JPH083617B2 - Dye fixing element - Google Patents

Description

TECHNICAL FIELD The present invention relates to a dye-fixing element, and more particularly to a dye-fixing element having a matte surface with improved surface smoothness and preventing transfer unevenness during color image transfer. .

(Prior Art) Conventionally, in a color diffusion transfer method or a heat development transfer method, a diffusible dye formed or released in an image by developing a photosensitive element after exposure is diffuse-transferred to a dye-fixing layer containing a mordant. It The dye image transferred and fixed on the dye fixing layer is observed as an image. Therefore, the dye fixing layer requires a mordant for fixing the diffusible dye and a binder in which the mordant is dispersed in a layered form, and the dye fixing layer should be matted to adjust the glossiness during observation. May be required.

(Problems to be Solved by the Invention) Conventionally, a method of adding a matting agent has been known as a matting direction, but the cheapest and most effective method is to emboss the support at the time of manufacturing the support. This is a method of providing an uneven surface. However, when a dye fixing layer consisting of a mordant and a binder is applied on a support having an uneven surface by embossing, the surface of the dye fixing layer opposite to the surface in contact with the support also corresponds to the uneven surface of the support. As a result, a dye-fixing layer having a smooth surface cannot be obtained. Transferring a diffusible dye image by superimposing such a dye-fixing element having poor surface smoothness on a photosensitive element causes transfer unevenness (uneven surface density unevenness), which is a problem.

In particular, in the heat development transfer method, as a base precursor in the image forming reaction system, a basic metal compound that is poorly soluble in water and a compound capable of undergoing a complex formation reaction with water as a medium and a metal ion that constitutes the sparingly soluble metal compound ( (Hereinafter referred to as "complex forming compound"), and the pH of the system is increased by the reaction of these two compounds when heated. In order to prevent these sparingly soluble metal compound and complex-forming compound from reacting before development processing, for example, a dye-fixing element having a support as a photosensitive element with a sparingly soluble metal compound and a complex-forming compound separately from the photosensitive element. Preferably contained in However, when a dye-fixing element having poor surface smoothness and a light-sensitive element are superposed on each other, the pH of the convex portion due to the reaction of the above two compounds.
However, the reaction hardly occurs in the concave portion, and the unevenness of the alkali concentration distribution occurs at the interface between the two elements, which causes remarkable unevenness in the transfer of the dye image, which is a serious problem.

Further, the particle size of the matting agent particles used in the photographic field is usually relatively larger than the thickness of the dye fixing layer. Further, if the particle size of the matting agent is made relatively small, sufficient matting performance cannot be obtained. Therefore, even in the method of adding the matting agent, a dye fixing element having a smooth surface has not been obtained.

Accordingly, an object of the present invention is to provide a dye fixing element having a matte surface which has excellent surface smoothness and prevents transfer unevenness during color image transfer.

(Means for Solving the Problems) An object of the present invention is to provide a dye-fixing element comprising a dye-fixing layer containing a mordant, a layer containing two or more kinds of polymer binder substances in a state of being microphase-separated from each other. Was achieved by a dye fixing element having

 Hereinafter, the present invention will be described in detail.

The present inventors have found that the polymeric binder materials used in the dye fixing layer or its adjacent layer form a uniform transparent film when used alone, but when used in combination of two or more,
In some combinations, the individual polymeric binder materials undergo phase separation and, upon agitation, are present as fine particles in the microphase separated state. At this time, it was discovered that particles having microphase separation were observed as if they were matted because the individual polymer binder materials had different refractive indices, and the present invention was completed.

In the present invention, a combination of two or more polymer aqueous solutions (0.
(5 to 10% by weight) at 20 to 40 ° C. in equal amounts, and after mixing and stirring, the mixture may be placed in a cylinder and allowed to stand at the above temperature to separate into two or more phases. There are the following. Combinations of polyvinyl alcohol / gelatin, polyvinyl alcohol / polyacrylic acid, polyvinyl alcohol / polyacrylamide and the like.

Particularly preferred is a polyvinyl alcohol / gelatin combination.

The ratio (weight ratio) in the combination of two or more kinds of polymer binder substances that causes these microphase separations varies depending on the kind of the polymer binder substances in each combination. For example, in the combination of polyvinyl alcohol / gelatin, 10 / 90 to 90/10 (weight ratio) is preferable, and 20/80 to 60/40 is particularly preferable.

Layers that use a combination of two or more polymeric binder materials that cause microphase separation are preferably dye-fixing layers, but may also be used over or underneath the layer or layers thereof.

In the present invention, the total coating amount of the two or more types of polymer binder substances that cause microphase separation is arbitrary. When a mordant is used, the mixing ratio of the mordant and the polymeric binder substance can be easily determined by those skilled in the art according to the amount of the dye to be mordant, the type and composition of the mordant, and the image forming method applied. be able to. Generally, the total coating weight of polymeric binder material is preferably from about 0.5 to about 10 g / m ² , especially 1
~ 5 g / m ² is preferred. The mordant / polymer binder material ratio is preferably 1/5 to 5/1 (weight ratio), particularly preferably 1/3 to 3/1.

A mordant is preferably used in the dye fixing layer in the present invention. The mordant can be arbitrarily selected from commonly used mordants.

Polymer mordants can also be used as mordants. Here, the polymer mordant is a polymer having a tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer having a quaternary cation group thereof, or the like.

Preferred specific examples of homopolymers and copolymers containing a vinyl monomer unit having a tertiary amino group include the following. The numbers of the monomer units represent mol% (the same applies hereinafter).

Such.

Specific examples of homopolymers and copolymers containing a vinyl monomer unit having a tertiary imidazole group, U.S. Pat.Nos. 4,282,305, 4,115,124, 3,148,061, JP-A-60-118834, 60-122941 and the like. The following are included, including the mordants described.

Such.

Preferred specific examples of homopolymers and copolymers containing a vinyl monomer unit having a quaternary imidazolium salt, British Patent Nos. 2,056,101, 2,093,041, and 1,594,
961, U.S. Pat.Nos. 4,124,386, 4,115,124 and 4,2
73,853, 4,450,224, and mordants described in JP-A-48-28,225 and the like are listed below.

Such.

Other preferred specific examples of homopolymers and copolymers containing a vinyl monomer unit having a quaternary ammonium salt include U.S. Patent Nos. 3,709,690 and 3,898,088.
3,958,995, JP-A-60-57836, 60-60643, 6
The followings are included, including mordants described in 0-122940, 60-122942, 60-235134 and the like.

Such.

