JPH05188554A - Heat development and diffusion transfer type color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain the heat development and diffusion transfer type color photosensitive material which can be produced with consistent and stable performance (particularly without a change in color separability) without adversely affecting other photographic characteristics. CONSTITUTION:At least >=2 kinds of the compds. varying in the the (Ball) groups of the compd. expressed by formula are used as the filter dyes of the heat development and diffusion transfer type color photosensitive material. In the formula, Dye denotes the structural section to determine the hue as the filter dye of the compd.; Ball denotes the structural section to immobilize the compd. in a photosensitive material film; (n) denotes an integer of >=1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-development diffusion transfer type color light-sensitive material, and particularly to a heat-development capable of being produced with stable and constant performance, which is excellent in color separation and image discrimination. The present invention relates to a diffusion transfer type color light-sensitive material.

[0002]

2. Description of the Related Art The photographic method using silver halide is superior to other photographic methods such as electrophotography and diazo photography in photographic characteristics such as sensitivity and gradation control. Has been. In particular, since the best image quality is obtained for color hard copy, it has been studied more vigorously these days.

Recently, with the progress of office automation, commercial image equipment, electronic still cameras, video,
With the spread of facsimiles, etc.,
Graphics needs have also increased. In particular, with the progress of computer graphics and the development of image sensor technology and digital processing technology, there is an increasing demand for obtaining a color hard copy from image information once converted into an electronic signal.

Conventional color light-sensitive materials usually have spectral sensitivities of blue, green, and red. To obtain an image by using image information once converted into an electronic signal in such color light-sensitive materials, color images are obtained. It is common to use a CRT (cathode ray tube) as an exposure light source, but the CRT is unsuitable for obtaining a large size print.

Further, as a writing head capable of obtaining a large size print, a light emitting diode (LED) is used.
And semiconductor lasers have been developed. However, none of these optical writing heads that efficiently emit blue light has been developed.

Thus, for example, a light emitting diode (LED)
When using, near infrared (800nm), red (670n
It is necessary to expose a color light-sensitive material having three layers spectrally sensitized to near infrared, red, and yellow by a light source combining three light emitting diodes of m) and yellow (570 nm). The system for recording images with a configuration is "Nikkei New Material", September 14, 1987, Issue 4
It is described on pages 7 to 57 and is partially used.

Further, a system for recording on a color light-sensitive material having three light-sensitive layers having spectral sensitivity at respective wavelengths by a light source combining three semiconductor lasers which emit light of 880 nm, 820 nm and 760 nm is disclosed in JP-A-61-161. 137
No. 149.

Due to the need for color hard copy as described above, in recent years, an image forming method for a light-sensitive material using silver halide has been changed from a conventional wet process to an inst photographic system containing a developing solution, and further. A system has been developed in which an image can be simply and quickly obtained by dry heat development processing by heating or the like. The simple and rapid processing method described above often employs a method of forming an image by a diffusion transfer method in order to prevent the image from being contaminated by a printout of silver halide after the image is formed.

The diffusion transfer method is a method of forming or releasing a diffusible dye imagewise and transferring the diffusible dye to an image-receiving material having a mordant with a solvent such as water. Angew.Chem.Int.Ed.Engl.22 (1983) 191
Are described in detail in. The present inventors continue to study diffusion transfer type color photosensitive materials, but it has become necessary to design a color photosensitive material corresponding to the above-described writing head (semiconductor laser, LED).

When designing a color light-sensitive material as described above, the spectral distribution of the wavelength of the light source mainly belongs to the infrared region of 600 nm or more, and it is necessary to select a three-color light source within a narrow wavelength range. It is very difficult to design the spectral sensitivity of silver halide. In such a case, a method of separating spectral sensitivity, that is, sharpening spectral sensitivity using a filter dye is generally used in the field. Known techniques for this method include, for example, US Pat.
As described in No. 6119892, a technique of increasing the sensitivity on the short wave side of the two spectral sensitivities and introducing a filter layer is known.

The present inventors have also examined the method of using the above filter dye. However, dyes used for color paper in the field are water-soluble because they need to be decolorized at the time of processing, and when used in a diffusion transfer type color light-sensitive material, they are transferred to an image-receiving material, and therefore they can be used. Can not. Therefore, an attempt was made to introduce oil-soluble ballast into the filter dye to emulsify oil or disperse fine particles in a solid state. Among them, the present inventor has found that, as described in Japanese Patent Application No. 3-63925, the emulsification of a filter dye with an oil protectant gives a preferable color separation property. In particular, it has been found that when a filter dye is emulsified and dispersed together with a non-diffusible dye-providing compound, a light-sensitive material excellent in color separation property, discrimination and raw storability can be obtained.

However, when the emulsion containing the filter dye is kept in a dissolved state for a long time, the filter dye and the non-diffusible dye-providing compound are deposited, and spotted unevenness occurs in the transferred image, and the color separation property is deteriorated. It has been found that it causes an unwanted photographic effect of being sick.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to provide a heat-development diffusion transfer type color light-sensitive material which is excellent in color separation property and image discrimination and can be manufactured with stable and constant performance. Especially. The photosensitive material that can be manufactured with stable and constant performance here means a photosensitive material that can be manufactured in a state in which photographic performance does not fluctuate significantly for a long period of several tens of hours or more. ..

[0014]

Such an object is achieved by the following constitutions (1) and (2). (1) A non-diffusible dye-donating compound which releases or forms a diffusible dye on a support at least in response to a reaction of reducing at least a photosensitive silver halide, a binder, and a silver halide to silver. In the heat development diffusion transfer type color light-sensitive material having a dye, and a filter dye, at least two kinds of compounds represented by the following general formula (I) having different (Ball) groups are used in combination as the filter dye. A heat development diffusion transfer type color photosensitive material. General formula (I) (Dye)-(Ball) _n [In the above general formula (I), Dye is a structural moiety that determines the hue of this compound as a filter dye,
Ball represents a structural site for immobilizing this compound in the sensitive material film. n represents an integer of 1 or more. ]

(2) The heat development diffusion transfer type color light-sensitive material as described in (1) above, wherein the filter dye is emulsified and dispersed together with the dye donating compound.

