JPH06118592A - Dye fixing element - Google Patents

Abstract

PURPOSE:To provide a dye fixing element giving a color image excellent in lightfastness when a dye is diffused and transferred and the diffused dye is fixed. CONSTITUTION:This dye fixing element contains a polymer mordant contg. >=90mol% units represented by the formula and further contains polyvinyl alcohol and gelatin in the same layer. In the formula, each of R1-R4 is H, straight chain or branched alkyl, L is a divalent combining group and (p) is 0 or 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dye fixing element which is an image forming material, and more particularly to a dye fixing element used in an image forming method for forming an image by heat development.

[0002]

2. Description of the Related Art A photographic method using silver halide is superior to other photographic methods such as an electrophotographic method or a diazo photographic method in photographic characteristics such as sensitivity and gradation control. Is used for.

In this photographic method, a light-sensitive element having a silver halide emulsion layer and a dye-fixing element having a dye-fixing layer are laminated, and an alkali processing composition is layered in the laminate. There is a wet processing type color diffusion transfer method in which the laminate is immersed in an alkaline processing liquid.

In recent years, when a photosensitive silver halide and / or an organic silver salt is reduced to silver by heat development, a diffusible dye is produced or released corresponding to or opposite to this reaction, A method of transferring this diffusible dye to a dye fixing element with a mordant has also been developed, for example, US Pat. Nos. 4,463,079 and 4,474,867.
No. 4, ibid. 4,478, 927, ibid. 4, 507, 380
No. 4,500,626, 4,483,914
No. 5, JP-A-58-149046, JP-A-58-14904
No. 7, No. 59-152440, No. 59-154445.
No. 59-165054 and No. 59-180548.
No. 59-168439, No. 59-174832
No. 59-174833, No. 59-174834.
No. 59-174835, No. 62-65038,
No. 61-23245, European Patent Publication 210,660A.
2 and 220,746A2.

While these methods provide excellent color images, they suffer from the poor light fastness of color image dyes, and improvements are desired. In order to solve this problem, a method of using an ultraviolet absorber or an antioxidant together, a method of using a binder or a layer having low oxygen permeability, and the like have been devised. However, even if these methods were used, the light fastness could not be improved significantly. further,
The former has drawbacks such as photo stains, and the latter has disadvantages such as transcription inhibition.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a dye-fixing element which gives a color image excellent in light fastness when the dye is transferred by diffusion and the diffused dye is fixed. is there.

[0007]

These and other objects have been achieved by the dye-fixing elements [1] to [2] shown below. [1] A polymer mordant containing at least 90 mol% of a unit represented by the following general formula (I) on a support, and polyvinyl alcohol and gelatin in the same layer as the polymer mordant. And a dye fixing element.

[0008]

[Chemical 2]

In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or an alkyl group, which may be linear or branched. L represents a divalent linking group. p represents 0 or 1. [2] In claim 1, the polyvinyl alcohol content is 5% to 9% by weight based on the weight of the polymer mordant.
Dye fixing element characterized by being 5%.

The specific constitution of the present invention will be described in detail below. Polyvinyl alcohol (P
As VA), those having a wide range of polymerization degree and saponification degree can be used. An average degree of polymerization of 300 or more is suitable.
The degree of saponification is appropriately 60 mol% or more, and particularly preferably 80 mol or more.

Further, the amount of PVA used together with the polymer mordant is preferably 5% to 200% by weight with respect to the polymer mordant, and particularly 10% to 90%, which has a further effect.

Gelatin used in the present invention is, in addition to lime-processed gelatin, acid-processed gelatin and Britain Society of the Scientific Photography.
Of Japan (Bull Soc Sci Phot Japan) No.16 (p) 30
The enzyme-treated gelatin as described in (1966) may be used, or a gelatin hydrolyzate or enzyme hydrolyzate may be used. Further, a gelatin derivative, a graft polymer of gelatin and another polymer, or a cross-linked product of gelatin and a hardener can be used.

The amount of gelatin used together with the polymer mordant is 20 in weight ratio with respect to the polymer mordant.
It is preferably 0% or less, and particularly preferably 100% or less.

