JPH0827527B2 - Color diffusion transfer photographic element - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a color diffusion transfer photographic material, and more particularly to a novel photographic material having improved raw storability and white background.

(Prior Art) A method in which a silver halide emulsion and a dye-releasing compound are combined in a color diffusion transfer method to release a diffusible dye according to silver development, and the dye is mordanted and fixed on an image-receiving layer containing a mordant. Is well known. Among these, in the case where the image receiving layer and the silver halide emulsion layer are present on the same support (for example, monosheet type color diffusion transfer method), the photographic characteristics are not changed during the storage period from photographing to processing after coating production. Many of them had a strong tendency to change and had poor so-called raw preservation properties.

(Problems to be solved by the invention) When the image receiving layer and the silver halide emulsion layer are present on the same support, the most important change in photographic characteristics during raw storage is the maximum density. The decrease in (Dmax) and the increase in minimum density (Dmin) both deteriorate image quality. This change is dependent on temperature and humidity, usually high temperature and / or
Or it will be accelerated when stored in high humidity. It has been strongly desired to develop a method for solving such a problem and maintaining the same high quality photographic characteristics as in manufacturing.

(Object of the Invention) A first object of the present invention is to develop a technology for reducing a decrease in Dmax during raw storage, and a second object is to develop a technology for suppressing an increase in Dmin during raw storage. The third is to provide a color diffusion transfer photographic element that solves these problems.

(Means for Solving the Problems) As a result of intensive studies, the present inventors have found that the following objects can be achieved by the following photographic elements. That is, a quaternary ammonium salt moiety represented by the general formula (M) is repeated in a color diffusion transfer photographic element having a silver halide emulsion layer combined with a dye-donor compound and a dye image-receiving layer containing a mordant on the same support. Contains a polymer contained in the unit as a mordant, and A color diffusion transfer process photographic element characterized by containing bromide ions corresponding to 0.2 to 10% of the total number of sites.

 X Is an anion that forms a salt with a quaternary ammonium ion
Represents the

Bromine ion is a mordant polymer Amount equivalent to 0.2-10% of the total number of sites is preferable 0.3-8
% Is particularly preferred.

In the present invention, The total number of sites is 1 × 10 ^{−4 to} 5 × 10 ⁻² eq / m ² (equivalent / m ² ), preferably 3 × 10 ^{−3 to} 1.2 × 10 ⁻² eq / m ² . Therefore, the bromine ion is Since it is 0.2 to 10% of the number of sites, it is 2 × 10 ^{-7 to} 5 × 10 ^-3 eq /
m ² , preferably 6 × 10 ^{−6 to} 1.2 × 10 ⁻³ eq / m ² .

As a method for incorporating bromide ions, a method of adding bromide or bromide salt is generally used. For example KB
A typical method is to add r, NaBr, LiBr or the like.

The layer to which bromine ions are added may be any layer in the above photographic elements, and may be a mordant layer, a pigment layer containing titanium dioxide or carbon black, a silver halide emulsion layer, a coloring material layer containing a dye-donating compound, and hydroquinones. It can be added to various layers such as a layer containing, and a protective layer.

The bromine ion (concentration) referred to in the present invention represents the free bromine ion concentration excluding the bromine ion in the silver halide crystal, and can be measured as the so-called film pAg (or silver potential) from the film surface of the coating material. It is a thing. For this, a surface silver electrode was used to obtain the relationship between the silver potential / bromine ion concentration for a sample with a known bromine ion concentration in the calibration curve, and then the surface silver potential of the unknown sample was measured to determine the bromine ion concentration. (Or content) can be calculated.

The mordant containing a repeating unit represented by the general formula (M) is a cationic polymer well known in the art, but in the present invention, the total number of carbon atoms of R ² , R ³ and R ⁴ is 6 or more. preferable.

The mordant containing the general formula (M) has the general formula (Ia) as described below.
Preferred are represented as (Iaa) (Iab) (Ib) (IIa), (IIaa), (IIab) and (IIb).

