JPH0511419A - Dye fixing element - Google Patents

Abstract

PURPOSE:To reduce light fading of a transferred dye image. CONSTITUTION:The polymer mordant to be used has as structural monomer units each represented by formula I in which R<1> is H or alkyl; R<2> is alkyl; R<3> is halogen, or alkyl, aryl, acylamino, sulfonamide group; R<4> is H, alkyl, or aryl group; each of L<1> and L<2> is a divalent bonding group; X<-> is an anion; m is an integer of 0-3; and n is an integer of 0-4.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a dye fixing element, and more particularly to a novel cationic polymer which is a good mordant for anionic dyes, and a dye fixing element using a layer containing the novel mordant.

[0002]

2. Description of the Related Art In the diffusion transfer method (a photographic technique for obtaining an image by fixing a diffusible dye formed imagewise on a dye fixing element), a diffused anionic dye is transferred onto the dye fixing element. Cationic polymeric mordants have been used for immobilization. Further, it has been proposed to use a cationic polymer mordant for fixing an anionic dye on a dye fixing element also in the ink jet method and the thermal transfer method of a dye.

US Pat. Nos. 3,898,088 and 3,9
58,995, 4,131,469, West German published application 2,941,818 and Japanese Patent Laid-Open No. 53-30328.
No. 56-17352 discloses such a polymer mordant.

The most important performance required of such a mordant is image storability. Although there are various mechanisms for deteriorating the image obtained by the diffusion transfer method, there are two problems in reality.
One is deterioration caused by migration of the dye within the dye fixing element or to another substance, and the other is deterioration caused by fading of the dye upon irradiation with light.

That is, an excellent mordant is to retain a dye,
It can be defined as one that has a high ability to fix (mordanting power) and that the dye that has been dyed does not easily cause fading due to light.

Much research has been done in the past to find excellent mordants, and British Patent 2,011,912
Nos. 2,056,101 and 2,093,041 and U.S. Pat. Nos. 4,115,124 and 4,273,85.
3, 4,282,305, JP-A-59-2323.
40, JP-A-60-118834 and JP-A-60-128.
No. 443, No. 60-122940, No. 60-1229.
Patents such as No. 21 and No. 60-235134 have been filed.

Although each of these techniques has achieved some success, it is still not sufficient, and further improvement is desired.

[0008]

Accordingly, an object of the present invention is to provide a dye-fixing element which has excellent mordant power, and has little fading due to light of the mordant dye, resulting in good image storability. To provide.

As a result of intensive studies, the present inventors have found that the object of the present invention can be achieved by a dye-fixing element containing a polymer mordant having a monomer unit represented by the following general formula (I) as a constituent. It was

[0010]

[Chemical 2]

In the formula, R ¹ is a hydrogen atom or an alkyl group, R ² is an alkyl group, R ³ is a halogen atom, an alkyl group, an aryl group, an acylamino group or a sulfonamide group, and R ⁴ is a hydrogen atom or an alkyl group. , An aryl group L ¹ ,
L ² represents a divalent linking group, X ⁻ represents an anion, m represents an integer of 0 to 3, and n represents an integer of 0 to 4.

The monomer unit represented by the general formula (I) will be described in detail below.

In the general formula (I), R ¹ represents a hydrogen atom and an alkyl group having 1 to 6 carbon atoms (including those having a substituent, for example, methyl group, ethyl group, isopropyl group, butyl group, hexyl group). . Of these, a hydrogen atom is preferred.

R ² has a total carbon number of 1 to 12, preferably 1
To alkyl groups (including those having a substituent, for example, methyl group, ethyl group, isopropyl group, t-butyl group, hexyl group, undecyl group), aryl groups (including those having a substituent, such as phenyl) Group, naphthyl group)
Represents

R ³ is a halogen atom and has a total carbon number of 1 to 12
, Preferably 1 to 6 alkyl groups (including those having a substituent, for example, methyl group, ethyl group, isopropyl group, t-butyl group, t-octyl group), aryl groups (including those having a substituent) For example, a phenyl group), an acylamino group (eg, acetylamino group, benzoylamino group, propionylamino group), a sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group).

R ⁴ is a hydrogen atom, having a total carbon number of 1 to 12,
It preferably represents an alkyl group having 1 to 6 (including those having a substituent, for example, a methyl group, an ethyl group, a butyl group) and an aryl group (for example, a phenyl group). These groups may further have a substituent.

L ¹ and L ² are each independently a total carbon number of 1 to
12 represents a divalent linking group. Preferred examples of L ¹ and L ² include alkylene groups (including those having a substituent.
For example, a methylene group, an ethylene group, a butylene group), an arylene group (including those having a substituent, for example, a phenylene group), or a divalent group in which two or more of these are bonded in series, or two or more divalent groups. Examples thereof include a divalent group which is bonded via a carbonyl group, an ester group or an ether group when the groups are bonded in series. It is particularly preferred that L ¹ is a phenylene methylene group.

L ² is an alkylene group or 2 in which two or more alkylene groups are bonded via an ether bond.
A valent group is particularly preferred.

Preferred substituents in the monomer unit of the present invention include halogen atom (eg chlorine, bromine), hydroxy group, alkoxy group (eg methoxy group, ethoxy group, methoxyethoxy group, benzyloxy group), aryloxy group ( For example, phenoxy group), alkyl group (for example, methyl group, ethyl group, decyl group, t-butyl group), aralkyl group (for example, benzyl group, phenethyl group), nitro group, cyano group, acylamino group (for example, acetylamino group, benzoyl group). Amino group, phenoxyacetylamino group), sulfonamide group (eg methanesulfonamide group, p-toluenesulfonamide group), ureido group, alkoxycarbonyl group (eg methoxycarbonyl group,
Benzyloxycarbonyl group), carbamoyl group (eg carbamoyl group, N-methylcarbamoyl group, N, N
-Diphenylcarbamoyl group), sulfamoyl group (for example, sulfamoyl group, N-methylsulfamoyl group,
N-phenylsulfamoyl group), acyl group (eg acetyl group, benzoyl group), acyloxy group (eg acetoxy group, benzoyloxy group), sulfonyl group (eg methylsulfonyl group, phenylsulfonyl group), aryl group (eg phenyl Group, naphthyl group) and the like.