[0016]

[Specific Structure] The specific structure of the present invention will be described in detail below. The filter dye used in the present invention is a compound represented by the following general formula (I). General formula (I) (Dye)-(Ball) _n

In the general formula (I), Dye represents a structural site that determines the hue of this compound. In the dye of the present invention, a residue having the same structure as a dye known in the art can be used in this Dye portion. As an example of such a dye part, for example, Theory of the Photographic Process (4th.Ed., THJ
ames edited by Macmillan, 1977) 194 to 233, cyanine dyes, 335 to 362, azomethine, indoaniline, indophenol, azine, amidrazone, dyes using azo dyes and the like. .. In particular, as described above, when a filter dye is used for color separation in the IR region, one having a λmax of 700 nm or more is selected from these dyes.
As such a dye, for example, the dye described in the functional material, June 1990, page 64, can be used as the infrared dye.

However, as the dye used in the present invention, a compound having one or more immobilizing groups represented by Ball is used in order to prevent transfer to the image receiving material during processing of the light-sensitive material. Such groups include ballast groups known in the art. For example, an alkyl group having 6 or more carbon atoms (eg, a substituted or unsubstituted hexyl group, octyl group, cyclohexyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, etc.), an aryl group (eg, a substituted or unsubstituted group). Phenyl group, tolyl group, xylyl group, cumyl group, butylphenyl group, amylphenyl group, naphthyl group, etc., and heterocyclic group (eg, substituted or unsubstituted pyridyl group, furyl group, quinolyl group, etc.) and the like. ..

Specific examples of the filter dye in the present invention include those shown in Chemical formula 1, and in this Chemical formula ¹ , combinations of R ¹ , Y and X ⁻ are Chemical formulas 2 to 4. The preferred examples are as follows. Moreover, the compounds shown in Chemical formulas 5 and 6 can also be given as specific examples. Further, the compound shown in Chemical formula 7 is mentioned, and in the compound shown in Chemical formula 7, the combination of R ² , R ³ , R ⁴ and R ⁵ is Chemical formula 8 is a preferable example.

[0020]

[Chemical 1]

[0021]

[Chemical 2]

[0022]

[Chemical 3]

[0023]

[Chemical 4]

[0024]

[Chemical 5]

[0025]

[Chemical 6]

[0026]

[Chemical 7]

[0027]

[Chemical 8]

In the case of the present invention, the above filter dyes are
In the above general formula (I), compounds having different Ball are 2
Used in combination with one or more species.

In this case, the different Ball compounds are
Not only the combination of completely different ones such as hexyl group and octyl group, octyl group and phenyl group, but also n
A combination of isomers such as -octyl group and 2-ethylhexyl group may be used.

When n is an integer of 2 or more, at least one Ball may be different.

In the present invention, the mixing ratio of each dye can be freely selected. Therefore, the mixing ratio may be freely selected within the range of the total addition amount described below.

In this way, two different compounds of Ball
The effect of the present invention can be obtained by combining two or more kinds.

Only one kind of such effects or Ba
It cannot be obtained by using two or more kinds of compounds in which 11 is the same as each other.

When the filter dye of the present invention is incorporated into a light-sensitive material, it can be used by emulsifying and dispersing it together with a dye-donor compound, or preferably by emulsifying and dispersing with a dye-donor compound. The emulsification / dispersion method is a known technique in the art, and a known method such as the method described in US Pat. No. 2,322,027 can be used as the method.

When emulsifying and dispersing together with the dye-providing compound, it is preferable to use all the filter dyes and the dye-providing compound as the co-emulsifying dispersion, but in some cases, a part of the co-emulsifying dispersion and the rest are used. You may use it as a separate independent dispersion. However, when forming a part thereof, it is preferable that the filter dye is a co-emulsified dispersion with a dye-donor compound and the dye-donor compound is a single dispersion.

Further, a silver halide emulsion layer, a coloring material layer, an intermediate layer, a protective layer or the like can be selected as an addition layer of the emulsion or dispersion of the filter dye, but in the present invention, a dye-donating property is provided. It is preferably added to the silver halide emulsion layer after being co-emulsified with the compound. There are two reasons.
First, the reaction between the silver halide and the dye-donor compound during development occurs most efficiently. The other is that sharpness is improved by the anti-irradiation effect of the filter dye. The latter effect is particularly remarkable in the false color light-sensitive material. The higher the extinction coefficient (ε) of the filter dye, the more preferable. The addition amount can be widely selected, but the molar absorption coefficient (ε) is 100.
In the case of dyes in the range of 00 to 500,000, the amount is 0.1 mg to 10 g, preferably ⁵ mg to 500 mg per m ² .
Further, the filter dye is a dye-donating compound,
The weight ratio is preferably 0.01 to 100, more preferably 0.1 to 10.

The color light-sensitive material of the present invention basically has a photosensitive silver halide, a dye-donating compound (which may also serve as a reducing agent as described later) and a binder on a support. Further, if necessary, an organic metal salt oxidizing agent or the like can be added. These components are often added to the same layer, but if they are in a reactive state, they can be added separately to separate layers. For example, when a dye-providing dye compound is present in the lower layer of the silver halide emulsion, the reduction in sensitivity can be prevented. The reducing agent is preferably incorporated in the light-sensitive material, but may be supplied from the outside by, for example, a method of diffusing from a dye fixing material described later.

In order to obtain a wide range of colors on the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, a combination of at least three silver halide emulsion layers sensitive to different spectral regions is used. .. For example, there are combinations of three layers of blue-sensitive layer, green-sensitive layer and red-sensitive layer, green-sensitive layer, red-sensitive layer and infrared-sensitive layer. Each of the light-sensitive layers can take various arrangement orders known in a normal color light-sensitive material. Further, each of these photosensitive layers may be divided into two or more layers if necessary.

The photosensitive material may be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, an antihalation layer and a back layer. Further, in the present invention, at least one layer containing the co-emulsified dispersion of the filter dye and the dye-providing compound is provided. This is for the following reason.

For example, when the layer B spectrally sensitized to 750 nm is provided on the layer A spectrally sensitized to 810 nm,
When the layer B side is exposed to the light of nm from the layer B side, the color of the layer A is mixed in a highly exposed portion, that is, a portion having a large amount of light, resulting in insufficient color separation. This tendency becomes remarkable especially when the sensitivity of the layer A spectrally sensitized to 810 nm is high.

