JPS61153636A - Photosensitive material for diffusion transfer - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material for diffusion transfer having superior adhesion resistance and an antistatic property by incorporating fine particles of a polymer having repeating units of a monomer contg. at least one fluorine atom (polymer contg. fluorine) into at least one of the outermost layers among the photosensitive elements of a photosensitive material for diffusion transfer. CONSTITUTION:At least one photosensitive silver halide emulsion layer and a protective surface layer are formed on one side of a support, and a nonphotosensitive layer (backing layer) is formed on the other side to obtain a photosensitive material for diffusion transfer. At this time, a matting agent made of a polymer contg. fluorine is preferably incorporated into the protective surface layer as the outermost layer on the emulsion layer side. When the backing layer is composed of two or more layers, the layer positioned farthest from the support is the outermost layer on the backing layer side.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a diffusion transfer photosensitive material (hereinafter simply referred to as a diffusion transfer photosensitive material), and more particularly to a diffusion transfer photosensitive material with improved adhesion and antistatic properties.

[Prior art and problems]

The method of forming an image by diffusion transfer is well known. This principle is
The exposed silver halide of the imagewise exposed light-sensitive layer is developed by the developing agent in the processing solution or the light-sensitive material, and at the same time, the silver halide in the unexposed region is developed by the silver halide solvent in the processing solution. It becomes a silver complex salt. A layer containing silver deposition nuclei (called an image-receiving layer) in which this silver complex salt is superimposed on the photosensitive layer.
The process consists of diffusion and transfer to a silver deposition nucleus, and reduction with a developing agent in the presence of silver deposition nuclei to obtain a silver image.

In recent years, with the shift to color in the photographic field in general, the majority of diffusion transfer sensitive materials have come to be occupied by color diffusion transfer sensitive materials. For color diffusion transfer sensitive materials and methods, see, for example, U.S. Pat.
No. 4, No. 3,345,163, No. 3,362.819
No. 3,415.644, No. 3,443,939, No. 3,485.628, No. 3,594,164,
3,594.165, 3,907,563, 3.928.312, 3,954.476, 4
, No. 053,312, No. 4.139.379, No. 4,
No. 198,235, British Patent No. 1,496,363, Japanese Patent Application Publication No. 54-130927, No. 55-33141, No. 55-33142, No. 56-16131, No. 56-
No. 71060, No. 56-71061, No. 56-710
No. 72, No. 56-142530, No. 56-16434
It is disclosed in many patents such as No. 2, No. 57-85055, No. 57-105738, No. 57-119345, No. 58-37645, No. 58-37646, and No. 58-42043.

Generally, the color diffusion transfer method can be explained as follows.

Typically, a light-sensitive element consisting of a light-sensitive silver halide emulsion layer combined with a dye image-providing material is immersed in an alkaline processing solution after imagewise exposure. The exposed silver halide is developed, and a cross-oxidation reaction occurs between the oxidized raw drug and the dye image-providing substance, and a diffusible dye or dye precursor is generated imagewise from the oxidized dye image-providing substance. and diffuses into the superimposed image receiving elements and is fixed by the mordant. The developing agent may be contained in the alkaline processing liquid, in the light-sensitive element, or in the image-receiving element.

The color diffusion transfer method using such an image forming method includes:
For example, U.S. Patent Nos. 2.983.606 and 3,415.
No. 644, 3,415°645, 3,415.6
No. 46, No. 3,594,164, No. 3,594.16
No. 5, No. 3,730.718, a viscous pasty alkaline processing composition contained in a small bag called a processing bod is applied between the photosensitive layer and the image-receiving layer or between the photosensitive element and the processing sheet. A so-called "bod" processing type sensitive material, which is processed by spreading it between the
No. 5.617, No. 3,405.618, No. 3,485
．． No. 628, No. 3,784.382, No. 4,419.
No. 434, British Patent No. 1,496,363, JP-A-57
-119345, 58-37645, 58-3
A photosensitive sheet in which a photosensitive layer and an image-receiving layer are coated on the same support with a non-viscous alkaline processing liquid having a viscosity substantially comparable to that of water described in No. 7646 and No. 58-42043. Alternatively, the photosensitive element is immersed, a processing solution is impregnated into the photosensitive layer, and the diffusible dye or its precursor formed as a result of development is diffusely transferred to an image-receiving layer provided on the same support. There is a "dipping" processing type sensitive material in which a color image is obtained by diffusing and transferring a liquid-impregnated photosensitive element onto an image-receiving element overlaid on the photosensitive element, and then peeling off the photosensitive element and image-receiving element. The present invention is preferably applied to the latter type of photosensitive material.

Generally, the outermost layer (uppermost layer or back layer) of a photosensitive material uses a hydrophilic colloid, typified by seratin, as a binder. Therefore, when the surface of a photosensitive material is exposed to high humidity, especially in an atmosphere of high temperature and high humidity, its adhesion or tackiness increases.
Easily adheres to other objects by contact with them. This adhesion phenomenon occurs between the photosensitive materials or between the photosensitive materials and other objects that come into contact with them during the production, storage, and processing of the photosensitive materials, and often causes serious failures. In particular, in color diffusion transfer sensitive materials, adhesion is a major problem because the photographic layer contains various additives such as dye image-providing substances. Furthermore, in the case of diffusion transfer sensitive materials in which the photosensitive layer and the image-receiving layer are laminated and kept in a highly alkaline wet state, adhesion poses a more serious problem.