The polymer mordant which can be used in the present invention contains 90 mol% or more of the unit represented by the general formula (I). In the general formula (I), R ₁ , R ₂ , R ₃ , and R
Each of ₄ independently represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-amyl group or an n-hexyl group, and hydrogen An atom, a methyl group or an ethyl group is particularly preferable. L represents a divalent linking group having 1 to about 20 carbon atoms, for example, an alkylene group, a phenylene group, an arylene group and the like. Preferred specific examples of these divalent linking groups are shown below.

[0015]

[Chemical 3]

Preferred specific examples of the monomer unit represented by the general formula (I) of the present invention are shown below. However, it is not limited to these.

[0017]

[Chemical 4]

The polymer mordant which can be used in the present invention may contain a monomer unit other than the general formula (I), and preferable monomer units include, for example, acrylic acid esters (for example, n-butyl acrylate) and methacrylic acid ester. Examples thereof include n-butyl methacrylate, acrylamides such as diacetone acrylamide, methacrylamides such as n-butyl methacrylamide, and styrenes such as styrenesulfinic acid. In addition, JP-A-60-122
No. 940, No. 60-235134, Japanese Patent Application No. 59-16
Comonomers described in JP-A No. 9042, JP-A No. 62-244036, etc. may be contained.

The molecular weight of the polymer mordant which can be used in the present invention is preferably 5 × 10 ³ to 1 × 10 ⁷ . If the molecular weight is too small, the polymer may easily move, and if the molecular weight is too large, coating may be hindered.

Specific examples of the polymer mordant of the present invention are shown below.

[0021]

[Chemical 5]

[0022]

[Chemical 6]

[0023]

[Chemical 7]

[0024]

[Chemical 8]

The method for synthesizing these polymers is described in JP-A-62 / 62.
No. 244043, etc., and can be easily synthesized.

The coating amount of the polymer mordant can be easily determined by those skilled in the art according to the amount of the dye to be mordanted, the kind and composition of the polymer mordant, and the image forming method to be applied. 0.2 to about 15 g / m ² are suitable, preferably used in inter alia 0.5 to 8 g / m ^2.

The present invention can be used in various image-forming materials, but as an example, it will be described in detail below with reference to an example of use in a dye-fixing element of a photothermographic material.

The present invention will be described in detail below. Examples of the water-soluble polymer used in the present invention include synthetic polymers, semi-synthetic polymers and natural polymers. Examples of synthetic polymers include high viscosity grade products such as polyacrylic acid or salts thereof, polyethylene oxide, and polyvinyl alcohol. Examples of the semi-synthetic polymer include high viscosity grade products such as carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose and xanthan gum. Natural polymers include tara gum, guar gum, locust bean gum, and natural polymer polysaccharides.
Examples include high-viscosity grade products such as tamarind gum and sodium alginate. The viscosity of the water-soluble polymer used in the present invention is 30 ° C., 1% aqueous solution viscosity is B type viscometer 6
1000 cp or more and 10000 cp under rpm measurement conditions
It is below, and 1500cp or more and 8000cp or less are especially preferable. If the viscosity is too high, the handleability is poor and it is not preferable in terms of production suitability. The addition amount of the water-soluble polymer of the present invention is 0.0
1 to 1 g / m ² is preferable, and more preferably 0.01 to
It is 0.5 g / m ² . The water-soluble polymer of the present invention may be added to any layer constituting the dye fixing element. A mordant layer is particularly preferred.

The photothermographic material used in the present invention basically has a photosensitive silver halide and a binder on a support and, if necessary, an organometallic oxidant,
A dye-donating compound (which may also serve as a reducing agent as described later) can be contained. These components are often added to the same layer, but if they are in a reactive state, they can be divided and added to separate layers. For example, when a colored dye-donor 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 photothermographic material, but may be supplied from the outside by, for example, a method of diffusing from a dye fixing element described later.