Specific preferred examples of L ² are shown below, but the present invention is not limited thereto.

[0021]

[Chemical 3]

R ³ and L or R ³ and R ⁴ may be bonded to each other to form a 5- to 8-membered ring. When n is 2 or more, R ^{3 s} may combine with each other to form a ring.

[0023] X ^- represents an anion. Preferred examples of X ⁻ include halide ions (eg Cl ⁻ , Br
^-, I ^-), hydroxide ions, p- toluenesulfonate ion, benzenesulfonate ion, acetate ion, propionate ion, methanesulfonate ion, sulfate monomethyl ion, PF ₆ ^-, BF ₄ ^- and the like is . Among these, halide ion, p-toluenesulfonate ion, and benzenesulfonate ion are particularly preferable.

M represents an integer of 0 to 3, with 0 being most preferred. n represents an integer of 0 to 4.

Specific preferred examples of the monomer unit represented by the general formula (I) are shown below, but the invention is not limited thereto.

[0026]

[Chemical 4]

[0027]

[Chemical 5]

Next, the polymer mordant of the present invention having a monomer unit represented by the general formula (I) as a constituent will be described in detail.

The polymer mordant of the present invention may be a homopolymer or a copolymer of one or more monomer units represented by the general formula (I),
It may be a copolymerized polymer composed of one or more monomer units represented by the general formula (I) and another one or two or more monomer units.

However, in the polymer mordant of the present invention, the ratio of the sum of the monomer units represented by the general formula (I) in all the monomer units is important, and preferably 10%.
(Wt%) or more, more preferably 50% (wt%) or more.

In the polymer mordant of the present invention, it has already been described that a monomer unit other than the monomer unit represented by the general formula (I) is also used as a copolymerization component. These are generally monomer units derived from ethylenically unsaturated monomers.

Examples of the ethylenically unsaturated monomer preferably used in the polymer mordant of the present invention include propylene, 1-butene, isobutene, styrene, α-methylstyrene, N-vinylimidazole, vinyl acetate, vinylpyridines and acrylic acid. , Acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylamide, methacrylamide, N-alkylacrylamides, acrylonitrile, methacrylonitrile, N-vinylpyrrolidone, butadiene, isoprene, styrene sulfinate, hydroxymethylstyrene, chloromethylstyrene And styrene derivatives having various cationic groups, which are synthesized from chloromethylstyrene and a tertiary amine or a nitrogen-containing heterocyclic compound.

Also, divinylbenzene, ethylene glycol dimethacrylate, isopropylene glycol diacrylate, tetramethylene glycol dimethacrylate, tetramethylene glycol diacrylate, etc.
Functional monomers are also preferably used. These bifunctional monomers are preferably used during emulsion polymerization. Also,
The mordant of the present invention, when used in the dye-fixing element of the present invention, is preferably one that is difficult to move from the mordant layer to another layer,
For example, water-insoluble mordants, aqueous sol mordants, or latex mordants are preferable.

A latex dispersion mordant is particularly preferable, and the particle diameter is 0.01 to 2.0 μm, preferably 0.0.
It is preferably 5 to 0.2 μm.

The latex-like polymer mordant preferably used in the present invention can be synthesized, for example, by the following method. That is, the bifunctional monomer and the monomer represented by the following general formula (I) (for example, chloromethylstyrene)

[0036]

[Chemical 6]

(Wherein X represents an anionic leaving group such as a halogen atom) and then emulsion-polymerized, and then the following general formula (II
This is a method of quaternization with an imidazole derivative represented by I).

[0038]

[Chemical 7]

(Provided that R ² , R ³ , R ⁴ , L, m and n
Is based on the definition in the general formula (I). However, in this case, the monomer of the general formula (II) may be partially hydrolyzed to incorporate the hydroxymethylstyrene unit into the polymer.

The above-mentioned emulsion polymerization is generally carried out by using an anionic surfactant (for example, commercially available from Rohm and Haas Company under the name of Triton 770), a cationic surfactant (for example cetyltrimethylammonium chloride), a nonionic surfactant ( It is carried out in the presence of at least one surfactant selected from, for example, polyvinyl alcohol and a radical initiator (for example, a combination of potassium persulfate and sodium bisulfite).

The above-mentioned quaternization reaction is carried out at a temperature of 0 ° C to 110 ° C, preferably 30 ° C to 80 ° C.

Preferred specific examples of the polymer mordant of the present invention are shown below, but the present invention is not limited thereto.

[0043]

[Chemical 8]

[0044]

[Chemical 9]

[0045]

[Chemical 10]

The synthetic examples of the compounds of the present invention are shown below, but the present invention is not limited thereto.

Synthesis Example 1 (1) Synthesis of Poly (divinylbenzene-co-chloromethylstyrene) Polymer Dispersion 350 ml of distilled water was placed in a reaction vessel and degassed with nitrogen gas. Triton 77010 ml, chloromethylstyrene 5
8.0 g (0.38 mol), divinylbenzene 2.6 g
(0.02 mol) was added and the mixture was heated to 60 ° C. 20 ml of degassed distilled water and 0.38 g of sodium bisulfite added to 10 ml of distilled water degassed with nitrogen gas
To the reaction vessel was added 1.00 g of potassium persulfate at the same time, and heating and stirring were continued for 5 hours. Then, the above mixture was cooled to room temperature and filtered to obtain a polymer dispersion (latex).

(2) To a quaternization reaction container, 150 g of the above latex having a solid content of 14.0% and 50 g of distilled water were added, and N- (p
80 ml of a solution of 24 g of -methoxyphenoxyethyl) imidazole in isopropyl alcohol was added. Then, the temperature was slowly raised to 70 ° C., and the mixture was heated and stirred for 2 hours. After cooling to room temperature, the mixture was filtered to obtain a polymer mordant dispersion (Exemplified Compound 2).