To solve this problem, the outermost layer contains fine particles of inorganic substances such as silicon dioxide, magnesium oxide, titanium dioxide, and calcium carbonate, and organic substances such as polymethyl methacrylate, cellulose acetate propionate, and polyvinyl resin. Methods have been proposed to increase surface roughness (called matting) to reduce adhesion. However, the addition of this matting agent often deteriorates the transparency of the image or impairs the image quality, and it is currently difficult to obtain satisfactory performance.

Furthermore, since photosensitive materials generally consist of a support having electrical insulation properties, accumulation of electrostatic charges is a major problem in addition to adhesion. In other words, contact with various substances, friction, or exposure to light may occur during manufacturing processes such as coating, drying, and processing, or during handling such as winding, unwinding, or transportation during use such as filming, processing, and projection. friction between materials,
The photosensitive emulsion layer becomes electrified due to peeling, and as a result of this discharge, the photosensitive emulsion layer is exposed to light, resulting in dot-like spots or streaks after development. This is what is called a static mark, and it significantly reduces product value. This phenomenon is a very troublesome problem because it becomes apparent only after development. In addition, the accumulated electrostatic charges may cause secondary failures such as dust adhesion to the surface of the film or the inability to apply uniformly.

Methods have been considered to improve the conductivity of the support and coated surface layer of photosensitive materials, and attempts have been made to utilize various hygroscopic substances, water-soluble inorganic salts, surfactants, polymers, and the like. However, it is extremely difficult to prevent static electricity on a hydrophilic colloid layer.
In many cases, the surface resistance is insufficiently lowered at low temperatures, or adhesive failure of photosensitive materials occurs in high temperature and high humidity environments. Moreover, if a large amount of antistatic agent is added to the hydrophilic colloid layer in order to obtain a sufficient antistatic effect, it will have adverse effects such as inhibiting the uniformity of coating and deteriorating the physical properties of the resulting film. This can be improved by appropriate selection of surfactants as coating aids, but these are often reduced due to the antistatic properties of the hydrophilic colloid layer. Belgian patent 742.680 teaches the effectiveness of fluorosurfactants as coating aids.

One means of solving the problem of #P electric charge while maintaining adhesion resistance is described in Japanese Patent Publication No. 44411/1983. That is, the combination of fine particles such as polymethyl methacrylate and a fluorine-based surfactant in the outermost layer of a photosensitive material having a silver halide emulsion layer has produced unexpected effects. However, this technology also causes a new problem in that fluorine-based surfactants are eluted into the processing solution for photosensitive materials and change the surface tension of the processing solution, resulting in changes in photographic properties depending on the amount of processing. Ta.

[Purpose of the invention]

An object of the present invention is to provide a diffusion transfer sensitive material having excellent adhesion resistance and antistatic properties. Another object of the present invention is to provide a diffusion transfer sensitive material whose photographic properties do not substantially change even when a large number of the materials are immersed in a processing solution.

[Structure of the invention]

As a result of various studies on adhesion and charging in diffusion transfer sensitive materials, the inventors discovered that at least one of the outermost layers of the photosensitive element of the diffusion transfer sensitive material has a repeating unit of a monomer containing at least one fluorine atom ( By incorporating fine particles of a fluorine-containing polymer (hereinafter referred to as a fluorine-containing polymer), the above-mentioned problems have been solved.

In the present invention, the diffusion transfer sensitive material consists of a photosensitive element mold, an image receiving element, and, in the case of a "bod" processing plate, a processing composition contained therein. A photosensitive layer and a non-photosensitive layer including a photosensitive layer are coated on a support, and the term "damaged element" refers to a structure in which a constituent layer mainly including a scratched layer for fixing a transferred image is coated on a support. The outermost layer refers to the surface layer and back layer of the photosensitive material or each element.

The present invention is characterized in that fine particles of a fluorine-containing polymer are present in the outermost layer on at least one side of the photosensitive element.9 For example, at least one layer of silver halide is present on one side of the support. In the case of a diffusion transfer sensitive material having an emulsion layer and one surface protective layer, and a non-photosensitive layer (hereinafter referred to as a backing layer) on the other side, the following three types of embodiments can be considered. . (1) A matting agent made of a fluorine-containing polymer is contained in the surface protective layer on the side of the photosensitive silver halide emulsion layer. (
2) The backing layer contains a matting agent made of a fluorine-containing polymer. (3) A matting agent made of a fluorine-containing polymer is contained in both the emulsion surface protective layer and the cooking layer.

Although the present invention includes any of the above three types, the embodiment (1) is particularly preferred.

In the present invention, the outermost layer is a surface protective layer on the photosensitive emulsion layer side, and on the backing layer side, it means the layer furthest from the support when the backing layer is composed of two or more layers. In the present invention, it is preferred that the backing layer generally has a thickness of 1 to 20 μm, especially 5 to 10 μm. When the backing layer is composed of two or more layers, the thickness of the backing layer furthest from the support is 0.1~
It is preferably 3 μm×0.5 to 2 μm. Moreover, when the backing layer consists of two or more layers, it is particularly preferable that the backing layer consists of two layers.

As the monomer having a fluorine atom constituting the polymer used in the present invention, any olefin thread compound having at least one fluorine atom can be used, but compounds represented by the following general formula [■] are preferred.