Therefore, in the layer A or in the layer between the layer A and the layer B, there is no substantial absorption in the vicinity of the spectral sensitization peak of the layer A. Shortwave and layer B
By incorporating a dye having an absorption maximum wavelength (λmax) at a position capable of absorbing the light emitted from the light source used for the exposure, the spectral sensitized portion on the short wave side of layer A is cut to improve color separation.

The silver halide usable in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide.

The silver halide emulsion used in the present invention may be either a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or an optical fogging. Further, it may be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. The silver halide emulsion may be monodisperse or polydisperse, and monodisperse emulsions may be mixed and used. The particle size is preferably 0.1 to 2 µ, and particularly preferably 0.2 to 1.5 µ. The crystal habit of the silver halide grains may be cubic, octahedral, tetrahedral, tabular with a high aspect ratio, or the like.

Specifically, US Pat. No. 4,500,626, column 50, US Pat. No. 4,628,012, Research Disclosure (hereinafter abbreviated as RD) 17029 (19).
1978), any of the silver halide emulsions described in JP-A No. 62-253159 and the like can be used.

The silver halide emulsion may be used as it is without being post-ripened, 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 singly or in combination for emulsions for conventional light-sensitive materials. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159).

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

When used in a heat development system as in the present invention,
In the light-sensitive element, an organic metal salt can be used as an oxidizing agent together with the light-sensitive silver halide. Among such organic metal salts, organic silver salts are particularly preferably used.

Organic compounds that can be used to form the above organic silver salt oxidizing agent include US Pat. No. 4,500,626.
There are benzotriazoles, fatty acids and other compounds described in Nos. 52 to 53 and the like. In addition, JP-A-60-1132
No. 35, a silver salt of a carboxylic acid having an alkynyl group such as silver phenylpropiolate, and JP-A-61-249.
Acetylene silver described in No. 044 is also useful. Two or more kinds of organic silver salts may be used in combination.

The above organic silver salts are photosensitive silver halides.
0.01 to 10 moles per mole, preferably 0.1.
01 to 1 mol can be used in combination. The total coating amount of photosensitive silver halide and organic silver salt is 50 mg / m ^{2 in} terms of silver.
Approximately 10 g / m ² is suitable.

Various antifoggants or photographic stabilizers can be used in the present invention. Examples thereof include azoles and azaindenes described on pages 24 to 25 of RD17643 (1978), JP-A-59-1684.
42-containing nitrogen-containing carboxylic acids and phosphoric acids,
Alternatively, mercapto compounds and metal salts thereof described in JP-A-59-111636, acetylene compounds described in JP-A-62-87957 and the like can be used.

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, US Pat. No. 4,617,257
No. 59-180550, 60-14033.
No. 5, RD17029 (1978) pages 12 to 13 and the like.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Patent No. 3615641, Japanese Patent Application No. 6
No. 1-222694, etc.).

These sensitizing dyes may be added to the emulsion during the chemical ripening or before or after the chemical ripening, or before or after the nucleation of silver halide grains according to US Pat. Nos. 4,183,756 and 4,225,666. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

A hydrophilic binder is preferably used as the binder of the constituent layers of the light-sensitive element and the dye-fixing element. As an example thereof, pages (26) to (2) of JP-A-62-253159.
8) The thing described in page is mentioned. Specifically, a transparent or translucent hydrophilic binder is preferable, and for example, gelatin, proteins such as gelatin derivatives or cellulose derivatives, natural compounds such as polysaccharides such as starch, gum arabic, dextran and pullulan, and polyvinyl alcohol, Examples thereof include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Furthermore, superabsorbent polymers described in JP-A-62-245260, i.e. -COOM or -SO ₃ M (M is a hydrogen atom or an alkali metal) homopolymer or a vinyl monomer together or with other vinyl monomers with A copolymer with a vinyl monomer (for example, sodium methacrylate, ammonium methacrylate, Sumika Gel L-5H manufactured by Sumitomo Chemical Co., Ltd.) is also used. These binders can be used in combination of two or more.

When a system in which a small amount of water is supplied for thermal development is adopted, it becomes possible to quickly absorb water by using the above superabsorbent polymer. Further, when the super absorbent polymer is used in the dye fixing layer or its protective layer, the dye can be prevented from being retransferred from the dye fixing material to another after the transfer.

In the present invention, the coating amount of the binder is 1
It is preferably 20 g or less per m ² , particularly 10 g or less, and more preferably 7 g or less.

The constituent layer (including the back layer) of the light-sensitive element or the dye-fixing element is used for the purpose of improving physical properties of the film such as dimensional stability, curl prevention, adhesion prevention, film cracking prevention, and pressure increase / decrease prevention. Various polymer latices can be included. Specifically, any of the polymer latexes described in JP-A Nos. 62-245258, 62-136648, 62-110066 and the like can be used. In particular,
When a polymer latex having a low glass transition point (40 ° C. or less) is used in the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used in the back layer, a curl preventing effect can be obtained. ..

As the reducing agent used in the present invention, those known in the field of light-sensitive materials can be used. Further, a dye-donor compound having a reducing property described later is also included (in this case, other reducing agents can be used together). Further, a reducing agent precursor which has no reducing property by itself but exhibits a reducing property by the action of a nucleophile or heat during the development process can also be used.

Examples of the reducing agent used in the present invention include:
U.S. Pat. No. 4,500,626, columns 49-50, 44
No. 83, col. 30, columns 31-43617;
No. 4,590,152, JP-A No. 60-140335, pages (17) to (18), Nos. 57-40245, 56.
-138736, 59-178458, 59-
No. 53831, No. 59-182449, No. 59-18
No. 2450, No. 60-119555, No. 60-128
436 to 60-128439, 60-1
No. 98540, No. 60-181742, No. 61-25.
9253, 624244044, 62-131
From 253 to 62-131256, there are reducing agents and reducing agent precursors described in EP 220746A2, pages 78 to 96, and the like.

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

When a diffusion resistant reducing agent is used, an electron transfer agent and / or an electron transferring agent may be optionally added in order to promote electron transfer between the diffusion resistant reducing agent and the developable silver halide.
Alternatively, an electron transfer agent precursor can be used in combination.

The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or its precursors. It is desirable that the electron transfer agent or the precursor thereof has a mobility higher than that of the diffusion resistant reducing agent (electron donor). A particularly useful electron transfer agent is 1-phenyl-3
-Pyrazolidones or aminophenols.