In order to obtain a wide range of colors in 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 a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, a combination of a green-sensitive layer, a red-sensitive layer and an infrared-sensitive layer. Each of the light-sensitive layers can take various arrangement orders known in a conventional type color light-sensitive material. Further, each of these photosensitive layers may be divided into two or more layers if necessary. For the photothermographic material,
Various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer and a back layer can be provided.

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 μm, particularly preferably 0.2 to 1.5 μm. The crystal habit of silver halide grains is cubic, octahedral,
It may be a tetrahedron, a flat plate having a high aspect ratio, or the like. Specifically, US Pat. No. 4,500,626, column 50, U.S. Pat. No. 4,628,021, 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. The known sulfur sensitizing method, reduction sensitizing method, noble metal sensitizing method, selenium sensitizing method and the like can be used alone or in combination for the emulsion for a conventional type light-sensitive material. These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-25315).
No. 9). The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

In the present invention, an organic metal salt may be used as an oxidizing agent together with the photosensitive 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 agents include those described in US Pat.
There are benzotriazoles, fatty acids and other compounds described in Nos. 0,626, columns 52 to 53. In addition, JP-A-60
No. 113235, a silver salt of a carboxylic acid having an alkynyl group such as silver phenylpropiolic acid, and JP-A-6-63.
The acetylene silver described in No. 1-249044 is also useful.
Two or more kinds of organic silver salts may be used in combination. The above organic silver salt may be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per 1 mol of photosensitive silver halide. The total coating amount of the photosensitive silver halide and the organic silver salt is preferably 50 mg to 10 g / m ² in terms of silver.

Various antifoggants or photographic stabilizers can be used in the present invention. Examples thereof include azoles and azaindenes described in RD17643 (1978), pages 24 to 25, JP-A-59-1684.
42-containing nitrogen-containing carboxylic acids and phosphoric acids,
Alternatively, the mercapto compound and its metal salt described in JP-A-59-111636, the acetylene compounds described in JP-A-62-87957, etc. may 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, U.S. Pat. No. 4,617,257 and JP-A-59-180550.
No. 60-140335, RD17029 (197).
8 years) sensitizing dyes described on pages 12 to 13 and the like.
These sensitizing dyes may be used alone or in combination thereof, 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 by itself or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. No. 3). , 615, 641, JP-A-63-23145, etc.). These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after the chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after the nucleation of silver halide grains. Good. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

A hydrophilic binder is preferably used for the binder of the constituent layers of the light-sensitive material and the dye fixing element. As an example thereof, pages (26) to (2) of JP-A No. 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, starch, gum arabic, dextran, natural compounds such as polysaccharides such as 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. Also, the use of superabsorbent polymers in the dye-fixing layer or its protective layer can prevent the dye from retransferring from the dye-fixing element to another after transfer. In the present invention,
The coating amount of the binder is preferably 20 g or less per 1 m ² , particularly 10 g or less, and more preferably 7 g or less.

The constituent layers (including the back layer) of the light-sensitive material or the dye-fixing element are used for the purpose of improving physical properties of the film such as dimensional stabilization, 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 photothermographic 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 itself but exhibits reducing property by the action of a nucleophile or heat during the development process can also be used. Examples of reducing agents used in the present invention include US Pat. No. 4,500,626.
No. 49-50, No. 4,483,914 No. 30
~ Column 31, ibid. 4,330,617, ibid. 4,590,1
52, JP-A-60-140335 (17)-
(18), No. 57-40245, No. 56-1387.
No. 36, No. 59-178458, No. 59-53831.
No. 59-182449 and 59-182450.
Nos. 60-119555, 60-128436 to 60-128439, 60-19854.
No. 0, No. 60-181742, No. 61-259253.
Nos. 62-244044, 62-131253 to 62-131256, European Patent No. 220,
There are reducing agents and reducing agent precursors described on pages 78 to 96 of 746A2. US Pat. No. 3,039,869
Combinations of various reducing agents such as those disclosed in US Pat.