In addition, U.S. Patent Nos. 2,548,564 and 2,484,430,
Vinyl pyridine polymers and vinyl pyridinium cation polymers disclosed in U.S. Pat. Nos. 3,148,161 and 3,756,814; US Pat. Nos. 3,625,694, and 3,8
59,096, No. 4,128,538, a polymer mordant capable of crosslinking with gelatin and the like disclosed in British Patent No. 1,277,453; U.S. Patent Nos. 3,958,995 and 2,721,852,
No. 2,798,063, JP-A Nos. 54-115228 and 54-145529.
No. 54-26027 and other aqueous sol type mordants; US Pat. No. 3,898,088, water insoluble mordants; US Pat. No. 4,168,976
4-137333) Reactive mordants capable of forming a covalent bond with the dyes disclosed in the specification, etc .; and US Pat. No. 3,709,690.
No. 3, No. 3,788,855, No. 3,642,482, No. 3,488,70
No. 6, No. 3,557,066, No. 3,271,147, No. 3,271,1
48, JP-A-50-71332, 53-30328, and 52-1555.
The mordants disclosed in Nos. 28, 53-125 and 53-1024 can be mentioned.

Other examples include mordants described in U.S. Pat. Nos. 2,675,316 and 2,882,156.

Among these mordants, a mordant having an imidazole group as a main mordant site (for example, compounds (4) to (1
1)) is preferable, and particularly (4), (6), (8),
(9) and the like are preferable.

The molecular weight of the polymer mordant of the present invention is 1,000 to 1,000,000.
Is suitable, and particularly preferably 10,000 to 200,000.

In the present invention, the dye fixing layer is composed of at least one layer and may contain a brittleness improver, a base or a base precursor in addition to a mordant and two or more kinds of polymer binder substances which cause microphase separation.

Other additives include hardeners, coating aids, antistatic agents, anti-adhesion agents, etc. for the purpose of preventing the precipitation of surfactants, antifoggants, anti-fading agents, UV absorbers, sliding agents, bases or base precursors. The target hydrophilic polymer, optical brightener, etc. may be contained.

For the purpose of improving the brittleness of the dye fixing layer, it is preferable to add oil droplets to the constituent layers (including the mordant layer) on the side where the dye fixing layer is present. In this case, oil droplets are preferably added in an amount of 2 to 100 vol%, particularly 5 to 50 vol% based on the total polymer in the addition layer.

In the present invention, the oil droplets are oil-based independent systems finely dispersed in a hydrophilic colloid, and are substantially water-insoluble liquid particles. The finer the size of the oil droplets, the better.
μm or less is preferable.

Oil droplets in the present invention can be obtained, for example, from US Pat.
No. 7, No. 2,533, 514, No. 2, 882, 157, Japanese Patent Publication No. 46-2
3233, British Patents 958,441, 1,222,753, JP Sho
50-82078, U.S. Pat.Nos. 2,353,262 and 3,676,142
No. 3,600,454, JP-A-51-28921, and JP-A-51-14
1623, Japanese Patent Application No. 60-148489 and the like (esters such as phthalates, phosphates and fatty acid esters), amides (such as fatty acid amides and sulfamides), ethers It is preferable to use a high-boiling-point organic solvent that is liquid at room temperature and does not evaporate at the heat treatment temperature, such as compounds, alcohols and paraffins. Among these, phosphoric acid ester type and paraffins are particularly preferable.

Further, even if it is a solid by itself, it is also included as an oil droplet that is a liquid droplet in the coating film due to the melting point lowering by using two or more kinds in combination.

Also, what is solid at room temperature, but exists as a liquid droplet when included in a hydrophilic binder or when incorporated with various photographic additives is also included as an oil droplet.

Examples thereof include stilbene, triazine, oxazole and coumarin compounds used as a whitening agent, and benzotriazole, thiazoline, cinnamic acid ester compounds used as an ultraviolet absorber.

The oil droplets suitable for use in the present invention include saturated or unsaturated hydrocarbons having 10 or more carbon atoms (including those in which a part or all of hydrogen is replaced with a halogen atom), or the following general formula (A ) To (G).

Formula _{^{(E) (R 28 -O 3}} P = O General formula (G) R _G —COO—R ₃₂ {In the above general formula (A), R _A represents a m + n-valent substituted or unsubstituted aliphatic hydrocarbon group, and R ²¹ represents a substituted or unsubstituted aliphatic group. It represents a hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, and m and n each represent an integer of 1 to 5.

In the above general formula (B), R _B represents a p + q-valent substituted or unsubstituted aliphatic hydrocarbon group or alicyclic hydrocarbon group, and R ²² and R ²³ may be the same or substituted with each other. Or represents an unsubstituted aliphatic hydrocarbon group or alicyclic hydrocarbon group, and p is 0, 1, 2 or 3
, Q represents 0, 1, 2 or 3, and p + q is 1 or more.

In the general formula (C), R _C is a hydrogen atom, or a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group, acyl group, amino group, acyloxy group, carbamoyl group, It represents a ureido group, an alkoxycarbonyl group, an aryloxycarbonyl group or a cycloalkyloxycarbonyl group, or a halogen atom, a hydroxyl group, a carboxyl group, a nitro group or a cyano group.

R ²⁴ represents a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group or aromatic hydrocarbon group.

r represents an integer of 1 to 5, s represents an integer of 1 to 4, and r + s is 6 or less.

When r is 2 or more, R _C may be the same or different.

When s is 2 or more, R ²⁴ may be the same or different.

In the general formula (D), R ²⁵ and R ²⁶ each represent a substituted or unsubstituted alkyl group, a monocyclic or polycyclic alicyclic hydrocarbon group, an aryl group or an aralkyl group.

R ²⁷ represents a substituted or unsubstituted alkyl group, aryl group, aralkyl group or amino group, or a halogen atom. Z represents an atomic group for forming a carbon ring condensed with a benzene ring.

l represents 0 or 1. v represents an integer of 0 to 2, w represents an integer of 0 to 7, and v + w is 7 or less.

R ²⁶ 0- and / or R ²⁷ - is substituted carbocycles benzene ring and / or condensation in the general formula (D).

In the general formula (E), R ²⁸ represents a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group or aryl group.

R ²⁸ may be the same or different.

In the above general formula (F), R ²⁹ represents a hydrogen atom or an n′-valent substituted or unsubstituted aliphatic hydrocarbon group.

R ³⁰ and R ³¹ each represent a hydrogen atom or a substituted or unsubstituted aliphatic hydrocarbon group or aromatic hydrocarbon group, and R ³⁰ and R ³¹ may be the same or different.

R ²⁹ and R ³⁰ and R ³⁰ and R ³¹ may be linked to each other to form a heterocycle.

 n'represents 1 or 2.