The dye fixing element using the polymer mordant of the present invention will be described in detail below.

The dye fixing element of the present invention comprises at least one layer comprising the polymer mordant of the present invention, and is a method for transferring an image to form an image (a typical example of this method is so-called instant photography). Method, ink jet method, thermal transfer method of dyes, etc.) as an image receiving layer or an image receiving element.

The dye-fixing element of the present invention may be coated with the polymer mordant of the present invention alone. However, gelatin is polyvinyl alcohol, polyvinyl pyrrolidone or the like, which is a natural or synthetic hydrophilic agent generally used in the field of photography. Different polymer (preferably polyvinyl alcohol etc.)
May also be included.

The dye fixing element of the present invention may comprise two or more mordants of the present invention, or may be used in combination with other mordants. Mordants which can be used in combination with the dye fixing element of the present invention are described in US Pat. No. 4,131,469.
No. 4,147,548, JP-A-52-13662.
No. 6, No. 54-126027, No. 54-145529.
The mordant described in the above item can be mentioned. The amount of the polymer mordant used depends on the amount of the dye to be mordant, the type and composition of the polymer mordant, and the image forming process used.
It can be easily determined by those skilled in the art, but as one guide, it is about 20 to 80% by weight of the mordant layer, or about 0.
5 to 15 g / m ² of polymer mordant, preferably 40 to 60
% By weight or 1 to 10 g / m ² .

In the present invention, a known anti-fading agent may be used in combination. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a kind of metal complex. These are used in a layer in which the polymer mordant of the present invention is present or in a layer adjacent to the layer, in such a form that it remains after the image forming process is completed.

Examples of 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 (U.S. Pat. No. 3,352,6
No. 81), benzophenone compounds (JP-A-46-
2784) and others, JP-A-54-48535,
There are compounds described in JP-A-62-136641, JP-A-61-188256 and the like. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective.

Examples of the metal complex include US Pat.
No. 1,155, No. 4,245,018, Nos. 3 to 36
No. 4,254,195, columns 3 to 8, JP-A-62.
-174741, 61-88256 (27)-
(29), Japanese Patent Application Nos. 62-234103 and 62-3.
1096 and Japanese Patent Application No. 62-230596.

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 image receiving 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. The above antioxidant, ultraviolet absorber,
The metal complexes may be used in combination with each other.

Now, the color diffusion transfer method (instant photography method), which is a useful embodiment of the present invention, will be described below. A typical form of a film unit used in the color diffusion transfer method is that a dye fixing element and a photosensitive element are laminated on one transparent support, and after the transfer image is completed, the photosensitive element is separated from the dye fixing element. It is a form that does not require peeling. More specifically, the dye-fixing element comprises at least the mordant layer described above, 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 magenta dye-donating substance, and a cyan dye-donating substance, each of which is composed (here, "infrared light-sensitive emulsion layer" is 700
nm or more, especially an emulsion layer having sensitivity to light of 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 dye-donating substance-containing layer so that the transferred image can be viewed through the transparent support.

A light-shielding layer may be further provided between the white reflective layer and the photosensitive layer so that the development process can be completed in a bright place. Further, if desired, a release layer may be provided at an appropriate position so that all or part of the light-sensitive element can be released from the dye-fixing element.
-67840 and Canadian Patent 674,082).

As another embodiment of the laminate type and peeling, a layer having at least (a) a neutralizing function, (b) a dye image-receiving layer, and (a) on a white support described in Japanese Patent Application No. 62-231374. c) a release layer, (d) a light-sensitive element sequentially having at least one silver halide emulsion layer combined with a dye image-forming substance, an alkali processing composition containing a light-shielding agent, and a transparent cover sheet. There is a color diffusion transfer photographic film unit characterized by having a layer having a light shielding function on the side opposite to the side where the processing composition is developed.

In another embodiment 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. .
For a mode in which an image receiving element, a white reflective layer, a peeling layer and a photosensitive element are laminated on the same support and the photosensitive element is intentionally peeled from the dye fixing element, see US Pat.
No. 718.

On the other hand, there are roughly two typical forms in which a light-sensitive element and a dye fixing element are separately coated on two supports, one is a peeling type and the other is a peeling-free type. Is. Explaining these in detail, in a preferred embodiment of the peelable film unit, at least one image receiving layer is coated on one support, and the photosensitive element is coated on a support having a light shielding layer. , The photosensitive layer coated surface and the mordant layer coated surface do not face each other before the exposure is completed, but after the exposure is completed (for example, during the development process), the photosensitive layer coated surface is turned over and overlapped with the image receiving layer coated 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. However, the photosensitive layer coated surface and the mordant layer coated surface face each other and are superposed.

A pressure-rupturable container (processing element) containing an alkaline processing liquid may be combined with the above-described form. Among others, in a non-release type film unit in which a dye fixing element and a light sensitive element are laminated on one support, this processing element is preferably arranged between the light sensitive element and a cover sheet overlaid thereon. Further, in the form in which the light-sensitive element and the dye-fixing element are separately coated on the two supports, it is preferable that the processing element be disposed between the light-sensitive element and the dye-fixing element at the time of development processing at the latest. The processing element preferably contains a light-shielding agent (such as carbon black or a dye whose color changes with 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 composed of a combination of a neutralization layer and a neutralization timing layer is incorporated in the cover sheet, the dye fixing element or the photosensitive element. .

In the present invention, the above-mentioned processing for image formation is carried out at a temperature of 50 ° C. or lower.

Dye image-forming materials useful in the light-sensitive element are non-diffusible compounds that release a diffusible dye (which may be a dye precursor) in connection with silver development, or their own diffusivity. The Theory of the Photographic Process
"4th edition. All of these compounds can be represented by the following general formula (A).