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, electron transfer agent precursors can be used in combination. The electron transfer agent or its precursor can be selected from the above-mentioned reducing agent or its precursor. It is desirable that the electron transfer agent or its precursor has a mobility higher than that of the diffusion resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be one that does not substantially move in the layer of the light-sensitive material among the reducing agents described above, and preferably hydroquinone, Examples thereof include sulfonamide phenols, sulfonamide naphthols, compounds described as electron donors in JP-A No. 53-110827, and dye-donating compounds having diffusion resistance and reducing properties described later. In the present invention, the reducing agent is added in an amount of 0.
The amount is 01 to 20 mol, particularly preferably 0.1 to 10 mol.

In the present invention, silver can be used as the image forming substance. Further, when the silver ion is reduced to silver under a high temperature condition, a compound that generates or releases a mobile dye in response to this reaction or vice versa, that is, a dye-donating compound may be contained. it can. Examples of the dye-donating compound that can be used in the present invention include a compound (coupler) that 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. The diffusion resistant group may form a polymer chain.
Specific examples of color developing agents and couplers can be found in T.W. H. Jam
es "The Theory of the Pho"
"graphical Process" 4th edition 291 ~
Pp. 334 and 354-361, JP-A-58-123
No. 533, No. 58-149046, No. 58-1490.
47, 59-11148, and 59-12439.
9, No. 59-174835, No. 59-231539.
No. 59-231540, No. 60-2950, No. 60-2951, No. 60-14242, No. 60-2.
No. 3474, 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 in an image form. 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 an image latent image. Corresponding to or opposite to the photosensitive silver salt having a difference in the diffusivity of the compound represented by (Dye-Y) n-Z, or releasing Dye and releasing Dye and (Dye- Y) n-Z represents a group having a property of causing a difference in diffusibility, n represents 1 or 2, and when n is 2, two Dy
e-Y may be the same or different. General formula [LI]
Specific examples of the dye-donating compound represented by are the following compounds (1) to (4). In addition, the following ~
Is to form a diffusible dye image (positive dye image) corresponding to the development of silver halide, and is a diffusible dye image (negative dye image) to correspond to the development of silver halide.
Is formed.

US Pat. Nos. 3,134,764, 3,362,819, 3,597,200, 3,544,545 and 3,482,972 are described. , 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 U.S. Pat. No. 4,503,137, 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. An example is U.S. Pat. No. 3,983.
Compounds releasing a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 4,199,
Compounds that release a diffusible dye by the intramolecular rewinding reaction of the isoxazolone ring described in JP-A No. 354 and the like.

US Pat. No. 4,559,290, European Patent 220,746A2, US Pat. No. 4,783,
As described in No. 396, Kokai Giho 6-6199, etc., a non-diffusible compound which releases a diffusible dye by reacting with a reducing agent remaining unoxidized by development can also be used.
Examples thereof include U.S. Pat. Nos. 4,139,389 and 4,139,379, JP-A-59-185333,
Compounds which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction described in US Pat. No. 4,232,107, JP-A-59-84453.
No. 101649, No. 61-88257, RD240
25 (1984), which releases a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 3,008,588A, JP-A-56-
No. 142530, U.S. Pat. Nos. 4,343,893 and 4,619,884, which release a diffusible dye by cleavage of a single bond after reduction, U.S. Pat. Examples thereof include nitro compounds described in U.S. Pat. No. 223, which release a diffusible dye after electron acceptance, compounds described in U.S. Pat. No. 4,609,610, which release a diffusible dye after electron acceptance, and the like.

