halide emulsion layer as a light-sensitive layer formed on a support and an image-receiving material having an image-receiving layer containing physical development nuclei formed on the support. It is composed of a processing solution containing a silver halide solvent. The principle of the silver complex salt diffusion transfer method is that the silver halide in the exposed area of the exposed photosensitive layer is developed by the processing solution or the developing agent in the photosensitive material, and at the same time the silver halide in the unexposed area is halogenated in the processing solution. It reacts with a silver solvent to form a soluble silver complex salt, diffuses into the image receiving material, and is deposited on physical development nuclei in the image receiving layer to form a silver image.

The silver complex salt diffusion transfer method based on such a principle is widely used for copying documents, and further as a plate material for plate making work. As the important quality of the image receiving material used in the silver complex salt diffusion transfer method, the silver image density (reflection and transmission density) is high, the color tone (reflection and transmission) is good (generally blue-black tone is desired), and the image receiving layer is Has a sufficient film strength and a high diffusion transfer rate.

Particularly, the film strength (image strength) of the image receiving layer is a very important quality. In recent years, there has been a demand for rapid processing of photographic materials, and therefore improvements are being made in response to the rapid processing of photographic materials themselves and improvements of processing solutions suitable for such photographic materials. For example, the amount of gelatin in photographic materials is reduced from the point where the rapid penetration of processing solutions is aimed,
Further thinning has been performed, but this not only deteriorates the physical properties of the coating, but also increases fog.
Accordingly, high-temperature short-time processing using an automatic processor or a powerful processing liquid has come into widespread use, and there is a demand for coating physical properties that are strong in mechanical strength and do not impair photographic characteristics.

Further, the silver image density (reflection and transmission density) is a very important quality, and in order to properly reproduce the image quality (fine lines and mesh) when used as a block material, the image density must be high. Is said to be desirable. Furthermore, the fact that the color tone of a silver image is blue-black is also a very important quality in recent years.

As a hardener which does not cause the above-mentioned various defects, JP-A-56-36645 and 59-203.
There are quaternary pyridinium compounds described in No. 69. These compounds not only have the above disadvantages,
It has been found that when it is used as a hardener for an image receiving material in the silver salt diffusion transfer method, the color tone and maximum density of the image area are significantly improved.

Further, JP-A-3-26044 and JP-A-4-26044
As described in JP-A-243248, the use of the compound represented by Chemical Formula 1 and / or Chemical Formula 2 as a hardener for gelatin gives a transferred image having improved color tone, maximum density, contrast and sharpness. It is known, but it cannot be said that the film strength of the image receiving layer (image strength) is sufficient.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver complex salt diffusion transfer image receiving material having a high image strength of the image receiving layer and a high maximum reflection density in the image area.

[0009]

SUMMARY OF THE INVENTION The above-mentioned object of the present invention is to image-wise expose a light-sensitive material having a silver halide photographic emulsion layer and develop the exposed emulsion layer with an alkaline processing solution containing a silver halide emulsion. , An image receiving material containing an image receiving layer containing physical development nuclei, in which a silver complex salt is diffused to form a silver transfer image in the layer, a compound represented by the following general formula 3 and / or It is achieved by containing a boiling-point organic solvent in the image-receiving layer containing physical development nuclei and / or the water-permeable hydrophilic colloid layer.

[0010]

[Chemical 3]

[0011]

[Chemical 4]

(In the formula, R represents an alkyl group or an aryl group.
And R₁ Represents an alkyl group or an aralkyl group, and R₁ But
In the case of a group containing a sulfo group or a carboxyl group, X^- 
Does not exist. X^- Indicates an anion. R₂ , R₃ , R
_Four And R_Five Are hydrogen atom, alkyl group and alkenyl group respectively.
Alternatively, it represents an alkoxy group. R₂ , R₃ , R_Four And R_FiveIs
May be the same or different from each other, or R
₂ And R₃ Or R₃ And R _Four And are linked together to form a carbocycle.
May be made. R₆ Is a carbon atom or a nitrogen atom
Bond to the carbonyl carbon forming the borate ester
Indicates the n-valent residue. n is 2, 3 or 4, m is 0 or
Indicates 1. )

The alkyl group represented by R in Chemical Formulas 3 and 4 may be linear or branched, and may be further substituted with an appropriate group (eg, halogen, alkoxy group, etc.). Preferably, it has 1 to 10 carbon atoms,
For example, methyl, ethyl, n-propyl, n-hexyl,
Aryl group such as trichloromethyl, phenyl group,
Aromatic groups such as naphthyl groups are preferred, and these aromatic groups may be substituted with a suitable group (eg halogen, alkyl group, nitro group, etc.).

