JPH01262541A - Image receiving element for silver salt diffusion transfer method - Google Patents

Abstract

PURPOSE:To make possible to form a continuous tone image having a good tone by incorporating a physical development nucleus substance prepared in a hydrophilic colloid solution contg. a fluorescence dyestuff, in the title element. CONSTITUTION:The image receiving element contains the physical development nucleus substance prepared in the hydrophilic colloid solution contg. the fluorescence dyestuff. The hydrophilic colloid solution usable for the preparation of the physical development nucleus is composed of a solution contg. 0.5-20wt.% of a hydrophilic colloid substance based on the solid matter. The amount of the fluorescence dyestuff used at the time of preparing the physical development nucleus is >=5wt.%, preferably 50-200wt.% based on the solid matter of the hydrophilic colloid substance. And, the concn. of the physical development nucleus is in a range of 1X10<-5>-1X10<-1>mol per 1l of a preparation solution of the nucleus. Thus, the continuous tone image having the good tone is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an image receiving element for use in silver salt diffusion transfer, and more particularly to a silver salt diffusion transfer image receiving element having improved image quality.

(Prior art) The principle of the silver salt diffusion transfer method is
It is stated in No. 4 etc. That is, in the silver salt diffusion transfer method, an imagewise exposed silver halide emulsion layer is placed in contact with, or brought into contact with, an image-receiving layer in the presence of a developing agent and a silver halide solvent. and convert the unexposed silver halide into a soluble silver complex. In the exposed parts of the silver halide emulsion layer, the silver halide is developed to silver so that it can no longer be dissolved and therefore cannot be diffused. In the unexposed portions of the silver halide emulsion layer, the silver halide is converted to soluble silver complexes which are transferred to the image receiving layer where they form a silver image, usually in the presence of physical development nuclei.

In a direct positive silver halide emulsion, the effects of exposed and unexposed silver halide are reversed.

The silver salt diffusion transfer method has a wide range of applications.

Among other things, in the process for producing printing materials it is necessary to obtain silver images of high maximum a degree, high contrast and sharpness in the image-receiving layer. Furthermore, the image reproduction characteristics, i.e., the characteristics of reproducing an image as faithful as possible to the original, are particularly important for originals that have a mixture of positive image lines i (black lines) on a white background and negative image lines (white 1tii) on a black background. It is extremely important to faithfully reproduce the ruled lines, or to reproduce a good halftone image by printing a continuous G4 original through a screen and performing diffusion transfer development.

Furthermore, in the silver salt diffusion transfer method, a continuous tone transferred silver image can be obtained depending on the design of the silver halide emulsion layer. In this case, richness of gradation and obtaining a neutral gray tone from the high agIL range to the low 1 degree range are important qualities.

It is well known that a toning agent is usually used in the image receiving element in the silver salt diffusion transfer method. For example, a representative example is 1-phenyl-5-mercagutotetrazole, a color toning agent described in Photographic Silver Halide Difference Process, published by Ichiriki Le Press, p. 61. However, these toning agents have the disadvantage of lowering transfer density and transfer speed. Furthermore, the use of known toning agents is hardly sufficient to obtain a neutral gray silver image from a low density range to a high a degree range in a continuous tone image.

The color tone of the transferred silver image also changes depending on the type of physical development nucleus. - Examples of physical development nuclei include heavy metals such as silver, gold, platinum, palladium, steel, cadmium, lead, cobalt, and nickel, or their sulfides and selenides. These physical development nuclear materials can be prepared by reducing the corresponding metal ions to create a metal colloid dispersion, or by mixing a metal ion solution with a soluble sulfide or selenide solution to form water-insoluble metal sulfides or metal selenides. It can be obtained by making a colloidal dispersion of Furthermore, even if metals, metal sulfides, or selenides of the same origin are formed, physical development nuclei with different physical properties such as shape are known to affect the color tone of transferred silver images. .

(Object of the Invention) The object of the present invention is to provide an image receiving g that provides a continuous tone image with good color tone.
! Dedicated to providing the basics.

Another object of the present invention is to provide a silver IIM image with a high maximum D11 degree, high contrast, high sharpness, and good color tone.
It is about providing the basics.

It is another object of the present invention to provide an image receiving element which provides a silver image with improved image reproduction characteristics.

Means for Solving the Problems The above objectives have been achieved by an image-receiving element characterized in that it contains a physical development nucleus material prepared in a hydrophilic colloid solution containing a fluorescent dye.

As a result of extensive research into improving color tone and image quality by methods for preparing physical development nuclei, the present inventors have found that good results can be obtained when a fluorescent dye is present during the preparation of physical development nuclei.