Further, as more preferable ones, European Patent No. 220,746A2, Open Technical Report 87-6199, US Pat. No. 4,783,396, Japanese Patent Laid-Open No. 63-2016.
No. 53, 63-2016654 and the like, compounds having an N—X bond (X represents oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule, JP-A-1-268.
No. 42, a compound having SO ₂ —X (where X is as defined above) and an electron-withdrawing group in one molecule, JP-A-63-2
No. 71344, a PO-X bond (X
Has the same meaning as above) and a compound having an electron-withdrawing group, C-X 'in one molecule described in JP-A-63-271341.
Examples thereof include a compound having a bond (X ′ is synonymous with X or represents —SO ₂ —) and an electron-withdrawing group. In addition, JP-A-1
Compounds described in JP-A-161237 and JP-A-1-161342, which release a diffusible dye by cleaving a single bond after reduction by a π bond conjugated with an electron-accepting group, can also be used. Among these, a compound having an N—X bond and an electron-withdrawing group in one molecule is particularly preferable. Specific examples thereof are EP 220,746A2 or US Pat. No. 4,783,3.
96-compounds (1)-(3), (7)-
(10), (12), (13), (15), (23)-
(26), (31), (32), (35), (36),
(40), (41), (44), (53) to (59),
(64) and (70), and compounds (11) to (23) described in Kokai Giho 6-6199.

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 oxidant of a reducing agent. Specifically, British Patent No. 1,330,524, Japanese Patent Publication No. 48-39165, and U.S. Patent Nos. 3,443,940 and 4,474,867.
No. 4,483,914 and the like. Reducible to silver halide or organic silver salt,
A compound that releases a diffusible dye when the other party is reduced (DR
R compound). Since this compound does not need to use another reducing agent, it is preferable because there is no problem of image contamination due to oxidative decomposition products of the reducing agent. A typical example thereof is US Pat. No. 3,92.
8,312, 4,053,312, 4,05
5,428, 4,336,322, JP-A-59-
No. 65839, No. 59-69839, No. 53-381.
9, 51-104343, RD17465, U.S. Pat. Nos. 3,725,062 and 3,728,113.
No. 3,443,939, JP-A-58-11653.
7, 57-179840, U.S. Pat. No. 4,50.
0,626 and the like. Specific examples of the DRR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626 in columns 22 to 44. Among them, the compounds (1) to
(3), (10) to (13), (16) to (19),
(28)-(30), (33)-(35), (38)-
(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 coupler and the general formula [LI] described above, a dye silver compound in which an organic silver salt and a dye are bound (Research Disclosure May 1978 issue, pages 54 to 58, etc.), Azo dyes used in the heat developable silver dye bleaching method (US Pat.
35,957, Research Disclosure, 1
(April 976, pages 30-32, etc.), leuco dyes (US Pat. Nos. 3,985,565, 4,022,617, etc.) can also be used.

Hydrophobic additives such as dye-donor compounds and antidiffusive reducing agents can be incorporated into the layer of the photographic material by known methods such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-83154
No. 59-178451 and No. 59-178452.
No. 59-178453, No. 59-178454.
No. 59-178455, No. 59-178457 and the like, a high-boiling point organic solvent can be used in combination with a low-boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C., if necessary. The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g per 1 g of the dye-donor compound used.
It is the following. Also, 1 cc or less, more preferably 0.5 cc or less, and especially 0.3 cc or less is suitable for 1 g of the binder. JP-B-51-39853, JP-A-51-59
A dispersion method using a polymer described in No. 943 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 hydrophilic colloid, various surfactants can be used. For example, the surfactants listed on pages (37) to (38) of JP-A-59-157636 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 material. Specific compounds preferably used are described in US Pat. No. 4,50.
0,626, columns 51-52.

In a system for forming an image by diffusion transfer of a dye, a dye fixing element is used together with a light-sensitive material. The dye fixing element may be applied separately on a support different from the light-sensitive material, or may be applied on the same support as the light-sensitive material. Regarding the relationship between the light-sensitive material and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer, the relationship described in column 57 of US Pat. No. 4,500,626 can be applied to the present application. If necessary, the dye fixing element can be provided with auxiliary layers such as a protective layer, a peeling layer and an anti-curl layer. In particular, it is useful to provide a protective layer.

In the constituent layers of the light-sensitive material and the dye-fixing element, a plasticizer, a slipping agent, or a high boiling point organic solvent can be used as an agent for improving the releasability between the light-sensitive material and the dye-fixing element. A specific example is (2) in JP-A-62-253159.
5), No. 62-245253 and the like. Further, various silicone oils (all silicone oils from dimethyl silicone oils to modified silicone oils obtained by introducing various organic groups into dimethyl siloxane) can be used for the above purpose. Examples thereof include various modified silicone oils described in "Modified Silicone Oil" technical material P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X
-22-3710) is effective. In addition, JP-A-62
Silicone oils described in JP-A-215953 and JP-A-63-46449 are also effective.