DYE-Y (A)

Here, DYE represents a dye or its precursor, and Y represents a component which gives a compound having a different diffusibility from the compound under alkaline conditions. According to the function of Y, it is roughly classified into a negative type compound which becomes diffusive in the silver developed area and a positive type compound which becomes diffusible in the undeveloped area.

Specific examples of the negative type Y include those which are oxidized as a result of development and cleaved to release a diffusible dye.

A specific example of Y is US Pat. No. 3,928,312.
No. 3, No. 3,993,638, No. 4,076,529
No. 4,152,153, 4,055,428
Issue 4,053,312, Issue 4,198,235
Issue No. 4,179,291 Issue No. 4,149,892
Issue No. 3,844,785 Issue 3,443,943
Issue No. 3,751,406, No. 3,443,939
No. 3,433,940 No. 3,628,952
No. 3,980,479, 4,183,753
No. 4,142,891, No. 4,278,750
Nos. 4,139,379 and 4,218,368.
Issue 3, Issue 4,421,964, Issue 4,199,355
Issue 4,199,354, Issue 4,135,929
No. 4,433,322, 4,139,389
JP-A-53-50736, JP-A-51-104343.
No. 54-130122, No. 53-110827
No. 56-12642, No. 56-16131, No. 57-4043, No. 57-650, No. 57-207.
No. 35, No. 53-69033, No. 54-130927.
No. 56-164342, No. 57-119345 and the like.

Among Y of the negative dye-releasing redox compound, a particularly preferable group is an N-substituted sulfamoyl group (the N-substituent is a group derived from an aromatic hydrocarbon ring or a hetero ring). it can. The representative groups of Y are illustrated below, but the present invention is not limited thereto.

[0072]

[Chemical 11]

For positive type compounds, Angevante Chemi Inst. Ed. Engl., 22, 191 (19)
82). Specific examples thereof include compounds (dye developers) that are initially diffusible under alkaline conditions, but are oxidized by development to become non-diffusible. Effective Y for this type of compound is described in US Pat. No. 2,983,606.
The ones listed in the issue are typical.

Another type is one in which a diffusible dye is released by self-ring closure under alkaline conditions, but the dye is substantially not released when oxidized by development. . Specific examples of Y having such a function are described in U.S. Pat. No. 3,980,479 and JP-A-53-53.
69033, 54-130927, and U.S. Pat. No. 3,42.
1, 964 and 4,199,355.

Another type is one that does not itself release a dye but releases a dye when reduced.
This type of compound is used in combination with an electron donor,
The diffusible dye can be imagewise released by reaction with the residual electron donor which has been imagewise oxidized by silver development. Regarding the atomic group having such a function, for example, U.S. Pat. Nos. 4,183,753, 4,142,891, 4,278,750, 4,139,379 and 4,2 are disclosed.
18,368, JP-A-53-1108827, U.S. Pat. Nos. 4,278,750, 4,356,249 and 4,3.
58,525, JP-A-53-1108827 and JP-A-54-1.
30927, 56-164342, and open technical report 87-6.
199, European Patent Publication 220746A2 and the like.

Specific examples are shown below, but the present invention is not limited thereto.

[0077]

[Chemical 12]

When a compound of this type is used, it is preferably used in combination with a diffusion-resistant electron donating compound (known as an ED compound) or its precursor (precursor). Examples of ED compounds include, for example, US Pat.
263,393, 4,278,750, JP-A-5
6-138736 and the like.

The following can also be used as specific examples of another type of dye image-forming substance.

[0080]

[Chemical 13]

(In the formula, DYE represents a dye having the same meaning as described above or a precursor thereof.) The details are described in US Pat.
19, 489 and 4,098,783.

On the other hand, specific examples of the dye represented by DYE of the above general formula are described in the following documents.

Examples of yellow dyes: US Pat. No. 3,597,
No. 200, No. 3,309,199, No. 4,013,6
No. 33, No. 4,245,028, No. 4,156,60
No. 9, No. 4,139,383, No. 4,195,992
No. 4,148,641 No. 4,148,643
No. 4,336,322: JP-A-51-11493
No. 0, No. 56-71072: Research Disclosure 1
7630 (1978) and 16475 (1977).

Examples of magenta dyes: US Pat. No. 3,453,353
No. 107, No. 3,544,545, No. 3,932,3
80, 3,931,144, 3,932,30
No.8, No.3,954,476, No.4,233,237
Nos. 4,255,509 and 4,250,246
No. 4,142,891, No. 4,207,104
No. 4,287,292: JP-A-52-106,7.
No. 27, No. 52-106727, No. 53-23, 62.
No. 8, No. 55-36, 804, No. 56-73, 057.
Nos. 56-71060 and 55-134.

Examples of cyan dyes: US Pat. No. 3,482,9
72, 3,929,760, 4,013,63
No. 5, No. 4,268,625, No. 4,171,220
No. 4,242,435, 4,142,891
Issue No. 4,195,994, No. 4,147,544
No. 4,148,642; British Patent 1,551,1
38; JP-A-54-99431 and JP-A-52-8827.
No. 53-47823, No. 53-143323,
54-99431, 56-71061; European Patent (EPC) 53,037, 53,040.
Issue; Research Disclosure 17,630 (1978)
And those described in No. 16,475 (1977).

The silver halide emulsion used in the color diffusion transfer method in the present invention may be a negative type emulsion forming a latent image on the surface of silver halide grains, or an internal latent image forming a latent image on the inside of silver halide grains. Direct type positive emulsion may be used.

The internal latent image type direct positive emulsion is, for example, a so-called "conversion type" emulsion formed by utilizing the difference in solubility of silver halide, or a metal ion doped or
Alternatively, a "core / shell" emulsion in which at least a light-sensitive site of an inner core (core) grain of silver halide chemically sensitized or both is coated with an outer shell (shell) of silver halide There are US Pat. Nos. 2,592,250, 3,206,313, British Patent 1,027,146, US Patents 3,761,276, 3,935,014, and 3,447. 927, 2,4
97,875, 2,563,785, 3,551
662, 4,395, 478, West German Patent 2,728,
108, U.S. Pat. No. 4,431,730 and the like.