The alkyl group represented by R ₁ may be linear or branched, and may be further substituted with a suitable group (eg, sulfo group or carboxyl group). Preferably, it has 1 to 10 carbon atoms, for example, methyl, ethyl, n-propyl, n-hexyl, carboxymethyl, sulfopropyl, etc., and the aralkyl group may be linear or branched. Well, it may be further substituted with a suitable group (eg, sulfo group, carboxyl group). It is preferably a group having 7 to 15 carbon atoms, for example, benzyl, phenethyl, phenylpropyl, 2-carboxybenzyl, etc. However, when R ₁ is a group containing a sulfo group or a carboxyl group, X ⁻ does not exist.

X ^- represents an anion, preferably a halogen ion, an alkyl sulfonate or an aryl sulfonate. The alkyl group represented by R ₂ , R ₃ , R ₄ and R ₅ may be linear or branched, and preferably has 1 to 10 carbon atoms, such as methyl, Ethyl, n-propyl, i-propyl, n-
An alkenyl group such as butyl, tert-butyl, n-hexyl and the like may be linear or branched and preferably has 1 to 8 carbon atoms, for example, allyl, butenyl, octenyl and the like. is there. Examples of the alkoxy group include methoxy, ethoxy, n-propoxy,
Examples include n-butoxy, n-octoxy, benzyloxy and the like. When R ₂ and R ₃ or R ₃ and R ₄ are connected to each other to form a carbocycle, examples of the carbocycle include a benzene ring or a condensed ring having 8 to 14 members, preferably a naphthalene ring. To be Substituents may be bonded to these carbocycles.

Among the compounds represented by Chemical formulas ₃ and ₄ , as the compound used in the present invention, it is particularly preferable that R ₂ , R ₃ , R ₄ and R ₅ are all hydrogen atoms or R ₂ and R _3. Alternatively, R ₃ and R ₄ may be linked to each other to form a benzene ring.

Examples of R ₆ include alkylene (ethylene, propylene, 1,2-dimethylethylene, tetramethylene, octamethylene, etc.), alkenylene (vinylene, ethynylene, propenylene, etc.), cycloalkylene (1,3-cyclopentyl, etc.). Len, 1,4-cyclohexylene, etc.), arylene (m-phenylene, p-phenylene, 1,3-naphthylene, etc.), alkylenediimino (tetramethylenediimino, hexamethylenediimino, etc.),
Examples include 1,4-cyclohexylene diimino and 1,3-phenylene diimino.

Specific examples of the compounds represented by Chemical formulas 3 and 4 used in the present invention are shown below, but the compounds used in the present invention are not limited thereto.

[0019]

[Chemical 5]

[0020]

[Chemical 6]

[0021]

[Chemical 7]

[0022]

[Chemical 8]

[0023]

[Chemical 9]

[0024]

[Chemical 10]

[0025]

[Chemical 11]

[0026]

[Chemical 12]

[0027]

[Chemical 13]

[0028]

[Chemical 14]

[0029]

[Chemical 15]

[0030]

[Chemical 16]

[0031]

[Chemical 17]

[0032]

[Chemical 18]

[0033]

[Chemical 19]

[0034]

[Chemical 20]

[0035]

[Chemical 21]

[0036]

[Chemical formula 22]

[0037]

[Chemical formula 23]

[0038]

[Chemical formula 24]

[0039]

[Chemical 25]

[0040]

[Chemical formula 26]

[0041]

[Chemical 27]

[0042]

[Chemical 28]

The compounds represented by Chemical formulas 3 and 4 used in the present invention are disclosed in JP-A-56-36645 and 59-2.
It can be synthesized very easily by referring to No. 0369.