An anti-fading agent may be used in the light-sensitive material and the dye fixing element. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a kind of metal complex.
Examples of the antioxidant include chroman compounds, coumarane compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective. Examples of ultraviolet absorbers include benzotriazole compounds (US Pat. No. 3,533,794), 4-thiazolidone compounds (US Pat. No. 3,352,681),
Benzophenone compounds (JP-A-46-2784 and the like), JP-A-54-48535 and JP-A-62-13
There are compounds described in Nos. 6641 and 61-88256. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective. Examples of the metal complex include U.S. Pat. Nos. 4,241,155, 4,245,018, columns 3 to 36, and 4,254,195, columns 3 to 8,
There are compounds described in JP-A-62-174741, JP-A-61-88256, pages (27) to (29), JP-A-63-199248, JP-A-1-75568 and JP-A-1-74272.

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 material. . 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 material and the dye fixing element. In particular, whether to incorporate a fluorescent whitening agent in the dye fixing element,
It is preferably supplied from the outside such as a photosensitive material. As an example, K. Venkataraman edition “Th
e Chemistry of Synthetic
Dyes ", Vol. V, Chapter 8, compounds described in JP-A-61-143752 and the like 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.

As the hardener used in the constituent layers of the light-sensitive material and the dye fixing element, US Pat. No. 4,678,739, No. 4 can be used.
Column 1, JP-A-59-116655 and JP-A-64-2452.
No. 61, No. 61-18942, etc. are mentioned. More specifically, aldehyde type hardeners (formaldehyde etc.), aziridine type hardeners, epoxy type hardeners, vinyl sulfone type hardeners (N, N'-ethylene-
Bis (vinylsulfonylacetamide) ethane etc.), N
-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 material and the dye-fixing element, various surfactants can be used for the purpose of coating aid, improvement of peeling property, improvement of sliding property, prevention of electrostatic charge, 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 material and the dye-fixing element may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, improving peelability and the like. As typical examples of organic fluoro compounds, JP-B-57-9053, columns 8 to 17, JP-A-61-20
No. 944, No. 62-135826, or the like, or a fluorochemical surfactant such as a fluorochemical compound such as a fluorocarbon oil or a solid fluorochemical resin such as a tetrafluoroethylene resin. Can be mentioned.

A matting agent can be used in the light-sensitive material and the dye fixing element. Matting agents such as silicon dioxide, polyolefins, polymethacrylates, etc.
In addition to the compounds described on page 1-88256 (29), benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like are disclosed in JP-A-63-274944.
No. 63-274952. In addition, the constituent layers of the light-sensitive material 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 disclosed in JP-A-61-8.
No. 8256, pages (26) to (32).

In the present invention, an image formation accelerator can be used in the light-sensitive material and / or the dye fixing element. The image formation accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a light-sensitive material layer. Has a function of accelerating the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, a base or a base precursor, a nucleophilic compound, a high boiling organic solvent (oil), a thermal solvent, a surfactant, silver Alternatively, they are classified into compounds that interact with silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. Details thereof are described in US Pat. No. 4,678,739, columns 38 to 40. Examples of the base precursor include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. A specific example is U.S. Pat. No. 4,511,493.
And JP-A-62-65038.

In a system in which heat development and transfer of a dye are carried out simultaneously in the presence of a small amount of water, it is preferable to add a base and / or a base precursor to the dye fixing element in order to improve the storability of the light-sensitive material. In addition to the above, European Patent Publication 210,660 and US Pat. No. 4,740,445.
Combination of a sparingly soluble metal compound and a compound capable of complex-forming reaction with a metal ion constituting the sparingly soluble metal compound (referred to as a complex-forming compound) described in JP-A-61-
Compounds that generate a base by electrolysis as described in No. 232451 can also be used as the base precursor.
The former method is particularly effective. The sparingly soluble metal compound and the complex-forming compound are advantageously added separately to the light-sensitive material and the dye fixing element.