Examples of the alkyl group for R ¹² , R ¹³ and R ¹⁴ include methyl group, ethyl group, n-propyl group, isopropyl group, n-
Butyl group, isobutyl group, n-amyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group or n-decyl group, etc.
20; substituted alkyl groups include, for example, alkoxyalkyl groups (eg, methoxymethyl group, methoxyethyl group, methoxybutyl group, ethoxyethyl group, ethoxypropyl group, ethoxybutyl group, butoxyethyl group, butoxypropyl group, butoxybutyl group). Group, vinyloxyethyl group), cyanoalkyl group (for example, 2-cyanoethyl group,
3-cyanopropyl group, 4-cyanobutyl group), halogenated alkyl group (for example, 2-fluoroethyl group, 2-chloroethyl group, 3-fluoropropyl group), alkoxycarbonylalkyl group (for example, ethoxycarbonylmethyl group), alkenyl or Alkynyl-substituted alkyl groups (eg, allyl group, 2-butenyl group, propargyl group) and the like.

As the aralkyl group, an unsubstituted aralkyl group, for example, a benzyl group, a phenethyl group, a diphenylmethyl group, a naphthylmethyl group and the like; a substituted aralkyl group, for example, an alkylaralkyl group (for example, 4-methylbenzyl group, 2,5-dimethylbenzyl group, 4- (isopropylbenzyl group),
Alkoxyaralkyl group (eg 4-methoxybenzyl group, 4-ethoxybenzyl group, 4- (4-methoxyphenyl) benzyl group), cyanoaralkyl group (eg 4-
Cyanobenzyl group), 4- (4-cyanophenyl) benzyl group), perfluoroalkoxyaralkyl group (eg 4-pentafluoropropoxybenzyl group, 4-undecafluorohexyloxybenzyl group), halogenated aralkyl group (eg 4 There are -chlorobenzyl group, 4-bromobenzyl group, 3-chlorobenzyl group, 4- (4-chlorophenyl) benzyl group, 4- (4-bromophenyl) benzyl group and the like.

L preferably represents a divalent group having 1 to about 12 carbon atoms, among which (Wherein l is 1 or 2) is preferably a divalent group,
From the point of alkali resistance Is more preferable. Especially from the viewpoint of emulsion polymerization and mordability Is preferred.

In the above formula, R ¹⁵ is an alkylene group (eg methylene, ethylene, trimethylene, tetramethylene, etc.);
Arylene group, aralkylene group (for example, (Wherein R ¹⁷ is alkylene having 0 to about 6 prime numbers), and R ¹⁶ is a hydrogen atom or a group as described for R ¹² .

The quaternary ammonium ion of the saturated cyclic amine formed by Z is preferably a quaternary ammonium ion of a 5- to 8-membered (especially 5 to 6-membered) nitrogen-containing heterocycle, and as the heteroatom, in addition to the nitrogen atom, an oxygen atom or sulfur. It may contain atoms. Specific examples thereof include quaternary ammonium ions of piperidine, pyrrolidine and morpholine.

 X₁ Specific examples of the acid group represented by
On (eg chlorine ion), alkyl sulfate ion, al
Kill or aryl sulfonate ion, acetate ion, sulfuric acid
Ions and the like, and chlorine ions are particularly preferable.

Specific examples of the copolymer having a repeating unit represented by the general formula (Ia) include, for example, the following general formulas (Iaa) and (Ia).
The items represented by b) can be mentioned.

The cross-linking monomer residue represented by A in the general formulas (Iaa) and (Iab) has the following general formula It is a monomer unit derived from a monomer having a structure represented by: However, m ² is an integer greater than 1, preferably 2 to 3, R ¹⁹ is a hydrogen atom or a methyl group, Q is a linking group [eg amide group (eg sulfonamide), ester group (eg sulfonate ester), An alkylene group (eg, methylene, ethylene, trimethylene), an arylene group (eg, phenylene, phenyleneoxycarbonyl), etc., or one or more combinations thereof].