When an internal latent image type direct positive emulsion is used, it is necessary to provide a fog nucleus on the surface by using light after image exposure or a nucleating agent.

As a nucleating agent therefor, US Pat.
Hydrazines described in U.S. Pat. No. 3,227,552, hydrazines, British patents 1,283,8.
35, JP-A-52-69613, US Pat. No. 3,615,
615, same 3,719,494, same 3,734,73
8, 4,094,683, 4,115,122 and the like, heterocyclic quaternary salt compounds, US Pat. No. 3,718,
470, a sensitizing dye having a substituent having a nucleating action in a dye molecule, U.S. Pat. Nos. 4,030,925, 4,031,127, 4,245,037 and 4,2.
55,511, 4,266,013, 4,276,
364, thiourea-bonding acylhydrazine compounds described in British Patent 2,012,443, and US Patents 4,080,270, 4,278,748, and British Patent 2,011,391B. Further, an acylhydrazine compound having a thioamide ring or a heterocyclic group such as triazole or tetrazole bonded as an adsorption group is used.

In the present invention, a spectral sensitizing dye is used in combination with these negative type emulsion and internal latent image type direct positive emulsion.
Specific examples thereof are described in JP-A-59-180550,
No. 60-140335, Research Disclosure (RD) 17029, US Pat. Nos. 1,846,300, 2,078,233, 2,089,129, and 2,1.
65,338, 2,231,658, 2,917,
516, 3,352,857, 3,411,91
6, the same 2,295,276, the same 2,481,698, the same 2,688,545, the same 2,921,067, the same 3,2
82,933, 3,397,060, 3,660,
103, same 3,335,010, same 3,352,68
0, 3,384,486, 3,623,881, 3,718,470, 4,025,349 and the like.

For the reproduction of natural color by the subtractive color method, a combination with the dye image-forming substance which provides a dye having a selective spectral absorption in the same wavelength range as the emulsion spectrally sensitized by the spectral sensitizing dye is used. Is used for the photosensitive layer. The emulsion and the dye image-forming substance may be coated separately as separate layers, or may be mixed and coated as a single layer. When the dye image-forming substance is coated and has absorption in the spectral sensitivity region of the emulsion combined with it, another layer is preferable. The emulsion layer may be composed of a plurality of emulsion layers having different sensitivities, and an arbitrary layer may be provided between the emulsion layer and the dye image-forming substance layer. For example, JP-A-60-1
A layer containing a nucleation development accelerator described in 73541, a partition layer described in JP-B-60-15267 are provided to increase the color image density, and a reflection layer described in JP-A-60-91354 is provided. You can also increase the sensitivity of the photosensitive element.

In a preferable multilayer structure, a combination unit of blue-sensitive emulsion, a combination unit of green-sensitive emulsion and a combination unit of red-sensitive emulsion are sequentially arranged from the exposure side. An arbitrary layer may be provided between the emulsion layer units as required.
In the case of using a compound which releases a diffusible dye by silver ion as described in 1), it is preferable to include a compound which traps silver ion in the intermediate layer.

In the present invention, an anti-irradiation layer, an isolation layer, a protective layer and the like are coated as necessary.

The processing composition used in the present invention is uniformly spread on the light-sensitive element after exposure of the light-sensitive element, and a light-shielding layer provided on the back surface of the support or on the opposite side of the light-sensitive layer from the processing solution, if necessary. In combination with the above, the photosensitive layer is completely shielded from external light, and at the same time, the photosensitive layer is developed by the components contained therein. Therefore, in the composition, an alkali, a thickener, a light-shielding agent, a developer, a development accelerator for controlling development, a development inhibitor, an antioxidant for preventing deterioration of the developer, and the like. Contains.

Alkali is sufficient to adjust the pH of the liquid to 12 to 14, and alkali metal hydroxides (eg sodium hydroxide, potassium hydroxide, lithium hydroxide),
Examples thereof include alkali metal phosphates (for example, potassium phosphate), guanidines, and quaternary amine hydroxides (for example, tetramethylammonium hydroxide). Of these, potassium hydroxide and sodium hydroxide are preferable.

The thickener is used to spread the treatment liquid uniformly.
Further, it is necessary to maintain the adhesion between the photosensitive layer and the cover sheet when the used photosensitive layer is peeled off together with the cover sheet. For example, an alkali metal salt of polyvinyl alcohol, hydroxyethyl cellulose or carboxymethyl cellulose is used, and preferably hydroxyethyl cellulose or sodium carboxymethyl cellulose is used. As the light-shielding agent, any dye or pigment, or a combination thereof, can be used as long as it does not diffuse to the dye image-receiving layer to generate stain. Carbon black is a typical example, but a combination of titanium white and dye can also be used. The dye may be a temporary light-shielding dye that becomes colorless after a certain time of treatment.

As the preferred developing agent, any developing agent can be used as long as it cross-oxidizes the dye image-forming substance and does not substantially produce stain when oxidized. Such developing agents may be used alone or in combination of two or more, and may be used in a precursor type. These developers may be included in the appropriate layers of the light sensitive element or in the alkaline processing liquid. Specific examples of the compound include aminophenols and pyrazolidinones. Of these, pyrazolidinones are particularly preferable because they generate less stain.

For example, 1-phenyl-3-pyrazolidinone, 1-p-tolyl-4,4-dihydroxymethyl-3
-Pyrazolidinone, 1- (3'-methyl-phenyl)-
4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidinone, 1-p-tolyl-4-methyl-
4-hydroxymethyl-3-pyrazolidinone, and the like.

In the color diffusion transfer film unit of the present invention, it is preferable to provide a neutralizing function between the support and the photosensitive layer, between the support and the image receiving layer or on the cover sheet.

