JPH0196650A - Image forming sheet - Google Patents

Abstract

PURPOSE:To prevent color transfer and adhesion fault and to improve a release property by incorporating the fine particles of a hydrophobic fluorine compd. into the front and/or rear face of a sheet. CONSTITUTION:The fine particles of the hydrophobic fluorine compd. are incor porated into the front and/or rear face of the image receiving sheet having at least one dye receiving layer on a base. The fine particles of the hydrophobic fluorine compd. refer to the fine particles of an oily fluorine compd. and solid fluorine compd. resin, etc., and are more preferably latex-like fine particles. The more specific example of the oily fluorine compd. is fluorine oil and the more specific example of the solid fluorine compd. resin is a poly tetrafluoroethylene resin, vinylidene fluoride resin, etc. The color transfer acci dent in the case of preserving the image receiving sheets in the face-to-face state under high humidity after the image formation is thereby prevented and the adhesive fault at the time of the preservation prior to the image formation is prevented; furthermore, the release property of the image receiving sheet of the type to be released from the photosensitive material after an image forming processing is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an image-forming sheet, and more particularly to an image-forming sheet with improved prevention of color transfer and prevention of adhesion failure, and further improved releasability.

(Prior art and its problems) The image-forming sheet of the present invention has at least one dye-receiving layer on a support. ), dye-fixing materials for thermal development methods, dye-receiving materials for ink-jet methods, dye-receiving materials for thermal transfer methods, and the like.

When these image forming sheets are stacked face to face and stored after image formation, there is a problem of color transfer failure due to dye migration from one image forming sheet to the other sheet. This color transfer failure is particularly likely to occur when the sheets are stored face-to-face under high humidity.

However, in color image forming methods such as color diffusion transfer methods and thermal development methods, in which diffusible dyes are formed or released into an image and then diffused and fixed on a dye-receiving layer, the diffusible dyes are generally anionic dyes. A cationic mordant is used in the dye-receiving layer that fixes this anionic dye. Increasing the mordant power of this mordant also increases the ability to take away the dye from the dye-receiving layer on the opposing side stacked one on top of the other, and conversely, weakening the mordant power makes it easier to demordant. Therefore, it has been difficult to completely prevent color transfer failures by improving mordants.

In addition, in the dye-receiving material of the inkjet method, when anionic or cationic dyes are fixed using a cationic or anionic mordant, it is the same as in the color image forming method using the color diffusion transfer method or heat development method. something happens.

Therefore, it has been desired to develop a technique to prevent these color transfer failures.

In addition, image forming sheets, especially color diffusion transfer type and heat development type image forming sheets (dye fixing materials) in which a silver halide photosensitive material is exposed and then overlaid with this photosensitive material for development and transfer processing. Before processing, they are cut into sheets and stored stacked one on top of the other, or they are stored in rolls. At this time, the dye-fixing materials may adhere to each other, causing adhesion failure. For example, cut sheets of dye-fixing materials may adhere to each other or may not slip properly.
If more than one sheet of dye-fixing material is conveyed at the same time, or if the roll-shaped dye-fixing material malfunctions in adhesion and paper cannot be fed or conveyed, or if the dye-fixing material is forcibly conveyed, the surface of the dye-fixing material may become rough. There is a problem. This adhesive failure is particularly likely to occur if the dye fixing material is stored under high humidity.

One way to prevent these adhesion failures is to increase the degree of hardening of the dye fixing material coating.
Although this method is effective in preventing adhesion failures, it is still insufficient when the dye-fixing material is stored under high humidity.

In addition, as described in US Pat. In the case of development or dye transfer under heat, increasing the degree of hardening increases the time required for the supplied water to completely penetrate the coated film, resulting in a shorter image forming process. I won't be able to do that.

Therefore, it has been desired to develop a technique that effectively prevents adhesion failure between dye-fixing materials before transfer processing.

Furthermore, in the color diffusion transfer method and thermal development method.

After development and transfer, the image forming sheet (dye fixing material) is peeled off from the silver halide photosensitive material, but at this time, the coating film of the photosensitive material and the coating film of the dye fixing material are integrated and cannot be easily peeled off. If the coating film is peeled off or forcibly peeled off, the coating film may peel off, causing damage or stains on the peeled surface, resulting in a problem in that a satisfactory clear image cannot be obtained.

In order to solve this problem of poor peelability after transfer, a fluorine-based surfactant may be present in the uppermost layer on the contact surface side of at least one of the photosensitive material and the dye fixing material (Japanese Patent Laid-Open No. 6
1-20944), and it has also been proposed to provide a release layer containing a fluorine-containing surfactant between a photosensitive element and an image receiving element of a heat-developable photosensitive material (Japanese Unexamined Patent Publication No. 62-50753). However, among the specific compounds of the fluorosurfactants listed here, most of the compounds that have a particularly large effect of improving peelability are poorly water-soluble compounds. This is the fluorine-containing group part (i.e. hydrophobic part) in the compound.
It is thought that when the effect of is increased, the effect of the hydrophilic group becomes relatively smaller, and the hydrophobicity/hydrophilicity balance of the compound is biased towards hydrophobicity. Therefore, water alone is insufficient as a solvent for adding and coating these compounds, and it is necessary to use a combination of an organic solvent and water or use an organic solvent alone. When an organic solvent is used in the coating solution, coating properties may change depending on the type of organic solvent.
New problems such as precipitation and changes in photographic performance may arise, and explosion-proof equipment is required to evaporate the organic solvent after coating, which is disadvantageous in terms of cost.

Therefore, it has been desired to develop a technique that improves the releasability after transfer and does not cause the above-mentioned problems.

Therefore, the first object of the present invention is to provide a post-image formation method.

To provide an image forming sheet with improved color transfer failure when the image forming sheets are stacked and stored facing each other under high humidity.

A second object of the present invention is to provide an image forming sheet with improved adhesion failure during storage before image formation.

Furthermore, a third object of the present invention is to provide an image forming sheet of a type that is peeled off from a photosensitive material after image forming processing,
An object of the present invention is to provide an image forming sheet with improved releasability.

Furthermore, a fourth object of the present invention is to provide an image forming sheet that has improved slipperiness and transportability when manufacturing the image forming sheet or during development processing. It is.

(Means for solving problems) These objects have been achieved by the invention described below.

1. An image forming sheet having at least one dye-receiving layer on a support, the sheet containing fine particles of a hydrophobic fluorine compound on the front and/or back surfaces of the sheet.

The present invention will be explained in detail below.

The hydrophobic fluorine compound fine particles of the present invention are fine particles of an oily fluorine compound, a solid fluorine compound resin, etc., and are preferably latex-like fine particles.

Specific examples of oily fluorine compounds include fluorine oil, and specific examples of solid fluorine compound resins include tetrafluoroethylene resin, vinylidene fluoride resin, trifluorochloroethylene resin, hexafluoropropylene resin, Examples include fluorinated ethylene-propylene copolymer resin.

