JPH0374820B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD This invention relates to photographic elements and, more particularly, to photographic elements in which cracking is prevented in photographic layers having polymeric mordants and hydrophilic colloids used in the photographic elements. (Background technology) In the field of photographic technology, U.S. Patent Nos. 3709690 and 3958995 are
Quaternary ammonium salt polymers described in JP-A-55-22766, etc., or British Patent No. 2056101 and US Patent No. 4115124.
No. 4282305, No. 4273853, etc. It is known to use a polymer having a tertiary imidazole ring in its side chain as a mordant. It is known that these mordants are usually used in the form of polymer latex or water-soluble polymer. This type of polymer mordant usually contains a hydrophilic colloid such as gelatin as a binder on a support: JP-A-48-33826, JP-A-53-50736;
Specific examples are described in European Patent No. 76492), o-sulfonamide phenols (including o-sulfonamide naphthols: JP-A-51-113624, JP-A-56)
−12642, No. 56-16130, No. 56-16131, No.
Specific examples are described in No. 57-4043, No. 57-650, US4053312, and European Patent No. 76492), hydroxysulfonamide heterocycles (Japanese Unexamined Patent Publication No. 51-104343,
Specific examples are given in European Patent No. 76492), 3-sulfonamide indoles (particularly used coated on top of other coatings; however, coatings with polymeric mordants and hydrophilic colloids of this type exhibits significantly different mechanical properties compared to coated films formed from hydrophilic colloids alone: a mixed film of a polymeric mordant and, for example, gelatin, exhibits significantly different tensile properties compared to a film of gelatin alone. It was found that the strength and elongation at break significantly decreased, resulting in a brittle film.This deterioration in the brittleness of the coating film is the cause of cracks caused by thermal and mechanical strain that occurs during the coating and drying processes. Then,
This significantly limits manufacturing conditions such as coating and drying. Furthermore, when the mixed film of the polymer mordant and gelatin is used as a mordant layer in a color diffusion transfer method or a heat-developable photographic element in which the image-receiving element is peeled off after being transferred, the image-receiving element is thermally or It has also been found that the mordant layer in the receiver element undergoes layer failure when subjected to mechanical strain. Such layer destruction does not occur in a film made of gelatin alone, but is caused by deterioration of the brittleness of the mixed film due to the mixing of the polymer mordant and gelatin, as described above. Such destruction of the mordant layer is a serious failure that significantly reduces the quality of photographs, and a solution to this problem has been desired. (Object of the Invention) The object of the present invention is, firstly, to coat a photographic layer containing a polymer mordant and a hydrophilic colloid on a support.
To provide a photographic element which is prevented from cracking during drying. A second object is to provide a photographic element in which the photographic layer is prevented from being destroyed by thermal or mechanical strain after coating and drying.
The third object is to provide a photographic element in which the photographic layer after development is not destroyed by thermal or mechanical strain. DESCRIPTION OF THE INVENTION The object of the invention is to provide a photographic element having an image-receiving layer on a support containing at least a polymer mordant and a hydrophilic colloid, the image-receiving layer further having a glass transition temperature of 40° C. or less, preferably a This is effectively accomplished by a photographic element characterized in that it contains a polymeric latex other than a polymeric mordant at a temperature below 20°C. Preferred examples of the polymer latex used in the present invention include styrene-butadiene copolymer latex, polyacrylic ester latex, polyvinyl acetate latex, ethylene-vinyl acetate copolymer latex, and vinyl chloride copolymer latex. Although it is a combined latex, it is not particularly limited to these. Specific examples of the polymer latex used in the present invention are shown below. Note that the glass transition points of these polymer latexes were all 40°C or lower. PR-1 (styrene) _a - (butadiene) _b copolymerization latex Copolymerization ratio a:b = 7:3 PR-2 Polymeryl acrylate latex PR-3 Polyethyl acrylate latex PR-4 Polyvinyl acetate latex PR-5 (Vinyl acetate) _a - (ethylene) _b copolymerization latex Copolymerization ratio a:b = 9:1 PR-6 (vinyl acetate) _a - (ethyl acrylate) _b
Copolymerization latex Copolymerization ratio a:b=1:1 PR-7 (vinyl chloride) _a - (ethyl acrylate) _b
Copolymerization latex Copolymerization ratio a:b=3:2 PR-8 (styrene)-(butadiene)-