In the formula, R1, R3 and R2 are a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group (having 1 to 3 carbon atoms and may be substituted with a fluorine atom), an alkoxy group (a carbon atom 3 to 9 may be substituted with a fluorine atom), -0(CFI)nOc6H1 (n represents an integer of 2 to 8), -COOR, (Rs is the number of carbon atoms substituted with a fluorine atom, from 1 to 10 alkyl group, which may be substituted with an atom or group other than fluorine), -Coo (CH!)mNco (CFri nR
y (Re is an alkyl group having 1 to 4 carbon atoms, R is a hydrogen atom or a fluorine atom, m is an integer of 2 to 3, n is 1 to 8
an alkyl group having 1 to 4 carbon atoms, m is an integer of 2 to 3, n
tri represents an integer from 1 to 8) or -〇〇〇 (
Crt) nRT (R? is a hydrogen atom or a fluorine atom, n
represents an integer from 1 to 8). However, R bird,
Rs and R4 may be the same or different, but at least one is a fluorine atom or a group containing at least an il fluorine atom.

Next, at least one preferably used in the present invention
Specific representative examples of monomers having fluorine atoms are listed below.

(I-1) CH,=CHF (I-5)
CHt=C(CF,)FCI-2) CH2=CF
* (1-6) CFx=C(CFa)F(I
-9) CH,=CH(OCR,(CF,)t,,F
(I −10) CF,=CFO(CF,),~,F
(I -11) CH,=C(Cmelon)COOCH,(
Crt)t~, H(I-12) CH,=CHC00
C%(Crt)z, 5H(I43) CH,=CHO
CO(CF2)t~, F(1-14) CHt=CH
OCO(CFx)t, sH(D-15) CI(,
=CHC00C Horse CH, N (C, Mountain) Co (CF Rit~
, F The polymer particles used in the present invention having at least one fluorine atom as a total repeating unit may be particles of a homopolymer consisting only of a fluorine-containing monomer17, or particles of a copolymer with each monomer. There may be. Representative monomers include, for example, acrylic acid, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, butyl methacrylate, acrylamide, N-dimethylacrylamide, diacetone acrylamide, vinyl acetate, diethylaminoethyl methacrylate, ethylene, styrene, Examples include propylene, divinylbenzene, vinyl chloride, vinylidene chloride, and imbutylene.

Next, specific examples of polymers used in the present invention will be listed.
It is not limited to this (numbers outside parentheses indicate the reaction molar ratio of monomers).

Exemplary compound 1 → CH, -CF, surface 2 → CFt CFI base Polyflon (manufactured by Daikin KK) 3 → CF, -CF straight Neoflon (manufactured by Daikin KK) surface CF.

CM.

Ha 10 -f-CF, TCFke 10,000 CH, -CHol
Neoflon (manufactured by Daikin KK) 11 CHs 12 CH*14
CHs19
CH.

20+il'H9 The polymer of the present invention can be polymerized by solution polymerization, emulsion polymerization, suspension polymerization,
Various polymerization reactions and conditions such as bulk polymerization can be arbitrarily adopted. For example, in solution polymerization, a suitable solvent (
For example, ethanol, methanol, etc.), a suitable concentration of monomers (usually 40% by weight or less, preferably 10 to 25% by weight based on the solvent) and a polymerization initiator (for example, benzoyl peroxide, azobisisomer, etc.). The polymerization reaction is carried out by heating to an appropriate temperature (for example, 40 to 120°C, preferably 100 to 100°C) in the presence of (butyronitrile, etc.). Thereafter, the unreacted mixture is separated off by pouring the reaction mixture into a medium such as water, allowing the product to settle, and then drying. The molecular weight of the polymer used as the matting agent of the present invention is 5.000 to i, ooo
, ooo is preferable, more preferably 10.000 to 1
It is 00.000.

The matting agent according to the present invention consists essentially of the polymer of the present invention, but here, "substantially" means that it may contain substances other than the polymer of the present invention to the extent that the effects of the present invention are not impaired. It means no problem.

The matting agent according to the present invention is finely dispersed and contained in the outermost layer of the photosensitive element. These matting agents are low-boiling organic solvents,
For example, ethyl acetate, ethyl acetate containing butanol (less than % by weight of butanol), methanol containing butanol (
It is formed by dispersing a uniformly dissolved solution of the polymer (less than 100 g of butanol by weight) into an aqueous gelatin solution under rapid stirring. The size of the matting agent of the present invention can be freely varied within a considerable range, but in the present invention
．． The range is preferably from 2 to 10 μm, particularly preferably from 5 to 5 μm. The aqueous gelatin solution containing the matting agent obtained above can be applied as the outermost layer of a photosensitive element by any method known in the photographic field.

The matting agent of the present invention is applied to the outermost layer at a concentration of 50 to 500% per square meter.
M? The content is preferably 100 to 400 Da.

In the present invention, examples of the hydrophilic colloid binder constituting the outermost layer include gelatin, gelatin derivatives (eg, acetylated gelatin, phthalated gelatin, etc.), albumin, collodion, and the like, with gelatin being particularly preferred. As the gelatin, any gelatin commonly used in the art, such as so-called lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin, etc., can be used.

Furthermore, in the present invention, the outermost layer (if necessary, a hardening agent,
Various additives such as a smoothing agent, a surfactant, an antistatic agent, a thickener, and a polymer latex can be included.

Examples of hardening agents include aldehyde compounds, compounds containing active halogens such as 2-hydroxy-4,6-dichloro-1,3,5-)riazine, vinyl sulfone thread compounds, N-methylol thread compounds, and mucochloric acid. A dihalogenated carboxyaldehyde compound and the like can be used. As the smoothing agent, for example, liquid paraffin, waxes, polyfluorinated hydrocarbons, silicones, etc. can be used. Examples of surfactants include natural surfactants such as saponin, nonionic surfactants such as alkylene oxide threads, cationic surfactants such as higher alkylamines and quaternary ammonium salts, and acidic groups such as carboxylic acid and sulfonic acid. Any anionic surfactant containing the following can be used. Examples of antistatic agents include the above-mentioned surfactants, alkali metal salts such as styrene-maleic acid copolymers and acrylonitrile-acrylic acid copolymers, and U.S. Pat. Nos. 3,206,312 and 3,428. 45
The antistatic agent described in No. 1 can be contained.