These hydrophobic fluorine compounds are commercially available and can be easily obtained. For example, fluorine oils are commercially available from Daikin Industries under the trade names Daifloil O and Demnum, and from DuPont under the trade name Krytx. 1514, 1525, 240AC1 LPV, 1506, 1618, and 1645 are commercially available.

Tetrafluoroethylene resins are manufactured by Daikin Industries under the trade names Lublon and Polyflon, and Mitsui-DuPont Fluorochemicals is manufactured by Mitsui DuPont Fluorochemicals under the trade names Teflon 30-J; vinylidene fluoride resins are manufactured by Daikin Industries under the trade names Neoflon. With VDF; as a trifluorochloroethylene resin, the product name is NEOFLON II CTFE from Daikin Industries.
In addition, the hexafluoropropylene resin is manufactured by Daikin Industries under the trade name NEOFLON FEP; fluoroethylene-
The propylene copolymer resin is commercially available as Teflon 120 from DuPont Mitsui Fluorochemical Company.

These hydrophobic fluorine compounds have a hydrophilic group moiety (for example, a carboxyl group,
Anionic groups such as sulfo groups and sulfonic acid groups; cationic groups such as amino groups; nonionic groups such as polyoxyethylene chains; amphoteric groups such as diamino acids).
It is insoluble in water, exhibits no surface activity, and is lipophobic due to the action of the fluorine atoms it contains.

The fluorine oil of the present invention is dispersed in the form of oil droplets in a hydrophilic colloid by an emulsion dispersion method known in the photographic field.

Further, the solid hydrophobic fluorine compound resin of the present invention is preferably dispersed in water as latex-like fine particles, and added to a coating liquid for an image forming sheet to be applied. In this way, when dispersing the hydrophobic fluorine compound of the present invention as fine particles in water, no auxiliary organic solvent is basically required, and therefore, the coating properties of the fluorine-based surfactant described above are improved. Problems such as deterioration, precipitation, and changes in photographic performance do not occur.

The coating layer to which fine particles of a hydrophobic fluorine compound are added is preferably the outermost layer on the front and/or back side of the image forming sheet.Depending on the type of image forming sheet, the surface layer may be a dye receiving layer or a surface protective layer. In any case, it is preferable that the hydrophobic fluorine compound fine particles be added to the outermost layer of the surface to prevent adhesion failure between the image forming sheets before image formation. It is sufficient to add hydrophobic fluorine compound fine particles to any one of the outermost layers, but in order to prevent color fading and improve releasability after transfer, it is necessary to add hydrophobic fluorine compound fine particles to at least the outermost surface layer. desirable.

The average particle diameter of the solid fine particles of the hydrophobic fluorine compound is about 0.01 to 10 μm when added to the outermost surface layer.

Preferably 0.02 to 5 μl, particularly preferably 0.05
~2 μm. When added to the outermost layer on the back side, approximately 0.
The particle size is from 0.01 to 30 μm, preferably from 0.05 to 15 μm, particularly preferably from 0.1 to 10 μm.

When using fluorine oil, the average particle size of the fine particles (oil droplets) is about 0.01-10 μm, preferably 0.02-5 μm.

The effect of the hydrophobic fluorine compound fine particles of the present invention is effective in preventing color transfer failure and adhesion failure in all image forming sheets having at least one dye-receiving layer on a support (for example, Image forming sheets for color diffusion transfer systems, thermal development systems, inkjet systems, thermal transfer systems, etc.), and systems that include a peeling process during image formation processing (for example, color diffusion transfer systems, thermal development systems)
In addition to the above-mentioned effects, this is even more effective in that it also improves releasability. In particular, in the thermal development method, in order to obtain sufficient transfer density, the heating temperature during transfer must be increased, the heating time must be extended, and the photosensitive material must be processed in the presence of trace amounts of water, bases, and/or base precursors. When a combination of image forming sheets (dye fixing materials) is heated to perform development and transfer at the same time, significant peelability may occur, and the hydrophobic fluorine compound fine particles of the present invention can effectively prevent this. It is particularly effective in

In the present invention, the binder in the outermost layer to which the hydrophobic fluorine compound fine particles are added may be lipophilic, but preferably hydrophilic. In particular, hydrophilic binders are preferred in the case of dye fixing materials for color diffusion transfer methods and dye fixing materials for thermal development photography in which a small amount of water is added during heat development or dye transfer. Examples include proteins such as gelatin and gelatin derivatives, polyvinyl alcohol, cellulose derivatives, polysaccharides such as starch, natural substances such as gum arabic, dextrin, pullulan, polyvinyl alcohol, sodium polyacrylate, sodium polymethacrylate, Synthetic polymeric substances such as a copolymer of vinyl alcohol and sodium acrylate, polyvinylpyrrolidone, a water-soluble polyvinyl compound such as an acrylamide polymer, or a water-soluble polyester compound are used. Among these, gelatin and polyvinyl alcohol are particularly effective.

In the present invention, in order to contain the hydrophobic fluorine compound fine particles in the outermost layer, a fine particle dispersion of the hydrophobic fluorine compound and a separately prepared coating liquid containing a binder are mixed and applied, or the hydrophobic fluorine compound fine particles are mixed and applied. as required, anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids and/or nonionic surfactants such as sorbitan sesquioleate and sorbitan monolaurate, preferably fluorine-based anions, cations, A surfactant such as betaine or a nonionic surfactant is mixed with a solution of a binder for the outermost layer such as gelatin, and the resulting dispersion is emulsified and dispersed using a high-speed rotation mixer, colloid mill, or ultrasonic dispersion device. Just paint it.

In the present invention, the amount of the hydrophobic fluorine compound fine particles contained in the outermost layer is preferably in the range of o, oos to l of the binder volume of the outermost layer in terms of volume ratio, particularly 0.01
The amount of the hydrophobic fluorine compound fine particles used is preferably in the range of 0.4 to 0.4, and the color transfer prevention effect, adhesion failure prevention effect, releasability improvement effect and slipperiness of the present invention are achieved within this range.
The effect of improving transportability is remarkable.

The method of using fine particles of solid hydrophobic fluororesin of the present invention involves adding an anionic polymer such as acrylic acid or methacrylic acid to the surface layer of an image forming sheet, as described in Japanese Patent Application No. 179441/1982. Particularly favorable results are obtained when used in combination with techniques to prevent color transfer. That is, the fine particles of the solid hydrophobic fluororesin of the present invention have a higher ability to improve anionic properties than the method of improving peelability, conveyance property, and paper feeding property using oil droplets described in, for example, JP-A No. 62-174747. It is possible to improve releasability, conveyance properties, and paper feeding properties without impeding the effect of preventing color transfer by the adhesive polymer.