In the general formula (G), R _G represents a substituted or unsubstituted aliphatic hydrocarbon group, and R ³² represents a substituted or unsubstituted aliphatic hydrocarbon group, alicyclic hydrocarbon group or aromatic hydrocarbon group. Represents } For a more detailed description of the above general formulas (A) to (G), see JP-A-59-178455, 59-178454, 59-178452, and JP-A-59-178455.
Although described in 59-178453, 59-178451, 59-178457 and the like, the compound represented by formula (E) is particularly preferably used.

Specific examples of the compound used to form the oil droplets are given below.

(1) Liquid paraffin (2) Chlorinated paraffin Furthermore, as an example of the compound of the formula (A) of the present invention, 1971 (Maruzen), Oil and Fat Chemistry Handbook (revised second edition), pp. 108-115 (Table 2-31, 2-34, 2-36, 2-39). , 2-47).

 (13) C₁₃H₂₇COOC₁₈H₃₇−iso (32) (C_FourH₉O₃P = O(34) (C₈H₁₇O₃P = O (35) (iso-C_TenH_{twenty one}O₃P = O (36) (n-C₁₆H₃₃O₃P = O (37) (n-C₁₈H₃₇O₃P = O(39) C₈H₁₇CH = CH (CH₂)₁₁CONH₂  (42) C₁₁H_{twenty three}CONC₂H_FourOCH₃)₂ (43) Leofos -65 (manufactured by Ajinomoto Co., Inc.) (44) Leofos -95 (Ajinomoto Co., Inc.) (45) Leofos -110 (manufactured by Ajinomoto Co., Inc.) These compounds are known and are commercially available.
Alternatively, it can be easily synthesized by a known synthesis method.

Among the above compounds, those having a low polarity are particularly effective in improving brittleness because the coating liquid (especially the coating liquid for the mordant layer) is less likely to aggregate. Above all, the organic / inorganic value is 3 or more, particularly 6 The above is preferable. Here, organic / inorganic is a concept for predicting the property of a compound, and the details thereof are described in, for example, "Chemical field", Vol. 11, page 719 (1957).

Although various known methods can be used to form oil droplets, as a typical example, the compound as described above is dissolved in a low boiling point organic solvent such as methyl acetate or ethyl acetate, if necessary, and Examples include a method in which an aqueous solution of a hydrophilic colloid such as gelatin is mixed with an activator, and the mixture is stirred to emulsify and disperse, and this dispersion is added to a coating solution for the hydrophilic colloid layer, followed by coating.

The hydrophilic colloid layer on the dye fixing layer side of the dye fixing element of the present invention advantageously contains a base or a base releasing agent. In particular, when the photosensitive element contains a sparingly soluble metal compound, as will be described later, a compound capable of forming a complex with a metal ion constituting the sparingly soluble metal compound and water as a medium (complex forming compound).
Is preferred to be added to the dye fixing element. Bases or base-releasing agents, such as complex-forming compounds, tend to precipitate in the film when used as salts. In order to prevent precipitation, it is preferable to use a polymer such as dextran or pullulan described in Japanese Patent Application No. 60-187600, or a compound containing a polyalkylene oxide described in Japanese Patent Application No. 60-206,092. How much is added
It is 0.01 to 5 g / m ² .

In the present invention, the dye fixing layer containing a mordant may contain various surfactants for the purpose of enhancing the coatability.

In the present invention, a gelatin hardener may be used in combination in the dye fixing layer. Examples of gelatin hardeners that can be used in the present invention include aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea,
Methylol dimethyl hydantoin etc.), dioxane derivative (2,3-dihydroxy dioxane etc.), active vinyl compound (1,3,5-triacryloyl-hexahydro-
s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-ethylene-bis (vinylsulfonylacetamide), N, N'-trimethylene-bis (vinylsulfonylacetamide), etc.], active halogen compound ( 2,4-
Dichloro-6-hydroxy-s-triazine etc.), mucohalogenic acids (mucochloric acid, mucophenoxycycloric acid etc.), epoxy compounds, isoxazoles, dialdehyde starch, 1-chloro-6-hydroxytriazinylated gelatin. And so on. Specific examples thereof include U.S. Patents 1,870,354, 2,080,019, and 2,726,
No. 162, No. 2,870,013, No. 2,983,611, No. 2,992,109
No. 3,047,394, No. 3,057,723, No. 3,103,437,
3,321,313, 3,325,287, 3,362,827, 3,4
90,911, 3,539,644, 3,543,292, British Patent 67
6,628, 825,544, 1,270,578, German patent 87
2,153, 1,090,427, 2,749,260, Japanese Patent Publication 34-7
133, 46-1872, etc.

Of these gelatin hardeners, especially aldehydes,
Active vinyl compounds, active halogen compounds, Japanese Patent Application No. 60-23
The epoxy compounds described in No. 1093 are preferable.

These hardeners may be added directly to the mordant layer coating solution, or may be added to another coating solution so as to diffuse into the mordant layer during the process of multilayer coating.

The amount of the gelatin hardener used in the present invention can be arbitrarily selected according to the purpose. Generally, about 0.1 to about 50 wt% of gelatin used is suitable, and preferably 1 to 3
It is 0 wt%.

In the present invention, a mordant can be used in combination with a metal ion in the dye fixing element to increase the transfer density of the dye. This metal ion is a mordant layer containing a mordant,
Alternatively, it can be added to the adjacent layer (which may be nearer to the support carrying the mordant layer or on the far side). The metal ions used here are colorless and heat,
It is desirable to be stable to light. Ie Cu ²⁺ , Zn
Multivalent ions of transition metals such as ²⁺ , Ni ²⁺ , Pt ²⁺ , Pd ²⁺ and Co ³⁺ ions are preferable, and Zn ²⁺ is particularly preferable. This metal ion is usually in the form of a water-soluble compound such as ZnSO ₄ , Z
_{n (CH 3 CO 2) 2} , in the addition, the addition amount thereof is from about 0.01 to about 5 g / m
² is suitable, preferably 0.1 to 1.5 g / m ² .

Image forming dyes mordanted on the dye fixing element of the present invention include the following. That is, azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, and phthalocyanine dyes having anionic groups such as phenolic hydroxyl groups, sulfonamide groups, sulfonic acid groups, and carboxyl groups.

The dye fixing element of the present invention is particularly advantageously used in the case of fixing this diffusible dye in a color image forming method in which a diffusible dye is imagewise formed or released, and then diffused and then fixed.

In the color image forming method described above, a method of developing using a developer at a temperature near room temperature [color diffusion transfer method] (for example, described in Belgian Patent 757,959), heat development in a substantially water-free state (Heat development method) (for example, European Patent No. 76492A2 and JP-A Nos. 58-79247 and 59-21844).
No. 61-238056, etc.), and the dye-fixing element of the present invention can be used in any of them.

The dye-providing substance useful in the above-mentioned color image forming method is represented by the following formula (V) and is used in combination with a silver halide emulsion.