Examples of the above copolymerizable monomers are trivinylcyclohexane, divinylbenzene, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, neopentyl glycol dimethacrylate, tetramethylene glycol diacrylate, tetramethylene glycol dimethacrylate, etc., Of these, trivinylcyclohexane and divinylbenzene are particularly preferable.

The copolymerizable unsaturated monomer residue represented by B is
A group derived from an ethylenically unsaturated monomer, and examples of the ethylenically unsaturated monomer include, for example, olefins (for example, ethylene, propylene, 1-butene, vinyl chloride, vinylidene chloride, isobutene, vinyl bromide, etc.). ), Dienes (eg butadiene, isoprene, chloroprene etc.), ethylenically unsaturated esters of fatty acids or aromatic carboxylic acids (eg vinyl acetate,
Allyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc.), esters of ethylenically unsaturated acids (for example, methyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate,
Benzyl methacrylate, phenyl methacrylate, octyl methacrylate, ethyl acrylate, n-butyl acrylate, n-octyl acrylate, amyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, maleic acid dibutyl ester, fumaric acid diethyl ester, crotonic acid ethyl, methylene malonic acid Dibutyl ester, etc., styrenic acid (eg,
Styrene, α-methylstyrene, vinyltoluene, chloromethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, etc.). Among these, styrenes and methacrylic acid esters are particularly preferable from the viewpoint of emulsion polymerizability and hydrophobicity. B may include two or more of the above monomers.

Next, referring to the component D, in the formula, R ¹⁸ is preferably a hydrogen atom or a carbon atom, preferably a lower alkyl group having 1 to about 6 (for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group or an n-butyl group). (Amyl group, n-hexyl group), of which a hydrogen atom and a methyl group are particularly preferred. L ₁ represents an alkylene group having preferably 1 to about 6 carbon atoms (eg methylene, ethylene, isopropylene, hexylene) or an arylene group having preferably 6 to about 10 carbon atoms (eg phenylene).

Specific examples of acrylonitrile and its derivatives include:
Examples thereof include acrylonitrile, methacrylonitrile, acryl cyanide, and crotonnitrile. Two or more kinds of the component D may be contained.

X, which is the ratio of the monomer components in the general formula (Iaa),
The preferable values of y and z are 1.0 to 10 mol% of x, and y
Is 20 to 60 mol%, z is 20 to 80 mol%, particularly preferably 30.
~ 70 mol%.

Specific examples of the polymer mordants represented by the general formulas (Iaa) and (Iab) are listed below.

For details of the method of synthesizing the polymer mordants represented by the general formulas (Iaa) and (Iab), see JP-A-57-202539 and 59-59.
219745 and 59-232340.

Next, a homopolymer or a copolymer having a repeating unit represented by the general formula (Ib) will be described.

Specific examples of the above mordants are listed below.

A polymer mordant having a repeating unit represented by formula (Ib) is described in JP-A-59-131931.

Other specific examples of the cyclic quaternary ammonium mordant that can be used in the present invention include, for example, U.S. Pat.
No. 452,878, No. 42,424,272, West German patent application publication (OLS)
The compounds described in 3,109,931A1 can be mentioned.

The mordant used in the present invention has the following general formula (IIa)
It also includes a homopolymer or a copolymer having a repeating unit represented by or (IIb).

Specific examples of the copolymer having a repeating unit represented by the general formula (IIa) include those represented by the following general formulas (IIaa) and (IIab).

The symbols in the formulas have the same meanings as in formulas (Iaa) and (IIa).

The symbols in the formulas have the same meanings as in formulas (Iab) and (IIa).

Specific examples of the polymer mordants represented by the general formulas (IIaa) and (IIab) are listed below.