The above-mentioned anionic polymer is particularly a polymer containing a repeating unit represented by the following formula (1) (homopolymer,
copolymers) are preferably used.

In the formula, Ri represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a chlorine atom or -COOM, and R2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a chlorine atom.

xl and x3 represent -COO-1-CONR3-1 or a substituted or unsubstituted phenylene group (provided that R3
represents a hydrogen atom or a substituted or unsubstituted alkyl group or aryl group), Yl, Y2, zl, z2 are 2
represents a valent linking group, preferably a substituted or unsubstituted alkylene group, an aralkylene group,
group, -R'COO-1-RsOCO-1-R'0COR
'-, -COO-1-Ra-N-1 or -R1(1-
o- (However, R4, R5, R6, R7, R''
2 and RIO represent a substituted or unsubstituted alkylene group, phenylene group, or aralkylene group, and R9 represents a substituted or unsubstituted alkyl group, phenyl group, or aralkyl group). D is -(RllhcooM, -(R11
)-6SO,M.

)R11)-,504M,-(R”)-1SO,A,
-(R11)-, PO and Ml represent 2, E is a hydrogen atom, )R11)-; C00M, -(R11)-6SO
,M,-(R"hsO,M,-(R"hso,M,-(
R11)-, PO4MIM2 (however, A, M2 represents a hydrogen atom or an alkali metal, and BAl
represents a substituted or unsubstituted alkylene group, phenylene group, or aralkylene group. a, b, c, d, e represent O or 1). 0, m, p, q represent 0 or 1, and n.

r represents an integer from 0 to 30.

Above, R3, R4, R5, R', R7, Ra, R9, R
Substituents for lo and R11 include aryl group (e.g. phenyl group), nitro group, hydroxyl group, cyano group, sulfo group, alkoxy group (e.g. methoxy group), aryloxy group (e.g. phenoxy group), acyloxy group (e.g. acetoxy group). group), acylamino group (e.g. acetylamino group), sulfonamide group (e.g. methanesulfonamide group), sulfamoyl group (e.g. methylsulfamoyl group), halogen atom, carboxy group, carbamoyl group (e.g. methylcarbamoyl group), alkoxy Examples include a carbonyl group (eg, methoxycarbonyl group), a sulfonyl group (eg, methanesulfonyl group), and when there are two or more substituents, they may be the same or different.

Other monomers for forming the copolymer include 1, such as acrylic esters, methacrylic esters, crotonic esters, vinyl esters, maleic diesters, acrylamides, methacrylamides, vinyl ethers, styrenes, and unsaturated nitriles. Examples include:

Furthermore, saponified copolymers obtained from these monomers can also be used as the anionic polymer in the present invention.

The average molecular weight of the anionic polymer used in the present invention is lX
Approximately 10' to 2X10' is preferable. In addition, in the case of a copolymer with other copolymerizable monomers, -COOM or -803
Vinyl heptamer unit with M group accounts for 1 mol% of total monomers
The content is preferably in the range of 99.5 mol%, particularly 10 mol% to 99 mol%.

Specific examples of the anionic polymer used in the present invention are shown below.

9) Sumikagel L-58 (manufactured by Sumitomo Chemical) The anionic polymer used in the present invention is usually in the range of 0.05 to 20 g, preferably 0.1 to 5 g, particularly preferably 0.1 to 2 g per square meter of the support. used in Within this range, the effects of the present invention can be exhibited without adversely affecting other photographic properties or coatability.

When the anionic polymer used in the present invention does not have a site that crosslinks with the hardening agent used in the image forming sheet, it can be used more preferably by blending it with a binder having crosslinking sites.

The anionic polymer used in the present invention must be contained at least in a layer substantially above the dye fixing layer, that is, in a layer far from the support for one dye fixing layer. Especially Mogami M (
In addition to this upper layer, it can be optionally contained in other constituent layers of the image forming sheet, but the preferred content is 50% of the total polymer in the constituent layers. % or less. In this case, the same type of anionic polymer according to the present invention used in the upper layer may be used, or a different type may be used.

The image forming sheet of the present invention has the above-described structure, and the dye fixing layer is a layer containing a mordant and a binder or a dye-receiving polymer.

As the mordant, those known in the photographic field can be used, and specific examples thereof include those described in JP-A-61-88256. Among these, polymer mordants are preferred.

Polymer mordants include polymers containing tertiary amino groups, polymers containing nitrogen-containing heterocyclic moieties, and polymers containing these quaternary cation groups, and are preferably combined with other wood-philic polymers (gelatin, etc.). Used in combination.

Regarding polymers containing vinyl monomer units having tertiary amino groups, JP-A-60-60643, JP-A-60
Specific examples of polymers containing vinyl monomer units having tertiary imidazolium include JP-A-60-118834 and JP-A-60-122.
No. 941, Japanese Patent Application No. 61-87180, No. 61-871
No. 81, U.S. Patent No. 4,282,305, U.S. Patent No. 4,1
No. 15,124, No. 3.148,061, etc.

Preferred specific examples of polymers containing vinyl monomer units having quaternary imidazolium salts include British Patent No. 2,0
No. 56,101, No. 2,093,041, No. 1.
No. 594,961, U.S. Patent No. 4,124,386;
Same No. 4゜115.124, Same No. 4,273,853, Same No. 4,450,224.

It is described in JP-A No. 48-28225 and the like.

Other preferred specific examples of polymers containing vinyl monomer units having quaternary ammonium salts include U.S. Pat. No. 3,709,690, U.S. Pat. No. 60-57836,
No. 60-60643, No. 60-122940, No. 6
It is described in No. 0-122942 and No. 60-235134.

The molecular weight of the polymer mordant used in the present invention is preferably 1,000 to 1,000,000. Especially 10,000
~200.000.

Such a polymer mordant is used in combination with a hydrophilic colloid as a binder in the mordant layer.

Typical examples of hydrophilic colloids include proteins such as gelatin and gelatin derivatives, natural substances such as cellulose derivatives, starch, polysaccharides such as dextran, pullulan, and gum arabic, polyvinyl alcohol, polyvinylpyrrolidone, and polyacrylamide. Contains synthetic polymers.

Among these, gelatin and polyvinyl alcohol are particularly preferred.

The mixing ratio of the polymer mordant and hydrophilic colloid and the coating amount of the polymer mordant can be easily determined by those skilled in the art depending on the amount of dye to be mordant, the type and composition of the polymer mordant, and the image forming method to be applied. You can, but
mordant/! 5 to aqueous colloid ratio of 20/80 to 80/2
0 (weight ratio), the amount of mordant applied is about 0.2 to about 15 g/
rrr is suitable, and it is particularly preferable to use 0.5 to 8 g/rrr.

A polymer mordant can increase the dye transfer density by using it in combination with a metal ion.