The high-boiling organic solvent used in the present invention generally has a boiling point of 150 ° C. or higher, and is disclosed in US Pat. Nos. 2,322,027, 3,676,137 and 3,779. , 765, West German Patent No. 1,152,610
U.S. Pat. No. 1,272,561, JP-A-53-1
No. 520, No. 55-25057, and No. 45-37
Phthalic acid ester as described in No. 376,
Phosphoric acid esters can be generally used, but are not limited to these, for example, US Pat.
The amide compounds disclosed in Japanese Patent No. 416,923, benzoic acid esters, and substituted paraffins can also be used advantageously.

The high boiling point organic solvent used in the present invention is
May be used alone, but may be used in British Patent No. 1,072,915
It is preferable to dissolve a fluorescent whitening agent in a high boiling point organic solvent and to emulsify and disperse this in a hydrophilic colloid such as gelatin together with a surfactant as exemplified in the above publication. As the oil-soluble optical brightener used at this time, for example, substituted stilbenes and substituted coumarins described in British Patent No. 786,234 and substituted thiophenes described in US Pat. No. 3,135,762 are useful. And Japanese Patent Publication No. 45-37
Fluorescent brighteners such as those disclosed in JP-A No. 376 and JP-A No. 50-126732 can be used particularly advantageously.

When the hardener according to the present invention is added to a coating solution for forming a gelatin film, the addition amount thereof varies depending on the kind, physical properties, photographic characteristics, etc. of the target gelatin film, but is generally applied. 0.01 to 100% by weight of the amount of gelatin in a dry state, preferably 0.
It is 1 to 10% by weight.

The hardener according to the present invention has neither hygroscopicity nor decomposability, and therefore does not deteriorate even when stored at room temperature for a long period of time and has good solubility in water, alcohol and the like.

When the hardener according to the present invention is used in combination with the high boiling point organic solvent used in the present invention to act on the gelatin film in the image receiving material, effective hardenability is obtained without any loss of photographic characteristics. In addition, since there is very little post-hardening over time, an image receiving material with stable quality can be obtained, and
It imparts more effective stability without adversely affecting storage of the image-receiving material for a long period of time, and further provides excellent hardenability capable of withstanding even high-temperature rapid processing and automatic processing.

The hardener according to the present invention may be used alone, but if necessary, two or more kinds may be used in combination.

When the amount of the high boiling point organic solvent used in the present invention is too small, the film strength (image strength) of the image receiving layer when used in combination with the hardener according to the present invention is not sufficient, and when it is too large, an image is obtained. 50mg ~ 5 to reduce the maximum concentration of some parts
Most preferably, it is used in the range of 00 mg / m ² .

The layers to which the hardener according to the present invention and the high boiling point organic solvent are applied may be the same, but it is even more preferable that they are contained in different layers in a two-layer structure.

The gelatin to which the hardening agent according to the present invention is applied may be partially partly made of colloidal albumin, casein, carboxymethyl cellulose, hydroxyethyl cellulose or other cellulose derivatives, agar, sodium alginate starch derivatives or other sugar derivatives, synthetic. Hydrophilic colloids such as polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamides or their derivatives, partial hydrolysates, etc. can be substituted, and so-called gelatin derivatives, that is, contained in the molecule Amino group, imino group, hydroxy group, or carboxyl group as a functional group treated with a reagent having one group capable of reacting with them, modified, or bound to the molecular chain of another polymer substance It may be replaced with a graft polymer.

Any kind of silver halide such as silver chloride, silver bromide, silver iodobromide, silver chlorobromide, and silver chloroiodobromide can be used as a light-sensitive component in the silver halide photographic light-sensitive material. , Sensitization with salts of noble metals such as ruthenium, palladium, rhodium, platinum and gold, sulfur sensitization with sulfur compounds,
Various chemical sensitizations such as selenium sensitization with a selenium compound, reduction sensitization with a stannous salt, polyamine, or the like, or further sensitization with a polyalkylene oxide compound can be performed. Furthermore, cyanine dyes, which can be spectrally sensitized with merocyanine dyes, further triazole compounds, azaindene compounds, stabilizers such as benzothiazolium compounds, wetting agents such as dihydroxyalkanes,
Antistatic agents, ultraviolet absorbers, water-dispersible particulate polymer materials obtained by emulsion polymerization, hydroquinone and its derivatives, developing agents such as 1-phenyl-3-pyrazolidone and its derivatives, and saponins and polyethylene glycol lauryl ether. , Sodium dodecylbenzene sulfonate, Japanese Patent Publication Nos. 47-9303 and 48-43130.
A coating aid such as a fluorinated surfactant as described in JP-A No. 2000-242242, and various other known photographic additives can be added.