Dy-Y (V) Here, Dy represents a dye portion (or a precursor portion thereof), and Y represents a substrate having a function of changing the diffusibility of the dye-donor substance (V) as a result of development.

Here, “diffusibility changes” means that (1) the dye-donor substance (V) is originally non-diffusible, and this changes to diffusible or a diffusible dye is released, Alternatively (2) means that the originally diffusible dye-donor substance (V) changes to non-diffusible. Further, this change may occur due to the oxidation of Y or the reduction thereof depending on the nature of Y.

As an example of "change in diffusivity" due to oxidation of Y, firstly p-sulfonamidonaphthols (including p-sulfonamidophenols: JP-A-48-33,826, 53-53)
50,736, European Patent No. 76,492 for specific examples),
o-sulfonamidophenols (including o-sulfonamidonaphthols: JP-A-51-113,624 and JP-A-56-126)
No. 42, No. 56-16130, No. 56-16131, No. 57-4043,
No. 57-650, U.S. Pat.No. 4,053,312, European Patent No. 76,4
92), hydroxysulfonamide heterocycles (JP-A-51-104,343, EP 76,492 for specific examples), 3-sulfonamidoindoles (JP-A-51-104). 104,343, 53-46,730, 54-13
0,122, 57-85,055, and European Patent No. 76,492 for specific examples), α-sulfonamido ketones (JP-A-
Examples thereof include so-called dye-releasing redox substrates such as 53-3,819, 54-48,534, and European Patent No. 76,492).

As another example, Y is a type that releases a dye by an intramolecular nucleophilic attack after being oxidized, as disclosed in JP-A-57-20735 and 59-59.
Intramolecular assist type substrates described in No. 65839 are mentioned.

Another example is a substrate that releases a dye by an intramolecular ring-closing reaction under basic conditions, but does not substantially release the dye when Y is oxidized (JP-A-51-63,618). There is a specific example in the issue). Further, as a modified form of this, a substrate in which the isoxazolone ring undergoes ring rewinding by a nucleophile to release a dye is also useful (specific examples are described in JP-A Nos. 49-111,628 and 52-4819).

Another example is a substrate in which the dye moiety is released by dissociation of an acidic proton under basic conditions, but the dye is not substantially released when Y is oxidized (JP-A-53-69,033). No. 54-130927).

On the other hand, as an example in which the diffusivity changes when Y is reduced, nitro compounds described in JP-A-53-110,827: JP-A-53-110,827, US Pat. No. 4,356,2
The quinone compounds described in No. 49 and No. 4,358,525 can be mentioned. These are remaining reducing agents that are not consumed during the development process (called electron donors).
By the intramolecular attack of the resulting nucleophilic group to release the dye. As this modification, a quinone-type substrate in which the dye portion is released by dissociation of the acidic proton of the reductant is also useful (JP-A-54-130927).
No. 56-164, 342 for specific examples).

When a substrate whose diffusivity is changed by the above reduction is used, it is essential to use an appropriate reducing agent (electron donor) which mediates between the exposed silver halide and the dye-donating substance. Specific examples thereof are described in the above-mentioned publicly known materials. A substrate (referred to as LDA compound) in which an electron donor coexists in the substrate Y is also useful.

As another dye-donating substance, there can be used one that undergoes a redox reaction with a silver halide or an organic silver salt at a high temperature, and as a result, the mobility of the compound having a dye moiety is changed. It is described in JP-A-59-165054.

Further, a dye-donor substance which releases a mobile dye upon reaction with silver ions in the light-sensitive material is described in JP-A-59-180548.

The dye-fixing element of the present invention can be used in combination with a light-sensitive element for a color diffusion transfer method which is developed with a processing solution at around room temperature, or can be used in combination with a photothermographic element which is developed by heating.

The silver halide that can be used in the above light-sensitive element may be any of silver chloride, silver bromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide.

Specifically, U.S. Pat. No. 4,500,626, column 50, Research Disclosure, June 1978, pp. 9-10 (RD17
029), JP-A-61-107240, Japanese Patent Application No. 60-225176, 60
Any of the silver halide emulsions described in -228267 etc. can be used.

The silver halide emulsion used in the present invention may be either a surface latent image type in which a latent image is mainly formed on the grain surface or an internal latent image type in which a latent image is formed inside the grain. A so-called core-shell emulsion having a different phase between the inside of the grain and the surface layer of the grain may be used. Further, in the present invention, a direct reversal emulsion in which an internal latent image type emulsion and a nucleating agent are combined can be used.

The silver halide emulsion may be used as it is without ripening, but it is usually chemically sensitized before use. Well-known sulfur sensitizing methods, reduction sensitizing methods, noble metal sensitizing methods and the like can be used alone or in combination for the emulsions for conventional type light-sensitive materials. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-58-126526 and JP-A-58-215644).

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

Specifically, JP-A-59-180550, JP-A-60-140335,
Sensitizing dyes described in Research Disclosure, June 1978, pages 12 to 13 (RD17029), and JP-A-60-111239.
And sensitizing dyes having thermal decolorization described in Japanese Patent Application No. 60-129767.

These sensitizing dyes may be used alone, or a combination thereof may be used.
Often used for the purpose of supersensitization.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. No. 2,933,390). , No. 3,635,721, No. 3,743,510
No. 3,615,613, 3,615,641, 3,617,295,
No. 3,635,721).

These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after chemical ripening, and U.S. Pat. No. 4,183,756.
No. 4,225,666, before or after nucleation of silver halide grains.

The addition amount is generally 10 ^{-8 to} 1 mol per mol of silver halide
It is about 10 ^-2 mol.

The dye-fixing element of the present invention may be provided on a support separate from the photosensitive element or may be a film unit associated with the photosensitive element.

A typical form of the film unit is that a dye-fixing element (hereinafter also referred to as “image-receiving element”) and a light-sensitive element are laminated on one transparent support, and after the transfer image is completed, it is exposed to light. The element does not need to be peeled off from the image receiving element. More specifically, the image-receiving element comprises at least one mordant layer, and in a preferred embodiment of the light-sensitive element, 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-donor substance for each emulsion layer, A combination of a magenta dye-donating substance and a cyan dye-donating substance (here, "an infrared light-sensitive emulsion layer is an emulsion layer sensitive to light of 700 nm or more, especially 740 nm or more. A white reflective layer containing a solid pigment such as titanium oxide is provided between the mordant layer and the photosensitive layer or the layer containing the dye-donating substance so that the transferred image can be viewed through the transparent support. . Completed development in the light A light-shielding layer may be further provided between the white reflective layer and the photosensitive layer for the purpose of enabling the light-sensitive element, and if necessary, at a suitable position so that all or a part of the light-sensitive element can be separated from the image-receiving element. A release layer may be provided (such an embodiment is disclosed, for example, in JP-A-56-67).
840 and Canadian Patent 674,082).