This metal ion can be added to a mordant layer containing a mordant or a protective layer. The metal ions used here are preferably colorless and stable against heat and light. That is, Cu 24p, Zn", Ni", p t
Polyvalent ions of transition metals such as 2 +, p d2 +, and co3+ ions are preferred, and z n 2 '' is particularly preferred. This metal ion is usually in the form of a water-soluble compound,
For example, ZnSO4, Zn(CH, CO2), etc. are added, and the amount added is suitably about 0.01 to about 5 g/rrr, preferably 0.1 to 1.5 g/rrr.

A hydrophilic polymer can be used as a binder in the layer to which these metal ions are added. As the hydrophilic binder, hydrophilic colloids such as those specifically listed above regarding the mordant layer are useful.

Further, as the image-forming sheet of the present invention, an organic synthetic or natural polymer material that accepts a sublimable dye or a diffusible hydrophobic dye can be used in the form of a layer or a support. The organic synthetic or natural polymer substance used for boat fishing has a glass transition temperature (Tg) of 40° C. or higher and 250° C. or lower. A specific example is the Special Public Interest Publication No. 62-1585.
Organic polymer substances described in No. 8 and JP-A-59-124339 are used, and polyesters such as polyethylene terephthalate and polycarbonate are particularly preferably used.

The image forming sheet, especially its protective layer, contains a hydrophilic heat solvent,
Plasticizers (e.g. oils, low rg polymer latex, etc.)
, anti-fading agent, υV absorber, slip agent.

A matting agent, an antioxidant, a dispersed vinyl compound for increasing dimensional stability, a surfactant, an optical brightener, etc. may be included.

In addition, especially in systems where thermal development and dye transfer are performed simultaneously in the presence of a small amount of water, it is preferable for the dye fixing element to contain a base and/or a base precursor in order to improve the storage stability of the photosensitive element. Specific examples of additives are described in JP-A-61-88256.

In addition, the dye fixing element may be provided with auxiliary layers such as a release layer and an anti-curl layer.

The image forming sheet of the present invention is particularly advantageously used when fixing a diffusible dye in a color image forming method in which a diffusible dye is formed or released into an image and then diffused and then fixed.・ 1'' The above color image forming methods include those in which development is performed using a developer at a temperature near room temperature [color diffusion transfer method] (for example, the method described in Belly Patent No. 757,959), which is substantially moisture-free. (thermal development method) (e.g. European Patent No. 76.492)
A2. 220,746A2. 210,660A2,
There are various forms such as those described in Japanese Patent Application Laid-open Nos. 58-79247, 59-218443, 61-238056, Japanese Patent Applications 61-89379, 62-168899, etc.), but the present invention The image forming sheet can be used for any of the above.

Examples of dye-providing substances useful in the above color image forming method include compounds (couplers) that form dyes through oxidative coupling reactions. This coupler may be a 4-equivalent coupler or a 2-equivalent coupler, and a 2-equivalent coupler that has a diffusion-resistant group as a leaving group and forms a diffusible dye through an oxidative coupling reaction is also preferred. Specific examples of the developer and the coupler is written by James “
"The Theory of Photographic Process" 4th Edition (T, H James "The Theory of Photographic Process"
thePhotographic Process”
) pp. 291-334, and pp. 354-361, JP-A No. 58-123533, No. 58-149046, No. 58-149047, No. 59-111148, No. 5
No. 9-124399, No. 59-174835, No. 59
-231539, 59-231540, 60-
No. 173548, No. 60-179739, No. 60-1
No. 89743, No. 60-203942, No. 60-21
No. 2762, No. 61-37042, No. 62-1298
No. 50, No. 62-14649, No. 62-44738, Japanese Patent Application No. 61-220523, Japanese Patent Application No. 60-2950
No. 60-2951, No. 60-14242, No. 6
No. 0-23474, No. 60-66249, No. 61-1
No. 77451, No. 61-61158, No. 61-148
No. 447, No. 62-123456, No. 62-5238
No. 52-49378, No. 61-57336, No. 61-57743, No. 61-61157, No. 61-
No. 28946, No. 59-124339, Patent Application No. 1983-
It is described in detail in No. 180981, etc.

Another example of the dye-donating substance is a compound that has the function of releasing or diffusing a diffusible dye in an imagewise manner. This type of compound can be represented by the following general formula (Ll).

(Dye-X)n-Y (L
I) Dye represents a dye group, a temporally shortened dye group or a dye precursor group, or a mere bond or linking group, Y corresponds to a photosensitive silver salt with an imagewise latent image or Correspondingly, (Dye -X) causes a difference in the diffusivity of the compound represented by -Y, or Dye
ye is released, and the released Dye and (Dye −X)
Represents a group that has the property of causing a difference in diffusivity between n-Y, where n represents 1 or 2, and when n is 2, the two Dye-Xs may be the same or different. .

General formula [L! For example, a dye developer in which a hydroquinone developer and a dye component are linked is disclosed in U.S. Pat. No. 3,134,764.
No. 3,362,819, No. 3,597,20
No. 0, No. 3, 544, 545, No. 3,482
, No. 972, Japanese Patent Application No. 87347/1983, etc. Furthermore, a substance that releases a diffusible dye through an intramolecular nucleophilic substitution reaction is disclosed in U.S. Pat. -111628
It is stated in the number etc.

Another example is to make a dye-releasing compound into an oxidized form without dye-releasing ability, coexist with a reducing agent or its precursor, and after development, reduce it with the reducing agent that remains unoxidized to produce a diffusible dye. A method of releasing dye has also been devised, and a specific example of the dye-donating substance used therein is disclosed in Japanese Patent Application Laid-Open No. 53
-110827, U.S. Patent No. 4,356,249,
No. 4,358,525, No. 54-130927, No. 56-164342, No. 53-35533, No. 59-166954, No. 59-124327, No. 5
No. 9-124329, Japanese Patent Application No. 61-88656, etc. European Patent No. 220.746A2, Published Technical Report No. 87-6199, Japanese Patent Application No. 88625/1986, No. 61
-87721, 61-130342, 62-3
No. 4954.

No. 62-34953 and No. 62-168899,
As a dye-donating substance that releases a diffusible dye by a similar mechanism, the remaining reducing agent acts as a dye-donating substance that releases an N-X bond (or an oxygen atom,
Compounds have been described in which a nitrogen or sulfur atom) is cleaved to release a diffusible dye.

Furthermore, as described in JP-A-59-185333, a donor-acceptor reaction occurs in the presence of a base and releases a diffusible dye, but when it reacts with an oxidized form of a reducing agent, dye release does not substantially occur. Non-diffusible compounds (LDA compounds) can also be used.

In all of these methods, the diffusible dye is released or diffused in areas where development has not occurred, and the dye is neither released nor diffused in areas where development has occurred.