In the present invention, various matting agents are used, such as an alkali-insoluble matting agent made of silicon dioxide, polymethacrylate, etc., and an alkali-soluble matting agent made of methyl methacrylate/methacrylic acid copolymer, or ethyl methacrylate/methacrylic acid copolymer. Can be used together. In this case, it is preferred to use relatively small amounts, for example up to 50 η/m 2 .

Dye image-providing materials useful in the present invention act on negatives and are migratory or non-migratory during processing with alkaline compositions. Mobile positive-working dye '#I image-providing materials useful in the present invention are disclosed in U.S. Pat. No. 184,
No. 3,482°972, No. 3,880.658 and No. 3,854.985. Examples of negative-acting dye-46 donor materials useful in the present invention are conventional couplers that react with oxidized aromatic primary amine developing agents to form or release dyes, such as U.S. Pat. No. 550 and Canadian Patent No. 602.6
This is what is described in No. 07.

In a preferred embodiment of the invention, the dye 46 donor material is a dye-releasing redox compound (DRR).

Such compounds are well known in the art and react with oxidized or non-oxidized dyeing agents or electron transfer agents to release dyes. Examples of such non-diffusive DRR include compounds that work on negatives:
For example, U.S. Patent No. 3.728°113, U.S. Pat.
．． No. 062, No. 3,698,897, No. 3,628°952, No. 3,443,939, No. 3,443,9
No. 40, No. 4,053°312, No. 4,076.52
No. 9 and JP-A-51-104343, JP-A No. 53-46
No. 730, No. 53-50736, No. 51-11362
No. 4, No. 53-3819, No. 54-54021, No. 56-16131, No. 57-85055, and Research Disclosure (les@arch Dis
Closure ) 15157 (1976), 1
5654 (1977).

In a preferred embodiment of the present invention, the above-mentioned Japanese Unexamined Patent Publication No. 51
Dye-releasing agents such as those described in No. 104343 and No. 57-85055 are used. Such compounds are stabilized sulfonamide compounds that can undergo alkaline cleavage upon oxidation to release a diffusible dye.

In other preferred embodiments of the invention, positively acting compounds, such as U.S. Pat.
, 199.354 and 4,199.355 can be used.

The photographic elements of this invention are used to form monochrome or multicolor positive images. The silver halide emulsion layer of a photographic element is associated with a dye image-providing material. The dye image-providing material has a major spectral absorption within the region of the visible spectrum to which the silver halide emulsion is sensitive. That is, the blue-sensitive silver halide emulsion layer contains a yellow dye image-forming substance, and the green-sensitive silver halide emulsion layer contains a magenta dye image-forming substance.
The red-sensitive silver halide emulsion layer is then associated with a cyan dye image-providing material. The dye image-providing material associated with each silver halide emulsion layer is contained in the emulsion layer itself and in the dye layer adjacent to the emulsion layer. Usually, the colorant layer containing the dye image-providing substance is applied as a separate layer below the emulsion layer with respect to the direction of exposure.

The silver halide emulsions 1-1 of the photographic elements used in this invention are constructed in the usual order, ie, from the exposed side, first a bone-sensitive silver halide emulsion layer, then a green-sensitive silver halide emulsion layer and a red-sensitive halogen emulsion layer. Although the silver oxide emulsion layers are arranged in this order, they can be arbitrarily changed depending on the purpose. A layer of yellow filter can be disposed between the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer.

The silver halide emulsion used in the diffusion transfer sensitive material having the photographic element of the present invention may be prepared by any method such as a conventional single jet method, double jet method, acid method, ammonia method, or neutral method. It is a hydrophilic colloidal dispersion of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, or a mixture thereof, and the halogen composition is suitable for use in diffusion transfer sensitive materials. Ashes are disposed of depending on the purpose and processing conditions.

The grain size of the silver halide used may be a normal grain size or a fine grain size, but the average grain size is about 0.1-2μ.
Those within the range of m are preferred. It is desirable that the particles be uniform depending on the purpose of use of the diffusion transfer sensitive material. The crystal shape of the particles used may be cubic, octahedral or mixed crystal. These silver halide emulsions are, for example, P. Glafkides.
) Author: Chlmie P
photography) J (2nd edition, 19
57: Paul Montel Paris) by conventional methods such as those described in Chapters 18-23.

In the present invention, one surface latent r# mainly forms a latent image on the particle surface.
Type 1 silver halide emulsions, so-called negative-working silver halide emulsions, can also be used, and type 1 internal latent image silver halide emulsions that mainly form latent images inside the grains can also be used. The surface latent image emulsion is research disclosure 17
643 (1978) [7].

Internal latent image type silver halide emulsions advantageously used in the present invention include U.S. Pat.
, No. 206,313, No. 3,447.927, No. 3,
Convergence type emulsions, core/shell type emulsions, which are described in No. 761.276 and No. 3,935.014, etc.
Examples include emulsions containing different metals.

After exposure, this type of emulsion is suitable for direct processing in the presence of a nucleating agent to obtain a positive result. Nucleating agents include hydrazines described in U.S. Pat. No. 2,588,982 and U.S. Pat. No. 2,563.785;
Hydrazides and hydrazones described in No. 2; British Patent No. 1,283.835, Japanese Patent Publication No. 49-38164,
U.S. Patent No. 3.734.738, U.S. Patent No. 3,719.494
No. 3,615.615, and a sensitizing dye having a nualeating substituent in the dye molecule, as described in U.S. Pat. No. 3,718.470. ; U.S. Patent 4,030°92
5, No. 4,031.127, and nine-acyl hydrazinophenylthiourea compounds are representative.