Next, a homopolymer or a copolymer having a repeating unit represented by the general formula (IIb) will be described.

Specific examples of the above mordants are listed below.

Details of the method for synthesizing the mordants represented by the general formula (IIaa) and the general formula (IIab) are described in JP-A-57-202539 and 59-219745, and the general formula (IIa) The polymer mordant having a repeating unit represented by the formula (1) is described in JP-A-59-131931.

Other specific examples of the mordant [II] that can be used in the present invention include, for example, JP-A-60-23851, JP-A-60-23852, and JP-A-60-2.
8650, U.S. Patents 4,288,511, 4,340,522, 4,32
2,489, 4,463,080, 4,424,272, 4,424,326
The compounds described in Japanese Patent Application Publication No. 2,075,034A, West German Patent Application Publication (OLS) 3,109,931A1 and the like can be further mentioned.

The silver halide emulsion used in the present invention is a hydrophilic colloidal dispersion of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide or a mixture thereof. The composition is selected according to the purpose of use of the light-sensitive material and the processing conditions, but the iodide content is 10 mole% or less and the chloride content is 30 mole%.
% Or less of silver bromide, silver iodobromide or silver chloroiodobromide is particularly preferable.

In the present invention, either a negative emulsion forming a surface latent image or a direct reversal emulsion can be used. The latter emulsion includes an internal latent image type emulsion and a direct reversal type emulsion which has been fogged in advance.

Internal latent image type silver halide emulsions can be advantageously used in the present invention. Examples of emulsions of this type are described in U.S. Pat.
No. 0, 3,206,313, 3,447,927, 3,761,276,
And conversion type emulsions, core / shell type emulsions, emulsions incorporating different metals, and the like described in JP-A-3,935,014.

As a nucleating agent for this type of emulsion, U.S. Pat.
And hydrazines described in Nos. 2,563,785; 3,22
Hydrazides and hydrazones described in 7,552; British Patent 1,283,835, Japanese Patent Publication No. 49-38164, US Patent 3,73
Quaternary salt compounds described in 4,738, 3,719,494 and 3,615,615; sensitizing dyes having a nucleating substituent in a dye molecule described in U.S. Pat. No. 3,718,470; U.S. Pat. The acylhydrazinophenyl thiourea compounds described in 4,030,925 and 4,031,127 are typical ones.

The silver halide emulsion used in the present invention can have a color sensitivity broadened by a spectral sensitizing dye, if desired.
As the spectral sensitizing dye, a cyanine dye, a merocyanine dye or the like can be appropriately used.

The dye-donor compound is preferably a dye-releasing redox compound, and among the dye-releasing redox compounds,
The compounds described in the following documents can be mentioned as compounds in which the compound that has been oxidized undergoes alkali hydrolysis to release the dye.

U.S. Patents 4,053,312, 4,055,428 and 4,076,529
No. 4,152,153, 4,135,929, JP-A-53-149328
No. 51, No. 51-34343, No. 53-46730, No. 54-130122, No.
53-3819, 56-12642, 56-16130, 56-16131
Among these, those which emit a yellow dye: US Pat. No. 4,013,633, JP-A-53-149328, 51-114
930, 56-71072, Research Disclosure 17630 ('78), 16475 ('7)
7) etc. that release magenta dye: US Pat. Nos. 3,954,476, 3,931,144, and 3,932,308
No. 53, JP-A-53-23628, JP-A-52-106727, JP-A-54-65034
Issue 54-161332, Issue 55-4028, Issue 55-36804, Issue 56
-73057, 56-71060, 55-134850, West German patent application (OLS) 2,847,371, etc. that release cyan dyes: U.S. Patents 3,942,987, 3,929,760, 4,013,635
No. 51-109928, No. 53-149328, No. 52-8827
No. 53-143323, No. 53-47823, No. 56-71061, etc.Also, as a redox compound that releases a dye by ring closure of a compound that has not been oxidized, the following documents are available. The ones mentioned can be mentioned.