On the other hand, as a substance that releases a diffusible dye in the area where development occurs, it is a coupler that has a diffusible dye as a leaving group and that releases a diffusible dye by reaction with an oxidized form of a reducing agent (DDR coupler). However, British Patent No. 1,330,52
No. 4, Japanese Patent Publication No. 48-39165, U.S. Patent No. 3,44
No. 3,940, JP-A No. 61-210351, JP-A-61-210351, No. 61-
No. 14633, No. 60-14242, No. 59-124
No. 31, No. 59-116642, No. 59-11664
No. 3, etc., and is preferably used in the present invention.

In addition, in methods using these reducing agents, image contamination due to oxidative decomposition products of the reducing agent may become a problem. Dye-releasing compounds (DRR compounds) have also been devised and are particularly advantageously used in the present invention. Typical examples are U.S. Pat. No. 3,928,312, U.S. Pat.
No. 053,312, No. 4.055,428, No. 4
, No. 336, 322, JP-A No. 59-65839, No. 5
No. 9-69839, No. 53-3819, No. 51-10
No. 4343, Research Disclosure Magazine 1746
No. 5, U.S. Patent No. 3,725,062, U.S. Patent No. 3,72
No. 8,113, No. 3,443゜939, JP-A-58
-116537 No. 179840, U.S. Patent No. 4
, No. 500,626, Japanese Patent Application No. 61-84274, Japanese Patent Application Publication No. 62122, No. 56-16131, No. 57-85
No. 055, No. 57-4043, No. 53-3819,
No. 57-650, No. 54-48534, No. 57-2
No. 0735, No. 59-65839, U.S. Patent No. 4,0
53°312, European Patent No. 76.492, etc. A specific example of this type of dye-donating substance is the aforementioned U.S. Pat. No. 4,500,62.
Examples of the compounds described in columns 22 to 44 of No. 6 include the compounds described in the above-mentioned U.S. patent (
1)-(3), (lO)-(13), (16)-(19
), (28) to (30), (33) to (35), (3
8) to (40) and (42) to (64) are preferred, and the compounds described in JP-A-61-124941 are also useful. In addition, as dye-donating substances other than those mentioned above, dye silver compounds that combine organic silver salts and dyes (research
Disclosure magazine, May 1978 issue, pages 54-58), azo dyes used in heat-developable silver dye bleaching methods (U.S. Patent No. 4,235,957, Research Disclosure magazine, April 1976 issue, 30- 32 pages, etc.), leuco dyes (U.S. Pat. No. 3,985,565, U.S. Pat. No. 4,0
No. 22,617, etc.) can also be used.

The image-forming sheet of the present invention can be used in combination with a color diffusion transfer photosensitive element that is developed using a processing solution at around room temperature, or with a heat-developable photosensitive element that is developed by heating. .

Silver halide that can be used in the above photosensitive element.

It may be silver chloride, silver bromide, silver chlorobromide, silver chloroiodide, or silver chloroiodobromide.

Specifically, U.S. Pat. No. 4,500,626, column 50;
Research Disclosure Magazine, June 1978 issue, pages 9-10 (RD17029), JP-A-61-10724
Any of the silver halide emulsions described in No. 0, No. 62-85241, No. 62-87957, etc. can be used.

The silver halide emulsion used in the present invention may be of the surface latent image type where the latent image is mainly formed on the grain surface, or the internal latent image type where the latent image is formed inside one grain, or may be of the internal latent image type where the latent image is mainly formed on the grain surface. It may be a so-called core-shell emulsion in which the grain surface layer has different phases.

Further, in the present invention, a direct reversal emulsion in which an internal latent image type emulsion and a nucleating agent are combined can also be used.

The image forming sheet (dye fixing material) of the present invention is used as a dye fixing material that fixes one dye together with a photosensitive material that forms or releases a dye upon development.

Typical forms of photosensitive materials and dye-fixing materials are broadly divided into two types: one in which the light-sensitive material and the dye-fixing material are coated on two supports separately, and the other in which they are coated on the same support. be done. The relationship between the light-sensitive material and the dye-fixing material, the relationship with the support, and the relationship with the white reflective layer are described in JP-A-61-147244, pages 58-59, and U.S. Pat. No. 4,500,626, No. 519. The relationships described are also applicable to the present application.

In the present invention, an image forming sheet (also referred to as an image receiving material)
may be provided on a support separate from the photosensitive material, or may be a film unit combined with the photosensitive material.

A typical embodiment of the present invention is one in which a light-sensitive material and an image-receiving material are separately coated on two supports. In a preferred embodiment, at least one dye-receiving layer (image-receiving layer) is coated on the surface of the support, and the light-sensitive material is coated on another support, and at least after exposure (e.g. During the development process), the surface coated with the photosensitive layer and the surface coated with the image-receiving layer are designed to overlap. After the transfer image is completed with the mordant layer, the light-sensitive material is immediately peeled off from the image-receiving material.

In another embodiment, the above image-receiving material and photosensitive material are laminated on one transparent support, and the photosensitive material is peeled off from the image-receiving material after the transferred image is completed. More specifically, the image-receiving material comprises at least one mordant layer, and in a preferred embodiment of the light-sensitive material, a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, or a green-sensitive emulsion layer. , a combination of a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, or a combination of a blue-sensitive emulsion layer, a red-sensitive emulsion layer and an infrared-sensitive emulsion layer, and a yellow dye-donating substance in each of the emulsion layers; A magenta dye-providing substance and a cyan dye-providing substance are each combined to form a structure (here, [
The infrared light-sensitive emulsion layer is 700 nm or more, especially 7401
(This refers to an emulsion layer that is sensitive to the above light), and between the mordant layer and the light-sensitive layer or the dye-donating substance-containing layer, there is a transparent support so that the transferred image can be viewed through the transparent support.
A white reflective layer containing a solid pigment such as titanium oxide is provided.

A light-shielding layer may be further provided between the white reflective layer and the photosensitive layer so that the development process can be completed in a bright place. In addition, a release layer may be provided at an appropriate position so that all or part of the photosensitive material can be peeled off from the image-receiving material. 082).

Furthermore, in another embodiment, the photosensitive material described above is coated on one transparent support, a white reflective layer is coated thereon, and an image-receiving layer is further laminated thereon. An image receiving material, a white reflective layer, a peeling layer, and a photosensitive material are laminated on the same support,
A method for intentionally peeling a photosensitive material from an image receiving material is described in U.S. Pat. No. 3,730,718.

In the above embodiment, if the photosensitive material and the image-forming sheet (dye-fixing material or image-receiving material) are coated on separate supports, the outermost layer on the front and/or back surface of the image-forming sheet The hydrophobic fluorine compound fine particles of the present invention are added to.

In addition, when the photosensitive material and the image forming sheet are laminated on the same transparent support, the back layer of the support or the outermost layer of the image forming sheet in contact with the photosensitive material (for example, a release layer, etc.) The hydrophobic fluorine compound fine particles of the present invention are added to.