[Formula] -(Acrylic acid) copolymer latex Butadiene content 40% by weight PR-9 (Styrene)-(Butadiene)- Copolymer latex Butadiene content: 30% by weight The mixing ratio of the polymer latex and polymer mordant used in the present invention can be easily determined by those skilled in the art depending on the type of polymer mordant and the composition. Polymer mordant ratio is 5/
It is preferable to use a ratio of 95 to 95/5, preferably 20/90 to 50/50. The effect of the polymer latex used in the present invention is particularly remarkable when a polymer mordant having a high glass transition point is used. The polymer latex used in the present invention is preferably contained in a mordant layer containing a polymer mordant, but may be contained in an adjacent layer. The polymer mordant used in the present invention is not particularly limited, but a polymer containing a vinyl monomer unit having a tertiary amine group or a quaternary ammonio group represented by the following general formula ()-() is preferred. General formula () [In the formula, R ₁ represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms. L is 1-20
represents a divalent linking group having 5 carbon atoms. E
represents a heterocycle containing as a constituent a nitrogen atom having a double bond with a carbon atom. n is 0 or 1. ] General formula () [In the formula, R ₁ , L, and n represent the same as in the general formula (). R ₄ and R ₅ each represent the same or different alkyl group having 1 to 12 carbon atoms, or an alkyl group having 7 to 20 carbon atoms, and R ₄ and R ₅ are interconnected and nitrogen A cyclic structure may be formed together with the atoms. n is 0 or 1. ] In the general formulas () to (), R ₁ is a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms, such as a methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, n- It represents a hexyl group, etc., and a hydrogen atom or a methyl group is particularly preferred. L is a divalent linking group having 1 to about 20 carbon atoms, such as an alkylene group (e.g., methylene, ethylene, trimethylene, hexamethylene, etc.), a phenylene group (e.g., O-phenylene,
p-phenylene group, m-phenylene group, etc.), arylene alkylene group (e.g.

[Formula] or

[Formula] etc. However, R ₂ represents an alkylene group having 1 to about 12 carbon atoms. ), -CO ₂ -, -CO ₂ -R ₃ - (wherein R ₃ represents an alkylene group, phenylene group, or arylene alkylene group), -CONH-R ₃ - (however, R ₃ represents the same as above) ),

[Formula] (However, R ₁ and R ₃ represent the same thing as above.) etc., and the general formula () [In the formula, R ₁ , L, and n represent the same as in the general formula (). G represents a heterocycle which is quaternized and contains as a constituent a nitrogen atom having a double bond with a carbon atom. X represents a monovalent anion. n is 0 or 1. ] General formula () [In the formula, R ₁ , L, and n represent the same as in the general formula (). R ₄ and R ₅ represent the same thing as in the general formula (). R ₆ is selected from the same ones representing R ₄ and R ₅ . X represents the same thing as in general formula (). R ₄ , R ₅ and R ₆ may be interconnected to form a cyclic structure together with the nitrogen atom. n is 0 or 1. ]

【formula】

【formula】

【formula】

[Formula] −CO ₂ −, −CONH−, −CO ₂ −CH ₂ CH ₂ −, −CO ₂ −
CH ₂ CH ₂ CH ₂ −, −CONHCH ₂ −, −CONHCH ₂
Particularly preferred are _CH2- , _{-CONHCH2CH2CH2- ,} and the _like . In the general formula (), E is a heterocycle containing a nitrogen atom having a double bond with a carbon atom as a constituent, such as an imidazole ring (e.g.

【formula】

【formula】

【formula】

[Formula] etc. ), triazole rings (e.g.

【formula】

[Formula] etc. ), pyrazole rings (e.g.

【formula】

【Formula】na degree. ), pyridine ring (e.g.

【formula】

【formula】

【formula】

[Formula] etc. ), pyrimidine rings (e.g.

[Formula] etc. ), with imidazole rings and pyridine rings being particularly preferred. Preferred specific examples of the polymer containing a vinyl monomer unit having a tertiary amino group represented by the general formula () include US Pat. No. 4,282,305;
The following may be mentioned, including the mordants described in No. 4115124 and No. 3148061.