Further, in another form in which peeling is not required, the above-mentioned photosensitive element is coated on one transparent support, a white reflective layer is coated thereon, and an image receiving layer is further laminated thereon. An embodiment in which an image receiving element, a white reflective layer, a release layer, and a photosensitive element are laminated on the same support, and the photosensitive element is intentionally peeled off from the image receiving element is described in US Pat. No. 3,730,718. On the other hand, there are roughly two representative forms in which a light-sensitive element and an image-receiving element are separately coated on two supports, one is a peeling type and the other is a peeling-free type. More specifically, in a preferred embodiment of the peelable film unit, a light reflecting layer is provided on the back surface of the support, and at least one image receiving layer is coated on the surface. The photosensitive element is coated on a support having a light-shielding layer. Before the end of the exposure, the surface coated with the photosensitive layer and the surface coated with the mordant layer do not face each other. Is turned upside down and overlaps the image receiving layer coating surface. After the transfer image is completed on the mordant layer, the light-sensitive element is rapidly separated from the image-receiving element.

In a preferred embodiment of the peel-free type film unit, at least one mordant layer is coated on a transparent support, and a photosensitive element is coated on a support having a transparent or light-shielding layer. The photosensitive layer coated surface and the mordant layer coated surface face each other and are superposed.

Any of the above-mentioned forms can be applied to both the color diffusion transfer system and the heat development system, but particularly in the former case, an alkaline processing liquid is further contained. A pressure-rupturable container (processing element) may be combined. Among others, in a peel-free type film unit in which an image receiving element and a photosensitive element are laminated on one support, the processing element is preferably arranged between the photosensitive element and a cover sheet overlaid thereon. Further, in the form in which the light-sensitive element and the image-receiving element are separately coated on the two supports, it is preferable that the processing element is disposed between the light-sensitive element and the image-receiving element at the latest during the development processing. The processing element preferably contains a light-shielding agent (such as carbon black or a dye whose color changes depending on pH) and / or a white pigment (such as titanium oxide) depending on the form of the film unit. Further, in the color diffusion transfer type film unit, it is preferable that a neutralization timing mechanism comprising a combination of a neutralization layer and a neutralization timing layer is incorporated in the cover sheet, the image receiving element, or the photosensitive element.

On the other hand, in a film unit of the heat development type, a heat generating layer containing metal fine particles, conductive particles such as carbon black or graphite is provided at an appropriate position of a support, a light-sensitive element or an image receiving element to perform heat development or Joule heat generated when electricity is applied may be used for diffusion transfer of the dye. A semiconductive inorganic material (eg, silicon carbide, molybdenum silicide, lanthanum chloride, barium titanate ceramics, tin oxide, zinc oxide, etc.) may be used instead of the conductive particles.

The case where the present invention is applied to a photothermographic material will be described below.

When the present invention is applied to a photothermographic material, an organic metal salt can be used as an oxidizing agent together with silver halide. In this case, the photosensitive silver halide and the organic metal salt need to be in contact with each other or in a close distance.

Among such organic metal salts, organic silver salts are particularly preferably used.

Examples of the organic compound that can be used to form the above organic silver salt oxidizing agent include compounds described in JP-A No. 61-107240, pages 37 to 39, U.S. Pat.No. 4,500,626, columns 52 to 53. There is. Also useful are silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in Japanese Patent Application No. 61-113235, and silver acetylene described in JP-A No. 61-249044. Two or more kinds of organic silver salts may be used in combination.

The above-mentioned organic silver salt can be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per 1 mol of photosensitive silver halide. The total coating amount of the photosensitive silver halide and the organic silver salt is preferably 50 mg to 10 g / m ² in terms of silver.

The above-mentioned dye-donor compounds and hydrophobic additives such as image-forming accelerators described below can be incorporated into the layers of the light-sensitive element by known methods such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-83154
No. 59-178451, 59-178452, 59-178453
No. 59-178454, No. 59-178455, No. 59-178457 and the like, a high-boiling organic solvent as described in combination with a low-boiling organic solvent having a boiling point of 50 ℃ ~ 160 ℃ , Can be used.

The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, with respect to 1 g of the dye-donor substance used.

Further, a dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 can also be used.

In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method.

When the hydrophobic substance is dispersed in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-
The surfactants listed on pages (37) to (38) of 157636 can be used.

In the present invention, it is desirable to incorporate a reducing substance into the photosensitive element. Examples of the reducing substance include those generally known as a reducing agent, and the dye-donating substance having the above-described reducing property. Further, it also includes a reducing agent precursor which has no reducing property itself but exhibits reducing property by the action of a nucleophile or heat during the development process.

Examples of the reducing agent used in the present invention include U.S. Pat.
Columns 49-50 of 500,626, Columns 30-31 of 4,483,914,
Pages 17-18 of JP-A-60-140335, JP-A-60-128438
Nos. 60-128436, 60-128439, 60-128437 and the like can be used. In addition, JP-A-56-1387
The reducing agent precursors described in US Pat. No. 36, 57-40245, US Pat. No. 4,330,617 and the like can also be used.

Combinations of various reducing agents such as those disclosed in US Pat. No. 3,039,869 can also be used.

In the present invention, the reducing agent is added in an amount of 1 mol of silver.
It is 0.01 to 20 mol, particularly preferably 0.1 to 10 mol.

In the present invention, a compound capable of activating development and stabilizing an image at the same time can be used in the light-sensitive element. For specific compounds preferably used, U.S. Pat.
No. 626, columns 51-52.

Various antifoggants or photographic stabilizers can be used in the present invention. Examples thereof include azoles and azaindenes described in Research Disclosure, December 1978, pages 24 to 25, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, or JP-A- The mercapto compounds and metal salts thereof described in JP-A-59-111636, the acetylene compounds described in Japanese Patent Application No. 60-228267, and the like are used.

In the present invention, the light-sensitive element may contain an image toning agent, if necessary. Specific examples of effective toning agents include compounds described in JP-A-61-147244, pp. 92-93.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors of yellow, magenta and cyan, it is necessary to use a photosensitive element having at least three silver halide emulsion layers sensitive to different spectral regions. Good. For example, there are a combination of three layers of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. Each of these photosensitive layers may be divided into two or more layers if necessary.

The photosensitive element used in the present invention is, if necessary, various additives known for heat-developable photosensitive elements 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 may have a release layer, a matte layer or the like for facilitating release from the fixing element. Examples of various additives include plasticizers, matting agents, sharpness improving dyes and antihalation dyes described in Research Disclosure, June 1978, pages 9 to 15 and JP-A-61-88256. , Surfactants, optical brighteners, anti-slip agents, antioxidants, and anti-fading agents.