US Pat. Nos. 4,139,379 and 3,980,479, West German patent application (OLS) 2,402,900, and 2,448,811.

In the practice of the present invention, dye-releasing redox compounds represented by the following general formula are preferred.

Y-X in the above formula, Y represents a redox mother nucleus (carrier), and X is a dye residue or a dye precursor residue directly bonded to Y or bonded through an intervening group L. Represents

L represents an intervening group such as an alkylene group (or alkylidene group) having 1 to 6 carbon atoms, an arylene group or a heterocyclic group, and the intervening group L is directly bonded to X or -O- _{, -S -, - SO 2 -} , - NR 0 - (R 0
Is a hydrogen atom or an alkyl group), —CO—, —CO—NH— or —SO ₂ —NH—.

The dye residue can in principle be the residue of any type of dye. However, the dye residue must be sufficiently diffusible to pass through the photographic layer in the light-sensitive material and reach the image-receiving layer. To this end, one or more water-solubilizing groups can optionally be attached to the dye residue. Examples of suitable water-solubilizing groups include: carboxyl groups, sulfo groups, sulfonamide groups, sulfamoyl groups, aliphatic or aromatic hydroxyl groups.

Examples of dyes particularly suitable for the present invention include: azo dyes, azomethine dyes, anthraquinone dyes,
Phthalocyanine dyes, indigoid dyes, triphenylmethane dyes, metal complex dyes, colored metal complexes.

The dye precursor (precursor) residue is an auxiliary color group (auxiliary group) in a color development system by oxidation in a conventional processing step in a photographic processing step or in an additional processing step.
Is the residue of a compound that can be converted into a dye by the liberation of (i.e., the auxiliary chromophore is released and this joins the chromophore). The dye precursor in this case may be a leuco dye or it may be a dye that is converted to another dye during photographic processing.

An example of Y useful for this redox compound is an N-substituted sulfamoyl group. For example, Y can be a group represented by the following formula (A).

In the formula, β represents a non-metal atom group necessary for forming a benzene ring, and a carbon ring or a hetero ring is condensed with the benzene ring to form, for example, a naphthalene ring, a quinoline ring, 5,6,7,8-
It may form a tetrahydronaphthalene ring, a chroman ring or the like. Further, the benzene ring or a ring formed by condensing a carbon ring or a hetero ring on the benzene ring has a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a nitro group, an amino group, an alkylamino group. ,
An arylamino group, an amide group, a cyano group, an alkylmercapto group, a keto group, a carboalkoxy group, a heterocyclic group and the like may be substituted.

α represents a group represented by —OG ¹ or —NHG ² . G here
¹ represents a hydrogen atom or a group which is hydrolyzed to form a hydroxyl group, preferably a hydrogen atom, Is a group represented by. Here, G ³ is an alkyl group, particularly a methyl group, an ethyl group, an alkyl group having 1 to 18 carbon atoms such as a propyl group, a chloromethyl group, a halogen-substituted alkyl group having 1 to 18 carbon atoms such as a trifluoromethyl group, Represents a phenyl group and a substituted phenyl group. G ² represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or a hydrolyzable group. Here, the preferable one as the hydrolyzable group of G ² is A group represented by -SO ₂ G ⁵ or -SOG ^5. Where G ⁴ is
An alkyl group having 1 to 4 carbon atoms such as a methyl group; mono,
Halogen-substituted alkyl groups such as di- or trichloromethyl groups and trifluoromethyl groups; Alkylcarbonyl groups such as acetyl groups; Alkyloxy groups; Substituted phenyl groups such as nitrophenyl groups and cyanophenyl groups; Substituted with lower alkyl groups or halogen atoms A substituted or unsubstituted phenyloxy group; a carboxyl group; an alkyloxycarbonyl group; an aryloxycarbonyl group; an alkylsulfonylethoxy group or an arylsulfonylethoxy group. G ⁵ represents a substituted or unsubstituted alkyl group or aryl group.