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

In the general formula (), R ₄ and R ₅ are alkyl groups having 1 to 12 carbon atoms, such as unsubstituted alkyl groups (methyl group, ethyl group, n-propyl group, n-butyl group, n-amyl group, hexyl group, n-nonyl group, n-decyl group, n-dodecyl group, etc.), substituted alkyl groups (methoxyethyl group, 3-cyanopropyl group, ethoxycarbonylethyl group, acetoxyethyl group, hydroxyethyl group, 2- butenyl group, etc.), or an aralkyl group having 7 to 20 carbon atoms, such as an unsubstituted aralkyl group (benzyl group, phenethyl group, diphenylmethyl group, naphthylmethyl group, etc.), substituted aralkyl group (4-
Methylbenzyl group, 4-isopropylbenzyl group, 4-methoxybenzyl group, 4-(4-methoxyphenyl)benzyl group, 3-chlorobenzyl group, etc. ) etc. In addition, as an example where R ₄ and R ₅ are interconnected to form a cyclic structure with a nitrogen atom, for example,

[Formula] (where m is an integer from 4 to 12 represent. ),

Examples include [Formula]. Preferred specific examples of the polymer containing a vinyl monomer unit having a tertiary amino group represented by the general formula () include the following. In the general formula (), G represents a quaternized heterocycle containing a nitrogen atom having a double bond with carbon as a constituent, an example of which is an imidazolium salt.

【formula】

【formula】

【formula】

[Formula] etc. ), Triazolium salts (e.g.

[Formula] etc. ), pyridinium salts (e.g.

【formula】

【formula】

【formula】

[Formula] etc. ), among which imidazolium salts and pyridinium salts are particularly preferred. Here R ₄ is the general formula ()
, and methyl, ethyl, and benzyl groups are particularly preferred. In the general formulas () and (), X represents an anion, such as a halogen ion (e.g. chloride ion,
bromide ion, iodide ion), alkyl sulfate ion (e.g. methyl sulfate ion, ethyl sulfate ion), alkyl or aryl sulfonate ion (e.g. methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid), acetate ion , sulfate ion, etc., and chloride ion and p-toluenesulfonate ion are particularly preferred. Preferred specific examples of polymers containing vinyl monomer units having a quaternary ammonio group represented by the general formula () include British Patent No. 2056101;
No. 2093041, No. 1594961, U.S. Patent No. 4124386,
The following may be mentioned, including mordants described in 4115124, 4273853, 4450224, and JP-A-48-28225.

【formula】

【formula】

【formula】

[p-TsO is

Represents [formula]. ] In the general formula (), as an example where R ₄ and R ₅ are interconnected to form a cyclic structure with the nitrogen atom, for example,

[Formula] (where m is an integer from 4 to 12 represents a number. ),

Examples of forming a cyclic structure with R ₄ , R ₅ , and R ₆ include [Formula].