Hydrophilic colloid binders used in silver halide emulsions include gelatin, modified gelatin, gelatin derivatives, carboxymethyl cellulose acid copolymers, polyacrylamide, etc. These may be used alone or in combination of two or more. It's okay.

Further, a latex-like water-dispersed vinyl compound can also be contained in the photographic constituent layer of the light-sensitive material according to the present invention. Such latexes include alkyl acrylates,
Alkyl methacrylate, acrylic acid, methacrylic acid,
Single or copolymers of glycidyl acrylate, styrene, vinyl chloride, vinylidene chloride, etc. are used.

The silver halide emulsion in the present invention can be chemically sensitized by conventional methods. For example, U.S. Patent 2.399.08
Gold compounds as shown in U.S. Pat. No. 3, U.S. Pat. Chemical sensitization can be carried out using sulfur compounds such as No. 3, other tin salts, amines, and the like.

A stabilizer or an antifoggant can be added to the silver halide emulsion in the present invention. For example, 4-hydroxy-6-methyl-1,3,3m, 7-tetrazaindene, 3-methyl-benzothiazole, 1-phenyl-
Many compounds such as 5-mercaptotetrasol, many heterocyclic compounds, mercury-containing compounds, mercapto compounds, metal salts, etc. can be used.

The silver halide emulsions used in the present invention may have color sensitivity extended by spectral sensitizing dyes, if desired. As the spectral sensitizing dye, cyanine dyes, merocyanine dyes, etc. can be used as appropriate.

Combinations of different developers can also be used, such as those disclosed in US Pat. No. 3,039,869. Such developers may be used in liquid processing compositions or in one or more of the photographic or image layers, such as in emulsion layers, activated by an alkaline processing composition. A developer can also be mixed into the material layer, intermediate layer or image-receiving layer.

Examples of the developer that can be used in the present invention are as follows.

Hydroquinone, amine phenol, e.g. ttfN-methylaminophenol, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-
3-pyrazolidinone, 1-p-tolyl-3-pyrazolidinone γ'p-tolyl-
4-Methyl-4-hydroxymethyl-3-pyrazolidinone, N,N-diethyl-p-7 22-diamine, 3-
Methyl-N,N-diethyl-p-phenylenediamine,
3-methoxy-N-ethoxy-p-phenylenediamine and the like.

Among those listed here, black-and-white color development agents, which generally have the property of reducing stain formation in the image-receiving layer, can be added anywhere in the diffusion transfer material; Preferably, the present 11 agent is a precursor as described in JP-A No. 55-5333Q, and in particular, as described in British Patent No. 2,056.101.
As described in the above issue, it is desirable that the phenolic agent be stabilized with a metal salt or the like.

The alkaline treatment or activating composition used in the present invention may be an alkaline substance, such as an alkali metal hydroxide, or a carbonate, such as sodium hydroxide or
c is sodium carbonate and the i ratio is a conventional aqueous solution of an amine, such as diethylamine, which is preferably
It has a pH value above 3.

The treatment composition contains antioxidants such as sodium sulfite, ascorbate, piperidinohexose reductone, and may contain silver ion concentration regulators such as potassium bromide. A viscosity-increasing liquid such as hydroxyethyl cellulose or sodium carboxymethyl cellulose may also be included.

In addition, in the present alkaline treatment composition, compounds such as benzyl alcohol and aliphatic primary acetic acid (e.g., 11-aminoundecane #1) that promote the phenomenon or promote the diffusion of the dye are added. May be included.

In addition, the processing composition may contain light-absorbing substances such as ffited titanium-bon black and pH indicators to prevent the silver halide emulsion from fogging due to external light during processing, and U.S. Pat. It may be advantageous in some situations to contain desensitizers such as those described in No. 333. Furthermore, a practical inhibitor such as benzito+1 azole can be added to the treatment agent.

The use of a neutralizing layer in the diffusion transfer sensitive material of the present invention increases the stability of the transferred l.

It is also possible to use one or more timing layers or inert spacers arranged superimposed (directly or indirectly) above or below the neutralization layer. This layer has a p-day drop of 1° as a function of the rate at which the alkaline treatment composition diffuses through the inert spacer layer.
' Has a timing I+ or control function. A sequence of such timing layers and their functionality is
JP-A-56-69629, JP-A No. 57-6842, JP-A No. 5
No. 7-6843, No. 52-145217, No. 55-5
No. 4341 and No. 57-60332.

The receptor layer used in the present invention is a layer for fixing the diffusion-transferred dye image 1 by mordant, and various mordants can be used.

As specific examples of mordants, violet-containing secondary and tertiary amines, nitrogen-containing heterocyclic compounds, and quaternary cationic compounds thereof are widely known.

U.S. Patent No. 2,548.564, 2,484°430
No. 3, 148, 061, No. 3,756, 8
No. 14 ICa, a vinylpyridine polymer and a vinylpyridinium thiombo) 1mer are disclosed.

US Pat. No. 2,675,316&C discloses the use of polymers containing dialkylamino groups as mordants.

Aminoguanidine derivatives are disclosed in US Pat. No. 2,882,156.

U.S. Pat. No. 3,625.694, 3,859.

No. 096, British Patent No. 1.277.453, British Patent No. 2゜01
No. 1.012 discloses a mordant capable of crosslinking with gelatin and the like.