In particular, the protective layer usually contains an organic or inorganic matting agent to prevent adhesion. Further, this protective layer may contain a mordant and an ultraviolet absorber. The protective layer and the intermediate layer may each be composed of two or more layers.

Further, the intermediate layer may contain a reducing agent for preventing fading or color mixing, an ultraviolet absorber, and a white pigment such as titanium dioxide. The white pigment may be added to the emulsion layer as well as the intermediate layer for the purpose of improving the sensitivity.

If necessary, the dye fixing element can be provided with auxiliary layers such as a protective layer, a peeling layer and an anti-curl layer. In particular, it is useful to provide a protective layer. One or more of the above layers may include a hydrophilic thermal solvent, a plasticizer, an antifade agent, a UV absorber, a slip agent, an antioxidant, a dispersed vinyl compound for increasing dimensional stability, and an interface. An activator, an optical brightener, etc. may be included. Further, particularly in a system in which heat development and transfer of a dye are simultaneously performed in the presence of a small amount of water, it is preferable that the dye-fixing element contains a base and / or a base precursor described later in order to enhance the storage stability of the photosensitive element. . Specific examples of these additives are described in JP-A-61-88256, 101.
Pp.-120.

In the present invention, an image formation accelerator can be used in the light-sensitive element and / or the dye fixing element. The image formation accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a light-sensitive material layer. Has a function of accelerating the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, a base or a base precursor, a nucleophilic compound, a high boiling organic solvent (oil), a thermal solvent, a surfactant, silver Alternatively, they are classified into compounds that interact with silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. These details are described in JP-A-61-93451.
Issue, pages 67-71.

There are various other methods for generating a base, and any compound used in the method is useful as a base precursor. For example, a method of generating a base by mixing a hardly soluble metal compound and a compound capable of forming a complex with a metal ion constituting the hardly soluble metal compound (referred to as a complex forming compound) described in Japanese Patent Application No. 60-169585. And
There is a method of generating a base by electrolysis as described in JP-A-61-232451.

The former method is particularly effective. Examples of the hardly soluble metal compound include carbonates such as zinc, aluminum, calcium and barium, hydroxides and oxides. As for the complex-forming compound, for example, A.E.
Co-authored by AEMartell, RMSmith, "Critical Stability Constants (Cr
itical Stability Constants, "Volumes 4 and 5, Plenum Press. Specifically, aminocarboxylic acids, iminodiacetic acids, pyridylcarboxylic acids, aminophosphoric acids, carboxylic acids (mono, di, tri, tetracarboxylic acids and also phosphono, hydroxy, oxo, ester, amide, alkoxy, mercapto, alkylthio, phosphino) And the like, and salts of hydroxamic acids, polyacrylates, polyphosphoric acids, and the like with alkali metals, guanidines, amidines, quaternary ammonium salts, and the like.

The sparingly soluble metal compound and the complex forming compound are advantageously added separately to the light-sensitive element and the dye-fixing element.

In the present invention, various development stoppers can be used in the light-sensitive element and / or the dye-fixing element for the purpose of always obtaining a constant image against variations in processing temperature and processing time during development.

The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or inhibits development by interacting with silver and a silver salt. Compound. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof (for example, No. 60-108837, No. 60-192939, No.
Compounds described in 60-230133 or 60-230134).

Compounds which release a mercapto compound upon heating are also useful, for example, JP-A-61-67851 and JP-A-61-147244.
Nos. 61-124941, 61-185743, 61-182039
Nos. 61-185744, 61-1884539, 61-188540
And No. 61-53632.

In the present invention, a hydrophilic binder can be used as the binder of the photosensitive element. As the hydrophilic binder, a transparent or translucent hydrophilic binder is representative, for example, gelatin, proteins such as gelatin derivatives, cellulose derivatives, starch, natural substances such as polysaccharides such as gum arabic, polyvinylpyrrolidone, Includes synthetic polymer materials such as water-soluble polyvinyl compounds such as acrylamide polymers. It is also possible to use a dispersed vinyl compound which is used in the form of a latex and which increases the dimensional stability of the photographic material. 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 1 m ² , preferably 10 g or less, more preferably 7 g or less.

The ratio of the high-boiling organic solvent and the binder to be dispersed together with the hydrophobic compound such as the dye-providing substance in the binder is 1 cc or less of solvent to 1 g of binder, preferably 0.5 cc or less, and more preferably 0.3 cc or less. .

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

Specific examples of the hardener include those described in JP-A-61-147244, pages 94 to 95 and JP-A-59-157636, page (38), which may be used alone or in combination. Can be used.

In order to promote dye transfer, a hydrophilic thermal solvent which is solid at normal temperature and dissolves at high temperature may be incorporated in the photosensitive element or the dye fixing element. The hydrophilic thermal solvent is a photosensitive element,
It may be incorporated in either of the dye fixing elements or in both. The layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and / or its adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides,
There are sulfonamides, imides, alcohols, oximes and other heterocycles. Further, in order to promote dye transfer, a high boiling organic solvent may be contained in the photosensitive element and / or the dye fixing element.

The support used in the present invention for the light-sensitive element and / or the dye-fixing element is one that can withstand the processing temperature. As a general support, not only glass, paper, polymer film, metal and its analogues are used, but also described as a support on pages 95 to 96 of JP-A No. 61-147244. You can use what you have.

The photosensitive element and / or the dye fixing element may have a form having a conductive heating element layer as a heating means for heat development or diffusion transfer of the dye.

In this case, the transparent or opaque heating element can be made using a conventionally known technique as a resistance heating element.
As the resistance heating element, there are a method of using a thin film of a semiconductive inorganic material and a method of using an organic thin film in which conductive fine particles are dispersed in a binder. Materials usable in these methods include those described in JP-A-61-29835.

In the present invention, the method for coating the photothermographic layer, the protective layer, the intermediate layer, the undercoat layer, the back layer, the dye-fixing layer and other layers described in U.S. Pat.

Radiation that also contains visible light can be used as a light source for image exposure for recording an image on the photosensitive element. In general, light sources used in ordinary color printing, for example, halogen lamps such as tungsten lamps, mercury lamps and iodine lamps, xenon lamps, laser light sources, CRT light sources, light emitting diodes (LEDs), etc., are disclosed in JP-A-61-147244.
The light source described on page 00 or column 56 of US Pat. No. 4,500,626 can be used.

In the present invention, the steps of heat development and dye transfer may be independent or simultaneous. Further, it may be continuous in the sense that the scratch transfer is performed for the development in one step.