[Formula] etc. Ru. Quaternary ammonio group represented by general formula ()
Preferred polymers containing vinyl monomer units with
Preferred specific examples include US Pat. No. 3,709,690;
Described in No. 3898088, No. 3958995, etc.
Including mordants, the following may be mentioned: Other polymeric mordants that can be used include rice
National Patent No. 2548564, National Patent No. 2484430, National Patent No.
Disclosed in No. 3148061, Specification No. 3756814, etc.
vinyl pyridine polymers, and vinyl pyridine polymers
nium cationic polymer; US Pat. No. 3,625,694;
No. 3859096, No. 4128538, British Patent No.
Gelatin etc. disclosed in Specification No. 1277453 etc.
Polymer mordants crosslinkable with; U.S. Patent No.
No. 3958995, No. 2721852, No. 2798063, Special
Kaisho 54-115228, Kaisho 54-145529, Kaisho 54-
Aqueous sol type medium disclosed in specification No. 126027 etc.
Dye; disclosed in U.S. Pat. No. 3,898,088
Water-insoluble mordant; US Pat. No. 4,168,976 (Special
1973-137333) Shared with the dye disclosed in the specification etc.
Reactive mordants capable of carrying out the binding; also US
Patent No. 3709690, Patent No. 3788855, Patent No. 3642482
No. 3488706, No. 3557066, No. 3557066, No. 3488706, No. 3557066, No.
No. 3271147, No. 3271148, JP-A-50-71332,
No. 53-30328, No. 52-155528, No. 53-125,
The mordant disclosed in No. 53-1024, U.S.
As described in Patent No. 2675316 and Specification No. 2882156
Examples include mordants and the like. The molecular weight of the polymer mordant used in the present invention is preferably
Preferably between 1000 and 1000000, especially between 10000 and 200000.
Ru. Such polymeric mordants form a mordant layer in a photographic element.
In combination with hydrophilic colloid as a binder
It is used as As a typical example of hydrophilic colloid
For example, proteins such as gelatin, gelatin derivatives, etc.
wood grains, cellulose derivatives, starch, Arabica
Natural substances such as polysaccharides such as
Coal, polyvinylpyrrolidone, polyacrylic
Contains synthetic polymers such as mido. Among these, gelatin and polovinyl alcohol
Particularly preferred. Even if this mordant layer is present in the light-sensitive material, it is also
In dye fixing materials for diffusion transfer method and heat development photography method.
It's okay to be hot. Mixing ratio of polymer mordant and hydrophilic colloid and
The amount of polymer mordant applied depends on the color to be mordanted.
amount of base material, type and composition of polymer mordant, and application
Depending on the image forming method to be used, a person skilled in the art can easily
mordant/hydrophilic colloid
The ratio is 20/80 to 80/20 (weight ratio), the amount of mordant applied
is about 0.2 to about 15g/m²is appropriate, especially 0.5
~8g/m²It is preferable to use it in Polymeric mordants interact with metal ions in photographic elements.
Increase dye transfer density by using in combination
be able to. This metal ion is a medium containing a mordant.
Dyed layer or nearby layer (supports mordant layer, etc.)
(Can be close to or far from the support)
Can be added. Metal ions used here
The material must be colorless and stable against heat and light.
is desirable. That is, Cu₂+, Zn₂+, Ni₂+,
Pt₂+, Pd₂+, Co₃A large amount of reduced metals such as + ions
Valid ions are preferred, especially Zn₂+ is preferable
stomach. This metal ion is usually in the form of a water-soluble compound,
For example ZnSO_Four, Zn(CH₃C.O.₂)₂, added with
The amount added is about 0.01 to about 5g/m²is appropriate,
Preferably 0.1-1.5g/m²It is. In the layer to which these metal ions are added, binder is added.
A hydrophilic polomer can be used as a
Ru. As a hydrophilic binder, it is necessary to first
Contains hydrophilic colloids as specifically listed in
It is for use. Mordant layer containing polymer mordant enhances coating properties
It can contain various surfactants such as
Ru. Also, gelatin hardener may be used in the mordant layer.
I can do it. Gelatin hardener that can be used in the present invention
For example, aldehydes (formaldehyde
De, glyoxal, glutaraldehyde
), N-methylol compounds (dimethylol urea,
methyloldimethylhydantoin, etc.), dioxin
San derivatives (2,3-dihydroxysidioxane
etc.), activated vinyl compounds [1,3,5-tria
Chryloyl-hexahydro-s-triazine, bi
(vinylsulfonyl)methyl ether, N,
N′-ethylene-bis(vinylsulfonylaceta)
), N,N'-trimethylene-bis(vinyls)
sulfonylacetamide)], active halogenation
Compound (2,4-dichloro-6-hydroxy-s-
triazine, etc.), mucohalogen acids (mucochloride, etc.)
chloric acid, mucophenoxychloric acid, etc.),
Sasols, dialdehyde starch, 1-chloro-
Examples include 6-hydroxytriazinylated gelatin.
You can get it. A specific example is U.S. Patent No.
No. 1870354, No. 2080019, No. 2726162, No.
No. 2870013, No. 2983611, No. 2992109, No.
No. 3047394, No. 3057723, No. 3103437, No. 3047394, No. 3057723, No. 3103437, No.
No. 3321313, No. 3325287, No. 3362827, No. 3321313, No. 3325287, No. 3362827, No.
No. 3490911, No. 3539644, No. 3543292, British special
Permit No. 676628, No. 825544, No. 1270578, Doi
Patent No. 872153, Patent No. 1090427, Patent No. 2749260,
Described in Publication No. 34-7133, Publication No. 46-1872, etc.