U.S. Patent: J, 958, 995, 2,7
No. 21.852 and No. 2,798.063 disclose aqueous sol type mordants.

Also, Tokukai Akira! ') No. 0-61228 discloses water-insoluble mordants.

Other U.S. Patent Nos. 3.709.690 and 3.788.
No. 85Fs, West German Publication (OL8) 2.

843, No. 320, JP-A No. 53-30328, No. 5
2-154') No. 528, +53-125, No. 5
No. 3-1024, No. 54-74430, No. 54-12
No. 4726, No. 55-22766, U.S. Patent No. 3,64
No. 2.482, No. 3,488.706, No. 3,557
．． No. 066, No. 3,271.147, No. 3,271.
No. 148, Special Publication Showa F) No. 5-29418, No. 56-36
Various rice mordants are disclosed in No. 414, No. 57-12139, and Research Disclosure 12045 (1974).

As a mordant, it is preferable to use one that does not easily migrate from the receiving layer to other layers.For this purpose, it may be necessary to crosslink it with gelatin or the like as listed above, or to use a water-insoluble mordant in a mixture of water and an organic solvent. Various methods have been used, such as applying the liquid more easily, emulsifying and dispersing it, and applying an aqueous sol using a latte/solst dispersion.

Particularly preferred is a mordant made of a polymer containing N-vinylimidazole, which has excellent stability against light during dye transfer.

In order to prevent the mordanted dye-1 dye from fading due to ultraviolet rays, the receiver 1# layer of the present invention contains, for example, JP-A-51-5
No. 6620, No. 57-157245, No. 58-111
942, as well as fluorescent brighteners and anti-fade agents such as stilbenes, coumarins, triazines, oxazoles CI/lJ
For example, chroma/-JL, -alkylphenol) may be included.

Furthermore, see for example U.S. Pat. No. 3,2 fi O, 59
No. 7, No. 3,575.699, No. 3,649゜267
GB 2,035.589 and their precursors can be included. The above compounds other than the mordant can also be contained in a separate layer adjacent to the receptor layer.

When the image forming substance from the diffusion transfer sensitive material is not a dye but a silver complex salt and one black and white image is formed in one layer of the receiver,
The physical phenomena in the crystal layer include heavy metals such as gold, silver, carbon dioxide, and palladium, which are called physical phenomena, and zinc, mercury, lead, and chromium, which are poorly soluble in water.
It contains sulfides of nickel, copper, silver, gold, etc., or silver deposition nuclei such as selenides.

In the practice of the present invention, the surface layer of the receiving layer 11 is made of hydrophilic colloids, such as gelatin, derivatized gelatin, Gungun, f-xtran, polyvinylpyrrolidone, a) hyalgum, carboxymethylcellulose, hydroxyethylcellulose, polyvinyl alcohol, guar gum, gum acacia. Hydrophilic binder containing etc.! - may be produced.

Photosensitive layer and/or d receiver 1 used in the present invention
For the overcoat layer of image 1-, any material described in Research Disclosure 15162 (1976) can be used, but especially when the photosensitive material of the present invention is used in the diffusion transfer method using the two sheets described above, Since it is preferable that the contact surface between the photosensitive layer and the photosensitive layer ensures uniform contact during handling, bending and curling, for example, JP-A-57-58144, JP-A-57-57
It is preferred to use compositions consisting of hydrophilic colloids and silica or ionic polyesters as described in No. 581.16.

The constituent layers of the diffusion transfer sensitive material according to the present invention may further contain various additives7. type compounds, quaternary onion A compounds, mordants such as tertiary aminated fragments, glycerin, gelatin plasticizers such as Japanese Patent Publication No. 43-4939, styrene-maleic acid copolymer, Japanese Patent Publication No. 36-21574 Thickeners, antioxidants, pi
(1i14 regulator etc. can be used.

As long as the support of the photographic material used in the present invention does not adversely affect the photographic properties and has dimensional stability,
Examples of such supports, which may be made of any material, include cellulose acetate films, polyethylene films, and ester films, such as polyethylene terephthalate films and polycarbonate films, which are commonly used in photographic materials. It will be done. In order to prevent capri due to the piping of the support Fi, finely divided titanium dioxide, a light scattering property such as carbon black, or a light absorbing pigment, or JP-A-47-1424 is used.
No. 5, No. 48-34958, Japanese Patent Publication No. 47-8735, British Patent No. 1,287.479, US Patent No. 3,728
．． No. 124, Ichikawa No. 3,822.132.

[Implementation row]

The present invention will be explained in more detail with reference to Examples below.
This does not limit the embodiments of the present invention.

Synthesis-1 (Exemplary Compound 7) CH, = CHCOOCH, (CF,)4) 1143.
9 (0.50 mol), methacrylic acid 43. O11(0
, 50 mol), azobisisobutyronitrile (hereinafter referred to as AI
(abbreviated as BN) 2. ON and ethanol 500M 3
The mixture was refluxed for 10 hours.
Thereafter, the reaction solution was poured into mixed water with vigorous stirring to precipitate the reaction product.7Then, the precipitate was filtered, washed with water, and dried in air at ω°C to produce the product according to the present invention. A copolymer exemplified sewing material (7) was obtained. Store 178.6
# (yield 96cm) and 72. NMR1 elemental analysis and the like confirmed that this substance had a composition of compound series (7).

Synthesis row-2 (Exemplary compound 11) Hs C) (, = C-C00CH, (CL), H150&
(0,60 mol)-su, tyrene 41.6.9 (0,4
0 mol) and AlBN2.oy are reacted and treated in the same manner as in Synthesis Example-1 to obtain a copolymer exemplified compound (11) according to the present invention.
I got it. The yield was 182.01 (yield 95%), and NMR, elemental analysis, etc. showed that this substance was found in the compound series (11
) was confirmed to have the following composition.