It is conventionally known that fluorescent dyes can be included in the image-receiving layer. However, fluorescent dyes are usually used only for the purpose of fluorescent whitening. The present invention is used to improve the image quality of transferred images, and the fluorescent dye used in such drainage alone is generally insufficient for the purpose of whitening the acupuncture layer. be.

The hydrophilic colloid solution used in the preparation of physical development nuclei of the present invention is a solution containing a solid content of the hydrophilic colloid substance from 0.5 to 20 mu. The most preferred examples of hydrophilic colloid substances include poly-N-vinylpyrrolidone or acrylamide-vinylimidazole copolymer, and combinations thereof, but other commonly used hydrophilic colloid substances such as gelatin, carboxymethylcellulose,
Diethyl cellulose in hydro, polyvinyl alcohol,
Polyacrylamide and the like can be used alone or in combination.

Fluorescent dyes include those commonly used and substances that can be used for the purpose of fluorescent whitening, such as bis(triazinylaminostilbene) disulfonic acid cast conductor, ogisazole'n4 body, trianol cast conductor, biphenyl soap. Water-soluble conductors such as imidazole 04 conductors, Kumari/-conductors, pyrazoline derivatives, and naphthalimide conductors are used. Preferably, compounds represented by the following general formulas (I) to (III) are used.

General formula (I) [wherein A1 and 2 each represent a hydrogen atom, a lower alkyl group, a hydroxyl group, a carboxyl group or a salt thereof, B1 and Bx each represent a hydrogen atom, (Bs and B4 each represent Represents a hydrogen atom, a hydroxyl group, or a substituted or unsubstituted lower alkoxy group, aryloxy group, polycyclic group, lower alkylthio group, arylthio group, thioheterocyclic group, or amino group.) -N HCOB s group (Bi represents a substituted or unsubstituted lower alkoxy group, aryl group, aryloxy group, heterocyclic group, lower alkylthio group, thioheterocyclic group, or amino group, respectively.) 9 represents a group of nonmetallic atoms necessary to form an unsubstituted aromatic ring, and 9 represents a hydrogen atom or a substituted or unsubstituted lower alkyl group. ] General formula (II) [In the formula, C1 and C! each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a sulfonyl group or a salt thereof, or a carboxyl group or a salt thereof, ]), sp and Ih each represent f
f1fi or unsubstituted diphenyl group, α-su7ter group, β-naphthyl group or i or a salt thereof, or a carboxyl group or a salt thereof, H4 is a hydrogen atom, ), rogen atom, lower alkyl group,
or a lower alkoxy group, Ds represents a hydrogen atom or a lower alkyl group. ) is expressed by the general formula (ill ”
) E I Es (where E, gg and B4 are each a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group or a salt thereof, a sulfonyl group or a salt thereof, or a substituted or unsubstituted lower alkyl group) and lower alkoxy groups, and zl and Z! each represent a group of nonmetallic atoms necessary to form a substituted or unsubstituted aromatic ring.) Examples of substituted compounds are shown below.

N(Cpo4011h N(C1
H40H)20CH3QC)in 5OzN1 bu3N! The amount of fluorescent dye used during the preparation of physical development nuclei can be arbitrarily determined by adding more than 0.5 times the solid wavelength of the hydrophilic colloid material used at that time, but it is preferably 50 to 200% by weight. It is.

Physical development nuclear liquid materials include silver, gold, platinum, palladium,
Metals such as copper, cadmium, lead, cobalt, and nickel, or their sulfides, selenides, etc., can be used or in combination of two or more, but preferably nickel sulfide or a metal compound consisting of cobalt sulfide and silver sulfide can be used. It's a boar.

The a ratio of physical development nuclei is approximately 1 x 10-1' per 14 preparation solutions.
It ranges from mol to about 1X10-'' mol.

The V4 physical development nucleus is preferably produced by reacting at a temperature of 30° C. to 100° C., preferably 50° C. to 70° C., for a desired period of time.

The prepared physical development nuclear solution was fJxxlo-7-about 1×
It is mixed with a parallel number for forming an image receiving layer so as to have a nuclear content of 10 mol/R.

As binders for Uke 1 and 1-, gelatin, phthalated gelatin, acylated gelatin, phenylcarbamylated gelatin, carboquine methyl cellulose, hydroquinoethyl cellulose, alginate, polyvinyl alcohol, partially saponified polyvinyl alcohol, Polyvinyl alcohol dehydrothermal maleic acid co-electrode, e.g.
Styrene - heat processed with maleic anhydride, ethylene maleic anhydride, etc., polyacrylamide, poly-N-vinylpyrrolid, latex (e.g., polyacrylic ester, polymethacrylic ester, polystyrene, polybutadiene) (or other compounds) can be used alone or in combination.