In the present invention, various development stoppers can be used in the light-sensitive material and / or the dye-fixing element for the purpose of always obtaining a constant image with respect to variations in processing temperature and processing time during development. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or to inhibit development by interacting with silver and a silver salt. Compound. Specific 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. For more details, see JP-A-62-25
No. 3159, pages (31) to (32).

In the present invention, the support for the light-sensitive material and the dye-fixing element is one that can withstand the processing temperature. Generally, paper, synthetic polymer (film)
Is mentioned. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing pigments such as titanium oxide are further prepared from polypropylene. The film method synthetic paper, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly cast coated paper), metal, cloth, glass and the like are used. These can be used alone,
It can also be used as a support having one or both sides laminated with a synthetic polymer such as polyethylene. In addition to these, the supports described in JP-A-62-253159, pages (29) to (31) can be used. A hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black and other antistatic agents may be coated on the surface of these supports.

As a method for exposing and recording an image on a light-sensitive material, for example, a method of directly photographing a landscape or a person using a camera, a method of exposing through a reversal film or a negative film 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 of image information, 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 material,
As described above, the light sources described in US Pat. No. 4,500,626, column 56, such as natural light, tungsten lamps, light emitting diodes, laser light sources, and CRT light sources can be used. Image exposure can also be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the nonlinear optical material is
It is a material that can develop the nonlinearity between the electric field and the polarization that appears when a strong optical electric field such as laser light is applied.
Lithium niobate, potassium dihydrogen phosphate (KDP),
Inorganic compounds represented by lithium iodate, BaB ₂ O _4, etc., urea derivatives, nitroaniline derivatives such as 3
-Methyl-4-nitropyridine-N-oxide (PO
Nitropyridine-N-oxide derivatives such as M) and the compounds described in JP-A Nos. 61-53462 and 62-210432 are preferably used. As the 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. The above-mentioned image information is an image signal obtained from a video camera, an electronic still camera or the like, a television signal represented by Nippon Television Signal Standard (NTSC), an image obtained by dividing an original image into many pixels such as a scanner. An image signal created by using a computer represented by Signal, CG and CAD can be used.

The light-sensitive material and / or the dye fixing element may have a form having a conductive heating element layer as a heating means for heat development or diffusion transfer of dye. The transparent or opaque heating element in this case is disclosed in JP-A-61-1.
Those described in No. 45544 and the like 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 about 80 ° C. to about 180 ° C. is particularly 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 it is more preferably 50 ° C. or higher and about 10 ° C. lower 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 (for these bases, an image). The one described in the section of the formation accelerator is used)
Can be mentioned. 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 may be contained in the solvent.

These solvents can be used by a method of applying them to the dye fixing element, the light-sensitive material 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). Examples of the method for applying a solvent to the photosensitive layer or the dye fixing layer include, for example, JP-A-61-147244 (2).
6) There is a method described on page. Alternatively, the solvent may be contained in a microcapsule, and may be incorporated in the light-sensitive material or the dye-fixing element or both in advance.

In order to promote dye transfer, a method in which a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperature is incorporated in the light-sensitive material or the dye fixing element can also be used. The hydrophilic thermal solvent may be incorporated in either the light-sensitive material 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 organic solvent may be contained in the light-sensitive material 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 contacted, or a hot plate, a hot presser, a heat roller, a halogen lamp heater, an infrared or far infrared lamp heater, etc. is contacted. And passing through a high temperature atmosphere. JP-A-61-1 is a method for applying a pressure condition or pressure when the light-sensitive element and the dye fixing element are superposed and closely contacted with each other.
The method described on page 27 of No. 47244 can be applied.

Any of a variety of thermal development 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.

[0067]

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

Example 1 A photosensitive element having the constitution shown in Table-A was prepared and designated as photosensitive element 101.