Synthesis row-3 (Exemplary compound 18) CH, = C) JOCO (CF,), F 79.8,
F (0.60 mol), divinylbenzene 52. OII
(0.40 mol) and 2.0 g of AlBN were reacted and treated in the same manner as in Synthesis Example 1 to obtain a copolyaniline compound (18) according to the present invention. Condensation, 126.5 If (yield 9
It was confirmed by NMR, elemental analysis, etc. that this substance had the composition of compound series (18).

Next, a production sequence of typical matting agents used in the present invention will be shown.

During production-1: 7150 g of the copolymer obtained in synthesis sequence-1 was added to a mixed solvent of 150 g of ethyl acetate, 40 g of n-butanol, and 40 g of F.
Make sure it dissolves at 0℃. In addition, sodium dodecylbenzenesulfonate is added to 40.9 parts of water. Og was dissolved. 30 more
Add 24g of gelatin to a 0ml beaker and add 20orL of water.
1 was added to cause swelling, and then dissolved at ω°C.

Next, after putting gelatin solution and 11um sodium dodecylbenzenesulfonate aqueous solution into three flasks,
It was heated to 5°C. A solution of copolymer (7) was added thereto, and the mixture was stirred at a speed of 800 revolutions per minute. As a result of observing the obtained emulsion with an optical microscope, it was found that 2 to 5
Polymer oil droplets with a diameter of 71 μm were observed. In addition, this emulsion was dried under reduced pressure at 100 nmHg and 45°C to remove the solvent. Then, by centrifugation, particle size 2
A single patch of ~5 μm was obtained.

Production Example-2 The copolymer (11) obtained in Synthesis Example-2 was treated in the same manner as in Production Series-1 to obtain a matting agent with a particle size of 2 to 5 μm.

Preparation Example 3 The copolymer (18) obtained in Synthesis Example 3 was treated in the same manner as in Production Series 1 to obtain a matting agent with a particle size of 2 to 5 μm.

Example 1 A laminated multicolor photosensitive sheet (photosensitive sheet) was prepared by sequentially coating the layers listed below on a coated opaque polyethylene terephthalate support with a thickness of 180 μm. Unless otherwise specified, the values are shown per ld, and I silver halide emulsions are shown in terms of silver).

Layer (1) Neutralization layer acrylic acid-butyl acrylate cobo 11 mer (superposition ratio 7
0/30) Neutralization layer containing 10II and silane coupling agent (manufactured by Toshi Silicon) 0.2II.

Layer (2) Timing layer poly(vinylidene chloride-acrylonitrile-acrylic acid) latex (overlapping ratio 75/15/10) 1 part,
It was prepared by hydrolyzing and lactonizing an aryl acetate-maleic anhydride copolymer and partially esterifying it with n-butanol (!2/butyl ester i
Timing layer containing 2.6 g of a mixture with 1 part of lactone polymer with a tt ratio of 15/85.

Layer (3) Cyan coloring material layer Cyan image 1 image donor substance o, 5i having the following structural formula.

0.25.9 tricresyl phosphate and 1.5 l of gelatin! A cyan coloring material layer.

Layer (4) Red-sensitive negative-working silver halide emulsion layer Red-sensitized negative-working silver iodobromide emulsion Q, 35 Ji', 2-3ec
-Octadecylhydroquinone-5-Possium sulfonate 0.04.9 and gelatin 0.7, li' Red 16 emulsion 1-0 Layer (5) Intermediate layer gelatin y 1.25 g and 2-acetyl-5- s
Medium 1ilJ1 layer containing 0.4 g of ec-octadecylhydroquinone.

111 (6) Magenta colorant layer Magenta paint donor substance having the following structure 0.461! ,
Tricresyl phosphate 0.231! and gelatin t, 5! A magenta color material layer consisting of i.

Layer (7) Green-sensitive negative-working silver halide emulsion layer Green-sensitized negative-working silver iodobromide emulsion 0.5. ? , 2-5eC-octaf
Potassium silhydroquinone-5-sulfonate 04
, F and gelatin 0.72.

Layer (8) Intermediate layer gelatin 1.25, P and 2-acetyl-5-s
Intermediate layer containing 0.4.9 ec-octadecylhydroquinone.

Layer (9) Yellow coloring material layer 0.7L of yellow m-11J donor substance having the following structural formula
Yellow forest layer consisting of 11 cresyl phosphate O,:(5,9 and gelatin 1°5I).

1m (10)-il? Sensitive Negative type silver iodobromide emulsion layer Blue sensitized negative type silver iodobromide emulsion 0.6,9,2-di-octadecylno-1-hydroquinone-5-potassium sulfonate 0.04! ! and gelatin 0.7! ! A T-sensitive emulsion layer consisting of.

Layer (11) Protection) - Gelatin 0°8112-acetyl-5-sec-ophtadefluhydroquinone 0.2F, G11 Oxal 0.
01.9 K Manufacturer according to the invention (according to production sequence 1) 100rR9 and coating aid 8 A -1,0,0
The trowel layer consists of 6F.

Next, samples (2), (3), (41, ( 51 and (6) were created・Table-1 8A-I CH,C00CH,CH(C,H,)C,)
j, 5A-2C,F,,80. KCHCOOCH,
CH(C,H,)C,H.