The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be any one of the above-mentioned reducing agents which does not substantially move in the layer of the light-sensitive material, and is preferable. Hydroquinones, sulfonamide phenols, sulfonamide naphthols, JP-A-53-
Examples thereof include compounds described as electron donors in No. 110827 and dye-donating compounds having diffusion resistance and reducing property described later.

In the present invention, the reducing agent is added in an amount of 0.001 to 20 mol, preferably 0.1 to 20 mol, per mol of silver.
It is from 01 to 10 mol.

In the present invention, a compound that produces or emits a movable dye (also referred to as a diffusible dye) corresponding to or opposite to the exposure amount, that is, a dye-donating compound is used.

Examples of the dye-donating compound that can be used in the present invention include a compound (coupler) which forms a dye by an oxidative coupling reaction. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. A 2-equivalent coupler having a diffusion resistant group as a leaving group and forming a diffusible dye by an oxidative coupling reaction is also preferable. This nondiffusible group may form a polymer chain. Specific examples of color developers and couplers are TH James
"The Theory of the Photographic Process" Fourth Edition 2
91-334 pages, and 354-361 pages, JP-A-58.
-123533, 58-149046, 58-
149047, 59-11148, and 59-1
24399, 59-174835, 59-23.
1539, 59-231540, 60-295.
No. 0, No. 60-2951, No. 60-14242, No. 60-23474, No. 60-66249 and the like.

As another example of the dye-donating compound,
Examples thereof include compounds having a function of releasing or diffusing a diffusible dye imagewise. This type of compound can be represented by the following general formula [LI].

(Dye-Y) n-Z [LI]

Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents a photosensitive silver salt having an imagewise latent image. Or, conversely, causes a difference in the diffusivity of the compound represented by (Dye-Y) nZ, or D
ye is released, and the released Dye and (Dye-Y) n-
Z represents a group having a property of causing a difference in diffusibility from Z, n represents 1 or 2, and when n is 2, two Dye-Y may be the same or different.

Specific examples of the dye-donating compound represented by the general formula [LI] include the following compounds. The following items (1) to (5) are for forming a diffusible dye image (positive dye image) in the opposite manner to the development of silver halide, and "and" are the diffusible dye image (corresponding to the development of silver halide). To form a negative dye image).

US Pat. Nos. 3,134,764 and 336.
2819, 3597200, and 3544545.
No. 3,482,972 and the like. A dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developing agent is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide.

As described in US Pat. No. 4,053,137, a non-diffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide can also be used. For example, US Pat.
Compounds releasing a diffusible dye by an intramolecular nucleophilic substitution reaction described in 980479 and the like, US Pat. No. 4,1993.
No. 54 and the like, compounds that release a diffusible dye by an intramolecular rewinding reaction of the isoxazolone ring can be mentioned.

US Pat. No. 4,559,290, European Patent No. 220746A2, US Pat. No. 4,783,396,
As described in Published Technical Report 87-6199, a non-diffusible compound which releases a diffusible dye by reacting with a reducing agent left unoxidized by development can also be used.

As an example, US Pat. No. 4,133,938.
No. 9, 4139379, JP-A-59-185333.
Nos. 57-84453 and the like, which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction, US Pat. No. 4,232,107, JP-A-59
No. 101649, No. 61-88257, RD240
25 (1984) and the like, which release a diffusible dye by intramolecular electron transfer reaction after reduction, West German Patent No. 3008588A, JP-A-56-14.
2530, US Pat. Nos. 4,343,893 and 4619.
Compounds which release a diffusible dye by cleavage of a single bond after reduction as described in US Pat.
Examples thereof include nitro compounds described in U.S. Pat. No. 223 and the like that release a diffusible dye after electron acceptance, compounds described in U.S. Pat. No. 4,609,610 and the like that release a diffusible dye after electron acceptance.

Further, as more preferable ones, European Patent No. 220746A2, Kokai Giho No. 87-6199, US Pat. No. 4,783,396, and Japanese Patent Laid-Open No. 63-201653.
No. 63, 2016-654, etc.
A compound having an -X bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group, Japanese Patent Application No. 62-106885.
No. ₂ within one molecule of SO ₂ -X (X is as defined above)
And a compound having an electron-withdrawing group, JP-A-63-2713
A compound having a PO-X bond (X has the same meaning as described above) and an electron-withdrawing group in one molecule described in JP-A-44-
The compound having a C—X ′ bond (X ′ has the same meaning as X or represents —SO ₂ —) and an electron-withdrawing group in one molecule described in No. 271341.

Of these, a compound having an N—X bond and an electron-withdrawing group in one molecule is particularly preferable. Specific examples thereof include the compound (1) described in EP 220746A2.
~ (3), (7) to (10), (12), (13),
(15), (23) to (26), (31), (32),
(35), (36), (40), (41), (44),
(53) to (59), (64), (70), Public Technical Report 8
And compounds (11) to (23) of No. 7-6199.

A compound (DDR coupler) which is a coupler having a diffusible dye as a leaving group and releases the diffusible dye by a reaction with an oxidized form of a reducing agent. Specifically, British Patent No. 1330524, Japanese Patent Publication No. 48-39165, US Patent Nos. 3443940, 4474867, and 448.
3914 and the like.

A compound (DRR compound) which is reducible to a silver halide or an organic silver salt and releases a diffusible dye when its partner is reduced. Since this compound does not need to use any other reducing agent, it is preferable because there is no problem of image contamination due to oxidative decomposition products of the reducing agent. Typical examples thereof are U.S. Pat. Nos. 3,928,312, 40,53312, and 405.
No. 5428, No. 4336322, JP-A-59-658.
No. 39, No. 59-69839, No. 53-3819,
51-104343, RD17465, U.S. Pat. Nos. 3,725,062, 3,728,113, and 3,443.
939, JP-A-58-116537, and JP-A-57-17.
9840, U.S. Pat. No. 4,500,626 and the like. Specific examples of the DRR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626, columns 22 to 44. Among them, the compounds (1) to (3) described in the above-mentioned U.S. Pat. (10) to (13), (1
6) to (19), (28) to (30), (33) to (3
5), (38) to (40) and (42) to (64) are preferable. The compounds described in US Pat. No. 4,639,408, columns 37 to 39 are also useful.