The layer having a neutralizing function is a layer containing an acidic substance in an amount sufficient to neutralize the alkali carried from the treatment composition, and if necessary, a neutralization rate adjusting layer (timing layer), It may have a multi-layered structure including layers such as an adhesion enhancing layer. A preferred acidic substance is a substance containing an acidic group having a pKa of 9 or less (or a precursor group which gives such an acidic group by hydrolysis), more preferably oleic acid described in US Pat. No. 2,983,606. Higher fatty acids, such as polymers of acrylic acid, methacrylic acid or maleic acid and their partial esters or anhydrides as disclosed in US Pat. No. 3,362,819; French Patent 2,290,699. Copolymers of acrylic acid and acrylates as disclosed in U.S. Pat. No. 4,139,383 and latex type as disclosed in Research Disclosure No. 16102 (1977). The acidic polymer can be mentioned.

Others, US Pat. No. 4,088,493,
Japanese Patent Laid-Open Nos. 52-153,739 and 53-1,023
No. 53-4,540, No. 53-4,541, No. 53-4,542, etc. can also be mentioned.

Specific examples of the acidic polymer include ethylene,
Examples thereof include copolymers of vinyl monomers such as vinyl acetate and vinyl methyl ether with maleic anhydride, and n-butyl esters thereof, copolymers of butyl acrylate and acrylic acid, and cellulose acetate hydroene phthalate.

The polymer acid can be used as a mixture with a hydrophilic polymer. As such a polymer,
Examples include polyacrylamide, polymethylpyrrolidone, polyvinyl alcohol (including partially saponified products), carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polymethyl vinyl ether and the like. Of these, polyvinyl alcohol is preferable.

The coating amount of the polymer acid is adjusted by the amount of alkali spread on the photosensitive element. The equivalent ratio of polymer acid and alkali per unit area is preferably 0.9-2.0. If the amount of the polymer acid is too small, the hue of the transfer dye is changed or stains are generated on the white background portion, and if it is too large, the hue is changed or the light resistance is deteriorated. A more preferred equivalent ratio is 1.0-1.3. If too much or too little hydrophilic polymer is mixed, the quality of the photograph will be degraded. The weight ratio of hydrophilic polymer to polymeric acid is 0.1-10, preferably 0.3.
It is −3.0.

Additives can be incorporated into the layer having a neutralizing function of the present invention for various purposes. For example, hardening agents well known to those skilled in the art for hardening this layer, and polyhydric hydroxyl compounds such as polyethylene glycol, polypropylene glycol, glycerin, etc. for improving the brittleness of the film can be added. Other as needed
Antioxidants, optical brighteners, dyes for bluing, and the like can also be added.

The timing layer used in combination with the neutralizing layer has a low alkali permeability such as gelatin, polyvinyl alcohol, a partial acetalization product of polyvinyl alcohol, cellulose acetate, and partially hydrolyzed polyvinyl acetate. Polymer; made by copolymerizing a small amount of hydrophilic comonomers such as acrylic acid monomer,
Latex polymers which increase the activation energy of alkali permeation; polymers having a lactone ring are useful.

Among them, JP-A-54-136328,
US Pat. Nos. 4,267,262 and 4,009,030
No. 4,029,849, and other timing layers using cellulose acetate; JP-A-54-128
335, 56-69,629, 57-6,84
3, U.S. Pat. Nos. 4,056,394 and 4,061,
No. 496, No. 4,199,362, No. 4,250,2
No. 43, No. 4,256,827, No. 4,268,60
Latex polymers made by copolymerizing a small amount of hydrophilic comonomers such as acrylic acid disclosed in U.S. Pat. No. 4, etc .; Polymers having a lactone ring disclosed in US Pat. No. 4,229,516; 56-25735
Nos. 56-97346, 57-6842, European Patent (EP) 31,957A1, 37,72.
The polymers disclosed in 4A1 and 48412A1 are particularly useful.

In addition, the materials described in the following documents can also be used. US Pat. Nos. 3,421,893 and 3,455
No. 686, No. 3,575, 701, No. 3,778, 2
No. 65, No. 3,785,815, No. 3,847,61
No. 5, No. 4,088,493, No. 4,123,275
No. 4,148,653, 4,201,587
No. 4,288,523, 4,297,431
, West German Patent Applications (OLS) 1,622,936, 2,162,277, Research Disclosure 15,
162 No. 151 (1976)

The timing layer using these materials can be used as a single layer or as a combination of two or more layers. Further, for the timing layer made of these materials, for example, US Pat. No. 4,009,029, West German Patent Application (OLS) 2,9
13,164, 3,014,672, JP-A-54
No. 155837, No. 55-138745, and the like, development inhibitors and / or their precursors, hydroquinone precursors disclosed in US Pat. No. 4,201,578, and other useful additives for photography. Or it is possible to incorporate the precursor etc.

[0110]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto.

First, a method for preparing a silver halide emulsion will be described. Preparation of tabular silver bromide emulsion: 1 liter of 0.8% by weight aqueous gelatin solution containing 0.08M potassium bromide,
While stirring it, 150 cc of a 2.00 M silver nitrate aqueous solution and a 2.00 M potassium bromide aqueous solution are added by the double jet method. During this time, the gelatin aqueous solution is at 30 ° C
Kept in. After the addition, the temperature was raised to 75 ° C. After the addition, 30 g of gelatin was added. After the addition of the first step above, 1.
90cc of 0M silver nitrate aqueous solution was added. Furthermore, after the addition, aging was carried out for 30 minutes. The particles thus formed (hereinafter referred to as seed crystals) were washed by a conventional flocculation method to obtain pH 5.0 and pAg at 40 ° C.
It was adjusted to be 7.5. 1/10 of the above seed crystals
It was dissolved in 1 liter of an aqueous solution containing 3% by weight of gelatin and kept at a temperature of 75 ° C. and a pBr of 1.60. After this 6
In 0 minutes 150 g of silver nitrate was added at an accelerated flow rate (end flow rate 19 times start flow rate). During this period p
Br was kept at 1.60. Further, silver nitrate was added in the presence of ammonium thiocyanate so that pBr would be 2.70. After that, the emulsion was cooled to 35 ° C., washed by a conventional flocculation method, and the pH at 40 ° C.
After adjusting to 6.5 and pAg 8.6, it was stored in a cool and dark place. The tabular grains have an average projected area circle equivalent diameter of 1.3.
The average thickness was 0.25 μm.