[0069]

[Table 1]

[0070]

[Table 2]

[0071]

[Chemical 9]

[0072]

[Chemical 10]

[0073]

[Chemical 11]

[0074]

[Chemical 12]

[0075]

[Chemical 13]

[0076]

[Chemical 14]

A dye fixing element having the constitution shown in Table B was prepared and designated as dye fixing element (1).

[0078]

[Table 3]

Water-soluble polymer (1) Sumika gel L5
-H (Sumitomo Chemical Co., Ltd.) Water-soluble polymer (2) Copper-Carrageenan (Taito Co., Ltd.) PVA (1) PVA-110 (Kuraray Co., Ltd.)

[0080]

[Chemical 15]

[0081]

[Chemical 16]

In addition, except that PVA (1) and its addition amount, mordant (1) and its addition amount and gelatin addition amount in the second layer of Table B were changed as shown in Table C, the dye fixing element ( Dye fixing elements (2) to (9) were prepared in the same manner as in 1).

[0083]

[Table 4]

PVA (2) PVA-105
(Kuraray Co., Ltd.) PVA (3) PVA-117 (Kuraray Co., Ltd.) PVA (4) PVA-203 (Kuraray Co., Ltd.) PVA (5) PVA-217 (Kuraray Co., Ltd.)

[0085]

[Chemical 17]

The above light-sensitive element and dye-fixing element were processed using the image recording apparatus described in JP-A-2-84634. That is, using a tungsten light bulb as the photosensitive element,
It was exposed for 1/10 seconds at 5000 lux through B, G, and R three-color separation filters with continuously changing densities. This photosensitive element was dipped in water kept at 40 ° C. for about 5 seconds, then squeezed with a roller, and then immediately superposed so that the dye-fixing element and the film surface were in contact with each other, and the water-absorbed film surface was adjusted to 80 ° C. 15 using a heat roller
Heated for seconds. Then, the light-sensitive element and the dye-fixing element were peeled off, and yellow, magenta, and cyan color images were obtained on the dye-fixing element corresponding to the B, G, and R three-color separation filters, respectively.

Next, the dye fixing elements having these color images were irradiated with xenon light (100,000 lux) for 1 week on the color images by using an Atlas C.I.65 weather meter. Reflection densitometer (X-Rit
e 310 TR), and the fastness of the color image to light was evaluated based on the residual dye ratio.

The dye residual rate was determined according to the following formula.

[0089]

[Equation 1]

The results are shown in Table D.

[0091]

[Table 5]

[0092]

[Table 6]

Comparative Example 1 Mordant (1) in the second layer of Table B and its addition amount, PVA
Dye-fixing elements (10) to (18) were prepared in the same manner as dye-fixing element (1) except that the addition amount of (1), its addition amount, and the addition amount of gelatin were changed as shown in Table E.

[0094]

[Table 7]

[0095]

[Chemical 18]

The above dye-fixing element was evaluated by obtaining the dye residual ratio in the same manner as in Example 1, and the results are shown in Table E. As can be seen from Table E, the dye fixing elements of the invention are
It can be seen that the dye residual rate is high.

[0097]

According to the present invention, polyvinyl alcohol,
A dye fixing element having gelatin and a polymer mordant containing 90 mol% or more of the unit represented by the above general formula has an effect that a color image excellent in light fastness can be provided. Furthermore, if the content of polyvinyl alcohol is 5% to 95% by weight with respect to the polymer mordant,
Further, it has an effect of improving light fastness.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] November 13, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0078

[Correction method] Change

[Correction content]

[0078]

[Table 3]

Claims (2)

[Claims] 1. A polymer mordant containing at least 90 mol% of a unit represented by the following general formula (I) on a support, and polyvinyl alcohol and gelatin in the same layer as the polymer mordant. A dye fixing element characterized by. [Chemical 1] In the formula, R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom or an alkyl group, and may be linear or branched. L represents a divalent linking group. p represents 0 or 1. 2. The dye fixing element according to claim 1, wherein the content of polyvinyl alcohol is 5% to 95% by weight based on the weight of the polymer mordant.