As the support of the photographic material used in the present invention, for example, paper, laminated paper, glass, films of cellulose acetate, polyester, polyamide, polystyrene and the like, sheets and the like can be used.

The processing solution for silver complex salt diffusion transfer in the present invention has a usual silver complex salt diffusion transfer processing solution composition, that is, a developing agent for developing exposed silver halide, such as hydroquinone and its derivative, 1- Undeveloped silver halide solvents such as phenyl-3-pyrazolidone and its derivatives, such as sodium thiosulfate, ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate, sodium sulfite as a preservative and potassium bromide as a development inhibitor. ,
Additives such as 1-phenyl-5-mercaptotetrazole as a toning agent, alkaline substances such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium triphosphate, thickeners such as carboxymethyl cellulose,
It can contain hydroxyethyl cellulose and the like.

[0056]

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

Example 1 <Preparation of high-boiling point organic solvent emulsion dispersion> Using n-dioctyl phthalate as the high-boiling point organic solvent, 8 g of the oil-soluble fluorescent whitening agent shown in Chemical formula 29 below was supplemented with n-dioctyl phthalate. A solution prepared by dissolving 200 ml of ethyl acetate as a solvent in 600 ml of 6% gelatin aqueous solution containing 1.5 g of sodium di (2-ethylhexyl) succinate as a solid content and about 60 ° C.
Were mixed with each other and stirred using a homogenizer to prepare an emulsified dispersion.

[0058]

[Chemical 29]

<Preparation of Physical Development Nuclei> Nickel nitrate, silver nitrate and sodium sulfide were reacted in equimolar amounts to prepare physical development nuclei consisting of nickel sulfide and silver sulfide in a 1% aqueous gelatin solution.

<Preparation of Image Receiving Material> The image receiving materials of Samples No. 1 and No. 7 were prepared as follows. Prepare the following coating liquid and adjust the pH
Was adjusted to 5.0 and kept at 40 ° C., 100 mg / m ^{2 of} the compound represented by Chemical formula 11 and 1.9 g / m ² of the above high boiling point organic solvent emulsified dispersion were added, and polyethylene was added on both sides. was coated with so that the hydrophilic colloid dry weight 2.1 g / m ² on one side of the paper support of the coated 110g / m ² dry.

Gelatin 21 g Water 300 ml Compound represented by Chemical formula 11 (10% aqueous solution) 10 ml Nuclear solution 40 ml High-boiling organic solvent emulsion dispersion 19 g Sodium dodecylbenzenesulfonate (5% aqueous solution) 10 ml (total 400 g)

Image receiving materials of Samples No. 2 to No. 6 and No. 8 and No. 9 were prepared as follows. 1 coated on both sides with polyethylene
An image-receiving layer was prepared by providing a gelatin image-receiving layer containing the above nuclei on one side of a 10 g / m ² paper support so that the dry weight of the hydrophilic colloid was 0.9 g / m ² . On the other hand, an aqueous gelatin solution containing 1-phenyl-5-mercaptotetrazole was applied so that the dry weight of the hydrophilic colloid would be 1.2 g / m ² to form the uppermost layer. The compound represented by Chemical formula 11 of the hardener was added to the solution before coating so as to be 100 mg / m ² and coated. The added layers are shown in Table 1. The high-boiling point organic solvent emulsified dispersion is 1.9 g / m ²
To each of the solutions before coating so that each coating solution was coated.
The added layers are shown in Table 1.