All of the above-mentioned forms can be applied to both the color diffusion transfer method and the heat development method, but especially in the former case, a container (processing element) containing an alkaline processing liquid and rupturable under pressure is also combined. You can. In particular, in a peelable film unit in which an image-receiving material and a photosensitive material are laminated on one support, this processing element is preferably disposed between the photosensitive material and a cover sheet superimposed thereon. Further, in the case where the light-sensitive material and the image-receiving material are separately coated on two supports, it is preferable that a processing element be placed between the light-sensitive material and the image-receiving material at the latest during development processing.

Depending on the form of the film unit, the processing element preferably contains a light blocking agent (such as carbon black or a pH-dependent dye) and/or a white pigment (such as titanium oxide). Furthermore, in color diffusion transfer film units, a neutralization timing mechanism consisting of a combination of a neutralization layer and a neutralization timing layer is provided in the cover sheet or in the image receiving material.
Alternatively, it is preferably incorporated into a photosensitive material.

On the other hand, in a heat-developable film unit, a support,
Joules generated when a heat-generating layer containing fine metal particles, conductive particles such as carbon black or graphite is provided at an appropriate position of a photosensitive material or image-receiving material and electricity is applied for thermal development or diffusion transfer of dyes. You can use heat,
Semiconductive inorganic materials (e.g. silicon carbide,
Molybdenum silicide, lanthanum chloride, barium titanate ceramics, tin oxide, zinc oxide, etc.) may be used.

The present invention particularly relates to a heat-developable image forming sheet,
The effect is remarkable.

The photosensitive material used in the present invention may contain various additives known for use in heat-developable photosensitive materials and layers other than the photosensitive layer, such as a protective layer, an intermediate layer, an antistatic layer, an antihalation layer, and a dye. It can have a release layer, a matte layer, etc. to facilitate peeling from the fixing material. Examples of various additives include plasticizers described in Research Disclosure Magazine, June 1978 issue, pages 9 to 15, JP-A-61-88256, etc., and plasticizers described in JP-A-61-156252. Water-absorbing polymers, matting agents, sharpness improving dyes, antihalation dyes, surfactants, optical brighteners, anti-slip agents, antioxidants, anti-fading agents, reducing agents as described in Japanese Patent Application No. 168899/1983 , color mixing inhibitors, development accelerators, organic silver salts, and other additives.

In particular, the protective layer may further contain an organic or inorganic matting agent to prevent adhesion. Further, this shin protection layer may contain a mordant and an ultraviolet absorber.

Each of the protective layer and the intermediate layer may be composed of two or more layers.

Further, the intermediate layer may contain a reducing agent to prevent color fading and color mixing, an ultraviolet absorber, and a white pigment such as titanium dioxide. A white pigment may be added not only to the intermediate layer but also to the emulsion layer for the purpose of improving sensitivity.

Photosensitive elements that can be used in the present invention include, for example, U.S. Pat.
No. 914, No. 4,500,626, No. 4,503
, No. 137, JP-A-59-154445, JP-A-59-Sho.
-165054, JP 59-180548, JP 59-218443, JP 60-120356, JP 61-88256, European Patent 210660A
2, 220746A2. Patent Application No. 1988-88623,
No. 67-97880, No. 62-106883, No. 6
Any of those described in No. 2-166885 etc. can be used.

In addition, as a positive type photosensitive element using an internal latent image type fogging emulsion, Japanese Patent Application Nos. 61-179439 and 1983-177
No. 440, No. 61-247563, No. 62-4042
No. 7, No. 62-20524, No. 62-53127,
Any of those described in JP-A-62-61056, JP-A-62-18540, JP-A-61-157643, JP-A-61-157641, etc. can be used.

In the present invention, various antifoggants, S/N improvers, or photographic stabilizers can be used in the light-sensitive material and/or the dye-fixing material. For example, research
Disclosure magazine December 1978 issue No. 24-25
Azoles and azaindenes described on page 1, JP-A-59-
Nitrogen-containing carboxylic acids and phosphoric acids described in No. 168442, or mercapto compounds and metal salts thereof described in JP-A-59-111636, JP-A-62-879
Acetylene compounds described in No. 57 are used.

In the present invention, an image formation accelerator can be used in the light-sensitive material and/or the dye-fixing material.

Image formation accelerators include accelerating redox reactions between silver salt oxidizing agents and reducing agents, accelerating reactions such as generation of dyes from dye-donating substances, decomposition of dyes, and release of diffusible dyes, and photosensitive material layers. Physicochemical functions include bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, It is classified as a compound that interacts with silver or silver ions. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. Details of these are described on pages 67 to 71 of JP-A-61-93451.

There are various other methods of generating bases.

Any of the compounds used in the method are useful as base precursors, e.g. European Patent No. 210.66
0A2, and a method of generating a base by mixing a poorly soluble metal compound and a compound capable of forming a complex with the metal ions constituting the hardly soluble metal compound (referred to as a complex-forming compound); There is a method of generating a base by electrolysis as described in No. 232451. The former method is particularly effective.

In the present invention, the light-sensitive material and/or dye-fixing material includes:
Various development stoppers can be used for the purpose of always obtaining a constant image despite fluctuations in processing temperature and processing time during development.

The development stopper referred to here is a compound that neutralizes the base immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that inhibits development by interacting with silver and silver salts. It is a compound that

Specifically, an acid precursor that releases acid upon heating;
Examples include electrophilic compounds, nitrogen-containing heterocyclic compounds, mercapto compounds, and their precursors that undergo a substitution reaction with a coexisting base when heated (for example, JP-A-60-10
No. 8837, No. 60-192939, No. 60-230
No. 134 or U.S. Pat. No. 4,610,957).

Compounds that release mercapto compounds upon heating are also useful, for example, JP-A No. 61-67851, JP-A No. 61-67851;
No. 147244, No. 61-124941, No. 61-1
No. 85743.

No. 61-182039, No. 61-185744, No. 61-184539, No. 61-184539, No. 6
There is a compound described in No. 1-53632.

In the present invention, a hydrophilic binder can be used for the photosensitive material and/or the dye fixing material. As the hydrophilic binder, the same binder as the binder of the outermost layer to which the fluorine-based fine particles are added can be used.

These binders can be used alone or in combination.

In the present invention, the binder is applied in an amount of 20 g or less per bag, preferably 10 g or less, more preferably 7 g or less.
g or less is appropriate.

The ratio of the binder to the high boiling point organic solvent dispersed in the binder along with oil droplets, anti-fading agents, and ultraviolet water absorbing agents to improve brittleness or peelability is relative to the binder (total polymer including polymeric compounds such as mordants) Ig. and solvent 1c
The appropriate amount is 0.3cc or less, preferably 0.5cc or less, and more preferably 0.3cc or less.