Preparation of emulsion for red light-sensitive layer: The temperature of the tabular silver bromide emulsion was adjusted to 55 ° C., sodium benzenethiosulfonate, sensitizing dyes S-1 and S-2, and 4-hydroxy-6- below. In the presence of methyl-1,3,3a, 7-tetrazaindene, Na ₂ SO ₃ , KAuCl ₄ , and ammonium thiocyanate were added for chemical ripening, and when the maximum sensitivity was reached, the temperature was lowered and the chemistry was lowered. End the sensitization,
An emulsion for the red photosensitive layer was prepared. Sensitizing dyes S-1 and S-
2, Na ₂ SO ₃ and KAuCl ₄ were added in such amounts that the highest sensitivity was obtained.

Preparation of emulsion for green light-sensitive layer: sensitizing dye S-3
An emulsion for a green light-sensitive layer was prepared in the same manner as the emulsion layer for a red light-sensitive layer except that the emulsion was changed to. Preparation of emulsion for blue photosensitive layer: An emulsion for green photosensitive layer was prepared in the same manner as the emulsion layer for red photosensitive layer except that the sensitizing dye S-4 was used.

[0114]

[Chemical 14]

[0115]

[Chemical 15]

Next, a method for preparing a gelatin dispersion of a dye-donor compound will be described. Yellow dye-donor compound (1)
^* The 18 g, high-boiling organic solvent (1) ^* was 12g weighed, ethyl acetate 51ml was added, dissolved under heating to about 60 ° C., to obtain a uniform solution. This solution, 100 g of a 10% aqueous solution of lime-processed gelatin, 60 cc of water and 1.5 g 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 compound dispersion. Dispersions of magenta and cyan dye-donor compounds were made with magenta dye-donor compound (2) ^* or cyan dye-donor compound (3) ^* as well as yellow dye-donor compound.

Next, a method for preparing a gelatin dispersion of an electron donor will be described. 20.6 g of the electron donor (1) ^* and 13.1 g of the high boiling point organic solvent (1) ^* were weighed, and ethyl acetate 12
0 ml was added and dissolved by heating at about 60 ° C. to obtain a uniform solution. This solution and 100% 10% aqueous solution of lime-processed gelatin
g, 60 cc of water and 1.5 g of sodium dodecylbenzenesulfonate with stirring, and then 1 with a homogenizer.
Dispersed for 0 minutes at 10,000 rpm. This dispersion is called a dispersion of electron donors.

Next, a method for preparing a gelatin dispersion of the diffusion resistant reducing agent for the intermediate layer will be described. Diffusion resistant reducing agent (1) ^*
23.5 g and high-boiling organic solvent (1) ^* 8.5 g were dissolved in 120 ml of ethyl acetate at about 60 ° C. to obtain a uniform solution. This solution, 100 g of a 10% aqueous solution of lime-processed gelatin, 15 ml of a 5% aqueous solution of a surfactant (3) ^* and 0.2 g of dodecylbenzenesulfonic acid were mixed with stirring and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is referred to as a dispersion of the diffusion resistant reducing agent for the intermediate layer. From these, a photosensitive element 101 having the constitution shown in Table 1 below was prepared.

[0119]

[Table 1]

[0120]

[Table 2]

[0121]

[Chemical 16]

[0122]

[Chemical 17]

[0123]

[Chemical 18]

[0124]

[Chemical 19]

Preparation of dye-fixing elements Comparative dye-fixing elements (201) and (202) having the structures shown in Tables 2-A and 2-B, and the dye-fixing elements (203 to 207) of the present invention were prepared. did. Each layer of these dye fixing elements is hardened by a hardener.

[0126]

[Table 3]

* Polymer latex (1) Weight ratio of styrene / butyl acrylate / acrylic acid / N-methylol acrylamide 49.7 / 42.3 / 4
Emulsion polymerized at / 4 polymer latex (2) Emulsion polymerized methyl methacrylate / acrylic acid / N-methylol acrylamide at a weight ratio of 933/4

[0128]

[Chemical 20]

[0129]

[Table 4]

[0130]

[Chemical 21]

The dye-fixing element (201) is a dye-fixing element containing a mordant disclosed in JP-A-59-232340 as a mordant which is less susceptible to fading by light.

The formulation of the treatment liquid is shown below. A destructible container was filled with 0.8 g of the treatment liquid having the following composition. 1-p-tolyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 10.0 g 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 4.0 g potassium sulfite (anhydrous) 4.0 g hydroxy Ethyl cellulose 40g Potassium hydroxide 64g Add water to make 1kg

Image Lightfastness Evaluation Method (Fade Test) For each of cyan, magenta, and yellow, the photosensitive element (101) is provided so as to obtain a monochromatic color image in which the image density changes stepwise. Was exposed from the emulsion layer side. Next, the image receiving layer side of the dye fixing elements (201) to (208) and the photosensitive layer side of the photosensitive element (101) are overlapped face-to-face, and the processing liquid is pressed between both materials so as to have a thickness of 60 μm. It was developed using a roller. This expansion process is 2
The photosensitive element (101) and the dye fixing element were peeled off after 1 minute and 30 seconds at 5 ° C.

The reflection density of the color image transferred to each dye fixing element was measured with an X-Rite 310 type densitometer. Each dye-fixing element was irradiated with light emitted from a xenon light, and after 3 days, the reflection density of the color image remaining on the dye-fixing element was measured. Next, the residual dye ratio after the fading test was plotted against the density before the fading test, and the residual dye ratio for the portion with an image density of 1.0 before the fading test was determined. The dye residual ratio after 3 days thus obtained is shown in Table 3.