In addition, as a dye-donor compound other than the above-mentioned coupler and general formula [LI], a dye silver compound in which an organic silver salt and a dye are bonded (Research Disclosure, May 1978, pp. 54-58). , Etc., azo dyes used in the heat-development silver dye bleaching method (US Pat.
957, Research Disclosure, 1976.
April issue, pages 30 to 32), leuco dyes (US Pat. Nos. 3,985,565 and 4,022,617), and the like can be used.

Hydrophobic additives such as dye-donor compounds and diffusion-resistant reducing agents can be incorporated into the layers of the light-sensitive element by known methods such as those described in US Pat. No. 2,322,027. In this case, JP-A-59-83154,
59-178451, 59-178452, 59-178453, 59-178454, 5
9-178455, 59-178457 and the like, a high boiling point organic solvent, if necessary, a boiling point of 50 ° C.
It can be used in combination with an organic solvent having a low boiling point of up to 160 ° C.

The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, relative to 1 g of the dye-donor compound used. Also, 1 cc or less, more preferably 0.5 cc or less, especially 0.3 cc or less is suitable for 1 g of the binder.

JP-B-51-39853, JP-A-51-
A dispersion method using a polymer described in 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 dispersing the hydrophobic compound in the water-immersive colloid, various surfactants can be used. For example, JP-A-59-157636 (37) to (3)
8) The surfactants listed on page 8 can be used.

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. The specific compounds preferably used are described in US Pat. No. 4,500,626, columns 51 to 52.

In the case of forming an image by diffusion transfer of a dye as in the present invention, a dye fixing element is used in combination with a light sensitive element. The dye fixing element may be coated on a support which is separate from the photosensitive element, or may be coated on the same support as the photosensitive element.
The relationship between the photosensitive element and the dye fixing element, the relationship with the support,
Regarding the relationship with the dye reflection layer, the relationship described in column 57 of US Pat. No. 4,500,626 can be applied to the present application.

The dye fixing element preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include US Pat. No. 4,500,626, columns 58 to 59 and JP-A No. 61-88256 (32).
The mordant described on page (41), JP-A-62-244043.
No. 62-244036 and the like. Further, a dye-receptive polymer compound described in US Pat. No. 4,463,079 may be used.

If necessary, the dye fixing element may be provided with auxiliary layers such as a protective layer, a peeling layer, an anti-curl layer and an undercoat layer. In particular, it is useful to provide a protective layer.

In the constituent layers of the light-sensitive element and the dye-fixing element, a high boiling point organic solvent can be used as a plasticizer, a slipping agent, or an agent for improving the releasability of the light-sensitive element and the dye-fixing element. Specifically, JP-A-62-253159, (2
5), No. 62-245253, etc.

Further, various silicone oils (all silicone oils from dimethylsilicone oil to modified silicone oils obtained by introducing various organic groups into dimethylsiloxane) can be used for the above purpose. As examples thereof, various modified silicone oils described in "Modified Silicone Oil" technical materials P1 to 18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X-22-3710) and the like are effective.

The silicone oils described in JP-A Nos. 62-215953 and 62-23687 are also effective.

An anti-fading agent may be used in the light-sensitive element and the dye fixing element. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a metal complex of some kind.

Examples of the antioxidants include chroman compounds, coumarane compounds, phenol compounds (eg hindered phenols), hydroquinone derivatives, hindered amine derivatives and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective.

As the ultraviolet absorber, benzotriazole compounds (US Pat. No. 3,533,794, etc.), 4-
Thiazolidone compounds (US Pat. No. 3,352,681, etc.), benzophenone compounds (JP-A-46-2784)
Etc.) and others, JP-A-54-48535 and JP-A-62-
There are compounds described in Nos. 136641 and 61-88256. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective.

Examples of the metal complex include US Pat.
55, 42425018, columns 3 to 36, 4254.
195, columns 3 to 8, JP-A-62-174741, JP-A-61-88256, pages (27) to (29), and JP-A-63-1.
No. 99248, Japanese Patent Application Nos. 62-234103 and 62-
There are compounds described in No. 230595 and the like.

Examples of useful anti-fading agents are disclosed in JP-A-62-21.
5272 (125)-(137).

The anti-fading agent for preventing the fading of the dye transferred to the dye-fixing element may be contained in the dye-fixing element in advance, or may be supplied to the dye-fixing element from the outside such as a light-sensitive element. May be.

The above-mentioned antioxidant, ultraviolet absorber and metal complex may be used in combination.

A fluorescent whitening agent may be used in the light-sensitive element and the dye-fixing element. In particular, it is preferable to incorporate a fluorescent whitening agent in the dye fixing element or supply it from the outside such as a light sensitive element. For example, see “The Chemis” edited by K. Veenkataraman.
try of Synthetic Dyes ", Volume V, Chapter 8, JP-A-61-
The compound described in 143752 etc. can be mentioned. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds and the like can be mentioned. The fluorescent whitening agent can be used in combination with an anti-fading agent.

The hardener used in the constituent layers of the light-sensitive element and the dye-fixing element is described in US Pat. No. 4,678,739, No. 41.
Column, JP-A-59-116655 and JP-A-62-24526.
The hardeners described in No. 1 and No. 61-18942 are listed. More specifically, aldehyde type hardener (formaldehyde etc.), aziridine type hardener, epoxy type hardener, vinyl sulfone type hardener (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane), N-
Examples thereof include methylol type hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157).

In the constituent layers of the light-sensitive element and the dye-fixing element, various surfactants can be used for the purpose of coating aid, improvement of releasability, improvement of slipperiness, prevention of electrification, acceleration of development and the like. Specific examples of the surfactant are disclosed in JP-A-62-173463.
No. 62-183457 and the like.

The constituent layers of the light-sensitive element and the dye-fixing element may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, improving releasability and the like. Typical examples of the organic fluoro compounds include Japanese Examined Patent Publication No. 57-9053, columns 8 to 17,
Fluorine-based surfactants described in JP-A Nos. 61-20944 and 62-135826, oil-based fluorine-based compounds such as fluorine oil, and solid fluorine-containing compound resins such as tetrafluoroethylene resin. Hydrophobic fluorine compounds may be mentioned.

A matting agent can be used in the light-sensitive element and the dye-fixing element. Matting agents such as silicon dioxide, polyolefins, polymethacrylates, etc.
Japanese Patent Application No. 62-110064, such as benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like, in addition to the compounds described on page 1-88256 (29).
No. 62-110065.