In the present invention, the constituent layers (photographic emulsion layer, dye fixing layer, etc.) of the light-sensitive material and/or dye fixing material may contain an inorganic or organic hardening agent.

Specific examples of hardening agents are given in JP-A-61-147244, pages 94 to 95, and JP-A-59-157636 (
Examples include those described on page 38), and these can be used alone or in combination.

When applying a small amount of water to the light-sensitive material or dye-fixing material during heat development or dye transfer to accelerate heat development or speed up dye transfer, water does not completely cover the coating film. In order to shorten the permeation time, it is preferable to keep the hardness of the photographic material to which water is applied below a certain value. Therefore, in such an embodiment, the hardening agent is cross-linked with the hardening agent. The use of hardeners in this range, preferably at a content of 10% by weight or less, particularly from 1 to 10% by weight, based on the total binder composition, improves the release properties to some extent, but by the means of the present invention, the release properties can be further improved by the means of the present invention.
Layer peelability can be improved.

Further, in order to promote dye transfer, a hydrophilic thermal solvent that is solid at room temperature and soluble at high temperature may be incorporated into the light-sensitive material or dye fixing material. The hydrophilic heat solvent may be incorporated into either the photosensitive material or the dye fixing material, or may be incorporated into both. The built-in layer may also be an emulsion layer, an intermediate layer, a protective layer, or a dye fixing layer, but the dye fixing layer and/or
Alternatively, it is preferable to incorporate it into a layer adjacent thereto. Examples of hydrophilic heat solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles. Further, in order to promote dye transfer, a high boiling point organic solvent may be included in the light-sensitive material and/or the dye fixing material.

The support used for the light-sensitive material and/or dye-fixing material in the present invention is one that can withstand processing temperatures. - Glass, paper, polymer films, metals and their analogues are used as supports for boat fishing, as well as pages 95 to 96 of JP-A-61-147244.
The supports listed on the page can be used.

The photosensitive material and/or dye fixing material is used as a heating means for heat development or diffusion transfer of dye as described in Japanese Patent Application Laid-open No. 61-29.
In the present invention, the heat development and dye transfer steps may be performed independently or simultaneously. There may be. Further, it may be continuous in the sense that transfer is performed following development in the -step.

For example, (1) after exposing the photosensitive material and heating it, 1
There are two methods: (1) a method in which dye-fixing materials are stacked and heated if necessary to transfer the mobile dye to the dye-fixing material; and (2) a method in which a light-sensitive material is imagewise exposed, and the dye-fixing materials are stacked and heated.

The methods (1) and (2) above can be carried out in the substantial absence of water or in the presence of a trace amount of water.

The heating temperature in the heat development step can be developed at about 0°C to about 250°C, and particularly useful is about 0°C to about 180°C. When heating in the presence of a trace amount of water, the upper limit of the heating temperature is below the boiling point. When the transfer step is performed after the heat development step, the heating temperature in the transfer step can be in the range from the temperature in the heat development step to room temperature, but in particular, it is about 10 degrees Celsius or higher than the temperature in the heat development step at 50 degrees Celsius or higher. It is more preferable to lower the temperature.

A preferred image forming method in the present invention involves heating in the presence of a trace amount of water and a base and/or a base precursor after or simultaneously with image exposure, and simultaneously with development, diffusion is generated in a portion corresponding to or inversely corresponding to a silver image. The coloring matter is transferred to the dye fixing layer. According to this method,
Since the production or release reaction of the diffusible dye proceeds extremely quickly and the transfer of the diffusible dye to the dye fixing layer also proceeds rapidly, a high-density color image can be obtained in a short time.

The amount of water used in this embodiment is at least 0.001 times, preferably 0.1 times or more, the weight of the total coating film of the photosensitive material and dye fixing material, and not more than the weight of the solvent corresponding to the maximum swelling volume of the total coating film. A small amount (particularly not more than the amount obtained by subtracting the weight of the entire coating film from the weight of the solvent corresponding to the maximum swelling volume of the entire coating film) may be sufficient.

The state of the film during swelling is unstable, and depending on the conditions, local bleeding may occur.To avoid this, add water equivalent to the maximum swelling volume of the total coating film thickness of the photosensitive material and dye fixing material. It is preferable that the amount is less than or equal to . Specifically, 1 g per square meter of the total area of photosensitive material and dye fixing material.
A range of 50g, particularly 2g to 35g, and even 3g to 25g is preferred.

The base and/or base precursor used in this embodiment can be incorporated into both the light-sensitive material and the dye-fixing material. It can also be supplied dissolved in water.

In the above embodiment, the image forming reaction system contains, as a base precursor, a basic metal compound that is sparingly soluble in water and a compound that can undergo a complex formation reaction with metal ions constituting the sparingly soluble metal compound using water as a medium; Preferably, the pH of the system is raised by the reaction of these two compounds upon heating; by image-reactive system here is meant the region in which the image-forming reaction takes place.

Specifically, layers belonging to both photosensitive materials and dye fixing materials can be mentioned. If there are two or more layers,
Any of these layers may be used.

It is necessary to add the poorly soluble metal compound and the complex-forming compound to at least separate layers in order to prevent them from reacting before the development process.For example, when the light-sensitive material and the dye fixing material are provided on the same support, In a so-called monosheet material, it is preferable to separate the above-mentioned two additive layers, with one or more layers interposed between them.In a more preferable form, the slightly soluble metal compound and the complex-forming compound are each added separately. For example, it is preferable to contain a poorly soluble metal compound in a light-sensitive material and a complex-forming compound in a dye-fixing material that has a support separate from the light-sensitive material. The complex-forming compound may be supplied after being dissolved in the coexisting water.
It is desirable to contain it as a fine particle dispersion prepared by the method described in No. 30, No. 53-102733, etc.
The average particle size is preferably 50 microns or less, especially 5 microns or less.

Slightly soluble metal compounds are used in photosensitive layers and intermediate layers of photosensitive materials.

It may be added to any layer such as the protective layer, or may be added after being divided into two or more layers.

The amount of a poorly soluble metal compound or complex-forming compound to be added to the layer on the support depends on the type of compound, the particle size of the poorly soluble metal compound, the rate of complex formation reaction, etc. It is appropriate to use it in an amount of 50 weight cents or less, more preferably in the range of 0.01 weight percent to 40 weight percent. In addition, when supplying a complex-forming compound dissolved in water,
A concentration of 0.005 mol to 5 mol, especially 0.05 mol to 2 mol per liter is preferred. Furthermore,
In the present invention, the content of the complex-forming compound in the reaction system is from 1/100 to 10 times the molar ratio of the content of the poorly soluble compound.
0 times, especially 1/10 times to 20 times is preferable.

The method for adding water to the photosensitive layer or dye fixing layer is as follows:
For example, page 101, line 9 of JP-A-61-147244~
There is a method described on page 102, line 4.