Method for evaluating mordant strength (competitive test) The light-sensitive element (101) was left unexposed and the dye-fixing element (2) was used.
01) and 60 μ of the above treatment liquid between both materials.
It was developed using a pressure roller so as to have a thickness of m.
This development treatment was carried out at 25 ° C., and the photosensitive element (101) and the dye-fixing element were peeled off after 1 minute and 30 seconds. Water is applied to the image receiving layer side of the black image (black solid) obtained by this treatment,
The dye-fixing elements (201) to (208) were superposed so that the image receiving layer sides thereof faced each other, heated to 83 ° C. and kept for 25 seconds, and both were peeled off. Dye fixing element (201) to (20
The visual density of the reflection density of the color image transferred to 8) was measured with an X-Rite 310 type densitometer. The results are shown in Table 3 together with the results of the fading test. In this test,
The higher the density of the obtained color image, the stronger the mordant strength of the mordant.

[0136]

[Table 5]

From Table 3, the dye fixing element of the present invention (203 to
208 is a comparative dye fixing element (201), (20)
It can be seen that, compared with 2), the mordant strength is strong and the light fastness of the image is very excellent. Example-2 The following photosensitive element (301) was prepared in order to further confirm the improving effect of the present invention.

Photosensitive Element 301 A polyethylene terephthalate transparent support was coated with the following layers to prepare a photosensitive sheet.

Back layer: (a) 4.0 g of carbon black
/ M ^2, the light-shielding layer having a gelatin 2.0 g / m ^2,

Emulsion layer side: (1) The following cyan dye-releasing redox compound 0.44 g / m ² , tricyclohexyl phosphate 0.09 g / m ² , 2,5-di-t-pentadecylhydroquinone 0.008 g / m ² , and a layer with gelatin 0.8 g / m ² .

[0141]

[Chemical formula 22]

(2) A layer containing 0.5 g / m ² of gelatin. (3) Red-sensitive inner latent direct positive silver bromide emulsion (0.6
g / m ² ), gelatin 1.2 g / m ² , the following nucleating agent 0.0
Red-sensitive emulsion layer containing 15 g / m ² and 2-sulfo -5-n-pentadecylhydroquinone sodium salt 0.06 g / m ^2.

[0143]

[Chemical formula 23]

[0144] (4) 2,5-di -t- pentadecylhydroquinone 0.43 g / m ^2, trihexyl phosphate 0.1 g / m ² and a layer containing gelatin 0.4 g / m ^2. (5) 0.3% of the following magenta dye releasing redox compound
g / m ² , tricyclohexyl phosphate (0.08 g
/ M ^2), 2,5- di -tert- pentadecylhydroquinone (0.009g / m ²⁾ and gelatin (0.5g / m ²⁾
Containing layers.

[0145]

[Chemical formula 24]

(6) Green-sensitive internal latent direct positive silver bromide emulsion (0.42 g / m ^{2 in} terms of silver amount), gelatin (0.9 g / m ² ),
A green-sensitive emulsion layer containing the same nucleating agent (0.013 g / m ² ) and 2-sulfo-5-n-pentadecylhydroquinone sodium salt (0.07 g / m ² ) as in layer (3).

(7) The same layer as (4). (8) yellow dye-releasing redox compound having the following structure (0.53 g / m ^2), tri-cyclohexyl phosphate (0.13g / m ^2), 2,5- di -t- pentadecylhydroquinone (0.014 g / m ² ) And gelatin (0.7 g / m ² ).

[0148]

[Chemical 25]

(9) Blue-sensitive internal latent direct positive silver bromide emulsion (0.6 g / m ^{2 in} terms of silver amount), gelatin ((10) Layer containing 1.0 g / m ² of gelatin 1.1 g / m ² ),
Layer (3) and the same nucleating agent (0.019 g / m ²⁾ and 2-sulfo -5-n-pentadecylhydroquinone sodium salt (0.05 g / m ²⁾ blue-sensitive emulsion layer containing a.

[0150] Processing liquid   1-p-tolyl-4-hydroxymethyl-4-methyl-3-     Pyrazolidone 6.9g   Methyl hydroquinone 0.3g   5-methylbenzotriazole 3.5 g   Sodium sulfite (anhydrous) 0.2g   Carboxymethyl cellulose / Na salt 58g   Potassium hydroxide (28% aqueous solution) 200cc   Benzyl alcohol 1.5cc   Water 835cc

After exposing the light-sensitive element 301 in the same manner as in Example 1, the dye-fixing element (20
1) to (208) were superposed, and the following treatment liquid was spread between both sheets so as to have a thickness of 60 μ (spreading was performed with the help of a pressure roller). The treatment is carried out at 25 ° C., and 90 seconds after the treatment, the light-sensitive element and the dye-fixing element (20
1) to (208) were peeled off and naturally dried.

The color fastness of the obtained color image was evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0153]

[Table 6]

From the results shown in Table 4, the dye-fixing elements (203) to (208) using the mordant of the present invention are more light-fast than the dye-fixing elements (201) and (202) for comparison. It turns out that he has excellent sex.

[0155]

From the above results, the dye fixing element using the polymer mordant of the present invention is excellent in mordant power and light fastness,
As a result, it can be seen that it has extremely good image storability.

Claims (2)

[Claims] 1. A dye fixing element comprising a polymer mordant having a monomer unit represented by the following general formula (I) as a constituent. [Chemical 1] In the formula, R ¹ is a hydrogen atom or an alkyl group, R ² is an alkyl group, R ³ is a halogen atom, an alkyl group, an aryl group, an acylamino group, a sulfonamide group, and R ⁴ is a hydrogen atom, an alkyl group, an aryl group. L ¹ and L ² are divalent linking groups, X ⁻ is an anion, m is an integer of 0 to 3,
Represents an integer of 0 to 4. 2. The dye fixing element according to claim 1, wherein L ¹ in the general formula (I) is a phenylene methylene group.