For example, (1) a method in which a photosensitive element is imagewise exposed and heated, and then a dye fixing element is overlaid, and when necessary, a movable dye is transferred to the dye fixing element, and (2) a photosensitive element is imagewise exposed. However, there is a method in which the dye fixing elements are stacked and heated. The methods (1) and (2) can be carried out in a state where water is not substantially present, or can be carried out in the presence of a small amount of water.

The heating temperature in the heat development step is about 50 ° C. to about 250 ° C., and development is possible, but about 80 ° C. to about 180 ° C. is particularly useful. When heating in the presence of a small amount of water, the upper limit of the heating temperature is the boiling point or lower. If the transfer step is performed after the heat development step,
The heating temperature in the transfer step can be in the range of from the temperature in the heat development step to room temperature, but is more preferably from 50 ° C. to about 10 ° C. lower than the temperature in the heat development step.

In the present invention, the preferred image forming method is heating in the presence of a trace amount of water and a base and / or a base precursor after or at the same time as the image exposure, and at the same time as the development, the diffusion generated in the portion corresponding to or inversely corresponding to the silver image. The sex dye is transferred to the dye fixing layer. According to this method, the formation or release reaction of the diffusible dye proceeds extremely rapidly, and the migration of the diffusible dye to the dye fixing layer also proceeds rapidly, so that a high-density color image can be obtained in a short time.

The amount of water used in this embodiment is at least 0.1 times the weight of the total coating film of the light-sensitive element and the dye-fixing element, preferably
It may be as small as 0.1 times or more and less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film (especially less than the amount obtained by subtracting the weight of the total coating film from the weight of the solvent corresponding to the maximum swelling volume of the entire coating film). .

The state of the film at the time of swelling is unstable, and local bleeding may occur depending on the conditions. To avoid this, water corresponding to the maximum swelling volume of the total coating thickness of the photosensitive element and the dye fixing element is required. Or less. Specifically, the total area of the light-sensitive element and the dye-fixing element is 1 g per square meter
Preferred is a range of 50 g, especially 2 g to 35 g, more preferably 3 g to 25 g.

The base and / or base precursor used in this embodiment can be incorporated in the photosensitive element as well as in the dye-fixing element. It can also be dissolved in water and supplied.

In the above aspect, the image-forming reaction system, as a base precursor, a water-insoluble basic metal compound and a metal ion constituting the hardly-soluble metal compound and a compound capable of a complex formation reaction in water as a medium, It is preferred to raise the pH of the system by the reaction of these two compounds on heating. Here, the image reaction system means a region where an image forming reaction occurs. Specific examples include layers belonging to both the light-sensitive element and the dye-fixing element. When there are two or more layers, any of them may be used.

The hardly soluble metal compound and the complex forming compound need to be added to at least another layer in order to prevent a reaction before the development processing. For example, in a so-called monosheet material in which a light-sensitive element and a dye-fixing element are provided on the same support, it is preferable that the additive layers of the both are separate layers and that one or more layers are interposed therebetween. Further, a more preferred form is
The hardly soluble metal compound and the complex forming compound are contained in layers provided on different supports, respectively. For example, it is preferable that the poorly soluble metal compound is contained in the light-sensitive element and the complex-forming compound is contained in the dye-fixing element having a support separately from the light-sensitive element. The complex-forming compound may be dissolved in water to be coexistent and supplied. The sparingly soluble metal compound is disclosed in JP-A-56-174830.
And a fine particle dispersion prepared by the method described in JP-A Nos. 53-102733 and the like, and the average particle size is preferably 50 microns or less, particularly preferably 5 microns or less. The sparingly soluble metal compound may be added to any layer of the photosensitive element such as the photosensitive layer, the intermediate layer and the protective layer, or may be added by dividing it into two or more layers.

The amount of addition when the hardly soluble metal compound or complex forming compound is contained in the layer on the support depends on the compound type, the particle size of the hardly soluble metal compound, the complexation reaction rate, and the like.
It is appropriate to use each coating film in an amount of 50% by weight or less in terms of weight, and more preferably in the range of 0.01% by weight to 40% by weight. When the complex-forming compound is dissolved in water and supplied, a concentration of 0.005 mol to 5 mol, particularly 0.05 mol to 2 mol per liter is preferable. Furthermore, in the present invention, the content of the complex-forming compound in the reaction system is preferably 1/100 to 100 times, particularly preferably 1/10 to 20 times, the molar ratio of the content of the sparingly soluble compound.

As a method for applying water to the photosensitive layer or the dye fixing layer, for example, JP-A-61-147244, page 101, line 9 to page 102, 4
There is a method described in the line.

As a heating means in the developing and / or transferring step, a hot plate, an iron, a hot roller and the like are disclosed in JP-A-61-1472.
No. 44, page 102 line 14 to page 103 line 11 Also,
A layer of a conductive material such as graphite, carbon black, or metal may be superposed on the photosensitive element and / or the dye fixing element, and an electric current may be passed through the conductive layer to directly heat the conductive layer.

The method described on pages 103 to 104 of JP-A No. 61-147244 can be applied to the pressure condition and the method of applying pressure when the light-sensitive element and the dye fixing element are superposed and brought into close contact with each other.

Any of a variety of thermal development apparatus can be used in processing the photographic elements of this invention. For example, JP-A-59-75247 and 59-75247.
-1777547, 59-181353, 60-18951, Shogan 6
An apparatus described in, for example, No. 0-116732 is preferably used.

(Examples) Hereinafter, the present invention will be described in more detail by showing specific examples of the present invention.

Example 1 A light-sensitive material 101 having the following constitution was produced.

High boiling organic solvent (1) Trinonyl phosphate Water-soluble polymer (1) Sumikagel L-5 (H) Sumitomo Chemical Co., Ltd. Surfactant (1) Aerosol OT Hardener 1,3-vinylsulfonyl-2-propanol The method for preparing the emulsion for the fifth layer will be described.

Emulsion (I) Well stirred gelatin aqueous solution (20g gelatin, 3g sodium chloride and compound in 800ml water) 0.015 g was dissolved and kept at 65 ° C.), and the following solutions I and II were added over 70 minutes. Simultaneously with the start of the addition of Solution I and Solution II A dye solution prepared by dissolving 0.24 g in a solution of (120 cc of methanol + 120 cc of water) was added and then added over 60 minutes.

Immediately after the addition of solution I and solution II, 2 g of KBr was dissolved in 20 ml of water and added, and the mixture was left for 10 minutes.

After washing with water and desalting, 25 g of gelatin and 100 ml of water were added to adjust the pH to 6.4, p.
The Ag was adjusted to 7.8. The resulting emulsion has a grain size of about 0.5.
It was a cubic monodisperse emulsion of μ.

Keeping this emulsion at 60 ° C, 1.3 mg of triethylthiourea,
Optimal chemical sensitization was performed by simultaneously adding 100 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene. Yield 6
It was 50 g.