Ru. Among these gelatin hardeners, especially aldehyde
compounds, active vinyl compounds, and active halogen compounds.
preferable. These hardeners are added directly to the mordant layer coating solution.
However, it may be added to other coating liquids for multilayer coating.
It is also possible to allow it to diffuse into the mordant layer during the process of
stomach. The amount of gelatin hardener used in the present invention is:
It can be selected arbitrarily depending on the purpose. Normally,
About 0.1 to about 0.20wt% of the gelatin used is appropriate.
It is preferably 1 to 8 wt%. Imaging dyes mordanted in photographic elements of the invention
There are the following. i.e. phenol
Hydroxyl group, sulfonamide group, sulfonic acid group, carbon
Azo color with anionic groups such as ruboxyl groups
base, azomethine dye, anthraquinone dye, naph
Toquinone dye, styryl dye, nitro dye, kino
Phosphorous dyes, carbonyl dyes and phthalocyanines
dyes etc. Photographic elements of the invention contain diffusible dyes in an imagewise manner.
Formation or release followed by diffusion followed by fixation.
In color image formation methods, this diffusive dye
It is particularly advantageously used when fixing. The color image forming method described above requires a temperature near room temperature.
Those that are developed using a developer [color diffusion transfer]
Copying method] (for example, the method described in Belgian patent No. 757959)
), heat-developed in a virtually moisture-free state.
[thermal development method] (for example, European patent 76492A2 and special
There are various forms such as those described in 1977-79247).
However, the photographic elements of the present invention may be used in any
Ru. Dye-providing properties useful in the above color image forming method
The substance is expressed by the following formula ( ), silver halide emulsion
used in combination with Dy-Y ( ) Here, Dy is a dye moiety (or its precursor moiety)
, and Y is a dye-donating substance as a result of development.
( ) with a functional substrate that changes the diffusivity of
represent. Here, "diffusivity changes" means (1) Dye donation
sexual substances ( ) is inherently non-diffusible;
Diffusive color change or release of diffusible dye
or (2) an inherently diffusive dye-donating substance.
( ) means that it changes to non-diffusive.
Also, this change is due to the oxidation of Y due to the nature of Y.
Sometimes it occurs, and sometimes it occurs as a result of reduction. As an example of “diffusivity changing” due to oxidation of Y,
First, p-sulfonamide naphthols (p
-Sulfonamide phenols 1977-104343
No. 53-46730, No. 54-130122, No. 57-
Specific examples are described in No. 85055 and European Patent No. 76-492.
), α-sulfonamide ketones (Unexamined Japanese Patent Publication No. 1983-
No. 3819, No. 54-48534, and European Patent No. 76492.
so-called dye-releasing redox such as
Examples include gas substrates. Another example is an intramolecular nucleophilic attack after Y is oxidized.
Unexamined Japanese Patent Publication No. 1983-1988 as a type that releases dye by
No. 20735, and the intramolecular atom described in Japanese Patent Application No. 177148/1983.
Examples include cyst-type substrates. Another example is that under basic conditions, intramolecular
The dye is released by the ring-closing reaction, but Y is oxidized.
List the substrates that virtually no longer cause dye release when
(Specific example in JP-A No. 51-63618)
). Furthermore, as a variation of this, nucleophile
The drug causes the isoxazolone ring to rewind.
Substrates that release dyes are also useful.
Specific examples are described in No.-111628 and No. 52-4819). Another example is that under basic conditions, acidic
Due to the dissociation of the roton, the dye part is released, but T
Substrates that virtually no longer release dye when oxidized
(Japanese Unexamined Patent Publications No. 53-69033, No. 54)
- Specific examples are described in No. 130927). On the other hand, the diffusivity changes due to the reduction of Y.
As an example of
Nitro compounds: JP-A-53-110827,
Keys listed in US.4356249 and US.4358525
Examples include non-compounds. These are developed
The reducing agent (element) that remains unconsumed in the process
(called a chthon donor), and its
The dye is released by intramolecular attack of the resulting nucleophilic group.
It is something to be released. As a variation of this, the reductant acid
The pigment part is released due to the dissociation of sex protons.
Quinone type substrates are also useful.
Specific examples are described in No. 130927 and No. 56-164342). Use a substrate whose diffusivity changes due to the above reduction.
If the exposed silver halide and the dye donor are
A suitable reducing agent (electronic
It is essential to use a thoron donor), and
Specific examples are described in the above-mentioned publicly known materials. Ma
In addition, electron donors coexist in substrate Y.
Substrates (referred to as LDA compounds) are also useful. Yet another dye-donating substance is
Performs redox reaction with silver halide or organic silver salt.
As a result, the mobility of the compound containing the dye moiety changes.
It is possible to use a method that converts into