Further, b is an integer of 0, 1 or 2. However, although there is a case where a compound corresponding to an alkyl group which renders the compound represented by the general formula (A) immobile and non-diffusible as G ₂ of -NHG ₂ as described above is introduced. , Except that, when α is a group represented by -OG ¹ , and α
Is represented by -NHG ₂ and G ₂ is a hydrogen atom or a carbon atom number of 1 to 8.
When it is an alkyl group of, or a hydrolyzable group, b
Is 1 or 2, preferably 1. Ball represents a group that renders the compound diffusion resistant. A specific example of this type of Y is disclosed in
48-33826, 53-50736, 54-54021 and 54-143
No. 230 is mentioned. Another example of Y suitable for this type of compound is a group represented by the following formula (B).

In the formula, Ball, a, and b have the same meanings as in formula (A),
β'represents an atomic group necessary for forming a carbon ring, for example, a benzene ring, and the benzene ring is further condensed with a carbon ring or a heterocyclic ring to form a naphthalene ring, a quinoline ring, 5,6,7,8
A tetrahydronaphthalene ring, a chroman ring or the like may be formed; Further, in the above various rings, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a nitro group, an amino group, an alkylamino group, an arylamino group, an amide group, a cyano group, an alkylmercapto group, a keto group, a carbo group, It may be substituted with an alkoxy group or a heterocyclic group. Specific examples of this type of Y are disclosed in JP-A-51-113624,
53-149328, 54-65034, 54-111344, 54-9
1187, U.S. Pat. No. 4,053,312 and the like.

In the present invention, European patent 220746 (Japanese Patent Application No. 60-244873)
The dye-releasing redox compounds described in, for example, Japanese Patent Application No. 61-88625 can also be used.

The coating amount of the dye releasing redox compound is 1 × 10 ⁻⁴ to 1
× 10 ^-2 mole / m ² , preferably 2 × 10 ^-4 to 2 × 10 ^-3 mole /
m ² .

The dye-releasing redox compound used in the present invention has a hydrophilic colloid as a carrier, depending on the type of the compound.
It can be dispersed in various ways. For example, a compound having a dissociative group such as a sulfo group or a carboxy group can be dissolved in water or an alkaline aqueous solution and then added to a hydrophilic colloid solution for dispersion. On the other hand, a compound which is hardly soluble in an aqueous medium and easily soluble in an organic solvent can be dispersed by a method known in the art.

Any color diffusion transfer photographic element of the present invention can be used as long as it is a film unit in which a light-sensitive silver halide photographic emulsion, a dye-releasing redox compound, and a dye image-receiving layer are carried on the same support. To be

A typical form of the film unit is one transparent support in which the above-mentioned dye image-receiving layer and a silver halide photographic emulsion layer combined with a dye-releasing redox compound are laminated, and after completion of a transfer image, In this mode, it is not necessary to peel off the image receiving layer and the like. More specifically, it comprises at least one dye image-receiving layer, and in a preferred embodiment of the silver halide emulsion layer, 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,
A yellow dye-donor substance, a magenta dye-donor substance and a cyan dye-donor substance are combined in each of the above emulsion layers. (Here, "the infrared light-sensitive emulsion layer means an emulsion layer having sensitivity to light having a wavelength of 700 nm or more, particularly 740 nm or more). And the image-receiving layer and the silver halide layer or the dye-releasing redox compound-containing A white reflective layer containing a solid pigment such as titanium oxide is provided between the layers so that the transferred image can be viewed through the transparent support. A light-shielding layer may be provided between the silver halide layers.
If desired, a release layer may be provided at an appropriate position so that all or part of the light-sensitive element can be peeled off from the image-receiving element (such an embodiment is described, for example, in JP-A-56-67840 and Canadian Patent 674,082). It is described in).