80, Na For each of the above samples, cut two pieces into 10 cIrL square pieces and heat them at 23°C at 80°C, taking care not to touch each other.
After incubating for a period of time in an atmosphere of 80011 RE-1, two protective layers of the same sample were brought into contact with each other.
Apply a load of
The product was measured and the adhesion was compared.

The evaluation criteria are as follows.

Rank Area of adhesive part A 0-20% 8 21-40% C41-60% D 61 inches or more The results are shown in Table 21C.

Table 2 From the results in Table 2, it is clear that the adhesion resistance of the matting agent of the present invention is superior to conventional matting agents.

Implementation row 2 Samples (1) to (6) coated and prepared in Example 1 were subjected to humidity control at β° C. and 20 R)I atmosphere for 4 hours, and then the friction zone xi between the neoprene rubber and the sample was measured and Z3' Cl2O
After adjusting the humidity for 4 hours in an atmosphere of %RH, the samples were rubbed with a neoprene rubber roller, and then a static mark generation test was conducted using the formulation described below and visually determined, and the results were as shown in Table 3.

The image-receiving sheet used in the static mark generation test was prepared by sequentially coating the layers shown below on a paper support (additional t
) Layer (1) Receptive layer styrene and N,N-dimethyl-N-benzyl-N-p-
(methacrylaminophenyl) terpolymer of methylammonium chloride and divinylbenzene (mole ratio: 48
/48/4) 2.7,? , gelatin 2.7 fI
and 0.33.9 of 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone.

In (2+ Intermediate layer gelatin 1.2.9. Ultraviolet absorber; 2-(2-hydroxy=3-tert-butyl-5-n-]tylphenyl)bensito-11 azole, 2-(2-hydroxy-3- tert -butyl-5-methylphenyl)-6-chloro-benzotriazole, 2-(2-hydroxy-3,5-dibutylphenyl)pencyto-11azole and 2-(2-hydroxy-5-n-butylphenyl)benzo mixture consisting of triazoles 0.8,
IF and glyoxal 0.06,? middle class.

Layer (3) Protective layer Protective layer of gelatin O, f'i5 N.

Layer (4) Overcoat layer gelatin 0.27,? and silica 14j! Overcoat layer consisting of.

Composition of Illustrative Solution Each sample subjected to the static mark generation test was immersed in a shallow tray-shaped processing device containing the above-mentioned Illustrative Solution at a temperature of 1° C., and the surface facing the image-receiving sheet was /(combined,
Next, it was passed between a pair of pressure rollers and brought into contact with each other. After 10 minutes, the sample and the receiving sheet were peeled off, and at this time, the degree of transfer to the image receiving sheet was observed, and evaluation was made according to the following evaluation criteria.

Grade Static Mark 1: No occurrence 2: Occurs slightly 3: Occurrence 4: Slightly frequent 5: Occurs all over the surface The above results are shown in Table-3.

From the results shown in Table 3, comparative samples (4) and (5) were highly charged and also had static marks. In addition, sample (6) had only a small amount of static marks, but a large amount of static marks. On the other hand, samples (]l, (21 and (3)) containing the matting agent of the present invention were electrostatically charged. It can be seen that it is excellent in that it has a small size and no static marks are generated.

Example 3 Sample coated and created in Example tj1 (] l (21 (5
1 and (6) to 17.6 crn x 12.5 c
Then, using an enlarger, a negative film with a wedge pattern photographed on a part of the screen was printed on the sample.T7 Then, using the image-receiving sheet shown in Example 2 and the image-receiving liquid, The exposed samples (11,100 sheets) were exposed in succession and received.
The photographic characteristics of the wedge-exposed portion transferred to the image sheet were investigated. Furthermore, after the 1st phenomenon of 100 samples is completed, the 1st phenomenon is
The surface tension of the electrolyte solution was measured. Similarly, the photographic properties of samples (21 (51) and (0) were investigated in the same manner using new phenolic solutions, and the surface and toughness of the phenolic solutions used were measured. The results are shown in Table 4. As is clearer, sample (6) containing a conventional matting agent in the protective layer and using a fluorine-based activator as a coating aid had poor reproducibility of characteristic values.
Sample phenomenon 1 phenomenon after phenomenon [51! The surface tension of the solution is reduced. In contrast, sample (1) containing the matting agent of the present invention and using SA-1 (a common activator in the field) as a coating aid and (21t/'i) had excellent reproducibility of the characteristic value; There is also a small decrease in surface tension of the solution after incubation.

Furthermore, the sample using the matting agent of the present invention had better peelability between the photosensitive sheet and the photosensitive sheet than the comparative sample containing silicon dioxide.

Practical row 4 Sample (7) was prepared by adding the matting agent of the present invention (exemplified sewing material 7) at 100 Da per 1 m' to the backing 1- of the sample (]) prepared in Example 1. Similar tests to M[N13.2 and 3 were conducted. Effects equivalent to or better than those of Sample (1) were obtained in terms of adhesiveness, band width, static marks, zero true property reproducibility, and reduction in surface tension of the optical solution.

Claims (4)

[Claims] (1) The photosensitive element of the photographic light-sensitive material for diffusion transfer is characterized in that at least one of its outermost layers contains polymer particles having a repeating unit of a monomer containing at least one fluorine atom. photosensitive material. (2) The photographic light-sensitive material for diffusion transfer according to claim 1, wherein the light-sensitive material is processed with a non-viscous alkaline processing liquid. (3) The photographic material for diffusion transfer according to claims 1 and 2, wherein the polymer particles have a particle size of 0.2 to 10 μm. (4) The photographic material for diffusion transfer according to claims 1, 2 and 3, wherein the polymer has a molecular weight of 5,000 to 1,000,000.