-Described in No. 39400. In addition, due to the reaction with silver ions in the photosensitive material, mobility is increased.
Regarding dye-donating substances that release dyes, patent application
No. 58-55692. The above-mentioned dye-providing substances can be used to transform light-sensitive materials into light-sensitive materials by development.
Inside, the image-like distribution of mobile pigments corresponding to exposure to light is shown.
These image dyes are dye-fixed.
Transfer it to a fixed material (so-called diffusion transfer) and visualize it.
For information on how to do this, please refer to the patents cited above or
is described in Japanese Patent Application No. 58-42092, No. 58-55172, etc.
It is listed. More details about the photographic elements of the present invention are provided below.
explain. Photographic elements of the invention support a silver halide emulsion layer.
A photosensitive material having at least one layer on a carrier,
It is also a dye-fixing material that does not have photosensitivity.
It's okay to be hot. Or such a photosensitive material (photosensitive
element) and dye-fixing material (image-receiving element) are combined.
It may also be a solid film unit. The typical form of a film unit is one
The above image receiving element and photosensitive element are placed on a transparent support.
are laminated, and after the transferred image is completed, the photosensitive element is
This is a form that does not require peeling off from the image receiving element. Change
Specifically speaking, the image receiving element is at least further
In a preferred embodiment of the photosensitive element, a mordant layer of
In this case, there is a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer.
Combination of emulsion layers, or green-sensitive emulsion layer, red-sensitive emulsion
combination of layers and infrared-sensitive emulsion layers, or blue sensitivity
red-sensitive emulsion layer, red-sensitive emulsion layer and infrared-sensitive emulsion layer
and yellow dye provision to each of the above emulsion layers.
coloring substance, magenta dye-donating substance and cyan dye
Constructed by combining each donor substance
(Here, "infrared light-sensitive emulsion layer is 700 nm or more,
Emulsion layer particularly sensitive to light of 740nm or more
). Then, the mordant layer and the photosensitive layer or dye
A transparent support is inserted between the donor substance-containing layers.
A hard material such as titanium oxide is used to make the transferred image visible.
A white reflective layer containing body pigment is provided. Present in bright light
White reflective layer to allow image processing to be completed
A light-shielding layer may be further provided between the photosensitive layer and the photosensitive layer. or,
If desired, all or part of the photosensitive element may be an image receiving element.
Peel it off at an appropriate position so that it can be peeled off.
A layer may also be provided (such an embodiment is described in, for example,
Described in 1984-67840 and Canadian Patent No. 674082.
ing). In another form that does not require peeling, one transparent support
The photosensitive element described above is coated on the holder, and a white layer is applied on top of the photosensitive element.
A color reflective layer is coated, and an image receiving layer is further laminated on top of it.
be done. An image receiving element and a white reflective layer are placed on the same support.
A release layer and a photosensitive element are laminated, and the photosensitive element
Regarding the mode of intentionally peeling off from the image receiving element
is described in US Pat. No. 3,730,718. other
On the other hand, a photosensitive element and an image receiving element are placed on two supports, respectively.
The typical forms in which the base is painted separately can be roughly divided into
There are two types, one is a peel-off type and the other is a peel-free type.
It is. To explain these in detail, peeling
In a preferred embodiment of the die film unit, the support
It has a light-reflecting layer on the back of its body, and a small amount on its surface.
At least one image-receiving layer is applied. Also photosensitive
The element is coated on a support with a light blocking layer.
Before the end of exposure, the surface coated with the photosensitive layer and the surface coated with the mordant layer are
Although they are not facing each other, after exposure (e.g. development processing)
In middle), the surface coated with the photosensitive layer is turned over and the image-receiving layer is coated.
It is designed to overlap with the surface. in the mordant layer
The photosensitive element receives the transferred image immediately after the transferred image is completed.
peeled from the image element. Also, it is preferable to use a film unit that does not require peeling.
In some embodiments, at least one layer of media is provided on the transparent support.
Coated with a dyed layer and also has a transparent or light-shielding layer
The photosensitive element is coated on the support, and the photosensitive layer
The coated surface and the mordant layer coated surface face each other and overlap.