Further, in another form in which peeling is not necessary, a photosensitive element is coated on one transparent support, a white reflective layer is coated thereon, and an image receiving layer is further laminated thereon. An embodiment in which an image receiving element, a white reflective layer, a release layer, and a photosensitive element are laminated on the same support, and the photosensitive element is intentionally peeled off from the image receiving element is described in US Pat. No. 3,730,718.

Furthermore, at least (a) a dye image-receiving layer on a white support,
(B) a release layer, (c) a photosensitive element sequentially having at least one silver halide emulsion layer combined with a dye-releasing redox compound, an alkali processing composition containing an opacifying agent, and a transparent cover sheet. A color diffusion transfer photographic film unit may also be used in the present invention.

(Example) Example 1 A laminate-integrated color diffusion transfer photosensitive sheet and a cover sheet were prepared as follows.

Preparation of Photosensitive Sheets Photosensitive Sheets 1 to 9 were prepared by coating each layer on a polyethylene terephthalate transparent support in the following order.

(1) Copoly [styrene-N-vinylbenzyl-N-methyl-piperidinium chloride] 3.0 g / m ² , gelatin
An image receiving layer containing 3.0 g / m ² .

The number of sites is 6.6 × 10 ^-3 equivalent / m ² .

(2) titanium dioxide 20 g / m ^2, a white reflective layer containing gelatin 2.0 g / m ^2.

(3) light-shielding layer containing carbon black 2.0 g / m ² gelatin 1.5 g / m ^2.

(4) The following cyan DRR compound was 0.36 g / m ² , tricyclohexyl phosphate was 0.09 g / m ² , 2,5-di-t-pentadecylhydroquinone 0.008 g / m ² , and gelatin 0.8.
Layer containing g / m ² .

(5) Red sensitive inner latent type direct positive silver bromide emulsion (1.03 in terms of silver amount)
g / m ² ), gelatin 1.2 g / m ² , the following nucleating agent 0.04 mg / m ² and 2-sulfo-5-n-pentadecylhydroquinone
Red-sensitive emulsion layer containing sodium salt 0.13 g / m ² .

(6) 2,5-di-t-pentadecylhydroquinone 0.43g
/ m ² , trihexyl phosphate 0.1 g / m ² and gelatin
Layer containing 0.4 g / m ² .

(7) 0.3g of the following magenta dye releasing redox compound
/ m ² , tricyclohexyl phosphate (0.08g / m ² ),
2,5-di-tert-pentadecylhydroquinone (0.009g /
m ² ) and a layer containing gelatin (0.5 g / m ² ).

(8) Green-sensitive inner latent type direct positive silver bromide emulsion (0.82 in terms of silver amount)
g / m ² ), gelatin (0.9 g / m ² ), the same nucleating agent (0.03 mg / m ² ) as in layer (5) and 2-sulfo-5-n-pentadecylhydroquinone sodium salt (0.08 g / m ² ). m ² ) containing a green-sensitive emulsion layer.

(9) The same layer as (6).

(10) Yellow dye-releasing redox compound (0.53 g / m ² ) having the following structure, tricyclohexyl phosphate (0.13 g / m ² ).
g / m ^2), 2,5- di -t- pentadecylhydroquinone (0.014g / m ²⁾ and a layer containing gelatin (0.7g / m ^2).

(11) Blue-sensitive internal latent direct positive silver bromide emulsion (1.09 in silver amount)
g / m ² ), gelatin (1.1 g / m ² ), the same nucleating agent as layer (5) (0.04 mg / m ² ), 2-sulfo-5-n-pentadecylhydroquinone sodium salt (0.07 g / m ² ). a blue-sensitive emulsion layer containing m ² ).

(12) Each of the UV absorbers with the following structures is 4 × 10mol /
m ^2, and the ultraviolet absorbing layer containing gelatin 0.30 g / m ^2.