In addition, the constituent layers of the light-sensitive element and the dye-fixing element may contain a thermal solvent, a defoaming agent, an antibacterial / antifungal agent, colloidal silica and the like. Specific examples of these additives are described in JP-A No. 61-88256, pages (26) to (32).

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 formation of a dye from a dye-donor compound or decomposition of the dye or release of a diffusible dye, and a photosensitive element layer. Has a function of promoting the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, it is 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 US Pat. No. 4,678,739, columns 38 to 40.

Examples of the base precursor include salts of an organic acid and a base which are decarboxylated by heat, compounds which release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. A specific example is US Pat. No. 45114.
93, JP-A-62-65038 and the like. Further, salts with 2-carboxycarboxamide described in US Pat. No. 4,088,496 and the like can be mentioned. Other British Patent No. 998945, US Pat. No. 322084
No. 6, the base precursor described in JP-A No. 50-22625 and the like can be used.

In a system in which heat development and dye transfer are carried out simultaneously in the presence of a small amount of water, it is preferable to add a base and / or base precursor to the dye-fixing element in order to enhance the storage stability of the light-sensitive element.

Further, as described in US Pat. No. 4,740,445, a sparingly soluble metal compound (for example, zinc oxide,
A method of generating a water-soluble base by reacting a compound (for example, guanidine picolinate) capable of forming a complexing reaction with metal ions constituting basic zinc carbonate, calcium carbonate, etc.) and water as a medium, and the sparingly soluble metal compound It can also be used. In this method, a dispersion of a sparingly soluble metal compound is contained in the light-sensitive element, and a water-soluble compound capable of undergoing a complex-forming reaction with this metal ion is contained in the dye-fixing element as a base precursor, and both are adhered in the presence of water. Since a base can be generated during the heat treatment, it is particularly effective in terms of storability of the light-sensitive element and the dye-fixing element over time.

In addition, the compounds which generate a base by electrolysis as described in JP-A-61-232451 can be used as the base precursor.

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

The term "developer stopping agent" as used herein means, after proper development,
A compound that rapidly neutralizes or reacts with a base to lower the concentration of the base in the film to stop development, or a compound that interacts with silver and a silver salt to suppress development. In particular,
Examples thereof 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. More specifically, JP-A-62-253
159, pages 31-32.

As the support for the light-sensitive element and the dye-fixing element of the present invention, those which can withstand the processing temperature are used. Generally, paper and synthetic polymer (film) are used. Specifically, polyethylene terephthalate (P
ET), polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing pigments such as titanium oxide, and synthetic film made by polypropylene or the like. Blended paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly Cascote paper), metal, cloth, glass and the like are used.

These can be used alone or
It can also be used as a support having one or both sides laminated with a synthetic polymer such as polyethylene.

In addition, the supports described in JP-A-62-253159, pages (29) to (31) can be used.

On the surface of these supports, a hydrophilic binder and a semiconductive metal oxide such as alumina sol or tin oxide,
You may apply carbon black and other antistatic agents.

As a method for exposing and recording an image on a photosensitive element, for example, a method of directly photographing a landscape or a person by using a camera, a method of exposing through a reversal film or a negative film by using a printer or an enlarger, A method of scanning and exposing an original image through a slit or the like using an exposure device of a copying machine, a method of exposing image information by emitting light from a light emitting diode or various lasers through an electric signal, a CRT, a liquid crystal display, There is a method of outputting to an image display device such as an electroluminescence display and a plasma display, and exposing directly or through an optical system.

As a light source for recording an image on a photosensitive element,
As described above, US Patent No. 4 of natural light, tungsten lamp, light emitting diode, laser light source, CRT light source, etc.
The light source described in 500626, column 56 can be used.

Image exposure can also be performed using a wavelength conversion element in which a nonlinear optical material and a coherent light source such as a laser beam are combined. Here, the non-linear optical material is a material capable of exhibiting non-linearity between polarization and an electric field that appears when a strong optical electric field such as laser light is applied, and includes lithium niobate and potassium dihydrogen phosphate (KD).
P), inorganic compounds represented by lithium iodate, BaB ₂ O _4, etc., urea derivatives, nitroaniline derivatives, for example, nitropyridine-N such as 3-methyl-4-nitropyridine-N-oxide (POM). -Oxide derivatives, JP-A-61-53462 and JP-A-62-210432
The compounds described in No. 10 are preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful.

Further, the image information is a video camera,
An image signal obtained from an electronic still camera or the like, a television signal represented by Nippon Television Signal Standard (NTSC),
An image signal obtained by dividing an original image into a large number of pixels such as a scanner, or an image signal created by using a computer represented by CG and CAD can be used.

The light-sensitive element and / or the dye-fixing element are
It may have a form having a conductive heating element layer as a heating means for heat development or dye diffusion transfer. In this case, the transparent or opaque heating element is disclosed in JP-A-61
Those described in, for example, the specification of 145544 can be used.
Note that these conductive layers also function as antistatic layers.

The heating temperature in the heat development step is about 50 ° C. to about 250 ° C., and development is possible, but especially about 80 ° C. to about 180 ° C.
C is useful. The dye diffusion transfer process may be performed simultaneously with the heat development, or may be performed after the heat development process is completed. In the latter case, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but especially 50 ° C.
Above all, it is more preferable that the temperature is lower by about 10 ° C. than the temperature in the heat development step.

Although the migration of the dye occurs only by heat,
Solvents may be used to facilitate dye transfer. Also,
As described in detail in JP-A-59-218443 and JP-A-61-238056, a method of performing development and transfer simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water) is also useful. is there. In this method, the heating temperature is preferably 50 ° C. or higher and not higher than the boiling point of the solvent. For example, when the solvent is water, it is preferably 50 ° C. or higher and 100 ° C. or lower.

Examples of the solvent used for accelerating the development and / or transferring the diffusible dye to the dye-fixing layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (these bases). Examples thereof include those described in the section of the image formation accelerator). Further, a low boiling point solvent, or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt and a complex-forming compound, etc. may be contained in the solvent.

These solvents can be used by a method of applying them to the dye fixing element, the photosensitive element or both.
The amount used may be as small as the weight of the solvent corresponding to the maximum swelling volume of the entire coating film or less (particularly the amount of the solvent corresponding to the maximum swelling volume of the entire coating film less the weight of the total coating film).