It is. All of the forms mentioned above are color diffusion transfer methods.
It can also be applied to the heat development method, but the former method is particularly useful.
In some cases, the pressure
Combined with a rupturable container (processing element)
Good too. Among them, the image receiving element and the sensing element are placed on one support.
Units, a film with laminated optical elements that does not require peeling
In this case, this processing element is superimposed on the photosensitive element.
is preferably placed between the cover sheets.
stomach. In addition, a photosensitive element and a receptor are placed on two supports, respectively.
In the form in which the image elements are painted separately, the
During image processing, the processing element is placed between the light-sensitive element and the image-receiving element.
Preferably. Processing elements include files
Depending on the form of the system unit, a light shielding agent (carbon,
dyes whose color changes depending on the pH, etc.) and
and/or white pigments (such as titanium oxide).
Delicious. In addition, color diffusion transfer film
At Nitz, we use a combination of neutralization layer and neutralization timing layer.
A neutralization timing mechanism consisting of a cover sheet,
or incorporated into the image receiving element or into the photosensitive element.
It is preferable to be there. On the other hand, in a heat-developable film unit, the support
metal at appropriate positions on the carrier, photosensitive element or image receiving element.
Sexual particulates, carbon black, graphite, etc.
A heat-generating layer containing conductive particles is provided, and heat development is performed.
Occurs when electricity is applied for the diffusion transfer of pigments and dyes.
Joule heat may also be used. Alternative to conductive particles
semiconductive inorganic materials (e.g. silicon carbide, molybum silicide)
Den, lanthanum chloride, barium titanate
Lamix, tin oxide, zinc oxide, etc.)
good. Next, the present invention will be explained in more detail with reference to Examples.
do. Example 1 Describes how to make benzotriazole silver emulsion.
Bell. 28g gelatin and 13.2g benzotriazole in water
Dissolve in 3000ml. Keep this solution at 40℃ and stir.
Ru. In this solution, 17g of silver nitrate was dissolved in 100ml of water.
Add liquid over 2 minutes. Adjust the pH of this benzotriazole silver emulsion,
Allow to settle and remove excess salt. Then PH 6.30
Yield 400g of benzotriazole silver milk
obtained the drug. How to make silver halide emulsions for the 5th and 1st layers
to write. A well-stirred gelatin solution (in 1000 ml of water)
Contains 20g of gelatin and 3g of sodium chloride at 75°C.
) and sodium chloride and potassium bromide.
600 ml of an aqueous solution containing aluminum and a silver nitrate aqueous solution
(0.59 mol of silver nitrate dissolved in 600 ml of water)
Additions were made simultaneously at equal flow rates over 40 minutes. this
Monodisperse cubes with an average particle size of 0.40μ
A silver chlorobromide emulsion (50 mol% bromine) was prepared. After washing with water and desalting, add 5 mg of sodium thiosulfate and
Droxy-6-methyl-1,3,3a,7-tet
Chemical sensitization was performed at 60℃ by adding 20mg of razaindene.
Summer. The yield of emulsion was 600 g. Next,
Describe how to make a silver halide emulsion for three layers. A well-stirred gelatin solution (in 1000 ml of water)
Contains 20g of gelatin and 3g of sodium chloride at 75°C.
) and sodium chloride and potassium bromide.
600 ml of an aqueous solution containing aluminum and a silver nitrate aqueous solution
(0.59 mol of silver nitrate dissolved in 600 ml of water)
Additions were made simultaneously at equal flow rates over 40 minutes. this
Monodisperse cubes with an average particle size of 0.35μ
A silver chlorobromide emulsion (80 mol% bromine) was prepared. After washing with water and desalting, add 5 mg of sodium thiosulfate and
Droxy-6-methyl-1,3,3a,7-tet
Chemical sensitization was performed at 60℃ by adding 20mg of razaindene.
Summer. The yield of emulsion was 600 g. Next, how to make a gelatin dispersion of the dye-donating substance.
Let's talk about. 5g of yellow dye-donating substance (A), interface
2-ethyl-hexyl succinate as activator
Sodium ester sulfonate 0.5g, triisononi
Weigh 10g of luosphate and add 30ml of ethyl acetate.
Add and heat to about 60℃ to dissolve to make a homogeneous solution.
Ru. This solution and a 10% solution of lime-processed gelatin 100
After stirring and mixing with g, use a homogenizer for 10 minutes.
Distributed at 10,000 RPM during the time. Inject this dispersion into
It is called a dispersion of a yellow dye-donating substance. Using magenta dye-donating substance (B) and high
Tricresyl phosphate as boiling point solvent
Perform the same procedure as above except using 7.5g.
A dispersion of Zenta's dye-donating substance was prepared. Yeah
Cyan dye is provided in the same way as the rho dye dispersion.
It was made using a chemical substance (C). As a result of these methods, a color photosensitive film with a multilayer structure as shown in the following table is used.
I made the materials.