(13) A protective layer containing polymethylmethacrylate latex (average particle size 4 μ, 0.10 g / m ² ), gelatin (0.8 g / m ² ), and triacroyltriazine (0.02 g / m ² ) as a hardener.

Configuration of cover sheet A In order on a transparent polyethylene terephthalate support,
The following layers (1 ') to (4') were applied to prepare a cover sheet.

(1 ') acrylic acid having an average molecular weight of 50,000 - butyl acrylate (weight ratio 8: 2) copolymer 10 g / m ² and 1,4-bis (2,3-epoxypropoxy) - butane 0.2 g / m ² The applied neutralization layer.

(2 ') A second timing layer formed by coating cellulose amotate having an acetylation degree of 51.0% and methyl vinyl ether maleic acid monomethyl ester alternating copolymer at a weight ratio of 95/5 at 7.5 g / m ² .

(3 ′) An auxiliary neutralizing layer containing 1.05 g / m ^{2 of} a methyl vinyl ether-maleic anhydride alternating copolymer and 0.98 mmol / m ² of 5- (2-cyano-1-methylthio) -1-phenyltetrazole.

(4 ') Styrene-n-butyl acrylate-acrylic acid-N-methylol acrylamide 49.7 to 42.3 to 3
Pair 5 copolymer latex and methyl methacrylate-
A 93: 4: 3 (weight ratio) copolymer latex of acrylic acid-N-methylolacrylamide was mixed so that the solid content ratio of the former latex and the latter latex was 6: 4, and the mixture was applied to a thickness of 2 μm. First timing layer.

Composition of treatment liquid A The photosensitive sheet produced in this way was designated as No. 1 and No. 2
~ No. 1 except No. 5 except that the kind and amount of salt shown in Table 1 was added
Was prepared in the same manner as in.

In order to examine the raw storability of No. 1 to No. 5 photosensitive sheets, the change in photographic property after storage under the forced temperature and humidity conditions shown in Table 1 was tested.

Regarding the photographic properties, after exposing the photosensitive sheet with a continuous wedge wedge, the processing solution and the cover sheet were combined and developed through a pair of pressure rollers. Dmax and Dmin are shown in Table 1 from the data obtained by measuring the density with a color densitometer after 1 hour.

As is clear from Table 1, in the photosensitive sheet of the present invention, the change in photographic property during life is extremely small.

Example 2 Photosensitive Sheets No. 2-1 to No. No. 2-1 to No. 2 were used in the same manner as in Example 1 except that the mordant shown in Table 2 was used in Layer 1 of Example-1 and bromine salt was added as shown in Table 2. .2-6 was produced. At this time, the amount of mordant applied was unified to 6.6 × 10 ^-3 equivalent / m ² .

 The evaluation of life time was performed in the same manner as in Example 1.

It can be seen from Table 2 that the decrease in Dmax in the photosensitive sheet of the present invention is small. In particular This is remarkable when a mordant having a large number of carbon atoms is used as a substituent around the site.

Claims (1)

[Claims] 1. A halogenation in combination with a dye-donor compound.
Silver emulsion layer and dye image receiving layer containing mordant on the same support
The quaternary ammonium salt portion represented by the general formula (M) is repeated in the color diffusion transfer photographic element having
Containing a polymer contained in the polymer unit as a mordant, andContains bromide ion equivalent to 0.2-10% of the total number of sites
Color diffusion transfer method photographic element characterized byWhere R¹Represents a hydrogen atom or an alkyl group. R²Is al
It represents a kill group, a substituted alkyl group or an aralkyl group. R³And R^FourMay be the same or different, hydrogen atom, halogen
Atom, alkyl group, substituted alkyl group, aralkyl group or
Represents an aryl group. R³And R^FourAre unitedYou may form the ring containing. However, R², R³, R^FourHas a total carbon number of 6 or more. L represents a divalent linking group. n represents 1 or 0.
X Is an anion that forms a salt with a quaternary ammonium ion
(However, excluding bromide ion).