As a method for applying a solvent to the photosensitive layer or the dye fixing layer, there is, for example, the method described in JP-A-61-147244, page (26). Alternatively, the solvent may be contained in a microcapsule, and may be incorporated in the light-sensitive element or the dye-fixing element or both in advance.

In order to promote dye transfer, a system in which a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperature is incorporated in the light-sensitive element or the dye-fixing element can also be adopted. The hydrophilic thermal solvent may be incorporated in either the photosensitive element or the dye fixing element, or may be incorporated 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, sulfonamides, imides, alcohols, oximes and other heterocycles.

Further, a high-boiling point organic solvent may be contained in the light-sensitive element and / or the dye-fixing element in order to promote dye transfer.

As a heating method in the developing and / or transferring step, a heated block or plate is brought into contact, or a hot plate, a hot presser, a heat roller, a halogen lamp heater, an infrared or far infrared lamp heater or the like is contacted. Or passing through a high temperature atmosphere.

Superimposing the light-sensitive element and the dye-fixing element,
For the pressure condition and the method of applying the pressure for the close contact, see Japanese Patent Laid-Open No.
The method described in page 1-147244 (27) can be applied.

Any of a variety of heat developing apparatus can be used in processing the photographic elements of this invention. For example, JP-A-59-7
No. 5247, No. 59-177547, No. 59-181.
No. 353, No. 60-18951, No. 62-259
The device described in No. 44 etc. is preferably used.

[0134]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1

Silver halide emulsions (I) for the third and first layers
Describe how to make.

A well stirred gelatin aqueous solution (water 10
600 ml of an aqueous solution containing 20 g of gelatin and 3 g of sodium chloride in 00 ml and kept at 75 ° C and containing sodium chloride and potassium bromide, and an aqueous solution of silver nitrate (600 ml of water in which 0.59 mol of silver nitrate is dissolved) )
Were added simultaneously at equal flow rates over 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (bromine 50 mol%) having an average grain size of 0.40 μm was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added, and chemical sensitization was carried out at 60 ° C. The yield of emulsion was 600 g.

Next, a silver halide emulsion (II) for the fifth layer
Describe how to make.

Well-stirred aqueous gelatin solution (water 10
600 ml of an aqueous solution containing 20 g of gelatin and 3 g of sodium chloride in 00 ml and kept at 75 ° C and containing sodium chloride and potassium bromide, and an aqueous solution of silver nitrate (600 ml of water in which 0.59 mol of silver nitrate is dissolved) )
Were added simultaneously at equal flow rates over 40 minutes. Thus, a monodisperse cubic silver chlorobromide emulsion (bromine 80 mol%) having an average grain size of 0.35 μm was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added, and chemical sensitization was carried out at 60 ° C. The yield of emulsion was 600 g.

Next, a method for preparing a gelatin dispersion of zinc hydroxide will be described.

12.55 g of zinc hydroxide having an average particle size of 0.25 μm, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 cc of 4% gelatin aqueous solution, and the average particle size was 0.75 mm with a mill.
The glass beads were crushed for 30 minutes. The glass beads were separated to obtain a gelatin dispersion of zinc hydroxide.

Next, a method for preparing a gelatin dispersion of the hydrophobic additive will be described.

The oil phase components in Table 1 were each mixed with ethyl acetate 5
It was dissolved in 0 cc to obtain a uniform solution at 60 ° C. To this, 6
The aqueous phase component heated to 0 ° C. was added, and the mixture was dispersed for 30 minutes at 5000 rpm with a dissolver having a diameter of 8 cm. To this was added post-hydration and stirred to form a uniform dispersion. This is referred to as the hydrophobic additive gelatin dispersion.

[0146]

[Table 1]

A heat-developable color photosensitive material 101 having a multilayer structure as shown in Tables 2 and 3 was prepared from these materials.

[0148]

[Table 2]

[0149]

[Table 3]

The compounds in Table 1, Table 2 and Table 3 are represented by Chemical Formulas 9 to 12 as the dye-donor compounds (1) to (4) and Chemical formula 13 as the auxiliary developing agent, respectively. Chemicals 14 and 2 as antifoggants
0, a high-boiling-point solvent represented by Chemical Formula 15, a surfactant represented by Chemical Formula 16, Chemical Formula 18, a water-soluble polymer represented by Chemical Formula 17, and a sensitizing dye represented by Chemical Formula 19. It is what is done. The hardener (10) is 1,2-bis (vinylsulfonylacetamide) ethane.

[0151]

[Chemical 9]

[0152]

[Chemical 10]

[0153]

[Chemical 11]

[0154]

[Chemical 12]

[0155]

[Chemical 13]

[0156]

[Chemical 14]

[0157]

[Chemical 15]

[0158]

[Chemical 16]

[0159]

[Chemical 17]

[0160]

[Chemical 18]

[0161]

[Chemical 19]

[0162]

[Chemical 20]

Next, a dye fixing material R-1 having the constitution shown in Table 4 was prepared.

[0164]

[Table 4]

In Table 4, the silicone oils shown in Chemical formula 21 and the surfactants in Chemical formulas 18 and 22 are shown.
Those shown in Chemical formula 23 as mordants,
The high boiling point solvent is shown in Chemical formula 24, and the hardener is shown in Chemical formula 25.

[0166]

[Chemical 21]

[0167]

[Chemical formula 22]

[0168]

[Chemical formula 23]

[0169]

[Chemical formula 24]

[0170]

[Chemical 25]

The matting agents and water-soluble polymers shown in Table 4 are shown below.

Matting agent (32); Benzoguanamine resin (average particle size 15 μ) Water-soluble polymer (25); Sumikagel L5-H (Sumitomo Chemical Co., Ltd.) Water-soluble polymer (26); Dextran (molecular weight 70,000) Fluorescence Whitening agent (29); 2,5-bis (5-tert-butylbenzoxazolyl (2)) thiophene

Next, with respect to the light-sensitive material 101, light-sensitive materials 102 to 116 having exactly the same composition as the light-sensitive material 101 except that the filter dyes added as shown in Table 5 were changed.
made. When the filter dye is used by emulsifying and dispersing it alone as in the case of adding it to the second layer, it is used by emulsifying and dispersing according to the following formulation, and when it is added to the first layer, the dye When used by co-emulsifying with a donating compound, a co-emulsified dispersion was prepared by adding a predetermined amount of filter dye when emulsifying the emulsion of the dye-donating compound. Although the filter dye F-1 is shown as a representative, other filter dyes were similarly prepared.