 The method for preparing the emulsion for the third layer will be described.

Emulsion (IV) Well stirred gelatin aqueous solution (800 ml of water, 20 g of gelatin, 2 g of sodium chloride and the compound 0.015 g was dissolved and kept at 65 ° C.), and the following solutions I and II were added over 60 minutes.

Simultaneously with the start of the addition of Solution I and Solution II A dye solution prepared by dissolving 0.16 g in 80 ml of methanol was added, and the mixture was added over 40 minutes.

After adding solution I and solution II, let them stand for 10 minutes, then lower the temperature, wash with water and desalting, then 25 g of gelatin and 100 ml of water.
Was added to adjust pH to 6.5 and pAg to 7.8.

After adjusting the pH and pAg, triethylthiourea and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added and optimum chemical sensitization was performed at 60 ° C.

The obtained emulsion was a cubic monodisperse emulsion having a grain size of about 0.35μ and the yield was 650 g.

 The method for preparing the emulsion for the first layer will be described.

Emulsion (VII) Well stirred gelatin aqueous solution (20g gelatin and 4g sodium chloride in 1000ml water) 600 ml of an aqueous solution containing 49 g of potassium bromide and 10.5 g of sodium chloride and an aqueous solution of silver nitrate (a solution of 0.59 mol of silver nitrate dissolved in 600 ml of water) at the same time Over 50 minutes. Washing with water,
After desalting, 25 g of gelatin and 200 ml of water were added to adjust the pH to 6.4, and optimum chemical sensitization was performed using triethylthiourea and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene. Conducted, cubic monodisperse emulsion (VII) 70 with an average grain size of 0.4μ
I got 0g.

 How to make an organic silver salt is described.

Organic Silver Salt (1) A method for preparing a benzotriazole silver emulsion will be described.

28 g of gelatin and 13.2 g of benzotriazole were dissolved in 300 ml of water. This solution was kept at 40 ° C. and stirred. A solution prepared by dissolving 17 g of silver nitrate in 100 ml of water was added to this solution over 2 minutes.

The pH of this benzotriazole silver emulsion was adjusted and allowed to settle to remove excess salt. Then adjust the pH to 6.30,
A yield of 400 g of benzotriazole silver emulsion was obtained.

Organic silver salt (2) 20 g of gelatin and 5.9 g of 4-acetylaminophenylpropiolic acid were dissolved in 1000 ml of 0.1% sodium hydroxide aqueous solution and 200 ml of ethanol.

 This solution was kept at 40 ° C. and stirred.

A solution prepared by dissolving 4.5 g of silver nitrate in 200 ml of water was added to this solution over 5 minutes.

The pH of this dispersion was adjusted and allowed to settle to remove excess salt. After that, the pH was adjusted to 6.3 to obtain a 300 g organic silver salt (2) dispersion.

Next, a method for preparing a gelatin dispersion of a dye-donor substance will be described.

12 g of yellow dye-donating substance (Y-1), (Y-
2) 3g, high boiling organic solvent (1) 7.5g, reducing agent (1) 0.3
g, and 0.3 g of mercapto compound (1) in 45 m of ethyl acetate
100 g of a 10% gelatin solution and 60 ml of a 2.5% aqueous solution of sodium dodecylbenzenesulfonate were stirred and mixed, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is called a yellow dye-donor substance dispersion.

15 g of magenta dye-donating substance (M), high boiling organic solvent (1) 7.5 g, reducing agent (1) 0.3 g and mercapto compound (1) 0.15 g were added and dissolved in ethyl acetate 25 ml, and 10% gelatin solution 100 g Of sodium dodecylbenzene sulfonate
After mixing with 60 ml of a 2.5% aqueous solution with stirring, the mixture was dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is called a dispersion of a magenta dye-donor substance.

Cyan dye-donating substance (C) 15 g, high boiling organic solvent (1) 7.5 g, reducing agent (1) 0.4 g, and mercapto compound (1) 0.6 g were added and dissolved in 40 ml of ethyl acetate to prepare a 10% gelatin solution. 100g and sodium dodecylbenzene sulfonate 2.
After stirring and mixing with 60 ml of 5% aqueous solution, 1 with a homogenizer
It was dispersed at 10000 rpm for 0 minutes. This dispersion is referred to as a dispersion of a cyan dye-donor substance.

Next, how to make the dye fixing material will be described.

Dye fixing materials R-1 to R-10 were prepared by coating on a polyethylene-laminated paper support in the constitution shown in the following table.

How to make and add oil droplets To 100 g of 10% aqueous gelatin solution, add 5 ml of 5% aqueous solution of sodium dodecylbenzene sulfonate, and further add 20 g of liquid paraffin and emulsify and disperse with a homoblender for 6 minutes at 10,000 rpm. Dye dispersion layer as the dye fixing layer (1st layer)
Carbonizes in the coating liquid of.

Images were formed using these as follows.

The color light-sensitive material 101 having the multilayer structure was exposed to 10 ⁻⁴ using a xenon flash tube. At that time, it was exposed through a three-color separation filter of G, R, and IR whose densities were continuously changed.

12 ml / m ² of water was supplied to the emulsion surface of the exposed light-sensitive material with a wire bar, and then the dye-fixing material (image receiving material) described above was superposed so that the film surface was in contact.

After heating for 25 seconds using a heat roller whose temperature has been adjusted so that the water-absorbed film temperature is 90 ° C, the dye fixing material is peeled off from the photosensitive material to form a three-color separation filter of G, R, and IR on the fixing material. Correspondingly, yellow, magenta and cyan images were obtained.

As shown in Table 3, the surface quality of the dye fixing material having the combination of the polymer binders of the present invention was matted.

In addition, the maximum density (D _max ) was decreased by about 0.2 as the measured value due to the surface matting (1.8 to 2.0), but the density was visually sufficient.

(Effect of the Invention) By containing the combination of two or more kinds of polymer binder substances which cause phase separation of the present invention, a dye fixing element can be prepared without adding a matting agent or embossing the support. The surface can be matted, and the surface smoothness is excellent, and uneven transfer during color image transfer is prevented.

Claims (2)

[Claims] 1. A dye-fixing element comprising a dye-fixing layer containing a mordant, characterized in that it contains two or more polymeric binder substances in a state of being microphase separated from each other. 2. The dye-fixing element according to claim 1, wherein the two or more types of macromolecular phase-separated polymeric binder materials are selected from combinations according to the following rules. Polymer binder material that separates into two or more layers when two or more aqueous solutions of the polymer binder material (0.5 to 10% by weight) are mixed and stirred in equal amounts at 20 to 40 ° C, and then placed in a cylinder and left standing at the above temperature. Combination of.