<Preparation of Light-Sensitive Material> As a light-sensitive material, an undercoat layer containing carbon black was provided as an antihalation layer on polyethylene laminated paper, and 0.35 μm was formed thereon.
Ortho-sensitized silver chlorobromide (silver bromide 5 mol%) having an average particle diameter of 1 was converted to silver nitrate and a gelatin silver halide emulsion layer containing 1.5 g / m ² of gelatin was provided. .
The silver halide emulsion layer is hardened by including a hardening agent so as not to hinder the diffusion transfer process.

<Treatment Liquid> The treatment liquid for diffusion transfer had the following composition. Water 800 ml Sodium hydroxide 25 ml Anhydrous sodium sulfite 100 ml Hydroquinone 20 g 1-Phenyl-3-pyrazolidone 1 g Potassium bromide 3 g Sodium thiosulfate 30 g 1-Phenyl-5-mercaptotetrazole 0.1 g Water is added to make 1000 ml.

The photosensitive material produced as described above is image-wise exposed, the emulsion surface and the image receiving surface of the photosensitive material are overlapped, and the resultant is passed through the processor having the squeezing roller containing the diffusion transfer processing liquid described above. After 30 seconds from the squeezing roller, both materials were peeled off. After washing the image-receiving material with water for 30 seconds, a cylindrical rubber with a diameter of 5 mm wrapped with absorbent cotton moistened with water is erected perpendicularly to the sample film surface, and a load of 300 g is applied to reciprocate the cylindrical rubber at a speed of 10 cm / sec. The mechanical strength was shown by examining the degree of damage to the sample image area when the sample was moved. The image receiving material was washed with water for 30 seconds and then dried, and the reflection density of the solid black portion was measured with a RD519 reflection densitometer manufactured by Masbeth. The results are shown in Table 1. Image strength (mechanical strength)
Was evaluated as follows according to the degree of damage to the sample image area. ◎ ・ ・ ・ No damage at all ○ ・ ・ ・ Slight damage occurs △ ・ ・ ・ Severe damage × ・ ・ ・ Great damage

[0066]

[Table 1]

It can be seen that Samples 1 to 6 having the constitution of the present invention have higher mechanical strength (image strength) and higher reflection density at the highest portion than Comparative Examples 7 to 9.

Example 2 Instead of the compound represented by Chemical formula 11 used as the hardener in Example 1, the compound represented by Chemical formula 6 was used, and bis (2-ethylhexyl) phthalate was used as the high boiling point organic solvent. Others were processed similarly to Example 1. The sample having the constitution of the present invention had higher mechanical strength (image strength) and higher reflection density at the highest portion than the comparative example.

[0069]

By using the present invention, it is possible to provide a silver complex salt diffusion transfer image receiving material in which the film strength (image density) of the image receiving layer is high and the maximum reflection density of the image area is high.

Claims (1)

[Claims] 1. An image-receiving material comprising an image-receiving layer containing physical development nuclei, which is obtained by image-wise exposing a light-sensitive material having a silver halide photographic emulsion layer, developing the exposed emulsion layer with an alkaline processing solution containing a silver halide solvent. In the image receiving material in which a silver complex salt is diffused into the layer to form a silver transferred image in the layer, a compound represented by the following general formula 1 and / or 2 and a high boiling point organic solvent are contained in the image receiving layer containing physical development nuclei. And / or a non-photosensitive hydrophilic colloid layer having a water-permeable relationship therewith, a silver complex salt diffusion transfer image-receiving material. [Chemical 1] [Chemical 2] (Wherein R represents an alkyl group or an aryl group, R ₁ represents an alkyl group or an aralkyl group, in the case of group R ₁ contains a sulfo group or a carboxyl group, X ^- is absent .X ^- Yin Indicates an ion: R ₂ , R ₃ , R ₄ and R ₅
Each represents a hydrogen atom, an alkyl group, an alkenyl group or an alkoxy group. R ₂ , R ₃ , R ₄ and R ₅ may be the same as or different from each other, or R ₂ and R ₃ or R ₃ and R ₄ may be linked to each other to form a carbocycle. Good. R ₆ represents an n-valent residue bonded to a carbonyl carbon forming a carboxylic acid ester with a carbon atom or a nitrogen atom. n is 2, 3 or 4, and m is 0 or 1. )