【table】

【table】

Next, a method for producing a dye-fixing material having an image-receiving layer will be described. First, gelatin hardener H-1 (0.75g), H-2
(0.25 g) and 160 ml of distilled water were added, followed by 100 g of 10% acid-treated gelatin and mixed uniformly. This mixed solution was uniformly applied onto a paper support laminated with polyethylene in which titanium oxide was dispersed to a wet film thickness of 60 μm, and then dried.
Next, add mordant P-1 (10 g) and 200 ml of distilled water, add 100 g of 10% lime-treated gelatin, mix uniformly, and apply the mixture uniformly on the above coating to form a wet film of 85 μm. did. This sample was dried to prepare sample (A). Samples (B) and (C) were prepared in exactly the same manner except that 2g of polymer latex PR-4 and PR-8 were added.
It was created. Gelatin hardener H-1 CH ₂ =CHSO ₂ CH ₂ CONHCH ₂ CH ₂ NHCOCH ₂
SO ₂ CH=CH ₂ Gelatin hardener H-2 A tungsten light bulb is used in the color photosensitive material with the above multilayer structure, and G, whose concentration continuously changes,
R, IR three-color separation filter (G is 500-600nm,
R is 600-700nm bandpass filter, IR is
The sample was exposed to light at 500 lux for 1 second through a filter (constructed using a filter that transmits at least 700 nm). Then 140℃
The mixture was heated uniformly for 30 seconds on a heat block heated to Next, 20 ml of water was supplied to the membrane side of the dye-fixing material ^per square meter, and the heat-treated photosensitive coatings were stacked on the fixing material so that the membrane surfaces were in contact with each other. After heating for 6 seconds on a heat block at 80°C, the dye fixing material is peeled off from the photosensitive material, and yellow, magenta, and cyan colors are displayed on the fixing material corresponding to the G, R, and IR three-color separation filters, respectively. The image was obtained. The maximum density (Dmax) of each color was measured using a Macbeth reflection densitometer (RD519). Next, the treated dye-fixing material was dried at 25° C. for 24 hours, and then cut into 5 cm x 5 cm samples. This sample was attached to the outside of a polyvinyl chloride cylinder with an outer diameter of 9 cm using adhesive tape at 60°C and relative humidity of 5.
% condition for 24 hours and a crack test was conducted. Table 1 shows the state of cracks in each sample before and after the crack test.

[Table] As is clear from Table 1, the dye fixing material of the present invention does not exhibit any cracks. Next, a transparent film with an ultraviolet absorbing layer is placed on the film surface of the dye fixing material having these negative images, and xenon light (100,000 lux) is applied onto the color image using an Atlas C.I65 Weather-Ometer. It was irradiated for 3 days. The color image density before and after xenon light irradiation was measured to evaluate the fastness of the color image to light. Table 2 shows the maximum density and dye residual ratio at a reflection density of 1.0 for the dye fixing materials (A) to (C).

[Table] Dye concentration before light irradiation As shown in Table 2, the dye fixing material of the present invention containing a polymer latex with a low glass transition point has a high density of the transferred color image and a high fastness under light irradiation. It is clear that cracking is significantly less likely to occur without reducing properties. This is surprising in light of the rule of thumb that the addition of chemicals to the mordant layer usually worsens color image fastness to light.

Claims (1)

[Claims] 1. A photographic element having an image-receiving layer on a support containing at least a polymer mordant and a hydrophilic colloid, which further contains a polymer latex other than the polymer mordant having a glass transition point of 40° C. or less in the image-receiving layer. A photographic element characterized by containing.