As a heating means in the development and/or transfer process, a hot plate, an iron, a hot roller, etc. are used.
There is a means described in No. 7244, page 102, line 14 to page 103, line 11. Alternatively, a layer of a conductive material such as graphite, carbon black, or metal may be applied to the photosensitive material and/or the dye fixing material, and the conductive layer may be heated directly by passing an electric current through it. .

The pressure conditions and method of applying pressure when overlapping the photosensitive material and the dye-fixing material and bringing them into close contact are described in Japanese Patent Application Laid-Open No. 1472-1983.
The method described in No. 44, pages 103 to 104 can be applied.

Any of a variety of thermal development equipment can be used to process photographic materials. For example, JP-A No. 59-75247, JP-A No. 59-75247;
No. 177547, No. 59-181353, No. 60-1
Apparatuses described in No. 8951, Utility Model Application Publication No. 60-116734, etc. are preferably used.

As a light source for image exposure to record an image on this heat-developable photosensitive material, a sealed wire containing visible light can be used. Typical light sources include natural light, ultraviolet light, and low-energy radiation sources. , visible light, infrared light, fluorescent lamps, tungsten lamps, mercury lamps, halogen lamps, xenon flash lamps, laser light sources (gas lasers, solid-state lasers, chemical lasers, semiconductor lasers, etc.), light-emitting diodes, plasma arc tubes, FOT, etc. Can be done. In special cases, X-rays, which are high-energy sources,
γ rays, electron beams, etc. can be used.

After the heat development and dye transfer are completed, the photosensitive material and the dye fixing material are peeled off. According to the present invention, this peeling can be carried out extremely easily. The peeling of both materials can also be done manually.
Also, JP-A-42-5474, JP-A-41-5676, JP-A-45-1354, JP-A-53-29713, JP-A-60
-135944 and the like may be used.

Photographic materials using this image forming method are easy to process and have high image quality, so they are used as print materials in many industrial fields.

Hereinafter, a specific example of the present invention will be shown and the present invention will be explained in further detail.

Example 1 A photosensitive material was prepared in the same manner as photosensitive material 101 of Example 1 of JP-A-62-183457.

A dye fixing material 100 for thermal development transfer image forming method was prepared with the composition shown in Table 1.The outermost layer on the front side (third layer: protective layer) and the outermost layer on the back side of the dye fixing material 100. Dye fixing materials 101 to 107 were produced in the same manner except that the fine particles shown in Table 2 were contained in the (second layer: back layer).

After the photosensitive material was imagewise exposed, 12g/n (of water was applied with a wire bar) and the photosensitive material and the dye fixing material 100 ~
107 so that the film surfaces are in contact with each other, and heat rollers adjusted so that the film surface temperature is 98 ° C.
After heating for seconds, the photosensitive material and the dye fixing material were peeled off.

At this time, the force required for peeling was determined in the same manner as in Example 1 of Japanese Patent Application No. 61-272895.

Table 2 shows the values and the surface condition of the peeled dye-fixing material.
It was shown to.

Table 1 ・l) Surfactant A -2) Surfactant B -3) Mordant -4) Oil drop Compound: liquid paraffin' and addition 5% aqueous solution of sodium dodecylbenzenesulfonate to 100 g of 10% aqueous gelatin solution Add 5+wQ, add 20g of liquid paraffin, and mix with a homo blender.
A dispersion of oil droplets prepared by emulsification and dispersion at , 000 rpm for 6 minutes was added to the coating liquid for the dye fixing layer (first layer).

*5) Hardener A n -6) Surfactant C Umbrella 7) Method for preparing a dispersion of fluorine-based fine particles manufactured by Nippon Shokubai Chemical Co., Ltd. (in the case of fluorine oil) Oil added to the dye fixing layer described above Prepared in the same manner except that in the method for preparing drops, a 5% methanol solution of fluorosurfactant A was used instead of a 5% aqueous solution of sodium dodecylbenzenesulfonate, and fluorocarbon oil (Demnum S-65) was used as the oily component. did.

<In the case of solid fluororesin> Add 5 g of solid fluororesin fine particles (Luburon L-2) and 5 cc of a 5% methanol solution of fluorosurfactant A to 100 cc of water, mix well, and then perform ultrasonic dispersion. A dispersion was prepared by dispersing in a machine for 5 minutes.

Adhesion color transfer test method> The photosensitive material was fully exposed to white light and 12 g/if was applied to the emulsion surface.
of water was supplied with a wire bar, and then the pre-dye fixing material and the membrane surface were overlapped so that they were in contact with each other. After heating the absorbed pus for 35 seconds using a heat roller whose temperature was adjusted to 93°C, the dye-fixing material was peeled off from the photosensitive material, and the dye was transferred to the entire surface black (this is called Sheet B). ), and the unexposed photosensitive material A was further processed in the same manner as above to obtain a white dye-fixing material (referred to as sheet W) in which no dye transfer occurred. The sheet B and the sheet W were cut into a size of 30 m x 30 m, and the white light density was measured using a Macbase reflection densitometer (RD-519).

The density of Sheet B was approximately 2.0 in all cases.

The density of the sheet W is assumed to be D1. Said sheet B and sheet W
After conditioning the humidity at 25° C. and 80% RH for 2 hours, they were stacked on top of each other so that the membrane surfaces were in contact with each other, and a load of 500 g was applied and left for another day. After that, this was peeled off and one color was transferred to the sheet W.The density of the dye was measured in the same manner as before the superposition (this density was measured as D
v), and the magnitude ΔDv of "adhesive color transfer" at this time is expressed as Dv-Dllv.

The results (Δo V) are shown in Table 2.

In addition, patent application for two dye fixing materials 100 to 107 was filed in 1986-2.
Based on the method of Example 1 of No. 72895 at 30°C 75%
A paper feeding test was conducted under RH. The results are shown in Table-2.

(Margins below) Table 2 $1) Surface condition of dye fixing material; C: Very large with emulsion film of photosensitive material B: Slightly present A: None, good gloss)・2) Paper feeding property: 50 sheets fed Table of number of times multiple sheets were fed while paper was being fed - 2
As is clear from the results in Table 1, the dye fixing material containing the fluorine-based fine particles of the present invention in the outermost layer can be easily peeled off after heat transfer and does not cause emulsion film adhesion to the film surface. It is also found that when the fine particles of the present invention are contained in the outermost layer of the front and/or back, paper feeding properties are particularly good under high humidity conditions. Furthermore, it can be seen that the effect of preventing color fading by acrylic acid is not inhibited.

Agent Patent Attorney (8107) Kiyotaka Sasaki Procedural Corrections Department June 1988

Claims (1)

[Claims] 1. An image forming sheet having at least one dye-receiving layer on a support, the sheet containing fine particles of a hydrophobic fluorine compound on the front and/or back surfaces of the sheet.