How to make an emulsified dispersion of filter dyes alone
Method Filter Dye F-1 2.8 g, sodium dodecylbenzene sulfonate as a surfactant 1.5 g and triisononyl phosphate 7.5 g were weighed and added with 40 ml of ethyl acetate and dissolved by heating at about 60 ° C. A different solution. 125 g of this solution and an 8% solution of lime-processed gelatin
After stirring and mixing, and with a homogenizer for 1 minute, 1
Dispersed at 0000 rpm. This dispersion is called a gelatin dispersion of filter dye F-1.

[0175]

[Table 5]

Furthermore, the emulsion having the filter dye was kept dissolved at 40 ° C. for 24 hours, and then a coating solution was prepared to apply the photosensitive materials 201 to 216 to the photosensitive materials 101 to 116, respectively. Had made. The light-sensitive materials 101 to 116 and 201 to 2 thus prepared
16 was exposed to laser under the conditions shown in Table 6.

[0177]

[Table 6]

While feeding the exposed light-sensitive material at a linear velocity of 20 mm / sec, 15 ml / m ² of water was supplied to the emulsion surface by a wire bar, and immediately thereafter, the dye-fixing material as the image-receiving material was brought into contact with the film surface. So that they overlap.

Using a heat roller whose temperature was adjusted so that the water-absorbed film had a temperature of 83 ° C., it was heated for 25 seconds.

Next, when the image receiving material was peeled off, a transferred image was obtained on the image receiving material. The results of sensitometry of this transferred image are shown in Table 7.

Sensitometry was carried out to find the highest density (D) of cyan (Cy) and yellow (Y) in the 750 nm track.
_max ) was used as an index of color separation property. That is, if the Y density is low, the color separation property is good. There was almost no difference in other sensitometric values.

[0182]

[Table 7]

As shown in Table 7, it can be seen that with the light-sensitive material of the present invention, a transferred image with good color separation and coated surface state can be obtained even in a sample in which the emulsion is kept in a dissolved state for a long time.

Further, in the above-mentioned light-sensitive material of the present invention,
Comparing the filter dye added to the first layer as a co-emulsion with the dye-donating compound to the filter dye added to the second layer as a single emulsion dispersion,
It was found that the co-emulsion is superior in terms of color separation property, and further superior in sharpness and the like.

[0185]

According to the present invention, it is possible to manufacture the photographic performance such as color separation and discrimination, which are stable and constant.

[Procedure amendment]

[Submission date] January 11, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0003

[Correction method] Change

[Correction content]

Recently, with the progress of office automation, commercial image equipment, electronic still cameras, video,
With the spread of facsimiles, etc.,
Graphics needs have also increased. In particular, with the progress of computer graphics and the development of image sensor technology and digital processing technology, there is an increasing demand for obtaining a color hard copy from image information once converted into an electric signal.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction content]

Conventional color light-sensitive materials usually have spectral sensitivities of blue, green, and red. To obtain an image by using image information once converted into an electric signal in such color light-sensitive materials, color images are obtained. It is common to use a CRT (cathode ray tube) as an exposure light source, but the CRT is unsuitable for obtaining a large size print.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction content]

However, when the emulsion containing the filter dye is kept in a dissolved state for a long time, the filter dye and the non-diffusible dye-donating compound are deposited, causing spot-like unevenness in the transferred image, and the color separation property is deteriorated. It has been found to cause undesired photographic effects, such as doing.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

In the general formula (I), Dye represents a structural site that determines the hue of this compound. In the dye of the present invention, a residue having the same structure as a dye known in the art can be used in this Dye portion. Examples of such a dye portion include, for example, Theory of the Photographic Process (4th.E).
d. , T. H. Edited by James Macmillan, 1
977) Cyanine dyes described on pages 194 to 233,
Examples thereof include dyes using azomethine, indoaniline, indophenol, azine, amidrazone, azo dyes and the like described on pages 335 to 362 thereof. In particular, as described above, when a filter dye is used for color separation in the IR region, λ of 700 nm or more is selected from these dyes.
Choose one that has max. Examples of such materials include, as infrared dyes, functional materials 1990 6
The dyes and the like described on page 64 of the monthly issue can be used.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

[0025]

[Chemical 6]

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction content]

In the case of the present invention, the above filter dyes are
In the above general formula (I), compounds having different Ball are 2
Used in combination with one or more species. Ball here means that
R ¹ in (Specific example: Chemical formulas 2 to 4), R ⁵ in Chemical formula 7 (Specific example: Chemical formula 8), and in Chemical formulas ^{5 to} 6, the number of carbon atoms substituted for the N atom or the β-position of the N atom is 6 or more. Represents a substituent (diffusion resistant group).

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction content]

The photosensitive material may be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, an antihalation layer and a back layer. Further, in the present invention, at least one layer containing the co-emulsified dispersion of the filter dye and the dye donating compound is provided, but this is for the following reason.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Name of item to be corrected] 0146

[Correction method] Change

[Correction content]

[0146]

[Table 1]

[Procedure Amendment 9]

[Document name to be amended] Statement

[Name of item to be corrected] 0165

[Correction method] Change

[Correction content]

The compounds shown in Table 4 are those represented by Chemical Formula 21 as silicone oil and Chemical formula 1 as a surfactant.
8, those shown in Chemical formula 22, those shown in Chemical formula 23 as mordants, those shown in Chemical formula 24 as high boiling point solvents, and those shown in Chemical formula 25 as hardeners.

Claims (2)

[Claims] 1. A non-diffusible dye donor that releases or forms a diffusible dye corresponding to or at least corresponding to a reaction of at least a photosensitive silver halide, a binder, and silver halide reduced to silver on a support. Thermal diffusion diffusion transfer type color light-sensitive material having a photosensitive compound and a filter dye, the filter dye is a compound represented by the following general formula (I) in which at least two different (Ball) groups are used in combination. A heat development diffusion transfer type color light-sensitive material characterized by: General formula (I) (Dye)-(Ball) _n [In the above general formula (I), Dye is a structural moiety that determines the hue of this compound as a filter dye,
Ball represents a structural site for immobilizing this compound in the sensitive material film. n represents an integer of 1 or more. ] 2. The heat development diffusion transfer type color light-sensitive material according to claim 1, wherein the filter dye is emulsified and dispersed together with the dye donating compound.