The carp can be hardened with a suitable hardening agent. Specific examples of hardening agents include aldehyde compounds such as formaldehyde and geltaraldehyde, diacetyl, and cyclopentanedione. Ketone compounds such as bis(2-chloroethylurea)-2-hydroxy-4,6-
Dichloro-1,3,5) riazine, US 1 yen! j 3rd
．． 288.775, divinyl sulfone, U.S. Pat. No. 3,635,
Compounds with reactive olefins as described in No. 718,
N-methylol compounds as described in U.S. Pat. No. 2,732,316, incyanates as described in U.S. Pat. No. 3,103,437, U.S. Pat. No. 3,017,280, U.S. Pat. No. 2,983,611 aziridine compounds as described, carbodiimide compounds as described in U.S. Patent No. 3,100,704, U.S. Pat.
Epoxy compounds as described in No. 1, halogenocarboxaldehydes such as mucochloric acid, beaten dioxane derivatives of dihydrox-7 dioxane, chromium alum, potash alum,
There are inorganic hardeners such as zirconium sulfate, and these can be used alone or in combination of two or more.

The image-receiving layer contains surfactants (such as natural surfactants such as saponin, 7-ion surfactants such as alkylene oxide type, glycerin type, and glycidol type, higher alkylamine steel, quaternary ammonium salts, pyridine and other complexes). Rings, cationic surfactants with sulfonium, carboxylic acids, sulfonic acids, phosphoric acids, sulfuric acid ester groups, anionic surfactants containing acidic groups such as phosphoric ester groups, amino acids, aminosulfonic acids, sulfuric acid or aminoalcohols. Amphoteric surfactants such as phosphoric acid esters, fluorine-containing anions containing fluorine, amphoteric surfactants, etc.), matting agents, fluorescent dyes for whitening in addition to nuclear preparation, discoloration inhibitors, color toning agents (e.g. As a substitute, 1-phenyl-5-mercagutotetrazole, published by Sonoike 7 Orcal Press,
Photographic Silver Halide Dif-Di, N-Process Color toning agents described on page 61, developing crude drugs (e.g., hydroquinone and its derivatives, x-;y Uniru-3-pyrazolidone and its derivatives, etc.) It may contain a solvent for silver genide (for example, sodium thiosulfate, ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate, etc.).

Further, an over layer may be provided on the image receiving layer, a neutralizing layer below the image receiving layer, and a subbing layer for improving adhesion to the support.

The silver halide emulsion used in the photosensitive layer of the light-sensitive material for silver salt diffusion transfer according to the present invention is an emulsion commonly used for diffusion transfer, and the silver salt is transferred at the speed necessary for the diffusion transfer method. Silver bromide, silver iodide, silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodide, salt Mention may be made of silver iodobromide and mixtures thereof. As mentioned above, the present invention is suitable as an image receiving element for forming a slow-print image, and is not limited to photosensitive materials for continuous use 1A.

Halogenated iron emulsions can be sensitized in a variety of ways when they are manufactured or processed. For example, by sodium thiosulfate, alkylthiourea,
Alternatively, it may be chemically sensitized by a method well known in the art, such as with a gold compound, such as gold rhodan, gold chloride, or a combination of both. Further, sensitization can be carried out as usual.

As the binder for the photosensitive RIA, polymeric materials commonly used in the production of silver halide emulsions, such as the binders described for the image-receiving layer, can be used. In addition, the photosensitive layer can be hardened by using a suitable hardener as described above in the image-receiving layer. Furthermore, the photosensitive layer contains additives generally used in non-rogenated photosensitive materials, such as surfactants, anti-capri agents, matting agents, fluorescent dyes, developing chemicals (for example), hydroquinone and its derivatives, 1- phenyl-3-pyrazolidone and its derivatives). Furthermore, in addition to the photosensitive layer, auxiliary materials such as a lower mni, an intermediate layer, a protective layer, and a release layer may be provided as necessary.

The support for the photosensitive material for silver salt diffusion transfer and the image-receiving material according to the present invention is any support that can be used for construction. They include paper, glass, films, e.g. cellulose acetate films, polyvinyl acetal films, polystyrene films, polyethylene 7-talate films, etc., metal supports coated on both sides with paper, coated on one or both sides with alpha-olefin polymers, e.g. Paper supports coated with / can also be used.

In general, the silver salt diffusion transfer method is divided into the so-called "mono-sheet method" in which the light-sensitive material and the image-receiving material are formed on the same support, and the so-called "mono-sheet method" in which the light-sensitive material and the image-receiving material are formed on separate supports. There is a so-called "two-sheet" method, in which two materials are stacked and pressed together with a roller to perform diffusion transfer and then peeled off, and the present invention is applicable to either of these methods.

The silver salt diffusion transfer treatment liquid in the present invention can have a suitable silver salt diffusion transfer treatment liquid composition.

That is, developing agents for developing exposed silver halogenide, such as hydroquinone and its derivatives,
1-phenyl-3-pyrazolidone and its derivatives, etc.
Solvent 1 for undeveloped silver halide, such as sodium thiosulfate, ammonium thiosulfate, sodium thiocyanate, potassium thiocyanate, etc., sodium sulfite as a preservative, potassium bromide as a development inhibitor, 1-phenyl- as a toning agent.
Contains additives such as 5-mercaptotetrazole, alkaline substances such as sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium phosphate, etc., and thickening agents such as dimethyl cellulose and hydroxyethyl cellulose in carboxylic acid. I can do it.

The present invention will be explained below with reference to Examples, but the present invention is not limited in any way.

Example 1 7 m of a 0.05 mol/I aqueous solution of nickel nitrate and 10 m of a 0.05 trty4/I aqueous solution of sodium sulfide in 30 ml of a trity aqueous solution of poly-N-vinylpyrrolidone
After vigorously stirring and reacting at 60 DEG C. for 1 minute, a 0.1 movI aqueous solution of silver nitrate 3- was added and reacted for 3 minutes to prepare physical development nuclei for comparison. Similarly, however, 1 g of fluorescent dye (Kikor PK, Shin Nisso Kako Co., Ltd. III) in an aqueous solution of poly-N-vinylpyrrolidone
) was added to prepare the physical development nucleus of the present invention. In each case, in addition to an aqueous gelatin solution of an appropriate concentration, IX 10-1'mo17 Gold M!
Drying of hydrophilic colloids to gelatin image-receiving layer containing sulfides”
Comparative and inventive image-receiving materials were each produced so that it2cy.

The light-sensitive material was prepared on the same paper support as the image-receiving material, with carbon black and 11-catechol for preventing halogenation, and 0.3 g// of 1-phenyl-4-methyl-3.
- Gelatin subbing layer containing pyrazolidone (3 g gelatin/
m'), and silver chloroiodobromide (8 mol of silver bromide,
Ortho-sensitized containing 1.8 Jd (1 molt of silver iodide) converted into silver nitrate, and further 0.15 g/? A gelatin silver halide emulsion layer (silver nitrate:gelatin = 1:4) containing catechol, etc. and a protective layer (gelatin 1.3 g/
Lol? ) was prepared.

The emulsion surface of the photosensitive material exposed to light for sensitometry and the image receiving surface of the image receiving material are superimposed and the following developing processing solution 1j is applied.
Squeegee Row 2-
Both materials were peeled off 30 seconds after exiting. Processing liquid temperature is 20℃
It is.

Diffusion transfer developer> A silver image with sufficient gradation to reproduce the continuous tone original was formed on the comparison image-receiving material, but the maximum density was insufficient (reflection density -1, 0) and the silver image was low. The color tone of the dark areas was brownish. The image-receiving material of the present invention forms a silver image with a gradation similar to that of the comparative sample, and the maximum density is also sufficient (
The reflection density was 1.8), and the image had a good neutral gray tone.

Example 2 Example 1 was repeated. However, the photosensitive material was prepared on the same paper support as in Example 1 with an undercoat layer containing carbon black for antihalation, and on the undercoat layer, an orthosensitized silver chlorobromide (bromochloride) with an average particle size of 0.3μ was applied. 1-phenyl-3-pyrazolidone of 1.5 f/n/ and hydroquinone of 0.7η♀, 4 f/n/ in terms of silver nitrate
r? A gelatin silver halide emulsion layer containing gelatin was provided.

The comparative image-receiving material has an insufficient maximum density (reflection 1 density = 1.1
), the image had a low contrast, but the image-receiving material of the present invention had a high maximum density (reflection density=1.6) and a high contrast image.

Example 3 Example 1 was repeated. However, when preparing physical development nuclei, instead of poly-N-vinylpyrrolidone 73% aqueous solution 130d, poly-N-vinylpyrrolidone 3% aqueous solution 15- and acrylamide-vinylimidazole copolymer 3% aqueous solution 15-
A mixed solution of

As in Example 1, only the image-receiving material of the present invention had good continuous tone and a neutral gray silver image.

Example 4 Example 2 was repeated, but using the same receiving material as in Example 3.

Only the image-receiving material of the present invention exhibited superior image reproduction characteristics with high density and high contrast.

Claims (1)

[Claims] 1. An image-receiving element produced by a silver salt diffusion transfer method, characterized in that it contains a physical development core material prepared in a hydrophilic colloid solution containing a fluorescent dye.